BLUEPRINT INC.

JOB CODE
4-152
DOCUMENT No.
R-L2-001
REV
0

DATE: 16-FEB-2022 SHEET 1 of 18

C. Buenaflor,
E. Gonzales,
Prepared Engineer F. Lleva
P. Manaog

Checked Lead Engineer J. Nunez

Approved Professor Engr. Aguilar

OWNER DOC. NO.:

PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE

FROM ETHYLENE

[BICOL UNIVERSITY]

REV. DATE PAGE DESCRIPTION PREP’D CHK’D APP’D

0 02-16-22 ALL ISSUED FOR REVIEW

 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
DRAFT PROPOSAL
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REVISION HISTORY

REV. SEC.
SECTION DESCRIPTION REVISIONS MADE
NO. NO.
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
DRAFT PROPOSAL
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TABLE OF CONTENTS

EXECUTIVE SUMMARY-----------------------------------------------------------------------------------------------4
ACKNOWLEDGEMENT------------------------------------------------------------------------------------------------4
List of Figures--------------------------------------------------------------------------------------------------------------4
List of Tables---------------------------------------------------------------------------------------------------------------4
List of Equations----------------------------------------------------------------------------------------------------------4
List of Acronyms----------------------------------------------------------------------------------------------------------4

CHAPTER 1 – PROJECT DESIGN BASIS AND MARKET----------------------------------------------------5

1.1 Project Background-------------------------------------------------------------------------------------------------5
1.1.1 Uses----------------------------------------------------------------------------------------------------------------5
1.2 Design Objectives---------------------------------------------------------------------------------------------------5
1.3 Process Description------------------------------------------------------------------------------------------------5
1.3.1 Block Flow Diagram--------------------------------------------------------------------------------------------6
1.3.2 Chemistry of Process------------------------------------------------------------------------------------------7
1.4 Plant Capacity and Location-------------------------------------------------------------------------------------7
1.4.1 Capacity-----------------------------------------------------------------------------------------------------------7
1.4.2 Location-----------------------------------------------------------------------------------------------------------8
1.4.3 Site Consideration----------------------------------------------------------------------------------------------8
1.4.4 Waste Disposal and Material Recovery------------------------------------------------------------------8
1.4.5 Environmental Consideration--------------------------------------------------------------------------------9
1.5 Key Feeds--------------------------------------------------------------------------------------------------------------9
1.5.1 Composition------------------------------------------------------------------------------------------------------9
1.5.2 Properties and Uses-------------------------------------------------------------------------------------------9
1.5.3 Chemical Safety Guide----------------------------------------------------------------------------------------11
1.6 Product Description------------------------------------------------------------------------------------------------11
1.6.1 Product Specifications-----------------------------------------------------------------------------------------11
1.6.2 Products (Main and By-products)--------------------------------------------------------------------------12
1.6.3 Properties and Uses (Main and By-products)-----------------------------------------------------------13
1.6.4 Chemical Safety Guide----------------------------------------------------------------------------------------14
1.7 Battery Limit Conditions------------------------------------------------------------------------------------------14
1.7.1 Feeds, Flare/vents, and Utitilies----------------------------------------------------------------------------15
1.8 Market--------------------------------------------------------------------------------------------------------------------16
1.8.1 Customer/Market Players------------------------------------------------------------------------------------17
1.9 Specific Design Requirement and Constrains-------------------------------------------------------------17
1.10 About the Company-----------------------------------------------------------------------------------------------17

REFERENCES--------------------------------------------------------------------------------------------------------------18

EXECUTIVE SUMMARY
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
DRAFT PROPOSAL
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ACKNOWLEGEMENT

List of Figures

List of Tables

List of Equations

List of Acronyms
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
DRAFT PROPOSAL
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CHAPTER 1 – PROJECT DESIGN BASIS AND MARKET

1.1. Project Background

The Philippine plastics sector is relatively new, having emerged in the mid-1960s with the introduction of
injection, extrusion, and blow molding techniques. Plastic pipe production began in the 1970s, in response to
rising demand for the commodity as a component of government waterworks projects.1

The demand for vinyl chloride monomer is predicted to expand at a CAGR (compound annual growth
rate) of over 4% over the forecast period. The major factor driving the growth of the market is the high demand
from the building & construction sector for various applications. Moreover, rising demand for vinyl chloride
monomer across the healthcare sector is predicted to increase the product demand further.2

In addition, local PVC manufacturers are currently reliant on imported VCM, with Mabuhay Vinyl
Corporation relying on imported VCM for around two-thirds of its rated capacity and Philippine Vinyl
Consortium, Inc. completely reliant.3 To address this problem, Blueprint Inc. proposes a plant design for the
production of vinyl chloride from ethylene.

Vinyl chloride is a colorless, flammable, and toxic gas with the chemical formula C2H3Cl. The
production of vinyl chloride begins with ethylene. There are two ways to make vinyl chloride from ethylene. In
one, ethylene is converted to 1,2-dichloroethane (ethylene chloride) by reaction with chlorine. Heating 1,2-
dichloroethane in the presence of a charcoal catalyst gives vinyl chloride and hydrogen chloride. Another way
is through the process called oxychlorination. In this kind of procedure, ethylene, hydrogen chloride, and
oxygen are heated in the presence of a copper catalyst to give vinyl chloride and water.

In this project, the designed vinyl chloride plant will integrate the two aforementioned procedures so that
the hydrogen chloride produced by heating 1,2-dichloroethane is used as a reactant in the oxychlorination
method.

1.1.1. Uses

Vinyl chloride can be as hard as industrial pipes, malleable as plastic wrap, or thin and flexible as
wall covering. It can also be entirely transparent or color-matched to any desired hue. It is used
primarily to make polyvinyl chloride (PVC).

PVC is the world's third-most widely produced synthetic polymer of plastic. It is economical,
versatile, and is used in a variety of applications in the building and construction, health care,
electronics, automobile and other sectors, in products ranging from piping and siding, blood bags and
tubing, to wire and cable insulation, windshield system components and more.

1.2. Design Objectives

The main focus of the design is to minimize environmental impact by reducing the hazardous
byproducts of the VMC production while maintaining profitability using CuCl2 catalyst. Reducing the amount of
waste produce will also prevent high-cost treatment and separation costs downstream in the process.
Environmental friendliness demands design that goes above the bare minimum of legal requirements while
also preserving plant profitability.
This project also aims to design a plant that can produce 25000 MT per year of vinyl chloride monomer,
utilizing both direct chlorination and oxychlorination processes. The proposed plant will be located at Ocampo,
Camarines Sur.

1.3. Process Description

The five main processes involved in the production of vinyl chloride monomer (VCM) are as follows: (a)
direct chlorination of ethylene to form ethylene dichloride (EDC), (b) oxychlorination of ethylene to form EDC
from recycled HCl and oxygen, (c) purification of EDC, (d) thermal cracking of EDC to form VCM and HCl, and
(e) the purification of VCM.
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1.3.1. Block Flow Diagram

Figure 1: Vinyl Chloride Plant PFD

a. Direct chlorination of Ethylene

The ethylene and chlorine direct chlorination process is an exothermic reaction that uses the EDC
product as the reaction medium. Typical operating temperatures range from 50 to 120°C, with applied
pressures ranging from atmospheric to 5 bar. The direct chlorination reaction is currently used in two
ways: low temperature chlorination and high temperature chlorination. For low temperature chlorination,
the reaction is operated at temperatures between 20 to 70°C which is lower than the EDC boiling point.
For high temperature chlorination, the reaction is operated at a temperature higher than the EDC boiling
point. The temperature range is approximately 85 to 200°C, with a most commonly used operation
temperature of approximately 100°C. Low temperature chlorination generates fewer byproducts than high
temperature chlorination. However, due to the need for EDC distillation, this process requires significantly
more energy inputs than high temperature chlorination.
b. Oxychlorination of Ethylene

In comparison to direct chlorination, the oxychlorination process produces less EDC but provides
the HCl sink required to complete the balanced process. The gas phase reaction of HCl, ethylene, and
oxygen over a catalyst at 220 to 250°C and 2 to 6 bar produces EDC and water. Temperature control is
critical in this highly exothermic reaction to reduce the production of undesirable by-products. The
oxychlorination stage produces waste streams that are not produced by direct chlorination, such as
impurities removed from the EDC as by-products of the EDC distillation section, process vents that
require treatment, aqueous effluents containing dissolved chlorinated organic compounds, traces of
catalyst material in aqueous effluents or spent catalyst, and dioxin-related compounds. These wastes,
however, are not directly emitted into the environment. Instead, additional control measures enable a
significant reduction of problematic substances prior to discharge.

c. EDC purification

EDC products must be purified, whether they come from direct chlorination or oxychlorination,
VCM purification recycling, or external sources, because EDC cracking can be inhibited and fouled by
trace amounts of impurities. Washing with water or caustic, azeotropic drying, heavy ends distillation, and
other methods of purification may be used.

d. EDC cracking

VCM is produced from EDC through a cracking reaction followed by quenching of the process gas
stream. Purified EDC splits into VCM and HCl with conversion rates ranging from 50 to 65 percent when
subjected to thermal cracking in heated furnaces at temperatures around 500°C. To reduce the formation
of tars and heavy by-products, the pyrolysis gases must be rapidly cooled. The purity of the EDC feed
must be very high, greater than 99.5 wt. to reduce the formation of coke and fouling of the reactor for
pyrolysis
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e. VCM purification

After the cracking reaction, HCl and unconverted EDC are separated from VCM using a two-stage
distillation process. Unconverted EDC is recycled to the cracking furnaces after being returned to EDC
purification. Distilled HCl is recycled as feedstock for oxychlorination after an optional hydrogenation stage
to remove any remaining traces of acetylene. The HCl flow to oxychlorination removes the majority of the
volatile by-products. After an optional step to remove the last traces of HCl, the liquid VCM product is
transferred to storage.

Flowsheet:

Figure 2: Vinyl Chloride Plant Flowsheet in DW Sim

1.3.2. Chemistry of Process

There are two options for the chlorination of ethylene, using chlorine (direct chlorination) or by using hydrogen
chloride and oxygen (oxychlorination). Thermal cracking of dry, pure EDC then produces VCM and HCl. When
all of the HCl produced during EDC cracking is re-used in an oxychlorination section, and no EDC or HCI is
imported or exported, the VCM unit is referred to as a ‘balanced unit’. Balanced units achieve a high level of
chlorine utilization without producing HCl as a by-product by using both direct chlorination and oxychlorination
for EDC production. The reactions are represented by the formula:

Direct chlorination: C 2 H 4 +C l 2 → C2 H 4 C l 2 ( EDC ) Eqn. (1)

A=11,493; E=17,929 Eqn. (2)
R1=k 1 [ C 2 H 4 ][ C l 2 ] Eqn. (3)
−E
k 1=A e RT Eqn. (4)

Pyrolysis: C 2 H 4 C l 2 →C 2 H 3 Cl ( VCM ) + HCl Eqn. (5)

14
A=1.14 ×10 ; E=242,672 Eqn. (6)
R3=k 3 [C 2 H 4 C l 2 ] Eqn. (7)
−E
k 3=A e RT Eqn. (8)

1.4. Plant Capacity and Location

1.4.1. Capacity

The proposed production plant will consist of one main plant with a capacity of 25000 MT per
year. In the study of Alberto Y. Francisco entitled "The feasibility of manufacturing vinyl chloride
monomer in the Philippines", in 1977, a proposed project will have a rated capacity of 25000 MT per
year vinyl chloride monomer starting from salt and ethanol. There is also stated capacity for the by-
products of the plant at full capacity utilisation which ranges from 850 to 14500 MT per year depending
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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on its type.

The market study shows that there is a big market for the Vinyl Chloride output of the plant.
Furthermore, it was assumed that by 1978 there was an annual growth rate of 30% in the demand, the
Vinyl Chloride demand-supply was almost 40000 MT even with the addition of 54600 MT of local VCM
capacity. Without additional VCM capacity, the demand-supply was 94000 MT. The capacity for the by-
products will also be based on the demand-supply gap of the plant. In the present day, the major factor
driving the growth of the market is the high demand from the building & construction sector for various
applications. Furthermore, rising demand for vinyl chloride monomers across the healthcare sector is
predicted to increase the product demand further.

1.4.2. Location

The proposed project will be located at Ocampo, Camarines Sur, specifically 13.5908615° N,
123.3970113° E and is approximately 40 hectares. Different factors such as environmental effects,
proximity to the market, regional factors, community considerations, and site-related factors. These
factors are ranked according to their importance to the success of the plant. These factors are all placed
on the same scale to not distort the weight of a factor that inherently has larger values than others.

Fig 3: Plant Location

1.4.3. Site Consideration

The selection of the area for the location of the proposed plant was affected by several factors.
The plant should be located where the minimum cost of production and distribution can be obtained.
First is the site’s characteristics, including the topography, geology, and as well as heritage values
surrounding the location. Further, the community near the location is also included.

The location was placed where people near the proposed plant would not be affected by any
activities that might happen near the plant. Moreover, the availability of raw materials was also
considered. The raw materials should be available within an economical distance. Since the cost of
distribution is an important item in the overhead expenses, the proximity of the production plant to the
market was also considered. Water Supply, energy availability and climate were also considered.

1.4.4. Waste Disposal and Material Recovery

Since vinyl chloride has been identified as a hazardous material, the recommended method of
disposal is destruction by incineration. This may be the only feasible method for the disposal of
contaminated laboratory waste from biological experiments. However, not all incinerators are suitable
for this purpose.
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The recommended temperature range for incineration is 450 ℃ to 1600 ℃ , with residence times
of seconds for gases and liquids, and horse for solids. Further, Wastewater from contaminant
suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and
evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower
than applicable environmental discharge or disposal criteria. Alternatively, pretreatment or discharge to
a permitted wastewater treatment facility is acceptable only after review by the governing authority and
assurance that "pass-through" violations will not occur. Moreover, Aqueous byproduct solutions from the
production of vinyl chloride are usually steam-stripped to remove volatile organic compounds,
neutralized, and then treated in an activated sludge system to remove nonvolatile organic compounds
remaining in the wastewater.

There are several steps for the material recovery process of vinyl chloride production. The
technology comprises the following steps: carrying out a polymerization reaction on a vinyl chloride raw
material to generate polyvinyl chloride, carrying out alkali washing technology treatment on the
unreacted gaseous vinyl chloride monomer, condensing the impurity removed vinyl chloride monomer,
and rectifying the condensed vinyl chloride monomer to complete recovery of the vinyl chloride
monomer. Furthermore, the recovered vinyl chloride monomer undergoes the polymerization reaction
as a raw material to greatly improve the quality of a polymerized product and reduce the dosage of parts
of assistants.

1.4.5. Environmental Consideration

For the location of the Vinyl Chloride Production Plant, factors affecting the environment were
considered. Studies show that Vinyl Chloride has low bioaccumulation potential. Very low
concentrations of a bio-accumulative substance in water can result in markedly higher concentrations in
the tissue of fish at higher levels of the aquatic food chain, as well as in people or wildlife eating those
fish. Therefore, the proposed plant should be kept out of lakes, streams, ponds, or other water sources.
Hence, the selected location was far from bodies of water to avoid contamination.

1.5. Key Feeds

In vinyl chloride plant that utilized both direct chlorination and oxychlorination the main feeds are
ethylene, chlorine, oxygen gas from air, and the recycled HCl in EDC pyrolysis. In direct chlorination the feeds
are ethylene and chlorine. In oxychlorination process the feeds are ethylene, oxygen from the air, and the
recycled HCl from EDC pyrolysis. In EDC pyrolysis the feed is the ethylene dichloride produced in the direct
chlorination and oxychlorination process.

1.5.1. Composition

Direct Chlorination Process

Pure ethylene is used in direct chlorination with a 30% composition. It is stored as a gas at 25 ℃
and 68.9 barg. Pure chlorine is used in direct chlorination with a 70% composition. It is stored as a
liquid at 25 ℃ and 10.3 barg. Normally, the reaction rate is controlled by mass transfer, with absorption
of ethylene as the limiting factor.

Oxychlorination Process
In oxychlorination process, 30% composition of pure ethylene is used, 39% composition of air,
and 31% composition of the recycled HCl from EDC pyrolysis.

1.5.2. Properties and Uses

Ethylene
Ethylene is the simplest of the organic compounds known as alkenes, which contain carbon-
carbon double bonds. It is a colourless, flammable gas having a sweet taste and odour. Natural sources
of ethylene include both natural gas and petroleum; it is also a naturally occurring hormone in plants, in
which it inhibits growth and promotes leaf fall, and in fruits, in which it promotes ripening.

Ethylene is an important industrial organic chemical. It is produced by heating either natural gas,
especially its ethane and propane components, or petroleum to 800–900 °C (1,470–1,650 °F), giving a
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mixture of gases from which, the ethylene is separated. The melting point of ethylene is −169.4 °C
[−272.9 °F], and its boiling point is −103.9 °C [−155.0 °F].

Ethylene use falls into two main categories: 1) as a monomer, from which longer carbon chains
are constructed, and 2) as a starting material for other two-carbon compounds. The first of these is the
single largest use of ethylene, consuming about one-half of the annual output. Polymerization (the
repetitive joining of many small molecules into larger ones) of ethylene gives polyethylene, a polymer
having many uses, particularly in the production of packaging films, wire coatings, and squeeze bottles.
When polymerization is carried out at high pressures and temperatures, the product is called low-
density polyethylene and has properties different from the high-density polyethylene formed by
polymerization under Ziegler-Natta catalytic conditions.

Ethylene is the starting material for the preparation of a number of two-carbon compounds
including ethanol (industrial alcohol), ethylene oxide (converted to ethylene glycol for antifreeze and
polyester fibres and films), acetaldehyde (converted to acetic acid), and vinyl chloride (converted to
polyvinyl chloride). In addition to these compounds, ethylene and benzene combine to form
ethylbenzene, which is dehydrogenated to styrene for use in the production of plastics and synthetic
rubber.

Chlorine
Chlorine is a greenish yellow gas at room temperature and atmospheric pressure. It is two and a
half times heavier than air. It becomes a liquid at −34 °C (−29 °F). It has a choking smell, and inhalation
causes suffocation, constriction of the chest, tightness in the throat, and—after severe exposure—
edema (filling with fluid) of the lungs. The gas is easily liquefied by cooling or by pressures of a few
atmospheres at ordinary temperature.

Chlorine has a high electronegativity and a high electron affinity, the latter being even slightly
higher than that of fluorine. The affinity of chlorine for hydrogen is so great that the reaction proceeds
with explosive violence in light.

Most of the chlorine produced is used for chemical processes involving the introduction of chlorine
into organic compounds, yielding carbon tetrachloride (used as a solvent, a fire extinguisher, and a dry-
cleaning agent), glycols (used as antifreeze), and other organic compounds for the manufacture of
plastics (polyvinyl chloride), dyes, and synthetic rubber. Sulfur chloride, made by the action of chlorine
on carbon disulfide or by combining sulfur and chlorine, is used in the vulcanization of rubber and as a
chlorinating agent in organic synthesis. Sulfur dioxide combines with chlorine to give sulfuryl dioxide.

Hydrogen Chloride
Hydrogen chloride (HCl), a compound of the elements hydrogen and chlorine, a gas at room
temperature and pressure. A solution of the gas in water is called hydrochloric acid.

Hydrogen chloride is a colourless gas of strong odour. It condenses at −85 °C (−121 °F) and
freezes at −114 °C (−173 °F). The gas is very soluble in water: at 20 °C (68 °F) water will dissolve 477
times its own volume of hydrogen chloride. Because of its great solubility, the gas fumes in moist air. A
water solution containing 20.24 percent by weight hydrogen chloride boils at 110 °C (230 °F) without
change in composition (azeotropic mixture). In aqueous solution the compound is extensively
dissociated into a hydronium ion (H3O+) and chloride ion (Cl−); in dilute solutions the dissociation is
essentially complete. Thus, hydrochloric acid is a strong acid.

Hydrochloric acid is an important and widely used chemical. The largest end uses for hydrochloric
acid are steel pickling, oil well acidizing, food manufacturing, producing calcium chloride, and ore
processing.

Hydrochloric acid is used in pickling operations for carbon, alloy and stainless steels. Steel
pickling is the process by which iron oxides and scale are removed from the surface of steel by
converting the oxides to soluble compounds. Pickling is required for steel products that undergo further
processing such as wire production, coating of sheet and strip, and tin mill products. Hydrochloric acid is
used primarily for continuous pickling operations in which hot-rolled strip steel is passed through a
countercurrent flow of acid solution.
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Hydrochloric acid is used both to remove rust, scale and undesirable carbonate deposits in oil
wells to encourage the flow of crude oil or gas to the well. This use is called "stimulation." Acidizing is
generally done in carbonate or limestone formations by stimulation. An acid solution is injected into the
formation, which dissolves a portion of the rock and creates a large pore structure in the formation,
increasing its effective permeability and the flow of oil.

1.5.3. Chemical Safety Guide

Ethylene
Ethylene gas can affect you when breathe in. skin contact with liquid ethylene can cause frostbite.
Exposure to ethylene can cause headache, dizziness, fatigue, lightheadedness, confusion, and
unconsciousness. It is also highly flammable and reactive chemical and a dangerous fire and explosion
hazard.

No occupational exposure limits have been established for ethylene. This does not mean that this
substance is not harmful safe work practice should always be followed. Large amount of ethylene will
decrease the amount of available oxygen. Oxygen content should be routinely tested to ensure that it is
at least 19% by volume.

Chlorine
Chlorine is corrosive. It can burn moist body surfaces, such as the eyes, nose, throat, lungs, and
wet skin, because it forms harmful acids when it reacts with moisture.

Repeated exposure to chlorine does not result in immunity or tolerance. Long-term exposure to
low concentrations of chlorine may cause a gradual decrease in lung efficiency. A single exposure to a
high concentration can cause immediate and potentially irreparable damage to the lungs.

Employers/workers are required to develop and implement an effective PPE program to protect
workers from chemical exposure, including inhalation exposure, eye exposure, and skin exposure. This
program must meet the requirements of the Regulation.

1.6. Product Description

Vinyl Chloride is an organochlorine compound that is a colorless, flammable gas that readily forms a
liquid under increased pressure or at reduced temperatures. It is the precursor to polyvinyl chloride (PVC),
which is used extensively in the construction, automotive, and plastics industry.

1.6.1. Product Specifications

Vinyl Chloride Monomer (C2H3Cl ) is produced by cracking EDC in PFR furnace. This colorless
compound is an important industrial chemical chiefly used to produce PVC. VCM is a gas with a sweet
odor, flammable, and highly toxic.

Table 1 Product Specification of Vinyl Chloride

Product Name: Vinyl Chloride
IUPAC Name: Chloroethene
Molar Mass 62.50 g·mol−1
Density 0.911 g/ml
Melting Point −153.8 °C Specification
Boiling Point −13.4 °C
Solubility in Water 2.7 g/L (0.0432 mol/L)
Vapor Pressure 2580 mm. Hg 20 °C
Parameter Unit
Min Max
Purity % wt 99.9
Moisture Content ppm wt 100
Acidity as HCl ppm wt 1
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Iron as Fe ppm wt 0.5

Acethylene ppm wt 2
1,3 Butadiene 10
Methyl Chloride ppm wt 70
Ethyl Chloride ppm wt 50
Total Dichloro
ppm wt 20
Compound
Non Volatile Matter ppm wt 30
Appearance Clear and NSM
Color APHA Colorless
Inhibitor Properly inhibited

1.6.2. Products (Main and By-products)

The main product of this capstone design project is Vinyl Chloride monomer (VCM). The main by-
product of direct chlorination is 1,1,2-trichloroethane. Homolytic dissociation of chlorine forms this by-
product. Oxygen inhibits the free radical reactions that produce 1,1,2-trichloroethane. Because of this,
addition of pure oxygen to the chlorine in a ratio of 0.5% of the chlorine feed is commonly performed to
reduce by-product formation. It also suggest that HCl is a by products as well, but only in small
amounts.

The reaction is modeled by using kinetic data obtained from a series of articles by Sai Prasad
(2001), and Gel’Perin (1979, 1983, 1984). Sai Prasad presents seven reactions that make up the
oxychlorination reaction (19). Gel’Perin provides more extensive by product formation kinetic data for
the reaction (5,6,7).

Table 2 presents the oxychlorination reactions and their stoichiometric equations.

Table 2 Oxychlorination Reactions

Set Reaction Stoichiometry
R-1 DCE formation C2H4 + 2CuCl2→ C2H4Cl2 + 2CuCl
R-2 TCE formation C2H4 + 3CuCl2→ C2H4Cl3 + 3CuCl +0.5H2
R-3 C2H4 combustion C2H4 + 3O2→ 2CO2 + 2H2O
R-4 CuCl Oxidation 2CuCl + 0.5O2→ CuO-CuCl2→ CuO + CuCl2
R-5 CuCl2 regeneration CuO + 2HCl → CuCl2 + H2O

Along with these five main oxychlorination reactions, nine other by-product formation reactions
were modeled. The oxychlorination reactor is a PFTR with the cupric chloride catalyst packed in the
tubes while cooling water flows on the shell side for temperature control. Some oxychlorination
processes utilize a fluidized bed reactor, but no heat recovery is possible with these reactors.

Pyrolysis (thermal cracking) of EDC produces vinyl chloride. Pyrolysis of EDC is an endothermic
reaction (∆H = 71 kJ/mol) that is carried out in a furnace. The main reaction which yields vinyl chloride
and hydrogen chloride is a homogeneous, first order free-radical chain mechanism. Several by products
are produced through free-radical and molecular mechanism, see equations 9-18.

ClCH2CH2Cl ↔ C2H3Cl + HCl Eqn. (9)

C2H3Cl ↔ C2H2 + HCl Eqn. (10)
H· + HCl ↔ H2 + Cl· Eqn. (11)
Cl + C2H4 ↔ HCl + C2H3· Eqn. (12)
C2H3· + C2H2 ↔ C4H5 · Eqn. (13)
C4H5· ↔ H· + C4H4 Eqn. (14)
C4H5· + HCl ↔ C4H6 +Cl Eqn. (15)
C4H5· + C2H2 ↔ C6H7 · Eqn. (16)
C6H7· ↔ c-C6H7· Eqn. (17)
c-C6H7· ↔ H + C6H6 Eqn. (18)

It is very difficult to verify the formation and amount of by-products. Also it is very difficult to obtain
kinetics parameters of the reactions involved. The pyrolysis kinetics were obtained from the study of
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Choi, Weissmann, and Kurtz. Using the kinetic data and conversion of EDC data given by Kirk-Othmer
and Choi the cracking furnace was modeled and then a conversion reactor was used in the Pro II
process simulation. Conversion of EDC is maintained at 50-55%. Operating the furnace at a higher
conversion decreased the selectivity to vinyl chloride.

The table below summarizes the main and by-products produce in direct chlorination,
oxychlorination, and EDC Pyrolysis.

Table 3 Main and By-products in 3 Processes

Direct Chlorination
Main Product Composition (%) By-product Composition (%)
Ethylene Dichloride
99.8 1,1,2-trichloroethane 0.0019
(EDC)
HCl 0.00019
Oxychlorination
Ethylene Dichloride
47.46 Triethyl citrate (TEC) 0.00045
(EDC)
Water 47.46 CO2 4.95
Acetylene 4.6 ×10−5
Cloral 8.8×10−5
CCl4 4.4×10−4
Methyl Chloride 4.2×10−5
Chloroform 3.9×10−5
Chloroethane 3.9×10−5
Chloroprene 3.5×10−5
Vinyl Acetylene 3.1×10−5
Dichloromethane 3.5×10−5
EDC Pyrolysis
selectivity of vinyl
HCl and other
Vinyl Chloride (VCM) chloride 98.8% at a -
Hydrocarbons
conversion of 60%

1.6.3. Properties and Uses (Main and By-products)

Vinyl Chloride
Vinyl Chloride is primarily used as a chemical intermediate and not a final product. The majority of
Vinyl Chloride is polymerized to produce polyvinyl chloride (PVC) or co-polymerized with other
monomers to produce specialized polymers with specific properties. More than half of the total Vinyl
Chloride consumption is for construction related products.

Trichloroethane
Trichloroethylene is a synthetic, light sensitive, volatile, colorless, liquid that is miscible with many
non-polar organic solvents. Trichloroethylene is used mainly as a degreaser for metal parts. Upon
combustion, it produces irritants and toxic gases. Occupational exposure to trichloroethylene is
associated with excess incidences of liver cancer, kidney cancer and non-Hodgkin lymphoma. It is
reasonably anticipated to be a human carcinogen.

Trichloroethylene appears as a clear colorless volatile liquid having a chloroform-like odor. Denser
than water and is slightly soluble in water. Noncombustible. Used as a solvent, fumigant, in the
manufacture of other chemicals, and for many other uses.

Table 4 Properties/Uses of By-products in Oxychlorination

By-products in Oxychlorination Properties/Uses
Triethyl citrate (TEC) Used as plasticizer in e.g. adhesives, inks,
sealants, plastics and coatings. Here it does
primarily reduce hardness of polymers and can be
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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further used to regulate viscosity.

Used as a refrigerant, in fire extinguishers, for
inflating life rafts and life jackets, blasting coal,
CO2 foaming rubber and plastics, promoting the growth
of plants in greenhouses, immobilizing animals
before slaughter, and in carbonated beverages.
Acetylene Used in welding and cutting processes.
Cloral Used in the short-term treatment of insomnia
Exists as a colorless liquid which emanates a very
CCl4 sweet odor. In the past, this compound was widely
used in cleaning agents.
A colorless, flammable, toxic gas that was used
widely as a refrigerant and has many current
industrial applications, including use as a local
Methyl Chloride anesthetic, a chemical intermediate in silicone
polymer production and drug manufacturing, an
extractant for oils and resins, a solvent in butyl
rubber
Volatile and colorless type of liquid. It was
Chloroform popularly used during surgery as an inhaled
anaesthetic.
Used to convert cellulose to ethylcellulose, a
Chloroethane thickening agent and binder in paints, cosmetics,
and similar products.
Used to produce insulating joints and coatings for
Chloroprene protecting environments that are in contact with
oils and other chemical products.
Colorless gas was once used in the polymer
Vinyl Acetylene
industry.
Major use of dichloromethane is as a solvent in
the pharmaceutical and chemical industry for
Dichloromethane
chemical reactions, purification and isolation of
intermediates or products.

1.6.4. Chemical Safety Guide

Vinyl Chloride is an extremely volatile and flammable gas, vapor, or liquefied gas. It should be
stored away from direct sunlight in a dry, cool and well-ventilated area away from incompatible
materials. Vinyl Chloride vapor concentrations between 3.6% and 33% by volume in air are explosive by
ignition. When exposed to open flames, open electrical elements, or electrical arcs, Vinyl Chloride liquid
or vapor can decompose to form toxic and corrosive fumes.

Depending on conditions, when Vinyl Chloride is exposed to high temperatures, heat, or ignition,
hydrogen chloride gas, which is highly irritating to the nose and throat, as well as trace levels of
phosgene gas, may be produced. As a result, all heat and ignition sources should be eliminated during
handling and storage. Fire and explosion hazards can be minimized by adequate ventilation, using the
proper types and arrangement of equipment, and taking reasonable precautions and care in handling.
All metal parts of equipment must be grounded to avoid ignition of vapors by static electricity discharge.

The following materials are incompatible with Vinyl Chloride, and contact can result in strong
exothermic reactions: oxygen, moisture, polymerization additives, copper, aluminum, oxidizing agents,
strong alkalis, and strong acids.

During Vinyl Chloride transfer operations, all equipment, including unloading pumps, must be
properly grounded and bonded to prevent the buildup of static electricity. If tank car valves are defective
or leaking, do not unload. Air should never be permitted to enter Vinyl Chloride tank cars or other
containers during or after unloading.

Close and seal all openings. Leave at least 10 psig of Vinyl Chloride vapor pressure or nitrogen
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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pressure in an empty tank car being returned, depending on the vinyl tank car unloading system setup.

Appropriate personal protective equipment, as described in the Vinyl Chloride Safety Data Sheet,
should always be worn to avoid contact with the eyes, skin and clothing or to prevent the inhalation of
the gas.

1.7. Battery Limit Conditions

A study by Azapagic, et al. (2006) identified the design specifications and assumptions for a VCM plant
design and is the basis for the battery limit conditions of the present paper.

1.7.1. Feeds, Flare/Vents, and Utilities

a. Gaseous Ethylene

Composition
Ethylene 99.9 mol% min.
Methane & Saturates 0.1 mol% max.
Acetylene 9 mol ppm max.
C3’s & heavier 10 mol ppm max.
CO 5 wt ppm max.
CO2 5 wt ppm max.
Sulfur as H2S 1 wt ppm max.

Pressure 16 kg/cm2G

Temperature 30℃

Phase Gas

b. Gaseous Chlorine

Composition
Cl2 99.2 mol% min.
O2 0.5 mol% max.
H2 0.03 mol% max.
CO2 0.3 mol% max.
Water 10 wt ppm max.

Pressure 3.0 bar

Temperature Ambient

Phase Gas

c. Gaseous Oxygen

Composition
Oxygen 99.5 mol% min.
PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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Pressure 4.0 bar

Temperature Ambient

Phase Gas

d. EDC (as cracker feed)

Purity 99% mol% min.

Impurities
C1 lights 2000 wt ppm max.
C2 lights 4000 wt ppm max.
C4 lights 100 wt ppm max.
C2 heavies 1000 wt ppm max.
C4 heavies 5000 wt ppm max.
β -trichloroethane 500 wt ppm max.
Water 0.3 mol% max.
Fe 1 wt ppm max.

INTERMEDIATE STREAMS
a. HCl

Separated from cracked gas 200 wt ppm VCM max.

b. EDC

Separated from cracked gas 200 wt ppm VCM max.

UTILITIES
a. Steam

Pressure Temperature
(bar) (℃ ¿

LP steam 3.1 155

IP steam 15.0 225

HP steam 42.4 270

b. Cooling water

Pressure Temperature
(bar) (℃ ¿

Cooling water supply 5 32 max.

Cooling water return 2 41 max.

 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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Sheet 17 of 18

c. Natural Gas

Composition
CH4 94 mol% max.
Ethane 4 mol% max.
N2 2 mol% max.

Pressure 4.5 bar

Temperature 35℃

1.8. Market

Vinyl chloride monomer is mainly used in the production of PVC, thus its demand is strongly linked to the
region’s PVC consumption. End user industries such as the construction, electronics, and packaging industry
are also showing a growing demand due to the booming e-commerce.

1.8.1. Customer/Market Players

According to the market study conducted by Francisco (1977), it shows that that there is a big
market for the VCM output of the plant. The two local PVC companies are currently dependent on
imported VCM, with Philippine Vinyl Consortium, Inc. and Mabuhay Vinyl Corporation dependent on
imported VCM for around two-thirds of its rated capacity. Domestic VCM producers are also available in
the Philippines. Mabuhay Vinyl Corporation is the first and largest chlor-alkali producer in the
Philippines. It is the country’s leading manufacturer of caustic soda and chlorine derivatives. While the
Vinyl Consortium established a plant with an annual capacity of 18,000 metric tons for the production of
Vinyl Chloride Monomer (VCM).
The Philippine Resins Industries, Inc., one of the most modern PVC manufacturing plants in the
Philippines and in Asia also imports its VCM and PVC requirements from Mitsubishi Corporation
(Japan) with plans to expand its current production capacity. According to a market analysis by Global
Industry Shares (2021), the COVID-19 pandemic has adversely affected several industries, including
the VCM market, across the globe and is expected to maximize by the end of 2025.

Vinyl chloride monomer is mainly used in the production of PVC, thus its demand is strongly linked
to the region’s PVC consumption. End user industries such as the construction, electronics, and
packaging industry are also showing a growing demand due to the booming e-commerce. The major
players of the plastic market in the Philippines are the JG Summit Petrochemicals Group, Chemrez
Technologies, Petron Corporation, Philippine Resins Industries, Inc. and NPC Alliance Corporation.
Considering that most of the VCM supply needed for the PVC industry are imported by these
companies abroad, this shows that there is a demand for a manufacturing plant in the Philippines.
Byproducts can also be recovered and sold from the VCM production. HCl produced from the thermal
cracking can be recycled using oxychlorination process or can be purified and sold to manufacturers
which can be used in the production of fertilizers, dyes, and textile.

1.9. Specific Design Requirement and Constrains

The Vinyl chloride production plant design based on previous literatures has specified requirements that
adhere to safety standards and environmental regulations. According to Benyahia (2005), the gas mixture has
to be kept above the dew point or very rapid corrosion will ensue, but industrial data shows that the onset of
corrosion occurs at temperatures well above the theoretically calculated dew point. The construction material
used for the reactor shell and cooler bundle should also be studied in a metallurgical analysis to avoid
corrosion. To prevent pressure build up by inert gases and to be operated to depressurize and flush
equipment during emergencies and prior to maintenance, vents are installed in process vessels.
 PLANT DESIGN FOR THE PRODUCTION OF VINYL CHLORIDE FROM ETHYLENE
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The Applied Analytics (2017), identified that moisture should be monitored in the vent gas in the EDC and
VCM from the distillation column since HCl an Cl2 is known to form a highly corrosive mixture with H2O above
100 ppm. Removal of moisture will improve the quality of the final product and reduce potential costs. For
safety, oxygen (O2) should be measured, monitored, and controlled below the flammable limit at 0-15% in the
vent gas at direct chlorination and 0-5% at the oxychlorination process.

1.10. About the Company

Blueprint Incorporated is a team of engineers who are planning to design a manufacturing plant of Vinyl
Chloride Monomer (VCM) from and create innovations on existing plants. The company plans to produce a
chemical plant with a capacity of 25000 MT per year of VCM to meet the demand trend of the country.

ATTACHMENTS

Attachment 1:
Attachment 2:
Attachment 3:

REFERENCES:

1. Merchant Research & Consulting Ltd., (2022). Philippines Polyvinyl Chloride (PVC) Market
Outlook 2022. Retrieved February 15, 2022 from
https://marketpublishers.com/report/thermoplastic/polyvinyl_chloride/philippines-polyvinyl-
chloride-market-outlook.html
2. Mordor Intelligence, (n.d.). VINYL CHLORIDE MONOMER MARKET - GROWTH, TRENDS,
COVID-19 IMPACT, AND FORECASTS (2022 - 2027). Retrieved February 15, 2022 from
https://www.mordorintelligence.com/industry-reports/vinyl-chloride-monomer-market#:~:text=The
%20vinyl%20chloride%20monomer%20market,construction%20sector%20for%20various
%20applications.
3. Dry, J., Lawson, B., et al. (2003). Vinyl Chloride Production. Retrieved February 16, 2022 from
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(PVC). Retrieved February 16, 2022 from
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05.pdf
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Chloride Process. Carnegie Mellon University Department of Chemical Engineering 1997.
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9. Davis, Robert J. and Robert F. Zeiss. Cyrogenic Condensation: Cost Effective Technology for
Controlling VOC Emissions. www.rizzo.com/pdf/library_cryogenic_condensation_1.pdf
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