Salman PDF

EH2248A/B
DESIGN PROJECT 1
SEPTEMBER 2018 – JANUARY 2019
PRODUCTION OF 50,000 METRIC TONNES PER YEAR OF
POLYVINYL CHLORIDE VIA PYROLYSIS OF ETHYLENE
DICHLORIDE WITH EFFICIENT WASTE TREATMENT PROCESSES
FINAL DESIGN PROJECT 1 REPORT

GROUP MEMBERS
MUHAMMAD SALMAN BIN SAMIN 2015430722
NUR SHAFIQAH BINTI JAMALUDDIN 2015429378
NOR ADILA BINTI MOHD. NASIR 2015408838
AKASHAH BIN ZABRI 2016691934
MOHAMAD HEIRY MOHD AZMI 2016691928
SUPERVISOR:
NUR FADZEELAH BINTI ABU KASSIM
FACULTY OF CHEMICAL ENGINEERING
UNIVERSITI TEKNOLOGI MARA
CAWANGAN PULAU PINANG
DECLARATION
“Thereby declare that this report is the result of my own work except for quotation
and summaries which have been duly acknowledge”
MUHAMMAD SALMAN BIN SAMIN MOHAMAD HEIRY MOHD AZMI

2015430722 2016691928
NUR SHAFIQAH BINTI JAMALUDDIN AKASHAH BIN ZABRI

2015429378 2016691962
NOR ADILA BINTI MOHD NASIR

2015408838
i
SUPERVISOR’S CERTIFICATION
“Thereby declare that I have read this thesis and in my own opinion this project report
is sufficient in terms of scope and quality for the award of the Bachelor in Chemical
Engineering (Hons).”
Signature : …………………………………………….
Name : NUR FADZEELAH ABU KASSIM
Date : 24 JUNE 2019
ii
AKNOWLEDGEMENT
In the name of Allah S.W.T my greatest appreciation and thanks to Him for rewarding
us with lots of perseverance and patience in enduring lots of obstacle throughout our
life. We would like to express our gratitude towards in any individuals who had given
us a chance to complete this chapter. Special thanks to Madam Nur Fadzeelah Binti
Abu Kassim who had being our supervisor and given us plenty of good advices. Not to
forget, we would like to thanks and acknowledge our deepest thanks to all group
members in helping each other’s to complete this report.
iii
TABLE OF CONTENTS
DECLARATION ...........................................................................................................I
SV SUBMISSION APPROVAL FORM DP 1 ...............................................................II
AKNOWLEDGEMENT ............................................................................................... III
TABLE OF CONTENTS ........................................................................................... IV
LIST OF FIGURES ................................................................................................... IX
LIST OF TABLES .................................................................................................... XII
EXECUTIVE SUMMARY ........................................................................................ XVI
CHAPTER 1 ........................................................................................................... 1-1
PROCESS BACKGROUND AND SELECTION ...................................................... 1-1
1.1 INTRODUCTION ...................................................................................... 1-1
1.1.1 About polyvinyl chloride (PVC) .......................................................... 1-1
1.1.2 Applications ....................................................................................... 1-4
1.1.3 Market Demand ................................................................................. 1-5
1.1.4 Raw Materials ................................................................................... 1-6
1.2 PROCESS BACKGROUND ..................................................................... 1-9
1.2.1 Ethylene Dichloride (EDC) Processes ............................................... 1-9
1.2.2 Synthesis of Vinyl Chloride Monomer (VCM) ....................................1-12
1.2.3 Polyvinyl Chloride (PVC) Processes .................................................1-17
1.3 PROCESS SELECTION..........................................................................1-22
1.3.1 Process Alternatives.........................................................................1-23
1.3.2 Concept Screening ...........................................................................1-26
1.3.3 Concept Scoring ...............................................................................1-27
1.4 CONCEPTUAL DESIGN AND FLOWSHEETING....................................1-30
1.4.1 Conceptual Design ...........................................................................1-30
1.4.2 Conceptual Flowsheeting .................................................................1-38
1.4.3 Polyvinyl Chloride Overall Process Flow Diagram (PFD) ..................1-45
1.5 PROCESS DETAILS ...............................................................................1-46

iv
1.5.1 Chemistry .........................................................................................1-46
1.5.2 Reaction Kinetics..............................................................................1-47
1.5.3 Thermodynamics ..............................................................................1-52
1.6 WASTE TREATMENT .............................................................................1-58
1.7 CONCLUSION ........................................................................................1-58
CHAPTER 2 ........................................................................................................... 2-1
MARKET ANALYSIS .............................................................................................. 2-1
2.0. ECONOMIC DATA/SUPPLY AND DEMAND ............................................... 2-1
2.1 Introduction ........................................................................................... 2-1
2.2 Applications of Polyvinyl Chloride ......................................................... 2-1
2.3 Global Consumption of Polyvinyl Chloride ............................................ 2-3
2.4 Production of Polyvinyl Chloride............................................................ 2-4
2.5 PRODUCTION RATE AND PROFITABILITY STUDY .............................. 2-7
2.5.1 Yearly Cost and Stream Factor ......................................................... 2-7
2.6 TOTAL CAPITAL INVESTMENT .............................................................. 2-7
2.7 OPERATING CAPITAL COST.................................................................2-16
2.7 Cost of Raw Material, CRM....................................................................2-16
2.8 Cost Operating Labor, COL ...................................................................2-17
2.9 Cost of Utilities, CUT .............................................................................2-19
2.8 OTHER MANUFACTURING COST .........................................................2-20
2.9 VARIABLE COST ....................................................................................2-22
2.10 BREAKEVEN ANALYSIS ........................................................................2-22
2.11 PAYBACK PERIOD (PBP) ......................................................................2-23
2.12 CONCLUSION ........................................................................................2-27
CHAPTER 3 ........................................................................................................... 3-1
SITE SELECTION .................................................................................................. 3-1
3.1 SITE SELECTION .................................................................................... 3-1
3.2 SITE SELECTION CRITERIA................................................................... 3-1
3.2.1 Raw materials Supply ........................................................................ 3-2
v
3.2.2 Transportation facilities and accessibility ........................................... 3-3
3.2.3 Availabilities of Utilities ...................................................................... 3-3
3.2.4 Availability of Suitable Land and Pricing ............................................ 3-3
3.2.5 Availability of labor ............................................................................ 3-3
3.2.6 Taxation and Government Incentives ................................................ 3-4
3.2.7 Local community consideration ......................................................... 3-4
3.3 SITE SELECTION EVALUATION ............................................................. 3-4
3.4 CONCLUSION ........................................................................................3-15
CHAPTER 4 ........................................................................................................... 4-1
4.1 INTRODUCTION ...................................................................................... 4-1
4.2 RELEVANT LAW, LEGISLATION, REGULATION AND ACT ................... 4-2
4.2.1 Factory and Machinery Act (FMA) 1967 ............................................ 4-2
4.2.2 Occupational Safety and Health Act (OSHA) 1994 ............................ 4-2
4.2.3 Environmental Quality Act (EQA) 1974.............................................. 4-3
4.3 WASTE IDENTIFICATION ....................................................................... 4-4
4.4 WASTE TREATMENT AND MANAGEMENT ........................................... 4-5
4.2.1 Flue Gas Treatment and Management .............................................. 4-5
4.2.2 Wastewater Treatment and Management .......................................... 4-8
4.5 HAZARD IDENTIFICATION, RISK ASSESSMENT AND RISK CONTROL

(HIRARC)............................................................................................................ 4-9
4.2.1 HIRARC PROCESS .......................................................................... 4-9
4.2.2 HAZARD IDENTIFICATION .............................................................4-10
4.2.3 RISK ASSESSMENT .......................................................................4-11
4.2.4 RISK CONTROL ..............................................................................4-13
4.2.5 HIRARC FORMS..............................................................................4-15
4.6 CONCLUSION ........................................................................................4-13
CHAPTER 5 ........................................................................................................... 5-1
5.1 INTRODUCTION ...................................................................................... 5-1
5.1.2 BASIS OF CALCULATION ................................................................ 5-2
vi
5.2 PROCESS FLOW DIAGRAM ................................................................... 5-3
5.3 PROCESS MASS BALANCE ON EACH UNIT ......................................... 5-7
5.3.1 BUBBLE COLUMN REACTOR (R-101) ............................................ 5-7
5.3.2 FURNACE (R-102) ...........................................................................5-10
5.3.3 DISTILLATION COLUMN (T-101) ....................................................5-15
5.3.4 DISTILLATION COLUMN (T-102) ....................................................5-19
5.3.5 POLYMERIZATION TANK ...............................................................5-15
5.3.6 STRIPPER COLUMN .......................................................................5-17
5.3.7 CENTRIFUGAL ................................................................................5-20
5.3.8 DRYER ............................................................................................5-23
6.1 INTRODUCTION ...................................................................................... 6-1
6.1.1 Assumption on Energy Balance......................................................... 6-1
6.2 EQUATION USED IN CALCULATIONS ................................................... 6-2
6.2.1 General Equation .............................................................................. 6-2
6.2.2 Equation for non-reactive process ..................................................... 6-2
6.2.3 Equation for reactive process ............................................................ 6-2
6.2.4 Phase Change Equation.................................................................... 6-2
6.2.5 Heat Capacity Equation ..................................................................... 6-3
6.2.6 Pressure Change equation in liquid phase ........................................ 6-3
6.3 SAMPLE CALCULATION FOR ENERGY BALANCE OF EACH UNIT ..... 6-7
6.3.1 Reactor (R-101) ................................................................................ 6-7
6.3.2 Pump (P-102) ...................................................................................6-10
6.3.3 Heater (E-102) .................................................................................6-11
6.3.4 Furnace (R-102) ...............................................................................6-13
6.3.5 Quench Tank (S-101) .......................................................................6-15
6.3.6 Valve (V-101) ...................................................................................6-18
6.3.7 Cooler (E-105)..................................................................................6-19
6.3.8 HCl Column (T-101) .........................................................................6-21
6.3.9 VC Column (T-102) ..........................................................................6-23
vii
6.3.10 Reactor (R-103) ...............................................................................6-25
6.4 CONCLUSION ........................................................................................6-27
CHAPTER 7 ........................................................................................................... 7-1
7.1 INTRODUCTION ...................................................................................... 7-1
7.2 PROCESS DESCRIPTION ...................................................................... 7-4
7.3 PROPERTY METHOD ............................................................................. 7-6
7.4 SET-UP SIMULATION MODEL ................................................................ 7-8
7.5 RAW MATERIAL FEED STREAM DESCRIPTION ..................................... 10
7.6 DESIGN OF REACTOR ..........................................................................7-11
7.6.1 Direct Chlorination Reactor (R-101) .................................................7-11
7.6.2 Pyrolysis Reactor(R-102) .................................................................7-12
7.7 QUENCHING VESSEL............................................................................7-14
7.8 DISTILLATION COLUMN ........................................................................7-15
7.8.1 Distillation Column 1 (T-101) ............................................................7-15
7.8.2 Distillation Column 2 (T-102) ............................................................7-18
7.9 RECYCLE AND WASTE STREAM..........................................................7-20
7.10 STREAM RESULT SUMMARY ...............................................................7-21
7.11 COMPARISON OF MANUAL CALCULATION AND WITH ASPEN PLUS7-28
7.12 CONCLUSION ........................................................................................7-29
REFERENCES ................................................................................................... 236
APPENDIX.......................................................................................................... 244
Appendix A ...................................................................................................... 244
Appendix B-1 ................................................................................................... 247
Appendix B-2 ................................................................................................... 250
Appendix C-1................................................................................................... 257
Appendix C-2................................................................................................... 260
viii
LIST OF FIGURES
Figure 1. 1: Molecular structure of vinyl chloride monomer (VCM) [3]. .................... 1-1
Figure 1. 2: Polymerization of vinyl chloride monomer (VCM) to polyvinyl chloride
(PVC) [6]. ............................................................................................................... 1-3
Figure 1. 3: Structure image of VCM and PVC [7]................................................... 1-3
Figure 1. 4: Global Market Demand of Polyvinyl Chloride (PVC) [9]. ...................... 1-5
Figure 1. 5: Production & Demand of Polyvinyl Chloride (PVC) Resin in Asian Region
[1]. .......................................................................................................................... 1-6
Figure 1. 6: Process flow diagram of direct chlorination of ethylene [16]. ...............1-10
Figure 1. 7: Oxychlorination process scheme showing the gas recycle for oxygen-
based alternative [19]. ...........................................................................................1-11
Figure 1. 8: Production of VCM via Acetylene-HCl route. ......................................1-12
Figure 1. 9: Schematic representation of the 1,2-dichloroethane (EDC) cracking
furnace. The feed is preheated and vaporised in the convection section while the
reaction occurs in the radiation section [16]. ..........................................................1-14
Figure 1. 10: Schematic representation of the suspension polymerization process of
vinyl chloride monomer for production of polyvinyl chloride [29].............................1-18
Figure 1. 11: Schematic representation of the emulsion polymerization process of vinyl
chloride monomer for production of polyvinyl chloride [29].....................................1-20
Figure 1. 12: Schematic representation of the bulk polymerization process of vinyl
chloride monomer for production of polyvinyl chloride [29].....................................1-21
Figure 1. 13: Input-output structure of Reaction 1. .................................................1-32
Figure 1. 14: Input-output structure of Reaction 2. .................................................1-33
Figure 1. 15: Input-Output of Reaction 3. ...............................................................1-33
Figure 1. 16: General plant structure for PVC plant design. ...................................1-35
Figure 1. 1.17: BFD of separators arrangement in PVC production plant design. ..1-35
Figure 1. 18: Recycling structure for polyvinyl chloride plant design ......................1-36
Figure 1. 19: Heat exchanger network for the design of polyvinyl chloride plant. ...1-37
Figure 1. 20: Conceptual Flowhseeting Alternative 1 for PVC production plant. .....1-39
Figure 1. 23: Overall process flow diagram of PVC plant. ......................................1-45
Figure 1. 24: The changes of phase of an ice from solid to gas [6]. .......................1-54
Figure 1. 25: The energy profile for endothermic reaction. .....................................1-56
ix
Figure 1. 26 : Generic potential energy diagram showing the effect of a catalyst in a
hypothetical exothermic chemical reaction X (acetylene) + Y (chlorine) to give Z (EDC)
[6] ..........................................................................................................................1-58
Figure 1. 27: Block flow diagram of wastewater treatment process for PVC plant. [71]
..............................................................................................................................1-60
Figure 2. 1: PVC application …………………………………………………………….2-1
Figure 2. 2: world consumption of polyvinyl chloride in 2016 [5] ............................. 2-3
Figure 2. 3: Malaysia PVC Demand, Exports, Imports and Capacity ...................... 2-4
Figure 2. 4: Malaysia PVC capacity ........................................................................ 2-6
Figure 2. 5: Graph Cash Flow Analysis for discounted data...................................2-23
Figure 2. 6: Cash Flow Analysis discounted criteria ...............................................2-24
Figure 2. 7: Cash flow analysis non-discounted criteria .........................................2-24
Figure 3. 1: Proposed site location in Teluk Kalong industrial area………………….3-5
Figure 3. 2: Proposed site location in Kerteh industrial area ................................... 3-5
Figure 3. 3: Proposed site location in Tanjung Langsat industrial area ................... 3-6
Figure 3. 4: Proposed site location in Gebeng industrial area ................................. 3-6
Figure 3. 5: Proposed site location in Pengerang industrial area ........................... 3-7
Figure 4. 1: Block flow diagram of the limestone scrubbing method ………………...4-5
Figure 4. 2: Block flow diagram of WWTP of PVC [69]. .......................................... 4-8
Figure 4. 3: Flowchart of HIRARCH Process [118]. .................................................. 10
Figure 4. 4: NIOSH Hierarchy of Controls [122]. ....................................................4-14
Figure 5. 1: Process Flow Diagram (Polyvivnyl Vhloride)……………………………..5-3
Figure 5. 2: Schematic diagram of Bubble Column Reactor (R-101)....................... 5-7
Figure 5. 3: Schematic diagram of the furnace reactor (R-102) .............................5-10
Figure 5. 4: Schematic diagram of distillation column T-101 ..................................5-15
Figure 5. 5: Schematic diagram for distillation column T-102 .................................5-19
Figure 5. 6: schematic diagram of Polymerization tank ..........................................5-15
Figure 5. 7: Schematic diagram of stripper column ................................................5-17
Figure 5. 8: Schematic diagram of Centrifugal .......................................................5-20
Figure 5. 9: Schematic diagram of Dryer ...............................................................5-23
Figure 6. 1: Process Flow Diagram (PFD) for the Production of Polyvinyl chloride
production with waste treatment facilities……………………………………………….6-6
Figure 6. 2: Bubble Column Reactor ....................................................................... 6-7
Figure 6. 3: Pump ..................................................................................................6-10
Figure 6.4:Heater ..................................................................................................6-11
Figure 6. 5: Furnace ..............................................................................................6-13
Figure 6. 6: Quench Tank ......................................................................................6-15
x
Figure 6. 7: Valve ..................................................................................................6-18
Figure 6. 8: Cooler .................................................................................................6-19
Figure 6. 9: HCl Column ........................................................................................6-21
Figure 6. 10: VCM Column ....................................................................................6-23
Figure 6. 11: Polymerization reactor ......................................................................6-25
Figure 7. 1: Rigorous process flow diagram of vinyl chloride monomer (VCM)
production used in Aspen Plus simulation………………………………………………7-4
Figure 7. 2: Guideline for choosing property method [2]. ........................................ 7-7
Figure 7. 3: Procedure for polar non-electrolyte compound [2]. .............................. 7-8
Figure 7. 4: METCBAR unit set selected for the process. ....................................... 7-9
Figure 7. 5: Component specification selected for the process. .............................. 7-9
Figure 7. 6: Method Selection ................................................................................7-10
Figure 7. 7: Ethylene and chlorine feed stream. .....................................................7-10
Figure 7. 8: Direct chlorination reactor (R-101). .....................................................7-11
Figure 7. 9: Reactor (R-102) feed preparation unit.................................................7-13
Figure 7. 10: Pyrolysis reactor (R-102) in VCM process model simulation .............7-13
Figure 7. 11: Cooler (E-104) that is used to represent quenching vessel. ..............7-15
Figure 7. 12:Distillation column (T-101) feed preparation unit. ...............................7-16
Figure 7. 13: Distillation column 1 RadFrac block (T-101)......................................7-16
Figure 7. 14: Distillation column 1 (T-101) top product setting. ..............................7-17
Figure 7. 15: Distillation column 2 (T-102) feed preparation unit. ...........................7-18
Figure 7. 16: Distillation column 2 RadFrac block (T-101)......................................7-19
Figure 7. 17: Distillation column 2 (T-102) top product setting. ..............................7-20
Figure 7. 18: Splitter used to split recycle (stream 26) and waste streams (stream 25).
..............................................................................................................................7-20
xi
LIST OF TABLES
Table 1.1: Physical properties of vinyl chloride [3]. ................................................. 1-2

Table 1.2 : Physical properties of Polyvinyl Chloride (PVC) [6], [7]. ........................ 1-3
Table 1.3: Physical and chemical properties of ethylene [11].................................. 1-7
Table 1.4: Physical and chemical properties of chlorine [12]................................... 1-7
Table 1.5: Physical and chemical properties of water [13]. ..................................... 1-8
Table 1.6: Advantages and disadvantages of direct chlorination process. .............. 1-9
Table 1.7 : Advantage and disadvantages of oxychlorination process [14]. ...........1-11
Table 1.8 Summary of advantage and disadvantages of acetylene process. .........1-13
Table 1.9: Summary of advantages and disadvantages of EDC Pyrolysis process. .. 1-
16
Table 1.10: Advantages and disadvantages of suspension polymerization process
[23]–[25]. ...............................................................................................................1-18
Table 1.11: Advantages and disadvantages of emulsion polymerization process [23],
[25], [27], [28]. .......................................................................................................1-19
Table 1.12: Advantages and disadvantages of bulk polymerization process [23]–[25].
..............................................................................................................................1-21
Table 1.13: Description for criterion selection for process comparison in process
selection. ...............................................................................................................1-23
Table 1.14: Process comparison of direct chlorination and oxychlorination for EDC
formation. ..............................................................................................................1-23
Table 1.15: Process comparison of pyrolysis and vinyilation of acetylene for VCM
formation. ..............................................................................................................1-24
Table 1.16: Process comparison for polymerization method for PVC formation. ....1-25
Table 1.17: Screening concept for EDC, VCM and PVC formation process alternatives.
..............................................................................................................................1-26
Table 1.18: Scoring concept for EDC, VCM and PVC formation process alternatives.
..............................................................................................................................1-28
Table 1.19: Comparison of batch and continuous processes [49]. .........................1-31
Table 1.20: Operating condition in Reaction 1. ......................................................1-32
Table 1.21: Operating condition Reaction 2. ..........................................................1-33
Table 1.22: Operating condition Reaction 3. ..........................................................1-34
Table 1.23: Stoichiometry table for Reaction 1. .....................................................1-51
Table 1.24: Stoichiometry table for Reaction 2. .....................................................1-52
xii
Table 1.25: Thermodynamic properties of substances used in PVC production process.
..............................................................................................................................1-53
Table 2.1: PVC resin data in Malaysia .................................................................... 2-5
Table 2.2: Cost of every component ....................................................................... 2-8
Table 2.3: Direct Cost ............................................................................................2-14
Table 2.4: Indirect Cost .........................................................................................2-15
Table 2.5: Number of Non-Particulate Processing Steps .......................................2-17
Table 2.6: Cost of Utilities ......................................................................................2-19
Table 2.7: Direct Manufacturing Cost ....................................................................2-20
Table 2.8: Indirect Manufacturing Cost ..................................................................2-21
Table 2.9: General Variable Cost...........................................................................2-22
Table 2.10: Cash Flow Analysis table ....................................................................2-25
Table 3. 1: List of Site Selection Criterion ............................................................... 3-2
Table 3. 2: Raw materials supplier.......................................................................... 3-2
Table 3. 3: Summary of comparison criteria between site locations ........................ 3-8
Table 3. 4: Screening method table .......................................................................3-13
Table 3. 5: Scoring method table ...........................................................................3-14
Table 4.1: Typical composition (by mass) of natural and FGD [108]. ...................... 4-7
Table 4.2: Likelihood of an event [112]. .................................................................4-11
Table 4.3: Severity of an event [112]. ....................................................................4-12
Table 4.4: Risk Assessment Matrix [113]. ..............................................................4-12
Table 4.5: Indication of risk level [113]. ..................................................................4-12
Table 4.6: Control Measure Matrix [112]. ...............................................................4-14
Table 4.7: HIRARC form of Ethylene. ....................................................................4-16
Table 4.8: HIRARC form of Ethylene. ....................................................................4-17
Table 4.9: HIRARC form of Chlorine. .....................................................................4-18
Table 4.10: HIRARC form of Ethelylene Dichloride. ...............................................4-19
Table 4.11: HIRARC form of Vinyl Chloride. ..........................................................4-20
Table 4.12: HIRARC form of Hydrogen Chloride. ..................................................4-21
Table 4.13: HIRARC form of Polyvinyl Chloride. ....................................................4-22
Table 4.14: HIRARC form of Benzoyl Peroxide. ....................................................4-23
Table 4.15: HIRARC form of Ferric Choride...........................................................4-24
Table 4.16: HIRARC form of Water. ......................................................................4-25
Table 5. 1: Overall Stream Data Table for Polyvinyl Chloride ................................. 5-4
Table 5. 2: The molar flowrate and mass flowrate of inlet and outlet stream of the
reactor .................................................................................................................... 5-9
xiii
reactor ...................................................................................................................5-14
Table 5. 4: Summary of molar flowrate of inlet and outlet streams of the distillation unit
..............................................................................................................................5-18
..............................................................................................................................5-14
Table 5. 6: Summary table flowrate of polymerization tank ....................................5-17
Table 5. 7: Summary flowrate of stripper tank........................................................5-19
Table 5. 8: Summary flowrate for centrifugal..........................................................5-22
Table 5. 9: Summary flowrate of dryer ...................................................................5-24
Table 6. 1: Main properties of chemical compounds in polyvinyl chloride production 6-
4
Table 6. 2: Specific heat capacity constant for liquid components in polyvinyl chloride
production .............................................................................................................. 6-5
Table 6. 3: Specific heat capacity of PVC ............................................................... 6-5
Table 6. 4: Inlet and output enthalpy table for bubble column reactor ..................... 6-7
Table 6. 5: Energy balance table for bubble column reactor ................................... 6-7
Table 6. 6: Inlet and output enthalpy table for heater .............................................6-11
Table 6. 7: Energy balance table for heater ...........................................................6-11
Table 6. 8: Inlet and output enthalpy table for furnace ...........................................6-13
Table 6. 9: Energy balance for furnace ..................................................................6-14
Table 6. 10: Input and output enthalphy for Quench Tank .....................................6-16
Table 6. 11: Energy balance for Quench Tank.......................................................6-16
Table 6. 12: Inlet and outlet enthalpy for cooler .....................................................6-19
Table 6. 13: Energy balance for cooler ..................................................................6-19
Table 6. 14: Inlet outlet enthalpy HCl column.........................................................6-21
Table 6. 15: Energy balance for HCl Column .........................................................6-21
Table 6. 16: Inlet outlet enthalpy VC column..........................................................6-23
Table 6. 17: Energy balance for VC Column ..........................................................6-23
Table 6. 18: Inlet outlet enthalpy table and energy balance for stream 17 and 18 ..6-25
Table 6. 19: Inlet outlet enthalpy table and energy balance for stream 19 and 20 ..6-26
Table 6. 20: List of equipment and total energy .....................................................6-27
Table 7.1: Stream information at reactor (R-101). ..................................................7-11
Table 7.2: Stream information at reactor 2 (R-102). ...............................................7-14
Table 7.3: Stream information at distillation column RadFrac block (T-101). .........7-17
Table 7.4: Stream information at distillation column (T-102). .................................7-19
Table 7.5: Stream information at splitter (M-103). ..................................................7-21
xiv
Table 7.6: Stream results summary. ......................................................................7-21
Table 7.7: Summary of mass flowrate of output streams on manual mass balance
calculation and Aspen Plus....................................................................................7-28
xv
EXECUTIVE SUMMARY
The propose of this project is to produce 50,000 metric tonne per annum (mtpa)
polyvinyl chloride (PVC) with efficient waste treatment system. PVC is the third most
produced commodity chemical in the world, only surpassed by polyethylene and
polypropylene with 40 million tonnes per annum been produced across the globe. The
properties of vinyl is suitable for the production of construction materials like siding and
windows frames that are extremely durable, affordable, and help in conserving energy
for heating and cooling at home. In fact, vinyl windows have three times the heat
insulation of aluminium windows which make PVC is highly demanded
nowadays.Market analysis is an important component to determine the market
potential of PVC for different segments of consumers. From the analysis, PVC can be
segregated across a broad range of industries due to the demand of PVC is increasing.
This report was focusing on the evaluation of economics analysis of polyvinyl chloride
production using CAPCOST. The polyvinyl chloride production plant will get the profit
after producing 5,218.33 tonne of polyvinyl chloride. Site location is also one of the
important decisions in designing a polyvinyl chloride plant. Kerteh which is located in
Terengganu was selected as the site location for PVC selected since it meets all major
criteria as a petrochemical plant compared to other proposed site locations which in
Pengerang (Johor), Tanjung Langsat (Johor), Gebeng (Pahang) and Telok Kalong
(Terengganu).Environmental and safety considerations is another criterion that must
be acknowledged before a chemical plant is built. In design project, relevant law,
legislation and regulation related to PVC production plant are identified and study
Hazard identification, risk assessment and risk control (HIRARC) for all chemicals
related to the process are acknowledged by the assessment made on HIRARC forms.
Also, production wastes and unwanted products from the process are identified before
constructing the plant and best methods of treatment and management are determined
in order to reduce the impact of PVC production towards the environment. The fifth
chapter of this report is focusing on the mass balance for the plant of PVC. The
production of PVC based on mass balance was 1130.497 kg/hr with molecular weight
of 62.5 kg/kmol. This was proved by some of estimation and calculation made in this
chapter. Energy balance for production polyvinyl chloride plant was calculated to
determine the energy requirement for the process plant. In order to get the energy
requirement, the enthalpies for each chemical species involved in polyvinyl chloride
production must determine first. From the calculated energy balance for polyvinyl
chloride plant, units such as heater (E-102), furnace (R-102) are undergoes
endothermic process since all the units absorb heat whereas Bubble column reactor
(R-101), quench tank (S-101), cooler (E-105), distillation column (T-101 and T-102)
undergo exothermic process. Process model simulation was generated using Aspen
Plus V8.8 software. However, only process model up to production of VCM is covered
in the simulation section as polymerization process required different software called
Aspen Polymer. Based on the simulation made, VCM with purity higher than 90% is
achieved using rigorous Aspen simulation model such as RPlug and RadFrac. In
comparison with the manual calculation made in chapter five, an acceptable amount of
5.5% calculation error is calculated.
xvi
CHAPTER 1
PROCESS BACKGROUND AND SELECTION
1.1 INTRODUCTION
1.1.1 About polyvinyl chloride (PVC)
Polyvinyl chloride, known as PVC, is one of the most widely produced and
chemical industry-valuable polymers worldwide. Nowadays, PVC is the world’s third-
most widely produced synthetic plastic polymer, after polyethylene and polypropylene
with 40 million tonnes of PVC have been produced per year [1]. PVC has relatively
good mechanical properties, durability, stability, and processability that make it has a
wide range of consumer products such as pipes, packaging, cables and toys. As some
products require higher ductility while other require higher tensile strength or impact
resistance, the required properties of PVC can slightly differ according to the finishing
product [2]. Vinyl chloride is a monomer of polyvinyl chloride. Structure and properties
of vinyl chloride is shown in Figure 1.1 and Table 1.1.
Figure 1. 1: Molecular structure of vinyl chloride monomer (VCM) [3].
1-1
Table 1. 1: Physical properties of vinyl chloride [3].
Properties Description
IUPAC Name Chloroethene
Chemical Formula Monomer: C2H3Cl
Polymer: (C2H3Cl)n
Colour Colourless
Odour Odourless
Physical State Gas
Molecular Weight 62.496 kg/kmol
Density 8 g/L
Boiling Point -13°C
Melting Point -154°C
Flash Point -78°C
Auto-Ignition Temperature 472°C
Solubility Slightly soluble in water.
Soluble in ethanol.
Very soluble in ethyl ether.
PVC is produced from vinyl chloride monomer (VCM) via polymerization

reaction. Polymerization is a chemical reaction which combines small monomer
molecules to form large chain-like molecules called polymers such as PVC. Figure 1.2
and Figure 1.3 shows the reaction of VCM to produce PVC [4]. In polymerization
reaction, PVC is formed in the presence of water, suspending agents, initiators and at
a controlled temperature. Approximately equal volumes of water and VCM are piped
into the autoclave creating the suspension which begins the polymerization. Table 1.2
shows the properties of common PVC. VCM and water are introduced in the reactor
along with a polymerization initiator and other additives. To maintain the suspension
and ensure a uniform particle size of the PVC resin, the contents of the reaction vessel
are pressurized and continually mixed. The reaction requires cooling as it is the
exothermic reaction. Water is continually added as the volume is reduced during the
reaction to maintain the suspension [5].
1-2
Figure 1. 2: Polymerization of vinyl chloride monomer (VCM) to polyvinyl chloride
(PVC) [6].
Figure 1. 3: Structure image of VCM and PVC [7].
Table 1. 2 : Physical properties of Polyvinyl Chloride (PVC) [6], [7].

Properties Rigid PVC Flexible PVC
Density [kg/m3] 1.3 – 1.45 1.1 – 1.35

Melting point [°C] 260 100
Tensile strength [MPa] 34 – 62 6.9 – 25

Young’s modulus [GPa] 3.4
Flextural strength [MPa] 72
Compression strength [MPa] 66
Thermal conductivity [W/(m.K)] 0.14 – 0.28 0.14 – 0.17
Resistivity [Ω m] 1016 1012 - 1015
Coefficient of thermal expansion 5*10-5

[mm/(mm.°C)]
1-3
1.1.2 Applications
The production of PVC usually comes in two basic forms which are rigid and
flexible. It is depending on the end user requirement. The rigid form of PVC are used
in construction for windows frame, electrical wiring and cables, piping and the others.
The properties of vinyl help produce siding and windows frames that are extremely
durable, affordable, and help conserve energy when heating and cooling homes. In
fact, vinyl windows have three times the heat insulation of aluminium windows which
make PVC is highly demanded nowadays. Vinyl also is able to withstand tough
conditions behind building walls such as exposure to changing temperatures and
dampness which are very useful for the life of the building. As a result, it is one of the
most prevalent and trusted materials used in electrical wiring and cables. PVC helps
conserve energy and water by creating virtually leak-free pipes that are not prone to
corrosion and resist environmental stress. In fact, PVC breakage rates are as low as
one percent of the breakage rates of cast metal systems. The lack of build-up in PVC
piping improves functionality and increases energy efficiency. Therefore, it is one of
the most prevalent and trusted materials used in electrical wiring and cables.
Flexible PVC end use are used in packaging, healthcare sector, household
products and the others. As the flexible PVC is durable, dependable and light weight,
it helps packaging by maintaining the integrity of the products inside, including
medicines. In healthcare sector, flexible PVC also play vital role for example in
dispensing life-saving medicine through IV bags and medical tubing. The advent of the
PVC blood-collection has is a significant breakthrough because blood bags are flexible
and unbreakable, enhancing the development of ambulatory medicine and serving as
the foundation for modern blood banks. The durability and water resistance properties
of PVC make it ideal for rain coats, boots and shower curtains [5]. The most important
applications for PVC are pipes and conduits, demanding over 16.1 million tonnes in
2016. It also mostly used for window frames, doors, sun protection applications,
facades and other cladding [8].
1-4
1.1.3 Market Demand
Global Market Demand has witnessed continuous growth in the recent years.
The market demand has increased from 38.3 million tons in 2013 to 41.3 million tons
in 2016 as shown in the Figure 1.4 [7].
Figure 1. 4: Global Market Demand of Polyvinyl Chloride (PVC) [9].
Market drivers contribute for this growth in demand by include demand from
end segment markets such as construction, automotive, packaging, footwear, medical
and the others. The PVC’s unique properties such as high performance, lightweight
and durability increase its demand from many sectors. The continuously research and
innovation that have been done for usage of this material in different forms or as the
replacement also fuel the market demand as shown in Figure 1.5 below.
1-5
Figure 1. 5: Production & Demand of Polyvinyl Chloride (PVC) Resin in Asian Region
[1].
Asia-Pacific region is the biggest market of PVC. In 2014, Taiwan were the
largest producer and consumer of polyvinyl chloride (PVC) polymer. During this period,
Taiwan, India, South Korea and Malaysia consumed more PVC polymer than its
production while Japan and Thailand had a surplus production than their domestic
demand [1].
The Malaysia plastics market was estimated at USD 3,305.39 million, by

revenue, in 2017 and is likely to expand at an estimated CAGR of 5.27%, during the
forecast period 2018-2023. The Malaysia plastics market is expected to show healthy
growth in the near future, due to the rising demand from the food and beverages and
pharmaceuticals industries. Additionally, the growing demand for electronic products
is also expected to propel the demand in the Malaysia market [9].
1.1.4 Raw Materials
In this plant design, production of polyvinyl chloride (PVC) will be introduced

from direct chlorination process. This process will involve the reaction between two
types of raw materials which are ethylene and chlorine. Ethylene which also known as
ethane is an organic compound with a chemical formula of C2H4 or H2C=CH2. Ethylene
is a colourless flammable gas with a sweet odour and taste. Meanwhile, chlorine is a
pure chemical element which is a part of the halogen series in the chemical periodic
table. Chlorine is a highly irritating, greenish-yellow gaseous halogen, capable of
1-6
combining with nearly all other elements, produced principally by electrolysis of sodium
chloride [10]. Direct chlorination of ethylene will produce ethylene dichloride (EDC)
which will then undergo decomposition process to produce vinyl chloride monomer
(VCM). This compound produced then will be polymerized into polyvinyl chloride
(PVC). Polymerization of VCM into PVC requires water which will allows initial VCM
dispersion to a mist of fine droplets before agglomeration to the final PVC grains, as
well as helps in removing the heat of reaction [4]. Table 1.3, Table 1.4 and Table 1.5
show the physical and chemical properties of raw materials used to produce PVC.
Table 1. 3: Physical and chemical properties of ethylene [11].

IUPAC Name Ethylene
Chemical Formula C2H4
Colour Colourless
Odour Sweet
Physical State Gas
Density 0.569 g/L
Flash Point 341°C
Auto-Ignition Temperature 490°C
Solubility 131 mg/L at 25°C in water
Table 1. 4: Physical and chemical properties of chlorine [12].

IUPAC Name Chlorine
Chemical Formula Cl2
Colour Greenish yellow
Odour Pungent suffocating
Physical State Gas
Density 2.898 g/L
1-7
Flash Point Not flammable
Auto-Ignition Temperature Not flammable
Solubility 6,300 mg/L at 25°C in water
Table 1. 5: Physical and chemical properties of water [13].

IUPAC Name Water
Chemical Formula H2O
Colour Colourless
Odour Odourless
Physical State Liquid
Density 997 g/L
Boiling Point 100 °C
Melting Point 0.00 °C
Flash Point Non-flammable
Auto-Ignition Temperature Non-flammable
1-8
1.2 PROCESS BACKGROUND
1.2.1 Ethylene Dichloride (EDC) Processes
1.2.1.1 Direct Chlorination
Chlorination of ehylene can be performed directly using chlorine with the

presence of a Lewis acid catalyst. The most commonly used catalyst is iron (III) chloride
(FeCl3). Figure 1.6 shows the process flow diagram for direct chlorination reaction.
Although the feed is clearly in vapour phase, the chlorination process is carried out
exclusively in the liquid phase. The conversion of liquid phase direct chlorination is
almost 100% with the possiblity of 99% selectivity [14]. Table 1.6 shows the strength
and weakness of direct chlorination process.
Table 1. 6: Advantages and disadvantages of direct chlorination process.

Advantages Disadvantages
By inhibiting the secondary reactions with small The formation of a larger

amounts of oxygen that often present in the chlorine spectrum of impurities
produced by electrolysis, the selectivity to EDC may might complicate even
increase [15]. more the EDC purification
[15].
The amount of heat that being released from the

reaction can be recovered and collected. The
production of 1 ton of 1,2-dichloroethane is enough to
generate approximately 1 ton of steam, according to
[16].
The reaction condition in anhydrous condition and

relatively low temperature make the carbon steel
material can be used as construction material. This
really help in term of the economical aspect [14].
1-9
Figure 1. 6: Process flow diagram of direct chlorination of ethylene [16].
1.2.1.2 Oxychlorination
The oxychlorination reaction shown in equation 1.1 occurs in gas phase in order
to avoid corrosive problem due to the presence of acid aqueous solutions. Liquid phase
oxychlorination has no industrial applications. Based on Figure 1.7, gaseous ethylene
and oxygen react with hydrogen chloride, which has been produced from the vinyl
chloride purification section, in presence of a heterogeneous catalyst, usually copper
(II) chloride, CuCl2. Typical values of selectivity and conversion are lower with respect
to the direct chlorination. Equation 1.2 shows the side products of 1,1,2-trichloroethane
is produced from further chlorination of 1,2-dichloroethane and carbon oxides coming
from ethylene combustion. Reaction in equation 1.3 represents the complete
combustion of ethylene to carbon dioxide. The strength and weakness of
oxychlorination process is shown in the Table 1.7.
CH2 =CH2 + 2HCl + 0.5 O2 → ClCH2-CH2 Cl + H2 O (1.1)
ClCH2-CH2 Cl + HCl + 0.5 O2 → ClCH2 -CHCl2 + H2 O (1.2)
CH2 =CH2 + 3O2 → 2CO2 + 2H2 O (1.3)
1-10
Table 1. 7 : Advantage and disadvantages of oxychlorination process [14].
Advantage Disadvantages
Polymerization grade ethylene is Feed composition changes according to

supplied in order to minimize the by- the process configuration for instance,
product formation and purification oxygen can supply in both as pure
problems. oxygen or as air. In term of economical,
it is highly cost process.
Produced more by-products that can be

found as traces in the outlet stream such
as 1,1-dichloroethane,
monochloroethane, etrachloroethane,
trichloroethylenes, vinyl chloride,
acetaldehyde and other chlorinated
derivatives.
Amount of acetylene can affect

selectivity of oxychlorination reactor.
Figure 1. 7: Oxychlorination process scheme showing the gas recycle for oxygen-
based alternative [19].
1-11
1.2.2 Synthesis of Vinyl Chloride Monomer (VCM)
1.2.2.1 Acetylene Process
In the mid-1930s, the acetylene route was one of the earliest VCM process ever
existed. The monomer of PVC which is VCM, was synthesized via a reaction between
acetylene and anhydrous hydrogen chloride in gaseous phase reaction with the
presence of a chloride catalyst like mercuric chloride in a tubular catalytic reactor as
shown in Figure 1.8 [17].
Figure 1. 8: Production of VCM via Acetylene-HCl route.
The reaction temperature is around 150.8oC to 200oC, in atmospheric pressure

and is highly exothermic. This process has a very high purity and yield. Acetylene can
be obtained from carbide in coal. Equation 1.4 and 1.5 shows the reaction of hydration
of calcium carbide to form acetylene and the chlorination of acetylene reactions,
respectively.
CaC2 + 2H2O → CH=CH + Ca(OH)2 (1.4)
CH=CH + HCl → CH2=CHCl (1.5)
1-12
The production of VCM from acetylene route was very common before ethylene
route was introduced and became very popular. This acetylene route became very
unattractive due to its hazard of storing and transporting acetylene as acetylene is
highly poisonous to human health. This means that the acetylene production plant must
be very close or connected to the VCM plant as it may cut off the need to provide a
proper and stringent storage for acetylene. VCM production with large coal reserves
still uses this method today [17]. Table 1.8 shows the summary of the advantage and
disadvantages of production of VCM via acetylene route.
Table 1. 8 Summary of advantage and disadvantages of acetylene process.

Simple process configuration. The cost of buying acetylene from

external suppliers is high.
Highly exothermic process which could Stringent control and monitoring on

provide an excellent heat integration if acetylene storage is required.
in conjunction with EDC pyrolysis plant
[18].
High selectivity and purity.
1.2.2.2 Pyrolysis of 1,2-dichloroethane (EDC)
Thermal cracking or also known as Pyrolysis is a process of using EDC as

reactant to produce vinyl chloride monomer. The thermal cracking of EDC happens in
a furnace and is a highly endothermic reaction (∆H = +97 kJ/mol) involving a
homogenous gas phase reaction. The furnace is divided into four main sections. The
sections are the radiation section (lower part) where the higher temperature reactions
occur, convection section (upper part) where the feed is heated up by the exhaust gas
to the point in which reaction rates become signiﬁcant (400-420◦C), shock section and
the stack [19]. The optimum superficial gas velocity is between 10-20 m/s. The length
of the coil should be able to maintain a space-time of 5-30 seconds [14].
The heat exchanger vaporizes the heat externally prior to supplying it into the
radiation section. The vaporization process is done with steam and the flue gas of
pyrolysis. This is to ensure maximum heat integration to save as much heat as
possible. The heat is obtained from a series of burners in the furnace chamber, fed by
natural gas. The reaction temperature is between 480 to 550oC with a pressure of 3 to
1-13
30 bar. Higher pressure is preferable in order to minimize the furnace size, maximize
heat integration and make downstream separation easier [14].
The process started with cracking of EDC into VCM approximately at 500oC
temperature followed by quenching of the gaseous output. The conversion of the
reaction is about 50-65%. Rapid quenching is required to prevent tars and heavy by-
products formation in the thermal cracker [19]. Equation 1.6 shows the pyrolysis
reaction of EDC.
CH2Cl—CH2Cl → CH2=CHCl + HCl (1.6)
Pyrolysis of EDC can be done in presence or in absence of catalyst. However,

with an appropriate design of the reactor, high conversion and yield close can be
achieved and hence the absence of catalyst is preferable due to the additional cost of
catalysts [14]. The yield is around 99% of VCM purity. However, the conversion range
must be maintained around 55% to control its selectivity. Improvements on the process
selectivity can be done by adding initiators and promoters such as chlorine which is
easily available since it enhances the chain propagation. Other chlorine delivering
compounds can also be used in this process. The other compounds are
tetrachloromethane (CCl4) and trichloroethane (chloroform, CHCl3) [18].
Figure 1. 9: Schematic representation of the 1,2-dichloroethane (EDC) cracking

furnace. The feed is preheated and vaporised in the convection section while the
reaction occurs in the radiation section [16].
1-14
The purity of the raw material must be at least around 99.5%. This is to ensure
coke formation and fouling can be prevented. However, despite the expedients and
precautions, it is possible for ethylene, acetylene, 1,3-butadiene, chloroprene,
vinylacetylene, benzene, chlorobenzene, dichloroethylenes, 1,1-dichloroethane,
trichloroethane, methyl chlorides, methylene chloride, chloroform and
tetrachloromethane to form as impurities [14]. Some of the side reactions are:
1,2-C2H4Cl2 (EDC) → C2H3Cl (VCM) + HCl (1.7)
C2H3Cl (VCM) → C2H2 + HCl (1.8)
1,2-C2H4Cl2 (EDC) → C2H4 + Cl2 (1.9)
C2H5Cl → C2H4 + HCl (1.10)
C2H4 + C2H2 → C4H6 (BUTD) (1.11)
C2H2 + C2H3Cl (VCM) → C4H5Cl (Chloroprene) (1.12)
Equation 1.7 is the main desired process reaction in pyrolysis of EDC. Reaction
in Equation 1.8 is the formation of acetylene as the intermediate that will further react
to form other impurities such as vinyl-acetylene and benzene. Meanwhile, reaction
Equation 1.9 and reaction in Equation 1.10 are the formation of light unsaturated
hydrocarbons such as ethylene. The reaction may extend to the formation of butadiene
and chloroprene as shown in reaction Equation 1.11 and reaction Equation 1.9,
respectively. These two reactions may occur in presence of free radicals. Next, the
formation of coke is also mentioned in Equation 1.13 to Equation 1.17:
1,2-C2H4Cl2 + Cl2 → C2H3Cl3 (TCE) + HCl (1.13)
C2H3Cl3 (TCE) → C2H2Cl2 (DCE) + HCl (1.14)
C2H3Cl2 + Cl2 → C2HCl3 (TRI) + HCl (1.15)
C2H4 + C2H2 → C4H6 (BUTD) (1.16)
2C2H4Cl2 → C4H8Cl3 (heavy impurity) + Cl2 (1.17)
The carbon deposition on the reactor wall is the highly undesired reaction. The
reaction only occurs in when the temperature of the reactor wall is very high. Coke
deposition is a major problem in EDC pyrolysis. Low temperature pyrolysis (below
500oC) prevents the coke formation in exchange of decreased reaction rate.
1-15
Table 1. 9: Summary of advantages and disadvantages of EDC Pyrolysis process.
Very economical process due to the Complex process configuration.

abundancy of ethylene as the raw
materials.
Does not require any catalysts. Highly endothermic reaction requires

high energy and heat consumption.
The by-product, anhydrous hydrogen Coke and fouling are very common to
chloride gas, can be recycled into other occur in the thermal cracker.
VCM producing plant such as Acetylene
process or direct chlorination plant [18].
Some side reactions are good reactions Multiple side reactions are unavoidable
as they could assist on the main VCM although they can be controlled.
reaction.
Could provide high volume of PVC,

purity and conversion if a well-
developed heat .integration is built in
conjunction with EDC acetylene plant.
[18].
High purity and selectivity if the

condition of the thermal cracker is
optimum.
1.2.2.3 Acetylene versus Pyrolysis Route
Generally, acetylene route has higher impact towards environment, cost and
risks on safe operation. Acetylene is a poisonous compound and is very flammable
which requires high capital and operational cost for storage. Moreover, although
acetylene route has higher conversion compare to pyrolysis, however it requires higher
capital and operational cost which is not beneficial to run a plant. Furthermore,
acetylene feedstock is very high in terms of cost. On the contrary, pyrolysis of EDC is
the best option for VCM production due to the availability of EDC feed from the bubble
column reactor (EDC production plant). Although the conversion of EDC to VCM is only
50%, the selectivity of the main reaction is 99.4%. Moreover, the side product from the
main reaction is the sellable and marketable HCl. The by-product could be a potential
side income to increase the profitability of the PVC plant.
1-16
1.2.3 Polyvinyl Chloride (PVC) Processes
Vinyl Chloride Monomer (VCM) is the main material from which Polyvinyl
Chloride (PVC) is made. The chemical process for making PVC involves taking the
simplest unit, called the monomer, and linking these monomer molecules together in
the polymerization process [20]. Polymerisation of PVC is an exothermic reaction. The
pressure in the reactor is usually in the range of 0.4 – 1.2 MPa and the reaction
temperature is between 35 – 70°C. During the polymerisation reaction 85 – 97% of the
VCM is converted into PVC [19]. Few polymerization methods of VCM are being
practiced by industries to produce PVC such as suspension polymerization, emulsion
polymerization and bulk polymerization.
1.2.3.1 Suspension Polymerization
Suspension polymerization is one of the methods used to polymerize VCM for

production of PVC. In suspension polymerization, an intimate mixture of at least one
polymerizable monomer and at least one suspending agent are suspended in aqueous
medium and subjected to suitable polymerization conditions of time, temperature, and
pressure [21]. Polymerization reaction is batch-wise operation, started by feeding raw
material into the reactor and finished by discharging PVC slurry after polymerization.
Into the reactor equipped with cooling jacket and agitator are charged pure (de-
mineralized) water, VCM and protective colloid (suspending agent) [22]. The reactor is
warmed up to a certain temperature. Polymerization catalyst is added for the radical
polymerization of VCM to be started. At the time the reaction pressure goes down to a
certain value, the polymerization reaction is stopped. Then unreacted VCM is
recovered. After discharge of PVC slurry, the reactor is rinsed and remaining VCM is
evacuated [22]. Schematic representation of the suspension polymerization process of
vinyl chloride monomer for production of polyvinyl chloride is shown in Figure 1.10.
Table 1.10 shows the advantages and disadvantages of suspension polymerization
process.
1-17
Table 1. 10: Advantages and disadvantages of suspension polymerization process
[23]–[25].
Stirring is easy due to low viscosity of the Only water insoluble monomers are
suspension. used.
Easy heat removal due to the high heat Must separate and purify polymer.
capacity of water.
Polymerization yields finely divided, Purity is less when compared to polymer

stable latexes and dispersions to be used that obtained by mass polymerization.
directly in coatings, paints, and
adhesives.
No chain transfer, mass transfer

problem.
The product obtained is in granular form

which is convenient to handle.
About 80% of production of PVC involves

suspension polymerization.
Figure 1. 10: Schematic representation of the suspension polymerization process of

vinyl chloride monomer for production of polyvinyl chloride [29].
1-18
1.2.3.2 Emulsion Polymerization
Emulsion polymerization is a radical type of polymerization. The technique is

commonly used for the larger production of commercial plastics & elastomers. This
method will stabilize monomer in water by addition of surfactant which has a hydrophilic
and hydrophobic end in its structure. When it is put into a water, the surfactant
molecules gather together into aggregates called micelles [26]. The system consists of
water insoluble monomer, dispersion medium & emulsifying agents or surfactants and
a water-soluble initiator [26]. Although this method is very similar to suspension
polymerization, the two schemes differ in two important aspects; the polymerization
initiator is located in the aqueous phase and the particles of polymer produced are
typically in the order of 0.1 micron in diameter, some ten times smaller than the smallest
encountered in suspension polymerization [27]. Monomer droplets disappear at about
80% completion and generally the polymerization is terminated at about 90%
completion [27]. The schematic representation of the emulsion polymerization process
of vinyl chloride monomer for production of polyvinyl chloride is shown on Figure 1.11.
Table 1.11 shows the advantages and disadvantages of emulsion polymerization
process.
Table 1. 11: Advantages and disadvantages of emulsion polymerization process [23],

[25], [27], [28].
No chain transfer problem and heat Polymer can easily become contaminated
transfer problem. The products with traces of the emulsifier. This can lead
obtained in the are directly usable. to poor transparency which can often be
an important property.
Very high molecular weightage can be Considerable technology is needed to

obtained in very less time nearly 1-2 recover the polymer in the solid form.
hours, high average chain lengths are
achievable.
Suitable for ionic or radical Use of very large quantities of water

condensation. lowers the yield per reactor volume.
About 12% of production of PVC

involves emulsion polymerization.
1-19
Figure 1. 11: Schematic representation of the emulsion polymerization process of
vinyl chloride monomer for production of polyvinyl chloride [29].
1.2.3.3 Bulk Polymerization
Bulk polymerization is carried out in the absence of any solvent or dispersant

and is thus the simplest in terms of formulation of all polymerization processes. In mass
or bulk polymerization, the reaction mixture consists mainly of monomers, and in the
case of free-radical or ionic polymerization, of vinyl monomers and a soluble initiator.
Thus, the polymerization is carried out in undiluted monomer [29]. It is used for most
step-growth polymers and many types of chain-growth polymers. Bulk polymerizations
can either by batch or continuous and can produce polymers which are either partially
or completely soluble in their producing monomers [30]. Schematic representation of
the bulk polymerization process of vinyl chloride monomer for production of polyvinyl
chloride is shown in Figure 1.12. Table 1.12 shows the advantages and disadvantages
of bulk polymerization process.
1-20
Table 1. 12: Advantages and disadvantages of bulk polymerization process [23]–[25].
Products relatively pure due to Longer polymerization time for high molecular weight
minimum contamination [6]. polymers (nearly 10-16 hrs.) [5].
High molecular weight and molecular Viscosity increases as conversion increases, making
weight distribution. heat removal and processing more difficult [6]
Product can be directly used, and no Stirring becomes difficult after 30-40% conversion. As
isolation is required due to its said above the molecular weight increases
resistance towards solvents [5]. enormously which leads to auto acceleration [5].
About 8% of production of PVC Product has broad molecular weight distribution [6].
involves bulk polymerization [7].
Removals of tracers of unreacted monomer difﬁcult
[5].
Hot spots may form, and explosion may possible [5].
Figure 1. 12: Schematic representation of the bulk polymerization process of vinyl

chloride monomer for production of polyvinyl chloride [29].
1-21
1.2.3.4 Comparison of Suspension, Emulsion and Bulk Polymerization.
Based on advantages and disadvantages of suspension, emulsion and bulk

polymerization shown in Table 1.10, Table 1.11 and Table 1.12 respectively,
comparison of these three polymerization processes can be discussed. In both
emulsion and bulk polymerization process, PVC with high molecular weight can be
achieved. However, bulk polymerization took a very long time in order to achieve the
same results as emulsion polymerization. Long residence time in polymerization is not
preferred as it will lower the production rate and consume high energy. Meanwhile,
suspension polymerization offers an ease in heat removal and granular form product
which is convenient to handle. It is also noted that both suspension and emulsion
polymerization processes are not problematic on chain, heat and mass transfer
problem. But, emulsion polymerization process could easily become contaminated with
traces of the emulsifier which can lead to poor transparency which can often be an
important property of polymerization. Viscosity in suspension polymerization is lower
compared to other processes which could lower the energy consumption for the
process and ease the stirring process in the reactor which maintain the mixture in
suspension for high conversion.
1.3 PROCESS SELECTION
Process selection is a step taken before plant design project can be carried out
which is important in order to evaluate the criteria of the processes to ensure that one
of the processes are selected based on the proposed criteria. Few methods of process
selection can be used such as concept screening method and concept scoring method.
This concepts in process selection can be applied in designing a chemical plant for
polyvinyl-chloride production. In this project, the criterion that have been chosen are
feedstock, type of reactor, by product, catalyst used, cost of catalyst, operating
pressure and temperature, conversion, selectivity and safety consideration. Table 1.13
describes each of the criterion selected to be compared in this project before selecting
the best alternative using concept screening and scoring. Table 1.14, Table 1.15 and
Table 1.16 show the process comparisons for ethylene dichloride (EDC) formation,
vinyl chloride (VCM) formation, and polyvinyl chloride (PVC) formation based on the
selected criterion.
1-22
Table 1. 13: Description for criterion selection for process comparison in process
selection.
Criterion Description
Feedstock Feedstock cost and availability commonly affect the
price of product and continuity of process.
Type of Reactor Type of reactor used need to be decided professionally
as it affect the cost and reaction of the process.
Operating Temperature Low operating temperature increase the utility cost and
reduce the chance of incident such as explosion.
Operating Pressure Low operating pressure increase the utility cost and
reduce the chance of incident such as explosion.
Residence Time Low residence time in batch process increase the rate
of production.
Reaction Phase Reaction phase affect the ease of reaction based on the
type of reaction and process.
Conversion In any process, higher conversion process is the most
desired criteria.
Selectivity Reaction selectivity is important to ensure high
production of desired product and low production of by-
product.
Catalyst/Initiator The use of catalyst could increase reaction selectivity
but also cause difficulties to separate it from products.
Catalyst/Initiator Cost Other than feedstock, cost of catalyst also affects the
price of products.
By-product By product produced from the process need to be
separated and treat.
Solvent Solvent used in process could affect cost operational of
and produce additional waste.
Safety consideration Safety of the process must be identified prevent accident
like explosion and provide safe for working condition.
1.3.1 Process Alternatives
1.3.1.1 Ethylene Dichloride (EDC) Formation
Table 1. 14: Process comparison of direct chlorination and oxychlorination for EDC
formation.
Criterion Alternative 1 Alternative 2
Process Direct Chlorination [31] Oxychlorination [31]
Name
Feedstock Ethylene, Chlorine[32] Ethylene, Hydrogen Chloride,
Oxygen [33]
Type of Bubble column reactor [32] Fixed Bed Reactor [33]
Reactor
Operating 40-90 ᴼC [32] 230-300 ᴼC [32]
Temperature
Operating 1.5-5 bar [32] 2-14 bar[32]
Pressure
1-23
Reaction Heterogeneous [34] Homogeneous (gas) [33]
Phase
Conversion >99% [32] >99% [34]
Selectivity >99% [32] 95-99% [32]
Initiator Ferric (III) Chloride [32] Copper (II) Chloride [34]
(catalyst)
Catalyst Cost RM527/ton [35] RM15,500/ton [36]
By-product Higher-C hydrocarbons [31] Ethyl Chloride [31]
Safety Strict monitoring & maintenance should be done to avoid reactor
consideration corrosion [32]
1.3.1.2 Vinyl Chloride (VCM) Formation
Table 1. 15: Process comparison of pyrolysis and vinyilation of acetylene for VCM
formation.
Criterion Alternative 1 Alternative 2
Process Pyrolysis [32] Vinylation of Acetylene [34]
Name
Feedstock Ethylene Dichloride Acetylene, Anhydrous
Hydrogen Chloride [34]
Type of Thermal Cracker [32] Tubular Catalytic Reactor [34]
Reactor
Operating 500 ᴼC [15] 150.8 ᴼC to 200 ᴼC [34]
Temperature
Operating 3-30 bar [15] 1.013 bar [34]
Pressure
Reaction Homogenous (gas) [15] Homogeneous (gas) [34]
Phase
Conversion 50% [32] >99% [34]
Selectivity >99% [32] >99% [34]
Initiator - Mercuric Chloride [34]
(catalyst)
Catalyst Cost - RM225,000/ton [35]
By-product Main by-product: Hydrogen Chloroprene, ethylbenzene,
Chloride butadienes, trichloroethane
[34]
Side reaction by-product (<1%):
Trichloroethane, chloroprene,
ethylbenzene, butadienes [15]
Safety High Temperature Hydrogen Acetylene is highly flammable
consideration Attack must be avoided [32] and poisonous
Environmentally friendly –
consume by-product toxic HCl
as feedstock [34]
1-24
1.3.1.3 Polyvinyl Chloride (PVC) Formation
Table 1. 16: Process comparison for polymerization method for PVC formation.
Criterion Alternative 1 Alternative 2 Alternative 3
Process Name Suspension Emulsion Bulk Polymerization
Polymerization [37] Polymerization [38] [39]
Feedstock Vinyl chloride monomer (from previous process)
Type of Reactor Jacket batch Autoclave glass batch reactor [4]

reactor [37]
Operating 50-100 ᴼC [40] 500 ᴼC [38] 30-40 ᴼC [39]
Temperature
Operating 7.4 bar [37] 7.8 bar [38] 1 bar [41]
Pressure
Residence Time 30 minutes [42] 72 hours [31] 3-9 hours
Reaction Phase Heterogeneous Heterogeneous [40] Heterogeneous [40]
[40]
Conversion 80% [37] 99% [31] 7-20% [43]
Initiator Benzoyl Peroxide Potassium Benzoyl Peroxide
(catalyst) [43] persulfate [43] [43]
Catalyst Cost RM355 per metric RM4,180 per metric RM355 per metric
ton [44] ton [45] ton [44]
Solvent Water [4] Water [4] -
Safety VCM is highly VCM is highly toxic, VCM is highly toxic,
consideration toxic, flammable, flammable, and flammable, and
and carcinogenic. carcinogenic. carcinogenic.
High operating
temperature always
need to be
monitored.
1-25
1.3.2 Concept Screening
Concept screening of polyvinyl chloride production shown in Table 1.17 only

includes the PVC formation processes with a total of 3 alternatives that have been
compared in Table 1.16. The comparison of 3 alternatives for PVC formation process
include suspension (alternative 1), emulsion (alternative 2) and bulk polymerization
(alternative 3) process by taking alternative 2 as reference of comparison. Result
obtained from concept screening for PVC formation process alternatives has ranked
emulsion polymerization process as the worst process compared to suspension and
bulk polymerization. Due to a very slightly different in score for emulsion polymerization
process, this process will be eliminated in concept scoring as shown in Table 1.18.
Therefore, only 2 alternatives for each process are remained that will include in concept
scoring.
Table 1. 17: Screening concept for EDC, VCM and PVC formation process
alternatives.
Criterion Polyvinyl Chloride (PVC) Formation
Alternative 1 Alternative 2 Alternative 3
Feedstock 0 0 0
Type of Reactor + 0 0
Operating Temperature + 0 +
Operating Pressure 0 0 +
Residence Time + 0 +
Reaction Phase 0 0 0
Conversion - 0 -
Selectivity 0 0 0
Catalyst/Initiator 0 0 0
Catalyst/Initiator Cost + 0 +
By-product 0 0 0
Solvent 0 0 +
Safety consideration + 0 +
Total Score 4 0 5
Rank 2 3 1
Note: (+) = Better than, (-) = Worse than and (0) = Same as
1-26
1.3.3 Concept Scoring
After concept screening is done, selected potential alternatives is entered into

concept screening. Concept scoring is carried out with the identical matrix used. In this
step, weightage is introduced to each criterion that reflects the importance of the
criterion. Each criterion then will be “assigned a value from 1 to 5, where 1 = much
worse, 2 = worse, 3 = same, 4 = better, and 5 = much better. Scoring of each alternative
will be calculated by considering the weightage and the score of each criterion of the
process. Based on Table 1.18, highest weightage of 15% is given to feedstock and
safety consideration criterion. This is due to their major concern for the industry to
maintain a sustainable process, obtain high of profit and to operate well at safe
condition. Meanwhile, the other criterion weight is distributed for 5% and 10%
weightage accordingly to its importance.
From Table 6 for EDC formation process, direct chlorination (alternative 1) has
scored 3.7 which is higher than oxychlorination process (alternative 2). It is mainly due
to the preferable feedstock and catalyst used in direct chlorination process. Oxygen
raw material and copper (III) chloride catalyst required in oxychlorination process is
expensive. Next, in VCM formation process selection, pyrolysis process (alternative 1)
ranked higher than vinylation of acetylene process (alternative 2). Although alternative
2 operates at lower temperature and pressure, it has scored lower in feedstock, catalyst
and by-product criterion. Acetylene is a very expensive gas which is not recommended
to be used directly for production of VCM compared to ethylene dichloride that is
supplied from previous process. Pyrolysis also does not require any catalyst, which is
therefore more economical.
Finally, for the comparison of PVC formation process, suspension

polymerization (alternative 1) has scored much higher than bulk polymerization
(alternative 2) process. Suspension polymerization has scored high for the biggest
weightage percent criterion that importance the residence time for polymerization
process. Since polymerization is a batch process, short residence time is highly
preferable to increase the rate of production and avoid the need for multiple equipment
for a high scale production.
1-27
Table 1. 18: Scoring concept for EDC, VCM and PVC formation process alternatives.
Ethylene Dichloride Vinyl Chloride (VCM) Polyvinyl Chloride

(EDC) Formation Formation (PVC) Formation
Weightage Weightage
Criterion Criterion
(%) (%)
Alternative Alternative Alternative Alternative Alternative Alternative
1 2 1 2 1 3
Feedstock 15 4 3 3 2 Feedstock 10 3 3
Type of Type of
10 4 3 3 3 10 3 3
Reactor Reactor
Operating Operating
5 5 3 3 4 5 2 3
Temperature Temperature
Operating Operating
5 4 3 3 4 5 2 3
Pressure Pressure
Reaction Residence
5 4 3 3 3 15 5 3
Phase Time
Reaction
Conversion 10 3 3 3 4 5 4 3
Phase
Selectivity 10 4 3 3 3 Conversion 15 4 3
Catalyst 5 3 3 3 1 Initiator 5 3 3
Catalyst Cost 10 5 3 3 2 Initiator Cost 10 4 3
By-product 10 4 3 3 2 Solvent 5 2 3
Safety Safety
15 3 3 3 4 15 3 3
consideration consideration
1-28
Total Score 3.7 4.05 3 2.9 Total Score 3.7 3.0
Rank 1 1 1 2 Rank 1 2
Note: (1) = Much worse, (2) = Worse, (3) = Same, (4) = Better and (5) = Much better.
1-29
1.4 CONCEPTUAL DESIGN AND FLOWSHEETING
Conceptual design and flowsheeting is the following step in designing a chemical

process plant after the screening and scoring concept in plant selection. The main objective
of this step is to develop the best process flow sheet and to find an optimal operating point.
The common method of conceptual design starts with concept sketches and modelling the
process plant. In order to construct the conceptual design for the chemical plant that produce
polyvinyl chloride with the capacity of 50,000 tonne per annum, Douglas’s Hierarchy approach
is applied. Douglas’s Hierarchy is established by James M. Douglas in 1988. The “Douglas
Method" is based on hierarchical decision-making, using economic feasibility as a main
criterion for process evaluation [46]. There are 5 steps of hierarchy for conceptual design of
chemical processes in Douglas’ Hierarchy which involves process mode selection, input and
output structure of the process, recycle structure of the process, general structure of the
separation system, and the heat-exchanger network or process energy recovery system in
respective steps [47].
1.4.1 Conceptual Design
1.4.1.1 Step 1: Batch versus Continuous Process
Production of polyvinyl chloride (PVC) from reaction of ethylene with chlorine requires
few steps of processes which are direct chlorination of ethylene, cracking ethylene dichloride
(EDC) via pyrolysis and suspension polymerization of vinyl chloride monomer (VCM). The
selected process mode in designing a chemical plant can be either batch process or
continuous process. In order to choose the mode of the process, the concept of batch process
and continuous process must be understood.
Batch process involves the processing of bulk material in batches through each step
of the desired process. Processing of subsequent batches must wait until the current batch is
finished. In other word, the work done by batch systems are in parts where one job is
processed then another job in the queue is processed [48]. Since batch processes are time-
dependent, they have a different structure and very different alternatives from continuous
plants [47]. A continuous process, on the other hand, refers to a processing that involves
moving a single work unit at a time between every step of the process without any breaks in
time, substance, sequence or extend [49]. Thus, in most applications, continuous process
1-30
increase productivity, saves cost and time. Table 1.19 shows the comparison of batch and
continuous process.
Table 1. 19: Comparison of batch and continuous processes [49].

No. Factor Batch Process Continuous Process
1. Rate of production Low High
2. Manufacturing cost Relatively higher Relatively lower
3. Workforce requirement High Low
4. Shut-down times Often Rare
5. Ease of automation Difficult Easy
6. Waste generation rate High Low
7. Product quality Low High
Based on Table 1.19, the rate of production for batch process is lower compared to
continuous process. The difference in rate of production is highly dependent on the shut-down
time. Shut-down times for continuous process is rare, whereas quite more often shut-down
times happens in batch process. When the reactor operation time of a process is high, reaction
takes place for conversion of reactants into products will be relatively higher. Furthermore,
higher number of workforces are required when shut-down time is frequent such as for batch
mode process. This is because, continuous process provides an automation mode which is
much easier compared to batch process mode. Moreover, the establishment of chemical plant
in continuous process mode is much lower than that in batch process mode. This is due to the
continuously fed of raw materials into the reactor for continuous process mode. Finally, the
quality of the product is much higher for continuous process mode than batch process mode.
As the raw materials are constantly fed into the reactor for continuous process mode, the
products are constantly removed from the reactor as well in order to maintain the steady state
of operation. This condition optimum the level of conversion the raw material into products and
limiting the probability for the side-reactions to take place. This also reduce the generation of
waste in continuous process mode. In regard to the comparisons that have been made,
continuous process mode is therefore become more efficient compared to the batch process
mode.
In this design project, production of 50,000 tonnes per annum of PVC requires high
rate of production, low manufacturing cost, minimum shut-down time, easy automation of the
process, low requirement of workforce, high production quality and low generation of waste.
Therefore, continuous process mode is selected as the mode of operation for the PVC
production plant.
1-31
1.4.1.2 Step 2: Input and Output Structure
Input and output structure of reaction system is one of the cores of chemical
engineering process after selection process. With proper selection and design of the chemical
reaction system, large production rate and selectivity can be achieved. The system reaction
is the starting point in chemical design for polyvinyl chloride plant [50]. Three different chemical
reaction involved in the polyvinyl chloride process. Therefore, each output and input structure
in each reaction is illustrated in block diagram. Figure 1.13 shows the input-output structure of
Reaction 1.
Reaction 1
Ethylene
1, 2 dichloroethane (EDC)
CH2 CH2 + Cl2 → ClCH2 CH2 Cl
Chlorine
Figure 1. 13: Input-output structure of Reaction 1.
The first reaction is called direct chlorination. In this reaction, ethylene and chlorine will
combine in a catalytic reaction to form EDC. Ferric chloride was chosen as the catalyst as
ferric chloride is high selectivity. Due to high selectivity, the conversion of ethylene is
approximately more than 90%. Table 1.20 shows the summarization of operating condition
involved in Reaction 1.
Table 1. 20: Operating condition in Reaction 1.

Operating Condition Description
Operating Temperature 90 ᴼC
Operating Pressure 4 bar
Reaction phase Liquid
Type of reactor used Bubble column reactor
Conversion 99.8%
Selectivity 95%-99%
1-32
Reaction 2
1,2 dichloroethane (EDC)
1, 2 dichloroethane ClCH2 CH2 Cl →

HCL (by-product)
CH2 CHCl + HCL
C2H3Cl (VCM)
Figure 1. 14: Input-output structure of Reaction 2.
The second reaction involved in polyvinyl chloride plant is converting EDC to VCM.
The reaction is called pyrolysis or thermal cracking. Additionally, hydrochloric acid is the by-
product of this reaction. This reaction occurs without any presence of catalyst. This is due to
the cost factor. Even though catalyst is absence in this reaction, but the conversion yield is
still considered high and effective. Table 1.21 shows the summarization of operating condition
involved in reaction 2.
Table 1. 21: Operating condition Reaction 2.

Operating Temperature 500 ᴼC
Operating Pressure 25 bar
Type of reactor used Thermal cracker
Conversion 50%
Selectivity 99%
Reaction 3
C2H3Cl (VCM) C2H3Cl → (C2H3Cl) n (C2H3Cl) n (PVC)
(Polymerization Process)
Figure 1. 15: Input-Output of Reaction 3.
The last reaction involved in order to produce polyvinyl chloride is polymerization.

Suspension polymerization was chosen among other type of polymerization such as bulk and
emulsion polymerization. Suspension polymerization processes are conducted in a
heterogeneous medium where monomer is insoluble in a continuous phase which is typically
water [51]. Therefore, water is added in polymerization process. Also, suspension
polymerization process requires benzoyl peroxide as initiator to carry out the reaction for
1-33
polymerization of VCM. Table 1.22 shows the summarization of operating condition involved
in reaction 3.
Table 1. 22: Operating condition Reaction 3.

Operating Temperature 60 - 70 ᴼC
Operating Pressure 7.4 bar
Type of reactor used Jacket batch reactor
Conversion 80%
1.4.1.3 Step 3: Recycle Structure
After input and output streams have been identified, the next step in designing polyvinyl
chloride plant is designing the recycle streams. Recycle is the best and common method in
industry to separate nearly all the unconverted reactants from the product stream. Recycle
stream for polyvinyl chloride production need to consider due to a few factors. The main factor
of recycling stream is catalyst and unreacted or unconverted components in the product
stream can be returned back into the reactor. This could avoid unconverted materials from
being waste. This leads to the reduction in the amount of waste generated, which turns the
process plant to be more environmentally friendly, as well as reducing the cost for numerous
of waste disposal. Even though recycle process require high cost due to the separation and
recycle equipment, higher profit from the purified product could be obtained [52]. Hence, in
this case, catalyst, unreacted ethylene dichloride and vinyl chloride monomer are decided to
be recycled from distillation column to reactor and produce purified polyvinyl chloride as
illustrated in Figure 1.16. Thus, purified vinyl chloride can be sold at higher profit.
Nevertheless, a few factors must be considered before establishing recycle stream in process.
The most critical factor is to ensure the recycle component does not produce an impurity. This
is due to the components of the impurities will lead to the ineffective separation and disturb
other process. After considering the catalyst, ethylene dichloride and vinyl chloride monomer
components, recycle streams has been established because the recycle components do not
produce any impurities towards polyvinyl chloride production process.
1-34
Reactor Bubble
Ethylene
Feed Column
Chlorine Preparation Reactor
EDC
Separator Reactor
HCl Distillation Pyrolysis
Feed Feed
Column Reactor
Preparation Preparation
VCM Water Wastewater

Treatment
VCM Reactor
Batch Reactor PVC
Storage Feed Centrifugal
(Polymerization)
Tank Preparation
Figure 1. 16: General plant structure for PVC plant design.
1.4.1.4 Step 4: General Structure of Separation Process
After considering the recycle stream in the process design for polyvinyl chloride plant,
the next crucial step is designing separator. A typical chemical plant must have separator.
This is because raw materials and products need to pre-purify and purify before and after
reaction takes place in the chemical reactor. Next, unreacted feed is separated from reaction
product and then recycle to the specific reactor. There are several types of separator in
chemical engineering separation method such as flash distillation column, batch distillation,
adsorption, stripping and extraction [53].
In this polyvinyl chloride plant, first separator used is flash column. Flash column is
designed to separate catalyst from the reactor outlet to reuse and recycle the catalyst into the
bubble column reactor. Second separator used in this plant design is distillation column. Main
function of this separator is to separate hydrogen chloride and unreacted EDC from the
decomposition process of EDC in the pyrolysis reactor. Finally, distillation column is also
designed to separate and return unconverted vinyl chloride monomer from suspension
polymerization process to the vinyl chloride monomer tank. Structure of the separator
arrangement is illustrated in Figure 1.17.
1-35
Catalyst
Reactor Bubble Separator

Ethylene Flash
Feed Column Feed
Column
Chlorine Preparation Reactor Preparatio
n
EDC EDC
HCl
Separator Reactor
Distillation Pyrolysis
Feed Feed
Column Reactor
VCM Water
VCM Reactor Separator

Batch Reactor
Storage Feed Feed
(Polymerization)
Tank Preparation Preparation
VCM Distillation
Column
Wastewater Centrifugal PVC

Treatment
Figure 1. 18: Recycling structure for polyvinyl chloride plant design
1-36
Step 5: Heat Exchanger Network or Process Energy Recovery System
Figure 1.18 shows the location of the main heat exchanger network in designing the
PVC plant. The heat exchanger network consists of cold stream and hot stream that exchange
energy in the form of heat in order to reduce amount of new energy or fuel needed to heat up
the reactants. High temperature outlet from the pyrolysis furnace is about 500°C and need to
be cooled to about 25°C in order to ensure complete the decomposition process of EDC into
VCM. Therefore, a heat exchanger network is used to transfer heat energy from the separator
feed preparation unit to the reactor feed preparation unit. The purpose of the heat exchanger
is to pre-heat EDC in order to prepare the material to undergo decomposition process in the
pyrolysis furnace at about 500°C. Pre-heating process could reduce the total heat energy
required to increase the temperature of EDC to 500°C in pyrolysis. Reducing amount of heat
required in pyrolysis means reducing the amount of energy required. Reducing amount of
energy will therefore reduce the amount of utility cost.
Catalyst
Ethylene Reactor Bubble Separator

Flash
Feed Column Feed
Column
Chlorine Preparation Reactor Preparatio
n
Heat
Exchanger
EDC EDC
Network
Separator Pyrolysis Furnace
HCl Distillation
Feed Furnace Feed
Column
Preparation (500°C) Preparation
VCM Water
VCM Reactor Separator
Batch Reactor
Storage Feed Feed
(Polymerization)
Tank Preparation Preparation
VCM Distillation
Column
Wastewater
Centrifugal
PVC
Treatment
Figure 1. 19: Heat exchanger network for the design of polyvinyl chloride plant.
1-37
1.4.2 Conceptual Flowsheeting
Process conception process is the first step in the sequence leading to the construction
of a process plant which is used in the manufacture of a product. Process selection and plant
conceptual design that have been discussed in the previous subchapters is important to be
implemented in this conceptual flowsheeting process. In this section, 3 conceptual design
flowsheeting alternatives for PVC plant will be discussed. Figure 1.19, Figure 1.20 and Figure
1.21 show the BFD of different concept design alternatives.
1-38
Conceptual Flowsheeting Alternative 1
TCE
Ethylene
Reactor Separator
Bubble Column Reactor Flash
Feed Feed
Chlorine (120ᴼC, 1.5 atm) Column
EDC
EDC
Separator Reactor
HCl Distillation VCM Pyrolysis Reactor
Feed Feed
Column HCl (500ᴼC, 26 atm)
Preparation Preparation Wastewater
Treatment
VCM Water
Water
VCM Reactor Polymerization Batch Separator
Distillation PVC
Storage Feed Reactor Feed Centrifugal
Column
Tank Preparation (70ᴼC, 7.4 bar) Preparation
VCM
Figure 1. 20: Conceptual Flowhseeting Alternative 1 for PVC production plant.
1-39
Catalyst
Ethylene
Reactor Separator
Feed Feed
EDC
EDC
Separator Reactor
HCl Distillation VCM Pyrolysis Reactor
Feed Feed
Treatment
VCM Water
Water
Distillation PVC
Column
VCM
1-40
Catalyst
Ethylene
Reactor Separator
Feed Feed
HCl Cl2 EDC EDC
Separator Reactor
Distillation VCM Pyrolysis Reactor
Feed Feed
Treatment
VCM Water
Water
Distillation
Column
VCM
PVC
1-41
Conceptual Flowsheeting Alternatives shown are the possible flowsheeting that
can be used to operate a PVC plant. However, detail comparison need to be conducted
in order to construct a PVC plant that is high profit, low operating cost and low energy
consumption. Firstly. based on the temperature point of view, Low Temperature
Chlorination (LTC) reaction, operating at 50 to 70° C, at a pressure of 4 bar, which is
below the mixture boiling point as seen in Alternative 2 is very advantageous to achieve
a significant selectivity of above 99%. Many methods such as internal heat-transfer like
cooling coil and application of heat exchangers can be used in LTC [33]. Although
rejecting the heat of reaction to the environment could prove disadvantageous, if it is
redirect onto the pyrolysis section, the amount of heat energy that can be saved is quite
efficient. On the other hand, High Temperature Chlorination (HTC) reaction as seen in
Alternative 1 operates above the boiling point of EDC which is between 90 to 150° C
and at a pressure of 1.5 to 5 bar [32]. The heat of reaction is seven times the heat of
EDC vaporization can be utilized for purification of product stream. The bubble column
reactor may act as a reboiler of a distillation column or as an independent equipment.
On the contrary, the selectivity of HTC is lower than LTC process, but some patents
claimed that the Ferric (III) Chloride catalysts can be modified until it can achieve the
similar or same selectivity of EDC as in LTC process. However, this is proved to be
cost inefficient since the cost of modified catalyst is very high compare to the cost of
conventional catalysts [19].
In terms of eliminating side reactions, proper heat integration system to

maintain the temperature during pyrolysis and EDC production is essential. To produce
EDC, LTC provides higher selectivity towards the desired product compared to HTC.
LTC reaction also provide better separation of product at the outlet stream which
eliminates azeotrope condition where the EDC could possibly mix with other by-
products, thus LTC eliminates the complication in obtaining high purity EDC for
pyrolysis. Furthermore, LTC reaction does not require any separation unit to separate
the EDC from other by-products due to the absence of by-products in the outlet stream.
The side reaction produces 1,1,2-trichlorethane (TCE) and trichloroethane (TRE).
Meanwhile, the stoichiometry equation of the desired reaction under high temperature
condition are as below;
∆H0298 = -218 kJ/mol C2H4 + Cl2 → C2H4Cl2 (1.18)
The most important by-product is TCE and the stoichiometry is as below;
C2H4Cl2 + 2Cl2 → C2H3Cl3 + HCl (1.19)
1-42
Under rare circumstances, chlorination of EDC produces TRE;
C2H4Cl2 + Cl2 → C2H3Cl3 + HCl (1.20)
High purity reactants could prevent the formation of impurities at significant

amount that might decrease the selectivity and yield of the EDC. Furthermore, in
pyrolysis reaction, it is essential to operate the furnace at temperature 500°C and at
26 atm pressure to raise the conversion of EDC to VCM to 50% [14]. Maintaining the
temperature at temperature 500°C could also raise the selectivity of EDC to VCM until
above 99%. Recycling EDC into the feed stream of the pyrolysis furnace could also
increase the production rate and yield of VCM produced since the amount of unreacted
EDC is high.
Moreover, recycling hydrogen chloride (HCl) into the feed stream as seen in
Alternative 3 could reduce the mass of toxic by-products from the top stream of the
distillation column after pyrolysis process. The recycled HCl can be converted into
chlorine to be used as the feed for EDC production by converting the HCl into chlorine
via the classical Deacon process:
2HCl + 0.5O2 → Cl2 + H2O (1.21)
The new process proposed by Kellogg, the oxidation of HCl utilizes the nitrosyl
sulfuric acid (HNSO5) at 4 bar of pressure and at a temperature of 260 to 320°C. The
number of by-products reduces significantly, raising the overall yield over 98% [54].
This greatly reduce the gaseous emission almost all of them. Chlorinated waste from
other processes can be eliminated through incineration. The incineration process
produces HCl which is to be recycled to the EDC feed stream. In this way, the chance
where oxygen to be contacted with hydrocarbon mixtures can be eliminated.
Consequently, Alternative 3 increases the operation and construction cost due to the
additional number of equipment and the requirement of Copper (II) Chloride catalyst
for the Deacon process which is very expensive [55].
The number of equipment used in the alternatives varied from one to another.
In Alternative 1 and Alternative 2, no extra equipment is required compared to
Alternative 3 since Alternative 3 requires an oxidizing vessel to convert the by-product
HCl to chlorine. Hence, in terms of fixed cost, Alternative 1 offers a better option
compare to Alternative 3 due to the elimination cost in buying the equipment for the
conversion of HCl to chlorine.
1-43
To conclude these comparison, Alternative 1 which is HTC operation, is clearly
not viable. The reaction produces large number of by-products which reduces the
selectivity of the desired EDC. Besides, HTC produces azeotrope product stream
which cause the separation of EDC from the by-products even more complicated. On
the other hand, LTC has no azeotrope condition at the product and the selectivity of
reactants towards EDC is above 99%. This leaves Alternative 2 versus Alternative 3.
The only differences between these two alternatives are the presence of additional
process and equipment for the conversion of HCl to chlorine at the recycle stream in
Alternative 3. Meanwhile, in Alternative 2 does not recycle the HCl to the feed. Instead
Alternative 2 chooses to sell the HCl as secondary product of the plant other than VCM
itself. The presence of HCl treatment reduces the cost of buying chlorine since it can
be recovered from the by-product HCl. In terms of environmental aspect, Alternative 3
eliminates the hazardous HCl to almost zero [54]. However, Alternative 3 increases the
cost of operating and constructing the chlorine recovery unit which uses catalysts such
as Copper (II) Chloride. The catalyst is very expensive, and this could reduce the profit
margin. Hence, Alternative 2 provides the better and safer choice to produce vinyl
chloride and polyvinyl chloride.
1-44
1.4.3 Polyvinyl Chloride Overall Process Flow Diagram (PFD)
Figure 1. 23: Overall process flow diagram of PVC plant.
1-45
1.5 PROCESS DETAILS
A successful process design for PVC plant must comprised the important
process details such as chemistry, kinetics, stoichiometry and thermodynamics. The
process details are important in order to determine the effectiveness of overall process.
It also provides any vital information about the production of PVC, in designing a PVC
plant.
1.5.1 Chemistry
Three reactions are involved in PVC plant which are direct chlorination,
pyrolysis and polymerization process. The first reaction is direct chlorination. Direct
chlorination is a one step process which chlorine in gas phase and pure ethylene
reacted. This reaction performed in the presence of ferric chloride catalyst in
homogeneous phase. Ferric chloride also is used to avoid contamination of ethylene
dichloride and reduce the corrosion risk in the process unit [56]. Hence, the reaction is
carried out in low temperature at 50ᴼC and pressure at 4 bar as it does not produce
any by-product. The product of this reaction is EDC with a chemical compound of 1, 2-
dichloroethane is mainly used to produce VCM. Therefore, EDC is a colourless liquid
and usually act as intermediate for any solvent and organic compounds [57]. The
reaction equation is as follow:
CH2CH2 (g) + Cl2 (g) → ClCH2CH2Cl (g) (1.22)
The second reaction is pyrolysis or thermal cracking of ethylene dichloride to

produce vinyl chloride monomer. Pyrolysis or commonly known as thermal cracking
was carried out in endothermic reaction with temperature at 500ᴼC and 26 bar pressure
[58]. High temperature reaction is required in order to decompose EDC to form VCM
and HCl. The heat in ther furnace is generated thru combustion of fuel gas. The
reaction performed in homogeneous phase since all phase in liquid phase. HCl
produced in this reaction is classified as by-product. The reaction equation is as follow:
ClCH2CH2Cl (g) → CH2CHCl (g) + HCl (g) (1.23)
The last reaction is suspension polymerization. The reaction is converting vinyl chloride
monomer to polyvinyl chloride. This reaction was carried out in a batch process called
autoclave vessel where vinyl chloride monomer and water was filled in the autoclave
and primary granulating agent (surfactant) as well small amount of initiator was added
1-46
in the reaction [59]. This process an exothermic reaction as it released heat to form
new bonds [60]. The water in the autoclave act as suspension medium. Thus, as
temperature of reaction in suspension polymerization increase, the molecule of
initiators dissociated and polymerization process will start [59]. The reaction equation
is as follow:
n·CH2CHCl (l) → (CH2CHCl)n (1.24)
1.5.2 Reaction Kinetics
The reaction kinetics is very important in designing polyvinyl chloride plant to

study the rate law, rate constant and stoichiometry in polyvinyl chloride plant design.
Additionally, kinetic studies are important for understanding reactions. For instance,
reaction kinetics may help to determine the time taken for reaction to be completed.
1.5.2.1 Rate Law
Rate law is the rate of the reaction that will express in a function of the concentration
of the reactants and products involved in reactions in polyvinyl chloride process.
First reaction
𝑘1 (1.25)
CH2 CH2 (l) + Cl₂(l) → ClCH2 CH2 Cl(g)
𝑘1 (1.26)
𝐴+𝐵→𝐶
From the reaction above, the rate law can be generated as follow:
−rA = k1 CA CB (1.27)
Where:
-rA : Rate of disappearance of ethylene, C2H2 (s-1)
k1 : Rate constant (dm3/mol·s)
CA : Concentration of ethylene, CH2 CH2 (mol/dm3 )
C : Concentration chlorine, Cl₂ (mol/dm3 )
1-47
Second reaction
𝑘2 (1.28)
ClCH2 CH2 Cl(l) → CH2 CHCl(l) + HCl (l)
𝑘2 (1.29)
D→E+F
−𝑟𝐷 = k 2 CD (1.30)
Where:
−rD : Rate of disappearance of ethylene dichlorine, ClCH2 CH2 Cl (s −1 )
K3 : Rate constant (dm3/mol·s)
CD : Concentration of ethylene dichlorine, ClCH2 CH2 Cl (mol/dm3 )
Third reaction
𝑘3 (1.31)
n ∙ CH2 CHCl(l) → (CH2 CHCl) n
𝑘3 (1.32)
G→H
−𝑟𝐺 = k 3 CG (1.33)
Where:
−rG : Rate of disappearance of vinyl chloride monomer, CH2 CHCl (s −1 )
K3 : Rate constant (dm3/mol·s)
CG : Concentration of vinyl chloride monomer, CH2 CHCl (mol/dm3 )
Based on the rate law for three reactions from PVC production, it can be
considered that all reactions are first order reaction. Therefore, previous study has
proved that reaction in PVC process can be considered as first order reaction as the
mechanisms are purely molecular and the reactions involved are irreversible [14].
1-48
1.5.2.2 Rate Constant, k
In chemical kinetics, rate constant. k can affect the rate of chemical reaction
due to many factors such as concentration of reactants, temperature and presence of
catalyst. It can be described in Arrhenius equation. According to Arrhenius
equation[61], rate constant increases as temperature increase. Therefore, in presence
of catalyst will lower the activation energy as well increase the rate constant and rate
of reaction. This is due to the minimum energy needed for the reaction occur.
−Ea⁄ (1.34)
k A (T) = Ae RT
Where:
A : Pre-exponential factor or frequency factor
E : Activation energy (J/mol)
R : Gas constant (8.314J/mol·K) or (1.987 Cal/mol·K)
T : Absolute temperature (K)
1.5.2.3 Stoichiometry
For a flow system, the concentration CA at a given point can be determined from
molar flowrate FA and the volumetric flowrate ʋ at that point:
FA (1.35)
CA =
ʋ
Where:
FA : Mole flowrate (mol/s)
CA : Concentration (mol⁄dm3 )
ʋ : Volumetric flowrate (dm3 /s)
FA0 − FA (1.36)
X=
FA0
Where:
X : Conversion rate
FA0 : Initial mole flowrate (mol/s)
1-49
Rearrange Equation 1.36:
FA0 X = FA0 − FA (1.37)
FA0 X = FA0 − FA (1.38)
FA = FA0 (1 − X) (1.39)
At liquid phase reaction:
ʋ = ʋ0 (1.40)
Substitute Equation 1.39 to Equation 1.36:
FA0 (1 − X) (1.41)
CA =
ʋ
Since ʋ = ʋ0 :
FA0 (1 − X) (1.42)
CA =
ʋ0
At initial concentration:
FA0 (1.43)
CA0 =
ʋ0
Substitute Equation 1.43 into Equation 1.42:
CA = CA0 (1 − X) (1.44)
At gas phase reaction:
ʋ ≠ ʋ0 (1.45)
𝑃0 𝑇 (1.46)
ʋ = ʋ0 (1 + 𝜀𝑋) ( ) ( )
𝑃 𝑇0
Where:
X : Conversion
P0 : Total pressure initial (atm)
T0 : Temperature initial (⁰C)
P : Pressure (atm)
T : Temperature (⁰C)
1-50
ε = yA0 δ (1.47)
Where:
yA0= mole fraction of A
δ= change in total number of moles/ moles of A reacted
Substitute equation 1.46 into equation 1.41:
FA0 (1 − X) (1.48)
CA =
P T
ʋ0 (1 + εX) ( P0 ) (T )
0
CA0 (1 − X) (1.49)
CA =
P T
(1 + εX) ( P0 ) (T )
0
1.5.2.4 Stoichiometry Table for PVC Production Process
Reaction 1: Production of EDC
FeCl2 (1.50)
C2 H4 (g) + Cl2 (g) → C2 H4 Cl2 (g)
Table 1. 23: Stoichiometry table for Reaction 1.

Initial Output
Effluent
Substanc Specie rate rate Concentration
rate
e s feed (kmol/h (kmol/𝐝𝐦𝟑 )
(kmol/h)
(kmol/h) )
CA
FA CA0 (1 − X)
=
Ethylene A FA0 −FAo X = FA0 (1 P T
(1 + εX) ( P0 ) (T )
− X) 0
CB
FB b
FB0 b = FA0 (θB CA0 (θB − a X) P0 T
Chloride B − FAo X = ( )( )
= θB FA0 a b 1 + εX P T0
− X)
a
FC
Ethylene FC0 c = FA0 (θC c
C F X
a Ao
CC = CA0 (θC + X)
Dichloride = θC FA0 c a
+ X)
a
1-51
Reaction 2: Production of VCM
C2 H4 Cl2 (g) → C2 H3 Cl(g) + HCl(g) (1.51)
Table 1. 24: Stoichiometry table for Reaction 2.

Substance Species Initial Output Effluent Concentration
rate feed rate rate (kmol/𝐝𝐦𝟑 )
(kmol/h) (kmol/h) (kmol/h)
Ethylene C FC0 −FCo X FC CC = CC0 (1 − X)
Dichloride = FC0 (1
− X)
Vinyl D FD0 d FD CD
F X
c Co
chloride = θD FC0 = FC0 (θD d
CC0 (θD + X)
monomer d = c
+ X) P0 T
c (1 + εX) ( P ) (T )
0
e
Hydrochloric E FE0 F X FE CE
c Co e
acid = θE FC0 = FC0 (θE CC0 (θE + c X)
e =
+ X) P T
c (1 + εX) ( 0 ) ( )
P T0
1.5.3 Thermodynamics
Production of PVC from ethylene will undergo few processes which will first
produce EDC and VCM. Both productions of EDC and PVC are exothermic reactions
while the production of VCM is an endothermic reaction. Changes of temperatures from
one process to another will involve thermodynamics process. Thermodynamic
properties will affect the reaction, product, and process in the manner of energy of
reaction. In this section for PVC plant design, examples of thermodynamics properties
that will be discuss are temperature, Gibb’s free-energy, heat of reaction and use of
catalyst.
1.5.3.1 Thermodynamic Properties
In designing a PVC production plant, thermodynamic properties of every

substances related to the process is important in developing information and
knowledge in chemical reaction prediction and designing chemical reactors. Table 1.25
shows the thermodynamic properties of the related substances in PVC production
process.
1-52
Table 1. 25: Thermodynamic properties of substances used in PVC production process.
Properties at Standard Ethylene Chlorine Ferric Ethylene Hydrochloric Vinyl Chloride Water
Condition Chloride Dichloride Acid
Monomer
Molecular weight (kg/kmol) 28.05 70.91 162.2 98.97 36.47 62.598 18.016
Melting point (°C) -169.2 -101.0 306 -35.3 -114.2 -153.84 0
Boiling point (°C) -103.7 -34.06 315 83.7 -85.0 -13.8 100.0
Critical temperature (K) 283.1 417.0 290 324.6 424.61 647.4
Critical pressure (bar) 51.17 77.1 53.6 82.58 57.55 220.55
Heat of vaporization (KJ/mol) 13.54 20.4 50.375 -169.7 16.1 20.9 40.656
Standard enthalpy of formation 52.28 -74.81 -396.02 -169.7 -92.31 38.10 -285.84
(kJ/mol)
Standard Gibbs energy of 68.46 -74.74 37.9 -80.33 41.87 -237.129

formation (kJ/mol)
1-53
1.5.3.2 Temperature
1.5.3.2.1 Direct Chlorination of Ethylene to Produce 1,2-Dichloroethane (EDC)
Temperature can be considered as the main factor in the rate of a chemical

reaction. The molecular kinetic energy shows that, as the temperature of substance
increases, its molecules will vibrate and bounce with more energy and at higher
speeds. Figure 1.24 shows the changes of phase of an ice from solid to gas. At specific
temperatures, vibrations break the bonding that cause the molecules stick to each
other, causing solids to melt into liquids, and liquids to boil into gases. Gases react to
heat with an increase in pressure as molecules collide against their container with
greater force.
Figure 1. 24: The changes of phase of an ice from solid to gas [6].
Direct chlorination of ethylene consists of reaction between dissolved gaseous

reactants in the liquid following the equation :
∆H°298 = -218 kJ/mol C2H4 + Cl2 → C2H4Cl2 (1.52)
1-54
Ethylene and chlorine are fed in stoichiometric amounts at 25°C and 1 atm to a
1.5 atm in a bubble column reactor. The circulation of reactant gases via sparger
dispersion through liquid 1,2-dichloroethane is maintained at 90°C by a cold-water
stream. The bubble column reactor design maximizes ethylene mass transfer and is
mostly applied in the industry. At this condition, the exiting of direct chlorination reactor
producing a 97% pure EDC with limited side reaction and unreacted feed compounds
[62]. The bubble column reactor should be maintained to have operating temperature
below the boiling point of the mixture. At low-temperature chlorination, it give higher
selectivity approximately over 99% [14].
1.5.3.2.2 Pyrolysis of 1,2-Dichloroethane (EDC)
Temperature plays a vital role in determining the selectivity and conversion of

EDC to vinyl chloride monomer. The optimum temperature is 500ᴼC which the
decomposition of EDC to form vinyl chloride occurs instantaneously. The yield will be
around 99% of VCM. However, increasing the temperature above 500ᴼC this could
greatly increase the conversion but it reduces the selectivity towards the desired
product [32]. Rapid quenching is required to prevent tars and heavy by-products
formation in the thermal cracker [19]. The thermal cracking of EDC happens in a
furnace and is a highly endothermic reaction and is shown in reaction 1 [14];
∆H = +97 kJ/mol CH2Cl—CH2Cl → CH2=CHCl + HCl (1.53)
The heat is obtained from a series of burners in the furnace chamber, fed by
natural gas. Higher pressure is preferable to minimize the furnace size, maximize heat
integration and make downstream separation easier. Figure 1.25 shows the energy
profile for endothermic pyrolysis reaction of EDC to produce VCM and HCl, assuming
A, B and C as EDC, VCM and HCl, respectively.
1-55
B+C
Figure 1. 25: The energy profile for endothermic reaction.
The pyrolysis of EDC requires a high amount of heat energy input to

decompose EDC into VCM. Therefore, it is very important to design an optimized heat
integration by using heat pinch from other heat releasing units such as the
polymerization batch reactor, gas burner and the bubble column reactor. These are the
sources of heat exothermic energy obtained from their respective reactions which are
very valuable in terms of economic considerations. It is very essential to install heat
exchangers and heat jackets across the system to allow the heat from hot unit to be
transferred to the pyrolysis chamber [14].
1.5.3.3 Gibb’s Free Energy
To calculate the maximum of reversible work that may be performed by a

thermodynamic system at a constant temperature and pressure such as isothermal or
isobaric condition, Gibbs energy or Gibbs’ function which also known as free enthalpy
can be used. The Gibbs energy is the maximum amount of non-expansion work that
can be extracted from a thermodynamically closed system. The maximum that have
been stated can be attained only in a completely reversible process. The Gibbs energy
also thermodynamic potential that is minimized when a system reaches chemical
equilibrium at constant pressure and temperature. With respect to the reaction
coordinate, its derivatives vanish at the equilibrium point. The reduction in Gibbs free
energy is necessary condition for the spontaneity of processes at constant pressure
and temperature. The Gibbs free energy is defined as:
G(p, T) = U + pV − TS (1.54)
Which is the same as:

1-56
G(p, T) = H − TS (1.55)
Where :
U : Internal energy (J)
P : Pressure (Pa)
V : Volume (m3)
T : Temperature (K)
S : Entropy (J/K)
H : Enthalpy (J)
1.5.3.4 Heat of Reactions
The heat of reaction or enthalpy is the changes in the enthalpy that occur during
a chemical reaction at constant pressure. Enthalpy is commonly used in
thermodynamic as it is very useful in determining the energy value per mole whether
they are released or absorbed. The heat of reaction determines the exothermicity or
endothermicity of a reaction by looking at the value of heat of reaction. A positive value
indicates endothermic behaviour while negative value indicates exothermic behaviour
[63]. In a PVC production plant, both exothermic and endothermic behaviour coexists
in a system as shown in Equation 1.52 and Equation 1.53. The EDC process and
suspension polymerization process both are exothermic and releases heat. An
exothermic reaction shows that the reaction releases their internal energy as heat
energy to form new bonds. These two proves useful in supplying heat of reaction to be
distributed across other equipment. On the other hand, the pyrolysis furnace works
endothermically. The heat of reaction shows positive value which indicates a positive
change in the internal energy of the pyrolysis of EDC reaction. The compound EDC
requires large amount of heat to break the bonds between the carbon, hydrogen and
chlorine atoms in EDC compound [63].
1.5.3.5 Catalyst
Catalyst is an adding substance that can increase the rate of reaction. In

general, the catalyst provides an alteration reaction mechanism with a lower activation
energy than the non-catalyzed mechanism. This has affected the chemical reaction to
occur faster. The catalyst usually reacts to form a temporary intermediate, which then
regenerates the original catalyst in a cyclic process. Figure 1.26 shows the presence
1-57
of the catalyst opens a different reaction pathway (shown in red) with a lower activation
energy.
Figure 1. 26 : Generic potential energy diagram showing the effect of a catalyst in a

hypothetical exothermic chemical reaction X (acetylene) + Y (chlorine) to give Z
(EDC) [6]
Based on Figure 1.24, the direct chlorination reaction that consist of acetylene
react with chlorine to produce EDC is consume less energy when there is presence of
a catalyst. The catalyst use is Lewis-acid type, in most cases iron (III) chloride, (FeCl3)
with the concentration of 0.1 to 0.5 wt.% [14]. This FeCl3 catalyst polarize the chlorine
to increase its electrophilic activity and encourage attack on ethylene’s double bond
[64].
1.6 WASTE TREATMENT
Waste treatment management is a collection, handling, processing and

managing waste materials. This includes the identification of major wastes, regulation
limit and waste treatment strategy. The purpose of this treatment is to give an overview
on how to a treat waste that come out from the reaction which is the waste might be
hazardous to environment and harmful to residential. As a fact, it is necessary to design
a plant that environmentally friendly towards the sustainable development.
Environmental, waste prevention and treatment are essential to the chemical process
industry. It is important to avoid any damage to human or environment as the waste
might be toxic and poisonous. Waste prevention is one of the environmental protecting
methods that eliminate the need of handling, transportation and treatment of waste. In
1-58
this production of Polyvinyl Chloride (PVC), the waste that need to be treated is
wastewater.
Waste water of this plant contain high biochemical oxygen demand (BOD),
chemical oxygen demand (COD), total organic carbon (TOC), chloride ion, sodium ion
and sulfate. This waste needs to treat because it may harm human, plant life and
animals. BOD shows the amount of oxygen that consumed by organics in water by
protozoa and bacteria. Diseases commonly caused by bacteria, viruses and protozoa
that get washed into drinking water. Many pathogens in wastewater may cause chronic
diseases such as stomach ulcer and degeneration. Bacteria have wide range of
infection to human body such as diarrhea, dysentery skin and tissue infections, gastritis
and others. There are many types of bacteria that may consists in waste water like E.
coli, Listeria, Salmonella, Vibrio. TOC is the number of carbon-containing compounds
in a waste water. When high TOC concentration in waste water means high oxygen in
water that be used up by aquatic life because they cannot survive. TOC is not directly
affected human health but intense cases where anaerobic (non-oxygenated)
conditions result, the toxic salts produced may bad effects (Total organic carbon or
COD/3). Semiconductor manufacturing processes have some of the most stringent
specifications for ionic and organic contamination in water. TOC in water
semiconductor manufacturers to improve product quality and maximize yields so it
needs. For sulfate, if the component in excess in water may affect human body can
irritate eyes, skin, and lungs for long-term use.The wastewater effluent is produced
from the pyrolysis process, regeneration of ferric chloride (FeCl3) catalyst, and the
polymerization of VCM. The wastewater treatment plant consists of collection tank,
equalization tank, coagulation tank, flocculation tank, sedimentation tank and sludge
treatment system [65]. The coagulant use in the coagulation tank is FeCl3 while the
flocculant use in the flocculation tank is alum. Sludge produced are treated in the
sludge treatment system until it is readily to be sent to the sludge disposal site. The
effluent from the wastewater treatment plant is monitored and controlled to comply with
the Standard B of the Environmental Quality (Industrial Effluent) Regulations 2009 [66].
Figure 1.27 shows the wastewater treatment process for PVC plant.
1-59
FLocculant Dosing Tank
Coagulant Dosing Tank
Industrial Effluent
Screening
pH Adjustment Tank
pH Adjustment Tank
Coagulation Tank Flocculation Tank
Equalization Tank
Secondary Clarifier Aeration Tank
Treated Effluent
Sludge Collecting Tank
Sludge
Filter Press
Figure 1. 27: Block flow diagram of wastewater treatment process for PVC plant. [71]
1-60
1.7 CONCLUSION
To conclude the design process background and selection for the plant design
for production of 50,000 tonnes PVC per annum, firstly, direct chlorination with low
temperature condition is the selected process in producing EDC. The process is
operating with pressure 1.5 atm at 90°C. The main raw materials used in the process
are ethylene and chlorine. In addition, VCM is produced by pyrolysis of EDC which
also known as thermal cracking process. The pyrolysis process is operating with
pressure 26 atm at 500°C. The by-product at pyrolysis process is mainly anhydrous
HCl. Furthermore, the suspension of polymerization of VCM is operating with pressure
7.4 atm at 100°C in the jacket batch reactor. The suspension agent use is polyvinyl
alcohol (PVA) and benzoyl peroxide is use as the initiator of the process. Besides, the
production of PVC in this design project begins with the production of EDC from direct
chlorination reaction. The EDC then is converted to the VCM in the pyrolysis process.
Finally, the polymerization of VCM is happen with the addition of the PVA as the
suspending agent in the suspension polymerization. Recycling system is also applied
in this design project.
Finally, for waste treatment in this design project, the wastewater effluent from
this design project is treat with coagulation and flocculation process in which ferric (III)
chloride, FeCl3 is the coagulant and alum is the flocculant. The wastewater effluent
from this design project need to be treated, monitored and controlled well so that it is
comply with the Standard B of the Environmental Quality (Industrial Effluent)
Regulations 2009.
1-58
CHAPTER 2
MARKET ANALYSIS
2.0. ECONOMIC DATA/SUPPLY AND DEMAND
2.1 Introduction
Generally, market analysis studies the market potential among the potential
buyer. A preliminary market analysis is the first step in determining whether a plant
will be profitable or not. No plant design should proceed to the final stages before the
overall economic feasibility is considered[67]. Additionally, the goal of market analysis
is looking into several important factors such as demand from end segment markets,
potential value, consumption and application of products. Therefore, market analysis
is an important component to determine the sales and production of polyvinyl chloride
for different segments of customers as well to increase profit of the plant.
2.2 Applications of Polyvinyl Chloride
Polyvinyl chloride (PVC) is one of the most used and valuable product of chemical
industry. It contributes to the cost effectiveness and quality. Due to its versatile nature,
PVC was used widely in industry and everyday applications such as in leisure
equipment, cables, packaging, pipes, medical, tensile roofs, flooring and windows as
illustrated in Figure 2.1.
Figure 2. 1: PVC application
2-1
PVC is a versatile plastic polymer that has applications in many industries.
Construction industry is one of it. Since 2015, over 50% of PVC manufactured was
used for construction as PVC has been replacing traditional building materials such
as wood, concrete and clay in highly growing segment with remarkable growth trends
around the globe[68]. PVC was also extensively used in windows, roofing, flooring
and windows especially as an alternative to traditional wood frames at low cost [69].
Besides that, PVC was commonly used in pipes industry. This popularity is
due to a unique combination of PVC properties like safety, durability, cost efficiency,
environmental performance and recyclability of PVC. Hence, PVC pipes was a safe
choice for transportation of drinking water. This is due to the high degree of resistance
to corrosion as well as PVC pipe was free from contamination of bio-film that can be
a breeding ground for bacteria[70].
In electrical and electronic industry, PVC was used as the insulation on electric
cables. It was first used in cables as a replacement of rubber since the cables made
from PVC do not crack easily and was used in a wide range varying from
telecommunications to electric blankets[69]. Therefore, PVC was used widely in
pharmaceutical industry for used as rigid packaging includes containers such as cups
and bottles(report). PVC’s durability and strength give it the flexibility necessary for
applications such as blood bags and IV containers. Thus, PVC products can be easily
sterilized using steam, radiation or ethylene oxide and with its excellent water and
chemical resistance, solutions can be kept sterile [71].
Apart from that, these resins have also made application in commercial
industry. In flat sheet form, PVC was often expanded and used to produce a wide
variety of commercial signage products[68] It can produced with different thickness
and colours according current demand. In addition, PVC was used in fabrics and
clothing such as coats, jackets and aprons because PVC is water resistant and
wrinkle free materials. Hence, it was also used widely to create artificial leather
materials as it is less expensive than original leather or latex [72].
As described above, PVC can be segregated across a broad range of
industries include construction, pipes, electrical and electronic, pharmaceutical and
commercial industry as PVC was a versatile polymer and has many special
characteristic. So, the growth of these industry is the key contributors to the demand
of polyvinyl chloride in near future.
2-2
2.3 Global Consumption of Polyvinyl Chloride
China is leading for consumption of polyvinyl chloride in 2016 compared to

other country. As shown in Figure 2.2, China is the dominant consumer of polyvinyl
chloride which consumed more than 35% of total world consumptions. United States,
Western Europe and Indian Subcontinent ranked as the highest consumer of
polyvinyl chloride with approximately more than 13% of PVC consumption and the
followed by South-East Asia and Middle East country with about 10% total world
consumption [73] . Malaysia is one of the listed country in South-East Asia. Other than
that are Thailand, Indonesia, Singapore, Brunei, Vietnam and Philippines. Among all
country in South-East Asia, Malaysia is the largest exporter of plastic products
including PVC product [74]Thus, it make Malaysia is the leading country in South-
East Asia for PVC consumption in 2016. Additionally, Malaysia PVC consumption was
expected increase in the near future due to the rising demand on industries such as
food and beverage, electronic and pharmaceuticals industries[74] Apart from that, the
countries that consumed less than 10% of polyvinyl chloride in 2016 are South
America, Africa, Japan and Baltic states.
Figure 2. 2: world consumption of polyvinyl chloride in 2016 [5]
2-3
2.4 Production of Polyvinyl Chloride
The global production of polyvinyl chloride (PVC) was rapid growth due to the
rising demand on industries such as food and beverage, electronic and
pharmaceuticals industries[74]. However, production of PVC in Malaysia doesn’t meet
the market demand. Figure 2.3 clearly shows that, production of Malaysia PVC has
decreased and the capacity is much lower than demand as well in import and export
activities.
Malaysia PVC
300
250
200
demand
150
import
capacity
100 export
50
0
2010 2015 2016 2017 2018 2019 2020
year
Figure 2. 3: Malaysia PVC Demand, Exports, Imports and Capacity
From analysis Figure 2.3, Malaysia PVC demand increase within year.
Increasing in PVC demand was effected by development of a country. This happen
due to the need of PVC in broad range of applications such as in leisure equipment,
cables, packaging, pipes, medical, tensile roofs, flooring and windows. The analysis
was further described in Table 2.1.
2-4
Table 2.1: PVC resin data in Malaysia
Needed
Needed in
Demand Import Capacity Export in Malaysia
Year
(ktpa) (ktpa) (ktpa) (ktpa) Malaysia -
(ktpa) Demand
(ktpa)
275 – 86 189 – 175
2010 175 50 275 86
=189 = 14
100 – 27 73 – 245
2015 245 204 100 27
=73 = -172
100 – 20 80 – 250
2016 250 205 100 20
=80 = -170
100 – 25 75 – 255
2017 255 210 100 25
=75 = -180
100 – 40 60 – 260
2018 260 220 100 40
=60 = -200
100 – 40 60 – 270
2019 270 225 100 40
=60 = -210
100 – 30 70 – 280
2020 280 230 100 30
=70 = -210
From data in Table 2.1, the demand of PVC was increase significantly from
2010-2018 about 85 kilotonnes per annum as the import and export activities of PVC
increase. However, the current PVC capacity in Malaysia is very low. Capacity of PVC
in Malaysia declined due to PVC plant in Malaysia which is PVC Malaysia Kerteh,
Terengganu retreated from PVC market in 2012. As result, PVC production in
Malaysia decreased since 2013 until now as illustrated in Figure 2.4. Thus, Malaysia
still lack of 200 kilotonnes per annum in order to meet PVC demand in Malaysia for
2018 demand trend. Additionally, the Malaysia PVC market was expected growing
rapidly until 2020. Therefore, a new PVC plant was needed to overcome this issue in
near future as well become the largest PVC supplier in Malaysia as the PVC demand
was expected to increase significantly.
2-5
300
250
200
150
100
50
0
2008 2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
Ind Resin Mal. Johor Bahru Malay Electro Penang

Kaneka Paste Poly Gebeng, Kuantan PVC Malaysia Kerteh, Terengganu
Figure 2. 4: Malaysia PVC capacity
2-6
2.5 PRODUCTION RATE AND PROFITABILITY STUDY
2.5.1 Yearly Cost and Stream Factor
In order to calculate the cost of labor and cost of utilities the stream factor and
yearly cost need to be consider. Stream factor is that proportion of the time, during
which a complete plant is in operation that any individual item of the plant is working.
Stream Factor usually in the range of 0.90 to 0.96. Equation 2.1 was used in order to
calculate yearly cost.
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑑𝑎𝑦𝑠 𝑝𝑙𝑎𝑛𝑡 𝑜𝑝𝑒𝑟𝑎𝑡𝑒 𝑝𝑒𝑟 𝑦𝑒𝑎𝑟 (𝑁)

𝑆𝐹 = (2.1)
365 𝑑𝑎𝑦𝑠
𝑁
0.96 = 365 𝑑𝑎𝑦𝑠
𝑁 = 0.96 𝑥 365 𝑑𝑎𝑦𝑠
𝑁 = 350.4 𝑑𝑎𝑦𝑠 ≈ 351𝑑𝑎𝑦𝑠 (14 days shutdown)
2.6 TOTAL CAPITAL INVESTMENT
Total Capital Investment include fixed capital investment and working capital. In
order to calculate the fixed investment, the cost of equipment need to be consider.
Table 2.2 shows the total cost that been used in order to construct PVC resin plant.
2-7
Table 2.2: Cost of every component
Power Purchased
Compres (kilowatts # Equipment Bare Module
sors Compressor Type ) Spares MOC Cost Cost
Carbon RM RM
C-101 Centrifugal 450 1 Steel 377,000.00 1,030,000.00
Area Purchased
(square Equipment Bare Module
Dryers Type meters) Cost Cost
RM RM
Dy-101 Tray 1.8 8,440.00 12,700.00
2-8
Continue
Tube
Shell Pressu Area Purchased
Exchang Pressure re (square Equipment Bare Module
ers Exchanger Type (barg) (barg) MOC meters) Cost Cost
Carbon Steel / RM RM
E-101 Double Pipe 2.07 Carbon Steel 3 3,670.00 12,100.00
E-103 Double Pipe 86 Carbon Steel 3 3,670.00 13,400.00
2-9
Continue
Steam
Super Purchased
Fired Heat Duty heat Pressure Equipment Bare Module
Heaters Type (MJ/h) (°C) MOC (barg) Cost Cost
Carbon RM RM
H-101 Pyrolysis Furnace 10800 Steel 26.3 414,000.00 910,000.00
Pumps Power Purchased

(with (kilowatts # Discharge Equipment Bare Module
drives) Pump Type ) Spares MOC Pressure (barg) Cost Cost
Carbon RM RM
P-101 Centrifugal 2 1 Steel 26.3 6,610.00 32,700.00
Carbon RM RM
2-10
Continue
Carbon RM RM
Carbon RM RM
Carbon RM RM
Carbon RM RM
Volume Purchased
(cubic Equipment Bare Module
Reactors Type meters) Cost Cost
Jacketed Non- RM RM
R-101 Agitated 30 33,400.00 50,100.00
RM RM
R-102 Autoclave 5 73,900.00 111,000.00
2-11
Continue
Volume Purchased
Storage (cubic Equipment Bare Module
Tanks Tank Type meters) Cost Cost
RM RM
Tk-101 Fixed Roof 90 53,300.00 58,600.00
RM RM
Tk-102 Fixed Roof 90 53,300.00 58,600.00
Diamet
er Purchased
Height (meter Tower Pressure Equipment Bare Module
Towers Tower Description (meters) s) MOC Demister MOC (barg) Cost Cost
10 Carbon Steel Carbon RM RM
T-101 Sieve Trays 3 0.5 Steel 10 12,700.00 22,500.00
10 Carbon Steel Carbon RM RM
T-102 Sieve Trays 3 0.5 Steel 10 12,700.00 22,500.00
Empty Vertical Carbon RM RM
T-103 Vessel 3 0.5 Steel 10 3,160.00 13,000.00
2-12
Continue
Diamet
Length/H er Purchased
eight (meter Pressure Equipment Bare Module
Vessels Orientation (meters) s) MOC Demister MOC (barg) Cost Cost
Carbon RM RM
V-101 Horizontal 3 0.5 Steel 10 3,760.00 11,400.00
Carbon RM RM
V-102 Horizontal 3 0.5 Steel 10 3,760.00 11,400.00
Total Bare RM
Module Cost 2,592,600.00
2-13
Table 2.3: Direct Cost
Direct cost
Component Estimation Cost(RM)
Total Equipment cost - 2592600
Piping system installation 8% of total equipment cost 207408
Instrumentation and control 2% total equipment cost 51852
Electrical system installation 3% of total equipment cost 77778
Services facilities 3% of total equipment cost 77778
Building, process and auxiliary 3% of total equipment cost 77778
Land (100 acre) RM45/acre 4500

Utilities Cooling water = RM 2788.75
57.50/hour
Electricity = RM 168.5/hour 8426.17276
Steam @ 100PSI = RM 9461.078

556.534/hour
Yard improvement 5% of total equipment cost 129630
Total Direct Cost 3240000.001
2-14
Table 2.4: Indirect Cost
Indirect Cost
Component Estimation Cost (RM)
Engineering and supervision 8% of total direct cost 259200.0001
construction fees
Legal expanses 5% of total direct cost 162000
Contractor fees 3% of total direct cost 97200.00002
Contingency 9% of total direct cost 291600.0001
Total indirect Cost 810000.0002

Fixed Cost Investment 4050000.001
Based on Table 2.3 and Table 2.4, the fixed cost investment was RM 4,
050,000.00. Using this value, working capital and total capital investment can be
calculate using Equation 2.2 and 2.3 respectively:
Working Capital = 17% X Fixed Cost Investment (2.2)
Working Capital = 17% X RM4,050,000.00
= RM 688,500.00
Total Capital Investment = Fixed Capital Investment + Working Capital (2.3)
Total Capital Investment = RM4,050,000.00 + RM688,500.00
= RM 4,738,500.00
2-15
2.7 OPERATING CAPITAL COST
According to Turton, et. al., the cost of manufacturing can be calculated if the
following operating capital costs are known or can be estimated.
1. Fixed capital investment (FCI)

2. Cost of operating labor (COL)
3. Cost of utilities (CUT)
4. Cost of waste treatment (CWT)
5. Cost of raw material (CRM)
2.7 Cost of Raw Material, CRM
2.7.1 Annual Cost for Ethylene
RM0.30 44960tonne 2204.623lb

Ethylene = X X
lb yr tonne
= RM 29,735,955.02/yr
2.7.2 Annual Cost for Chlorine
RM0.18 113440tonne 2204.623lb

Chlorine = X X
lb yr tonne
= RM 45,016,637.96/yr
2.7.3 Expected Revenue
The expected revenue from production of Polyvinyl chloride and Hydrochloric acid:
RM0.60 50000tonne 2204.623lb

Polyvinyl chloride = X X
lb yr tonne
= RM 66,138,690.00 /yr
2-16
RM0.25 29200tonne 2204.623lb
Hydrochloric acid = X X
lb yr tonne
= RM 16,093,747.90 /yr
(RM66,138,690.00 + RM 16,093,747.90)
Profit Margin =
yr
(RM 29,735,955.02 + RM 45,016,637.96)
−
yr
= RM 7,479,844.92 /yr
2.8 Cost Operating Labor, COL
Equation 2.4 was used in order to calculate the number of operators needed
per shift:
NOL = (6.29 + 31.70P2 + 0.23Nnp )0.5 (2.4)
Where:
NOL= number of operators per shift
P= number of processing steps involving the handling of particulate solids and in
general, the value of P = 0
Nnp= number of non-particulate processing steps such as compression, tower,
heating and cooling, mixing and reaction
Table 2.5: Number of Non-Particulate Processing Steps

Equipment Units Nnp
Reactor 2 2
Heat Exchanger 9 9
Pump 6 -
Furnace 1 1
Storage Tank 2 2
Compressor 1 1
Distillation column 3 3
Vessel 2 2
2-17
Dryer 1 1
Total 27 21
Based on Table 2.5, the number of non-particulate processing step was 21.
According to Malaysian Investment Development Authority (MIDA), the normal
working hours are not exceeding 8 hours in a day or 48 hours in a week. In average,
a single operator work on 49 weeks per year which equal to 245 shifts per year. If the
operator work six shifts per week then the number of shift required per year is:
351 Days 1week 6shifts

X X = 300.86shifts/(operator. year)
Year 7 days operator. week
≈301 shifts/ (operator.year)
Production of Polyvinyl chloride covered 24 hours per day:

24 hours shifts
X = 3shifts/day
day 8 hours
3shifts 351 days
X = 1053 shifts/year
day 1 year
Operator needed in a year:

1053 shifts operator. year
X = 3.5 operator
year 301 shifts
The NOL value:

NOL = (6.29 + 31.70(0)2 + 0.23(21))0.5
= 3.33/ shifts
Number of operating labour:

3.33
Number of operating labour = X3.5 operator
shifts
= 11.655 operator/ shifts
≈ 12 operator/ shifts
As a backup if any emergency occur, the number of operating labour need to be

double:
12 operator
Total number of operating labour = X2 X 3 shifts
shifts
2-18
= 72 operators
Assume that the salary for a single operating labour is RM 18,000 per year. The
Cost of Operating Labour, COL:
𝑅𝑀18,000
𝐶𝑂𝐿 = 72 𝑜𝑝𝑒𝑟𝑎𝑡𝑜𝑟𝑠 𝑋
𝑦𝑒𝑎𝑟
= RM 1,296,000/ year
2.9 Cost of Utilities, CUT
Table 2.6 shows the utilities cost values that obtained from MIDA.
Table 2.6: Cost of Utilities

Utilities
Name Fluid Rate unit Cost per Cost
hours units
Electricity KW 168.5 RM/hour
cooling water water MMGAL/H 57.5 RM/hour
Steam @100PSI steam KLB/H 556.53 RM/hour
Total Utilities Cost 782.53 RM/hour
2-19
2.8 OTHER MANUFACTURING COST
In order to calculate the cost of manufacturing, there is to criteria that need to

be considered which is direct manufacturing cost and indirect manufacturing cost.
Table 2.7 show direct manufacturing cost while Table 2.8 show indirect manufacturing
cost.
Table 2.7: Direct Manufacturing Cost

Direct manufacturing
Component Estimation Cost
Raw Material - 74752592
Utilities - 6592032.73
Operating Labour - 1,296,000
Direct supervision and clerical labor 15%COL 194400
Maintenance and repairs 4%FCI 162000
Operating supplies 0.9%FCI 36450
Laboratory charges 10%COL 129600
Patents and royalties 2%FCI 81000
Total Direct manufacturing Cost 83244074.73
2-20
Table 2.8: Indirect Manufacturing Cost
Fixed Manufacturing Cost
Depreciation 10%FCI 405000
Local taxes and insurance 2%FCI 81000
Plant overhead cost 60% COL + 3.6% FCI 923400
Total Fixed Manufacturing Cost 1409400
Total Manufacturing Cost, COM 84653474.73
2-21
2.9 VARIABLE COST
Based on the Cost of manufacturing that been calculate at Table 2.8, total variable
cost was calculate in Table 2.9.
Table 2.9: General Variable Cost

General Expense
Raw Material - 74752592.98
Administration cost 16.7% COL + 540432

8% FCI
Distribution and selling cost 9% COM 7491966.726
Research and development 5% COM 4162203.737
Total Variable Cost 86947195.44
2.10 BREAKEVEN ANALYSIS
Breakeven analysis is used to measure the payback period (PBP), breakeven

analysis can be measure using Equation 2.5 using variable cost (calculate using
Equation 2.6):
Fixed Cost Investment,FCI

Breakeven Analysis = (2.5)
(unit selling price−variable cost)
Total Variable Cost

Variable Cost = Target Polyvinyl Chloride Production
(2.6)
2-22
RM 86947195.44
Variable Cost =
79200 tonne
= RM 1,097.82/ tonne
RM 4,050,000
Breakeven Analysis =
(RM 1,873.93/tonne − RM 1,097.82/ tonne)
=5,218.33 tonne
2.11 PAYBACK PERIOD (PBP)
The shorter the Payback period, the higher the profit. Based on Equation 2.7,
the payback period been calculated:
Breakeven Analysis
Payback Period = (2.7)
Production rate
5,218.33 tonne
Payback Period =
79200 tonne/year
= 0.07 year ≈ 1 year
Figure 2. 5: Graph Cash Flow Analysis for discounted data
2-23
In Figure 2.5 shows that, the profit for this project will increase within 3 year after the
construction of the plant.
Figure 2. 6: Cash Flow Analysis discounted criteria
Figure 2. 7: Cash flow analysis non-discounted criteria
In Figure 2.6 shows the discounted profitability criteria while in Figure 2.7
shows the non-discounter profitability criteria for cash flow analysis. Table 2.10 shows
the cash flow analysis table using CAPCOST.
2-24
Table 2.10: Cash Flow Analysis table
Year Investment dk FCIL-Sdk R COMd (R-COMd-dk)*(1-t)+dk Cash Flow Cash Flow Cumulative Cumulative
(Non- (discounted) Cash Flow Cash Flow
discounted) (discounted) (Non-
discounted)
0 0.00 4.05 (0.00) (0.00) (0.00) (0.00)
1 1.62 4.05 (1.62) (1.47) (1.48) (1.62)
2 1.22 4.05 (1.22) (1.00) (2.48) (2.84)
3 1.90 4.05 (1.90) (1.43) (3.91) (4.74)
4 0.41 3.65 822.23 84.65 427.97 427.97 292.31 288.39 423.22
5 0.73 2.92 822.23 84.65 428.10 428.10 265.82 554.21 851.32
6 0.58 2.33 822.23 84.65 428.04 428.04 241.62 795.83 1279.37
7 0.47 1.87 822.23 84.65 427.99 427.99 219.63 1015.46 1707.36
8 0.37 1.49 822.23 84.65 427.95 427.95 199.64 1215.10 2135.31
9 0.30 1.19 822.23 84.65 427.92 427.92 181.48 1396.58 2563.23
10 0.27 0.93 822.23 84.65 427.91 427.91 164.98 1561.56 2991.14
11 0.27 0.66 822.23 84.65 427.91 427.91 149.98 1711.54 3419.05
12 0.26 0.40 822.23 84.65 427.91 427.91 136.34 1847.88 3846.95
13 0.26 0.13 822.23 84.65 428.14 428.83 124.22 1972.10 4275.79
2-25
2.12 CONCLUSION
In this chapter, economy analysis been done to measure the profit and the loss of
plant design that we proposed in Chapter 1. The main objective in this chapter is to
identify the profit that gain. In the third year after the construction of plant, was increasing
rapidly, due to demand from the world. The payback period based on calculation shows
that at the year 0.07 less than 1 year to payback the investment that been made by our
company.
2-27
CHAPTER 3
SITE SELECTION
3.1 SITE SELECTION
Site location is the first decision in designing a polyvinyl chloride plant. Several
factors have been considered carefully as site location could affect the profitability and
future expansion. There are five site location in industrial zone given by authority have
been shortlisted for polyvinyl chloride plant which is in Gebeng (Pahang), Kerteh
(Terengganu), Telok Kalong (Terengganu), Pengerang (Johor) and Pasir Gudang
(Johor).
3.2 SITE SELECTION CRITERIA
Site selection criteria is a very important aspects in order to identify the most
potential site location. The criteria will be used for the screening and metric scoring
method. In designing polyvinyl chloride plant, the criterion that have been chosen are
raw material supply, transportation facilities and accessibility, availability of utilities,
availability of suitable land and pricing, availability of labor and government incentives.
The criteria for site selection was given priority to the location which near to raw materials
supply to reduce transportation cost. Table 3.1 shows the site selection criteria for
polyvinyl chloride plant. A clear view of site selection criteria will be further described in
the foregoing paragraphs.
3-1
Table 3. 1: List of Site Selection Criterion
NO Site Selection Criterion
1 Raw Material Supply
2 Transportation Facilities
3 Availability of Suitable land and Pricing
4 Availability of utilities
5 Availability of Labor
6 Taxation and Government incentives
7 Local Community Consideration
3.2.1 Raw materials Supply
The availability and cost of suitable raw materials is one of the most important
factor to determine the plant location. Attention has be given to the purchased price of
the raw materials and distance from the source of raw materials to reduce the cost of
transportation. Therefore, polyvinyl chloride plant should be located in a place where the
raw materials can be obtained in huge volume and low cost [75]. Table 3.2 shows the
potential supplier of raw materials for polyvinyl chloride in Johor and Terengganu.
Table 3. 2: Raw materials supplier

Region in State Raw materials
Malaysia ethylene chlorine
South Johor Titan Petchem (M) CCM Chemicals
Sdn Bhd Sdn Bhd
East cost Terengganu Ethylene Malaysia Malay Sino
Sdn Bhd Chemical
Industries Sdn Bhd
Optimal Olefins
Sdn Bhd
3-2
3.2.2 Transportation facilities and accessibility
Transportation facilities is also one of a major site criteria for plant location. This
is to ensure adequate delivery of raw materials or polyvinyl chloride to the specific
location. Polyvinyl chloride can be transport via roads, rail, water and air. Transportation
by road is common for local distribution from central warehouses whereas transportation
by rail is more preferable for long distance [76]. Hence, transportation by seaport and
airport was commonly used to save time. Moreover, the site location must easy to
access. For instance, the site location must near to important facilities such as police
station, fire station and hospital.
3.2.3 Availabilities of Utilities
Plant utilities play a critical role in supporting the operation of the facility in
chemical plant. To produce polyvinyl chloride, large amount of water supply needed for
cooling and heating process. Other than that, power and electrical supply must available
continuously in in polyvinyl chloride plant for daily operation [76]. So, the plant location
must typically close to the low cost of utilities in order to minimize plant cost.
3.2.4 Availability of Suitable Land and Pricing
The characteristics of the land at a proposed plant site must be examined carefully.
The ideal land is flat and well-drained. The next considerations is the land must free from
earthquakes zone [77]. Thus, the land must have additional space to expand the future
facilities of polyvinyl chloride plant. Additionally, the land price for polyvinyl chloride has
been considered to reduce the start-up-capital cost of a new plant.
3.2.5 Availability of labor
Potential supply of requisite type of labor governs plant location to major extent
as it drive force and helps to the plant move toward its strategic goals. There should be
a local pool of unskilled labor in proposed site location that can be trained to operate the
plant, and of skilled craft workers such as engineers to maintain the process units[78].
Thus, having skilled and unskilled labor in the polyvinyl chloride plant, the labor cost can
be reduced.
3-3
3.2.6 Taxation and Government Incentives
Taxation and government incentives in the proposed site location is one of

significant criteria to be considered in deciding location of polyvinyl chloride plant.
Taxation and incentives are one of ways of reducing taxes for businesses and individuals
in exchange for specific investments. The aim of taxation and incentives is to encourage
business and give benefits the community [79]. However, the taxation and incentives
must be consider since each taxation and incentives from government are vary from
each proposed location as well it can affect the start-up capital plant cost.
3.2.7 Local community consideration
The plant location need to fit and acceptable with the community location. Buffer
zone need to construct appropriately to ensure safety and to avoid any accident happen.
Therefore, the guidelines for sitting and zoning of industry and residential areas was
used as guidance to ensure the suitability of a site location for industrial activity. Hence,
to avoid or minimise environmental conflict which would arise between PVC
manufacturing plant and neighbourhood.
3.3 SITE SELECTION EVALUATION
Five site locations of industrial area in Malaysia have been chosen and shortlisted
for polyvinyl chloride plant which the location is in Pengerang, Tanjung Langsat, Gebeng,
Kerteh and Telok Kalong as illustrated which in the red circle area in Figure 3.1 until
Figure 3.5. However, only one site location among five site locations will be chosen to
be the most suitable site location. Screening and metric scoring method have been used
based on site selection criteria. The importance of both method is to choose the best site
location that suitable for polyvinyl chloride plant in term of economic aspect. Besides,
screening and metric scoring method can give a clear comparison between all sites
whereas scoring method. Table 3.3 shows the comparison of site selection between five
different locations.
3-4
Figure 3. 1: Proposed site location in Teluk Kalong industrial area
Figure 3. 2: Proposed site location in Kerteh industrial area
3-5
Figure 3. 3: Proposed site location in Tanjung Langsat industrial area
Figure 3. 4: Proposed site location in Gebeng industrial area
3-6
Figure 3. 5: Proposed site location in Pengerang industrial area
3-7
Table 3. 3: Summary of comparison criteria between site locations
Location Johor Pahang Terengganu
Site Location Pengerang[80] Tanjung Gebeng[82] Kerteh[83] Telok Kalong[84]

Langsat[81]
Raw Material 79 KM 12 KM 74.1 KM 2.60KM 38 KM
Supply 1 hr 21 min drive to 16 min drive to Lotte 1 hr 45 min drive to 5 min drive to 41 min drive to
Ethylene Lotte Chemical Titan Chemical Titan Sdn Ethylene Malaysia Ethylene Malaysia Ethylene Malaysia
Sdn Bhd Bhd SDN BHD SDN BHD SDN BHD
Raw Material 81 KM 79 KM 47 KM 39 KM 8.9 KM
Supply 1 hr 15 min drive to 18 min drive to CCM 1hr 1 min drive to 38 min drive to Malay 10 min drive to Malay
Chlorine CCM Chemicals Sdn Chemicals Sdn Bhd Malay Sino Chemical Sino Chemical Sino Chemical
Bhd Industries Industries Industries
Transport Facilities i Highway i Highway i East Coast i Jalan i Jalan

kota tinggi- Johor-Pasir Expressway Kemaman- Kemaman-
(Road)
pengerang Gudang Dungun Dungun
ii Highway
Senai-
Desaru
3-8
Transport Facilities i KTM Johor ii KTM Johor iii Kerteh- iv Kerteh- i Kerteh-
Bharu, Bharu, Kuantan Kuantan Kuantan
(Railway)
Kempas Kempas Railway Railway Railway
Transport Facilities i Johor port i Tanjung i Sultan i Kemaman ii Kemaman

langsat port Ahmad Shah Port Port
(Port)
Airport,
Kuantan
Accesibility 36 km from nearby 55 km from nearby 34 km from nearby 9.2 km from nearby 17 km from nearby
fire station fire station fire station fire station fire station
80 km from nearby 36 km from nearby 39 km from nearby 8.1 km from nearby 23 km from nearby
hospital hospital hospital hospital hospital
107 km from nearby 31 km from nearby 20 km from nearby 7.8 km from nearby 3.9 km from nearby
police station police station police station police station police station
[80] [81] [82] [83] [84]
Availabilities of Water Supply: Syarikat air Johor (SAJ)[85] Water Supply: Water Supply: Syarikat air Terengganu
Utilities Pengurusan Air (SATU)[87]
(Water Supply) 0 - 35 m3 = RM 2.80 Pahang Berhad
More than 35 m3 = RM 3.30 (PAIP)[86]
Minimum charge = RM 30.00 0 - 35 m3 = RM 1.15
0 – 227 m 3 3
Less than 70 m = RM 0.95
3-9
=RM 0.92 More than 70 m3 = RM 1.15
More than 227 m3 Minimum charge = RM 50.00
=RM0.84
Minimum charge
=RM30.00
Availabilities of Electrical Supply: Tenaga Nasional Berhad (TNB) Malaysia

Utilities
(Electrical Supply) TARIFF D - LOW VOLTAGE INDUSTRIAL TARIFF
For the first 200 kWh (1 -200 kWh) per month:38.00 sen/kWh
For the next kWh (201 kWh onwards) per month:44.10 sen/kWh
The minimum monthly charge is RM7.20
TARIFF E1 - MEDIUM VOLTAGE GENERAL INDUSTRIAL TARIFF

For each kilowatt of maximum demand per month: 29.60 RM/kW
For all kWh: 33.70 sen/kWh
TARIFF E2 - MEDIUM VOLTAGE PEAK INDUSTRIAL TARIFF

For each kilowatt of maximum demand per month: 37.00 RM/kW
For all kWh during peak period: 33.50 sen/kWh
For all kWh during off peak period: 21.90 sen/kWh
3-10
TARIFF E3 - HIGH VOLTAGE PEAK/OFF-PEAK INDUSTRIAL TARIFF

For each kilowatt of maximum demand per month during the peak period: 35.50 RM/kW
For all kWh during the peak period: 33.70 sen/kWh
For all kWh during the off-peak period: 20.20 sen/kWh
The minimum monthly charge is RM600.00 [88]
Land Price RM 25.00 – RM 90.00[88] RM 5.00 – RM45.00 – RM60.00[88]

RM 21.00[88]
Availability of labors 4.5 % unemployed rate[89] 2.9 % 3.4 % unemployed rate[89]

(unemployed rate) unemployed
rate[89]
Taxations and Iskandar Develop Region (IDR) receive 10 Investment Tax Exempt from income tax for 10 years and get
incentives years income tax exemption on statutory Allowance (ITA) double deduction for expense for promote
income from the provision of qualifying receive 100% of the ECER Industrial Park[92].
services to a person situated within qualifying capital
designated nodes in the IDR or outside expenditure within 5
Malaysia[90]. years[91].
3-11
Local community More than 300 m More than 300 m More than 300 m
Consideration
(Buffer zone
distance)
3-12
Table 3.4 shows the screening details in five proposed site selection. Telok
Kalong has been chosen as baseline location as a reference for calculation in
screening method. Three symbol were used for rating scale in screening method which
are ‘+’ symbol mean better than reference, ‘-’ symbol means worse than reference and
‘0’ symbol means same as reference.
Table 3. 4: Screening method table

Criterion Site Selection
Pengerang Tanjung Gebeng Kerteh Telok
Langsat Kalong
Raw Material - - - + 0
Supply
Transport Facilities - 0 - + 0
and accessibility
Utilities - - + 0 0
Land Price (per - - + 0 0
sqft)
Availability of + + - 0 0
Labor
Taxation and 0 0 - 0 0
Government
incentives
0 0 0 0 0
Local community
consideration
Top Score -4 -3 -2 2 0
Rank 5 4 3 1 2
Remarks: Symbol represents are: (+) = better (-) = worse (0) = same as reference
Based on Table 3.4, three top sites location which are Gebeng, Kerteh and
Telok Kalong location will be further evaluated in metric scoring method. Concept
scoring is carried out with the identical matrix used. In this step, weightage is introduced
to each criterion that reflects the importance of the criterion. Each criterion then will be
assigned a value from 1 to 5, where 1 = much worse, 2 = worse, 3 = same, 4 = better,
3-13
and 5 = much better. Scoring of each alternative will be calculated by considering the
weightage and the score of each criterion of the process.
Table 3. 5: Scoring method table

Criterion Site Selection
Weightage % Gebeng Kerteh Telok kalong
Raw Material Supply 25 1 4 3

Transport Facilities 15 3 5 3
and Accessibility
Availability of Utilities 15 4 3 3
Land Price (per acres) 15 4 3 3
Availability of labor 10 4 3 3
(Unemployment Rate)
Taxation and incentive 10 2 3 3
Local community 10 3 3 3
consideration
(Buffer zone distance)
Top Score 2.8 3.55 3

Rank 3 1 2
Based on Table 3.5, highest weightage of 25% is given to raw material supply
criterion to reduce transportation cost. Meanwhile, transport facilities and accessibility,
availability of utilities, land price contributed 15% weightage due to its significant.
Hence, availability of labor, government incentives and buffer zone distance
contributed 10% weightage accordingly.
From screening and scoring method, the most potential and suitable plant
location for polyvinyl chloride plant is in Kerteh industrial zone, Terengganu. Kerteh is
the most potential and suitable location for polyvinyl chloride plant due to several
factors. The most significant factor is Kerteh site location is the nearest from raw
materials supplier compared to Telok Kalong and Gebeng. It only take 5 min drive to
Ethylene Malaysia Sdn Bhd for ethylene and 38 min drive to Malay Sino Chemical for
chlorine. Thus, the transportation cost will be low. Next, the taxation and government
incentives in Kerteh give beneficial to investor as an industry can exempt from income
3-14
tax for 10 years and get double deduction for expense by promoting the ECER
Industrial Park tax incentive.
Next, the transport facilities in Kerteh are well developed. Jalan kemaman-Dungun
highway, Kerteh-Kuantan railway and Kerteh-Kuantan Port are available for polyvinyl
chloride transportation. Therefore, the accessibility of site location in Kerteh is better
compared to Gebeng and Telok Kalung which the site location is 9.2 km from nearby
fire station, 8.1 km from nearby hospital and 7.8 km from nearby police station. In
addition, Kerteh site location has equipped with reasonable price of water and electrical
utilities by Syarikat Air Terengganu and Tenaga Nasional Berhad.
3.4 CONCLUSION
In a nutshell, the plant location must be determined by considering many

factors. Therefore, after considering seven site location criterion, Kerteh has become
the site location for polyvinyl chloride plant. Besides that, screening and scoring
methods were used in order to evaluate all the criteria. As result, Kerteh which is
located in Terengganu was selected as the site location due to its advantages
compared to other site locations such as Pengerang, Tanjung Langsat, Gebeng and
Telok Kalong.
3-15
CHAPTER 4
ENVIRONMENTAL AND SAFETY CONSIDERATIONS
4.1 INTRODUCTION
In recent years the importance of safety and environmental issues in chemical

process design has increased. An increase in the number of accidents in the chemical
industries and growing environmental concerns have caused many governments to
ask industries to study worst case scenarios, to control the risk of accidents and to
handle hazardous wastes and gases produced [93]. In Malaysia, the Ministry of Human
Resources through Department of Occupational Safety & Health (DOSH) places
considerable emphasis on inculcating a culture of safety and health in all workplaces.
The two occupational safety & health acts in Malaysia are Factory & Machinery Act
(FMA) 1967 and Occupational Safety and Health Act (OSHA) 1994. Both FMA &
OSHA are Acts that provide the legislative framework to secure the safety, health and
welfare among all Malaysian workforce and to protect others against risks to safety or
health at the workplace [94]. The Occupational Safety and Health Act (OSHA) 1970
established National Institute for Occupational Safety and Health (NIOSH) as a
research agency focused on the study of worker safety and health, and empowering
employers and workers to create safe and healthy workplaces [95]. Other than
occupational safety, chemical manufacturing business or chemical plant may need a
permit, licence, authorisation or exemption to prevent the industrial activities from
causing pollution or harming human health [96]. Chemical industry includes producer
of commodity chemicals, speciality chemicals and chemical products and preparations
such as paints, pesticides, inks, detergents and cosmetics. In Malaysia, Department of
Environment (DOE) of Malaysia is responsible for the prevention, control and
abatement of pollution in the country through the enforcement of the Environmental
Quality Act (EPA) 1974 and its subsidiary legislation [97].
4-1
4.2 RELEVANT LAW, LEGISLATION, REGULATION AND ACT
4.2.1 Factory and Machinery Act (FMA) 1967
Factory and Machinery Act (FMA) 1967 is an act to provide for the control of
factories with respect to matters relating to the safety, health and welfare of person
therein, the registration and inspection of machinery and for other related matters [98].
FMA was approved and came into force by the Parliament of Malaysia in year 1967.
The objectives of the act are to provide for the control of factories with respect to
matters relating to safety, health and welfare of persons at work and to provide control
on registration and inspection of machinery [99]. The relevant regulations for the
production plant of polyvinyl chloride are as follows [98]:
1. Factories and Machinery (Noise Exposure) Regulations 1989.

2. Factories and Machinery (Mineral Dust) Regulations 1989.
3. Factories and Machinery (Building Operations and Works of
Engineering Construction (Safety) Regulations 1986.
4. Factories and Machinery (Administration) Regulations 1970.
5. Factories and Machinery (Notifications of Fitness and Inspections)
Regulations 1970.
6. Factories and Machinery (Safety, Health and Welfare) Regulations
1970.
7. Factories and Machinery (Steam Boiler and Unfired Pressure Vessel)
Regulations 1970.
4.2.2 Occupational Safety and Health Act (OSHA) 1994
Occupational Safety and Health Act (OSHA) 1994 is an act to make further
provisions for securing the safety, health and welfare of persons at work, for protecting
others against risks to safety or health in connection with the activities of persons at
work, to establish the National Council for Occupational Safety and Health, and for
other related matters [100]. Occupational Safety & Health (OSH) standards are
mandatory rules and standards, enforced to eliminate or reduce occupational safety
and hazards in the workplace. Occupational Safety & Health (OSH) standards aim to
provide at least the minimum acceptable degree of protection that must be afforded to
every worker in relation to the working conditions and dangers of injury, sickness or
4-2
death that may arise by reason of his or her occupation [101]. The list of related
regulations under OSHA 1994 with this design project is as follow [100]:
1. Occupational Safety and Health (Classification, Labelling and Safety

Data Sheet of Hazardous Chemicals) Regulations 2013.
2. Occupational Safety and Health (Notification of Accident, Dangerous
Occurrence, Occupational Poisoning and Occupational Disease)
Regulations 2004.
3. Occupational Safety and Health (Use of Standards of Exposure of
Chemical Hazardous to Health) Regulations 2000.
4. Occupational safety and Health (Safety and Health Officer)
Regulations 1997.
5. Occupational Safety and Health (Classification, Packaging and
Labelling of Hazardous Chemicals) Regulations 1997.
6. Occupational Safety and Health (Safety and Health Committee)
Regulations 1996.
7. Occupational Safety and Health (Control of Industrial Major Accident
Hazards) Regulations 1996.
8. Occupational Safety and Health (Employers' Safety and Health
General Policy Statements) (Exception) Regulations 1995.
4.2.3 Environmental Quality Act (EQA) 1974
In the promotion of environmentally sound and sustainable development, the

Government of Malaysia has established the necessary legal and institutional
arrangements such that environmental factors are considered at the early stages of
project planning [102]. Environmental Quality Act (EQA) 1974 is an act relating to the
prevention, abatement, control of pollution and enhancement of the environment, and
for purposes connected therewith [103]. EQA 1974 and other environmental laws are
administered by the Division of Environment (DOE). The National Policy on the
Environment which integrates the three elements of sustainable development:
economic, social and cultural development and environmental conservation was
formulated and approved in 2002. The Policy aims at continued economic, social and
cultural progress and enhancement of the quality of life of Malaysians through
environmentally sound and sustainable development [102]. The relevant regulations of
4-3
EQA 1974 for the chemical plant of the production of polyvinyl chloride are as follows
[102]:
1. Environmental Quality (Licensing) Regulations 1977.

2. Environmental Quality (Clean Air) Regulations 1978.
3. Environmental Quality (Prescribed Activities) (Environmental Impact
Assessment) Order 1987.
4. Environmental Quality (Scheduled Wastes) Regulations 2005.
5. Environmental Quality (Industrial Effluent) Regulations 2009.
4.3 WASTE IDENTIFICATION
Wastes are defined as materials that are no longer suitable for their intended
purpose which includes materials that are waste products of a procedure, old outdated
products that have not been used or new products purchased in excess [104].
Hazardous waste is a waste with a chemical composition or other properties that make
it capable of causing illness, death, or some other harm to humans and other life forms
when mismanaged or released into the environment [105]. Waste identification in
production plant is important in order to ensure proper management of waste, prevent
pollution of schedule waste into environment and monitor the movement of schedule
wastes to registered facility.
In this project, there are two production lines includes vinyl chloride monomer
(VCM) production line and polyvinyl chloride (PVC) production line. In VCM production
line, ethylene dichloride (EDC) is initially produced via direct chlorination process that
combines ethylene and chlorine with presence of ferric chloride catalyst. EDC will be
heated up to 500 ᴼC in pyrolysis reactor to decomposed into VCM and hydrochloric
acid (HCl) with about 50% efficiency. In this production line, flue-gas will be generated
at pyrolysis reactor due to combustion of fuel with air. Therefore, flue-gas need to be
treated before it can be released through the flue-gas stack at some elevation from
ground level and safe location.
Next in PVC production line, VCM is polymerized with water, suspending

agents and initiator through high speed agitation to produce PVC slurry. PVC slurry will
be centrifuged to separate water and unreacted VCM to be recycled into the
polymerization reactor. About 50% of the water separated will also be recycled back
4-4
into the reactor while the remaining will be classified as wastewater that need to be
treated in the wastewater treatment facility. Meanwhile, moist slurry PVC separated will
be dried to produce PVC resin and stored in silo. Top product of the drying process will
be channel to flue-gas stream which will be treated before released into the
environment.
4.4 WASTE TREATMENT AND MANAGEMENT
4.2.1 Flue Gas Treatment and Management
Combustion of natural gas fuel produces harmful precursor of smog called flue
gas which contains nitrogen oxides (NOx), carbon monoxide, carbon dioxide, water
and sulfur dioxide [106]. Most of the harmful flue gas were originated from the furnace,
which utilizes most of the energy from natural gas for pyrolysis of EDC. Flue gas has
been always linked with public health issues such as asthma, bronchitis, lung cancer
and cardiovascular diseases [107]. Therefore, a flue gas desulfurization (FGD) plant is
required to treat the products of natural gas combustion before discharging into the
environment. The block flow diagram of the limestone scrubbing method is shown in
Figure 4.1.
Figure 4. 1: Block flow diagram of the limestone scrubbing method

4-5
The reaction of sulfur dioxide absorption by the scrubber as following;
SO2 + CaCO3 → CaSO3 + CO2 (4.1)
The flue gases trigger some oxidation reaction and the final product of the
treatment system is a wet mixture of (CaSO4) and calcium sulfite (CaSO3) as sludge.
A forced oxidation process occurs in the in the scrubber or the separate reaction
chamber [108]. The injection of air produces a marketable by-product, gypsum CaSO4
• 2H2O by the following reaction;
SO2 + CaCO3 + 2O2 + 2H2O → CaSO4 • 2H2O + CO2 (2)
The main stages in this treatment system are the preparation of raw material
primarily limestones, absorption of the pollutants, pH adjustment in the scrubber
suspension, oxidation of sulfite to sulfate, gypsum separation and effluent treatment
system. Gypsum storage installation also required in this treatment method.
For the preparation of absorber suspension, limestone is mixed with town water
into the absorber feed tank to form a homogeneous suspension. The pH of the
suspension is 7 and contains 20 wt.% of CaCO3. The suspension is the feed of the
absorber. The flue gas flows through the absorber and the sulfur dioxide is absorbed
by the limestone suspension. Then, the sulfite will be oxidized by air, blown from the
bottom part of the absorber, to form sulfate. The absorber has an efficiency depends
on the length of contact time between the limestone suspension and the flue gases.
The clean gases are then reheated above 72ᴼC to be discharged.
With the absorption of sulfur dioxide, the pH value of the suspension drops. The
absorption rate depends greatly on the pH value, since for low pH values the SO2
solubility diminishes; therefore, the suspension is neutralized with fresh feed sorbent
suspension to keep pH value between 5 and 6.5. By this, there is enough chemical
absorption, and the quality of the gypsum produced is maintained.
The gypsum suspension is drawn off from the bottom of the absorber and has
a solid matter content of 7–18 wt%. The gypsum suspension is fed into the gypsum
separator, where most of the water content is drained off. Final removal of water is
completed by centrifuge, and the gypsum is recovered as fine crystals. Upgrading of
4-6
gypsum depends on the intended use of the gypsum produced. The amount of gypsum
is proportional to the SO2 mass flow separated from the flue gases. The quality of the
gypsum is determined by the share of impurities contained, such as silicates, iron,
aluminium, and magnesia compounds (see Table 1.1).
Table 4. 1: Typical composition (by mass) of natural and FGD [108].

Constituents Gypsum
Natural (%) FGD (%)
Moisture 1 7 – 10
Gypsum 78 - 95 94 – 99
Cl < 0.001 < 0.01
Na2O 0.02 < 0.01
MgO (soluble in water) 0.1
Fe < 0.05
F (soluble in water) < 0.05
SO2 < 0.05
CO2 1
K2O (soluble in water) 0.5
pH 6-7 5-8
These compounds enter gypsum via fly ash and limestone. The quality of
gypsum depends also on the installations for the separation of gypsum. Compared to
natural gypsum, the FGD gypsum, in most of the cases, has more constant chemical
composition.
The clarified water is returned to the absorber feed tank, where fresh limestone
is continuously added to replace that converted to gypsum. The high content of
suspended solids and other trace elements in the waste water requires special
treatment in a separate unit. The sludge produced is concentrated and then dewatered
in a chamber filter press. The resulting press cake is disposed of. The purified water is
drawn off in the outfall ditch since it contains heavy metals from the fuel combustion.
Basically, the limestone scrubbing method can be installed downstream of any

boiler with a maximum of 2 x 106 Nm3/h flue gases flow rate. Where there are higher
flow rates of flue gases, the FGD is carried out using two or more lines. To achieve
high SO2 efficiencies, removal of the dust from of flue gases is necessary prior to entry
into the absorber. The method can be used for fuels with sulfur content of up to 3.5%.
There are many limestone scrubbing FGD suppliers in the market. The sulfur
dioxide removal efficiency achieved, in most of the cases, is greater than 95% [109].
The capital cost of the limestone scrubbing method is influenced mainly by the volume
flow of the flue gas. Retrofitting a boiler with FGD installation increases capital costs
4-7
by 16%, due to differences resulting from factors of space and boiler recondition. The
operating costs are influenced by the annual full load operating hours as well as by the
sulfur dioxide mass flow to be separated and by the flue gases flow rate [110].
4.2.2 Wastewater Treatment and Management
The objective of the wastewater treatment plant is to treat the wastewater

effluent from the pyrolysis process, regeneration of ferric chloride (FeCl3) catalyst, and
the polymerization of vinyl chloride monomer (VCM). Wastewater from regeneration of
FeCl3 is rich with hydrogen chloride. Wastewater from polymerization of VCM process
is rich with contaminated water, benzoyl peroxide, and the polyvinyl alcohol (PVA)
which is the suspending agent. The wastewater treatment plant consists of collection
tank, equalization tank, coagulation tank, flocculation tank, sedimentation tank and
sludge treatment system as shown in Figure 4.2 [65].
Collection Equalization
Coagulation Flocculation
Tank Tank
Plant
influent
Effluent Sedimentation
pH and flowrate
adjustment
Sludge Sludge
collection Treatment
Figure 4. 2: Block flow diagram of WWTP of PVC [69].
The contaminated water which is the water used for the cleaning of reactors
containing VCM, transfer lines and suspension, pass through a water stripper to
remove the VCM which is recycled while the water is sent to the wastewater treatment
plant (WWTP) as well as the final effluent containing residual PVC particles and PVA
which are considered as total organic compound (TOC). This effluent is characterized
by being slightly alkaline (ammonia), having low chemical oxygen demand (COD), high
PVA/COD ratio, and containing both aluminium and solids made of fine PVC particles
[65].
4-8
The WWTP of PVC plant is starting with collection of the wastewater at the
settling tank. Next, in the equalization tank, the adjustment of wastewater flow and pH
are happening. It then continues with the coagulation process where ferric chloride
(FeCl3) is used as the coagulant. Next, by using alum as the flocculant, the wastewater
is treats in the flocculation tank. As the flocs had formed, the wastewater treatment is
then proceed in sedimentation tank to remove all the flocs [111]. Finally, all sludges
that formed is then go to the sludge treatment system until it is ready to send to Kualiti
Alam.
The effluent from the wastewater treatment plant is monitored and controlled to
comply with the Standard B of the Environmental Quality (Industrial Effluent)
Regulations 2009 [66].
4.5 HAZARD IDENTIFICATION, RISK ASSESSMENT AND RISK CONTROL
(HIRARC)
Hazard is defined as anything (e.g. condition, situation, practice, behaviour) that

has the potential to cause harm, including injury, disease, death, environmental,
property and equipment damage [112]. Under OSHA 1994, the workplace must be
reduced in its hazard & risk with a systematic manner. In recent years, Hazard
Identification, Risk Assessment and Risk Control (HIRARC) has become fundamental
to the practice of planning, management and the operation of a business as a basic of
risk management. A hazard identification and risk assessment are processes used to
identify and evaluate both existing and potential hazards on a worksite and the
methods used to control or eliminate the hazards identified [112]. By strictly
implementing it, it will eliminate, reduce/control the possibility for any accidents to
occur. Positive changes in working practice have been reported by the party who have
carried out risk assessment at work as the necessary corrective action can be taken
and developed from the recognized substandard act and working condition.
4.2.1 HIRARC PROCESS
Process of HIRARC requires 4 simple steps [113]:
1) Classifies work activities

2) Identify hazard
4-9
3) Conduct risk assessment (analyse and estimate risk from each hazard), by
calculating or estimating:
a) likelihood of occurrence, and
b) severity of hazard;
4) Decide if risk is tolerable and apply control measures (if necessary).
Figure 4. 3: Flowchart of HIRARCH Process [118].
4.2.2 HAZARD IDENTIFICATION
The Hazard Identification Process is to identify the hazards that may cause
major potential accidents for various operational modes, including normal operation,
start-up, and shutdown, as well as potential disturbances, emergency or abnormal
conditions. The goal of hazard identification is to find and record possible hazards that
may be present in workplace. Some process of hazard identification includes knowing
physical work environment, equipment, materials and products that are used, look into
injury and incident records, look into the way the work is organized or done, determine
whether a product, machine or equipment can be intentionally or unintentionally
changed, examine risks to visitors or the public and other related requirements [114].
4-10
4.2.3 RISK ASSESSMENT
Hazard strongly related to risk. Risk means a combination of the likelihood of

an occurrence of a hazardous event with specified period or in specified circumstances
and the severity of injury or damage to the health of people, property, environment or
any combination of these caused by the event Risk assessment means the process of
evaluating the risks to safety and health arising from hazards at work [113]. Risk is
presented in variety of ways to communicate the distribution of the risk throughout a
plant and area in a workplace [112]. Risk can be calculated using the following formula
[115]:
Risk (R) = Likelihood (L) x Severity (S) (4.56)
Likelihood is an event likely to occur within the specific period or in specified

circumstances. Meanwhile, severity is outcome from an event such as severity of injury
or health of people, or damage to property, or insult to environment, or any combination
of those caused by the event.
Table 4. 2: Likelihood of an event [112].
LIKELIHOOD (L) EXAMPLE RATING
Most likely The most likely result of the hazard / event being 5
realized
Possible Has a good chance of occurring and is not unusual 4
Conceivable Might be occur at some time in future 3
Remote Has not been known to occur after many years 2
Inconceivable Is practically impossible and has never occurred 1
4-11
Table 4. 3: Severity of an event [112].
SEVERITY (S) EXAMPLE RATING
Catastrophic Numerous fatalities, irrecoverable property damage

5
and productivity
Fatal Approximately one single fatality major property

4
damage if hazard is realized
Serious Non-fatal injury, permanent disability 3
Minor Disabling but not permanent injury 2
Negligible Minor abrasions, bruises, cuts, first aid type injury 1
Table 4. 4: Risk Assessment Matrix [113].
Likelihood of Severity of Hazard

Hazard
Insignificant Minor Moderate Major Fatal
(1) (2)
(3) (4) (5)
Rare (1) 1 2 3 4 5
Unlikely (2) 2 4 6 8 10
Possible (3) 3 6 9 12 15
Likely (4) 4 8 12 16 20
Almost certain
5 10 15 20 25
(5)
Table 4. 5: Indication of risk level [113].
RISK LEVEL DESCRIPTION ACTION
A risk identified as LOW may be considered

as acceptable and further reduction may not
be necessary. However, if the risk can be
1-4 LOW
resolved quickly and efficiently, control
measures should be implemented and
recorded.
4-12
A MEDIUM risk requires a planned approach
to controlling the hazard and applies
5 - 12 MEDIUM temporary measure if required. Actions taken
must be documented on the risk assessment
form including date for completion.
A HIGH risk requires immediate action to

control the hazard as detailed in the
15 - 25 HIGH hierarchy of control. Actions taken must be
documented on the risk assessment form
including date for completion.
4.2.4 RISK CONTROL
Risk control is the elimination or inactivation of hazard in a manner such that

the hazard does not pose a risk to workers. Hazards should be controlled at their
source where the problem is created [113]. Four characteristics of risk that are
commonly identified according to the measures taken to protect the plant from risk
exposure are [116]:
i. Excellent: the facility has taken measures exceeding industry standards and
the best practices. Loss potential is considered significantly reduced.
ii. Good: the fatality has taken measures that are consistent with industry
standards and best practices. Loss potential is considered to be average.
iii. Fair: the fatality has taken some measures that approach industry standards
and best practices, however deficiencies exist. Loss potential is considered
somewhat increased.
iv. Poor: the fatality has major deficiencies and does not approach industry
standards and best practices. Loss potential is considered to be significantly
increased.
4-13
Table 4. 6: Control Measure Matrix [112].
CONTROL MEASURES LEVEL
Control measures exceeding industry standards and the Excellent 3.1 – 4.0
best practices. Loss potential is considered significantly
reduced.
Control measures that are consistent with industry Good 2.1 - 3.0
standards and best practices. Loss potential is considered
to be average.
Control measures that approach industry standards and Fair 1.1 - 2.0
best practices, however deficiencies exist. Loss potential
is considered somewhat increased.
A control measure has major deficiencies and does not Poor 0 – 1.0
approach industry standards and best practices. Loss
potential is considered to be significantly increased.
All hazards that have been assessed should be dealt with in order of priority.
The most effective control options should be selected to eliminate or minimise risks.
The Hierarchy of Controls ranks control options from highest level of protection and
reliability to lowest that should be used to determine the most effective controls [113].
Figure 4.4 shows the hierarchy of controls sorted by NIOSH.
Figure 4. 4: NIOSH Hierarchy of Controls [122].
4-14
4.2.5 HIRARC FORMS
In section presents the HIRARC forms for all chemicals involved in the reaction
of PVC production. Intermediate chemicals such as EDC and VCM are also included
in as safety precaution although the chemicals will only remain in the process streams
at most of them time. HIRARC form are presented in the Table 4.7, Table 4.8, Table
4.9, Table 4.10, Table 4.11, Table 4.12, Table 4.13, Table 4.14, Table 4.15 and Table
4.16 below:
4-15
Table 4. 7: HIRARC form of Ethylene.
Hazard Identification Risk Analysis Risk Control
Work Hazard Effect Existing risk control Likelihood Severity Risk Recommended Control
activity (if any) Measures
Handling Flammable Fire or  Use unmanned 3 4 12  Extinguish fires of

and explosion hose holder or this gas by
storage of monitor nozzles. shutting-off the
ethylene source of the gas.
 Increase
as raw
ventilation (in  Use water spray to
material
enclosed areas) to cool fire-exposed
prevent flammable containers,
mixture formation. structures, and
equipment.
Exposure  Self-Contained 3 3 9  Remove victim(s)

of Breathing to a safe location.
chemicals Apparatus is used.
 Clear the affected
to workers
 Locate and seal area and allow the
due
the source of the liquid to evaporate
inhalation
leaking gas. and the gas to
dissipate.
4-16
Table 4.0 8: HIRARC form of Ethylene.
4-17
Table 4. 9: HIRARC form of Chlorine.
4-18
Table 4. 10: HIRARC form of Ethelylene Dichloride.
4-19
Table 4. 11: HIRARC form of Vinyl Chloride.
4-20
Table 4. 12: HIRARC form of Hydrogen Chloride.
4-21
Table 4. 13: HIRARC form of Polyvinyl Chloride.
4-22
Table 4. 14: HIRARC form of Benzoyl Peroxide.
4-23
Table 4. 15: HIRARC form of Ferric Choride.
4-24
Table 4. 16: HIRARC form of Water.
4-25
4.6 CONCLUSION
In conclusion, the workplace should be a safe environment where employees

can do their jobs without the fear of injury or death. Unfortunately, sometimes accidents
and even deaths do occur while on the job. Therefore, there are many ways businesses
can reduce the risk of workplace accidents through the implementation of various
safety plans. In this chapter, the relevant law such as Factory and Machinery Act (FMA)
1967, Occupational Safety and Health Act (OSHA) 1994 and Environmental Quality
Act (EQA) 1974 was stated as the aims of this Acts are to provide for the control of
factories with respects to all matters relating to safety and health. Besides, it is also to
promote an environmentally sound and sustainable development. Additionally, it
consists of Hazards Identification, Risk Assessment and Risk Control (HIRARC), waste
management based on the related Acts. Moreover, the main waste in the production
of polyvinyl chloride are flue gas and wastewater. In order to treat the flue gas, a flue
gas desulfurization (FGD) plant is required to treat the products of natural gas
combustion before discharging into the environment. In addition, wastewater effluent
from the pyrolysis process, regeneration of ferric chloride (FeCl3) catalyst, and the
polymerization of vinyl chloride monomer (VCM) will undergo physical-chemical
wastewater treatment such as flocculation and coagulation as act in accordance with
the Standard B of the Environmental Quality (Industrial Effluent) Regulations 2009.
4-13
CHAPTER 5
MASS BALANCE
5.1 INTRODUCTION
Mass balance or also known as material balance. Mass balance approaching

100% indicates that the reaction product and by-products have been satisfactorily
quantified, and the disposition of the reaction product and by-product is well
understood.
Input + Generations − Output − Consumption = Accumulation (5.1)
Where:
Input = Enters through the system boundaries.
Output = Leaves through the system boundaries.
Generations = Product that produce from reaction.
Consumption = Reactant that has been used in this process
Accumulation = The built in the system
5-1
5.1.2 BASIS OF CALCULATION
The expected polyvinyl chloride produce was 50,000 tonnes per year. Equation 5.2,
5.3 and 5.4 shows the main reaction of polyvinyl chloride from ethylene and chlorine.
CH2CH2 (g) + Cl2 (g) → ClCH2CH2Cl (g) (5.2)
ClCH2CH2Cl (g) → CH2CHCl (g) + HCl (g) (5.3)
n·CH2CHCl (l) → (CH2CHCl)n (5.4)
Calculation been made show the flowrate need to produce in order to achieve the
annual production rate of polyvinyl chloride which is 50,0000 tonne per year based on
its operating time 351 days.
Polyvinyl chloride
50,000 tonne 1year 1days 1000 kg

× × ×
year 351 days 24 hours 1 tonne
=5,935.42 kg/hr
In order to achieve the production of PVC of 50000 tonne/year, the production line
needs to produce 5935.42 kg/hr for mass flowrate and 94.9667 kmol/hr for molar
flowrate.
Hydrochloric acid
29,200 tonne 1year 1days 1000 kg

× × ×
year 351 days 24 hours 1 tonne
= 3,466.29 kg/hr
5-2
5.2 PROCESS FLOW DIAGRAM
Figure 5. 1: Process Flow Diagram (Polyvivnyl Vhloride)
5-3
Table 5. 1: Overall Stream Data Table for Polyvinyl Chloride
Streams 1 2 3 4 5 6
Mole
flow
kmol/hr
Ethylene 0 96.11692 0.576702 0.576702 0.576702 0.57670
Chlorine 96.11692 0 0.576702 0.576702 0.576702 0.00346
HCl 0 0 0 0 0 95.5402
EDC 0 0 95.54022 95.54022 63.69348 63.6935
VCM 0 0 0 0 0 94.9669
TCE 0 0 0 0 0.57324 0.57324
Table 5.1 : Continue

Streams 7 8 9 10 11 12
Mole
flow
kmol/hr
Ethylene 0.57670 0.57670 0.57670 0.576702 0 0
Chlorine 0.00346 0.00346 0.00346 0 0.00346 0.00346
HCl 95.5402 95.5402 95.5402 95.54022 0 0
EDC 63.6935 63.6935 63.6935 0 63.69348 63.6935
VCM 94.9669 94.9669 94.9669 0 94.9669 94.9669
TCE 0.57324 0.57324 0.57324 0 0.57324 0.57324
5-4
Streams 13 14 15 16 17 18
Mole
flow
kmol/hr
Water 0 0 0 0 0 4792.95
Chlorine 0.00346 0 0 0 0 0
PVC 0 0 0 0 0 0
EDC 0 63.6935 63.6935 63.6935 63.6935 0
VCM 94.9669 0 0 0 0 0
TCE 0 0.57324 0.57324 0.57324 0.57324 0

Streams 19 20 21 22 23 24
Mole
flow
kmol/hr
Water 0 86346.25 82892.4 3453.85 2935.77 518.08
Chlorine 0 0 0 0 0 0
PVC 0 63.8178 0 63.8178 3.19089 2049.82
EDC 0 0 0 0
VCM 79.77226 15.95445 15.31627 0.63818 0.5425 0.0957
TCE 0 0 0 0 0 0
5-5
Streams 25 26
Mole
flow
kmol/hr
Water 440.368 77.712
Chlorine 0 0
PVC 0 60.627
EDC 0
VCM 0.081345 0.01436
TCE 0 0
5-6
5.3 PROCESS MASS BALANCE ON EACH UNIT
5.3.1 BUBBLE COLUMN REACTOR (R-101)
A bubble column reactor (R-101) is utilized in which a chemical reaction takes place
where for this plant design, it consists of 1 reaction. The product stream from a mixer
(M-101) is passing through a compressor (C-101) to increase the pressure to 1.5 atm
and a heater (E-101) to increase the temperature to 90°C from room temperature
before feeds into the bubble column reactor (R-101) where the operated pressure is
1.5 atm. Thus, Figure 5.2 shows the schematic diagram of a bubble column reactor
(R-101).
Kmol/hr
Kmol/hr
Figure 5. 2: Schematic diagram of Bubble Column Reactor (R-101)
5-7
Degree of freedom analysis :
3 unknown labelled variables (n1, n2, n3)
+ 1 independent reaction
- 3 independent reactive species (Cl2, C2H4, C2H4Cl2)
- 1 additional information (99.4% conversion of C2H4)
0 degree of freedom
Main Reaction : Cl2 + C2H4 → C2H4Cl2 ᶓ1
Assumptions :
1. The operating condition for the reactor is at temperature 90°C and pressure of
1.5 atm.
2. The reaction is operating at continuous process and in steady state condition.
3. The limiting reactant is ethylene, C2H4.
4. The total conversion for chlorine (Cl2) is 99.4%.
5. The selectivity for 1-2 dichloroethane (C2H4Cl2) is 100% [Giovanni].
6. The catalyst in the reactor does not affect the mass balance since it does not
react in the process.
7. The calculation for the reactor will be performed by the extent of reaction
balance
5-8
Extent of reaction :
n1 C2H4Cl2 = ᶓ1 (5.5)
Balance at the outlet stream (S3) :
The selectivity of 1,2-dichloroethane, C2H4Cl2 can be determined by multiplying the

conversion of chlorine and the selectivity of 1,2-dichloroethane as referred from
equation ᶓ1. Selectivity of 1,2-dichloroethane :
C2H4Cl2 = 0.994 x 1.0 = 0.994
96.11692 kmol/hr x 0.994 = 95.54022 kmol/hr
n1 C2H4Cl2 = ᶓ1
n1 C2H4Cl2 = 95.54022 kmol/hr
ᶓ1 = 95.54022 kmol/hr
Outlet molar flowrate of chlorine (Cl2), n2:
99.11692 kmol/hr x (1-0.994) = 0.576702 kmol/hr
Outlet molar flowrate of ethylene (C2H4), n3:
99.11692 kmol/hr x (1-0.994) = 0.576702 kmol/hr
reactor
Component Molar Flowrate, kmol/hr Mass Flowrate, kg/hr

Inlet Inlet Outlet Inlet Inlet Outlet
Stream Stream Stream Stream Stream Stream
(S1) (S2) (S3) (S1) (S2) (S3)
Cl2 96.11692 0 0.576702 6815.651 0 40.89391
C2H4 0 96.11692 0.576702 0 2696.08 16.17648
C2H4Cl2 0 0 95.54022 0 9454.66
Total 96.11692 96.11692 96.69362 6815.651 2696.08
TOTAL 9511.731 9511.731
5-9
5.3.2 FURNACE (R-102)
Furnace reactor is utilized in this plant design to decompose 1,2-dichloroethane to

vinyl chloride monomer and hydrogen chloride by thermal cracking process. The
product stream from R-101 is passing through P-102 and P-103 to increase the
pressure and it also passing through E-102 and E-103 to increase the temperature
before feeds into the furnace. This unit is operated at 500°C and 26 atm. Thus, Figure
5.3 shows the schematic diagram of furnace (R-102).
Kmol/hr
Kmol/hr
Kmol/hr
Kmol/hr
Figure 5. 3: Schematic diagram of the furnace reactor (R-102)
5-10
6 unknown labelled variables (n1, n2, n3, n4, n5, n6)

+ 2 independent reactions (ᶓ1, ᶓ2)
- 6 independent reactive compounds (Cl2, C2H4Cl2, C2H4, HCl, C2H3Cl, C2HCl3)
- 2 additional information (60% conversion of C2H4Cl2, 99.4% selectivity of C2H3Cl and HCl)
0 degree of freedom
Main reaction C2H4Cl2 → C2H3Cl + HCl ᶓ1
:
Second reaction C2H4Cl2 → C2HCl3 + HCl ᶓ2

:
Assumptions :
1. The operating condition for the reactor is at temperature 500°C and pressure
of 26 atm.
2. The reaction is operating at continuous process and in steady state condition.
3. The total conversion for 1,2-dichloroethane (C2H4Cl2) is 60%.
4. The selectivity for vinyl chloride monomer (C2H3Cl) and hydrogen chloride
(HCl) is 99.4% while the selectivity for 1,1,2-trichloroethane (C2HCl3) and
hydrogen chloride (HCl) at second reaction is 0.06%.
5. The calculation for the reactor will be performed by extent of reaction
balances.
Extent of reaction :
C2H4Cl2 → C2H3Cl + HCl ᶓ1
C2H4Cl2 → C2HCl3 + HCl ᶓ2
As referred from the main reaction equation ᶓ1, in order to obtain the production of
vinyl chloride monomer, C2H3Cl, the selectivity of it is 99.4%. Besides that, as referred
from second reaction, ᶓ2, the selectivity of the 1,1,2-trichloroethane and hydrogen
chloride are 0.06% respectively.
5-11
Balance at the outlet stream (S6):
Solving for (C2H3Cl), n1 :
The selectivity of vinyl chloride monomer, C2H3Cl can be determined by multiplying

the conversion of 1,2-dichloroethane and the selectivity of vinyl chloride monomer as
referred from equation ᶓ1. Selectivity of vinyl chloride monomer :
C2H3Cl = 0.6 x 0.994 = 0.5964
159.2337 kmol/hr x 0.5964 = 94.96698 kmol/hr
n1 C2H3Cl = ᶓ1
n1 C2H3Cl = 94.96698 kmol/hr
ᶓ1 = 94.96698 kmol/hr
Solving for (HCl), n2 :
The selectivity of hydrogen chloride, HCl can be determined by multiplying the

conversion of 1,2-dichloroethane and the selectivity of hydrogen chloride as referred
from equation ᶓ1 and equation ᶓ2. Selectivity of hydrogen chloride in ᶓ1 :
= 0.6 x 0.994
= 0.5964
Selectivity of hydrogen chloride in ᶓ2 :
= 0.6 x 0.006
= 0.0036
Total HCl in ᶓ1 and ᶓ2 :
= (159.2337 kmol/hr x 0.5964) + (159.2337 kmol/hr x 0.0036)
= 95.54022 kmol/hr
5-12
n2 HCl = ᶓ1 + ᶓ2
95.54022 kmol/hr = 94.96698 kmol/hr + ᶓ2
ᶓ2 = 0.57324 kmol/hr
Outlet molar flowrate of 1,2-dichloroethane (C2H4Cl2), n3 :
n3 C2H4Cl2 = n C2H4Cl2 - ᶓ1 - ᶓ2
n3 C2H4Cl2 = (159.2337 – 94.95598 – 0.57324) kmol/hr
n3 C2H4Cl2 = 63.69348 kmol/hr
Outlet molar flowrate of 1,1,2-trichloroethane (C2HCl3), n4 :
n4 C2HCl3 = ᶓ2
n4 C2HCl3 = 0.57324 kmol/hr
Outlet molar flowrate of hydrogen chloride (HCl), n5 :
n5 Cl2 =n Cl2 - ᶓ2
n5 Cl2 = (0.576702 – 0.57324) kmol/hr
n5 HCl = 0.00346 kmol/hr
Outlet molar flowrate of ethylene (C2H4), n6 :
n C2H4 = n6 C2H4
n6 C2H4 = 0.576702 kmol/hr
5-13
reactor
Component Molar Flowrate, kmol,hr Mass Flowrate, kg/hr

Inlet Stream Outlet Stream Inlet Stream Outlet Stream
(S5) (S6) (S5) (S6)
C2H3Cl 0 94.96698 0 5935.436
HCl 0 95.54022 0 3483.396
C2H4Cl2 159.2337 63.69348 15757.77 6303.107
C2HCl3 0.573241 0.573241 76.477039 76.477039
Cl2 0.576702 0.00346 40.89391 0.245363
C2H4 0.576702 0.576702 16.17648 16.17648
Total 160.9603 255.3541 15891.31 15891.31
5-14
5.3.3 DISTILLATION COLUMN (T-101)
As for the distillation column (T-101), a mixture of two or more substances in vapor or
liquid phase are separated into its component fractions in which known as distillate,
D and bottom, B as product depends on the differences in the boiling points of the
individual components. As a consequence, the desired purity targeted 98%-100% of
hydrogen chloride can be achieved. The product stream from furnace reactor (R-102)
is passing through two coolers which are E-104 and E-105 before feeds into the
distillation column (T-101) where this unit is operated at 6°C and 12 atm. Thus, Figure
5.4 shows the schematic diagram of a distilled column (T-101).
Kmol/hr
Kmol/hr
Kmol/hr
Kmol/hr
Kmol/hr
Kmol/hr
Figure 5. 4: Schematic diagram of distillation column T-101
5-15
- 6 independent reactive compounds (Cl2, C2H4Cl2, C2H4, HCl, C2H3Cl, C2HCl3)
0 degree of freedom
Assumptions :
The distillation column operates at 500°C and 12 atm.
The distillation column operates at steady state conditions and n reaction is occurring
inside the unit.
No heat generation inside the unit.
Total amount of hydrogen chloride and ethylene will be removed as the distillate.
Overall Balance :
F=D+B
255.3541 kmol/hr = D + B
Balance at the Distillate Product Stream (S10) :
Distillate (D) = Total mole HCl + Total mole C2H4
= (95.54022 x 1.0) kmol/hr + (0.576702 x 1.0) kmol/hr
= 96.11692 kmol/hr
Balance at the Bottom Product Stream (S11) :
F=D+B
255.3541 kmol/hr = 96.11692 kmol/hr + B
B = 159.2372 kmol/hr
5-16
Balance on Hydrogen Chloride, HCl :
Distillate : 95.54022 kmol/hr x 1.0 = 95.54022 kmol/hr
Bottom : 95.54022 kmol/hr x 0 = 0 kmol/hr
Balance on Ethylene, C2H4 :
Balance on Vinyl Chloride Monomer, C2H3Cl :
Distillate : 94.96698 kmol/hr x 0 = 0 kmol/hr
Bottom : 94.96698 kmol/hr x 1.0 = 94.96698 kmol/hr
Balance on 1,2-dichloroethane, C2H4Cl2 :
Balance on 1,1,2-trichloroethane, C2HCl3 :
Balance on chlorine, Cl2 :
5-17
Table 5. 4: Summary of molar flowrate of inlet and outlet streams of the distillation
unit
Component Molar Flowrate kmol/hr

Inlet Stream (S9) Outlet Stream Outlet Stream
(S10) (S11)
C2H3Cl 94.96698 0 94.96698
HCl 95.54022 95.54022 0
C2H4Cl2 63.69348 0 63.69348
C2HCl3 0.573241 0 0.573241
Cl2 0.00346 0 0.00346
C2H4 0.576702 0.576702 0
Total 96.11692 159.2372
TOTAL 255.3541 255.3541
5-18
5.3.4 DISTILLATION COLUMN (T-102)
The distillation column (T-102) is made up of a series stacked plates which it

is a process used to separate a mixture of two or more components by heating the
mixture. The bottom product stream from a distillation column (T-101) is passing
through a heater (E-107) to increase the temperature from 6°C to 93°C before feeds
into the distillation column (T-102). This unit is operated at 93°C and 4.8 atm where
the liquid flows down the column over the plates, and vapour bubbles up through the
liquid via holes in the plates. Thus, Figure 5.5 shows the schematic diagram of a
distilled column (T-102).
Kmol/hr
Kmol/hr
Kmol/hr
Kmol/hr
Figure 5. 5: Schematic diagram for distillation column T-102
4 unknown labelled variables (n1, n2, n3, n4)
- 4 independent reactive compounds (Cl2, C2H4Cl2, C2H3Cl, C2HCl3)
0 degree of freedom
5-19
Assumptions :
1. The distillation column operates at temperature 93°C and pressure 4.8 atm.
2. The distillation column operates at steady state conditions and no reaction is
occurring inside the unit.
3. No heat generation inside the unit.
4. There are only 4 components that enter the column T-102 as the total amounts
of hydrogen chloride and ethylene have already been removed at stream 10
of T-101.
5. Total amount of vinyl chloride monomer and chlorine will be removed in the
top product which is at stream 13.
Overall Balance :
F=D+B
159.2372 kmol/hr = D + B
Balance at the Distillate Product Stream (S13) :
Distillate (D) = Total mole C2H3Cl + Total mole Cl2
= (94.96698 x 1.0) kmol/hr + (0.00346 x 1.0) kmol/hr
= 94.97044 kmol/hr
5-20
Balance at the Bottom Product Stream (S14) :
F=D+B
159.2372 kmol/hr = 94.97044 kmol/hr + B
B = 159.2372 kmol/hr
Balance on Vinyl Chloride Monomer, C2H3Cl :
Balance on Chlorine, Cl2 :
Balance on 1,2-dichloroethane, C2H4Cl2 :
Balance on 1,1,2-trichloroethane, C2HCl3 :
5-13
Component Molar Flowrate kmol/hr

Inlet Stream (S12) Outlet Stream Outlet Stream
(S13) (S14)
C2H3Cl 94.96698 94.96698 0
C2H4Cl2 63.69348 0 63.69348
C2HCl3 0.573241 0 0.573241
Cl2 0.00346 0.00346 0
Total 94.97044 64.26672
TOTAL 159.2372 159.2372
5-14
5.3.5 POLYMERIZATION TANK
Polymerization tank carried a chemical reaction that usually used catalyst, heat
or light in which a large number of relatively simple olefin derivatives combine to form
a high-molecular weight product. In this polymerization tank, the catalyst that been
used was benzoyl peroxide and water in order to combine vinyl chloride monomer into
polyvinyl chloride. Figure 5.6 shows the schematic diagram of polymerization tank.
nC2H3Cl = 79.77226 kmol/hr
nH20 = 86346.25 kmol/hr
nC2H3Cl = n1
ncatalyst = 1365.9 kmol/hr
nH20 = n2
n(C2H3Cl)n = n3
Figure 5. 6: schematic diagram of Polymerization tank
5-15
4 unknown labelled variables (n1, n2, n3)
+ 1 independent reaction (ɛ1)
- 4 independent reactive compound (C2H3Cl, H2O, (C2H3Cl)n)
- 1 additional information (80% conversion of VCM)
0 degree of freedom
Main reaction: C2H3Cl  (C2H3Cl)n ɛ1
Assumptions:
1. The operating condition for the tank is at temperature 100⁰C and pressure at
7.4 bar.
2. The reaction is operating at batch process.
3. The total conversion for vinyl chloride monomer is 80%.
4. The water in and out are the same
5. The calculation for the reactor will be performed by extent of reaction balances.
Extent of reaction:
n2 (C2H3Cl)n = ɛ1 0
Balances at the outlet stream:
In order to calculate the selectivity of polyvinyl chloride, (C2H3Cl)n the

conversion of vinyl chloride monomer was multiplied with the selectivity of polyvinyl
chloride in Equation ɛ1.
(C2H3Cl)n = 0.8 X 1.0 = 0.8
Based on Equation 5.5:
(79.77226 kmol/hr X 0.8) = 63.817 kmol/hr
n3 (C2H3Cl)n = 63.817 kmol/hr
ɛ1 = 63.817 kmol/hr
Outlet mol flowrate of vinyl chloride monomer
5-16
n1 = 79.77226 kmol/hr X (1- 0.8)
n1 = 15.954 kmol/hr
Outet mol flowrate of water
n2 = 86346.25 kmol/hr
Table 5. 6: Summary table flowrate of polymerization tank

Compoent Inlet stream Inlet stream 18 Outlet stream 20
kmol/hr kg/hr kmol/hr kg/h kmol/hr kg/hr
VCM 79.77226 3947.132 0 0 15.95445 789.4263
PVC 0 0 0 0 63.8178 3157.706
Water 0 0 86346.25 4792.945 86346.25 4792.945
Total 79.77226 3947.132 86346.25 4792.945 86426.02 8740.077
5.3.6 STRIPPER COLUMN
Suspension resin is produced as aqueous slurry with 10% to 20% unconverted

monomer. Removal by depressurizing can reduce that amount to 1% to 3% but
stripping is required to take the vinyl chloride amount below the 1 ppm level [4]. Figure
5.7 shows the schematic diagram of stripper column.
S21
S20 nAIR = n1
nC2H3Cl = 15.95445 kmol/hr nC2H3Cl = n2
nH2O = 86346.25 kmol/hr nH2O = n3
n(C2H3Cl)n = 63.818 kmol/hr
S22
nC2H3Cl = n4
input
nH2O = n5
nAIR = 1
n(C2H3Cl)n = n6
Figure 5. 7: Schematic diagram of stripper column
5-17
- 4 independent reactive (C2H3Cl, H2O, (C2H3Cl)n)
- 2 additional info (96% selectivity of C2H3Cl and H2O)
0 degree of freedom
Assumptions
1. The stripper column operates at 90⁰C and 1.0atm.

2. Assume the mole flowrate of air is 100 kmol/hr
3. The stripper column at semi batch reaction.
4. 96% selectivity of vinyl chloride monomer and water.
Overall mass balance
S20 + input = S21 + S22
(nC2H3Cl + nH2O + n(C2H3Cl)n) + input = S21 + S22
86426.02 kmol/hr + 100 kmol/hr = S21+ S22
S21 + S22 = 86526.02 kmol/hr
Mole compound of C2H3Cl:
Liquid inlet stream
S20nC2H3Cl = 15.95445 kmol/hr
Vapor outlet stream
S21n2 = 0.96 X S20nC2H3Cl
S21n2 = 0.96 X 15.95445 kmol/hr
S21n2 = 15.31627 kmol/hr
Liquid outlet stream
S22n4 = (1-0.96) X S20nC2H3Cl
S22n4 = 0.04 X 15.95445 kmol/hr
5-18
S22n4 = 0.63818 kmol/hr
Mole compound of H2O:
Liquid inlet stream
S20nH2O = 86346.25 kmol/hr
Vapor outlet stream
S21n3 = 0.96 X S20nH2O
S21n3 = 0.96 X 86346.25 kmol/hr
S21n3 = 82892.4 kmol/hr
Liquid outlet stream
S22n5 = (1-0.96) X S20nH2O
S22n5 = 0.04 X 86346.25 kmol/hr
S22n5 = 3453.85 kmol/hr
Table 5. 7: Summary flowrate of stripper tank

Compoent S20 S21 S22
kmol/hr kg/hr kmol/hr kg/hr kmol/hr kg/hr
VCM 15.95445 789.4263 15.31627 757.8493 0.638178 31.57705
PVC 63.8178 3157.706 0 0 63.8178 3157.706
Water 86346.25 4792.945 82892.4 4601.228 3453.85 191.7178
Total 86426.02 8740.08 83180.9 5360.205 3518.31 2381.0
5-19
5.3.7 CENTRIFUGAL
Centrifugal unit is a type of physical separator used to remove heavy

constituent from light constituents in a mixture. A centrifuge is a piece of equipment
that puts an object in axial rotation, exerting a perpendicular force that pushes the
heavier components towards the wall. By weight, the heavier components move
towards the wall of the centrifugal separator. The efficiency of the unit is 85% removal
of water and VCM. The average PVC loss due to centrifugal force is 5%. The inlet of
centrifugal unit is Stream 22, while the outlet containing removed water and VCM is at
Stream 23 which is directly connected to the wastewater treatment plant. Stream 24
contains 98.3% PVC. The purity of PVC changes from 91.1% to 98.3% in this unit.
Figure 5.8 shows the schematic diagram of centrifugal.
nC2H3Cl = n4
nC2H3Cl = 0.638178 kmol/hr
nH2O= 3453.85 kmol/hr nH2O= n5
n(C2H3Cl)n = 63.8178 kmol/hr n(C2H3Cl)n = n6
nC2H3Cl = n1
nH2O= n2
n(C2H3Cl)n = n3
Figure 5. 8: Schematic diagram of Centrifugal
5-20
- 2 additional information (85% efficiency removal of C2H3Cl and H2O and 5%

PVC loss)
0 degree of freedom
Assumptions
1. The centrifugal operates at steady state.

2. 85% efficiency removal of water and vinyl chloride monomer.
3. 5% of polyvinyl chloride loss due to centrifugal force.
4. No heat generation of the unit.
Mass balance at stream 23:
Vinyl chloride monomer
n1 = 0.85 X nC2H3Cl
n1 = 0.85 X 0.638178 kmol/hr
n1 = 0.5425 kmol/hr
Water
n2 = 0.85 X nH20
n2 = 0.85 X 3453.85 kmol/hr
n2 = 2935.77 kmol/hr
Polyvinyl chloride
n3 = 0.05 X n(C2H3Cl)n
n3 = 0.05 X 63.8178 kmol/hr
n3 = 3.19089 kmol/hr
Mass balance of stream 24:
5-21
n4 = (1- 0.85) X nC2H3Cl
n4 = 0.15 X 0.638178 kmol/hr
n4 = 0.0957267 kmol/hr
Water
n5 = (1-0.85) X nH20
n5 = 0.15 X 3453.85 kmol/hr
n5 = 518.08 kmol/hr
Polyvinyl chloride
n6 = (1-0.05) X n(C2H3Cl)n
n6 = 0.95 X 63.8178 kmol/hr
n6 = 60.62691 kmol/hr
Table 5. 8: Summary flowrate for centrifugal

Component S22 S23 S24
VCM 0.6382 31.577 0.5425 26.84 0.0957 4.7366
H2O 3453.85 191.7178 2935.77 162.96 518.08 28.7577
PVC 63.8178 2157.706 3.19089 107.885 60.627 2049.82
Total 3518.31 2381.0 2939.50 297.685 578.80 2083.31
Purity of PVC in S24:
= 2049.82 / 2083.31 x 100%
= 98.3%
Purity of PVC in S22:
= 2157.706 / 2381.0 x 100%
= 91.1%
Difference in purity:
= 98.3 – 91.1
= 7.2%
5-22
5.3.8 DRYER
Dryer is a type of physical separator used to remove water from a mixture. A
dryer applies heat into the PVC resin at 100oC at 1atm to remove water at its boiling
point. The efficiency of the unit is 85% removal of water and VCM. The inlet of dryer is
Stream 24, while the outlet containing removed water and VCM is at Stream 25 which
are condensed and directly connected to the wastewater treatment plant. Stream 26
contains 0.2% water. The moisture content changes from 1.3% to 0.2% in this unit.
nC2H3Cl = n3
nC2H3Cl = 0.0957 kmol/hr nH2O= n4
nH2O= 518.08 kmol/hr n(C2H3Cl)n = n5
n(C2H3Cl)n = 60.627 kmol/hr
nC2H3Cl = n1
nH2O= n2
Figure 5. 9: Schematic diagram of Dryer
5 unknown labelled variables (n1, n2, n3, n4, n5)
- 2 additional info ( 85% removal of C2H3Cl and H2O)
0 degree of freedom
Assumptions
1. The dryer operates at 100⁰C and 1 atm.

2. 85% efficiency removal of vinyl chloride monomer and water.
3. No heat generation in this unit.
5-23
Mass balance of stream 25:
n1 = 0.85 X nC2H3Cl
n1 = 0.85 X 0.0957 kmol/hr
n1 = 0.081345 kmol/hr
Water
n2 = 0.85 X nH2O
n2 = 0.85 X 518.08 kmol/hr
n2 = 440.368 kmol/hr
Mass balance of stream 26
n3 = (1-0.85) X nC2H3Cl
n3 = 0.15 X 0.0957 kmol/hr
n3 = 0.014355 kmol/hr
Water
n4 = (1-0.85) X nH2O
n4 = 0.15 X 518.08 kmol/hr
n4 = 77.712 kmol/hr
Polyvinyl chloride
n5 = 60.627 kmol/hr
Table 5. 9: Summary flowrate of dryer

S24 S25 S26
Component
VCM 0.0957 4.7366 0.081345 4.0261 0.01436 0.7105
Water 518.08 28.7577 440.368 24.444 77.712 4.3137
PVC 60.627 2049.82 0 0 60.627 2049.82
Total 578.80 2083.31 440.449 28.0261 138.353 2054.84
5-24
Moisture content of PVC in S24:
= 28.7577/ 2083.31 x 100%
= 1.3%
Moisture content of PVC in S26:

= 4.3137 / 2054.84 x 100%
= 0.2%
Difference in purity:
= 1.3% - 0.2%
= 1.1%
5-25
CHAPTER 6
ENERGY BALANCE
6.1 INTRODUCTION
Energy balance is a conversion of energy where it is applying the first law of

thermodynamics which means energy cannot be neither created nor destroyed but it
can only be transferred [52]. The important of energy balance in polyvinyl chloride plant
is to determine the requirement energy that needed in a process plant. Therefore, it is
important to calculate energy across each unit in production of polyvinyl chloride. First
law of thermodynamics was applied for conservation of energy in production of
polyvinyl chloride. First law thermodynamics as stated in Equation 6.1
Accumulation of energy in a system = Energy input – Energy output (6.1)
6.1.1 Assumption on Energy Balance
Several assumptions have been made in production of polyvinyl chloride plant which
are listed as follows:
1. The processes follow the law of conservation of energy where:

Energy Out = Energy In + Generation – Consumption – Accumulation
2. System assume as open system at steady state condition
3. For the standard reference state for enthalpy, P=1 atm and T=25℃
4. Assume as an ideal gas system where V∆P assume to be 0
5. Kinetics and potential energies are neglected and consider there is only
enthalpy changes
6. Assume no ΔH of mixing or pressure effect on ΔH
6-1
7. Effect of catalyst used in each process is neglected because they are elemental
species and not involved in the reaction.
6.2 EQUATION USED IN CALCULATIONS
6.2.1 General Equation
The general equation is stated in Equation 6.2 and Equation 6.3 since kinetics and
potential energies are neglected
Q = ΔH (6.2)
6.2.2 Equation for non-reactive process
  
Q  H  
output
n j Hˆ j   n j Hˆ j
input
(6.3)
stream stream
6.2.3 Equation for reactive process
Equation 6.4 is the formula of standard heat of reaction stoichiometric ( Ĥ r ) from the

standard heat of formation of a compound ( Ĥ f ).
Hˆ r   vi Hˆ fi   vi Hˆ fi   v Hˆ  i fi (6.4)

i products reac tan ts
Where
vi = coefficient
6.2.4 Phase Change Equation
For any phase changes, heat of vaporization was used from liquid phase to gas phase
whereas for -ΔHv will be used for phase change from gas to liquid.
6-2
6.2.5 Heat Capacity Equation
For polyvinyl chloride production, the main chemical properties in the process are
ethylene, chlorine, ethylene dichloride, 1;1;2 1;1;2-trichloro-ethane, vinyl chloride
monomer and polyvinyl chloride. Therefore, the value of constant each components
was determined to calculate heat capacity in Equation 6.6. The value for each
coefficient a, b, c, and d can be found in Table 6.1 for gas and Table 6.2 for liquid state.
kJ kJ
Cp (mol . K) or (mol . °C) = a + bT + cT 2 + dT 3 (6.5)
Thus, the Integration equation of heat capacity:
T2 T2
Hˆ   CpdT   (a  bT  cT
2
 dT 3 )dT
T1 T1 (6.6)
After integration, the equation can be described in Equation 6.6
bT2 cT3 dT4

ΔH = [aT + 2
+ 3
+ 4
](T2-T1) (6.7)
6.2.6 Pressure Change equation in liquid phase
H = V∆P (6.8)
Where v is the specific volume of each species based on Coulson & Richardson,
Chemical Engineering, Volume 6
6-3
Table 6. 1: Main properties of chemical compounds in polyvinyl chloride production
COMPONENTS MW CONSTANTS (gas) Boiling Specific Heat Heat
g/mol point volume Formation vaporization
a b c d (KJ/mol) (KJ/mol)
Ethylene C2H4 28 3.806 0.15659 -0.00008348 1.755 -103.8 24.307 52.33 20.4
E-08
Chlorine Cl2 70.9 26.929 0.033838 -0.00003869 1.547 -34.5 24.166 0 13.553
E-08
Ethylene C2H4Cl2 98.9 20.486 0.23103 -0.0001438 3.388 83.4 0.0847 -129.79 32.029
dichloride E-08
Vinyl chloride C2H3Cl 62.5 5.949 0.20193 -0.0001536 4.773 -13.4 23.981 35.27 20.641
monomer E-08
Hydrogen HCl 36.4 30.291 -0.0072 0.00001246 -3.89 -85.1 24.319 92.36 16.1
chloride E-09
1;1;2- C2H3Cl3 133 6.322 0.34307 -0.0002958 9.792 113.7 - -138.58 33.327
Trichloro- E-08
ethane
Water H2O 18 32.243 0.001924 0.00001055 3.596 100 0.001 224.83 56.522
E-09
(Source from Coulson & Richardson’s Chemical Engineering, Volume 6)
6-4
Table 6. 2: Specific heat capacity constant for liquid components in polyvinyl chloride production
COMPONENTS MW CONSTANTS (liquid)
(g/mol)
C1 C2 C3 C4 C5
Ethylene C2H4 28.05
Chlorine Cl2 70.91 63936 46.35 -0.1623 0 0
EDC C2H4Cl2 98.96 179170 -444.74 0.93009 0 0
VCM C2H3Cl 62.5 0 0 0 0 0
Hydrogen chloride HCl 36.46 0 0 0 0 0
1;1;2Trichloroethane C2H3Cl3 133.4 103350 159.3 0 0 0
Water H20 18 276370 -2090.1 8.125 -0.014116 9.3701E-06
(Source from Perry Chemical Engineers’ Handbook Seventh Edition)
Assumptions: Since there are no available value of specific heat capacity constant, Cp of polyvinyl chloride, the specific heat capacity was taken
from reliable journal
Table 6. 3: Specific heat capacity of PVC

PVC Cp = 85.06036403 kJ/kmol.K
6-5
Figure 6. 1: Process Flow Diagram (PFD) for the Production of Polyvinyl chloride production with waste treatment facilities
6-6
6.3 SAMPLE CALCULATION FOR ENERGY BALANCE OF EACH UNIT
6.3.1 Reactor (R-101)
S1 B8
S3
S2
T = 90℃ C2H4 (S1) T = 90℃ C2H4
P = 1.5 atm Cl2 (S2) P = 1.5 atm Cl2
Phase =gas Phase = gas C2H4 Cl2
Figure 6. 2: Bubble Column Reactor
Reference state: 𝐶2 𝐻4 (𝑔), 𝐶𝑙2 (𝑔), 𝐶2 𝐻4 𝐶𝑙2 (𝑙) at 25℃ 𝑎𝑛𝑑 1 𝑎𝑡𝑚
Table 6. 4: Inlet and output enthalpy table for bubble column reactor
Substance Nin 1 Hin1 NIn 2 Hin 2 Nout 3 Hout 3
(kmol/h) (kJ/mol) (kmol/hr) (kJ/mol) (kmol/hr) (kJ/mol)
Ethylene 96.12 52.33 - - 0.58 0.813
Chlorine - - 96.12 0 0.58 1.867
Ethylene - - - - 95.58 -126.14

Dichloride
Table 6. 5: Energy balance table for bubble column reactor

Substance QIn (kJ/hr) QOut (kJ/hr) QOut - Qin (kJ/hr)
Ethylene 5029959.6 471.54 -5029488.06
Chlorine 0 1082.86 1082.86
Ethylene 0 −1.2x107 −1.2x107

Dichloride
QTotal -17028405.2
6-7
Sample calculation of ethylene, C2H4 at inlet stream (S1)
KJ
Reference state= Ethylene (25℃, 1 atm, gas,∆Hf = 52.33 mol)
25°C, 1 atm, (g) 𝐻𝑜𝑢𝑡 25°C, 1.5 atm, (g)
Ha Hb
25 °C, 1 atm, (g)
Hin = Ha + Hb +Hf
25
Ha = ∫ [(3.806) + (0.15659)T + (−8.48 × 10−5 )T 2 + (17.551 × 10−8 )T 3 ]dT
25
KJ
=0 kmol
Since substance was assumed ideal gas, so enthalpy can be zero at ideal gas when
changing the pressure.
Hb = V∆P
=0
KJ
Hf = 52.33 mol
KJ KJ KJ
Hin = 0 + 0 + 52.33
mol mol mol
KJ
= 52.33
mol
Q in = nHin
kmol kJ mol
= (96.12 hr
) (52.33 mol) (1000 kmol)
kJ
= 5029959.6 hr
6-8
Sample calculation of ethylene dichloride, C2H4Cl2 at outlet stream (S3)
25°C, 1 atm, (l) 𝐻𝑜𝑢𝑡 90 °C, 1.5 atm, (g)
Ha + Hv
Hb
83.4 °C, 1.0 atm, (g)
KJ
Reference state= Ethylene dichloride (25℃, 1 atm, gas,∆Hf = −129.79 mol)
Hout = Ha + Hb ++Hf
83.4
Ha = ∫ [(20.486) + (0.23103)T + (−0.0001438)T 2 + (3.388x10−8 )T 3 ]dT
25
+ Hv
KJ KJ
= 2.161 + 32.029
mol mol
KJ
= 2.193 mol
90
Hb = V∆P+∫83.4[(20.486) + (0.23103)T + (−0.0001438)T 2 + (3.388x10−8 )T 3 ]dT
KJ KJ
= 0 mol
+ 1.457 mol
KJ
= 1.457 mol
KJ
Hf = -129.79
mol
Hout = Ha + Hb +Hf
KJ KJ
= 2.193 mol + 1.457 + (−129.79 mol)
KJ
= −126.14
mol
Q out = nHout
kmol KJ mol
= (95.54 ) (−126.14 ) (1000 )
hr mol kmol
6-9
kJ
= −1.2x107 hr
Q total =QOut - Qin
kJ KJ
= (−1.2x107 ) − (−0 )
hr hr
= −1.2x107 kJ/hr
6.3.2 Pump (P-102)
S4
S3
T=90 C2H4
T=90 C2H4
P = 1.5 atm Cl2
P= 26 atm Cl2
Phase = gas C2H4 Cl2 Phase = gas C2H4 Cl2
B14
Figure 6. 3: Pump
Sample calculation for pump for ethylene dichloride at outlet stream
90
Hpump = V∆P+∫25 [(20.486) + (0.23103)T + (−0.0001438)T 2 +
(3.388x10−8 )T 3 ]dT
KJ KJ
= 0 mol+2.161 mol
KJ
= 2.161mol
Q pump = nHpump
kmol kJ mol
= (95.58 hr
) (2.161 mol) (1000 kmol)
kJ
= 2066548.38 hr
∆Q pump inlet and outlet = 0 due to similarities of reference state with inlet condition
6-10
6.3.3 Heater (E-102)
4 5
T = 91.3℃ C2H4 T = 242℃ C2H4
P = 26 atm Cl2 P = 26 atm Cl2

Phase = gas C2H4 Cl2
Phase = gas C2H4 Cl2
B7
Figure 6. 4: Heater
Table 6. 6: Inlet and output enthalpy table for heater

Substance Nin 4 Hin4 Nout 5 Hout 5
(kmol/h) (kJ/mol) (kmol/hr) (kJ/mol)
Ethylene 0.58 0.82 0.58 4.98
Chlorine 0.58 1.90 0.58 6.65
Ethylene Dichloride 95.54 34.24 95.54 42.52
Table 6. 7: Energy balance table for heater

Substance QIn QOut QOut - Qin
Ethylene 475.6 2850.14 2374.54
Chlorine 1102 3859.32 2757032

Ethylene 3271829.6 4062074.18 790244.58
Dichloride
QTotal 3549651.12
6-11
Sample calculation of chlorine, Cl2 at outlet stream
Reference state= Chlorine (25℃, 1 atm, gas)
Hout = Ha + Hb + Hc +Hd
𝐻𝑜𝑢𝑡
25°C, 1 atm, (g) 242 °C, 26 atm, (g)
Hb Hc
242 °C, 1 atm, (g)
242
Ha = ∫ [(26.929) + (0.033838)T + (−0.00003869)T 2 + (1.547x10−8 )T 3 ]dT
25
KJ
=6.654 mol
Hb = V∆P
=0
Hout = Ha + Hb
KJ KJ
= (6.654 mol
) + (0 mol)
= 6.654
Q out = nHout
kmol kJ mol
= (0.58 ) (6.654 ) (1000 )
hr mol kmol
kJ
= 3859 hr
6-12
6.3.4 Furnace (R-102)
B8 C2H4
S5 S6 Cl2
C2H4 Cl2
C2H3 Cl
T = 242℃ C2H4
T = 500℃
C2H3 Cl3
P = 26 atm Cl2 P = 26 atm
HCl
Phase = gas C2H4Cl2 Phase = gas
Figure 6. 5: Furnace
Reference state: C2 H4 (g), Cl2 (g), C2 H4 Cl2 (g) at 25℃ and 1 atm
Table 6. 8: Inlet and output enthalpy table for furnace

Substance Nin 5 Hout5 NIn 6 Hout 6
Ethylene 0.6 57.31 0.6 70.49
Chlorine 0.6 6.65 0.24 15.64
Ethylene Dichloride 99.4 -87.27 39.76 -64.69
Vinyl Chloride - - 59.28 57.62
1;1;2- - - 0.36 -103.59

Trichloroethane
Hydrochloric acid - - 59.64 106.31
6-13
Table 6. 9: Energy balance for furnace
Substance QIn(kJ/hr) QOut(kJ/hr) QOut - Qin(kJ/hr)
Ethylene 34386 42275 7889
Chlorine 3990 3753.6 -236.4
Ethylene -8674638 -2572074.4 6122563.6

Dichloride
Vinyl Chloride 0 3515710 3515710
1;1;2- 0 -37294 -37294

Trichloroethane
Hydrochloric 0 3151020 3151020
acid
QTotal 12759652.2
Sample calculation of C2H4at outlet stream
KJ
Reference state= Ethylene (25℃, 1 atm, gas,∆Hf = 52.33 mol )
𝐻𝑜𝑢𝑡
25°C, 1 atm, (g) 500 °C, 26 atm, (g)
Ha
Hb
500 °C, 1 atm, (g)
Hout = Ha + Hb + Hc +Hf
500
Ha = ∫ [(3.806) + (0.15659)T + (−8.48 × 10−5 )T 2 + (17.551 × 10−8 )T 3 ]dT
25
KJ
=18.129 mol
6-14
Hb = V∆P
=0
KJ
Hf = 52.33mol
Hout = Ha + Hb +Hf
KJ KJ KJ
= (18.129 mol) + ( 0 mol) + (52.33 mol)
KJ
= 70.459
mol
Q out = nHout
kmol kJ mol
= (0.6 hr
) (70.459 mol) (1000 kmol)
kJ
= 42275
hr
6.3.5 Quench Tank (S-101)
C2H4 S6 S7
Quench
C2H4
Cl2
Tank
Cl2
C2H4 Cl2
C2H4 Cl2
C2H3 Cl
T = 500℃ T = 170℃ C2H3 Cl
C2H3 Cl3
P = 1.5 atm P = 26 atm C2H3 Cl3
HCl Phase = gas Phase = gas
HCl
Figure 6. 6: Quench Tank
6-15
Table 6. 10: Input and output enthalphy for Quench Tank
Substance Nin 6 Hin6 Nout 7 Hout 7
Ethylene 0.6 70.49 0.6 2.63
Chlorine 0.6 15.64 0.24 4.32
Ethylene Dichloride 99.4 -64.69 39.76 38.09
Vinyl Chloride 0 57.62 59.28 3.48
1;1;2-Trichloroethane 0 -101.59 0.36 38.05
Hydrochloric acid 0 106.31 59.64 5.3
Table 6. 11: Energy balance for Quench Tank

Ethylene 42275 1578 -40697

Chlorine 3753.6 1036.8 130
Ethylene -2572074.4 1514458.4 2716.8
Dichloride
Vinyl Chloride 3515710 206290 -3308880
1;1;2- -37294 13698 50992
Trichloroethane
Hydrochloric 3151020 316092 -3150703
acid
QTotal -6446441
Sample calculation of vinyl chloride, C2H3Cl at outlet stream
Reference state= Vinyl chloride (25℃, 1 atm, gas)
𝐻𝑜𝑢𝑡
25°C, 1 atm, (g) 170 °C, 26 atm, (g)
Ha Hb
170°C, 1 atm, (g)
6-16
Hout = Ha + Hb
170
Ha = ∫ [(5.949) + (0.20193)T + (−1.536 × 10−4 )T 2 + (47.730 × 10−9 )T 3 ]dT
25
KJ
=3.4766 mol
Hb = V∆P
=0
Hout = Ha + Hb
KJ KJ
= 3.4766 mol + (0 mol)
KJ
= 3.4766 mol
Q out = nHout
kmol kJ mol
= (59.28 hr
) (3.4766 mol) (1000 kmol)
kJ
= 206290 hr
6-17
6.3.6 Valve (V-101)
C2H4
B1
C2H4
Cl2
Cl2
S7 S8 C2H4 Cl2
C2H4 Cl2
T=170 T=170 C2H3 Cl
C2H3 Cl
P = 1.5 atm P = 26 atm C2H3 Cl3
C2H3 Cl3
Phase = gas Phase = gas
HCl
HCl
Figure 6. 7: Valve
Sample calculation for pump for vinyl chloride at outlet stream
170
Hpump = V∆P+∫25 [(5.949) + (0.20193)T + (−1.536 × 10−4 )T 2 + (47.730 ×
10−9 )T 3 ]dT
KJ
= 0+ =3.4766 mol
KJ
= 3.476mol
Q pump = nHvalve
kmol kJ mol
= (59.28 hr
) (3.476 mol) (1000 kmol)
kJ
= 206057.28 hr
∆Q valve inlet and outlet = 0 due to similarities of reference state with inlet condition
6-18
6.3.7 Cooler (E-105)
C2H4 C2H4 (g)
Cl2 Cl2 (g)
C2H4 Cl2 C2H4 Cl2 (l)
C2H3 Cl T = 170℃ T = 6℃ C2H3 Cl (g)

P = 1.5 atm P = 26 atm
C2H3 Cl3 C2H3 Cl3 (l)
Phase = gas Phase = gas
HCl and liquid HCl (g)
Figure 6. 8: Cooler
Table 6. 12: Inlet and outlet enthalpy for cooler

Substance Nin 8 Hin 8 Nout 9 Hout 9
(mol/h) (kJ/mol) (mol/hr) (kJ/mol)
Ethylene 0.6 2.63 0.6 -1.18
Chlorine 0.24 4.32 0.24 -0.52
Ethylene Dichloride 39.76 38.09 39.76 -223.42
Vinyl Chloride 59.28 3.48 59.28 -1.7
1;1;2- 0.36 38.05 0.36 -2633.2
Trichloroethane
Hydrochloric acid 59.64 5.30 59.64 -6.1
Table 6. 13: Energy balance for cooler

Ethylene 1578 -0.708 -1578

Chlorine 1036.8 -0.120 -106.92
Ethylene 1514458.4 -8882384 -10396842.4

Dichloride
Vinyl Chloride 206290 -100.776 -206390.78
1;1;2- 13698 -947.952 -14645.95

Trichloroethane
Hydrochloric 316092 -363.804 -316455.804
acid
Qtotal -10936019.85
6-19
Sample calculation of hydrogen chloride, HCl at outlet stream
Reference state= Hydrogen chloride (25℃, 1 atm, liquid)
𝐻𝑜𝑢𝑡
25°C, 1 atm, (l) 6 °C, 26 atm, (l)
Ha
Hb
6°C, 1 atm, (l)
Hout = Ha + Hb
6
Ha = ∫ [(20.486) + (0.23103)T + (−0.0001438)T 2 + (3.388x10−8 )T 3 ]dT
25
KJ
= −0.4
mol
Hb = V∆P
m3 101.325 kPa 1kJ

= 0.0847 × (1 − 26)atm × ×
mol 1 atm 1 kPa.m3
KJ
= -223
mol
Hout = Ha + Hb
KJ KJ
= (−0.4 )+ ( −223 )
mol mol
KJ
= −223.4 mol
Q out = nHout
kmol KJ mol
= (39.76 hr
) (−223.4 mol) (1000 kmol)
kJ
= −8882384 hr
6-20
6.3.8 HCl Column (T-101)
-26℃, 12atm
6℃, 26 atm C2H4
C2H4 HCl
Cl2
C2H4 Cl2 6.5℃, 12 atm

C2H4 Cl2
C2H3 Cl
C2H3 Cl
C2H3 Cl3
C2H3 Cl3
HCl
Figure 6. 9: HCl Column
Table 6. 14: Inlet outlet enthalpy HCl column

Substance Nin 9 Hin9 Nout 10 Hout 10 Nout 11 Hout 11
Ethylene 0.58 208.77 0.577 -45.41 - 28.16820739
Chlorine 0.004 -1211.96 - 0 - -507.85
Ethylene 63.69 -1880.75 - 0 63.69 -200.37
Dichloride
Vinyl chloride 94.97 428.10 - 0 94.97 20.25
Hydrochloric 95.54 -573.47 95.540 -1545.16 - -558.35
acid
1;1;2- 0.57 -2510.53 - 0 0.57 -71.63
Trichloroethane
Table 6. 15: Energy balance for HCl Column

Ethylene 121086.86 -26200.77126 147.2876281

Chlorine -4847.84 0 -4.847842406
Ethylene -119784991.3 0 -107023.5301
Dichloride
Vinyl Chloride 40656478.93 0 38733.27749
Hydrochloric -54789507.7 -147624833.4 92835.33
acid
1;1;2- -1431004.28 0 -1390.17
Trichloroethane
QTotal 23297.34043
6-21
Sample calculation of ethylene dichloride, C2H4 Cl2 at inlet column
Reference state= Ethylene dichloride (25℃, 1 atm, gas)
25°C, 1 atm, (g)
Ha
Hb
25 °C, 26 atm, (l) 6.5 °C, 26 atm, (l)
Hout = Ha + Hb
6
Ha = ∫ [(20.486) + (23.103 × 10−2 )T + (−1.438 × 10−4 )T 2 + (33.888 × 10−9 )T 3 ]dT
25
KJ
= −118.00
mol
Hb = V∆P
= (0.129)(1215.9 − 101.325)
= 326.77 kJ/mol
Hout = Ha + Hb
KJ KJ
= −118.00 + ( 326.77 )
mol mol
KJ
= 208.77 mol
Q out = nHout
kmol KJ mol
= (0.58 hr
) (208.77 mol) (1000 kmol)
kJ
= 121.09 hr
6-22
6.3.9 VC Column (T-102)
146℃, 4.8 atm, (g)
C2H3 Cl
58℃, 4.8 atm, (l)
Cl2
C2H4 Cl2
C2H3 Cl 32℃, 4.8 atm, (l)
C2H3 Cl3 C2H4 Cl2
HCl C2H3 Cl3
Figure 6. 10: VCM Column
Table 6. 16: Inlet outlet enthalpy VC column

Substance Nin 12 Hin12 Nout 13 Hout 13 Nout 14 Hout 14
Ethylene 98.96 4420.91 - - 63.693 992.25
Dichloride
Vinyl chloride 62.5 528.87 94.96 2720.84 - -
1;1;2- 133.4 5114.30 - - 0.573 160.69
Trichloroethane
Chlorine 70.91 932.73 0.003 3570.30 0 0
Table 6. 17: Energy balance for VC Column

Ethylene 435902065.4 63199.60135 435838865.8

Dichloride
Vinyl Chloride 33054480.53 258371203.6 -225316723.1
1;1;2- 682248033.5 92.07639471 682247941.5
Trichloroethane
Chlorine 66139573.2 0 66139573.2
QTotal 958909657.4
6-23
Sample calculation of ethylene dichloride, C2H4 Cl2 at VC column
Reference state= Ethylene dichloride (25℃, 1 atm, gas)
𝐻𝑜𝑢𝑡
25°C, 1 atm, (g) 32 °C, 4.8 atm, (l)
Ha Hb Hc
25°C, 1 atm, (l) 32 °C, 1 atm, (l)
Hout = Ha + Hb
32
Ha = ∫ [(20.486) + (0.23103)T + (−1.4 × 10−4 )T 2 + (3.388 × 10−8 )T3 ]dT
25
KJ
= 907.545787 mol
Hb = V∆P
= (0.22)(486.36 − 101.325)
= 84.7077 kJ/mol
Hout = Ha + Hb
KJ KJ
= 907.545787 + ( 84.7077 )
mol mol
KJ
= 992.253487 mol
Q out = nHout
kmol kJ mol
= (63.693 ) (992.253487 ) (1000 )
hr mol kmol
kJ
= 63199.60135
hr
6-24
6.3.10 Reactor (R-103)
B9
17 VCM
20 Water
VCM
Water 18
B.P.
B.P. PVC
19
T = 25℃ T = 85℃
P = 1 atm P = 7.30323 atm
Phase = Mixed Phase = Mixed
Figure 6. 11: Polymerization reactor
Table 6. 18: Inlet outlet enthalpy table and energy balance for stream 17 and 18
Component Stream 17 Stream 18
Mole Enthalpy, Heat Mole Enthalpy, Heat

flowrate, ΔH transfer, flowrate, ΔH transfer, Q
inlet (kJ/mol) Q (kJ/h) outlet (kJ/mol) (kJ/hr
(kmol/hr) (kmol/hr)
VCM 79.7722 993.28402 79236.5 0 0 0
Water 0 0 0 266.27 63.867 17006.296
PVC 0 0 0 0 0 0
Total 79236.51 17006.29
6-25
Table 6. 19: Inlet outlet enthalpy table and energy balance for stream 19 and 20
Component Stream 19 Stream 20
Mole Enthalpy, Heat Mole Enthalpy, ΔH Heat
flowrate, ΔH transfer, flowrate, (kJ/mol) transfer, Q
inlet (kJ/mol) Q (kJ/h) outlet (kJ/hr
(kmol/hr) (kmol/hr)
VCM 0 0 0 15.9544 10793.60378 172206

Water 0 0 0 266.274 63.86747798 17006.2
Benzoyl 0.0232 1454.39 33.856 273.175 34126.32 9322468
Peroxide
PVC 0 0 0 1156.51 -112.1312 129681
Total 33.856 9381999
Sample calculation in R-103
85
ΔHVCM in = ∫25 CP ΔT+Hf
ΔHVCM in = 356.94 + 666.369 + (-30.6432) + 0.618223+35.27
= 993.2840228 kJ/mol
QVCM in = (993.2840228 kJ/mol)(79.77226 kmol/h)
= 79236.5134 kJ/h
Q = 9381999.329 - (79236.5134 + 17006.29647 + 33.856067)
= -9285834.795kJ/h
6-26
Table 6. 20: List of equipment and total energy
List of equipment Total energy (KJ/hr) Type of energy
Rector, R-101 -3487950.6 Exothermic
Pump, P-102 27844000 Endothermic
Heater, E-102 917133.93 Endothermic
Furnace, R-102 14957870 Endothermic
Quench Tank, S-101 -573300 Exothermic
Cooler, E-105 -3321655.44 Exothermic
HCl Colum, T-101 -50311 Exothermic
VC Column, T-102 -3121184.50 Exothermic
Reactor, R-103 9381999 Endothermic
6.4 CONCLUSION
Energy balance for the specific plant is calculated based on formula,

assumptions and information given. Therefore, energy balance was calculated based
on the first law of thermodynamics which has stated that energy cannot be created or
destroyed but only can be modified. From the energy balance in polyvinyl chloride
production is assume to be an open systems at steady state. The heat transfer with
positive value represents the heat absorb which is as endothermic process. Then
negative value represent heat release and as exothermic process. From the calculated
energy balance for polyvinyl chloride plant, units such as heater (E-102), furnace (R-
102) are undergoes endothermic process since all the units absorb heat whereas
Bubble column reactor (R-101), quench tank (S-101), cooler (E-105), distillation
column (T-101 and T-102) undergo exothermic process.
6-27
CHAPTER 7
PROCESS SIMULATION
7.1 INTRODUCTION
Process simulation is one of the basis in process design. A good process

simulation is essential in designing a process, it will use for the study of plant operation
and trouble shooting. It also can be used to check performance against design, to
extend the often limited data available from the plant instrumentation, to check
instrument calibration and to locate sources of material loss. Process simulation over
the complete process will determine the quantities of raw materials required and
products produced. Aspen Plus V8.8 is a process simulator software used for modelling
of the behaviour of a chemical process in steady state, by means of the determination
of pressures, temperatures, and flows. Developed for firms in the Oil, Gas, Chemicals,
Engineering & Construction and other process industries, Aspen Plus V8.8 is a
powerful software release featuring user-friendly, streamlined workflow innovations
that allow users to minimize capital costs, improve plant productivity and boost
operational profitability [1]. AspenTech delivers the technology enhancements needed
to achieve operational excellence, enabling leading global firms to improve margins,
increase yields, meet customer demand, gain competitive advantage and implement
innovation across the enterprise. AspenTech allows to:
1. Predict the behaviour of the process.

2. Analyse in a simultaneous way different cases, changing the values of main
operating variables.
3. Optimize the operating conditions of new or existing plants.
4. Track a chemical plant during its whole useful life, in order to foresee
extensions process improvements.
Chemical process simulation aims to represent a process of chemical or

physical transformation through a mathematic model that involves the calculation of
mass and energy balances coupled with phase equilibrium and with transport of
chemical kinetics equations. In other words, the objective of undergoing a process
7-1
simulation is to predict how a defined process will behave under a given set of operating
conditions. The outputs of the process when the flowsheet and the inputs are given are
aimed to be predicted via a process simulation. After a process flowsheet is
synthesized, the detailed characteristics of the process simulation are predicted via
various process simulation tools to develop into an optimum flowsheet. The
mathematical model in the process simulation contains linear, non-linear, and
differential algebraic equations which represent equipment or process operations,
physical-chemical properties, connections between the equipment and operations and
their specifications. All of these connections are summarized in the process flow
diagram.
The process flow diagram (PFD) is a critical component of process design. It is

absolutely necessary for all chemical plant to have its very own PFD it is the primary
tool required in detailing the process and design information. The information that a
process flow diagram conveys can be categorized into one of the following three
groups which are process topology, stream information and equipment information.
Process topology is defined as the interactions and locations of the different equipment
and streams. PFD shows the flow of the process from the raw materials to the products
with a complex structure of pipelines, equipment units, utilities and also controls
equipment.
There are several advantages that can be obtained when using Aspen Plus as
chemical process simulations:
1. Allows the designer to quickly test the performance of synthesized process
flowsheets and provided feedback to the process synthesis activities.
2. It can be coordinate with the process synthesis to develop optimum
integrated designs.
3. Minimized experimental and scaled-up effort.
4. Explores process flexibility and sensitivity by answering “what-if” questions.
5. Quantitatively models the process and sheds insights on process
performance.
In Aspen Plus V8.8 that has been chosen as the simulation model, there are
several units operation that commonly being used which are reactors, separator,
heater, cooler, mixer, splitter, compressor and pump.
7-2
This design project targeted to produce 50,000 metric tonnes per annum of
polyvinyl chloride (PVC) via pyrolysis of ethylene dichloride (EDC) with efficient waste
treatment processed. However, in this chapter Aspen Plus simulation will only cover
for vinyl chloride monomer (VCM) production process as polymerization process is a
complex process and requires a different AspenTech simulation software named
Aspen Polymers. Vinyl chloride monomer is produced from direct chlorination of
ethylene before its product, EDC, undergo pyrolysis reaction to decomposed into
(VCM) and polymerized into PVC. The first reaction of direct chlorination involves the
chlorination of ethylene to produce EDC at 90˚C and 1.5 atm. Second reaction involves
the decomposition of EDC into VCM and hydrochloric acid (HCl) via pyrolysis reaction
at high temperature and pressure. Also in part, side reaction occur that produce 1,1,2-
trichloroethane (TCE) from the reaction of EDC with unreacted chlorine from the first
reaction.
7-3
7.2 PROCESS DESCRIPTION
M-101 M-102 M-103 C-101 P-101 P-102 P-103 V-101 V-102 V-103
Mixer Mixer Splitter Compressor Pump Pump Pump
Valve Valve Valve
V-104 V-105 E-101 E-102 E-103 E-104 E-105 E-106 E-107 E-108
Heater Heater Heater Cooler Cooler Heater Cooler Heater
Valve Valve
E-109 E-110 E-101 E-101 R-101 R-102 T-101 T-102
Cooler Cooler Heater Heater Reactor Reactor Distillation Distillation
Column Column
TO
ENVIRONMENTAL
CONTROL
TO VCM
STORAGE
TANK
TO
WWTP
Figure 7. 1: Rigorous process flow diagram of vinyl chloride monomer (VCM) production used in Aspen Plus simulation.
7-4
Figure 7.1 shows the rigorous process flow diagram of vinyl chloride monomer
production by direct chlorination of ethylene and pyrolysis of ethylene dichloride. The
process illustrated is designed to produce VCM at purity about 97.5%. Herein this
chapter explaining the process of direct chlorination of ethylene in reactor (R-101),
pyrolysis of EDC in reactor (R-102) and the separation processes were carry out in
distillation columns (T-101) and (T-102).
The process starts with feeding of the raw materials which are ethylene and
chlorine into the feed preparation process. In feed preparation process, raw materials
that are initially stored at standard temperature and pressure of 25˚C and 1 atm is
mixed before being pressurised and heated to 1.5 atm and 90˚C by using compressor
(C-101) and heater (E-101). Then, the mixture prepared will be directly feed into the
Bubble Column reactor that is represented by the rigorous Plug Flow reactor (R-101)
in this simulation process to undergo the process of direct chlorination of ethylene. In
this process, ferric chloride catalyst is being used to enhance the kinetic reaction of
VCM production and increase selectivity. The reactor that operate at 1.5 atm and 90˚C
will finally yield EDC through the reaction expressed in Equation 7.1. At this condition,
the exiting of direct chlorination process reactor (R-101) will produce a 97% pure EDC.
C2H4 + Cl2 → C2H4Cl2 (7.1)
Next, Aspen Plus model simulate the steady-state production of VCM from
EDC. The process is based on the dehydrochlorination of EDC in a gas-phase reaction.
Temperature plays a vital role in determining the selectivity and conversion of EDC to
VCM. This process is carried out in the pyrolysis reactor (R-102) with absence of any
catalyst. The operating temperature of the reactor is 500ᴼC at 26 atm which the
decomposition of EDC to form vinyl chloride occurs instantaneously and yield around
97.5% of VCM. Series of pumps, (P101), (P-102) and (P-103), and heaters (E-102)
and (E-103) are constructed to bring the stream into the desired temperature and
pressure before it is fed into the reactor. Reactor outlet from this process requires rapid
quenching which is represented by cooler (E-104) in this process simulation to control
the temperature in order to prevent tars and heavy by-products formation in the thermal
cracker unit connected. However, this process has a 60% conversion EDC into VCM
with 99.4% selectivity in the second reactor (R-102). Therefore, there are 0.6%
selectivity that favour the side reaction to produce 1,1,2-trchloroethan (TCE) from EDC.
Both reaction occurs in this reactor (R-102) are expressed in Equation 7.2 and 7.3.
7-5
CH2Cl—CH2Cl → CH2=CHCl + HCl (7.2)
CH2Cl—CH2Cl + Cl2 → CH2Cl—CHCl2 + HCl (7.3)
After quenching, the stream (stream 14) containing mixtures of chemical is

prepared for separation process. In separation feed preparation process, the stream
pressure is firstly reduced to 12 atm via valve (V-101) and then cooled to 6ᴼC with
cooler (E-105). The mixture is then fed at above-stage 8 into the first 12-stages
distillation column (T-101) in order to separate HCl. In this separation process, nearly
100% separation of HCl and unreacted ethylene is achieved, leaving the bottom
product rich in VCM, EDC. HCl recovered will be sent to the environmental control
equipment to avoid uncontrolled emission or release of HCl into the environment.
The bottom product of the separator is then reduced to 4.8 atm before it is feed
into the second distillation column (T-102). In the second distillation column, (stream
22) is fed above the 4th stage of the 8 stages distillation column. The main purpose of
this separator is to recover VCM from the mixture for further processes. About 99%
VCM from the mixture is recovered from this equipment with about 97.5% purity of
VCM in the top product.
Bottom product of the second separator is rich in unreacted EDC due to low
conversion of EDC into VCM in the pyrolysis reactor (R-102). By using splitter (M-103),
90% of the bottom product will be recycled back to the pyrolysis reactor to increase the
rate of production while 10% of the stream will be sent to the wastewater treatment
plant to avoid accumulation in the plant due to unseparated TCE content in the stream.
7.3 PROPERTY METHOD
A global property method that applies to an entire flowsheet may be selected.

If, however, the simulation involves a situation where more than property method is
required, for example, a process involving distillation (vapor–liquid equilibrium) and
extraction (liquid–liquid equilibrium), each block in the flowsheet is identified as part of
a unique flowsheet section when the flowsheet is created and identified with a particular
property method [48]. This process can be done by choosing the Method in Properties.
A thermodynamic model is a set of equations that permit the estimation of pure
component and mixture properties. In order to represent the chemical processes,
modifications, new design of equipment’s, the selection of a thermodynamic model that
7-6
represent accurately the physical properties of the substances interacting in the
process need to be conducted. The thermodynamic model is also known as property
package. It is the aspect of equations used for the determination of physical properties
of the components to simulate the reference [2].
There are four main group of thermodynamic models which is the ideal model,
the activity coefficients models, the equations of state and the special methods. The
ideal model is for the thermodynamic model simulation based on the ideal conditions
of the system. The activity coefficients models are to describe the nonideality of the
system in liquid phase while the equation of state is being used to calculate the
nonideality of the system in vapor phase [2].
Figure 7. 2: Guideline for choosing property method [2].
. The first criteria in selection of the property method is the polarity of the
components. The polarity is important aspect because it determines the type of
molecular interaction that can take place between the substances. Figure 7.2 shows
the guideline for choosing the property method to run a simulation process in Aspen
Plus V8.8. In VCM production, the polarity of the component is polar and non-
electrolyte component.
7-7
In the polar non-electrolyte component as shown in Figure 7.3, the condition of
the process in reactor are at pressure below that 10 bars which is around 1.5 bars. In
the system, there are interaction parameter between the component and there are
involving liquid-liquid component process that can be specified in the separation
process. Based on the property method, UNIQUAC method has been used to predict
the performance of the process of VCM production. UNIQUAC method has been
identified based on polar component operating conditions and presence of light gas in
the system.
Figure 7. 3: Procedure for polar non-electrolyte compound [2].
7.4 SET-UP SIMULATION MODEL
To start the simulation, unit setup and component specifications for the process
must be first selected. In this process, METCBAR unit set is preferred and selected in
the Aspen Plus V8.8 as shown in Figure 7.4. The Unit set for this process is metric bar
which used all the units in metric unit and the pressure in bar.
7-8
Figure 7. 4: METCBAR unit set selected for the process.
Figure 7.5 shows the components that are key entered into the simulation
process. All these components are specified as they are related to the simulation
process for VCM production. The component specified will commonly labelling by the
component ID.
Figure 7. 5: Component specification selected for the process.
. Next, the UNIQUAC method has been selected for the simulation model of
VCM production. This method is being chosen based on the property method selection
procedure discussed in Section 7.3. After the method being chosen, the simulation
need to run to simulate the properties of each component in the system.
7-9
Figure 7. 6: Method Selection
7.5 RAW MATERIAL FEED STREAM DESCRIPTION
Figure 7.7 shows the raw material feed streams in the process model
simulation. Stream 1 and 2 content ethylene and chlorine respectively at 96.117
kmol/hr being fed to the system from separate storage tank at 25˚C and 1 atm. Before
getting feed into the reactor, the streams are mixed with mixer (M-101) and brought to
reaction condition at 1.5 atm and 90˚C by heater (E-101) and compressor (C-101).
Refer Appendix A for block setup.
Figure 7. 7: Ethylene and chlorine feed stream.

7-10
7.6 DESIGN OF REACTOR
7.6.1 Direct Chlorination Reactor (R-101)
Figure 7.8 shows the first reactor (R-101) used in the process model simulation
for the VCM production which is bubble column reactor in which a continuous process
reaction occurs in this reaction at steady-state. The reactor equipment used
representing the bubble column reactor to simulate this process is plug flow reactor or
also known as RPlug in Aspen Plus software. Rplug (R-101) used is a rigorous reactor
which operates at continuous and steady-state condition. The conversion of ethylene
to produce EDC is very high at 99.4%. Reaction stoichiometry in this process is the
same expressed in Equation 7.1 and the stream results are shown in Table 7.2. Refer
Appendix B-1 for block setup.
Figure 7. 8: Direct chlorination reactor (R-101).
Table 7.1: Stream information at reactor (R-101).

Stream 5 6
Mole Flow kmol/hr
ETHYLENE 96.11692 0.5767015
CHLORINE 96.11692 0.5767015
HCL 0 0
EDC 0 95.54022
VCM 0 0
TCE 0 0
Mass Flow kg/hr
ETHYLENE 2696.441 16.17865
CHLORINE 6815.209 40.89125
HCL 0 0
EDC 0 9454.58
VCM 0 0
TCE 0 0
Mass Frac
ETHYLENE 0.2834883 0.00170093
CHLORINE 0.7165117 0.00429907
7-11
HCL 0 0
EDC 0 0.994
VCM 0 0
TCE 0 0
Total Flow kmol/hr 192.2338 96.69362

Total Flow kg/hr 9511.65 9511.65
Temperature C 90 90
Pressure bar 1.519875 1.519875
Vapor Frac 1 0.0381907
Liquid Frac 0 0.9618093
7.6.2 Pyrolysis Reactor(R-102)
Reactor (R-101) product (stream 6) content high amount of EDC at purity higher
than 99%.Figure 7.9 shows the feed preparation of the raw materials to achieve the
temperature of the reactor (R-102) at 500˚C and 26 atm. Firstly, components in stream
6 leave reactor (R-101) at 90˚C and 1.5 atm will be compressed using pump (P-101)
to 4.8 atm. At this point, mixer (M-103) is installed to mixed components from stream
27 with the same pressure of 4.8 atm that content high amount of unreacted EDC,
separated from second distillation column (T-102). Then, mixed components in stream
8 will next be compressed to 12 atm and next to 26 atm via pump (P-102) and pump
(P-103) respectively.
When desired reactor (R-102) feed pressure is achieved in stream 10, further
feed preparation process in term of temperature is carried on to increase the
temperature to 500˚C from the current temperature of 105˚C in stream 10. Therefore,
multiple heater of E-102 and E-103 is used to first increase the temperature to the
boiling point of EDC at 242ºC and then to reactor (R-102) desired feed temperature at
500ºC. Refer appendix B-2 for stream setup.
7-12
Figure 7. 9: Reactor (R-102) feed preparation unit.
Figure 7.10 shows the second reactor (R-102) used in the process model
simulation for the VCM production which is pyrolysis reactor in which a continuous
process reaction occurs in this reaction at steady-state. The reactor equipment used
representing the pyrolysis reactor to simulate this process is plug flow reactor or also
known as RPlug in Aspen Plus software. Rplug (R-102) used is for this reaction is a
rigorous reactor which operates at continuous and steady-state condition. The
decomposition of EDC to produce VCM in this reaction could achieved 60% conversion
with 99.4% selectivity. This reaction is expressed in Equation 7.2. Also, side reaction
also occurred in this reactor yield TCE from the reaction of EDC with chlorine as
expressed in Equation 7.3. The stream results for pyrolysis reactor (R-102) are shown
in Table 7.3. Refer Appendix B-2 for block setup.
Figure 7. 10: Pyrolysis reactor (R-102) in VCM process model simulation
7-13
Table 7.2: Stream information at reactor 2 (R-102).
Stream 12 13
Mole Flow kmol/hr
ETHYLENE 0.5767015 0.5767015
CHLORINE 0.5767015 0.2327567
HCL 0 57.32413
EDC 95.54022 38.21609
VCM 0 56.98019
TCE 0 0.3439448
Mass Flow kg/hr
ETHYLENE 16.17865 16.17865
CHLORINE 40.89125 16.50371
HCL 0 2090.075
EDC 9454.58 3781.832
VCM 0 3561.177
TCE 0 45.88358
Mass Frac
ETHYLENE 0.00170093 0.00170093
CHLORINE 0.00429907 0.00173511
HCL 0 0.2197384
EDC 0.994 0.3976
VCM 0 0.3744016
TCE 0 0.00482394
Total Flow kmol/hr 96.69362 153.6738

Total Flow kg/hr 9511.65 9511.65
Temperature C 500 500
Pressure bar 26.3445 26.3445
Vapor Frac 1 1
Liquid Frac 0 0
7.7 QUENCHING VESSEL
After pyrolysis reaction in reactor (R-102), rapid quenching is required to

prevent tars and heavy by-products formation in the thermal cracker. Quenching is a
process of rapid cooling. However, in Aspen Plus V8.8, there is no equipment that
have the same working principle as quenching vessel. But, the importance of
quenching vessel is not negligible. Therefore, in this simulation model, cooler (E-104)
is used to represent quenching vessel which will be used to cool the outlet stream
(stream 13) from reactor (R-102) from 500˚C to 170˚C (stream 14) as illustrated in
Figure 7.11 without any reaction. Refer Appendix B-2 for block setup.
7-14
Figure 7. 11: Cooler (E-104) that is used to represent quenching vessel.
7.8 DISTILLATION COLUMN
7.8.1 Distillation Column 1 (T-101)
In this design project for VCM production line, EDC produced from the reaction
of ethylene with chlorine in the first reactor (R-101) are directly feed into the second
reactor (R-102) to produce VCM, HCl and by-product TCE. The second reactor 2 (R-
102) product (stream 13) content all components related in the reaction of VCM
production, mixed together at different fraction. Therefore, it is necessary to separate
the components accordingly to the importance.
The first distillation column (T-101) is used in this process design to separate
HCl as HCl is the component with the lowest boiling point, in other words, the most
volatile component. Figure 7.12 shows the feed preparation for the output from
quenching vessel represented by cooler (E-104) to achieve the pressure and
temperature desired to separate HCl in the first distillation column (T-101) at 12 atm
and 6˚C. To achieve the desired pressure and temperature, valve (V-101) and cooler
(E-105) is used to lower the stream pressure to 12 atm and lower the stream
temperature to 6˚C. Refer Appendix C-1 for block setup.
7-15
Figure 7. 12:Distillation column (T-101) feed preparation unit.
Figure 7.13 shows the first distillation column (T-101) used in the process model
simulation for the VCM production. The distillation column equipment used to perform
the separation of HCl is RadFrac which is rigorous simulator block in Aspen Plus
software used for separation. In this process, separation of HCl achieved in the
RadFrac (T-101) is almost 100% due to a very low boiling point of HCl compared to
other components. Also in this separator, unreacted ethylene is separated to the top
product at almost 100%. Therefore, the bottom product of the separation content high
amount of VCM, unreacted EDC and by-product TCE. Finally, the top product will be
set to 1 atm and 25˚C before it sent to the environmental control unit as shown in Figure
7.14. The stream results for distillation column (T-101) are shown in Table 7.3. Refer
Appendix C-1 for block setup.
Figure 7. 13: Distillation column 1 RadFrac block (T-101).
7-16
Table 7.3: Stream information at distillation column RadFrac block (T-101).
Stream 16 17 18
Mole Flow kmol/hr
ETHYLENE 0.5767015 0.5767006 9.59418E-07
CHLORINE 0.2327567 0.2124859 0.0202708
HCL 57.32413 57.32413 1.434E-09
EDC 38.21609 4.1852E-12 38.21609
VCM 56.98019 3.718175 53.26201
TCE 0.3439448 2.3949E-17 0.3439448
Mass Flow kg/hr
ETHYLENE 16.17865 16.17862 2.69153E-05
CHLORINE 16.50371 15.0664 1.43731
HCL 2090.075 2090.075 5.22846E-08
EDC 3781.832 4.1416E-10 3781.832
VCM 3561.177 232.3805 3328.797
TCE 45.88358 3.1949E-15 45.88358
Mass Frac
ETHYLENE 0.00170093 0.0068737 3.76019E-09
CHLORINE 0.00173511 0.00640116 0.000200799
HCL 0.2197384 0.8879953 7.3044E-12
EDC 0.3976 1.7596E-13 0.5283401
VCM 0.3744016 0.0987298 0.4650489
TCE 0.00482394 1.3574E-18 0.00641016
Total Flow kmol/hr 153.6738 61.83149 91.84232
Total Flow kg/hr 9511.65 2353.7 7157.95
Temperature C 6 -26.04361 95.98322
Pressure bar 12.159 12.159 12.159
Vapor Frac 0.2849657 0 0
Liquid Frac 0.7150343 1 1
Figure 7. 14: Distillation column 1 (T-101) top product setting.
7-17
7.8.2 Distillation Column 2 (T-102)
The second distillation column (T-102) is used in this process design to recover
the desired product VCM from the mixture. Figure 7.15 shows the feed preparation for
the output from the first distillation column (T-101) bottom product (stream 18) to
achieve the pressure and temperature desired to separate VCM in the second
distillation column (T-102) at 4.8 atm and 57.7˚C. To achieve the desired pressure and
temperature, valve (V-103) and cooler (E-107) is used to lower the stream pressure to
4.8 atm and lower the stream temperature to 57.7˚C. Refer Appendix C-2 for block
setup.
Figure 7. 15: Distillation column 2 (T-102) feed preparation unit.
Figure 7.16 shows the second distillation column (T-102) used in the process
model simulation for the VCM production. The distillation column equipment used to
perform the separation of VCM is RadFrac which is rigorous simulator block in Aspen
Plus software used for separation. In this process, separation of VCM achieved in the
RadFrac (T-102) is above 97%. Also in this separator, unreacted chlorine is separated
to the top product at almost 100%. Therefore, the bottom product of the separation left
with high amount of unreacted EDC and by-product TCE. Finally, the top product of the
separator will be set to 1 atm and 25˚C before it sent to the VCM storage tank for further
process in polymerization to produce PVC in a dynamic state (batch) process shown
in Figure 7.17. The stream results for distillation column (T-102) are shown in Table
7.4. Refer Appendix C-2 for block setup.
7-18
Figure 7. 16: Distillation column 2 RadFrac block (T-101).
Table 7.4: Stream information at distillation column (T-102).

Stream 22 23 24
Mole Flow kmol/hr
ETHYLENE 9.59418E-07 9.59418E-07 1.0069E-15
CHLORINE 0.0202708 0.0202706 1.94328E-07
HCL 1.434E-09 1.434E-09 1.6709E-18
EDC 38.21609 0.3401808 37.87591
VCM 53.26201 53.2507 0.0113103
TCE 0.3439448 9.81821E-05 0.3438466
Mass Flow kg/hr
ETHYLENE 2.69153E-05 2.69153E-05 2.8248E-14
CHLORINE 1.43731 1.437297 1.37789E-05
HCL 5.22846E-08 5.22846E-08 6.0923E-17
EDC 3781.832 33.664 3748.168
VCM 3328.797 3328.09 0.7068776
TCE 45.88358 0.0130978 45.87049
Mass Frac
ETHYLENE 3.76019E-09 8.00287E-09 7.4441E-18
CHLORINE 0.000200799 0.000427359 3.63106E-09
HCL 7.3044E-12 1.5546E-11 1.6054E-20
EDC 0.5283401 0.0100095 0.9877258
VCM 0.4650489 0.9895592 0.000186278
TCE 0.00641016 3.89447E-06 0.0120879
Total Flow kg/hr 7157.95 3363.204 3794.745
Temperature C 57.7 31.71698 143.5582
Pressure bar 4.8636 4.8 4.8
Vapor Frac 0.1274232 0 0
Liquid Frac 0.8725768 1 1
7-19
Figure 7. 17: Distillation column 2 (T-102) top product setting.
7.9 RECYCLE AND WASTE STREAM
Bottom product (stream 24) of the distillation column 2 (T-102) has high amount
of unreacted EDC at high purity above 95%. However, a by-product TCE also content
in the stream (stream 24). TCE will not react with any of the components in the process
if it is also recycled with EDC. But, total recycle of will cause accumulation of TCE in
the equipment. To install a new separator will increase the cost of investment to the
plant construction. Therefore, a splitter as shown in Figure 7.18 is used to split 10% of
the bottom product (stream 24) of the distillation column 2 (T-102) to wastewater
treatment plant. Therefore, 90% of the bottom product (stream 24) will be recycled to
the pyrolysis reactor (R-102) feed preparation via mixer (M-102) at stream 7. The
stream results for distillation column (T-102) are shown in Table 7.6. Refer Appendix
D for block setup.
Figure 7. 18: Splitter used to split recycle (stream 26) and waste streams (stream 25).
7-20
Table 7.5: Stream information at splitter (M-103).
Stream 22 23 24
Mole Flow kmol/hr
ETHYLENE 8.6541E-16 8.6541E-17 7.7887E-16
CHLORINE 2.24436E-08 2.24436E-09 2.01992E-08
HCL 3.4392E-18 3.4392E-19 3.0953E-18
EDC 53.40973 5.340973 48.06875
VCM 0.00834459 0.000834459 0.00751013
TCE 5.030934 0.5030934 4.527841
Mass Flow kg/hr
ETHYLENE 2.4278E-14 2.4278E-15 2.185E-14
CHLORINE 1.59137E-06 1.59137E-07 1.43223E-06
HCL 1.254E-16 1.254E-17 1.1286E-16
EDC 5285.382 528.5382 4756.844
VCM 0.5215247 0.0521524 0.4693722
TCE 671.1463 67.11463 604.0317
Mass Frac
ETHYLENE 4.0755E-18 4.0755E-18 4.0755E-18
CHLORINE 2.6714E-10 2.6714E-10 2.6714E-10
HCL 2.105E-20 2.105E-20 2.105E-20
EDC 0.8872482 0.8872482 0.8872482
VCM 8.75475E-05 8.75475E-05 8.75475E-05
TCE 0.1126642 0.1126642 0.1126642
Total Flow kg/hr 5957.05 595.705 5361.345
Temperature C 145.5805 145.5805 145.5805
Pressure bar 4.8 4.8 4.8
Vapor Frac 0 0 0
Liquid Frac 1 1 1
7.10 STREAM RESULT SUMMARY
Table 7.6: Stream results summary.

Streams 1 2 3 4 5 6
M-101 M-101 C-101 E-101 R-101 P-101
M-101 C-101 E-101 R-101
VAPOR VAPOR VAPOR VAPOR VAPOR MIXED
Mole Flow
kmol/hr
ETHYLENE 96.11692 0 96.11692 96.11692 96.11692 0.576702
CHLORINE 0 96.11692 96.11692 96.11692 96.11692 0.576702
HCL 0 0 0 0 0 0
EDC 0 0 0 0 0 95.54022
7-21
VCM 0 0 0 0 0 0
TCE 0 0 0 0 0 0
Mole Frac
ETHYLENE 1 0 0.5 0.5 0.5 5.96E-03
CHLORINE 0 1 0.5 0.5 0.5 5.96E-03
HCL 0 0 0 0 0 0
EDC 0 0 0 0 0 0.988072
VCM 0 0 0 0 0 0
TCE 0 0 0 0 0 0
Mass Flow kg/hr
ETHYLENE 2696.441 0 2696.441 2696.441 2696.441 16.17865
CHLORINE 0 6815.209 6815.209 6815.209 6815.209 40.89125
HCL 0 0 0 0 0 0
EDC 0 0 0 0 0 9454.58
VCM 0 0 0 0 0 0
TCE 0 0 0 0 0 0
Mass Frac
ETHYLENE 1 0 0.283488 0.283488 0.283488 1.70E-03
CHLORINE 0 1 0.716512 0.716512 0.716512 4.30E-03
HCL 0 0 0 0 0 0
EDC 0 0 0 0 0 0.994
VCM 0 0 0 0 0 0
TCE 0 0 0 0 0 0
Total Flow
kmol/hr 96.11692 96.11692 192.2338 192.2338 192.2338 96.69362
Total Flow kg/hr 2696.441 6815.209 9511.65 9511.65 9511.65 9511.65
Total Flow l/min 39191.7 39191.7 78383.39 58719.99 63647.89 1356.181
Temperature C 25 25 25 61.88329 90 90
Pressure bar 1.01325 1.01325 1.01325 1.519875 1.519875 1.519875
Vapor Frac 1 1 1 1 1 0.038191
Liquid Frac 0 0 0 0 0 0.961809
Solid Frac 0 0 0 0 0 0
Table 7.6: Continue.

Streams 7 8 9 10 11 12
M-102 P-102 P-103 E-102 E-103 R-102
P-101 M-102 P-102 P-103 E-102 E-103
LIQUID LIQUID LIQUID LIQUID VAPOR VAPOR
Mole Flow
kmol/hr
ETHYLENE 0.576702 0.576702 0.576702 0.576702 0.576702 0.576702
CHLORINE 0.576702 0.576702 0.576702 0.576702 0.576702 0.576702
HCL 0 3.10E-18 3.10E-18 3.10E-18 3.10E-18 3.10E-18
EDC 95.54022 143.6064 143.6064 143.6064 143.6064 143.6064
VCM 0 7.51E-03 7.51E-03 7.51E-03 7.51E-03 7.51E-03
7-22
TCE 0 4.527833 4.527833 4.527833 4.527833 4.527833
Mole Frac
ETHYLENE 5.96E-03 3.86E-03 3.86E-03 3.86E-03 3.86E-03 3.86E-03
CHLORINE 5.96E-03 3.86E-03 3.86E-03 3.86E-03 3.86E-03 3.86E-03
HCL 0 2.07E-20 2.07E-20 2.07E-20 2.07E-20 2.07E-20
EDC 0.988072 0.961896 0.961896 0.961896 0.961896 0.961896
VCM 0 5.03E-05 5.03E-05 5.03E-05 5.03E-05 5.03E-05
TCE 0 0.030328 0.030328 0.030328 0.030328 0.030328
Mass Flow kg/hr
ETHYLENE 16.17865 16.17865 16.17865 16.17865 16.17865 16.17865
CHLORINE 40.89125 40.89125 40.89125 40.89125 40.89125 40.89125
HCL 0 1.13E-16 1.13E-16 1.13E-16 1.13E-16 1.13E-16
EDC 9454.58 14211.17 14211.17 14211.17 14211.17 14211.17
VCM 0 0.469399 0.469399 0.469399 0.469399 0.469399
TCE 0 604.0307 604.0307 604.0307 604.0307 604.0307
Mass Frac
ETHYLENE 1.70E-03 1.09E-03 1.09E-03 1.09E-03 1.09E-03 1.09E-03
CHLORINE 4.30E-03 2.75E-03 2.75E-03 2.75E-03 2.75E-03 2.75E-03
HCL 0 7.59E-21 7.59E-21 7.59E-21 7.59E-21 7.59E-21
EDC 0.994 0.955518 0.955518 0.955518 0.955518 0.955518
VCM 0 3.16E-05 3.16E-05 3.16E-05 3.16E-05 3.16E-05
TCE 0 0.040613 0.040613 0.040613 0.040613 0.040613
Total Flow
kmol/hr 96.69362 149.2951 149.2951 149.2951 149.2951 149.2951
Total Flow kg/hr 9511.65 14872.74 14872.74 14872.74 14872.74 14872.74
Total Flow l/min 140.5828 218.4357 218.7482 219.3543 4045.436 6071.492
Temperature C 99.86106 99.86119 100.8321 102.7013 242 500
Pressure bar 4.8 4.8 12.159 26.3445 26.3445 26.3445
Vapor Frac 0 0 0 0 1 1
Liquid Frac 1 1 1 1 0 0
7-23
Streams 13 14 15 16 17 18
E-104 V-101 E-105 T-101 V-102 V-103
R-102 E-104 V-101 E-105 T-101 T-101
VAPOR MIXED VAPOR MIXED LIQUID LIQUID
Mole Flow
kmol/hr
ETHYLENE 0.576702 0.576702 0.576702 0.576702 0.576701 8.96E-07
CHLORINE 0.059719 0.059719 0.059719 0.059719 0.055793 3.93E-03
HCL 86.16383 86.16383 86.16383 86.16383 86.16383 2.73E-09
EDC 57.44255 57.44255 57.44255 57.44255 1.51E-11 57.44255
VCM 85.65435 85.65435 85.65435 85.65435 7.733858 77.92049
TCE 5.044816 5.044816 5.044816 5.044816 9.57E-16 5.044816
Mole Frac
ETHYLENE 2.45E-03 2.45E-03 2.45E-03 2.45E-03 6.10E-03 6.38E-09
CHLORINE 2.54E-04 2.54E-04 2.54E-04 2.54E-04 5.90E-04 2.80E-05
HCL 0.366745 0.366745 0.366745 0.366745 0.911495 1.94E-11
EDC 0.244497 0.244497 0.244497 0.244497 1.60E-13 0.409101
VCM 0.364577 0.364577 0.364577 0.364577 0.081814 0.554943
TCE 0.021473 0.021473 0.021473 0.021473 1.01E-17 0.035929
Mass Flow kg/hr
ETHYLENE 16.17865 16.17865 16.17865 16.17865 16.17862 2.51E-05
CHLORINE 4.234371 4.234371 4.234371 4.234371 3.956058 0.278314
HCL 3141.588 3141.588 3141.588 3141.588 3141.588 9.94E-08
EDC 5684.467 5684.467 5684.467 5684.467 1.49E-09 5684.467
VCM 5353.27 5353.27 5353.27 5353.27 483.3547 4869.916
TCE 672.9983 672.9983 672.9983 672.9983 1.28E-13 672.9983
Mass Frac
ETHYLENE 1.09E-03 1.09E-03 1.09E-03 1.09E-03 4.44E-03 2.24E-09
CHLORINE 2.85E-04 2.85E-04 2.85E-04 2.85E-04 1.09E-03 2.48E-05
HCL 0.211231 0.211231 0.211231 0.211231 0.861871 8.85E-12
EDC 0.382207 0.382207 0.382207 0.382207 4.10E-13 0.506291
VCM 0.359939 0.359939 0.359939 0.359939 0.132605 0.433743
TCE 0.04525 0.04525 0.04525 0.04525 3.50E-17 0.059941
Total Flow
kmol/hr 234.942 234.942 234.942 234.942 94.53018 140.4118
Total Flow kg/hr 14872.74 14872.74 14872.74 14872.74 3645.078 11227.66
Total Flow l/min 9554.554 5231.563 11398.24 2156.451 59.6476 196.1027
Temperature C 500 170 152.5455 6 -25.9894 98.29942
Pressure bar 26.3445 26.3445 12.159 12.159 12.159 12.159
Vapor Frac 1 0.951876 1 0.263319 0 0
Liquid Frac 0 0.048125 0 0.736681 1 1
7-24
Table 7.6: Continue..
Streams 19 20 21 22 23 24
E-106 E-107 T-102 V-104 M-103
V-102 E-106 V-103 E-107 T-102 T-102
MIXED VAPOR MIXED MIXED LIQUID LIQUID
Mole Flow
kmol/hr
ETHYLENE 0.576701 0.576701 8.96E-07 8.96E-07 8.96E-07 8.65E-16
CHLORINE 0.055793 0.055793 3.93E-03 3.93E-03 3.93E-03 2.24E-08
HCL 86.16383 86.16383 2.73E-09 2.73E-09 2.73E-09 3.44E-18
EDC 1.51E-11 1.51E-11 57.44255 57.44255 4.032823 53.40973
VCM 7.733858 7.733858 77.92049 77.92049 77.91215 8.34E-03
TCE 9.57E-16 9.57E-16 5.044816 5.044816 0.013882 5.030934
Mole Frac
ETHYLENE 6.10E-03 6.10E-03 6.38E-09 6.38E-09 1.09E-08 1.48E-17
CHLORINE 5.90E-04 5.90E-04 2.80E-05 2.80E-05 4.79E-05 3.84E-10
HCL 0.911495 0.911495 1.94E-11 1.94E-11 3.33E-11 5.88E-20
EDC 1.60E-13 1.60E-13 0.409101 0.409101 0.049203 0.913783
VCM 0.081814 0.081814 0.554943 0.554943 0.95058 1.43E-04
TCE 1.01E-17 1.01E-17 0.035929 0.035929 1.69E-04 0.086074
Mass Flow kg/hr
ETHYLENE 16.17862 16.17862 2.51E-05 2.51E-05 2.51E-05 2.43E-14
CHLORINE 3.956058 3.956058 0.278314 0.278314 0.278312 1.59E-06
HCL 3141.588 3141.588 9.94E-08 9.94E-08 9.94E-08 1.25E-16
EDC 1.49E-09 1.49E-09 5684.467 5684.467 399.0848 5285.382
VCM 483.3547 483.3547 4869.916 4869.916 4869.394 0.521525
TCE 1.28E-13 1.28E-13 672.9983 672.9983 1.851911 671.1463
Mass Frac
ETHYLENE 4.44E-03 4.44E-03 2.24E-09 2.24E-09 4.77E-09 4.08E-18
CHLORINE 1.09E-03 1.09E-03 2.48E-05 2.48E-05 5.28E-05 2.67E-10
HCL 0.861871 0.861871 8.85E-12 8.85E-12 1.89E-11 2.11E-20
EDC 4.10E-13 4.10E-13 0.506291 0.506291 0.075719 0.887248
VCM 0.132605 0.132605 0.433743 0.433743 0.923877 8.75E-05
TCE 3.50E-17 3.50E-17 0.059941 0.059941 3.51E-04 0.112664
Total Flow
kmol/hr 94.53018 94.53018 140.4118 140.4118 81.96278 58.44901
Total Flow kg/hr 3645.078 3645.078 11227.66 11227.66 5270.609 5957.05
Total Flow l/min 12773.84 38544.7 3566.945 1084.7 96.69071 93.03266
Temperature C -81.6972 25 66.52018 57.7 33.29992 145.5805
Pressure bar 1.01325 1.01325 4.8636 4.8636 4.8 4.8
Vapor Frac 0.515007 1 0.252156 0.069091 0 0
Liquid Frac 0.484993 0 0.747844 0.930909 1 1
7-25
Streams 25 26 27 28
V-105 E-110 M-102 E-108
M-103 M-103 E-110 V-104
LIQUID LIQUID LIQUID MIXED
Mole Flow
kmol/hr
ETHYLENE 8.65E-17 7.79E-16 7.79E-16 8.96E-07
CHLORINE 2.24E-09 2.02E-08 2.02E-08 3.93E-03
HCL 3.44E-19 3.10E-18 3.10E-18 2.73E-09
EDC 5.340973 48.06875 48.06615 4.032823
VCM 8.34E-04 7.51E-03 7.51E-03 77.91215
TCE 0.503093 4.527841 4.527833 0.013882
Mole Frac
ETHYLENE 1.48E-17 1.48E-17 1.48E-17 1.09E-08
CHLORINE 3.84E-10 3.84E-10 3.84E-10 4.79E-05
HCL 5.88E-20 5.88E-20 5.88E-20 3.33E-11
EDC 0.913783 0.913783 0.913779 0.049203
VCM 1.43E-04 1.43E-04 1.43E-04 0.95058
TCE 0.086074 0.086074 0.086078 1.69E-04
Mass Flow kg/hr
ETHYLENE 2.43E-15 2.19E-14 2.18E-14 2.51E-05
CHLORINE 1.59E-07 1.43E-06 1.43E-06 0.278312
HCL 1.25E-17 1.13E-16 1.13E-16 9.94E-08
EDC 528.5382 4756.844 4756.586 399.0848
VCM 0.052152 0.469372 0.469399 4869.394
TCE 67.11463 604.0317 604.0307 1.851911
Mass Frac
ETHYLENE 4.08E-18 4.08E-18 4.08E-18 4.77E-09
CHLORINE 2.67E-10 2.67E-10 2.67E-10 5.28E-05
HCL 2.11E-20 2.11E-20 2.10E-20 1.89E-11
EDC 0.887248 0.887248 0.887243 0.075719
VCM 8.75E-05 8.75E-05 8.76E-05 0.923877
TCE 0.112664 0.112664 0.11267 3.51E-04
Total Flow
kmol/hr 5.844901 52.6041 52.6015 81.96278
Total Flow kg/hr 595.705 5361.345 5361.086 5270.609
Total Flow l/min 9.303266 83.7294 77.84722 7182.892
Temperature C 145.5805 145.5805 99.86106 -12.3789
Pressure bar 4.8 4.8 4.8636 1.01325
Vapor Frac 0 0 0 0.243419
Liquid Frac 1 1 1 0.756581
Solid Frac 0 0 0 0
7-26
Streams 29 30 31
E-109
E-108 V-105 E-109
VAPOR MIXED LIQUID
Mole Flow
kmol/hr
ETHYLENE 8.96E-07 8.65E-17 8.65E-17
CHLORINE 3.93E-03 2.24E-09 2.24E-09
HCL 2.73E-09 3.44E-19 3.44E-19
EDC 4.032823 5.340973 5.340973
VCM 77.91215 8.34E-04 8.34E-04
TCE 0.013882 0.503093 0.503093
Mole Frac
ETHYLENE 1.09E-08 1.48E-17 1.48E-17
CHLORINE 4.79E-05 3.84E-10 3.84E-10
HCL 3.33E-11 5.88E-20 5.88E-20
EDC 0.049203 0.913783 0.913783
VCM 0.95058 1.43E-04 1.43E-04
TCE 1.69E-04 0.086074 0.086074
Mass Flow kg/hr
ETHYLENE 2.51E-05 2.43E-15 2.43E-15
CHLORINE 0.278312 1.59E-07 1.59E-07
HCL 9.94E-08 1.25E-17 1.25E-17
EDC 399.0848 528.5382 528.5382
VCM 4869.394 0.052152 0.052152
TCE 1.851911 67.11463 67.11463
Mass Frac
ETHYLENE 4.77E-09 4.08E-18 4.08E-18
CHLORINE 5.28E-05 2.67E-10 2.67E-10
HCL 1.89E-11 2.11E-20 2.11E-20
EDC 0.075719 0.887248 0.887248
VCM 0.923877 8.75E-05 8.75E-05
TCE 3.51E-04 0.112664 0.112664
Total Flow
kmol/hr 81.96278 5.844901 5.844901
Total Flow kg/hr 5270.609 595.705 595.705
Total Flow l/min 33420.34 811.4802 7.857567
Temperature C 25 85.80906 25
Pressure bar 1.01325 1.01325 1.01325
Vapor Frac 1 0.280679 0
Liquid Frac 0 0.719321 1
Solid Frac 0 0 0
7-27
7.11 COMPARISON OF MANUAL CALCULATION AND WITH ASPEN PLUS
The comparison of the overall balance of mass flowrate inlet obtained from the
Aspen Plus with the mass flowrate outlet of manual calculations that have been
performed for each equipment involved in the plant design:
Mass flowrate inlet (Aspen Plus) = Mass flowrate outlet (Manual)

Stream 4 = Stream 20 + Stream 29
9511.65 kg/hr = 3499.57 kg/hr + 5935.68 kg/hr
9511.65 kg/hr = 9435.25 kg/hr
(9511.65 − 9435.25)
% Error (overall mass balance) = × 100%
9511.65
% Error (overall mass balance) = 𝟎. 𝟖𝟎𝟑%
Another comparison of the overall balance of mass flowrate outlet obtained from the
Aspen Plus with the mass flowrate outlet of manual calculations that have been
performed for each equipment involved in the plant design:
Mass flowrate outlet (Aspen Plus) = Mass flowrate outlet (Manual)

Stream 17 + Stream 23 = Stream 17 + Stream 23
3645.078 kg/hr + 5270.609 kg/hr = 3499.57 kg/hr + 5935.68 kg/hr
8915.687 kg/hr = 9435.25 kg/hr
(9435.25 − 8915.687 )
% Error (overall mass balance) = × 100%
9435.25
% Error (overall mass balance) = 𝟓. 𝟓𝟏%
Table 7.7 shows the comparison of the overall balance of mass flowrate outlet
obtained from the Aspen Plus with the mass flowrate outlet of the manual calculations
that have been performed for each equipment involved in the plant design:
Table 7. 7: Summary of mass flowrate of output streams on manual mass balance

calculation and Aspen Plus.
Outlet mass flow rate (kg/hr)
Stream Manual calculation Aspen Plus
17 3499.57 3645.078
23 5935.68 5270.609
Total 9435.25 8915.687
7-28
7.12 CONCLUSION
As the conclusion, the production of vinyl chloride monomer (VCM) at the end
of the process is lower than the value of the inlet production which is 9511.65 kg/hr in
order to achieve 50,000 tonne/annum of production of polyvinyl chloride (PVC). Thus,
the targeted purity of acetic acid is 99.89% where the percentage error of the overall
system is 5.51%. This process model simulation has been completely run to achieve
the target above 97% by mass purity of VCM.
7-29
REFERENCES
[1] “Production and Demand of Polyvinyl Chloride (PVC) Resin in Asian Region
(2014).” .
[2] S. Altarazi, M. Ammouri, and A. Hijazi, “Artificial neural network modeling to

evaluate polyvinylchloride composites’ properties,” Comput. Mater. Sci., vol.
153, no. January, pp. 1–9, 2018.
[3] “Compound Summary for CID 6338 - Vinyl Chloride,” PubChem. .
[4] “Manufacturing PVC | Australian Vinyls — Australian Vinyls.” .
[5] “Polyvinyl Chloride.” .
[6] Creative Mechanisms Staff, “Everything You Need to Know About PVC Plastic,”
July 6, 2016. .
[7] “Polyvinyl Chloride (PVC) Properties, Production, Price, Market and Uses.” .
[8] “Ceresana Market Research Since 2002.” .
[9]. “Malaysia Plastics Market – Segmented by Type, Technology, and Application

– Growth, Trends, and Forecast (2018-2023).” .
[10] “Chlorine Properties.” .
[11] “Compound Summary for CID 6325 - Ethylene,” PubChem. .
[12] “Compound Summary for CID 24526 - Chlorine,” PubChem. .
[13] “Compound Summary for CID 962 - Water,” PubChem. .
[14] F. Bezzo Correlatori, S. Spatenka Ing Filipe Calado Laureando, and G.

Rossanese, “Modelling of an industrial plant for vinyl chloride production,” 2015.
[15] C. S. Bildea and A. C. Dimian, “7 Vinyl Chloride Monomer Process,” Chem.

Process Des. Comput. Case Stud., pp. 201–229, 2008.
[16] M. Benje., “Method of producing ethylene (di)chloride (EDC),” vol. 6, p. 708–

841,.
[17] “Vinyl Chloride Monomer (VCM) - Chemical Economics Handbook (CEH) | IHS
Markit.” .
[18] J. Dattani, D. Devani, and O. Sahu, “Cleaner Production of Vinyl Chloride

236
Monomer (VCM),” Int. J. Sci. Eng. Res., vol. 4, no. 5, pp. 701–705, 2013.
[19] E. P. Declarations and E. P. Manufacturers, “Vinyl chloride ( VCM ) and Polyvinyl

chloride ( PVC ) PlasticsEurope / The European Council of Vinyl Manufacturers
( ECVM ) May 2015,” no. May, pp. 1–5, 2015.
[20] “How is PVC made ? - PVC,” The European Council of Vinyl Manufacturers. .
[21] all of T. Dale R. Muehlenbrock, Pasadena; John R. Prihoda, Houston;

LeonardSingleton, Jr., Baytown, “PROCESS FOR POLYMERIZATION OF
POLVINYL CHLORIDE AND VCM MONOMER,” 1980.
[22] Y. Saeki and T. Emura, “Technical progresses for PVC production,” in Progress
in Polymer Science (Oxford), 2002.
[23] “Methods of Polymerization.” .
[24] C. Frank, “Chemical Engineering 160 / 260 Polymer Science and Engineering
Lecture 13 - Polymerization Techniques - Dispersed Systems,” 2001.
[25] “IPPE PVC Plant,” International Process Plant. .
[26] “Polymerization Techniques.” .
[27] “Emulsion.” .
[28] S. Moore, “Organic Chemistry,” 2016. .
[29] “Bulk or Mass Polymerization,” Polymer Properties Database, 2015. .
[30] “Bulk.” .
[31] R. Baxter, N. Hastings, A. Law, and E. J. . Glass, Product and Process Design
Principles, vol. 39, no. 5. 2008.
[32] T. Dalgleish et al., Product And Process Design Principles: Synthesis, Analysis
And Evaluation, vol. 136, no. 1. 2007.
[33] Å. Lindqvist, “Process integration study for increased energy efficiency of a PVC
plant,” 2011.
[34] R. Baxter, N. Hastings, A. Law, and E. J. . Glass, Industrial Organic Chemistry,

vol. 39, no. 5. 2008.
[35] Alibaba, “Chinese supplier industrial grade ferric chloride anhydrous.” .
237
[36] G. Members, “Chapter 1 : Process Background and Selection,” no. September
2017, 2018.
[37] R. N. Wheeler, “Poly ( vinyl Chloride ) and Processes,” vol. 41, pp. 123–128,
2014.
[38] H. Laudie, “Emulsion polymerization of vinyl chloride,” 1977.
[39] J. Boissel and N. Fischer, “Bulk Polymerization of Vinyl Chloride: Nucleation

Phase,” J. Macromol. Sci. Part A - Chem., vol. 11, no. 7, pp. 1249–1269, 1977.
[40] R. Arshady, “Leading Contribution Suspension , emulsion , and dispersion

polymerization : A methodological survey,” vol. 732, 1992.
[41] J. N. Farber, “Some aspects of the reactor design for bulk polymerization of vinyl
chloride .,” no. February, 2014.
[42] M. Zerfa, “Vinyl chloride drop behaviour in suspension polymerisation reactors,”

PhD Thesis, Univ. Loughbrgh., p. 292, 1994.
[43] “PVC chemistry and production.” .
[44] “Benzoyl Peroxide 99% 94-36-0.” .
[45] “99% Potassium Persulfate (K2O8S2).” .
[46] K. C. Dee, “Chemical engineering process hierarchical design with Ascend,”

CEPHDA, pp. 1–14, 1992.
[47] J. M. Douglas, “A Hierarchical Decision Procedure For The Synthesis Of

Complex Plants,” AlChE J., vol. 31, no. 3, pp. 353–362, 1989.
[48] “What are advantages and disadvantages of batch processing systems.” .
[49] “Difference between Continuous and Batch Process.” .
[50] “Chapter 8 Synthesis of reaction systems,” Comput. Aided Chem. Eng., vol. 13,
pp. 299–350, Jan. 2003.
[51] A. T. Jensen et al., “Synthesis of polymer/inorganic hybrids through heterophase

polymerizations,” Recent Dev. Polym. Macro, Micro Nano Blends, pp. 207–235,
Jan. 2017.
[52] R. M. Felder and R. W. Rousseau, Elementary principles of chemical processes.
238
Wiley, 2005.
[53] P. C. Wankat, Separation process engineering : includes mass transfer analysis.

Prentice Hall, 2012.
[54] P. Schmittinger, Chlorine: Ullmann’s Encyclopedia of Industrial Chemistry.

Wiley-VCH Verlag GmbH & Co, 2006.
[55] M. K. Moraveji, R. Davarnejad, A. Filsoof, and M. Asgari, “Reactor modeling of

ethylene oxychlorination for 1, 2 dichloroethane production,” World Appl. Sci. J.,
vol. 21, no. 8, pp. 1113–1115, 2013.
[56] “Determination of ferric chloride in liquid phase EDC - AppliTek.” [Online].

Available: https://www.applitek.com/products/ferric-chloride-in-liquid-phase-
edc. [Accessed: 25-Oct-2018].
[57] “ETHYLENE DICHLORIDE (EDC) HANDBOOK,” 2014.
[58] K. E. Howlett, “The pyrolysis of 1 : 2-dichloroethane,” Trans. Faraday Soc., vol.
48, no. 0, p. 25, Jan. 1952.
[59] “PVC autoclave model.”
[60] Eduardo Vivaldo-Lima, * and Philip E. Wood, A. E. Hamielec, and A. Penlidis†,

“An Updated Review on Suspension Polymerization,” 1997.
[61] H. S. Fogler, Essentials of chemical reaction engineering. .
[62] R. E. Lenz, “Vinyl Chloride Production,” United States Pat., pp. 2–4, 1956.
[63] S.-S. Chang, “Heat capacity and thermodynamic properties of poly(vinyl

chloride),” J. Res. Natl. Bur. Stand. (1934)., vol. 82, no. 1, p. 9, 1977.
[64] S. Wachi and Y. Asai., “Kinetics of 1, 2-dichloroethane formation from ethylene

and cupric chloride.,” Ind. Eng. Chem. Res., vol. 33, pp. 259–264, 1994.
[65] D. Prieto et al., “Drivers and economic aspects for the implementation of
advanced wastewater treatment and water reuse in a PVC plant,” Water Resour.
Ind., vol. 14, pp. 26–30, 2016.
[66] “Department of Environment, Environmental,” Requir. A Guid. Investors, Minist.

Nat. Resour. Environ., pp. 1–78, 2010.
[67] J. J. Carberry et al., McGraw-Hill Chemical Engineering Series Editorial Advisory

239
Board Building the Literature of a Profession. .
[68] J. D. N. Martins, E. Freire, and H. Hemadipour, “Applications and market of PVC

for piping industry,” Polímeros, vol. 19, no. 1, pp. 58–62, 2009.
[69] BPF, “Polyvinyl Chloride PVC.” [Online]. Available:

http://www.bpf.co.uk/plastipedia/polymers/PVC.aspx. [Accessed: 17-Oct-2018].
[70] “Why PVC pipes? | PVC4Pipes.” [Online]. Available:

https://pvc4pipes.com/resources/why-pvc-pipes/. [Accessed: 17-Oct-2018].
[71] Sevenster, “PVC The most widely used polymer in medical applications - PVC.”
[Online]. Available: http://www.pvc.org/en/p/pvc---the-most-widely-used-
polymer-in-medical-applications. [Accessed: 17-Oct-2018].
[72] “PVC Production, Trading Price and Market Demand.” [Online]. Available:
https://www.plasticsinsight.com/resin-intelligence/resin-prices/pvc/. [Accessed:
17-Oct-2018].
[73] “Chemical Research and Analysis | IHS Markit.” [Online]. Available:

https://ihsmarkit.com/research-analysis/chemical.html. [Accessed: 17-Oct-
2018].
[74] “Malaysia Plastics Market | Growth, Trends and Forecast (2018-2023).” [Online].
Available: https://www.mordorintelligence.com/industry-reports/malaysia-
plastics-market. [Accessed: 17-Oct-2018].
[75] Sujatha Trivikram, “Plant Location Decisions and Factors Affecting Plant
Location - MyVenturePad.com.” [Online]. Available:
http://myventurepad.com/plant-location-decisions-factors-affecting-plant-
location/. [Accessed: 17-Oct-2018].
[76] Smriti Chand, “Top 10 Factors Affecting Plant Location – Explained!” [Online].
Available: http://www.yourarticlelibrary.com/industries/plant-layout/top-10-
factors-affecting-plant-location-explained/34618. [Accessed: 17-Oct-2018].
[77] Sindujha S, “Factors Affecting Plant Location | Industries.” [Online]. Available:

http://www.businessmanagementideas.com/industries/factors-affecting-plant-
location-industries/9220. [Accessed: 17-Oct-2018].
[78] “Process location and layout decisions - processdesign.” [Online]. Available:

https://processdesign.mccormick.northwestern.edu/index.php/Process_locatio
240
n_and_layout_decisions. [Accessed: 31-Oct-2018].
[79] “Chapter 25. Changing Policies | Section 3. Using Tax Incentives to Support
Community Health and Development | Main Section | Community Tool Box.”
[Online]. Available: https://ctb.ku.edu/en/table-of-contents/implement/changing-
policies/tax-incentives/main. [Accessed: 31-Oct-2018].
[80] “industrial estate near Pengerang, Johor - Google Maps.” .
[81] “Tanjung Langsat Industrial Estate - Google Maps.” .
[82] “industrial estate near Gebeng, Balok, Pahang - Google Maps.” .
[83] “kawasan perindustrian near Kerteh, Terengganu - Google Maps.” .
[84] “industrial estate near Kampung Teluk Kalong, Kijal, Terengganu - Google
Maps.” .
[85] “MIDF RESEARCH.”
[86] “PAIP Online Payment : Pengurusan Air Pahang Berhad (PAIP).” [Online].
Available: https://onlinepay.paip.com.my/. [Accessed: 18-Oct-2018].
[87] “SATUWATER - Home.” [Online]. Available: http://www.satuwater.com.my/.

[Accessed: 18-Oct-2018].
[88]. : “MIDA | Malaysian Investment Development Authority :. Perihal MIDA.”

[Online]. Available: http://www.mida.gov.my/home/. [Accessed: 29-Oct-2018].
[89] “Department of Statistics Malaysia Official Portal.” [Online]. Available:

https://www.dosm.gov.my/v1/index.php?r=column/cone&menu_id=ZmVrN2Fo
YnBvZE05T1AzK0RLcEtiZz09. [Accessed: 23-Oct-2018].
[90] “Malaysia - Corporate tax credits and incentives.” [Online]. Available:

http://taxsummaries.pwc.com/ID/Malaysia-Corporate-Tax-credits-and-
incentives. [Accessed: 31-Oct-2018].
[91] “The Official PKNP’s One-Stop-Agency Portal.” [Online]. Available:

http://www.investinpahang.gov.my/. [Accessed: 31-Oct-2018].
[92] “ECER incentive package.” [Online]. Available:

http://www.mida.gov.my/env3/uploads/IncentivesCompilation/ECERDC/2013/A
ppVIII.pdf. [Accessed: 31-Oct-2018].
241
[93] S. Shah, U. Fischer, and K. Hungerbühler, “A hierarchical approach for the
evaluation of chemical process aspects from the perspective of inherent safety,”
Process Saf. Environ. Prot. Trans. Inst. Chem. Eng. Part B, vol. 81, no. 6, pp.
430–443, 2003.
[94] “Health and Safety,” Linde Malaysia. .
[95] “The National Institute for Occupational Safety and Health (NIOSH),” Centers of
Disease Control and Prevention, 2018. .
[96] “Chemical Manufacturing Environmental Regulations,” In Business Info. .
[97] L. H. Keng, “Malaysia Department of Environment,” AECEN. .
[98] FACTORIES AND MACHINERY ACT 1967 (REVISED - 1974), vol. 64.
Malaysia: The Commissioner of Law Revision, Malaysia, 2006.
[99] O. Siti Norsalehah, “A Study on the Compliance of Manufacturing Company to

the Factory and Machinery Act 1967 (ACT 139): A Case Study,” vol. 1967, no.
Act 139, 2011.
[100] Law of Malaysia Act 514 Occupational Safety and Health Act 1994, no. 1.
Malaysia: The Commissioner of Law Revision, Malaysia, 2014.
[101] L. Laxman, “LAW ON SAFETY AND HEALTH IN MALAYSIA,” 2007. .
[102] P. 4 F. G. A. C. 62574 P. Department of Environment Ministry of Natural

Resources and Environment Wisma Sumber Asli, “Environmental
Requirements: A Guide For Investors,” Environ. Requir. A Guid. Investors, vol.
11, pp. 1–71, 2010.
[103] ENVIRONMENTAL QUALITY ACT, 1974 (Act 127). Malaysia: The

Commissioner of Law Revision, Malaysia, 1974.
[104] “Hazardous Waste Identification - Hazardous Waste Management -

Environmental Management Programs - EHS - UW-Superior.” .
[105] U.S. Environmental Proctection Agency, “Hazardous Waste Identification (40

CFR Parts 261),” Solid Waste Emerg. Response, vol. EPA530-K-0, no.
September, 2005.
[106] and S. P. H. Alvarez, R.A., S.W. Pacala, J.J. Winebrake, W.L. Chameides, and
S.P. HamburgAlvarez, R.A., S.W. Pacala, J.J. Winebrake, W.L. Chameides,
242
Greater focus needed on methane leakage from natural gas infrastructure.
Proceedings of the National Academy of Sciences, 2012.
[107] C. E. P. A. A. R. Board., “Health Effects of Air Pollution.” .
[108] A. Poullikkas, “Review of Design, Operating, and Financial Considerations in

Flue Gas Desulfurization Systems,” Energy Technol. Policy, vol. 2, no. 1, pp.
92–103, 2015.
[109] Y. Dou, B.; Pan, W.; Jin, Q.; Wang, W.; Li, “Prediction of SO2 Removal Efficiency
for Wet Flue Gas Desulfurization. Energy Conversation Management,” 2009.
[110] J. Stergarek, A.; Horvat, M.; Frkal, P.; Stergarek, “Removal of Hg0 from flue
gases in Wet FGD by Catalytic Oxidation With Air—An Experimental Study.,”
pp. 3167–3177, 2010.
[111] K. Hu, “Contribution to modeling of treatment and reuse of industrial

wastewater,” no. September 2016, 2017.
[112] A. C. Ahmad, I. Nianti, M. Zin, M. K. Othman, and N. H. Muhamad, “Hazard

Identification , Risk Assessment and Risk Control ( HIRARC ) Accidents at
Power Plant,” MATEC Web Conf., vol. 00105, no. 66, pp. 1–6, 2016.
[113] Guidelines for Hazard Identification, Risk Assessment and Risk Control
(HIRARC). Malaysia: Department of Occupational Safety and Health, Ministry of
Human Resources, 2008.
[114] A. C. Ahmad, “Hazard Identification,” Canadian Center for Occupational Health

and Safety, 2018. .
[115] A. AI-Hammad and S. Assaf, “ASSESSMENTOF WORK PERFORMANCE OF

MAINTENANCE CoNTRACTORS IN SAUDI ARABIA,” J. Manag. Eng., pp. 44–
49, 2010.
[116] C. Verbano and K. Venturini, “Managing Risks in SMEs : A Literature Review

and Research Agenda,” vol. 8, no. 3, pp. 186–197, 2013.
243
APPENDICES
Appendix A
244
245
246
Appendix B-1
247
248
249
Appendix B-2
250
251
252
253
254
255
256
Appendix C-1
257
258
259
Appendix C-2
260
261
262
263
252

Salman PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Salman PDF

Uploaded by

Copyright:

Available Formats

EH2248A/B

FINAL DESIGN PROJECT 1 REPORT

MUHAMMAD SALMAN BIN SAMIN MOHAMAD HEIRY MOHD AZMI

NUR SHAFIQAH BINTI JAMALUDDIN AKASHAH BIN ZABRI

NOR ADILA BINTI MOHD NASIR

SV SUBMISSION APPROVAL FORM DP 1 ...............................................................II

AKNOWLEDGEMENT ............................................................................................... III

TABLE OF CONTENTS ........................................................................................... IV

LIST OF FIGURES ................................................................................................... IX

LIST OF TABLES .................................................................................................... XII

EXECUTIVE SUMMARY ........................................................................................ XVI

CHAPTER 1 ........................................................................................................... 1-1

PROCESS BACKGROUND AND SELECTION ...................................................... 1-1

1.1 INTRODUCTION ...................................................................................... 1-1

1.1.1 About polyvinyl chloride (PVC) .......................................................... 1-1

1.1.2 Applications ....................................................................................... 1-4

1.1.3 Market Demand ................................................................................. 1-5

1.1.4 Raw Materials ................................................................................... 1-6

1.2 PROCESS BACKGROUND ..................................................................... 1-9

1.2.1 Ethylene Dichloride (EDC) Processes ............................................... 1-9

1.2.2 Synthesis of Vinyl Chloride Monomer (VCM) ....................................1-12

1.2.3 Polyvinyl Chloride (PVC) Processes .................................................1-17

1.3 PROCESS SELECTION..........................................................................1-22

1.3.1 Process Alternatives.........................................................................1-23

1.3.2 Concept Screening ...........................................................................1-26

1.3.3 Concept Scoring ...............................................................................1-27

1.4 CONCEPTUAL DESIGN AND FLOWSHEETING....................................1-30

1.4.1 Conceptual Design ...........................................................................1-30

1.4.2 Conceptual Flowsheeting .................................................................1-38

1.4.3 Polyvinyl Chloride Overall Process Flow Diagram (PFD) ..................1-45

1.5 PROCESS DETAILS ...............................................................................1-46

1.5.2 Reaction Kinetics..............................................................................1-47

1.5.3 Thermodynamics ..............................................................................1-52

1.6 WASTE TREATMENT .............................................................................1-58

1.7 CONCLUSION ........................................................................................1-58

CHAPTER 2 ........................................................................................................... 2-1

MARKET ANALYSIS .............................................................................................. 2-1

2.0. ECONOMIC DATA/SUPPLY AND DEMAND ............................................... 2-1

2.1 Introduction ........................................................................................... 2-1

2.2 Applications of Polyvinyl Chloride ......................................................... 2-1

2.3 Global Consumption of Polyvinyl Chloride ............................................ 2-3

2.4 Production of Polyvinyl Chloride............................................................ 2-4

2.5 PRODUCTION RATE AND PROFITABILITY STUDY .............................. 2-7

2.5.1 Yearly Cost and Stream Factor ......................................................... 2-7

2.6 TOTAL CAPITAL INVESTMENT .............................................................. 2-7

2.7 OPERATING CAPITAL COST.................................................................2-16

2.7 Cost of Raw Material, CRM....................................................................2-16

2.8 Cost Operating Labor, COL ...................................................................2-17

2.9 Cost of Utilities, CUT .............................................................................2-19

2.8 OTHER MANUFACTURING COST .........................................................2-20

2.9 VARIABLE COST ....................................................................................2-22

2.10 BREAKEVEN ANALYSIS ........................................................................2-22

2.11 PAYBACK PERIOD (PBP) ......................................................................2-23

2.12 CONCLUSION ........................................................................................2-27

CHAPTER 3 ........................................................................................................... 3-1

SITE SELECTION .................................................................................................. 3-1

3.1 SITE SELECTION .................................................................................... 3-1

3.2 SITE SELECTION CRITERIA................................................................... 3-1

3.2.1 Raw materials Supply ........................................................................ 3-2

3.2.3 Availabilities of Utilities ...................................................................... 3-3

3.2.4 Availability of Suitable Land and Pricing ............................................ 3-3

3.2.5 Availability of labor ............................................................................ 3-3

3.2.6 Taxation and Government Incentives ................................................ 3-4