Recent Developments in Refractories & Clean Steel Making Technology

Andreas Buhr, Almatis, Frankfurt, Germany Ralf Bruckhaus, AG der Dillinger Httenwerke, Dillingen, Germany Reinhard Fandrich, Stahlinstitut VDEh, Dsseldorf, Germany International Conference on Advances in Refractories and Clean Steel Making, June 26 28, 2013, Isphat Bhawan, SAIL, Ranchi, India

Content

Trends in steel making technology

Requirements on high purity resp. high quality (HQ) steel grades Focus on secondary metallurgy

Impact of refractories and trends

Interaction between steel and refractories Refractories as tools for clean steel making Economics in refractory usage

Conclusion & Literature

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General trends in steel making technology

Ongoing development of new steel grades with tailored properties for various very different applications High purity steel grades with tight specifications for undesired impurities and alloying elements Extended processing of liquid steel in secondary metallurgy Zero error strategies with max. productivity and flexibility Near net-shape casting technologies in order to reduce the energy consumption (e.g. thin slab vs. conventional CC -50%) Share between oxygen and electrical steel making depending on maturity of steel market (availability of scrap) in a region: Americas, Europe, Japan 40-50% EAF China <10% EAF India 60% EAF; limited scrap but HBI/DRI instead
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Requirements on HQ steel grades: impurity content

Elements: C, S, O, N, H

Achievable contents after secondary metallurgical treatment between 1960 and 2010
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Requirements on HQ steel grades: alloying agents and relevant aggregates for ladle treatment

Red = Min. Target Blue = Max. Target

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Source: A. Viertauer, Siemens VAI Metals Technologie GmbH, VDEh refractory seminar April 2012

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Secondary metallurgy for BOF and EAF process routes

Steel treatment in the ladle defines quality of the steel grades

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Secondary metallurgical process routes flexibility and diversity

Scheduling in a steel shop more and more important Reliable availability of the equipment mandatory (incl. Refractories!) power outages a challenge in India Re-heating of steel required due to extended processing time

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Vaccum treatment plants world-wide 1990 2010 RH & VD types

About 350 VD units and 200 RH units in operation ww 2010

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Technological evaluation of continuous casting processes

Special requirements on steel oxide cleanliness for thin slab casting to avoid clogging Page relatively high share of thin slab in Indian production

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The steel ladle as a metallurgical reactor

Source: H. Lachmund, AG der Dillinger Httenwerke, VDEh steel ladle lining seminar September 2012

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Refractories and clean steel making in secondary metallurgy Slag resistance against metallurgical reactive slag composition Thermodynamic stability of refractory oxides to avoid re-oxidation of steel Lower carbon content to avoid or limit C-pick up after vacuum treatment

Insulation layer in ladle lining to reduce heat losses during extended treatment times

Purging plugs (or lances) as functional refractories essential for treatment Wear resistance of sliding gate plates for automated flow control or Ca-treated steel Page 12 (thin-slab casting)

Slag resistance of ladle refractories

Metallurgically reactive top slag, low melting & viscosity More aggressive for refractory linings Use of higher quality refractories in ladles

Source: A. Viertauer, Siemens VAI Metals Technologie GmbH, VDEh refractory seminar April 2012

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Slag resistance of ladle refractories

Slag line:
MgO/C bricks based on fused magnesia and higher carbon content (incl. graphite) Often bottleneck for balanced lining life, no compromise on quality

Side wall and bottom:

High alumina materials changed from andalusite or bauxite to higher purity synthetic alumina based materials (tabular alumina, spinel) Doloma replaced by MgO/C in order to achieve higher lining life in some steel works, but still in use elsewhere
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Slag resistance of high alumina ladle refractories

Dortmund steelworks (1995): CaO 30%, C/A = 0.6 OK for andalusite C/A 1 andalusite 50 heats (SiO2!) vs. bauxite 130 heats IJmuiden steelworks (2001): direct strip plant (DSP = near net-shape casting) Ca treatment & C/A ratio of slag andalusite bricks -70% lifetime at 20% DSP heats -90-95% at 100% DSP replaced by high purity fired spinel bricks Today, andalusite and bauxite in back lining but not wear lining
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Re-oxidation of steel thermodynamic stability of oxides

Decreasing stability with: - increasing temperature - decreasing PO2 - decreasing CO2/CO - decreasing H2O/H2

Si + O2 = SiO2 2 SiO + O2 = 2 SiO2 4/3 Al + O2 = 2/3 Al2O3

The further down a curve, the more stable the oxide. MgO unstable at high temperature & low PO2

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Re-oxidation & steel oxide cleanliness - Decline of bauxite and andalusite lined steel ladles in Europe 2000 - 2008

Replaced by MgO/C, AMC, or synthetic alumina based castables or bricks (alumina-spinel)

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High alumina raw materials

Andalusite Mulcoa 60 Mulcoa 70 Al2O3 SiO2 TiO2 Fe 2O3 Alkaline Earths Alkalies Bulk Density Apparent Porosity Water Absorption % % % % % % g/cm % % 56-59 38-40 0.2-0.5 0.8-1.5 0.1-0.3 0.2-0.8 3.1 60 35.8 2.4 1.2 0.2 0.2 2.78 5.7 70 25.6 3 1.2 0.2 0.15 2.89 6.2 Bauxite 85 - 90 5 - 10 3-4 1-2 0.4 - 0.8 0.2 - 0.8 3.1 - 3.4 10-15% 3-5% Brown Fused Alumina 94 - 97 0.8 - 1.5 1.5 - 2.5 0.15 - 0.5 0.4 - 0.6 0.2 - 0.4 3.8 - 3.9 1.5 0.4 White Fused Alumina 99.5 0.02 0.01 0.08 0.03 0.3 3.5-3.9 0-9 0-3 Tabular Alumina 99.6 0.01 0 0.04 0.02 0.33 3.55 1.5 0.5 Sinter Spinels AR78/AR90 > 99 (Al2O3+MgO) 0.08 0 0.1 0.2 (CaO) 0.12 3.3/3.4 1.8 0.5 Bonite (dense CA6) 90 0.9 0 0.1 9.0 0.15 3.0 8.5 2.7

Silica content in natural based materials critical for thermodynamic stability and re-oxidation of steel Synthetic alumina based raw materials have high chemical purity
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Carbon pick up in laboratory tests

Source: H. Lachmund, AG der Dillinger Httenwerke, VDEh steel ladle lining seminar September 2012

Limited C-pick up from carbon bond in bricks (mainly 1. heat) Ongoing C-pick up for higher carbon refractories, also valid for MgO/C bricks with >10% C (slag line bricks)
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Kinetic of decarburisation by use of different material in the slag zone

Source: H. Lachmund, AG der Dillinger Httenwerke, VDEh steel ladle lining seminar September 2012

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Influence of refractory material on achievable carbon content

Disadvantage especially for MgO/C bricks (higher C) Low carbon or carbon-free lining for side wall and bottom Alumina materials carbon free as castables or bricks Fired dolomite bricks for stainless steel applications
Source: H. Lachmund, AG der Dillinger Httenwerke, VDEh steel ladle lining seminar September 2012
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Steel ladle wear lining alumina materials

Synthetic alumina based castables or bricks AluMagCarbon bricks Monolithic ladle with relining technique lowest specific refractory consumption Spinel castables pre-reacted vs. in situ formed spinel slag resistance thermo-mechanical properties (see presentation Shankha Chatterjee)
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Steel ladle purging plug

Temperature changes due to cold stirring gas

Source: BFI/VDEh presentation at refractory committee meeting Feb. 2010

Reliable function, high erosion resistance (hot strength) and thermal shock resistance Highest performance alumina-spinel materials
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Evolution of residence time of liquid steel in the ladle from tapping to start of casting

Source: H. Lachmund, AG der Dillinger Httenwerke, VDEh steel ladle lining seminar September 2012

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Ladle insulation

Spinel castable

Reduce heat losses during extended treatment times High C refractories have higher thermal conductivity (heat losses) Energy saving, CO2 reduction gaining importance
Example:6 mio t steel works -1 K heat losses = 300,000 cost saving per year

Bx brick

Microporous Insul board brick

Reduced lining thickness for higher steel capacity of ladle

200 t ladle: - 10mm lining thickness = steel capacity +2.5 t

Insulation of steel ladles is standard in Europe

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Ladle insulating refractories

Material Thermal conductivity Max. service at 300 - 1000 C [W/mK] temperature [C] Insulating fireclay brick 1.2 - 1.4 1260 / 1430 Vermiculite board 0.24 - 0.31 (600C) 800 - 1000 Fiber cont. gunning 0.2 - 0.3 1000 - 1100 Microporous CA6 gunning 0.37 - 0.36 1500 Ceramic fiber board 0.07 - 0.22 1260 Microporous board 0.03 - 0.06 800 - 1000 for comparison: Fireclay brick 1.2 - 1.4 1500 Forsterite brick 1.3 1550 IMPORTANT: STABILITY AND CONTACT REACTIONS!
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Economic aspects
Refractory related operational costs beyond purchase price & installation: Production losses due to unavailability of vessels (relining, lack of reliability, unexpected failure or even worse, incidents) Effect on steel quality Energy losses Yield Environmental, Health & Safety etc Refractory related operational cost directly spend refractory cost Flexibility in secondary metallurgy process routes requires performance reserves of refractories Refractory is a tool to produce steel
(Rinus Siebring, TATA, VDEh Refractory Seminar part 2)
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Conclusion
Secondary metallurgy is the key area in clean steel making technology Production routes are becoming increasingly complex in order to achieve the metallurgical targets Flexibility of the metallurgical equipment is needed to achieve the desired quality of steel and the performance of refractories is a contributing factor here Re-heating of the steel is often required due to long process times Higher purity refractories are used for clean steel making and synthetic materials replace natural ones for high alumina refractories Energy and resource efficiency is becoming even more Page 28 important and thermal insulation contributes here

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Literature
R. Fandrich, B. Kleimt, H. Liebig, T. Pieper, F. Treppschuh und W. Urban: Stand der Pfannenmetallurgie und aktuelle Trends (Status of secondary metallurgy and present trends), stahl und eisen 131 (2011) Nr. 6/7, 75-89 R. Bruckhaus, R. Fandrich: Trends in Metallurgy 2012, 55th International Colloquium on Refractories, Aachen, Germany, 19-20 September 2012 R. Bruckhaus, R. Fandrich: Ist Indiens Stahlindustrie auf dem Sprung? (Indian steel industry leaping forward?), stahl und eisen 133 (2013), Nr. 1, 33-38 A. Buhr, M. Spreij, J. Dutton: Technical and Economic Review of High Alumina Raw Materials for Steel Refractories, IREFCON 2010, Kolkata H. Lachmund: Demands on refractory material for secondary metallurgy, 7th international symposium steel ladle lining, Steel Academy VDEh, Hannover, Germany, September 2012 A. Viertauer: Ladle Metallurgical Treatments & Refractory Stress for a Steel Teeming Ladle, Refractory seminar Steel Academy VDEh, Cologne, Germany, April 2012
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Thank you for your attention!

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