Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
School of Engineering
Department of Chemical Engineering
PRODUCTION OF GRAPHENE
Authors:
Alya’a Alzurqan
Dawood Ghazi
Dena Nazzal
Rawan Radi
Qusai Ghaleb
May, 2018
Submitted in Partial Fulfillment of the Requirements for the Degree of B.Sc. in
Chemical Engineering
“If You Are Working On Something That You Really Care About, You Don’t
”Have To Be Pushed. The Vision Pulls You.
" أﻗﻮى أﺳﻠﺤﺘﻚ ﻫﻮ ﺳﻼﺣﻚ اﻟﺪاﺧﻠﻲ اﻟﺬي ﻟﻢ ﻳﻤﻨﺤﻚ إﻳﺎﻩ أﺣﺪ ﻟﻜﻦ أﻧﺖ.
ﻟﻦ ﺗﺴﺘﻄﻴﻊ أي ﻗﻮة أن ﺗﻄﻔﺊ ﻧﻮرك اﻟﻜﺎﻣﻦ اﻟﺘﻲ وﻟًﺪﺗﻬﺎ روﺣﻚ اﻟﺨﺎﻟﺼﺔ ﻟﻠﻨﻮر اﻷوﺣﺪ ،ﻟﻠﻨﻮر اﻟﻤﻄﻠﻖ "
Executive Summary
Graphene is at the core of a rapidly growing research, because of its unique versatile
properties it became especially interesting for projected applications. Graphene was found
to be undoubtedly emerging as one of the most promising nanomaterial due to its unique
combination of superb properties of electrical and thermal conductivity. This innovation
is one of the first discovered two dimensional (one atom thick) material, therefore it can
absorb only 2.3 % of light. The production of high purity graphene can be achieved by
chemical vapor deposition (CVD), or by electrochemical reactor. Some examples of its
forthcoming applications are in biomedical technologies, electronic industries, water
treatment sector, also in material science, efficient solar panels, aerospace, sensors,
anticorrosion coatings, and high capacity batteries.
This project was experimentally approached to reach the desired product of graphene,
choosing the electrochemical cell method; being the easiest way for large scale
production. Which is also considered to be a clean process besides its high efficient energy
consumption and cost effectiveness of construction. The objectives of this project are to
experimentally producing good quality of graphene nanoplatelets. Testing the product on
different test mechanisms such as the adsorption of heavy metals detected by atomic
adsorption spectrophotoscopy and adsorption of dyes in addition to TEM, SEM and XRD.
Alongside with constructing a theoretical pilot plant based on the experimental results.
To comply with the project goals, results of the applied experiments reveal adequate
outcomes based on the available workspace conditions. The produced graphene was in
the form of nanoplatelets which were tested using the aforementioned methods. Bulk
density was experimentally found to be 0.147 g/cm3, and the particle size is 0.711
micrometer. Adsorption of dye performance using graphene was observed to be
exceptionally better than commercial coarse activated carbon due to its high surface area
as well as better pore network distribution. Results of adsorption of cadmium, lead and
iron indicated a great capacity and capability of adsorption. To produce graphene, it is
evident that the discounted payback period is three years after plant start-up and
production starts.
III
Acknowledgment
This acknowledgement is written profoundly, since this project was a beautiful journey that
we are glad we finished. The last year was really interesting and a challenging we are proud of
accomplishing it.
First of all, we express our deep sense of gratitude to our supervisor Dr. Ali Matar whose
devoted effort and interest to make it possible and we give him a big thank for his patience and
motivation. And for sure the academic staff of the chemical engineering department, especially
Engineer Arwa Sandouqa for her motivation, patience, guidance and valuable advices which is
unforgettable.
One of the essential people that walked this journey step-by-step with us, is Faisal Daba’een.
To whom we thank, for his hard work and undivided attention on all experimental work.
Moreover, we would also like to thank our fellows for standing by our sides especially
Mohammad Saif, Suhaib Hamdan, Mohammad Abo-Qwaider, Fuad Dweik, Batool Nafiz and
Omar Yousef for their motivation, and technical assistance.
We would like to thank Dr. Fadwa and Miss Abeer from department of Chemistry and Dr.
Yousef Abu Salha from the Department of Geology, also Dr. Rand from Hamdi Mango
Academic Research Center for their valuable moral support.
Last but not least we thank to our families, which without their love, prayers, motivation and
support we would never reach this far and we wouldn’t achieve our goals, we will always be
sincerely appreciated.
IV
Disclaimer
This report was written by students at the Chemical Engineering Department, School of
Engineering, The University of Jordan. It has not been altered or corrected, other than editorial
corrections, as a result of assessment and it may contain language as well as content errors. The
views expressed in it together with any outcomes and recommendations are solely those of
students. The University of Jordan accepts no responsibility or liability for the consequences
of this report being used other than the purpose for which it was commissioned.
V
Table of Contents
Acknowledgment IV
Disclaimer V
Nomenclature XII
3.1 Introduction 24
3.1.1 Graphene Preparation 24
3.1.2 Raw Materials Used 27
3.1.3 Apparatus 28
3.2 Experimental Procedure 29
3.3 Results 31
3.4 Discussion of Results 32
3.5 Graphene Characterization 33
VI
3.5.1 Particle Size 33
3.5.2 Bulk Density 34
3.6 Study of Process Variables 35
3.6.1 Effect of Concentration 35
3.6.2 Effect of Voltage 36
3.7 Graphene Performance Testing 37
3.7.1 Adsorption of Dye 37
3.7.2 Adsorption of Metals 41
3.7.3 Particle Size Distribution 45
3.7.4 X-Ray Diffraction 45
3.7.5 Scanning Electron Microscopy 47
3.7.6 TEM 48
VII
Chapter Six: Energy Balance 75
6.1 Mixers 76
6.2 Electrochemical Reactor 77
6.3 Filter 78
6.4 Dryer 78
6.5 Summary of Results 80
VIII
8.3 Equipment Control Loops 105
8.3.1 Electrochemical Cell Control Loop 106
8.3.2 Pumps Control Loop 106
8.3.3 Filtration Control System 107
8.3.4 Tank Control Loop 108
8.3.5 Dryer (Oven) Control System 108
8.3.6 Ultra-Sonication Tank Control Loop 108
8.4 Hazard and Operability 109
8.4.1 Tanks 110
8.4.2 Mixers 111
8.4.3 Electrochemical Reactor 113
8.4.4 Filters 114
8.4.5 Ultra-Sonication 116
8.4.6 Dryers 117
IX
10.1.1 Introduction to Estimation of Fixed Capital Investment 137
10.1.2 Estimation of Fixed Capital Investment 138
10.1.3 Estimation of Fixed Capital Cost 140
10.1.4 Grass Roots and Total Module Cost 141
10.2 Cost of Manufacturing (COM) 142
10.2.1 Cost of Operating Labor (COL) 143
10.2.2 Cost of Utilities (CUT) 144
10.2.3 Cost of Raw Material (CRM) 144
10.3 Revenue Estimation 145
10.4 Profitability Analysis 145
10.4.1 The Cumulative Cash Flow Diagram 146
10.4.2 Cash Profitability Criteria 147
10.4.3 Time Profitability Criteria 148
10.4.4 Interest Rate Profitability 148
X
Appendix A 161
Appendix B 167
References 177
XI
Nomenclature
Wt. Weight Kg
Conversion -
Molar Flow rate of Component i Kmol/hr
Initial Molar Flow rate of Component i Kmol/hr
Ratio Parameter -
∗ Partial Pressure Pa
Molar Composition in Vapor Phase of Component i -
Molar Composition in Liquid Phase of Component i -
Molar Composition in Feed Stream of Component i -
Distribution Coefficient -
Saturation Pressure Pa
Feed Flow Rate kmol
Liquid Flow Rate kmol
Vapor Flow Rate kmol
Heat Flow Rate J/s
Mass Flow Rate Kg/s
Heat Capacity kJ/kmol.K
Temperature K
Sensible Heat Flow kJ/s
Mixture Heat Capacity kJ/kmol.K
Latent Heat Flow kJ/s
Latent Heat of Vaporization kJ/kg.s
Efficiency -
3
Volumetric Flow Rate m /
Pressure Pa
∆ Pressure Drop Pa
Power Watt
Density Kg/m3
Gravitational Force m /s
∆ Height Difference m
∆Ĥ° Heat of Reaction kJ/kg.s
Stoichiometric Coefficient -
∆Ĥ° Heat of Formation kJ/kg.s
XII
XIII
K Thermal Conductivity ⁄ .
Lc Characteristic Length m
V Velocity ⁄
A Coil Diameter m
B Space Between Coils m
Vapor Density ⁄
Liquid Density ⁄
Surface Tension Factor -
Flooding Factor -
Active Area
Safety Factor -
Total Column Cross-Sectional Area
Cross-Sectional Area of Down Comer
Net Area Available for Vapor-Liquid Disengagement
Active, Or Bubbling Area
Hole Area
Perforated Area
Total Head Pressure Drop m
Dry Plate Drop m
Weir Height m
Weir Crest m
Residual Loss -
Lowest Liquid Flow Rate ⁄
Minimum Vapor Velocity Through the Holes ⁄
Orifice Coefficient -
Hole Diameter m
FC Flow Controller -
PC Pressure Controller -
TC Temperature Controller -
LC Level Controller -
CC Composition Controller -
R Refrigerant -
XIV
List of Figures
XV
Figure (3.15): Concentration of Standards Vs. The Absolute Mean 44
Figure (3.16): Structural Characterization XRD Patterns of Graphene Nanoplatelets 47
Figure (3.17): SEM image of graphene 48
Figure (3.18): TEM images of graphene platelets 48
Chapter Four: Process Description
Figure (4.1): The Onion Model of Process Design 50
Figure (4.2): BFD for The Graphene Production 53
Figure (4.3): PFD for The Graphene Production 54
Figure (4.4): Gantt Chart for The Graphene Production Process 55
XVI
Figure (8.4): Pump (P-101 A/B) Control Loop 107
Figure (8.5): Filter (F-102) Control Loop 107
Figure (8.6): Storage Tank (TK-101) Control Loop 108
Figure (8.7): Oven Dryer (D-102) Control Loop 108
Figure (8.8): Ultra-Sonication Unit (S-101) Control Loop 109
Figure (9.2): Factors that must be considered when selecting a suitable site location 124
Figure (9.6): Factors that must be considered when selecting a plant layout 129
XVII
List of Tables
XVIII
Table (8.5): Electrochemical reactor HAZOP study 113
Table (8.6): Filters HAZOP study 114
Table (8.7): Ultra-Sonication unit HAZOP study 116
Table (8.8): Dryers HAZOP study 117
Chapter Nine: Plant Layout
Table (9.1): Advantages and disadvantages of product layout 122
Table (9.2): Advantages and disadvantages of process layout 123
Table (9.3): Advantages and disadvantages of fixed position layout 124
Table (9.4): Spacing 130
Table (9.5): Typical area of preliminary site layout 130
Table (10.1): Fixed capital investment for production of Graphene process using Excel 140
Table (10.2): The factors in calculating the cost of manufacturing (COMd) from EXCEL 143
Table (10.3): Cost of Utilities Estimation for Production of Graphene 144
Table (10.4): Cost of raw material (generated using EXCEL) 144
Table (10.6): Discounted profitability criterion for the graphene production 148
XIX
Overview
Chapter 1, a general
introduction for
graphene is presented in
this chapter. The
properties and
applications of graphene
are mentioned.
Moreover, the future
market of graphene is
discussed. A brief
description for the
content of this project.
Introduction
Graphene is a word combination of graphite and the suffix–ene which means a mono
layer of graphite. Graphene is a two-dimensional (2-D) material, which consists of a single
layer of carbon atoms arranged in a honeycomb structure. Although it is the thinnest
material known, yet it is also one of the strongest materials there is. It conducts electricity
as well as copper, moreover is a better conductor of heat than all other materials. [1, 2]
The following table lists some of the important thermal, electrical, and mechanical
properties of graphene, also in comparison to graphite and steel. Graphene has other
properties making it really special: it is ultra-light yet immensely tough, and two hundred
times stronger than steel although incredibly flexible, it is the thinnest material and it is a
superb conductor. [2]
Table 1.1: Mechanical properties of graphene, and compares it to graphite and steel [3, 4, 5, 6, 7, 8]
Properties of Graphene Graphite Mild Carbon
Steel
Electrical Mobility [cm2/V.s] 200,000 300 -
Density 0.77 mg/m2 1.61-2.49 mg/m3 7.87 mg/m3
Breaking strength [N/m] 42 295-326 0.084-0.40
Young’s modulus [GPa] 2400 4.1-27.6 200-216
Elastic modulus 0.25 TPa 4.8-76 MPa 205 GPa
Electrical Conductivity [S/cm] 96 x 104 3000 1.392 x 106
Thermal Conductivity [W.m/K] 5000 25-470 54
2 | P a g e
Introduction
Graphene is a fast-changing field, there are constant studies concerning it. Furthermore,
graphene is a material that can be utilized in numerous fields, some of which include:
1. Biological Engineering
2. Optical Electronics
3. Ultrafiltration
4. Composite Materials
5. Photovoltaic Cells
6. Energy Storage
Even though all of these uses of graphene are just hypothetical at this point, but scientists
are working on them and they could be real before we know it. [9]
3 | P a g e
Introduction
Predected Growth Rate
35
30
Millions of Dollars
25
20
15
10
5
0
2015 2016 2017 2018 2019 2020 2021 2022 2023 2024 2025
Years
The main objective of this project is to produce graphene with high quality and purity from
graphite sheet using electrochemical cell process. In Addition, scaling up the process to
evolve into a pilot plant.
This project is divided into 12 chapters, where the steps for reaching the graphene pilot
plant is clearly stated. In chapter 1 and 2 define and explain the advantages and applications
for producing graphene. While in chapter 3 all the laboratory work is explained with the
superb testing of the product. The selected process is described in chapter 4 where the
material and energy balances are calculated upon. Chapter 7 includes detailed design on
major equipment that are controlled in chapter 8, also showing a process HAZOP analysis.
The plant layout and site selection are shown in chapter 9 followed by the economic
analysis in chapter 10 then chapter 11 explains the safety on chemicals, and personnel.
Finally closing with the comprehended conductions of the project and suggested
recommendation in chapter 12.
4 | P a g e
Overview
Chapter 2, in this
chapter Graphene is
described in details,
including its discovery.
It includes the possible
applications usages in
the near future. In
addition too, it involves
a process selection
study including an
opening economic
analysis.
Literature Survey
Graphene is literally a marvelous innovation, it is the thinnest material currently known,
and also the world’s strongest material (about 200 times stronger than steel). Furthermore,
graphene has extraordinary thermal and electrical conductivity and has interesting light
absorption abilities. Additional characteristics is that it has thin, light, flexible and
transparent texture. [11]
Despite all the superior aspects revolving around graphene, it has several challenges to
overcome. Being a new material still under studies, it yet lacks having internationally well-
known standards. Also there is always different types and variations in the experimentally
produced graphene based on varying conditions and methods. Unfortunately, high quality
graphene requires high production cost as the process gets more complicated. Another
disadvantage of graphene is that it has uniformity issues which indicates that complex
transportation and handling methods are needed. The graphene market is still at an early
stage, it is still disarrayed and complicated.
6 | P a g e
Literature Survey
2.1 General Definition
Graphene is made from plain carbon, one of the most common and familiar elements
out there. Carbon comes in many crystalline forms called allotropes, resulting in different
chemical and physical properties.
Figure 2.1: Common types of carbon: (a) coal, (b) graphite, (c) diamond,
(d) buckminsterfullerene, (e) nanotube, and (f) graphene
What is graphene? Graphene is the building block of graphite, it is a sheet of carbon atoms
in a honeycomb structure. Pure graphene sheets are considered to be two dimensional
materials, meaning it is only one atom thin.
Graphene has become the most studied nanomaterial; due to its ultra-thin, 2-dimensional
nature and its unprecedented combination of physical properties. It is truly a material that
could change the world, with unlimited potential for integration in almost any industry.
During the next decade graphene is likely to find commercial applications in many areas
from high-frequency electronics to smart coatings. [12]
7 | P a g e
Literature Survey
8 | P a g e
Literature Survey
2.2 Historical Information
Graphene is a thermodynamically stable form of carbon
nanomaterial and extremely intriguing composition of two
individual sp2-hybridised carbon sheets (two dimensional).
Scientists have focused on the development of new
technologies using chemically modified graphene. [13]
The innovative step that made the scientists into Nobel Prize
winners was to find a way of transferring the ultra-thin flakes
of graphene from sticky tape to a silicon wafer. Due to their
results, they detected extraordinary electrical properties of
graphene. [14]
Figure 2.4: History of graphene
9 | P a g e
Literature Survey
2.3 Applications of Graphene
Graphene was found to be undoubtedly emerging as one of the most promising
nanomaterial due to its unique combination of superb properties of electrical and thermal
conductivity. This innovation became especially interesting for researches and projected
applications. Some of the promising forthcoming applications of graphene are in
biomedical technologies, electronic industries, water treatment sector, sensors, and
composites and coatings.
1. Biomedical Technologies
The unique properties of graphene that accommodates for biomedical technologies, include
high surface area, electron mobility and functionalization potential. To illustrate, the
surface area of graphene makes an excellent platform for drug delivery and the conductivity
makes for effective biosensors. Recent researches have shown that graphene can be
integrated with a polymer to make exceedingly sensitive electromechanical sensors.[15]
2. Electronic Industries
Graphene can encourage the upcoming state-of-the-art innovative technologies from chips
and interconnects for data communication to wearable adjustable screens. Moreover,
coupling graphene’s thinness with its conductivity highly indicates that it minimizes a vital
driving factor of the electronics industry. [15]
Because of the superb properties that graphene offer, it can be used in enhancing the
efficiency of batteries. New research reported that a working model of a graphene-
enhanced lithium-ion battery for household usage will be ready. [11]
10 | P a g e
Literature Survey
3. Water Treatment Sector
Graphene, only one atom thick, was found that it has tremendous potential for drastically
improving the water permeability. It has been broadly used for water treatment as an
adsorbent for heavy metal, and organic molecules, and even salts. Due to its remarkable
capacity for excellent immobilization of various contaminants, and the high surface area
of graphene. Studies show that graphene can let water through at more than 100 times the
permeability of existing membranes, while still rejecting salt.
4. Sensors
The latest researches of composites and coatings can be upgraded by graphene. It has
astounding strength, conductivity, flexibility, lightweight nature and barrier properties
which makes graphene useful for an extensive variety of applications. Enhancing boundary
properties while also improving stiffness, strength, and scratch-resistance without
diminishing sturdiness. From anti-static and anti-corrosion coatings through to ultra-strong
and ultra-lightweight composites, graphene can upgrade the execution of current materials
as well as empower new application fields.
11 | P a g e
Literature Survey
2.4 Process Selection
One of the main challenges in the graphene scope is to find an economical procedure for
large scale production of functionalized single- and few-layered graphene sheets. As to be
applied in this project, the electrochemical reactor techniques was the chosen route.
Although, various synthesis methods for graphene sheets can be obtained using three
primary methods: (i) mechanical exfoliation, (ii) chemical vapor deposition (CVD), and
(iii) liquid-phase exfoliation.
Figure 2.5: Several methods of mass-production of graphene in terms of quality and price for
targeted applications [12]
12 | P a g e
Literature Survey
2.4.1 Available Processes
The graphene sheets are arranged in parallel layers, which are adhered by weak
interatomic interactions (Van der Waals bonds) acting between the adjacent layers (as
shown in figure 2.4). The exfoliation of graphene sheets using high energy process can be
summarized as a breakage of the weak bonds between the layers of graphite in order to
obtain graphene sheets. Exfoliation using the traditional milling techniques like ball milling
occurs due to the exposure of graphite layers to compressive and shear stresses. The
compressive stress is a result of the collision of milling balls and is followed by in-plane
fracture and subsequent formation of small graphite fragments in the graphite suspension.
Moreover, the shear stress is parallel to the basal planes and enables the delamination of
the graphene sheets. It needs to be noted that usage of glass beads as the milling media
leads to a reduction in the compressive stress, thus increasing the yield of graphene
sheets.[16]
Figure 2.6: Deformations of the graphite in between colliding balls during ball milling [16]
13 | P a g e
Literature Survey
Assessments reveal this system can be a profitable and a promising method to tackle the
challenges posed by graphene synthesis in comparison to the other techniques. Moreover,
the production time decreased significantly due to contact gear teeth containing an infinite
number of contacts that leads to the acceleration of the shear rate and decrease of the
residence time. [16]
The following figure illustrates the steps required in the mechanical exfoliation production
process. Where (a) shows LE-EG suspension preparation, (b) and (c) exfoliation process,
(d) prepared graphene storage, (e) sonication process, (f) centrifugation process, and (g)
gathered graphene product and DMF.
Figure 2.7: Schematic flowchart for the mechanical exfoliation production process [16]
14 | P a g e
Literature Survey
Method 2: Chemical vapor deposition (CVD)
The chemical vapor deposition CVD method has been used extensively for production
of graphene. In order to synthesize mono- and few-layered graphene sheets with CVD
method, precursors react on transition metal substrates at high temperature. The CVD is
able to produce few-layered graphene with superior quality. However, this approach
requires extreme manufacturing conditions, which increase the costs and may raise safety
factor, such as high vacuum and high temperature. Note that the CVD method is also size-
limited caused by hydrogen, which is one of the major problems of this method. [17]
CVD involves depositing gaseous reactants and the subsequent chemical reaction followed
by the formation of a stable solid deposit over a suitable substrate. The gases are mixed in
the reactor and then deposited onto a chosen substrate generally copper, nickel or silicon.
When the combined gases come into contact with the substrate within the heated reaction
chamber, a reaction occurs that create a material film on the substrate surface. The
temperature of the substrate is a primary condition that defines the type of the reaction. The
resulting product is graphene on the substrate, which will later be washed away so that it
[19] [20]
may be transferred onto a desired substance.
15 | P a g e
Literature Survey
Figure 2.9: Complete apparatus setup for chemical vapor deposition of graphene [21]
The liquid-phase exfoliation of graphite into graphene is one of the most promising ways
to achieve large-scale production at an extremely low cost. The weak van der Waals
interactions can thus provide a mean to exfoliate bulk graphite into thin graphene flakes
measured in nanometer. This approach utilizes very cheap raw material, and as such may
be very promising for industrial scale-up. Liquid-phase exfoliation refers to a different
approaches that exfoliate bulk graphite into graphene directly in the liquid media.
Therefore, elimination of the chemical oxidation step is an advantage of this method. [17]
16 | P a g e
Literature Survey
Figure 2.10: Pilot-plant for large-scale production of graphene by liquid-phase exfoliation using
ultrasound-assistance [17]
Table 2.1: Advantages and challenges associated with each graphene production route
considered. [16] [18]
Safe process
Non-uniformity in product
Mechanical Exfoliation Eco-friendly
Cost-effective
Cost-effective
Electrochemical High yield Affect the conductivity of product
Eco-friendly
17 | P a g e
Literature Survey
Statistical quality control technique is used for analyzing and interpreting process. In this
case, where we have a demerits system in place to indicate the best method selection is a
more appropriate measure. The demerits control chart can be constructed using the
approach in the table below, showing the values that were taken into consideration for all
alternative.
Table 2.2: Demerit table for the best alternative of graphene production
Mechanical
Electrochemical Liquid-Phase Chemical Vapor
Exfoliation
Reactor Exfoliation Deposition
using Ball-Mill
Experimental
4 1 4 1
Availability
Safety 4 2 3 1
Cost Effective 4 3 2 1
Environmentally
3 4 2 2
Friendly
Simplicity 3 3 4 1
Operation
4 4 2 1
Conditions
Total 22 17 17 7
To conclude from the previous table, it can be noticed that the production of graphene
using the electrochemical cell is the most fitting method to be utilized. Since this method
got the highest rank over the other process alternatives.
18 | P a g e
Literature Survey
2.5 Preliminary Economical Analysis
At an early stage of the production of graphene process it is advised to provide a brief
economical view. The cost of raw materials and the markets of product are considered,
along with other suppliers of graphene.
The following table gives an approximate preliminary cost for the major plant materials
cost.
Graphite Sheet 10
Acetone 1.03
Water 0.002
The price of graphene is directly linked to its quality, therefore different graphene
qualities have different applications. Nowadays the price of graphene vary from $100-
$500 per gram, depending on the manufacturing method and quality. In several years, bulk
graphene prices will drop, enabling graphene to enter all markets in its wide domain of
applications. In the meantime, graphene will continue to be used for applications that other
materials simply cannot support.
19 | P a g e
Literature Survey
2.5.3 Other Producers
Table 2.4: Basic synthesis method, production capacity of several big graphene manufacturers[23]
200,000 m2 (2014)
20 | P a g e
Literature Survey
GLOBAL PRODUCTION OF GRAPHENE
Netherlands Others
3% 8%
Japan USA
3% 24%
Italy
3%
Canada
4%
Turkey
6%
Spain China
10% 17%
UK India
11% 11%
Figure 2.11: Number of manufactures of graphene includes 76 companies globally (2015) [24]
21 | P a g e
Overview
Chapter 3, in this
chapter all the
laboratory experiments
are described with their
results. In addition to
the composed graphene
performance testing on
the produced product.
Laboratory Experiments
3.1 Introduction
There are different techniques to convert graphite into graphene or graphene oxide in
laboratories. Although not all of these methods were carried out in this study due to many
reasons, as listed in the table below. The following experiments were conducted within the
limit of available capabilities.
Table 3.1: Reasons why these methods were not preformed [25] [26] [27] [28]
24 | P a g e
Laboratory Experiments
Figure 3.1: Schematic diagram of the mechanism of electrochemical exfoliation of few layer
graphene sheet (FLGN). [30]
This experiment can be blended for somewhere between 20 to 75 minutes of overall time.
It is going to exfoliate better the longer it blends, or the more liquid in proportion to the
graphite, because it will foam. It does not have a particularly good yield on the first run,
therefore reuse of the sediment is preferred to produce greater yield.
25 | P a g e
Laboratory Experiments
Figure 3.2: Schematic diagram of the mechanism of graphite exfoliation using surfactant
This method was approached to test if substituting graphite with activated carbon can result
in the production of graphene.
26 | P a g e
Laboratory Experiments
Furthermore, the graphene sheets readily climb hydrophilic solid substrates, forming a
homogeneous thin film one to four layers thick.
Sodium Sulfate 3
Steel Sheet 4
All materials used were already available in the chemical engineering laboratories, except
for the graphite. Very fine graphite powder was ordered from Inoxia Ltd., with particle size
of 300 mesh (< 53 µm) and typical purity of 98.6%. Also the graphite sheet roll ordered
from Laird Technologies vendor with 30 cm x 30 cm x 0.3 mm dimensions. Graphite rods
were purchased locally with low purity.
27 | P a g e
Laboratory Experiments
3.1.3 Apparatus
Laboratory equipment needed to complete the experiments:
Erlenmeyer Flask
Filter Paper
Funnel
Petri Dish
Spatula
28 | P a g e
Laboratory Experiments
Measure 417 mL of Acetone using a cylinder and pour it into a 1L Grinded flask
Add 88 mL of distilled water
Incorporate 3 g of graphite powder
Attach the mixer blade in the flask and blend at 2000 rpm for 30 minutes.
Make up the solution and sonicate for at least 3 hours
29 | P a g e
Laboratory Experiments
(a) i (a) ii
(b)
Figure 3.3: In lab experiment (a) Electrolysis experiment i) using graphite rod, ii) using
graphite sheet, (b) exfoliation with surfactant experiment setup
30 | P a g e
Laboratory Experiments
3.3 Results
Figure 3.4: Results (a) Acetone experiment, using graphite powder, (b) Electrolysis experiment
i) using graphite rod, ii) using graphite sheet, (c) Soap exfoliation experiment, i) top layer after
drying ii) executing this experiment using very fine activated carbon, iii) executing this
experiment using very fine graphite.
31 | P a g e
Laboratory Experiments
After settling for a day, the beaker consisted of three visible parts: settled activated
carbon or graphite, water, suspended particles with bubbles. The top layer was scraped to
a filter paper and dried, and the results are shown in figure 3.4c. It is clear that no visible
product was produced in this experiment, and we conclude that activated carbon cannot
be used to produce graphene.
Increasing the sonication time affects the graphene/graphite fraction and increases
it where more of the graphite flakes gets to be exfoliated.
Also tap water should not be used because the solubility parameters are heavily
affected by ion concentration, which tap water already has.
32 | P a g e
Laboratory Experiments
33 | P a g e
Laboratory Experiments
Average 0.146
Figure 3.6 Density experiment, (a) 2 mL water with 0.02 g graphene in cylinder, (b) water is
made up to 4 mL in cylinder using pipette, (c) difference in volume in pipette
34 | P a g e
Laboratory Experiments
This experimental part was divided into two parts, in each part one of the parameters will
be studied while the other parameters will be kept fixed. The studies variables are the effect
of concentration of the electrolyte and the applied voltage.
As prepared earlier, a beaker was filled to 250 ml of varying concentrations (0.5, 1.0,
1.5) M respectively of sodium sulfate solution as electrolyte. The graphite and steel sheets
were connected and placed in the beakers, the graphite sheet being the anode and steel
sheet being the cathode. A constant current was applied across the two electrodes, and the
potential of 2-10 V could drive the anions into the intercalation space and make the
exfoliation to proceed. Firstly, run the voltage at 2 volt for 2 minute to let the graphite
disintegrate, then increase the voltage up to 10 volt. The cell was left working for half an
hour, then the solution was poured into the filter paper then washed with 75 ml of 30 %
HCl then with 75 ml distilled water. The filter paper was dried for 2 hours to get rid of all
the liquids. Moreover, 250 mL of acetone was poured over the product in a reagent bottle
to prepare for sonication, this lasts for 3 hours. Finally, the product is filtered and dried.
Three trails were conducted to observe the effect of changing the concentration of the
electrolyte, the results are shown in table A1. The optimum concentration that yields in the
greatest amount of product at 10 volt is 1.34 mol/L as shown in figure bellow.
35 | P a g e
Laboratory Experiments
Repeating the same procedure as before, but with keeping the concentration constant at
0.5 M. Three trails were conducted to observe the effect of changing the voltage applied to
the electro cell. The three trials were exposed to 2 V for 2 minutes for all, then each one
was exposed to different voltage potentials (5 V, 15 V, 20 V) respectively for 30 minutes.
The results are tabulated in table A2. The optimum voltage that yields in the maximum
product at 0.5 M is 13 V as shown in figure 3.8.
36 | P a g e
Laboratory Experiments
Physical adsorption or physisorption results from the action of Van Der Waals forces,
which are composed of London dispersion forces and classical electro-static forces
between adsorbate and adsorbent. [32]
37 | P a g e
Laboratory Experiments
Firstly, to test if that the product could adsorb dye solution then study the adsorption
kinetics.
Later, this experiment was conducted at different conditions to be compared with
activated carbon.
Activated carbon adsorption is one of the physical purification techniques, which offers
one of the most efficient process available for removing certain materials from water. [32]
The apparatus comprises of 500 ml beakers, 4 variable motors, 4 small bottles, dropper, 4
test tubes, and visible spectrophotometer.
This test is about graphene adsorption of 25 ppm dye solution with equal volume 250
mL, and constant speed motor agitator at 250 rpm, and same particle size but with different
weights of graphene. The experimental data was recorded as in table A3, in addition
calculations are tabulated in table A4 and figure 3.9 demonstrates the percentage removal
of graphene at different weights. After the test in two days, figure 3.10 was taken, although
the transmittance readings were not included in the plot because it is considered an outlier.
This experiment concludes that the rate of absorption increases as the amount of graphene
flake used.
38 | P a g e
Laboratory Experiments
Figure 3.9: Dye concentration percentage vs. time for different weights of graphene
39 | P a g e
Laboratory Experiments
After providing an evidence that the produced graphene does adsorb dyes, it was
compared to commercial activated carbon using the same adsorption of dyes experiment
but in different conditions. The produced graphene showed particle size 125 - 250 µm after
sieving, as mentioned in section 3.5.1. To achieve fare comparison all affecting variables
are kept constant, the concentration of the dye was 10 ppm in a volume of 250 ml dye
solution, the weight of all adsorbents is 0.4 g and the speed of mixing is 250 rpm. To keep
the particle size somewhat constant, the available activated carbon has particle size greater
than 420 µm (coarse activated carbon) which was grinded to a close range to the graphene
produced (fine activated carbon). The experimental data was recorded as in table A5 to
compare between adsorbents. In addition, calculations are tabulated in table A6 and figure
3.11 demonstrates the percentage removal of graphene, coarse activated carbon, and fine
activated carbon. After the test in two days figure 3.12 was taken, although the
transmittance readings were not included in the plot because it is considered an outlier. The
results show that the produced graphene preforms better than commercial activated carbon,
and quite close to that of crushed activated carbon powder.
Figure 3.11: Dye concentration percentage vs. time for different adsorbents
40 | P a g e
Laboratory Experiments
Figure 3.12: Dye solutions after 2 day, coarse activated carbon, and graphene respectively
41 | P a g e
Laboratory Experiments
Lead
Iron
The apparatus comprises of 5 100 ml volumetric flask, pipette, balance, and atomic
absorption spectroscopy. The materials used are heavy metal solution, graphene powder,
and distilled water.
Lead ions arising from both natural and anthropogenic sources, are harmful to humans
and living things. Long-term drinking of lead polluted water will cause serious disorders,
such as anemia, cancer, kidney disease and mental retardation. Many techniques have been
applied to remove Pb (II) ions such as distillation, carbon filtration, and reverse osmosis.
[33]
The preparation for this test involves dilution of stock lead solution from 1000 ppm to 5,
10, 15, 20, and 25 ppm in different volumetric flasks. In the available 20 ppm flask 0.15 g
of graphene powder was added, and for the adsorption to reach equilibrium it was set for
the next day. Later the sample was filtered and the clear solution is to be tested, and the 5,
10, 15, and 25 ppm are the standards for the atomic absorption spectrometer.
The results of the adsorption experiments showed that the graphene was an excellent
adsorbent because of its high uptake capacity at a low dose. Table A7 show the data
collected from the spectrometer screen, and figure 3.14 demonstrate the relationship
between the concentration of the standards and the absolute mean with a best fit line. It was
noticed that the concentration of lead decreases from 20 ppm to 1.19 ppm, which indicate
that that the graphene was a good adsorbent. The parameters affecting the adsorption
42 | P a g e
Laboratory Experiments
include: pH value, initial Pb (II) concentration, adsorbent dose, adsorption time, and
temperature.
The preparation for this test involves dilution of stock iron solution from 1000 ppm to 10,
15, 20, 20, 30 and 50 ppm in different volumetric flasks. In one of the available 20 ppm
0.15 g of graphene powder was added, and for the adsorption to reach equilibrium it was
set for the next day. Later the sample was filtered and the clear solution is to be tested, and
the 10, 15, 20, 30 and 50 ppm are the standards for the atomic absorption spectrometer.
43 | P a g e
Laboratory Experiments
The results of this adsorption experiments showed that the graphene adsorbs iron less than
lead. Table A8 show the data collected from the spectrometer screen, and figure 3.15
demonstrate the relationship between the concentration of the standards and the absolute
mean with a best fit line. It was noticed that the concentration of iron decreases from 20
ppm to 7.8 ppm, which indicate that that the graphene was a good enough adsorbent.
44 | P a g e
Laboratory Experiments
Summary Data
MV(um): 0.718
MN(um): 0.697
MA(um): 0.711
CS: 8.44
SD: 0.0754
PDI: 0.0199
Mz: 0.716
Si: 0.0728
Ski: -0.01271
Kg: 0.899
Bragg’s Law
2 sin (3.1)
Where;
45 | P a g e
Laboratory Experiments
Scherrer’s Formula
* (3.2)
cos
Where;
Bragg’s law used to calculate the maximum distance between two parallel successive
planes which is 1.83 nm. Furthermore, the Scherrer’s formula provides additional
information such as the crystallite size that is 5.68 nm. As represented in the figure below,
the only graphene peak is the one with highest intensity, the other peaks are of aluminum
from the sample holder. Calculations are clearly presented in appendix A.
46 | P a g e
Laboratory Experiments
(a)
(b)
Figure 3.16: Structural characterization XRD patterns of graphene nanoplatelets (a) XRD test
on produced graphene (b) XRD test on Graphene from theory
However, the SEM has difficulties in graphene imaging; because imaging of one-atomic
thick graphene layer is challenging due to the resolution limitations of SEM.
47 | P a g e
Laboratory Experiments
(a) (b)
Figure 3.17: SEM image of graphene (a) SEM test on produced graphene (b) SEM test from
theory
(a) (b)
Figure 3.18: TEM images of graphene platelets (a) TEM test on produced graphene (b) TEM
test from theory
48 | P a g e
Overview
Chapter 4, the
sequential steps for
composing the graphene
production process
based. In this chapter
BFD and PFD diagrams
are presented.
Process Description
The hierarchy of process design can be represented sequentially by the layers of the “onion
diagram” (Figure 4.1). The onion model is a very important tool for designing any chemical
process, where a reactor is needed before the separation and recycle system can be designed
and so on. [34]
50 | P a g e
Process Description
The onion model starts from the reactor because it is basically where the raw material
convert into products. Regarding the production of graphene process, an electrochemical
reactor carries out the physical reaction that breaks graphite to produce graphene
nanoplatelets. Moreover, to produce higher qualities of graphene ultrasonic atomizer
minimizes the number of layers of the product.
The next step of the onion diagram is separation of the product and recycle streams.
Separation techniques can be chemical or physical processes, and sometimes a combination
of operations are preformed to reach the desired results. The effluent materials from the
reactor, which consists of a mixture of liquid and solid is separated in a filter. The filter
separated the materials into two parts, the filter cake contains the product, while the filtrate
consists of the electrolyte which is recycled to the electrochemical rector. Although to dry
the wet filter cake an oven is required, which is the next separation technique.
Lastly to finalize the steps in this method heat transfer network and utilities are decided.
Most heat exchangers need utilities such as steam and cooling water to heat and cool
fluid. In the production of graphene heat transfer units are omitted due to little variation
in temperatures. Therefore, the utilities needed to run the plant are electrical supplies, or
solar panels.
51 | P a g e
Process Description
4.2.1 Process Overview
After experimental procedures a certain process was conducted. Briefly describing the
process overview for the production of graphene the simple process is followed.
Prior to the electrolysis process, the salt is manually handled to be mixed with pumped
distilled water in a vessel to reach a certain concentration. Which are fed to the
electrochemical reactor at ambient conditions, where a new graphite sheet with specific
dimensions and weight is added each batch. The effluent gets distributed on the filter then
washed with hydrochloric acid then water, which get stored separately and the electrolyte
recycled. The filter cake consists of the desired product, being discharged in the oven dryer
to evaporate the water.
The dry product gets introduced to acetone in a second mixer then fed to the ultra-
sonication tank that gets separated by the second filter. Filtrate exiting stream gets recycled
back to the mixer, while the filter cake comprises of the graphene product. The wet solid
finally gets dried and the graphene nanoparticles pass through quality testes then gets sent
to packing and storage units.
52 | P a g e
Process Description
4.2.2 Block Flow Diagram
Block flow diagram (BFD) is a visual representation that consists of a series of blocks
that represent different industrial equipment. It is the simplest form of process diagrams
used to simplify industrial chemical processes. [35]
Due to laboratory experimental procedures the following sequential order of operating
units was concluded (figure 4.2).
53 | P a g e
Process Description
Feed Streams
<1> Sodium Sulfate, solid crystals, RT
<2>, <6> Distilled water, liquid, RT
<5> Hydrochloric acid, liquid, RT, for washing
<10> Acetone, liquid, RT, for washing
Effluent Streams
<14> Graphene product, solid powder, 60oC
54 | P a g e
Process Description
4.2.5 Rate of Production
For this process the production rate of one batch cycle is 1 kilogram of graphene. As
shown in figure 4.4 the Gantt chart demonstrates the actual time needed in each operating
unit. It can be said that the duration of one batch is 6.5 hours, if two batches were produced
each day at different working shifts the production will increase to 2 kilograms per day.
Therefore, this graphene nanoplatelets production would be expected to produce 600
kilograms annually.
55 | P a g e
Overview
Chapter 5, in this
chapter material balance
calculations are solved
for all main equipment
in this project, which
are mixers,
electrochemical cell,
filters, dryer and
sonication unit at
laboratory scale then
scaled up.
Material Balance
5.1 Introduction
Material balance is the first step executed when designing a new process or analyzing an
existing one. It is used to determine the quantities of raw materials required and product
produced, as well as calculate the flow rate of streams at any point in the process. It is
almost an essential step to all other calculations in the process design, such as energy
transfer problems and design of equipment. Material balances are the simple application of
the principle of mass conservation, which implies that mass can neither be created nor
destroyed. Which they can be written for any material that enters or leaves a chemical or
physical process.[37]
This is the general material balance equation for any operation in this case.
M in = M out (5.2)
5.2 Scale Up
When new technologies are developed there is a certain procedure for elevating the initial
concept into a large-scale production plant. Which includes developing of the commercial
process, optimization, scale-up from bench-scale to a pilot plant, then from the pilot plant
to a large-scale process. [38]
Figure 5.1 shows the detailed material balance on the bench-scale process, all flow rates
are in grams for one batch. Material balance calculation on most equipment used in the
laboratory is presented below, refer to appendix B.
58 | P a g e
Material Balance
Material Balance on Mixers
The electrolyte in beaker one is first mixed to dilute sodium sulfate, to reach a
concentration of 1.5 M.
53.3
0.176 %
, 303.3
250
0.824 %
, 303.3
59 | P a g e
Material Balance
53.3
0.175 %
, 303.93
250
0.823 %
, 303.93
0.63
0.002 %
, 303.93
60 | P a g e
Material Balance
, ,
1.23
, 0.161 %
, 7.632
53.3 1.23
, 0.176 %
, 296.298
5.771
, 0.756 %
, 7.632
250 5.771
, 0.824 %
, 296.298
0.63
0.083 %
, 7.632
61 | P a g e
Material Balance
, ,
1.23
, 0.014 %
, 85.994
12.5
, 0.155 %
80.859
0.289
, 0.11558 %
, 2.497
62 | P a g e
Material Balance
68.3588
, 0.845 %
80.859
1.578
, 0.632 %
, 2.497
68.4 1.578
, 0.777 %
, 85.994
0.63
0.252 %
, 2.497
, ,
75
1 %
75
1.731
, 0.733 %
, 2.361
63 | P a g e
Material Balance
75 1.731
, 0.979 %
, 74.847
1.578
, 0.021 %
, 74.847
0.63
0.267 %
, 2.361
, ,
1.731
1 %
, 1.731
0.63
1 %
, 0.63
64 | P a g e
Material Balance
Material Balance on Sonication Bath
After drying, graphene is mixed with acetone in a beaker and placed in a sonication bath.
Which does not change anything only helps break down the layers more.
196
, 0.997 %
, 196.63
0.63
0.003 %
, 196.63
Scale-up Ratio
To scale this process to a pilot plant the production rate must be determined. Which
depends on studying variable parameters such as the demand on the product, and selling
price. Considering the production rate is one kilogram per batch, the following calculations
present the scale-up ratio:
(5.3)
1587
.
65 | P a g e
Material Balance
5.3 Electrochemical cell (ECR-101)
, 481.429 1 482.429
84.6
0.1754 %
, 482.429
396.8
0.8226 %
, 482.429
1
0.0021
, 482.429
66 | P a g e
Material Balance
5.4 Filter (F-101)
, ,
1.953
, 0.1612 %
, 12.114
84.603 1.953
, 0.1757 %
, 470.314
9.161
, 0.7562 %
, 12.114
396.825 9.161
, 0.8243 %
, 470.314
1
0.0825 %
, 12.114
67 | P a g e
Material Balance
, ,
1.953
, 0.0143 %
, 136.498
19.841
, 0.1546 %
128.347
0.458
, 0.11558 %
, 3.963
108.506
, 0.8454 %
128.347
68 | P a g e
Material Balance
2.505
, 0.6321 %
, 3.963
108.506 2.505
, 0.7766 %
, 136.498
1
0.2523 %
, 3.963
, ,
, 2.748 1 3.748
119.048
1 %
119.048
2.748
, 0.7332 %
, 3.748
119.048 2.748
, 0.9789 %
, 118.804
69 | P a g e
Material Balance
2.505
, 0.0211 %
, 118.804
1
0.2668 %
, 3.748
84.603
0.1757 %
, 481.429
396.825
0.8243 %
, 481.429
70 | P a g e
Material Balance
5.6 Dryer (D-101)
, ,
, 3.748 1 2.748 Kg
2.748
1 %
, 2.748
1
1 %
, 1
The overall material balance on the sonication bath is neglected since no change in
masses occur.
71 | P a g e
Material Balance
5.8 Process Diagrams
72 | P a g e
Material Balance
73 | P a g e
74 | P a g e
Stream Number 1 2 3 4 5 6 7 8 9 10 11
Material Balance
Mass Flow (Kg/batch) 1.953 9.161 481.429 1 482.429 470.314 12.114 128.347 136.498 3.963 119.048
Component Flow (Kg/batch)
Sodium Sulfate 1 0 0.1757 0 0.1754 0.1757 0.1612 0 0.0143 0 0
Graphite 0 0 0 1 0 0 0 0 0 0 0
Water 0 1 0.8243 0 0.8226 0.8243 0.7562 0.1546 0.2091 0.1156 1
Graphene 0 0 0 0 0.0021 0 0.0825 0 0 0.2523 0
Hydrochloric Acid 0 0 0 0 0 0 0 0.8454 0.7766 0.6321 0
Acetone 0 0 0 0 0 0 0 0 0 0 0
Stream Number 12 13 14 15 16 17 18 19 20 21 22
Mass Flow (Kg/batch) 118.804 3.748 2.748 1 9.46 312.111 312.111 301.651 10.46 9.46 1
Component Flow (Kg/batch)
Sodium Sulfate 0 0 0 0 0 0 0 0 0 0 0
Graphite 0 0 0 0 0 0 0 0 0 0 0
Water 0.9789 0.7332 1 0 0 0 0 0 0 0 0
Graphene 0 0.2668 0 1 0 0.0032 0.0032 0 0.0956 0 1
Hydrochloric Acid 0.0211 0 0 0 0 0 0 0 0 0 0
Acetone 0 0 0 0 1 0.9968 0.9968 1 0.9044 1 0
Chapter 6, in this
chapter energy balance
is made on each unit to
determine the required
energy for the whole
process as heating and
power required.
However, energy is
consumed in this
process.
Energy Balance
6.1 Mixers
Shaft work needed by impeller
∗ ∗ ∗ (6.1)
Where;
Reynolds number must be calculated to enable the usage of the correlations in figure A1
to estimate the power number for each mixer. For MIX-101 a four baffles high-efficiency
impeller is required (curve 6), while for MIX-102 a four baffles propeller is needed
(curve 4). [39]
∗ ∗
(6.2)
Where;
The average density of the mixture is calculated by using the mass fraction ratio for each
component as in equation (6.3).
(6.3)
(6.4)
77 | P a g e
Energy Balance
Mixi
Average Rotation Impeller Power
ng Reynolds Impeller
Density* al Speed Diameter Number
Time Number* Power[W]
[Kg/m3] [rps] [m] *
[min]
MIX-
15 2*104 1292 30 0.1 0.3 105
101
MIX-
10 5*105 784 20 0.1 0.8 50
102
*Calculations available in appendix A-2
/ ∗ (6.6)
Where; [40]
: Current Efficiency
t: Time in second
z: Oxidation state
F: Faraday's constant
78 | P a g e
Energy Balance
Referring to equation (6.5) the current efficiency for the electrolysis process is 0.37.
Therefore, the specific energy consumption as per equation (6.6) is in 435.3 kW.
6.3 Filter
For filters pressure drop is most commonly the studied variable, although since the
viscosity of the solution is considered low the pressure drop is almost negligible. The
Carmen-Kozeny equation (6.7) is used to calculate the pressure drop across the filter. [39]
(6.7)
6.4 Dyers
For the dryers energy balance to be calculated, two methods are approached. The first
method is regarding the recovery of the lost power. Which depends upon the power
absorbed by material and container in raising its temperature as required in a certain time,
and Power losses from oven surface and extracted air. To compare, the second method
calculates the exact amount of heat needed for conduction, convection, and radiation. The
time for drying for the D-101 is 2 hours while its 1 hour for D-102. [41]
Method I:
∑ (6.8)
∗
79 | P a g e
Energy Balance
∗ . ∗ ∗
3600
Table 6.4: Total energy for heating in dryers using the first method
∗ ∗ ∗
)
80 | P a g e
Energy Balance
∗ ∗
Table 6.5: Total energy for heating in dryers using the second method
Q Q Q Total Heat
Energy
Radiation Convection Conduction Transfer
Needed [kJ]
[kW] [kW] [kW] [kW]
D-101 3 0.6 189 192.6 6.9*105
D-102 0.6 0.08 25.2 25.9 9.3*104
81 | P a g e
Overview
Chapter 7, in this
chapter equipment
description mentioned
for several units and
designed to provide the
sequence of the
operations units,
specification,
dimensions and material
of construction of these
equipment.
Equipment Description & Design
ECR Selection
The types of electrochemical cells are parallel plate, tank cell, flow cells, fluidized bed cell,
and swiss-roll cell. Parallel plate flow are used in water electrolysis and in the production
of chlorine. Tank cell can be applied in metal electroplating and aluminum extraction.
Fluidized bed cells are used for nitrification and dinitrification of wastewater. The
application of swiss-roll cells lies in waste water treatment and electro-organic synthesis.
The selection of the tank cell is based on the available process condition being a batch
process, operates at ambient conditions, and relatively simpler in design than the other
types of ECRs. [40]
82 | P a g e
Equipment Description & Design
Method of Connection
As known that ECRs operate on DC current, therefore the supplied AC current must be
transformed using a rectifier into DC current. The types of electricity connections are either
mono-polar or bipolar, where mono-polar connections are utilized for high voltage and
bipolar connections for high current intensity. Hence, the required connection for this
process in ECR-101 are bipolar connections, because high current is required to exfoliate
the graphite sheets. [40]
Current Distribution
Current distribution is the actual dispersion of current intensity in a container, three types
of current distributions are present primary, secondary, and tertiary. The primary current
distribution is applied when the over-potential can be neglected. The secondary current
distribution is utilized when the concentration gradient in the reactor can be neglected but
the over-potential must be regarded. The tertiary current distribution is used when neither
the over-potential nor the concentration gradient can be neglected.
Scale up Philosophy
To scale up the ECR from lab scale to pilot scale many criteria must be considered. Several
similarity is a main aspect to be studied to properly scale up this unit. The geometrical,
over-potential, kinematic, and thermal similarities are mostly focused on between reactors.
In this case of scaling the ECR geometrical and over-potential similarities are
accomplished. Since the available reactor is an electrochemical reactor, the kinematic, and
thermal similarities are neglected.
83 | P a g e
Equipment Description & Design
Geometrical and over-potential similarity between two scales results in a constant ratio
known as Wagner number (Wa). [44]
(7.1)
Where;
L: characteristic length
Material of Construction
Most ECRs should be made out of non-conductive materials, so that it would not affect the
electrolysis process. Therefore, concrete is widely chosen as a material of construction,
although in this case concrete is not resistant to sodium sulfate (electrolyte). As a result it
was recommended that glass-lined cast iron material used for the ECR.
The main factor of ECR design extremely dependent on the current density and electrode
potential. Electrochemical reactions that depend on voltage driving force reached by
Butler-Volmer relation which describes the interrelationship between reaction rate in terms
of current density and electrode potential: [40]
(7.2)
Where;
: oxidation state
84 | P a g e
Equipment Description & Design
: faraday's constant
Electrode reaction rate can be replaced by the activation over-potential of the anodic
(graphitic anode), and the symmetry factor represents the fraction of the potential change
that accelerates the cathodic reaction. While exchange current density defined as the redox
reactions occur on the electrode at equilibrium and demonstrate how fast the reaction
proceeds.
To determine the exchange current density, surface over-potential and current density must
be calculated. Over-potential of electrode when electrical field is applied determined by
the relation: [40]
V (7.3)
Where;
V: cell voltage
: ionic potential
: reaction potential
This relation specifies the over-potential in the process which found to be 0.26V. On the
other hand, current density can be reached by Nernst-Planck equation: [40]
∑ ∑ ∑ (7.4)
The first term eliminated since there is no concentration gradient and the second term
ignored due to absence of bulk flow then electro neutrality applied in the cell. The only
factor controlling the current density is migration of ions in presence of electric field. The
resulted relation is: [40]
85 | P a g e
Equipment Description & Design
(7.5)
Where;
The value of the current density is 0.218 A/cm2. Here, exchange current density can be
calculated from equation (7.2) which equals 6.5*10-3 A/cm2. This value means that the
reaction is irreversible. Here, in order to scale up, a dimensionless number must be
specified which is 'Wagner Number' that describes the throwing power and the effect of
over-potential on the current distribution. In this process, qualitatively it implies the ability
of the sulfate ions to peel off and exfoliate the layers of graphene uniformly to the surface
of the solution.
86 | P a g e
Equipment Description & Design
Type of Filters
A drum filter consists essentially of a large hollow drum round which the filter medium is
fitted. The drum is partially submerged in a trough of slurry, where vacuum drags the
filtrate through the filter medium. Washing agent can be sprayed on to the drum surface
and multi-compartment drums are placed so that the washing agent can be kept separate
from the filtrate. Rotating drum filters are essentially continuous in operation, and handling
large throughputs.
Bag filters are used in the presence of high flow and high capacity liquid filtration. Serving
as a strainer, with a perforated basket to support the filter medium. Multiple filter bag styles
are available and variety of combinations providing wide range of coverage for process
requirements.
87 | P a g e
Equipment Description & Design
88 | P a g e
Equipment Description & Design
For this process two filter are located, one after the electrochemical rector (EC-101) and
the other after the ultra-sonication unit (S-101). The electrocell effluent contains the
electrolyte and solid graphene particles, therefore a filter is required to separate the desired
product. As well as the outlet from the sonication unit has the graphene product dispersed
in solution.
After the filtration of the electrolyte, the filtrate is disposed in a storage tank (T-101). Then
the cake needs to be washed, therefore hydrochloric acid is distributed followed by washing
by water. Each washing agent is stored separately in storage tanks (T-102) and (T-103)
controlled manually by appropriate valves. Finally the filter cloth gets handled by operators
and transferred to the next unit (D-101).
89 | P a g e
Equipment Description & Design
Distributor
A distributor is used to equally distribute the solution to the entire surface area of the filter.
Although since the stream contains solid particles then the area of the opening must be
wide enough so that they do not get blocked. The chosen distributor device is a simple
through distributor. Which is widely used in the heavy liquid and gas load, high viscosity
liquid and liquid with suspended solid. Moreover, if blockage occurs or corrosion of metal
this piece of equipment can be easily replaced due to its availability and cheap cost.
Filter Medium
The material of the synthetic cloth can either be polyvinyl chloride (PVC),
polytetrafluoroethylene (PTFE), or Polypropylene. Due to their good resistance to acids
and alkalies and appropriate temperature limits. Since the sieving test showed that graphene
flakes has size between 125 and 250 micron (chapter 3) then the appropriate mesh number
would be 140 mesh or even more. The cloth would have the same diameter of the filter
with edges to go around the filter from outside. A perforated metal plate fixed at a certain
height to support the cloth.
90 | P a g e
Equipment Description & Design
Material of Construction
The material of construction (MOC) is an issue in this case since the feed electrolyte is a
weak alkali and the washing agent is concentrated hydrochloric acid. Therefore corrosion
is the main factor in the decision of the MOC, to help prolong the equipment’s life-time.
According to table C, titanium appeared to be the most compatible material.
91 | P a g e
Equipment Description & Design
F-101 F-102
Several considerations should be taken in the selection of dryer and drying method:
Dryer Selection
Drying operation may either be continuous or batch, each type has its advantages and
drawbacks which affect the choosing of dryer will be used.
Continuous dryers types are: continuous tunnel, rotary, drum, spray, and freeze dryers.
92 | P a g e
Equipment Description & Design
Several factors affect the selection of dryer task, where the following points are
considered:
1) Temperature and pressure in the dryer
2) Heating medium
3) Capacity of material
4) Properties of material
5) Time needed for drying
The chosen dryers for this batch process are electric oven dryers (D-101) and (D-102).
Since the graphene product being dried has low densities, air flow must be as low as
possible.
Heat is supplied to the oven by electric heating element, where the inlet air gets heated by
radiation. While the trays get heated through conduction heat transfer from the metal. Even
though convection method is available but can be neglected.
As the dryer is selected in certain specification, the most suitable dimensions are chosen
depending on the quantity of the product that will be dried and how can be distributed in
separated trays. The suitable dimensions are 2.5×2 m with insulation thickness of 10cm to
minimize heat losses and saving energy.
93 | P a g e
Equipment Description & Design
Dimensions Calculations
(7.6)
Where;
V: mixture volume, m3
D: diameter of mixer, m
L: height of mixer, m
The volume of mixture in M-101 is 0.43 m3, it is assumed that D = L based on heuristics.
D = L = 1.04 m
The volume of mixture in M-102 is 0.40 m3,
D = L = 1.03 m
Material of Construction
The material of construction mainly affects the cost of the equipment. For M-101 sodium
sulfate solid (Na2SO4) is prepared, therefore many metals can be selected based on its
resistance. Stainless steel 304 was suitable in terms of resistance and relatively cheap.
Moreover, for M-102 cast iron was found to be an appropriate choice.
Wall Thickness
When the vessel diameter is between 1.0 m to 2.0m the minimum thickness should not be
less than 7 mm, so the thickness of the cylinder shell of both mixers will be taken as 7 mm.
94 | P a g e
Equipment Description & Design
The agitator design include: impeller selection, impeller diameter and height, blade width
and length, tip speed, and maximum torque. Baffles are usually used to improve mixing
and reduce problems such as dead zones.
Selecting the suitable impeller depends on the viscosity of the liquid, volume of the reactor,
and its function. Since in M-101 dissolving sodium sulfate (Na2SO4) solid in water then it
requires moderate features, therefore a high-efficiency impeller. Moreover, in M-102 a
propeller blade is chosen to homogenize the solution.
95 | P a g e
Equipment Description & Design
According to the rules of thumb, both impeller diameter and height are equal to one third
of the vessel diameter. The blade width is one fifth of the tank diameter and the blade length
is one fourth the diameter. These parameters are calculated as follows:
M-101 M-102
Diameter 0.347 0.343
Height 0.347 0.343
Blade Width 0.208 0.206
Blade length 0.260 0.258
The dimensions of cylindrical tanks are calculated the same method as for the dimensions
of mixers. The total volume per day is twice the amount of one batch. Therefore the
capacity of the vessels is specified to withstand one operating day (two batches).
96 | P a g e
Equipment Description & Design
According to the wall thickness of vessels heuristically data was used. When the vessel
diameter is between 1.0 m to 2.0m the minimum thickness should not be less than 7 mm,
so the thickness of the cylinder shell of both mixers will be taken as 7 mm.
The most important step in the design of storage tanks is selecting the material of
construction. The table below presents the material of construction for all the storage tanks
for our process.
Vessels MOC
TK-101 CS
TK-102 SS
TK-103 CI
TK-104 CS
The design of the piping system includes finding the dimensions of pipes needed to
transport stream materials from equipment to another, and its material of construction.
Simpson (1968) gives values for the optimum velocity in terms of the fluid density. The
maximum velocity should be kept below that at which erosion is likely to occur.
97 | P a g e
Equipment Description & Design
Fluid density
Velocity m/s
Kg/m3
1600 2.4
800 3.0
160 4.9
7.357x10-2
<2> 9.161 1000 2.85 9
5.223x10-1
<9> 312.111 784 3.05 5
5.228x10-1
<11> 312.111 782 3.05 7
98 | P a g e
Equipment Description & Design
High frequency
Effective circulation
Heat exchanger
The vibration amplitude is amplified up to about 70 - 100 microns that is due to the high
frequency that is 20 kHz. In the recirculating configuration shown above, the material
passes through the reactor chamber multiple times, which increases the cumulative
exposure time. Heat exchanger control system maintains the temperature of the solution at
room temperature, so that it would not affect the structure of the produced graphene.
99 | P a g e
Overview
Chapter 8, control
system is
interconnection of
elements that manage,
direct and regulate the
system to provide the
desired response. In
order to reach this
response, control
systems were applied on
the units to prevent any
bad response of the
process and stabilize the
system.
Controlling Systems
Variables such as pressure, temperature, flow-rate, or level detectors often have to be set
on large equipment or systems. The required setting should not change even when errors
occur, such tasks are attempted by implementing a closed-loop controller. [45]
Controlling a chemical plant from all aspects prevents the occurrence of disasters. Effective
control system design is the desired goal for control engineers. Unfortunately, many
problems might affect this target such as:
The main objectives taken into consideration when designing instrumentation and control
schemes are the safety of plant operation, product quality, production rate and the cost of
production. Keeping the process equipment within known and safe limits. Detecting
dangerous situations as they advance and to prevent them from expanding, providing alarm
bells, interlocks, and automatic shut-down systems. Also product quality is maintained by
control systems, to maintain the product composition within the specified or desired quality
standards. [36]
Controlling the process can also be accomplished through a process HAZOP analysis. To
start the HAZOP study some information should be available, like process flow diagrams,
piping and instrumentation diagrams (P&IDs), material safety data sheets, and energy and
mass balances. [48]
102 | P a g e
Controlling Systems
1- Feedback
2- Feed Forward
103 | P a g e
Controlling Systems
1. Proportional (P), in which the corrective action is proportional to the error signal.
2. Integral (PI), in which the corrective action at time t is proportional to the integral
of the error up to that time.
3. Derivative (PD), in which the corrective action is proportional to the rate at which
the error is being generated.
The distinguishing feature of feed forward control is that the disturbance variable is
measured, but the controlled variable is not. The important advantage of feed forward
control is that corrective action is taken before the controlled variable deviates from the set
point. Ideally, the corrective action will cancel the effects of the disturbance so that the
controlled variable is not affected by the disturbance. [46]
104 | P a g e
Controlling Systems
Symbol Meaning
TC Temperature Controller
CC Concentration Controller
PC Pressure Controller
Control Valve
Pneumatic Signal
105 | P a g e
Controlling Systems
ECR‐101
AC
Power
DC
Rectifier
106 | P a g e
Controlling Systems
FIC
P‐101 A/B
LIC
F‐102
107 | P a g e
Controlling Systems
LIC
TK‐101
The drying step takes place in an oven dryer, the evaporation inside the dryer caused by
a pre –heated air then distribute it by a propeller fan. Temperature and pressure inside the
dryer is very important that effect on dryness required in the end product.
TC
CC
14
D‐102
108 | P a g e
Controlling Systems
Internal control system are implemented in this selected unit. The temperature and
frequency required are controlled therefore only extra addition variables are to be
controlled.
PC
TC
11
S‐101
109 | P a g e
Controlling Systems
8.4.1 Tanks
Table 8.3: Tanks HAZOP study
Guide
Element Cause Consequences Action
word
No inlet Loss of material, Flow controller
Damage in inlet pipe
flow production delay installation
Shortage of solution in Delay in Level control of
Solution tank production tank
No outlet
flow Delay in
Clogging of outlet pipe/ Maintenance, flow
production, over
outlet pump failure control needed
flow
No inlet Loss of material, Flow controller
Damage in inlet pipe
HCl with flow production delay installation
Solution More
traces Pumping system failure Level controller
inlet
(that of inlet stream) Over flow installation
volume
No inlet Loss of material, Flow controller
Damage in inlet pipe
flow production delay installation
Water with
HCl traces More
Pumping system failure Level controller
inlet Over flow
(that of inlet stream) installation
volume
No inlet Loss of material, Flow controller
Damage in inlet pipe
flow production delay installation
Delay in
Clogging of outlet pipe production, over
No outlet flow Maintenance, flow
flow Delay in control needed
Acetone Outlet pump failure production, over
flow
More
Pumping system failure Level controller
inlet Over flow
(that of inlet stream) installation
volume
More Pressure control
Increase in temperature Fire / Explosion
pressure device installation.
110 | P a g e
Controlling Systems
8.4.2 Mixers
Table 8.4: Mixers HAZOP study
Guide
Element Cause Consequences Action
word
Installing a level or
Delay in supplying flow controller on the
Supply shortage
the next unit supplying unit or water
source, respectively
No flow
Pumping failure
Installing a stand-by
due to physical
Delay in production pump, change
or electrical
immediately, repair
causes
Distilled
Water Increase in the Installing a level
More flow level of Decrease in controller on water
supplying unit concentration of supplying tank
solution
Usage of Distillation unit Get rid of solution
Lower product grade
tap water system failure before entering the cell
increase in
Flow controller
Less flow Supply shortage concentration of
installation
solution
Delay in supplying Increasing stock
Supply shortage
the next unit amount
No flow Installing a level
Introducing water
controller on salt
only to the cell
supplying tank
More Human error
Salt Increase in Installing a level
amount
concentration of controller on salt
than
solution supplying tank
required
Decrease in
Installation of a
Less flow Supply shortage concentration of
concentration controller
solution
Supply shortage
Delay in production Circuit breaker
No flow Electric source required, repairing
damage
Electricity
Circuit breaker
Instant increase
More flow Motor failure required,
from source
changing/maintenance
111 | P a g e
Controlling Systems
Guide
Element Cause Consequences Action
word
Increase in Backward flow to
Solution More flow solution level of storage tanks, delay
mixer in production Installation of a flow
Pumping system controller
More failure; of inlet
amount stream Loss of material, over
than flow
required Clogging of Installing a level
outlet stream controller
Loss in material,
Less
Lower product
amounts Supply shortage quality and quantity
Acetone Loss of material or
Level controller
and delay of
Damage in pipe installation
Reversible production
flow Damage in inlet
Back flow to storage
valve control
tanks
system
Increase in
More Good ventilation
temperature, Fire
evaporation system
distributing.
Less than
instructed Lower product Weighting and
Graphite Human error quality measuring before
More than loading
instructed
Loss of material
112 | P a g e
Controlling Systems
Guide
Element Cause Consequences Action
word
Circuit breaker
Supply shortage
No required
Electricity Delay in production
electricity Damage in
Maintenance
electrodes
Exceeding normal
Ventilation system
temperatures of
Current More than required, Electric
Instant increase solution, significant
optimum controller needed
in current supply evaporation
values
Reducing the quality Electric controller
Voltage
of product needed
Pumping system
More Loss of material, Level controlling of
failure; of inlet
volume over flow cell
stream
Flow controller
Failure in inlet installation, increasing
Less pumping system volume to required
Lower product
volume value
quality and loss of
than
material Level controller
required
Solution Leakage in tank installation, closing
inlet and outlet valves
Increase in Level control element
Back flow
Reversible solution level required
flow Damage in inlet Leakage and loss of Installation of a flow
stream material controller
Other than
Human error, No guarantee on
Sodium Get rid of solution
Supplier error product quality
Sulfate salt
Larger Measuring dimensions
sheet than Human error Loss of material before loading the
instructed sheet
Graphite
Other than:
Human error, Get rid of solid
high pure Low grade product
Supplier error product by filtration
sheet
113 | P a g e
Controlling Systems
8.4.4 Filters
Table 8.6: Filters HAZOP study
Guide
Element Cause Consequences Action
word
Installing a flow
Pump failure; of
More controller at inlet
inlet stream
amount Loss of material, stream
Solution
than over flow Installing a level
allowed Clogging of outlet
controller, cleaning and
stream or filter
changing filter sheet
Unclear filter or
More than Clogging of filter, Using a new filter for
more solid in inlet
instructed over flow each cycle
stream
Solid
Solid as sediment in
less than Clogging of inlet Regular cleaning and
cell, delay in
that in cell stream maintenance
production
Damage in outlet Loss of material due
Reversible valve control to over flow, back
Level control of filter
Solid flow system or flow to cell and
solution clogging of filter delay of production
mixture Unclear filter or
More than Enter stage cleaning for
more solid in inlet Clogging of filter
instructed each cycle
stream
Pump system Installing a flow
failure; of inlet controller at inlet
More stream stream
amount Loss of material,
than over flow Installing a flow
required Clogging of outlet controller on outlet
HCl
stream or filter stream, cleaning and
changing filter sheet
Loss of material,
less than Leakage in inlet Flow control on outlet
unclear solid from
required stream stream of filter
solution
More
Outlet valve
amount Over flow, loss of
Acetone failure, clogged Outlet level controller
than material
filter sheet
required
Unclear filter or
More than Clogging of filter, Enter stage cleaning for
Graphite more solid in inlet
instructed over flow each cycle
stream
114 | P a g e
Controlling Systems
Guide
Element Cause Consequences Action
word
Water, Loss of material due
Damage in outlet
HCl and Reversible to over flow or back
valve or clogging Level control on filter
solid flow flow to F-101, delay
of filter
mixture of production
Pumping system Installing a flow
More failure; of inlet controller at inlet
amount stream Loss of material, stream
than over flow Installing a level
Distilled required Clogging of outlet
controller, cleaning and
water stream of filter
changing filter sheet
Loss of material,
Less than Leakage in inlet Flow control on outlet
unclear solid from
instructed stream stream of filter
solution
Acetone- Damage in outlet Unclear filter or Level controller
Reversible
solid valve or clogging more solid in inlet installation, cleaning of
flow
mixture of filter stream filter
Solution, Loss of material due
Damage in outlet
HCl and Reversible to over flow or back Level control on outlet
valve or clogging
solid flow flow to F-101, delay stream of filter
of filter
mixture of production
More than Unclear filter or
Solid-HCl Enter stage cleaning for
designed more solid in inlet Clogging of filter
mixture each cycle
for stream
115 | P a g e
Controlling Systems
8.4.5 Ultra-Sonication
Table 8.7: Ultra-Sonication unit HAZOP study
116 | P a g e
Controlling Systems
8.4.6 Dryers
Table 8.8: Dryers HAZOP study
117 | P a g e
Overview
Chapter 9, in this
chapter selecting of
suitable location, chosen
carefully due to the
definite effect on the
profitability of this
project. Minimum
spacing between
equipment are set for
safety purposes. Plant
layout shows the
arrangement of the
whole plant areas and
arrangements of
equipment to give
optimum arrangement to
minimize the cost as
possible. Also, in this
chapter suggested
projection of the plant
was made using
AutoCAD Plant 3D.
Plant Layout
Plant layout is a technique of locating different machines and plant services within the
factory so that the greatest possible output of high quality at the lowest possible total cost
can be available. Plant layout is an important part of process plant design as it is one of the
keys for success in factory management. [49]
The location of the plant can have a definite effect on the profitability of a project, and
the scope for future expansion. Many factors must be considered when selecting a suitable
site, with respect to many variables.
120 | P a g e
Plant Layout
9.1 Introduction
Plant layout refers to the arrangement of physical facilities (machines, equipment, tools,
furniture, etc.), in such a manner so as to have quickest flow of material at the lowest cost
and with the least amount of handling in processing the product from the receipt of raw
material to the delivery of final product.
It begins with the design of the factory building and goes up to the location and movement
of a work table. All the facilities like equipment, raw materials, machinery, tools, furniture,
workers, etc. are given a proper place. In deciding the place for equipment, the supervisors
and workers who have to operate them should be consulted.
The location of the plant can have a definite effect on the profitability of a project, and the
scope for future expansion. Many factors must be considered when selecting a suitable site,
such as location, with respect to the marketing area, raw material supply, transport
facilities, availability of labor and availability of utilities. [36]
121 | P a g e
Plant Layout
9.1.2 Types of Plant Layout
Types of Plant
Layout
Product or Combined
line layout or group
layout
Fixed
Process or position or
functional location
layout layout
Product Layout
In this type of layout the machines and equipment are arranged in one line depending upon
the sequence of operations required for the product, hence it is also called as line layout.
The material moves to another machine sequentially without any backtracking or deviation,
the output of one machine becomes input of the next machine.
122 | P a g e
Plant Layout
Process Layout
Process or functional layout is the arrangement of machines of similar types are arranged
together at one place. This type of layout is used for batch production. It is preferred when
the product is not standardized and the quantity produced is very small.
Combined Layout
This type is a combination of process and product layout that is known as combined layout.
Manufacturing concerns when several products are produced in repeated numbers with no
likelihood of continuous production, therefore combined layout is followed.
123 | P a g e
Plant Layout
Table 9.3: Advantages and disadvantages of fixed position layout
Marketing Area
Political Raw Material
Consideration Supply
Transport
Climate
Facilities
Factors
Local
Availability of
Community
Labour
Consideration
Environmental Availability of
Impact Utilities
Availability of
Land
Figure 9.2: Factors that must be considered when selecting a suitable site location
124 | P a g e
Plant Layout
9.2.1 Hierarchy of Decisions
Combinations of the critical factors were taken into consideration for site location. The
following steps show some of these factors that affect the site selection:
125 | P a g e
Plant Layout
If the plant is located in a cold climate, costs may be increased by the necessity for
construction of protective shelters around the process equipment, and special cooling
towers or air-conditioning equipment may be required. Excessive humidity or extremes of
hot or cold weather can have a serious effect on the economic operation of a plant, thus
these factors should be examined when selecting a plant site.
126 | P a g e
Plant Layout
9.2.2 Location of the Plant
The production of graphene plant location is selected based upon the aforementioned
steps.
127 | P a g e
Plant Layout
Selection of the Exact Site
Future changes may make it desirable or necessary to expand the plant facilities. Therefore,
the plant should be constructed at a location where additional space is available.
Changchun, Jilin, China is the exact selected location based on all the previous factors.
128 | P a g e
Plant Layout
9.3 Plant Layout
The layout of the plant plays an important role in determining construction and
manufacturing costs. The economic construction and efficient operation of process unit
will depend on how well the plant and equipment specified on the process flow sheet is
laid out.
Economic
Consideration
Future Process
Expansion Requirements
Control Operation
Factors
Safety &
Maintenance
Health
Productivity Construction
Figure 9.6: Factors that must be considered when selecting a plant layout
129 | P a g e
Plant Layout
Table 9.4: Spacing (meter)
M-101 ECR-101 P-101 A/B F-101 D-101 M-102 S-101 P-102 A/B F-102 D-102
M-101 - 5 x x x 5 x x x x
ECR-101 5 - 0 7 x x 5 5 x x
P-101 A/B x 0 - 7 x x 5 5 x x
F-101 x 7 7 - 5 x x x 5 x
D-101 x x x 5 - x x x x 5
M-102 5 x x x x - 5 x x x
S-101 x 5 5 x x 5 - 0 7 x
P-102 A/B x 5 5 x x x 0 - 7 x
F-102 x x x 5 x x 7 7 - 5
D-102 X x x x 5 x x x 5 -
x: Not required distance for equipment that are not in series
Site Area
130 | P a g e
Plant Layout
131 | P a g e
Plant Layout
132 | P a g e
Plant Layout
9.3.3 Three-Dimensional Layout
Here is a projection of graphene plant in simple design that projected using AutoCAD
Plant 3D software in order to simplify the vision of the plant. All dimensions that resulted
based on the previous work are taken into consideration.
133 | P a g e
Overview
A capital investment is required to start any industrial process and the determination of
the enquired investment is an important part of any plant design project. The total
investment for any process consists of fixed capital investment of physical equipment and
facilities in the plant and working capital cost which must be obtained to pay salaries. In
addition to that, raw materials, products, and utilities cost must be obtained in which the
feasibility study can be calculated. So, in the analysis of plant cost, capital investment cost,
manufacturing costs, and general expenses including taxes must be taken into
consideration.[53]
136 | P a g e
Profitability Analysis
8. Utilities (Services), provision of plant for steam, water, air, firefighting services (if
not estimated separately).
In addition to the direct cost of the purchase and installation of equipment, the capital cost
of a project will include the indirect costs listed below. These can be estimated as a function
of the direct costs:
1. Design and engineering costs, which cover the cost of design and the cost of
“engineering” the plant: purchasing, procurement and construction supervision.
Typically, 20 per cent to 30 per cent of the direct capital costs.
137 | P a g e
Profitability Analysis
138 | P a g e
Profitability Analysis
(10.1)
Where;
CBM◦: bare module cost (at base condition: ambient temperature & pressure and carbon
steel).
CP◦: purchased cost (base).
FBM: bare module factor which equals to B1 B2fpfm [56]
Grass root cost must be calculated, grass roots refer to a completely new facility in which
the construction is on undeveloped land (grass field). Where CBM is the total bare module
cost, considering the pressure and material of construction. While CBM◦ refers to the total
bare module cost at the base operating conditions (T=0-100◦ C; P =0.5-10 bar and material
of construction is carbon steel).
0.5 1.18 (10.2)
Updating the total bare module cost using Chemical Engineering Plant Cost Index
(CEPCI). CEPCI is used to consider the effect of inflation rate on the purchase cost of the
equipment. We were used CEPCI in 2001 as a base cost. All the equipment prices are
updating using the CEPCI in 2017 (CEPCI2001 =397 and CEPCI2017 =558.3).
139 | P a g e
Profitability Analysis
Table 10.1: Fixed capital investment for production of Graphene process generated using Excel
Purchased
Bare Module Bare Module
Equipment Equipment Cost
Cost $(CBM) Cost $(C°BM)
$(CP)
MIXERS
MIX-101 16,027 32,053 32,053
MIX-102 14,968 29,936 29,936
ELECTROCHEMICAL CELL
C-101 30,000 60,000 98,100
DRYERS
D-101 8,000 16,000 16,000
D-102 8,000 16,000 16,000
FILTERS
F-101 27,818 55,636 55,636
F-102 33,197 66,395 66,395
SONICATOR
S-101 35,000 70,000 114,450
Total Bare Module Cost $346,020.482
Total Bare Module Cost° $428,570.482
Total Purchased Equipment Cost $173,010.241
140 | P a g e
Profitability Analysis
In this project, grass root is the case; because we are planning the plant from the zero and
not expanding it on already prepared land. Additional costs other than direct and indirect
must be estimated first, such costs are divided into two groups:
1.18 ∑ (10.3)
Unless otherwise stated, these costs are assumed to be equal to 50% of the bare module
costs for the base case conditions. Adding these costs to the total module cost provides the
grassroots cost. [57]
Thus; the grass root cost can be evaluated using the following equation:
0.5 ∑ (10.4)
141 | P a g e
Profitability Analysis
Using equation (10.1), (10.2) and the data of table 10.1, the grass root cost for production
of graphene process.
The fixed capital investment without the land cost is (FCIL) is equal to the total grass root
cost to produce graphene ($970,908). The working capital is estimated to be 20% of the
FCI which is equal to ($194,511).
142 | P a g e
Profitability Analysis
The cost of manufacturing with depreciation (10%) is calculating using equation (10.6):
1.23 2.73 0.12 (10.6)
Table 10.2: The factors in calculating the cost of manufacturing (COMd) from EXCEL
FCI $970,908
COL $194,511
CUT $2,197
CRM $222,538
CWT ‐
COMd= 1.23 [CRM + CUT] + 2.73 COL + 0.18 FCI = $ 982,202
But in our project, we operate the plant in batches, which means that the shift per day is
not 8 hours. The single batch takes 6.5 hours until the graphene is produced, and we have
two batches every single day, which means 4160 hours per year.
To estimate the cost of operating labor, the average payment for each labor is estimated to
be $8,457/year assuming all of plant operators are engineers.
.
6.23 31.7 0.23 (10.7)
Where;
P: number of processing steps involving the handling of particulate solids = 4
Nnp: number of process for fluid-base process
NOL = (6.29 +31.7*(4) 2+ 0.23* 6)) 0.5 =22.69 =23 operator/shift
143 | P a g e
Profitability Analysis
Table (10.3) was generated using EXCEL program and represent the cost each utility used.
It was found to be $ 132,407,900 per year.
144 | P a g e
Profitability Analysis
On the other hand; another key parameter called Equivalent Annualized Operating Cost
(EAOC), which represents the amount of money that would have to be spent each year to
calculate the find the capital, operating and maintenance requirements of transient vehicle
into the future.
It’s generally an analytical abstraction and does not reflect actual cash outlays. It can be
calculated by converting the fixed capital investment FCI into equivalent annual operating
cost. The FCI can annualized using the following equation:
(10.8)
Assuming an interest rate of 10% and a project life of 12 year, the FCI is annualized and
then added to the cost of manufacturing to compute the EAOC. The calculated EAOC of
graphene production process is $ 158,011.
The Graphene process was expected to make revenue from selling Graphene product. The
total annual revenue was found to be $ 192,000,000.
145 | P a g e
Profitability Analysis
zero. The resulting discounted cumulative cash flow diagram is then used to evaluate
profitability. Discounted techniques are used to evaluate the Graphene process using
EXCEL program.
146 | P a g e
Profitability Analysis
Cash Flow Diagram
178
158
CUMMULATIVE CASH FLOW X107
138
118
98
78
58
38
18
‐2
0 2 4 6 8 10 12
PROJECT LIFETIME (YEARS)
Figure 10.1: The cumulative cash flow diagram for Graphene production process, generated
using EXCEL
147 | P a g e
Profitability Analysis
Figure 10.2: The cumulative cash flow diagram for production of graphene
148 | P a g e
Overview
Chapter 11, in this
chapter process safety
analysis was done in
order to increase the
safety level of the plant
from chemical, thermal,
physical hazards.
The safe operation of such processes depends on the design and provision of engineered
safety devices, and on good operating practices, to prevent a dangerous situation
developing, and to minimize the consequences of any incident that arises from the failure
of these safeguards. Engineered safety covers the provision in the design of control
systems, alarms, trips, pressure-relief devices, automatic shut-down systems, duplication
of key equipment services; and fire-fighting equipment, sprinkler systems and blast walls,
to contain any fire or explosion.
The aim of process safety analysis is to increase the safety level of the plant and minimize
economic loss by minimizing the accidents occurs due to lack of knowledge of dealing
with equipment and materials, know how to act if any sudden accidents take place.
150 | P a g e
Safety & Hazard Prevention
11.1.1 Chemical Hazards
Can be classified to; corrosive chemicals, flammable chemicals, toxic chemicals and
others. Such materials, should be treated with caution and must be kept away from any
source of heat or direct contact with human. [61]
Corrosive Chemicals: Materials cause rapid erosion and visible destruction of
metals and organic tissues, such as sodium hydroxide and hydrochloric acid.
Flammable Chemicals: Materials that will burn or ignite, causing fire or
combustion like.
Toxic Chemicals: Material that may cause harm to an individual if it enters the body
like hydrochloric acid if absorbed through skin, dermal contact, eye contact and
Inhalation, also ethylene glycol is a moderate toxic material.
151 | P a g e
Safety & Hazard Prevention
152 | P a g e
Safety & Hazard Prevention
11.3 Materials Safety
Materials safety data sheet (MSDS) is very important to know in the plant design, to
know the nature of the materials and how to deal with it. Mentioned below some of safety
data for raw materials and product: [64]
Acetone: a highly flammable liquid; heating will cause pressure to rise in the storage tank with
the risk of explosion. Vapor/air mixtures are explosive, the LFL and UFL are 2.6% and 12.8 %
by volume of air, respectively.
4 →3 3
0.25 0.5
3 0.25 6 0.5 1 4
4
0.8
1 4 1
0.596
0.159
153 | P a g e
Safety & Hazard Prevention
At these maximum values, the process is safe from any occurrence of fire, but safety precautions
must be added as described in the HAZOP analysis. Sodium sulfate evaporation may form
Sulfuric acid, and causes acid rain, but it effect is regional and remains for a short period of time
in comparison with other greenhouse gases.
Acetone has a minimal effect on environment; soil, water and air. HCl affects the air by its
vapor, causing local acid rain. Graphite or Graphene powders or sheets do not affect
environment in a direct way, since they exist in it and can be easily decomposed.
LD50 (mg/kg)
3000 900 5989 --
TSS (µg/m3)
-- -- 250 25
154 | P a g e
Safety & Hazard Prevention
Injuries due to electric shock by touching uncovered cables or equipment failure.
Slipping, and or tripping of workers on floor due to solution, filtering liquids or
Acetone.
Burns from touching the dryers during operation.
Ignition of Acetone either by electric causes or workers.
11.4.1 Safeguards
Protective clothes must be worn whenever being inside the plant.
All workers should know an organized safety procedure of accidents and the basic
safety knowledge.
Regular maintenance of equipment and electric wiring.
Reducing the connections of pipes and wires between equipment.
Report immediately when seeing any form of danger or irregularities of operation
or other personnel.
155 | P a g e
Overview
Chapter 12, many
conclusions and
parameters are gained
which may affect the
productivity of
graphene.
Recommendations may
be available under
investigation in order to
improve the process,
and this chapter reviews
these points.
Conclusion & Recommendation
12.1 Conclusions
1. Graphene is very useful material; it enters in many applications in the industrial,
biomedical, science, water treatment and high capacity batteries.
2. Electrochemical cell is the best alternative than chemical vapor deposition (CVD)
to produce graphene from power consumption, environmental and economic point
of view.
3. In the near future this project can be easily applied because it can be run on solar
cells.
4. Adsorption of dye performance using graphene was observed to be exceptionally
better than commercial coarse activated carbon. Results of adsorption of lead and
iron indicated a great capacity and capability of adsorption.
5. Microscopy tests revealed and confirmed that the experimentally produced
graphene is truly graphene, using XRD, TEM, and SEM tests.
6. A suggested process flow was constructed based on the laboratory work, leading to
material and energy balances along with equipment design or selection.
7. The most important control variables are the flow rates, level and the temperature,
because the final product size and yield are very sensitive to these variables.
8. The feasibility study of this project gave promising results, the pay –back period
and the discounted cash flow rate of return indicated a profitable project to invest
in.
9. The location of graphene production according to the sires of decisions was set to
be in northeast of China, where the raw material is widely available.
10. Safety considerations should be taken in this plant to reduce the toxic substances
emitted from the electrochemical cell, corrosion and flammable material.
158 | P a g e
Conclusion & Recommendation
12.2 Recommendations
In order to increase the quantity of the graphene produced, it's recommended to
study many parameters mentioned below:
1. Use different electrolyte with higher conductivity; to increase the rate of
exfoliation.
2. Use another type of cathode to study the effect of changing the electrode
conductivity.
It's recommended to study the effect of adding high efficient impeller after ECR
unit; for assuring that the product has better distribution of monolayers sheets.
As the demand of the product increases, it's recommended to scale up the process
to plant scale instead of pilot scale.
159 | P a g e
Appendix A
For section 3.6, variation in concentration and voltage was tested and the experimental results are
tabulated in table A1 and A2.
Table A1: Results for the variation of the concentration of the electrolyte (Na2SO4) effecting the
product
Concentration
Before After Before After
(mol/L)
Table A2: Results for the variation in voltage experiment
Many performance tests were conducted on the produced graphene, as in section 3.7. Therefore, all
the recorded data, related graphs and detailed calculations are tabulated bellow.
164 | P a g e
Appendix A
Adsorption of Dye:
Figure A1: Transmittance-concentration curve []
0 2 2
5 2.5 3
10 2.5 3.5
20 2.5 4
50 2.5 5
80 2.5 6
200 3 11
2 days 3 60
165 | P a g e
Appendix A
Table A4: Kinetics of adsorption calculations (part 1)
Concentration Final / Initial Concentration
0 25 25 1 1
166 | P a g e
Appendix A
Table A6: Kinetics of adsorption calculations (part 2)
Concentration Final / Initial Concentration
Adsorption of Metals:
Table A7: Data shown on the spectrometer screen for lead adsorption
167 | P a g e
Appendix A
Table A8: Data shown on the spectrometer screen for iron adsorption
X‐Ray Diffraction:
From figure 3.
2 26
13
2 sin
1 1.54
1.83
2 sin 2 ∗ sin 13
0.94 ∗ 1.54
5.68
cos 1.4934 ∗ cos 13
168 | P a g e
Appendix B
B.1 Material Balance Calculations
B.1.1 Lab Scale Calculations
B.1.1a Weight of Na2SO4 needed to reach concentration of 1.5 M:
Moisture on filter paper = 10.6 g (after filtration and washing, blank experiment #1)
53.3
∗ 10.6 1.23
459.1588
250
∗ 10.6 5.771
459.1588
68.35875
∗ 10.6 1.578
459.1588
12.5
∗ 10.6 0.289
459.1588
170 | P a g e
Appendix B
75
∗ 10.6 1.731
459.1588
Moisture on filter paper = 5.96 g (after washing with acetone, blank experiment #2)
5.96
Dilution of HCl:
30 75
62.5
36
Amount of HCl:
Amount of H2O:
171 | P a g e
Appendix B
B.1.2 Pilot Scale Calculations
B.1.2a Scale up of Raw Material:
Moisture on filter paper = 10.6 g (after filtration and washing, blank experiment #1)
84.603
∗ 16.8254
728.823
1.953
396.825
∗ 16.8254
728.823
9.161
172 | P a g e
Appendix B
108.506
∗ 16.8254
728.823
2.505
19.841
∗ 16.8254
728.826
0.458
119.048
∗ 16.8254
728.823
2.748
173 | P a g e
Appendix B
B.2.2 Calculations
B.2.2a Mixer energy balance MIX-101:
∗ ∗ 1292 ∗ 30 ∗ 0.1
2 ∗ 10
0.01975
Np = 0.3
∗ ∗ ∗
174 | P a g e
Appendix B
784 /
∗ ∗ 784 ∗ 20 ∗ 0.1
5 ∗ 10
0.000316
Np = 0.8
∗ ∗ ∗
0.8 ∗ 784 ∗ 20 ∗ 0.1 50.2
Method 1
0.947 1.17
1.0585 /
2 2
12 ∗ 1.0585 ∗ 1.004 ∗ 100 20
0.28
3600
175 | P a g e
Appendix B
Power needed for drying 15.23785048 kW
Energy for drying 5.486E+04 kJ
B.3 Design
B.3.1 Figures
176 | P a g e
Appendix B
An R indicates that the material is resistant to the named chemical up to the temperature
shown, subject to the limitations given in the notes. The notes are given at the end of the
table. A blank indicates that the material is unsuitable. ND indicates that no data was
available for the particular combination of material and chemical.
B.3.2 Design of Filter
∗ ∗
∗
∗ 2
3∗
∗
177 | P a g e
[1] Ali Ashjaran, Hanieh Oshaghi, “Sciences Graphene as Single Layer of Carbon
Atoms: Perusal on Structure, Properties and Applications”, Research Journal of
Pharmaceutical, Biological and Chemical
[3] Lee, Jae-Ung, Duhee Yoon, and Hyeonsik Cheong. "Estimation of Young’s modulus
of graphene by Raman spectroscopy." (2012)
[6] Table of Electrical Resistivity and Conductivity Flow of Electric Current through
Materials “https://www.thoughtco.com/table-of-electrical-resistivity-conductivity-
608499” (January, 2018)
[8] “Material Data Book”, 3rd edition, Cambridge University Engineering Department
[9] Papageorgiou, Dimitrios G., Ian A. Kinloch, and Robert J. Young, "Mechanical
properties of graphene and graphene-based nanocomposites", Progress in Materials
Science (2017)
[10] Ren, Wencai, and Hui-Ming Cheng, “The global growth of graphene”, Nature
nanotechnology (2014)
179 | P a g e
[12] Novoselov, K. S. et al, “A roadmap for graphene”, Nature (2012)
[13] Hansora, Dharmesh P., and Satyendra Mishra, “Graphene nanomaterials: fabrication,
Properties, and applications”, 2017
[18] Yu Lin Zhong, Zhiming Tian, George P. Simon, Dan Li, “Scalable production of
graphene via wet chemistry: progress and challenges”, Materials Today (2015)
[21] De Arco, Lewis Gomez, Yi Zhang, and Chongwu Zhou. "Large scale graphene by
chemical vapor deposition: synthesis, characterization and applications" Graphene-
Synthesis, Characterization, Properties and Applications, InTech (2011)
[22] Ying Wei, Zhenyu Sun, “Liquid-phase exfoliation of graphite for mass production of
pristine few-layer graphene”, Current Opinion in Colloid & Interface Science (2015)
[23] Ren, Wencai, Cheng, Hui-Ming, “The global growth of graphene”, Nature
nanotechnology (2014)
180 | P a g e
[26] Geim, Andre K., and Konstantin S. Novoselov. "The rise of graphene." (2007)
[29] Shi, P. C., et al. “Large-scale production of high-quality graphene sheets by a non-
electrified electrochemical exfoliation method.” Carbon (2018)
[30] Parveen, Nazish, Mohd Omaish Ansari, and Moo Hwan Cho. “Correction: Simple
route for gram synthesis of less defective few layered graphene and its electrochemical
performance” RSC Advances (2016)
[33] Huang, Zheng-Hong, et al. “Adsorption of lead (II) ions from aqueous solution on
low-temperature exfoliated graphene nanosheets.” Langmuir (2011)
[34] Smith, Robin. Chemical process: design and integration. John Wiley & Sons, 2005.
[35] Richard Turton, "Analysis, Synthesis, and Design of Chemical Processes, 4th
Edition", 2012.
181 | P a g e
[38] Wood-Black, Frankie. "Considerations for scale-up–Moving from the bench to the
pilot plant to full production." Academia and Industrial Pilot Plant Operations and Safety.
American Chemical Society, 2014
[42] Incropera, ‘Fundamentals of Heat and Mass Transfer’ 7th Edition, 2011.
[43] M. Marcotte ‘WIT Transactions on State of the Art in Science and Engineering’,
[47] James R. Couper, W. Roy Penney, James R. Fair and Stanley M. Walas, Chemical
Process Equipment: Selection and Design, 2005, Second Edition, Gulf Professional
Publishing.
[48] Marvin Rausand, Hazard and Operability Study,, 2 ed., october 7, 2005.
[49] http://www.businessmanagementideas.com/industries/plant-layout/plant-layout-
meaning-factors-and-tools/6758
[50] Kyusang Han, S. C. (2013). Optimal layout of a chemical process plant to minimize
182 | P a g e
[51] Plant Location. (n.d.), from Slide share:
[53] http://electroiq.com/blog/2004/08/approximating-facilities-costs/
[54] https://chemicalprojects.wordpress.com/2014/05/09/the-factorial-method-of-cost-
estimation/
engineering-plant-cost-index-cepci-of-2016-and-2017/
[56] https://www.investopedia.com/terms/f/fixed-capital.asp
[57] http://www.investopedia.com/terms/e/eac.asp
183 | P a g e