201805graphene PDF

University of Jordan
School of Engineering
Department of Chemical Engineering
PRODUCTION OF GRAPHENE
Authors:
Alya’a Alzurqan
Dawood Ghazi
Dena Nazzal
Rawan Radi
Qusai Ghaleb
Supervised by Dr. Ali Matar
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.‬‬
‫”‪“IGNIS AURUM PROBAT‬‬
‫" 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.
Keywords: Graphene, Electrochemical Reactor, Sodium Sulfate, Bag Filter,

Adsorption, X-Ray Diffraction, Electricity.
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
Executive Summary III
Acknowledgment IV
Disclaimer V
Nomenclature XII
List of Figures XVI
List of Tables XIX
Chapter One: Introduction 1

Chapter Two: Literature Survey 5
2.1 General Definition 7
2.2 Historical Information 9
2.3 Applications of Graphene 10
2.4 Process Selection 12
2.4.1 Available Processes 13
2.4.2 Demerit Control Chart 18
2.5 Preliminary Economical Analysis 19

2.5.1 Cost of Materials 19
2.5.2 Available Markets 19
2.5.3 Other Producers 20
Chapter Three: Laboratory Experiments 23
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
Chapter Four: Process Description 49

4.1 Hierarchy of Decisions 50
4.2 Process Description 51
4.2.1 Process Overview 52
4.2.2 Block Flow Diagram 53
4.2.3 Process Flow Diagram 53
4.2.4 Main Process Streams 54
4.2.5 Rate of Production 55
Chapter Five: Material Balance 57

5.1 Introduction 58
5.2 Scale Up 58
5.3 Electrochemical Cell (CE-101) 66
5.4 Filter (F-101) 67
5.5 Mixer (MIX-101) 70
5.6 Dryer (D-101) 71
5.7 Sonication (S-101) 71
5.8 Process Diagrams 72
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
Chapter Seven: Equipment Description and Design 81

7.1 Electrochemical Reactor Design 82
7.1.1 ECR Description 82
7.1.2 Design Procedure 84
7.2 Filter Design 86
7.2.1 Filter Selection 86
7.2.2 Filter Description 89
7.2.3 Design of Filter 91
7.3 Dryer Design 92
7.3.1 Dryer Selection and Description 92
7.3.2 Sizing of Dryer 93
7.4 Mixer Vessel Design 93
7.4.1 Design of Mixer 93
7.4.2 Design of Impeller 95
7.5 Storage Vessel Design 96
7.5.1 Dimensions of Tanks 96
7.5.2 Material of Construction 97
7.6 Pipes Design 97
7.7 Rating of Ultra-Sonication Unit 99
Chapter Eight: Controlling Systems 101

8.1 Control Loop Elements 103
8.2 Process Control Strategies 103
8.2.1 Feedback Control Strategy 104
8.2.2 Feed Forward Control Strategy 104
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
Chapter Nine: Plant Layout 119

9.1 Introduction 121
9.1.1 Objectives of Good Plant Layout 121
9.1.2 Types of Plant Layout 122
9.2 Site Selection 124
9.2.1 Hierarchy of Decisions 124
9.2.2 Location of the Plant 127
9.3 Plant Layout 128
9.3.1 Spacing between Equipment 129
9.3.2 Main Units Located in Plant Layout 130
9.3.3 Three-Dimensional Layout 133
Chapter Ten: Profitability Analysis 135

10.1 Estimation of Total Investment 137
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
Chapter Eleven: Safety and Hazard Prevention 149

11.1 Process Safety Analysis 150
11.1.1 Chemical Hazards 151
11.1.2 Thermal Hazards 151
11.1.3 Physical Hazards 151
11.2 Safety of Equipment 152
11.3 Material Safety 153
11.4 Accident Caused By Hazards 154
11.4.1 Safeguards 155
11.4.2 Personnel Hygiene 155
Chapter Twelve: Conclusion and Recommendation 157

12.1 Conclusions 158
12.2 Recommendations 159
X
Appendix A 161
Appendix B 167
References 177
XI

Nomenclature
Symbol Description Unit (SI)
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

Heat Duty J/s

Overall Coefficient kJ/m . .
A Area of Heat Transfer m
Log Mean Temperature K
Inlet Hot Fluid Temperature, K
Outlet Hot Fluid Temperature K
Inlet Cold Fluid Temperature K
Outlet Cold Fluid Temperature K
Outside Fluid Film Coefficient kJ/m . .
Thermal Conductivity of The Tube’s Wall Material W/m. ͦC
Fluid Thermal Conductivity W/m. ͦC
Reynolds Number -
Prandtl Number -
Heat Transfer Factor -
Cross-Flow Area for The Hypothetical Row Of Tubes At Shell Equator m
Tube Pitch -
Baffle Spacing m
The Shell-Side Mass Velocity m/s
Linear Velocity m/s
Fluid Flow-Rate on The Shell Side kg/s
Density kg/m
Shell-Side Equivalent Diameter m
Tube Side Pressure Drop ⁄m
Number Of Tube Passes -
Tube Side Velocity m/s
Turnover Number -
Residence Time S
Molecular Weight kg/kmol
Tank Diameter m
Kinematic Viscosity m /
SG Specific Gravity -
Capacity Correction Factor -
Z Compressibility Factor -
S Maximum Permissible Stress Pa
t Wall Thickness m
Flow Number, -
N Radial Velocity rps
Viscosity Pa.s
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
Chapter One: Introduction

Figure (1.1): Projected Graphene Growth 4
Chapter Two: Literature Survey
Figure (2.1): Common Types of Carbon 7
Figure (2.2): Possible Graphene Applications 8
Figure (2.3): Andre Geim and Konstantin Novoselov 9
Figure (2.4): History of Graphene Source 9

Figure (2.5): Several Methods of Mass Production 12
Figure (2.6): Deformations of The Graphite 13
Figure (2.7): Schematic Flowchart for The Chemical Exfoliation Production Process 14
Figure (2.8): Schematic Illustration of Chemical Vapor Deposition 15
Figure (2.9): Complete Apparatus Setup for Chemical Vapor Deposition of Graphene 16
Figure (2.10): Pilot Plant for Large Scale Production of Graphene 17
Figure (2.11): Number of Manufactures of Graphene (2015) 21
Chapter Three: Laboratory Experiments

Figure (3.1): Schematic Diagram of the Mechanism of Electrochemical Exfoliation 25
Figure (3.2): Schematic Diagram of the Mechanism of Graphite Exfoliation Using
Surfactant 26
Figure (3.3): In Lab Experiments 30

Figure (3.4): Results 31
Figure (3.5): Sieving Trays Setup 33
Figure (3.6): Density Experiment 34
Figure (3.7): Plot of The Concentration Vs. Yield of Product 36
Figure (3.8): Plot of Change in Voltage Vs. Product Produced 37
Figure (3.9): Dye Concentration Percentage Vs. Time for Different Weights of Graphene 39
Figure (3.10): Dye Solutions After Two Days 39
Figure (3.11): Dye Concentration Percentage Vs. Time for Different Adsorbents 40
Figure (3.12): Dye Solutions After Two Days 41
Figure (3.13): A Schematic Diagram of Atomic Absorption Spectrometer 41
Figure (3.14): Concentration of Standards Vs. The Absolute Mean 43
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
Chapter Five: Material Balance

Figure (5.1): Materia Balance Based on Bench-Scale Process 72
Figure (5.2): Materia Balance Based on Pilot-Scale Process 73
Figure (5.3): Flow Summary Table Based on Pilot-Scale Process 74
Chapter Six: Energy Balance

Figure (6.1): Heat and Mass Transfer Phenomena 79
Chapter Seven: Equipment Description and Design

Figure (7.1): Tank Cell Schematic 82
Figure (7.2): Rotary Drum Filter 87
Figure (7.3): Bag Filter Liquid Strainer 87
Figure (7.4): Belt Filter 88
Figure (7.5): Plate and Frame Filter Press 88
Figure (7.6): Through Liquid Distributor 89
Figure (7.7): Filter Cloth Sketch 90
Figure (7.8): Filter Design (F-101) 91
Figure (7.9): Electric Hot Air-Drying Oven 93
Figure (7.10): (M-101) Outer Dimensions 95
Figure (7.11): High-Efficiency Four Blade Impeller and Three Blade Propeller 95
Figure (7.12): A Schematic of The ISP-3000 Ultrasonic Processor 99
Chapter Eight: Controlling Systems

Figure (8.1): Block Diagram of Feedback Control Strategy 104
Figure (8.2): Block Diagram of Feed Forward Control Strategy 105
Figure (8.3): Electrochemical Reactor (ECR-101) Control Loop 106
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
Chapter Nine: Plant Layout

Figure (9.1): Types of Plant Layout 122
Figure (9.2): Factors that must be considered when selecting a suitable site location 124
Figure (9.3): Steps to select a suitable site location 125

Figure (9.4): Sketch map of resource distribution in China 127
Figure (9.5): Changchun, China location (Google Maps) 128
Figure (9.6): Factors that must be considered when selecting a plant layout 129
Figure (9.7): Production of graphene plant layout 131

Figure (9.8): Production of graphene plant area layout 132
Figure (9.9): Graphene 3D Plant Using AutoCAD Plant 3D Software 133
Chapter Ten: Profitability Analysis

Figure (10.1): The cumulative cash flow diagram for Graphene production process, 147
generated using EXCEL
Figure (10.2): The cumulative cash flow diagram for production of graphene 148
Chapter Eleven: Safety and Hazard Prevention

Figure (11.1): Layers of Safety 150
Figure (11.2): Flammability Triangle for Graphene Production Plant 152

XVII

List of Tables
Chapter One: Introduction

Table (1.1): Mechanical properties of graphene, steel and graphite 2
Chapter Two: Literature Survey
Table (2.1): Advantages and challenges for each graphene production route 17
Table (2.2): Demerit table for the best alternative of graphene production 18
Table (2.3): Preliminary costs of major materials in the production of graphene 19
Table (2.4): Basic synthesis method, production capacity of graphene manufacturers 20
Chapter Three: Laboratory Experiments
Table (3.1): Reasons why these methods were not preformed 24
Table (3.2): Materials needed in each experiment 27
Table (3.3): Results of density experiment 34
Chapter Four: Process Description
Table (4.1): Feed streams to the process 54
Table (4.2): Effluent streams from the process 54
Chapter Six: Energy Balance
Table (6.1): Impeller power calculation for both mixers 77
Table (6.2): Final internal energy for both mixers 77
Table (6.3): Total work done by both filters 78
Table (6.4): Total energy for heating in dryers using the first method 79
Table (6.5): Total energy for heating in dryers using the second method 80
Chapter Seven: Equipment Description and Design

Table (7.1): Filters Design Summary (F-101) and (F-102) 91
Table (7.2): Mixers Design Summary (M-101) and (M-102) 96
Table (7.3): Dimensions of Each Storage Tank in The Process 96
Table (7.4): Selection of Material of Construction for Each Storage Vessel 97
Table (7.5): Typical Velocity Values Regarding Fluid Density 98
Table (7.6): Plant Pipe Dimension 98
Chapter Eight: Controlling Systems
Table (8.1): Control loop basic terminology 103
Table (8.2): Keys for Controllers’ Elements 105
Table (8.3): Tanks HAZOP study 110
Table (8.4): Mixers HAZOP study 111
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
Chapter Ten: Profitability Analysis
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 (10.5): Cost of product 145
Table (10.6): Discounted profitability criterion for the graphene production 148
Chapter Eleven: Safety and Environmental Analysis

Table (11.1): Environmental and Health Impacts 154
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
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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]
Graphene is undoubtedly the most promising nanomaterial because of its unique

combination of superb properties and wide possible uses. On the other hand, one of the
greatest challenges being faced in commercializing graphene is how to produce high
quality material on a large scale at low cost, and in a reproducible manner. The global
graphene market is projected to grow to $67 million in 2015. But the global graphene
market size actually was valued at $23.7 million in 2015 and is projected to grow at a
growth rate of 36.7% from 2016 to 2025. The annual global demand for semiconductor
silicon is approximately 2500 tons. If graphene substitutes even one tenth quantity of
crystalline silicon, the demand of graphene will be over $80 billion. For graphene oxide
the production was 100 tons per year in November 2013, which produced by big graphene
manufacturers as Sixth Element Materials (China). Other segment of production of
graphene is graphene sheets, that production was valued approximately 1.5 tons per year
in October 2012 and projected to increase to 300 ton per year in 2017–2019. [10]

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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
Figure 1.1: Projected graphene growth
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.

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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.
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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]
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Literature Survey

Figure 2.2: Possible graphene applications
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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 study of graphene can be traced back to the 19th century,

although its isolation from graphite was first archived in
2004. The credit goes to Professor Sir Andre Geim and
Professor Sir Kostya Novoselov of the University of
Manchester. They received the Nobel Prize in Physics in
2010 in recognition of their breakthrough. [12]
Figure 2.3: Andre Geim and Konstantin Novoselov [12]
Geim and Novoselov first attempt to achieve thin flakes of

graphene was by using sticky tape to get thinner flakes of
carbon graphite. Then by repeatedly peeled off further layers
from the originally taken flake until they managed to reach
flakes that were only a few atoms thick. [14]
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
Source: Graphene Flagship Website [15]
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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]
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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
As previously established, the exceptional properties of graphene qualifies it to be a good

candidate for the application as sensors. Ultra-sensitive graphene-based sensors vary from
traditional sensors, they are smaller, lighter and cheaper. Graphene-based sensors could be
utilized in a variety of different ways relying upon the desired measurements; from
chemical-based gas, pH and environmental pollution sensors, through to pressure and strain
sensors.
5. Composites and Coatings
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.
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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]

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2.4.1 Available Processes
Method 1: Mechanical Exfoliation Ball Mill
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]
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Losses of material in the developed milling system mostly occurred as a result of

mechanical losses. Additionally, leakage losses, specifically in orifice and sealing system,
and this type of loss often occurs in closed systems at higher applied pressures.
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]
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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]
Figure 2.8: Schematic illustration of chemical vapor deposition [18]
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.
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Figure 2.9: Complete apparatus setup for chemical vapor deposition of graphene [21]
Method 3: Liquid-phase exfoliation
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]
This method of shear-exfoliation of graphite to yield defect-free graphene nanoplatelets

that is industrially scalable. The exfoliation tended to occur in both laminar and turbulent
regimes. However, this technique requires harsh conditions such as extreme temperatures
and pressures, which is the biggest challenge in scaling up this process. [22]
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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]
Production routes Advantages Challenges
Safe process
Non-uniformity in product
Mechanical Exfoliation Eco-friendly
Cost-effective
High purity Usage of harsh conditions
Chemical Vapor Deposition Low waste disposal Specialized equipment
High energy consumption
Simple Low graphene yield

Liquid-phase exfoliation Non-oxidative Low disperse ability
Potentially scalable Low process ability
Cost-effective
Electrochemical High yield Affect the conductivity of product
Eco-friendly
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2.4.2 Demerit Selection Criteria
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
(1: Minor, 2: Moderately Low, 3: Moderately High, 4: High)
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.

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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.

2.5.1 Cost of Materials
The following table gives an approximate preliminary cost for the major plant materials
cost.
Table 2.3: Preliminary costs of major materials in the production of graphene
Materials Material Cost ($/kg)
Graphite Sheet 10
Sodium Sulfate 0.1
Hydrochloric Acid 0.2
Acetone 1.03
Water 0.002
2.5.2 Available Markets
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.

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2.5.3 Other Producers
Table 2.4: Basic synthesis method, production capacity of several big graphene manufacturers[23]
Country Manufacturer Synthesis Method Production

Capacity
Angstron Materials Liquid Exfoliation 300 tonnes.yr-1
Vorbeck Materials Oxidation-Thermal 40 tonnes.yr-1 (2012)

USA
Exfoliation
XG Sciences Intercalation Exfoliation 80 tonnes.yr-1 (2012)
UK Thomas Swan Liquid Exfoliation 1 kg.day-1 (2014)

10 tonnes.yr-1 (2020)
China Sixth Element Oxidation-Exfoliation- 100 tonnes.yr-1

Materials Reduction (2013)
Ningbo Morsh Intercalation– Expansion– 300 tonnes.yr-1

Exfoliation (2013)
Deyang Carbonene Intercalation– expansion– 1.5 tonnes.yr-1 (2012)

Tech exfoliation 300 tonnes.yr-1
(2017-2019)
2D Cabon Tech CVD 30,000 m2 (2013)
200,000 m2 (2014)
Wuxi Graphene CVD 80,000 m2 (2013)

Film
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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]
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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]
Experiments Not Executed Reasons
Chemical vapor deposition (CVD) Not available
Adhesive Tape Not an industrial way
Chemical Exfoliation Safety (high Acid), graphene oxide
From Table Sugar Not an industrial way, Graphene oxide
3.1.1 Graphene Preparation

A) Electrochemical Cell
Graphene produced by electrochemical exfoliation of graphite employing intercalation

of ions (SO4-2, NO-3, Cl-, Li+ etc.), graphite sheets were used as anode while using steel
electrode as cathode. Electrochemical exfoliation of graphite sheet is cleaving layers of
graphene from weakly bonded structural lattice layers of graphite. It can be done by
applying voltage source (2- 35 V) to allow the cleavage of layers. The graphite sheet placed
in the solution in order to let the electrolyte penetrate the sheet to ease graphene layers
peeling off and to pop them up directly after increasing the voltage potential. [29]
This is an improved synthesis of high-quality graphene demonstrated in a vertical cell

configuration via multiple electrochemical exfoliation of graphite sheets, enables multiple
exfoliation processes to improve both the quality and yield of graphene sheets. Various
voltages were applied on the electrochemical cell, with different concentration on that
electrolyte.
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Electrochemical method is an economical method for mass production of graphene. This

approach can produce high-quality graphene with a narrow distribution of layer numbers
(>60% products belong to 2-3 layers), as well as large flake size with simple processes and
gentle conditions. [30]
Figure 3.1: Schematic diagram of the mechanism of electrochemical exfoliation of few layer
graphene sheet (FLGN). [30]
B) Shear Exfoliation with Surfactant

This experiment follows a simple methodology, scalable, cheap, and environmentally
friendly. Briefly explaining this method, shear mixing mechanism provided enough energy
to break the graphite layers producing graphene which is suspended in solution, then
graphene connects to surfactant molecules.
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.
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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.
C) Shear Exfoliation without Surfactant
This method is based on liquid phase exfoliation of graphite to give graphene,

proclaiming it is possible to prepare low-cost graphene on a large scale, using
acetone/water mixture. This experiment is based on the strategy of tailoring Hansen
solubility parameters (HSP), mixing water and acetone can tailor the solubility parameters
to obtain ideal solvent systems. This method has vital advantages because water is an
entirely green solvent and acetone is a frequently used cheap solvent with a low boiling
point of 58 ºC. [31]
D) Sonication in Heptane Solution
In this experiment we supposed to show the use of an interfacial trapping technique to

assemble laterally macroscopic films of pristine graphene that are up to 95% transparent.
This is accomplished by modest sonication of natural flake graphite in a water/heptane
mixture to form continuous films at the interface between two immiscible liquids.
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Furthermore, the graphene sheets readily climb hydrophilic solid substrates, forming a
homogeneous thin film one to four layers thick.
3.1.2 Raw Materials Used

Each experiment requires different raw materials to execute the required procedure.
Table 3.2 lists all chemical materials used in the conducted experiments.
Table 3.2: Materials needed in each experiment
(A) (B) (C) (D)
Acetone 1 Activated Carbon Acetone 1 Distilled Water
Distilled Water Distilled Water Distilled Water Graphite Powder
Graphite Sheet Isopropyl Alcohol Graphite Powder Heptane
Hydrochloric Acid 2 Surfactant 5
Sodium Sulfate 3
Steel Sheet 4
(1: Az Chem-China, 2: LOBA Chems-India, 3: C.B.H Lab Chemicals-UK, 4: University Workshop, 5:

Fairy Surfactant)
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.
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3.1.3 Apparatus
Laboratory equipment needed to complete the experiments:
Beakers 50, 500, 1000 mL
Erlenmeyer Flask
Filter Paper
Funnel
Glass Scintillation Vial 20 mL
Graduated Cylinder 20,100 mL
Grinded Flask 1000 mL
Petri Dish
Reagent Bottle 1000 mL
Spatula
Laboratory devices needed to complete the experiments:
Analytical Balance, KERN PLS
Sonication Bath, ULTRASONIC LC 20H
Furnace, Tickstone England
Voltmeter, Philip Harris 25V supply ac.dc.
Mixer, VELP Scientifically
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3.2 Experimental Procedure

 Prepare 1.5 M solution of Na2SO4 as electrolyte

 Connect the graphite on the anode and the steel plate on the cathode
 Start the process by 2 V for 2 minutes, then increase to 10 V for some time
 Filter out the electrolyte and solid particles on filter paper.
 Wash the filter cake of graphene and solution with 75 mL of 30% HCl followed by
75 mL of distilled water
 Dry the solid in the furnace at 60 ºC for 2 hours to get rid of the moisture.
 In a 1000 mL reagent bottle mixing the product with a 250 mL of acetone
 The sonication process is carried out for 3 hours
 Graphene is collected and dried.
This experiment was conducted using graphite sheets and rods.

 Combine 25g of graphite powder to 0.5 L of deionized water in a beaker
 For 25g of graphite add 3.125g of soap (ratio is 8:1)
 Mix at 2000 rpm for 10 minutes
 Add 250 ml of isopropyl alcohol, to kill the foam
 Settle for the next day
 Scrap top layer and transferred to filter paper and dry
 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
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 Filtered the solution using filter paper and funnel

 Dry the filter cake is dried
Activated carbon powder was also experimented the same way.
 Place 2 mg of bulk pristine graphite into a 20 mL glass scintillation vial

 5.0 mL of n-heptane was added
 Briefly sonicate up to 30 minutes
 Then sonicate with closed tube for 15 minutes
 Add 5.0 mL of water
 Repeat both of the sonication steps again
 Transfer the film on a slide
 Dip the slide into a beaker of water
(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
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3.3 Results
(a) (b) i (b) ii
(c) i (c) ii (c) iii
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.
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3.4 Discussion of Results

The voltage was maintained in static bias of 2V for several minutes to wet the graphite
sheet and allow the SO4-2 ions to penetrate between graphite layers. Then high voltage
applied to start the peeling of the graphite layers into the top of solution. It is observed that
all of the submerged graphite in electrolyte transferred to graphene. This experiment
showed promising results, in respect to quantity and quality.
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.

Note that this experiment did not give the desired results due to the lack of required
equipment; a 100 Watts sonication could not do the job of a 300 Watts for both activated
carbon nor graphite powder. Nevertheless here are some of the concluded results from
these experiments:
 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.

This procedure was successful in producing good quality graphene nanoplatelets. Although
large amount of power is consumed compared to the actual amount produced.
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3.5 Graphene Characterization

Critical physical properties of the produced graphene seemed to be concluded only by
experiments, such as particle size and bulk density. These experiments were based on the
graphene produced from the electrochemical cell experiment.
3.5.1 Particle Size

The particle size of the produced graphene was required in the adsorption of dye tests, to
achieve fare comparison. To evaluate the particle size a simple sieving experiment was
conducted, six sets of sieves with apertures of 350, 250, 180, 125, 90 and 70 µm
respectively. This experiment resulted that the produced graphene has particle size between
125 and 250 µm. Even though this is not a precise method it was conducted just to provide
an initial idea, later in section 3.7 a more accurate particle size test was evaluated.
Figure 3.5: Sieving trays set up
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3.5.2 Bulk Density

The density of the produced graphene was needed in classifying the product, and in some
calculations. The procedure is a simple application of Archimedes' principle, using a 5 mL
cylinder, and a 2 mL pipette. In the cylinder 2 mL of water was added, then 0.02 g of
graphene mixed into the water and left for 10 minutes. Using the filled pipette, water was
added into the cylinder until the mark on the cylinder reached 4 mL, therefore the difference
in volume was read from the pipette, to reduce errors.
Table 3.3: Results of density experiment
Graphene (g) Volume (mL) Density ( g/cm3)
Run 1 0.021 0.15 0.140
Run 2 0.021 0.13 0.154
Run 3 0.021 0.14 0.143
Average 0.146
(a) (b) (c)
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
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3.6 Study of Process Variables

Based on the electrochemical cell experiment, since it resulted in actual products, testing
of variable was conducted on it. The variables affecting this experiment are the properties
of the cell as in voltage and current applied, time of the experiment, type and volume of
the electrolyte, and types of electrodes.
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.
3.6.1 Effect of Concentration
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.
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Figure 3.7 Plot of the concentration vs. yield of product
3.6.2 Effect of Voltage
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.
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Figure 3.8: Plot of Change in voltage vs. product produced
Variation of concentration and voltage parameters controlling the weight of graphene

produced. When applying higher voltage, it was observed that high amount of heat
produces as loss and as it increases low yield of graphene produces. On the other hand,
when increasing the concentration of electrolyte higher yield produced due to lower ohmic
drop in the solution. One curious aspect observed that some to sheets settled down to the
bottom which supposedly multilayer graphene because of the high thickness.
3.7 Graphene Performance Testing

3.7.1 Adsorption of Dye
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]
A spectrophotometer is an instrument that measures the amount of photons (the intensity

of light) absorbed after it passes through a sample solution in a test tube. With this device
the amount of a known chemical substance (concentrations) can also be determined by
using the transmittance-concentration curve (figure A1).
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This test was conducted for many reasons:
 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.
Part One: Adsorption Kinetics
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.
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Figure 3.9: Dye concentration percentage vs. time for different weights of graphene
Figure 3.10: Dye solutions after 2 days
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Part Two: Adsorption Comparison
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
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Figure 3.12: Dye solutions after 2 day, coarse activated carbon, and graphene respectively
3.7.2 Adsorption of Metals

Atomic absorption spectroscopy is a very common technique for detecting concentration
of metals and metalloids in samples, it can analyze over 62 elements. The technique uses
the principle that free atoms (gas) generated in an atomizer can absorb radiation at specific
frequency, in order to measure the concentration.
Figure 3.13: A schematic diagram of atomic absorption spectrometer
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Graphene possesses a special two-dimensional (2D) structure and excellent mechanical,

thermal, and electrical properties, and it would serve as an effective adsorbent for the
removal of heavy metal ions. Hence, this test was taken into consideration to check if the
produced graphene provide acceptable results. This test was conducted to test the
adsorption of some metals by graphene:
 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.
Part One: Lead
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
include: pH value, initial Pb (II) concentration, adsorbent dose, adsorption time, and
temperature.
Figure 3.14: Concentration of standards vs. the absolute mean
Part Two: Iron
Iron is a major component in the Earth’s crust, therefore it is found naturally in

groundwater and surface waters. Drinking of iron polluted water in low concentrations is
not known to cause serious damage to humans. The most common applied techniques used
to remove iron ions from water are water softeners, and reverse osmosis.
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
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.
Figure 3.15: Concentration of standards vs. the absolute mean
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3.7.3 Particle Size Distribution

The particle size distribution test was conducted to analyze the produced graphene.
According to the results in table 3.4 the particle dispersion index (PDI) appears to be less
than 2 revealing a fully dispersed sample. Moreover, the average particle size is calculated
to be 711 nanometer.
Table 3.4: Particle size distribution results
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
3.7.4 X-Ray Diffraction

X-ray diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions.
XRD consist of three basic elements: an X-ray tube, a sample holder, and an X-ray detector.
Angle of x-ray source and the sample is theta and between sample and detector is also theta
so they add up into two theta. The x-ray source and the detector are constantly movable in
synchronization, each at the same theta angle. Sample holder is kept in place and the ray
intensity is constant, but the only changing variable is theta. At first the sample absorbs the
x-ray subjected to it, therefore no readings are detected. The absorption of x-ray begins
when Bragg’s equation is accomplished, at a specific two-theta. Intensity is greater when
the plane contains the greater number of atoms therefore diffraction is greater.
Bragg’s Law
2 sin (3.1)
Where;
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d: Normal distance between two parallel successive planes
θ: Bragg angle, XRD position at one half of 2θ
n: Order of diffraction (n=1)
λ: Wavelength of incident radiation (λ=1.54 )
Scherrer’s Formula

* (3.2)
cos
Where;
: Average crystallite size [nm]
K: Scherrer constant (K=0.94 for spherical crystallites with cubic symmetry)
B: Full width at half maximum of XRD peak
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
(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
3.7.5 Scanning Electron Microscopy

As the phase formation was studied and investigated, the microstructure graphene
product was observed by SEM. Since the SEM displays the morphology of any substrates,
voids and impurities; it indicates that graphene is pure and clear of any defects.
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
(a) (b)
Figure 3.17: SEM image of graphene (a) SEM test on produced graphene (b) SEM test from
theory
3.7.6 Transmission Electron Microscopy

TEM image shows individual graphene sheets extended from graphite sheet. It indicates
thickness of graphene layers. From figure below, it can be observed that the graphene
produced has distribution of monolayer and multilayer of graphene.
(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

4.1 Hierarchy of Decisions

One of the first stages of designing a process is deciding whether a batch or a continuous
operation is to be chosen. For this production of graphene, a batch operating process was
selected for the following reasons:
 Small scale production

 Graphene is a new product
 High product quality
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]
Figure 4.1: The onion model of process design [34]
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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.

4.2 Process Description

Mostly the way to communicate information regarding a process is through the usage of
visual aids and flow diagrams. [35]
Synthesis of graphene flakes is produced via the multiple electrochemical exfoliation
method. Where the physical exfoliation process production starts when a certain voltage
across the electrodes is applied. Where at 2 volts the electrolyte penetrates through the
graphite sheet, then at 10 volts the graphite sheet starts to peel off and the flakes reduce in
size.
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).
Figure 4.2: BFD for the graphene production
4.2.3 Process Flow Diagram

Process flow diagram (PFD) is the buildup of additional information on the BFD. Most
PFDs basically contain all operating units each with a unique number and abbreviation,
numbered streams, and basic control loops. The process flow diagram for the production
of graphene is illustrated in figure 4.3.
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Process Description

Figure 4.3: PFD for the graphene production
4.2.4 Main Process Streams

Table 4.1: Feed streams to the process
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
Table 4.2: Effluent streams from the process
Effluent Streams
<14> Graphene product, solid powder, 60oC

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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.
2 ∗ 300 600 (4.1)
Figure 4.4: Gantt chart for the graphene production process
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]
Material In – Material Out + Generation – Consumption = Accumulation (5.1)
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]
As for chemical engineers scaling up a process is essential knowledge. The process

described in chapter 4 is the scale up of the laboratory scale into a pilot plant, on which
material balance is calculated on. In this section, the bench-scale material balance is
discussed, and a detailed calculation of how the process was scaled up is shown.
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.
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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.
Overall Balance on the beaker:
53.3 + 250 = 303.3 g
Component Balance on Na2SO4:
53.3
0.176 %
, 303.3
Component Balance on H2O:
250
0.824 %
, 303.3
Material Balance on Electrochemical Cell

Steel sheet is connected to the cathode (negative electrode) and graphite sheet to the
anode (positive electrode). The graphite sheet is completely submerged in the electrolyte,
which is weighted to be 0.63 grams. The electrochemical cell provides enough forces to
break down all the graphite to graphene flakes.
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Material Balance

Overall Balance on the Cell:
303.3 + 0.63 = 303.93 g
53.3
0.175 %
, 303.93
250
0.823 %
, 303.93
Component Balance on Graphene:
0.63
0.002 %
, 303.93
Material Balance on Filter 1

The mixture of liquid and solid exiting the electrocell is filtered and washed in the
process. Graphene flakes on the filter paper contain some electrolyte solution and washing
material, these amounts are calculated in appendix B.
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Material Balance

Overall Balance on the Filter:
, ,
, 1.23 5.771 0.63 7.632
, 303.93 7.632 296.298 g
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
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Material Balance

, ,
, 1.578 0.289 0.63 2.497
68.3588 12.5 80.859
, 7.632 80.859 2.497 85.994 g
1.23
, 0.014 %
, 85.994
12.5
, 0.155 %
80.859
0.289
, 0.11558 %
, 2.497
5.771 12.5 0.289

, 0.209 %
, 85.994
Component Balance on HCl:
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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
, ,
, 1.731 0.63 2.361
, 2.497 75 2.361 74.847 g
75
1 %
75
1.731
, 0.733 %
, 2.361
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Material Balance

75 1.731
, 0.979 %
, 74.847
1.578
, 0.021 %
, 74.847
0.63
0.267 %
, 2.361
Material Balance on Dryer

Drying process takes place after filtration, to evaporate the moisture in the solid. Two
dryers are presented in the described process.
Overall Balance on the Dryer:
, ,
, 2.361 0.63 1.731 g
1.731
1 %
, 1.731
0.63
1 %
, 0.63
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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.
Overall Balance on the Sonication Bath:
, 196 0.63 196.63 g
Component Balance on C3H6O:
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
.
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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
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Material Balance

5.4 Filter (F-101)
Overall Balance on the Filter for electrolyte:
, ,
, 1.953 9.161 1 12.114
, 482.429 12.114 470.314 Kg
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
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Material Balance

Overall Balance on the Filter when cake washing:
, ,
, 2.505 0.458 1 3.963
108.506 19.841 128.347
, 12.114 128.347 3.963 136.498 Kg
1.953
, 0.0143 %
, 136.498
19.841
, 0.1546 %
128.347
0.458
, 0.11558 %
, 3.963
9.161 19.841 0.458

, 0.2091 %
, 136.498
108.506
, 0.8454 %
128.347
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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
, 3.963 119.048 3.748 118.804 Kg
119.048
1 %
119.048
2.748
, 0.7332 %
, 3.748
119.048 2.748
, 0.9789 %
, 118.804
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Material Balance

2.505
, 0.0211 %
, 118.804
1
0.2668 %
, 3.748
5.5 Mixer (M-101)

, 84.603 82.65 1.953
, 396.825 387.664 9.161
, 1.953 9.161 470.314 481.429
84.603
0.1757 %
, 481.429
396.825
0.8243 %
, 481.429
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Material Balance

5.6 Dryer (D-101)
Overall Balance on the Dryer:
, ,
, 3.748 1 2.748 Kg
2.748
1 %
, 2.748
1
1 %
, 1
5.7 Sonication (S-101)
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

Figure 5.1: Material balance based on bench-scale process
72 | P a g e

Material Balance

Figure 5.2: Material balance based on pilot-scale process
73 | P a g e

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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
Figure 5.3: Flow summary table based on pilot-scale process

Overview
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;
Np: Power number
ρavg: density of the components [Kg/m3]
rps: Revolution per second
Dimp: Diameter of the impeller [m]
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;
μ: Dynamic viscosity of the solution [Pa.s]
The average density of the mixture is calculated by using the mass fraction ratio for each
component as in equation (6.3).
(6.3)
Final internal energy for the solution
(6.4)
Where; work is the change in internal energy.
77 | P a g e
Energy Balance
Table 6.1: Impeller power calculation for both mixers
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
Table 6.2: Final internal energy for both mixers
Initial Internal Final Internal

Work* [kJ]
Energy** [kJ] Energy [kJ]
MIX-101 94.1 2.7 96.8
MIX-102 30.1 1.8 31.9
**Calculated from reference [P. Marliacy]
6.2 Electrochemical Reactor

 ∗ ∗ / ∗ (6.5)
/ ∗ (6.6)
Where; [40]
 : Current Efficiency
M: Molar Mass of Product
I: Current Applied in the cell (Ampere)
t: Time in second
z: Oxidation state
F: Faraday's constant
Ecell: Voltage Applied.
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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)
Table 6.3: Total work done by both filters
Pressure Drop* [Pa] Total Work Done* [Watt]

F-101 2.9*10-9 3.7*10-12
F-102 5.1*10-12 9.8*10-16
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)
ower Absorbed by Material and Container

∗ ∗
3600
∗
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Energy Balance

∗ . ∗ ∗

3600
Table 6.4: Total energy for heating in dryers using the first method
Power Power Losses Power Total Power Energy

Absorbed by from Losses for Heating Needed*
Material and Equipment from [kW] [kJ]
Container* Surface* [kW] Heating
[kW] Air* [kW]
D-101 9.65 5.3 0.28 15 1.1*105
D-102 2.64 5.3 0.14 8 2.9*104
Method II: [42]
Figure 6.1: Heat and mass transfer phenomena [43]
∗ ∗ ∗
)
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Energy Balance
∗ ∗
K ∗ Surface Area ∗ Temperature Differance

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
6.6 Summary of Results

Table 6.6: Summary of total power on equipment
Equipment Total Power [kW]

M-101 0.105
M-102 0.05
F-101 3.7*10-15
F-102 9.8*10-19
D-101 15
D-102 8
ECR-101 435.3
S-101 3
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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
7.1 Electrochemical Reactor Design

Factors affect ECR are investigated and demonstrated to provide proper design of the
ECR, which it is the main unit and the heart of this plant.
7.1.1 ECR Description
An electrochemical reaction can be conducted in batch or continuous (mixed/plug flow)

mode. Further, the reactors can be operated with or without recycle. Further classifications
are possible on the basis of flow arrangement (parallel/series flow) or electrical connections
(monopolar/bipolar).
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]
Figure 7.1: Tank cell schematic [40]
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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.
According to the available conditions in this process secondary current distribution is

applied since the over-potential must be regarded unlike the concentration gradient of
electrolyte in the ECR. The over-potential in this process cannot be neglected due to high
potential requirement since the equilibrium potential of the anode graphite sheet is
relatively high. [44]
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.
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Geometrical and over-potential similarity between two scales results in a constant ratio
known as Wagner number (Wa). [44]
(7.1)
Where;
k: conductivity of the electrolyte
L: characteristic length
: over-potential at certain current density
To correctly achieve scaling to an industrial equipment some constrains must be overcome.

To maintaining the electrode gap fixed while increasing the area of the ECR. Moreover,
stacking individual cells in mono-polar or bipolar multi cell reactor.
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.
7.1.2 Design Procedure
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;
: exchange current density
: symmetry factor, typical value=0.5
: oxidation state
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: faraday's constant
: surface over-potential (Activation)
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
: equilibrium electrode 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]
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 (7.5)
Where;
k: Conductivity of the electrolyte
: Electrical field in the cell
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.
7.2 Filter Design

Since in this process the separation of solid that is suspended in liquid is present, then
liquid filtration is required. Filtration is essentially a mechanical operation and needs less
energy than evaporation or drying. In the illustration shown in figure 7.2, the cake gradually
builds up on the medium and the resistance to flow proportionally increases. During the
initial period of flow, particles are deposited in the surface layers of the cloth to form the
true filtering medium, which might may be formed from a special precoat material. The
most important factors on which the rate of filtration depends on:
 pressure drop
 the area of the filtering surface
 the viscosity of the filtrate
 the resistance of the filter cake
 the resistance of the filter medium and initial layers of cake
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7.2.1 Filter Selection
Type of Filters
1. Disc and drum
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.
Figure 7.2: Rotary drum filter

2. Tank filter
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.
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Figure 7.3: Bag filter liquid strainer

3. Belt filters
A belt filter consists of a reinforced rubber belt, with drainage hole along its center, which
supports the filter medium. The belt passes over a stationary suction box, into where the
filtrate is sucked. Slurry inlet and washing agent are passed on to the top of the belt, and
dry solid scraped at the edge of the belt.
Figure 7.4: Belt filter

4. Filter Press
Plate and frame filter press is the oldest and most commonly used batch filter. Most of its
advantages are that they are made in a variety of materials, versatile equipment, and capable
of handling viscous liquids and cakes with a high specific resistance.
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Figure 7.5: Plate and frame filter press

Filter Selection Criteria
The selection of a filter must begin with the specification of the required job that the filter,
the desired outlet, some specification of the feed, the filtrate and the filter cake. The suitable
type of separation unit is chosen to be a modified version of basket strainers. It was chosen
based on the following reasons:
 Ease of design and operation

 Low capital and operating cost
 Simple controlling system
 High product recovery
7.2.2 Filter Description
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).
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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.
Figure 7.6: Through liquid distributor
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.
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Figure 7.7: Filter cloth sketch
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.
7.2.3 Design of Filter
Figure 7.8: Filter design F-101
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Table 7.1: Filters design summary F-101 and F-102
F-101 F-102
Area of Cloth [m2] 1.03 1.7
Radius of Cloth [m] 0.6 0.7
Height of Cake [m] 0.02 0.01
Volume of Cone [m3] 0.84 0.77
Height of Cone [m] 2.5 1.4
7.3 Dryer Design

Drying can be defined as the removal of small amounts of water or other liquids from a
solid material by the application of heat. Several different ways are used to classify the
drying method. The drying process can be classified to be batch when the material is placed
in the dryer unit then after a certain time the product is released. On the other hand, the
drying process can be classified to be continuous, when the material is continuously added
to the dryer and the product continuously removed. Another way to classify the drying
process can be through the physical conditions used for the addition of heat. Either by direct
contact between the heated air and the water vapor, or by vacuum drying where it is at low
pressures and the heat is added indirectly by radiation, otherwise by freeze drying.
7.3.1 Dryer Selection and Description
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.
Batch dryers types are: oven, tray, and disc dryers.
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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.
Figure 7.9: Electric hot air drying oven

Mechanical Description
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.
7.3.2 Sizing of Dryer
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.
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7.4 Mixer Vessel Design

Mixers are cylindrical tanks containing mechanical agitators, where mixing of phases is
accomplished. In this process for production of graphene two agitators are utilized to
homogenize the inlet streams to other equipment. The first mixing unit is necessary to
dissolve solid sodium sulfate (Na2SO4) in water before ECR. The second mixer
homogenizes the inlet solution of acetone and graphene product to the ultra-sonication unit.
7.4.1 Design of Mixer

Assuming that the mixer is a cylindrical tank with standard geometry with an impeller
inside it, the mixer mechanical design calculations will include: dimensions calculations,
specification of the material of construction, wall thickness and selection of support.
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
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.
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Figure 7.10: M-101 outer dimensions
7.4.2 Design of Impeller
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.
Figure 7.11: High-efficiency four-blade impeller and three blade propeller
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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:
Table 7.2: Mixer design summary M-101 and M-102
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
7.5 Storage Vessel Design

A storage tank is a container, usually for holding gas, liquid or solid materials. Different
available features in many shapes spherical, cylindrical or conical. Storage tanks are often
cylindrical in shape because the fabrication of cylindrical tanks are easier than other types.
7.5.1 Dimensions of Tanks
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).
Table 7.3: Dimensions of each storage tank in the process
Volume of One Batch[m3] Total Volume [m3] Diameter = Length [m]
TK-101 0.419 0.838 1.15
TK-102 0.121 0.242 0.98
TK-103 0.118 0.236 0.98
TK-104 0.385 0.77 1.13
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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.
7.5.2 Material of Construction
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.
Table 7.4: Selection of material of construction for each storage vessel
Vessels MOC
TK-101 CS
TK-102 SS
TK-103 CI
TK-104 CS
7.6 Pipes Design

Process pipes are thin cylinders which have a specific thickness to resist the internal
pressure with an allowance of corrosion.
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.
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Table 7.5: Typical velocity values regarding fluid density
Fluid density
Velocity m/s
Kg/m3
1600 2.4
800 3.0
160 4.9
Table 7.6: Plant pipe dimension
Stream Flow rate Density Velocity Length Inner

No. Kg/batch Kg/m3 m/s m Diameter m
7.357x10-2
<2> 9.161 1000 2.85 9
<3> 481.429 1292 2.63 5 5.463x10-1
<4> 482.429 1289 2.63 7 5.474x10-1
<6> 119.048 1000 2.85 8 2.864x10-1
5.223x10-1
<9> 312.111 784 3.05 5
5.228x10-1
<11> 312.111 782 3.05 7
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7.7 Rating of Ultra-Sonication Unit

This unit was selected from suppliers because in general sonication units are complicated
to design. From Industrial Sonomechanics, ISP-3000 industrial-scale processor was
selected based on the following reasons:
 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.
Figure 7.12: A schematic of the ISP-3000 ultrasonic processor
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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:
 Large and complex operations

 Large number of theoretical and practical considerations
 Safety and stability of the operation
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]
In general all closed-loop control technology operate this way: [45]
1. The controlled variable is measured and an electrical signal is created, to allow an

independent controller to control the variable.
2. The measured value in the controller must then be compared with the desired value.
3. The result of this comparison determines if any action needs to be taken.
4. A suitable location must be found in the system where the controlled variable can
be changed.
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]
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Controlling Systems
8.1 Control Loop Elements

The major components of a control system include a transmitter, a controller and a final
control element.
Table 8.1: Control loop basic terminology
Measuring Elements Instrument measuring changes in the process and reporting a

process variable measurement. (pressure sensing diaphragms,
thermocouples, orifice plates)
Transmitters Device that converts a reading from a sensor into a standard
signal then transmits to a monitor or controller. (pressure,
temperature, flow, and level transmitter)
Signals Transmit the process variable measurement from the instrument
to a centralized control system. (pneumatic signal, analog signal,
and digital signal)
Indicators A human-readable device that displays information about the
process. (pressure or temperature gauge)
Recorders Device that records the output of measurement devices, to meet
regulatory requirements.
Controllers Device that receives data from a measurement instrument,
compares that data to a programmed reference variable, and if
necessary signals a control element to take corrective action.
Final Control Elements In most cases, a valve used to restrict or cut off fluid flow, pump
motors, louvers.
8.2 Process Control Strategies

In large-scale, integrated processing plants, thousands of process variables such as
compositions, temperatures, and pressures are measured and must be controlled.
Fortunately, large numbers of process variables (mainly flow rates) can usually be
manipulated for this purpose. [46]
There are two main strategies of process control:
1- Feedback
2- Feed Forward
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Controlling Systems
8.2.1 Feedback Control Strategy

The distinguishing feature of feedback control is that the controlled variable is measured,
and that the measurement is used to adjust the manipulated variable. For feedback control,
the disturbance variable is not measured. [46]
In a feedback controller when an offset is generated in the controlled variable, the controller
acts to eliminate or reduce this offset, usually an oscillation is produced in the value of the
controller variable whose amplitude, period and damping depend on the nature of the
system and mode of action of the controller. [47]
Figure 8.1: Block diagram of feedback control strategy
Controllers provide one, two, or three of these modes of corrective actions:
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.
8.2.2 Feed Forward Control Strategy
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]
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Controlling Systems
Figure 8.2: Block diagram of feed forward control strategy
8.3 Equipment Control Loops

Control systems for the major equipment in this graphene production is developed to
regulate the process operating conditions. These equipment include: electrochemical
reactor, pump, filters, dryers, and ultra-sonication. The notation used for the controllers
and control elements in this section are shown in the table below. A plant control flow sheet
was developed in this section.
Table 8.2: Keys for Controllers’ Elements
Symbol Meaning
FIC Flow Indicator Controller
LIC Level Indicator Controller
TC Temperature Controller
CC Concentration Controller
PC Pressure Controller
Control Valve
Pneumatic Signal
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Controlling Systems
8.3.1 Electrochemical Cell Control Loop

The schemes used for reactor control depend on the process and the type of reactor.
Control is applied automatically to maintain the desired product composition and yield.
More often, the operator is the final link in the control loop, adjusting the controller set
Points to maintain the product within specification, based on periodic laboratory analysis.
Pressure and temperature is usually held constant, so no need for pressure control.
Although it is essential to convert the supplied current to DC using the DC rectifier.
DC Current 3
ECR‐101
AC
Power
DC
Rectifier
Figure 8.3: Electrochemical Reactor (ECR-101) control loop
8.3.2 Pumps Control Loop

Pumps are used to increase the pressure of process streams. Pumps can be considered as
positive displacement pump within constant flows and variable discharge pressures due to
variety in pump head.
Therefore, in order to regulate the flow of process streams, a portion of the output stream
from the pump must be recycled. This is accomplished by returning a stream to the suction
side of the pump. Since the flow rate of liquid in the pump is almost constant, regulation
for the main process stream is provided. The following suggested flow rate control loop on
the centrifugal pump can provide a good performance and significant energy savings at
lower rates. It is important to place control valves after the pump in a given pipe. Placing
valves after the pump ensure that even if the pump does not shut off, it is still filled with
the proper fluid.
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Controlling Systems
FIC
P‐101 A/B
Figure 8.4: Pump (P-101A/B) control loop
8.3.3 Filtration Control System

Filtration of graphene takes place in the filter cloth. To control the filter, the control
systems measures the level for determining the properties and the amount of products
flowing into the filter.
LIC
F‐102
Figure 8.5: Filter (F-102) control loop
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Controlling Systems
8.3.4 Tank Control Loop
LIC
TK‐101
Figure 8.6: Storage Tank (TK-101) control loop
8.3.5 Dryer (oven) Control System
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
Figure 8.7: Oven Dryer (D-102) control loop
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Controlling Systems
8.3.6 Ultra-Sonication Tank Control Loop
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
Figure 8.8: Ultra-Sonication unit (S-101) control loop
8.4 Hazard and Operability (HAZOP)

Hazard and Operability Study (HAZOP) is a systematic and structured assessment of a
planned or existing plant, it is applied to identify, classify and evaluate the problems that
may appear as danger or a risk to personnel or equipment. It is preferably applied to new
plants at an early stage, or to existing plants where a major redesign is planned. The
HAZOP is usually carried out as a final check after a complete design is done. Types of a
HAZOP study can be categorized into four compartments. Process HAZOP, this technique
assess and evaluates plants and process systems. Human HAZOP, mostly focus on human
errors than technical failures. Procedure HAZOP, re-evaluate of procedures or operational
sequences. And finally software HAZOP, detection of possible errors in the development
of software. All these types of a HAZOP study are considered to be a main element is the
control and stability of the plant. [48]
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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
HCl with flow production delay installation
Solution More
traces Pumping system failure Level controller
inlet
(that of inlet stream) Over flow installation
volume
Water with
HCl traces More
Pumping system failure Level controller
inlet Over flow
(that of inlet stream) installation
volume
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.
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Controlling Systems
8.4.2 Mixers
Table 8.4: Mixers HAZOP study
Guide
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
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Controlling Systems
Continue Table 8.4: Mixers HAZOP study
Guide
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
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Controlling Systems
8.4.3 Electrochemical Reactor

Table 8.5: Electrochemical reactor HAZOP study
Guide
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
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Controlling Systems
8.4.4 Filters
Table 8.6: Filters HAZOP study
Guide
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
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
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Controlling Systems
Continue Table 8.6: Filters HAZOP study
Guide
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
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
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Controlling Systems
8.4.5 Ultra-Sonication
Table 8.7: Ultra-Sonication unit HAZOP study
Element Guide word Cause Consequences Action

Circuit breaker
Supply shortage
No electricity Delay in production required
Internal damage Maintenance
Less than Supply shortage
lower product quality
Electricity instructed or controlling
and loss of material
values error Ventilation system
Exceeding normal required, Electric
More than controller needed
Instant increase temperatures of
operating
in current supply solution, significant
values
evaporation
Pumping system
More volume Loss of material, over Level control
failure; of inlet
than allowed flow required
stream
Inlet pump Increasing level,
system failure Maintenance
Lower product
Less volume Level controller
quality and loss of
than required installation,
Leakage in tank material
closing inlet and
Acetone-
outlet valves
Solid
mixture Reversible Increase in Level control
Back flow
flow solution level element required
Other than:
No guarantee on
Sodium product quality
Sulfate salt Human error,
Get rid of solution
supplier error
Other than
highly pure Low grade product
salt
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Controlling Systems
8.4.6 Dryers
Table 8.8: Dryers HAZOP study
Element Guide word Cause Consequences Action

Dry again and
More amount than Poor performance Wet solid, Loss
control the outlet
allowed of F-101 of material
flow of F-101
Less distilled Having traces of Flow control on
Less than expected water inlet to F- HCl in the dried top-inlet stream
Distilled
101 solid of F-101
Water
Install
Other than Distilled Error caused by concentration
Low grade
water: using tap the supplier or controller on
product
water workers D.W. inlet of F-
101
More heat than
Error in Loss of energy Temperature
Electric required for drying
temperature set controller
heat Less heat than point Wet solid installation
required for drying
Using Error caused No guarantee
another by the supplier on product
Other solvent or by workers quality
Get rid of batch
than Using low
Error caused Low grade
grade
by the supplier product
solvent
Acetone
Loss of both Decreasing the
Less amount than Leakage in inlet
material and drying time
expected stream
energy slightly
Increasing the
More amount than Poor performance
Loss of material drying time
allowed of F-102
slightly
Distilled water Increase amount
Low purity of
HCl If existed in D-101 used was not of distilled water
product
enough used in F-101
More than Increasing the
Accumulated on Increases time
recommended drying time
filter3 needed for drying
/expected slightly
Solid Leakage in inlet
Containing
stream or Loss of material
Less than expected leakage, Regular
accumulated on and energy
cleaning
F-102
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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]
Chemical process layout optimization is a task to efficiently determine the relative

position of the equipment or facility of the process. Process safety might be considered as
the most important area to improve several aspects in the process industry design. Ways of
dealing with hazards include means to either control them or totally remove them. Both
control and removal ways can be applied during the design stage to produce inherently
safer designs. [50]
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.
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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]
9.1.1 Objectives of Good Plant Layout

A well designed plant layout is one that can be beneficial in achieving one of the
following objectives:
 Proper and efficient utilization of available floor space

 Transportation of work from one point to another without delay
 Proper utilization of production capacity
 Reduce material handling costs
 Utilize labor efficiently
 Reduce accidents
 Provide availability for expansion and product flexibility
 Provide ease for supervision and control
 Provide for employee safety and health
 Allow easy maintenance of machines and plant
 Improve productivity
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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
Figure 9.1: Types of plant 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.
Table 9.1: Advantages and disadvantages of product layout
Advantages of product layout Disadvantages of product layout

Low cost of material handling Higher initial capital investment in
Smooth and continuous operations special purpose machine
Continuous flow of work High overhead charges
Optimum use of floor space Breakdown of one machine will disturb
Lower manufacturing cost per unit the production process
Effective inspection of work Lesser flexibility of physical resources
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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.
Dept. Dept. Dept.
Dept. Dept. Dept.
Table 9.2: Advantages and disadvantages of process layout
Advantages of process layout Disadvantages of process layout

Lower initial capital investment is required Material handling costs are high
High degree of machine utilization More skilled labor is required
The overhead costs are relatively low Greater storage space needed
Supervision can be more effective More frequent inspection is needed
Greater flexibility of resources

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.
Fixed Position Layout

Fixed position or location layout involves the movement of manpower and machines to the
product which remains stationary. The movement of men and machine is advisable as
moving them would be cheaper. This type of layout is preferred where the size of the job
is bulky and heavy.
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Plant Layout

Table 9.3: Advantages and disadvantages of fixed position layout
Advantages of fixed position layout Disadvantages of fixed position layout

The investment on layout is very small Capital investment is very high
Changes can be incorporated Greater storage space needed
Adjustments can be made to meet shortage Possibility of confusion among different
of materials or absence of workers workgroups
9.2 Site Location

The location of the plant can have a crucial effect on the profitability of a project, and
the scope for future expansion.
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

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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:
Figure 9.3: Steps to select a suitable site location

Selection of the Country
The first step in location a plant is to decide whether the plant is located domestically of
internationally. Due to globalization the issue of home or foreign is gaining more relevance.
The choice of particular country depends on such factors like political stability, export and
import quotas, and exchange rates. [51]
Selection of the Region

As manufacturing unit is engaged in the conversion of raw materials on to finished
products, it is very essential that it should be located in a place where the supply of raw
materials is maximum.
The location of markets or intermediate distribution centers affects the cost of product
distribution and the time required for shipping. It should be noted that markets are needed
for by-products as well as for major final products.
Power and steam requirements are high in most industrial plants, and fuel is ordinarily
required to supply these utilities. Electrolytic processes require a cheap source of
electricity, and plants using electrolytic processes are often located near large hydroelectric
installations. If the plant requires large quantities of coal or oil, location near a source of
fuel supply may be essential for economic operation. The local cost of power can help
determine whether power should be purchased or self-generated.
Water, railroads, and highways are the common means of transportation used by major
industrial concerns. The kind and amount of products and raw materials determine the most
suitable type of transportation facilities.
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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.
Selection of the Community

Consideration should be given to prevailing pay scales, restrictions on number of hours
worked per week, competing industries that can cause dissatisfaction or high turnover rates
among the workers, and variations in the skill and productivity of the workers. Labor will
be needed for construction of the plant and its operation. Skilled tradesmen will be needed
for plant maintenance. [52]
Selection of the Exact Site

The characteristics of the land at a proposed plant site should be examined carefully. The
topography of the tract of land and the soil structure must be considered, since either or
both may have a pronounced effect on construction costs. The cost of the land is important,
as well as local building costs and living conditions. Future changes may make it desirable
or necessary to expand the plant facilities. Therefore, even though no immediate expansion
is planned, a new plant should be constructed at a location where additional space is
available.
All industrial processes produce waste products, and full consideration must be given to
the difficulties and cost of their disposal. The disposal of toxic and harmful effluents will
be covered by local regulations. Recently, many legal restrictions have been placed on the
methods for disposing of waste materials from the process industries. The site selected for
a plant should have adequate capacity and facilities for correct waste disposal.

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Plant Layout

9.2.2 Location of the Plant
The production of graphene plant location is selected based upon the aforementioned
steps.
Selection of the Country

The plant was selected to be in China, where the industry of similar plants are available.
China was chosen to be the site location of graphene production process based on the
political stability, export and import quotas, and exchange rates in the country.
Selection of the Region

It is very essential that the plant should be located in a place where the supply of raw
materials is maximum, therefore the northeast region was selected. International shipping
can be achieved because the availability of ports to location of markets and ease of common
means of transportation. Power and steam requirements are high in most industrial plants,
electrolytic processes require a cheap source of electricity, where China is one of the
cheapest countries in electrical source. Located near large hydroelectric installations
because this plant uses large electrolytic processes
Figure 9.4: Sketch map of resource distribution in China
Selection of the Community

Jilin, China is selected due to availability of industrial area, where labor is available with
low minimum wage salary. No restrictions on number of hours worked per week, where
the operation time is 13 hours per day.
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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.
Figure 9.5: Changchun, China location (Google Maps)
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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

9.3.1 Spacing between Equipment

The minimum spacing between equipment should be set early on in the design. These
distances are set for safety purposes, maintenance, and economic design of piping system.
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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
9.3.2 Main Units Located in Plant Layout

The equipment will be arranged to give an optimum arrangement to reduce cost as
possible as it can be. This is done by arranging equipment in the sequence of production
steps, so the pipe lines will be as short as possible.
Table 9.5: Typical area of preliminary site layout
Site Area
Plant Area 15x20 m2
Administration Office 15x20 m2
Workshop & Maintenance + Laboratories + Research & 20x30 m2

Development + Fire station
Quality & Safety + Warehouse + Production Office + 30x30 m2
Supply Chain
Storage Area 15x20 m2
Total roads areas 8x50 m2

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Plant Layout

Figure 9.7: Production of graphene plant layout
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Plant Layout

Figure 9.8: Production of graphene plant area layout
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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.
Figure 9.9: Graphene 3D plant using AutoCAD Plant 3D software
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Overview
Chapter 10, in this

chapter economic
analysis was made to
determine if the
production of graphene
is economical process
and can be applied in
reality and to determine
the payback period of
this project. Cash flow
diagram was generated
to show the flow of
needed investment and
revenue in each year.
Profitability Analysis
The purpose of any manufacturing industry is to make money. This is perceiving by

produce product with a high market value from raw material with a low value. The
chemical process industry produces high value chemicals from law value of raw materials.
Many engineering design projects are developed to provide sizing information from which
estimates of capital and operating costs can be made. In this chapter an estimation of fixed
capital cost and operation cost for production of graphene process, and profitability
analysis will be done manually by Microsoft Excel. So, an economic evaluation can be
carried out to determine if the process generates money, or if the process is attractive
compared to other process.
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]
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10.1 Estimation of Total Investment

10.1.1 Introduction to Estimation of Fixed Capital Investment
There are many quick estimates methods can be done to evaluate the total investment of
the plant, as step counting method. Cost estimates for chemical process plants are often
based on an estimate of the purchase cost of the major equipment items required for the
process. The other costs being estimated as factors of the equipment cost and must be
determined as accurately as possible. [54]
The direct-cost items that are incurred in the construction of a plant, in addition to the cost
of equipment are: [54]
1. Equipment, including foundations and minor structural work.
2. Piping, including insulation and painting.
3. Electrical, power and lighting.
4. Instruments, local and control room.
5. Process buildings and structures.
6. Ancillary buildings, offices, laboratory buildings, workshops.
7. Storages, raw materials and finished product.
8. Utilities (Services), provision of plant for steam, water, air, firefighting services (if
not estimated separately).
9. Site, and site preparation.
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.
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2. Contractor’s fees, if a contractor is employed his fees (profit) would be added to

the total capital cost, it ranges from 5 per cent to 10 per cent of the direct costs.
3. Contingency allowance, this is an allowance built into the capital cost estimate to
cover for unforeseen circumstances (labor disputes, design errors, adverse
weather). Typically, 5 per cent to 10 per cent of the direct costs.
10.1.2 Estimation of Fixed Capital Investment

A systematic study of the cost is needed to start up and conduct business, even at minimal
stages. Fixed capital investment has a reusable value, it doesn’t deal with actual production
of products. It represents the total system cost, capital needed to purchase land, build the
necessary facilities and install the required equipment for system. [55]
For process involving only few pieces of equipment, estimating the capital cost of the plant
by hand is relatively easy. For complex process with many pieces of equipment, these
calculations become dull. The program Microsoft Excel was used in the processing
calculations. [56]
To find the fixed capital investment (FCI) using EXCEL program, the following steps is
used:
1. Estimating the purchased costs for main equipment (Cp). The price of equipment at
this point are related to price in 2001, which will be projected to 2017 using the
Chemical Engineering Plant Cost Index (CEPCI).
2. Estimating the pressure factor (Fp) and the material of construction factor (Fm) to
account for operating the equipment away from mild operating conditions.
3. Estimating the bare module factor (FBM), which reflects step (2) and the installed
equipment cost.
4. Calculating the bare module costs, which accounts for direct (equipment and
indirect costs for each piece of equipment in the plant.
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(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).
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10.1.3 Estimation of Fixed Capital Cost

The purchased cost and bare module cost of the major pieces of equipment by using
MICROSOFT EXCEL program, for the production of graphene.
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
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10.1.4 Grass Roots and Total Module Cost

The concepts of grass roots and total module cost were introduced in order to make
estimation of the total capital required to build the plant. The expression grass roots refer
to a completely new facility in which we start the construction essentially undeveloped
land. The expression total module refers to the cost of making small to moderate alternation
to an existing facility. [56]
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. Contingency are fee costs:

The contingency cost varies depending on the reliability of the cost data and completeness
of the process flow sheet available. This factor is included in the evaluation of the cost as
a protection against oversights and faulty information. Unless otherwise stated, values of
15% and 3% of the bare module cost are assumed for contingency costs and fees,
respectively. These are appropriate for systems that are well understood. Adding these
costs to the bare module cost provides the total module cost. [57]
1.18 ∑ (10.3)
2. Auxiliary Facilities Costs

These include costs for site development, auxiliary buildings, and off-sites and utilities.
These terms are generally unaffected by the materials of construction or the operating
pressure of the process. A review of costs for these auxiliary facilities by Miller gives a
range of approximately 20% to more than 100% of the bare module cost.
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)
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Using equation (10.1), (10.2) and the data of table 10.1, the grass root cost for production
of graphene process.
CGR = $570,908 generated using MICROSOFT EXCEL.
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).
10.2 Cost of Manufacturing (COM)

Manufacturing costs are the cost needed to convert raw material into products. There are
many elements that influent the cost of manufacturing such as: [58]
Direct manufacturing costs: costs that varies with production rate such as raw material or
might slight depend on production rate such as maintenance. When product demand drops,
production rate is reduced to less than the design capacity.
Fixed manufacturing costs: these are independent of change in the production rate and are
charged at constant rate even when the plant is not operating. They include property taxes,
insurance and depreciation.
General manufacturing expanses: these costs represent an overburden that is necessary to
carry out business function, which do not vary with production rate. They include
management, sales, financing, research functions and development.
To estimate the cost of manufacturing, the following cost items should be known: [58]
1- Fixed capital investment (FCI)
2- Cost of Operating Labor (COL)
3- Cost of Utilities (CUT)
4- Cost of Raw Materials (CRM)
5- Cost of waste treatment (CWT)
COM is calculated in MICROSOFT EXCEL without depreciation according to the
following equation:
1.23 2.73 0.18 (10.5)
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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
10.2.1 Cost of Operating Labor (COL)

The number of operators required to run the process per shift depends on the major
equipment exist in the plant. A single operator works 49 weeks a year on average, five days
a week, 8-hours shift a week for continuous process. However, a chemical plant operates
around 8322 hours per year (around 320 days a year on average). Which means that there
is around (8322/8) =1041 shifts per year approximately.
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.
Number of operators per shift: [58]
.
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
The labor cost is estimated using EXCEL to be ($194,511)
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10.2.2 Cost of Utilities (CUT)

The cost of utilities was estimated using EXCEL program. It was calculated for the
process.
Table 10.3: Cost of utilities estimation for production of graphene
Equipment Utility Used Actual Usage Annual Utility Cost

MIX-101 Electrical 94.1 KJ $1
C-101 Electrical 435.3 KJ $5
F-101 Electrical 3.7E-15 KW $0
D-101 Electrical 110000 KJ $1,183
MIX-102 Electrical 30.1 KJ $0
S-101 Electrical 3 KW $697
F-102 Electrical 9.8E-19 KW $0
D-102 Electrical 29000 KJ $312
Total =$2,197
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.
10.2.3 Cost of Raw Material (CRM)

Raw material is the total cost of all component parts currently in stock that are used in
process production. In most cases, raw material takes a huge part of the cost (35% - 85%
of 97 the total cost). Material used in graphene process are listed in table (10.4), price
($/Kg) were obtained from chemical market reporter. [59]
Table 10.4: Cost of raw material (generated using EXCEL)
Material Flow Rate [Kg/year] Price $/Kg Annual Cost

Na2SO4 54146.0 0.09 $4,873
H 2O 330159.0 0.002 $660
Acetone 199111.1 1.0 $199,111
HCl 69443.8 0.2 $11,493
Graphite 640 10.0 $6,400
Total (CRM) $222,538
144 | P a g e
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.
10.3 Revenue Estimation

Estimated revenue is the amount of money that a project generates during a specific
period.
Table 10.5: Cost of product
Material Flow Rate [Kg/year] Price $/Kg Annual Cost

Graphene 640 300000 $192,000,000
The Graphene process was expected to make revenue from selling Graphene product. The
total annual revenue was found to be $ 192,000,000.
10.4 Profitability Analysis

Profitability of project is involving both capital expenditures and yearly operating costs.
Several criteria for profitability. The three bases criteria used to assess profitability analysis
are: time, cash and interest rate. For each these bases, discounted or non-discounted
techniques may be considered. The non-discounted techniques do not consider the time
value of money and are not recommended for evaluating new, large projects. On the other
hand, discounted criteria is that for which the yearly cash flow is discounted back to time
145 | P a g e
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.
10.4.1 The Cumulative Cash Flow Diagram

Cumulative flow diagram is used to evaluate profitability. The inputs are the cash which
are paid for the plant design and construction, plant operation and that which is needed for
research and development. The cash outputs are the products from the process which are
goods for sale and cash returns. The net cash flow is the difference between the expenditure
and the earnings. The importance of the cash flow is that it gives a clear picture of the
timing of the earnings and the resources that are required for the project. [59]
EXCEL spread sheet is used to construct the cash flow diagram. The project life is assumed
to be 12-year, with a cost of land to be $ 400,000 in China. Moreover, the taxation rate is
20% and the annual interest rate is 10%. The depreciation method used in EXCEL. This
method uses the DDB (Double Declining Balance) method and switches to a straight-line
method when the latter yield greater deprecation allowance for that year. The diagram
below shows the project cash flow of the production of Graphene.
146 | P a g e
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
10.4.2 Cash Profitability Criteria

To calculate the discounted cash profitability criterion, we must introduce the Net Present
Value (NPV), the NPV method is a classic economic method for calculating the
investment.
It is a technique that recognize the time value of money. The NPV of project is greatly
affected by fixed capital investment. The NPV is calculation by converting all non-
discounted cash flow at each year to equivalent present worth (discounted cash flow) by
using the equation below:

(10.9)
147 | P a g e
10.4.3 Time Profitability Criteria

Another main factor used as a criterion for determining the success of a project
economically is the payback period. Payback period is the time required for the plant to
start gaining profit. This is indicated through an increase in the slope of the curve in the
cash flow diagram. To produce graphene, it is evident that the payback period is three years
after plant start-up and production starts.
Figure 10.2: The cumulative cash flow diagram for production of graphene
10.4.4 Interest Rate Profitability

The discounted profitability of the cumulative cash diagram for the production of
Graphene is shown in table (10.6). The results are from EXCEL spread sheet. It is shown
that the net present value is $ million.
Table 10.6: Discounted profitability criterion for the graphene production
Discounted Cash Flow Rate of Return 10.0%
Discounted Payback Period (years) 3
Net Present Value (millions) $727,255,403
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.
Safety of equipment and

materials taken into
consideration in order to
know how to deal with
it.
Safety & Hazard Prevention

11.1 Process Safety Analysis
All manufacturing processes are to some extent hazardous, but in chemical processes
there are additional, special hazards associated with the chemicals used also the process
conditions. Thus, aware must be considered of these hazards, and ensure, through the
application of sound engineering practice, that the risks are reduced to acceptable levels.
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.
Figure 11.1: Layers of safety
150 | P a g e


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.
11.1.2 Thermal Hazards

An exothermic reaction can lead to thermal runaway, which begins when the heat
produced by the reaction exceeds the heat removed. The surplus heat raises the temperature
of the reaction mass, which causes the rate of reaction to increase, but in our project the
amount of energy produced have no noticeable effect. [61]
11.1.3 Physical Hazards

Physical hazards associated with moving machine parts which cause injury to the workers.
Noise hazard is also a physical hazard to health and safety, long exposure to high noise levels
can cause permanent damage to hear. At lower levels, noise is a distraction and causes
fatigue.[62]
151 | P a g e


Figure 11.2: Flammability triangle for graphene production plant
11.2 Safety of Equipment

Materials movement and storage activities including load, transport and storage
equipment; should be fully integrated process for general safety standards and laws. These
Equipment should be daily checked if maintenance is required, also, it should work for its
specific purpose only, the design of a material handling system depends on the type and
the characteristics of the materials to be handled. [63]
152 | P a g e


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
Stoichiometric line equation for (O2):
4
0.8
1 4 1
Based on Raoult's law. The calculation of the operational conditions:

∗
( )
The mole fraction of Acetone in air at 20oC is calculated

.
0.245
0.596
0.159
153 | P a g e


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.
Table 11.1: Environmental and health impacts
Acetone HCl Sodium Sulfate Graphene powder

LC50 (mg/m3)
44000 1108 -- --
LD50 (mg/kg)
3000 900 5989 --
TSS (µg/m3)
-- -- 250 25
Eye irritation (mg/L)

500 250 90 0.0025
Odor threshold (ppm)

62 0.25-10 -- --
[H2O] (mg/L) 6.3 6.5-8.5 pH 1000–1200 --
11.4 Accident caused by hazards

 Inhalation of acetone while inspecting tanks or filters.
 Inhalation of Sodium Sulfate gas leaving the electric cell or mixers.
 Direct contact with solid Sodium Sulfate salt while loading or cleaning storage
tanks.
 Inhalation of Graphite or Graphene powder while emptying the tray after drying or
when packaging the product.
 Direct contact with HCl solution during inspecting its tank or moving the filter sheet.
154 | P a g e


 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.
11.4.2 Personnel hygiene

 No smoking must be allowed or the use of any source of fire or sparks.
 Eating and drinking are not allowed inside working place.
 Use working clothes and safe guards.
 Avoid touching, tasting or smelling any liquid or gas.
 Wash any part of body in case of contacting liquids or solids.
 Use face mask to prevent inhalation of gases, while working next to liquid sources
of gas or any other volatile liquids.
 Having a medical kit and an easy access to hospital for major or minor injuries
when required.
 Seeking clean air when inhaling any vapor with any dose.
 Rinsing eyes immediately with running water after contacting with any vapor or
liquid.
 Cleaning and covering any burns with clean water and bandages or any clean
clothing.
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
Graphite Sheet (g) Filter Paper (g) Product (g)
Concentration
Before After Before After
(mol/L)

0.5 3.4 3.07 1.46 1.7 0.24

1 3.5 2.89 1.487 2.058 0.571

1.5 3.6 2.97 1.47 2.1 0.63
Table A2: Results for the variation in voltage experiment
Graphite Sheet (g) Filter Paper (g) Product (g)
Voltage (V) Before After Before After

5 2.76 2.67 1.478 1.63 0.152

15 2.88 2.247 4.39 5.76 1.37

20 2.694 2.241 4.51 4.99 0.58
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 []
Table A3: Recorded transmittance readings from spectrophotometer (part 1)
Time (min) Graphene (0.1g) Graphene (0.3g)
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
Time (min) Graphene (0.1g) Graphene (0.3g) Graphene Graphene (0.3g)

(0.1g)
0 25 25 1 1
5 23 21 0.92 0.84
10 23 20 0.92 0.8
20 23 19 0.92 0.76
50 23 17 0.92 0.68
80 23 15 0.92 0.6
200 21 12 0.84 0.48
2 days 21 2.2 0.84 0.088
Table A5: Recorded transmittance readings from spectrophotometer (part 2)
Time (min) Graphene Coarse Activated Carbon Fine Activated Carbon
0 15 15 15
10 35 19 42
15 44 19 50
25 56 20 66
35 65 21 75
2 days 94 47 100
166 | P a g e

Appendix A

Table A6: Kinetics of adsorption calculations (part 2)
Concentration Final / Initial Concentration
Coarse Fine Coarse Fine

Time
Graphene Activated Activated Graphene Activated Activated
(min)
Carbon Carbon Carbon Carbon
0 10 10 10 1 1 1
10 5.5 8.5 4.5 0.55 0.85 0.45
15 4.1 8.5 3.5 0.41 0.85 0.35
25 2.8 8.25 1.8 0.28 0.825 0.18
35 1.9 8 1 0.19 0.8 0.1
2 days 0.1 4 0 0.01 0.4 0
Adsorption of Metals:
Table A7: Data shown on the spectrometer screen for lead adsorption
Concentration ppm %RSD ABS Mean Readings
Blank 0.00 0.001 0.000 0.001 0.001

Standard 1 5.00 0.6 0.145 0.145 0.146 0.145
Standard 2 10.00 0 0.263 0.263 0.264 0.263
Standard 3 15.00 0.3 0.328 0.327 0.327 0.329
Standard 4 25.00 0.7 0.530 0.534 0.530 0.526
167 | P a g e

Appendix A

Table A8: Data shown on the spectrometer screen for iron adsorption
Concentration ppm %RSD ABS Mean Readings
Blank 0.00 0.000 0.001 0.000 0.001

Standard 1 10.00 0.5 0.299 0.300 0.300 0.297
Standard 2 15.00 0.3 0.451 0.453 0.451 0.450
Standard 3 20.00 0.8 0.545 0.546 0.540 0.549
Standard 4 30.00 1.2 0.723 0.713 0.727 0.728
Standard 5 50.00 0.5 0.925 0.923 0.931 0.922
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:
Solving for weight:
∗ ∗ 1.5 ∗ 0.250 ∗ 142.04 ] = 53.265 g
B.1.1b Calculation of the moisture absorbed by the first filter paper:
Moisture on filter paper = 10.6 g (after filtration and washing, blank experiment #1)
Area of filter paper = 0.049 m2
Mass (g) Cumulative *10.6

Na2SO4 53.3 0.116 1.230
H2O 250 0.544 5.771
HCl 68.35875 0.149 1.578
H2O 12.5 0.027 0.289
H2O 75 0.163 1.731
Total 459.1588 1 10.6
After Filtration of Electrolyte:
53.3
∗ 10.6 1.23
459.1588
250
∗ 10.6 5.771
459.1588
After Washing with HCl:
68.35875
∗ 10.6 1.578
459.1588
12.5
∗ 10.6 0.289
459.1588
After Washing with H2O:
170 | P a g e

Appendix B

75
∗ 10.6 1.731
459.1588
B.1.1c Calculation of the moisture absorbed by the second filter paper:
After Filtration of Acetone:
Moisture on filter paper = 5.96 g (after washing with acetone, blank experiment #2)
5.96
B.1.1d Calculation for HCl:
Dilution of HCl:
30 75
62.5
36
Amount of HCl:
∗ ∗ 30 ∗ 0.0625 ∗ 36.458 ] = 68.3588 g
Amount of H2O:
0.075 0.0625 0.0125
∗ρ 0.0125 1000 12.5
B.1.1e Calculation for Acetone:
ρ ∗ 784 ∗ 0.25 196
171 | P a g e

Appendix B

B.1.2 Pilot Scale Calculations
B.1.2a Scale up of Raw Material:
0.0533 ∗ 1587 84.6
0.25 ∗ 1587 396.8
0.06836 ∗ 1587 108.506
, 0.0125 ∗ 1587 19.841
, 0.075 ∗ 1587 119.048
0.196 ∗ 1587 311.111
B.1.2b Calculation of the moisture absorbed by the first filter paper:
Moisture on filter paper = 10.6 g (after filtration and washing, blank experiment #1)
0.0106 ∗ 1587 16.8254
Mass (Kg) Cumulative *16.8254

Na2SO4 84.603 0.116 1.953
H 2O 396.825 0.544 9.161
HCl 108.506 0.149 2.505
H 2O 19.841 0.027 0.458
H 2O 119.048 0.163 2.748
Total 728.823 1 16.8254
After Filtration of Electrolyte:
84.603
∗ 16.8254
728.823
1.953
396.825
∗ 16.8254
728.823
9.161
After Washing with HCl:
172 | P a g e

Appendix B

108.506
∗ 16.8254
728.823
2.505
19.841
∗ 16.8254
728.826
0.458
After Washing with H2O:
119.048
∗ 16.8254
728.823
2.748
B.2 Energy Balance Calculations

B.2.1 Figures

Figure B1: Power Correlations for various impellers and baffles
173 | P a g e

Appendix B

Figure B2: Radiation losses from heated metal surface
B.2.2 Calculations
B.2.2a Mixer energy balance MIX-101:
0.176 2660 0.824 1000 467.5 824.3 1292 /
∗ ∗ 1292 ∗ 30 ∗ 0.1
2 ∗ 10
0.01975
Power number from figure A1 by intersecting curve 6 with Reynolds number.
Np = 0.3
∗ ∗ ∗
0.3 ∗ 1292 ∗ 30 ∗ 0.1 104.6
∗ 104.6 ∗ 900 /1000 94.1
94.1 2.7 96.8
B.2.2b Mixer energy balance MIX-102:
174 | P a g e

Appendix B

784 /
∗ ∗ 784 ∗ 20 ∗ 0.1
5 ∗ 10
0.000316
Power number from figure A1 by intersecting curve 4 with Reynolds number.
Np = 0.8
∗ ∗ ∗
0.8 ∗ 784 ∗ 20 ∗ 0.1 50.2
∗ 50.2 ∗ 600 /1000 30.1
30.1 1.77 31.87
B.2.2c Dryer energy balance D-101:
Method 1
3.748 100 ∗ 4.187 ∗ 100 20

ower needed A B 9.65
3600
2.5146 ∗ 2.1082 ∗ 1 5.3
0.947 1.17
1.0585 /
2 2
12 ∗ 1.0585 ∗ 1.004 ∗ 100 20
0.28
3600
9.65 5.3 0.28 15.2
Inlet 3.748 [Kg]

T(initial) 20 [oC]
T(final) 100 [oC]
Cp Water 4.187 [kJ/Kg.K]
Cp Air 1.004 [kJ/Kg.K]
Density of Air (20oC) 1.17 [Kg/m3]
Density of Air (100oC) 0.947 [Kg/m3]
Power needed A+B 9.653175022 kW
Power needed C1 5.30127972 kW
Power needed C2 0.283395733 kW
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
Figure B3: Mesh to Micron conversion chart
176 | P a g e

Appendix B

Figure B4: Suitable MOC for concentrated hydrochloric acid
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

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University of Jordan

Supervised by Dr. Ali Matar

‫”‪“IGNIS AURUM PROBAT‬‬

Keywords: Graphene, Electrochemical Reactor, Sodium Sulfate, Bag Filter,

Executive Summary III

List of Figures XVI

List of Tables XIX

Chapter One: Introduction 1

2.5 Preliminary Economical Analysis 19

Chapter Three: Laboratory Experiments 23

Chapter Four: Process Description 49

Chapter Five: Material Balance 57

Chapter Seven: Equipment Description and Design 81

Chapter Eight: Controlling Systems 101

Chapter Nine: Plant Layout 119

Chapter Ten: Profitability Analysis 135

Chapter Eleven: Safety and Hazard Prevention 149

Chapter Twelve: Conclusion and Recommendation 157

Symbol Description Unit (SI)

Heat Duty J/s

Chapter One: Introduction

Figure (2.4): History of Graphene Source 9

Chapter Three: Laboratory Experiments

Figure (3.3): In Lab Experiments 30

Chapter Five: Material Balance

Chapter Six: Energy Balance

Chapter Seven: Equipment Description and Design

Chapter Eight: Controlling Systems

Chapter Nine: Plant Layout

Figure (9.3): Steps to select a suitable site location 125

Figure (9.7): Production of graphene plant layout 131

Chapter Ten: Profitability Analysis

Chapter Eleven: Safety and Hazard Prevention

Chapter One: Introduction

Chapter Seven: Equipment Description and Design

Chapter Ten: Profitability Analysis

Table (10.5): Cost of product 145

Chapter Eleven: Safety and Environmental Analysis

Graphene is undoubtedly the most promising nanomaterial because of its unique

Figure 1.1: Projected graphene growth

Figure 2.2: Possible graphene applications

The study of graphene can be traced back to the 19th century,

Figure 2.3: Andre Geim and Konstantin Novoselov [12]

Geim and Novoselov first attempt to achieve thin flakes of

Source: Graphene Flagship Website [15]

As previously established, the exceptional properties of graphene qualifies it to be a good

5. Composites and Coatings

Method 1: Mechanical Exfoliation Ball Mill

Losses of material in the developed milling system mostly occurred as a result of

Figure 2.8: Schematic illustration of chemical vapor deposition [18]

Method 3: Liquid-phase exfoliation

This method of shear-exfoliation of graphite to yield defect-free graphene nanoplatelets

Production routes Advantages Challenges

High purity Usage of harsh conditions

Chemical Vapor Deposition Low waste disposal Specialized equipment

High energy consumption

Simple Low graphene yield

2.4.2 Demerit Selection Criteria

(1: Minor, 2: Moderately Low, 3: Moderately High, 4: High)

2.5.1 Cost of Materials

Table 2.3: Preliminary costs of major materials in the production of graphene

Materials Material Cost ($/kg)

Sodium Sulfate 0.1