1)Introduction to VCM process

Chlorinating hydrocarbons is the basic idea behind the production of vinyl chloride monomer
(VCM). Chlorinated hydrocarbons (CHCs) are 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. PVC products are highly
resistant to weathering, petroleum products, and UV radiation. PVC, a flame-resistant material,
has been examined extensively in regards to fire prevention. There are so many positive aspects
of using PVC that it is imperative that it be produced. Many CHCs are created during the
production of PVC; this is a growing concern. Therefore, VCM needs to be produced in a way
that will minimize or totally eliminate the release of CHCs into the environment . VCM is a gas
with a molecular weight of 62.5 and boiling point of -13.9°C, and hence has a high vapour
pressure at ambient temperature. It is therefore manufactured under strict quality and safety
control. There are two ways to manufacture VCM from ethylene (obtained from thermal
cracking); the direct chlorination method and oxychlorination method.

1.1Vinyl Chloride from Acetylene

The process that produces vinyl chloride from acetylene employs the use of a catalyst. Most of
the time the catalyst used is mercuric chloride deposited on active carbon. In this process the
feed gases are purified, dried, and mixed at the entrance to the tubular fixed bed reactors, which
are packed with mercuric chloride on active carbon pellets as catalysts. Usually, a slight excess
of HCl is used over stoichiometry. “About 99% conversion of acetylene and 98% conversion of
HCl are achieved. The selectivity to vinyl chloride is good – more than 98% -- and the only
significant side reaction is the further addition of HCl to vinyl chloride to form 1,1-
dichlorethane” . The major issue with this process is that fact that the catalyst used, mercuric
chloride, is a very volatile compound. It is so volatile that much of the development work on this
process has been devoted to this problem. Consequently, the acetylene route is currently of little
commercial importance

1.2 Vinyl Chloride from Ethane

Many attempts have been made to develop a process that will use ethane to directly produce vinyl
chloride. This is due to relative inexpensiveness of ethane. 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. “The most promising routes appear to be those based on high temperature
oxychlorination that use special catalysts to achieve a worthwhile selectivity to vinyl chloride and useful
major by-products such as ethylene, ethyl chloride, and EDC” . The ethylene may be chlorinated to EDC
and recycled along with the ethyl chloride. 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 500o C . At
this temperature chlorine becomes very aggressive to most construction materials.
1.3 Vinyl Chloride from Ethylene
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 patent 7 literature recommends using
inert fluid beds for heat transfer and diluting gases in the feeds. Substantial amounts of vinyl
chloride are formed when the oxychlorination reactor is operated above 350o C. The common
problems with the direct routes of production are poor selectivity’s to vinyl chloride and
substantial production of chlorinated by-products, many of which have no direct commercial
utility. “This has substantially hindered the industrial application of direct-conversion
processes”. Therefore, for our we use direct ethylene direct chlorination method.

2.Reactions and Thermodynamics property analysis

2.1 Thermodynamics and Reaction
A large number of chemical species are present in the vinyl chloride plant. Generally, most of
the compounds are non-ideal and somewhat polar. The modified Suave-Redlich Kwong ( POLY-
SRK) equation of state was used to simulate the vinyl chloride plant. This equation of state
handles polar-nonpolar systems well . It is recommended for hydrocarbon and water mixtures, as
is the case in the production of vinyl chloride. The modified SRK equation of state does not
accurately predict liquid densities; therefore, liquid density estimations were made using Rackett
correlation . This correlation was selected because of its accurate prediction of hydrocarbon
liquid densities .
The chemical reaction is the following;

 Direct chlorination of ethylene to 1,2 - ethylene dichloride (EDC) : C2H4 +

Cl2→C2H4Cl2
 Thermal cracking (pyrolysis) of EDC to VCM: C2H4Cl2→C2H3Cl +HCl

2.2Thermodynamics property analysis

Fig 1.1 T-xy diagram for CL/C2H4

Fig 1.2P-xy diagram for CL2/C2H4

Fig1.3 y-x diagram for CL2H4
 Fig1.4 T-x for CL2/C2H4
2.2Process step for VCM simulation

 Pure ethylene, stored as a gas at 70F AND 1000Psia,with the flow rate of 20ton/hr and
pure chlorine, stored as a liquid at 70F and 150pisawith the flow rate of 50ton/hr enter the
mixer block operated at 20atm.
 The mixer outlet goes to the reactor (running at 363k and 1.5atm)
 In the stoichiometric reactor, following reaction (chlorination takes place with 98%
conversion of ethylene).
 C2H4 + Cl2→C2H4Cl2
 Next the mixer is operated at 1.4 atm allowing mixing of the recycle stream with the
reactor product.
 Outlet is then condensed fully to the liquid phase in the condenser(298k) before being
pumping to an evaporator.
 The pump discharge liquid at 26atm.the evaporator change the phase and also increase
the temperature to 515k.
 The outlet stream from the evaporator is then feed to the react or.Rstoic,in which
following reaction takes place: C2H4Cl2→C2H3Cl +HCl,the reaction is takes place
spontaneously at 773k and 25atm with 65%conversion.
 To avoid the formation of coke in the subsequent heat exchanger the hot outlet vapor
stream leaving the reactor is then quenched to saturated vapor at 443k
 Quenched stream is then feed to the heat exchanger to condense it to liquid at279k and
then feed to a distillation column (DSTWU)
 Further the bottom stream of this column if feed to the next column(DSTWU);
 The first column separate HCl from the component and second,the VCM from
the rest.(both column have 10 stage including condenser/reboiler)
 Recovery LK/HKin distillate Pressure(atm)
Column LK HK condenser Reboiler
1 99.9HCL 0.1VCM% 20 22
2 99.9%VCM 0.1%dichlorane 7.5 8

 Finally outlet,(bottom) of the distillation column 2 splitted enshuring 99.999% of

recycle go to the process again. The purge is done here to ensure the accumulation of
un reacted components.

3)Modeling and simulation reactor, Heat exchangers and separation system

4. Discuss your results based material balance for each units operation
Table 1:Mixer1material balance table
 Heat and Mater i al Balance Tabl e
Str eam ID C2H4 CL2 3
Temper a tur e C 21.1 21.1 -53.6

Pr essur e bar 68.948 10.342 2.027

Vapor Fr ac 1.000 0.000 0.497
Mole Fl ow kmol/ hr 646.747 639.715 1286.462
Ma ss Fl ow kg/hr 18143.695 45359.237 63502.932

Volume Flow cum/hr 81.104 32.285 5595.869

Enthal py Gcal /hr 7.026 -2.862 4.163
Mole Fl ow kmol/ hr
CL2 639.715 639.715

HCL
C2H4 646.747 646.747
C2H3CL

C2H4CL2

In this unit operation Cl2 and C2H4 were feeds with mole flow of 646.747 and
639.715,and were mixed together with the temperature of 21c0 with out reaction
Table 2: material balance on Rstoic

He a t a nd Mat e ria l Bala nce Ta ble

Stre am ID 3 4
Te mpe ra ture C -5 3 . 6 8 9. 8
Pre ssure ba r 2. 02 7 1. 52 0
Va por F ra c 0. 49 7 0. 13 1
Mole F low kmol/hr 12 86. 46 2 652 . 65 0
Ma ss F low kg/hr 6 3502 . 93 2 63 50 2 . 93 2
Volume F lo w cum/hr 55 95. 86 9 16 95. 1 78
Ent ha lpy Gca l/hr 4. 16 3 -22. 9 59
Mole F low kmol/hr
CL2 639 . 7 15 5. 90 2
HCL
C2 H4 646 . 7 47 12. 9 35
C2 H3 CL
C2 H4 CL2 633 . 81 2

.
On this operation(Rstoic) the feeds Cl2 and C2H4 with the molar flow rate of
639.715 and 647.747kmol/hr respectively were reacted. dichlorate(C2H4Cl2) were
produce with molar flow rate of 633.812kmol/hr. the unreacted amount Cl2 and
C2H4 were 5.902kmol/hr and and 12.935kmol/hr respectively. There for the
efficient conversion were takes place. Table 3:material balance on mixer 3

Function of mixer 3 is to mix the recycled and the product output from Rstoic
3,so C2H4Cl2 from Rstoic with the flow rate of 633.812kmol/hr and recycled
unreacted product with the flow rate of 340.754kmol/hr were mixed and were
given 975.566kmol/hr of output.
Table 4:heat and material balance on Heater1

H eat and M ater ial B alan c e T ab le

S tream ID 6 7
T emp eratu r e C 91.6 24.9
P r essu re b ar 1.419 1.175
V ap o r Fr ac 0.195 0.000
M ole F lo w k mo l/hr 994.037 994.037
M ass F lo w k g/h r 97263.225 97263.225
V olu me F lo w c um/h r 4084.716 78.478
E nth alpy G cal/h r -34.808 -38.293
M ole F lo w k mo l/hr
CL2 5.903 5.903
HC L tr ace tr ace
C 2H 4 12.935 12.935
C 2H 3C L 0.633 0.633
C 2H 4C L2 974.566 974.566
The purpose of this heater1 is to liquify the gas since the pressure required is
high(26atm) and it is a better pressurize the liquid ta high level than compressing
gases.as result the input and output flow rate(974.566kmol/hr) were the same but
the temperature was reduced.
Table5:heat and material balance on heater2

Heat and Mater ial Balance Table

Str eam ID 8 10
Temper atur e C 25.8 241.8
Pressur e ba r 26.000 28.748
Vapor Fr ac 0.000 1.000
Mole Flow kmol/hr 994.037 994.037
Mass Flow kg/hr 97263.225 97263.225
Volume Flow cum/hr 78.568 1012.723
Enthalpy Gcal/hr - 38.224 - 26.447
Mole Flow kmol/hr
CL2 5.903 5.903
HCL trace trace
C2H4 12.935 12.935
C2H3CL 0.633 0.633
C2H4CL2 974.566 974.566

At this operation(heater2) the evaporator increased the temperature to 241.8oC

that were discharged by pump so input and output molar flow rate were the same
except the temperature change.
Table5: heat and material balance on Rstoic

H eat and M aterial B alance Table

S tream I D 10 11
T em perature C 241.8 501.9 Rstoic was
P ressure
V apor Frac
bar 28.748
1.000
25.331
1.000
used to
M ole F low k mol/hr 994.037 1627.505 crake
M ass F low k g/hr 97263.225 97263. 225
V olum e F low cum/hr 1012.723 4124.596
C2H4Cl2 to
E nthalpy G cal/hr -26.447 -8.376
HCl and
M ole F low k mol/hr
C L2 5.903 5.903 VCM, and
HC L
C 2H 4
trace
12.935
633.468
12.935
on this
C 2H 3C L 0.633 634.101 reaction
C 2H 4C L2 974.566 341.098
only 65%
conversion(633.448kmol/hr) was performed.in addition the unreacted output was
35% that is 341.098kmol/hr, the reaction was almost good.
Table 6: material balance on heater 2 and 3
 Heat and Material Balance Table Heat and Material Balance Table

Stream ID 11 12 Stream ID 12 S1
Temperature C 501.9 169.8 Temperature C 169.8 5.8
Pressure bar 25.331 41.776 Pressure bar 41. 776 12. 855
Vapor Frac 1.000 1.000 Vapor Frac 1.000 0.000
Mole Flow kmol/hr 1627.505 1627.505 Mole Flow kmol/hr 1627.505 1627.505
Mass Flow kg/hr 97263.225 97263.225 Mass Flow kg/hr 97263. 225 97263. 225
Volume Flow cum/hr 4124.596 1132.227 Volume Flow cum/hr 1132.227 92. 196
Enthalpy Gcal/hr -8.376 -18.093 Enthalpy Gcal/hr -18. 093 -28. 879
Mole Flow kmol/hr Mole Flow kmol/hr
CL2 5.903 5.903 CL2 5.903 5.903
HCL 633.468 633.468 HCL 633.468 633.468
C2H4 12.935 12.935 C2H4 12. 935 12. 935
C2H3CL 634.101 634.101 C2H3CL 634.101 634.101
C2H4CL2 341.098 341.098 C2H4CL2 341.098 341.098

on
above two heater 3&4 tabular result the only temperature was reduced with with
the constant amount of molar flow rate of in put and output.
Table7: material balance on DSTWU1

H eat and M aterial B alance Table

S tream I D S1 S8 S 15
T emperature C 5.8 -8.9 127.1
P ressure bar 12.855 20.265 22.291
V apor Frac 0.000 0.000 0.000
M ole F low kmol/hr 1627.505 646.615 980.890
M ass F low kg/hr 97263.225 23491.237 73771.988
V olume F low cum/hr 92.196 25.078 87.153
E nthalpy G cal/hr -28.879 -16.057 -9.516
M ole F low kmol/hr
C L2 5.903 0.216 5.687
HC L 633.468 632.834 0.633
C 2H 4 12.935 12.931 0.004
C 2H 3C L 634.101 0.634 633.467
C 2H 4C L2 341.098 341.098

The above result show that 99.9% of HCl with 0.1% of VCM was separated on the
top of the DSTWU column, that is 632.834kmol/hr. and the remain were passed
through to the second DSTWU.since the boiling point of HCl is -85oC it Vapored
first.
Table 8: material balance on DSTWU2
 H eat an d Mate rial Balan ce T ab le
S tre am ID S 15 S 27 S 36
T em pe ratu re C 1 27 .1 48 .3 1 68 .4
P re ssure b ar 2 2 .2 9 1 7 .5 9 9 8 .1 0 6
V ap o r Frac 0 .0 0 0 0 .0 0 0 0 .0 0 0
Mole Flo w kmo l/ hr 9 8 0.8 90 6 3 9.4 99 3 4 1.3 91
Mass Flo w kg/ h r 73 7 71 .9 88 40 0 11 .3 58 33 7 60 .6 31
V olu me Flo w c um / hr 8 7 .1 5 3 4 6 .3 9 5 3 3 .5 9 0
E nt h alp y Gcal/ hr -9 .5 1 6 1 .5 1 9 -1 1 .8 5 0
Mole Flo w kmo l/ hr
CL2 5 .6 8 7 5 .6 8 7 < 0. 0 0 1
HCL 0 .6 3 3 0 .6 3 3 t rac e
C2 H 4 0 .0 0 4 0 .0 0 4 t rac e
C2 H 3CL 6 3 3.4 67 6 3 2.8 34 0 .6 3 3
C2 H 4CL2 3 4 1.0 98 0 .3 4 1 3 4 0.7 57

Our main required product was produced on this distillation column,That we have
gotten 99.9% of VCM on top of column,633.467kmol/hr was supplied to the
column 2 and 632.834kmol/hr(99.9%) was found.from this 0.1% was dechlorane.
At the bottom of the column 99.9% of dechlorane(340.757kmol/hr) was removed
for recycling.
Table9:material balance on final mixer.

H eat and M aterial B alance Table

S tream I D S 36 S 37 P URG E
T emperature C 168.4 168.4 168.4
P ressure bar 8.106 8.106 8.106
V apor Frac 0.000 0.000 0.000
M ole F low kmol/hr 341.391 341.387 0.003
M ass F low kg/hr 33760.631 33760.293 0.338
V olume F low cum/hr 33.590 33.589 < 0.001
E nthalpy G cal/hr -11.850 -11.850 > -0.001
M ole F low kmol/hr
C L2 < 0.001 < 0.001 trace
HC L trace trace trace
C 2H 4 trace trace trace
C 2H 3C L 0.633 0.633 trace
C 2H 4C L2 340.757 340.754 0.003

This mixer the remain unseparated compound such as Cl2 H3Cl with molar flow
rate of 0.633kmol/hr and unreacted dechlorane with the molar flow rate of
340.757kmpl/hr. were mixed together and recycled to the second mixer. Remain
unnecessary product were removed to the purge.
5)Conclusion and recommendation
The vinyl chloride monomer product is 99.9 mol% pure, this composition allows for production
of vinyl chloride and polymer feedstock . ASPEN PLUS simulations show that from
974.566kmol/hr dechlorane could be produced 632.834kmol/hr VCM.this implies that we
have a chance of production of VCM above 35% of raw material (dichlorane) for one cycle.if we
increase the number of stage in the last distillation column the conversion of product of VCM
will increase. profitability. The VCM plant produces a number of by-products resulting waste
streams. The Clean Air and Clean Water Acts, enforced by the Environmental Protection
Agency, regulate the procedure by which we dispose of the different waste streams. An
integrated waste treatment system utilizing incineration, absorption, caustic scrubbing and
activated carbon adsorption is developed in order to avoid releasing any hazardous waste into the
environment.