Production of Vinyl Chloride Monomer Via Thermal Cracking of Ethylene Dichloride

Production of Vinyl Chloride Monomer via Thermal
Cracking of Ethylene Dichloride
Submitted by:
Miss. Momina Asghar 2017-CH-05
Mr. Umar Hayat 2017-CH-59
Miss. Anaiha Iftikhar 2017-CH-69
Mr. Marwan Bahgan 2017-CH-199
Supervised by: Dr. Zafar Noon

Dr. Umair Aslam
Year: 2021
Department of Chemical Engineering

University of Engineering and Technology Lahore
The Final year project titled "Production of Vinyl Chloride Monomer via thermal cracking of
ethylene dichloride" is being submitted to the Department of Chemical Engineering, University
of Engineering and Technology Lahore in partial fulfillment of the requirement for the Degree
of
Bachelor of Science in Chemical Engineering
Internal Examiner External Examiner
Chairperson

University of Engineering and Technology Lahore
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Declaration
We declare that the work contained in this report has been checked for similarity and the
similarity index is within acceptable limits.
Name Registration No. Signature
Momina Asghar 2017-CH-05
Umar Hayat 2017-CH-59
Anaiha Iftikhar 2017-CH-69
Marwan Bahgan 2017-CH-199
Date:
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Contribution Statement
We, members of the FYP group, endorse the level of contribution in the project titled, "Vinyl
Chloride Monomer Production via thermal cracking of ethylene dichloride” as indicated below.
Registration No. %Contribution Signature
2017-CH-05 48%
2017-CH-59 14%
2017-CH-69 25%
2017-CH-199 13%
Date:
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Dedications
Dedicated to
Our beloved Parents and respected Teachers
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Acknowledgement
First of all, we are appreciative to Almighty Allah who helped us in the effective
accomplishment of our final year project. We would like to express our appreciation towards our
parents for their motivating assistance, kind support and inspiration.
We are highly beholden and thankful to our project supervisors Dr. Zafar Noon and Dr. Umair
Aslam for their priceless encouragement, continuous guidance and steady direction as well as for
giving us their precious time, attention and necessary information regarding the project.
We would like to extend our earnest thanks to all who have readily helped us with their abilities
in developing the project.
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Table of Contents
Declaration....................................................................................................................................iii
Contribution Statement.................................................................................................................iv
Dedications.....................................................................................................................................v
Acknowledgement.........................................................................................................................vi
List of Figures..............................................................................................................................xii
List of Tables...............................................................................................................................xiv
Abbreviations..............................................................................................................................xvi
Abstract........................................................................................................................................xx
CHAPTER 1: INTRODUCTION...............................................................................................1
1.1 Defining the Problem............................................................................................................1

1.2 Background Information......................................................................................................2
1.2.1 Environmental Effects...................................................................................................2
1.2.2 Health and Safety...........................................................................................................2
1.3 Structure and Properties........................................................................................................2
1.4 Production and Demand Analysis........................................................................................3
1.5 Literature and Market Survey...............................................................................................4
CHAPTER 2: PROCESS SELECTION....................................................................................5
2.1 Background...........................................................................................................................5
2.2 Production Routes.................................................................................................................5
2.2.1 Vinyl Chloride from Acetylene.....................................................................................6
2.2.2 Vinyl Chloride from Ethane...........................................................................................6
2.2.3 Vinyl Chloride from Ethylene.......................................................................................7
2.3 Process Comparison.............................................................................................................7
2.4 Process Description..............................................................................................................8
2.4.1 Direct Chlorination......................................................................................................10
2.4.2 EDC Purification..........................................................................................................11
2.4.3 Thermal Cracking........................................................................................................12
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2.4.4 Quenching and Purification.........................................................................................14
2.5 Site Selection......................................................................................................................15
2.5.1 Site Comparison...........................................................................................................16
2.5.2 Location.......................................................................................................................17
2.5.3 Raw Materials..............................................................................................................17
2.5.4 Markets........................................................................................................................18
2.5.5 Energy Supply..............................................................................................................18
2.5.6 Transportation..............................................................................................................18
CHAPTER 3: MATERIAL AND ENERGY BALANCE.......................................................18
3.1 Overall Mass Balance.........................................................................................................18

3.2 Overall Energy Balance......................................................................................................18
3.3 Production Demand and Calculation Basis........................................................................19
3.4 Unit Mass and Energy Balance..........................................................................................19
3.4.1 Direct Chlorinator Reactor...........................................................................................20
3.4.1.1 Mass Balance.........................................................................................................20
3.4.1.2 Energy Balance.....................................................................................................21
3.4.2 Mixer............................................................................................................................21
3.4.2.1 Mass Balance.........................................................................................................22
3.4.2.2 Energy Balance.....................................................................................................22
3.4.3 Lights Column.............................................................................................................22
3.4.3.1 Mass Balance.........................................................................................................22
3.4.3.2 Energy Balance.....................................................................................................23
3.4.4 Heavies Column...........................................................................................................24
3.4.4.1 Mass Balance.........................................................................................................24
3.4.4.2 Energy Balance.....................................................................................................24
3.4.5 Pump............................................................................................................................25
3.4.5.1 Mass Balance.........................................................................................................25
3.4.5.2 Energy Balance.....................................................................................................25
3.4.6 Evaporator....................................................................................................................26
3.4.6.1 Mass Balance.........................................................................................................26
3.4.6.2 Energy Balance.....................................................................................................26
3.4.7 Pyrolysis Furnace.........................................................................................................26
3.4.7.1 Mass Balance.........................................................................................................27
3.4.7.2 Energy Balance.....................................................................................................29
3.4.8 Mixer............................................................................................................................30
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3.4.8.1 Mass Balance.........................................................................................................30
3.4.8.2 Energy Balance.....................................................................................................30
3.4.9 Cooler...........................................................................................................................30
3.4.9.1 Mass Balance.........................................................................................................31
3.4.9.2 Energy Balance.....................................................................................................31
3.4.10 Flash Column.............................................................................................................31
3.4.10.1 Mass Balance.......................................................................................................31
3.4.10.2 Energy Balance...................................................................................................33
3.4.11 Top Cooler.................................................................................................................33
3.4.11.1 Mass Balance.......................................................................................................33
3.4.11.2 Energy Balance...................................................................................................33
3.4.12 Bottom Cooler............................................................................................................34
3.4.12.1 Mass Balance.......................................................................................................34
3.4.12.2 Energy Balance...................................................................................................34
3.4.13 Mixer..........................................................................................................................34
3.4.13.1 Mass Balance.......................................................................................................34
3.4.13.2 Energy Balance...................................................................................................35
3.4.14 HCL Column..............................................................................................................35
3.4.14.1 Mass Balance.......................................................................................................35
3.4.14.2 Energy Balance...................................................................................................36
3.4.15 VCM Column.............................................................................................................37
3.4.15.1 Mass Balance.......................................................................................................37
3.4.15.2 Energy Balance...................................................................................................38
3.5 Aspen plus Simulation........................................................................................................38
3.5.1 DC Reactor Balance.....................................................................................................40
3.5.2 Lights Column Balance................................................................................................40
3.5.3 Heavy Column Balance...............................................................................................42
3.5.4 Pyrolysis furnace Balance............................................................................................43
3.5.5 Quench Tank Balance..................................................................................................44
3.5.6 HCL Column Balance..................................................................................................44
3.5.7 VCM Column Balance.................................................................................................46
CHAPTER 4: DETAILED EQUIPMENT DESIGN..............................................................48
4.1 Pyrolysis Furnace...............................................................................................................48

4.1.1 Required Design Data..................................................................................................48
4.1.2 Design Calculation.......................................................................................................48
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4.1.3 Aspen Simulation.........................................................................................................55
4.2 Evaporator..........................................................................................................................57
4.2.1 Required Design Data:.................................................................................................57
4.3 Direct Chlorinator Reactor (CSTR)....................................................................................65
4.4 VCM Distillation Column..................................................................................................69
CHAPTER 5: PROCESS CONTROL AND INSTRUMENTATION..................................81
5.1 Instrumentation...................................................................................................................81
5.2 Control................................................................................................................................81
5.3 Inducements for Chemical Process Control.......................................................................81
5.4 Fundamentals of Control System.......................................................................................82
5.5 Approaches to Control........................................................................................................82
5.5.1 Varieties of Control Actions........................................................................................82
5.6 Instrumentation and Control on Distillation Column.........................................................83
5.6.1 Disturbances.................................................................................................................83
5.6.2 Manipulated Variables.................................................................................................84
5.6.3 Control Variables.........................................................................................................84
5.7 Instrumentation and Control over VCM Purification Section............................................84
CHAPTER 6: HAZARD AND OPERABILITY ANALYSIS................................................86
6.1 Introduction........................................................................................................................86
6.2 HAZOP Process..................................................................................................................86
6.3 HAZOP Deviation Guide...................................................................................................87
6.4 HAZOP Study on Reactor..................................................................................................87
6.4.1 Hazards........................................................................................................................88
6.4.2 Safety Precautions........................................................................................................88
6.5 HAZOP Study on Pump.....................................................................................................89
6.5.1 Hazards........................................................................................................................89

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6.6 HAZOP Study on Furnace..................................................................................................90
6.6.1 Hazards........................................................................................................................90
6.7 HAZOP Study on Distillation Column...............................................................................91
6.7.1 Hazards........................................................................................................................92
6.7.2 Safety Precaution.........................................................................................................92
CHAPTER 7: COST ESTIMATION.......................................................................................93
7.1 Chlorinator Reactor (CSTR)...............................................................................................93

7.2 Reactor Pump (P-100)........................................................................................................94
7.3 Evaporator (E-105).............................................................................................................94
7.4 Pyrolysis Furnace...............................................................................................................95
7.5 Quench Tank.......................................................................................................................96
7.6 Coolers Cost (E-106, E-111, E-112)..................................................................................98
7.7 Distillation Columns (VCM, HCl, Lights, Heavies)..........................................................99
7.8 Mixing Tanks (V-1, V-2, Mix).........................................................................................100
7.9 Storage Tanks (VCM, HCl)..............................................................................................101
7.10 Total Purchased Equipment Cost...................................................................................102
7.11 Direct Cost......................................................................................................................102
7.12 Indirect Cost...................................................................................................................103
7.13 Total Capital Investment................................................................................................103
7.14 Plant Cost........................................................................................................................103
REFRENCES............................................................................................................................104
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List of Figures
Figure 1- 1: Product wise application of PVC in 2018..................................................................1
Figure 1- 2: Vinyl Chloride Monomer Structure...........................................................................3
Figure 2- 1: Routes to manufacture PVC.......................................................................................5

Figure 2- 2: PFD for Vinyl Chloride Monomer Production Plant.................................................9
Figure 2- 3: Schematic of Chlorinator..........................................................................................11
Figure 2- 4: Schematic Of EDC Cracking Furnace......................................................................13
Figure 2- 5: Schematic of Quench Tank......................................................................................15
Figure 2- 6: Price Data For Ethylene 2019..................................................................................15
Figure 2- 7: Plant Location at GIEDA.........................................................................................17
Figure 2- 8: Major Ethylene Producing Countries.......................................................................18
Figure 2- 9: Railways Network of CPEC.....................................................................................19
Figure 3- 1: I/O Diagram for Process...........................................................................................18

Figure 3- 2: Pictorial for MB of Chlorinator Reactor..................................................................20
Figure 3- 3: Pictorial for EB of Chlorinator Reactor...................................................................21
Figure 3- 4: Pictorial for MB of Mixer........................................................................................22
Figure 3- 5: Pictorial for MB of Lights Column..........................................................................23
Figure 3- 6: Pictorial for MB of Heavies Column.......................................................................24
Figure 3- 7: Pictorial for MB of Pump.........................................................................................25
Figure 3- 8: Pictorial for MB of Evaporator................................................................................26
Figure 3- 9: Pictorial for MB of Furnace.....................................................................................29
Figure 3- 10: Pictorial for MB of Mixer......................................................................................30
Figure 3- 11: Pictorial for MB of Cooler.....................................................................................31
Figure 3- 12: Pictorial for MB of Flash Column..........................................................................33
Figure 3- 13: Pictorial for MB of Top Cooler..............................................................................33
Figure 3- 14: Pictorial for MB of Bottom Cooler........................................................................34
Figure 3- 15: Pictorial for MB of Mixer......................................................................................35
Figure 3- 16: Pictorial for MB of HCL Column..........................................................................36
Figure 3- 17: Pictorial for MB of VCM Column.........................................................................37
Figure 3- 18: PFD on Aspen Plus.................................................................................................39
Figure 3- 19: Aspen Generated Material Balanced of DC Reactor..............................................40
Figure 3- 20: Aspen Generated Energy Balanced of DC Reactor................................................40
Figure 3- 21: Aspen Generated Material Balanced of Lights Column........................................41
Figure 3- 22: Aspen Generated Energy Balance of Light Column..............................................41
Figure 3- 23: Aspen Generated Energy Balance of Heavy Column............................................42
Figure 3- 24: Aspen Generated Energy Balance of Heavy Column............................................42
Figure 3- 25: Aspen Generated Material Balance of Pyrolysis Furnace......................................43
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Figure 3- 26: Aspen Generated Energy Balance of Pyrolysis Furnace........................................43
Figure 3- 27: Aspen Generated Material Balance of Quench Tank.............................................44
Figure 3- 28: Aspen Generated Fractions of Quench Tank.........................................................44
Figure 3- 29: Aspen Generated Material Balance of HC1 Column.............................................45
Figure 3- 30: Aspen Generated Energy Balance of HC1 Column...............................................45
Figure 3- 31: Aspen Generated Material Balanced of VCM Column.........................................46
Figure 3- 32: Aspen Generated Energy Balance of VCM Column..............................................47
Figure 4- 1: Graph to Determine Flue Gas Temperature.............................................................49

Figure 4- 2: Radiation Between a Plane and One or More Tube Rows Parallel to the Plane......51
Figure 4- 3: Gas Emissivity as Function of Partial Pressure and Mean Beam Length................53
Figure 4- 4: Overall Heat-Exchange Factor in Radiant Section...................................................53
Figure 4- 5: Aspen Hysys Model for Fired Heater.......................................................................55
Figure 4- 6: Overall Summary of Aspen Generated Results........................................................55
Figure 4- 7: Correction Factor for 1-shell 2-Tube Pass Heat Exchanger.....................................58
Figure 4- 8: Conventional Tube-Plate Layouts in Shell-And-Tube Heat Exchangers.................60
Figure 4- 9: Shell and Tube Evaporator.......................................................................................63
Figure 4- 10: Aspen Generated Results for Geometry of Exchanger..........................................63
Figure 4- 11: Aspen Generated Results for Process of Exchnager..............................................64
Figure 4- 12: Temperature Profile for Heat Exchanger...............................................................64
Figure 4- 13: Direct Chlorinator Stirred Tank Reactor................................................................68
Figure 4- 14: Aspen Plus Results for DC Reactor.......................................................................69
Figure 4- 15: Flooding Velocity, Sieve Plates.............................................................................72
Figure 4- 16: Liquid Flow Pattern................................................................................................75
Figure 4- 17: Weir Length............................................................................................................76
Figure 4- 18: Weep Point Correlation..........................................................................................77
Figure 4- 19: Discharge Coefficient of Sieve Plates....................................................................78
Figure 4- 20: VCM Distillation Column......................................................................................79
Figure 4- 21: Aspen Results for VCM Column...........................................................................80
Figure 5- 1: Control Scheme of Distillation Column...................................................................83

Figure 5- 2: Instrumentation and Control over VCM Purification Section.................................85
Figure 6- 1: The HAZOP Process................................................................................................86
Figure 7- 1: Purchased Cost for Jacketed and Stirred Reactors...................................................93

Figure 7- 2: Purchased Cost for Chemical Inline Pump..............................................................94
Figure 7- 3: Purchased Cost for Shell And Tube Heat Exchanger...............................................95
Figure 7- 4: Cost for Pyrolysis box-type Furnace,1980...............................................................96
Figure 7- 5: Purchase Cost for Flash Tank...................................................................................97
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Figure 7- 6: Material Factor for different Packing Types............................................................97
Figure 7- 7: Purchased Cost for Shell and Tube Heat Exchangers..............................................98
Figure 7- 8: Purchased Cost for Distillation Columns.................................................................99
Figure 7- 9: Purchased Cost for Mixing Tanks including Driving Unit....................................100
Figure 7- 10: Purchased Cost for Storage Tanks.......................................................................101
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List of Tables
Table 1- 1: Properties of Vinyl Chloride........................................................................................3
Table 1- 2: Current and Expected Future Cost for VCM...............................................................5
Table 2- 1: Process Comparison.....................................................................................................7

Table 2- 2: List of Components Formed During Pyrolysis..........................................................12
Table 2- 3: Plant Location Comparison.......................................................................................16
Table 3- 1: Heat of Reactions for Chlorinator Reactor at 90°C...................................................21

Table 3- 2: Conversion Data for Reactions..................................................................................27
Table 3- 3: Extent of reactions inside furnace..............................................................................29
Table 3- 4: Heat of formation at 500°C.......................................................................................29
Table 3- 5: Pressure verification for Flash Column.....................................................................32
Table 3- 6: Flash Calculations......................................................................................................32
Table 4- 1: Initial Required Data For Design Calculation of Furnace.........................................48

Table 4- 2: Typical Radiant Fluxes And Process Temperatures..................................................48
Table 4- 3: Mean Length of Radiant Beams in Various Gas Shapes...........................................52
Table 4- 4: API Sheet for Box-type Fired Heater........................................................................56
Table 4- 5: Initial Required Data for Design Calculation of Evaporator.....................................57
Table 4- 6: Properties Required for Calculation..........................................................................57
Table 4- 7: General Range for Heat Transfer Coefficient and Fouling Resistances for Sensible
Heat Transfer in Exchanger...................................................................................................57
Table 4- 8: Approximate Design Values for Overall Heat Transfer Coefficient.........................58
Table 4- 9: Carbon Steel Tube Dimensions.................................................................................59
Table 4- 10: Number of Tubes in Conventional Tube Layout.....................................................60
Table 4- 11: Initial Required Data for Design Calculation of Furnace........................................65
Table 4- 12: Data for design calculation......................................................................................70
Table 4- 13: Feed, Top & Bottom Compositions.........................................................................70
Table 4- 14: K-Values of Components........................................................................................70
Table 6- 1: Detail of HAZOP Deviation Guide Words...............................................................87

Table 6- 2: HAZOP Analysis of Reactor.....................................................................................87
Table 6- 3: HAZOP Analysis of Pump........................................................................................89
Table 6- 4: HAZOP Analysis of Furnace.....................................................................................90
Table 6- 5: HAZOP Analysis of Distillation Column..................................................................91
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Abbreviations
Cp Heat Capacity
Cpi Heat Capacity of Individual
Component ΔTm Log Mean Temperature
Difference
m Meter
mm Millimeter
cm Centimeter
m2 Square Meter
m3 Cubic Meter
kJ Kilo Joule
kg Kilogram
h Hour
kmol Kilo mole
L Length
Do Outer diameter of tubes
Di Internal diameter of tubes
μ Absolute Viscosity
λ Latent Heat of Vaporization
v Velocity
A Area
xi Liquid Fraction of Individual
Component yi Vapor Fraction of Individual
Component T Temperature
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f Joint factor
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tw Wall Thickness
k Thermal Conductivity
Rd Dirt Factor
ε Void Fraction
ft Foot
g Gram
s Second
vi Stoichiometry Coefficient
ΔH25° Standard Heat of Reaction at 25oC
Hrxn Heat of Reaction at Temperature T
ΔHF° Heat of Formation
ni Moles Reacted of Individual Component
H Enthalpy
ΔH Change in Enthalpy
Td Dew Point Temperature
TBP Bubble Point Temperature
TF Feed Temperature
R Actual Reflux Ratio
Rmin Minimum Reflux Ratio
𝖺i Relative Volatility of Individual Component
Nt Number of tubes
ΔT Temperature Difference
ṁ Mass flow rate
Q Energy
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°C Degree Centigrade
K Kelvin
P Pressure
ρ Density
kJ/kg Kilo Joule per kilogram
Ds Shell Diameter
B Baffle Spacing
Ft Friction Factor
Re Reynolds Number
ΔP Pressure Drop
TCI Total Capital Investment
Uo Overall Heat Transfer Coefficient
hi Inner Heat Transfer Coefficient
ho Outer Heat Transfer Coefficient
OD Outer Diameter
Ln Liquid Molar Flowrate at Top of the Column
Lm Liquid Molar Flowrate at Bottom of the Column
Vm Vapor Molar Flowrate at Bottom of the Column
Vn Vapor Molar Flowrate at Top of the Column
QC Condenser Duty
QB Reboiler Duty
dP Particle Diameter
VR Reactor Volume
uf Superficial Velocity
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σ Surface Tension
M.W. Molecular Weight
Dc Column Diameter
FCI Fixed Capital Investment
SP Set Point
FT Flow Transmitter
LC Level Controller
FC Flow Controller
PC Pressure Controller
PT Pressure Transmitter
LT Level Transmitter
TC Temperature Controller
TT Temperature Transmitter
Pr Prandtl Number
Nu Nusselt Number
De Equivalent diameter
Tref Reference Temperature
CEPCI Chemical Engineering Plant cost index
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Abstract
Vinyl chloride (VCM) is one of the vital commodities, the main chemical in the polyvinyl
chloride (PVC)'s production. VCM is primarily produced via the thermal cracking of Ethylene
Dichloride (EDC) in a pyrolysis furnace which require Ethylene and Chlorine as the raw
material. This Project is designed for VCM production plant capacity of 167 kton/year located
at Gwadar port to cover the present deficit and the future demand. Feasibility study for process
is done and comparison of VCM production by other methods is studied and selection is done
on the basis of high purity product attainment (99.9%), cheaply available raw material and less
energy intensive process. Material and energy balance on process is performed on MS Excel.
Manual calculation of equipment design including direct chlorinator reactor, evaporator,
Pyrolysis furnace and distillation column are performed on MS Excel and results are verified
via 'ASPEN Plus V10' and 'ASPEN Exchanger design and rating V10'. Instrumentation and
control studies is done for the distillation column and HAZOP study is performed on major
process equipment (Reactor, pump, furnace, distillation column). At the end, cost estimation is
done for the Vinyl Chloride monomer production plant.
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CHAPTER 1: INTRODUCTION
1.1 Defining the Problem
The global production capacity of PVC in the year 2005 was approximately 36 million tons per
year, with an approximate yearly growth of nearly 3%. In Pakistan, Production of VCM and in
turn PVC is done by only one industrial unit and the growing need of PVC dictate the need of
another plant to reduce the import expenditure associated with it and also meet the future
demands.
The applications of VCM as intermediate product is wide in production of useful products.

Around the percentage of 95 of the world's production in vinyl chloride is used in the
manufacturing of thermoplastic PVC (Poly Vinyl Chloride) which is then used as a raw
material in producing many useful products for applications in building and constructions,
health care, electronics and many other things ranging from siding, piping and tubing to wire
and cable insulations such as pipes for water & gas, construction goings-on, medical devices
manufacturing, roofing membranes, credit and debit cards, children playing appliances. [3]
While the balance is used as an intermediate in the methanol or methyl chloroform (CH3CCl3)
production and the rest of vinyl chloride used in generating some of the commonly used
chlorinated solvents and manufactures ethylenediamine which is then used in formulation of
various resins. It is also being used as an aerosol propellants. [13]
FIGURE 1- 1: PRODUCT WISE APPLICATION OF PVC IN 2018
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1.2 Background Information
1.2.1 Environmental Effects
The manufacturing of vinyl chloride raised concerns regarding the hazards, pollution and safety
to the environment as the production, uses and disposal of the product was resulting in the
release of chlorine-based chemicals which are toxic to the environment as VCM and mono-
chloroethylene disclosure occurred formerly in polymerization plants where vinyl chloride was
under intense heat was transformed to form polyvinyl chloride during plastic manufacturing and
then caused the inhalation of the toxic gases in the process. [1]
Therefore, certain measurement for the improvement in the VCM production, dumping and
usage were taken and by improving ventilation (exposure to air), minimizing leaks, modifying
reactor designs by using different types and different process conditions and using unlike
chemical pathways and greater automation for the process resulted in making the vinyl chloride
manufacturing technology among one of the firsts to profit from the improvements. Now, the
modern Vinyl chloride plants are among the cleanest and safest running plants in the list of
chemical process industries of the world. [4]
1.2.2 Health and Safety
Health and safety guidelines to produce vinyl chloride are set up by the occupational safety
and health administration (OSHA). And it involves the proper checking of presence of
amounts of detrimental species in all amenities where VCM is either formed or castoff. The
bodies should not be wide-open to more than 1 ppm concentration of VCM above 8 hours, or
for no longer than 5 ppm concentration for more than 15 minutes. Long-lasting contacts to
further 100 ppm level may head to severe harms. Because of the possibility of formation of
peroxides, vinyl chloride must be stored and elated under inert conditions of atmosphere. The
practice of adding stabilizers during VCM production can forbid the polymerization throughout
stages of handling and storage. It is commonly conveyed by trucks or by railroad tankers.
Moreover several mechanical and chemical recycling processes have been formulated for the
proper disposal of PVC. [4]
1.3 Structure and Properties
Vinyl chloride monomer (VCM), exist as a gas at ambient conditions of pressure and
temperature. Hence, it is handled and used as a compressed volatile liquid in all operations of
polymerization. Its vapor pressure ranges in between 800–1250 kPa in the temperature range of
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50–70◦C which
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is defined as the typical polymerization range. Vinyl chloride also more commonly called as
chloroethylene or ethylene monochloride or chloroethene depending upon the different
processes used for its production. It is a colorless and flammable gas at room conditions of
temperature and pressure with indistinctly slight sweetish odor, a smell similar to that of
chloroform. It is heavier than air and soluble in most commonly occurring organic liquids and
solvents.
FIGURE 1- 2: VINYL CHLORIDE MONOMER STRUCTURE
Vinyl chloride is an organo-chloride consisting of two carbon atoms bonded to each other by a
double bond between them and these carbon atoms are then connected to a single chloride atom
and three hydrogen atoms represented as (H2C=CHCl). Vinyl chloride is not used directly as a
product but due to its flame retardant properties, low cost and its unique use as an intermediate,
it is widely used component in the industries [1]
TABLE 1- 1: PROPERTIES OF VINYL CHLORIDE
PROPERTIES MEASURED VALUES UNITS

Molecular Weight 62.5 g/mol
Viscosity at 20°C 0.19×10−3 Pa.s
density at 20 °C 0.910 g/cm3
Solubility in water at 20 ◦C 0.11 wt.%
Critical temperature 429.8 K
Critical pressure 5600 kPa
Freezing Point -153.7 °C
Boiling Point -13.8 °C
Flash Point -78.9 °C
Vapor pressure at -20 °C 78 kPa
at 20°C 333
1.4 Production and Demand Analysis
Vinyl chlorine lies in the list at 183 position out of 1225 for being the most traded product.
China is the leading producer of vinyl chloride and PVC, with production of over seven million
tons per year (making it to 26% of the marketplace share worldwide). Pakistan lies on the 4 th in
the list of highest import tariffs of VCM (13.7%). [12]
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Total demand for the vinyl chloride to produce PVC in Pakistan showed a healthy growth of
around 39% from year 2018 making it to 278 kilo tons PVC required per year. [18]
 Engro Polymer and Chemicals Limited (EPCL) is the only industry in Pakistan producing
vinyl chloride, the plant has an installed capacity of 195 kilo tons. The rest of the demand is
gratified through imports from other countries. EPCL sells VCM under the name “SABZ”.
 The demand of VCM and PVC is subjugated by the pipes and fittings industries and hence
donating more than half i.e. 57% of Pakistan's demand. The other major uses of it are
included in the Film or packaging industries of about 10%, for footwear manufacturing and
garden hose related products manufacturing the consumption is about 9% for each and the
balance of about 7% is required for the Cable compounds.
 Construction sectors in Pakistan witnessed an increase of around 9% in the year 2017 due to
the increase in the CPEC activities and hence resulted in the increased demand of both
VCM and PVC.
 The industry indirectly benefits from the imposition of import duty on PVC.
 Due to the 0% duty levied on the import of raw material (Ethylene) promoted the local
production of VCM.
 Imposition of anti-dumping duty also had an optimistic impact on industry margins. [5]
In 2018, international demand for PVC in major applications raised for around 65% and to
around 30% for minor PVC directed industries. Total PVC ultimatum is projected to propagate
by a near value of 4% per unit time of year concluded from forecast period, and hence will be
reaching a high record by the year 2023. China is set to be the foremost demand driver over the
next 5 years, and thus will be accounting for nearly 40% of the whole worldwide requirement.
The Indian Subcontinent and Africa are estimated to be the fastest-growing regions in the
equivalent time frame, but on a relatively smaller scale. [12]
1.5 Literature and Market Survey
Market study let us learn about the current and future demand for product and let us determine
the plant capacity for the production. Also it helps in determining the cost and availability of
raw materials. For the case of VCM production, the cost depends on multiple factors but the
most important of them all is energy, processing methods and the cost of raw materials.
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TABLE 1- 2: CURRENT AND EXPECTED FUTURE COST FOR VCM
YEAR VCM Cost ($/ton)

2018 986.32
2019 1160.36
2020 1365.13
2021 1606.04
2022 1889.46
2023 2222.86
2024 2615.12
2025 3076.67
It is deceptive that there exist a substantial increase in the expense of VCM due to its increased
usage in the production of Poly Vinyl Chloride, because of the upsurge in expansion in most
countries.
5|Pag
CHAPTER 2: PROCESS SELECTION
2.1 Background
VCM was chiefly produced by dehydrating ethylene dichloride by the use of alcoholic caustic
potash. However, at first VCM was industrially prepared by hydro-chlorination of acetylene but
this route was almost abandoned after 1940's when ethylene became plentiful. Now almost 90%
of the world's VCM production is done through the balanced process using EDC which is
produced via ethylene. This production process has been advanced and the mark for this
operation has pointedly increased, but no other new process have achieved such commercial
practicability. Even though this is factual, but still it’s a need to inspect the alternative routes.
All present VCM production plants takes C2 hydrocarbons as feed particularly acetylene,
ethylene or ethane. Marketable and profitable operations for these 3 are narrowed to gas-phase
processes. Production of VCM from acetylene is comparatively simpler and is a distinct (single)
stage process, but the cost of acetylene is comparatively higher in comparison to ethylene.
Ethane is observed to be the least expensive C2 hydrocarbon for VCM manufacture, but it is
transformed to product with a much low selectivity.
2.2 Production Routes
Vinyl Chloride is manufactured using different raw materials. The following figure summarizes
the routes of VCM production:
FIGURE 2- 1: ROUTES TO MANUFACTURE PVC
5|Pag
2.2.1 Vinyl Chloride from Acetylene
The reaction of acetylene with hydrochloric acid can be done either in gaseous or in liquid
phase in either fixed bed or multi tubular reactors in almost close to isothermal conditions. The
reaction is carried out on catalyst which is mercuric chloride extended on activated carbon.
HgCl2
C2H2+ HCl → CH2=CHCl
Acetylene was initially obtained from calcium carbide but high energy associated with it
outweighs its drawback. Acetylene can be acquired and then used from high temperature
cracking of either naphtha or methane. The process produces both acetylene and ethylene and
not much expensive operations are essentially required for their separation. But the process
offers downside as acetylene being expensive than ethylene. The acetylene as a raw material is
required to be totally free of toxins (i.e. S, P, Ar etc.) and the unsaturated hydrocarbons should
be present in lesser amount so to avoid the choke and de-activating of the catalyst during the
process of polymerization. Hydrochloric acid required should also be free of Cl 2 so to avoid any
risk of detonation or catalyst poisoning, water should also not be present throughout as it leads
to the corrosion risks. The catalyst volatilization poses a greater risk here and due to this reason
some additives are added but still the catalyst loss is encountered either by flow reversal or by
using double reactors with second one containing the fresh catalyst. , the acetylene route is
currently of little commercial importance as much of the development is devoted in this to
recover the volatility issues. [7]
2.2.2 Vinyl Chloride from Ethane
VCM is also produced by the de-hydro chlorination of dichloroethane over some suitable catalyst.
Cl−CH2−CH2−Cl → CH2 =CHCl + HCl
This route shows the plus of higher selectivity of VCM and less carbon deposition due to the
low temperature ranges but shows the conversion of only 60-70% per pass and also pose the
high cost due to the expensive catalytic operation and wide shut down. Thus, yields are quite
low, i.e. only 20–50% per pass. Due to the molecular symmetry of the ethane compound, the
direct use of ethane to produce VCM cannot be realized although it reduces the expenses
associated to raw material but it leads to the wide range of byproducts due to the substitution
reactions as the method
6|Page
makes the use of oxy clines at high-temperatures and distinct catalysts to produce the
worthwhile by products such as EDC, ethylene, ethyl chloride and also ensure the high VCM
selectivity but due to the high temperatures of about 500oC the chlorine can become violent and
effect the construction and material of reactor. [6]
Ethane can be transformed to vinyl chloride by various routes:


High-temperature chlorination: C2H6 + 2Cl2  C2H3Cl + 3HCl

High temperature oxy-chlorination: C2H6 + HCl + O2  C2H3Cl + 2H2O

High temperature oxidative chlorination

(Combination of above 2): 2 C2H6 + 3/2O2 + Cl2  C2H3Cl + 3H2O
2.2.3 Vinyl Chloride from Ethylene
VCM from ethylene is acquired as an outcome of thermal cracking of ethylene dichloride. The
exothermic reaction during direct chlorination or/and oxy-chlorination of ethylene is followed
by the endothermic cracking reaction in furnace.
Direct chlorination: CH2CH2 + Cl2  C2H4Cl2

Oxy-chlorination: C2H4 + 2HCl + ½ O2  C2H4Cl2 + H2O
EDC pyrolysis: 2 C2H4Cl2  2 C2H3Cl + 2HCl
Prior to the thermal cracking of ethylene dichloride, it is prepared either in direct or oxy
chlorinators whose choice is dependent on the less number of by-products formation which is
achieved by direct chlorination with higher selectivity.
2.3 Process Comparison
TABLE 2- 1: PROCESS COMPARISON
ACETYLENE ETHANE ETHYLENE
RAW MATERIAL  Acetylene  Ethane  Ethylene

 Hydrogen chloride  Ethylene  Chlorine
 1,2-dichloroethane  1,2-dichloroethane
CATALYST
Mercuric (II) chloride Cupric chloride for oxy- Ferric chloride for direct
on chlorination of chlorination
activated carbon ethane and potassium
chloride to lower
the melting point of
copper catalyst
7|Page
LIMITATIONS Acetylene forms Chlorine with ethane Several Chlorinated by-
explosion mixtures lead to products are formed
(acetylides) with explosive mixtures.
alloys such as
copper, mercury,
and silver
MAIN  Reactor  Reactor  Reactor

EQUIPMENT  Heavies  Condenser  Furnace
stripper  Separation  Quench (cooler)
 Vent wash column  Distillation
tower  Distillation columns
 Cooler columns
 Knockout drum
CATALYST
PROS AND Mercuric chloride Copper catalysts show FeCl3 proves an excellent
CONS makes an excellent volatile behavior at the catalyst and show 99.5%
catalyst to achieve 98% desired reaction
HCl and 99% acetylene Temperatures and the Conversion of raw

conversion but during catalyst mass is unable to materials.
However if oxy-
Hydro-chlorination, retain its activity over an
chlorination is used, the
AuCl sublime and extensive period of time
side reaction of ethylene
catalyst de-activation due to the loss of copper lead to slight deterioration
causes regeneration and is required to be of catalytic activity and
problem. replaced with time. hence increasing the
resistance to permeability
and selectivity for EDC.
COST ($/ton) 5795 (2020-2030 600 (Nov 2019) 900-1200 (March 2019-
forecast) 2020)
2.4 Process Description
The procedure for producing vinyl chloride monomer encompasses the following main steps:
1. Imperiling 1, 2-dichloroethane (EDC) in a pyrolysis furnace to produce a gas mixture

mainly consisting of a complex mixture mainly consisting of VCM, HCl and unreacted
EDC.
2. Quenching the gas mixture to form a liquid complex mixture.
3. Subjecting the liquid mixture to a separation units particularly a distillation column to
remove significantly all the HCl present in the mixture leaving a stream comprising mainly
VCM and EDC.
4. Subjecting this stream to a second separation to get essentially pure Vinyl Chloride
8|Page
Monomer and remaining mixture is recycled. [8]
9|Page
In the process Ethylene, HCl and chlorine are gases where VCM can be used as liquid at low
value of temperatures and suitable pressure, whereas ethylene dichloride exist in both liquid and
gaseous phase. For that reason high pressures and low temperatures are projected in various
processing steps.
FIGURE 2- 2: PFD FOR VINYL CHLORIDE MONOMER PRODUCTION PLANT
10 | P a g e
2.4.1 Direct Chlorination
Ethylene (C2H4) and Chlorine (Cl2) react together in homogenous catalytic reaction to form 1,
2- dichloro ethane (EDC). Secondary reaction takes place and the catalyst used is ferric (III)
Chloride FeCl3 which is of Lewis-acid type and is used in concentrations ranging in between 0.1
to 0.5 wt.% and proceeds via a polar mechanism to polarizes the Chlorine molecules which then
the acts as an electrophilic reagents to attack the double bond of ethylene as [7]
1)
FeCl3+Cl2 ⇌ FeCl4- + Cl+
2)
FeCl4- + Cl+ + C2H4 → FeCl3 + C2H4Cl2
Highly exothermic reaction occurs in the reactor (chlorinator) and hence the reaction is designed
to perform by the gases being dissolved in the liquid phase of Ethylene dichloride (EDC) for
improved temperature regulations.
C2H4 +Cl2  C2H4Cl2 ΔHo298 = -182 kJ/mol
The most important by-product produced is TCE shorted for 1,1,2-trichloroethane in the
presence of excess chlorine or it can be produced by the chlorination of liquid EDC present in
the reactor
C2H4 + 2Cl2→C2H3Cl3 (TCE) +HCl
Or
C2H4Cl2 + Cl2→C2H3Cl3 (TCE) +HCl
Due to the realization of chlorine radicals, impurities form so, the reactants of high purity are
used to avoid the contaminations production. Also the excess of ethylene is used to minimize
by- product formation. [4]
The direct chlorination may be carried out by two techniques namely
1. Low temperature chlorination
2. High temperature chlorination
In low temperature chlorination or LTC, the reactions occurs at a temperature lower than the
mixture's boiling point at about 50-70°C. And attains a higher selectivity for EDC i.e. about
99%. In this case the reactor is mostly a gas-liquid contact column and controls the heat of
reaction either by external circulation of a little cooler EDC or by using internal devices such as
cooling coils. But this particular technique lists some drawbacks as
 Rejection of the heat of reaction to the environment at lower temperatures represents an
incompetent process.
 The removal of the catalyst from EDC is an expensive operation and lead to sources of
pollution.
11 | P a g e
In high temperature chlorination or HTC, the reaction occurs at boiling point of EDC i.e. in
temperature range of 90-150°C in a pressure range of 1.5-5 bar. The selectivity by this process
is a little less than LTC but can be increased by using inhibitors and temperature up to 150°C. In
this case the reactor is an independent equipment and the heat of reaction produced is 7 times
greater than the LTC reactor and proves advantageous for purification process. [4]
FIGURE 2- 3: SCHEMATIC OF CHLORINATOR

2.4.2 EDC Purification
Ethylene di-chloride used in pyrolysis is required to be of higher purity as contaminated EDC

could lead to fouling and reserves built-up. Some impurities do not separate easily from VCM
during its purification e.g. chloroprene produced along with EDC in furnace and then recycling
of EDC as it is at later point could lead to the foundation of polymeric residue which could
further lead to fouling deposition of the tubes. Some impurities such as Chloromethane (tri-
chloromethane) acts as a good impurity and leads to the increase in more good selectivity of
VCM and a higher reaction rate at markedly lower temperatures. Its optimum value is observed
at around 2000 ppm.
Crude EDC (both recycled and from chlorinator) is decontaminated in the two consecutive
distillation columns. In the lights column, EDC is unglued from lighter impurities i.e. butadiene,
chloroprene and unreacted raw materials then from the heavy column, EDC is separated from
the compounds like tri-chloroethane and di-chlorobutane. [6]
Since, production of chlorinated products are less in absence of oxy-chlorination step and at the
end the units required for purification are smaller and also cut the capital and operating cost. [8]
12 | P a g e
2.4.3 Thermal Cracking
1,2-dichloroethane after the purification step goes to pyrolysis furnace where it decays into
Vinyl chloride and hydrochloric acid HCl by a multifarious or complex reaction mechanism.
The endothermic reaction (ΔH=67 kJ/mol) takes place in between a temperature range of 480-
550°C and at pressure in between 3-30 bar and the heat for this reaction is provided by the set
of burners along the walls of furnace. The main reaction commences at 480°C, but an efficient
reaction rate is achieved at higher temperatures and 50% conversion is achieved at temperature
above 550°C but it is kept lowered as higher temperatures lead to deposition of impurities as
well as more coke formation. Therefore, the reaction temperature is set at 500°C. [7]
TABLE 2- 2: LIST OF COMPONENTS FORMED DURING PYROLYSIS
COMPONENT FORMULA NORMAL B.P ORIGIN EXIT

(OC)
Vinyl chloride C2H3Cl -13.8 Thermal cracking VCM Column,
monomer (VCM) product
Ethylene 1,2-C2H4Cl2 82.4 Direct chlorination Intermediate, to
dichloride cracking
(EDC)
Acetylene C2H2 -84 Thermal cracking HCl Column as
impurity
Hydrochloric HCl -66.5 Thermal cracking HCl Column, side
acid product
Ethylene C2H4 -103.7 Thermal cracking EDC purification, in
lights waste
Chlorine Cl2 61.3 Thermal cracking EDC purification, in
lights waste
Butadiene C4H6 -4.5 Thermal cracking EDC purification, in
(BUTD) lights waste
Chloroprene C4H5Cl 37 Thermal cracking EDC purification, in
(CLP) lights waste
Tri-chloro C2H3Cl3 113.9 Direct EDC purification, in
ethane (TCE) chlorination heavies waste
Di-chloro C4H8Cl2 155.1 Thermal cracking EDC purification, in
butane heavies waste
13 | P a g e
The reaction device is a long tubular coil placed in a furnace, the preheated gas feed enters at
the top of the convection zone to get heated up and reach the superheated state in order to reach
its cracking temperature of about 400-420°C where the heat here is provided by both modes of
convection and radiation as from flue gases and firebox respectively. EDC is then cracked to
VCM, HCl and by products in the radiation section. Natural gas is generally used to drive the
furnace, some industries also use Hydrogen gas if abundantly and cheaply available. [10]
The reactions in the radiation zone occur with the residence time of 5-30 s and varies with the
coil length. The diameter of tube is selected such that to give the superficial velocity in between
the 10-20 ms-1 range. Chromium-Nickle alloys are generally used to tackle high temperatures in
the radiation zone.
FIGURE 2- 4: SCHEMATIC OF EDC CRACKING FURNACE
Some reactions occurring inside furnace reactor are given below:
1,2-C2H4Cl2  C2H3Cl (VCM) + HCl (ΔH= 67kJ/mol) [4]

C2H3Cl  C2H2 + HCl
These two reactions lead to the main products formation VCM, HCl and acetylene which
further may lead to the formation of some impurities i.e. benzene, vinyl acetylene etc.
1,2-C2H4Cl2  C2H4 + Cl2
The further reactions lead to the formation of lighter unsaturated hydrocarbons.

14 | P a g e
C2H4 + C2H2  C4H6 (butadiene)
C2H2 + C2H3Cl  C4H5Cl (chloroprene)
With the occurrence of free radicals, a range of higher molecular species including butadiene
and chloroprene forms, among these chloroprene is needed to be removed as otherwise if
present above 8 wt. % concentration leads to such product formation which leads towards
polymerization inside the furnace. Its maximum allowable value is 100 ppm. [4]
1,2-C2H4Cl2 + Cl2  C2H3Cl3 (TCE) + HCl

2C2H4Cl2  C4H8Cl3 (heavies) + Cl2
These reactions lead to the formation of heavy chlorinated hydrocarbons. By maintaining the
temperature of reaction further down to 500°C can avert the coke formation but it also drops the
reaction rate and hence initiators such as nitromethane, chloroform CHCl3 or carbon
tetrachloride CCl4 are added before entering the cracking furnace which causes the formation of
free chlorine radical and hence increases the conversion to EDC at lower temperatures. [4] [7]
2.4.4 Quenching and Purification
After the thermal cracking (pyrolysis), the mixture is subjected to rapid cooling by the process
of quenching to create liquid and gas mixture. It prevents the further decomposition of VCM
also the more by-products formation and removes the higher molecular weight impurities and
the coke produced, several alternatives are used for this purpose as the quenching not just act as
a cooling unit but aids the coarse separation prior to distillation.
The furnace effluent gas mixture is first quenched or cooled in a condenser to reach to the flash
conditions, then fed to the flash column to create 2-phases, for cooling purpose, the liquid
mixture of VCM, HCl and EDC recycled from column. The temperature is usually dropped
below 150°C preferably to about 120°C.
The quenched mixture is then transported to the distillation column and around 99% of
anhydrous HCl is recovered as the top product from the HCl distillation column. The remaining
mixture then moves to the second column. Where VCM as essentially pure product is obtained
from the top and EDC along with impurities is recycled from the bottom of column towards
EDC purification column. [4]
15 | P a g e
FIGURE 2- 5: SCHEMATIC OF QUENCH TANK
2.5 Site Selection
The determination process of where to place the plant or facility is mainly dependent on the
effectiveness with which the products (services) are conveyed to the customers. The plant
location is based on many other factors such as the company’s future expansion plan (if any)
and policy, branching out plan for the products, fluctuating market conditions, the exchanging
sources of raw materials and others. The contiguity to customers and providers, labor costs, and
conveyance costs are also considered while selecting the particular location.
FIGURE 2- 6: PRICE DATA FOR ETHYLENE 2019
16 | P a g e
The raw materials for VCM production are ethylene and chlorine. Chlorine is easily available in
Pakistan at various industries. Whereas, ethylene is not produced in Pakistan and hence being
imported from other countries, the main importers and exporters in Pakistan are:
 Seller: Abu Dhabi national oil company, UAE

 Seller: Me global international FZE, Kuwait
 Buyer: Engro polymer and chemicals ltd.
 Buyer: Ibrahim fabrics and Rupafil ltd., ICI Ltd.
2.5.1 Site Comparison
As Ethylene have to be imported from outside countries, the three main industrial cities of
Pakistan i.e. Lahore, Karachi and Gwadar were selected initially for further analysis as two of
them have wide sea ports available and all three have good transportation facilities as well as
good import/export relations with most of the world. Whereas for availability of another raw
material i.e. chlorine, the major producers of this compound are located in the surrounding
localities of all these selected regions for analysis purposes.
TABLE 2- 3: PLANT LOCATION COMPARISON
FACTORS LAHORE KARACHI GWADAR

Location Sundar Industrial Estate Bin Qasim port Gwadar port
Raw Material C2H4: Imported C2H4: Imported C2H4: Imported
Cl2: Available Cl2: Available Cl2: Available
Market Available Available Not Available
Climate Moderate Hot Dry and Hot
Water Ground water Sea Sea
Transportation facility Lahore Dry port Karachi Port Gwadar port
Natural Disaster Stable Stable Stable
Electricity Lahore Electricity K-Electric Coal power plant
Supply Company Gwadar
Labor Available Available Available
Up till now the only producer of VCM in Pakistan is EPCL which is located in Karachi at Bin-
Qasim port and hence outweighs the disadvantage of the location despite availability of all other
advantages such as market, Sea port for import purposes. For plant in Lahore, main difficulty is
water as there is no water resource in Lahore that we can excessively use for industry. Raw
17 | P a g e
material can be imported through Dry port in Lahore. So the final selection is made as Gwadar
Industrial state, Gwadar.
2.5.2 Location
The proposed location is Industrial zone M2, Gwadar illustrated in Gwadar Smart Port City
Master Plan by Gwadar Development Authority. It is near GIEDA (Gwadar Industrial Estate
Development Authority) which is commercial industrial project from government of
Baluchistan.
FIGURE 2- 7: PLANT LOCATION AT GIEDA

2.5.3 Raw Materials
Ethylene and Chlorine are the essential raw materials required to produce Ethylene Dichloride
which then produces Vinyl Chloride Monomer through cracking. Ethylene can be imported
from major ethylene producing countries such as Saudi Arabia and China through Gwadar Port.
Trade with these ethylene rich countries in the region will now be convenient and economical
than ever due to the tax exemptions at the Gwadar Free Zone. Saudi Arabia is a global player in
ethylene and its derivatives as most petrochemical companies and industries in the country are using
ethane as a key feedstock. And having it as a feedstock gives high production yield of ethylene. [13]
Saudi Arabia has current Ethylene production capacity of 17.5 Mt/year (9% of the total global
capacity). China which will be leading the world by 2030 in terms of strategic and announced
ethylene capacity addition with an overall capacity of about 27.24 Mt/year (by year 2030).
According to a latest report by Global Data, there will be around 167 announced and planned
plants in Asia and the Middle East in coming years. [14]
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FIGURE 2- 8: MAJOR ETHYLENE PRODUCING COUNTRIES
2.5.4 Markets
The domestic sales of PVC has been uniformly increasing at the rate of 5% per annum. The
global consumption was estimated to be 38.4 Mt in 2013, raised by 1.1 Mt from 2012. The
demand of PVC is mainly driven by construction, infrastructure and development projects
which is happening in Gwadar and will continue to do so under CPEC projects. Under the short
term plan of Gwadar Smart Port City the industrial zone M0 and M1 is to be built soon on
priority basis in next 2-3 year which include setting the industries related to construction and
building materials, packaging, piping and textile with some other sectors. All the mentioned
industries consumes VCM. It is very likely that with the formation of these industries in the
zone our products will be purchased at our door step.
2.5.5 Energy Supply
Gwadar is currently powered through imported 100 MW electricity from Iran. To make Gwadar
self-sufficient in its electricity demands, establishment of 300 MW imported coal based power
project is in progress in Gwadar. The ground breaking of the project was done on November 4,
2019 and it is anticipated to be completed by the end of 2022. [15]
2.5.6 Transportation
The connection of Pakistan’s railway tracks setup from Afghanistan and China to the deep sea
port Gwadar is of utmost importance for both countries Pakistan and China under CPEC. The
overall proposal will help conveyance of goods from central Asian points and China to the port
city. It has been planned to construct a railway line of 1328 km from point of Jacobabad and
19 | P a g e
Quetta via Basima to Gwadar. It will connect the port city not only with China but also with the
rest of the Pakistan.
It will boost trade and shipment of goods and transportation ease within the country. It is also
part of a plan to lay a railway track of 560 km from point of Quetta to Kotla Jam on ML-2 via
Zhob and DI Khan. Pakistan Railway has also planned to build a railway line in Afghanistan
from Peshawar to Torkham. According to the bureau of development and planning, the complex
would be protracted to Kabul in order to connect the Central Asian points with Gwadar via
railway line. The roads shown in following map are making a very wide network providing
convenient access and solutions for all areas of industrial, residential and commercial. Highway
which was previously called as Northern Bypass is the biggest road in Gwadar Road Network
Map. There is a wide network of Road Network which will bring transportation ease from
Gwadar to the rest of country also connecting them to the China. Many highway projects are
already completed and others are in progress. [16]
FIGURE 2- 9: RAILWAYS NETWORK OF CPEC
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CHAPTER 3: MATERIAL AND ENERGY
BALANCE
The process assumption include a continuous and steady state process

3.1 Overall Mass Balance
Material balance is merely the law of conservation of mass, which says that mass can neither be
created nor be destroyed. A balance on a quantifiable masses in a system is generalized as:
Input + Generation – Output – Consumption = Accumulation
The accumulation term for steady-state continuous process is zero, thus:
Input + Generation – Output + Consumption = 0
598 kg/h 1423 kg/h

Lights waste Heavies waste
ETHYLENE (C H )
2 4
9061 kg/h VINYL CHLORIDE MONOMER
(C H Cl) 17709 kg/h
I/O 2 3
Diagra
CHLORINE (Cl )
2 m Hydrogen Chloride Gas (HCl)
22667 kg/h 11998 kg/h
FIGURE 3- 1: I/O DIAGRAM FOR PROCESS

3.2 Overall Energy Balance
The First Law of Thermodynamics is a statement of energy conservation. Energy cannot be

created nor destroyed, it can only be changed from one form to another. Energy transfer can
take place by flow of heat, by performance of work or by transport of mass.
𝑢𝑖2 𝑢𝑖2
Rate of energy accumulation= ∑ 𝑚 (𝐻𝑖 + + 𝑔𝑧𝑖) - ∑ 𝑚(𝐻𝑖 + + 𝑔𝑧𝑖) + Q - Ws
𝑖𝑛𝑝𝑢𝑡 2 𝑜𝑢𝑡𝑝𝑢𝑡 2
18 | P a g e
The standard heat of reaction is found using
ΔH 25
o
= (Σv ΔH
i
o
) − (Σv ΔH
f P i
o
f
)
The heat of reaction at desired temperature is found using

𝑇 𝑇
Hrxn = ΔH o + ((Σ∫ niCpidT) P − (Σ∫ niCpidT) R)
25
25 25
The enthalpy of reactants and products are found using
𝑇
H=ṅ �
𝑇𝑟𝑒𝑓 𝐶pdT
∫ = (A+BT+CT2+DT3+ET4) dT
ṅ∫𝑇𝑟𝑒𝑓
The enthalpy of phase change is found as
H = A*(1- 𝑇 )n
𝑇𝑐
Reference Condition
Temperature = 273 K
3.3 Production Demand and Calculation Basis
Vinyl Chloride Monomer to be produced = 170 kton/yr = 17709 kg/h
Initially with 5000 kg/h of Cl2 as basis for calculation produced 9857 kg/h VCM. However the
required amount of VCM produced is 17709 kg/h. So, multiplying Chlorine flowrate with the
scale up factor = 4.533, Desired product requirement is achieved. The new flowrate of
Chlorine is found to be:
Calculation Basis (Chlorine Flowrate) = 5000*4.533

= 22667 kg/h
= 319.7 kmol/h
With 1% excess of Ethylene = 319.7*(1+0.01) kmol/h

= 322.9 kmol/h
= 9061 kg/h
19 | P a g e
3.4 Unit Mass and Energy Balance
3.4.1 Direct Chlorinator

Reactor
𝐹𝑒𝐶𝑙3
Main: 𝐶2𝐻4 + 𝐶𝑙2 →−−→ 𝐶2𝐻4𝐶𝑙2
Side: 𝐶2𝐻4𝐶𝑙2 + 𝐶𝑙2 𝐶2𝐻3𝐶𝑙3 +HCl

3.4.1.1 Mass Balance
Data Available:
Selectivity towards Ethylene Dichloride = 99 [7]
Conversion of Ethylene = 98 % [18]
Equations for Extent of reaction:
C2H4: Out = In - Ɛ1
Cl2: Out = In - Ɛ1-Ɛ2
C2H4Cl2: Out = In + Ɛ1 -Ɛ2
C2H3Cl3: Out = In + Ɛ2
HCl: Out = In + Ɛ2
With Input=0 for all except chlorine and ethylene, out molar flowrate for ethylene is
found using conversion data given for ethylene and for Ethylene dichloride using
selectivity data given and then solving the simultaneous equations:
EXTENT 1 = 316.45 kmol/h

EXTENT 2 = 3.1645 kmol/h
Putting these values in above equations, molar flowrates for rest 3 components were found out
and on multiplication with molecular weight of individual, mass flowrate was found out.
Component kmol/h kg/h

Ethylene 323 9061 Component kmol/h kg/h
Direct
Ethylene 6.48 181
Chlorinator Chlorine 0.09 6.8
Ethylene Dichloride 313 31002
Reactor Tri Chloroethane 3.16 422
Component kmol/h kg/h Hydrogen Chloride 3.16 115
Chlorine 319.7 22667 31728
FIGURE 3- 2: PICTORIAL FOR MB OF CHLORINATOR REACTOR

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3.4.1.2 Energy Balance
Operating Temperature = 90°C
Operating Pressure = 1.5 bar
TABLE 3- 1: HEAT OF REACTIONS FOR CHLORINATOR REACTOR AT 90°C
o
Reaction 1 ΔH90 = -182 kJ/mol
o
Heat of Condensation = 9.57E+06 kJ/h
Component Mole % kJ/h Component Mole % kJ/h

Ethylene 100 1.32E+06 Direct Ethylene 1.98 1.59E+03
Chlorin ator
Chlorine 0.029 3.66E-01
Reactor
Ethylene Dichloride 96 3.57E+06
Tri Chloroethane 0.97 4.28E+02
Hydrogen Chloride 0.97 3.04E+02
Component Mole % kJ/h 3.57E+06
Chlorine 100 9.80E+05
FIGURE 3- 3: PICTORIAL FOR EB OF CHLORINATOR REACTOR
Q = Hout - ƩHin - Hcond + Ɛ*Hrxn

Q = -6.62E+07
Temperature after
cooler
T = (Q/m.Cp) + Tref
T = 31.6°C
Water flowrate for ΔT=20°C
m = Q/ (Cp.ΔT)
m = 157160 kg/h
3.4.2 Mixer
For the purpose of recycling, a mixer is used to mix up fresh and recycled stream, the flowrates
being recycled were used as, initially 0 components were assumed in the recycled stream and
material balance on entire flowsheet was performed, the results of flowrate from bottom of
VCM Column were then added to recycled stream and material balance was updated, this was
performed once again to attain steady state.
21 | P a g e
STREAM 3FIGURE 3- 4: PICTORIAL

STREAM 14 FOR MB OF MIXER
COMPONENT kg/h kg/h COMPONENT kg/h
Tri chloroethane 422 H3 at 90°C 628 = 3.57E+06 kJ/h Tri chloroethane 1050
Hydrogen Chloride 115 Hydrogen Chloride 115
Ethylene 181
H 14 at 142°C = 3.24E+06 kJ/h
Ethylene 181
Temperature after
Ethylene Dichloride 31002 19167 Ethylene Dichloride 50170
M
mixing Chlorine 6.84 Chlorine 6.845
Vinyl Chloride 0.136 Vinyl Chloride 0.136
Butadiene 99 Butadiene 99
Chloroprene T =169(Q/m.Cp) + Tref Chloroprene 169
Di chlorobutane 367
T = 93.7°C Di chlorobutane 367
31728 20432 52160
3.4.3 Lights Column
Heavy key = ethylene dichloride

Light key = Chloroprene
Assumptions
Let purity of heavy key in top product is 6% and purity in bottom product is 97.8%
Overall balance
Feed = Distillate + Bottom

531 = D + W
D = 531 - W
Ethylene Dichloride
balance
Fxfi = Dxdi + Wxwi
(531*0.954) = (531 - W)*0.978 + (0.06*W)
W = 517.5 kmol/h
D = 13.67 kmol/h
22 | P a g e
As no intermediate non keys are present all species lighter than LK will go on top and
all heavier than HK will go to bottom.
FIGURE 3- 5: PICTORIAL FOR MB OF LIGHTS COLUMN TOP BOTTOM

COMPONENT kg/h
Tri chloroethane 1050 COMPONENT kg/h kg/h
Hydrogen Chloride 115 Tri chloroethane 1050
Ethylene 181 Hydrogen Chloride 115
Lights Column Ethylene 181
Ethylene Dichloride 50170
Chlorine 6.845
Chlorine 6.8
Vinyl Chloride 0.136
Vinyl Chloride 0.136
Chloroprene 169 Chloroprene 114 55
Di chlorobutane 367 Di chlorobutane 367
52160 598 51561
With all given temperature from source [4]. Enthalpies were calculated directly
Top temperature = 214 K = -58.7°C

Bottom Temperature = 367.8 K =
94.8°C
Heat of vaporization in reboiler at bottom temperature = 1.56E+07 kJ/h
Heat of Condensation in total condenser at top temperature = 1.048E+05 kJ/h
H5 at -58.7°C = -2.17E+04 kJ/h

H4 at 94.8°C = 6.19E+06 kJ/h
Feed temperature = 93.7°C
H3A = 5.58E+06 kJ/h
Condenser Duty
Qc = Hout -Hin - Hcond

Qc = -5.7E+06 kJ/h
Reboiler Duty
Qb = Hout -Hin + Hvap

Qb = 1.62E+07 kJ/h
Flowrate for saturated steam in reboiler at 120.21°C and 2 bar

m = Q/ (Cp.ΔT)
23 | P a g e
m = 7.58E+03 kg/h
Flowrate for cooling water with ΔT = 15°C and Tin = 25°C
m = Q/ (Cp.ΔT)
m = 90307 kg/h
3.4.4 Heavies Column
Heavy key = Tri-Chloroethane

Light key = Ethylene dichloride
Assumptions
Let purity of light key in top product is 99.87% and purity in bottom product is 0.01%
Overall balance

517.5 = D + W
D =517.5 - W
Ethylene Dichloride
balance
Fxfi = Dxdi + Wxwi
(517.5*0.978) = (517.5 - W)*0.01 + (0.9987*W)
W = 506.7 kmol/h
D = 10.83 kmol/h
As INKs are absent, all species lighter than LK will go on top and all heavier than HK will go to
bottom,
FIGURE 3- 6: PICTORIAL FOR MB OF HEAVIES COLUMN TOP BOTTOM

COMPONENT kg/h COMPONENT kg/h kg/h
Tri chloroethane 1050 Heavies Column Tri chloroethane 5.37 1045
Chloroprene 55 Chloroprene
With all given temperature from source [4]. Enthalpies were calculated directly 55
Ethylene Dichloride 50089 Ethylene Dichloride 50078 10.73
Di chloro Butane 367 Di chloro Butane 367
51561Top temperature = 357 K = 84.2°C 50138 1423
24 | P a g e
Bottom Temperature = 400 K = 127°C
H7 at 84.2°C = 5.58E+06 kJ/h

H6 at 127°C = 1.13E+07 kJ/h
Feed temperature = 94.8°C, H4 = 6.19E+06 kJ/h
Condenser Duty
Qc = -1.69E+07 kJ/h
Reboiler Duty
Qb = 5.37E+06 kJ/h

m = Q/ (Cp.ΔT)
m = 2.51E+03 kg/h
m = Q/ (Cp.ΔT)
m = 200217 kg/h
3.4.5 Pump
For pump, mass balance is simply mass getting in equal to the mass getting out
COMPONENT kg/h3- 7: PICTORIAL FOR MB OF

kmol/hFIGURE PUMP
Tri chloroethane 0.04 5.37 Tri chloroethane 0.04 5.37
3.4.5.2Chloroprene
Energy Balance 0.62 55 Chloroprene 0.62 55
Ethylene Dichloride 506 W50078 Ethylene dichloride 506 50078
s= ΔP/ϼ + 0.5Kv2 + GΔz +E f
50138 50138
Assumption: No elevation change, No change in energy, No friction in pump & pipes so,
25 | P a g e
Ws=ΔP/ϼ
Inlet Pressure = P1 = 1.2 bar =120000 Pa
Outlet Pressure = P2 = 26 bar = 2600000 Pa
Total density of mixture = 1250 kgm-3
Q = Ws = (2600000-120000)/1250
Ws = 1984.5 J/kg = 37 hp
3.4.6 Evaporator
For heat exchanger, mass balance is simply mass getting in equal to the mass getting out
COMPONENT PICTORIAL FOR MB OF COMPONENT

kmol/h3- 8:kg/h
FIGURE EVAPORATOR kmol/h kg/h
Tri chloroethane 0.04 5.37 Tri chloroethane 0.04 5.37
Chloroprene 0.62 55 Chloroprene 0.62 55
3.4.6.2 Energy Balance Ethylene Dichloride 506 50078
Entering
50138 temperature = 84.2°C 50138
Leaving Temperature = 252°C
Heat of vaporization in Evaporator at leaving temperature = 8.96E+06 kJ/h
H7A at 84.2°C = 1.13E+07 kJ/h

H8 at 252°C = 1.17E+07 kJ/h
Evaporator Duty
Q = Hout -Hin + Hvap
Q = 9.34E+06 kJ/h
Flowrate for superheated steam in evaporator at 280°C and 12 bar and ΔT=15°C
m = Q/ (Cp.ΔT)
m = 325866 kg/h
3.4.7 Pyrolysis Furnace

𝐶2𝐻4𝐶𝑙2 𝐶2𝐻3Cl + HCl
26 | P a g e
𝐶2𝐻4𝐶𝑙2 𝐶2𝐻4 + 𝐶𝑙2
𝐶2𝐻3Cl 𝐶2𝐻2 + HCl
𝐶2𝐻4 + 𝐶2𝐻2 𝐶4𝐻6
𝐶2𝐻2 + 𝐶2𝐻3𝐶𝑙 𝐶4𝐻5𝐶𝑙

𝐶2𝐻4𝐶𝑙2 + 𝐶𝑙2 𝐶2𝐻3𝐶𝑙3 +HCl
Data Available:
TABLE 3- 2: CONVERSION DATA FOR REACTIONS

Component Conversion Reference
Chloroprene 0.5 Acetylene
Tri chloroethane 1 Chlorine
Di chlorobutane 1-S Ethylene Dichloride
Butadiene 1 Ethylene
Overall EDC Conversion = 60% [7]

Assumptions:
To make the Degree of Freedom zero and solve the system. The following assumptions have
been made based on results obtained in book [7]
95% of overall Ethylene dichloride will convert to VCM

4% VCM formed will convert to Acetylene
95% of (0.5 acetylene) will convert to butadiene
Also, Equation for Selectivity for Ethylene Dichloride is given as, [7]
S=0.989+0.0506X-(0.0652*X^2)
With X=0.6
S= 0.9959
Hence,
1-S=4.11E-03
Flow rates via general conversion:
Ethylene Dichloride IN = 506 kmol/h

Ethylene Dichloride consumed = (0.6-4.113E-03)*506 = 302 kmol/h
27 | P a g e
Ethylene Dichloride OUT = (1-0.6)*506 =202 kmol/h
Di-chlorobutane OUT = (4.11E-03*506)/2 = 1.04 kmol/h
Chlorine produced according to 1:1 mole ratio =1.04 kmol/h
As assumed 0.95 of EDC will go to VCM and remaining VCM will be distributed in reaction 2
and 6.
VCM produced = 0.95*302 = 287 kmol/h
Out of VCM produced, majorly will leave the furnace and rest will decompose into (Acetylene
+ HCl) and also react with Acetylene in stoichiometric proportion.
Acetylene = HCl produced =0.04*287 =11.5 kmol/h
As 50% of Acetylene produced will give Chloroprene with VCM
Chloroprene OUT = 0.5*11.5 = 5.7 kmol/h

Hence, VCM consumed is also same, so,
VCM OUT = 287-11.5-(0.5*11.5) = 269 kmol/h
For rest of Acetylene, 95% will react further as assumed and 5% will leave out
Acetylene OUT = 0.05*5.7 = 0.29
Ethylene required to produce butadiene is in stoichiometric proportion with acetylene and its
required amount is same as for 95% acetylene left to react i.e. Ethylene =0.95*5.7 =5.4 kmol/h
i.e. 5.4/15.1 = 0.361 fraction of lest ethylene dichloride would be consumed in 2nd reaction to
form ethylene and chlorine which will be completely consumed within the furnace so,
Chlorine Produced = 5.4 kmol/h

Butadiene OUT = 5.4 kmol/h
Now EDC left is = (1-0.361)*15.1 = 9.6 kmol/h
All Chlorine produced along with ETH and HVS would consume in to produce Tri chloroethane
Tri chloroethane OUT = Total Chlorine = 5.4+1.04 = 6.5 kmol/h
HCl produced according to 1:1 mole ratio = 6.5 kmol/h
28 | P a g e
HCl OUT = 11.4+6.4+287 = 305 kmol/h
Ethylene Dichloride not consumed = 9.6-6.5 = 3.16 kmol/h

Vinyl chloride Monomer 269 16814
Component kmol/h kg/h Hydrogen chloride 304.8 11113
Ethylene Dichloride 507 50078 Pyrolysis Furnace Ethylene 0 0
Chloroprene 0.62 54.7 Chlorine 0 0
Tri Chloroethane 0.04 5.4 Acetylene 0.29 7.45
50138 Butadiene 5.4 295
Chloroprene 6 535
Tri chloroethane 6.5 871
Di chlorobutane 1.04 132
50138
FIGURE 3- 9: PICTORIAL FOR MB OF FURNACE
Extent of reactions:
Reactions extent are later on calculated using:
𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑒𝑛𝑑 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛−𝑚𝑜𝑙𝑒𝑠 𝑎𝑡 𝑠𝑡𝑎𝑟𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

Ɛ=
𝑠𝑡𝑜𝑖𝑐ℎ𝑖𝑜𝑚𝑒𝑡𝑟𝑖𝑐 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
TABLE 3- 3: EXTENT OF REACTIONS INSIDE FURNACE

No. Values
extent 1 287
extent 2 6.5
extent 3 11.5
extent 4 5.45
extent 5 6.05
extent 6 6.5
extent 7 1.04

Operating Pressure = 26 bar
TABLE 3- 4: HEAT OF FORMATION AT 500°C
o
Reaction 1 ΔH500 = 67.4 kJ/mol
o
Reaction 2 ΔH500 = 180 kJ/mol
o
o
o
o
Reaction 6 ΔH500 = -96.7 kJ/mol
o
29 | P a g e
Component
Mole% kJ/h
Ethylene Dichloride 99.87 1.17E+6
Chloroprene 0.12 21.4
Tri Chloroethane 0.008 0.08 Pyrolysis Furnace
1.17E+06
Component Mole% kJ/h
Ethylene Dichloride 25.7 2.82E+06
Vinyl chloride Monomer 33.7 3.44E+06
Hydrogen chloride 38 1.71E+06
Ethylene 0 0.00E+00
Chlorine 0 0.00E+00
Acetylene 0.036 2.83E+00
Butadiene 0.68 2.15E+03
Chloroprene 0.76 2.98E+03
Tri chloroethane 0.82 3.15E+03
Di chlorobutane 0.13 1.20E+02
7.97E+06
FIGURE 3.10: PICTORIAL FOR EB OF FURNACE
Q = Hout - ƩHin + Hvap + Ɛ*Hrxn

Q = 1.59E+07 kJ/h
3.4.8 Mixer
STREAM L STREAM 9
FIGURE 3- 10: PICTORIAL FOR MB OF MIXER
3.4.8.2Vinyl chloride
Energy Balance 16814 1493 Vinyl chloride 18307
Hydrogen chloride 11113 H9 at 500°C
495 = 7.97E+06 kJ/h Hydrogen chloride 11609
Ethylene 0 0 Ethylene 0
M
Chlorine 0 HL at 6°C0 = 6.19E+04 kJ/h Chlorine 0

Acetylene 7.45 0.34 Acetylene 7.8
Temperature after Butadiene 425
mixingButadiene 295 130
Chloroprene 696
Chloroprene 535 160
Tri chloroethane 871 538 Tri chloroethane 1409
T =186
(Q/m.Cp) + Tref
50138 13941 64079
T = 361.2°C
30 | P a g e
3.4.9 Cooler
11: PICTORIAL FOR MBCOMPONENT

COMPONENT kmol/h kg/h kmol/h kg/h
FIGURE 3- OF COOLER
Ethylene Dichloride 316 31305 Ethylene Dichloride 316 31305
Vinyl chloride 293 18307 Vinyl chloride 293 18307
Hydrogen chloride 318 11609 Hydrogen chloride 318 11609
Acetylene 0.3 Entering
7.8 temperature = 361.2°CAcetylene 0.3 7.8
Butadiene 6.43 425 Butadiene 6.43 425
Chloroprene 9 Leaving
696 Temperature = 120°C Chloroprene 9 696
Tri chloroethane 12.6 1409 Tri chloroethane 12.6 1409
Di chlorobutane 2.5 319 Di chlorobutane 2.5 319
Heat of Condensation in cooler at leaving temperature = 5.98E+06 kJ/h
60479 60479
HE at 361.2°C = 1.4E+07 kJ/h
HF at 120°C = 4.2E+06 kJ/h
Cooler Duty
Qc = -1.58E+07 kJ/h

m = Q/ (Cp.ΔT)
m = 150172 kg/h
3.4.10 Flash Column

For Flash calculations, pressure is verified first as if it falls in between dew and bubble pressure

Operating Pressure = 12 bar
31 | P a g e
TABLE 3- 5: PRESSURE VERIFICATION FOR FLASH COLUMN
COMPONENT P (modified Antoine eq.) (bar) Mole% Pbubb (bar) Pdew (bar)
Ethylene Dichloride 2.8 33 0.92 0.12
Vinyl chloride 31.8 30.6 9 0.009
Hydrogen chloride 298.5 33 99 0.001
Acetylene 350 0.031 0.11 8.9-07
Butadiene 18.7 0.67 0.125 0.0003
Chloroprene 0.09 0.94 0.0008 0.09
Tri chloroethane 1.19 1.3 0.02 0.01
Di chlorobutane 0.38 0.26 0.0009 0.007
110 4.9
Hence 12 bar is the pressure that lies exactly in the range of dew and bubble pressures.
For iterations, value of Vapor flowrate (V) was randomly taken and fixed when summation of
fraction set equal to 1.
V= 0.71365 kmol/h
TABLE 3- 6: FLASH CALCULATIONS
COMPONENT Equilibrium constant (Ki) 𝒛 ∗ 𝑲𝒊 Xi=yi/Ki

∑ =𝟏
(Aspen Plus) 𝟏 + 𝑽 ∗ (𝑲𝒊 − 𝟏)
Ethylene Dichloride 0.27 0.19 0.68
Vinyl chloride 2.45 0.36 0.15
Hydrogen chloride 5.42 0.43 0.08
Acetylene 5.06 0.0004 8E-05
Butadiene 1.27 0.007 0.005
Chloroprene 0.46 0.007 0.015
Tri chloroethane 0.129 0.004 0.035
Di chlorobutane 0.041 0.0003 0.008
1.0078 0.98
And, as L+V=1 so,
L=0.28635 kmol/h
Hence, mole percentages for both liquid and vapor streams are known so moles leaving out are
calculated by multiplying the individual component fractions with total moles of that stream
obtained as
Flowrate (bottom) = 0.71365*958.5 = 684 kmol/h

Flowrate (top) = 0.28635*958.5 = 274 kmol/h
32 | P a g e
TOP BOTTOM
Ethylene Dichloride 31305 Ethylene Dichloride 12656 18648
Vinyl chloride 18307 Flash Column Vinyl chloride 15733 2573
Hydrogen chloride 11609 Hydrogen chloride 10809 800
Acetylene 7.8 Acetylene 7.2 0.57
Butadiene 425 Butadiene 264.3 161
Chloroprene 696 Chloroprene 426 269
Tri chloroethane 1409 Tri chloroethane 410 999
Di chlorobutane 319 Di chlorobutane 29 289
64079 40337 23742
FIGURE 3- 12: PICTORIAL FOR MB OF FLASH COLUMN
Assumptions:
 No heat losses
 Perfect separation
Hence, with enthalpy in = enthalpy out, Q = 0
3.4.11 Top Cooler

COMPONENT kmol/h kg/h COMPONENT kmol/h kg/h

Ethylene Dichloride 128 12656 Ethylene Dichloride 128 12656
Hydrogen chloride 296 10809 Hydrogen chloride 296 10809
Acetylene 0.28 7.2 Acetylene 0.28 7.2
Butadiene 5 264.3 Butadiene 5 264.3
Chloroprene 4.8 426 Chloroprene 4.8 426
40337 40337
FIGURE 3- 13: PICTORIAL FOR MB OF TOP COOLER
Entering temperature = 120°C
Leaving Temperature = 6°C
Heat of Condensation in cooler at entering temperature = 5.98E+06 kJ/h
HG of vapors at 120°C = 1.34E+06 kJ/h

HH at 6°C = 1.35E+05 kJ/h
33 | P a g e
Cooler Duty
Q = Hout -Hin - Hcond

Q = -7.2E+06 kJ/h

m = Q/ (Cp.ΔT)
m = 94544 kg/h
3.4.12 Bottom Cooler

COMPONENT kmol/h kg/h COMPONENT kmol/h kg/h

FIGURE 3- 14: PICTORIAL FOR MB OF BOTTOM
Ethylene COOLER
Dichloride 188 18648
3.4.12.2 Energychloride
Hydrogen Balance 22 800 Hydrogen chloride 22 800
Acetylene 0.02 Entering
0.57 temperature = 120°C Acetylene 0.02 0.57
Butadiene 1.5 161 Butadiene 1.5 161
Chloroprene 4.2 Leaving
269 Temperature = 6°C Chloroprene 4.2 269
HI of liquid at 120°C = 2.18E+06 kJ/h
23742 23742
HJ at 6°C = 1.05E+05 kJ/h
Cooler Duty
Q = Hout -Hin
Q = -2.07+06 kJ/h

m = Q/ (Cp.ΔT)
m = 27314 kg/h
3.4.13 Mixer
34 | P a g e
STREAM L STREAM H
Vinyl chloride 2573 15733 Vinyl chloride 18307
Hydrogen chloride 800 10809 Hydrogen chloride 11609
Acetylene 0.57 7.2 Acetylene 7.8
M
Butadiene 161 264.3 Butadiene 425
Chloroprene 269 426 Chloroprene 696
Tri chloroethane 999 410 Tri chloroethane 1409
Di chlorobutane 289 29 Di chlorobutane 319
23742 40337 64079
FIGURE 3-15: PICTORIAL FOR MB OF MIXER

As both liquid streams being mixed contain same number of components and both are same
temperatures so out temperature would also be same i.e. 6°C
3.4.14 HCL Column
Heavy key = Vinyl Chloride

Light key = Hydrogen Chloride
Assumptions
Let purity of light key in top product is 98% and purity in bottom product is 0.03%

Overall balance

962 = D + W
D =962 - W
Hydrogen Chloride
balance
Fxfi = Dxdi + Wxwi
(962*0.331) = (962 - W)*0.98 + (0.0003*W)
W = 637 kmol/h
D = 324 kmol/h
As no intermediate non keys are present all species lighter than LK will go on top and all
heavier than HK will go to bottom.
35 | P a g e
TOP BOTTOM
COMPONENT COMPONENT kg/h kg/h
kg/h
Vinyl chloride 388 17918
Vinyl chloride 18307 HCl Column
Hydrogen chloride 11602 6.97
Hydrogen chloride 11609
Acetylene 7.8 Acetylene 7.4
Chloroprene 696 Chloroprene 695.9
Tri chloroethane 1409 Tri chloroethane 1409
64079 11997 52081
FIGURE 3- 16: PICTORIAL FOR MB OF HCL COLUMN
Top temperature = 184 K = -88.5°C

H12 at -88.5°C = -8.01E+05 kJ/h

H11 at 105°C = 1.26E+06 kJ/h
Feed temperature = 93.7°C
H3A = 5.58E+06 kJ/h
Condenser Duty

Qc = -6.47E+06 kJ/h
Reboiler Duty

Qb = 9.01E+06 kJ/h

m = Q/ (Cp.ΔT)
m = 4.25E+03 kg/h
Flowrate for Refrigerant (Tetrafluoromethane) with ΔT = 15°C and Tin = -100°C
36 | P a g e
m = Q/ (Cp.ΔT)
m = 270529 kg/h
3.4.15 VCM Column

Heavy key = ethylene dichloride

Light key = Vinyl Chloride
Assumptions
Let purity of light key in top product is 99.91% and purity in bottom product is 1%
Overall balance

637.7 = D + W
D = 637.7 - W
Vinyl Chloride balance
Fxfi = Dxdi + Wxwi

(637.7*0.954) = (637.7 - W)*0.9991 + (0.01*W)
W = 283 kmol/h
D = 354 kmol/h
LNK is one i.e. HCl while HNK and HHNK are Tri chloroethane and di chlorobutane
respectively. INKs are two i.e., Butadiene and chloroprene, for which assumptions for their
mole fractions are made in the top product as 0.01% for Butadiene and (1-Ʃmole fractions) for
chloroprene which come out to be 0.0095%. Also the percentage of ethylene di chloride is
assumed as 0.003%. Then via equation of specie balance, mole fraction of each intermediate
non key and of Heavy key are found.
FIGURE 3- 17: PICTORIAL FOR MB OF VCM COLUMN TOP BOTTOM

Ethylene Dichloride 31305 Ethylene Dichloride 0.84 31304
Vinyl chloride 17918 VCM Vinyl chloride 17697 221
Hydrogen chloride 6.97 Column Hydrogen chloride 6.97
Butadiene 425 Butadiene 1.53 424
Chloroprene 695.9 Chloroprene 2.38 693
Tri chloroethane 1409 Tri chloroethane 1409
52081 17708 34371
37 | P a g e
Top temperature = 305 K = 31.6°C

H15 at 31.6°C = 1.86E+06 kJ/h

H14 at 139°C = 3.1E+06 kJ/h
Feed temperature = 105°C, H11 = 1.26E+06 kJ/h
Condenser Duty
Qc = -4.76E+06 kJ/h
Reboiler Duty
Qb = 4.44E+06 kJ/h
m = Q/ (Cp.ΔT)
m = 2.14E+03 kg/h
m = Q/ (Cp.ΔT)
m = 75358 kg/h
3.5 Aspen plus Simulation
For the purpose of simulating flowsheet for material and energy balance, shortcut models for
equipment were used i.e. RSTOIC for direct chlorinator reactor in place of RCSTR and also for
furnace simulation which is initially devised to be modeled as PFR, the RSTOIC model is
selected as it do not require reactions kinetics and require only reaction conversion or extent,
DSTWU is taken for all distillation columns as it require reflux ratio or no. of stages obtained
from shortcut models and HEATER model for all exchangers including cooler and heater which
involve only one inlet and one outlet for processing.
38 | P a g e
FIGURE 3- 18: PFD ON ASPEN PLUS
39 | P a g e
3.5.1 DC Reactor Balance
With specified reactions and conversion achieved in two reactions along with the reactor
conditions and stream flows, the following results for material balance were obtained which
coincides exactly with the manually calculated material balance i.e. the desired 97.7% EDC
purity is being attained.
FIGURE 3- 19: ASPEN GENERATED MATERIAL BALANCED OF DC REACTOR
Whereas heat balance show a little difference in value from manual calculation i.e. of 1.8%.
FIGURE 3- 20: ASPEN GENERATED ENERGY BALANCED OF DC REACTOR
The exchanger E-101 will remove this amount of heat by recycling a part of product stream at
slight lower temperature in order to make the reactor operate isothermally.
3.5.2 Lights Column Balance
With reflux ratio set equal to 10.3 and recovery set as 0.00055 for EDC and 0.995 for
chloroprene as light and heavy key respectively, material balance show purity of 97.2 % for
EDC emitting from bottom.
40 | P a g e
FIGURE 3- 21: ASPEN GENERATED MATERIAL BALANCED OF LIGHTS COLUMN
For DSTWU model, in energy balance, the top temperature coincides with our manual
calculated value whereas bottom temperature shows a difference of 4 degree Celsius. Heat duty
however shows a larger difference from manually calculated i.e. Aspen generated result require
a more 41% for heat for reboiler and is showing a release of 46% less heat for condenser.
FIGURE 3- 22: ASPEN GENERATED ENERGY BALANCE OF LIGHT COLUMN
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3.5.3 Heavy Column Balance
With reflux ratio set equal to 1.3 and recovery set as 0.001 for tri-chloroethane and 0.99988 for
EDC as heavy and light key respectively, material balance show purity of 99.99 % for EDC
emitting from top under total condenser condition.
FIGURE 3- 23: ASPEN GENERATED ENERGY BALANCE OF HEAVY COLUMN
FIGURE 3- 24: ASPEN GENERATED ENERGY BALANCE OF HEAVY COLUMN
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For DSTWU model, in energy balance, the bottom temperature is nearly same as manually
calculated value whereas top temperature shows a difference of 5 degree Celsius. Heat duty
however shows a relatively large difference from manually calculated i.e. Aspen generated
result require a 25.5% less heat for reboiler and is showing a release of 15.5% more heat from
condenser.
3.5.4 Pyrolysis furnace Balance
With specified reactions and conversion achieved in seven reactions along with the reactor
conditions and stream flows in RSTOICHO model, the following results for material balance
were obtained which coincides exactly with the manually calculated material balance i.e. the
desired 60% conversion of EDC to VCM is being attained.
FIGURE 3- 25: ASPEN GENERATED MATERIAL BALANCE OF PYROLYSIS FURNACE
Whereas heat balance show a little difference in value from manual calculation i.e. of 6.3%.
FIGURE 3- 26: ASPEN GENERATED ENERGY BALANCE OF PYROLYSIS FURNACE

43 | P a g e
3.5.5 Quench Tank Balance
Quenching is done in a flash column operating at 120°C and 12 bar and hence pressure is
reduced via valve and temperature is reduced via recycle stream passing through heat exchanger
to achieve flash conditions.
FIGURE 3- 27: ASPEN GENERATED MATERIAL BALANCE OF QUENCH TANK

The Flash results show following fractions
FIGURE 3- 28: ASPEN GENERATED FRACTIONS OF QUENCH TANK

3.5.6 HCL Column Balance
With reflux ratio set equal to 3 and recovery set as 0.02085 for Vinyl chloride and 0.99999 for
Hydrogen chloride as heavy and light key respectively, material balance show purity of 96.7 %
for HCl emitting from top under partial condenser condition.
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FIGURE 3- 29: ASPEN GENERATED MATERIAL BALANCE OF HC1 COLUMN
FIGURE 3- 30: ASPEN GENERATED ENERGY BALANCE OF HC1 COLUMN
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For DSTWU model, in energy balance, the bottom and top temperatures are nearly same as
manually calculated value. The difference of heat duties from manually calculated is that Aspen
generated result shows a 7.5% less heat for reboiler and is showing a less heat of 3.7% from
condenser.
3.5.7 VCM Column Balance
With reflux ratio set equal to 0.58 and recovery set as 0.98325 for Vinyl chloride and 1e-07 for
EDC as light and heavy key respectively, material balance show purity of 99.5 % for VCM
emitting from top under total condenser condition.
FIGURE 3- 31: ASPEN GENERATED MATERIAL BALANCED OF VCM COLUMN
For DSTWU model, in energy balance, the bottom and top temperatures are nearly same as
manually calculated value. The difference of heat duties from manually calculated is that Aspen
generated result shows a 0.3% less heat for reboiler and is showing a more heat release of 4%
from condenser.
46 | P a g e
FIGURE 3- 32: ASPEN GENERATED ENERGY BALANCE OF VCM COLUMN
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CHAPTER 4: DETAILED EQUIPMENT DESIGN
4.1 Pyrolysis Furnace
4.1.1 Required Design Data
TABLE 4- 1: INITIAL REQUIRED DATA FOR DESIGN CALCULATION OF FURNACE
No. Factors Values

1. Total required furnace duty (from energy balance) 1.59E+07 kJ/h
2. Efficiency (assumed) 72%
3. Fuel name (selected) Natural gas
4. Calorific Value of Fuel 4.24E+04
kJ/kg
5. Temperature of inlet air (selected) 204.4°C
6. TUBES SIZE (selected) (3 inch) [21] 0.1016 m
Outer Diameter 0.091 m
Pitch 0.0057 m
Thickness
7. Exposed Tube length (Selected) 8.68 m
8. Heat Capacity for air 1 kJ/kg.K
Average heat capacity for flue gases 0.75 kJ/kg.K
4.1.2 Design Calculation
1. Radiant Section Heat Flux:
Range of q = 113630-124,993 kJ/hr-m2 for cracker feed heater in temperature range of 482-
565°C Selected average flux q =113630 kJ/hr-m2. [19]
TABLE 4- 2: TYPICAL RADIANT FLUXES AND PROCESS TEMPERATURES
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By convention for natural convection (h=2) so, 𝜮𝑸
𝑎𝑨𝑪𝑷 = 2 * average flux = 227260 kJ/hr.m²
Where 𝛼 = actual heat transfer between hot and cold surface and Acp = cold plane surface
Assumption for overall exchange factor f = 0.57
Effective flux: 𝛴𝑄
𝛼𝐴𝐶𝑃 𝑓
=
227260 = 3.98E+05 kJ/hr.m²
0.57
252+500
Let assume Ts = + 204.4 = 853 K
2
2. Flue Gas Temperature:
At average tube surface temperature (Ts) and average flux
FIGURE 4- 1: GRAPH TO DETERMINE FLUE GAS TEMPERATURE
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3. Heat liberated by fuel:
ℎ𝑒𝑎𝑡 𝑑𝑢𝑡𝑦
Qf = ὴ =
1.59𝐸+07 = 2.20E+07 kJ/hr
0.72
4-Air to fuel ratio:
Calculated assuming the complete combustion of natural gas mainly methane)
CH4 + 2(O2+3.76N2) → CO2 + 2H2O + 7.52N2

𝐴 2∗4.76∗29
𝐹 = 1∗!6 = 17.25
5. Mass of fuel
𝑄𝑓
and air:
mfuel =
= 42400 = 486 kg/hr
2.20E+07
𝑓𝑢𝑒𝑙
𝑣𝑎𝑙𝑢𝑒
𝐴
mair = 1.25*(( ) ∗mfuel ) = 10400 kg /hr (25% excess air for natural/induced draft) [20]
𝐹
6. Inlet heat by air (Qair):
Qair = mair *Cpair *(Tair in- Tref) = 2.12E+06 kJ/h
7. Heat absorbed by furnace wall (Qwall):
Qwall = 2% Qf = 0.02*2.2E+07 = 2.65E+05 kJ/hr [20]
8. Heat of leaving exhaust gases (Qexhaust):
𝐶𝑝 𝑎𝑣𝑔 =ΣC𝑝𝑔𝑎𝑠𝑒𝑠 ∗𝑥𝑔𝑎𝑠𝑒𝑠

Where gases are xCo2 = 0.5, xsteam = 0.2, xNOx = 0.3
𝐴
Qexhaust = mfuel * (1+ ) * Cp average * (Tg-520) = 5.93E+06 kJ/hr , with T in degree Rankine
𝐹
9. Net heat liberated (Q):
Q = Qfuel +Qair – Qwall – Qexhaust = 1.8E+07 kJ/hr
10. Number of tubes (Nt):

𝑄
Ntubes =
𝜋𝐷𝐿.𝑞 =
1.8𝐸+07 = 58 tubes
𝜋∗8.68∗0.01016∗3.98𝐸+05
11. Cold plane area (Acp):

𝑃𝑖𝑡𝑐ℎ
= 2.7 for long radius and 180° bend
𝑂𝐷
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Acp = Pitch *L*N = 0.899*8.68*58 = 138 m2
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12. Calculation of effectiveness factor (α):
𝑃𝑖𝑡𝑐ℎ
α = 0.765 (At = 2.7 And curve of total to one row) [21]
𝑂𝐷
FIGURE 4- 2: RADIATION BETWEEN A PLANE AND ONE OR MORE TUBE ROWS PARALLEL TO THE
PLANE.
13. Radiant Section Dimensions and area:
No. of tubes on each wall = 23
As commonly 3 rows above radiant section contributes to radiant section so, no. of shield tubes
are selected as,
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No. of tubes in shield section =12
Clearance = Pitch -Outer Diameter of Tube = 0.56
 Height= (no. of wall tubes*OD)+((no. of wall tubes-1)*clearance) = 6.14 m

 Width= (no. of shield tubes*OD)+((no. of shield tubes-1)*clearance) = 3.12 m
 Exposed length = 8.68 m
 End walls = 2*H*W = 38.3 m2
 Side wall = W*L = 27.09 m2
 Bridge wall = L*(H/3) = 12.5 m2
 Floor = 2*W*L = 106 m2
Total Exposed area of radiant section (At) = 184.6 m2
14. Mean beam length:
Length: Height: Width = (3:2:1) [20]
TABLE 4- 3: MEAN LENGTH OF RADIANT BEAMS IN VARIOUS GAS SHAPES
L = 2/3 *(volume) 0.333 = 3.66 m
15. Effective refractory surface (AR):
AR = At – αAcp = 184.6 - (0.765*138) = 78.83 m2
𝐴𝑅
𝛼𝐴𝐶𝑝 = 0.743
53 | P a g e
16. Gas Emissivity and Overall Exchange Factor:
P=0.288−0.229x+0.09x² = 0.211 atm (x = excess air fraction) [21]
PL = 0.211*3.66*3.28 = 2.53 atm-ft.
Gas Emissivity as function of PL from graph = 0.41
FIGURE 4- 3: GAS EMISSIVITY AS FUNCTION OF PARTIAL PRESSURE AND MEAN BEAM LENGTH
Overall exchange factor f from plot of 𝐴𝑅

𝛼𝐴𝐶𝑝 vs f as function of Ɛ is 0.55
FIGURE 4- 4: OVERALL HEAT-EXCHANGE FACTOR IN RADIANT SECTION
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17. Actual flue gas temperature:
Ʃ𝑄 𝑇𝑔 4
= 0.173(( ) - ( 𝑇𝑠 )4) + 7(Tg-Ts) with T in Rankine and L.H.S in Btu/hr.ft2
𝛼.𝐴𝑐𝑝.𝑓 100 100
L.H.S of equation = 30447 kJ/hr.m²
With fixed Ts, after iterations when L.HS=R.H.S Tg = 1180.9 K
As this is quite close to the previous value found from assumed flux calculations, hence no
changing will occur in number of tubes
18. Convection zone area and dimensions:
𝑄𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛 = (𝑄𝑡𝑜𝑡𝑎𝑙−𝑄r𝑛𝑒𝑤) = 1.59E+07-30447 = 1.56E+07 kJ/h

4.5
Uconvection = (a+bG’+cG’²) * ( )0.25 G’ = 0.034 kJ/h.m²
𝑂𝐷
a = 2.461−0.759z+1.625z² = 3.23
b = 0.7655+21.373z−9.6625z² = 12.4
c = 9.7938−30.809z+14.333z² = -6.56
Where z =𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 𝑓𝑖𝑙𝑚 𝑇𝑒𝑚𝑝𝑒𝑟𝑒𝑡𝑢𝑟𝑒 = (𝑇𝑓)/1000 = 0.96

With, Tf = 0.5 * [Tin + Tout + LMTD] = 786 K
(𝑇𝑔−𝑇𝑖𝑛)−(𝑇𝑠−𝑇𝑜𝑢𝑡)
𝐿𝑀𝑇𝐷 ln(
(𝑇𝑔−𝑇𝑖𝑛) = 529 K
(𝑇𝑠−𝑇𝑜𝑢𝑡)
𝑄𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛
Aconvection =
𝑈𝑐𝑜𝑛𝑣𝑒𝑐. 𝐿𝑀𝑇𝐷 = 71.6 m²
Surface per linear ft. for outer diameter = 0.281 m [22]
𝐴𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛
No. of tubes = 𝐿𝑖𝑛𝑒𝑎𝑟 𝑙𝑒𝑛𝑔𝑡ℎ = 30
No. of rows in Convection section = no. of shield tubes in radiant section = 12
 Height H = (no. of Rows * OD)+ (no. of Rows -1) * Clearance = 2.11 m

 Width W = (no. of tubes in one row * OD) + (no. of tubes of row -1)* Clearance = 0.3 m
Efficiency:
𝑛𝑒𝑡 ℎ𝑒𝑎𝑡
η=
𝑙𝑖𝑏𝑒𝑟𝑎𝑡𝑒𝑑 *100 = 73.6 % hence true efficiency is close to the initial selected one.
𝑄𝑓
55 | P a g e
4.1.3 Aspen Simulation
Rigorous Fired Tube Heater Design on 'ASPEN EXCHANGER DESIGN AND RATING V10'
FIGURE 4- 5: ASPEN HYSYS MODEL FOR FIRED HEATER
For BOX TYPE fired Heater with REFRACTORY BACKED tube row layout and
HORIZONTAL orientation of main tubes in WELL-STIRRED calculation model and with all
known dimensions, the HEATER GEOMETRY was specified. STREAM COMPOSITION
were specified as known from material balance along with process conditions in the PROCESS
DATA. The method selected for the property estimation of components was NRTL-RK.
FIGURE 4- 6: OVERALL SUMMARY OF ASPEN GENERATED RESULTS
The overall result summary shows the efficiency of 70.38 % which shows an error of around
4% from the manually calculated value. The efficiency increases by increasing excess air and
decreasing fuel flowrate but it cannot be done due to the physical limitation as it leads to lower
56 | P a g e
flame temperature and less heat transfer. As it was observed on increasing excess air to 50% and
decreasing fuel flowrate by 100 kg/hr lead to an efficiency increase to 75% but lowering the
flue gas temperature to a lower value of 1033 K.
The difference in manually calculated and aspen generated results might be due to the fact as
various assumptions are included in manual design and hence cause error. However, the current
error is not too much to worry about. As flue gas temperature came close to our calculated value
with a difference of 5K only. Also the outlet temperature is just 6°C above the set value.
TABLE 4- 4: API SHEET FOR BOX TYPE FIRED HEATER
57 | P a g e
Specification sheet mainly show the inlet and outlet conditions inside tube and pressure drop
inside the tube both in convection and firebox (Radiant) section as indicated by arrows on the
sheet. The pressure drop inside tubes is not significant as observed.
4.2 Evaporator
4.2.1 Required Design Data:
1- Shell 2- tube passes heat exchanger, fixed tube sheet. Mixture of tri-chloroethane,
chloroprene and ethylene dichloride in shell side and superheated steam at 26 bar in tube side.
TABLE 4- 5: INITIAL REQUIRED DATA FOR DESIGN CALCULATION OF EVAPORATOR
Tube side Shell side

Temperature in (°C) 280 84.12
Temperature out (°C) 265 252
The physical properties of each fluid are taken at the average temperature for each side from
ASPEN Hysys property set:
Tshell = 168°C for process stream
Ttube = 273°C for steam
TABLE 4- 6: PROPERTIES REQUIRED FOR CALCULATION
Properties Tube side Shell side

ρ (kg/m )
3
11.02 3.32
k (W/m.K) 0.0415 0.07025
µ (Pa.s) 17.4E-06 1.37E-05
Pr. no 2.3 4.43
The thermal conductivity (kw) for shell and the tube material (Carbon steel) is 43 W/m.K. [22]
The fouling factors for Mixture and steam are given as:
Rf, mixture = 4E-04 (m2.K/W) and Rf, steam = 2.5E-04 (m2.K/W)
TABLE 4- 7: GENERAL RANGE FOR HEAT TRANSFER COEFFICIENT AND FOULING RESISTANCES FOR
SENSIBLE HEAT TRANSFER IN EXCHANGER
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Qmixture = 9.34E+06 kJ/h from energy balance
calculation ṁsteam = 325866 kg/h Calculated in chapter
After trial and error value of the overall heat transfer coefficient for steam-to-organic heat
exchanger is assumed to be 30 W/m2. K [22]
TABLE 4- 9: APPROXIMATE DESIGN VALUES FOR OVERALL HEAT TRANSFER
COEFFICIENT
The friction factor (F) is found by the chart below:
FIGURE 4- 7: CORRECTION FACTOR FOR 1-SHELL 2-TUBE PASS HEAT EXCHANGER

Where R&P are defined as
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Th, in − Th, out 280 − 265
𝑅= = = 0.083
Tc, out − Tc, in 252 − 84.12
Tc, out − Tc, in 252 − 84.12
𝑃= = = 0.857
Th, in − Tc, in 280 − 84.12
From the above figure; F = 0.98
ΔTm = FT * ΔTLM
The flow is assumed to be counter current flow: (𝑇ℎ, −𝑇𝑐, 𝑜𝑢𝑡) − (𝑇ℎ, 𝑜𝑢𝑡−𝑇𝑐, 𝑖𝑛)
(Th, in − Tc, out) − (Th, out − Tc, in )
∆𝑇𝐿𝑚 =
Th, in − Tc, out
ln(Th, out − Tc, in )
(288 − 252) − (265 − 84.12 )
∆𝑇𝐿𝑚 = 288 − 252
ln(265 − 84.12)
∆𝑇𝐿𝑚 = 90.09°𝐶
ΔTm = FT * ΔTLM = 0.98 * 90.09 = 88.3°C
Then A = 237.554 m2 from Q=U.A.ΔTLM
Heat Exchanger Design:

The design is done under these assumptions:
 Outside diameter of tubes (OD) = 1 in = 0.0254 m
 Birmingham wire gauge (BWG) = 16
 Tube length (Lt) = 16 ft = 4.88 m
TABLE 4- 10: CARBON STEEL TUBE DIMENSIONS
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The inside diameter for the tube (ID) = 0.87 in = 0.022098 m.
The thickness of the tube (tw) = OD-ID = 3.302 mm
A = Nt Do 𝜋 Lt , Where Nt = number of tubes
𝐴 237.554
𝑁= = = 609
𝜋𝐷𝑜𝐿𝑡 3.14 × 0.0254 × 4.88
FIGURE 4- 8: CONVENTIONAL TUBE-PLATE LAYOUTS IN SHELL-AND-TUBE HEAT

EXCHANGERS
In most shell and tube exchangers, the tube pitch for economic reasons is maintained between
1.25 - 1.5 times the outside tube diameter with a minimum clearance of no less than 0.0048 m.
It is assumed that the pitch (Pt) = 1.25* OD = 0.03175 m
Clearance = Pt - OD = 0.03175 – 0.0254 = 0.00635 m
TABLE 4- 11: NUMBER OF TUBES IN CONVENTIONAL TUBE LAYOUT
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By using interpolation, Dshell, in = 0.898 m
Baffle spacing (B) is suggested to be :
(Ds /5) < B < Ds, an Ds/4 is taken: B = 0.2245 m
𝐿𝑡 4.88
Number of baffles (Nb) = − 1 = − 1 = 21
𝐵 0.2245
The cross flow area, Velocity and Reynolds number for the tube side are defined as:
𝜋𝐷𝑖²𝑁𝑡
𝐴𝑐, 𝑖𝑛 = = 5.28 𝑚2
4𝑁𝑝
Velocity inside tubes (Vin) = mass flow inside / (Ac, in * fluid density inside)
Velocity inside tubes (Vin) = 325866 / 5.28 * 3600 * 11.08 = 1.546 m/s
𝜌𝑉𝑖𝑛𝐷𝑖𝑛 11.08 ∗ 1.546 ∗ 0.022098

𝑅𝑒, 𝑖𝑛𝑠𝑖𝑑𝑒 = = = 21763
𝜇𝑖𝑛 17.4 ∗ 10−6
Re > 2300 so Flow is Turbulent
Friction factor f (Rein) = (1.58 ∗ ln (𝑅𝑒) - 3.28)-2

= 0.0064
𝖥 1
I I
𝑁𝑢𝑖𝑛 = f (Rein ) I (𝑅𝑒 − 1000) ∗ 𝑃𝑟 I
2 ∗I I I
f (Rein ) 0.5 32
I
I1 + 12.7 ∗ ( 2 ) (Pr − 1)I
[ ]
Nu, in = 99.65
𝑁𝑢𝑖 ∗ 99.65 ∗ 0.0415

ℎ𝑖 = =
𝑘𝑖 0.022098
𝐷𝑖
= 187.143 W/m2.K
The cross flow area, Velocity and Reynolds number for the shell side are defined as:
𝐷𝑠 ∗ 𝐶𝑡 ∗ 𝐵
𝐴𝑐, 𝑜 = = 1.791 𝑚2
𝑃𝑖𝑡𝑐ℎ
Shell side fluid velocity (Vo) = mass flow in shell / (Ac for shell * fluid density in shell side)
Velocity = (50138/3600)/ (1.791*3.32) = 2.34 m/s.
𝑅𝑒, 𝑜𝑢𝑡𝑠𝑖𝑑𝑒 =
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𝜌(𝑚𝑖𝑥𝑡𝑢𝑟𝑒)
𝑉𝑜𝐷𝑒
𝜇(𝑚𝑖𝑥𝑡𝑢𝑟𝑒)
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Where De is the equivalent diameter for a triangular pitch
4 ∗ (0.86𝑃𝑡2 − 0.25𝜋𝐷𝑜2)
𝐷𝑒 = = 0.018 𝑚
𝜋𝐷𝑜
Re in shell =
10205
Re > 2300, Turbulent flow in shell side
Friction factor f (Reshell) = exp (0.576 - 0.19 ∗ ln (Reout)) = 0.308
Nuout = 0.36 Re o 0.55 Pr1/3

Nuout = 94.76
𝑁𝑢𝑜 ∗ 118.8 ∗ 0.07025
ℎ𝑜 = =
𝐾𝑜 0.018
𝐷𝑒
= 369.82 W/m2.K
The total heat transfer areas for both fluids:

Ai = 𝜋.Di.𝐿𝑡.𝑁𝑡 = 206.212 m2
Ao = 𝜋.Do.𝐿𝑡.𝑁𝑡 = 237.025 m2
The overall heat transfer coefficient (U):
U0 = 29 W/m2.K
Tube side pressure drop (ΔPi)
= 256 Pa = 0.0026 bar

Shell side pressure drop (ΔPo)
= 3034 Pa = 0.0303 bar

The velocities and pressure drop is perfectly in range of good design figures and after trial
and error value of overall heat transfer coefficient also converged with percentage error of
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3.3%.
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Shell and tube Heat exchanger design on 'ASPEN plus V10'
FIGURE 4- 9: SHELL AND TUBE EVAPORATOR
For HEATX model with COUNTERCURRENT flow in rigorous mode of SHELL AND TUBE
HEAT EXCHANGER, Tube pattern was stated as '30-Triangular' with outer diameter of
0.025m and baffle orientation was specified as 'horizontal single segmental' with 'carbon steel,
as material of construction. Sizing including shell ID/OD, tube length and baffle spacing were
also specified as known from manual calculation. As well as 'outside packed floating head' is
selected due to large variation in temperature
FIGURE 4- 10: ASPEN GENERATED RESULTS FOR GEOMETRY OF EXCHANGER
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The method selected for the property estimation of components was NRTL-RK. For process
data, flowrates, composition and temperature pressure were specified. After sizing outlet
temperature of hot stream came out to be 261.3°C which is approximately 4 degree less than the
assumed outlet temperature of 265°C for the calculated flowrate. This may be due to the
assumptions made in heat balance during manual calculation or different property estimation.
FIGURE 4- 11: ASPEN GENERATED RESULTS FOR PROCESS OF EXCHNAGER

The overall result of rigorous design is quite close to the manually calculated. Also the pressure
drop is also within the allowable limit for shell side. However, pressure drop in tube side is seen
exceeding the set limit and standard value. The temperature profile came as:
FIGURE 4- 12: TEMPERATURE PROFILE FOR HEAT EXCHANGER
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4.3 Direct Chlorinator Reactor (CSTR)
TABLE 4- 12: INITIAL REQUIRED DATA FOR DESIGN CALCULATION OF FURNACE
No. Factors Values

1. Conversion of ethylene in main reaction 98 %
2. Value of k at required Temp 30220 l/mol.s
3. Chlorine Density, Gas @ 0° C, 1 atm 3.214 kg/m3
4. Ethylene Density, Gas @ 0° C, 1 atm 1.260 kg/m3
5. Optimum height to diameter ratio 1
6. Radial velocity (N) 3.3 rps
7. f (design stress) 115142.45 kN/m2
8. Joint factor (J) 0.9
9. Pi (internal Pressure) 1.5 bar
10. Thermal conductivity k at 100°C 16.2 W/mK
11. Average viscosity 0.000170193 kg/m.s
12. Average density 248.6635813 kg/m3
Assumptions
• Liquid phase reaction.
• Single reaction.
• First order reaction.
• Isothermal and non-adiabatic system.
• The feed is well stirred or properly mixed.
• Steady state operation.
• Constant density system.
• Cylindrical tank.
1. Volume of Reactor:
Operating Pressure = 1.5 bar
FeCl3
Main: C2H4+ Cl2 → C2H4Cl2
Side: C2 H4Cl2 + Cl2 → C2 H3Cl3 + HCl
68 | P a g e
Rate law: rA = kD1CC2H4 CCl2
k = 11493 exp (-2156.58/T) m3/mol.s [4]
𝑉
𝐶a𝑜 ∗ 𝑋𝑎
𝑉𝑜 = −𝑟𝐴
𝐶𝑎𝑜 ∗ 𝑋𝑎 ∗ 𝑉𝑜
V= −𝑟𝐴
𝑚3
V=
𝐶𝑎𝑜 ∗ 𝑋𝑎 ∗ 𝑉𝑜
𝑘 ∗ 𝐶𝑎𝑜(1−𝑋𝑎) ∗ 𝐶𝑏𝑜(1−𝑋𝑏) ( ℎ𝑟
3600𝑠 )
𝑙 𝑚𝑜𝑙 ∗
𝑚𝑜𝑙.𝑠 ∗ 𝑙 ℎ𝑟
(2132.80 + 2172.64) ∗ 0.98

𝑉=
30220 ∗ 0.0453 ∗ (1 − 0.99) ∗ (1 − 0.98) ∗ 3600
Vreactor = 3.931 m3
For 10% allowance (m3) = 4.324 m3
2. Diameter and height
𝜋∗𝑑^2
V= 4 h
Optimum Height / Diameter ratio of CSTR is taken as 1 [25]
V = 𝜋∗𝑑^2
4
(1D)
Diameter = 1.543 m
Height = 1.543 m
3. Dimensions of Agitator [25]
Impeller diameter (m) = Diameter / 3 = 0.514 m
Height of impeller above bottom = Impeller diameter = 0.514 m
Blade Length = Impeller diameter * 0.25 = 0.129 m
Blade Width = Impeller diameter / 5 = 0.103
m Baffle Width = Diameter / 10 = 0.154 m
4. Power of the Impeller
𝑁∗𝑝∗𝐷^2
Reynolds Number = Re = 1275161.333
= ս
69 | P a g e
It is a turbulent region
So, power no. from [25] is
NP = 6
Power delivered = P = (Np * N3 * p * D5)

Power = 137868.4938 Watt = 184.81 hp
Allowing 25% of losses = 246.4137512
5. Wall Thickness
In the ASME Pressure Vessel Code the maximum allowable stress is only 16,700 psi for 316L
SS. [26]
16,700 psi = 115142.45 kN/m2

𝑃𝑖∗𝐷𝑖
Wall thickness (t) =
2𝑓−𝑃𝑖
150 ∗ 1.543
= 2 ∗ 115142.45 − 150
Wall thickness (t) = 0.001005714 m
With 0.002m corrosion allowance
Wall thickness = 0.003005714 m
6. Head Thickness
𝑃𝑖∗𝐷𝑖
Head thickness (m) =
(2∗𝑓∗𝐽−0.2𝑃𝑖)
150 ∗ 1.543
= 2 ∗ 115142.45 ∗ 0.9 − 0.2 (150)
Head thickness t head = 0.001116894 m
With 0.002m Corrosion allowance
Head thickness t head = 0.003116894 m
7. Longitudinal Stress
𝑃∗𝐷𝑖
Longitudinal Stress = = 1.5 ∗ 1.543
4𝑡 4 ∗ 0.003005714
Longitudinal Stress Ω L = 192.5083054 bar
8. Circumferential Stress
(𝑃∗𝐷𝑖)
Circumferential Stress Ω (bar) =
2𝑡
70 | P a g e
1.5 ∗ 1.543
= 2 ∗ 0.003005714
Circumferential Stress Ω = 385.0166108 bar

9. Pressure and Axial Stresses
𝑃∗𝐷𝑖
Axial Stress Ω (bar) =
4(𝑡𝑠−𝐶𝐴)
1.5 ∗ 1.543
= 4 (0.003005714−0.002)
Axial Stress Ω = 575.33725 bar
10. Heat Dissipation and Insulation:

Delta T = (Treactor - T ambient) = 65 K
A (surface area) = 2πrh = 7.4749209 m2
𝑑𝑇
Heat transfer (Q) = 𝑘𝐴
𝑑𝑠
16.2 ∗ 7.4749209 ∗ 65
= 0.003005714
Heat transfer = 2618709.054 W
11. Material of Construction:
316 L Stainless Steel is our preferred chosen material of construction for the reactor to
accommodate allowable stress value in the wall thickness calculations carried out below.
Continuous Stirred tank reactor design on 'ASPEN plus V10'
FIGURE 4- 13: DIRECT CHLORINATOR STIRRED TANK REACTOR

For RCSTR model with Reactions described as in 'power law', kinetics data for 2 reactions (2 nd
and 3rd order) from source [4] was inserted along with 'liquid' as in reacting phase and rate basis
as 'reac (vol)' with To specified as 0°C .Under specification of reactor, conditions and residence
71 | P a g e
time were specified along with valid phases as 'vapor-liquid'. The residence time was initially
set as 2.58 hours according to source [27] and varied until desired compositions were achieved
as indicated in material balance chapter 3.
FIGURE 4- 14: ASPEN PLUS RESULTS FOR DC REACTOR

The overall results shows approximately same heat duty as calculated by energy balance in
chapter 3. However the volume indicated a difference of 21.8% as compared to calculation from
manual design value.
4.4 VCM Distillation Column
Feed Temperature = 378.15 K

Column’s Pressure = 4.8 bar
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Feed flow rate = 637.7295 kmol/h
Viscosity of feed at average column temperature = 𝜇𝑓,𝑎𝑣𝑔 = 0.213 centipoise
Molecular Weight of Mixture = 62.4831 kg/kmol
TABLE 4- 13: DATA FOR DESIGN CALCULATION
TOP BOTTOM
Density Liquid [29] 892 kg/m3 1050 kg/m3
Density Vapor [29] 19.4196 kg/m3 14.1396 kg/m3
Temperature 304.15 K 412.15 K
flow rate 283.4201 kmol/h 354.3094 kmol/h
TABLE 4- 14: FEED, TOP & BOTTOM COMPOSITIONS
STREAMS 13 15 14
Components Xf Xd Xb
Ethylene Dichloride 0.496 0.00003 0.89
Vinyl Chloride 0.449 0.9991 0.01
Hydrogen Chloride 0.0003 0.00067
Butadiene 0.005 0.0001 0.0089
Chloroprene 0.020 9.49E-05 0.036
Tri-Chloroethane 0.025 0.045
Di-Chlorobutane 0.004 0.0071
1. K-Values:
Light Key = Vinyl Chloride

Heavy Key = Ethylene Dichloride
TABLE 4- 15: K-VALUES OF COMPONENTS
K-Value K-Value K-Value Relative Relative Relative

Components (Feed) (Top) (Bottom) Volatility Volatility Volatility
(Feed) (Top) (Bottom)
Ethylene Dichloride 0.4184 0.0532 0.9142 1 1 1
Vinyl Chloride 4.7806 0.9872 6.8358 11.4248 18.5672 7.4773
Hydrogen Chloride 11.413 7.4225 27.2758 139.6055 4.0961
Butadiene 2.2656 0.4579 3.7447 5.4145 8.6134 1.6339
Chloroprene 0.7298 0.0925 1.4938 1.7441 1.7397 0.4819
Tri-Chloroethane 0.1805 0.4406 0.4314 0.1704
Di-Chlorobutane 0.0517 0.1558 0.1236 4.0961
73 | P a g e
2. Minimum Reflux Ratio
Minimum reflux ratio can be found by using Underwood equation.
As feed is entering as two liquid phases at boiling point, therefore q = 0.
𝑛
∑ 𝛼𝑖𝑥𝑓,𝑖 = 1 − 𝑞̅
𝑖=1 𝛼𝑖 − 𝜃
𝜃 = 6.82
𝑛
𝛼𝑖𝑥𝑑,𝑖
∑
𝛼𝑖 = 𝑅𝑚𝑖𝑛 + 1
𝑖=1 −𝜃
𝑅𝑚𝑖𝑛 = 0.5803
3. Flowrates
Ln =197.3605 kg/h and Lm = 835.09 kg/h
Vm = Vn = 480.7806 kmol/h
4. Actual Reflux Ratio
As a rule of thumb R = (1.2-1.5) * Rmin [28]

Ractual = 0.6963
5. Minimum Number of Stages
Minimum number of stages can be found by using Fenske’s equation
𝑥 𝑥ℎ𝑘
log[(𝑥 �) 𝐵
Nmin+1 = ℎ𝑘𝛼 𝐷 𝑥𝑙𝑘 ]
log ( 𝑙𝑘 )𝑎𝑣𝑔
𝛼ℎ𝑘
Minimum number of stages = Nmin = 5

6. Theoretical Number of Stages
Gilliland gives the correlation which relates minimum number of stages with minimum reflux
ratio to find theoretical number of stages.
Theoretical number of stages = 13.58

7. Actual Number of Stages
Actual stages are calculated by first calculating the efficiency of column. Efficiency is
calculated by Drickamer and Bradford correlation.
74 | P a g e
𝐸𝑜 = 17 − 61.6𝑙𝑜𝑔(𝜇𝑓,𝑎𝑣𝑔)
Efficiency of column = 58.4%
Actual number of stages = N (theoretical)/ 0.584
Actual number of stages = 23
8. Location of Feed Plate
The Kirk Bride method is used to determine the number of trays above and below the feed point.
Number of Plates above the feed tray = 2
9. Flooding Velocity at top
First, we have to calculate Flooding velocity, given by
uf = K1 ∗ (ρl ρ
− ρv 0.5
)
v
FIGURE 4- 15: FLOODING VELOCITY, SIEVE PLATES
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𝐿𝑛 𝜌𝑣
𝐹𝑙𝑣 = [√ ]
�
𝑛
�𝑙
𝐹𝑙𝑣 = 0.06
𝐾1 = 0.11
𝜕
𝐾1 = 0.11 ∗ ( )0.2
20
K1 = 0.1027
𝜌𝑙 − 𝜌𝑣
𝑢𝑓 = 𝐾1 ∗
𝜌𝑣
√
𝑢𝑓 = 0.6934 𝑚𝑠−1
At 80% Flooding [18]
𝑢𝑓,80 = 0.8 ∗ 𝑢𝑓
𝑢𝑓,80 = 𝟎. 𝟓𝟓𝟒𝟕 𝒎𝒔−𝟏
10. Column's Diameter at top
𝐿𝑛 ∗ 𝑀
𝑀𝑎𝑠𝑠 𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 =
3600
Mass Flowrate = Vn = 8.3446 kg/s
Volumetric Flowrate = 𝑚̇
𝜌𝑣 = 0.4357 𝑚3/𝑠
̇
Area = 𝑉
𝑢𝑓,80 = 0.7854 m2
Assume 12% down comer area [28]
= 0.7854 / 0.88
= 0.8926 m2
4∗𝐴
Diameter = √ = 1.39 m
𝜋
11. Flooding Velocity at bottom
𝐿𝑛 𝜌𝑣
𝐹𝑙𝑣 = [√ ]
�
𝑛 �𝑙
𝐹𝑙𝑣 = 0.2015
From figure, 4.15
𝐾1 = 0.073
76 | P a g e
𝐾1 𝜕
= 0.11 ∗ ( )0.2
20
K1 = 0.0.07191
𝜌𝑙 − 𝜌𝑣
𝑢𝑓 = 𝐾1 ∗
𝜌𝑣
√
𝑢𝑓 = 0.6157 𝑚𝑠−1
At 80% Flooding [18]
𝑢𝑓,80 = 0.8 ∗ 𝑢𝑓
𝑢𝑓,80 = 0.4925 𝑚𝑠−1
12. Column's Diameter at bottom
𝐿𝑚 ∗ 𝑀
𝑀𝑎𝑠𝑠 𝐹𝑙𝑜𝑤𝑟𝑎𝑡𝑒 =
3600
Mass Flowrate = 13.9625 kg/s
Volumetric Flowrate = 𝑚̇
𝜌𝑣 = 0.9409 𝑚3/𝑠
̇
Area = 𝑉
𝑢𝑓,80 = 1.9103 m2
Assume 12% down comer area,
= 1.9103 / 0.88
= 2.17 m2
4∗𝐴
Diameter = √ = 1.66 m
𝜋
As difference between top and bottom column diameter is less than 20% so we use same
column diameter i.e. 1.66 m.
13. Liquid Flow Pattern
𝐿𝑛∗𝑀.𝑊(𝑇𝑜𝑝)
Volumetric Flowrate at top =
𝜌𝑙,𝑡𝑜𝑝∗3600
= 0.00384 m3/s
Mass Flowrate at top = 𝑉̇ ∗ 𝜌𝑙,𝑡𝑜𝑝 = 0.00384 ∗ 892
= 3.4253 m/s
𝐿𝑚∗𝑀.𝑊(𝐵𝑜𝑡𝑡𝑜𝑚)
Volumetric Flowrate at bottom =
𝜌𝑙,𝑏𝑜𝑡𝑡𝑜𝑚∗3600
= 0.022 m3/s
Mass Flowrate at bottom = 𝑉̇ ∗ 𝜌𝑙,𝑏𝑜𝑡𝑡𝑜𝑚 = 0.022 ∗ 1050
77 | P a g e
= 23.09 m/s
78 | P a g e
Maximum Flowrate occurs at bottom.
FIGURE 4- 16: LIQUID FLOW PATTERN
So, from figure 4.16 liquid flow lies in cross flow regime.
14. Plate Design
𝐷𝑐 = 1.66 𝑚
𝐴𝑐 = 2.17 𝑚2
𝐷𝑜𝑤𝑛 𝑐𝑜𝑚𝑒𝑟 𝐴𝑟𝑒𝑎 = 𝐴𝑑 = 0.12 ∗ 𝐴𝑐 = 0.2604 𝑚2
𝑁𝑒𝑡 𝑎𝑟𝑒𝑎 = 𝐴𝑛 = 𝐴𝑐 − 𝐴𝑑 = 1.9096 𝑚2
𝐴𝑐𝑡𝑖𝑣𝑒 𝑎𝑟𝑒𝑎 = 𝐴𝑎 = 𝐴𝑐 − 2𝐴𝑑 = 1.6492 𝑚2
𝐻𝑜𝑙𝑒 𝑎𝑟𝑒𝑎 = 𝐴ℎ = 0.1 ∗ 𝐴𝑎 = 0.1649 𝑚2
Weir Height = 50 mm [28]
Holes Diameter = 5 mm [28]
79 | P a g e
Plate Thickness = 5 mm [28]
FIGURE 4- 17: WEIR LENGTH
𝑙𝑤
𝐷𝑐 = 0.75
𝑙𝑤 = 0.75 ∗ 𝐷𝑐 = 1.245 𝑚
15. Weeping Check
Max. Liquid Flowrate = Lw, max = 23.09 m/s
At 70% turndown = 0.7*Max.liquid rate [28]
Lwq, min = 0.7*23.09 = 16.163 m/s
(2)
ℎ𝑜𝑤 = 750 ∗ 𝐿𝑤,𝑚𝑎𝑥 3
∗𝑙 ]
𝑙,𝑏𝑜𝑡𝑡𝑜𝑚 𝑤
2)
23.09 3
(
ℎ𝑜𝑤,𝑚𝑎𝑥 = 750 ∗ [ ]
1050 ∗ 1.245
ℎ𝑜𝑤,𝑚𝑎𝑥 = 50.876 mm
2
16.163 ( )
3
ℎ𝑜𝑤,𝑚𝑖𝑛 = 750 ∗ [ ]
1050 ∗ 1.245
ℎ𝑜𝑤,𝑚𝑖𝑛 = 40.1024 𝑚𝑚
80 | P a g e
At minimum rate,
ℎ𝑤 + ℎ𝑜𝑤 = 50 + 40.1024 = 90.1024 𝑚𝑚
FIGURE 4- 18: WEEP POINT CORRELATION
K2 = 30.7
(𝐾2 −0.9(25.4−𝑑ℎ )
Velocity at min. rate = 𝑢̌ =
√𝜌𝑣
𝑢̌ = 3.2826
0.7∗𝑉̇𝑏𝑜𝑡𝑡𝑜𝑚
Actual min. Velocity =
𝐴ℎ
0.7 ∗ 0.9409
=
0.1649
Actual min. Velocity = 4 m/s
As, actual minimum velocity is greater than velocity at minimum rate. So, minimum operating
rate is above weep point.
16. Plate Pressure Drop
𝑉̇
Maximum vapor velocity through holes =
𝐴ℎ = 0.9409/0.1649
= 5.7059 m/s
Plate thickness/Holes diameter = 5/5 = 1
81 | P a g e
Ah/Aa = Ah/Ap = 0.1649/1.649 = 0.1
FIGURE 4- 19: DISCHARGE COEFFICIENT OF SIEVE PLATES
Co = 0.84
𝑢ℎ 2𝜌
𝑣
𝐷𝑟𝑦 𝑃𝑙𝑎𝑡𝑒 𝐷𝑟𝑜𝑝 = ℎ𝑑 = 51 ∗ [ ]
�𝑜 𝜌𝑙
hd = 51*[5.7059/0.84]2 *[14.1316/1050] = 31.6710 mm Liquid
3
Residual Head = 12.5∗10 = 11.9048 𝑚𝑚 𝐿𝑖𝑞𝑢𝑖𝑑
1050
Total Pressure Drop = hd + hr + (hw + how)

= 31.6710 + 11.9048 + 66.67 = 100.2458 mm Liquid
17. Down Comer Liquid
hap = Weir Height – 10 = 50-10 = 40 mm
Aap = hap * lw = 40 * 10-3 * 1.245 = 0.0498
m
𝐿𝑤,𝑡𝑜𝑝
hdc = 166 * [ ]2
𝜌𝑙𝐴𝑎𝑝
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hdc = 32.368 mm Liquid
83 | P a g e
hb = (hw + how) + ht + hdc = 66.67 + 100.2458 + 32.368 = 199.2838 mm Liquid
hb = 199.2838 * 10-3 = 0.1992 m
1/2 (plate spacing + weir height) = 0.325
As 1/2 (plate spacing + weir height) > hb so plate spacing is acceptable
18. Residence Time
𝐴𝑑ℎ𝑏𝜌𝑙
𝑡𝑟 =
�𝑤,𝑏𝑜𝑡𝑡𝑜𝑚
0.2604 ∗ 0.1992 ∗ 1050
𝑡𝑟 = = 2.3650 𝑠
23.03
10.34 > 2 is satisfactory
19. Number of Holes
Area of one hole = (𝜋) ∗ 𝐷2
4 ℎ
Area of one hole = ( ) ∗ (5 ∗ 10−3)2 = 1.963*10-5 m

𝜋
4
Number of holes =0.1649/1.963*10-5 = 8400.4075
4.4.3 ASPEN Simulation
'DSTWU' model Column Design on 'ASPEN Plus'
FIGURE 4- 20: VCM DISTILLATION COLUMN
STREAM COMPOSITION were specified as known from material balance along with process
conditions in the feed stream to column. The method selected for the property estimation of
components was NRTL-RK.
The overall result summary shows that against minimum reflux ratio of 0.58, 13 equilibrium
stages are obtained which are equal to the theoretical no. of stages as indicated by figure 3-32, if
instead of reflux ratio, actual no. of stages which are calculated as 23 is entered, the reflux ratio
shows a drop as well as heat duties for reboiler and condenser also show a quite change in their
values. However the purity to be achieved for VCM stays same i.e. 99.57% as indicated by
84 | P a g e
figure
85 | P a g e
3-31 and the temperatures for top and bottom also stays the same.
FIGURE 4- 21: ASPEN RESULTS FOR VCM COLUMN
86 | P a g e
CHAPTER 5: PROCESS CONTROL AND
INSTRUMENTATION
5.1 Instrumentation
Instrumentation is carried out via monitoring of the fundamental process variables in the course
of plant operation. These variables are classified as either automatic or manual adjustable
variables. Instruments checking the key process variables are fixed with automatic alarms to
prepare the operators for any hazardous states. A wide-ranging computing devices, ranging from
set in microprocessors to out-and-out computers, is commonly engaged throughout the industry
[29].
5.2 Control
Instrumentation not only measures the field parameters but it also allow for the ability to alter
some of these parameters to cling to that of the process ones at a desired or set value.
5.3 Inducements for Chemical Process Control
A chemical plant includes series and parallel arrangement of processing units incorporated to
one another in a methodical and balanced style. The plants overall aim is to translate certain raw
materials into desired products using existing resources of energy, in the utmost cost-effective
way.
 Production Requirement: A control structure warranties the production specifications

and desired purity achievement.
 Operational Constrictions: The different categories of equipment used in industrial

plants have limitations congenital to their working. Such restrictions are met during the
course of the operation of the plant.
 Safety: The harmless process operation is a chief requirement for the well-being of the
personnel and other staff in the plant and for its sustained involvement to the profitable
development.
 Economics: The process of a plant must adapt to the market surroundings means the
accessibility to raw materials and the ultimatum of the desired products. It must be as
cost-
87 | P a g e
effective and efficient as possible in the exploitation of energy, raw materials and
capacity and labor. [29]
5.4 Fundamentals of Control System
In nearly every control structure, the following hardware elements are found.
 The chemical process
 Measuring element or sensors
 Transducers
 Transmission lines Controllers
 Final control element

5.5 Approaches to Control
There exist several manners by which a process is monitored and then controlled. These
methods depend upon the controller kinds and the action done to handle any process parameter.
This controller action is influenced by the output signal from transmitter which is then related
with the set (desired) point to the controller and on the deviation or error in between the two
parameters.
5.5.1 Varieties of Control Actions
On the recommended basis, following are the different types of control

 Proportional Controller
 On-Off Controller
 Integral Controller
 Derivative or Rate Controller
 Composite Controller (P, PI, PID)
5.5.2 Control Loops

For instrumentation and control of any equipment as part of process plants following control
loops are most often uses:
 Feed Backward Control Loop
 Feed Forward Control Loop
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 Cascade Control Loop
89 | P a g e
 Ratio Control Loop
 Split Range Control Loop
5.6 Instrumentation and Control on Distillation Column
FIGURE 5- 1: CONTROL SCHEME OF DISTILLATION COLUMN

5.6.1 Disturbances
 Column Pressure
 Feed Flow Rate / Composition

 Reboiler Steam Pressure
90 | P a g e
 Overhead Product Flow Rate
 Cooling Water Flow Rate
 Steam pressure or flowrate
5.6.2 Manipulated Variables
 Reflux Rate
 Distillate Flow Rate
 Bottom Flow Rate
 Steam Flow Rate
5.6.3 Control Variables
 Top and Bottom Temperature / Concentration

 Liquid height in Reflux Drum
 Liquid height in Column Base
 Pressure of column
5.7 Instrumentation and Control over VCM Purification Section
The HCl column is controlled by control loop over the overhead and bottom section with
control loop over bottoms employing a 'low select switch control steam flow rate'. I.e. both the
composition and differential pressure controller acquire steam flow and the smallest one is taken
up by low select switch. The desired (set) point for both controller is set equivalent to the
'maximum tray pressure drop' in case of differential pressure controller. While in case of
composition controller, the set point is defined as the 'to be achieved composition' for bottom
products. The control loop at overhead section make use of the level controller over reflux drum
in order to control the column's reflux ratio.
The VCM column is also controlled by control loop over bottom and overhead sections. The
bottoms temperature is refrained from changing value by adjusting the flowrate of the steam
flowing to the reboiler. While for overhead control loop, distillate flowrate is varied in order to
control the level inside reflux drum. Also the composition controller is employed which
maintains reflux ratio close to its set point in order to control the distillate composition.
91 | P a g e
FIGURE 5- 2: INSTRUMENTATION AND CONTROL OVER VCM PURIFICATION SECTION
92 | P a g e
CHAPTER 6: HAZARD AND OPERABILITY
ANALYSIS
6.1 Introduction
The determination of hazards is compulsory for the harmless operation and working in process
plant. There are countless methodologies accessible for the determination of these hazards. The
most common and significant of them is hazard and operability (HAZOP) study/analysis.
HAZOP study is a well-thought-out method for the identification of likely hazards and
challenging operations of a process by investigating the different disagreements from process
design factors. To authorize best engineering performances and to look over mishaps, or to lead
in the formation of system as regards of safety supervision and management. This method is
industrious and effective to diagnose the hazards that could heighten the safety levels and
upsurge the reliability and steadfastness of the system. [23]
6.2 HAZOP Process
The detailed step by step procedure is described below:
FIGURE 6- 1: THE HAZOP PROCESS
93 | P a g e
6.3 HAZOP Deviation Guide
TABLE 6- 1: DETAIL OF HAZOP DEVIATION GUIDE WORDS

GUIDE WORDS
PARAMETER No Less More Part of As well Other Reverse

as than
Level Empty Low level High level Low High
interface Interface
Temperature Freezing Low High Auto
temperature temperature refrigeration
Pressure Open to Low High Vacuum
atmosphere Pressure Pressure
Flow No flow Low rate High rate Missing Mis- Wrong Back flow
ingredient direction material
6.4 HAZOP Study on Reactor
TABLE 6- 2: HAZOP ANALYSIS OF REACTOR

Guide word Event that Consequence of Additional Process Note and
and could cause this deviation implication of indication question
Deviation this on item of this
from deviation equipment consequence
operating under
Conditions consideration
Less level  Reactor  Pump cavities Damage to Level Maintenance
vessel run  Reagent pump controller of Level
dry released installed at indicator?
 Product mid-way up PID
valve open of reactor controller for
or broken more
accuracy?
Have a stand
by pump?
More level  Feed A  Error in flow Over flow and Level What is the
reactant controller at release of toxic controller maximum
valve open inlet feed A chemicals installed at capacity of
or broken  Error in flow mid-way up the reactor?
 Feed B controller at of reactor Effect of
reactant inlet feed B excess raw
valve open material on
or broken the reaction?
 Product
valve close
94 | P a g e
More  Cooling  No circulation Temperature What is the
temperature water valve of cooling controller set point?
closed water installed over Operation
 Fouling  Low heat Reactor temperature
transfer for the
coefficient reactor?
 No make-up
water
 Increasing
Heat of
mixing
Less  Low  Increase Temperature
temperature surrounding viscosity of controller
temperature product installed over
 Low  Conversion of Reactor
cooling reaction
water
temperature
Less pressure  Relief valve No reaction Phase change of Pressure What is the
open or product from controller maximum
broken liquid to vapor installed over allowable
 Pressure Reactor pressure?
controller
failure
More  Relief valve Explosion Pressure
pressure closed controller
 Pressure installed over
controller Reactor
failure
6.4.1 Hazards
 Bursts from unrestrained chemical reactions due to overpressure or due to release of

energy from exothermic reactions (a result of mechanical destruction or corrosion).
 Unexpected release of toxic constituents from a reactor due to the work- related mishap
or because of human error.
 Failure due to elevated temperature from a chemical reaction.
6.4.2 Safety Precautions
 Inspect occasionally electrical tools for safety before use and call a competent electrician
for analyzing and repairing of defective or suspect electrical equipment.
 Set up nominal exhaust ventilation and air cooling system, especially in the operator's
workspace, to prevent air adulteration and heat stress.
95 | P a g e
6.5 HAZOP Study on Pump
TABLE 6- 3: HAZOP ANALYSIS OF PUMP

Guide Word Event that Consequence Additional Process Notes and
and could cause of this implication of indications questions
Deviation this deviation deviation on this
from item of consequence
operating equipment
Conditions under
consideration
No Flow Suction Line Pump Installed flow
plugs cavitation and Controller
pump damage
More Flow Disruption in  Reagent Damage to Installed flow Estimate

upstream unit Release pump Controller Release
operation  Upset in quantity.
downstream
operations
More Discharge line Deadhead Damage to Installed Can reagents
Pressure plugs pump pump Pressure explode due to
controller over pressure?
Less pressure Suction line Pump Deadhead Installed Any other
plugs cavitation pump and Pressure problem with
pump damage controller deadhead?
More Closed outlet Deadhead Damage to Installed
Temperature valve pump pump Temperature
controller
6.5.1 Hazards
Many hazards are associated with pumps like operating hazards where the flow rate of the
pumped liquid is too high or the flow rate is too low (due to many reasons like reservoir is
almost empty, air (air bubbles) in the pipes, also deposits in pipes), in addition to that, electrical
failure may cause hazards (no electricity, circuit failure, overheating due to incorrect/ loose
wires connection or high charge supply), System malfunction, Over pressurization, deadheads
etc.
 Driver power must be locked out to avoid electrical shock or accidents while start-up
and shutdown.
 Use the suitable material of construction for the pump while working while corrosive
liquids, also a temperature should be mounted if the liquid is temperature- sensitive.
 Make sure that all discharge and suctions are opened before operating the pump.
 Always operate the pump above the recommended minimum flow rate when dry.
96 | P a g e
 Work at the required NPSH (Net positive suction head).
6.6 HAZOP Study on Furnace
TABLE 6- 4: HAZOP ANALYSIS OF FURNACE

Deviation Event that Consequence Additional Process Notes and
from could cause of this implication of indications questions
operating this deviation deviation on this
Conditions item of consequence
equipment
under
consideration
High  High fuel  Unable to get Harm to Temperature Inspect the
Temperature amount desired downstream controller adjustment in
supplied to products. unit operations installed at set point of
the furnace  Pressure radiant and flowrate.
 Decreased accumulation convection Check pipes/
inlet lead to section. equipment
flowrate explosion function.
 Release of Shut down if
harmful flue temperature is
gases. too high.
Low  Less than Effect the Not desired Temperature Check valves,
Temperature required translation quality product controller set point and
heat of product installed at pipes for their
Provided radiant and proper
 Inlet convection functionality.
flowrate is section.
too high
6.6.1 Hazards
 Failure of air suction fan and increasing of concentration of hazardous substances inside
the furnace
 Closing of the valve to suction/emergency ventilation system
 Opening the furnace doors during the operation and outflow of hazardous substances
from the furnace
 Power outage and increasing of concentration of hazardous substances inside the furnace
 Vacuum, Plaster and dirt cause hazards around your furnace.

 Retain Air Flow
 Plan and program Inspections.
 Keep Combustible Items Away.
97 | P a g e
 Examine Smoke Alarms.
6.7 HAZOP Study on Distillation Column
TABLE 6- 5: HAZOP ANALYSIS OF DISTILLATION COLUMN

Guide word Event that Consequence Additional Process Notes and
and could cause of this implication of indications questions
Deviation this deviation deviation on this
from item of consequence
operating equipment
Conditions under
consideration
No Flow  Pipe  Dry out in No Production Flow Set up low
blockage column controller temperature
 Valves fail  Possible installed above alarm and
open dangerous condenser Direct towards
 Tube concentration inlet. maintenance
leakages  No operation procedure and
plan
Less Flow  Blockage of  Dry out in Equipment Flow Set up low
pipeline column shutdown controller temperature
 Valves  Product installed above alarm and
failure quality condenser Direct towards
 Tube variations inlet. maintenance
leakages schedule.
More Flow  Fully open  Flooding in Rise in Flow Set up high
valve the column condenser and controller temperature
 Control  Changes in reboiler duty. installed above alarm and
valve failure product condenser Direct towards
 Increase quality inlet. maintenance
pumping Temperature planning.
capacity decrease
High Level Blockage  Over high Over flow to Installed What is the
At output pressure in downstream Level maximum
reflux drum unit operation. controller over level required?
 Back flow of reflux drum Check for
condensed reflux drum.
liquid to
column
Low level Pipe partial Back flow can Damage to Installed At how much
clogged and occur to fulfill column Level low level can
leakage the controller over reboiler
requirement. reflux drum damage?
More Pressure High Level Failure of Column may Pressure What can be
pressure relief explode controller the maximum
valve installed at top operating
and bottom of pressure?
column.
98 | P a g e
High Less feed in  Pressure Damage to Temperature Install high
Temperature the column buildup in reboiler and controller temperature
column condenser installed over alarm.
 Undesired condenser and How much
components reboiler high
temperature
can yield
undesired
product?
Low Malfunctioning  Desired Damage to Temperature Set up low
temperature of reboiler components reboiler and controller temperature
will not condenser installed over alarm and
separate condenser and Direct towards
 Undesired reboiler maintenance
product procedure and
plan
6.7.1 Hazards
There are many failures that may occur while operating a distillation column like flooding (at
the bottom of the tower), reboiler failure, bursting in the column, Emission through pressure
release valve, tray defect, internal fire or explosion, poor separation (foaming, entrainment,
weeping).
 Reliable level of monitoring

 Good material of construction.
 Check the stability if control loops (temperature and pressure through the column)
 Regular cleaning and maintenance.
99 | P a g e
CHAPTER 7: COST ESTIMATION
𝐼𝑛𝑑𝑒𝑥 𝑣𝑎𝑙𝑢𝑒 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑜𝑓 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑐𝑜𝑠𝑡
Present cost = Original cost * 𝑖𝑛𝑑𝑒𝑥
( 𝑣𝑎𝑙𝑢𝑒 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑜𝑓 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑐𝑜𝑠𝑡 )
The original time for graph availability is 2002 with CEPCI value from [31] which it is to be
scaled up to 2021 but last available cost index was for year 2019 from [32] for which it is scaled
up by 9.6% as indicated by [33].
7.1 Chlorinator Reactor (CSTR)
Volume (Capacity) of Reactor = 4.324 m3

FIGURE 7- 1: PURCHASED COST FOR JACKETED AND STIRRED REACTORS
Cost of stainless steel at 50 psia = $50,000 (which is nearest one to our pressure)
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 = 2.60*50,000 = $85,550
100 | P a g e
7.2 Reactor Pump (P-100)
FIGURE 7- 2: PURCHASED COST FOR CHEMICAL INLINE PUMP
Density of stream = 1249 kg/m3 = 4.73 kg/gal

Flowrate = 50138 kg/hr = 835.6 kg/min
Pressure = 26 bar = 377.1 psia
Capacity factor = (835.6 * 377.1)/4.73 = 6.7E+04 (gal/min*psia)
Purchased Cost = $74000
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 = 1.711*74,000 = $126,614
7.3 Evaporator (E-105)
Surface area for evaporator = 237.554 m2 (from section 4.2)
101 | P a g e
Pressure of stream = 26 bar =2600 kPa
FIGURE 7- 3: PURCHASED COST FOR SHELL AND TUBE HEAT EXCHANGER
Purchased Cost = $27,000

Adjustment factor against 2600 kPa for tube is 1.0276 and for tube and shell it is1.063
So, cost = purchased cost * adjustment factors
= $27,000*1.0276*1.063 = $ 29493
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 = 1.711*29,493 = $50,462
7.4 Pyrolysis Furnace
Heat required to achieve 500°C temperature is 1.59E+07 kJ/hr = 15.07 Million Btu/hr
Purchased Cost (c.p) = $ 230,000
Cost = FI * Fp * FT *c.p = 403,928 $
FI [Installation factor] = 1.52
Fp [pressure factor] = 1.06
102 | P a g e
FT [Type factor (pyrolysis)] = 1.09
677
Index ratio (1980/2021) =
260 = 2.60
Cost of furnace at (2021) = $ 1,051,766
FIGURE 7- 4: COST FOR PYROLYSIS BOX-TYPE FURNACE, 1980
7.5 Quench Tank
Average density of inlet stream to flash tank = 1225 kg/m3

Flow towards column after including recycle quench stream =64079 kg/h (chapter 3)
Volumetric capacity = 64079/1225 = 52.26 m3/h
103 | P a g e
For time of 1 hour, volumetric capacity =52.26 m3 = 1846 ft3
FIGURE 7- 5: PURCHASE COST FOR FLASH TANK
The purchase cost for Interlox saddles (porcelain) Packing type with 2 in packing size is around
15.5 $/ft3.
FIGURE 7- 6: MATERIAL FACTOR FOR DIFFERENT PACKING TYPES
Ratio for carbon type packing = 2.35

Purchase cost ($) = 15.5*1846 *2.35 = $67,230
104 | P a g e
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 = 1.711*67,230 = $115,030
7.6 Coolers Cost (E-106, E-111, E-112)
FIGURE 7- 7: PURCHASED COS FOR SHELL AND TUBE HEAT EXCHANGERS
Operating pressures for each exchanger is 12 bar = 1200 kPa

Pressure adjustment factor would be 1.006 for tube and shell and approximately 1 for tube
Approximating same surface area s for evaporator
Surface area for evaporator = 237.554 m2 (from section 4.2)

So, cost = purchased cost * adjustment factors
= $27,000*1*1.006 = $ 27,162
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 for 3 = 3*1.711*27,162 = $139,423
105 | P a g e
7.7 Distillation Columns (VCM, HCl, Lights, Heavies)
Based on complete design of VCM column, specification for other 3 columns is assumed to be
same for cost estimation
FIGURE 7- 8: PURCHASED COST FOR DISTILLATION COLUMNS

Column’s height = 13.2 m (chapter 4)
Column's diameter is taken the largest of both top and bottom =1.66 m
Purchased Cost = $40,000

Cost = Fm*FP*CP
Fm = [material Factor] = 3 for stainless steel
Fp = [Pressure Factor]:
For VCM column at 4.8 bar (4800 kPa) = 3.119

For HCl column at 12 bar (12000 kPa) = 5.42
For Lights and heavies columns at 1.2 bar (1200 kPa) = 1.667
Cost (VCM) = 3.119*3*40000 = $374,280
106 | P a g e
Cost (HCl) = 5.42*3*40000 = $650,400
Cost (Lights and heavies) = 1.667*3*40000 = $200,040
CEPCI (2002) = 395.6
CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 for VCM = 1.711*374,280 = $640,393
Cost in 2021 for VCM = 1.711*650,400 = $1,112,834
Cost in 2021 for VCM = 1.711*200,040 = $342,268
7.8 Mixing Tanks (V-1, V-2, Mix)
FIGURE 7- 9: PURCHASED COST FOR MIXING TANKS INCLUDING DRIVING UNIT

Average density is taken to be 1250 kg/m3 for all 3 mixing points
Flowrate towards V-1 is Stream (14+3) = 52160 kg/h
Volume for 1 h time = 52160/1250 = 41.728 m3
Flowrate towards V-2 is Stream (9+J) = 73880 kg/h
107 | P a g e
Volume for 1 h time = 59.104 m3
Flowrate towards mix is Stream (H+L) = 64079 kg/h
Volume for 1 h time = 51.26 m3
So,
Purchased cost for stainless steel tank for each
is V-1 = mix =$ 90,000
V-2 = $100,000
CEPCI (2002) = 395.6

CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 for V-1 and mix = 1.711*90,000*2 = $307,980
Cost in 2021 for V-2 = 1.711*100,000 = $171,100
7.9 Storage Tanks (VCM, HCl)
FIGURE 7- 10: PURCHASED COST FOR STORAGE TANKS
VCM mass flowrate = 17708 kg/h
Density of VCM = 911 kg/m3
108 | P a g e
Volumetric flowrate of VCM = 17708/911 = 19.43 m3/h
And
HCl mass flowrate = 11997 kg/h
Density of HCl = 1.6423 kg/m3
Volumetric Flowrate = 1199/1.6423 = 7315 m3/h
For carbon steel tank
Cost of VCM tank = $30,000
Cost of HCl tank = $180,000
CEPCI (2002) = 395.6

CEPCI (2021) = 677
Index Ratio = (677/395.6) = 1.711
Cost in 2021 for VCM tank = 1.711*30,000 = $51,330
Cost in 2021 for HCl tank = 1.711*180,000 = $307,980
7.10 Total Purchased Equipment Cost
Cost of Tanks = $51,330 + $307,980

Cost of Mixing tanks = $307,980 + 171,100
Cost of Heat exchangers = $139,423 + $50,462
Cost of Distillation Columns = $342,268 + $1,112,934 + $640,393
Cost of Reactor = $85,550
Cost of Furnace = $1,051,766
Cost of Pump = $126,614
Cost of quench tank = $115,030
Total purchased equipment Cost = $4,502,830
7.11 Direct Cost
Installation cost (40% of equipment cost) = $1,801,132
Instrumentation and control cost (13% of equipment) = $585,368
Piping cost (32% of equipment) = $1,440,906
Electric cost (10% of equipment) = $450,283
109 | P a g e
Building (29% of equipment) = $1,305,821
Land cost (6% of equipment cost) = $270,170
Total Direct Cost = $5,853,680
7.12 Indirect Cost
Engineering and supervision cost (32% of equipment cost) =
$1,440,906 Construction expenses (30% of equipment cost) =
$1,350,849 Contractor fee (18% of equipment cost) = $810,509
Contingency cost (30% of equipment cost) = $1,350,849
Total Indirect Costs = $4,953,113
7.13 Total Capital Investment
Fixed capital investment = Direct cost + Indirect cost
Fixed capital investment = $10,806,793

Working capital (18% of fixed capital cost) = $1,945,223
Total Capital Investment = Working capital + Fixed capital investment
= $12,752,016
7.14 Plant Cost
Assume that the fixed capital investment devaluates by straight line method for 10 years.
Assuming 5% salvage value at the end of plant life
Depreciation = D = (V-Vs)/N
V= Fixed capital investment
VS= 0.05*Fixed Capital Investment
VS= $540,339
N= no. of years = 10
D = $1,026,645
Total Plant Cost = Total Capital Investment + Depreciation
Total Plant Cost = $13,778,661
110 | P a g e
REFRENCES
1. R.W. Kapp Jr. Encyclopedia of Toxicology, 3rd Ed., 2014.
2. Bönnighausen Dreher. EHS 215 Vinyl chloride, 1986.
3. Jnny Heumann. Polyvinyl Chloride, 2010.
4. Alexandre C. Dimian & Costin Sorin Bildea. Integrated design and simulation of Chemical
Processes, Vinyl chloride monomer process chapter 7, 2008.
5. M. Hassan & Hamza ghalib. PVC sector study Maria Fátima Costa Farelo, Advance
modelling of VCM production via thermal cracking of EDC, 2018.
6. Jeremy Dry. Vinyl chloride production, University of Oklahoma, 2003.
7. Andrea Salto, Maria Martin Carnicero, Paul Julius Degraeve & Michel Lempereur. Process
for manufacturing VCM and PVC, 2012.
8. Francisco Jose Freire, Bruce Arthur Kaiser, Dennie Turin Mah & Vinci Martinez Felix.
Production of EDC by direct chlorination and VCM by chlorine recycle apparatus, 1996.
9. E.L. Dreher, T.R. Torkelson & K.K. Beutel. Chloroethanes & Chloroethylenes in Ullman’s
Encyclopedia of Industrial Chemistry, Wiley–VCH, 2012.
10. Bryce Lawsn. Observatory of economic complexity, Vinyl chloride polymers, 2012.
11. Maria Joana. Technavio, Global VCM market 2017-2021, 2017.
12. Fumiko Dobashi, Hui Heng & Miranda Zhang, feedstock supplies to Saudi petrochemical
firms improve, 2019.
13. GlobalData Energy, China leads globally in terms of planned and announced ethylene
capacity additions, 2020.
14. IHS Markit, Polyvinyl chloride (PVC) resins, 2018.
15. Private power and infrastructure board, ground breaking of 300MW coal, 2019.
16. Hagler Bailley. Pakistan Expansion of Engro Polymer and Chemicals Limited’s PVC and
VCM Manufacturing Plant, 2018.
17. Ullmann's Encyclopedia, Chlorinated Hydrocarbons, vol.A6, 1993.
18. Seader. Henly. Roper. Separation Process Principles, 4th edition John Willey and Sons
19. Dr. Reyad Shawabkeh. Steps for design of Furnace/Fired. King Fahd University of
Petroleum & Minerals, 2015.
20. Donald Q. Kern. Process Heat Transfer. TATA McGraw-Hill edition, 1983.
21. Robert H, Perry, Don W Green. Perry’s Chemical Engineer’s Handbook. McGraw-Hill
publication, 1999.
22. Max S. Peter, Klaus D. Timmerhaus. Plant Design and economics for chemical engineers.
McGraw-Hill 4th edition, 1991.
23. R. Turton, R. C. Bailie, W. B. Whiting, and J. A. Shaeiwitz, Analysis, synthesis and design
of chemical processes. Pearson Education, 2008.
24. Octave Levenspiel. Chemical Reaction Engineering. Jhon Wiley and sons 3rd edition,1999
25. Trambouze and P. Euzen. Chemical reactors. JP Publications, 2004.
26. NSY Steel. Comparison of 316 and 316L application data, 2010.
27. A Lakshmanan, W.C. Rooney, LT Biegler. A case study for reactor network synthesis: the
vinyl chloride Process. ELSEVIER, 1998.
28. Coulson and Richardson. Chemical Engineering Design (R.K. SINNOTT). ELSEVIER,2005
29. Carl L. Yaws. Chemical Properties Handbook. McGRAW-Hill, 1999.
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30. G. Stephanopoulos. Chemical Process Control, 'An Introduction to Theory and Practice's. 696. P
T R Prentice Hall.
31. Scibrdaglab. CEPCI Index 1950 - 2015. SCRIBD, 2018.
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112 | P a g e

Production of Vinyl Chloride Monomer Via Thermal Cracking of Ethylene Dichloride

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Production of Vinyl Chloride Monomer via Thermal

Cracking of Ethylene Dichloride

Supervised by: Dr. Zafar Noon

Department of Chemical Engineering

Bachelor of Science in Chemical Engineering

Internal Examiner External Examiner

Department of Chemical Engineering

Name Registration No. Signature

Momina Asghar 2017-CH-05

Umar Hayat 2017-CH-59

Anaiha Iftikhar 2017-CH-69

Marwan Bahgan 2017-CH-199

Registration No. %Contribution Signature

Our beloved Parents and respected Teachers

1.1 Defining the Problem............................................................................................................1

CHAPTER 2: PROCESS SELECTION....................................................................................5

CHAPTER 3: MATERIAL AND ENERGY BALANCE.......................................................18

3.1 Overall Mass Balance.........................................................................................................18

CHAPTER 4: DETAILED EQUIPMENT DESIGN..............................................................48

4.1 Pyrolysis Furnace...............................................................................................................48

CHAPTER 5: PROCESS CONTROL AND INSTRUMENTATION..................................81

CHAPTER 6: HAZARD AND OPERABILITY ANALYSIS................................................86

6.5.2 Safety Precautions........................................................................................................89

CHAPTER 7: COST ESTIMATION.......................................................................................93

7.1 Chlorinator Reactor (CSTR)...............................................................................................93

Figure 2- 1: Routes to manufacture PVC.......................................................................................5

Figure 3- 1: I/O Diagram for Process...........................................................................................18

Figure 4- 1: Graph to Determine Flue Gas Temperature.............................................................49

Figure 5- 1: Control Scheme of Distillation Column...................................................................83

Figure 6- 1: The HAZOP Process................................................................................................86

Figure 7- 1: Purchased Cost for Jacketed and Stirred Reactors...................................................93

Table 2- 1: Process Comparison.....................................................................................................7

Table 3- 1: Heat of Reactions for Chlorinator Reactor at 90°C...................................................21

Table 4- 1: Initial Required Data For Design Calculation of Furnace.........................................48

Table 6- 1: Detail of HAZOP Deviation Guide Words...............................................................87

CEPCI Chemical Engineering Plant cost index

The applications of VCM as intermediate product is wide in production of useful products.

FIGURE 1- 1: PRODUCT WISE APPLICATION OF PVC IN 2018

1.2.1 Environmental Effects

1.2.2 Health and Safety

1.3 Structure and Properties

FIGURE 1- 2: VINYL CHLORIDE MONOMER STRUCTURE

TABLE 1- 1: PROPERTIES OF VINYL CHLORIDE

PROPERTIES MEASURED VALUES UNITS

1.4 Production and Demand Analysis

1.5 Literature and Market Survey

YEAR VCM Cost ($/ton)

2.2 Production Routes

FIGURE 2- 1: ROUTES TO MANUFACTURE PVC

2.2.2 Vinyl Chloride from Ethane

Cl−CH2−CH2−Cl → CH2 =CHCl + HCl

Ethane can be transformed to vinyl chloride by various routes:

2.2.3 Vinyl Chloride from Ethylene

Direct chlorination: CH2CH2 + Cl2  C2H4Cl2

2.3 Process Comparison

TABLE 2- 1: PROCESS COMPARISON

ACETYLENE ETHANE ETHYLENE