10.1007@978 3 030 36540 0 PDF

11th International
Symposium on
High-Temperature
Metallurgical
Processing
EDITED BY
Zhiwei Peng
Jiann-Yang Hwang
Jerome P. Downey
Dean Gregurek
Baojun Zhao
Onuralp Yücel
Ender Keskinkilic
Tao Jiang
Jesse F. White
Morsi Mohamed Mahmoud
The Minerals, Metals & Materials Series
Zhiwei Peng Jiann-Yang Hwang
• •
Jerome P. Downey Dean Gregurek

• •
Baojun Zhao Onuralp Yücel

• •
Ender Keskinkilic Tao Jiang

• •
Jesse F. White Morsi Mohamed Mahmoud

•
Editors
11th International
Symposium
on High-Temperature
Metallurgical Processing
123
Editors
Zhiwei Peng Jiann-Yang Hwang
Central South University Michigan Technological University
Changsha, China Houghton, MI, USA
Jerome P. Downey Dean Gregurek

Montana Technological University RHI Magnesita
Butte, MT, USA Leoben, Austria
Baojun Zhao Onuralp Yücel

The University of Queensland Istanbul Technical University
Brisbane, QLD, Australia Istanbul, Turkey
Ender Keskinkilic Tao Jiang

Atilim University Central South University
Ankara, Turkey Changsha, China
Jesse F. White Morsi Mohamed Mahmoud

Elkem Carbon AS King Fahd University of Petroleum
Kristiansand, Norway and Minerals
Dhahran, Saudi Arabia
ISSN 2367-1181 ISSN 2367-1696 (electronic)

The Minerals, Metals & Materials Series
ISBN 978-3-030-36539-4 ISBN 978-3-030-36540-0 (eBook)
https://doi.org/10.1007/978-3-030-36540-0
© The Minerals, Metals & Materials Society 2020
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Preface
This book presents selected papers submitted for the 11th International Symposium
on High-Temperature Metallurgical Processing organized in conjunction with the
TMS 2020 Annual Meeting and Exhibition in San Diego, California, USA. More
than 120 abstracts were received. After reviewing them and the submitted manu-
scripts, over 90 were accepted for publication in this book.
As the title of the symposium suggests, the interest of the symposium is on
thermal processing of minerals, metals, and materials that intends to promote
physical and chemical transformations of materials to enable the extraction and
production of valuable materials such as metals, alloys, ceramics, and compounds.
The symposium was open to participants from both industry and academia and
focused on innovative high-temperature technologies including those based on
non-traditional heating methods as well as their environmental aspects such as
handling and treatment of emission gases and by-products. Because
high-temperature processes require high-energy input to sustain the temperature at
which the processes take place, the symposium addressed the needs for sustainable
technologies with reduced energy consumption and lowered emission of pollutants.
The symposium also welcomed contributions on thermodynamics and kinetics of
chemical reactions, phase transformations that take place at elevated temperatures,
as well as simulation of high-temperature metallurgical processes. We hope the
book will serve as a reference for both new and experienced metallurgists, partic-
ularly those who are actively engaged in exploring innovative technologies and
routes that lead to more energy-efficient and environmentally sustainable solutions.
v
vi Preface
We would like to acknowledge the contributions from the authors of included

papers, the time and effort that reviewers dedicated to the manuscripts, and the help
from the publisher. We also thank Dr. Foquan Gu for his help in identifying and
screening manuscripts.
Zhiwei Peng
Jiann-Yang Hwang
Jerome P. Downey
Dean Gregurek
Baojun Zhao
Onuralp Yücel
Ender Keskinkilic
Tao Jiang
Jesse F. White
Morsi Mohamed Mahmoud
Contents
Part I Simulation of High-Temperature Processes

Hydraulic Model Study of Combined Blowing in 65t Electric Arc
Furnace (EAF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Xuetao Wu, Rong Zhu, Guangsheng Wei, Kai Dong and Lingzhi Yang
A New and Highly Efficient Argon Blowing Mode for a 70t
Steelmaking Ladle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Zhanpeng Tie, Qun Hu, Xiaosong Li, Jinwen Liu, Jiaquan Zhang,
Zhanbing Yang and Haiyan Tang
A Kinetic Model for the Interaction of FeO with MgO-14.5 wt% C
Refractory Under the Conditions of the Novel Flash Ironmaking
Technology (FIT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Rahul Sarkar and Hong Yong Sohn
The Narrow Window Evaluation Model of Converter Operation
Process Based on the Logistic Regression Algorithm . . . . . . . . . . . . . . 33
Chao Chen, Nan Wang, Haiyang Yu and Min Chen
The Development of a Heat and Mass Transfer Model for a Shaft
Kiln to Preheat Manganese Ore with Hot Air, Model Development
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Sifiso N. Sambo, Carolina S. A. Hockaday and Tumisang Seodigeng
Numerical Simulation Study on Optimization of Large-Capacity
Single-Strand Tundish Flow Control Devices . . . . . . . . . . . . . . . . . . . . 55
Ai-ping Zhang, Ming-mei Zhu, Yong Zhong and Bing Huang
Predictive Modeling and Optimization of the Variant Combinations
of Material Ratios in the Gasification–Reduction Coupling Process . . . 67
Yiru Yang, Lei Guo, Qipeng Bao and Zhancheng Guo
vii
viii Contents
Part II Energy Efficient Clean Metallurgical Technologies

Clean and Efficient Recovery of Precious Metals from Ag-Rich
Lead Slime Anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Bin Yang, Guozheng Zha, Xiaofeng Zhang, Xiangfeng Kong,
Daxin Huang, Wenlong Jiang, Dachun Liu and Baoqiang Xu
Effects of Electrolytic Parameters on the Deposition of Boron
at the Cathode During Molten Salt Electrolysis of Silicon . . . . . . . . . . 93
Tao Wang, Zhongliang Tian, Shu Yang and Yanqing Lai
The Application of an Effective Equilibrium Reaction Zone Model
Based on CALPHAD Thermodynamics to Steel Making . . . . . . . . . . . 101
Paul Mason, A. Nicholas Grundy, Ralf Rettig, Lina Kjellqvist,
Johan Jeppsson and Johan Bratberg
Optimization Dephosphorization Process of the Early Stage in 300t
Steelmaking Converter with Top and Bottom Combined Blowing . . . . 115
Chao Feng, Rong Zhu, Baochen Han, Kai Dong, Weifeng Li
and Guangsheng Wei
Mechanical Properties of a Laser Deposited Spherical
Ti4822 Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Monnamme Tlotleng, Samuel Skhosane and Sisa Pityana
Study on the Relationship Between Process Reconstruction
and Energy Saving of Iron and Steel Manufacturing Process
in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Shuangping Wu, Anjun Xu, Qi Zhang and Ji Li
Effect of Magnetic Field on CaO–SiO2–CaF2 Mould Flux:
New Insight from Molecular Dynamic Simulation . . . . . . . . . . . . . . . . 147
Qi Jiang, Weitong Du and Yu Wang
Investigation of the Crack Initiation and Propagation in Super
Duplex Stainless Steel During Hot Working . . . . . . . . . . . . . . . . . . . . . 157
Wei Shen, Fuming Wang, Zhanbing Yang, Changrong Li, Ping Lin
and Xiaojie Zhu
Part III Fundamentals of Metallurgical Processes

Corrosion Behaviors of Al2O3 and ZrO2 Refractories in Contact
with High-Basicity Refining Slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
Liwen Xue, Tongsheng Zhang and Wanlin Wang
Phase Equilibria in the System Al2O3–MnO–SiO2:
Thermodynamic and Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Yunhui Hua and Baojun Zhao
Contents ix
Thermodynamic Analysis of Chlorination of Zinc-Bearing Phases

in Pyrite Cinder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Deqing Zhu, Dingzheng Wang, Congcong Yang, Jian Pan, Hongyu Tian
and Yuxiao Xue
Numerical Simulation Study of Arrangement Height and Angle
of Rotary Hearth Furnace Burner . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
Yang Wang, Chengbo Wu, Yun Huang, Gaopeng Zhang and Ning Mao
Estimation of Thermodynamic Properties of Sodium Magnesium
Silicates by the Polyhedron Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Zhongping Zhu, Jinxiang You, Xin Zhang, Jian Wang, Jiaoyang Duan,
Tao Zhang, Zhiwei Peng, Tao Jiang and Mingjun Rao
Numerical Simulation on Distributor Optimization of Twin-Roll
Strip Continuous Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Yong Zhong, Mingmei Zhu, Aiping Zhang and Bing Huang
Effect of Al and Ca Content on the Behavior of the Inclusion
in High-Grade 304 Type Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . 239
Tongsheng Zhang, Hualong Zhang, Wanlin Wang, Liwen Xue, Shifan Dai
and Guomin Ying
Development of Online Control Software for Precise Calcium
Treatment of Steels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Yan Luo, Weijian Wang, Lifeng Zhang, Yang Liu, Ying Ren
and Wen Yang
Part IV High-Temperature Processing

Effect of CO2 on Vanadium Extraction and Thermal Effect
in Top-Bottom Combined Blowing Converter . . . . . . . . . . . . . . . . . . . 263
Qi Lu, Yu Wang and Pan Li
Control of the Distribution of Vacuum Arcs Within Vacuum Arc
Remelting with Externally Applied Magnetic Fields . . . . . . . . . . . . . . . 273
Paul E. King, Matthew Cibula and Joshua Motley
High Temperature Processing of Tungsten Slag . . . . . . . . . . . . . . . . . . 289
Xu Wang, Xiaodong Ma, Chunfa Liao and Baojun Zhao
Non-isothermal Kinetics of Carbothermic Reduction of Fayalite . . . . . 295
Zhi Li, Guojun Ma, Xiang Zhang and Wei Zhang
Upgrading Pilot-Scale Facility at MINTEK to Evaluate the Effect
of Preheating on Smelter Operations . . . . . . . . . . . . . . . . . . . . . . . . . . 303
Joalet Dalene Steenkamp, Glen Michael Denton and Tertius Pieters
x Contents
Preparation of Expanded Slag Ball with Blast Furnace Slag

by Rotary Cup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
Feifei Pan, Xuewei Lv, Wenchao He and Guishang Pei
Ripening Behavior of Carbides in Low-Carbon Low Alloy Steel
FAS3420H During Spheroidizing Annealing Process . . . . . . . . . . . . . . 329
Shuai Liu, Fuming Wang, Zhanbing Yang, Yongliang Li, Xi Chen
and Lijuan Sun
Study of the Influence of the Angle Between the Bottom Blowing
Elements on the Dynamic Conditions in a 300t Converter . . . . . . . . . . 341
Liujie Yao, Rong Zhu, Huixiang Yu, Kai Dong, Qiang Feng
and Yixing Tang
Part V Extraction and Recovery of Metals

Recovery of Chromium from Ferronickel Slag via Alkaline Roasting
Followed by Water Leaching: Effect of Roasting Atmosphere . . . . . . . 359
Foquan Gu, Yuanbo Zhang, Zhiwei Peng, Huimin Tang, Manman Lu,
Shuo Liu, Zijian Su, Mingjun Rao, Guanghui Li and Tao Jiang
Purification of Crude Selenium and Recovery of Gold and Silver
by Vacuum Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
Guozheng Zha, Xiangfeng Kong, Daxin Huang, Bin Yang, Wenlong Jiang,
Dachun Liu and Qinsong Mei
Effect of P2O5 on the Recovery of Ti from Ti-Bearing Blast Furnace
Slag by Super-Gravity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 381
Yu Du, Jintao Gao, Xi Lan and Zhancheng Guo
A Study on Recovery of Iron from Red Mud by Solid State Reduction
Followed by Magnetic Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Said Eray, Ender Keskinkilic, Mustafa Varol, Yavuz A. Topkaya
and Ahmet Geveci
Self-reduction of Core-Shell EAF Dust-Biochar Composite Pellets
Under Microwave Irradiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
Liancheng Wang, Zhiwei Peng, Lei Yang, Leixia Zheng, Jie Wang,
Wenxing Shang, Anton Anzulevich, Mingjun Rao, Guanghui Li
and Tao Jiang
Recovery of Copper from Copper Smelting Slag Using a Green
Reductant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417
Guorui Qu, Yonggang Wei, Bo Li, Hua Wang, Yindong Yang
and Alexander McLean
Contents xi
Separation of Vanadium from Iron in Vanadium-Rich

Molten Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
Guangfen Liang, Xiangyong Lv, Yandong Li, Huamei Duan,
Dengfu Chen, Mujun Long and Song Xu
Effect of Additives on Semi-molten State Reduction for Titanium
Slag Production from Ilmenite Concentrate . . . . . . . . . . . . . . . . . . . . . 445
Wei Lv, Shiyuan Liu, Junyi Xiang, Xuewei Lv and Yindong Yang
Part VI Treatment and Recycling of Wastes

Effect of La Content on Inclusions and Microstructure of C–Mn Steel
Treated By Ti–Mg–Ca . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Lei Wang, Bo Song, Zhen Liu, Xiaokang Cui and Longfei Li
Research on the Database Construction of Furnace Material
Consumption in EAF Steelmaking Process . . . . . . . . . . . . . . . . . . . . . . 465
Botao Xue, Lingzhi Yang, Yu-feng Guo, Feng Chen, Fuqiang Zheng,
Jinlai Zhang, Hongguo Yao and Xiaolei Hou
Experimental Study on Water Model of Continuous Smelting
Reduction Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
Haijuan Li, Yan Liu, Xiaolong Li and Ting’an Zhang
Theoretical Analysis and Experimental Verification of Formation
of As-Bearing Rare Earth Inclusions in Steel . . . . . . . . . . . . . . . . . . . . 489
Bin Bai, Hongpo Wang, Silu Jiang, Lifeng Sun and Yu Wang
Parameters Affecting the Phosphorus Distribution Between Slag
and Liquid Metal in BOF . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
Abdelrhman Hassan and Mohammed Meraikib
Solid-State Reduction Studies for Recovery of Iron from Red Mud . . . 511
Ender Keskinkilic, Saeid Pournaderi, Ahmet Geveci
and Yavuz A. Topkaya
Precipitation Behavior of B2O3 Addition on CaO–Al2O3–Sc2O3 Slag
System Through in Situ Observation . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Fei Wang, Wenke Zhi, Ling Zhang, Zhuangzhuang Liu, Yongnian Dai,
Bin Yang and Muxing Guo
Part VII Preparation of Alloys and Materials

Effect of Intercritical Heat Treatment on Microstructure
and Mechanical Properties of Sn Bearing 33MnCrB5 Steel . . . . . . . . . 531
Lijuan Sun, Fuming Wang, Zhanbing Yang, Changrong Li, Wei Shen,
Shuai Liu and Liang Tan
xii Contents
Production of a Cobalt–Nickel–Iron Alloy from Low-Grade Ore . . . . . 541

Yotamu R. S. Hara, Shadreck Chama, Golden Kaluba,
Douglas Musowoya, Kennedy Chikontwe, Choolwe Muchindu,
Haggai Simfukwe and Stephen Parirenyatwa
Combining Discrete Element Method and Artificial Neural Network
to Predict the Particle Segregation Behaviors at Bell-Less Top Blast
Furnace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Zhehan Liao, Chengfeng Sun, Yang Xu, Muyang Wu, Yizhang Yang,
Chao Wang and Jian Xu
A New Approach for the Production of Li4SiO4 Powder . . . . . . . . . . . 561
Kağan Benzeşik, Ahmet Turan and Onuralp Yücel
Preparation of Metallized Pellets from Blast Furnace Dust
and Electric Arc Furnace Dust Based on Microwave
Impedance Matching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
Lei Ye, Zhiwei Peng, Qing Ye, Liancheng Wang, Robin Augustine,
Joonho Lee, Yong Liu, Mudan Liu, Mingjun Rao, Guanghui Li
and Tao Jiang
Flow Field in a Continuous Casting Tundish with a Novel
Single-Induction Heater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Hong Xiao, Shuo Zhang, Jinwen Liu, Guanghui Wu, Haiying Yao,
Haiyan Tang and Jiaquan Zhang
Modification of Inclusions by Adding Mg to 16MnCrS5
Gear Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
Hui Liu, Yikui Xie, Qiankun Yang, Qi Zhou and Jie Ma
Preparation of Transition Metal Nitrides via Reduction–Nitridation
with Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Yongjie Liu, Yu Zhang, Zhixiong You and Xuewei Lv
Part VIII Sintering and Pelletizing

Evaluation of the Liquid Phase Fluidity During Iron
Ore Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
Huaiying Ma, Zhixing Zhao, Yue Xin, Shuhai Ou and Wen Pan
Magnetite Carbon-Free Sintering Process Based on Electromagnetic
Induction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
Xuangeng Zhou, Xuewei Lv, Zhongci Li, Mingrui Yang, Gang Li,
Zihang Deng, Yongda Li and Linpei Li
A Study of Double Layer Pre-sintering Toward Super-High Bed
Height . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
Mingshun Zhou, Yidong Wang, Dongming Zhao, Jianwei Zhu, Huibo Liu,
Qiang Zhong, Guanghui Li and Tao Jiang
Contents xiii
Reduction Behavior of In-flight Fine Hematite Ore Particles

by CO + H2 Mixtures in a High-Temperature Drop Tube Furnace . . . 653
Liyong Xing, Yingxia Qu, Fanchao Meng, Chunsong Wang
and Zongshu Zou
Effect of Distributor Structure on the Uniformity of Multiphase
System in Fluidized Ironmaking Process . . . . . . . . . . . . . . . . . . . . . . . 663
Wang Tao, Liu Yan, Li Xiaolong, Cao Xuejiao and Zhang Tingan
Prediction of Iron Ore Sinter Strength Using Statistical Technique . . . 673
Zhongci Liu, Xuangeng Zhou, Gang Li, Shanshan Wu and Xuewei Lv
Reducing Carbon and Nitrogen Oxides Emission in Iron Ore
Sintering Process by Double-Layer Pre-sintering Technology . . . . . . . 681
Mingshun Zhou, Yidong Wang, Dongming Zhao, Yan Gu, Jianwei Zhu,
Huibo Liu, Qiang Zhong and Tao Jiang
Research on Mechanism of Ring Formation in Grate-Kiln
of Titanium-Containing Pellets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693
Haoyu Cai, Jianliang Zhang, Zhengjian Liu, Gele Qing and Yan Zhang
Part IX Ironmaking and Steelmaking

Influences of Li2O on the Properties of Ultrahigh-Basicity Mold
Fluxes for Continuous Casting of Peritectic Steel . . . . . . . . . . . . . . . . . 705
Min Li, Yuan bing Wu, Sheng ping He, Qiang qiang Wang
and Qian Wang
Optimization of Process Parameters for the Synthesis of Mo2C
on an Activated Carbon Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
Grant C. Wallace, Jerome P. Downey, Jannette Chorney
and Katie Schumacher
Effect of Refining Slag Composition on the Cleanliness
of 25Cr2Ni4MoV Rotor Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 725
Chao Zhuo, Yimin Zhang, Yanhui Sun, Ruimei Chen and Sicheng Song
Prediction Model of End-Point Molten Steel Temperature
in RH Refining Based on PCA-CBR . . . . . . . . . . . . . . . . . . . . . . . . . . 741
Maoqiang Gu, Anjun Xu, Dongfeng He, Hongbing Wang and Kai Feng
FactSage-Based Design Calculations for the Production
of High-Carbon Ferromanganese on Pilot-Scale . . . . . . . . . . . . . . . . . . 757
Joalet Dalene Steenkamp
Characterization and Formation Mechanism of Oxide Inclusions
in Low-Aluminum Non-oriented Electrical Steels . . . . . . . . . . . . . . . . . 773
Zhiyuan Hu, Qiang Ren, Yan Luo and Lifeng Zhang
xiv Contents
Effect of CO2 Mix Ratios on Materials and Heat Balances

of Bottom-Blowing O2–CaO Converter . . . . . . . . . . . . . . . . . . . . . . . . 779
Weifeng Li, Rong Zhu, Kai Dong, Shaoyan Hu, Guangsheng Wei
and Chao Feng
Numerical Simulation and Optimization of Temperature Field
in the Baking of RH Vessel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 791
Fei Yuan, Xiao Sun, Peiling Zhou and Shuai Deng
Part X Utilization of Complex Ores

Ni Recovery from Nickeliferous Pyrrhotite Concentrates
via a Thermal Concentration Process: Effects of Heat
Treatment Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
Feng Liu and Mansoor Barati
Method to Quantify the Effect of Temperature and Rotational
Speed on the Decrepitation of South African Manganese Ores
in a Rotary Kiln . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
M. S. Moholwa, J. D. Steenkamp and H. L. Rutto
Production of High-Carbon Ferrochromium by Carbothermal
Reduction of Vanadium Extraction Tailings with High Chromium
Content . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
Guang Wang, Jiang Diao, Liang Liu and Bing Xie
Effect of Magnesium Flux on Metallurgical Performance of Pellets . . . 835
Kaikai Bai, Haibin Zuo, Qingguo Xue, Yajie Wang, Jiansheng Chen
and Jun Zhao
Study of Properties and Mineralization of Cu–Ni Bearing Industry
Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
Mudan Liu, Yong Liu, Zhiqiang Chen, Haozi Lv and Bo Li
Utilization of Ground Sinter Feed for Oxidized Pellet Production
and Its Effect on Pellet Consolidation and Metallurgical
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 857
Hongyu Tian, Jian Pan, Deqing Zhu, Dingzheng Wang and Yuxiao Xue
Slag-Metal Separation Behaviors of Vanadium Titanomagnetite
Metallized Pellets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 867
Jianjiang Xin, Nan Wang, Min Chen and Chen Chen
Strengthening Sintering of Limonitic Nickel Laterite by Substituting
Ferronickel Tailings for Sintering Fluxes . . . . . . . . . . . . . . . . . . . . . . . 879
Deqing Zhu, Yuxiao Xue, Jian Pan, Congcong Yang, Zhengqi Guo,
Hongyu Tian and Dingzheng Wang
Contents xv
Part XI Poster Session

Effect of Mechanical Carbon Coating on Reduction of Magnetic
Ore Powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 895
Suju Hao, Tianhao Sun, Wufeng Jiang and Yuzhu Zhang
Effect of Plastic-Coal Mixed Carbonization Reducing Agent
on Direct Reduction Behavior of Carbon-Bearing Pellets . . . . . . . . . . . 901
Jianhao Dong, Guang Wang, Hao Zhang, Jingsong Wang
and Qingguo Xue
Experimental Study of CO2 for Vanadium Extraction by Segmented
Combined Blowing in Converter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 911
Pan Li, Yu Wang and Zheng-Lei Guo
Gasification Behaviors of Biomass with Vanadium Titanomagnetite
as Oxygen Carrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
Wei Cai, Zhucheng Huang, Lingyun Yi, Ronghai Zhong, Xiong Jiang,
Baizhou Tian, Chengfei Hu and Yunyun Jin
Influence of Atmosphere on Melting Behaviour of Synthetic Slags
from Ta Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 931
Dominik Hofer, Stefan Luidold and Ulrich Bartmann
Influence of Process Parameters on the Metal Quality at Electron
Beam Melting of Molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
Katia Vutova, Vania Vassileva, Vladislava Stefanova
and Maria Naplatanova
Preparing Cuspidine Glass-Ceramics from Iron-Removed Stainless
Steel Pickling Sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 953
Guanghui Li, Jian Wang, Jing Chen, Jing-xiang You, Tao Zhang,
Jiao-yang Duan, Qing Ye, Zhiwei Peng, Mingjun Rao and Tao Jiang
Pyrolysis of Waste Steel Tailings and Iron Recovery . . . . . . . . . . . . . . 963
Na Wang, Wei Liu, Junwei Han, Xun Wang, Zihan Li and Wenqing Qin
Research of Gas–Liquid Multiphase Flow in Oxygen-Enriched
Bottom Blowing Copper Smelting Furnace . . . . . . . . . . . . . . . . . . . . . 975
Li Dongbo, Dong Zeshang, Yao Xin, Liu Cheng, Guo Tianyu, Li Bing
and Li Peng
Selective Recycling of Cu Alloys from Metal-Rich Particles
of Crushed Waste Printed Circuit Boards by High-Temperature
Centrifugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 987
Long Meng, Yiwei Zhong, Zhe Wang and Zhancheng Guo
Super-Gravity Field Enrichment of Silver and Antimony Contained
in Pb–Ag–Sb Melts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1001
Xiaochun Wen, Lei Guo, Qipeng Bao, Jintao Gao and Zhancheng Guo
xvi Contents
Synthesis of Na2(Ni, Fe)(SO4)2 Cathode Materials from Nickel

Sulfide Concentrate by Combined Pyro- and Hydrometallurgical
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1013
Guangshi Li, Lizhen Wei, Caixiang Yu, Xiaolu Xiong, Hongwei Cheng,
Qian Xu and Xionggang Lu
Thermodynamic Analysis of Preparation of Cermet
from Zinc Kiln Slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1023
Ning Wang, Hongyan Yan, Chao Luo, Hui Li, Jinglong Liang
and Jun Peng
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
About the Editors
Zhiwei Peng is a Professor in the School of Minerals

Processing and Bioengineering at Central South
University, China. He received his B.E. and M.S.
degrees from Central South University in 2005 and
2008, respectively, and his Ph.D. degree in Materials
Science and Engineering from Michigan Technological
University in 2012. His research interests include heat
transfer in microwave heating, dielectric characteriza-
tion of materials, nonthermal microwave effects,
extractive metallurgy, computational electromagnetics,
microwave absorbing materials, and biomaterials.
Dr. Peng has published more than 120 papers,
including more than 80 peer-reviewed articles in journals
such as International Materials Reviews; Journal of
Hazardous Materials; ACS Sustainable Chemistry &
Engineering; Resources, Conservation & Recycling;
Journal of Cleaner Production; Metallurgical and
Materials Transactions A; Metallurgical and Materials
Transactions B; JOM; Journal of Power Sources;
Fuel Processing Technology; Energy & Fuels; IEEE
Transactions on Magnetics; IEEE Transactions
on Instrumentation and Measurement; Ceramics
International; Powder Technology; and Separation and
Purification Technology. He has served as a Guest Editor
for JOM since 2013 and as an Editor for PLOS ONE and
Cogent Chemistry since 2018. He has been a member
of the editorial boards of Journal of Minerals and
Materials Characterization and Engineering since 2012
and Scientific Reports since 2019, and has served as a
reviewer for more than 50 journals. He received a TMS
Travel Grant Award for the 141st TMS Annual Meeting
xvii
xviii About the Editors
& Exhibition, the Doctoral Finishing Fellowship and

Dean’s Award for Outstanding Scholarship of Michigan
Technological University in 2012, and the Bhakta Rath
Research Award of Michigan Technological University
in 2013.
Dr. Peng is an active member of The Minerals, Metals
& Materials Society (TMS). He has co-organized
8 TMS symposia (Characterization of Minerals,
Metals, and Materials in 2013–2018, and the 9th and
10th International Symposia on High-Temperature
Metallurgical Processing in 2018 and 2019) and
co-chaired 20 TMS symposia sessions since 2012. He
is a member of the Pyrometallurgy and Materials
Characterization Committees and was the Chair of the
Continuing Education Sub-Committee of the Materials
Characterization Committee. He was a winner of the
TMS EPD Young Leaders Professional Development
Award in 2014.
Jiann-Yang Hwang is a Professor in the Department

of Materials Science and Engineering at Michigan
Technological University. He is also the Chief Energy
and Environment Advisor at the Wuhan Iron and Steel
Group Company, a Fortune Global 500 company. He
has been the Editor-in-chief of the Journal of Minerals
and Materials Characterization and Engineering since
2002. He has founded several enterprises in areas
including water desalination and treatment equipment,
microwave steel production, chemicals, fly ash pro-
cessing, antimicrobial materials, and plating wastes
treatment. Several universities have honored him as a
Guest Professor, including the Central South
University, University of Science and Technology
Beijing, Chongqing University, Kunming University
of Science and Technology, and Hebei United
University. Dr. Hwang received his B.S. from
National Cheng Kung University in 1974, and M.S.
in 1980 and Ph.D. in 1982, both from Purdue
University. He joined Michigan Technological
University in 1984 and served as its Director of the
Institute of Materials Processing from 1992 to 2011 and
the Chair of Mining Engineering Department in 1995.
He has been a TMS member since 1985. His research
interests include the characterization and processing of
materials and their applications. He has been actively
About the Editors xix
involved in the areas of separation technologies,

pyrometallurgy, microwaves, hydrogen storage, ceram-
ics, recycling, water treatment, environmental protec-
tion, biomaterials, and energy and fuels. He has more
than 28 patents and has published more than 200
papers. He has chaired the Materials Characterization
Committee and the Pyrometallurgy Committee in TMS
and has organized several symposia. He is the recipient
of TMS Technology Award and of Michigan Tech’s
Bhakta Rath Research Award.
Jerome P. Downey earned his Ph.D. in Metallurgical

and Materials Engineering at Colorado School of Mines
and his B.S. and M.S. degrees in Metallurgical
Engineering at Montana Tech. Dr. Downey is a
Registered Professional Engineer with active licenses
in Colorado and Montana. He has over 40 years of
professional experience that includes industrial opera-
tions, applied process research and development, and
corporate management. His technical expertise includes
chemical and metallurgical thermodynamics, thermal
processing, materials synthesis and processing, and
hazardous materials treatment.
Dr. Downey is presently the Goldcorp Professor of
Extractive Metallurgy at Montana Tech where he serves
as Department Head of Metallurgical and Materials
Engineering as well as the Campus Director of the
Montana University System Materials Science Ph.D.
program. Dr. Downey’s research efforts are currently
focused on the study of fundamental properties of slags,
molten salts, and glasses; vapor phase extraction and
refining of rare earth elements; synthesis and sintering
of non-oxide ceramic and composite materials; and
applications of nanocomposite particles for water
remediation.
xx About the Editors
Dean Gregurek has been a Senior Mineralogist at the

RHI Magnesita Technology Center in Leoben, Austria
since 2001. Dr. Gregurek received his M.Sc. degree at
the University of Graz in 1995 and his doctorate degree
in Applied Mineralogy from the University of Leoben in
1999. Prior to RHI Magnesita, he worked for 2 years for
Luzenac Europe in the talc business. His current
research interests and technical expertise are focused
on chemical and mineralogical studies related to inter-
actions between refractories, molten metals, and slags
from pyrometallurgical furnaces. Dr. Gregurek has been
a TMS member since 2012 and was JOM advisor
(2014–2017), Chair of the Pyrometallurgy Committee,
and a Co-organizer for the 7th–11th International
Symposia on High-Temperature Metallurgical
Processing (TMS Annual Meetings 2016–2020).
Baojun Zhao is the Codelco-Fangyuan Professor in

the School of Chemical Engineering at The University
of Queensland, Brisbane, Australia. His primary fields
of research are fundamental and applied investigations
relevant to high-temperature processing of metals and
materials. He has developed a number of novel research
techniques to enable high-quality research to be carried
out. He has published over 170 refereed journal and
conference papers and received a number of interna-
tional awards to demonstrate his leading research
achievements. He has long-term collaborations with
many international companies on metallurgy and
resources including Baosteel, Dongying Fangyuan
Nonfrrous Metals, Codelco, HBIS, Pangang Group,
Rio Tinto, and Shougang.
About the Editors xxi
Onuralp Yücel completed his technical education

with a Ph.D. in Metallurgical Engineering from
Istanbul Technical University (ITU) where he has held
the position of Professor since 2002. He was a Visiting
Scientist at Berlin Technical University between 1987
and 1988. He carried out post-doctoral studies at New
Mexico Institute of Mining and Technology, Socorro,
USA between 1993 and 1994. Dr. Yücel has as many as
330 publications/presentations to his credit, which
include topics such as technological developments in
the production of a wide range of metals, ferroalloys,
advanced ceramic powders, and the application of
carbothermic and metallothermic processes among
others. He was the Vice Chairman of the ITU
Metallurgical and Materials Engineering Department
(MMED) between 2004 and 2007, Director of the ITU
Applied Research Center of Material Science &
Production Technologies between 2006 and 2012, and
Chairman of the ITU MMED between 2016 and 2018.
Dr. Yücel is a member of the international advisory
board of International Symposium on Boron, Borides,
and Related Materials (ISBB), and has been a
Co-organizer of the TMS International Symposium on
High-Temperature Metallurgical Processing. He also
has been involved with the International Symposium
on Self Propagating High-Temperature Synthesis
(SHS) and International Metallurgy and Materials
Congress (IMMC).
Dr. Yücel’s areas of interest include:
• Pyrometallurgy: Pretreatment of concentrates (pro-

duction of WO3, Sb2O3, As2O3, MoO3); smelting
and reduction of slags; production of ferroalloys,
alloys, and metals carbothermic and metallothermic
processes in EAF or in ladle (copper, cobalt, vana-
dium, chromium, ferroboron, cobalt boron, nickel
boron, ferromolybdenum, ferromanganese, silico-
manganese, ferrovanadium, ferrotungsten, fer-
rochromium, nickel–chromium–molybdenum–iron
and aluminum–titanium–boron alloys).
• Ceramic powder production and processing:
Production of carbide, nitride, boride powders, and
their processing by explosive consolidation or sin-
tering techniques (B4C, TiB2, ZrB2, SiC, CrB2).
xxii About the Editors
• Beneficiation of industrial wastes: Production of

metals and compounds from galvanizing ash, brass
production wastes, and vanadium sludges produced
aluminum production; grit production from alu-
minum, copper, and steel slags.
Ender Keskinkilic earned his undergraduate degree

from the Department of Metallurgical and Materials
Engineering of Middle East Technical University
(METU), Ankara (the capital city of Turkey), in
1999. He continued his M.S. and Ph.D. studies in the
same department. He worked as a Research Assistant at
METU between 1999 and 2003. After receiving his
master’s degree in 2001, he progressed further in the
field of extractive metallurgy. During the Ph.D. period,
he moved to Eregli-Zonguldak in 2003 and worked in
the Quality Metallurgy and RD Department of Eregli
Iron and Steel Works Co. (ERDEMIR), the leading
steel company in Turkey in terms of production
capacity. After earning his Ph.D. degree in 2007, he
returned to university to work in the Department of
Metallurgical and Materials Engineering of Atilim
University, Ankara, in 2008. He has been working as
a faculty member there since then. He was Assistant
Professor between 2009 and 2014. He has been
working as an Associate Professor since 2014. His
primary field of interest is extractive metallurgy, and
more specifically, pyrometallurgical processes such as
ironmaking and steelmaking, ladle metallurgy, ferroal-
loy production, and non-ferrous extractive metallurgy.
He has been acting as the Chairman of the Department
of Metallurgical and Materials Engineering of Atilim
University since July 2018.
About the Editors xxiii
Tao Jiang received his M.S. in 1986 and Ph.D. in

1990, both from Central South University of
Technology. Then he joined the university and served
as an Assistant Professor (1990–1992) and Full
Professor (1992–2000). From 2000 to 2003, he was a
Visiting Scientist in the Department of Metallurgical
Engineering at the University of Utah. Since 2003,
Dr. Jiang has been a Professor in the School of
Minerals Processing and Bioengineering at Central
South University. He was elected as Specially
Appointed Professor of Chang Jiang Scholar Program
of China in 2008 and has been the Dean of the School
since 2010. His research interests include sintering,
pelletizing and non-coke ironmaking of iron ores, and
extraction of refractory gold ores. He has completed
more than 50 projects from government and industry,
including the National Science Fund for Distinguished
Young Scholars Program. He and co-workers invented
the direct reduction process of composite binder pellets,
and three plants were set up in China based on the
invention. He proposed the innovative composite
agglomeration process of iron ore fines, which was
put into production in Baotou Steel Company, China.
He has been actively involved in the areas of utilization
of non-traditional ferrous resources such as complex
ores and various solid wastes. Dr. Jiang has published
more than 300 technical papers, and six books includ-
ing Direct Reduction of Composite Binder Pellets and
Use of DRI, Principle & Technology of Agglomeration
of Iron Ores, Chemistry of Extractive Metallurgy of
Gold, and Electrochemistry and Technology of
Catalytical Leaching of Gold. He holds 42 patents
and has more than 40 conference presentations.
xxiv About the Editors
Jesse F. White holds a Ph.D. in Materials Science and

Engineering from the KTH Royal Institute of
Technology, an M.Sc. in Metallurgical and Materials
Engineering from the Colorado School of Mines, and a
B.S. in Metallurgical Engineering from the South Dakota
School of Mines and Technology. He began his career in
1996 as a Process Engineer at the Kaiser Aluminum
Mead Works. In 1997, he moved to Luleå, Sweden, and
began as a Research Engineer at MEFOS working mainly
in strip casting of steel. In 2002, he moved to Oslo,
Norway and spent 5 years at Alstom as a Project Engineer
designing, building, commissioning, and troubleshoot-
ing gas treatment systems for aluminum smelters around
the world. Since 2007, he has been employed by Elkem in
Kristiansand, Norway; starting out at Elkem Solar as a
Research Engineer specializing in silicon refining, later
moving to Elkem Technology, and since 2015 at Elkem
Carbon. He is currently Technology Director at Elkem
Carbon, supporting the production facilities in Brazil,
China, Malaysia, Norway, and South Africa. In parallel,
Dr. White is also currently an Affiliated Faculty Member
of the Materials Science and Engineering Department at
the KTH Royal Institute of Technology in Stockholm,
where he teaches thermodynamics and conducts research
in the areas of high-temperature experimental thermo-
dynamics and metallurgical reactor design.
Morsi Mohamed Mahmoud joined the Mechanical

Engineering Department at King Fahd University of
Petroleum and Minerals (KFUPM), Saudi Arabia, in
August 2016. He also holds an Associate Professor
position at the Advanced Technology and New
Materials Research Institute (ATNMRI), City for
Scientific Research and Technological Applications
(SRTA City), Egypt. From December 2009 until
August 2016, he worked as a Visiting Assistant
Professor and then as a Senior Scientist at Institute of
Applied Materials—Applied Materials Physics
(IAM-AWP) at Karlsruhe Institute of Technology
(KIT), Germany. Dr. Mahmoud earned his Ph.D. and
M.Eng. degrees in Materials Science and Engineering
from Virginia Tech, Blacksburg, USA in 2007. He has
accumulated unique experience and skills in advanced
materials processing techniques such as microwave
About the Editors xxv
processing, glasses, ceramics, and structure–property–

processing relationship in materials, in addition to a
deep knowledge in materials characterization tech-
niques. He also has had experience organizing and
editing several technical publications, conferences,
web-seminars, and scientific events. He is serving as
the Chairman and the Organizer of the Processing
and Performance of Materials Using Microwaves,
Electric and Magnetic Fields, Ultrasound, Lasers,
and Mechanical Work at the Materials Science &
Technology Technical Meeting and Exhibition 2019
(MS&T19), USA. Furthermore, he served as a
Co-editor for nine books and published 32 technical
papers in the top 10 ISI ranked journals in Materials
Science and Engineering. He was given several pres-
tigious awards such as Virginia Tech Citizen Scholar
Award; an Honor Scholarship from Virginia Tech
Graduate School, USA; and Two German Academic
Exchange Service (DAAD) Fellowships.
Part I
Simulation of High-Temperature Processes
Hydraulic Model Study of Combined
Blowing in 65t Electric Arc Furnace
(EAF)
Xuetao Wu, Rong Zhu, Guangsheng Wei, Kai Dong and Lingzhi Yang
Abstract A hydraulic model with a similarity ratio of 1:4 was used to simulate
the blowing parameters of 65t electric arc furnace (EAF). The molten bath stirring
effects of different bottom blowing arrangements and flow rates under different com-
bined blowing conditions were studied. On this basis, orthogonal experiments were
designed to study the effects of bottom blowing rate, side blowing rate, and bot-
tom blowing arrangement on the mixing time of molten bath. The results showed
that the bottom blowing arrangement has little effect on the mixing time of molten
pool. Under the condition of combined blowing, the degree of influencing factors on
mixing time from big to small was the side blowing rate, bottom blowing rate, and
bottom blowing arrangement. The industrial experiment showed that, compared with
traditional process, the combined blowing process can increase the decarbonization
rate and reduce the consumption of iron and steel materials.
Keywords Electric arc furnace · Hydraulic model · Combined blowing
Introduction
The electric arc furnace (EAF) has played a very important role in the modern
steelmaking process. However, a prominent disadvantage in the process of EAF
steelmaking is that the stirring of the molten pool is weak and the smelting time is
long. The heat generated by the arc directly heats the molten steel in the upper part
of the molten pool, while the molten steel near the bottom and outside the arc zone
X. Wu · R. Zhu (B) · G. Wei · K. Dong

School of Metallurgical and Ecological Engineering, University of Science and Technology
Beijing, Beijing 100083, China
e-mail: zhurong12001@126.com
Beijing Key Laboratory of Research Center of Special Melting and Preparation of High-End
Metal Materials, University of Science and Technology Beijing, Beijing 100083, China
L. Yang
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083,
China
© The Minerals, Metals & Materials Society 2020 3

Z. Peng et al. (eds.), 11th International Symposium on High-Temperature
Metallurgical Processing, The Minerals, Metals & Materials Series,
https://doi.org/10.1007/978-3-030-36540-0_1
4 X. Wu et al.
are heated mainly by convective diffusion of heat. The bottom blowing technique
for EAF steelmaking process was proposed to promote the molten bath fluid flow,
accelerate the metallurgical reaction, and improve the quality of molten steel.
As the EAF steelmaking is a high-temperature and high-pressure process, and
it is accompanied by high-power electric energy transmission, water models and
numerical simulations have been widely used to study the metallurgical effects of
EAF steelmaking [1–4]. Wei [1] established a mathematical model and water model
to study the physical and chemical properties of molten bath with bottom blowing,
and the results showed that bottom blowing could promote mass transfer and increase
the capacity of EAF production. Schade [5] compared the major effects of bottom
blowing with traditional melting conditions without bottom blowing in Lukens steel
company. Li [6] studied the effect of bottom stirring condition on the rising height
of the EAF bath and the mixing characteristics of bottom blowing in EAF through
water model experiments. Li [7] studied the fluid flow and mixing process in a
bottom stirring EAF experimentally and numerically and found that with the bottom
blowing nozzles moving off-center, the angular velocities were increased, and the
stirring efficiency was improved significantly.
Combined blowing technology of EAF combines the characteristics of side blow-
ing and bottom blowing of EAF, which can improve the productivity of EAF and
the quality of steel, reduce energy consumption. In the present study, a hydraulic
model with a similarity ratio of 1:4 was used to simulate the blowing parameters of
65t EAF. The molten bath stirring effects of different bottom blowing arrangements
and flow rates under different combined blowing conditions were studied.
Hydraulic Experiment
In this study, a hydraulic model experiment was carried out to analyze the effect
of combined blowing on the molten bath stirring in EAF, whose instruments were
shown in Fig. 1. The side and bottom blowing gas were injected into the hydraulic
bath through three oxygen lance and three porous plugs. The side oxygen lance
consisted of stainless steel, while the porous plugs consisted of copper rod and
plexiglass. The KCl was applied as the tracer and two conductivity electrodes were
set at different locations to record the mixing time by monitoring the hydraulic
electronic conductivity in the molten bath. In order to make sure that the experiment
results were reliable, two experiments were carried out for each experimental scheme,
and the results should deviate less than 10%.
Table 1 lists the dimensions of hydraulic model which was scaled down by a ratio
of 1:4. The hydraulic and compressed air were, respectively, used to represent the
molten steel and the combined blowing gases (oxygen and argon).
As previously reported, the fluid flow and mixing are caused by momentum
transfer by blowing gases and liquids [8–11]. To ensure the similarity between the
hydraulic model and real EAF, the modified Froude number of two models should
be maintained, and the equations can be expressed by Eqs. (1)–(2).
Hydraulic Model Study of Combined Blowing in 65t … 5
Fig. 1 Combined blowing experimental instruments of hydraulic model experiment
Table 1 Characteristics
Items Prototype Hydraulic model
parameters of prototype and
model Hydraulic diameter(mm) 2274 568.5
Furnace height(mm) 1700 425
Molten bath depth, H(mm) 1300 325
Lance height(mm) 500 125
Lance angle (°) 45 45
Molten bath density (kg/m3 ) 7000 1000
Side blowing gas density 1.429 1.293
(kg/m3 )
Bottom blowing gas density 1.783 1.293
(kg/m3 )
ρgp (π/4)d 2p u 2p ρgw (π/4)dw2 u 2w

Fr = Fr1 , that is = (1)
gρlp (π/4)D 2p H p2 gρlw (π/4)Dw2 Hw2
2 2 2
Qp dp Dp Hp ρlp ρgw
= × × × × (2)
Qw dw Dw Hw ρlw ρgp
where ρ lw , ρ lp , ρ gw , and ρ gp are, respectively, the liquid density of the hydraulic

model, the liquid density of the prototype, the gas density of the hydraulic model,
and the gas density of the prototype, kg m−3 ; d w and d p are the nozzle diameters
of the hydraulic model and the prototype, m; H w and H p are the molten bath depth
of the hydraulic model and the prototype, m; uw and up are the gas velocities of
the hydraulic model and the prototype, m s−1 ; Qw and Qp are the gas flow rates of
the hydraulic model and the prototype, m3 h−1 ; g is the gravity acceleration, m s−2 .
Dw and Dp are the molten bath hydraulic diameter of the hydraulic model and the
prototype, m, and it can be calculated by Eq. (3).
6 X. Wu et al.
Fig. 2 The combined blowing arrangements in EAF model
Table 2 Gas flowrates of

Bottom blowing Side blowing flow
prototype and model (single
flow rate rate (Nm3 · h−1 )
node)
(NL · min−1 )
Prototype 50/100/150/200 1000/1500/2000
Hydraulic model 1.42/2.12/2.82/3.53 12.4/18.6/24.8
D1
π × A
+ D2
× B
+ 2 × L1
D= 2 360 2 360
, (3)
π
where D is the molten bath hydraulic diameter, m.
The oxygen lance and bottom blowing arrangements are shown in Fig. 2, four
different bottom blowing arrangements (A1A2, A1B2, B1A2, and B1B2) will be
analyzed in this study. Based on Eqs. (1)–(3), the parameters of combined blowing
are shown in Table 2.
In this study, the mixing time was defined as the time when the conductivity
between the two electrodes converged and remained stable. The mean mixing time
(T mix ) was calculated by Eq. (5).
T1 + T2
Tmi x = , (5)
2
where T 1 and T 2 are the mixing time of the two experiments for each experimental
scheme, s.
Results and Discussion
Analysis of Hydraulic Model Experiment Results
Orthogonal test design and analysis method is the most commonly used method
of process optimization test design and analysis, and is the main method of par-
tial factor design. Based on probability theory, mathematical statistics, and practi-
cal experience, orthogonal test is a scientific calculation method for dealing with
multi-factor optimization problems efficiently. It arranges test schemes by using
standardized orthogonal table and calculates and analyzes the results. In this experi-
ment, three variables (side blowing flow rate, bottom blowing flow rate, and bottom
blowing arrangements) were taken into consideration and 16 groups of orthogonal
experiments were designed by SPSS (Statistical Product and Service Solutions). The
experimental results are shown in Table 3.
In multivariate analysis of variance, it is required that the data must conform to the
normal distribution of the population, and then the data samples should satisfy the
homogeneity of variance. Therefore, the NPar test is carried out by SPSS software
to determine whether the result is in conformity with normal distribution. As shown
in Table 4, it can be seen that Z = 0.582, P = 0.887 > 0.05, which are in agreement
with the normal distribution of the whole population.
Table 3 Mixing time of different flowing conditions

Variables Side blowing Bottom blowing Bottom blowing Mixing time(s)
flow rate (Nm3 flow rate arrangements T1 T2 T
· h−1 ) (NL · min−1 )
1 18.6 2.12 B1B2 59.2 57.0 58.1
2 18.6 1.42 A1B2 67.4 70.8 69.1
3 12.4 1.42 B1B2 77.0 73.6 75.3
4 24.8 2.12 A1A2 42.0 43.8 42.9
5 24.8 1.42 B1A2 50.1 50.3 50.2
6 12.4 2.82 B1B2 56.9 54.7 55.8
7 12.4 1.42 A1A2 72.0 73.0 72.5
8 12.4 3.53 A1B2 51.8 55.6 53.7
9 24.8 3.53 B1B2 33.0 34.2 33.6
10 12.4 2.12 B1A2 62.5 62.9 62.7
11 12.4 2.12 A1B2 63.0 68.4 65.7
12 12.4 3.53 B1A2 49.8 55.8 52.8
13 18.6 3.53 A1A2 50.0 50.6 50.3
14 24.8 2.82 A1B2 34.5 37.5 36.0
15 12.4 2.82 A1A2 53.4 58.4 55.9
16 18.6 2.82 B1A2 48.7 51.5 50.1
8 X. Wu et al.
Table 4 Kolmogorov–
Mixing time
Smirnov test of single
sample N 32
Normal parametera,b Mean value 55.294
Standard deviation 11.86
The most extreme Absolute value 0.103
difference
Positive 0.068
Negative −0.103
Kolmogorov-Smirnov Z 0.582
Progressive significance 0.887
(bilateral)
a The test distribution is normal distribution
b Calculated from data
The significance level P > 0.05 can be found by the difference homogeneity test,
so it can be inferred that the homogeneity of variance of the analysis data is valid
and the variance analysis can be carried out, as shown in Table 5.
When the significant level P is less than 0.01, the factors have a remarkable impact
on the experimental results; when the significant level is in the range between 0.01
and 0.05, the factors have an important impact on the experimental results; when
the significant level is greater than 0.05, the factors have no significant impact on
the experimental results. As can be seen from Table 5, the significant level P of side
blowing flow rate and bottom blowing flow rate is less than 0.01, which means that
the two factors have a remarkable impact on the mixing time. But the degree of
influence varies greatly, the F value of side blowing flow rate is 439.172 and that
of bottom blowing flow rate is 223.164. It can be seen that side blowing flow rate
has the greatest influence on mixing time, followed by bottom blowing flow rate.
Table 5 Analysis of variance of different elements

Source Square sum of type III df Mean square F Sig.
Correction model 2132.056c 8 266.507 194.455 0.000
Intercept 40640.625 1 40640.625 29653.094 0.000
Side blowing flow rate 1203.802 2 601.901 439.172 0.000
Bottom blowing flow 917.562 3 305.854 223.164 0.000
rate
Bottom blowing 10.692 3 3.564 2.600 0.134
arrangements
Error 9.594 7 1.371
Sum 51060.030 16
Total corrections 2141.649 15
cR square = 0.996 (correction R square = 0.990)
The significant level of bottom blowing arrangements was 0.134, which is bigger
than 0.05, so the influence of bottom blowing arrangements on mixing time was
not significant. The influence of three factors on mixing time is in the order of side
blowing flow rate > bottom blowing flow rate > bottom blowing arrangements.
Table 6 lists the single factor descriptive statistics of the variables. It shows that
the mixing time is the smallest when the side blowing flow rate is 24.8 Nm3 · h−1 .
The average value is largest when the side blowing flow rate is 12.4 Nm3 · h−1 , and
the minimum average mixing time of the bottom blowing flow rate is 3.53 NL·min−1 .
The significant level P is less than 0.05 between the three levels of 12.4, 18.6, and
24.8 Nm3 · h−1 , which reflects that there are significant differences on mixing time
by the side blowing flow rate. Similarly, there has no significant impact on mixing
time between the bottom blowing flow rate is 2.82 NL · min−1 and 3.53 NL · min−1
(P > 0.05), but have remarkable difference among other flow rates (P < 0.01). The
average mixing time was smallest when the bottom blowing position was B1A2, and
there was no significant difference among the bottom blowing arrangements (P >
0.05).
Figure 3 shows the chart of mixing time variation trends. By observing and com-
paring the average mixing time under different combined blowing flow rates, it can
be found that the mixing time of the EAF also follows the rule that the mixing
time decreases with the increase of combined blowing flow rate. From the above
results, the optimum scheme of water model orthogonal test is side blowing flow
rate 24.8 Nm3 · h−1 , bottom blowing flow rate 2.82 NL · min−1 , and bottom blowing
arrangements B1A2.
Table 6 Univariate
Factors Levels Mean value Standard error
descriptive statistics
Side blowing flow 12.4 61.800 0.414
rate 18.6 56.900 0.585
24.8 40.675 0.585
Bottom blowing 1.42 64.606 0.593
flow rate 2.12 55.181 0.593
2.82 47.281 0.593
3.53 45.431 0.593
Bottom blowing A1A2 53.231 0.593
arrangements A1B2 53.956 0.593
B1A2 51.781 0.593
B1B2 53.531 0.593
10 X. Wu et al.
Fig. 3 Chart of mixing time

variation trends
Analysis of Industrial Test Results
The results of hydraulic simulation experiment show that the combined blowing can
effectively stir the molten pool. In order to further study the industrial application
effect of combined blowing, the smelting data of 550 heats with combined blowing
and without bottom blowing were counted.
Table 7 shows the average industrial results of two kinds of flowing patterns.
It can be seen that bottom blowing stirring can reduce the content of FeO in slag,
thereby increasing the yield of metal and reducing the consumption of iron and steel
materials. At the same time, bottom blowing stirring can increase the contact area
of [C], [O] in molten steel, accelerate its mass transfer rate, promote the process of
carbon–oxygen reaction, increase the decarbonization rate, and reduce the end-point
carbon–oxygen deposition. Because of the effect of bottom blowing and stirring, the
slagging process is accelerated, the utilization efficiency of lime is improved, and
the consumption of lime per ton of steel is indirectly reduced.
Figure 4 shows the distribution of main contents in slag with the two conditions,
the content of FeO in slag is reduced by 3.25% under combined blowing conditions
compared with the experimental results without bottom blowing. With the increase of
Table 7 Average industrial results of two kinds of flowing patterns

Item Iron and steel Lime Average [C][O] (10−4 )
consumption consumption decarbonization
(kg · t−1 ) (kg · t−1 ) rate (% · min−1 )
Traditional 1141 69.9 0.127 0.0046
condition
Combined 1130 59.1 0.138 0.0032
blowing
Fig. 4 Distribution of main

contents in slag
bottom blowing, the mass transfer rate from slag (FeO) and molten steel to slag–metal
interface is increased, and the reaction (FeO) + [C] = Fe + CO(g) is intensified.
Therefore, the content of FeO in slag and the oxidation of slag are reduced.
Conclusion
In this study, a hydraulic model with a similarity ratio of 1:4 was used to simulate the
blowing parameters of 65t EAF, and the conclusions can be expressed as follows:
(1) By comparing the average mixing time under different combined blowing flow
rates, it can be found that the mixing time of the EAF also follows the rule that
the mixing time decreases with the increase of combined blowing flow rate.
(2) By measuring the mixing time of different schemes, the optimum combined
blowing scheme is selected as follows: side blowing flow rate 24.8 Nm3 · h−1 ,
bottom blowing flow rate 2.82 NL · min−1 (corresponding to prototype flow
2000 Nm3 · h−1 , bottom blowing flow 150 NL · min−1 ), and bottom blowing
arrangement B1A2.
(3) Through the orthogonal scheme analysis, the influence of each factor on mixing
time is in the order of side blowing flow rate > bottom blowing flow rate >
bottom blowing arrangements.
(4) The industrial test results show that under combined blowing conditions, the
molten pool can be better stirred, the decarbonization and dephosphorization
rate can be increased, and the consumption of iron and steel materials can be
reduced.
Acknowledgements The work was supported by the National Natural Science Foundation of China
(Nos. 51734003 and 51604022).
12 X. Wu et al.
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bath behaviour in the BOF. ISIJ Int 44(5):809–16
A New and Highly Efficient Argon
Blowing Mode for a 70t Steelmaking
Ladle
Zhanpeng Tie, Qun Hu, Xiaosong Li, Jinwen Liu, Jiaquan Zhang,
Zhanbing Yang and Haiyan Tang
Abstract A new argon blowing mode with different flowrates for two purging
bricks of a 70t steelmaking ladle has been explored in the present work. The mixing
behaviour of the molten steel and the slag eye change were revealed by using a 1:3
scale factor of water model. The results show that, compared with the conventional
mode with the same flowrate for each brick, the new mode effectively decreases the
mixing time, and the total area of the slag eye changes slightly. The shortest mixing
time was obtained by the case in which the brick locations are at 0.6 R with a 180°
relative angle and a 22 L/min total flowrate.
Keywords Ladle · Argon blowing mode · Mixing · Slag eye
Introduction
Argon stirring is one of the most effective refining methods for ladle metallurgy in
steelmaking process. It can homogenize the temperature of molten steel and chemi-
cal composition, along with deoxidation, desulphurisation, and removing inclusions
[1–8].
The stirring efficiency is closely related to the argon blowing modes. For a large
capacity ladle, two porous bricks are usually set at the bottom of ladle for argon
injection. In the conventional argon blowing mode (short for S-Mode herein), each
brick is at the same gas flowrate. However, our previous studies [9, 10] for a 120t
ladle provided a novel gas blowing mode (D-Mode) with different gas flowrates for
the two bricks, by which both the mixing time and the slag eye proportion decreased.
Z. Tie · Q. Hu · X. Li · J. Liu · J. Zhang · Z. Yang (B) · H. Tang (B)

University of Science and Technology Beijing, No. 30 Xueyuan Road, Haidian District, Beijing,
China
e-mail: yangzhanbing@ustb.edu.cn
H. Tang
e-mail: tanghaiyan@metall.ustb.edu.cn
Z. Tie
Xining Special Steel Co. Ltd, Xining, China
https://doi.org/10.1007/978-3-030-36540-0_2
14 Z. Tie et al.
Subsequently, the production efficiency and the cleanness of the billet castings in
steel plant were improved.
A 70t ladle with dual porous bricks was adopted in Xining Special Steel. The
industrial trials found that the ladle inner refractory lining was generally eroded
to a great degree, and large size inclusions occupied the high proportion in steel,
which are suspected to be related with the argon blowing system. Therefore, an
optimization of the system in the ladle has been performed by using a water model
in the present work. Additionally, the metallurgical effect of the novel argon blowing
mode mentioned above has been verified on this small-size 70t ladle. A review of
the previous ladle refining work has been reported in the reference [10].
Experimental Principle and Method
A water model was designed for the 70t industrial ladle with a scale of 1:3. The
geometrical size of the ladles is shown in Table 1.
According to the similarity principle, the Froude numbers (Fr ) for the water model
and prototype ladle should be equal, which is given by
ρg u 2
Fr = , (1)
ρl g H
in which
4Q
u= . (2)
(π d 2 )
Based on (Fr )m = (Fr )p ,

21
ρg,p ρl,m dm 4 Hm
Qm = · Qp, (3)
ρg,m ρl,p dp Hp
where ρ g and ρ l represent the densities of gas and liquid, respectively; u is the gas
outlet velocity; H is the bath depth; Q is gas flowrate; d is porous brick diameter;
subscripts p and m denote prototype and model, respectively.
Table 1 Main parameters of

Parameters Prototype Model
prototype and model ladles
Top diameter, mm 2450 817
Bottom diameter, mm 2184 728
Bath depth, mm 2330 777
Top diameter of porous brick, mm 100 33
A New and Highly Efficient Argon Blowing Mode for a 70t … 15
Gas flowrate of the water model is determined by Eq. (3) according to the prototype
flowrate. Their corresponding relationship is shown in Table 2.
Figure 1 shows the water model setup. The mixing of molten steel is studied by an
electric conductivity method. Nitrogen is adopted as the stirring gas to be injected into
the water bath through porous bricks at the bottom of the ladle. 150 mL of saturated
NaCl solution is added into the bath as a tracer. Three electrodes are employed to
determine the conductivity of the tracers. Two electrodes are installed in the active
zones at the top and the middle of the bath, respectively; the third one is installed
in the stagnant zone at the bottom of the bath. The output signal of conductivity
meter is collected by DJ800 multifunctional signal recording system together with a
computer.
The mixing time τ m is adopted as the longest time beyond which the changes of
the electrical conductivities of three electrodes are less than 5% of the steady state
Table 2 Corresponding relationship between gas flowrate of prototype and model, L/min
Prototype, Q p 100 200 300 400 500 600 700 800
Model, Q m 2.8 5.7 8.5 11.4 14.2 17.0 19.9 22.7
Fig. 1 Ladle water model setup

16 Z. Tie et al.
after the addition of a tracer. Each experiment was repeated for five to eight times,
and the average value was taken as the final mixing time.
The experimental variables are given in Table 3. The water model implementation
was divided into S-Mode blowing and D-Mode blowing. For the S-Mode, the total
flowrate of blowing gas was equally allocated to the two bottom porous bricks. For
the D-Mode, however, the blowing gas was divided into a weaker flow of 2.8 L/min
through one brick, and a stronger flow with different flowrates through the other
brick.
A total of 70 experimental cases were designed and performed in the present study.
Concisely, the experimental results of four group cases among them are discussed
here, which are T11-T15, T6-T10, T12-T15, T17-T20, as shown in Fig. 2. In each
case, the mixing behaviours and slag eye proportions are compared under S-Mode
and D-Mode.
Table 3 Experimental variables

Items Prototype Water Model
Brick locations 0.5R 0.33R, 0.5R, 0.6R, 0.70R
Relative angles, º 180 60, 90, 120, 135, 180
Total gas flowrates, L min−1 100–800 2.8–22.7
Fig. 2 Brick locations in the

model ladle
Figure 3 shows the comparison of the mixing time of cases T11-T15, T6-T10, T12-
T15, and T17-T20 under S-Mode and D-Mode, in which T11 and T15 are the loca-
tions of the porous bricks. Case T11-T15-S means that each brick has the same
gas flowrate, that is, the S-Mode, and the given flowrates are 100 + 100 (meaning
T11:100, T15:100), 150 + 150, 250 + 250, 350 + 350, and 450 + 450 L/min,
respectively. Case T11-100-T15-D denotes the gas flowrate for every brick is differ-
ent under D-Mode, in which the flowrates are given through the combination of 100
+ 200, 100 + 400, 100 + 600, and 100 + 800 L/min, respectively.
It should be pointed out that the mixing time decreases with the increase of gas
total flowrate. Because the mixing time is closely related to the stirring energy, while
stirring energy is promoted by the increased gas flowrate. For the same case, the
mixing time of D-Mode is generally shorter than that of S-Mode. For example, for
the case of T6-T10, the bricks are located at 0.6 R away from the centre of the bottom
of the ladle (R is the radius of ladle bottom) with a relative angle of 180°. At S-Mode,
the mixing time is 50, 43, 39, and 33 s corresponding to the total gas flowrate of 300,
500, 700, and 900 L/min, respectively; while at D-Mode, it is 46, 36, 32, and 30 s,
respectively. Similarly, for the case of T17-T20 with the 0.33 R brick position and
the 135° relative angle, the mixing time at D-Mode is shortened for 4, 12, 2, 5 s under
the corresponding flowrates, compared with S-Mode.
For the ladle of dual bricks, when the gas is injected in through bricks, two
circulation flows will form at the sides of every plume. One flow exists between the
plume and ladle wall, and another one is between the two plumes. The circulation
flows between plumes interfere or collide with each other, which leads to a loss
of the stirring energy. The mixing of molten steel in a ladle is mainly governed
by the stirring action from those circulation flows. For D-Mode, the interference
and collision between the plumes are weak; subsequently, more stirring energies are
Fig. 3 Comparison of
mixing time for different
cases under two gas blowing
modes
18 Z. Tie et al.
Fig. 4 Comparison of slag

eye area ratios (ST : total slag
surface area) of case
T11-T15 at two gas blowing
modes
obtained to mix the molten bath, and a circulation trend forms from the strong plume
side to the weak plume side. Therefore, the mixing time is shortened.
It is shown that the D-Mode shortens the mixing time compared with the S-Mode.
However, it has been found at the same time that the dominant slag eye in D-Mode
blowing is larger under the given total flowrate, which possibly leads to an increase
of steel reoxidation. For this consideration, it is necessary to compare the change of
slag eye between the two modes at various gas blowing parameters.
Figure 4 presents the area ratio of slag eyes for the case T11-T15 under the different
blowing modes. The area ratio increases with the increasing gas flowrate. When the
total flowrate is 200 L/min, the slag eye ratio is 0.182 for D-Mode, and 0.184 for
S-Mode; when at 400 L/min, it is 0.264 for D-Mode, and 0.259 for S-Mode. There
is only a slight difference between the two modes.
Morphology of the slag eye for the case T11-T15 is illustrated in Fig. 5. Under
S-Mode, the two slag eyes are almost equal in size. At D-Mode, the strong flowrate
induces a larger eye size, and the weak flowrate produces a smaller one.
For the comprehensive consideration of mixing and slag eye behaviour, it is clear
to see that the new gas blowing mode, D-Mode, fits for this small-sized 70t ladle as
fine as the previous 120t ladle.
Conclusions
(1) Ladle gas blowing mode exerts an influence on the mixing of molten steel and
the size of slag eye. As to the D-Mode, compared with the conventional S-Mode,
the mixing time of the molten steel decreases and the area ratio of the total slag
eye changes slightly.
(2) For the given 70t ladle, with the increase of the gas blowing flowrate, the mixing
time decreases and the slag eye size is enlarged.
Fig. 5 Morphology of slag eye for case T11-T15 at different gas blowing flowrates and modes
(3) The new gas blowing D-Mode fits well for the 70t ladle. The shortest mixing
time is obtained by brick locations at 0.6R with a 180° relative angle and a 22
L/min total flowrate.
Acknowledgements This research was financially supported by the National Natural Science
Foundation of China (No. 51874033, U1860111) and the Beijing Natural Science Foundation (No.
2182038).
References
1. Conejo AN, Rishikesh M, Mazumdar D (2019) Effects of nozzle radial position, separation
angle, and gas flow partitioning on the mixing, eye area, and wall shear stress in ladles fitted
with dual bricks. Metall Mater Trans B 50(3):1490–1502
2. Morales RD, Calderon-Hurtado FA, Chattopadhyay K (2019) Demystifying underlying fluid
mechanics of gas stirred ladle systems with top slag layer using physical modeling and
mathematical modeling. ISIJ Int 59(7):1224–1233
3. Yang F, Jin Y, Zhu CY, Dong XS, Lin P, Cheng CG, Li Y, Sun L, Pan JH, Cai Q (2019) Physical
simulation of molten steel homogenization and slag entrapment in argon blown ladle. Processes
7(8):479
4. Eshwar KR, Ville-Valtteri V, Petri S, Riku M, Timo F (2019) Modeling of the effect of the gas
flow rate on the fluid flow and open-eye formation in a water model of a steelmaking ladle.
Steel Res Int 90(2):1800365
5. Tang HY, Li JS, Xie CH, Sun KM, Wen DS (2009) Rational argon stirring for a 150-t ladle
furnace. Int J Miner Metall Mater 16(4):383–386
20 Z. Tie et al.
6. Mandal J, Patil S, Madan M, Mazumdar D (2005) Mixing time and correlation for ladles stirred
with dual porous plugs. Metall Mater Trans B 36(4):479–487
7. Huang HG, Meng Y, Sun JN (2018) Heat transfer of calcium cored wires and CFD simulation
on flow and mixing efficiency in the argon-stirred ladle. Ironmak Steelmak 45(7):626–634
8. Krishnapisharody K, Irons GA (2006) Modeling of slag eye formation over a metal bath due
to gas bubbling. Metall Mater Trans B 37(5):722–763
9. Tang HY, Liu JW, Zhang S, Guo XC, Zhang JQ (2019) A novel dual bricks gas blowing mode
for efficient ladle metallurgy. Ironmak Steelmak 46(5):405–415
10. Tang HY, Guo XC, Wu GH, Wang Y (2016) Effect of gas blown modes on mixing phenomena
in a bottom stirring ladle with dual bricks. ISIJ Int 56(12):2161–2170
A Kinetic Model for the Interaction
of FeO with MgO-14.5 wt% C Refractory
Under the Conditions of the Novel Flash
Ironmaking Technology (FIT)
Rahul Sarkar and Hong Yong Sohn
Abstract In this work, the interaction of FeO with MgO-14.5 wt% C refractory
under the conditions of the novel flash ironmaking technology (FIT) has been investi-
gated. Carbon from the refractory was oxidized and the formation of magnesiowustite
(Mgx Fe1−x O) solid solution took place as a result of the interaction between FeO and
MgO. A kinetic model for the growth of magnesiowustite was developed based on
the counterdiffusion of Fe2+ and Mg2+ cations and experiments were conducted with
FeO and MgO-14.5 wt% C refractory in the temperature range 1200–1400 °C. The
analyses of samples using SEM-EDX and EPMA confirmed the oxidation of carbon
and the formation of magnesiowustite. Using the kinetic model and the composition
profiles determined from EPMA scans, the values of interdiffusion coefficient, aver-
aged over the composition range ( D̄ Fe−Mg ), were calculated at all the experimental
temperatures. The activation energy for the solid-state diffusion process was obtained
to be 398 kJ/mol.
Keywords Flash ironmaking · Magnesia–carbon · Solid-state diffusion ·

Magnesiowustite
Introduction
A novel flash ironmaking technology (FIT) has been developed in the University of
Utah. In this process, a falling stream of iron ore concentrate is directly converted
to metallic iron by reducing gases such as hydrogen, natural gas, or coal gas in a
flash process. This novel flash ironmaking technology (FIT) aims at overcoming the
shortcomings of the conventional blast furnace (BF) technology. First of all, this
process can be run without the problematical pelletization/sintering steps since it
directly uses iron oxide concentrates. Secondly, the cokemaking step is not required
in the FIT since a gaseous reducing agent is used instead of solid carbon. These
factors greatly influence the energy consumption and the greenhouse emissions and
R. Sarkar (B) · H. Y. Sohn

Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT 84112, USA
e-mail: rahulsarkarmet.89@gmail.com

https://doi.org/10.1007/978-3-030-36540-0_3
22 R. Sarkar and H. Y. Sohn
this process can operate with ~30% less energy input and 39–51% less CO2 emissions
as compared to a BF [1, 2]. Moreover, since the FIT can be operated over a wide of
temperature, it is possible to produce iron in both solid and liquid form through this
process [3–5].
A proper choice of refractory will play an important role in the development of
FIT and its proposed scale-up. Refractories in pyrometallurgical operations are often
quite expensive because they have to endure high temperatures and if the refracto-
ries fail, there is a resultant loss in production and equipment time. These issues are
greatly affected by economic factors and the refractory most appropriate for the FIT
may not necessarily be the one that lasts the longest but rather the one that provides
the best balance between its performance and the initial installation cost [6]. For iden-
tifying a suitable refractory suitable for FIT, understanding the interactions between
iron/iron oxides and the candidate refractories under flash ironmaking conditions is
necessary. This article summarizes the interaction of ferrous oxide (FeO) powder
with magnesia–carbon (MgO–C) refractory under flash ironmaking conditions.
Theory
Thermodynamics
Oxidation of Carbon from MgO–C Refractory
Oxidation of carbon takes place from the MgO–C refractory under flash ironmak-
ing conditions. In the present case, carbon oxidation can take place through either
the direct burnout by O2 (from oxidizing gases such as CO2 and H2 O) or via the
extrinsic oxidation by FeO. The relevant reactions for carbon oxidation via these two
mechanisms are mentioned as follows:
1
C(s) + O2 (g) = C O(g) (dir ect bur nout) (1)
2
FeO(s, l) + C(s) = Fe(s) + C O(g) (extrinsic oxidation) (2)
Under flash ironmaking conditions, both Reactions (1) and (2) are thermodynam-
ically feasible. Therefore, in the actual scenario, carbon oxidation can take place
through either Reaction (1) or (2) or both. Other mechanisms of carbon oxidation
from the MgO–C refractory are available in the literature [7, 8] but in this case, these
two mechanisms are most probable as described in detail elsewhere [9].
A Kinetic Model for the Interaction of FeO with MgO-14.5 wt% C … 23
Interaction of FeO and MgO
The system that needs to be considered for studying the interaction between FeO and
MgO–C refractory is the FeO–MgO system because as already discussed carbon from
the magnesia–carbon refractory oxidizes. Thus, the phases formed in this system as
a result of interaction under FIT conditions were determined from the FeO–MgO
phase diagram. To account for the effect of gas atmospheres, the pseudo-binary
FeO–MgO phase diagrams for p O2 values relevant to FIT were considered. The
only solid solution phase that forms in this system is magnesiowustite (Mgx Fe1−x O)
solid solution [10]. Therefore, under flash ironmaking conditions, the only phase
that is expected to form as a result of interactions between FeO and MgO (from the
magnesia–carbon refractory) is the magnesiowustite solid solution phase.
Kinetic Modeling of FeO–MgO Interaction
In this section, a kinetics model is developed for the growth of magnesiowustite

formed as a result of interaction between FeO and MgO using solid-state diffusion.
Model Assumptions
The following assumptions are first made in the development of this model:
i. The reactions occur isothermally.
ii. The magnesiowustite formed is completely compact and does not contain any
pores.
iii. The molar volume of magnesiowustite (VM W ) has a linear dependence on its
composition.
Interaction Mechanism
Although a number of different mechanisms are possible for the growth of mag-
nesiowustite, the solid-state diffusion in the FeO–MgO system is described by the
counterdiffusion of Fe2+ and Mg2+ cations through a relatively rigid oxygen ion lat-
tice of the rock salt structure of magnesiowustite [11–14]. Therefore, in this work,
the counterdiffusion of Fe2+ and Mg2+ cations through magnesiowustite is chosen as
the dominant interaction mechanism. A schematic representation of this mechanism
is shown in Fig. 1.
Fig. 1 Schematic representation of the interaction mechanism between FeO and MgO (from the
MgO–C refractory) under flash ironmaking conditions
Model Development
The FeO–MgO system follows the regular solution model [15] and hence the volume
change associated with the mixing process of FeO and MgO is zero. This postulation,
along with the assumption of linear dependence of molar volume of magnesiowustite
(VM W ) on its composition, gives
VM W = x · VMg O + (1 − x) · VFeO , (3)
where VMg O and VFeO are the molar volumes of MgO and FeO, respectively.
Furthermore, the difference between VMg O and VFeO is less than 10% at the
experimental temperatures [16] and VM W is expected to be a weak function of the
magnesiowustite composition. In this model, therefore, VM W is assumed to be a
constant over the entire range of magnesiowustite composition.
The quantitative treatment of the problem is done by performing a shell mass
balance of species i (where i can be Fe2+ or Mg2+ ) over a control volume of unit
cross-sectional area and width z in the magnesiowustite layer and taking the limit
z → 0. This gives
∂Ci ∂ Ni
=− , (4)
∂t ∂z
where Ni is the molar flux and Ci is the molar concentration of cation i.

The relationship between Ni and diffusive molar flux (Ji ) is given as
Ni = Ji + X i · N T , (5)
where X i is the mole fraction of cation i with respect to total cations, and N T is the
total molar flux expressed as
N T = N Fe + N Mg . (6)
Since the molar volumes of FeO, MgO, and magnesiowustite are nearly equal,
as discussed, there is no volume change associated with the formation of magne-
siowustite from FeO and MgO. Therefore in the case of FeO–MgO interaction, the
diffusion can be represented as equimolar counterdiffusion and the convective flux
(N T = N Fe + N Mg ) which is the contribution to total flux due to the bulk motion of
the solid is zero. Applying this condition to Eqs. (6) and (5), we get
NT = 0 (7)
Ni = Ji (8)
Using Eq. (8) in Eq. (4), we get
∂Ci ∂ Ji
=− (9)
∂t ∂z
Fick’s first law for binary diffusion is
∂Ci
Ji = − D̄ Fe−Mg · (10)
∂z
where
D̄ Fe−Mg is the interdiffusion coefficient in the Fe2+ –Mg2+ binary system. In gen-
eral, the interdiffusion coefficient is a function of composition. However, as reported
by Liermann and Ganguly [17] in the case of Fe2+ and Mg2+ counterdiffusion, this
dependence is weak. In this work, D̄ Fe−Mg represents the value of the interdiffusion
coefficient averaged over the entire magnesiowustite composition range.
Substituting Eq. (10) in Eq. (9), we get
∂Ci ∂ 2 Ci
= D̄ Fe−Mg · (11)
∂t ∂z 2
The relationship between Ci and X i is given by
Ci = X i /VM W (12)
Substituting Eq. (12) in Eq. (11), we get
∂ Xi ∂2 Xi
= D̄ Fe−Mg · (13)
∂t ∂z 2
It is evident from Eq. (13) that if D̄ Fe−Mg is independent of composition, the

concentration profile for both cations (i.e., Fe2+ and Mg2+ ) will be symmetric about
z = 0, where the origin (i.e., z = 0) is chosen at the initial point of contact between
FeO and MgO. Therefore, it is sufficient to solve Eq. (13) for half of the computational
domain, i.e., in the range 0 < z < ∞. The boundary conditions are given by

X = 0.5
At z = 0 Fe f or all t > 0 (14)
X Mg = 0.5

X Fe = 0
At z = ∞ f or all t > 0 (15)
X Mg = 1.0
The initial condition is given by

X Fe = 0
At t = 0 f or all z > 0 (16)
X Mg = 1.0
The solution to Eq. (13) for these boundary and initial conditions is obtained, after
Crank [18] as
z
X Fe = 0.5 · er f c (17)
2 D̄ Fe−Mg t
z
X Mg = 1 − 0.5 · er f c (18)
2 D̄ Fe−Mg t
From Eq. (17), we get

z X Fe
= er f c−1 =ω (19)
2 D̄ Fe−Mg t 0.5
Thus if the composition profiles at a particular time t are known, D̄ Fe−Mg can be
calculated from the slope of ω versus z plot.
Experimental Work
Excess amounts of FeO powder were applied on both sides of an MgO–C refractory
sample placed inside an alumina crucible. The alumina crucible containing the FeO
and MgO–C was then placed on a carved out fire brick and the entire assembly was
inserted into the hot-zone of a horizontal tubular furnace. After a specific interaction
time, the entire assembly was quickly removed from the hot-zone of the furnace using
a Ti-rod, and the sample along with the crucible was quenched in water and preserved
for analyses. Experiments were conducted at three different temperatures, viz., 1200,
1300, and 1400 °C and at each temperature, experiments were carried out for at least
Fig. 2 p O2 versus
temperature plot for
FeO–MgO–C refractory
experiments compared with
the corresponding values for
Fe–FeO and FeO–Fe3 O4
equilibria
three different interaction times. The gas atmospheres were so maintained that FeO
was the stable oxide of iron at the experimental temperatures. A gas composition of
X H2 = 0.25, X C O = 0.25, and X C O2 = 0.50 satisfied this condition. Hence this gas
composition was used as the initial gas composition for calculating the corresponding
equilibrium gas compositions at the experimental temperatures using HSC version
5.1 [19]. The equilibrium gas compositions were then used for determining the flow
rates of H2 , H2 O, CO, and CO2 . Figure 2 shows the p O2 values for FeO–MgO–C
experiments.
Interaction Mechanism
Carbon Oxidation
As discussed in Sect. 2.1.1, carbon oxidation is thermodynamically possible under

FIT conditions through either direct burnout by O2 or via the extrinsic oxidation
by FeO. SEM-EDX confirmed this possibility and examination of affected refrac-
tory cross-sections from all experiments with FeO and MgO–C refractory showed
that carbon from the refractory was completely oxidized. Figure 3 shows the SEM
micrograph of the unaffected MgO zone of the refractory after interaction with FeO
for 12 h at 1300 °C and p O2 = 1.15 × 10−10 atm (henceforth referred to as sample
FeO–MgO–C-1300-1).
Fig. 3 SEM micrograph of

unaffected MgO zone of the
refractory for sample
FeO–MgO–C-1300-1
Interaction Between FeO and MgO
Since carbon oxidizes from the MgO–C refractory, it is essentially the MgO in the
refractory that interacted with FeO. The interaction of FeO with MgO in the MgO–C
refractory resulted in the formation of magnesiowustite solid solution (Mgx Fe1−x O)
at all temperatures and for all interaction times. Figure 4a shows the SEM micrograph
of the reacted MgO–C cross-section after interaction for sample FeO–MgO–C-1300-
1. Three separate regions were distinguished from the SEM micrograph as shown
in Fig. 4a. They were identified using EDX as ferrous oxide (FeO) at the left, the
MgO–C refractory at the right, and the magnesiowustite (Mgx Fe1−x O) solid solution
in between the two.
Fig. 4 a SEM micrograph of reacted MgO–C refractory cross-section for sample FeO–MgO–C-
1300-1 (MW: Magnesiowustite (Mgx Fe1-x O)); b Concentration profiles for FeO and MgO across
the reacted MgO–C refractory cross-section for sample FeO–MgO–C-1300-1 (Point A is in the
pure FeO region, point B is deep inside the MgO–C refractory, and point C is initial point of contact
between FeO and MgO–C)
Accurate determination of the magnesiowustite (Mgx Fe1−x O) composition as a

function of distance was done using EPMA. Figure 4b shows the concentration
profiles obtained from EPMA line scan for reacted MgO–C cross-section after inter-
action with FeO for sample FeO–MgO–C-1300-1. In Fig. 4b, point A is deep inside
an essentially pure FeO region and point B is in deep inside the unaffected MgO–C
refractory. An elemental line scan from A to B shows that the FeO and MgO concen-
tration remained fairly constant as long as the point analyzed was in the pure FeO
region. Thereafter, the magnesiowustite started to appear in the reacted refractory
cross-section as a result of which there was a continuous decrease in FeO concentra-
tion accompanied by a concurrent increase in MgO concentration. This phenomenon
continues until a point is reached where the magnesiowustite was almost pure MgO
and beyond that point, the concentration profiles flattened out. At point B, there-
fore, the magnesiowustite composition was essentially that of pure MgO. Also, as
evident from Fig. 4b, the concentration profiles for FeO and MgO were symmetric.
Therefore, initial point of contact between FeO and MgO–C can be located from the
concentration profile by identifying the point corresponding to X Fe = X Mg = 0.5.
In Fig. 4b, this point is denoted by C.
Determination of Interdiffusion Coefficient ( D̄ Fe−M g )
After the composition profiles were obtained using EPMA line scans, the interdiffu-
sion coefficient of Fe2+ and Mg2+ cations ( D̄ Fe−Mg ) were obtained using the kinetic
model discussed in Sect. 2.2. For this, the function ω was plotted as a function of z
and from the slope of this curve, D̄ Fe−Mg was calculated using Eq. (19). Figure 5a
shows the plot of ω versus z for sample FeO–MgO–C-1300-1 in which case D̄ Fe−Mg
Fig. 5 a ω versus z plot for sample FeO–MgO–C-1300-1 (z = 0 corresponds to the initial point
of contact between FeO and MgO–C refractory); b Arrhenius plot for interdiffusion coefficient
D̄ Fe−Mg in magnesiowustite
was calculated as 7.5 × 10−13 m2 /s. For a particular temperature, D̄ Fe−Mg values
calculated independently for different interaction times were averaged and plotted in
Fig. 5b as function of inverse of temperature. From the Arrhenius plot, the activation
energy for D̄ Fe−Mg was calculated as 398 kJ/mol.
Conclusions
The following are the conclusions from this work:

1. Carbon from MgO–C refractory was oxidized through either the direct burnout
of carbon by oxidizing gases or the extrinsic oxidation of carbon by FeO or both.
2. The formation of magnesiowustite (Mgx Fe1−x O) occurred as a result of interac-
tion between FeO and MgO from the MgO–C refractory.
3. A kinetics model based on solid-state diffusion has been formulated for the
growth of magnesiowustite (Mgx Fe1−x O) by considering the counter diffusion
of Fe2+ and Mg2+ ions through the magnesiowustite.
4. Using the kinetics model and accurately determined compositional profiles
obtained from EPMA line scans, the values of interdiffusion coefficient ( D̄ Fe−Mg )
were determined at 1200, 1300, and 1400 °C. The activation energy (E a ) for
D̄ Fe−Mg was calculated to be 398 kJ/mol.
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www.hsc-chemistry.net/
The Narrow Window Evaluation Model
of Converter Operation Process Based
on the Logistic Regression Algorithm
Chao Chen, Nan Wang, Haiyang Yu and Min Chen
Abstract The narrow window control of the converter end-point carbon content
and temperature is the main target for improving the refining level and achieving
intelligent manufacturing. According to the practical data of Q235 steel obtained in
converter production, the operation process parameters were discreted based on the
chi-square boxing method combined with the ideal target interval of end-point carbon
content and temperature. At the same time, the key process parameter affecting the
ideal end-point of the converter was guided by WOE value, and the coded data was
scored by logistic regression algorithm. The evaluation model of converter operation
process established in this paper can reasonably identify the bad operating process
parameters, and the recall ratio of the converter production data that does not meet
the ideal end-point target interval is 84%, and the accuracy ratio of evaluation model
is 88%. In addition, the evaluation results indicate that the carbon content and silicon
content of the hot metal are the main factors affecting the convert end-point of this
steel plant, and thus, optimizing the condition of hot metal can achieve the purpose
of narrow window control on the converter endpoint.
Keywords Converter processing parameters · Narrow window control · Evaluation

model · Chi-square boxing method · Logistic regression
C. Chen · N. Wang (B) · H. Yu · M. Chen

School of Metallurgy, Northeastern University, Shenyang 110819, China
e-mail: wangn@smm.neu.edu.cn
C. Chen
e-mail: chen493827846@163.com
H. Yu
e-mail: 1836110212@qq.com
M. Chen
e-mail: chenm@smm.neu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_4
34 C. Chen et al.
Introduction
Intelligent manufacturing is an important symbol showing the modernization level

of the iron and steel enterprise. It is also an important condition to achieve the
minimum cost and energy consumption in the process of production. The converter
steelmaking process is a key part of the steel process, and its stability in hot metal
conditions have an important impact on the quality of steel products. The precise
control of the hot metal condition and smelting operation in the converter is beneficial
to obtain a stable end-point carbon content and temperature, thereby promoting the
smelting process narrow window control. The converter production is the multi-factor
interaction process, so that the condition of hot metal, the operating, and the smelting
cycle have an important effect on the converter end-point temperature and carbon
content. Therefore, the development of converter operation process evaluation model
will help to identify the main factor affecting the converter end-point control, and
optimize the relevant process parameters and precise control of the narrow window.
The twenty-first century is the information era, and the steel company has the massive
data [1]. At the same time, with the rapid development of the cloud platform and the
distributed system technology, the data storage and the computing capability have
been greatly improved [2–4], which makes the data collection from steel companies,
and refining the valuable production information through machine learning possible.
Bai [5] developed a quality control system and realized online production of steel
production, which benefited Cheng De Steel. Rot [6] collected the flame image
data of the converter smelting, and utilized the convolutional neural network to
predict the carbon content of the converter end-point, which brings a high prediction
precise. Liu [7] established an intelligent control system for the quality of the sintering
production line by collecting the actual production data of the sintering plant, which
has improved the yield rate of sinter. These research works are of great significance to
improve the level of intelligent manufacturing of steel mill production. However, the
current production information of the steel plant has combined the human experience
information and machine sensing information, so it is necessary to utilize the big data
to construct the model, which provides more production information for human,
to adjust the production in time. Based on the chi-square box method and logistic
regression algorithm, this paper utilizes the actual production data of the converter to
divide the converter production data and score the operation parameter, then evaluates
the influence degree of the process parameters on the ideal target interval of the
converter according to the WOE value. The evaluation model constructed in this
paper can feedback the converter production process parameters timely, thus guiding
the practice production to narrowly control the end-point of the converter.
The Narrow Window Evaluation Model of Converter Operation … 35
Converter Process Parameters Selection
Based on the actual production data collected at the mill, the total converter produc-
tion data about 1 year was sorted out. The data parameter is shown in Table 1, which
mainly includes the raw material condition, the process operation parameter, and the
end-point target. Among them, the end-point temperature and carbon content are the
target variables, and the steel scrap addition, the hot metal condition, and the smelt
cycle, etc., are processing operation parameters. This paper intends to divide the
ideal target interval reasonably based on the actual requirements of steel production,
and according to the ideal target interval, we utilize the chi-square box method and
logistic regression algorithm to construct the converter evaluation model with non-
linear evaluation function, so as to guide the converter actual production and realize
the narrow window control of the end-point.
Figure 1 is the frequency distribution histogram of the end-point temperature
and carbon content. It can be seen that the overall distribution of the end-point
carbon content and temperature are approximately normal distribution. If the range
of ideal target interval is too large, the constructed evaluation model will bring lower
evaluation efficiency; if the range of ideal target interval is too narrow, the constructed
evaluation model will be too harsh. Therefore, dividing the ideal target interval range
should consider the above two aspects comprehensively.
Table 1 Relative parameters of converter production

Hot metal condition Process operation parameters End-point target
Hot metal w(C)/% Smelt cycle/min End-point temperature/°C
Hot metal w(Si)/% Converter consumption O2 End-point carbon content/%
quantity/Nm3 · h−1
Hot metal w(Mn)/% Lime addition/kg
Hot metal w(P)/% Steel scrap addition/t
Hot metal addition/t Light roasting addition/kg
Hot metal temperature/°C
Fig. 1 Frequency distribution histogram of end-point target

36 C. Chen et al.
Considered with the requirement of the low carbon steel Q235B, the ideal target
interval was reasonably divided. The ideal target interval of the end-point carbon
content is 0.02–0.05%. In order to satisfy the temperature of the refining process, the
ideal target interval of the end-point temperature is 1660–1680 °C. According to the
selected ideal target interval, the actual converter production data of the end-point
carbon content and temperature are re-divided and classified. The data which is in
the ideal target interval is classified as Class I, being seen as ideal data, and the data
which is not in the ideal target interval is classified as Class II, being seen as non-ideal
data.
Evaluation Model Construction
For converter steel production, there are many process parameters affecting the end-
point carbon content and temperature, mainly including the hot metal conditions and
the operating conditions. Figure 2 shows the Pearson correlation coefficient between
the process parameters of the steelworks and the end-point target. It can be seen
that there is no significant linear correlation between all process factors and the end-
point temperature or carbon content, which undoubtedly increases the difficulty of the
precise control in the converter operation to achieve the ideal end-point temperature
and carbon content.
With rapid development of big data, the analysis thing mode has changed from
the causal relationship model to the correlation relationship model [8]. With the help
of a big data model, the relevant factors affecting converter production can be found.
Fig. 2 Correlation
coefficient between converter
process parameters and
end-point objectives
By collecting the actual production data of the converter steel plant, based on the
big data technology, the potential law among the parameters of hot metal, operating
parameters, and smelting cycle is deeply excavated, and the narrow window precise
control of the converter end-point temperature and carbon content can be realized.
Establishment of the Chi-Square Boxing Method Model
The chi-square box method is an applying statistical model. By statistical analysis of

existing data, the degree of influence for the variable on the target can be evaluated [9,
10]. The chi-square box method is used to group the converter production parameter,
then the mass production data is summarized and analyzed, which is a benefit to
analyze the relationship between the converter process factors and the end-point
target.
The algorithm flow of the chi-square box method is (i) sorting every parameters
from low to high; (ii) treating the data with the same value as the same interval; (iii)
using Eqs. (1) and (2) to calculate the chi-square value of each interval; (iv) compare
the chi-square values of adjacent intervals, and merge the similar value intervals
that don’t exceed the chi-square threshold, then repeat steps (i)–(iii) until the proper
number of bins.
Ej = Ni × Cj (1)
2 2
Aj − Ej
X =
2
(2)
j=1
Ej
where Aj is the number of instances of class j in each interval; Ej is the expected

frequency number of Aj ; Ni is the total number of each group; Cj is the total number
of samples in each group of j samples.
The purpose of the chi-square box method is to discretize the continuous data,
which is convenient for further data analysis. Through the chi-square box method,
every parameter will be divide to a certain number interval, and to every interval,
its target distribution will be maximized differently, so that each interval represents
a specific operation. By analyzing the importance of each interval, we can evaluate
the impact of different converter process parameters on the end-point target.
The importance of each interval is determined by the WOE value. The WOE value
of each interval represents its effect on the end-point target. A positive WOE value
indicates that the interval has a good effect on the end-point target, and a negative
WOE value indicates a bad impact on the end-point target. The larger the absolute
value of WOE, the greater is the impact on the end-point target. The calculation of
the WOE value is as shown in the Eq. (3).
38 C. Chen et al.

Pbad
W OE = ln (3)
Pgood
where subscript good represents ideal data and subscript bad represents non-ideal
data. Pgood represents in each interval the proportion of good in all good; Pbad rep-
resents in each interval the proportion of bad in all bad. It can be seen from the
expression on the Eq. (3) that the positive WOE value represents a large negative
influence, while the negative WOE value represents a large positive influence.
In addition, through the chi-square box method and the WOE value calculation,
it is possible to determine the interval contribution of each process parameter in the
converter production to the ideal target interval of the converter endpoint. Generally,
the number of boxes is based on people’s experience. This paper uses an iterative
method to calculate the reasonable number of boxes. The IV value represents the
amount of information contained in the variable. The higher IV value represents the
more information on the end-point target. The calculation of the IV value is as shown
in the Eq. (4).

n

IV = Pbad − Pgood × W OEi (4)
i=1
Through iterative calculation, when the IV value reaches the maximum value, the
number of bins corresponding to the variable is the optimal number of bins, and the
iterative termination condition is taken as the IV value convergence. The information
of the final IV value and the final binning number are shown in Fig. 3. As can be
Fig. 3 IV value of related

parameters and the number
of bins
seen from the figure, the number of boxes in the smelting cycle is 10, the number of
converter consumption O2 quantities is 16, the number of hot metal additions is 4,
the number of steel scrap additions is 30, and the number of light roasting additions
is 5. The number of hot metal w(C) is 48, the number of hot metal w(Si) is 25, the
number of hot metal w(Mn) is 5, the number of hot metal w(P) is 22, the number
of hot metal temperature is 14, and the number of lime addition is 12. The IV value
represents the converter end-point information contained in the different converter
process parameters. The IV value of the hot metal w(C) and the hot metal w(Si) is
high, indicating that the hot metal composition of the steelmaking plant is the most
important for the converter end-point.
Process Parameters WOE Value Statistics
Utilizing statistic knowledge to count the WOE situation of 2418 production data
collected from the steelmaking plant, the result is shown in Table 2. It can be seen
that the WOE mean value of the converter process parameters is −0.1, indicating that
the overall operation of the converter has a good influence on the end-point target;
the WOE variance is 0.72, indicating that the converter operation fluctuates greatly;
the WOE maximum is 2.1, indicating that in the past, the operation of converter has
been a high negative impact operation and should be avoided in actual production.
Figure 4 is a comparison between Class I and Class II with each process parameter
WOE mean value. It can be seen that the WOE value of each parameter in the class I
target data is lower than the WOE value of the class II data, and the WOE value of each
parameter of the class I data is less than 0, and the WOE value of each parameter of the
class II data is higher than 0, indicating that the WOE is available. The positive and
negative values represent the influence of the converter operating process on the ideal
target interval of the endpoint. The WOE computing result indicates that the binning
situation in this paper is reasonable. The difference in WOE mean value between the
hot metal w(C) and the hot metal w(Si) is the largest, indicating that the values of
these two process parameters have a great influence on the ideal target interval of the
converter. The WOE values of hot metal w(Mn), light roasting addition, smelt cycle,
and hot metal addition are all around 0, indicating that these four process parameters
have a relatively stable influence on the ideal target interval of the converter.
Table 2 WOE statistical result of converter process parameters

WOE index The total Mean Variance Min Max Q1 Q2 Q3
number of
boxes
Numerical 191 −0.1 0.72 −2.46 2.1 −0.4 −0.05 0.26
value
40 C. Chen et al.
Fig. 4 Comparison of WOE

mean values between class I
and class II parameters
Establishment of Logistic Regression Model
Every WOE value represents the influence of the data box to the end-point target. By
adding the WOE values linearly, the total influence of the relevant parameters can
be obtained. The higher total influence value means the less likely to reach the ideal
interval. Using the logistic regression algorithm shown in Eqs. (5) and (6), through
the −θ T x, the total influence of each parameter can be calculated, and then through
the function 1+e1 −x , the nonlinear relationship can be mapped.
1
hθ (x) = (5)
1 + e−θT x
p(y/x;θ) = (hθ (x))y (1 − hθ (x))1−y (6)
where θ represents a linear regression coefficient.

Equation (6) is a logistic regression function. The model is using the built-in
logistic regression model of Python sklearn version 0.19. For the calculation results,
the mean value of the class I data is 0.7, and the mean value of the class II data is
0.8. In order to identify the bad data, we set the threshold as 0.7. So if the calculation
result exceeds 0.7, we determine that the data is unqualified.
As can be seen from Table 3, the total data number is 2418. From the results of
the model calculations, the comprehensive accuracy is 79%. For Class II data, the
recall rate is 84% and the accuracy rate is 88%, indicating that the constructed model
can find unqualified data well.
Table 3 Model effectiveness

End-point target Qualified Unqualified Total
assessment
I class 299 218 517
II class 294 1607 1901
Conclusion
Based on the actual production data of the converter, this paper utilizes the chi-
square box method to discretize the data. To the discretized data, we calculate each
box WOE value, and then evaluate the impact of box on the end-point target according
to the WOE value. We found that the hot metal w(C) and the hot metal w(Si) have
higher influence on the end-point target. So in order to achieve the narrow window
control, we should first stable the hot metal w(C) and the hot metal w(Si). To the
discrimination model, the comprehensive accuracy rate of the converter operation
process evaluation model is 79%, and for the data that does not meet the ideal target
interval, the discriminative accuracy rate is 88% and the recall rate is 84%.
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system. Banker 7:20–23
The Development of a Heat and Mass
Transfer Model for a Shaft Kiln
to Preheat Manganese Ore with Hot Air,
Model Development Methodology
Sifiso N. Sambo, Carolina S. A. Hockaday and Tumisang Seodigeng
Abstract This work models the design of a preheater (shaft kiln) to demonstrate
preheating of manganese ores with hot air at 800 °C produced by concentrating
solar thermal energy on a pilot scale. This paper reports the methodology for the
development of a heat and mass transfer model that informs the effective control of the
shaft kiln air flow rates. A continuum approach is followed through the discretisation
of the fluid and solid phases of a packed bed of randomly packed lumpy mineral ore.
The fluid dynamics of the packed bed is solved using correlations for fluid flow
through packed beds and the dimensionless constants for flow, heat convection and
conduction are quantified for a packed bed of manganese ore. The required pressure
drop across the shaft kiln with fluid flow up to 5 m/s is less than 100 kPa. It was also
found that a lumped system does not exist in the solid phase. The validity of the model
will be studied theoretically and through experimental work. Outstanding work on
the methodology includes the solution to the radiative heat transfer, convective mass
transfer, and the method to measure the extent to which the wall effect impacts on
the radial temperature distribution.
Keywords Shaft kiln · Packed bed · Heat and mass transfer · Convection ·
Radiation · Conduction
S. N. Sambo (B) · C. S. A. Hockaday

MINTEK, 200 Malibongwe Drive, Randburg, Johannesburg 2194, South Africa
e-mail: sifisos@mintek.co.za
C. S. A. Hockaday
e-mail: linah@mintek.co.za
T. Seodigeng
Vaal University of Technology Vanderbijlpark, Andries Potgieter Blvd, Vanderbijlpark 1900,
South Africa
e-mail: tumisangs@vut.ac.za

https://doi.org/10.1007/978-3-030-36540-0_5
44 S. N. Sambo et al.
Introduction
This research study models a shaft kiln with packed manganese ore where air is used
for thermal energy transfer in the fluid–solid interface. This is a part of on-going
studies on the implementation of concentrated solar thermal energy in minerals pro-
cessing to eliminate the burning of fossil fuels. If commercialized, this will be the
first application of concentrated solar thermal energy for high temperatures above
400 °C [1]. Heating manganese ore up to 600 °C in oxidizing environment decom-
poses carbonate minerals and vaporizes hydroxides [2] which reduce the amount
of carbon monoxide and water vapor released during smelting in a submerged arc
furnace to save furnace power consumption.
Packed beds provide a high surface area to volume ratio [3], and give effective
heat and mass transfer between fluid and solids in various unit operations. This work
studies the heat transfer process from the fluid (air) to the solids (Mn ore) and the
mass transfer from Mn ore to the fluid phase in the shaft kiln. Several studies [3–5]
have developed heat and mass transfer models for packed beds with fluid to solid
heat transfer. The influence of material and fluid properties, packing arrangement,
and fluid dynamics has appeared to play an important role in these fluid–solid heat
transfer models. Packing structural arrangement is one of the first fundamentals that
need to be understood before an analysis of heat transfer can be carried out. This
is because the characterization of the fluid–solid medium interface is the defining
factor of the transfer process rather than the thermo-physical property of the bed [6].
The column wall affects the geometry of the packing structure both in the radial and
axial direction. This results in existing temperature gradients in the radial direction
due to fluid channelling at the wall surface [7]. The wall effect extends to five particle
diameters in both directions but the axial effect is generally negligible due to the
column height [6]. The axial temperature gradients exist due to the fluid–solid heat
transfer up the column. The axial and radial thermal conductivity contributes to the
overall heat transfer coefficient and a two-dimensional axial dispersion (2DADPF)
model [8] presents the general energy balance for a plug flow model which includes
both the axial and radial bed conductivity as Eq. 1, and the boundary condition
applied at the wall as Eq. 2.

∂T ∂ ∂T ∂2T
GC f = ker r + keax 2 (1)
∂x r ∂r ∂r ∂x
∂T
ker = h w T f − Tw (2)
∂r
G (kg/s) is the fluid mass flux in the axial direction, Cf (J/g K) is the fluid heat
capacity, Tf and Tw are the fluid temperature and bed temperature, respectively, ker
and keax (W/m k) are the radial and axial bed thermal conductivities.
The continuum approach to heat and mass transfer modeling of randomly packed
beds made up of randomly shaped lumpy mineral ores in fluid–solid transport systems
requires a proper fluid dynamic model. This is because the fluid dynamics governs
The Development of a Heat and Mass Transfer Model … 45
the heat transfer in the fluid–solid interface. This problem becomes more complex
because of the random flow pattern and the mixing of the fluid in the void regions.
In principle, the governing Navier Stokes equations of flow must be applied [4]. The
application of the Navier Stokes equations requires well-defined boundary conditions
for all the particles in the packed bed which complicate the solution to the fluid
dynamics problem. Computational discretization allows for the description of the
packed bed as an assembly of discrete particles and provides a solution for the
fluid flow problem. However, the elementary approach (DEM) requires sophisticated
algorithms and high computational power. The continuum approach is simplified in
this work and the fluid flow problem is solved using the experimentally derived
correlations of fluid flow in packed beds.
Methodology
Approach to Packed Bed Modelling
The fluid stream pressure drop is the driving force that ensures the flow of air through
the packed Mn ore up in a shaft kiln. The flow parameters are studied by first defin-
ing the flow regime and relating the pressure drop to the fluid flow velocity using
empirical correlations of flow through packed beds. In principle, packed beds of solid
material of uniform particle size (Dp ) distribution have an equal surface area per unit
volume. This allows for the discretization of the fluid–solid interfaces as a bundle of
tubes within the column cross-sectional area. The fluid tube’s equivalent diameter
(Deq ) and the bed void fraction determine how many such tubes (n) occupy the given
column cross-sectional area (S0 ). The visualization of the packed bed model can be
seen in Fig. 1a, b. Due to the fluid flow pattern, the model length (Lm ) is less than
the actual flow length. However, this is corrected by a constant value determined by
applying the empirical correlations for flow through packed beds.
To define the Mn ore packed bed geometry, assumptions of the shaft kiln dimen-
sions and the characterization of Mn ore size distribution are required. The lumpy Mn
(a) (b)
Dpm
ΔLm
∆h
Fig. 1 a Actual packed bed of length L. b Packed bed model of length Lm
Table 1 Mean particle diameter

Dp range (mm) Dp intervals (mm) Cumulative mass Weight fraction (x) x/Dp i
(kg)
5.6–10.0 7.8 35 0.201 0.0258
10.0–16.0 13 95 0.345 0.0265
16.0–20.0 18 174 0.454 0.0252

Sum x/Dp i 0.0775

Mean particle diameter = 1/ x/Dp i 12.897
ore particle size distribution (Dp ) has shown that particle’s size bigger than 20 mm
contributes over 80% of the Mn ore sample total mass. However, in this work, we
consider the particle’s size of 5.6–20 mm. An internal report on characterization of
the UMK Mn ores has shown equal distribution of mineral’s composition across all
size fractions and this makes it possible to select the desired size fraction. The small
size fraction gives some tolerance for the porosity variation in the radial direction
in small scale columns. To characterize the packed bed as a bed of uniform size
particles, the mean particle diameter (Dpm ) was determined based on the particle’s
size distribution presented in Table 1.
The lumpy Mn ore was characterized as broken solids and the value of sphericity
was adopted from Kunni and Lavenspiel [9] as 0.63. A 200 mm column diameter
(D) and 1200 mm height are used in this work. A column of similar dimensions will
be used for the lab experimental work to validate the model. The Buckingham Pi
theorem and similitudes will be used to scale for larger applications. The packed
bed properties specified above allows for the evaluation of porosity variations across
the packed column but the packed bed average porosity was used for simplicity.
The average bed porosity of the Mn ore was evaluated in the laboratory using fluid
displacement method and was found to be 0.48. The column cross-sectional area
is related to the solid phase and the fluid phase tubes by Eqs. 3 and 4 and the two
equations equate to solve for the equivalent diameter, Eq. 5. The actual fluid flow
velocity (V) is related to the superficial velocity (V0 ) and the porosity (ε) as shown
in Eq. 6. This equation is employed for the evaluation of convection heat and mass
transfer parameters in the fluid–solid interphase. For the given bed porosity, particle
mean diameters (Dpm ) and sphericity (Fs ), and the bed total surface area (S0 ), the
fluid tubes equivalent diameter was found to be 8.03 mm and 298 fluid phase tubes.

6
n π Dpm L = S0 L(1 − ε) (3)
s Dpm

1
n π Deq L = S0 Lε
2
(4)
4

2 × D 2pm × Φs ε
Deq = × (5)
3 (1 − ε)
V0
V = (6)
ε
Convective Heat Transfer
The arrangement of the fluid–solid interface as a bundle of tubes simplifies the

bed characterisation and the heat transfer problem but does not give the correct
dimensionless constants for fluid flow parameters. The pressure drop per unit length
to the fluid flow superficial velocity for flow in packed beds at low Reynolds numbers,
(Rep < 2300) is given by the Kozeny Carmen correlation [9]. At high Reynolds
numbers (Rep > 2300), the effect of the friction factor becomes low (f → constant) and
the pressure drop is evaluated using the Burke Plummer equation [9]. The correlations
enable the assumptions of the fluid velocity given the required pressure drop across
the length of the packed bed. This means that a fully developed velocity profile can be
assumed and the convective heat transfer governing equations can be evaluated. Both
the Kozeny Carmen and the Burke Plummer equations combine to form the Ergun
equation which is used to solve problems where the flow is transitional, however one
term always dominates depending on the Rep values [9].
The value of the measured Mn ore packed bed average porosity is high (0.48) for
randomly shaped particles compared to spherical particles of the same size. This is
caused by the low sphericity values for non-spherical materials. Empirical correla-
tions for porosity values of spherical particles ( = 1) relate the particle’s diameter
to the column diameter as presented in Eq. 7 [6, 8]. The required pressure drop across
the bed of lumpy Mn ore is expected to be lower due to high porosity. However, for
the same Reynolds number, the friction factor is high due to low sphericity of the
Mn ore particles. The friction factor was evaluated using Eq. 8 and the results were
plotted against the values of Rep at a log scale in Fig. 2. It can be seen from Fig. 2 that
the friction factor becomes a constant at high Rep values which shows the transition
from laminar to turbulent flow. All values of the fluid properties, density (ρ), and
viscosity (μ) used were taken at a bulk mean temperature assuming that 80% of the
fluid temperature (800 °C) is lost to the solid phase in the column. The fluid delivery
pressure of 250 kPa was used. Figure 3 below shows the relationship between fluid
superficial velocity and pressure drop for both lumpy Mn ore and spherical Mn ore
of the same size.

D
ε = 0.375 + 0.34 × f bed (7)
Dp
150 1, 75
f bed = + (8)
s Rep
2 s
9.00
8.00
7.00
Friction factor 6.00
5.00
4.00
3.00
2.00
1.00
0.00
2.1 2.9 3.2 3.3 3.5 3.6 3.6 3.7
Log(R e)
bed fric on factor φs =0,63 bed fric on factor φs = 1
Fig. 2 Friction factor against log scale Rep values for spherical and lumpy Mn ore
80.0
70.0
60.0
Pressure drop (Kpa)
50.0
40.0
30.0
20.0
10.0
0.0
0.1 0.8 1.4 2.0 2.6 3.3 3.9 4.5
Velocity (m/s)
Pressure drop φs = 1 Pressure drop φs = 0,63
Fig. 3 Pressure drop against superficial velocity
The packed bed heat transfer coefficient will be evaluated with dimensionless
numbers at an entry region until fully developed temperature profiles are established.
When the whole packed bed is a fully developed region, the local heat transfer
coefficient and the temperature gradients across the bed length remain the same.
Parameters of the entry region determine the start-up time before a continuous flow
of the Mn ore stream to ensure that the furnace feed is at the required temperature of
600 °C. Hot air (800 °C) will be supplied at a constant rate to heat the solids which
are at a lower temperature; this means that a constant wall heat flux arrangement
can be assumed given that the bed is made up of material with constant thermal
conductivity (k), specific heat capacity (Cp ), and thermal diffusivity (α). All Mn ore
thermo-physical properties will be evaluated at the bulk mean temperature. Assuming
that the velocity profile is fully developed, the heat transfer coefficient (h) will be
evaluated using the dimensionless Nusselt number over a length L. For the thermal
entrance region, NuDL is evaluated as a function of a dimensionless axial distance
16.0
14.0
12.0
10.0
NuD
8.0
6.0
4.0
2.0
0.0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2
∆L (m)
Fig. 4 Nusselt number reduction with column length
(L* ) given by Eq. 10 and used in Eq. 9. Two empirical correlations that relate NuD
and L* with limits to the values of L* are presented in Eqs. 11 and 12. ReD (Eq. 13)
is the dimensionless Reynolds number evaluated based on the flow path equivalent
diameter (Deq ) and the fluid viscosity (μ). The dimensionless Prandtl number (Pr )
can be obtained using Eq. 14 and was taken to be 1 for air. Values of the Nusselt
number based on the characteristic length were evaluated for the given packed bed
properties and 1.56 m/s actual fluid velocity and plotted against the column length
(L) in Fig. 4. It can be seen that NuD values decrease across the column length
which indicates that the thermal resistance increases up the column. This indicates
that constant temperature profiles have not been established across the column.
hL
Nu D = (9)
K
L
L∗ = D
(10)
ReD Pr
1
Nu D = 1.953 L ∗ 3 f or L ∗ < 0.03 (11)
0.0722
Nu D = 4.364 + f or L ∗ ≥ 0.03 (12)
L∗
ρV Deq
ReD = (13)
μ
C pμ
Pr = , ≈1 (14)
K
When fully developed temperature profiles are established, the flow of materials
down the column can be assumed. This calls for the evaluation of the fully developed
temperature profiles in axial segments of length L, that is, the temperature profile
(Tn − Tn+1 ) of a given tube segment must remain the same when the solid materials
flow down the column. This means Mn ore at a constant temperature will exit the
column. If this is achieved, the residence time of the materials in the column can be
realized and controlled based on the thermal transport processes that take place. At
this point, the mathematical definition of temperature as a function of the tube radius
(r), the length (L), and a constant (C1 ) that relates the temperature distribution to the
constant wall heat flux (−q/A) can be employed (Eq. 15) and the general energy
equation for laminar flow in a tube of constant properties can be reduced to Eq. 16.
T = f (r ) + C1 L (15)
dT C1 2
r dr = α r VL = Cα1 r Vmax (1 − RR 2
d
dr (16)
at r = 0 : dT
dr
= 0; at r = R(tube wall) : K dTdr
= qA w
The above correlations of convective heat transfer are only applicable for laminar
flow of the fluid through the packed bed. The effect of the boundary conditions and
the thermal entry length becomes small at high Reynolds numbers [10]. For fully
developed velocity and temperature profiles, the local heat transfer coefficient in the
Nusselt number format can be evaluated using the Dittus–Boelter correlation [10, 11]
in Eq. 17. This correlation holds true for 0.3 < Pr < 100, and 2300 < ReD < 1.2 × 105 .
A linear relationship exists between the Nusselt number and the Reynolds number
for the packed Mn ore under fully developed velocity and temperature profiles. The
relationship was evaluated for turbulent flow and the Reynolds number was plotted
against the heat transfer coefficient in Fig. 5.
Nu D = 0.023 × ReD
0.8
× Pr0.4 (17)
4500
4000
3500
h (w/m2K)
3000
2500
2000
1500
2.39 2.73 3.07 3.41 3.75 4.10 4.44 4.78 5.12 5.46 5.80 6.14 6.48 6.83
ReD (10-3)
Fig. 5 The fluid phase heat transfer coefficients for different values of ReD
Conduction Heat Transfer
To study the conduction heat transfer, the focus switches to the solid phase of the
packed bed. An infinitely long cylinder of diameter Dpm subjected to the fluid phase
temperature Tf was considered. Equation 19 gives the unsteady state conduction
general differential equation on a one-dimensional coordinate system neglecting
the heat generation term. Heat generation is negligible because the decomposition
reactions of the carbonate minerals in the Mn ore take place at temperatures above
650
∂2T ∂T
K = ρC p (19)
∂x 2 ∂t
where Cp is the specific heat capacity of the solid materials.
For the given particle size distribution, the significance of internal temperature
gradients was evaluated using the dimensionless Biot number (Bi ) [10] which takes
into account the convective thermal resistance at the surface of the solid materials.
The value of Bi is given by the ratio of the product of the thermal resistance to
convection at the surface (h) and the characteristic length (R) of the material to the
internal thermal resistance (k). Values of Bi > 0.1 indicate that significant temperature
gradients exist for the characteristic length of the solid material when exposed to
the fluid which is at high temperature [10, 11]. The thermo-physical properties of
the Mn ore (Cp and α) were analysed using the laser flesh method using an LFA
457 Microflash at a 100 °C increments. The values of thermal conductivity were
calculated for each temperature using Eq. 20. The analysis results are presented in
Table 2, adopted from PreMa internal report D3.1.
k(T ) = α(T )C p(T )ρ(T ) (20)
The Bi number for the cylindrical slab (Dpm ) evaluated on the fluid bulk mean
temperature and the fluid thermal resistance (h) has given values above 4. To quantify
the temperature gradients, a solution can be obtained by solving for both the length
Table 2 Thermo-physical
T (°C) α (mm2 /s) Cp (J/gK) k (W/mK)
properties of UMK Mn ore
100 0.717 0.846 2.33
200 0.620 0.927 2.20
300 0.548 0.937 1.96
400 0.493 0.976 1.87
500 0.451 0.991 1.68
600 0.402 0.985 1.49
700 0.339 0.886 1.12
800 0.279 0.765 0.79
and the time differential terms in the unsteady state conduction general differential
Eq. (19). The solution to temperature distribution will be obtained as a function of
the dimensionless measure of time (Fourier number (Fu )), dimensionless measure
of location (r/R), and the Biot number. The temperature distribution results are
presented graphically using chart that presents the temperature history at the centre
of an infinitely long cylinder and the ratio of the temperature at any point in an
infinitely long cylinder to the temperature at the centre line [10, 11]. Covered chapters
on unsteady state conduction and presented the product solution in Eq. 21.

θ θr / R=0 θ
= × (21)
θ0 θ0 θr R = 0
where θ = T − T f and θ0 = T0 − T f and θ0 = T0 − T f .
Conclusion
Only the dimensionless parameters of fluid flow, convective, and conduction heat
transfer were evaluated for the shaft kiln and further work on the method to study
the radiative heat transfer and convective mass transfer is outstanding. The required
pressure drop is below 100 kPa for fluid actual flow velocity less than 5 m/s. The
low-pressure requirements will allow for the evaluation of the heat and mass transfer
at a wider range of fluid flow velocity. Bi > 1 indicates that the Mn ore residence
time will play an important role in heat transfer. For a given column diameter and
height, the residence time will be specified at the point where the Mn ore at the kiln
exit point is at 600 °C. The wall effect on the porosity variation in the radial direction
of the packed bed needs to be quantified before attempting to study the temperature
distribution in the radial direction. Manually calculating the transport parameters for
a high number of segments can be challenging and Python has been identified as a
suitable tool for solving problems of this nature. When all the modes of heat transfer
have been defined, the heat transfer coefficients will be summed up to give an overall
heat transfer coefficients for the axial and radial temperature gradients to complete
the model. This will enable the tuning of the fluid flow rate per mass of solid materials
in a shaft kiln of specific dimensions (bed diameter and bed height). The validation
face of this work will be done both theoretically and through lab experiments. This
will give indications in areas where the approach needs to be re-evaluated.
Acknowledgements Sincere gratitude to Mintek and Vaal University of Technology for provid-
ing their facilities for this study and the PreMa project for the funding they put in to make this
work possible. The PreMa project has received funding from the European Union’s Horizon 2020
Research and Innovation Programme under Grant Agreement No 820561.
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simulation study of end effects and D/d ratio on mass transfer in packed beds. Int J Heat &
Mass Transfer 127:234–244
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61(11):3532–3542
9. Daizo H, Octave L (1992) Fluidisation engineering, 2nd edn. Massachusetts Institute of
Technology, USA
10. Holman JP (2010) Heat transfer, 10th edn. South Methodist University, McGrow-Hill, New
York
11. Geankoplis CJ (1993) Transport process and unit operations, 3rd edn. Englewood Cliffs, PTR
Prentice-Hall, New Jersey
Numerical Simulation Study
on Optimization of Large-Capacity
Single-Strand Tundish Flow Control
Devices
Ai-ping Zhang, Ming-mei Zhu, Yong Zhong and Bing Huang
Abstract In this paper, according to the large-capacity tundish with single-strand

and rectangular structure, the mathematical simulation method is used to study the
effect of the flow control devices of the weir and the dam on the flow field, temperature
field, and inclusions trajectories of molten steel. The orthogonal experiment method is
used to study the effect of the distance between the weir and the bottom of the tundish,
the distance from the weir to the long nozzle, the distance between the weir and the
dam, the height of the dam on the flow pattern, temperature distribution, and inclusion
removal rate of the molten steel in tundish. The reasonable flow control devices and
the installation position could be obtained by analyzing the results of mathematical
simulation, and it can provide theoretical guidance for actual production.
Keywords Numerical simulation · Flow control devices · Orthogonal test ·

Residence time distribution curve · Inclusion removal rate
Introduction
The tundish plays a vital role in the continuous casting process. The molten steel
from the ladle flows through the long nozzle to the tundish and flows through the
tundish to the mould for continuous casting. The flow pattern and residence time
of molten steel in the tundish will affect the flow pattern and the inclusion removal
rate, which is related to the quality of subsequent continuous casting [1–4]. A large
A. Zhang · M. Zhu (B) · Y. Zhong · B. Huang

College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China
e-mail: zhumingmei@cqu.edu.cn
A. Zhang
Y. Zhong
B. Huang

https://doi.org/10.1007/978-3-030-36540-0_6
56 A. Zhang et al.
number of researches and practices have proved that the flow control device in the
tundish will improve the flow of molten steel, strengthen the contact with the surface
molten steel, reduce the dead volume, and increase the residence time of the molten
steel in the tundish and the inclusion removal rate [5]. Therefore, it is especially
important to improve the purity of molten steel by studying the flow pattern of steel
liquid in the tundish and the inclusion removal rate.
Tassot. P et al. pointed out that tundish as an important metallurgical reactor,
setting a reasonable flow control device is conducive to the removal of inclusions
and improves the quality of steel products. The wire can prevent the upward backflow
of molten steel, which not only increases the chance of collision of inclusions, but also
reduces the flow of steel slag to the outlet [6–9]. Therefore, in order to obtain an ideal
flow pattern and clean molten steel, it is necessary to provide a flow control device in
the tundish. However, the influence of the flow control devices of different sizes and
positions in the rectangular large-capacity single-flow tundish on the molten steel
needs further study. In this paper, a rectangular large-capacity tundish with a volume
of 66t is taken as the research object. By comparing the flow field, temperature field,
fluid residence time (Residential Time Distribution) curve, and inclusion removal
rate in the tundish under the combination of no flow control device and different flow
control devices, the optimal flow control device is determined. Finally, it provides
guidance for the design of flow control devices for large-capacity tundishes.
Numerical Simulation Research Method
Model Hypothesis
The flow of molten steel in the actual tundish is very complicated, and the high tem-
perature working environment makes experimentation and measurement extremely
difficult. In order to facilitate the study of the flow phenomenon in the tundish, this
study has the following assumptions:
(1) The flow of molten steel in the tundish is a steady-state incompressible viscous
fluid;
(2) The inclusions are spherical particles and the movements are independent of
each other;
(3) Ignoring the effect of temperature on flow, density and viscosity are constant;
(4) The movement of molten steel is turbulent motion.
Numerical Simulation Study on Optimization of Large-Capacity … 57
Model Formulation
The flow of molten steel in the continuous casting tundish is a three-dimensional tur-
bulent flow, the mass equation, momentum equation, energy equation, and turbulent
kinetic energy equation used in the calculation are as follows.
Continuity equation:
∂P ∂(ρμi )
+ =0 (1)
∂t ∂ xi
Momentum equation:

∂ ρμi μ j ∂P ∂ ∂μi ∂ ∂μ j
=− + μe f f + μe f f + ρgi (2)
∂x j ∂x j ∂x j ∂x j ∂ xi ∂ xi
Standard k-ε equation describing the turbulent viscosity coefficient:

∂(ρμi ) ∂ μt ∂k
= μe f f + + G − ρε (3)
∂ xi ∂ xi σk ∂ xi

∂(ρμi ε) ∂ μt ∂ε ε ε2
= μe f f + + c1 G − c2 ρ (4)
∂ xi ∂ xi σε ∂ xi k k
among them,

∂μ j ∂μ j ∂μ j k2
G = μt + ; μe f f = μ + μt = μ + cμ ρ
∂ xi ∂x j ∂x j ε
Energy equation related to temperature field calculation:

∂T ∂T ∂ ∂T
ρ + Cp = ke f f (5)
∂t ∂ xi ∂ xi ∂ xi
Equation of transport behavior of inclusions in tundish:

du pi 18u C D Re ρp − ρ
= . u i − u pi + g p + Fi (6)
dt ρ p d 2p 24 ρp
Mass transfer equation of tracer in tundish:

∂C μt C
+ ∇ × Uc = ∇ × ρ Dc + ∇× + SC (7)
∂t Sct ρ
where ρ is the density, kg m−3 ; ui and uj are the velocity of molten steel in the i and
j directions, m s−1 ; p is the pressure, Pa; μeff is the effective viscosity, kg m−1 S−1 ;
58 A. Zhang et al.
C1 , C2 , Cμ , Ck , Cε are empirical constants, and their values are 1.44, 1.93, 0.99, 1.0,
1.3; keff is the effective thermal conductivity, W m−1 K−1 ; ρp is the particle density,
kg m−3 ; dp is the particle diameter, m; upi is the particle velocity, m · s−1 ; CD is the
drag coefficient; Re is the relative Reynolds coefficient; Fi is the force, N; Sc is the
volume source phase, is the residual mass per unit volume of the tracer unit time,
kg/(m3 s); Dc tracer diffusion coefficient, this paper takes 1.1 × 10−8 m2 /s; μt is the
turbulent viscosity of molten steel, kg/(m s); SCt is the turbulent Schmielt number of
the tracer, taken as 0.9.
Boundary Conditions
This study defines the ladle shroud as the velocity inlet, and assumes that the velocity
profile on the inlet section is the same; the outlet is the pressure outlet; the liquid–
solid interface is considered to have no slip boundary, the velocity value on the solid
wall is 0; the free surface is zero shear stress. The heat radiation loss of the wall and
the free surface is neglected; the inclusion particles are adsorbed and removed by
the molten steel surface slag layer; the inclusions in contact with the wall surface of
the intermediate tundish are considered to be completely rebounded. The simulation
parameters involved in the numerical simulation calculation are shown in Table 1.
Simulation Scheme
The prototype tundish studied in this paper has no flow control device, and there
is a dead zone in the flow of molten steel in the empty tundish and the inclusion
removal rate is low. Therefore, orthogonal experiments were designed for the key
factors affecting flow.
Table 1 Important physical parameters for simulation of fluid flow in tundish

Parameters Values Parameters Values
Viscosity 0.0067 kg m−1 s−1 Thermal conductivity 41 W m−2 K−1
Specific heat 750 J kg−1 K−1 Free surface heat flow 15 kW m−2
Density 7020 kg m−3 Bottom wall heat loss 1.4 kW m−2
Turbulent kinetic energy 0.01V2in m2 /s2 Long wall heat loss 3.8 kW m−2
at the inlet
Dissipation rate at the 33.33K1.5 2 3
in m /s Short wall heat loss 3.2 kW m−2
inlet
Inlet temperature 1823 K Inlet diameter 160 mm
Inlet velocity 0.744 m/s Tracer diffusion 1.1 × 10−8 m2 /s
coefficient
During the simulation, the submergence depth of the shroud is 300 mm and the
depth of molten steel is 1300 mm. The detailed tundish structure and flow control
device distribution are shown in Fig. 1.
The change level of the test factors is shown in Table 2. The four factors and three
levels are designed to study the influence of the size and position of the weir and the
dam on the flow behavior of molten steel.
According to the orthogonal factor level table shown in Table 2, the experimental
scheme can be listed as shown in Table 3. Case0 is an empty tundish, which is
compared with the case where there is a weir to block the dam.
Fig. 1 Geometry of tundish
Table 2 Level table of experimental factors (Unit: mm)

Factors (mm) Level 1 Level 2 Level 3
Distance between weir and long nozzle L1 1300 1550 1800
Distance between weir and dam L2 300 500 700
Distance of the weir from the bottom of the tundish H1 300 400 500
Dam height H2 450 550 650
Table 3 The experimental scheme (Unit: mm)

Scheme L1 (mm) L2 (mm) H1 (mm) H1 (mm)
Case0 – – – –
Case1 1300 300 300 450
Case2 1300 500 400 550
Case3 1300 700 500 650
Case4 1550 300 400 650
Case5 1550 500 500 450
Case6 1550 700 300 550
Case7 1800 300 500 550
Case8 1800 500 300 650
Case9 1800 700 400 450
60 A. Zhang et al.
The flow field of the molten steel in the tundish under different working conditions
was calculated by FLUENT software, and then the temperature field, the movement
of the inclusions, and the concentration of the tracer were changed with time under the
condition of the flow field convergence. Finally, the calculated results are imported
into Tecplot for post-treatment to obtain the flow and temperature distribution of
molten steel. The RTD curve can be obtained by processing the curve of the tracer
concentration over time, and the volume fraction of the different flow patterns is
calculated as shown in Table 4.
It can be seen from Table 4 that the dead volume fraction of the empty tundish is
28.8%, and the dead volume fraction with flow control device is significantly reduced.
Figure 2 shows the RTD curves for different operating conditions. In the Fluent
software, the mass transfer equation is used to calculate the converged flow field,
and then the calculated data is imported into Tecplot for dimensionless processing
to obtain the RTD curves. Where θ represents the dimensionless time; C represents
the dimensionless concentration. It can be seen that the peak value of the curve
corresponding to Case3 is to the right, and the peak corresponding to the peak is not
low. It indicates that the residence time of the molten steel in the tundish increases,
which is consistent with the results of the different flow mode volume fractions
calculated in Table 4.
Table 4 Flow characteristics of the tundish with different schemes

Scheme ta , s tmin , s tpeak , s Vd , (%) Vp , (%) Vm , (%) Vp /Vd
Case0 448 39 200 28.8 19.0 52.2 0.7
Case1 489 94 352 22.3 35.5 42.2 1.6
Case2 498 97 416 20.8 40.8 38.4 2.0
Case3 551 57 444 12.4 39.8 47.8 3.2
Case4 514 78 387 18.3 37.0 44.7 2.0
Case5 528 57 431 16.1 38.8 45.1 2.4
Case6 483 60 330 23.2 31.0 45.8 1.3
Case7 480 91 242 23.7 26.5 49.8 1.1
Case8 525 85 405 16.5 39.0 44.5 2.4
Case9 510 75 410 18.9 38.6 42.5 2.0
Note ta the average residence time, s; tmin the minimum residence time, s; tpeak the time to obtain
the peak concentration, s; Vd dead volume fraction, Vp plug volume fraction, Vm mixed volume
fraction
Fig. 2 RTD curves
Comparison of Flow Fields
The installation of a flow control device in the tundish will significantly affect the
flow of molten steel. The left side of Fig. 3 is the empty tundish speed vector diagram,
and the right side is Case3 with the flow control device.
Case0 does not have any flow control device, and the fluid impacts the bottom
after entering the tundish through the inlet. A portion of the fluid forms a backflow in
the narrower region of the injection point; a portion flows directly along the bottom
to the outlet into the continuous casting stage. At the same time, the fluid above the
outlet is hardly involved in the movement, and it is easy to form a dead zone. The
Case3 is provided with a weir and a dam. After the fluid enters the tundish, it is
blocked by the weir and exchanged with the liquid surface fluid. The fluid flowing
along the bottom is blocked by the blocking dam and increases the contact area with
the liquid surface. At the same time, a vortex is formed between the dam and the
Case0 Case3
Fig. 3 Velocity vector of symmetrical plane

62 A. Zhang et al.
outlet to increase the stirring of the fluid. The dead zone above the exit is clearly
eliminated.
Comparison of Temperature Fields
After calculating the temperature field with FlUENT software, the temperature value
can be read directly. As shown in Fig. 4, the temperature difference between the
temperature difference of the flow control device and the empty tundish is 33.1 K
and 18.8 K, respectively.
The temperature distribution in the tundish has a direct impact on the next contin-
uous casting. Tundish metallurgy is the last metallurgical link before pouring molten
steel. The smaller the temperature difference in the tundish, the uniform temperature
distribution throughout the tundish, and the later continuous casting makes it easier
to obtain a slab of uniform quality. Otherwise, the larger the temperature difference
is, the lower the temperature will first solidify the crust, and the post-solidified part
and the first solidified part will have defects such as stress and crack.
Figure 5 is a cloud diagram of the tundish liquid level temperature, and the Case0
temperature is distributed in a symmetrical form. There is a significant difference
between the temperature around the inlet and the temperature around the outlet.
Moreover, the temperature is low along the direction of the symmetry plane, and the
temperature on both sides of the symmetry plane is high. It can be seen that the fluid
in the tundish is not uniformly mixed, and there is a distinct low temperature zone
Fig. 4 Temperature difference diagram

Case0 Case3
Fig. 5 Temperature diagram of top plane
above the outlet. This phenomenon corresponds to the Case0 velocity vector diagram,
indicating that there may be a dead zone above the outlet. However, the temperature
distribution of the tundish liquid level of the flow control device is diffused in the
direction of the spherical crown, the low temperature region is significantly reduced,
and the liquid surface temperature distribution is uniform.
Comparison of Inclusion Removal Effects
When there is no flow control device in the tundish, after the molten steel enters
from the inlet, a part of the molten steel directly carries the inclusions into the mould
along the bottom through the outlet. The inclusions are formed in the slab, which
seriously affects the quality of the slab.
The weir and the dam provided in the tundish changes the trajectory of the fluid.
When the fluid collides with the weir or the dam, it will promote the mutual stirring
of the molten steel. As a result, the probability of collision of inclusion particles
in the molten steel increases. The radius of inclusion particles is 50 μm and the
density is 3500 kg m−3 . When the molten steel inside the tundish is in contact with
the surface of the molten steel, the adsorption of the surface slag layer can remove
the inclusions. Case3 has a weir to block the dam and the inclusion removal rate has
increased by 27.9%. Detailed results are shown in Fig. 6.
Conclusions
In this paper, the influence of the flow control device in the large-capacity single-
strand tundish on the flow field, temperature field, and inclusion removal rate of
molten steel is studied by mathematical simulation. By analyzing the RTD curve to
compare the flow patterns of different schemes, the conclusions are as follows:
(1) The weir and the dam sets in the large-capacity single-flow tundish will affect the
fluid movement trajectory and enhance the agitation of the fluids. The temper-
ature is distributed along the plane of symmetry when empty. The temperature
64 A. Zhang et al.
Fig. 6 Inclusion removal rate
along the symmetry plane is low, the temperature on both sides of the symmetry
plane is high, and the temperature difference reaches 33.1 K. The temperature
difference of the improved tundish is reduced by 14.3 K, and the temperature is
distributed into the spherical crown in the direction of the exit, and the whole
temperature distribution is more uniform.
(2) The positional dimensions of the improved Case3 flow control device are the
distance L1 of the weir from the long nozzle is 1300 mm; the distance L2
between the weir and the dam is 700 mm; the distance from the bottom of the
weir is H1 is 500 mm; the height of the dam H2 is 650 mm. The temperature
difference in the improved tundish was 18.8 K; the inclusion removal rate was
84.3%, and the dead volume fraction was 12.4%.
References
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metallurgical performance of a given tundish. J Iron Steel Res (Int) 21(10):915–922
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curtain in tundish of ultrathick slab continuous casting. Metall Mater Trans B. Process Metall
Mater Process Sci 45B(2):392–398
3. Chen Chao, Cheng Guoguang, Zhang Jiaquan et al (2012) Effects of salt tracer amount, con-
centration and kind on the fluid flow behavior in a hydrodynamic model of continuous casting
tundish. Steel Res Int 83(12):1141–1151
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for optimal performance. Ironmak Steelmak 39(3):171–179
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107(5):179–185
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casting tundish using analysis of RTD curves. J Iron Steel Res Int 16(2):22–29
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Predictive Modeling and Optimization
of the Variant Combinations of Material
Ratios in the Gasification–Reduction
Coupling Process
Yiru Yang, Lei Guo, Qipeng Bao and Zhancheng Guo
Abstract The combined coal gasification and flash ironmaking process (CG-FI)
was the latest technology practice of the alternative ironmaking process, and it can
also be recognized as a multi-generation system for high-quality syngas and reduced
iron. The computational fluid dynamics (CFD) model was established to explore
the process conditions based on the pilot-scale equipment. The turbulent flow, gas–
particle coupling, and kinetic reaction model were considered in the model, which
was already validated in the prior researches. In this study, the different material
ratio combinations, including oxygen/coal ratio (0.6–0.8) and ore/coal ratio (0.2–
1.6), were investigated to illuminate the interrelationship during the gasification–
reduction coupling process. The results demonstrated that the qualified reduced iron
(Reduction Degree = 52.47%) could be obtained even in the worst case (oxygen/coal
ratio = 0.6, ore/coal ratio = 1.6). Moreover, the dispersed hematite particles replaced
the role of H2 O as the coolant and partial oxidant in the traditional coal gasification
process to improve the gasification performance.
Keywords Predictive modeling · Condition optimization · Gasification–reduction

coupling process · Flash ironmaking · Coal gasification · CFD method ·
Multi-generation system
Introduction
The long process with traditional blast furnace and converter is the most popular
ironmaking process, which occupies more than 80–85% of the production in the
world. However, it has been criticized for decades due to more and more serious
environmental problems, especially in developing countries [1]. Therefore, the alter-
native ironmaking processes that do not rely on coke have been developed by both
the experimental method and industrial practice [2, 3].
Y. Yang · L. Guo · Q. Bao · Z. Guo (B)

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, 30
Xueyuan Road, Beijing 100083, China
e-mail: zcguo@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_7
68 Y. Yang et al.
The combined coal gasification and flash ironmaking process (CG-FI) proposed
was the innovative scheme to realize the industrialization of flash ironmaking pro-
cess. The flash ironmaking is actually a kind of gas-based direct reduction process,
proposed by Sohn [4]. However, the reduction time was expected to be reduced to
several seconds under the extremely high temperature (>1473 K). Benefit from the
short reaction time, the production efficiency was significantly improved, and the
steep reduction degree of the ore can be easily obtained [5, 6]. Due to the rigorous
high-temperature conditions, the traditional fluidized bed cannot be utilized due to
the possible sticking phenomenon. Therefore, the industrial flash ironmaking equip-
ment was designed based on the high-temperature flash furnace, which was already
applied in the nonferrous metallurgical industry [7, 8].
Different from the oxygen–hydrogen combustion in the laboratory-scale
researches [9], the more mature coal gasification was adopted in the Outokumpu
furnace to generate sufficient heat and provide reducing gas. The hematite concen-
trate replaced the copper concentrate to be injected into the shaft and expected to be
reduced to metallic status rapidly. The qualified syngas and hot metal can be obtained
separately in the uptake and settler, as shown in Fig. 1; hence, the process was also
recognized as a promising multi-generation system.
However, the designed gasification–reduction coupling process faced the lack of
relevant researches or experience. For example, the high-temperature coupling reac-
tion mechanism was unclear; the flow characteristic in the shaft was unknown; the
internal temperature distribution was invisible. Since the pilot-scale facility was still
Fig. 1 The sketch of the flash furnace equipment

Predictive Modeling and Optimization of the Variant … 69
under construction, and the relevant questions were worthy of being studied, the
numerical simulation was conducted firstly as a pre-design tool in the author’s previ-
ous researches. Based on the kinetic theory of the metallurgy and chemical industry,
the complex reaction system was described by mathematical equations and coupled
into the classical computational fluid dynamics (CFD) solution. The feasibility of
basic cases had been established, and the characteristics were investigated. The pre-
dictive modeling was conducted in this research to explore the optimum condition
(oxygen/coal ratio and ore/coal ratio) of the gasification–reduction coupling process,
in which the variation rule of the product quality was our focus point. This application
also examines the adaptability and robustness of the model for further improvement
through the comparison between different cases.
Equations
Conservation Equations for Gas Flow and Particle Tracking
The continuous phase flow mixed with the sparse discrete particles was the classical
CFD problem, which can be solved by the Eulerian–Lagrangian Method (ELM). The
solution of continuous phase flow was composed of the mass conservation Eq. (2.1),
momentum conservation Eq. (2.2), and energy conservation Eq. (2.3) as shown in
Table 1. In addition, the other auxiliary modules, including the species transport
model, radiation model, and boundary condition treatment, were coupled into the
solution to enrich the details of the model.
For the discrete phase, the Lagrangian method calculates the velocity and posi-
tion of particles with the time scale according to the force balance Eq. (2.4). The
fundamental forces include gravity, buoyancy, and fluid drag in this study.
Table 1 Basic governing equation of the comprehensive model

Equations
Continuous phase flow
∂
∂ xi (ρu i ) = Sm (2.1)
∂
∂p ∂
∂t ρu i u j = − ∂ xi + ∂ x j (τi j − ρu i u j ) + ρgi + Fi (2.2)
∂
∂ ∂T
∂ xi ρu i h g = ∂ xi (ke f f ∂ xi ) + Q r + Sh (2.3)
Discrete particle tracking
+ ( ρpp )
du p up g ρ −ρ (2.4)
dt = τr
70 Y. Yang et al.
Theory of Coal Gasification/Flash Ironmaking
As a interdisciplinary product, the gasification–reduction coupling process conforms

to the reported researches on the coal gasification and flash ironmaking. The descrip-
tion of the reaction mechanism and determination of kinetic parameters were impor-
tant to establish the mathematical descriptions of the complex reactions, especially
for the reacting flow CFD problem.
Generally, the coal gasification process can be divided into the devolatilization
process, gas–solid heterogeneous reactions, and gas–phase homogeneous reactions.
The volatile matter was recognized as the reductive gas mixture, including CO,
H2 , CH4 , and C6 H6 , and the two-competing devolatilization model was adopted in
this study. The relevant details were elaborated in the previous research on the coal
gasification process, while the included reactions were listed in Table 2.
The flash ironmaking process was the latest result of the metallurgy, which
may draw different conclusions from the previous studies. The hematite reduction
was recognized undergoing a step-by-step process (Fe2 O3 –Fe3 O4 –FeO–Fe) in the
gas-based direct reduction studies. However, the research on the flash ironmaking
had proved that the multi-stage reduction process was not clear under the high-
temperature (1373–1623 K) condition, and the single-step reduction (Fe2 O3 –Fe)
was determined [6, 10]. The kinetic expressions of hematite and magnetite were
determined by the experimental method, and the magnetite reduction expression
was already coupled into the CFD model. In our research, the hematite reduction
by H2 and CO was also investigated by the drop tube reactor (DTR) in the higher
temperature range (1523–1823 K). The single-step kinetic expressions were coded
as the user-defined function (UDF) into the CFD model to predict the reduction
Table 2 Summary of
Equations
reactions in the
comprehensive model Devolatilization module
Coal → α1 Volatiles + α2 H2 O + α3 Char + α4 Ash
Volatiles → aCO + bH2 + cCH4 + dC6 H6 + eN2
Gas–solid heterogeneous gasification
C(s) + 21 O2 → CO C(s) + CO2 → 2CO
C(s) + H2 O → CO + H2
Gas–phase homogeneous reactions
CO + 21 O2 → H2 O C6 H6 + 3O2 → 6CO + 3H2
H2 + 21 O2 → H2 O C6 H6 + 6H2 O →
6CO + 9H2 O
CH4 + 21 O2 → CO + 2H2 CO + H2 O → CO2 + H2
CH4 + H2 O → CO + 3H2
Hematite Reduction
Fe2 O3 + 3CO → 2Fe + 3CO2 Fe2 O3 + 3H2 → 2Fe + 3H2 O
Fig. 2 The sketch of the flash furnace equipment
degree of the reduced ore. The experimental and calculated results were compared,
and the certain credibility of the programmed kinetic expressions was demonstrated.
The verified codes for the flash ironmaking were transplanted to the comprehensive
model for the gasification–reduction coupling process
Test Case
Because of the high symmetry of the reaction shaft in the flash furnace, the model
can be simplified to the 1/4 cylinder with sudden expansion structure, as shown in
Fig. 2. According to the pre-check stage, grid independence had been proved, and
the internal flow characteristic can be represented in the 1/4 grid.
Due to the maturity of CFD researches and functional adaptability of the classical
algorithm, the commercial CFD software Ansys Fluent 16.0 was used to simulate
the gasification–reduction coupling reacting flow. The user-defined function was also
adopted to enhance the model. In this study, the different combinations of the material
ratios (oxygen/coal ratio, ore/coal ratio) were investigated to figure out the variation
rule of the product quality and explore the optimum condition. The part of basic
operating conditions and model settings were listed in Table 3.
Thermodynamics Analysis of the Gasification–Reduction

Coupling Process
The reducing gas components in the coal gas generated during the coal gasification
process was mainly carbon monoxide and hydrogen, the ratio of which is about 3:1.
72 Y. Yang et al.
Table 3 Model parameters

Boundary Value Model settings Value
and operation conditions
condition
Gasifying 0.6–0.8 Turbulent Realizable
agent (kg/s) model k-epsilon
Gas C2 -Epsilon 1.9
component
O2 1 TKE Prandtl 1
number
Pre-heated 25 TDR Prandtl 1.2
temperature number
(°C)
Ore feed (kg/s) 0.2–1.6 Dispersion 0.75
Prandtl number
Ore component Near-wall Standard wall
treatment function
Fe2 O3 0.949 Particle steady
tracking
Gangue 0.051 Max. number 40000
tracking
Coal feed 3.6 Step length 5
(kg/s) factor
Coal Radiation DO
component model
Fixed carbon 0.572 Internal 0.7
emissivity
Volatile matter 0.285 Theta divisions 4
Ash 0.143 Phi divisions 3
Therefore, the gas-based reduction of the gas mixture was a competing/promoting

reaction system between the carbon monoxide and hydrogen. The analysis was con-
ducted firstly according to the thermodynamic data. Figure 3 shows that the equi-
librium carbon monoxide proportion, in which the ore can be reduced to metallic
iron, increased with the rising temperature, and the hydrogen proportion was the
opposite. Therefore, the low utilization ratio of coal gas can be predictable during
the high-temperature reduction process. However, the residual carbon can further
react with the oxidation product during the reduction process to compensate for the
decrease of the reducing gas, because the oxygen/coal ratio of CG-FI was relatively
lower than coal gasification.
On the other hand, the low-utilized coal gas was also recognized as high-quality
syngas that can be used to the synthesis industry after reforming. While the low
calorific value blast furnace coal gas can only be used for combustion to recycle the
energy. From this point of view, the combined coal gasification and flash ironmaking
process is different from the previous gas-based direct reduction process and has the
Fig. 3 Equilibrium reduction components with varied temperature during ore reduction
potential to improve the efficiency of the comprehensive utilization of material and

energy.
Predicted Gas Components and Temperature
For the further application of the coal gas after the coupling process, the proportion of
different components should be obtained for the reforming process. Figure 4 shows
the influence of the different oxygen/coal ratios (0.6–0.8) on the composition of syn-
gas under the low-ore/coal-ratio condition (ore/coal ratio = 0.4). With the increasing
ore/coal ratio, the carbon monoxide proportion decreased rapidly from 72.67 to
59.94%, while the hydrogen proportion is kept at a specific value of around 25%. In
addition to the deterioration of the effective-gas as ϕCO + ϕH2 ), the crit-
ratio (defined
ical index hydrogen/carbon ratio (defined as ϕH2 − ϕCO2 / ϕCO + ϕCO2 ) decreased
rapidly due to the rising carbon dioxide proportion, which was disadvantageous for
the reforming process. Therefore, the relatively low oxygen/coal ratio was recog-
nized to be better for the coupling process. It should be noticed that the hematite ore
provides the oxygen element to gasify the residual carbon furtherly, and the carbon
conversion rate increased to 99.9% even when the oxygen/coal ratio was 0.6. As
a reference, the corresponding carbon conversion ratio in the separate gasification
model was predicted to be 71.4%.
The cases with high ore/coal ratio were also compared, as shown in Fig. 5. The
carbon monoxide proportion decreased from 64.26 to 33.85% continuously, while the
hydrogen proportion shows a significant trend of dropping first and rising latterly. In
74 Y. Yang et al.
Fig. 4 The predicted composition of syngas under different combinations (ore/coal ratio = 0.4)
Fig. 5 The predicted composition of syngas under different combinations (ore/coal ratio = 1.6)
addition to the fluctuation of hydrogen proportion, the deterioration of the effective-

gas ratio and the hydrogen/carbon ratio were still observed in our model.
The conclusions can be safely drawn that the lower oxygen/coal ratio is advan-
tageous for the improvement of the syngas quality. At the same time, the higher
ore/coal ratio consumed more reductive components leading to the degraded syn-
gas quality. However, the influence of adding oxidizing ore is significantly weaker
than the direct addition of oxygen, which is due to the decreasing efficiency of ore
reduction process under the high-ore/coal-ratio condition. For example, the carbon
monoxide proportion in Figs. 4a and 5a show the minor variation (72.67–64.26%)

with the significantly increased ore/coal ratio from 0.4 to 1.6, while the similar
variation can be observed with different oxygen/coal ratio from 0.6 to 0.7 in Fig. 4b.
The utilization ratios of the reductive components with complete condition com-
binations were illustrated in Fig. 6. Both carbon monoxide and hydrogen utilization
ratio show an upward trend with the increasing ore/coal ratio on the whole. However,
the utilization ratio of CO in the high-oxygen-ratio interval (1.0–1.6) decreased. The
reasonable explanation was that the reaction rate of hydrogen reduction was faster
than that of carbon monoxide reduction. In addition, the reduction efficiency also
reduced with increasing hematite feed, and the utilization ratio decreased eventually
with higher ore/coal ratio. The realization of the flash reduction process depended
on the reaction temperature, which influenced the reaction rate significantly.
However, the utilization ratio with different cases shows an unusual rule that the
hydrogen utilization ratio almost kept zero in Fig. 6c. The kinetic parameter of the
water gas shift reaction (WGSR) was borrowed from the coal gasification research,
while the temperature should have a range of application. The equilibrium tempera-
ture of cases with high oxygen/coal ratio in our model may be beyond the reasonable
scope of temperature, and the exaggerated reaction ratio of WGSR made the car-
bon monoxide consume the generated steam rapidly. The unreasonable utilization
ratio variation was attributed to this distortion. The reverse water gas shift reaction
Fig. 6 Utilization ratio of the variant combination of the material ratio

76 Y. Yang et al.
Fig. 7 Exhaust temperature with different combinations of the material ratio
(rWGSR) was included to offset the too fast reaction rate at the high-temperature
condition to make up for this distortion in the next version model.
Figure 7 shows the exhaust temperature of all combinations of conditions that
represent the temperature level in the reaction shaft to a certain extent. The significant
positive proportional relationship of the oxygen/coal ratio on the temperature was
observed, while the ore/coal ratio shows the negative influence. The excessive oxygen
combusted the reductive gas and released a large amount of the chemical energy,
which was essential for the ore reduction. The cold ore particles absorbed much
heat to reach the flash reduction temperature range (1473–1873 K). It should be
noticed that the reduction of hematite by hydrogen (Fe2 O3 + H2 ) was an endothermic
reaction. However, the carbon monoxide reduction (Fe2 O3 + CO) was an exothermic
process, that was also a reasonable explanation of the flatter temperature variation
in the high-oxygen/coal-ratio cases.
Predicted Reduction Degree of Hematite
For the two-step smelting reduction processes, the corrosive ferrous oxide caused
the severe erosion of the refractory brick. Therefore, a large amount of pulverized
coal or even coke had to be sprayed into the settler to avoid corrosion. However, the
CG-FI process was expected to reduce the hematite to a certain degree in the reaction
shaft to avoid erosion of ferrous oxides.
Figure 8 shows the predicted reduction degree in all of the material ratio com-
binations, and the corresponding effective-gas ratio was also presented. In the low-
oxygen/coal-ratio cases, the reduction degree decreased continuously. The worst
Fig. 8 Ore reduction degree and the corresponding effective-gas ratio
reduction degree was obtained at the trial (oxygen/coal ratio = 0.6, ore/coal ratio =
1.6) as low as 52.47%. With the increasing oxygen/coal ratio, the reduction degree
increased significantly and kept 100% in the low-ore/coal-ratio cases. The reduced
reduction degree should mainly attribute to the decreasing temperature, as shown in
Fig. 7, which leads to the lower reduction efficiency of flash ironmaking.
The consistent and credible trends were observed between the cases with ore/coal
ratio = 0.6 and 0.7 according to the quality variation curves. However, the cases
with oxygen/coal ratio were already beyond the reasonable reduction temperature
range (1473–1873 K). According to the mentioned reason, the variation curved may
exaggerate the reduction efficiency due to the too fast WGSR.
Conclusion
The numerical model was established based on the gasification–reduction coupling

process, and the predictive modeling was conducted to investigate the cases with
different material ratio combinations. The variation rule of the product quality was
explored, and optimum conditions were determined. The conclusions were listed as
follows:
(1) With the increasing oxygen/coal ratio, the syngas quality deteriorated according
to the decreasing effective-gas ratio and hydrogen–carbon ratio. However, the
temperature was increased significantly, and corresponding reduction degree
kept rising until it reached 100%.
(2) With the increasing ore/coal ratio, the effective-gas rate decreased continuously,
and the utilization ratio of the reductive gas raised in the certified range of
ore/coal ratio (0.2–1.6). Since the excessive ore feed absorbs a large amount of
heat, the lower efficiency of the ore reduction process was observed in high-
ore/coal-ratio cases.
78 Y. Yang et al.
(3) Although the excellent quality of reductive gas and reduced iron can be obtained
simultaneously according to the variation curves, the production efficiency of
the reduced iron was the essential restrictive link. The range that oxygen/coal
ratio = 0.6–0.7 and ore/coal ratio = 0.2–1.2 can be reasonable according to the
actual production requirements.
References
1. Zhang CX, Qi YH, Yan DL, Hu CQ, Zhang XX (2016) Energy-saving and environmental
protection of ironmaking system in China. Iron and Steel 41(11):1–5
2. Meijer K, Zeilstra C, Teerhuis C et al (2013) Developments in alternative ironmaking. Trans
Indian Inst Met 66(5–6):475–481
3. Hasanbeigi A, Arens M, Price L (2014) Alternative emerging ironmaking technologies for
energy-efficiency and carbon dioxide emissions reduction: a technical review. Renew Sustain
Energy Rev 33:645–658
4. Sohn HY, Mohassab Y (2016) Development of a novel flash ironmaking technology with
greatly reduced energy consumption and CO2 emissions. J Sustain Metall 2(3):216–227
relevant to a novel flash ironmaking process. Metall Mater Trans B 44(1):133–145
6. Chen F, Mohassab Y, Jiang T, Sohn HY (2015) Hydrogen reduction kinetics of hematite
concentrate particles relevant to a novel flash ironmaking process. Metall Mater Trans B
46(3):1133–1145
7. Zhou J, Zhou J, Chen Z, Mao Y (2014) Influence analysis of air flow momentum on concentrate
dispersion and combustion in copper flash smelting furnace by CFD simulation. JOM-US
66(9):1629–1637
8. Ahokainen T, Jokilaakso A (2013) Numerical simulation of the outokumpu flash smelting
furnace reaction shaft. Can Metall Quart 37(3–4):275–283
9. Sohn HY, Perez-Fontes SE (2016) Computational fluid dynamics modeling of hydrogen-
oxygen flame. Int J Hydrog Energy 41(4):3284–3290
10. Chen F, Mohassab Y, Zhang S, Sohn HY (2015) Kinetics of the reduction of hematite concen-
trate particles by carbon monoxide relevant to a novel flash ironmaking process. Metall Mater
Trans B 46(4):1716–1728
Part II
Energy Efficient Clean Metallurgical
Technologies
Clean and Efficient Recovery of Precious
Metals from Ag-Rich Lead Slime Anode
Bin Yang, Guozheng Zha, Xiaofeng Zhang, Xiangfeng Kong, Daxin Huang,
Wenlong Jiang, Dachun Liu and Baoqiang Xu
Abstract Lead anode slime (LAS), a significant by-product for Ag and Au recovery,
is produced from lead electro-refining process. The volume of Ag recycled from LAS
accounts for approximately 60% share of global silver production. Limited under-
standing of complex characteristics of the metals in LAS and prominent problems of
difficult efficient separation, complex process, and serious environmental pollution
in traditional LAS processing for PMs recovery have been highlighted as significant
knowledge gaps. An innovative directional vacuum volatilization of LAS for Ag and
Au enrichment is therefore proposed. Results indicated that Ag and Au were suc-
cessfully enriched in residues, while impurities of As2 O3 , Sb2 O3 , etc., were collected
in volatiles. The direct recovery of Ag and Au reached 99.0%. Vacuum strategy not
only effectively extracted Ag and Au but also avoided arsenic contamination. The
finding will be significant to benefit decision-making direction for clean-efficient
utilization of LAS.
Keywords Lead anode slime · Precious metal · Vacuum separation · Cleaner

recovery
Introduction
Silver and Au are the most concerned precious metals playing an important role in
the development of human civilization. Silver and Au have excellent physical and
chemical properties and are widely used as indispensable key materials in aerospace,
B. Yang · G. Zha · X. Zhang · X. Kong (B) · D. Huang · W. Jiang · D. Liu · B. Xu

National Engineering Laboratory of Vacuum Metallurgy, Kunming University of Science and
Technology, Kunming 650093, Yunnan, People’s Republic of China
e-mail: xfkong@csu.edu.cn
Faulty of Metallurgical and Energy Engineering, Kunming University of Science and Technology,
68 Wenchang Road, Kunming 650093, Yunnan, People’s Republic of China
X. Kong · D. Liu · B. Xu
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming
University of Science and Technology, Kunming 650093, Yunnan, People’s Republic of China

https://doi.org/10.1007/978-3-030-36540-0_8
82 B. Yang et al.
new energy, electronic information, and other high-tech fields. In 2018, the inventory
of Ag reached 19481 tons. The volume of Ag produced from lead anode slime (LAS)
accounts for approximately 60% share of global silver production, and the ratio is
still increasing [1]. Therefore, it is of great significance to improve the utilization
rate of Ag in LAS [2].
LAS is the by-product produced from crude lead electrolytic refining, estimating
1.2–2.0% of crude lead production [3]. The characteristics of LAS are (1) complex
composition, LAS contains elemental Ag and Au, intermetallic compounds formed
with As, Sb, Bi, etc., and oxides such as arsenic, antimony, and bismuth. (2) complex
structure, Au, Ag and As, Sb, Bi constitute a molecular structure of various valence
states, and the particles are embedded with each other. Efficient extraction of precious
metals from LAS is difficult to achieve [4].
LAS treatments usually adopt thermal metallurgy process (fire smelting, heat
refining, and/or electrolytic refining), including reduction smelting, oxidative refin-
ing of silver, reduction smelting and refining of antimony, slag smelting and subse-
quent electrolytic refining [5, 6]. These processes lead to the generation of metal dust
and waste. Subsequent treatments of these residues are the most critical because they
contain large amounts of heavy metals and toxic substances [7, 8]. Even with dust
collection systems, they inevitably pollute the local environment through rainfall
[9]. It is particularly noteworthy that As will accumulate in the ecosystem through
atmospheric activities, causing secondary pollution of soil and water, further endan-
gering human health. Hydrometallurgical process of LAS usually requires the steps
of pretreatment, leaching, reduction, etc. This method has poor adaptability to LAS,
low purity of recovered rare metals, many kinds of chemical reagents, complicated
process equipment, strong medium anti-corrosion, and high maintenance cost.
In order to maximize the economic and environmental benefits of extracting valu-
able metals from LAS, the harmful elements in metallurgical by-products should be
appropriately removed in an environmentally friendly and low-cost manner, and the
valuable elements should be comprehensively utilized [10, 11]. Arsenic impurities
must be removed, because they will greatly reduce the economic value of LAS and
require additional treatment to avoid the interference of harmful substances. There-
fore, development of a sustainable, economic, and novel strategy to separate and
recover valuable metals from LAS is a key target of the lead industry.
Vacuum technology has been widely used in separation, purification, and recov-
ery of metals in nonferrous alloys and waste slag, because of its advantages includ-
ing simplified process, high recovery, low pollution, low energy consumption, etc.,
therefore eliminating the drawbacks of traditional metallurgy [12–18]. This paper
describes a new process for the efficient recovery of precious metals from LAS using
vacuum distillation. Calculation and analysis of the separation/recovery effect under
saturated steam pressure, and vacuum process required for recovery of precious met-
als are considered. Finally, this work attempts to understand the behavior of elements
after vacuum distillation and their impact on the environment.
Clean and Efficient Recovery of Precious Metals … 83
Table 1 Chemical composition of LAS (wt%)

Component As Ag Te Bi Pb Sb Cu Au (g/t) Other
LAS 2.38 9.24 0.21 15.62 15.25 37.88 2.17 670 17.25
Fig. 1 X-ray patterns of LAS
Materials and Methods
Characterization of LAS Materials
LAS samples were collected from Henan, placed in wooden boxes, and sent to the
laboratory. Metal contents of samples were analyzed by inductively coupled plasma
atomic emission spectrometry (ICP-AES) and chemical titration (Table 1). Samples
were also polished to a flat surface, 20 × 20 mm, and analyzed by X-ray powder
diffraction (XRD) using a RIGAKUD/MAX-2400 with Cu Ka (40 kV) radiation.
XRD patterns were collected from 10 to 90° with fine scanning (Fig. 1). XRD phases
were identified by means of the Research/Match analysis package (S/M focus on
major, minor, or trace phases).
Vacuum Separation Experiment
The experimental equipment is a small vertical vacuum distillation furnace (Fig. 2).
The homogeneous LAS sample (100 g) was separately introduced into a graphite
84 B. Yang et al.
Fig. 2 Structure
representation of vacuum
distillation furnace. 1,
stainless steel shell; 2, valve;
3, thermocouple; 4,
insulation materials; 5,
graphite resistance; 6, raw
material; 7, crucible; 8,
condenser; 9, vacuum gauge
crucible (high-density cylindrical graphite: 9 cm OD × 8 cm ID × 12 cm Ht), placed

in the bottom distillation zone, and then evacuated to a residual pressure of 15 Pa
using a mechanical pump. The condenser (stainless steel) was located approximately
6 cm above the graphite crucible to collect volatiles. The heating principle involves
heating the graphite resistor by radiation generated continuously from the electric
current. Radiation heat is transferred to volatile components on the surface of the
LAS, and then is transferred to the inside. The effects of distillation temperature
(1073, 1123, 1173, 1223, 1273 K) and distillation time (25, 50, 75, 100, 125 min) on
separation and enrichment of precious metals were investigated. During the vacuum
evaporation, volatile materials were evaporated into a gas phase and condensed on
the condenser. Finally, the temperature of the furnace reached to room temperature,
opening the furnace cover, and the volatiles in the condenser and the residues in the
crucible were collected, weighed, and sampled, respectively.
Method of Analysis
The crystalline phase of products was identified by X-ray diffraction (XRD) using Cu
Kα (λ = 1.5418 Å) radiation with a scanning rate of 2°/min on an instrument manufac-
tured by Rigaku Corporation of Japan. Volatilized and non-volatilized residues were
collected at random at six locations. Samples were then mixed to form are presenta-
tive concentration. High-content elements were determined by chemical titration. The
contents of As, Te, and Sb in the residue were determined by ICP-AES.
Theory and Calculation
Principle of Separation
The solid and liquid state of any substance has a tendency to volatilize into a gaseous
state, and the gaseous state also has a tendency to condense into a solid state or
condense into a liquid state in response to the heart. Vacuum distillation technology
is a typical physical method for separating and purifying metals, alloys, and oxides
using this property. Each substance has a specific vapor pressure in a specific tem-
perature range, and the vapor pressure has an important influence on the evaporation
characteristics of the substance. Materials with a higher vapor pressure usually have
a higher vapor pressure. This is essential for separating LAS secondary materials in
order to separate and recover precious metals in a vacuum environment.
Saturated Vapor Pressure Determination
The different vapor pressures of metal species in LAS secondary materials are theo-
retically calculated to estimate the feasibility of separation. The result of the relation-
ship between metal pressure and temperature (Fig. 3) shows that the pressures of As,
Te, and Sb are much higher than other elements in the same temperature range. As,
Te, and Sb preferentially evaporate at relatively low temperatures, separated from
the LAS (Fig. 3), while Ag and Au are more difficult to evaporate at lower saturated
vapor pressures and remain in the crucible. Therefore, rational use of the vacuum
distillation process can effectively separate and enrich Au and Ag from LAS.
Effect of Distillation Temperature on Impurities Separation
The effect of distillation temperature on the volatile release of As and Te was investi-
gated under pressures of 15 Pa at a constant distillation time of 25 min. Evaporation
of As and Te into the vapor to the maximum possible requires two elements that
maintain the lowest content in the residue to achieve a higher removal. The content
of impurity elements in the residue and the removal rate of As and Te are shown in
Fig. 4a. The evaporation ratio is shown in Fig. 4b.
Removal rate = (wa − wb )/wa
Evaporation ratio = m a /m 0
86 B. Yang et al.
Fig. 3 Separation predication diagrams of a main elements and b main oxides in LAS
where wa is the content of As, Te, and Sb in raw material (%), wb is the content of
As, Te, and Sb in residue (%). m0 is the mass of raw material (g), ma is the mass of
condensate (g).
The results showed that the content of As and Te in the residue decreased with an
increase of the temperature. When the temperature was 1223 K, Te was not detected
in the residue, indicating that the Te removal rate was 100%, and the As content
was reduced from 2.38 to 0.62%. The removal curves of As and Te indicated that
separation of Te and As from LAS is feasible. When the temperature is between 1073
Fig. 4 Effect of distillation temperature on a removal rate and b evaporation ratio (1073–1273 K,
25 min, 15 Pa)
and 1173 K, the removal rate of Te increased significantly (Fig. 4a). As the rate of
removal of As and Te continued to increase temperature without significant changes,
it was determined that 1173 K was the optimum distillation temperature. When the
distillation temperature was 1173 K and the holding time was 25 min, the contents
of As and Te in the residue were 0.62% and 0.042%, respectively, and the removal
rates were 80% and 72.69%, respectively.
88 B. Yang et al.
Effect of Distillation Time on Impurities Separation
Effect of distillation time (25–125 min) on volatilization behavior of the elements at

the optimum temperature of 1173 K was investigated, and the results were shown in
Fig. 5a. The effect of distillation time on the evaporation ratio was shown in Fig. 5b.
Fig. 5 Effect of distillation time on a removal rate and b evaporation ratio (25–125 min, 1173 K,
15 Pa)
Fig. 6 XRD patterns of a volatile and b residue obtained from the optimal conditions (1173 K,
15 Pa, 75 min)
Results showed that As, Te, and Sb were preferentially evaporated in a short period
of time and separated from Au and Ag, which is consistent with the calculation of sat-
urated vapor pressure. From the kinetics of the evaporation rate, with distillation time
increasing, As, Te, and Sb with higher evaporation rate were volatilized completely.
However, Ag and Au volatilized slowly and were enriched in the residue. With dis-
tillation time increasing, the removal rates of As, Te, and Sb increased (Fig. 5a), and
the removal rate of Te reached the maximum at 75 min. Extending the distillation
time, the Te removal rate did not change significantly. There is a steep slope of the
90 B. Yang et al.
Sb removal rate curve at 75 min ago. At this range, the removal rate increased from
16.01 to 75.61% (Fig. 5a). During the 75–125 min period, the removal rate of Sb
was not significantly improved. At the optimal condition of 1173 K and 75 min,
the contents of As, Te, and Sb in the residue were 0.43%, 0.0047%, and 9.24%,
respectively, and the removal rates were 81.93%, 97.76%, and 75.61%, respectively.
Figure 6 was a graphical representation of the XRD of the residue and condensate
under the optimal conditions.
This paper described a new vacuum method to separate and enrich precious met-
als in LAS. The traditional high temperature metallurgy process has high energy
consumption, heavy pollution, and long process time, which can be replaced by
vacuum separation process. The vacuum distillation process is simple, efficient, and
clean, especially for avoiding the repeated smelting processes, which can signifi-
cantly reduce the high consumption rate of production. Therefore, vacuum processing
of LAS is more suitable for the sustainable development.
Conclusions
This work proposed a new vacuum technology strategy to extract and recover precious
metals from LAS. The precious metals were enriched from the LAS using a vacuum
distillation process. The contents of As, Te, and Sb in the residue were 0.43%,
0.0047%, and 9.24%, respectively, and the removal rates were 81.93%, 97.76%, and
75.61%, respectively, at the distillation temperature of 1173 K and the holding time
of 75 min. Au and Ag in LAS were successfully enriched, and the direct recovery
reached 99.0%. As, Te, and Sb were collected in the volatilization stage. These
findings are valuable because they help to separate valuable metals from the LAS
and contribute to the decision-making process for clean utilization.
Acknowledgements This project was funded by the construction of high-level talents of Kunming
University of Science and Technology (EmpNo. 20180050), the Fund of National Natural Science
Foundation of China (Grant No. U1502271), the National Key Research and Development Program
of China (Grant No. 2016YFC0400404), the Leader in Science and Technology of Yunnan Province
(Grant No. 2014HA003), and the Program for Nonferrous Metals Vacuum Metallurgy Innovation
Team of Ministry of Science and Technology (Grant No. 2014RA4018), National Natural Science
Foundation of China (Grant No. 51874156). The authors sincerely acknowledge the anonymous
reviewers for their insights and comments to further improve the quality of the manuscript.
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6. He YL, Xu RD, He SW, Chen HS, Li K, Zhu Y, Shen QF (2017) –pH diagram of As–N–
Na–H2 O system for arsenic removal during alkaline pressure oxidation leaching of lead anode
slime. Trans Nonferrous Metals Soc China 27(3):676–685
7. Chen XP, Guo CX, Ma HR, Li JZ, Zhou T, Cao L, Kang DZ (2018) Organic reductants based
leaching: a sustainable process for the recovery of valuable metals from spent lithium ion
batteries. Waste Manag 75:459–468
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stabilisation of arsenic from arsenic-rich lead anode slime. J Clean Prod 176:26–35
9. Havuz T, Çelik C (2010) Optimization of removal of lead from bearing-lead anode slime. J Ind
Eng Chem 16(3):355–358
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using a mixed NaOH–Na2 S leach. Hydrometallurgy 108:165–170
11. Han JW, Liang C, Liu W, Qin WQ, Jiao F, Li WH (2017) Pretreatment of tin anode slime using
alkaline pressure oxidative leaching. Sep Purif Technol 174:389–395
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13. Dai YN, Yang B (2000) Vacuum metallurgy of nonferrous metal materials. Metallurgical
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Effects of Electrolytic Parameters
on the Deposition of Boron at the Cathode
During Molten Salt Electrolysis of Silicon
Tao Wang, Zhongliang Tian, Shu Yang and Yanqing Lai
Abstract The element boron has an important influence on the conversion effi-
ciency of solar cells of silicon. In this study, the effects of the electrolytic parameters
(electrolysis temperature, current density, and concentration of Si in melt) on the
deposition of B at the cathode were studied during the molten salt electrolysis for
silicon in Na3 AlF6 –SiO2 melt. ICP analysis shows that the deposition content of B at
the cathode is decreased with the increase in electrolysis temperature, but is increased
with the increase in current density. Moreover, increasing the concentration of Si in
melt is unfavorable for B to deposit at the cathode. Accordingly, by adjusting the
electrolytic parameters, the deposition of B can be controlled.
Keywords Na3 alf6 –SiO2 melt · Boron deposition · Electrolytic parameters ·

Molten salt electrolysis for silicon
Introduction
Green and sustainable energy has attracted much attention worldwide due to the
problems of energy and environment. National government attaches great importance
to the solar energy and photovoltaic industry [1]. At present, solar grade silicon is the
most widely used photovoltaic material [2]. Tremendous research to achieve cheap
and environmentally friendly production process of solar grade silicon has been
conducted. Currently reported methods mainly include chemical [3] and metallurgy
methods [4]. As one of the metallurgy methods, the molten salt electrolysis is regarded
to be promising due to its advantages of convenient operation, short process, and low
cost [5].
For the molten salt electrolysis process, the removal of impurities is the main
objective, especially boron and phosphorous which have a great influence on the
conversion efficiency and stability of solar cells [6]. Mounier and Barakat [7] made
T. Wang · Z. Tian (B) · S. Yang · Y. Lai

School of Metallurgy and Environment, Central South University, 932 Lushan South Road,
Changsha 410083, Hunan, China
e-mail: tianzhongliang@126.com

https://doi.org/10.1007/978-3-030-36540-0_9
94 T. Wang et al.
the first attempt to conduct electrorefining of silicon using metallurgical grade silicon
in SiO2 /Na3 AlF6 system. By using liquid Al as the cathode and Cu–Si alloy as the
anode, Jia et al. [8–10] performed electrolytic refining of silicon in NaF–AlF3 –
K2 SiF6 melt. The removal rate of B can reach 60%. After further processing, silicon
with the purity of higher than 99.99% could be obtained. In CaCl2 –NaCl–CaO–Si
melt, Cai [11] reported the results of the electrorefining of metallurgical grade silicon.
The boron and phosphorus contents were found to be reduced by 87.2% and 88.8%,
respectively. Later, it was found that the boron removal rate was controlled by kinetic
factor [12]. When the average solidification temperature decreases, the apparent
segregation coefficient of boron decreases, and the average width and mass of primary
silicon flakes decrease with increasing cooling rate. Recently, a purification model
was developed to purify MG–Si using a combined process of Si–Sn solvent refining
and CaO–SiO2 –CaCl2 slag treatment [13]. The results indicated that increasing Sn
content favors B removal. With the increase of Sn to 50% of the alloy, the B content
decreased to 1.1 × 10−4 wt%, reaching a removal rate of 93.9%. Although lots of
research has been conducted on the purification in molten salt electrolysis process,
the removal rate of boron in silicon remains low and a further study is needed.
Therefore, in this study, the molten salt electrolysis of silicon was conducted with
the liquid Al as the cathode and the high-purity graphite as the anode in Na3 AlF6 –
SiO2 molten salt system. The effects of the electrolytic parameters including electrol-
ysis temperature, current density, and concentration of Si in melt on the deposition of
B at the cathode were investigated. The objective was to obtain data for the removal
of B in deposited silicon by molten salt electrolysis method.
Experimental
Chemicals and Materials
The main materials include analytical grade Na3 AlF6 , SiO2 , AlF3 , B2 O3 , and AlCl3 .
In order to remove the water, all the materials were heated at 120 °C in a vacuum
for over 24 h before the experiment. The B2 O3 was kept in a dry environment, and
added quickly in the feeding process to prevent the water absorption. Al block with
purity of 99.99% was treated by HCl to remove the oil stain and the Al2 O3 film.
Cell Design and Electrolysis Procedure
The schematic diagram of the electrolytic cell is shown in Fig. 1. The cell consists
of graphite crucible and corundum crucible with an orifice of ø25 mm at the bottom.
The electrolyte was Na3 AlF6 –SiO2 (CR = 2.2), whose total mass was 400 g. In order
to cover the bottom of the crucible and form a stable cathode, 40–60 g aluminum
Effects of Electrolytic Parameters … 95
Fig. 1 Schematic drawing

of the electrolytic cell,
A-stainless steel rod
B-insulation cover
C-graphite anode, D-liquid
Al cathode E-corundum
sleeve F-corundum crucible,
G-graphite crucible
H-electrolyte I-iron plate
block was added. The electrolyte was thoroughly mixed before the experiment, and
then the crucible was placed in a resistance furnace to heat to a setting temperature in
a protective atmosphere. The temperature of the melt was measured by Pt/Pt-10%Rh
thermocouple, the uncertainty of temperature control was ±1 °C.
After the electrolysis, the melt was naturally cooled. The gray-black deposit prod-
uct was obtained and ground into a powder with a size of 200 mesh. The ground
product was added to a 20% AlCl3 solution to stir at 10 r/min for 12 h in a 70 °C
water bath. The product was rinsed with deionized water and then dried.
Material Characterization
The composition of the deposited silicon is characterized by X-ray Diffractometer

(XRD) (D/max2500X). The concentration of element in the molten salt electrolyte is
analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-AES)
(PerkinElmer Optima 5300DV).
96 T. Wang et al.
Deposition Product
Under the Na3 AlF6 –SiO2 molten salt system, the experiments were conducted at
electrolysis temperature of 1010 °C, the current density of 500 mA/cm2 , and the
electrolysis time of 6 h. The appearance of electrolysis product is shown in Fig. 2a,
b. It can be seen that the electrolysis product is well layered, the bottom layer is a
metal-like substance with metallic luster, and the middle layer is a gray-black and
dense layer with a thickness of 5–20 mm. The upper of the gray-black deposit layer
is covered with a white electrolyte. Figure 2c shows the powder of the treated gray-
black deposit, and its XRD analysis result is shown in Fig. 2d. Apart from the main
element Si, aluminum and a small amount of Al2 O3 which are easy to be removed also
appear, but no other impurity peaks are found. After electrolysis process and further
treatment, the product is obtained and separation from the electrolyte is basically
achieved.
Fig. 2 a, b morphology of cathode product, c morphology of the gray-black deposition product

after treatment, and d its XRD images
Fig. 3 Effect of electrolysis

temperature on the
concentration of B in the
melt
Electrolysis Temperature
The effect of electrolysis temperature on the concentration of B in electrolyte is

shown in Fig. 3. At the same temperature, the concentration of B in electrolyte
decreases with the extension of electrolysis time. After 4 h of electrolysis at 1010
°C, the concentration of B in electrolyte decreases from 0.276 to 0.175%. After
6 h of electrolysis, when the electrolysis temperature changes from 1000 to 1030
°C, the concentration of B in electrolyte is 0.116%, 0.125%, 0.129%, and 0.132%,
respectively. It is indicated that increasing temperature is beneficial to the retention
of B in the electrolyte. However, when the temperature is higher than 1010 °C, the
concentration of B in electrolyte changes little, and the evaporation of electrolyte
increases. Therefore, a suitable electrolysis temperature of 1010 °C is selected.
Current Density
The effect of current density on the concentration of B in electrolyte is shown in

Fig. 4. After 6 h of electrolysis, when the electrolysis current is increased from 400
to 600 mA/cm2 , the concentration of B in electrolyte is decreased to 0.135%, 0.138%,
0.125%, 0.108%, and 0.096%, respectively. Studies have shown that increasing the
current density leads to an increase in the potential of the cathode, and impurities
in the electrolyte that are more negative than the electrode potential of Si are more
likely to be precipitated [14]. Therefore, as the current density increases, element B
whose electrode potential is slightly negative than that of Si is more likely to deposit
at the cathode, resulting in a decrease in the concentration of B in electrolyte.
98 T. Wang et al.
Fig. 4 Effect of current

density on the concentration
of B
Concentration of Si in Melt
Figure 5 shows the variation of the concentration of B with the concentration of

silicon in melt when the electrolysis temperature is 1010 °C, current density is
500 mA/cm2 , and electrolysis time is 6 h. When the concentration of Si in melt
is 0.924%, 1.926%, 2.889%, and 4.025%, the concentrations of B in electrolyte is
0.104%, 0.253%, 0.261%, and 0.265%, respectively. According to the initial con-
centration of B in electrolyte of 0.276% (tested by ICP), the deposition content of B
calculated is 0.172%, 0.023%, 0.015%, and 0.011%, respectively. It can be seen that
as the concentration of Si in the electrolyte increases, the deposition content of B at
the cathode decreases. To make it clear, the electrode potential difference between
Fig. 5 Effect of
concentration of silicon in
melt on the concentration of
B
the Si and B is calculated to be −0.009 V, 0.020 V, 0.033 V, 0.042 V, respectively.

Under the same condition, the electrode potential difference between the Si and B
increases with the increase of concentration of Si in melt. Therefore, Si is more likely
to deposit at the cathode with B remaining in the electrolyte.
Conclusion
In the molten salt electrolysis of silicon, the effects of the electrolysis temperature,
current density, and concentration of Si in Na3 AlF6 –SiO2 melt on the deposition of
B at the cathode were studied. Silicon was obtained from the deposited product and
separated from the electrolyte thoroughly. ICP analysis showed that the deposition of
B at the cathode decreased with the increase in electrolysis temperature. Considering
the evaporation of electrolyte, a suitable electrolysis temperature of 1010 °C was
selected. As current density increased, elemental B was more likely to deposit at
the cathode. Deposition of B at the cathode decreased as the concentration of Si in
the melt increased. At an electrolysis temperature of 1010 °C, current density of
500 mA/cm2 and electrolysis time of 6 h, the Si concentration in melt increased
from 0.924 to 4.025%, and the B deposition at the cathode decreased from 0.172 to
0.011% (removal rate of 93.6%).
Acknowledgements The authors gratefully acknowledge the financial support from the State
Natural Science Fund (No. 51674301).
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The Application of an Effective
Equilibrium Reaction Zone Model Based
on CALPHAD Thermodynamics to Steel
Making
Paul Mason, A. Nicholas Grundy, Ralf Rettig, Lina Kjellqvist,

Johan Jeppsson and Johan Bratberg
Abstract TCOX9 is a thermodynamic database (developed using CALPHAD)

which describes the thermochemical interactions between liquid steel and slag during
steel making and refining. It contains all the major steel alloying elements (Fe–C–
Co–Cr–Cu–Mn–Mo–Nb–Ni–V–W–Ti) as well as the most important slag elements
(Ca–Mg–Si–Al–F–O–P–S). The ionic liquid model describes the liquid phase over
the whole composition range from metallic liquid (steel) to oxide liquid (slag). The
database also contains the most important metallic and non-metallic solid phases,
allowing the calculation of inclusion formation, inclusion modification, steel solidi-
fication, slag solidification, steel–refractory reactions, slag–refractory reactions, and
steel–mould powder reactions. For use with this database, a new process metallurgy
module has been developed within Thermo-Calc which makes it easy to set up cal-
culations for steel and slag. An extension to the module is under development that
incorporates a kinetic model of the steelmaking process based on the concept of
effective equilibrium reaction zones. This model is outlined in detail in this paper
and applied to a ladle furnace steel refining process.
Keywords Steel · Slag · Process metallurgy · Steel making · Steel refining ·

Kinetic modelling · CALPHAD
Introduction
Computational thermodynamics, and specifically CALPHAD (CALculation of

PHase Diagrams) [1], allows for the prediction of the thermodynamic properties
and phase stability of chemical systems, under stable and metastable conditions. The
current version of Thermo-Calc Software’s CALPHAD database for oxide materials
(TCOX9, released in June 2019 [2]) has seen significant development in recent years
P. Mason (B)
Thermo-Calc Software Inc, McMurray, PA, USA
e-mail: paul@thermocalc.com
A. N. Grundy · R. Rettig · L. Kjellqvist · J. Jeppsson · J. Bratberg
Thermo-Calc Software AB, Solna, Sweden
https://doi.org/10.1007/978-3-030-36540-0_10
102 P. Mason et al.
and now contains all the important elements for most steels, steelmaking slags, and
refractory materials (Fe–C–Co–Cr–Cu–Mn–Mo–Nb–Ni–V–W–Ti, Ca–Mg–Si–Al–
F–O–P–S). Physical properties of liquid and solid phases such as molar volume,
surface tension, interfacial energies, and viscosity are planned for inclusion in the
near future. The database is thus excellently suited for the calculation of reactions
occurring during the steel making and steel refining process, for example, carbon
removal by oxidation, dephosphorization, desulphurization, deoxidation (killing),
alloying, refractory wear, inclusion formation, and modification.
CALPHAD is a phase-based approach, whereby the thermodynamic properties of
each phase are described through the Gibbs free energy which is evaluated through a
critical assessment of all experimental and theoretical information available on phase
equilibria and thermochemical properties in a system. This methodology enables the
prediction of temperature and compositional effects on phase stability. The approach
assumes thermodynamic equilibrium, but by incorporating kinetic models, or impos-
ing certain constraints on the results, non-equilibrium/metastable equilibrium states
can be predicted.
It is well known that the reactions occurring during steelmaking and refining do
not reach thermodynamic equilibrium and are limited by kinetics, the limiting factor
being mass and heat transfer to and from the phase interface where the reactions
occur. A simple but powerful model to account for reaction kinetics was originally
developed at Brian Thomas’ group by Peter et al. [3] and has more recently become
known as the effective equilibrium reaction zone (EERZ) model [4–6]. In this paper,
we first present the TCOX9 database that is developed based on the CALPHAD
methodology. Then the EERZ model is outlined and applied in its simplest form to
simulate the kinetics of the ladle refining process of a Ti-stabilized ULC published
by Graham and Irons [7]. When coupled with TCOX9, despite the simplifications,
the experimental data from the plant trial can be well reproduced.
The TCOX Database
In TCOX9, the Gibbs energy of the liquid phase is described using the ionic two-
sublattice liquid model [8, 9]. This model allows the composition of the liquid
phase to continuously change from metallic to oxidic. The liquid steel and the slag
phase are thus described in a physically correct manner as one and the same phase
(IONIC_LIQUID) that can have different compositions which are separated by one
or more miscibility gaps. In equilibrium, all elements partition to either side of the
miscibility gap. This means the concentration and activities of all elements in the
liquid steel and the slag phase are calculated as a function of bulk composition,
temperature, oxygen activity, etc., by the condition of thermodynamic equilibrium.
Apart from the liquid phase, TCOX9 contains all the solid oxide and sulfide phases
that are relevant for secondary steel making, the major solid metallic phases and a gas
phase. This means that not only the composition of the liquid steel and slag phase can
be calculated, but also the amounts and compositions of all other solid phases that
The Application of an Effective Equilibrium Reaction Zone Model … 103
Fig. 1 Calculated versus measured S content in various CMAS slags in equilibrium with liquid Cu
might be present. It also means that most steel-making processes can be simulated
using this single database.
The database has been developed using the well-established CALPHAD method
using many different types of experimental data and has been expanded and improved
by careful curation and validation over many years. Currently, the database contains
about 360 phases and a total of 250 binary systems, 220 ternary systems, 90 pseudo-
ternary oxide systems, and 30 oxy-fluoride and oxy-sulfide systems have been fully
assessed. The reliability of the database in the multi-component composition space
has been validated against a large number of critically assessed experimental data-
points. For illustration, Fig. 1 shows the calculated S content in ladle slags compared
with experimental data from Allertz [10]. More details on the TCOX database and
its applications to alloy process design can be found in the recent review by Dilner
et al. [11].
Description of the Kinetic Model for Steelmaking

and Refining
A simple but powerful way to combine kinetic effects with thermodynamic equilib-
rium calculations, that has been widely used to simulate the steelmaking process [3–
6], has come to be known as the effective equilibrium reaction zone (EERZ) model.
This kinetic model is currently being implemented within Thermo-Calc Software’s
new Process Metallurgy Module that was introduced in June 2019 and is expected to
be released in 2020. Kinetic simulation will lead to a better understanding of existing
steelmaking and steel refining processes and allow the fine tuning and optimization
of process parameters. It will also allow the development of process parameters for
new steel grades that are to be added to the steel producer’s product portfolio.
The kinetic model assumes local equilibrium at phase interfaces, such as the
interface between liquid steel and slag. The kinetics of the reactions are limited by
the mass and heat transfer to and from the reaction interface along compositional and
thermal gradients. In the EERZ model, this is accomplished by assuming that only
104 P. Mason et al.
a fraction of the liquid steel and the slag phase reach thermodynamic equilibrium
during a certain time step. The details of how this is done is outlined below.
Kinetics of the Reaction Between Liquid Steel and Slag
Considering only the reaction between the slag phase and the steel liquid phase, one
time step can be subdivided as follows (sketches 1–6 in Fig. 2).
(1) Initial situation with a liquid steel (steel zone) and slag phase (slag zone) next
to each other but not in equilibrium.
(2) An effective equilibrium reaction zone (EERZ) is defined encompassing a frac-
tion of the liquid steel phase and a fraction of the slag phase. The size of the zone
determines the kinetics. A large EERZ results in fast kinetics, a small EERZ
in slow kinetics. The factor defining the size of the EERZ is thus mass trans-
port to and from the reaction zone. Empirical relations between mass transport
and parameters such as viscosity of the liquid steel and slag, stirring intensity,
number and positioning of porous plugs, and surface area can be found in the
literature (for example Harada et al. [12] and references therein).
(3) The bulk chemical composition within the EERZ is calculated.
(4) The equilibrium phase fractions and phase compositions within the EERZ are
calculated.
Slag (1) (2) (3)
Define EERZ Mix EERZ

composiƟon.
before
Liquid
steel
(4) Mix slag (5) Slag (6)
Calculate equilib. in EERZ

ComposiƟon
Liquid
. aŌer
steel
Mix liquid steel
Fig. 2 Schematic of the kinetic model assuming only the reaction between the liquid steel and the
slag phase
(5) The oxide phases in the EERZ are mixed with the rest of the slag phase, the
metallic phases in the EERZ are mixed with the rest of the liquid steel.
(6) A new liquid steel and slag composition is achieved that is closer to equilibrium.
In the next time step, the cycle restarts at 1.
These six steps outline the general principle of the EERZ model without addition of
alloys or other materials and without considering heat input or heat loss.
Material Additions at Each Time Step
In steelmaking and steel refining, various materials are added to the ladle at different
points in time. These can be distinguished as one-time bulk additions (e.g., Scrap
addition to a converter, addition of ferroalloys, addition of bulk slag formers, etc.,
…) or additions with a feeding rate (e.g., injection of a gas such as oxygen, carbon
or lime powder injection, wire feeding, etc., …). The method by which the material
is added determines the predominant way it dissolves and reacts. Ferroalloys such as
ferromanganese will sink through the slag phase then melt and dissolve in the liquid
steel. Carbon, lime, or gas injection displaces the slag on the surface and the added
elements react partially with the slag phase and partially with the liquid steel. Bulk
additions of slag formers such as lime (CaO) could be added to the top of the slag.
When setting up a kinetic model, these considerations define the most reasonable
zone the materials should be added to; the slag zone, the liquid steel zone, or the
EERZ itself.
Figure 3 illustrates the material additions outlined above during one time step of
the kinetic model.
(1a) (2) (2a)

Slag formers
dissolve in slag
Define EERZ
Injected
Ferroalloys material
dissolve in liquid dissolves in
steel EERZ
Fig. 3 Schematic of the kinetic model for material additions

106 P. Mason et al.
Material Additions with Formation of New Phases: Phase

Transfer
The assumption made above is that the added material simply melts and is dissolved
in the zone to which it is added. This assumption is mostly true if a ferro-alloy
addition is made to the liquid steel zone or a slag former is added to the slag phase.
However, certain additions will result in the formation of a “foreign” phase (i.e.,
non-metallic phases in the liquid steel zone and metallic phases in the slag zone).
The most typical example for this is the addition of a deoxidizing agent such as Al
or Si to the liquid steel coming from the converter or EAF, that contains a large
amount of dissolved oxygen. Such an addition will result in the formation of Al2 O3
(corundum), SiO2, or other more complex solid oxides or even liquid oxide droplets.
These phases (often referred to as inclusions) have a lower density than the liquid
steel and gradually float upwards aided by rising gas bubbles from purging gas that
is fed through porous plugs at the bottom of the ladle. At every time step, a certain
fraction of these inclusions will combine with the slag phase and be removed from
the liquid steel. The rate at which this happens is governed by the phase transfer per
time step given in percent per minute.
The same approach is used to model the transfer of metallic phases formed in the
slag zone. If, for example, due to slag carryover from the furnace, the slag contains
high amounts of FeO and MnO, then strongly reducing slag conditioners (metallic
Al or CaC2 ) can be added to the top of the slag. These melt and reduce the FeO and
MnO, possibly even SiO2 and other slag components to metallic Fe, Mn, and Si.
The resulting liquid metal droplets sink through the slag and combine with the liquid
steel. This process of phase transfer is outlined in Fig. 4.
Fract. of met. phases (1e) (1d) (1c)

transfer to steel CondiƟoners
Metallic phases form (e.g. Al, CaC2)
in slag zone added to slag
Deoxidizers or
FracƟon of non- Non-metallic oxides added to
met. Phases phases form in steel
transfer to slag steel zone
Fig. 4 Schematic of the kinetic model for material additions resulting in the formation of new
phases and the transfer of these newly formed phases from one zone to another
Isothermal Versus Isenthalpic or Adiabatic Equilibrium

Calculations
In the EERZ model, there are two ways to define the conditions of thermodynamic
equilibrium. The first is to fix temperature (isothermal condition). This requires
that heat evolving from exothermal reactions, for example the heat evolved by the
oxidation of C to CO gas by oxygen blowing in a converter, is dissipated out of the
system and the enthalpy of the system gets lower. The heat required for endothermic
reactions must flow into the system thereby increasing the enthalpy. In most cases,
this is not a good approximation of what happens in reality.
The second possibility is to fix the enthalpy of the system (adiabatic conditions).
This allows work to be exchanged with the surroundings, but not heat. The work that is
exchanged is volume change against the external pressure (p.dV). This term becomes
important for calculations involving the gas phase and significant differences are
obtained for calculations under vacuum conditions or ambient conditions. Fixing the
enthalpy means that heat evolving from an exothermic reaction stays in the system
and results in a temperature increase and vice versa for an endothermic reaction.
Heat Addition and Heat Loss at Each Time Step
For adiabatic calculations, heat can also be added or removed from the system. For
example, heat can be lost through the ladle walls or heat can be input by electric arc
heating. The increase or decrease of enthalpy in the system results in an increase or
decrease of the temperature. The heat added to or removed from the system must
be attributed to a certain zone. The most reasonable choices might be that heat lost
by conduction through the ladle walls is removed from the steel zone, heat loss by
radiation off the top of the ladle is removed from the slag zone, and heat added by
electric arc heating is probably best accounted for by adding enthalpy to the EERZ. It
is important to note that heat is also added when materials are added. The added heat
corresponds to the enthalpy of the added materials at the temperature they have on
addition. The enthalpy of added materials is not only dependent on its temperature
and composition, but also on its phase assemblage. Adding a mechanical mixture
of SiO2 (as quartz) and CaO (as halite) with a temperature of 25 °C will result
in a different enthalpy input compared to the addition of a crushed glass with the
composition CaO. SiO2 and temperature of 25 °C.
Heat Exchange Between the Various Zones
When implementing adiabatic conditions, different amounts of heat can be added

to or removed from the different zones. This evidently results in the zones having
108 P. Mason et al.
(2c) (5a) (5b)

RadiaƟve heat loss from
slag zone
Heat from electric
arc added to EERZ
Thermal balance
Heat loss from steel
zone through ladle between steel and
slag zone by heat
walls
transfer
Fig. 5 Heat added to and removed from system and heat exchange between different zones
different temperatures and these differences propagate from one time step to the next.
There are two ways to alleviate this problem.
(1) Impose thermal equilibrium between the liquid steel and the slag phase at the
end of each time step. This is computationally expensive as it requires iterative
calculations to determine the exact distribution of enthalpy between the zones
to achieve equal temperatures.
(2) Assume a certain heat transfer between the liquid steel and slag phase in the
form Q. T at the end of each time step. This is simple to implement and allows
the different zones to have slightly different temperatures, which is certainly a
realistic assumption. However; care must be taken, that Q is not too large, as
this would result in an inversion of the temperature difference (Fig. 5).
Application of the Model to the Ladle Refining

Process—Proof of Concept
In a previous paper [12], the model outlined above was applied to the whole steel-
making and steel refining process from scrap to fully refined steel, ready for casting.
However, little detail was given and no comparison with actual experimental data
was presented. Here, we simulate the kinetics of the ladle refining process of a
Ti-stabilized ULC published by Graham and Irons [7].
Graham and Irons [7] have published experimental data of the steel refining pro-
cess at AM Dofasco plant in Hamilton (ON). AM Dofasco has an annual production
of app. 4.5 mt of flat products (hot strip) from two melt shops, a basic oxygen furnace
(BOF) converter shop with a 265 t heat size and an AC electric arc furnace (EAF)
melt shop with a 165 t heat size. The BOF shop has a single ladle furnace (LF) and
a single tank type vacuum degasser (VD). For the EAF shop, they have a twin ladle
furnace, but no vacuum degasser. The experimental data are from the EAF shop.
Unfortunately, the process data reported by Graham and Irons is incomplete.
Nevertheless, Van Ende and Jung [4] have taken the published data and estimated the
missing process parameters as well as they could to set up a process simulation based
on their effective equilibrium reaction zone (EERZ) model that uses thermodynamic
data coming from the FactSage database system [14]. For the kinetic simulation
presented in this paper, the process parameters as reported by van Ende and Jung
are used, with the only exception, that we include the element Ti, that was for some
reason not considered by these authors. Unlike van Ende and Jung, who performed
an elaborate simulation with many time steps and fine-tuned kinetic parameters, we
have set up the simulation in the simplest possible way, using only six simulation
steps and constant kinetic parameters throughout. The aim is to clearly outline the
principles of the simulation method, so that it can be easily repeated without any
knowledge of programming and can serve as a basis of a more elaborate model
using, for example, one of Thermo-Calc Software’s APIs such as TC-Python.
In spite of the extreme simplification made in this work, the experimental plant
data reported by Graham and Irons can be well reproduced, as shown in Fig. 6, clearly
demonstrating the robustness of the model and the reliability of the TCOX database
for such calculations.
Fig. 6 Calculated results of this work compared to experimental data from Graham and Irons [7]
and simulation by van Ende and Jung [4]
110 P. Mason et al.
Initial conditions:
Liquid steel zone:165 t of liquid steel at 1600 °C. Composition in wt%: Fe-0.12
Mn-0.008 Si-0.001 Al-0.001Ti-0.06 S-0.01 O (Taken from [4], see note below on
oxygen content).
Slag zone: 4.95 t of slag at 1600 °C. Composition in wt%: 50 CaO-31.2 Al2 O3 -8
MgO-6.0 SiO2 -0.8 MnO-1.9 FeO-2.19 TiO2 -0.01 S (Taken from [4] but adjusted to
include TiO2 )
Process parameters:
1 min: 105 kg Al added (taken from [4]).
20 min: add 100 kg CaO, 140 kg Al, 50 kg FeMn (amount taken from [4],
composition assumed 78 Mn–22 Fe).
27–34 min: electric arcing (heating is assumed to add 600 kJ/min of heat to system,
heat addition chosen to fit experimental temperature measurement).
39 min: add 46 kg FeTi (amount taken from [4], composition assumed 80 Ti–20
Fe).
Kinetic parameters. All parameters kept constant throughout the simulation.
Size of equilibrium reaction zone: 5% of liquid steel and 5% of slag volume per
minute.
Inclusion removal rate (phase transfer): 4.5% per minute (instead of 6% per minute
as given in [4]).
Heat loss: −200 kJ/min (assumed value to fit experimental temperature measure-
ment).
Heat transfer from slag to steel zone: 5 kJ/min (assumed value to keep steel and
slag in thermal equilibrium)
Calculation steps for kinetic simulation
Calculation times are chosen to correspond approximately to sampling time.
Initial (time = 0): Add the 165 t of liquid steel to steel zone and 4.95 t of slag to
the slag zone. Calculate the enthalpy of the steel and slag zone. For all subsequent
calculations, the enthalpy is used as a condition and not the temperature. This means
that temperature changes on heat loss (enthalpy removed from the system) or active
heating (enthalpy added to the system) are calculated. Temperature also changes due
to endothermic or exothermic reactions that might take place due to alloy or other
additions.
Step 1 (time = 1 min): Add 105 kg Al to the liquid steel zone (see note on Al addition
below). App. 35 kg of solid Al2 O3 deoxidation products are formed (inclusions). This
reaction is strongly exothermic, and the temperature of the steel zone is increased by
3 °C.
Step 2 (time 1–7 min): 30% of the non-metallic phases (inclusions) in the steel zone
transferred to the slag zone. The EERZ is defined containing 30% of the steel zone
and 30% of the slag zone. Equilibrium in the EERZ is calculated. Resulting metallic
phases are added to the steel zone, resulting in non-metallic phases added to the slag
zone. 1800 kJ of heat removed from the steel zone. 30 kJ of heat transferred from the
slag zone to the steel zone to achieve thermal balance between steel and slag zone.
Step 3 (time 7–16 min): Same as step 2, except scaled for the longer time step of
9 min instead of 6 min.
Step 4 (time 16–25 min): 50 kg of FeMn is added to the steel zone. 100 kg CaO and
140 kg Al added to the EERZ (see note on Al addition below). Other steps identical
to step 3.
Step 5 (time 25–34 min): 4.5 MJ of heat added to the EERZ. Other parameters like
step 3.
Step 6 (time 34–43 min): Add 50 kg of Fe–Ti to steel zone (see note on Ti below).
Other parameters like step 3.
Note on O content.
Van Ende and Jung [4] assume an initial oxygen content of 100 ppm before the first
deoxidation with Al. This assumption is probably not realistic. The dissolved oxygen
in the liquid steel coming from the EAF is typically much higher, but unfortunately,
this data is not reported in the paper by Graham and Irons [7], who only report oxygen
content in the ladle furnace after initial deoxidation. We have, nevertheless, accepted
the assumed 100 ppm, in order to be consistent with the simulation of van Ende and
Jung.
Note on Al addition.
Graham and Irons [7] give the times at which Al is added (at 0 and 19 min), but do
not give the amounts. The amounts of 105 kg at 1 min and 140 kg at 20 min are taken
from van Ende and Jung [4], who probably determined the amounts using the steel
and slag chemical analysis. The zones to which alloys are added have a profound
influence on the results of the simulation. Only when adding the first Al addition of
105 kg to the steel zone and the second Al addition of 140 kg to the EERZ is the
experimental data well reproduced. It is reassuring that this choice is also the one
that best represents the method by which Al was added. The first addition of 105 kg
was probably performed during tapping resulting in quick and complete melting and
mixing with the liquid steel. The second addition of 140 kg was into the “stirring
eye”, where the slag layer is thin and enhanced mixing between the steel and the slag
occurs.
Note on Ti addition.
Van Ende and Jung [4] did not consider Ti at all, despite the importance of this
addition for further processing of the steel. As already mentioned, the data given
by Graham and Irons [7] is incomplete; for example, no mention is made on the
C and N content of the steel. The fact that Fe–Ti was added close to the end of
treatment suggests that the steel being produced was Ti-stabilized low or even ultra-
low-carbon steel for deep-drawing applications. The reason Ti is added to these
steels is because it combines with the N and O dissolved in the liquid steel to form
stable Ti(C, N) precipitates. These serve a dual purpose: (1) N and C to some extent
are scavenged from the matrix (ferrite /austenite) improving the drawability (2) the
formed precipitates result in grain refining that improves the mechanical properties
of the final product. Ti addition is also a means to produce low-carbon steels with
acceptable drawability when no vacuum degassing is available for lowering the C
and N content during steel refining.
112 P. Mason et al.
Summary and Outlook
Thermo-Calc’s oxide database, TCOX9, is excellently suited to simulate steel-slag-

gas phase reactions occurring during steel making and steel refining. However, these
reactions never achieve thermodynamic equilibrium in practice, but are limited by
heat and mass transfer to and from the reaction zone. A simple but powerful method to
simulate the kinetics of steel making and refining is the effective equilibrium reaction
zone model (EERZ). In this model, it is assumed that only a fraction of the liquid steel
phase and slag phase reach thermodynamic equilibrium during a given time step. This
volume fraction reaching thermodynamic equilibrium is the effective equilibrium
reaction zone. The larger this volume is, the faster are the reaction kinetics. The model
is explained in detail and has been used to simulate real steel plant data taken from
the literature. Even though the model has been implemented in a highly simplified
way with only very few adjustable kinetic parameters and only six calculation steps,
all experimental data can be satisfactorily reproduced, indicating that both the model
and the thermodynamic database, TCOX9, is well suitable for such simulations.
The model outlined here is currently being implemented in Thermo-Calc Software’s
recently released Process Metallurgy Module. This will allow quick and easy set-up
of kinetic simulations of the steel making and steel refining process.
References
1. Kaufman L, Bernstein H (1970) Computer calculation of phase diagrams (With special

reference to refractory metals). Academic Press Inc., New York
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Optimization Dephosphorization Process
of the Early Stage in 300t Steelmaking
Converter with Top and Bottom
Combined Blowing
Chao Feng, Rong Zhu, Baochen Han, Kai Dong, Weifeng Li

and Guangsheng Wei
Abstract The effect of oxygen supply systems and slag composition on dephospho-
rization rate in the early stage of smelting was studied. Metal samples, slag samples,
and molten steel temperatures of a 300t converter at different smelting stages were
analyzed. The alkalinity of slag was found to be the lowest at 1.33 during the early
stage of the experiment, superheat was 7 °C, the mass fraction of C3 MS2 phase was
35 wt%, and average dephosphorization rate was 32.2%. By optimizing the oxy-
gen supply system and charging system of the converter, the alkalinity of slag was
controlled in the range of 1.6–2.1 and the average content of T.Fe was 15 wt%. The
results demonstrated a 10.2% increasment in dephosphorization rate during the early
stage of smelting, 5.9% increasment in the scrap steel ratio, 31 °C increasment in
the tapping temperature, and 0.65% increasment in the final dephosphorization rate.
Keywords Slag · Dephosphorization rate · Basicity
Introduction
High-performance clean steel has strict requirements for phosphorus content espe-
cially employing large scale converter, because phosphorus is recognized as an unde-
sirable element in most steel grades. An increase in the phosphorus content leads
to a decrease in the ductility and deterioration of the weldability of steel. High-
grade pipeline and marine steel have a strict requirement that phosphorus content
is generally less than 100 ppm. When manufacturing steel, the phosphorus content
in converter steel tapping has a considerable impact on the phosphorus content of
steel produced; therefore, to achieve the desired content of phosphorus in steel as
per the composition requirements, it is important to control the phosphorus content
C. Feng (B) · R. Zhu · B. Han · K. Dong · W. Li · G. Wei

e-mail: ustbfengchao@163.com

https://doi.org/10.1007/978-3-030-36540-0_11
116 C. Feng et al.
during converter steel tapping. Many researchers [1–7] have conducted theoretical
research and industrial experiments and summarized several methods to realize con-
verter smelting of low-phosphorus steel. Tomiyama et al. [8] proposed a new two-step
dephosphorization control system for steelmaking process and validated its perfor-
mance. Yang et al. [9] proposed a process for producing low-phosphorus steel using
a double slag method. Steel with a final phosphorus content of less than 0.007%
was achieved using double slag smelting. In addition, Tian et al. [10] studied the
production of low-phosphorus steel using a double slag process in a 210-tons con-
verter and verified that the phosphorus content of tapping steel was less than 0.005%.
Pak and Fruehan [11] studied the phosphorus distribution ratio of Na2 O–SiO2 –P2 O5
slag to carbon saturated iron and the dephosphorization ability of slag. Liu et al.
[12] studied the efficiency of dephosphorization reaction and phosphorus fixation
of low-alkalinity steel slag in converter steelmaking. By using low-alkalinity and
low-iron oxide slag system, the consumption of auxiliary materials in steelmaking
was reduced. Wu et al. [13] adopted the method of retaining slag and double slag
in the converter to control factors such as the temperature of converter, alkalinity of
final slag, and content of FeO in slag, such that the mass fraction of phosphorus in
tapping steel of converter was less than 0.007%.
In this paper, the dephosphorization process in a 300t converter was studied and
the oxygen lance operation process and converter smelting process were optimized
to achieve the desired phosphorus content of tapping steel.
Sampling and Analysis
Currently, to achieve less than 0.015% of phosphorus content and a scrap steel ratio of
5.53% once converter smelting is completed, and to utilize the returned mineralized
slag, an amount of 40 kg/t ore is added during the smelting process. As a result of the
excessive amount of sinter added during the smelting process, the furnace temperature
considerably fluctuates, slag amount increases, and consumption of lime and iron
loss are considerably increased; the final tapping is well controlled. A temperature in
the range 1600–1620 °C is achieved that helps prevent high temperature phosphorus
recycling. An analysis of the smelting production data demonstrates that the average
phosphorus content at the end of smelting process is 11.6%. Owing to the low tapping
temperature of the converter, further LF and RH refining is required before continuous
casting leads to an increase in energy consumption. To this end, the existing smelting
process needs to be analyzed and its shortcomings need to be addressed.
The metal and slag samples are extracted and temperature was measured at four
different time points: 5 min into the process, 10 min into the process, TSC, and
TSO after the start of oxygen supply in smelting. TSC is the time of 85% oxygen
supply and TSO is the time after the end of oxygen supply. Four stoves of samples
were extracted and measured, numbered NO.1, NO.2, NO.3, and NO.4, respectively.
The temperature at each of different time points in the process of smelting was
measured by a converter sub-lance equipment and system, and then metal samples
Optimization Dephosphorization Process … 117
Table 1 Composition changes of metal samples at different times of smelting

Time (min) Molten steel element (%) Temperature (°C)
C Si Mn P
0 5.33 0.45 0.19 0.09 1389
5 3.22 0.05 0.056 0.071 /
10 1.98 / 0.08 0.058 /
TSC 0.635 / 0.108 0.038 /
TSO 0.061 / 0.056 0.009 1624
Table 2 Composition change of slag samples at different times in smelting

Time (min) Slag sample (%) R
T.Fe SiO2 CaO P2 O5 MgO
5 9.35 28.33 37.79 3.27 7.3 1.33
10 11.98 25.19 38.87 3.4 7.4 1.54
TSC 12.26 21.15 43.25 3.44 8.33 2.04
TSO 23.51 12.24 39.3 2.45 9.87 3.21
were extracted. Subsequently, the slag samples were extracted after rotating the
converter mouth to a certain angle. Owing to the complexity of the smelting process
and the influence of production rhythm, the NO.2 (5 min. timepoint) metal samples
were not extracted, as well as the NO.3 (10 min. timepoint) slag samples. Data on
the composition of metal and slag samples accompanying the smelting process are
listed in Tables 1 and 2.
Table 1 indicates that during the process of smelting, carbon (C) in molten steel
decreases with time. Further, the residual amount of silicon (Si) was very small after
about 5 min into smelting. Phosphorus content decreased with an increase in the
oxygen supply time. The final dephosphorization rate was 90%; the dephosphoriza-
tion efficiency after 5 min of oxygen supply was only 21.1%. The dephosphorization
in this furnace occurs when oxygen was supplied. Having oxygen supply during a
late stage in the smelting process is however not very conducive for achieving the
final composition stability of low-carbon steel smelting. Table 2 indicates that during
the process of smelting, the content of T.Fe in the slag increases with time and the
T.Fe content at the end of smelting is approximately 23.51% and this has a negative
impact on final metal yield. The alkalinity of slag is found to be 1.33 in the NO.1
sample (collected 5 min into the smelting process), and this is probably due to the
insufficient dissolution of lime; further, this low alkalinity is not conducive to the
early dephosphorization of the converter. The superheat of slag can be estimated by
determining the fluidity of the slag. When the NO.3 sample is further smelted for
5 min, the temperature of slag is found to be 1373.3 °C and the temperature of molten
metal pool is 1380 °C, and therefore, the superheat of slag at the 5 min point in the
smelting process can be estimated as 6.7 °C. This indicates that the temperature of
118 C. Feng et al.
Table 3 Dephosphorization rate at different stages

Moment (min) Number (%) Average value
NO.1 NO.2 NO.3 NO.4
5 22.2 / 48.5 26.2 32.2
10 35.6 74.7 66 42.1 54.6
slag is higher, temperature of molten pool is lower, and fluidity of slag is higher.
These conditions are not conducive to the dephosphorization reaction during the
early stage of smelting.
Table 3 lists the dephosphorization rate obtained from samples extracted 5 and
10 min after the converter smelting process commenced. The table indicates that the
average dephosphorization efficiency is only 32.2% in the early stage and 54.6% in
the middle stage. This indicates that the main dephosphorization reaction occurred
during the later stages of the smelting process. This can be attributed to the low-
oxygen flow rate and the increasment in FeO content in slag during TSC temper-
ature sampling. While this is advantageous to the dephosphorization reaction, it is
not conducive for the stable control of the end-point phosphorus content in a large
converter.
To achieve the required phosphorus content at the end point of molten steel smelt-
ing, it is important to control the high oxidation and alkalinity of slag as well as the
tapping temperature in a lower range; this is not ideal from the perspective of the
smelting cost and quality control. An optimization process that optimizes the smelt-
ing process and improves the pre-dephosphorization efficiency of converter is thus
required. The final phosphorus content of molten steel can then be stably controlled.
Figure 1 shows the slagging route of NO.1 sample, which has been extracted
during the initial stage of smelting. The main phase of acid slag is C3 MS2 and it
Fig. 1 Slag forming route in

NO.1 smelting process
accounts for 35% of the total mineral phases present. The melting point of magnesia–
wollastonite (C3 MS2 ) is 1598 °C. The mineral phase composition indicates that the
amount of lime and dolomite is small, alkalinity of slag is low, and content of T.Fe
in slag is low; these conditions are not conducive for the dephosphorization reaction.
The content of magnesite and calcium silicate increased with the alkalinity of slag
during the middle stage of the smelting process. The main mineral phase of the TSC
slag is dicalcium silicate, accounting for 50%, improving the fluidity of slag. The
main mineral phases found in the slag extracted at the end of the blowing step in the
smelting process are calcium silicate (45%) and calcium ferrite (C2 F) 32%. This slag
has strong dephosphorization properties, and therefore, the dephosphorization rate
at the end of blowing approaches 90%. The ratio of calcium ferrite ore is observed to
be high, resulting in faster lining erosion. Hence, it is desirable to reduce the content
of T.Fe in the final slag.
Optimizing and Discussing
The average temperature of the molten pool in the fourheats at 5 min was 1400 °C
and this satisfied the thermodynamic requirements for slag melting. During the early
stage of the smelting process, it is also necessary to improve the dynamic conditions
of the molten pool, which speed up lime dissolution and increase the alkalinity of
the slag to design conditions that are conducive to dephosphorization.
Optimizing oxygen supply system and the operating lance position
The original oxygen lance nozzle had five holes, a throat diameter of 48.5 mm, and an
outlet diameter of 64.5 mm. The angle between the nozzle and the nozzle center line
is 15° and the oxygen flow rate is 52000 Nm3 /h and the average oxygen supply time
is 15.5 min. The primary function of the nozzle is to cause stirring of the molten pool.
The number of nozzles and the position of oxygen lance is the key parameters that
influence the stirring energy of the nozzle during the smelting process. Assuming
that the supply of oxygen flow has to be maintained constant, an increase in the
number of nozzles will increase the stirring energy of the jet into the molten pool.
An optimized design of the nozzle for the oxygen lance is proposed that used six
holes and has a throat diameter of 41.5 mm, an outlet diameter of 56 mm and is
oriented at 15.5° from the nozzle center line.
Figure 2 shows the variation in stirring energy of the molten pool with the origi-
nal 5-hole nozzle and the optimized 6-hole nozzle. Under the same operating lance
position, the optimized 6-hole nozzle exhibits an 8.1% increasment in the stirring
energy compared with the original 5-hole nozzle. This increasment in the stirring
energy resulted in a better dissolution of lime during the early stages of the smelt-
ing process and an increasment of slag alkalinity, which was both favorable for
dephosphorization.
The operating position of oxygen lance influences the stirring energy of the oxygen
jet in the molten pool. In the original configuration, the lance position of the oxygen
lance was 2.5 m. In our testing, the operating lance position is reduced to 2.1 m
120 C. Feng et al.
Fig. 2 Variations in the

stirring energy of jet to
molten pool before and after
optimization
during the early stage of smelting and 2.0 m during the middle stage of the smelting
(the decarbonization stage); further, the lance position is maintained at 1.7 m up to
1 min prior to the end point of the smelting process. The stirring ability of the oxygen
jet in the molten pool decreases with an increasment in the pre-stage lance position,
which is not favorable to the dissolution of lime. Low lance position operation in
a long time at the pre-smelting stage reduces the FeO content in the slag that leads
to the rapid decarburization, which leads to dry slag. Therefore, it is necessary to
optimize the pre-stage lance position and the holding time carefully.
Figure 3 shows the optimized schedule of the oxygen lance position. To realize
a stable phosphorus content during the converter smelting process, the operating
parameters for the oxygen lance operation with a scrap steel ratio in the range of
10–15% was determined. The lance operation level in the early stage of the smelting
process was reduced to 1.8 m, and after 2.5 min was increased to 2.15 m. It was
then maintained at this level during the TSC temperature measurement and sampling
stage. Subsequently, it was lowered to 1.9 m about 1.5 min prior to the end of the
Fig. 3 Oxygen lance

position model
blowing stage and then further reduced to 1.15 m and then 0.7 m. By reducing the
lance level of the oxygen lance during the early stage of smelting resulted in an
increase of 25.56% in the stirring energy of the jet into the molten pool providing
for a good dynamic condition for lime dissolution. The oxygen supply time of this
optimized process was also shortened by about 30 s compared with the original
process.
Optimizing the Loading System
The original process achieved a stable and lower P content by adding large amounts
of sinter to produce high amounts of oxidizing slag. Adding a large amount of sin-
ter results in a large quantity of slag, which negatively affects the metal yield and
accelerates the erosion of the lining. Therefore, it is necessary to reduce the amount
of sinter added to increase the scrap steel ratio and increase the yield of contain-
ing Fe materials. An optimized smelting process using a new charging system for
the convertor has been determined. The mixture of 70% lime, 100% lightly burned
dolomite, and 60% ore was added after oxygen lance ignition and the remaining
slagging agents were added within 4–8 min of the converter smelting process. This
optimized oxygen lance operation resulted in a quick dissolution of lime and the
amount of added sinter was reduced by 14.6% and added metal content of 25.4 kg/t
per ton of steel was realized. The scrap ratio increased by 5.9%. The slag produc-
tion of converter is calculated by material balance and showed 9.5% reduction in
comparison with the original process.
The average alkalinity of slag reached 1.78 during the early stage of the furnace
smelting, and the fluidity of slag was observed by rotating the furnace mouth. The
average dephosphorization rate during the early stages of the smelting process was
more than 48% and this reduced the dephosphorization requirement in the later
stages of the smelting process. Based on the analysis of the smelting data, the final
dephosphorization rate for SPHC steel and IF steel increased by 0.65% on average
as a result of using the optimized smelting process. The tapping temperature for
the original smelting process was between 1600–1620°C, and this necessitated LF
refining to be heated prior to being poured into the continuous caster. This resulted in
increased energy consumption and process cost. To pour directly into the continuous
caster from the tapping of converter at the end of the RH refining, it is necessary
to control the tapping temperature at the end of converter. The optimized smelting
process helps realize an average tapping of the converter. The temperature of steel
is greater than 1655 °C and this provides sufficient heat to enable the production of
high-quality steel and process flexibility.
122 C. Feng et al.
Summary
Optimizing the charging system, oxygen supply system, and oxygen lance nozzle
parameters of converter can improve the efficiency of dephosphorization at the initial
stage of converter smelting, and control the phosphorus content and temperature
of tapping steel. The main reason for the low dephosphorization efficiency of the
original process in the early stage of smelting is the slow dissolution rate of lime
and the basicity of slag, which is 1.33. By optimizing the parameters of the oxygen
lance nozzle, the stirring energy of the jet increased by 25.56%, and the dynamic
conditions of the molten pool were improved. The average basicity of slag reached
1.78 and the average dephosphorization rate exceeded 48% in the initial stage of
smelting. The optimized feeding system reduced the amount of sinter content by
14.6%, the amount of scrap by 5.9%, and the amount of slag by 9.5%. The final
dephosphorization rate of converter is 0.65% higher than that of the existing process.
The tapping temperature of molten steel is higher than 1655 °C, which improved the
production efficiency and reduced the energy consumption and cost of the process.
Acknowledgements The authors would like to express their thanks for the support by the National
Nature Science Foundation of China (No. 51574021).
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17(4):797–804
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Mechanical Properties of a Laser
Deposited Spherical Ti4822 Alloy
Monnamme Tlotleng, Samuel Skhosane and Sisa Pityana
Abstract A crack-free cube was manufactured by depositing spherical GE Ti4822

alloy powder using a laser direct metal deposition technique. Tensile specimens were
wire cut and tested for tensile properties. Three kinds of specimen were tested: the
as-built and those that were heat treated in an argon rich environment at 1200 °C and
1400 °C and oven cooled. The results showed that the as-built samples had high UTS
(440.68 MPa) and very poor elongation (0.11%) while samples that were heat treated
at 1200 °C and 1400 °C had UTS of 382.95 MPa and 297.60 MPa, respectively. All
samples lacked plasticity. This study concluded that a coarse-grained fully lamellar
microstructure had low tensile strength which would suggest moderate toughness
and ductility at room temperature.
Keywords Direct energy deposition · Hardness · Microstructure · Laser

deposition · Ti4822 alloy · Tensile properties
M. Tlotleng (B)
Senior Scientist, Additive Manufacturing Research Group, Laser Enabled Manufacturing,
National Laser Centre, Council for Scientific and Industrial Research, Pretoria Campus, Pretoria,
South Africa
e-mail: mtlotleng@csir.co.za
Department of Mechanical Engineering Science, Faculty of Engineering and the Built
Environment, University of Johannesburg, Auckland Park Campus, Johannesburg, South Africa
S. Skhosane
Researcher, Additive Manufacturing Research Group, Laser Enabled Manufacturing, National
Laser Centre, Council for Scientific and Industrial Research, Pretoria Campus, Pretoria, South
Africa
e-mail: SSkhosane@csir.co.za
S. Pityana
Principal Scientist, Additive Manufacturing Research Group, Laser Enabled Manufacturing,
National Laser Centre, Council for Scientific and Industrial Research, Pretoria Campus, Pretoria,
South Africa
e-mail: SPityana@csir.co.za

https://doi.org/10.1007/978-3-030-36540-0_12
124 M. Tlotleng et al.
Introduction
Metal materials with good creep and fracture toughness properties are required in
the manufacturing of turbomachinery parts. The fourth generation alloys such as
Nickel (Ni) superalloys, with perfect homogenous microstructures post manufac-
turing and improved creep properties, are necessary for the manufacturing of these
turbomachinery parts. Ni superalloys are somewhat lighter than traditional steel and
titanium alloys, and are able to withstand operational temperatures to about 700 °C
without deformation. Hence they are preferred for non-conventional applications
including aerospace parts and nuclear energy reactors. Currently, Inconel (IN) 713/8
is used in the manufacturing of airfoil blades of compressors; even though stronger,
stiffer, hotter, and lighter materials are the perfect candidates. These required proper-
ties are synonymous with the gamma (γ) titanium aluminides (TiAl) alloys. γ–TiAl
alloys are lighted than IN alloys given that they have half their density, and can
perform better in temperature ranges of about 800–1000 °C. These attributes are
due to their well-ordered structure (long-range ordered super-lattice structure) that is
able to reduce dislocation motions at high temperatures. However, they lack room to
moderate temperature ductility hence they are difficult to cast into finished products
[1, 2].
Understanding their brittleness and heat sensitivity properties, research since their
early discovery is on improving their room temperature performance and ductility so
that they can be easily casted and machined. General information on Ti–Al alloys can
be reviewed from a publication by Nochavnaya et al. [3]. According to the available
phase diagrams, when Ti and Al are reacted, thermodynamically, they will form
three stable intermetallic phases, viz, α2 –, γ–, and (α2 + γ)–TiAl. The relevance
of the stable TiAl for structural engineering has been studied over the years. It has
become noticeable that the γ–TiAl phase is more stable when compared to α2 –
TiAl and dual-phase (α2 + γ)–TiAl. But, there are competing arguments around
which is more stable and has good structural properties for engineering; hence the
developments are now tailored towards the part being manufactured. In general, the
most favoured alloyed is the general electric Ti–Al with composition of Ti–48Al–
2Cr–2Nb (Ti4822). Chromium (Cr) and Niobium (Nb) are mainly ductility and phase
stabilizing micro-alloys, respectively. This alloy possesses a balanced combination
of cast and production properties, but has a low strength with tensile properties not
exceeding 490 MPa [3].
Most notable research that reported on a crack-free sample of Ti4822 alloy did not
come from those who use traditional casting. However, cast components followed
with hot isostatic pressing (HIPing) are successful and additive manufacturing tech-
niques excluding laser based direct energy deposition platforms. HIPing is able to
transform the microstructure of the cast from lamellar into duplex or equiaxed [2,
3]. The latter microstructures have improved ductility [4]. Electron beam melting
(EBM), an AM technique, is the most successfully used technique in the manufac-
turing of valuable Ti4822 alloy components [5]. The success of this technique is
attributed to low thermal residual stress that resulted in the built part as opposed to
Mechanical Properties of a Laser Deposited Spherical Ti4822 Alloy 125
laser-based manufacturing platforms [5, 6]. These thermal residual stresses can be
cured by heat treatment, post manufacturing in the built part [7], but if not controlled
during manufacturing, they lead to a crack-infested part being produced. Thermal
cracking in EBM platforms is controlled by pre-heating of the deposition base and
chamber to about 1000 °C. To date, to my knowledge, there hasn’t been a study that
has reported a crack-free Ti4822 component [7]. This study is probably the first to
report on the tensile properties of a laser manufactured Ti4822 alloy, and the effects
of heat treatment on the resulting hardness and ductility of such a successful built.
Materials
A commercially available GE Ti4822 powder was deposited in this study. The power
was supplied by WEARTECH (Pty) Ltd, Johannesburg and was spherical with a
particle size distribution of about 45–90 μm. The powder was used as received and
deposited onto Ti–6Al–4V base plates with dimensions of 70 × 70 × 7 mm3 . Before
deposition, the base plates (substrates) were sand-blasted and cleaned with acetone.
Direct Energy Deposition
Direct energy deposition system called Eskom laser was used in this study to produce
Ti4822 samples that were studied. This platform uses a 3 kW maximum power output
fibre laser as an energy source. The co-axial head is used to feed the depositing
powder into a laser melt-pool that would be created on the substrate. A Kuka robot
arm is used for motion control and deposition. During processing, the effects of
laser power (W), carrier gas (l/min), powder flow-rates (g/min), and composition
were investigated. The results reported here are on the optimized energy density,
re-determined continuously substrate heating temperature and soaking/stress relief
temperature. The process is summarised in Fig. 1 where (a) is the laser set-up and
(b) the produced sample.
Heat Treatment
Heat treatment was conducted on the tensile specimens that were cut out from the
built shown in Fig. 1b using wire cutting. Carbolite tube furnace was used for the
heat treatment experiments. Two heat treatment temperatures (1200 °C and 1400 °C)
were studied. Heat treatment was conducted under argon rich environment. A hold
Fig. 1 a Process set-up and b produced sample
Fig. 2 Tensile specimens

for heat treatment
time of 2 h before cooling to room temperature, in an oven, was used. The furnace
was ramped at 20 °C/min. In total, 12 tensile specimens, as shown in Fig. 2, were
prepared and four were used for each heat treatment temperature.
Sample Preparation and Characterisation
After heat treatment, both the as-built and heat-treated tensile specimens were taken
for metallographic preparations. The samples were mounted and polished to a 0.04
micron (OP–S suspension) surface finish using a Struers TegrsForce-5 auto/manual

polisher. The fine polished and finished samples were etched with Kellers’ reagent.
The samples were for about 30 s by immersing in a Kroll’s reagent. Olympus
BX51 M mounted with the SC30 camera was used for the microstructural and
defects observations. The samples were analysed for chemical composition using
Joel, JSM-6010Plus/LAM scanning electron microscopy (SEM) that was equipped
with energy dispersive X-ray analysis (EDS). Hardness measurements were con-
ducted with Zwick/Roell (ZHVμ) Vickers hardness machine. Pin loading of 500 gf,
dwelling time of 10 s, and spacing of 200 μm were used for hardness measurements.
All tensile specimens were pulled at room temperature using Instron tensile tester
machine following ASTM E8. A speed of 0.5 mm/min was used.
Results
Microstructure
The microstructures of the laser deposited Ti4822 alloy as-built sample and tensile
heat-treated specimens are reported in Fig. 3. The microstructures of the as-built sam-
ple and tensile specimen heat treated at 1400 °C are fully lamellar. The microstruc-
tures of the tensile specimen that was heat treated to 1200 °C looked nearly lamellar
and that of the 25 °C tensile specimen seemed tempered or friable and maybe can
be defined as duplex microstructure given that there is clear evidence of dark and
lighter contrasted phases. γ–TiAl phase appears darker under the optics while α2
(Ti3Al) appears bright white. There is a defined relationship between the result-
ing microstructure and its mechanical properties and by translation performance. A
coarse-grained and nearly lamellar microstructures exhibit high fracture toughness
and creep resistance and of course poor ductility and strength at room temperature
while a fine-grained equiaxed near gamma and duplex microstructure, with some
features of lamellae grain colony structure, would have low fracture toughness and
creep resistance and moderate tensile ductility and strength at room temperature.
With this analogy, we expect the sample heat treated to 1400 °C to have almost zero
ductility due to its coarsened grained lamellar structure followed by the As-built
specimen and only sample heat treated to 1200 °C would be expected to have good
mechanical properties and moderate room temperature tensile. The hardness profile
of these samples is reported next.
Hardness
The hardness profile of the As-built sample is shown in Fig. 4 while that of the tensile
specimens is shown in Fig. 5.
Fig. 3 SEM microstructure of the As-built sample a, and tensile specimen b 25 °C, c 1200 °C, and
d 1400 °C
Fig. 4 Hardness profile of the As-built sample
The hardness profile shows that the as-built sample had a rather homogenous
microstructure. The average hardness was calculated to be 400 HV0.5 . The profile of
the tensile specimens is given in Fig. 5. The hardness profile of the tensile specimens
is wavy; especially of the unheated specimen while that of the heat-treated specimens
Fig. 5 Hardness profile of the tensile specimens
shows a similar hardness trend with the 1400 °C tensile specimen looking at least
homogenous. The overall hardness of these specimens was calculated to be 286
HV0.5 , 328 HV0.5 , and 325 HV0.5 for the non-heat treated specimen, 1200 °C and
1400 °C, respectively. In general, these hardness results indicating that heat treatment
increased the hardness of the tensile specimens but the as-built sample would have
higher hardness. From these results, we expected the as-built sample to fracture easily
followed by heat-treated samples and the only cut and tested tensile specimen to have
some room temperature ductility. The tensile properties are reported next.
Tensile
Figure 6 reports the tensile measurements of the specimens. These tensile properties
are summarised in Table 1.
It can be deduced from both Fig. 6 and Table 1 that all samples lacked plasticity
and that the as-built sample had lowest toughness and ductility since it has the highest
tensile strength. The elongation of sample that was heat treated to 1200 °C is similar
to that of the sample that was heat treated to 1400 °C, but their strength was totally
different. Liu et al. [8] observed similar results as the results presented in this paper.
Fig. 6 Tensile profiles of the samples
Table 1 Tensile properties

Sample ID UTS (MPa) Elongation (%)
As-built 440.68 0.11
1200 HTT 377.68 1.45
1400 HTT 297.60 1.35
It was reviewed that cast Ti4822 has UTS of 490 MPa showing that to somewhat
promote good ductility and toughness heat treated must be performed on the Ti4822
laser manufactured parts. Unfortunately, as reviewed in the microstructure section,
we expected the sample that was heat treated to 1400 °C to have poor ductility and
strength while the as-built and 1200 °C tensile specimens to have moderate ductility.
However, the results suggest otherwise.
Conclusion
This paper studied the effects of heat treatment on the tensile properties of laser
manufactured a crack-free Ti4822 built sample. The following can be deduced:
• The tensile property of a laser manufactured sample is better than cast.
• Heat treated above 1200 °C led to a coarse-grained fully lamellar microstructure.
• The coarse-grained fully lamellar microstructure had low tensile strength which
would suggest moderate toughness and ductility at room temperature.
• All samples lacked plasticity.
Acknowledgements The authors wish to acknowledge the Council for Scientific and Indus-
trial Research (CSIR) and the National Research Foundation for funding. My gratitude goes to
Dr. Bathusile Masina and Mr. Nana Arthur for their continued support and assistance.
References
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018-3789-5
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Study on the Relationship Between
Process Reconstruction and Energy
Saving of Iron and Steel Manufacturing
Process in China
Shuangping Wu, Anjun Xu, Qi Zhang and Ji Li
Abstract As people pay more and more attention to environmental protection,

energy conservation in the whole process of steel manufacturing has become a hot
research object. China’s steel manufacturing process has a history of energy con-
servation for more than 40 years. The total energy consumption per ton of steel of
large and medium-sized enterprises has dropped from 1.646tce/t to 555.24kgce/t.
This paper puts forward a new theory of process reconstruction, which is mainly
explained from the following three aspects: analysis-optimization of the set of pro-
cedures’ functions, coordination-optimization of the set of procedures’ relations,
and reconstruction-optimization of the set of process’ procedures. Then, the paper
expounds the relationship between process reconstruction and energy saving from
two aspects: interface technology and synergy of material flow and energy flow.
After applying the new process reconstruction technology, the energy-saving effect
of about 5% was achieved in the steel plant experiment. Finally, the research direction
of energy conservation in steel manufacturing process is proposed.
Keywords Energy saving · Process reconstruction · Interface technology ·

Material flow
Introduction
With the outbreak of the “oil crisis” in the 1970s and the urgent requirements for
environmental protection in recent years, researchers have gradually realized the
importance of energy conservation and have invested in the tide of energy conserva-
tion research. In the past 40 years, the history of energy saving in China’s iron and
steel enterprises (CISE) can be divided into the following four stages (Fig. 1).
S. Wu · A. Xu (B) · J. Li
e-mail: anjunxu@126.com
Q. Zhang
College of Materials and Metallurgy, Northeastern University, Shengyang 110819, China

https://doi.org/10.1007/978-3-030-36540-0_13
134 S. Wu et al.
Fig. 1 Changes of energy 1.8

1.646 1.56
consumption in four stages 1.6
1.4 1.285
Energy consumption
1.18
1.2 1.017
1
0.781
0.8 0.555
0.6
0.496
0.4
0.2
0
1980 1990 2000 2018
years
comparable energy consumption per ton of steel (tce/t)
total energy consumption per ton of steel (tce/t)
(1) 1978–1980: The phase belongs to the energy-saving start-up stage. Enterprises
began to pay attention to publicizing the significance of energy saving, which
changed the history that enterprises did not assess energy consumption and did
not count energy data.
(2) 1981–1990: This stage paid great attention to monomer energy saving, devel-
oped monomer technologies such as improving the combustion and thermal
efficiency.
(3) 1991–2000: The energy-saving aim was to save energy and save non-energy
by changing the method from the energy saving of the monomer equipment
to the overall energy saving of iron and steel manufacturing process (ISMP).
Through a series of production structure adjustment, such as open hearth to
converter and ingot casting to continuous casting, and the implementation of
“continuous casting as the center” process optimization, ISMP gradually tended
to be continuous, compact, and reduced.
(4) 2001–2018: This stage is based on energy flow optimization, strengthening
the energy conversion function of CISE. Researchers developed key common
technologies such as coke dry quenching (CDQ), and top-pressure recovery
turbines (TRT). Meanwhile, the energy flow network optimization technology
is studied and the enterprise energy management center is established.
As can be seen from Table 1, the energy-saving effect of large and medium-sized
enterprises in the last 10 years is obvious. The total energy consumption per ton
of steel had been in the downward trend, and the converter procedure had realized
the negative energy steelmaking. The realization of such remarkable energy-saving
effects is not only the positive application of related single energy-saving technolo-
gies, but also thanks to several important changes, such as the complete replacement
of open hearth by converters, the rapid development and application of the continuous
casting technology, and so on. These changes reflect the evolution and optimization
of the steel manufacturing process [1] (Fig. 2), which is the essence of process
reconstruction and the important idea of metallurgical process engineering. With the
Table 1 Energy consumption table of large and medium-sized steel and steel plants in China from 2007 to 2018a
Energy consumption per 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018
ton of steel
Total energy 628.23 630.40 619.43 606.69 601.72 602.71 591.98 586.21 573.72 583.11 570.51 555.24
consumption (kgce/t)
Power consumption 480.00 476.40 466.73 467.35 475.11 474.79 464.11 470.31 473.98 475.86 468.29 451.99
(kWh/t)
Pelletizing (kgce/t) 30.12 30.41 29.96 29.14 29.60 28.84 28.26 26.94 27.31 26.33 25.59 25.36
Sintering (kgce/t) 55.47 55.32 54.95 55.27 54.34 50.60 49.14 48.90 47.89 48.53 48.53 48.60
Coking (kgce/t) 126.89 118.97 112.28 109.10 106.65 102.72 100.50 98.15 99.65 97.46 99.67 104.88
Iron making (kgce/t) 428.28 432.13 410.65 407.58 404.07 401.82 398.09 395.31 387.99 391.52 390.75 392.13
Steelmaking—BOF 6.32 6.01 3.24 0.22 −3.21 −6.08 −7.71 −9.99 −11.57 −13.40 −13.93 −13.39
Study on the Relationship Between Process Reconstruction …
(kgce/t)
Steelmaking—EAF 80.94 80.81 72.53 73.80 69.00 67.53 60.82 59.15 60.36 55.59 58.11 55.70
(kgce/t)
Rolling (kgce/t) 59.52 59.58 57.66 61.69 60.93 60.72 59.53 59.22 58.14 57.89 56.89 54.32
a Data source China Iron and Steel Industry Association Network
135
136 S. Wu et al.
Initial rolling mill /

BF Metal mixer BOF Ingot casting Soaking pit HF Secondary material
Billet opener
a 1
b Des BOF
c
Desi Des Dep
d
Secondary
Des Desi - Dep BOF metallurgy CC Cold cleaning HF HC
2
3 Hot cleaning HF HC
Blast furnace BF; Basic oxygen furnace – BOF; Hot rolling – HC;
Heating furnace HF; Continuous casting – CC; Desulfurization - Des
Desiliconization Desi; Dephosphorization – Dep; Decarbonization - Dec 4 HF HC
BF BOF: 5
a: The molten iron is put into the mixer and then converted into BOF.
b: The molten iron is desulfurized and mixed into BOF.
c: Desi in BF outlet ditch; Des in hot-metal bottle. 6 Corner heating HC
Dep in pretreatment converter ; Dec and temperature rise in BOF.
d: Des in hot-metal bottle; Desi and Dep in pretreatment converter.
Dec and temperature rise in BOF.
7
After BOF: Buffer heating Finishing mill
1: ingot casting cold charging rolling (IC-CCR).
2: continuous casting billet cold charging rolling (CC-CCR).
3: continuous casting billet hot charging rolling (CC-HCR).
4: defect-free continuous casting billet direct hot charging rolling (CC-DHCR). Batching device
5: continuous casting billet direct rolling (CC-DR).
6: thin slab continuous casting-continuous rolling.
7: strip continuous casting.
Fig. 2 Evolution and optimization of iron and steel manufacturing process
gradual transition of iron and steel manufacturing process from intermittent to quasi-
continuous or continuous, the process is continuously more continuous and compact,
and the process structure of steel work is becoming more and more specialized.
Since the problem of energy-saving in iron and steel enterprises has been put
forward, many scholars at home and abroad have been glad to carry out research.
Brunke and Blesl [2]. adopted a bottom-up approach to research the potential of 32
energy-saving measures in the German steel industry and to estimate the energy-
saving effect in the future. William et al. [3]. also conducted a bottom-up approach
to the assessment of 25 energy-saving measures in the Indian steel industry and
predicted future steel needs and energy-saving effects. Rafael et al. [4] analyzed the
energy-saving measures of Brazilian iron and steel enterprises and determined the
economically feasible energy efficiency measures. Hasanbeigi et al. [5] quantitatively
analyzed the influence of different factors on the energy consumption trend of China’s
iron and steel industry. Zhang et al. [6] adopted a bottom-up modeling method to
study the potential of energy saving and emission reduction in China’s future steel
industry, and put forward some ways to improve energy efficiency. Cai and Sun [7]
analyzed the decreasing trend of energy consumption per ton of steel, the present
situation of energy consumption, and its influencing factors in Chinese iron and steel
Study on the Relationship Between Process Reconstruction … 137
enterprises from 1980 to 2010. Kun and Li [8] made a detailed analysis of the energy-
saving measures of the global steel industry, which help the readers to understand
the energy usage.
In summary, for a long time, the way of energy saving in iron and steel enterprises
is to divide the iron and steel manufacturing process into several procedures and
equipment. Then, analyze the procedures and equipment into various physical and
chemical reaction processes, as well as mass transfer, heat transfer, and momentum
transfer processes. Such an incomplete understanding leads to the energy-saving way
that is limited to the local work and fails to perform the macro-process control of the
whole process.
Basic Theory of Process Reconstruction
The reconstruction of ISMP can be divided into three steps. The first step is the
analysis-optimization of the set of procedures’ functions. The second step is the
coordination-optimization of the set of procedures’ relations. The third step is the
reconstruction-optimization of the set of process’ procedures [1].
(1) Analysis-optimization of the set of procedures’ functions
In the ISMP, the procedure’ function is likely to be diversified. In addition, a spe-
cific function may be implemented in a variety of procedures or devices. Therefore,
only by reasonably allocating complex and diverse functions to each procedure and
device, rather than stacking them in a certain procedure and device, the structure of
the steel manufacturing process can be better optimized. For example, the oxygen
converter can be optimized from its original multiple functions to only complete
decarburization and temperature rise. The functions of desilication, desulfurization,
and dephosphorization are decomposed to the completion of hot metal pretreatment.
Degassing, deoxidizing, alloying, and other functions are decomposed into secondary
metallurgy and other procedures to complete. In this way, the optimized unit process
function set, that is, the oxygen converter function set, is obtained.
(2) Coordination-optimization of the set of procedures’ relations
The optimization degree of the matching between the procedures will directly affect
the dynamic and orderly operation of the entire process. For example, secondary
metallurgical procedure matches the two major procedures of the converter and
the caster, which has two advantages. One is that the procedure, as a buffer and
coordination means between the converter and the caster, ensures the stability of
providing molten steel to the caster and extends the continuous casting heats. The
other is that the procedure shares several functions of the converter, shortens the
smelting time of the converter, accelerates the smelting rhythm of production, and
improves the quality of molten steel through refining means.
138 S. Wu et al.
(3) Reconstruction-optimization of the set of process’ procedures

Analysis-optimization of the set of procedures’ functions and coordination-
optimization of the set of procedures’ relations are the basis of reconstruction-
optimization of the set of process’ procedures. When the two steps are combined
to realize the reconstruction and optimization of the procedure set, the realization of
each function in the process and the vertical coordination and horizontal compati-
bility of the procedure device are fully taken into account, so that the existing IRMP
can have a great breakthrough. As a whole, the reconstructed and optimized pro-
cess eliminates procedures and devices that do not adapt to the optimization mode,
shortening the production cycle and improving the continuation degree of the whole
process.
The Relationship Between Process Reconstruction

and Energy Saving
Based on the theoretical basis of process reconstruction, it is necessary to make

it clear that the object of reconstruction is the whole production process, and the
method is to adjust and optimize the procedure /device and the interface technology
between them, which affects the flow state of material flow and energy flow in the
whole manufacturing process. The final purpose is to make the whole manufacturing
process continuous and compact, coordinated, and orderly operation, and to enable
the mass flow-energy flow to be co-optimized, to reduce the dissipation, and to
achieve an energy-saving requirement. The expression of the process reconstruction
is to optimize the interface technology and to achieve the co-optimization of the
material flow and energy flow. The following introduces the application of related
technology, taking Jingtang Iron and Steel plant (JTISP) as an example.
Interface Technology
Interface technology refers to the connection-matching, coordination-buffering tech-

nology, and the corresponding devices between the various procedures [9] (Fig. 3).
There are three main types of interface technologies in ISMP: ironmaking–steelmak-
ing interface, steelmaking—continuous casting interface, and continuous casting–hot
rolling interface.
Ironmaking–Steelmaking Interface
At present, JTISP has adopted the multi-functional molten iron ladle interface
technology, and has obtained obvious results in the actual production, as follows:
Blast Furance Converter Continuous casting Hot rolling

Interface between processes or devices
Fig. 3 Schematic diagram of the interface between the procedures
(1) Efficient connection between blast furnace and converter, concise and compact
layout of iron works and steel works, short transmission lines, smooth logistics.
(2) The turnover speed of ladle is increased, the turnover time is shortened, the
number of online ladle is effectively reduced, and the operation management of
ladle is optimized.
(3) The quality of molten iron can be precisely controlled to ensure a stable amount
of molten iron, which creates favorable conditions for the accurate and stable
operation of downstream procedures.
(4) The rapid turnover of the ladles and the use of capping technology can effec-
tively reduce the fluctuation of molten iron temperature and the molten iron
temperature drop during the turnover of ladles.
(5) Under the condition of high molten iron temperature and high silicon con-
tent, the desulfurization effect of Kambara Reactor (KR) device is better, the
desulfurization treatment cycle is shortened, the consumption of desulfurizer is
reduced;
(6) Compared with metal mixer and torpedo tank, this technology reduces the emis-
sion of CO2 , dust, and slag in the production process, which not only saves the
investment cost, but also provides a basis for green and clean production.
In addition, the De[S]–De[Si]/[P] pretreatment production technology is also devel-
oped, that is, the technology of desulfurization, desilication, and dephosphorization
of the full amount of molten iron on line. By referring to the steel work of Sumitomo
metal and Wakayama iron and steel institute of Japan, JTISP combined this tech-
nology with multi-functional molten iron ladle interface technology, and achieved
certain results in practical application, which are embodied in the following aspects:
(1) By implementing analysis-optimization of converter function, coordination-
optimization of procedures’ relations, and process reconstruction, it realizes
efficient operation rhythm matching, stable molten steel quality, and greatly
improved production efficiency in steel mills.
(2) It realizes less slag smelting, reduces the total slag of dephosphorization con-
verter and decarbonization converter, and makes full use of the converter
slag.
140 S. Wu et al.
(3) The coordination of the sequence of desulfurization, desilication, and dephos-

phorization, and the improvement of the thermodynamic and kinetic conditions
have fully improved the removal efficiency.
(4) The high efficiency, stability, and batch production of clean steel is realized,
and the cleanliness is very high.
The application of ironmaking–steelmaking interface technology has the following
three effects on energy conservation:
(1) The ratio of De[S]–De[Si]/[P] pretreatment production in JTISP increased.
Before the optimization, the proportion was about 30%, now it is about 40%,
and there is a possibility of improvement in the latter period.
(2) It improves the production efficiency of the converter, reduces the empty furnace
time about 30 min, and reduces the iron temperature drop of 15 °C.
(3) It can effectively address the problem of melting large scrap steel, and further
improve the scrap consumption ratio in the production process.
Steelmaking—Continuous Casting Interface
Steelmaking—continuous casting interface technology includes secondary metallur-

gical equipment, molten iron ladle, continuous casting tundish, steelmaking work-
shop layout, and transportation capacity configuration, as well as the number (capac-
ity) of each procedure and equipment and corresponding matching design. At present,
many steel mills in China, such as Han Steel, Tang Steel, and Benxi Steel have put thin
slab continuous casting into operation. Combined with the technology of improving
the stable operation of continuous casting machines, the steel mills have achieved
certain results, with the breakout rate greatly reduced and the slab quality improved.
These are all the results of the practice of steelmaking—continuous casting interface
technology.
For JTISP production optimization problem, this article puts forward the idea
of a steel ladle intelligent platform, and has developed a set of software for ladle
management system (Fig. 4). This work is closely in the steelmaking, continuous
casting and ladle, crane and other procedures or equipment, realizing the process
monitoring and real-time optimization of liquid iron flow.
Application of the software, combined with ladle cover heat preservation and
other related technologies, JTISP’s optimization effect is obvious:
(1) Combined with ladle cover and energy-saving baking technology (Fig. 5), the
lining temperature of ladle is increased by about 220 °C, effectively improving
the insulation effect.
(2) Train schedules are strictly controlled through ladle tracking. The production
process time from the completion of the blast furnace to the start of the casting
machine is shortened by 8–11 min. The optimization of ladle allocation in the
production process is realized, which accelerates ladle turnover and reduces the
turnover time by about 21 min.
Fig. 4 Software main interface of ladle management system
Fig. 5 Ladle cover and ladle baking site drawing
(3) Real-time monitoring of the location of the crane and the ladle, and instruction
control of the crane, they obviously optimized the operation of the crane, reduced
the waiting time of the ladle, and accelerated the overall production pace. Based
on the actual field data, using the optimal scheduling method of crane in the
management system, the operating rate of the crane was reduced by 5.16%
(Table 2).
142 S. Wu et al.
Table 2 Comparison of various operating rates of crane

Index Optimized scheduling Manual scheduling (%) Difference (%)
(%)
Crane operation rate 23.67 28.82 -5.16
Crane load operating 52.21 46.91 5.30
rate
rate with an weight
ladle
rate with an empty ladle
Crane no-load rate 48.59 53.03 -5.30
Table 3 Comparison of the

Steel plants Overall tapping Tapping
current state of converter
temperature (°C) temperature of IF
tapping temperature
steel (°C)
Jingtang steel ~1652 (before ~1657
plant optimization
1670–1690)
Zhanjiang steel ~1665 ~1670
plant
Korea (Posco, ≤1650 ~1650
Gwangyang)
Nippon Steel 1640–1650 ~1650
(4) The software realizes the rapid turnover of ladles and the optimized regulation
of cranes, and optimizes the temperature of molten steel from converter steel-
making to continuous casting by combining the existing technologies of ladle
and tundish baking, which reduces the original temperature by nearly 20 °C and
greatly saves energy consumption (Table 3).
Continuous Casting—Hot Rolling Interface
The research on this interface is mainly theoretical, and there is no practical ver-
ification for the time being. This interface focuses on the optimal scheduling of
heating furnaces. It can be observed in Table 4 that reasonable optimal scheduling
can effectively reduce the slab’s waiting time in the heating furnace and avoid the
quality problems caused by too long heating time. At the same time, the produc-
tion efficiency of heating furnace needs to be improved and energy consumption is
reduced.
Table 4 Comparison of optimal operation results of heating furnaces

Number of Before optimization (manual After optimization Reduced
slabs/piece scheduling) waiting time
The objective Slab’s The objective Slab’s (min)
function waiting time function waiting time
in the heating in the heating
furnace (min) furnace (min)
50 38994 650 35758 596 54
88 101127 1685 89396 1490 195
130 225998 3766 203173 3386 380
Co-optimization of the Material Flow and Energy Flow
The material flow in ISMP is mainly iron material flow, including iron ore, pig iron,
molten steel, etc. Energy flow is mainly carbon energy flow, including coal, coke,
gas, etc. The ISMP can be abstractly described as the input–output process of iron
material flow, the input–output process of energy flow, and the interaction process
of material–energy flow. Therefore, it is necessary to explore the co-optimization
between material flow and energy flow.
The production process of ISMP is essentially a transformation process of material
flow, driven by energy flow, from raw materials to steel products along a given flow
network. Material flow is the main body that is transformed by processing. Most
of the energy flow is accompanied by material flow, coupled in each procedure and
steel product material flow (such as high-temperature molten iron and continuous
casting billet). There is also a part of energy flow independent of material flow (such
as various gas). It constitutes the ISMP’s energy conversion network according to
a certain program (Fig. 6). In order to promote the rapid transformation of material
flow, the impetus of energy flow is often surplus, which is manifested as a large
amount of residual heat and energy. The process of material flow and energy flow in
ISMP is a synergistic process of efficient production of steel products and efficient
conversion of energy products. Optimizing this coupling makes it possible for ISMP
to have low energy consumption, low cost, and low pollution emissions.
Aiming at the synergistic problem of material flow and energy flow, combined with
the actual situation of JTISP, a set of energy comprehensive optimized dispatching
system is developed to optimize the coupling of gas, steam, power, and other energy
media. In theory, the system can improve the efficiency of energy utilization. At
present, it is in the process of practice.
During the simulation optimization of the system (Fig. 7), the energy consumption
of most procedures is lower than that before the optimization. The largest reduction
is the coking procedure energy consumption, which reduces 25.54kgce/t, but the
energy consumption in the steelmaking procedure is increased, from −13.70kgce/t
to −8.28kgce/t, which is caused by the change of the molten iron ratio, resulting in
the reduction of converter gas recovery. The optimized global energy consumption
144 S. Wu et al.
Raw ore
Fluxes
Coal
Coke
COG COG
COG BFG Electricity
Sinter Plant Coke Plant Power Plant
Electricity Electricity Electricity Electricity
BOFG
Coke
Sinter ore
Lump ore
Coke
Pellet
Coal
COG BFG
Air
Blast Furnace
Electricity BOFG
COG: Coke Oven Gas
BFG: Blast Furnace Gas
Slag
Hot Metal
BOFG: Basic Oxygen Furnace Gas

Scrap
Basic Oxygen Molten Steel Continuous Slab

Rolling
Furnace Casting
Fig. 6 Schematic diagram of the synergistic process between material flow and energy flow
material flow and energy
flow before and after
co-optimization
has been reduced from 616.08 kgce/t to 530.45 kgce/t. The optimization degree of
global energy consumption has reached 13%, and the overall energy utilization has
been effectively improved.
After 3 years of research on energy saving in JTISP, the energy saving effect is
obvious by using the related energy-saving technology introduced above. By the end
of 2015, the total energy consumption of per ton of steel in the steelmaking plant of
the Jingtang company reached 640 kgce/t. Figure 8 shows the fluctuation of the total
energy consumption per ton of steel in the steelmaking plant from January 2016 to the
end of 2018. As can be seen from the figure, the fluctuation is more frequent, coupled
with the requirement of production restrictions, such as November 2017 reached an
total energy consumption per ton of steel (kgce/t) 740.62

740.00
720.00
698.00
700.00
680.00 669.74
658.00
660.00 648.50
649.55
645.00
637.88 639.10 645.60
634.89 641.20
640.00
622.50 622.02 639.00
623.72
620.00 623.90 614.70 616.16
620.45
615.72
609.31
600.00 606.50
594.50 594.21
580.00
date
Fig. 8 Total energy consumption per ton of steel in Jingtang steelmaking plant from 2016 to 2018
all-time high of 740.62kgce/t. However, there is an overall downward trend, with

a minimum value of 594.21kgce/t (October 2018). Under the key problems of the
13th five-year Plan, based on the historical value of 2015, reducing the total energy
consumption per ton of steel in Jingtang steelmaking plant by 5% (about 32 kgce/t)
can be realized and may be overreached.
Discussion and Conclusion
Energy consumption involves every link of ISMP, and adjusting the structure of ISMP
is an important means of energy saving. The idea of process reconstruction is based
on the synergism-optimization of the entire manufacturing process. Therefore, the
future energy-saving direction of iron and steel enterprises are as follows:
(1) The structural adjustment and optimization of the steel manufacturing process
are carried out based on the principle of process reconstruction.
(2) In the existing process, the interface technology should be further studied to
master the influence of various transportation devices and production devices
in the interface of the production process.
(3) The interaction regularity of material flow and energy flow in the production pro-
cess is deeply studied in order to improve the coupling optimization of material
flow and energy flow.
Over the past 40 years, as people began to realize energy saving, to strive to
develop a variety of new technologies and new theories to achieve energy saving, the
total energy consumption of large and medium-sized enterprises from 1.646tce/t to
555.24kgce/t. It can be said to be a significant effect. But compared with the advanced
level of foreign countries, the efficiency of energy saving is still insufficient. With the
rise of metallurgical process engineering, the idea of process reconstruction has grad-
ually become accustomed to people. Combined with the actual situation of JTISP,
146 S. Wu et al.
we research and implement the related technology of process reconstruction, such as

the multi-functional molten iron ladle interface technology, and ladle management
system, to reduce the energy consumption of about 5%. When the subsequent process
reconstruction technology is more mature and the production process is more stable,
the energy saving effect will be more noticeable.
Acknowledgements The authors are grateful for the financial support of the Program of National
Natural Science Foundation of China (Grant No. 51674030) and the National Key Research and
Development Program of China (Grant No. 2016YFB0601301).
References
1. Yin RY (2009) Metallurgical process engineering. Metallurgical Industry Press, Beijing

2. Brunke JC, Blesl M (2014) A plant-specific bottom-up approach for assessing the cost-effective
energy conservation potential and its ability to compensate rising energy-related costs in the
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12.024
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iron and steel industry: fuel and electricity conservation supply curves for integrated steel mills.
Energy 153:816–824. https://doi.org/10.1016/j.energy.2018.04.055
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1016/j.jclepro.2014.03.065
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energy efficiency improvement of China’s steel industry. Iron Steel 54(2):7–14
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and steel industry in china. Iron Steel 47(5):1–8
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52(6):1–12
Effect of Magnetic Field
on CaO–SiO2 –CaF2 Mould Flux: New
Insight from Molecular Dynamic
Simulation
Qi Jiang, Weitong Du and Yu Wang
Abstract Mould flux is of great importance in the metal continuous casting process,
and mainly the calcium fluoride is always added. On the other hand, electromagnetic
field is also used in the mould for improving the quality of metal. Thus, the knowledge
of the structural and transported properties of CaO–SiO2 –CaF2 flux under magnetic
field are relevant properties for industry applications for the sake of prevention of
operation problem and product defect. In this paper, molecular dynamics is used to
investigate the effect of magnetic field on the CaO–SiO2 –CaF2 fluxes at 1773 K,
applying 12 models changed on their chemical compositions and intensities of mag-
netic field. The results show that the magnetic field can increase the complexity of
micro-structures and the mobility of F− ion in fluxes, revealing the growth of sum-
mation of Q3 and Q4 species as the intensity of magnetic climbing, as well as with
the concentration of bridging oxygen rising.
Keywords CaO–SiO2 –CaF2 flux · Magnetic field · Structural property ·

Molecular dynamics
Introduction
In metallurgical processes, electromagnetic technology is essentially employed for

promoting the quality of products, which results in liquid metal movement and change
in microstructure. Covering the liquid metal, the molten slag can also rotate notably
under externally applied magnetic field (the intensity of it varying from 0 to 0.5 T)
[1–4]. Due to its ionic structure, the molten slag is easily affected by Lorentz Force
under magnetic field. Thus, melting and working under magnetic field in the mould,
mould fluxes can also be influenced structurally, which are of strategic importance
Q. Jiang · W. Du · Y. Wang (B)

College of Materials Science and Engineering, Chongqing University, Chongqing 400044,
People’s Republic of China
e-mail: wangyu@cqu.edu.cn
Chongqing Key Laboratory of Vanadium-Titanium Metallurgy and Advanced Materials,
Chongqing University, Chongqing 400044, People’s Republic of China

https://doi.org/10.1007/978-3-030-36540-0_14
148 Q. Jiang et al.
in improving the quality of metallic products during the continuous casting process.
This may be a plausible explanation that many fluxes show unstable performances in
industrial production—even fluctuation of their physical properties, especially vis-
cosity. Only a few investigations [5, 6] were carried out to study the influence of
electromagnetic field on transport properties of mould flux. And a lot of simulations
and experiments [7–11] have been implemented to investigate the microstructural
features and viscosity of fluoric mould flux without electromagnetic field in contin-
uous casting. The CaO–SiO2 -based flux is purely ionic from previous experiments
and simulations, which means it can be affected by magnetic field and ions can
travel because of Lorentz Force. Since the CaO–SiO2 –CaF2 mould flux belongs to
the silicate system, it will get affected in high temperature under electromagnetic
field because of Lorentz force. Wang et al. [12] found that the viscosity of mould
flux will climb remarkably under high-frequency electromagnetic field. Zhao et al.
[5] investigated the effect of low-frequency magnetic field on the viscosity of mould
flux.
In this study, MD simulations are implemented to investigate the influence of
magnetic field on the structural and dynamical properties of CaO–SiO2 –CaF2 fluxes.
The self-diffusion coefficients of atoms, calculated from MD simulations, reveal
the element migrations under magnetic field. The results can build up a theoretical
foundation for the effect of magnetic field to CaO–SiO2 –CaF2 slag system.
Computational Details
On the purpose of studying the effect of magnetic field, we change the intensity of
magnetic field reported in Table 1 and apply these different intensities of magnetic
field tovariety of samples which have the same basicity but with different contents
of CaF2 . The exact detail about composition is shown in Table 1. The composition
of the flux is designed according to the experimental and simulation results [2, 3, 5,
13, 14]. The condition of magnetic field is set according to previous investigations.
The basicity (CaO/SiO2 ) of each model is kept as constant as 1, for in continuous
casting, the basicity of mould flux is around this value.
Normally, in silicate systems, parameters of ionic force field such as the BMH pair
potential are chosen. It is reported that the details of structural features in silicates can
be expressed reasonably well by using the BMH potential. The long-range Coulomb
interactions are treated by Ewald summation method with a precision of 10−5 . All
simulations are employed in an NVT ensemble. The box size of each simulation
model is obtained from density according to previous studies. The atoms, nearly
5000, are placed randomly in a box with periodical boundary conditions.
Through a lot of preliminary simulations, we determine a stable simulation process
as follows: The system is first equilibrated for 50 ps at 4000 K to avoid the effect
of the initial random configuration, after this period, the temperature is decreased
continuously to 1773 K for 80 ps and is kept at constant for 170 ps. We take the
last 100 ps of the resulting structure to analyse structure properties. We set the final
Table 1 MD models of ternary CaO–SiO2 –CaF2 systems under different magnetic field
Model Number of atoms Initial weight fraction Cell side Intensity of magnetic field
Ca Si O F Total CaO (%) SiO2 (%) CaF2 (%) Å T
1.1 1070 930 2852 152 5004 47.5 47.5 5 41.7587 0
1.2 1070 930 2852 152 5004 47.5 47.5 5 41.7587 0.1
1.3 1070 930 2852 152 5004 47.5 47.5 5 41.7587 0.3
1.4 1070 930 2852 152 5004 47.5 47.5 5 41.7587 0.5
2.1 1099 885 2715 304 5003 45 45 10 41.9335 0
2.2 1099 885 2715 304 5003 45 45 10 41.9335 0.1
2.3 1099 885 2715 304 5003 45 45 10 41.9335 0.3
Effect of Magnetic Field on CaO–SiO2 –CaF2 Mould Flux …
2.4 1099 885 2715 304 5003 45 45 10 41.9335 0.5

3.1 1128 840 2579 455 5002 42.5 42.5 15 42.2160 0
3.2 1128 840 2579 455 5002 42.5 42.5 15 42.2160 0.1
3.3 1128 840 2579 455 5002 42.5 42.5 15 42.2160 0.3
3.4 1128 840 2579 455 5002 42.5 42.5 15 42.2160 0.5
149
150 Q. Jiang et al.
Table 2 Parameters for BMH potential

Atom 1 Atom 2 Aij (eV) Bij (1/Å) Cij (eV·Å6 )
Si Si 2163.3 6.25 0
Si O 62821.4 6.06 0
Si Ca 26686.2 6.25 0
Si F 43406 6.06 0
Ca Ca 329193.3 6.25 4.34
Ca O 718136 6.06 8.67
Ca F 496191.5 6.06 8.67
F F 730722.8 5.88 17.34
F O 1046135.4 5.88 17.34
O O 1497693.5 5.88 17.34
temperature as 1773 K, for we want to compare our result with experimental and
simulation results. Total MD simulations last for 300 ps.
The program Materials Explorer (FUJITSU LIMITED) has been used for the
present work. For the integration of the equations of motion, the Verlet–Leapfrog
algorithm is applied with a time-step of 1 fs. In this work, the force field parameters
are due to Hirao’s [15] work listed in Table 2. These parameters have been used and
have good agreement with experiments in previous modelling studies of CaO–SiO2 –
CaF2 slag system. The valance states of Si, Ca, F, and O are +4, +2, −1, and −2,
respectively.
Pairwise Radial Distribution Function (PRDF)
Our work focusses on research of the magnetic field, especially its effect on the
structure of silicate melt. For this purpose, we have chosen PRDFs with/without
magnetic field for comparison. It is universally acknowledged [16] that the silicon
atoms are always linked with four oxygen atoms in silicate melts and form SiO4 4−
tetrahedral because of strong Si–O chemical bond. Other alkali and alkali earth metal
ions are surrounded by these anion groups to keep the balance of local charge.
The local environment around Si and Ca atoms under magnetic field in slag struc-
tures is investigated through the PRDF shown in Fig. 1a, b, respectively. Figure 1a
displays the Si–O pair distribution function for models from 1.1–3.4. It can be seen
that the length of Si–O bond keeps unchanged at 1.62 Å in all slags, but the peak of
g(r) for Si–O increases modestly as the intensity of magnetic field and the content of
CaF2 increase as shown in Table 1, showing that both magnetic field and the addi-
tion of CaF2 can make the content of Si–O increasing slightly. It also can be noted
Effect of Magnetic Field on CaO–SiO2 –CaF2 Mould Flux … 151
Fig. 1 a and b Radial distribution functions of Si–O, Ca–O, and Si–F pair in 1.1–3.4, respectively
that near the first minimum of gSi–O (r), which is about 2.00 Å, the value of gij (r) is
almost zero, reflecting the regularity of Si–O network structure. Thus, we employ
this feature and naturally define the nearest neighbours of a silicon atom, and in the
next part, we will utilise this feature.
At the same time, the Ca–O bond will also not be affected under magnetic field,
whose length keeps constant as 2.31 Å, shown in Fig. 1b. The distance between those
atoms pair (Si–F) which does not have chemical bond, fluctuates slightly because of
different compositions and intensity of magnetic field. Based on the radius of Si4+
(0.40 Å), F− (1.33 Å), we conclude that there is no chemical bond between Si–F,
Fig. 2 Distribution of different types of oxygen from 1.1 to 3.4

152 Q. Jiang et al.
Fig. 3 Distribution of Qn species from 1.1 to 3.4
for the sum of ionic radius between Si–F (1.73 Å) is much smaller than first peak
position (about 4.30 Å) of them. From above discussion, we find that F in molten
slags has the weakest chemical interaction, which may induce its mobility is the
highest.
Distribution of Oxygen Types and Qn Species
In this study according to afore-mentioned cut-off radius from PRDF, we make use of
2.00 Å as our distance criterion between Si and O to distinguish and count all kinds of
oxygen types. And those which are not connected to other atoms are labelled as free
oxygen (FO). The results are shown in Fig. 4. Based on this, we find that when the
amount of CaF2 increases, the amount of free oxygen (FO) and non-bridging oxygen
(NBO) grow, while the percentage of bridging oxygen (BO) has increasement, and
this is consistent with other simulation and experiment results [9, 17, 18] revealing
that CaF2 is of importance to decrease the degree of depolymerization. When this
degree climbs, the Si–O structure is more subjected to have change for the slope of
each curve is increasing as the amount of CaF2 grows. From models 3.1–3.4, the
concentration of NBO and FO see a considerable decline which also corresponds to
the results of Qn species discussed in the next part (Fig. 2).
In slags, the existence of Calcium can make the Qn distribution shift toward lower
n value. Thus, in our simulations because of high Calcium contents, simple units
such as Q0 , Q1 , and Q2 are commonly found, while Q3 and Q4 only cover a small
Fig. 4 MSDs for 1.4, 2.4, and 3.4, respectively
percentage. Thus, we investigated the summation of Q0 , Q1 , and Q2 , as well as

the summation of Q3 and Q4 under different magnetic fields with varying intensity.
Figure 5 shows that the summation of Q0 , Q1 , and Q2 grows as the intensity of
magnetic field rises, whereas the summation of Q3 and Q4 has an opposite trend. In
1.1, 2.1, and 3.1, namely without magnetic field, the total amount of Q0 , Q1 , and
Q2 climbs from 80.718 to 85.511% as the compositions of F increases, while the
summation of Q3 and Q4 falls from 19.282 to 14.489%. We favour the view that the
magnetic field plays an active role in disorganizing the Si–O network structure as is
pointed out by the result of angle distribution. And this may be the explanation that
the viscosity of mould flux will grow noticeably under magnetic field (Fig. 3).
Mean Square Displacement
In order to further investigate the motion of ions under magnetic field, we again
calculated two different direction vectors of MSDs, parallel to the magnetic field
vector (D ) and perpendicular to that (D ). Figure 8 shows the results of two directions
of MSDs in 1.4, 2.4,and 3.4. The regularity in digraphs is notably clear: the MSDs
of perpendicular direction and their slopes are strikingly larger than those of parallel
direction, which is a powerful evidence that the motion of ions, especially F ion, will
change under magnetic field, resulted from the feature of Lorentz Force. Another
thing on which we should attach importance is that the gap of D and D for F
drops substantially from 8.29 to 1.91 Å2 as the weight percentage of CaF2 grow
from 5 to 15%, since when the amount of CaF2 climbs from 5 to 15%, the degree
of depolymerization declines and the motion of ions become more active, the atoms
154 Q. Jiang et al.
(D ) trigger the movement of other atoms (D ) more effectively because of atomic

interaction.
Generally, there is a strong evidence that the magnetic field presently applied for
MD simulations of slags do have an influence on the mobility of ions, especially F− .
The MSDs of ions and their slopes are clearly lower than these data under magnetic
field, and as the intensity of magnetic field increases, the mobility of ions climbs too.
Therefore, the results from MSD curves illustrate the force effect of magnetic field
to ions in these computer simulation slags.
Conclusions
In summary, we have identified several important properties of the effect of indus-

trial magnetic fields on the CaO–SiO2 –CaF2 fluxes. On a qualitative level, the results
about the middle-range structures under no externally magnetic field agree with the
experimental observation, which prove our simulations are reasonable. A widening
tendency of distribution of O–Si–O angle distribution and that the summation of Q3
and Q4 species increase as the intensity of magnetic climbs, also with the concentra-
tion of bridging oxygen increasing. The mobility of F and Ca will grow to different
degrees and the dynamic homogeneity increases for stronger magnetic fields. The
magnetic field has less influence on the Si and O ions diffusivities. It is a challenge
to devise experiments, at such high temperature, which are able to prove these obser-
vations and which may then help to understand the underlying information content
of magnetic field effect.
Acknowledgements We thank National Natural Science Foundation of China (Project No.

51574051) for the financial support.
References
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the steel/slag interface behavior in a slab mold. Metall Mater Trans B 48:2389–2402. https://
doi.org/10.1007/s11663-017-1030-9
5. Zhao L, Wang Y, Zhao LM (2018) Viscosity of mould flux under electromagnetic field. Miner
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6. Li T, Nagaya S, Sassa K, Asai S (1995) Study of meniscus behavior and surface properties
during casting in a high-frequency magnetic field. Metall Mater Trans B 26:353–359. https://
doi.org/10.1007/BF02660978
7. Gao J, Wen G, Huang T, Tang P, Liu Q (2016) Effects of the composition on the structure and
viscosity of the CaO–SiO2 -based mold flux. J Non Cryst Solids 435:33–39
8. Ueda S, Koyo H, Ikeda T, Kariya Y, Maeda M (2008) Infrared emission spectra of CaF2 –CaO–
SiO2 melt. ISIJ Int 40:739–743. https://doi.org/10.2355/isijinternational.40.739
9. He S, Wang S, Jia B, Li M, Wang Q, Wang Q (2019) Molecular dynamics simulation of the
structure and properties of CaO–SiO2 –CaF2 slag systems, Metall. Mater. Trans B Process
Metall Mater Process Sci 50:1503–1513. https://doi.org/10.1007/s11663-019-01547-7
10. Persson M, Görnerup M, Seetharaman S (2007) Viscosity measurements of some mould flux
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12. Xingjuan W, Liguang Z, Ran L, Xiangming J, Zhihao L (2013) Viscosity properties of flux
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13. Park JH, Kim DS, Lee YD, Song HS, Min DJ (2004) The viscosities and structures of calcium
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Investigation of the Crack Initiation
and Propagation in Super Duplex
Stainless Steel During Hot Working
Wei Shen, Fuming Wang, Zhanbing Yang, Changrong Li, Ping Lin
and Xiaojie Zhu
Abstract A better understanding of crack initiation and propagation in duplex stain-

less steel (DSS) during hot working process is significant for improving production
efficiency, due to the frequent occurrence of cracking during deformation process
of duplex stainless steels. In this work, the cracking mechanism of S32750 super
duplex stainless steel (SDSS) during hot rolling was researched in detail. The results
showed that uneven deformation can easily cause the crack initiation and propaga-
tion. The hard and brittle sigma phases with high Cr and Mo, which were observed
near the cracks, seriously damaged the hot working properties of SDSS. During hot
deformation, nitride, as another high temperature phases, precipitated along grain
boundaries to prevent grain boundary migration, and further to reduce the hot duc-
tility of steel. Inclusions can also cause crack initiation and propagation, especially
Al2 O3 . In addition, the surface microcracks resulting from oxide layer rolled into the
matrix.
Keywords SDSS · Cracks · Hot working · Precipitates · Inclusions
W. Shen · F. Wang · Z. Yang (B)

W. Shen
e-mail: shenweiustb@163.com
F. Wang
e-mail: wangfuming@metall.ustb.edu.cn
C. Li
School of Materials Science and Engineering, University of Science and Technology Beijing,
Beijing 100083, People’s Republic of China
e-mail: crli@mater.ustb.edu.cn
P. Lin · X. Zhu
TSINGSHAN, Qingtian 303903, China
e-mail: lp@ruipt.com
X. Zhu
e-mail: zxj@ruipt.com

https://doi.org/10.1007/978-3-030-36540-0_15
158 W. Shen et al.
Introduction
Due to the high strength and excellent corrosion resistance, duplex stainless steel
has been widely used in oil and gas, petrochemical, paper manufacturing, pollution
control, and nuclear industries [1–3]. It is well known that such good properties
of DSS strongly rely on a balanced two-phase microstructure consisting of approxi-
mately equal amounts of δ-ferrite and austenite (γ) [4, 5]. Compared with the second-
generation standard duplex stainless steel (2205), the third-generation super duplex
stainless steel (2507) has higher strength and corrosion resistance. These excellent
performances derive from the higher alloy contents in SDSS, such as Cr, Mo, and N
[6].
However, the higher alloy contents of SDSS result in the precipitation of large
amounts of secondary phases, high deformation resistance, and poor thermal conduc-
tivity, which lead to the worse hot working performance and higher risk of cracking of
SDSS during hot rolling or forging process. Cabrera [7] reported that hot deformation
of these two-phase materials was still a critical point because the different mechanical
responses of austenite and ferrite often lead to the formation of edge cracks. In order
to better understand the softening mechanism of δ-ferrite and austenite (γ) under hot
deformation, many researchers paid attention to the effects of temperature and strain
rates on flowing behavior and microstructural evolution of DSS [8–14]. Zou [12] and
Kingklang [13] reported that the flow stress increased with the increase of strain rate
and the decrease of temperature. The softening degree of ferrite increased and the
austenite gradually spheroidized when the strain rates decreased and deformation
temperature increased. Ming [14] reported that most of the flow curves exhibited a
characteristic of dynamic recrystallization (DRX). Therefore, the adoptions of high
deformation temperature and low strain rates are beneficial to avoid the hot-cracking
problem of DSS.
There are many researches [9, 11, 14–17] about the hot deformation of DSS,
but most of them were based on the heat treatment process, mechanical properties,
deformation parameters (such as the strain rates and temperature), and deformation
behavior. There are few reports about the systematic study on the cracking charac-
teristic of the SDSS. Therefore, the aim of this work is to investigate the effect of
microstructure, precipitation, inclusion, and surface oxide layer on the crack initiation
and propagation of S32750 super duplex stainless steel during hot rolling.
The experimental materials were industrial SDSS hot rolled bars with a diameter of
75 mm. This industrial test material was known to have poor hot rolling properties
with frequent occurrence of edge crack. The chemical compositions of this industrial
SDSS are listed in Table 1. The hot rolling schematic diagram is shown in Fig. 1.
Continuous casting billets were first reheated to 1200 °C and kept at this temperature
Table 1 The chemical composition of the tested steel (mass%)
Steel C Si Mn P S Cr Ni Mo Al V N
S32750 0.021 0.46 0.70 0.023 0.0017 25.47 6.17 3.48 0.003 0.16 0.284
Investigation of the Crack Initiation and Propagation …
159
160 W. Shen et al.
Fig. 1 The schematic

diagram of hot rolling
process for SDSS
for 2 h. The total size was then reduced from 180 * 180 to 120 * 120 mm by roughing
1–8 passes on the reversing mill. Finally, the rough rolled billets were hot rolled on
9–14 consecutive finishing mills to the final hot rolling diameter of 75 mm.
The hot-cracking samples were cut from industrial SDSS hot rolled bars by the
electrospark wire-electrode cutting. For optical microscopy (OM), electrolytic etch-
ing in KOH solution (20 g KOH + 100 ml H2 O, 10 V, 10 ~ 20 s) was used. This
etching gave ferrite grains in a darker color and austenitic ones in bright grey. The
equilibrium precipitation of the tested steel was calculated and analyzed by Thermo-
Calc and FE-SEM equipped with EDS, respectively. The inclusions and surface oxide
layer were also examined by OM and FE-SEM+EDS.
Microstructure Evolution in Hot Processing
Figure 2a–c shows the optical micrographs of industrial SDSS at different processing
stages. As shown in Fig. 2a, a lot of Widmanstätten γ grains distribute in δ-ferrite
matrix. Martin [18] reported that allotriomorphic γ nucleated at existing δ grain
boundaries first. As the temperature decreases, Widmanstätten γ laths nucleated
Fig. 2 Optical microstructures of industrial SDSS obtained at different processing stages: a as-cast
conditions; b roughing conditions; c final conditions
Investigation of the Crack Initiation and Propagation … 161
Fig. 3 Microstructures of cracks propagation and microcracks initiation: a, b, c cracks propagation;

d, e, f microcracks initiation
from the allotriomorphic γ with a Kurdjumov–Sachs orientation relationship. This

K-S relation was removed during the subsequent stages of deformation. Meanwhile,
both the ferrite and austenite phases elongate along the rolling direction forming a
banded structure, as shown in Fig. 2b, c.
As shown in Fig. 3a–c, the microstructure of crack propagation exhibits a typical
flow localization band. Zou [12] reported that this flow localization band was caused
by the uneven deformation. And Fang [19] reported that the lower temperature and
higher strain rate facilitated the occurrence of instability. Generally, uneven defor-
mation can easily cause the crack initiation and propagation. As shown in Fig. 3d, e,
the microcracks generally occur between δ and γ dual-phases. As is known, δ-ferrite
and austenite (γ) have different softening mechanisms under hot deformation [10,
12, 17]. Therefore, when hot working temperature or strain rate is not properly con-
trolled, uneven distribution of stress and strain in the dual-phases structure is easily
formed. This is the reason for crack initiation and propagation at the dual-phases
boundaries.
The Effect of Precipitation on the Cracking
The precipitates not only have influence on corrosion resistance, but also on hot
workability for SDSS. In order to comprehensively analyse precipitates in steel,
Thermo-Calc is used to carry out thermodynamic calculation from 400 to 1600 °C.
As shown in Fig. 4a, the calculation results show that there are main HCP, σ, M23 C6 ,
M3 P, and Z equilibrium precipitation phases in the tested steels. Obviously, only HCP,
σ, and M23 C6 may have an impact on thermoplastic, since the SDSS hot working
temperature is ordinary above 950 °C. The chemical composition of the HCP, σ, and
162 W. Shen et al.
Fig. 4 Thermodynamic calculation results: a the equilibrium precipitation in tested steel; the
compositions of HCP phase (b), σ phase (c), and M23 C6 phase (d)
M23 C6 are shown in Fig. 4b–d. HCP phase mainly contains Cr, N, and V elements;
σ phase mainly contains Fe, Cr, and Mo elements; M23 C6 mainly contains Cr, Mo,
Fe, and C elements.
Figure 5 shows the FE-SEM observation results of microstructure and σ precipi-
tates in the tested steels. Austenite islands distributed in ferrite grains and two typical
locations of σ phase were observed. As illustrated in Fig. 5a, b, σ phase preferably
precipitates at the δ/γ interfaces. As shown in Fig. 5c, σ phase is rich in Cr and Mo
and a brittle phase. And its formation leads to preferential cracking of SDSS at the
δ/γ interfaces, since uneven deformation is easy to occur around σ phases during hot
working. Another typical σ precipitate location, as illustrated in Fig. 5d, is within
δ grains. Figure 5e shows the microstructure of eutectoid decomposition of ferrite
(δ → σ + γ2 ). The γ2 has lower Cr content than that of γ, as illustrated in Fig. 5f.
Figure 6 shows the FE-SEM observation results of microstructure and Cr2 N pre-
cipitates in the tested steels. Obviously, the amount and size of Cr2 N are much smaller
than those of σ, as shown in Fig. 6a. During hot deformation, nitride precipitated
along grain boundaries to prevent grain boundary from migrating, and further to
reduce the hot ductility of steel. The EDS results in Fig. 6b, c show that Cr2 N phase
Fig. 5 Morphologies and EDS of σ precipitates in the steel sample with cracks: a, b δ/γ boundaries
precipitation; c EDS of pt1 in (b); d, e precipitation in ferrite grains; f EDS of pt2 in (e)
Fig. 6 Morphology and EDS of Cr2 N precipitates: a SEM morphology; b and c EDS of pt1 and
pt2, respectively
contains more Cr, N, and V elements than those of the matrix. Cr and N are important
for SDSS to keep high strength and corrosion resistance. Vanadium, as a residual
element, should be reduced to prevent Cr2 N precipitates. SDSS is ultra-low carbon
steel, no distinct M23 C6 precipitates were observed in the tested steels.
Figure 7 shows the FE-SEM observation results of precipitate around the cracks.
Near δ/γ interfaces, cracks initiate in the ferrite grains, and propagate along the δ/γ
interfaces. And σ phase can be observed around the cracks source or on the cracks
propagation boundary. It is said that σ phases can seriously damage the hot working
properties of SDSS. Therefore, finish rolling temperature should be controlled above
σ precipitation temperature.
164 W. Shen et al.
Fig. 7 SEM morphology of

precipitates around the
cracks
The Effect of Inclusions on the Cracking
Inclusion is one of the main factors affecting the hot workability of SDSS. In SDSS,
alloying elements, such as Al, Si, Ca, Ti, and Mg, may form non-metallic inclusions
during deoxidation or continuous casting solidification process. As illustrated in
Fig. 8, when the size and number of inclusions are not properly controlled, the cracks
are easily initiated and propagated, since non-deformable inclusions are prone to
result in uneven deformation during hot working. As shown in Fig. 8a, microstructure
around inclusion was broken, and further many microcracks occurred. The EDS
Fig. 8 SEM morphology and EDS of inclusions around cracks: a crack initiation; EDS of pt1 (b),
pt2 (c); d crack propagation; e EDS of pt3
Fig. 9 Morphology and EDS of oxide layers rolled into the matrix: a OM in transection; b SEM
of polished surface; c EDS results of pt1 in (b)
results in Fig. 8b, c show that inclusions in the crack initiation are main Al2 O3
and Si–Ca–Mg–Al composite inclusions. Al2 O3 inclusions were also observed in
the crack propagation boundaries, as shown in Fig. 8d, e. Therefore, the size and
number of Al2 O3 in SDSS should be strictly controlled to reduce crack initiation and
propagation during hot working.
The Effect of Oxide Layer on Cracking
Figure 9 shows the OM and FE-SEM observation results of oxide layer rolled into
the matrix. The cracks propagating into matrix from surface oxide layer was shown
in Fig. 9a. After being polished, we can observe several oxide layers embedded in
the matrix, and there are obvious microcracks along the oxide layers, as shown in
Fig. 9b. The EDS results in Fig. 9c show that oxide layer mainly contains Fe, Cr, and
O elements.
Conclusions
The effects of microstructure evolution, precipitates, inclusions, and surface oxide

layer on hot workability of industrial super duplex stainless steel have been investi-
gated, the mechanism of crack initiation and propagation have also been discussed.
The conclusions are as follows:
(1) After hot rolling, both ferrite and austenite phases were elongated in rolling
direction. The microcrack generally occurs between δ and γ dual-phases, and
the microstructure of crack propagation exhibits a typical flow localization band,
which is caused by uneven deformation.
(2) Sigma and HCP are main precipitates in the hot working temperature range.
Sigma has accounts for the largest amount of all precipitation and preferably
precipitates at δ/γ interfaces, which seriously damage the hot workability of
166 W. Shen et al.
SDSS. Nitride, as another high temperature phases, precipitated along grain

boundaries to prevent grain boundary from migrating, and further to reduce
the hot ductility of steel. SDSS is ultra-low carbon steel, so no distinct M23 C6
precipitates were observed in the tested steels.
(3) Inclusion is one of the main factors affecting the hot workability, especially
Al2 O3 . Non-deformable Al2 O3 inclusions are prone to bring about stress con-
centration and uneven deformation during hot working, and further to cause the
cracks initiation and propagation. Besides, the surface microcracks resulting
from the oxide layers rolled into the matrix.
Acknowledgements This work is financially supported by National Nature Science Foundation of

China under grant No. 51674020, China’s 13th Plan of Five-year National Key Research and Devel-
opment Program under Grant No. 2016YFB0300102-5 and Open Funds of State Key Laboratory
of Advanced Metallurgy (KF18-01).
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Part III
Fundamentals of Metallurgical Processes
Corrosion Behaviors of Al2 O3 and ZrO2
Refractories in Contact
with High-Basicity Refining Slag
Liwen Xue, Tongsheng Zhang and Wanlin Wang
Abstract Al2 O3 and ZrO2 refractories are widely used in the steel industry as lining
materials for many metallurgical reactors. Since the refractory material is in direct
contact with the slag and molten steel, it is susceptible to corrosion and degrada-
tion, particularly on the slag line. The corrosion behavior of high-basicity refining
slag to refractories was studied in this paper. The results show that Al2 O3 refrac-
tories would partially dissolve into the slag, and form a transition layer composed
of CaAl12 O19 and CaAl4 O7 . For ZrO2 refractories, the slag and the ZrO2 crucible
produce a transition layer composed of CaZrO3 , CaZr4 O9 , and Ca6 Zr19 O44 , which
prevents the further corrosion of the crucible. The corrosion mechanism was studied
by experiments combined with thermodynamic calculations and the establishment of
new corrosion models. This study is expected to serve as a guide for the production
and industrial application of the refractory materials.
Keywords Refractory · Corrosion · Thermodynamic simulation · High-basicity

refining slag
Introduction
The refractories are widely used in various aspects of the ferrous metallurgical indus-
try [1, 2], such as acidic and alkaline lining materials, high alumina bricks, magnesia
chrome bricks, the stoppers, and nozzles made by ZrO2 –C, MgAl2 O4 –C Al2 O3 –C,
MgO–C [3–5]. Actually, the refractory material, especially in the position of the slag
line, suffers severe corrosion effect from the molten steel and the slag, which will
reduce the service life of the refractory material. Furthermore, the corrosion products
of the refractory material often become a source of harmful inclusions during the
refining process [6], which will affect the quality of the steel product. Therefore, it
L. Xue · T. Zhang (B) · W. Wang

School of Metallurgy and Environment, Central South University, Changsha,
e-mail: tongsheng.zhang@csu.edu.cn
National Center for International Cooperation of Clean Metallurgy, Changsha, China
https://doi.org/10.1007/978-3-030-36540-0_16
172 L. Xue et al.
is important to study the interaction behavior between the refractory materials and
the refining slag in steelmaking process.
Tse et al. [7] observed the dissolution behavior of Al2 O3 particles in different
types of slags by confocal scanning laser microscopy (CSLM) and found that the
dissolution rate in 50% CaO–50% Al2 O3 slag was faster than that in 40% CaO–
40% SiO2 –20% Al2 O3 slag. Although many studies have been conducted on the
dissolution behavior of Al2 O3 in slag, such as the study of inclusions dissolved in
slag and the dissolution of alumina cylinders or discs into slag.
Anezirise et al. [8] found that Na and Si invade into the interior of the ZrO2 -
based ceramic through a chemical dissolution process, causing localized corrosion
at the grain boundaries. The micro cracks and serrated grains can provide conditions
for further penetration and catalytic dissolution of the slag, resulting in increased
corrosion. Himpel et al. [9] studied the corrosion of ZrO2 -based refractories by
coal ash. It has been found that the calcium zirconate was produced by the reaction
between zirconia and alkaline coal ash, and it is almost completely detached from
the ceramic surface during cooling. Some researchers also found that Mg-aluminate
crystals and a phase containing no Zr and a phase containing Zr were precipitated on
the surface of the material of the zirconia-slag joint. Some researchers also focused
on the corrosion mechanism of MgO–CaZrO3 –calcium silicate material and the slag
resistance of MgO–ZrO2 refractories [10].
Experimental Apparatus and Procedure
The experiment was carried out in a high-frequency induction heating furnace, as

shown in Fig. 1. The chemical composition of industrial pure iron is shown in Table 1.
The experimental internal diameter of the crucible is 45 mm, the outer diameter is
50 mm, and the height is 100 mm. According to the composition of the initial slag
in Table 2, the chemical pure reagents CaO, Al2 O3 , SiO2 , MgO MnO, and TiO2
Fig. 1 High-frequency
induction heating furnace
Table 1 Chemical compositions of industrial pure iron in present works (wt%)
C Si Al Ti Mg Mn Ca P S Fe
0.003 0.005 0.035 \ \ 0.03 \ 0.011 0.005 99.80
Corrosion Behaviors of Al2 O3 and ZrO2 Refractories …
173
174 L. Xue et al.
Table 2 The major compositions of initial slag in present work (wt%)

CaO SiO2 Al2 O3 MgO MnO TiO2
44.42 8.08 32.00 4.50 5.00 6.00
were uniformly mixed, and then pre-melted by an intermediate frequency induction

furnace to make the composition uniform. After 500 g of industrial pure iron was
placed in a crucible, it was heated to 1600 °C (1873 K) in an induction furnace, and
25 g of refining slag was added. It was observed that the slag began to be timed after
the slag was melted, and the slag sample was taken out at 1 min, 5 min, 10 min,
20 min, 30 min, and 40 min, respectively. After the heat is kept for 30 min, the
furnace stops heating and is cooled with the furnace. High purity argon (99.99%)
was used as a shielding gas during the experiment to maintain the atmosphere inside
the furnace. When the temperature reaches room temperature, take out the crucible.
The crucible cross section of the slag was made into a mosaic sample, then polished,
and its microstructure and composition were analyzed by SEM and EDS.
Evolution of Refining Slag Composition
The composition of slag always changed during the contact between the crucible and
slag. Figure 2 shows the variations of slag components in Al2 O3 and ZrO2 crucible
with time. As the interaction time between the crucible and slag increases, the content
of CaO in the slag decreases gradually, while the Al2 O3 in the slag increases gradually,
Fig. 2 Variations of slag components in Al2 O3 crucible and ZrO2 crucible with time. (Al2 O3
crucible (a), ZrO2 crucible (b))
Corrosion Behaviors of Al2 O3 and ZrO2 Refractories … 175
as shown in Fig. 2a. It indicates that Al2 O3 in the crucible enters the slag during the
corrosion process, and CaO can be consumed. The same phenomenon occurred in
the experiment of ZrO2 , as shown in Fig. 2b. During the interaction between slag and
crucible, the CaO content of the slag is lower than that of the initial slag, and ZrO2
appears in the slag. It can be seen from Fig. 2 that the slag composition remained
stable from 20 min.
Corrosion Characteristics and Slag Seepage Into Various

Crucibles
(1) Corrosion of refining slag on Al2 O3 crucible

The SEM-image and line scan results of the slag–Al2 O3 crucible interface are given
in Fig. 3. The overall values of the red and black lines in the Y-axis direction from
the region I to the region III in Fig. 3b are increased constantly. From the trend of
the red line and the black line, the Al and O contents gradually increase from the
slag layer, the transition layer to the crucible layer. It can be seen in Fig. 3b that the
content of Ca gradually decreases from the slag layer to the crucible layer, and the
content in the crucible region is almost zero.
The components of points A1, A2, A3, A4, A5, and A6 in Fig. 3a were analyzed
by SEM andEDS, and the results are shown in Table 3. It is referring to the region
II in Fig. 3b, the transition layer which has a thickness of about 15 µm is composed
of CaAl12 O19 and CaAl4 O7 , wherein the composition near the side of the refining
slag is CaAl4 O7 . On the one hand, the mass transfer of Al2 O3 to the refining slag
is inhibited due to the high content of Al2 O3 in the slag. On the other hand, it can
be seen from the present study that the high melting point phase of CaAl12 O19 and
Fig. 3 SEM-image and line scan results of the slag–Al2 O3 crucible interface (a SEM-image b line
scan results)
176 L. Xue et al.
Table 3 SEM and EDS results of points in Fig. 4a

Sample O Mg Al Ca Total Probable phase
A1 41.80 \ 43.40 14.80 100.00 CaAl4 O7
A2 45.70 \ 48.60 5.70 100.00 CaAl12 O19
A3 40.15 \ 44.01 15.84 100.00 CaAl4 O7
A4 44.80 \ 50.20 5.00 100.00 CaAl12 O19
A5 46.00 \ 54.00 0.00 100.00 Al2 O3
A6 40.30 \ 43.00 16.70 100.00 CaAl4 O7
CaAl4 O7 at the interface between the refining slag and the crucible can also reduce
the corrosion of the slag on the Al2 O3 crucible.
(2) Corrosion of refining slag on ZrO2 crucible
The microscopic observations of the interface between the refining slag and ZrO2
crucible are displayed in Fig. 4. The compositions of points Z1, Z2, Z3, Z4, Z5,
and Z6 in Fig. 4b were analyzed by SEM andEDS, and the results are shown in
Table 4. As can be seen from the table, the transition layer is mainly composed
of Ca, Zr, O, and a small amount of Ti. In Fig. 4b, the small amount of Ti in the
transition layer may be the small amount of CaTiO3 formed in the slag that enters
the transition layer. In summary, the transition layer consisting of high melting point
phases (CaZrO3 , Ca6 Zr19 O44 ) and a small amount of CaZr4 O9 with a thickness of
about 60 µm isolates the slag and crucible, inhibiting the further interaction of the
refining slag and crucible.
Fig. 4 SEM-image (a) and line scan results of the slag–ZrO2 crucible interface (b). ((a) SEM-image
(b) line scan results)
Table 4 SEM and EDS results of points in Fig. 4a
Sample O Mg Al Si Ca Ti Mn Zr Total Probable phase
Z1 41.40 1.90 25.40 3.30 27.40 0.50 0.50 \ 100.00 Slag
Z2 25.10 \ \ \ 23.10 1.60 49.20 100.00 CaZrO3
Z3 26.50 \ \ \ 21.37 2.00 50.13 100.00 Ca6 Zr19 O44
Z4 29.50 \ \ \ 19.70 1.70 49.63 100.00 CaZr4 O9
Corrosion Behaviors of Al2 O3 and ZrO2 Refractories …
Z5 26.70 \ \ \ 9.37 1.30 62.63 100.00 ZrO2

Z6 26.12 \ \ \ \ \ 73.98 100.00 Ca6 Zr19 O44
177
178 L. Xue et al.
Thermodynamic Simulation of Corrosion of Al2 O3 and ZrO2

by Refining Slag
The corrosive reactions are usually not in a thermodynamic equilibrium, which is

however a prerequisite of the performed calculations. It is known that the slag reacts
immediately after contacting with the crucible, and the reaction product continues to
react with the crucible, and the above steps are repeated again and again [11–13]. At
the constant temperature of 1873 K and the pressure of 1 atm, the weight of the slag
remains unchanged, while the weight of the crucible matrix are used as a variable.
All possible ratios between the refining slag and the crucible matrix were studied as
a function of the reaction rate X = C/(S + C), where C represents crucible weight,
S represents the weight of the slag. This ratio can reflect the degree of corrosion of
the crucible. The larger the value of the index X, the more severe the corrosion. At
the beginning of the reaction, both X is 1, indicating a reaction near the crucible
position. As the reaction progresses, X decreases, the weight percent of each phase
formed as a function of X, and the slag composition as a function of X are shown in
Figs. 5 and 6.
(1) Simulation of Al2 O3 crucible corrosion
The corrosion from the crucible to slag is explained as follows. As shown in Fig. 5a,
when 1.0 < X < 0.74, along with the decrease of X, the contents of CaAl12 O19
and Ca2 Mg2 Al28 O46 increase, while the contents of Al2 O3 decline sharply. When
X = 0.80, the content of CaAl12 O19 reached a maximum of 69%. When X = 0.74,
the content of Al2 O3 was zero. In this interval, CaAl12 O19 and Ca2 Mg2 Al28 O46 are
generated by the reaction Eqs. (1) and (2), respectively.
CaO(slag) + 6Al2 O3(crucible) = CaAl12 O19(crucible) (1)
Fig. 5 The corrosion behavior predicted by thermodynamic simulations in an Al2 O3 crucible as

a function of the reaction rate X (a weight percent of each phase b change of the liquid slag
composition)
Fig. 6 The corrosion behavior predicted by thermodynamic simulations in a ZrO2 crucible as

a function of the reaction rate X (a weight percent of each phase b change of the liquid slag
composition)
2CaO(slag) + 2MgO(slag) + 14Al2 O3(crucible) = Ca2 Mg2 Al28 O46(crucible) (2)
When 0.74 < X < 0.59, the CaAl4 O7 phase appears in the system. When X =
0.59, the content of CaAl12 O19 is zero, while the content of Ca2 Mg2 Al28 O46 reached
a maximum of 20%. As X decreases, the content of CaAl12 O19 decreases and the
content of CaAl4 O7 increases. In this interval, CaAl12 O19 is gradually converted by
Eq. (3) to CaAl4 O7 .
CaAl12 O19(crucible) + CaO(slag) = 3CaAl4 O7(crucible) (3)
When 0.59 < X < 0.54, the content of CaAl4 O7 increased gradually with the
decrease of X. The content of Ca2 Mg2 Al28 O46 decreased gradually, which con-
tinues to be converted to CaAl4 O7 by Eq. (4). When X = 0.54, the content of
Ca2 Mg2 Al28 O46 was zero, while the content of CaAl4 O7 reached the maximum
content of 44.75%.
Ca2 Mg2 Al28 O46(crucible) = 2CaAl4 O7(crucible) + 2MgO(slag) + 10Al2 O3(slag) (4)
When the value of X is 0.54 < X < 0.41, there are liquid slag and CaAl4 O7 in the
system. When X = 0.41, the content of CaAl4 O7 is zero and the amount of liquid
slag constantly raises. When X < 0.41, liquid slag is the only existing phase. In this
interval, CaAl4 O7 content decreases rapidly through Eq. (5).
CaAl4 O7(crucible) = 2Al2 O3(slag) + CaO(slag) (5)

180 L. Xue et al.
Figure 5b shows the variation of the slag composition as X decreases. Com-

bined with experimental results and thermodynamic simulation, it is obvious that the
corrosion endpoint exists in the range of 0.41–0.74.
(2) Simulation of ZrO2 crucible corrosion
The corrosion process is discussed as follows. As shown in Fig. 6a, when 1.0 <
X < 0.73, with the decrease of X, the relative contents of CaZr4 O9 and liquid slag
increased. However, the content of ZrO2 in liquid slag decreased sharply. At X =
0.73, the content of CaZr4 O9 reached a maximum of 68%, while the relative content
of ZrO2 decreased to zero. However, as shown in Fig. 6b, the composition of the
refining slag is unchanged in the range of 1.0 < X < 0.73. In this interval, CaZr4 O9
is produced by the reaction (6).
4ZrO2(crucible) + CaO(slag) = CaZr4 O9(crucible) (6)
The fact ZrO2 in slag drops when 0.66 < X < 0.73 indicates with the addition of
slag (decreasing of X), there isn’t enough ZrO2 (decrease of ZrO2 activity) to react
with CaO and hence there is an increase of CaO in slag, which corresponds to the
increase of CaO content in the slag in Fig. 6b.
When 0.66 < X < 0.62, the Ca6 Zr19 O44 phase appears in the curve and the rel-
ative content reached 52% at X = 0.62. As the X decreases, the relative content
of CaZr4 O9 decreases rapidly, whereas the relative content of Ca6 Zr19 O44 increases
sharply. When X = 0.62, the relative content of CaZr4 O9 was zero. It is correspond-
ing to Fig. 6b, the content of each component of the refining slag is relatively stable.
In this interval, CaZr4 O9 is converted to Ca6 Zr19 O44 by Eq. (7).
6CaZr4 O9(crucible) = Ca6 Zr19 O44(crucible) + 5ZrO2(slag) (7)
When it is 0.62 < X < 0.45, the content of Ca6 Zr19 O44 decreases gradually with
the decrease of X, but the relative content of CaZrO3 increases sharply. When X =
0.45, the content of Ca6 Zr19 O44 is zero, while the relative content of CaZrO3 reaches
30%. In this interval, CaZrO3 is generated by Eqs. (8) and (9).
Ca6 Zr19 O44(crucible) = 6CaZrO3(crucible) + 13ZrO2(crucible) (8)
When 0.45 < X < 0, the overall content of CaZrO3 is decreasing with the decrease
of X, but the relative content of liquid slag gradually increases. In this interval,
CaZrO3 is generated by Eq. (9).
CaO(slag) + ZrO2(crucible) = Ca Zr O3(crucible) (9)
Combining the experimental results with the thermodynamic simulation, it is

obvious that the corrosion endpoint exists in the range of 0.45–0.66.
Conclusion
Laboratory experiments and thermodynamic simulations were carried out to study the
effect of high basicity slag on the corrosion behavior of Al2 O3 and ZrO2 refractories.
(1) The slag corrosion mechanism of refractory materials can be explained by the
thermodynamic model in current research. The experimental results are in good
agreement with the thermodynamic model.
(2) For Al2 O3 refractories, Al2 O3 in the crucible matrix dissolves into the slag,
and some part of the crucible is significantly thinner. The refining slag forms a
dense layer of 15 µm thickness with alumina crucible, and its main components
are CaAl12 O19 and CaAl4 O7 . The liquid phase is the driving force for the slag
to penetrate, and the formed solid oxides create obstacles that hinder further
penetration of the slag.
(3) For ZrO2 refractories, the refining slag and ZrO2 crucible can form a transition
layer of about 60 µm thick, which is composed of some high-melting composite
oxides (CaZrO3 , Ca4 Zr19 O44 , and CaZr4 O9 ). The transition layer isolates the
contact of the slag with ZrO2 crucible, prevents the reaction between them,
thereby protecting and improving the corrosion resistance of the crucible.
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83rd steelmaking conference, ISS, Pittsburgh, USA, pp 219–229, March 2000
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Phase Equilibria in the System
Al2 O3 –MnO–SiO2 : Thermodynamic
and Application
Yunhui Hua and Baojun Zhao
Abstract Al2 O3 –MnO–SiO2 is an important base system related to steelmaking,

ferromanganese and silicomanganese production, and lithium ion battery treatment.
Phase equilibria in this system have been extensively and repeatedly studied since
1943 due to significant discrepancies. The early experimental studies were carried
out under nitrogen gas flow which was considered as inert atmosphere. Recent stud-
ies showed that nitrogen can dissolve into the oxide melts under reducing conditions
causing different liquidus temperatures and phase compositions. Clearly, the exper-
imental conditions and results have to be identified to be N-containing or N-free
for various applications. Careful experiments and comparison of experimental tech-
niques explained the discrepancies in this system reported by different researchers.
Thermodynamic modeling calculations are also performed for the N-containing and
N-free systems to demonstrate the importance in the selection of the parameters.
Keywords Al2 O3 –MnO–SiO2 · Phase equilibria · EPMA · Nitrogen
Introduction
The Al2 O3 –MnO–SiO2 ternary system plays an important role in many metallurgical
processes. It is closely related to the refining slag and inclusions in steelmaking
like tire-core steel, high Ni-steel [1], and high Mn-steel [2]. They are the major
components of the slags in ferromanganese and silicomanganese production [3].
In pyrometallurgical treatment of tungsten slag [4–6] and polymetallic deep-sea
nodule [3, 7–12], Al2 O3 –MnO–SiO2 is also the major system of the slag. The Al2 O3 –
MnO–SiO2 system is becoming more important in pyrometallurgical recycling of
lithium ion batteries (LIBs) because Mn-containing cathode is commonly used in the
batteries. Recycling of LIBs is more and more important for sustainable development
and environmental protection [13–15] as a result of rapidly increased used batteries.
Y. Hua · B. Zhao (B)

The University of Queensland, Brisbane, Australia
e-mail: baojun@uq.edu.au

https://doi.org/10.1007/978-3-030-36540-0_17
184 Y. Hua and B. Zhao
Due to the importance of the Al2 O3 –MnO–SiO2 system, phase equilibrium study
in this system has been repeated many times since 1943 [16–20]. However, there are
still discrepancies among experimental data [16, 17, 19, 20] and thermodynamic cal-
culations [18]. The same research group, using the same research technique, reported
two versions of the phase diagram for the system Al2 O3 –MnO–SiO2 but they did
not give the explanation [17, 19, 20]. In recent studies by the authors, it was found
that nitrogen can participate in the high-temperature reactions at certain conditions.
Nitrogen cannot be considered as an inert atmosphere. The experiments in the system
Al2 O3 –MnO–SiO2 were carried out in nitrogen by Snow [16] and Roghani et al. [17],
in argon by Haccuria et al. [19, 20]. FactSage is a popular thermodynamic model to
predict liquidus temperature and phase equilibria of metallurgical slags [21]. N-free
and N-containing oxide liquid slags have been included in the current database of the
FactSage 7.3. This paper will explain the reasons to cause discrepancies and com-
pare the results from different sources. Model developers will be able to select the
experimental data carefully to optimize different solid-solutions and the industrial
operators will be able to use the appropriate phase diagrams to assist their operations.
Different Versions of the Phase Diagram Al2 O3 –MnO–SiO2
Different techniques were used by these researchers to determine the phase diagrams.
Snow [16] prepared melts in a platinum boat and heat for 0.5–48 h in nitrogen.
MnCO3 was used to be the source of the MnO. Roghani et al. [17] synthesized
slag from purified oxide and prepared Mn–Si alloy from melting metal in a carbon
crucible in nitrogen. The slag was equilibrated with the Mn–Si alloy in nitrogen
followed by quenching and electron probe x-ray microanalysis (EPMA) [17]. Jung
applied modified quasichemical model for the evaluation of thermodynamic and
phase equilibrium data of Al2 O3 –MnO–SiO2 system [18]. Haccuria et al. [19, 20]
from the same research group of Roghani [17] repeated the study in argon gas.
Phase diagrams reported by these researchers are shown in Figs. 1, 2,
3, and 4, respectively. All of the authors reported cristobalite and tridymite
(SiO2 ), mullite (3Al2 O3 ·2SiO2 , A3S2), corundum (Al2 O3 ), galaxite (MnO·Al2 O3 ,
MA), tephroite (2MnO·SiO2 , M2S), rhodonite (MnO·SiO2 , MS), and spessartite
(3MnO·Al2 O3 ·3SiO2 , M3AS3) as primary phase fields. Roghani et al. [17], Jung
et al. [18], and Haccuria et al. [19, 20] also reported manganosite (MnO) primary
phase field in the system. Snow [16] and Jung et al. [18] claimed the existence of
Mn-cordierite (2MnO·2Al2 O3 ·5SiO2 , M2A2S5) which is believed to be isostructural
with cordierite (Mg2 Al4 Si5 O18 ). However, Roghani et al. [17] and Haccuria et al.
[19, 20] decided Mn-anorthite (MnO·Al2 O3 ·2SiO2 , MAS2) rather than M2A2S5 as
a primary phase. Roghani et al. reported galaxite melts congruently while Jung et al.
and Haccuria et al. believed that galaxite has incongruent melting. Jung et al. and
Haccuria et al. also disagreed with the report by Roghani et al. that the liquidus
between galaxite and corundum is eutectic. Two researchers believed that it should
be a peritectic instead. In Roghani et al. and Haccuria et al’s reports, they considered
Phase Equilibria in the System Al2 O3 –MnO–SiO2 … 185
Fig. 1 Phase diagram of Al2 O3 –MnO–SiO2 determined by Snow 1943 in nitrogen [16]
Fig. 2 Phase diagram of Al2 O3 –MnO–SiO2 determined by Roghani et al. 2002 in nitrogen [17]
Fig. 3 Phase diagram of Al2 O3 –MnO–SiO2 predicted by Jung et al. 2004 [18]
Fig. 4 Phase diagram of Al2 O3 –MnO–SiO2 determined by Haccuria et al. 2015 in argon [20]
that corundum and mullite have their boundary joined with the tridymite phase while
Jung et al. believed that corundum and mullite should join with the galaxite phase.
Snow, Jung et al., and Haccuria et al. all reported a relatively larger primary phase
field for spessartine than that reported by Roghani et al.
Effect of Atmosphere on the Experimental Results
In Snow and Roghani’s experiments, they used purified N2 as “inert” atmosphere.

Haccuria et al. used high-purity Ar gas instead but the authors did not explain the
difference between nitrogen and argon. Haccuria et al. confirmed, in most part of the
phase diagrams, the liquids reported by Roghani et al. Some differences in liquidus
between Roghani et al. and Haccuria et al. can be attributed to the difference between
atmospheres. In a recent study by the present authors on the system Al2 O3 –MnO–
SiO2 –CaO in nitrogen, it was found that MnSiN2 phase is always present in the
quenched sample together with the glass, primary solid, and Mn–Si alloy. Up to 4
wt%, N can be present in the liquid, melilite, and Mn–Si alloy. However, neglectable
N is present in other oxide phases. This indicated that nitrogen can be dissolved into
the silicate slag and certain silicate solid structures. These results confirmed those
reported by Schurmann et al. [22] that up to 0.16 wt%, N can be present in the blast
furnace slags and the nitrogen concentration in the slag increases with increasing hot
metal temperature.
The thermodynamic data in the system Al2 O3 –MnO–SiO2 evaluated by Haccuria
et al. [18] have been incorporated in the FactSage model. FactSage 7.3 is used to cal-
culate the liquidus temperatures in the system Al2 O3 –MnO–SiO2 with and without
nitrogen. The calculations are present in the pseudo-binary phase diagrams Al2 O3 –
MnO at fixed 30 and 40 wt% of SiO2 . For the calculations without nitrogen, solutions
“FToxid-SLAGA”, “FToxid-SPINB”, “FToxid-MeOB”, “FToxid-Mull”, “FToxid-
CORU”, “FToxid-TSpi”, “FToxid-Bxib”, and “FToxid-Brau” were selected. For cal-
culations under N2 , “FToxid-SLAG?” and “FToxid-MeO?” were selected to replace
“FToxid-SLAGA” and “FToxid-MeOB”. “FToxid-SLAG?” and “FToxid-MeO?” are
not the final solution approved but they contain nitrogen. The comparisons are shown
in Figs. 5 and 6.
It can be seen from Fig. 5 that, at 30% SiO2 , the liquidus temperatures from Ar
and N2 atmosphere are identical in tephorite (Mn2 SiO4 ) primary phase field. When
the slag moves to Mn–Al spinel primary phase field, the liquidus temperatures in N2
become increasingly higher than those without nitrogen. In the corundum primary
phase field, this difference becomes even larger. At 30% SiO2 and 36% Al2 O3, the
liquidus temperature in nitrogen is 126 °C higher than that without nitrogen. At
40% SiO2 , the liquidus temperatures in rhodonite (MnSiO3 ) have no significant
difference in both atmospheres. When it comes to spessartine (Mn3 Al2 Si3 O12 ) and
mullite (Al6 Si2 O13 ) primary phase fields, the liquidus temperatures in N2 atmosphere
are higher than those without nitrogen. The difference in the liquidus temperatures
increases with increasing Al2 O3 concentration.
30% SiO2
1700
Liquidus Temperature (ºC)

N-containing N-free
1600
1500
1400 Al2O3
1300
1200 M2S MA
1100
1000
0.0 10.0 20.0 30.0 40.0 50.0
Al2O3 (wt%)
Fig. 5 Pseudo-binaries of MnO–Al2 O3 at 30 wt% SiO2 in N2 -free and N2
Fig. 6 Pseudo-binaries of 40%SiO2

1600
MnO–Al2 O3 at 40 wt% SiO2 N-containing

in N2 -free and N2 1500
1400
N-free
1300
A3S2
1200
MS
M3AS3
1100
1000
0.0 10.0 20.0 30.0 40.0
Al2O3 (wt%)
To compare experimental results and FactSage predictions, four sets of liquidus

temperatures at 20% SiO2 are shown in Fig. 7. It can be seen from the figure that
experimentally determined liquidus temperatures by Roghani et al. [17] and Hac-
curia et al. [19, 20] are close in the composition range compared. In MnO primary
phase field, the liquidus temperatures without nitrogen (Haccuria et al. [19, 20]) are
slightly higher than those in N2 (Roghani et al. [17]) which has the same trend as
those predicted by FactSage. In the Mn–Al spinel primary phase field, FactSage pre-
dicted much higher liquidus in the N-containing slag than those without nitrogen. In
both MnO and Mn–Al spinel primary phase fields, there are still significant differ-
ences in liquidus temperature between the experimental measurements and FactSage
predictions. In all experiments in nitrogen [16, 17], nitrogen concentration was not
measured and they might have been used for development of N-free database. It is
clear that FactSage databases need to be optimized with more reliable experimental
data, in particular, N-containing data.
20% SiO2
1650
N-containing
1600
Haccuria 2015 N-free
1550
1500
1450
Roghani 2002
1400 MnO MA
1350
1300
0.0 10.0 20.0 30.0 40.0 50.0
Al2O3 (wt%)
Fig. 7 Comparison of pseudo-binaries MnO–Al2 O3 at 20 wt% SiO2 in Ar and N2 from calculations

and experiments
Applications of the Phase Diagrams in Operations
Both N-free and N-containing phase diagrams can be applied to support industrial
operations with careful consideration of the operating conditions. In steelmaking
process, where Ar gas is used or under vacuum, the phase diagram produced without
nitrogen is applicable. In the pyrometallurgical processes where air is involved, the
partial pressure of nitrogen is between 0 and 1. The liquidus temperatures of the
slags will be between those generated in nitrogen and argon. An example is that
for the pyro-treatment of spent lithium ion batteries in Umicore, air atmosphere is
applied in the furnace [23]. During the real production, the partial pressure of N2
could vary from 0 to 1 because the gas contains CO, CO2 , and N2 . A combination
of both systems with and without nitrogen will be considered to design a suitable
process.
Conclusions
Experimental determined phase equilibria data of oxide slags are important for
both pyrometallurgical operations and thermodynamic modeling optimization. It is
demonstrated from the present study that nitrogen cannot be always considered as
inert atmosphere which can participate in certain chemical reactions under reducing
conditions. Nitrogen should always be measured when it is involved in the reaction
system. Development of thermodynamic databases for nitrogen-containing systems
must use the experimental data including nitrogen as one of the components. In prac-
tice, nitrogen is usually present in the open system where the condensed phases are
exposed to air. It is safe to use argon as inert atmosphere in high-temperature reac-
tions. Only the experimental data generated in argon can be used for optimization of
the thermodynamic databases without nitrogen.
References
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and inclusion chemistry in Mn/Si killed tire-cord steel. J Min Metall Sect B 48(1):37–43
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manganese steel welds. Metall Mater Trans A 45(4):2046–2054
3. Wellbeloved DB, Craven PM, Waudby JW (2012) Manganese and manganese alloys. Ullmann’s
Encyclopedia of Industrial Chemistry, vol 22, 7th ed, pp 175–221
4. Zhu HL, Deng HB, Wu CH, He XM (2010) The Current Comprehensive Recovery Technology
of Tungsten Slag. China Tungsten Ind 25(4):15–18
5. Luo JS, Wang LL (1998) Research on comprehensive utilization of Tungsten Slag. Jiangxi
Metall 18(6):31–32
6. Yang DQ, Fu SY, She DL, Wang FT (1982) Research on comprehensive utilization of Tungsten
Slag. Hunan Metall (4)
7. Agarwal S, Sahu KK, Jana RK, Mehrotra SP (2009) Recovery of Cu, Ni, Co and Mn from
sea nodules by direct reduction smelting. In: Proceedings of the eighth ISOPE ocean mining
symposium, Chennai, India, 20–24 September, 2009, pp 131–136
8. Agarwal S, Sahu KK, Godiwalla KM, Rajak DK, Smita K, Jana RK (2010) An experimental
and thermodynamic study on reduction smelting of sea nodules to recover valuable metals. In:
Proceedings of the XI international seminar on mineral processing technology, Jamshedpur,
India, 15–17 December 2010, pp 1024–1031
9. Friedmann D, Pophanken AK, Friedrich B (2017) Pyrometallurgical treatment of high
manganese containing deep sea nodules. J Sustain Met 3(2):219–229
10. Sommerfeld M, Friedmann D, Kuhn T, Friedrich B (2018) “Zero-Waste”: a sustainable
approach on pyrometallurgical processing of manganese nodule slags. Minerals 8:544. https://
doi.org/10.3390/min8120544
11. Friedmann D, Friedrich B (2016) Optimized slag design for maximum metal recovery during
the pyrometallurgical processing of polymetallic deep-sea nodules. In: Advances at the 10th
international conference on molten slags, fluxes and salts, Washington, US, 22–25 May 2016,
pp 97–104
12. Premchand P, Jana RK (1999) Processing of polymetallic sea nodules: an overview. In: Paper
present in Third ISOPE ocean mining symposium, Goa, India, 8–10 November 1999, pp 237–
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13. Yun L, Linh D, Shui L, Peng X, Garg A, Le MLP, Sandoval J et al (2018) Metallurgical and
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16. Snow RB (1943) Equilibrium relationships on the liquidus surface in part of the MnO-Al2O3-
SiO2 system. J Am Ceram Soc 26(1):11–20
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Affairs Development Bank of South Africa (Project No. DB-074 (RW1/1016). 1
Thermodynamic Analysis
of Chlorination of Zinc-Bearing Phases
in Pyrite Cinder
Deqing Zhu, Dingzheng Wang, Congcong Yang, Jian Pan, Hongyu Tian
and Yuxiao Xue
Abstract Thermodynamic analysis of chlorination of zinc-bearing phases in pyrite

cinder was conducted by FactSage thermochemical software. The effects of temper-
ature and main components of pyrite cinder on the chlorination of ZnO and ZnFe2 O4
were studied. The results show that the presence of CaO and MgO has no effect on
the chlorination of ZnO while the starting chlorination temperatures of ZnO decrease
from 1525 °C to 1200, 950, 850 °C with the presence of Fe2 O3 , SiO2 , and Al2 O3 ,
respectively. In contrast, the presence of Fe2 O3 and MgO has no effect on the chlori-
nation of ZnFe2 O4 while the starting chlorination temperatures of ZnFe2 O4 change
from 1350 °C to 825, 1075, 1525 °C with the presence of SiO2 , Al2 O3 , and CaO,
respectively. The thermodynamic analysis is consistent with the experimental results
available in the literature.
Keywords Thermodynamic analysis · Chlorination · Zinc oxide · Zinc ferrite
D. Zhu · D. Wang (B) · C. Yang · J. Pan · H. Tian · Y. Xue

School of Minerals Processing and Bioengineering, Central South University,
Changsha, Hunan, People’s Republic of China
e-mail: wangdingzheng@csu.edu.cn
D. Zhu
e-mail: dqzhu@csu.edu.cn
C. Yang
e-mail: smartyoung@csu.edu.cn
J. Pan
e-mail: pjcsu@csu.edu.cn
H. Tian
e-mail: 155611031@csu.edu.cn
Y. Xue
e-mail: yxxue@csu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_18
194 D. Zhu et al.
Introduction
Pyrite cinder is a byproduct of acid making from pyrite ores and it contains abundant
iron as well as considerable amounts of zinc, lead, and copper, etc. Currently, more
than ten million tons of pyrite cinders are generated in China annually, most of which
are disposed by land filling. However, this may lead to serious environmental pollu-
tion and land occupation [1, 2]. Therefore, utilization of pyrite cinder has received
considerable attention from researchers worldwide. The persistently strong demand
for iron ores in China has necessitated the research of recovering iron from pyrite
cinders. However, according to previous studies, traditional recycling methods like
gravity separation, magnetic separation, froth flotation, and chemical beneficiation
are inefficient in upgrading iron and removing nonferrous metals (e.g., Zn, Pb and
Cu, etc.) in pyrite cinder [3–5].
The chlorination technology has been proved to be an effective method to deal with
pyrite cinder and metallurgical wastes due to high efficiency of nonferrous metals
removal at high temperature [6–8]. Nonferrous metals are transferred into metal chlo-
rides and volatilized in the chloridizing roasting process, while iron remains as metal-
lic iron or magnetite which can be used as a high-quality material for iron-making [9,
10]. Over 90% nonferrous metals like zinc, lead, and copper can be removed from
pyrite cinder under optimal conditions [11, 12]. The chlorination behaviors of zinc
and lead during the chloridizing roasting of the pyrite cinder have been studied by
some researchers [9, 10]. However, the reactions involved in the chloridizing roasting
process are complicated owing to complex chemical composition of pyrite cinders. In
addition, the contents of zinc and lead are relatively low in pyrite cinders which lead
to their inconspicuous chlorination during the chloridizing roasting. Consequently,
to better understand the chloridizing roasting process of pyrite cinders, the effects of
main components of pyrite cinder were taken into account and a detailed thermody-
namic study was performed using the FactSage thermochemical software. Hence, the
effects of temperature and main components of pyrite cinder on chlorination process
of ZnO and ZnFe2 O4 can be revealed. The theoretical calculation results were also
compared with experimental results available in the literature.
The pyrite cinder used herein was collected from the Ningxia Province. Its chemical
compositions and Zn phase compositions are listed in Tables 1 and 2, which are
determined by using chemical titration methods. Table 3 lists the simplified chemical
compositions of pyrite cinder for thermodynamic calculation. The mole ratio of Zn
to other elements in Table 3 is equal to that in Table 1. In order to ensure sufficient
chlorinating agent for chlorination, the mole ratio of Cl to Zn in Table 3 is set at 4.0.
The effect of K2 O, Na2 O, Cu, Pb, P, and As are considered negligible in this paper
because of their low contents.
Thermodynamic Analysis of Chlorination of Zinc-Bearing Phases … 195
Table 1 Chemical compositions of pyrite cinder /wt%

TFe FeO Fe2 O3 SiO2 Al2 O3 CaO MgO K2 O
49.90 2.84 68.18 10.34 2.18 3.08 2.03 0.10
Na2 O Cu Pb Zn P S As LOI
0.064 0.082 0.29 1.23 0.29 1.65 0.064 5.91
Table 2 Phase compositions of Zn in the pyrite cinder /wt%

Zn phases ZnFe2 O4 ZnO ZnS Others Total
Contents 9.76 86.18 3.25 0.81 100.00
Table 1 and Table 2 show that the iron in the pyrite cinder mainly exists in the form
of Fe3 O4 and Fe2 O3 while the zinc mainly exists in the form of ZnO, ZnFe2 O4 , and
ZnS. In terms of high temperature oxidizing-chlorination process, the ZnS and Fe3 O4
will be oxidized to ZnO and Fe2 O3 , respectively [13]. Therefore, the thermodynamic
calculation in present work only concerns about the initial and final state of above
phases.
The chemical compositions listed in Table 3 were calculated by FactSage7.1. The
Equilib module was chosen to calculate the equilibrium composition of different
systems given above, while the Reaction module was used to calculate standard Gibbs
free energy of chlorination reactions against temperature. The FactPS, FToxid, and
FTsalt databases were selected for all calculations under atmospheric pressure and
air atmosphere.
Chlorination Behavior of ZnO
ZnO–CaCl2 , ZnO–CaCl2 –CaO, and ZnO–CaCl2 –MgO Systems
Figure 1 shows the effects of temperature on equilibrium compositions of the ZnO–

CaCl2 , ZnO–CaCl2 –CaO, and ZnO–CaCl2 –MgO system. As can be seen in Fig. 1,
ZnO disappears and ZnCl2 appears when the temperature increases to 1525 °C in
these three systems, in accordance with Eq. (1). Therefore, CaO and MgO have no
influence on the chlorination of ZnO in these systems.
ZnO + CaCl2 = ZnCl2 (g) + CaO (1)

196
Table 3 Simplified chemical compositions for thermodynamic calculation /wt%

System no. Fe2 O3 SiO2 Al2 O3 CaO MgO ZnO ZnO·Fe2 O3 CaCl2 Total
1 0 0 0 0 0 26.83 0 73.17 100
2 91.54 0 0 0 0 2.27 0 6.19 100
3 0 64.40 0 0 0 9.55 0 26.05 100
4 0 0 27.63 0 0 19.41 0 52.96 100
5 0 0 0 34.97 0 17.44 0 47.59 100
6 0 0 0 0 26.19 19.79 0 54.02 100
7 0 0 0 0 0 0 52.07 47.93 100
8 87.08 0 0 0 0 0 6.72 6.19 100
9 0 54.23 0 0 0 0 23.83 21.94 100
10 0 0 20 0 0 0 41.65 38.35 100
11 0 0 0 26.05 0 0 38.50 35.45 100
12 0 0 0 0 18.86 0 42.25 38.89 100
D. Zhu et al.
80 60
50
ZnO 50
60 ZnO CaCl2
CaCl2 40
Contents / %
Contents / %
40 CaO ZnCl2
Contents / %
CaO 30 ZnO CaCl2 MgO
40 30
ZnCl2(g) CaO ZnCl2(g)
20 20
20
10 10
ZnO-CaCl2 ZnO-CaCl2-CaO ZnO-CaCl2-MgO
0 0 0
1000 1100 1200 1300 1400 1500 1600 1000 1100 1200 1300 1400 1500 1600 1000 1100 1200 1300 1400 1500 1600
Temperature / °C Temperature /°C Temperature /°C
Fig. 1 Equilibrium compositions of ZnO–CaCl2 , ZnO–CaCl2 –CaO, and ZnO–CaCl2 –MgO as a

function of temperature
ZnO–CaCl2 –Fe2 O3 , ZnO–CaCl2 –SiO2 , and ZnO–CaCl2 –Al2 O3 Systems
The effect of temperature on equilibrium compositions of ZnO–CaCl2 –Fe2 O3 , ZnO–

CaCl2 –SiO2 , and ZnO–CaCl2 –Al2 O3 systems is shown in Fig. 2. When the tempera-
ture exceeds 1200 °C, the contents of ZnO, CaCl2 , and Fe2 O3 decrease. Meanwhile,
ZnCl2 and CaFe4 O7 appear as products in the ZnO–CaCl2 –Fe2 O3 system according
to chemical reaction Eq. (2), indicating that the starting chlorination temperature of
ZnO was decreased to 1200 °C with the presence of Fe2 O3 . In contrast, SiO2 can
largely decrease starting chlorination temperature of ZnO to approximately 825 °C
in terms of ZnO–CaCl2 –SiO2 system due to the formation of CaSiO3 , corresponding
to the chemical reaction of Eq. (6). When Al2 O3 is added to ZnO–CaCl2 system, the
starting chlorination temperature of ZnO decreases from 1525 to 950 °C due to the
formation of CaAl12 O19 . The sequence of the formation of CaAlx Oy is CaAl12 O19 ,
CaAl4 O7 , and CaAl2 O4 with the increase of temperature and the possible chemi-
cal reaction are Eqs. (3)–(5). The results are in good agreement with experimental
results, showing that SiO2 and Fe2 O3 are capable of improving Zn removal from
ZnO in the process of high temperature oxidizing–chloridizing roasting [14].
ZnO + CaCl2 + 2Fe2 O3 = ZnCl2 (g) + CaFe4 O7 (2)
ZnO + CaCl2 + SiO2 = ZnCl2 (g) + CaSiO3 (3)
100 70
90 60 ZnCl2(g) Al 2O3
50 50
80 SiO 2 CaCl2 CaCl2 CaAl12O19 CaAl2O4
Fe2O3 CaCl2
12
24 ZnSiO4 CaSiO3 40 ZnO
ZnO ZnCl2(g)
Contents / %
Contents / %
Contents / %
ZnCl2(g) CaAl4O7
CaFe4O7 16 30
8
20
4 8
10
ZnO-CaCl2-Fe2O3 0
ZnO-CaCl2-SiO2 ZnO-CaCl2-Al2O3
0 0
600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600
Temperature /°C Temperature /°C Temperature /°C
Fig. 2 Equilibrium compositions of ZnO–CaCl2 –Fe2 O3 , ZnO–CaCl2 –SiO2 , and ZnO–CaCl2 –

Al2 O3 as a function of temperature
198 D. Zhu et al.
ZnO + CaCl2 + 6Al2 O3 = ZnCl2 (g) + CaAl12 O19 (4)
ZnO + CaCl2 + 2Al2 O3 = ZnCl2 (g) + CaAl4 O7 (5)
ZnO + CaCl2 + Al2 O3 = ZnCl2 (g) + CaAl2 O4 (6)
Gibbs Free Energy Gθ Versus Temperature T Relationships

of the Reactions Eqs. (1)–(6)
As can be seen in Fig. 3, the values of standard Gibbs free energy of each reaction
continuously decreases with the increase of temperature. According to the results,
the starting thermodynamic reaction temperature of Eq. (1) is 1355 °C while the addi-
tion of Fe2 O3 , SiO2 , and Al2 O3 can drastically reduce the starting thermodynamic
chlorination temperatures of ZnO from 1355 °C to 1185, 715, 935, 975, 1090 °C,
respectively, because of the formation of CaFe4 O7 , CaSiO3 , CaAl12 O19 , CaAl4 O7 ,
CaAl2 O4 , according to Eqs. (2)–(6). It can be concluded that SiO2 has the greatest
effect on reducing the starting chlorination temperature of ZnO, then followed by
Al2 O3 and Fe2 O3 .
Fig. 3 Correlation of standard Gibbs free energy Gθ with temperature for Eqs. (1)–(6)
90
50 40
85
40 80 ZnFe2O4 CaCl2
ZnFe2O4 CaCl2 30 MgO CaFe4O7
Fe2O3 CaCl2
Contents / %
Contents / %
75
Contents / %
30 CaFe4O7 Ca2Fe2O5 Ca2Fe2O5 ZnCl2(g)
70 ZnFe2O4 CaFe2O4
ZnCl2(g) 20
20 20
ZnCl2(g)
10 10
10
ZnFe2O4-CaCl2 0 ZnFe2O4-CaCl2-Fe2O3 ZnFe2O4-CaCl2-MgO
0 0
600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600
Temperature / °C Temperature / °C Temperature / °C
Fig. 4 Equilibrium compositions of ZnFe2 O4 –CaCl2 , ZnFe2 O4 –CaCl2 –Fe2 O3 , and ZnFe2 O4 –
CaCl2 –MgO as a function of temperature
Chlorination Behavior of ZnFe2 O4
ZnFe2 O4 –CaCl2 , ZnFe2 O4 –CaCl2 –Fe2 O3 , and ZnFe2 O4 –CaCl2 –MgO

Systems
The effect of temperature on equilibrium compositions of the ZnFe2 O4 –CaCl2 ,

ZnO–CaCl2 –Fe2 O3 , and ZnO–CaCl2 –MgO systems is shown in Fig. 4. As can
be seen in Fig. 4, ZnFe2 O4 begins to react with CaCl2 to form ZnCl2 (g) and
CaFe2 O4 (Ca2 Fe2 O5 ) when the temperature reaches 1350 °C in terms of Eq. (7).
It is known that the Fe2 O3 and MgO have no influence on chlorination of ZnFe2 O4
in these systems. The starting chlorination temperature of ZnFe2 O4 (1350 °C) is
much lower than that of ZnO (1525 °C) when no other additives are added. Hamano
[14] investigated the chlorination behavior of ZnO and ZnO·Fe2 O3 in Ar–Cl2 –O2
gas stream and found that ZnO·Fe2 O3 is easier to be chlorinated than ZnO, which is
consistent with the finding in the present study.
3ZnFe2 O4 + 3CaCl2 = CaFe4 O7 + Ca2 Fe2 O5 + 3ZnCl2 (g) (7)
ZnFe2 O4 –CaCl2 –SiO2 , ZnFe2 O4 –CaCl2 –Al2 O3 ,

and ZnFe2 O4 –CaCl2 –CaO Systems
Figure 5 illustrates the effect of chlorination temperature on the equilibrium composi-

tions of the ZnFe2 O4 –CaCl2 –SiO2 , ZnFe2 O4 –CaCl2 –Al2 O3 , and ZnFe2 O4 –CaCl2 –
CaO systems. For the ZnFe2 O4 –CaCl2 –SiO2 system, the contents of ZnFe2 O4 ,
CaCl2 , and SiO2 decrease and the contents of ZnCl2 and Ca3 Fe2 Si3 O12 increase
when the temperature is higher than 825 °C. This means that the starting chlori-
nation temperature of ZnFe2 O4 is 825 °C in ZnFe2 O4 –CaCl2 –SiO2 relevant to the
reaction Eq. (8). The Al2 O3 can also decrease the starting chlorination temperature
of ZnFe2 O4 to 1075 °C due to the formation of CaAl12 O19 and Al2 Fe2 O6 accord-
ing to the probable reactions Eqs. (10)–(12). The starting chlorination temperature
200 D. Zhu et al.
60
40 ZnFe2O4 40
50 CaO
CaCl2
Ca2Fe2O5
Contents / %
Contents / %
40 30 Al2O3 30
Contents / %
ZnFeO4 ZnO
30 CaCl2 20 20
20 SiO2 ZnFe2O4-CaCl2-CaO
10 10 10
0
ZnFe2O4-CaCl2-SiO2 ZnFe2O4-CaCl2-Al2O3
0 0
600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600 600 800 1000 1200 1400 1600
30 40
CaAl12O19 Al2Fe2O6 40 ZnFe2O4-CaCl2-CaO
Ca3Fe2Si3O12 CaSiO3
30 CaAl4O7 Fe2O3
Fe2O3 ZnCl2(g)
20 Contents / % 30
Contents / %
Contents / %
20 CaCl2
CaFe4O7
20 CaO(CaCl2)4
10 10 ZnCl2(g) ZnCl2(g)
10
ZnFe2O4-CaCl2-SiO2 0
0 ZnFe2O4-CaCl2-Al2O3
0
800 1000 1200 1400 1600 1000 1200 1400 1600 600 800 1000 1200 1400 1600
Fig. 5 Equilibrium compositions of ZnFe2 O4 –CaCl2 –SiO2 , ZnFe2 O4 –CaCl2 –Al2 O3 , and
ZnFe2 O4 –CaCl2 –CaO as a function of temperature
of ZnFe2 O4 increases from 1350 to 1525 °C when CaO is added to the ZnFe2 O4 –
CaCl2 system. This result agrees well with previous finding reported in literature that
CaO can deteriorate Zn removal from ZnO·Fe2 O3 [15]. The thermodynamic study
shows CaO can react with ZnFe2 O4 to form ZnO and Ca2 Fe2 O5 . As can be seen in
Sect. “Chlorination Behavior of ZnO”, the initial chlorination temperature of ZnO
is 1525 °C which is much higher than 1350 °C. Therefore, the presence of CaO will
restrict the chlorination of ZnFe2 O4 due to the formation of ZnO, corresponding to
the chemical reaction Eq. (13).
3ZnFe2 O4 + 3CaCl2 + 3SiO2 = Ca3 Fe2 Si3 O12 + 2Fe2 O3 + 3ZnCl2 (g) (8)
ZnFe2 O4 + CaCl2 + SiO2 = CaSiO3 + Fe2 O3 + ZnCl2 (g) (9)
ZnFe2 O4 + CaCl2 + 7Al2 O3 = CaAl12 O19 + Al2 Fe2 O6 + ZnCl2 (g) (10)
ZnFe2 O4 + CaCl2 + 2Al2 O3 = CaAl4 O7 + Fe2 O3 + ZnCl2 (g) (11)
3ZnFe2 O4 + 3CaCl2 + 4Al2 O3 = 2CaAl4 O7 + Fe2 O3 + CaFe4 O7 + 3ZnCl2 (g)

(12)
ZnFe2 O4 + 2CaO = Ca2 Fe2 O5 + ZnO (13)

Fig. 6 Correlation of standard Gibbs free energy Gθ with temperature for Eqs. (7)–(13)
Gibbs Free Energy Gθ Versus Temperature T Relationships

of the Reactions Eqs. (7)–(13)
As can be seen in Fig. 6, the values of standard Gibbs free energy of each reaction
continuously decrease with the increase of temperature. The starting thermodynamic
reaction temperature of Eq. (7) is 1350 °C while the starting thermodynamic reaction
temperatures of Eq. (8) and Eq. (10) are 795 °C and 1025 °C, respectively. Hence, it
is easy to know that the presence of SiO2 and Al2 O3 can decrease the Gθ values of
chlorination reactions of ZnFe2 O4 . The standard Gibbs free energy of Eq. (13) shows
the negative values within the temperature range of 600–1600 °C, which implies that
CaO can react with ZnFe2 O4 to form ZnO and Ca2 Fe2 O5 and increase the starting
chlorination temperature of ZnFe2 O4 . It can be concluded that SiO2 and Al2 O3 can
reduce starting chlorination temperature of ZnFe2 O4 while CaO shows a negative
effect on the chlorination of ZnFe2 O4 .
Conclusion
In terms of the ZnO–CaCl2 binary system, ZnO begins to react with CaCl2 to form
ZnCl2 (g) and CaO at a high temperature of 1525 °C. Extra addition of either CaO or
MgO into the system presents no direct effect on the chlorination of ZnO. However,
the addition of Fe2 O3 , SiO2 , and Al2 O3 in ZnO–CaCl2 system can reduce staring
chlorination temperature of ZnO by forming CaFe4 O7 , CaSiO3 , and CaAl12 O19 at
1200 °C, 825 °C, and 950 °C, respectively. As with the ZnFe2 O4 –CaCl2 binary sys-
tem, ZnFe2 O4 begins to react with CaCl2 to form ZnCl2 (g) and CaFe4 O7 (Ca2 Fe2 O5 )
202 D. Zhu et al.
at 1350 °C. Extra addition of either Fe2 O3 or MgO into the system presents no
direct effect on the chlorination of ZnFe2 O4 . The addition of SiO2 and Al2 O3 in
ZnFe2 O4 –CaCl2 system can reduce the starting chlorination temperature of ZnFe2 O4
by forming Ca3 Fe2 Si3 O12 and CaAl12 O19 at 825 and 1075 °C. In contrast, the CaO
can react with ZnFe2 O4 to form ZnO and increase starting chlorination temperature
of ZnFe2 O4 from 1350 to 1525 °C.
References
1. Li EP, Qiu YQ, Xiang RJ, Cheng YX (2014) Min Metall Eng 34:79–82
2. Vamerali T, Bandiera M, Mosca G (2011) In situ phytoremediation of arsenic- and metal-
polluted pyrite waste with field crops: effects of soil management. Chemosphere 83:1241
3. Bi WL, Wu WH, Li J (2011) Hydrometall. China 30:229–230
4. Zeng ZF, Li ML (2006) Min Metall 26:29–32
5. He B, Tian X, Sun Y, Yang C, Zeng Y, Wang Y, Zhang S, Pi Z (2010) Hydrometallurgy
104:241–246
6. Chen D, Zhu DQ, Chen Y (2014) ISIJ Int 54:2162–2168
7. Matsuura H, Tsukihashi F (2006) Metall Mater 37B:413–420
8. De Micco G, Fouga GG, Bohe AE (2007) Metall Mater 38B:853–862
9. Matsuura, Yajima, Tsukihashi (2011) Chlorination and evaporation behaviours of zinc and lead
at chlorinating and oxidising atmosphere. Miner Process Extr Metall 120(4)
10. Tee, Fray (2004) Reaction of zinc, copper and iron in air and chlorine mixtures. Miner Process
Extr Metall 113(3)
11. Chen D, Guo HW, Xu JF, Lv YN, Xu ZM, Huo HJ (2017) Recovery of iron from pyrite
cinder containing non-ferrous metals using high-temperature chloridizing-reduction-magnetic
separation. Metall Mater Trans B 48(2):933
12. Yang C-C, Zhu D-Q, Pan J, Li S-W, Tian H-Y (2018) A novel process for Fe recovery and Zn,
Pb removal from a low-grade pyrite cinder with high Zn and Pb contents. Int J Miner Metall
Mater 25(09):981–989
13. Peng RQ (2003) Metallurgy of Lead and Zinc. Science Technology Press, Beijing, p 55
14. Matsuura H, Tsukihashi F (2006) Chlorination kinetics of ZnO with Ar-Cl2 -O2 gas and the
effect of oxychloride formation. Metall Mater Trans B 37(3)
15. Zhu D, Chen D, Pan J (2011) Chlorination Behaviors of Zinc Phases by Calcium Chloride in
High Temperature Oxidizing-chloridizing Roasting. ISIJ Int 51(11):1773–1777
Numerical Simulation Study
of Arrangement Height and Angle
of Rotary Hearth Furnace Burner
Yang Wang, Chengbo Wu, Yun Huang, Gaopeng Zhang and Ning Mao
Abstract Based on the problem of the height and angle of the burner setting of a
rotary furnace in a steel plant, the three-dimensional model was built using ANSYS
software to simulate the influence of the burner on the temperature field and flow field
in the rotary hearth furnace at different heights and different inclination angles. The
results show that the lower the height of the burner, the more uneven the temperature
distribution near the carbon-containing pellet layer and the lower the temperature;
the inclination angle of the burner is too small, which will cause the temperature
near the layer to be too high; large, will cause the flow field near the material layer
to be disordered, which is not conducive to the reduction reaction. By comparing
the simulation results, a reasonable arrangement height and angle are obtained to
provide reliable data for the production of the rotary hearth furnace.
Keywords Rotary hearth furnace · Burner · Height · Angle · Temperature
Introduction
The rotary hearth furnace process is a coal-based rapid direct reduction technology
for rapid heating and reduction of carbon-containing pellets in a short time at high
temperatures. Because of its wide adaptability, low investment, simple process, and
reliable operation, it is widely favored by various steel mills, especially in dealing
with metallurgical dust and environmental protection [1–3]. At present, there are
few studies on the mathematical model of the rotary hearth furnace. Zhou [4] took
the burner of the rotary hearth furnace as the research object, and established the
mathematical model of the rotary hearth furnace by using the CFD commercial
software FLUENT, and analyzed the temperature field and flow of the flat flame
burner and the regenerative burner in each section of the rotary hearth furnace. The
impact of the field.
Y. Wang · C. Wu (B) · Y. Huang · G. Zhang · N. Mao

e-mail: wuchengbo@cqu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_19
204 Y. Wang et al.
In this paper, the position and angle of the rotary hearth burner arrangement are
studied, the structure of the rotary hearth furnace is simplified, the mathematical
model of flow and combustion in the furnace is established, and the furnace internal
flow is simulated by FLUENT simulating different heights and arrangement angles of
the burner, the flow field and temperature field distribution. The result is a reasonable
arrangement of burner, which provide a reference for further improving the thermal
efficiency of the rotary hearth furnace and optimizing the furnace structure.
Mathematical Model
Basic Assumptions
(1) The gas in the furnace is an incompressible fluid, and the gas flows in a turbulent
flow, and the viscous heat is not considered;
(2) The feed inlet and the discharge port have no effect on the mass transfer and
heat transfer process in the furnace;
(3) The mass transfer and heat transfer processes in the furnace are steady state
processes.
Control Equation
(1) Continuity equation [5]:
∂ρ ∂(ρu x ) ∂(ρu y ) ∂(ρu z )

+ + + =0 (1)
∂t ∂x ∂y ∂z
ρ is density (kg/m3 ); ux , uy , uz are velocity components in three directions: x, y, z

(m/s); t is time (s);
(2) Momentum equation [5]:
∂(ρu x ) ∂ p ∂τx x ∂τ yx ∂τzx

+ ∇(ρu x u) = − + + + + ρ fx (2)
∂t ∂x ∂x ∂y ∂z
∂(ρu y ) ∂ p ∂τx y ∂τ yy ∂τzy
+ ∇(ρu y u) = − + + + + ρ fy (3)
∂t ∂y ∂x ∂y ∂z
∂(ρu z ) ∂ p ∂τx z ∂τ yz ∂τzz
+ ∇(ρu z u) = − + + + + ρ fz (4)
∂t ∂z ∂x ∂y ∂z
Numerical Simulation Study of Arrangement Height and Angle … 205
P is the pressure on the fluid micro-body (pa); τx x , τx y , τx z , etc., are the components
of the viscous force τ (Pa); fx , fy , fz are unit mass forces in three directions;
(3) Energy equation [5]:
∂(ρ E)
u (ρ E + P)] = ∇[ke f f ∇T −
+ ∇[ h j J j + (τe f f u)] (5)
∂t j
E is the total energy of the fluid micelle (J/kg); h j is the enthalpy of the j (J/kg); ke f f
is the effective heat transfer coefficient (W/(m K)); J j is the diffusion flux of j;
(4) Chemical composition conservation equation [6]:
∂(ρv j m l ) ∂ ∂m l
= (l ) (6)
∂x j ∂x ∂x j
m l is the mass percentage of l; l is the exchange coefficient of l (l = ρ Dl ), Dl is

the diffusion flux of l;
(5) k − ε equation [6]:
k equation:

∂ ∂ u i ∂k
(ρu j k) = u+ + G − ρε (7)
∂x j ∂x j σk ∂ x j
ε equation:

∂ ∂ u i ∂ε ε
(ρu j ε) = u+ + (c1 G − c2 ρε ) (8)
∂x j ∂x j σε ∂ x j k
in the equation:

∂u i ∂u j ∂u i
G = ui + u i = Cμ ρk 2 /ε (9)
∂x j ∂ xi ∂ xi
u i , u j is speed vector; xi , x j is direction vector; k is turbulent energy; ε is turbulent

energy dissipation rate; Cμ , σk , σε , c1 , c2 are the k − ε equation constant, Cμ = 0.99,
σk = 1.0, σε = 1.3, c1 = 1.44, c2 = 1.92.
206 Y. Wang et al.
Geometric Model
The research object of this paper is the rotary hearth furnace of an existing design.
The structural parameters of the rotary hearth furnace are shown in Table 1, and the
structure is shown in Fig. 1.
Table 1 Rotary hearth furnace structure parameters

Parameter Numerical value Parameter Numerical value
Outer diameter 5.4 m Heating section crossing 60º
angle
Inner diameter 2.6 m Reduction section 120º
crossing angle
Preheating section furnace 0.45 m Discharge section crossing 80º
height angle
Other section furnace 1.5 m Retaining wall from the 0.6 m
height height of the bottom of
Preheating section 55° the furnace
crossing angle
Fig. 1 Rotary hearth structure

Table 2 Chemical composition of mixed gas

Ingredient CO CO2 H2 N2 O2 CH4 C2 H6
Volume fraction 26.6 7.9 18.3 21.9 0.4 24.6 0.3
Fig. 2 Burner heights
Boundary Conditions
(1) Import boundary conditions. Given the inlet velocity and temperatures of air
and gas, as well as the volume fraction of air and gas. Given the inlet turbulence
intensity and hydraulic diameter. The volume fraction of O2 in the air is 21%,
and the volume fraction of N2 is 79%. The composition of the mixed gas is
shown in Table 2.
(2) Export boundary conditions. Given the flue gas outlet pressure.
(3) The wall is made of a non-slip static wall, and the thermal conditions of the wall
are mixed boundary conditions of convection and radiation.
Burner Placement Height
In this paper, the numerical simulation is carried out for three cases of burner heights
of 0.55, 0.75, and 0.95 m (burner inclination angle is 0). The definition of burner
height is shown in Fig. 2.
Burner Inclination Angle
In this paper, the numerical simulation is carried out for the angles of the burners of
−15, 0, and 15 (the height of the burner is 0.75 m). The definition of the inclination
angle of the burner is shown in Fig. 3.
208 Y. Wang et al.
Fig. 3 Burner angles
Calculation Results and Discussion
Effect of Burner Height
Figure 4 is a temperature distribution of the section of the burner arranged at 0.55 m,

z = 0.12 m, z = 1 m, and a velocity vector diagram of the section at y = 0 m. When
the burner is arranged at 0.55 m, the gas ejected from the burner forms a recirculation
(1) Z = 0.12m Temperature distribution (2) Z = 1m Temperature distribution
(3) Y = 0m Velocity vector
Fig. 4 Burner at 0.55 m

zone above the burner. The gas mixing in the recirculation zone is more sufficient,
the temperature of this region is higher, and the temperature distribution is more
uniform. At the same time, below the burner. It also forms a small recirculation zone
where the temperature of this region is lower than the temperature of the upper part
of the furnace and the temperature distribution is not uniform enough. At the section
of z = 1 m, the maximum temperature is between 1629 ~ 1714 k; at the section of
z = 0.12 m, the maximum temperature is between 1543 ~ 1629 k. When the burner
height is arranged at 0.55 m, the flow rate of the mixed gas sprayed from the burner
reaches up to 30 m/s, resulting in uneven distribution of velocity at z = 0.12 m cross
section, which disturbs the carbonaceous pellet layer. The atmosphere is reduced
to accelerate the efflux of the CO gas, resulting in a decrease in the utilization of
reduced carbon.
Figure 5 is a temperature distribution of the section of the burner at 0.75 m, z =
0.12 m, z = 1 m and the velocity vector diagram of the section at y = 0 m. When the
burner is arranged at 0.75 m, the gas ejected from the burner forms a recirculation
zone above and below the burner, the gas in the recirculation zone is fully mixed, the
temperature distribution is uniform, and the maximum temperature of the reduction
section is between 1629 ~ 1714 k. The local temperature overheating occurs in the
heating section of z = 1 m section, reached 1714 ~ 1800 k, which is due to the
formation of a small recirculation zone here, resulting in excessive temperature.
The gas velocity distribution in the upper portion of the carbonaceous pellet layer
(1) Z = 0.12m Temperature distribution (2) Z = 1m Temperature distribution

210 Y. Wang et al.
(1) Z = 0.12m Temperature distribution (2) Z = 1.25m Temperature distribution
is uniform, which is advantageous for maintaining the reducing atmosphere layer

without being damaged, and improving the utilization ratio of the reduced carbon.
Figure 6 is a temperature distribution of the burner arranged at 0.95 m, z = 0.12 m,
z = 1.25 m section and a velocity vector diagram of the section at y = 0 m. When the
burner is arranged at 0.95 m, the gas ejected from the burner forms a recirculation
zone under the burner, the gas in the recirculation zone is thoroughly mixed, the
furnace temperature distribution is uniform, and the temperature is high. z = 0.12 m
section is located in the recirculation zone, its temperature distribution is uniform,
the highest temperature reached 1629 ~ 1714 k; z = 1.25 m section is above the
burner, the temperature distribution is not as uniform as in the recirculation zone.
It can be seen from the height of the three different burners that the temperature
distribution in the furnace is basically the same, that is, the temperature of the reduc-
tion section is the highest, the heating section and the discharge section are second,
and the temperature of the preheating section is the lowest. However, due to the small
recirculation zone in the local area, the local temperature is too high.
Fig. 7 Burner inclination angle 15º
Effect of the Inclination Angle of the Burner
Figure 7 is a temperature distribution of the sections at z = 0.12 m, z = 1.2 m, and a

velocity vector diagram of the section at y = 0 m when the burner inclination angle
is 15º. When the burner is tilted at an angle of 15º, the gas ejected from the burner
forms a recirculation zone above the burner. The z = 1.2 m section is located above
the burner and in the recirculation zone. The maximum temperature reached 1688 ~
1771 k. However, due to the downward inclination of the burner, the gas impact the
inner wall of the furnace causes the temperature near the inner wall to be too high;
z = 0.12 m, this section is located below the burner, the temperature is low, and the
temperature distribution on the section is uneven due to the gas impact the inner wall.
Since the angle of inclination of the burner is 15, the gas ejected from the burner
will disturb the reducing atmosphere in the carbonaceous pellet layer, resulting in a
decrease in the utilization of reduced carbon.
Figure 8 is a temperature distribution of the section at z = 0.12 m, z = 1.2 m, and
a velocity vector diagram of the section at y = 0 m when the burner inclination angle
is −15º. When the burner is tilted at an angle of −15º, the gas ejected from the burner
forms a recirculation zone below the burner. The z = 0.12 m section is located in the
recirculation zone, and the temperature distribution is relatively uniform. However,
due to the gas impact the inner wall, the temperature near the wall is too high, and the
maximum temperature reached 1714 ~ 1800 k, which causes the carbon-containing
212 Y. Wang et al.
Fig. 8 Burner inclination angle −15º
pellet to adhere to the bottom surface of the converter, it is difficult to discharge. Z

= 1.2 m is located above the burner, and the temperature on the section is lower than
z = 0.12 m. However, after the gas impact, the inner wall of the furnace, some gas
forms a small recirculation zone in the upper part of the furnace, causing the local
temperature to be too high.
Conclusions
(1) The height of the burner of the rotary hearth furnace should not be too low.
If the height is not enough, the temperature at the bottom of the rotary hearth
furnace will be uneven, and the reducing atmosphere of the material layer will
be destroyed, which is not conducive to the reduction reaction.
(2) The optimal inclination angle of the rotary hearth burner is 0º, too much incli-
nation angle will cause the reducing atmosphere of the material layer to be
destroyed. If the inclination angle is too small, the local temperature near the
material layer will be too high.
References
1. Hu J, Du X, Zhou W (2013) Present and evaluation of industrialized rotary hearth furnace

ironmaking technology. Sintered Pellet 38(1):36–40
2. Lufang Z (2012) Study on the technology of treating zinc-containing dust in steel plant by rotary
hearth furnace in China. Sintered Pellet 37(3):57–60
3. Gao W, Dong L (2008) Development status of coal-based direct reduction and rotary hearth
furnace technology. Min Metall 17(2):68–73
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Ind Heat 39(6):43–45
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Estimation of Thermodynamic
Properties of Sodium Magnesium
Silicates by the Polyhedron Method
Zhongping Zhu, Jinxiang You, Xin Zhang, Jian Wang, Jiaoyang Duan,
Tao Zhang, Zhiwei Peng, Tao Jiang and Mingjun Rao
Abstract A simple method for calculating thermodynamic properties such as

enthalpy, entropy, and molar heat capacity of sodium magnesium silicates from
their constituent polyhedra is introduced in this work. If it is assumed that the
complex silicates are made up of different polyhedron constituents, the thermo-
dynamic properties of complex compounds can be calculated from the linear combi-
nation of their polyhedron constituents. Thermodynamic properties of 18 polyhedra
were obtained by weighted multiple linear regression analysis based on thermody-
namic properties of 48 silicates compounds, which were collected from FactSage
database. Standard enthalpy, entropy, Gibbs free energy, and molar hear capac-
ity for the formation of five different sodium magnesium silicates (Na2 MgSiO4 ,
Na2 Mg2 Si2 O7 , Na4 Mg2 Si3 O10 , Na2 MgSi4 O10 , Na2 Mg2 Si6 O15 ) provide the foun-
dation for evaluating the possibilities and priorities of reactions involving these
compounds.
Keywords Sodium magnesium silicates · Polyhedron method · Standard

formation enthalpy · Entropy · Molar heat capacity
Introduction
Sodium salt-assisted roasting is a common method for the utilization of serpentine-

bearing iron ores, e.g., laterite and ludwigite ore, along with the formation of sodium
magnesium silicates. The physicochemical properties of these compounds are of
importance when evaluating formation of target compounds in the chemical reac-
tion process. However, lack of thermodynamic data for sodium magnesium silicates
Z. Zhu · J. You · X. Zhang · J. Wang · J. Duan · T. Zhang · Z. Peng · T. Jiang · M. Rao (B)
School of Minerals Processing & Bioengineering, Central South University, Changsha 410083,
Hunan, China
e-mail: mj.rao@csu.edu.cn
Organization National Engineering Laboratory for High Efficiency Recovery of Nonferrous
Metals, Changsha 410083, Hunan, China

https://doi.org/10.1007/978-3-030-36540-0_20
216 Z. Zhu et al.
hinders the thermodynamic analysis of the involved chemical reactions during the
roasting process.
A thermodynamic database built by the thermodynamic modeling of oxide phase
diagrams, thermodynamic properties and chemical reactions using CALPHAD
method has become an important tool for new materials design and process opti-
mization in many fields of ceramics and metallurgy. Accurate thermodynamic cal-
culations of various compounds and solution phases are necessary to create new
databases. Although a substantial amount of thermodynamic properties have been
experimentally measured, the data are questionable for numerous compounds. Exper-
imental determinations of thermodynamic properties are labor-intensive and time-
consuming, and some oxide compounds are difficult to be synthesized under conven-
tional conditions. Although the first-principles calculations have been widely used
in metallic systems, their applications to oxide systems are still rather limited [1].
Various models and methods have been proposed to estimate thermodynamic data.
The standard enthalpy and standard Gibbs free energy of formation of solid inorganic
salts can be estimated from the group contributions as presented by Mostafa in 1995
[2]. The analysis is done by data regression for H 298 f of 938 and G298 f of 687
solid inorganic compounds. Predictions of H f and G298
298
f have a mean error of
2.57%, and 2.60%, respectively. Li et al. introduced a simple method of estimation
of Gibbs free energy and enthalpy of complicate silicates in 2001 [3]. It is assumed
that the complicate silicates are made up of acidic oxides and alkaline oxides. And
the most alkaline oxide initially reacts with the most acidic oxide. Then the Gibbs
free energy (or enthalpy) of complicate silicates approximately equals the sum of
the Gibbs free energy (or enthalpy) of all oxides and the free energy of reactions (or
enthalpy of reaction) between acidic oxides and alkaline oxides. The method is very
simple without any estimated parameters and the Gibbs free energy and enthalpy at
any temperature can be calculated.
Regarding entropy, Latimer [4, 5] used entropy of elements to estimate entropy of
oxide compounds. Fyfe et al. [6] calculated the entropy of binary or ternary oxides
from their constituent oxides. Helgeson et al. [7] improved the accuracy of entropy
estimation by taking structurally analogous minerals as components instead of con-
stituent oxides and considering differences in coordination state between the com-
ponents. Robinson and Haas [8] determined a set of fractional entropy of polyhedral
components with varying coordination states to accurately reproduce the entropies
of silicates and other types of oxides by multiple regression techniques. However,
their analysis neglected the volume correction which potentially induced more errors
in the estimation.
Heat capacities of binary and ternary oxides can be estimated by the summation
of the heat capacities of constituent oxides or elements based on the Neumann-Kopp
rule (NKR) [9]. By comparing experimental and estimated values of heat capacity at
298.15 K, Leitner et al. [10] showed that NKR provides an estimate of heat capacity
with an average error of 3.3%. However, Stevens et al. [11, 12] and Richet and Fiquet
[13] pointed out that the NKR can give a much larger error at both lower and very
higher temperatures than room temperature. Leitner et al. [14] also analyzed the error
of NKR approach for heat capacity with temperature.
Estimation of Thermodynamic Properties … 217
Hazen [15] expounded that structures and properties of oxide minerals can be
modeled by considering cation polyhedra with specific coordination as basic build-
ing blocks. This so-called “polyhedron method” assumes: (i) each polyhedron has
its own characteristic properties which are invariant from structure to structure and
(ii) thermodynamic properties of an oxide compound can be derived from the lin-
ear summation of constituent polyhedron properties in a given formula unit of the
oxide compound. Recently, the polyhedron model was updated and expanded by
Hinsberg et al. [16, 17]. The enthalpies, entropies, and heat capacities of 35 poly-
hedra were determined using a weighted multiple linear regression analysis. On
Hinsberg’s basis, Jung et al. further analyzed and optimized the thermodynamic
properties of 18 polyhedra based on thermodynamic properties collected from the
FactSage database. Therefore, through comparative calculations using several dif-
ferent approaches (including Li’s method, Mostafa’s method, Neumann-Kopp rule
(NKR), Latimer’s method, polyhedron method and so on.), the calculation results
show that the polyhedron method is more accurate and concise in calculating the
thermodynamic data of complex silicates. Therefore, the polyhedral method is used
to calculate the thermodynamic data of sodium magnesium silicates in this paper.
Concept of the Polyhedron Method
The basic assumption of polyhedron method is that the thermodynamic properties

of mixed oxides (mostly silicates) can be described as linear combinations of the
fractional thermodynamic properties of their constituent polyhedra. According to the
polyhedron method, H 0 298.15 K S0 298.15 K , and C p (T) of mixed oxide compounds
can be calculated [1]:

H θ i (298.15 K) = nj hθ j (298.15 K) (1)

S θ i (298.15 K) = nj sθ j (298.15 K) (2)

Cpi (T) = nj cj (T) (3)
where i is the specific oxide phase, j is the constituent polyhedron, nj is the stoichiom-
etry of the polyhedron component of j. The capital letters H, S, and Cp represent
enthalpy, entropy and molar heat capacity of oxide, respectively, and lower-case h, s,
and c represent enthalpy, entropy and molar heat capacity of polyhedron component
(Table 1).
218 Z. Zhu et al.
Table 1 Polyhedron components defined in the model as the oxide building blocks
Component Element Coordination Component Element Coordination
Ti-oct Ti4+ Octahedral Mg-tet Mg2+ Tetrahedral
Si-tet Si4+ Tetrahedral Mg-oct Mg2+ Octahedral
Al-tet Al3+ Tetrahedral Ca-oct Ca2+ Tetrahedral
Al-oct Al3+ Octahedral Ca-Multi Ca2+ Multi-coordination
Fe3-oct Fe3+ Octahedral Li-tet Li+ Tetrahedral
Fe-tet Fe2+ Tetrahedral Li-oct Li+ Octahedral
Fe-oct Fe2+ Octahedral Li-Multi Li+ Multi-coordination
Mn-tet Mn2+ Tetrahedral Na-Multi Na+ Multi-coordination
Mn-oct Mn2+ Octahedral K-Multi K+ Multi-coordination
Estimation of Thermodynamic Data of Sodium Magnesium

Silicates
Taking Na2 MgSiO4 for an example, as the schematic representation of the struc-
ture shown in Fig. 1. Using this method, one mole Na2 MgSiO4 can be thought of
as composed of two moles of sodium multi-coordination, one mole of magnesium
tetrahedra (MgO4 ) and one mole of silicon tetrahedra (SiO4 ). According to the poly-
hedron model, the thermodynamic properties of Na2 MgSiO4 can be determined from
these polyhedron properties using Eqs. (1)–(3).
H θ Na2 MgSiO4 (298 K) = 2hθ Na-Multi (298K) + hθ Mg-tet (298 K) + hθ Si-tet (298 K)
= 2 × (−304.86846) + (−603.01384) + (−920.50054)
= −2132.887 kJ/mol (4)
Fig. 1 Schematic diagram of Na2 MgSiO4 crystal, a unit cell, and b polyhedron structure
Table 2 Thermodynamic properties of the polyhedron components derived from the present
regression analysis and their associated uncertainties (standard deviation, SD) [1]
Polyhedron hθ i,298 k (J/mol) SD sθ i,298 k (J mol−1 k−1 ) SD
Si-tet −920500.54 3085.30 48.47 1.32
Mg-tet −603013.84 20907.37 39.62 8.97
Mg-oct −627400.20 5546.51 18.71 2.38
Na-multi −304686.46 3087.88 38.34 1.33
S θ Na2 MgSiO4 (298 K) = 2sθ NaNa-Multi (298 K) + sθ Mg-tet (298 K) + sθ Si-tet (298 K)
= 2 × 38.34 + 39.62 + 48.47
= 164.77 J mol−1 K−1 (5)
Table 2 shows the relevant polyhedron contributions of H θ f (298 K) and S θ

(298 K) provided by polyhedron method. According to the method, we can obtain
f is −2132.887 kJ/mol and S
that H 298 298
is 164.77 J mol−1 K−1 .
That the part of resulting values for the heat capacity of the polyhedrons in sodium
magnesium silicates are shown in Table 3 for their respective temperatures derived
from Hinsberg’s work [17]. According to Eq. (3), the molar heat capacity values
of sodium magnesium silicates at different temperatures can be acquired from the
calculation.
Structures of five kinds of sodium magnesium silicates are generated from the
Crystallographic Information File (CIF) taken from the database, Crystallography
Open Database 28 and generated from Vesta Visualization software for Electronic
and Structure Analysis.29 and relevant literature [18–20]. The polyhedral consists
of five sodium magnesium silicates that are given in Table 4.
Following polyhedron method, the H 298 f , S
298
, and heat capacities at different
temperatures of five kinds of sodium magnesium silicates were calculated, respec-
tively. For condensed phase (solid and liquid phase), thermochemical calculations
usually use C p and C p as a function of temperature. It is usually fitted into the
following form:
Cp = a + b × 10−3 T + c × 105 T−2 + d × 10−6 T2 (6)
where a, b, c, and d are the characteristic constants of substance, which is called the
heat capacity temperature coefficient of the substance. The units of a, b, c, and d are,
respectively J mol−1 K−1 , J mol−2 K−1 , J mol−1 K, and J mol−1 K−3 .
The relationships of sodium magnesium silicates between heat capacity and tem-
perature were also fitted in Table 5. Enthalpy and entropy are, respectively calculated
from Eqs. (7) to (8) at different temperatures. The Gibbs free energy of substance at
different temperatures can be calculated by using Eq. (9). As can be seen from Fig. 2,
the basic thermodynamic data in different temperatures (including enthalpy, entropy,
molar heat capacity, Gibbs free energy) of five kinds of sodium magnesium silicates
220
Table 3 The value of the heat capacity contribution parameters of the corresponding polyhedron in sodium magnesium silicates
Polyhedron Thermodynamic properties Cp of the polyhedron components derived from the regression analysis at different
temperature/J mol−1 K−1
300 400 500 600 700 800 900 1000 1100 1200
Na-Multi 31.9 31.0 32.5 34.2 35.6 36.7 37.4 37.7 37.9 37.8
Mg-Tet 44.9 46.5 47.6 48.7 49.9 51.1 52.2 53.3 54.4 55.3
Mg-Oct 38.7 44.4 47.8 50.0 51.6 52.8 53.8 54.6 55.2 55.7
Si-Tet 45.5 54.1 59.6 63.3 66.1 68.2 69.9 71.3 72.5 73.5
Na2 MgSiO4 154.2 162.6 172.2 180.4 187.2 192.7 196.9 200.0 202.7 204.4
Na2 Mg2 Si2 O7 232.2 259 279.8 295 306.6 315.4 322.2 327.2 331.2 334
Na2 MgSi4 O10 284.5 322.8 351.2 371.6 387.2 399 408.2 415.2 421 425.3
Na4 Mg2 Si3 O10 341.5 375.1 404.4 426.7 443.9 457 466.9 473.9 479.5 483.1
Na2 Mg2 Si6 O15 420.4 477.5 518 546.9 569.3 586.5 600.2 611.1 620.4 627.6
Z. Zhu et al.
Table 4 Polyhedral constituent matrix for the sodium magnesium silicates

Compounds Na-Multi Mg-Tet Mg-Oct Si-Tet
Na2 MgSiO4 2 1 0 1
Na2 Mg2 Si2 O7 2 0 2 2
Na2 MgSi4 O10 2 1 0 4
Na4 Mg2 Si3 O10 4 1 1 3
Na2 Mg2 Si6 O15 2 1 1 6
Table 5 Thermodynamic data of five kinds of sodium magnesium silicates

Compounds H 298 −1 S 298 /J mol−1 Cp = a + b × 10−3 T + c × 105 T−2 + d ×
f /kJ mol
K−1 K−1 10−6 T2
a b c d
Na2 MgSiO4 −2132.887 164.77 112.166 147.952 2.364 −59.829
Na2 Mg2 Si2 O7 −3705.174 211.04 209.102 205.763 −28.547 −84.136
Na2 MgSi4 O10 −4982.957 341.04 306.828 200.284 −69.571 −77.730
Na4 Mg2 Si3 O10 −5298.979 378.01 275.000 329.959 −8.184 −131.674
Na2 Mg2 Si6 O15 −7447.715 492.04 447.950 286.934 −104.417 −110.427
Fig. 2 The estimated thermodynamic properties of five sodium magnesium silicates a enthalpy
b entropy c heat capacity d Gibbs free energy
222 Z. Zhu et al.
listed in this paper were, respectively obtained. With these fundamental data, ther-
modynamic calculations become possible for reactions involving these compounds
using Eq. (10), which will provide relevant theoretical guidance for our future work.
Where H, S, G, and G, respectively represent the enthalpy change, entropy
change, Gibbs free energy, and Gibbs free energy change. Equations (7)–(10) are
from Physical Chemistry.

H = CP dT (7)

cp
S = dT (8)
T
G = H − TS (9)
G = ΣνG (10)
Data Assessment and Verification
To verify the accuracy of the estimated results, a comparison was made between
the estimated and FactSage values of certain silicates. Jung et al. calculated the
thermodynamic properties of total of 67 typical oxides, including 48 silicates and 19
titanates by polyhedron method. Comparison of their results of the current polyhedron
analysis with the FactSage values shows that the R2 values representing the goodness-
of-fit of the regression model are 0.9999 for H θ298K , 0.9975 for S θ298K , respectively.
The standard deviations for H θ298K , S θ298K are 0.56%, 3.50%, respectively [1].
Meanwhile, the estimated thermodynamic properties of two kinds of sodium mag-
nesium silicates with available thermodynamic data were compared with those of
FactSage values in Fig. 3. The results demonstrate that the polyhedron method is
quite satisfactory in calculating enthalpy and molar heat capacity of compounds, but
the error in calculating entropy is relatively large. Pure Na2 MgSiO4 was synthesized
and its molar heat capacity was measured at different temperatures. The measure-
ment of C p,m (T) of Na2 MgSiO4 was carried out using a heat flow-type differential
scanning calorimeter (TA, Q2000) in the temperature range 300–820 K. The high-
purity argon gas was passed over the sample with a flow rate of 8.3 × 10−4 dm3 s−1
and sample was heated with a heating rate of 0.17 K s−1 . The data in Fig. 4 shows
that the measured experimental values are very close to the calculated results. Com-
paring the results of the molar heat capacity measured by other researchers, it can
be expected that the polyhedral method can accurately calculate the thermodynamic
parameters of silicates.
Fig. 3 Comparison between estimated and FactSage values for a enthalpy, b entropy, c molar heat
capacity and d Gibbs free energy
Fig. 4 Comparison between

calculated C p values and
experimentally measured
values of Na2 MgSiO4
Following polyhedron method, the basic thermodynamic data of sodium magne-

sium silicates are, respectively, acquired from calculation. And then, it is possible
to discuss the chemical reactions relevant to these sodium magnesium silicates. The
224 Z. Zhu et al.
focus was on the formation of five kinds of sodium magnesium silicates. The rel-
evant reactions are listed in Table 6, and the Gibbs free energy changes with tem-
perature can be seen in Fig. 5. As can be seen in Fig. 5a, when the reactants are
sodium oxide, magnesium oxide, and silica, the Gibbs free energy of forming dif-
ferent sodium magnesium silicates are negative demonstrating that these reactions
are spontaneous. While the trend of forming different sodium magnesium silicates
is as follows: Na4 Mg2 Si3 O10 > Na2 Mg2 Si6 O15 > Na2 MgSi4 O10 > Na2 Mg2 Si2 O7 >
Na2 MgSiO4 . When the reactants are sodium carbonate, magnesium oxide, and sil-
ica, the trend is almost consistent. From the results, the priority of reactions can be
determined.
Table 6 Chemical reactions of forming different sodium magnesium silicates

Equation no. Reaction G0 /kJ mol−1
(1) Na2 O + MgO + SiO2 = Na2 MgSiO4 −207.585 − 0.0095T
(2) Na2 O + 2MgO + 2SiO2 = Na2 Mg2 Si2 O7 −218.762 − 0.0299T
(3) 2Na2 O + 2MgO + 3SiO2 = Na4 Mg2 Si3 O10 −425.700 − 0.0241T
(4) Na2 O + MgO + 4SiO2 = Na2 MgSi4 O10 −222.222 − 0.0656T
(5) Na2 O + 2MgO + 6SiO2 = Na2 Mg2 Si6 O15 −220.157 − 0.1044T
(6) Na2 CO3 + MgO + SiO2 = Na2 MgSiO4 + CO2 104.523 − 0.1428T
(7) Na2 CO3 + 2MgO + 2SiO2 = Na2 Mg2 Si2O7 93.346 − 0.1632T
(8) 2Na2 CO3 + 2MgO + 3SiO2 = Na4 Mg2 Si3 O10 + 198.515 − 0.2908T
2CO2
(9) Na2 CO3 + MgO + 4SiO2 = Na2 MgSi4 O10 + CO2 89.888 − 0.1989T
(10) Na2 CO3 + 2MgO + 6SiO2 = Na2 Mg2 Si6 O15 + 91.953 − 0.2378T
CO2
Fig. 5 Gibbs free energy changes with temperature for reactions a Eqs. (1)–(5) b Eqs. (6)–(10)
Conclusions
The crystal structure of sodium magnesium silicates was determined by the optimized
polyhedron method; the basic thermodynamic data of five kinds of sodium magne-
sium silicates were obtained, including the standard formation enthalpy, entropy,
molar heat capacityMolar heat capacity, and Gibbs free energy. The thermodynam-
ics of chemical reactions involving these compounds were studied, and by calculating
the Gibbs free energy changes for the reactions to generate the corresponding mineral,
the feasibility and priority of each reaction were acquired. The data generated in this
work provides data necessary to optimize chemical processes of involving sodium
magnesium silicates, and will contribute theoretical guidance in the sodium salt-add
roasting process. The methodology used in this work is also a valuable approach for
the estimation of thermodynamic properties involving other inorganic compounds
without experimental data.
Acknowledgements This work was supported by the Graduate Research and Innovation Project
of Central South University (2018zzts781) and the Natural Science Foundation of China of Hunan
Province (2019JJ50767).
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Numerical Simulation on Distributor
Optimization of Twin-Roll Strip
Continuous Casting
Yong Zhong, Mingmei Zhu, Aiping Zhang and Bing Huang
Abstract In this paper, the influence of distributor structure on the flow uniformity
of molten steel in the twin-roll thin strip continuous casting pool with 900 mm roll
diameter and 1800 mm roll width is studied by numerical simulation. The effects of
the length of distributor, the number of side holes, and the arrangement of side holes
on the fluctuation of molten pool level and the mixing of molten steel in the upper
part of molten pool are studied. The optimal structure of the distributor is analyzed
and obtained. The research results can provide theoretical guidance for the design of
twin-roll strip distributor in practical production.
Keywords Twin-roll strip casting · Distributor · Numerical simulation · Side hole

flow rate
Introduction
The stability and quality of twin-roll strip casting process are directly affected by the
distributor system, and the distributor is the most important link in the distributor
system of twin-roll strip casting and the key factor affecting the quality of Cast-
rolled strip. The structure and size of the distributor directly affect the flow field
in the molten pool of twin-roll strip casting and rolling and the uniformity of the
upper molten pool. Therefore, the distributor structure has also become the focus of
many researchers. At present, the product width of thin strip blank is narrow and its
productivity is low. The product width is usually about 1000–1600 mm [1]. Under
special circumstances, it cannot meet the needs of industry, and improving the width
of thin strip products is also a major research direction at present.
At present, the research on a wide molten pool twin-roll strip distributor mainly
includes wedge, V-type inclined groove, ship-type, etc. Some researchers [2] used
wedge distributors to study the effect of the inclination angle of the side hole of
distributors on the solidification and temperature distribution of molten steel in the
Y. Zhong · M. Zhu (B) · A. Zhang · B. Huang

e-mail: zhumingmei@cqu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_21
228 Y. Zhong et al.
molten pool. The results show that when the inclination angle of the side nozzle of the
wedge distributor is 0°, the kiss point of molten steel in the molten pool is moderately
high and the temperature difference along the width direction of the casting band is
small, which can effectively reduce or avoid transverse and longitudinal cracks in the
strip. Bouchard et al. [3] used physical experiments to find that the surface stability
of molten pool plays a key role in improving the quality of Cast-rolled strip. Kim
et al. [4] carried out numerical simulation and analysis of coupled turbulent flow and
heat transfer in two different nozzle casting modes during twin-roll thin strip casting
and rolling process. The results show that it is easier to obtain free surface with less
fluctuation by using submerged nozzle.
Once the width of the roll surface is increased, the difficulty of homogeneity of
upper molten pool surface of twin-roll molten pool will be doubled [5]. So in this
paper, a three-dimensional model of distributor and molten pool is established by
mathematical simulation for the distribution system of twin-roll strip casting with
900 mm roll diameter and 1800 mm roll width. The effects of the length of ship-type
distributor and the arrangement of distributor side holes on the liquid level uniformity
of molten pool were studied. By analyzing the flow field of molten pool, turbulent
kinetic energy, variance of residence time distribution of molten pool, and flow rate
of side hole of distributor, the optimum structure scheme of distributor is obtained,
which provides basis for uniform solidification of molten steel and improvement of
quality of thin strip.
Numerical Simulation Research Method
Model Hypothesis
The flow of molten steel in the twin-roll pool is very complicated. In order to facilitate
the simulation calculation and conform to the actual state of molten steel flow, it is
considered that molten steel is a steady incompressible three-dimensional Newtonian
fluid, ignoring the influence of temperature on the flow, i.e., the density and viscosity
are constant. The flow of molten steel is described by continuity equation and Navier-
Stokes equation [6]. It is considered that the flow of molten steel is turbulent flow,
and the standard k − ε two-equation model is adopted. The following equations are
used to describe the physical phenomena of molten steel between two rollers.
Continuity equation
∂P ∂(ρμi )
+ =0 (1)
∂t ∂ xi
Momentum equation
Numerical Simulation on Distributor Optimization … 229

∂ ρμi μ j ∂P ∂ ∂μi ∂ ∂μ j
=− + μe f f + μe f f + ρgi (2)
∂x j ∂x j ∂x j ∂x j ∂ xi ∂ xi
Describe the standard k − ε equation for turbulence

∂(ρμi ) ∂ μt ∂k
= μe f f + + G − ρε (3)
∂ xi ∂ xi σk ∂ xi

∂(ρμi ε) ∂ μt ∂ε ε ε2
= μe f f + + c1 G − c2 ρ (4)
∂ xi ∂ xi σε ∂ xi k k
among them

∂μ j ∂μ j ∂μ j
G = μt + (5)
∂ xi ∂x j ∂x j
k2
μe f f = μ + μt = μ + cμ ρ (6)
ε
Component transport equation

∂C μt C
+ ∇ × Uc = ∇ × ρ Dc + ∇× + SC (7)
∂t Sct ρ
where: ρ is the density, kg m−3 ; ui and uj are the velocity of molten steel in the i and
j directions, m s−1 ; μeff is the effective viscosity, kg m−1 s−1 ; C1, C2, Cμ, Ck, and
Cε are empirical constants with values of 1.44, 1.93, 0.09, 1.0, and 1.3, respectively;
keff is the effective thermal conductivity, W m−1 K−1 . Dc tracer diffusion coefficient,
this paper takes 1.1 × 10−8 m2 /s; turbulent viscosity of μt molten steel, kg/(m s);
SCt is the turbulent Schmielt number of the tracer, taken 0.9 [7, 8].
Boundary Conditions
In this paper, the model only establishes the molten pool between twin rollers and
uses gambit software to divide tetrahedron meshes. Boundary layer meshes are set
at the molten pool level and the roll gap exit. The total number of meshes is about
700,000. The boundary conditions are velocity inlet boundary conditions, inlet veloc-
ity 1.1 m/s, pressure outlet boundary conditions, and non-slip boundary conditions
on roll surface. The velocity value on the solid wall is 0, and the non-slip boundary
condition is adopted. The flow field and residence time distribution are solved in the
commercial software fluent.
230 Y. Zhong et al.
Simulation Scheme
As shown in Figs. 1 and 2, the distributor is of ship-type. After the molten steel enters
the distributor from the inlet, it reaches the distributor through the bottom outlets on
both sides and distributes to the molten pool through the side holes and left and right
holes of the distributor. The effects of different lengths of conveying system and
different arrangement of side holes on the mixing uniformity of the upper molten
pool of 1800 mm wide twin-roll molten pool were studied. There are three types
of edge hole layout, which are straight type (edge hole is 70 mm from the bottom
of the delivery system), staggered type 1 (the center three side holes are moved up
by 20 mm), and staggered type 2 (the leftmost and rightmost two holes moved up
20 mm), as shown in Fig. 3. Each group of delivery system has 7 edge side holes
and 2 side holes with a diameter of 16 mm. The opening direction of the edge hole
is parallel to the bottom of the delivery system, and the opening inclination angle is
0°. The specific structure size of the distributor is shown in Table 1.
Fig. 1 Overall structure of flow distribution system
Fig. 2 Structural sketch of distributor

Fig. 3 Schematic diagram of edge hole arrangement of distributor
Table 1 Structure layout of double roller delivery system

Case Delivery system Edge hole arrangement Edge hole distance
length/mm C1/mm C2/mm C3/mm
1 1600 Straight type 250 200 150
2 1600 Staggered type 1 250 200 150
3 1600 Staggered type 2 250 200 150
4 1550 Straight type 250 200 125
5 1550 Staggered type 1 250 200 125
6 1550 Staggered type 2 250 200 125
7 1500 Straight type 250 200 100
8 1500 Staggered type 1 250 200 100
9 1500 Staggered type 2 250 200 100
Simulation Results and Discussion
Flow Field
The mixing of upper molten pool in twin-roll strip continuous casting is directly
related to the quality of the solidified shell. The more stable the upper molten pool
is, the more stable the initial shell will be, especially when the liquid surface of the
molten pool and the roll surface just contact. Therefore, the upper mixing quality of
twin-roll molten pool is an important index to judge the quality of distributor. As
shown in the Figs. 4 and 5, the upper molten pool velocity vectors of scheme 2 and
scheme 4 are shown. After the molten steel enters the distributor from the inlet, the
232 Y. Zhong et al.
Fig. 4 Scheme 2 molten pool level velocity vector
Fig. 5 Scheme 4 molten pool level velocity vector
speed is high, and the flow back is formed after it impacts the distributor surface. It
distributes to the molten pool through the distributor side hole and plays the role of
uniform distribution. From the vector diagram, it can be seen that the liquid surface
velocity distribution of scheme 2 is concentrated between 0.2 and 0.3 m/s, while
that of scheme 4 has a large range of velocity variation and some dead zones, which
results in slow surface liquid steel renewal speed and easy to cause Non-uniform
solidification and formation of endogenous inclusions.
Turbulent Kinetic Energy of Liquid Surface
As shown in the Figs. 6 and 7, according to the turbulent kinetic energy diagram, the
turbulent impact area of scheme 2 is more uniform, which indicates that the impact of
the side hole of distributor on the liquid surface is also more uniform. The turbulent
kinetic energy in the central region is larger, and the contact area of molten steel on
the roll surface is smaller. It does not affect the formation of solidified billet shell
Fig. 6 Scheme 2 turbulent kinetic energy of the liquid surface

Fig. 7 Scheme 6 turbulent kinetic energy of the liquid surface
Table 2 Comparison of turbulent kinetic energy between two schemes

Case Turbulent kinetic energy Turbulent kinetic energy Turbulent kinetic energy
(Max) (Min) (Average)
2 0.01 8.22e−05 0.009
6 0.003 8.13e−05 0.005
while updating the molten steel on the surface. However, the turbulent kinetic energy
region of case 6 is not uniform, mainly concentrated in the area near the side hole.
The weak impact in the central area may lead to the slow liquid level renewal and the
phenomenon of early solidification due to the non-uniform temperature of molten
steel. As shown in Table 2, the turbulent kinetic energy of scheme 2 is larger than
that of other schemes, which is conducive to the rapid updating of liquid steel and the
reasonable distribution of turbulent kinetic energy at the contact point between edge
and roll surface. With the smaller length of the distributor, the turbulent kinetic energy
of the liquid surface increases on both sides and the center decreases gradually.
Side Hole Flow Rate of Distributor
The outlet flow rate of side hole and side hole of distributor directly affects the
uniformity of molten pool. The closer the flow rate of the side holes on the left and
right sides of the distributor is, the easier it will be to stabilize and evenly distribute
the molten steel into the molten pool. If the flow rate difference between the two
sides is large, it may cause fluctuation of liquid level or uneven velocity. So this
paper counts the flow rate of the side holes and side holes on the left and right sides
of the flow distribution under different schemes. As shown in Figs. 8 and 9, the flow
rate on both sides of scheme 2 is close, so the situation of molten pools on both
sides may be more stable. In contrast, the flow deviation between the two sides of
scheme 8 is large, especially at the outlet of the center, which may lead to reflux in
the molten pool, resulting in the difficulty of pool mixing.
234 Y. Zhong et al.
Fig. 8 Statistical flow chart of side holes on both sides of scheme 2
Fig. 9 Statistical flow chart of side holes on both sides of scheme 8
Upper Pool Mixing
In the upper part of the twin-roll molten pool, the calculated residence time distri-
bution curve is used to reflect the fluid flow in the molten pool. The obtained curve
shows a normal distribution, and the variance of the curve is a measure of the degree
of backmixing. The variance of residence time distribution in a non-ideal flow reactor
should be between 0 and 1. The larger the variance, the closer the molten pool is to
full mixing, indicating that the updating of the upper part of the molten pool is more
timely. Since the upper pool of twin rollers is a symmetrical structure, a quarter of
the pool is taken to study. As shown in Fig. 10, 8 points (P1–P8) are taken from
the position shown in Fig. 5 mm away from the roll surface and the residence time
distribution of 8 points is calculated. The distribution curve of scheme 2 is shown
in Fig. 11. The variance of 8 points distribution curve is calculated and the average
value is obtained. The results are shown in Fig. 12. The average variance of 8 points
in Scheme 2 is larger than that of other schemes, with a value of 0.65. This shows
that the upper molten pool between the two rollers in scheme 2 can update the molten
steel contacting the roll surface in time, the temperature is more uniform, the possi-
bility of solidification ahead of time is small, and the speed of the billet shell is more
stable.
Fig. 10 Diagram of point selection for calculating melt level mixing in molten pool
Fig. 11 Residence time distribution curves at 8 points in scheme 2

236 Y. Zhong et al.
Fig. 12 Comparison of mean-variance of upper molten pool under different schemes
Conclusion
In this paper, based on ANSYS fluent software, a set of the flow distribution system of
stamping twin-roll thin strip is established. The twin-roll melting pool with 900 mm
roll diameter and 1800 mm roll width is analyzed. The influence of different side hole
arrangement and length of distributor on the mixing of upper molten pool between
two rollers was studied. The following conclusions are drawn.
For a twin-roll molten pool with a width of 1800 mm, the length of distributor
should be 1600 mm. As the length of distributor decreases, the liquid level renewal
speed of molten pool becomes worse, some dead zones appear, and the turbulent
kinetic energy distribution of liquid level concentrates.
The double roll pool with a wide pool should be arranged in staggered 1 mode to
make the outlet flow closer on both sides. The more likely the liquid level is uniform
in the central area and the two sides, the greater the variance of the pool distribution
curve and the better the mixing situation.
References
1. Dong J-H, Min C, Nan W (2015) Characteristics of fluid flow and temperature field of twin-roll
steel strip casting with a novel-type delivery system. J Iron Steel Res Int 22(10):885–891
2. Xu M, Zhu M (2016) Numerical simulation of the fluid flow, heat transfer and solidification
during the twin-roll continuous casting of steel and aluminum. Metall Mater TransB 47(2):740–
748
3. Xu Z-Q, Meng Z-R, Xue S-H, Zhang D-Q, Du F-S (2018) Effect of oscillation parameters to
flow field in the pool during the oscillating twin-roll strip casting process. Chin J Mech Eng
31(06):187–194
4. Zhang H, Zhou C, Wei C (2018) Mathematical and physical modeling of metal delivery system
during top side-pouring twin-roll casting. J Mater Process Tech 254
5. Haga T, Takahashi K, Ikawa M, Watari H (2004) Twin roll casting of aluminum alloy strips. J
Mater Process Technol 153–154:42–47
6. Bouchard D, Hamel FG, Turcotte SF, Nadeau J-P (2001) Water modeling evaluation of metal
delivery in a twin roll strip caster using pool level and residence time distribution measurements.
ISIJ Int 41(12):1465–1472
7. Numerical and physical simulation of a twin-roll strip caster. J Univ Sci Technol Beijing (English
edition), 2006 (05):393–400
8. Numerical simulation of the temperature fields of stainless steel with different roller parameters
during twin-roll strip casting. Int J Miner Metall Mater, 2009, 16(03):304–308
Effect of Al and Ca Content
on the Behavior of the Inclusion
in High-Grade 304 Type Stainless Steel
Tongsheng Zhang, Hualong Zhang, Wanlin Wang, Liwen Xue, Shifan Dai
and Guomin Ying
Abstract The experiments were carried out to determine the transient behavior of
the inclusion in Si-deoxidized stainless steel for high-grade plate. The samples were
taken from three heats of the steel during the whole production process from the
AOD to the mold, which were subsequently examined by an automatic scanning
electron microscope with field energy dispersive spectrometer (FE-SEM and EDS).
It can be summarized that appropriate calcium treatment intensity could modify
inclusions into liquid ones. Excessive calcium treatment above ([Ca] = 25 ppm) will
increase the melting point of the inclusions, which cannot keep in the liquid region
at the solidification temperature. Therefore, the calcium addition in Si-deoxidized
stainless steel should be controlled to a relatively lower value ([Ca] = 10 ppm). In
addition, the content of aluminum in steel also has an important influence on the
control of inclusion. When the content of aluminum ([Al] = 0.012%) is too high, the
inclusions in steel are difficult to be controlled within the liquid phase. The chemical
evolution of the inclusions in steel at high temperature and during solidification
process were comprehensively calculated, considering all types of inclusions such
as calcium oxide, aluminum oxide, silicon oxide, calcium aluminate, calcium silicate,
mullite, and liquid inclusion. The thermodynamic calculations are in good agreement
with experimental results, which can predict the formation of the inclusions in Si-
deoxidized stainless steels.
Keywords Inclusion · Si-deoxidized stainless steel · Thermodynamic
T. Zhang (B) · H. Zhang · W. Wang · L. Xue · S. Dai · G. Ying

School of Metallurgy and Environment, Central South University, Changsha, People’s Republic of
China
e-mail: tongsheng.zhang@csu.edu.cn
National Center for International Cooperation of Clean Metallurgy, Changsha, China

https://doi.org/10.1007/978-3-030-36540-0_22
240 T. Zhang et al.
Introduction
High-grade type 304 stainless steel products, such as 2A, BA, 8K grade mirror plate,
have high requirements for surface quality. However, there are always defects in the
final products such as surface line-scale defect and point-shape defect after polish-
ing, which seriously affect the appearance of the finished product [1]. It is mainly
caused by the inclusions in stainless steel. Although the amount of B-type inclusion
in Si-deoxidised stainless steel is very low, it is enough to cause various defects of the
product. Calcium treatment can effectively modify the solid inclusions into the liquid
ones in steelworks, which is advantageous for the mechanical properties of final steel
production [2, 3]. Owing to the importance of inclusions, scholars have conducted
many types of research on the inclusion control in stainless steel, such as size dis-
tribution, thermodynamic calculation, formation mechanism, reaction kinetics, and
dynamic evolution of the nonmetallic inclusions [4, 5], mostly for Al-deoxidised
stainless steel at steelmaking temperature. Until now, the researches involved in Si-
deoxidised 304 stainless steel, especially the discussions on the relationship between
industrial trial and thermodynamic calculation, are limited [6–8]. Jong et al. [6] and
Kim et al., [7] respectively, clarified the formation mechanism of CaO-SiO2 -Al2 O3 -
MgO-TiO2 complex inclusion and spinel inclusions in Si-deoxidised stainless steel.
Li et al. [8] studied the reoxidation behavior and inclusions in Si-deoxidised stainless
steel in the tundish a casting sequence with three heats. It is not good for the opti-
mization of refining process and the inclusion control in Si-deoxidised stainless steel.
In addition, the composition and morphology of the inclusions at the solidification
temperature are directly related to the properties of the inclusions in the final product.
Less attention has been paid to the oxide inclusions at the solidification temperature.
In current work, the experiments with different element contents were conducted.
The objective is to clarify the influence of initial aluminum content and calcium
treatment intensity on the characteristics of inclusions in Si-deoxidized type 304
stainless steel. The samples were collected from the AOD process to mold process,
and the inclusions were detected and analyzed by Field Emission-Scanning Elec-
tronic Microscope (FE-SEM). Meanwhile, the thermodynamics calculations on the
stable phase diagrams including all possible inclusions in the range from 1673 to
1823 K were conducted. Present works would provide a few guides for the process
optimization of Si-deoxidized type 304 stainless steel.
Experimental Apparatus and Procedure
The process route of Si-deoxidized stainless in a Chinese plant is as follows: sub-

merged arc furnace → AOD (including ferrosilicon deoxidation) → ladle furnace
(LF) refining (including feeding Ca–Si wire) → tundish → continuous casting. Three
experimental heats were performed, in which two heats were deoxidized with low-
Al ferrosilicon and the other one with high-Al ferrosilicon. When the ladle reached
Effect of Al and Ca Content on the Behavior … 241
the LF station, different amounts of Ca–Si wires were added into the ladle to mod-
ify the inclusions during the calcium treatment process. Thereafter, liquid melt was
cast into a six-strand curved-type continuous caster. The composition of ferrosilicon,
ferromanganese and Ca–Si wire adopted in current research are listed in Table 1.
Specimens of molten steel and top slag were taken with pail samplers at the
AOD end of every heat, LF start, after calcium treatment, tundish and mold. The
distribution of nonmetallic inclusions in different positions into the samples can be
heterogeneous, as was reported in some articles [9, 10]. Therefore, the same position
in the samples was selected for analyzing. The red area in the figure is the sampling
position. The central parts of each steel specimen were cut into two parts. One-half
of the steel samples were used for chemical analysis by the inductively coupled
plasma optical emission spectrometry (ICP-OES) with an accuracy of ±0.5 ppm,
and the total oxygen level of the sample was measured by the inert gas fusion-
infrared absorptiometry technique with an accuracy of ±1 ppm. Tables 2 and 3
show the compositions of the top slags and molten steel of the three heats. The
same composition refining slag was adopted for all heats. In order to investigate the
influence of the aluminum and calcium contents on the type of inclusion in steels,
three aluminum and calcium addition content levels were designed and conducted
in the present study. The experimental melts were divided into three types: low-Al–
low-Ca (No. 1 heat), low-Al–high-Ca (No. 2 heat) and high-Al–high Ca (No. 3 heat).
In other words, two different levels of Ca–Fe wires were added to the steel, which
represent different calcium treatment intensities.
The other halves of the steel sample were prepared for characterization analysis of
the inclusions. The morphology and composition of the inclusions were detected and
analyzed by field scanning electron microscopy and energy dispersive spectroscopy
(Zeiss Ultra-Plus) under 10-kV accelerating voltage to obtain the morphology, size,
and chemical composition of the inclusions. Considering the accuracy, the smallest
size of the inclusions that were analyzed in the present study is 0.5 µm. The planar size
distribution of particles in the polished cross section of each sample was evaluated in
this work. The total observed area of each sample was 19.86 mm2 which corresponds
to the 36 observation areas consisting of the continuous six observation areas to the
horizontal direction and the continuous six observation areas to the vertical direction
at the magnification of 500 by using FE-SEM and EDS.
Evolution of the Inclusion Composition during the Whole

Process
The liquidus temperature, as well as solidus temperature of the steel adopted in the
current work, can be evaluated by using the empirical formula reported by Choudhary
and Ghosh [11]. According to the steel composition listed in Table 3, the liquidus
242
Table 1 The compositions of the ferrosilicon, ferromanganese and Ca–Si wire (mass%)
Location C Si Mn P S Al Ca Fe Other
Low-Al ferrosilicon – 75.42 – – – 0.42 – 23.10 1.06
High-Al ferrosilicon – 71.55 – – – 3.25 – 23.80 1.40
Ferromanganese 6.69 – 75.77 0.148 0.007 – – 16.55 0.835
Si–Ca wire – 55.91 – – – – 29.04 12.74 2.31
T. Zhang et al.
Table 2 Chemical compositions of the refining slag samples (mass %)

Location CaO SiO2 Al2 O3 MgO
LF station 55.3 34.8 2.6 7.3
and the solidus temperature are, respectively, about 1463 °C (1736 K) and 1446 °C
(1719 K) by calculation.
To assess the transient behavior of the inclusion, the compositions obtained from
FE-SEM and EDS are converted into mass fractions of Al2 O3 , SiO2 , MgO, and CaO
which are then plotted on the above system phase diagram, as presented in Figs. 1, 2
and 3. Each plot represents an individual inclusion, and the red lines are the 1673 K
(1400 °C) liquid line. The experiment found that the oxide inclusions were mainly of
the Al2 O3 -SiO2 -MgO system at the end of the AOD process and the start of the LF
process. Thereafter, the inclusions were modified to the ones that contained a small
amount of MgO (about 5 mass percent) at Ca treatment process in the LF refining
process, the tundish process, and the mold process. It can be clearly seen in Fig. 1a
and b that most oxide inclusions in No. 1 heat at the end of the AOD process and the
start of the LF process is complex inclusion of mullite or(and) MgO. It is because
that the aluminum content of No. 1 heat is about 30 ppm, and it is relatively low
after deoxidation process. The compositions of all inclusions in the LF sample after
Ca treatment locate in the CaSiO3 (CaO·SiO2 ) or CaAl2 Si2 O8 (CaO·Al2 O3 ·2SiO2 )
region, and the composition of the inclusion in tundish process and mold process
gradually move into the CaAl2 Si2 O8 region. The compositions of the inclusion in
the samples after Ca treatment ([Ca] = 10 ppm) all locate in the liquid region.
It can be seen from the composition table that No. 2 heat has a similar composition
to No. 1 heat, especially the content of aluminum. Therefore, the compositions of
the inclusions in LF start stage samples of No. 2 heat are also located in the SiO2 or
Mullite phase region as shown in Fig. 2a. It makes that the position of the inclusion
compositions shifts throughout the process. Greater strength of the calcium treatment
is adopted in No. 2 heat, namely, No. 2 heat has higher calcium content (about
25 ppm). Therefore, after the calcium treatment, the inclusion composition is not
only located in the region of CaSiO3 or CaAl2 Si2 O8 but also located in the region of
Ca2 SiO4 and Ca2 Al2 SiO7 . The increase of CaO content of inclusions significantly
increases the melting point of the inclusions, and some other inclusions have deviated
from the liquid phase region. Even pure CaO inclusions can be observed in the
sample. Subsequently, the inclusions in the tundish and mold samples are completely
transformed into CaSiO3 or CaAl2 Si2 O8 complex inclusions. Therefore, excessive
calcium treatment can reduce the proportion of liquid phase inclusions.
A higher amount of aluminum is added into the steel during AOD deoxidation
process of No. 3 heat, to further decrease the oxygen content of the steel. However,
a relatively higher content of aluminum (120 ppm) has a significant influence on the
type and composition of the inclusion existed in steel. As shown in Fig. 3a and b,
the type of the inclusions in the samples took from the end of the AOD process and
the start of the LF process are spinel inclusions except for SiO2 or mullite phase
244
Table 3 The compositions of the steel samples in different stages of all heats (mass%)
No. Location C Si Mn P S Cr Ni N Ti Ca Alsol T.O
1. AOD end 0.036 0.49 1.03 0.0302 0.0059 18.41 7.79 0.060 0.003 0.004 0.0046
LF start 0.037 0.47 1.03 0.0301 0.0027 18.42 8.05 0.042 0.003 0.003 0.0045
Ca treatment 0.038 0.47 1.03 0.0298 0.0030 18.32 8.06 0.043 0.003 0.0010 0.004 0.0040
Tundish 0.040 0.47 1.03 0.0312 0.0037 18.17 8.04 0.045 0.003 0.0010 0.003 0.0042
Mold 0.042 0.47 1.03 0.0308 0.0036 18.21 8.09 0.044 0.003 0.0010 0.003 0.0032
2. AOD end 0.040 0.39 1.00 0.0294 0.0037 18.20 8.06 0.055 0.004 0.004 0.0048
LF start 0.055 0.39 1.05 0.0302 0.0026 18.24 8.09 0.043 0.003 0.003 0.0044
Ca treatment 0.066 0.45 1.06 0.0304 0.0023 18.18 8.09 0.042 0.003 0.0028 0.003 0.0042
Tundish 0.057 0.45 1.06 0.0298 0.0022 18.24 8.03 0.042 0.003 0.0025 0.003 0.0038
Mold 0.056 0.50 1.06 0.0300 0.0023 18.14 8.03 0.044 0.003 0.0020 0.003 0.0035
3. AOD end 0.039 0.43 1.02 0.0284 0.0044 18.11 7.82 0.050 0.006 0.013 0.0025
LF start 0.044 0.49 1.05 0.0288 0.0036 18.09 7.94 0.038 0.007 0.013 0.0030
Ca treatment 0.045 0.47 1.05 0.0280 0.0043 18.13 7.96 0.041 0.006 0.0030 0.012 0.0032
Tundish 0.045 0.47 1.05 0.0285 0.0042 18.08 8.02 0.043 0.007 0.0025 0.012 0.0028
Mold 0.048 0.47 1.06 0.0285 0.0039 18.06 8.02 0.042 0.007 0.0018 0.012 0.0025
T. Zhang et al.
Fig. 1 The phase diagram, 1673 K liquidus (Red line), and 1823 K liquidus (Blue line) of the
Al2 O3 –SiO2 –MgO and Al2 O3 –SiO2 –CaO–5%MgO systems and with experimental data in No. 1
heat
observed in No. 1 and No. 2 heat. As observed in the samples after calcium addition,
the composition of the inclusions shows significant scattering trend. However, the
compositions of inclusions in the tundish and mold samples are mainly distributed
in the regions of CaMg2 Al16 O27 (CaO·6Al2 O3 + 2MgO·Al2 O3 ) and alumina. The
inclusions are mostly solid, and such hard inclusions are easy to produce defects in
246 T. Zhang et al.
heat
final products. It can be easily seen that the content of aluminum in steel also plays
an important role in the control of inclusions.
Thermodynamic Consideration of Si–Al–Ca–O System

Complex Inclusions in Si-deoxidized Stainless Steel
Thermodynamic calculations were carried out to explain the modification of inclu-

sions in different processes. Therefore, the equilibrium relationships of [Al], [Ca]
content and the generated inclusions at 1823 K (1550 °C) and 1673 K (1400 °C)
were calculated using Factsage 7.2 with the FToxid, FactPS, and FSstel databases,
to get a clear understanding of the evolution mechanism of the inclusions in
Fe-Cr-Ni-Si-Al-Ca-O melt, as shown in Fig. 4.
Figure 4a and b show that the initial steel compositions of Fe-Cr-Ni-Si-Al-Ca-O
in mass pct with various aluminum and calcium contents were calculated at 1823 K
(1550 °C). As shown in Fig. 4a, when [Al] = 0.003 pct in the melts, there is a
heat
248 T. Zhang et al.
Fig. 4 Equilibrium precipitation of inclusions for Fe-Cr-Ni-Si-Al-Ca-0.005O in mass pct steel

different temperature, a Al = 0.003 pct, T = 1823 K, b Al = 0.012 pct, T = 1823 K, c Al = 0.003
pct, T = 1673 K, and d Al = 0.012 pct, T = 1673 K
liquid inclusion region in the melt with a relatively lower calcium content (less than
25 ppm). When Ca content of the melt is higher than 30 ppm, Ca2 SiO4 type oxide
inclusions are generated in the melt. However, when [Al] = 0.012 pct in the melt,
the precipitation curves are the very opposite of the above situation. It can be clearly
seen in Fig. 4b that liquid inclusion would be formed in the melt, which contains
more calcium (more than 24 ppm). If the calcium content of the melt increases to
40 ppm, the solid Ca2 SiO4 phase begins to appear in the melt.
Although the refining temperature is about 1823 K (1550 °C), as calculated above,
the solidification temperature of the steel is over 1673 K (1400 °C). The characters
of inclusions during the solidification process are crucial to the final product quality.
Therefore, the equilibrium relation between the inclusion and the element content
of molten steel are also calculated and shown in Fig. 4c and d. Figure 4c shows that
when [Al] = 30 ppm in the melts, the liquid region of the inclusions only exist under
low Ca content (less than 10 ppm). Although in the interval of Ca addition amount
between 10 and 25 ppm, the inclusion in steel are liquid at the refining temperature,
it is gradually transformed into Ca2 Al2 SiO7 type solid-phase inclusion during the
solidification process. The same situation happens in high aluminum content (0.012
mass%) of steel. There is hardly any liquid inclusion precipitated at 1673 K (1400 °C),
Fig. 5 Equilibrium precipitation of inclusions during solidification for steel where the composition
is: Fe-Cr-Ni-Si-Al-Ca-0.005O in mass pct, a Al = 0.003 pct, Ca = 0.001 pct b Al = 0.003 pct, Ca
= 0.0025 pct and c Al = 0.012 pct, Ca = 0.003 pct
and no matter how much calcium content in the steel. The hard inclusions produced
in the solidification process will have much adverse effect on the quality of steel
products.
For the usual case of Si-deoxidized stainless steel in the current article, the typical
inclusions generated in the steel during solidification process were also analyzed. As
presented in Fig. 5a, when [Al] = 30 ppm and [Ca] = 10 ppm, the liquid phase
exists at 1823 K (1550 °C) in steel. During the solidification process of the steel,
the transformed trajectory of oxide inclusions is liquid inclusion→CaO·6Al2 O3 →
CaAl2 Si2 O6 → Mullite → Al2 O3 . However, if the calcium content of steel reaches
to 25 ppm, solid inclusion (Ca2 Al2 SiO7 ) can be generated at a relative high tempera-
ture (1793 K). As the temperature decreases, CaO·2Al2 O3 , CaO·6Al2 O3 , Al2 O3 will
successively precipitate, as shown in Fig. 5b. On the other hand, the precipitation
phase and amount of the melt with 0.012 pct aluminum and 30 ppm calcium are very
different from the above. The main inclusions in the melt are solid calcium alumi-
nates during solidification process, replacing the Ca-Si-Al-O complex inclusion, as
presented in Fig. 5c.
It can be summarized that an appropriate calcium treatment level contributes
to modify inclusions to liquid ones in Si-deoxidized steel, comparing the observed
inclusions with the thermodynamic calculation results. Different amounts of calcium
250 T. Zhang et al.
should be added to the steel with different initial aluminum content. It is easily
summarized that lower aluminum content is necessary to modify the inclusions into
the liquid phase ones by calcium treatment. If aluminum content is too high, liquid
inclusion is only generated at 1823 K, and it will be modified to the solid ones during
the following process. Therefore, the calcium addition amount of Si-deoxidized steel
needs to control to a relatively lower value.
Conclusion
Inclusion evolutions after calcium addition in Si-deoxidized stainless steels with

different aluminum content have been carried out by the experiments and thermody-
namics calculations. The main findings can be summarized as follows:
The morphology, composition and size distribution of the oxide inclusions in
Si-deoxidized stainless steels are significantly influenced by aluminum and calcium
content during the whole production process. It can be summarized that appropriate
calcium treatment intensity could modify inclusions into liquid ones in the molten
steel. Although spherical inclusions can also be formed under excessive calcium
treatment ([Ca] = 25 ppm), the melting point is obviously increased. Therefore, the
calcium treatment intensity of Si-deoxidized stainless steels should be controlled
to a relatively lower value ([Ca] = 10 ppm). In addition, the content of aluminum
in steel also has an important influence on the inclusion control. When the con-
tent of aluminum ([Al] = 0.012%) is too high, the inclusions in steel are difficult
to be controlled within the liquid phase. The evolution of the inclusions in steel
at high temperature and during solidification process were comprehensively calcu-
lated by considering all types of inclusions. The thermodynamic calculations are in
good agreement with experimental results, which can predict the formation of the
inclusions in Si-deoxidized stainless steels.
References
1. Park JH, Todoroki H (2010) Control of MgO·Al2 O3 spinel inclusions in stainless steels. ISIJ
Int 50:1333–1346
2. Zhang T, Min Y, Liu C, Jiang M (2015) 4. Effect of Mg addition on the evolution of inclusions
in Al-Ca deoxidized melts. ISIJ Int 55:1541–1548
3. Zhang T, Min Y, Liu C, Jiang M (2017) Effect of Ti content on the characteristics of inclusions
in Al-Ti-Ca complex deoxidized steel. ISIJ Int 57:314–321
4. Park JH (2008) Thermodynamic investigation on the formation of inclusions containing
MgAl2 O4 spinel during 16Cr–14Ni austenitic stainless steel manufacturing processes. Mater
Sci Eng A 472:43–51
5. Ren Y, Zhang L, Pistorius PC (2017) Transformation of oxide inclusions in type 304 stainless
steels during heat treatment. Metall Trans B 48B:2281–2292
6. Kim JW, Kim KS, Kim DS, Lee DY, Yang KP (1996) Formation mechanism of Ca-Si-Al-Mg-
Ti-O inclusions in type 304 stainless steel. ISIJ Int 36:S140–S143
7. Ehara Y, Yokoyama S, Kawakami M (2007) Formation mechanism of inclusions containing

MgO·Al2 O3 spinel in type 304 stainless steel. Tetsu-to-Hagané 93:208–214
8. Li S, Zhang L, Ren Y, Fang W, Yang W, Shao S, Yang J, Mao W (2016) Transient behavior of
inclusions during reoxidation of Si-killed stainless steels in continuous casting Tundish. ISIJ
Int 56:584–593
9. Ericsson OT, Karasev AV, Jönsson PG (2011) Effect of slag protection system and sample
geometry on homogeneity of total oxygen content in samples from liquid steel. Steel Res Int
82:222–229
10. Zhang Z, Tilliander A, Karasev A, Jönsson PG (2010) Simulation of the steel sampling process.
ISIJ Int 50:1746–1755
11. Choudhary SK, Ghosh A (2008) Thermodynamic evaluation of formation of oxide-Sulfide
duplex inclusions in Steel. ISIJ Int 48:1552–1559
Development of Online Control Software
for Precise Calcium Treatment of Steels
Yan Luo, Weijian Wang, Lifeng Zhang, Yang Liu, Ying Ren and Wen Yang
Abstract Calcium treatment is an important method to reduce nozzle clogging and

modify inclusions in steel. However, the problems of the low yield and stability of
Ca in the molten steel, and the low accuracy of the modification inclusions caused
by the experiential calcium addition are always a key issue of the calcium treatment
for high-quality steels. The current modeling of Precise Calcium Treatment was
built according to the laboratory experiment, theoretical calculation, and plant trial.
Compared with the traditional method, the modeling first built a database based on
the actual molten steel composition. Considering the different operating parameters
in the plant, the calculation results of the suitable calcium wire were returned in
time. The software was mainly composed of four parts: input of steel composition,
calculation result, operation parameter, and function selection. The current modeling
can save costs, improve efficiency, and give precise guiding suggestions.
Keywords Precise calcium treatment · Modeling · Online prediction
Introduction
Aluminum is widely used during steel refining as a strong deoxidizer since it can
effectively reduce the oxygen content in the molten steel to a lower level. However,
it is entirely possible to cause nozzle clogging and some defects in the slab as the
formation of alumina in steel is inevitable [1–6]. Calcium treatment technology is
one of the most common, direct and effective methods for nonmetallic inclusions
in modified steel [7–11]. The purpose of calcium treatment is usually to add cal-
cium to the molten steel to modify the nonmetallic inclusions in steel to control
the composition, size, shape, and distribution of the nonmetallic inclusions in steel,
thereby improving the pouring of molten steel and reducing the risk of nonmetal-
lic inclusions. Calcium in molten steel reacts with solid Al2 O3 inclusions to form
Y. Luo · W. Wang · L. Zhang (B) · Y. Liu · Y. Ren · W. Yang

School of Ecological and Metallurgical Engineering, University of Science and Technology
e-mail: zhanglifeng@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_23
254 Y. Luo et al.
low-melting CaO-Al2 O3 inclusions [12]. However, Al2 O3 inclusions modified by cal-

cium treatment can form various calcium aluminate inclusions such as CaO·6Al2 O3 ,
CaO·2Al2 O3 , CaO·Al2 O3 , 12CaO·7Al2 O3, and 3CaO·Al2 O3 . The various kind of
inclusions has different effects on continuous casting and the performance of steel.
Among them, CaO·6Al2 O3 and CaO·2Al2 O3 with higher melting point are solid
inclusions at continuous casting temperature, which easily lead to nozzle clogging,
while 12CaO·7Al2 O3 and 3CaO·Al2 O3 inclusions with lower melting point are in
liquid states at continuous casting temperature. Liquid inclusions will hardly cause
nozzle clogging while they are easy to form large-sized long-chain inclusions after
rolling off the steel, which may lead to product flaw detection and affect the mechan-
ical properties of steel [13]. High CaO inclusions produced by excessive calcium
treatment can also cause nozzle clogging and large-scale inclusions. Many studies
have reported that partially liquidized inclusions can ensure the castability of molten
steel and avoid the formation of large and long-chain inclusions after rolling off the
steel.
However, during the calcium treatment process of high-quality steels, the low
yield and stability of Ca in the molten steel and the poor accuracy of the modification
effect of inclusions caused by the experiential calcium addition is always a key issue
in the calcium treatment of high-quality steels. The effects of Ca-containing alloy
quality and the calcium addition parameters on the yield of Ca in the molten steel
will be revealed. Software for the precise addition of calcium to modify inclusions
will be developed to predict the optimal calcium in the molten steel based on the
steel composition, temperature, and parameters of Ca wires.
Factors Influencing the Yield of Calcium
Since calcium has a low boiling point of 1484 °C, it is easily vaporized at the steel-
making temperature, and its chemical properties are active, calcium and molten steel
can be effectively reacted by adding calcium to the deep part of the molten pool, but
molten steel is seriously splashed, so that the calcium yield is low, and the production
level is unstable. The way of adding calcium from the beginning is to mix calcium
and iron powder into the molten steel, and gradually develops into the spraying
method [14–16], the projection method [17], the feeding core method [18], and so
on. The feeding core method is the main method of calcium treatment in the current
manufacturing process. In order to improve the calcium yield, the various calcium
wire, and the injection speed were carried out in the current study.
Table 1 shows the results of the different calcium wires. The seamless thick-walled
calcium wire has the highest calcium yield, basically maintained at 20–40%.
Figure 1 shows the effect of wire injection speed on the average yield of calcium
alloys. The trials were completed in the wire injection speed 90 m/min, 120 m/min,
and 150 m/min. Experiments of each wire injection speed were tried out at least three
heats. The highest yield of calcium alloy was 21% when the wire injection speed was
120 m/min, indicating that there was an optimal rate of the yield of calcium alloy.
Development of Online Control Software … 255
Table 1 Characteristic of various calcium wire

No. Type Exterior Characteristic Yield (%)
1. Conventional silicon calcium Iron shell crimping 8–15
wire Thin iron sheet
Silicon calcium powder
Serious splashing
2. Seamless calcium wire Iron shell weld 15–30
Thick iron sheet
Pure calcium
Serious splashing
3. Seamless thick-walled Iron shell weld 20–40
calcium iron wire Thicker iron sheet
Calcium iron
Nonserious splashing
Fig. 1 Effect of wire 30

injection speed on the yield
of calcium alloys
25
Ca yield (%)
20
15
10
90 120 150
Wire injection speed (m/min)
Precise Calcium Treatment Software
Many scholars has proposed that there is a liquid window for calcium treatment
technology [19–21]. But the difficulty in the calcium treatment is precise control,
which can affect the pouring of molten steel regardless of excess or deficiency.
At present, the application of calcium treatment in steel plants is still based on
experience to guide production. There is no clear quantitative index, but there are
obvious drawbacks in this way, the production cost is improved, and the quality effect
is not satisfactory. If other operating conditions are not ideal, it is easy to make the
calcium treatment unstable. It is not only difficult to improve efficiency, quality, but
also the opposite effect, dragging down production.
In this regard, a database for the calcium treatment process was built that com-
bines the experimental results of calcium treatment and the relevant thermodynamic
calculation data. According to different steel grades and different operating con-
ditions, the database is customized. Then through the Matlab software to create a
256 Y. Luo et al.
visual interface, call the data in the database, packaged into a software client form to
provide to the user. Compared with the traditional method, the system design builds
a database based on the actual molten steel composition. Considering the different
operating parameters in the plant, the calculation results are returned in real time,
which can save costs, improve efficiency, and give precise guiding suggestions.
Figure 2 shows the operation interface of calcium treatment software. It mainly
includes three parts: parameter input, running result, and functional operation. The
molten steel composition and the operating parameter module can display the current
heat information, such as the molten steel composition and the amount of molten
steel in real time on the interface. In the operation result module, information such
as the average calculated composition of inclusions, the inclusion phase present in
the current molten steel, and the amount of calcium required can be output to the
interface. Used to control the running and stopping of the program on the control
interface module.
Figure 3 shows the running results of the program. The heat information and
calculation results can be obtained in real time. At the same time, after the calculation
is completed, a picture of the ternary phase diagram of the inclusions will pop up,
which more intuitively displays the current inclusion level. Here is the amount of
calcium to be fed and the number of calcium feeds required to calculate the current
yield. This result is also saved in the background for subsequent review.
Figure 4 shows the application of calcium treatment software in different steels.
These samples treated calcium treatment by the software were cut, embedded, and
mechanically polished. Nonmetallic inclusions were observed with an automated
ASPEX system. The solid five-pointed star represents the average value of the inclu-
sions in steel detected by ASPEX, and the hollow five-pointed star is calculated by
the software. From the values of the two, it is basically consistent, which shows the
reliability and feasibility of the software.
Fig. 2 Operation interface of calcium treatment software

(a) Interface
(b) Ternary phase diagram in the current condition
Fig. 3 Running results of calcium treatment software
Conclusions
In the current study, increasing the calcium yield can be achieved by the injection
method and speed of calcium, dissolved oxygen in steel, etc. The online software
is beneficial to improve the stability and accuracy of the inclusion modification by
calcium treatment during the production process of high-quality steels.
258 Y. Luo et al.
Average composition CaS

ated by software
Calcula 0.00
1.00
Liquidus line @1873K
Dmax =21.76 µm
Dmin =1.05 µm 0.25
5
0.75
0.50
0.50
0.75
0.25
5
1.00
0.00
CaO0.000 0.25 0.50 0.75 00 Al O
1.0
2 3
(a) 0.2%C-0.2 Mn-0.03%Al-0

2%Si-0.55%M 0.95%Cr-0.2% Mo-0.0025 %Ca-0.003%S--0.001%O
Average composition
CaS
0
Calculated by software 100
Liquidus line @1873K
Dmax =14.59 µm
Dmin =1.05 µm 25
75
50
50
75
25
100
0
CaO 0 25 50 75 100 Al2O3
(b) 0.18%C-0.2%Si-1.3%Mn-0.025%Al-0.0026%Ca-0.02%Ti-0.004%S-0.001%O
Fig. 4 Application of calcium treatment software in different steels
Acknowledgements The authors are grateful for support from the National Science Foundation
China (Grant No. U1860206 and No. 51725402), the Fundamental Research Funds for the Central
Universities (Grant No. FRT-TP-18-096A1), Beijing International Center of Advanced and Intel-
ligent Manufacturing of High Quality Steel Materials (ICSM), Beijing Key Laboratory of Green
Recycling and Extraction of Metals (GREM) and the High Quality Steel Consortium (HQSC) at
University of Science and Technology Beijing (USTB), China.
References
1. Choudhary SK, Ghosh A (2008) Thermodynamic evaluation of formation of oxide—sulfide

duplex inclusions in steel. ISIJ Int 48(11):1552–1559
2. Zhang L, Thomas BG, R Associate (2002) Alumina inclusion behavior during steel deoxidation.
In: 7th European electric steelmaking conference. Venice, Italy, pp. 77–86
3. Zhang L, Thomas BG (2006) State of the art in the control of inclusions during steel ingot
casting. Metall Mater Trans B 37(5):733–761
4. Wang QY, Bathias C, Kawagoishi N, Chen Q (2002) Effect of inclusion on subsurface crack
initiation and gigacycle fatigue strength. Int J Fatigue 24(12):1269–1274
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by the BOF → LF → billet casting process. Iron Steel Technol 9(4):59–67
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hardened spring steel. Metal Sci J 9(3):235–245
7. Yang W, Zhang L, Wang X, Ren Y, Liu X, Shan Q (2013) Characteristics of inclusions in low
carbon Al-killed steel during ladle furnace refining and calcium treatment. ISIJ Int 53(8):1401–
1410
8. Yang G, Wang X, Huang F, Yang D, Wei P, Hao X (2014) Influence of calcium addition on
inclusions in LCAK steel with ultralow sulfur content. Metall Mater Trans B 46(1):145–154
9. Ito YI, Suda M, Kato Y, Nakato H, Sorimachi KI (1996) Kinetics of shape control of alumina
inclusions with calcium treatment in line pipe steel for sour service. ISIJ Int 36(S1):S148–S150
10. Abdelaziz S, Megahed G, El-Mahallawi I, Ahmed H (2013) Control of Ca addition for improved
cleanness of low C, Al killed steel. Ironmak Steelmak 36(6):432–441
11. Yuan F, Wang X, Yang X (2006) Influence of calcium content on solid ratio of inclusions in
Ca-treated liquid steel. J Univ Sci Technol Beijing, Miner Metall Mater 13(6):486–489
12. Verma N, Pistorius PC, Fruehan RJ, Potter M, Lind M, Story SR (2011) Transient inclusion
evolution during modification of alumina inclusions by calcium in liquid steel: part II. Results
and discussion. Metall Mater Trans B 42B(4):720–729
13. Wang X, Li X, Li Q, Huang F, Li H, Yang J (2014) Control of stringer shaped non-metallic
inclusions of CaO–Al2 O3 system in API X80 linepipe steel plates. Steel Res Int 85(2):155–163
14. Forster E, Richter H, Spetzler E, Wendorff J, Klapdar W, Rommerswinkel HW (1976) Method
of desulfurization of a steel melt. US
15. Klapdar W, Richter H, Rommerswinkel HW, Spetzler E, Wendorff J (1978) Deoxidation,
desulfurization with calcium. US
16. Kawawa T, Imai R (1977) Advanced techniques of alloying elements into molten steel in the
ladle (secondary steelmaking). Tetsu-to-Hagane 63(13):1965–1974
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lets shooting method into molten steel in ladle (secondary steelmaking). Tetsu-to-Hagane
63(13):2110–2125
18. Yamaji K, Dietrich O, Abe H, Tamura K (1980) Method of production of a wire-shaped
composite addition material. US
19. Holappa L, Hämäläinen M, Liukkonen M, Lind M (2003) Thermodynamic examination of
inclusion modification and precipitation from calcium treatment to solidified steel. Ironmak
Steelmak 30(2):111–115
20. Bielefeldt WV, Vilela ACF (2015) Study of inclusions in high sulfur, Al-killed Ca-treated steel
via experiments and thermodynamic calculations. Steel Res Int 86(4):375–385
21. Geldenhuis JMA, Pistorius PC (2013) Minimisation of calcium additions to low carbon steel
grades. Ironmak Steelmak 27(6):442–449
Part IV
High-Temperature Processing
Effect of CO2 on Vanadium Extraction
and Thermal Effect in Top-Bottom
Combined Blowing Converter
Qi Lu, Yu Wang and Pan Li
Abstract In order to better study the application of CO2 in the vanadium extraction
process of a combined blowing converter, the simulation experiment of combined
injection was carried out under laboratory conditions by changing the injection ratio
of CO2 and O2 at the initial injection temperature of 1:10, 2:10 and 3:10 (the flow
rate of O2 is 600 ml/min and the flow rate of CO2 varies proportionally according to
the flow rate of O2 ). The oxidation of carbon and vanadium in the molten pool and
the thermal effect of molten pool under different bottom blowing flow rates were
studied. The experimental result shows that with the increase of bottom blowing
strength, vanadium-extraction and carbon conservation can be improved. If the flow
rate of CO2 increases by 10%, the temperature of molten pool decreases by about
5–7 °C and the heat from molten pool decreases by about 1.3857–2.0214 kJ.
Keywords Vanadium extraction · Thermal effect · Injection ratio · Flow rates
Introduction
The emission of greenhouse gas such as carbon dioxide has caused a series of environ-
mental problems. Nowadays the world is faced with the severe challenge of green-
house gas [1–3]. For metallurgical industry, a large amount of carbon dioxide is
produced in the blast furnace and coke oven. CO2 emitted directly into the atmo-
sphere not only pollutes the surrounding environment but also wastes a lot of carbon
resources. Therefore, how to efficiently utilize the carbon dioxide has become the
focus of many metallurgical workers at home and abroad.
In the traditional process of vanadium extraction from steelmaking, pure oxygen
is directly injected to extract vanadium. The reaction of oxygen with silicon and
manganese produces a lot of heat, which makes the temperature of the molten pool
rise sharply. If the temperature exceeds the conversion temperature of carbon and
vanadium, the oxidation of vanadium will be inhibited and the yield of vanadium
Q. Lu · Y. Wang (B) · P. Li
e-mail: wangyu@cqu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_24
264 Q. Lu et al.
will be reduced. A proper amount of coolant is added in the traditional process so

that the temperature of the molten pool is not too high. However, the introduction
of impurity elements reduces the quality of vanadium slag. Lv et al. reported the
reaction mechanism between CO2 and molten pool elements in steelmaking process
and carried out relevant thermodynamic and kinetic analysis. However, CO2 was not
used as bottom blowing gas in top-bottom Combined Blowing Converter to study
the oxidation law of carbon and vanadium elements in vanadium-containing molten
iron and the change of thermal effect of molten pool [4].
In this study, carbon dioxide was used to replace part of oxygen according to the
weak oxidation of carbon dioxide. The reaction of CO2 with C and Fe in the molten
pool is endothermic. The heat released by the reaction of CO2 with Si and Mn is
30% of that of the reaction with oxygen [5, 6]. It can also inhibit the rapid rise of
molten pool temperature and promote the process of vanadium extraction, and has
little effect on the quality of vanadium slag[7–11]. The purpose of this paper aims
to study the oxidation of carbon and vanadium in the molten pool and the thermal
effect of the molten pool under different bottom blowing flow rates.
Experiment
Experimental Equipment
The main equipments needed in the experiment are 5K-10-16 Si-Mo high temper-
ature electric furnace, MTLQ-2 temperature controller, and self-made gas injection
device. The crucible used for experiments is corundum crucible and graphite cru-
cible. The specifications are, respectively, as follows: D:53 mm, d:46 mm, H:124 mm,
h:120 mm; D:72 mm, d:55 mm, H:155 mm, h:135 mm.
The tungsten and rhenium thermocouple (W-Re5/26) is used in the experimental
temperature measurement. The injection pipe (D:6 mm, d:4 mm) is made of 99%
corundum.
Experimental Materials and Method
The material used in the experiment is pig iron containing vanadium produced by
Panzh Iron and steel group. The contents of each element are shown in Table 1. The
injection gases CO2 and O2 are both industrial grade gases, and the purity is 99.8%.
Table 1 Composition table of the vanadium pig iron, wt%

C V Si Mn P S
3.73 0.325 0.053 0.14 0.075 0.145
Effect of CO2 on Vanadium Extraction … 265
The experimental apparatus is shown in Fig. 1. The 350 g iron block was put into
a corundum crucible, coated with a graphite crucible and put into a silicon molyb-
denum high temperature furnace. After the iron block was melted completely, the
temperature of molten iron in the furnace was stabilized at about 1320 °C. The simu-
lation experiment of combined injection was carried out under laboratory conditions
by changing the injection ratio of CO2 and O2 at the initial injection temperature
of 1:10, 2:10 and 3:10(the flow rate of O2 is 600 ml/min and the flow rate of CO2
varies proportionally according to the flow rate of O2 ). The hot metal was sampled
by glass tube at the first, third, sixth, tenth, and fifteenth minute of injection process,
and 3–8 g hot metal was taken each time. The contents of C, V, and other elements
in the iron samples were obtained by chemical analysis. The temperature of molten
pool is determined by thermocouple.
Effect of Different Bottom Blowing Flow Rate

on Carbon-Vanadium Oxidation
As shown in Fig. 2, with the increase of bottom blowing flow rate, the endpoint
[C] content in the molten pool increases, while the endpoint [V] content decreases.
This indicates that increasing the bottom blowing flow rate of CO2 is beneficial
to vanadium extraction and carbon conservation. Both [C] and [V] have a higher
Fig. 1 Schematic drawing of experimental apparatus

266 Q. Lu et al.
(a) Change of [C] content (b) Change of [V] content
Fig. 2 Changes of [C] and [V] elements in hot metal with time under different bottom blowing
oxidation rate at the initial stage of the reaction, and they will increase with the
increase of bottom blowing flow. This is due to the increase of bottom blowing flow
rates and the greater chaos of the molten pool at the initial stage, which increases the
possibility of contact between [C] and oxygen and makes them oxidize rapidly. For
[V], the lower temperature of the molten pool is beneficial to the vanadium extraction
reaction. In the middle stage of the reaction, [C] and [V] oxidation slowed down.
This is because the state of the molten pool tends to be stable with the process of
blowing. At this time, the temperature of the molten pool is relatively low, which
inhibits the oxidation of [C]. With the rapid oxidation of [V], the content of [V]
decreases continuously, and the mass transfer in the molten pool becomes more
difficult. Therefore, the oxidation rate of [V] gradually slows down. At the end of the
reaction, about 600 s later, the oxidation rate of [C] becomes faster and the oxidation
of vanadium tends to be stable, which is due to the dominant oxidation zone of [C] at
this stage, and the higher temperature of molten pool is not conducive to the oxidation
of vanadium.
From Fig. 2 and Table 2, it can be seen that the oxidation rate of vanadium
increases gradually with the increase of the bottom blowing flow rate. Comparing
the two groups of CO2 and N2 with the bottom blowing flow rate of 2:10, it can be
found that under the same conditions, CO2 can reduce the vanadium oxidation rate
by 0.034%, and increase the endpoint [C] content by 0.117%. The oxidation rate of
Table 2 End-point parameters under different bottom blowing strengths

Bottom-blown Bottom Endpoint Endpoint Vanadium Endpoint
gas blow rates carbon vanadium oxidation rate C/V ratio
content /% content /% /%
CO2 1:10 2.791 0.0203 92.862 137
2:10 2.831 0.0178 93.767 159
3:10 2.861 0.0124 95.656 231
N2 2:10 2.714 0.0144 94.931 188
vanadium increases by 0.905% and 1.889%, respectively, with the increase of bottom
blowing flow rate by 10%, and the content of terminal [C] increases by 0.54% and
0.03%, respectively.
Analysis of Thermal Effect of CO2 Under Combined Blowing

Conditions
As shown in Fig. 3, the endpoint temperature of molten pool is 1382 °C for bottom
blowing N2 and 1375 °C for bottom blowing CO2 at injection temperature of 1320 °C.
And the temperature of the molten pool is lower than N2 for bottom blowing CO2
during the whole experiment, which shows that CO2 can restrain the rise of molten
pool temperature. The temperature rise of molten pool can be divided into four stages:
the first stage is about 0–120 s, the temperature rise of molten pool is unstable and
fast, the heating rate of bottom blowing N2 is about 12.5 °C/min, and the heating rate
of bottom blowing CO2 is about 10 °C/min, the latter is about 2.5 °C/min lower than
the former. The second stage is about 120–300 s: the heating rate of molten pool is
relatively stable. The heating rate of bottom blowing N2 is 7.33 °C/min, and that of
bottom blowing CO2 is 6.67 °C/min. From Fig. 2, it can be seen that the oxidation
of [C] is inhibited, while the oxidation of [V] slows down with the decrease of [V]
content, which makes the heating rate of molten pool decrease by about 0.66 °C/min.
The third stage is about 300–600 s: the element content in the molten pool is low, and
the heating rate of the molten pool is further reduced. The fourth stage is about 600–
900 s. The heating rate of molten pool remains basically unchanged. The elements in
molten pool are close to oxidation equilibrium. The heating rate of bottom blowing
N2 is 0.5 °C/min and that of bottom blowing CO2 is 0.4 °C/min.
Fig. 3 The change of molten

pool temperature with CO2
participation in the reaction
268 Q. Lu et al.
As shown in Table 3, the physical heat absorption of O2 , CO2, and N2 with different
injection flow rates under experimental conditions are calculated according to the
endpoint temperature of molten pool.
Table 3 shows that under the same other conditions, the heat absorption of CO2
is 0.3525 kJ and that of N2 is 0.2294 kJ. When CO2 is used as bottom blowing gas,
the total heat absorption of injection gas is 1.4581 kJ. When N2 is used as bottom
blowing gas, the total heat absorption of injection gas is 1.4382 kJ. On the whole,
under the experimental conditions, the bottom-blown CO2 gas absorbed 0.0199 kJ
more heat than the bottom-blown N2 gas.
The actual temperature difference of different bottom blowing gases at the same
proportion is shown in Table 4.
Table 4 shows that the pool temperature decreases by 6.94 °C when CO2 par-
ticipates in a chemical reaction compared with N2 . When CO2 : O2 = 2:10, CO2
participates in the pool reaction to release chemical heat, which slows down the pool
temperature by 2.331 kJ.
Analysis of Thermal Effect of CO2 Under Different Bottom

Blowing Flow Rates
As shown in Fig. 4, the temperature variation of the molten pool at different bottom
blowing rates is recorded by the thermocouple.
As shown in Fig. 4, the terminal temperature of the molten pool decreases with
the increase of bottom blowing flow rate. Based on the bottom blowing ratio of 1:10,
the end temperature of molten pool decreases by about 5 °C and 7 °C for every 10%
Table 3 Physical heat absorption by blowing different gases

Blown gas Endpoint temperature /°C Gas Gas heat absorption /J
CO2 + O2 1375 CO2 352.5067
O2 1105.614
N2 + O2 1382 N2 229.4389
O2 1208.804
Table 4 Actual temperature difference between blowing different gases

Blown gas CO2 : O2 N2 : O2
Endpoint temperature /°C 1375 1382
Injection flow ratio 120:600 120:600
Physical temperature drop /°C 4.97 4.91
Real temperature of chemical reaction /°C 1379.97 1386.91
Temperature difference of chemical reaction /°C 6.94
increase of the bottom blowing flux, which indicates that CO2 has an obvious effect
on the control of the end temperature of molten pool.
According to the data in Table 5, the physical heat absorption of CO2 and the
total physical heat absorption of injection gas at different bottom blowing rates are
plotted, and Fig. 5 is obtained.
As shown in Fig. 5, the physical heat absorption of CO2 increases by 0.1645 and
0.1269 kJ for each 10% increase in bottom blowing flux. The results show that the
total physical heat absorption of injection gas at different bottom blowing intensity
is 1.3763, 1.4581, and 1.4818 kJ, respectively. The physical temperature drop of
corresponding gas is 4.70 °C, 4.97 °C, and 5.07 °C, and the trend of physical heat
absorption of gas is similar to that of CO2 , which is mainly affected by physical
heat absorption of CO2 . According to Table 5, the actual temperature of molten
pool chemical reaction is 1384.70 °C, 1379.97 °C, and 1373.07 °C, respectively.
Based on CO2 :O2 = 2:10, the proportion of CO2 decreases by 10%, which makes
the temperature of molten pool increase by 4.73 °C due to chemical reaction. If
the proportion of CO2 increases by 10%, the temperature of molten pool will be
reduced by 6.90 °C, that is, the heat of molten pool will be increased by 1.3857 kJ
and decreased by 2.0214 kJ, respectively.
Fig. 4 Effect of bottom

blowing flow rates on molten
pool temperature
Table 5 Physical heat

Injection ratio Endpoint Gas Gas heat
absorption of gases at
temperature /°C absorption /J
different bottom blowing flow
rates 1:10 1380 CO2 188.0036
O2 1179.321
2:10 1375 CO2 352.5067
O2 1105.614
3:10 1368 CO2 479.4091
O2 1002.423
270 Q. Lu et al.
Fig. 5 Change of CO2 and

blowing gas heat absorption
under different bottom
blowing strengths
Conclusion
Based on the variety of elements and thermal effect in molten pool under different
bottom blowing flow rates, the research team draws the following conclusions:
Under the experimental conditions, increasing the bottom blowing rates of CO2
is beneficial to extract vanadium and retain carbon.
With the increase of bottom blowing flow rates, the chemical heat released by
CO2 in the reaction will increase. On the basis of CO2 :O2 = 2:10, if the proportion
of CO2 is reduced by 10%, the heat released from chemical reaction will increase
the temperature of molten pool by 4.73 °C. If the proportion of CO2 increases by
10%, the temperature of molten pool decreases by 6.90 °C due to heat released from
chemical reaction.
If the flow rate of CO2 increases by 10%, the temperature of the molten pool
decreases by about 5–7 °C and the heat from the molten pool decreases by about
1.3857–2.0214 kJ.
Acknowledgements The authors wish to thank NSFC for the financial support to carry out this
research (No. 51334001).
References
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Pittsburgh
Control of the Distribution of Vacuum
Arcs Within Vacuum Arc Remelting
with Externally Applied Magnetic Fields
Paul E. King, Matthew Cibula and Joshua Motley
Abstract Ampere Scientific has previously developed and provided industrial val-
idation of the VARmetricTM measurement system to measure the location of electric
arcs during vacuum arc remelting (VAR) of high temperature specialty alloys. With
the advent of VARmetricTM , it is now possible to continuously monitor and control arc
distributions in order to tailor the heat flux that drives solidification during the VAR
process. Laboratory experiments have applied transverse magnetic fields to generate
specified Lorentz forces as a control mechanism across the arc gap in order to drive
arc locations to predetermined distributions. This type of control makes it possible
to react to undesirable arc conditions during VAR operations or to provide a contin-
uous control to specify a thermal profile for heat input to the melt pool necessary for
ensuring defect-free ingots.
Keywords Vacuum arc remelting · Computational fluid dynamics · Solidification ·

Defects · Segregation · Arc control
Introduction
Vacuum Arc Remelting (VAR) furnaces are the workhorse for the manufacture of
high-value metals and alloys (Ni, Ti, Nb, Zr, Hf, etc.). During VAR operations, the
high-value material (electrode) to be melted is lowered into a water-cooled copper
crucible under vacuum and an electric arc is struck, the arc cathode spots melt the
surface of the electrode while the liquid metal drips into the crucible generating a
molten pool which solidifies into a homogeneous ingot [1]. The controllable param-
eters of the VAR are important in determining the solidification process since they
dictate the heat flux at the liquid metal boundary. These parameters include the cur-
rent and voltage (heat flux), vacuum pressure, melt rate, and cooling rate, and are
critical to the production of defect-free homogeneous materials [2]. Yet, there is
P. E. King (B) · M. Cibula · J. Motley

Ampere Scientific, 1546 SW Industrial Way, Albany 97322, OR, USA
e-mail: paul@amperescientific.com; info@AmpereScientific.com
URL: https://www.amperescientific.com

https://doi.org/10.1007/978-3-030-36540-0_25
274 P. E. King et al.
little information obtainable from VAR systems that can correlate the controllable
parameters to melt quality beyond statistical approaches currently utilized [3]. Yet,
changes in these parameters, whether desired or not, can manifest as defects such as
white spots, freckles, or tree-rings [4, 5] (Fig. 1).
Despite the importance of producing defect-free ingots for safety-critical appli-
cations, including jet engines and medical devices, the VAR process has remained
relatively unchanged since its introduction in the 1940s. Notable improvements in
control include the addition of cameras to visually monitor the annulus around the
electrode for improved safety in operations [6, 7]; and the introduction of drip-short
control over the vertical position of the electrode to fix the melt rate, which pro-
vides a consistent means of obtaining a measure of the level and extent of process
perturbations [8, 9]. While drip-short control may provide more consistent melting
and heating over time, it does not affect direct control over the location of the arcs
(the spatial distribution of heat flux at the surface of the melt pool) and, therefore,
cannot be used to predict melt quality. In an effort to predict product quality and
the probability of generating defects during operations, it is desirable to know the
location of the arcs responsible for melting as well as to be able to affect the arc
location by external control.
Notably, arcs are composed of individual cathode spots that move across the
electrode surface in a semi-random nature. Each arc contains clusters of cathode
spots, with each cathode spot carrying 79–190 amps [7]. The remaining current is lost
Fig. 1 VAR furnace with

VARmetricTM sensors to
monitor the distribution of
arcs beneath the electrode
Control of the Distribution of Vacuum Arcs … 275
through the plasma between the crucible wall and electrode. In a diffuse arc mode,
the cathode spots are generally well dispersed across the electrode surface. This
provides a macro-uniform heat input into the melt pool. Changes in electrode or gas
composition within the arc gap can concentrate the cathode spots into a constricted
mode. In this mode the arc is highly localized and contains higher densities of cathode
spots. Constricted arcs are known to reduce electrical efficiency and subsequently
lead to lower melt rates and the formation of defects.
In this work, we present a measurement system capable of locating the precise
position of the electric arcs during processing and explore the impacts of the arc
locations on the potential for defect formation. Arc position sensing is accomplished
through the deployment of the VARmetricTM measurement system [10, 11]. VAR-
metricTM employs a series of magnetic field sensors external to the VAR in order to
measure the magnetic flux associated with the electric current conduction pathway
associated with the moving arcs within the furnace. Arc distributions taken from an
industrial application of VARmetricTM are utilized to develop time-averaged transient
heat and current boundary conditions due to the dynamic arc motions. Solidifica-
tion modeling utilizing a specially modified version of Melt Flow-VAR to employ
dynamic heat flux boundary conditions is used to investigate impacts of transient
behavior on the solidification profiles to investigate the probability of melt defects.
Finally, a dynamic feedback control system for tailoring arc distributions is pre-
sented. The control mechanism utilizes feedback from the VARmetricTM measure-
ment system to drive external, transverse magnetic field generators in order to control
the time-averaged distribution of arcs over the electrode. This approach allows opera-
tors to drive operating conditions to measurable standard conditions to ensure quality
product production.
Arc Measurement System
The energy input for VAR melting is provided by a large (>5 kA) DC electrical cur-
rent. The current bridges the gap between the electrode and the melt pool generating
a metal-vapor plasma and generating heat for melting. The current path across the
arc gap generates a time-varying magnetic field as the arc moves within the arc gap.
Recently, methods utilizing measurements of the magnetic field to monitor the arc
have been established to study the arc behavior [12, 13]. VARmetricTM combines
an array of magnetic field sensors with simultaneous measurement of the furnace
current and knowledge of the furnace’s electrical geometry to calculate the centroid
of the arc [14]. This measurement can be utilized to generate a detailed map of the
spatial distribution of the heat input to the melt pool. These results have already
shown that the heat distribution is not generally axisymmetric about the center of the
furnace or constant throughout the melt, in contrast to the typical parameters used
in modeling solidification. For example, some computational models have shown
that changing the heat distribution from a Gaussian shape to a toroidal shape may
alter the solidification angle near the sidewall, impacting sidewall yield and quality
[5, 15]. Because most solidification models assume a static Gaussian, axisymmetric
heat input, not much is known about the correlation of arc locations to ingot quality.
The few papers that relax axisymmetric or Gaussian assumptions indicate that the
real time arc dynamics have a profound effect on solidification models [13]. For
example, the Rayleigh number is used as an indicator of freckle formation; transient
models show a 300 times increase in defect generation due to thermal perturbations
provided by a rotating arc [10].
Figure 2 plots arc distribution results from data taken from an industrial VAR
melting a titanium alloy. Several measured arc distributions were observed within
the melting of a single ingot during steady-state operations, with no apparent variation
in the standard signals. Each of these distributions lasted more than 720 s and were
separated by a period of time ranging up to 30 min. For the purposes of this work,
we consider the ‘Center’ and ‘Ring’ distributions in particular since these are the
only distributions that can be modeled as axisymmetric. In regards to the ‘Center’
distribution, this particular plot represents either a constricted distribution in the
center of the electrode or a diffuse distribution covering the entirety of the electrode
surface. Without further analysis of the measurements and measurement error, we can
not determine the difference between these two unique modes. Since the solidification
and segregation of Ni-alloys are more sensitive to processing parameters, we chose to
simulate the effect of time-varying axisymmetric arc distributions on IN718 utilizing
the assumption that time-averaged arc distributions from previous measurements
could be applied.
The radial and angular position of the arcs is measured at 120 Hz and used to
examine collections of arc distributions in 5–35 min intervals. The arc radial posi-
tion data was binned in 12.7 mm increments and histograms were used to plot the
arc distribution over the interval. In this case, the choice of 40 mm for the current
density full-width half-max is somewhat arbitrary because it is not known if the arc
is constricted or diffuse over the surface of the ingot. It is important here to note
that this process treats the data as purely axisymmetric, which is often not the case,
but the lack of a robust 3D VAR solidification modeling capability necessitates this
approach.
Fig. 2 3 distinctly different distributions measured during the production of a Ti ingot. Courtesy
of Woodside et al
Simulations were completed using a modified version of MeltFlow-VAR [16].

MeltFlow-VAR is a multiscale numerical simulation package developed for VAR
processing. It provides a computational solution for mass, momentum, heat transfer,
phase change, and thermal history. The software provides a means of examining
the metallurgical structure and the probability of defect formation due to changing
boundary conditions. Metallurgical properties for IN718 were used for this study
due to its wide use and highly studied properties. The model used axisymmetric
boundary conditions about the center axis. The boundary condition at the pool surface
includes the current density and heat flux and radiative loss. Heat transfer through
the side incorporates an ingot shrinkage factor that determines the contact resistance.
Momentum transfer is solved by using the two-equation k-ε model for turbulent flow.
The Rayleigh number, Ra, is calculated in Eq. 1 where the interdendritic length scale
is ‘l’, ρ is the fluid density, T is the temperature, μ is the viscosity, k the thermal
conductivity and Cp the heat capacity given by the effective permeability with respect
to gravity [16]. The characteristic length scale of the dendrite spacing is calculated
by the method proposed by Auburtin et al. [15].

∂ρ ∂T
g ∂T ∂x
Ra = l4 (1)
μ k
ρCp
The transient current density and heat flux boundary conditions for the top of the
pool follow an axisymmetric Gaussian distribution shown in Eq. 2, where σ is the
arc spread factor, ucenter is the mean center of the distribution, and Ringot is the ingot
radius, jo is the current density and r is the radial position. The arc spread factor and
center were varied with time during the simulations allowing for the effects of arc
dynamics and time-averaged distributions similar to those observed experimentally.
2
−3 r−u center (t)
j(r, t) = jo e σ(t)R ingot (2)
All melts were simulated with parameters as in Table 1. Since the objective was
to study the implications of a time-varying arc distribution during steady-state, the
Table 1 Melt parameters

Parameter Value Units
utilized in the axisymmetric
modeling Furnace current 6 kA
Melt rate 250 kg/hr
Total melt time 526 min
Electrode diameter 440 mm
Ingot diameter 500 mm
Electrode voltage 25 V
Current partition to melt Pool 0.6
simulations did not include initial transient or hot top melting conditions, and the
only input variable that was altered during the simulation was the arc distribution.
The ingot was melted using a centered diffuse arc (σ = 5) for the first 300 min
to allow the melt pool to reach a steady-state so any effects were independent of
the startup dynamics associated with heat transfer to the bottom of the pool. After
301 min the arc center and spread factor were changed and held constant for a set
time, then returned to the original diffuse distribution. The arc parameters used in
the simulations are shown in Fig. 3 which plots the corresponding distributions.
Since the model is axisymmetric, the offset arc condition represents a constricted
arc rotating at the midsection of the pool radius. The diffuse condition, with a large
σ, is representative of a diffuse arc condition while the centered arc with a narrow
distribution represents a constricted arc focused in the center of the melt pool. All
arc conditions were normalized to the furnace current and power.
Computational Results
Figure 4 plots the liquid velocities and the liquid fraction for the centered diffuse,
center focused, and the constricted offset distributions for the 30 min interrupt cases.
In all cases, the pool volume increased under the introduced transient. This could be
due to melting back from the shallower pool and an increase in flow velocity. For the
centered arc, this is likely due to the focused current density entering the center of
the pool. The increase in downward flow along the outer edges of the pool results in
the mushy zone becoming depressed and broadening. The depth of the melt pool at
which solidification begins increased from 160 mm below the pool surface to 190 and
Fig. 3 Axisymmetric arc power distributions used for transient arc boundary conditions simulations
using MeltFlow-VAR
200 mm for both the offset and centered cases. Zanner et al. produced simulations that
predicted the pool to decrease in volume and for the solidification time to increase
for the case of a constricted arc [3]. The discrepancy in results may be attributed to
the constant melt rate across the electrode, which may not be radially constant with
varying arc conditions. It is known that the mode the arc is operating in affects the
melt rate and likely the distribution of metal transfer to the pool. Simulations of a
3D rotating arc and melt pool indicate that the motion and heat input from the arc
generates considerable melt back in the mushy zone [17]. Diffuse modes have higher
electrical efficiencies and higher melting rates [2]. For these studies the melt rate and
efficiencies were kept the same for all conditions.
The liquid flow profile is greatly influenced by the arc distributions chosen here. In
the diffuse condition, the flow is primarily driven by buoyancy forces. The offset arc
condition generates two flow cells shown in Fig. 4. This is due to the greater Lorentz
forces generated by the increase in current density, especially for the centered focused
arc. The max pool velocity increases from 3 mm/s to 9 mm/s for the offset arc, and
to 17 mm/s for the center focused arc. The maximum velocities for the two interrupt
cases are about 50–60 mm below the pool surface nearest the walls. In all cases, after
the interruption, the pool returns to a shallower state.
Fluctuations in pool depth have already been linked to certain defect formations.
For example, tree-ring formation can occur as the solidification front adjusts to the
transient conditions at the pool surface [18]. Variations in the solidification front
cause irregularities in the growth of dendrite tips and promote segregation [2]. A
proposed mechanism for white spot formation is that fragments from the crown (or
shelf) reenter the melt pool [4]. Simulations show these particles may not completely
dissolve in the deeper, cooler liquid if they are above 3–6 mm in diameter [19]. Such
Fig. 4 Pool liquid fraction and fluid velocities during the diffuse and interrupt conditions. Interrupt
began at t = 301 min and was maintained for 30 min. All plots shown at t = 330 min
remelting of the crown may occur if the arc transitions between offset and centered
modes. Finally, one of the consequences of the increased liquid velocities is the
increased likelihood of dendrites breaking and reentering the liquid pool, which has
been a proposed mechanism for white spot formations [2].
Figure 5 shows the Rayleigh number during solidification for each of the cases,
at a specified solid fraction of 0.5. It is believed that the theoretical critical Rayleigh
number for the prevention of freckles should be kept below 1, however, studies show
that the critical Rayleigh number for IN718 is 0.2–0.6 [15, 20]. From a qualitative
analysis the higher Rayleigh numbers indicate greater chances for freckle formation.
The Ra numbers in the midsection increased from 0.2 to 0.32.
The longitudinal variation in Rayleigh number is evident for both short and long
duration interruptions where longer interruptions have larger effects on solidification
and subsequently increase the chances for freckle formation in the midsection. The
onset of the interruption affects the flow dramatically, reducing the Ra number. The
effects of these interruptions are seen later in the history which is attributed to the
melt pool reshaping to a narrower profile with higher solidification angles.
During the onset of the interrupt, the melt pool broadens and becomes deeper
while the mushy zone decreases in vertical thickness. After the interrupt is finished
and the diffuse condition is returned, the pool goes through a rapid reshaping with
the solidification angle in the midsection reaching a maximum value higher than the
steady-state diffuse solidification angle. This is due to the heat transfer being greater
Fig. 5 Rayleigh numbers in the interdendritic region at a solid fraction of 0.5. The transition from
the arc conditions is evident and influences the remaining melt after returning to diffusive conditions.
The Ra number is strongly affected near the walls where solidification is strongly influenced by the
heat flux to the crucible
near the crucible walls causing the regions nearest the wall to solidify quicker. After
about 60 min, the pool returns to similar conditions observed before the interruption.
However, the Ra number reaches a maximum and remains high well after the return
to diffuse conditions.
Arc Control Furnace
This computational study shows a theoretical linkage between arc distributions and
the probability of defect generation in IN718 ingots. With the advent of a mea-
surement system (VARmetricTM ) that is capable of measuring arc distributions, post-
process computation could be used to predict regions within an ingot that have higher
potential of defects, thus providing a means of culling those regions for safety-critical
applications. Additionally, if a control mechanism were available to control arc dis-
tributions, the measurement system also provides feedback to a control system in an
effort to optimize melt conditions while avoiding defect prone conditions. To such an
end, a coupled measurement and control system has been developed for vacuum arc
remelting applications. Here, the VARmetricTM system is affixed to a laboratory VAR
special-built for arc imaging and investigations. Overlaid on top of the measurement
system is a series of magnetic coil pairs designed to provide transverse fields across
the arc gap in order to provide magnetic field forces capable of pushing arcs in known
and deterministic ways.
Figure 6 shows the experimental apparatus built for this study, including the
vacuum chamber, vacuum pump, gas feed valve, horizontal adjustment feed-troughs,
electrodes, electrical input and output feed troughs, and a 15 kW power supply.
The measurement system to monitor the arc locations in real time is affixed to the
exterior of the furnace shell and data is taken at 150 Hz while synchronized video
cameras were used to visually confirm the arc location measurements. The system is
configured with a fixed lower electrode and a movable upper electrode to draw the arc
to a fixed gap size of 0–3 cm. The electrodes are copper with a 5.08 cm diameter while
the cathode is steel of 7.62 cm which is machined to provide molten metal capture.
This scale was chosen to keep the density of arcs on the electrode surface similar to
industrial conditions. Assuming 70A/arc, the experimental furnace provides an arc
density of 0.044–0.088 arcs/cm2 , while industrial furnace may melt up to 100 cm
diameter electrodes with 5–50kA, resulting in a typical density between 0.0091 and
0.36 arcs/cm2 . Therefore, in terms of spacing between arcs, the experimental arc
furnace is within the industrial operating regime for VAR.
Arcs within the furnace can typically be defined as diffuse, constricted, or semi-
constricted. A spatially diffuse arc is shown in Fig. 7a, over an exposure time of 6 ms,
there appears to be a single dim arc column whose width nearly covers the entire
electrode. The centroid measured on this type of arc appears as a slowly varying,
confined spot near the center of the electrode. Alternatively, a semi-constricted arc
distribution is composed of a few constricted columns, approximately 1 cm in diam-
eter, Fig. 7b and c. The cathode spots and their plasma columns move rapidly across
Fig. 6 a Arc furnace

arrangement including 3-axis
Helmholtz coils, with the
inset showing VARmetricTM
sensor locations. b Copper
and steel electrodes
configured with a copper
bridge to calibrate sensors.
c Electrodes upon
completion
the surface of the electrode, typically moving out from the center and travelling up
the side of the electrode before extinguishing. Finally, for a constricted arc, all of the
arc columns are focused in a tight (1–2 cm) region on the electrode for an extended
period of time (>5 s).
The location of the arcs in this furnace can be measured by analyzing the video
images independently of the installed VARmetricTM . The ‘single-arc’ method of
APS applies the Biot-Savart law to calculate the arc centroid from electromagnetic
measurements of the furnace [9]. For example, and as the only nonunique case, a
completely random distribution of many arc columns over the surface of the electrode,
a homogeneous glow discharge, and a centered constricted arc would all result in a
measurement of the centroid of the arcs at the center of the electrode and are only
distinguishable by higher-order statistical measurements. Similarly, video images are
analyzed by measuring the center of mass of the light intensity distribution emitted
by the plasma beneath the electrode. For tests ranging from 10–60 s, with 1500–
9,000 measurements, the correlation coefficient between the two measurements was
>0.95, indicating good agreement between the two measurements.
Fig. 7 a Diffuse, b semi-constricted, and c constricted arcs over 5.08 cm diameter electrodes with
a 1 cm gap. Images taken with a 6 ms exposure time
Vacuum Arc Control
In order to apply active control of the arcs, an external magnetic field is introduced
by appropriately designed Helmholtz Coils. The coil system was designed to apply
uniform fields (–40 to 40 Gauss, >92% uniformity) in any direction in a 5.08 cm
diameter sphere around the center of the furnace. This is approximately the same
order of magnitude as the stirring coils used on some industrial furnaces, which
are known to affect the distribution of arcs beneath the electrode. The fields were
generated with a set of switching DC power supplies, which were able to reverse the
direction of the field within 0.1 s.
Figure 8 shows the effect of a transversely oriented magnetic field on the dis-
tribution of arcs over 10 s compared to an uncontrolled arc. Prior to activating the
translational control of the arc, the camera images also show a semi-constricted arc
Fig. 8 Arc distribution before (left) and after (right) applying a uniform, a transverse magnetic
field to the arc gap in the x-direction. Initially, the arc is free to roam about the 5.08 cm diameter
electrodes, but after the control is applied the arc moves in the direction of the Lorentz force. For
the duration of these tests, the arc remained pinned to that side of the electrode until the control
field was changed
with 1–3 columns that move across the parallel surfaces. Meanwhile, the arc distri-
bution is nearly centered and spread out, and covers most of the electrode surface.
Histograms of the arc radius and angle measurements show a broad distribution,
indicating that the arc is moving freely about the electrode as might be expected.
After applying the control field, the arc moves predictably in response to the Lorentz
force, FL , to one side of the electrode and remains focused at that location. Arc radius
and angle are commensurately constricted as indicated in the histograms. This action
was verified with at least 30 tests at varying control field strengths and directions.
At higher field strengths, it was possible to extinguish the arc by pushing the arc to
the edge of the electrode, while at lower levels the average arc radius was reduced.
It should be noted that unlike a VAR, this arc furnace does not have sidewalls that
could conduct the arc beyond the edge of the electrode, so it might be expected that
this behavior could push the arc from the melt pool to the sidewall or vice versa.
Using the transverse magnetic field controller, the distribution of the arc overtime
was continuously controlled by switching the orientation of the magnetic field every
second between 8 different directions over 180 degrees. The results for each control
step are provided in Fig. 9a, while Fig. 9b shows the total controlled arc distribution
over the control period and compares this to an uncontrolled take just prior to the
control experiment, Fig. 9c. While the uncontrolled arc forms a Gaussian distribution
around the center of the electrode, the control fields focus the arc off-center to about
2/3 of the electrode radius and pushes the arc around the electrode.
Conclusions
This paper combines computational evidence of the importance of arc distributions

on ingot solidification with evidence of active feedback control of arcs in an exper-
imental furnace. In particular, if the heat flux at the pool surface is known at every
given moment, the overall effect on the melt pool can be simulated accurately. Heat
flux distributions were developed using measurements of arc distributions during
industrial VAR melting. These distributions were then used to model solidification
Fig. 9 a Arc distributions, each of which shows 1 s of measurements, over a total of 8 s for a
controlled arc as the control field is rotated around 180 degrees. The direction of the Lorentz force
is indicated by the overlaid arrow for each time step. The total arc distribution over the 8 s control,
b, shows that the arc spends more time near the edge of the electrode than an uncontrolled arc
distribution over the same time period, c
responses for IN718. Although this scenario is a bit contrived, we feel it is instruc-
tional in understanding solidification dynamics under axisymmetric assumptions and
leads to the importance of controlling the distributions to reduce the occurrence of
melt related defects.
A purpose-built experimental vacuum arc remelting furnace was constructed to
accommodate both the Arc Position Sensing Technology, VARmetricTM as well as
the vacuum arc control mechanism to exacting laboratory standards for accuracy in
measurements. The VAC comprised a series of orthogonally positioned Helmholtz
coils designed to provide a uniform field in a specified direction at the center of the
VAR and across the electrode area. By actuating the different fields individually, the
resultant control force vector is completely tailorable with response characteristics
in the millisecond time frame. Through varying the application of the coil current,
arbitrary control vectors in the x-y plane are achievable as a continuous function of
time.
While the type of control demonstrated here did not utilize active feedback from
the APS, further developments in the hardware and software for the test furnace
enabled longer melting times (up to 90 s at 500 Amps) for real time control. The
user interface for the controller software allowed the user to choose the direction of
the desired Lorentz force with the mouse and hence provide a corresponding field
from the Helmoltz coils to accommodate the desired force. This controller interface
was provided side-by-side with a real time arc distribution plot so that the user could
act in response to changes in the arc distribution. The tests proved that this type of
control enabled the user to ‘push’ the arc out of constrictions and apply more even
heating to the surface of the unmelted electrode, while uncontrolled arcs typically
stuck to one side of the electrode and rapidly melted the surface in that region.
Acknowledgements We wish to acknowledge the deep insights into arc position sensing provided
by Dr. Rigel Woodside without whom this body of work could not have been completed. Some or
all of this work was supported by the National Science Foundation SBIR Phase I Grant Number
1647655 and the National Science Foundation SBIR Phase II Grant Number 1831255 as well
as Business Oregon Grant Numbers C2018096 and C2018335. We are greatly appreciative of
the support provided by the National Science Foundation and Business Oregon in support of our
efforts. Additionally, we would like to acknowledge the discussions and contributions provided by
Dr. Gordon Alanko of ATI Specialty Alloys, Mr. Warren George (ret) and Dr. Rodney Williamson
(ret) for the insightful discussions and Mr. Nathan Pettinger for contributions to the project.
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High Temperature Processing
of Tungsten Slag
Xu Wang, Xiaodong Ma, Chunfa Liao and Baojun Zhao
Abstract Tungsten is extraordinarily important for a broad range of industrial pro-

cesses. It has the highest melting point of all metals (3410 °C) and a high density
of 19.3 g/cm3 . Tungsten carbide is known as one of the hardest materials. Tung-
sten is economically extractable from the two minerals wolframite ((Fe,Mn)WO4 )
and scheelite (CaWO4 ) through the intermediate ammonium paratungstate (APT).
Tungsten concentrates are usually digested either by concentrated NaOH solution
or by soda to form sodium tungstate solution which is further converted to APT.
The leaching residue (tungsten slag) separated from the sodium tungstate solution
consists of significant valuable metals such as W, Mo, Cu, Sn, Mn and Fe. These
metals can be efficiently recovered by high temperature process with optimum con-
ditions. Experimental work and thermodynamic calculations confirmed that most of
the valuable metals can be concentrated to a low-melting point alloy and the clean
slag can be used for cement additives.
Keywords Tungsten slag · Thermal reduction · Alloy · Pyrometallurgical recovery
Introduction
Tungsten, also known as wolfram, is one of the important nonferrous metals. It has
the highest melting point of all non-alloyed metals (3422 °C) and the highest ten-
sile strength at temperatures above 1650 °C. 54% tungsten is used for production of
hard metals, 27% for steel and other alloys, 13% for mill products, and 5% for other
applications. The average abundance of tungsten in the Earth’s crust is estimated to
be 1.25–1.50 ppm. The average concentration in workable ores is usually between
0.1 and 1.0% tungsten trioxide (WO3 ). The most common tungsten minerals are
wolframite (Fe,Mn)WO4 and scheelite CaWO4 [1–3]. Tungsten processing usually
X. Wang · C. Liao
Jiangxi University of Science and Technology, Ganzhou, China
X. Ma · B. Zhao (B)
The University of Queensland, Brisbane, Australia
e-mail: baojun@uq.edu.au
https://doi.org/10.1007/978-3-030-36540-0_26
290 X. Wang et al.
includes four steps: (1) leaching from the minerals by NaOH or Na2 CO3 ; (2) precipi-
tation of intermediate tungsten compounds such as ammonium paratungstate (APT);
(3) calcination of APT under oxidizing conditions to obtain WO3 ; (4) reduction of
WO3 at high temperature to obtain tungsten metal powder which is further used
for production of tungsten carbide or various alloys. At present, the consumption of
tungsten resources is huge and fast, and a lot of tungsten residues become wastes after
the tungsten resource is processed in tungsten smelting plant or used as the products.
The recovery of valuable metals from primary and secondary resources becomes
increasingly important, especially for low concentrated resources such as tungsten
[2, 4]. Tungsten can also be recovered from used carbide scrap, catalyst, and leaching
residue [5–8]. The tungsten residue may contain tungsten, scandium, niobium, tanta-
lum, zirconium, titanium, and other valuable elements [7, 8]. The hydrometallurgical
route is usually used to treat the tungsten residue to recover the valuable elements
and generate discarded residue [9]. However, the residue is already the product of
high-pressure leaching which contains remaining Na2 O. Further, leaching by NaOH
or Na2 CO3 cannot completely decompose the residue to recover the valuable ele-
ments. Leaching the residue by acid will consume extra acid to balance the base
Na2 O first and the decompositions are also limited [9]. High temperature process is,
therefore, proposed to treat the tungsten residue.
Experimental
A vertical furnace with lanthanum chromate heating elements was used to conduct
the experiments. Pure graphite powder (99.99 wt%) was used as a reductant. Differ-
ent amounts of graphite were added in the experiments. Tungsten residue was well
mixed with graphite powder in a mortar and then pressed into pellets. The pelletized
sample was then placed into an alumina crucible (ID: 18 mm, H: 25 mm). The sam-
ple was heated under an Ar atmosphere at 1100 °C for 60 min to remove moisture
and start reduction. Then, each pre-reduced sample was heated to the smelting tem-
peratures of 1450–1500 °C for 60 min. The samples were directly quenched into
water after the experiments. After drying, they were mounted in resin and polished
for metallographic analysis. The microstructures were examined by scanning elec-
tron microscopy coupled with x-ray energy-dispersive spectroscopy analysis (SEM-
EDS). Compositions of the liquid and solid phases present in the quenched samples
were measured by electron probe X-ray microanalysis (EPMA). The analysis was
conducted at an accelerating voltage of 15 kV and a probe current of 15 nA. The
ZAF correction procedure supplied with the electron probe software was applied.
EPMA can only measure elemental concentrations. The oxide concentrations were
obtained by assuming the electronic state of the element. The average accuracy of
the EPMA measurements is within ±1 wt%.
High Temperature Processing of Tungsten Slag 291
Experimental Results
The composition of a typical leaching residue is shown in Table 1. It can be seen

from the table that 2.2 wt% WO3 is present in the residue. In addition, MnO, Fe2 O3,
and Na2 O are also present. At 1100 °C, liquid slag containing these oxides is formed.
The reactions between liquid and solid graphite are much faster than those between
solid oxides and graphite. The oxides Fe2 O3 , MnO, and WO3 in the liquid slag can
be rapidly reduced by graphite to form Fe-Mn-W alloy. Solids Fe2 O3 , MnO, and
WO3 in the residue will be dissolved into the liquid slag and then reduced again. The
liquid slag plays a role similar to catalyst. The pre-reduction at 1100 °C is important
to (1) remove H2 O and CO2 present in the residue; (2) form Na2 O based liquid slag;
(3) start reduction. If the residue and graphite are brought to 1450–1500 °C directly,
a large amount of gas (H2 O and CO2 ) will explore the liquid system and Na2 O will
vaporize as well. However, reduction reactions at 1100 °C are not completed and
the formed solid alloy is not separated from the oxides. It is necessary to raise the
temperature to complete the reduction reactions and separate liquid alloy from the
liquid slag.
After the reduction at 1450 °C for 60 min, only liquid slag and alloy were present
in the quenched sample which indicates that the liquidus temperature of the slag is
lower than 1450 °C. Typical microstructures of a sample quenched from 1450 °C
after the reduction is shown in Fig. 1. It can be seen that some fine carbides were
precipitated from the alloy during cooling.
Table 1 The composition of a typical leaching residue for tungsten (wt%)

CaO Fe2 O3 MnO SiO2 Na2 O Al2 O3 WO3 CO2
34.1 27.3 10.8 11.4 3 2.6 2.2 8.6
(a) slag (b) alloy
Fig. 1 Typical microstructures of a sample quenched from 1450 °C after reduction

292 X. Wang et al.
Table 2 The compositions of slag and alloy after reduction at 1450 °C (wt%)
CaO FeO MnO SiO2 Na2 O Al2 O3 WO3
Slag 50.4 0.2 10.7 20.8 0.4 17.5 0.0
Ca Fe Mn Si Na Al W
Alloy 0.0 80.0 13.5 0.0 0.0 0.0 6.4
The compositions of the slag and alloy in the quenched sample are given in Table 2.
It can be seen that all tungsten and iron have been reduced to the alloy and MnO was
partially reduced. It is possible to reduce all MnO to the alloy. However, lowering
MnO in the slag will increase its liquidus temperature. Higher temperature and more
reductant and flux will be required to further reduce MnO which may not have an
economic benefit. The Fe-Mn-W alloy can be used directly in the steelmaking where
Mn and W are required. The slag generated can be used as additives for cement or
ceramic. It is noticed that Na2 O in the slag is only 0.4 wt% which indicates that
it was vaporized during the high temperature processing. The smelting temperature
can be further decreased if the liquidus temperatures of the slag and alloy are deter-
mined. It is anticipated that the alloy is approaching carbon saturation which makes
the liquidus temperature of the alloy below 1200 °C. The addition of flux such as
SiO2 can decrease the liquidus temperature of the slag and, therefore, the operating
temperature. If necessary the Fe-Mn-W alloy can be treated to obtain the pure metals
or alloys available on the market.
Thermodynamic Considerations
FactSage 7.3 [10] was used to predict the reduction of tungsten leaching residue.
The databases selected in FactSage 7.3 are “FactPS”, “FToxide” and “SpMCBN”,
and the main solution species selected in calculations are “FToxide-SLAGA”,
“FToxide-SPINA”, “FToxide-bC2SA”, “SpMCBN-LIQU”, and “SpMCBN-BCC1”.
The leaching residue has much higher CaO/SiO2 ratio which results in high liquidus
temperature. Flux must be added to decrease the slag liquidus. A leaching residue
with addition of silica (Table 3) is used for FactSage calculations. 100 g of the feed
(leaching residue plus silica) is mixed with different amounts of carbon at 1500 °C.
The reduction process is shown in Fig. 2. It can be seen from the figure that Fe is
reduced first when 3 g carbon is added and tungsten starts to form at 4 g carbon. When
5 g carbon is added, all WO3 has been reduced to W. When Mn starts to form at 7 g
carbon, almost all FeO has been reduced to Fe. Note that when the carbon is higher
Table 3 The composition of a leaching residue plus silica flux for FactSage calculation (wt%)
CaO Fe2 O3 MnO SiO2 Na2 O Al2 O3 MgO WO3 CO2
27.1 20.7 8.4 30.0 2.3 2.0 0.7 2.0 6.8
High Temperature Processing of Tungsten Slag 293
Fig. 2 Reduction of 100 g 16

tungsten leaching residue by 14 Fe
Weight of metals (g)

carbon at 1500 °C,
12
calculated by FactSage 7.3
10
8
6
4
Mn
2
W
0
0 2 4 6 8 10 12
Carbon (g)
than 7 g, significant carbon is dissolved into Fe-W alloy to form liquid Fe-W-Mn-C
alloy. According to the reduction process described in Fig. 2, three approaches can
be used to produce three alloy products, respectively.
The first approach is to produce Fe-W-Mn-C alloy with deep reduction. At least
10 g carbon is needed to reduce all FeO and WO3 . However, there is still 3.6 wt%
MnO remaining in the liquid slag even more carbon is added into the system. Higher
temperature and additional flux are required to fully reduce the MnO in the slag. This
is confirmed by the experimental results shown in Fig. 1 and Table 2. The second
approach is, at 7 g carbon addition, to fully reduce FeO and WO3 to obtain Fe-W
alloy which consists of nearly 90% Fe and 10% W. This alloy may be used in the
steelmaking where tungsten is required. It can be seen from the figure that 7 g carbon
addition will be able to obtain this alloy and leave most of the MnO in the slag. The
third approach is to only fully reduce WO3 and partially reduce FeO to maximize
W in the alloy. It can be seen from Fig. 2 that when 5 g carbon is added, all WO3
is reduced to the Fe-W alloy and W in the alloy is 17%. Tungsten can be recovered
from this alloy by oxidation roasting with Na2 O.
Figure 3 shows the oxidation process of 100 g 83Fe–17 W alloy at 600 °C. 5.8 g
Na2 O (10 g Na2 CO3 ) is mixed with the alloy powder and oxidized in air for the
controlled time. The WO3 from the oxidation will react with Na2 O to form Na2 WO4
which can be leached with water to produce tungsten. It can be seen from Fig. 3
Fig. 3 Roasting oxidation of 30

100 g 83Fe–17W alloy at
Na2WO4
Weight of oxide (g)
600 °C, FactSage calculation 25
20
15
10
5 FeO
0
0 1 2 3 4 5 6
Oxygen (g)
294 X. Wang et al.
that oxidation needs to be controlled to minimize the formation of FeO. In this case
neglectable FeO is formed if the oxygen is below 4.5 g. In practice, the temperature
and reaction time need to be optimized to maximize the recovery of tungsten. The
remaining high purity Fe is also a valuable product.
Conclusions
Experimental study and thermodynamic calculations have been used to identify the
optimum conditions to recover valuable elements from the leaching residue of tung-
sten. It is possible to fully recover Fe, W, and Mn at high temperature reduction.
However, economics has to be taken into account to treat the residue. Different
approaches have been discussed for industry to make decision. Both processing cost
and product market need to be considered in selection of the processing conditions.
Fundamental studies provide possibility and base for industrial operations.
References
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Council
2. Premchand (1996) Processing of low-grade tungsten ore concentrates by hydrometallurgical
route with particular reference to India. Bull Mater Sci 19(2):295–312. https://doi.org/10.1007/
bf02744668
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market and methods for processing tungsten concentrates to obtain competitive products. Theor
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4. Willersinn S, Bart H-J (2017) Reactive extraction and critical raw materials: industrial recovery
of tungsten. Chem Ing Tech 89(1–2):82–91. https://doi.org/10.1002/cite.201600079
5. Katiyar PK, Randhawa NS, Hait J, Jana RK, Singh KK, Mankhand TR (2014) An overview
on different processes for recovery of valuable metals from tungsten carbide scrap. In: 18th
international conference on nonferrous minerals and metals, Nagpur, India, 11–12, July, 2014
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WO3 /TiO2 catalyst, extraction 2018. Miner Metal Mater Ser 2455–2469
7. Zhong X (2002) Technology of extracting scandium oxide by primary amine. Chin J Rare
Metal 26(6):527–529
8. Shaoquan X, Li S (1996) Review of the extractive metallurgy of scandium in China (1978–
1991). Hydrometallurgy 42(3):337–343
9. Zhong X, Maosheng F, Qin Y (2014) Study on the decomposition of the tungsten residue using
concentrated hydrochloric acid by reflux method. Adv Mater Res 1033–1034:395–398
10. Bale CW, Bélisle E, Chartrand P, Decterov SA, Eriksson G, Gheribi AE, Hack K, Jung IH,
Kang YB, Melançon J, Pelton AD, Petersen S, Robelin C, Sangster J, Spencer P, Van Ende MA
(2016) FactSage thermodynamic software and databases 2010–2016. CALPHAD 54:35–53
Non-isothermal Kinetics
of Carbothermic Reduction of Fayalite
Zhi Li, Guojun Ma, Xiang Zhang and Wei Zhang
Abstract Fayalite is one of the major components in many metallurgical slags, such
as copper slag and nickel slag, which contains higher iron grade than that in minable
iron ores. It is believed that the carbothermal reduction process at high temperature is
an effective way to reutilize fayalite-bearing slags. In this paper, the non-isothermal
reduction kinetics of fayalite were conducted using a thermogravimetric differential
thermal analyzer heated to 1400 °C with different heating rates. The methods of
Flynn-Wall-Ozawa and Málek were adapted to handle the kinetic data. The results
show that the activation energy increases until the conversion rate is 50% due to
the deterioration of kinetic conditions, and then decreases. The average activation
energy is 514.20 kJ/mol. When the conversion rate is lower than 50%, the reaction
model is the secondary chemical reaction model with the integral form of (1−α)2 .
Subsequently, with the conversion rate increasing, the model changes to the uniform
growth of one-dimensional nucleation with the integral form of lnα.
Keywords Fayalite · Non-isothermal kinetics · Carbothermal reduction ·

Activation energy
Introduction
Non-ferrous metallurgical slags, like nickel slag and copper slag, have attracted
metallurgists’ attention due to its large output, low utilization rate, high economic
value, and hazard. Fayalite (Fe2 SiO4 ) is a kind of the main component that existed
in these metallurgical slags, which makes iron grade higher in these slags than the
ones in iron ore. Aiming to make full use of these slags, it is meaningful to extract
iron from fayalite.
Z. Li · G. Ma (B) · X. Zhang · W. Zhang

Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education,
Wuhan University of Science and Technology, Wuhan 430081, China
e-mail: gma@wust.edu.cn
Hubei Provincial Key Laboratory for New Processes of Ironmaking and Steelmaking, Wuhan
University of Science and Technology, Wuhan 430081, China

https://doi.org/10.1007/978-3-030-36540-0_27
296 Z. Li et al.
Because of the weak magnetic of fayalite, the recovery ratio of iron is not high
with direct magnetic separation. Therefore, there are some researchers proposing to
change the properties of fayalite to recover iron, for instance, make fayalite oxidized
to iron oxide and then magnetic separation [1–4]. However, in the process of oxida-
tion, the viscosity and melting point of the slags would be increased with the increase
of the content of Fe3 O4 , resulting in that the magnetite phase is not easy to aggregate
and grow, and the iron grade is only about 60 wt% [4]. Therefore, one of the most
effective ways to utilize fayalite is to use the carbothermic reduction process. It was
proved that the initial temperature of the reduction of fayalite was about 1042.23 K
in copper slag [5]. The addition of CaO could significantly reduce the reaction tem-
perature to 757.48 K, and increase the ratio of recovery of iron [5]. Prince et al. [6]
have investigated that the recovery ratio of iron is nearly 90% in the carbothermal
reduction process of copper slag, and the secondary slag could be reused to prepare
the glass-ceramics. Li et al. [7] utilized two-step carbothermal reduction to recycle
the nickel slag, and could simultaneously gain the pig iron and cementing material.
For studying the kinetics of carbothermic reduction of fayalite, Warczok et al. [8]
utilized the synthetic fayalite slags to react with a floating graphite disk or immersed
graphite rod from 1250 to 1450 °C. They found that the reaction was controlled by
the Boudouard reaction like the carbothermic reduction of other iron oxides [9–11],
and the activation energy was found to be 246 ± 29 kJ/mol. However, the synthetic
fayalite contained some of the other iron oxides, which would affect the determination
of the activation energy of fayalite. On the other hand, the studies about the kinetics
of reduction of fayalite were mainly with the isothermal method. It was demonstrated
that the activation energy would change with the heating ratio [12], which means
that even at the same temperature range, the different heating ratio would result in
the varieties of kinetics parameters.
In this paper, pure fayalite was used in order to gain more accurate kinetics param-
eters of carbothermal reduction. The non-isothermal method was chosen, and a series
of experiments were conducted with different heating rates, and the activation energy
dependence of conversion was depicted, which can understand the reaction mecha-
nism. The method of Flynn-Wall-Ozawa(FWO) [13] and the method of Málek [14]
were adapted to handle the kinetics data. The former is applicable to the value of
E/RT >20 and could give the relationship between conversion and activation energy,
and the latter could give the reaction model by comparing the solid reaction models.
Non-isothermal Kinetics of Carbothermic Reduction of Fayalite 297
Experimental
Experimental Method
In this experiment, the pure fayalite (Fe2 SiO4 , Alfa Aesar, USA, 96 wt%) and
graphite(chemical pure, Macklin, Shanghai China, 99.99 wt%) were used. The exper-
imental device was a comprehensive thermal analyzer (STA449C, NETZSCH, Ger-
many). High pure Ar(99.99 vol.%) was used as a purge gas with a flow rate of
50 ml/min. The data of TG and DTG would be gained from the analyzer, which
could find the reaction trend and calculate the conversion of reaction. The reaction
of carbothermal reduction of fayalite is shown in Eq. (1):
Fe2 SiO4 (s) + 2C(s) = 2Fe(s) + 2CO(g) + SiO2 (s) (1)
For investigating the variety of activation energy, the kinetics parameters were
gained by non-isothermal kinetics with different heating rate from the value of
2.5 °C/min to 20 °C/min. For the reduction could be reacted completely, the content
of graphite is 2.30 g per 10.00 g pure fayalite in the value of C/O 2.0. After mechan-
ically mixing 10.00 g pure fayalite and 2.30 g graphite, the mass of the sample was
about 10–15 mg in each experiment, and the temperature was raised from ambient
temperature to 1400 °C with different heating rate.
Analysis of Kinetic Data
While the fayalite was reduced by graphite, the mass of the sample would be
decreased due to the formation of CO and CO2 . Therefore, the reduced mass would
be used to calculate the conversion of reaction, which was defined as the Eq. (2):
α = (m0 − mt )/m × 100% (2)
where α is the conversion of reaction, m0 and mt are the initial mass and the mass
at fixed time t, respectively. m is the reduced mass according to the theoretical
calculation.
Using the method of FWO (Eq. 3) to calculate the relationship between conversion
and activation energy of carbothermic reduction of fayalite:
lgβ = lg[AE/RG(α)] − 2.315 − 0.4567 × E/RT (3)
where β is the heating rate, A is the preexponential factor, E is the activation energy, R
is the gas constant (8.314 J/(mol·K)), G(α) is an integral form of the reaction model,
and T is the absolute temperature, K. While the conversion α is constant, the values
298 Z. Li et al.
Table 1 The general solid

No. Differential equation Integral equation
reaction models [12, 15]
1 1−α −ln(1 − α)
2 (1 − α)3/2 2[(1 − α)−1/2 − 1]
3 (1 − α)2 (1 − α)−1 − 1
4 1 α
5 2(1 − α)1/2 1 − (1 − α)1/2
6 3(1 − α)2/3 1 − (1 − α)1/3
7 α lnα
8 1/2α α2
9 3(1 − α)2/3 /2[1 − (1 − [1 − (1 − α)1/3 ]2
α)1/3 ]
10 3/2[(1 − α)−1/3 − 1] 1 − 2α/3 − (1 − α)2/3
11 −1/[ln(1 − α)] (1 − α)ln(1 − α) + α
of G(α), A, E and Rare constant. It means that lgβ has a linear relationship with 1/T
when α is constant, and the E would be calculated by the slope of the line.
The method of Málek (Eq. 4) was utilized to determine the reaction model:
y(α) = G(α)f(α)/G(0.5)f(0.5) = (T/T0.5 )2 (dα/dt)/(dα/dt)0.5 (4)
where f(α) is a differential form of the reaction model, T0.5 and (dα/dt)0.5 are the
temperature and reaction rate when α = 0.5, respectively. According to the general
solid reaction models in Table 1 [12, 15] and the left-hand side of Eq. 4, the curves
could be depicted by the calculated plots of y(α) against α, which was called standard
curves. Based on the experimental data, the experimental value of y(α) would be
gained with the right-hand side of Eq. 4. By comparing the calculated values with
the experimental values, the reaction models could be gained.
Figure 1 shows the variety of mass and conversion of the sample with different heat-
ing ratio from room temperature to 1400 °C. From Fig. 1, the mass of the sample
decreases slightly from room temperature to 1100 °C, due to that the direct reduc-
tion is not easy to happen at low temperature. When the temperature is raised, the
gasification of graphite would happen and provide enough CO to make the indirect
reduction of fayalite reacting, both of which make the mass decreased sharply.
Based on the relationships between heating ratio and temperature in Fig. 1, and
the method of FWO (Eq. 3), the linear fitting between the logarithm of heating ratio
(lgβ) and reciprocal of temperature (1/T) would be depicted in Fig. 2.
Fig. 1 The variety of mass

(a) and conversion (b) of the
sample with different heating
ratio
The variety of activation energy, which is the slope of each line in Fig. 2, is shown
as a function of conversion in Fig. 3. By calculating, each value of E/RT is higher than
20, which means that the method of FWO is suitable for the experiment. With the
increase of conversion, the value of activation energy increase firstly and then drops
down. The highest value obtained is 928.35 kJ/mol when the value of the conversion
is 50%.
This tendency indicates that the reaction is possibly limited by the solid diffusion
in the early reaction stage. From Fig. 1b, when the value of the conversion is 50%,
the temperature is about 1200 °C, which is close to the molten point of fayalite. The
molten sample would make a liquid film to hinder the volatilization of inner gas and
deteriorate the kinetic condition. Therefore, when the value of conversion reaches
50%, the value of activation energy is highest. In the stage of higher conversion, the
300 Z. Li et al.
Fig. 2 The relationship

between lgβ and 1/T when
the value of the conversion is
constant
Fig. 3 The variation of

activation energy
dependence on conversion
gasification of graphite makes the diffusion transformed from solid-solid to gas-solid,

which could improve the kinetics condition, and decrease the activation energy.
The average activation energy of carbothermal reduction of fayalite is
527.41 kJ/mol. As shown in Table 2, this value of activation energy is higher than
the previously reported values [8, 16, 17]. The most important reason is that the
sample in previous researches is fayalite containing iron oxide impurities, which
would make the reduction easier and decrease the activation energy of reduction
reaction. On the other hand, with the isothermal condition, the solid reaction would
happen before reaching the experimental temperature, which also could decrease the
activation energy.
According to the method of Málek (Eq. 4), the standard curves of the plots of
y(α) against α and experimental data (αi , y(αi )) (i = 0.1,0.2…0.9) are shown in
Fig. 4. The numbers in Fig. 4 correspond to the reaction models in Table 1. The
reduction of fayalite is expressed initially by secondary chemical reaction model (α
= 0–0.5), with the integral form of (1−α)2 , and subsequently by uniform growth of
one-dimensional nucleation (α = 0.5–0.9), with the integral form of lnα.
Conclusions
(1) The activation energy of carbothermal reduction of fayalite increases with the
increase of conversion firstly and then drops down when the conversion is higher
than 50%.
(2) The average activation energy of carbothermal reduction of fayalite is
527.4 kJ/mol.
Table 2 Activation energy of carbothermal reduction of fayalite

Authors Type of sample Temperature range Activation energy Ref.
(°C) (kJ/mol)
Warczok et al. Synthetic fayalite Isothermal kinetics: 246.0 [8]
and graphite disk or 1250–1450
immersed graphite
Lin et al. Carbon-bearing Isothermal kinetics: 373.6 [16]
pellet in copper slag 1000–1200
Zhang et al. Carbon-bearing Isothermal kinetics: 118.1 [17]
pellet in copper slag 1000–1200
Present work Pure fayalite and Non-isothermal 527.4 –
graphite powder kinetics: room
temperature to 1400
Fig. 4 The standard curves

of the plots of y(α) against α
and experimental data
302 Z. Li et al.
(3) The reaction model of reduction of fayalite is expressed initially by secondary

chemical reaction model (α = 0–0.5), with the integral form of (1−α)2 , and
subsequently by uniform growth of one-dimensional nucleation (α = 0.5–0.9),
with the integral form of lnα.
Acknowledgements This work was supported by Joint Research Fund of National Natural Sci-
ence Foundation-China BaoWu Steel Group Co., Ltd (No. U1960108) and Hubei Provincial Spe-
cial Project on Technology Innovation (Foreign Scientific and Technological Cooperation) (No.
2017AHB042).
References
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extraction in copper slag. China Nonferrous Metall 1:71–74
2. Palacios J, Sánchez M (2013) Wastes as resources: update on recovery of valuable metals from
copper slags. Miner Proc Extr Metall 120(4):218–223
3. Li KQ, Ping S, Wang HY, Ni W (2013) Recovery of iron from copper slag by deep reduction
and magnetic beneficiation. Int J Miner Metall Mater 20(11):1035–1041
4. Cao HY, Fu NX, Wang CG, Zhang L, Xia SF, Sui ZT, Feng NX (2009) Selective precipitation
and separation of Fe components from copper smelting slags. Multipurp Utilization Miner
Resour 2:8–11
5. Li L, Hu JH, Wang H (2011) Thermodynamic analysis of iron smelting reduction from copper
residue. Mater Rev 25(14):114–117
6. Sarfo P, Wyss G, Ma GJ, Das A, Young C (2017) Carbothermal reduction of copper smelter
slag for recycling into pig iron and glass. Miner Eng 107:8–19
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comprehensive utilization of nickel slag. Mater Rev 31(3):100–105
8. Warczok A, Utigard TA (1998) Fayalite slag reduction by solid graphite. Can Metall Q
37(1):27–39
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11. Shalimov MP, Boronenkov VN, Lyamkin SA (1980) Mechanism and kinetics of reaction of
FeO·SiO2 melts with carbon. Russ Metall 6:31–34
12. Vyazovkin S, Wight CA (1997) Kinetics in solid. Annu Rev Phys Chem 48:125–149
13. Ozawa T (1965) A new method of analyzing thermogravimetric data. Bull Chem Soc Japan
38(11):1881–1886
14. Málek J (1989) A computer program for kinetic analysis of non-isothermal thermoanalytical
data. Thermochim Acta 138:337–346
15. Luo SY, Zhang JY, Zhou TP (2000) Models for kinetic analysis of solid-solid reactions and
their applications. Mater Rev 14(4):6–8
16. Lin QL (2017) Study on the reduction of carbon-bearing pellet of RHF treatment. Master thesis,
Chongqing University
17. Zhang H, Wang G, Zhang SH, Wang JS, Xue QG (2019) Direct reduction kinetics of copper
slag. Nonferrous Metals Sci Eng 10(1):28–33
Upgrading Pilot-Scale Facility at
MINTEK to Evaluate the Effect of
Preheating on Smelter Operations
Joalet Dalene Steenkamp, Glen Michael Denton and Tertius Pieters
Abstract MINTEK in South Africa is investigating the effect of preheating on

smelter operations mainly to reduce the electrical energy requirement for smelters.
A pilot-scale facility is being developed which includes a one t/h rotary kiln coupled to
an electric arc furnace (EAF) optionally served by either an alternating current (AC)
or direct current (DC) power supply. The facility also includes integrated materials
handling, product handling, and water-cooling systems. It allows for the evaluation of
cold versus hot feed (up to 900 °C) on smelter operations over periods of 2–3 weeks
continuous operation. The first application will study the effect of preheating on the
smelting of titaniferous magnetite (15% TiO2 ) using a DC-furnace as part of the
TiMag project. The second application will evaluate the effect of preheating on the
production of high carbon ferromanganese (targeting 78%Mn) using an AC-furnace
as part of the PreMa project. The paper presents the results of the basic engineering
of the project.
Keywords Pilot-scale · EAF · DC · AC · Rotary kiln
Introduction
South Africa is resource-rich, with large deposits of titaniferous magnetite and man-
ganese amongst others. Titaniferous magnetite ore was smelted in the past to recover
its iron and vanadium contents [1] and manganese ore for its manganese and iron
J. D. Steenkamp · G. M. Denton
MINTEK, 200 Malibongwe Road, Randburg 2125, South Africa
e-mail: glend@mintek.co.za
J. D. Steenkamp (B)
University of the Witwatersrand, 1 Jan Smuts Ave, Johannesburg 2000, South Africa
e-mail: joalets@mintek.co.za
T. Pieters
Allied Furnace Consultants, 60 Kelly Road, Jet Park 1459, South Africa
e-mail: tertius@alliedfc.co.za

https://doi.org/10.1007/978-3-030-36540-0_28
304 J. D. Steenkamp et al.
contents [2]. Both of these processing routes are electrically energy-intensive. Over
the past 15 years, the average electricity tariff in South Africa has increased by more
than 250% in real terms [3]. Extensive increases in tariffs were amongst the factors
that culminated in the closure in 2016 of the only plant that smelted titaniferous mag-
netite ore and resulted in the mothballing of some of the manganese ore smelting
facilities. The situation created the need for research into the possibility of reducing
the electrical energy requirement of both processes by introducing a preheating step
prior to smelting.
Mintek has over 45 years’ experience in the research and development of titanif-
erous magnetite resources dating back to 1969. Overall, Mintek has conducted some
30 laboratory-scale projects, several pilot-scale prereduction or smelting trials (1–10
ton), and five smelting campaigns at the 100 ton demonstration scale. Mintek devel-
oped and patented the DC arc smelting of both titaniferous magnetite and ilmenite
with the latter being the first to be commercially implemented. While various process
options have been technically proven, their economics are markedly less attractive
without a preheating or prereduction step to optimise electrical energy consumption.
Although ore pre-treatment itself is not a technical challenge, the direct coupling of
pre-treated titaniferous ore to a DC arc furnace has not been demonstrated and there
is still a risk perception which provides a barrier to commercialisation. Application
for state funding to demonstrate the direct coupling of the two stages was successful
and the TiMag project (2018–2022) was born.
High carbon ferromanganese (HCFeMn) is an alloy consisting of 74–82% Mn,
7.5% C, 1.2% Si, 8–16% Fe [5]. It is mainly produced in electric submerged arc
furnaces (SAFs) through carbothermic reduction of manganese ores. The HCFeMn
production process is energy-intensive with requirements ranging between 2.0 and
3.5 MWh per ton alloy [6–9]. The process is also a significant producer of CO2 emis-
sions, especially in countries where the electrical energy is supplied by coal-fired
power stations, i.e. South Africa. The PreMa project (2018–2022) aims at demon-
strating a suite of innovative technologies to reduce the consumption of electrical
energy and production of CO2 emissions during the production of HCFeMn in SAFs.
A preheating unit will be added to the flowsheet and various technologies are con-
sidered, the pilot-scales of which lie outside the scope of this paper. Included in the
test program is a pilot-scale campaign, to be conducted at Mintek, where the effect
of preheating ore to 600 °C on SAF operation will be evaluated. Although special
emphasis will be on the reduction of electrical energy consumption and production
of CO2 , design and operational requirements of integrating a SAF with a preheating
unit will also be studied.
In order to execute these two projects, the pilot facilities at Mintek are currently
being upgraded. As a preheating unit, a one t/h, electrically heated rotary kiln will be
coupled to an electric arc furnace (EAF) optionally served by either an alternating
current (AC) or direct current (DC) power supply. The facility also includes integrated
materials handling, product handling, and water-cooling systems. It allows for the
evaluation of cold versus hot feed (up to 900 °C) on smelter operations over periods
of 2–3 weeks of continuous operation. The choice of an electrically heated rotary kiln
Upgrading Pilot-Scale Facility at MINTEK … 305
was made for practical reasons and would not be the ideal solution at an industrial-
scale when the aim is to “reduce the consumption of electricity”.
The design phase of the pilot plant project is done in two stages: basic engineering
followed by pilot-scale engineering of new equipment and structures as well as
management of interfaces between existing and new systems. The paper presents the
results of the basic engineering of the project.
Method
The method followed for the basic engineering study was as follows:
1. As a first step in the flowsheet design, the block flow diagram (BFD) was drawn
to identify the function of each step in the flowsheet. Each function was then
further described in the functional specification. No equipment pilot-scales were
discussed.
2. In the second step, specific equipment was added to the flowsheet and material
flows described in the process flow diagram (PFD) and process specifications.
The purpose of the BFD is to represent the main processing sections in terms of
functional blocks. The BFD basically summarizes the principal processing section
and the functional specification describes the BFD in text [10].
The PFD provides a more pilot-scale view of the process. All major processing
units in the process are displayed in the PFD as well as stream information and major
control loops that will allow the process to be regulated under normal operating
conditions [10]. Processing units are displayed using specific icons for each unit.
Arcs or lines between the icons represent the process streams. Directed arcs, flowing
from left to right wherever possible, represent the streams and are numbered for
reference using a numbered circle. By convention, when lines cross, horizontal lines
are shown as continuous arcs and vertical lines broken. Properties of each stream are
provided in a separate table to be found in the process specification.
During the detailed engineering phase, the process control strategy will be
described in the piping and instrumentation diagram (P&ID) and control specifi-
cations. The P&ID transmits the process engineering design to the engineers respon-
sible for plant construction. It is also used during start-up, process operation, and for
operator training. It contains items that do not appear on the PFD, i.e. the location and
type of all measurement and control instrumentation, positioning of valves (including
isolation and control), and the size, schedule, and materials of construction of, pip-
ing [10]. Detailed engineering will therefore, entail the final functional description,
PFDs, equipment datasheets, P&IDs, mechanical, electrical and instrumentation,
civil and structural design, and the final capital cost which includes construction on
site.
Block Flow Diagram and Functional Specification
The BFD for the new facility is presented in Fig. 1. What follows are the functional
specifications for TiMag and PreMa.
Raw materials are received and cleared at the main gate (1). Raw materials are
then dumped at the storage area for temporary storage (2). At the storage area, the
materials are prepared by air-drying and manual bagging, if required (3). Once cold
material is required at Bay 2, bags are transported from the storage area to Bay 2
where the material is loaded into the feed system (4). Under cold feed conditions,
all raw materials are fed directly into the smelter (8). Under hot feed conditions, the
material is first heated in the preheater (5). All raw materials are fed through the
preheater for mixing as well as preheating purposes. Energy for heating of the raw
materials is supplied to the preheater in the form of electricity (6). Hot material is
fed (7) from the preheater into the smelter (8).
At the DC smelter (8), gangue minerals report to the liquid slag phase and a CO-
rich off-gas forms during the reduction process. The smelter is operated in an open
bath, open arc mode which means that the single, centrally located graphite electrode,
is not in direct contact with the liquid slag and the energy input is transferred via
a plasma arc jet. The energy required for the net endothermic reduction process,
is provided in the form of electricity (9). The containment system is based on a
conductive design philosophy. Cooling water is pumped from the water-cooling plant
to the smelter for cooling of critical equipment (10). Hot water is returned (11) to the
water-cooling plant for cooling (12). Molten slag (13.1) and iron (13.2) are tapped
alternately from dedicated tap-holes, via oxygen lancing, into dedicated containers
(14) where it is allowed to cool (15), and subsequently tipped in the storage area (16)
from where both are disposed of (17).
At the AC smelter (8), the raw materials are choke-fed through the roof and
reduced to form a liquid alloy phase which collects at the bottom of the smelter for the
PreMa project. Gangue minerals report to the liquid slag phase. During the reduction
process, a CO-rich off-gas forms. The smelter is operated in submerged arc mode
which means that the electrode tips are in contact with a wet coke-bed that is again in
contact with the liquid alloy. The wet coke-bed consists of carbonaceous reductant
and slag. The energy required for the net endothermic reduction process, is provided
in the form of electricity (9). The containment system is based on insulating design
philosophy. Cooling water is pumped from the water-cooling plant to the smelter for
cooling of critical equipment. Hot water is returned (11) to the water-cooling plant
for cooling (12). Liquid alloy and slag are both tapped from the AC smelter through
a single tap-hole (13) into a container (14) where it is allowed to solidify and cool
(15). Once cooled, the block is tipped in the storage area and the slag separated from
the alloy (16). The slag and alloy are subsequently stored separately, from where
both are disposed of (17).
For both furnaces, the off-gas formed is extracted and combusted to eliminate
any CO or H2 present (18). The hot, dust-laden, combusted off-gas is cooled and
cleaned (19) with the clean gas subsequently vented to atmosphere (20) and the dust
collected and stored (21) from where it is disposed of (22).
Fig. 1 Block flow diagram of the new facility

Process Flow Diagrams and General Layouts
PFDs were drawn for both TiMag and PreMa, based on the BFD presented in Fig. 1.
The PFDs are too extensive to include in this paper but an attempt was made to
describe the process flow and equipment in the subsections presented here. It was
only the rotary kiln, DC and AC furnaces, and their associated feed systems that
had to be designed from scratch. The raw materials receiving and handling, slag and
alloy handling, off-gas and dust handling, and water-cooling systems were already
existing. The discussion that follows includes both existing and new equipment.
Raw Materials Receiving and Handling
Raw materials are delivered by truck, either in bags or in bulk, and cleared at the
main gate. Raw materials are then dumped at the storage area for temporary storage
(Fig. 2a). During storage of materials received in bulk, care is taken to identify each
type of raw material to prevent confusion or mix-ups, to prevent contamination of
raw materials by other raw materials i.e. leaves, etc., and to prevent contamination
of the environment. If required, the materials are prepared by screening, air-drying
(Fig. 2b), and/or manual bagging (Fig. 2c). Again, the contamination of raw materials
is prevented. Each bag is clearly marked to identify its contents. Bags are then stored
in a covered area until further use (Fig. 2d).
Feed System
When material is required at the plant, bags are transported by forklift from the storage
area to Bay 2 where the material is loaded by overhead crane into one of eight 1.5 m3
day bins. Each day bin is equipped with a grate at its inlet and a manual rod gate at
its outlet. To prevent contamination, day bins are clearly marked as containing ore,
reductant, and flux.
To prepare cold feed, raw materials are fed in batches from the four day bins
positioned above the cold feed belt conveyor using electromagnetic feeders. The bay
bins are positioned on load cells should a blend of raw materials need to be prepared.
The cold feed belt conveyor feeds raw materials into a bucket elevator which feeds
into one of two 0.35 m3 surge bins. Material is directed via a flopper gate. The
raw material is fed from surge bin into a loss-in-weight (LIW) feeder in batches by
opening and closing the slide gate at the bottom of the surge bin.
To prepare hot feed, the ore is fed in batches from the four-day bins positioned
above the hot feed belt conveyor using electro-magnetic feeders. The day bins are
positioned on load cells which will allow for a blend of raw materials to be prepared
for preheating. The hot belt conveyor feeds raw materials into a bucket elevator which
Fig. 2 Examples of raw material handling in preparation for a campaign: a raw materials stored
in bulk under tarpaulins to minimise contamination, b raw materials being air-dried in a covered
area, c dried raw material being bagged in bulk bags, and d bulk bags clearly marked and stored in
covered area
feeds into a 0.35 m3 surge bin. The raw material is fed from the surge bin into a LIW
feeder in batches by opening and closing the slide gate at the bottom of the surge
bin. The LIW feeder, with a bin capacity of 0.5 m3 , continuously feeds the rotary
kiln which preheats the raw material.
DC Furnace
The rotary kiln continuously charges hot feed to the furnace, via a single feed chute
and through a dedicated hot feed port located in the furnace roof. A gas seal, com-
prising a choke-fed screw is incorporated in the feed chute design to prevent the
counter flow of furnace process gases. The LIW feeders, with a bin capacity of 0.5
m3 , continuously feed cold material to the furnace, via a single feed chute, through
a dedicated cold feed port located in the furnace roof. Electricity is supplied to the
process via one graphite electrode, which enters the furnace through the roof, and a
Fig. 3 Layout of DC furnace and associated feed system as per basic engineering design
conductive hearth created by ramming refractory between steel pins. The electrode
arm is operated hydraulically. Slag and iron are tapped alternately from dedicated,
bi-level tap-holes.
The general arrangement of the feed system and DC furnace is presented in Fig. 3.
The design criteria on which the layout was based are summarised in Table 1.
AC Furnace
The rotary kiln continuously feeds hot material via a chute into a mixing bin.The
LIW feeder, with a bin capacity of 0.5 m3 , continuously feeds cold material into
the mixing bin. From the mixing bin, the raw materials are choke-fed into the AC
furnace using a feed pipe with its outlet positioned at the furnace roof in the center.
This is done to ensure that the AC furnace is operated in SAF-mode. Electricity is
supplied to the process via three equilateral-spaced graphite electrodes which enter
the furnace through the roof. The electrode arms are operated hydraulically. Slag and
alloy is tapped from a single, single tap-hole.
Table 1 Design criteria for DC furnace and associated feed system

Parameter Value Unit
Process energy requirement (cold feed) 2.33 MWh/ton liquid iron
Process energy requirement (hot feed) 1.72 MWh/ton liquid iron
Maximum ore temperature 900 °C
Slag tap temperature 1700 °C
Iron tap temperature 1500 °C
Off-gas temperature 1700 °C
Process power input 1500 kW
Energy losses 30 %
Calculated feedrate cold ore 836 (max) kg/h
Calculated feedrate cold anthracite 242 (max) kg/h
Bulk density ore 2.5 ton/m3
Bulk density anthracite 0.8 ton/m3
Particle size range for all raw materials 1–12 mm
Hearth power density 500 kW/m2
Shell power density 300 kW/m2
Refractory inner diameter 2000 mm
Shell inner diameter 2468 mm
Shell refractory thickness 230 mm
Total external height (base to roof) 3000 mm
The general arrangement of the feed system and AC furnace is presented in Fig. 4.
The design criteria on which the layout was based are summarised in Table 2. The
mass and energy balance calculations on which the criteria were based are reported
in another paper submitted to the symposium.
Slag and Alloy Handling
At the DC smelter liquid slag or liquid alloy are tapped at different time intervals
through bi-level tap-holes via a launder into a slagpot or into ladles stacked in series—
see Fig. 5.
At the AC smelter, liquid alloy and slag are tapped simultaneously through a
single-level tap-hole via a launder and into ladles stacked in series—see Fig. 6.
When the tap-hole is closed, the ladles or slag pots are transferred by forklift to
the cooling area where the contents are allowed to solidify and cool. Once cooled, the
ladles or slag pots are transferred to the slag waste area where the blocks are tipped
and the slag separated manually from the alloy, should any slag be present in the
Fig. 4 Layout of AC furnace and associated feed system as per basic engineering design
ladle (see Fig. 7a). The solidified and cooled contents of slag pots are also dumped
in this area. The slag is stored in the slag waste area from where it is disposed of
typically at a waste dump. The alloy is stored at the high-value storage shed (see
Fig. 7b) and disposed of or sold.
Off-Gas and Dust Handling
For both furnaces, the off-gas formed is extracted via an off-take on the furnace roof
and combusted at a slip-gap between the off-take and the off-gas stack to eliminate
any CO or H2 produced during the reduction process (see Fig. 8).
The hot, dust-laden, combusted off-gas is cooled during transfer through a water-
cooled duct and trombones. Dust is removed in a baghouse. The clean gas is subse-
quently vented to the atmosphere via an off-gas stack. The dust is collected in bulk
bags positioned below the baghouse and stored from where it is also disposed of
typically at a waste dump. The off-gas fan is positioned between the baghouse and
Table 2 Design criteria for AC furnace and associated feed system

Parameter Value Unit
Process energy requirement (cold feed) 1.187 MWh/ton ore
Process energy requirement (cold feed) 2.304 MWh/ton alloy
Process power input 700 kW
Energy losses 50 %
Calculated feedrate Ore#A 202 kg/h
Calculated feedrate Ore#B 127 kg/h
Calculated feedrate coke 78 kg/h
Calculated feedrate quartz 76 kg/h
Bulk density Ore#A and Ore#B 2 ton/m3
Bulk density coke 0.62 ton/m3
Bulk density quartz 1.28 ton/m3
Particle size range for all raw materials 6–20 mm
Angle of repose of mixture 42 degrees
Feed chute tip height below roof 100 mm
Electrode pitch circle diameter (PCD) power density 2 470 kW/m2
Hearth power density 399 kW/m2
Shell power density 300 kW/m2
PCD 601 mm
Refractory inner diameter 1496 mm
Shell inner diameter 1724 mm
Shell refractory thickness 114 mm
Distance from refractory to outside of electrode 297 mm
Height from bottom plate to tap-hole 380 mm
Height from tap-hole to top of sidewall 722 mm
Total height 1102 mm
the stack. An aerial view that includes the off-gas cleaning plant for Bay 2 is provided
in Fig. 9b.
A secondary off-gas system collects fugitive emissions at the raw material transfer
points and the respective tap-holes. Dust removal takes place at a second baghouse,
refferred to as the environmental baghouse. Clean gas is vented to atmosphere via a
stack and dust collected in bulk bags which are also stored and disposed of typically
at a waste dump. Again, the off-gas fan is positioned between the baghouse and the
stack.
Fig. 5 Typical ladle arrangement when tapping slag from a slag tap-hole and alloy from an alloy
tap-hole in bi-level arrangement
Fig. 6 Typical ladle arrangement when tapping alloy and slag from a single-level tap-hole
Fig. 7 Typical examples of a slag and alloy being manually separated in the slag waste area and
b alloy being stored in the high-value shed
Fig. 8 Typical example of process off-gas being combusted at the slip-gap between the off-take at
the furnace roof and the off-gas stack
Water-Cooling System
For both furnaces, cooling water is pumped from the cold well at the water-cooling
plant to the smelter for cooling of critical equipment. Water is pumped through a
supply line to the main header from where it is distributed to the copper busbars
and electrode clamps; sidewalls, roof panels, and tap blocks (should they require
cooling); and the off-gas duct. Return water is collected in a tundish from where it
Fig. 9 Aerial view of the bays and office blocks at Mintek from the North-Western side of campus.
Bay 2 (a), the off-gas cleaning plant for Bay 2 (b), and the water-cooling plant for all of the
pilot-scale facilities (c) are indicated
is returned to the hot well at the water-cooling plant. Hot water is pumped from the
hot well to cooling towers from where the cooled water is gravity fed into the cold
well. Make-up water is received from the municipality and added to either the hot
well or the cold well. An emergency water tank at Bay 2 can supply water to critical
furnace components, i.e. tap-hole blocks in cases where the main supply fails. The
emergency tank is kept full at all times either by pumping water from the cold well
or by supply with municipal water. An aerial view that includes the water-cooling
plant for all of the pilot-scale facilities is provided in Fig. 9.
Conclusions
A pilot-scale facility to evaluate the effect preheating of ore has one electric arc fur-
nace operation is currently being developed at Mintek. The basic engineering of the
facility was recently completed and the results were described in the paper. The BFD
and functional specification described the flow of materials overall and identified the
function of each step in the flowsheet. The PFD and process specification described
the specific equipment utilised in the flowsheet. The design consist of a combination
of existing and new equipment. Photographs were provided for existing equipment
and general arrangement drawings for the new equipment. For the purpose of titan-
iferous magnetite smelting, a DC furnace was considered and for the production of
high carbon ferromanganese, an AC furnace. As the preheating unit, a rotary kiln was
selected and included in the design of the feed system. Existing equipment included
the raw materials receiving and handling, slag and alloy handling, off-gas and dust
handling, and parts of the water-cooling circuits.
Next Steps
The next steps will include (a) the pilot-scale engineering design of the facility and
(b) the execution of the pilot-scale campaigns in 2020 for the TiMag project and
2021 for the PreMa project.
Acknowledgements The TiMag project is funded by the Medium Term Expenditure Framework
(MTEF) funding by the South African National Treasury. The PreMa project is funded by the
European Union’s Horizon 2020 Research and Innovation Programme under Grant Agreement No
820561 and industry partners: Transalloys, Eramet, Ferroglobe, OFZ, and Outotec.
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Preparation of Expanded Slag Ball
with Blast Furnace Slag by Rotary Cup
Feifei Pan, Xuewei Lv, Wenchao He and Guishang Pei
Abstract Molten blast furnace (BF) slag is a kind of liquid resource with abundant
waste heat which has not been recycled in the iron and steel industry. At present,
the treatment of blast furnace slag is usually water quenching and air cooling accu-
mulation. But, there are some disadvantages in this way to the treatment of blast
furnace slag, such as serious air pollution and high water consumption. This paper
describes the preparation of expanded slag ball with blast furnace slag by rotary cup.
The effects of rotating speed, diameter of rotary cup and water content on particle
size distribution, vitreous content, and grind ability of slag ball were studied. The
blast furnace slag ball produced by this method is capable of self-drying because of
its own heat. It does not need follow-up dehydration, drying, and other processes to
save energy.
Keywords Molten blast furnace slag · Rotary cup · Vitreous content · Grind ability
Introduction
Blast furnace slag is the main by-product in the iron-making process, and has a yield
of 300–350 kg/t-pig iron [1]. It is composed of the components (quartz, clay minerals,
carbonate, and apatite) in iron ore and limestone (or dolomite) solvent combination,
and at 1673–1873 K temperature into a molten state. The heat contained in molten
BF slag reaches up to 1600 MJ/t. In 2018, the production of pig iron in China was
nearly 771 million t [2], and about 230 million t of BF slag were produced. The
total energy carried by molten BF slag amounted to the equivalent of 1.8 million t of
standard coal. At present, water quenching is widely used to treat blast furnace slag
in most iron and steel plants at home and abroad. However, it has caused a series
of environmental problems, including heat waste, water consumption, and pollution
emissions [3–7]. Water quenching treatment of blast furnace slag does not meet the
requirements of sustainable development.
F. Pan · X. Lv (B) · W. He · G. Pei

e-mail: lvxuewei@163.com

https://doi.org/10.1007/978-3-030-36540-0_29
320 F. Pan et al.
Facing the pressure of saving water, reducing emission, and recycling waste slag,
the preparation of expanded slag ball with blast furnace slag has begun to develop in
the early 1990s [8–10]. The technical concept of this technology is to use water to
evaporate and expand the slag ball to produce a large amount of gas into the slag, and
then break the expanded blast furnace slag due to the mechanical stress generated by
the drum, forming a hollow slag ball of about 2 mm, and forming a hollow slag ball
in the center. This ideal glass slag ball is usually used to replace Portland cement.
Previous studies mainly focused on the open environment without heat recovery,
and did not quantitatively study the relationship between the amount of water added,
the rotational speed and the strength of slag particles, and the volume fraction of
glass. Combining with the closed granulator and previous research on heat recovery
[11–14] of granulation, it is proposed to produce expanded blast furnace slag pellets
by granulator and air heat exchange method to realize heat recovery.
By controlling the disc diameter (110, 130, and 150 mm), rotational speed (800,
1000, 1500, and 2000 rpm), and water flow (0.1, 0.2, and 0.3 l/min) of the cen-
trifugal granulator, the different variables under the granularity distribution, glass
volume content, and wear resistance of the slag ball were found. It provides some
references for the follow-up utilization of blast furnace slag, especially at the present
time of energy saving and emission reduction, this treatment method has certain
popularization value.
Experimental
The blast furnace slag used in this experiment was from Laiwu Iron & Steel Group
Co, Ltd, Shandong province, China. The main chemical compositions of the blast
furnace slag shown in Tables 1 and 2 shows the experimental scheme of expanding
slag ball.
It can be seen from the composition table that blast furnace slag can be used
as cement admixture. Figure 1 is the schematic diagram of the blast furnace slag
Table 1 Chemical compositions of the blast furnace slag

Composition CaO MgO Al2 O3 SiO2 Others
Content (wt%) 40.6 7.1 11.1 35.3 5.9
Table 2 Experimental
Raw material Rotary speed Diameter of Flow of
scheme of expanding slag
(rpm) disc (mm) water
ball
(L/min)
BF slag 800, 1000, 110, 130, 150 0.1, 0.2, 0.3
1500, 2000
Preparation of Expanded Slag Ball … 321
Stopper
Induction furnace
Valve
Observation Water
hole
Air outlet
Camera Rotary disc
Motor
Control cabinet
Lifting
Water tank handle
Expanded slag ball
Fig. 1 Schematic diagram of the blast furnace slag expansion slag ball experimental facility
expansion slag ball experimental facility. It mainly consists of four parts: feeding
system, granulation system, heating furnace unit, observation, and detection system.
The massive furnace slag is added into the graphite crucible and put into the
induction furnace. The temperature of the control cabinet is raised to 1673 K for half
an hour. When the slag sample is in the state of complete melting, the flow of water
is controlled by flowmeter, then the motor driving the turntable is opened, and the
stopper is finally pulled out. The molten blast furnace slag contacts the water layer
and evaporates when the water is heated, which instantaneously generates a large
amount of steam. At this time, the gas content in the slag increases greatly far more
than the solubility of the slag to gas at atmospheric pressure. Internal gas cannot exist
in slag in the form of dissolution, but in the form of bubbles. Because of centrifugal
force, the expanded gas-containing slag slides to the edge of the rotary disc until
it flies away from the rotary disc, the slag particles cool rapidly in the air, the slag
viscosity rises sharply, and the surface solidifies rapidly, which makes a considerable
number of bubbles stabilize inside the slag. When the slag particles fly in the air, due
to the surface tension, the bubbles in the slag form micropores and the slag particles
form an expanding slag ball. The heat generated is discharged through the air outlet
and can be used to preheat the furnace charge through collection.
322 F. Pan et al.
Mass Fraction Distribution
The slag balls from the collection tray are screened by sieve, then weighed and
counted. Draw the histogram as shown in Fig. 2 (Diameter of disc-110 mm), Fig. 3
(Diameter of disc-130 mm) and Fig. 4 (Diameter of disc-150 mm).
Figure 2 shows the mass fraction distribution of the particles at different rotary
speeds. When the Q of water is 0.1 L/min, Q = 0.2 L/min and Q = 0.3 L/min,
respectively. A large part of the particle size is populated in the range of 2.0–3.0 mm
for all rotary speeds and Q, which accounts for over 30% mass fraction on average.
From Fig. 2 (Q = 0.1 L/min), the particle mass fraction increases of rotary speeds for
particle size in the range of 0.0–2.0 mm except for the nRCA = 1000 rpm. However, the
tendency is opposite when the particle size is over 2.0 mm, the particle mass fraction
reduces by increasing rotary speeds except for the nRCA = 1000 rpm. From Fig. 2 (Q =
0.2 L/min) and (Q = 0.3 L/min), the particle mass fraction increases of rotary speeds
for particle size in the range of 0.0–2.0 mm. However, the tendency is opposite when
the particle size is over 2.0 mm, the particle mass fraction reduces by increasing rotary
60 50
DRCA=110mm,Q=0.1L/min DRCA=110mm,Q=0.2L/min
50 nRCA=800rpm nRCA=800rpm
nRCA=1000rpm 40 nRCA=1000rpm
nRCA=1500rpm nRCA=1500rpm
40 nRCA=2000rpm nRCA=2000rpm
Fraction(wt.%)
Fraction(wt.%)
30
30
20
20
10
10
0
0-0.5 0.5-1 1-2 2-3 3-5 5- 0 0-0.5 0.5-1 1-2 2-3 3-5 5-
Granule (mm) Granule (mm)
60
DRCA=110mm,Q=0.3L/min
50 nRCA=800rpm
nRCA=1000rpm
nRCA=1500rpm
40 nRCA=2000rpm
Fraction(wt.%)
30
20
10
0
0-0.5 0.5-1 1-2 2-3 3-5 5-
Granule (mm)
Fig. 2 Diameter of disc is 110 mm, the mass fraction distribution of slag ball at different rotary
speeds
40
DRCA=130mm,Q=0.1L/min 40 DRCA=130mm,Q=0.2L/min
30
nRCA=2000rpm 30
nRCA=2000rpm
Fraction(wt.%)
Fraction(wt.%)
20
20
10
10
0 0
0-0.5 0.5-1 1-2 2-3 3-5 5- 0-0.5 0.5-1 1-2 2-3 3-5 5-
50
DRCA=130mm,Q=0.3L/min
nRCA=800rpm
40
nRCA=1000rpm
nRCA=1500rpm
nRCA=2000rpm
Fraction(wt.%)
30
20
10
0
0-0.5 0.5-1 1-2 2-3 3-5 5-
Granule (mm)
speeds
speeds. The increase of water flow will increase the mass distribution of particles
larger than 2 mm at low rotating speed. Such as when the Q = 0.1 L/min, nRCA =
800 rpm, the particle mass fraction in the range of 2.0–3.0 mm is 40%, when the
Q = 0.2 L/min, Q = 0.3 L/min, the particle mass fraction is 47, 48%. Figures 3
and 4 show the mass distribution of different particle sizes with diameter of 130 and
150 mm. Figures 3 and 4 show the mass distribution of different particle sizes with a
diameter of 130 and 150 mm. The particle mass fraction is more regular. It increases
of rotary speeds for particle size in the range of 0.0–2.0 mm and when the particle
size is over 2.0 mm, the particle mass fraction Reduces by increasing rotary speeds.
The increase of flow rate is helpful to increase the mass of particles larger than 2 mm
at low rotating speed.
Vitreous Content
Blast furnace slag as cement admixture needs not only similar components, but also
more than 60% of the glass volume. Up to 50% can be added [15]. Figure 5 shows
the actual diameters of the rotating disc 130 mm, flow rate 0.3 L/min and at different
rotational speed.
324 F. Pan et al.
40 DRCA=150mm,Q=0.1L/min 40 DRCA=150mm,Q=0.2L/min
30 30 nRCA=2000rpm
nRCA=2000rpm
Fraction(wt.%)
Fraction(wt.%)
20 20
10 10
0 0
0-0.5 0.5-1 1-2 2-3 3-5 5- 0-0.5 0.5-1 1-2 2-3 3-5 5-
40 DRCA=150mm,Q=0.3L/min
nRCA=800rpm
nRCA=1000rpm
nRCA=1500rpm
30 nRCA=2000rpm
Fraction(wt.%)
20
10
0
0-0.5 0.5-1 1-2 2-3 3-5 5-
Granule (mm)
speeds
The mineral phase of the particles is observed. Because of the limited space, only
130 mm diameters of the rotating disc, 0.1 L/min flow rate, and 3 mm particle size at
different rotational speeds are given. Figure 6 shows the observation results. There
are holes in the particles, which verifies that a large number of gases accumulate in
the slag and no obvious crystalline shape is observed except for 800 rpm. When the
flow rate is 0.1 L/min, the rotational speed must be greater than 800 rpm to facilitate
the formation of amorphous crystals, and the hydration of cement is better.
XRD tests were carried out on water quenched slag, dry granulated slag, and
expanded slag ball. As shown in Fig. 7, the vitreous content of the three types of slag
calculated by jade software is about 95%, 80%, and 60%, respectively.
Grind Ability
As cement admixture, blast furnace slag needs to be grinded down to less than 4900
holes/cm2 , so the grind ability of treated blast furnace slag needs to be tested. The
economic value of easily grinded blast furnace slag particles is higher. The grind
ability tests of expanded ball and water quenched slag were carried out in a single
barrel ball mill (20 kW motor) in the laboratory. The fineness (4900 holes/cm2 sieving
Fig. 5 Expanding slag ball is in diameters of the rotating disc 130 mm, flow rate 0.3 L/min, and
different rotational speed
allowance) of each 100 g loading sample is measured every hour. The fineness of
expanded ball and water quenched slag is similar at the same grinding time. Generally
speaking, the difference of grind ability between them is not significant. Under the
experimental conditions, the grind ability of 0.3 L/min water was the best, and the
sieve allowance reached 85% in the first hour.
Conclusions
In this paper, the particle size distribution, glass content and grind ability of expanded
ball under different rotating speeds, water addition, and rotating disk diameter were
studied. The conclusions are summarized as follows, A large part of the particle size
is populated in the range of 2.0–3.0 mm for all rotary speeds and Q, the particle
mass fraction increases of rotary speeds for particle size in the range of 0.0–2.0 mm
and when the particle size is over 2.0 mm, the particle mass fraction reduces by
increasing rotary speeds. The increase of flow rate is helpful to increase the mass of
particles larger than 2 mm at low rotating speed. Vitreous contents of the expanded
slag ball calculated by jade software are about 80%, it’s vitreous content can meet
326 F. Pan et al.
Fig. 6 3 mm expanding slag ball of mineral phase is in diameters of the rotating disc 130 mm, flow
rate 0.3 L/min, and different rotational speed
Fig. 7 XRD pattern of the

expanded slag ball, water
quenched slag and dry
granulation
the requirements as cement admixture. The difference of grind ability between them
is not significant. Under the experimental conditions, the grind ability of 0.3L/min
water was the best, and the sieve allowance reached 85% in the first hour.
Acknowledgements The authors are grateful for the financial support by National Key R&D
Program of China (Grant No. 2018YFC1900500).
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Ripening Behavior of Carbides
in Low-Carbon Low Alloy Steel
FAS3420H During Spheroidizing
Annealing Process
Shuai Liu, Fuming Wang, Zhanbing Yang, Yongliang Li, Xi Chen

and Lijuan Sun
Abstract Cold heading process has been applied in the production of gear to improve
production efficiency and reduce energy and steel consumption. To increase the duc-
tility of FAS3420H steel and solve the cracking problem during cold heading, the
Ostwald ripening behavior of carbides in steel was studied during different anneal-
ing processes. Intercritical annealing process not only reduces the formation of
spheroidal carbides, but also causes pearlite to become coarser and larger, deteri-
orating the cold heading performance of the steel. After 850 °C normalizing and 705
°C subcritical annealing, the lamellar pearlite in the sample was almost dissolved
and a large number of small, evenly dispersed spherical carbides formed, meeting the
requirements of cold heading. In addition, a formula was presented to quantitatively
characterize the progress of Ostwald ripening of the carbides and the spheroidiza-
tion mechanism of carbides was analyzed from the perspective of kinetics and the
experimental results.
Keywords Low-carbon low alloy steel FAS3420H · Subcritical annealing ·

Ostwald ripening behavior · Carbides
S. Liu · F. Wang · Z. Yang (B) · Y. Li · X. Chen · L. Sun

S. Liu
e-mail: liushuai_ustb@sina.com
F. Wang
Y. Li
X. Chen
e-mail: vickychen2011@hotmail.com
L. Sun
e-mail: sunlijuan0102ustb@163.com

https://doi.org/10.1007/978-3-030-36540-0_30
330 S. Liu et al.
Introduction
Low-carbon low alloy gear steel is suitable for heavy-duty carburizing components
manufactured by cold heading, such as gears, gear shafts, nuts, etc. [1]. Cold head-
ing process is currently the main forming method for medium carbon high quality
alloy steel to manufacture fasteners such as bolts, which has the advantages of high
production efficiency and good product quality, greatly reducing production cost and
energy consumption, and can improve the tensile strength of processed workpieces
and improve the performance of processed products through cold work hardening.
With the development of the cold heading process, more and more steel will be
machined by the cold heading process.
Though FAS3420H steel has good plasticity performance due to high metallurgi-
cal quality and less inclusions, it still cannot meet the requirements of cold heading
process. The banded microstructures forming after rolling causes stress concentra-
tion at the pearlite–ferrite interface, which makes the steel easy to crack during cold
heading [2]. Therefore, the heat treatment is necessary for the steel to obtain a mate-
rial with good cold deformation properties of low hardness and high plasticity [3]. At
present, there are few studies on spheroidizing annealing in low-carbon gear steel.
The spheroidization of carbide is a diffusion-based process [4]. As a consequence
of the energy-dissipating mechanism [5], spherical carbides have a smaller interfa-
cial energy than lamellar carbides, so spontaneous transformation of carbides from
lamellar to spherical transitions can occur in heating conditions. Many researchers
have used different methods, such as intercritical annealing, cyclic heat treatment,
and subcritical annealing, to obtain spheroidization technology, meanwhile, the Ost-
wald ripening behavior of carbides during heat treatment has been researched and it
is found that temperature and soaking time of heat treatment has a large influence on
the spheroidization of carbides [6–8].
In this paper, different annealing processes have been performed on low-carbon
low alloy gear steels FAS3420H to study the Ostwald ripening behavior of carbides
in samples during heat treatment. The Ostwald ripening process of carbides has a
great influence on the microstructure and mechanical properties of the samples and
a suitable spheroidizing annealing process is necessary for the samples to obtain the
proper microstructure and mechanical properties.
Experimental Procedure
The chemical composition of FAS3420H is given in Table 1, and microstructure of

samples as-cast and after rolling is shown in Fig. 1. As is shown in Fig. 1, the sample
as-cast is primarily composed of ferrite and pearlite, the samples after rolling have
Table 1 Chemical composition of FAS3420H (wt%)

C Si Mn P S Cr Ni Mo N
0.2 0.25 0.85 – 0.02 0.55 0.55 0.2 0.008
Ripening Behavior of Carbides in Low-Carbon Low Alloy Steel … 331
Fig. 1 Microstructure of samples a as-cast and b after rolling
an obvious banded structure, which reduces the ductility of the steel, and is easy to
cause stress concentration at the boundary of the two phases to crack during cold
heading.
The heat treatment temperature and soaking time of the spheroidizing annealing
process have a great influence on the spheroidized microstructure [9]. For the inter-
critical spheroidizing annealing process, this work extended the soaking time and
increased the heat treatment temperature, and studied the effects of soaking time
and temperature on the carbide spheroidization of FAS3420H. In order to obtain a
spheroidized microstructure and reduce time and energy consumption, a subcritical
annealing process was proposed. The thermal schedule is shown in Fig. 2, and param-
eters 770 °C/7 h, 770 °C/10 h, 780 °C/10 h, 705 °C/28 h were marked as Process 1,
Process 2, Process 3, Process 4, respectively.
Fig. 2 The thermal schedule

of different annealing
processes
332 S. Liu et al.
Results
The annealed samples were ground, polished, and then etched with 4% natal for
5–10 s to reveal the microstructure of the samples, and the distribution of carbides
in the ferrite matrix was observed based on scanning electron microscopy(SEM).
Table 2 shows the spheroidization level for different processes and Fig. 3 shows the
microstructures of samples. It can be seen that the microstructures of samples after
Process 1, 2, and 3 is ferrite + pearlite, but the number of spheroidal carbides grad-
ually decreases. The microstructure of sample after Process 4 is spherical carbides
and polygonal ferrite.
Table 2 The spheroidization level for different annealing process

Process 1 2 3 4
Spheroidization level 3 2.5 2 6
Fig. 3 Microstructure of samples after a process 1, b process 2, c process 3, d process 4

Spheroidization Effect of Intercritical Annealing Process
As is shown in Fig. 3a pearlite has not been dissolved in a large amount, only a
small amount of spherical carbides are formed in the ferrite matrix, indicating that
soaking time is not long enough or holding temperature is not high enough [10].
Careful observation of the internal structure of the pearlite which is shown in Fig. 4
reveals that a part of the lamellar cementite is melted and forms into fine dot-chain
carbides during the heat treatment. This kind of microstructure cannot achieve the
purpose of improving the ductility and reducing cracking possibility of FAS3420H,
so the intercritical annealing process needs to be improved. The effect of intercritical
annealing process on spheroidization level is studied by extending soaking time and
increasing heating temperature.
Effect of Extended Heat Treatment Soaking Time
Soaking time of the heat treatment was prolonged. The pearlite in samples became
smaller, but the number of spherical carbides decreased which is shown in Fig. 3b.
With the extension of soaking time, a small part of pearlite in the hot-rolled samples
was dissolved but the precipitation of spherical carbides reduced. The reason may
be that as soaking time is prolonged, the original spherical carbide nucleation sites
in the matrix dissolves, which eventually leads to the decrease of spherical carbides
precipitation, indicating that the nucleation sites of spheroidal carbides in the matrix
has a large influence on precipitation of carbides in the intercritical annealing process.
Fig. 4 Microstructure of a
sample after process 1
334 S. Liu et al.
Effect of Increased Heat Treatment Temperature
Heat treatment temperature was befittingly increased. As is shown in Fig. 3c, the
number of spheroidal carbides obviously decreased compared to Process 2, and the
thickness of lamellar cementite increased. The increase of heat treatment temper-
ature further promotes the dissolution of lamellar cementite. But when soaked at
the temperature under A1 for a long time, the dissolved carbon precipitates on the
undissolved lamellar cementite, eventually leading to thicker lamellar cementite and
area larger pearlite. Meanwhile, it is inhomogeneity of the original microstructure
and randomness of microstructure dissolution that causes the distribution and size of
the microstructure after heat treatment more uneven. Such microstructure like this
seriously would affect the quality of the steel product and it would not be conducive
to improve the cold heading performance of low-carbon low alloy steel.
Spheroidization Effect of Subcritical Annealing Process
The effect of subcritical annealing process on spheroidization was very obvious,

but spheroidal carbides still existed in the original pearlite region, as is shown in
Fig. 3(d). During the subsequent carburizing process of gear steel, austenite would
first nucleate and grow at the interface between ferrite and pearlite [11, 12]. Due to the
uneven distribution of spheroidal carbides, the nucleation position and sequence of
austenite would be different, which would affect the initial grain size and uniformity
of the microstructure after austenitization, thus affecting the gear steel quality, and
providing unfavorable conditions for subsequent heat treatment.
Therefore, 850 °C normalizing and 705 °C subcritical annealing which is marked
as Process 5, is used to treat the samples. With Process 5, the original pearlite in
the samples had been almost dissolved, a large number of fine, uniform dispersed
spherical carbides were precipitated in the steel matrix and a small amount of carbides
were precipitated near the grain boundary. As is shown in Fig. 5, compared with
Process 4, the size of spheroidal carbides in the samples after Process 5 was slightly
increased, but their distribution was more uniformly dispersed. The reason may be
that the refinement of the microstructure after normalizing treatment results in a
shorter diffusion path of carbon, thus at the same temperature and soaking time,
more fine, dispersed carbides precipitate. Such microstructure would be beneficial
to improve the plasticity and toughness of the studied steel, reduce the anisotropy of
the steel, and improve the cold forming process performance.
In summary, 850 °C normalizing and 705 °C subcritical annealing is a suitable
process parameter that can improve the spheroidization level of low-carbon low alloy
steel and improve mechanical and process performance.
Fig. 5 Microstructure of
samples after normalizing
and subcritical annealing
Discussion
Mechanism of Nucleation of Spherical Carbides
Figure 4 indicates that the nucleation of spheroidal carbide first occurred inside
the pearlite because part of lamellar cementite inside the pearlite melted and
spheroidized. Parusov et al. [13] believe that the high-density dislocation can be used
as nucleation sites and reduce the nucleation energy. This also explains why there
is a lot of spheroidal carbides precipitating in the ferrite matrix during subcritical
annealing process.
It is known that a groove will develop on the surface of a hot polycrystal wherever
a stationary grain boundary emerges to intersect the surface [14]. There are crystal
defects such as dislocation in the pearlite which can be used as nucleation sites
and subgrain boundaries form between cementite and ferrite, under the action of
interfacial tension, a groove will appear at the contact point between these subgrain
boundaries. It is assumed that the groove be coronal, as is shown in Fig. 6. Let α
be ferrite, β be cementite, α-β be non-coherent grain boundary, interfacial energy
be γα−β , radius of groove be r. A1α−β and A2α−β are respectively the interfacial area
between α and β before and after nucleation.
Fig. 6 Schematic diagram

of lamellar cementite fusing
and spheroidization process
336 S. Liu et al.
During the nucleation and growth of cementite, the change of the Gibbs free
energy is [15]:
G = - VGP + (A2α−β - A1α−β )γα−β (1)
When homogeneous nucleation, the critical radius is r∗ = 2γα−β /GP , and the
critical Gibbs free energy difference is G∗ = (16/3)π · γα−β 3
/G2P .
When heterogeneous nucleation, the critical radius is r = (1/(2 + cos θ))r∗ and
the critical Gibbs free energy difference is G = ((1 − cos θ)/(4 + 2 cos θ))2 G∗ .
If θ → 90°, cos θ = 0 and r = (1/2)r∗ , G = (1/16)G∗ , but if θ → 0°, cos θ =
1 and r = (1/3)r∗ , G = 0. As θ increases, the critical nucleation energy increases.
The critical nucleation energy at the site which θ = 0° is 0 (shown in Fig. 6), there
is no nucleation barrier at all, and a new phase can form without thermal activation
energy.
This formula shows that the critical nucleation energy inside the groove is always
higher than that at the planes near the groove, therefore, it is preferred to nucleate
at these planes, of which curvature radius approaches infinity, according to colloidal
equilibrium theory, there is relatively low concentration of carbon in matrix near the
planes, however, the curvature radius at the groove is small so the carbon concen-
tration is high, resulting in a diffusion of carbon from high to low concentration. In
order to maintain a dynamic balance of carbon in a tiny area between cementite and
adjacent ferrite, carbide is precipitated on the planes near the groove but cementite
inside the groove is dissolved. As soaking time increases, the lamellar cementite
gradually melts, and is finally spherized.
Effect of Soaking Time on Spherical Carbides
DICTRA was used to simulate the size charge of carbide during heat treatment, which
is a general software package for simulation of Diffusion Controlled Transforma-
tions in multicomponent systems and is particularly suitable for treating problems
involving a moving boundary. Figure 7 shows the schematic diagram of the Cell
model for the present DICTRA simulation and the calculation result.
As is shown in Fig. 7b, a carbide particle grows rapidly in the initial stage of the
heating process. When the time exceeds 5 h, the growth rate of the carbide particle
becomes slower and the carbide particle hardly grows up until 15 h later.
In order to study Ostwald ripening behavior of carbides during the annealing
process, the samples were kept at 705 °C for different time according to the thermal
schedule in Fig. 2. Thirty fields of view were observed based on SEM and the size of
carbides was counted, as shown in Fig. 8a. The radius of carbides increased with the
increase of soaking time and was the same as the spherodization ratio. In the early
stage of the annealing process, carbides began to nucleate and grow rapidly so the
radius was a little bit small. It was till 6 h that nucleation of carbides ended and the
samples entered the second stage in which carbides grew up slowly. The concentration
Fig. 7 Schematic diagram of the Cell model in DICTRA (a) and the result of calculation (b)
Fig. 8 Parameters of spheroidized samples after different soaking time
of carbon in the matrix decreased, resulting in a decreasing in the growth rate of

carbides but the spheroidization process was still going on. When the soaking time
was 16 h, the samples entered a third stage in which the supersaturation of carbon
in the matrix was low. At this moment, the size of carbides hardly changed and
only short distance diffusion of carbon occurred in this stage, so the spheroidization
ratio increased faster, as is shown in Fig. 8a. The experimental results are in good
agreement with the simulation results of DICTRA.
According to Wagner [16],
r3 = βD σ c0 t/(RT) + A (2)
where r is the average radius of the carbides at time t, D is the diffusion coefficient
of carbon, D = 0.013 · exp(−81400/RT) cm2 /s, is the mole volume, 23.395
cm3 /mol, σ is the interface energy between carbide and matrix, 2.27 J/m2 , R is the
universal gas constant 8.314 J mol−1 K−1 and T is absolute temperature, 978 K, and
the limit concentration c0 of carbon in the matrix is 0.77%, A is constant and β is
a correction factor. Based on the measured value, the average value of correction
338 S. Liu et al.
Table 3 The relative errors between the calculated and the experimental size of carbides
Time (h) 3 6 9 16 22 28
The relative error (%) 15.92 2.23 3.14 5.83 8.57 12.41
factor β and constant A is calculated, which is 7.02E-05 and 1.2E-21, respectively.

The relative errors between the calculated and the experimental size of carbides is
shown in Table 3. The nucleation process of carbides and the decrease of carbon
concentration is not considered during the first and last stage respectively in the
theoretical calculation, so the relative errors is a little larger than that of the second
stage.
In summary, the subcritical annealing process which chooses 16 h soaking time
can achieve better spheroidization effect. Compared with the intercritical annealing
process, which needs 24 h for the furnace loading time, the subcritical annealing
process only needs 19 h, not only saves a lot of time and reduce energy consumption
but also improves the spheroidization level.
Conclusions
The effect of different annealing processes on spheroidization level of low-carbon low

alloy steel FAS3420H has been studied, and the Ostwald ripening behavior has also
been studied during different soaking time, a formula is promoted to quantitatively
characterize the progress of Ostwald ripening of the carbide particles. The results
are as follows:
(1) Intercritical annealing process not only reduces the precipitation of spheroidal
carbides of studied steel, but also makes the pearlite become coarser and larger
which distributes more unevenly, this microstructure is not beneficial to improve
the performance of cold heading.
(2) After normalizing and subcritical annealing, the lamellar pearlite in the sam-
ple has been almost dissolved and a large number of small, evenly dispersed
spherical carbide particles forms, meeting the requirements of cold heading.
The heat treatment process of 850 °C normalizing/0.5 h + 705 °C subcritical
annealing/16 h + subsequent air cooling is a suitable spheroidizing process for
studied steel.
(3) The formula characterizes three stages of Ostwald ripening of carbides in low-
carbon low alloy steel FAS3420H. During the early stage, the nucleation of
carbides occurs so the size of carbides is small. With soaking time increasing, the
growth of carbides is gradually dominant. When soaking time reaches 16 h, the
size of carbides nearly do not change, at this time only short distance diffusion
of carbon occurs in the third stage, so the spheroidization rate increases faster.
Acknowledgements The authors gratefully acknowledge the financial support provided by

National Natural Science Foundation of China (Grant No. 51674020) and National Key Research
and Development Program of China (No. 2016YFB0300102).
References
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at 800 °C. J Iron Steel Res Int 24(8):858–864
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Study of the Influence of the Angle
Between the Bottom Blowing Elements
on the Dynamic Conditions in a 300t
Converter
Liujie Yao, Rong Zhu, Huixiang Yu, Kai Dong, Qiang Feng and Yixing Tang
Abstract In this paper, the converter steelmaking process is studied using numerical
simulations and hydraulic model experiments, in order to examine the influence of
the angle between the bottom blowing elements and the gas flow rate, on the flow
characteristics of the molten pool. A 300t converter is used. The results demonstrated
that the mixing time and velocity field distribution, of the molten pool, changed
with the angle between the bottom blowing nozzles. Increasing the bottom blowing
gas flow rate improved the dynamic conditions of the bath, accelerating the mass
transfer process and reducing the volume fraction of the dead zone. Two arrangements
with angles of 90° and 105° were applied to two furnace regimes. The industrial
experiments showed that a large angle between the nozzles was favorable because
it accelerated the decarburization and dephosphorization. This reduced the endpoint
carbon–oxygen equilibrium of molten steel and reduced the content of iron oxide
and TFe in the endpoint slag.
Keywords 300t converter · Hydraulic model · Numerical simulation · Angle

between the elements
Introduction
The converter steelmaking process is complex, involving thermodynamics and

dynamics. Factors involved include a top-blown supersonic jet, the movement of
the bottom blow stream, the flow of molten steel, and slag and the mass transfer
L. Yao · R. Zhu (B) · H. Yu · K. Dong · Q. Feng · Y. Tang

e-mail: zhurong1_1201@126.com
H. Yu

https://doi.org/10.1007/978-3-030-36540-0_31
342 L. Yao et al.
process between the molten steel and slag. Among these factors, the bottom blow
stream has the greatest influence on the dynamics.
Since the middle of the twentieth century, with the development of numerical sim-
ulation technology, researchers have carried out many studies of the fluid dynamics in
the process of converter steelmaking and used hydraulic simulation results to verify
these tests [1–4]. Lou et al. [5] used numerical simulations and hydraulic experi-
ments to analyze the dynamics of the pool in the converter. They considered that
when the bottom blowing component is distributed in the range of 0.3–0.4 D (D is
the diameter of the converter furnace), the bottom blowing stream has the greatest
stirring effect on the molten pool. Liu et al. [6] established a three-dimensional model
for the converter, and carried out numerical simulations and hydraulic experiments
of different schemes. They determined a mixing law for the bottom blowing stream
on the molten metal pool. Caffery [7] established a model for energy exchange in
molten metal pools and deduced that the bottom blow stream is beneficial to the uni-
form distribution of bath temperature. Ramirez [8] conducted a numerical simulation
study on the electric arc furnace to investigate the flow characteristics of the molten
metal pool. Gu et al. [9] used an Euler-Lagrangian model to perform a two-phase
flow, numerical simulation study of a steelmaking process, with two bottom blowing
elements.
In summary, research on the bottom blowing process of the converter has always
been an important topic. Therefore, in this paper we look at a 300t converter, and
adjust the influence of the bottom blowing stream on the dynamic characteristics of
the molten pool, by adjusting the angle between the bottom blowing elements.
Mathematical Modeling
In this study, a three-dimensional full-scale mathematical model is established for

a 300t converter. The numerical simulation process used the volume of fluid (VOF)
[10] approach, to investigate the effect of the bottom blowing gas on the dynamics
of molten steel, while altering the angles of the elements.
A. Assumptions
The assumption is specific: (1) The bottom blowing gas (argon and compressed air)
and liquid (steel and water) are non-isothermal fluids. (2) The bottom blowing gas is a
compressible Newtonian fluid, and the molten steel is an incompressible Newtonian
fluid. (3) Chemical reactions in the pool are ignored. (4) The wall of the converter is
nonslip, and the velocity near the wall is calculated according to the standard wall
Eq. (5) The viscosity of each fluid phase and the surface tension between the phases
are considered to be constant.
B. VOF Modeling
The VOF model is a multi-phase model, that is commonly used for numerical
simulations of steelmaking. For the ith phase, the continuity equation is as follows,
Study of the Influence of the Angle … 343
1
n
∂αi Sα
+ νi · ∇αi = i + (ṁi j − ṁ ji ) (1)
∂t ρi ρi i=1

where ν i is the speed in the direction i, ms−1 , ṁi j is the mass transfer from phase i to
phase j, kg, and ṁ ji is the mass transfer from phase j to phase i, kg. Sαi is the source
term, which is zero. The sum of the volume fractions of the phases in the calculation
process is 1 as shown in the following equation.

n
αi = 1 (2)
i=1
All variable properties that appeared in the transport equation were determined
for each phase, the equations are expressed as

n
n
ρ= αi ρi μ = αi μi (3)
i=1 i=1
where ρ is the average density of fluid, kg m−3 , ρi is the density of ith phase, kg m−3 ,
and the gas satisfied the ideal gas equation, i.e. p = ρ RT , and the density of the liquid
was considered to be constant; μ is average viscosity of volume fraction, kg m−1 s−1 ,
μi is the viscosity of ith phase, kg m−1 s−1 .
In the VOF model, the momentum equation was given in Eq. 5.
∂
ρ ν + ∇ · (ρ ν ν ) = −∇ p + ∇ · μ ∇v + ∇v T + ρ g + F (4)
∂t

where ρ and μ are given in Eqs. (3) and (4); ν is the instantaneous velocity of phase,
m s−1 ; p is static pressure, Mpa; g is the force of gravity, N; F is volume force, N.
In the VOF model, the surface tension is regarded as a volume force, and the
continuum surface force model is used, this is expressed as follows,

fσ = σ κ · ∇αd V =σ κi · (∇αi )Vi (5)
V
where σ is surface tension coefficient, N m−1 , in this paper the

value σ is 1.5 N m−1 ;
of
∇α
κ is surface curvature, constrained by the equation κi = − ∇ · |∇α|
i
C. Energy Model
The energy equation is shared among the phases, this is shown in the following
expression.
∂
(ρ E) + ∇ · (ν (ρ E + p)) = ∇ · ke f f ∇T + Sh (6)
∂t
344 L. Yao et al.
D. Turbulence Modeling
In this paper, the turbulence model used is a standard k-ε turbulence model. The
expression of the turbulence kinetic energy, k, and rate of dissipation, ε, are as follows,

∂ δ δ μt δk
∂t
(ρk) +
δxi
ρku i =
δx j
μ+
σk δx j
+ G k + G b − ρε − Y M + Sk (7)

∂ δ δ μt δε ε ε2
∂t
(ρε) +
δxi
ρεu i =
δx j
μ+
σε δx j
+ C1ε G k + C3ε G b − C2ε ρ
k k
+ Sε (8)
where C1ε , C2ε , and C3ε are constants [11], σk and σε are the turbulent Prandtl numbers
for k and ε, respectively. Sk and Sε are user-defined source terms, that are set to zero
for this study.
E. Computation Methodology
In this study, the influence on the molten pool dynamic characteristics, from the
angles between the four bottom blowing elements, was examined. This was done for
a 300t converter, using numerical and water simulations. The experimental scheme
is shown in Table 1.
In order to ensure the accuracy and effectiveness of the numerical simulation
results, three-dimensional full-scale modeling of the 300t converter was carried out.
Figure 1 is a schematic diagram of the converter geometry model and the bottom
blowing nozzle arrangement, Table 2 shows the specific values of the geometrical
parameters. Spatial discreteness is an unobtainable step in the numerical simulation,
Table 1 Parameters used in the present simulation and experiments

Scheme γ (°) δ (°) Bottom blowing flow rate (Nm3 /h))
Prototype Hydraulics experiment
1 22.5 22.5 600/800/1000 1.61/2.15/2.68
2 30 30 600/800/1000 1.61/2.15/2.68
3 45 45 600/800/1000 1.61/2.15/2.68
4 60 45 600/800/1000 1.61/2.15/2.68
Fig. 1 Geometric
representations of the
converter and the bottom
blowing nozzles arrangement
Table 2 Parameters used in the present simulation and experiments

Items Converter prototype Water model
Converter capacity (ton) 300 –
D1 (mm) 3600 514.3
D2 (mm) 6532 933.1
H (mm) 10257 1465.3
h1 (mm) 1748 249.7
h2 (mm) 5328 761.1
α (°) 25 25
β (°) 30 30
R1 (mm) 5567 795.3
R2 (mm) 1618 231.1
Bottom blowing arrangement diameter, D3 (mm) 3266 466.6
Bottom nozzle hydraulic diameter, d (mm) 8.3 1.2
Molten bath depth, h (mm) 1844 263.4
Bottom blowing flow rate (Nm3 /h) 600/800/1000 1.61/2.15/2.68
as shown in Fig. 2. In order to verify the number of grids that is most suitable for
the calculation model used in this paper, the area-weighted average velocity of the
molten bath was monitored under the conditions of a coarse mesh (423759), a fine
mesh (612896), and a medium mesh (562685). Figure 3 is the average velocity curve
for the monitoring surface, with respect to the calculation time. The results showed
that the average velocity for the fine mesh and the medium mesh surface differed
by 1.5%, and the average velocity of the medium mesh and the coarse mesh surface
differed by 4.6%. Therefore, in the subsequent numerical simulations, medium grids
are used.
The choice of boundary conditions in the numerical simulation calculation pro-
cess is especially important for the accuracy of the results and the stability of the
Fig. 2 Detailed grid

arrangements of numerical
simulation model (scheme 4)
346 L. Yao et al.
Fig. 3 Fluid flow velocity of

the molten bath under three
grid levels (scheme 4)
calculation. The inlet boundary condition of bottom blowing elements was a mass
flow inlet, and the inlet pressure was set at 2.0 × 105 Pa. The outlet boundary condi-
tion was a pressure outlet, and the pressure was set at 1.10 × 105 Pa. For the walls,
a nonslip condition was used and the standard wall function was adopted.
During the numerical simulation process, the first-order implicit transient method,
using a pressure-based solver, was applied. The pressure-velocity coupling scheme
was achieved using the PISO algorithm, the pressure discrete format used PRESTO!,
and the interpolation scheme used a Geo-Reconstruct method. A second-order
upwind scheme was applied to the momentum equations and a first-order upwind
scheme was applied to the turbulent kinetic energy equation and turbulent dissipation
rate equation. In this paper, when the energy residuals were less than 1 × 10−6 , and
the residuals of other variables were less than 1 × 10−3 , the calculation process was
considered to have reached convergence. The numerical simulation process used a
time step of 1 × 10−5 s.
Hydraulics Experiment and Computational Verification
A. Hydraulics Experiment
The model scale used for the hydraulics experiment was 1/7, and the mold was made
of plexiglass. The water model experimental apparatus are shown in Fig. 4. Table 3
shows the physical properties of the fluid used in this study.
During the steel making process, bubbles are mainly subject to inertial forces and
gravity . In order to satisfy the dynamic similarity, the Froude number of the water
Fig. 4 Experimental instruments of water model experiment
Table 3 Physical properties of fluid

Item Steel Water Argon Air
Density, kg/m3 7200 1000 1.63 1.225
Viscosity, kg/m/s 6.4 × 10-3 0.001 2.125 × 10-5 1.789 × 10-5
Surface Tension, N/m 1.5 0.071 – –
Thermal conductivity, W/m/K 15 0.6 0.0158 0.0242
Specific heat, J/kg/K 670 4182 520.64 1006.43
Temperature, K 1873 300 300 300
model must be equal to the Froude number of the prototype. The equations are as
follows,
Frw = Fr p (9)
Q 2w ρgw Q 2p ρgp
π
· = π
· (10)
gL w (n · 4 · Lw · 3600)
2 2 ρlw − ρ gw gL p (n · 4 · L p · 3600)
2 2 ρlp − ρgp
25 1 1
Lw ρgp 2 ρlw − ρgw 2
Qw = Q p · · · (11)
Lp ρgw ρlp − ρgp
25 1 1
Lw ρgp 2 ρlw 2
Qw = Q p · · · (12)
Lp ρgw ρlp
where the subscripts w and p represent the water model and the prototype respec-
tively; u is the bottom blowing gas velocity, m/s; g is the gravitational acceleration,
m/s2 ; ρ is the density, kg/m3 ; L is the characteristic size, m; Q is the bottom blowing
gas flow, Nm3 /h; n is the number of bottom blowing components. Since the liquid
density is much larger than the gas density, the effect of gas density is ignored in the
fourth term on the right side of the Eq. 11. The bottom blowing gas flow rate for the
hydraulics experiment and the prototype are shown in Table 2.
348 L. Yao et al.
In the water model experiment, a saturated potassium chloride solution (generally

30 ml) was used as a tracer; two DJS-10C conductivity electrodes are arranged in an
asymmetric position at the bottom of the furnace, to detect the change in conductivity
of the molten pool, thereby obtaining a mixing time for the pool. In order to eliminate
human error, each group of experiments was repeated three times, and the arithmetic
mean was obtained.
B. Computation Validation
In order to verify the applicability of the model, during the numerical simulation
process in Sect. 2, the same model was used as in the water model experiment. During
the calculation, the tracer was added at the same position as that of the conductivity
electrode in the water model. When the mole fraction of the tracer reached 95% of
the final mole fraction, it was considered that this was the mixing moment.
Figure 5 shows the conductivity curve for the molten pool, with respect to the
monitoring time, in the water model experiment of Scheme 4. It can be seen from the
figure that the conductivity of the two electrodes is equal before the addition of the
tracer, this is consistent with the fluid continuity characteristics. When the tracer was
added, the conductivity at that point increases. As time passes, the conductivity again
becomes equal. For this study, when the difference between the two conductivity
curves is less than 5%, the moment of mixing is considered to have been reached.
Figure 6 shows the tracer mole fraction curve during the numerical simulation of the
water model. It can be seen from the figure that the mole fraction at the detection
point gradually decreases with time, it is considered that when the difference between
the two mole fraction curves is less than 5%, the mixing time is reached.
Fig. 5 The electronic conductivity change in the water model experiment (scheme 4)
Fig. 6 The tracer mole fraction change in the numerical simulation (scheme 4)
Table 4 The mixing time of pool under water model experiment and numerical simulation
Item The bottom blowing gas flow Scheme
rate 1 2 3 4
Water model experiment (s) 600 82.3 78.2 74.7 72.8
800 67.4 63.3 60.5 58.7
1000 62.9 57.9 56.2 55.7
Numerical simulation (s) 600 84.1 75.3 79.4 74.2
800 70.9 66.9 59.5 58.3
1000 63.5 56.5 56.8 55.8
Table 4 shows the mixing times for the water model experiment and the numerical
simulation. It can be seen from the table that the maximum absolute error of the
mixing time is less than 6.4%. Therefore, it can be considered that the model selected
for the numerical simulation process is applicable.
A. Analysis of the Water Model Experiment
For the hydraulic experiment of the steelmaking process, the mixing time of the
molten pool is an important evaluation index for the experimental scheme.
It can be seen from Fig. 7 that while increasing the bottom blowing flow rate
350 L. Yao et al.
Fig. 7 The mixing time of water model experiments
from 600 Nm3 /h to 1000 Nm3 /h, the mixing time is gradually reduced and the ampli-
tude decrease gradually slows down. The mixing time of the molten pool, in each
experimental scheme, is positively correlated with the angle of the bottom blowing
element.
B. Analysis of the Numerical Simulation
In this study, the influence of the angle of the bottom blowing element, on the dynamic
characteristics of the molten pool is studied by numerical simulation. Figures 8 and
9 show velocity distribution diagrams of the longitudinal section of the molten pool
and the cross sections at different depths, with different colors representing different
speeds. Red represents a high-speed zone and blue represents a low-speed zone.
According to the results of the water model experiment, and in the literature, when
the bottom blowing flow rate is increased, it improves the stirring of the molten pool.
scheme 1 scheme 2 scheme 3 scheme 4
Fig. 8 Velocity distribution on longitudinal section in the molten pool


Bath depth of 700 mm

Bath depth of 1800 mm
Fig. 9 Velocity distribution at the cross section of the molten pool
Therefore, the following discussion focuses on the numerical simulation results when
the bottom blowing flow rate is 800 Nm3 /h, because it is an intermediate speed value.
It can be seen from Fig. 8 that the low velocity zone in the molten pool is mainly
distributed between the central region and near the furnace wall region. The velocity
of the molten pool, near the bottom blow stream, is relatively large. As the angle is
increased, the uniformity of the velocity distribution in the molten pool gradually
increases.
It can be seen from Fig. 9, that as the depth of the molten pool increases, the
uniformity of the velocity distribution increases. The reason for this is that the volume
gradually expands during the ascending of the bottom blowing gas, therefore the
kinetic energy is gradually transferred to the molten pool, and the velocity of the
molten bath gradually increases. For a constant molten pool depth, as the angle
between the bottom blowing elements increases, the velocity of the molten pool
gradually increases. At the same time, the distribution area of the low velocity region
in the molten pool gradually decreases. It can be seen that the center and the near
wall, low velocity regions, in Scheme 1, are gradually reduced to the near wall area
in Scheme 4. This feature correlates well with the position of the dead zone in the
water simulation process.
C. Chemical Reactions in the Molten Bath
1. Decarburization efficiency and endpoint carbon–oxygen equilibrium
For converter steelmaking, the decarburization reaction is the central subject of
research. The main reaction formula is Eq. 13.
352 L. Yao et al.
[C] + [O] = C O(g) G θ = −22200 − 38.34T (J/mol) (13)
pC O pC O
Kc = = (14)
a[c] · a[O] fC [%C]f O [%O]
Equation 14 is the reaction equilibrium constant of Eq. 13, where pCO is the partial
pressure of carbon monoxide, generally taken as 1 atm; a[C] and a[O] are the activity of
carbon and oxygen, respectively, in molten steel, fc and fo are the activity coefficients
of carbon and oxygen, [%C] and [%O] are the mass percentages of carbon and oxygen
in molten steel. For the end-point molten steel, the carbon content is relatively low,
so fc and fo are both 1, therefore Eq. 14 can be simplified to Eq. 15.
1
Kc= (15)
[%C][%O]
According to the physicochemical principle, the Gibbs free energy analysis of

Eq. 14 can be obtained from Eq. 16. It is observed that the product of the carbon
and oxygen mass fraction in the molten steel is only related to temperature, and m
= [%C][%O] is defined as the carbon and oxygen concentration of molten steel.
1160
lg([%C][%O])= − − 2.003 (16)
T
The tapping temperature of the converter is generally around 1873 K. When pCO
= 1 atm, the content of carbon–oxygen equilibrium in the molten steel is 0.0024.
In the industrial experiment process, a total of 3282 test data were taken for the
entire furnace campaign. The distribution of the scatter plots is shown in Fig. 10. It
Fig. 10 Distribution of decarburization efficiency in the molten pool

can be seen that the distribution of carbon–oxygen equilibrium in the steel sample,
at the end of Scheme 4, was lower than that in Scheme 3; Fig. 11 is an average of the
test data. It was found that the content of carbon–oxygen equilibrium in Scheme 4
was 9.52% lower than in Scheme 3. From this result, it can be seen that the stirring
of the molten pool, at the bottom of Scheme 4, is better than that shown in Scheme 3.
2. Dephosphorization effect
Phosphorus in molten steel can cause a cold and brittle phenomenon. Therefore, the
dephosphorization reaction is important in the steelmaking process. In the actual
production process, the dephosphorization reaction is carried out by using calcium
oxide, the reaction formula is shown in Eqs. 17, 18 and 19 is a simplified equation
of the dephosphorization reaction.
2[P] + 5(FeO) + 3(Ca O) = (3Ca O · P2 O5 ) + 5Fe(l) (17)
2[P] + 5(FeO) + 4(Ca O) = (4Ca O · P2 O5 ) + 5Fe(l) (18)
a(P2 O5 ) 36850
2[P] + 5[O] = (P2 O5 ) lg K P = = − 29.07 (19)
[%P] [%O]
2 5 T
The dephosphorization reaction is a typical slag-steel reaction. Under the con-

dition of certain bath temperature and alkalinity, a good kinetic performance of the
molten pool increases the mass transfer rate of the elements in the molten steel. In the
industrial test process, a total of 1992 samples were taken for the dephosphorization
rate, and the average value distribution is shown in Fig. 12. It can be seen from the
industrial experimental results that the dephosphorization rate of Scheme 4 is 1.06
times that of Scheme 3. This conclusion indicates that the mass transfer rate of the
elements in the molten pool of Scheme 4 is faster than that of Scheme 3, and thus is
favorable to the reaction of the slag steel in the furnace.
Fig. 11 Average endpoint

carbon–oxygen equilibrium
of scheme 3 and scheme 4
354 L. Yao et al.
Fig. 12 Average
dephosphorization rate of
scheme 3 and scheme 4
Endpoint Slag Composition
The slagging regime has a huge impact on steelmaking. The FeO has a great influence
on the consumption of steel materials, the utilization rate of alloys, and the refining
process. However, due to the kinetic conditions of the molten pool, a part of FeO still
exists in the slag. The higher the FeO content in the slag, the greater the consumption
of the steel material.
(FeO) + [C] = Fe + C O(g) (20)
It can be seen that the molten pool dynamic conditions have a significant impact
on the control of FeO content, under certain conditions of the top blowing process.
In the industrial experiment, 1777 sampling samples were taken and analyzed. The
results are shown in Fig. 13. The FeO content in Scheme 4 is reduced by 3.67% more
than in Scheme 3. This conclusion is in good agreement with both the numerical and
water simulation results.
Fig. 13 Content of FeO of

scheme 3 and scheme 4 in
endpoint slag
Conclusions
This study has established a 300t converter experimental water model, a three-
dimensional numerical simulation model, and industrial experiments have been con-
ducted. The influence of the bottom blowing stream, on the dynamic characteristics
and chemical reactions in the molten pool, under different angles of bottom blowing
elements, is studied.
The mathematical model applied in the numerical simulation process shows good
consistency with the experimental results from the water model. With an increase
in the angle between the bottom blowing elements, the stirring ability of the bottom
blowing stream on the molten pool is enhanced. This conclusion is clearly verified in
both the numerical simulation and water simulation process. With an increase in the
angle between the bottom blowing elements, the carbon and oxygen concentration,
FeO, dephosphorization rate and other indicators of impurities in the actual pro-
duction process, show a decreasing trend. The results from the production process
experiments not only correlate well with the results of the water model experiment,
but also show a good level of consistency with the numerical simulation results.
References
1. Zhang MY, Sun XK, Wang GD, Liu XH, Zhang MH (2000) Current conditions and development
of application of mathematical simulation technology in China’s iron and steel industry. Res
Iron Steel 3:53–58
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parameters in LBE. J Mater Metall 2(1):21–24
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vessel using cold model study and thermodynamic analysis. ISIJ Int 46(8):1171–1176
4. Chen R, Luo ZG, Yang CG, Zou ZS (2008) A study of water model on size and space distribution
of slag dispersed phase on combined blowing of converter. Special Steel 1:13–15
5. Lou WT, Li Y, Zhu MY (2011) Numerical simulation of gas-liquid two-phase popularity in
top-bottom combined blowing converter. Chin J Process Eng 11(6):926–932
6. Liu F, Zhu R, Dong K, Bao X, Fan SL (2015) Simulation and application of bottom-blowing
in electrical arc furnace steelmaking process. ISIJ Int 55(11):2365–2373
7. Luomala Matti J, Fabritius Timo MJ, Härkki Jouko J (2004) The effect of bottom nozzle
configuration on the bath behavior in the BOF. ISIJ Int 44(5):809–816
8. Lai ZY, Xie Z, Zhong LC (2008) Influence of bottom tuyere configuration on bath stirring in
a top and bottom combined blown converter. ISIJ Int 48(6):793–798
9. Gu L, Irons GA (2001) Physical and mathematical modeling of bottom stirring and gas evolution
in electric arc furnaces. Iron Steelmak 28(1):57–68
10. Hirt CW, Nichols BD (1981) Volume of fraction (VOF) method for the dynamics of free
boundaried. J Comput Phys 39:201–225
11. Launder BE, Spalding DB (1972) Lectures in mathematical model of turbulence. Academic
Press, London
Part V
Extraction and Recovery of Metals
Recovery of Chromium from Ferronickel
Slag via Alkaline Roasting Followed
by Water Leaching: Effect of Roasting
Atmosphere
Foquan Gu, Yuanbo Zhang, Zhiwei Peng, Huimin Tang, Manman Lu,
Shuo Liu, Zijian Su, Mingjun Rao, Guanghui Li and Tao Jiang
Abstract Ferronickel slag is a hazardous industrial waste containing a relatively

high amount of chromium, which poses a great potential threat to the environment.
It is of great significance to recover chromium from the slag for both economic and
environmental benefits. In this study, recovery of chromium from ferronickel slag
via alkaline roasting followed by water leaching was investigated, with an emphasis
on the effect of roasting atmosphere on the phase transformation of ferronickel slag
during the alkaline roasting process.
Keywords Ferronickel slag · Alkaline roasting · Water leaching · Chromium ·

Recovery · Roasting atmosphere
Introduction
With the development of the rotary kiln-electric furnace (RKEF) process for the pro-
duction of ferronickel alloy from laterite ores in China, the generation of ferronickel
slag has exceeded 40 million tons in 2018 [1–3]. However, it had a very low utiliza-
tion percentage (<10%) [4, 5]. Because ferronickel slag contains a relatively high
amount of chromium, which poses a great potential threat to the environment, it is
important to recover the element from the slag [6, 7].
Extraction of chromium from primary ores and secondary resources through alkali
extraction has been investigated by many researchers [8–10]. The main processes
include alkaline roasting-water leaching, alkaline leaching, and acid leaching. At
F. Gu · Y. Zhang (B) · Z. Peng (B) · H. Tang · M. Lu · S. Liu · Z. Su · M. Rao · G. Li · T. Jiang

School of Minerals Processing and Bioengineering, Central South University, Changsha, Hunan
410083, China
e-mail: sintering@csu.edu.cn
Z. Peng
e-mail: zwpeng@csu.edu.cn
National Engineering Laboratory for High Efficiency Recovery of Refractory Nonferrous Metals,

https://doi.org/10.1007/978-3-030-36540-0_32
360 F. Gu et al.
present, because of economic and technical problems, only the alkaline roasting-
water leaching processes have been used widely [11]. The traditional recovery of
chromium from chromite ore is based on roasting with Na2 CO3 at temperatures above
1100 °C [12], which is very energy-intensive. For this reason, it is not economical
for the treatment of low grade chromium resources. More seriously, chromium is
dissolved in the solution as toxic Cr (VI), which is harmful to the human health and
environment.
Recently, a novel method for selective recovery of chromium from ferronickel slag
without generation of toxic Cr (VI) by using a relatively small addition of Na2 O2 as
additive for low-temperature lime-free alkaline roasting, followed by water leaching
was proposed [4]. It showed that 92.33% of Cr was obtained under the optimal
conditions of the mass ratio of ferronickel slag to Na2 O2 of 1, roasting temperature
of 600 °C, roasting time of 1 h, leaching temperature of 50 °C, leaching time of 1 h,
and liquid-to-solid ratio of 10 mL/g. Because of its promising environmental and
economic benefits, this method was considered viable for the selective extraction of
chromium from ferronickel slag. However, the influence of roasting atmosphere on
the recovery of chromium from ferronickel slag is still unclear.
In the present study, the effect of roasting atmosphere on the selective extraction
of chromium from ferronickel slag on the basis of alkaline roasting using Na2 O2
followed by water leaching was investigated in detail based on the thermodynamic
analysis and the experimental exploration.
Experimental
Materials
The ferronickel slag was obtained from a ferronickel smelting plant in China. The
main chemical composition of the slag is shown in Table 1. It was featured by high
contents of silica and magnesia, with the Cr2 O3 content of 2.11 wt %. The main
mineral phase of the slag was olivine (Mg1.8 Fe0.2 SiO4 ), except for a small amount
of glassy phase [5]. The sodium peroxide (Na2 O2 ) of analytical grade was used for
roasting before water leaching.
Table 1 Main chemical compositions of ferronickel slag (wt %)

Component SiO2 MgO FeO Al2 O3 CaO Cr2 O3
Content 48.29 30.95 7.39 4.04 2.40 2.11
Recovery of Chromium from Ferronickel Slag … 361
Methods
Thermodynamic Calculation
For thermodynamic analysis of the process, the software FactSage 7.2

(Thermfact/CRCT, Montreal, QC, Canada; GTT-Technologies, Herzogenrath, Ger-
many) was used to calculate the phase diagrams of the Cr2 O3 -Na2 O2 system in dif-
ferent atmospheres and the diagram of Gibbs free energy changes versus temperature
(r G
m -T) for relevant reactions.
Alkaline Roasting and Water Leaching
In the beginning, the ferronickel slag sample (all particles passing 0.074 mm sieve)
was mixed homogeneously with a predetermined amount of alkaline agent (Na2 O2 )
before loading in an alumina crucible. Then, the mixture was loaded in a horizontal
tube furnace, which was maintained at 600 °C. The N2 –O2 mixed gas was introduced
to the furnace for roasting. The O2 concentration in the mixed gas was precisely
adjusted by flowmeters and the flow rate was fixed at 4.0 L/min. After roasting for
given periods of time, the samples were cooled to room temperature.
For leaching, the roasted sample was ground to all particles passing 0.074 mm
sieve. Then, 10 g of roasted sample was taken for water leaching at the stirring speed
of 300 rpm in a 200 mL beaker heated using a water bath. After vacuum filtration,
the concentrations of Cr and other relevant elements in the solution were measured.
Their contents in the roasted sample and leaching residue were also analyzed to
determine their leaching percentages. The leaching percentage was calculated using
the following equation:

W2 M 2
η= 1− × 100% (1)
W1 M 1
where η is the leaching percentage of the element; W1 and W2 are the elemental
contents of leaching residue and roasted sample, respectively; M1 and M2 are the
masses of leaching residue and roasted sample, respectively.
Analytical Methods
The contents of Cr2 O3 in the leach liquor and roasted mixture were measured by
ion coupled plasma atomic emission spectroscopy (ICP-AES, ICAP7400 Radial,
Thermo Fisher Scientific, USA). The contents of other elements in the raw material
and residue after alkaline roasting followed by water leaching were measured by
X-ray fluorescence spectrometry (XRF, Axios Max, PANalytical, Netherlands). The
phase constituents of the samples were determined by using an X-ray diffraction
spectrometer (XRD, D/max 2550 PC, Rigaku Co., Ltd, Japan) using a Cu anode
with the wavelength of 1.54056 Å, step scan mode, and step length of 0.02°.
362 F. Gu et al.
The reaction behavior of Cr2 O3 –Na2 O2 with in the ferronickel slag in different atmo-
spheres can be deduced from the phase diagram of the Cr2 O3 –Na2 O2 system. Fig-
ures 1, 2, 3 and 4 show the phase diagrams of the Cr2 O3 –Na2 O2 system under the
oxygen pressure of 0 atm, 0.2 atm, 0.4 atm, and 1 atm, respectively. As shown
in Fig. 1, when the oxygen pressure is 0 atm, NaCrO2 and Na2 CrO4 are the two
main products of the reactions between Na2 O2 and Cr2 O3 . As the oxygen pressure
increases to 0.2 atm, the phase diagram of the Cr2 O3 –Na2 O2 system is similar to
that at 0 atm. The suitable Na2 O2 /(Cr2 O3 +Na2 O2 ) mass ratio to ensure the complete
reaction between Na2 O2 and Cr2 O3 is 0.42–0.6. As shown in Fig. 3, when the oxygen
pressure is 0.4 atm, Na2 CrO4 is the only product of the reaction between Na2 O2 and
Cr2 O3 . As shown in Fig. 4, when the oxygen pressure is 1 atm, the phase diagram of
the Na2 O2 –Cr2 O3 system is similar to that at 0.4 atm.
Based on the above analysis, it is deduced that NaCrO2 and Na2 CrO4 in the
Na2 O2 –Cr2 O3 system can be formed according to the following reactions:
Fig. 1 Phase diagram of the Cr2 O3 –Na2 O2 system (p(O2 ) = 0 atm)

Fig. 2 Phase diagram of the Cr2 O3 –Na2 O2 system (p(O2 ) = 0.2 atm)
3Na2 O2 + Cr2 O3 = 2Na2 CrO4 + Na2 O (2)
2Na2 O2 + 2Cr2 O3 = 4NaCrO2 + O2 (3)
4Na2 O2 + O2 + 2Cr2 O3 = 4Na2 CrO4 (4)
The r G m -T diagram of Eqs. (2), (3), and (4) is shown in Fig. 5. It shows that
both NaCrO2 and Na2 CrO4 can be formed in the temperature range up to 1000 °C
(r Gm < 0). The NaCrO2 is more prone to generate, which would prevent formation
of toxic Cr (VI). In view of the phase diagram of the Cr2 O3 –Na2 O2 system at dif-
ferent oxygen pressure, it is concluded that with the oxygen pressure less than 0.4,
the reactions between Na2 O2 and Cr2 O3 (Eqs. 2 and 3) will result in NaCrO2 and
Na2 CrO4 . However, when the oxygen pressure exceeds 0.4, the reactions between
Na2 O2 and Cr2 O3 , as given by Eq. (4), will produce Na2 CrO4 . Thus, it is feasible
to obtain NaCrO2 by controlling the oxygen pressure, preventing the generation of
toxic Cr (VI).
364 F. Gu et al.
Fig. 3 Phase diagram of the Cr2 O3 –Na2 O2 system (p(O2 ) = 0.4 atm)
Effect of Roasting Atmosphere on the Phase Transformation

of Ferronickel Slag During Na2 O2 Roasting
Figure 6 shows the XRD patterns of the samples roasted in different atmospheres,
indicated by different oxygen concentrations (O2 /(O2 + N2 )). The experimental
conditions were the mass ratio of ferronickel slag to Na2 O2 of 1, roasting temperature
of 600 °C, and roasting time of 1 h. When the oxygen concentration was 0–20 vol
%, the main phases of the roasted sample were disodium magnesiosilicate, sodium
ferrate, and sodium chromate. However, when the oxygen concentration was 40 vol
%, the diffraction peaks of disodium chromate, instead of sodium chromate, appeared.
It indicated that as the oxygen concentration increased, the Cr (III) changed to toxic Cr
(VI). By further increasing the oxygen concentration, the main phases of the roasted
samples changed slightly. These results demonstrated that the roasting atmosphere
significantly affected the existing form of chromium in the roasted sample, which
agreed well with the above thermodynamic analysis.
Fig. 4 Phase diagram of the Cr2 O3 –Na2 O2 system (p(O2 ) = 1 atm)
Fig. 5 r G
m -T diagram
366 F. Gu et al.
Fig. 6 XRD patterns of the samples roasted in atmospheres at different oxygen concentrations
Effect of Roasting Atmosphere on the Recovery of Cr

from Ferronickel Slag
The effect of roasting atmosphere on the leaching percentage of Cr and the content
of Cr2 O3 in the leaching residue was studied by fixing the mass ratio of ferronickel
slag to Na2 O2 of 1, roasting temperature of 600 °C, roasting time of 1 h, leaching
temperature of 50 °C, leaching time of 1 h, and liquid-to-solid ratio of 10 mL/g.
As shown in Fig. 7, when the oxygen concentration increased from 0 to 20 vol %,
the leaching percentage of Cr increased significantly. As the oxygen concentration
increased continuously, the leaching percentage of Cr declined slightly. In specific,
as the oxygen concentration increased from 0% to 20 vol %, the leaching percent-
age of Cr increased from 51.68% to 92.33%. The content of Cr2 O3 in the leaching
residue decreased from 0.53 wt % to 0.06 wt %. When the oxygen concentration
increased further to 100 vol %, the leaching percentage of Cr decreased to 81.84%,
and the content of Cr2 O3 in the leaching residue increased to 0.18 wt %. This phe-
nomenon might be attributed to the fact that more Na2 O2 was required to produce
Na2 CrO4 instead of NaCrO2 (Eqs. 2–4). However, the addition of Na2 O2 was not
enough to completely convert Cr2 O3 to Na2 CrO4 in the atmosphere at 100 vol %
oxygen concentration. It was obvious that the absence of oxygen or pure oxygen
Fig. 7 Effect of oxygen concentration on the leaching percentage of Cr and the content of Cr in
the leaching residue
atmosphere were harmful to recovery of Cr from ferronickel slag, and the suitable
oxygen concentration for recovering Cr from ferronickel slag was about 20 vol %.
Conclusions
The effect of roasting atmosphere on the recovery of chromium from ferronickel

slag by alkaline roasting with Na2 O2 followed by water leaching was studied. The
thermodynamic analysis demonstrated that NaCrO2 and Na2 CrO4 are formed easily.
When the oxygen pressure is less than 0.4, the reactions between Na2 O2 and Cr2 O3
produce NaCrO2 and Na2 CrO4 . However, when the oxygen pressure exceeds 0.4,
the reactions between Na2 O2 and Cr2 O3 only lead to Na2 CrO4 . The XRD results
confirmed that when the oxygen concentration was less than 40 vol %, sodium chro-
mate (NaCrO2 ) appeared in the roasted sample. On the contrary, disodium chromate
(Na2 CrO4 ), instead of sodium chromate, appeared, when the oxygen concentration
exceeded 40 vol %. It was found that the leaching percentage of Cr reached 92.33%
and the content of Cr in the leaching residue decreased to 0.06 wt % under the opti-
mal alkaline roasting and water leaching conditions of the mass ratio of ferronickel
slag to Na2 O2 of 1, oxygen concentration of 20 vol %, roasting temperature of 600
°C, roasting time of 1 h, leaching temperature of 50 °C, leaching time of 1 h, and
liquid-to-solid ratio of 10 mL/g.
368 F. Gu et al.
Acknowledgements This work was partially supported by the National Natural Science Founda-
tion of China under Grants 51774337, 51504297 and 51811530108, the Natural Science Foundation
of Hunan Province, China, under Grant 2017JJ3383, the Science and Technology Planning Project of
Hunan Province, China, under Grant 2019RS2008, the Key Laboratory for Solid Waste Management
and Environment Safety (Tsinghua University) Open Fund under Grant SWMES2017-04, the Open
Project of State Key Laboratory Cultivation Base for Nonmetal Composites and Functional Materi-
als under Grant 17kffk11, the Fundamental Research Funds for the Central Universities of Central
South University under Grants 2018zzts220 and 2018zzts779, the Open Sharing Fund for the Large-
Scale Instruments and Equipments of Central South University under Grant CSUZC201905, and
the Co-Innovation Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources
under Grant 2014-405.
References
1. Saha AK, Sarker PK (2017) Sustainable use of ferronickel slag fine aggregate and fly ash in
structural concrete: mechanical properties and leaching study. J Clean Prod 162:438–448
2. Gu F, Peng Z, Zhang Y et al (2019) Valorization of ferronickel slag into refractory materials:
effect of sintering temperature. JOM 71:1024–1032
3. http://free.chinabaogao.com/nengyuan/201807/0G234V102018.html. Accessed 18 July 2019
4. Gu F, Zhang Y, Peng Z et al (2019) Selective recovery of chromium from ferronickel slag via
alkaline roasting followed by water leaching. J Hazard Mater 374:83–91
5. Peng Z, Gu F, Zhang Y et al (2018) Chromium: a double-edged sword in preparation of
refractory materials from ferronickel slag. ACS Sustainable Chem Eng 6:10536–10544
6. Gu F, Peng Z, Zhang Y et al (2018) Facile route for preparing refractory materials from
ferronickel slag with addition of magnesia. ACS Sustainable Chem Eng 6:4880–4889
7. Peng Z, Tang H, Augustine R et al (2019) From ferronickel slag to value-added refractory
materials: a microwave sintering strategy. Resour Conserv Recy 149:521–531
8. Antony M, Tathavadkar VD, Calvert CC et al (2001) The soda-ash roasting of chromite ore
processing residue for the reclamation of chromium. Metall Mater Trans B 32:987–995
9. Zhang Y, Zheng S, Du H et al (2010) Effect of mechanical activation on alkali leaching of
chromite ore. Trans Nonferrous Met Soc China 20:888–891
10. Zhao Q, Liu C, Shi P et al (2014) Sulfuric acid leaching of South African chromite, Part 1:
study on leaching behavior. Int J Miner Process 130:95–101
11. Kim E, Spooren J, Broos K et al (2015) Selective recovery of Cr from stainless steel slag by
alkaline roasting followed by water leaching. Hydrometallurgy 158:139–148
12. Wang Z, Zheng S, Wang S et al (2014) Research and prospect on extraction of vanadium from
vanadium slag by liquid oxidation technology. Trans Nonferrous Met Soc China 24:1273–1288
Purification of Crude Selenium
and Recovery of Gold and Silver
by Vacuum Distillation
Guozheng Zha, Xiangfeng Kong, Daxin Huang, Bin Yang, Wenlong Jiang,
Dachun Liu and Qinsong Mei
Abstract In this paper, vacuum distillation technology was developed to purify

crude selenium produced by the hydrometallurgical selenium removal treatment of
copper anode slime and recover gold and silver. Theoretical analysis of the saturated
vapor pressure was performed to determine the feasibility of vacuum distillation.
Laboratory and semi-industrial experiments were carried out to determine the opti-
mum process parameters. The kilogram-scale experiments showed that the purity of
selenium can be increased from 91.35 to 98.91% under the conditions of 50 Pa, 693 K,
and 90 min. It is difficult to separate selenium and tellurium completely by vacuum
distillation. The semi-industrial experiments showed that when the feed mass was
100 kg, under the conditions of 50 Pa, 693 K, and 160 min, the daily output of refined
selenium was more than 350 kg, the comprehensive power consumption for produc-
ing refined selenium (per ton) was 587 kW h, the direct yield of Se was 96.78%, and
the direct yields of Au and Ag were 99.72% and 99.56%, respectively, representing
enrichment by more than 20 times. The process is an environmentally friendly and
efficient metallurgical cleaning process in the treatment of crude selenium.
Keywords Selenium · Vacuum distillation · Purification · Recovery · Copper

anode slime
Introduction
As an important rare metal, selenium has been widely used in the fields of electron-
ics, metallurgy, the chemical industry, biology, and medicine [1, 2]. Crude selenium
extracted from copper anode slime by hydrometallurgical methods contains many
G. Zha · X. Kong · D. Huang · B. Yang (B) · W. Jiang · D. Liu · Q. Mei

National Engineering Laboratory for Vacuum Metallurgy, Kunming University of Science and
Technology, Kunming 650093, China
e-mail: kgyb2005@126.com
B. Yang · D. Liu
State Key Laboratory of Complex Non-Ferrous Metal Resources Clear Utilization, Kunming
University of Science and Technology, Kunming 650093, China

https://doi.org/10.1007/978-3-030-36540-0_33
370 G. Zha et al.
impurities and precious metals, such as gold and silver, and cannot meet the require-
ments of engineering and technology. It is necessary to purify crude selenium and
recover gold and silver, which have high economic value [3]. At present, the methods
for purifying selenium fall into chemical and physical processes [4, 5]. Chemical pro-
cesses are characterized by a long processing time, complex operation, low recovery
of selenium and limited application. The physical purification of selenium mainly
includes zone refining [6], which is one of the effective means to prepare high-purity
substances. However, zone refining has a lower efficiency for purifying crude sele-
nium. The above methods can improve the purity of selenium, but most of them have
the shortcomings of a long process time, serious pollution, high cost, and difficulty in
large-scale production, which limit the industrial application of selenium and cannot
meet the development needs of the selenium metallurgical industry in China.
Vacuum distillation, as a new technology in the metallurgical field, is a metal-
lurgical process performed under atmospheric pressure. Compared with traditional
metallurgical methods, vacuum metallurgy has the advantages of high metal recov-
ery, short process flow, simple operation and environmental friendliness [7, 8]. In this
work, we studied the application of vacuum distillation to purify crude selenium and
recover gold and silver and determined the optimum technological parameters; the
results lay a foundation for the industrial industrialization of purifying crude sele-
nium and demonstrate the feasibility of applying this method in the metallurgical
industry.
Theoretical Analysis of Saturated Vapor Pressure
The purification of metals by vacuum distillation is a metallurgical method for sep-

arating and enriching metals at low atmospheric pressure. Elements with a higher
saturated vapor pressure are preferentially volatilized into the vapor phase, and other
elements are not volatilized and remain in the residues. Under the same system pres-
sure, the saturated vapor pressure of a pure metal is only related to temperature. The
saturated vapor pressure (P, Pa) at different temperatures (T, K) can be calculated by
formula (1).
lgP = AT −1 + BlgT + CT + D (1)
where the required parameters A, B, C, and D are evaporation constants, which can
be found in the literature [9]. We calculated the saturated vapor pressure of Se and
the main impurities in crude selenium in the temperature range of 473 to 973 K, as
shown in Fig. 1.
Figure 1 shows that the saturated vapor pressure of each component in the crude
selenium increases with increasing temperature. At the same temperature, the satu-
rated vapor pressure of Se is much larger than that of other components, especially
Ag, Cu, Au, and Fe. In the vacuum distillation process, Se is easily volatilized into
Purification of Crude Selenium … 371
Fig. 1 P-T diagram of the components in crude selenium
the vapor phase, and the nonvolatilized impurities are concentrated and separated as
residues.
Experimental
Experimental Material
The experimental raw material was crude selenium produced by a hydrometallurgical

selenium removal process for treating copper anode slime from a copper smelting
enterprise in Yunnan. The chemical composition of the crude selenium is shown in
Table 1.
Table 1 Assay results of the crude selenium

Element Se Te Pb Cu Au (g t−1 ) Ag (g t−1 )
wt% 91.35 1.66 1.29 2.47 112 2560 For kilogram-scale
experiments
wt% 92.62 3.29 0.65 1.57 85 1365 For semi-industrial
experiments
372 G. Zha et al.
Experimental Equipment and Method
The vacuum distillation equipment for kilogram- and semi-industrial-scale experi-

ments was self-designed. The components include a vacuum furnace, vacuum pump,
control system, water cooling system, and other auxiliary equipment. The vacuum
furnace is mainly composed of a heating chamber, a condenser, and a collecting
chamber. Vacuum pressure is obtained by a vacuum pump. A graphite heater is used
to heat the crucible containing raw materials. The maximum temperature of the cru-
cible is 1473 K, and the system pressure limit is 30–50 Pa. A schematic diagram of
the vacuum distillation furnace is shown in Fig. 2.
During the experiment, a certain amount of raw selenium was placed into the
crucible in the vacuum furnace. Then, the cover of the furnace was tightened, and
the circulating cooling water valve and the vacuum pump valve were opened. After
reaching the predetermined vacuum degree, the switch was opened to begin heating.
The volatilized selenium was condensed and collected in the collection chamber.
Heavy metal impurities such as Pb, Cu, Au, and Ag were enriched in the crucible.
After distillation, the heating switch was immediately disconnected, and the circu-
lating cooling water was continued. When the furnace temperature dropped to room
temperature, the vacuum furnace was stopped; the condensate in the collection cham-
ber and the residues in the crucible were removed, weighed, and used for analysis
and detection.
Fig. 2 Schematic diagram of the vacuum distillation furnace

Kilogram-Scale Experiment
According to the above experimental method, a kilogram-scale experiment was car-

ried out. After the end of the experiment, the volatility of the material was calculated
according to formula (2).
mrawselenium − mresidues
Volatility = × 100% (2)
mrawselenium
Effect of Distillation Temperature
According to the theoretical analysis above, distillation temperature is the main

factor affecting the purification of selenium. At 573 K, the saturated vapor pressure
of selenium is only 31.7 Pa, while at 603 K, it is 86 Pa. Therefore, the initial feed
amount was set to 10 kg, the system pressure was 50 Pa, the distillation time was
90 min, and the distillation temperatures were 603 K, 633 K, 663 K, 693 K, and 723 K.
The effect of different distillation temperatures was investigated. The experimental
results are shown in Fig. 3 and Fig. 4, respectively.
From Fig. 3, it can be seen that the volatility increased gradually with increasing
distillation temperature. When the temperature increased from 603 K to 663 K, the
100
90
80
Volatility (%)
70
60
50
40
30
20
600 620 640 660 680 700 720 740

Distillation temperature/K
Fig. 3 The effect of distillation time on volatility

374 G. Zha et al.
100
98
Se and Te content in volatiles (%) 96 Se

94 Te
92
90
0
600 620 640 660 680 700 720 740
Distillation temterature/K
Fig. 4 The effect of distillation temperature on Se and Te content in volatiles
volatility increased rapidly from 23.24 to 82.36% because with increased tempera-
ture, a large amount of Se volatilizes into the vapor phase. The volatility increased
slightly when the temperature reached 693 K because the selenium in the raw mate-
rial had essentially evaporated completely after the temperature reached 693 K. As
shown in Fig. 4, with increased distillation temperature, the content of Se in volatile
changed slightly, ranging from 98.43 to 98.91%, and the content of Te increased
gradually from 0.63 to 1.37%. Compared with the Te content of 1.66% in the raw
materials, the content of Te in the volatiles decreased, but Te remained the main
impurity in the selenium, indicating that Se and Te cannot be separated completely
by vacuum distillation due to the small difference in saturated vapor pressure between
the two elements.
Effect of Distillation Time
The distillation temperature was set at 693 K, the feed amount was 10 kg, and the
system pressure was 50 Pa. The distillation times were 30, 60, 90, 120, and 150 min.
The experimental results are shown in Figs. 5 and 6.
As shown in Fig. 5, with prolonged distillation time, the volatilization rate of
the material increased rapidly and then remained stable. The volatility was 32.24%
when the distillation time was 30 min and 90% when the distillation time was 90 min.
The volatility increased rapidly to 90.43% because Se could be volatilized into the
vapor phase with the extension of distillation time. The volatility remained steady
when the distillation time was extended to 150 min. The selenium in the raw material
had evaporated completely, while the metals with a small saturated vapor pressure,
100
90
80
70
Volatility (%)
60
50
40
30
20
30 60 90 120 150
Distillation time/K
Fig. 5 The effect of distillation time on volatility
35000
Au and Ag content in residues (g·t-1)
30000
25000
Au
20000 Ag
15000
10000
2500
2000
1500
1000
500
0
30 60 90 120 150
Distillation time/min
Fig. 6 The effect of distillation time on Au/Au content in residues
such as lead, copper, gold, and silver, were basically nonvolatile. Figure 6 shows
that with increased distillation time from 30 to 90 min, the content of Au in the
residue increased from 737 to 2365 g/t, and the content of Ag increased from 1560
to 32786 g/t. The reason is that after the volatilization of Se and Te, Au and Ag are
enriched in the residues. When the distillation time was prolonged, the content of
Au and Ag in the residue increased from 1560 to 32786 g/t.
376 G. Zha et al.
Semi-Industrial Experiment
Semi-industrial experiments were carried out on the basis of the kilogram-scale

experiments. The experimental equipment was developed on the basis of expanding
and improving the kilogram-scale experimental equipment. The operation methods
of the experiments were basically the same as above. According to the crucible size,
the feeding quantity in the semi-industrial experiment was set at 100 kg per furnace.
Study on the Optimum Distillation Time
The effects of distillation time on the contents of Se and Te in volatiles, the Se direct
yield, Se recovery and the residue ratio were investigated at 693 K and 50 Pa. The
experimental results are shown in Figs. 7 and 8.
mvolatiles × wSeinvolatiles
Se direct yield = × 100% (4)
mrawselenium × wSeinrawselenium
mvolatiles × wSe in volatiles + mresidues × wSe in residues
Se recovery = × 100% (5)
mraw selenium × wSe in raw selenium
mresidues
Residue ratio = × 100% (6)
mraw selenium
100
98.02 97.56 98.00 97.62 97.79
Se and Te contents in volatiles (%)
80
Se
60 Te
40
20
1.96 2.41 1.99 2.32 2.15

0
140 150 160 170 180
Fig. 7 The effect of distillation time on Se/Te content in the volatiles

100
99.12 98.21
94.09 90.41 92.56
98.82 97.99
90.91
80 89.29
82.95
Se direct yield
Se recovery
wt/%
60
residue ratio
40
20
12.19 12.52
7.4 5.94 6.56
0
140 150 160 170 180
Fig. 8 The effect of distillation time on the Se direct yield, Se recovery, and the residue ratio
From Fig. 7, it can be seen that the contents of Se and Te in the volatiles remained
essentially unchanged with increased distillation time. The contents of Se and Te in
the volatiles were approximately 98% and 2%, respectively. According to theoretical
analysis and the kilogram-scale experiment, the vacuum distillation method cannot
separate Se and Te well. The high content of Te in the raw materials leads to more
Te entering the volatiles during vacuum distillation, which reduces the purity of the
selenium. Figure 8 shows that the residue ratio gradually decreased with increasing
distillation time. When the distillation time was 160 min, the residue ratio was 6.56%,
and at this time, the direct yield and recovery of Se reach a maximum (98.82%
and 99.12%, respectively), so the optimum distillation time for the semi-industrial
experiments was 160 min.
Continuous Production Experiment
Based on the above experiments, the optimal experimental conditions for the semi-
industrial experiment were determined to be 100 kg, a distillation temperature of
693 K, a distillation time of 160 min, and a system pressure of 50 Pa. Under the
optimum experimental conditions, the contents of Se and main impurities in the
volatiles, the stability of single-furnace output, the direct yield, the recovery of Au
and Ag, and the energy consumption of the equipment were investigated through 10
continuous furnace experiments. The experimental results are shown in Table 2.
Table 2 shows that the main elements in the volatiles are Se and Te, but the volatiles
also contain a small amount of Pb, Cu, and Ag. Au was not detected. Among the
378 G. Zha et al.
Table 2 The results of 10 consecutive experiments

No. Input Output (refined selenium) The contents of Se and main impurities in volatiles
kg kg Se (%) Te (%) Pb (%) Cu (%) Ag/g t−1
1 100 91.0 97.85 2.10 0.0249 0.0012 9
2 100 92.0 97.78 2.11 0.0502 0.0016 4
3 100 90.0 97.53 2.40 0.0499 0.0012 3
4 100 88.5 98.26 1.71 0.0139 0.0008 8
5 100 89.0 97.98 1.98 0.0344 0.0009 9
6 100 91.5 97.74 2.15 0.0558 0.0009 8
7 100 92.0 98.45 1.53 0.0035 0.0006 4
8 100 91.0 97.00 2.83 0.1293 0.0017 11
9 100 90.5 97.77 2.19 0.0195 0.0012 5
10 100 93.0 98.19 1.78 0.0055 0.0001 6
detected elements, the fluctuation range of Se content was 97.00–98.45%, and the Te
content was 1.53–2.83%. The total content of Se and Te was 99.83–99.97%, which
meets the sales requirements of a certain enterprise in Yunnan. The single-furnace
output was essentially stable, with an average output of 90.9 kg. The refined selenium
ingots and Au–Ag enriched residue are shown in Figs. 9 and 10, respectively. Au was
not detected in the volatiles, and the Ag content was only 6.7 g t−1 ; almost all Au
and Ag were enriched in the residue. The contents of Au and Ag in the residue were
enriched from 85 g t−1 and 1365 g t−1 to 1790 g t−1 and 29200 g t−1 , respectively, an
enrichment of 21.06 and 21.39 times, which is convenient for the subsequent recovery
Fig. 9 Refined selenium ingots

Fig. 10 Au–Ag enriched residue
of precious metals. Through energy consumption statistics, the average electricity

consumption of the 10-furnace continuous production experiment was 533.29 kW·h,
and the comprehensive power consumption for obtaining refined selenium ingots
(per ton) was 587 kW·h, which represents remarkable energy savings.
Conclusions
In this paper, a systematic study on the purification of crude selenium and recov-
ery of gold and silver by vacuum distillation was carried out. The theoretical and
experimental studies have led to the following conclusions.
(1) Thermodynamic calculation of the saturated vapor pressure of each component
in crude selenium shows that a large amount of Se can be volatilized into the
vapor phase and other impurities remain in the residue.
(2) The kilogram-scale experiments showed that the purity of selenium can be
increased from 91.35 to 98.91% under the conditions of 50 Pa, 693 K, and
90 min. It is difficult to separate selenium and tellurium completely by vacuum
distillation. The contents of Au and Ag were enriched from 112 g t−1 and 1560 g
t−1 to 2365 g t−1 and 32786 g t−1 , respectively, enrichments of 21.12 and 21.02
times.
(3) Semi-industrial experiments showed that when the feed mass was 100 kg, under
the conditions of 50 Pa, 693 K, and 160 min, the daily output of refined selenium
was more than 350 kg, the comprehensive power consumption for producing
380 G. Zha et al.
refined selenium (per ton) was 587 kWh, the direct yield of Se was 96.78%, and
the direct yields of Au and Ag were 99.72% and 99.56%, respectively.
(4) Theoretical analysis and the experimental results showed that the process of
purifying selenium and recovering gold and silver by vacuum distillation of
crude selenium is feasible. Compared with other methods, it has the advan-
tages of simple equipment, short process flow, low energy consumption, and
environmental friendliness, which reduces the production cost. It is of great
significance to improve the selenium-producing ability of enterprises and the
recovery ability of the precious metals gold and silver.
References
1. Rayman MP, Lyons TP, Cole DJA (2000) The importance of selenium to human health. Lancet
356(9225):233–241
2. Hou J, Zhao H, Fei H, et al. (2018) Facile one-step fabrication of CdS0.12Se0.88 quantum dots
with ZnSe/ZnS—passivation layer for highly efficient quantum dot sensitized solar cells. J Mater
Chem A 10.1039.C8TA01048 J
3. Yavuz Ö, Ziyadanoğullari R (2000) Recovery of gold and silver from copper anode slime. Sep
Sci Technol 35(1):133–141
4. Nielsen S, Heritage RJ (1959) A method for the purification of selenium. J Electrochem Soc
106(1):39–43
5. Jiafeng Z, Bao Z, Xueyi G, et al. (2011) Study on crude selenium purifying by a sulfite sodium
leaching method. Rare Met Mater Eng 1
6. Burger A, Henderson DO, Morgan SH et al (1990) Purification of selenium by zone refining. J
Cryst Growth 106(1):34–37
7. Yang B, Zha G, Hartley W et al (2019) Sustainable extraction of lead and re-use of valuable
metals from lead-rich secondary materials. J Clean Prod 219:110–116
8. Zha G, Yang C, Wang Y et al (2019) New vacuum distillation technology for separating and
recovering valuable metals from a high value-added waste. Sep Purif Technol 209:863–869
9. Dai YN, Yang B (2004) Non-ferrous metal vacuum metallurgy. Metallurgical Industry Press,
Beijing, pp 24–28
Effect of P2 O5 on the Recovery of Ti
from Ti-Bearing Blast Furnace Slag
by Super-Gravity
Yu Du, Jintao Gao, Xi Lan and Zhancheng Guo
Abstract For the efficient recovery of Ti from Ti-bearing blast furnace slag, an
innovative method was proposed in this paper by investigating the effect of P2 O5
on the recovery of Ti by super-gravity. Firstly, the precipitation behaviors of rutile
in Ti-bearing blast furnace slag with different P2 O5 content were investigated. The
mineral compositions and microstructure of rutile precipitated from various slags
with different P2 O5 content were analyzed through XRD and SEM-EDS methods,
which presented that the P2 O5 in slag could effectively enrich Ti element through
promoting the nucleation and growth of rutile. As the P2 O5 content in slag increased
from 0 to 3 wt%, the volume fractions and equivalent diameters of rutile increased
from 2.64% to 25.25% and 19.75 μm to 61.9 μm, respectively. Subsequently, the
separation of rutile from the slag was conducted in a super-gravity field. After super-
gravity separation with G = 800 at 1310 °C for 5 min, the slag melt went through
the filter and entire high-purity rutile was intercepted by the filter and effectively
recovered from Ti-bearing blast furnace slag.
Keywords Ti-bearing blast furnace slag · P2 O5 · Rutile · Super-gravity separation
Introduction
China is rich in mineral resources of titanium, 92.4% of which is located in the

vanadium-titanium bearing magnetite, deposited mostly around the southwestern
part [1]. After blast furnace process, almost all the Ti was turned into the slag and
formed the blast furnace slag containing 22–25% TiO2 , which was also a useful
resource for Ti industry. However, due to the dispersed distribution of Ti component
in various fine-grained mineral phases with the complex interfacial combination,
the application of traditional mineral and leaching processes to separate and extract
titanium from the slag may result in poor recovery and high cost [2, 3].
Y. Du · J. Gao (B) · X. Lan · Z. Guo

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing,
e-mail: jintaogao@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_34
382 Y. Du et al.
If the Ti in Ti-bearing blast furnace slag could be enriched into a high-grade Ti

containing phase and recovered from Ti-bearing blast furnace slag employing an
efficient separation method, it would be a better choice for the recovery of Ti. Rutile
(TiO2 ) is one of the most widely used metal oxides, which has a broad range of
applications, including pigments [4], gas and humidity sensors [5], catalyst support
[6], solar cells [7], and capacitors [8]. Moreover, as a coveted high-grade Ti mineral
phase, the TiO2 content in rutile was almost closed to 100% in theory, which caused
extremely high attention in recent years. Sui [9] investigated the mineral composition
and microstructure of original Ti-bearing blast furnace slag, finding that the primary
precipitation phase of slag was perovskite (CaO·TiO2 ). Although the precipitation
amount, crystal size of perovskite was improved after dynamic oxidation, it was
difficult to obtain high-grade Ti product directly as a result of the low theoretical
content of TiO2 in perovskite which was only 58.87%. Li [10] and Wang [11] have
found that reducing slag basicity could promote the transformation from the primary
perovskite to rutile, while the little precipitation amount and fine crystal size of rutile
make it difficult to effectively recover Ti from Ti-bearing blast furnace slag through
separating rutile. As reported by Ren [12] and Sun [13], a small amount of acidic oxide
such as B2 O3 and P2 O5 could promote the precipitation of rutile in Ti-bearing blast
furnace slag, because these added acidic oxides could restrain the linkage between
CaO and TiO2 to form CaTiO3 . Inspired by the specific function for acidic oxide to
restrain the precipitation of CaTiO3 , the effect of P2 O5 on the precipitation of rutile
was investigated to promote the Ti recovery ratio from Ti-bearing blast furnace slag.
For the separation of rutile from Ti-bearing blast furnace slag, many technologies
have been developed including leaching and mineral methods. However, the mass
of obvious shortcomings such as high cost and large waste acid and sludge derived
by these conventional methods appeared due to the fine rutile embedded intimately
with other mineral phases [14]. Super-gravity, as a physical method of strengthening
mass transfer, can effectively overcome the resistance between phases caused by large
viscosity and separate valuable components from complex slags [15]. Based on the
investigations about the precipitation of rutile above, if the super-gravity could be
employed at an appropriate solid–liquid temperature range in which rutile precipitate
as a solid phase while other phases forming the liquid melt slag, it was better for the
separation of rutile from slag melt.
In this study, a novel method was proposed to efficiently recover Ti from Ti-bearing
blast furnace slag. The precipitation of rutile was significantly enhanced through
investigating the effect of different P2 O5 content on the precipitation behaviors of
rutile. Furthermore, the application of super-gravity technology makes it realizable
to effectively separate rutile from slag melt.
Effect of P2 O5 on the Recovery of Ti … 383
Experimental
Materials
Based on the main compositions of Ti-bearing blast furnace from Panzhihua Iron and
Steel Corporation of China [16], the reagent grade chemical agents of CaO, SiO2 ,
TiO2 , Al2 O3 , MgO, and P2 O5 were used to prepare the simulated slag to eliminate
the impact of minor elements in the industrial slag, whose compositions are shown
in Table 1. Based on the CaO–MgO–SiO2 –Al2 O3 –TiO2 phase diagram calculated
through Factsage 7.2 as shown in Fig. 1, the basicity of modified slag was altered
Table 1 Chemical composition (wt%) of the experimental materials

Composition CaO SiO2 TiO2 Al2 O3 MgO Others P2 O5
Ti-bearing blast furnace slag 28.64 25.44 22.35 12.09 7.06 4.42 1.13
Modified slag-1 20.00 40.00 22.00 12.00 6.00 – 0.00
Modified slag-2 19.67 39.33 22.00 12.00 6.00 – 1.00
Modified slag-3 19.00 38.00 22.00 12.00 6.00 – 3.00
Modified slag-4 18.33 36.67 22.00 12.00 6.00 – 5.00
Fig. 1 Phase diagram of CaO–MgO–SiO2 –Al2 O3 –TiO2 system

384 Y. Du et al.
Fig. 2 Systematic diagram of centrifugal apparatus: (1) thermocouple, (2) temperature controller,
(3) conductive slipping, (4) centrifugal axis, (5) counterweight (6) rutile, (7) heating furnace, (8)
alumina crucible
from 1.1 to 0.5 with the purpose of transforming primary precipitation phase from
perovskite to rutile. In order to investigate the effect of P2 O5 on the precipitation of
rutile, the P2 O5 content in modified slag was adjusted further from 0 to 5 wt%.
Apparatus
For effectively separating rutile from slag melt at solid–liquid temperature range, the
super-gravity field in this work was generated by a centrifugal apparatus incorporated
with a heating furnace with a counterweight fixing symmetrically onto the horizontal
rotor as shown in Fig. 2. When the centrifuge was commenced, the rotor rotated from
vertical to horizontal orientation. The temperature was controlled by a programmed
controller with a B-type thermocouple within the observed precision range of ±3 °C.
Effect of P2 O5 on the Precipitation of Rutile in Ti-Bearing

Blast Furnace Slag
The precipitation behaviors of rutile in Ti-bearing blast furnace slag with different
P2 O5 content were investigated firstly through hot quenching method combined with
ex situ characterization. Each 20 g of modified slag with various P2 O5 contents of
0, 1.0, 3.0, and 5.0 wt% was evenly mixed and filled into an alumina crucible (ID
19 mm and H 60 mm), which was heated to 1500 °C in the muffle furnace under
argon atmosphere and maintained for 30 min to ensure that the slag was fully melted.
Afterwards, the slags were cooled slowly to 1230 °C with a cooling rate of 3 °C/min
for the sake of sufficient precipitation of rutile and subsequently quenched in water
to obtain the instantaneous state of slags. The mineral compositions and microstruc-
tures were analyzed by X-ray diffraction (XRD) and scanning electron microscope
combined with energy-dispersive X-ray spectrum (SEM-EDS), respectively. More-
over, an average of 20 fields of scanning electron micrograph in each sample were
characterized further on image analyzer (LEICA Qwin 500) to conduct the statisti-
cal analysis on the variations in volume fractions and equivalent diameters of rutile
phases with different P2 O5 content.
Separation of Rutile from Slag Melt in a Super-Gravity Field
Based on the precipitation behaviors of rutile with different P2 O5 content, the sepa-
ration of rutile from Ti-bearing blast furnace slag was conducted in a super-gravity
field subsequently. 20 g of water-quenched slag with P2 O5 content of 3% was placed
on an alumina filter with 0.5 mm pore size, which was fixed onto an alumina cru-
cible with 19 mm inner diameter as shown in Fig. 1. When the sample was heated
to 1310 °C, the centrifugal device was rotated at an angular velocity of 1692 rpm to
achieve the gravity coefficients of G = 800 as calculated via Eq. (1). After centrifugal
rotating for 5 min, the device was shut off, and the alumina crucible was taken out
and rapidly quenched in water. Meanwhile, the parallel experiments were conducted
at 1310 °C for 5 min with gravity coefficients of G = 1.

π x 2
2 2
g2 +(ω2 x)2 g2 +( N900 )
G= = (1)
g g
where G is gravity coefficient, g is the normal gravitational acceleration (g =

9.8 m/s2 ), ω is the angular velocity (rad/s), x is the distance between the centrifugal
axis and sample center (m), N is the rotating speed (r/min).
After separation of rutile from slag melt in a super-gravity field, the samples were
sectioned longitudinally along the center axis, and then analyzed via SEM-EDS,
XRD, and XRF methods to investigate the microstructure, mineralogical constitution,
and chemical composition of the samples held on and went through the filter. The Ti
recovery ratio in the separated rutile phase was calculated via Eq. (2).
mR × ωTi−R
εTi = × 100% (2)
mR × ωTi−R + mS × ωTi−S
where, εTi is recovery ratio of Ti in the separated rutile phase, mR and mS are the
mass fractions of the separated rutile and slag phases, and ωTi−R and ωTi−S are mass
fractions of Ti in the separated rutile and slag phases, respectively.
386 Y. Du et al.
Effect of P2 O5 on the Precipitation of Rutile
Variations in the mineral compositions of modified slags with different P2 O5 content

after slow cooling are shown in Fig. 3. It was obvious that the primary precipita-
tion phase of modified slag was transformed from perovskite to rutile after the slag
basicity was altered from 1.1 to 0.5, indicating that the appropriate slag basicity
for the precipitation of rutile was 0.5, which was in accordance with the thermody-
namic calculation results in Fig. 1. The diffraction peak intensity of rutile increased
significantly with the P2 O5 content of slags increasing to 3 wt%, indicating that a
small amount of P2 O5 could effectively facilitate the precipitation of rutile from slag.
While as the P2 O5 content increased from 3 to 5 wt%, the diffraction peak intensity
of rutile possessed slight reduce.
The variations in the microstructures, volume fractions, and equivalent diameters
of rutile precipitated in modified slag as a function of P2 O5 content are shown in
Figs. 4 and 5, respectively. It was obvious that only a certain amount of square rutile
precipitated in the slag melt when the P2 O5 content in slag was 0% as shown in
Fig. 4a. Corresponding with the EDS image and EDS data in Fig. 4e and Table 2,
respectively, the rutile precipitated was only consisted of two elements as titanium
(Ti) and oxygen (O), for which the mole ratio was almost closed to 1:2. As the P2 O5
content in the slag increased from 0 to 3 wt%, rutile was still the single precipitated
phase in the slag, the precipitation amount and crystal size of rutile were extremely
enhanced, which was in accordance with of the XRD patterns in Fig. 3. All the P
1 1-rutile 2-perovskite 3-diopside
1 1 1
1 Modified slag 4 (w(P2O5)=5%)
1
1 1 1 1 Modified slag 3 (w(P O )=3%)

2 5
1
Intensity
1 1 1 Modified slag 2 (w(P O )=1%)

1 2 5
1
1 1 1 1 Modified slag 1 (w(P2O5)=0)
2
3
2
3 3
2 3 3 3 33 3 3 2
Ti-bearing blast furnace slag
10 20 30 40 50 60 70 80 90
2-Theta-Scale(degree)
Fig. 3 Variations in XRD patterns of various slags as a function of P2 O5 content

Fig. 4 Variations in SEM-EDS images of various slags with different P2 O5 content: a w(P2 O5 ) =
0, b w(P2 O5 ) = 1%, c w(P2 O5 ) = 3%, d w(P2 O5 ) = 5%, e EDS image of rutile, f EDS image of
slag melt
Fig. 5 Variations in volume 30

fractions and equivalent
80
diameters of rutile as a
Volume fraction/(%)
function of P2 O5 content
equivalent diameter/(μm)
20
60
40
10
20
0
0 1 3 5
P2O5 content/(wt%)
Table 2 Energy-dispersive spectrum data (wt%) for various phases

Positions Samples Ti O Ca Si Al Mg P
Figure 4 Pt.1 Rutile phase 61.36 38.64 – – – – –
Figure 4 Pt.2 Slag phase 7.46 40.30 18.98 16.46 7.51 4.96 4.33
388 Y. Du et al.
element existed in the slag through EDS data in Table 2 and EDS image in Fig. 4f.
While as the P2 O5 content increased to 5%, the average size and precipitation amount
of rutile started to decrease.
Combined with the image analysis results in Fig. 5, as P2 O5 content increased
from 0 to 3 wt%, the volume fractions of rutile increased from 2.64% to 25.25% and
equivalent diameters increased from 19.75 μm to 61.9 μm, respectively, indicating
that small amount of P2 O5 could effectively promote the nucleation and growth of
rutile. Based on the thermodynamic reaction data between CaO, TiO2 , and P2 O5 , the
standard Gibbs free energy change for the reaction of CaO and P2 O5 was extremely
lower than that of CaO and TiO2 , thus CaO preferentially reacted with P2 O5 instead
of TiO2 , inhibiting the formation of perovskite thus promoting the precipitation of
rutile. While as the P2 O5 content increased to 5 wt%, slight reduction has appeared
for both volume fractions and equivalent diameters of rutile, mainly because sudden
increase of slag viscosity caused by excess P2 O5 . Hence, the optimal P2 O5 content
for promoting the precipitation of rutile was 3 wt%, which was a favorable condition
for subsequent recovery of rutile from modified Ti-bearing blast furnace slag.
Separation of Rutile from Slag Melt in a Super-Gravity Field
Cross profiles of the sample (w(P2 O5 ) = 3%) attained in a super-gravity field (G =

600) compared with normal-gravity field (G = 1) are shown in Fig. 6. It was obvious
that all of the slag was blocked to the top alumina crucible by the filter with an even
structure in a normal super-gravity field. In contrast, the sample was separated into
Fig. 6 Cross profiles of the samples (w(P2 O5 ) = 3%) attained in a super-gravity field compared
with normal gravity field: a G = 1, b G = 800, c macrostructure of separated rutile
Fig. 7 XRD patterns and SEM-EDS images of the separated samples attained in a super-gravity
field (G = 800, T = 1310 °C): a XRD patterns of rutile, b SEM of rutile, c SEM of slag
two parts by the filter in a super-gravity field. The above parts presented a yellow
needle-like structure compared with the glass state below the filter.
XRD patterns and SEM-EDS images of the separated samples attained in a super-
gravity field with G = 800, T = 1310 °C are shown in Fig. 7. It was obvious
that after super-gravity separation, the top and below parts as shown in Fig. 6 pre-
sented entirely different mineral compositions and microstructures. The single high-
intensity diffraction peak of rutile appeared in rutile phase as shown in Fig. 7a with
an independent rod shape in the microscopic perspective as shown in Fig. 7b. In
contrast, the part below the filter presented a typical dispersion peak in mineral com-
position with a uniform state. It was evidenced that rutile was the only solid phase
in slag at the temperature of 1310 °C, while the other minerals formed the slag melt.
The slag melt went through the filter in a super-gravity field, while the high-purity
solid rutile was held up by the filter.
Furthermore, the mass fractions of TiO2 in the separated samples obtained by
super-gravity are given in Table 3. After separating in a super-gravity field with
gravity coefficient of G = 800 at 1310 °C for 10 min, the mass fraction of TiO2 in
rutile phase was up to 93.42 wt%. The recovery of Ti was 52.16%. In contrast, the
mass fraction of TiO2 in slag phase was decreased to 12.46 wt%.
Table 3 Recovery ratio of Ti in the separated samples obtained by super-gravity

Sample Mass fraction (%) Chemical composition of TiO2 Ti recovery ratio (%)
(wt%)
Rutile phase 12.7 93.42 52.16
Slag phase 87.3 12.46 47.87
390 Y. Du et al.
Conclusion
In this paper, a novel method was proposed with a purpose of efficient recovery of Ti
from Ti-bearing blast furnace slag. The effect of P2 O5 on the precipitation of rutile
in modified Ti-bearing blast furnace slag and super-gravity separation of rutile from
slag melt were investigated. The following two conclusions could be drawn:
(1) The precipitation behaviors of rutile with different P2 O5 content was inves-
tigated firstly. The P2 O5 in slag could effectively enrich Ti element through
promoting the nucleation and growth of rutile. The volume fractions and equiv-
alent diameters of rutile increased from 2.64% to 25.25% and 19.75 μm to
61.9 μm, respectively with P2 O5 content increasing from 0 to 3 wt%.
(2) The high-purity rutile was effectively intercepted by the filter along the super-
gravity direction and separated from the slag melt in a super-gravity field. After
separation by super-gravity with G = 800 at 1310 °C for 5 min, the mass fraction
of TiO2 in the separated rutile crystals was up to 93.42 wt%, whereas that of
the slag phase was reduced to 12.46 wt%.
Acknowledgements This study is supported by the National Natural Science Foundations of China
(No.51774037 and No.51404025).
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A Study on Recovery of Iron from Red
Mud by Solid State Reduction Followed
by Magnetic Separation
Said Eray, Ender Keskinkilic, Mustafa Varol, Yavuz A. Topkaya

and Ahmet Geveci
Abstract Red mud is a waste material of the Bayer process for alumina production
from bauxite ore. Red mud is generally pumped to disposal in an artificial pond which
is accompanied by great land occupation and environmental issues. Many researches
in different fields have been carried out to evaluate the red mud. Of these, researches
on recovering valuable metals from red mud are the most successful. In this study,
recovery of iron, which is the most abundant metal in red mud, was investigated. A red
mud sample with 34% Fe2 O3 was used. Solid state carbothermic reduction followed
by wet magnetic separation was performed to recover iron. Reduction was carried
out at temperatures 1000–1200 °C. Reduced samples were ground and subjected to
wet magnetic separation. The effect of reduction temperature and grinding time were
investigated on the metallization of iron and the iron content of the final concentrate.
Keywords Red mud · Iron recovery · Reduction · Magnetic separation
Introduction
Red mud is a waste material of the Bayer process for alumina production from bauxite
ore. Red mud is generally pumped to disposal in an artificial pond [1]. In addition
to the vast area of the land occupied, red mud pollutes water resources and leads to
environmental issues [2] because of its high alkalinity (pH of 10–12.5). Leading to
large economic losses, red mud continued to remain as a challenge to the aluminum
industry.
S. Eray (B) · M. Varol

Ağrı İbrahim Çeçen University, 04100 Ağrı, Turkey
e-mail: seray@agri.edu.tr
E. Keskinkilic
Department of Metallurgical and Materials Engineering, Atilim University, 06830 Ankara, Turkey
Y. A. Topkaya · A. Geveci
Department of Metallurgical and Materials Engineering, Middle East Technical University, 06800
Ankara, Turkey

https://doi.org/10.1007/978-3-030-36540-0_35
394 S. Eray et al.
Eti Alüminyum A.Ş. is the only company in Turkey which produces aluminum
from bauxite ore. Red mud disposal by the company is 0.996 tons per ton of alumina
produced. More than 6.7 million tons (dry basis) of red mud has been disposed since
1974.
Parallel with the other countries worldwide, researches have been conducted in
Turkey on the utilization of Seydişehir red mud. Red mud contains an appreciable
amount of industrial metals [3–5] such as Fe, Al, and Ti and rare earth elements
like Sc, Ce, and La [6, 7]. Recycling of valuable elements is the most economically
attractive method of evaluating this industrial waste [8–10].
Red mud contains several valuable elements at very different concentrations and
with very different chemical characteristics. The situation makes it difficult to recover
them all in an integrated process. However, as the most abundant element in the red
mud, recovery of iron at the beginning of the recovery process will significantly
decrease the material to be treated at the next stages.
In this paper, the recovery of iron from Turkish red mud was studied. Red mud
sample was reduced at solid state with coal. The iron particles formed during the
reduction were then separated by wet magnetic separation method to obtain iron
reach concentrates.
Red mud sample to be used in the experiments were supplied from Eti Alüminyum
A.Ş. in Turkey. The chemical analysis of the sample, determined by ICP, is given
in Table 1. Coal was used to reduce iron oxide in red mud. The coal used as the
reductant was Ukrainian hard coal whose analysis is given in Table 2.
Assuming that the iron in the red mud is in hematite form and the reduction takes
place with carbon, Reaction 1 was considered to determine red mud and coal ratios.
Fe2 O3 + 3C → 2Fe + 3CO (Reaction 1)
Based on the stoichiometry of the above reaction, the iron content of the red mud
samples and the carbon content of the coal, the theoretically required minimum coal
ratio was calculated to be 10.1%. In the experiments, coal ratios of 10–40% higher
than the theoretically required ratio were tested.
Red mud and finely ground coal were mixed thoroughly before they were charged
into the alumina crucibles. The weight of the total mixture was chosen as 50 g
according to the preliminary tests and the capacity of the alumina crucible used.
Vertical tube furnace was used for the reduction of the samples. The sample was
placed in the furnace at room temperature and then heated to a desired temperature
between 1000–1200 °C at a rate of 7 °C/min. The sample was retained at the desired
temperature for 40 min after which it was cooled to room temperature again at 7 °C/
min. Nitrogen gas at 50 ml/min flow rate was passed through the furnace throughout
Table 1 Chemical analysis of the Turkish red mud sample
A Study on Recovery of Iron from Red Mud …
SiO2 Al2 O3 Fe2 O3 CaO Na2 O TiO2 Y Ce La Sc Gd

wt% ppm
14.6 22.8 34 3.18 8.9 4.95 118 581 201 91 32.7
395
396 S. Eray et al.
Table 2 Chemical composition of the reductant coal (wt%)

Carbon Volatile Matter Moisture S Ash
76.06 17.64 1.77 0.33 4.2
Fig. 1 Vertical tube furnace and gas supply unit used in reduction experiments
the experiment. The gas flow rate was controlled by a gas supply unit consisting of
a manometer and a capillary tube (Fig. 1).
Partially sintered samples obtained from reduction of the mixture were pulverized
in a ring mill. A ball mill was used to further reduce the grain size of the roughly
pulverized samples in the ring mill.
The bromine-methanol method, described in more detail below, was used to deter-
mine the degree of metallization of iron oxide in the reduction step. This method can
be used to determine the proportion of metallic iron in samples containing a mixture
of various oxides and metallic iron. For this analysis, 50 ml of a bromine-methanol
solution (5%) was added to the 1 g finely ground sample and stirred for 1 h. The
solution was passed through a filter paper and collected into a 1000 ml beaker. 25 ml
of 20% sulfuric acid solution was added to the filtered solution. The solution was
boiled to evaporate all bromine and methanol. 1 ml of hydrogen peroxide was added
to the solution during boiling. After the boiling, 200 ml of distilled water and 25 ml of
HCl (37%) were added to the residue and boiled again for 30 min. The final solution
was analyzed with AAS for iron.
A wet magnetic separator was prepared to recover metallic iron from the reduced
and ground samples. Strong neodymium magnets of 1.2 T magnetic field strength
were used in the setup. The separator and its operating principle are schematically
shown in Fig. 2. Five grams of ground sample were dispersed in 1 L of distilled water
A Study on Recovery of Iron from Red Mud … 397
Fig. 2 Schematic
representation of the wet
magnetic separator
and the suspension was passed through the separator. Magnetic particles were trapped
in the magnetic field of the magnets while non-magnetic fraction passed and collected
in the beaker located at the other end of the tube. The magnetic particles were then
washed out and collected in another beaker. This process was repeated several times
until it was ensured that no magnetic particles remained in the suspension.
Mineralogical Composition of the Red Mud
XRD pattern of the as-received red mud sample is shown in Fig. 3. The sample was
mainly composed of hematite, hydroxycancrinite, gibbsite, calcite, and rutile. It is
seen that the only iron bearing mineral is hematite.
Determination of Appropriate Coal Ratio
Coal was used to reduce iron oxide in red mud. As mentioned before, the theoretically
required ratio and also 10–40% of excess coal were used to study the effect of coal
398 S. Eray et al.
Fig. 3 XRD pattern of the as-received red mud sample
amount. The residual carbon in the reduced samples was analyzed on a LECO brand
and SC-144DR model carbon-sulfur analyzer.
Figure 4 shows the change in residual carbon content and percentage of reacted
coal. The percentage of reacted coal was defined by Eq. 1.
T otal Coal I nput − Residual Coal

Reacted Coal(%) = × 100 (1)
T otal Coal I nput
As can be seen, as the proportion of coal in the mixture increased, so did the
amount of residual coal. In addition, the reacted carbon percentage decreased which
shows that coal was used inefficiently by increasing the coal ratio.
The change in degree of metallization, which is defined as the ratio of metallic
iron to the total iron oxide input, is shown in Fig. 5. It is seen that metallization
increased by increasing coal amount, but its rate was decreased after 20% excess
coal.
The amount of coal used and the degree of metallization were taken into con-
sideration in order to determine the optimum coal ratio. In the reduction step, it is
preferred to obtain as high metallization as possible using as little coal as possible.
Fig. 4 Effect of excess coal addition on a residual carbon content, b percentage of reacted coal
Fig. 5 Effect of excess coal

addition on iron
metallization
Fig. 6 Variation of coal

efficiency with excess coal
added
In this case, the higher the ratio defined below, the more effective the coal usage.
Moles o f ox ygen eliminated f r om ir on oxide

Coal E f f iciency = (2)
Moles o f car bon added
where moles of oxygen eliminated can be calculated from degree of metallization.

In Fig. 6, the change in the coal efficiency is plotted against the excess coal used.
According to this graph, the 20% excess coal at which coal efficiency reaches the
highest value was chosen as the most suitable coal ratio.
Microstructure of the Reduced Samples
Figure 7 shows SEM images of the red mud sample reduced at 1000 °C. Metallic
iron particles of light gray color can be distinguished from the dark oxide matrix.
Although the size of the metallic particles sometimes exceeded 10 µm, it generally
varied between 1 and 5 µm. The distribution of metal particles in the oxide matrix
is shown in Fig. 7a–c at lower magnification.
EDS analysis of four different metallic particles is presented in Table 3. It was
observed that the non-ferrous elements in the red mud were not reduced and that the
metallic phase formed contained only iron and a small amount of carbon.
400 S. Eray et al.
Fig. 7 Representative SEM micrographs of the reduced red mud samples
Table 3 Representative EDS analysis of the metallic particles

EDS analysis—1 EDS analysis—2 EDS analysis—3 EDS analysis—4
Fe 99.18 96.4 95.7 93.2
C 0.82 3.6 4.3 6.8
XRD analysis of the reduced sample is shown in Fig. 8. According to this analysis,
the reduced sample consists of metallic iron, nepheline, and perovskite phases.
Effect of Temperature
Experiments were conducted at 1000, 1100, and 1200 °C to examine the effect of
temperature. 20% excess coal was used in these experiments. Figure 9 shows the
change in the degree of metallization for these samples. Increasing temperature from
1000 to 1100 greatly improved the metallization. However, further increase to 1200
°C had a slight effect.
Fig. 8 XRD pattern of the reduced red mud sample
Fig. 9 Effect of temperature

on the degree of
metallization of iron
Magnetic Separation
Wet magnetic separation was used to recover the iron in the reduced samples. The
particle size of the sample closely affects the magnetic separation process. For suc-
cessful separation, the Fe particles shown in Fig. 7 must be completely liberated
from the oxide matrix. Therefore, the coarsely ground samples in the ring mill were
subjected to a second grinding in the ball mill. Figure 10 compares the metallic iron
content of the magnetic concentrates for different samples.
It is seen that grinding had the minimum effect on the iron content of the concen-
trates obtained from the samples reduced at 1000 °C. In contrast, it had great impact
on the iron content of the concentrates obtained from samples reduced at higher
temperatures. For these samples, the grinding process increased the iron content of
the concentrates from about 30% to about 75%. Comparing the samples reduced at
1100 and 1200 °C, the highest yield belongs to 1100 °C. The comparatively lower
iron content of the samples reduced at 1200 °C may be attributed to the lower grind-
ability of these samples. Higher reduction temperatures results in severe sintering
402 S. Eray et al.
Fig. 10 Effect of grinding

time on the iron content of
the magnetic concentrate
of the sample which in turn makes it harder to liberate fine metallic particles upon
grinding.
Conclusions
Turkish red mud waste supplied by Eti Alüminyum A.Ş. was studied to recover iron.
The red mud sample was subjected to solid state reduction followed by wet magnetic
separation. The main findings of the research are as follows:
– The as-received sample contained 34% iron oxide. XRD analysis revealed that the
sample was mainly composed of hematite, hydroxycancrinite, gibbsite, calcite,
and rutile.
– The optimum amount of coal was determined to be 20% higher than the
theoretically required amount.
– The increasing of temperature from 1000 to 1100 °C had a significant effect on
metallization, but further increase did not appear to have much effect.
– Under the best temperature and grinding conditions (1100 °C, 20% excess coal,
48 h milling), a concentrate containing 75% iron was obtained. Iron recovery for
this sample was about 95%.
Acknowledgements The Scientific and Technological Research Council of Turkey (TÜBİTAK)

is greatly acknowledged for the financial support under the project no: 117M185.
References
1. Paramguru RK, Rath PC, Misra VN (2005) Trend in red mud utilization—a review. Miner
Process Extr Metall Rev Int J 26:1–29
2. Mayes W et al (2015) Risks, remediation and recovery: lessons for bauxite rsidue management
from Ajka. Paper presented at the bauxite residue valorisation and best practices, Leuven, 5–7
October 2015
3. Li G, Liu M, Rao M, Jiang T, Zhuang J, Zhang Y (2014) Stepwise extraction of valuable

components from red mud based on reductive roasting with sodium salts. J Hazard Mater
280:774–780
4. Samouhos M, Taxiarchou M, Tsakiridis PE, Potiriadis K (2013) Greek “red mud” residue:
a study of microwave reductive roasting followed by magnetic separation for a metallic iron
recovery process. J Hazard Mater 254–255:193–205
5. Zhu D, Chun T, Pan J, He Z (2012) Recovery of iron from high-iron red mud by reduction
roasting with adding sodium salt. J Iron Steel Res Int 19(8):1–5
6. Borra CR, Pontikes Y, Binnemans K, Gerven TV (2015) Leaching of rare earths from bauxite
residue (red mud). Miner Eng 76:20–27
7. Wang W, Pranolo Y, Cheng CY (2013) Recovery of scandium from synthetic red mud leach
solutions by solvent extraction with D2EHPA. Sep Purif Technol 108:96–102
8. Liu Y, Naidu R (2014) Hidden values in bauxite residue (red mud): recovery of metals. Waste
Manag 34(12):2662–2673
9. Liu Z, Li H (2015) Metallurgical process for valuable elements recovery from red mud—a
review. Hydrometallurgy 155:29–43
10. Piga L, Pochetti F, Stoppa L (1993) Recovering metals from red mud generated during alumina
production. JOM 45(11):54–59
Self-reduction of Core-Shell EAF
Dust-Biochar Composite Pellets Under
Microwave Irradiation
Liancheng Wang, Zhiwei Peng, Lei Yang, Leixia Zheng, Jie Wang,
Wenxing Shang, Anton Anzulevich, Mingjun Rao, Guanghui Li
and Tao Jiang
Abstract Electric arc furnace (EAF) dust is an important secondary resource from
which valuable elements can be recovered. The recovery process can be intensified by
the self-reduction of core-shell EAF dust-biochar composite pellets under microwave
irradiation. In this study, the effects of various parameters on reduction of the core-
shell EAF dust-biochar composite pellets in N2 were explored. It was demonstrated
that under the optimal conditions of reduction temperature of 1050 °C, dwell time
of 20 min, total C/Fe mass ratio of 0.24, C/Fe mass ratio of pellet core of 0.30,
and diameter of pellet core of 6–8 mm, the resulting metallized pellets had total iron
content of 70.13 wt %, iron metallization degree of 97.97%, volatilization percentage
of zinc of 99.52%, volatilization percentage of lead of 98.49%, manganese content of
2.83 wt % and chromium content of 0.22 wt %. The great reduction performance was
attributed to strong gasification of carbon in association with selective distribution
of biochar in the composite pellets with good microwave absorption.
Keywords EAF dust · Biochar · Core-shell structure · Gasification efficiency ·

Selective distribution · Self-reduction
Introduction
Electric arc furnace (EAF) dust is a metallurgical waste produced in the EAF steel-
making process. In general, the output of EAF dust is about 1–2% of the EAF charge.
The dust has been categorized as a dangerous waste in need of safe disposal [1].
L. Wang · Z. Peng (B) · L. Yang · L. Zheng · J. Wang · W. Shang · M. Rao · G. Li · T. Jiang

410083, China
Changsha, Hunan 410083, China
A. Anzulevich
Chelyabinsk State University, Chelyabinsk 454001, Russia

https://doi.org/10.1007/978-3-030-36540-0_36
406 L. Wang et al.
EAF dust contains a large amount of valuable elements, e.g., Fe, Zn, and heavy
metals, such as Cr, Pb, and Cd [2]. The valuable elements mainly exist in the forms
of oxides and spinels, with high thermal and chemical stability [3]. Owing to the
complex composition and refractory characteristics of EAF dust, there has been
limited progress in its treatment although various techniques were developed [4–6].
The EAF dust can be recycled by microwave reduction to obtain higher quality
iron-rich concentrate and zinc product, in comparison with those obtained by con-
ventional methods [7]. It was found that the activation energy of reduction reaction
of ZnO under microwave irradiation was 335 kJ/mol, which was lower than that of
conventional reduction [8].
Very recently, the authors’ group proposed a method for intensifying reduction of
iron ore by reducing core-shell iron ore-biochar composite pellets under microwave
irradiation. It took advantage of microwave induced directional migration of different
elements. The results showed that microwave played an important role in intensifying
the self-reduction of core-shell composite pellets [9–11]. The biochar was used as
the reducing agent mainly because of its high chemical reactivity and low impurity
content [12].
This study was devoted to the recovery of valuable elements from EAF dust by
microwave-assisted self-reduction of core-shell EAF dust-biochar composite pellets.
The proper structure of the pellets could promote carbon gasification and microwave
absorption for higher reduction performance. The effects of various parameters on
the reduction were explored in detail.
Experimental
Materials
The EAF dust used in this study was obtained from a steelmaking plant in China. Its
main chemical composition is shown in Table 1.
Table 1 shows that the dust contained a large amount of valuable elements, includ-
ing Fe, Zn, Mn, and Mg, as well as heavy metals, such as Pb and Cr. Moreover, the
gangue minerals mainly included CaO, SiO2, and Al2 O3 .
Figure 1a shows that the main phases of EAF dust were franklinite, magnetite,
magnesium ferrite, hematite, and calcium magnesium silicate. Zinc was mainly in
the form of franklinite which was featured by high thermal and chemical stability.
From the particle size distribution of the dust (Fig. 1b), 90% of the particles were
less than 2.041 μm and more than 50% of the particles were less than 0.188 μm.
Figure 2a shows that most of the particles were spherical with large pores between
them.
According to the industrial analysis of biochar, it had fixed carbon content of
73.47 wt % and ash content of 11 wt %. It had 96.18% of particles passing 44 μm
Table 1 Main chemical composition of EAF dust (wt %)
Component Fe Zn Mn Mg Pb Cr CaO Al2 O3 SiO2 K Na Cl
Content 51.53 4.69 2.74 2.48 0.13 0.24 8.96 1.27 3.02 1.07 1.03 0.66
Self-reduction of Core-Shell EAF Dust-Biochar Composite Pellets …
407
408 L. Wang et al.
(a) (b)
Fig. 1 a XRD pattern and b particle size distribution of EAF dust
Fig. 2 Microstructures of a EAF dust and b biochar
sieve. Figure 2b shows that the biochar had a porous structure that would promote
the Boudouard reaction by providing channels for diffusion of reducing gas.
Methods
With different C/Fe mass ratios of core and shell, the EAF dust and biochar were
mixed to prepare qualified green pellets with the size of 10–12 mm. The qualified
pellets were dried in an oven at 110 °C for 24 h. The dried pellets were then reduced
using a microwave tube furnace (maximum power of 1.4 kW, 2.45 GHz, Change
Microwave Technology Co., Ltd., Changsha, China). After reduction, the metallized
pellets obtained were collected for analysis. The total iron grade (TFe), iron metal-
lization degree (ηFe ), and manganese content (TMn ) were determined by chemical
titration. The contents of zinc, lead, and chromium (TCr ) were measured using induc-
tively coupled plasma-optical emission spectrometry (ICP-OES, ICAP7400 Radial,
Self-reduction of Core-Shell EAF Dust-Biochar Composite Pellets … 409
Thermo Fisher Scientific, America). The volatilization percentages of zinc (VZn ) and
lead (VPb ) were then calculated. The phase compositions of the metallized pellets
were determined using an X-ray diffraction spectrometer (XRD, D/max 2550 PC,
Rigaku., Ltd., Japan). The microstructures of the metallized pellets were character-
ized using a scanning electron microscope (SEM;FEI QUANTA200; FEI, Eindhoven,
The Netherlands) equipped with an EDAX energy-dispersive X-ray spectroscopy
(EDS) detector (EDAX Inc., Mahwah, NJ, USA).
Effect of C/Fe Mass Ratio of Pellet
Under the conditions of reduction temperature of 1050 °C, dwell time of 20 min,
and N2 flow rate of 0.2 L/min, the effect of C/Fe mass ratio of pellet on the reduction
was studied. The results are shown in Fig. 3.
When the C/Fe mass ratio increased from 0.18 to 0.20, the TFe increased from
65.18 to 70.35 wt %. As it continued to increase to 0.24, the TFe decreased slightly to
68.78 wt %. The ηFe increased significantly from 78.00% to 94.96% with increasing
of C/Fe mass ratio. The VZn and VPb increased sharply from 81.87% and 61.09%
to 95.07% and 93.24%, respectively, as the C/Fe mass ratio increased from 0.18 to
0.20. They reached the maximum volatilization percentages of 99.35% and 97.52%,
respectively, when the C/Fe mass ratio was 0.24. The TMn increased slightly with
increasing C/Fe mass ratio, while the TCr had a slight decreasing trend. The variations
of these values were resulted from stronger carbon gasification at higher C/Fe mass
ratios.
Fig. 3 Effect of C/Fe mass ratio of pellet on the reduction of EAF dust-biochar composite pellets
410 L. Wang et al.
Fig. 4 XRD patterns of metallized pellets obtained by reduction of EAF dust-biochar composite
pellets with different C/Fe mass ratios
Figure 4 shows the XRD patterns of metallized pellets obtained by reduction of

EAF dust-biochar composite pellets with different C/Fe mass ratios. As the C/Fe mass
ratio increased from 0.18 to 0.22, the peak intensity of metallic iron increased contin-
uously. On the contrary, the peak intensities of wüstite and kirschsteinite decreased.
When the C/Fe mass ratio reached 0.24, the peak intensity of metallic iron decreased
slightly and only several peaks of kirschsteinite remained. Obviously, the suitable
C/Fe mass ratio was 0.24.
Effect of C/Fe Mass Ratio of Pellet Core
Under the conditions of reduction temperature of 1050 °C, dwell time of 20 min, N2
flow rate of 0.2 L/min, C/Fe mass ratio of pellet of 0.24, and diameter of the pellet
core of 6–8 mm, the effect of C/Fe mass ratio of pellet core on the reduction was
studied. The results are shown in Fig. 5.
Figure 5 demonstrates that with the increase of the C/Fe mass ratio of pellet
core, the TFe had a small fluctuation. Meanwhile, the ηFe increased from 94.85% to
97.97%. When the C/Fe mass ratio of pellet was 0.24, the change of the C/Fe mass
ratio of pellet core had little effect on the VZn , which maintained above 99.50%. How-
ever, the changing trend of VPb varied apparently. The maximum VPb was 98.49%
when the C/Fe ratio was 0.30. The change of TCr was similar to that of VPb . As for
TMn , it changed slightly.
Fig. 5 Effect of C/Fe mass ratio of pellet core on the reduction of EAF dust-biochar composite
pellets
Figure 6 shows the XRD patterns of metallized pellets obtained by reducing EAF
dust-biochar composite pellets with different C/Fe mass ratios in the pellet core.
The peak intensity of the metallic iron continuously increased when the C/Fe mass
ratio of pellet core increased from 0.22 to 0.28. Conversely, the peak intensities
Fig. 6 XRD patterns of metallized pellets obtained by reducing EAF dust-biochar composite pellets
with different C/Fe mass ratios in the pellet core
412 L. Wang et al.
of kirschsteinite and wüstite decreased. When the ratio increased to 0.30, the peak
intensity of metallic iron and wüstite became slightly lower, with the disappearance
of kirschsteinite. Compared with the reduction of homogeneous composite pellets
(the ratio was 0.24 in Fig. 6), the self-reduction of core-shell composite pellets was
intensified by the selective distribution of biochar which had better gasification.
The improved reduction performance could also be attributed to the distinct heat
diffusion in microwave heating by which the temperatures of pellet core and shell
might increase simultaneously, accelerating chemical reactions.
Effect of Diameter of Pellet Core
Under the conditions of reduction temperature of 1050 °C, dwell time of 20 min, N2
flow rate of 0.2 L/min, C/Fe mass ratio of pellet of 0.24, the effect of diameter of
pellet core was studied. The results are shown in Fig. 7.
Figure 7 reveals that all the indexes of metallized pellets increased first and then
declined as the diameter of pellet core increased. When the diameter was 6–8 mm
(average diameter was 7 mm), they had the optimal values. The TFe, ηFe , VZn ,
VPb , TMn, and TCr were 70.13 wt %, 97.97%, 99.52%, 98.49%, 2.83 wt %, and
0.22 wt %, respectively.
Fig. 7 Effect of diameter of pellet core on the reduction of core-shell EAF dust-biochar composite
pellets
Fig. 8 XRD patterns of metallized pellets obtained by reducing core-shell EAF dust-biochar
composite pellets with different core diameters
Figure 8 shows the XRD patterns of metallized pellets obtained by reducing

core-shell EAF dust-biochar composite pellets with different core diameters. With
increase of diameter from 5–6 to 6–8 mm, the peak intensity of metallic iron kept
stable, but those of wüstite and kirschsteinite decreased. When the diameter was
8–10 mm, the peak intensity of metallic iron increased slightly, with slight increases
of wüstite and kirschsteinite. The results showed that a proper diameter of pellet core
was of significance for the microwave-assisted self-reduction of core-shell composite
pellets because both chemical compositions and structures of the pellets controlled
the microwave dissipation.
Figure 9 shows the SEM-EDS results of metallized pellets obtained by reducing
core-shell EAF dust-biochar composite pellets with core diameter of 6–8 mm. The
metallized pellets were mainly constituted by the metallic iron (spot 1), calcium
containing silicate minerals (spot 2), and residual carbon (spot 3). Overall, the pellets
had good self-reduction.
Conclusions
In this study, the core-shell EAF dust-biochar composite pellets were prepared and
reduced using microwave energy. The results revealed that the core-shell EAF dust-
biochar composite pellets had nearly complete reduction. Owing to the higher carbon
content in the core than the shell, the microwave passing through the shell could be
absorbed effectively in the core. By controlling the pellets with the C/Fe mass
ratio of pellet of 0.24, C/Fe mass ratio of pellet core of 0.30, and diameter of pellet
core of 6–8 mm, reduction temperature of 1050 °C, dwell time of 20 min, N2 flow
414 L. Wang et al.
Fig. 9 SEM-EDS analysis of metallized pellets obtained by reducing core-shell EAF dust-biochar
composite pellets with core diameter of 6–8 mm
rate of 0.2 L/min, the core-shell EAF dust-biochar composite pellets achieved opti-
mal reduction performance, and the TFe, ηFe , VZn , VPb , TMn, and TCr were 70.13
wt %, 97.97%, 99.52%, 98.49%, 2.83 wt %, and 0.22 wt %, respectively. The results
showed that almost all iron oxides were converted into metallic iron, and zinc and
lead were removed by volatilization. It verified the strong self-reduction of core-shell
EAF dust-biochar composite pellets under microwave irradiation.
tion of China under Grants 51774337 and 51504297, the Natural Science Foundation of Hunan
Province, China, under Grant 2017JJ3383, the Science and Technology Planning Project of Hunan
Province, China, under Grant 2019RS2008, the Hunan Provincial Innovation Foundation for
Postgraduate under Grant CX20190230, and the Fundamental Research Funds for the Central
Universities of Central South University under Grants 2019zzts174 and GS201910533550.
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Recovery of Copper from Copper
Smelting Slag Using a Green Reductant
Guorui Qu, Yonggang Wei, Bo Li, Hua Wang, Yindong Yang

and Alexander McLean
Abstract A new process is proposed for recovering copper from smelting slag using
waste cooking oil as a green reductant. More than 70% of waste cooking oil pyrolysis
products is hydrogen. In this study, a 70% H2 -30% N2 gas mixture was used to
simulate pyrolysis products for copper slag reduction experiments. The equilibrium
composition, oxygen potential, reduction degree of Fe3 O4 and the content of copper
dissolved in the slag were calculated using FactSage software. The experimental
results show that the Fe3 O4 in the slag is reduced from 12.9 to 2.9%, and the copper
from 17.82 to 0.53%. The unrecovered copper is mainly dissolved in the slag.
Keywords Copper smelting slag · Biomass reductant · Cleaning process
Introduction
There are two main types of copper production processes: pyrometallurgy and
hydrometallurgy. At present, nearly 80% of copper is produced by pyrometallur-
gical smelting [1]. Copper slag is the main by-product of the copper pyrometallurgy
processes. Among them, the oxygen enrichment smelting process is widely used.
The high oxygen potential increases the content of magnetite in the slag, which
increases the viscosity of the slag and reduces the recovery of copper [2]. Therefore,
the copper slag produced by this process usually has a high copper content [3–5]. In
G. Qu · Y. Wei (B) · B. Li · H. Wang

State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming
650093, China
e-mail: weiygcp@aliyun.com
G. Qu · Y. Wei · B. Li
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China
Y. Yang · A. McLean
Department of Materials Science and Engineering, University of Toronto, Toronto, ON M5S3E4,
Canada

https://doi.org/10.1007/978-3-030-36540-0_37
418 G. Qu et al.
order to recover the copper in the slag, it is necessary to reduce the content of mag-
netite, thereby increasing the fluidity of the slag and promoting the settling of matte
droplets. The cleaning of copper slag usually uses coal, coke, diesel, and natural gas
as reductant. However, as energy shortages and environmental pollution intensify,
the metallurgical industry needs a clean and sustainable reductant, such as biomass,
to replace traditional reductants.
As a renewable resource, biomass is characterized by sustainability and extensive
sources. The use of biomass as a reductant has recently attracted much attention. Zou
et al. [6] analyzed biomass as a reducing agent in the cleaning of copper slag from
the perspective of thermodynamics. Kumar et al. [7] studied the production of iron
with waste macadamia as a reductant. Zhou et al. [8] used walnut shell char to reduce
waste copper slag. As a waste biomass resource, waste cooking oil has low carbon
emissions and reuses the waste [9, 10]. China produces nearly 3.0–4.5 million tons
of waste cooking oil per year [11] and most is not used properly [12]. In this work, a
new process is proposed for cleaning copper slag with waste cooking oil as a green
reductant. The results show that waste cooking oil can reduce the magnetite content
in copper slag to less than 3% with a reduction efficiency of more than 90% [13].
The main gas produced by the high-temperature pyrolysis of waste cooking oil is
hydrogen, which accounts for more than 70% and is an ideal substitute for traditional
reductant [14]. Based on previous research, this paper examines the effect of hydrogen
on the cleaning of copper slag with the aid of thermodynamic calculations, high-
temperature experiments and microscopic examination of the product.
Experimental
Materials
The sample was obtained from slag that was generated during the oxygen enrichment
copper smelting process. The chemical composition shown in Table 1 indicates that
the Cu content was 17.82% and the Fe3 O4 content was 12.9%. Due to the fact that the
copper slag was produced by the oxygen enrichment process, the copper and Fe3 O4
contents are relatively high. XRD results (Fig. 1) show that the main phases in the
slag are fayalite and magnetite while copper is present in the form of matte.
Figure 2 shows the microstructure and EDS spectra of the phases in the slag
sample. The EDS results show that the white phase is matte (point 1), the gray
phase is magnetite (point 2), and the dark gray phase is fayalite (point 3). The matte
is distributed in the slag as large particle agglomerates as well as small spherical
particles.
Table 1 Chemical analysis of the copper slag
Component Cu Fe(Total) SiO2 S Al2 O3 CaO MgO Zn Fe3 O4
Recovery of Copper from Copper Smelting Slag …
Content, wt% 17.82 33.06 19.13 8.07 2.96 2.12 1.95 1.83 12.9
419
420 G. Qu et al.
Fig. 1 XRD pattern of the copper slag sample
Fig. 2 Microstructure and EDS analyses of the copper slag sample
Apparatus and Procedure
Figure 3 is a schematic view of the experimental apparatus. First, 300 g of copper

slag was placed in a crucible, and then the crucible was located within a vertical
tube furnace. The corundum reaction chamber of the furnace was evacuated using
a mechanical rotary pump; nitrogen gas was then introduced (100 mL/min) and
controlled by a rotameter. The furnace was heated to the required temperature and
held for 30 min to fully melt the slag. A mixed gas of 70% H2 -30% N2 was blown
into the slag through a spray gun. After the end of blowing, the temperature was kept
Recovery of Copper from Copper Smelting Slag … 421
Fig. 3 Schematic of laboratory equipment
constant for 30 min, in order to ensure the remaining matte particles fully settled
within the slag. Finally, the molten slag was slowly cooled to room temperature.
FactSage software was used for relevant thermodynamic calculations. The sample
was analyzed by electron probe microscopy using the backscattered electron (BSE)
mode. The Fe3 O4 content in the slag was determined using a Satmagan 135 type
magnetic analyzer.
The following reactions may occur when the copper slag is exposed to a 70% H2 -30%
N2 gas mixture:
Fe3 O4 + H2 (g) = 3FeO + H2 O (1)
FeO + H2 (g) = Fe + H2 O (2)
2FeO · SiO2 + 2H2 = 2Fe + 2H2 O + SiO2 (3)
According to the Gibbs free energy minimization principle, when the Gibbs free
energy change is less than zero, the reaction can proceed spontaneously. Figure 4
shows the change in Gibbs free energy with temperature for the above reactions. It
can be seen from this figure that the Gibbs free energy for all the reactions decreases
422 G. Qu et al.
Fig. 4 Gibbs free energy change curves of reactions with change of temperature
with increasing temperature. In the smelting reduction region (1498–1573 K), H2 can
only react with Fe3 O4 to form FeO (Eq. (1)). H2 cannot reduce FeO or 2FeO·SiO2
to form Fe. Therefore, H2 is an effective reductant for the cleaning of copper slag.
The equilibrium composition was calculated by the Factsage equilibrium mod-
ule. The content of the main components was calculated by molar weight, and the
results are shown in Table 2. The thermodynamic analysis was conducted taking the
following conditions into account:
(i) The mass of copper slag is 100 g, and the atmospheric pressure is 0.1 MPa.
(ii) The mixed gas is 70% H2 -30% N2 .
(iii) Phases with contents lower than 0.5% are not discussed.
Figure 5a shows the change of equilibrium composition with the amount of mixed
gas. It can be seen that as the amount of mixed gas increases, the Fe3 O4 content
decreases, while no Fe is formed. This indicates that H2 can reduce Fe3 O4 to produce
FeO but not Fe. Also, the content of SiO2 decreases with the increase in amount of
mixed gas while the content of Fe2 SiO4 increases gradually, which indicates that
the reduced product FeO reacts with SiO2 to form Fe2 SiO4 . The Gibbs free energy
calculation shows that the reduction of Fe2 SiO4 with hydrogen is not feasible.
The reduction degree of Fe3 O4 can be calculated by using the change of Fe3 O4
content in the equilibrium component. The calculation formula is as follows:
Table 2 Phase compositions of initial copper slag

Component Cu2 S FeS Fe3 O4 FeO SiO2 CaO Al2 O3 MgO
Mole/(mol) 0.139 0.085 0.056 0.310 0.319 0.053 0.029 0.049
Fig. 5 Effects of mixed gas on equilibrium compositions and reduction degree
n0 Fe3 O4 − nFe3 O4
η= (4)
n0 Fe3 O4
where n0 Fe3 O4 is the molar quantity of Fe3 O4 in copper slag before reduction and
nFe3 O4 is the molar quantity of Fe3 O4 in copper slag after reduction.
Figure 5b shows that the degree of reduction increases as the amount of mixed
gas amount increases. When the amount of the mixed gas is 0.08 mol, the reduction
degree is 0.75.
Numerical Determination of Chemically Dissolved Copper

in Slag
It is well known that copper losses in slag fall into two major categories: mechanical
entrainment and chemical dissolution [15–17]. The cleaning of copper slag mainly
recovers the copper present in the form of mechanical entrainment, which is due to
the fact that chemically dissolved copper cannot be recovered by physical deposition.
Therefore, it is particularly important to clarify the content of chemically dissolved
copper in the slag after cleaning.
The dissolved copper in the slag exists in the form of sulfide and oxide [18]. Thus,
the total dissolved copper in slag is the sum of the sulfidic and oxidic dissolution.
The expression for total dissolved copper is given by Eq. (5):
(%Cu)t = (%Cu)o + (%Cu)s (5)
where (%Cu)t is total dissolved copper, (%Cu)o is oxidic dissolved copper, and
(%Cu)s is sulfidic dissolved copper.
424 G. Qu et al.
Toguri and Santander [19] proposed the following expression for oxidic dissolved
copper:
(%Cu)O = 29.73aCuO0.5 (6)
The oxidation of copper is represented by
Cu + 1/4O2 = CuO0.5 (7)
aCuO0.5
K= 1/4
(8)
PO2 aCu
Here K is the equilibrium constant of the reaction expressed by Eq. (7), aCuO0.5 is
CuO0.5 activity, aCu is Cu activity, and PO2 is oxygen partial pressure.
Hence, aCuO0.5 can be represented as
1/4
aCuO0.5 = Kacu PO2 (9)
Inserting Eq. (9) into Eq. (6), the oxidic dissolved copper is eventually expressed
by
1/4
(%Cu)O = 29.73KaCu PO2 (10)
In Eq. 10, aCu ≈ 1, and PO2 can be calculated using the Factsage pair. The cal-
culation results are shown in Fig. 6a. The calculation assumes that the matte has
settled.
Mackey [20] further clarified the calculation model of the sulfidic dissolved copper
proposed by Nagamori [18], and obtained the following formula for the sulfidic
copper dissolved in commercial slag:
Fig. 6 Effects of Fe3 O4 content on: a PO2 ; b dissolved Cu in slag

(%Cu)S = 0.00495[S]SI [Cu]mt (11)
where [S]Sl = 2.2 − 3.75x + 1.25x2 ,X = 0.01 [Cu]mt , [Cu]mt is copper content of
matte.
The total dissolved copper content in the slag is calculated by Eqs. (5)–(11). As
shown in Fig. 6b, the dissolved copper content at different temperatures decreases
with the decrease of Fe3 O4 content. In the initial stage, the dissolved copper content
decreased slightly as the Fe3 O4 content decreased. When the Fe3 O4 content is reduced
to less than 14%, the content of dissolved copper is significantly decreased. However,
when the Fe3 O4 is less than 2%, the dissolved copper does not change significantly
and remains almost constant at about 0.45%. These results show that the slag always
contains a certain amount of dissolved copper. It is also evident that when Fe3 O4 is
less than 2%, further reduction of Fe3 O4 does not improve the recovery of copper.
Experimental Evaluation of the Cleaning of Copper Slag

with 70% H2 -30% N2 Gas Mixture
Under the conditions of 0.4 L/min gas flow and blowing time of 10 min, the effects
of reduction temperature on the Fe3 O4 and copper contents of slag in the cleaning
process were investigated. As shown in Fig. 7a, at 1225 °C, the reduction effect
is small, and the content of Fe3 O4 and copper in the slag are both high. As the
temperature increased to 1250 °C, the Fe3 O4 and the copper contents in the slag
decreased significantly. At this temperature, the Fe3 O4 content was 5%, and the slag
contained 1.2% copper. Between 1250 and 1300 °C, the Fe3 O4 and copper contents
of slag decreased by a relatively small amount. For this reason, 1250 °C was selected
for the subsequent experiments. The decrease in Fe3 O4 and copper contents with
increasing temperature is mainly attributed to: (1) the decrease in Gibbs free energy
for Reaction (1) and the shift in equilibrium towards the right. (2) The increased
liquefaction of the slag resulting in a decrease in the slag viscosity. The viscosity of
the slag is closely related to the settling velocity of the matte droplets as indicated
by the following expression [21, 22]:
V = 2gr2 (ρm − ρs )/9μ (12)
where V is the matte droplet settling velocity (m/h), g is gravitational acceleration

(m/s2 ), r is the radius of the matte droplet (m), ρm is the matte density (kg/m3 ), ρs is
the density of the slag(kg/m3 ), and μ is the viscosity of the slag.
As can be seen from Eq. (12), with a decrease in the viscosity of the slag, the
setting velocity markedly increases. Thus, an increase in temperature leads to an
increase in the fluidity of the slag, which produces an increase in the sedimentation
rate of the matte droplets, and this is advantageous for the recovery of copper.
426 G. Qu et al.
Fig. 7 Cu and Fe3 O4 contents in the slag as a function of: a temperature; b gas flow rate; c blowing
time
The copper slag cleaning experiment was carried out at 1250 °C and a blowing
time 20 min. The results are shown in Fig. 7b. With the increase in gas flow rate, the
Fe3 O4 content in the slag decreases, but the copper content in the slag increases. The
reason for this is that the drastic agitation of the molten slag by the gas can hinder the
sedimentation of the matte droplets. Based on these findings, 0.2 L/min was selected
for the subsequent experiments.
Figure 7c shows the effect of blowing time on the contents of Fe3 O4 and copper
in the slag at 1250 °C and a gas flow rate of 0.2 L/min. When the blowing time
was 5 min, the Fe3 O4 and copper contents in the slag were high at 12%, and 14%,
respectively. When the blowing time was increased to 10 min, the Fe3 O4 and the
copper were significantly reduced. With the availability of hydrogen for a longer
period of time the reduction of Fe3 O4 is increased and this will lead to a decrease
in slag viscosity which is conducive to the settling of matte. As the blowing time is
extended to 20 min, the Fe3 O4 content in the slag is reduced to 2.9%, and the copper
content to 0.53%. As can be seen from Fig. 7, when the temperature is 1250 °C and the
Fe3 O4 content is 3%, the dissolved copper content in the slag is 0.5%. These results
indicate that copper in the slag after cleaning is mainly composed of chemically
dissolved copper.
SEM Analysis of the Reduced Sample
EPMA analysis of the cleaned copper slag sample was conducted and the results are
shown in Fig. 8. Figure 8a is a photo of the copper slag sample showing the upper,
middle and lower parts of the slag layer as well as the matte layer. Figure 8e shows
the microstructure of the matte layer, which is obviously different from the other
zones. Based on the EDS analysis, the gray areas can be identified as matte and the
light gray areas as copper. These results indicate that after cleaning, the matte and
copper will settle at the bottom of the crucible. Figures 8b, c correspond to the upper
and middle parts, respectively, of the slag layer. There was no significant difference
in microstructure between the two regions. The main phase is largely composed of
fayalite with a small amount of magnetite. Very little residual matte is embedded
in the fayalite. Figure 8d shows that the lower part of the slag layer contains large
particles of matte which is in contrast to the upper and middle parts of the slag layer.
The EMPA analysis results provide further proof that the copper loss in the cleaned
slag is mainly chemically dissolved copper. Only a small amount of mechanical
entrained copper is present in the lower part of the slag layer.
Fig. 8 Microstructures and EDS analyses of the copper slag sample: a copper slag sample; b upper
part of slag layer; c middle part of slag layer; d lower part of slag layer; e matte
428 G. Qu et al.
Conclusions
Theoretical analysis shows that a 70% H2 -30% N2 gas mixture can effectively reduce
Fe3 O4 to FeO without excessive reduction. Based on the experimental results, the
Fe3 O4 in the slag is reduced from 12.9 to 2.9%, and the copper from 17.82 to 0.53%.
After the cleaning process, the matte settles at the bottom of the crucible to achieve
enrichment recovery. Copper loss in the cleaned slag is mainly chemically dissolved
copper. These findings confirm that it is feasible to use waste oil as a reducing agent,
thus achieving the cleaning process and utilization of waste resources.
Acknowledgements This work was supported by the National Natural Science Foundation of
China (51664039 and 51974142); and the Analysis and Testing Foundation of Kunming University
of Science and Technology (2017P20161102004, 2018M20172228012).
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8. Zhou S, Wei Y, Li B, Wang H (2019) Cleaner recycling of iron from waste copper slag by using
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9. de Araújo C D M, de Andrade C C, e Silva E D S, Dupas F A (2013) Biodiesel production
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Manag 168:74–84
11. Chen S, Xu L (2018) A rustic opinion for govern and control of waste cooking oil. China Food
Drug Adm Mag 4:50–53 (In Chinese)
12. Liu T, Liu Y, Wu S, Xue J, Wu Y, Li Y, Kang X (2018) Restaurants’ behaviour, awareness,
and willingness to submit waste cooking oil for biofuel production in Beijing. J Clean Prod
204:636–642
13. Li B, Wang X, Wang H, Wei Y, Hu J (2017) Smelting reduction and kinetics analysis of
magnetic iron in copper slag using waste cooking oil. Sci Rep 7(1):2406
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15. Suh IK, Waseda Y, Yazawa A (1988) Some interesting aspects of non-ferrous metallurgical
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16. Liow JL, Juusela M, Gray NB, Šutalo ID (2003) Entrainment of a two-layer liquid through a
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17. Cardona N, Hernandez L, Araneda E, Parra R, Bahamondes L, Parada R, Artigas M (2010) Eval-
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Separation of Vanadium from Iron
in Vanadium-Rich Molten Iron
Guangfen Liang, Xiangyong Lv, Yandong Li, Huamei Duan, Dengfu Chen,
Mujun Long and Song Xu
Abstract A large number of studies of vanadium extraction based on sodium roast-

ing experiments have been carried out in the laboratory through the self-designed
converter vanadium extraction device. The content of the main elements was ana-
lyzed by X-ray fluorescence spectrometer. The optimal conditions of roasting process
of vanadium slag were obtained as follows: addition of 19% Na2 CO3 , roasting tem-
perature of 800 °C, roasting time of 120 min, and the particle size of vanadium slag
was less than 125um. While the leaching process was conducted by water and the
optimal conditions were obtained as follows: the leaching temperature of 90 °C,
leaching time of 30 min, and the liquid–solid ratio of 8.0 mL/g. Under those optimal
conditions, the leaching efficiency of vanadium was greater than 89.4%. And the
enlarged experiments confirmed the stability of those parameters.
Keywords Vanadium extraction · Vanadium slag · Sodium roasting · Water

leaching
Introduction
Vanadium, as an important strategic resource, is widely used in steel, chemical indus-

try, national defense, and other fields [1, 2]. Vanadic titanomagnetite, waste catalyst
and other vanadium containing minerals are the main raw materials for vanadium
extraction. At present, there are three main technologies for vanadium extraction
G. Liang · X. Lv · H. Duan (B) · D. Chen · M. Long

e-mail: duanhuamei@cqu.edu.cn
Chongqing Key Laboratory of Vanadium-Titanium Metallurgy and New Materials, Chongqing
University, Chongqing 400044, China
Y. Li
College of Materials Science and Engineering, Yangtze Normal University, Chongqing 408100,
China
S. Xu
Bekaert (Asia) R&D Center, Jiangyin, China
https://doi.org/10.1007/978-3-030-36540-0_38
432 G. Liang et al.
from vanadic titanomagnetite ore [3]: direct vanadium extraction process, vanadium
extraction process from steel slag and vanadium extraction process from vanadium
slag. And the Vanadium extraction from vanadium slag is the main method of vana-
dium extraction over the word, mainly including sodium roasting method, calci-
fication roasting method, sub-molten salt method, sulfuric acid leaching method,
chlorination method and so on [4]. While the sodium roasting [5] to extract vana-
dium pentoxide from vanadium slag is the most widely used technology in industry
at present. The basic principle of sodium roasting is to convert valence state of vana-
dium into water-soluble high valence state of vanadate by roasting vanadium slag
mixed with sodium salt under oxidation atmosphere. In industry, cheap sodium chlo-
ride is used as the sodium agent, and the economic benefit is better. However, a large
amount of chlorine, hydrogen chloride, and other chlorides are produced in the roast-
ing process, which can seriously corrode the equipment and buildings and pollute
the environment [6]. Moreover, due to the complex structure of raw materials, the
conversion of the sodium roasting process is different and needs detail research.
In recent years, scholars have done a lot of relevant research for extraction vana-
dium. Vuuren [7] studied the oxidation kinetics of FeV2 O4 at 200–580 °C. It was
pointed out that V (+3) was oxidized to V (+5) and combined with Fe2 O3 to form
FeVO4 at 400–470 °C. Barker and Hooper [8] proposed A sodium modification–
direct reduction coupled process for extraction of V and Fe from Vanadic titano-
magnetite. The recoveries of vanadium, iron, and titanium reached 84.52%, 89.37%,
and 95.59%, respectively. Moreover, the acid decomposition efficiency of titanium
slag reached 96.45%. Chen et al. [9] reported the comprehensive recovery of Fe, Ti,
and V from vanadium titanium magnetite. The recovery efficiency of titanium and
vanadium reached 96.3% and 96.6%, respectively. Aarabi-Karasgain [10] studied
the extraction of vanadium from steel slag containing vanadium (V2 O5 1.97%, CaO
44.29%) of a steel plant by using acid leaching process. The study proposed that the
size of roasting slag has a certain impact on the leaching efficiency of vanadium,
the suitable size of roasting slag is no more than 0.85 mm. Although the leaching
efficiency of the V was high in these studies, the use of the acid rising the cost of the
process and cause the severe corrosion of the equipment.
In this work, sodium carbonate was added to oxidize and roast vanadium slag to
get the clinker. The clinker was leached with water. XRD was used to analyze the
phase and XRF was used to perform the main chemical components of vanadium
slag, clinker, and leaching residue elements. Besides, the enlarged experiments were
carried out to verify the results.
Separation of Vanadium from Iron in Vanadium-Rich Molten Iron 433
Experimental
Raw Material
Analysis of the chemical composition of vanadium slag was performed in X-ray

fluorescence spectrum, operating at Rh Ka radiation source at 60 kV and 1400 mA.
And the main elements were shown in Table 1. X-ray diffraction (XRD) data in the
2θ range of –10 to 146° were collected the D/Max2500pc using a rotating anode
target radiation source at 25 kV. The pattern is shown in Fig. 1.
Reagents
Vanadium pentoxide (V2 O5 , AR), ammonium ferrous sulfate

((NH4 )2 Fe(SO4 )2 ·6H2 O, AR), the urea (H2 NCONH2 , AR), sodium nitrite (NaNO2 ,
AR), potassium permanganate (KMnO4 , AR), sodium carbonate (Na2 CO3 , AR),
phosphate (H3 PO4 , AR), and concentrated sulfuric acid (H2 SO4 , AR) were
purchased from Chongqing xingguang chemical glass co. LTD and used as received.
Method
20 g vanadium slag, purchased from a steel plant as raw material, was mixed with
3.8 g Na2 CO3 and roasted in a muffle furnace. After roasting, the obtained clinker was
crushed and ground to less than 120um. Then 5 g clinker was leached, filtered, and
separated by a sand suction filter. The leaching solution was kept to a constant volume
to 500 ml, then 10 ml of leaching solution was titrated by potassium permanganate
oxidation - ammonium ferrous sulfate titration method. Then the soluble vanadium
content in clinker was obtained. The leaching efficiency could be calculated through
the total vanadium in leaching solution and the vanadium content in vanadium slag.
m 0 ω0 − m 1 ω0
η= × 100% (1)
m 0 ω0
where: m0 is the mass of clinker, g; ω0 is the content of clinker; m1 is the mass of

residue, g; ω1 is the content of residue.
434
Table 1 XRF spectral analysis of vanadium slag (wt%)

Element O Mg Al Si P Ca Ti V Cr Mn Fe
wt% 25.3 2.31 1.73 8.54 0.196 3.14 4.98 7.60 2.75 6.69 36.8
G. Liang et al.
Fig. 1 XRD patterns of

vanadium slag
Results
There are many parameters influencing the conversion rate of vanadium roasting,
such as roasting temperature, roasting time, amount of additives, roasting atmo-
sphere, roasting method, the particle size of materials, and roasting equipment.
Figure 2 is the effect of roasting parameters of amount of Na2 CO3 , roasting tem-
perature, roasting time and particle size of vanadium slag on vanadium leaching
efficiency. The effects of different leaching parameters, such as temperature, time
and ratio of solid to liquid, on the leaching efficiency of vanadium were studied. The
results are presented in Fig. 3.
Figure 4a is the XRD pattern of clinker and leaching residue and Fig. 4b is the
XRD pattern of leaching residue.
The clinker and leaching residue were performed on an X fluorescence spectrum.
And the results are showed in, Tables 2 and 3, respectively.
The optimized parameters were obtained through experiments in the roasting and
leaching processes. The reliability and reproducibility of the obtained parameters
were checked by the increase of vanadium slag. 200 g, 500 g, and 1000 g vanadium
slag were conducted. The results are as follows:
Discussion
The Study of Roasting Conditions on Vanadium Leaching

Efficiency
It can be seen from Fig. 2a that vanadium leaching efficiency increases gradually
with the increase of the addition sodium carbonate. When sodium carbonate content
is 15%, vanadium leaching efficiency is only 78%. When the sodium carbonate
436 G. Liang et al.
Fig. 2 Effects of roasting parameters on leaching efficiency of vanadium slag. a Amount of

Na2 CO3 . b Roasting temperature. c Roasting time d Particle size of vanadium slag
content increases to 19%, the leaching efficiency of vanadium is about 89%. Further
increasing the amount of sodium carbonate, vanadium leaching efficiency increases
slowly. Considering the cost, the addition amount of sodium carbonate is 19%. As
can be seen from Fig. 2b, the leaching efficiency of vanadium increases first and then
decreases with the increase of roasting temperature. When the roasting temperature is
about 800 °C, the leaching rate of vanadium reaches its maximum value, close to 90%.
When the roasting temperature exceeds 840 °C, the leaching efficiency of vanadium
decreases sharply with the increase of temperature. Considering energy loss caused
by high temperature, the roasting temperature in this experiment was selected as
800 °C. From Fig. 2c, when the roasting time is less than 120 min, the leaching
efficiency of vanadium gradually increases with the roasting time lengthening. When
the roasting time is more than 120 min, the leaching rate of vanadium decreases.
Obviously, the leaching efficiency of vanadium is the highest when the roasting time
is around 120 min, so it is appropriate to choose the roasting time of 120 min. As
can be seen from Fig. 2d, the leaching efficiency of vanadium increases first and
then decreases with reduction of particle size. When the particle size was less than
125 μm, vanadium leaching efficiency was the highest (nearly 90%). Combined
with the results of this experiment, the particle size of vanadium slag should be
controlled less than 120um. From what has been discussed above, the optimum
Fig. 3 Effect of leaching parameters on vanadium leaching efficiency. a Leaching temperature.

b Leaching time. c Ratio of liquid to solid
Fig. 4 XRD patterns of a Clinker b Leaching residue
technological parameters of the roasting process of vanadium slag were as follows:

sodium carbonate content of 19%; roasting temperature of 800 °C; roasting time of
120 min, particle size of raw material was less than 125 μm.
438
Table 2 XRF spectral analysis of clinker (wt%)

Element O Na Mg Al Si P Ca Ti V Cr Mn Fe
wt% 28.20 8.43 2.10 1.32 9.46 0.14 3.20 3.82 6.42 4.01 5.10 23.50
G. Liang et al.
Table 3 XRF spectral analysis of leaching residue (wt%)
Element O Na Mg Al Si P Ca Ti V Cr Mn Fe
wt% 30.40 4.30 3.21 1.49 10.82 0.19 3.65 4.49 1.03 3.35 6.10 30.97
Separation of Vanadium from Iron in Vanadium-Rich Molten Iron
439
440 G. Liang et al.
The Study of Leaching Conditions on Vanadium Leaching

Efficiency
As can be seen from Fig. 3a, the leaching efficiency of vanadium gradually increases
with the increase of the leaching temperature, reaching a peak of nearly 90% at
90 °C. To obtain a higher vanadium leaching efficiency, the leaching temperature
should be set as high as possible. However, as the water bath temperature rises and
approaches the boiling point of water, the more difficult it is to achieve. Therefore,
considering the above factors, the optimal leaching temperature in this study was set
at 90 °C. As can be seen from Fig. 3b, the leaching efficiency of vanadium gradually
increases with the increase of leaching time. When the leaching time is 10 min, it can
reach more than 84.5%. And when the leaching time is more than 30 min, the leaching
efficiency does not change with time. Indicating that the clinker has completely
dissolved in water and reached its equilibrium, and all soluble vanadium in the clinker
has dissolved into the leaching solution. Therefore, the optimized leaching time was
30 min. Figure 3c shows that the leaching efficiency of vanadium increases with
the increase of liquid–solid ratio. When the liquid–solid ratio exceeds 8.0 mL/g, the
leaching efficiency of vanadium remains unchanged. Therefore, 8.0 mL/g is more
suitable for leaching process. Therefore, the optimal technological parameters of
leaching process are as follows: the leaching temperature of 90 °C, leaching time of
30 min, and the liquid–solid ratio of 8.0 mL/g.
XRD Analysis
From the XRD diagram of vanadium slag (Fig. 1), it can be seen that the main min-
eral phases in vanadium slag are vanadium spinel (Mn, Fe)(Cr, V)2 O4 , peridot(Fe,
Mg)2 SiO4 , pyroxene Ca(Fe, Mg)Si2 O6 , and iron oxide Fe2 O3 .Vanadium in vanadium
slag mainly occurs in spinel phase, mainly in the form of (Mn, Fe)(Cr, V)2 O4 and
MgV2 O4 . V2 O3 , Cr2 O3 , TiO2 , Fe2 O3, and MgO in vanadium slag are concentrated in
spinel phase, mainly in the form of Mg2 TiO4 and FeCr2 O4 . SiO2 and forms silicate
phase with other basic oxides. From the XRD pattern of the clinker (Fig. 4a), it can
be seen that the diffraction peaks of the main phases such as Fe2 O3 , NaFeSi2 O6,
and NaTiSi2 O6 have appeared. Indicating that the roasting process has been fully
reacted. Some vanadium magnesium spinel (MgV2 O4 ) did not oxidize or oxidized
to form insoluble compound Mg2 VO4 . The silicon, calcium and other harmful ele-
ments in the vanadium slag form vanadium coated substances with low eutectic
points with sodium carbonate in the roasting process, such as Na2 O·Fe2 O3 ·4SiO2
and CaMnSi2 O6 . The formation of these substances has a harmful impact on the
oxidation of vanadium in the roasting process. Compared with the XRD pattern of
vanadium slag (Fig. 1), it can be found that the main vanadium spinel phase (Mn,
Fe)(Cr,V)2 O4 peak in vanadium slag has completely disappeared, indicating that
the spinel has all been oxidized. Meanwhile, new soluble compounds NaVO3 and
NaV3 O8 were generated from V2 O5 and sodium carbonate. From the XRD pattern
of the leaching residue (Fig. 4b), it can be seen that the phases in the residue are
mainly Fe2 O3 , NaFeSi2 O6 , and NaTiSi2 O6 . Compared with the XRD picture of the
clinker (Fig. 4a), the most obvious change is the absence of sodium vanadate phase
in the clinker. Indicating that it has been completely dissolved in aqueous solution.
There are still some vanadium containing phase in the residue, mainly MgV2 O4 and
Mg2 VO4 , which cannot be dissolved in aqueous solution.
XRF Analysis
As can be seen from Table 2, the element V content of clinker is 6.42%, which is
lower than that of V (7.62%) in vanadium slag (Table 1), for 19% of the additive
sodium carbonate is added in vanadium slag, which is equivalent to diluting the
content of V. The content of Na element is 8.43%, indicating that almost all the
sodium carbonate added before roasting goes into the clinker. As can be seen from
Table 3, after the leaching process, the vanadium content in the residue is 1.03%.
Indicating that some vanadium in the residue has not been leached. The reasons
may be that the vanadium in this part cannot be dissolved in water, or the leaching
process is not perfect, leading to incomplete leaching. Besides, the original clinker
impurity elements in most are left in the residue, this is due to the impurity elements
composition does not dissolve in water or hydrolysis precipitation during leaching
into the residue, but some silicate and phosphate hydrolysis still generate insoluble
compounds, remaining in the leaching solution, which is consistent with the XRD
results.
Enlarged Experiment
As can be seen from Table 4, the leaching efficiency of vanadium is at a high level
(about 88%). The leaching efficiency of 20 g vanadium slag reached 89.41%. With
the increase of the quality of vanadium slag, the difficulty of contacting the vanadium
Table 4 Vanadium leaching efficiency of different vanadium slag masses

Mass of Addition Mass of mixture Vanadium Leaching
vanadium slag amount (g) (g) content in efficiency of
(g) residue (%) vanadium (%)
20 3.80 23.90 1.03 89.4
200 38 238.10 1.07 87.9
500 95 595.20 1.11 87.6
1000 190 1192.00 1.15 86.9
442 G. Liang et al.
slag at the bottom of the roasting container with oxygen also increases, which affects
the oxidation effect of vanadium slag. Resulting in a slight reduction of the leaching
efficiency of vanadium. This proves that the optimum vanadium extraction process
parameters proposed have high accuracy and stability.
Conclusions
The technology of sodium roasting, leaching, and extracting vanadium from vana-
dium slag was studied. The effects of different parameters on the efficiency of vana-
dium extraction from vanadium slag were discussed. The optimum conditions of
roasting process were obtained based on experiments: addition of 19% Na2 CO3 ,
roasting temperature of 800 °C, roasting time of 120 min, and the particle size of
vanadium slag was less than 125um. The leaching experiments showed that the opti-
mal parameters of the leaching process were as follows: the leaching temperature of
90 °C, leaching time of 30 min, and the ratio of liquid–solid was 8.0 mL/g. Under
the optimal roasting-leaching process, the leaching efficiency of vanadium can reach
89%. After leaching, the residue contained vanadium about 1.17%, and the vanadium
phase was mainly magnesium vanadate.
Acknowledgements This research was financially supported by the Natural Science Foundation of
Chongqing: cstc2018jcyjAX0792 and the Fundamental Research Funds for the Central Universities:
Project No. 2019CDXYCL0031. The project name: Cutting-edge Technological Innovation of New
Materials and New Metallurgical Technologies.
References
1. Wang T, Longjun XU, Liu C, Zhang Z (2014) Calcified roasting-acid leaching process of
vanadium from low-grade vanadium-containing stone coal. Chin J Geochem 33(2):163–167
2. Bao SX, Liang L, Zhang YM, Han S, Yangjia HU (2015) Effect of calcium on the vanadium
extraction from high calcium type stone coal. J Wuhan Univ Technol (Mater Sci Ed) 30(2):
320–324
3. Zhu YH, Feng YL, Dong-Hai L, Zhang N, Zhu ZX (2012) Determination of Fe, Ti and V in
vanadium titanomagnetite ore by inductively coupled plasma-atomic emission spectrometry.
Rock Miner Anal 31:258–262
4. Zheng HY, Yu S, Lu JW, Dong JH, Zhang WL, Shen FM (2017) Vanadium extraction from
vanadiumbearing titanomagnetite by selective chlorination using chloride wastes (FeClx). J
Cent South Univ 24(02):311–317
5. Li HY, Fang HX, Wang K, Zhou W, Yang Z, Yan XM, Ge WS, Li QW, Xie B (2015) Asyn-
chronous extraction of vanadium and chromium from vanadium slag by stepwise sodium
roasting–water leaching. Hydrometallurgy 156:124–135
6. Jiang DD, Zhang HL, Xu HB, Yi Z (2017) Chlorination and purification of vanadium pentoxide
with anhydrous aluminum chloride. J Alloy Compd 709:505–510
7. Vuuren CPJV, Stander PP (1995) The oxidation kinetics of FeV2 O4 in the range 200–500°C.
Thermochim Acta 254:227–233
8. Barker MG, Hooper AJ (1973) Reaction of sodium oxide with the oxides VO2 , V2 O3 , vo and
vanadium metal (ChemInform Abstract). Chemischer Informationsdienst 4(15):1517–1519
9. Chen D, Zhao L, Liu Y, Qi T, Wang J, Wang L (2013) A novel process for recovery of iron,
titanium, and vanadium from titanomagnetite concentrates: NaOH molten salt roasting and
water leaching processes. J Hazard Mater 244–245:588–595
10. Aarabi-Karasgani M, Rashchi F, Mostoufi N, Vahidi E (2010) Leaching of vanadium from LD
converter slag using sulfuric acid. Hydrometallurgy 102(1–4):14–21
Effect of Additives on Semi-molten State
Reduction for Titanium Slag Production
from Ilmenite Concentrate
Wei Lv, Shiyuan Liu, Junyi Xiang, Xuewei Lv and Yindong Yang
Abstract In this study, a novel process is proposed to produce titanium slag from
Panzhihua ilmenite concentrate. The carbothermic reduction of ilmenite concentrate,
followed by wet magnetic separation, was performed to generate metallic iron and
a titanium-rich slag in the presence of sodium sulfate and sodium carbonate. This
work investigated the influence of reaction time, sodium sulfate additive, and sodium
carbonate additive on the metallization, the TiO2 grade in the non-magnetic fractions,
and recovery of titanium dioxide. The results show that sodium carbonate increases
the metallization, while sodium sulfate decreases the metallization of the reduced
sample. In the presence of sodium carbonate, the highest metallization and recovery
of titanium dioxide can reach up to 90.57% and 0.83, respectively. In addition, the
mechanism of additives influence on the reduction process is also discussed.
Keywords Ilmenite concentrate · Carbothermic reduction · Semi-molten ·

Titanium slag · Additives
Introduction
The Panzhihua-Xichang region is the biggest vanadium-titanium magnetite deposit in

China, with titanomagnetite reserves of 9.66 billion tons [1, 2]. The titanium reserves
in Panzhihua-Xichang area account for 90.5% of the total titanium reserves in China
and 35.17% worldwide [3–5]. The Panzhihua ilmenite concentrate obtained during
the beneficiation of Panzhihua vanadium-titanium magnetite ores is of rock-type
origin, featuring a dense structure and containing high contents of CaO and MgO.
In this regard, the chlorination of this ilmenite concentrate with the production of
TiO2 pigment is not favored due to the low reduction kinetics [5, 6]. Therefore, the
W. Lv (B) · S. Liu · J. Xiang · X. Lv

e-mail: yjlvwei@163.com
W. Lv · Y. Yang
Department of Materials Science and Engineering, University of Toronto, Toronto, ON M5S 3E4,
Canada

https://doi.org/10.1007/978-3-030-36540-0_39
446 W. Lv et al.
Panzhihua ilmenite concentrate is usually smelted in an electric arc furnace (EAF)

to produce titanium slag which is then leached by sulfuric acid to produce titanium
dioxide. For the current smelting practice, the slag is required to contain 10–12
mass% FeO so as to ensure favorable slag properties, i.e., low melting temperature
and suitable viscosity. This strategy, however, results into the reduction in the titanium
slag grade (only 74 mass% TiO2 ) and increase in the energy consumption [7, 8].
To reduce the energy consumption of EAF smelting process and obtain a higher
grade of titanium slag, semi-molten state reduction of ilmenite concentrate followed
by magnetic separation for titanium slag production has been proposed. The effects
of reaction time and type of additives on the metallization, the TiO2 grade in the
non-magnetic fractions, and recovery of titanium dioxide were studied.
Experimental
The ilmenite concentrate (<150 mesh) used in this study was supplied by Panzhi-
hua Iron and Steel Group. The mineralogy of this concentrate was examined by
X-ray diffraction (XRD). As shown in Fig. 1, the main phases consisted of FeTiO3 ,
MgTiO3, and Fe3 O4 . The chemical composition of the ilmenite concentrate was listed
in Table 1. It is seen that the main impurities in the concentrate include MgO (5.66
mass%) and SiO2 (3.23 mass%). Graphite powder (≥99.9% purity, <13 µm) was
used as the reducing agent. Two types of additives were investigated in this work,
sodium carbonate (chemical grade, Aladdin Industrial Corporation) and sodium
sulfate (chemical grade, Aladdin Industrial Corporation).
The ilmenite concentrate was mixed thoroughly with the graphite powder and
additive (sodium sulfate or sodium carbonate) at a fixed C to O (the O atoms in
iron oxides only) molar ratio of 1.2:1.0. The addition of sodium sulfate was set as 8
mass%, while in the case of sodium carbonate, the addition was 5.97 mass% which
Fig. 1 XRD pattern of raw

ilmenite concentrate powder
Table 1 Chemical composition of the ilmenite concentrate (mass%)
TiO2 FeO Fe2 O3 MgO SiO2 Al2 O3 CaO MnO V2 O5 S P
Ilmenite concentrate 46.82 34.52 6.10 5.66 3.23 1.00 0.842 0.635 0.058 0.14 <0.005
Effect of Additives on Semi-molten State Reduction …
447
448 W. Lv et al.
Fig. 2 Schematic diagram of the experimental apparatus of MoSi2 furnace
ensured an equimolar amount of Na in both mixtures. The mixtures of 10 g were

filled into the mold with an inner diameter of 16 mm and pressed into briquettes under
the uniaxial pressure 8 MPa. The carbothermic reduction was conducted in a vertical
tube furnace (MoSi2 furnace, Fig. 2) under argon atmosphere (99.999%, 0.6 L/min).
The temperature for the isothermal carbothermic reduction was 1400 °C. When the
furnace temperature reached 1400 °C, briquettes placed in the alumina crucible was
put into the hot zone, heat-treated for 10 min or 50 min, and then withdrawn from the
furnace and quenched in air. The reduced sample was crushed by vibration grinding
machine and then the composition of the resulting powder was analyzed.
The wet magnetic separation was performed using a Davis Tube Tester (XCQS-
F50, Nanchang hengye mining and metallurgy machinery factory). The wet magnetic
separation was performed in two stages. First, the ground material was separated at
a nominal magnetic intensity of 0.16 T. Second, the magnetic fraction obtained from
the first separation was re-separated at 0.05 T to produce the final magnetic fraction.
The non-magnetic fraction generated from the second separation was combined with
the non-magnetic fraction from the first to produce the final non-magnetic fraction.
The concentrations of TiO2 and Fe in the final magnetic and non-magnetic fractions
were analyzed.
The metallization of the reduction products is defined as
MFe
MR = × 100% (1)
TFe
where MFe and TFe are the weight percentages of the metallic iron and the total iron
in the products, respectively.
Effect of Additives on Semi-molten State Reduction … 449
Reduction Process
The metallization of the products as a function of reduction time when different

types of additives were used is shown in Fig. 3. In the absence of additives, the met-
allization increases from 85.45 to 88.27% with increasing reduction time from 10 to
50 min. However, when the additives Na2 SO4 and Na2 CO3 were used, no significant
change in metallization was observed when the reduction time increases from 10 min
to 50 min. This points to the fact that both Na2 SO4 and Na2 CO3 can accelerate the
reduction of ilmenite concentrate. It has been shown that the addition of Na2 SO4
and Na2 CO3 can accelerate the carbothermic reduction of ilmenite concentrate by
enhancing the gasification of carbon, specifically, shifting the CO/CO2 equilibrium
as a result of reactions between Na2 SO4 /Na2 CO3 with ilmenite concentrate or carbon
[8]. The metallization with the addition of Na2 SO4 is lower than that in the absence
of additive. This is due to the fact that the addition of Na2 SO4 consumed parts of
reductant and then reacted with iron oxides form FeS [8, 9]. In contrast, the metal-
lization with the addition of Na2 CO3 is higher than that without additive addition.
The maximum metallization can reach up to 90.57%. The increased metallization in
the case of Na2 CO3 addition is caused by the enhanced gasification of carbon that
accelerates the carbothermic reduction and chemical liberation of Fe from FeTiO3
as FeO by FeTiO3 + Na2 CO3 = Na2 TiO3 + FeO + CO2 ↑.
The Ti2 O3 content in the reduced products as functions of reduction time and
types of additive is shown in Fig. 4. The Ti2 O3 content in the reduced products
increases with increasing reduction time. The Ti2 O3 content without adding addi-
tives is higher than with adding additives. As mentioned above, the Na2 SO4 - and
Na2 CO3 -containing briquettes involve the reaction of additives with ilmenite con-
centrate and carbon, which results in the generation of CO by Boudouard reaction
Fig. 3 The metallization as

a function of reduction time
and types of additive
450 W. Lv et al.
Fig. 4 Ti2 O3 content in the

reduced products as
functions of reduction time
and types of additive

CO2(g) + C(s) 2CO(g) . The reduction of iron oxides by CO then follows, which
reduces the amount of carbon available for the reduction of TiO2 . As a result, the
amount of Ti2 O3 in the reduced products due to the reduction of TiO2 by CO is lower
when Na2 SO4 and Na2 CO3 are present. Without the addition of Na2 CO3 or Na2 SO4 ,
the significant carbon dissolution was delayed to higher temperatures (>1000 °C),
and thus the amount of carbon available for reducing TiO2 to Ti2 O3 was higher.
Magnetic Separation
The TiO2 recovery into the final non-magnetic fractions as functions of reduction
time and types of additives is shown in Fig. 5. The TiO2 recovery increases with
Fig. 5 TiO2 recovery into

the non-magnetic fractions
as functions of reduction
time and types of additives
Effect of Additives on Semi-molten State Reduction … 451
Fig. 6 TiO2 grade in the

non-magnetic fractions as
functions of reduction times
and types of additives
increasing reduction time. This is because the prolonged reduction time causes the
coarsening of metallic particles, which is beneficial to the magnetic separation. The
positive effect of additives on the TiO2 recovery is due to the fact that the addition
of Na2 SO4 and Na2 CO3 promoted the liberation of Fe from ilmenite in the form of
either FeS or Fe. However, the maximum recovery of TiO2 , i.e., 0.83, is found to be
relatively low compared with the EAF smelting process (≥0.90).
The TiO2 grade in the non-magnetic fractions as functions of reduction is shown
in Fig. 6. The TiO2 grade in the non-magnetic fraction increases with increasing
reduction time. The TiO2 grade for the additive-free sample is slightly higher than
that in the presence of Na2 SO4 and Na2 CO3 , of which the trend is opposite to the
TiO2 recovery. At the highest TiO2 recovery (0.83), the grade of TiO2 in the non-
magnetic fraction (titanium slag) is only 66.46 mass% which is lower than the EAF
smelting process (74 mass%). Therefore, further studies on the optimization of wet
magnetic separation of iron and slag are needed.
Conclusions
1. Both Na2 SO4 and Na2 CO3 accelerate the carbothermic reduction of ilmenite con-
centrate. The Na2 CO3 addition increases the metallization, but Na2 SO4 decreases
the metallization of the reduced products. The Ti2 O3 content in the reduced
products increases with increasing reduction time.
2. The TiO2 recovery increases with increasing reduction time. This is due to the
coarsening of the metallic particles upon prolonged reduction time, which is
beneficial to magnetic separation. Given the same reduction conditions, the TiO2
recovery increases with the addition of Na2 SO4 and Na2 CO3 .
452 W. Lv et al.
Acknowledgements This work was supported by the Fundamental Research Funds for the Cen-
tral Universities (2018CDYJSY0055). Wei Lv acknowledges the financial support of the China
Scholarship Council.
References
1. Zheng FQ, Chen F, Guo YF, Jiang T, Travyanov AY, Qiu GZ (2016) Kinetics of hydrochloric
acid leaching of titanium from titanium-bearing electric furnace slag. JOM 68:1476–1484
2. Zhao LS, Wang LN, Qi T, Chen DS, Zhao HX, Liu YH (2014) A novel method to extract iron,
titanium, vanadium, and chromium from high-chromium vanadium-bearing titanomagnetite
concentrates. Hydrometallurgy 149:106–109
3. Yu W, Wen XJ, Chen JG, Kuang JZ, Tang QY, Tian YC et al (2017) Preparation of direct reduced
iron and titanium nitride from Panzhihua titanomagnetite concentrate through carbothermic
reduction-magnetic separation. Minerals 7:220
4. Huang R, Lv XW, Bai CG, Zhang K, Qiu GB (2013) Enhancement reduction of Panzhihua
ilmenite concentrate with coke and conglomeration of metal with ferrosilicon. Steel Res Int
84:892–899
5. Lv W, Lv XW, Xiang JY, Wang JS, Lv XM, Bai CG et al (2017) Effect of pre-oxidation on the
carbothermic reduction of ilmenite concentrate powder. Int J Miner Process 169:176–184
6. Chen D, Zhao L, Liu Y, Qi T, Wang J, Wang L (2013) A novel process for recovery of iron,
titanium, and vanadium from titanomagnetite concentrates: NaOH molten salt roasting and water
leaching processes. J Hazard Mater 244–245:588–595
7. Pistorius PC, Coetzee C (2003) Physicochemical aspects of titanium slag production and
solidification. Metall Mater Trans B 34:581–588
8. Lv W, Bai CG, Lv XW, Hu K, Lv XM, Xiang JY et al (2018) Carbothermic reduction of ilmenite
concentrate in semi-molten state by adding sodium sulfate. Powder Technol 340:354–361
9. Lv W, Lv XW, Xiang JY, Zhang YY, Li SP, Bai CG et al (2017) A novel process to prepare high-
titanium slag by carbothermic reduction of pre-oxidized ilmenite concentrate with the addition
of Na2 SO4 . Int J Miner Process 167:68–78
Part VI
Treatment and Recycling of Wastes
Effect of La Content on Inclusions
and Microstructure of C–Mn Steel
Treated By Ti–Mg–Ca
Lei Wang, Bo Song, Zhen Liu, Xiaokang Cui and Longfei Li
Abstract Experiments with different lanthanum (La) addition were carried out to
investigate the component, size and distribution of inclusions and the change of
microstructure in C-Mn steel treated by Ti-Mg-Ca. The samples exacted from the
experimental steels were analyzed by scanning electron microscope (SEM), energy
dispersive spectrometer (EDS), and optical microscope (OM). The results showed
that inclusions in steel changed from MgO–Al2 O3 , CaO+Tix Oy, and MnS to La2 O2 S,
LaAlO3, and MnS after adding La. The content of La2 O2 S gradually increased, while
the content of LaAlO3 and MnS in the composite inclusions decreased with the
increase of La content. In addition, the amount of inclusions increased first and then
decreased with increasing La content. The size of effective inclusions was mainly
less than 3 µm in different samples. The distribution of inclusions was dispersive
and more acicular ferrite (AF) were obtained when the content of La was in the range
of 0.011–0.025 wt%.
Keywords Lanthanum · Acicular ferrite · Complex inclusions · C–Mn steel
L. Wang · B. Song (B) · Z. Liu · X. Cui · L. Li

e-mail: songbo@metall.ustb.edu.cn
L. Wang
e-mail: wanglei_ustb020@163.com
Z. Liu
e-mail: liuzhen_ustb@163.com
X. Cui
e-mail: cuixiaokang126@126.com
L. Li
e-mail: aifei_0105@126.com

https://doi.org/10.1007/978-3-030-36540-0_40
456 L. Wang et al.
Introduction
At present, oxide metallurgy technology has become an important approach to

improve the strength and toughness of heat affected zone (HAZ) of C–Mn steel
and high strength low alloy steel [1]. ‘Oxide metallurgy’ is defined as a new way
of steel making to induce the formation of intragranular acicular ferrite (AF) using
tiny dispersed nonmetallic inclusions. The AF laths have a chaotic crystallographic
orientation, this will refine grain and prevent the propagation path for a cleavage
crack in the metal [2].
Small amounts of rare earth added into steel can play the role of deoxidation,
desulphurization, and inclusion modification. Wang et al. [3] studied the influence of
La on inclusions and microstructure of 16Mn steel. They manifested that inclusions
transformed into LaAlO3 , La2 O2 S, and La2 S3 after La was added into steel, and Mn-
depleted zone (MDZ) formed in the vicinity of La-containing inclusions promoted
the formation of AF. Song et al. [4] found that the inclusion of rare earth treated
C–Mn steel changed from MnS+Al–Si–O to La2 O2 S+LaAlO3 +MnS + Al–Si-O,
and a large amount of acicular ferrite was achieved in steel. Inclusions in Ti–Ca
treated steel were mainly Ti–Ca–O–Mn–S, and these inclusions have strong ability
to induce the formation of AF [5, 6]. Lou et al. [7] derived that the addition of Mg
and Ca played an important role in the type and size of inclusions. The inclusions
were mainly Ti–Ca–Mg–Al–O, and they facilitated the heterogeneous nucleation of
AF. Chai et al. [8] have studied the influence of Mg on the microstructure and impact
toughness of the coarse grain heat affected zone (CGHAZ) in the Ti treated steel, they
derived that Mg added into Ti-containing steel was able to refine inclusions, which
resulted in high volume percent of AF in CGHAZ. Lou et al. [9] studied the effect of
Ti–Mg–Ca treatment on heat affected zone of large heat input welding, they found
that the number of inclusions in Ti–Mg–Ca treated steel were significantly more than
Ti–Ca treated and C–Mn steel, and the size of inclusions was much smaller.
Up to now, there are many papers studying on the characteristics of nucleation
inclusions for AF formation in La or Ti–Mg/Ca treated steel, especially on the best
inclusion size and composition for AF nucleation. Researchers have paid more atten-
tion to the effect of La or Ti–Mg/Ca on inclusions and microstructure. However, few
research works have been carried out to understand the influence of La content on
inclusions and microstructure of C-Mn steel treated by Ti-Mg-Ca. Therefore, this
study focused on the influence of Ca, Mg and La on inclusions and compared the
microstructure of the C-Mn steel treated with different La content.
Experimental
The smelting experiment was carried out in the high-temperature molybdenum wire
furnace. About 400 g C–Mn steel was melted within the corundum crucible, sub-
sequently the furnace was heated to1600 °C and held at that temperature for 5 min
Effect of La Content on Inclusions and Microstructure … 457
Fig. 1 Process of the alloy

elements addition
under argon protection. Then, different treatment agents of Ti–Fe, Si–Ca, Ni–Mg,
and La was added into the molten steel, and the addition process of treatment agents
is shown in Fig. 1. Keeping the temperature for 5 min again, and then turn off the
power. After cooling to 1100 °C, the crucible was taken out quickly and quenched
in water. The specific chemical composition is shown in Table 1.
The samples, which size of 10 × 8 mm, were sectioned from the middle of ingots.
After inlaying, pre-grinding and polishing, 50 fields of view were randomly selected
under 1000-fold field of view using OM, and Image J was used to analyze inclusions
in the samples, then the morphology and composition of inclusions were analyzed by
SEM-EDS. After the sample was etched by a 4% Nital solution, the microstructure
of the sample was observed by OM and SEM. Effective inclusions were randomly
selected under 2000-fold field of view by SEM, and the size distribution composition
of effective inclusions was analyzed by Image J and SEM-EDS.
Thermodynamic Calculation
Precipitation of inclusions during solidification was calculated using the “Equilib”

module in thermodynamic software FactSage. The composition of the molten steel
is shown in Table 1. Calculation results are shown in Fig. 2. La content has little
effect on the oxides of Al2 O3 , CaO, MgOMgO, and Tix Oy , however, with further
decrease of temperature, the precipitation of MnS were affected by La content. With
the increase of La content, the amount of La2 O2 S increased, while the amount of
LaAlO3 and MnS reduced. Without La addition, the main inclusions were a large
amount of MnS and a small amount of Al2 O3 , CaO, MgOMgO, and Tix Oy , as shown
in Fig. 2a; with the addition of 0.011 wt% La, a lot of LaAlO3 and La2 O2 S were
formed, and a small amount of Al2 O3 , CaO, MgO, and Tix Oy could also be found, as
shown in Fig. 2b. Increasing the La content to 0.025 wt% developed more La2 O2 S as
458
Table 1 Chemical compositions of each tested steel/wt%

Steel C Si Mn S Al Ti Mg Ca La T.O Fe
TL0 0.17 0.19 1.16 0.014 0.002 0.016 0.0019 0.0015 0.008 Bal.
TL1 0.17 0.19 1.16 0.014 0.002 0.02 0.0023 0.0010 0.011 0.0085 Bal.
TL2 0.17 0.19 1.16 0.014 0.002 0.02 0.0026 0.0012 0.025 0.009 Bal.
TL3 0.17 0.19 1.16 0.014 0.002 0.02 0.0018 0.0009 0.048 0.007 Bal.
L. Wang et al.
Fig. 2 Calculation results of inclusions in C-Mn steel by FactSage, a TL0; b TL1; c TL2; d TL3
illustrated in Fig. 2c, while the content of AlLaO3 and MnS slightly decreased. When
La content increase to 0.048 wt%, the amount of La2 O2 S was significantly increased,
and LaAlO3 disappeared, as shown in Fig. 2d. The amount of MnS significantly
reduced when La content reached 0.048wt%. Therefore, the number of La2 O2 S
gradually increased with the increase of La content, while the amount of AlLaO3
gradually decreases and then disappeared under the experimental conditions.
Effect of La Content on Inclusions
The morphology and composition of inclusions treated by La is shown in Fig. 3.

The figure shows that inclusions in steel were mainly multilayered inclusions with
oxide core. The main oxide core of inclusions were Ti–Mg–Ca–Al–O in steel with-
out the addition of La, and a small quantity of MnS precipitated outside the oxide
core (Fig. 3a). When La was added in steel, the main inclusion changed into La–
O–S–Mg, and MnS was precipitated on the surface of the oxide core, as shown
in Fig. 3. The oxide core were La–Mg–Al–S–O type inclusions in steel TL1, and
the oxide core were mainly La2 O2 S and LaAlO3 , furthermore, a small quantity of
CaO+Tix Oy +MgO and MnS also formed in the vicinity of the oxide core, as shown
in Fig. 3b. The composition of the oxide core was mainly La2 O2 S and a small amount
460 L. Wang et al.
Fig. 3 Compositions of typical nonmetallic inclusions by SEM-EDS, a TL0; b TL1; c TL2; d TL3
of MgO in steel TL2, the percentage of La in the inclusions increased compared with
TL1, and the outside of oxide core was mainly La2 O2 S and MnS. When La content
was increased to 0.048 wt%, the La content in the inclusions increased significantly,
and the oxide core of major inclusions changed from complex phase to single phase
of La2 O2 S in steel TL3 (Fig. 3d). The number of La-containing inclusions increased
with the increase of La content. The main reason is that the density of inclusions
containing La was larger, therefore, they cannot be removed by floating and will sink
to the bottom of molten steel. In terms of the composition of inclusions, there were
more La2 O2 S formed in steel, therefore, the percentage of La and S in the inclusions
increases with the increase of the La content in the range of 0–0.048 wt%.
Fig. 4 Size distribution and number density of inclusions
Effect of La Content on the Size and Number Density

of Inclusions
The size distribution of inclusions in different samples is depicted in Fig. 4. The

average size of inclusions slightly increased with the increase of La content, and the
size of inclusions was mainly less than 2 µm. The average size of inclusions was
smaller when La was added into steel. The number density of inclusions smaller
than 3 µm first increased and then decreased slightly with the increase of La con-
tent, in addition, these inclusions (<3 µm) accounted for a large proportion among
different samples and the percentages were 94.63%, 94.86%, 97.46%, and 91.34%,
respectively. However, as the La content in the molten steel increased, the number
of inclusions larger than 3 µm in samples significantly increased, and the percent-
ages were 8.66% when La content was 0.048%. On the one hand, the probability of
collision of small particle inclusions was significantly increased, and it was easy to
aggregate and grow up when temperature was kept at 1600 °C; on the other hand,
the molecular of La is larger than other elements, so some composite inclusions con-
taining La will not be removed by floating and stayed in the molten steel. Therefore,
when the La content increased to 0.048wt%, the number of inclusions larger than
3 µm in steel was increased. Under the experimental conditions, the suitable La
content which was favorable for the dispersion of fine inclusions in steel was in the
range of 0.011–0.025 wt%.
Effect of La Content on the Size of Effective Inclusions
The morphology of effective inclusions and microstructure is shown in Fig. 5. The

figure shows that several AF plates emanated from the inclusions. Statistical results
of size distribution and number density of inclusions are shown in Fig. 6. La content
462 L. Wang et al.
Fig. 5 Morphology of AF and effective inclusions, a TL0; b TL1; c TL2; d TL3
Fig. 6 Size distribution and the average size of effective inclusions
had little effect on the distribution of effective inclusions, and the size of effective
inclusions was mainly smaller than 3 µm, as can be seen in Fig. 6a. While the
mean size of effective inclusions was affected by La content, the size of effective
inclusions increased with the increase of La content in the range of 0–0.011 wt% and
0.025–0.048 wt% (Fig. 6b). However, the average size of effective inclusions was
almost invariable when La content was 0.011 and 0.025 wt%. As can be seen from
Figs. 4 and 6 that the number of inclusions with the same size as effective inclusions
(smaller than 3 µm) in TL1 and TL2 were larger than other samples, meanwhile,
these inclusions could induce more acicular ferrite nucleation. Hence, the size of
inclusions had an effect on the formation of AF, and the size of inclusions could
induce the formation of AF were mainly less than 3 µm, meanwhile, the appropriate
content of La was in the range of 0.011–0.025 wt%.
Effect of La Content on the Microstructure
The microstructure and morphology is shown in Fig. 7. There is a large number

of bainite (B), parallel lath ferrite (LF), and pearlite (P), a small amount of acicular
ferrite (AF) in steel TL0 as shown in Fig. 7a. When the content of La increase to 0.011
and 0.025wt%, the dominated microstructures of samples TL1 and TL2 changed
into acicular ferrite (Fig. 7b, c). As the La content up to 0.048wt% in sample TL3,
the microstructure turned into bainite and pearlite, the acicular ferrite content was
significantly reduced as shown in Fig. 7d. As can be seen from Figs. 4 and 6 that
the number of inclusions with size smaller than 3 µm in sample TL1 and TL2 was
the highest, which meant the effective inclusion was highest, so the AF content in
four samples was higher (Fig. 7b, c). From the foregoing discussion, we could draw
the conclusion that the addition of rare earth La was beneficial for the formation of
Fig. 7 Microstructure with different content of La, a TL0; b TL1; c TL2; d TL3
464 L. Wang et al.
acicular ferrite, while excessive La content was not conducive for the formation of
acicular ferrite. The optimized La content for acicular nucleation was in range of
0.011–0.025 wt% in this study.
Conclusions
1. When La was added into steel, the main oxides in the steel transformed into
La2 O2 S and LaAlO3 . With the increase of La content, the amount of La2 O2 S
increases, while the amount of LaAlO3 decreases gradually and then disappeared.
The inclusions were mainly oxide core with MnS precipitated on the surface.
2. The content of La has a great influence on the size of inclusions and microstruc-
ture. The total number of inclusions and the content of acicular ferrite increases
and then decreases with increasing La contents, and the size of effective inclu-
sions was mainly less than 3 µm. When the content of La was in the range of
0.011–0.025 wt%, the inclusions were finely dispersed and more AF could be
obtained.
Acknowledgements This work is financially supported by the National Nature Science Foundation
of China under Grant No.51774024.
References
1. Zhong-zhu L, Kuwabara M (2007) Recent progress in oxide metallurgy technology and its
application. Steelmaking 4:1–6
2. Liu C, Bhole SD (2013) Challenges and developments in pipeline weldability and mechanical
properties. Sci Technol Weld Join 18(2):169–181
3. Li-yong W, Bo S, Hong-ke L (2014) Effect of lanthanum on inclusions and microstructure of
16Mn steel. T Mater Heat Treat 7:59–64
4. Song M-M, Song B, Yang Z-B (2015) Microstructure and inclusion evolution in rare earth treated
C–Mn steel. Chinese J Eng 37(12):1564–1569
5. Wang C, Wang X, Kang J (2019) Effect of austenitization conditions on the transformation
behavior of low carbon steel containing Ti–Ca oxide particles. Materials 12(7):1070
6. Wang C, Wang X, Kang J (2019) Effect of thermomechanical treatment on acicular ferrite
formation in Ti–Ca deoxidized low carbon steel. Metals. 9(3):296
7. Lou H, Wang C, Wang B (2019) Evolution of inclusions and associated microstructure in Ti–Mg
oxide metallurgy steel. ISIJ Int 59(2):312–318
8. Chai F, Yang C, Su H (2009) Effect of magnesium on inclusion formation in Ti-killed steels and
microstructural evolution in welding induced coarse-grained heat affected zone. J Iron Steel Res
Int 16(1):69–74
9. Lou H, Wang C, Wang B (2019) Effect of Ti–Mg–Ca treatment on properties of heat-affected
zone after high heat input welding. J Iron Steel Res Int 26(5):501–511
Research on the Database Construction
of Furnace Material Consumption
in EAF Steelmaking Process
Botao Xue, Lingzhi Yang, Yu-feng Guo, Feng Chen, Fuqiang Zheng,
Jinlai Zhang, Hongguo Yao and Xiaolei Hou
Abstract As the three-level management system for material consumption in the

EAF steelmaking plant cannot obtain statistics and carry calculation of material
consumption for each furnace, the data from the system cannot provide guidance
for actual smelting operation. In this paper, the field PLC process smelting data of
the material consumption in “EAF-LF-CC” process were collected from Kepware
as OPC Server and by VS2010 as development tool. Then, they were classified (in
categories of scrap charging, auxiliary materials, gas consumption, injection informa-
tion, power supply data, etc.) and stored into Microsoft SQL Server 2008 database to
build a database of furnace material consumption. The database construction provides
guidance for reducing the material consumption and optimizing smelting operation
for each furnace.
Keywords EAF steelmaking · Material consumption · PLC data collection · Cost

analysis
Introduction
The electric arc furnace (EAF) short steelmaking process has become one of the two
main steel production processes in the world [1] because of its advantages in low
energy consumption [2] and short smelting time [3]. With the continuous develop-
ment of process and equipment technologies [4–6] in steelmaking plants, effectively
reducing the production cost of EAF steel has become a major work [7–9]. At present,
the most important way to reduce the production cost of iron and steel enterprises
is to control the consumption of furnace materials [10, 11] during the smelting pro-
cess. Therefore, how to quickly, accurately, and efficiently collect data of raw material
consumption in steelmaking process, providing the basis for optimizing raw material
consumption and reducing production cost is a problem to be solved.
B. Xue · L. Yang (B) · Y. Guo · F. Chen · F. Zheng · J. Zhang · H. Yao · X. Hou

Hunan, China
e-mail: yanglingzhi@163.com

https://doi.org/10.1007/978-3-030-36540-0_41
466 B. Xue et al.
Some researchers have done a lot of researche on controlling the production cost
of EAF steelmaking plant, mainly through the collection of original data, apply-
ing the database data processing technology, the development of cost analysis and
process guidance software which have data collection function, management, and
information query function [12, 13]. These methods cannot obtain detailed statis-
tics of burden consumption and, therefore, cannot provide accurate guidance for the
consumption of furnace materials [14]. Song et al. realized real-time data collection
of PC stations by OPC technology on Siemens s7-300 industrial control platform
and developed the cost control model with Visual Studio.Net 2008 as development
tool. This technology can ideally solve the problem of material consumption in the
EAF steelmaking plants. However, due to the complex environment in the EAF steel-
making process in China, many main controllers and data sources, problems such as
lack of data and insufficient accuracy will be faced in the data acquisition process,
so the technology cannot be accurately applied in the actual production process. In
addition, there are also studies on cost control based on MES system data [15], but
this method only realized cost accounting and does not play a guiding role.
In the process of analyzing the material consumption of steelmaking furnace, the
material consumption database is the core [16], which can realize data collection,
arrangement, storage, retrieval, update, statistics and transfer, and other operations
[17]. Its performance directly affects the material cost statistics of the furnace. In
this paper, material consumption in the production process of 50 t “EAF-LF-CC”
(Electric arc furnace—Ladle furnace—Continuous Casting) in a steel works is taken
as the research object, the field PLC process data were collected by KEPServerEX,
which was analyzed and stored into database. At the same time, combined with the
developed material consumption database application model, it provides the guidance
for the material consumption optimization in EAF steelmaking process [18, 19].
Database Construction of Batch Consumption
“EAF-LF-CC” is one of the most important processes in steel production, including

many process parameters and equipment operating parameters such as scrap feeding,
auxiliary feeding, gas consumption, spraying information, power supply, oxygen
supply, and other data directly reflecting the production status of the steelmaking
process. In order to accurately confirm the production situation and optimize the
furnace material consumption, it is necessary to collect the field PLC smelting data
and store them into the database.
Research on the Database Construction of Furnace Material … 467
Basic Configuration
In order to ensure the stability and convenience of the data collection system, reduce
the difficulty of system development and shorten the time of system development, this
paper chose KEPServerEX software as the third-party OPC Server Kepware to build
the data collection platform. This software has the characteristics of ‘one interface,
multiple protocols’, that is, multiple different devices can be read and written through
one OPC Server interface [20]. Data of the industrial field were stored by Microsoft
SQL Server 2008, which is widely recognized by users due to its advantages such
as rapid data processing rate, wide application range, and convenient background
development [21].
In terms of hardware, it is necessary to build a Server with good performance
and a computer equipped with Windows XP or above. The Server is in charge of
collecting real-time production data, managing quality standards and model oper-
ation, and is the core component of the model. The computer and OPC Server is
connected by industrial Ethernet, and the fixed IP address 192.168.4.50 computer
is configured, the network segment 192.168.1.1–192.168.1.254 of other computers
in EAF and refining furnace network is set, and the network segment 192.168.2.1–
192.168.2.254 of computer in continuous casting production network is set. The
three-level IP addresses of energy management, logistics management, and analy-
sis center are 192.168.3.1, 192.168.3.2, and 192.168.3.3, respectively. The specific
network architecture is shown in Fig. 1.
L3
Energy system Logistics system Quality system
Energy Plan Logistics Plan Production Plan
L2
Ethernet Database Server Ethernet
Ethernet Ethernet
Exchanger Exchanger Exchanger

(EAF) (LF) (CC)
PC PC PC
Guidance Transmission Guidance Transmission Guidance Transmission
Network(EAF) Network(LF) Network(CC) L1
EAF-PLC LF-PLC CC-PLC
Fig. 1 Industrial network structure of a steel plant

468 B. Xue et al.
The Structure of Furnace Material Database
With the application of database technology and the development of computer tech-
nology, the management, and processing of field production data become easier. In
order to meet the needs of users, the collected smelting data, and the data in the
three-level system are structurally designed to facilitate data conversion and mutual
reference.
Due to a large amount of smelting data collected, it is necessary to design the
database structure and set up the corresponding data table according to the technical
characteristics of the site. It mainly includes the data of electric furnace, refining
furnace, continuous casting furnace, power supply, feeding, blowing, temperature
measurement and other process data, material consumption cost data, three-level
system logistics data, energy data, analysis data, and other information. The database
structure is shown in Fig. 2.
(1) EAF process information
The information of EAF process mainly includes furnace time data (recording time,
furnace, steel grade, shift, total carbon powder consumption, various kinds of gas
consumption data), the process data (trigger signal in the process of smelting, gas
flow data), and scraps charging data, auxiliary material charging data, power supply
data, temperature measurement data, etc.
(2) LF process information
The information of refining furnace process mainly includes the furnace time data
(recording time, furnace number, shift group, argon gas consumption data), pro-
cess data (argon blowing start signal, top blowing start signal, gas flow data), alloy
consumption data, power supply data, temperature measurement data and other
information.
EAF-LF-CC Furnace Material Database
Three-level
EAF Process Data LF Process Data CC Process Data Other Information Cost Data
system Data
Furnace Data Furnace Data Furnace Data Production plan

Logistics Data Material Cost
production
Real-time Data Real-time Data Real-time Data schedule
Group Cost
Scrap Data Alloy Data Spare parts Data energy Data Interrupt Event
Process Cost
Gas Data Gas Data Manual Data Quality Data History Data
... ... ... ... Furnace Cost
Fig. 2 Data structure diagram of a steel plant

(3) CC process information

The information of continuous casting process mainly includes furnace time data
(recording time, furnace number, shift, casting length, casting number, casting weight
data), process data (casting speed, casting temperature and other information), spare
parts consumption data, temperature measurement data, manual input, and other
information. Among them, manual data input includes manual feeding data such as
mould fluxes, stuffing sand, and temperature probe, which cannot be collected by
PLC in the production process.
(4) Three-level system information
The information of data acquisition by three-level system includes energy manage-
ment data (power supply, electricity, gas, purchase price, etc.), logistics management
data (scrap purchase quantity, scrap price, alloy purchase quantity, alloy price, lime
purchase quantity, lime price, etc.), laboratory analysis data (steel composition data,
standard steel composition data, etc.).
(5) Other information
Other information mainly includes production plan information (smelting furnace
number, steel grade, route code, specification, etc.), task release, interruption oper-
ation record information (time, fault, solution, etc.), furnace number summary,
etc.
(6) Cost information
Cost information contains material cost, shift cost, process cost, and batch cost data.
According to the scrap consumption data, auxiliary material consumption data, elec-
tricity supply data, gas consumption data, and other consumables consumption data
generated by each furnace, and combined with the energy information and logistics
information in the three-level system, to calculate the material cost of each furnace.
Design of Furnace Consumption Data Table
The EAF steelmaking process furnace consumption database created consists of a

number of discrete tables, each with data from a different process. In order to system-
atically analyze the material consumption data of each furnace, SQL (standardized
query language) is needed to create a view of furnace material consumption in the
database and correlate these scattered data tables to provide more complete and
convenient information for furnace consumption analysis (Fig. 3). The view builds
relationships as follows:
470 B. Xue et al.
EAF_Process EAF_Material EAF_Heat

Heat_ID nchar(10)(PK) Heat_ID nchar(10)(PK) Heat_ID nchar(10)(PK)
Charging_1_W float Material_TIME datetime RCD_TIME datetime
Charging_2_W float Material_NO nchar(10) Steel_ID nchar(10)
Total_oxygen_W float Material_CAR nchar(10) Tapping_W float
Total_CH4_W float Material_W float C_Powder_W float
LF_Process LF_Charge LF_Heat

LF_Heat_ID nchar(10)(PK) LF_Heat_ID nchar(10)(PK) LF_Heat_ID nchar(10)(PK)
Cost_Price_Heat_Steel_Unit_V
LF_Power_Q float LF_Charge_TIME datetime LF_Shift_Nam nchar(10)
LF_Actual_1_Ar_F float LF_Charge_NO nchar(10) LF_Shift_TYPE nchar(10) Heat_MAT_ID nchar(25)(PK)
LF_Actual_2_Ar_F float LF_Charge_NAME nchar(10) LF_Argon_W float Heat_ID nchar(10)
LF_Water_F float LF_Charge_W float LF_Start_TIME datetime Process nchar(10)
Type nchar(10)
Name_C nchar(10)
CC_Process CC_Hand_Sum CC_Hand_Sum_Heat Price float
CC_Heat_ID nchar(10)(PK) CC_Heat_NO_ID nchar(10)(PK) Unit nchar(10)
NO nchar(20)(PK)
CC_RCD_TIME datetime CC_RCD_TIME datetime Shift_TYPE nchar(10)
Name nchar(20)
CC_Start_W float CC_Heat_ID nchar(10) W float
Name_C nchar(10)
CC_Start_T nchar(20) Name nchar(20) RCD_TIME datetime
Unit nchar(10)
CC_Strand_1_SPEED float Add_W float
L3_M_work L3_RE_SVdata Price

bm nchar(10)(PK) DateTime datetime(PK) NO nchar(10)(PK)
ggxh float SV1 float Type nchar(10)
jldw float SV2 float Name_C nchar(10)
j_lb float SV3 float Price float
j_kfdl float SV4 float Auto nchar(10)
Fig. 3 Construction relationship of furnace consumption view
Application Model of Database
In order to verify the EAF steelmaking process furnace time database is practical,
In this paper, based on the material consumption of the “EAF-LF-CC” steelmaking
process in the steel plant, cost analysis model have been established, the model can
realize steelmaking furnace costs, such as material, the electricity consumption of
real-time analysis, dynamic management and assessment of cost, enhanced the real
record of EAF steelmaking process furnace material, energy cost of online, in order
to optimize the furnace material consumption, reduce production costs.
Development Tools
The database application model is developed on Visual Studio.NET 2010 software

by C# language. C# programming language is a currently widely-used programming
language, it is fully object-oriented and one of the most important development
language on the .Net platform. C# language is derived from C language and C++
language, but it has abandoned the complex memory management and pointer oper-
ation of C++ and integrated the simple visual operation of VB and the powerful
function of C++, which has higher running efficiency than C++. And C# is a secure
language with automatic memory management, easy use, and portability, etc.
Visual Studio 2010 integrates access to objects, relational data, and XML in
a more concise language. This software provides wizards, tools, and components
that simplify the development of code to build and manage SQL Server databases,
Windows workflow applications, enterprise Server solutions, etc.
Model Interface and Function
The “EAF-LF-CC” steelmaking process furnace material cost analysis model has
been developed by using Visual Studio.NET 2010 software, which can dynamically
display current smelting furnace consumption information real time, such as process
smelting basic data, metal material consumption, auxiliary material consumption,
gas consumption, spray consumption, electrical energy consumption and other data,
and the detailed cost of the furnace can also be calculated. The interface is shown in
Fig. 4.
The furnace material cost analysis model is a complex and comprehensive system
based on EAF steelmaking process database. By using the system of the furnace
material, such as electricity consumption statistics, analysis, and processing, the
operator can learn about process production status, by the model calculation result.
Thus, according to the consumption of raw materials, timely adjust the amount of
auxiliary materials such as power supply, oxygen supply, carbon powder injection,
lime addition, etc., so as to minimize the consumption of materials in this furnace,
optimize the smelting effect, and provide guidance for enterprises with further control
of the production cost of steelmaking.
Fig. 4 Interface of furnace material cost analysis model

472 B. Xue et al.
Model Analysis and Discussion
The furnace material cost analysis model based on the PLC network, real-time acqui-
sition data field of smelting, furnace number times as the main factors, calculates
the material cost in the process of smelting, effectively solves the problem of three-
level cost accounting management system and provides more accurate and effective
guidance for furnace material optimization.
(1) The smelting operation of EAF steelmaking process is more standardized,
reducing the fluctuation of smelting cost and quality.
(2) The model provides different charging schemes according to different types
of smelting steel, so that operators of electric arc furnace can have a basis for
operation.
(3) The model records various operation interruption events in the smelting process
of electric furnace, providing basis for equipment personnel to judge the equip-
ment state, facilitating maintenance of equipment personnel and reducing the
time for fault cleaning.
Conclusion and Further Research
The furnace material consumption plays an important role in optimizing smelting

operation and reducing material consumption of steelmaking for each furnace. Usu-
ally, such furnace material consumption data are roughly counted in three-level man-
agement system that cannot make statistics and calculation of material consumption
for each furnace. With the development of communication technology and database
technology, more perfect and accurate furnace material consumption data will be
needed in the future.
In this paper, the field PLC process smelting data of the material consumption
in a steel plant 50 t “EAF-LF-CC” process is collected from KEPServerEX as OPC
Server, which is classified (scrap charging, auxiliary materials, gas consumption,
injection information, power supply data, etc.) and stored into Microsoft SQL Server
2008 database to build database of furnace material consume. Based on the data of
furnace consumption in this database, the cost analysis model of EAF steelmaking
process has been developed by Visual Studio.Net 2010. The model can be used
to adjust the addition of auxiliary materials such as power supply, oxygen supply,
carbon powder spraying and lime in the smelting process, so as to provide basis
for optimizing the consumption of furnace materials and support for enterprises to
control costs.
In the future, the existing database needs to be systematically improved, so that
the material consumption database will play a greater role.
References
1. Zhao J (2005) Research on new technology of short process steelmaking. Master thesis,
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Experimental Study on Water Model
of Continuous Smelting Reduction
Reactor
Haijuan Li, Yan Liu, Xiaolong Li and Ting’an Zhang
Abstract Non-blast furnace ironmaking technology of metallurgical slags with

high-grade iron and low grade iron ore is of great importance and becoming increas-
ingly valued. This paper presents a new type of continuous smelting reductive reaction
for non-blast furnace ironmaking technology. Cold water model experiment based
on principle of similitude establishes a new type of reactor. This paper studies the
core problem of two-phase separation and investigates the relationship among mate-
rial factors, operating factors, equipment factors. Finally, according to the analysis
of theoretical and experimental data, we can obtain the empirical equation between
the oil phase entrainment and each factor, in order to provide a theoretical basis for
further thermal experiments and has certain reference value.
Keywords Physical simulation · Metallurgical slags · Smelting reduction · Oil

phase entrainment
Introduction
Metallurgical slags are usually considered a waste and the accumulation of metallur-
gical slag increases year by year [1]. However, the grade of iron in a large number of
metallurgical slags is generally higher than the average iron ore grade in the indus-
try. If iron resources in slag can be utilized to realize the effective recovery of iron
resources in slag, It can not only form an effective supplement to the demand for iron
resources, alleviate the pressure brought by the rise of iron ore prices on the iron and
steel industry, but also make resource utilization of slag and reduce the harm to the
environment. How to utilize and recover metals from slags is an urge problem to be
solved in order to optimize their economical and environmental balance [2–5].
H. Li · Y. Liu (B) · X. Li · T. Zhang

Key Laboratory of Ecological Metallurgy of Multi-Metal Intergrown Ores of Ministry of
Education, Special Metallurgy and Process Engineering Institute, Northeastern University,
Shenyang 110819, China
e-mail: liuyan@smm.neu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_42
476 H. Li et al.
Many metallurgical scholars have done some research on the technology of recov-
ering iron from slag. Liu et al. [6] proposed a new method for the treatment of slag by
weak oxidation roasting and magnetic separation. Finally, they obtained the iron con-
centrate with 54.79% iron grade and tailing with 22.12% iron and the recovery rate
of iron was 80.14% from the copper slag. Hu et al. [7] studied the method of direct
smelting reduction and magnetic separation to recover iron. Using copper slag as raw
material, reduce iron concentrate with iron grade of 67.47% by magnetic separation
and iron recovery of 92.32% is obtained. Smelting reductive process is a popular
kind of non-blast furnace ironmaking technology for recovering metallurgical slag
due the advantages [8]. A vortex stirring smelting reduction ironmaking method
independently developed by Northeastern University has made a breakthrough in
the technology of extracting iron from slag, and the reduction rate of iron can reach
more than 95.5%. The iron content in the smelting slag is less than 0.35%. How-
ever, the melting and ironmaking process is intermittent. After the completion of
the reduction reaction, the temperature decreases and the heat is lost. If the next
furnace reaction continues, it needs to be reheated, which not only wastes energy but
also affects the production efficiency and leads to the high energy consumption in
the smelting reduction ironmaking process. In the case of cold and heat exchange,
the unstable heating state of refractories leads to a decrease in the life of refrac-
tories. Because of the high energy consumption and difficult operation of the high
temperature experimental process, this study uses the physical model to carry out
the experiment, find the suitable operating conditions, and realize the continuity of
the melting reduction process to solve the shortcomings of the above process.
In this experiment, the model is made of plexiglass and the structure and size of the
reactor are reasonably designed by using continuity equation and similarity principle
so that the flow of the simulated liquid is approximate to the flow state of the liquid
in the melting reduction process [9–11]. The experiment uses different material flow
rate and height from the bottom of the agitator, six straight blade agitator, stirring
mode as the center, the rotating speed of the agitator is 0–60 r/min, and the ratio
of material is 1.2, 1.5, and 1.8. The specific gravity method is used to study the
various factors affecting the oil phase entrainment, and the quasi-number equation
between the oil phase entrainment and the parameters is obtained by combining the
dimensional analysis and the experimental data, which provides a theoretical basis
for further hot state experiments [12]. It has a certain reference value.
Experimental
Establishment of Physical Model
The viscous force and surface tension have a significant effect on the stirring, so the
Reynolds number and Euler number between the model and the prototype are equal.
The Bernoulli equation should be satisfied in the process of physical model design,
Experimental Study on Water Model of Continuous Smelting … 477
and the continuity equation should be satisfied in the process of realizing continuity.
v21 ρ1 v2 ρ1 v2 ρ2
P0 + ρ1 gH1 + = P0 + ρ1 gH2 + ρ2 gH3 + 1 + 2 (1)
2 2 2
The relationship in static condition is obtained that is:
H1 = H2 + H3 ρ2 /ρ1 (2)
where H1 , H2, and H3 are the heights of smelting furnace, separation furnace, and
steel ladle
The schematic diagram of the model and the actual physical model in this
experiment are shown in the Fig. 1.
The slag bag in Fig. 1a is replaced by a beaker in this experiment. The specific
dimensions of the equipment are shown in Table 1.
(a) (b)
Smelting furnace Smelting furnace
Separation furnace
Pump
Steel ladle
Cinder ladle Separation furnace Steel ladle
Fig. 1 Physical model in the experiment
Table 1 Physical model size

Size/mm Smelting Separation Steel ladle
furnace furnace
Diameter 100 140 140
Height 100 320 250
Upper – 240 –
opening
position
Lower 360 20 20
opening
position
478 H. Li et al.
Table 2 Physical parameters

Species Density ρ/g· Viscosity Temperature
of the system
μ/pa·s T/°C
Smelting slag 3.5–4.3 0.077–0.366 1250–1500
oil 0.8024 0.085 25
Hot metal 7.138 0.248–0.417 1250–1500
Glycerol 1.2610 0.56 25
Material
In the water model experiment of this study, the oil is selected as the simulation of
hot metal, and the simulation system of slag is selected by calculation. The flow state
of the two liquids is mainly affected by the surface tension of the liquid, so the We
criterion in the kinetics is equal.
Wem = Wep (3)
where and are the Weber numbers of water model experiments and hot metallurgical
engineering. In this experiment, it can be expressed as:
V2Gly × ρOil V2Iron × ρIron

1/2 = 1/2 (4)
σGlycerol − Oil × g × ρGly − ρOil σIron −Slag × g × ρIron − ρSlag
VGly and VIron are the velocity and molten steel; The densities of glycerol, molten
steel, oil, and slag are represented by are represented by ρOil , ρIron and ρSlag , and σ
are expressed, as the difference of surface tension between two phases. The physical
parameters of the system are given in Table 2.
Experimental Scheme
In the process of pre-experiment, according to the influence of different types of

paddles on the fluid, the six straight blade turbine oars are selected for the experiment.
In this paper, the effects of different rotating speed, position, material ratio, and flow
rate on the effect of two-phase separation were studied. The specific test parameters
Analytical Method
In this paper, the two liquids used in the experiment are satisfied:
Table 3 Operating parameters inf the experiment

Variable parameters
Agitator speed r/min 0 10 20 30 40 50 60
position of agitator mm 100 140
Material ratio 1.2:1 1.5:1 1.8:1
flow rate mL/min 50 100

∂ux ∂uy ∂uz
+ + dx dy dz dt = 0 (5)
∂x ∂y ∂z
Therefore, the two liquids are incompressible Newtonian fluid. No change in

mixing volume of two liquids. The specific gravity method can be used to measure
the oil phase entrainment in the overflow liquid to indicate the effect of two-phase
separation. The working curve of glycerol ratio in overflow liquid is shown in the
Fig. 2.
The following relationships can be obtained from Fig. 2:
y = 0.4586x − 1.7497 (6)
After linear fitting, the correlation coefficient is 0.99737. the relative error of this
method is small, which shows that the specific gravity method is reliable and can be
used in this experiment.
Fig. 2 Working curve of

glycerol ratio
480 H. Li et al.
Determination of Separation Speed in Static State
A certain amount of glycerol and oil was added to the reactor at 1:1. After static
10 min, add the mixed liquid to the reactor with a glass rod. At the height from the
bottom of 5, 7, 9, 11, and 13 cm, the solution was taken out for every 5 min and
weighed on the electronic analytical balance. The results are shown in the Figs. 3
and 4.
Fig. 3 Variation of liquid

content at different positions
with time
Fig. 4 Variation of liquid content with position in different time

a P=1.2 b P=1.5 c P=1.8
Fig. 5 Effect of flow rate on separation effect under different material ratio
As can be seen from Figs. 3 and 4, taking into account the production efficiency
and investment cost of the process, it can be considered that the state after 15 min can
be separated. Then select the traffic for 50 and 100 ml/min for the next experiment.
Effect of Flow Rate on Separation
An important parameter investigated in this research was the effect of the flow rate
at which the mixed liquid enters. The variation of oil phase entrainment with a flow
rate in overflow liquid is shown in Fig. 5 for the material ratio 1.2, 1.5 and 1.8.
With the increase of the material flow rate, the residence time of the mixed liquid
in the reactor decreases, so the liquid has not been completely separated. Therefore,
the oil entrainment of the mixed liquid that of 100 ml/min is always larger than when
the flow rate of the mixed liquid is 50 ml/min. And the rising rate of oil phase impurity
with a speed of 100 ml/min is faster than that of 50 ml/min. The experimental effect
of 50 ml/min is good, so the following experiments are carried out with a flow rate
of 50 ml/min.
Effect of the Position of Agitator on Separation
Under the experimental condition that the material ratio of four straight blade agitator
is 1.2–1.8, the continuous production process is simulated by using the reactor made
of plexiglass. The experimental results of the effect of position of the agitator on
separation are shown in Fig. 6.
Figure 6 shows that the oil entrainment in the overflowing liquid increases obvi-
ously with the increase of the height from the bottom of the agitator. There is a
critical speed to make the best separation effect. When the rotating speed of the
agitator is greater than the critical speed, the oil phase entrainment of the overflow
liquid increases rapidly, and the separation effect becomes worse.
482 H. Li et al.
a P=1.2 b P=1.5 c P=1.8
Fig. 6 Effect of agitator position on separation effect under different material ratio
In the actual production process, when the solid material is added, the solid mate-
rial melts rapidly due to the high temperature in the production, and the hot metal is
reduced by reduction reaction, which takes a very short time. Therefore, the continu-
ity of the experimental production process is mainly affected by the separation rate
of slag and gold. The position and speed of the agitator are very important in produc-
tion. Through the simulation experiment, it can be seen that the optimum rotating
speed corresponding to different material ratio is different, so the rotating speed of
the agitator corresponding to the ore of different taste is different in the production.
Effect of Material Ratio on Separation
The material ratio indicates the volume ratio of the added oil to glycerol, which
reflects the proportion of iron contained in the slag in production, that is, the grade of
iron. The higher the material ratio, the lower the corresponding iron content. Under
the condition of 50 ml/min flow rate and 100 mm off-bottom height of agitator, the
experimental results of the effect of material ratio on the separation effect under
different rotational speed are shown in Fig. 7.
It shows that when the ratio of the material is 1.8 (when the grade of iron is
about 35.7%), the effect of two-phase separation is better. From the point of view of
physical simulation, continuous smelting reduction technology has high application
value to low-grade iron ore.
Dimensional Analysis
Through the analysis of experimental data, we can know separation efficiency was
effected mainly by the following factors:
1. Height from the bottom of agitator in reaction chamber: h;
2. Rotating speed of agitator in reaction chamber: n;
3. Flow rate when liquid enters: Q.
Fig. 7 Effect of material

ratio on separation effect
under different rotational
speed
4. Summarize previous research on the separation, we found the separation effect

has also been related to the density of glycerol (heavy oil) phase ρ1 ; the density
of oil (light oil) phase ρ2 ; the viscosity of glycerol (heavy oil) phase μ1 ; the
viscosity of vegetable oil (light oil) phase μ2 ; the diameter of agitator d; the
reactor diameter D; the speed of liquid separation v; the acceleration of gravity g
and other factors, but they are constant in this experiment, so we do not discuss
in this paper.
Dimension of variables are in Table 4.
According to the Buckingham π theorem, it can be obtained that the expression
of oil phase entrainment can be expressed as:
(7)
In this experiment, where ρ1 , ρ2 , μ1 , μ2 , D, H1 , H, Q, V, and g are quantitative,

so
(8)
The criterion relations of various phenomena can often be expressed in the form of
power function in a certain range of independent variables. From the above analysis,
we can fit the empirical criterion formula as follows:
(9)
or
484
Table 4 Dimension of variables

ρ1 ρ2 μ1 μ2 d D h n V Q g
M 1 1 1 1 0 0 0 0 0 0 0
L −3 −3 −1 −1 1 1 1 0 1 3 1
T 0 0 −1 −1 0 0 0 −1 −1 −1 −2
H. Li et al.

the experimental value and
theoretical value
(10)
where K, A, B, and C were the fitting coefficients.

According to the experimental results, the value of the fitting coefficients could
be as follows:
K
So
(11)
Figure 8 shows that the theoretical values of the experiment are in good agreement
with the experimental values. Therefore, the given operating parameters can be used
to predict the effect of two-phase separation, which provides a certain theoretical
basis for the realization of continuity in the melting reduction process.
Conclusions
(1) With the increase of the flow rate of the material, the residence time of the
mixture in the reactor decreases, and the liquid does not have time to separate
completely, which leads to the poor separation effect when the flow rate is
100 ml/min, indicating that the effect of two-phase separation becomes worse
with the increase of flow rate.
(2) The experimental effect of 100 mm from the bottom of the agitator is better
than that of 140 mm from the bottom of the agitator. It shows that the position
of the agitator near the overflow port is more beneficial to the separation.
486 H. Li et al.
(3) When the material mix is relatively high, the oil phase entrainment does not
increase obviously. The experimental results show that from the point of view
of physical simulation, the continuous melting reduction process is more suitable
for low grade iron ore.
(4) By using the combination of dimensional analysis and experimental method, it
is concluded that:
It provides a certain theoretical basis for the next experiment of continuous

smelting reduction process at high temperature.
Acknowledgements This study was financially supported by the National Natural Science Fund
Committee (U1760120), and the National Key R&D Program of China (2017YFC0210404,
2017YFC0210403-04).
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Theoretical Analysis and Experimental
Verification of Formation of As-Bearing
Rare Earth Inclusions in Steel
Bin Bai, Hongpo Wang, Silu Jiang, Lifeng Sun and Yu Wang
Abstract It is a feasible method to improve the quality of steel products by adding

rare earth to change the state of arsenic in steel to avoid its harm. In this study, the
As-bearing rare earth inclusions in steel were extracted by non-aqueous electrolysis
method, and their types were fully understood. Wagner activity model and non-
equilibrium solidification model were used to calculate the formation process of rare
earth inclusions in liquid and solidification process. The formation mechanism of
single-phase and complex As-bearing rare earth inclusions was verified by laboratory
experiments. The results showed that La2 O3 and La2 O2 S were formed in the liquid
phase, then the As-bearing rare earth inclusions La–S–As and La–As began to form
during the solidification process of steel liquid. The composite inclusions of La–O–
S–As with distinct stratification were further precipitated.
Keywords Electrolysis · The As-bearing inclusions · Rare earths · Solidification
Introduction
The harm of residual elements in steel is one of the major problems faced by the
contemporary steel industry [1], such as Sn and As. The presence of these ele-
ments seriously affects the quality and performance of steel products [2, 3]. Residual
element arsenic mainly comes from molten iron and scrap steel in the process of
steelmaking [4], and is usually segregated at the grain boundary, which significantly
reduces the toughness and thermal processability of steel products.
Generally, the inclusion is observed by optical microscope and scanning electron
microscope on the polished steel sample to obtain the information of morphology,
composition and size [5–7]. However, due to the three-dimensional shape of the
B. Bai · H. Wang (B) · S. Jiang · Y. Wang

e-mail: wanghp@cqu.edu.cn
L. Sun
Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education),
Northeastern University, Shenyang 110819, Liaoning, China

https://doi.org/10.1007/978-3-030-36540-0_43
490 B. Bai et al.
inclusion, two-dimensional analysis cannot accurately characterize the inclusion[8–

11]. Therefore, it is necessary to extract inclusions from steel matrix by electrolysis
method to observe its three-dimensional morphology.
In addition, the final step of collecting inclusions is filtering. To collect small
inclusions, the mesh size of the filter membrane used in this paper is 0.25 µm.
Experimental Materials and Methods
In this paper, two kinds of steel samples with different As contents were prepared,
and their chemical compositions are shown in Table 1. In order to extract more
inclusions and maintain their original shape, a non-aqueous electrolyte was used. A
cylindrical sample with a diameter of 10 mm is used as an anode, and a stainless
steel sheet is used as a cathode. The electrolyte consisted of 1%4-methylammonium
chloride, 5%triethanolamine, 5%glycerol, and 89%methanol. During the electrolysis
process, a regulated DC power supply is used to keep the current density between
60–90 mA/cm2 . The electrolyte temperature is maintained between 268 K and 278 K,
and the electrolyte is stirred with nitrogen to improve the mixing conditions. After
13 h of electrolysis, the anode was transferred to a 100 ml beaker containing 50 ml
of alcohol, ultrasonically washed for 5 min, and repeated three times, and then the
liquid in the beaker was transferred to a watch glass and dried at room temperature
for 8 h.
Inclusion Type
The inclusions obtained by electrolysis and metallographic experiments mainly

include La2 O3 inclusions, La2 O2 S inclusions, La–S–As inclusions, and La–O–As
inclusions. The La–S–As inclusions are irregularly elongated, the La2 O2 S inclu-
sions are spherical, and the La2 O3 inclusions have irregular shapes (Figs. 1, 2, 3, and
4).
The formation mechanism of La2 O3 , La2 O2 S, and LaAsO4 has been described in
detail in this research group [12, 13]. This section analyzes the mechanism of the
formation of La–As and La–S–As. The precipitation of inclusions is determined by
the solubility product of the inclusions. In order to evaluate whether the inclusions
Table 1 Main chemical composition of experimental steel (wt%)
Numbering C Si Mn P S T.Al O As La
3 0.79 0.21 0.61 0.011 0.014 0.001 0.004 0.03 0.15
20 0.79 0.21 0.61 0.011 0.014 0.001 0.004 0.10 0.15
Theoretical Analysis and Experimental Verification of Formation …
491
492 B. Bai et al.
Fig. 1 Morphology and energy spectrum of La2 O3 inclusions with As content of 0.10%
Fig. 2 Morphology and energy spectrum of La2 O2 S inclusions with As content of 0.10%
Fig. 3 Morphology and energy spectrum of La–S–As inclusions with As content of 0.03%
precipitated in the liquid phase, the liquidus and solidus temperatures were first
calculated to be 1731 and 1636 K, respectively.
Theoretical Analysis and Experimental Verification of Formation … 493
Fig. 4 Morphology and energy spectrum of LaAsO4 inclusions with As content of 0.03%
Thermodynamic Analysis of LaAs Rare Earth Inclusions
Based on the equilibrium analysis, the activity product of LaAs is calculated [14]
(Fig. 5).
LaAs(s) = [La] + [As] G θ = 355328.09 − 187.1 · T (1)
log(a La · a AS )eq = −18559.87/T + 9.77 (2)
Figure 5 shows that the composition of the steel is in the solid phase region.
Obviously, LaAs inclusions cannot be formed in the liquid phase.
During the solidification, La, As elements in the solidification front are continu-
ously enriched due to the redistribution of solutes in semi-solid area. When they are
enriched to a certain extent, the actual activity product of elements La, As will be
greater than the equilibrium activity product; Then, LaAs will be generated.
Fig. 5 Concentration
required to generate LaAs in
liquid form
494 B. Bai et al.
Therefore, Schell’s model [16] was used to analyze the non-equilibrium solidifi-
cation process. The microsegregation equation is as follows:
[ pct M] L = [ pct M]0 (1 − f S )kW −1 (3)
where [pctM]0 represents the initial concentration of M in the molten steel, [pctM]L
represents the concentration of M in the liquid phase during solidification, f S is the
solidification coefficient, and kM is the M equilibrium partition coefficient. Balance is
the correlation coefficient reference [14], assuming that these values remain constant
during the solidification process.
The actual concentration product Q during solidification can be expressed as
Q M x = [ pct X ] L [ pct M] L = [ pct X ]0 [ pct M]0 (1 − f S )kM−1 (1 − f S )k X −1 (4)
The relationship between the solidification fraction and temperature is
(T0 − TL )
T = T0 − −TS )
(5)
1 − f S (TTL0 −TS
where T is the liquidus temperature during solidification, TL and TS are liquid and
solid phase temperatures, respectively, and T0 is pure iron melting point (1809 K). The
equilibrium solubility product can also be expressed as a function of the solidification
coefficient using equation [5].
Figure 6 calculates and compares the values of logKLaAs and logQLaAs for LaAs
inclusions. As can be seen from the figure, when the solidification coefficient
exceeds 0.59, logQLaAs is larger than logKLaAs , so LaAs can be precipitated during
solidification.
Fig. 6 Calculation results of

Schell’s model of LaAs
during solidification
Thermodynamic Analysis of La–S–As Rare Earth Inclusions
Wu et al. [15]. gave the chemical formula of La–S–As inclusion and its standard
Gibbs free energy.In order to verify whether La–S–As can be generated at the melt-
ing temperature, the Wagner activity model is applied in this section. The activity
coefficient is calculated by equation [7]. Activity is calculated by equation [8]. The
interaction coefficient of each element in the calculation is referenced [14]. In the
calculation, 0.03 mass% As and 0.10 mass% As were chosen.
1/2(LaAs · LaS)(s) = [La] + 1/2[S] + 1/2[As] G θ = 400276.55 − 161.39 · T

(6)

n
j
Log f i = ei [wt% j] (7)
j=1
ai = f i [wt%i] (8)
The actual activity product of La, S, and As under 1600 °C was calculated to be
1.74906 × 10−8 (0.03% As) and 6.118 × 10−8 (0.10% As) respectively.
On the other hand, the relationship between the equilibrium activity product of
La, S, and As and temperature can be expressed by equation [9], and it is calculated
to be 1.86 × 10−3 under 1600 °C.

1/2 1/2
log a La · a S · a As = −20909.06/T + 8.43 (9)
eq
We put the two activity products of La, S, and As in the same picture, Fig. 7 shows
that the LaAs·LaS cannot be generated under 1600 °C.
During the solidification process of molten steel, La, S, and As in the solidification
front are continuously enriched due to the redistribution of solid–liquid two-phase
Fig. 7 The equilibrium

activity product of La, S, and
As and the activity product
496 B. Bai et al.
Fig. 8 Relationship between

logQ and logK of LaAs·LaS
and f S in solidification
process
solute. When La, S, and As are enriched to a certain extent, their actual activity prod-
uct may be greater than their equilibrium activity product. At this point, LaAs·LaS
inclusions will be generated at the solidification front.
(1) The actual active product of La, S, and As during solidification
This paper uses the Schell model to calculate the non-equilibrium solidification
process. The microsegregation equation is based on equation [3]. Since the solute par-
tition coefficient of the rare earth element La is not found in the literature, considering
the chemical properties of the rare earth element La and the rare earth element Ce,
the solute partition coefficient of Ce is used instead of the solute partition coefficient
of La.
The equilibrium activity product of La, S, and As in the solidification process is
obtained by the equations [5, 9].
(2) Balanced active product of La, S, and As during solidification
Figure 8 shows that the value of logQ of the La–S–As inclusion exceeds the value
of log K, so La–S–As inclusions are always formed during solidification.
Distribution of Inclusions
In this section, the distribution of the As-bearing rare earth inclusions in the sample
were studied experimentally. From the above calculations and previous work of the
group, it can be inferred that the As-bearing rare earth inclusions are produced due
to the solute redistribution during the non-equilibrium solidification of Solidification
frontier, and are generated in the segregation region of the solute.
However, due to the lack of relevant thermodynamic data, it is not possible to
perform relevant thermodynamic and kinetic calculations for all the As-bearing rare
Fig. 9 Morphology and energy spectrum of La–O–S–As inclusions in steel after corrosion
Fig. 10 Morphology and energy spectrum of La–S–As inclusions in steel after corrosion
earth inclusions. Therefore, the formation mechanism of the As-bearing rare earth
inclusions was verified by corrosion experiments.
The figure below shows the energy spectrum of the As-bearing rare earth
inclusions obtained after the corrosion test (Figs. 9 and 10).
In the figure, La–O–S–As inclusions and La–S–As inclusions are distributed near
the grain boundaries or on the grain boundaries. It is indicated that the As-bearing
rare earth inclusions are formed by segregation at the grain boundary due to the solute
redistribution.
Inclusion Generation Process
When La is added to the steel, the rare earth first reacts with O and S in the steel
to form La2 O3 , La2 O2 S, and LaS inclusions. When the amount of La added in the
steel is 0.15%, the type of inclusions in the steel also changes as the content of As
increases. When the As content is 0.03%, it is mainly La–S–As and a small amount
of LaAsO4 inclusions. With the increase of As content in steel, [La] + [S] + [As]
= La–S–As. The reaction proceeds in the forward direction, and a large amount of
498 B. Bai et al.
La–S–As inclusions are formed. When the As content is 0.1%, the steel is mainly
a large piece of La–S–As inclusions, a small amount of LaAsO4 inclusions, and a
composite inclusion of LaAs with LaAsO4 as the core.
Conclusions
(1) In this study, the inclusions in the As-bearing rare earth steels were successfully
extracted by non-aqueous electrolysis. The results show that the inclusions are
mainly La2 O3 , La2 O2 S, La–S–As.
(2) Through the calculation of the non-equilibrium solidification process, it is con-
firmed that La–As and La–S–As can form during the solidification process due
to the enrichment of the solidification frontier La and As.
Acknowledgements This research is financially supported by National Natural Science Foundation

of China (No. 51704051), Foundation of Key Laboratory for Ecological Metallurgy of Multimetallic
Mineral (Ministry of Education) (No. NEMM2018001) and Chongqing Postdoctoral Funds (No.
Xm2017192).
References
1. Yikang W, Wenli L, Yuanqi Han (1985) The problem of impurity elements in smelting high-
quality alloy steel with industrial scrap. Ordnance Mater Sci Eng 2:1
2. Kondo Y (2004) ISI J Int 44:1576–1580
3. Matsuoka H, Osawa K, Ono M, Ohmura M (1997) ISlJ Int 37:255–262
4. Wang Y, Zhai A, Zhang D (1998) The problem of trace elements in steel[J]. In: Proceedings
of the national conference on direct reduction iron production and application
5. Yang W, Zhang L, Wang X, Ren Y, Liu X, Shan Q (2013) ISIJ Int 53:1401–1410
6. Furuya Y, Matsuoka S, Abe T (2004) Metall Mater Trans A 35A:3737–3744
7. Verma N, Pistorius PC, Fruehan RJ, Potter M, Lind M et al (2011) Metall Mater Trans B
42B:720–729
8. Karasev A, Suito H (1999) Metall Mater Trans B 30B:259–270
9. Ohta H, Suito H (2006) ISIJ Int 46:14–21
10. Takahashi J, Suito H (2001) Acta Mater 49:711–719
11. Doostmohammadi H, Karasev A, Jonsson PG (2010) Steel Res Int 81:398–406
12. Wang HP, Xiong L, Zhang L et al (2017) Investigation of RE–O–S–As inclusions in high
carbon steels [J]. Metall Mater Trans B 48(6):2849–2858
13. Wang HP, Bai B, Jiang SL et al, An in situ study of the formation of rare earth inclusions
in arsenic high carbon steels [J]. ISIJ Int. https://doi.org/10.2355/isijinter-national.ISIJINT-
2018-853
14. Xin W (2016) Effect of arsenic on steel properties and improvement of rare earths [D].
University of Science and Technology Beijing
15. Yichuan W, Guoguang C (2013) The role of rare earth elements in residual arsenic and tin
09Cr2AlMoRE Steel[J]. Chin J Rare Earths 31(5):597–604
16. Scheil E (1942) Zeitschrift Metallkunde 34:70–72
Parameters Affecting the Phosphorus
Distribution Between Slag and Liquid
Metal in BOF
Abdelrhman Hassan and Mohammed Meraikib
Abstract The phosphorus content of the hot metal is higher than the range and
optimal content of hot metal normally used for steel making in LD converters at
EISCO. Therefore, adequate care is necessary to investigate slag/metal partition of
phosphorus. The activity of total ferrous oxide in the slag was estimated according
to the model of regular ionic solutions, it was used to find the concentration of
oxygen in the metal. The activity coefficient of phosphorus and oxygen in the metal
is 1.1195 and 0.8367, respectively. By using the phosphate capacity, phosphorus
distribution between slag and metal could be calculated; the effect of temperature
on both phosphate capacity and phosphorus distribution ratio is large, while the
influence of slag composition is small.
Keywords Blast furnace · Phosphorus distribution · Phosphate capacity ·

Basicity · Temperature effect
Introduction
Iron ores used for sintering at the Egyptian Iron and Steel Company (EISCO) have
relatively high contents of manganese, phosphorus, zinc barium together with alkali
chlorides and alkali oxides. In the sintering process, phosphorus oxides remain in
the sinter used as blast furnace feed. Consequently, the hot metal produced contains
relatively high proportions of phosphorus, which should be brought down to the
required level in the steel grade to be produced in the LD converter.
The aim of the present work is to investigate the distribution of phosphorus
between slag and bath in the LD converter by using the concept of phosphate capacity
of slag.
A. Hassan (B) · M. Meraikib

Tabbin Institute for Metallurgical Studies (TIMS), Cairo, Egypt
e-mail: discover3030@gmail.com
M. Meraikib
e-mail: mmeraikib@hotmaill.com

https://doi.org/10.1007/978-3-030-36540-0_44
500 A. Hassan and M. Meraikib
The effect of the main process parameters, such as temperature and slag basicity,
on the factors influencing phosphorus distribution, e.g., activity of P2 O5 in the slag
and phosphate capacity, will be studied. The data used for this purpose were obtained
on three identical 90 ton LD converters of EISCO at Tabbin, Helwan, Egypt.
Experimental Work
The trial heats were conducted on the three identical 90 ton LD converters at EISCO.
At first, steel scrap was charged into the converter. This was followed by pouring the
hot metal having the composition given in Table 1.
The vessel was then put in an upright position and oxygen blowing through a water-
cooled lance at a rate of 200 to 240 Nm3 /min was started. The distance between the
tip of the lance and the surface of the metal ranged from 12 to 20 cm and the oxygen
pressure was 13 to 15 ATM.
With the start of blowing, the first portion of burnt lime having about 90% CaO
and 2% SiO2 and/or dolomite was fed into the converter. The rest of the flux was
added during blowing.
Because of the high phosphorus content of the hot metal, double slagging tech-
nique was used. Just before slagging-off, the temperature was measured and a slag
and corresponding metal samples were taken for analysis. After the removal of the
first slag, oxygen blowing was resumed and the required fluxes were added to make
a fresh slag.
At the end of the second stage of blowing, the temperature was measured and a
slag and the corresponding metal sample were collected for analysis. Then the slag
was removed and the steel was tapped.
The composition of slag was determined by X-ray Fluorescence technique
PL72000 Model and the metal analysis was done by using an Emission Quantometer
PL31000 Model. Tapped steel was deoxidized and brought to the desired composition
by adding deoxidation materials and ferroalloys in the ladle [2].
The average analysis of hot metal used for steel production at EISCO is given in
Table 1. For comparison, the range of analysis and optimal composition of hot metal
normally used for steelmaking in LD converters is given in Table 2 [3].
Table 1 average composition of EISCO hot metal, weight % [1]

Element C Si Mn P S
Composition, % 4.01 0.74 2.25 0.32 0.015
Parameters Affecting the Phosphorus Distribution …’ 501
Table 2 Range and optimal composition of hot metal for steel making in LD converter, weight %
[3]
Element C Si Mn P S
Range, % 3.60–4.60 0.05–2.50 0.30–3.50 ≤0.30 ≤0.04
Optimum, % 4.20 0.50–0.80 0.60–0.90 ≤0.12 ≤0.03
It is obvious that both the range and average of phosphorus concentration in the hot
metal used at EISCO are higher than the average and optimal contents of phosphorus
in the hot metal normally used for steelmaking in LD converters. This is attributed
to the high concentration of phosphorus oxide in the ore P2 O5 equal to 0.45% [3].
Because of the high level of phosphorus in the hot metal and the deleterious effect
of its removal in the converter on the steel yield, the distribution of phosphorus
between slag and metal and the main process parameters affecting the distribution
are closely investigated in the present work.
Oxidation of Phosphorus in LD Process
The concept of phosphate capacity used in this research to study the partition ratio of
phosphorus between slag and metal is based on the oxidation of phosphorus according
to the reaction:
5
[P] + [O] = (P O2.5 ) (1)
2
According to this reaction, the phosphate capacity, CP , can be defined as [4, 5]
(%P)
CP = 5/2
(2)
a[P] · a[O]
where (P) is the phosphorus equivalence of P2 O5 in the slag, a[P] and a[O] are the
activities of phosphorus and oxygen in the metal.
Activity of phosphorus in liquid steel
The activity of phosphorus aP is determined according to the dilute solution model
[4, 5, 8] as follows:
a[P] = f[P] [P] (3)
where f[P] and P are the activity coefficient and concentration, in weight %, of
phosphorus in liquid steel. The activity coefficient can be calculated from
log f[P] = e(P) (S) (C) (O) (Mn)

P [P] + eP [S] + eP [C] + eP [O] + eP [Mn] + e(Si)
P [Si] (4)
(i)
Table 3 Values of interaction parameters, eP [6, 8]
(P) (S) (C) (O) (Mn) (Si)
Parameter eP eP eP eP eP eP
Value 0.062 0.028 0.13 0.13 0 0.12
0.5
Phosphorus activity in liquid
0.4 y = 1.1195x
R2= 0.9989
0.3
steel a[P]
0.2
0.1
0
0 0.1 0.2 0.3 0.4
Phosphorus concentration in liquid steel [P] ,wt %
Fig. 1 Variation of the activity with the concentration of phosphorus in liquid steel
The interaction parameters e(i)P [6, 8] are given in Table 3.

By using the values of interaction parameters given in Table 3 and Eqs. 3 and 4,
the variation of activity with the concentration of phosphorus in liquid steel given in
Fig. 1.
The straight line satisfies Eq. 5.
a[P] = 1.1195[P] r = 0.994 (5)
The correlation coefficient is practically equal to unity, indicating a very strong

correlation between activity and concentration of phosphorus in liquid steel.
Comparing this equation with 3, it follows that:
f[P] = 1.1195 (6)
Activity Coefficient and Activity of Total Ferrous Oxide in Slag
The activity of total ferrous oxide in the slag was found, according to the model of
regular ionic solutions [7, 8].
2303
ln γ(Fet O) = 2.18x(MnO) xSiO + 5.9 x(CaO) + x(MgO) xSiO + 10.50x(CaO) xP O (7)
T 2 2 2 5
where γ(FeO) is the activity coefficient of total ferrous oxide in the slag.
The activity of total ferrous oxide a(Fet O) is given by:
a(Fet O) = γ(Fet O) x(Fet O) (8)
Effect of Temperature and Basicity on Activity of Total Ferrous

Oxide
The activity coefficient of total ferrous oxide in the slag varies with the temperature
as shown in Fig. 2.
The regression line resulting from the plotting of ln a(Fet O) against the reciprocal
of the absolute temperature, is straight and satisfies the next formula
11087
ln γ(Fet O) = − 5.4491 r = 0.7063 (9)
T
(%CaO)
The activity coefficient correlates with the basicity B = (%SiO 2)
over the whole
range of temperature as well as in a narrow range. The results obtained over the
whole range of temperature are shown in Fig. 3.
The straight line can be described by the following equation:
3.1907
γ(Fet O) = + 1.1876 r = 0.782 (10)
B
0.55
coefficient of total ferrous oxide
Natural logarithm of activity
0.45
y = 1.1087x - 5.4491
R2= 0.4988
0.35
0.25
0.15
5.12 5.16 5.2 5.24 5.28 5.32
10000/T.K-1
Fig. 2 Variation of the activity coefficient of total ferrous oxide with the reciprocal of the absolute
temperature in the range of basicity 6.6374 ≥ B ≥ 5.4837
Fig. 3 Variation of the 3
Activity coefficient of total

activity coefficient of total
ferrous oxide with the
reciprocal of basicity B
ferrous oxide
2
1
0 0.2 0.4 0.6
Reciprocal of Basicity, 1/B
Estimation of Oxygen Concentration in Liquid Steel
The oxygen concentration can be found from the following relation [4, 8]
[O]
a(Fet O) = (11)
[O]max
where [O] and [O]max are the concentration of oxygen in the metal when it’s in
equilibrium with the steelmaking slag and the maximum concentration when the
metal is in equilibrium with a slag of ferrous oxide.
The maximum concentration of oxygen can be calculated from

14552
[O]max = exp 6.2953 − (12)
T
From Eqs. 11 and 12, the oxygen content in the metal can be calculated for any
temperature and activity of total ferrous oxide.
Activity of Oxygen in Liquid Steel
According to the dilute solution model, the activity of oxygen dissolved in molten
steel is given by [6, 7]
a[O] = f[O] [O] (13)
where f[O] and [O] are the activity coefficient and concentration, in weight %, of
oxygen in liquid steel. The activity coefficient can be calculated from
log f[O] = e(O) (S) (Mn) (C) (P) (Si)

O [O] + eO [S] + eO [Mn] + eO [C] + eO [P] + eO [Si] (14)
(i)
Table 4 Values of interaction parameters, eO [4, 6, 8]
(O) (S) (Mn) (C) (P) (Si)
Parameter eO eO eO eO eO eO
Value – 0.20 – 0.133 – 0.021 – 0.45 0.070 – 0.131
0.14
Oxygen activity in liquid steel, a[O]
y = 0.8367x
0.12
R2= 0.8361
0.1
0.08
0.06
0.04
0.06 0.09 0.12 0.15
Oxygen concentration in liquid steel [O] ,wt%
Fig. 4 Variation of the activity with the concentration of oxygen in liquid steel
The interaction parameters e(i)

P [4, 6, 8] are given in Table 4.
The interaction parameters in Table 4 were used to calculate the activity coefficient
of oxygen, according to Eq. 14 and the activity by using Eq. 13.
The results are shown in Fig. 4 which satisfies the regression equation
a[O] = 0.8376[O] r = 0.9144 (15)
Comparing Eq. 15 with Eq. 13, the value of the activity coefficient of oxygen was
obtained:
f[O] = 0.8367
Effect of the Temperature on Phosphate Capacity
The phosphate capacity varies with the temperature and slag composition [4, 9] the
relationship between the logarithm of phosphate capacity and the reciprocal of the
absolute temperature over the whole range of basicity is given in Fig. 5, which can
be described by the equation
60156
lnC P (T ) = − 21.296 r = 0.5513 (16)
T
Fig. 5 Variation of the 12

logarithm of phosphate y = 6.0156x - 21.296
capacity with the reciprocal R² = 0.3039
of the absolute temperature 11
ln CP
10
8
5.1 5.15 5.2 5.25 5.3 5.35
10000/T, K-1
The correlation coefficient of this equation indicates marginal linear correlation

between ln CP and the reciprocal of the absolute temperature.
According to Eq. 16, the phosphate capacity decreases with increasing tempera-
ture. This agrees with the findings of other investigators [4, 9–11].
Effect of Basicity and Temperature on Phosphate Capacity
Figure 6 shows the variation of ln CP with 1/T at constant values of basicity B =

(%CaO)
(%SiO2 )
, the straight lines are more or less parallel and have an average slope equal to
57886. The slope depends on temperature, whereas the intercept has different values
depending on the basicity, where A is the average slope and m represents the different
values of intercept at constant basicity.
A
ln CP = +m (17)
T
m(B) = −20.744 r = 0.6298 at B = 4.0924 (18)
m(B) = −20.645 r = 0.6234 at B = 5.5073 (19)
m(B) = −19.418 r = 0.6214 at B = 5.9873 (20)
m(B) = −20.099 r = 0.7057 at B = 6.7887 (21)
m(B) = −20.084 r = 0.9278 at B = 7.5252 (22)
The variation of intercept with B is given in Fig. (7) which satisfies the formula
m(B) = 0.2202B − 21.5151 r = 0.5416 (23)

(a) (b)
10.2 10.8
10 10.4
10
Ln CP
ln Cp
9.8
9.6
9.6 y = 5.8717x - 20.744 y = 5.8904x - 20.645
9.2
R² = 0.3966 R² = 0.3886
9.4 8.8
5.16 5.18 5.2 5.22 5.24 5.26 5.12 5.16 5.2 5.24 5.28 5.32
10000/T, K-1 10000/T, K-1
(c) (d)
10.8 10.8
10.4 10.4
Ln C P
10 Ln Cp 10
9.6 y = 5.6323x - 19.418 9.6 y = 5.7932x - 20.099

R² = 0.3861 R² = 0.498
9.2 9.2
5.12 5.16 5.2 5.24 5.28 5.32 5.12 5.16 5.2 5.24 5.28 5.32
10000/T, K -1 10000/T, K-1
(e)
10.4
10.2
Ln Cp
10
y = 5.7554x - 20.084
9.8 R² = 0.8609
9.6
5.16 5.2 5.24 5.28
10000/T, K-1
Fig. 6 Variation of the logarithm of phosphate capacity with the reciprocal of the absolute
temperature at the basicity B = (a) 4.0924, (b) 5.5075, (c) 5.9873, (d) 6.7887, (e) 7.5252
Fig. 7 Variation of the -19.2

intercept m, with the basicity
B -19.6 y = 0.2202x - 21.515
R² = 0.2933
-20
Intercept, m
-20.4
-20.8
-21.2
3 4 5 6 7 8
Basicity, B
Substituting the value of the average slope and the intercept from Eq. 23 in Eq. 17
gives:
57886
ln C P (B, T ) = + 0.2202 − 21.5151 (24)
T
Phosphorus Distribution Between Slag and Metal
The distribution ratio of phosphorus between slag and molten steel η P , can be defined
as:
(%P)
ηP = (25)
[%P]
From Eqs. 25 and 2 it follows

5/2
η P = C P f [P] a[O] (26)
In order to compare the calculated phosphorus distribution ratio at different basic-

ities and temperatures with the observed values, the above equations showing the
dependence of phosphate capacity on basicity and temperature are substituted in
Eq. 26.
Figure 8 shows the relationship between calculated and observed distribution
ratios. They can be described by the following equations:
η P (B, T ) = 0.9235η(obs) r = 0.7706 (27)

Calculated phosphorus distribution ratio ηP (cal)
140
120
100
80
y = 0.9235x
60 R² = 0.5939
40
20
0
0 50 100 150
Observed phosphorus distribution ratio ηP(Obs)
Fig. 8 Relationship between calculated and observed phosphorus distribution ratios between slag
and liquid steel in the ranges of temperature and basicity 1670 ≥ t ≥ 1610 and 7.6798 ≥ B ≥ 3.9253
Conclusions
The data were used to investigate the effects of temperature and slag composition on
the activity of total ferrous oxide in the slag as well as in the phosphate capacity, which
was utilized for the estimation of the slag metal distribution ratio of phosphorus. The
following conclusions can be made.
1. The activity coefficient of Fet O decreases with increasing basicity.
2. The activity coefficient of phosphorus in liquid steel is equal to 1.1195.
3. The activity coefficient of oxygen in the steel is equal to 0.8367.
4. The temperature effect on the phosphate capacity is large compared with the
small influence of basicity, the capacity decreases with increasing temperature
and increases slightly with increasing basicity.
5. The distribution ratio of phosphorus between slag and metal is investigated by
using the phosphate capacity. Calculated results correlate strongly with the actual
(%CaO)
data obtained from slag and metal analysis at basicity B = (%SiO 2)
.
6. The phosphate capacity and distribution ratio are mainly dependent on and
inversely proportional to the temperature and increases slightly with increasing
basicity.
Acknowledgements The authors acknowledge the support of Egyptian Iron and Steel Company for
the data of LD converters measurements and analysis. Thanks to the Tabbin Institute for metallurgical
Studies (TIMS).
References
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the residual manganese at the end of the blow during the process of top-blowing. M.Sc. thesis,
Tabbin institute for metallurgical studies
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1140
Solid-State Reduction Studies
for Recovery of Iron from Red Mud
Ender Keskinkilic, Saeid Pournaderi, Ahmet Geveci and Yavuz A. Topkaya
Abstract Red mud or bauxite residue can be regarded as a by-product of aluminum

extraction process since it contains a significant amount of iron and some valuable
elements. Therefore, the treatment of red mud has been a hot topic for some decades.
Last year, the authors started a laboratory-scale project dealing with stepwise recov-
ery of valuable elements from red mud of Seydisehir Aluminum Plant, Turkey. The
first step is related to the recovery of iron and pyrometallurgical methods (solid-state
reduction and smelting) are currently being performed. Nonferrous metals will then
be selectively leached in the second step. In TMS 2019, the authors outlined the
literature related to the smelting studies for iron recovery from bauxite residue. In
the extent of the present work, a literature review relevant to the solid-state reduction
studies for recovery of iron from red mud was presented.
Keywords Red mud · Pyrometallurgy · Solid-state reduction · Iron
Introduction
Red mud, or bauxite residue, is a waste material produced from the Bayer process
for alumina production. Treatment of wastes has become more important since a
couple of decades. Dozens of studies have been conducted for the treatment of red
mud, which contains significant amount of iron, titanium, aluminum, sodium, and
rare earth elements. Pyrometallurgical methods have been employed for the recovery
of iron and these kind of studies will most probably be more important in the future
when high-iron containing ores are depleted in the earth’s crust. Elements other than
E. Keskinkilic (B)
Department of Metallurgical and Materials Engineering, Atilim University, 06830 Ankara, Turkey
e-mail: ekeskinkilic@gmail.com
S. Pournaderi
Agri Ibrahim Cecen University, Ataturk Mah., 04500 Patnos, Agri, Turkey
A. Geveci · Y. A. Topkaya
Department of Metallurgical and Materials Engineering, Middle East Technical University, 06531
Ankara, Turkey
https://doi.org/10.1007/978-3-030-36540-0_45
512 E. Keskinkilic et al.
iron are recovered hydrometallurgically. There are many well-written reviews for
the treatment of bauxite residues and their different usage areas. China is one of the
major alumina producers. Therefore, treatment and utilization of red mud in China
were reviewed by Liu et al. [1]. Likewise, Samal et al. performed a similar review
for re-use options of bauxite residue in India [2]. Liu and Naidu reviewed the hidden
values in the red mud from recovery of metals point of view [3]. The readers can
consult more examples of such reviews [4–7].
Last year, the authors started a laboratory-scale project dealing with stepwise
recovery of valuable elements from red mud of Seydisehir Aluminum Plant, Turkey.
The first step is related to the recovery of iron and pyrometallurgical methods (solid-
state reduction and smelting) are currently being performed. Nonferrous metals will
then be selectively leached in the second step. In TMS 2019, the authors outlined
the literature related to the smelting studies for iron recovery from bauxite residue
[8]. In the extent of the present work, a literature review relevant to the solid-state
reduction studies for recovery of iron from red mud was presented.
Examples to Solid-State Reduction Studies for Recovery

of Iron
In this paper, examples to solid-state reduction were outlined. These can be

grouped mainly into four categories as carbothermic reduction, reduction roasting-
magnetic separation, gaseous reduction using H2 and/or CO, and microwave heating
applications.
1. Carbothermic Reduction
Actually, the phrase “carbothermic reduction,” in general, includes all of them indi-
cated above except for the gaseous reduction. However, in the extent of this work,
the term “carbothermic reduction” was used for the experimental studies, in which
a source of carbon was only blended with bauxite residue and subjected to the con-
ventional reduction like the dozens of the work related to carbothermic reduction of
various iron ores. Therefore, a more emphasis here was on the others, which can be
regarded as more recent variants of carbothermic reduction.
In solid-state carbothermic reduction studies, different kinds of carbon containing
reducing agents have been used. One of the most commonly used reducing agent is
coal. Qiu et al. investigated the effect of coal type on direct reduction behavior of
a red mud. The bauxite residue obtained from Guangxi Province (China) was used
in the experiments. The average chemical composition of the red mud was reported
as 54.60% Fe2 O3 , 15.08% Al2 O3 , 8.90% SiO2, and 1.85% Na2 O. Five types of
coal having different fixed carbon, volatile matter, ash, and reactivity were used as
reducing agents. Therefore, their reduction performances were compared. According
to the runs conducted at 1373 and 1423 K, the authors concluded that carbon with
theoretical amount and high reactivity should be introduced to the system and that
large ratio of Fc +V
A
m
and (Al(SiO 2 + TFe )
2 O3 + others)
should be satisfied, where Fc is the fixed carbon,
Solid-State Reduction Studies for Recovery of Iron from Red Mud 513
Vm is the volatile matter, A is the ash, and the second ratio is the ratio derived from
ash composition, all being the weight percentages. The authors underlined that the
ease of forming moderate porosity in coal + red mud agglomerates was of upmost
importance [9].
2. Reduction Roasting-Magnetic Separation
Liu et al. studied recovery of iron from bauxite residue by reduction roasting-
magnetic separation (RRMS). The red mud supplied from an alumina plant in
Chiping of Shandong Province (China) was used in the experiments. The chem-
ical composition of the bauxite residue was reported as 27.93% Fe2 O3 , 22.00%
Al2 O3 , 6.23% CaO, 20.98% SiO2 , 2.30% TiO2 , 1.32% MgO. and 10.50% Na2 O.
Commercial grade activated carbon powder was used as a reducing agent. CaCO3
and MgCO3 were used as additives for reduction roasting experiments. Magnetic
separation was performed under a working electrical current of 1 A. The effect of
temperature, time, carbon/red mud ratio and additive amount were determined as the
experimental variables. According to the experiments performed in the temperature
range of 1150–1300 °C, roasting at 1300 °C for 110 was found to yield the optimum
iron grade, metallization and recovery. The optimum conditions related to the reduc-
tant and additives were reported as carbon/red mud ratio of 0.18 and additives/red
mud ratio of 0.06. The authors outlined that the optimum conditions yielded iron
grade of 88.77% with a corresponding metallization and recovery values of 97.69%
and 81.40%, respectively. The residue obtained after magnetic separation was used
for building material production but the details of the work were not included here
in the scope of the present manuscript [10].
Zhu et al. investigated recovery of iron from red mud using RRMS. The red mud
obtained from Shandong Aluminum Corporation was a kind of high iron red mud.
The major components of the bauxite residue were reported as 50.60% TFe, 8.36%
Al2 O3 , 4.63% SiO2, and 1.32% Na2 O, while the others were less than 1%. Coal was
used as a reductant. Reduction roasting was conducted with the addition of Na2 CO3 .
The authors indicated that sodium sulfate would also be used as an additive but high
sulfur content in the final product was the problem when it was used. The amount
of additive, reduction roasting temperature and its period were determined as the
variables. According to the experiments performed between 900 and 1100 °C, the
optimum iron grade and recovery were reported at 1050 °C. It was reported further
that 80 min was sufficient for reduction. Beyond 1050 °C, iron grade and recovery
were found to decrease. This decrease was attributed to the formation of difficult
to reduce compounds such as fayalite (2FeO.SiO2 ) and hercynite (FeO.Al2 O3 ). For
the optimum iron grade and recovery, 8% Na2 CO3 addition was suggested. Roasted
pellets were then subjected to magnetic separation under the magnetic field intensity
of 0.08 T. The final concentrate was reported to contain 90.87% Fe and overall iron
recovery was found as 95.76% [11].
Rao et al. studied iron recovery from bauxite residue by RRMS. The red mud
supplied from Shandong Aluminum Corporation was reported to contain 48.23%
TFe, 7.31% Al2 O3 , 7.96% SiO2 , 1.42% TiO2, and 1.35% Na2 O, as the major com-
ponents. Lignite containing 52.63% fixed carbon was used as reducing agent. The
authors used both Na2 SO4 and Na2 CO3 as additives. The amount of additive, tem-
perature, and time of roasting were the experimental variables. RRMS of red mud
was investigated both in the absence and in the presence of additive(s). Reduction
roasting experiments were conducted in the temperature range from 750 to 1050 °C.
It was concluded that 1050 °C and 60 min were the optimum temperature and time,
respectively. In the absence of additive, metallization of iron was found to be less
than 80%. Iron metallization was reported to increase from 78.20% to 87.60% with
the addition of 10% Na2 CO3 . Iron metallization was found to rise from the same
initial value to 88.10%, when 10% Na2 SO4 was used. The authors underlined that
better results were obtained when both additives were used together. In the absence
of additive, iron particles were finely distributed in the matrix having 1–5 µm aver-
age size. With the use of additive(s), average iron particle size was reported to be
around 100 µm. Therefore, additives were found to be beneficial for aggregation of
metallic iron particles. Considering the high S content problem in the final concen-
trate when sodium sulfate was used, the authors suggested the use of a mixture of
additives as 6% Na2 CO3 and 6% Na2 SO4 . After magnetic separation under magnetic
field intensity of 0.1 T, the optimum conditions resulted in iron grade and recovery
values as 90.12% and 94.95%, respectively [12]. In the further study conducted by
Li et al. dealing with stepwise recovery of valuable elements from red mud [13], the
following reduction roasting reaction was proposed for conversion of hercynite and
quartz into sodium aluminosilicate when sodium salts were used as additive(s):
FeO · Al2 O3 + Na2 O + SiO2 + CO → Fe + NaAlSiO4 + CO2 (1)
Chun et al. performed an experimental study to obtain metallic iron powder from
red mud using RRMS. The red mud obtained from Shandong Aluminum Corpo-
ration had the following main components with their weight percentages: 36.61%
TFe, 16.97% Al2 O3 , 16.23% CaO, 8.74% SiO2 , 2.84% Na2 O. Bituminous coal hav-
ing 52.12% fixed carbon was used as a reductant. Na2 SO4 and CaO were used as
additives. Authors indicated that CaO was added to obtain calcium aluminate during
reduction roasting. Amount of additions, amount of reductant, roasting tempera-
ture, and time were determined as the experimental variables. According to the runs
performed between 1050 and 1250 °C, the optimum temperature and time were
determined as 1150 °C and 80 min, respectively. 9% Na2 SO4 , 9.46% CaO, and 16%
coal additions were reported to yield the optimum results. Magnetic separation was
conducted with a magnetic field intensity value of 0.08 T. Under these conditions,
the concentrate’s iron grade was found to be 90.28% with a metallization degree
of 94.87% and a recovery of 92.14%. The authors concluded that Na2 SO4 addition
both enhanced the growth of iron particles and increased the iron grade and the
corresponding recovery [14].
Chun et al. investigated iron recovery from red mud using RRMS. The baux-
ite residue supplied from Shandong Aluminum Corporation was reported to con-
tain 42.45% TFe, 10.34% Al2 O3 , 6.89% SiO2, and 1.36% Na2 O. Coal fines having
78.99% fixed carbon were used as the reductant. Analytical grade sodium borate
was added as a flux in reduction roasting experiments. The runs were performed
both in the absence and presence of sodium borate and the results were compared.
Temperature, time, coal amount, and sodium borate quantity were determined as
experimental variables. Magnetic separation was performed under a magnetic field
intensity of 0.08 T. According to the runs conducted between 1200 and 1350 °C,
reduction roasting at 1300 °C for 30 min was found as optimum temperature and
period, respectively. Under these conditions, 12% coal and 4% sodium borate addi-
tions yielded the optimum results, which were reported as iron grade of 90.78% with a
metallization degree of 91.26% and a recovery of 88.20%. Around 10% increase was
noted in the grade of iron with the presence of sodium borate. It was also shown that
the growth of iron grains was enhanced with the addition of sodium borate, enabling
better magnetic separation performance. Based on a previous work which could not
be reached, the authors outlined the requirements for a material to be charged to an
electric arc furnace as iron grade > 88%, metallization degree > 90%, S < 0.06%,
and P < 0.06%. Therefore, they concluded that the concentrate obtained from RRMS
experiments could be used as a feed in an electric arc furnace to replace scrap [15].
Grudinskii et al. investigated the effects of alkali metal salts on the solid-state
carbothermic reduction of red mud and especially iron grain growth. The bauxite
residue supplied from Ural Aluminum Plant (Russia) was used in the experiments.
The dealkalized red mud was reported to contain 36.90% Fe2 O3 , 11.80% Al2 O3 ,
23.80% CaO, 8.71% SiO2 , 3.54% TiO2 , 1.01% MgO, and 0.27% Na2 O. Graphite
powder was used as a reducing agent. The authors used alkali sulfates and alkali car-
bonates as Na2 SO4 , Na2 CO3 , K2 SO4, and K2 CO3 . Among the experiments conducted
in the temperature range of 1000–1200 °C, the run performed at 1100 °C and with
the addition of 10% Na2 SO4 was reported to give the optimum results. Under these
conditions, more than 62% of iron particles were found to be larger than 0.04 mm.
Sodium and potassium sulfate additions were reported to yield a significant increase
in iron particle size compared to the ones observed in the experiments without these
additions. The authors emphasized that alkali metal carbonates were also beneficial
to enlarge the iron particle size but their extent were not as high as the ones obtained
with sulfate additions. The authors also compared the potassium sulfate and sodium
sulfate in that potassium sulfate necessitated higher temperatures than sodium sulfate
to begin to increase the iron particle size [16].
3. Gaseous Reduction with H 2 and/or CO
Samouhos et al. proposed a method involving hydrogen reduction of red mud fol-
lowed by magnetic separation. The authors indicated that hydrogen could be used for
controlled reduction of iron oxides present in red mud. They argued that expensive
nature of the hydrogen gas might be counterbalanced by operating at sufficiently
lower temperature than the ones needed for carbothermic reduction, by eliminating
agglomeration step necessitated for solid-state reduction and by eliminating car-
bon contamination in the reduced concentrate. Therefore, the authors performed
laboratory-scale experiments for hydrogen reduction of red mud. The bauxite residue
obtained from Aluminum of Greece S. A. was reported to contain the following major
components with their relative amounts: 43.59% Fe2 O3 , 18.45% Al2 O3 , 11.38%
CaO, 6.00% SiO2 , 5.54% TiO2, and 1.82% Na2 O. Time, temperature, and H2 supply
were determined as the experimental variables. The experiments conducted in the

extent of this work actually aimed to convert hematite present in the red mud into
magnetite, which could then be recovered in subsequent magnetic separation. A hor-
izontal tube furnace was used for hydrogen reduction experiments. The runs were
performed in the temperature range from 300 to 480 °C. The term stoichiometric
hydrogen was defined as the H2 quantity required for 100% conversion of hematite
to magnetite. According to experiments conducted, the maximum conversion was
achieved when 2.5 × stoichiometric H2 was supplied to the system. The maximum
conversion degree was reported to be higher than 87% at 480 °C. Transmission elec-
tron microscopy studies showed that unreduced sub-micron hematite particles were
surrounded by Al–Ca containing powder, which might result in ineffective hydro-
gen diffusion. The authors concluded that the magnetite concentrate obtained from
hydrogen reduction-magnetic separation could be used as a raw material in the pig
iron industry. The authors suggested that the extent of hydrogen diffusion might be
enhanced with the use of a fluidized bed [17].
Man and Feng performed a kinetic study involving the use of H2 and CO for
the reduction of hematite in red mud. The bauxite residue supplied from Shandong
Aluminum Corporation was used in the gaseous reduction experiments. The major
components of the red mud were reported as 47.60% TFe, 8.42% Al2 O3 , 10.40%
SiO2 , 1.71% TiO2, and 1.73% Na2 O. The experiments were performed in the tem-
perature range from 700 to 1100 °C in H2 and CO atmospheres. The outcomes of
different atmospheres were compared. The authors indicated that the rate of reduction
under H2 atmosphere was significantly higher than the one under CO atmosphere
above 900 °C although they showed similar behavior below 800 °C. The authors con-
cluded that 1100 °C and H2 atmosphere were determined as the optimum conditions
yielding higher metallic iron quantity than the one obtained from CO atmosphere
[18].
Gostu et al. studied low temperature reduction of red mud under CO/CO2 /N2 atmo-
sphere. ~60% hematite containing bauxite residue obtained from Jamaica (chemical
composition was not provided) was used in the experiments. Gaseous reduction was
conducted in the temperature range of 475–600 °C for 10, 20, and 30 min using a
horizontal tube furnace. The gas mixture was adjusted in such a way that CO/CO2
ratios of 1:1, 1:1.5, and 1.5:1 were utilized in the runs. According to the results
of the experiments, the optimum conditions for the reduction were reported as 540
°C ± 10 °C, 30 min and CO/CO2 ratio of 1:1 (each of 0.070 atm ± 0.001 atm).
The authors also included a mathematical model for reduction of hematite to mag-
netite. The authors outlined the compositions of the products obtained as ranges:
56.40–80.50% Fe3 O4 , 0–20% Fe2 O3 , 4.80–6.80% Fe3 C and the remaining being
paramagnetic phases. The authors indicated that large batches of magnetite could be
obtained with these conditions [19].
4. Microwave Heating Applications
In the recent years, applications of microwave heating have come into picture in
extractive metallurgy. Major advantages of microwave heating can be listed as its
ability to heat inside of the furnace instantaneously and its clean and easily managed
nature. In literature, certain examples to microwave reduction of red mud can be

found. Samouhos et al. investigated microwave reductive roasting of Greek red mud
followed by magnetic separation. The bauxite residue obtained from Aluminum
of Greece S.A. was reported to contain 43.19% Fe2 O3 , 14.63% Al2 O3 , 12.03%
CaO, 7.37% SiO2 , 6.05% TiO2, and 2.14% Na2 O. Lignite having 30.15% fixed
carbon was used as a reducing agent. Effects of time, carbon/red mud wt. ratio, and
microwave power supply were studied. After magnetic separation under intensity
of 0.3 A, the optimum conditions (12 min, 2.5 × stoichiometric carbon, 1000 W)
yielded a concentrate with 35.10% TFe and 69.30% metallization degree. The authors
concluded that the microwave reduction roasting went to completion in a time 40%
shorter than the conventional reduction roasting period and that microwave process
gave higher metallization degree. After examination of levels of Na, S, C as well as
radioactive elements, the authors underlined that the concentrate could be used as a
raw material in the iron industry [20].
Agrawal et al. studied microwave reduction of red mud obtained from India. The
bauxite residue supplied from Hindustan Aluminum Corporation Ltd. (HINDALCO)
was reported to contain 36.80% Fe2 O3 , 22.07% Al2 O3 , 1.89% CaO, 11.81% SiO2 ,
15.60% TiO2, and 10.21% Na2 O. Charcoal was used as a reductant (Carbon con-
tent was not provided). Temperature, time, and reductant dosage were determined as
experimental variables. Other than iron reduction, the behavior of other elements as
aluminum, silicon, sodium. and titanium were also investigated. Microwave reduc-
tion experiments were performed in the temperature range of 700–1000 °C for 10-
50 min with a reducing agent dosage in the range of 8–12%. Red mud subjected
to carbonation pretreatment for pH reduction was then mixed with charcoal and
microwave heated (800 W, 2.45 GHz). Reduced samples were water quenched and
subjected to low intensity magnetic separation under 0.3 kA/m. Magnetite and fer-
rite were reported to be present as ferromagnetic phases whereas ilmenite, pseu-
dobrookite, wustite, and hercynite were found as paramagnetic ones. The authors
outlined the optimum conditions for two cases: 1. Microwave reduction at 1000 °C
for 50 min at 10% charcoal yielded a concentrate having iron grade of 48.50% with
a corresponding recovery of 95%, which could be regarded as a raw material for
titanium production. 2. Microwave reduction at 850 °C for 30 min at 10% charcoal
produced a concentrate which had an iron grade of 46.50% with an iron recovery of
94.30% (magnetite as the major constituent), which could be processed in alternative
iron-making technologies. The authors finally concluded that microwave reduction
provides a significant increase in the grade and recovery of the iron concentrate with
a much lower energy supply compared to the one in conventional reduction [21].
The same research team conducted a more detailed study involving the compari-
son of microwave and conventional carbothermic reduction using a bauxite residue
obtained from an Indian aluminum company. The major components of the red mud
were reported with their percentages as 47.85% Fe2 O3 , 22.64% Al2 O3 , 1.86% CaO,
12.51% SiO2 , 3.58% TiO2, and 10.25% Na2 O. A similar experimental procedure was
performed as the one explained above. One of the most important findings of this
work was related to the comparison of performances of the aforementioned methods.
The authors concluded that the microwave carbothermic reduction was much faster
and cleaner technology and that formation of ferrite balls was more pronounced in
microwave route (~8–10% of the iron content of the concentrate) with a larger size
as 1 ± 0.5 mm and higher iron content and purity as ~92% and 94%, respectively
[22]. Apart from these advantages, the high equipment cost due to the factors includ-
ing short life of microwave source and its limited ability to supply the maximum
power was noted as a disadvantage of microwave reduction [20]. Actually, efforts
have been made to scale up the process. As an example to this, the work conducted
by Hara et al. related to continuous pig iron making could be given. Microwave
heating with 12.5 kW at 2.45 GHz. was applied. According to the data of eight
experiments, average load to the microwave furnace was 1,725 g with a maximum
value of 4,800 g. Average weight of pig iron was reported as ~500 g with a maximum
weight of 922 g. Average total time was measured as ~200 min with a maximum
period of 258 min [23]. These data are important to imagine the size and duration
of an enlarged microwave reduction system and to compare it with the commercial
pyrometallurgical operations.
Conclusions
Since the end of sixties, smelting of red mud has been deeply investigated for recovery
of iron and/or enhancement of subsequent leaching recoveries of aluminum and other
elements including the rare earths. In relation to solid-state reduction studies, the
following main conclusions can be drawn:
• In carbothermic reduction, the properties of carbon source were important. Other
than high reactivity, large ratio of Fc +V
A
m
and (Al(SiO 2 + TFe )
2 O3 + others)
should be satisfied,
where Fc is the fixed carbon, Vm is the volatile matter, A is the ash, and the second
ratio is the ratio derived from ash composition, all being the weight percentages.
• Use of oxides and carbonates of some IA and IIA group elements as additives
in reduction roasting were found to be beneficial to increase the iron grade and
corresponding recovery as well as the metal particle size in the reduced concentrate.
• With the use of gaseous reduction with H2 and/or CO, hematite could be con-
verted primarily to magnetite, which can be used as a raw material in iron making.
Reduction performance of H2 was reported to be better than CO above 900 °C.
• Like many areas in extractive metallurgy, microwave heating was applied for reduc-
tion of bauxite residue. The authors concluded that microwave reduction yielded
higher iron grade and recoveries with a much lower energy supply compared to
the conventional route.
Acknowledgements The authors would like to thank The Scientific and Technological Research
Council of Turkey (TUBITAK) for the financial support given under the Project No: 117M185.
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Precipitation Behavior of B2 O3 Addition
on CaO–Al2 O3 –Sc2 O3 Slag System
Through in Situ Observation
Fei Wang, Wenke Zhi, Ling Zhang, Zhuangzhuang Liu, Yongnian Dai,
Bin Yang and Muxing Guo
Abstract This study focuses on the recycling of scandium from high-temperature

processing metallurgical slags through pyrometallurgical routes. For the optimization
of the rare earth (scandium) recycling route, the distribution of scandium in CaO–
Al2 O3 –Sc2 O3 slag system is worth investigation, and the precipitation behavior of
scandium in CaO–Al2 O3 –Sc2 O3 slag system during slag cooling progress is of sig-
nificance. In this work, the precipitation and solidification behaviors were recorded
by a confocal scanning laser microscope (CSLM) combined with an infrared imag-
ing furnace heating (IIF). The compositions and microstructures of the equilibrated
phases of these systems were determined by an electron probe microanalyzer with
standardized wavelength dispersive spectroscopy (EPMA/WDS). It is observed that
there is a remarkable influence of B2 O3 addition on the precipitation and solidifica-
tion behaviors in the CaO–Al2 O3 –Sc2 O3 system. By choosing different cooling rates
(20, 50, and 100 K/min) the CCT diagram was constructed, which can be employed
to guide the rare earth recovery in industrial practice.
Keywords In situ observation · Precipitation · Solidification · CaO–Al2 O3 –Sc2 O3
F. Wang · W. Zhi · Y. Dai · B. Yang

State Key Laboratory of Complex Nonferrous Metal Resources Clear Utilization, National
Engineering Laboratory for Vacuum Metallurgy, Key Laboratory for Nonferrous Vacuum
Metallurgy of Yunnan Province, Kunming University of Science and Technology, Kunming
650093, Yunnan, People’s Republic of China
L. Zhang · Z. Liu · M. Guo
Department of Materials Engineering, KU Leuven, Kasteelpark Arenberg 44 Bus 2450, 3001
Leuven, Belgium
e-mail: muxing.guo@kuleuven.be
B. Yang (B)
National Engineering Laboratory for Vacuum Metallurgy, Kunming University of Science and
Technology, Kunming 650093, Yunnan, People’s Republic of China
e-mail: kgyb2005@126.com

https://doi.org/10.1007/978-3-030-36540-0_46
522 F. Wang et al.
Introduction
Rare earth sesquioxides (RE2 O3 , RE = rare earth) are important compounds in

various applications, such as microelectronic, optoelectronic, and optical devices [1–
8]. Rare earths are recognized as critical raw materials due to their increasing demands
and supply shortages, and the recycling of rare earth elements from end-of-life REEs-
containing products are put forward [9, 10]. At present, there are two main methods
for recovering rare earth, which are pyrometallurgical and hydrometallurgical [11].
As a traditional method, hydrometallurgy will use a large amount of acid which will
produce a large amount of waste acid, wastewater that are serious pollution to the
environment. Morais et al. [12] studied the recovery of europium and yttrium from
colour TV screens using sulphuric acid as the leaching agent. In this study, the Eu
and Y solubilisation was 90 and 95 wt%, respectively, when conducted at 363 K,
2 h of leaching, acid/sample ratio of 1000 kg/t and 40% solids. At 343 K, 1500 kg/t
acid/sample ratio, 2 h of leaching, and 40% solids, the solubilisation of both metals
was 80%. On the contrary, the combination with pyrometallurgy is considered to
be an alternative route; it has a potentially lower impact on the environment and
economy [11]. It has the following advantages: short time, less water consumption,
high capacity and no restrictions on the recovered rare earth. Muller and Friedrich
[13] used CaO–SiO2 –CaF2 slag system to absorb nearly 100 pct of the REs, resulting
in 50 to 60 pct RE-containing slag.
B2 O3 ,which is commonly used as fluxing agent in metallurgy [14] has remarkable
influence on the melting and precipitation behavior in high-processing metallurgical
slag. The present research focuses on the recycling of rare earths through pyrometal-
lurgical routes. In order to optimize the recycling route, the distribution of rare earth
elements in slag and the precipitation behavior of rare earth elements during slag
solidification are important.
From previous studies [15], we know that the phase relations of the CaO–Al2 O3 –
Sc2 O3 system and two possible REE recycling schemes. In this paper, it aims to inves-
tigate precipitation and solidification behavior of the CaO–Al2 O3 –Sc2 O3 ternary sys-
tem through in situ CSLM observation. In addition, the CSLM experiment was also
carried out on the ternary system with an addition of B2 O3 , so that it optimizes the
cooling process for high-REEs recovery. Study of the precipitation behavior of the
slag can help in understanding the enrichment and precipitation of rare earth in the
slag.
Experimental
Sc2 O3 (99.999 wt%), CaO (99.9 wt%), Al2 O3 (99.9 wt%), and B2 O3 (99.9 wt%)
are used as the raw materials, as shown in Table 1. For the quaternary CaO–Al2 O3 –
Sc2 O3 -B2 O3 system, 20 wt% B2 O3 and 30 wt% B2 O3 were added to the ternary
Precipitation Behavior of B2 O3 Addition on CaO–Al2 O3 –Sc2 O3 … 523
Table 1 Initial component partition ratio of samples

Sample CaO (wt%) Al2 O3 (wt%) Sc2 O3 (wt%) B2 O3 (wt%)
1 20 30 50 20
2 20 30 50 30
sample, respectively. The selected slags were prepared according to the isothermal-
quenching procedure at 1773 K. The slag samples were placed in the platinum (Pt)-
20% rhodium (Rh) crucible on the sample holder inside the confocal scanning laser
microscope (CSLM) heating chamber. The temperature calibration was performed
using pure copper, nickel and palladium, separately, as references and the sample’s
temperature was observed to be 358 ± 5 K lower than the measured temperature using
the thermocouple. Before the experiment began, CSLM chamber was evacuated and
flushed with argon three times. During the experiment, a constant rate of argon
(AR) was continuously injected into the gas. The two slag samples have four CSLM
experiments of heating and cooling, and their heating and cooling rates are increased
from 20, 50, and 100 K/min, respectively. The laser-scanned images of this heating
and cooling process were captured and used for further investigation.
For microstructure and phase composition analysis, the samples after the CSLM
experiments were embedded in epoxy resin and polished. In order to analyze the
microstructure and phase composition better, these samples were coated with either
a gold or graphite thin layer to obtain a good surface conductivity. The samples
were then analyzed by an electron probe microanalyzer (EPMA, JEOL JXA-8530F)
equipped with standardized wavelength dispersive spectroscopy (WDS) and operated
at 15 kV and a probe current of 10 nA was performed. The standard samples are
CaO, Al2 O3 , Sc2 O3, and B2 O3 . The average accuracy of EPMA measurements on
the main elements is ± 1 wt%.
According to the previous studies [15], there are two possible schemes to recover
REEs: precipitation of high REEs solid phase in Ca2 Sc6 Al6 O20 –L region and con-
centrating of REEs in CaO·Sc2 O3 –L region, respectively. By collecting any of these
precipitates from the slag, a REE-rich product can be obtained, which can be used
as a rich REE input stream for the next step in the REE recovery process. In order
to further prove its feasibility and to study the effect of B2 O3 on the slag sample, 20
wt% B2 O3 and 30 wt% B2 O3 were selected to be added to the sample. The CSLM
experiments were carried out on these slag samples. There are lower rare earth ele-
ments in metallurgical slags, which can be enriched by changing different cooling
trajectory. Therefore, the slag samples quenched at 1773 K were selected for CSLM
experiment. At 1773 K, the sample was remelted in the heating chamber, and then
cooled at different cooling rates of 20, 50, and 100 K/min, respectively. The slag was
524 F. Wang et al.
transparent before the first phase precipitates, the collection of the precipitates was
detected by holding the focus of the microscope at the bottom of the crucible, by the
appearance and the new structure in the liquid.
Through CSLM experiment, the change of cooling process during the experi-
ments was obtained, as shown in the Figs. 1, 2, 3, 4, 5, and 6, respectively. Only
the main images of this process were given (some representative images were
selected),the composition and microstructure of the precipitates are further confirmed
by EPMA/WDS with the back scattering electron (BSE) images of the equilibrated
samples, as shown in Fig. 7a. The presence of Ca2 Sc6 Al6 O20 and Sc2 O3 were deter-
mined at 1773 K by quantification analysis through EPMA/WDS. In Figs. 1, 3, and 5,
with the increase of cooling rate, the slag samples can be completely precipitated in a
very short time. It can be explained that under certain conditions of B2 O3 , increasing
cooling rate can reduce the time and temperature of complete precipitation. In Figs. 2,
4, and 6, with the increase of cooling rate, the time of complete precipitation of slag
samples is shorter than that of Figs. 1, 3, and 5. It can be explained that the cooling
rate and the addition of B2 O3 have a great influence on the complete precipitation of
the slag samples. The new precipitate samples prefer to form at the grain boundaries
of the crucible. The BSE image of the samples indicates that the precipitate has a
Fig. 1 Slag system samples of 30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-20 wt% B2 O3 , cooling
rate at 20 K/min: a first precipitates appearing; b second type of precipitate appearing; c complete
solidification
solidification
solidification
solidification
solidification
uniform phenomenon (Fig. 7b). In particular, in Figs. 2, 4, and 6a, b, the new precip-
itate samples prefer to form at the grain boundaries of the crucible. The BSE image
of the samples indicates that the precipitate has a uniform phenomenon (Fig. 7c). In
addition, no other type of precipitate was further formed during the cooling of the
slag, which is in good agreement with the compositional analysis (Fig. 7).
Comparisons between Figs. 1 and 2, when the cooling rate is 20 K/min, the slag
sample (30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-30 wt% B2 O3 ) has a shorter
526 F. Wang et al.
solidification
Fig. 7 BSE images of the quenched slag samples from equilibrium at 1773 K. a Slag system
samples of 30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO; b Slag system samples of 30 wt% Al2 O3 -
50 wt% Sc2 O3 -20 wt% CaO-20 wt% B2 O3 ; c Slag system samples of 30 wt% Al2 O3 -50 wt%
Sc2 O3 -20 wt% CaO-30 wt% B2 O3
precipitation time and a lower temperature, which indicates that B2 O3 plays a good
role as flux. Comparisons between Figs. 3 and 4, when the cooling rate is 50 K/min,
the slag sample (30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-30 wt% B2 O3 ) has a
shorter precipitation time and a lower temperature than the slag sample (30 wt%
Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-20 wt% B2 O3 ), which indicates that B2 O3 pro-
motes sample precipitation and temperature reduction. Comparisons between Figs. 5
and 6, when the cooling rate is 100 K/min, the slag sample (30 wt% Al2 O3 -50 wt%
Sc2 O3 -20 wt% CaO-30 wt% B2 O3 ) has a shorter precipitation time and a lower tem-
perature than the slag sample (30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-20 wt%
B2 O3 ), which indicates that B2 O3 plays a good role as flux. In addition, in Figs. 1, 2,
3, 4, 5, and 6a, the first image represents the sample in a first precipitates appearing
at the indicated temperature, square frames were used to mark visible precipitates,
which appear as a brighter or darker color, depending on their positions. In Figs. 1, 2,
3, 4, 5, and 6b, the image shows a second type of precipitate appearing in the ternary
slag. As the temperature decreased, this image represents a complete precipitation
of the sample, as shown in Figs. 1, 2, 3, 4, 5, and 6c.
With the increase of cooling rate, the slag samples reach complete precipitation at a
certain time. Suitable slag composition, cooling rate, and process optimization can be
selected for rare earth recovery companies. CSLM experiments and EPMA analysis
Fig. 8 a Precipitation and complete solidification temperatures of 30 wt% Al2 O3 -50 wt% Sc2 O3 -
20 wt% CaO-20 wt% B2 O3 slags and b 30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-30 wt% B2 O3
slags with cooling rate at a: a: 20 K/min b: 50 K/min c: 100 K/min
will be done at different cooling rates and different compositions. In Figs. 1, 2, 3, 4, 5,

and 6, first precipitates appearing, second type of precipitate appearing and complete
precipitation are seen, which provides a potential reference for the construction of
continuous cooling transition (CCT) diagram, as shown in Fig. 8a, b, the results show
that the addition of B2 O3 has a significant effect on the precipitation behavior of slag
composition, and also reduces the liquidus and solid-phase temperature of slag; it
was a practical tool for the REE recyclers to select appropriate slag compositions
and cooling rates and to optimize the process.
Conclusion
Under the conditions of 30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-20 wt% B2 O3
and 30 wt% Al2 O3 -50 wt% Sc2 O3 -20 wt% CaO-30 wt% B2 O3 with cooling rates of
20, 50, and 100 K/min, respectively, the precipitation of rare earth-rich compounds
was observed in situ. When B2 O3 is a certain amount, increasing the cooling rate
can promote the precipitation and temperature reduction of the slag samples. When
the cooling rate is constant, increasing the amount of B2 O3 can promote the pre-
cipitation and temperature reduction of slag samples. It can be seen from this that
the process of recovering rare earth from waste containing rare earth can be found
by choosing appropriate additives. In addition, the solidification and precipitation
behavior resulting from the change of cooling path shows that the efficiency of rare
earth recovery and slag recycling can be improved by the reasonable design of slag
treatment process.
Acknowledgements Academician Free Exploration Fund of Yunnan Province, China

(No.2019HA006) and NSFC-FWO exchange project (Grant No. 5171101430).
528 F. Wang et al.
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Sc2 O3 ternary system. J Am Ceram Soc 102:2863–2870
Part VII
Preparation of Alloys and Materials
Effect of Intercritical Heat Treatment
on Microstructure and Mechanical
Properties of Sn Bearing 33MnCrB5
Steel
Lijuan Sun, Fuming Wang, Zhanbing Yang, Changrong Li, Wei Shen,
Shuai Liu and Liang Tan
Abstract With the recycling of scrap steel, the accumulation of Sn deteriorates

the properties of high-strength low-alloy structural steel. The effect of intercritical
heat treatment (IHT) on microstructure and the mechanical properties of Sn bearing
33MnCrB5 steel has been studied. Results indicated that a composite microstructure
of ferrite and martensite was obtained by adding the intercritical quenching to the
conventional quenching and tempering. Compared with the conventional heat-treated
samples, the impact energy increased evidently from 30 J to 77 J and the strength
decreased slightly. The loss of strength resulting from the IHT is reduced by the mod-
ification of tempering conditions. Furthermore, AES showed that the grain boundary
segregation of Sn can be alleviated via the IHT. Based on different heat treatment
results, the optimum heat treatment technology, that is, 910 °C normalizing, 860 °C
pre-quenching, 770 °C intercritical quenching, 450 °C tempering, was obtained to
balance the strength and toughness.
L. Sun · F. Wang · Z. Yang (B) · W. Shen · S. Liu

Beijing, 100083 Beijing, China
L. Sun
e-mail: sunlijuan0102ustb@163.com
F. Wang
W. Shen
e-mail: shenweiustb@163.com
S. Liu
e-mail: liushuai_ustb@sina.com
C. Li
School of Materials Science and Engineering, University of Science and Technology Beijing,
100083 Beijing, People’s Republic of China
e-mail: crli@mater.ustb.edu.cn
L. Tan
Jiangyin Xingcheng Special Steel Works Company Ltd, 214400 Jiangyin, China
e-mail: tanliang@citicsteel.com
https://doi.org/10.1007/978-3-030-36540-0_47
532 L. Sun et al.
Keywords Intercritical heat treatment · Sn · Microstructure · Mechanical

properties · Grain boundary segregation
Introduction
Tramp elements are those elements that are present in steel but usually not inten-
tionally added and are difficult to refine from the steel, and therefore will be kept
in the steel cycle once entered, coming back over and over again when the steel is
recycled. Some of these have detrimental effects on the steel properties, such as Sn,
Sb, and As. In particular, Sn segregate at grain boundaries, thus deteriorating the hot
ductility and mechanical properties apparently.
It is reported that intercritical heat treatment (IHT) can be used to reduce the
harmfulness of Sn on steel properties [1]. The IHT is performed by quenching from
a suitable temperature in the intercritical range between the lower transformation
temperature (Ac1 ) and the upper transformation temperature (Ac3 ) and holding some
time, followed by subsequent cooling. In this intercritical quenching the austenite
transforms to martensite, and finally a ferrite–martensite structure can be obtained
[2–5]. Dual-phase microstructure produced by intercritical heat treatment makes
low- alloy steels have superior strength–ductility combination. The ferrite provides
the ductility while the martensite provides the strength [6].
Kang et al. [7] found that, by adding intercritical heat treatment between conven-
tional quenching and tempering, the impact toughness of HSLA steel improved the
interlocking arrangement of banded ferrite and the ferrite–martensite interfaces with
high-angle misorientations, which exhibited effective resistance to the crack propa-
gation. Previous researchers [8–11] investigated the effect of additional quenching
from the intercritical range on the microstructure and the mechanical properties of
steels. Intercritical quenching with tempering leads to a significant increase in the
impact energy as compared to that produced by the conventional quenching from the
Ac3 temperature. After intercritical heat treatment, the steels have outstanding per-
formance. So it can be a new attempt to reduce the harmfulness of residual elements
on the impact energy of steel, and to obtain the required mechanical properties.
This work aims at improving Charpy impact energy of Sn bearing 33MnCrB5
steel through adding intercritical quenching to the conventional quenching and tem-
pering treatment. The effect of the IHT on microstructure and mechanical properties
will be studied. Moreover, the mechanism how intercritical heat treatment improves
toughness will be elucidated.
The steel used was a type of 33MnCrB5 alloy steel in the form of bar. Table 1
shows the chemical compositions of the investigated steel. For this study, the AC1
and AC3 were calculated by Thermo-Calc to be 710 and 781 °C, respectively. The
Table 1 Chemical composition of investigated steel (wt%)
Element C Si Mn P S Cr Ni V Mo Ti B Sn
Composition 0.33 0.25 1.25 0.018 0.002 0.52 0.04 0.005 0.01 0.032 0.0022 0.021
Effect of Intercritical Heat Treatment on Microstructure …
533
534 L. Sun et al.
Fig. 1 Schematic illustration of different heat treatments: (a) conventional heat treatment and
(b) intercritical heat treatment (IHT)
key modification to the conventional heat treatment is the introduction of intercritical

quenching between the conventional quenching and tempering, as shown in Fig. 1. In
the present work, in order to clarify the effect of intercritical heat treatment, different
heat treatment procedures were designed to find out an optimum IHT condition and
to balance the strength and toughness.
The specimens for microstructural characterization were polished and etched with
a 4% nital solution, and were analyzed by optical microscopy (OM, MX6R) and
field emission scanning electron microscopy (FE-SEM, JSM-6701F). Ferrite volume
fraction of the sample was determined by ImageJ software on the SEM micrographs.
In order to investigate the influence of intercritical heat treatment on the impact
toughness and strength of the steel, a series of Charpy impact tests and tensile tests
were carried out at ambient temperature. For Charpy impact tests, full-size standard
Charpy V-notch specimens with a 10 mm × 10 mm × 55 mm size were machined
according to GB/T 229-2007. Tensile tests were carried out on round specimens
with a diameter of 5 mm and a gage length of 25 mm according to GB/T 228.1-
2010. Then the macrographs and micrographs of tensile and impact fracture surface
were observed by scanning electron microscope (SEM, JSM6480LV) and FE-SEM,
respectively. Macro-hardness tests were performed using Vickers hardness testing
machine on the steel specimens. Grain boundary segregation of Sn was characterized
by Auger Electron Spectrometer (AES, PHI-700).
The Effect of IHT on the Microstructural Evolution

Characteristics
Figure 2 presents the FE-SEM micrographs showing microstructural evolution dur-

ing intercritical heat treatment. The as-received specimen consists largely of ferrite
matrix phase and pearlite. Ferrite exists together with the lamellar form of pearlite,
as shown in Fig. 2a. After normalizing at 910 °C, as shown in Fig. 2b, there is a
Effect of Intercritical Heat Treatment on Microstructure … 535
Fig. 2 Typical FE-SEM micrographs showing microstructural evolution
large amount of granular bainite and a small amount of ferrite. The microstructure
of specimen after 910 °C normalizing and 860 °C conventional pre-quenching is
typical lath martensite, as shown in Fig. 2c. Figure 2d–f show the micrographs of
the normalized and pre-quenched specimens subjected to intercritical quenching at
three different temperatures: 760, 770, and 780 °C. A composite microstructure of
ferrite and martensite was obtained. One can observe that increasing the intercriti-
cal quenching temperature increases the martensite content of the steel as expected.
Martensite volume fractions are found to be 60, 73, and 95% for the steel heat-treated
intercritically at temperature of 760, 770, and 780 °C, respectively. Martensite formed
in lath shape and is clustered, making the distribution not even. Figure 2g–i show the
tempered microstructure of Fig. 2d–f at 450 °C, which are the composite structure
of tempered martensite and ferrite.
The intercritical temperature and holding time are the key controlling parameters
for microstructural characteristics of the steel [7]. The volume fraction of ferrite at
different intercritical temperature (760, 770, 780 °C) and the selected holding time
(3 h) are presented in Table 2. With the increase of intercritical quenching temper-
ature from 760 °C to 780 °C, the ferrite content decreased from 40% to 5%. The
soft and ductile ferrite and hard martensite play an important role in determining
the properties of dual-phase steel. Intercritical quenching temperature directly influ-
ences the hardness value since at higher intercritical quenching temperature, more
martensite will form. As shown in Table 2, it is obvious that there is direct correlation
536 L. Sun et al.
Table 2 The volume fraction of ferrite and hardness at different intercritical temperature (%)
Intercritical temperature/°C 760 770 780
Volume fraction of ferrite/% 40 27 5
Volume fraction of martensite/% 60 73 95
Hardness/HRV 452 477 582
of hardness with the amount of martensite. As the volume fraction of martensite was
increased, the hardness was increased accordingly.
The Effect of IHT on the Mechanical Properties
In order to determine an optimum IHT technology, impact testing and tensile test-
ing were performed at room temperature for the specimens heat-treated at various
intercritical quenching temperature and various tempering temperature. Figure 3a–d
present the mechanical properties of Charpy impact energy (Akv ), elongation (δ),
Fig. 3 The mechanical properties of the samples under different intercritical heat treatment
technologies
tensile strength (Rm ), and yield strength (Rel ), respectively. Compared with the sam-
ples treated by conventional heat treatment, the impact energy is increased from less
than 30 J to more than 50 J after the application of IHT. This is closely related to
the composite microstructure composed of soft ferrite and hard martensite, where
the soft phase ensures good deformability and the hard phase provides high tensile
strength [12]. The ferrite phase enhances the toughness of steel due to the large plas-
tic deformation occurring at ferrite to release the stress concentration [13]. Maleque
et al. [14] found the correlation of tensile strength–intercritical quenching tempera-
ture. For water quenched specimens with the same carbon content, tensile strength
increases with intercritical temperature. As shown in Fig. 3b–d, it is apparent that
with an increase in the intercritical quenching temperature of the steel, the yield and
tensile strength increase significantly.
When intercritical quenching at 780 °C, the impact energy increased with the
increasing tempering temperature from 450 °C to 550 °C. When the intercritical
quenching processes were performed at 760 and 770 °C, respectively, the impact
energy value of the sample tempered at 450 °C was greater than that tempered at
500 °C, as shown in Fig. 3a. When tempering temperature increases from 450 °C to
550 °C after intercritical quenching, the elongation increases and the tensile strength
and yield strength decrease, as shown in Fig. 3b–d. Based on the above heat treatment
experimental results, the optimum intercritical quenching temperature is 770 °C
and the optimum tempering temperature is 450 °C. This heat treatment technology
balances the strength and toughness of Sn bearing 33MnCrB5 steel.
The Effect of IHT on the Fractographic Features Analysis
To investigate the difference in micro-fracture mechanisms during impact testing,

the macrostructures and microstructures of the fracture surfaces were observed on
SEM and FESEM. The impact overall fracture morphology could be classified into
three zones: ductile region, brittle region, and shear lips as shown in Fig. 4. From
Fig. 4a–c, there is no significant difference in the area fractions of the shear lips.
And in the ductile region, the number of tiny dimples of (d) appears to be the highest
shown in Fig. 4d–f, which is consistent with the high-impact performance at 92 J.
In the brittle region, Fig. 4g exhibits quasi-cleavage morphology, Fig. 4h shows
intergranular morphology, and Fig. 4i shows intergranular dimple morphology. In
shear lips, morphology is composed of intensive, uniform, and plat dimples for all
samples, just as Fig. 4j–l shows. Figure 5 shows the macroscopic and microscopic
morphology of tensile fracture of experimental steel under 770 °C IHT. It can be
seen that samples show a typical ductile fracture. From Fig. 5a–c, it is clear that the
overall morphology of fracture is a typical cup-and-cone. As shown in Fig. 5d–f,
the ductile region in the center of specimens is composed of cracks and dimples,
indicative of classic ductile fracture. The morphology of shear lips zone at the edge
of specimens is characterized by flat and elongated dimples and some voids caused
by inclusions dropping from matrix, as presented in from Fig. 5g–i.
538 L. Sun et al.
Fig. 4 Macroscopic and microscopic fracture morphology of impact specimens under 770 °C IHT
Fig. 5 Macroscopic and microscopic fracture morphology of tensile specimens under 770 °C IHT
Fig. 6 Typical AES spectra for the specimens treated by conventional heat treatment (a) and IHT
(b)
AES for Grain Boundary Segregation of Sn
Typical AES spectra for the specimens treated by conventional heat treatment and
novel IHT are shown in Fig. 6. It can be qualitatively seen from Fig. 6a that after
conventional heat treatment, Sn segregates at grain boundaries, obviously. As shown
in Fig. 6b, no obvious Sn was detected at the grain boundaries, which indicates that
intercritical heat treatment improves the distribution of Sn, reduces the brittleness of
grain boundary. This also explains why intercritical heat treatment improves tough-
ness markedly of the Sn bearing 33MnCrB5 steel. The decrease of Sn segregation at
grain boundaries may be attributed to the factor: the presence of a certain amount of
ferrite by the intercritical heat treatment, and all the elements which reduce γ region
are concentrated in α phase. Therefore, the ferrite forming element Sn is enriched in
the ferrite, which reduces the chance for the harmful residual elements to segregate
at grain boundaries.
Conclusions
The effect of intercritical heat treatment on the microstructures and mechanical prop-
erties of Sn bearing 33MnCrB5 steel was investigated in this work. Some conclusions
are summarized as follows:
(1) By adding intercritical quenching process to the conventional heat treatment
of quenching and tempering, the Sn bearing 33MnCrB5 steel with composite
microstructure of ferrite phase and martensite was produced. The ferrite phase
improves the toughness of the steel, which is attributed to the large plastic defor-
mation that occurs at ferrite to release the stress concentration. More importantly,
the existence of ferrite reduces the Sn segregation at grain boundaries.
540 L. Sun et al.
(2) Based on different heat treatment results, the optimum heat treatment technol-
ogy, that is, 910 °C normalizing, 860 °C pre-quenching, 770 °C intercritical
quenching, 450 °C tempering, was obtained to balance the strength and tough-
ness. The yield strength, tensile strength, total elongation, and Charpy impact
value at room temperature are 995, 1086 MPa, 15.44%, and 77 J, respectively.
Acknowledgements This work was financially supported by the National Nature Science
Foundation of China (Grant No.51674020).
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mechanical properties of AISI 3115 stee. J Mater Process Technol 153–154:482–487
Production of a Cobalt–Nickel–Iron
Alloy from Low-Grade Ore
Yotamu R. S. Hara, Shadreck Chama, Golden Kaluba, Douglas Musowoya,

Kennedy Chikontwe, Choolwe Muchindu, Haggai Simfukwe
and Stephen Parirenyatwa
Abstract A novel way of producing a cobalt–nickel–iron alloy containing 55% Co,

9% Ni, and 36% Fe from an oxide ore with 1.8% copper, 0.26% cobalt, 2.8% iron,
and 0.08% nickel has been established. The ore is initially treated hydrometallurgi-
cally via leaching and precipitation steps to upgrade copper, cobalt, iron, and nickel
as a bulk sulphide concentrate. Precipitation is carefully carried out to lower down
iron in the bulk sulphide concentrates. The sulphide concentrate is smelted at 1,220
°C to produce blister copper and slag containing 11% Co, 1.8% Ni, and 7.2% Fe.
The effects of basic and acidic fluxes in promoting good metal/slag separation were
studied. The slag is then smelted under reducing environment at 1,400 °C to yield
cobalt–nickel–iron alloy. There is a broad agreement between thermodynamic pre-
diction and experimental results. The alloy was characterised using scanning electron
microscopy (SEM) technique.
Keywords Heterogenite · Cobalt alloy · Nickel alloy · Leaching
Introduction
Ternary cobalt–nickel–iron alloys play an important role in modern society being

critical to multiple industries. Commercial cobalt–nickel–iron alloys with the com-
position 16–28% Co, 27–35% Ni, and the remainder Fe find applications as glass-to-
metal seals—primarily for making hermetic seals with borosilicate glass and ceramic
materials used in power tubes, microwave tubes, transistors, and diodes, as well as
in integrated circuits—due to having similar thermal expansion properties [1–3].
The low-expansion properties are likely a result of magnetorestriction cancelling out
the regular thermal expansion of the alloy [3]. Co–Ni–Fe alloys exhibit good soft
magnetic properties, where such materials are key components of electromagnetic
devices such as step motors, magnetic sensors, transformers, and magnetic recording
Y. R. S. Hara (B) · S. Chama · G. Kaluba · D. Musowoya · K. Chikontwe · C. Muchindu ·

H. Simfukwe · S. Parirenyatwa
The Copperbelt University, 21692 Kitwe, Zambia
e-mail: yotamuhara@gmail.com

https://doi.org/10.1007/978-3-030-36540-0_48
542 Y. R. S. Hara et al.
heads. Magnetic materials are classified as ‘soft’ when they have a low critical field
strength Hc required to flip the direction of magnetization—referred to as coercivity
[4].
Cobalt–nickel–iron alloys are typically prepared by vacuum melting [5]. Alter-
native methods for Co–Ni–Fe alloy fabrication involve mechanical alloying and
electrodeposition of thin films from electrolyte solutions [6, 7].
The relatively intensive primary extraction and production methods of cobalt and
nickel from their respective ores is associated with significant societal and environ-
mental impacts, which include considerable energy consumption and large emissions
of acid-rain gases, solid waste, and greenhouse gases [8, 9]. Declining ore grades
further increases the environmental impact of primary extraction while challenging
the sustainability of the nickel and cobalt supply.
The novel process for ternary alloy production directly from oxide ore described
in this paper was developed in order to address the long-term challenges associated
with Ni–Co–Fe alloy production. The new method reduces the environmental impact
and enhances the supply chain sustainability by simplifying processing and utilising
a single ore body for alloy manufacture.
Leaching
Low grades of copper—cobalt ore is treated via hydrometallurgical methods in which

leaching is the initial step. Leaching involves selective dissolution of the desired
metal into the solution. In Zambia and DRC, most of the cobalt is contained in the
heterogenite mineral phase. Therefore, cobalt is associated with nickel, manganese,
and iron which also dissolve in the solution during leaching.
Precipitation of Copper, Cobalt, and Nickel from the Solution
Even though copper and cobalt can be recovered from the leach solution via elec-
trowinning, precipitation is commonly used at small-scale production. Copper,
cobalt, and nickel may be precipitated with lime (CaO) and magnesium oxide (MgO)
to form hydroxide. Nonetheless, iron removal via precipitation is necessary because
it heavily contaminates the precipitate. The major downside of precipitating cobalt
with lime or magnesium oxide is that there is significant loss of cobalt.
The sulphides of copper, cobalt, and nickel are more stable than that of iron which
means selective precipitation of copper, cobalt, and nickel may be achieved without
an iron removal stage. The Gibbs free energy for the precipitation of various sulphides
are compared in Fig. 1 from which it can be observed that the thermodynamic stability
decreases in the following order CuS, NiS, CoS, FeS, and MnS. Therefore, by adding
the stoichiometric amounts, only copper, cobalt, and nickel may be precipitated. The
Production of a Cobalt–Nickel–Iron Alloy from Low-Grade Ore 543
Fig. 1 Plot of Gibbs free MnSO4 + Na2S = MnS + NaSO4

2
energy against temperature -180
for the precipitation of Cu,
Gibbs Free Energy (kJ)

Co, Ni, Fe, and Mn with -200 FeSO4 + Na2S = FeS + Na
2
SO4
sodium sulphide
-220 CoSO4 + Na2S = CoS + NaSO4
2
-240
NiSO4 + Na2S = NiS + Na
2
SO4
-260
-280
-300 CuSO4 + Na2S = CuS + Na

2
SO4
0 10 20 30 40 50 60
Temperature (0C)
Table 1 Chemical composition of the as-received Oxide Kalaba Material (wt%)

Cu Co Fe Ni Si Mg Al Ca
1.82 0.21 2.82 0.083 26.81 18.5 4.78 0.2
main advantage is that the sulphide precipitated may easily be smelted to obtain
important alloys.
Experimental
Materials
The ore used in this study was obtained from North-Western province of Zambia. Its
chemical composition is shown in Table 1 where it can be observed that the sample
has 1.8 wt% copper and 0.21 wt% cobalt. The major gangue elements in the sample
are silicon (Si), magnesium (Mg), and aluminium (Al).
Leaching
The material was crushed and ground down to particle size of less than 150 µm.
The material was leached out at room temperature for 1.5 h at 33% solids. Sodium
metabisulphite (SMBS) was added in powder form in order to reduce cobalt from the
trivalent to divalent state as the later is soluble in acid. The optimised SMBS addition
was 0.6 wt% of the weight of the ore. The pH of the solution was maintained at 1.8
throughout the experiment by adding sulphuric acid. The optimised sulphuric acid
consumption was 70 kg per ton of ore. The leach slurry was filtered off in order to
separate the leach liquor from the residue.
Precipitation
Copper, cobalt, and nickel were recovered from the solution via precipitation with
sodium sulphide. The pH of the solution was raised to 4 in order to neutralise any free
acid. This is because free acid may react with sodium sulphide to yield the poisonous
hydrogen sulphide (H2 S) gas as shown in Eq. 1. Precipitation was only carried out
for 5 min and at room temperature.
Na2 S + H2 SO4 = H2 S(g) + Na2 SO4 (1)
Smelting
For the smelting process, the bulk sulphide concentrate was transferred into the
salamander crucible. The material was then smelted in air for one hour at 1250 °C.
Sulphur dioxide gas was generated during smelting owing to the oxidation of sulphur
in the material. The smelted material was removed from the furnace and allowed to
cool down to room temperature.
Production of Co–Ni–Fe Alloy
Slag produced during smelting was transferred into the graphite crucible. Graphite
crucible was used because it contains carbon which then reduces cobalt, nickel, and
iron oxides into their metallic state. The experiment was carried out at 1400 °C for
a period of 1 h.
Analysis of the Samples
The as-received, leached, precipitated samples were analysed by atomic absorption

spectroscope (AAS) and scanning electron microscope (SEM), respectively. The
SEM machine is equipped with energy dispersive x-ray fluorescence (EDX) which
allows both overall and phase quantification of the sample.
Fig. 2 Scanning electron microscope image under backscattered electron imaging. The bright
phases are the copper, cobalt, nickel, and iron bearing minerals
Scanning Electron Microscope Examination of the Ore
Scanning electron microscope (SEM) image for the as-received sample is shown in
Fig. 2. The bright particles are the Cu–Co bearing minerals whereas the dark ones
are the gangue minerals. Several particles of the sample were analysed individually
in order to characterise the different phases in the feed ore. It was found that copper
was present in the malachite and heterogenite phases, whereas cobalt and nickel were
only present in the heterogenite phase.
Leaching Test Results
The results from the leaching tests under optimal conditions are shown in Table 2
from which it can be observed that the recoveries of copper, cobalt, and nickel were
87%, 85%, and 78% respectively. On the other hand, very less iron was leached out
Table 2 Chemical analysis of the leach residue and % recovery

Cu Co Fe Ni
%Grade in leach residue 0.23 0.04 2.39 0.018
%Recovery 87.2 84.6 14.6 77.5
Table 3 Analysis of the concentrates in wt%

Cu Co Fe Mn Ni
35.25 3.95 2.95 0.14 0.50
as the recovery was only 15%. The acid consumption at pH of 1.8 was 70 kg per ton
of ore. Decreasing the pH of the leach solution increased the recoveries of copper
and cobalt to about 90% but acid consumption increased to 120 kg per ton of ore.
Precipitation of Copper, Cobalt, and Nickel from Leach

Solution
Copper, cobalt, and nickel were precipitated as a bulk sulphide precipitate with
sodium sulphide (Na2 S). Sodium sulphide was added at 1.1 × stoichiometric amount
required for precipitation of copper, cobalt, and nickel in order to allow complete
precipitation. The results for the precipitate are presented in Table 3 from which it
can be observed that copper, cobalt, and nickel were upgraded to 35%, 4%, and 0.5%,
respectively. The bulk sulphide concentrate or precipitate has 2.95 wt% Fe which
was caused by excess (0.1 above the stoichiometric) amount of sodium sulphide. The
balance in the precipitate was sulphur.
Smelting
Two phases were obtained during smelting of the bulk sulphide concentrate and they
are blister copper and slag phases. The chemical analysis of blister copper and slag
phases are shown in Table 4. It is evident from Table 4 that blister copper has 97.81
weight % of copper. The main impurity is sulphur which is at 0.6 weight %. On the
other hand, cobalt, nickel, and iron were recovered in the slag phase. The slag phase
analysed was reported to contain 11% cobalt, 1.8 weight % nickel, and 7.2 weight
% iron.
From the chemical analysis results in Table 4, it can be concluded that there was
preferential metallisation of copper and oxidation of nickel, cobalt, and iron. Copper
in the bulk sulphide concentrate exists as CuS and hence reactions (2) and (3) might
Table 4 Chemical analysis in weight % for the blister copper and slag obtained from smelting
stage
Cu Co Ni Fe S
Blister copper 97.81 0.34 0.29 0.13 0.61
Slag 3.72 11 1.8 7.2 –
have occurred during metallisation of copper.
2CuS + O2 (g) = Cu2 S + SO2 (g) (2)
Cu2 S + O2 (g) = 2Cu + SO2 (g) (3)
Cobalt, nickel, and iron have high affinity for oxygen and hence oxidation occurred
after metallisation. The oxidised cobalt, nickel, and iron oxide then formed a slag
phase.
Scanning electron microscope images for the blister copper and slag are presented
in Figs. 2 and 3, respectively. Two phases can be observed from the blister copper
in Fig. 2 (areas A and B). Sulphur was in the form of Cu2 S (area A). Area B was
pure metallic copper (more than 99 weight %). The phase segregation agrees with
the Cu–S phase diagram where Cu co-exists with Cu2 S.
Three phases can be observed from the SEM images in Fig. 3. The bright particles
are the metallic copper phase which could have been lost into the slag due to entrap-
ment. The main phase (grey area) analysed 1.5 weight % copper, 19 weight % cobalt,
4 weight % nickel, and 5 weight % iron. The dark area is sodium silicate (Na2 SiO3 )
which might have been formed due to the reaction of sodium in the concentrate and
SiO2 from the crucible (Fig. 4).
Fig. 3 Scanning electron microscope image under backscattered electron imaging. Phase A is Cu2 S
whereas B is pure metallic copper (99.99)
Fig. 4 Scanning electron

microscope image under
backscattered electron
imaging for the slag
Reductive Smelting of Slag
The above analysis has shown that cobalt, nickel, and iron exist in the oxide form.
Therefore, the presence of carbon from the graphite crucible allowed reduction of Co,
Ni, and Fe oxides into their metallic state at 1400 °C. The overall reaction occurring
reductive smelting is shown in Eq. 4, where M represents Co, Ni, and Fe.
MO + C = M + CO(g) (4)
The reduced Co, Ni, and Fe from Eq. 4 formed a Co–Ni–Fe alloy whose compo-
sition is shown in Table 5. It is worth noting that nickel has been upgraded to more
than 100 times from such a low-grade concentration in the ore (see Table 1). The
results in Table 5 were obtained after a series of three test works.
Table 5 Chemical analysis

Cu Co Ni Fe
of the alloy obtained after
three test works 5.5 55.16 9.28 36.40
Conclusions
From the experimental results, the following conclusions were made:

1. The leach efficiency for copper, cobalt, and nickel were 87%, 85%, and 78%,
respectively. However, only 14% of the iron was leached out (see Table 2).
2. Bulk precipitation with sodium sulphide yielded a sulphide concentrate with 35
weight % copper, 4 weight % cobalt, 3 weight % iron, and 0.5 weight % nickel.
This means that the leach step upgrades copper and cobalt by a factor of 19 times.
3. Preferential metallisation of copper occurred whereas cobalt, nickel, and iron
were oxidised and hence slagged off when the bulk sulphide concentrates were
smelted at 1523 K (see Table 5).
4. A cobalt–nickel–iron alloy containing 55% Co, 9% Ni, and 36% Fe was produced
after reductive smelting of the slag at 1400 °C.
References
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2. Chirnside RC, Cluley HJ (1947) The analysis of nickel-cobalt-iron alloys used in glass-to-metal
seals. Analyst 72(857):351–359
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of Industrial Chemistry
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film with high saturation magnetic flux density and low coercivity. Nature 392(6678):796
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23(3):53
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of nanocrystalline Fe–Co–Ni alloy processed by mechanical alloying. J Magn Magn Mater
398:190–195
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J Appl Phys 87(9):5410–5412
8. Norgate TE, Jahanshahi S, Rankin WJ (2007) Assessing the environmental impact of metal
production processes. J Clean Prod 15(8–9):838–848
9. Eckelman MJ (2010) Facility-level energy and greenhouse gas life-cycle assessment of the global
nickel industry. Resour Conserv Recycl 54(4):256–266
Combining Discrete Element Method
and Artificial Neural Network to Predict
the Particle Segregation Behaviors
at Bell-Less Top Blast Furnace
Zhehan Liao, Chengfeng Sun, Yang Xu, Muyang Wu, Yizhang Yang,
Chao Wang and Jian Xu
Abstract The inevitable particle segregation behaviors of granular materials are

undesirable in the industrial processes. It will directly affect the heat transfer effi-
ciency between gas and solid phases during the ironmaking process of blast furnace.
Therefore, the understanding and prediction on the particle segregation behaviors
are vital to optimize the process and improve the production efficiency. This work
first employs the Discrete Element Method (DEM) to investigate the effects of the
parameters, such as the particle density, the mean diameter, the mass of particles,
the particles mass ratio, and the angle of chute, on the mass segregation and size
segregation behaviors at the bell-less top blast furnace with the serial type hopper.
Then, the Artificial Neural Network (ANN) model is proposed to predict the afore-
mentioned behaviors in the radial direction based on the numerical data. The results
show that the predicted segregation behaviors by the established ANN model are in
a good agreement with the simulated results.
Keywords Particle segregation · Discrete element method · Artificial neural

network · Bell-less top · Blast furnace
Introduction
The blast furnace is a typical reactor to produce hot metals from iron ores in the iron-
making process. After the burden distribution, either physical changes or chemical
reactions happen inside the furnace, which are occurred by the interaction of the ore
and coke particles. Due to the differences in particle properties, hopper types, and
rotating chute parameters, etc., the particle segregation [1] behaviors inevitability
occur during the burden distribution process, such as size segregation, mass segre-
gation, motion segregation, and so on. However, those phenomena sometimes are
Z. Liao · C. Sun · Y. Xu · M. Wu · Y. Yang · J. Xu (B)

College of Materials Science and Engineering, Chongqing University, 400044 Chongqing, China
e-mail: jxu@cqu.edu.cn
C. Wang
College of Mechanical Engineering, Chongqing University, 400044 Chongqing, China
https://doi.org/10.1007/978-3-030-36540-0_49
552 Z. Liao et al.
undesirable for the blast furnace smooth operation, because they can directly affect
the heat transfer efficiency and the gas flow permeability. Therefore, the under-
standing of the particle segregation behaviors helps in optimizing the process and
improving the production efficiency.
In the previous studies, most works were mainly carried out by experimental
measurements [2] and DEM simulations [3, 4] to analyze the particle segregation
behaviors. As early as 1976, Williams [5] had pointed out that the particle size is the
most important factor affecting the particle segregation behaviors. Moreover, Yu and
Saxén [6] studied the segregation behaviors of the ternary size particles in a blast
furnace top bunker model based on DEM and experiment methods, and the results
showed that the main factors, such as fine mass fraction, particle friction coefficients,
and filling method, affect the segregation behaviors during the discharging process.
However, the large-scale DEM simulation costs increasing computational
resource [7]. As a result, in order to reduce the demand for the large-scale simulation
by the DEM simulations, the Artificial Neural Network (ANN) model is proposed
to predict the particle segregation behaviors, which is based on the numerical data.
Hence, this work firstly employs the DEM simulation to investigate the effects of
initial particle mass ratio on the size and mass segregation. Then, the Artificial Neural
Network (ANN) model is developed to predict the aforementioned behaviors in the
radial direction.
Numerical and Analytical Methods
DEM Model
The DEM simulation developed by Cundall and Strack [8] is employed to numeri-
cally investigate the particle-scale behaviors during the discharge process. The cor-
responding governing equations for the interactions between particles i and j can be
given by
dui K

mi = Fcn,ij + Fdn,ij + Fct,ij + Fdt,ij + mi g (1)
dt j=1
dωi K
Ii = Tt,ij (2)
dt j =1
The explanations on the parameters can be found everywhere, as well as in the

authors’ previous work [9]. The geometries of the burden distribution model are
demonstrated in Fig. 1 [10]. Meanwhile, the parameters used in the DEM simulation
are listed in Table 1.
Combining Discrete Element Method and Artificial Neural Network … 553
Fig. 1 Geometries of the established mathematical model of the bell-less top blast furnace with
the serial type hopper for the DEM simulation [10]
Table 1 The parameters used in the DEM simulation [10]. (The parameters with underline are
used for the particle segregation analysis)
Parameters Value
Particle diameter, d(mm) 4, 6, 8
Particle density, ρ(kg/m3 ) 1400, 2800, 4200
Initial mass ratio, ms :ml (–) 0.3:0.7, 0.5:0.5, 0.7:0.3
Mass of particles, m (kg) 1-10
Young’s modulus, E (Pa) 3.75 × 108
Poisson ratio, υ (–) 0.22
Rotation speed of chute ω(rad/s) 2π/5
Inclination angle of chute, α(°) 27, 30, 33
Coeff. of interparticle restitution, e (–) 0.6
Coeff. of interparticle friction, μ (–) 0.4
Coeff. of particle-wall restitution, e (–) 0.7
Coeff. of particle-wall friction, μ (–) 0.6
Time step, Δt (s) 1.0 × 10−5
554 Z. Liao et al.
ANN Model
The ANN model used in this study is a multi-layer feedforward neural network which
is based on the back-propagation algorithm. The network consists of the output layer,
the input layer, and the one or more hidden layers. Each layer contains multiple
neurons, and the neurons in the same layer are not connected to other neurons, but
the neurons can connect to the neurons which are in the next layer through the weights
and bias. So, the neurons only affect the neurons in the next layer. The schematic
diagram of the neural network is shown in Fig. 2. The summation of input (Xn ) is
passed through an activation function (f) to get the output (a) of the particular neurons,
where b and wi represent the bias and weights, respectively. Furthermore, the accurate
prediction of particle segregation behaviors can be achieved by constantly optimizing
the values of b and wi .
Analysis Method for Particle Segregation Behaviors
In order to quantitatively analyze the characteristics of the particle segregation behav-

iors. The furnace throat is divided into five parts with the equal area, and remarked
as ring I to V, respectively (shown in Fig. 3). When the binary-sized particles are
discharged and packed in the furnace throat, through calculating the total mass and
the mass fraction of small particles (MFs) in each region, the mass and size segre-
gation of particles can be analyzed. And MFs in the binary-sized particle mixture is
calculated by Eq. (3):
Fig. 2 The principle of the Artificial Neural Network [7]

Fig. 3 Schematic diagram of mapping the furnace throat [10]
ms
M Fs = (3)
mt
where ms and mt represent the mass of small particles and the total mass at the
specific region.
ANN Model Fitting
In this study, the five input parameters, particle density, mean diameter, mass of
particles, angle of chute and particles mass ratio, are used to the train network for
prediction of the mass segregation and the size segregation behaviors. The complete
scheme for the ANN model is shown in Fig. 4. And a total of 64 input–output
data sets are generated, which are based on the DEM simulations. In the process
of selecting the best Artificial Neural Network architecture for the prediction, the
assignment of training, verification and testing data is random but fixed. Where
70% of the data sets are used for the training, 20% of the data sets are used for
the testing, and the remaining 10% of data sets are used for the cross-validation of
556 Z. Liao et al.
Fig. 4 The structure of Artificial Neural Network (ANN)
Table 2 The MSE of the ANN model with different parameters

The number of The number of Training error Validation error Testing error
hidden layers hidden layer
neurons
1 5 0.0079 0.0058 0.010
6 0.013 0.043 0.012
7 0.014 0.011 0.011
8 0.0080 0.017 0.0082
9 0.0085 0.0088 0.0049
10 0.0084 0.013 0.0066
11 0.014 0.013 0.017
2 5 0.010 0.0064 0.0041
6 0.0082 0.012 0.0075
7 0.0064 0.021 0.0089
8 0.0083 0.022 0.0066
9 0.0082 0.016 0.011
10 0.0087 0.0031 0.0055
11 0.0081 0.013 0.0070
the selected network. Then, we use the MFs simulation data in the ring 1 for the
best network architecture selection process. And Table 2 collects the MSE (mean-
square error) of different ANN model architectures during the model fitting process,
in terms of training, validation, and testing errors with the different hidden neurons
(5–11) and the different hidden layers (1 or 2). And the results indicate that the 5-9-1
structure with 1 hidden layer which is highlighted in Table 2 is the most appropriate
Fig. 5 The comparison

between the targets and the
predicted results by the
selected ANN model
architecture for our study, because its MSE results for each data set is lower than
others, and the training error is close to the validation error. Moreover, we further
test the above-mentioned structure and Fig. 5 shows the testing results. The results
show that the values are closer between the predictions and targets. Besides, the R2
(coefficient of determination) is about 0.928 which is close to 1, and it indicates
that the selected neural network is capable of providing a good correlation between
targets and predicted results of the particle segregation behaviors.
The Applicability of the Established ANN Model
In order to further analyze the influence of the different initial mass ratios on binary-
sized particles with the mass segregation and the size segregation behaviors, the initial
mass ratio of the small particles (ms) is changed to 0.3, 0.5, and 0.7, respectively,
and the total mass of particles are retained at 120 kg. Other parameters are shown
in Table 1 with underline. First of all, the results are shown in Table 3, and it can be
seen that 0.88 is the minimum value of R2 at the different cases, which indicates that
the established ANN model will capture the particles interaction behaviors which
are determined by the DEM simulation. Then, the mass of particles at the ring 2 is
the largest while that of the ring 1 is the smallest in each case, of which the results
Table 3 The values of R2 at different initial mass ratio

Mass MFs
ms:ml = ms:ml = ms:ml = ms:ml = ms:ml = ms:ml =
0.3:0.7 0.5:0.5 0.7:0.3 0.3:0.7 0.5:0.5 0.7:0.3
R2 0.97 0.98 0.98 0.88 0.99 0.99
558 Z. Liao et al.
Fig. 6 Comparison on (a) mass and (b) MFs distribution in the radial direction between the DEM
simulation and the ANN model prediction
are shown in Fig. 6a. For example, when the initial mass ratio of the small particles
is 30%, from the center to the edge at the furnace throat, the mass first increases
from 2.361 kg to 3.445 kg, then decreases to 2.746 kg. In addition, the MFs results
are shown in Fig. 6b where the values of MFs decrease from the center to the edge.
Therefore, the small particles are mainly concentrated in the center area, while the
large particles are mainly concentrated in the edge area during the discharge process.
Conclusions
When the binary-sized particles are discharged from the bell-less top blast furnace
with the serial type hopper, the DEM model and the ANN model are combined to
predict the particle segregation behaviors in the radial direction. The best ANN model
for the present work is found to be the 5–9–1 structure with 1 hidden layer, which is
able to predict the mass segregation and the size segregation behaviors of particles in
the radial direction with reasonable accuracy, and the minimum value of R2 is 0.88.
Moreover, the mass distribution at the ring 2 is the largest while that at the ring 1
is the smallest. Meanwhile, the small particles are mainly concentrated in the throat
center, while the large particles are distributed to the edge area.
Acknowledgements The authors are grateful to the project supported by the Natural Science
Foundation of Chongqing, China (cstc2019jcyj-msxmX0089).
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9. Xu J, Hu Z, Xu Y et al (2017) Transient local segregation grids of binary size particles discharged
from a wedge-shaped hopper. Powder Technol 308:273–289
10. Xu Y, Xu J, Sun C et al (2018) Quantitative comparison of binary particle mass and size
segregation between serial and parallel type hoppers of blast furnace bell-less top charging
system. Powder Technol 328:245–255
A New Approach for the Production
of Li4 SiO4 Powder
Kağan Benzeşik, Ahmet Turan and Onuralp Yücel
Abstract Li4 SiO4 is a promising material for CO2 capture at high temperatures.
A high capture capacity up to 36.7 wt% between 450 and 700 °C, fast carbona-
tion/decarbonation kinetics, good mechanical properties, and also cyclic usage can
be counted as the advantages of this solid. Li4 SiO4 can be synthesized using dif-
ferent methods: the solid-state reaction, the precipitation method, the impregnation
suspension method, and the sol–gel method. However, all the processes which are
mentioned above requires high energy consumption and result in products having a
large grain size. Combustion synthesis techniques are energy-efficient and advanta-
geous in terms of obtaining nano-sized ceramic powders. Therefore, the main pur-
pose of this study is producing Li4 SiO4 powders with volume combustion synthesis
(VCS) available to use as a high temperature sorbent in CO2 capture, instead of the
conventional and commercial methods.
Keywords Volume combustion synthesis · Lithium orthosilicate · Ceramic

materials
Introduction
The huge CO2 emission emitted by human activities, including the combustion of
fossil fuels, has been recognized as one of main contributors to climate change, as
the atmospheric CO2 concentration increases by 40% since the industrial revolution.
K. Benzeşik · O. Yücel (B)

Faculty of Chemistry & Metallurgy, Metallurgical and Materials Engineering Department,
Istanbul Technical University, 34469 İstanbul, Turkey
e-mail: yucel@itu.edu.tr
K. Benzeşik
e-mail: kaganbenzesik@gmail.com
A. Turan
Faculty of Engineering, Chemical and Process Engineering Department, Yalova University, 77200
Yalova, Turkey
e-mail: aturan@yalova.edu.tr

https://doi.org/10.1007/978-3-030-36540-0_50
562 K. Benzeşik et al.
To address this global problem, carbon dioxide capture and storage (CCS) tech-
nologies including oxy-combustion, pre-combustion, and post-combustion carbon
capture have been developed [1].
One of the most promising techniques for CO2 capture consists in its separation
by the reversible reaction with a sorbent (post-combustion). Three suitable materials
are known to have good capacities for the sorption of CO2 at high temperatures: CaO-
based materials, hydrotalcites (HT), and lithium-based materials. Activated carbons
and zeolites have been widely used, though the low equilibrium temperature for
adsorption (25–150 °C) limits their application at high temperature.
The lithium-based ceramics such as lithium oxide (Li2 O), lithium zirconate
(Li2 ZrO3 ), lithium orthosilicate (Li4 SiO4 ), lithium aluminate (Li5 AlO4 ), lithium fer-
rite (LiFeO2 ), and lithium titanate (Li4 TiO4 ) have been used for CO2 capture. Among
the lithium-based compounds, Li4 SiO4 is a candidate material for CO2 capture at
high temperatures. The reaction of this solid is attributed to the mechanism by which
the Li2 O within the crystal structure of Li4 SiO4 reversibly reacts with CO2 , as given
by Eq. (1).
Li4 SiO4 (s) + CO2 (g) ↔ Li2 SiO3 (s) + Li2 CO3 (s) (1)
The advantages of this solid include a relatively high capture capacity (theoret-
ical value of 36.7 wt%) at temperatures of 450–700 °C, fast kinetics of carbona-
tion/decarbonation, good mechanical properties and also the possibility of use in
repeated carbonation/decarbonation cycles. Although there are some ongoing stud-
ies about the regeneration potential of this material, the main features of regeneration
mechanism could not have been introduced yet [2].
Conventionally and commercially Li4 SiO4 is synthesized via solid-state synthe-
sis. This technique requires very high energy consumption to heat up the reactant
materials (Li2 CO3 and SiO2 ) at about 950 °C resulting in synthesized powders having
very large particle size and crystallite size. Combustion synthesis methods provide
synthesized ceramic powders with low energy requirements and in nano-size [3].
With this study, it is aimed to optimize the volume combustion synthesis conditions of
the Li4 SiO4 and for this purpose; the present study was conducted in two main stages:
volume combustion synthesis experiments and characterization of synthesized pow-
ders. In the experimental series, the starting materials were technical grade lithium
carbonate (Li2 CO3 , min. 99% by mass) as lithium source and high-quality silicon
(Si, min. 99.5% by mass, −325 mesh) powder. The volume combustion synthesis
process took place according to Eq. (2).
2Li2 CO3 + Si + O2 → Li4 SiO4 + 2CO2 (2)

A New Approach for the Production of Li4 SiO4 Powder 563
Fig. 1 Initial powder mixture and selected products
Since the specific heat value of the above reaction was calculated as −3295.97 J/g
by means of FactSage 7.1 thermochemical simulation software, it was predicted that a
combustion synthesis technique could be applicable for synthesis of Li4 SiO4 . Indeed,
an SHS process was tried to carry out by using stoichiometric mixture in Eq. 2 before
VCS experiments, but the reaction was not self-sustainable due to low volume of Si
powders in initial powder mixture. The authors, therefore, designed experimental
series by using VCS principles. Before VCS experiments, the initial powders were
mixed by a turbula mixer for 15 min in order to obtain homogeneous mixtures. Then,
the powders were put into alumina boats which have 100 × 30 × 12 mm dimensions
as it is seen in Fig. 1.
Samples were put in the muffle furnace in order to conduct the volume combustion
synthesis reaction. In the beginning, furnace temperature was at room temperature
and heated up to 500, 550, 600, 650, 700, 750, 800, 850, and 900 °C to optimize the
reaction temperature with the holding duration of 60 min. Once the temperature was
optimized, 45 and 75 min of holding durations were also studied for the temperatures
which have resulted in higher weight loss. Also, in Fig. 1, the photographs of selected
reaction products were given.
Before the experimental studies, a thermochemical simulation was performed in order

to simulate the possible products by FactSage thermochemical simulation software
(Fig. 2). As it is seen in the figure, Li4 SiO4 starts to form after 700 °C.
Theoretical weight loss of the reaction given in Eq. 2 is 31.85%, so the remaining
solid ratio is 68.15%. It can indicate the degree of reaction conversion rate. In Fig. 3,
remaining solid ratios of reaction products are given. At the temperatures equal and
greater than 650 °C, the remaining product ratio started to remarkably decrease from
approximately 90% to the values closer to 68.15% which is the calculated-theoretical
Fig. 2 Thermochemical simulation of the VCS reaction
Fig. 3 Change of remaining product ratio with increasing reaction temperature and duration
Fig. 4 XRD patterns of reaction products from 500 to 675 °C for 60 min
value. The change between 700 and 900 °C was very low in the experiments carried
out for 60 min. However, in the experiments conducted for 75 min, remaining product
ratio was almost same as the theoretical value at the temperatures equal and greater
than 800 °C. Thus, it was clear to see the reaction reaches equilibrium at 800 °C for
reaction duration of 75 min. Additionally, for the experiments conducted for 45 min,
reaction was fully achieved after 850 °C.
XRD patterns of synthesized powders were given in Figs. 4, 5, 6 and 7. Patterns
indicate the formation Li4 SiO4 phase with increasing process temperature and dura-
tion successfully. From 500 to 675 °C for 60 min, the formation of Li4 SiO4 occurred.
But at 675 °C there were still unreacted and other phases such as Li2 CO3 , Si, and
SiO2 (Fig. 4). In the experiments conducted for 60 min, intensity of Li4 SiO4 peaks
remarkably increased with the increase of temperature, particularly at the tempera-
tures equal to and greater than 700 °C. In the experiment conducted at 900 °C, the
product consisted of mainly Li4 SiO4 and slight amounts of Li2 CO3 and SiO2 (Fig. 5).
When the reaction duration increased to 75 min, the amount of formed Li4 SiO4 phase
slightly increased (Fig. 6).
Conclusions
VCS process was carried out to synthesize Li4 SiO4 . Increasing temperature (from 700
to 900 °C) and process duration (45–75 min.) were the investigated VCS parameters.
Almost pure Li4 SiO4 was obtained at the temperatures equal to and greater than
800 °C and for the process duration of 75 min. For the temperatures equal to and
greater than 850 °C, the process duration of 45 min was enough to synthesize pure
Li4 SiO4 .
It is an ongoing study and, it is planned to investigate the CO2 uptake capacity of

the sorbents synthesized under optimum conditions in the future.
References
1. Zubbri NA et al (2018) Parametric study and effect of calcination and carbonation conditions
on the CO2 capture performance of lithium orthosilicate sorbent. Chin J Chem Eng 26:631–641
2. Amorim SM, Domenico MD, Dantas TLP, José HJ, Moreira RFPM (2016) Lithium orthosilicate
for CO2 capture with high regeneration capacity: Kinetic study and modeling of carbonation
and decarbonation reactions. Chem Eng J 283:388–396
3. Izquierdo MT, Turan A, Garcia S, Maroto-Valer MM (2018) Optimization of Li4 SiO4 synthesis
conditions by a solid state method for maximum CO2 capture at high temperature. Mater Chem
A 6:3249
Preparation of Metallized Pellets
from Blast Furnace Dust and Electric
Arc Furnace Dust Based on Microwave
Impedance Matching
Lei Ye, Zhiwei Peng, Qing Ye, Liancheng Wang, Robin Augustine,
Joonho Lee, Yong Liu, Mudan Liu, Mingjun Rao, Guanghui Li
and Tao Jiang
Abstract Blast furnace dust and electric arc furnace dust are two typical solid
wastes in iron and steel industry. In order to overcome the shortcomings of tra-
ditional processes, such as low metal recovery efficiency and high secondary pol-
lution, microwave energy was applied in this study to intensify the self-reduction
of core-shell BF dust-EAF dust composite pellets based on impedance matching
for realizing highly efficient migration and separation of iron, zinc, and lead. By
reducing the composite pellets in microwave field, it was found that under the opti-
mal conditions of proportion of EAF dust in shell to all EAF dust in the pellet of
20%, reduction temperature of 1000 °C, and dwell time of 15 min, metallized pellets
with the total iron content of 68.73 wt %, iron metallization degree of 95.87%, zinc
removal percentage of 88.78%, lead removal percentage of 94.38%, and compressive
strength of 190.4 N/p were obtained.
Keywords BF dust · EAF dust · Microwave · Impedance matching ·

Self-reduction
L. Ye · Z. Peng (B) · Q. Ye · L. Wang · M. Rao · G. Li · T. Jiang

410083, China
Central South University, Changsha, Hunan 410083, China
R. Augustine
Department of Engineering Sciences, Uppsala University, Uppsala 75121, Sweden
J. Lee
Department of Materials Science and Engineering, Korea University, Seoul 02841, South Korea
Y. Liu · M. Liu
Guangdong Provincial Key Laboratory of Development and Comprehensive Utilization of
Mineral Resources, Guangdong 510650, China

https://doi.org/10.1007/978-3-030-36540-0_51
570 L. Ye et al.
Introduction
According to the statistics of the World Steel Association, the world crude steel
production has been sharply increasing in the past two decades, reaching 1.8086
billion tons in 2018 [1]. In general, the production of metallurgical dust accounts for
about 10% of iron and steel production [2]. Among them, blast furnace (BF) dust
and electric arc furnace (EAF) dust are two important metallurgical dusts, both of
which are rich in Fe and Zn. In general, BF dust contains 25–50 wt % Fe, 1–5 wt
% Zn, and 15–25 wt % C [3, 4], while EAF dust had 30–45 wt % Fe, 3–17 wt %
Zn, and 2–7 wt % Pb [5]. In particular, EAF dust was categorized as hazardous solid
waste by U.S. Environmental Protection Agency (EPA) [6]. Heavy metal elements,
such as Pb and Cr, would infiltrate into groundwater under the action of rainwater,
endangering animals, plants, and also human living environment if the dusts are piled
up randomly [7]. Meanwhile, valuable elements, e.g., Fe and Zn, in the dust are not
recovered, resulting in serious waste of valuable resources. Evidently, it is important
to seek optimal methods for their treatment.
In recent years, many novel processes have been developed for the efficient treat-
ment of BF dust and EAF dust, which can be divided into three categories: pyromet-
allurgical processes, hydrometallurgical processes, and physical methods [8]. Tradi-
tional pyrometallurgical processes, such as the rotary kiln process, are featured by
high metal recovery, with low iron metallization degree, low productivity, serious
environmental pollution, and massive energy consumption [9–11]. Unlike pyromet-
allurgical processes, hydrometallurgical processes are usually performed to extract
zinc from the dust by dissolving the dust in solution [12]. They are confronted with
the problems of high production cost, large consumption of leaching agents, and dif-
ficult treatment of leaching waste liquor. The physical methods can be used to recycle
iron and zinc. However, they have low efficiency in recycling valuable metals [13].
As clean and renewable energy, microwave has been extensively used for extrac-
tive metallurgy due to its unique advantages, such as selective and volumetric heating
[14, 15]. It was found that based on the rule of impendence matching, the BF dust
could be totally distributed in the pellet core, while EAF dust might be selectively dis-
tributed in the pellet core and shell to reduce microwave reflection loss for improving
reduction performance.
The aim of this study was to provide a new method for efficient treatment of
hazardous EAF dust and BF dust by microwave-assisted self-reduction of BF dust-
EAF dust composite pellets according to the rule of impendence matching. The
method offered is expected to be useful for treatment of hazardous solid wastes in
the iron and steel industry.
Preparation of Metallized Pellets from Blast Furnace Dust … 571
Experimental
Materials
The raw materials included BF dust and EAF dust, both of which were taken from
Baosteel, China. The main chemical compositions of BF dust and EAF dust are
shown in Table 1. The BF dust had 42.47 wt % Fe and 19.43 wt % C, with little Zn,
Pb, and Cr. The EAF dust contained 51.53 wt % Fe, 4.690 wt % Zn, 0.125 wt % Pb,
and 0.236 wt % Cr.
Figure 1 shows that the main phase compositions of BF dust and EAF dust. The
main phase components of BF dust were hematite and magnetite, whereas those
of EAF dust were hematite, magnetite, and franklinite. Besides, there were certain
amounts of gangue phases in both kinds of dusts.
Table 1 Main chemical compositions of BF dust and EAF dust (wt %)

Sample TFe Zn Pb Cr CaO Al2 O3 SiO2
BF dust 42.47 0.015 0.008 0.006 8.81 3.14 4.61
EAF dust 51.53 4.690 0.125 0.236 8.96 1.27 3.02
Sample S P K Na Mg Mn Cl C*
BF dust 0.16 0.21 0.22 0.08 1.22 0.13 0.01 19.43
EAF dust 0.47 0.46 1.07 1.03 2.48 2.74 0.06 0
C*-Fixed carbon
Fig. 1 XRD patterns of BF dust and EAF dust

572 L. Ye et al.
Fig. 2 Morphologies and particle size distributions of BF dust and EAF dust
Figure 2 shows the morphologies and particle size distributions of BF dust and
EAF dust. The BF dust was mainly constituted by large irregular particles, while the
EAF dust mainly consisted of irregular agglomerates accumulated by fine spherical
dust particles. Figure 2 also shows that the mean particle size of BF dust (d0.5 =
34.805 μm) was much larger than that of EAF dust (d0.5 = 0.188 μm), agreeing with
the morphology analysis of the dusts.
Table 2 lists the pelletizing properties and other physical properties of BF dust
and EAF dust, mainly including the maximum capillary water content, migration
velocity of capillary water, and pelletizing index (K). It shows that the pelletizing
indexes of BF dust and EAF dust were, respectively, 0.75 and 3.70, showing the
much better pelletizing property of EAF dust than that of BF dust. The BF dust and
EAF dust used in this study should be pre-dried as they had low migration velocities
of capillary water (2.14 mm/min and 6.96 mm/min, respectively).
In order to reduce the reflection loss of microwave on the surface of composite
pellets and to improve the utilization of microwave energy, according to the rule
Table 2 Pelletizing and other physical properties of BF dust and EAF dust
Sample Maximum Migration Maximum Pelletizing True Bulk
capillary velocity of molecular index density density
water (wt capillary water (wt (g/cm3 ) (g/cm3 )
%) water %)
(mm/min)
BF dust 36.71 2.14 15.73 0.75 3.22 1.19
EAF dust 25.44 6.96 20.03 3.70 2.79 0.81
(a) (b)
Fig. 3 Relative permittivities and permeabilities of a BF dust and b EAF dust
of impedance matching, the impedance value of microwave in air (μ0 /ε0 )1/2 , that
of pellet shell (μs /εs )1/2 and that of pellet core (μc /εc )1/2 should obey the following
relation: (μ0 /ε0 )1/2 > (μs /εs )1/2 ≥ (μc /εc )1/2 .
Figure 3 shows the values of relative permittivity and permeability of BF dust and
EAF dust in the frequency range of 2–4 GHz. The results showed that the relative
dielectric constant (εr ) of BF dust was higher than that of EAF dust. Its relative
magnetic constant (μr ) was close to 1.5, lower than that of EAF dust, which had
slight fluctuations in the examined frequency range. When the microwave frequency
was 2.45 GHz, the relative magnetic loss factor (μr ) of BF dust was close to that of
EAF dust. The BF dust had higher dielectric loss factor (εr ) than that of EAF dust.
Therefore, the impedance matching degree of microwave on the surface of BF dust
was less than that on the surface of EAF dust.
Methods
Preparation of Composite Pellets
The mass of BF dust for pelletizing was fixed to be 2 kg, and the mass of EAF dust
was adjusted according to the change of C/O molar ratio in the composite pellets.
Subsequently, the raw materials for pelletizing were divided into two parts according
to the proportion of EAF dust in the pellet shell to all EAF dust in the pellet. The first
part of the materials consisting of BF dust and EAF dust was used for preparation of
pellet core; the second part of the materials containing only EAF dust was used for
producing pellet shell. After pre-adding 5% water to the raw materials, the composite
pellets were prepared using a disc pelletizer with edge height of 150 mm, tilt angle
of 47° and diameter of 1000 mm. During pelletizing, the size of pellet core was
controlled at 10 ± 0.5 mm and the total size of core-shell BF dust-EAF dust composite
574 L. Ye et al.
pellets was controlled at 11 ± 13 mm. The drop number and compressive strength
of the green pellets and the compressive strength of dried pellets were measured by
the methods reported in literature [16].
Microwave-Assisted Reduction
After drying for 12 h at 105 °C, 40 g of core-shell BF dust-EAF dust composite pellets
were loaded into a corundum crucible which was then transferred to a horizontal
microwave furnace (2.4 kW, 2.45 GHz, Hunan Huae Microwave Technology Co.
Ltd., China) for reduction in N2 . The composite pellets were heated with an average
ramp rate of 35 °C/min. After reduction, the metallized pellets were obtained and
collected for analysis.
Effect of Proportion of EAF Dust in the Pellet Shell to All

EAF Dust in the Pellet on the Qualities of Green and Dried
Composite Pellets
For reduction, the C/O molar ratio in the composite pellets was set as 0.9. In other
words, the mass ratio of BF dust to EAF dust was 2.125. There was no additive
used for preparing composite pellets. The effect of the proportion of EAF dust in the
pellet shell to all EAF dust in the pellet on the qualities of green and dried pellets was
studied by fixing the pelletizing time of 16 min and rotation speed of disc pelletizer
of 20 r/min. The results are shown in Fig. 4.
As shown in Fig. 4, when the proportion of EAF dust in the pellet shell to all EAF
dust in the pellet increased from 0 to 30%, both qualities of green and dried composite
pellets increased first and then decreased. When the proportion of EAF dust in pellet
shell to all EAF dust in the pellet was 20%, the drop number and compressive strength
of green pellets and compressive strength of dried pellets reached their maximum
values of 4.5 times/0.5 m, 12.1 N/p and 42.2 N/p, respectively. The EAF dust acted as
raw material and also pelletizing binder due to its much better pelletizing properties
than those of BF dust, as demonstrated in Table 2. Obviously, the pellet had the best
quality when the proportion of EAF dust in the pellet shell to all EAF dust in the
pellet was 20%.
Fig. 4 Effect of proportion of EAF dust in the pellet shell to all EAF dust in the pellet on the quality
of green and dried composite pellets
Effect of Proportion of EAF Dust in the Pellet Shell to All

EAF Dust in the Pellet on the Quality of Metallized Pellet
The effect of the proportion of EAF dust in the pellet shell to all EAF dust in the
pellet (i.e., the thickness of shell) on the quality of metallized pellet was studied by
fixing the reduction temperature of 1000 °C, dwell time of 15 min, mass of composite
pellets of 40 g, and N2 flow rate of 0.2 L/min. The results are shown in Fig. 5.
As shown in Fig. 5, when the proportion of EAF dust in the pellet shell to all
EAF dust in the pellet increased from 0 to 30%, the total iron content, iron metal-
lization degree and compressive strength of the metallized pellets first increased and
then decreased, and their maximum values were 68.73 wt %, 95.87%, and 190.4 N/p,
respectively. The removal percentages of zinc and lead in metallized pellets decreased
from 90.72% and 95.59% to 87.22% and 93.64%, respectively. It was beneficial to
the utilization of microwave energy by reducing the reflection loss of microwave
on the pellet shell which contained a higher amount of EAF dust. It was believed
that the carbothermal reduction was prone to start from the pellet core. Meanwhile,
microwave-assisted reduction of core-shell BF dust-EAF dust composite pellets can
improve the utilization of carbon, reducing heat loss and increasing the CO concen-
tration of the reduction, which was conducive to the indirect reduction of FeOX and
ZnFe2 O4 . However, when excessive EAF dust was transferred to the pellet shell, the
pellet shell thickened, leading to difficult diffusion of reductive gases generated in
the pellet core to the surface of the pellets, easily causing cracking of pellet. The
cracking would not only reduce the utilization of reducing gas but also affect the
576 L. Ye et al.
Fig. 5 Effect of proportion of EAF dust in the pellet shell to all EAF dust in the pellet on the quality
of metallized pellet
mechanical strength of the pellet. In addition, the porosity of pellets was the main
factor affecting the removal of lead chloride. When more EAF dust was used for
producing pellet shell, the removal of lead would be restrained due to the dense
structure of the pellet shell. Considering the effects of the proportion of EAF dust in
the pellet shell to all EAF dust in the pellet on the quality of metallized pellet, the
suitable proportion was 20%. At this time, the removal percentages of zinc and lead
were 88.78% and 94.38%, respectively.
Comparison Between Metallized Pellets C1 , C2, and C3
In order to further identify the unique advantages of microwave-assisted reduction of

core-shell BF dust-EAF dust composite pellets, microwave/conventional reduction
of pellets with different structures were carried out, respectively, under the same
experimental conditions. By fixing the heating temperature of 1000 °C, dwell time of
15 min, mass of composite pellets of 40 g, N2 flow rate of 0.2 L/min, and average ramp
rate of 35 °C/min, the metallized pellets obtained by microwave-assisted reduction
of core-shell BF dust-EAF dust composite pellets, microwave-assisted reduction of
homogeneous BF dust-EAF dust composite pellets, and conventional reduction of
core-shell BF dust-EAF dust composite pellets were obtained and named C1 , C2 ,
and C3 , respectively. The chemical compositions and reduction indexes of the three
types of metallized pellets are shown in Table 3 and Fig. 6.
Table 3 shows that the total iron content of metallized pellets C1 was much higher
than those of C2 and C3 . The gangue elements, including Ca, Mg, Al, and Mn, and
Table 3 Main chemical compositions of C1 , C2 , and C3 (wt %)

Sample Fe Zn Pb Cr Na SiO2 Al2 O3
C1 68.73 0.392 0.004 0.051 0.833 6.01 3.95
C2 64.04 0.331 0.002 0.036 0.743 5.89 3.50
C3 58.94 0.685 0.003 0.053 0.472 5.53 3.33
Sample MgO S P CaO K Mn C
C1 4.22 0.13 0.18 13.92 0.40 1.41 4.63
C2 3.92 0.11 0.15 11.90 0.32 1.20 3.67
C3 3.74 0.24 0.13 11.65 0.27 1.21 6.76
Fig. 6 Comparison of reduction indexes of C1 , C2, and C3
harmful elements, including Pb, P, K, and Na, were higher than those of C2 and C3 ,
which can be ascribed to the enrichment of those elements caused by the removal
of oxygen and carbon during the reduction. It is noteworthy that the content of Cr
in the metallized pellets was 0.051 wt %, 0.036 wt %, and 0.053 wt %, respectively.
It varied greatly, which was mainly related to the reduction degree of chromium-
containing phases in the composite pellets and to the removal of C, O, Zn, Pb, and
other elements. Figure 6 also shows that the total iron content, iron metallization
degree, removal percentages of zinc and lead and compressive strength of C1 were
higher than those of C3 . Meanwhile, the residual carbon content was lower than that
of C3 .
In fact, the differences between reduction indexes of C1 , C2, and C3 were consistent
with the phase compositions of the metallized pellets. As shown by the XRD patterns
of C1, C2 , and C3 in Fig. 7, C1 was reduced more thoroughly in comparison with
C2 and C3 . It had the strongest iron crystallization and the least impurities. This
observation agreed with the compressive strength values of the metallized pellets in
Fig. 6 because the strength of the metallized pellets is positively correlated with their
metallic iron contents.
578 L. Ye et al.
Fig. 7 XRD patterns of C1 , C2 , and C3
Conclusions
According to the rule of impedance matching, the BF dust-EAF dust composite

pellets with core-shell structure were prepared for microwave-assisted reduction to
produce metallized pellets. All of the BF dust with lower impedance value was
selectively distributed in the pellet core for strong reduction. The EAF dust with
higher impedance value and smaller particle size was divided into two parts. The
first part was distributed in the pellet shell to form impedance matching layer; the
second part was loaded in the pellet core, which could be used together with BF
dust for pelletizing to improve the qualities of green and dried composite pellets.
The results showed that the composite pellets had good mechanical property and
high reduction performance. The total iron content, iron metallization degree, and
compressive strength of the metallized pellets first increased and then decreased
when the proportion of EAF dust in the pellet shell to all EAF dust in the pellet
increased from 0 to 30%. Under the conditions of reduction temperature of 1000 °C,
dwell time of 15 min, and proportion of EAF dust in the pellet shell to all EAF dust in
the pellet of 20%, their maximum values were 68.73 wt %, 95.87%, and 190.4 N/p,
respectively. The removal percentages of zinc and lead were 88.78% and 94.38%,
respectively.
tion of China under Grants 51774337 and 51504297, the Natural Science Foundation of Hunan
Province, China, under Grant 2017JJ3383, the Science and Technology Planning Project of Hunan
Province, China, under Grant 2019RS2008, the Co-Innovation Center for Clean and Efficient Uti-
lization of Strategic Metal Mineral Resources under Grant 2014-405, the Innovation-Driven Pro-
gram of Central South University under Grant 2016CXS021, the Shenghua Lieying Program of
Central South University under Grant 502035001, and the Fundamental Research Funds for the Cen-
tral Universities of Central South University under Grants 2018zzts798, 2018zzts779, 2018zzts220,
2018zzts222, and 2018dcyj056.
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Flow Field in a Continuous Casting
Tundish with a Novel Single-Induction
Heater
Hong Xiao, Shuo Zhang, Jinwen Liu, Guanghui Wu, Haiying Yao,
Haiyan Tang and Jiaquan Zhang
Abstract Tundish with induction heating appliance has been attracting more and
more attention in steelmaking process in recent years. The double induction heater
will occupy a large tundish capacity, which consequently decreases the output of
steel plant. A single-induction heater tundish technology has been put forward in the
present work. Its flow characteristic is studied by water modelling with considering
both non-isothermal and isothermal service situations and compared with that of dou-
ble induction heater. The results show that the flowing consistency between different
strands is a bit weaker with single-induction heater than with double induction heater.
Despite this, the optimized case can completely meet the industrial requirement with
its dead volume fraction 15% and the minimum break time 92 s.
Keywords Tundish with channel type induction heating · Single-induction heater ·

Flow field · Non-isothermal flowing · Temperature difference
Introduction
Tundish is an important metallurgical vessel in the continuous casting process for

distributing molten steel between ladle and mold, promoting the removal of non-
metallic inclusions, and improving the surface and inner quality of castings conse-
quently [1–6]. However, with casting proceeding, the temperature of molten steel
will drop remarkably both in ladle and tundish due to heat loss, which will lead to a
change of casting speed for smooth operation and the instability of fluid flow in the
tundish and mold. To keep steady casting under a given constant temperature, the
H. Xiao · S. Zhang · J. Liu · G. Wu · H. Tang (B) · J. Zhang (B)

University of Science and Technology Beijing, No. 30 Xueyuan Road, Haidian District, Beijing,
China
e-mail: tanghaiyan@metall.ustb.edu.cn
J. Zhang
e-mail: jqzhang@metall.ustb.edu.cn
H. Xiao · H. Yao
Hunan Zhongke Electric Co., Ltd, Yueyang, China
https://doi.org/10.1007/978-3-030-36540-0_52
582 H. Xiao et al.
heating technology of molten steel by plasma gun or induction channel in tundish

has been paid more and more attention in recent years. Under this situation, both the
surface quality and a consistent inner quality can be expected to achieve for cast-
ing products. However, due to the installment of the induction heater, the effective
volume of a tundish will deduce and the flowing characteristics of fluid will vary,
compared with a conventional tundish.
A 7-strand tundish with symmetrical induction heating channel has been in service
in a steel plant of China, which is used to produce high-quality bearing and spring
steels. However, the industrial trails found that the non-metallic inclusions in the
billets of strand 2 and strand 6 are more than other strands, which was suspected to
be the results of irrational tundish structure when adopting the induction channel.
Therefore, a structural optimization was conducted by us and an optimized case
was provided based on the double induction heater. Compared with the prototype
structure, the dead zone volume fraction of the optimized case was decreased by
30.2%, and the average residence time is prolonged by 278 s [7, 8]. To enlarge
the effective volume of the tundish and increase the production efficiency, a single-
induction heater is expected to adopt in this steel plant. Therefore, in the present work,
the structure of this 7-strand tundish with single-induction heater will be optimized
by physical model, and the flow characteristics and behaviors of fluid in it will be
revealed. The research will be beneficial to the application of this innovative vessel
in industry.
For an induction heating tundish, the previous studies have been summarized in
Ref. [8], and are, therefore, not discussed in this paper.
Physical Modelling
Description for Tundish
As described in Ref. [8], an industrial size of 7-strand metallurgical tundish with

induction heating was used as a prototype to design the experimental water model.
Its schematic is shown in Fig. 1.
Fig. 1 Schematic of the tundish [8]

Flow Field in a Continuous Casting Tundish with a Novel … 583
The pouring chamber and discharging chamber are connected by the couple heat-
ing channels, and two heaters are around channels. The molten steel flows from the
pouring chamber into the discharging chamber only through the channels.
According to a similar principle, the geometrical and dynamic similarities need
to be met between the prototype tundish and the model [3]. The experimental scale
factor is taken 1:3. The dynamic similarity condition can be expressed as:
Frm = Frp (1)
where m represents the model of the tundish, p represents the prototype.
u2
Fr = (2)
gL
where u is the flow velocity, g is the acceleration of gravity, and L is the characteristic
length.
Thus, the main geometrical and operation parameters between model and
prototype can be formulated with scale factor λ as follows:
L m /L p = λ, Vm /Vp =λ3 , u m /u p =λ0.5 , Q m /Q p =λ2.5 (3)
where V is the volume of tundish, Q is the volumetric flow rate of the molten steel.
Substituting into the actual operation parameters in the industry into this formula,
Vm and Q m can be obtained.
The motion behavior of molten steel in tundish depends on the natural convection
and forced convection, which are controlled by the buoyancy force and inertia force,
respectively. Therefore, the dimensionless Archimedes number (Ar) can describe the
convection pattern as the ratio of buoyancy force to inertia force [8]. According to
the similarity principle:
Arm = Arp (4)
The Ar is expressed as:
Gr
Ar = (5)
Re2
where Gr is Grashof number, Re is Reynolds number.
gβ L 3 T
Gr =
ν2
uL
Re = (6)
ν
where ν is kinematic viscosity.
584 H. Xiao et al.
Substituting the Eq. (6) into Eq. (5), Ar is obtained as
βgLT
Ar = (7)
u2
where β is the thermal expansion coefficient and T is the temperature difference
of fluid inside and outside the channel.
Substituting βp = 3.9 × 10−4 (1/◦ C), βm = 3.48 × 10−4 (1/◦ C) [5] and the
relationship of L, u between model and prototype in Eq. (3) into Eqs. (4) and (7), the
following formula can be obtained as:
Tm ∼
= 1.12T (8)
Equation (8) is used to calculate the temperature difference of fluid in the model,
corresponding to the inducting heating effect in the prototype.
Experimental Method
As described in Ref. [8], the traditional stimulation-response method was adopted in

the hydrodynamic model with ambient temperature water and heated water. When
the water levels in both ladle and tundish in the hydrodynamic system were stable,
the saturated KCl solution of 75 mL was injected as a pulse tracer at a side port
mounted at the upper position of the ladle shroud; meanwhile, the conductivities of
water at the submerged entry nozzle of 1st to 7th strands were online measured by a
conductivity meter. All the conductivity data were collected by a recorder (DJ800)
and input into a computer to obtain residence time distribution (RTD) curves, and
then these data were further processed to calculate the flow characteristics of the
fluid. Each experiment was repeated three times, and the characteristic parameters
take their average values.
According to Singh’s mixing model of flow [1], the volume fractions of plug flow
Vp , dead zone Vd , and well-mixed zone Vm are determined respectively by:
Vp = (tmin + tpeak )/2ta , Vd = 1 − tf /ta , Vm = 1 − Vp − Vd (9)
where tmin is minimum breakthrough time of tracer, tpeak is peak time, and they are the
average of seven strands. ta is the theoretical mean residence time, which is obtained
by Vm /Q m . tf is the actual mean residence time of the whole tundish, which is also
the average of seven strands. For a specific strand j, its tf, j is determined by:
N
i=1 C j (ti ) × ti
tf, j = N
i=1 C j (ti )
ti ∈ [0, 2ta ] (10)
where C j (ti ) is the molar concentration of tracer measured in this strand at given
time ti .
The flow consistency between strands is expressed by the standard deviation S in
Eq. (11) in this paper:

n
j=1 (x j − x̄)2
S= (11)
n−1
where x j represents the measured value of strand j for certain parameter, x̄ is the
averaged value of seven strands; n is the total number of strands, n = 7. Herein,
the standard deviations Stf , Smin and Speak of the average residence time, minimum
residence time and peak time were calculated, respectively, by the above equation.
To observe the fluid flowing, the ink was added from the position where KCl was
injected in the experiment, and its dispersion was recorded by the camera.
For Non-isothermal Experiments
In industrial operations, when the molten steel flows through the induction channels,
it will be heated by the induction heater. Various heating effects can be obtained by
the given electric powers for temperature control. To observe the effects of induction
heating on the liquid flow, non-isothermal experiments with various temperature
differences of fluid were firstly performed for the prototype tundish with a single-
induction heater, which is characterized by an upward inclined channel of 5º and
300 mm height from the channel export to tundish bottom. The structural schematic is
shown in Fig. 2. For water modeling, various temperatures of hot water were injected
from the channel inlet to simulate its heating effect. The experimental scheme is listed
in Table 1.
Fig. 2 Structural schematics of tundish with single-induction heater

586 H. Xiao et al.
Table 1 Scheme of the non-isothermal experiment

Temperature difference, T (◦ C)
Case P0 P1 P2 P3 P4
Prototype 0 5 10 20 30
Model 0 5.6 11.2 22.4 33.6
The overall characteristic parameters of fluid in the tundish for different cases are
shown in Table 2, and the RTD curve of every strand is illustrated in Fig. 3.
From Table 2, for case P0 (T = 0 ◦ C), tmin is only 35 s, the dead volume
fraction reaches 54.6%, which means that about a half of tundish fluid flows very
slowly. It can be explained by the RTD curves shown in Fig. 3a as follows: both
the peak concentrations C/C 0 of strands 2 and 6 in case P0 exceed 5.0 with a sharp
curve shape, which suggests that most tracers flow directly to outlet 2 and outlet 6,
forming a “short-circuiting flow”. Comparing case P0 with the prototype double-
induction heater case A0 from the reference [8], the dead zone Vd of the former, and
the standard deviations Stf and Speak are all larger than the latter, indicating that the
flow field of the prototype single-induction heater is more unreasonable under the
condition without temperature difference.
For case P1 (T = 5 ◦ C), the overall tmin is 45 s and there is a big difference
among the RTD curves of the seven strands. However, the dead zone fraction of the
tundish is only 3.7%, much lower than that under case P0. With the increase of the
temperature difference, the minimum break time and peak time of cases P2 to P4
are extended obviously and the dead zone disappears. Comparing cases P1 through
P4, the RTD curves of the seven strands become more consistent with the increase
in T , and the standard deviations (S) in Table 2 show a decreasing tendency.
To explain the above phenomena, the ink trajectories of cases P0 and P3 were
illustrated in Figs. 4 and 5, respectively.
For case P0, the black ink first flows along the tilted channel (Figs. 4a). At 78 s,
some ink disperses to the bath surface, while the other directly flows to outlet 2,
forming a “short-circuiting flow”. In this situation, the non-metallic inclusions in the
strand will not have enough time to float up and remove. From Fig. 4c, d, the ink
hardly reaches outlet 4, which is mostly concentrated on both sides of the tundish,
suggesting that the region near outlet 4 is the main source of dead zone. From
Table 2, the Vd reaches 54.6%, occupying more than a half of the tundish volume.
In addition, the St f and Speak are 122.4 and 101.9, respectively, indicating there is a
big flow difference among the seven strands. Therefore, it is necessary to optimize
the inner structure of the prototype tundish with single-induction heater under the
condition of T = 0.
Different from case P0, the ink in case P3 firstly floats towards the bath surface,
following the hot water flow from the channel (Fig. 5a) due to the thermal buoyancy,
which is called an “upward flow”. Then the ink accumulates and spreads out to
the whole liquid surface (Fig. 5b), and no short-circuiting flow is observed in this
process. Owing to density difference, the cold flow will stay at the bottom of the
Table 2 Overall characteristic parameters of flow in non-isothermal experiment cases
Case tmin (s) tpeak /s tf (s) Vd (%) Vp (%) Vm (%) Stf Smin Speak
A0 [8] 38 80 501.27 45.57 6.41 48.02 91.01 61.39 88.15
P0 35 78 483.74 54.58 5.31 40.11 122.4 25.62 101.94
P1 45 671 1026 3.66 33.62 62.72 94.28 171.87 281.51
P2 353 705 1067.48 0 49.67 50.33 36.89 71.25 49.95
P3 401 748 1103.38 0 53.94 46.06 35.31 57.61 74.52
Flow Field in a Continuous Casting Tundish with a Novel …
P4 463 674 1161.74 0 53.38 46.62 23.96 41.00 31.22

587
588 H. Xiao et al.
Fig. 3 RTD curves of the non-isothermal experiment at different ΔT: a case P0, ΔT = 0 °C; b P1,
5 °C; c P2, 10 °C; d P3, 20 °C; e P4, 30 °C
tundish. When the hot flow gathers to a certain degree, however, it begins to sink
gradually as shown in Fig. 5c due to the heat exchange with the cold flow at the
interface. The whole tundish will be filled up with ink in the following time as shown
in Fig. 5d. During this period, the ink undergoes a longer time before reaching each
outlet, thus the tmin is significantly prolonged as compared with case P0. Additionally,
the hot flow can fill up the whole tundish finally, and there is no dead zone observed
in case P3.
Fig. 4 Ink dispersion trajectory in case P0
Fig. 5 Ink dispersion trajectory in case P3

590 H. Xiao et al.
Table 3 Scheme of the

Case Inclination Height of Height of dam
isothermal experiment
angle of channel (mm) (mm)
channel (°)
G1 0 340 0
G2 0 340 340
G3 0 340 420
G4 0 340 500
For Isothermal Experiments
As described in Ref. [8], the T inside and outside the induction channel will
decrease during the overall heating process. Eventually, the temperature difference
will disappear and the molten steel in tundish becomes an isothermal flowing. In
addition, the induction heating operation is usually used for some special steel grades
such as bearing and spring steels for economical consideration. For most conventional
steel grades, the heating function of channels will be kept in a power-off state.
Under this case, the flow of molten steel through the channel is also isothermal.
Therefore, for the structural optimization of a tundish with single-induction heater,
the isothermal experiment of the water model is necessary.
Based on the experience of double-induction heater [8], the case of a single-
induction heater is designed as follows: the induction channel is set as horizontal
one with a height 340 mm away from the tundish bottom. Two dams are designed
at each side of the tundish which is symmetrically distributed between outlets. The
dam1 is located at the position 375 mm to outlet 2, and dam 2 is 240 mm to outlet 3.
The heights of the dams in the experiments are given to be 0, 340, 420, and 500 mm,
respectively, as listed in Table 3. The flow characteristic parameters for the tundish
are presented in Table 4, and the RTD curve of each strand is shown in Fig. 6.
From Table 4, the average residence time of case G1 is increased by 292 s and
the dead zone fraction is decreased by half compared with case P0, indicating that
the elevation of the induction channel is favorable for the improvement of flow field.
However, the induction channel cannot be too high due to the limits of the liquid
surface of the tundish and the residence steel.
Comparing cases G2 through G4, the average residence time prolongs, and the
dead zone fraction and peak concentration decrease with the increase in the dam
height, suggesting that the high dam is beneficial to the optimization of flow field of
this tundish. This is because the fluid flows upwards rather than directly to outlet 2
and outlet 6 under the guide of high dam. Under this situation, the short-circulating
flowing is eliminated. The flowing parameters of case G3 is close to that of case G4,
thus case G3 is believed to be optimal, considering the actual production and the
amount of residual steel.
By the way, it is noted from the RTD curves in Fig. 6, there is a larger flowing
difference among the seven strands as compared with our earlier double induction
Table 4 Overall characteristic parameters of flow in isothermal experiment
Case tmin (s) tpeak (s) tf (s) Vd (%) Vp (%) Vm (%) St f Smin Speak
P0 35 78 484 54.58 5.31 40.11 122.49 25.62 101.94
G1 33 54 776 27.14 4.08 68.78 93.53 62.61 114.92
G2 70 207 803 24.57 13.00 62.42 43.09 27.71 41.39
G3 92 266 896 15.83 16.81 67.36 61.71 39.46 108.50
Flow Field in a Continuous Casting Tundish with a Novel …
G4 110 249 903 15.24 16.85 67.91 69.21 44.57 72.82

591
592 H. Xiao et al.
Fig. 6 RTD curves of the isothermal experiment at different cases: a G1; b G2; c G3; d G4
heating system, which should be the results of the asymmetric geometry of tundish
with a single-induction heater presently.
Conclusions
Flow characteristics for an innovative casting tundish with channel-type single induc-
tion heater are revealed by the water model method, based on isothermal and non-
isothermal working conditions of tundish, and the optimal flow control design is put
forward. The following conclusions are drawn:
Under the non-isothermal situation, the fluid from heating channel flows upwards
directly to the liquid surface, which is potentially favorable for the removal of non-
metallic inclusions in steel. The larger the temperature difference inside and outside
heating channel is, the more obvious upward flow. When the temperature difference
reaches 10 °C, the dead zone of the tundish is wholly eliminated, and the mini-
mum residence time of fluid and average residence time reach 353 s and 1067 s,
respectively, much longer than that under the condition of no temperature difference.
Under the isothermal situation, the elevation of induction channel and the set of
double dams in tundish can reduce the dead zone fraction, and the high dam has
advantage over a low dam. The dead zone fraction of cases G3 and G4 are decreased
from 45.6% in prototype tundish and 54.6% in case P0 to below 16%. Considering
the depth of molten bath and the amount of residual steel in the tundish, case G3
(induction channel height 340 mm, two dams height 420 mm) is the optimal choice
for an actual production.
Acknowledgements This research is financially supported by the National Natural Science

Foundation of China (No.51874033, U1860111) and Beijing Natural Science Foundation (No.
2182038).
References
1. Singh V, Ajmani SK, Pal AR (2012) Single strand continuous caster tundish furniture comparison
for optimal performance. Ironmak Steelmak 39(3):171–179
2. Tang HY, Li JS, Gao JG, Zuo Z (2008) Effect of flow control devices of tundish on cleanliness
of billets. J Iron Steel Res Int 15:499–504
3. Tang HY, Li JS, Yu M, Jiang J (2010) A study on water modeling of gas curtain in a four-strand
tundish. Spec Steel 31(4):1–3
4. Chakraborty S, Sahai Y (1992) Mathematical modelling of transport phenomena in continu-
ous casting tundishes II. Transient effects owing to varying ladle stream temperature. Ironmak
Steelmak 19(6):488–494
5. Jha PK, Rao PS, Dewan A (2008) Effect of height and position of dams on inclusion removal
in a six strand tundish. ISIJ Int 48(2):154–160
6. Tang HY, Yu M, Li JS (2009) Numerical and physical simulation on inner structure optimization
of a continuous casting tundish and its metallurgical effect. J Univ Sci Technol B 31(suppl.1):38–
42
7. Wu GH, Tang HY, Xiao H, Yao HY, Zhang JQ (2017) Physical simulation on a 7-strand
continuous casting tundish with channel type induction heating. Iron Steel 52(11):20–26
8. Tang HY, Guo LZ, Wu GH, Xiao H, Yao HY, Zhang JQ (2018) Hydrodynamic modeling and
mathematical simulation on flow field and inclusions removal in a 7-strand continuous casting
tundish with channel type induction heating. Metals 8(6):374–401
Modification of Inclusions by Adding Mg
to 16MnCrS5 Gear Steel
Hui Liu, Yikui Xie, Qiankun Yang, Qi Zhou and Jie Ma
Abstract The strength, ductility, and cutting performance can be seriously affected
by the size and distribution of inclusions in the steel. Using a high-temperature tube
electric resistance furnace, the effect of Mg addition on the evolution of inclusions in
16MnCrS5 steel was investigated. Besides, the deformation behavior of inclusions
was carried out by a simulated testing rolling mill (Gleeble-3500). The results showed
that the ratio of compound inclusions (MgO·Al2 O3 wrapped by MnS) increased after
Mg addition in steel, and the same trend was obtained in the aspect ratio of inclusion
together with the ability of resisting the deformation of inclusions after hot-extruding.
With the increasing of Mg addition from 8 ppm to 42 ppm, the mean area of inclusions
in experimental ingots first decreased and then increased. Additionally, the peak mean
area of inclusions occurred under the Mg content of 35 ppm.
Keywords Mg treatment · MnS inclusions · Morphology · Relative plasticity
Introduction
16MnCrS5 was a kind of sulfur free-cutting gear steel, and the MnS inclusions in steel
had a great influence on the properties. MnS reduced the cutting force by lubrication
and stress concentration during the cutting process and increased the life of tools. At
the same time, the MnS inclusions could avoid the harmfulness of oxide inclusions
and increase the fatigue life of steel by wrapping [1–3].
At present, Ca treatment was taken to improve the properties of 16MnCrS5 steel.
There are two advantages of Ca treatment [4, 5]: one is Al2 O3 inclusions that can be
converted into low melting point calcium aluminates and the other one is composite
H. Liu (B) · Q. Zhou · J. Ma

School of Materials and Chemical Engineering, Anhui Jianzhu University, 230601 Hefei, People’s
Republic of China
e-mail: liuhui6172@163.com
Y. Xie · Q. Yang
State Key Laboratory of Advanced Special Steel, Shanghai University, 200072 Shanghai, People’s
Republic of China

https://doi.org/10.1007/978-3-030-36540-0_53
596 H. Liu et al.
inclusions of MnS where wrapped oxide can be formed, leading the accelerating
floatation of inclusions and improvement of fatigue life and cutting properties of steel
matrix. However, calcium treatment cannot optimize the morphology of inclusions
and increase the risks of nozzle blockage. Mg treatment had a remarkable effect
on inclusions in steel. Mg could transform agminated Al2 O3 inclusions to fine and
dispersed spinel inclusions [4]. Xiao et al. [6] studied the effect of Mg content on
sulfides in non-quenched and tempered steels, and the results showed that the type
II MnS transformed to type I+III after Mg treatment. The effect of Mg treatment on
sulfide inclusions in resulphurised steel also were studied by Tian et al. [7], showing
that Mg–Al–O oxide inclusions were wrapped by MnS and reduced the amount of
MnS precipitated along grain boundary after Mg treatment.
The evolution of inclusions after magnesium treatment was studied in 16MnCrS5
gear steel. The micro-analysis was taken to acquire the law of inclusions and ana-
lyzed the deformation behavior of inclusions. It provided the research foundation for
improving the quality of 16MnCrS5 gear steel.
Experimental Methods
The experimental material used in this research was a gear 16MnCrS5 steel, the
chemical compositions of samples used in present work were shown in Table 1. The
samples were cut from a casting slab by an electric spark cutting machine and weigh-
ing about 600 g. Subsequently, the grinding treatment of sample surface was applied
to ensure cleanliness. The processed sample was put into the corundum crucible
inside of the experimental device, and the schematic diagram of the experimental
equipment is shown in Fig. 1a. As can be seen below, the tubular resistance furnace
was performed for sample heating and cooling.
The current experimental procedure is presented in Fig. 1b; the sample was heated
up to 1550 °C and holding for 30 min for full-homogenization, then the prepared
nickel–magnesium alloy was added into the liquid steel from the observation window.
In order to homogenize the reaction; a Mo bar was used to stir the liquid steel for
60 s. After that, the oxygen content was measured by an oxygen detector (Leco RO-
416 DR). Finally, the sample was cooled to room temperature in the furnace with
power failure. The addition of nickel–magnesium alloy in the current research was 0,
0.49, 1.04, 1.13, 1.78, and 4.18 g, respectively. After the experimental procedure, the
samples were collected from each ingot. The obtained samples were in size of 14 ×
12 × 10 mm, as shown in Fig. 1c. The hot-processing experiment was used to find
better schemes of Mg addition for modifying the morphologies of the MnS inclusions,
and the experiments were carried out by a simulated testing rolling device (Gleeble-
3500). The content of Mg in each sample was measured by an inductively coupled
plasma emission spectrometer (ICP-OES). The polished sample was characterized
by an optical microscope (Carl Zeiss, A2 m, Germany) and a scanning electron
microscope combined with Energy Dispersive Spectrometer (SEM-EDS) (Phenom,
Pro X, Netherlands). Image-Pro Plus 6.0 software was used to measure the size of
objects.
Table 1 Chemical compositions of specimens used in this work (wt%)
Steel C Si Mn P S Cr Al Ca O Fe
16MnCrS5 0.16 0.16 1.18 0.0065 0.0278 1.023 0.031 0.0012 0.0019 Balance
Modification of Inclusions by Adding Mg to 16MnCrS5 Gear Steel
597
598 H. Liu et al.
Fig. 1 a Schematic diagram of experimental equipment; b experimental procedure and c process

of obtained sample
Detection of Magnesium Addition
Figure 2 shows the morphologies and compositions of inclusions in S0 sample (with-

out Mg treatment). As can be seen, the majority inclusions presented dark gray in
the view of backscatter mode of the SEM, and the EDS analysis indicated that the
inclusions were mainly MnS particles and is rod-like.
Fig. 2 Morphologies and EDS analysis of sample inclusion in gear steel

Modification of Inclusions by Adding Mg to 16MnCrS5 Gear Steel 599
Table 2 Mg content and activity oxygen with different experiments

No. Ni–Mg Alloy (g) Mg content (ppm) Yield rate (%) Activity oxygen (ppm)
S0 0 0 – 17
S1 0.49 8 3.26 15
S2 1.04 13 2.50 13
S3 1.13 19 3.36 13
S4 1.78 35 3.93 9
S5 4.18 42 2.01 8
The MnS precipitated along the grain boundaries in the matrix can improve the
cutting performance of steel, and also can lead the decline of the mechanical proper-
ties of steel [8, 9]. The rod-like MnS distributed along the grain boundaries can lead
the formation of microcracks, which will decrease the fatigue performance of steel
matrix. Therefore, the distribution of inclusions in 16MnCrS5 gear steel after cal-
cium modification needs to be improved. And a more effective modification method,
Mg treatment was adopted in present research to improve the distribution as well as
the morphology of inclusions and mechanical properties of the steel.
The Mg content and activity oxygen in different samples are shown in Table 2. As
can be seen from the table, the yielding rate of magnesium was about 3.00%. Hence,
Mg treatment in the industry is a little difficult to be implemented. The magnesium
was a kind of strong deoxidizing element during steelmaking. The activity of oxygen
in liquid steel decreased with the increasing of Mg content.
Effect of Mg Content on the Morphology of Inclusions
The metallographic observation of the obtained samples with different Mg content

are shown in Fig. 3. As presented in Fig. 3, the inclusions observed in the S0 sample
(without Mg treatment) were the majority of rod-like MnS and distributed along
the grain boundaries in dispersion; a small part of MnS were spherical. Comparing
with the various Mg content samples (S1–S5), it can be found that the percentage of
rod-like MnS inclusions was significantly reduced with Mg addition. The percentage
of MnS precipitated along the grain boundaries decreased and the average size of
MnS inclusions increased with increasing of Mg content. Besides, the distribution
of inclusions tend to disperse uniformly. As evidence in Fig. 3, Mg treatment has a
positive effect on the modification of MnS inclusions in the current steel matrix.
The statistical results were collected from the metallographic observation by using
Image-Pro Plus 6.0 software. Figure 4 shows average area (Aa ) and distribution
density (Dd ) of MnS inclusions under various Mg content (wMg ). As can be seen
from Fig. 4, with the increasing of Mg content, the distribution density of inclusions
first decreases and then increases. And the average area of inclusions shows an
opposite trend compared to Dd . The value of Dd does not change obviously when the
600 H. Liu et al.
Fig. 3 Comparison of inclusions distribution with various Mg addition: a 0 ppm; b 8 ppm; c 13 ppm;
d 19 ppm; e 35 ppm; f 42 ppm
average area and distribution
density of MnS inclusions
wMg is no more than 19 ppm and decreases rapidly when wMg exceeds to 35 ppm.
The number of particles in the same area decreases with the increasing addition of
Mg content, leading the coarsening of MnS inclusions. It was apparent that Aa and
Dd had a reverse trend during the Mg treatment on MnS inclusions.
The size distribution of MnS inclusions in various Mg content samples is shown
in Fig. 5, which shows that most of MnS inclusions in the current steel samples
are within 10 µm2 . Large size inclusions decrease and small ones increase with Mg
content increasing to 19 ppm. The addition of Mg has a significant effect on MnS
inclusions refinement. As the Mg content continues increasing, the size of the MnS
inclusions does not have an obvious refinement effect.
Fig. 5 Comparison of area distribution of inclusions
Effect of Mg Content on the Compositions of Inclusion
The SEM images are shown in Fig. 6. The morphology of typical MnS inclusions
changes with increasing of Mg content. Without the addition of Mg content, the
inclusions are mainly pure MnS and part of them are MnS wrapped oxide inclusions.
With the addition of Mg, the composition of core changed and Mg element was
detected. And the composite oxides were changed from Al–Ca–O inclusions to Al–
Mg–O inclusions. As illustrated in Fig. 6, the size of oxides core increased with Mg
content increasing. And the morphologies of outside wrapped MnS were changed
from irregularity to ellipsoid.
Statistical results on the composition of inclusions are presented in Fig. 7. The
percentage of pure MnS decreased with increasing of Mg content. Meanwhile, the
percentage of MnS wrapped Al–Mg oxides increased with increasing of Mg content,
indicating that the number of inclusion as cores for MnS precipitation increased. With
Mg content of 8–35 ppm, the percentage of composite MnS inclusions was further
increased. A new kind of Mg–Mn–S fine inclusions were collected while the Mg
content reached to 42 ppm, resulting in decreasing of average size and increasing of
number density compared to other samples. The high hardness of precipitated oxides
can lead to a negative effect on the fatigue life of steel matrix [10, 11]. Therefore, the
MnS wrapped oxide inclusions can reduce the deformability of composite inclusions,
meanwhile, improve the cutting performance of the steel matrix.
602 H. Liu et al.
Fig. 6 Morphologies of typical composite inclusions with EDS analysis under various Mg addition:
a 0 ppm; b 8 ppm; c 13 ppm; d 19 ppm; e 35 ppm; f 42 ppm
Fig. 7 Percentage of various

inclusions type
Fig. 8 a Aspect ratio of composite inclusions; b Relative plasticity of composite inclusions
Deformation Behavior of Inclusions in Steel Matrix
The hot processing samples (5 mm in diameter and 10 mm in height) were cut from
experimental ingots. The rolled samples were heated at 5 °C s−1 to 1200 °C and
held for 5 min. Then, the samples were rolled by the Gleeble-3500, and the total
deformation was 60% along the transverse-axis direction. The rolled samples were
cooled to room temperature by air after rolling. Figure 8a shows the aspect ratio
(defined as length/width of, λ) of inclusions after the rolling process. Most of the
MnS inclusions in the sample are spherical (λ ≤ 3), followed by rod-like (3 ≤ λ
≤ 6) and long strips (λ > 6). With the increasing of Mg content, the percentage of
spherical MnS inclusions increases and the opposite trend is obtained in rod-like and
long strips MnS inclusions.
As described above, easy deformation ability of MnS inclusions can lead a neg-
ative influence on the mechanical properties of the steel matrix. The relative plas-
ticity of composite MnS inclusions during the rolling process can be calculated by
Malkiewicz and Rudnik formula [12] as expressed in Eq. (1).
εi 2 ln λ/λ0
v= = × (1)
εm 3 ln h/ h 0
where εi and εm are the true strain of MnS and steel matrix, λ0 and λ are the aspect
ratio of MnS before and after rolling process, h0 and h are the length of the samples
along deformation direction before and after rolling process.
Figure 8b shows the relative plasticity of composite MnS inclusions after rolling
the procedure. It is obvious that the relative plasticity (σ ) of composite MnS inclu-
sions changes along with the content of Mg addition. The value of σ decreases
with Mg content, and the turning point appears when the content of Mg exceeds to
35 ppm. The smaller value of σ means that the composite MnS inclusions have lower
deformability and can lead a better mechanical performance. Besides, the relative
plasticity of composite MnS inclusions shows the same trend with its aspect ratio.
604 H. Liu et al.
In order to reduce the relative plasticity of composite MnS inclusions, the suitable
content of Mg addition should be considered.
Conclusions
The morphologies and size evolution of the MnS inclusions in 16MnCrS5 gear steel
with Mg treatment were investigated in the current work. The percentage of compos-
ite inclusions (MnS wrapped oxide) increased after the addition of magnesium. With
Mg content increasing in the steel matrix, the number density of MnS inclusions first
decreased and then increased, and the opposite trend was obtained on the average area
of MnS inclusions. The relative plasticity of composite MnS inclusions decreased,
meanwhile the spherical composite inclusions increased with Mg addition. And the
suggested content of Mg addition was approximately 35 ppm in the steel matrix.
Acknowledgements This work is sponsored by the National Natural Science Foundation of China
(51874195 and 51671124).
References
1. Wang YN, Bao YP, Wang M, Zhang LC (2013) Smelting process and machinability of BN-type
free cutting steel. J Univ Sci Technol Beijing 35(7):869
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evolution of inclusions during calcium treatment. Metall Mater Trans B 49(2):610–626
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free-cutting steels investigated by nano-indentation measurements. Metall Mater Trans A
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of steel components. J Fail Anal Prev 15(2):169–178
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in free-cutting steel. J Univ Sci Technol Beijing 26(5):471–473
9. Xu J, Yang QK, Cheng J et al (2017) The evolution and thermodynamic analysis of inclusions
in gear steel after magnesium treatment. In: Paper presented at international conference on
manufacturing engineering and intelligent materials, Guangzhou, China, 25–26 February 2017
10. Chiang YM, Kingery WD (1989) Grain-boundary migration in nonstoichiometric solid solu-
tions of magnesium aluminate spinel: i, grain growth studies. J Am Ceram Soc 72(2):271–277
11. Zhang TS, Wang DY, Jiang MF (2014) Effect of magnesium on evolution of oxide and sulphide
in liquid iron at 1873K. J Iron Steel Res Int 21(12):1073–1080
12. Jiang L, Cui K (1997) Quantitative study of modification of sulphide inclusions by calcium
and its effect on the impact toughness of a resulfurised alloy steel. Steel Res 68(4):163–168
Preparation of Transition Metal Nitrides
via Reduction–Nitridation
with Ammonia
Yongjie Liu, Yu Zhang, Zhixiong You and Xuewei Lv
Abstract High-quality transition metal nitrides have been prepared by direct reduc-
tion and nitridation of transition metal oxides with ammonia as reductant and nitrogen
source. The thermodynamics of reduction and nitridation process was initially ana-
lyzed. Then, two kinds of nitrides prepared by the specified process were compared.
The effects of reaction temperature and reaction time on the product quality were
investigated. It was found that the reaction temperature and time had a significant
effect on the reduction and nitridation process. With the increase of reaction temper-
ature and time, the oxygen content was decreased in the product. This method avoids
the introduction of other impurity elements except the negligible trace elements
accompanied with the raw materials. In the meantime, the final product contains
relatively high-nitrogen content and low residual oxygen content. The quality of
the products has been greatly improved and fully meets the standards of industrial
products.
Keywords Transition metal oxides · Nitrides · Ammonia · Reduction · Nitridation
Introduction
Transition metal nitrides have been widely studied for its excellent properties, such
as extreme hardness, high toughness, high-temperature stability, excellent corrosion
resistance, and thermal and electrical conductivity [1–4]. Due to their superior per-
formance, transition metal nitrides have many applications in structural materials,
electric and magnetic components, electrode materials, and industrial catalysts [5, 6].
Y. Liu · Y. Zhang · Z. You (B) · X. Lv

e-mail: youzx@cqu.edu.cn
Z. You · X. Lv
Laboratory of Vanadium-Titanium Metallurgy and New Materials, Chongqing University,
Chongqing 400044, China

https://doi.org/10.1007/978-3-030-36540-0_54
606 Y. Liu et al.
Conventionally, transition metal nitrides have been extensively synthesized by

thermal, mechanochemical, hydrothermal, self-propagating high-temperature syn-
thesis and sol–gel methods under ambient or supercritical conditions. In particular,
vanadium nitride (VN) and titanium nitride (TiN) have been widely concerned for
their excellent physical and chemical properties [7–9]. Among the methods above,
nitrogen sources are usually ammonia, nitrogen, and other nitrogenous organic
compounds. The carbothermic reduction–nitridation method directly uses transi-
tion metal oxide as raw materials, which reduces the production cost and energy
consumption. During the process, although impurities are not introduced, there is
still some residual carbon content in the final product. At the same time, too high-
carbon ratio (C/O) will lead to an increase in the carbon content of products, which
affects the quality of products. The sol–gel method can be used to prepare nitride at
a lower temperature, but the gel contains a large number of liquid phases or pores.
This method tends to cause serious agglomeration of products during heat treatment,
reducing the quality of the nitride. In addition, the high raw material price and the
use of organic solvent limit the popularization and use of this process [3, 7, 10–14].
Zhang et al. [15] and Kim and Kumta [16] prepared nano titanium nitride powder
with a particle size of about 40 nm by direct nitrogen nitridation using a precursor of
nano-titanium dioxide prepared by sol–gel method. The experimental results showed
that the reaction temperature and reaction time have a great influence on the yield
of titanium nitride, and the yield of titanium nitride increases with the increase of
reaction temperature and reaction time. However, the preparation of nano titanium
nitride by the sol–gel method is costly and complicated.
In this study, TiN and FeV45N were prepared using ammonia as a reductant
and nitrogen source. In the meantime, the final product contained only a relatively
high-nitrogen content and low residual oxygen content except the negligible trace
elements of the raw materials. The quality of the products has been greatly improved
and fully meets the standards of industrial products.
Experimental
Materials
The solid powder raw materials for preparing titanium nitride (TiN) and ferric vana-
dium nitride (FeV45N) are anatase (TiO2 , >99.9 wt%), a mixture of vanadium oxide
(VO2 , >99.6 wt%) and ferric oxide (Fe2 O3 , >99.6 wt%), respectively. Theoretically,
the vanadium and nitrogen contents of FeV45N alloy are approximately 45 wt% and
10 wt%, respectively, assuming the alloy is composed of Fe and VN.
Preparation of Transition Metal Nitrides … 607
For preparing titanium nitride, anatase was placed in an alumina crucible and put
into the constant-temperature zone of a horizontal resistance furnace. Similarly, a
mixture of vanadium oxide and ferric oxide were loaded in the crucible for preparing
ferrovanadium nitride. Initially, at the heating stage, a flow of Ar gas (99.999%)
was introduced into the furnace tube to get rid of O2 and H2 O. The flow rate of
Ar gas was kept at about 150 ml/min. When the furnace was heated to the desired
temperature (600–1200 °C) at the rate of 10 °C min−1 , the nitridation reaction of the
raw materials was performed in a tube furnace at a constant heating temperature of
flowing ammonia (NH3 , 99.999%) gas at the flow rate of 150 ml/min. After holding
at the desired temperature for various times (1–8 h), the tube furnace was cooled
down under flowing Ar gas.
After reaction and nitridation, the obtained products were examined by X-ray pow-
der diffraction (Rigaku D/max 2500). Scanning electron microscope (JSM-7800F)
was carried out to monitor overall morphology, and the powders were tested for
oxygen and nitrogen content by the German Eltra On-900N/O elemental analyzer.
The main reactions and their standard Gibbs free energies during reduction–nitrida-
tion process were calculated by FactSage 6.2, as shown in Table 1. The results in
Table 1 indicate that iron and vanadium oxides are capable of being reduced to low
valence oxide as well as forming nitrides. The starting reaction temperature is less
than 800 °C, revealing that the reactions are possible to occur under the experimental
temperatures. It is worthy to mention that Fe4 N formed during the roasting process
is easy to decompose (Eq. 5). Actually, the alloy of FeVN was composed of metallic
iron and VN. Compared to the nitridation reaction of Eq. 7, it can be observed that
TiN is a little difficult to be generated bearing a starting reaction temperature of
773 °C under standard condition. Thermodynamic analysis proved that the reduction
as well as nitridation of transition metal oxides is feasible and the corresponding
nitrides would be formed.
Phase Evolution During Reduction and Nitridation
The phase transformation during the preparation of FeV45N is shown in Fig. 1. As

shown in Fig. 1a under different duration time, after reacting for 1 h, the sample
consisted of V2 O3 , VN, and Fe. It can be concluded that, in this case, the reaction
608 Y. Liu et al.
Table 1 Main reactions and their standard Gibbs free energies

Eq. Chemical equation r G (KJ/mol) Starting reaction temperature
(°C)
1 2NH3 + Fe2 O3 = 2/3Fe3 O4 + 106.47-0.2591T 138
1/3H2 O + N2 + 8/3H2
2 2NH3 + Fe3 O4 = 3FeO + H2 O 167.59-0.2910T 303
+ N2 + 2H2
3 2NH3 + FeO = Fe + H2 O + 123.42-0.2405T 240
N2 + 2H2
4 2NH3 + Fe2 O3 = 1/2Fe4 N + 172.01-0.2890T 322
3H2 O + 3/4N2
5 2NH3 + Fe4 N = 4Fe +3/2N2 123.68-0.2884T 156
+ 3H2
6 2NH3 + VO2 = 1/2V2 O3 + 86.10-0.2382T 88
1/2H2 O
7 2NH3 + V2 O3 = 2VN + 3H2 O 144.00-0.1452T 719
8 2NH3 + TiO2 = TiN + 2H2 O 206.60-0.1975T 773
+ 1/2N2 + H2
Fig. 1 XRD patterns of the products obtained under different conditions: a reaction at 1000 °C for
various reaction times; b reaction for 4 h at various temperatures
time was not sufficient to completely reduce vanadium oxides. With the increase
of reaction time to 4 h, the diffraction peak of V2 O3 disappeared leaving only the
diffraction peaks of VN and Fe. When the reaction time was 6 h, all diffraction peaks
were assigned to VN and Fe. Figure 1b shows the XRD patterns of the Fe2 O3 and
VO2 composite powders after reduction and nitridation at various temperatures for
4 h. When the temperature is in the range of 600–800 °C, a small amount of Fe4 N was
detected in the product. However, as the reaction temperature was increased above
900 °C, the diffraction peaks attributable to Fe4 N disappeared and all the remaining
Fig. 2 XRD patterns of the products obtained under different conditions: a reaction at 1000 °C for
various reaction times; b reaction for 8 h at various temperatures
peaks were VN and Fe. The results indicate that Fe4 N would decompose when the
temperature was above 900 °C.
The phase transformation during the preparation of TiN is shown in Fig. 2.
Figure 2a shows the XRD patterns of the Ti(N,O) composite powders obtained at
1000°C after reacting for 1 h, 3 h, 5 h, and 8 h, respectively. Among them, Ti(N,O)
is a solid solution of TiN and TiO, indicating that a certain amount of oxygen was
contained in TiN. Similarly, the same situation exists in VN. Compared with the
sample reacted at 1000 °C for 3 h, TiO2 (rutile) was present in the sample reacted at
1000 °C for 1 h, indicating that the reaction was carried out more thoroughly with the
extension of reaction time. When the reaction time was prolonged to 3 h, the diffrac-
tion peak of rutile TiO2 disappear, and only Ti(N,O) phases could be detected. It can
be seen from Fig. 2b that the diffraction peaks in the sample were only Ti(N,O) after
reacting for 8 h in the range 900–1200 °C, and as the reaction temperature increased,
the peak strength of Ti(N,O) intensified significantly.
In order to more clearly explain the effect of reaction time and temperature on the
products, the lattice parameters and nitrogen–oxygen content of TiN under different
reaction conditions are compared in Table 2. As can be seen from Table 2, with the
extension of the reaction time, the cell parameters of the sample gradually increase,
Table 2 Lattice parameters and N, O contents of samples obtained under various conditions
Temperature (°C) Reaction time (h) Lattice parameter (Å) TiNx O1–x
1000 3 4.20874 ± 0.001125 TiN0.54 O0.46
1000 5 4.21416 ± 0.000379 TiN0.62 O0.38
1000 8 4.21983 ± 0.001403 TiN0.71 O0.29
1100 8 4.22857 ± 0.001026 TiN0.85 O0.15
1200 8 4.23443 ± 0.000332 TiN0.94 O0.06
610 Y. Liu et al.
which approach its theoretical value of 4.241 Å. It can also be seen that the O
content of Ti(N,O) in the product gradually decreases, while the N content gradually
increases, correspondingly. Meanwhile, increasing reaction temperature was also
favorable to nitridation by decreasing the O content.
Morphological Analysis
The micromorphology of the products obtained under different reaction conditions

was investigated by scanning electron microscope (SEM), and the results are plotted
in Fig. 3. It can be seen from Fig. 3a that when reducing 800 °C for 4 h, the powder
particles of the reduced samples were accumulated. The bright phase and the gray
phase were mainly Fe and VN, respectively, and these two phases had a certain
connection. By reducing at 1000 °C for 6 h, the powder particles of the samples
accumulated to larger size and showed obvious sintering phenomenon, as shown in
Fig. 3b. Figure 3c and d shows the SEM photographs of titanium nitride obtained with
the reaction time of 8 h at 1100 °C and 1200 °C, respectively. When the temperature
was 1100 °C, particle agglomeration was evident forming larger particles by grain
bonding. Compared with Fig. 3c, the results in Fig. 3d shows that the phenomenon
Fig. 3 Micro-morphology of the products obtained under different reaction conditions: a Fe45VN
at 800 °C for 4 h; b Fe45VN at 1000 °C for 6 h; c TiN at 1100 °C for 8 h; d TiN at 1200 °C for h
Table 3 Results of O and N

Reaction Reaction O content N content
contents of FeV45N
temperature time (h) (%) (%)
(°C)
900 4 1.11 11.75
1000 4 0.74 11.79
1000 6 0.25 11.85
of particle agglomeration was more obvious as the temperature was increased to

1200 °C.
Characterization of the Products
In order to determine whether the prepared sample meets commercial application

standard, the sample needs to be tested for oxygen and nitrogen contents. The equip-
ment used in the experiment was the German Eltra On-900N/O elemental analyzer.
The sample is heated and fused in an ink crucible. The oxygen in the sample reacts
with carbon to form carbon monoxide, and nitrogen is released in the elemental state.
Table 3 shows the experimental results of nitrogen and oxygen contents of FeV45N
prepared under different conditions. It can be seen from Table 3 that as the reaction
time and the reaction temperature increase, the O content of the product decreases
and the nitrogen content increases, correspondingly. After reacting at 1000 °C for
6 h, the O content was as low as 0.25%, and the N content was increased 11.85%,
which had reached the requirement of FeV45N that the element content of N was
not less than 9%.
Table 4 shows the oxygen content of the sample which was reacted at 1200 °C
for 8 h. It can be seen that compared with the purchased pure TiN sample (purity
99.5%) of Aladdin, the oxygen content of the experimental sample is a little higher
than that of the commercial product. However, according to different application
fields of TiN, the sample obtained from the experiment conditions meets industrial
application value in coating materials.
Table 4 O content of
Samples O content (%)
samples under different
conditions Pure TiN (99.5%) 0.31
Reducing at 1200 °C for 8 h 0.51
612 Y. Liu et al.
Conclusions
High-quality nitrides including FeV45N and TiN can be prepared using ammonia
as reductant and nitrogen source. Thermodynamic analysis proved the feasibility
by reduction and nitridation with ammonia. The effects of reaction time and tem-
perature on the preparation of titanium nitride powder were also discussed. It was
found that the reaction temperature and time had significant effect on the reduction
and nitridation process. With the increase of reaction temperature and time, the oxy-
gen content was decreased gradually in the product. The maximum nitrogen and
minimum oxygen content of FeV45N reached 11.85% and 0.25%, respectively, by
roasting at 1000 °C for 6 h. Based on the same process, a TiN product with oxygen
content of 0.51% was obtained by reducing TiO2 at 1200° for 8 h. The quality of the
products meets the standards of industrial products.
Acknowledgements The authors wish to express their thanks to the National Key R&D Program
of China (2018YFC1900500) and Project supported by the Fundamental Research Funds for the
Central Universities (2018CDQYCL0026) for the financial support of this research.
References
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Opin Solid State Mater Sci 1(2):241–249
3. Huang HH, Hon MH (2002) Effect of N2 addition on growth and properties of titanium nitride
films obtained by atmospheric pressure chemical vapor deposition. Thin Solid Films 416(1–
2):54–61
4. Pierson HO (1996) Handbook of refractory carbides and nitrides: properties, characteristics,
processing and applications. William Andrew, New York, p 224
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metal nitrides and applications. Prog Mater Sci 70:50–154
6. Joshi UA, Chung SH, Lee JS (2005) Low-temperature, solvent-free solid-state synthesis of
single-crystalline titanium nitride nanorods with different aspect ratios. J Solid State Chem
178(3):755–760
7. Fix R, Gordon RG, Hoffman DM (1993) Chemical vapor deposition of vanadium, niobium,
and tantalum nitride thin films. Chem Mater 5(5):614–619
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of vanadium nitride. J Eur Ceram Soc 30(10):2099–2107
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P, Mitlin D (2011) High rate electrochemical capacitors from three-dimensional arrays of
vanadium nitride functionalized carbon nanotubes. J Phys Chem C 115(49):24381–24393
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titanium carbonitride. US. Patent 417,952. 23 May 1995
11. Hou X, Qiu P, Yang T, Chou KC (2014) Synthesis of titanium nitride nanopowder at low
temperature from the combustion synthesized precursor and the thermal stability. J Alloy
Compd 615:838–842
12. Zhao D, Cui Z, Wang S, Qin J, Cao M (2016) VN hollow spheres assembled from porous
nanosheets for high-performance lithium storage and the oxygen reduction reaction. J Mater
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a reductant and nitrogen source. JOM 70(11):2493–2498
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nanostructured titanium nitride. Mater Sci Eng B 98(2):123–134
Part VIII
Sintering and Pelletizing
Evaluation of the Liquid Phase Fluidity
During Iron Ore Sintering
Huaiying Ma, Zhixing Zhao, Yue Xin, Shuhai Ou and Wen Pan
Abstract The liquid phase fluidity of iron ores reflects the effective bonding range
in the binder phase. It is usually evaluated by a liquid fluidity index, which increases
with the liquid amount and decreases with the liquid viscosity. The liquid fluidity
index compares the area growth rate of iron ore sample before and after melting. Other
parameters such as the liquid flowing time also have an important impact on the liquid
phase fluidity. The composite liquid fluidity index is proposed to characterize liquid
phase fluidity of iron ore. The composite liquid fluidity index is calculated from
area growth rate, initial melting temperature, liquid flowing time, heating rate and
maximum temperature. Compared with liquid fluidity index, the composite liquid
fluidity index is better suited as a means to evaluate the liquid fluidity of iron ores
and predict the liquid fluidity of iron ore by its chemical composition.
Keywords Liquid fluidity · Iron ores · Composite liquid fluidity index · Liquid
flowing time
Introduction
Sinter is produced by thermal agglomeration of iron ore fines, fluxes, and coke. The
quality and yield of sinter are determined mostly by the properties of iron ore fines.
The melts generated in the sintering process play an important role in determining
the mineral components and the strength of sinter. Thus, a significant amount of
research has been carried out to study the behavior of the melts, and especially the
melt fluidity [1–4].
The liquid fluidity index, which is calculated by an area growth rate before and
after melting of a compressed tablet of calcium oxide and iron ore powder, has been
widely used to evaluate the liquid phase fluidity of iron ore. But it does not consider
H. Ma (B) · Z. Zhao · W. Pan

Research Institute of Technology, Shougang Group Corporation, Beijing, China
e-mail: captainma@163.com
Y. Xin · S. Ou
Beijing Shougang Co., Ltd, Beijing, China
https://doi.org/10.1007/978-3-030-36540-0_55
618 H. Ma et al.
other important melting process parameters, such as initial melting temperature and
flowing time.
Evaluation of liquid phase fluidity using devices similar to horizontal tube fur-
nace has also been attempted [5–7]. Some of the characteristic points measured and
defined by the sample height or profile include the deformation temperature (TD ),
the complete liquid phase formation temperature (TH ), the free-flowing temperature
(TF ) [8], liquid forming temperature (LFT), and inflexion temperature (IT) [7]. The
methods for defining these characteristic points based on height or profile are not
intuitive and differ from each other.
In the present study, the entire process of melting iron ore was tested and recorded
by a vertical electrical resistance furnace equipped with a CCD video. Some impor-
tant points were determined to analyze the melting characteristics of iron ores. The
composite liquid fluidity index was proposed aiming to evaluate the melting process
of iron ore comprehensively and accurately.
Experimental
Figure 1 shows the schematic diagram of the experimental apparatus. The stationary
sample is heated and cooled by moving the vertical electrical resistance furnace down
and up. The heating rate of the iron ore sample is adjusted by the speed at which
the furnace moves. The partial chemical compositions of the seven iron ore samples
used in the present study are listed in Table 1.
The experiment was carried out as follows: first, the iron ore samples were dried
for 2 h at 105 °C and then ground and sieved. Particles smaller than 149 µm were
used in the experiments. An 0.8 g mixture of iron ore and calcium oxide (CaO) was
compressed at 10 Mpa to form a single 8 mm diameter tablet. In order to ensure
Fig. 1 Schematic diagram CCD camera

of experimental apparatus
Stand
Computer Heating
furnace
Thermocouple
Tablet
Disk
Alumina tube
Evaluation of the Liquid Phase Fluidity During Iron Ore Sintering 619
Table 1 Partial chemical compositions of iron ore samples (mass%)

Ore TFe FeO SiO2 Al2 O3 CaO MgO LOI
A 64.8 0.70 1.97 1.68 0.12 0.10 3.01
B 68.1 28.5 3.96 0.51 0.31 0.50 −2.51
C 60.3 0.42 4.43 2.28 0.56 0.16 5.77
D 58.2 0.22 4.44 1.58 0.16 0.10 10.34
E 59.8 0.26 5.73 2.79 0.10 0.083 5.48
F 58.6 0.35 9.74 2.37 0.11 0.19 3.62
G 63.2 0.42 5.10 2.39 0.19 0.092 1.30
sufficient liquid formation during the sintering process, the basicity of the mixture
was established at 4.0 in this study. The tablet was placed in the center of a smooth
alumina disk. The disk and the tablet were placed on the alumina tube and sintered in
air according to a pre-set heating curve as depicted in Fig. 2. The tablet was sintered at
a maximum temperature of 1573 K for 4 min. Once the tablet was cooled to 1273 K,
the furnace moved up quickly and left the tablet cooling at room temperature.
The melting process was recorded by capturing a sample image per second. And
each image was analyzed by ImageJ software to obtain the vertical-projected area
of the tablet. Some critical images of the tablet were listed in Fig. 3. Generally, the
iron ore sample undergoes several processes, such as expansion Fig. 3b, shrinkage
Fig. 3c, melting Fig. 3d, flowing Fig. 3e, and cooling Fig. 3f.
The curve of the vertical-projected area of the tablet is listed in Fig. 4. The liquid
fluidity index (η) was calculated according to Eq. (1).
1600 1573
1400 1423 1423

1273 1273
1200
Temperature/K
1000
873
800
600 Natural cooling
400
200
0 200 400 600 800 1000 1200 1400

Time/s
Fig. 2 Heating curve used in the experiment

620 H. Ma et al.
Fig. 3 Images and the relative diameters of the tablets following sintering at 298 K a1370 K,
b1573 K, c, d, e, and 1273 K (f)
100000
80000
Area/pixel
60000
40000
20000
1202 1572 1575 1313

Temperature/K
Fig. 4 Vertical-projected area of the tablet
η = Aafter − Abefore /Abefore , (1)
where Aafter is the vertical-projected area after experiment (pixel), and Abefore is the
vertical-projected area before experiment (pixel). Two characteristic temperatures
were identified by observing the change in the appearance of the tablet: the liquid
phase formation temperature (TL ) and the free-flowing temperature (TF ). The liquid
phase formation temperature is the temperature when the liquid phase first appears,
and the free-flowing temperature is the temperature at which the liquid phase area is
90% of Aafter . Also, t which represents the time between TL and TF is defined as the
liquid flowing time.
The thermodynamic calculations were performed using the commercial software

FactSage 7.0. The existence forms of Fe in the iron ores are converted to Fe2 O3 on
the basis of proportion of TFe.
The liquid amount, computed by FactSage, and Aafter , are shown in Fig. 5. The
liquid amount ranges from 39.4 to 98.2%, and Aafter tends to increase with the liquid
amount. Ore E shows a different trend with other iron ores in Aafter and the liquid
amount. Compared to ore F and ore G, the lower Aafter of ore E is caused by its thicker
liquid cake after sintering. High Al2 O3 content which increases the liquid viscosity
is suspected to be the reason for the thick liquid cake of ore E.
Table 2 shows the properties of liquid formation during sintering of the iron ore
samples. A considerable difference exists between the liquid fluidity. The liquid
fluidity index of the liquid of the iron ore samples has a rank of A > B > C > D > E
> F > G. Ore A takes the shortest time as 99 s, whereas ore G takes a flowing time
of 261 s. For ore G, the long flowing time may be caused by its liquid amount which
is almost 2.2 times greater than that of ore A. However, no relationship is apparent
between the flowing time and the liquid amount. Flowing takes a long time with ore
B, which has a small liquid fluidity index; the iron ore type (magnetite) and its high
density are suspected to be the reason for the long flowing time and a small liquid
fluidity index.
Ore B was mixed in equal proportions with Ores C, D, and, E, respectively. The
liquid flowing times of the three mixtures are shown in Fig. 6. In each case, the liquid
14
area
Liquid amount 100
12
10
Aafter /10000 pixels
Liquid amount/
80
8
6
60
2 40
0
A B C D E F G
ore
Fig. 5 Liquid amount and Aafter of seven iron ores

622 H. Ma et al.
Table 2 Properties of liquid formation in the iron ore samples

Ore η TL (K) TF (K) t (s)
A 0.62 1573 1552 99
B 2.20 1573 1557 256
C 3.79 1573 1573 203
D 4.00 1573 1573 189
E 4.21 1573 1573 222
F 4.41 1573 1573 170
G 5.31 1573 1551 261
300
Single
Mixture B+E
250
B+C B+D
200
Time/s
150
100
50
0
B C D E
Ore
Fig. 6 Liquid flowing time of different cases
flowing time increased to approximately 250 s, which was almost the same as that
of ore B. The liquid flowing time of iron ore mixture seems to be determined by the
iron ore with long liquid flowing time. The variation in the liquid flowing time of
single iron ore and iron ore mixtures indicates that the liquid flowing time should be
considered when evaluating the liquid fluidity of iron ore.
In order to fully characterize the liquid fluidity characteristics of iron ores, a
composite liquid fluidity index F, was calculated according to the following equation:
η(Tm + (Tm − TL ))
F= (2)
vt
F
16
12
0
A B C D E F G
Ore
Fig. 7 Composite liquid fluidity index (F) and liquid fluidity index (η) of seven iron ores
where Tm is the maximum temperature used in the heating curve, TL is the initial
melting temperature, t is the flowing time of the liquid, and v is the heating rate
between 1423 K and Tm .
Comparison of the composite liquid fluidity index (F) and the liquid fluidity index
(η) of seven iron ores is shown in Fig. 7. Clearly, η increases from iron ore A to iron
ore G, whereas F decreases in iron ore E and G. The decreases in F of iron ore E and
G are caused by the greater growth rate of t than that of η.
Liquid viscosity is another important factor that affects the liquid fluidity. Both
the liquid amount and the liquid viscosity are determined by the composition of
iron ore. The content of SiO2 in the iron ore is known to affect the liquid amount
significantly [9]. And, viscosity is reported to depend on the contents of Al2 O3 and
SiO2 [10]. The correlations of Al2 O3 + SiO2 content and F, η of seven tested iron
ores are shown in Figs. 8 and 9. Approximate linear relationships between Al2 O3
+ SiO2 content and F, η are also illustrated. The Adj. R-Square of Al2 O3 + SiO2
content and F is higher than that of Al2 O3 + SiO2 content and η, which means F has
a higher fitting degree with Al2 O3 + SiO2 content than η. It would be more suitable
to use F instead of η to evaluate the liquid fluidity of iron ores and make a prediction
of the liquid fluidity of iron ores through chemical composition.
624 H. Ma et al.
F
16 Linear Fit of F
12
y=2.14x-1.91
Adj.R-Square=0.81
F
0
0 2 4 6 8 10
SiO2+Al2O3/
Fig. 8 Correlation between Al2 O3 + SiO2 content and F
Linear Fit of
4
y=0.65x-0.32
Adj.R-Square=0.53
0
0 2 4 6 8 10
SiO2+Al2O3/
Fig. 9 Correlation between Al2 O3 + SiO2 content and η

Conclusions
The following conclusions were formed based on the study results:

(1) In addition to the liquid amount, the liquid flowing time during sintering of
different iron ores is also significantly different. The liquid flowing time should
be considered when evaluating the liquid fluidity of iron ore.
(2) The composite liquid fluidity index includes key parameters such as heating
rate, maximum temperature, initial melting temperature and the liquid flowing
time. Compared with liquid fluidity index, it has a higher fitting degree with the
components of Al2 O3 and SiO2 which affect the liquid amount and the liquid
viscosity.
Acknowledgements The authors gratefully acknowledge support from National Key R&D
Program of China (2017YFB0304300 & 2017YFB0304302).
References
1. Kasai E, Omori Y (1993) Subjects on the evaluation of process and products in the sintering
of iron ore. Tetsu Hagane 79(11):1217–1223
2. Wu SL, Liu Y, Du JX (2002) New concepts of the fundamental high temperature properties of
iron ores. J Univ Sci Technol B 24(3):254–257
3. Kasai E, WU SL, Omori Y (1991) Factors governing the strength of agglomerated granules
after sintering. ISIJ Int 31(1): 17–23
4. Jin MF, Li GS, Jiang X (2008) Effect of penetration behavior of calcium ferrite melts into
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iron ore powder during sintering. J Iron Steel Res 23(6):13–18
6. Wu K, Shen W, Du RL (2015) Establishing the characteristic number equation about liquid
phase fluidity of iron ore powder during sintering. J Chongqing Univ 38(5):26–31
7. Li HG, Zhang JL, Pei YD (2011) Melting characteristics of iron ore fine during sintering
process. J Iron Steel Res Int 18(5):11–15
8. Yao L, Ren S, Wang XQ (2017) Study on liquid phase formation and fluidity of iron ores.
Metall Res Technol. https://doi.org/10.1051/metal/2016062
9. Peng J, Zhang L, Liu LX (2017) Relationship between liquid fluidity of iron ore and generated
liquid content during sintering. 48(1):538–544
10. Machida S, Nushiro K, Ichikawa K (2005) Experimental evaluation of chemical composition
and viscosity of melts during iron ore sintering. ISIJ Int 45(4):513–521
Magnetite Carbon-Free Sintering Process
Based on Electromagnetic Induction
Xuangeng Zhou, Xuewei Lv, Zhongci Li, Mingrui Yang, Gang Li,
Zihang Deng, Yongda Li and Linpei Li
Abstract The existing sintering process is to add a certain proportion of water to the
sintering raw materials such as iron ore powder, coke powder, and quicklime. After
mixing and pelletizing, the raw materials are sintered on the pallet train to cause a
series of high temperature physical and chemical changes. Existing sintering pro-
cesses have high energy consumption and high pollution. In order to reduce energy
consumption and pollution in the existing sintering process, it was developed as
Magnetite carbon-free sintering process based on electromagnetic induction. Com-
pared with the existing sintering process, this new magnetite sintering process could
achieve high thermal efficiency, with no coke added. It could reduce pollutant emis-
sion, e.g. COX, NOX, SOX. etc., decreasing energy consumption and return fines
rate. In this study, we focus on the influences of iron powder’s addition amount, insu-
lation time, insulation temperature, and heating power on sinter, and we will evaluate
its performances by using the mineral phase composition of sinter, XRD analysis,
compressive strength, and other indicators. Moreover, we find that this new sintering
process can achieve better metallurgical properties and mechanical strength.
Keywords Carbon-free sintering · Electromagnetic induction · Energy and

emission reduction
Introduction
The definition of the sintering process can be summarized as follows: it refers to the
various powdery iron-containing raw materials, which are matched with a certain
amount of fuel and flux as required, uniformly mixed and granulated, and then clothed
X. Zhou · X. Lv (B) · Z. Li · M. Yang · G. Li · Z. Deng · Y. Li · L. Li

College of Materials Science and Engineering, Chongqing University, 400044 Chongqing,
e-mail: lvxuewei@cqu.edu.cn
X. Zhou · X. Lv · Z. Li · M. Yang · G. Li
University, 400044 Chongqing, People’s Republic of China

https://doi.org/10.1007/978-3-030-36540-0_56
628 X. Zhou et al.
to the sintering equipment for ignition and sintering; the fuel combustion produces
a high-temperature zone and high temperature. A series of physical and chemical
reactions occur in the zone. Some of the fusible materials in the mixture soften
and melt, producing a certain amount of liquid phase, and the liquid phase material
wets other not melted ore particles; the high-temperature zone continuously draws
negative pressure under the action of suction [1–3]. Existing sintering processes
have problems such as large energy consumption for sintering and large pollutant
emissions. Energy consumption problems and environmental pollution problems
have attracted the attention of steel companies [4]. It can be seen that it is increasingly
important to advocate energy conservation and emission reduction.
In recent years, in view of the shortcomings of the existing sintering process, schol-
ars have carried out different research to develop new fields of sintering technology.
Sun supposed that strengthening sintering is a new process for producing alumina,
which has certain advantages over the traditional sintering method. He compares the
traditional sintering method with the intensified sintering method in theory, briefly
describes the difference between the traditional sintering method and the intensified
sintering method in the working principle and technical characteristics, and compares
the traditional sintering method [5]. Hu Bing studied the pre-reduction sintering tech-
nology. It is suggested that as a blast furnace burden,pre-reduction sinter possesses an
apparent advantage of saving energy, improving quality, and increasing production
because of its unique product performance and structural characteristics. Therefore,
it has been highly valued by the domestic and international steel industry, and a series
of basic research work has been carried out by researchers. However, because of the
unreasonable structure of material layer, re-oxidation, over melting, and difficult to
treatment of high CO flue gas, the industrial application is harder to implement.
In order to solve aforementioned problems, a flue gas recirculation pre-reduction
sintering process has been developed which makes the industrialization of this new
technology possible [6]. Ren Wei of Chongqing University studied the microwave
external field sintering of magnetite, mainly from the quality, protective atmosphere
(N2 ) and Fe3 O4 added amount to the magnet concentrate microwave burning [7, 8].
At present, in the field of sintering, for the problems of high energy consumption and
high pollution, some scholars have focused their research on external field sintering.
In this study, we introduced electromagnetic induction and pre-compression technol-
ogy, which can achieve the following advantages: (1) reduce energy consumption;
(2) use carbon-free sintering technology, green and environmentally friendly, reduce
pollution gas emissions; (3) using pre-compacting technology, the powdering rate is
low, and the return fines rate is reduced.
Induction heating (IH) provides contactless, fast, and efficient heating of conduc-
tive materials. It is becoming one of the preferred heating technologies in industrial,
domestic, and medical applications, among other applications, due to its advan-
tages when compared with other classical heating techniques such as flame heating,
resistance heating, or traditional ovens or furnaces [9–12].
Among the advantages of IH, the following ones are commonly recognized [13–
15]: generation of heat sources inside the workpiece to be heated in very short times;
energy savings; improvement of workplace operating environment; high production
Magnetite Carbon-Free Sintering Process … 629
rates, due to the possibility of using high power densities and to realize very short
heating times, thus leading to reduction of labor costs; rational use of electrical
energy for heat generation, also in some processes where it substitutes fuel heating.
Induction heating can be conducted at high rates from 100 to 1400 °C min−1 . As the
alternating current is switched off, cooling of the induction sintered samples occurs
at 500–600 °C min−1 [16, 17].
The role of coke powder in the sintering process is mainly combustion exotherm,
providing the heat required for sintering. This process not only consumes a lot of
coke, but also produces a large amount of sulfur and carbon oxides in the sintering
process [18]. We hope that sintering can be carried out by induction heating to reduce
the use of coke powder and achieve energy saving and emission reduction. Induc-
tion sintering was suggested as a less costly process compared with conventional
sintering [19], as the induction units are smaller, simpler, and easier to maintain than
conventional sintering furnaces. Induction heating uses the principles of electromag-
netic induction and metal thermal effects. The induction heating furnace generates
an induced eddy current by applying an alternating magnetic field, and the metal
conductor generates heat by the presence of electric resistance to achieve heating,
and is a heating method that can generate heat from the inside of the heating medium.
Experimental
Raw Materials
Raw materials include vanadium–titanium magnetite, iron powder, quicklime, cal-

cium ferrite. The vanadium–titanium magnetite is from the Panxi area, and the sample
composition table is shown in Table 1. Quicklime is analytically pure. Calcium fer-
rite was prepared by laboratory and prepared according to n(Fe2 O3 ):n(CaO) = 1:1.
The preparation process of calcium ferrite is shown in Fig. 1. The purity of the iron
powder is above 90%.
Experiment Methods
In this study, based on the principle of electromagnetic induction heating, the exper-
iment of sintering vanadium–titanium with iron powder was first tested accordingly.
Under conditions of basicity of 1.7, 2.1 and 2.5, respectively, the magnetite was
added with calcium oxide and calcium ferrite sintering experiments, and the related
tests were also carried out. The experimental scheme is shown in Tables 2 and 3.
The experiment includes raw material preparation, induction sintering, analytical
testing, etc. First, the sintering raw materials are weighed, mixed, and pre-compacted.
Next, the pressed raw material is placed in an electromagnetic induction furnace for
630
Table 1 Vanadium–titanium magnetite composition (%)

Items TFe CaO FeO SiO2 MgO Al2 O3 S V2 O5 TiO2
Components 56.66 0.448 34.09 3.74 3.57 3.64 0.374 0.719 10.39
X. Zhou et al.
Fig. 1 Flow chart of preparation of calcium ferrite
Table 2 Exploring the experimental scheme of the effect of iron powder on sintering experiment
Holding time Holding Magnetite Iron powder Basicity CaO addition
(min) temperature addition (g) addition (g) amount
(°C)
1 10 1200 40 0 2.5 3.722
2 10 1200 36 4 2.5 3.205
3 20 1200 40 0 2.5 3.722
4 20 1200 36 4 2.5 3.205
Table 3 Induction sintering experimental scheme under three basic conditions

No. Basicity Magnetite CaO amount No. Basicity Magnetite CF addition
addition addition amount
1 1.7 40 2.36 4 1.7 40 9.09
2 2.1 40 2.96 5 2.1 40 11.38
3 2.5 40 3.56 6 2.5 40 13.69
sintering. The heating rate of the induction furnace is changed at any time, and the
heating rate can be controlled by adjusting the opening degree. It takes about 500 s to
raise the temperature from room temperature to 1200°, and it takes about 540 s to rise
to 1250°. Lastly, the sample is air-cooled by XRD analysis, microscopic observation,
and compressive strength test. The experimental process is shown in Fig. 2.
Fig. 2 Experimental flow chart

632 X. Zhou et al.
XRD Phase Analysis
Figures 3 and 4 show the XRD analysis of the sintered ore with the addition of iron
powder. It can be seen from Fig. 3 that the main phases are Ti-magnetite, ferrous
oxide and perovskite. Since the formation of the ideal binder phase calcium ferrite
in the sintered ore needs to participate in the formation of Fe2 O3 , Fe3 O4 cannot
directly react with CaO to form calcium ferrite. Therefore, the characteristic peak
of calcium ferrite is not detected in the XRD results, and the sintering oxidation
is also reflected. The titanium magnet mineral phase is retained after the sintering
process. Since titanium in vanadium–titanium magnetite is mainly in the form of
Fig. 3 XRD—No iron powder added
Fig. 4 XRD—iron powder added

Fig. 5 Magnetite with calcium ferrite XRD results
ilmenite (FeTiO3 ), it reacts with quicklime to form perovskite and ferrous oxide
during sintering, which explains the existence of perovskite and ferrous oxide in
XRD result’s reason. As shown in Fig. 4, the main phase of the iron powder sample is
ferrous oxide, perovskite, magnetite, and iron powder. The iron powder has a thermal
effect in the induction sintering process, which provides a part for the sintering of
vanadium–titanium magnetite. At the same time, the iron powder acts as a reducing
agent and reacts with the magnetite to form ferrous oxide. Due to the limited sintering
time, some iron powder remains in the sample, which can be confirmed by mineral
phase microscopy. In the observation of the ore phase, a small amount of calcium
ferrite was observed, and in the XRD analysis, the formation of calcium ferrite was
not detected, probably because the amount generated was small.
Figures 5 and 6 are XRD patterns of vanadium–titanium magnetite with calcium
ferrite and calcium oxide in the case of R = 1.7, R = 2.1, and R = 2.5. From the XRD
pattern obtained, the maximum number of characteristic peaks is Fe3 O4 , followed
by CaTiO3 . The XRD pattern shown in Fig. 5 has more CaTiO3 than that shown in
Fig. 6. In addition, a small amount of characteristic peaks of CF, C2 F, and FeO were
also found.
Microstructure Analysis of Sample Ore Phase
Figures 7, 8, 9, 10, 11, and 12 show the results of sinter ore phase obtained by
adding calcium oxide and calcium ferrite to magnetite under three different alkalinity
conditions of R = 1.7, R = 2.1, and R = 2.5. From Figs. 7, 8, 9, 10, 11, and 12, it
634 X. Zhou et al.
Fig. 6 Magnetite with calcium oxide XRD results
Fig. 7 R = 1.7 Mineral structure of magnetite with calcium oxide sample
Fig. 8 R = 1.7 Mineral structure of magnetite with calcium ferrite sample

can be seen from the microscopic mineral phase structure diagram that the mineral
phase composition is mainly magnetite, and the crystal plane is porous. The mineral
phase results show that CF, C2 F, and hematite exist, and the Fe3 O4 in the sinter is
silicate cemented.
636 X. Zhou et al.
In the above microscopic mineral phase structure diagram: H: hematite; M:

magnetite; CF: calcium ferrite; C2 F: dicalcium ferrite; S: vitreous; K: hole
Conclusions
(1) X-ray diffraction analysis and sinter mineral phase analysis show that CF can
also be generated by electromagnetic induction sintering technology to improve
the strength and reduction of sinter, and the amount of CF is gradually increased
with the increase of alkalinity.
(2) The pre-compacting process reduces the return rate and increases the contact
area of the reactants, making the reactions such as solid phase reaction and
liquid phase formation more likely to occur.
(3) This technology can reduce energy consumption and reduce the production of
pollutants such as COx, SOX, and dust.
References
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2. Wen G (1993) Iron metallurgy. Chongqing University Press, Chongqing (in Chinese)
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Chinese)
4. Wang SP (2013) Study on energy saving and environmental protection of iron ore sintering.
PhD thesis, Wuhan University of Science and Technology (in Chinese)
5. Sun J (2018) Effect of strengthening sintering process on new alumina process. World Non-ferr
Metals (8):171–172 (in Chinese)
6. Hu B, Gan M et al (2017) The research on the pre-reduction of the original sintering technology
and the development of new technology. Sintered Pellet. 42(06):22–26 (in Chinese)
7. Ren W, Bai CG et al (2016) Carbon-free sintering of magnetite concentrate. J Chongqing Univ
(Natural Science Edition) (08):115–118 (in Chinese)
8. Ren W(2006). Microwave sintering of magnet concentrate. PhD thesis, ChongQing University
(in Chinese)
9. Lucia O, Maussion P et al (2013) Induction heating technology and its applications:
past developments, current technology, and future challenges. IEEE Trans Industr Electron
61(5):2509–2520
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IEEE Trans Ind Appl 9(1):81–85
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31(2):235–251
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14. Dudina DV, Georgarakis K et al (2009) A magnesium alloy matrix composite reinforced with
metallic glass. Comp Sci Tech 69:2734–2736
15. Dudina DV, Georgarakis K et al (2010) Cu-based metallic glass particle additions to
significantly improve overall compressive properties of an Al alloy. Compos A 41:1551–1557
16. Kim HC, Oh DY et al (2004) Sintering of nanophase WC-15vol%Co hard metals by rapid
sintering process. Int J Refract Metals Hard Mater 22:197–203
17. Khalil KA, Almajid et al (2012) Effect of high-frequency induction heat sintering conditions
on the microstructure and mechanical properties of nanostructured magnesium/hydroxyapatite
nanocomposites. Mater Des 36:58–68
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reduction. PhD thesis, Central South University
19. Hirschho JS, Samat M et al (1970) Induction sintering has potential for powder metal parts.
Metal Progress 97:135–138
A Study of Double Layer Pre-sintering
Toward Super-High Bed Height
Mingshun Zhou, Yidong Wang, Dongming Zhao, Jianwei Zhu, Huibo Liu,
Qiang Zhong, Guanghui Li and Tao Jiang
Abstract Aiming at the problem of low efficiency in high bed sintering, a new
process, namely double layer pre-sintering was developed by AISC Iron and Steel
Research Institute. The new process can obviously improve the bed permeability
and sintering productivity with a large proportion of fine iron concentrate. However,
the cold strength of sinter for the new process decreases to a certain extent, which
is mainly caused by the lack of oxygen in the lower sintering layer. At present,
by properly prolonging the pre-sintering time, the oxygen deficiency in the lower
sintering layer can be alleviated to a certain extent, and the cold strength of sinter
can be significantly improved. The industrial test results of 360 m2 sintering machine
in No. 2 sintering workshop and the No. 4 and No. 5 blast furnaces of Iron-making
Plant of Angang Steel Co. Ltd for nearly 7 months show that the new double layer
pre-sintering process is completely feasible in production practice, and 16.11% of
the sintering output has been achieved. The blast furnace runs smoothly with the
sinter of double layer pre-sintering process. Furnace productivity, fuel ratio and air
volume are basically consistent with the reference period. The implementation of
this new process is the first case in China. However, the new process needs to be
further improved in order to achieve the best sintering output, reduce sinter solid fuel
consumption and emission of nitrogen oxides and carbon oxides.
Keywords Iron ore sintering · Super-high bed height · Double layer pre-sintering
M. Zhou (B) · J. Zhu

Iron and Steel Research Institute, AnSteel Group Corporation, No. 63, Wuyi Road, Anshan
114009, Liaoning, China
e-mail: zms4652@163.com
H. Liu · Q. Zhong · G. Li · T. Jiang
China
e-mail: jiangtao@csu.edu.cn
Y. Wang
Ansteel Group Corporation Ltd., Anshan 114000, Liaoning, China
D. Zhao
Iron-Making Plant, Angang Steel Co. Ltd., Anshan 114000, Liaoning, China

https://doi.org/10.1007/978-3-030-36540-0_57
640 M. Zhou et al.
Introduction
Focusing on the topics of high quality and efficiency sintering, energy saving and
emission reduction, researchers have made a lot of research on new sintering methods
and technologies [1–5]. High bed sintering can not only reduce sintering energy
consumption, reduce emissions of carbon oxides, nitrogen oxides, sulfur oxides and
other gas pollutants but also improve sinter quality.
In sintering research and practice abroad, Soviet A. Nicolaev first proposed a
double layer ignition sintering method in 1930. According to the literature [6, 7], an
industrial test of double layer ignition sintering was carried out in a sintering plant in
the former Soviet Union with a thickness of 300 mm. Because the lower fuel is often
extinguished during combustion, the method has not been popularized. Double layer
ignition sintering must be carried out under the condition of combining with oxygen-
enriched sintering. On the basis of former research, Cairo Institute of Metallurgy of
Egypt adopted the method of using industrial oxygen to solve its problems to a certain
extent. However, the oxygen content in industrial oxygen used by Cairo Institute of
Metallurgy reached 95%, which can only be studied in laboratory. After all, it can
not be used in industrial production, nor solve the problem of material layer height
of ultra-thick material layer sintering [9]. Sumitomo Metal Industry Co. Ltd., of
Japan has carried out some laboratory research on double layer sintering process,
designed two-stage ignition sintering production methods and equipment, and even
three-stage ignition sintering methods and equipment. It is also due to the extinction
of lower fuel when it burns, and the design results have not been implemented [10].
The former Soviet Union did not continue the industrial application of double layer
sintering and the Japanese Sumitomo Metal Industry Co. Ltd., did not carry out the
industrial implementation of double layer sintering, because it could not achieve the
effect of increasing sintering production.
Aiming at the problem of low output of sintering machine and short plate affecting
the balance of blast furnace iron due to the use of large proportion of fine iron
concentrate in sintering workshops of Iron-making Plant of Angang Steel Co. Ltd
and poor permeability of bed layer and low sintering productivity, a new process of
pre-sintering with ultra-thick material layer has been developed by Angang Iron and
Steel Research Institute. In the absence of oxygen-enriched sintering, the relationship
between pre-sintering time and the thickness of upper and lower layers of double
layer materials has been successfully developed and optimized with independent
intellectual property rights, and 19 patents for inventions with the core of “a method
of sintering super-thick layers using pre-sintering” have been granted [8, 11], which
are in the sintering industry. On the aspect of industrial test, the reformation scheme
of feeding system and igniter of 360 m2 old sintering machine is put forward, and a
series of test research and industrial test tracking work are carried out. The results
show that double layer sintering greatly increases production and the sinter quality
meets the requirements of blast furnace smelting.
This paper is a summary of the laboratory research on the new technology of
double layer pre-sintering with super-thick material layer and the industrial test
A Study of Double Layer Pre-sintering … 641
carried out in the 360 m2 sintering machine in the second sintering workshop and the
No. 4 and No. 5 blast furnaces of Iron-making Plant of Angang Steel Co. Ltd., for
nearly seven months. A new pre-sintering process is proposed in order to enrich the
sintering technology and theoretical system of ultra-thick bed, to provide technical
support for the wide application of ultra-thick bed sintering technology in China and
to promote the high-quality, efficient and clean development of sintering industry.
Test Materials and Research Methods
Test Material
The experimental iron is taken from the second sintering workshop of the main
iron-making plant of Anshan Iron and Steel Co. Ltd. The chemical composition of
iron-containing raw materials is shown in Table 1 and the particle size composition
is shown in Table 2. The iron-bearing raw material used in the test is blended ore
(about 65% of fine iron concentrate produced by AISC and 35% of iron ore powder
purchased from abroad). The granularity of blended ore is relatively fine, its content
of−0.5 mm is as high as 73.24%, and the permeability of sintering mixture is poor.
As a result, the thickness of sinter layer in each sintering workshop of AISC’s iron-
making plant can not exceed 720 mm, which is favorable for sintering. The coefficient
of use is lower than 1.3 t/(m2 h). The flux (quicklime, limestone and magnesite
powder) and fuel (coke powder) used in the sinter pot experiment are also taken
from the material yard of the second sintering workshop of the iron-making plant.
Experimental Device and Research Method
Experimental Device
A large-scale sinter pot automatic control experimental system is used in laboratory

research. All sintering process parameters are automatically collected, processed
and output by computer without human interference. Sinter pot diameter is 300 mm,
height is 1100 mm. The system schematic diagram of sinter pot experimental device
is shown in Fig. 1.
Research Methods
In a large number of previous laboratory studies, the relationship between pre-

sintering time and the thickness of upper and lower layers of double layer materials
642
Table 1 Main chemical constituents of iron-containing raw materials and their burnout/%
Ferrous raw material TFe FeO CaO SiO2 MgO Al2 O3 S P LOI
Blended ore 57.86 16.17 4.28 5.02 1.02 0.93 0.044 0.035 5.84
M. Zhou et al.
Table 2 Particle size composition of iron-containing raw materials/%

Particle size/mm +8 8~5 5~3 3~1 1 ~ 0.5 −0.5
Iron-containing raw materials 1.17 1.56 4.70 10.80 8.54 73.24
Fig. 1 Systematic schematic diagram of a large sinter pot experimental device. 1. Air; 2. Ther-
mocouple; 3. Sintering pot; 4. Material; 5. Sintering pot lower box; 6. Exhaust fan; 7. Exhaust
gas discharge pipe; 8. Gas analyzer; 9. Flow sensor; 10. Thermocouple; 11. pressure sensor; 12.
clamping parts; 13. Thermocouple components (13.1–13.4 thermocouples); 14. Control system and
15. Computer and other components
has been successfully optimized. In this part, the sintering effects of conventional sin-
gle layer sintering (material layer thickness 700 mm) and double layer pre-sintering
(material layer thickness 1000 mm) have been compared and introduced to charac-
terize double layer pre-sintering. Characteristics of new sintering process. The sinter
pot mixing scheme refers to the actual sintering mixing conditions in the second
sintering workshop of the iron-making plant. The basicity of the sinter is R = 2.05
and MgO = 1.7%. The comparative experiments are described as follows:
(1) Conventional single layer sintering benchmark experiment: conventional single
layer sintering, bed thickness is 700 mm.
(2) Double layer pre-sintering experiment: The total bed thickness of double layer
pre-sintering is 1000 mm, and the upper and lower layer thickness are 350 mm
and 650 mm, respectively. First, the lower layer is distributed to 650 mm thick-
ness, then ignition, heat preservation and sintering are carried out by single
644 M. Zhou et al.
Table 3 Processing
Substrate thickness 20 mm
conditions of conventional
single layer and double layer Single layer height 720 mm (including base
sinter pot material)
Double layer height 1020 mm (including base
material)
Ignition temperature of 1050 ± 50 °C
single layer and double layer
Single layer ignition time 90 s
Negative ignition pressure of −8000 Pa
single layer and double layer
Single and double sintering −10780 Pa
negative pressure
First ignition time 90 s
Second ignition time 90 s
layer sintering. When the pre-firing time is 1.0 min from the sintering to the
test setting, the upper secondary distribution is quickly carried out, and then
secondary ignition, heat preservation and sintering are immediately completed
after the second distribution. The sintering end point of the lower layer is judged
by the highest point of waste gas temperature, and the sintering end point of
the upper material layer is judged by the exterior thermocouple on the wall of
the sinter pot. The time required to reach the highest temperature is the total
sintering time, that is, the sintering time of the whole bed.
The benchmark test and double layer pre-sintering test reached the sintering end
point, and then cooled in the sinter pot by air exhaust for 3 min. Then the sinter cake
is unloaded by the self-weight of the tilting sinter pot. The sinter cake is crushed
by a single-tooth roller to obtain the sinter sample to be tested. The technological
conditions of sinter pot for benchmark experiment and double layer pre-sintering
experiment are shown in Table 3.
Basic Laboratory Research on Double Layer Pre-sintering

of Super-Thick Material Layer
Comparison of Different Sintering Processes
The indexes of single layer sintering process and double layer pre-sintering process
are compared as shown in Table 4. The bed thickness of single layer sintering process
is 700 mm, the bed height of double layer pre-sintering process is 1000 mm, the
upper and lower bed heights are 350 mm and 650 mm, respectively, and the pre-
sintering time is 20 min. Table 4 shows that, compared with traditional single layer
Table 4 Comparison of different sintering process indexes

Material Vertical Yield/% Drum Productivity/t Solid fuel
height/mm sintering strength/% (m2 h)−1 consumption/kg
speed/mm t−1
min−1
Single layer 18.37 68.37 61.53 1.26 46.13
sintering
Double layer 20.30 66.76 60.87 1.60 45.81
pre-sintering
sintering, using double layer pre-sintering process, the sintering utilization coefficient
increased from 1.26 to 1.60 t/(m2 h), which increased by nearly 27%. The solid
fuel consumption of sinter decreased but the sinter yield and sinter drum strength
decreased.
Study on Reaction Behavior of Double Layer Pre-sintering
Flue Gas Properties of Double Layer Pre-sintering
The flue gas properties of double layer sintering at 850 mm from the material level
were studied under the conditions of 1000 mm height, 350 mm in upper layer and
650 mm in lower layer, respectively, and 12 min pre-sintering time. The variation
of O2 , CO2 and CO gas composition with sintering time in 850 mm bed sintering
process is shown in Fig. 2.
Figure 2 shows that after the first ignition, the oxygen content in the material
layer decreases dramatically, from 21% in the air to 4% due to the large amount of
oxygen consumed by ignition. After ignition, the content of O2 increases, while the
content of CO2 decreases accordingly. After ignition, the content of O2 and CO2
tends to be stable, about 12% and 10%, respectively. The results show that a certain
amount of oxygen will be consumed by single layer sintering, and the content of
oxygen will be reduced from 21 to 12%. The residual gas of single layer sintering
moves downward into the lower sinter layer, and the oxygen is further consumed in
the second sintering layer. The oxygen content decreases from about 12 to 4%, and
the CO2 content increases from about 10 to 22%. As the sintering process continues,
the content of O2 increases rapidly and the content of CO2 decreases sharply. At this
time, the sintering reaction of 850 mm bed is completed, forming sinter zone.
Reaction Mechanism of Double Layer Pre-sintering
The reaction mechanism of double layer sintering is shown in Fig. 3.

646 M. Zhou et al.
1200
24 First 1 Temperature The end
ignition of sintering
↓ 2 O2
1 1000
20 3 CO2
4 CO 3 2
800
Temperature ( )
Content (%)
16 Second
ignition start
12 600
The end of
second ignition
8 400
4 The end of 4 200

first ignition ↓
↓ ↓
0
↓ ↑ 0
0 10 20 30 40
Sintering time (min)
Fig. 2 Gas composition of double layer pre-sintering process
Fig. 3 Reaction of double

layer pre-sintering process
From Fig. 3, it can be seen that the structure and properties of double layer sintering
material layer are more complex than single layer sintering, which can be divided
into upper layer, middle layer and lower layer. The upper layer is a normal sinter cake,
its structure and properties are the same as those of single layer sintering, from top to
bottom, it can be divided into sinter zone, combustion zone, pre-tropical zone, super-
humid zone and raw material zone. Air containing 21% O2 flows downward from
the surface of the upper material layer, and reacts with Fe and C in the material layer
to consume oxygen, generate nitrogen oxides, water vapor, etc. When the gas flows
to the original material layer, the main composition of the gas is (10% O2 ) + CO2
+ CO + H2 O + N2 , etc. The middle layer is a sinter zone formed by pre-sintering,
the sintering process of this layer is the same as that of the single layer sintering
process and the height of the layer is mainly determined by the pre-sintering time.
The sintering process of the lower material layer is a double layer sintering process
synchronized with that of upper material layer. The lower material layer structure
is also divided into sinter zone, combustion zone, pre-tropical zone, super-humid
zone and raw material zone from top to bottom. Oxygen is further consumed in the
material layer, and its content is reduced from about 10% to about 4%.
Study on Optimization of Pre-sintering Time
The influence of different pre-sintering time on double layer sintering speed, pro-
ductivity and drum index are shown in Table 5. From Table 5, it can be seen that
different pre-sintering time has a great influence on the sintering indexes. When the
pre-sintering time is 20 min, the sinter productivity increases and the drum strength
improves significantly.
Under the conditions of 10, 12, 14, 16 and 20 min pre-sintering time, the sinter
yield and drum strength are the highest and solid fuel consumption is the lowest when
the pre-sintering time is 20 min. The main reasons are as follows: for double layer
pre-sintering, since the lower layer is first ignited and sintered, then the upper layer
is laid and then ignited and sintered, there must be two combustion zones moving
simultaneously in the sinter layer. In the absence of oxygen enrichment, after the
second ignition, the waste gas from upper layer is accepted by the lower layer.
Table 5 Effect of different pre-sintering time on sintering index

Pre-sintering Sintering Yield/% Drum Productivity/t Solid fuel
time/min speed/mm strength/% (m2 h)−1 consumption/kg
min−1 t−1
20 20.30 66.76 60.87 1.60 45.81
16 21.94 65.39 59.90 1.63 46.93
14 22.59 63.06 58.92 1.71 47.65
12 22.72 62.95 58.67 1.76 48.02
10 23.70 60.22 57.00 1.80 49.99
648 M. Zhou et al.
Obviously, the low oxygen content of sintering waste gas affects the combustion
of carbon in the lower layer, thus the mineralization process is adversely affected,
resulting in lower productivity and lower drum strength. Obviously, the longer the
pre-sintering time is, that is, the later the second layer distribution is, the later sintering
exhaust gas with low oxygen content from the upper layer is accepted by the lower
layer, the more time the lower layer will have to complete the mineralization process.
The sinter yield and drum strength will inevitably increase, and at the same time,
it will bring about a good impact on the reduction of solid fuel consumption of
sintering. The double layer pre-sintering process can prolong the pre-sintering time
as far as possible on the premise of guaranteeing the solid fuel consumption of the
upper sintering mixture, which is beneficial to improving the sinter quality of the
whole bed and reducing the consumption of solid fuel.
Sintering and Blast Furnace Industrial Test of New Double

Layer Pre-sintering Process
Starting from February 29, 2016, industrial tests were carried out on 360 m2 sintering
machine in No. 2 sintering workshop of AISC Iron-making Plant and No. 4 and
No. 5 blast furnace of AISC Iron-making Plant. The sketch of double layer pre-
sintering process of 360 m2 sintering machine in No. 2 sintering workshop is shown
in Fig. 4. Because the sintering industrial test was completed on the old sintering
machine which has been running for nearly 20 years, there are many processes that
are not suitable for double layer sintering process in the original single layer sintering
process. Especially, there are many problems, such as the incompatibility between
the supply and output of double layer sintering and the original design ability, such
as the unstable secondary feeding, uneven material surface, interruption of material
Fig. 4 Double layer pre-sintering process diagram of 360 m2 sintering machine

Table 6 Quality comparison of different sintering processes

Sintering process FeO/% Drum strength/% Sieving index/% Fraction of small
particles/%
Single layer 8.66 80.31 3.96 34.7
sintering
Double layer 9.00 78.92 4.54 37.57
pre-sintering
Difference +0.34 −1.39 +0.58 +2.87
flow, etc. Even if there are many problems mentioned above, the double layer pre-
sintering process of super-thick bed still achieves obvious sintering improvement.
As for the production effect, the new process still needs to be improved in some
technological parameters and processes.
Sintering Mineral and Quality Evaluation
Sinter Output
In the No. 2 sintering plant, the output of sintering machine has been greatly increased
by using double layer sintering technology with super-high material layer. The output
of sintering machine has increased from 450.6 t in the base period to 523.2 t in the
test period, which has increased by 16.11%.
Sinter Quality
The product quality of ultra-thick material layer double layer pre-sintering process
and conventional single layer sintering process is shown in Table 6. From Table 6, it
can be seen that sinter drum strength decreased from 80.31% in conventional single
layer sintering process to 78.92% in double layer sintering industrial test period, and
decreased by 1.39%. The cold strength of sinter is reduced and the proportion of small
size fraction is increased by using double layer sintering process with super-thick
material layer, but it still meets the requirements of BF for sinter quality.
Brief Evaluation of Blast Furnace Operation Effect
The industrial test results of No. 4 and No. 5 blast furnaces show that the sinter with
the new double layer pre-sintering process is in good condition. Although the cold
strength of sinter is reduced and the proportion of small size fraction is increased,
the blast furnace‘s running condition is basically unaffected, which may be related to
the double layer sintering strengthening of finished ore screening system. In general,
650 M. Zhou et al.
the powder sieve is relatively clean. During the test period, the average daily output
of BF is 4925 t/d and the air volume is 3880 m3 /min. The utilization coefficient, fuel
ratio and air volume of BF are basically the same as those of the baseline period. The
sinter quality of the new double layer pre-sintering process meets the requirements
of blast furnace smelting.
Conclusion
(1) Compared with the traditional single layer sintering, the new double layer pre-
sintering process can significantly improve the permeability of the sinter bed,
accelerate the vertical sintering speed, greatly increase the sintering productiv-
ity, and reduce the solid fuel consumption of the sinter. Under the same large
proportion of fine concentrate raw materials, the bed thickness of the new dou-
ble layer pre-sintering process can be raised from about 700 mm. As high as
1000 mm, the effect of sintering yield increase is remarkable, which solves the
bottleneck problem of low sintering yield and difficult production increase in
super-thick bed.
(2) The new double layer pre-sintering process has the problem of decreasing sinter
yield and cold strength to a certain extent. the main reason is the lack of oxygen
in the lower sintering process. By prolonging the pre-sintering time properly,
the oxygen deficiency can be alleviated to a certain extent and the cold strength
of sinter can be improved obviously.
(3) The industrial test results of 360 m2 sintering machine and No. 4 and No. 5
blast furnaces show that the new double layer pre-sintering process is feasible
in production practice, and 16.11% sintering effect has been achieved. The new
double layer pre-sintering process is in good condition with high sinter yield.
Furnace productivity, fuel ratio and air volume are basically the same as those
of conventional sinter.
(4) The new double layer pre-sintering process is a subversive technological inno-
vation in the sintering field in China, representing the development direction of
thick-bed sintering. The new process still needs to be improved in some techno-
logical parameters and processes in order to achieve the best sintering output,
reduce solid fuel consumption of sinter and carbon oxide emissions.
Acknowledgements This work was supported by the Anshan Iron and Steel Group Co. Ltd under
Grant 738010261.
References
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2. Kenichi H, Takuya K, Masanori K, Yoshiki T, Yohei T, Yohei I, Shingo F (2006) Nippon Steel
Tech Rep 94:31
3. Jiang T, Li G, Fan X (2016) China Metall News 0204:006
4. Jiang T, Yu Z, Peng Z, Rao M, Zhang Y, Li G (2015) ISIJ Int 55:1599
5. Kang H, Choi S, Yang W, Cho B (2011) ISIJ Int 51:1065
6. Weigman E (1991) Sinter Pelletiz 16:34
7. Frank AB, Robert CM, Ronald KAMM, Gaby JMJ (1996) WISCO Technol 6:10
8. Tang F, Zhou M, Wang Y (2017) Patent no 201610144762.8, CN, May
9. Cao Z (1995) Sinter Pelletiz 20:29
10. Feoktistov AV, Odintsov AA (2014) Metallurgist 58:469
11. Zhai L, Zhou M, Tang F (2017) Patent no 201610815437, CN, June
Reduction Behavior of In-flight Fine
Hematite Ore Particles by CO + H2
Mixtures in a High-Temperature Drop
Tube Furnace
Liyong Xing, Yingxia Qu, Fanchao Meng, Chunsong Wang and Zongshu Zou
Abstract The ironmaking processes that directly use the raw materials of iron ore
fines are expected to significantly reduce energy consumption, carbon dioxide emis-
sion and have great advantages in iron ore resource utilization. In this paper, the
reduction behavior of the in-flight fine hematite particles in CO and H2 mixture
atmosphere is studied with a modified high-temperature drop tube furnace. The
kinetic mechanism of the gas-solid reduction of hematite ore fines is determined
in the temperature range of 1450 ~ 1550 K. The particle size is 53 ~ 64 µm and the
reaction time is less than 2 s. The effect of carbon monoxide concentration in the gas
mixture on the reaction rate is examined. Based on the kinetic analysis and the mor-
phology observation, the unreacted shrinking core model is used as the mathematical
description for the reduction mechanism. The reaction rate equation is obtained and
the calculated results are in good agreement with the experimental ones.
Keywords Hematite ore fines · Morphological observation · Reduction kinetics ·

Hydrogen · Carbon monoxide
Introduction
The novel ironmaking technologies based on the direct gaseous reduction of iron
ore fines during the in-flight process have significant advantages in raw material
utilization and reduction of carbon dioxide emission. The HIsarna and Suspension
ironmaking processes are considered to be very promising flash ironmaking processes
[1–5]. The reaction temperature in the melting cyclone of the HIsarna and the flash
shaft of the Suspension ironmaking technology is at the range of 1473 ~ 1873 K.
The iron ore fines are rapidly heated and reduced by the reducing gas during the
in-flight process. Most of the previous studies focused on the reduction of iron ore
fines at low temperatures (below 1173 K), which were carried out under the fluidized
bed reactor conditions. There are few studies on the flash reduction taking place at
L. Xing · Y. Qu (B) · F. Meng · C. Wang · Z. Zou

School of Metallurgy, Northeastern University, Shenyang 110819, China
e-mail: xingly229@qq.com

https://doi.org/10.1007/978-3-030-36540-0_58
654 L. Xing et al.
high temperatures (above 1400 K). Hydrogen is considered to be a good reductive

agent as well as an environment-friendly material. Wang et al. [6] investigated the
reduction kinetics of magnetite relevant to the suspension ironmaking process with
a drop tube furnace. The reduction reaction took place in the hydrogen atmosphere
at the temperature ranging from 1423 to 1673 K. The nucleation and growth model
was applied to obtain the kinetic parameters. Chen et al. [7] investigated the flash
reduction kinetics of hematite relevant to the suspension ironmaking process with the
same reactor in the CO atmosphere. In the reactor, the reaction above the isothermal
zone was eliminated but it still cannot be avoided below the isothermal zone. As a
preliminary study of the present work, Qu et al. [8] investigated the reduction kinetics
of fine ore particles in gas mixtures of H2 + CO with the different post combustion
ratios. The temperature was ranged from 1550 to 1750 K and a part of the iron ore
fines was melted. The reactor used in the experiment was a High-temperature Drop
Tube Furnace (HDTF). A water-cooled sampling probe was inserted into the furnace
to collect the reduced particles and to avoid the reduction below the isothermal zone.
However, the water-cooled sampling probe in the reactor lowered the temperature
at the lower part of the isothermal zone, which has a significant influence on the
isothermal reaction zone.
In this work, the water-cooled sampling probe used by Qu [8] is replaced by a
sampling probe filled with inert gas. In this way, the sampling probe has very little
influence on the high-temperature zone. In addition, the length of the isothermal
zone can be varied by changing the position of the water-cooled injection probe. The
morphology of the individual iron ore particles is observed with an optical microscope
and SEM. The effect of the gas composition on the reaction rate is investigated. The
kinetic model for the gas-solid reduction of iron ore fines at high temperatures is
established and the kinetic parameters are determined.
Experimental Work
The schematic diagram of the high-temperature drop tube furnace (HDTF) is shown
in Fig. 1. The HDTF mainly consists of a vertical tube furnace and an automatic
feeding system. An alumina tube with an inner diameter of 100 mm is used as the
reactor tube. At the top of the furnace, a water-cooled injection probe is inserted into
the reactor to avoid the reduction of iron ore fines before entering the isothermal
zone. The length of the isothermal zone can be varied by changing the position of
the injection tube. At the bottom of the furnace, a sampling tube filled with inert
gas is used to prevent the iron ore fines from further reduction. The gas mixture is
divided into two parts as the main gas and the carrier gas, respectively. The reducing
gas flows downward through the reactor, which is in a laminar state. The reduction
reaction takes place only in the isothermal zone which begins from the tip of the
water-cooled injection probe and ends at the top of the sampling tube. This modified
reactor provides a reaction zone with a more uniform temperature profile.
Reduction Behavior of In-flight Fine Hematite … 655
Fig. 1 Schematic diagram of the high-temperature drop tube furnace
Industrial hematite ore fines are used as the raw material in this study and the
particle size is in the range from 53 ~ 64 µm. The reaction temperature is varied
from 1450 ~ 1550 K. The gas mixtures are 20% CO + 20% H2 + 60% N2 , 30% CO
+ 20% H2 + 50% N2 and 40% CO + 20% H2 + 40% N2 . The particle feeding rate
is fixed at 5 g/h to avoid collision and agglomeration during the in-flight process.
The reaction time of iron ore fines in the reaction zone is calculated by applying
Newton’s second law and Stokes’ law to the motion of an individual particle through
fluids. The force balance regarding an individual particle is expressed as Eq. (1).
When the reaction temperature is 1500 K and the reducing gas is composed of 20%
CO + 20% H2 + 60% N2 , the particle velocity and reaction time in the isothermal
zone are calculated and shown in Fig. 2. When the iron ore fines from the injection
probe enter the reaction zone, the velocity is rapidly reduced by the drag force until
reaching the terminal falling velocity. The reduction time generally increases linearly
with the length of the reaction zone.
2
du p ρg u g − u p
mp = C D Ap + Vp g ρp − ρg (1)
dt 2
656 L. Xing et al.
Fig. 2 Hematite particle

velocity and reaction time in
the isothermal zone
where, ρ g and ρ p are the gas density and the hematite ore density (kg m−3 ); ug and
up are the gas velocity and the hematite particle velocity (m s−1 ); mp is the mass
of an individual iron ore particle (kg); V p is the volume of particle (m3 ); Ap is the
projection area of particle (m2 ).
Effect of Gas Concentration on Reduction Degree
The reduction degree (R) is defined as the ratio of the oxygen mass loss to the initial
reducible oxygen mass in the hematite ore fines, and it is calculated based on the
results of chemical titration. The experimental results of reduction degree in different
reducing gas atmospheres are shown in Fig. 3a–c. The reduction degree of hematite
ore fines increases rapidly with the increase of temperature and the reduction rate is
very fast at high temperatures. At the present experimental conditions, the highest
reduction degree can reach 50% at 1.7 s. When the reducing gas is composed of 20%
CO + 20% H2 + 60% N2 and the reaction time is 1.3 s, the reduction degrees at 1450
~ 1550 K are 14.1%, 20.6% and 28.5%, respectively. When the temperature rises by
50 K, the reduction degree increases by an average of 8% at the same reaction time.
When the reaction temperature is 1450 K, the reduction degree versus time profiles
of hematite ore fines in the different reducing gas atmosphere are shown in Fig. 3d.
The H2 concentration is fixed at 20%, and the CO concentrations are 20%, 30% and
40%, respectively. When the reaction zone is 50 cm, the reaction times in 20, 30 and
40% CO concentration are 1.634, 1.652 and 1.670 s. This is due to the viscosity of
N2 is smaller than that of CO, and the viscosity of the gas mixture increases with
the increase of the CO concentration. The effect of reducing gas composition on
the reduction time is negligible at current experimental conditions. It can be found
that the reduction degree increases with the increase of CO concentration. Figure 3d
Fig. 3 Reduction degree of hematite in a 20% CO + 20% H2 , b 30% CO + 20% H2 , c 40% CO

+ 20% H2 and d different gas compositions at 1450 K
shows that the reduction degrees of hematite ore fines are 18.47, 21.53 and 27.29%,
when the length of the reaction zone is 50 cm and the CO concentrations are 10%,
20% and 30%, respectively. When the CO concentration rises by 10%, the reduction
degree only increases by an average of 3% at the same experimental temperature and
the same reaction time.
Morphological Observation
The surfaces and cross-sections of the individual partially reduced particles are
observed by the SEM and optical microscope as shown in Fig. 4. It can be seen
that the particle surface becomes rough and porous due to the reduction reaction.
The porous layer formed from solid iron product. Figure 4b shows the cross-section
of the individual particle, and the different iron containing phases inside the particle
can be distinguished by colors. According to the chemical titration result and XRD
analysis, the gray phase inside the particle is wüstite and the white color outside
658 L. Xing et al.
Fig. 4 Observation of the individual partially reduced hematite ore particles: a surface morphology,
b cross-section morphology, R = 45.1%
the wüstite phase is metallic iron. When the reduction degree is 45.1%, the mass
fractions of the wüstite and the metallic iron in the hematite ore fines are 69.7% and
15.9%, respectively. The reduction process takes place at the interface between the
two phases, and the unreacted shrinking core model can describe the reduction of
hematite ore fines.
Kinetic Analysis
Based on the morphological observation, the unreacted shrinking core model is used
to establish the reaction rate equation for the in-flight reduction of hematite fines.
According to the unreacted shrinking core model, the rate-controlling step can be
external gas diffusion, interfacial chemical reaction or internal gas diffusion. In this
study, the external gas diffusion is eliminated by increasing the total gas flow rate
during the experiments. The correlation coefficients of the identification equations
of chemical reaction control and internal gas diffusion control are calculated with
Eqs. (2) and (3). The results show the plots of the chemical reaction control have the
best linear relationship [9]. Therefore, the rate-controlling step is determined to be
the interface chemical reaction. The forward reaction rate constants are calculated
with Eq. (4). When the reducing gas composition is 20% CO + 20% H2 , the plots of
the forward reaction rate constant versus the experimental temperatures are shown
in Fig. 5a. The forward reaction rate constant increases with the increase of temper-
ature. When the temperatures are 1450, 1500 and 1550 K, the forward reaction rate
constants are 2.58 × 10−2 m s−1 , 4.36 × 10−2 m s−1 and 5.59 × 10−2 m s−1 , respec-
tively. According to the Arrhenius equation, the relationship between the forward
Fig. 5 Kinetic curves of a forward reaction rate constants at different reduction temperatures,
reducing gas: 20% CO + 20% H2 and b Arrhenius plot for the calculation of activation energy
reaction rate and the temperature is expressed by Eq. (5). The plots of lnk + versus
1/T are shown in Fig. 5b, and the activation energy and the pre-exponential factor are
determined to be 157 kJ mol−1 and 1.27 × 104 m s−1 . The reduction rate equation of
the hematite ore fines during the in-flight process can be expressed by Eq. (6). The
comparison between the experimental results and the calculated reduction degrees
is shown in Fig. 6. It can be seen that the calculated reduction degrees are in good
agreement with the experimental reduction degrees. The correlation coefficient is
calculated to be 0.96 by the least square method. The average relative deviation
between calculated values and the experimental reduction degrees is 8.5%.
1 − (1 − R)1/3 = kt (2)

the calculated and the
experimental reduction
degrees
660 L. Xing et al.
1 − 2R/3 − (1 − R)2/3 = kt (3)
1
k+ C 0 − C e (1 + K )
H2 H2
1 − (1 − R) =
3 t (4)
ρorp K
−E a
ln k+ =+ ln A (5)
Rg T

dR −157000 3 C 0 − C e (1 + K )
= 1.27 × 10 exp
4
(1 − R)2/3 (6)
dt Rg T Kρorp
where R is the reduction degree (−); k is the apparent rate constant (s−1 ); k + is the
forward reaction rate constant (m s−1 ); ρ o is the initial oxygen density (mol m−3 ); r p
is the initial particle radius (m); K is the equilibrium constant; CH0 2 is the initial H2
concentration (mol m−3 ); CHe 2 is the equilibrium H2 concentration (mol m−3 ); E a is
the activation energy (kJ mol−1 ); A is the pre-exponential factor (m s−1 ).
Conclusions
The experiments of the flash reduction of hematite ore fines in CO + H2 atmosphere

are carried out with the modified high-temperature drop tube furnace. The gas-solid
reduction behavior of hematite ore fines has been investigated, and the following
conclusions are drawn.
(1) At a constant H2 concentration, the reduction degree slightly increases with the
increase of the CO concentration. When the CO concentration rises by 10%, the
reduction degree only increases by an average of 3% at the same experimental
temperature and the same reaction time.
(2) The surface of the partially reduced particle becomes rough and porous due to
the reduction reaction and the unreacted shrinking core model can describe the
reduction of hematite ore fines.
(3) The reaction rate equation is established based on the unreacted shrinking
model. The activation energy and pre-exponential factor are determined to be
157 kJ mol−1 and 1.27 × 104 m s−1 . The calculated reduction degrees are in
good agreement with the experimental reduction degrees.
Acknowledgements The authors are grateful for the financial support from the National Nat-
ural Science Foundation of China (Grants Nos. 51504056, 51604068 and 51574046), and the
Fundamental Research Funds for the Central Universities (Grant No. N182504012).
References
1. Quader MA et al (2016) Present needs, recent progress and future trends of energy-efficient
ultra-low carbon dioxide (CO2 ) steelmaking (ULCOS) program. Renew Sustain Energy Rev
55:537–549
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Int 55:149–157
9. Xing L et al (2019) Gas-solid reduction behavior of in-flight fine hematite ore particles by
hydrogen. Steel Times Int 90. https://doi.org/10.1002/srin.201800311
Effect of Distributor Structure
on the Uniformity of Multiphase System
in Fluidized Ironmaking Process
Wang Tao, Liu Yan, Li Xiaolong, Cao Xuejiao and Zhang Tingan
Abstract For the uneven gas–solid distribution in the process of fluidized bed iron-
making, the effect of the distributor on gas–solid homogeneity in fluidized bed was
investigated by using physical simulation. Statistical analysis and spectral analysis
were used to investigate the pressure fluctuations in the fluidized bed with the dis-
tributor of different perforated ratio, and the results were verified by optical analysis.
The results reveal that the smaller perforated ratio of the distributor can reduce the
bubble size of the whole bed and reduce the pressure fluctuation. Thus, the gas–solid
dispersion is uniform, and the fluidization quality of the fluidized bed is improved.
However, the distributor has a limited effect area, which has a great influence on the
lower part of the fluidized bed. As the gas velocity and the height increase, the effect
becomes weaker. Under the operating conditions of 100 L/min, the perforated ratio
of 0.91% can reduce the pressure drop of the entire bed by 65%. It can also reduce
the pressure drop deviation in the lower part of the bed by more than 79%.
Keywords Fluidized bed · Physical simulation · Pressure fluctuation · Gas–solid

distribution · Perforated ratio
Introduction
Because of the uneven distribution of gas and solid, the fluidization quality is poor. It is
not conducive to the stable operation of the fluidized ironmaking process. At present,
domestic and foreign scholars have carried out physical simulation experiments on
the multiphase reaction system of fluidized ironmaking. Yan Yun [1] studied the
narrow particle size distribution of iron concentrate ore in the fluidized bed and found
that the particle size distribution of the material in the multi-bed diameter bubbling
fluidized bed is more obvious. ZOU Zongshu [2] studied the relationship between
W. Tao · L. Yan (B) · L. Xiaolong · C. Xuejiao · Z. Tingan

Key Laboratory of Ecological Metallurgy of Multi-metal Intergrown Ores of Ministry of
Education, Special Metallurgy and Process Engineering Institute, Northeastern University,
Shenyang 110819, China
e-mail: liuyan@smm.neu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_59
664 W. Tao et al.
flow rate and pressure drop and expansion rate. He also established the theoretical
formulas of initial fluidization velocity, void fraction and fluidization height in the
fluidized ironmaking process. Zhu Kuisong [3] investigated the fluidization of iron
ore fines under different particle size, and used the experimentally calculated particle
sphericity and bed void fraction, which modifies the parameter C1 in the derivation of
wen-yu and Gupta equations. The accuracy of the correction results was verified by
utilizing the Brazilian and Australian iron ore powder experiments. At present, these
physical simulation experiments focus on the study of fluidization characteristics
parameters. However, there are few studies on gas–solid uniformity in fluidized
beds. In this paper, from the perspective of the reactor structure, the influence of the
distributor on gas–solid uniformity in the fluidized bed is investigated through the
method of physical simulation.
The distributor plays an important role in the stable operation of the fluidiza-
tion process. It can evenly distribute the gas before it contacts with the solid [4] and
reduces the flow loss, which improves the heat and mass transfer between the gas and
solid. A reasonable distributor can improve the fluidization quality of the fluidized
bed, making the whole fluidization process stable and reducing the consumption of
gas kinetic energy. The pressure fluctuation in the fluidization process can provide
valuable information in the bed. Thus, the fluidization process is generally studied
through the analysis of the pressure signal. Statistical analysis is simple and conve-
nient. The standard deviation and probability density function of pressure pulsation
can directly reflect the fluctuation of pressure [5]. Spectral analysis can not only
distinguish the fluidization but also analyze the law of pressure signal [6]. Wavelet
analysis can decompose pressure signals at different scales, and further analyze pres-
sure fluctuations from the perspective of signal energy characteristics. [7]. Optical
analysis can visually observe the distribution between the gas phase and the solid
phase in the fluidized bed.
Dong S analyzed the influence of the perforated ratio on the pressure drop of the
distributor and solid phase with numerical simulation and physical simulation. He
found that a reasonable perforated ratio can reduce the fluctuation of the solid phase,
and cut down the gas kinetic energy consumption [8]. But the results are still not
clear.
In this paper, the physical simulation system of the fluidized ironmaking process
was designed. Based on the pressure pulsation experiment, the influence of the dis-
tribution plate with different perforated ratios on the uniformity of phase distribution
was studied. The main functional areas of the distribution plate are discussed, which
provides the theoretical basis for the thermal experiment and the scale-up of the
reactor.
Effect of Distributor Structure on the Uniformity … 665
Experimental
Experimental Equipment and Materials
The physical simulation system is shown in Fig. 1. The physical simulation platform
of the fluidized ironmaking process consists of four parts. The first part is the gas
control system, including an air compressor, a gas buffer tank, and a gas flow meter.
The second part is a fluidized bed reactor system with a diameter of 100 mm
and the height of 1200 mm, respectively. The pre-distributor is an inverted cone gas
chamber with the cone angle of 40 degrees. The distributor with different perforated
ratios is used, and a 200-mesh screen is added on the upper part to prevent leakage.
There are 91 perforations in the distributor, which are arranged in a communication
circumference. The numbers from the inside to the outside are 1, 6, 12, 18, 24, and
30. The perforated ratios of the three distributors are 0.91%, 3.64%, and 8.19%,
respectively, and the corresponding straight hole diameters are 1, 2, and 3 mm,
respectively.
The third part is the pressure measurement system. Five CGYL-300B pressure
sensors are installed on the sidewall of the fluidized bed. The vertical height from the
bottom of the pre-distributor is—50, 25, 50, 150, and 250 mm. The voltage signal
obtained by the pressure sensor is collected into the computer through the Advantech
USB-4716 data acquisition module. Then the acquired voltage signal is converted
into pressure data by LabVIEW software. To ensure the accuracy of sampling, the
sampling frequency is controlled by programming to 200 Hz, and the number of
samples is 10000.
Fig. 1 Apparatus of
1. Air compressor
lab-scale fluidized bed
2. Gas tank
3. Control valve
4. Pressure meter
5. Flow meter
6. High speed camera
10 7. Gas distributor
11 8. Pressure transducer
9. Data acquisiƟon
10. Computer
11. Fluidized bed reactor
8
6
2
1
9 3
7
5 4
666 W. Tao et al.
The fourth part is the optical analysis system. The fluidization process was
recorded by the high-speed camera. The recording speed was 400 frames per sec-
ond. The video was converted into pictures by i-SPEED Suite, and then the param-
eters such as length, area, and equivalent diameter are measured by Image-Pro Plus
software.
In this experiment, for normal distribution of hematite, 0.1–1 mm glass beads
were screened for an average particle size of 0.41 mm and a density of 2500 kg/m3 .
The air with a density of 1.29 kg/m3 and a dynamic viscosity of 1.8 × 10−5 was
selected as the fluidized medium. The static bed height was 300 mm.
Experimental Method
Time-Domain Analysis
The fluidization quality of the gas–solid fluidized bed is generally analyzed by data
statistics. In this paper, the raw data of pressure fluctuation is processed by the
standard deviation to study the fluidization quality of the fluidized bed. The standard
deviation of the pressure signal can directly reflect the fluctuation of the pressure in
the fluidized bed, which is a relatively simple method for evaluating the fluidization
state. Its calculation is implemented by the STDEV.S function in the excel software,
and the calculation formula is:

1 n
2
σP = Pi − P̄ (1)
n − 1 i=1
Frequency Domain Analysis
The fluid dynamics state of the fluidized bed can be determined by frequency domain
analysis of the pressure signal. the presence of bubbles in the fluidized bed can be
observed from the power spectrum of the pressure signal. The peak of the spectrum
corresponds to the bubble of the relevant frequency [9]. The power spectrum is
obtained by the fast Fourier transform module in the origin software.
Result and Discussion
Figure 2 shows the pressure drop curve. It can be seen that the bed lamination drop
has no relationship with the perforated ratio of the distributor [10, 11]. The initial
fluidization velocity was determined to be 0.17 m/s by the “deceleration method”,
Fig. 2 Relationship between 4000
bed pressure drop and 3500

superficial gas velocity
3000
Pressure drop, p(Pa)

2500
2000
0.91%
1500
3.64%
8.19%
1000 100%
500
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Superficial gas velocity,Ug(m/s)
whereas the initial fluidization velocity calculated according to the formula was
0.13 m/s. This is because the initial fluidization velocity is calculated according
to the average particle diameter of 0.41 mm, while the experimental particles are
normally distributed, and the main particle size is concentrated at about 0.49 mm, so
the initial fluidization velocity calculated by the formula is smaller.
Time-Domain Analysis
The pressure drop is the differential pressure between the two pressure measurement
positions. The difference calculation can eliminate other factors affecting the pressure
fluctuation between the two positions. The bubble size can be characterized by the
standard deviation of the pressure fluctuation signal [12]. Figure 3 is the relationship
between the standard deviation of the entire bed lamination drop and the perforated
ratio of the distributor at different gas velocities. Under different gas flows, the
Fig. 3 The standard 700

deviation of pressure Q=140 L/min
fluctuation in the fluidized 600 Q=120 L/min
bed with different gas flows Q=100 L/min
500
H=(-50)-250 mm
400
dp/Pa
300
200
100
0
100% 8.19% 3.64% 0.91%
Perforated Ratio
668 W. Tao et al.
standard deviation of the total pressure drop of the bed will decrease with the decrease
of the perforated ratio of the distributor. It can be seen from formula [13] that, under
the same conditions, the reduction in the cross-sectional area of each orifice on
the distributor reduces the equivalent diameter of the bubbles of each height in the
fluidized bed, thereby reducing the standard deviation of the entire bed lamination.
Figure 4 is the variation of the standard deviation of the differential pressure of
adjacent beds under different flow rates with the perforated ratio. It can be seen
that under the same gas flow, the standard deviation of pressure drop between adja-
cent beds decreases with the decrease of the perforated ratio of the distributor, and
decreases with the decrease of the height. However, the degree of decrease in pressure
drop deviation at different heights is different. At high gas flow (Q = 140 L/min), the
decrease of the opening ratio of the distribution plate is obvious to the middle and
lower part of the fluidized bed (H = 0–150 mm), but the pressure drop fluctuation
of the fluidized bed (H = 150–250 mm) has little effect. The gas is injected into the
fluidized bed through the distributor, and after reaching a certain height, bubbles are
generated, the bubbles move upward, and the polymerization is broken. Due to the
400 600
H=(-50)-25 mm H=(-50)-25 mm
H=25-50 mm H=25-50 mm
H=50-150 mm H=50-150 mm
300 H=150-250 mm 450 H=150-250 mm
dp/Pa
dp/Pa
200 300
100 150
0 0
100% 8.19% 3.64% 0.91% 100% 8.19% 3.64% 0.91%
Perforated Ratio Perforated Ratio
(a) Q=100 L/min (b) Q=120 L/min
800
H=(-50)-25 mm
H=25-50 mm
H=50-150 mm
600 H=150-250 mm
dp/Pa
400
200
0
100% 8.19% 3.64% 0.91%
Perforated Ratio
(c) Q=140 L/min
Fig. 4 Standard deviation of differential pressure of adjacent beds at different gas flows
gas jet and the decrease of the initial diameter of the bubble, at a certain height, it
is the area where the distributor mainly acts. When it exceeds this height, the effect
of the distributor is weakened, and the main function is the polymerization crack
between the bubbles. Especially at high gas flow, the number and size of bubbles
are larger, and the polymerization is more likely to occur. It is consistent with the
research results of FAN [10].
Comparing the perforated ratio-pressure drop deviation curves of Fig. 4a–c, it can
be found that the standard deviation of the bed lamination decreases as the increase
of the gas flow and the bed height increase. That is the bubble diameter increases as
the gas flow rate and the bed height increase.
Frequency Domain Analysis
Figure 5 is a power spectrum diagram of the pressure fluctuations of different bed

layers in a fluidized bed. With the decrease of the perforated ratio of the distributor,
the main frequency shifts to the left in the region of H = 0–50 mm, and the main
frequency changes are not obvious in the 50–250 mm area. Because the injection
of gas on the distributor reduces the frequency of bubble generation, and in the
region above the ejection height, the frequency of bubble growth and rupture does
not substantially change.
In addition, with the decrease of perforated ratio of distributor, the amplitude of
the mains frequency is greatly reduced at H = 0–150 mm, that is, the size of the
bubbles in each frequency segment is significantly reduced in this region, although
the amplitude of the mains frequency is also reduced in the area of H = 150–250 mm,
the magnitude of the reduction is much smaller than the area of H = 0–150 mm.
That is, the effect of the distributor on the fluidized bed is weakened as the height
increases.
Optical Analysis
Figure 6 shows the growth and movement behavior of bubbles at different perforated
ratios. The results indicated that the bubble in the gas–solid fluidized bed without
distributor is significantly large. The fluidization quality of the entire bed is quite
poor, and the gas–solid distribution is uneven. When the perforated ratio decreased,
the number of bubbles in the gas–solid fluidized bed is gradually reduced, and the
bubble size also remarkably decreased. In the 0–200 mm region (in the red region of
the figure), the size of bubbles decreases significantly with the increase of porosity.
When the porosity decreases to 0.91%, the region is substantially free of bubbles and
670 W. Tao et al.
25 25 25 25
Amplitude/Pa
20 20 20 20
Amplitude/Pa
Amplitude/Pa
Amplitude/Pa
15 15 15 15
10 10 10 10
5 5 5 5
0 0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
Frequency/Hz Frequency/Hz Frequency/Hz Frequency/Hz

Perforated Ratio 100% Perforated Ratio 8.19% Perforated Ratio 3.64% Perforated Ratio 0.91%
(a) H=(-50)-25 mm
25 25 25 25
Amplitude/Pa
20 20 20 20
Amplitude/Pa
Amplitude/Pa
Amplitude/Pa
15 15 15 15
10 10 10 10
5 5 5 5
0 0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
(b) H=25-50 mm
120 120 120 120
Amplitude/Pa
100 100 100 100

Amplitude/Pa
Amplitude/Pa
Amplitude/Pa
80 80 80 80
60 60 60 60
40 40 40 40
20 20 20 20
0 0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
(c) H=50-150 mm
180 180 180 180
Amplitude/Pa
150 150 150 150

Amplitude/Pa
Amplitude/Pa
Amplitude/Pa
120 120 120 120

90 90 90 90
60 60 60 60
30 30 30 30
0 0 0 0
0 5 10 15 20 0 5 10 15 20 0 5 10 15 20 0 5 10 15 20
(d) H=150-250 mm
Fig. 5 Power spectrum of different bed heights in a fluidized bed
the gas–solid distribution is uniform. Therefore, when the open porosity is 0.91%,
the fluidization quality in the gas–solid fluidized bed is better, and the gas–solid
distribution in the bed is more uniform, which is more favorable in the fluidized iron
making process.
(a) Perforated Ratio 100% (b) Perforated Ratio 8.19%
(c) Perforated Ratio 3.64% (d) Perforated Ratio 0.91%
Fig. 6 Bubble growth process under different perforated ratios
Conclusions
(1) For the fluidization characteristic parameters, the perforated ratio of the
distributor does not affect the initial fluidization speed.
(2) Through time-domain analysis, as the perforated rate of the distributor
decreases, the amplitude of the bed pressure signal fluctuation and the pres-
sure drop fluctuation deviation decreases. And the lower part of the fluidized
bed is reduced by a larger amount than the upper part.
(3) Through frequency domain analysis, in the lower part, the reduction of the
perforated ratio of the distributor not only reduces the frequency of bubble, but
also significantly reduces the size of the bubble. In the upper part, the perforated
ratio of the distributor has an effect on the size of the bubble, while the change
of the frequency of the bubble is not obvious.
(4) Through optical analysis, with the perforated ratio of the distributor decreases,
the bubble size decreases. When the perforated ratio is 0.91%, the gas–solid
distribution in the gas–solid fluidized bed is uniform. And it is the particulate
fluidization in the middle and lower part of the fluidized bed.
Acknowledgements This study was financially supported by the National Natural Science Fund
Committee (U1760120), and the National Key R&D Program of China (2017YFC0210404,
2017YFC0210403-04).
672 W. Tao et al.
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pp 566–575
3. Kuisong Z (2014) Cold model experiment and numerical simulation of iron ore powder bubbling
fluidized bed. Chongqing University
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Technol 327(3):358–367
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27(3):388–396
10. Baoliang L, Jianchun J, Jinfang Y et al (2007) Study on fluidization velocity of wood chips in
cold bubbling fluidized bed. Chem Ind Ind 27(3):49–52
11. Luo Z, Zhao Y, Chen Q et al (2004) Effect of gas distributor on performance of dense phase
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fluidized bed: an evaluation. Chem Eng Sci 65(11):3485–3493
13. Dartonr C (1977) Bubble due to coalescence in fluidized beds. Trans Inst Chem Eng 55(3):134–
140
Prediction of Iron Ore Sinter Strength
Using Statistical Technique
Zhongci Liu, Xuangeng Zhou, Gang Li, Shanshan Wu and Xuewei Lv
Abstract Sinter is the main iron-containing raw material for blast furnaces. As iron
ore resources are gradually depleted, the types of raw materials for sinter are compli-
cated, so their chemical composition often changes. At present, the common method
for studying the sintering performance of iron ore is the sintering pot test. This
method is cumbersome and needs a long process time, and it is impossible to rec-
ognize the rapid reaction change of the raw material. Therefore, a prediction model
was established by building a sintering experimental database and using statistical
analysis methods such as correlation, regression and sequence quadratic program-
ming analysis to analyze the relationship between the chemical composition and
the tumbler strength of sinter, so as to simplify the sintering blending technology.
The regression coefficient of the model is 0.803, indicating that the model has good
prediction potential for sinter strength.
Keywords Sinter strength · Sequence quadratic programming · Prediction model
Introduction
In spite of the development and introduction to industrial production of a large number

of new iron-making processes, blast furnace iron-making is still dominant in the world
[1]. Sinter is the main iron-containing feed to the blast furnace, and its quality is a key
element for the stable operation of blast furnace [2]. With the development of iron
and steel industry, the consumption of high-grade iron ore accelerates, resources
gradually become depleted. Therefore, some industrial raw materials and wastes
containing iron are widely used, whereas the chemical composition of sinter raw
materials changes frequently. At present, the commonly used method for studying
the sintering performance is the sintering pot test. However, it is a heavy work, long
time process and unable to identify a rapid reaction change of the raw material [3].
Z. Liu · X. Zhou · G. Li · S. Wu · X. Lv (B)

e-mail: lvxuewei@163.com

https://doi.org/10.1007/978-3-030-36540-0_60
674 Z. Liu et al.
Therefore, researchers have started focusing on finding a relationship between

output and input characteristics of sinter, using extensive data analysis to construct
a prediction model. This model should have the capability of predicting the desired
sinter quality well in advance, so that minor modifications can be made to achieve
the optimum quality requirements for smooth function of blast furnace [4]. Vikash
et al. constructed the prediction model for Mean particle size (MPS), tumbler index
(TI) and reduction degradation index (RDI) based on back propagation (BP) neural
network, which was trained and tested by actual plant data [4]. Xiao-hui Fan et al
constructed the prediction model for moisture content, fuel ratio, sintering speed and
the sintering drum strength by using stepwise regression analysis and BP artificial
neural network [3].
In present work, impact of sinter chemical composition (Total iron content, Al2 O3 ,
MgO, CaO and SiO2 ) on the sinter product qualities have been studied using statistical
tools such as correlation, regression and sequence quadratic programming analysis.
Construction of the Prediction Model
Due to the main components of gangue in iron ore and flux are total iron (The
following is expressed in TFe), MgO, SiO2 , Al2 O3 and CaO, the mass fraction of the
above five components is selected as the independent variables, and tumbler index
(TI) of the sinter is regarded as the dependent variable.
The correlation analysis focuses on finding some quantitative indicators between
variables to describe the depth of relationship between variables and regression anal-
ysis focuses on finding some approximate functional relationship between variables.
The Pearson Product-Moment correlation is a measure of the linear relationship
between two typically continuous variables. The mathematical definition of the
Pearson Product-Moment correlation coefficient is the following:

n
(xi −x)(yi −y)
i=1
n−1 covxy
r= = (1)
sx · sy sx · sy
where sx and sy are the standard deviations of the two variables. The numerator of
r is the covariance, denoted by covxy . The covariance is divided by the product of
standard deviations, sx ·sy, to standardize the covariance and provide a dimensionless
measure of a linear relationship between variables x and y. The range of r is between
−1 and +1. The results of the analysis are shown in Table 1.
It can be seen that the Pearson correlation between TI and TFe was equal to
0.195 as well as the one-tailed under the test of significance was 0.035, which was
statistically significant at the 0.05 level of significance. The correlation between other
variables is the same as above.
Prediction of Iron Ore Sinter Strength Using Statistical Technique 675
Table 1 Correlations analysis between variables

TI TFe Al2 O3 SiO2 CaO MgO
Pearson correlation TI 1.000 0.195 −0.457 0.291 0.423 −0.220
TFe 0.195 1.000 −0.679 −0.612 −0.460 −0.557
Al2 O3 −0.457 −0.679 1.000 0.426 0.291 0.193
SiO2 0.291 −0.612 0.426 1.000 0.778 0.194
CaO 0.423 −0.460 0.291 0.778 1.000 0.168
MgO −0.220 −0.557 0.193 0.194 0.168 1.000
Sig. (1-taild) TI 0.035 0.000 0.003 0.000 0.021
TFe 0.035 0.000 0.000 0.000 0.000
Al2 O3 0.000 0.000 0.000 0.003 0.037
SiO2 0.003 0.000 0.000 0.000 0.036
CaO 0.000 0.000 0.003 0.000 0.060
MgO 0.021 0.000 0.037 0.036 0.060
Subsequent to the correlation analysis, the identified input parameters are used
for regression analysis. The multiple linear regression model with five variables is
as follows:

Y = β0 + β1 x1 + β2 x2 + β3 x3 + β4 x4 + β5 x5 + ε,
(2)
ε ∼ N (0, σ 2 )
where β i (i = 0, 1,…, 5) are regression coefficients and ε is the error in prediction.

Select the parameters (β 0 , β 1 , …, β 5 ) that minimize the error of the model as the
estimate of the regression coefficient, that is:

n
min εi2 (3)
β1 ,β2 ,··· ,β5
i=1
The results of the regression are shown in Tables 2 and 3.

R represents the coefficient of multiple correlations between the TI and the five
predictors considered simultaneously (TFe, Al2 O3 , MgO, CaO and SiO2 ). R-square
is the coefficient of multiple correlations squared (called the multiple determina-
tion coefficient) and represents the proportion of variance in the response variable
Table 2 Model summary for the regression

R R2 Adjusted R square Std. error of the estimate Durbin-Watson
0.783 0.614 0.590 3.981 1.126
676 Z. Liu et al.
Table 3 Coefficients for the model

β Std. error t sig Tolerance VIF
(Constant) 67.129 14.930 4.496 0.000
TFe −0.027 0.204 −0.134 0.894 0.258 3.871
Al2 O3 −3.957 0.587 −6.736 0.000 0.488 2.051
SiO2 1.499 0.715 2.097 0.039 0.300 3.335
CaO 1.093 0.274 3.994 0.000 0.392 2.553
MgO −2.685 1.062 −2.527 0.013 0.593 1.685
accounted for or “explained” by simultaneous knowledge of the predictors. Durbin-

Watson is used to test whether there is collinear relationship between variables lead-
ing to over-fit, and its value of 1.126 indicates that there is no significant correlation
between residuals, that is, residuals are independent and there is no collinearity.
As can be seen from Table 3, β i (i = 1, 2, …, 5) is the coefficients of the multiple
linear regression equation. It indicates the effect for one-unit increase of independent
variable on the tumbler index, given the inclusion of all other predictors in the model.
The Constant is the β 0 in the model. The estimated standard errors in the next
column are used in computing a t-test for each coefficient to determine whether the
coefficient is statistically significant at p < 0.05. Collinearity statistics are generally
taken tolerance or variance inflation factor (VIF) as diagnostic indexes. The values
in the last two columns in Table 3 indicate that there is no collinear relationship
between independent variables.
From many sintering experiments, it can be seen that the influence of the gangue
composition in ore on the sinter strength is not a simple linear relationship. In indus-
trial production, the simpler the form of the prediction model is more convenient
for the actual production operation. Therefore, in the present study, the multino-
mial regression was used to construct the model and the sample repetition method
was used to calculate the standard error for nonlinear fitting. The sample repetition
method needs the support of sequential quadratic programming algorithm. Sequen-
tial quadratic programming was first proposed by Wilson in 1963. Its basic idea is to
determine a descending direction by solving a quadratic programming sub-problem
in each iteration, obtain the moving step size of the current iteration point by reducing
penalty function, and repeat these steps until the solution of the original problem is
obtained. In this study, the solution of the original problem is corresponding param-
eters of regression function. The penalty condition is the minimum sum of squares
of residuals. The regression function sees Eq. (4), and its corresponding parameters
y(TI ) = a0 + a1 · x(TFe) + a2 · x(Al O ) + a3 · x2 + a4 · x(MgO) + a5 · x(CaO) + a6 · x2 + a7 · x(SiO2 )

2 3 (MgO) (SiO2 )
(4)
The coefficients of Eq. (4) are available from Table 4. The regression coefficient
of the model is 0.803. The constant of the model is the a0 . It is the predicted value for
Table 4 Corresponding parameters of regression function

Coefficients Estimation Std. error 95.0% confidence interval for
coefficients
Lower bound Upper bound
a0 61.439 15.899 29.794 93.085
a1 −0.150 0.203 −0.554 0.254
a2 −4.205 0.603 −5.406 −3.005
a3 −2.793 1.208 −5.197 −0.389
a4 8.095 4.871 −1.600 17.790
a5 1.261 0.276 0.711 1.811
a6 −0.237 0.299 −0.833 0.358
a7 3.145 3.275 −3.375 9.665
the TI when the values of TFe, Al2 O3 , MgO, CaO and SiO2 all equal to 0. Obviously,
this situation makes little sense. For this reason, predictors in a model are sometimes
mean centered if one wishes to interpret the constant in a meaningful way. In addition,
the coefficient for TFe, equal to −0.150, represents for a one-unit increase in TFe,
on average, TI decreased by 0.15 units, given the inclusion of all other predictors in
the model.
The coefficient for Al2 O3 (−4.205) represents a one-unit increase in Al2 O3 result-
ing in a decrease of TI by 4.205 units, on average. A similar conclusion was reported
that the sinter tumbler index deteriorates as the alumina content increases. There are
three views on the effect of alumina on the strength of sinter [5–8]. As the alumina
content increases, more alumina will dissolve into the lattices of hematite, SFCA
and the glass phase, causing a decrease in the strength of the sinter. An increase in
alumina content in sinter increased columnar shaped SFCA phases, but decreased
needle shaped SFCA-1 which is beneficial to high sinter strength. An increase in alu-
mina content would make the sinter structure more porous and hence cause weaker
strength.
The coefficient for CaO (1.261) represents a one-unit increase in CaO resulting
in an increase of TI by 1.261 units, on average. A similar conclusion was reported
that the amount of calcium ferrite increased with basicity, when the SiO2 content
is fixed. The columnar shaped SFCA is gradually reduced, and the needle shaped
SFCA-1 having a good strength is rapidly increased [9, 10, 17].
The multinomial for MgO is −2.793x2 + 8.095x. It can be seen that when the
MgO content increases within a certain range, the TI will increase accordingly, after
which tumbler index decreased when the MgO content further increased. A similar
conclusion was reported that the effect of MgO content on sinter strength is of
a dual character. The initial strength increases with the increase of MgO content,
and the intensity begins to decrease when the maximum is reached [6, 11]. Since
the ionic radii of Mg2+ and Fe2+ are relatively close, Mg2+ enters the magnetite
lattice and mainly exists in magnetite to form magnesium spinel [(Fe,Mg)O·Fe2 O3 ],
which is more refractory than calcium ferrite [14]. Calcium ferrite phase decreases
678 Z. Liu et al.
whereas magnetite and silicate melt/gassy phase increase with increase in MgO.
The formation of vitreous glassy matrix and dicalcium silicates are harmful to sinter
strength because these structures exhibit a high degree of stress and therefore result
in a remarkable drop in sinter TI [6, 11–14].
The multinomial for SiO2 is −0.237x2 + 3.145x. It can be seen that when the SiO2
content increases within a certain range, the tumbler index will increase accordingly,
after which tumbler index decreased when the SiO2 content further increased. Within
a certain range, the increase of SiO2 content contributes to the development of calcium
ferrite from short column or plate shape to needle shape, which is beneficial to high
sinter strength. The SiO2 content continues to increase, and the silicate content in
the sinter increases, so that the amount of calcium ferrite is reduced and the drum
strength is greatly decreased [15, 16].
Conclusions
The composition of the sinter is increasingly complex and significantly affected by the
gangue composition. In present work, a statistical model for predicting sinter strength
is proposed by the sequence quadratic programming algorithm. The regression value
of the model is highly fitted to the actual value (regression coefficient is 0.803),
which indicates that the model has good prediction potential for sinter strength. The
developed model can act as a tool for prediction of tumbler index, well in advance,
which will greatly facilitate the optimization of sinter strength. The shortcomings
are that because the data volume is not large enough, future work should continue to
expand the database to improve accuracy of model.
Acknowledgements The authors are grateful to the financial support of National Key Research
and Development Program of the Ministry of Science and Technology (2018YFC1900501).
References
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technique. Trans Indian Inst Met 70(6):1661–1670
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sintering performance. Ironmaking Steelmaking 42(1):34–40
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mina contents of iron ore sinter influence its mineralogy and properties. J South Afr Inst Min
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in iron ore sintering. Baosteel Techn Res 11(3):7–11
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Pelletiz 39(6):12–16
Reducing Carbon and Nitrogen Oxides
Emission in Iron Ore Sintering Process
by Double-Layer Pre-sintering
Technology
Mingshun Zhou, Yidong Wang, Dongming Zhao, Yan Gu, Jianwei Zhu,
Huibo Liu, Qiang Zhong and Tao Jiang
Abstract Aiming at reduction of carbon and nitrogen oxides emission in Iron

ore sintering process and increasing of sintering productivity, a new technology of
double-layer pre-sintering has been developed. The new technology is quite different
from the conventional single-layer sintering and has been adopted in No. 2 sintering
workshop of Anshan Iron and Steel Group Co. Ltd. During the industrial-scale pilot
at a 360 m2 sintering machine for 26 weeks, the total emission of carbon and nitrogen
oxides was decreased by 45239.8 tons and 615.4 tons, respectively, the productivity
of sintering machine increased from 450.6 to 523.2 t/h that is equal to a 16.11%
increase of output. The blast furnace used for the sinter produced through the new
process is in good condition and a good economic and environmental result has been
achieved.
Keywords Iron ore sintering · Double-layer pre-sintering · Carbon oxides and

nitrogen oxides · Emission
M. Zhou (B) · J. Zhu

Iron and Steel Research Institute, AnSteel Group Corporation, No. 63, Wuyi Road, Tiedong
District, Anshan 114009, China
e-mail: zms4652@163.com
H. Liu · Q. Zhong · T. Jiang
China
e-mail: jiangtao@csu.edu.cn
Y. Wang · Y. Gu
Ansteel Group Corporation Ltd, Anshan 114000, China
D. Zhao
Iron-Making Plant, Angang Steel Co. Ltd, Anshan 114000, China

https://doi.org/10.1007/978-3-030-36540-0_61
682 M. Zhou et al.
Introduction
The crude steel yield of China accounts for 50% of that in the world. A large amount
of NOx -containing waste gas is discharged during the steel production process, caus-
ing serious pollution and damage to the environment. The emission of NOx in the
sintering and pelletizing processes in China accounts for 54.66% of the total emission
of NOx in iron and steel industry. The concentration of NOx in sintering exhaust gas
in China is generally 200–400 mg/m3 . In recent years, the Ecological Environment
Ministry of China has put forward more stringent requirement on concentration of
NOx in sintering exhaust gas, which is less than 50 mg/m3 . At present, for the existing
nitrogen oxides controlling technology in sintering process, the cost is huge. There-
fore, how to advance the end nitrogen oxides control in existing sintering process
to achieve the maximum reduction of emission has great practical significance to
reduce NOx emission in total.
Focusing on high quality, efficient, energy saving and emission reduction, the
researchers have done a lot of exploration of new sintering methods and technologies
[1–8]. Thick bed sintering, which can raise sinter yield and improve tumbler strength,
reduce pollutant emission, represents a developing direction of iron ore sintering and
has been paid much attention recently. However, the sintering productivity decreases
once the height of sintering layer exceeds 720 mm. The most sintering workshops
in Ansteel use fine concentrate that may negatively influence the green mix bed
permeability and the productivity of sinter machine.
In order to realize low emission of nitrogen oxides and carbon oxides in Sintering
waste gas and use a large proportion of fine iron concentrate, a new technology has
been developed with pre-sintering and ultra-thick bed layer [9–12]. In the condition
of normal oxygen content, the relationship between pre-sintering time and the height
ratio of upper and lower layer for double-layer sintering were successfully explored
and optimized. In the industrial test, the feeding system was improved and the igniter
was moved forward in the sintering machine, and a series of testing and follow-
up work were carried out. The results showed that double-layer sintering greatly
increased production, and the sinter quality met the requirement of blast furnace
very well.
In the paper, the laboratory research and the industrial pilot of double-layer pre-
sintering technology with ultra-thick bed layer were introduced. The industrial pilot
was conducted at a 360 m2 sinter machine in No. 2 Sintering Workshop of Anshan
Iron and Steel Co., Ltd for nearly 7 months. A new pre-sintering process was proposed
to provide technical support to achieve the goal of high-quality, efficient and green
production in sintering industry.
Reducing Carbon and Nitrogen Oxides Emission … 683
Materials
The experimental materials were taken from the second sintering workshop of the
main iron-making plant of Anshan Iron and Steel Co., Ltd. The chemical composition
of raw materials is shown in Table 1. The iron-bearing raw material used in the
research is blended ore that is made up of 65% of fine iron concentrate produced by
AISC and 35% of iron ore powder purchased from abroad. The size of the blended
ore is fine relatively, its content of −0.5 mm reaches up to 73.24%, resulting in
the poor permeability of sintering mixture. The main content of the limestone and
quicklime is CaO, 46.85% and 62.36%, respectively. The lol of coke breeze is as
high as 84.85%.
Methods
Aiming at reducing NOx and COx emission and increasing yield of iron ore sintering,
the new process is quite different from the conventional single-layer sintering process.
In the new process, the first feed mixture layer (lower layer) is distributed on the
sinter machine pallet, then the first feed mixture layer is ignited for one minute.
After approximate 10 to 20 min sintering (the length of pre-sintering time is up
to the height ratio of upper and lower layer), the second sinter feed mixture layer
(upper layer) is distributed on the top of the first layer and ignited for 1.5 min. The
total height of sinter feed mixture bed is Approximate 1000 mm. The schematic
diagram of double-layer pre-sintering new process is shown on Fig. 1. The 10 to
20 min sintering in the first layer is named as pre-sintering that is very important to
the whole process. Through the pre-sintering process, the NOx and COx emission in
sintering can be largely reduced. This came from both the laboratory sinter pot test
and the industrial-scale sinter machine pilot.
Concentrations of NOx and COx in Sinter Waste Gas Decrease
Sinter pot tests were conducted in laboratory. Comparing with the conventional
single-layer sintering process that the sinter-mix bed height was 700 mm, and total
height of the sinter-mix bed of double-layer pre-sintering was 1000 mm. The pre-
sintering time was fixed to 20 min. The result of NOx and COx emission reduction
is analyzed below.
684
Table 1 Chemical composition of all the raw materials in sinter mixture (mass%)
Raw materials TFe FeO CaO SiO2 MgO Al2 O3 S P LOI
Blended ore 57.86 16.17 4.28 5.02 1.02 0.93 0.044 0.035 5.84
Limestone 0.65 0.45 46.85 5.09 2.95 1.05 0.040 0.019 40.74
Quicklime 0.38 0.036 62.36 2.69 3.20 0.43 0.068 0.011 27.75
Coke breeze 1.08 – 0.51 7.54 0.13 4.17 0.008 0.036 84.85
M. Zhou et al.
Bedding bin Blending bin First Igniter Blending bin Second Igniter
Moving Direction
Sinter Machine
Fig. 1 Schematic diagram of double-layer pre-sintering new process
The main pollutants in sintering process are carbon oxides and nitrogen oxides.
The nitrogen oxides produced during sintering process are mainly fuel-type NOx ,
which came from the transformation of N component in fuel. More than 90% of the
nitrogen oxides is NO, and the rest is mainly NO2 . The carbon oxides are carbon
monoxide and carbon dioxide, which are produced by chemical reactions such as
combustion of C component in fuel.
For 700 mm bed height single-layer sintering and 1000 mm bed height double-
layer sintering, the concentrations of carbon oxides and nitrogen oxides in emission
gas are shown in Figs. 2, 3, 4, 5, 6, 7, 8, and 9. The data (NO, NO2 , CO, CO2 ) in
all the diagrams (Figs. 2, 3, 4, 5, 6, 7, 8, and 9) obtained from the experiment are
400
350
300
250
NO/ppm
200
150
100
50
-50
-5 0 5 10 15 20 25 30 35 40
Time/min
Fig. 2 NO concentration in exhaust gas with conventional single-layer sintering process (700 mm
bed height)
686 M. Zhou et al.
10
6
NO2/ppm
-5 0 5 10 15 20 25 30 35 40
Time/min
Fig. 3 NO2 concentration in exhaust gas with conventional single-layer sintering process (700 mm
bed height)
30
25
20
CO2/%
15
10
0
-5 0 5 10 15 20 25 30 35 40
Time/min
Fig. 4 CO2 concentration in exhaust gas with conventional single-layer sintering process (700 mm
bed height)
10
6
CO/%
-5 0 5 10 15 20 25 30 35 40
Time/min
Fig. 5 CO concentration in exhaust gas with conventional single-layer sintering process (700 mm
bed height)
400
350
300
250
NO/ppm
200
150
100
50
-50
-5 0 5 10 15 20 25 30 35 40 45
Time/min
Fig. 6 NO concentration in exhaust gas with conventional double-layer sintering process (1000 mm
bed height)
calculated by integral method. The emission of Carbon oxides and Nitrogen oxides
per ton of sinter are shown in Table 2.
688 M. Zhou et al.
10
6
NO /ppm
4
2
-5 0 5 10 15 20 25 30 35 40 45
Time/min
Fig. 7 NO2 concentration in exhaust gas with conventional double-layer sintering process
(1000 mm bed height)
30
25
20
CO /%
15
2
10
0
-5 0 5 10 15 20 25 30 35 40 45
Time/min
Fig. 8 CO2 concentration in exhaust gas with conventional double-layer sintering process
(1000 mm bed height)
10
6
CO/%
-5 0 5 10 15 20 25 30 35 40 45
Time/min
Fig. 9 CO concentration in exhaust gas with conventional double-layer sintering process (1000 mm
bed height)
Table 2 Emission of carbon oxides and nitrogen oxides per ton of sinter with different sintering
methods
Sintering method NO/kg NO2 /kg CO2 /kg CO/kg
700 mm conventional sintering 0.57 0.0089 145.20 9.36
1000 mm double-layer pre-sintering 0.24 0.0065 132.80 8.47
The NOx concentration in exhaust gas decreases after the second ignition because
the NOx produced in the upper layer reacts with CO and Fem On in the lower pre-
sintered layer and forms N2 (g). The temperature of sintering combustion zone is
about 700–1400 °C, under which the NO can easily react with CO, C, and Fem On
in the first sintering layer. The lower sinter layer is likely as the filter screen to NOx ,
and it holds back the gas of NOx and changes it to N2 . So, the NOx concentration in
exhaust gas is decreased greatly (Figs. 6 and 7). The possible reduction reactions in
the lower sintering layer are as follows:
2CO(g) + 2NO(g) = 2CO2 (g) + N2 (g) (1)
C(g) + 2NO(g) = CO2 (g) + N2 (g) (2)
3FeO + NO(g) = Fe3 O4 + 1/2N2 (g) (3)
2Fe3 O4 + NO(g) = 3Fe2 O3 + 1/2N2 (g) (4)

690 M. Zhou et al.
Table 3 Comparison of different sintering process indexes

Sintering Sintering Tumbling Utilization Solid fuel
method speed/mm index/% coefficient/t (m2 consumption/kg
min−1 h)−1 t−1
700 mm 18.37 61.53 1.26 46.13
conventional
sintering
1000 mm 20.30 60.87 1.60 44.01
double-layer
pre-sintering
Sinter Productivity of Double-Layer Pre-sintering
The indexes of sinter pot of conventional single-layer process and double-layer pre-
sintering new processes are compared in Table 3.
For double-layer pre-sintering, the first layer (lower layer) is firstly ignited and
sintered, then the second layer (upper layer) is laid, ignited, and sintered, Therefore,
there are two combustion zones moving simultaneously in the sintering layer. After
the upper layer ignition, the lower layer has to use the sintering waste gas from the
upper layer. However, the low oxygen content of the exhaust gas from the upper
layer affects carbon combustion in the lower layer, further affects the mineralization
process, which will result in lower yield and lower drum strength, Table 3.
From Table 3, the double-layer pre-sintering can significantly increase the ver-
tical sintering speed Comparing with the 700 mm conventional sintering, result in
increased sintering utilization coefficient and tumbling index. And the solid fuel con-
sumption decreased from 46.13 to 44.01 kg/t, equaling 2.12 kg/t reduction in sinter
pot test.
Industrial-Scale Pilot of Double-Layer Pre-sintering
Double-layer pre-sintering process Industrial-scale pilot was conducted in a 360 m2

sinter machine in Iron-making Plant, Ansteel. The pilot results showed that the height
of sinter-mix bed can be increased from 700 mm in the conventional single-layer
sintering process to 1000 mm in the double-layer pre-sintering new process without
oxygen enrichment. The sinter output per hour increased from 450.6 to 523.2 t,
which is equal to 16.11% increase without increasing the capacity of sinter fan. At
the same time, the concentration of carbon oxides and nitrogen oxides has been
greatly decreased (Table 4).
For the 360 m2 sinter machine, nitrogen oxides emission decreased 0.2908 kg
per ton of sinter. During the 26 weeks of the double-layer pre-sintering new pro-
cess industrial-scale pilot, the sinter output is 2,115,000 tons. The total emission
reductions of nitrogen oxides and carbon oxides are 615.4 tons and 45239.8 tons,
Table 4 Emissions of carbon oxides and nitrogen oxides per ton of sinter with different sintering
method
Sintering method NO/kg NO2 /kg CO2 /kg CO/kg
700 mm conventional sintering 0.55 0.0078 155.28 9.19
1000 mm double-layer pre-sintering 0.26 0.0070 134.85 8.23
Table 5 Electric power and

Sintering process Electric power Solid fuel
solid fuel consumption of
consumption consumption (kg/t)
different sintering processes
(kwh/t)
700 mm 46.42 51.88
conventional
sintering
1000 mm 43.48 49.90
double-layer
pre-sintering
700 mm −2.94 −1.98
conventional
sintering
respectively. The electric power and solid fuel consumption of different sintering
processes are shown in Table 5.
In the industrial-scale pilot of double-layer pre-sintering new process, compared
with conventional single-layer sintering, the consumption of solid fuel decreased
from 51.88 to 49.90 kg/t, which is 1.98 kg/t reduction in 26 weeks. According to
2,115,000 tons sinter output in this period, the total solid fuel consumption reduction
is 4187.7 tons. The sinter produced by the new double-layer pre-sintering process
was used in No. 1 Blast furnace in Iron-making Plant, and the blast furnace run well.
The coke ratio decreased 1.2 kg/t and better economic and environmental benefits
have been achieved.
Conclusion
(1) Double-layer pre-sintering new process can reduce carbon oxides and nitrogen
oxides emission during Iron Ore sintering. For the industrial-scale pilot with a
360 m2 sinter machine in 26 weeks, the total emission reductions of nitrogen
oxides and carbon oxides are 615.4 tons and 45239.8 tons, respectively.
(2) By adopting the double-layer pre-sintering new process, the height of the sinter
bed layer was raised from 700 mm to1000 mm, thus the sinter output per hour
increased from 450.6 tons to 523.2 tons, which is a 16.11% increase without
increasing capacity of sinter fan.
692 M. Zhou et al.
(3) During the industrial-scale pilot, compared with conventional single-layer sin-
tering, the total solid fuel consumption of the new process decreased 4187.7
tons.
(4) The sinter produced by the new double-layer pre-sintering process was used in
No. 1 blast furnace and it ran well. The coke ratio decreased 1.2 kg/t and better
economic and environmental benefits have been achieved.
(5) The cold strength of sinter in the new process decreased a little. It might be
caused by the lack of oxygen in the lower layer sintering process. Some techno-
logical parameters of the new process need to be further optimized to achieve
better sintering output, solid fuel consumption reduction and lower emission of
nitrogen and carbon oxides.
Acknowledgements This work was supported by the Anshan Iron and Steel Group Co. Ltd under
Grant 738010261.
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11. Zhou MS, Tang FP, Liu J (2017) A method for judging the burning end point of super-thick
material layer by pre-sintering: China, 201610815324. X
12. Zhou MS, Tang FP, Ren ZP (2017) A method and device for improving the combustion
permeability of super-thick material layer: China, 201610815533. 4
Research on Mechanism of Ring
Formation in Grate-Kiln
of Titanium-Containing Pellets
Haoyu Cai, Jianliang Zhang, Zhengjian Liu, Gele Qing and Yan Zhang
Abstract The growth rate of ring formation increased when titanium-containing

powder had been added into Shougang grate-kiln to produce titanium-containing
pellets, which had a strong impact on the production processes. In this article, the
mechanism and influencing factors of the ring formation problem had been studied,
based on sampling and analyzing samples from different parts of kiln. The result
indicated that liquid phase of low-melting point and particles were the main reason
of ring formation. The ring formation was difficult to clean up because its strength
increased in the high-temperature oxidability atmosphere. The desiccation and pre-
heat of green-ball were degraded when the titanium-containing fines had been added.
A large amount of powder and particles were produced in kiln because of the lower
compressive strength of dry-ball, which led to the rapid growth of rings.
Keywords Titanium-containing pellet · Grate-kiln · Ring formation
Introduction
Titanium-containing ore is used by ironmaking workers frequently [1, 2], to bring

down the temperature of erosion area and protect the hearth of blast furnace [3].
For the purpose of prolonging the service life of blast furnace, outsourcing titanium-
containing pellets and import titanium ore were added into raw materials from 2015.
The hot metal cost also increased because the titanium ore was too expensive. In May
2018, Shougang began to add some titanium-containing powder into grate-kiln to
produce titanium-containing pellets. But the growth rate of ring formation increased
soon after the industrial test began, which had a strong impact on the production
processes. Different kinds of explanations of ring formation growth haven been
given out by different researchers [4–7].
H. Cai (B) · J. Zhang · Z. Liu

University of Science and Technology Beijing, Beijing, China
e-mail: caibo890107@163.com
H. Cai · G. Qing · Y. Zhang
Shougang Research Institute of Technology, Beijing, China
https://doi.org/10.1007/978-3-030-36540-0_62
694 H. Cai et al.
Table 1 Material ratio of experiment on titanium-containing pellet

Scheme Self- mined powder Imported powder (%) Dust (%) Titanium-containing
(%) powder (%)
A 57 40 3 0
B 54 40 3 3
C 52 40 3 5
In this paper, sampling and analyzing of ring formation from different positions
in rotary kiln have been taken during maintenance, which would reveal the causes
of ring formation growth and provide some effective control methods.
The Production of Titanium-Containing Pellet
The main raw material of producing titanium-containing pellets in Shougang includes

self-mined mineral powder, imported powder, dust, and a certain proportion of
titanium-containing powder. The ratio of material is shown in Table 1.
The compositions of raw materials used are shown in Table 2. Both self-mined
and imported powders are high-grade magnetite powders with low silicon. Especially
imported magnetite powders have a grade of 69.52%, but with high content of harmful
elements. Titanium-containing powder is a kind of low-Ti powder with fine particle
size. The proportion of particles less than 200 mesh is 81.14%, the content of titanium
dioxide occupying for 12.45%. The added dust is mainly electrostatic dust, which is
added to pellets as solid waste for recycling.
Sampling of Ring Formation in Rotary Kiln
The palletizing rotary kiln of Shougang has a diameter of 4.7 m, an effective length of
35 m and a rotational speed of 1.3 r/min. In order to study the causes of ring formation
in different areas of the rotary kiln, in the longitudinal direction of the rotary kiln,
we divided the kiln into three parts—the head area, the middle area, and the tail area,
as it is shown in Fig. 1. The position of the head is 0–8 m from the discharge end,
and the temperature is about 1050–1200 °C; the distance of the middle kiln from the
discharge end is 8–18 m, the temperature is about 1200–1250 °C; the distance from
the kiln tail to the discharge end is 18–35 m, the temperature about 900 to 1250 °C.
A total of 8 ring formation samples were taken in three areas of the rotary kiln.
The sampling positions are shown in Table 3.
Observing and analyzing the kiln-ringing in the rotary kiln, the results show that
there are many relatively ring formations in the middle area, while less in the head area
Table 2 Chemical composition and particle size of materials (mass %)
Materials TFe FeO SiO2 CaO MgO Al2 O3 TiO2 K2 O Na2 O S ≤200 meshes
Self-mined powder 67.36 28.48 4.67 0.4 0.58 0.76 0.23 0.017 0.026 0.078 83.85
Research on Mechanism of Ring Formation …
Import powder 69.52 28.95 1.83 0.39 0.66 0.33 0.08 0.065 0.26 0.16 88.23
Dust 61.56 7.26 6.88 0.75 0.74 2.74 0.22 0.094 0.5 0.22
——
Titanium-containing powder 56.68 29.17 4.06 1.87 1.24 1.38 12.45 0.048 0.26 0.19 81.14
695
696 H. Cai et al.
Fig. 1 Sketch of ring formation in rotary kiln
Table 3 Sampling location in rotary kiln

Location Head Middle Tail
Distance from head 2m 6m 9m 12 m 15 m 18 m 22 m 30 m
Sample number 1 2 3 4 5 6 7 8
and the tail area, and the ring characteristics of different parts are also significantly
different.
Figure 2 shows the head area ring formation and the sample. The kiln head area
is relatively flat and the ring formation is about 30 cm. Due to the machine stopping
and temperature lowering, many cracks appear in rings followed by a large surface
spall. The surface of the sample is rough and can be seen to have many powders and
small particles.
Figure 3 shows the ring formation and sample in the middle area. Rings in the
middle area is thick and irregular in shape. Lumps are mostly columnar or conical,
and the thickness is about 30–70 cm. Most of the lumps have broken and peeled off as
shown in Fig. 3a. The obvious stratification phenomenon occurs in the lumps obtained
in the middle kiln. As shown in Fig. 3b, the upper layer is mainly composed of
Fig. 2 Ring formation and sample in the head of kiln

Research on Mechanism of Ring Formation … 697
Fig. 3 Ring formation and sample in the middle of kiln
powders, small particles, and residual pellets. Its structure is loose and the strength is
low because of short forming time; the upper layer has high compact strength because
of long-term high-temperature calcination, where powders and small particles have
formed as a whole.
Figure 4 shows the ring formation and sample in the tail area. The tail area has thin
rings, with about 10 cm thickness. The surface is relatively flat, and occasionally there
are local lumps. The samples obtained from the kiln tail have many surface cracks,
with low strength and easy cracking, accompanied by large pieces of refractory
material.
Fig. 4 Ring formation and sample in the tail of kiln

698 H. Cai et al.
Reason Analysis on the Growth of Ring Formation
Analysis on the Structure and Composition
The composition of the samples obtained in the head area, the middle area and the
tail area were analyzed and compared with the composition of the fired pellets. The
results are shown in Table 4.
The results show that the compositions of the samples from different areas in the
kiln are quite different. The content of TFe in the head and the tail sample are low,
while the content of SiO2 , Al2 O3 , CaO, and the like are higher than that in the fired
pellets, which indicates that the lumps in the head and tail area have more liquid
phases.
The samples obtained in the middle kiln were observed by SEM, as shown in Fig. 5.
It can be seen from the figure that powders and small particles are main elements
in the lumps, and a large amount of liquid phase structure formed by low-melting
substances exists, which wraps and bonds the solid phase structure.
Combining with the analysis above, it can be seen that because of the existence of
the liquid phase, the powders and particles in the rotary kiln can be bonded together.
Due to the high temperature and the oxidizing atmosphere, the solid-phase reaction
between the bonded particles can be fully conducted, and the ringing strength can
be improved. Therefore, the formation of low-melting liquid phase and the existence
of a large number of particulate matters in the kiln are the main reasons resulting in
the ringing growth in the rotary kiln. Besides, it is difficult to remove the rings due
to high strength in the long-term high-temperature oxidation roasting atmosphere.
The results of the elemental analysis of solid and liquid phases indicate that the
composition of solid phases is similar to that of finished pellets. The reason could be
that the solid phase should be formed by consolidation of pellets or powders peeled
off from pellets in high-temperature area. The mechanism of consolidation should be
the same as that of pellets. The liquid phase is formed in soft melting by low-melting
substances with high contents of Si, Al, Ca, and Mg, but Ti is not found. Most of the
Ti elements in the lump formation are in the solid phase, while there are few in the
liquid phase. The Ti element is not the direct reason resulting in ringing formation
in the rotary kiln.
Analysis of the Quality of Dry Pellet and Fired Pellet
Sampling the dried pellets the tail and fired pellets from the head of rotary kiln,
the research was carried out to study the quality changes of dried pellets and fired
pellets before and after adding titanium-containing powders. The results are shown
in Table 5.
From the comparison results in Table 5, it can be seen that when the proportion of
titanium-containing powders increase, the quality of dried pellet decreases and the
Table 4 Chemical composition of samples
Sample TFe FeO SiO2 Al2 O3 CaO MgO TiO2 K2 O Na2 O
Research on Mechanism of Ring Formation …
Sample in head 63.87 1.33 4.53 1.17 0.62 0.85 0.56 0.095 0.3
Sample in middle 64.98 0.25 3.80 0.91 0.52 0.56 0.49 0.072 0.3
Sample in tail 62.96 0.32 4.89 1.61 0.95 0.86 0.43 0.067 0.25
Fired pellets 65.61 0.29 3.99 0.80 0.50 0.58 0.58 0.045 0.14
699
700 H. Cai et al.
Analysis points O Na K Mg Al Si Ca Fe Ti
Point 1 56.17 4.18 0.58 2.72 3.45 24.12 3.55 5.82
Point 2 33.03 0.00 0.47 1.05 0.14 0.22 65.09 0.87
Point 3 54.75 3.02 0.55 3.65 3.16 24.84 3.38 7.20
Point 4 37.46 0.17 0.00 0.40 0.16 0.01 61.79 0.54
Fig. 5 Analysis result of scanning electron microscope
Table 5 Quality of dried pellet and fired pellet

Scheme Quality of dried pellet Quality of fired
pellet
Compressive Shocked pellet Black pellet ratio Compressive
strength (N/P) ratio (%) (%) strength (N/P)
A 681 5 13 1911
B 673 11 17 1819
C 675 10 15 1823
compressive strength decreases slightly. The shocked pellet ratio increases. Com-
pared with the scheme A, when 3–5% titanium-containing powders are added, the
shocked pellet ratio of scheme B and scheme C are doubled. The proportion of black
pellets increases by 2–4%, and the compressive strength of the fired pellets from the
head of rotary kiln decreases from 1911 to 1819–1823 N/P.
It’s obvious that, after adding titanium-containing powders in pellet production,
the quality of dried pellets and fired pellets both decrease. The strength of dried pellets
decrease, the explosion rate and black ball increase, and the compressive strength of
kiln-fired pellets decrease, which leads to the increase of crushed pellets and powders
entering the rotary kiln, then resulting in the explosive growth of ringing formation
in the kiln.
In summary, the formation of low-melting liquid phases and the existence of a large
number of particulate matters in the kiln are the main reasons resulting in the ringing
growth in the rotary kiln. In pellet production, the growth rate of ring formation
accelerates after adding titanium powders, which is mainly because the drying and
Research on Mechanism of Ring Formation … 701
preheating effect of green pellets becomes worse, the compressive strength of dried
pellets decreases, and a large number of crushed pellets and powders enter the rotary
kiln, leading to the rapid growth of ringing formation in the rotary kiln. Therefore,
if we want to further increase the proportion of titanium powders, we must optimize
the drying system of green pellets, improve the strength of dried pellets, reduce the
powders entering the rotary kiln, and restrain the growth of rings.
Conclusions
1. The formation of low-melting liquid phases and the existence of a large number of
particulate matters in the kiln are the main reasons resulting in the growth of ring
formation in the rotary kiln. However, it is difficult to remove the ring formation
because of the long-term high-temperature oxidation roasting atmosphere, and
increasing ringing strength.
2. The Ti element in titanium powders is not the main reason leading to aggravating
ring formation in the rotary kiln. Because of the decreasing strength of dried
pellets after adding titanium powders, the number of crushed pellets and pow-
ders entering the rotary kiln increases, which causes the acceleration of ringing
growth.
References
1. Jiang S, Wen Y, Sihong D, Zhang H (2012) Industrial test and application of high titanium-
containing pellet in blast furnace. Res Iron Steel 40(3):46–48
2. Li C, Chen Y (2010) Research on roasting technology of high titanium-containing pellet. Sinter
Pelletiz 35(6):12–16
3. Cai H, Cheng S, Ma J (2012) Furnace maintenance law of iron ore titanium-bearing in blast
furnace. Iron Steel 47(11):16–20
4. Liu J, Zhang G, Luo G (2013) Study on ring-forming cause of baosteel oxidized pellet rotary
kiln. Sinter Pelletiz 38(5):31–35
5. Fan X, Gan M, Yuan L (2008) Study of mechanism on ring formation in grate-kiln of acid pellet.
Iron Steel 43(3):15–20
6. Si J, Jia Y, Liu J (2014) Structure of rings and ring-forming mechanism of rotary pelletizing kiln
49(1):17–21
7. Chatterjee A, Mukhopadhyay PK (1983) Flow of materials in rotary kilns used for sponge iron
manufacture: part III. effect of ring formation within the kiln. 14(3):393
Part IX
Ironmaking and Steelmaking
Influences of Li2 O on the Properties
of Ultrahigh-Basicity Mold Fluxes
for Continuous Casting of Peritectic Steel
Min Li, Yuan bing Wu, Sheng ping He, Qiang qiang Wang and Qian Wang
Abstract The ultrahigh-basicity (R = 1.75) mold flux has been proved to be effective
in coordinating heat transfer and lubrication during continuous casting of peritec-
tic steel in industry, Properties of the mold flux may be further improved through
the adjustment of the Li2 O content in the flux. The effects of Li2 O content on the
properties of ultrahigh-basicity mold flux were systematically investigated. With the
increase of the Li2 O content from 0.8 to 2.4%, the viscosity of the ultra-high basic-
ity mold flux at the temperature of 1573 K increased and then decreased, and the
maximum viscosity was 0.148 Pa·s at the Li2 O content of 2.0%. With the increase of
the Li2 O content from 0.8 to 2.4%, the break temperature was reduced from 1484 to
1435 K, the initial crystallization temperature, which was measured by an in-house
apparatus, could decline by approximately 100 K with 2.4% Li2 O addition while
the crystallization rate represented an increasing trend except for the case with 2.0%
Li2 O. This study enhances the understanding of specified mold flux for peritectic
steel.
Keywords Ultrahigh-basicity mold flux · Li2 o · Viscosity · Crystallization

properties
Introduction
Mold fluxes have been indispensable metallurgical material in the continuous casting
process since they appeared in the 1960s. They are critical to ensure continuous
casting and improve the surface quality of slab. The most important function of
mold fluxes is to control the heat transfer as well as lubricate solidified shells [1–
4]. The realization of these functions is highly related to the viscosity, the melting
temperature and the crystallization properties of the slag [2, 5]. Longitudinal cracks
M. Li · Y. Wu · S. He (B) · Q. Wang · Q. Wang

e-mail: heshp@cqu.edu.cn
400044, China
https://doi.org/10.1007/978-3-030-36540-0_63
706 M. Li et al.
often occurred on the slab surface of peritectic steel with the carbon content of
0.08–0.16% of continuous casting, resulting from the peritectic reaction with 4.7%
volume contraction [6, 7]. The ultra-high basicity mold flux (R = 1.75) with low
break temperature and rapid crystallization rate has been developed to reduce the
occurrence of longitudinal cracks [8, 9]. The improvement of the heat transfer and
lubrication of the ultra-high basicity mold flux was related to the Li2 O addition into
the flux. In general, Li2 O was a kind of alkaline metal oxide which could significantly
reduce the melting temperature and the viscosity [9, 10]. Besides, it also deeply
affected the crystallization behavior of mold flux. However, to date, only a few
studies concentrate on Li2 O, especially with respect to its crystallization. In a study
employing the double hot thermocouple technique (DHTT), Lu [11] found that the
Li2 O can suppress crystallization via decreasing the initial crystallization temperature
in the CaO-Al2 O3 mold fluxes for the casting of high-Al steels. On the contrary, Yang
[12] determined that the Li2 O can enhance the crystallization capability by improving
the crystallization fraction in a CaO-SiO2 -Al2 O3 mold flux with 8% Na2 O through
differential scanning calorimetry (DSC) measurements. MYUNG-DUK SEO [13]
reported that the initial crystallization temperature decreased with Li2 O addition
in CaO-SiO2 -Al2 O3 -Na2 O-CaF2 -Li2 O mold fluxes. It was demonstrated that the
influences of Li2 O were complex in various mold fluxes. Therefore, it is necessary to
systematically investigate the influence of Li2 O on the properties of ultrahigh-basicity
mold fluxes.
Experimental Apparatus and Procedures
Materials
Five mold fluxes with different Li2 O content were investigated. All the fluxes were
prepared by melting pure chemical reagents (CaCO3 , SiO2 , CaF2 , Na2 O, Li2 CO3
MgO, Al2 O3 , Fe2 O3 ). The basicity of mold fluxes were approximately 1.75, and the
Li2 O content was within 0–2.4%. In order to resemble the condition in steel plant,
some Fe2 O3 was added into the five mold fluxes, whose specific compositions were
shown in Table 1.
Table 1 Chemical composition of mold fluxes (wt%)

Mold flux CaO SiO2 Na2 O Li2 O F− Al2 O3 MgO Fe2 O3
CSF 1 34.54 28.61 6 0 10.5 4 3 1.5
CSF 2 34.03 28.32 6 0.8 10.5 4 3 1.5
CSF 3 33.52 28.03 6 1.6 10.5 4 3 1.5
CSF 4 33.78 28.17 6 2.0 10.5 4 3 1.5
CSF 5 34.29 28.46 6 2.4 10.5 4 3 1.5
Influences of Li2 O on the Properties of Ultrahigh-Basicity Mold … 707
(1) In the current study, the viscosity, the break temperature, and the melting tem-
perature of the ultra-high basicity mold flux were measured through the rotating
cylinder method [8], and hemisphere point method [8], respectively.
(2) The crystallization properties of ultrahigh-basicity mold fluxes were investi-
gated by digital optical microscopy with an isolated observation system in an
infrared furnace (IR-MOP). As shown in Fig. 1, a halogen lamp was applied to
heat the sample. The crystallization process was recorded by digital microscopy
with a wide field of view. The equipment can effectively avoid the volatiliza-
tion of fluorides with a quartz glass over the platinum crucible. Besides, the
ToupView software can adjust the color, contrast, and brightness of the images
in a suit to avoid the high temperature irradiation interference.
In every experiment, a 6–80 mg mold powder from the mold flux CSF 1–CSF 5
was heated through the IR-MOP apparatus to 1300 °C at the heating rate of 10 °C/s
and held for 60 s to eliminate bubbles and homogenize the chemical composition.
Then, the sample was cooled to room temperature at the rate of 1, 2, 3, 4 °C/s. The
phase transformation from molten to the crystalline state was observed and recorded
via the CCD camera. The temperature of sample was monitored and recorded using
the temperature acquisition system. The image processing software Photoshop was
used to measure the crystallinity of the flux. Afterwards, based on the relationships
among the temperature, time, and phase fraction a CCT diagram was constructed.
At the 5% degree of crystallinity, the corresponding temperature was defined as the
initial crystallization temperature. When the degree of crystallinity reached 85%, the
corresponding temperature was defined as the end of crystallization temperature.
Fig. 1 Schematic of experimental devices

708 M. Li et al.
In Figure 2, the viscosity-temperature curves of ultra-high basicity mold fluxes with

different Li2 O contents was shown. The viscosity at 1300 °C, the break temperature
and the melting temperature were recorded in Table 2, with the increase of Li2 O con-
tent in the mold fluxes from 0 to 2.4%, the viscosity at 1300 °C increased from 0.034
to 0.148 Pa s and then decreased to 0.109 Pa s. The break and the melting temperatures
decreased from 1232 °C to 1162 °C and 1192 °C to 1068 °C, respectively.
The CCT diagrams from the relationship among the temperature, time and crys-
tallization fraction of CSF1–CSF5 was shown in Fig. 3. With the increase of the
Li2 O content from 0 to 2.4%, at the cooling rate of 1 °C/s, the initial crystallization
temperatures were 1225 °C, 1173 °C, 1155 °C, 1145 °C, and 1116 °C, respectively.
At the higher cooling rate, namely 4 °C/s, the initial crystallization temperatures were
1194 °C 1161 °C, 1143 °C, 1114 °C, and 1060 °C, respectively. With the gradual
increase of Li2 O by 0.8%, the initial crystallization temperature decreased on aver-
age by 42 °C. Additionally, with the increase of the cooling rate, the decrease of the
initial crystallization temperature was also observed. This observation was related
to the high viscosity and iron migration resistance in mold fluxes as a function of
Fig. 2 Viscosity-
temperature cures of
ultra-high basicity mold
fluxes with different Li2 O
contents
Table 2 Viscosity (1300 °C) and break temperature of ultra-high basicity mold fluxes
Mold flux Viscosity/(Pa·s) Break temperature/°C Melting temperature/°C
CSF 1 0.034 1232 1192
CSF 2 0.062 1211 1134
CSF 3 0.104 1196 1098
CSF 4 0.148 1180 1072
CSF 5 0.109 1162 1068
Fig. 3 CCT diagrams of Ultra-high basicity mold fluxes with different Li2 O contents
decreased temperature. Therefore, the formation of crystals required a large degree

of undercooling.
The crystallization process is related to both nucleation and crystal growth rate,
relationships of temperature, and the degree of undercooling. Therefore, the detailed
kinetics analysis is discussed below in the next chapter.
Analysis Through Avrami Equation
Avrami equation [14] has been widely used in the study of crystallization kinet-
ics of mold fluxes. The theory is based on the assumption that the non-isothermal
crystallization process which has a constant cooling rate can be approximated as an
isothermal crystallization process. The specific equation is:
ln[− ln(1 − X (t))] = ln Z t + N A lnt (1)
where X(t) represents the relative crystallinity at a given time, Zt is the compound
crystallization rate constant, and N A is the Avrami exponent. The relative crystallinity
and the compound crystallization rate are related to the temperature, the rate of
nucleation, and crystal growth. The value of N A was the slope from the plots of
ln[-ln(1-X(t))] versus lnt.
Plots of ln[-ln(1-X(t))] and lnt with different Li2 O contents in ultra-high basicity
mold fluxes are demonstrated in Fig. 4. It should be mentioned that, the plots based on
710 M. Li et al.
(a) (b)
1 1
0 0
-1 -1
ln [-ln(1-X)]
ln [-ln(1-X)]
-2 -2
-3 -3
-4 -4
-5 -5
-6 -6
-2 -1 0 1 2 3 4 -2 -1 0 1 2 3 4
ln t ln t
(c) (d)
1 1
0 0
-1 -1
ln[-ln(1-X)]
-2 ln[-ln(1-X)] -2
-3 -3
-4 -4
-5 -5
-6 -6
-2 -1 0 1 2 3 4 -2 -1 0 1 2 3 4
ln t ln t
(e)
1
-1
ln [-ln(1-X)]
-2
-3
-4
-5
-6
-2 -1 0 1 2 3 4 5
ln t
Fig. 4 Plots between ln[-ln(1-X(t))] and lnt with different Li2 O content of a 0%, b 0.8%, c 1.6%,
d 2.0% and e 2.4% under different cooling rates
the Avrami equation are not linear, which verified the inappropriateness of Avrami
equation in describing the non-isothermal crystallization process of mold fluxes.
However, it does not affect the calculation that Avrami exponent. Actually, N A is a
function of crystallinity, temperature, and the cooling rate in the non-crystallization
process. Therefore, compared with the isothermal crystallization, it does not have
physical meaning. However, it can be employed to obtain the non-isothermal crystal-
lization kinetics parameter No, associated with the m value in the Mo equation [14].
Besides, there is a positive correlation between No and the crystallization rate, the
higher the No, the faster the crystallization speed and the stronger the crystallization
ability.
Analysis Through Mo Equation
The Mo equation [14] is also commonly employed in non-isothermal analysis of

mold flux.
ln Φ = ln F(T ) − m lnt (2)
where F is the cooling rate, and F(T) is the crystallization rate constant. The crys-
tallization rate constant is related to both the crystallinity and the cooling rate and
has a negative correlation with the crystallization rate, which means the higher the
No, the slower the crystallization speed and the weaker the crystallization ability.
The No mentioned above can be obtained by m = N A /N O . The relationships between
lnF and lnt of CSF1–CSF5 were presented in Fig. 5. All plots show a good linear
relationship between lnF and lnt, which verifies the applicability of the Mo equations
in describing the non-isothermal crystallization process of ultrahigh basicity mold
fluxes.
Relationships between crystallization fraction and lnF(T) as well as, crystalliza-
tion fraction and No from Mo equation are shown in Figs. 6 and 7, respectively.
Figure 6 shows that with the increase of Li2 O content from 0 to 2.4%, the lnF(T)
increased and then decreased, reaching the maximum at the Li2 O content of 2.0. It
was indicated that the Li2 O could suppress the crystallization with the addition of less
than 2.0%. The non-isothermal crystallization kinetic parameter No firstldecreased
with the content of Li2 O below 2.0%, and then increased rapidly when the content
exceeded 2.0%. Therefore, the opposite trends between lnF(T ) and N O indicated
similar results.
Conclusions
Effects of the Li2 O content on properties of ultra-high basicity mold fluxes were
systematically investigated. The viscosity at 1300 °C, the break and the melting
temperatures, as well as, the crystallization properties were measured. Results are
summarized as follows:
(1) With the increase of Li2 O content in mold fluxes from 0 to 2.4%, the viscosity
at 1300 °C increased from 0.034 to 0.148 Pa s and then decreased to 0.109 Pa
s. The break temperature decreased from 1232 to 1162 °C, and the melting
temperature from 1192 to 1068 °C.
712 M. Li et al.
(a) (b) 1.6

1.6
X=0.1 X=0.1
X=0.2 X=0.2
1.2 X=0.3
1.2 X=0.3
X=0.4 X=0.4
X=0.5 X=0.5
X=0.6
ln Φ
ln Φ
X=0.6
0.8 0.8 X=0.7
X=0.7
X=0.8 X=0.8
0.4 0.4
0.0 0.0
1.5 2.0 2.5 3.0 3.5 4.0 4.5 1.5 2.0 2.5 3.0 3.5 4.0 4.5
ln t ln t
(c) (d) 1.6
1.6
X=0.1 X=0.1
X=0.2 X=0.2
1.2 X=0.3 1.2 X=0.3
X=0.4 X=0.4
X=0.5 X=0.5
X=0.6
ln Φ
X=0.6
ln Φ
0.8 X=0.7 0.8 X=0.7

X=0.8 X=0.8
0.4 0.4
0.0 0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 1.5 2.0 2.5 3.0 3.5 4.0 4.5
ln t ln t
(e)
1.6
X=0.1
X=0.2
1.2 X=0.3
X=0.4
X=0.5
X=0.6
ln Φ
0.8 X=0.7
X=0.8
0.4
0.0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

ln t
Fig. 5 Relationship between lnF and lnt for non-isothermal crystallization of different Li2 O
contents in ultra-high basicity mold fluxes
(2) With the increase of the Li2 O content from 0 to 2.4%, at the cooling rate of 1
°C/s, the initial crystallization temperatures were 1225 °C, 1173 °C, 1155 °C,
1145 °C, and 1116 °C, respectively. At the cooling rate of 4 °C/s, the initial
crystallization temperatures decreased from 1194 to 1060 °C. With the gradual
Fig. 6 Non-isothermal
crystallization kinetic 8
parameter lnF(T ) based on
MO equation of ultra-high 7
basicity mold fluxes of
CSF1–CSF5
6
ln F(T)
5
Li2O=0%
4 Li2O=0.8%
Li2O=1.6%
3 Li2O=2.0%
Li2O=2.4%
2
0.0 0.2 0.4 0.6 0.8 1.0
crystallization fraction
Fig. 7 Non-isothermal
crystallization kinetic Li2O=0%
parameter No based on MO Li2O=0.8%
4
equation of ultra-high Li2O=1.6%
basicity mold fluxes of Li2O=2.0%
CSF1–CSF5
Li2O=2.4%
3
NO
0.0 0.2 0.4 0.6 0.8

crystallization fraction
increase of Li2 O by 0.8%, the initial crystallization temperature decreased in

average by 42 °C.
(3) The non-isothermal crystallization kinetic parameter lnF(T) and No were
obtained by Mo equation which is associated with the Avmavi equation. The
lnF(T) increased with the Li2 O content from 0 to 2.0%. However, the No
decreased when Li2 O content was less than 2.0%. The results No and lnF(T)
showed that the Li2 O can suppress the crystallization when the Li2 O content was
below 2.0%, On the other hand, the higher Li2 O content (>2.0%) has promoted
the crystallization.
714 M. Li et al.
Acknowledgements This work was financially supported by the National Science Foundation of
China (project no. 51874057).
References
1. Mills KC, Däcker CÅ (2017) The casting powders book. Springer, Berlin
2. Mills KC, Fox AB (2003) The role of mould fluxes in continuous casting so simple yet so
complex. ISIJ Int 43(10):1479–1486
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free mold flux. ISIJ Int 46(3):441–449
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mold flux for casting high-aluminum TRIP steels. Metall Mater Trans B 46(1):345–356
Optimization of Process Parameters
for the Synthesis of Mo2 C
on an Activated Carbon Matrix
Grant C. Wallace, Jerome P. Downey, Jannette Chorney
and Katie Schumacher
Abstract Commercial production of carbide materials is often associated with high

energy costs due to the high temperatures and long milling times required to pro-
duce a powder carbide product. A process for synthesizing Mo2 C was developed to
reduce carburization temperatures and product particle size. Precursor material, pro-
duced by adsorbing molybdate anions onto activated carbon, was carburized under
a reducing gas atmosphere to produce Mo2 C at temperatures below 800 °C. Molyb-
denum adsorption was measured using inductively coupled plasma spectroscopy,
and carburization products were characterized using X-ray diffraction and scanning
electron microscopy. Response surface analyses were used to mathematically model
the adsorption and carburization processes and to determine optimal parameters for
Mo-loading and Mo2 C synthesis. The effects of temperature, time, pH, and initial
Mo concentration were used to model adsorption behavior while the carburization
process was modelled using the effects of temperature, reaction time, and reducing
gas atmosphere on the synthesis of Mo2 C.
Keywords Molybdenum carbide · Synthesis · Statistical optimization
Introduction
Known for their high hardness values and resistance to abrasion and chemical attack,
transition metal carbides are used for a number of industrial applications including
improving the wear resistance of cutting tools and drill bits, the heat resistance of
rocket nozzles, and the toughness of certain steel alloys [1]. Although traditionally
used as a steel additive [2], molybdenum carbide (Mo2 C) has become an interest
in catalysis research due to the possibility that Mo2 C and other transition metal
carbides, could replace the more expensive noble metal catalysts such as platinum
G. C. Wallace (B) · J. P. Downey · J. Chorney · K. Schumacher

Montana Technological University, 1300 W. Park St., Butte, MT 59701, USA
e-mail: gwallace@mtech.edu
J. P. Downey
e-mail: jdowney@mtech.edu
https://doi.org/10.1007/978-3-030-36540-0_64
716 G. C. Wallace et al.
and palladium [3]. Molybdenum carbide has been shown to be an effective catalyst
in the production of synthesis gas from methane gas when supported on alumina
(Al2 O3 ) or zirconia (ZrO2 ) [4]. Research has also shown that Mo2 C could be used to
catalyze H2 evolution reactions for use in the development of solar energy-derived
hydrogen fuel [5].
Like most transition metal carbides, conventional methods of synthesizing Mo2 C
involve the carburization of molybdenum metal in the presence of solid carbon at
temperatures exceeding 1500 °C under an inert or reducing atmosphere [2]. This
conventional method of carburization generally produces a coarse final product that
is less suitable for catalytic applications or requires extensive milling in order to
produce a more usable final powder product. Alternatively, the use of the tempera-
ture-programmed reduction method (TPR), where molybdenum oxides are subjected
to a reducing/carburizing gas atmosphere such as methane, carbon monoxide, or mix-
tures of carbon-containing gases and H2 , has been shown to reduce the final particle
size of Mo2 C crystals formed during carburization while also lowering carburiza-
tion temperatures [3, 6, 7]. The use of molybdenum-containing solutions has been
shown to also promote the production of nano-crystalline Mo2 C. Nano-crystalline
Mo2 C can be formed from aqueous solution via the impregnation of an ultrahigh
surface area carbon material with ammonium molybdate solution. Carburization of
this material under H2 yielded Mo2 C crystals as small as 10 nm at temperatures
considerably lower than conventional methods [8]. Nano-crystalline Mo2 C has also
been synthesized from solutions of ammonium molybdate and sucrose following
carburization at temperatures as low as 800 °C [9].
The Metallurgical and Materials Engineering Department at Montana Tech is
developing alternative methods for synthesizing Mo2 C. Precursor materials for Mo2 C
are synthesized by adsorbing sodium molybdate, onto an activated carbon matrix
[10]. The research elaborates on improvements to the research presented previously
on the Mo2 C synthesis process including the mathematical modelling and statistical
optimization of the carburization behavior of the Mo-loaded precursor.
Carburization Precursor Production
Precursor material was prepared by adsorbing molybdate anions onto commercially

available activated carbon (Sigma Aldrich, −100/+400 Mesh). The conditions for
maximizing Mo-adsorption were determined with statistical validation using a design
of experiments. The details of this adsorption optimization process have been previ-
ously presented by the authors [10]. The Mo-loaded precursor was prepared in 50 g
batches using 2 L of molybdate solution with an approximate Mo concentration of
18,000 ppm. Each solution was prepared in a 2 L volumetric flask by adding 90.78 g
of sodium molybdate dihydrate (Na2 MoO4 ) and 5.84 g of sodium chloride (NaCl)
Optimization of Process Parameters for the Synthesis of Mo2 C … 717
before diluting to the mark with 18 M deionized water. The molybdate solution
was transferred to a 4 L beaker and the pH of the solution was brought to 2.0 with
additions of 37% hydrochloric acid. A 50 g sample of activated carbon was then
added to the solution and the mixture was agitated for 2 h. The activated carbon
was then separated from the solution by vacuum filtration and dried overnight. From
previous adsorption optimization work, this procedure produces precursor material
with a Mo-loading of 0.32 g Mo/g C [10].
Carbide Synthesis
Carburization experiments were conducted using an ATS 3210 rotary furnace. Sam-
ples of Mo-loaded precursor were prepared in 25 g batches and loaded into a fused
quartz kiln (Allen Scientific Inc.). The samples of Mo-loaded precursor were heated
to a specified carburization temperature (500 °C, 675 °C, or 850 °C) at a rate of
5.3 °C/min under a constant flow of argon gas (0.5 L/min). Once the sample reached
the specified carburization temperature, the argon atmosphere was replaced with a
mixture of carbon monoxide, hydrogen, and methane gas. The flow rate of each gas
was regulated using a series of Omega rotameters calibrated to each gas using a
DryCal Defender 530+ primary calibrator. The total flow rate of the gas mixture was
held at 0.5 L/min. The volumetric ratios of methane and hydrogen were altered for
each experiment while the flowrate of carbon monoxide was fixed at 10% of the total
volume. Samples were held at temperature for 1, 5, and 8 h after which the reducing
gas mixture was replaced with argon gas and the carburized samples were cooled to
room temperature. A 2-factorial design of experiments was prepared using Design-
Expert9 software consisting of 11 carburization experiments. These experiments
were carried out using the experimental conditions presented in Table 1.
Once the samples reached ambient conditions, the samples were removed from
the kiln and analyzed via X-ray diffraction (XRD) and scanning electron microscopy
(SEM). A Rigaku Ultima IV X-ray diffractometer with a Cu-kα X-ray source was
used to analyze the composition of the carburized samples. The relative weight
percentages of the crystalline species formed during carburization were determined
using the whole pattern powder fitting method (WPPF). Images of the carburized
samples were taken using a Tescan MIRA3 scanning electron microscope (SEM)
using electron back scattering detection (EBSD) and secondary electron imaging
(SE).
Carburization Modelling
A preliminary model of carburization behavior was produced using DesignExpert9

software (StatEase Inc.). Modelling was carried out on the WPPF relative weight
Table 1 Experimental
Sample name Time (h) Temperature Gas
conditions for the
(o C) composition
Mo-carburization design of
(CH4 :H2 )
experiments
Mo_DM1 1 500 2.9
Mo_DM2 8 500 2.9
Mo_DM3 1 850 2.9
Mo_DM4 8 850 2.9
Mo_DM5 1 500 8
Mo_DM6 8 500 8
Mo_DM7 1 850 8
Mo_DM8 8 850 8
Mo_DM9 4.5 675 5
Mo_DM10 4.5 675 5
Mo_DM11 4.5 675 5
percentages of Mo2 C from the XRD data from each carburization experiment. Car-
burization data was modelled using a square root transform and a modified 2FI
relationship. The statistical model generated from the XRD data was verified using
multiple statistical diagnostic methods including analysis of variance (ANOVA), and
Cook’s distance formula.
The X-ray diffraction patterns presented in Fig. 1 are examples of the behavior that
was observed in the samples carburized at 500 and 850 °C regardless of reaction
time or gas composition.
Samples carburized at 850 °C were observed to contain two crystalline species:
Mo2 C and MoC, with no other crystalline species present. Samples carburized at
500 °C were observed to contain MoC and a molybdenum oxide, MoO2 , with no
Mo2 C present.
The relative weight percent values for Mo2 C detected in each of the carburized
samples by XRD are presented in Table 2.
The XRD data from the 2-factorial design were used to produce a mathematical
model of carburization behavior. The model for the production of Mo2 C from the
Mo-loaded precursor can be defined by the expression:

% Mo2 C = −12.92 + 0.03T,
where “T” represents carburization temperature in degrees Celsius. A three-

dimensional representation of the carburization model is presented in Fig. 2.
Mo2C (850oC)
MoO2 (500oC)
MoC
Fig. 1 X-ray diffraction patterns for Mo_DM1 (500 °C) and Mo_DM3 (850 °C)
Table 2 Carburization results for the Mo-loaded precursor design of experiments

Sample name Time (h) Temperature (o C) Gas composition Mo2 C content (wt%)
(CH4 :H2 )
Mo_DM1 1 500 2.9 0
Mo_DM2 8 500 2.9 0
Mo_DM3 1 850 2.9 89.6
Mo_DM4 8 850 2.9 90.1
Mo_DM5 1 500 8 0
Mo_DM6 8 500 8 0
Mo_DM7 1 850 8 85.3
Mo_DM8 8 850 8 72.0
Mo_DM9 4.5 675 5 36.6
Mo_DM10 4.5 675 5 11.1
Mo_DM11 4.5 675 5 25.3
From the model, it can be observed that carburization of the Mo-loaded precursor
is a primarily thermodynamically driven process within the confines of the parameter
ranges used in these experiments. High degrees of conversion to Mo2 C (85–90%)
were observed in carburization experiments conducted at 850 °C regardless of reac-
tion time or gas composition. While reaction kinetics are always critical, it is evident
(a) 100.0
83.3
Avg % Mo2C (%)

66.7
50.0
33.3
16.7
0.0
8
7
6
850
5 780
Gas Comp (CH4:H2) 4 710
640
3 570
2 500 Temp (deg C)
(b)
100.0
83.3
Avg % Mo2C (%)
66.7
50.0
33.3
16.7
0.0
8
7
6
5 850
4 780
Time (hr) 710
3 640
2 570
1 500 Temp (deg C)
Fig. 2 Three-dimensional model of carburization at constant time (8 h) (a) and gas composition
(8) (b)
that a carburization time of 1 h was sufficient to the extent that longer reaction times
did not statistically affect conversion to Mo2 C. It may be possible that, if the overall
reaction time were reduced below 1 h in additional experimentation, time would be
considered a statistically significant variable.
The carburized samples were also analyzed via SEM. Secondary electron micro-
graphs of a high-temperature sample (Mo_DM7) and a low-temperature sample
(Mo_DM6) are presented in Figs. 3 and 4 along with corresponding XRD patterns
for each sample.
It was determined from the XRD pattern that Mo_DM7 contained only two crys-
talline species following carburization: Mo2 C (85.3%) and MoC (14.7%). The SEM
image shows two distinct types of crystals forming on the surface of the activated
carbon: a series of larger “flakes” interspersed with smaller “needle-like” crystals that
Mo 2C
MoC
Fig. 3 XRD pattern and SEM image of carburized Mo_DM7

MoO2
MoC
MoC
Fig. 4 XRD pattern and SEM image of carburized Mo_DM6

are submicron in width. The WPPF analysis of the diffraction pattern for Mo_DM6
determined that the sample contained two crystalline species: MoC (21.8%) and
MoO2 (78.4%). The micrograph of Mo_DM6 (Fig. 4) also revealed the presence of
needle-like crystals as well as larger clusters of a third type of crystal with a shorter,
more jagged, morphology.
From a comparison of the diffraction patterns, micrographs, and literature sources
regarding morphologies of molybdenum carbides and oxides, it is possible to identify
the three crystal types observed in the samples carburized at 850 and 500 °C. Because
the needle-like crystals were observed in micrographs of both high-temperature and
low-temperature samples, it is most likely that these crystals are composed of MoC
as this molybdenum species was detected in both sample types. The crystal “flakes”
present in samples carburized at 850 °C are proposed to be composed of Mo2 C
and the crystal “clusters” observed in samples carburized at 500 °C are proposed
to be composed of MoO2 . Due to the size of the crystals and the magnification
required to observe these morphologies, spot elemental analysis by SEM (EDAX) is
not a viable method of characterization. However, it is known that similar Mo-oxide
morphologies have been observed in existing carburization literature [11] and Mo2 C
“flakes” have been observed as well [7].
Conclusions and Future Work
Molybdenum carbide, Mo2 C, has been synthesized from the carburization of a Mo-
loaded precursor at conversion rates approaching 90%. A preliminary mathematical
model of the carburization process has been produced that indicates that this process
is primarily thermodynamically driven with high degrees of conversion to Mo2 C
possible at 850 °C. The model may indicate that shorter reaction times and less
aggressive gas atmospheres may be more effective than originally expected though
further refinement of the model is necessary in order to confirm this possibility.
Micrographs of the products carburized at 850 °C indicate that the carbide crystals
produced by this process are submicron in size and may be suitable for both structural
and catalytic applications.
Acknowledgements Research was sponsored by the Combat Capabilities Development Com-

mand Army Research Laboratory and was accomplished under Cooperative Agreement Number
W911NF-15-2-0020. The views and conclusions contained in this document are those of the authors
and should not be interpreted as representing the official policies, either expressed or implied, of the
Combat Capabilities Development Command Army Research Laboratory or the U.S. Government.
The U.S. Government is authorized to reproduce and distribute reprints for Government purposes
notwithstanding any copyright notation herein.
References
1. Oyama ST (2012) The chemistry of transition metal carbides and nitrides. Blackie Academic
& Professional, Glasgow, UK
2. Pierson HO (1996) Characteristics and properties of molybdenum carbide. In: Handbook
of refractory carbides and nitrides: properties, characteristics, processing and applications,
Westwood, New Jersey, Noyes Publications, Westwood, NJ, pp 110–112
3. Lee JS, Oyama ST, Boudart M (1987) Molybdenum carbide catalysts: I. Synthesis of
unsupported powders. J Catal 106(1):125–133
4. Brungs AJ, York AP, Claridge JB, Marquez-Alvarez C, Green ML (2000) Dry reforming of
methane to synthesis gas over supported molybdenum carbide catalysts. Catal Lett 70(3):117–
122
5. Yabo W, Wenguang T, Jindui H, Wei Z, Rong X (2016) Molybdenum carbide microcrystals:
efficient and stable catalyst for photocatalytic H2 evolution from water in the presence of dye
sensitizer. J Mater 2(4):344–349
6. Arnoldy P, de Jonge JCM, Moulijn JA(1985) Temperature-programmed reduction of MoO3
and MoO2 . J Phys Chem 89(21):4517–4526
7. Covington L, Munirathinam K, Islam AW, Roberts KL (2012) Synthesis and characterization
of nanostructured molybdenum & tungsten carbide materials, and study of diffusion model.
Polish J Chem Technol 14(1):28–34
8. Changhai L, Pinliang Y, Can L (2002) Nanostructured β-Mo2 C prepared by carbothermal
hydrogen reduction on ultrahigh surface area carbon material. Chem Mater 14:3148–3151
9. Patel M, Subrahmanyam J (2008) Synthesis of nanocrystalline molybdenum carbide (Mo2 C)
by solution route. Mater Res Bull 43(8):2036–2041
10. Wallace G et al (2018) Synthesis of nanocrystalline carbide ceramics via reduction of anion-
loaded activated carbon precursors. In: Paper presented at the 148th TMS annual meeting,
Phoenix, AZ, 11–15 March 2018
11. Hanif A, Tiancun X, York APE, Sloan J, Green MLH (2002) Study on the structure and
formation mechanism of molybdenum carbides. Chem Mater 14(3):1009–1015
Effect of Refining Slag Composition
on the Cleanliness of 25Cr2Ni4MoV
Rotor Steel
Chao Zhuo, Yimin Zhang, Yanhui Sun, Ruimei Chen and Sicheng Song
Abstract The effect of different refining slag components on the cleanliness of

25Cr2Ni4MoV turbine rotor steel was studied through four industrial experiments.
It is found that less total oxygen, dissolved oxygen, inclusion quantity and smaller
inclusion size could be obtained with a basicity of the refining slag between 3 and 4
and a C/A ratio between 7 and 10. FactSage7.0 was used to study the influence of slag
composition on dissolved oxygen in molten steel and Al2 O3 inclusion adsorption.
The results reveal that high basicity is beneficial to reduce dissolved oxygen in
molten steel, and less Al2 O3 inclusions exist with high basicity and high C/A. Then,
the evolution of typical inclusions in the refining process was discussed. Next, the
physicochemical parameters of refining slag were analyzed, the viscosity and melting
point of the four groups of refining slag showed that the addition of SiO2 and Al2 O3
in the slag can reduce the amount of CaF2 . Finally, the influence of the composition
of refining slag on the lining erosion was investigated.
Keywords 25Cr2Ni4MoV steel · Cleanliness · Inclusion · Slag
Introduction
Rotor steel is used as steam turbine rotor which is one of the most important parts
of steam turbine in modern power plant [1]. Fatigue cracking and creep will occur
because the rotor of steam turbine is loaded with alternating stress at high tempera-
ture, and this is the main reason for the decrease in service life [2, 3]. In industrial
production of 25Cr2Ni4MoV steel, the inclusion of large equivalent is the main rea-
son for the ultrasonic test defects. Therefore, it is of great importance to control the
cleanliness of liquid steel. To control the cleanliness of molten steel is to control the
total oxygen content and inclusions of molten steel [4].
C. Zhuo · Y. Zhang · Y. Sun (B) · R. Chen · S. Song

Collaborative Innovation Center of Steel Technology, University of Science and Technology
e-mail: ustb420@126.com

https://doi.org/10.1007/978-3-030-36540-0_65
726 C. Zhuo et al.
Refining slag has a good effect on deoxidation and inclusion removal. In recent
years, quite a few scholars had studied the physicochemical parameters of refining
slag, such as basicity, C/A, viscosity, fluidity, and steel slag interfacial tension on
the cleanliness of steel [5, 6]. Wang et al. [7] believed that the adsorption capacity
of refined slag decreased with the increase of viscosity and interfacial tension, and
calculated the critical size of inclusions that could be adsorbed under different slag
systems. Reis et al. [8] verified that the adsorption efficiency of refining slag to
inclusions had a linear relationship with the ratio of supersaturation and viscosity of
refining slag, that was to say, high supersaturation and low viscosity were conducive
to inclusions adsorption. Yoon et al. [9] optimized the bearing steel refining slag
and considered that the total oxygen content of the bearing steel could be reduced
to range from 5 to 8 ppm when the C/A ratio of the refining slag was between 1.7
and 1.8. Ren et al. [10] believed that high basicity refining slag could significantly
reduce the total oxygen content and inclusion quantity density of molten steel, and
adding 15% MgO could reduce the erosion of furnace lining. Li et al. [11] conducted
reaction experiments of four groups of slag and steel in the laboratory, and found
that high MgO solubility and low viscosity were easy to corrode crucible.
This paper proceeds as follows: Four groups of industrial experiments of
25Cr2Ni4MoV steel produced by a factory were followed and sampled, and the
changes of oxygen content and inclusions in molten steel during the refining pro-
cess were analyzed. And the influence of basicity of refining slag and C/A ratio on
deoxidation and inclusions adsorption was studied, so as to provide theoretical and
practical guidance for improving liquid steel cleanliness in this factory.
Experimental
The required composition of 25Cr2Ni4MoV steel is shown in Table 1 and the pro-
duction process of 25Cr2Ni4MoV is as follows: electric arc furnace (EAF) → ladle
furnace (LF) → vacuum degassing (VD) → vacuum casting. When the ladle moved
into the LF station, active lime and fluorite were added into the ladle. When heating
for minutes, electrode powder was added to the furnace as a deoxidizing agent. The
ladle was carried into the VD station when the alloy was added to make the liquid
steel composition up to standard. The vacuum processing time lasted about half an
hour, where the vacuum was between 2600 and 4000 Pa. Finally, vacuum casting
was performed after VD tapping. The initial refining slag composition of four heats
are shown in Table 2. The slag 1 is used before and has high basicity. The slag 2, 3,
and 4 are designed to study the effect of R and C/A on the cleanliness of steel.
The sampling point was at beginning of LF, middle of LF, end of LF, after of VD,
after vacuum casting.
The total oxygen (T.O) of steel samples was measured by an Oxygen–Nitrogen
Analyzer (LECO TCH600). Other compositions of steel samples were determined
by photoelectric direct reading spectrometry. The morphologies and compositions
of inclusions on steel samples were analyzed by scanning electron microscopy with
Table 1 Chemical composition of 25Cr2Ni4MoV (%)
Component C Si Mn P S Cr Ni Mo Cu Al V
Range 0.25 ≤0.1 0.3 ≤0.007 ≤0.005 1.75 3.4 0.4–0.45 ≤0.1 ≤0.01 0.1
Effect of Refining Slag Composition on the Cleanliness …
727
728 C. Zhuo et al.
Table 2 Chemical composition of initial refining slag (%)

Slag CaO SiO2 Al2 O3 CaF2 MgO R C/A
1 53–55 7–9 4–6 17–19 4 6–8 9–14
2 53–55 14–16 6–8 15–17 4 3–4 6–9
3 55–57 15–17 6–8 15–17 4 3–4 7–10
4 51–53 15–17 4–6 17–19 4 3–4 9–14
energy-dispersive spectrometric (SEM-EDS). The slag samples were ground into

powder and determined by X-ray fluorescence spectrometer. The quantity and particle
size distribution of inclusion were analyzed by optical microscope, and the number
density of inclusion was estimated by the following relationship:
n 2
i=1 di n i
I = × 106 (1)
π D 2 N B 2 /4
where I is the number of inclusions of equivalent diameter B per unit area, di is

average diameter of inclusions in different size ranges, n i is the number of inclusions
in a range of sizes, B is equivalent diameter of inclusion, D is the diameter of the
field of view, N is number of consecutive fields of view.
The compositions of final slag and steel sample after LF are shown in Tables 3 and
4, respectively.
The Total Oxygen and Dissolved Oxygen
The total oxygen and dissolved oxygen of different experiments are shown in Fig. 1.
It indicates that basicity has a great influence on the dissolved oxygen. Experiment 1
Table 3 Chemical composition of final refining slag (%)

Heat CaO SiO2 Al2 O3 CaF2 MgO R C/A
1 54.3 8.9 4.6 22.00 7.4 6.1 11.8
2 54.0 15.6 6.0 16.4 6.3 3.5 9.0
3 55.9 16.2 5.9 17.3 3.8 3.5 9.5
4 52.8 16.3 5.0 18.6 5.6 3.2 10.5
Table 4 Chemical composition in steel after LF refining (%)
Heat C Si Mn P S Cr Mo Alt V [O] T[O]
1 0.250 0.048 0.279 0.005 0.002 1.726 0.429 0.002 0.093 0.00050 0.0050
2 0.234 0.021 0.287 0.004 0.002 1.710 0.405 0.001 0.072 0.00095 0.0064
3 0.245 0.053 0.287 0.005 0.002 1.700 0.412 0.001 0.092 0.00062 0.0032
Effect of Refining Slag Composition on the Cleanliness …
4 0.244 0.034 0.285 0.006 0.002 1.700 0.412 0.001 0.085 0.00108 0.0037
729
730 C. Zhuo et al.
Fig. 1 The total oxygen and dissolved oxygen of different slags after LF refining
has lowest dissolved oxygen of 5 ppm. The highest dissolved oxygen is in experiment
4 up to 10.8 ppm.
When the steel slag reaches equilibrium, the dissolved oxygen in the steel can be
expressed by the following equation:
[Si] + 2[O] = (SiO2 ) (2)
G = −576440 + 218.2T (J/mol)

G
aSiO2 e RT
[O] = (3)
[%Si] f Si f O2
j
lg f i = ei [% j] (4)
where [O] is the dissolved oxygen, aSiO2 is activity of SiO2 in slag, [%Si] is silicon
content in molten steel, f Si and f O are activity coefficient of silicon and oxygen
in molten steel, respectively. f Si and f O were calculated by substituting the data in
Table 5 into Eq. (4). Equations (2)–(4) combined with Factsage7.0 could be used to
calculate the iso-oxygen line between steel and slag, which is shown in Fig. 2.
Figure 2 manifests that basicity and C/A of slag have great influence on dissolved
oxygen in steel, the dissolved oxygen decreases with increasing basicity of slag and
C/A of slag. This is consistent with the pattern shown in Fig. 1, the dissolved oxygen
in steel made of slag 1 is the lowest for the highest basicity. For experiment 2 and
Effect of Refining Slag Composition on the Cleanliness … 731
Table 5 Interaction coefficient of O and Si (1600 °C) [11]

C Si Mn P S Cr
j
eO −0.421 −0.131 −0.021 0.07 −0.133 −0.055
j
eSi 0.18 0.11 −0.0146 0.09 0.066 −0.0003
Ni Mo Cu Al V O
j
eO 0.006 0.005 −0.013 −1.17 −0.3 −0.17433
j
eSi 0.005 0 0.0144 0.058 0.025 −0.119
Fig. 2 Iso-[O] line in CaO–SiO2 –Al2 O3 –%6MgO at 1873 K
experiment 3, they have the same basicity, but the C/A of the latter is greater than
that of the former, so the dissolved oxygen of experiment 3 is 6.2 ppm lower than
that of experiment 2 (9.5 ppm).
Composition and Morphology of Inclusions
The compositions of inclusions in different heats after refining are shown in Fig. 3.
It can be seen from Fig. 3 that the inclusions before the end of refining are MgO–
Al2 O3 –SiO2 –CaO system. The CaO content in the inclusion of heat 1 is much higher
than that in the other three heats, because the amount of lime added in the first heat
is too large, the CaO in the slag is oversaturated.
732 C. Zhuo et al.
Fig. 3 Inclusion composition of each heat before the end of refining
In the production of 25Cr2Ni4MoV steel, the Al2 O3 inclusions may cause unqual-
ified flaw detection due to local aggregation, which affected the rate of qualified
products. Therefore, it is necessary to study the adsorption of Al2 O3 inclusions by
refining slag. The iso-activity lines of CaO and Al2 O3 in CaO–SiO2 –Al2 O3 –6%MgO
under 1873 K were calculated by using FactSage7.0 software, as shown in Fig. 4.
According to Fig. 4, as the basicity of refining slag and C/A increase, the activity of
Al2 O3 gradually decreases, while the activity of CaO gradually increases, which is
conducive to adsorption of Al2 O3 inclusions. Therefore, the steel of first heat with
Fig. 4 Iso-activities for Al2 O3 and CaO in CaO–SiO2 –Al2 O3 –6%MgO phase diagram (a Al2 O3 ,
b CaO)
Fig. 5 Evolution of inclusions in the third furnace during refining
high basicity refining slag contains the least amount of Al2 O3 inclusions before the
end of refining.
The composition evolution of inclusions in the third heat refining process was
counted and mapped, as shown in Fig. 5. It can be seen from Fig. 5 that in the early
stage of refining, the inclusions was mainly composed of Al2 O3 , and as the reaction
proceeded, the Mg in the lining and slag entered the molten steel and combined
with Al2 O3 to form a magnesium–aluminum spinel. After the start of refining, lime
was added to the ladle, resulting in an increase in the content of SiO2 and CaO in
the inclusions. At the end of refining, the CaO content in the inclusions increased
because during the VD process, [Al] in molten steel reacted with CaO in slag to
produce [Ca] in molten steel, then combined with Al2 O3 to form calcium aluminate.
The CaO content of the inclusions at the end of refining in the third heat is much
lower than that of the first heat because the basicity of the first furnace is high and
CaO is excessive. Due to the vacuum casting, when the molten steel flowed from the
tundish into the ingot mold, the calcium aluminosilicate floats with the gas, leaving
the Al2 O3 which was not easy to float, so the proportion of Al2 O3 in the steel ingot
was increased. The typical morphology of the inclusions in the third furnace refining
process is shown in Fig. 6.
734 C. Zhuo et al.
Fig. 6 Typical morphology of inclusions in the third heat refining process
The Number Density and Particle Size Distribution

of Inclusions
The number density of inclusions after LF refining are shown in Fig. 7, reflect the abil-
ity to the removal inclusion of different slag. It can be seen from Fig. 7 that the largest
inclusion density is the first heat and the smallest is the third heat, which is consistent
with the change trend of total oxygen content mentioned above. It demonstrates that
the strongest ability to absorb inclusion is slag 3. Some researchers suggested that
the ability of refining slag to absorb inclusions increases with increasing basicity [7];
however, the basicity and inclusion of the first heat are both maximum. The basicity
of the third heat is moderate, but the inclusion density is minimal. It indicates that
the basicity and C/A of the refining slag should not be too high, and the influence on
the fluidity of the refining slag should be considered.
The particle size distribution of inclusions after LF refining was also plotted, as
shown in Fig. 8. For small inclusions of 0–2 µm, the third heat has the highest
proportion of 88%, and the lowest proportion of first heat is 67%. The inclusions
larger than 6 µm are only available in the second heat, and the ratio is 5%. The
proportion of inclusion with 2–6 µm in the first furnace, second furnace, and fourth
furnace is higher than that in the third heat. In other words, the size of inclusion in
third heat is smaller than others.
Fig. 7 The number density of inclusion after LF refining
Fig. 8 The particle size distribution of inclusion after LF refining

736 C. Zhuo et al.
Table 6 The melting point and liquid phase ratio of experimental slags
Slag 1 2 3 4
Melting point (°C) 1997.5 1879.3 1875.7 1840.2
Liquid ratio (%) 70.56 85.85 87.73 88.29
Physicochemical Parameters of Refining Slag
The physicochemical parameters of refining slag have an important influence on

its metallurgical properties, such as melting point, liquid ratio, viscosity, and the
solubility of MgO.
There is no doubt that the fluidity of refining slag is significant for the kinetic
conditions of the reaction of slag and steel. The melting point and liquid ratio of
the final slag in each experiment could be calculated by thermodynamic calculation
software Factsage7.0 combined with the data in Table 3, which are shown in Table 6.
Table 6 makes clear that the liquid phase ratio of refining slag decreases with the
increase of basicity of refining slag. Many researchers thought that when the basicity
is the same, the liquid phase ratio of the slag increases as the C/A ratio decreases.
However, the actual situation of refining slag 2 and 3 was opposite, because in the
actual production process, some fluorite was added to the slag to adjust the fluidity.
CaF2 in fluorite significantly reduces the melting point of slag. This could reduce the
addition of SiO2 and Al2 O3 .
The viscosity of refining slag was obtained by combining FactSage7.0 with
Roscoe–Einstein Eq. (5). Where ηs+l is the viscosity for solid and liquid mixture, ηl
is the viscosity for liquid, f s is solid phase ratio in the refining slag. Table 7 shows
the viscosity of slag at the end of different refining experiments. It indicates that slag
3 and 4 had lower viscosity and better fluidity.
ηs+l ≈ ηl (1 − f s )−2.5 (5)
The MgO content of slag after refining is shown in Fig. 9. It indicates that the MgO
content of refining slag 3 is the lowest and the MgO content of refining slag 1 is the
highest. However, the initial MgO content of the slags was the same. In other words,
slag 1 had the most serious erosion on furnace lining. Some researchers thought that
the erosion of furnace lining by refining slag is related to their MgO solubility and
viscosity [11]. They believed that the erosion degree of refining slag increases with
the increase of MgO solubility and the decrease of viscosity. Therefore, the MgO
solubilities of the refining slag after refining were calculated, as shown in Table 8.
Referring to Tables 6 and 7, it can be seen that the viscosity of slag 1 is the largest in
Table 7 The viscosity of experimental slags

Slag 1 2 3 4
Viscosity (Pa s) 0.065 0.056 0.051 0.049
Fig. 9 MgO content of slags after refining
Table 8 The MgO solubility of experimental slags

Slag 1 2 3 4
MgO solubility (%) 3.69 4.05 3.56 3.83
the four slags and the solubility of MgO is also at a low level; the erosion of furnace
lining was the most serious, because CaF2 content in slag 1 was the highest, CaF2
could significantly improve the fluidity of slag, but the erosion of furnace lining was
also very serious.
In general, the melting point of slag 1 was too high to melt easily. The viscosity
of slag 2, 3, and 4 had little difference, but the MgO solubility of refining slag 3
was the minimum, and the CaF2 content in slag was the smallest, so slag 3 could
maintain good fluidity and achieve better metallurgical effect under the condition of
low erosion on furnace lining, such as strong adsorption ability to inclusions and low
oxygen content in steel.
In the summary, slag 3 is the optimal refining slag for 25Cr2Ni4MoV steel. On the
count of low total oxygen and dissolved oxygen, low number density of inclusion,
small size of inclusion and less erosion on the lining.
738 C. Zhuo et al.
Conclusions
Through the analysis of the total oxygen content of the four groups of industrial exper-
iments, the composition, size and quantity of inclusions, and the physicochemical
properties of the refining slag, the following conclusions can be obtained:
(1) When the basicity of refining slag is 3–4 and the viscosity is 7–10, it has better
deoxidation effect and stronger adsorption capacity of inclusions, which can
improve the cleanliness of liquid steel. At the end of refining, the total oxygen
content can be reduced to 32 ppm, and the inclusion quantity density can be
reduced to 3.18/mm2 .
(2) Dissolved oxygen in molten steel decreases with increasing basicity and C/A
ratio of refining slag.
(3) The adsorption capacity of refining slag to Al2 O3 inclusions increases with the
increase of basicity and C/A ratio of refining slag.
(4) In the refining process, the initial inclusion was mainly Al2 O3 , which was then
combined with [Mg] introduced in the molten steel by slag or refractory to form
MgO–Al2 O3 . Finally, it combined with the [Si], [Ca], and [Mn] in the molten
steel formed the MgO–Al2 O3 –SiO2 –CaO(–MnO) system inclusions.
Acknowledgements This work was supported by the Natural Science Foundation of China (No.
51774030, No. U1860104).
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steel. Ironmak Steelmak 46(5):416–423
Prediction Model of End-Point Molten
Steel Temperature in RH Refining Based
on PCA-CBR
Maoqiang Gu, Anjun Xu, Dongfeng He, Hongbing Wang and Kai Feng
Abstract The end-point temperature prediction model of molten steel for RH refin-
ing process, based on principal component analysis (PCA) and case-based reasoning
(CBR), was established for the precise control of end-point molten steel temperature.
Six principal components were selected from eleven factors influencing molten steel
temperature based on PCA, which were taken as the principal component analysis
and case-based reasoning (PCA-CBR) model inputs to construct the corresponding
model. The precision of the model was verified by the actual production data of a
steel plant, which was compared with the prediction model based on conventional
CBR model as well as the back propagation neural network (BPNN) model. The
results show that the precision of the model based on PCA-CBR reaches 69.67%,
83.67%, and 97%, respectively, when its prediction error is in the range of [−5, 5],
[−7, 7], and [−10, 10], respectively. Therefore, the model can predict the end-point
temperature of molten steel for RH refining process more precisely.
Keywords Principal component analysis · Case-based reasoning · RH refining ·

Molten steel temperature · Prediction model
Introduction
RH refining process is a necessary intermediate buffering link between the converter

and the continuous caster during a high-quality steel manufacturing process. The
control of end-point temperature of molten steel for RH refining process can directly
influence the prediction accuracy of molten steel temperature in the tundish. With
the increasing demand for high efficiency and fast production rhythm in steel plants,
M. Gu · A. Xu (B) · D. He · K. Feng
e-mail: anjunxu@126.com
H. Wang
School of Computer and Communication Engineering, University of Science and Technology

https://doi.org/10.1007/978-3-030-36540-0_66
742 M. Gu et al.
the requirements for the control accuracy of RH end-point temperature of molten

steel have also become higher. In such a context, traditional molten steel temperature
monitoring and control methods and the mechanical models could hardly meet the
requirements [1, 2]. The data-driven model based on machine learning algorithms,
on the other hand, has provided an alternative solution to the problem.
With the development of artificial intelligence (AI) technology, AI-based data-
driven models have been widely used for end-point control in steelmaking. Com-
monly used AI algorithms include neural networks and case-based reasoning
(CBR). With respect to neural networks, Tian, and Mao integrated the improved
AdaBoost.RT into the extreme learning machine (ELM) algorithm and realized the
prediction of end temperature of molten steel in LF furnace [3]; Han and Liu built
the membrane-algorithm-improved ELM model to realize the prediction of con-
verter end-point temperature [4]; He et al. established the ladle thermal state and
neural-network-based hybrid model to predict the end-point temperature in LF refin-
ing [5]; Feng et al. built the self-organizing data-mining-centered GMDH neural
network model to predict LF end-point molten steel temperature [6]; Wang et al.
built a tree-structure-based integrated general regression neural network model to
predict the end-point molten steel temperature in LF refining [7]. Neural network
algorithm boasts strong, non-linear mapping and self-learning capabilities; yet it has
been proved to be slow in learning speed and susceptible to being trapped in local
extrema, and other problems.
Compared with the neural network algorithm, CBR can solve new problems by
searching for the same or similar cases in the case library and their solutions. Nowa-
days, scholars have already applied it to end-point prediction in steelmaking. Wang
et al. established a complete CBR model to predict the end-point molten steel tem-
perature in an AOD furnace [8]; Wang and Han established a causality-based CBR
model to predict oxygen blowing volume and coolant feed amount for the converter,
aiming to realize the control of converter end-point molten steel temperature [9]. Han
and Wang built a mutual information-based CBR model to target the issue of case
property determination and to predict the oxygen blowing volume for the converter
and thereby realized the control of molten steel temperature in the converter [10];
Wang et al. built a CBR model integrating the search methods of sorting, rough-
ing, refining, and prioritizing to clarify the issue of case retrieving efficiency and
accuracy to predict refining starting temperature [11]; Han and Cao established an
improved CBR model based on fuzzy C mean, mutual information, and support vec-
tor machine (SVM) to address the case retrieving accuracy and case reutilization
strategy to predict the end-point control of a converter [12]. Focusing on the case
retrieving accuracy, Wang and Dong built a fuzzy similarity-based CBR model to
predict the oxygen blowing volume for a converter and thereby realized the control
of end-point temperature in the converter [13].
Currently, research on CBR algorithm mainly focuses on case retrieval, while
the availability of case property optimization-related research is rare to find. If the
dimension of case properties was set too high, the data density would be reduced,
thus impeding the improvement of model accuracy; PCA, on the other hand, could
effectively reduce the data dimension. Therefore, this paper combines PCA and
Prediction Model of End-Point Molten Steel Temperature … 743
CBR by first reducing the data dimension with PCA, then determining the principal
components before inputting them into the CBR model. In the end, a corresponding
PCA-CBR model was established on such a basis to predict the end-point molten
steel temperature in RH refining process and verified by actual production data of a
steel plant.
PCA-CBR Model
Principal Component Analysis
Principal component analysis is a multivariate technique that analyzes data in which

observations are described by several inter-correlated quantitative dependent vari-
ables. Its goal is to extract the important information from the data, to represent it as
a set of new orthogonal variables called principal components.
Suppose that a dataset has n samples, each sample is represented by
a p-dimensional variable, namely x 1 , x 2 , …, x p , the original data matrix can be
expressed as X = (x ij )n×p . The steps of principal component analysis are as follows:
(1) Standardize the original variable as formula (1).
xi j − x j
yj = (1)
sj
where
1 n 1 2
xj = xi j , s2j = xi j − x j .
n i=1 n−1
(2) Calculate the correlation coefficient matrix:

⎡ ⎤
r11 r12 · · · r1 p
⎢ r21 r22 · · · r2 p ⎥
⎢ ⎥
R=⎢ . .. . . .. ⎥ (2)
⎣ .. . . . ⎦
r p1 r p2 · · · r pp
where
n
(xki − xi )(xk j − x j )
ri j = k=1 n 2 (i, j = 1, 2, . . . , p).
n
k=1 (x ki − x i ) k=1 x k j − x j
2
(3) Calculate the eigenvalues and the eigenvectors of formula (2).

744 M. Gu et al.
(4) Calculate the principal component contribution rate and the cumulative contri-
bution rate, and extract m principal components according to the cumulative
contribution rate criterion. The contribution rate of the ith principal component
is

p
li = λi λk (i = 1, 2, . . . , p) (3)
k=1
The cumulative variance contribution rate is

p
m
K= λi λk (4)
i=1 k=1
Generally, the eigenvalues λ1 , λ2 , …, λm whose cumulative contribution

ratio is 75–95% or more are corresponding to the first, second, …, mth (m ≤ p)
principal components.
(5) Calculate the principal component loads and principal components. The load
amount of original variable X i on the principal component F k can be calculated
as formula (5):

P(Kk , Xi ) = λk eki (k = 1, 2 . . . , m; i = 1, 2 . . . , p) (5)
The m principal components of the original data samples can be calculated

as formula (6):
Fk = e1k X 1 + e2k X 2 + · · · + e pk X p (k = 1, 2, . . . , m) (6)
Case-Based Reasoning
Case-based reasoning is a reasoning mode that retrieves similar problems and solu-
tions which were solved in the past and compares the background and time differences
with the new and old problems, then adjusts and modifies old case solutions to solve
new problems. The case-based reasoning process mainly includes case representa-
tion, case retrieval, case reuse, and case revision and preservation. Among them, case
retrieval is the key link.
This paper uses the nearest neighbor method for case retrieval. The specific steps
are as follows:
(1) Influencing factors weight calculation:
In this paper, the entropy weight method is used to calculate the weight of the
influencing factors. The formula is as follows (7)–(11):
(a) Data normalization, the normalization method used in this paper is [−1, 1]
normalization as formula (7):
xi j − min(xi j )
i
ri j = −1 + 2 · (7)
max(xi j ) − min(xi j )
i i
where i is the number of data, j is the subscript of the influencing factor, mini (xi j )
is the minimum value of the original data, maxi (xi j ) is the maximum value of
the original data, xi j is the value before normalization, ri j is the normalized
value.
(b) Calculate the information entropy of the jth factor as the formula (8)–(10):

N
H j = −k f i j · ln f i j (8)
i

N
f i j = ri j ri j (9)
i
k = 1/ ln N (10)
where: H j is the entropy value of the jth indicator; k is the information entropy
coefficient; N is the number of rows of the original data.
(c) Calculate the weight of the jth factor.
⎛ ⎞

M
Wj = 1 − Hj ⎝M − Hj⎠ (11)
j=1
where: M is the number of influencing factors.
(2) Similarity calculation

This paper uses Euclidean distance similarity. Suppose the number of influencing
factors of the case is n, the jth factor of the case in the case library is X j , the jth
influencing factor in the new case is Y j , and the weight of the jth factor is W j , then
the new case and case base of the Euclidean distance between the cases is as formula
(12).

n

d(X, Y) = W j (Yi − Y j )2 (12)
i=1
The similarity between the cases as formula (13).

746 M. Gu et al.
1
Gsim (X, Y) = (13)
1 + d(X, Y)
After the case retrieval finds a similar case, the case is reused. The formula is
expressed as formula (14).
N
Gi · Ti
T= i=1
N (14)
i=1 Gi
PCA-CBR
In the PCA-CBR model, PCA is used to extract the principal components from the
original data, and then the obtained principal components were used as the input of
the case-based reasoning model. The process of PCA-CBR prediction model process
is shown in Fig. 1.
Fig. 1 Process of the PCA-CBR model

Experiments and Results
Analysis of Influencing Factors
The process of RH refining process includes decarburization, alloying, temperature

control, and calm treatment. Influencing factors of end-point molten steel temperature
include starting temperature in RH, mass of scrap, volume of oxygen blowing, ladle
heat state (ladle waiting time, ladle life), refining cycle, thickness of slag, mass of
molten steel, temperature of RH vessel, vacuum refining time, and mass of alloy
additions. In this paper, actual production data of RH refining in the Qian’an Steel
Corporation from January 2014 to June 2015 were collected and preprocessed. The
statistical results are shown in Table 1.
Table 1 Statistical results of factors affecting RH refining end-point molten steel temperature
Symbols Variables Units Minimum Maximum Mean Standard
deviation
X1 Starting °C 1592 1641 1618.27 9.877
temperature in
RH
X2 Mass of scrap t 0 3.785 0.416 0.656
X3 Volume of Nm3 0 198 27.52 47.841
oxygen blowing
X4 Ladle waiting min 34 1399 172.07 238.692
time
X5 Refining time min 19 89 39.73 12.419
X6 Ladle life – 2 58 22.59 13.644
X7 Thickness of mm 60 90 79.45 5.802
slag
X8 Mass of molten t 200.8 235.5 221.716 5.4516
steel
X9 Temperature of °C 896 1131 1012.89 45.785
RH vessel
X10 Vacuum min 13 42 13.93 3.884
refining time
X11 Amount of alloy t 0.638 4.001 1.216 0.629
additions
Y End-point °C 1580 1603 1590.33 4.502
temperature in
RH
748 M. Gu et al.
Principal Component Analysis of Influencing Factors
Through the correlation analysis of the 11 influencing factors of RH refining, the

obtained correlation matrix and total variance are explained in Tables 2 and 3.
According to the cumulative contribution rate of the principal components,
six principal components are obtained as formula (15)–(20), and the cumulative
contribution rate of the six principal components reaches 79.812%.
F1 = 0.603 · X1 + 0.848 · X2 − 0.663 · X3 − 0.190 · X4 − 0.451 · X5 + 0.031 · X6

− 0.014 · X7 + 0.107 · X8 + 0.133 · X9 − 0.178 · X10 + 0.838 · X11 (15)
F2 = 0.149 · X1 + 0.385 · X2 − 0.556 · X3 + 0.071 · X4 − 0.595 · X5 + 0.175 · X6

− 0.019 · X7 + 0.259 · X8 − 0.228 · X9 − 0.819 · X10 + 0.436 · X11 (16)
F3 = −0.128 · X1 + 0.080 · X2 + 0.054 · X3 + 0.238 · X4 − 0.196 · X5 + 0.600 · X6

+ 0.681 · X7 − 0.515 · X8 − 0.033 · X9 + 0.072 · X10 + 0.075 · X11 (17)
F4 = 0.156 · X1 − 0.001 · X2 + 0.030 · X3 + 0.578 · X4 + 0.164 · X5 + 0.190 · X6

− 0.313 · X7 − 0.076 · X8 + 0.737 · X9 − 0.038 · X10 + 0.005 · X11 (18)
F5 = 0.588 · X1 − 0.194 · X2 − 0.220 · X3 + 0.036 · X4 + 0.392 · X5 + 0.447 · X6

+ 0.013 · X7 + 0.158 · X8 − 0.338 · X9 − 0.278 · X10 − 0.217 · X11 (19)
F6 = 0.039 · X1 − 0.013 · X2 − 0.021 · X3 + 0.591 · X4 − 0.155 · X5 − 0.310 · X6

+ 0.459 · X7 + 0.561 · X8 − 0.107 · X9 − 0.043 · X10 − 0.025 · X11 (20)
Model Results and Analysis
Among 1928 data sets, 1628 sets were selected as case-base data, the remaining 300
sets of data were used as test data.
CBR Model
In order to verify the prediction accuracy of the PCA-CBR model, the traditional
CBR model was also established. The weight calculation method in the CBR model
used the entropy weight method, the similarity calculation method used the Euclidean
Table 2 Correlation analysis matrix
X1 X2 X3 X4 X5 X6 X7 X8 X9 X10 X11
X1 1.000 – – – – – – – – – –
X2 0.428 1.000
X3 −0.384 −0.296 1.000
X4 −0.044 −0.102 0.129 1.000
X5 0.090 −0.229 0.497 0.080 1.000
X6 0.078 0.051 0.027 0.039 0.087 1.000
X7 −0.015 0.004 0.035 0.075 −0.135 0.114 1.000
Prediction Model of End-Point Molten Steel Temperature …
X8 0.137 0.093 0.016 0.010 0.073 −0.113 −0.059 1.000

X9 0.025 0.052 −0.090 0.066 −0.138 −0.010 −0.090 −0.052 1.000 – –
X10 −0.101 0.152 0.509 0.035 0.375 0.064 0.030 0.094 −109 1.000 –
X11 0.376 0.975 −0.246 −0.079 −0.176 0.055 −0.022 −0.091 0.030 0.195 1.000
749
750 M. Gu et al.
Table 3 Total variance interpretation

Initial eigenvalue Extracting the sum of squared loads
Component Total Percentage Cumulative Total Percentage Cumulative
of variance contribution of variance contribution
rate rate
1 2.578 23.439 23.439 2.578 23.439 23.439
2 1.850 16.816 40.256 1.850 16.816 40.256
3 1.221 11.098 42.354 1.221 11.098 42.354
4 1.070 9.724 61.078 1.070 9.724 61.078
5 1.054 9.553 70.631 1.054 9.553 70.631
6 1.010 9.181 79.812 1.010 9.181 79.812
7 0.798 7.256 87.067
8 0.730 6.633 93.701
9 0.385 3.501 97.202
10 0.288 2.614 99.816
11 0.020 0.184 100.000
distance similarity, and the number of case reuse was 5. The weights of the influencing
factors were shown in Table 4.
The statistics of the prediction accuracy of the CBR model was shown in Fig. 2.
BPNN Model
Similar to the CBR model, a BP neural network (BPNN) model was also established.
The neural network model (BPNN) uses a typical three-layer network with an input
layer, an implicit layer, and an output layer. The input layer has 11 nodes representing
all the influencing factors, the hidden layer has 13 nodes, the activation function
selects the Sigmoid function, the output layer has 1 node, and the activation function
is the purelin function. The prediction accuracy of the BPNN model was shown in
Fig. 3.
PCA-CBR Model
The weight calculation method in the PCA-CBR model used the entropy weight
method and the similarity calculation method used the Euclidean distance similarity,
and the number of case reuse was 5. The weight calculation results of the principal
components in the PCA-CBR model were shown in Table 5.
The prediction accuracy of the PCA-CBR model was shown in Fig. 4.
Table 4 Weights of influencing factors in the CBR model
Influencing factors X1 X2 X3 X4 X5 X6 X7 X8 X9 X10 X11
Weight 0.020 0.236 0.343 0.197 0.042 0.061 0.008 0.007 0.015 0.015 0.058
Prediction Model of End-Point Molten Steel Temperature …
751
752 M. Gu et al.
Fig. 2 Prediction accuracy of the CBR model
Fig. 3 Prediction accuracy of the BPNN model
Table 5 Principal component weights of PCA-CBR model

Principal components F1 F2 F3 F4 F5 F6
weights 0.211 0.089 0.152 0.257 0.154 0.137
Fig. 4 Prediction accuracy of the PCA-CBR model
Table 6 Comparison of
[−5, 5] [−7, 7] [−10, 10]
prediction accuracy of each
model PCA-CBR (%) 69.67 83.67 97.33
CBR (%) 67.00 82.67 97.33
BPNN (%) 67.00 81.00 97.00
Analysis of Prediction Results
The statistical summary of the prediction results of each model is shown in Table 6
and Fig. 5.
As can be seen from the above table, the prediction errors of the model based on
PCA-CBR is 69.67%, 83.67%, and 97% in the range of [−5, 5], [−7, 7], and [−10,
10], respectively. Compared with the best results in the CBR model and the BPNN
model, the hit rate in the range of [−5, 5] and [−7, 7] is increased by 2.67% and 1%,
respectively, indicating that the model established is valid.
Conclusion
This paper introduced a PCA-CBR model to predict the end-point molten steel tem-
perature in RH refining process. The model first reduced 11 influencing factors of
the molten steel temperature in RH refining to seven principal components using
754 M. Gu et al.
Fig. 5 Comparison of prediction accuracy of every model
PCA, then input the seven principal components into the CBR model to predict the
end-point molten steel temperature in RH refining. To verify the prediction accuracy
of the PCA-CBR model, a CBR model and a BPNN model were also established
in this paper, and the actual production data of a steel plant were introduced for
verification. The results indicate that
(1) PCA can effectively reduce the data dimension and improve the prediction
accuracy of the case-based reasoning model.
(2) The accuracies of prediction errors of the PCA-CBR model within [−5, 5], [−7,
7], and [−10, 10] are 69.67%, 83.67%, and 97.33%, respectively. Compared
with the CBR model and the BPNN model, the accuracies of errors in [−5, 5] is
2.67% higher, and 1% higher in [−7, 7]. The PCA-CBR model can hence more
accurately predict the end-point molten steel temperature in RH refining.
Acknowledgements This work is supported by the National Key Technology R&D Program of
China (2017YFB0304000 & 2017YFB0304001) and the National Natural Science Foundation of
China (51674030).
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FactSage-Based Design Calculations
for the Production of High-Carbon
Ferromanganese on Pilot-Scale
Joalet Dalene Steenkamp
Abstract The EU-funded PreMa project investigates the potential for a preheating
stage to reduce the electrical energy requirement and CO2 emissions produced, during
the production of high-carbon ferromanganese in a submerged arc furnace. A pilot-
scale campaign will be conducted at MINTEK in South Africa to demonstrate the
potential effect of preheating on furnace operation. For the pilot-scale campaign, the
design of the process flowsheet and sizing of the furnace and ancillary equipment were
based on predictive mass and energy balance calculations. FactSage thermodynamic
software and Microsoft Excel were utilised. The paper reports on the method applied
and results obtained.
Keywords FactSage · High carbon · Ferromanganese · Pilot-scale
Introduction
High-carbon ferromanganese (HCFeMn) is an alloy consisting of 74–82% Mn, 7.5%

C, 1.2% Si, 8–16% Fe, and minor impurities, i.e. P, S, As, Sn, Pb, and Cr [1]. It is
mainly produced in electric submerged arc furnaces (SAFs), where the tips of the
electrodes are submerged in a burden of raw materials, as illustrated in Fig. 1. Typical
raw materials fed into the furnaces are manganese ores, carbonaceous reductants,
and fluxes. The furnaces are typically round with three Söderberg electrodes, in
equilateral triangular arrangement, supplying the electrical energy to the process.
Electrical energy is converted to heat mainly through the resistive heating of the
wet coke-bed. The wet coke-bed primarily consists of a mixture of liquid slag and
coke. Alloy collects in the hearth of the furnace. Liquid slag and alloy are tapped
intermittently through single- or bi-level tap-holes for further handling downstream.
J. D. Steenkamp (B)
e-mail: joalets@mintek.co.za
University of the Witwatersrand, 1 Jan Smuts Ave,
Johannesburg 2000, South Africa

https://doi.org/10.1007/978-3-030-36540-0_67
758 J. D. Steenkamp
Fig. 1 Simple schematic of the process flow in a submerged arc furnace utilised in the production
of high-carbon ferromanganese
Dust laden offgas is collected from the top of the furnace for further downstream
treatment. Furnaces can be open, where a gap between the top of the sidewalls and
the furnace roof allows for CO-rich offgasses to be combusted prior to cleaning and
venting, or closed, where CO-rich offgas is cleaned and utilised downstream as a
source of energy.
The HCFeMn production process is energy intensive with requirements ranging
between 2.0 and 3.5 MWh per ton alloy [2–5]. The process is also a significant
producer of CO2 emissions, especially in countries where the electrical energy is
supplied by coal-fired power stations.
The PreMa project (2018–2022) aims at demonstrating a suite of innovative tech-
nologies to reduce the consumption of electrical energy and CO2 emissions during
the production of HCFeMn in SAFs. A preheating unit will be added to the flowsheet
and various technologies are considered, the details of which lie outside the scope
of this paper.
Included in the test program is a pilot-scale campaign where the effect of preheat-
ing ore to 600 ◦ C on SAF operation will be evaluated. As part of the design of the
process flowsheet for the pilot-scale facility, and to size the furnace and upstream
and downstream equipment, a number of questions were raised:
1. What alloy specification will be targeted in terms of the major components (Mn,
Fe, Si, and C)?
2. What raw materials will be selected?
3. What will the ore blend be to meet the selected alloy specification?
FactSage-Based Design Calculations for the Production … 759
4. What will the stoichiometric reductant requirement be?

5. What will the flux requirement be to optimize the recovery of Mn, ensuring tap-
ability of the slag at the same time?
6. What will the process energy requirement be at equilibrium?
Answers were obtained through a review of literature and predictive mass and
energy balance calculations.
Alloy Specification
ASTM standard A99-03 [1] defines the typical grades for high-carbon ferroman-
ganese (HCFeMn). The grades vary in terms of their Mn-content with Grade A
ranging from 78 to 82% Mn, Grade B from 76 to 78% Mn, and Grade C from 74
to 76% Mn. For design purposes, the lower end of Grade A was targeted: 78% Mn,
7.5% C, 1.2% Si, and 12% Fe (calculated by difference), and a Mn/Fe ratio of 6.5.
Raw Materials
South Africa accounts for 78% of the world’s identified manganese resources and
29% of the world’s reserves [6]. In typical smelter operations, especially in South
Africa, more than one type of commercially available manganese ore is utilised. This
fact is explained by the geology of the Kalahari Manganese Field (KMF), the main
source of manganese ores commercially available in South Africa.
Three ore types may be distinguished in the KMF deposit on the basis of their geo-
logical alteration styles and mineral assemblages [7–9]. Mamatwan-type represents
the least altered, low-grade type of ore in the deposit, and typically contains between
20 and 38% Mn. Wessels-type represents hydrothermally altered, high grade type of
ore and typically contains between 45 and 60% Mn. The third type of ore is supergene
altered ore, which is of variable grade, depending on the degree of alteration.
Key to the definition of these ore types is their different mineral assemblages.
Mamatwan-type ores are enriched in Mn-bearing carbonates, compared to Mn oxide-
rich Wessels-type ores. The oxidation state of the manganese in both types of ores
is limited to the bivalent and trivalent state. The supergene ores are defined by the
presence of tetravalent Mn-oxide minerals, and are of intermediate grade [9].
Mamatwan ore accounts for the bulk of the commercial ore in the KMF (around
95%) and the supergene ore accounts for a very small portion of the deposit. Due
to its abundance, the Mamatwan-type ore forms the basis of any HCFeMn smelting
facility in South Africa. Due to its low Mn-content, and increasing smelting costs,
the Mamatwan-type ore is blend with Wessels-type or supergene ore.
760 J. D. Steenkamp
Table 1 Chemical compositions of raw materials in % by mass

Component Al2 O3 CaO Fe Fe2 O3 MgO Mn SiO2 Total Mn/Fe
Ore #A 0.13 13.21 4.94 – 3.30 37.78 5.60 64.96 7.65
Ore #a 0.14 14.94 5.79 – 2.59 35.11 5.01 63.58 6.06
Ore #B 0.09 15.33 3.86 – 4.21 34.29 4.72 62.50 8.88
Ash in coke 17.01 20.53 – 33.04 2.25 – 27.17 100.00 –
Quartz 1.20 – – – – – 98.80 100.00 –
Producers of manganese ferroalloys typically operate their processes with a num-

ber of carbonaceous reductants (i.e., see [10]), and in South African operations,
quartz is often added as flux.
For the pilot-scale campaign, five types of raw materials were considered: three
types of ores, coke as carbonaceous reductant, and quartz as flux. Ore from Mine
A formed the baseline, blended with ore from Mine B in order to meet the Mn/Fe
requirement of the alloy due to its higher Mn/Fe ratio (see Table 1). Two grades of ore
from Mine A were considered and referred to as Ore #A and Ore #a, respectively. Ore
from Mine B was referred to as Ore #B. As carbonaceous reductant, only one coke
was considered in order to simplify the process control during the campaign. The
coke consisted of 2.62% volatile matter, 10.03% ash, and 87.35% fixed carbon (all dry
basis) with 3.96% moisture being typical. Table 1 contains the chemical compositions
of the manganese ores, ash in coke, and quartz considered in the design calculations.
Ore Blend
To determine the types and ratios of the different manganese ores to utilise in the
design calculations, the recovery of Mn was assumed to be 80% and of Fe 100%.
These assumptions were based on a review of publications available in literature.
Results for accounting balances, based on industrial (closed SAF) [2–4, 11, 12] or
pilot (open SAF) [13, 14] plant data, as well as predictive balances [2, 5, 11, 15]
were summarised in Table 2. Equation 1 defines basicity (B3 ) where all components
were expressed in % by mass.
%CaO + %MgO
B3 = (1)
%SiO2
Taking the recoveries for Mn and Fe into account, the Mn/Fe ratio of the respective
ores then reduces to 6.12 for Ore #A, 4.85 for Ore #a, and 7.11 for Ore #B. To produce
an alloy with Mn/Fe ratio of 6.5, Ore #A and Ore #B have to be blend at a ratio of
61.38/38.62, and Ore #a and Ore #B at 26.90/73.10. As ore from mine A had to form
the baseline and ore from mine B only had to be added as ‘sweetener’, the use of
Ore #a was not further considered due to its unfavourable ratio to Ore #B.
Table 2 Summary of relevant parameters for mass and energy balance calculations mentioned
in literature where raw material input temperatures were 25 ◦ C in all instances except for *[11]
where raw materials were preheated to 600 ◦ C using an external rotary kiln. Where applicable,
mass percent applies
Reference Unit [2] [3] [4] [11] [14] [13] [5] [15]
Mn Rec (%) 70–80 82 85 43–68 82–83
Fe Rec (%) 100 100 100 80–100 100
Mn/Fe Or e (%/%) >6 >6.2 5.4 1.0–2.7
C E xcess (%) 10–30 <10
Energy Pr edict (MWh/ton 2.196 2.207 2.3 2.413 3.15 1.924–
alloy) (*1.878) 3.001
Energy Actual (MWh/ton 2.5–3.5 2.2 2.1–2.3 2.0 2.7
alloy)
Energy Lost (%) 27 20 20 20
(16–38)
T Alloy (C) 1500 1500 1500 1440,
1490,
1540
T Slag (C) 1500 1500 1500 1440, 1500
1490,
1540
TGas (C) 200– 200 400 25
500
MnO Slag 18.8 34.6 30 45.6 15.1– 25.5– 20
32.0 27.4
B3 1.3–1.6 1.0 0.9 1.1 1.3
Thermodynamic Calculations
As the South African process for the production of HCFeMn is considered to be

near equilibrium [3], equilibrium mass and energy balance calculations were initially
considered sufficient for design purposes, both in terms of the carbonaceous reductant
and energy requirements.
The calculations were conducted in the Equilib module of the FactSage 7.2 ther-
modynamic software [16]. As solution databases, FToxid was applied for the oxide
systems and a custom-made database (FeMn) [17] for the alloy systems. The pure
specie database (FactPS) was also selected.
As the phase chemistry could play a role, the chemical analyses of the ores and
reductant were converted to mineral phases available in the FactSage databases (see
Table 3). The conversions were based on the following assumptions:
1. Braunite consisted of MnSiO3 and 3Mn2 O3 ; all SiO2 present as MnSiO3 .
2. Jacobsite consisted of MnFeO4 and Fe is primarily present as MnFeO4 .
3. Hausmanite consisted of Mn3 O4 and accounted for the remainder of the Mn.
4. Hematite consisted of Fe2 O3 and accounted for Fe when Mn3 O4 became negative.
5. Dolomite consisted of CaMg(CO3 )2 and contained all Mg.
762
Table 3 Input parameters for thermodynamic calculations in FactSage 7.2—composition normalised, i.e., mass in grams equals per cent by mass
Item Al2 O3 C CaO CaCO3 CH4 Fe2 O3 H2 O MgO (Ca, MnO·SiO2 Mn2 O3 Mn3 O4 MnFe2 O4 SiO2 Total
Mg)(CO3 )2
1 0.12 – – 23.15 – 1.35 – – 16.56 11.49 41.53 – 5.80 – 100.00
2 0.16 – 16.39 – – 1.77 – 4.09 – 15.15 54.77 – 7.65 – 100.00
3 0.08 – – 25.47 – – – – 21.16 9.70 35.05 2.85 5.69 – 100.00
4 0.12 – 20.12 – – – – 5.53 – 13.51 48.83 3.97 7.93 – 100.00
5 1.2 – – – – – – – – – – – – 98.8 100.00
6 1.6 83.9 2.0 – 2.5 3.2 4.0 0.2 – – – – – 2.6 100.00
7 Solid-1 Solid-1 Solid – Gas Solid-1 Liquid Solid – Solid Solid-1 Solid-1 Solid Solid-1 –
gamma graphite(s) lime hematite periclase rhodonite bixbyite solid-A quartz(l)
8 FToxid FeMn FToxid – FactPS FToxid FactPS FToxid – FToxid FToxid FactPS FactPS FactPS –
9 25 25 25 25 25 25 25 25 25 25 25 25 25 25 –
10 25 25 25 25 25 25 25 25 25 25 25 25 25 25 –
11 600 – 600 600 – 600 – 600 600 600 600 600 600 – –
Where items are
1. Ore #A with calcite and dolomite
2. Ore #A with CaO and MgO
3. Ore #B with calcite and dolomite
4. Ore #B with CaO and MgO
5. Quartz
6. Coke
7. Phase selected in FactSage
8. Database selected in FactSage
9. Temperature #1 (◦ C)—All raw materials
10. Temperature #2 (◦ C)—Coke and quartz
11. Temperature #2 (◦ C)—Ore
J. D. Steenkamp
6. Calcite consisted of CaCO3 and accounted for the remainder of the Ca.
7. Volatile matter in the coke only consisted of CH4 .
Each of these streams were predefined in the Mixture module of the FactSage 7.2
thermodynamic software. The ore streams were specified at two temperatures: 25
and 600 ◦ C. In all calculations the initial conditions of the phases were specified as
indicated in Table 3.
In the Equilib module, all ideal gas species were selected as well as all pure solids
and pure liquid species, with duplicates suppressed and the solution databases having
priority over the pure specie database. For the oxide systems, all solution phases were
selected, except in cases where more than one option existed, for which the A-phase
was selected, i.e., Slag-A. For the alloy system, all solution phases were selected.
Equilibrium was calculated for normal and transition states.
Other input conditions were summarised in Table 4 on a case-by-case basis. The
results of the calculations were summarised in Table 5 which can be found just before
the sub-section on sensitivity analysis.
Stoichiometric Reductant Requirement
As a first iteration, a flux-less operation was analysed by reacting 100 g of ore blend
with 0–100 g coke, at intervals of 10 g at 1500 ◦ C. Two cases were evaluated. In Case
#1, all input materials were considered to be at 25 ◦ C. In Case #2, the ore blend were
input at 600 ◦ C and coke and quartz at 25 ◦ C. Products were produced at 1500 ◦ C.
The results were analysed in terms of mass of alloy (FEMN-Liqu) and graphite
(FEMN-C(s)) phases formed per 100 g ore blend, as a function of coke additions.
The reductant requirement was estimated as the point just before the formation of
graphite as reaction product, as it was assumed that the formation of graphite indicated
a surplus of coke. For both Case #1 and Case #2, 22.03 g of coke is required per
100 g of ore blend forming 38.87 g of alloy. Preheating of the ore streams neither
influenced the reductant requirement nor the formation of alloy phase.
Process Energy Requirement at Equilibrium
To determine the process energy requirements, the thermodynamic calculations in

FactSage 7.2 were done in three steps:
1. In the first step, the phases produced at 1500 ◦ C when reacting Ore #A and Ore #B,
and coke were calculated. Also calculated, was the energy required to produce
these phases at 1500 ◦ C. The amounts and compositions of the gas and alloy
phases produced were saved as streams to be used in subsequent calculations.
764 J. D. Steenkamp
Table 4 Inputs for various cases evaluated using the Equilib module in FactSage 7.2 with the
FACTPS, FToxid, and custom alloy database. For ease of reference, the variables that changed from
the previous case was indicated in italics for each case
Case Ore Ore Quartz Coke H2 O T Mi x A/B T Mi x C T Mi x D T H2 O T Slag TGas T Alloy
#A #B (g) (g) (g)
(g) (g)
#1 61.38 38.62 – 22.03 – 25 – 25 – 1500 800 1400
#2 61.38 38.62 – 22.03 – 600 – 25 – 1500 800 1400
#3 61.38 38.62 12.86 21.54 – 25 25 25 – 1500 800 1400
#4 61.38 38.62 12.86 21.54 – 600 25 25 – 1500 800 1400
#5 61.38 38.62 – 23.49 – 25 – 25 – 1500 800 1400
#6 61.38 38.62 – 23.49 – 600 – 25 – 1500 800 1400
#7 61.38 38.62 10.24 23.06 – 25 25 25 – 1500 800 1400
#8 61.38 38.62 10.24 23.06 – 600 25 25 – 1500 800 1400
#9 61.38 38.62 10.24 21.91 – 25 25 25 – 1500 800 1400
#10 61.38 38.62 10.24 21.33 – 25 25 25 – 1500 800 1400
#11 61.38 38.62 10.24 20.75 – 25 25 25 – 1500 800 1400
#12 61.38 38.62 10.24 19.60 – 25 25 25 – 1500 800 1400
#13 61.38 38.62 10.24 18.45 – 25 25 25 – 1500 800 1400
#14 61.38 38.62 15.36 23.06 – 25 25 25 – 1500 800 1400
#15 61.38 38.62 5.12 23.06 – 25 25 25 – 1500 800 1400
#16 61.38 38.62 10.24 23.06 – 25 25 25 – 1450 750 1350
#17 61.38 38.62 10.24 23.06 – 25 25 25 – 1400 700 1300
#18 61.38 38.62 10.24 23.06 – 25 25 25 – 1500 700 1400
#19 61.38 38.62 10.24 23.06 – 25 25 25 – 1500 600 1400
#20 61.38 38.62 10.24 23.06 – 25 25 25 – 1500 500 1400
#21 61.38 38.62 10.24 23.06 – 25 25 25 – 1500 400 1400
#22 61.38 38.62 10.24 23.06 1.00 25 25 25 25 1500 800 1400
#23 61.38 38.62 10.24 23.06 2.00 25 25 25 25 1500 800 1400
#24 61.38 38.62 10.24 23.06 4.00 25 25 25 25 1500 800 1400
#25 61.38 38.62 10.24 23.06 8.00 25 25 25 25 1500 800 1400
2. In the second step, the phases produced and energy required when cooling the gas
to 800 ◦ C were calculated. This was done to quantify the effect of the gas cooling,
as it percolates through the burden, on the energy required.
3. In the final step, the phases produced and energy required when cooling the alloy
to 1400 ◦ C were calculated. This was done to quantify the effect of alloy typically
leaving the process at a lower temperature, on the energy required.
The process energy requirements for Case #1 and Case #2 calculated in this manner
were 3.301 and 2.932 MWh/ton alloy, respectively.
Table 5 Results of various cases evaluated using the Equilib module in FactSage 7.2 with the FACTPS, FToxid, and custom alloy database. Where applicable,
mass percent applies
Case Energy Energy Alloy (g) Mn Alloy Fe Alloy Si Alloy C Alloy Mn/Fe Mn Rec Fe Rec (%) Slag/Alloy MnO Slag Solids Slag B3
(MWh/ton (MWh/ton (%) (%) (%) (%) (g/g) (%) (g/g) (%) (%)
ore) alloy)
#1 1.279 3.301 38.8 82.8 10.0 0.0 7.2 8.28 95 100 0.79 3.1 93.5 3.73
#2 1.137 2.932 38.8 82.8 10.0 0.0 7.2 8.28 95 100 0.79 3.1 93.5 3.73
#3 1.318 3.566 36.9 81.9 10.5 0.7 6.9 7.83 89 100 1.23 7.8 0.0 1.33
#4 1.175 3.180 36.9 81.9 10.5 0.7 6.9 7.83 89 100 1.23 7.8 0.0 1.33
#5 1.147 2.158 53.1 83.3 9.5 0.0 7.2 8.77 97 100 0.61 3.0 92.8 3.75
#6 1.022 1.923 53.1 83.3 9.5 0.0 7.2 8.77 97 100 0.61 3.0 92.8 3.75
#7 1.187 2.304 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#8 1.062 2.061 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#9 1.152 2.323 49.6 83.1 10.1 0.3 6.5 8.23 90 100 0.93 10.4 0.0 1.35
#10 1.133 2.340 48.4 83.3 10.3 0.2 6.1 8.08 89 100 0.98 12.4 0.0 1.34
#11 1.115 2.363 47.2 83.5 10.6 0.1 5.8 7.91 86 100 1.03 14.6 0.0 1.34
#12 1.078 2.422 44.5 83.7 11.1 0.1 5.1 7.52 82 100 1.16 19.2 0.0 1.33
#13 1.040 2.506 41.5 83.5 11.9 0.0 4.6 7.03 76 100 1.32 24.2 0.0 1.33
FactSage-Based Design Calculations for the Production …
#14 1.223 2.447 50.0 81.6 10.1 1.9 6.4 8.11 90 100 1.00 10.8 0.0 1.13
#15 1.156 2.197 52.6 83.4 9.6 0.1 7.0 8.71 96 100 0.72 6.1 67.8 1.56
#16 1.088 2.189 49.7 82.7 10.1 0.1 7.0 8.17 90 100 0.94 11.4 1.3 1.33
#17 0.982 2.065 47.5 82.5 10.6 0.0 6.9 7.79 86 100 0.98 17.5 4.1 1.29
#18 1.060 2.058 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#19 0.946 1.837 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#20 0.892 1.730 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#21 0.866 1.681 51.5 82.7 9.8 0.6 7.0 8.46 93 100 0.86 6.9 0.0 1.38
#22 1.196 2.382 50.2 82.9 10.0 0.4 6.7 8.27 91 100 0.91 9.2 0.0 1.36
#23 1.204 2.475 48.6 83.3 10.3 0.3 6.1 8.05 89 100 0.97 11.8 0.0 1.34
#24 1.211 2.582 46.9 83.5 10.7 0.2 5.6 7.78 86 100 1.05 14.6 0.0 1.34
#25 1.218 2.706 45.0 83.6 11.2 0.1 5.1 7.48 83 100 1.14 17.7 0.0 1.33
765
766 J. D. Steenkamp
Calculated Mn and Fe Recovery
From the results of the calculations in FactSage 7.2, the amount of alloy produced
as well as the composition and Mn/Fe ratio of the alloy was derived. The recoveries
of Mn and Fe at equilibrium conditions were calculated as follows:
1. The molar compositions of each of the phases formed were extracted from the
dataset.
2. From the set of results, the number of moles of Fe and number of moles of Mn
per phase was derived, totalized, and the recovery of the Fe and Mn to the alloy
phase was calculated.
3. Calculated in this manner, the mass and molar recovery will be the same.
Flux Requirement
The other product phases that formed for both Case #1 and Case #2 were 40.9% gas,
1.7% liquid slag, and two types of solid phases: 12.5% monoxide and 12.5% (Ca,
Mg, Mn)2 SiO4 . Of the monoxide phase formed, 1.0% was associated with the gas
phase formation, the remainder of the oxide phases would be considered as ’slag’
phase. The ‘slag’/alloy mass ratio is calculated at 0.9, which is similar to the 0.8
typically associated with South African operations [18] or pilot-scale testwork [13].
The solids content of the ‘slag’ phase is very high at 93.5% by mass, which means
that the ‘slag’ will not be able to tap from the furnace and ‘slag’/alloy separation will
be difficult amongst other problems.
At South African operations, quartz is used as a flux and is also considered here.
The calculations in FactSage 7.2, were based on Case #1, to which 0–20 g quartz was
added at 2 g intervals, with equilibrium calculated at 1500 ◦ C. The quartz requirement
is estimated as the point where no solids (excluding graphite) are formed as reac-
tion product and was found to be 12.86 g quartz per 100 g ore blend. The reductant
requirement will also be less as indicated by the formation of graphite. To account for
the effect of flux addition, the results obtained for Case #1 were subsequently revised
as Case #3 and Case #2 as Case #4, taking the reduction in reductant requirement
into account.
Revising Raw Material Phase Composition
Comparing the results obtained for Cases #1 to #4 in terms of energy required, the
results were significantly higher than those published in literature (see Table 2). The
results reported in literature varied between 1.8 and 3.2 MWh/ton of alloy whilst the
energy required for Cases #1 to #4 ranged between 2.9 and 3.6 MWh/ton of alloy.
It was therefore decided to disregard the energy required for the decompositioning
of calcite (CaCO3 ) and dolomite (CaMg(CO3 )2 ). Dolomite still contained all MgO
but it now consisted of CaO and MgO in a molar ratio of 1:1. Calcite accounted for
the remainder of the CaO and consisted of CaO only. The calculations for Cases #1
to #4 were subsquently revised as Cases #5 to #8.
Sensitivity Analysis
A sensitivity analysis was conducted to study the effects of the changes listed below
on the energy requirement, product amount and quality, manganese recovery, and
amount of slag. Case #7 formed the base case for the analysis. The following changes
were considered:
1. Reducing the amount of coke by 2.5, 5, 7.5, 10, 15, and 20% to account for
the effect of reaction kinetics (Cases #9 to #13). As FactSage calculates the
equilibrium conditions only, and it is known that the manganese reduction in
HCFeMn production is not at equilibrium, the amount of coke fed to the process
was reduced. According to the training material provided with the software, this
is typically done when using FactSage for mass and energy balance calculations
when processes are not at equilibrium.
2. Increasing and decreasing the amount of flux by 50% to study effect of flux
additions on solids in slag (Cases #14 and #15).
3. Reducing the output temperatures of all products by 50 and 100 ◦ C (Cases #16
and #17), and the temperature of the offgas only at intervals of 100 ◦ C up to 400 ◦ C
(Cases #18 to #21) to study effect of output temperatures.
4. Introducing moisture at intervals of 1 g up to 8 g to study the effect of moisture
associated with wet ore (Cases #22 to #25).
The effect of the reduction on manganese recovery and energy required were
presented in Fig. 2a. The conditions typical of operating conditions (80% recovery)
will therefore probably be met at between 15 and 20% reduction in coke, which is
within the range of excess carbon added typically for coke-bed management. For mass
and energy balance calculation purposes, the stoichiometric reductant requirement
was selected to be 15% less than the base case, i.e., 19.601 g/100 g ore instead of
23.06 g/100 g ore. The associated increase in process energy requirement would be
between 5.1 and 8.7%. The increase in process energy requirement, when expressed
as MWh/ton alloy, was not due to an actual increase in energy but due to a decrease
in alloy produced though as can be seen in Fig. 2b. The actual reduction in process
energy requirement was also evident when expressed as MWh/ton ore.
The process energy requirement for the base case was calculated for ore and quartz
on a dry basis. In reality, the ore fed into the SAF would probably contain some
moisture. The effect of ore containing moisture on the process energy requirement
was therefore calculated. Addition of moisture significantly influenced the process
energy requirement as well as the manganese recovery (Fig. 3a), with 4% moisture
resulting in a 17.4% increase in process energy requirement and 11.7% decrease in
768 J. D. Steenkamp
Fig. 2 Effect of reduction in coke on a energy requirement and manganese recovery and b energy
requirement and alloy produced, where the baseline was 23.06 g coke/100 g ore (Case #7)
Fig. 3 Effect of moisture addition on a energy requirement and manganese recovery and b energy
requirement and alloy produced, where the baseline was 0% moisture/100 g ore, i.e., at increments
of 1 g moisture/100 g ore (Case #7)
manganese recovery. The increase in process energy requirement was partially due
to an actual increase in process energy required as well as a reduction in the amount
of alloy produced, as indicated in Fig. 3b.
The assumptions made about the product temperatures have a significant influence
on the calculated process energy requirement. The effects of the reduction in product
temperature and reduction in offgas temperature on the process energy requirement
and manganese recovery are presented in Fig. 4. As expected, the reduction in tem-
Fig. 4 Effect of reduction in temperature of a slag, alloy, and offgas, and b offgas only on energy
requirement and manganese recovery where the baseline was 1500 ◦ C for slag, 1400 ◦ C for alloy,
and 800 ◦ C for offgas (Case #7)
perature of all products will have a significant influence on both the process energy
requirement as well as the manganese recovery, at reduction of 10.4% and 8.0%,
respectively, for a reduction of 100 ◦ C (Fig. 4a). Simultaneously, the solids content
of the slag increases to 4.1%. The reduction in offgas temperature will have a signif-
icant influence on the process energy requirement (27% for a reduction of 400 ◦ C)
but none on the manganese recovery (Fig. 4b).
Conclusion
Based on the work presented here, the answers to the questions raised in the intro-
duction are summarised. The answers form the basis of the process flowsheet and
equipment design during the basic engineering study:
1. The target alloy composition will be 78% Mn, 12% Fe, 7.5 % C, 1.2% Si, and a
Mn/Fe ratio of 6.5.
2. Four types of raw materials will be utilised, two manganese ores, one reductant,
and one flux. The manganese ores will be Ore #A and Ore #B. Ore #A ore will
consist of 37.78% Mn. 4.94% Fe, 0.13% Al2 O3 , 13.21% CaO, 3.30% MgO, and
5.6% SiO2 . Ore #B will consist of 34.29% Mn. 3.86% Fe, 0.09% Al2 O3 , 15.33%
CaO, 4.21% MgO, and 4.72% SiO2 . The flux will be quartz and will consist of
1.2% Al2 O3 and 98.8% SiO2 . The reductant will be coke and will consist of 2.62%
volatile matter, 10.03% ash, and 87.33% fixed carbon—all determined on a dry
770 J. D. Steenkamp
basis—and 3.96% moisture. The ash will consist of 17.01% Al2 O3 , 20.52% CaO,
33.04% Fe2 O3 , 2.25% MgO, and 27.17% SiO2 .
3. The two ores will be fed at a ratio of 61.38 to 38.62, Ore #A to Ore #B.
4. The reductant requirement will be 19.601 g/100 g ore.
5. The flux requirement will be 23.06 g/100 g ore.
6. The process energy requirement under equilibrium conditions will be 1.187
MWh/ton ore or 2.304 MWh/ton alloy for cold feed, and 1.062 MWh/ton ore
or 2.061 MWh/ton alloy for hot feed.
During the pilot-scale campaign, the values obtained for the predictive mass and
energy balance will be confirmed through accounting mass and energy balances.
Acknowledgements The PreMa project is funded by the European Union’s Horizon 2020 Research
and Innovation Programme under Grant Agreement No 820561 and industry partners: Transalloys,
Eramet, Ferroglobe, OFZ, and Outotec.
References
1. ASTM-A99 (2009) Standard specification for ferromanganese. West Conshohocken, PA, 2003.
ASTM International
2. Ahmed A, Halfa H, El-Fawakhry M, El-Faramawy H, Eissa M (2014) Parameters affecting
energy consumption for producing high carbon ferromanganese in a closed submerged arc
furnace. Int J Iron Steel Res 21(7):666–672
3. Olsen S, Tangstad M, Lindstad T (2007) Production of manganese ferroalloys. Tapir Academic
4. Swamy K, Robertson D, Calvert P, Kozak D (2001) Factors affecting carbon consumption in
the production of high carbon ferromanganese, Quebec City, Canada, pp 293–301
5. Healy G (1990) Ferromanganese material and energy balances calculation of electrical resis-
tance mix. In: Proceedings of the international symposium on ferrous and non-ferrous alloy
processes, Hamilton, Canada, pp 85–96
6. Corathers L (2017) Mineral commodity summaries 2017. Technical report, U.S. Geological
Survey
7. Van Averbeke N (2005) SAMI—South Africa’s minerals industry 2004–2005. Technical report,
Directorate, Mineral Economics
8. Cairncross B, Beukes N, Gutzmer J (1997) The manganese adventure—The South African
manganese fields. Associated Ore & Metal Corporation
9. Chetty D, Gutzmer J (2018) Quantitative mineralogy to address energy consumption in smelting
of ores from the Kalahari Manganese Field, South Africa. In:INFACON XV, Cape Town, South
Africa
10. Steenkamp J, Maphutha P, Makwarela O, Banda W, Thobadi I, Sitefane M, Gous J, Sutherland
J (2018) Silicomanganese production at transalloys in the twenty-tens. J South Afr Inst Min
Metall 118:309–320
11. Tangstad M, Olsen S (1995) The ferromanganese process-material and energy balance, Trond-
heim, Norway, pp 621–630
12. Tangstad M, Ichihara K, Ringdalen E (2015) Pretreatment unit in ferromanganese production.
In: Energy efficiency and environmental friendliness are the future of the global Ferroalloy
industry, Kiev, Ukraine, pp 99–106
13. Lagendijk H, Xakalashe B, Ligege T, Ntikang P, Bisaka K (2010) Comparing manganese fer-
roalloy smelting in pilot-scale AC and DC submerged-arc furnaces. In: Infacon XII: sustainable
future, Helsinki, Finland, pp 497–508
14. Eissa M, Ghali S, Ahmed A, El-Faramawy H (2011) Optimum condition for smelting high
carbon ferromanganese. Ironmak Steelmak
15. Kalenga M, Xiaowei P, Tangstad M (2013) Manganese alloys production: impact of chemical
compositions of raw materials on the energy and materials balance. In: Efficient technologies
in ferroalloy industry, Almaty, Kazakhstan, pp 647–654
16. Bale C, Belisle E, Chartrand P, Decterov S (2016) FactSage thermochemical software and
database, 2010–2016. Elsevier 54:35–53
17. Tang K, Olsen S (2006) Computer simulation of equilibrium relations in manganese ferroalloy
production. Metall Mater Trans B 37:599–606
18. Steenkamp J, Hockaday C, Gous J, Nzima T (2017) Dissipation of electrical energy in
submerged arc furnaces producing silicomanganese and high-carbon ferromanganese. JOM
69(9):1712–1716
Characterization and Formation
Mechanism of Oxide Inclusions
in Low-Aluminum Non-oriented
Electrical Steels
Zhiyuan Hu, Qiang Ren, Yan Luo and Lifeng Zhang
Abstract It is recently found that oxide inclusions played a significant effect on

the microstructure and magnetic properties in low-aluminum non-oriented electrical
steels. In the current study, inclusions with different characteristics were generated
through different production process. Inclusions were characterized using an auto-
matic scanning electron microscope and thermodynamic analysis was conducted
using FactSageTM . It is observed that the deformation behavior of SiO2 –Al2 O3 –
MnO inclusions was closely related to their composition. Inclusions forming during
the solidification process showed a smaller size and a higher fraction of SiO2 , which
was hardly deformed after rolling and had little pinning effect on the grain growth. On
the contrast, large inclusions had a lower fraction of SiO2 and were easily deformed
after rolling process. From the view of improving the magnetic properties of non-
oriented electrical steels, inclusions should be controlled to be undeformed and larger
composite SiO2 –Al2 O3 –MnO inclusions should be removed.
Keywords Non-oriented electrical steels · Low-aluminum content · Oxide

inclusions
Introduction
Non-oriented electrical steels are widely used as core materials in motors and genera-
tors. In order to save energy and improve efficiency, low core loss and high magnetic
induction are the most significant requirements [1, 2]. Silicon-killed non-oriented
electrical steels have a cost advantage and get rid of the deterioration of aluminum
nitride. However, due to the low affinity of silicon and oxygen, oxide inclusions play
a significant role in the magnetic properties in silicon-killed non-oriented electrical
steels. In order to lower the core loss of steels, the grain size of final annealed sheets
is expected to grow due to the deterioration effect of grain boundaries on hysteresis
Z. Hu · Q. Ren · Y. Luo · L. Zhang (B)

Beijing (USTB), Beijing 100083, China
e-mail: zhanglifeng@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_68
774 Z. Hu et al.
loss [3–5]. Kurosaki et al. [6] studied the effect of oxide shape on the magnetic prop-
erties and found that inclusions with less MnO and much SiO2 did not inhibit the
grain growth and the average grain size became large. In our previous study [7], it
has been concluded that inclusions with higher CaO are much easier to be elongated
during the hot-rolling process and are more detrimental to the magnetic properties.
Therefore, controlling the chemical composition of oxide inclusions in silicon-killed
non-oriented electrical steels are of great significance on improving their magnetic
properties. The objective of the current study is to analyze the inclusion characteristic
in three samples produced by different alloying processes.
Experimental Method
The production route of the non-oriented electrical steel is BOF → RH refining

→ continuous casting → hot-rolling → cold-rolling → recrystallization anneal-
ing. Decarburization, deoxidization, and alloying process were conducted in the RH
refining process. Three experimental heats were conducted by adjusting the alloy-
ing process. Samples were taken on the final annealing sheets. Inclusions on the side
section of the final annealing sheets were observed by an automatic scanning electron
microscope. The composition, size, and morphology of inclusions were analyzed.
Composition and Morphology of Inclusions
Figure 1 shows the composition distribution of inclusions in Al2 O3 –SiO2 –MnO

ternary diagrams. For all of the three samples, oxide inclusions were mainly com-
posed of SiO2 , Al2 O3, and MnO, but the mass fraction varied much, especially for the
content of Al2 O3 . The frequency distribution of Al2 O3 content in inclusions is shown
in Fig. 2. Inclusions in Heat 1 showed the highest content of Al2 O3 , while inclusions
in Heat 3 showed the lowest content of Al2 O3 . Besides, the distribution of Al2 O3
in inclusions in Heat 1 and 3 conformed to the normal distribution. However, the
Al2 O3 frequency distribution in inclusions in Heat 2 showed two peaks, indicating
that there were two types of inclusions in Heat 2.
The morphology and composition of typical inclusions in the three heats are
shown in Fig. 3. Inclusions were divided into two types including angular shape and
spherical shape according to their morphologies. Most of the inclusions in Heat 1
showed angular shape, as shown in Fig. 3a. Inclusions in Heat 3 were all of spherical
shape, as shown in Fig. 3d. These two types of inclusions were observed in the steel
of Heat 2, as shown in Fig. 3b, c. Spherical inclusions with higher fraction of SiO2
were formed during the solidification process due to the reaction of the dissolved
oxygen and silicon [7]. It is demonstrated in our previous study that oxide inclusions
Characterization and Formation Mechanism of Oxide Inclusions … 775
(a) (b)
0 100 0 100
3 µm 3 µm
Avg. comp. Avg. comp.
25 75 25 75
50 50
O
O
50 50
SiO
SiO
Mn
Mn
2
2
75 25 75 25
100 0 100 0
0 25 50 75 100 0 25 50 75 100
Al2O3 (wt. %) Al2O3 (wt. %)
(c)
0 100
3 µm
Avg. comp.
25 75
50
O
50
SiO
Mn
75 25
100 0
0 25 50 75 100
Al2O3 (wt. %)
Fig. 1 Composition distribution of inclusions in Al2 O3 –SiO2 –MnO ternary diagrams. a Heat 1,
b Heat 2, c Heat 3
Fig. 2 Frequency 18
distribution of Al2 O3 in Heat 1
16 Heat 2
inclusions
Relative frequency (%)
Heat 3
14
12
10
8
6
4
2
0
0 10 20 30 40 50
Content of Al 2 O3 (%)
776 Z. Hu et al.
(a)
(b)
(c)
(d)
Fig. 3 Morphology and composition of typical inclusions. a Angular inclusions in Heat 1,

b spherical inclusions in Heat 2, c angular inclusions in Heat 2, d spherical inclusions in Heat
3
were mainly deformed during the hot-rolling process [7]. It is shown that several
angular-shaped inclusions tended to distribute along the rolling direction, which can
be attributed to that they were from one oxide inclusion and were deformed and
fractured during the rolling process.
Characterization and Formation Mechanism of Oxide Inclusions … 777
Fig. 4 Frequency 40
distribution of the viscosity Heat 1 Viscosity of steel
Heat 2
of inclusions Heat 3
Relative frequency (%)

30
20
10
0
0 3 6 9 12 15
log(Viscosity (Pa s))
Viscosity of Inclusions
The viscosity of inclusions was calculated using FactSageTM according to the compo-
sition of inclusions. The temperature was assumed to be 1000 °C, which was regarded
as the temperature during the hot-rolling process. The frequency distribution of the
inclusion viscosity is shown in Fig. 4. The apparent viscosity of the steel matrix at
1000 °C was 1.2 × 107 Pa s [6], and was labeled in Fig. 4. It is shown that a large
amount of inclusions in Heat 1 showed a lower viscosity than the steel matrix, which
was the reason that most of the inclusions in Heat 1 were deformed and fractured.
Most of the inclusions in Heat 3 showed a higher viscosity than the steel matrix,
causing them undeformed after rolling. For Heat 2, the two types of inclusions each
account for half. Inclusions with higher larger viscosity than steel matrix was hard to
be deformed during the hot-rolling process, whereas inclusions with lower viscosity
than the steel matrix tended to be elongated along the rolling direction [7]. From
the view of controlling inclusions undeformed, inclusions in Heat 3 were better than
those in Heat 1 and 2.
778 Z. Hu et al.
Conclusions
The composition and morphology of inclusions in three samples with different alloy-
ing process were analyzed by an automatic scanning electron microscope. The main
conclusions were summarized as follows:
(1) Two types of inclusions were observed in the final annealed sheets. One was of
spherical shape with a lower content of Al2 O3 , the other was of angular shape
with a higher content of Al2 O3 .
(2) Inclusions with spherical shape were formed during the solidification process
and were hardly deformed during the rolling process, while inclusions with
angular shape were formed in the molten steel and were easily deformed and
fractured during the rolling process due to the low viscosity of inclusions.
Acknowledgements The authors are grateful for support from the National Science Foundation
China (Grant No. U1860206 and No. 51725402, Beijing International Center of Advanced and
Intelligent Manufacturing of High Quality Steel Materials (ICSM), Beijing Key Laboratory of Green
Recycling and Extraction of Metals (GREM) and the High Quality Steel Consortium (HQSC) at
the School of Metallurgical and Ecological Engineering at University of Science and Technology
Beijing (USTB), China.
References
1. Shimanaka H, Ito Y, Matsumara K, Fukuda B (1982) Recent development of non-oriented

electrical steel sheets. J Magn Magn Mater 26(1):57–64
2. Matsumura K, Fukuda B (1984) Recent developments of non-oriented electrical steel sheets.
IEEE Trans Magn 20(5):1533–1538
3. Stephenson ET, Marder AR (1986) The effects of grain size on the core loss and permeability
of motor lamination steel. IEEE Trans Magn MAG-22(2):101–106
4. Shiozaki M, Kurosaki Y (1989) The effects of grain size on the magnetic properties of
nonoriented electrical steel sheets. J Mater Eng 11(1):37–43
5. PremKumar R, Samajdar I, Viswanathan NN, Singal V, Seshadri V (2003) Relative effect(s) of
texture and grain size on magnetic properties in a low silicon non-grain oriented electrical steel.
J Magn Magn Mater 264(1):75–85
6. Kurosaki Y, Shiozaki M, Higashine K, Sumimoto M (1999) Effect of oxide shape on magnetic
properties of semiprocessed nonoriented electrical steel sheets. ISIJ Int 39(6):607–613
7. Ren Q, Zhang L, Yang W (2018) Effect of oxide inclusions on the magnetic properties of
non-oriented electrical steel. Steel Res Int 89(12):1800047
Effect of CO2 Mix Ratios on Materials
and Heat Balances of Bottom-Blowing
O2 –CaO Converter
Weifeng Li, Rong Zhu, Kai Dong, Shaoyan Hu, Guangsheng Wei
and Chao Feng
Abstract Bottom-blowing O2 –CaO converters have been used in steelmaking plants

for a long time owing to their superior metallurgical performance. Furnace life has
been known to restrict their wide application; however, this can be overcome by
mixing CO2 with a bottom-blowing gas to reduce the temperature of the fire spot
zone above the tuyere, thus prolonging the furnace life. In our study, a materials
and heat balance model was established, and the effect of bottom-blowing O2 –CaO
mixed with CO2 was studied. Results showed that with increased CO2 in the gas mix,
surplus heat decreased, and the amount of ore required was reduced. The optimal
mixing ratio for bottom-blown CO2 was 55.6%, at which point the fire spot zone
temperature decreased by 795 °C and the ferrous charge consumption requirement
decreased by 10.1 kg/t.
Keywords Bottom-blown O2 –CaO converter · CO2 mixing ratio · Fire spot zone
temperature
Introduction
Steelmaking is a high-temperature metallurgical process in which qualified molten

steel is produced from molten iron and scrap. Steadying the smelting rhythm, improv-
ing steel quality, and reducing production costs are universal steelmaking technology
development directions. The common converter steelmaking process is dominated by
the method involving top-blown oxygen assisted by bottom-blown nitrogen/argon;
W. Li · R. Zhu (B) · K. Dong · G. Wei · C. Feng

School of Metallurgical and Ecological Engineering, University of Science and Technology,
Beijing 100083, China
e-mail: zhurong12_01@126.com
S. Hu (B)
Shagang School of Iron and Steel, Soochow University, Suzhou, China
e-mail: hushaoyanvip@126.com

https://doi.org/10.1007/978-3-030-36540-0_69
780 W. Li et al.
this common method has several issues associated with it; however, including high
levels of iron and steel materials consumption, low oxygen utilization, high levels of
smoke and dust emissions, and poor levels of cleanliness [1–3]. These issues have
proven to be difficult to overcome, and affect the efficiency of high-quality steel
making.
With oxygen as the carrier gas, the powder is blown into the melting pool from
the bottom of the furnace, in a process that greatly enlarges the contact area between
the powder and the liquid metal, and increases the local concentration of the powder.
At the same time, due to the stirring effect of the gas, the mass transfer process is
accelerated, which helps optimize the kinetic conditions of the reaction in the molten
pool, and increases reaction speed.
In the bottom-blown O2 –CaO converter steelmaking process, part of the oxygen is
blown directly into the molten pool from the bottom of the converter. This technique
has many advantages, such as low the ferrous charge consumption, less dust emis-
sion and less contamination (high levels of cleanliness) of the molten steel [4–6].
Metallurgists [7] have developed the bottom-blown O2 –CaO converter steelmaking
process, and have pointed out that it has remarkable advantages, including improved
steelmaking stability, high oxygen utilization rates, lower slag discharge, and clear
metallurgical benefits. Bottom-blowing, O2 –CaO converter steelmaking technology
is regarded by industry experts as an important opportunity for China’s steelmaking
sector to become more efficient and environmentally friendly in the future.
However, in the process of bottom-blown O2 –CaO converter steelmaking, oxygen
is blown into the molten pool from the bottom, to form a high-temperature fire spot
zone above the tuyere. The temperature at the tuyere and the surrounding magnesia-
carbon bricks reaches as high as 2500 °C [8], which causes high-speed melting loss,
and reduces the life of the converter.
In the steelmaking industry, metallurgists [9] currently apply CO2 in the converter.
Because CO2 has weak oxidation at high temperature, it can participate in chemical
reactions in the high-temperature molten pool. CO2 reacts endothermically with [C],
and [Fe] molten pool, and exothermically with [Si], and [Mn], but the heat gener-
ated by these reactions is much less than that generated by reaction with oxygen. In
addition, the reaction of CO2 with elements in the molten pool can produce CO gas,
which can enhance the molten pool stirring effect, thereby improving the metallur-
gical reaction dynamic conditions. Therefore, mixing part CO2 into the carrier gas
used for bottom powder injection is helpful in reducing fire spot zone temperature,
therefore prolonging the life of the furnace bottom.
The heating rate of the molten pool decreases due to the incorporation of CO2
in the bottom-blowing carrier gas, which changes the amount of ore added in the
smelting process and ultimately affects the tapping capacity. In order to understand
the effect of bottom-blown CO2 on materials and heat balances in the bottom-blown
O2 –CaO converter steelmaking process, a materials and heat balance calculation
model has been established, based on a 120-ton, bottom-blown O2 –CaO steel plant
converter. The effect of varied CO2 ratios on the bottom-blown O2 –CaO converter
steelmaking process has been analyzed, and the results can be used as a reference
for steelmaking in a 120-ton, bottom-blown O2 –CO2 –CaO converter.
Effect of CO2 Mix Ratios on Materials and Heat Balances … 781
Calculation Model
A 120-ton, bottom-blown inert gas combined with a top-blown oxygen converter was
transformed into a bottom-blown O2 –CaO combined blown converter in a steel plant.
The bottom-blown lance took the form of an annular slot sleeve, with the central pipe
injecting O2 –CaO, and the annular slot injecting natural gas, supplemented with top-
blown, high-speed oxygen flow. Based on the actual working conditions applicable
in bottom-blown O2 –CaO converter steelmaking, the carrier gas in the central tube of
the bottom-blown lance was blown with CO2 , and the resultant changes in material
use and heat production were calculated.
Raw and Accessory Material Conditions
Balance calculations were carried out based on the conditions of the metal material
entering the furnace, with a scrap ratio of 15%, i.e. 19.5 t scrap and 110.5 t hot metal.
When the smelting target is low-carbon steel, the end carbon content is controlled to
concentrations between 0.03 and 0.05%, so the end carbon content selected for the
model was 0.04%. Table 1 lists the various compositions and temperatures of hot
metal and scrap steel, and the amounts of elemental oxidation, and Table 2 shows
Table 1 Composition and temperature of metal materials

Raw material C/% Si/% Mn/% P/% S/% Temperature/°C
Hot metal 4.53 0.50 0.76 0.104 0.045 1316
Scrap 0.10 0.15 0.25 0.017 0.013 25
Average quantity 3.87 0.55 0.51 0.083 0.014 –
Target 0.04 0 0.17 0.008 0.026 –
Oxidizing capacity 3.83 0.45 0.51 0.083 0.014 –
Table 2 Composition of slag-making materials/%

Project CaO/% SiO2 /% MgO/% Al2 O3 /% CaS/% Fe2 O3 /% MnO/% Burn
down/%
Lime 91.41 1.21 4.34 0 0.11 1.87
powder
Ore 0.90 3.50 0.30 1.00 0.22 91.00 1.50
Dolomite 49.00 2.00 37.00 9.00
Lining 2.00 0.90 77.00 4.00
782 W. Li et al.
the types and compositions of slag-making materials added during the steelmaking
process.
Assumptions
In order to establish a more practical equilibrium model, combined with the produc-
tion data from 300 bottom-blowing O2 –CaO converters, the following assumptions
were made in relation to the conditions applicable to bottom-blowing mixed with
CO2 .
(1) The single slag method was adopted for smelting, based on the silicon content
in the hot metal.
(2) The bottom-blown gas volume in the bottom-blowing gun was 30% of the total
oxygen consumption, and the gas in the central pipe included O2 and CO2 . For
calculation purposes, the CO2 volume proportion in the central pipe of the
bottom-blowing gun was 10%.
(3) CH4 injected into the annular slot tube of the bottom-blowing gun made up
10% of the total gas volume in the central tube. It was assumed that the CH4
was completely cracked into CO and H2 O.
(4) Oxygen purity was 99.60%. All the CO2 injected at the bottom participated in
the metallurgical reaction at high temperature.
(5) 75% of the total carbon in the metal materials was oxidized to CO, and 25%
to CO2 .
(6) The average furnace gas temperature was 1450 °C, and the free oxygen content
was 0.50%.
(7) The proportion of smoke and dust was 1.15%, consisting of 20% WFe2 O3 and
70% WFeO .
(8) Splash losses accounted for 0.5% of the metal content—and it was assumed
that the splashing temperature was 1580 °C.
(9) The basicity of the slag was 2.8, and the amount of metal iron beads in the slag
accounted for 5.00% of the total slag amount. WFeO and WFe2 O3 proportions
in the slag were 9.0% and 10.1%, respectively.
(10) The amount of refractories entering the slag was 0.08% of the metal content.
(11) The amount of dolomite added was 1.7% of the total amount of metal. The
tapping temperature was 1650 °C, and the final slag temperature was 20 °C
lower than the tapping temperature.
(12) The remaining manganese constituted 25% of the total manganese, the dephos-
phorization rate was 91%, and the desulfurization rate was 35%—of which the
oxidation desulfurization rate was 1/3.
Material and Heat Balance Model
In the process of bottom-blowing O2 –CaO converter steelmaking, CO2 is mixed with

the bottom-blowing gas, and materials changes are divided into materials income and
expenditure. Materials income includes hot metal, scrap, lime powder, lightly burned
dolomite, furnace lining, oxygen, carbon dioxide, and natural gas, while materials
expenditure includes molten steel, slag, furnace gas, smoke and dust, metal beads,
and spraying materials.
Based on the above analysis, the final materials and heat balances for bottom-
blown O2 –CaO, when mixed with different CO2 ratios, are shown in Tables 3 and 4,
respectively.
Heat change includes heat income and expenditure. Heat income includes the
physical heat of molten iron, the oxidation and slagging heats of metal elements,
and dust oxidation heat. Heat expenditure includes the physical heat of molten steel,
slag, furnace gas, smoke and dust, metal beads in the slag, and splashing metal, plus
the decomposition heat of lightly burned dolomite, pyrolysis heat of natural gas, heat
carried away by the cooling water, and heat dissipation from the furnace itself.
In the process of blowing, the amount of heat income over and above heat expendi-
ture is the surplus heat, which is offset by adding ore to control the heating process of
the molten pool. The final material balance and heat balance are corrected according
to the materials and heat changes caused by the addition of ore.
Table 3 Final material balance

Income Expenditure
Project Weight/kg Ratio% Project Weight/kg Ratio%
Hot metal 110.50 73.35 Molten steel 122.74 81.80
Scrap 19.50 12.94 Slag 9.81 6.45
Oral 4.10 2.72 Furnace gas 15.38 9.99
Lime 3.42 2.27 Dust 1.51 1.01
Dolomite 1.95 1.29 Iron beads in slag 0.48 0.32
Lining 0.09 0.06 Splash 0.65 0.43
Oxygen 10.39 6.90
Natural gas 0.24 0.16
Carbon dioxide 0.45 0.30
Total 150.65 100.00 Total 150.57 100.00
784 W. Li et al.
Table 4 Final heat balance

Heat income Heat expenditure
Project Heat/103 kJ Ratio% Project Heat/103 kJ Ratio%
Physical heat of 132,940 51.82 Physical heat of 174,942 68.19
molten iron molten steel
Slagging and 118,767 46.29 Slag 21,390 8.34
oxidation heat of
elements
Oxidation heat of 4852 1.89 Furnace gas 24,370 9.50
dust
Dust 2455 0.96
Iron beads in slag 682 0.27
Splash 900 0.35
Lime 1069 0.42
Natural gas 6171 2.41
pyrolysis
Ore decomposition 16,884 6.58
Other heat losses 7697 3.00
Total 256,559 100.00 Total 256,559 100.00
Using a materials and heat balance model for the bottom-blown O2 –CaO converter
steelmaking process, the influence of the ratio of CO2 mixed into the bottom-blown
gas on the materials and heat balance was analyzed, by changing the CO2 gas ratio.
Thermal Analysis
The silicon content in the molten iron was 0.50%, and the scrap ratio was 15%.
When CO2 was mixed into the gas feed of the bottom-blowing gun central tube, the
effects of the increased CO2 ratio in the molten pool heat income and expenditure
were recorded and are shown in Fig. 1.
From the figure, it can be seen that the molten pool heat income decreased with
the increased CO2 proportion in the mixed bottom-blowing gas in the steelmaking
process of bottom-blown O2 –CaO, but the heat expenditure increased, and the molten
pool surplus heat decreased continuously. For every 10% increase in the CO2 ratio,
the molten pool surplus heat decreased by 3223 × 103 kJ. When the ratio of bottom-
blowing CO2 was 74%, the heat income became equal to the heat expenditure, and
no surplus heat was available in the molten pool.
Considering the weak oxidation property of CO2 at a high temperature, the reac-
tion between CO2 and elements in the molten pool is endothermic with only a slight

between heat with the ratio
of bottom-blowing CO2
exothermic element. Therefore, compared with pure oxygen bottom-blowing, when

the proportion of CO2 mixed in the bottom-blowing stream increases, the heat gen-
erated by the bottom-blowing oxidizing gas participating in the reaction becomes
less and less.
With the increased CO2 bottom-blowing gas proportion, the amount of dust and
slag increased, the heat carried away by metals in the furnace gas and slag also
increased, so that the heat expenditure of the molten pool increased with increased
bottom-blowing CO2 .
In summary, the difference between heat income and expenditure gradually
decreased—that is, the surplus heat decreased with increased bottom-blowing CO2 .
Although the higher the proportion of bottom-blown CO2 , the longer the life of the
bottom-blown furnace will be, when the proportion of bottom-blown CO2 became
> 74%, the heat expenditure was > the heat income. This meant that the end-point
temperature could not reach the tapping steel target temperature, indicating that the
maximum possible proportion of bottom-blown CO2 in the blowing gas proportion
was estimated at 74%.
In the bottom-blown O2 –CaO converter steelmaking process, oxygen is directly
blown into the molten pool from the bottom of the furnace. As the oxygen jet flows
into a certain depth of the molten pool, it reacts with elements of the molten pool to
form a high-temperature fire zone. At this time, the surplus heat of the molten pool
is Q1 . When the bottom-blown gas includes CO2 , the surplus heat of the molten pool
is reduced, the surplus heat is Q2 , and the surplus heat is reduced by Q = Q1 − Q2 .
Since almost all the CO2 participates in the oxidation reaction in the fire spot zone,
after blowing into the molten pool, Q is the reduced heat in the fire spot zone caused
by the reaction between CO2 with elements.
Yun [10] used a 100 KW, medium-frequency induction furnace to measure the
temperature distribution around a bottom-blown oxygen tuyere. It was found that
when the radial distance from the bottom-blown oxygen tuyere exceeded 18Dgun ,
the refractory temperature was no longer sensitive to changes in the bottom-blown
786 W. Li et al.
medium. This research showed that the radial range of the bottom-blowing medium
and the reaction zone was limited, so it was assumed for our modeling that the fire
spot zone was a cylindrical zone with a radius of 504 mm and a height 0.5 times that
of the molten pool.
Q = Cmt (1)
where t is temperature reduction in the fire spot zone, in °C.
T = 2500 − t (2)
where T is the temperature in the fire spot zone, as °C.

According to our calculations, when pure oxygen was blown at the bottom, the
ignition zone temperature was 2500 °C.
Figure 2 shows how the temperature in the fire spot zone changed with increased
CO2 in the bottom-blowing gas mix ratio. As shown in this figure, with the increase
of bottom-blowing CO2 ratio, the fire spot zone temperature gradually decreased. For
every 10% CO2 ratio increase, the fire spot zone temperature decreased by 137 °C.
Because CO2 participated in the oxidation reactions instead of O2 , the heat generated
by CO2 participating in metallurgical reactions in the fire spot zone was less than
that generated by pure oxygen. So the higher the proportion of CO2 , the lesser the
volume of bottom-blowing O2 , and the lower the fire spot zone temperature.
This proved that mixing CO2 into the bottom-blowing gas was beneficial in
reducing fire spot zone temperature, thus prolonging furnace life.

between the temperature of
fire spot zone and CO2 ratio

between the amount of ore
added and CO2 ratio
Materials Analysis
The variation curve for ore addition versus CO2 ratio, as calculated using the mate-
rial balance calculation model applied to bottom-blown O2 –CO2 –CaO converter
steelmaking is shown in Fig. 3.
In this figure, it can be seen that with CO2 ratio increase, the amount of ore
added decreased—in fact, for every 10% CO2 ratio increase, the amount of ore
added decreased by 0.64 t. When the CO2 proportion reached 74%, the amount
of ore added was zero, demonstrating that, with the injection of increasing CO2
proportions, the amount of surplus heat gradually decreased—and so the amount of
ore added gradually decreased.
The variation curve for tapping capacity vs the CO2 ratio plot is shown in Fig. 4.
Under the same charging conditions, the tapping capacity for conventional bottom-
blown inert gas, combined with a top-blown oxygen converter, was 121 t. It can
then be seen from the figure that with the increased CO2 ratio, the tapping capac-
ity gradually decreased. Because molten steel mainly comes from iron elements in
molten iron, scrap, and ore, with the increased CO2 proportion, the surplus heat grad-
ually decreased, and the amount of ore added decreased, resulting in the reduction
of molten steel. Eventually, when the CO2 ratio was more than 55.60%, the tapping
capacity was less than that achieved using a conventional converter, so the optimum
bottom-blowing CO2 ratio was determined to be 55.6%.
In order to simplify the calculations, ferrous charges consumption was defined as
(molten iron + scrap + ore addition)/steel, and calculation results showed that the
consumption of ferrous charges decreased as bottom-blowing CO2 ratio increased.
For every 10% increase in the CO2 ratio, consumption of ferrous charges decreased
by 1.8 kg/t. When the proportion of CO2 reached 55.6%, the ferrous charges
consumption decreased by 10.1 kg/t.
788 W. Li et al.

between the tapping capacity
and CO2 ratio
Conclusions
In the bottom-blowing O2 –CaO converter steelmaking process, mixing CO2 into the
bottom-blowing gas can reduce the fire spot zone temperature, and prolong furnace
life. Using a 120-ton bottom-blown O2 –CaO converter in a steel plant as a prototype, a
materials and heat balance model for bottom-blown CO2 mixing has been established,
and the effects of CO2 on materials and heat balances were analyzed. The following
conclusions were drawn:
(1) Molten pool surplus heat continuously decreased as the CO2 ratio increased.
For each 10% CO2 ratio increase, surplus heat was reduced by 3223 × 103 kJ,
up to the point where it was determined that the maximum mixing ratio for
bottom-blowing CO2 was 74%.
(2) For every 10% CO2 ratio increase, the amount of ore added decreased by 0.64 t,
and the tapping capacity decreased by 0.38 t. The optimum proportion of CO2
mixed was determined to be 55.6%, and at this time, consumption of ferrous
charges decreased by 10.1 kg/t.
(3) With the increased CO2 ratio, the fire spot zone temperature decreased. When
the bottom-blowing CO2 ratio was 55.6%, the fire spot zone temperature was
1705 °C, which was 795 °C lower than the temperature reached when using
bottom-blown pure oxygen.
Acknowledgements This work was financially supported by the National Natural Science 240
Foundation of China (Grant No. 51574021 and No. 51474024).
References
1. Aleksashin AL, Schnaltzger I, Hollias G (2007) Creation and growth of oxygen-converter

steelmaking. Metallurgist 51(1–2):60–65
2. Koria SC (1992) Studies of the bath mixing intensity in converter steelmaking processes. Can
Metall Q 31(2):105–112
3. Hirai M, Okohira K, Murakami S et al (1982) Converter steelmaking process
4. Guangting WGTPY (1991) An analysis of stirring energy of bottom blown O2 and CH, in the
combined-blown converter. J Chongqing Univ (Natl Sci Edn)
5. Gou H, Irons GA, Lu WK (1993) Mathematical modeling of postcombustion in a KOBM
converter. Metall Mater Trans B 24(1):179–188
6. Wu W, Zou ZS, Guo ZH et al (2004) Optimum slag forming route for BOF with top and bottom
blowing oxygen. J Iron Steel Res 16(1):21–24
7. Gou H, Irons GA, Lu WK (1992) Mathematical modelling of post combustion in Dofascos
KOBM. EG and G Idaho, Inc., Idaho Falls, ID (United States); McMaster University, Hamilton,
ON (Canada). Department of Materials Science and Engineering
8. Harada N (1983) Measurement of the fire zone temperature under the condition of bottom
blowing oxygen. Tetsu-to-Hagane 69:1010–1011
9. Ming L, Rong Z, Wei X et al (2012) Research on top and bottom mixed blowing CO2 in
converter steelmaking process. Steel Res Int 83(1):11–15
10. Yun L, Qinian S, Shanchang S et al (1990) Measurement and analysis of bottom temperature of
top-bottom oxygen-blowing converter bottom gun and its surrounding. Steelmaking 6(05):41–
45
Numerical Simulation and Optimization
of Temperature Field in the Baking
of RH Vessel
Fei Yuan, Xiao Sun, Peiling Zhou and Shuai Deng
Abstract In order to optimize the baking of RH vessel, numerical simulation of

gas flow, combustion and heat transfer in vacuum vessel during the baking process
was conducted. The FLUENT code with finite volume and SIMPLEC methods was
adopted to investigate the influence of top lance position on the temperature dis-
tribution of RH vessel. The numerical model was verified with the experimental
data. Results show that the different height of RH top lance could cause significant
changes of temperature distribution in the vertical direction. There is an ideal and
uniformity in temperature distribution when the top lance height is 4.5 m, which is
benefited for removing the remaining solid steel in RH vessel. When the height of
top lance is 5 m, the bottom of the vacuum vessel and the immerge tube are in high
baking temperature. The two baking schemes could be used in combination in the
production process to improve the baking effect.
Keywords RH vessel · Baking · Numerical simulation
With the advancement of metallurgical technologies, the main functions of steelmak-

ing steps have seen significant evolution. The functions of the converter gradually
become less significant, while steps including degassing, alloying, inclusion mor-
phology control, and purification of molten steel have transformed from secondary
refining to those of the major functions [1]. An RH refiner is an important refining
equipment for secondary metallurgical processes that are indispensable for high-
quality steel production. The effect of RH refining directly affects the quality of the
F. Yuan (B) · X. Sun · S. Deng

School of Metallurgical and Engineering, University of Science and Technology Beijing, Beijing
100083, China
e-mail: 609339659@163.com
School of Information Engineering, University of Science and Technology Beijing, Beijing
100083, China
P. Zhou
Beijing Research Center of Urban System Engineering, Beijing Academy of Science and
Technology, Beijing 100035, China
e-mail: pellyzhou@163.com

https://doi.org/10.1007/978-3-030-36540-0_70
792 F. Yuan et al.
product in many aspects. The thermal state of the vacuum vessel before the start of
refining plays an important role in affecting the temperature drop of the molten steel
during refining and in affecting the service life of the refractory in the vacuum vessel
[2]. After the vacuum vessel is heated, the uneven temperature field will not only
lead to an increase in the temperature drop of the molten steel during refining but also
cause the splashed molten steel to solidify and form solid drops at lower temperature
spots inside the vacuum vessel, which will result in issues including the reduction
of refractory life. Empirical data on the temperature distribution inside the vacuum
vessel can be obtained by the limited temperature measurement points inside the
vacuum vessel, but the measured values during the actual process cannot fully reflect
the temperature distribution inside the vacuum vessel. Therefore, it is necessary to
carry out a numerical simulation study on the actual combustion of baking with RH
vacuum vessel. At present, the majority of researchers in China have only carried out
numerical simulation studies on the molten steel flow field during refining, without
involving the temperature field of high-temperature combustion during baking with
RH vacuum vessel, thus failing to propose direct optimization measures for on-site
production [3–5].
In this paper, a steelmaking plant’s RH vacuum vessel was taken as the research
object, a three-dimensional mathematical model for gas flow, combustion, and heat
transfer during baking with vacuum vessel was established, the numerical simulation
of the combustion in the RH vacuum vessel during the baking was carried out with
ANSYS Fluent and through the finite volume method; the baking and combustion
under different lance positions were studied to optimize the on-site baking process
system through the temperature distribution of the flame field inside the vacuum
vessel. Therefore, this paper provides a reference for the optimization of parameters
of baking.
Numerical Simulation
Basic Equations
Model of Fluid Flow
The K-epsilon (k−ε) turbulence model is used as the basic model of fluid flow. The
continuity equation and the momentum equation are as follows:
∂ρ
+ ∇ · (ρv) = 0 (1)
∂t
∂
(ρv) + ρ(v · ∇)v = −∇ P + ∇ · μeff ∇v + ∇v T + ρg (2)
∂t
Numerical Simulation and Optimization of Temperature Field … 793
where ρ is the density; t is the time; v is the velocity vector; P is the pressure; μeff
is the effective viscosity; g is the acceleration of gravity.
The kinetic energy equation and the diffusion equation are as follows:

∂(ρk) ∂(ρku i ) ∂ μt ∂ε
+ = μ+ + G k + G b − ρε (3)
∂t ∂ xi ∂x j σk ∂ x j

∂(ρε) ∂(ρεu i ) ∂ μt ∂ε ε ε2
+ = μ+ + C1ε (G k + C3ε G b ) − C2ε ρ
∂t ∂ xi ∂x j σε ∂ x j k k
(4)
where u i is the component of the velocity v; k is the turbulent energy; ε is the turbulent
energy dissipation rate; i and j represent different directions; C1ε = 1.44, C2ε = 1.92
and C3ε = 1.0 are constants; G k and G b are the turbulent energy due to the average
velocity and the turbulent energy due to the density unevenness, respectively.
Combustion Model
During the baking with the RH vacuum vessel, gas and oxygen are separately injected
into the vacuum vessel for burning and heat release. Therefore, the probability density
function (PDF) of the non-premixed fuel gas and combustion-supporting oxygen can
be used to simulate the combustion process of the gas in the vacuum vessel. The fuel
gas and the combustion-supporting oxide are not premixed, and the transport equation
of the average mixing fraction f and its root mean square pulsation scale is

∂ μt ∂ f
ρμ j f − =0 (5)
∂x j σt ∂ x j

∂ μt ∂g f ∂f 2 ε
ρμ j g f − = Cg μt − Cd ρ g f (6)
∂x j σt ∂ x j ∂x j k
where σt = 0.7, Cg = 2.86, Cd = 2.0 are constants.
Model of Heat Transfer by Radiation
During baking with RH vacuum vessel, gas and oxygen burn in a vacuum vessel to
produce a high-temperature flame. Therefore, radiative heat transfer is an important
way of heat transfer in a vacuum vessel. Due to the large volume of RH vacuum vessel,
radiation heat transfer accounts for a large proportion of the total heat transfer [6].
The method of discrete ordinates is particularly suitable for coupling calculation
of flow, combustion, and heat transfer, so it was adopted for the simulation in this
paper. The weighted-sum-of-gray-gases model (WSGGM) was used to calculate the
absorption rate of radiation [7].
794 F. Yuan et al.
Fig. 1 Calculation domain
Calculation Model
Grid Partition
The numerical simulation of the baking process in the RH vacuum vessel in the plant
was carried out using the model listed above. The calculation domain is shown in
Fig. 1. The inner diameter of the RH vacuum vessel is 2138 mm, the internal height
of the vacuum vessel is 7000 mm, the inner diameter of the dip tube is 650 mm, the
length of the dip tube is 1725 mm, the diameter of the injection inlet of oxygen is
25 mm, and the diameter of the injection inlet of gas is 50 mm. The injection inlet of
oxygen and the injection inlet of the gas were arranged in a ring shape. Combustion
products were discharged from the dip tube. Since only the temperature distribution
inside the vacuum vessel of the baking process was calculated, and the calculated
area did not include the lining of the vacuum vessel, meshing was only done for the
area of combustion [8]. The meshing is as shown in Fig. 2. The total number of mesh
in the entire calculation area was approximately 10 × 105 .
Initial Conditions and Boundary Conditions
Initial conditions: the ambient temperature was 305 K; the ambient pressure was
101,325 Pa; the initial temperature of fuel and oxygen was 300 K; the fuel was coke
Fig. 2 Meshing of the

model
Table 1 Components of coke oven gas (volume fraction)/%

CH4 H2 N2 O2 CO CO2
24.44 60.74 5.22 0.68 6.77 2.15
oven gas, and the volume ratio of fuel to oxygen was 1:1.16. The components of
coke oven gas are as shown in Table 1.
Boundary conditions: the conditions of the gas and oxygen inlet were of velocity-
inlet conditions. Given the inlet speed of gas and oxygen, the turbulent energy k at
the inlet and the turbulent energy dissipation rate ε can be obtained by the equation:
kin = C1 vin
2
; εin = kin
1.5
/(C2 din ) (7)
The subscript in indicates the inlet, v is the gas flow rate, and d is the hydraulic
diameter of the nozzle. C1 and C2 are constants, and are 0.002 and 0.3, respectively.
The boundary conditions of the outlet take those of the pressure outlet. The RH
vacuum vessel’s wall is a fixed wall and defined by standard wall function, with no
slip and no internal heat source. All the walls of the RH vacuum vessel were set to
the temperature boundary, and the temperature was the measured 1100 K of the inner
wall.
796 F. Yuan et al.
Calculation Results
Based on the actual RH refining baking system, the gas flow of 273 m3 /h was adopted
for calculation. The calculation was conducted for the four lance positions (the dis-
tance from the lance to the top of the RH vacuum vessel), including 4, 4.5, 5, and
5.5 m. The calculation results are shown in Fig. 3. Since the gas flow remained the
same throughout the simulation, during baking, the heat released from the combus-
tion of gas remained the same, and the temperature of combustion was 2200 K.
Therefore, the temperature difference of the lining was not too large [9]. The results
accord with the law of combustion reaction. However, the change in the position
of lance caused the change in the distribution of the high-temperature areas on the
lining of the vessel. With the lowering of the position, the high-temperature baking
area rose higher. When the lance was at 4 m, the flame was slender and the high-
temperature area was small; the reasons were that the spitting flame did not reach
the bottom of the vacuum vessel and that the gas and oxygen were not preheated.
However, with this lance position, the position of the high-temperature area of the
lining was the highest; the gas in RH received the most complete combustion with
the highest utilization rate of heat, but the baking flame did not reach the part of
the dip tube that was in direct contact with the molten steel in the lower part of the
vessel, which might lead to a large temperature decrease of the molten steel during
the refining [10].
When the lance position was as high as 4.5 m, the spitting flame started to reach
the bottom of the vacuum vessel, ensuring sufficient baking on the refractory material
at the bottom of the vacuum vessel, and ensuring high temperature at the lining, but
Fig. 3 Temperature distribution (K) in RH vacuum vessel under different lance positions
under this position, the flame did not reach the dip tube, hence failing to achieve
high-temperature baking on the dip tube. When the lance position was as low as 5 m,
the flame reached the bottom of the vacuum vessel and the high-temperature area
was expanded to the dip tube, which achieved full and high-temperature baking of
the bottom of the vacuum vessel and the dip tube. When the lance position was 5.5 m,
the high-temperature area of the flame reached the bottom of the dip tube, and the
flame blew out of the vacuum vessel from the bottom of the dip tube, which caused a
lot of heat loss. Obviously, the position of 5.5 m is not conducive to high-efficiency
baking.
Model Verification and Analysis of Results
Verification by Experiment
To verify the accuracy of experimental results, the actual temperature at the top of
the vacuum vessel during baking was measured. The location of the temperature
measurement point is shown in Fig. 4. The temperature measuring point No. 17 is
the position of the thermocouple that actually measured the wall temperature in the
vacuum vessel. The locations of temperature measuring points No. 1 to No. 16 were
Fig. 4 Illustration of the

locations of actual points and
calculated points for
temperature monitoring
798 F. Yuan et al.
experimental and simulated
results under different lance
positions (temperature
measuring point No. 17)
the locations where the temperature of simulated results were collected. The points
were located on the vertical line of the center of the dip tube in the vacuum vessel, and
their specific positions are shown in the figure. According to the on-site recording
and measurement of the baking temperature, the actual measured temperatures under
the four lance positions were selected to verify the accuracy of the model. As shown
in Fig. 5, the maximum calculation error is about 50 K, the difference between
the temperature distribution reflected in the calculation results and the measured
results is within an acceptable range, and the temperature at the top of the vacuum
vessel decreases with the rise of the lance position. It can be concluded that the
measured results are basically consistent with the simulated results and can provide
optimization reference for actual production.
Analysis of Results
As shown in Fig. 6, the lance position of 5 m is comparatively suitable for the actual
baking with the vacuum vessel. Under this lance position, the gas can be well burned;
the temperature at the bottom of the vacuum vessel can reach 1750 K and that of the
Fig. 6 Simulation results by

monitoring points under
different RH lance locations
dip tube can reach about 1850 K, which guarantees that the refractory temperature
of the part in contact with molten steel meets the requirements; the high-temperature
area is larger than that of the lance position of 5.5 m; the baking is comparatively
uniform; the baking temperature reaches the requirements, and the temperature of the
vacuum vessel reaches around 1400 K. Considering that in practice, during refining,
solidification of molten steel occurs at 2.5–3.5 m above the interior lining of the
vacuum vessel [11], which causes a series of issues, such as poor refining effect and
reduced life of refractory materials [12]. The solutions include melting the solidified
steel at high temperatures and raising the temperature of the lining to prevent further
solidification. As shown in Fig. 6, the area of solidification of molten steel is at the
monitoring points No. 8 to No. 11. With the lance positions of 4 and 4.5 m, the high
baking temperature can be reached at the solidified steel on the lining, but the dip
tube must always be kept in the high-temperature area during baking. Therefore, for
the efficient baking of the spots of solidified steel on the dip tube and in the vacuum
vessel, the lance position should be kept at 4.5 m or 5 m. The lance position of 4.5 m
reduces solidification of molten steel on the lining of the vacuum vessel. Therefore,
considering the effective utilization of energy, uniformity of baking, solidification
of steel on the lining, and environmental friendliness, the lance position of 4.5 m
should be adopted for the early phase of baking and the lance position of 5 m should
be adopted for the latter phase of baking to optimize the baking operation system of
RH vacuum vessel, so as to improve the efficiency and effectiveness of baking.
Conclusion
(1) If the fuel and oxide gases are not preheated, the gas will burn in slender flames,
resulting in small high-temperature areas and low utilization rate of heat from
the gas. Fuel injection into the bottom of RH allows for the full mixing with
oxygen and increases the range of high-temperature areas, which improves the
efficiency for baking.
(2) Lowering the position of the lance enlarges the high-temperature areas under
the vacuum vessel’s lining. The position at 4.5 m is ideal, and with this position,
the high-temperature area of the vacuum vessel’s lining contains the area where
the molten steel solidifies during the refining, and the dip tube is guaranteed to
be in the high-temperature area of the baking flame. The position at 5 m results
in a good baking effect on the refractory at the bottom and on the dip tube of the
vacuum vessel and prevents insufficient gas combustion and heat loss from the
bottom of the dip tube. Therefore, vacuum vessel baking should be divided into
two steps. During the first step, the lance position at 4.5 m should be adopted to
remove solidified molten steel of the lining. During the second step, the lance
position at 5 m should be adopted to increase the baking temperature of the
bottom of the vacuum vessel and the dip tube and to reduce the heat loss of
molten steel during refining.
800 F. Yuan et al.
(3) The results of the numerical calculation are basically consistent with the mea-
sured results from the on-site baking process. The calculated distribution of
temperature field can reflect the actual on-site conditions and hence is suitable
when used as a reference for optimizing on-site baking parameters.
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Hebei Metall 206(2):55–57
Part X
Utilization of Complex Ores
Ni Recovery from Nickeliferous
Pyrrhotite Concentrates via a Thermal
Concentration Process: Effects of Heat
Treatment Time
Feng Liu and Mansoor Barati
Abstract Nickeliferous pyrrhotite (Pyrr) tailings represent a promising Ni resource.

Previous work has demonstrated that heating of nickeliferous Pyrr in the presence of
suitable additives under a non-oxidizing atmosphere is capable of recovering the Ni
value in the form of ferronickel alloy. In this study, the Pyrr concentrate, a flotation
product of nickeliferous Pyrr tailings, was thoroughly mixed with metallic Fe and
activated carbon, and then pressed into briquettes. The resultant briquettes were heat-
treated at 900 °C for varying periods of time in Ar, followed by an Ar-quenching
operation to retain the high-temperature structure. The calcine microstructure was
examined as a function of treatment time, together with the composition of Ni-bearing
phases. It was shown that progression of the iron sulfidization was companied by the
formation of ferronickel alloy via multiple mechanisms, and prolonged treatment
time promoted the uniformity of phase compositions and coarsening of the alloy
particles.
Keywords Pyrrhotite tailings · Thermal concentration · Ferronickel · Sintering ·

Coarsening
Introduction
Nickeliferous pyrrhotite (Pyrr) tailings which are a by-product of the beneficiation of

Ni-Cu sulfide ores are receiving increasing amounts of attention from both industrial
and academic communities. Our estimate shows that the accumulated Pyrr tailings in
Sudbury, Canada amount to 75–100 Mt on a dry basis, which are equivalent to 600–
800 kt Ni [1]. Currently, Sudbury Pyrr tailings are directly dumped in the carefully
constructed tailings impoundments; as a consequence, none of the values (Fe, Ni, S,
and energy) associated with this material are recovered. Furthermore, due to the on
going oxidative dissolution of highly reactive Pyrr, the direct dumping strategy may
not be sustainable or friendly sound. In view of these, i.e., huge revenue potential
F. Liu (B) · M. Barati

University of Toronto, 184 College Street, Toronto, ON M5S 3E4, Canada
e-mail: fengutsg.liu@mail.utoronto.ca

https://doi.org/10.1007/978-3-030-36540-0_71
804 F. Liu and M. Barati
and hazardous nature of Pyrr tailings, we are investigating a novel process, in which
the Ni-bearing Pyrr is converted to a mixture of “waste” iron sulfide with reduced
reactivity and iron-based alloy enriched with Ni [2, 3]. One of the proposed flowsheet
variants is to mix the Pyrr material with metallic Fe, followed by heat-treating the
mixture in a neutral atmosphere.
The main purpose of the present work was to study the effects of treatment time
on the microstructure and phase composition of the briquettes consisting of Pyrr
concentrate, metallic Fe, and activated carbon when heat-treated at 900 °C in Ar.
In this investigation, finely ground Pyrr concentrate (<75 µm) obtained by flotation
of the Pyrr tailings which were produced by the Strathcona mill (Glencore, Sudbury,
Canada) was used. Table 1 presents the chemical composition of the Pyrr concentrate
determined by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-
OES) and LECO sulfur analyzer.
The minerology of the Pyrr concentrate was analyzed by X-ray Diffraction (XRD),
and was found to consist mainly of Pyrr of both monoclinic and hexagonal types.
The presence of magnetite was also detected and its amount was estimated to be
about 5 wt%. Although pentlandite, another Ni carrier in Pyrr concentrate, was not
identified from the XRD pattern, its presence was undoubted if one calculated the
mass balance of Ni.
Green briquettes were prepared by thoroughly blending Pyrr concentrate with
chemical-grade iron powder (>99% purity, Alfa Aesar, <75 µm) and activated carbon
powder (Darco G-60, Aldrich) at a mass ratio of 50:10:1, and pressing the resulting
mixture using a hydraulic press under a uniaxial pressure of 5,000 lb.
All green briquettes were heat-treated in an electric horizontal tube furnace. The
schematic diagram of the furnace and the employed thermal treatment schedule are
shown in Fig. 1a, b, respectively. The hot zone temperature of the furnace was kept
at 900 °C during the entire duration of experiments. For each batch, the briquettes
were loaded on an Al2 O3 -made plate coated with a thin layer of boron nitride, and
placed in the cold zone of the furnace. A porous alumina brick was attached to the
plate so that the cold zone temperature was less than 100 °C. This brick, on one
hand, effectively prevented the briquettes from being pre-heated by radiation during
Ar flushing, and on the other hand, ensured efficient Ar quenching. After Ar flushing
Table 1 Chemical composition of the Pyrr concentrate (wt%)

Technique Elements
Ni Cu Co Fe S Zn Other
ICP-OES 1.59 0.30 0.04 53.29 – 0.03 7.42
LECO – – – – 33.86 – –
Ni Recovery from Nickeliferous Pyrrhotite Concentrates … 805
Fig. 1 a Schematic diagram of the horizontal tube furnace; b thermal treatment schedule
for 30 min, the briquettes were pushed to the hot zone, held for a pre-determined
period of time, and quenched by pushing the brick together with the briquettes back
to the cold zone. The thermally treated briquettes were mounted in epoxy, polished,
carbon-coated, and examined by Scanning Electron Microscopy (SEM) and Electron
Probe Micro-Analysis (EPMA).
The treatment time affects the productivity and energy consumption. Whereas the
oxidative roasting of Pyrr tailings is an autogenous process [4]; the thermal concen-
tration under the non-oxidizing atmosphere is energy-intensive. To assess the effects
of the treatment time, the investigation was conducted by heat-treating the briquettes
at 900 °C for 10, 40, and 160 min.
We have demonstrated in the previous work [5] that metallic Fe could be sulfidized
by metal-deficient Pyrr in a neutral atmosphere. This iron sulfidization served as the
key step for removing the sulfur from the pre-existing Pyrr, thereby inducing the
precipitation of ferronickel alloy. Shown in Fig. 2a was the microstructure of the
briquette obtained that was heat-treated at 900 °C for 10 min. Large pieces of remnant
metallic Fe were easily distinguishable, and their morphology was characterized by
Fig. 2 BSE micrographs of the cross section of the thermally treated briquettes obtained at 900 °C
for various treatment times: a 10 min; b 40 min; and c 160 min. Bright area is metal, light gray area
is iron sulfide, dark gray area is oxides, and black area is voids filled with epoxy
a rugged surface. Note that within the remnant metallic Fe particles there was iron
sulfide (Figs. 2a, 3a), the formation of which was attributed to the porous structure of
the pre-existing metallic Fe. This might help disintegration of metallic Fe particles,
which in turn accelerated the sulfidization of metallic Fe particles. The Ni migration
into the remnant metallic Fe particle was evident (Fig. 3a); however, the appearance
of “spikes” in the profile of Ni concentration indicated that the Ni penetration into
the remnant metallic Fe particles was not uniform and probably influenced by the
presence of iron sulfide formed inside them. Besides large pieces of remnant metallic
Fe, the thermally treated briquette was found to contain an appreciable number of
tiny alloy particles measuring <10 µm, most of them being ~5 µm (Fig. 4a). The
exact origin of these tiny alloy particles, i.e., formed directly from the sulfide phase
or from disintegrated remnant metallic Fe upon sulfidization, seemed impossible to
determine without knowing the Ni concentration profile within them. Another feature
with respect to the briquette’s morphology was that the sulfide phase was not well
sintered, and thus the cross-grain diffusion was probably very limited.
At 40 min, the most striking morphological changes included well-sintered sulfide
phase and the absence of discernable remnant metallic Fe particles. The coarsening
of alloy particles with increasing treatment time was confirmed, and based on the
observation that the population of alloy particles measuring ~5 µm was significantly
reduced compared with the case when heat-treated for 10 min (Fig. 4b). In Fig. 3b,
the concentration profile of elements including Fe, Ni, and S across a gourd-shaped
alloy particle was displayed. It is seen that the nickel was enriched at the surfaces of
Fig. 3 BSE micrographs and relative concentration profiles of elements across the alloy/sulfide
interface in the thermally treated briquettes at 900 °C for various treatment times: a 10 min; b 40 min;
c 160 min. For BSE micrographs, bright area is metal, light gray area is iron sulfide, dark gray area
is oxides, and black area is voids filled with epoxy
Fig. 4 Frequency plots of the size distribution of alloy particles formed in thermally treated bri-
quettes at 900 °C for various treatment times a 10 min; b 40 min; c 160 min. Note ImageJ was used
for the analysis [7] and the area under investigation for all samples was 1196 × 897 µm
the alloy particle with a depth of a few micrometers. The accumulation of Ni at the
surfaces was considered to result from the fact that the diffusivity of Ni in the metallic
Fe is lower than in the iron sulfide by over three orders of magnitude [6]. The Ni
enrichment at the surfaces of alloy particles might help establish “local equilibria”
and thus inhibited the Ni migration from the sulfide to alloy phase. The drop in the Ni
concentration and rise in the Fe concentration at the gourd neck seemed to suggest
this gourd-shaped alloy particle originated from the remnant metallic Fe.
Whereas little morphological change was observed (Fig. 2c), further increase in
treatment time to 160 min continued to promote the coarsening of alloy particles, as
shown in Fig. 4c. One of the interesting alloy particles together with concentration
profiles of Fe, Ni, and S was displayed in Fig. 3c. Featuring markedly higher Ni
contents at its center region; this alloy particle should precipitate directly from the
sulfide phase. This is because the alloy nuclei formed via direct precipitation were
highly enriched in Ni; however, the evening of the concentration profile of Ni in alloy
particles was inhibited due to the slow Ni diffusion during the subsequent growth
stage.
The Ni concentration of randomly selected alloy and sulfide grains was measured
by EPMA, and the results are presented in the form of boxplots (Fig. 5). For the
Fig. 5 Boxplots showing the Ni concentration in alloy and sulfide phases measured by EMPA.
Note Box corresponded to the range of 25–75% and average values were connected
products obtained at 10 min, a highly Ni-enriched alloy particle containing ~44.0%Ni

was found, the formation of which was undoubtedly related to pentlandite. The Ni
concentration in the remnant metallic Fe particles varied between 2.0 and 15.7%Ni
depending upon the depth of measurement away from the sulfide/alloy interface.
It is noted from Fig. 5 that as the treatment time was increased from 10 to 40 min,
the average Ni concentration in the sulfide phase was increased from 0.48 to 0.57%Ni.
This unexpected result might stem from the choice of insufficient number of analyses
since within such a short treatment time should the Ni concentration of the sulfide
phase span a wide range, partly because the newly formed iron sulfide was quite low
in Ni concentration [3]. As a result, the boxplots at 10 min shown in Fig. 5 might not
be representative of the whole sample.
Further increase in the treatment time from 40 to 160 min resulted in a slight reduc-
tion in the Ni concentration of the sulfide phase from on average 0.57 to 0.53%Ni
(Fig. 5). In addition, compared with the results obtained at 10 and 40 min, the Ni
concentration of alloy particles at prolonged treatment time (160 min) was found to
fall into a narrower range.
Conclusions
In this study, effects of the treatment time on the microstructure and phase compo-
sition of the briquettes that were heat-treated at 900 °C in Ar were investigated. At
least two concurrent mechanisms were responsible for the formation of alloy parti-
cles so that the Ni value could be recovered: direct precipitation of alloy particles
from the sulfide phase and Ni penetration into the pre-existing metallic Fe. A treat-
ment time of 10 min was not sufficient to produce well-sintered Pyrr mass, and the
iron sulfidization was not complete. Prolonged treatment time promoted not only the
Ni migration from Pyrr to alloy but also the coarsening of alloy particles.
Acknowledgements The financial supports from Natural Sciences and Engineering Research
Council of Canada (NSERC Fund # STPGP 479533-15) and Process Research Ortech Inc. are
gratefully acknowledged. The authors also thank Tony Deng from Glencore for preparing pyrrhotite
samples.
References
1. Rezaei S, Liu F, Marcuson S, Muinonen M, Lakshmanan VL, Sridhar R, Barati M (2017) Can
Metall Q 56
2. Yu D, Liu F, Zhang J, Barati M (2019) Metall Mater Trans B
3. Liu F, Yu D, Marcuson S, Wang F, Li B, Barati M (2019) Miner Eng 134:206
4. Conard BR (2013) CIM J 4:61
5. Liu F, Yu D, Marcuson S, Wang F, Li B, Barati M (2019) Miner Eng 134
6. Sridhar R, Dalvi A, Bakker HF, Illis A (1976) Can Metall Q 15:255
7. Schneider CA, Rasband WS, Eliceiri KW (2012) Nat Methods 9:671
Method to Quantify the Effect
of Temperature and Rotational Speed
on the Decrepitation of South African
Manganese Ores in a Rotary Kiln
M. S. Moholwa, J. D. Steenkamp and H. L. Rutto
Abstract The lack of knowledge regarding the mineralogical and metallurgical

properties of Mn ores is a common problem in the production of ferromanganese
alloys. Decrepitation, which is the breakage of solid particles upon heating, is an
important quality parameter of manganese ores which has not been adequately stud-
ied. This work will study the effect of different parameters on the decrepitation index
when the ores are preheated in a rotary kiln. These parameters are the rotational speed,
heating rate, temperature, and mineralogical composition. Three South African ores,
two from the same mine, will be used for this study. The purpose of the paper is to
report on method development.
Keywords Decrepitation · Manganese ores · Rotary kiln
Introduction
Manganese ores are mostly used as raw material to produce manganese ferroal-
loys. There are several grades of ferromanganese alloys among them is low car-
bon (LCFeMn), medium carbon (MCFeMn), and high carbon ferromanganese
(HCFeMn) [1]. These alloys typically contain 85–90% Mn and 0.75% C, 80–85%
Mn and 1.5% C, and 78% Mn and 7.5% C, respectively [1]. Of the global con-
sumption of manganese, 92% is directly related to the steel industry, seeing that
manganese improves the malleability, toughness, and hardness of the steel [2]. The
non-ferrous applications of manganese include the production of dry-cell batteries
and animal feed. There is a total global reserve of approximately 690,000 tons, of
which 63% is found in South Africa, Ukraine, Australia, Brazil, and India [3]. A
common problem in the production of ferromanganese alloys is the lack of knowl-
edge about the mineralogical and metallurgical properties of manganese ores [4].
M. S. Moholwa (B) · H. L. Rutto

e-mail: SamMO@mintek.co.za
J. D. Steenkamp · H. L. Rutto
Vaal University of Technology, Andries Potgieter Blvd, Vanderbijlpark 1900, South Africa
https://doi.org/10.1007/978-3-030-36540-0_72
812 M. S. Moholwa et al.
Commercially, HCFeMn is produced by carbothermic reduction of manganese ores,

primarily in electric submerged arc furnaces (SAFs) [5]. Carbothermic reactions
involve the reduction of metal oxides using carbon as a reducing agent. SAFs are
generally circular and have three electrodes, each connected to a separate electrical
phase [5]. The electrodes are submerged into a mineral bed and the electric current
runs through the area below the electrode tips where electrical energy is converted
to heat [5].
PREMA is a Horizon 2020 project, funded by the European Union, and aims at
demonstrating an innovative suite of technologies, involving utilization of industrial
off-gases and solar thermal energy [6]. This is done to reduce energy consumption
and CO2 emissions from manganese production [6]. A pilot-scale campaign will be
conducted at Mintek in 2021 to study the effect of preheating the Mn ore to 600 °C
in a rotary kiln before charging into a submerged arc furnace (SAF).
In terms of the rotary kiln operation, one of the unknown parameters is the potential
for decrepitation of the manganese ore. Decrepitation is the breakage or disintegration
of particles upon heating, resulting in the production of fine particles that cause
efficiency losses and reduces the gas permeability of the particle bed in the SAF [2].
Consequently, the process gas will be trapped beneath the burden of raw material
which may cause an eruption or an explosion [7]. Furthermore, insufficient reduction
can occur due to the process gas containing CO being channeled unevenly across the
burden.
Currently, a master’s research project looks into the potential for decrepitation
of manganese ore during preheating in a rotary kiln. The purpose of the study is to
determine if the specific manganese ores considered for the campaign will decrepitate
during the preheating process. The effects that the particle size, heating rate, kiln
rotation speed, temperature, and mineralogy will have on the decrepitation index
(DI) of the ore will be investigated. The purpose of the paper is to report on the
method development process.
Method
The method development consisted of two parts: (1) a review of literature and
(2) preliminary test work conducted at a commercial laboratory that quantifies the
decrepitation of iron ore.
Review of Literature
Decrepitation of Manganese Ore
Faria et al. [2] studied the effect of mineralogy, moisture content, and porosity of ore
on the decrepitation behavior within the context of SAF production of HCFeMn. It
was found that all three play a role in the decrepitation of ore.
Method to Quantify the Effect of Temperature and Rotational … 813
In the investigation, they studied four different types of ores of which one was
from South Africa. 500 g of sample was heated in a muffle furnace at 700 °C for
30 min. To determine the DI, the sample was screened using a sieve size of 6.3 mm
after heating. After screening, the particles that passed the screen was weighed. The
equation they used to calculate the DI is presented in Eq. 1. The mineralogy and
chemical analysis of the ores in the study is summarized in Tables 1 and 2.
D I = (M1/M2) ∗ 100 (1)
M1 Mass of particles below 6.3 mm in g

M2 Total mass of the sample in g.
The study claims that manganese oxides decrepitates mainly due to the decom-
position of the cryptomelane and pyrolusite minerals during heating [2]. Manganese
oxides (MnO2 ) experience phase transformation at 700 °C causing volumetric change
[2]. The transformation of MnO2 to Mn2 O3 , began at close to 700 °C for Azul
and Urucum samples. This led to a volumetric expansion that contributed to the
decrepitation of Azul and Urucum ore.
Table 1 Mineralogy of four types of ores utilized in the study by Faria et al.
Ore Mineral type DI
Name Country Size Cryptomalene Bixbyite Pyrolusite Todorokite (I−6.3 )
(mm) (%)
KMnO8 O16 (Mn, MnO2 (Na, Ca,
Fe)2 O3 K)2 Mn6 O12
·3a4·5(H2 O)
Urucum Brazil −19 >50% – <20% – 6
+ 6.3
Morro Brazil −19 – – – – 1
da Mina + 6.3
Azul Brazil −19 >50% – – <20% 6
+ 6.3
Wessel South −19 – <20% – – 12
Africa + 6.3
Table 2 Chemical analysis of four ore types utilized in the study by Faria et al.
Sample Mn (%) Fe (%) Al2 O3 CaO (%) MgO SiO2 P (%) Total
(%) (%) (%)
Azul 46.96 4.12 6.11 0.09 0.12 3.99 0.097 61.59
Morro 24.48 2.89 5.42 2.87 2.23 23.02 0.076 60.99
da mina
Urucum 32.58 6.92 0.78 0.07 0.05 2.11 0.109 42.62
Wessels 40.16 8.08 0.4 7.45 2.05 5.51 0.019 63.67
This volume change yields anisotropy that induces stress in specific regions of the
particle, which leads to the formation of cracks [2]. Urucum ore has a higher con-
centration of pyrolusite, which undergoes a considerable reduction in volume when
it transforms into bixbyite, and this could cause intense decrepitation [2]. Bixbyite
and pyrolusite have a crystal structure of isometric and tetragonal, respectively.
Another factor affecting decrepitation is the removal of structural water from the
hydrated phases during pretreatment [2]. Heating the ore gradually eliminated the
physical shock caused by the sudden release of moisture and in turn reduces the
decrepitation intensity. When water is heated, its vapor pressure gradually rises until
it reaches the pressure in the surrounding atmosphere, starts boiling and eventually
evaporates. The vapor pressure from the water molecules trapped in ore pores is in
some cases enough to rupture particles [2]. The study by Faria et al., revealed that
decrepitation intensity increases considerably because of moisture for Azul, Urucum,
and Wessel ores.
Ores of bigger diameter and micropores volume have smaller DIs compared to
ores with a smaller diameter and volume [2]. Bigger volume pores can promote a
vapor pressure relief inside the pores of the ore particles, this reduces stress on the
lump ore and in turn decreases decrepitation intensity [2]. The pressure build-up
causes more stress in closed pores than in open pores, therefore ores with closed
pores are more susceptible to decrepitation compared to the ores with open pores
[5].
Decrepitation of Iron Ore
Decrepitation of iron ore in blast furnaces is such an extensive field of study that
a standardized method exists to characterize the ore. One such example is the ISO
standard 8173. The steps followed can be summarized as follows:
• The sample with a size range of −25 to +20 mm is dried in an oven at 105 °C
overnight.
• 500 g of the sample is weighed.
• The muffle furnace is switched on to heat up gradually until the desired temperature
of 700 °C is reached.
• The 500 g sample is then fed into the rest portion holder.
• Once the furnace reaches the desired temperature, the test portion holder is then
placed into the muffle furnace.
• The test portion is left in the furnace for a duration of 30 min, and thereafter the
sample is removed and allowed to cool down.
• After cooling the sample is screened with a sieve size of 6.3 mm.
• And the DI is determined using Eq. 1.
Preliminary Investigation
For the project presented here, a preliminary investigation was done at Anglo Amer-
ican Research and Development laboratories on two types of South African man-
ganese ore, Ore #A and Ore #B. The purpose of the preliminary investigation was to
determine if there was potential for a research project. The Anglo American Research
and Development laboratories were chosen because they are currently conducting
extensive decrepitation test work on iron ores, and they have good understanding of
the procedure. Ore #A and Ore #B were chosen because they were readily available at
Mintek from previous test work. The chemical composition of the ores are presented
in Table 3. Both ores decrepitated to some extent during heating and there was also
a difference in the extent to which they decrepitated, as indicated by their respective
Dis.
The method from ISO standard 8371 DI of iron ores was applied in the preliminary
investigation and the results were presented below. The DI was calculated using Eq. 1
(Table 4).
Based on the results of the literature review and the preliminary investigation, it was
decided to continue with the project using the manganese ores that will be used during
the campaign. The manganese ores were sourced from the Kalahari manganese field
(KMF), located in the Northern Cape province of South Africa. Three types of ores
were considered: Ore #C and Ore #c were sourced from the same mine and Ore #D
Table 3 Typical composition of two types of manganese-bearing ores sourced for the campaign
(mass%)
Raw Mn Fe Al2 O3 SiO2 CaO MgO H2 O P S Total
material
Ore #A 36.5 5.5 0.2 5.1 13.6 4.1 0.8 0.02 0.01 65.83
Ore #B 44.8 10.7 0.3 5.4 7.4 1.5 0.8 0.04 0.18 71.12
Table 4 Preliminary investigation results

Ore type Test no M1 (g) M2 (g) DI (%) Average DI (%)
Ore #A 1 482.4 61.7 12.8 13.0
2 480.0 63.1 13.1
Ore #B 1 480.7 47.2 9.8 10.8
2 479.0 56.1 11.7
from a different mine. Ore of 6–75 mm in particle size distribution was used for the
preliminary tests.
Research Questions
In order to achieve the objective of the study, the research question was tailored as
shown below.
• How does the size distribution of particles affect the DI of manganese ore?
• How does the temperature affect the DI of manganese ore?
• How does the heating rate affect the DI of manganese ore?
• How does the rotation speed of the rotatory kiln affect the DI of manganese ore?
• How does the mineralogy of the ore affect the DI of manganese ore?
Method
In order to obtain answers to these questions, a laboratory-based method was devel-

oped at MINTEK. At the heart of the method lies the tumbling and decrepitation
tests. However, the method will include material preparation and characterization
i.e. Particle size distribution, bulk chemistry, and bulk and specific phase chemistry.
Decrepitation Test
The decrepitation test will adopt a method from ISO 8371 (DI of iron ores).
• 1 kg of the sample will be weighed using a balance.
• The sample will then be fed into the rotary kiln.
• The kiln power and rotation speed will then be switched on to control the desired
parameters (heat rate and rotational speed) stated in the experimental design matrix
for each run.
• Once the desired temperature is reached, the sample will be kept at the temperature
for 30 min.
• The kiln will then be switched off and the sample will be allowed to cool down
inside the kiln.
• After cooling the sample will be screened to determine the fraction below the
lower limit of a particular size range, 6 mm screen for +6–20 mm, 20 mm screen
for +20–40 mm and 40 mm screen for +40–75 mm.
• The rotating tube will be cleaned by blowing it with compressed air after every
run to avoid contamination.
Fig. 1 Experimental set-up of a rotatory kiln
• The control panel is equipped with a rotational speed controller and it will be
validated by observing the rotation and count the revolution per minute.
• The thermocouples will be calibrated prior to the experiment.
The experimental set-up is illustrated in Fig. 1.
Tumbling Test
• A tumbling drum will be used for the test (Fig. 2). The drum has a capacity of 5 kg
and the rotational speed can be varied between 5 and 30 rpm.
• The different size fractions for each of the three sample types will be split using a
rotary splitter to obtain representative samples that will be used for the tumbling
tests.
• One kilogram will be fed into the drum which will be switched on, starting with
a rotational speed of 5 rpm for 30 min.
• The step above will be repeated with the rotational speed of 10 rpm and again with
the speed of 20 rpm.
• After the tumbling test, the sample will then be screened to obtain the percentage
of particles reporting below the lower limit of a particular size fraction that was
used for that test and also to determine if there have been changes in the particle
size distribution of the sample.
Fig. 2 A picture of a tumbling drum that will be used for the test
Overall Procedure
The overall procedure is outlined in Fig. 3.

• 250 kg of each sample will be sieved to the size fraction of +6–20, +20–40, and
+40–75 mm using screens.
Fig. 3 Methodology flowsheet

• The sample will be split and the representative sample will be obtained using a
rotary splitter in order to obtain samples for the decrepitation test, tumbling test,
and for crushing as shown by 1.1, 2.1, and 5.1 in Fig. 1.
• After the decrepitation and tumbling tests, the samples will be screened as shown
by 3.1 and 4.1 in Fig. 1.
• The crushed sample will be split using a rotary splitter (6.1) to obtain a sample
to be milled for bulk chemical and phase chemical analyses (7.1), to stores as a
reference sample, and for a sample to be analyzed by scanning electron microscopy
with energy dispersive spectroscopy (SEM-EDS).
• The milled sample will then be used for bulk analysis inductively coupled
plasma optical emission spectrometry (ICP-OES), x-ray fluorescence (XRF), and
qualitative x-ray diffraction (QXRD).
• Contamination will be prevented by thorough cleaning of the equipment before it
is used for another sample.
Method Comparison
The method used in the preliminary investigation has minor similarities to the decrepi-
tation test method developed at Mintek. The preliminary test method was developed
to only investigate if manganese ore decrepitates when heated to 700 °C for 30 min,
whereas the method developed at Mintek will also investigate the effect of experi-
ment temperature, heating rate and the rotational speed of the rotary kiln on the DI.
From literature, it was discovered that another factor affecting DI of manganese ore
is the removal of structural water from hydrated phases [2]. Heating the material to
temperatures higher than 700 °C will remove more structural water from hydrated
phases, which will increase the DI of the sample. Using a higher heating rate will
cause the removal of moisture to happen at higher rate, which may result in bringing
the issue of thermal shock into play. This will be even more intense for the moisture
that is trapped in the closed pores of the sample. When the moisture experience a
sudden change in temperature the vapor pressure of the moisture will also increase
suddenly, sometimes the pressure increase may be enough to rupture the walls of the
pore and break the sample into smaller particles sizes. This will increase the DI of
the sample.
Heat decomposition cryptomelane and pyrolusite to Mn2 O3 , according to Faria
this may contribute to the decrepitation phenomenon [7]. This is because according
to Faria cryptomelane and pyrolusite have their volumes, respectively, 5.4 and 0.6%
higher than Mn2 O3 [7]. This means that the decomposition will cause a reduction in
volume for these phases, and this induces stress in specific regions of the particles
leading to formation of cracks. The formation of cracks can lead to particle disin-
tegration especially when the sample is being rotated. Therefore if the ores sourced
from the KMF have cryptomelane and pyrolusite as their mineral type, it means that
the ore that will be used for the test work has a potential to have elevated DIs.
The rotation makes the sample more susceptible to disintegration which will
be regarded as decrepitation in this test work because the mechanical breakage of
particles come into play as a result of collision between particles. The collision will
be caused by the rotation movement of the kiln. The mechanical breakage of particles
will depend on the strength of the sample and the rotary speed of the kiln. Increasing
the rotation speed of the kiln will result in the particles of the sample colliding
more with more force and more frequently this can increase the disintegration index
(dI) of the sample, The dI is calculated the same way as the DI. When the particles
collide more frequently with more force they become more susceptible to mechanical
breakage. For the decrepitation test both the disintegration due to thermal treatment
and the rotating of the sample will be the main factors having an impact on the
DI compared to the preliminary investigation where the mechanical breakage was
absent. The material that is not strong enough in terms of strength will be more
susceptible to disintegration because they will break easily when they collide with
each other.
Conclusions
After reviewing the literature and conducting a preliminary investigation based on

a standard test for iron ore, a method has been developed at Mintek to determine
the potential for decrepitation of manganese ore in a rotary kiln. Three types of
ores will be split into three size fractions each, and the DI determined based on the
experimental plan in Table 5.
Table 5 Experimental plan

Particle size Rotational Heating rate Temperature
range (mm) speed (rpm) (°C/min) (°C/min)
+6–20 10 2 600
+6–20 10 2 700
+6–20 10 2 800
+6–20 10 1.5 700
+6–20 10 2 700
+6–20 10 2.5 700
+6–20 5 2 700
+6–20 20 2 700
+20–40 10 2 700
+40–75 10 2 700
References
1. ASTM Standards A99-03 (2009) Standard specification for ferromanganese. ASTM Interna-
tional
2. Faria GL, Jannoti N, Da Silva Araujo FG (2012) Decrepitation behavior of manganese lump
ores. Elsevier
3. Corathers LA (2017) Mineral commodity summaries 2017. US Geol Surv
4. Faria GL, Vianna NCS, Jannoti N, Vieira CB, Da Silva Araujo FG (2010) Decrepitation of
Brazillian manganese lump ores. INFACON, Sep 2010
5. Olsen E, Tangstad M, Lindstad T (2007) Production of manganese ferroalloys. Tapir Academic
6. PREMA (2019) [Online] Available https://www.spire2030.eu/PREMA. Accessed 20 Feb 2019
7. Faria GL, Tenório JAS, Jannotti N Jr, da Silva Araújo FG (2013) Disintergration on heating of
a Brazillian manganese lump ore
Production of High-Carbon
Ferrochromium by Carbothermal
Reduction of Vanadium Extraction
Tailings with High Chromium Content
Guang Wang, Jiang Diao, Liang Liu and Bing Xie
Abstract A novel method to smelt high-carbon ferrochromium by synergistic reduc-

tion with vanadium extraction tailings with high content chromium and chromite is
proposed in this paper, which can efficiently recover chromium and iron from vana-
dium extraction tailings with high content chromium and produce high value-added
products. The recoveries of chromium and iron reach 95.79% and 98.06%, respec-
tively, and decrease with the increase of mass ratio. The smelting time has little
influence on the recoveries of chromium and iron. The recoveries of chromium and
iron decreased with the increase of reductant amount. The content of chromium
and iron in the high-carbon ferrochromium is between 47.00% to 52.00%, and
35.00% to 60.00%, respectively. The contents of impurity elements in the high-
carbon ferrochromium meet the expected requirements except nos. 7 and 8. The con-
tent of chromium reached 52.01% in the high-carbon ferrochromium. The optimum
smelting conditions are mass ratio at 5:1, smelting 10 min, and C/O at 1.
Keywords Tailings · High-carbon ferrochromium · Mass ratio · Smelting time ·

Reductant amount
Introduction
Vanadium and chromium are that are widely used in metallurgic, building materials,
and chemical industry due to their unique properties such as high hardness, high
oxidation resistance, and high fatigue resistance [1–3]. Vanadium is also regarded
as “vitamins of modern industry”. About 88% world production of vanadium is
extracted from vanadium titano-magnetite ore [4]. U.S. Geological Survey (2016)
indicated that more than half of vanadium (about 42,000 metric tons of vanadium) in
G. Wang · J. Diao (B) · L. Liu · B. Xie

College of Materials Science and Engineering, Chongqing University, No. 174 Shazheng Street,
Shapingba District, Chongqing 400044, People’s Republic of China
e-mail: diaojiang@163.com
Chongqing Key Laboratory of Vanadium–Titanium Metallurgy and Advanced Materials,
Chongqing University, Chongqing 400044, People’s Republic of China

https://doi.org/10.1007/978-3-030-36540-0_73
824 G. Wang et al.
the world is supplied by China [5]. In China, the blast furnace–basic oxygen furnace
(BF-BOF) process is the mainstream process for extracting vanadium from vana-
dium titano-magnetite ore [6]. Vanadium slag, the by-product of BF-BOF process,
is one of the most main feedstocks in China for vanadium extraction [7]. Chromium
is also enriched into vanadium slag since vanadium and chromium have similar
chemical properties [8]. Normally, Chromium is removed as an impurity element in
the subsequent hydrometallurgical vanadium extraction process with low-chromium
vanadium slag [9]. With the increasing demand for vanadium products in recent years,
the normal vanadium titano-magnetite ore has been utilized in a large scale, and its
reserves are decreasing every year. Therefore, the resources of high-chromium vana-
dium titano-magnetite with huge reserves in China and high-chromium vanadium
slag have gradually begun to be exploited and utilized [10]. For high-chromium vana-
dium slag, chromium can no longer be ignored due to its comparable content, and
high-chromium vanadium slag is a potential raw material for chromium extraction.
Recently, high-chromium vanadium slag has become a research focus in the field
of extraction and separation of vanadium and chromium, and many methods have
been developed and reported [11–14]. Although high recovery of vanadium and
chromium can be obtained by different extraction processes. Nevertheless, these
processes still have unavoidable disadvantages, such as emission of corrosive gases
(HCl, Cl2 , SO2 , and SO3 ) the ring forming in rotary kiln arose in sodium roasting–
water leaching method, and large consumption of salts and energy in NaOH–NaNO3
molten salt process. In addition, the chromium products produced by the above
methods are all chromium oxides or chromium salts with lower economy. To a
certain extent, this restricts the popularization and application of the above process.
While high-chromium vanadium slag is not used in a large scale until now due to
lack of the separation technology of vanadium and chromium with high efficiency
and low cost. In addition, the tailings and wastewater containing toxic vanadium
and chromium with high valence states also restrict its development. What’s more,
it is feasible to enrich chromium into vanadium extraction tailings by controlling
the roasting temperature. Hence, the research on utilization and treatment of vana-
dium extraction tailings with high chromium (“tailings” is used hereafter) is carried
out in this study. Smelting high-carbon ferrochromium with carbothermal reduction
by adding certain proportions of chromite to tailings is proposed. The effects of
mass ratio of chromite and iron (“mass ratio” is used hereafter), smelting time and
reductants amounts on the recovery of chromium, iron, and impurity elements are
discussed in this study.
Production of High-Carbon Ferrochromium by Carbothermal … 825
Table 1 Chemical composition of slags and chromite/wt (%)

V2 O3 Cr2 O3 FeO TiO2 SiO2 MnO Al2 O3 MgO CaO P2 O5 S
Tailings 0.56 10.39 39.96 10.13 15.62 4.38 2.00 2.70 5.21 0.016 0.01
Chromite / 46.89 24.11 / 2.14 / 11.88 9.31 0.70 0.018 0.004
Experimental
Materials
The tailings and chromite samples used in the experiments are obtained from indus-
trial test of smelting high-chromium vanadium titanomagnetite at Panzhihua Iron
and Steel Group Corporation, Sichuan Province, China. Table 1 shows the chemi-
cal compositions of tailings and chromite. The reductant is graphite (C > 99.5%).
The main phases of tailings are iron oxides (Fe2 O3 ), iron titanium oxide (Fe2 TiO5 ),
and iron chromium oxide ((Fe0.6 Cr0.4 )2 O3 ). The main phase in chromite is spinel
((Mg, Fe)(Cr, Al, Fe)2 O4 ). The particle sizes of both the raw materials and reductant
graphite are less than 74 µm.
Experiments
The experimental scheme is shown in Table 2. The purpose of nos. 1–4 is to explore
the effect of mass ratio of tailings and chromite on the recoveries of chromite and iron.
No. 3 and nos. 5, 6 aim for investigating the effect of smelting time on the recoveries
of chromite and iron. No. 3 and nos. 7, 8 are designated to study the effect of reductant
amounts on the recoveries of chromite and iron. In the reduction and smelting process,
the mixed materials were charged into graphite crucibles. Then placed the graphite
crucible into an induction furnace which is used for reduction reaction and melting
Table 2 Experimental scheme

No. Tailings/g Chromite (g) Graphite (g) SiO2 (g) Time (min)
1 200.00 100.00 48.46 / 10
2 133.33 166.67 54.31 2.24 10
3 50.00 250.00 61.61 13.72 10
4 33.33 266.67 63.01 16.01 10
5 50.00 250.00 61.61 13.72 15
6 50.00 250.00 61.61 13.72 20
7 50.00 250.00 73.93 13.72 10
8 50.00 250.00 86.25 13.72 10
826 G. Wang et al.
separation. The heating power is 12 kVA. The reaction temperature is about 1700–
1800 °C. The graphite crucible was taken out from the furnace with air cooling
to ambient temperature after the experiment is finished. The samples were ground
to obtain high-carbon ferrochromium and reduced slag. The recoveries of iron and
chromium are calculated by Eq. (1).
Mm × γ[Fe/Cr]
R[Fe/Cr] = × 100% (1)
Mt[Fe/Cr]
where R[Fe/Cr] is the recoveries of iron and chromium. M m is the weight of metal
after melting. γ [Fe/Cr] is the content of iron or chromium in the metal. M [Fe/Cr] is the
theoretical weight of iron or chromium.
Characterization
The chemical compositions of raw materials were determined by X-ray Fluores-

cence (XRF, Shimadzu XRF-1800). The mineral phases were characterized by X-ray
diffraction (XRD, INCA Energy 350, UK). The chemical compositions of the sam-
ples in the solution are established with the help of inductively coupled plasma-optical
emission spectrometry (ICP-OES, PerkinElmer, USA).
Effect of Mass Ratio
Recoveries of Cr and Fe
As is shown in Fig. 1, the recoveries of chromium and iron decreased gradually

with the increase of mass ratio of chromite and tailings. The recoveries of chromium
and iron decreased from 95.79% and 98.06% to 87.84% and 90.27%, respectively.
Chromium exists in dense spinel of (Mg,Fe)(Cr,Al,Fe)2 O4 in chromite. However,
tailings have undergone two high temperature treatments, making the structure less
compact compared to chromite and a part of the chromium-containing phase has
transformed. In addition, according to the experiments of chromite ore reduction
by coke, Hu reported that the activity of the component MgCr2 O4 in the partially
reduced ore will decrease to a very low level, which makes further reduction very
difficult during the reduction process [15]. Therefore, tailings are easier to melt and
more reactive than chromite.
As is shown in Fig. 2, the content of chromium in high-carbon ferrochromium
increased from 29.78 to 52.01% with the increase of mass ratio. While the content of
Fig. 1 Relationship of mass

ratio and recoveries of Cr
and Fe
Fig. 2 Relationship of mass

ratio and content of Cr and
Fe
iron decreased from 59.98 to 37.72%. The content of iron in tailings reaches 31.08%,
and chromium is just 7.06%, but the content of chromium is 32.08%, and iron is only
18.75%, which caused the total content of iron to be high, and chromium to be low in
raw materials when the mass ratio is a low value. While the total content of chromium
increases, and iron decreases with the increase of mass ratio.
Concentration of Impurity Elements
Figure 3 shows the contents of impurity elements of high-carbon ferrochromium

at different mass ratios. It can be found that the content of C, P, and S elements
fluctuates in a small range. The content of Si element decreased from 1.79 to 0.10%
as the increase of mass ratio, which is due to the high content of Si in tailings
828 G. Wang et al.
Fig. 3 Relationship of mass ratio and impurity elements content
(7.29%) and low content of Si in chromite (1.00%). All impurity elements in high-
carbon ferrochromium meet the requirements of Chinese national standard (P, S <
0.06%, Si < 3.00%, C < 10.00%) [16].
Effect of Smelting Time
Figure 4 shows the recoveries of Cr and Fe at different smelting times. It can be

seen that both recoveries of Cr and Fe fluctuate in a small range, indicating that
the smelting time has a little influence on the recovery. The reason may be that the
reduction reaction in liquid phase can be fully carried out at such high temperature in
a short time. As is shown in Fig. 5, the content of chromium and iron in high-carbon
ferrochromium keeps stable at different smelting times, which means that smelting
time also has little influence on it. Hence, the smelting time of 15 min is appropriate
with considering the production cost.
Figure 6 shows the contents of impurity elements of high-carbon ferrochromium at

different smelting times. It can be found that the contents of harmful elements of P
and S elements fluctuate in a small range. The content of Si element increased from
0.81 to 1.93%, and C decreased from 8.77 to 7.21% with the increase of smelting
Fig. 4 Relationship of smelting time and recoveries of Cr and Fe
Fig. 5 Relationship of
smelting time and content of
Cr and Fe
time. All impurity elements in high-carbon ferrochromium meet the requirements of

Chinese national standard.
Effect of Reductants Amount
As shown in Fig. 7, the recoveries of Cr and Fe decreased from 90.18 and 91.49%
to 75.56 and 77.77% with the increase of reductant amount, respectively. A large
amount of gas will be generated when the graphite amount is added too much at
830 G. Wang et al.
Fig. 6 Relationship of smelting time and impurity elements content
reductant amount and
recoveries of Cr and Fe
high temperature, which will take away a part of raw materials. Moreover, when the
graphite amount exceeds the required amount for reducing chromium oxides and iron
oxides, surplus graphite will reduce other oxides such as SiO2 and MnO. It is also
detected that the content of Ti, Mn, and Si increased from 0.19%, 0.35%, and 0.81%
to 1.61%, 0.55%, and 6.32%, respectively, which not only caused the decrease of
recoveries of Cr and Fe, but also decreased the content of Cr and Fe in high-carbon
ferrochromium as shown in Fig. 8.
reductant amount and
content of Cr and Fe
Figure 9 shows the contents of impurity elements of high-carbon ferrochromium at

different reductant amounts. It can be seen that the contents of C, P, and S elements
fluctuate in a small range, and meets the requirements of Chinese national standard.
However, the content of Si element increased rapidly from 0.81 to 6.32%, which
highly exceeded the requirements of Chinese national standard.
Fig. 9 Relationship of reductant amount and impurity elements content

832 G. Wang et al.
Conclusions
The present study proposed a novel process to recover chromium and iron form
tailings by synergistic carbothermal reduction of chromite and the tailings to smelt
high-carbon ferrochromium. The experimental results demonstrate the feasibility of
this method. The recoveries of chromium and iron reached 95.79% and 98.06%,
respectively, and decreased with the increase of mass ratio. The smelting time has
little influence on the recoveries of chromium and iron. The recoveries of chromium
and iron decreased with the increase of reductant amount. The content of chromium
and iron in the high-carbon ferrochromium are between 47.00% to 52.00%, and
35.00 to 60.00%, respectively. The contents of impurity elements in the high-
carbon ferrochromium meet the expected requirements except the content of Si in
nos. 7 and 8. The content of chromium reached 52.01% in the high-carbon fer-
rochromium. The optimum smelting conditions are mass ratio at 5:1, smelting 10 min,
and C/O at 1.
China (Nos. 51604047 and 51974047).
References
1. Zhang XF, Fang DA, Song SZ, Cheng GJ, Xue XX (2019) Selective leaching of vanadium over
iron from vanadium slag. J Hazard Mater 368:300–307
2. Li M, Liu B, Zheng SL, Wang SN, Du H, Dreisinger DB, Zhang Y (2017) A cleaner vanadium
extraction method featuring non-salt roasting and ammonium bicarbonate leaching. J Clean
Prod 149:206–217
3. Karasgani MA, Rashchi F, Mostoufi N, Vahidi E (2010) Leaching of vanadium from LD
converter slag using sulfuric acid. Hydrometallurgy 102:14–21
4. Moskalyk RR, Alfantazi AM (2003) Processing of vanadium: a review. Min Eng 16:793–805
5. Ober JA (2017) Mineral commodity summaries 2017 54:202–205
6. Li HY, Wang K, Hua WH, Yang Z, Zhou W, Xie B (2016) Selective leaching of vanadium in
calcification-roasted vanadium slag by ammonium carbonate. Hydrometallurgy 160:18–25
7. Ji YL, Shen SB, Liu JH, Xue Y (2017) Cleaner and effective process for extracting vana-
dium from vanadium slag by using an innovative three-phase roasting reaction. J Clean Prod
149:1068–1078
8. Song WC, Li H, Zhu FX, Li K, Zheng Q (2014) Extraction of vanadium from molten vanadium
bearing slag by oxidation with pure oxygen in the presence of CaO. J Trans Nonferrous Met
Soc China 24:2687–2694
9. Wen J, Jiang T, Zhou WY, Gao HY, Xue XX (2019) A cleaner and efficient process for extraction
of vanadium from high chromium vanadium slag: Leaching in (NH4 )2 SO4 -H2 SO4 synergistic
system and NH4+ recycle. Sep Purif Technol 216:126–135
10. Zhang XF, Liu FG, Xue XX, Jiang T (2016) Effects of microwave and conventional blank
roasting on oxidation behavior, microstructure and surface morphology of vanadium slag with
high chromium content. J Alloy Comp 686:356–365
11. Li HY, Fang HX, Wang K, Zhou W, Yang Z, Yan XM, Ge WS, Li QW, Xie B (2015) Asyn-
chronous extraction of vanadium and chromium from vanadium slag by stepwise sodium
roasting-water leaching. Hydrometallurgy 156:124–135
12. Wen J, Jiang T, Xu YZ, Cao J, Xue XX (2019) Efficient extraction and separation of vanadium
and chromium in high chromium vanadium slag by sodium salt roasting-(NH4 )2 SO4 leaching.
J Ind Eng Chem 71:327–335
13. Liu B, Du H, Wang SN, Zhang Y, Zheng SL, Li LJ, Chen DH (2013) A novel method to extract
vanadium and chromium from vanadium slag using molten NaOH–NaNO3 binary system.
AIChE J 59:541–552
14. Ji YL, Shen SB, Liu JH, Yan SY, Zhang ZT (2017) Green and efficient process for extracting
chromium from vanadium slag by an innovative three-phase roasting reaction. ACS Sustain
Chem Eng 5:6008–6015
15. Hu X, Okvist L, Sundqvist S, Yang Q, Bjorkman B (2015) Thermogravimetric study on
carbothermic reduction of chromite ore under non-isothermal conditions. Ironmak Steelmak
42:409–416
16. People’s Republic of China standard GB/T 5683-2008, ferrochromium
Effect of Magnesium Flux
on Metallurgical Performance of Pellets
Kaikai Bai, Haibin Zuo, Qingguo Xue, Yajie Wang, Jiansheng Chen
and Jun Zhao
Abstract In blast furnace smelting, MgO can play a role in improving slag per-
formance. In the production process of pellets, the suitable MgO content is easy
to reduce the strength of pellets, but other metallurgical properties of pellet can be
improved. In this paper, dolomite is used as the main additive of MgO, and the effects
of 0, 1, 3, 8, and 11% different magnesium additive contents on the metallurgical
performance of pellets are studied. The results show that with the increase of mag-
nesium additive, the drop strength of the green ball increases, and it increases to 8.3
times when the magnesium additive content is 1.5%. The compressive strength of
the green ball first decreases and then rises. When the content is 1.5%, the highest
value of 1.5N was reached. The strength of the finished ball gradually decreased
to 1990N. The highest reduction degree increased to 80%, and reduction swelling
index decreased 10.02%. Meanwhile, the softening and smelting properties of mag-
nesium pellets are improved. The softening and smelting temperature range of single
magnesium pellets and mixed burden becomes narrow.
Keywords Magnesium flux · MgO · Pellet · Metallurgical performance
K. Bai · H. Zuo (B) · Q. Xue · Y. Wang · J. Chen · J. Zhao

Beijing 100083, China
e-mail: zuohaibin@ustb.edu.cn
K. Bai
e-mail: bk668666@163.com
Q. Xue
e-mail: xueqingguo@ustb.edu.cn
Y. Wang
e-mail: 18810634675@163.com
J. Chen
J. Zhao
e-mail: zjwitchina@163.com

https://doi.org/10.1007/978-3-030-36540-0_74
836 K. Bai et al.
Introduction
As a main iron-bearing burden for blast furnace ironmaking, the development speed
of pellet production in China has gradually exceeded the annual growth rate of blast
furnace ironmaking in recent years [1]. Pellet ore has many advantages compared to
sinter, such as small and uniform particle size, high cold compressive strength and
iron grade, good reducibility, and low environmental pollution. The metallurgical
properties of pellets play a crucial role in reducing coke ratio and increasing blast
furnace productivity [2]. However, the blast furnace charge structure is mainly com-
posed of sinter in China. But sinter production is the main source of pollution for
steel plants, and it has gradually received the attention of the Chinese environmental
protection department. Except for this reason, MgO easily forms glassy dicalcium
silicate and suppresses calcium ferrite formation during sinter. MgO also reduces the
formation of liquid phase, which increases the porosity resulting in reducing sinter
strength. The porosity in the sinter provides a channel for the reducing gas, which
increases the reduction index and decreases the low-temperature reduction degra-
dation. Therefore, the replacement of sinter production by pellets has become an
inevitable trend. Many researchers have studied the effect of adding different mag-
nesia fluxes on the metallurgical properties of pellets [3–7]. The purpose is to find
suitable magnesium additives to produce pellets with better metallurgical properties,
thereby reducing the dependence of blast furnaces on sinter. Dwarapudi studied the
effects of alkalinity and MgO content on the quality and microstructure of Indian
hematite. The result shows that the addition of MgO promotes the formation of more
low FeO slag and reduces the reduction stress [8]. In this paper, the metallurgi-
cal properties of magnesium flux pellets were mainly studied for Peruvian iron ore
concentrate. The softening and smelting experiments of pellets and high alkalinity
sinter were carried out to study the effect of magnesium pellets on the softening and
smelting properties of mixed burden.
Experimental
In this experiment, Peruvian iron ore concentrate, dolomite, and bentonite were,
respectively, used as iron raw materials, magnesium flux, and binder for experi-
mental research. Their components are presented in Table 1. Figure 1 and Table 2,
respectively, show the particle size distribution and their morphology of iron ore
concentrate and experimental raw material ratio and their quality. It can be seen from
particle size detection and scanning electron microscopy analysis. Iron ore concen-
trate particle size <200 mesh accounted for about 85%, and its particle structure is
compact and surface is smooth.
Table 1 Chemical composition of raw materials (%)
Composition TFe CaO SiO2 MgO Al2 O3 FeO Na2 O K2 O P S Fe2 O3 LOI
Iron ore concentrate 69.07 0.38 1.62 0.73 0.35 29.28 0.04 0.042 0.044 0.24 66.14 –
Dolomite 1.35 30.7 1.98 16.7 1.22 0.3 – 0.058 1.6 – – 41.9
Bentonite 5.19 1.88 47.1 1.74 12.9 0.43 – 1.08 – – 6.95 –
Effect of Magnesium Flux on Metallurgical Performance of Pellets
837
838 K. Bai et al.
6 100
Particle size distribution
5 Volume accumulation
80
Volume accumulation (%)

Volume density (%)
4
60
40
2
20
1
0 0
0.01 0.1 1 10 100 1000 10000
Particle size distribution (μm)
Fig. 1 Iron ore concentrate particle size and morphology of iron ore concentrate under SEM
Table 2 Experimental raw material ratio and their quality

Raw Iron ore Dolomite Bentonite Green pellet quality
materials concentrate (%) (%)
Program (%) Drop number Green
crushing
strength
(kg/pellet)
1 98 0 2 4 1.31
2 97 1 2 4.9 1.36
3 95 3 2 6.7 1.22
4 90 8 2 7.4 1.33
5 87 11 2 8.3 1.5
The experimental process mainly includes green pellets preparation, drying, pre-
heating, roasting, and finished pellets reduction. The mixture of different ratios was
balled in a 500 mm-diameter disc pelletizer, and 10–12.5 mm-diameter pellets were
screened as experimental samples. The experimental conditions for drying, preheat-
ing, and roasting: drying at 500 °C for 15 min,preheating at 950 °C for 15 min, and
roasting at 1250 °C for 20 min. Electrically heated hearth furnace is used to roast
pellet. The cold compression strength (CCS) of finished pellets, reduction swelling
index (RSI) ,and reducibility index (RI) were tested according to ISO4700, ISO4698,
and ISO4695-1984 (Fig. 2).
Effect of Magnesium Flux on Metallurgical Performance of Pellets 839
(1) (2)
(3) (4)
(5)
Pore
Fig. 2 Mineral phase microstructure
Table 3 Cold compression strength (CCS) of finished pellets

Program 1 2 3 4 5
CCS(N) 2110 2337 2560 2010 1990
Physical and Microstructured Analysis of Finished Pellets
Cold compression strength and X-ray diffraction (XRD) of finished pellets with dif-
ferent flux ratios are tested. Their tests, respectively, use universal testing machines
and DMAX-RB91-0459 X-ray diffractometer. The test results of compressive
strength and the analysis of XRD are shown in Table 3 and in Fig. 3. Figure 2 is
mineral phase microstructure.
Quality of Finished Pellets
Table 3 shows the cold compressive strength of finished pellets with varying dolomite
content. When dolomite content increased from 0 to 3%, the cold compressive
strength of pellets increased from 2110N to 2560N. With the further increase of
dolomite content, the compressive strength of pellets tends to decrease from 2560N
840 K. Bai et al.
16000 Mg 0.64 Fe2.36 O4

Fe 3 O4
14000
Fe 2 O3
12000 Ca 3 Mg(SiO4)2
Intensity (cps)
11%
10000
8%
8000
3%
6000
1%
4000
0%
2000
10 20 30 40 50 60 70 80 90 100
2θ/(º)
Fig. 3 X-ray diffraction of finished pellets
to 1990N. Because the addition of dolomite can gradually increase the strength of
the green pellets, the drop number and green crushing strength, respectively, increase
from 4 times/pellet to 8.3 times/pellet and from 1.31N to 1.5N. The strength of green
pellets lays the foundation for the process of roasting pellets. Therefore, with a small
amount of dolomite, the compressive strength of the finished pellets is still rising.
However, when the dolomite content is further increased, the dolomite absorbs heat
and decomposes in the process of pellet roasting, which tends to produce more pores,
as shown in Fig. 2, resulting in poor compactness of the pellet structure and decreas-
ing the compressive strength. Besides, the main component of dolomite is CaCO3
and MgCO3 , The radius of Mg2+ is similar to that of Fe2+ . During the oxidation
process, Mg2+ enters the magnetite crystal lattice and occupies the vacancies that
the diffusion of iron ions generate, which stabilizes the magnetite crystal lattice and
hinders the oxidation of Fe3 O4 . This leads to weakening of the Fe2 O3 microcrystal
bond inside the pellet [9]. Simultaneously, as MgO increases, the amount of liq-
uid phase decreases and the viscosity of the liquid phase increases, resulting in the
porosity increases, the volume shrinkage deteriorates, and the presence of irregularly
shaped pores to promote the stress concentrates [10]. Based on the influence of many
factors above, the compressive strength of the finished pellets is increasing and then
decreasing.
Reducibility
The reduction index of finished pellets determines the amount of indirect reduction
of the raw materials in the blast furnace resulting in lower coke rate and high produc-
tivity. Figure 4 is a schematic view of reduction furnace and softening and smelting
Fig. 4 Reduction furnace and softening and smelting furnace
furnace. Figure 5 shows the reduction index and reduction swelling index of mag-
nesium pellet, which indicates that with the increase of magnesium flux content, the
reduction index is greatly increased from 60 to 80%. On the contrary, the reduction
swelling index is gradually reduced from 21.06 to 10.02%. This is mainly because
MgO increased the melting point of slag [11]. The decrease of reduction swelling
index is due to the fact that the gradual increase of the magnesium flux content pro-
duces more stable MgO·Fe2 O3 during the roasting process. It can be seen from the
X-ray diffraction of Fig. 2 that the diffraction peak of magnesioferrite in the finished
pellets is gradually enhanced. Magnesioferrite is a high melting temperature slag.
Fig. 5 The reduction index 22

and reduction swelling index 21.06% 80%
80 Reduction index
of pellets
20
Reduction Swelling Index (%)
Reduction swelling index

18.41%
75
Reduction Index (%)
18
70
16
65 64% 14
61%
60%
60 11.28% 12
10.83%
55 10
55% 10.02%
0 1 3 8 11
Magnesium flux content (%)
842 K. Bai et al.
The formation of magnesioferrite, the stress caused by the transformation of Fe2 O3

to Fe3 O4 is reduced during the reduction process, thereby reducing the reduction
index of pellets [12]. In addition, the presence of MgO, the less amount of liquid
slag is formed, resulting in an increase of reduction index of the pellets [13].
Softening and Smelting Property
Table 4 shows the softening and smelting property of a single magnesium pellet.
Table 5 shows the smelting and softening of the mixture of magnesium pellets and
high alkalinity sinter. As shown in the results of Tables 4 and 5, the addition of
magnesia flux reduces the softening and melting temperature range, and narrows
the cohesive zone. Since MgO can form high melting point phase of MgFe2 O4
and MgSiO3 , t 10 and t s of pellets rises. t 1 and t 2 decreases from 101 °C and
Table 4 Softening and smelting property of magnesium pellet

Program t 10 t 40 t 1 t s (°C) Pm /Pa td t 2 S/(kPa°C)
(°C) (°C) (°C) (°C) (°C)
1 1109 1210 101 1293 337 * 9.8 1481 188 649.8
2 1115 1215 100 1290 349 * 9.8 1487 197 557.25
3 1129 1200 71 1260 791 * 9.8 1447 187 1357.96
4 1138 1221 83 1316 222 * 9.8 1448 132 222.50
5 1137 1225 88 1312 238 * 9.8 1482 170 313.21
Table 5 Softening and smelting property of the mixture of magnesium pellets and high alkalinity
sinter
Program t 10 t 40 t 1 t s (°C) Pm /Pa td t 2 S/(kPa°C)
(°C) (°C) (°C) (°C) (°C)
Sinter 1205 1327 122 1408 347 * 9.8 1532 124 360.91
90%S + 1206 1339 133 1421 322 * 9.8 1525 104 277.22
10%P
70%S + 1200 1307 107 1357 613 * 9.8 1476 119 656.57
30%P
50%S + 1182 1284 102 1398 176 * 9.8 1486 88 108.66
50%P
25%S + 1144 1266 122 1420 156 * 9.8 1483 63 65.44
75%P
Note t 10 —softening start temperature (°C), the burden lays contraction of 10%; t 40 —softening
end temperature (°C), the burden lays contraction of 40%; t 1 —melting zone interval (Td −
Tm ) (°C); t s —smelting start temperature; Pm —maximum differential pressure (Pa); t d —dripping
temperature (°C), the temperature at which dripping starts; t 2 —cohesive zone interval (Td −
TS ) (°C); S—permeability index (kPa °C)
188 °C to 88 °C and 170 °C. Pm and S obviously drop. In short, magnesium pellets
have better softening and smelting properties. According to softening and smelting
property of the mixture of magnesium pellets and high alkalinity sinter, although
magnesium pellet can decrease the t 10 , t 40 , t s, and t d , t 2 , Pm , and S are greatly
reduced. As the proportion of magnesium pellets blended into the mixed burden
increases, the minimum values of t 2 , Pm , and S can reach 63 °C, 156 * 9.8 Pa,
and 65.44 kPa °C, respectively. Therefore, the magnesia pellets can further improve
the gas permeability of the blast furnace production.
Conclusions
(1) In the study of magnesium pellets, magnesium flux can further improve the
quality of green pellets. The drop strength or crushing strength of green pellets
is significantly increased.
(2) More pores are produced by the decomposition of dolomite, and Mg2+ occu-
pies the Fe2+ lattice to hinder the oxidation of iron oxide, which reduces the
compressive strength of the finished pellets.
(3) Results of the reduction tests showed that the addition of magnesium flux pro-
motes the improvement of the reduction performance of the pellets. Reduction
index increases from 60 to 80% and reduction swelling index decreases from
21.06 to 10.02%.
(4) Magnesium flux forming a high melting point phase can greatly improve the
softening and smelting property of pellets. Magnesium pellets are beneficial to
improve the softening and smelting properties of mixed burden, which increase
the internal gas permeability of mixed burden.
Acknowledgements The authors gratefully acknowledge the financial support of the National
Natural Science Foundation of China (No. U1960205) and State Key Laboratory of Advanced
Metallurgy (No. 41618029).
References
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Metallurgical Newspaper, Beijing, China, 6 Aug 2013
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Effect of pellet basicity and MgO content on the quality and microstructure of hematite pellets.
3. Yadav US, Pandey BD, Das BK, Jena DN (2002) Influence of magnesia on sintering
characteristics of iron ore. Ironmaking Steelmaking 29(2):91–95
4. Frazer FW, Westenberger H, Boss KH, Thumm W (1975) The relationship between basicity
and swelling on reduction of iron ore pellets. Int J Miner Process 2:353–365
844 K. Bai et al.
5. Ling TK, Yang L, Lu WK (1983) The role of magnesia in iron ore pellets. Scand J Metall
4:166–176
Effect of MgO in the form of magnesite on the quality and microstructure of hematite pellets.
7. Panigraphy SC, Verstraeten P, Dilewijns J (1984) Influence of MgO addition on the mineralogy
of iron ore sinter. Metall Trans B 15:23–32
Effect of pyroxenite flux on the quality and microstructure of hematite pellets. Int J Miner
Process 96:45–53
9. Li J, Han CC, Yang AM, Liu WX, Zhang YZ, Liu LJ, Xiao H (2017) Effect of MgO on the
performance of magnesian fluxed pellets. Sintering and Pelletizing (China) 42(2):31–37
10. Zhang YP, Fu JY, Jiang T, Yang YB (2002) The influence of gangue contents on properties of
pellet. Sintering and Pelletizing (China) 27(4):11–14
11. Sugiyama T, Shirouchi S, Tsuchi O, Onoda M, Fujta I (1983) High temperature reduction and
softening properties of pellets with magnesite. Trans ISIJ 23:153–160
12. Li YR, Li JL, Zhang LG, Ren W, Yuan H (2009) Effects of additives on reduction swelling of
iron ore pellets. Iron Steel 44(10):14–17
13. Frill JJ, Erichson ES Jr (1980) Chemical, microstructure and reduction characteristics of
dolomite fluxed magnetite pellets. Metall Trans B 11:233–243
Study of Properties and Mineralization
of Cu–Ni Bearing Industry Sludge
Mudan Liu, Yong Liu, Zhiqiang Chen, Haozi Lv and Bo Li
Abstract The properties and mineralization behaviour of a heavy metal industrial

sludge with Cu and Ni content of 2.61 and 2.28% were investigated. The main phases
of the sludge are calcium hydrophosphate, gypsum and amorphous hydroxide, silica
gel. Heavy metals such as copper and nickel are dispersed in various physical phases,
and the mixture of calcium hydrogen phosphate is the main carrier of the valuable
metals nickel and copper, which are difficult to be extracted by physical methods.
Mineralization test results show that a concentrate with Cu content of 6.96% and Ni
content of 6.15% can be obtained by flotation of the sintered product under these
conditions: the dosages of bituminous, sodium sulfate, quartz and borax are 15%,
20%, 20% and 2% respectively, the sintering temperature is 1150 °C, the sintering
time is 60 min. The recoveries of copper and nickel in concentrate are 87.63% and
88.64%, respectively, and the Cu and Ni grade in tailing can reduce to 0.54% and
0.44%, respectively.
Keywords Industrial sludge · Low grade · Copper · Nickel · Mineralization ·

Flotation
Introduction
Cu–Ni bearing industrial sludge is a hazardous industrial waste, containing a large

amount of heavy metals such as copper and nickel. It is produced in the treatment pro-
cess of various wastewater discharged from metal manufacturing industries. Heavy
metal ions in sludge are easy to migrate to ecosystem when mixed with acidic ground
water, because sludge is unstable and easy to be decomposed. The sludge will pose
serious threat to the environment and human health, if not properly disposed of. On
M. Liu · Y. Liu (B) · Z. Chen · H. Lv · B. Li

Guangdong Institute of Resource Comprehensive Utilization, State Key Laboratory of Separation
and Comprehensive Utilization of Rare Metals, the Key Laboratory for Mineral Resources R&D
and Comprehensive Utilization of Guangdong, Guangzhou 510650, China
e-mail: gzly11@163.com

https://doi.org/10.1007/978-3-030-36540-0_75
846 M. Liu et al.
the other hand, the content of some heavy metals in sludge is much higher than that
in ores. Therefore, the sludge should be effective recycled.
At present, researches on the reutilization of Cu–Ni bearing industrial sludge
have been extensively carried out in the past decades, which generally can be clas-
sified into four aspects, namely solidification method, leaching method, thermal
treatment method and materialization method. Solidification is an important tech-
nology for the innocuous treatment of solid waste. The key point is to use solidifying
agent to sealed heavy metals in solidified body. However, this method occupies large
area, and the risky heavy metal that should be removed or separated still remains
in the product [1–3]. Leaching method is characterized by high adaptability to mate-
rials, high recovery of heavy metals, but the process is long, and a large amount
of waste water and slag is produced which needs further treatment [4–6]. Thermal
treatment method has remarkable capacity reduction effect. However, it requires high
grade heavy metals in sludge, and the treatment is high-energy consumption [7, 8].
Materialization technology usually prepares magnetic materials, modified plastics,
ceramics, bricks or producing cement, fertilizer, etc. from heavy metal sludge. Rele-
vant research is still in the exploratory stage, and it is difficult to guarantee the leaching
toxicity of heavy metals in products [9–11]. Therefore, the future research focus is
developing economic and reasonable technology to realize the efficient utilization
of heavy metal sludge.
The material used in this study is a heavy metal industrial sludge with copper and
nickel content less than 3%. The main physicochemical properties and morphology
of the heavy metals in the sludge are studied. Mineralization-beneficiation test is
carried out to obtain Cu–Ni bearing concentrate. The effects of the type and dosage
of flux, sintering temperature and sintering time on the mineralization of sludge are
studied. It is expected to provide a practicable strategy for reliable reutilization of
toxic industrial sludge.
Properties of the Materials
Chemical Composition
The main chemical components of the heavy metal industrial sludge are shown in
Table 1.
The reducing agent is bituminous coal, which is ground to the size of −0.1 mm,
and the industrial analysis results are shown in Table 2.
The sulfide agents include sodium sulfate, sodium sulphide and pyrite. Sodium
sulfate and sodium sulphide are chemically pure agent. The particle size of pyrite is
less than 0.1 mm, in which the S content is more than 42%.
The fluxes include sodium carbonate, quartz powder and sodium silicate. Sodium
carbonate and sodium silicate are analytical reagent. The particle size of quartz
powder is less than 0.1 mm and the content of SiO2 is more than 99%.
Table 1 Main component chemical analysis results of the industrial sludge
Component Ni Cu P2 O5 Al2 O3 SiO2 TFe Sn Zn CaO
Content (%) 1.88 2.61 14.42 8.17 4.5 3.12 0.32 0.42 16.98
Study of Properties and Mineralization of Cu–Ni Bearing …
847
848 M. Liu et al.
Table 2 Industry analysis results of the bituminous coal

Industry analysis (%) Cinder features
Mad Ad Vdaf FCad
11.64 3.60 41.27 43.49 2
It can be seen from Table 1 that the content of Cu and Ni of sludge is 2.61% and
1.88% respectively. The impurity elements are mainly Al2 O3 , SiO2 , CaO and P2 O5 ,
with corresponding content of 8.17%, 4.5%, 16.98% and 14.42% respectively. It can
be seen from Table 2 that both fixed carbon content and volatile matter of bituminous
coal are more than 41%, and the ash content is only 3.6%.
Material Composition and Occurrence Form
The material composition of heavy metal sludge is studied by optical microscope,

scanning electron microscope (SEM), X-ray diffraction analysis (XRD) and MLA
mineral automatic detection system, and the results are shown in Table 3.
Clearly, the heavy metal sludge is mainly composed of calcium hydrophosphate,
gypsum and amorphous aluminum hydroxide, iron hydroxide, nickel hydroxide,
chromate, calcium carbonate, silica gel, as well as a little feldspar, quartz, alloy and
mineral residues.
The microstructural characterization of the sludge is studied by optical microscope
and SEM. The results show that calcium hydrophosphate is the main carrier of
valuable metals such as nickel and copper, and valuable metals are also existed
in aluminum hydroxide, iron hydroxide, nickel hydroxide and tin hydroxide. The
existence of sludge is fine crystallization or amorphous substances, and all phases
are seriously mixed and contained each other. Copper and nickel are dispersed in all
phases. Thus, it is difficult to be extracted and recovered by physical methods.
Table 3 Main composition of heavy metal sludge

Calcium Gypsum Aluminum Chromate Iron Nickel
hydrogen hydroxide/silica colloid hydroxide hydroxide
phosphate gel colloid
35.77 20.60 18.89 5.81 9.77 1.49
Tin Quartz calcium feldspar alloya
hydroxide carbonate
0.19 1.36 2.05 0.51 0.21
a Alloy mainly includes iron chromium alloy, iron nickel alloy, iron zinc alloy, iron manganese
alloy
Study of Properties and Mineralization of Cu–Ni Bearing … 849
Fig. 1 Mineralization and Reducing agent Sludge Sulfurizing reagent, flux

beneficiation process flow of
heavy metal industry sludge
Mix and pelletization
Mineralization
Grinding
Flotation
Concentrate Tailing
Research Methods
The test method includes four main steps: pelletizing, mineralization, grinding and
flotation. The technological process is shown in Fig. 1.
Sulfurizing Agent Type Test
The sulfurizing reagent type test is carried out to examine the mineralization effect
of copper and nickel. Pyrite, sodium sulfide and sodium sulfate are selected as sul-
furizing reagent. The reducing agent is bituminous coal with the dosage of 15%,
the borax dosage is 2%, the flux including sodium carbonate and quartz, and their
dosages both are 7.5%, the sintering temperature is 1150 °C and the sintering time
is 60 min. The results are shown in Table 4.
It can be seen from Table 4 that most copper and nickel are enriched in concentrate,
and all the three sulfide agents can achieve sulfide mineralization of heavy metals
in sludge. The enrichment effect of copper and nickel in concentrate is better when
sodium sulfate or sodium sulfide is used as sulfurizing agent. When sodium sulfate
is used alone, the grade of copper and nickel in concentrate is higher by using single
sodium sulphate as sulfurizing agent, where the copper and nickel content is 5.88%
and 5.16% respectively, and the recoveries of copper and nickel are 72.88% and
73.21% respectively. So sodium sulfate is selected as the sulfurizing agent.
850 M. Liu et al.
Table 4 Influence of sulfurizing agent types on the mineralization effect of copper and nickel
Sulfurizing agent/w (%) Product Yielda Grade (%) Recovery (%)
Sodium Sodium Pyrite (%) Cu Ni Cu Ni
sulfide sulfate
10 0 0 Concentrate 32.11 5.73 4.96 70.49 69.85
Tailing 54.52 1.41 1.26 29.51 30.15
Feeding 86.63a 2.61 2.28 100.00 100.00
0 10 0 Concentrate 32.35 5.88 5.16 72.88 73.21
Tailing 53.38 1.33 1.14 27.12 26.79
Feeding 85.73 2.61 2.28 100.00 100.00
0 0 10 Concentrate 35.93 5.15 4.36 70.90 68.71
Tailing 51.69 1.47 1.38 29.10 31.29
Feeding 87.62 2.61 2.28 100.00 100.00
5 5 0 Concentrate 33.32 5.55 4.86 70.85 71.02
Tailing 52.90 1.44 1.25 29.15 28.98
Feeding 86.22 2.61 2.28 100.00 100.00
5 0 5 Concentrate 33.15 5.42 4.86 68.84 70.66
Tailing 54.49 1.49 1.23 31.16 29.34
Feeding 87.64 2.61 2.28 100.00 100.00
0 5 5 Concentrate 33.67 5.46 4.73 70.44 69.85
Tailing 53.07 1.45 1.30 29.56 30.15
Feeding 86.74 2.61 2.28 100.00 100.00
5 5 5 Concentrate 31.81 5.82 5.12 70.93 71.43
Tailing 55.13 1.38 1.18 29.07 28.57
Feeding 86.94 2.61 2.28 100.00 100.00
a Sintering process has burning loss, so the weight of concentrate and tailings is less than sludge
weight
Sulfurizing Agent Dosage Test
The sodium sulfate dosage test is carried out under the following conditions: the
bituminous coal dosage is 15%, the borax dosage is 2%, the sodium carbonate and
quartz dosage are both 7.5%, the sintering temperature is 1150 °C, and the sintering
time is 60 min. The results as shown in Table 5.
As observed from Table 5, when sodium sulfate dosage increases from 5 to 25%,
the enrichment effect of copper and nickel improves greatly, the grade of copper
and nickel in concentrate increases from 5.32% and 4.57% to 6.23% and 5.76%
respectively, and the recovery increases from 66.16% to 77.19% and from 65.06%
to 81.7% respectively. So the proper sodium sulfate dosage is about 20%.
Table 5 Influence of sodium sulfate dosage on the mineralization effect of copper and nickel
Sodium sulfate/w (%) Product Yielda (%) Grade (%) Recovery (%)
Cu Ni Cu Ni
5 Concentrate 32.46 5.32 4.57 66.16 65.06
Tailing 52.70 1.68 1.51 33.84 34.94
Feeding 85.16 2.61 2.28 100 100
10 Concentrate 32.35 5.88 5.16 72.88 73.21
Tailing 53.38 1.33 1.14 27.12 26.79
Feeding 85.73 2.61 2.28 100.00 100.00
15 Concentrate 32.57 5.96 5.28 74.37 75.43
Tailing 56.19 1.19 1.00 25.63 24.57
Feeding 88.76 2.61 2.28 100 100
20 Concentrate 32.49 6.08 5.34 75.69 76.10
Tailing 57.58 1.10 0.95 24.31 23.91
Feeding 90.07 2.61 2.28 100 100
25 Concentrate 32.34 6.23 5.76 77.19 81.70
Tailing 58.35 1.02 0.72 22.81 18.30
Feeding 90.69 2.61 2.28 100 100
weight
Flux Type Test
In sintering process, proper addition of some flux can reduce the melting point of
sintering material, promoting agglomeration and growth of metal grains, which is
benefit for flotation. Sodium carbonate, quartz and sodium silicate is chosen as the
flux. Flux type test is carried under these conditions: the bituminous coal dosage
is 15%, the sodium sulfate dosage is 20%, the borax dosage is 2%, the sintering
temperature is 1150 °C and the sintering time is 60 min. The results are shown in
Table 6.
The mineralization effect of sludge is negligible without flux. Copper and nickel
are not enriched significantly, and the flotation index is bad. The use of quartz, sodium
silicate or sodium carbonate all can improve the mineralization effect. In comparison,
the effect of sodium carbonate is weak, and the effect of sodium silicate or quartz is
significant. This is because SiO2 forms low melting point compound with CaO and
Al2 O3 in the mineralization process, which is conducive to the aggregation of grains.
When quartz dosage is 15%, the grade of copper and nickel in the concentrate reaches
6.42% and 5.73%, respectively, and the recoveries both exceeds 81%. Furthermore,
the grade of copper and nickel in tailings decreases to 0.83% and 0.65% respectively.
Considering comprehensively, it is advisable to select quartz as the flux.
852 M. Liu et al.
Table 6 Influence of flux type on the mineralization effect of copper and nickel
Flux type/w (%) Product Yielda Grade (%) Recovery (%)
Sodium Quartz Sodium (%) Cu Ni Cu Ni
carbonate silicate
0 0 0 Concentrate 41.72 3.56 3.14 56.91 57.46
Tailing 42.64 2.64 2.27 43.09 42.54
Feeding 84.36 2.61 2.28 100 100
15 0 0 Concentrate 37.12 4.89 4.23 69.55 68.87
Tailing 50.30 1.58 1.41 30.45 31.13
Feeding 87.42 2.61 2.28 100 100
0 15 0 Concentrate 33.12 6.42 5.73 81.47 83.24
Tailing 58.56 0.83 0.65 18.53 16.76
Feeding 91.68 2.61 2.28 100 100
0 0 15 Concentrate 33.23 6.38 5.58 81.23 81.33
Tailing 58.33 0.84 0.73 18.77 18.67
Feeding 91.56 2.61 2.28 100 100
7.5 7.5 0 Concentrate 32.49 6.08 5.34 75.69 76.10
Tailing 57.58 1.10 0.95 24.31 23.91
Feeding 90.07 2.61 2.28 100 100
7.5 0 7.5 Concentrate 32.87 5.71 4.93 71.91 71.07
Tailing 57.31 1.28 1.15 28.09 28.93
Feeding 90.18 2.61 2.28 100 100
0 7.5 7.5 Concentrate 32.87 6.41 5.62 80.73 81.02
Tailing 59.31 0.85 0.73 19.27 18.98
Feeding 92.18 2.61 2.28 100 100
5 5 5 Concentrate 32.81 6.22 5.54 78.19 79.72
Tailing 58.76 0.97 0.79 21.81 20.28
Feeding 91.57 2.61 2.28 100 100
weight
Flux Dosage Test
The flux dosage test is carried out under these conditions: the bituminous coal dosage
is 15%, the sodium sulfate dosage is 20%, the borax dosage is 2%, the sintering
temperature is 1150 °C and the sintering time is 60 min. The results are shown in
Table 7.
The mineralization effect of sludge is improved significantly when quartz dosage
increases from 5 to 20%, the copper and nickel grade in concentrate increases from
5.37% and 4.82% to 6.96% and 6.15% respectively, the recoveries of them increase
Table 7 Influence of flux dosage on the mineralization effect of copper and nickel
Quartz/w (%) Product Yield (%) Grade (%) Recovery (%)
Cu Ni Cu Ni
5 Concentrate 36.12 5.37 4.82 74.32 76.36
Tailing 54.23 1.24 0.99 25.68 23.64
Feeding 90.35 2.61 2.28 100 100
10 Concentrate 32.85 6.08 5.36 76.52 77.23
Tailing 58.57 1.05 0.89 23.48 22.77
Feeding 91.42 2.61 2.28 100 100
15 Concentrate 33.12 6.42 5.73 81.47 83.24
Tailing 58.56 0.83 0.65 18.53 16.76
Feeding 91.68 2.61 2.28 100 100
20 Concentrate 32.86 6.96 6.15 87.63 88.64
Tailing 59.48 0.54 0.44 12.37 11.36
Feeding 92.34 2.61 2.28 100 100
25 Concentrate 33.27 6.82 6.16 86.94 89.89
Tailing 60.12 0.57 0.38 13.06 10.11
Feeding 93.39 2.61 2.28 100 100
from 74.32% and 76.36% to 87.63% and 88.64% respectively. The copper and nickel
grade in tailings decreases from 1.24 and 0.99% to 0.54 and 0.44%. With further
addition of quartz, no significant change occurs with respect to the indexes. Therefore,
the proper quartz dosage is about 20%.
Sintering Temperature Test
Temperature is an important factor affecting the sintering effect. The sintering tem-
perature test is carried out under these conditions: the bituminous coal dosage is
15%, the sodium sulfate dosage is 20%, the borax dosage is 2%, the quartz dosage
is 20% and the sintering time is 60 min. The results are shown in Table 8.
When the temperature increases from 1050 °C to 1200 °C, the enrichment effect of
copper and nickel improves obviously, the grades of copper and nickel in concentrate
increase from 6.14% and 5.68% to 7.24% and 6.51% respectively, and recoveries of
them increase from 63.8 and 67.56% to 90.24 and 92.88% dramatically. Meanwhile,
the copper and nickel grade of tailings decrease from 1.41% and 1.1% to 0.45% and
0.29% respectively. So increasing sintering temperature can promote the melting of
sintering materials, thereby improving the migration ability of metal compounds,
which is benefit for the full mineralization of heavy metals in sludge. Considering
effect of mineralization and energy costs, the proper sintering temperature is selected
to 1150 °C.
854 M. Liu et al.
Table 8 Influence of sintering temperature on the mineralization effect of copper and nickel
Sintering temperature (°C) Product Yield (%) Grade (%) Recovery (%)
Cu Ni Cu Ni
1050 Concentrate 27.12 6.14 5.68 63.80 67.56
Tailing 67.23 1.41 1.10 36.20 32.44
Feeding 94.35 2.61 2.28 100 100
1100 Concentrate 33.24 6.18 5.76 78.71 83.97
Tailing 59.18 0.94 0.62 21.29 16.03
Feeding 92.42 2.61 2.28 100 100
1150 Concentrate 32.86 6.96 6.15 87.63 88.64
Tailing 59.48 0.54 0.44 12.37 11.36
Feeding 92.34 2.61 2.28 100 100
1200 Concentrate 32.53 7.24 6.51 90.24 92.88
Tailing 56.63 0.45 0.29 9.76 7.12
Feeding 89.16 2.61 2.28 100 100
Sintering Time Test
The sintering time test is carried out under these conditions: the bituminous coal
dosage is 15%, the sodium sulfate dosage is 20%, the borax dosage is 2%, the quartz
dosage is 20% and the sintering temperature is 1150 °C. The results are shown in
Table 9.
Table 9 Influence of sintering time on the mineralization effect of copper and nickel
Sintering time (min) Product Yield (%) Grade (%) Recovery (%)
Cu Ni Cu Ni
30 Concentrate 30.76 6.82 6.07 80.38 81.89
Tailing 59.75 0.86 0.69 19.62 18.11
Feeding 90.51 2.61 2.28 100 100
60 Concentrate 32.86 6.96 6.15 87.63 88.64
Tailing 59.48 0.54 0.44 12.37 11.36
Feeding 92.34 2.61 2.28 100 100
90 Concentrate 33.12 7.05 6.13 89.46 89.05
Tailing 55.30 0.50 0.45 10.54 10.95
Feeding 88.42 2.61 2.28 100 100
120 Concentrate 33.27 7.02 6.17 89.48 90.03
Tailing 54.57 0.50 0.42 10.52 9.97
Feeding 87.84 2.61 2.28 100 100
The mineralization effect of sludge is improved when sintering time increases

from 30 to 60 min. The copper and nickel grade in concentrate slightly increase
from 6.82 and 6.07% to 6.96 and 6.15%, and the recoveries of the two significantly
increase from 80.38% and 81.89% to 87.63% and 88.64% respectively. With the
further extension of sintering time, the indexes have no obvious change. So the proper
sintering time is 60 min, where the copper and nickel grade of tailings decrease to
0.54% and 0.44% respectively.
Conclusion
A heavy metal industrial sludge with Cu and Ni content of 2.61 and 2.28% is mainly
composed of calcium hydrophosphate, gypsum and amorphous hydroxide, silica gel.
Heavy metals such as copper and nickel are dispersed in various physical phases, and
the mixture of calcium hydrogen phosphate is the main carrier of nickel and copper.
Meanwhile, copper and nickel also exist in aluminum hydroxide, iron hydroxide,
nickel hydroxide and tin hydroxide, which are difficult to be extracted by physical
methods. Mineralization test results show that a concentrate with Cu content of
6.96% and Ni content of 6.15% can be obtained by the flotation of the sintered
product prepared under these conditions: the dosages of bituminous, sodium sulfate,
quartz and borax are 15%, 20%, 20% and 2% respectively, the sintering temperature
is 1150 °C, the sintering time is 60 min. The recoveries of copper and nickel in
concentrate are 87.63% and 88.64% respectively, and the Cu and Ni grade in tailing
can reduce to 0.54% and 0.44% respectively.
Acknowledgements This paper is supported by Guangdong public welfare research and capacity
building special project (2017A070702011, 2017A070701020), Guangdong collaborative innova-
tion and platform environment building special project (2017B090904035), Guangdong academy
of sciences innovation capacity building special project (2017gdascx-0109).
References
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containing sludge and its application effect of compound fertilizer. J Northwest Light Ind Univ
20(2):8–10
Utilization of Ground Sinter Feed
for Oxidized Pellet Production and Its
Effect on Pellet Consolidation
and Metallurgical Properties
Hongyu Tian, Jian Pan, Deqing Zhu, Dingzheng Wang and Yuxiao Xue
Abstract With a growing demand for high-grade pellet feeds as well as a con-
siderable increase in ore price, using cost-effective and high-grade sinter feeds for
oxidized pellets production becomes more attractive. In this paper, one hematite
concentrate from the wet grinding of a typical coarse sinter feed (GSF# ) was used
as raw material for manufacturing oxidized pellets. The effect of GSF# proportion
in ore mixture, up to 40 wt% on roasting and metallurgical properties of oxidized
pellets was investigated. Moreover, the effects of binary basicity and MgO content
were also studied. The results show that in the case of natural basicity and MgO
content, increasing the proportion of GSF# improves high-temperature softening–
melting properties of oxidizing pellets, whereas imposes negative impacts on pellet
strength as well as reduction swelling performance. The adverse effects can be elim-
inated by increasing binary basicity and MgO content to produce Mg-bearing fluxed
pellets, which indicates the feasibility of using high proportion of ground sinter feed
to manufacture high-quality oxidized pellets at low production cost.
Keywords Pellet · Sinter feed · Grinding · Consolidation · Metallurgical

properties
Introduction
Iron ore oxidized pellets are a high-quality burden for blast furnace with respect
to their irreplaceable superiority of good metallurgical properties, low energy con-
sumption, and less emission of harmful particulates and gases during the production
process [1]. According to recent statistics, the world output of oxidized pellets in
2017 has reached 0.44 billion tons, approximately 70% of which were used in blast
furnace [2, 3]. In modern ironmaking process, blast furnace has certain requirements
H. Tian · J. Pan (B) · D. Zhu · D. Wang · Y. Xue

Changsha, People’s Republic of China
e-mail: pjcsu@csu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_76
858 H. Tian et al.
regarding the chemical composition of slag. Generally, molten slag can achieve opti-
mal performance at slag basicity (CaO/SiO2 ) of 1.0–1.2, Al2 O3 content of 13–15 wt%
and MgO content of 10–12 wt%. Therefore, fluxed pellets and magnesia-containing
fluxed pellets are burdens charged into blast furnace. On the other hand, increasing
pellet basicity and MgO content can also improve the induration and metallurgical
properties of pellets [1, 4].
Magnetite and hematite concentrates are two primary pellet feeds for the pro-
duction of oxidized pellets. However, with the depletion and increasing purchase
cost of pellet feed, it is extremely attractive to produce oxidized pellets from more
cost-effective and coarse sinter feeds, and can hence reduce the production cost
and improve the market competitiveness [5]. Some hematite ore fines with high
iron grade, low silicon, and detrimental impurities, in accordance with the chemical
composition requirement of oxidized pellet are desirable raw materials. However, an
effective grinding process is necessary to pretreat coarse sinter feeds to obtain appro-
priate particle size distribution and specific surface areas [6, 7]. Many studies have
tried to deal with the problem through installation of a wet grinding process before
pelletizing [8]. It was found that increasing the proportion of ground sinter feed is
capable of improving the balling performance of ore mixture, which can reduce the
dosage of bentonite [9, 10]. However, there were no relevant studies regarding the
effect of addition of ground sinter feed on induration and metallurgical properties of
oxidized and Mg-bearing fluxed pellets at present.
In this study, one hematite concentrate from the wet grinding of a typical coarse
sinter feed (GSF# ) was used as raw material for manufacturing oxidized pellets. The
effect of GSF proportion in ore mixture, up to 40 wt% on roasting and metallurgi-
cal properties of oxidized pellets was investigated. Moreover, the effects of binary
basicity and MgO content were also studied.
Materials
Three imported iron ore concentrates (named GSF# , H# and M# ), collected from
Zhanjiang pelletizing plant, Zhanjiang, China, were tested for palletization. Ore
GSF# , a sinter feed which is coarse-grained, was beforehand wet-ground for pellet
production. Superior quality bentonite (B# ) was used as the blinder for improving
the ballability, and a limestone (L# ) and light-burned dolomite (D# ) was used for
adjusting the binary basicity and magnesium content of the pellets. The chemical
compositions, size distributions, and specific surface areas of raw materials are listed
in Tables 1 and 2, respectively. The X-ray diffraction pattern of iron ore concentrates
is shown in Fig. 1, and the microparticle morphology of iron ore concentrates is given
in Fig. 2.
Table 1 Chemical compositions of raw materials (%)
Sample TFe FeO SiO2 CaO MgO Al2 O3 K2 O Na2 O S P LOI*
GSF# 65.66 1.93 1.97 0.07 0.07 0.98 0.008 0.021 0.015 0.064 2.63
H# 66.63 0.32 3.59 0.07 0.01 0.50 0.010 0.003 0.005 0.017 0.16
M# 68.98 29.15 1.50 0.49 0.73 0.61 0.047 0.058 0.036 0.012 -2.81
B# 11.59 46.80 1.72 2.27 15.86 0.18 2.52 0.053 0.081 8.25
Utilization of Ground Sinter Feed for Oxidized Pellet …
L# / / 0.42 55.39 0.42 0.09 / / 0.011 0.003 42.54

D# 0.48 / 3.82 1.61 89.97 0.044 / / 0.034 0.041 2.76
*LOI—Loss on ignition at 1000 °C for 1 h in air
859
860 H. Tian et al.
Table 2 Size distributions and specific surface areas of raw materials

Sample Size distribution/mm/mass% SSA (cm2
+0.074 0.045–0.074 0.038–0.045 0.025–0.038 −0.025 g−1 )
GSF# 10.44 23.58 6.92 20.35 38.71 1680

H# 9.64 18.95 9.62 23.32 38.47 1110
M# 12.83 16.04 9.35 18.23 43.55 1599
B# 2.50 19.50 8.21 15.35 54.44 –
L# 1.04 56.11 12.15 17.37 13.33 4831
D# 9.18 12.61 5.29 14.31 58.61 7808
Fig. 1 X-ray diffraction pattern of iron ore concentrates
Fig. 2 Microparticles morphology of iron ore concentrates
As shown in Table 1 and Fig. 1, Ores GSF# , H# and M# all have high iron grade
and M# also has high FeO contents of 29.15 wt%, indicating that both GSF# and
H# are hematite and M# belongs to magnetite. Furthermore, they all have low alkali
metals, sulfur, and phosphorus. Simultaneously, the silica content in Ore GSF# is
1.97 wt%, which is much lower than that in the other hematite (H# ).
Utilization of Ground Sinter Feed for Oxidized Pellet … 861
From Table 2, the iron ore concentrates are all over 85 wt% passing 0.074 mm,
but the Ore H# has lower specific surface areas, only 1110 cm2 g−1 on account of
its particle morphology characteristic of smooth surface and regular corner angle
(Fig. 2). Bentonite (B# ), limestone (L# ), and light-burned dolomite (D# ) are all fine
enough for pelletizing with over 90 wt% passing 0.074 mm and own ultrahigh specific
surface areas.
Experimental Procedures
In the ore blends for testing, the proportion of GSF# varied in the range of 0 ~ 40 wt%
while that of M# was fixed at 20 wt% and that of H# changed accordingly. Green balls
were prepared from ore mixtures consisting of different proportions of GSF using a
laboratory disc pelletizer with a diameter of 1.0 m and a rim depth of 0.2 m, rotating
speed of 32 rpm and inclining angle of 47° to the horizon. Besides, the balling time
was fixed at 12 min, which was pre-determined in earlier tests. The moisture content
and bentonite dosage of green pellets are also fixed 8.8% and 0.75%, respectively,
while the dosage of limestone and light-burned dolomite varied depending on the
binary basicity and MgO content. The green balls of 10.0–12.5 mm were dried at
105 °C for 2 h in a drying oven for subsequent preheating and roasting tests.
To reveal the effect of different proportion (0–40 wt%) of ground sinter feed
(GSF# ) on the roasting performance and metallurgical properties of pellets, approxi-
mately 8–10 dry pellets were used for each test and roasted in an electric tube furnace
under typical heating and cooling profile. Specifically, the pellets were pre-heated
at 950 °C for 8 min and then roasted at 1260 °C for 15 min. The cold compressive
strength (CCS) of fired pellets was measured by an intelligent pellet compression
strength tester. The metallurgical properties of fired pellets include reduction swelling
index (RSI) and soft-melting performance, measured according to Chinese national
standards GB/T 13240-2018 and GB/T 34211-2017, respectively.
The chemical compositions of raw materials were determined by using a chemical
titration method. The crystalline phase compositions of iron ores were determined
using an X-ray diffractometer (XRD, D8 ADVANCE, BRUKER Ltd., Switzerland),
and was analyzed using MDI Jade 6.0 software. The microstructural analysis of the
fired pellets was performed using a Leica DMLP optical microscope.
862 H. Tian et al.
Effect of Proportion of Ground Sinter Feed on Oxidation

and Metallurgical Properties
Table 3 shows the effect of proportion of ground sinter feed (GSF# ) on oxidation
and metallurgical properties. As can be seen from that with the proportion of GSF#
increased from 0 to 50 wt%, the cold compressive strength of fired pellet (CCS)
decreased from 2910N·pellet−1 to 2339N·pellet−1 , and reduction swelling index
(RSI) increased from 17.07 to 23.37%, which imposed a certain negative impact
for pellet production. While it was beneficial for softening–melting properties as
the proportion of GSF# increased, which specifically included the increase of soft-
ening begin temperature (T 10 ), softening end temperature (T 40 ), softening–melting
begin temperature (T s ) and dropping temperatures (T d ) as well as the decrease of
softening range (T 1 ) and softening-melting range (T 2 ). In overall consideration,
the proportion of ground sinter feed was recommended at 40 wt% for subsequent
strengthening test.
Improvement of Oxidation and Metallurgical Properties

of Pellet
The effect of binary basicity and MgO content on oxidation and metallurgical prop-
erties was investigated and results are illustrated in Fig. 3 and Table 4, respectively.
With the increase of binary basicity, CCS of fired pellets improved obviously and
the reduction swelling index increased first then decreased to 21.67%, which was
still too high for the production of blast furnace, while the softening–melting prop-
erties were slightly improved than that of natural basicity pellets. In addition, with
the addition of light-burned dolomite to increase the content of MgO, CCS was
decreased dramatically, while the compressive strength of 2951N·pellet−1 can still
meet the requirements of large-scale blast furnace as the binary basicity of 0.8 and
Table 3 Effect of proportion of ground sinter feed on oxidation and metallurgical properties
Proportion CCS/N·pellet−1 RSI T 10 T 40 Ts Td T 1 T 2
(wt%) (%) (°C) (°C) (°C) (°C) (°C) (°C)
0 2910 17.07 981 1119 1159 1330 138 171
10 2844 18.18 989 1123 1164 1333 134 169
20 2803 18.83 1003 1133 1169 1338 130 169
30 2685 20.15 1009 1136 1175 1340 127 165
40 2517 21.10 1018 1142 1180 1343 124 163
50 2339 23.37 1021 1144 1183 1345 123 162
Fig. 3 Effect of binary

basicity and MgO content on
oxidation performance
MgO content of 1.0 wt%. Meanwhile, the reduction swelling decreased to 15.37%
and softening-melting properties were further optimized, illustrating the feasibility
of adding high proportion of ground sinter feed to the production of fluxed pellet
and magnesia-containing fluxed pellet for meeting the requirement of oxidation and
metallurgical properties.
Microstructure of the Fired Pellets
The microstructure of the fired pellets is shown in Fig. 4. It is clear that with increasing
the proportion of GSF# from 0 to 40% (Fig. 4a–c), the interconnection degree of
hematite crystalline grain obviously became worse and the size of crystal particle was
also smaller than before, resulting in larger porosity and poor compressive strength
of fired pellets. With the optimization of binary basicity, the pellet was evidently
denser with lower porosity than the former one. Furthermore, the calcium ferrite, a
low-melting-point liquid phase, existed in the gaps of hematite particles, which tends
to reshape the grains by dissolving their sharp corners into liquid phase, eliminate the
pores and consolidate particles into a denser structure to enhance the compressive
strength of fired pellets. As can be seen from Fig. 4e, the addition of light-burned
dolomite to adjust ω(MgO) accelerated the formation of magnesium ferrite, which
existed in the form of solid solution combining with hematite. The presence of
magnesium ferrite was beneficial to the reduction swelling and softening–melting
properties of fired pellets, but went against the consolidation of pellets.
864
Table 4 Effect of binary basicity and MgO content on metallurgical properties

Sample R ω(MgO) (%) RSI (%) T 10 (°C) T 40 (°C) T s (°C) T d (°C) T 1 (°C) T 2 (°C)
PA 0.06 0.17 21.10 1030 1158 1180 1343 128 163
PB 0.4 0.17 23.80 1039 1165 1189 1347 126 158
PC 0.8 0.17 21.67 1045 1070 1198 1353 125 155
PD 0.8 0.5 18.89 1056 1079 1210 1362 123 152
PE 0.8 1.0 15.37 1074 1094 1221 1372 120 151
H. Tian et al.
Fig. 4 Microstructure of fired pellets (H—Hematite; C—Calcium ferrite; M—magnesium ferrite;

P—Pore) a–c 0, 20 and 40 wt% GSF# in the mixture; d 40 wt% GSF# and basicity of 0.8; e 40 wt%
GSF# , basicity of 0.8 and MgO dosage of 1.0 wt%
Conclusions
One hematite concentrate from the wet grinding of a typical coarse sinter feed (GSF#)
was used as raw material for manufacturing oxidized pellets. The effect of GSF#
proportion in ore mixture, up to 40wt% on roasting and metallurgical properties
of oxidized pellets were investigated. Moreover, the effects of binary basicity and
MgO content were also studied. The results show that in the case of natural basicity
and MgO content, increasing the proportion of GSF# improves high-temperature
softening–melting properties of oxidizing pellets, whereas imposes negative impacts
on pellet strength as well as reduction swelling performance. The adverse effects can
be eliminated by increasing binary basicity and MgO content to produce Mg-bearing
fluxed pellets, which indicates the feasibility of using high proportion of ground sinter
feed to manufacture high-quality oxidized pellets at low production cost.
References
1. Fu JY, Zhu DQ (2005) Fundamentals technology and equipment of iron ore pelletization.
Central South University Press, Changsha
2. Kawatra SK, Halt JA (2011) Binding effects in hematite and magnetite concentrates. Int J
Miner Process 99(1–4):39–42
3. Qiu G, Jiang T, Fan X, Huang Z (2004) Effects of binders on balling behaviors of iron ore
concentrates. ISIJ Int 33(1):39–46
866 H. Tian et al.
4. Yang CC, Zhu DQ, Pan J (2016) Oxidation and induration characteristics of pellets made from
Western Australian ultrafine magnetite concentrates and its utilization strategy. J Iron Steel Res
Int 23(9):924–932
5. Pan J, Tian HY, Zhu DQ (2017) Particle size and wettability effect of ultrafine magnetite
concentrate on ballability. Chin J Eng 39(6):830–837
6. Wang DJ, Wu SL (2014) Estimation of oxidized pellets of a Brazilian hematite concentrate by
adding serpentine. ISIJ Int 54(4):715–720
7. Shen FM (2006) Proper MgO addition in blast furnace operation. ISIJ Int 46(1):65–71
8. Li XB, Li MT, Yi LJ (2018) Analysis of proportioning structure of Zhanjiang pelletizing plant.
Sinter Pelletizing 43(4):49–53
9. Ao AG, Yi LJ (2018) Production of grate-kiln pellet in Zhanjiang Iron and Steel Co., Ltd.
Baosteel Technol 1:34–37
10. Chen XL, Huang YS, Fan XH (2016) Oxidation roasting behavior and concretion properties
of vanadium-titanium magnetite pellet. J Cent South Univ 47(2):359–366
Slag-Metal Separation Behaviors
of Vanadium Titanomagnetite Metallized
Pellets
Jianjiang Xin, Nan Wang, Min Chen and Chen Chen
Abstract The effects of smelting temperature, slag basicity and smelting time on the
slag-metal separation and slag phase after smelting-separation for vanadium titano-
magnetite metallized pellets were investigated in the present work. The results show
that the increase of smelting temperature could decrease the viscosity of molten slag
and promote slag-metal separation. Meanwhile, the diffraction peaks intensity of
magnesia-alumina spinel in slag obviously increases. Within proper basicity range,
increasing slag basicity is conductive to decreasing the liquidus temperature and vis-
cosity of molten slag, and accelerating the settling velocities of iron drops. However,
further increasing slag basicity to 1.0 would cause abundant generation of perovskite
with high melting point in slag. Appropriate extension of smelting time contributes
to the coalescence and settlement of iron droplets, but excessive smelting time may
lead to the formation of TiC in slag, which is bad for the slag-metal separation.
Keywords Vanadium-bearing titanomagnetite · Metallized pellets ·

Smelting-separation · Slag phase
Introduction
Vanadium-bearing titanomagnetite ore is an important mineral resource containing

vanadium, titanium, and iron. It is widely distributed around the world mainly includ-
ing China, Russia, America, and North Africa [1]. Especially in the Panxi region of
China, the proven deposits account for more than 90% of total reserves in China
[2, 3]. At present, the blast furnace (BF) process is widely used by most countries
to produce hot metal containing vanadium and titanium-bearing blast furnace slag
[4–7]. However, the BF process needs to consume a large amount of expensive coke
and tends to have a low recovery of V less than 50%, resulting in a serious waste
of valuable elements [8]. Therefore, as an alternative route of conventional BF pro-
cess, direct reduction with subsequent smelting-separation of metallized pellet in
J. Xin · N. Wang (B) · M. Chen · C. Chen

School of Metallurgy, Northeastern University, Shenyang, Liaoning Province, China
e-mail: wangn@smm.neu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_77
868 J. Xin et al.
electric furnace has gained increasing attention to increase the utilization level of
valuable elements. Zheng [9] performed researches on the coal-based direct reduc-
tion of vanadium-titanium magnetite by using rotary kiln–electric furnace and found
that the metallization rate showed a remarkable increase within the low reduction
temperature, reduction time and carbon amount ranges. Sheng et al. [10] exam-
ined the effects of n(C)/n(Fe) ratio and temperature on the behaviors of vanadium
and chromium during coal-based direct reduction and magnetic separation, and the
recovery ratios of V, Cr, and Ti were only about 45.3%, 76.0%, and 20%, respectively.
The effects of magnetic intensity, reduction temperature, reduction time, carbon ratio,
and coal particle size on the efficiency of direct reduction and magnetic separation
were investigated by Chen et al. [11], and the recovery of V was concluded to be
75%. Tang et al. [12] studied the slag-metal separation behavior of high-chromium
vanadium-bearing titanomagnetite metallized pellet obtained from gas-based direct
reduction. With the optimized parameters, the recovery ratios of Fe, V, and Cr could
reach around 99%, 97%, and 92%, respectively.
So far, most of the research works are mainly focused on the direct reduction
of vanadium-bearing titanomagnetite ore and less attention is paid to the smelting-
separation of metallized pellets and relevant mechanisms. In the present study, the
effects of smelting parameters including smelting temperature, slag basicity and
smelting time on the slag-metal separation of metallized pellets were investigated.
Moreover, to elucidate the smelting-separation mechanism, the slag phase after
smelting-separation was also analyzed by X-ray diffraction.
Experimental
Raw Materials
The metallized pellets produced by the coal-based direct reduction were supplied by
a steel plant in China. The typical chemical composition and XRD analysis results
are listed in Table 1 and Fig. 1, and the metallization degree and original basicity
of the metallized pellets are 73% and 0.1, respectively. Besides, the metallized pel-
let contains 7.01% carbon used for further reduction of iron and vanadium oxides
and carburization during the smelting-separation process. The main phases in the
metallized pellet are Fe, Fe3 O4 , Fe2 O3 , FeTiO3 , FeV2 O4, and C.
Table 1 Chemical compositions of the metallized pellet (wt%)

TFe MFe SiO2 CaO MgO Al2 O3 MnO TiO2 V2 O5 S P C
61.12 44.39 9.18 1.00 2.64 4.66 0.53 6.76 0.30 0.11 0.11 7.01
Slag-Metal Separation Behaviors of Vanadium Titanomagnetite … 869

metallized pellet
Before performing the smelting-separation experiment, the metallized pellets were

crushed and mixed with pure additive CaO in a certain proportion to obtain the
required slag basicity (CaO/SiO2 (R) = 0.1–1.0). Next, the well-mixed powder was
pressed into a tablet and loaded into a corundum crucible (diameter × height: 30
× 40 mm). Then the crucible was placed into a high temperature electric resistance
furnace and heated to the desired high temperature (T = 1450–1600 °C) to separate
the molten metal and slag phases under high-purity argon gas flow. After a different
smelting-separation time (t = 20–60 min), the crucible was taken out rapidly and
quenched in liquid argon and the slag phase was analyzed by XRD.
Effect of Smelting Temperature
The influences of smelting temperature on the separation behavior between the slag
and metal phases of metallized pellet were studied under the conditions of slag
basicity of 1.0 and smelting time of 40 min. Figure 2 presents the photographs of
slag and metal phases under different smelting temperatures. It can be observed that
the metal phase can be separated well from the slag phase in the temperature range
of 1450–1600 °C, and no iron nugget is found among the slag phase, indicating that
the coalescence of the metallic iron droplets during smelting-separation process is
complete and the molten slag has a good fluidity.
870 J. Xin et al.
Fig. 2 Photographs of metal and slag phases after smelting-separation under different smelting
temperatures
During the smelting-separation process of metallized pellets, the generated metal-

lic iron droplets through reduction reaction undergo coalescence and settlement pro-
cesses, and the settling velocities of iron droplets inside the molten slag can be
described by Stokes equation [13], expressed by Eq. (2).
2gr 2 (ρm − ρs )
v= (2)
9η
where v is the settling velocities of droplet, (kg/m3 ); g is the acceleration due to

gravity, (m/s2 ); r is the droplet radius, (m); ρ m is the iron density, (kg/m3 ); ρ s is the
density of molten slag, (kg/m3 ); η is the viscosity of molten slag, (Pa·s). The slag-
metal separation could be promoted under higher smelting temperature. Increasing
smelting temperature would significantly decrease the viscosity and density of molten
slag discussed in the authors’ previous papers [14, 15], which improve the fluidity
of molten slag and decrease the settling resistance of the iron droplet.
The XRD spectra results of the slag phase after smelting-separation under dif-
ferent smelting temperatures are shown in Fig. 3. The main phases in the slag are
complex pyroxene (Al0.433 Ca0.968 Fe0.23 Mg0.578 O6 Si1.728 Ti0.059 ), perovskite (CaTiO3 ,
melting point of 1960 °C), and magnesia-alumina spinel (MgAl2 O4 , melting point of
2250 °C). With the increment of smelting temperature, the diffraction peaks intensity
Fig. 3 XRD patterns of the

slag phase after
smelting-separation under
different smelting
temperatures
of MgAl2 O4 obviously increases. This observation can be explained by the increas-

ing solubility of alumina in molten slag under higher smelting temperature, which
causes the erosion of corundum crucible by molten slag. In the subsequent vana-
dium extraction process, the conversion temperature between carbon and vanadium
is usually thought to be 1350–1400 °C [16]. In view of vanadium-extracting and
carbon-maintaining, lower temperature is recommended during the early smelting
stage, and the proper smelting temperature should be maintained at about 1450 °C.
Effect of Slag Basicity
Under the condition of different slag basicities, the photographs of slag and metal
phases after smelting-separation at 1450 °C for 40 min are presented in Fig. 4.
Although effective separation of slag and metal could be achieved, a few small iron
nuggets still exist in the slag with a basicity of 0.1, as presented in Fig. 4a. On the
872 J. Xin et al.
Fig. 4 Photographs of metal and slag phases after smelting-separation under different slag basicities
other hand, no iron nugget was found in the slag when the slag basicity was equal
or greater than 0.4, as shown in Fig. 4b–d. It is suggested that the coalescence of
metallic iron droplets is incomplete with the slag basicity of 0.1. With increasing the
slag basicity, the fluidity of molten slag was improved and coalescence and settlement
of metal droplets were accelerated in smelting-separation process. Consequently, the
iron nuggets in the slag finally almost vanish.
The XRD spectra of molten slag with different slag basicities are shown in Fig. 5.
It is revealed that with the slag basicities of 0.1 and 0.4, the slag phase contains only
pseudobrookite (Fe2 TiO5 ) that has not been reduced by carbon. With the increase
of slag basicity to 0.7, the diffraction peak of Fe2 TiO5 disappeared and complex
pyroxene and small amounts of CaTiO3 and MgAl2 O4 were detected in slag. When
slag basicity was further increased to 1.0, the CaTiO3 peak became stronger obvi-
ously. To verify the effect of slag basicity, the liquidus of SiO2 -CaO-TiO2 system was
calculated using FactSage 7.0, as shown in Fig. 6, and the liquidus temperature of
SiO2 –CaO–TiO2 system decreases gradually with the slag basicity increasing from
0.1 to 0.7. However, when the basicity is further increased to 1.0, the slag composi-
tion is located in CaTiO3 region and the liquidus temperature increases, which will
bring adverse effects on the smelting-separation of metallized pellets.
To investigate the influences of slag basicity on the fluidity of molten slag, the
viscosity of smelting-separation slag with different basicities was measured using a
rotating viscometer (RTW-10, China) by adjusting CaO contents. As shown in Fig. 7,
the viscosity of molten slag obviously decreases as the basicity increases from 0.1 to

slag phase after
different slag basicities
0.7 under temperature range of 1450–1600 °C. Meanwhile, further increasing basicity
from 0.7 to 1.0 did not have any obvious changes on the viscosity values, indicating
that excessive high temperature has a weak improvement for the fluidity of molten
slag in slag basicity range of 0.7–1.0. The optimum slag basicity is recommended at
about 0.7.
Effect of Smelting Time
The photographs of metal and slag phases after smelting-separation under conditions
of smelting temperature of 1450 °C and slag basicity of 0.7 are presented in Fig. 8.
The metal phase can be well separated from slag phase under different smelting
times. However, when the smelting time is 20 min, a few small iron nuggets were
found among the slag (Fig. 8a), indicating the incomplete coalescence of metallic
874 J. Xin et al.
Fig. 6 Liquidus of CaO–SiO2 –TiO2 system
Fig. 7 Effect of slag

basicity on the viscosity of
molten slag
iron droplets during smelting separation process due to short smelting time. As the
smelting time reached or exceeded 40 min, the coalescence of the metallic iron
droplets is improved and the iron nugget in slag vanishes (Fig. 8b–c). Figure 9 shows
the XRD patterns of smelting-separation slag obtained under different smelting times.
The basic phase is complex pyroxene in slag. Besides, it also contains a small amount
of CaTiO3 . It is found that there is no obvious change for slag phase as increasing
the smelting time. On the one hand, both the coalescence and settlement of metal
Fig. 8 Photographs of metal and slag phases after smelting-separation under different smelting
times

slag phase after
different smelting times
876 J. Xin et al.
droplets need to take certain times. On the other hand, excessive smelting time may
lead to the formations of TiC in slag, which would decrease the recovery of TiO2 in
slag and deteriorate the kinetics of slag-metal separation. Therefore, the appropriate
smelting time should be controlled to around 40 min.
Conclusions
The slag-metal separation and slag phase of vanadium-bearing titanomagnetite met-

allized pellets have been studied under different smelting temperatures, slag basicities
and smelting times in the present work, and the following main conclusions can be
drawn:
(1) Increasing smelting temperature would promote the slag-metal separation of
metallized pellets and decrease the viscosity of molten slag. In view of vana-
dium-extracting and carbon-maintaining in the subsequent vanadium extraction
process, the smelting temperature is recommended to be maintained at about
1450 °C.
(2) Within slag basicity range of 0.1–0.7, increasing slag basicity is conductive
to the smelting-separation between slag and metal phases and decrease of liq-
uidus temperature and viscosity of molten slag. However, further increasing
slag basicity to 1.0 would cause abundant generation of perovskite with high
melting point, which is bad for slag-metal separation. The proper slag basicity
should be about 0.7.
(3) Appropriate extension of smelting time contributes to the coalescence and set-
tlement of iron droplets inside molten slag, while the basic phase is complex
pyroxene in slag with basicity of 0.7. However, excessive smelting time may
lead to the formations of TiC in slag, which would deteriorate the separation
between slag and metal phases. The proper smelting time should be controlled
to 40 min.
Acknowledgements The authors gratefully acknowledge the National Natural Science Foundation
of China [Grant numbers, 51574066, 51774072, 51774073 and 51974080].
References
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Strengthening Sintering of Limonitic
Nickel Laterite by Substituting
Ferronickel Tailings for Sintering Fluxes
Deqing Zhu, Yuxiao Xue, Jian Pan, Congcong Yang, Zhengqi Guo,
Hongyu Tian and Dingzheng Wang
Abstract Ferronickel tailings, by-products from nickel laterite direct reduction-

magnetic separation process, are now stored up in large quantities with low utilization
because of the high MgO content. In this paper, ferronickel tailing with 5.82% Fe,
0.51% Ni, 44.08% SiO2, and 31.98% MgO was adopted to replace the traditional
Mg-bearing flux, i.e. serpentine. The laboratory pot sintering tests show that, this
new technique increases sinter productivity and tumble index by 4.12% and 10.63%,
respectively, and reduces solid fuel rate by 6.35%. The mineralogical study of product
sinter shows that the addition of ferronickel tailing contributes to the increase of the
amount of SFCA by 4.03%. Mg and Al elements were found to migrate into magnetite
grains to form three types of spinel solid solutions, i.e. (Fe, Mg)Fe2 O4 , Fe (Fe, Al)2 O4,
and (Fe, Mg)·(Fe, Al)2 O4 . Meanwhile, eutectic compound melts were obtained by
the co-melting of kirschsteinite (CaO·FeO·SiO2 ), monticellite (CaO·MgO·SiO2 ), and
fayalite (2FeO·SiO2 ).
Keywords Limonitic nickel laterite · Ferronickel tailing · Flux · Sintering

performance · Sintering mineralogical study
Introduction
Due to the increasing depletion of nickel sulfide ores and limited export of high-grade
lateritic nickel ores, the import volume of middle-low grade lateritic nickel ores,
especially limonitic nickel laterite, was expected to be increased gradually in China
[1–4]. With worldwide demand for stainless steel increased drastically, the efficient
utilization of abundant limonitic nickel laterite became increasingly important.
In China, the smelting processes of middle-low grade lateritic nickel ores mainly
included direct reduction-magnetic separation process, sintering-blast furnace pro-
cess, and rotary kiln-electric furnace smelting (RKEF) process [5–9]. Limonitic
D. Zhu · Y. Xue (B) · J. Pan · C. Yang · Z. Guo · H. Tian · D. Wang

School of Minerals Processing and Bioengineering, Central South University, Changsha, China
e-mail: yxxue@csu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_78
880 D. Zhu et al.
nickel laterite was used mostly to produce stainless steel at low cost by sintering-
blast furnace process due to its high total iron grade and low nickel grade [10, 11]. On
the other hand, in nickel laterite direct reduction-magnetic separation process, gen-
erally, the output ratio of ferronickel tailings came up to 70% of lateritic nickel ores
consumed [12]. Meanwhile, ferronickel tailings may not be used to produce high-
grade cement attributed to the high MgO content, and can only be stored up in large
quantities, which led to enormous waste of land and nickel resources and secondary
pollution of heavy metals [13]. Through previous chemical analysis, it was found
that ferronickel tailing possessed similar chemical composition with traditional Mg-
bearing flux such as serpentine, and, simultaneously, also contained about 0.5% Ni.
Hence, ferronickel tailing was possibly used to substitute for sintering flux, i.e. ser-
pentine, not only for environmental protection but also for sustainable development
of steel enterprises.
According to the reference [12], industrial tests of application of ferronickel tail-
ings in sintering production were carried out in a steel plant in China, but the strength-
ening mechanism of sintering was still unclear. In this study, the characterization of
ferronickel tailing and serpentine was compared and sinter pot tests were conducted
by ferronickel tailing substituting for serpentine, and mineralogy of product sinter
was investigated systematically to reveal the strengthening mechanism of sintering
of limonitic nickel laterite.
Experimental
Raw Materials
The raw materials include laterite ore, fluxes, and solid fuel. Limonitic nickel lat-
erite imported from Philippines, and ferronickel tailing, serpentine, burnt lime, and
anthracite supplied by Chinese steel mills, were used in the sintering pot test. Chem-
ical compositions of raw materials and industrial analysis of anthracite are docu-
mented in Tables 1 and 2, respectively. Limonitic nickel laterite, assaying 0.86%
Ni and 2.36% total Cr, is characterized by its relatively low iron grade, i.e. 45.09%
total iron, and high gangue mineral content of SiO2 , MgO, and Al2 O3 . And its LOI
reaches as high as 12.49%, due to high crystal water content. Anthracite, used as solid
fuel for sinters, has a high fixed carbon content of 79.66% and a calorific value of
28.27 MJ/kg, providing sufficient heat for the sintering process. Ferronickel tailing
possesses similar chemical compositions with serpentine such as high MgO and SiO2
contents. Meanwhile, 0.51% Ni and 0.59% total Cr were also analysed in ferronickel
tailing. All the raw materials possess low phosphorus content (<0.01%) and sulfur
content (<0.1%), which is good for stainless steel production at low cost.
Table 3 shows the size distributions of raw materials. Limonitic nickel laterite is
a coarse ore with 16.16% passing 0.5 mm. The particles of 1–3 mm fractions with
a content of 44.78% are defined as nuclear particles contributing to the granulation
Table 1 Chemical composition of raw materials (wt%)
Sample Fetotal Ni Crtotal SiO2 CaO Al2 O3 MgO P S LOI
Limonitic nickel laterite 45.09 0.86 2.36 5.70 0.12 4.50 5.58 0.001 0.011 12.49
Serpentine 4.64 – – 35.46 3.00 0.04 37.92 0.004 0.024 1.16
Ferronickel tailing 5.82 0.51 0.59 44.08 1.04 1.34 31.98 0.001 0.005 6.84
Strengthening Sintering of Limonitic Nickel Laterite …
Burnt lime 0.22 – – 4.20 82.07 1.18 1.81 0.009 0.091 10.42
Anthracite 0.75 – – 7.46 0.31 3.7 0.28 0.009 0.091 –
LOI: Loss on ignition
881
882 D. Zhu et al.
Table 2 Industrial analysis

Fixed carbon (FCdaf ) Ash (Ad ) Volatile (Vdaf ) LOI
of anthracite (wt%)
79.66 5.96 14.38 85.64
d: dry basis, daf: dry ash free basis
process [14]. Compared with serpentine, ferronickel tailing possesses a finer granu-
larity with 94.81% passing 1.0 mm, leading to better reaction activities in sintering.
The contents of −3 mm fractions of burnt lime, serpentine, ferronickel tailing, and
anthracite are all over 70%, agreeing with the requirement for sinter production.
Figure 1 presents the main phases identified in the serpentine and ferronickel tail-
ing. Serpentine mainly contains lizardite [Mg3 (Si, Fe)2 O5 (OH)4 ], calcite (CaCO3 ),
chlorite [Mg3 Si4 O10 (OH)2 ], forsterite (Mg2 SiO4 ), and olivine (Fe0.2 Mg1.8 SiO4 ). Fer-
ronickel tailing consists mainly of forsterite (Mg2 SiO4 ), quartz (SiO2 ), Mg-rich
forsterite [(Fe, Mg)SiO3 ], and three common polymorphs of MgSiO3 , i.e. clinoen-
statite, proto-enstatite, and enstatite. In analysis results above, we can find out that the
minerals compositions of serpentine and ferronickel tailing are different, probably
having different effects on sintering.
Limonitic nickel laterite as the only iron-bearing raw material and anthracite as the
high-quality solid fuel were adopted for sintering tests conducted at pilot scale pot.
The ratio of return fines, serpentine, and ferronickel tailing were maintained at 30%,
1.5%, and 1.5% on a total dry mix basis, respectively. Burnt lime was used not only as
binder to improve granulation of sinter mixture but also as a flux to adjust basicity of
sinter mixture. The detail methods of sintering process were similar to the reference
[15] except for some process conditions.
All raw materials in the required proportions were blended and mixed manually by
adding 15%–19% water, then loaded into a rolling drum with a diameter and length
of 600 mm and 1400 mm, respectively, and granulation of the sinter mixture was
carried out at 25 rpm for 5 min. Some of the granulated sinter mixture was sampled to
measure the moisture, size distributions, and permeability. Subsequently, about 30 kg
granulated sinter mixture was loaded into the sinter pot with 200 mm in diameter
and in 700 mm height. The ignition was controlled at 1100 °C for 1.5 min. The
ignition and sinter suction were strictly controlled at 6 kPa and 10 kPa, respectively.
The hot sinter was subjected to cooling for 5 min at 5 kPa. Finally, after cooling,
the productivity, yield, size distribution, and tumble index of sinter products were
measured. The sinter product samples were collected to determine their mineralogy
according to the reference [15].
Table 3 Size distributions of raw materials (wt%)
Sample Size/mm
+10 8−10 6.3−8 5−6.3 3−5 1−3 0.5−1 0.25−0.5 0.15−0.25 −0.15
Limonitic nickel laterite 2.80 3.30 4.06 6.00 22.35 44.78 6.43 5.83 1.17 3.28
Serpentine 0.00 0.00 0.00 0.00 7.86 47.29 10.01 13.89 4.07 16.88
Ferronickel tailing 0.00 0.00 0.00 0.01 1.62 3.56 17.75 25.78 8.08 43.20
Burnt lime 0.00 0.00 0.63 1.75 21.27 20.11 5.19 2.96 0.81 47.29
Anthracite 1.68 1.58 1.70 3.70 18.08 15.23 15.46 14.10 5.22 23.25
883
884 D. Zhu et al.
Fig. 1 X-ray diffraction patterns of serpentine and ferronickel tailing
Sintering Performance
As the base case test, traditional sintering test using serpentine as sintering flux was
carried out, the moisture and coke levels for sintering were optimised. And the optimal
sintering results were compared with those of the new sinter process with ferronickel
tailing substituted for serpentine, as shown in Table 4. It can be seen that, with the
new sintering process adding 1.5% ferronickel tailing, sinter productivity, and tumble
index were increased from 0.97 t·m2 ·h−1 and 42.60% to 1.01 t·m2 ·h−1 and 47.13%,
respectively, and solid fuel rate was decreased dramatically from 172.57 kg·t−1 to
161.61 kg·t−1 , indicating that substituting ferronickel tailing for serpentine was a
very effective way to improve sintering performance of limonitic nickel laterite.
Table 4 Comparison of sintering indices obtained by different sintering processes of 100%

limonitic nickel laterite (8.5% anthracite, 17.5% moisture, and 1.4 basicity of sinters)
Blends Sinter Flame Tumble Productivity/t·m2 ·h−1 Solid R
basicity speed/mm·min−1 index/% fuel/kg·t−1
1.5% 1.4 34.87 42.60 0.97 172.57 0.99
serpentine
1.5% 1.4 35.32 47.13 1.01 161.61 0.95
ferronickel
tailing
R: Return fine balance
Strengthening Sintering of Limonitic Nickel Laterite … 885
Mineralogy of Product Sinter
Figure 2 compares X-ray diffraction patterns of product sinter with the addition of
1.5% serpentine and ferronickel tailing, respectively. As 1.5% serpentine was added,
product sinter consisted of two solid phases, i.e. hercynite [(Fe, Mg)·(Fe, Al)2 O4 ] and
wustite (FeO), and four liquid binding phases, i.e. kirschsteinite (CaO·FeO·SiO2 ),
monticellite (CaO·MgO·SiO2 ), fayalite (2FeO·SiO2 ), and silico-ferrite of calcium
and alumina (SFCA). Hercynite, as the main compound, was formed by the immi-
gration of Mg and Al elements entering into the magnetite lattice. The diffraction
peaks intensity of kirschsteinite (CaO·FeO·SiO2 ) and silico-ferrite of calcium and
alumina (SFCA) were increased in product sinter with ferronickel tailing substi-
tuted for serpentine. Meanwhile, the diffraction peak of wustite (FeO) disappeared
and the diffraction peaks intensity of hercynite [(Fe, Mg)·(Fe, Al)2 O4 ] and fayalite
(2FeO·SiO2 ) remained substantially unchanged. The XRD results suggest that sub-
stituting ferronickel tailing for serpentine has a favorable impact on the formation
of silico-ferrite of calcium and alumina (SFCA), contributing to the improvement of
sinter strength.
Figure 3 illustrates the microstructure of product sinter with the addition of 1.5%
serpentine. The large size and irregular pores with thinner wall existed in sinter and
mesopores grew up and captured neighbor mesopores, leading to the short crack and
connection of micropores, as shown in Fig. 3-1, which was adverse to sinter strength.
Three types of eutectic compound melts, i.e. K-1[CaO·FeAl2 O4 ·SiO2 ], K-2[CaO·(Fe,
Mg)O·SiO2 ], and K-3[CaO·(Fe, Mg)Al2 O4 ·SiO2 ], acting as the main binder phases in
sinter, were formed by the co-melting of kirschsteinite (CaO·FeO·SiO2 ), monticellite
(CaO·MgO·SiO2 ), and fayalite (2FeO·SiO2 ) in different proportions illustrated in
Fig. 3a–c. Hercynite, characterized into three categories, i.e. (Fe, Mg)Fe2 O4 , Fe (Fe,
Al)2 O4, and (Fe, Mg)·(Fe, Al)2 O4 , due to the substitution of Mg and Al elements,
Fig. 2 X-ray diffraction patterns of product sinter at 1.4 basicity

886 D. Zhu et al.
H-(Fe, Mg)·(Fe, Al)2O4, H-1- Fe (Fe, Al)2O4, H-2- (Fe, Mg)Fe2O4, W-Wustite, K-1-
CaO·FeAl2O4·SiO2, K-2- CaO·(Fe, Mg)O·SiO2, K-3- CaO·(Fe, Mg)Al2O4·SiO2, SFCA-silico-ferrite
of calcium and alumina, N- NiFe2O4, C-(Fe, Mg)·(Cr, Fe, Al)2O4, P-Pore
Fig. 3 Microstructure of product sinter at 1.4 basicity (1.5% serpentine)

disseminated scatteredly in the three types of eutectic aforementioned with granular

and tabular. Meanwhile, silico-ferrite of calcium and alumina (SFCA) was found
formed near the edge of pores existing as a porous melting corrosion structure (Fig. 3-
2 and -d). The strength of this type of SFCA was low. A fraction of wustite was also
observed near the edge of pores, as shown in Fig. 3-1. In addition, small quantity of
nubbly chromite spinel [(Fe, Mg)·(Cr, Fe, Al)2 O4 ] and small crystals of nickel-ferric
spinel (NiFe2 O4 ) in form of approximately scattered spots existed in sinter (Fig. 3b,
c) (Table 5).
Figure 4 demonstrates the microstructure of product sinter with 1.5% ferronickel
tailing. The pores in sinter existed as regular round or elliptical structures and the
connectivity with each other was decreased with ferronickel tailing substituted for
serpentine (Fig. 4-1). Hence, although sinter still presented a macroporous thin-
walled structure, sinter strength was obviously improved. Figure 3-2 and -d shows
that substituting ferronickel tailing for serpentine was favorable for the formation
of fine acicular and acicular silico-ferrite of calcium and alumina (SFCA), indicat-
ing a higher sinter strength obtained. Meanwhile, wustite disappeared leading to
an increase of liquid binding phases, which was advantageous to the improvement
of sinter strength. The distribution of other binding phases was not quite different
(Table 6).
Table 7 presents minerals composition and porosity of product sinter. As fer-
ronickel tailing substituted for serpentine with the content of 1.5%, the porosity was
decreased by 1.05%, and the content of SFCA was increased by 4.04%. Hence,
substituting ferronickel tailing for serpentine was in favor of the improvement of
structures of pores, sinter porosity, and the formation of high strength liquid binding
phase, i.e. SFCA, furthermore, leading a significant increase of sinter strength.
Conclusion
(1) Ferronickel tailing possesses similar chemical compositions with serpentine

such as high MgO and SiO2 contents, meanwhile, assaying 0.51% Ni and 0.59%
total Cr. Substituting ferronickel tailing for serpentine to strengthen sintering of
limonitic nickel laterite is feasible.
(2) As ferronickel tailing substituted for serpentine with the content of 1.5%, pro-
ductivity and tumble index of product sinter were increased by 4.12% and
10.63%, respectively, and solid fuel rate was decreased by 6.35%. The sintering
performance of limonitic nickel laterite was significantly improved.
(3) Substituting ferronickel tailing for serpentine was favorable for the formation
of regular round or elliptical pores and fine acicular and acicular silico-ferrite
of calcium and alumina (SFCA), leading to an increase of the amount of SFCA
by 4.03% and a reduction of sinter porosity by 1.05%, effectively improving
mineralogical constitution and quality of product sinter.
888
Table 5 EDS analysis results of product sinter at 1.4 basicity (1.5% serpentine)
Area no. Elemental compositions/(atomic conc,%) Mineral phases
Fe Cr Ni Mg Al Si Ca O
1 42.51 – – 2.10 – – – 55.39 (Fe, Mg)Fe2 O4
2 46.50 – – 2.52 2.61 0.31 0.44 47.62 (Fe, Mg)·(Fe, Al)2 O4
3 10.21 9.75 – 5.16 13.98 – 0.14 60.75 (Fe, Mg)·(Cr, Fe, Al)2 O4
4 7.47 0.10 0.06 1.94 0.38 13.26 12.94 63.86 CaO·(Fe, Mg)O·SiO2
5 5.34 0.10 0.03 – 6.87 13.67 16.00 57.98 CaO·FeAl2 O4 ·SiO2
6 46.09 0.46 0.66 – 2.73 – – 50.06 Fe (Fe, Al)2 O4
7 6.05 0.19 0.04 2.36 3.34 15.30 14.20 58.51 CaO·(Fe, Mg)Al2 O4 ·SiO2
8 32.00 – 21.03 – 3.21 3.76 2.78 37.22 NiFe2 O4
9 24.85 0.02 0.17 0.54 1.65 3.72 17.69 51.37 SFCA
D. Zhu et al.
H-(Fe, Mg)·(Fe, Al)2O4, H-1- Fe (Fe, Al)2O4, H-2- (Fe, Mg)Fe2O4, K-1- CaO·FeAl2O4·SiO2, K-2-
CaO·(Fe, Mg)O·SiO2, K-3- CaO·(Fe, Mg)Al2O4·SiO2, SFCA-silico-ferrite of calcium and alumina, N-
NiFe2O4, C-(Fe, Mg)·(Cr, Fe, Al)2O4, P-Pore
Fig. 4 Microstructure of product sinter at 1.4 basicity (1.5% ferronickel tailing)

890
Table 6 EDS analysis results of product sinter at 1.4 basicity (1.5% ferronickel tailing)
Area no. Elemental compositions/(atomic conc,%) Mineral phases
Fe Cr Ni Mg Al Si Ca O
1 36.04 – – 2.45 3.54 – – 57.97 (Fe, Mg)·(Fe, Al)2 O4
2 41.67 – – 2.37 0.36 – 0.34 55.26 (Fe, Mg)Fe2 O4
3 6.99 – – 3.21 1.52 13.16 14.61 60.11 CaO·(Fe, Mg)Al2 O4 ·SiO2
4 36.04 – – 0.45 5.54 – – 57.97 Fe (Fe, Al)2 O4
5 7.59 – – – 8.09 8.36 15.42 60.54 CaO·FeAl2 O4 ·SiO2
6 7.78 – 0.64 4.11 0.49 12.86 15.18 58.93 CaO·(Fe, Mg)O·SiO2
7 11.73 16.41 – 3.92 6.85 0.58 – 60.51 (Fe, Mg)·(Cr, Fe, Al)2 O4
8 35.20 – 6.24 1.06 2.51 0.40 0.46 51.84 NiFe2 O4
9 16.66 0.20 – – 7.44 0.59 21.07 54.04 SFCA
D. Zhu et al.
Table 7 Minerals composition and porosity of product sinter at 1.4 basicity (%)
Blends Hercynite Chromite spinel Nickel-ferric spinel Wustite Eutectic compounds SFCA Porosity
H H-1 H-2 K-1 K-2 K-3
1.5% serpentine 10.63 23.45 30.12 2.56 1.09 5.75 2.96 4.75 13.55 5.14 49.97
1.5% ferronickel 15.14 21.81 29.94 2.55 1.05 – 2.13 3.89 14.32 9.17 48.92
tailing
891
892 D. Zhu et al.
Acknowledgements Financial support from the Major Project of Master Alloy Manufacture for
Heat Resistant Stainless Steel Production No. (AA18242003) is sincerely acknowledged. We are
also thankful to the Analytical and Testing Center of Central South University, which supplied us
the facilities to fulfil the measurement.
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8. Zhu DQ, Cui Y, Vining K (2012) Upgrading low nickel laterite ores using selective reduction
followed by magnetic separation. Int J Miner Process 106:1–7
9. Pan LT, Yang J, Xu YB (2013) Industrial test of laterite nickel ore sintering proportioned with
additives. Sinter Pelletizing 38(2):25–27 (In Chinese)
10. Lv XW, Bai CG, He SP (2010) Mineral change of philippine and indonesia nickel Lateritic ore
during sintering and mineralogy of their sinter. ISIJ Int 50:380–385
11. Zhang T, Zuo HB, Zhang JL (2013) Analysis of application of high proportion laterite nickel
ore in sinter production. Sinter Pelletizing 38(2):6–9 (In Chinese)
12. Pan LT, Li LF, Cai XX (2015) Industrial test of application of ferro-nickel tailings in sintering
production. Sinter Pelletizing 40(1):42–44 (In Chinese)
13. Chen AA (2012) A resource utilization technology of Josephinite tailing. Master thesis, South
China University of Technology (In Chinese)
14. Zhu DQ, Zhou XL, Pan J (2016) Granulation behaviour of specularite fines in ferrous sinter
mixtures. Miner Process Extr Metall 125(3):172–177
15. Zhu DQ, Guo ZQ, Pan J (2016) A study of pre-briquetting granulation sintering of the mixtures
with high ratio of Brazilian specularite concentrate. Ironmak Steelmak 43(10):1–9
Part XI
Poster Session
Effect of Mechanical Carbon Coating
on Reduction of Magnetic Ore Powder
Suju Hao, Tianhao Sun, Wufeng Jiang and Yuzhu Zhang
Abstract The growth of iron whiskers during the reduction of iron ore fines is the
main cause of fluidized bed bond loss. In this paper, the influence of mechanical
carbon coating on the reduction behavior of magnetic ore powder is studied in detail.
Firstly, the reduction kinetics of bituminous coal-coated magnetic ore powder and
anthracite-coated magnetic ore powder under different conditions is studied. Then,
the influence of reduction temperature on the surface morphology of bituminous
coal-coated magnetic ore powder and anthracite-coated magnetic ore powder after
reduction is studied. The scanning electron microscope results show that the carbon
source of bituminous coal-coated magnetite ore powders can effectively inhibit the
formation of iron whiskers in the reduction process of iron ore powders.
Keywords Mechanical carbon coating · Magnetic ore powder · Iron whiskers ·

Reduction
Introduction
Compared with blast furnace iron-making process, non-blast furnace iron-making

process is characterized by short process, no dependence on coke and environmental
friendliness. Fluidized reduction is a kind of non-blast furnace iron-making process,
which uses CO, H2 reducing gas direct reduced iron ore powder at high temperature,
the contact condition of gas and solid two phases, has high mass transfer, heat transfer
efficiency, temperature uniformity, etc., and get rid of the iron ore powder sintering
process, so the energy consumption is low, is a development prospect of iron-making
process, and thus is valued in the metallurgical industry. However, in the process of
fluidization and reduction, iron ore powder is prone to bond and flow loss, which
S. Hao · T. Sun · W. Jiang (B) · Y. Zhang

College of Metallurgy and Energy, North China University of Science and Technology, Ministry
of Education Key Laboratory of Modern Metallurgy Technology, Tangshan 063210, Hebei, China
e-mail: jwufeng@163.com
S. Hao
e-mail: sujuh@sina.com

https://doi.org/10.1007/978-3-030-36540-0_79
896 S. Hao et al.
leads to production interruption and failure to continue. Therefore, bond and flow loss
is an important bottleneck in the application of fluidized bed reduction process. The
production of iron whisker in the process of fluidized bed reduction is one of the main
reasons for fluidized bed loss [1–6]. Pretreatment of iron ore powder by cladding
is an effective method to restrain the growth of iron crystal whiskers. At present,
the surface of iron ore powder is mainly coated with nitrate [7] and phosphate [8],
which is called chemical cladding. Because these salts are harmful to the subsequent
reduction process, it is urgent to find a new method for the pretreatment of iron ore
powder. In this paper, magnetic ore powder and coal powder are mixed and ground
to make the coal powder coated on the surface of iron ore powder, which is called
mechanical carbon coating. In this paper, the influence of mechanical carbon coating
on the reduction behavior of magnetic powder is studied in detail.
Experimental
Raw Materials
The raw materials used in the experiment are magnetite powder, bituminous coal,
and anthracite. The initial particle size is <0.15 mm. First, the magnetite powder,
bituminous coal, and anthracite were placed in a constant temperature oven, dried
at 100 °C for 4 h until the water was completely evaporated. In order to eliminate
the influence of volatiles in bituminous coal and anthracite on the experiment, the
bituminous coal and anthracite coal were firstly put into a high temperature tube
furnace at 1100 °C for 2 h, and the obtained product was still called bituminous coal
and anthracite. Then, dried magnetite powder and the dry-distilled bituminous coal
or anthracite are placed in the grinding machine for grinding for a certain period of
time, and then the excess bituminous coal and anthracite that have not been coated
are removed by a magnet. Thereby, the bituminous coal-coated magnetite powder
(BCMP) and the anthracite-coated magnetite powder (ACMP) were prepared.
Experimental Equipment
The experimental device is a T-1600MT high temperature vacuum tube furnace.

The heating elements are U-shaped silicon molybdenum rod. The temperature of
the furnace was measured by double platinum and rhodium thermocouple. Through
the adjustable temperature control program to control the heating rate, the control
accuracy is ±1 °C.
Effect of Mechanical Carbon Coating on Reduction … 897
Analysis of Weight Loss Curve
The weight loss rate curves of BCMP and ACMP at different heating rates in N2
atmosphere (5, 10, 15, 20 K/min) are shown in Fig. 1. Overall, the different heating
rates have little effect on the final result of the weight loss rate. The weight loss rate
of BCMP is in the range of 57.3 ~ 62.1%, and the weight loss rate of ACMP is in
the range of 60 ~ 63.2%.
Calculation of Reaction Activation Energy
The data of TG-DSC curves of BCMP and ACMP were processed by FWO extrap-
olation method, and the initial activation energy of BCMP and ACMP was obtained
by linear fitting of logβ and 1/T. Figure 2 is a fitting result of a conversion rate at
0.03–0.1 under low temperature, and Fig. 3 is a fitting result of a conversion ratio at
0.1–0.9. From the figure, the fitting result is quite close to the experimental results.
The activation energy of the corresponding conversion rate at a certain temperature
can be calculated according to the slope of the fitted straight line, as shown in Fig. 4. It
can be seen from the figure that the reaction activation energy of the ACMP is greater
than the reaction activation energy of the BCMP. When the conversion rate is less than
0.4, the activation energy of ACMP increases with the increase of conversion rate.
When the conversion rate is 0.4, the maximum value is 1215.22 kJ/mol. When the
conversion rate is 0.4 ~ 0.6, the activation energy is greatly reduced as the conversion
rate increases. When the conversion rate is greater than 0.6, the activation energy
increases with the increase of the conversion rate, but the change range is not large.
(a) BCMP (b) ACMP
Fig. 1 Weight loss rate curves of BCMP and ACMP

898 S. Hao et al.
(a) BCMP (b) ACMP
Fig. 2 Relationship between logβ and 1/T of TG in low conversion zone
(a) BCMP (b) ACMP
Fig. 3 Relationship between logβ and 1/T of TG in the high conversion zone
The reaction activation energy of BCMP gradually increased with the increase of
conversion rate, and the maximum activation energy was 738.66 kJ/mol. The higher
the activation energy of the reaction, the more difficult the reaction is, and it is
concluded that the BCMP is more susceptible to reduction than the ACMP.
SEM and EDS Analysis
Figure 5 is a scanning electron microscope and energy spectrum analysis of BCMP

and ACMP after reduction at 1000 °C. It can be seen from Fig. 5a that there is no
iron whisker on the surface of BCMP, The EDS test results show that the O peak
and the C peak disappears, indicating that the bituminous coal-coated on the surface
Effect of Mechanical Carbon Coating on Reduction … 899
Fig. 4 Relationship between activation energy and conversion
BCMP
ACMP
Fig. 5 SEM and EDS of BCMP and ACMP

900 S. Hao et al.
of the magnetite powder has fully reacted with the magnetite powder and the newly
formed metal iron content Higher. It can be seen from Fig. 5b that iron whiskers are
formed after ACMP reduction, and the surface is smooth and metallic luster. The
EDS test results show that the O peak and the C peak are no longer present. It shows
that the magnetite powder has been reduced, and the metal Fe is the main product.
Conclusions
(1) Under the same conditions, the reaction activation energy of bituminous coal-
coated magnetite powder is lower than that of anthracite-coated magnetite pow-
der. Therefore, bituminous coal coating is more conducive to the reduction of
magnetite powder.
(2) The bituminous coal-coated with magnetite powder can effectively inhibit the
growth of iron whiskers.
Funding Support: National Natural Science Foundation of China (NO. 51274084), Hebei Nat-
ural Science Foundation (E2018209323, E2017209231), and Project of North China University of
Science and Technology GP201507.
References
1. Zhao Z, Tang H, Guo Z, Shao J, Wang Z, Chen Y (2010) In situ observation of growth of iron
whiskers under CO atmosphere. J Chin Rare Earth Soc 28(s):354–358
2. Komatina M, Gudenau HW (2004) The sticking problem during direct reduction of fine iron ore
in the fluidized bed. Metalurgija 10(4):309
3. Gudenau HW, Fang J, Hirata T et al (1989) Fluidized bed reduction as the prestep of smelting
reduction. Steel Res 60(3/4):138
4. Mikami T, Kamiya H, Horio M (2002) The mechanism of defluidization of iron particles in a
fluidized bed. Powder Technol 124:28–39
5. Pawlik C, Schuster S, Eder N (2007) Reduction of iron ore fines with CO-rich gases under
pressurized fluidized bed conditions. ISIJ Int 47(2):217–225
6. Sturn J, Voglsam S, Weiss B, Schenk J, Winter F (2009) Evaluation of the limiting regime in iron
ore fines reduction with H2 -rich gases in fluidized beds: Fe2 O3 to Fe3 O4 . Chem Eng Technol
32(3):392–397
7. Lei G, Han G, Zong-liang Z, Zhan-cheng G (2015) Sticking resistance of iron ore fines with
coating Ca3 (PO4 )2 method and mixing ores method. Iron Steel 50(6):15–20
8. Zhi-Long Z, Hui-qing T, Zhan-cheng C (2011) In situ observation and mechanism research of
the influence of CaO on the growth of iron whiskers under CO atmosphere. J Univ Sci Technol
Beijing 33(7):817–822
Effect of Plastic-Coal Mixed
Carbonization Reducing Agent on Direct
Reduction Behavior of Carbon-Bearing
Pellets
Jianhao Dong, Guang Wang, Hao Zhang, Jingsong Wang and Qingguo Xue
Abstract In order to solve the pollution caused by waste plastics and improve the
reduction rate of carbon-bearing pellets, a new idea of co-carbonization of plastics
with different kinds of coal was put forward in order to achieve the purpose of clean
treatment of waste plastics and cost-saving in iron and steel industry. Basic research
on the application of this new type of mixed carbonization reductant has been carried
out. Effects of reduction temperature, types of reducing agents, types of iron ores and
batching methods on the metallization degrees, and morphologies of reduced carbon-
bearing pellets were systematically studied. The results show that when the raw
material is magnetite iron concentrate, the addition of mixed carbonization reductant
carbonized by anthracite and PE plastics can improve the reduction rate of carbon-
bearing pellets, but it will cause a certain degree of expansion.
Keywords Waste plastics · Carbonization · Reducing agent · Carbon-bearing

pellets
J. Dong · G. Wang (B) · H. Zhang · J. Wang · Q. Xue

e-mail: wangguang@ustb.edu.cn
J. Dong
e-mail: dongjianhaoustb@163.com
H. Zhang
e-mail: zhanghaoustb@163.com
J. Wang
e-mail: wangjingsong@ustb.edu.cn
Q. Xue
e-mail: xueqingguo@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_80
902 J. Dong et al.
Introduction
Plastic has the characteristics of light weight, waterproof, durability, mature pro-
duction technology, and low cost. With the development of related disciplines and
industries, plastic products have been widely used in the world but also produced
a large amount of plastic waste. In 2017, the annual output of plastic products in
China reached 75.16 million tons. However, in that year, the recovery of waste plas-
tics in China was only 16.93 million tons. The rest of the waste plastics that were
not recycled were buried in landfills or accumulated in the natural environment [1].
The accumulation of waste plastics has caused many problems, such as visual pol-
lution, biological poisoning, wasting of resources, and atmospheric environmental
pollution, which have seriously affected people’s daily life and destroyed the natural
environment of the earth.
In order to solve the pollution problem caused by the waste plastics, a new type of
mixed reductant was prepared by co-carbonization of plastics and pulverized coal.
The effects of reduction temperature, reducing agent type, iron ore type, and burden
method on the metallization degrees and morphologies of reduced carbon-bearing
pellets were studied. The direct reduction reaction behavior of mixed carbonization
reductant in reduced carbon-bearing pellets was compared and analyzed.
Raw Materials
The iron ore powders used in the experiment are hematite chemical powders and
magnetite concentrate powders, whose main components are shown in Table 1. The
reductants used in the experiment are coke, coke/plastics carbonization products,
anthracite and anthracite/plastics carbonization products. The proximate analysis of
each reductant is shown in Table 2. The plastics used in the experiment are PE plastics
films.
Table 1 Chemical compositions of magnetite concentrate (wt%)

TFe FeO SiO2 Al2 O3 CaO MgO P S
64.6 29.3 7.21 0.81 0.17 0.58 0.024 0.21
Effect of Plastic-Coal Mixed Carbonization … 903
Table 2 Proximate analysis of reductants (wt%)

Category FCd Vd Ad
Coke 79.72 2.14 18.14
Coke carbonization products 52.56 34.33 52.56
Anthracite 81.33 7.23 9.08
Anthracite carbonization products 60.69 30.44 8.59
PE plastics films were mixed with coal powders with a fineness of −80 mesh at a
mass ratio of 1:5. Under the protection of high-purity N2 with a flow of 3 L/min,
the carbonization products were prepared by heating in a shaft resistance furnace at
450 °C for 30 min. In the preparation of the raw materials, the molar ratio between
the fixed carbon in the reducing agent and the oxygen in the iron oxide in the iron ore
powder was set as 1.0. Magnetite concentrate powders and hematite chemical pow-
ders were fully blended with coke, coke/plastics carbonization products, anthracite
and anthracite/plastics carbonization products, respectively. The moisture of the raw
material was set as 7%.
The mixture of 8 g was placed in the steel mold and pressed into a cylindrical
pellet with a diameter of 20 mm. The pelletizing process was performed through a
manual ball press under the pressure of 20 MPa. The pressed pellets were dried at
105 °C for 12 h before the reduction experiment. Samples were reacted in a shaft
resistance furnace at different temperatures for 30 min to determine the metallization
degree of reduced pellets. The morphologies and metallization degrees of reduced
coke pellets and reduced coke/plastics carbonization products pellets at 1000 °C,
1050 °C, 1100 °C, 1150 °C, and 1200 °C were observed to analyze the effect of tem-
perature on pellet reduction. Coke, coke/plastics carbonization products, anthracite
and anthracite/plastics carbonization products were pelleted with magnetite concen-
trate powders respectively, and the reaction was conducted at 1000°C and 1200°C to
observe the morphologies of reduced pellets and determine the metallization degrees
of reduced pellets. Hematite chemical powders and magnetite concentrate powders
were pelleted with anthracite/plastics carbonization products respectively, and their
morphologies were observed at 1200°C to study the effect of iron species on the
reduction. The hematite chemical powders were pelleted with anthracite and mixed
carbonization reductant respectively, and the morphologies of these reduced pellets
were observed and the metallization degrees of these reduced pellets were determined
to study the effect of batching method on the reduction.
904 J. Dong et al.
Results
Effect of Temperature on the Reduction of Carbon-Bearing

Pellets
The reducing agent is the coke and coke/plastics carbonization products. The raw
materials of iron ore are magnetite concentrate powders. When the reduction tempera-
tures are 1000 °C, 1050 °C, 1100 °C, 1150 °C, and 1200 °C respectively, the metalliza-
tion degrees of the carbon-bearing reduced pellets are shown in Fig. 1. It can be seen
that temperature has a great influence on the metallization degrees of reduced pellets.
With the increase of temperature, the metallization degrees of reduced carbon-bearing
pellets increases continuously, and the metallization degrees of reduced coke pellets
are significantly higher than those of reduced coke/plastics carbonization products
pellets. This indicates that the carbonization products formed by carbonization of
plastics and coke together will hinder the reduction of carbon-bearing pellets.
The morphologies of reduced carbon-bearing pellets at different temperatures are
shown in Fig. 2. It can be seen that when the reducing agent is coke, the volume of
the pellet after reduction at 1000 °C is not much different from that before reduction,
which is due to the low reaction temperature and the low reduction degree of the
reduced pellet at this time. When the reaction temperature is higher than 1050 °C,
the volume of reduced pellets decreases with the increase of temperature. When the
reducing agent is the coke/plastics carbonization products, a large number of holes
100
coke
90 coke/plastics carbonization products
80
Metallization degree( )
70
60
50
40
30
20
10
1000 1050 1100 1150 1200

Temperature(
Fig. 1 Metallization degrees of reduced pellets at different reduction temperatures

Room
1000℃ 1050℃ 1100℃ 1150℃ 1200℃
temperature
Coke
Room
1000℃ 1050℃ 1100℃ 1150℃ 1200℃
temperature
Coke/plastics
carbonization
products
Fig. 2 Morphologies of reduced pellets at different reduction temperatures
appear on the surface of the reduced pellet at 1000 °C. This is because the plastic in
the pellet decomposes sufficiently at 1000 °C and produces a large number of gases.
The decomposition of plastic components and the formation of gases result in a large
number of holes on the surface of the reduced pellet. The volume of reduced coke
pellet is similar to that of reduced coke/plastics carbonization products pellet, which
proves that the addition of coke/plastics carbonization products has little effect on
the volume of reduced pellets.
Effect of Reductant Types on the Reduction

of Carbon-Bearing Pellets
The raw materials of iron ore are magnetite concentrate powders. When the
reducing agents are coke, coke/plastics carbonization products, anthracite and
anthracite/plastics carbonization products, the metallization degrees of reduced
carbon-bearing pellets are shown in Fig. 3. It can be seen that changing the type
of reducing agent will affect the metallization degrees of reduced carbon-bearing
pellets. When the reducing agent is anthracite, the metallization degrees of reduced
carbon-bearing pellets are the highest, which is because the reactivity of anthracite
is much higher than that of coke. When the reducing agent is the anthracite/plastics
carbonization products, the metallization degrees of reduced pellets are similar to
those of reduced anthracite carbon-bearing pellets, which indicate that adding PE
plastics to anthracite coal for direct reduction will not deteriorate the metallization
degrees of reduced pellets. Therefore, compared with coke reducing agent, choosing
anthracite/plastics carbonization products as reducing agent is a better choice.
906 J. Dong et al.
100
1000
1200
80
Metallization degree(
60
40
20
0
Coke Coke/plastics Anthracite Anthracite/plastics
carbonization carbonization
products products
Fig. 3 Effect of different reducing agents on metallization degrees of reduced pellets
The morphologies of reduced carbon-bearing pellets with different reducing

agents are shown in Fig. 4. It can be seen that compared with reduced coke pellet, the
volume shrinkage of reduced anthracite carbon-bearing pellet is more at 1000 °C,
which indicates that anthracite carbon-bearing pellets have begun to react at this time,
and the transformation of iron oxides to iron particles has taken place in reduced pel-
lets. When the reducing agent is the anthracite/plastics carbonization products, the
reduced carbon-bearing pellets expand malignantly, and there are a lot of cracks on
the surface of the pellet, and the volume of the reduced pellets is larger than those
Type of reductant Coke/plastics Anthracite/plastics
Coke carbonization Anthracite carbonization
Temperature products products
1000
1200
Fig. 4 Morphologies of reduced carbon-bearing pellets with different reductants

of the other reducing agents pellets. The volume of reduced anthracite/plastics car-
bonization products pellets decreases when the temperature increased to 1200 °C,
and the cracks on the surface of pellets decrease also, which is due to the formation
of a large number of metal iron particles in the pellets at 1200 °C. With the reaction
proceeding, the metal iron particles further consolidate to form large-sized metal
iron, resulting in the shrinkage of reduced carbon-bearing pellets and the healing
of cracks on the surface of pellets [2, 3]. Therefore, it is a better choice to choose
anthracite/plastics carbonization products as the reducing agent for reduced carbon-
bearing pellets, which will not degrade the metallization degrees of reduced pellets
while consuming PE plastics but will result in the malignant expansion of reduced
pellets.
Effect of Iron Ore Types on the Morphologies

The reductant is the anthracite/plastics carbonization products. The raw materials

of iron ore are hematite chemical powders and magnetite concentrate powders. The
morphologies of reduced carbon-bearing pellets are shown in Fig. 5 at 1200 °C. As
can be seen, when the raw material of iron ore is magnetite concentrate powders, there
are cracks on the surface of carbon-bearing pellet. When the raw material of iron ore
is hematite chemical powders, the reduced carbon-bearing pellet expands sharply,
and the pellet cracks, and the pellet is no longer columnar. This is because during
the process of transformation from hematite to magnetite, the structure of crystalline
system was changed and reconstructed, which caused the increase of reduced pellet
volume. By the meanwhile, hematite shows anisotropy in the reduction speed. Dur-
ing the reduction process, magnetite layers of different thickness are generated in
different directions in hematite, resulting in different tensions on all sides, leading to
the expansion and fracture of pellet [4]. Therefore, in order to avoid the expansion
and rupture of reduced pellets and ensure the strength of reduced pellets, it is better
to use magnetite concentrate powders as raw material.
Magnetite concentrate Hematite chemical

Types of iron ore
powders powders
Morphologies of reduced
pellets
Fig. 5 Morphologies of reduced carbon-bearing pellets of different types of iron ores at 1200 °C
908 J. Dong et al.
Effect of Batching Method on the Reduction

Anthracite/plastics carbonization products and the remaining anthracite powders

after carbonization reaction were mixed and broken to −80 mesh to make the mixed
carbonization reductant. In order to find a way to reduce the expansion of pellet during
the reduction process, hematite chemical powders which tend to swell in the reaction
process were selected as the raw materials of iron ore. When the reducing agents
are anthracite, anthracite/plastics carbonization products and mixed carbonization
reductant, the morphologies of reduced carbon-bearing pellets with different batch-
ing methods are shown in Fig. 6. It can be seen that the expansion degree of reduced
mixed carbonization reductant pellet is lower than that of carbonization products
pellet and higher than that of ordinary carbon-bearing pellets, and there are a few
cracks on the surface of mixed carbonization reductant pellet. This proves that the
expansion of reduced pellet caused by the addition of carbonization products can be
effectively inhibited by changing the batching method and making the carbonization
products into mixed carbonization reductant.
The metallization degrees of reduced carbon-bearing pellets with different batch-
ing methods are shown in Fig. 7. It can be seen that the change of batching method
will affect the metallization degrees of reduced carbon-bearing pellets. When the
reaction temperatures are 1000 and 1200 °C, the metallization degrees of reduced
mixed carbonization reductant pellets are higher than those of anthracite pellets,
which proves that using mixed carbonization reductant can improve the metalliza-
tion degrees of reduced carbon-bearing pellets. Therefore, combined with the above
conclusions, the use of mixed carbonization reductant as reducing agent for reduced
carbon-bearing pellets is the best choice. The use of mixed carbonization reductant
can improve the metallization degrees of reduced carbon-bearing pellets. At the same
time, the mixed reductant will not cause the malignant expansion of carbon-bearing
pellets during reduction.
Anthracite/plastics Mixed carbonization

Type of reductant Anthracite
carbonization products reductant
Morphologies of
reduced pellets
Fig. 6 Morphologies of reduced pellets with different batching methods at 1200 °C

Fig. 7 Effect of different 100

batching methods on 1000
metallization degrees of 1200
reduced pellets 80
Metallization degree(
60
40
20
0
Anthracite Mixed
carbonization
reductant
Conclusions
Reduction temperature, reductant type, iron ore type, and batching method all affect
the morphologies and the metallization degrees of reduced carbon-bearing pellets.
Among them, reduction temperature has the greatest influence on the metallization
degrees of reduced pellets. The metallization degree of the reduced pellets is the
highest at 1200°C. The addition of coke/plastics carbonization products has little
effect on the expansion of reduced pellet, but it will reduce the metallization degree
of pellet. Although the addition of anthracite/plastics carbonization products will
make the reduced pellet expand sharply, it will not reduce the metallization degree
of the pellet. Hematite chemical powders will aggravate the expansion of reduced
pellets. Mixed carbonization reductant can inhibit the expansion of hematite chemical
powders pellet with carbonization products, and improve the metallization degree of
reduced pellets.
Acknowledgements The work was supported by the National Natural Science Foundation of China
(No.51804024, No.U1960205) and the Fundamental Research Funds for the Central Universities
(No.FRF-TP-18-008A2).
References
1. Chen W, Xie Z, Zhang H, Zhao Z, Wu W (2015) Effect of plastic addition on direct reduction
of carbon-containing pellets. J Iron Steel Res 27(10):11–18
2. Pi X, Sun Q, Luo G, Wang Y, Zhu J (2017) Research review on reduction expansion mechanism
of pellets. Sinter Pelletizing 42(4):28–34
910 J. Dong et al.
3. Wang G, Wang J, Xue Q (2018) Kinetics of the volume shrinkage of a magnetite/carbon

composite pellet during solid-state carbothermic reduction. Metals 8(12):1050
4. Wang HT, Sohn HY (2011) Effect of CaO and SiO2 on swelling and iron whisker formation
during reduction of iron oxide compact. Ironmak Steelmak 38(6):447–452
Experimental Study of CO2
for Vanadium Extraction by Segmented
Combined Blowing in Converter
Pan Li, Yu Wang and Zheng-Lei Guo
Abstract In order to further explore the application of CO2 in vanadium extrac-

tion in combined blowing converter, the initial injection temperature was 1300 and
1320 °C, and the CO2 ratio changed with the injection time of 1, 3, 6, and 10 min
when the initial proportion was 10, 15, 20, and 25%, and finally reached 40% for
segmented combined blowing. The variation of C and V contents and bath temper-
ature at different initial injection temperatures was investigated, and compared with
the constant-ratio combined blowing with CO2 ratio of 10, 15, 20, 25% at 1320 °C.
It was concluded that the optimal initial injection temperature of segmented blow-
ing is 1300 °C and the optimal initial injection flow is 15%, which has little impact
on the vanadium oxidation rate, and the carbon retention effect is better than the
constant-ratio blowing, and the end temperature can be properly controlled.
Keywords Carbon dioxide · Vanadium extraction · Segmented combined blowing
Introduction
Vanadium is a valuable strategic resource. It improves the strength, toughness, wear

resistance, and fatigue resistance of steel by refining matrix grains. Vanadium is also
used as a catalyst in chemical industry and as a stabilizer and intensifier for titanium
alloys in aerospace industry, so that the alloys have good plasticity and ductility [1].
In addition, vanadium has the potential for use in functional materials that are used
to treat diabetes and cancer [2]. Carbon dioxide gas is widely distributed in nature.
Because of its association with the greenhouse effect, international pressure to reduce
carbon dioxide emissions is prominent [3, 4]. Methods for reducing carbon dioxide
emissions and improving carbon dioxide utilization have become one of the main
objectives of many steel industry projects [5, 6].
Vanadium occurs in nature mainly in vanadium–titanium magnetite accompanied
by titanium and iron, and its distribution is very dispersed [7]. Vanadium extraction
P. Li · Y. Wang (B) · Z.-L. Guo


https://doi.org/10.1007/978-3-030-36540-0_81
912 P. Li et al.
Table 1 Partial composition of vanadium containing hot metal

Composition C V Si Mn P
wt% 4.23 0.285 0.043 0.15 0.017
from converter is currently the main production method. The use of carbon dioxide
as a weak oxidant and coolant in vanadium extraction converter has been verified.
Using CO2 as a gas coolant was proved conducive to vanadium extraction, and
oxygen consumption was reduced [8].
Existing studies have shown that, the top-blowing style saved more carbon during
the vanadium extraction process, whereas it oxidized more vanadium to the slag phase
compared with the bottom-blowing style [9]. In comparison with the constant-ratio
mixed blowing, the CO2 –O2 segmented mixed blowing is effective for controlling
the molten bath temperature in the middle and late stages, and in achieving vana-
dium extraction and carbon preservation [10]. Compared with mixed CO2 –O2 blow-
ing in converter, CO2 –O2 combined blowing can increase the proportion of CO2
in reaction, shorten the time of vanadium extraction, and reduce the temperature
of molten bath [11].
This paper describes the relationship between segmented combined blowing
(SCB) and constant-ratio combined blowing (CCB) was experimentally studied, and
the advantages of segmented combined blowing were further demonstrated.
Experimental
Materials and Equipment
The partial composition of the vanadium-bearing metal provided for this study by
Panzhihua Iron and Steel Group Company is shown in Table 1.
A diagram of the experimental apparatus is presented in Fig. 1. The apparatus
includes a MoSi2 electric resistance furnace and flow rate control system. The device
uses a silicon molybdenum rod as the heating element with a maximum temperature
of 1500 °C. The flow rate control enables the operator to decide the flow rates at
which one or both of the two gases is blown into the furnace.
Method
Three hundred and fifty grams (350 g) of molten iron were used in each experiment.
The top-blown oxygen and bottom-blown carbon dioxide (top insertion) are used,
and the gas was injected at 600 ml/min (temperature: 20 °C, pressure: 101 kPa).
Samples were taken at 1, 3, 6, 10, and 15 min, respectively.
Experimental Study of CO2 for Vanadium Extraction … 913
Fig. 1 Schematic drawing of experimental apparatus
Experiment 1:
Constant-ratio combined blowing (CCB) at the initial injection temperature of
1320 °C, CO2 and O2 was blowing for combined blowing, and the proportions of
CO2 were 10%, 15%, 20%, and 25%, respectively. The injection ratio of CO2 is
constant.
Experiment 2:
Segmented combined blowing (SCB) at the initial injection temperatures of 1300
and 1320 °C, CO2 ratio changed with the injection time of 1, 3, 6, and 10 min when
the initial proportion was 10, 15, 20, and 25%, and finally reached 40% (Table 2).
Table 2 Segmental combined blowing

Initial Blowing Blowing Blowing Blowing
proportion of time (1 min) time (3 min) time (6 min) time
CO2 (%) (10 min)
Proportion of 10 17 25 32 40
CO2 (%) 15 21 27 34 40
20 25 30 35 40
25 29 32 36 40
914 P. Li et al.
Fig. 2 The Carbon

Oxidation Rate change with
initial ratio of CO2
Fig. 3 The Vanadium

Oxidation Rate change with
initial ratio of CO2
The important requirement of extracting vanadium from converter is “extracting

vanadium and keeping carbon”, and the appropriate temperature of molten pool for
the next steelmaking preparation. Under the conditions of ensuring the oxidation rate
of vanadium extraction (>90%) and the carbon content of semi-steel (>2.5%), the
injection mode and parameters of molten pool temperature at 1350–1360 °C were
optimized.
C, V Oxidation Analysis
As shown in Figs. 2, 3, and 4, under the conditions of segmented blowing with

initial injection temperature of 1300 and 1320 °C, the oxidation rate of C decreases
with the increase of the initial CO2 injection ratio, and the content of the end point
[C] increases accordingly; the oxidation rate of V and C/V increases first and then
decreases as the ratio increases. When the initial injection ratio at 1300 °C is 15%, the
oxidation rate of C is 25.03%, the oxidation rate of vanadium is 94.76% at the highest,
and the end point C/V is the largest. In general, the higher the end point carbon–
vanadium ratio is, the better the effect of vanadium removal and carbon preservation
is. Therefore, it is considered that the optimal initial injection temperature and flow
rate of segmented combined injection are 1300 °C and 15%, respectively.
Constant-ratio combined blowing at initial injection temperature of 1320 °C,
compared with the proportion of CO2 injection, when the proportion of CO2 is 20%,
the oxidation rate of C and V is 27.56% and 94.39%, respectively. At this time, the
ratio of C/V is the largest. Therefore, it is considered that the optimum CO2 injection
ratio is 20% for constant-ratio combined injection.
Compared with segmented blowing with 15% initial CO2 injection and constant-
ratio blowing with 20% initial CO2 injection, segmented blowing has lower oxidation
rate of C, higher oxidation rate of V, and larger C/V ratio. It is concluded that
the segmented blowing has little effect on the oxidation rate of vanadium at the
appropriate initial injection temperature and proportion, and its carbon retention
effect is better than that of constant-ratio combined blowing, and the participation
rate of CO2 is higher.
Fig. 4 Final C/V ratio

change with initial ratio of
CO2
916 P. Li et al.
Fig. 5 Temperature–Time relationship of molten pool in segmented combined blowing at 1320 °C

(a). Temperature–Time relationship of molten pool in constant-ratio combined blowing at 1320 °C
(b)
Temperature Analysis of Molten Pool
In order to study the molten pool temperature at different initial injection temperatures
and at different initial CO2 injection ratios under different conditions, the temperature
data recorded by the experimental thermocouples are statistically plotted, and Fig. 5
is obtained.
As shown in Fig. 5, in the segmented blowing with initial injection temperature of
1320 °C, the temperature of molten pool rises rapidly in the early stage of reaction,
but changes slightly after the reaction lasts about 500 s, and the temperature changes
between 5 and 10 °C. This is due to large amount of oxidation of various elements
in the molten pool during the first 500 s of the reaction, while the rate of oxidation
of elements in the molten pool is relatively low in the later stage of the reaction.
Although the oxidation of C increases with the increase of the bath temperature, the
oxidation of C decreases with the increasing proportion of CO2 in the bath during
the reaction process compared with the constant-ratio combined blowing, and more
CO2 reacts with C in the molten pool, which makes the temperature of molten pool
rise slowly. The results show that the segmental combined blowing can play a role of
CO2 inhibiting the temperature rise of molten pool, which is beneficial to extracting
vanadium and preserving carbon.
According to the data presented in Table 3, the rising temperature of molten pool
decreases gradually with the increase of initial CO2 injection ratio. Comparison of
initial injection ratio between 10 and 25%, the maximum temperature difference of
molten pool can reach 20 °C; from the end point temperature of the molten pool, when
the initial blowing temperature is 1300 °C and the initial injection ratio is 10 and
15%, the final temperature of molten pool can reach 1350–1360 °C; when the initial
injection temperature is 1320 °C and the initial injection ratio is 15 and 20%, the final
temperature of molten pool can reach 1350–1360 °C, compared with 1320 °C, the
temperature of the final molten pool at 1300 °C is lower, but the increment is larger.
Table 3 Change of molten pool end temperature

Initial blowing Initial proportion of End pool Molten pool
temperature/°C CO2 (%) temperature/°C temperature
increment/°C
1300 (segmental 10 1358 58
blowing) 15 1350 50
20 1343 43
25 1338 38
1320 (segmented 10 1365 45
blowing) 15 1360 40
20 1353 33
25 1348 28
1320 (constant-ratio 10 1375 55
blowing) 15 1368 48
20 1360 40
25 1355 35
Compared with constant-ratio blowing at 1320 °C initial injection temperature, the

molten pool temperature changes less and is 7–10 °C lower in the same proportion.
The results show that the segmented blowing can meet the requirements of industrial
vanadium extraction and carbon preservation, and can effectively control the terminal
temperature of the molten pool, so that the temperature of the molten pool can reach
the specified temperature range.
In order to better study the temperature change of the molten pool, the temperature
rise of the molten pool in the above experimental group was analyzed and plotted,
and the heating rate of the molten pool was obtained in Fig. 6. The heating rate of the
molten pool in the experimental group of constant-ratio CO2 combined blowing is
higher than that of the segmented blowing in the reaction time as a whole; the heating
Fig. 6 Heating rate comparison curve (a). Heating rate comparison curve (b)
918 P. Li et al.
rate of molten pool fluctuates greatly when CO2 is injected by segmented blowing,
but the temperature of molten pool is relatively low in general; the temperature of
segmented blowing molten pool tends to balance faster than that of constant-ratio
blowing, and it begins to balance in 450–500 s, 50–100 s faster than that of constant-
ratio blowing. The heating rate of molten pool is in the highest stage around 180 s
at the beginning of the reaction, and it decreases in a primary function. At this time,
the heating rate can reach about 15 °C/min, when the reaction time is between 180
and 600 s, the heating rate of the molten pool is relatively small. After 650 s, the
heating rate of the molten pool tends to zero, at this time, the reaction of the molten
pool tends to be balanced and the endothermic and exothermic heats are basically
the same.
Conclusion
The effects of varying carbon and vanadium oxidation rates and carbon dioxide on the
temperature of molten bath was evaluated in a series of experiments. The following
conclusions were obtained:
(1) The optimal initial injection temperature of segmented combined blowing is
1300 °C and the optimal initial CO2 flow rate is 15%.
(2) Segmented blowing has little effect on vanadium oxidation rate at appropriate
initial injection temperature and proportion, but its carbon retention effect is
better than constant-ratio combined blowing, and the participation rate of CO2
is higher.
(3) Segmented blowing can meet the requirements of industrial vanadium extraction
and carbon preservation, and can effectively control the end point temperature
of the molten pool, so that the temperature of the molten pool can reach the
specified temperature range.
(4) The heating rate of the molten pool in the constant-ratio combined blowing
experimental group is higher than that of the segmented combined blowing in
the reaction time, but the temperature of the segmented blowing molten pool
tends to balance faster than that of the constant-ratio combined blowing.
References
1. Ye GZ (2006) Recovery of vanadium from LD-slag, a state of the art report, part 1-facts and
metallurgy of vanadium. In: Internet MEFOS Report, pp 76–79
2. Heyliger CE, Tahiliani AG, McNeill JH (1985) Effect of vanadate on elevated blood glucose
and depressed cardiac performance of diabetic rats. Science 227:1474–1477
3. Grimston MC et al (2001) The European and global potential of carbon dioxide sequestration
in tackling climate change. Clim Policy 2:155–171
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and steel industry. Energy Policy 35(4):2320–2335
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emissions reduction opportunities in the US iron and steel sector. Energy 26(5):513–536
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Metals Soc China 20(1):27–31
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coolant in vanadium-extraction converter. JOM 69(10):1785–1789
9. Du WT, Jiang Q, Chen Z et al (2019) Experimental characterization of CO2 and CaCO3 used
in a pyrometallurgical vanadium-extraction process. JOM
10. Wang SC (2016) Research on the influence factors of vanadium oxidation in vanadium-
containing hot metal by blowing CO2 -O2 mixed gas. MS thesis, Chongqing University,
China
11. Guo ZL (2019) Simulated experimental study on the application of CO2 in vanadium extraction
by composite blowing. MS thesis, Chongqing University, China
Gasification Behaviors of Biomass
with Vanadium Titanomagnetite
as Oxygen Carrier
Wei Cai, Zhucheng Huang, Lingyun Yi, Ronghai Zhong, Xiong Jiang,
Baizhou Tian, Chengfei Hu and Yunyun Jin
Abstract Gasification behaviors of biomass using vanadium titanomagnetite

(VTM) as oxygen carrier was studied in this paper. Effects of temperature and pres-
ence of VTM on the gasification rate of C and H, and syngas components were
investigated. The results of biomass gasification without VTM showed that the gasi-
fication rate of C and H increased from 24.8 and 34.8% to 42.5 and 54.8%, and the
proportion of CO and H2 in syngas increased from 34.9 and 2.6% to 40.4 and 5.2%,
respectively, as the temperature increased from 700 to 1000 °C. When the VTM
was added in biomass gasification at 1000 °C, the gasification rate of C and H and
proportion of CO increased by 14.8%, 10.2%, and 14.0%, respectively. The VTM
promoted the cracking of tar, and the lattice oxygen participated in biomass gasifica-
tion. Meanwhile, the iron metallization ratio and reduction degree were 82.6% and
90.1%.
Keywords Biomass · Gasification · Vanadium titanomagnetite · Oxygen carrier
Introduction
Biomass is a potential energy, because of its abundance, environmental advantages,

and economic benefits [1, 2]. Agricultural waste, wood and forest industry waste,
livestock manure, and energy plants are important sources of biomass resources [3,
4]. Biomass gasification, which converts biomass to small quantities of solids char,
bio-oil, and high quantity of synthesis gas under the presence of gasifying agent, is
one of the most important technologies for biomass utilization [5, 6].
The quality of the gasification products (solids char, bio-oil, and syngas) depend
on the gasifying agents [7]. The typical gasifying agents are air, oxygen, and steam.
Air is the most practical gasifying agent due to its low cost and availability. However,
the heating value of the product gas is quite low due to the dilution of nitrogen. When
W. Cai · Z. Huang · L. Yi (B) · R. Zhong · X. Jiang · B. Tian · C. Hu · Y. Jin

e-mail: ylycsu@126.com

https://doi.org/10.1007/978-3-030-36540-0_82
922 W. Cai et al.
oxygen is used as the gasification agent, heating value is improved. However, due to
the high cost of rich and pure oxygen production and the high concentrate of CO2 in
syngas, it is now rarely used alone during gasification [8]. Gasification with steam can
improve heating value and syngas purity (high hydrogen content). However, because
of the low energy efficiency and strict requirements of gasifier, it is not utilized in
large-scale industrial application [9].
Recently, chemical looping combustion and gasification technology has been
researched intensively [10]. The lattice oxygen in the recyclable oxygen carriers
(for instance, metal oxides) was used as biomass gasification agents, and a mixture
syngas of CO and H2 were obtained [11, 12]. The recyclable oxygen carriers are
much cheaper than oxygen, a higher purity and tractable products could be obtained.
Studies indicated that during the gasification process, biomass is well or partially
transformed when cheap iron-bearing materials (such as peridot and ilmenite) were
used as oxygen carriers. Otherwise, some iron-bearing materials show good catalytic
performance for cracking of large molecular components such as tar, which promoted
gasification of biomass [13, 14].
Vanadium titanomagnetite has huge reserves, which is characterized by stable
structure, complex mineral phases, and difficult smelting and extraction [15]. As an
oxygen carrier for biomass gasification, vanadium titanomagnetite has advantages of
high selectivity, good recycling, and low cost. On the other side, the converted active
pre-reduction materials of vanadium titanomagnetite can be returned to the smelting
process, which can effectively reduce the smelting difficulty and improve the smelting
efficiency. Therefore, the study of vanadium titanomagnetite on biomass gasification
behavior is of great significance for the sustainable development of metallurgical and
energy industries.
Experimental
Raw Materials
The biomass for the experiments was obtained from Hunan province, China.
Biomass was crushed and milled into powders (≤149 μm accounted for 75.3%).
The proximate and elemental analysis are shown in Table 1.
The measurement with Fourier transform infrared spectroscopy (FTIR) is shown
in Fig. 1.
Table 1 Proximate and elemental analysis of biomass

Proximate analysis, W ad (%) Elemental analysis, W ad (%) Qnet (J·g−1 )
M A V Fc [C] [H] [N] [S] [O]
8.00 6.03 73.27 12.70 43.00 4.48 0.32 0.08 39.72 15250
Gasification Behaviors of Biomass with Vanadium … 923
Fig. 1 FTIR spectra of

biomass raw materials
Table 2 Chemical composition of vanadium titanomagnetite (wt%)

TFe FeO TiO2 V2 O5 MgO Al2 O3 SiO2 P S CaO MnO
55.62 30.13 12.46 0.64 4.39 4.97 4.79 0.022 0.23 0.95 0.35
Figure 1 shows that there is a strong stretching vibration absorption peak of

hydroxyl (-OH) at 3420 cm−1 , which indicates that there are more hydroxyl groups
in biomass. The absorption peaks of bending and stretching vibration in C–H plane
indicate that methyl and methylene are contained in biomass raw materials, and
the absorption peaks at 2925 cm−1 are mainly formed by asymmetric methylene.
The absorption peak between 1700 and 1450 cm−1 is caused by C = C stretching
vibration. The absorption peak at 1060 cm-1 in the range of 1350 and 1000 cm−1 is
the C–O stretching vibration peak. In addition, C–H out-of-plane bending vibration
occurs between 1000 and 625 cm−1 .
The oxygen carrier used in the experiment is Panxi vanadium titanomagnetite
(≤74 μm accounted for 50%). The main chemical composition is shown in Table 2.
It is mainly composed of magnetite, ilmenite, and small amount of forsterite (Fig. 2).
Methods
The schematic diagram of the experimental setup is shown in Fig. 3. The main equip-
ment includes controllable temperature horizontal roasting tube furnace, quartz tube,
U-type drying tube, and filter. The mixtures of dried biomass, vanadium titanomag-
netite and 5% water were pressed into cylindrical aggregates (φ20 mm × 20 mm).
The aggregates were dried at 120 °C for 4 h. The tube furnace was heated to the
desired temperature before experiments. Then, the N2 (purity higher than 99.9%)
924 W. Cai et al.
Fig. 2 X-ray diffraction analysis pattern of vanadium titanium magnetite
1-N2 2-flowmeter 3-quartz tube 4-temperature control system 5- horizontal roasting tube furnace 6-
cold trap 7-dewar 8-gas washing bottle 9-U-tube 10-filter 11-gas collector 12-porcelain boat
13-anhydrous calcium chloride
Fig. 3 Schematic diagram of the experimental setup
was inlet to the quartz tube with flow rate of 0.6 L/min to get the air out. After
10 min, the flow rate of N2 was decreased to 0.06 L/min. Porcelain boat carried
10 g dried lumps were placed in the center of quartz tube. The electronic flowmeter
recorded the flow rate of gas products every 30 s, and gas collector was used to collect
the generated gas. After gasification, the volume of gas products was measured, and
gas samples were detected by gas chromatography–mass spectrometry (GC-MS, ISP
7000, Thermo Fisher, USA). The collected liquid products were washed with acetone
and weighed, and analyzed by liquid chromatography–mass spectrometry (LC-MS,
LC20A-QP8040, Shimadzu, Japan). The solid products were weighed after cooled
to room temperature within N2 atmosphere, and characterized by X-ray diffraction
(XRD, Advance D8, Bruker, Germany), Fourier transform infrared spectroscopy

(FTIR, VERTEX 70, Bruker, Germany).
The effective gasification rate of carbon and hydrogen obtained in the gasification
process was calculated according to the Eq. (1):
Ni
ϕi = × 100% (1)
n Ti
where ϕi is the gasification rate of carbon or hydrogen, %; Ni is the carbon moles

(CO, CH4 , CO2 , C2 H4 , and Cx Hy ) or the hydrogen moles (H2 , CH4 , C2 H4 , and
Cx Hy ) in the gas phase; n Ti is the total carbon moles or total hydrogen moles of the
aggregates.
The metallization ratio was calculated according to the Eq. (2):
M Fe
η= × 100% (2)
T Fe
where the η is metallization ratio, %; the MFe is metallic iron ratio, %; the TFe is
the total iron ratio, %.
Effect of Temperature on Biomass Gasification
The effect of temperature on the effective gasification rate of carbon and hydrogen
of pure biomass (roasted for 40 min) is shown in Fig. 4.

on the effective gasification
rate of carbon and hydrogen
without VTM
926 W. Cai et al.

on the syngas components
rate without VTM
The effective gas rate of carbon and hydrogen during biomass pyrolysis without
VTM increased with the increase of temperature. The gasification rate of carbon
and hydrogen increased from 24.8 and 34.8% to 42.5 and 54.8%, as the temperature
increased from 700 to 1000 °C. The pyrolysis of biomass intensified at higher tem-
perature, and the large molecular organic matter decomposed into small molecular
gas [16, 17]. Therefore, as the number of carbon and hydrogen atoms in the syngas
increased, the effective gasification rate increased.
The effect of temperature on the syngas components is shown in Fig. 5. With the
increased temperature from 700 to 1000 °C, the proportion of CO and H2 increased
from 34.9 and 2.6% to 40.4 and 5.2%. The proportion of CO2 and Cx Hy decreased
from 26.8 and 3.7% to 22.8 and 2.8%, and the proportion of CH4 and C2 H4 remained
unchanged.
During biomass pyrolysis without VTM, the oxygen in CO and CO2 mainly
originates from the oxygen in biomass. With the increase of temperature, the decom-
position of Cx Hy and the disproportionation of carbon dioxide were promoted [18].
Therefore, the proportion of Cx Hy and CO2 decreased, whereas the proportion of H2
and CO increased.
Effect of Oxygen Carrier on Biomass Gasification
The effect of oxygen carrier (VTM) on the effective gasification rate of carbon and
hydrogen is shown in Fig. 6. When the VTM was added in biomass gasification
at 1000 °C, the gasification rate of carbon and hydrogen increased from 42.5% and
54.8% to 57.4% and 65.0%, respectively. This was caused due to VTM that promoted
the cracking of tar [13, 14]. Additionally, the lattice oxygen in VTM participated in
the biomass gasification [18].
Fig. 6 Effect of oxygen

carbon
carrier on the effective
hydrogen
gasification rate of carbon
and hydrogen (The
Effective gasification rate/%

temperature was 1000 °C,
the time was 40 min, and the
oxygen carrier ratio was
C/Fe = 1.2)
without oxygen carrier oxygen carrier
The effect of oxygen carrier (VTM) on the syngas components is shown in Fig. 7.
Due to VTM addition in biomass gasification at 1000 °C, the proportion of CO
increased from 40.4 to 48.9%, whereas the proportion of CO2 and C2 H4 decreased
from 21.7% to 18.6%, and from 10.5% to 6.7%, respectively. The lattice oxygen in
VTM participated in the biomass gasification, and the disproportionation of carbon
dioxide was intensified [17, 18]. The decrease of C2 H4 may be due to the oxidation
reaction with lattice oxygen.
Fig. 7 Effect of oxygen CO

carrier on the syngas CH4
components rate CO2
C2H4
Syngas compositions rate/%
CxHy
H2
without oxygen carrier oxygen carrier

928 W. Cai et al.
Fig. 8 FTIR spectra of solid

products after biomass
gasification at 1000 °C
oxygen carrier
Transmittance /%
without oxygen carrier
Wavenumbers /cm-1
Transformation Mechanism
The effect of oxygen carrier on the structure of solid products is shown in Fig. 8. After
biomass was calcined for 40 min at 1000 °C, the absorption peaks of hydroxyl (-OH)
(at 3420 cm−1 ), methylene (at 2925 cm−1 ), and methyl (at 1460 cm−1 ) disappeared.
The absorption peak of C = C at 1640 cm−1 was decreased. When the VTM was
added during biomass gasification at 1000 °C, the absorption peak of C = C at
1640 cm−1 was significantly decreased, and the absorption peaks of C–O from 1350
~ 1000 cm−1 and of C–H from 1000 ~ 625 cm−1 were enhanced. These results
indicated that during biomass gasification, the large molecular organic matter in
solid products has decomposed, and the lattice oxygen in VTM has participated.
Figure 9 shows XRD phase analysis of solid products that were mainly iron, and
small amount of ilmenite and magnetite. The iron metallization ratio and reduction
degree were 82.6% and 90.1%, respectively.
Conclusions
The gasification behaviors of biomass using vanadium titanomagnetite (VTM) as

oxygen carrier was studied. The main results of this study can be summarized as:
Fig. 9 X-ray diffraction A-Fe3O4

analysis pattern of solid B-FeTiO3
products C-Fe
Intensity /a.u.
2-theta /°
(1) At higher temperature, the effective gasification rate of carbon and hydrogen
significantly increased; the proportion of CO and H2 in syngas increased, while
that of CO2 decreased.
(2) The addition of oxygen carrier promotes the conversion of carbon and hydrogen
elements into the gas phase and it improves the effective gasification rate of
carbon and hydrogen. The proportion of CO and H2 increased, while that of
CO2 decreased.
(3) The transformed oxygen carrier has higher metallization rate and reduction
degree. It can be used as active pre-reducing materials in smelting process.
Acknowledgements I would like to acknowledge Central South University and School of Minerals
Processing & Bioengineering for the assistance. And this work was supported by the National
Natural Science Foundation of China under Grant 51504230.
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conditions. J Energy Inst 92:1329–1336
930 W. Cai et al.
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gasification of biomass e modeling and experiment. Energ Convers Manag 52:1583–1588
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multipurpose model. Energ Convers Manag 129:216–226
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from biomass using chemical looping gasification method. Int J Hydrog Energ 41:10346–10353
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overview of chemical looping combustion technology. Renew Sust Energ Rev 59:597–619
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Influence of Atmosphere on Melting
Behaviour of Synthetic Slags from Ta
Recycling
Dominik Hofer, Stefan Luidold and Ulrich Bartmann
Abstract Tantalum joined the list of 43 critical raw materials (CRM) within the
latest report of the European Commission, published in 2017. Global Ta and Nb ore
production, publicly known as Coltan, is dominated by D.R. Congo and Rwanda
accounting for a combined share of at least 60%. Recycling constitutes an evolving
chance for European countries to lower their complete reliance on importation. Con-
sequently, tin slags as well as process residues like dusts or sludges are processed
by pyrometallurgical treatment and hence offer great economic potential due to the
content of valuable Ta2 O5 . Flowability tests with various atmospheres are performed
to evaluate the similarity of industrial and synthetic slags. These experiments, ther-
modynamic FactSage simulations plus slag viscosity calculations provide a solid
foundation for follow up high-temperature furnace rheometer trials which deepen
fundamental knowledge about such melts and improve existing process steps.
Keywords Critical raw material · Synthetic slag · Hot stage microscope ·

Flowability
D. Hofer (B)
Chair of Nonferrous Metallurgy, Montanuniversitaet Leoben,
Franz-Josef-Str. 18, 8700 Leoben, Austria
e-mail: dominik.hofer@unileoben.ac.at
S. Luidold
Chair of Nonferrous Metallurgy, CD Laboratory for Extractive Metallurgy of Technological
Metals, Montanuniversitaet Leoben, Franz-Josef-Str. 18, 8700 Leoben, Austria
e-mail: stefan.luidold@unileoben.ac.at
U. Bartmann
H.C. Starck Smelting GmbH & Co. KG, Ferroweg 1, 79725 Laufenburg, Germany
e-mail: ulrich.bartmann@hcstarcktanb.com

https://doi.org/10.1007/978-3-030-36540-0_83
932 D. Hofer et al.
Introduction
Tantalum, atomic number 73, is a hard, dense transition metal. Due to the high melt-
ing point of around 3000 °C, it is a part of the so-called refractory metal group (Nb,
Mo, Ta, W, and Re). Below 100 °C, Ta metal forms a compact oxide layer with a
protective effect against chemical attack (excepting hydrofluoric acid), also enabling
the production of capacitors with unique electrical properties. Therefore, the main
application area is the electronics industry accounting for nearly half of the 2000
t annual production (capacitors 34% and sputtertargets 15%), followed by superal-
loys, chemicals, mill products, and carbides. Despite today’s need for component
miniaturization, a yearly 3% demand growth rate is estimated. Because of the enor-
mous economic importance and supply risk, tantalum was evaluated as a critical raw
material (CRM) by the European Commission in 2017. In total, 23 were identified as
individual CRMs and an additional 20 belong to three critical raw material groups:
HREEs (10), LREEs (5), and PGMs (5). All assessed materials are pictured in Fig. 1,
labelled as red dots for critical (Ta highlighted as red star, listed with a supply risk of
1.0 and economic importance of 3.9) and blue ones for non-critical. The European
Union as a leading tantalum and tantalum bearing product consumer is completely
dependent on importation (100% import dependency) of tantalum concentrate/raw
materials. Figure 2 is based on published data [1–5] and visualizes all countries with
Fig. 1 European commission CRM matrix of the 2017 assessment [9]

Influence of Atmosphere on Melting Behaviour … 933
Fig. 2 World mine production of tantalum content in ores and respective country risk evaluation
significant (higher than 25 t/a Ta content) ore (commonly known as Coltan) pro-
duction as well as the respective country risk, evaluated by social, environmental,
and economic aspects, ranging from 1 (very good) to 5 (severe). Global supply is
essentially provided by nine nations, from which five have at least an alarming rating
higher than 3.5. D.R. Congo and Rwanda together account for 65%, with artisanal
and small scale mining as most common practice. Typical mineability nowadays
varies between 0.01 and 1.0% Ta2 O5 . Therefore, ore processing via crushing, grind-
ing, screening, and separation is necessary to produce concentrate grades of 5–30%
Ta2 O5 [6–9].
Rapidly increased metal variety in products presents new challenges to existing
procedures and requires constant adjustment. Thus, carrier metal and by-product
classification via the metal wheel clearly depicts recovery potential as well as loss
analysis. Originally designed for ore processing, the updated metal wheel is equally
valid for end-of-life products (EoL), since both are complex raw materials (see Fig. 3).
Industries’ primary/carrier metals are represented in the inner circle, whereas the
three outer rings (indicating existing and utilized metallurgical infrastructure) con-
tain respective impurities and minor elements. Losses are inevitable (yellow and red
dots), but with adequate operations design, by-products are of great economic inter-
est. Increased recycling and a circular economy approach present opportunities for
future price stability and an improvement regarding EoL recovery rate, nowadays
assumed below 1% for Tantalum. Reuse in superalloys and pyrometallurgical syn-
thetic concentrate fabrication from tin slags and other low-grade residues constitute
best practice for secondary Ta production. The latter accounting for around 10%
of the annual demand. Slag viscosity and liquidus temperature are pivotal for high-
temperature processes. Usually a liquid slag layer covers the metal, therefore, it takes
on substantial functions like removal of impurities, atmosphere reaction prevention,
934 D. Hofer et al.
Fig. 3 Metal wheel evaluating metallurgical infrastructure and metal recovery for complex end-
of-life products [13–15]
and heat loss reduction. Flow behaviour tests and thermodynamic calculations pro-
vide good indication for operating conditions (e.g., temperature range and applied
atmosphere) in further furnace rheometer tests [7, 10–12].
The hot stage microscope testing (HSM) procedure as well as synthetic slag compo-
sitions are already published in previous work [16, 17], thus only briefly described
and visualized in the following section. Figure 4 depicts the design of experiments
in a SiO2 –Al2 O3 –CaO–MgO phase diagram, covering typical slags arising through-
out a pyrometallurgical production process for synthetic tantalum concentrate from
low-grade residues. All 16 samples (varying: SiO2 , CaO, Al2 O3 ; constant: w = 3%
MgO, w = 4% TiO2 , w = 2% ZrO2 ) are produced with laboratory grade oxide pow-
ders via annealing, weighing, homogenisation, induction furnace smelting, swing
mill grinding, and sieving. HSM furnace temperatures up to 1700 °C enable flow
behaviour characterisation of pressed cylinders (Ø = 3 mm, height = 3 mm). The
gas flow rate preset to 0.15 l/min, equalling three times the furnace volume, is large
enough to ensure constant atmosphere (reducing: CO/CO2 , Varigon H2 ; inert: Ar;
oxidizing: syn. air). Figure 5 pictures the hot stage microscope and gas flow setup
existent at the Chair of Nonferrous Metallurgy, Montanuniversitaet Leoben. Mea-
sured data were analysed via Hesse-Instruments-method, a slightly modified version
Fig. 4 Design of experiments compiled by the statistical software MODDE 12 within a SiO2 –
Al2 O3 –CaO phase diagram (calculated with w = 3% MgO by FactSage 7.2)
of ISO 540:2008 for evaluating characteristic temperatures like deformation tem-

perature (DT), sphere temperature (SpT) hemisphere temperature (HST), and flow
temperature (FT). All characteristic temperatures are automatically recorded, but
within this study, the main focus is the flow temperature assessment.
Figure 6 displays the influence of Al2 O3 , CaO, and SiO2 fractions on the flow temper-
ature at various atmospheres (reducing: CO/CO2 , Varigon H2 ; inert: Ar; oxidizing:
syn. air) varying from 1314 to 1577 °C and liquidus temperature (LT), ranging from
1453 to 1877 °C, calculated with FactSage 7.2. Every graph increases one main
component, labelled at the bottom, whereas the other two decrease according to
the respective ratio listed at the top. All lines exhibit similar progression with high
temperatures at ascending CaO content and lower ones at rising SiO2 proportion.
Furthermore, Al2 O3 indicates subordinate influence (LT decrease by 100 °C and FT
936 D. Hofer et al.
Fig. 5 Experimental setup including the hot stage microscope and atmosphere regulation as well
as a CO warning device
by 40 °C at its minimum around w = 18%). Hence, slag basicity, commonly defined

as CaO/SiO2 (C/S), evidently controls the flowability (modification of LT by 300 °C
and FT by 150 °C). Measurements correlate among every tested gas composition
(average variance of 28 °C). Figure 7a, c additionally visualize LT and FTCO/CO2 , as
well as the deviation between liquidus and minimal flow temperature (FTmin ), see
Fig. 7e, in a ternary plot. Maximum LT-FTmin (T1 ) region clearly is discernible at
highest C/S factor. The unanimously positive values of T1 can be explained by the
presence of solid particles in a liquid with low viscosity and interfacial tension at
flow temperature. Respective slag viscosities at flow and liquidus temperature, based
on FactSage simulations, are portrayed in Fig. 7b, c and depict the trade-off between
low melting and low viscous properties. Viscosity calculations with other models like
Iida, NPL, Riboud, and Urbain result in good accordance. Based on these test series
results, further high-temperature furnace rheometer investigations are in progress.
Three hot stage microscope experiments with an industrial slag are compared to
synthetic ones in Table 1 and Fig. 8 at Ar atmosphere and look alike with all four
applied gases. The main component ratio (Al2 O3 , CaO, MgO, SiO2 , TiO2 , and ZrO2 )
amounting to 98% is similar, but additional minor constituents like Cr2 O3 , Fe2 O3 ,
MnO, SnO2 as well as Na2 O effect small divergence in sample alteration throughout
heating. Deformation and flow temperature only differentiate by 7 °C and 26 °C,
respectively, for Slag 1 and 3. Slag 2 is treated as an outlier regarding its character-
istic temperatures because of data leaps. However, height progression corresponds
to all three trials, verifying sufficient repeatability as well as comparability to syn-
thetic specimens. Furthermore, measured deformation (DT) and calculated solidus
Fig. 6 Overlay prediction plot of the Al2 O3 , CaO, and SiO2 influence on liquidus as well as flow
temperatures (reducing, inert, and oxidizing atmosphere applied)
temperatures (ST) match within 25 °C for most compositions, linking the HSM tests
with relevant FactSage simulations.
Conclusion
Pyrometallurgical recycling of low-grade tantalum bearing residues accounts for

around 10% of the annual demand and constitutes a flexible, conflict free alterna-
tive to primary production from ores. Throughout several complex high-temperature
process steps, huge amounts of slag arise. Good metal/slag separation is essential
to ensure process yield as well as economic efficiency. Flow behaviour experiments
with synthetic and industrial slags are performed to test accordance and evaluate
slag composition modifications. Slight deviation due to minor components (Cr2 O3 ,
938 D. Hofer et al.
Fig. 7 Influence of Al2 O3 , CaO, and SiO2 content on a liquidus temperature* (LT), b slag viscosity
at LT*, c flow temperature in CO/CO2 atmosphere (FTCO/CO2 ), d slag viscosity at FTCO/CO2 *, and
e difference between LT and FTmin ; *calculated with FactSage 7.2
Table 1 Deformation (DT) and flow temperature (FT) from HSM experiments as well as solidus
(ST) and liquidus temperature (LT) calculated with FactSage 7.2 for industrial and fitting synthetic
slags
CSA1 CSA2 CSA3 CSA6 CSA11 Slag 1 Slag 2 Slag 3
DT (°C) 1261 1347 1255 1356 1223 1169 1275 1162
ST (°C) 1267 1333 1228 1262 1229 1057 1057 1057
FT (°C) 1322 1427 1329 1393 1378 1371 1410 1397
LT (°C) 1479 1672 1453 1577 1517 1592 1592 1592
Fig. 8 Flow behaviour evaluation of industrial (Slag 1 to 3) and synthetic slags (CSA1 to 16)
Fe2 O3 , MnO, SnO2 , and Na2 O), accounting for maximum w = 2%, is recorded. The
design of experiments accurately replicates a vast majority of process slag composi-
tions, despite these compositions depending heavily on the available input feedstock.
Flow temperature investigations in a hot stage microscope and thermodynamic Fact-
Sage simulations are a good indication of necessary process conditions. Modification
of CaO and SiO2 contents promise decent optimization potential (LT 300 °C and FT
150 °C variation), whereas atmosphere influence is rather low. All graphs align
with 28 °C average variance, whereby follow up high temperature viscosity experi-
ments become feasible. Commonly applied refractory metal (typically molybdenum
alloy) experimental setup heavily oxidizes and sublimates at temperatures higher than
500 °C and ambient air. This study demonstrated that a protective, inert, or reducing
atmosphere can easily be utilized without impact on the high-temperature specimen
behaviour. Rheometer measurements will conclude the extensive investigations of
940 D. Hofer et al.
Ta recycling slags later on, to examine the correlation with viscosity model data as
well as flow and liquidus temperatures. All those findings deepen the fundamental
process knowledge and enable further optimization, to ensure faster treatment time
and yield of a sustainable Tantalum production route.
Acknowledgements The financial support by the European Institute of Innovation and Technology
is gratefully acknowledged.
References
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26–29 August 2018
Influence of Process Parameters
on the Metal Quality at Electron Beam
Melting of Molybdenum
Katia Vutova, Vania Vassileva, Vladislava Stefanova and Maria Naplatanova
Abstract Molybdenum belongs to the group of refractory and alloying rare ele-
ments, which are used in industry mainly as pure metals and as alloying components
in ferrous and non-ferrous alloys. The effect of the electron beam melting and refining
technology on the processing of molybdenum concentrate under different process
conditions is examined in the present work. The influence of the electron beam power
and refining time on the composition variation, microstructures of the metal samples,
and degree of refining of molybdenum is studied in order to improve the quality of
the obtained metal ingots. Thermodynamic conditions of melting and refining of
molybdenum and the removal efficiency of the controlled impurities are also eval-
uated and discussed. The results show that a maximal overall removal efficiency
is seen at 17 kW beam power for a 5 min melting time and allow us to formulate
requirements on the process conditions in order to improve the quality of the obtained
metal material.
Keywords Molybdenum · Electron beam · Melting and refining
Introduction
Molybdenum (Mo) is in the group of refractory and alloying rare elements (B, Ti,
Zr, Hf, W, Mo, Ta, Nb, and V). Molybdenum and its alloys have unique physical and
mechanical properties and are used in different branches of economy: in metallurgy
as an alloying component in steels and in the production of high-temperature and
corrosion-resistant alloys, in the electrovacuum production as a base construction
material in lighting industry, and in the manufacturing of laser mirrors in powerful gas
dynamic lasers. Molybdenum compounds such as molybdates, oxides, and sulfides
K. Vutova (B) · V. Vassileva · M. Naplatanova

Institute of Electronics, Bulgarian Academy of Sciences, 72 Tzarigradsko shosse,
1784 Sofia, Bulgaria
e-mail: katia@van-computers.com
V. Stefanova
University of Chemical Technology and Metallurgy, 1756 Sofia, Bulgaria

https://doi.org/10.1007/978-3-030-36540-0_84
942 K. Vutova et al.
are good catalysts of chemical reactions, pigments of colorants, and also components
in glazes and mixtures [1–3]. There is a considerable quantity of Mo and molybdenum
alloys, which is used as heaters and screens in high-temperature vacuum furnaces,
in cooling pipes, and other essential parts in nuclear reactors, in rocket science. The
consumption of molybdenum is on the rise and its increase will continue [4].
Similar to tungsten, molybdenum is also brittle. The brittleness temperature
threshold of molybdenum depends on the metal purity as well as on its produc-
tion method and on the size of grains in its structure. The effect of oxygen is strong,
while the presence of Zr, Nb, Ti, and Hf may decrease the harmful effect of oxygen
upon the fragility of molybdenum.
New usages of molybdenum and its alloys in contemporary technologies and fields
presume higher requirements to the composition, structure, and properties, which can
be achieved through the application of contemporary metallurgical methods. The
greatest are the possibilities of the methods occurring at high temperatures and high
and super high vacuum. The practical realization of these processes requires powerful
heating sources with high energy density. One good possibility is the electron beam
melting (EBM) and refining method, which combines the advantages of the vacuum
metallurgy and the high-energy special electrometallurgy [2, 5–9]. There are no
special requirements for the initial (raw) material at EBM. Important advantages
of EBM appear to be the purity of the vacuum, where the processes occur, the
possibility of the liquid metal to get overheated to high temperatures, the lack of
additional pollution from the contact of the material with ceramic melting pots, due
to the usage of water-cooled copper crucible, where the final block flows out, the
possibility to sustain the liquid metal in an overheated state for a sufficiently long time.
The method is suitable for the production of pure high-temperature metals (such as
Ta, W, and V) with low impurity content when concentrates are melted, formed when
processing natural resources, but also when processing waste materials containing
other refractory metals [5, 7, 10–15].
Electron beam drip melting process was used to obtain an ultra-high purity Mo
ingot using a molybdenum bar feeder produced from Mo powder [16]. Molybdenum
is an entirely recyclable metal. In Ref. [17], results concerning electron beam melting
and recycling of Mo scrap till the production of ingots or semi-finished products of
pure Mo were reported.
The present paper investigates the effect of electron beam melting when processing
molybdenum concentrate and the influence of the technological process parameters
(the beam power and refining time) on the changing of the composition, structure,
and hardness of the Mo samples and the material efficiency for the improvement of
the quality of the produced metal ingots.
Influence of Process Parameters on the Metal Quality … 943
Table 1 Concentration of
Sample no Process parameters C imp (%)
metal impurities at EBM of
Mo P (kW) τ (min)
Mo-11 15 5 1.97
Mo-12 15 10 2.05
Mo-21 17 5 1.85
Mo-22 17 10 2.35
Concentration before EBM 4.41
Experiments
The experiments for EBM of molybdenum material were performed using 60 kW

electron beam furnace ELIT 60 in the laboratory of electron beam technologies,
Institute of electronics at the Bulgarian Academy of Sciences. The furnace consisted
of a melting chamber, an optical system (one electron gun with an accelerating voltage
of 24 kV), a water-cooled copper crucible, a vacuum system, and the working vacuum
pressure was 5–8 × 10−3 Pa [7, 10].
The content of molybdenum in the initial material was 95.59%. The impurities
with concentrations more than 1% were Sb (2%) and Si (1%). The content of the
other metal impurities (Al, W, Nb, Zr, Cu, and Fe) in the initial samples was between
5000 ppm and 100 ppm. Oil-free dry pieces of the initial material have been melted
once (single processing) and the temperatures (T ) were determined by an optical
pyrometer QP-31 using special correction filters.
The effect of the electron beam power (Pb ) and the time (τ ) of electron beam
processing on the changes of the metal impurities concentrations in the refined metal
after each refining cycle (regime) was examined. A series of experiments were per-
formed with different electron beam powers—15 kW (T = 2900 K) and 17 kW (T
= 3000 K) and refining times of 5 and 10 min. The chemical composition varia-
tion of the metal samples before and after EBM is defined using emission spectral
analysis. The data in Table 1 represents the values of the total concentrations of the
investigated impurities under the different EBM processings.
Thermodynamic Conditions at EBM of Mo
Depending on the thermodynamic conditions of melting and the type of impurities,

the refining at EBM processing occurs through evaporation of impurities, which
have a vapor pressure (pi ) higher than the vapor pressure of the base metal (pR ),
i.e., pi > pR (degassing), or through evaporation of volatile compounds of the metal
impurities (distillation). Figure 1 shows the vapor pressure values of Mo and of the
Fig. 1 Vapor pressures of

metals for the temperature
rage of 2000–3000 K
controlled metal impurities under the EBM conditions (temperature range of 2000–
3000 K, working pressure in the chamber—10−1 –10−3 Pa). The vapor pressure of
the impurities W, Nb, and Zr are lower than the pressure of the base metal (Mo) and
they cannot be removed under the process conditions. For the other controlled metal
impurities Al, Fe, Sb, Cu, and Si, the vapor pressures are higher than the pressure of
Mo for the investigated temperature range and it is possible for them to get separated
from the liquid metal/vacuum reactive surface.
For the multicomponent metal system, which is the metal melted in vacuum, a
criterion for evaluation of the refining efficiency is the relative volatility α, which is
calculated using
√
p R Mi
αi = √ , (1)
pi M R
where pR and pi are the vapor pressures of the base metal and of the impurity, M R and
M i are the molecular weights of the base metal and of the metal impurity, respectively
[18].
The values of the relative volatility α i for the metal impurities in the molybdenum
concentrate at the working temperature of 3000 K are calculated using Eq. (1) and
are shown in Fig. 2. The parameter α i is in the range of 10−7 –105 .
1,00E+03
1,00E+01
1,00E-01 Al Fe Cu Sb Si Mo Nb Zr W
ai
1,00E-03
1,00E-05
1 00E-07
Fig. 2 Values of the relative volatility α i for the metal impurities in Mo at 3000 K
For the more volatile impurities, situated on the left of Mo (Fig. 2), the values
α i 1 and their removal from the refined metal is expected to be possible. For
the non-volatile impurities, situated on the right of Mo (Fig. 2), α i 1 and their
removal is not possible at none of the investigated process regimes. The removal of
the impurities, whose values of α i are approximately 1, is possible but difficult and is
accomplished under certain conditions and at a loss of the base metal. It is important
that optimal conditions should be determined for the achievement of the best refining
at minimal mass losses by evaporation of the refined metal.
At EBM of metals, the refining processes include and are often influenced by
chemical reactions between the metal impurities and the gasses in the liquid metal.
The possibility for each chemical reaction to happen is estimated through the iso-
static–isothermal potential, i.e., the free energy F. The values of F vary with the
change of the pressure and temperature and are given by
F = F 0 −RT ln p n , (2)
where F 0 and F are the free energies for a reaction to proceed at an atmospheric
pressure and in vacuum, respectively, R is the gas constant, T is the working temper-
ature, p is the pressure at which the refining process occurs (10−3 Pa), and n is the
number of atoms taking part in the chemical reaction. F < 0 is the condition under
which the chemical reaction proceeds [19].
Table 2 presents the calculated values of the free energy F of the base metal and
of the controlled impurities at the working temperature of 3000 K. At higher vapor
pressures (Fig. 1) and stable bonds in the molecules of the formed oxides (F MeO <
0, Table 2), the oxides are removed from the liquid metal surface through distillation
(for the impurities Al, Si, Fe). At higher vapor pressures (Fig. 1) and unstable bonds
in the molecules of the formed oxides (F MeO > 0, Table 2), the impurities removal
from the molten metal surface is carried out in an atomic form by degassing (for the
impurities Cu, Sb).
Table 2 Free energies for

Reactions F 3000 K (kJ/kg)
oxides of Mo and metal
inclusions 4Al + 3O2 = 2Al2 O3 −6803.9
Si + O2 = SiO2 −6057.41
4Nb + 5O2 = 2Nb2 O5 −2899.2
Zr + O2 = ZrO2 −1534
2Fe + O2 = 2FeO −1230.4
W + O2 = WO2 −1140.4
2W + 3O2 = 2WO3 −1118.4
2Mo +3O2 = 2MoO3 −556.8
4Cu + O2 = 2Cu2 O + 88.64
4Sb + 3O2 = 2Sb2 O3 +3197.4
The conclusions about the behavior of the impurities as a result of the discussed
values of the vapor pressure, relative volatility, and the free energies of the chemical
processes that take place are also confirmed by the results obtained from the emission
spectral analysis.
The refining efficiency is also influenced by the technological parameters—the
electron beam power (overheating temperature of the liquid metal) and the melting
rate (the duration of the electron beam processing). The concentrations of W, Nb,
and Zr do not change for the investigated temperature conditions and the duration of
refining. The duration of the electron beam processing influences the concentrations
of the impurities Sb, Al, Cu, and Fe. The calculated values of the refining efficiency
at each regime are in the range of 46.7–58%. The best refining is achieved at 17 kW
beam power for a 5 min melting time and the metal purity is 98.15%.
Microstructures During the Heat Processing
The effects of the beam power and refining time on the microstructures of the molyb-
denum ingots were also investigated and light microscopy was used to observe the
metal microstructure. The information available in the literature about the influence
of the EBM parameters on the macro- and microstructures of the formed Mo ingots
is still very scarce. According to Glebovski [2], this is due to the considerable dif-
ferences in the melting rate and cooling of the ingots, the melting temperature, the
residence time, the content of the impurities, etc. All these parameters influence the
purity and the properties of the pure Mo and determine its application in the thin-film
metallization in microelectronics. At the low melting rate, the mean grain size is 5–
6 mm, while at the high rate, it is 1–2 mm, and the lengths of the grain are ~100 mm
and ~10 mm, respectively [2].
During the solidification process, the temperature gradient and solidification rate
are the main parameters which influence the macro and microstructure of Mo [2, 20].
When the temperature gradient is high and the solidification rate is low, the solidifi-
cation structure grows as planar grains. With the increase of the solidification rate,
the microstructure of Mo is transformed to equiaxed grains and dendrite structure.
During the solidification process at the presence of impurities and fast cooling, the
dendrite matrix is firstly formed from the liquid phase, and then the eutectic structure
is formed, and the remaining liquid phase of the base metal solidifies.
The microstructure of the Mo material was investigated by a Leica DM2500 opti-
cal metallographic microscope with a Leica EC3 digital camera and the Leica LAS
software was used for image processing. Specimens for metallographic examinations
were cut and polished according to standard procedures and etched with a solution
consisting of 68% HNO3 , 98% H2 SO4 , and water in proportion 1:1:1 for 20 s.
Figures 3 and 4 show the metallographic microstructures of the Mo samples before
and after EBM. The results of the chemical analysis show that in the initial material,
the content of Sb (2%), Si (1%), and Al (0.5%) is the highest. All of these three
metals form solid solutions with Mo [21, 22]. However, unlike Si and Al, according
to the phase diagram Mo–Sb at cooling to a temperature less than 1073 K, a solid
solution of Mo and the intermetallic compound Mo3 Sb7 will be formed [21]. The
total content of the other investigated impurities (Nb, Zr, W, Cu, and Fe) in the sample
is less than 1%. Therefore, their influence on the macro- and microstructure of Mo
can be neglected.
At a higher magnification of the structure of the initial material (Mo-00), a dendrite
matrix on the inside of which there is a crystallized light inhomogeneous Mo melt can
be seen (Fig. 3b). The presence of phases of different colours is due to the formation
of solid solutions and eutectic melts between molybdenum and the other metals (Sb,
Si, Al, etc.) in the concentrate.
The chemical analysis showed that after EBM at T = 2900 K the purity of the
obtained ingots is higher than the purity of the initial material. At this refining tem-
perature, the content of Sb (about 1–1.5%) is still the highest. The Sb removal during
the EBM is complicated because of the formation of a solid solution and intermetallic
(a) (b)
200 μm 50 μm
Mo-00 (x 100) Mo-00 (x 400)
Fig. 3 Optical micrographs of the molybdenum material before EBM: a 100x magnification, b 400x
magnification
(a) (b)
200 μm 200 μm
Mo-11 (x100) Mo-12 (x100)
(c) (d)
200 μm 200 μm
Mo-21 (x100) Mo-22 (x100)
Fig. 4 Microstructures of the molybdenum samples (100x magnification) obtained at different

EBM conditions: a Pb = 15 kW, τ = 5 min; b Pb = 15 kW, τ = 10 min; c Pb = 17 kW, τ = 5 min;
d Pb = 17 kW, τ = 10 min
compounds with Mo. It has been found that at this melting temperature, the refining
time does not significantly affect the total impurities content after EBM process-
ing. It can be seen that the Mo-11 and Mo-12 sample microstructures are similar
(Fig. 4a, b). In both samples (Fig. 4a, b), a netlike dendrite structure, which is much
more expressive in comparison to the Mo-00 initial sample (Fig. 3), can be seen. The
structure is inhomogeneous. The inhomogeneity of the composition is a result of the
presence of melts, which are formed between Mo and the metal impurities (~2%),
which are still available in the material.
The chemical analysis of the samples obtained after refining at a higher tempera-
ture (T = 3000 K) for 5 and 10 min melting times shows that the impurities’ content
is almost unchanged. In spite of this, the structures of the refined metal processed for
different lengths of melting time vary considerably (Fig. 4c, d). The Mo-21 sample
microstructure (Fig. 4c) is still inhomogeneous. Large light grains of elongated shape
and a torn netlike dendrite structure are observed. This can be explained with the
homogenization of melts formed between Mo and the metal impurities present in the
material. The Mo-22 sample, obtained for a refining time of 10 min, is characterized
Fig. 5 Microstructure of the 50 μm

Mo ingot (400x
magnification) manufactured
at a beam power of 17 kW
for a 10 min melting time
Mo-22 (x400)
Table 3 Average hardness

Sample no HVav (kgf/mm2 ) Standard deviation
and standard deviation
measured at molybdenum Mo-00 406.629 49.23
samples Mo-11 377.871 45.18
Mo-12 344.057 23.48
Mo-21 297.957 28.04
Mo-22 186.614 16.83
by a body-centered cubic structure with a mean grain diameter of ~100 µm, which
is formed at slow cooling of pure molybdenum (Figs. 4d and 5).
In summary, it was seen that the higher melting temperature and the longer refining
time led to the homogenization of the melt (to a less heterogeneous material). At slow
cooling of such a melt, even in the presence of impurities (of about 2%), well-formed
large grains with a shape close to a cubic one were formed, which is characteristic
of pure molybdenum.
The average Vickers hardness (HVav ) of Mo samples and the standard deviation
values at different EBM regimes are presented in Table 3. The results show that the
hardness values decrease by prolonging the refining time and with a higher beam
power. The hardness decrease will secure a good processing of the obtained material.
Conclusions
The specific physical and mechanical properties of molybdenum determine its appli-
cation in various fields of industry such as metallurgy, electronics, electrical engi-
neering, chemical industry, glass production, instrumentation, and medicine. The
influence of the beam power and refining time on the metal quality at electron beam
melting of molybdenum concentrate was studied in this work. Experiments have
been performed at different technological regimes. Thermodynamic conditions of
EBM and refining of molybdenum were analyzed. It has been shown that there are
no thermodynamic limitations for the removal of Al, Si, Fe, Cu, and Sb impurities at
EBM of the investigated molybdenum material. It was found that with longer refining
time and higher electron beam power, the hardness decreases and the metal ingots are
with an improved structure. The highest molybdenum purity (98.15%) was achieved
at 17 kW beam power for a 5 min melting time and the maximal overall removal
efficiency was 58%. The results allow us to formulate requirements on the process
conditions in order to improve the quality of the obtained metal material.
Acknowledgements The work has been supported by the Bulgarian National Science Fund under
contract DN17/9.
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Preparing Cuspidine Glass-Ceramics
from Iron-Removed Stainless Steel
Pickling Sludge
Guanghui Li, Jian Wang, Jing Chen, Jing-xiang You, Tao Zhang,
Jiao-yang Duan, Qing Ye, Zhiwei Peng, Mingjun Rao and Tao Jiang
Abstract Stainless steel pickling sludge is a kind of hazardous solid waste, which
mainly contains CaF2 , CaSO4 , and Fe(OH)3 depending on the pickling and pre-
cipitating procedure. In order to depress the decomposition of CaF2 to form toxic
fluorine-containing gas at high-temperature metallurgical process, this work was
aiming at the utilization of CaF2 from stainless pickling sludge by preparing cuspi-
dine glass-ceramics. Firstly, carbothermic reduction and magnetic separation were
conducted to recover iron, in which pickling sludge was reduced at 1000 °C for 1 h
by using 5% coke as a reducing agent and separated by magnetic separation with the
magnetic intensity of 0.1 T. The main composition of the magnetic concentrate was
Fe and Fe3 O4 with the corresponding iron recovery more than 80%. Subsequently,
the non-magnetic material was mixed with Ca(OH)2 and cullet to prepare cuspi-
dine glass-ceramic. After roasted at 900 °C for 2 h, a cuspidine glass-ceramic with
compressive strength of 65 MPa and porosity of 39.74% could be obtained.
Keywords Stainless steel pickling sludge · CaF2 · Iron removal · Cuspidine

glass-ceramics
Introduction
According to the report from the international stainless steel forum, the global output
of crude stainless steel reached 50.729 million tons in 2018 [1]. The stainless steel
surface pickling process results in large amount of pickling sludge accounting for
3–5 wt% of the output of stainless steel [2]. Stainless steel pickling sludge is one
of hazardous waste which mainly contains CaSO4 , CaF2 , and various heavy metal
elements such as Ni and Cr. On the other hand, it can be regarded as an important
secondary resource, because it commonly contains 10–20% iron, 2–3% chromium,
and 10–40% calcium fluoride [3, 4]. The utilization of pickling sludge is imperative,
G. Li · J. Wang · J. Chen · J. You · T. Zhang · J. Duan · Q. Ye · Z. Peng · M. Rao (B) · T. Jiang

School of Minerals Processing & Bioengineering, Central South University, Changsha 410083,
Hunan, People’s Republic of China
e-mail: mj.rao@csu.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_85
954 G. Li et al.
not only to solve the disposal and environmental problem caused by heavy metal
ions, but also to utilize the pickling sludge by recovering the valuable components.
In recent years, a lot of researches focused on utilizing the stainless steel sludge
have been conducted. The hydrometallurgy process is one of the wildly used methods
to recycle the valuable metal elements [5, 6]. Inorganic acid such as sulfuric acid,
hydrogen nitrate, and hydrochloric acid has been widespread used to leach the Fe, Ni,
Cr in the pickling sludge. It is reported that the leaching efficiency of the iron, nickel,
and chromium could be up to 99.8, 99.3, and 99.2% [7]. Although hydrometallurgy
process could efficiently recover metal components, this method needs complicate
steps and yields a large quantity of waste water which may cause additional pollution.
Compared to hydrometallurgy process, pyrometallurgy is more suitable for the
disposal of pickling sludge because of its simple process flow, such as smelting
reduction and direct reduction [8–10]. By smelting pickling sludge together with a
high-phosphorus-content oolitic hematite ore at 1550 °C for 90 min, the recovery of
Fe, Ni, and Cr could be up to 98.91%, 99.44%, and 98.46%, respectively [11]. The
metal in the pickling sludge was recovered by carbothermal direct reduction in the
form of alloy [12, 13].
In addition, the pickling sludge usually contains a high level of CaF2 which is a
common nucleating agent used in the preparation of glass-ceramics. Fluorine ions
enter the glass network and break the network, promoting glass crystallization [14].
It has been reported that the pickling sludge mixed with cullet was melted at 1460 °C
for 2 h, and then quenched into water to prepare a precursor for glass-ceramics. After
that, the rest melt was heated at 600 °C for 0.5 h to residual stress relaxation. Finally,
glass-ceramics with cuspidine as the main phase and Vickers hardness of 2690 MPa
were obtained [15]. However, preparing glass-ceramics by melting crystallization
requires high energy consumption [16, 17].
In this paper, the stainless pickling sludge was firstly treated by carbothermal
reduction– magnetic separation to recover iron, and meantime obtain a non-magnetic
material mainly containing CaF2 , which was further mixed with Ca(OH)2 and
cullet to prepare cuspidine glass-ceramics solidified heavy metal ions by reactive
crystallization.
Experimental
Materials
The stainless steel pickling sludge, collected from Desheng Stainless Steel Company
of Baosteel, Fujian, China, was used in this study. The main chemical composition
of the stainless steel pickling sludge sample was shown in Table 1. It’s iron and
Calcium content was 19.59% and 22.50%, respectively. The concentrations of other
elements including F, Cr, Ni, C were 16.71%, 3.48%, 0.7%, and 3.69%, respectively.
The coke breeze with particle size less than 100 mesh was used as the reducing agent.
Preparing Cuspidine Glass-Ceramics from Iron-Removed Stainless … 955
Table 1 Chemical composition of stainless steel pickling sludge (wt%)

Element F Na S Cl K Ca Fe Ni Cr C
Content 16.71 0.10 0.20 0.04 0.03 22.50 19.59 0.77 3.48 3.69
Its proximate analysis was shown in Table 2. The cullet regarded as silicon source
was ground to less than 200 mesh, and its chemical composition is shown in Table 3.
The XRD pattern of the stainless pickling sludge is shown in Fig. 1. Calcium
occurs mostly with calcium fluoride and calcium carbonate. The particle size of the
pickling sludge is quite small, about 50% of the particle size is less than 8.18 um, and
90% of the particle size is less than 29.304 um. Its size distribution curve is shown
in Fig. 2.
The thermogravimetric analysis of the pickling sludge is shown in Fig. 3. 2.20%
graphite was added into the stainless steel pickling sludge as reducing agent, the
mixture was heated up to 1200 °C in nitrogen, using a heat rate of 10 °C/min. The
mass loss at 500 °C is due to the loss of the hydrated water of calcium sulphate and
the metal hydroxide decomposition. The mass loss between 500 and 1000 °C occurs
Table 2 The proximate analysis of reducing agent (wt%)

Mad Aad Vad FCad
0.51 13.12 1.77 84.60
ad air-dried basis, M moisture, A ash, V volatile, FC fixed carbon
Table 3 The chemical analysis of cullet (wt%)

Formula SiO2 Na2 O CaO MgO Al2 O3 K2 O
Content 70.42 15.25 9.19 3.55 0.82 0.072

pickling sludge
956 G. Li et al.
Fig. 2 Particle size distribution of the pickling sludge
Fig. 3 TG-DSC curves of pickling sludge (Atmosphere: nitrogen gas, Temperature range: 25–
1200 °C; Heating rate: 10 °C/min)
because of the calcium carbonate decomposed at about 750 °C and the iron oxide was
slowly reduced. The increase of temperature promotes the reduction of iron oxide.
Method
According to the theoretical calculation, the theoretical required carbon content that
the iron oxide in the sludge is completely reduced to metal iron and carbon dioxide
(Fe2 O3 + 1.5C = 2Fe + 1.5CO2 ) is 3 wt%. Hence, the dried stainless steel pickling
sludge powder firstly mixed with the addition amount of reducing agent was deter-
mined to be 5 wt%. The mixture was reduced at 1000 °C for 60 min. After magnetic
separation, the non-magnetic material, mixed with Ca(OH)2 and cullet to prepare
cylindrical mass with diameter of 10 mm. Lastly, cylindrical mass was roasted at
900 °C for 2 h to prepare cuspidine glass-ceramics.
The phases of dried and calcined products of stainless steel pickling sludge were
identified using D8 Advance X-ray diffraction (BRUKER-AEX, Germany). The ther-
mal properties of the dried pickling sludge sample was studied by thermogravimetry
(TG) and differential scanning calorimetry (DSC), using STA-449F3 Jupiter (Net-
zsch, Germany) thermodynamic analyzer. The micro-structure was examined by
scanning electron microscopy (SEM Tescan mira3).
Reduction—Magnetic Separation for Iron Recovery
To optimize the reduction—magnetic separation index, the reduced temperature,

reduce time, and grind time were studied while keeping other process parameters
constant. The result of the reduction—magnetic separation was shown in Fig. 4.
As shown in Fig. 4, the metallization ratio and magnetic concentrate gradually
increased with the increasing reduction temperature, and the maximum of the iron
recovery appeared at 1000 °C The result can explain that with the temperature
increased, a large amount of liquid phase which promoting the growth of iron par-
ticles will be formed in the sludge. Nevertheless, the excess liquid phase will also
cause the phenomenon of inclusion and, leading to the reduction of iron recovery.
With the increase of reduced time, the calcine metallization rate sharply increased,
the iron recovery was slowly raised to more 80% as the reduced time increased from
30 to 60 min, and then the level off with the time exceeds 60 min. It is mainly because
the iron particle size increased with roasting time prolonged which provides better
separation conditions for magnetic separation.
Extending grinding time, the iron metal and magnetite dissociated from non-
magnetic minerals, thus the magnetic concentration increased sharply, the maximum
of the recovery appeared at 10 min. Further, prolong the grinding time, the magnetic
particle size was too small to separate from the non-magnetic minerals.
XRD pattern of roasting products at different reduction temperatures is shown in
Fig. 5. The iron oxide was gradually reduced to magnetite, ferrous, and metal iron
when the temperature was up to 900 °C. As the temperature continues to increase, the
ferrous oxides disappeared which means all iron oxides were converted to magnetic
minerals.
958 G. Li et al.
Fig. 4 Effect on iron recovery. a Effect of roast temperature on iron recovery under reduction—
magnetic separation conditions: roast time 60 min, grind time 10 min. b Effect of roast time on
iron recovery under reduction—magnetic separation conditions: roast time 1000 °C, grind time
10 min. c Effect of grind time on iron recovery under reduction—magnetic temperature separation
conditions: roast time 1000 °C grind time 60 min
Fig. 5 XRD pattern of calcine under various temperatures

Table 4 The compositions and physical characteristics of cuspidine glass-ceramics

Sample Mass ratio Molar ratio Compressive Porosity (%) Volume
(tailings: (CaF2 : SiO2 : strength (MPa) density
cullet: CaO) (g/cm3 )
Ca(OH)2 )
S1 1:2:2 1:3.05:3.94 5.00 58.61 1.07
S2 1:3:1 1:4.58:2.40 30.00 47.30 1.40
S3 1:3.5:0.5 1:5.34:1.63 65.00 39.74 1.65
S4 1:4:0 1:6.10:0.85 16.50 47.56 1.35
S5 0.5:3.5:1 1:10.68:5.01 43.00 44.24 1.45
Glass-Ceramic Preparation
The physical characteristics of different composition cuspidine glass-ceramics are

shown in Table 4. Keeping the proportion of tailings which contains 60 wt% CaF2
as constant, the ceramic compressive strength increased as the proportion with the
increase of waste glass, however, without addition of Ca(OH)2 , the compressive
strength quickly decreased. It is mainly because the liquid phase formed in the sinter-
ing process of waste glass with low melting point densifies the ceramics and improves
the compressive strength of the ceramics. Nevertheless, too much liquid phase dam-
ages the structure of ceramics, leading to an increase in voids and a decrease in
strength.
In this study, the XRD analysis was utilized to obtain crystal composition of
powder glass-ceramics specimens. It can be seen from Fig. 6, the cuspidine appeared
in all the samples, with the cullet content increased the major phase translated into
CaSiO3 . For sample S4, it remains a lot of Calcium fluoride which is not involved
in the reaction, thus the compositions of the ceramic play an important role in the
crystals formation process.
The microstructure of glass-ceramic was shown in Fig. 7, The glass-ceramics
consist of a continuous glass base and a few irregular micropores. With the cullet
content increased, the aperture of ceramic decreases at first and then increases. For the
S3 sample, the ceramic compact structure is composed of crystals with particle size
of about 4um, the microstructure and physical properties are highly consistent. Wang
suggested that Fe2 O3 residue from tailings in glass-ceramics can induce the formation
of small amorphous droplets distributed homogeneously in the glass matrix before
nucleation [18]. The interfaces between the amorphous droplets and glass matrix
phases serve as the heterogeneous nucleation sites for the final crystallization.
960 G. Li et al.
Fig. 6 XRD patterns of glass-ceramics (the sample composition (tailings: cullet: Ca(OH)2 mass
ratio: S1 = 1:2:1, S2 = 1:3:1, S3 = 1:3.5:0.5, S4 = 1:4:0, S5 = 0.5:3.5:1))
Fig. 7 The microstructure of glass-ceramic
Conclusions
In this study, the stainless steel pickling sludge was treated to prepare cuspidine
glass-ceramic and to recover iron. The iron oxide of the pickling sludge was reduced
to metallic iron with metallization ratio up to 80% at the temperature of 1000 °C
for 60 min. The metallic iron and magnetite were separated from the non-magnetic
material at the magnetic intensity of 0.1 T, meanwhile the iron recovery reached to
85%. Magnetized tailing containing 60% calcium fluoride was mixed with waste
glass and calcium hydroxide to produce cuspidine glass-ceramics by roasting at
900 °C for 2 h. The cuspidine glass-ceramics with compressive strength up to 65 MPa

and porosity of 39.74% could be prepared.
Acknowledgements This work was funded by “the National Natural Science Foundation of China
(51804346) and Hunan Provincial Innovation Foundation for Postgraduate (2019zzts173)”.
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pickling sludge: a review. J Iron Steel Res Int (6):547–557
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heavy metals in sodium sulfide hydrate stabilized stainless steel pickling sludge. Process Saf
Environ 123:79–86
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from sulfuric acid leaching solution of stainless steel pickling sludge. Environ Prot Chem Ind
38(03):353–357
7. Liu PY, Tan DS, Ding WZ (2017) A study on leaching heavy metals from stainless steel pickling
sludge. Nonferrous Met Mater Eng 38(03):149–153
8. Yoshikawa N, Mashiko KI, Sasaki Y, Taniguchi S, Todoroki H (2008) Microwave carbo-thermal
reduction for recycling of Cr from Cr-containing steel making wastes. ISIJ Int 48(5):690–695
9. Li XM, Xie G, Hojamberdiev M, Cui YR, Zhao JX (2014) Characterization and recycling of
nickel-and chromium-contained pickling sludge generated in production of stainless steel. J
Cent South Univ 21(8):3241–3246
10. Sun Y, Zhang J, Li T, Li QJ (2016) Experimental study on reduction Ni from stainless steel
sludge. Shanghai Met 38(02):64–68
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16. Si W, Xiong C, Zhang WY (2016) Properties of cuspidine glass-ceramics prepared by reactive
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17. Beall GH, Megles JE Jr (1984) Potassium fluorrichterite glass ceramics and method. U.S. Patent
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18. Wang SM (2010) Effects of Fe on crystallization and properties of a new high infrared radiance
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Pyrolysis of Waste Steel Tailings and Iron
Recovery
Na Wang, Wei Liu, Junwei Han, Xun Wang, Zihan Li and Wenqing Qin
Abstract Pyrolysis has recently received much attention as a promising technology

for recycling all the valuable materials from wastes. This study investigated the
thermal degradation behaviors of the waste steel tailings and the recovery of iron from
waste steel tailings using magnetic separation after pyrolysis. Thermogravimetric
(TG) and differential thermogravimetric (DTG) analyses were performed to study
the mass loss characteristics. The main pyrolysis temperature range of the waste
steel tailings was approximately from 100 to 800 °C and the total mass loss was
about 30%. The pyrolysis process of waste steel tailings could be classified into four
stages. The optimum pyrolysis temperature and pyrolysis time of waste steel tailings
were at 700 °C for 60 min. The pyrolysis residues generated during the process
under optimal condition were detailed analyzed by X-ray powder diffraction (XRD).
The result showed that the phase composition of iron in the pyrolysis residues was
magnetite. The results of magnetic separation showed that the recovery of iron was
92.66%.
Keywords Waste steel tailings · Pyrolysis · Magnetic separation · Secondary

resources · Thermogravimetric analysis (TGA)
Introduction
The iron and steel industry is an important part of the national economy and in general,
the mineral industry often accounts for a major percentage of the gross national
product in many countries [1]. Currently, with the rapid development of steel industry,
a large number of steel tailings are produced every year [2]. Steel tailings are by-
products of the steel industry, accounting for 10–15% of steel output [3]. According to
statistics, China’s crude steel output was 808.1 million tons in 2016, and steel tailings
output exceeded 100 million tons [4]. However, the utilization rate is only about
N. Wang · W. Liu · J. Han (B) · X. Wang · Z. Li · W. Qin

Peace Building, No. 101, Changsha 410083, China
e-mail: hanjunwei2008@163.com

https://doi.org/10.1007/978-3-030-36540-0_86
964 N. Wang et al.
29.5% [5], causing enormous resource waste and serious environmental pollution. At
present, there are some different ways of utilization of waste steel tailings. On the one
hand, steel tailings can be used as water treatment adsorbents, in glass ceramics, as
building materials, and as mineral fertilizers for its chemical properties and physical
structure [6]. On the other hand, steel tailings can be used to recycle useful metals
such as Fe, Co, Ni, and Cu [7]. In addition, with the continuous exhaustion of mineral
resources, iron ore resources in China become increasingly scarce [8]. Therefore, it
is of great significance to seek a scientific and environmental method to recycle iron
from waste steel tailings for resource utilization and environmental protection.
Pyrolysis, as a cost-effective and environment-friendly technology, has aroused
great concern in the field of recycling plastics [9–11], biomass [12, 13], waste printed
circuit boards [14–17], waste power batteries [18–21], and so on. Pyrolysis, the ther-
mal decomposition processing of waste steel tailings in the absence of oxygen or
under an inert atmosphere, is flexible in obtaining a combination of solid, liquid, and
gaseous products and emits fewer air pollutants (e.g., NOx and SO2 ) compared to
combustion [22]. Heavy metals can be retained in the char product during the pyroly-
sis process, and the liquid and gaseous products of pyrolysis can be further converted
into chemicals and fuels [23, 24]. Song et al. [25] investigated the synergistic dis-
posal of oil sludge and steel slag in a self-designed continuous pyrolysis-magnetic
(CPM) separation process. The results indicated that steel slag addition caused the
weight loss rate of oil sludge to increase. The recovery of steel slag from the solid
pyrolysis products of oil sludge containing steel slag was conducted in a magnetic
separator, and the maximum recovery rate could reach 55.03%. Therefore, pyrolysis
would be a promising and practicable method for waste steel tailings to achieve all
resource recovery as well as zero emissions. As we all know, the most economic and
environmental-friendly method to recover iron is magnetic separation. Hence, we
proposed a pyrolysis and magnetic separation process to dispose of the waste steel
tailings.
This paper aims to study the pyrolysis behavior of waste steel tailings in pyrolysis
reactors and the recovery of iron from pyrolysis solid products. Thermogravimetry
(TG) analysis was performed to describe the pyrolysis behaviors. The effect of reac-
tion temperature and time were investigated to optimize the experimental conditions
under the pyrolysis of waste steel tailings. The effects of high voltage separation
and magnetic separation were investigated to recover iron from pyrolysis waste steel
tailings.
Experimental
Materials
The waste steel tailings used in this study were obtained from a local steel plant in
Hunan, China. The waste steel tailings consist of metals and nonmetallic powders.
Pyrolysis of Waste Steel Tailings and Iron Recovery 965
This experiment mainly took the nonmetallic powders as the research object. These
samples were screened with a sieve of 10 mm to separate the coarse material from
the fine material. The samples under the screen were dried at 105 °C for 12 h in
an electric oven thermostat in order to remove moisture. After drying, the waste
steel tailings were used for subsequent use and chemical composition, TG and XRD
analysis.
Experimental Process
The pyrolysis processes of waste steel tailings were conducted in a closed pyrolysis
system, schematic of which was shown in Fig. 1. The pyrolysis reactions were per-
formed in a well type furnace, the temperature of which was controlled by a program
controller. Nitrogen (N2 ) was provided as a protective gas. About 100 g of dried waste
steel tailings were put into a crucible and then were loaded into the well-type furnace.
The furnace was then sealed under the atmosphere of nitrogen gas (N2 ) at a flow rate
of 1 L/min. Thereafter, the samples were heated at a heating rate of 60 °C/min from
room temperature to the scheduled temperature and roasted at this temperature for the
required pyrolysis time. When the pyrolysis finished, the pyrolysis residues cooled
to room temperature at a flow rate of 1 L/min N2 . The pyrolysis residues were then
removed from the well-type furnace, weighed and stored for analysis and subsequent
magnetic separation experiment. During magnetic separation process, the pyrolysis
residues obtained under the optimum pyrolysis conditions were ground to—0.5 mm.
For each test, 20 g of pyrolysis residues were used for magnetic separation experi-
ments. The iron recovery test was performed in a low-intensity magnetic separator
(model: XCGS-F50) to investigate the magnetic separation performance of iron from
the pyrolysis residues.
Fig. 1 Schematic diagram of thermal decomposition furnace: (1) nitrogen cylinder, (2) pyrolysis
reactor, (3) electric heating furnace, (4) samples, (5) crucible, (6) temperature controller, (7) primary
condensation collection device, (8) secondary condensation collection device, (9) airbag
966 N. Wang et al.
Characterization Techniques
In the present study, the percentage composition of iron was determined by induc-
tively coupled plasma (ICP-AES, IRIS Intrepid II XSP) while the percentage com-
position of other elements was analyzed by X-ray fluorescence (XRF, Rigaku, ZSX
Primus II). The chemical composition of the waste steel tailings was shown in Table 1.
The qualitative and quantitative information about crystalline phases were deter-
mined by X-ray powder diffraction (XRD, Rigaku, TTR-III) and chemical methods,
respectively. Thermogravimetric (TG, PerkinElmer STA8000) analysis and Fourier
transform infrared spectroscopy (FTIR, PerkinElmer Spectrum Two) were used to
investigate the pyrolysis behaviors of the samples, respectively. The TG analysis was
carried out from 10 to 1000 °C at heating rates of 5, 10, and 20 °C/min under nitrogen
atmosphere, and the flow rate of nitrogen was regulated to 50 mL/min.
TG and DTG Analysis
Thermogravimetric (TG) and differential thermogravimetric (DTG) analyses were

performed to study the mass loss characteristics. Figure 2a, b showed TG and DTG
curves of the waste steel tailings pyrolysis under nitrogen atmosphere from 10 to
1000 °C at heating rates of 5–20 °C/min. The pyrolysis characteristic parameters of
the waste steel tailings were presented in Table 2. The main temperature range of the
waste steel tailings pyrolysis was approximately 100–800 °C. Maximum degradation
temperatures were observed at peak 1 (235, 239, and 257 °C at heating rates from 5
to 20 °C/min), peak 2 (371, 400, and 410 °C at heating rates from 5 to 20 °C/min)
and peak 3 (645, 654, and 690 °C at heating rates from 5 to 20 °C/min). The weight
loss at the final temperature was around 30%. It could be observed that the TG
curves and DTG peaks were moved from low temperature to high temperature as
the heating rate increased. In addition, the initial reaction temperature and terminal
reaction temperature were improved as heating rates increased from 5 to 20 °C/min.
The pyrolysis of waste steel tailings could be divided into four separate stages, which
was shown in Table 3. The first part of waste steel tailings pyrolysis was Stage I,
which ranged from 104 to 271 °C, 115 to 282 °C, and 129 to 307 °C at heating rates
from 5 to 20 °C/min, respectively. The weight loss of waste steel tailings in this stage
is about 7.27% relating to the low boiling volatiles released. Stage II corresponded to
the temperature range of 271–495 °C, 282–500 °C, and 307–520 °C for heating rates
from 5 to 20 °C/min, respectively. About 8.38% mass of the total mass of original
samples occurred in this stage. The reason for this pyrolysis reaction at Stage II was
that the high boiling volatiles were released. The third part of waste steel tailings
pyrolysis was Stage III, relating to the pyrolysis reaction of waste steel tailings with
the temperature range of 495–687 °C, 500–695 °C, and 520–790 °C for heating
Table 1 Chemical composition of the waste steel tailings
Element Fe O Si Ca Zn Al Mg Ti Na K
Pyrolysis of Waste Steel Tailings and Iron Recovery
wt% 48.15 20.04 8.15 5.96 6.42 2.36 1.53 4.06 0.39 0.45
967
968 N. Wang et al.
Fig. 2 TG (a) and DTG (b) curves of waste steel tailings
Table 2 Pyrolysis characteristics of waste steel tailings

Sample Heating rate β Main pyrolysis Maximum Weight loss at
(°C/min) range (°C) degradation 1000 °C (wt%)
temperatures (°C)
Tm1 Tm2 Tm3
Waste steel 5 104–687 235 371 645 29.25
tailings 10 115–695 239 400 654 33.76
20 129–790 257 410 690 22.07
Table 3 Pyrolysis reaction stages of waste steel tailings

Sample Heating rate β Temperature range (°C)
(°C/min) Stage I Stage II Stage III Stage IV
Waste steel tailings 5 104–271 271–495 495–687 687–1000
10 115–282 282–500 500–695 695–1000
20 129–307 307–520 520–790 790–1000
rates from 5 to 20 °C/min, respectively. The high boiling volatiles were continuously
generated in this pyrolysis stage. Stage IV took place in high temperature range of
687–1000 °C, 695–1000 °C, and 790–1000 °C for heating rates of 5–20 °C/min,
respectively. The thermal decomposition was basically completed with some small
molecules released.
Pyrolysis Experiments
Effect of Pyrolysis Temperature and Time
According to the TG and DTG analysis, pyrolysis temperature of waste steel tailings
started around 100 °C and ended around 800 °C. Hence, the experiments were con-
ducted in the pyrolysis temperature range from 200 °C to 800 °C at 1.0 L/min N2 flow
rate lasting 60 min. The relationship between weight loss rate of waste steel tailings
and pyrolysis temperature was shown in Fig. 3a. It showed that the weight loss rate
of waste steel tailings increased significantly with an increase of temperature. When
the pyrolysis temperature was 700 °C, the weight loss rate of waste steel tailings
reached 35.5%. With the pyrolysis temperature over 700 °C, the weight loss rate of
waste steel tailings reached approximately 36.2%. Waste steel tailings no longer had
the change of quality loss, which indicated that the pyrolysis reaction was basically
complete. Therefore, the optimal pyrolysis temperature of waste steel tailings was
700 °C.
The effect of pyrolysis time on weight loss rate of waste steel tailings was inves-
tigated in the range from 30 to 80 min at 1.0 L/min N2 flow rate. Figure 3b showed
that the weight loss rate of waste steel tailings at different holding times under the
condition of final pyrolysis temperature of 700 °C. As shown in Fig. 3b, with the
increase of the holding time, the weight loss rate of waste steel tailings increased.
When the holding time was 30 min, the weight loss rate of waste steel tailings was
10.8%. A significant increase appeared at 50 min, where the weight loss rate of waste
steel tailings jumped to 25.9% from 16.5% under the 40 min. The weight loss rate
of waste steel tailings reached 32.7% when the holding time was 60 min. When
the holding time was more than 60 min, the weight loss rate of waste steel tailings
remained basically the same. The reason for this phenomenon could be explained
that pyrolysis reaction of waste steel tailings was basically complete. Therefore, the
optimal pyrolysis time of waste steel tailings was 60 min.
Fig. 3 Effects of pyrolysis temperature (a) and pyrolysis time (b) on the pyrolysis behaviors of
waste steel tailings
970 N. Wang et al.

pyrolysis residues
Analysis of Pyrolysis Residues
XRD analysis was carried out on the pyrolysis residues under the best pyrolysis
conditions (700 °C, 60 min), as shown in Fig. 4. The result showed that the phase
composition of iron in the pyrolysis residues was magnetite. Besides magnetite,
pyrolysis residues also contained quartz and calcite. Magnetite was a magnetic min-
eral which could be used to recover iron by magnetic separation. Therefore, iron
could be recovered from pyrolysis residues by magnetic separation.
Magnetic Separation
Effect of Magnetic Field Intensity
The magnetic separation was performed on the pyrolysis residues to investigate

the possibility of iron recovery using the proposed method. The effects of different
magnetic field intensity on the grade of magnetic concentrate and iron recovery rate
were shown in Fig. 5. As shown in Fig. 5, by the separation of magnetic separator, the
grades of magnetic concentrate were all over 64% Fe, meeting the required standard
of iron making. With the increased magnetic field intensity, the recovery rate of iron
increased gradually. When the magnetic field intensity was 300 mT, the recovery of
iron reached the maximum value of 92.66%.
XRD Analysis
The magnetic concentration and tailing with magnetic field intensity of 300 mT were
carried out for XRD analysis, respectively. XRD pattern was shown in Fig. 6. It could
be seen from Fig. 6 that the magnetic concentrate was mainly magnetite (Fe3 O4 ) with
Fig. 5 Effects of different magnetic field intensity on the grade of magnetic concentrate and iron
recovery rate
Fig. 6 XRD pattern of the magnetic concentration (a) and tailing (b) with magnetic field intensity
of 300 mT
a small amount of quartz and calcite while the magnetic tailings were mainly quartz,
calcite, and mica, with only a small amount of magnetite (Fe3 O4 ). The crystal phase
of magnetite (Fe3 O4 ) was further confirmed by X-ray diffraction. These indicated
that the best recovery effect of iron was achieved when the magnetic field intensity
was 300 mT.
Conclusions
Pyrolysis is a promising and practicable method for waste steel tailings to achieve the
requirements of cyclic utilization and green development. This study investigated the
thermal degradation behaviors of the waste steel tailings and the recovery of iron from
waste steel tailings using magnetic separation after pyrolysis. Thermogravimetric
972 N. Wang et al.
(TG) and differential thermogravimetric (DTG) analyses were performed to study

the mass loss characteristics. The main pyrolysis temperature range of the waste steel
tailings was approximately from 100 to 800 °C and the total mass loss was about
30%. The pyrolysis process of waste steel tailings could be classified into four stages.
In Stage I, low boiling volatiles were formed. In Stage II, high boiling volatiles were
released. In Stage III, high boiling volatiles were continuously generated. In Stage
IV, pyrolysis reaction was basically completed with few small molecules released.
The optimum pyrolysis temperature and pyrolysis time of waste steel tailings were at
700 °C for 60 min. The pyrolysis residues generated during the process under optimal
condition were detailed analyzed by X-ray powder diffraction (XRD). The result
showed that the phase composition of iron in the pyrolysis residues was magnetite.
The results of magnetic separation showed that the recovery of iron was 92.66%.
Acknowledgements The authors gratefully acknowledge the financial support by the National
Natural Science Foundation of China (No. 51804342 and No. 51874356), the Natural Science
Foundation of Hunan Province (No. 2019JJ50805), the Innovation-Driven Plan of Central South
University (No. 2015CX005), Key Laboratory of Hunan Province for Clean and Efficient Utilization
of Strategic Calcium-containing Mineral Resources (No. 2018TP1002), and the Scientific Research
Starting Foundation of Central South University (No. 218041).
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Research of Gas–Liquid Multiphase Flow
in Oxygen-Enriched Bottom Blowing
Copper Smelting Furnace
Li Dongbo, Dong Zeshang, Yao Xin, Liu Cheng, Guo Tianyu, Li Bing
and Li Peng
Abstract Based on ENFI’s self-developed bottom-blowing continuous copper

smelting process, the normal operation bottom-blown copper smelting furnace is
the research object. Based on the determination of the physical parameters of the
slag phase and matte phase in the furnace, the bottom-blow furnace model consis-
tent with the actual bottom blowing system is established by using the commercial
software platforms. The VOF multiphase flow model and the standard k−ε turbu-
lence model are used to simulate the three-phase flow process of gas-slag-matte in
the furnace. The gas–liquid two-phase flow law in the furnace, the velocity field of
each phase in the furnace, and the splashing mechanism of the melting furnace are
analyzed. The characteristics of each flow region in the furnace are obtained. This
study can also provide a reference for the design and operational system formulation
of the bottom blowing furnace.
Keywords Continuous copper refining · Copper smelting furnace · Gas–liquid

two-phase flow · Numerical simulation · Oxygen rich bottom blowing
Introduction
In recent years, with global warming, environmental deterioration and shortage of

energy resources and other issues, high energy consumption, and high pollution
enterprises are facing tremendous pressure [1]. Industrial furnaces are important
production equipment in machinery, building materials, and metallurgy sectors, and
also high energy consumption equipment [2]. At present, there are still some energy-
saving shortboards in China’s non-ferrous metallurgical furnaces, which have great
energy-saving potential [3]. In this context, new non-ferrous metallurgical smelting
technology and equipment emerge in endlessly. The bottom blowing technology in
non-ferrous metallurgical industry was initiated by ENFI, China. It has the advantages
of low investment, good environmental protection, and low energy consumption [4].
L. Dongbo · D. Zeshang · Y. Xin (B) · L. Cheng · G. Tianyu · L. Bing · L. Peng

China ENFI, 12 Fuxing Avenue, Beijing, China
e-mail: yaoxin@enfi.com.cn

https://doi.org/10.1007/978-3-030-36540-0_87
976 L. Dongbo et al.
It was initially applied in the lead smelting industry [5]. It has brought tremendous
technological progress in the lead smelting industry. Since the 1990s, the first gen-
eration of bottom blowing copper smelting technology and the second generation of
bottom blowing copper smelting technology have been developed one after another
[6]. Substituting bottom blowing for continuous copper smelting technology, success-
ful industrialization, and achieved good results, with strong competitiveness, market
share continues to expand. The “One Shoulder Pole” copper technology, which is
currently under development [7], is leading the future development direction of cop-
per smelting technology. The bottom blowing technology will certainly occupy a
place in the future copper smelting industry. Bottom blowing furnace (BBF), as the
core device of bottom blowing technology, is attracting more and more attention
from experts and scholars [8, 9]. Its core feature is that high-pressure gas is injected
from the bottom of the furnace at high speed to improve the smelting effect. This
feature is widely used in the smelting and refining process of various metals. Gas
is injected into metallurgical melt from the bottom which converts the gas kinetic
energy into the melt kinetic energy, and completes a series of complex metallurgical
physical and chemical processes, such as pool mixing, mass transfer, and reaction
between gas and liquid. In order to optimize the reactor structure, injection mode,
and technical parameters, it is necessary to understand the internal mechanism of
these phenomena, but it is difficult to observe and analyze these phenomena directly
in the actual smelting process. Therefore, it is necessary to realize visual analysis by
means of simulation. The numerical simulation method has the advantages of full
information, short cycle, low cost, safety, and reliability. At present, it has become
an important method to study complex gas–solid–liquid multiphase fluid systems in
various industrial furnaces. Most of the existing simulation models of BBF [10] are
slot models or local models, only considering single lance or two lances. There are
few studies on the whole furnace model. There are several lances distributed in the
length direction of the actual BBF. The lances interact with each other and stir the
molten pool, which results in different flow phenomena in the furnace. The purpose
of this paper is to establish a mathematical model about the BBF through a series of
commercial software such as ANSYS Fluent and SolidWorks. The VOF multiphase
flow model and standard k-ε turbulence model were used to simulate the three-phase
flow of matte, slag and gas in the BBF, and the flow pattern of fluid in the furnace
was analyzed in order to provide a reference for the design and operation of the BBF.
Pre-process of the BBF Simulation
Taking the bottom blowing smelting furnace developed and designed by ENFI, China,
as the research object, the smelting process of the bottom blowing smelting furnace
is briefly described as follows [6]: After pelletizing copper sulfide concentrate, other
copper-containing materials, and flux, it is put into the furnace at the top of the
furnace to produce high-grade matte and smelting slag, and the flue gas is cooled by
the waste heat boiler. Then it is sent to the electrostatic precipitator to purify the dust,
Research of Gas–Liquid Multiphase Flow in Oxygen-Enriched … 977
and last sent to the acid plant to produce sulphuric acid. The commercial software
is used to pre-process the whole furnace, such as geometric modeling, meshing, and
boundary condition parameter calculation.
Establishment of Geometric Model and Grid Division
Figure 1 shows the geometric model of BBF by the commercial software SolidWorks
with a scale of 1:1 to the actual size. The left side of the furnace is a flue, and there
are 14 (7 groups) lances at the bottom. During the actual operation, some lances can
be blocked according to the furnace conditions. In order to facilitate the maintenance
and repair of the furnace, the flue and the axis of the furnace center deviate from a
certain distance, and the direction of the lance is 15° from the vertical direction.
The discretization strategy of block partition and local refinement is adopted.
Structured grid partition is used in the calculation area. The lance and its surround-
ing area are partially refined. The mesh number in the area far from the lance is
reduced. The results of mesh generation are shown in Fig. 2. To ensure computa-
tional efficiency, the mesh number is ultimately controlled within 1 million. The
grid parameters are shown in Table 1. The mesh quality meets the requirement of
computational accuracy.
Fig. 1 Geometric model of the BBF
Fig. 2 Grid diagram

Table 1 Grid parameters

Name Value
Grid type Hexahedral
Grid number 850000
Determinant >0.5
Angle >27°
Selection of Calculation Methods
Model Hypothesis
The complex phenomena of mass, momentum, and heat transfer are involved in the
copper BBF. It is difficult to calculate the multi-physical field coupling numerical
value. In the simulation, the multiphase flow in the furnace is assumed and simplified
as follows: (1) the initial melt is stationary; (2) the high temperature melt in the
molten pool is incompressible fluid; (3) the feeding and discharging do not take
into consideration; (4) the effects of chemical reactions between gas and liquid and
reaction exothermic on gas–liquid two-phase flow are not considered.
Basic Governing Equations
The VOF multiphase flow model is used to simulate the gas–liquid multiphase flow
in the molten pool furnace [11]. For the gas–liquid multiphase flow, the volume
function α (the ratio of fluid volume to unit volume) is defined in the calculation,
and the position of the free surface is determined by establishing and solving the
transport equation of α. When α = 1, the unit volume is filled with liquid; α = 0,
there is no liquid in the unit volume; between 0 and 1, the unit volume is filled with
both liquid and gas, and this unit is a free surface unit.
(1) Mass conservation equation
In the VOF model, the tracking interface is mainly completed by solving the con-
tinuity equation of the volume fraction of one or more phases, which is shown as
follows:
∂ ·
n
·
(αq ρq ) + ∇ · (αq ρq vq ) = Sαq + (m pq − m q p ) (1)
∂t p=1
In the formula: t is the simulation time; αq represents the volume fraction of the
Q phase; ρq represents the density of the Q phase; vq represents the velocity of the
· ·
Q phase; m pq represents the mass transfer from P phase to Q phase; m q p represents
the mass transfer from Q phase to P phase; Sαq represents the source term of the Q
phase; ∇ represents the operator symbol whose expression is

∂ ∂ ∂
∇= + + (2)
∂x ∂y ∂z
(2) Momentum conservation equation
In the VOF model, the velocity field obtained by solving a single momentum equation
in the region is shared among all phases, as shown below.
∂
(ρv) + ∇ · (ρvv) = −∇p + ρg + ∇[μ(∇v + (∇v)T ] + ρg + F (3)
∂t
where: ρ represents fluid density; v represents the fluid velocity; μ represents the
dynamic viscosity; p means pressure; F represents the volume force acting on the
control volume.
Turbulence Model
In the copper sulfide concentrate oxidizing smelting furnace, oxygen-rich gas injected
by bottom lance enters the molten pool in the form of jet. The flow behavior is a strong
turbulent process. For turbulence, the standard k−ε model is used to describe it. The
K equation is an exact equation, and the e equation is derived from the empirical
formula. The equation is as follows:

∂ μT,m
(ρk) + ∇ · (ρkv) = ∇ · [ ∇k ] + G k,m + G b,m − ρε (4)
∂t σk

∂ μT,m ε
(ρε) + ∇ · (ρεv) = ∇ · [ ∇ε ] + (C1 G k,m + C1 C3 G b,m − C2 ρε) (5)
∂t σε k
In the formula, ρ represents the density;

v represents the velocities; μT,m represents
the turbulent viscosities, μT,m =ρCμ k2 ε, Cμ represents the empirical constants, 0.9;
Gk,m represents the turbulent energy due to the average laminar velocity gradient;
Gb,m represents the turbulent energy due to buoyancy; σk , σε represents the turbulent
Prandtl number of K and ε, respectively. The empirical constants of turbulence in the
model are usually C1 = 1.44, C2 = 1.92, C3 = 1.0, σk = 1.0, σε = 1.3, respectively.
Process Conditions
The boundary conditions of the numerical simulation are calculated by MetCal. The
parameters of the BBF operation are obtained. The number of lances is 7 (one for
each group and the other one for blocking guns). The melt heights are determined
Table 2 The boundary conditions

Name Density (kg m−3 ) Dynamic Melt height Gas supply
viscosity (mm) (Nm3 h−1 )
(kg m−1 s−1 )
Oxygen-enriched 1.32 1.79 × 10−5 – 12362.00
air
Matte 5300–5500 0.004 1100.00 –
Smelting slag 3400–3600 0.900 600.00 –
according to the actual working conditions. The physical parameters and boundary
conditions of the melt used in this calculation are listed in Table 2.
Solver Settings
Explicit Volume Fractional parameter and Implicit Body Force equations are used in
this model. The unsteady calculation is used for the multiphase flow. The adaptive
step size is adopted, and the Coulomb number is set to 5.0. The pressure–velocity
coupling mode adopts the SIMPLE format. Pressure discretization using PRESTO!
format. The second-order upwind is used for momentum calculation. The Compres-
sive format is used for volume ratio calculation. The first order upwind is used for
other parameter calculation. The convergence residuals are set to 1.0 × 10−3 .
Calculation Results and Discussion
Model Verification
It is necessary to verify the accuracy of the mathematical model calculation results

for the following analysis, so the calculation results are compared with the water
model experimental results. As shown in Fig. 3, the figures show the changes of the
gas morphology in the two models after it is injected from the bottom lance into the
molten pool. When it enters the molten pool, because the molten pool has a high
pressure and the bubbles also have a high pressure, so the bubble column appears
smaller. With the increase of the bubble column, the pressure of the molten pool
decreases, and the bubble column expands until it reaches the surface of the molten
pool. The numerical simulation results are very similar to the experimental results
of the water model, which proves that the assumptions and calculation methods
of this mathematical model are reasonable. Because of the limitation of the water
model experiment, it is necessary to analyze the results of the numerical model in
more detail. This part lays the foundation for the detailed analysis of the simulation
results.
Fig. 3 Numerical simulation results versus water model experimental results
Characteristics of Gas–Liquid Flow Characteristics

at the Initial Stage of Smelting
There are mainly three phases in the BBF: gas, slag, and matte. The density of each
phase is matte > slag > gas. In order to observe the gas–liquid distribution law in the
furnace, the liquid density contour on the lance longitudinal and transverse sections
at the initial stage of smelting are drawn in Fig. 4. As shown in Fig. 4, the color depth
represents the density, thus representing different kinds of phases.
As can be seen from Fig. 4, oxygen-rich gas is continuously injected into the
furnace from the bottom. Because of the strong pressure of the gas, it can break
through the gravity of the molten pool and rapidly rise through the matte layer and
slag layer. The intermittent bubble column generated in this process, when the bubbles
diffuse to the surface of the molten pool, the gas pressure decreases sharply, and the
bubbles break up and overflow the molten pool surface, and the pressure energy and
kinetic energy are also transferred to the surface melt and produce fluctuation. The
surface melt will flow around and collide with the wall to produce reflected waves.
The reflected wave collides with the newly generated wave to realize the agitation of
the molten pool surface. The stirring of the molten pool mainly exists in two areas:
the intense stirring near the bubble column and the molten pool surface, while the
melt in other areas fluctuates only slightly. Therefore, the reaction area in the molten
pool corresponds to the strong stirring area, while other areas provide conditions for
the settlement separation of matte and slag. The lance distribution of this furnace
can not only accelerate the reaction progress in the gas–liquid reaction zone, but also
facilitate the separation of matte and slag settling. Therefore, the bottom blowing
method improves production efficiency and greatly reduces the slag entrainment
phenomenon when matte is discharged.
0.0s
0.5s
1.0s
1.5s
2.0s
12.0s
Fig. 4 Gas-liquid distribution characteristics at the initial stage of smelting
Velocity Field in Furnace
According to the actual operation conditions of BBF, there are low- and high-speed
flow zones in the BBF. The smelting characteristics of BBF determine the distribution
law of each zone. The flow law of each zone has important guiding significance for
furnace design and operation optimization. Therefore, a stable time is selected to
show the range of fluid velocity in 0–2.0 m/s and 0–50.0 m/s, respectively. The
velocity contour of the fluid on the cross section of the lance is plotted as shown in
Fig. 5.
Firstly, the low-speed (0–2.0 m/s) flow region is observed. The fluids in this region
mainly include the gas area far from the flue and the settlement area. It can be seen
that there is a strong flow near the bubble column produced by the gas injection and
the surface of liquid slag. The fluids in the high-speed (0–50.0 m/s) flow zone mainly
Fig. 5 Schematic diagram of melt velocity zone in the furnace at a certain moment
include the gas area near the flue and the high-speed gas at the exit of the lance, one
is the fast-flowing area of the flue gas and the other is the area with intense gas–liquid
reaction.
Through the above analysis, we can roughly describe the flow law of the gas
injected into the furnace. The high-speed gas injected by the bottom lance impacts
the high-temperature melt, contacts the matte and slag in turn, stirring the melt while
continuously occurring gas–liquid reaction. The flue gas generated by the reaction
diffuses into the flue, and is pumped out from the flue into the waste heat boiler. The
furnace body is divided into four zones by bottom oxygen lance arrangement: matte-
slag settlement separation zone: in the molten pool area without lance arrangement,
the two melts flow slowly to achieve smooth separation; gas–liquid violent reaction
zone: near the bubble column area produced by the lance and the surface of the
molten pool, the melt stirs strongly and reacts; gas-phase low-speed flow zone: gas
area far away from the flue, the gas in this part flows horizontally to the flue, and the
velocity increases gradually; gas-phase high-speed flow area: located at the entrance
of the lance and lower part of the flue.
Spatter Analysis
Because of the high stirring intensity of the BBF, it is easy to produce melt splashing in
the furnace, which causes blockage of feeding inlet. Cleaning feeding inlet consumes
a lot of manpower and material resources, and affects smelting progress. Therefore, it
is necessary to analyze the splashing behavior of melt under this working condition.
Figure 6 shows that the equivalent surface of the matte and slag phase volume
fraction of 0.1 (assuming minimum splashing concentration) at different times. For
the convenience of comparing the gas-phase volume fraction of 0.9 equivalent sur-
faces at the same time is also made. The law of splashing in the smelting process is
qualitatively analyzed. It is obvious that the height of the matte is much higher.
Then the volume fraction distributions of matte and slag in the radial height of the
furnace are analyzed quantitatively on the lance section at a certain moment which
is shown in Fig. 7. The horizontal axis represents the height and the vertical axis
represents the volume fraction of the phase. It is also clear that the matte exists at a
higher height.
Matte 0.1
Slag 0.1
Gas 0.9
Fig. 6 Equivalent surfaces of different fluid volume fractions at a certain time
3.06 m 2.51 m
Fig. 7 The volume fraction of matte and slag at different furnace heights at a certain moment
It can be seen from the figures that the spattering height of matte is obviously
higher than that of slag. It is preliminarily judged that the spattering substance is
mainly in the lower layer of the molten pool. Then the gas-phase volume fraction
of 0.9 equivalent surface is observed. The shape of the equivalent surface is similar
to that of copper matte volume fraction 0.1. The vertical solid black line in Fig. 7
represents the maximum height of the spray. It is obvious that the splash height
3.06 m of matte is higher than that of 2.51 m of slag. The splashing mechanism of
bottom blowing smelting furnace can be obtained as follows: the gas injected from
the bottom lance first contacts with the matte layer, which drives the violent stirring
of matte, and copper mattes are involved in smelting slag during ascent. In actual
production, the most effective way to control splashing is to select a reasonable
height of the molten pool. By optimizing the feeding system and gas supply system
the appropriate height of molten pool can be obtained, which can not only ensure
high production efficiency but also prevent production interruption caused by the
melt splashing.
Conclusion
An actual size bottom-blown copper smelting furnace mathematical model is estab-

lished based on the original data such as the principle of bottom-blown copper
smelting, engineering experience, metallurgical calculation, and design drawings.
The process parameters of actual production are used for simulation calculation, and
the results are analyzed. The rationality of the mathematical model is verified by
comparing it with the water model experimental results. The gas–liquid two-phase
flow law, the velocity field of each phase and the spraying mechanism of smelting in
the furnace are analyzed, and some basic data which cannot be obtained in produc-
tion site or laboratory are obtained. The conclusions are as follows: the gas–liquid
chemical reaction in bottom blowing smelting furnace mainly occurs near the bubble
column and the surface of the molten pool produced by injecting gas, and there are
only minor fluctuations in other melt areas, thus realizing the rational separation of
the strong smelting area and the settlement separation area; the flow area in furnace
is mainly divided into the matte-slag settlement separation area, gas-liquid violent
reaction area, gas-phase low-speed flow area, and gas-phase high-speed flow area.
The different zone realizes different smelting functions in the BBF and achieves good
functional zoning. The most effective way to control splashing in the BBF production
is to select reasonable bath height. By optimizing the feeding system and gas supply
system, the appropriate bath height can be obtained.
References
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and short process copper smelting—“One Shoulder Pole” copper technology. Nonferrous Met
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on bottom blown molten pool melting process. J China Nonferrous Met 8:2393–2400
Selective Recycling of Cu Alloys
from Metal-Rich Particles of Crushed
Waste Printed Circuit Boards
by High-Temperature Centrifugation
Long Meng, Yiwei Zhong, Zhe Wang and Zhancheng Guo
Abstract High-temperature centrifugation is an efficient and environmentally

friendly method for separating and recycling comminuted waste printed circuit
boards (WPCBs). In this research, it was used to recover copper (Cu) from metal-rich
particles of WPCBs. Two steps separation process were conducted, and two alloys
(Sn–Cu and Cu–Zn) were obtained at different temperatures. The results indicate
that temperature has a great influence on the composition of Cu alloy, while the
gravity coefficient only affects the recovery rate. At an optimized temperature of
1300 °C and a gravity coefficient of 1000, the total recovery values of Cu, Zn, Pb,
and Sn were 98.84%, 86.96%, 98.33%, and 92.62%, respectively. By a combination
of appropriate hydrometallurgical process and centrifugal separation of metals, this
clean and efficient technology achieved a new way of recycling valuable metals from
PCBs and effectively preventing environmental pollution of WPCBs.
Keywords Printed circuit boards · High-temperature centrifugation · Recovery ·

Copper alloys
Introduction
Due to the technological advances and the obsolescence of electrical and electronic
equipment (EEE) on the market, the amount of electronic waste (e-waste) is growing
quickly [1]. In 2016, about 45 million tons of waste EEE (WEEE) was produced
L. Meng · Y. Zhong · Z. Wang · Z. Guo (B)

State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, 30
Xueyuan Road, Beijing 100083, People’s Republic of China
e-mail: zcguo@ustb.edu.cn
L. Meng
National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology,
Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, People’s
Republic of China
Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese
Academy of Sciences, Beijing 100190, People’s Republic of China

https://doi.org/10.1007/978-3-030-36540-0_88
988 L. Meng et al.
globally, and this value grows by 2 million tons per year [2, 3]. Printed circuit
boards (PCBs), the key central components of EEE, accounted for about 3% of
the total WEEEs generated [4]. PCBs are composed of different materials such as
polymers, ceramics, and metals, which make the process more difficult. However,
the concentrations of several metals present in PCBs are much higher than those
typically found in corresponding ores. If there is no appropriate treatment, it not
only causes a great waste of resources but also has great harm to the environment.
Therefore, it is an urgent problem to recover the valuable components from waste
PCBs (WPCBs) for preventing environmental pollution and protecting the resource.
Metal elements are the most valuable and widely used components in WPCBs.
PCBs contain many valuable metals such as Cu, Pb, Sn, Cd, Au, and Ag. As the
high electrical conductivity, Cu in PCBs is economically and ecologically the most
interesting metal for recovery and used as a secondary raw material because of its
relatively high content compared to the corresponding content in explorable ores
and its economic value [5]. Many reports have been investigated on the recovery of
Cu. The existing processes of recycling WPCBs used pyrometallurgical methods [6,
7], or hydrometallurgical processes [8, 9], which generated atmospheric pollution
through the release of dioxins and furans or high volumes of spent acid and effluents.
Some researchers have investigated the bio-leaching processes [10, 11], which were
difficult in selecting some suitable bacteria and had a long cycle of reaction. As to
physical methods, some authors used disassemble, magnetic separation, electrostatic
separation, and vacuum distillation to concentrate the metals in fraction and polymers
and ceramics in another [5, 12, 13]. Although physical methods had some drawbacks,
to some extent, it was the earliest and most widely used method for separating and
recovering metals from WPCBs. However, due to the heterogeneity and difference
of the WPCBs composition, the traditional physical methods were easy to isolate the
metals. Therefore, it was urgent and necessary to find new technology to recycle the
valuable metals in WPCBs. Centrifugal separation, as one of the physical methods, is
an efficient way for strengthening the multiphase flow transfer and reaction process.
On earth, a centrifugal field is achieved by rotating a centrifugal apparatus to pro-
duce a stable and adjustable centrifugal force field instead of a conventional gravi-
tational field. The different melting points between the solid particle and liquid melt
would result in particles distributing and separating gradually along the centrifugal
direction in a centrifugal field. It is a highly attractive and promising technology with
many advantages such as environmental friendliness, high efficiency, low investment,
and wide application in practice. The technology has been successfully applied to
the enrichment of valuable elements from different slags [14, 15], the fabrication
of functionally graded materials [16, 17], the removal of impurities from alloys or
metals [18, 19], and the treatment of gas, liquid, solid wastes [20, 21]. However, the
centrifugal technology was usually applied to ambient temperature or low tempera-
ture, and seldom used in high temperature conditions. Our groups have retrofitted a
medical centrifuge equipment so that it can be used for high-temperature centrifu-
gation. Most of the low-melting-point metals (Pb and Sn) have been recovered from
WPCBs in a previous study [22]. In addition, recycling of Cu from WPCBs by high-
temperature centrifugation has not been reported in the literature. The main objective
Selective Recycling of Cu Alloys from Metal-Rich Particles … 989
of the present study was to recover Cu alloys from WPCB residues in the two-step
process by high-temperature centrifugation.
Experimental
In this study, the waste computer PCBs (CPCBs) were purchased from an enterprise
in the Hunan province of China. Prior to their receipt, the PCBs were crushed,
sorted, and sieved to obtain a particle size of less than 1.0 mm, and the majority of
nonmetallic materials were removed from the PCBs. The obtained PCBs consisted
of metals and alloys with different melting points, and the molten metals and alloys
could be separated rapidly from the solid particles using a centrifugal field. Most of
the low-melting-point metals in the metal-rich particles of PCBs were preferentially
recycled by centrifugal separation, and high-melting-point metals (Cu, Zn, Au, Ag,
and Pd) remained in the residues. Therefore, the residues need to be reheated, rotated
and centrifuged to allow the recovery of Cu.
Equipment
The schematic and physical diagrams of the centrifugal apparatus are illustrated in
Fig. 1, with the heating furnace and the counterweight fixed symmetrically onto the
horizontal rotor. The centrifugal apparatus was retrofitted from a medical centrifuge
(Fig. 1b). It has the merits of wide applicability, small volume, low energy consump-
tion, easy operation, and maintenance. The centrifugal apparatus consisted of two
centrifugal tanks: one was used for heating and centrifuging samples (the separation
tank), while the other was used for balancing the equipment to keep the centrifu-
gal process stable (the counterweight tank). The counterweight tank should have a
weight and center of gravity in line with those of the separation tank. The two tanks
are shown in the stationary state by the red line in Fig. 1a. The separation tank con-
tained an insulating layer and a heating system. The temperature of the separation
tank was controlled by a program controller with an R-type thermocouple, with a
precision range of ±3 °C. The gravity coefficient (G) was calculated as the ratio of
super gravitational acceleration to normal gravitational acceleration via Eq. (1).
2
2 N 2π 2 R
g2 + ω2 R g2 + 900
G= = (1)
g g
990 L. Meng et al.
(a) (b)
10 cm
Fig. 1 Schematic and physical diagrams of centrifugal separation apparatus (1. Counterweight; 2.
Centrifugal axis; 3. Thermocouple; 4. Motor; 5. Resistance coil; 6. Furnace chamber; 7. Refrac-
tory materials; 8. Filter hole; 9. Metal-rich particles of crushed PCBs; 10. Graphite crucible; 11.
Refractory brick; 12. Horizontal rotor; 13. Conductive slipping; 14. Dashboard.)
where ω is the angular velocity (rad/s); N is the rotating speed of the centrifuge
(rev/min); R is the distance from the centrifugal axis to the center of the sample (R
= 0.25 m); and g is the normal gravitational acceleration (g = 9.8 m2 /s).
Experimental Procedures
A 36 g sample was placed into a set of graphite crucibles of inner diameter 19 mm. The
bottom of the upper graphite crucible included small holes (1 mm), through which
metals in the liquid state could pass. Graphite felt (thickness 3 mm) was laid at the
bottom of the upper crucible to retain small solid particles. Similarly, graphite felt
(thickness 5 mm) was laid on the metal-rich particles to avoid oxidization during the
separation process. In a previous study, Pb and Sn were separated from the metal-rich
particles of crushed PCBs at a temperature of 410 °C, gravity coefficient of 1000,
and separation time of 5 min. After the separation of Pb–Sn alloy, the metal-rich
residues were reheated to 650–900 °C and held at this temperature for 30 min before
the centrifugal apparatus was rotated. After the separation time of 5 min, the apparatus
was shut down and the lower graphite crucible was removed rapidly and quenched
in water. Finally, the separation residues in the upper graphite crucible were again
heated to 950–1300 °C, and then separated and quenched in water. Figure 2 shows
the flowchart of the centrifugal separation of metals from PCB particles. The main
research is shown in the red line frame. The residues after the separation of Pb–Sn
alloy were reheated, rotated, and centrifuged two times to recover alloys of Sn–Cu
and Cu–Zn from the metal-rich residues. The Cu–Zn alloy with high Cu content will
Fig. 2 Flow chart of the centrifugal separation of metals from PCB particles
be refined by electrolysis or used in other commercial and industrial applications.

The final residues will be treated with hydrometallurgy to recycle precious metals.
Analysis and Treatment of Data
The metal-rich particles of crushed PCBs were characterized by inductively coupled

plasma-optical emission spectroscopy (ICP-OES, Optima 7000DV, Perkin Elmer,
USA), and the results are shown in Table 1. In this research, the obtained alloys
were sectioned longitudinally along the center axis. One portion of alloys was
characterized by scanning electron microscope and energy-disperse X-ray spec-
trum (SEM/EDS, MLA 250, FEI Quanta, USA), X-ray diffraction (XRD, SmartLab,
Rigaku Corporation, Japan), and the other portions were dissolved by acid leaching
and analyzed by ICP-OES.
Table 1 Chemical compositions of metal-rich particles of crushed PCBs

Element Cu Sn Zn Fe Pb
Content/wt% 52.36 10.31 7.19 3.38 5.01
992 L. Meng et al.
The recovery (Ri ) of Pb, Sn, Zn, or Cu was calculated by Eq. (2).
mi
Ri = × 100% (2)
m C × ωi
where mi is the mass of Pb, Sn, Zn, or Cu that was separated from the metal-rich
particles of crushed PCBs (g); mC is the mass of the metal-rich particles of crushed
PCBs (g); ωi is the mass fraction of Pb, Sn, Zn, or Cu in the metal-rich particles of
crushed PCBs. The experimental data were collected three times.
In a previous study, 54.41% Pb and 41.94% Sn recoveries were achieved using a

gravity coefficient of 1000, a temperature of 410 °C, and a separation time of 5 min
[22]. However, due to the low contents of other metals in the metal-rich particles and
the formation of solid solutions with Cu during the heating process, it was difficult
to separate completely. The metal-rich residues were separated and recovered in two
steps to obtain Cu alloys with different components in the study. The effects of some
parameters on the recovery of Cu were investigated, including the gravity coefficient
and the process temperature.
Separation of Sn–Cu Alloy
Effect of Gravity Coefficient on the Sn–Cu Alloy Recovery
In the separation process, the resistance between liquid metals and solid particles was
large. Therefore, the centrifugal separation was required to overcome the resistance
involved in Cu recovery. The gravity coefficient is an important parameter in the
separation process. A series of gravity coefficients were conducted to discuss the
recovery of Cu, Zn, Pb, and Sn in the first step separation at 800 °C, and the results
are presented in Fig. 3. It was not possible to increase the gravity coefficient beyond
1000 due to the limited rotation speed of the centrifugal apparatus. As indicated, upon
increasing the gravity coefficient from 200 to 1000, the recoveries of Cu, Zn, Pb, and
Sn increased both linearly and gradually, giving recoveries of 19.72, 18.68, 17.78,
and 23.25% for Cu, Zn, Pb, and Sn, respectively, at the maximum gravity coefficient.
Table 2 shows the chemical compositions of obtained alloys using different gravity
coefficients, where it is apparent that although this variable affected the Cu recovery
rate, it had little effect on the composition of the recovered Cu. Under a gravity
coefficient of 1000, the alloy had 66.22 wt% Cu, 16.96 wt% Sn, 5.94 wt% Pb, and
6.54 wt% Zn, respectively. In the alloy, the contents of Sn and Cu were higher those
of Pb and Zn, and it was called Sn–Cu alloy.
Fig. 3 Effect of gravity

coefficient on the recovery of
Cu, Zn, Pb, and Sn
Table 2 Chemical compositions of obtained alloys under different gravity coefficients

G Cu wt% Zn wt% Pb wt% Sn wt%
200 66.87 6.62 4.93 16.18
400 66.12 7.15 4.98 15.10
600 67.62 5.78 4.88 15.69
800 68.01 6.25 6.47 15.43
1000 66.22 5.94 6.54 16.96
Effect of Temperature on the Sn–Cu Alloy Recovery
According to the DTA data, the temperature range was selected from 650 to 900 °C in
this separation stage [20]. Figure 4 shows the effect of temperature on the recovery of
Cu, Zn, Pb, and Sn. The results indicated that the recovery values of Cu, Zn, Pb, and Sn
increased from approximate 0–45.29%, 48.60%, 24.13%, and 29.19%, respectively,
as the temperature increased from 650 to 900 °C under the gravity coefficient of 1000.
Table 3 lists the chemical compositions of obtained alloys at different temperatures.
The results show that the content of Cu in the alloy increased with the temperature
prolonged to 900 °C. In the Sn–Cu alloy, the main element content (Cu, Zn, Pb, and
Sn) was more than 95 wt%. This Sn–Cu alloy will be refined for the next application
in the future. The Sn–Cu alloy is used in the manufacture of bearings, worm gears,
gears, etc.
Figure 5 shows the profile of Sn–Cu alloy by centrifugal separation at 800 °C
and a gravity coefficient of 800. Most Cu remained in the upper graphite crucible,
only Sn–Cu alloy, as lower melting point alloy, was separated from solid metal-rich
residues of PCBs. The XRD pattern of Sn–Cu alloy was presented in Fig. 6. The
results suggested that the diffraction peaks were Sn–Cu, Cu–Zn, and Pb. According to
994 L. Meng et al.

on the recovery of Cu, Zn,
Pb, and Sn
Table 3 Chemical compositions of obtained alloys at different temperatures

T/°C Cu wt% Zn wt% Pb wt% Sn wt%
650 24.13 3.70 28.04 39.79
700 54.23 5.96 13.40 24.74
750 64.35 4.30 4.53 24.28
800 66.22 5.94 6.54 16.96
850 72.04 8.71 5.47 11.60
900 75.71 10.72 3.09 9.57
Fig. 5 Profile of Sn–Cu

Centrifugal direction
alloy by centrifugal
separation at T = 800 °C and
G = 800
Sn-Cu
Fig. 6 XRD pattern of

Sn–Cu alloy
the phase diagram of binary Cu–Sn alloy, it is easy to form intermetallic compounds
between 600 and 800 °C [23]. Molten metals or alloys overcome resistance, allowing
the separation of liquid-phase metal from solid particles.
The SEM mapping of Sn–Cu alloy obtained at 800 °C was given in Fig. 7. The
results indicated that there was no macroscopic segregation in the Sn–Cu alloy, Sn
and Cu were uniformly distributed in the alloy. Pb was dispersed in the alloy in the
form of agglomeration. A small amount of Zn was evenly distributed in the alloy.
Fig. 7 SEM mapping of Sn–Cu alloy by centrifugal separation at 800 °C (a SEM of Sn–Cu alloy;
b–e distribution of Cu, Sn, Pb, and Zn in the SEM of Sn–Cu alloy, respectively.)
996 L. Meng et al.
Fig. 8 Effect of gravity

coefficient on the recovery of
Cu, Zn, Pb, and Sn
Separation of Cu–Zn Alloy
Effect of Gravity Coefficient on the Cu–Zn Alloy Recovery
Using the conditions G = 1000 and T = 800 °C in the previous step of the separation
process, 19.72% Cu, 18.68% Zn, 17.78% Pb, and 23.25% Sn were achieved. In this
step, 2# PCB residues were reheated to 950–1300 °C and separated again using
super-gravity technology. Under the temperature of 1200 °C, the effect of gravity
coefficient on the separation alloy was investigated, and the results are shown in
Fig. 8. It can be seen that metal recovery shows a steady increase as G increases from
100 to 1000. At an optimum gravity coefficient of 1000, the recovery values of Cu,
Zn, Pb, and Sn were 77.17%, 71.63%, 27.12%, and 30.24%, respectively.
Effect of Temperature on the Cu–Zn Alloy Recovery
The maximum temperature of the furnace was 1300 °C. Therefore, a series of sepa-
ration experiments were carried out by varying the heating temperature from 950 to
1300 °C. Figure 9 shows the effect of temperature on the alloy with a gravity coeffi-
cient of 1000. As the temperature increased from 950 to 1300 °C, Cu recovery was
gradually increased. As to Pb, Sn, and Zn recovery, the recovery values increased,
then gradually decreased. It was found that the values on Cu, Zn, Pb, and Sn recovery
were 79.12%, 68.28%, 26.14%, and 27.43%, respectively, at the maximum temper-
ature of 1300 °C. The majority of Cu and Zn are separated and recycled from the
metal-rich residues of PCBs, so the alloy is called Cu–Zn alloy. The temperature
also has an effect on the chemical compositions of Cu–Zn alloys (Table 4). With
increasing the temperature from 950 to 1300 °C, Cu content increased from 74.27
to 79.48 wt%.

on the recovery of Cu, Zn,
Pb, and Sn
Table 4 Chemical compositions of Cu–Zn alloys at different temperatures

T/°C Cu wt% Zn wt% Pb wt% Sn wt%
950 74.27 10.01 3.54 8.37
1000 75.86 10.45 3.42 8.55
1050 76.31 10.04 3.23 8.89
1100 76.33 9.92 2.86 7.79
1150 77.06 9.78 2.81 6.75
1200 78.29 9.79 2.57 5.91
1250 78.73 9.73 2.46 5.76
1300 79.48 9.75 2.37 4.94
Figures 10 and 11 show the profile and XRD pattern of Cu–Zn alloy obtained at
T = 1200 °C and G = 1000, respectively. The results indicated that most Cu was
recovered from PCB residues by melting and separating in a centrifugal field. It was
an efficient way to separate different alloys step by step. The XRD showed that the
diffraction peaks were Cu–Zn, Cu–Sn, Fe–Zn, and Pb in the alloy.
In order to further study the microstructure of Cu–Zn alloy, the sample was char-
acterized by SEM/EDS, and the corresponding results are presented in Fig. 12. Cu
and Zn were uniformly distributed and no macro-segregation was observed in the
sample. Pb and Sn were dispersed in the alloy. A small amount of Fe was also sep-
arated and dispersed in the form of agglomeration in the alloy. In this separation
process, the mass fractions of Cu and Zn in the alloy were 78.29 wt% and 9.78 wt%,
respectively, while those of Pb and Sn were 2.81 wt% and 5.91 wt%, respectively.
This Cu–Zn alloy is used in the manufacture of sheet, strip, and casting parts. This
blister Cu will be recovered to obtain refined Cu through an electrochemical process.
998 L. Meng et al.
Fig. 10 Profile of Cu–Zn
Centrifugal direction
alloy obtained by centrifugal
separation at T = 1200 °C
and G = 1000
Cu-Zn
Fig. 11 XRD pattern of

Cu–Zn alloy
Copper electrodeposition is a conventional process to recover Cu from a solution. It

is widely used under acidic conditions, which is also the current industrial practice.
After the two-step separation process, the total recovery values of Cu and Zn
were 98.84% and 86.96%, respectively. In the total separation processes, including
the separation of Pb–Sn alloy, the total recovery values of Pb and Sn were 98.33%
and 92.62%, respectively. A small amount of off gases (furans and dioxins) produced
in the laboratory were discharged into the air after activated carbon adsorption and
catalyst treatment. The next steps will concentrate and recycle precious metals (Au,
Ag, Pt, and Pd), and evaluate the energetic costs of the processes. In addition, larger-
scale experiments and energy consumption evaluation will be required to evaluate
the possibilities of application on the industrial scale.
Fig. 12 SEM mapping of Cu–Zn alloy obtained by centrifugal separation at 1200 °C (a SEM of
Cu–Zn alloy; b–f distribution of Cu, Zn, Pb, Sn and Fe in the SEM of Cu–Zn alloy, respectively.)
Conclusions
Centrifugal separation is an efficient method for separating and recovering Cu from

metal-rich particles of crushed PCBs. In the separation process, the alloys of Sn–Cu
and Cu–Zn were obtained at different temperatures. In the separation of Sn–Cu alloy,
45.29% Cu, 48.60% Zn, 24.13% Pb, and 29.19% Sn were recovered from the metal-
rich particles at 900 °C and a gravity coefficient of 1000. Based on the separation of
Sn–Cu alloy at 800 °C, Cu–Zn alloy was recycled and separated, and the values on Cu,
Zn, Pb, and Sn recovery were 79.12%, 68.28%, 26.14%, and 27.43%, respectively,
at the maximum temperature of 1300 °C and the optimum gravity coefficient of
1000. In addition, the temperature has a great influence on the composition of the
alloy, while the gravity coefficient only affects the recovery values of alloy in each
separation process. In the complete process, the total recovery values of Cu, Zn,
Pb, and Sn were 98.84%, 86.96%, 98.33%, and 92.62%, respectively. These copper
alloys will be applied to different industrial fields. Recycling precious metals and
larger-scale experiments are required to further evaluate the separation process. This
study provides further evidence for the use of intrinsic properties and controlled
temperatures for the generation of valuable metals from the recycling of WPCBs,
with significantly reduced amounts of secondary wastes.
Acknowledgements This work was financially supported by the key projects of National Natural
Science Foundation of China (Grant No. 51704022).
1000 L. Meng et al.
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Super-Gravity Field Enrichment
of Silver and Antimony Contained
in Pb–Ag–Sb Melts
Xiaochun Wen, Lei Guo, Qipeng Bao, Jintao Gao and Zhancheng Guo
Abstract Lead–silver–antimony (Pb–Ag–Sb) melts are obtained during the

pyrometallurgical processing of jamesonite (Pb4 FeSb6 S14 ). This work examined a
new method of super-gravity technology to effectively enrich silver and antimony
metals contained in Pb–Ag–Sb. The experimental results demonstrate that the sil-
ver mainly migrates to the denser lead matrix while most of the antimony-rich phase
accumulates above it. Following super-gravity enrichment under conditions of 533 K
(260 °C), G = 600 and t = 5 min, the mass fraction of Sb in the antimony-rich phase
reached 90 wt%, and more than 95 wt% of the silver migrated to the lead-rich phase,
which could be further recovered during the subsequent electrolytic refining process
of lead. The microstructures of samples obtained by super-gravity enrichment and
the corresponding enrichment mechanism are discussed.
Keywords Enriching behaviors · Silver · Antimony · Pb–Ag–Sb melts ·

Super-gravity technology
Introduction
Crude Pb–Ag–Sb alloy melts are produced by blast furnace reduction smelting of
jamesonite (Pb4 FeSb6 S14 ), which is a composite metallic ore that is the most impor-
tant ore resource with large reserves and high-yield in China [1]. The Pb–Ag–Sb alloy
melts are difficult to separate due to the fact that these elements respond similarly in
the metallurgical process [2–4]. The material is currently processed by: blowing in a
reverberatory furnace [5, 6], vacuum distillation [7], fractional crystallization using
directional lifting process [8], separating the alloy melts in chloride system [9] and
the slurry electrolysis technology, and sodium sulfide leaching-electrolysis process
X. Wen · L. Guo · Q. Bao · J. Gao (B) · Z. Guo

e-mail: jintaogao@ustb.edu.cn

https://doi.org/10.1007/978-3-030-36540-0_89
1002 X. Wen et al.
[10]. However, this process is complicated due to requiring the high energy con-
sumption for the blowing process, the generation of a large number of slags, and the
production of exhaust gases that are highly harmful to the environment and human
health. Additional factors are the low-purity of antimony produced by oxidization to
Sb2 O3 and then reduction to metal, and the low direct recovery ratio of silver during
the blowing and smelting process. Moreover, the long cycle process, high production
cost, huge alkali consumption, and discontinuity of the process are difficulties that
affect the application in the industry. Thus, it is worthwhile to investigate efficient
and pollution-free alternative methods of enriching the silver and antimony metals
from the Pb–Ag–Sb alloy melts.
In this study, a new method of super-gravity technology was introduced. Super-
gravity technology, inspired by Ramshaw’s utilization of centrifugal apparatus [11],
can effectively improve the mass migration of heterogeneous phases. Recently,
the super-gravity approach was proposed for use in pyrometallurgical processes to
recover metals from molten slag, remove impurities from metallic melts, and sepa-
rate valuable metals from electronic wastes, among other applications. For instance,
Super-gravity technology represents an effective means for separating Fe-bearing
and P-bearing phase from steelmaking slag [12], the anosovite crystals [13] and
the perovskite crystals [14] from molten Ti-bearing slag, and the copper phase and
iron-rich phase from copper slag [15]. Wang et al. [16] investigated the feasibility of
recovering zinc from the industrial galvanizing dross by super-gravity and over 79
wt% zinc was recovered with a purity of about 99 wt%. Li et al. [17] proposed that
high-purity suanite crystals were efficiently attained from boron bearing slag, provid-
ing an essential ceramic reinforced phase for ceramic–metallic composite material
and glass–ceramic. Yang et al. [18] reported the copper impurity could be effectively
enriched and separated from the Pb-3 mass pct Cu melt by super-gravity technology
and the separation efficiency up to 96.18 pct. Lan et al. [19] investigated a green
method of respectively recovering rare earths (Ce, La, Pr, Nd) from rare-earth tail-
ings under the super-gravity field. In addition to these, the super-gravity method also
has been successfully applied in preparing functionally graded materials [20] and
fabrication of W–Cu composites [21]. Based on the above-mentioned results, it is
speculated that the enrichment of the silver and antimony metals from the Pb–Ag–Sb
melts is feasible in a super-gravity field.
This manuscript describes the separation and enrichment of silver and antimony
metals contained in the Pb–Ag–Sb alloy melts under the super-gravity field. The
microstructure of the silver and antimony metals obtained by super-gravity enrich-
ment were investigated. In addition, the corresponding mechanism of enriching is
discussed in detail.
Super-Gravity Field Enrichment of Silver and Antimony … 1003
Fig. 1 a Enrichment device of the graphite crucible; b schematic diagram of the centrifugal appa-
ratus: (1) counterweight; (2) centrifugal axis; (3) centrifugal rotor; (4) base; (5) resistance heating
furnace; (6) resistance wire; (7) graphite crucible; (8) lead–silver phase; (9) antimony-rich phase;
(10) temperature controller; (11) conductive slipping; (12) cylindrical corundum chamber
Experimental
Apparatus
The enrichment device was a graphite crucible with an inner diameter of 20mm
and 70 mm in length as shown in Fig. 1a. The super-gravity field was generated
by a laboratory-scale centrifugal apparatus with an incorporated heating function,
as illustrated in Fig. 1b. To effectively enrich silver and antimony metals from the
Pb–Ag–Sb alloy melts with super-gravity, the apparatus was mainly configured by a
heating furnace and counterweight that was fixed symmetrically onto the centrifugal
rotor and rotated from vertical to horizontal orientation when the centrifugal rotor
started operation. In addition, the heating furnace had a cylindrical alumina chamber
of 40 mm in diameter and an isothermal zone of 80 mm in length that was heated
by resistance wire; temperature was controlled by a programmable controller with a
K-type thermocouple within the observed precision range of ±3 K.
Materials and Preparation
The Pb–0.8wt% Ag, and 45wt% Sb alloy selected to serve as the raw material in
this study is based on the main compositions of the crude alloy melts from Guangxi
Province in China. The alloy was prepared by blending lead (99.99 wt pct), silver
(99.9 wt pct) and antimony (99.999 wt pct) and placing the mixture in graphite
crucibles (inner diameter of 18 mm). The loaded crucibles were put in the furnace,
which was heated by molybdenum disilicide elements. The mixture was heated under
1004 X. Wen et al.
an argon gas shield to 1273 K (1000 °C) for 1 h. Afterward, the samples were cooled
to room temperature for the enrichment experiments.
In the enrichment experiments, a sample mass of 30.46 g was put in the graphite
crucible (inner diameter of 20 mm), which was, in turn, placed in the furnace outfitted
with the centrifugal apparatus. The sample was heated to 533 K (260 °C) for 30 min.
The super-gravity apparatus was set in motion and adjusted to target rotating speed
(1465 r/min, G = 600). Simultaneously, the operation was maintained for 5 min,
after which the sample was cooled in air.
The gravity coefficient, which evaluates the super-gravity field, was calculated as
the ratio of super-gravitational acceleration to the normal-gravitational acceleration,
according to Eq. (1):

2π R 2
2
g2 +(ω2 R)2 g 2 + ( N 900 )
G= = (1)
g g
where G denotes gravity coefficient, g is the normal-gravitational acceleration (g =

9.8 m/s2 ), ω denotes the angular velocity (rad/s), N is the rotational speed (r/min), R
denotes the distance between the centrifugal axis and sample center (R = 0.25 m),
especially, when N = 0 r/min, G = 1.
Analytical Methods
The solidification characteristics of the Pb–Ag–Sb alloy melt were investigated by

differential scanning calorimetry (DSC, TA Instrument, USA) analysis. The DSC
was carried out from 500 °C with a cooling rate of 1 °C/min. After the super-gravity
enrichment experiment, the samples were sectioned longitudinally into halves along
the center axis of super-gravity to form a micrograph view. Subsequently, half of
which was polished and analyzed via the scanning electron microscope and energy-
dispersive X-ray spectroscopy (SEM-EDS, MLA 250, FEI Quanta, USA) and opti-
cal microscopy (Leica DM6000) to investigate the variations in micro-structure and
phase compositions of the lead–silver melts and antimony-rich phase. In addition,
the other half was measured further by Inductively Coupled Plasma Optical Emis-
sion Spectrometry (ICP-OES, Optima7000DV, Perkin Elmer, USA) to determine the
chemical components of the enriched lead–silver melts and the antimony-rich phase.
Fig. 2 a DSC curves of the Pb–0.8wt%Ag–45wt%Sb alloy specimens; b Pb–Sb equilibrium phase
diagram
Theoretical Analysis of the Pb–Sb Alloy’s Phase Diagram
As shown in Fig. 2a, the solidification characteristics of the solidified Pb-0.8wt%Ag-

45wt%Sb alloy melt samples were examined using DSC. The results show that an
intense endothermic peak at approximately 250 °C which corresponds to the eutectic
temperature in the Pb–Sb system as illustrated in Fig. 2b; it means that a small amount
of silver does not affect the Pb–Ag–Sb system. In addition, the lead-rich melt and
β-Sb solid solution began to precipitate when the temperature dropped to the point
P (on the diagram), notably, the lead-rich phase and β-Sb solid solution will be
continuously crystallized from the alloy melts in terms of approaching the eutectic
temperature.
To evaluate the enriching influence of Pb–0.8wt%Ag–45wt%Sb alloy melts in a
super-gravity field, the mass fraction of antimony in the upper of the sample and
the mass fraction of silver in the lower of the sample as analyzed by ICP-OES were
expressed as ωSb-upper and ωAg-lower , respectively.
The enrichment silver (E Ag ) was calculated by Eq. (2):
Mlower ω Ag−lower
E Ag = × 100% (2)
Mraw ω Ag
where M lower is the mass of the lower of sample, M raw is the mass of Pb-0.8wt%Ag-
30wt%Sb alloy specimens, and ωAg denotes the mass fraction of silver in the raw
materials.
1006 X. Wen et al.
The Micro-structure of Samples Obtained by Super-Gravity

Enrichment
The Pb-0.8wt%Ag-45wt%Sb alloy specimens were used as raw material for the
enrichment experiments which were conducted for 5 min at 533 K (260 °C), in
the normal-gravity field (G = 1) and super-gravity field (G = 600), respectively.
The micro-structure characteristics and energy-dispersive spectrum of the samples
attained by normal-gravity (G = 1) as noted in Fig. 3, it could be observed that the
light area was almost of lead-rich phase, and the dark area were mainly of antimony-
rich phase. Especially, a small number of Ag–Sb compounds were embedded in
the lead-rich melt in Fig. 3e and the results of SEM images further presented the
distribution of the silver and antimony metals in Fig. 4.
As the micro-structure attained by super-gravity with gravity coefficient of G =
600 at 533 K (260 °C) shown in Fig. 5a, it is apparent that a multilayer structure
consisting of the top, middle and bottom layers (layers 1, 2, and 3) were presented
in the entire sample along the direction of super-gravity. In the top areas, the matrix
of the sample mainly consisted of bulk-like antimony phase and lead-rich phase,
and almost no silver phase was observed at the top layer of the sample as shown in
Fig. 5d–f. Moreover, the dividing lines between the top, middle, and bottom layers
of the sample are evident in Fig. 5g and h, respectively.
As seen in Fig. 6, the middle layer of the sample mainly consisted of irregular
bulk-like antimony phase and dendrite Ag–Sb compounds which were discretely
Fig. 3 Micro-structure characteristics and energy-dispersive spectrum of the sample attained by

normal-gravity with the condition of T = 533 K (260 °C), G = 1 and t = 5 min
Fig. 4 SEM mappings of the sample obtained by normal-gravity with the condition of T = 533 K
(260 °C), G = 1 and t = 5 min
distributed in the matrix of the lead-rich phase with the results of SEM mappings
described by Fig. 6e. On the contrary, the bottom layer almost consisted of fine tree
Sb–Pb crystals and Ag–Sb crystals which were distributed in the lead matrix combing
in Fig. 6g, i, j. In addition, the bottom layer was much thinner than other layers along
the super-gravity direction in terms of their higher density (11.34 g/cm3 for Pb and
10.49 g/cm3 for Ag) than the antimony phase (6.84 g/cm3 ), and the moving velocity
was extremely increased under the super-gravity field based on Stokes’s law [22].
The enrichment efficiencies of the samples obtained by super-gravity are given
in Table 1. As the thin thickness of the bottom layer, the upper sample was defined
as the top layer which was mainly of antimony-rich phase, while the lower sample
was defined as the middle layer and the bottom layer which was almost of Ag–Sb
compounds and the lead matrix. After enriching by super-gravity under conditions
of 533 K (260 °C), G = 600 and t = 5 min, the mass fraction of antimony in the
upper sample increased to 90.8 wt%, and more than 95 wt% of the silver in the Pb–
0.8wt%Ag–45wt%Sb alloy migrated to the lower sample, and could be recovered
during electrolytic refining of lead.
1008 X. Wen et al.
Fig. 5 Micro-structure of the sample attained by super-gravity with the condition of T = 533 K
(260 °C), G = 600 and t = 5 min
Fig. 6 The middle and bottom layer of the sample attained by super-gravity with the condition of
T = 533 K (260 °C), G = 600 and t = 5 min
Table 1 The enrichment efficiencies of the samples obtained by super-gravity

Samples ωPb (wt%) ωAb (wt%) ωSb (wt%) M (g) EAg (%)
Upper sample 9.09 0.07 90.82 12.18 –
Lower sample 84.65 1.26 14.05 18.27 95.02
Fig. 7 Schematics of the mechanism of the enrichment under the super-gravity field
Mechanism of the Enrichment by Super-Gravity
Figure 7 describes the mechanism of the enrichment under the super-gravity field
and determines the migration behaviors of antimony and silver metals from the Pb–
0.8wt%Ag–45wt%Sb melt. After heat treatment, silver metal migrated to the lead
matrix at the bottom of the sample in the direction of super-gravity. Conversely,
most of the antimony-rich phase accumulated along the opposite direction due to the
difference in density and state of matter. Therefore, enriching silver and antimony
metals from the Pb–0.8wt%Ag–45wt%Sb melt was shown to be feasible in a super-
gravity field.
Conclusion
An innovative approach of enriching silver and antimony metals from the Pb–
0.8wt%Ag–45wt%Sb melts by super-gravity technology has been introduced. The
microstructures of samples obtained by super-gravity enrichment and the correspond-
ing mechanism of enriching were investigated. The main conclusions drawn from
the analysis of the experimental results are as follows:
(1) In the super-gravity field, a multilayer structure formed in the sample along
the direction of super-gravity. Silver predominantly migrated to the lead at the
bottom of the sample, while most of the antimony-rich phase accumulated above
due to the difference in density.
(2) After super-gravity enrichment with the condition of T = 533 K (260 °C), G =
600 and t = 5 min, the mass fraction of Sb in the upper sample was up to 90.82
wt%, and more than 95 wt% of the silver in the Pb–0.8wt%Ag–45wt%Sb alloy
melts migrated to the lower sample which could be further recovered during the
subsequent electrolytic refining process of lead.
1010 X. Wen et al.
Acknowledgements This work was financially supported by the National Natural Science Foun-
dation of China (No. 51804030), and the project of State Key Laboratory of Advanced Metallurgy
(41618024).
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bearing slag melt in a reducing atmosphere by supergravity. Metall Mater Trans B 48:749–753
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Materials 2:2510–2525
Synthesis of Na2 (Ni, Fe)(SO4 )2 Cathode
Materials from Nickel Sulfide
Concentrate by Combined Pyro-
and Hydrometallurgical Processes
Guangshi Li, Lizhen Wei, Caixiang Yu, Xiaolu Xiong, Hongwei Cheng,
Qian Xu and Xionggang Lu
Abstract In this study, a compact process was introduced to prepare the sulfate-
based polyanionic nano cathode material Na2 (Ni, Fe)(SO4 )2 from nickel sulfide
concentrate. The Na2 (Ni, Fe)(SO4 )2 was synthesized with a four-step process,
including sulfate roasting, leaching-purification, co-precipitation, and annealing pro-
cesses. The crystalline phase identification and microstructure characterization of the
final product was performed by X-ray diffraction (XRD) and Scanning electronic
microscopy (SEM), respectively. The XRD result shows that the obtained prod-
uct which was composed of eldfellite compounds Na2 (Ni, Fe)(SO4 )2 and sodium-
rich phase Na6 Fe(SO4 )4 . The SEM reveals that the synthesized material was with
a microstructure of nanopore, which might be owing to the nanocarbon powder
as nucleation particles can promote the formation of nanometer pore. The nano-
material Na2 (Ni, Fe)(SO4 )2 , expected to be a promising candidate in energy stor-
age applications as sodium-ion battery, has been synthesized from nickel sulfide
concentrate.
Keywords Sulfide minerals · Sulfation roasting · Co-precipitation · Cathode

materials
Introduction
Recently, due to resource and environmental problems, intermittent renewable energy

has been increasingly favored by human beings. In order to integrate renewable
energy into the power grid, a large-scale energy storage system is essential. For
G. Li (B) · L. Wei · C. Yu · X. Xiong · H. Cheng · Q. Xu · X. Lu (B)

School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
e-mail: lgs@shu.edu.cn
X. Lu
e-mail: luxg@shu.edu.cn
G. Li · H. Cheng · Q. Xu · X. Lu
State Key Laboratory of Advanced Special Steel & Shanghai Key Laboratory of Advanced
Ferrometallurgy, Shanghai University, Shanghai 200444, China
https://doi.org/10.1007/978-3-030-36540-0_90
1014 G. Li et al.
lithium-ion batteries, due to its low abundance, uneven distribution, declining avail-
able lithium resources, and high prices, which seriously restrict its development in
large-scale energy storage [1]. Sodium has similar chemical properties to lithium,
abundant crustal resources, and low cost, so sodium-ion batteries have come into
people’s vision gradually. For sodium-ion batteries, the exploration of cathode mate-
rials is extremely important. Generally, the cost of cathode materials accounts for
about 26% of the total sodium-ion battery, which the top cost in SIBs [2]. However,
most of the cathode materials are synthesized by a commercial pure reagent, which
might lead to a relatively high cost of SIBs. In recent research, Wang et al. stud-
ied the hydrometallurgical production of Lithium-ion battery cathode material from
high-grade nickel matte [3]. And the obtained LiNi0.80 Co0.15 Al0.05 O2 materials show
comparable electrochemical performance to that prepared from analytical reagents.
However, during this process, sulfur failed to utilize and the high-grade nickel matte
is already close to industrial products. At present, nickel sulfide concentrate is mainly
melted into low nickel matte by the electric furnace or flash furnace, and then con-
verted into high-grade nickel matte [4]. The traditional pyrometallurgical process is
long, complex, and high consumption of pure reagents. In the process of converter
blowing, about 70% of cobalt, some nickel and copper will be oxidized into con-
verter slag, resulting in a large loss of valuable metal [5]. Li et al. [6] studied the
sulfate roasting and water leaching process of nickel sulfide concentrate to achieve
high-efficiency and simultaneously extraction of valuable metals (Co, Ni, and Cu).
The obtained leachate mainly contains Ni2+ , Co2+ , Cu2+ , Na+ , and SO4 2− . However,
the deep separation of various metals in the leaching solution still needs further
treatment.
In recent years, polyanionic electrode materials of sodium ion have attracted
wide attention. Compared with other polyanionic electrode materials, sulfate-based
polyanionic compounds have stronger electronegativity, which is conducive to
obtain higher redox potential [7]. Barpanda [8] reported that sulfate framework,
Na2 Fe2 (SO4 )3 , registering the highest ever Fe3+ /Fe2+ redox potential at 3.8 V (ver-
sus Na, and hence 4.1 V versus Li). Recently, a series of sulfate-based polyanionic
compounds have been studied in depth. Such as NaFe(SO4 )2 [9], Na2.32 Co1.84 (SO4 )3
[10], Na2.44 Mn1.79 (SO4 )3 [11], Na2 Ni1/2 Mn1/2 (SO4 )2 [12], et al. Additionally, Rey-
naud et al. [13] found that Na2 Fe(SO4 )2 shows electrochemical activity at potential
between 2.5 and 4.5 V. Ri [14] used the first principles to confirm that mixed eldfel-
lite compounds Nax (Fe1/2 M1/2 )(SO4 )2 (x=0–2, M = Mn, Co, Ni) can be suitable for
high-performance cathodes for SIBs.
With the aim to realize the integration of nickel sulfide concentrate (low-end
materials) to materials (high-end materials). Basing on making full use of sulfur in
nickel sulfide ore and avoid deep separation of metal ions in leaching solution. We
proposed a four-step process to prepare cathode material Na2 (Ni, Fe)(SO4 )2 from
nickel sulfide ore directly. Phase analysis and purity determination of the obtained
substances were carried out. In the process of purification, iron powder was used
to remove Cu2+ , which replacement with Cu2+ to form Fe2+ and Cu. The remaining
small amount of Cu2+ and Co2+ , which could not be removed deeply, has been proved
to have a positive effect on the electrochemical performance of the cathode material
[15].
Synthesis of Na2 (Ni, Fe)(SO4 )2 Cathode Materials from Nickel … 1015
Raw Materials
In this study, the raw material is nickel sulfide flotation concentrate from Jinchuan
Group Ltd. (Gansu, China). The main chemical composition of the sample is shown
in Table 1. Figure 1 is the X-Ray diffraction (XRD) pattern of the nickel con-
centrate sample. Phase identification analysis shows that the main valuable metal
phases of the concentrated sample are chalcopyrite (CuFeS2 ), pentlandite ((Ni, Fe,
Co)9 S8 ), small amount of cubanite (CuFe2 S3 ), pyrite (FeS2 ), and pyrrhotite (Fe7 S8 ).
The gangue minerals mainly include serpentine (Mg3 (Si2 O5 (OH)4 ), ferromagnesite
(Mgx Fe3-x O4 ), quartz (SiO2 ), and talc (Mg3 (OH)2 Si4 O10 ). The chemical reagent used
in the test is commercially pure sodium sulfate.
Table 1 Chemical composition of the nickel sulfide flotation concentrate sample (mass fraction,
%)
Fe Ni Cu S Si Co Others
32.13 27.01 18.58 15.21 0.52 0.38 6.16
Fig. 1 XRD pattern of the flotation nickel sulfide concentrate sample

1016 G. Li et al.
Characterization Methods
The chemical element composition and content of the sulfide concentrate sample
were tested by XRF (XRF-1800, SHIMADZU LIMITED) with full-spectrum scan-
ning at 8°/min. The crystal phase composition of the raw materials and final product
was characterized by XRD (D8 ADVANCE, Bruker). The X-ray powder data were
collected at 50 kV/50 mA and with a 2 theta range from 10° to 90° (0.02°/step,
0.3 s/step). The concentration of metal ions in the leachate, filtrate, and final product
were analyzed by using an inductively coupled plasma optical emission spectrometer
(ICP-OES, Optima 7300DV, PerkinElmer). The microstructure of the final product
was characterized by a tungsten filament scanning electron microscope (SEM, NOV
NANOSEM 450).
Experiment Procedure
The preparation of cathode material Na2 (Ni, Fe)(SO4 )2 from nickel sulfide concen-
trate (low-end material) could be divided into four steps, sulfate roasting, leach-
ing-purification, co-precipitation, and annealing. Figure 2 shows the process flow
sheet.
Sulfate Roasting Process
According to our previous study, the sulfate roasting of nickel sulfide concentrate
was conducted [6]. The mixture of 1 g nickel sulfide concentrate and 0.1 g Na2 SO4
was ground in a mortar to grind for 30 min and then roasted in a vertical furnace in air.
The calcination conditions are as follows: the heating rate of 2°/min rises to 600 °C,
holding for 2 h, and then quenched to room temperature to achieve the calcine.
Water Leaching Purified Process
After calcination, the calcine was poured into a conical bottle, 50 ml deionized water
was added, heated in a constant temperature water bath at 80 °C and stirred for 30–
50 min. The leachate was filtered quickly while it was hot. The filtrate was cooled to
room temperature and poured into a volumetric bottle at constant volume for testing
of the element content.
Chose the replacement method to remove copper by adding iron powder [16].
The amount of iron powder was 1.5 times the theoretical amount of copper removal.
The iron powder was added slowly three times from the feeding port, and the dosage
of iron powder were 50%, 30%, and 20% of the total amount, respectively. The
reaction temperature was 50 °C and the reaction time was 30 min. After the reaction,
Fig. 2 The flow diagram for the preparation of Na2 (Ni, Fe)(SO4 )2 cathode materials from nickel
sulfide concentrate
the filtrate was obtained by thermal filtration. In addition to copper removal, the loss
rate of nickel and cobalt should not exceed 1%.
Co-precipitation Process
The ratio of Fe, Ni, and Na in the solution was adjusted to 1:1 by adding appropriate
Na2 SO4 into the filtrate. The precursor was prepared by co-precipitation using the
ethanol insolubility of sulfate [17]. The device for preparing the precursor is shown
in Fig. 3. First, nanocarbon powders were dispersed in 100 ml anhydrous ethanol
under ultrasonic for 2 h to build a uniform suspension (A). 20 ml of the above-mixed
solution (B) was weighed so that the volume ratio of the mixed solution to absolute
ethanol was 1:5. The mixed solution (B) was slowly added to the anhydrous ethanol
under strong stirring. At the same time, the Ar atmosphere was used to prevent ferrous
ions from being oxidized. After sufficient precipitation (~30 min), the product was
filtered and washed with ethanol. Then, the product was dried in a vacuum at 70 °C
to achieve the precursor.
1018 G. Li et al.
Fig. 3 Experimental device

diagram for preparation of
precursors
Annealing
The obtained precursor was annealed at 200 °C for 2 h and 350 °C for 6 h with the
heating rate of 2 °C/min in Ar atmosphere and then quenched to room temperature
to achieve the final product.
The nickel sulfide concentrate was leached by sulfate roasting. The main chemical
composition of the leaching solution is shown in Table 2. It can be seen that the ratio
of nickel to copper in leaching solution is close to 1, while there is less content of iron.
In this experimental system, a large amount of copper is not expected, and a small
amount of copper has been proved to have the advantage of stabilizing material
structure in lithium-ion batteries. It is noteworthy that iron is expected to exist in
large quantities but the content of leaching solution is very small. Combining with
removing copper and introducing iron, iron powder was selected for removing copper
in the process of purification.
According to the content of copper in leaching solution, the amount of iron pow-
der needed for Cu removal was determined. Firstly, the theoretical copper removal
Table 2 Chemical composition of leaching solution (mass fraction, %)

Ni S Cu Na Fe Co Others
36.93 32.92 22.90 5.22 1.10 0.71 0.22
Fig. 4 Rietveld refinement

results of XRD data of final
product
amount mFe was calculated according to the replacement reaction, and the actual
amount of iron powder was 1.5 mFe according to the references. The molar ratio of
sodium ion to the transition metal element is 2:1.
The precursor was prepared by co-precipitation and the final product was obtained
by annealing. Figure 4 is the Rietveld refinement results of the final product. It can
be obtained that there are only two phases of the final product, eldfellite compounds
Na2 (Ni, Fe)(SO4 )2 and sodium-rich phase Na6 Fe(SO4 )4 [18] with the same structure
as vanthoffite Na6 Mg(SO4 )4 . Additionally, Na6 Fe(SO4 )4 is accompanied by forma-
tion in liquid-state reaction [17]. From the results of XRD, the purity of the final
product is relatively high, which indicates that the process can obtain high purity
electrode materials, and has certain feasibility.
The morphology of the final product was characterized. Figure 5 is the scanning
electron microscopy (SEM) of the final product at different magnifications. It can be
seen that under the current technological conditions, the final samples have certain
nanopores on the surface with the size between 25 and 350 nm. The advantages of
porous materials at the electrolyte/electrode interface are beneficial to the penetration
of electrolyte and rapid ion transport [19].
The final product was dissolved in deionized water and its purity was further
determined by the ICP test. Table 3 is the chemical composition of the final product.
From the ICP test results, it can be concluded that the final product contains a certain
amount of Si. Silicon is the metal element which is not expected to exist in the system.
Therefore, combining the XRD results and ICP determination, further Si removal is
needed, and subsequent use for electrode materials. Silicon is relatively sensitive to
PH, so the follow-up work is to remove Si by adjusting pH of the solution in order
to obtain higher purity electrode materials.
1020 G. Li et al.
Fig. 5 SEM images of the final product
Table 3 Chemical composition of final product (mass fraction, %)

Na Ni Fe Si Co Others
46.24 31.03 20.32 1.38 0.59 0.44
Conclusions
The final product was obtained by co-precipitation mainly composed of eldfellite

compounds Na2 (Ni, Fe)(SO4 )2 and sodium-rich phase Na6 Fe(SO4 )4 , There is also a
small amount of silicon in the synthesized material, which still needs further removal.
Additionally, the nanoporous microstructure of synthesized material is beneficial
to the penetration of electrolyte and rapid ion transport. It indicates that the final
product is expected to be electrode material in the system of sodium-ion battery.
This study has a certain guiding significance for realizing the integration of nickel
sulfide concentrate (low-end material) and nanomaterial (high-end material). It may
become a potential way to reduce the cost of materials for sodium-ion batteries in
the future.
Acknowledgements This work was financially supported by the China Postdoctoral Science Foun-
dation, the Super Postdoctoral Incentive Program in Shanghai, the Steel Joint Research Foundation
of National Natural Science Foundation of China–China Baowu Iron and Steel Group Co. Ltd.
(Grant No. U1860203), the National Natural Science Foundation of China (Grant No. 51576164),
National Basic Research Program of China (973 Program) (Grant 2014CB643403), and the CAS
Interdisciplinary Innovation Team.
References
1. Fang Y, Chen C, Ai X (2017) Recent developments in cathode materials for Na ion batteries.
Acta Phys Chim Sin 33:211–241
2. Chen M, Liu Q, Wang SW (2019) High-abundance and low-cost metal-based cathode materials
for sodium-ion batteries: problems, progress, and key technologies. Adv Energy Mater 1803609
3. Xi Z, Wang Z, Yan G (2019) Hydrometallurgical production of LiNi0.80 Co0.15 Al0.05 O2 cathode
material from high-grade nickel matte. Hydrometallurgy 186:30–41
4. Li C (2007) Review on industrialization of the hydrometallurgy for high nickel mattes refining
in Fukang Smelter. China Nonferrous Metall 13:20–24
5. Shen M, Ji C, Zhu C (2012) Yunnan Metall 41:32–34
6. Li G, Cheng H, Chen S (2018) Mechanism of Na2 SO4 promoting nickel extraction from sulfide
concentrates by sulfation roasting-water leaching. Metall Mater Trans B 49:136–1148
7. Liu Y, Chen C, Zhao N (2007) Research and application of key materials for sodium-ion
batteries. J Electrochem 21:437–452
8. Barpanda P, Oyama G, Nishimura S (2014) A 3.8-V earth-abundant sodium battery electrode.
Nat Commun 21:4358
9. Singh P, Shiva K, Celio H (2015) Eldfellite, NaFe(SO4 )2 : an intercalation cathode host for
low-cost Na-ion batteries. Energy Environ Sci 8:3000–3005
10. Dwibedi D, Gond R, Dayamani A (2017) Na2.32 Co1.84 (SO4 )3 as a new member of the alluaudite
family of high-voltage sodium battery cathodes. Dalton Trans 46:55–63
11. Dwibedi D, Araujo RB, Chakraborty S (2015) Na2.44 Mn1.79 (SO4 )3 : a new member of the
alluaudite family of insertion compounds for sodium ion batteries. J Mater Chem A 3:18564–
18571
12. Marinova DM, Kukeva RR, Ekaterina N (2018) Selective sodium intercalation into sodium
nickel-manganese sulfate for dual Na–Li-ion batteries. Phys Chem Chem Phys 20:12755–
12766
13. Reynaud M, Rousse G, Artem M (2014) Design of new electrode materials for Li-ion and Na-ion
batteries from the bloedite mineral Na2 Mg(SO4 )2 ·4H2 O. J Mater Chem A 2:2671–2680
14. Ri GC, Choe SH, Yu CJ (2018) First-principles study of mixed eldfellite compounds
Nax (Fe1/2 M1/2 )(SO4 )2 (x=0–2, M = Mn Co, Ni): a new family of high electrode potential
cathodes for the sodium-ion battery. J Power Sources 378:375–382
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16. Li J, Li X, Zhou Y (2009) Purification of leaching solution of spent NixCoyMnz battery material
by removing Cu and Fe. Chin J Process Eng 9:676–681
17. Meng Y, Tiantian Y, Zhang S (2016) Top-down synthesis of muscle-inspired alluaudite
Na2+2x Fe2-x (SO4 )3 /SWNT spindle as a high-rate and high-potential cathode for sodium-ion
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sulfate Na2+2x Fe2-x (SO4 )3 as an advanced sodium battery cathode material. ChemElectroChem
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19. Wang W, Liu X, Qunjie X (2018) A high voltage cathode of Na2+2x Fe2-x (SO4 )3 intensively
protected by nitrogen-doped grapheme with improved electrochemical performance of sodium
storage. J Mater Chem A 6:4354–4364
Thermodynamic Analysis of Preparation
of Cermet from Zinc Kiln Slag
Ning Wang, Hongyan Yan, Chao Luo, Hui Li, Jinglong Liang and Jun Peng
Abstract The use of zinc kiln slag to prepare cermet can realize the recycling of zinc
kiln slag and promote sustainable development. The thermodynamic analysis of the
preparation process was carried out to develop a new method based on sintering with
suitable temperature and atmosphere, and obtain suitable component ingredients to
prepare excellent properties cermet. The preparation method was powder metallurgy
method, sintering temperature was 1300–1600 °C. Fe2 O3 , Al2 O3, and Fe powder
were added to the zinc kiln slag to balance the content of each component in the kiln
residue. The mass ratio of Fe2 O3 to Al2 O3 in cermet was 0.53. The content of CaO
should be minimized. The content of SiO2 should be 2–5%, and the content of TiO2
should be 24%.
Keywords Zinc kiln slag · Cermet · Powder metallurgy · Thermodynamics
Background
The zinc kiln slag has been widely concerned. Some problems such as large annual
output, large stacking amount, and large environmental pollution were presented.
The resource treatment of zinc kiln slag is a difficulty for metallurgical workers.
There are two main sources of zinc kiln slag. One is tail slag produced by wet zinc
smelting [1]. The other is tail slag after zinc leaching in the rotary kiln [2]. At present,
N. Wang · H. Yan (B) · H. Li · J. Liang

College of Metallurgy and Energy, North China University
of Science and Technology, Tangshan 063210, China
e-mail: xiaoniji@126.com
C. Luo · J. Peng
School of Materials and Metallurgy, Inner Mongolia University
of Science and Technology, Baotou 014010, China
C. Luo
Hesteel Group Tangsteel Company, Tangshan 063000, China

https://doi.org/10.1007/978-3-030-36540-0_91
1024 N. Wang et al.
the treatment methods for zinc kiln slag are mainly fire process and wet process. The
fire process is the extraction of valuable metals by solid carbon reduction, which
consumes a large amount of energy, but a low metal yield. The wet process extracts
valuable metals from the zinc kiln slag through a series of wet processing methods
[3], but the process is long and the waste liquid is seriously polluted. In order to
solve the above problems, some researchers try to use zinc kiln slag as a roadbed
material and building materials. This treatment method has a low cost and short
process, but the added value of the obtained product is low. The iron-based cermet
has a high added value and combines the excellent physicochemical properties of Fe
and iron–aluminum spinel ceramics. It is significant to prepare zinc-based kiln slag
into iron-based cermet.
The preparation of iron-based cermet depended on the sintering reaction of metal
phase Fe and FeAl2 O4 [4], and the formation of FeAl2 O4 was a prerequisite. In
this paper, the reaction temperature and atmosphere of iron-based ceramics were
prepared by thermodynamic theoretical analysis using FactSage. Combined with the
chemical composition of zinc kiln, the effects of CaO, SiO2 , TiO2, and MnO2 on the
preparation of iron-based cermet were investigated.
Preparation Method and Conditions
Preparation Method
The sample composition of the zinc kiln slag used in this study was shown in
Table 1. Powder metallurgy was the most common preparation method for cer-
met. The ceramic phase powder was mixed with the metal binder and metal phase
according to a certain ratio, then pressed into an embryo body, finally sintered under
conditions slightly higher than the melting point of the metal [5, 6]. The preparation
method of this study was powder metallurgy method. The process flowchart was
shown in Fig. 1.
Table 1 Zinc kiln slag composition table (mass fraction)

Composition Content Composition Content
Slag 100 MnO2 0.76
Fe2 O3 23.74 Na2 O 0.59
SiO2 15.71 K2 O 0.20
CaO 15.74 SO3 18.80
Al2 O3 6.04 As2 O3 7.07
MgO 2.88 C 7.00
TiO2 0.36 Other 1.11
Thermodynamic Analysis of Preparation of Iron-Based Cermet … 1025
Slag Crush and sieve Wash and dry Charge and mix
Cermet Sinter under Ar Shape Ball-milling

atmosphere treatment
Fig. 1 Process flowchart for preparing cermet from zinc kiln slag
Fig. 2 FeO–Al2 O3 phase diagram at 1 atm
Sintering Temperature
In order to prepare the Fe/FeAl2 O4 cermet, it was necessary to form a FeAl2 O4 com-
pound during sintering. The formation conditions of spinel with FeO and Al2 O3 were
explored. It was beneficial to determine the sintering temperature and the protective
atmosphere. The phase diagram of FeO and Al2 O3 was simulated to obtain Fig. 2. It
was ensured that the product contained Fe and iron–aluminum spinel, and the phase
diagram showed that the Fe and Fe–Spinel phase is stable.
1026 N. Wang et al.
In summary, the sintering temperature can be controlled at 1300–1600 °C to

prepare metal-based ceramics. Fe was a metal phase, FeAl2 O4 was ceramic phase.
It corresponded to the preparation of cermet.
Effect of Component
The content of component in zinc kiln slag may affect the performance of cermet.
It was necessary to study the content of the component. In this paper, the effect was
studied by Factsage at 1450 °C. There were three reasons. First, the sintering tem-
perature was 1300–1600 °C, 1450 °C met the temperature requirements. Second, the
types of products obtained by phase diagram simulation were the same as tempera-
ture was between 1300 and 1600 °C. Meanwhile, the area occupied by each phase in
the phase diagram was not much different. Third, Fe/FeAl2 O4 cermet were prepared
by using Fe, Fe2 O3, and Al2 O3 obtained the best performance in the literature [7].
Theoretical Ratio
The FeAl2 O4 and Fe were obtained by reacting Fe2 O3 , Al2 O3, and Fe powder in the
kiln slag. To obtain excellent performance cermet, it was necessary to strictly control
the content of Fe2 O3 , Al2 O3, and Fe powder [8].
In Fig. 3, the addition of Fe powder can produce Fe and Fe-Spinel target phase
by sintering at 1450 °C. It proved that the preparation of Fe/FeAl2 O4 cermet using
zinc kiln slag was feasible. The reactions were shown as follows:
6Fe2 O3 = 4Fe3 O4 + O2 (g) (1)
2Fe3 O4 = 6FeO + O2 (g) (2)
FeO + Al2 O3 = FeAl2 O4 (3)
Fe + Fe2 O3 + 3Al2 O3 = 3FeAl2 O4 (4)
FeO was all obtained by Fe2 O3 and Fe with the step as Fe2 O3 → Fe3 O4 → FeO.
FeO reacted with Al2 O3 to form the FeAl2 O4 phase. From reaction (4), each 1 g
of FeAl2 O4 phase required 0.17 g of Fe powder, 0.307 g of Fe2 O3, and 0.586 g of
Al2 O3 . The ratio of Fe2 O3 and Al2 O3 was a fixed value at 8:15. The Fe powder was
added in an excessive amount to form a metal phase in the cermet (Fig. 4).
Fig. 3 Fe2 O3 –Al2 O3 –Fe phase diagram at 1450 °C
Effect of CaO
CaO has a melting point of 2580 °C and a boiling point of 2850 °C. It is hardly
soluble in water and insoluble in alcohol. The content of CaO in the zinc kiln slag
was 15.74%, it is necessary to analyse the effect on cermet. The Factsage was used
to simulate the Fe2 O3 –Al2 O3 –CaO phase diagram at 1450 °C to explore the effect of
CaO on the preparation process. The result was shown in Fig. 5. The reaction among
Fe2 O3 , Al2 O3 , CaO were as Eqs. (5)–(10).
CaO + Al2 O3 = CaAl2 O4 (5)
CaO + 2Al2 O3 = CaAl4 O7 (6)
CaO + 6Al2 O3 = CaAll2 O19 (7)
CaO + Fe2 O3 = CaFe2 O4 (8)
CaO + 2Fe2 O3 = CaFe4 O7 (9)

1028 N. Wang et al.
Fig. 4 Fe2 O3 –Al2 O3 –CaO phase diagram at 1450 °C
CaO + 6Fe2 O3 = CaFe12 O19 (10)
Figure 4 showed that a variety of CA and CF low melting point oxides were
formed. It resulted in the loss of Fe and Al elements. The low melting point of
CA and CF seriously affected the mechanical properties of cermets. Therefore, the
presence of CaO adversely affects the properties of cermet.
Effect of SiO2
SiO2 cannot react with Fe2 O3 , Al2 O3 , but reacted with CaO, MgO in kiln slag at
1450 °C. The CaO–MgO–SiO2 phase diagram was analyzed. The reactions were
shown as follows:
2CaO + SiO2 = 2CaO·SiO2 (11)
2MgO + SiO2 = 2MgO·SiO2 (12)

Fig. 5 CaO–MgO–SiO2 phase diagram at 1450 °C
CaO + MgO + SiO2 = CaO·MgO·SiO2 (13)
The above reaction can reduce the influence of CaO and MgO on the preparation
of FeAl2 O4 during sintering. The 2CaO·SiO2 , 2MgO·SiO2, and CaO·MgO·SiO2 had
high melting points. However, it was difficult to reduce the reaction product, which
also affected the mechanical properties of the cermet.
The low melting point phase of SiO2 –CaO–Al2 O3 –MnO was easily produced at
reducing the atmosphere [9]. The formation of a low-melting point phase allowed the
system to generate a large amount of liquid phase at low temperature. It can promote
sintering. The increase of SiO2 content and the decrease of CaO/SiO2 value were
beneficial to the formation of low-melting point phase of SiO2 –CaO–Al2 O3 –MnO.
A small amount of SiO2 can promote low temperature sintering of cermet. However,
Fe2+ was also easily desolvated into the liquid phase, resulting in a decreased solid
solubility of FeO and reducing the amount of iron–aluminum spinel.
The sintering temperature can be significantly decreased with a 2% addition of
SiO2 . And the bulk density of the samples at different sintering temperatures can
reach the maximum. When the addition added more than 5%, a large amount of low-
density liquid phase hindered the formation of iron–aluminum spinel with increased
1030 N. Wang et al.
temperature, and the bulk density of the sample decreased rapidly [10]. Therefore,
the content of SiO2 in the raw material should be controlled between 2 and 5%.
Effect of TiO2
The content of TiO2 in the zinc kiln slag was 0.36%. TiO2 may be reduced to TiO
at 1450 °C, the TiO oxide layer can be formed at the interface of the metal/ceramic
matrix [11]. TiO oxide layer had great metallic properties. It can promote the combi-
nation of metal and ceramic, and optimized the mechanical properties of metal-based
ceramics. However, excessive TiO2 will hinder the production of FeAl2 O4 . TiO2 can
react with Al2 O3 and Fe2 O3 at a low temperature to form Al2 TiO5 and Fe2 TiO5
solid solutions, which can only be decomposed at higher than 1550 °C. Al2 TiO5
and Fe2 TiO5 inhibited the synthesis of Fe–Al-based spinel phase [12]. The reactions
involved were as follows:
2TiO2 + C = 2TiO + CO2 (14)
TiO2 + Al2 O3 = Al2 TiO5 (15)
TiO2 + Fe2 O3 = Fe2 TiO5 (16)
The mass percentage of Fe2 O3 in the slag of zinc extraction kiln was 23.74, the
mass percentage of Al2 O3 is 6.04, and Al2 O3 /(Al2 O3 + Fe2 O3 ) = 0.20. When the
addition of TiO2 was less than 24%, the formation of iron and aluminum oxide
(Al2 Fe2 O8 ) could be promoted, and spinel could be generated by decomposition.
Al2 TiO5 or Fe2 TiO5 will be produced in the system with more than 24% of TiO2
(Fig. 6).
Conclusion
The preparation process of cermet from zinc kiln slag was discussed. The influence
of component in the zinc kiln slag on cermet preparation was analyzed by using the
ternary phase diagram. Fe2 O3 and Al2 O3 were the main reactants in the preparation
process, and it was necessary to control the mass ratio of Fe2 O3 and Al2 O3 to 0.53.
The content of CaO should be controlled to a minimum. The effect of SiO2 , TiO2, and
MnO2 on cermet preparation was analyzed. The content of SiO2 should be 2–5%,
the content of TiO2 should be less than 24%, and the content of MnO2 should be less
than 4%.
Fig. 6 Phase diagram of Fe2 O3 –Al2 O3 –TiO2 at 1450 °C
China (No. 51804126), Natural Science Foundation of Hebei Province (No. E2018209266).
References
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MnO system. Chin J Eng 29(6):574–577
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spinel. Chin J Eng 47(3):161–165
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Author Index
A D
Anzulevich, Anton, 405 Dai, Shifan, 239
Augustine, Robin, 569 Dai, Yongnian, 521
Deng, Shuai, 791
Deng, Zihang, 627
B Denton, Glen Michael, 303
Bai, Bin, 489 Diao, Jiang, 823
Bai, Kaikai, 835 Dongbo, Li, 975
Bao, Qipeng, 67, 1001 Dong, Jianhao, 901
Barati, Mansoor, 803 Dong, Kai, 3, 115, 341, 779
Bartmann, Ulrich, 931 Downey, Jerome P., 715
Benzeşik, Kağan, 561 Duan, Huamei, 431
Bing, Li, 975 Duan, Jiao-yang, 953
Bratberg, Johan, 101 Duan, Jiaoyang, 215
Du, Weitong, 147
Du, Yu, 381
C
Cai, Haoyu, 693
Cai, Wei, 921 E
Chama, Shadreck, 541 Eray, Said, 393
Chen, Chao, 33
Chen, Chen, 867
Chen, Dengfu, 431 F
Chen, Feng, 465 Feng, Chao, 115, 779
Cheng, Hongwei, 1013 Feng, Kai, 741
Cheng, Liu, 975 Feng, Qiang, 341
Chen, Jiansheng, 835
Chen, Jing, 953
Chen, Min, 33, 867 G
Chen, Ruimei, 725 Gao, Jintao, 381, 1001
Chen, Xi, 329 Geveci, Ahmet, 393, 511
Chen, Zhiqiang, 845 Grundy, A. Nicholas, 101
Chikontwe, Kennedy, 541 Gu, Foquan, 359
Chorney, Jannette, 715 Gu, Maoqiang, 741
Cibula, Matthew, 273 Guo, Lei, 67, 1001
Cui, Xiaokang, 455 Guo, Muxing, 521
https://doi.org/10.1007/978-3-030-36540-0
1034 Author Index
Guo, Yu-feng, 465 Liang, Jinglong, 1023

Guo, Zhancheng, 67, 381, 987, 1001 Liao, Chunfa, 289
Guo, Zheng-Lei, 911 Liao, Zhehan, 551
Guo, Zhengqi, 879 Li, Bo, 417, 845
Gu, Yan, 681 Li, Changrong, 157, 531
Li, Gang, 627, 673
Li, Guanghui, 359, 405, 569, 639, 953
H Li, Guangshi, 1013
Han, Baochen, 115 Li, Haijuan, 475
Han, Junwei, 963 Li, Hui, 1023
Hao, Suju, 895 Li, Ji, 133
Hara, Yotamu R. S., 541 Li, Linpei, 627
Hassan, Abdelrhman, 499 Li, Longfei, 455
He, Dongfeng, 741 Li, Min, 705
He, Sheng ping, 705 Lin, Ping, 157
He, Wenchao, 319 Li, Pan, 263, 911
Hockaday, Carolina S. A., 43 Liu, Dachun, 81, 369
Hofer, Dominik, 931 Liu, Feng, 803
Hou, Xiaolei, 465 Liu, Hui, 595
Huang, Bing, 55, 227 Liu, Huibo, 639, 681
Huang, Daxin, 81, 369 Liu, Jinwen, 13, 581
Huang, Yun, 203 Liu, Liang, 823
Huang, Zhucheng, 921 Liu, Mudan, 569, 845
Hua, Yunhui, 183 Liu, Shiyuan, 445
Hu, Chengfei, 921 Liu, Shuai, 329, 531
Hu, Qun, 13
Liu, Shuo, 359
Hu, Shaoyan, 779
Liu, Wei, 963
Hu, Zhiyuan, 773
Liu, Yan, 475
Liu, Yang, 253
Liu, Yong, 569, 845
J
Liu, Yongjie, 605
Jeppsson, Johan, 101
Jiang, Qi, 147 Liu, Zhen, 455
Jiang, Silu, 489 Liu, Zhengjian, 693
Jiang, Tao, 215, 359, 405, 569, 639, 681, 953 Liu, Zhongci, 673
Jiang, Wenlong, 81, 369 Liu, Zhuangzhuang, 521
Jiang, Wufeng, 895 Li, Weifeng, 115, 779
Jiang, Xiong, 921 Li, Xiaolong, 475
Jin, Yunyun, 921 Li, Xiaosong, 13
Li, Yandong, 431
Li, Yongda, 627
K Li, Yongliang, 329
Kaluba, Golden, 541 Li, Zhi, 295
Keskinkilic, Ender, 393, 511 Li, Zhongci, 627
King, Paul E., 273 Li, Zihan, 963
Kjellqvist, Lina, 101 Long, Mujun, 431
Kong, Xiangfeng, 81, 369 Luidold, Stefan, 931
Lu, Manman, 359
Luo, Chao, 1023
L Luo, Yan, 253, 773
Lai, Yanqing, 93 Lu, Qi, 263
Lan, Xi, 381 Lu, Xionggang, 1013
Lee, Joonho, 569 Lv, Haozi, 845
Liang, Guangfen, 431 Lv, Wei, 445
Author Index 1035
Lv, Xiangyong, 431 Ren, Ying, 253

Lv, Xuewei, 319, 445, 605, 627, 673 Rettig, Ralf, 101
Rutto, H. L., 811
M
Ma, Guojun, 295 S
Ma, Huaiying, 617 Sambo, Sifiso N., 43
Ma, Jie, 595 Sarkar, Rahul, 21
Mao, Ning, 203 Schumacher, Katie, 715
Mason, Paul, 101 Seodigeng, Tumisang, 43
Ma, Xiaodong, 289 Shang, Wenxing, 405
McLean, Alexander, 417 Shen, Wei, 157, 531
Mei, Qinsong, 369 Simfukwe, Haggai, 541
Meng, Fanchao, 653 Skhosane, Samuel, 123
Meng, Long, 987 Sohn, Hong Yong, 21
Meraikib, Mohammed, 499 Song, Bo, 455
Moholwa, M. S., 811 Song, Sicheng, 725
Motley, Joshua, 273 Steenkamp, Joalet Dalene, 303, 757, 811
Muchindu, Choolwe, 541 Stefanova, Vladislava, 941
Musowoya, Douglas, 541 Sun, Chengfeng, 551
Sun, Lifeng, 489
Sun, Lijuan, 329, 531
N Sun, Tianhao, 895
Naplatanova, Maria, 941 Sun, Xiao, 791
Sun, Yanhui, 725
Su, Zijian, 359
O
Ou, Shuhai, 617
T
Tang, Haiyan, 13, 581
P Tang, Huimin, 359
Pan, Feifei, 319 Tang, Yixing, 341
Pan, Jian, 193, 857, 879 Tan, Liang, 531
Pan, Wen, 617 Tao, Wang, 663
Parirenyatwa, Stephen, 541 Tian, Baizhou, 921
Pei, Guishang, 319 Tian, Hongyu, 193, 857, 879
Peng, Jun, 1023 Tianyu, Guo, 975
Peng, Li, 975 Tian, Zhongliang, 93
Peng, Zhiwei, 215, 359, 405, 569, 953 Tie, Zhanpeng, 13
Pieters, Tertius, 303 Tingan, Zhang, 663
Pityana, Sisa, 123 Tlotleng, Monnamme, 123
Pournaderi, Saeid, 511 Topkaya, Yavuz A., 393, 511
Turan, Ahmet, 561
Q
Qing, Gele, 693 V
Qin, Wenqing, 963 Varol, Mustafa, 393
Qu, Guorui, 417 Vassileva, Vania, 941
Qu, Yingxia, 653 Vutova, Katia, 941
R W
Rao, Mingjun, 215, 359, 405, 569, 953 Wallace, Grant C., 715
Ren, Qiang, 773 Wang, Chao, 551
1036 Author Index
Wang, Chunsong, 653 Xu, Baoqiang, 81

Wang, Dingzheng, 193, 857, 879 Xue, Botao, 465
Wang, Fei, 521 Xuejiao, Cao, 663
Wang, Fuming, 157, 329, 531 Xue, Liwen, 171, 239
Wang, Guang, 823, 901 Xue, Qingguo, 835, 901
Wang, Hongbing, 741 Xue, Yuxiao, 193, 857, 879
Wang, Hongpo, 489 Xu, Jian, 551
Wang, Hua, 417 Xu, Qian, 1013
Wang, Jian, 215, 953 Xu, Song, 431
Wang, Jie, 405 Xu, Yang, 551
Wang, Jingsong, 901
Wang, Lei, 455
Wang, Liancheng, 405, 569 Y
Wang, Na, 963 Yang, Bin, 81, 369, 521
Wang, Nan, 33, 867 Yang, Congcong, 193, 879
Wang, Ning, 1023 Yang, Lei, 405
Wang, Qian, 705 Yang, Lingzhi, 3, 465
Wang, Qiang qiang, 705 Yang, Mingrui, 627
Wang, Tao, 93 Yang, Qiankun, 595
Wang, Wanlin, 171, 239 Yang, Shu, 93
Wang, Weijian, 253 Yang, Wen, 253
Wang, Xu, 289 Yang, Yindong, 417, 445
Wang, Xun, 963 Yang, Yiru, 67
Wang, Yajie, 835 Yang, Yizhang, 551
Wang, Yang, 203 Yang, Zhanbing, 13, 157, 329, 531
Wang, Yidong, 639, 681 Yan, Hongyan, 1023
Wang, Yu, 147, 263, 489, 911 Yan, Liu, 663
Wang, Zhe, 987 Yao, Haiying, 581
Wei, Guangsheng, 3, 115, 779 Yao, Hongguo, 465
Wei, Lizhen, 1013 Yao, Liujie, 341
Wei, Yonggang, 417 Ye, Lei, 569
Wen, Xiaochun, 1001 Ye, Qing, 569, 953
Wu, Chengbo, 203 Yi, Lingyun, 921
Wu, Guanghui, 581 Ying, Guomin, 239
Wu, Muyang, 551 You, Jing-xiang, 953
Wu, Shanshan, 673 You, Jinxiang, 215
Wu, Shuangping, 133 You, Zhixiong, 605
Wu, Xuetao, 3 Yuan, Fei, 791
Wu, Yuan bing, 705 Yu, Caixiang, 1013
Yücel, Onuralp, 561
Yu, Haiyang, 33
X Yu, Huixiang, 341
Xiang, Junyi, 445
Xiao, Hong, 581
Xiaolong, Li, 663 Z
Xie, Bing, 823 Zeshang, Dong, 975
Xie, Yikui, 595 Zha, Guozheng, 81, 369
Xing, Liyong, 653 Zhang, Ai-ping, 55
Xin, Jianjiang, 867 Zhang, Aiping, 227
Xin, Yao, 975 Zhang, Gaopeng, 203
Xin, Yue, 617 Zhang, Hao, 901
Xiong, Xiaolu, 1013 Zhang, Hualong, 239
Xu, Anjun, 133, 741 Zhang, Jianliang, 693
Author Index 1037
Zhang, Jiaquan, 13, 581 Zhao, Zhixing, 617

Zhang, Jinlai, 465 Zheng, Fuqiang, 465
Zhang, Lifeng, 253, 773 Zheng, Leixia, 405
Zhang, Ling, 521 Zhi, Wenke, 521
Zhang, Qi, 133 Zhong, Qiang, 639, 681
Zhang, Shuo, 581 Zhong, Ronghai, 921
Zhang, Tao, 215, 953 Zhong, Yiwei, 987
Zhang, Ting’an, 475 Zhong, Yong, 55, 227
Zhang, Tongsheng, 171, 239 Zhou, Mingshun, 639, 681
Zhang, Wei, 295 Zhou, Peiling, 791
Zhang, Xiang, 295 Zhou, Qi, 595
Zhang, Xiaofeng, 81 Zhou, Xuangeng, 627, 673
Zhang, Xin, 215 Zhu, Deqing, 193, 857, 879
Zhang, Yan, 693 Zhu, Jianwei, 639, 681
Zhang, Yimin, 725 Zhu, Mingmei, 55, 227
Zhang, Yu, 605 Zhuo, Chao, 725
Zhang, Yuanbo, 359 Zhu, Rong, 3, 115, 341, 779
Zhang, Yuzhu, 895 Zhu, Xiaojie, 157
Zhao, Baojun, 183, 289 Zhu, Zhongping, 215
Zhao, Dongming, 639, 681 Zou, Zongshu, 653
Zhao, Jun, 835 Zuo, Haibin, 835
Subject Index
A Angle, 5, 13, 17, 19, 117, 119, 153, 154, 203,

AC furnace, 310 204, 206, 207, 211, 212, 227, 228,
Acicular ferrite, 456, 463, 464 230, 275, 280, 284, 313, 341, 342,
Activation energy, 21, 30, 295–297, 299– 350, 351, 355, 532, 551, 553, 555,
301, 336, 406, 659, 660, 897–900 573, 590, 665, 861, 978
Activity coefficient and activity of total fer- Angle between the elements, 342, 344, 351,
rous oxide in slag, 502 355
Activity of oxygen in liquid steel, 504 Annealing, 1018
Additives, 199, 289, 292, 435, 445, 446, ANN model, 554
449–451, 513, 514, 518, 527, 803, ANN model fitting, 555
836 Antimony, 82, 1001–1007, 1009
AES for grain boundary segregation, 539 Applicability of the established ANN model,
Alkaline roasting, 359–361, 367 557
Application model of database, 470
Alloy, 94, 103, 106, 110, 123–125, 127, 158,
Arc control, 281, 283, 286
184, 187, 254, 276, 289, 291–293,
Arc control furnace, 281
304, 306, 308, 310–315, 317, 330,
Arc measurement system, 275
334, 359, 456, 457, 468, 469, 531,
Argon blowing mode, 13, 14
532, 541, 542, 544, 548, 549, 596,
Artificial neural network, 551, 552, 554–
599, 606, 607, 726, 747, 757–761,
556, 674
763–770, 803–809, 848, 939, 954,
As-bearing inclusions, The, 489, 496–498
987, 990, 992–999, 1001–1007, 1009
Avrami equation, 709
Alloy specification, 759
Al2 O3 –MnO–SiO2 , 183–187
Alternating current (AC), 108, 303, 304, 306, B
308, 310–313, 629, 317
Baking, 140–142, 791–794, 796–800
Ammonia, 605–607, 612 Basic configuration, 467
Analysis method for particle segregation Basic governing equations, 978
behaviors, 554 Basicity, 122, 148, 181, 382, 383, 386, 500,
Analysis of hydraulic model experiment 503–509, 619, 629, 631, 643, 677,
results, 7 705–709, 711–713, 725, 726, 728,
Analysis of industrial test results, 10 730–734, 736, 738, 760, 782, 857,
Analysis of influencing factors, 747 858, 861–865, 867–869, 871–874,
Analysis of kinetic data, 297 876, 882, 884–886, 888–891, 936
Analysis of the numerical simulation, 350 Basic theory of process reconstruction, 137
Analysis of the water model experiment, 349 Bell-less top, 551, 553, 558
https://doi.org/10.1007/978-3-030-36540-0
1040 Subject Index
BF dust, 569–576, 578 Cermet, 1023–1030

Biochar, 405, 406, 408, 410–414 Characterization methods, 1016
Biomass, 418, 921–923, 925–928, 964 Characterization of the products, 611
Blast furnace, 21, 67, 72, 139, 140, 187, 263, Chemical composition, 846
319–321, 323, 324, 381, 383, 475, Chemical reactions in the molten bath, 351
476, 499, 551–553, 558, 569, 570, Chi-square boxing method, 33, 37
628, 639, 640, 648–650, 673, 674, Chlorination, 193–195, 197–202, 432, 445
681, 682, 691–693, 824, 835, 836, Chromium, 124, 359, 360, 364, 367, 405,
840, 843, 857, 858, 862, 867, 879, 408, 577, 823–828, 830, 832, 848,
880, 895, 1001 868, 953, 954
Bottom-blown O 2 –CaO converter, 780, 784, Cleaning process, 369, 425, 428
785, 788 Cleanliness, 140, 596, 725, 726, 738, 780
Boundary conditions, 58, 229 C–Mn Steel, 456, 459
BPNN model, 750 Coal gasification, 67, 68, 70–72, 75
Burner, 203, 204, 207–212 Coarsening, 451, 600, 803, 806, 807, 809
Burner inclination angle, 207 Combined blowing, 3–6, 9–11, 263, 264,
Burner placement height, 207 267, 911–913, 915–918
Combustion model, 793
Comparison of flow fields, 61
C Comparison of inclusion removal effects, 63
CaF2 , 147–150, 152–154, 522, 706, 725, Comparison of temperature fields, 62
728, 736, 737, 953, 954, 959 Complex inclusions, 243, 246
Calculated Mn and Fe recovery, 766 Composite liquid fluidity index, 617, 618,
CALculation of PHase Diagrams (CAL- 622, 623, 625
PHAD), 101–103, 216 Composition and morphology of inclusions,
CaO–Al 2 O3 –Sc2 O3 , 521, 522 731, 774
CaO–SiO 2 –CaF2 flux, 147, 148, 154 Computational fluid dynamics, 67, 69
Carbides, 291, 329, 330, 332–338, 715, 716, Computation methodology, 344
723, 932 Concentration of impurity elements, 827,
Carbide synthesis, 717 828, 831
Carbon-bearing pellets, 901, 902, 904–909 Concentration of Si in melt, 98
Carbon dioxide, 73, 263, 264, 562, 653, 685, Conduction, 43, 51, 52, 107, 275
783, 911, 912, 918, 926, 927, 956 Conservation equations for gas flow and
Carbon-free sintering, 627, 628 particle tracking, 69
Carbonization, 901–909 Consolidation, 698, 863
Carbon monoxide, 44, 71–73, 75, 76, 352, Construction of the prediction model, 674
611, 653, 685, 716, 717 Continuous casting–hot rolling interface,
Carbon oxidation, 27 142
Carbon oxides and nitrogen oxides, 685, Continuous copper refining, 976
687, 689–691 Continuous production experiment, 377
Carbothermal reduction, 295–297, 300, 301, Convection, 43, 46, 51, 207, 583
575, 824, 832, 954 Converter processing parameters, 35–37, 39
Carbothermic reduction, 296, 297, 304, 393, Converter process parameters selection, 35
445, 448, 449, 451, 512, 515, 517, Co-optimization of the material flow and
518, 606, 812, 953 energy flow, 143
Carburization modelling, 717 Copper, 4, 68, 194, 273, 281, 295, 296, 301,
Carburization precursor production, 716 315, 371, 375, 417–428, 476, 523,
Case-based reasoning, 741, 742, 744, 746, 541–547, 549, 845, 846, 848–853,
754 850–855, 942, 943, 975, 976, 978,
Cathode materials, 1014, 1017 979, 984, 985, 987, 998, 1002, 1014,
CBR model, 748 1016–1018
Cell design and electrolysis procedure, 94 Copper alloys, 999
Ceramic materials, 541 Copper anode slime, 369, 371
Subject Index 1041
Copper smelting furnace, 975, 985 E

Co-precipitation, 1013, 1016, 1017, 1019, EAF dust, 405–408, 410–414, 569–576, 578
1020 EAF steelmaking, 405, 465, 466, 469–472
Co-precipitation process, 1017 Effect of batching method on the reduction
Core-shell structure, 413, 578 of carbon-bearing pellets, 908
Corrosion, 76, 82, 158, 161, 163, 171, 172, Effect of CaO, 1027
175, 176, 178–181, 432, 497, 605, Effect of component, 1026
887, 941 Effect of distillation temperature on impuri-
Cost analysis, 466, 470–472 ties separation, 85
Cracks, 157, 158, 161, 163–166, 172, 228, Effect of distillation time on impurities sep-
537, 696, 697, 705, 706, 814, 819, aration, 88
906–908 Effect of gas concentration on reduction
Critical raw material, 932 degree, 656
Crystallization properties, 705, 707, 711 Effect of IHT on the fractographic features
Current density, 97 analysis, 537
Cuspidine glass-ceramics, 953, 954, 957, Effect of IHT on the mechanical properties,
959 536
C, V oxidation analysis, 915 Effect of IHT on the microstructural evolu-
tion characteristics, 534
Effect of inclusions on the cracking, 164
D
Effect of iron ore types on the morphologies
DC furnace, 309
of carbon-bearing pellets, 907
Decarburization efficiency and endpoint car-
Effect of La content on inclusion, 459
bon–oxygen equilibrium, 351
Decrepitation, 811–816, 819, 820 Effect of La content on the microstructure,
Decrepitation of iron ore, 814 463
Decrepitation of manganese ore, 812 Effect of La content on the size and number
Decrepitation test, 816 density of inclusions, 461
Defects, 62, 127, 240, 245, 253, 274, 275, Effect of La content on the size of effective
281, 286, 335, 725 inclusions, 461
DEM model, 552 Effect of oxide layer on cracking, 165
Dephosphorization effect, 353 Effect of oxygen carrier on biomass gasifi-
Dephosphorization rate, 11, 115, 117–119, cation, 926
121, 122, 353–355, 782 Effect of precipitation on the cracking, 161
Deposition product, 96 Effect of reductant types on the reduction of
Description for Tundish, 582 carbon-bearing pellets, 905
Design of furnace consumption data table, Effect of SiO2 , 1028
469 Effect of slag basicity, 871
Detection of magnesium addition, 598 Effect of smelting temperature, 869
Determination of appropriate coal ratio, 397 Effect of smelting time, 873
Determination of separation speed in static Effect of temperature on biomass gasifica-
state, 480 tion, 925
Development tools, 470 Effect of temperature on the reduction of
Direct current (DC), 275, 283, 303, 304, 306, carbon-bearing pellets, 904
308–311, 317, 490 Effect of the proportion of ground sinter
Direct energy deposition, 124, 125 feed on oxidation and metallurgical
Discrete element method, 551 properties, 862
Distribution of inclusions, 496 Effect of TiO2 , 1030
Distribution of oxygen types and Q n species, Electric Arc Furnace (EAF), 3, 4, 6, 9, 11,
152 106, 108, 111, 135, 303, 304, 316,
Distributor, 227, 228, 230–233, 236, 663– 342, 405–408, 410–414, 446, 451,
669, 671 465–472, 515, 569–576, 578, 726
Double layer pre-sintering, 639, 640, 643– Electrolysis, 93–99, 489, 490, 498, 991,
650, 681–683, 685, 689–692 1001
1042 Subject Index
Electrolysis temperature, 97 Flow rates, 3–5, 9, 27, 43, 263, 264, 266,
Electrolytic parameters, 93, 94 268–270, 668, 912
Electromagnetic induction, 627–629, 636 Fluidized bed, 68, 516, 653, 663–671, 895,
Electron beam, 124, 941–943, 946, 949, 950 896
Electron Probe X-ray Microanalysis Flux, 24, 25, 44, 48, 50, 147, 148, 153, 205,
(EPMA), 21, 29, 30, 184, 290, 427, 269, 273–275, 277, 285, 292, 293,
521, 523, 524, 526, 805, 807 308, 500, 514, 526, 627, 641, 674,
Emission, 83, 95, 136, 139, 240, 241, 263, 705–708, 711, 757, 759, 760, 763,
320, 361, 408, 500, 534, 561, 596, 766, 767, 769, 770, 839, 842, 846,
627–629, 639, 640, 653, 681–683, 849, 851–853, 879, 880, 882, 884,
685, 687, 689–692, 780, 804, 819, 976
824, 826, 943, 946, 991, 1004, 1016 Flux dosage test, 852
Endpoint slag composition, 354 Flux requirement, 766
Energy and emission reduction, 628, 629, Flux type test, 851
636 Frequency domain analysis, 669
Energy model, 343
Energy saving, 133, 134, 136–138, 144–146,
320, 629, 640, 682 G
Entropy, 215–217, 219, 221–223, 225, 744, Gasification, 67, 70, 71, 73, 298, 300, 405,
745, 748, 750 406, 412, 449, 921, 922, 924–929
Establishment of logistic regression model, Gasification–reduction coupling process,
40 67–71, 77
Evaluation model, 33–36, 41 Gas–liquid two-phase flow, 975, 978, 985
Evaluation model construction, 36 Gas–solid distribution, 663, 669–671
Experimental device, 641 Geometric model, 206
Export boundary conditions, 207 Geometric model and grid division, 977
Extended heat treatment soaking time, 333 Grain boundary segregation, 531, 534, 539
Grate-kiln, 693
Grid partition, 794
F Grind ability, 319, 324–326
Factors influencing the yield of calcium, 254 Grinding, 325, 393, 401, 402, 448, 457, 596,
FactSage, 109, 184, 187, 188, 193–195, 215, 849, 857, 858, 865, 896, 933, 934,
217, 222, 223, 246, 292, 293, 361, 957
383, 417, 421, 422, 424, 457, 459,
563, 607, 621, 725, 730, 732, 736,
757, 761–767, 872, 931, 935–939, H
1024, 1026, 1027 Hardness, 125, 127–129, 330, 534–536, 601,
Fayalite, 295–302, 418, 427, 513, 879, 885 605, 715, 811, 823, 942, 949, 950,
Feed system, 308 954
Ferromanganese, 105, 183, 241, 242, 303, Heat addition and heat loss at each time step,
304, 317, 757–759, 811 107
Ferronickel, 359, 360, 803, 805, 879, 880 Heat and mass transfer, 43, 44, 46, 52, 112,
Ferronickel slag, 359–362, 364, 366, 367 664
Ferronickel tailing, 879–885, 887, 889–891 Heat exchange between the various zones,
Fire spot zone temperature, 779, 780, 786, 107
788 Heat treatment, 125
Flash ironmaking, 21–24, 67, 68, 70–72, 77, Height, 4, 5, 44, 46, 52, 55, 59, 64, 172, 203,
653 206–210, 212, 311, 313, 476, 477,
Flotation, 194, 803, 804, 845, 849, 851, 855, 480–482, 573, 585, 590, 593, 603,
1015 618, 640, 641, 644, 645, 647, 663–
Flowability, 931, 936 666, 668, 669, 682, 683, 685–691,
Flow control devices, 55, 56 786, 791, 794, 869, 882, 934, 936,
Flow field, 55, 56, 60, 63, 203, 204, 227–229, 980, 983–985
231, 586, 590, 792 Hematite ore fines, 653, 655–660, 858
Subject Index 1043
Heterogenite, 542, 545 475, 476, 482, 486, 489, 494, 499,
High basicity refining slag, 171, 726, 733 511–518, 541, 542, 544–549, 569,
High carbon, 303, 304, 317, 606, 757–759, 570, 575–578, 607, 617–619, 621–
811 623, 625, 627, 629, 631–633, 639–
High carbon ferrochromium, 823, 824, 826– 643, 648, 650, 653–658, 663, 664,
828, 829–832 670, 673, 674, 681–683, 690, 691,
High temperature centrifugation, 987–989 708, 779, 780, 782–784, 787, 803–
Hot stage microscope, 934, 936, 939 809, 812, 814, 820, 823–828, 830,
Hot working, 157, 158, 161–166 832, 836–838, 840, 843, 848, 855,
Hydraulic experiment, 4 857, 858, 860, 861, 867–874, 876,
Hydraulic model, 3–7, 11, 341 880, 882, 895, 896, 898, 900–909,
Hydraulics experiment and computational 911, 912, 921, 922, 925, 928, 953,
verification, 346 954, 956, 957, 960, 963–966, 970–
Hydrogen, 21, 68, 71–77, 396, 417, 418, 422, 972, 1002, 1014, 1016, 1018, 1019,
426, 432, 515, 516, 544, 654, 716, 1024, 1025, 1029, 1030
717, 845, 848, 855, 922, 925–927, Ironmaking–steelmaking interface, 138
929, 954 Iron ores, 194, 215, 295, 499, 512, 551, 617,
618, 621–623, 625, 815, 816, 861,
901, 907
Iron ore sintering, 681–683, 691
I
Iron recovery, 402, 476, 511–514, 517, 953,
Ilmenite concentrate, 445–447, 449, 451
957, 958, 960, 965, 970, 971
Impedance matching, 569, 573, 578
Iron removal, 542
Import boundary conditions, 207 Iron whiskers, 895, 900
Improvement of oxidation and metallurgical Isothermal versus isenthalpic or adiabatic
properties of pellet, 862 equilibrium calculations, 107
Inclusion, 13, 14, 55–58, 58, 60, 63, 101,
102, 106, 110, 157, 158, 160, 164–
166, 171, 172, 183, 232, 239–241, K
243, 245, 246, 248–250, 253, 254, Kilogram-scale experiment, 373
256, 257, 330, 455–457, 459–464, Kinetic analysis, 658
489, 490, 492–498, 537, 581, 582,
586, 592, 595, 596, 598–604, 676,
677, 725, 726, 728, 731–735, 737, L
738, 773–778, 791, 946, 957 Ladle, 13–19, 55, 58, 101–103, 105–108,
Inclusion generation process, 497 111, 138–142, 146, 240, 241, 311,
Inclusion removal rate, 55, 56, 58, 63, 64, 312, 314, 466, 477, 500, 581, 584,
110 726, 733, 742, 747
Increased heat treatment temperature, 334 Lanthanum, 290
Industrial sludge, 845–847, 855 Laser deposition, 124, 127
Injection ratio, 263, 265, 269, 913, 915, 916 LAS materials, 83
Interaction between FeO and MgO, 28 Leaching, 82, 289–294, 359–361, 366, 367,
Interaction mechanism, 23, 27 381, 382, 431–433, 435–437, 439–
Intercritical heat treatment, 531, 532, 534, 442, 518, 522, 541–543, 545, 570,
536, 539 846, 954, 988, 991, 1001, 1013, 1014,
Interface technology, 133, 138–140, 145, 1016, 1018, 1023
146 Leaching conditions on vanadium leaching
Iron, 3, 10, 11, 21, 22, 27, 34, 67, 72, 78, 95, efficiency, 440
116, 133–140, 143, 145, 146, 172– Lead anode slime, 81, 82
174, 194, 195, 254, 255, 264, 265, Limonitic nickel laterite, 879–884, 887
292, 295, 296, 300, 303, 306, 310, Li2 O, 562, 705, 706, 708–713
311, 319, 320, 383, 393, 394, 396– Liquid flowing time, 617, 620, 622, 625
402, 405, 406, 408, 410–414, 418, Liquid fluidity, 617, 619, 621–623, 625
432, 440, 445, 446, 448–451, 465, Lithium orthosilicate, 562
1044 Subject Index
Logistic regression, 33–35, 40 619, 630, 642, 643, 674–678, 684,

Low-carbon low alloy steel FAS3420H, 338 695, 699, 706, 726, 728, 731, 732,
Low grade, 360, 475, 482, 486, 548, 759, 736–738, 760, 762, 767, 769, 770,
879, 933, 934, 937 781, 813, 815, 825, 835–837, 840–
842, 857–859, 861–865, 868, 879–
881, 885, 887, 902, 923, 934–936,
M 955, 1024, 1028, 1029
Magnesia–carbon, 22, 23, 780 Mg treatment, 596, 598–600, 604
Magnesiowustite, 21, 29, 30 Microstructure, 123, 124, 127, 128, 130,
Magnesium flux, 836, 841, 843 147, 158, 160–162, 164, 165, 174,
Magnetic field, 147–151, 153, 154, 275, 281, 330–335, 338, 381, 382, 385, 399,
283, 285, 396, 397, 513–515, 629, 418, 420, 427, 456, 457, 461, 463,
970, 971 464, 523, 524, 531, 532, 535, 537,
Magnetic ore powder, 895, 896 539, 633, 773, 803–805, 808, 836,
Magnetic separation, 194, 296, 393, 394, 839, 863, 865, 885–887, 889, 946–
401, 402, 445, 446, 448, 450, 451, 949, 959, 960, 997, 1002, 1013, 1016,
476, 512–517, 868, 879, 880, 953, 1020
954, 957, 958, 963–965, 970–972, Microstructure analysis of sample ore phase,
988 633
Manganese ores, 43, 303, 304, 757, 759, 760, Microstructure evolution in hot processing,
769, 811, 812, 815 160
Mass ratio, 360, 367, 405, 409–411, 413, Microstructure of the fired pellets, 863
551–553, 555, 557, 574, 766, 804, Micro-structure of samples obtained by
823–828, 832, 903, 959, 960, 1023, super-gravity enrichment, 1006
1030 Microstructures during the heat processing,
Material and heat balance model, 783 946
Material consumption, 465, 466, 468–472 Microwave, 405, 406, 408, 412–414, 512,
Material flow, 133, 138, 143–145, 476, 481, 516–518, 541, 569, 570, 572–576,
649 578, 628
Materials analysis, 787 Mineralization, 648, 690, 845, 846, 849–855
Mathematical modeling, 342 Mineralogy of product sinter, 885
Mean square displacement, 153 Mixing, 3, 4, 6–11, 13, 15–19, 24, 45, 111,
Mechanical carbon coating, 895, 896 209, 227, 230, 231, 233–236, 297,
Mechanical properties, 111, 127, 158, 240, 306, 310, 341, 342, 348–350, 490,
254, 330, 531, 532, 536, 539, 561, 584, 627, 643, 779, 780, 786, 788,
562, 599, 603, 941, 949, 1028–1030 793, 799, 976
Mechanism of nucleation of spherical car- MnS inclusions, 595, 596, 599–601, 603,
bides, 335 604
Mechanism of the enrichment by super- Model development, 24
gravity, 1009 Model formulation, 57
Melting and refining, 941 Model hypothesis, 56, 228, 978
Metallized pellets, 405, 408–414, 569, 574– Model of fluid flow, 792
578, 867–870, 872, 876 Model of heat transfer by radiation, 793
Metallurgical performance, 779, 835 Modeling, 23, 44, 136, 183, 189, 216, 253,
Metallurgical properties, 277, 627, 736, 811, 275, 276, 342, 344, 585, 786, 977
835, 836, 857, 858, 861–865 Model verification, 980
Metallurgical slags, 184, 295, 475, 521, 523 Mo equation, 711
Method of Analysis, 84 Molar heat capacity, 215, 217, 219, 222, 223
MgO, 21–30, 110, 117, 171, 172, 174, 193, Molecular dynamics, 147
195–197, 199, 201, 202, 218, 224, Molten blast furnace slag, 321
240, 243, 245–247, 292, 320, 383, Molten salt electrolysis for silicon, 93
419, 422, 440, 445–447, 455, 457, Molten steel temperature, 741–743, 747,
459, 460, 513, 515, 542, 577, 595, 753, 754
Subject Index 1045
Molybdenum, 265, 456, 715, 716, 718, 723, Ostwald ripening behavior, 329, 330, 336,
896, 912, 939, 941–944, 946–950, 338
1003 Oxidation of phosphorus in LD process, 501
Molybdenum Carbide, 715, 716, 723 Oxide inclusions, 240, 243, 248–250, 595,
Morphological analysis, 610 596, 601, 773, 774
Morphological observation, 657, 658 Oxygen carrier, 921–923, 926–929
Morphology, 18, 19, 96, 163–165, 240, 241, Oxygen-rich bottom blowing, 979, 981
250, 457, 459, 461–463, 489, 490,
492, 493, 497, 537, 538, 596, 599,
601, 607, 610, 653, 654, 658, 723, P
731, 733, 734, 774, 776, 778, 791, P2 O5 , 116, 117, 381–388, 390, 500, 501,
805, 806, 836, 838, 846, 858, 860, 825, 847, 848
861, 895, 980, 1019 Packed bed, 43, 45–52
Multi-generation system, 67, 68 Pairwise Radial Distribution Function
(PRDF), 150
Particle segregation, 551–554, 557, 558
N Pb–Ag–Sb melts, 1002
Na3AlF6–SiO2 melt, 93, 99 PCA-CBR, 746
Narrow window control, 33–35, 41 PCA-CBR model, 750
Nickel, 124, 295, 296, 523, 541, 542, 544– Pellet, 203, 209, 211, 212, 301, 405, 409–
549, 596, 806, 845, 846, 848–854, 413, 569, 570, 573–576, 578, 698,
855, 879, 880, 887, 891, 954, 1013– 700, 835, 836, 838, 840–843, 857,
1018, 1020 858, 861–863, 865, 867–869, 903–
Nickel alloy, 848 909
Nitridation, 605–608, 610, 612 Perforated ratio, 663, 664, 666–669, 671
Nitrides, 605–607, 612 Phase equilibria, 102, 183, 184, 189
Nitrogen, 15, 183–185, 187–190, 394, 420, Phosphate capacity, 499–501, 505–509
490, 605–607, 609, 611, 612, 639, Phosphorus distribution, 116, 499, 500, 508
640, 647, 681, 682, 685, 690–692, Phosphorus distribution between slag and
726, 779, 921, 955, 956, 965, 966 metal, 508
Non-isothermal flowing, 585, 592 Physical and microstructured analysis of
Non-isothermal kinetics, 301 finished pellets, 839
Non-oriented electrical steels, 773, 774 Physical simulation, 482, 486, 663–665
Numerical and analytical methods, 552 Physicochemical parameters of refining
Numerical simulation, 58, 69, 207, 227, slag, 736
228, 277, 342, 344–346, 348–351, Pilot-scale, 67, 68, 303–305, 316, 317, 757,
354, 355, 664, 791, 792, 794, 976, 758, 760, 766, 770, 812
979–981 Polyhedron method, 217, 219, 222, 223, 225
Numerical simulation research method, 228 Powder metallurgy, 1023, 1024
Precious metal, 81, 82, 84, 85, 90, 370, 379,
380, 991, 998, 999
O Precipitates, 111, 161–166, 334, 523–527
Off-gas and dust handling, 312 Precipitation, 158, 160–163, 165, 248, 249,
Oil phase entrainment, 475, 476, 479, 481, 290, 333, 338, 381, 382, 384–386,
483, 486 388, 390, 441, 457, 490, 521–524,
Online prediction, 257 526, 527, 541–544, 546, 549, 561,
Optical analysis, 669 601, 805, 807, 808, 1017
Optimizing oxygen supply system and the Precise calcium treatment software, 253, 255
operating lance position, 119 Predicted gas components and temperature,
Optimizing the loading system, 121 73
Optimum distillation time, 376 Predicted reduction degree of hematite, 76
Ore blend, 760 Prediction model, 673, 674, 676, 741, 746
Orthogonal test, 7, 9 Predictive modeling, 69, 77
1046 Subject Index
Preparation method, 1024 Reduction, 49, 67, 68, 70–77, 82, 121, 136,
Pre-process of the BBF simulation, 976 143, 203, 206, 209, 210, 212, 290–
Pressure fluctuation, 663, 664, 666, 667 294, 296–298, 300–302, 304, 306,
Principal component analysis, 741, 743, 748 312, 320, 342, 388, 393, 394, 396,
Principle of separation, 85 398, 401, 405, 406, 408–414, 417,
Printed circuit boards, 964, 987, 988 418, 422, 423, 425, 426, 428, 432,
Process conditions, 979 436, 442, 445, 446, 448–451, 476,
Process metallurgy, 101, 103, 112 482, 485, 486, 512–518, 526, 527,
Process parameters WOE value statistics, 39 548, 569, 570, 574–578, 605, 607,
Process reconstruction, 133, 134, 137–139, 608, 612, 628, 629, 636, 640, 648,
145, 146 653–660, 668, 669, 671, 674, 681–
Process energy requirement at equilibrium, 683, 689–692, 716, 766–769, 786,
763 787, 792, 808, 812, 814, 819, 823,
Production of titanium-containing pellet, 825, 826, 828, 835, 836, 838, 840–
The, 694 843, 846, 857, 861–863, 865, 867,
Purification, 82, 94, 370, 373, 379, 791, 868, 870, 879, 880, 887, 895, 896,
1013, 1014, 1016, 1018 898, 900–905, 907–909, 921, 922,
Pyrolysis, 417, 418, 783, 784, 926, 963–966, 928, 929, 934, 954, 956–958, 1001,
968–972 1002, 1024
Pyrometallurgy, 417, 522, 954 Reduction kinetics, 295, 445, 654, 895
Pyrrhotite tailings, 803 Reduction process, 449
Reduction temperature, 578
Q Reductive Smelting of Slag, 548
Quality of finished pellets, 839 Refractory, 14, 21–24, 26–30, 76, 101, 102,
171, 172, 181, 310, 311, 313, 406,
677, 697, 738, 785, 792, 796, 799,
R 932, 939, 941, 942, 990
Radiation, 58, 69, 72, 83, 84, 107, 207, 433, Relationship between process reconstruc-
793, 804 tion and energy saving, 138
Rare earths, 518, 522, 1002
Raw and accessory material conditions, 781 Relative plasticity, 603, 604
Raw materials, 629, 759, 868, 880, 896, 902, Research methods, 641, 849
922, 1015 Residence time distribution curve, 234
Raw materials receiving and handling, 308 Revising raw material phase composition,
Reagents, 433 766
Recover, 823 RH refining, 116, 121, 741, 743, 747, 748,
Recoveries of Cr and Fe, 826, 828, 829 753, 754, 774, 791, 796
Recovery, 81, 82, 90, 134, 143, 290, 294,
296, 320, 359, 360, 366, 367, 370, RH vessel, 747, 791
376–382, 385, 388–390, 393, 394, Ring formation, 279, 693, 694, 696–698,
417, 425, 428, 432, 445, 446, 450, 700, 701
451, 475, 511–515, 517, 518, 521– Roasting atmosphere, 359, 360, 364, 366,
523, 526, 527, 545, 546, 569, 570, 367, 435, 698, 701
759, 760, 766–769, 824, 828, 846, Roasting conditions on vanadium leaching
850–854, 867, 868, 876, 902, 933, efficiency, 435
934, 954, 957, 963, 964, 970–972, Rotary cup, 319
987–989, 992–994, 996–999, 1002
Red mud, 393–395, 397–402, 511–518 Rotary hearth furnace, 203, 204, 206, 212
Reducibility, 840 Rotary kiln, 303, 304, 308–310, 317, 359,
Reducing agent, 21, 406, 418, 428, 446, 512, 570, 694, 696, 698, 700, 701, 761,
513, 515, 517, 633, 812, 846, 849, 811, 812, 816, 819, 820, 824, 868,
902–908, 953–955 879, 1023
Reductant amount, 823, 829–832 Rutile, 381, 382, 384–390, 397, 402, 609
Subject Index 1047
S 342, 353, 354, 359, 360, 381–390,

Sample preparation and characterisation, 417–428, 432, 445, 446, 451, 475–
126 478, 482, 499–505, 508, 509, 521–
Saturated vapor pressure determination, 85 527, 541, 544, 546–549, 705, 725,
Scanning electron microscope examination 726, 728, 730–734, 736–738, 747,
of the ore, 545 757, 759, 763, 765–767, 769, 780–
Secondary resources, 290, 359 785, 826, 835, 836, 841, 842, 846,
Segmented combined blowing, 911–913, 858, 867–876, 931, 933, 936–939,
916, 918 964, 975, 976, 980–985, 1002, 1014,
Segregation, 94, 276, 279, 494, 496, 497, 1023, 1024, 1026, 1028, 1030
539, 547, 551, 552, 554, 555, 557, Slag and alloy handling, 311
558, 995, 997 Slag eye, 13, 16, 18, 19
Selection of calculation methods, 978 Slag phase, 102, 104–106, 108, 112, 306,
Selective distribution, 405, 412 387, 389, 390, 546, 547, 867–876,
Selenium, 369–374, 377–380 912, 975, 983
Self-reduction, 405, 406, 412–414, 569, 570 Smelting, 544, 546
SEM analysis of the reduced sample, 427 Smelting reduction, 76, 422, 476, 482, 486,
Semi-industrial experiment, 376 954
Semi-molten, 446 Smelting-separation, 867–876
Sensitivity analysis, 767 Smelting time, 3, 137, 465, 823–825, 828–
Separation of Cu–Zn alloy, 996 830, 832, 867–869, 873, 874, 876
Separation of Sn–Cu alloy, 992 Sn, 94, 289, 489, 531–534, 537, 539, 757,
Sequence quadratic programming, 673, 674, 847, 987, 988, 990–999
678 Sodium magnesium silicates, 215, 217–225
Shaft kiln, 43–45, 52 Sodium roasting, 431, 432, 442, 824
Side hole flow rate, 233 Softening and smelting property, 842
Si-deoxidized stainless steel, 239, 246, 249
Solidification, 94, 101, 164, 227, 228, 232,
Silver, 81, 82, 369, 370, 375, 379, 380,
233, 235, 239, 240, 248–250, 273,
1001–1007, 1009
275, 276, 278–280, 285, 286, 457,
Simulation scheme, 58, 230 489, 493–496, 498, 521, 522, 524–
Single-induction heater, 582, 585, 586, 590, 527, 773, 774, 778, 799, 846, 946,
592 947, 1004, 1005
Sinter feed, 683, 857, 858, 861–863, 865
Solid-state diffusion, 21, 23, 30
Sintering, 21, 34, 135, 401, 499, 610, 617,
Solid-state reduction, 511, 512, 515, 518
619–621, 625, 627–629, 631–633,
636, 639–641, 643–645, 647–650, Solver settings, 980
673, 674, 676, 681–683, 685–692, Spatter analysis, 983
845, 846, 849–855, 879, 880, 882, Spherical carbides, 336
884, 887, 895, 959, 1023–1026, 1029 Spheroidization effect of intercritical
Sintering mineralogical study, 879 annealing process, 333
Sintering performance, 673, 884, 887 Spheroidization effect of subcritical anneal-
Sintering temperature, 1025 ing, 334
Sintering temperature test, 1028 Stainless steel pickling sludge, 953–955, 957
Sintering time test, 854 Standard formation enthalpy, 225
Sinter output, 649 Statistical optimization, 716
Sinter quality, 649 Steel, 3, 4, 10, 11, 13–15, 17, 18, 33–37,
Sinter strength, 673, 676–678, 836, 885, 887 39, 55–63, 84, 95, 101–108, 110–
Slag, 10, 11, 18, 56, 58, 63, 82, 94, 101, 103– 112, 115–118, 120–122, 124, 133–
107, 110–112, 115–122, 139, 147, 140, 142–145, 157–163, 165, 166,
148, 150, 171, 172, 174–181, 183, 171, 183, 203, 227–233, 235, 239–
184, 187, 188, 241, 243, 289, 291– 241, 243, 244, 246, 248–250, 253–
293, 295, 296, 301, 306, 308, 310– 258, 264, 281, 289, 310, 319, 320,
312, 314, 315, 317, 319–326, 341, 329–331, 334, 338, 341, 342, 347,
1048 Subject Index
352–354, 383, 431–433, 446, 455– 311, 319, 321, 330, 331, 333, 334,
461, 463–470, 472, 475, 477, 478, 337, 342, 347, 352, 353, 360, 361,
489–491, 493–495, 497–502, 504, 363, 366, 367, 370, 372–374, 377,
505, 508, 509, 531–535, 537, 539, 382, 384, 389, 393, 394, 400–402,
569, 570, 581–583, 585, 590, 592, 405, 409, 410, 412, 413, 418, 420–
593, 595–601, 603, 604, 628, 639– 422, 425, 426, 431, 435–437, 440,
641, 650, 673, 681–683, 705, 706, 442, 446, 448, 456, 457, 461, 468,
715, 725, 726, 728–730, 732, 733, 469, 476, 478, 482, 486, 490, 494,
736–738, 741–743, 747, 754, 774, 495, 499, 500, 503–509, 513–517,
777–781, 783–785, 787, 788, 791, 521, 523, 524, 526, 527, 532, 534–
792, 796, 799, 811, 825, 836, 868, 537, 540, 543, 544, 561–565, 569,
879, 880, 901, 903, 911, 912, 914, 575, 581, 584, 585, 595, 596, 603,
953–955, 960, 963, 964 605–612, 617–620, 623, 625, 627,
Steel making, 101, 102, 112, 346, 499, 501, 628, 631, 644, 653–660, 689, 693,
780 694, 696–698, 701, 705–712, 715–
Steelmaking−continuous casting interface, 720, 723, 725, 741, 742, 747, 761–
140 764, 767–777, 779–782, 784–786,
Steel refining, 101–103, 105, 108, 111, 112, 788, 791–800, 803, 804, 811, 812,
253, 726 814, 816, 819, 820, 824, 826, 828,
Stoichiometric reductant requirement, 763 835, 836, 841, 842, 845, 846, 849–
Structural property, 148 855, 857, 862, 865, 867–873, 876,
Structure of the furnace material database, 895–897, 901–904, 907, 909, 911–
The, 468 918, 921, 923–927, 929, 931, 933–
Subcritical annealing, 329–331, 334, 335, 939, 941, 942, 944–949, 953, 956–
338 958, 960, 963–966, 968, 969, 972,
Sulfate roasting process, 1016 978, 983, 987–990, 992–994, 996,
Sulfation roasting, 1013, 1014, 1016, 1018 997, 999, 1003–1005, 1016, 1018,
Sulfurizing agent dosage test, 850 1023–1026, 1029, 1030
Sulfurizing agent type test, 849 Temperature analysis of molten pool, 916
Super-gravity separation, 381, 389 Temperature difference, 62, 64, 108, 228,
Super-gravity technology, 382, 1001, 1002, 268, 584, 586, 590, 592, 796, 916
1009 Temperature effect, 509
Super-high bed height, 644
Temperatures, 854, 911, 957, 958
Synthesis, 72, 561–563, 606, 715–717, 921,
1030 Tensile, 129
Synthetic slag, 934 Tensile properties, 123–125, 129, 130
Theoretical analysis of saturated vapor pres-
sure, 370
T Theoretical analysis of the Pb–Sb alloy’s
Tailings, 803–805, 823–827, 832, 850–853, phase diagram, 1005
855, 879, 880, 959, 960, 963, 964,
Theoretical ratio, 1026
971, 1002
TCOX database, The, 102 Thermal analysis, 784
Temperature, 4, 13, 21, 22, 26, 27, 30, 33– Thermal concentration, 805
37, 39, 43, 44, 47–52, 55–58, 60, 62– Thermal effect, 263, 264, 267, 268, 270, 633
64, 68, 70, 72, 73, 75–77, 84–88, 90, Thermodynamic, 72, 101–104, 107, 109,
93–99, 102, 107, 110, 115–127, 129, 112, 119, 140, 161, 162, 171, 178,
130, 137, 139, 140, 142, 143, 148, 181, 183, 184, 187, 189, 190, 194–
150, 154, 157, 158, 160, 161, 163, 196, 198, 200, 201, 215–223, 225,
165, 166, 174, 178, 184, 187, 188, 239, 240, 246, 249, 250, 255, 264,
190, 193–195, 197–204, 208–212, 289, 292, 294, 361, 379, 386, 388,
216, 219, 220, 222, 224, 227, 228, 418, 421, 457, 496, 541, 542, 621,
233, 235, 239–241, 243, 248–250, 736, 757, 761–763, 931, 934, 939,
254, 263–270, 273, 277, 289–301, 941, 943, 949, 950, 957, 1024
Subject Index 1049
Thermodynamic analysis, 193, 216, 360– Vacuum Arc Remelting (VAR), 273, 281,
362, 364, 367, 421, 422, 490, 493, 286
495, 607, 612, 773, 1023 Vacuum distillation, 82–85, 90, 369, 370,
Thermodynamic analysis of La-S-As rare 372, 374, 377, 379, 380, 988, 1001
earth inclusions, 495 Vacuum separation, 83, 90
Thermodynamic analysis of LaAs rare earth Vanadium, 163, 263–267, 270, 303, 381,
inclusions, 493 431–433, 435–437, 440–442, 445,
Thermodynamic calculation, 457 606–608, 629, 630, 632, 633, 823–
Thermodynamic conditions at EBM of Mo, 825, 867, 868, 871, 876, 911, 912,
943 914–916, 918, 921–924, 928
Thermodynamic calculations, 761 Vanadium-bearing titanomagnetite, 867,
Thermodynamics, 22, 71, 101, 178, 179, 868, 876
225, 240, 250, 341, 418, 605 Vanadium extraction, 263–266, 431, 432,
Thermodynamics analysis of the gasifica- 442, 823, 824, 871, 876, 911, 912,
tion–reduction coupling process, 71 914, 917, 918
Thermodynamic simulation, 178, 180 Vanadium slag, 264, 431–437, 440–442, 824
Thermogravimetric analysis (TGA), 966, Velocity field in furnace, 982
971 Viscosity, 47, 49, 56–58, 102, 104, 148, 153,
300t converter, 115, 116, 341, 342, 344, 355 228, 229, 277, 296, 321, 342, 343,
Ti-bearing blast furnace slag, 381–385, 388, 347, 382, 388, 417, 425, 426, 446,
390 478, 483, 583, 617, 621, 623, 625,
Ti4822 alloy, 123–125, 127 656, 666, 705–708, 711, 725, 726,
Time-domain analysis, 666, 667 736–738, 777, 778, 793, 840, 867,
Titanium-containing pellet, 694 870, 872–874, 876, 931, 933, 936,
Titanium slag, 432, 445, 446, 451 938–940, 979, 980
Titanomagnetite, 431, 432, 445, 825, 867, Vitreous content, 319, 323–325
921–923, 928 VOF modeling, 342
Total oxygen and dissolved oxygen, 728 Volume combustion synthesis, 561–563
Transformation mechanism, 928
Transition metal oxides, 605, 607
Tumbling test, 817 W
Tundish with channel type induction heating, Waste plastics, 901, 902
581, 582 Waste steel tailings, 963–969, 971, 972
Tungsten slag, 183, 289 Water-cooling system, 315
Turbulence model, 979 Water leaching, 359–361, 367, 824, 1014,
Turbulence modeling, 344 1016
Turbulent kinetic energy of liquid surface, Water leaching purified process, 1016
232
Twin-roll strip casting, 227, 228
25Cr2Ni4MoV steel, 725, 726, 732, 737 X
XRD analysis, 440
XRD phase analysis, 632
U XRF analysis, 441
Ultrahigh-basicity mold flux, 705
Upper pool mixing, 234
Z
Zinc ferrite, 193–196, 199, 201, 202
V Zinc kiln slag, 1023–1027, 1030
Vacuum arc control, 283 Zinc oxide, 194–202

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11th International

Jerome P. Downey Dean Gregurek

Baojun Zhao Onuralp Yücel

Ender Keskinkilic Tao Jiang

Jesse F. White Morsi Mohamed Mahmoud

Jerome P. Downey Dean Gregurek

Baojun Zhao Onuralp Yücel

Ender Keskinkilic Tao Jiang

Jesse F. White Morsi Mohamed Mahmoud

ISSN 2367-1181 ISSN 2367-1696 (electronic)

We would like to acknowledge the contributions from the authors of included

Part I Simulation of High-Temperature Processes

Part II Energy Efﬁcient Clean Metallurgical Technologies

Part III Fundamentals of Metallurgical Processes

Thermodynamic Analysis of Chlorination of Zinc-Bearing Phases

Part IV High-Temperature Processing

Preparation of Expanded Slag Ball with Blast Furnace Slag

Part V Extraction and Recovery of Metals

Separation of Vanadium from Iron in Vanadium-Rich

Part VI Treatment and Recycling of Wastes

Part VII Preparation of Alloys and Materials

Production of a Cobalt–Nickel–Iron Alloy from Low-Grade Ore . . . . . 541

Part VIII Sintering and Pelletizing

Reduction Behavior of In-ﬂight Fine Hematite Ore Particles

Part IX Ironmaking and Steelmaking

Effect of CO2 Mix Ratios on Materials and Heat Balances

Part X Utilization of Complex Ores

Part XI Poster Session

Synthesis of Na2(Ni, Fe)(SO4)2 Cathode Materials from Nickel

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1033

Zhiwei Peng is a Professor in the School of Minerals

& Exhibition, the Doctoral Finishing Fellowship and

Jiann-Yang Hwang is a Professor in the Department

involved in the areas of separation technologies,

Jerome P. Downey earned his Ph.D. in Metallurgical

Dean Gregurek has been a Senior Mineralogist at the

Baojun Zhao is the Codelco-Fangyuan Professor in

Onuralp Yücel completed his technical education

• Pyrometallurgy: Pretreatment of concentrates (pro-

• Beneﬁciation of industrial wastes: Production of

Ender Keskinkilic earned his undergraduate degree

Tao Jiang received his M.S. in 1986 and Ph.D. in

Jesse F. White holds a Ph.D. in Materials Science and

Morsi Mohamed Mahmoud joined the Mechanical

processing, glasses, ceramics, and structure–property–

Keywords Electric arc furnace · Hydraulic model · Combined blowing

X. Wu · R. Zhu (B) · G. Wei · K. Dong

© The Minerals, Metals & Materials Society 2020 3

Fig. 1 Combined blowing experimental instruments of hydraulic model experiment

ρgp (π/4)d 2p u 2p ρgw (π/4)dw2 u 2w

where ρ lw , ρ lp , ρ gw , and ρ gp are, respectively, the liquid density of the hydraulic

Fig. 2 The combined blowing arrangements in EAF model

Table 2 Gas flowrates of

Results and Discussion

Analysis of Hydraulic Model Experiment Results

Table 3 Mixing time of different flowing conditions

Table 5 Analysis of variance of different elements

Fig. 3 Chart of mixing time

Analysis of Industrial Test Results

Table 7 Average industrial results of two kinds of flowing patterns

Fig. 4 Distribution of main

Keywords Ladle · Argon blowing mode · Mixing · Slag eye

Z. Tie · Q. Hu · X. Li · J. Liu · J. Zhang · Z. Yang (B) · H. Tang (B)