International Journal of Scientific & Engineering Research, Volume 4, Issue 5, May-2013 701

ISSN 2229-5518

Cleaner Production of Vinyl Chloride

Monomer (VCM)
Jemish Dattani, Darshan Devani, Omprakash Sahu

Abstract - Cleaner production eliminates pollution throughout the entire production process. It is a way of reducing pollution damage to both the
environment and the human population by increasing the efficiency of resource use – decreasing pollution discharge by improving management
and technology. Cleaner production is implemented at the factory level. The factories get both economic and environmental benefits from
implementing cleaner production. The implementation of cleaner production involves a combination of reorganization, improved technology in the
factories, power saving and decreasing consumption, improved management and competent resource use. The eventual goal of clean production
is to achieve a 'closed loop' operation in which all excess materials are recycled back into the process, which is utmost necessary in today’s world.
..Here we have included a case study of vinyl chloride monomer (VCM) production using cleaner production (CP), which includes Material
Balance, Energy Balance, Cost Estimation and Simulation.

Index Terms- cleaner production, vinyl chloride monomer, eco efficiency

——————————  ——————————

1 INTRODUCTION based on different techniques. These techniques are

classified into three main categories as which are

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c
leaner Production (CP) is the continuous shown in figure no.1 [3].
application of an integrated preventive
environmental strategy to processes, products,
and services to increase overall efficiency, and
reduce risks to humans and the environment.
Cleaner Production can be applied to the processes
used in any industry, to products themselves and to
various services provided in society [1]. It is a broad
term that encompasses terms such as eco-efficiency,
pollution prevention and green productivity. In essence,
applying cleaner production protects the environment,
the consumer and the worker while improving industrial
efficiency, profitability and competitiveness. The Key F ig.1: Technique of Cleaner production
element of the CP is to reach the precautionary, In 1993, a CP demonstration project targeting SMEs was
preventive, integrated and holistic approach with initiated by UNIDO, in cooperation with the Indian
democratic control. The basic principle of CP is focus National Productivity Council and other industry
on the primary function of the economic activities for associations. This desire project focused on different
process input resources (raw material, energy, water, sectors such as agro-based pulp and paper, textile dying
etc.) into usable outputs [2]. However, all the inputs are and printing, polymeric material and pesticides
not transformed into the usable outputs. The portion formulation [4]. From the all other product we choices the
that does not get transformed into useful outputs comes polymeric Vinyl chloride for the cleaner production, Vinyl
out as waste. This transformation of waste depends on chloride (CH 2 =CHCl) is a haloginated alkane. It is the
the technology employed and efficiency of the process. building block for its polymer poly-vinyl chloride (PVC)
However, with the growth of the economic activities, on and other co-polymers with acetate and vinyl chloride.
one hand the withdrawal of resources from nature has Poly (vinyl chloride), PVC, is a common commodity
increased, while on the other hand the discharge of the plastic, and its production is the third largest, after
wastes into the environment as amplified. The current polyethylene and polypropylene [5]. It is cost-effective,
trends as well as the pace in the economic activity of highly versatile and is used in many construction
our country are resulting in the generation of wastes at applications as water, sewage and drainage pipes, and a
a much higher pace than the assimilative capacity of variety of extruded profiles [6]. Thousands of rigid, semi-
the environment. This new & creative approach to flexible and flexible (plasticized) materials and products
enable the production process less waste intensive is based on PVC are widely used in practically all spheres

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 International Journal of Scientific & Engineering Research, Volume 4, Issue 5, May-2013 702
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of the world economy and will remain so for a very long expensive C2 hydrocarbon, but it cannot be converted to
time. From volume estimates, the world production of vinyl chloride with high selectivity.
PVC grew from a few hundred million pounds to about 44
billion pounds in 2000 [7] as new uses and markets were 2.1 Chlorination followed by Thermal Cracking and
developed. However, it is known that PVC degrades at Vinylation
elevated temperatures, giving off hydrochloric acid (HCl)
that in turn accelerates the degradation process.
Depending on the number of conjugated double bonds
formed, it becomes yellow, orange, red, brown and finally
black [8]. The splitting-off of HCl from the polymer
backbone affects the physical, chemical and the
mechanical properties of the polymer. Until the discovery
of thermal stabilizers, PVC was not an industrially very
useful polymer, as it could not be processed to useful
articles without degradation at elevated temperatures.
Quantum improvements in extrusion and injection
moulding machinery and extrusion die design, together
with significant improvements in stabilizers and lubricant
technology have all contributed to increased tonnage
production and usage of PVC. The goal of this study is to
produce an environmentally friendly, safe, and

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economically profitable vinyl chloride production in plant
and to achieve a 'closed loop' operation in which all
excess materials are recycled back into the process. 2.2 PROCESS DESCERIPTIONS
For the production of Vinyl chloride from ethylene
2. MATERIAL AND METHODS dichloride, initially ethylene is allowed to react with gaseous
Ethylene dichloride (EDC)
Vinyl chloride was first produced using the process of chorine to obtain EDC. Ethylene is reacted with Chlorine
dehydrating ethylene dichloride (EDC) with alcoholic gas at temperature of 65C in the pre s e nce of Fe Cl2, the
caustic potash. However, the first effective industrial resultant product is Ethylene dichloride (Reaction - 1). The
process was based on the hydro-chlorination of acetylene. reaction is highly exothermic in nature. The conversion is
Until the late 1940s, this process was used almost 100% and selectivity for this step is above 99% for this
exclusively. The normal method of producing acetylene reaction. To produce Vinyl chloride from EDC, thermal
was from calcium carbide. “The high-energy requirement pyrolysis process is carried out at a temperature of 480-
for carbide production was a serious drawback to the 550oC and 4 atmospheric pressure(Reaction-2). At this
continuing mass production of vinyl chloride by this operating condition, thermal cracking of EDC is taking
method”. However, as ethylene became more plentiful in place in tubular pyrolysis (cracking) furnace. Additionally
the early 50’s, commercial processes were developed to Vinylation (Reaction – 3) is carried out to utilize co –
produce vinyl chloride from chlorine and ethylene via EDC, product HCl produce in thermal cracking reaction (Reaction
namely, the balanced ethylene route. Today the balanced – 2).In vinylation reaction, acetylene and HCl (produced in
ethylene is responsible for well over 90% of the world’s thermal pyrolysis reaction) are allowed to react at
vinyl 6 chloride production. “This process has been refined temperature 200oC and 1 atmospheric pressure. The
and the scale of operation has greatly increased, but no reaction of acetylene and hydrogen chloride is carried out
fundamentally new processes have achieved commercial in the vapor phase at 150–250oC over a mercuric chloride
viability”. Although this is true, it is still necessary to catalyst. The acetylene route is usually coupled with
examine the alternative processes and determine if they ethylene chlorination unit so that the hydrogen chloride
can still be utilized. All current production plants for vinyl derived from cracking dichloroethane can be consumed in
chloride depend on the use of a C 2 hydrocarbon feed the reaction with acetylene. HCl being now a raw material,
stocks, specifically, acetylene, ethylene, or ethane. the entire environment in a plant producing vinyl chloride
Commercial operations using these compounds are has to be kept perfectly dry atmosphere. Since the tubular
confined to gas-phase processes. “Manufacture from reactor containing carbon pellets impregnated with HgCl2
acetylene is a relatively simple single-stage process, but is used, initially temperature used is 160oC which is
the cost of acetylene is high”. Ethane is by far the least increased to 200 C progre s s ive ly de pe nd i ng on the
deactivation of catalyst due to carbon deposition. Proper
heating of raw material must be done to avoid deactivation.

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Control of temperature is the most essential parameter to highly endothermic in nature. Energy required in terms of
increase the conversion level. Thus one mole each of heating 58 x 107 kJ / day. Since the conversion of the
ethylene, acetylene, and chlorine give two moles of vinyl process is 63%, the product comes out of the reactor at
chloride with a minimum of by-products. Hard cracking of the end of reaction contains main product vinyl chloride
hydrocarbons to a 1:1 molar mixture of ethylene and 500 TPD (8000 kgmoles / day), by – product HCl 292
acetylene for use as feedstock for vinyl chloride production TPD (8000 kgmoles / day) and unreacted EDC 465.1
is done. The crude stream from the tubular reactor contains TPD (4698.4 kgmoles / day). This product stream is
the main product, as well as unreacted amount of allowed to cool and separate in separation unit. Energy
acetylene and HCl, the unreacted amount is stripped off in that must be required in terms of cooling is 74.8 x 107 kJ
a stripper and recycled to the reactor to reduce the raw / day to cool the product stream. In this reaction,
material requirements. Hence at the end more amount of unreacted quantity of EDC 465.1 TPD (4698.4 kgmoles /
vinyl chloride is obtained, as a result the overall plant day) is recycled with fresh EDC. Hence the raw material
production capacity can thus be increased. The flow requirement can thus be reduced. By – product – HCl
diagram is shown in figure 2. generated is also fully utilized in this route. In vinylation,
reaction is carried out by using acetylene as a raw
material with HCl produced in thermal pyrolysis reaction i.
e. in second step. Acetylene 208 TPD (8000 kgmoles /
day) and HCl 292 TPD (8000 kgmoles / day) is allowed to
preheat initially before reaction to takes place. Heat
required to preheat the raw material is 1.92 x 107 kJ /
day. The vinylation is exothermic reaction, so as to

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remove the exothermic heat 79.49 x 107 kJ / day; energy
is required in terms of cooling. The conversion of this
process is considered as 100%. The product leaving the
reactor contains main product vinyl chloride 500 TPD
(8000 kgmoles / day). The product stream is allowed to
cool and impurities are separated in the separator. Hence
19.57 x 107 kJ / day of energy is required in terms of
Fig.2: Production of VCM via Acetylene-HCl route
cooling to cool and separate the product. Hence, finally in
this route total 1000 TPD (16000 kgmoles / day) of vinyl
3. RESULT AND DISCUSSION chloride is obtained. Here, HCl produced is fully utilized to
3.1 Production by route-III: The vinyl chloride is react with acetylene so that liquid waste generated is
produced by the unit processes namely chlorination, zero. Hence, raw material requirement reduces to half
thermal pyrolysis and vinylation respectively. To produce and also energy requirement in terms of cooling and
1000 TPD (16000 kgmoles / day) of Vinyl chloride, heating also reduces to half. Thus this is the most
process is initiated by chlorination using raw material as favorable route in terms of energy conservation and
ethylene and chlorine (equimolar) in a quantity 224 TPD waste minimization.
(8000 kgmoles / day) and 568 TPD (8000 kgmoles / day) 3.2 Comparison of routes based on Material Balance
respectively. These raw materials for chlorination process Principles:
are preheated and fed to the rector. During preheating, Finally we can summarize the entire three routes in
energy requirement is 0.106 x 107 kJ / day. Since common table by material balance principles for the
chlorination is highly exothermic in nature, the amount of production of 1000 TPD of vinyl chloride as under:
heat that must be removed from the reactor is 145 x 107
kJ / day. As the conversion is 100% for chlorination TABLE 1:
process, the product ethylene dichloride (EDC) come out COMPARISON OF MATERIAL BALANCE
of reactor is 792 TPD (8000 kgmoles / day). Here, energy Route Product Intermediate Reactants Reactants

that must be required in terms of cooling is 23.26 x 107

Unit VCM HCl* EDC C 2 H4 Cl 2 C 2 H2 HCl* O2
kJ / day to cool the product. In second step, thermal
pyrolysis is done with the raw material EDC. In this stage, R
TPD 1000 584 2514.3 448 1136 -- -- --

fresh EDC 792 TPD (8000 kgmoles / day) from -I

Kgmoles
chlorination process with recycled quantity 465.1 TPD 16000 16000 25396.9 16000 16000 -- -- --
(4698.4 kgmoles / day) is preheated and sent to thermal / day

cracking. Energy required for preheating is 74.8 x 107 kJ

/ day. Since the cracking reaction is thermodynamically

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 International Journal of Scientific & Engineering Research, Volume 4, Issue 5, May-2013 704
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Unit VCM HCl* EDC C 2 H4 Cl 2 C 2 H2 HCl* O2

TOTAL ENERGY REQUIRED (kJ / day) 842.5 x 107
TPD 1000 584 2514.3 448 568 -- 584 64
R
-II Step:1 0.1065 x
Kgmoles 145 x 107 23.27 x 107 168.4 x 107
Chlorination 107
16000 16000 25396.9 16000 8000 -- 16000 4000
/ day
Step: 2
R- III Thermal 74.8 x 107 58 x 107 74.8 x 107 207.6 x 107
Unit VCM HCl* EDC C 2 H4 Cl 2 C 2 H2 HCl* O2 Pyrolysis

R TPD 1000 292 1257.1 224 568 208 292 -- Step: 3

1.92 x 107 79.49 x 107 19.57 x 107 100.98 x 107
- Vinylation

III Kgmoles
16000 8000 12698.4 8000 8000 8000 8000 --
TOTAL ENERGY REQUIRED (kJ / day) 476.98 x 107
/ day

It can be seen from above table that among three routes

As could be seen from above table, Route – II and Route
for the production of 1000 TPD of vinyl chloride, the
– III can be considered as environmentally friendly route.
energy requirement in Route – III is the lowest than the
Since by – product – HCl comes out at the end of
conventional route i. e. Route – I. Route – II requires 10%
pyrolysis reaction is being fully utilized in these above
additional energy than the conventional route though it is
mentioned routes. Raw material requirement as
considered as environmentally friendly route as the
compared to other conventional route also reduces to
emission of pollutant (Cl2) quantity reduces to half and
half. Chlorine quantity requirements in route - II are
the liquid effluent (HCl) is also fully utilized by this route. If
reduced to half; as a result intensity of pollutant-Cl2 in

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comparison can be made between Route – I and Route –
gaseous effluent stream also gets reduced considerably.
II, then energy requirement in step – 1 of Route – II is
Quantity of CO2 emission in atmosphere gets reduced to
approximately half to that of step – 1 of Route – I, but
half quantity – equivalent carbon credits are obtained.
oxychlorination step in Route – II needs more energy.
Thus, Route-III is more environmentally friendly in
Hence, Route – II almost needs more energy (10%) than
comparison to Route-II.
Route – I. Finally, if one can analyses and compare the
entire three routes, Route – III is more energy efficient as
3.3 Comparison of routes based on Energy Balance
well as eco – friendly route. More energy conservation
Principles: The Energy requirement for entire three
compared to other two routes can be obtained in this
routes can be summarized with respect to energy
Route – III and also the by – product – HCl generated is
balance in a common table as under:
fully utilized by this route. The requirement of energy is
also reduced by 66%. Hence more carbon credits can be
TABLE 2:
earned. So, Route – III can be considered as the more
COMPARISONS OF ENERGY BALANCE
Heat to be environmentally route than Route – II.
Route
Preheating absorbed / Separation TOTAL
4 CONCULSION
(kJ / day) removed (kJ / day) (kJ / day)
(kJ / day)
This route is more environmental friendly than the other
routes in terms of waste minimization and energy
Step:1
Chlorination
0.213 x 107 291 x 107 46.54 x 107 337.75 x 107 conservation. Vinylation reaction (step – 3) is carried out
R- I to utilize the by – product – HCl generated in pyrolysis
Step: 2
Thermal 149.6 x 107 116 x 107 149.6 x 107 415.2 x 107
reaction, as a result the quantity of liquid waste generated
Pyrolysis in this route is zero. The most important conclusion for
this route can be drawn by material and energy balance
TOTAL ENERGY REQUIRED (kJ / day) 752.95 x 107
calculation, when compared with other routes. To
produce 1,000 TPD of vinyl chloride, 224 TPD of
Step:1
Chlorination
0.106 x 107 145 x 107 23.27 x 107 168.4 x 107 ethylene and 568 TPD of chlorine is required in
chlorination (step – 1) to produce EDC. In thermal
Step: 2
pyrolysis (step – 2), 1257.1 TPD of EDC is fed to reactor
R – II Thermal 149.6 x 107 116 x 107 149.6 x 107 415.2 x 107
Pyrolysis to produce vinyl chloride, 292 TPD of HCl as a by –
product and some unreacted amount of EDC which is
Step: 3
Oxychlorination
6.51 x 107 191 x 107 61.39 x 107 258.9 x 107 recycled to the reactor, so that requirement of fresh raw
material EDC is reduced. To utilize by – product HCl
generated in thermal pyrolysis, this by – product becomes

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the feed stock for vinylation reaction and is allowed to

react with 208 TPD of acetylene to produce vinyl chloride.
Thus total 1,000 TPD of vinyl chloride is er routes
produced. So, in this route also quantity of liquid effluent
generated is practically zero, also intensity of pollutant –
Cl2 gets reduced to half compared to ot. Here, in this
route, as compared with other two routes, raw material
requirement also gets reduced to half, although plant
capacity for the production of vinyl chloride remains the
same. The total energy requirement for this entire route
for vinyl chloride production is 476.98 x 107 kJ / day.
Compared with the energy requirement in other two
routes, the energy requirement in this route gets reduced
almost to 50%. Thus, from the environmental point of
view, this route has provided the best platform for
implementation of Cleaner Production Principles. This
route is thus, a more environmentally friendly route in
terms of waste minimization, reduction in raw material
requirements and energy conservation than other routes.
Hence, in this industrial case study for production of vinyl
chloride Cleaner Production Principles can be

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implemented successfully.
ACKNOWLEDGEMENTS:
Authors acknowledge to department of chemical
engineering KIT Jamnagar and Ministry of Technical
Education Gujarat (India) for their support.
Reference
[1]Puranik, S.A.; “Capacity Building for Students And
Academicians In Environment Related Issues With
Special Emphasis On Cleaner Production”, 2nd
International Conference on Cleaner Production (Deptt.
Of Forests & En.) February 6-8, 2012.
[2]Gujarat Cleaner Production Centre, “Cleaner
Production Manual”, p: 5 – 14, 65 – 78, 117 – 125(2010).
[3]Gujarat Cleaner Production Centre, “Draft of Cleaner
Production Manual”, www.gcpcgujarat.org, P15-29(2011).
[4]“Implementation Cleaner Production” Pollution
Prevention and Abatement Handbook World Bank Group,
July 1998.
[5] Yoshioka T, Kameda T, Leshige M, Okuwaki A ;
Dechlorination behaviour of flexible poly(vinyl chloride) in
NaOH/EG solution. Polym. Degrad. Stab., 93: 1822-1825
(2008).
[6]Van Es DS, Steenwijk J, Frissen GE, van der Kolk HC,
van Haveren J, Geus JW, Jenneskens LW (2008). The
compatibility of (natural) polyols with heavy metal- and
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50-58(2008).
[7]Skip.T.;“WhatisPVC”,http://www.plastics.com/articlelive
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