Vinyl Chloride

Laxminarayan Institute of Technology 2015
CHAPTER ONE: INTRODUCTION[1,2]

Vinyl Chloride is an organochemical with the formula CH2CHCl that is also called as Vinyl
Chloride Monomer (VCM) or Chloroethene. It is one of the worlds most important commodity
chemicals. Chlorinating hydrocarbons is the basic idea behind the production of vinyl chloride
monomer (VCM).Chlorinated hydrocarbons (CHCs) is much more resilient to biodegradation,
unlike simple hydrocarbons. This is due mainly to the inherent strength of the C-Cl bond.
Consequently, man-made CHCs are beginning to accumulate in the environment. However,
production of VCM is essential to the production of polyvinyl chloride (PVC). Construction
materials made of PVC are light, low-maintenance, and long lasting. About 13 billion kilograms
of VCM are produced annually. About 25% of the worlds total chlorine production is required
for its production. VCM is among the top twenty largest petrochemicals (petroleum-derived
chemicals) in world production. The United States currently remains the largest VCM
manufacturing region. China is also a large manufacturer and one of the largest consumers of
VCM.
VCM is an OSHA regulated material. Chloroethylene is a colourless gas at normal
temperature and pressure. Industrially it is handled as liquid with boiling point 259.6K. No
Human contact with the material is allowed as it is highly toxic, flammable, and
carcinogenic. It can also be formed in the environment naturally when soil organisms break
down chlorinated solvents.
HISTORY
The early history of vinyl chloride has been documented by Justus von Liebig and
his student Henri Victor Regnault at the university of Giessen, Germany and Justus won
the distinction of being the first person to synthesis vinyl chloride. In the 1830s, he reacted
the so-called oil of the Dutch chemists, dichloroethane with alcoholic potash to make vinyl
chloride. Victor confirmed his discovery and was allowed to publish it as sole author in
1835.
Vinyl Chloride Monomer
Page 1
In 1872, E. Baumann observed that white flakes precipitated from vinyl chloride
upon prolonged exposure to sunlight in a sealed tube. This material was further
investigated in the early 1900s by Ivan Ostromislensky, who named it Kauprenchlorid.
(cauprene chloride), and gave it the empirical formula (C2H3Cl)16. However, vinyl chloride
was of little commercial interest until Waldo Semons work with plasticized PVC for the
B. F. Goodrich Company beginning in 1926. Some years earlier, Fritz Klatte had
developed the first practical route to vinyl chloride while looking to find uses for acetylene
for Chemische Fabrik Griesheim-Elektron. This process, in which hydrogen chloride is
added to acetylene over a mercuric chloride catalyst, was patented in 1912, By 1926,
Griesheim Elektron had concluded that the patent held no commercial value and allowed it
to lapse. Klattes process eventually formed the basis of the vinyl chloride industry for
many years from its beginnings in the 1930s. From 1940-1950 on, acetylene could be
replaced by ethylene, from which vinyl chloride was produced by direct chlorination to 1,2
dichloroethane and subsequent thermal cracking.
Page 2
CHAPTER TWO: HEALTH AND SAFETY FACTORS &

PROPERTIES[1]
HEALTH AND SAFETY FACTORS
1) OSHA lists vinyl chloride as a Class IA Flammable Liquid. Because of its low boiling point,
liquid VCM will undergo flash evaporation upon its release to atmospheric pressure. It has a
wide flammability range from 3.6 to 33% by volume in air. As a gas mixed with air, VCM is a
fire and explosion hazard on standing VCM can form peroxides, which may then explode.
2) Contact with liquid vinyl chloride can cause frostbite. Chronic exposure to vinyl chloride at
concentrations of 100 ppm or more is reported to have produced Raynauds syndrome. Chronic
exposure has also reported to have produced a rare cancer of liver (angiosarcoma) in a small
number of workers after continued exposure for many years to large amounts of vinyl chloride
gas.
3) Short term exposure is limited to 5 ppm averaged over any 15 min period. Contact with liquid
vinyl chloride is prohibited. Where concentrations cannot be lowered below the 1 ppm, the
employer must establish a regulated area with controlled access.
4) Vinyl chloride also poses a significant fire and hazard explosion. Large fires of compound are
very difficult to extinguish, while vapours represent a severe explosion hazard.
5) Because hazardous peroxide can form on standing vinyl chloride in air, especially in the
presence of iron impurities, vinyl chloride should be handled and transported under an inert
atmosphere. The presence of peroxide from vinyl chloride and air can initiate polymerization of
stored vinyl chloride.
6) Vapours of vinyl chloride are more than twice as dense as air and tend to collect in low lying
areas, increasing the risk of fire. Workers entering these low lying areas risks suffocation, which
can occur at levels above 18,000 ppm. The mild, sweet odour of vinyl chloride becomes
detectable around 250 ppm.
Page 3

USES AND ECONOMIC ASPECTS
(1) Vinyl Chloride has gained worldwide importance because of its industrial use as the precursor to
PVC. It is also used in a wide variety of copolymers. The inherent flame retardant properties,
wide range of plasticized compounds and low cost of polymers from vinyl chloride have made it
a major industrial chemical.
(2) About 95% of current vinyl chloride production worldwide ends up in polymer or copolymer
applications.
(3) Vinyl chloride also serves as starting material for the synthesis of a variety of industrial
compounds, as suggested by the number of reaction in which it can participate, although none of
these applications will likely ever come anywhere near PVC in terms of volume.
(4) The primary nonpolymeric uses of vinyl chloride are in the manufacture of vinylidene chloride,
vinyl stearate and tetrachloroethylene.
Page 4
PHYSICAL AND CHEMICAL PROPERTIES OF VINYL CHLORIDE:

PROPERTY
VALUE
Molecular weight
62.4985
Melting point (1atm), K
119.36
Boiling point (1atm), K
259.25
Heat capacity at constant pressure, J/(mol.K)

Vapour at 200C
Liquid at 200C
53.1
84.3
Critical Temperature, K
Critical Pressure, MPa
Critical Volume, cm3/mol
Critical compressibility
Autoignition temperature, K
Acentric factor
Dipole moment, C-m
Enthalpy of fusion (melting point), kJ/mol.
Enthalpy of vapourisation (298.15), kJ/mol.
Enthalpy of formation (298.15K), kJ/mol.
Explosive limit in air, vol%
Lower limit
Upper limit
Gibbs energy of formation (298.15K), kJ/mol
Vapour pressure, kPa
-300C
-200C
-100C
00 C
Viscosity, mPa.s
-400C
-300C
-200C
-100C
Explosive limit in air, vol%
432
5.67
1.79
0.283
745
0.100107
4.84E-30
4.744
20.11
41.95
3.6
33
49.3
78.4
119
175
0.345
0.305
0.272
0.244
4-22
Table no: 1 Physical and chemical properties of vinyl chloride.
Page 5
IMPORT DATA OF VINYL CHLORIDE[3]
SR.NO
YEAR
QUANTITY(TONNES)
2007
114988
2008
120303
2009
154636
2012
180202
2013
189036
Table No: 2 Import data of Vinyl Chloride.

350000
300000
y = 12654x - 3E+07
R = 0.9435
quantity in tons
250000
200000
150000
100000
50000
0
2006
2008
2010
2012
2014
2016
Year
2018
2020
2022
2024
Figure no.1: Projected Increase in Demand of Vinyl Chloride
Page 6
MAJOR PRODUCERS OF VINYL CHLORIDE IN INDIA.

Sr.no.
Industries
Design capacity(TPA)
1.
IPCL, Vadodara
57300
2.
IPCL, Dahej
170000
3.
NOCIL,
30,000
4.
RIL, Hazira
270000
5.
Finolex Pipes Limited, Ratnagiri
240000
6.
DCW Ltd.
100000(MT)
Table no.3: Major Producers of Vinyl Chloride in India.
Page 7
CHAPTER THREE: MANUFACTURING PROCESSES [2]

Early the Industrial production of vinyl chloride is based on only two reactions:
(1) Hydrochlorination of acetylene:
C2H2 + HCl
CH2 = CHCl , H= -99.2 KJ/mol
(2) Thermal cracking of 1, 2-dichloroethane:
CH2CH2 + Cl2
Cl-CH2 CH2-Cl
Cl-CH2 CH2-Cl
CH2 = CHCl + HCl , H=100.2 KJ/mol
Acetylene hydrochlorination was mainly used in the past, when acetylene produced via calcium
carbide from coal, was one of the most important basic feedstock for the chemical industry.
However with time and large scale production of ethylene-derived polymers, such as
polyethylene and polystyrene and the general trend toward natural gas, naphtha and gas oil as
basic feedstocks. The cracker capacity increased substantially and ethylene became readily
available at very competitive prices.
Besides the economical disadvantage of the higher priced hydrocarbon feed, the
acetylene hydrochlorination has the drawback of not being balanced on the chloride as a chlorine
source. With increasing demand for vinyl chloride and technical progress, the first balanced
processes were established in the 1940s and 1950s, when acetylene was partially replaced by
ethylene, which was converted to 1,2-dichloroethane and subsequent thermal cracking. The
hydrogen chloride from cracking could then be used for acetylene hydrochlorination:
C2H4 + Cl2
C2H4 Cl2
C2H4 Cl2
CH2 = CHCl + HCl
Page 8
C2H2 + HCl
CH2 = CHCl
C2H2 + C2H4 + Cl2
2CH2 = CHCl
By direct use of crack gas, without separation of ethylene and acetylene, this process still
pursued with some modifications. With the introduction of the first large scale oxy-EDC plant by
The Dow chemical in 1958, a balanced process based only on inexpensive ethylene became
available and found rapid acceptance within the chemical industry.
In this direct chlorination of ethylene, pyrolysis of EDC and
oxychlorination of ethylene are combined for the production of VCM, with no net consumption
or production of HCl.
Direct chlorination: CH2 = CH2 + Cl2
C2H4Cl2
EDC pyrolysis: CH2 = CH2 + 2HCl + O2
C2H4Cl2 + H2O
Oxychlorination: 2C2H4 Cl2
2CH2 = CHCl + 2HCl
Overall Reaction: 2CH2 = CH2 + O2 + Cl2
2CH2 = CHCl + H2O
Page 9
SELECTION OF PROCESS [1, 4]

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. Along with that, the major issue with this
process is that fact that the catalyst used, mercuric chloride, is a very volatile compound
which causes environmental problem.
The relative inexpensiveness of ethane has lead to many
attempts to develop a process that will use ethane to directly produce vinyl chloride. In
this processes oxychlorination is required. Although possible, this process has not
progressed beyond the conceptual stage. This is due to the fact that the oxychlorination
reactor design presents a severe challenge in terms of materials of construction because
the reaction temperature may go up to 500 oC. At this temperature chlorine becomes very
aggressive to most construction materials. Along with it, the major problem associated
with the use of ethane is its molecular symmetry. In particular, the addition of chlorine to
ethane gives rise to a wide product spectrum.
Ethylene can be converted to vinyl chloride in a single stage, i.e.,
without isolating the intermediate ethylene dichloride by either chlorination or
oxychlorination routes, as is the case with the balanced ethylene route. Direct
chlorination routes require a high temperature and a large excess of ethylene to minimize
soot formation. The common problems with the direct routes of production are poor
selectivities to vinyl chloride and substantial production of chlorinated by-products, many
of which have no direct commercial utility. Hence commercially mainly the balanced
method is used.
Page 10
CHAPTER FOUR: PROCESS DESCRIPTION [1, 4]

The process chosen for vinyl chloride production is a combination of three processes,
direct chlorination, EDC pyrolysis and oxychlorination. This process is referred to as the
balanced process. Direct chlorination by itself is a process that operates at lower temperatures
and produces fewer by-products when compared to oxychlorination. Oxychlorination process
uses all the HCl produced during EDC pyrolysis in vinyl chloride production.
(1) Direct Chlorination: CH2 = CH2 + Cl2
C2H4 Cl2
(2) EDC Pyrolysis: CH2 = CH2 + HCl + O2

(3) Oxychlorination: C2H4 Cl2
Overall:
C2H4 Cl2 + H2O

2CH2 = CHCl + HCl
2CH2 = CH2 + O2 + Cl2
2CH2 = CHCl + H2O
On this basis, EDC production is about evenly split between direct chlorination and
oxychlorination, and there is no net production or consumption of HCl.
4.1 DIRECT CHLORINATION:

Ethylene and chlorine combine in a homogeneous catalytic reaction to form EDC.
Normally, the reaction rate is controlled by mass transfer, with absorption of ethylene as the
limiting factor. Due to high selectivity, ferric chloride is the common catalyst of choice for
chlorination of ethylene. The catalytic reaction utilizes an electrophilic addition mechanism. The
catalyst polarizes chlorine and then the polarized chlorine molecule acts as an electrophilic
reagent to add Cl- to the double bond of Ethylene.
EQUATIONS:
1. FeCl3 + Cl2
FeCl4-Cl+
2. FeCl4 - - Cl+ + CH2=CH2
FeCl3 + ClCH2CH2Cl
Page 11
Page 12
OXYGEN BASED OXYCHLORINATION.

FIG.2: TYPICAL (GEON) BALANCED VINYL CHLORIDE PROCESS WITH
chlorine
Ethylene
HCl
ethylene
oxygen
D ire c t c h lo r in a tio n
R e a c to r (3 5 3 K )
O xy c h lo r in a t io n
R e a c to r (5 0 3 K )
Q ue nc h
H e a v y e nd s
S e p e ra to r
EDC recycle
EDC pyrolysis
Furnace (723K)
Waste water
Wet Crude EDC

Decanter (700C)
Vent Gases
L ig h t e n d s e p a ra t in g
C o lu m n (D is t n . C o lu m n )
E D C p yro ly s is
Q ue nc h (7 0 0 C )
Light ends
H C l se p e r a tin g
c o lu m n
V in y l c h lo r id e
S ep e rat in g c o lu m n
Vinyl
Chloride
product

Conversion of the limiting component is essentially 100% and selectivity to EDC is greater than
99%.The direct chlorination reaction is very exothermic and requires heat removal for
temperature control. Early direct chlorination reactors were operated at moderate temperatures of
50-650C to take advantage of lower by product formation, and utilized conventional water
cooling for heat of reaction were devised. A widely used method involves operating the reactor
at boiling point of EDC, allowing the pure product to vaporize and then recovering heat from the
condensing vapour or replacing one or more EDC fractionation column reboilers with the reactor
itself.
4.2 OXYCHLORINATION OF ETHYLENE :

When compared with direct chlorination, the oxychlorination process is characterized
by higher capital investment, higher operating costs, and slightly less pure EDC product.
However, use of the oxychlorination process is dictated by the need to consume the HCl
generated in EDC pyrolysis.
In oxychlorination, ethylene reacts with dry HCl and either air or pure oxygen to
produce EDC and water. Various commercial oxychlorination processes differ from one another
to some extent, but in each case but in each case the reaction is carried out in the vapour phase in
either a fixed or fluidized bed reactor containing a modified Deacon catalyst . Oxychlorination
catalyst typically contains cupric chloride as the primary active ingredient, impregnated on a
porous support.
CuCl2 is widely recognized as the active chlorinating agent. The CuCl produced during the
ethylene chlorination step is rapidly reconverted to CuCl is thought to be advantageous because
it readily complexes with ethylene, bringing it into contact with CuCl 2 under reaction conditions,
and the presence of some CuCl is thought to be advantageous because it readily complexes with
ethylene, bringing it into contact with CuCl2 long enough for chlorination to occur. A very
simple represented of this heterogeneous catalytic cycle.
EQUATION:
1.
CH2=CH2 + 2CuCl2
2.
O2 + 2CuCl
3.
2HCl + CuOCuCl2
2CuCl + ClCH2CH2Cl
CuOCuCl2
2CuCl2 + H2O
Page 13

Usually fixed bed multitubular reactor is used for oxychlorination. Fixed- vertical
tubes held in a tubesheet at top and bottom. Uniform packing of catalyst within the tube is
important to ensure uniform pressure drop, flow and residence time through each tube. Reaction
heat can be removed by the generation of steam on the shell side of the reactor or by some other
heat transfer fluid. Fixed bed oxychlorination generally operates at higher temperature (2303000C) and pressure (150-1400 KPa). In the air-based oxychlorination process with either a
fluidized or fixed bed reactor, ethylene air are fed in slight excess of stoichiometric requirements
to ensure high conversion of HCl and to minimize losses of excess ethylene that remains in the
vent gas after product condensation. Under these conditions, typical feedstock conversion are 9499% for ethylene and 98-99.5% for HCl.bed reactors resembles multitube heat exchangers, with
the catalyst packed in.
The use of oxygen instead of air in the oxychlorination process with either a fixed or
fluidized bed reactor, permits operation at lower temperatures and results in improved operating
efficiency and product yield.
4.3 PURIFICATION OF ETHYLENE DICHLORIDE FOR PYROLYSIS:

EDC used for pyrolysis to vinyl chloride must be high purity, typically greater
than 99.5% because the cracking process is highly susceptible to inhibition and fouling by trace
quantities of impurities. It must also be dry to prevent excessive corrosion downstream.
Direct chlorination usually produces EDC with purity greater than 99.5%,
so that except for removal of the FeCl3, little further purification is necessary. Ferric chloride can
be removed by adsorption of a solid or the EDC can be distilled from the FeCl3 in a boiling
reactor as noted above.
EDC from the oxychlorination process is less pure than EDC from direct chlorination and
requires purification by distillation. It is usually first washed with water and then with caustic
solution to remove chloral and other water extractable impurities. Subsequently, water and low
boiling impurities are taken overhead in a first distillation column and finally pure dry EDC is
taken overhead in a second column
Page 14
4.4 ETHYLENE DICHLORIDE PYROLYSIS:

Thermal pyrolysis or cracking of EDC to vinyl chloride and HCl occurs as a homogeneous, first
order, free radical chain reaction. The accepted general mechanism involves the four steps as
follow:
(1) Initiation:
ClCH2CH2Cl
(2) Propagation: Cl + ClCH2CH2Cl

ClCH2C.HCl
(3) Termination: Cl + ClCH2CH2
ClCH2CH2 + Cl
ClCH2CHCl + HCl
CH2 = CHCl + Cl
CH2 = CHCl + HCl
The endothermic cracking of EDC is relatively clean at atmospheric pressure and at

temperatures of 425-5500C. Commercial pyrolysis units, however, generally operate at pressure
of 1.4-3 MPa and at temperature of 475-5250C to provide for better transfer. EDC conversion per
pass through the pyrolysis reactor is normally maintained at 53-63%, with the residence time of
2-30s.
Quenching of pyrolysis reactor effluent quickly minimizes coke formation. Substantial
yield losses to heavy ends and tars can occur if cooling is done too slowly. Therefore the hot
effluent gases are normally quenched and partially condensed by direct contact with cold EDC in
a quench tower. Alternatively the pyrolysis effluent gases can first be cooled by heat exchange
with cold liquid EDC furnace feed in a transfer line exchanger prior to quenching in the quench
tower.
Although there are minor differences in the HCl-vinyl chloride recovery section from one
vinyl chloride producer to another, in general the quench column effluent is distilled to remove
first HCl and then vinyl chloride. The vinyl chloride is usually further treated to produce
specification product, recovered HCl is sent to the oxychlorination process and unconverted
EDC is purified for removal of light and heavy ends before it is recycled to the cracking furnace.
The light and heavy ends are either further processed, disposed of by incineration or other
Page 15

methods or completely recycled by catalytic oxidation with heat recovery followed by chlorine
recovery as EDC.
Page 16
CHAPTER FIVE: THERMODYNAMICS[5]

The science of thermodynamics deals with energy and
its transformation.
Thermodynamics finds extensive application in chemical engineering. In chemical processes like

synthesis ammonia from mixture of nitrogen and hydrogen, thermodynamics enables us to
determine the maximum yield of ammonia obtained under given condition of temperature and
pressure. Thermodynamics also helps to lay down the criteria for predicting feasibility or
spontaneity of a process, including a chemical reaction, under a given set of conditions. It also
helps to determine the extent to which a process, including a chemical reaction, can proceed
before attainment of equilibrium.
From the values of standard free energy change, we formulate an approximate criterion
for the feasibility of chemical reaction, which will be useful in preliminary exploratory work. It
would be worthwhile to have some idea about whether or not the equilibrium is favourable,
before we search for catalyst and other condition necessary to cause the reaction. If the reaction
is not thermodynamically feasible, there is no point in pursuing a long and expensive
experimental investigation on improving the rate of equation. Therefore, to determine the
feasibility of a chemical reaction Gibbs free energy change of chemical reaction is determine
and the conditions for the feasibility of a chemical reaction are mentioned below:
Go < 0, the reaction is promising.(543)
0 < Go < 40,000 kJ/kmol, the reaction may or may not be possible and needs further study.
Go > 40,000 kJ/kmol, the reaction is very unfavorable.
Go = 0 (reaction is in a state of equilibrium), reaction proceeds t considerable extent before
equilibrium is reached.
Reactions:
1) CH2=CH2 + Cl2
2) CH2=CH2 + 2 HCl + O2
1) Cl CH2-CH2 Cl
Cl CH2-CH2 Cl
Cl CH2-CH2 Cl + H2O
CH2=CH Cl + HCl
Page 17

Data: Enthalpy and free energy of various compounds at standard temperature.
COMPONENT
Ho298 (
Ethylene
Go298 (
)
54.19
)
50.7
Hydrogen chloride
-22.063
-22.769
Ethylene dichloride
-39.44
-19.506
8.4
12.31
-68.311
-56.689
Vinyl chloride
Water
Now, H
o
T
o
T1
C P dT
T1
H o T T T1
1
H o T H ' T
2
3
2
3
T T1
(T T1 )
2
3
2 3
T
T .......(1) , where H ' constant
2
3
Page 18
POLYNOMIAL CONSTANTS FOR VARIOUS COMPONENTS[6]
COMPONENT
ALPHA
BETA
GAMMA
Chlorine
0.2914E-5
0.0918 E-5
0.949E-3
Oxygen
0.291 E-5
0.1004 E-5
2.526 E-3
Water
0.3336 E-5
0.2679 E-5
2.6105 E-3
Ethylene
0.3338 E-5
0.9479 E-5
1.596 E-3
Hydrogen chloride
0.2916 E-5
0.0905 E-5
2.0938 E-3
Vinyl chloride
0.4236 E-5
0.8735 E-5
1.6492 E-3
Hydrogen
0.2762 E-5
0.0956 E-5
2.466 E-3
Carbon monoxide
0.2911 E-5
0.0877 E-5
3.0851 E-3
Carbon dioxide
0.2937 E-5
0.3454 E-5
1.428 E-3
Ethylene dichloride
37.275
0.14362
1.04 E-5
Now,
Reaction
Direct chlorination
37.27499
0.1436
-2.5346E-3
Oxychorination
37.279
0.1435
-4.426E-3
Pyrolysis
-37.2749
-0.1436
3.723E-3
Enthalpy and free energy of reaction is given by

Ho298 =
Go298 =
Page 19
REACTIONS
Ho298 (
Direct Chlorination
Go298 (
-391.91E6
-293.86E6
Oxychlorination
-493.176 E6
-340.54 E6
Pyrolysis
107.897 E6
37.868 E6
For Direct Chlorination:

Put T = 298 K
+ 37.2749 298 +
= 391.9 10
Since,
0.1436 298
0.1436 298
+
2
3
391900
dlnK H o
dT
RT ..........................(1)
This gives,
H'
lnK
lnT
TA
RT
R
2R
Also, G
o
298
RTlnK
(2)
At T = 298K
293.86 10
=
+
298 391.9 10 37.2749 298 298

2.5346 10
6
. 1436 298
2
298
Page 20

= 329.152 10
Putting D in eqn (2), At T = 353K
= 293.861 10
As the free energy is negative, therefore the reaction is feasible.

2) Oxychlorination
Similarily,
= 493154
/kmolK.
= 512.272
= 492.937 10

3) Pyrolysis
Similarily,
We get, =
= 126949.91
= 30.87 10
Page 21
CHAPTER SIX: MATERIAL BALANCE [7]

Production capacity of vinyl chloride is 100 tonnes/day. Molecular weight of vinyl
chloride is 62.5. Thus production capacity is 66.66 kmoles/hr.
Basis : 1 hour of operation.
= 100
= 100 1000
= 4166.667 Kg/hr.
= 66.666 Kmoles
Now, the conversion of EDC after pyrolysis is 58%.
.
.
= 114.9425 kmol/hr
= 11379.31 Kg/hr.
50% of Ethylene dichloride is formed from oxychlorination and rest from direct chlorination.
MASS BALANCE ON DIRECT CHLORINATION REACTOR:

Ethylene and chlorine dissolve in the liquid phase and combine in homogeneous catalytic
reaction to form Ethylene dichloride.
The limiting reactant is ethylene with 100% conversion.
Ethylene required =
= 57.47126
114.9425
2
Chlorine is taken in 3.5% excess.

Chlorine required = 57.47126 1.035
Page 22

= 59.4268 Kmol/hr.

= 59.4268 57.47126
= 2.011494 Kmol/hr.
= 57.47126
Now taking mass balance on the reactor:
REACTANTS IN:
COMPONENT
KMOLES
MOLECULAR WEIGHT
MASS (KG)
Ethylene
57.47126
28
1609.195
Chlorine
59.4268
71
4223.276
TOTAL
116.954
5832.471
PRODUCTS LEAVING:
COMPONENT
KMOLES
MOLECULAR WEIGHT
MASS (KG)
Ethylene dichloride
57.47126
99
5689.655
Chlorine
2.011494
71
142.8161
TOTAL
59.48276
Therefore mass in = mass out
5832.471
MASS BALANCE ON OXYCHLORINATOR REACTOR:

Ethylene dichloride obtained =
114.9425
= 57.4716
2
The conversion for ethylene is 96% and for Hydrogen chloride is 98%
Amount of Ethylene required =
57.47126
0.96
Page 23

= 59.8659
Amount of Hydrogen chloride required =
57.47126 2
= 117.2883
0.98
Pure O2 is taken as reactant and it is taken in 20% excess

Amount of Oxygen required =
57.47126 1.2
= 34.48276
2
HCl remained unconverted = 117.2883 114.9425 = 2.345766
Amount of Heavies formed = 59.8659 57.47126

= 2.39464
REACTANTS ENTERING:
COMPONENTS
KMOLES
MOLECULAR
WEIGHT
MASS (KG)
Ethylene
59.8659
28
1676.245
HCl
117.2883
36.5
4281.023
Oxygen
34.48276
32
1103.448
TOTAL
211.637
7060.716
PRODUCTS LEAVING:
COMPONENTS
KMOLES
MOLECULAR
WEIGHT
MASS (KG)
Ethylene dichloride
57.47126
99
5689.655
Water
57.47126
18
1034.483
Byproducts
2.394636
133.5
319.6839
Therefore, mass in = mass out

Page 24
MATERIAL BALANCE ON WET CRUDE EDC DECANTER:

From literature, it is given that for 1Kg of vinyl chloride formed, vent gases out are
CO2 out = 0.0116 Kg
CO out = 0.0032 Kg
H2O out = 0..07Kg
O 2 out = 0.04 Kg
4166.667
CO2 out = 48.33333 Kg
= 1.09848485 Kmol.
CO out = 13.33333 Kg
= 0.47619048 Kmol.
H2O out = 291.1667Kg
= 16.230 Kmol.
O 2 out = 166.6666 Kg
= 5.20833 Kmol.
EDC coming in = EDC coming out = 57.47126 kmol/hr
REACTANTS ENTERING DECANTER:

COMPONENTS
KMOLES
MASS (KG)
57.47126
MOLECULAR
WEIGHT
99
Ethylene dichloride
Water
57.47126
18
1034.483
Byproducts
2.394636
133.5
319.6839
TOTAL
117.3372
5689.655
7043.822
Page 25
PROCUCTS LEAVING THE DECANTER:

COMPONENTS
KMOLES
MASS (KG)
57.4712644
MOLECULAR
WEIGHT
99
Ethylene dichloride
Water
47.4482759
18
854.069
Carbon dioxide
1.09848485
44
48.33333
Carbon monoxide
0.47619048
28
13.33333
Water vapours
16.2037037
18
291.6667
Light ends
0.1872
133.5
24.9912
Oxygen
5.20833
32
166.6666
TOTAL
128.093449
5689.655
7088.715
MATERIAL BALANCE ON LIGHT END DISTILLATION COLUMN:

Light end mainly consists of ethyl chloride. 99.8% Light ends are separated from the top
of the distillation column, while 99.6% EDC is separated from the bottom of the
distillation column.
For a distillation column,
F=D +W
F xf = D xd + W x w
For this distillation column;
xd = 0.9968, xw = 0.002
Taking overall balance over distillation column.
57.65846= D
+W
..............(1)
Page 26

Now taking balance on ethylene dichloride
57.47126 = 0.9968 D + 0.002 W
..............(2)
Solving equation 1 and 2 simultaneously, we get

D = 57.47126 Kmol/hr
W = 0.1872 Kmol/hr
FEED ENTERING THE DISTILLATION COLUMN:

COMPONENTS
KMOLES
MASS (KG)
57.47126
MOLECULAR
WEIGHT
99
Ethylene dichloride
Light ends
.18272
64.5
12.0744
TOTAL
57.65846
5689.655
5701.73
TOP PRODUCT FROM DISTILLATION COLUMN:

COMPONENTS
KMOLES
MASS (KG)
0.229885
MOLECULAR
WEIGHT
99
Ethylene dichloride
Light products
0.186826
64.5
12.05025
TOTAL
.416711
22.75862
34.80887
BOTTOM PRODUCTS FROM DISTILLATION COLUMN:

COMPONENTS
KMOLES
MASS (KG)
57.24138
MOLECULAR
WEIGHT
99
Ethylene dichloride
Light products
0.000374
64.5
0.024149
TOTAL
57.24175
5666.897
5666.921149
Page 27

Total mass out = Top product from stripping column + bottom product from stripping column
Therefore mass in = mass out.
MATERIAL BALANCE OVER HEAVY END SEPERATOR:

Assuming 100% conversion in heavy end separator. The heavy ends mainly consists of
1,1,2-trichloroethane (molecular wt. =133.5).
Total EDC entering the separator = 57.47126 + 57.47126
= 114.9425 kmol/hr
FEED ENTERING THE SEPERATING COLUMN:
COMPONENTS
KMOLES
MASS (KG)
114.9425
MOLECULAR
WEIGHT
99
Ethylene dichloride
Chlorine
2.011494
71
142.8161
Heavy ends
0.58
133.5
77.43
11379.31
TOP PRODUCT FROM SEPERATING COLUMN:

COMPONENTS
KMOLES
MOLECULAR
MASS (KG)
WEIGHT
Ethylene dichloride
114.9425
99
11379.31
Chlorine
2.011494
71
142.8161
TOTAL
116.95399
11522.1261
Page 28
BOTTOM PRODUCTS FROM SEPERATING COLUMN:

COMPONENTS
KMOLES
MOLECULAR
MASS (KG)
WEIGHT
Heavy ends
0.58
133.5
77.43
MATERIAL BALANCE OVER EDC PYROLYSIS FURNACE:

Conversion for EDC in pyrolysis furnace is 58%.
Vinyl chloride obtained = 0.58 114.9425
= 66.666Kmol/hr.
HCl obtained = 66.666
Ethylene dichloride unconverted = 114.9425 66.666

= 48.27586 Kmol/hr
FEED TO THE PYROLYSIS FURNACE:

COMPONENTS
KMOLES
MASS (KG)
114.9425
MOLECULAR
WEIGHT
99
Ethylene dichloride
Chlorine
2.011494
71
142.8161
TOTAL
116.95399
11379.31
11522.1261
Page 29
PRODUCT FROM PYROLYSIS FURNACE:

COMPONENTS
KMOLES
MASS (KG)
66.666
MOLECULAR
WEIGHT
62.5
Vinyl chloride
HCl
66.666
36.5
2433.333
Ethylene dichloride
48.27586
99
4779.31
Chlorine
2.011494
71
142.8161
TOTAL
183.6207
4166.667
11522.13
MATERIAL BALANCE OVER PYROLYSIS QUENCH:

The converted products from pyrolysis furnace are cooled by direct quenching into the
liquid. So the total mass coming in is equal to the total mass coming out.
MATERIAL BALANCE OVER HCl SEPERATING COLUMN:

Products from pyrolysis quench consist mainly of vinyl chloride, Ethylene dichloride and HCl.
Considering 100% conversion in separating column. Total HCl and Cl2 separated from the top of
separating column.
FEED TO THE HCl SEPERATING COLUMN:

COMPONENTS
KMOLES
MASS (KG)
66.666
MOLECULAR
WEIGHT
62.5
Vinyl chloride
HCl
66.666
36.5
2433.333
Ethylene dichloride
48.27586
99
4779.31
Chlorine
2.011494
71
142.8161
TOTAL
183.6207
4166.667
11522.13
Page 30
TOP PRODUCT FROM HCl SEPERATING COLUMN:

COMPONENTS
KMOLES
MASS (KG)
66.666
MOLECULAR
WEIGHT
36.5
HCl
Chlorine
2.011494
71
142.8161
TOTAL
68.677494
2433.333
2576.149
BOTTOM PRODUCTS FROM SEPERATING COLUMN:

COMPONENTS
KMOLES
MASS (KG)
66.666
MOLECULAR
WEIGHT
62.5
Vinyl chloride
Ethylene dichloride
48.27586
99
4779.31
TOTAL
114.94186
4166.667
8945.977
Total mass out = Top product from separating column + bottom product from separating column
TOTAL RECYCLE:
Now the top product from the seperating column is combined along with the Hydrogen
gas to convert unconverted chlorine to HCl. This combined stream is returned to the reactor as a
recycle stream. This total recycle stream is joined along with the make up streams of the
reactants and this combined stream is fed to the reactor.
Page 31
MATERIAL BALANCE OVER VINYL CHLORIDE SEPERATOR

(DISTILLATION COLUMN):
99.5% Vinyl chloride as MVC is separated from the top of the distillation column, while 99.8%
Ethylene dichloride is separated from the bottom of the distillation column.
For a distillation column,
F=D + W
F xf = D xd + W x w
For this distillation column;
xd = 0.995, xw = 0.0002, xf = 0.58
Taking overall balance over distillation column.
114.94186 = D + W
..............(1)
Now taking balance on vinyl chloride

66.666= 0.9968 D + 0.002 W
..............(2)
Solving equation 1 and 2 simultaneously, we get

D = 66.66667
Kmol/hr
W = 48.27586 Kmol/hr
FEED ENTERING THE DISTILLATION COLUMN:

COMPONENTS
KMOLES
MOLECULAR WEIGHT
MASS (KG)
Vinyl chloride
66.666
62.5
4166.667
Ethylene dichloride
48.27586
99
4779.31
TOTAL
114.94186
8945.977
Page 32
TOP PRODUCT FROM DISTILLATION COLUMN:

COMPONENTS
KMOLES
MOLECULAR WEIGHT
MASS (KG)
Vinyl chloride
66.33333
62.5
4145.833
Ethylene dichloride
0.096552
99
9.558621
TOTAL
66.42989
4155.392
BOTTOM PRODUCTS FROM DISTILLATION COLUMN:

COMPONENTS
KMOLES
MOLECULAR
MASS (KG)
WEIGHT
Vinyl chloride
48.17931
62.5
4769.752
Ethylene dichloride
0.333333
99
20.83333
TOTAL
48.51264
4790.585
Page 33
CHAPTER SEVEN: ENERGY BALANCE[9]

POLYNOMIAL GAS CONSTANTS FOR ALL THE
COMPONENTS[6,8]:
COMPONENT
Chlorine
0.2914E-5
0.0918 E-5
0.949E-3
Oxygen
0.291 E-5
0.1004 E-5
2.526 E-3
Water
0.3336 E-5
0.2679 E-5
2.6105 E-3
Ethylene
0.3338 E-5
0.9479 E-5
1.596 E-3
Hydrogen chloride
0.2916 E-5
0.0905 E-5
2.0938 E-3
Vinyl chloride
0.4236 E-5
0.8735 E-5
1.6492 E-3
Hydrogen
0.2762 E-5
0.0956 E-5
2.466 E-3
Carbon monoxide
0.2911 E-5
0.0877 E-5
3.0851 E-3
Carbon dioxide
0.2937 E-5
0.3454 E-5
1.428 E-3
Ethylene dichloride
37.275
0.14362
1.04 E-5
Ethyl Chloride
0.456 E-5
1.2962 E-5
1.5992 E-3
1,1,2 trichloroethane
34.934
.8505
-2.3306 E-3
Table No. 4: Polynomial constants for the components

The enthalpy is calculated as follows:
=
( +
= 34.48276
(0.291
+ 0.1004
+ 2.526
)dT
= 79176.40872 J/hr.
= 79.176408 kJ/hr.
Page 34
HEAT BALANCE ON OXYCHLORINATION REACTOR:

Oxygen and ethylene enters the reactor at 308K, while the recycle HCl enters the reactor at
343K. An exothermic reaction takes place in the reactor, during which a lot of heat is evolved.
This heat has to be removed from the reactor.
HEAT ENTERING THE REACTOR:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Oxygen
34.48276
79.17641
Ethylene
59.8659
86.85221
HCl
117.2883
902.4308
TOTAL
1068.459
HEAT LEAVING THE REACTOR:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
57.47126437
1136.71732
Water
57.47126437
4990.56532
Oxygen
5.20833
437.62937
Ethylene
2.394636015
127.131438
HCl
2.345765893
163.378356
TOTAL
6855.42181
Now the heat of reaction can be given as follows:
= 493.304 10 /
= 493.304 10
/
Page 35

For 28.732 kmol/hr of Ethylene dichloride formed
= 493.304 10 57.47126437
= 28350.80442 10
Total heat to be removed from the reactor can be calculated as follows:

=
= 6855.42181 - 1068.459 + 28350.80442 10
= 28356.591 10
This heat can be removed with the help of cooling water.

Cp = 4.186 kJ/kg,
=
T = 200C.
28356.591 10 =
4.186 20
m = 94.130 kg/s of cooling water will be required.
Page 36
HEAT BALANCE ON THE OXYCHLORINATION QUENCH:

Products from oxychlorination reactor are cooled quickly by quenching with water.
Products from oxychlorinator reactor enters the quench tower at 503K
And leaves at 329.8K.
HEAT ENTERING THE QUENCH:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
57.47126437
1136.71732
Water
57.47126437
4990.56532
Oxygen
5.20833
437.62937
Ethylene
2.394636015
127.131438
HCl
2.345765893
163.378356
TOTAL
6855.42181
HEAT LEAVING THE QUENCH:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
57.47126437
218.184194
Water
57.47126437
687.689687
Oxygen
5.20833
60.3044058
Ethylene
2.394636015
17.5185104
HCl
2.345765893
22.513194
TOTAL
Therefore, total heat removed by water = Hin - Hout
1006.20999
= 6855.42181 1006.20999
Page 37

= 5849.21191
As, Quenching is carried in water Cp = 4.184 kJ/kg. T = 400C
=
5849.21191 =
4.186 40
m = 34.9498 kg/hr of cooling water will be required.

Therefore, 34.9498 kg of quenching water required.
HEAT BALANCE OVER EDC DECANTER:

Since, the temperature change in the decanter is zero, therefore the heat added or heat
removed from the decanter is zero. Therefore there is no need to determine heat balance over the
decanter.
HEAT BALANCE OVER LIGHT END SEPARATING COLUMN:

Total feed entering to column = 57.47126 + 0.1872
= 57.65846 kmol/hr.
Mol fraction of Ethylene dichloride = 57.65846 / 57.47126
= 0.996
Therefore, Temperature of feed
= 355.67K
HEAT ENTERING THE SEPARATING COLUMN:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
57.47126
282.7743
Ethyl chloride
0.1872
1.830573
TOTAL
284.6049
Page 38

Temperature of the top product is 296.8K.
HEAT LEAVING THE SEPARATING COLUMN FROM TOP:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
0.229885
-1.15341
Ethyl chloride
0.186826
-1.85831
TOTAL
Temperature of the bottom product is 356.5K.
-3.01172
Bottom product mainly consists of Ethylene dichloride

Therefore, heat leaving from bottom product = 4.2675 kJ/hr.
The heat balance over distillation column is
F . hf + Qr = D . hd + W . hw + Qc
For R = 30 and 50C water for condensing vapour.
=
= ( + 1).
=673448.28
284.6049 +
= -3.01172+4.2675+673448.28
= 673164.92
This much amount of heat is supplied to the reboiler by condensing steam in the reboiler at
1000C
= 2676
Page 39
673164.92
2676.0
= 0.06988
Therefore, 0.06988kg/sec steam is required in reboiler
BALANCE OVER DIRECT CHLORINATION REACTOR:

Chlorine and ethylene enters the reactor at 308K. Ethylene dichloride and chlorine leaves
the reactor at 503K. An exothermic reaction takes place in the reactor, during which a lot of heat
is evolved. This heat has to be removed from the reactor with the help of coolent.
HEAT ENTERING THE REACTOR:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene
57.47126
83.37812
Chlorine
59.48276
51.35576
TOTAL
134.7339
HEAT LEAVING THE REACTOR:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
57.47126437
230.136082
Chlorine
2.011494253
18.8686657
TOTAL
= 391.84 10
249.004748
Therefore, for 28.732 kmol/hr Ethylene dichloride formed
= 391.84 10 57.47126
Page 40

= 22516.692 10
Total heat to be removed from the reactor can be calculated as follows:

=
= 249.004 134.7339 + 22516.692E3

= 22516.806 3
This heat can be removed with the help of cooling water.

Cp = 4.186 kJ/kg,
=
T = 200C.
22516806 =
4186 20
m = 269.08kg/hr of cooling water will be required.

Total feed entering to column = 172.1839 +2.011494 + 0.58
= 174.775kmol/hr.
Therefore, Temperature of feed mixture = 353 0.3466 + 356.59 0.637
+238.4 0.012 + 347 0.0035
= 353.57 K
Temperature of top product mixture
= 356.590.987 + 3470.0035
= 354.57
Page 41
HEAT ENTERING THE SEPARATING COLUMN:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
172.1839
814.8298
Chlorine
2.011494
11.18269
1,1,2-trichloroethane
0.58
2.144423
TOTAL
828.1569
HEAT LEAVING THE SEPARATING COLUMN AS TOP PRODUCT:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
172.1839
834.84996
Chlorine
2.011494
11.49121
TOTAL
846.3409
Temperature of product leaving from the bottom = 347.195K
HEAT
LEAVING
THE
SEPARATING
COLUMN
AS
BOTTOM
PRODUCT:
COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
1,1,2-trichloroethane
0.58
2.179632
Ethylene dichloride
1.3774713
6.6788
TOTAL
8.858432
Page 42

F . hf + Qr = D . hd + W . hw + Qc
For R = 30 and 50C water for condensing vapour.
.
= ( + 1).
= 2025.081 /
828.1569 +
= 846.3409+8.854 + 2025.081
= 2052.839 /
1000C
= 2676
=
=
.
2052.839
2676.0
= 0.7571
Therefore, .7571kg/hr steam is required in reboiler.
Page 43
ENERGY BALANCE OVER THE PYROLYSIS FURNACE:

Ethylene dichloride and chlorine enters the furnace at 354.83K, while the products from
furnace leaves at temperature 723K. The reaction is endothermic and heat is supplied by
condensing steam.
HEAT ENTERING THE PYROLYSIS FURNACE:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
114.9425
557.3097
chlorine
2.011494
11.49121
TOTAL
568.8009
HEAT LEAVING THE PYROLYSIS FURNACE:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
12752.28
Chlorine
2.011494253
221.5939
HCl
66.66666667
16189.96
Ethylene dichloride
48.27586207
2327.296
TOTAL
= 107.507 10
31491.13
Therefore, for 33.33 kmol/hr Ethylene dichloride formed
= 107.507 10 66.66
= 7166.416 3 /
Page 44

Total heat to be supplied to the reactor can be calculated as follows:
=
= 34491.13-568.8009+ 3583208.31
= 7200.3389 3
This heat will be supplied bysteam at 4 bar condensing at 1430C

= 2737.6
Therefore, amount of steam required is
.
7200338.9
2737.6
= 0.7306
Therefore, 0.7306 kg/s steam is required in reboiler.
HEAT BALANCE ON THE OXYCHLORINATION QUENCH:

Products from pyrolysis furnace are cooled quickly by quenching with water. Products
from pyrolysis furnace enters the quench tower at 723K
And leaves at 343K.

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
12752.28
Chlorine
2.011494253
221.5939
HCl
66.66666667
16189.96
Ethylene dichloride
48.27586207
2327.296
TOTAL
31491.13
Page 45

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
503.9714916
Chlorine
2.011494253
8.757366433
HCl
66.66666667
639.8249739
Ethylene dichloride
48.27586207
183.2747232
TOTAL
1335.828555
Therefore, total heat removed by water = Hin - Hout

= 31491.13 1335.82
= 30155.31 kJ/hr
As, Quenching is carried in water
Cp = 4.184 kJ/kg. T = 400C
=
30155.31 =
4.186 40
m = 0.04668 kg/sec of cooling water will be required.

Therefore, 0.04668 kg/sec of quenching water required.
Page 46
ENERGY BALANCE OVER COOLER:

The product mixture from quenching are cooled to 259K with the help of coolant and
then distilled.
HEAT ENTERING THE COOLER:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
503.9714916
Chlorine
2.011494253
8.757366433
HCl
66.66666667
639.8249739
Ethylene dichloride
48.27586207
183.2747232
TOTAL
1335.828555
HEAT LEAVING THE COOLER:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
-328.703417
Chlorine
2.011494253
-5.71177223
HCl
66.66666667
-417.309656
Ethylene dichloride
48.27586207
-146.448353
TOTAL
-898.173198
Total heat that must be removed is:

=
= 1355.82 + 898.173
= 2253.993 /
Page 47

This heat will be removed by refrigerant vapourising in cooler.
Therefore, amount of refrigerant required is
.
2253.993
380.1
= 5.93
Therefore, 0.00163 kg/s refrigerant is required.

Temperature of feed mixture = 259.15K
Temperature of top product mixture is 189.5K and Temperature of bottom product mixture is
301.14 K
HEAT ENTERING THE HCl SEPARATING COLUMN:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Vinyl chloride
66.66666667
-328.703417
Chlorine
2.011494253
-5.71177223
HCl
66.66666667
-417.309656
Ethylene dichloride
48.27586207
-146.448353
TOTAL
-898.173198
Page 48
HEAT LEAVING THE HCl SEPARATING COLUMN AS TOP PRODUCT:

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
HCl
66.66666667
-384.5732
Chlorine
2.011494253
-6.682579
TOTAL
-391.255768
HEAT LEAVING THE HCl SEPARATING COLUMN AS BOTTOM

PRODUCT:
COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
66.66666667
456.25092
Vinyl chloride
48.27586207
158.76068
TOTAL
615.01159
The heat from top gases can be removed by refrigerant at T = 170K

= 504.5kJ/kg
For R = 30
=
= ( + 1).
= 17179.92

F . hf + Qr = D . hd + W . hw + Qc
898.173 +
= -399.255+ 615.01159+ 17179928
= 18301.87 /
Page 49

1000C
= 2676
=
=
18301.87
2676.0
= 6.839
ENERGY BALANCE
COLUMN:
OVER
VINYL
CHLORIDE
DISTILLATION
HEAT ENTERING THE VINYL CHLORIDE DISTILLATION COLUMN

COMPONENT
KMOLES/HR
ENTHALPY (KJ/HR)
Ethylene dichloride
66.66666667
456.25092
Vinyl chloride
48.27586207
158.76068
TOTAL
615.01159
TOTAL HEAT LEAVING FROM THE TOP OF THE DISTILLATION COLUMN
=-
197073.4 kJ/hr
TOTAL HEAT LEAVING FROM THE BOTTOM OF THE DISTILLATION COLUMN
= 239.95 kJ/hr
The heat from top gases can be removed by refrigerant at T = 170K
= 504.5kJ/kg
For R = 30
Page 50

=
= ( + 1).
= 45871279.08

F . hf + Qr = D . hd + W . hw + Qc
615.01159 +
= -197073.4 + 239.95 +45871279.08
= 45665399
1000C
= 2676
=
=
.
45665399
2676.0
= 4.74
Page 51
CHAPTER EIGHT: DESIGN OF REACTOR[10,11,12,13]

AIM:- TO DESIGN FIXED BED MULTITUBULAR REACTOR
Figure no.3: Diagram of Multitubular reactor.

REACTION OCCURING:
CH2=CH2 + 2 HCl + O2
Cl CH2-CH2 Cl + H2O
CONDITIONS:1) Reaction temperature

2) Reactor pressure
= 2300C
= 6 atm
3) Catalyst: Deacon Catalyst with higher loading of CuCl2
Page 52

(1) VOLUME OF REACTOR:
The design equation is given as:
=
The rate expression for the given oxychlorination reaction is given by:
C2H4 Cl2
2CH2 = CHCl + HCl
r = k [C2H4 Cl2]
Activation Energy= 58kcal/mol
=
(1 0.67 0.52
0.14 (1 )
) . 2( + 2) + 3.13 0.67( + 2)
+ 0.71
Where,
= {( + 2) + 3.13( + 2) + 1.23
W = weight of catalyst
F = flow rate of ethylene
For synthesis of ethylene dichloride diluted with inert gas
Constants d = 8.78
P = 6 atm.
=
5.04(1 )
21.74 22.56 + 362.936
21.74
22.56 + 362.936
5.04(1 )
For conversion of 99%, x = 0.99

Therefore, Integrating equation between 0 to 0.99
Page 53

.
21.74
22.56 + 362.936
5.04(1 )
= 4225
Flow rate of ethylene = F = 59.8659 kmol/hr
= 4225 59.8659
= 252933.4275
There are two reactors in parallel.
252933.4275
2
= 126466.71
As density = 3054 kg/m3
.=
12466.7
3054
= 41.410 m3
(2) TUBE DIAMETER AND LENGTH:

Internal diameter = 3 =7.62 cms
= 0.0762 m
Tube thickness
= 3 mm = 0.003 m.
=
+2
=7.62 + 2(0.3)
= 8.22 cm
= 0.0822 m.
Considering length of each tube = L = 5 m
Page 54
(3) NUMBER OF TUBES:
3.14
4
Where, Di = Internal diameter of tube

L = length of each tube
3.14 0.0762
5
4
= 0.0228 m3
41.410
0.0228
= 1826 tubes
(4) SHELL DIAMETER:

We take triangular spacing, therefore the area occupied by each tube is given by
= 0.866
Where, s is pitch of tubes
= (1.25
Therefore, Area required for N number of tubes

=
0.866
To provide pass partition, the actual area of the tube sheet, for locating the tubes will be
greater than the area given by the above equation, so we have to divide it by proportionality
factor, B = 0.95.
This area corresponds to the area of the shell
Page 55
4 1826 0.866 (1.25 0.0762)

3.14 0.95
= 19.1431
D = 4.37m
Thus diameter of shell is 4.37 meters.
(4) COOLING ARRANGEMENT:

Water is used for cooling. The inlet for it is at the bottom and outlet at the top.
(i) Heat to be removed (from energy balance)
= 28356591.56 /
About 10% of this heat is lost
= 2.35659 10 /
= 25520.9324
10
2
= 12760.4662 10 /
This amount of heat is removed by cooling water
Cp = 4.186 kJ/kg
= 20
12760.4662 10 =
= 42.3384
4.186 20
Therefore, water flow rate to reactor is 42.3385 kg/s.
Page 56
(ii) Area available for heat transfer:

For single tube = 3.14DoL
Therefore, total area for heat transfer from 1826 tubes
= 1826 3.14 0.0762 5
= 2184.51 m
(iii) Determination of overall heat transfer coefficient:
The gas side heat transfer coefficient is given by
= 0.813
exp 6
Where, Dp = Diameter of catalyst particals

kg = Thermal conductivity of gas mixture
G = mass flow rate of gas mixture
= viscosity of gas mixture
Now, for a fixed bed with
= 0.16
And G = 0.0024 gm/cm2

K = 0.02 Cal/sec.m.K
Putting these values in equation for hi , we have
hi = 0.1593 cal/s.m2.K
hi = 0.6665W/m2.K
Since, the internal heat transfer coefficient is controlling factor we take
hi = U = 0.6665W/m2.K
Page 57

Q = U. A.(T)lm
Temperature in reactor
= 2300C
Temperature of inlet water
= 300C
Temperature of outlet water = 500C

(230 30) (230 50)
200
ln 180
( )
( )
= 189.82
Therefore, minimum area required for heat transfer
. ( )
25520932.4
2 3600
= 3544.5739 10 /
= 2085
This area is less than the available area therefore cooling is possible.
Page 58
MECHANICAL DESIGN:
(1) SHELL THICKNESS
Pressure = 1atm + static head
= 1 kg/cm2 + 0.5 kg/cm2
= 1.5 kg/cm2
Considering the stresses due to support we will overdesign it for pressure of 2.5kg/cm2

Where, f is allowable stress of material = 1210 kg/cm2

J is joint efficiency = 0.85
=
2.5 473
+ .3
2 1210 0.85 2.5
= ..875cm
= 9 mm.
2) CONICAL BOTTOM:
For better distribution of gasses conical bottom is used. It consists of a gas inlet at its apex.
=
.
2
P = Design pressure
= 1.1 working pressure
= 1.1 6
Page 59

= 6.6 kg/cm2
Z = factor depending on apex angle = 3.2
We will have apex angle as 600
=
6.6 473 3.2

+ .3
2 1210 0.85
= 50 mm.
(3) TOP HEAD (TORISPHERICAL HEAD):
Here, t is thickness of head
Ri is internal crown radius
ri is internal knuckle radius
ho is height of head
Sf is straight flange portion = 3t
Crown radius = Do =outside diameter of shell
So we have crown radius = Ri =473 + 2(0.1)
= 473.2 cm
Knuckle radius = 6% Di = 0.06 4.73
= 0.2838 m
Now,
=
Where w = stress intensity factor
3+
Page 60
1
4.73
3+
4
. 2838
=1.77
=
6.6 473 1.77

+ .3
2 1210 0.85
=30 mm
Sf = 3t = 3 30
= 90 mm
ho =
r = r + t = .2838 + 30
h = 31.38cm
(4) TUBE SHEET:
It is a flat plate having provision for making a gasketed joint around the periphery. A large
number of holes are drilled in the tube sheet according to the pitch requirements of the tubes. The
common method of fixing the tube in these holes consists of expanding the ends of the tubes.
The relation giving effective tube sheet thickness is
=
Where, F is constant which varies according to the type heat exchanger.

G is mean gasket diameter
P is design pressure
And
Page 61

For k = 0.055
F = 0.9
= 0.9 473
0.25 6.6
1210
= 15
(5) GASKET DESIGN:
d
y Pm
=
d
y P(m + 1)
Where, P is internal design pressure
Y is minimum design yield stress = 260 kg/cm2
m = 2.75
The thickness of gasket is taken as = 2mm
d
260 6.6 2.75
=
d
260 6.6(2.75 + 1)
= 1.028
d = 1.028 4.73
= 4.862 m.
Mean gasket diameter = G =
G = 4.79m
Minimum gasket width =
= 0.066 m.
Page 62

(6) BOLT AND FLANGES:
Diameter of bolt selected = 20 mm
Bolt spacing = 2.5 d = 2.5 20
= 50 mm.
Bolt circle diameter = outer diameter of gasket + 2 diameter of bolt + 0.015
= 4.862 +2 0.02 +0.015
= 4.9 m
3.14
5
3.14 4.9 10
5
= 307 bolts
Flange thickness:
P
K. f
1
1.5 .
0.3 +
.
Where, W is total bolt load

h is radial distance from gasket load reaction to bolt circle.
H is total hydrostatic end force
f is permissible stress
As, K = 4.4
Page 63

6.6
4.4 1210
= 479
= 16.86
+ 2(
= 4.73 + 2 0.02
= 47.7 cm = 18 inch
(8) NOZZLE DESIGN:

(a) Water nozzle
Flow rate of water = 9 kg/s
Density of water = 998 kg/cm2
So, the selected nozzle size is
Nominal diameter = 10.16 cm
Outside diameter = 11.36cm
=
Thickness = 15 mm
Height of nozzle = 15.24 cm
Page 64
CHAPTER NINE: COST ESTIMATION AND ECONOMICS[14]

DETERMINING PURCHASED EQUIPMENT COST (PEC):Cost index of 2007-2008 = 582
Cost index of 2015 = 1024
Fixed Capital Investment for that year: 9.46E+07 Rs
Hence, Fixed Capital Investment for 2015: (1024 9.46E+07)/ 582
= 1.66E+08 Rs
Estimation of total investment cost:
1. Direct cost:
Purchased equipment cost(PEC) = 15-40% FCI
= 5.82E+07 Rs
Installation cost (IC) = 35-45% PEC
= 2.33E+07 Rs
Instrument and control installed (I&CI) = 6-30% PEC
= 1.75E+07 Rs
Piping installation cost (PIC) = 10-75% PEC
= 3.49E+07 Rs
Electrical installation cost (EIC) = 10-40% PEC
= 2.33E+07 Rs
Building process and auxiliary (BP&A) = 10-65% PEC
= 3.49E+07 Rs
Page 65

Service facilities (SF) = 30-75% PEC
= 4.08E+07 Rs
Yard improvement (YI) = 10-15% PEC
= 8.74E+06 Rs
Land (L) = 4-8% PEC
= 4.66E+06 Rs
TOTAL DIRECT COST (TDC): 2.46E+08 Rs
2. Indirect cost:
Expenses which are not directly involved with material and labour of actual installation or
complete facility.
Engineering and supervision (E&S) = 5-30% DC
= 7.39E+07 Rs
Construction expenses (CE) = 10% DC
= 2.46E+07 Rs
Contractor's fee (CF) = 2-7% DC
= 1.72E+07 Rs
Contingency (Cntg.) = 8-20% DC
= 4.93E+07 Rs
TOTAL INDIRECT COST (TIC): 1.65E+08 Rs
3. Fixed capital investment:

TCI = FCI + WCI
= 4.11E+08 Rs
4. Working capital investment (WCI) : 10-20% FCI= 6.17E+07 Rs
5. Total capital investment(TCI): FCI + WCI = 4.73E+08 Rs
Page 66

Estimation of total product cost (TPC):
1) Fixed charge:
Depreciation: 10% FCI (machinery)
= 4.11E+07 Rs
Insurances : 0.4-1% of FCI
= 4.11E+06 Rs
Local taxes (LT) = 3-4% FCI
= 1.65E+07 Rs
TOTAL FIXED CHARGES (TFC): 1.11E+08 Rs
But, Fixed charges = 10-20% TPC
TOTAL PRODUCT COST: 1.11E+09 Rs
2) Direct production:
Raw material (RM) = 10-50% TPC
= 3.33E+08 Rs
Maintenance: 2-10% of FCI
= 2.47E+07 Rs
Operating labour (OL) = 10-20% TPC
= 1.67E+08 Rs
Direct supervisory & electric labour (DS&EL) = 10-25% OL
= 2.50E+07 Rs
Laboratory charges (LC) = 10-20% OL
= 2.50E+07 Rs
Utilities = 10-20% TPC = 1.67E+08 Rs
Patent and royalties (P&R) = 2-6% TPC
= 4.44E+07 Rs
Operating supplies (OS) = 10-20% of Maintainance
= 3.70E+06 Rs
PLANT OVERHEAD COST (POC) = 50-70% (OL+OS+M)
= 1.17E+08 Rs
Page 67

TOTAL DIRECT COST= 7.89E+08 Rs
3) General expenses:
Administration cost (AC) = 40-60% OL
= 9.16E+07 Rs
Research and development cost( R&DC) = 3% TPC
=3.33E+07 Rs
Distribution and selling price (D&SP) = 2-30% TPC
=1.67E+08 Rs
GENERAL EXPENSES (GE): 2.92E+08 Rs
Therefore, Manufacturing cost = Total Direct Cost + TFC + POC
MC = 1.02E+09 Rs
Therefore, Total production cost = MC + GE
T ProC = 1.31E+09 Rs
Gross earning and rate of return:
The plant is working for say: 300 days
SP = 50 Rs/kg
Total income (Rs) = Capacity No. Of working Days Capacity
= 1.50E+09 Rs
Gross income = Total income TPC
GI= 1.91E+08 Rs
Tax (%) = 45
Net profit= GI GI Tax
= 1.05E+08 Rs
Rate of Return= Net Profit 100 / Total Capital Investment
=22.22%
Payback Period = 1/ rate of return
= 4.50 years
Page 68
CHAPTER TEN: PROCESS CONTROL AND

INSTRUMENTATION[15,16}:
The process information segment such as temperature, flow rate etc are communicated
between process plant and PLC control Unit.
Sr.
No
Control Equipment
SENSOR
INFORMATION
COMMUNICATED
Oxychlorination Reactor
(i)Thermocouple
(ii)composition
measurement
(i) measuring temperature of

ethylene dichloride.
(i) Thermocouple
(ii)composition
measurement
(i) measuring temperature of

ethylene dichloride.
(i)Thermocouple
(i)For measuring Temperature

of Ethylene dichloride.
Direct chlorination
reactor
Quench
(ii)Flowmeter
(ii)For measuring composition

of feed stream.

of feed stream.
(ii)for measuring flow rate of

the outlet.
4
Distillation column
(i)Flowmeter
(ii)composition measurent
(i)for measuring flow rate of

the outlet.
of feed.
EDC Still
(i)Flowmeter
i)for measuring flow rate of

the feed.
of feed.
Tubular pyrolysis
furnace
(i)Thermocouple
(ii)Flowmeter
(iii)composition measurent

the outlet.
of product stream.
Page 69

7
Heat exchanger
(i)Thermocouple
(ii)Flowmeter

the water.
Quench
(i)Thermocouple
(ii)Flowmeter

of vinyl chloride.
the outlet stream.
HCL separator
(i)Flowmeter
(Distillation column)

the feed stream.
of feed stream.
10
Vinyl chloride separator

(Distillation column)
(i)Flowmeter

the feed stream.

of feed stream.
Table No.: 5 Process Information communicated between process plant and PLU control unit .
DIRECT DIGITAL FEEDFORWARD FEEDBACK CONTROL OF

DIRECT CHLORINATION REACTOR FOR EXOTHERMIC REACTION:
The direct digital control for direct chlorination reaction is given in fig. shown below. The
Temperature and composition of feed to the reactor is controlled and monitored by feedforward controller
which is monitored by computer.This controller measures the readings and compare it with set point and
minimizes error and feed flow and temperature is controlled.
The temperature of reaction mixture and coolant is measured by thermocouple and compared with
set point through feedback controller monitored by computer. The error is generated which is minimized
by controller and controller gives signals to the transducer which regulate the flow rate of coolant and
temperature of both reaction mixture and coolant is determined.
Page 70
Fig.4: Direct digital control feedforward feedback control of direct chlorination reactor for
exothermic reaction
Page 71
CHAPTER ELEVEN:PLANT LAYOUT AND SITE

SELECTION[17]:
The location of the plant can have a crucial effect on the profitability of a project, and the
scope for future expansion. Many factors must be considered when selecting a suitable site, the
principal factors to consider are:
1. Location, with respect to the marketing area.
2. Raw material supply.
3. Transport facilities.
4. Availability of labour.
5. Availability of utilities: water, fuel, power.
6. Availability of suitable land.
7. Environmental impact, and effluent disposal.
8. Local community considerations.
9. Climate.
10. Political and strategic considerations.
Page 72

RAW MATERIALS:
The availability and price of suitable raw materials will often determine the site location.
Plants producing bulk chemicals are best located close to the source of the major raw material;
where this is also close to the marketing area.
TRANSPORT:
The transport of materials and products to and from the plant will be an overriding
consideration in site selection. If practicable, a site should be selected that is close to at least two
major forms of transport: road, rail, waterway (canal or river), or a sea port. Road transport is
being increasingly used, and is suitable for local distribution from a central warehouse. Rail
transport will be cheaper for the long-distance transport of bulk chemicals. Air transport is
convenient and efficient for the movement of personnel and essential equipment and supplies,
and the proximity of the site to a major airport should be considered.
UTILITIES (SERVICES):
Chemical processes invariably require large quantities of water for cooling and general
process use, and the plant must be located near a source of water of suitable quality. Process
water may be drawn from a river, from wells, or purchased from a local authority. At some sites,
the cooling water required can be taken from a river or lake, or from the sea; at other locations
cooling towers will be needed. Electrical power will be needed at all sites.It is suitable get steam
supply from common boiler such type of facility is available in gujrat G.I.D.C ankleshwar.
ENVIRONMENTAL IMPACT AND EFFLUENT DISPOSAL:
All industrial processes produce waste products, and full consideration must be given to
the difficulties and cost of their disposal. The disposal of toxic and harmful effluents will be
covered by local regulations, and the appropriate authorities must be consulted during the initial
site survey to determine the standards that must be met. An environmental impact assessment
should be made for each new project, or major modification or addition to an existing process.
Page 73

LOCAL COMMUNITY CONSIDERATIONS:
The proposed plant must fit in with and be acceptable to the local community. Full
consideration must be given to the safe location of the plant so that it does not impose a
significant additional risk to the community. On a new site, the local community must be able to
provide adequate facilities for the plant personnel: schools, banks, housing, and recreational and
cultural facilities. VCM is mostly required for production of PVC so plant must be situated near
PVC manufacturing plant. Such type of industries mostly found in Gujarat.
LAND (SITE CONSIDERATIONS):
Sufficient suitable land must be available for the proposed plant and for future expansion.
The land should ideally be flat, well drained and have suitable load-bearing characteristics. A full
site evaluation should be made to determine the need for piling or other special foundations.
CLIMATE:
Adverse climatic conditions at a site will increase costs. Abnormally low temperatures
will require the provision of additional insulation and special heating for equipment and pipe
runs. Stronger structures will be needed at locations subject to high winds (cyclone/hurricane
areas) or earthquakes.
POLITICAL AND STRATEGIC CONSIDERATIONS:
Capital grants, tax concessions, and other inducements are often given by governments to
direct new investment to preferred locations; such as areas of high unemployment. The
availability of such grants can be the overriding consideration in site selection.
Page 74
Future
Utilities
Scrap
Yard
ExpaGeneransion
Main Plant
ETP
Storage
Control
Building
Room
Tank Yard
W.
B.
Fire
Station
Wash and
Changing
Room
Quality
Control
Laboratory
Cante-
Medical
Centre
Cooling
towers
Maintenance
Building
Research
and
Development
Centre
en
Administration Building
Parking
Training
Centre
Space
Security
Power
Station
Green Belt
Fig 5: General Plant Layout for a Chemical Industry.
Page 75
STORAGE AND TRANSPORTATION[18]:

Vinyl chloride is stored as a liquid at -14C to -22C. The presently accepted upper limit of
safety as a health hazard is 500 ppm. Often, the storage containers for the product vinyl chloride
are high capacity spheres with 56 ppm of hydroquinone stabilizer. The spheres have an inside
sphere and an outside sphere. Several inches of empty space separate the inside sphere from the
outside sphere. This void area between the spheres is purged with an inert gas such as nitrogen.
As the nitrogen purge gas exits the void space it passes through an analyzer that is designed to
detect if any vinyl chloride is leaking from the internal sphere. If vinyl chloride starts to leak
from the internal sphere or if a fire is detected on the outside of the sphere then the contents of
the sphere are automatically dumped into an emergency underground storage container.
Transporting VCM presents the same risks as transporting other flammable gases such as
propane, butane (LPG) or natural gas (for which the same safety regulations apply).The
equipment used for VCM transport is specially designed to be impact and corrosion
resistant.Vinyl Chloride may contain acetylene as impurity hence contact with copper,
magnesium, silver, etc. Any contact with any ignition source or heat is avoided. A distance from
oxidizing agents, caustic soda and reactive metals is kept. Goggles, self-contained breathing
apparatus and rubber over clothing are to be worn while contacting with it. VCM stabilized
liquid is shipped in spherical refrigerated steel tanks. Between loads, the vessel tank must be
carefully dried, then purged with nitrogen. VCM in a gaseous form must be controlled carefully
under refrigeration. Vinyl chloride tends to acquire an electrostatic charge during movement and,
therefore, as a safeguard all pipe work and equipment in transfer system need to be grounded and
earthed. Safety valves should be provided only on bulk containers and tank cars to avoid build up
of excessive pressure. In an area where vinyl chloride monomer is handled, all the electrical
equipments and fittings must be flame proof type. In an area where vinyl chloride monomer is
handled, all the electrical equipments and fittings must be flame proof type.
Page 76
ENVIRONMENT EFFECTS[18,19]:
If released to soil, VCM is expected to have high mobility. Volatilization from moist soil
surfaces is expected to be an important fate process based on its vapor pressure. If VCM is
released into water, it is not expected to adsorb to suspended solids and sediment in the water.
The biodegradation half-life of vinyl chloride in aerobic and anaerobic waters was reported as 28
and 110 days, respectively. Volatilization from water surfaces is expected to be an important fate
process. The estimated volatilization half-lives for a model river and model lake are 1 hour and 3
days, respectively. VCM is practically non-toxic to fish on an acute basis. If released to air,
VCM will exist solely as a gas in the ambient atmosphere. It will be degraded in the atmosphere
by reaction with photochemically produced hydroxyl radicals.
MARKING AND LABELLING[19]:

All containers of vinyl chloride shall bear an identifying label as depicted in IS: 1260
(Part I)1973*. Containers of vinyl chloride shall labelled as follows:
VINYL CHLORIDE
DANGER
EXTREMELY FLAMMABLE AND TOXIC LIQUID AND GAS UNDER PRESSURE
KEEP THE CONTAINER CLOSED IN A COOL PLACE.
KEEP AWAY FROM HEAT, SPARKS, FLAME AND OXIDIZING AGENTS.
INJURIOUS TO HEALTHAVOID CONTACT.
AVOID CONTACT WITH SKIN AND PROLONGED BREATHING OF THE
VAPOUR.
USE WITH ADEQUATE VENTILATION.
GROUND THE CONTAINER WHEN EMPTYING.
Page 77
REFERENCES:
(1) Encyclopedia of chemical technology, Fifth edition, vol. 25, Kirk
Othmer, Page no. 628-651
(2) Ulmans Encyclopedia of Industrial Chemistry, Vol.8, Ulman,
Page no. 56-57
(3) Encyclopedia of Chemical processing & Design, John J. Mcketta.
Page no. 313-320
(4) Chemical Weekly, February 22, 2011, pageno-253-254
(5) Physical chemistry, Puri Sharma and Pathania
(6) Perrys Chemical Engineering handbook, Robert H. Perry, D W Green and J O
Maloney.
(7) Handbook of chemistry and physics, Yawns
(8) Stichiometry, Bhutt and Vora.
(9) Transport Processes and Separation Process Principles, Fourth Edition,
Christie John Geankoplis, Page no. 61, 291, 706.
(10) Process Equipment Design, M.V. Joshi, Page no. 139, 236.
(11) Chemical Engineers Handbook, Page no. 4-25.
(12) Chemical Equipment Design, B C Bhattacharya, Page no. 35, 49, 103
(13) Chemical Reaction Engineering, Third Edition, Octave Levenspiel.
(14) Plant design & economics for chemical engineers, Max Peters & Klaus Timmerhaus.
(15) Process Automation and modelling, R. P. Vyas, Page no. 365
(16) Process control and Instrumentation, R. P. Vyas, Page no. 229.
(17) Industrial Engineering & Management by, O.P.Khanna & A. Sarup, Ganpatrai Pub.
Page no. 4.1-4.30
Page 78
(18) Indian Standard CODE OF SAFETY FOR VINYL CHLORIDE (VCM)

Chemical Hazards Sectional Committee, (July 1981).
(19) Occidental Chemical Corporation, Product Stewardship Summary Vinyl Chloride
Monomer (2008), Page no 3 &4.
Page 79

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Laxminarayan Institute of Technology 2015

CHAPTER ONE: INTRODUCTION[1,2]

Laxminarayan Institute of Technology 2015

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

CHAPTER TWO: HEALTH AND SAFETY FACTORS &

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

PHYSICAL AND CHEMICAL PROPERTIES OF VINYL CHLORIDE:

Melting point (1atm), K

Boiling point (1atm), K

Heat capacity at constant pressure, J/(mol.K)

Table no: 1 Physical and chemical properties of vinyl chloride.

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

IMPORT DATA OF VINYL CHLORIDE[3]

Table No: 2 Import data of Vinyl Chloride.

Figure no.1: Projected Increase in Demand of Vinyl Chloride

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

MAJOR PRODUCERS OF VINYL CHLORIDE IN INDIA.

Finolex Pipes Limited, Ratnagiri

Table no.3: Major Producers of Vinyl Chloride in India.

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

CHAPTER THREE: MANUFACTURING PROCESSES [2]

CH2 = CHCl , H= -99.2 KJ/mol

(2) Thermal cracking of 1, 2-dichloroethane:

CH2 = CHCl + HCl , H=100.2 KJ/mol

CH2 = CHCl + HCl

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

C2H2 + C2H4 + Cl2

Direct chlorination: CH2 = CH2 + Cl2

EDC pyrolysis: CH2 = CH2 + 2HCl + O2

Oxychlorination: 2C2H4 Cl2

2CH2 = CHCl + 2HCl

Overall Reaction: 2CH2 = CH2 + O2 + Cl2

2CH2 = CHCl + H2O

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

SELECTION OF PROCESS [1, 4]

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

CHAPTER FOUR: PROCESS DESCRIPTION [1, 4]

(2) EDC Pyrolysis: CH2 = CH2 + HCl + O2

C2H4 Cl2 + H2O

2CH2 = CH2 + O2 + Cl2

2CH2 = CHCl + H2O

4.1 DIRECT CHLORINATION:

2. FeCl4 - - Cl+ + CH2=CH2

Vinyl Chloride Monomer

Vinyl Chloride Monomer

OXYGEN BASED OXYCHLORINATION.

Wet Crude EDC

Laxminarayan Institute of Technology 2015

Laxminarayan Institute of Technology 2015

4.2 OXYCHLORINATION OF ETHYLENE :

Vinyl Chloride Monomer

Laxminarayan Institute of Technology 2015

4.3 PURIFICATION OF ETHYLENE DICHLORIDE FOR PYROLYSIS:

Vinyl Chloride Monomer