‫﷽‬

‫ٱلِلَ َ‬
‫غ ِن ٌّی‬ ‫لِلِ َو َمن یَ ۡشك ُۡر فَ ِإنَ َما یَ ۡشك ُُر ِلنَ ۡف ِ‬
‫س ِۖۦه َو َمن َكفَ َر فَ ِإ َن َ‬ ‫﴿ولَقَ ۡد َءات َ ۡینَا لُ ۡق َم ٰـ َن ۡٱل ِح ۡك َمةَ أ َ ِن ۡ‬
‫ٱشك ُۡر ِ َ ِۚ‬ ‫َ‬
‫ࣱ‬
‫َح ِمید﴾‬

‫]لقمان ‪[ ١٢‬‬
 Dedication
We are deeply grateful to the remarkable individuals who have played vital roles in the
completion of this research project. Their unwavering support, guidance, and encouragement
have been instrumental in its success.

First and foremost, we would like to express our profound appreciation to our families. Their
unconditional love, understanding, and patience have been our rocks throughout this
challenging journey. Their constant support and unwavering belief in us have fueled our
academic pursuits and inspired us to overcome obstacles.

We also extend our heartfelt gratitude to our friends, whose unwavering encouragement,
insightful discussions, and unwavering friendship have enriched this journey beyond
measure. Their companionship and camaraderie have not only made the academic aspect
fulfilling but have also provided us with immeasurable joy and growth.

Lastly, we dedicate this work to our cherished friends and families. Their unwavering
support and love have been our greatest blessings. Their mere presence in our lives has
granted us strength, inspiration, and boundless joy. It is with deep gratitude that we
acknowledge their profound impact on our personal and academic endeavors.

To all those who have contributed to this project, we are forever indebted to your kindness
and belief in our abilities. Thank you for being integral parts of this journey and for helping
us achieve this milestone.
 Acknowledgements

We would like to express our deepest appreciation to all those who provided the possibility
to complete this research. A special gratitude we give to Prof. Dr. AMMAR AL-BAAJ,
whose contribution in stimulating suggestions and encouragement, helped us to coordinate
our project especially in writing this report. Furthermore, we would also like to acknowledge
with much appreciation the crucial role of POLYMER & PETROCHEMICAL
DEPARTMENT, who gave the permission to use all required equipment and the necessary
materials to complete the task. A special thanks goes to our team members, who have
worked tirelessly with us.
 Table of Contents
Table of Contents .................................................................................................... I
List of Tables ........................................................................................................ III
List of Figure ........................................................................................................ III
Abbreviations ......................................................................................................... V
Abstract ................................................................................................................. VI
Chapter One: Introduction
1.1. Introduction ...................................................................................................... 1
1.2. Background Information .................................................................................. 2
1.2.1. Environmental Effects ................................................................................... 2
1.2.2. Health and safety ........................................................................................... 2
1.3. History .............................................................................................................. 3
1.4. Physical and Chemical Characteristics ............................................................ 4
1.5. USES ................................................................................................................ 6
1.6. Production and Demand Analysis .................................................................... 6
1.7. Market analysis ................................................................................................. 7

CHAPTER Two: PROCESS DESCRIPTION AND SIMULATION WITH

ASPEN HYSYS
2.1. Background....................................................................................................... 9
2.2. ASPEN HYSYS ............................................................................................. 10
2.3. Production Routes .......................................................................................... 10
2.3.1. Vinyl Chloride from Acetylene ................................................................... 10
2.3.2. Vinyl Chloride from Ethane ........................................................................ 11
2.3.3. Vinyl Chloride from ethylene ..................................................................... 12
2.3.3.1. Direct Chlorination Reactors System ....................................................... 15
2.3.3.2. Oxychlorination of ethylene Reactors System ......................................... 16
2.4. Ethylene Dichloride Purification.................................................................... 20
2.5. Ethylene Dichloride Pyrolysis ........................................................................ 22
2.6. Vinyl chloride purification ............................................................................. 23
I
 CHAPTER Three: EQUIPMENT DESIGN
3.1. Simulation of Rigorous Distillation Column (C1 & C2) ............................... 26
3.2. CSTR Volume Calculation: ........................................................................... 33
Weight of catalyst .................................................................................................. 34
3.3. Plug Flow Reactor Calculation (Oxychlorination Reactor): ......................... 35
Catalyst Void Fraction........................................................................................... 36
Weight of catalyst PFR.......................................................................................... 36
3.4. Wash Tower Calculation: ............................................................................... 37
3.5. Separator (V-100) ........................................................................................... 38
3.6. Fired Heater (FH-100) .................................................................................... 38
3.6.1. Rigorous design of a fired heater in Aspen HYSYS .................................. 39
3.7. Pyrolysis Reactor ............................................................................................ 41
3.8. Pump Design .................................................................................................. 41
3.8.1 Pump Selection ............................................................................................. 41
3.8.2. Pump Calculation ........................................................................................ 42

CHAPTER Four: SITE LOCATION & PLANT LAYOUT

4.1. Plant Layout.................................................................................................... 44
4.1.1. Background.................................................................................................. 44
4.1.2. Objectives of Plant Layout .......................................................................... 44
4.1.3. Factors taken into considerations in plant layout ........................................ 44
4.2. Plant Location and Site Selection .................................................................. 47
4.3. VCM Plant location ........................................................................................ 48

CHAPTER Five: CONCLUSION & RECOMMENDATIONS

5.1. Conclusion ...................................................................................................... 49
5.2. Recommendations .......................................................................................... 50

References............................................................................................................. 51

II
List of Tables

Table 1-1: Physical Properties of Vinyl Chloride .................................................................. 4

Table 2-1: inlet stream condition ..................................................................................... 18
Tables 3-1: Column Internals Summary (C1) ........................................................................ 28
Table 3-2: Downcomer geometry (C1) .................................................................................. 29
Tables 3-3: Column Internals Summary (C2) ........................................................................ 31
Table 3-4: Downcomer geometry (C2) .................................................................................. 32
Table 3-5: Nozzle Parameters CSTR ..................................................................................... 33
Table 3-6: Nozzle Parameters PFR ........................................................................................ 35
Table 3-7: separator sizing .................................................................................................... 38
Table 3-8: Nozzle Parameters separator................................................................................. 38
Table 3-9: Overall Heater performance ................................................................................. 40
Table 3-10: Firebox Dimension……………… ..................................................................... 40
Table 3-11: Firebox and bank performance ..................................................................... 40
Table 3-12: Nozzle Parameter (Pyrolysis Reactor) ................................................................ 41

List of Figure

Figure 1-1: VCM & PVC……………………………………………………………………1

Figure 1-2: Amount of recycled PVC according to its application between 2001 and 2014..8
Figure 1-3: Average size of VCM plant capacity by country ................................................ 8
Figure2.1 Block diagram for balanced vinyl chloride monomer process. ............................. 13
Figure 2-2: Component list .................................................................................................... 14
Figure 2-3: fluid package ....................................................................................................... 14
Figure 2-4: kinetics parameters .............................................................................................. 16
Figure 2-5: oxychlorination reaction parameter ..................................................................... 17
Figure 2-6: Simulation of the direct chlorination and oxychlorination reactors system. ...... 19
Figure 2-7: Ethylene dichloride purification flowsheet. ........................................................ 21
Figure 2-8: Inlet and outlet streams to Purification process .................................................. 21
Figure 2-9: Ethylene Dichloride Pyrolysis flowsheet ............................................................ 23

III
Figure 2-10: Case study, dependence of boiling points on pressure for each species ........... 24
Figure 2-11: The final simulation flowsheet for vinyl chloride monomer manufacture ...... 25
Figure 3-1: Setting up a splitter to evaluate pressure effect on top and bottoms temperatures. ....................26

Figure 3-2: Rigorous Distillation Column C1 ....................................................................... 28

Figure 3-3: Hydraulic plot tray 1 (C1) ................................................................................... 29
Figure 3-4: Hydraulic plot feed tray (C1) ........................................................... 29
Figure 3-5: Hydraulic plot tray 13 (C1) ................................................................................. 30
Figure3-6: Setting up a splitter to evaluate pressure effect on top and bottoms temperature ……....………30

Figure 3-7: Rigorous Distillation Column C2 ....................................................................... 31

Figure 3-8: Hydraulic plot tray 1 (C2) ................................................................................... 32
Figure 3-9: Hydraulic plot feed tray (C2) ............................................................................. 32
Figure 3-10: Hydraulic plot tray 11 (C2) ............................................................................... 33
Figure 3-11: COMPONENTS OF FIRED HEATER ........................................................... 39
Figure 3-12: stream inlet and outlet from fired heater in Aspen Hysys ................................. 40
Figure 4-1: Plant layout .......................................................................................................... 46
Figure 4-2: Plant location ....................................................................................................... 48

IV
Abbreviations

V Volume of Reactor
𝜏 Residence Time
𝜐 Volumetric Flow Rate
D Diameter
FA Molar Flow Rate
K Rate Constant
A Frequency Factor
EA Activation Energy
R Gas Constant
T Temperature
P Pressure
-rA Rate of Reaction
W Weight of Catalyst
∈ Catalyst Void Fraction
𝜌𝑏 Particle Density
Vg Pore Volume
X Conversion Ratio
N Number of Tray
Xf Conc. of Solute in Feed on Solute Free Basis
Xn Conc. of Solute in Raffinate on Solute Free Basis
Ys Conc. of Solute in Solvent on Solute Free Basis
m Distribution Coefficient
E Extraction Factor
𝜂 Efficiency
Hp Pump Head
𝛾 Specific Weight of Fluid

V
Abstract

Vinyl chloride monomer (VCM) is a crucial component and the primary chemical used in
the manufacturing of polyvinyl chloride (PVC). VCM is predominantly produced by
thermally decomposing ethylene dichloride (EDC) in a pyrolysis furnace, utilizing ethylene
and chlorine as the essential raw materials. The objective of this project is to establish a
VCM production facility with a capacity of around 59 kilotons per year. Graduation project
aims to investigate the production of VCM from ethylene using Aspen HYSYS, a powerful
process simulation software widely used in the chemical engineering industry. The project
begins with a highlighting the industrial importance of VCM and the various methods
employed for its production. It explores the advantages and challenges associated with the
ethylene-based route, focusing on the reaction mechanism and process conditions. The
primary objective of this research is to develop a process simulation model for the
production of VCM from ethylene using Aspen HYSYS. The model is designed to
incorporate the necessary reaction kinetics, thermodynamics, and mass and energy balances
to accurately represent the industrial-scale VCM production process. Various process
parameters, such as temperature, pressure, reactant ratios, and catalyst types, are investigated
to optimize the production efficiency and product quality. Aspen HYSYS offers a
comprehensive platform for designing and analyzing chemical processes, enabling the
simulation of reaction kinetics, separation units, heat exchangers, and other equipment. The
project utilizes this software to model the VCM production process, considering the reactor
design, distillation columns, and other unit operations. The simulation results are analyzed to
evaluate the process performance.

VI
 CHAPTER ONE
INTRODUCTION

|Page1
1.1. Introduction

Vinyl chloride monomer (VCM) serves as the building block for polyvinyl chloride
(PVC). PVC is a widely utilized plastic with diverse applications in packaging, construction
materials, medical devices, and clothing. This versatility arises from the ability to modify the
properties of PVC using additives, enabling adjustments to its rigidity and other
characteristics. Consequently, there is a significant demand for PVC, resulting in the
production of over 40 million tons of this plastic annually. As a result, VCM holds
substantial value as a chemical. The primary usage of VCM (approximately 90%) lies in
PVC manufacturing, while its alternative application involves the production of chlorinated
solvents.

VCM PVC

Figure 1-1: VCM & PVC

There are various methods for industrially producing VCM, depending on the initial
materials used. In countries where oil is abundant, the most commonly employed process is
called the balanced process. It involves a combination of chlorination and oxychlorination
reactions using ethene derived from oil as the starting material. Another simpler approach is
the direct hydrochlorination of acetylene, which is derived from coal. Traditionally, this
reaction has been catalyzed by carbon-supported mercuric chloride. This method was
historically used for VCM production and is still prevalent in China due to the availability of
inexpensive coal, resulting in an annual production of over 13 million tons of VCM.
However, the deactivation of mercury-based catalysts poses a significant problem. Aside
from reduced activity, the leaching of toxic mercury from the catalyst leads to environmental

|Page1
concerns. The use of mercury and the associated environmental issues prompted the need for
a new catalyst. [1]

1.2. Background Information

1.2.1. Environmental Effects

Vinyl chloride (VC) is a gas that is flammable and colorless at room temperature. It
possesses a mild, sweet odor. However, when subjected to low temperatures or high
pressure, VC can exist in a liquid state. The primary sources of VC found in the environment
are attributed to human activities. In terms of air pollution, detectable amounts of VC are not
typically found in urban or rural air. However, it can be detected in the air surrounding VC
manufacturing facilities, hazardous waste sites, and landfills. Occupational exposure to VC
primarily occurs through inhalation of VC-contaminated air and direct contact with the skin.
When VC is absorbed by the skin or comes into contact with the eyes, it can enter the body.
In the atmosphere, VC degradation results in the formation of various byproducts including
hydrochloric acid, formaldehyde, formyl chloride, acetylene, chloroacetaldehyde,
chloroacetylchloranil, and chloroethylene epoxide. [2]

1.2.2. Health and safety

regulations (OSHA) require the monitoring of concentrations of harmful species in all

facilities where VCM is produced or used. The employees should not be exposed to more
than 1 ppm over 8 h, or no more than 5 ppm for periods exceeding 15 min. Chronic
exposures to more than 100 ppm may lead to serious diseases. On the other hand, VCM is
flammable by heat, flame and oxidizing agents. Large fires are difficult to extinguish.
Because of possible peroxide formation, the VCM must be stored or transported under an
inert atmosphere. The use of stabilizers prevents polymerization during processing and
storage. VCM is generally transported in railroad tank cars and tank trucks. [3]

|Page2
1.3. History

Vinyl chloride was first synthesized in 1833. The polymerization process was discovered
some 100 years later in Germany in the mid 1930. There after the industry developed
rapidly, both in Europe, which accounts for about 50 percent of world production, and in the
United States, which currently accounts for some 25 percent of world production. The fire
and explosion risks of vinyl chloride were fully appreciated from the beginning of the
industry, as was the acute narcotic effect induced by exposure to high concentrations of the
gas. Indeed, as early as 1933 Peoples and Leake had investigated the use of vinyl chloride as
a possible general anaesthetic. It was abandoned principally because of the adverse cardiac
effects it produced in dogs at anaesthetic concentrations. Apart from the acute narcotic
effect, vinyl chloride was regarded as being relatively non-toxic, and the first maximum
acceptable concentration published by the Manufacturing Chemists Association (1954) in the
United States recommended 500 ppm for worker exposure on the premise that 'in
concentrations well above 500 ppm vinyl chloride acts as a mild general anaesthetic'. Until
1960 when two fatalities were recorded in a Canadian polymerization plant (Danziger,
1960), there had been no reported industrial fatalities, and these only served to underline the
need for further precautions to prevent narcosis and effect rescue and resuscitation if it
should occur. In 1961, the Dow Chemical Company reported slight liver damage in animals
exposed to levels of 100 ppm and recommended that worker exposure levels be reduced to a
50 ppm time-weighted average (TWA) level. Despite this report, in 1962 the American
Conference of Governmental Industrial Hygienists, on the basis of further work at Yale,
adopted a recommendation that a TWA of 500 ppm provided an adequate margin of safety
for human exposure. This standard was subsequently. Notwithstanding, updating of the
epidemiological surveys continued, and on 22 January 1974 three deaths due to
angiosarcoma of the liver in former employees were reported to the National Institute of
Occupational Safety and Health from the B. F. Goodrich Plant in Louisville, Kentucky
(Creech and Johnson, 1974). [4]

|Page3
1.4. Physical and Chemical Characteristics

Vinyl chloride (VC), CH2 = CHCL, is gaseous at normal ambient temperature and
pressure having a boiling point of —135 °C. It is approximately twice as heavy as air. It is
only slightly soluble in water, but soluble in ethanol, ethyl ether and polyvinyl chloride
(PVC). The gas is highly flammable and explosive, having a lower explosive limit of 4
percent and an upper explosive limit of 22 percent in air. It is easily liquified by pressure,
and in this form has the property of being readily polymerized at temperatures in the range of
40-70 °C by exothermic reaction to form PVC, each molecule of which contains between
500- 1500 molecules of vinyl chloride, and which in the raw state has the appearance of a
fine white powder. [4]

Table 1-1: Physical Properties of Vinyl Chloride

Property Information
Molecular weight 62.5 g/mole
Color Colorless
Physical state Gas
Melting point -153.8 °C
Boiling point -13.37 °C
Odor Pleasant
Flash Point -77.75˚C
Density 0.969 g/ml
Solubility in water 2.7 g/L (0.0432 mol/L)
Vinyl Chloride is also called Chloroethene; chloroethylene; 1-chloroethylene; ethylene
monochloride; monovinyl chloride; monochloroethene; monochloroethylene; MVCs; VC;
VCM; vinyl chloride monomer. [5]

Chemical structure of vinyl chloride monomer

|Page4
The primary chemical process of vinyl chloride involves its conversion into polymers and
copolymers when a radical-generating initiator is present.

Furthermore, when vinyl chloride undergoes gas phase oxidation, it produces 74% formyl
chloride and 25% carbon monoxide when there is a high ratio of oxygen to chlorine.
Complete oxidation of vinyl chloride in the gas phase can be accomplished by utilizing a
cobalt chromite catalyst. Additionally, when vinyl chloride reacts with ozone in either the
liquid or gas phase, it results in the formation of formic acid and formyl chloride. [6]

|Page5
1.5. USES

Approximately 98% of the vinyl chloride (VC) produced in the United States is utilized in
the creation of a polymer known as polyvinyl chloride (PVC). PVC is composed of extended
repeating units of VC and serves as a chemical intermediate rather than a final product.
Compared to the monomer, PVC is highly stable, easily storable, and less hazardous. It finds
extensive application in various industries, including pipes, wire, cable coatings, packaging
materials, bottles, furniture, wall coverings, housewares, and automotive components. In
1974, the Environmental Protection Agency (EPA) prohibited the use of VC as aerosol hair
spray propellants and as an ingredient in pharmaceutical and cosmetic products.
Additionally, VC is employed in the production of 1,1,1-trichloroethane and copolymers
alongside vinyl acetate, vinyl stearate, and vinylidene chloride. [2]

1.6. Production and Demand Analysis

The origin of many commercially viable materials can be traced back to recycled waste
from the production of other materials. A notable example is vinyl chloride and its
derivative, polyvinyl chloride (PVC). In the 1920s, chemists at Union Carbide began
exploring polymers based on vinyl chloride. They discovered that the ethylene oxide plant of
the company generated significant quantities of ethylene dichloride waste, which could be
used to produce vinyl chloride, the monomer for PVC. However, the resulting polymer was
rigid and brittle. In the early 1930s, a scientist named Waldo Semon from Goodyear
successfully introduced "plasticizers" like tritolyl phosphate into the polymer, making it
more moldable and flexible. Goodyear marketed this material as Koroseal for wire and cable
insulation. Both Union Carbide and Goodyear found that adding heat stabilizers and
lubricants improved the performance of PVC, leading to its use in tubing, wall coverings,
draperies, and insulation. Throughout the 1930s, new applications for PVC emerged,
including vinyl coats and wall

coverings. Rigid and flexible sheets were introduced in 1938 and 1939, respectively. The
rigidity of PVC also made it suitable for fabricating pressure and sewer drainpipes.
|Page6
However, domestic production of PVC grew slowly, with less than 1 million pounds
produced in 1939. The production of PVC received a boost during World War II due to its
use in underwater cable insulation and flameproofing garments. Vinyl chloride monomer
production increased, reaching 120 million pounds per year by the end of the war. The
technology for producing vinyl chloride monomer remained largely unchanged until the
1950s, with two main processes being used: direct reaction of acetylene with hydrogen
chloride and thermal decomposition of ethylene dichloride. During this period, the major
producers of vinyl chloride monomer - Union Carbide, Goodyear, Dow Chemical, Allied
Chemical, Goodrich, Diamond Alkali, and Monsanto - also produced PVC. In 1955, Dow
Chemical began selling the monomer independently, leading to the development of a vibrant
merchant market for PVC. Engineering firms developed simple, off-the-shelf processing
technologies for less sophisticated producers. The entry of numerous producers into the
market and the increasing demand for PVC led to a decline in the price of vinyl chloride.
Despite vinyl chloride production reaching 2 billion pounds in 1965, demand continued to
rise. This resulted in falling prices and greater investments in production capacity. By the
mid-1970s, it became evident that the low price of vinyl chloride monomer, the presence of
many producers, and intense market competition without a dominant player meant that
substantial profits were unlikely for any participants, even though the market continued to
grow steadily. [7]

1.7. Market analysis

Vinyl chloride is primarily used to produce polyvinyl chloride (PVC). The demand for
vinyl chloride is heavily influenced by the PVC market, which accounts for over 98% of its
usage. The remaining 2% is utilized in the production of polyvinylidene chloride and
chlorinated solvents. PVC is the third most widely used synthetic plastic polymer in the
thermoplastic

family, following polyethylene (PE) and polypropylene (PP). The PVC market relies
significantly on the construction industry, which consumes approximately 75% of the total
output. Common applications of PVC include window profiles, pipes, conduits, fittings, and
|Page7
electrical wiring insulation due to its fire retardant properties. Due to the economic downturn
in the construction sector, PVC has experienced slower growth compared to other
commodity polymers in Europe. Additionally, European countries have made notable
progress in recycling PVC, particularly in France and Poland, leading to an increase in
recycled PVC volume. Figure 1.3 illustrates the growth of PVC usage in key applications.

Figure 1-2: Amount of recycled PVC according to its application between 2001 and 2014.

production capacity of ethylene-based vinyl chloride monomer (VCM). In the 1990s, the
largest VCM plant in the USA had a capacity of approximately 635,000 tons per year.
However, currently, there are several plants with capacities exceeding one million tons per
year. [8]

Figure 1-3: Average size of VCM plant capacity by country

|Page8
 CHAPTER TWO
PROCESS DESCRIPTION AND
SIMULATION WITH ASPEN HYSYS

|Page9
2.1. Background

Vinyl chloride was first produced using the process of dehydrating ethylene dichloride
(EDC) with alcoholic caustic potash. However, the first effective industrial process was
based on the hydro-chlorination of acetylene. Until the late 1940s, this process was used
almost exclusively. The normal method of producing acetylene was from calcium carbide.
“The high-energy requirement for carbide production was a serious drawback to the
continuing mass production of vinyl chloride by this method”. However, as ethylene became
more plentiful in the early 50’s, commercial processes were developed to produce vinyl
chloride from chlorine and ethylene via EDC, namely, the balanced ethylene route. Today
the balanced ethylene is responsible for well over 90% of the world’s vinyl chloride
production. “This process has been refined and the scale of operation has greatly increased,
but no fundamentally new processes have achieved commercial viability”. Although this is
true, it is still necessary to examine the alternative processes and determine if they can still
be utilized. All current production plants for vinyl chloride depend on the use of a C2
hydrocarbon feed stocks, specifically, acetylene, ethylene, or ethane. Commercial operations
using these compounds are confined to gas-phase processes. “Manufacture from acetylene is
a relatively simple single-stage process, but the cost of acetylene is high”. Ethane is by far
the least expensive C2 hydrocarbon, but it cannot be converted to vinyl chloride with high
selectivity. [9]

|Page9
2.2. ASPEN HYSYS

HYSYS, a powerful engineering simulation tool, stands out due to its unique program
architecture, interface design, engineering capabilities, and interactive operation. Its
integration of steady state and dynamic modeling capabilities, allowing for the evaluation of
the same model from different perspectives while sharing process information, represents a
significant advancement in engineering software. The various components of HYSYS offer a
robust approach to steady state modeling, providing a wide range of operations and property
methods to confidently model various processes. Furthermore, HYSYS maximizes the return
on simulation time by enhancing process understanding. Its strong thermodynamic
foundation, combined with flexible design and accurate property package calculations,
contributes to the creation of realistic models. HYSYS is widely used in educational
institutions, particularly in chemical engineering courses, and finds applications in research,
development, modeling, and design within various industries. It serves as an engineering
platform for modeling processes across different stages, from upstream and gas processing to
cryogenic facilities, refining, and chemical processes. [10]

2.3. Production Routes

2.3.1. Vinyl Chloride from Acetylene

The use of a catalyst is essential in the production of vinyl chloride from acetylene.
Typically, mercuric chloride deposited on active carbon is the catalyst of choice. In this
method, the feed gases undergo purification, drying, and mixing before entering the tubular
fixed bed reactors. These reactors are filled with pellets of mercuric chloride on active
carbon, which act as catalysts. It is common to employ a slight excess of HCl compared to
the stoichiometric ratio. The process achieves a high conversion rate, with approximately
99% conversion of acetylene and 98% conversion of HCl. Moreover, the selectivity to vinyl
chloride is favorable exceeding 98%.

| P a g e 10
The primary side reaction observed is the additional reaction of HCl with vinyl chloride,
resulting in the formation of 1,1-dichloroethane. However, a significant drawback of this
process is the volatility of the catalyst used, mercuric chloride. As a result, the acetylene
route is currently not commercially significant. [11]

2.3.2. Vinyl Chloride from Ethane

Numerous efforts have been made to create a method for directly producing vinyl chloride
using ethane, primarily because ethane is relatively inexpensive. However, a major obstacle
encountered when utilizing ethane is its molecular symmetry. Specifically, introducing
chlorine to ethane results in a wide range of products. Among the most promising
approaches are those involving high-temperature oxychlorination, employing specialized
catalysts to achieve desirable selectivity towards vinyl chloride and significant by-products
like ethylene, ethyl chloride, and EDC (ethylene dichloride). The ethylene can be chlorinated
to produce EDC and then recycled together with the ethyl chloride. Despite the feasibility of
this process, it has not progressed beyond the conceptual stage. The primary reason for this is
the significant challenge posed by the design of the oxychlorination reactor, as it requires
construction materials capable of withstanding temperatures reaching up to 500 degrees
Celsius. At such high temperatures, chlorine becomes highly corrosive to most construction
materials. [11]

| P a g e 11
2.3.3. Vinyl Chloride from ethylene

The method selected for manufacturing vinyl chloride involves a combination of two
processes known as direct chlorination and oxychlorination. This combined process is
commonly referred to as the balanced process. Direct chlorination, when used alone,
operates at lower temperatures and generates fewer secondary products compared to
oxychlorination. However, oxychlorination is employed in vinyl chloride production because
it effectively consumes hydrochloric acid (HCl), a significant by-product of the vinyl
chloride manufacturing process. [11]

Vinyl chloride monomer (VCM) is exclusively manufactured through the integrated

balanced ethylene route. In this balanced process, 1,2-dichloroethane (also known as
ethylene dichloride) is synthesized by directly chlorinating ethylene. The resulting ethylene
dichloride is then subjected to dehydrochlorination, which leads to the formation of VCM.
The hydrogen chloride (HCl) produced during this process is subsequently utilized in
oxychlorination to generate more ethylene dichloride. As a result, this overall process offers
the advantage of consuming HCl, the by-product, while efficiently converting both chlorine
atoms (which are expensive reactants) into VCM. This ensures a tightly closed material
balance, with VCM being the sole final product. [12]

| P a g e 12
The balanced process can be divided into four primary stages: (1) direct chlorination and
oxychlorination, (2) purification of EDC (ethylene dichloride), (3) pyrolysis of EDC, and (4)
purification of VCM (vinyl chloride monomer. [13]

Figure 2-1: Block diagram for balanced vinyl chloride monomer process.

direct chlorination reactor receives chlorine (Cl2), while the oxychlorination reactor receives
air or oxygen (O2). The outputs from these reactors are combined and passed through an
EDC purification process to obtain EDC (ethylene dichloride). The EDC then undergoes
pyrolysis, or thermal cracking, to produce VCM (vinyl chloride monomer) and HCl
(hydrochloric acid). The resulting mixture is further processed in a VCM purification system
to separate VCM from other components. The EDC is recycled back to the EDC purification
process, while the HCl is recycled back to the oxychlorination reactor, with no net
production or consumption.

| P a g e 13
To simulate this process in Aspen HYSYS, all the chemical components involved, such as
C2H4, Cl2, 1,2-dichloroethane, C2H3Cl, HCl, H2O, O2, and N2, are entered into the
component list. For air, it is assumed to consist of (21% O2 and 79% N2).

Figure 2-2: Component list

Subsequently, a suitable thermodynamic model, referred to as a "fluid package" in Aspen
HYSYS, is selected. In this case, the choice is the Soave-Redlich-Kwong (SRK) fluid
package.

Figure 2-3: fluid package

| P a g e 14
2.3.3.1. Direct Chlorination Reactors System

The direct chlorination of ethylene to produce EDC (ethylene dichloride) can be carried
out under two sets of conditions. The first option is to conduct the process at low
temperatures ranging from ( 50 to 70) degrees Celsius and at low pressures of (0 to 2)
atmospheres. Alternatively, the process can be performed at high temperatures between (90
and 150) degrees Celsius and at pressures of (1.5 to 5) atmospheres. The reaction is
facilitated by a catalyst consisting of (0.1 to 0.5) weight percent of ferric chloride (FeCl3),
and it is known to be highly exothermic. [13]

of 70%, due to its ability to achieve high selectivity for EDC, up to 99%. However, this
process requires the removal of the catalyst and external temperature control. On the other
hand, the high-temperature process allows for efficient heat recovery but results in lower
selectivity. For this particular case study, we have chosen to simulate the low- temperature
chlorination process using a temperature of 60 degrees Celsius and a pressure of 1.5
atmospheres. with the activation energy given in kilojoules per kilomole and concentrations
in kilomoles per cubic meter. [14]

………..(2-1)
……(2-2)

| P a g e 15
Therefore, as shown in Figure in the Reactions properties of the Aspen HYSYS equation

(2-2) is entered as a kinetic equation, with kinetics parameters.

Figure 2-4: Direct chlorination kinetics parameters

2.3.3.2. Oxychlorination of ethylene Reactors System

The balanced oxychlorination process involves the reaction of ethylene with hydrogen
chloride gas, which is obtained by pyrolysis EDC. This reaction is usually carried out in
either a fixed bed reactor (operating at temperatures of 230-300°C and pressures of 1.5- 14
atm gauge) or a fluidized bed reactor (operating at temperatures of 220-235°C and pressures
of 1.5-5 atm gauge). The reactor contains a catalyst consisting of copper chloride supported
on porous alumina. [15]

The procedure is additionally extremely exothermic, necessitating precise temperature

regulation. [16]

……(2-3)
The value of Ka was determined as 630 m3/kmol, indicating the adsorption capacity. The ɣ
alumina powder had a particle density of 1369 kg/m3 and a solid density of 3075 kg/m3 The

| P a g e 16
particles exhibited an internal surface area of 221,000 m2/kg. The copper loading on the
alumina carrier was 4.23 wt%, which corresponds to a CCl2 value of 0.993 kmol/m 3. [16]

Therefore, Eq. becomes:

……..(2-4)

Figure 2-5: oxychlorination reaction parameter

| P a g e 17
The oxychlorination reactor operates simultaneously with direct chlorination, with the
objective of producing 1,2-dichloroethane. However, it exhibits distinct behavior and
characteristics compared to the direct chlorination process. Firstly, the oxychlorination
reaction takes place in the gas phase to prevent corrosive issues caused by acid aqueous
solutions. Liquid phase oxychlorination is not employed in industrial applications. Gaseous
ethylene and oxygen react with hydrogen chloride, sourced from the vinyl chloride
purification section, in the presence of a heterogeneous catalyst, typically copper(II)
chloride.[8]

After adding all reactions into fluid package, Based on the information provided below, we
can enter the simulation environment to construct the process flowsheet, ensuring that all
streams and unit operations are defined accordingly.

Table 2-1: inlet stream condition

Above stream with the following assumptions:

1- The C2H4 stream is divided equally between direct chlorination reactor and
oxychlorination reactor.

2- Unless otherwise stated, there is no change in pressure throughout the system.

3- The reactors are maintained at the designated temperatures by removing or adding heat
externally, resulting in an isothermal modeling approach.

4- The C2H4 feed is provided with a slight excess (1.04 times more than the stoichiometric
amount) in the presence of Cl2 and HCl as the limiting agents in R1 and R2, respectively.

5- A pseudo HCl is generated as one of the feeds for R2, and it will be modified later by a
recycle stream.
| P a g e 18
R1 is represented as a continuous-stirred-tank-reactor (CSTR) with a residence time of
2.5814 hours. [17]

To achieve this residence time based on the volumetric flow rate, an "Adjust" logical
operation tool and a "Spreadsheet" are utilized.

….(2-5)
The "Adjust" tool is employed to modify the "Adjusted Variable," which corresponds to the
tank volume in order to satisfy the specified residence time of 2.5814 hours.
[17]
R2 is represented as a plug flow reactor (PFR) with a residence time of 0.09 hour.
initial PFR volume and its diameter are assumed, and a “Spreadsheet” is created to modify
the "Adjusted Variable," which corresponds to the PFR Volume in order to satisfy the
specified residence time of 0.09 hour.

Figure 2-6: Simulation of the direct chlorination and oxychlorination reactors system.

| P a g e 19
2.4. Ethylene Dichloride Purification

To prevent coking and fouling of the pyrolysis reactor, it is necessary to ensure that the
products obtained from direct chlorination, oxychlorination, and other recycle streams (to be
added later) have a minimum EDC purity of 99.5%. These products not only contain EDC
but also significant amounts of water, as well as small quantities of C2H4, HCl, and air. It is
important to note that other by-products, such as trichloroethane, have not been considered in
this particular case study. [12]

The purification process for industrial EDC involves the use of a wash tower and a reboiler
type thermosiphon to separate water from EDC and other organic compounds. This is
necessary because water readily forms a minimal azeotrope with EDC and many other
organic compounds in the process. To better simulate the actual system, it is suggested to
implement a reboiled absorption process, which includes a condenser and a decanter. This
helps to improve the representation of the real system. [17]

In this situation starting with a flash unit to separate the lighter gas components. This is
followed by a liquid-liquid extractor that combines aqueous washing with certain properties
of azeotropic separation. The final step involves a reboiled absorber, which is employed to
achieve the desired purification objective. By employing water as an extraction agent and
operating at specific conditions of 15°C temperature and 4 atm pressure, the first purification
stage effectively removes impurities and raises the purity of EDC. This results in an
increased EDC purity of 93% in the second purification stage. The reboiled absorber is
established in the final stage of EDC purification, maintaining a constant temperature and
pressure of 15°C and 4 atm throughout the process. This purification stage ensures that the
EDC purity reaches 99.5%, which satisfies the minimum requirement of 99.5%. The purified
EDC is obtained as a liquid product (Stream 17) at the bottom, with a loss of 16.98% of EDC
to the vapor product (Stream 16). The vapor product is then cooled to 90°C (to prevent
evaporation during mixing) and recycled back to the Flash column to repeat the purification
process. [12]

| P a g e 20
 Figure 2-7: Ethylene dichloride purification flowsheet.

Figure 2-8: Inlet and outlet streams to Purification process

| P a g e 21
2.5. Ethylene Dichloride Pyrolysis

The purified EDC is introduced into the endothermic pyrolysis unit, typically operating
at temperatures between 480 and 530 degrees Celsius .[18] , and under gauge pressures
ranging from 6 to 35 atmospheres. This process takes place within a lengthy coiled tube
located in a furnace. As a result, VCM is generated along with various secondary substances
[19]
including acetylene, ethylene, butadiene, trichloroethane, and vinyl acetylene. In this
context, we are focusing solely on the primary reaction of EDC converting into VCM. with
kinetics parameters:

. . . . . . . . . . . . (2-6)

To bring the result closer to the industrial data the value of k. [13]

........(2-7)

The provided kinetic information is incorporated as a fresh kinetic equation within the
Reactions" properties of the Properties mode. Once this reaction is included in the fluid
package, a plug flow reactor (PFR) is utilized to represent the pyrolysis reactor in the
simulation flowsheet. The PFR operates at a temperature of 550°C and a pressure of 26 atm.

The procedure can be conducted with or without a catalyst, but manufacturers generally
prefer the latter option. By appropriately designing the reactor, it is possible to achieve
conversion and yield levels similar to those obtained with the former configuration, while
also avoiding the additional expenses associated with catalysts. It is important to maintain
the conversion within the range of 50-60% to ensure a high level of selectivity. [8]

| P a g e 22
 Figure 2-9: Ethylene Dichloride Pyrolysis flowsheet

2.6. Vinyl chloride purification

In order to reduce the formation of coke and halt any additional reactions, it is crucial to
have a quench system or a transfer line exchanger that can rapidly cool down the pyrolysis
product. Subsequently, the VCM purification section comes into play, which aims to
separate the end product of VCM from a mixture containing primarily VCM, HCl, and EDC.
[12].
Therefore, it is necessary to have at least one separation unit for this purpose. Rapid
cooling of the furnace waste gas through quenching is necessary to halt pyrolysis reactions,
impede further decomposition of vinyl chloride, and reduce the formation of additional by-
products. [8]

Two distillation columns are utilized to achieve the separation of VCM from EDC, HCl, and
other by-products. The initial column, known as the HCl column, operates by distilling the
mixture containing hydrogen chloride to obtain a pure product as the overhead. This pure
HCl is then reused by recycling it back into the oxychlorination reactor. The residue obtained
as the bottom product from the HCl column is directed to the second column, referred to as
the VCM column. In the VCM column, an overhead product with a VCM purity of 99 wt%
is produced. The lower portion of the VCM column, which is the bottoms, is recycled back
to the lights column for further purification. [11]

| P a g e 23
In order to provide support for the argument, one can create a graph using the "Case Studies"
feature in Aspen HYSYS to visualize how the boiling points of different species vary with
changes in pressure.

Figure 2-10: Case study, dependence of boiling points on pressure for each species

Due to the significant disparity in boiling points among various substances, employing
distillation columns may be the most cost-effective approach. Initially, HCl appears to be a
favorable choice for extraction since it has a comparatively lower boiling point than EDC
and VCM. To ensure cost-effective processes, it is common practice to regulate the
separation equipment to function with a reboiler temperature below 186°C (366°F) and a
condenser temperature ranging from 25-49°C (80-120°F). [12]

| P a g e 24
Figure 2-11: The final simulation flowsheet for vinyl chloride monomer manufacture

| P a g e 25
 CHAPTER THREE
EQUIPMENT DESIGN

|Page1
3.1. Simulation of Rigorous Distillation Column (C1 & C2)

Step 1: Justification of Operating Pressure with Splitter: One possible approach to

examine the impact of pressure is by utilizing the splitter, where the initial input is a
saturated liquid feed at a temperature of 10.56 C and a pressure of 16 atm.

Figure3-1: Setting up a splitter to evaluate pressure effect on top and bottoms temperatures

The assumption is made that the pressure drop across the column is minimal, so all stream
pressures are balanced. Then, the fractions for separation are determined, with HCl exiting as
distillate (D), and a mixture of EDC and VCM as the bottom product (W). distillate
temperature of -26.44C and a bottoms temperature of 147 C.

| P a g e 26
Step 2: Estimation of Reflux Ratio, Number of Trays, and Feed Stage with Shortcut
Distillation Model:

Once the desired operating pressure is determined, a simplified distillation column is built
to estimate the appropriate reflux ratio, number of trays, and optimal stage for feeding. In
this configuration, HCl, which is the light component, is recovered as a liquid in tray D1
with a mole fraction of 0.0001, while the remaining components are collected as bottoms in
tray B1, with VCM being the heavier component. The distillate contains VCM with a mole
fraction of 0.0001. By choosing a reflux ratio 1.75 times greater than the minimum reflux
calculated using Aspen HYSYS software, the column is successfully optimized, providing us
with the necessary information to proceed.

Step 3: Modeling with Rigorous Distillation Column:

Before the distillation process begins, a cooler is utilized to simulate the quench tower.
Its purpose is to lower the temperature of the pyrolysis outlet vapor stream (Stream 20) to its
dew point, which is 157°C at 26 atm (Stream 21). To establish an operating pressure of 16
atm for the first column, a condenser (also modeled as a cooler) is employed. This condenser
produces a saturated liquid feed at 30°C, followed by a control valve that reduces the
pressure from 26 atm to 16 atm.

In order for the column to reach a state of convergence, two variables need to be specified.
One of these variables can be the reflux ratio, which is set at 1.75 times the minimum reflux.
The other variable can be the column component recovery parameter. The desired
component recovery for HCl from the feed is set at 99.99%. With no degrees of freedom
remaining, we initiate the convergence process by clicking the "Run" button, and the column
reaches a converged state.

| P a g e 27
 Figure 3-2: Rigorous Distillation Column C1

Tables 3-1: Column Internals Summary (C1)

Property Value Unit
Number of stages 13
Total height 7.925 m
Number of sections 2
Number of diameters 2

Sections
Section Start End Diameter Section Internals Type Tray
(m) Height (m) Type

CS-1 Stage 1 Stage 6 0.61 3.658 Trayed Bubble-Cap

CS-2 Stage 7 Stage 13 0.92 4.267 Trayed Bubble-Cap

| P a g e 28
 Table 3-2: Downcomer geometry (C1)
Property Side Unit

Downcomer clearance 0.0381 m

Downcomer width top 0.09545 m

Downcomer width bottom 0.09545 m

Downcomer area top 0.02922 m2

Downcomer area bottom 0.02922 m2

Figure 3-3: Hydraulic plot tray 1 (C1)

Figure 3-4: Hydraulic plot feed tray (C1)

| P a g e 29
 Figure 3-5: Hydraulic plot tray 13 (C1)

For the second column, we have chosen an operating pressure 5 atm. A control valve is
placed at the feed to Column 2 to reduce the pressure from 16 atm to 4.8 atm. The same
procedure follows to set up the second rigorous distillation column.

Figure 3-6: Setting up a splitter to evaluate pressure effect on top and bottoms temperatures.

| P a g e 30
 Figure 3-7: Rigorous Distillation Column C2

Tables 3-3: Column Internals Summary (C2)

Property Value Unit
Number of stages 11
Total height 6.600 m
Number of sections 1
Number of diameters 1
Maximum Weir Loading 33.24 (m3/h-m)
Weir Height 5.000e-002 m
Tray Volume 0.9719 m3

| P a g e 31
 Table 3-4: Downcomer geometry (C2)

Property Side Unit

Downcomer clearance 0.03730 m
Downcomer width top 0.1252 m
Downcomer width bottom 0.1252 m
Downcomer area top 0.05027 m2
Downcomer area bottom 0.05027 m2

Figure 3-8: Hydraulic plot tray 1 (C2)

Figure 3-9: Hydraulic plot feed tray (C2)

| P a g e 32
 Figure 3-10: Hydraulic plot tray 11 (C2)

3.2. CSTR Volume Calculation:

𝑉𝑜𝑙𝑢𝑚𝑒 (𝑉)
Residence Time (𝜏)=
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 (𝜐)

V=𝜏 ∗ 𝜐
𝑚3
V=(2.5814 h)(1039.355 )
ℎ

V=2683 m3

Geometry:
Shape: Sphere
4 𝜋
V= 𝜋 ∗ 𝑟 3 = 𝐷3
3 6
𝜋
2683 m3= ∗ 𝐷3
6

D=17.24 m
Table 3-5: Nozzle Parameters CSTR
a 6 7
Elevation (Base) (m) 8.62 17.24 0
Elevation (Ground) 8.62 17.24 0
(m)
Diameter (m) 0.862 0.862 0.862

| P a g e 33
 𝐹𝐴 ∗ 𝑋
Weight of catalyst (W) =
−𝑟𝐴

−𝑟𝐴 = 𝑘 [𝐶2𝐻4][𝐶𝑙2]
𝑃𝐶2𝐻4 152∗ 103 𝑃𝑎 𝐾𝑚𝑜𝑙
[C2H4]= = 𝑃𝑎∗𝑚3
∗ 0.5312 = 0.0292
𝑅∗𝑇 8314 𝐾𝑚𝑜𝑙∗𝐾∗(60+273)𝐾 𝑚3

𝑃𝐶𝑙2 152∗ 103 𝑃𝑎 𝐾𝑚𝑜𝑙𝑒

[Cl2] = = 𝑃𝑎∗𝑚3
∗ 0.4688 = 0.0257
𝑅∗𝑇 8314 𝐾𝑚𝑜𝑙∗𝐾∗(60+273)𝐾 𝑚3

𝐸
(– 𝑅∗𝑇)
k=A𝑒
17930
(−8.134∗(60+273))
k = 11493 * 𝑒
𝑚3
k= 17.6937
𝐾𝑚𝑜𝑙∗𝑠

𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙
−𝑟𝐴 = 17.6937 ∗ 0.0292 ∗ 0.0257 = 0.01328 = 47.8
𝑚3 ∗ 𝑠 𝑚3 ∗ ℎ

𝑘𝑚𝑜𝑙
47.8
−𝑟𝐴 = 𝑚3 ∗ ℎ = 0.0165 𝑘𝑚𝑜𝑙
𝑘𝑔 𝑘𝑔 ∗ ℎ
2900 3
𝑚

𝑘𝑚𝑜𝑙
29.05 ∗ 0.997
𝑊= ℎ = 1755.3 𝑘𝑔 𝑓𝑜𝑟 𝑒𝑎𝑐ℎ 𝐶𝑆𝑇𝑅
𝑘𝑚𝑜𝑙
0.0165
𝑘𝑔 ∗ ℎ

| P a g e 34
3.3. Plug Flow Reactor Calculation (Oxychlorination Reactor):

𝑉𝑜𝑙𝑢𝑚𝑒 (𝑉)
Residence Time (𝜏)=
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 (𝜐)

V=𝜏 ∗ 𝜐
𝑚3
V=(0.09 h)*(3070 )
ℎ

V=276 m3

Geometry:
Shape: Cylinder
L=1.5*D
𝜋
V= 𝐷2 ∗ 𝐿
4
𝜋
V= ∗ 1.5𝐷3
4
𝜋
276 m3 = ∗ 1.5𝐷3
4

D=6.164 m
L=9.24 m
Material Construction– stainless steel ( shell and nozzle)

Table 3-6: Nozzle Parameters PFR

8 Feed2 Heated
Elevation (Base) (m) 0 0
Elevation (Ground) (m) 0 0
Diameter (m) 0.05 0.05

| P a g e 35
Catalyst Void Fraction
∈= 𝜌𝑝 ∗ 𝑉𝑔
𝐾𝑔
𝜌𝑝 = 1369
𝑚3
𝑐𝑚3 𝑚3
𝑉𝑔 = 0.5 = 0.0005
𝑔 𝑘𝑔

𝑘𝑔 𝑚3
∈ = 1369 3 ∗ 0.0005
𝑚 𝑘𝑔
∈ = 0.6845

Weight of catalyst PFR

𝑑𝑋 −𝑟𝐴
=
𝑑𝑊 𝐹𝐴
𝐾𝑚𝑜𝑙 𝐾𝑚𝑜𝑙
−𝑟𝐴 = 1.037 ∗ 10−2 = 37.332
𝑚3 ∗ 𝑠 𝑚3 ∗ ℎ

𝑘𝑚𝑜𝑙
−𝑟𝐴 37.332 3
−𝑟𝐴 = = 𝑚 ∗ ℎ = 0.0385 𝑘𝑚𝑜𝑙
𝜌𝑏 𝑘𝑔 𝑘𝑔 ∗ ℎ
970.2 3
𝑚
𝐹𝐴 1
W=
−𝑟𝐴
∫0 𝑑𝑋
𝑘𝑚𝑜𝑙
60.51 ℎ
W= 𝑘𝑚𝑜𝑙 ∗ 0.967 = 1520 𝑘𝑔
0.0385 𝑘𝑔∗ℎ

| P a g e 36
3.4. Wash Tower Calculation:

By using Kremser Equation

𝑌
𝑋𝑓 − 𝑚𝑠 1 1
log [ 𝑌𝑠 ](1−𝐸)+𝐸
𝑋𝑛 − 𝑚
N= log 𝐸

0.224
Xf = =0.2887
1−0.224

0.065
Xn = =0.06952
1−0.065
1
Ys= =1
1−0

𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡 𝑖𝑛 𝑒𝑥𝑡𝑟𝑎𝑐𝑡 𝑝ℎ𝑎𝑠𝑒 1

m= = =15.4
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑟𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒 𝑝ℎ𝑎𝑠𝑒 0.0.65

E=(S/F)*(m)=(312/312)*(15.4)=15.4

1
0.2887− 1 1
log[ 15.4
1 ](1−15.4)+15.4
0.06952−
15.4
N= =1.384
log[15.4]

1.384
Actual Number of tray = =2
0.7

Tray space =0.5

Column height (h) = 0.5 * 2 =1 m

| P a g e 37
3.5. Separator (V-100)
Shape: sphere
Table 3-7: separator sizing
Volume (m3) 0.4003
Diameter (m) 0.9144
Material Type Carbon Steel
Allowable Stress [kPa] 94458.2
Corrosion Allowance [mm] 3.175

Table3-8: Nozzle Parameters separator

Stream 10 Stream 11 Stream 12
Diameter (m) 0.05 0.05 0.05
Elevation (Base) (m) 0.4572 0.9144 0.00
Elevation (Ground) (m) 0.4572 0.9144 0.00
Elevation (% of Height) 50% 100% 0%

3.6. Fired Heater (FH-100)

A fired heater, also known as a furnace or process heater, is a type of heat exchanger that
utilizes the hot gases produced by combustion to increase the temperature of a substance
flowing through a network of tubes within the heater. Its purpose can vary, with some
heaters merely raising the temperature of the substance for further processing, while others
facilitate chemical reactions within the substance as it passes through the tubes. Fired heaters
are used throughout hydrocarbon and chemical processing industries such as refineries, gas
plants, petrochemicals, chemicals and synthetics, olefins, ammonia and fertilizer plants.
Most of the unit operations require one or more fired heaters as start-up heater, fired reboiler,
cracking furnace, process heater, process heater vaporizer, crude oil heater or reformer
furnace.20

| P a g e 38
 Figure 3-11: COMPONENTS OF FIRED HEATER

3.6.1. Rigorous design of a fired heater in Aspen HYSYS

The rigorous design of a fired heater in Aspen HYSYS involves modeling and simulating
the heater's components and processes to optimize performance and efficiency. The software
provides tools for parameter optimization and visualization of temperature profiles, pressure
drops, and overall heater performance.

| P a g e 39
 Table 3-9: Overall Heater performance

Heater Duty [kJ/h] 1.518e+007

Heater Efficiency (%) 92.74
Fuel Flow [kg/h] 327.19
Oxidant Flow [kg/h] 5884
Excess Oxidant (%) 5
Heat from fuel [kJ/h] 1.637e+007
Firebox Gas Temperature [C] 741.3
Bridgewall Temperature [C] 624
Stack Inlet Temperature [C] 145.7
Stack O2 (Mass % dry) 1.192
Draft at Bridgewall [kPa] -4.352e-002

Table 3-10: Firebox Dimension

Height (m) 12
Inner diameter (m) 4
Elevation of floor of firebox (m) 0.25
Elevation of top of firebox (m) 12.25
Material Construction Stainless steel

Figure 3-12: stream inlet and outlet from fired heater in Aspen Hysys
Table 3-11: Firebox and bank performance

Firebox Bank 1 Bank 2

Stream 18 18 18
Stream Duty [kJ/h] 1.136e+007 1.278e+006 2.542e+006
Stream Inlet T [C] 238.69 217.866 138.797
Stream Outlet T [C] 550 238.69 217.866
Peak Tube Wall T [C] 559.128 279.4199 281.705

| P a g e 40
3.7. Pyrolysis Reactor

𝑉𝑜𝑙𝑢𝑚𝑒 (𝑉)
Residence Time (𝜏)=
𝑉𝑜𝑙𝑢𝑚𝑒𝑡𝑟𝑖𝑐 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 (𝜐)

V=𝜏 ∗ 𝜐
𝑚3
V=(0.0 39425 h)(507.3 )
ℎ

V=20 m3
Geometry:
Shape: Cylinder
Material Construction– stainless steel ( shell and nozzle)

Table 3.12 Nozzle Parameter (Pyrolysis Reactor)

20 Feed Heated
Elevation (Base) (m) 0 0
Elevation (Ground) (m) 0 0
Diameter (m) 0.05 0.05

3.8. Pump Design

3.8.1 Pump Selection
The selection of pumping equipment is a critical factor that determines both the process
parameters and the performance of the unit being developed. When choosing a pump, three
groups of criteria can be identified:

1. Process and design requirements: This includes considering the specific needs and
specifications of the process and design.

2. Nature of the pumped medium: It is important to take into account the characteristics of
the fluid being pumped, such as its viscosity, temperature, and corrosiveness.

| P a g e 41
3. Key design parameters: These are the essential factors in the design of the pump, such as
flow rate, pressure, and efficiency.
The term "pump" typically refers to devices used for transferring liquids. Similar to
compressors, pumps can be classified into two main categories based on their operating
principles:
1. Positive-displacement pumps: These pumps generate pressure by trapping a certain
amount of liquid in a chamber and then compressing it to the desired discharge pressure.
Reciprocating and rotary pumps are the most common types of positive-displacement
pumps.
2. Dynamic pumps: Dynamic pumps work by first imparting kinetic energy to the fluid,
which is then converted into pressure. Centrifugal and axial pumps are the most common
types of dynamic pumps.

In the chemical process industry, the single-stage, horizontal, overhung, centrifugal pump is
the most widely used type. Other types of pumps are employed when specific requirements,
such as high head or unique process considerations, are specified.

3.8.2. Pump Calculation

Available information
𝑘𝑔
𝜌 = 1061
𝑚3
𝑃1 = 405.3 ∗ 103 𝑃𝑎
𝑃2 = 2634 ∗ 103 𝑃𝑎
𝜂 = 75%
𝑘𝑔
ṁ = 1.957 ∗ 104
ℎ
𝑚3
𝜐 = 18.44
ℎ

| P a g e 42
𝑃1 𝑉1 𝑃2 𝑉2
+ 𝑍1 + + 𝐻𝑝 = + 𝑍2 +
𝛾 2𝑔 𝛾 2𝑔
There is no change in elevation 𝑍1 = 𝑍2

At constant Flow rate 𝑉1 = 𝑉2

Equation become
𝑃2 − 𝑃1
𝐻𝑝 =
𝛾

𝑘𝑔 𝑚
𝛾 = 𝜌 ∗ 𝑔 = 1061 ∗ 9.81
𝑚3 𝑠2
𝑘𝑔
𝛾 = 10408.41
𝑚2 ∗ 𝑠 2
103 ( 2634 − 405.3 )
𝐻𝑝 =
10408.41
𝐻𝑝 = 214.125 𝑚

Power = 𝐻𝑝 ∗ 𝜐 ∗ 𝜌 ∗ 𝑔
18.44
Power = 214.125 ∗ ∗ 10408.41
3600

Power=11415.9 watt

11415.9
Power At 75% efficiency =
0.75

Power = 15.22 Kw

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 CHAPTER FOUR
SITE LOCATION & PLANT LAYOUT

| P a g e 26
4.1. Plant Layout

4.1.1. Background

A facility layout is an integration of the physical arrangement of departments,

workstations, machines, equipments, materials, common areas etc, within an existing or
proposed industry. Most plant layouts are designed properly for the initial conditions of the
business. However these layouts provide many bottlenecks during growth period. Hence as
long as capacity grows, it has to adapt the internal and external changes for which a re-
layout is necessary. The reasons for a re-layout are due to changes in production volume,
changes in process and technology and changes in the product. [21]

4.1.2. Objectives of Plant Layout

The main objective consists of organizing equipment and working areas in the most
efficient way, and at the same time satisfactory and safe for the personnel doing the work.

1-Sense of Unity: The feeling of being a unit pursuing the same objective.

2-Minimum Movement of people, material and resources.

3-Safety: In the movement of materials and personnel work flow.

4-Flexibility: In designing the plant layout taking into account the changes over short and
medium terms in the production process and manufacturing volumes.22

4.1.3. Factors taken into considerations in plant layout

The final solution for a Plant Layout has to take into account a balance among the
characteristics and considerations of all factors affecting plant layout, in order to get the
maximum advantages. The factors affecting plant layout can be grouped into 8 categories:

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1-Materials: The layout of the productive equipment will depend on the characteristics of
the product to be managed at the facility, as well as the different parts and materials to
work on. Main factors to be considered: size, shape, volume, weight, and the physical-
chemical characteristics, since they influence the manufacturing methods and storage and
material handling processes. The sequence and order of the operations will affect plant
layout as well, taking into account the variety and quantity to produce.

2-Machinery: Having information about the processes, machinery, tools and necessary
equipment, as well as their use and requirements is essential to design a correct layout.

3-Labour: Labour has to be organized in the production process (direct labour, supervision
and auxiliary services). Environment considerations: employees’ safety, light conditions,
ventilation, temperature, noise, etc.

4-Material Handling: Material handling does not add value to the product; it’s just waste.

Objective: Minimize material handling as well as combining with other operations when
possible, eliminating unnecessary and costly movements.

5-Waiting Time: Objective: Continuous Material Flow through the facility, avoiding the cost
of waiting time and demurrages that happen when the flow stops.

6-Auxiliary Services: Support the main production activities at the plant: Related to labor:
Accessibility paths, fire protection installations, supervision, safety, etc.

7-The building: If it has been already selected, its characteristics will be a constraint at the
moment of designing the layout, which is different if the building has to be built.

8-Future Changes: One of the main objectives of plant layout is flexibility. It’s important to
forecast the future changes to avoid having an inefficient plant layout in a short term.22

| P a g e 45
Figure 4-1: Plant Layout

| P a g e 46
4.2. Plant Location and Site Selection

Facility location is a critical aspect of strategic planning for a broad spectrum of public
and private firms. Whether a retail chain siting a new outlet, a manufacturer choosing where
to position a warehouse, or a city planner selecting locations for fire stations, strategic
planners are often challenged by difficult spatial resource allocation decisions. 23

When determining an appropriate site, numerous factors need to be taken into consideration.
The primary considerations include:

1- Proximity to Market: Select a location that is close to your target market to reduce
transportation costs, lead times, and improve customer service. Consider factors such as
access to major roads, highways, ports, and distribution networks.

2- Availability of Resources: Assess the availability and cost of essential resources like raw
materials, labor, energy, and water. Ensure that the chosen location has an adequate supply
of these resources to support your plant's operations.

3-Infrastructure: Evaluate the quality and availability of infrastructure, including

transportation networks, utilities (electricity, water, gas), telecommunications, and waste
management systems. A well-developed infrastructure can facilitate smooth operations and
timely delivery of goods.

4- Labor Force: Consider the availability of skilled and semi-skilled labor in the area.
Evaluate the local labor market's size, quality, wage rates, and labor laws. Also, assess
factors like workforce education levels, training facilities, and labor unions.

5- Government Regulations and Incentives: Understand the regulatory environment and

government policies in the potential plant location. Consider factors such as zoning
regulations, environmental regulations, taxation policies, and any available incentives or
grants for businesses.

6- Access to Suppliers: Consider the proximity and accessibility of suppliers. Being close to
key suppliers can reduce transportation costs, improve supply chain efficiency, and minimize
inventory carrying costs.

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7- Risk Assessment: Evaluate potential risks and vulnerabilities associated with the location,
such as natural disasters, political instability, social unrest, and security concerns. Implement
risk mitigation strategies and consider contingency plans.

4.3. VCM Plant location

Considering the aforementioned factors, the suggested site for the proposed plant is in
Basra, specifically in the Al-Zubair area, close to petrochemical factory.

Figure 4-2: VCM Plant location

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 CHAPTER FIVE
CONCLUSION & RECOMMENDATIONS

| P a g e 49
5.1. Conclusion

After studying this Graduation Project, individuals should possess the ability to create a
process flowsheet and provide justification for the usage of recycle streams, various reactor
types, and their kinetics. They should also be familiar with operational tools such as Adjust,
Set, and Spreadsheet. Furthermore, readers should have a solid understanding of the Splitter-
Shortcut Distillation & Rigorous Distillation approach when designing a distillation column.
Additionally, they should know how to determine physical and chemical properties using
Aspen HYSYS through the utilization of features like Case Study. Lastly, individuals should
be capable of independently exploring more advanced features and options in Aspen HYSYS
and other software to address additional chemical engineering challenges.

| P a g e 49
5.2. Recommendations

To enhance the efficiency, technical robustness, cost-effectiveness, and sustainability of

the existing vinyl chloride production process, there is significant scope for improvement. It
is advisable to prioritize the following measures:

1. Mass integration optimization should be undertaken to decrease the expenditure on fresh

feed. By analyzing the entire process, opportunities can be identified for reducing fresh feed
requirements through process modifications, recycling streams, and utilizing waste streams
from other plant processes. This would result in a reduction in overall production costs.

2. Close control of the reactor temperature is crucial to maintaining a sustainable vinyl

chloride yield, minimizing or eliminating side reactions, and preventing catalyst
deactivation. Maintaining the reactor temperature within the optimal range will help ensure
efficient production and extend the catalyst's lifespan, thereby reducing the need for frequent
replacement.

3. It is recommended to enhance the quality of separation in the vinyl chloride monomers

(VCM) column. By improving the separation efficiency, the discharge of chemicals into the
environment can be reduced. This can be achieved through process optimization, equipment
upgrades.

4. Conduct a heat integration study to identify opportunities for optimizing energy usage
within the plant. By analyzing the heat exchange processes and implementing energy-
efficient practices, overall energy consumption can be minimized, leading to cost savings
and improved sustainability.

By implementing these recommendations, the vinyl chloride production plant can achieve
greater efficiency, technical reliability, cost-effectiveness, and sustainability.

| P a g e 50
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