UNIVERSITI TUN HUSSEIN ONN MALAYSIA

PROCESS PLANT & EQUIPMENT

DESIGN (BNQ 30204)
ASSIGNMENT 1
SEMESTER II SESSION 2017/2018
GROUP: FIVE (5)
TITTLE: VINYL CHLORIDE PRODUCTION
(PLANT DESIGN)

GROUP MEMBERS MATRIC NUMBER

AHMAD WAHIDEE BIN HALID DN150278

AMIR HAMZAH BIN ABD RASHID DN150243

JENICA R.JAMES MAJANAU AN150325

NUR FADHILA SHAFIKA BT YUSOP AN150404

ZURIANI BINTI MOHAMAD TARMIDI AN150287

NOR ALIFFAH BT PUASA AN150297

1
 1. INTRODUCTION
Vinyl Chloride Monomer (VCM) is used almost exclusively in polyvinyl chloride
(PVC). They are used to make PVC for construction application. Vinyl chloride also mostly
been used in automotive industry, electrical wire insulation and cables, piping, industrial and
household equipment, medical supplies, which is depended upon heavily by the rubber, paper
and glass industries. Vinyl Chloride production has been commercialized since 1920s based
on the catalytic hydro chlorination of acetylene but this route suffered from high energy cost
and too expensive to use. Another reaction is the direct chlorination of ethylene to vinyl
chloride which can occurs to a negligible extent at conditions where the following reaction
occurs at high conversion, so this reaction is not feasible.

In fact, there are two routes commonly used to make 1,2 dichloroethane(EDC) direct
chlorination using pure chlorine and ethylene, and ox chlorination in which the ethylene
reacts with chlorine in hydrogen chloride. The EDC is then converted to VCM by thermal
cracking and the hydrogen chloride by-product can be recycled to an oxychlorination plant to
make more EDC. For economic reasons, many EDC/VCM complexes use an integrated
chlorination-oxychlorination process which proceeds in three stages: the chlorination of
ethylene in the liquid or vapour phase to make EDC; the thermal cracking of EDC to form
VCM and hydrogen chloride; and the oxychlorination of ethylene with recycled hydrogen
chloride to make more EDC.

Basically the overall of this process will be using the chlorination reactor,
oxychlorination reactor and pyrolysis reactor. The oxychlorination reaction takes place in
either a fixed bed or fluid bed reactor, the latter being preferred as it easier to control the
temperature. The oxychlorination unit can use air or pure oxygen but the oxygen route is
favoured on environmental and efficiency grounds. The process chosen for vinyl chloride
production is a combination of direct chlorination and oxychlorination called 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 is used in
vinyl chloride production because it consumes the hydrochloric acid (HCl) generated by 1,2
dichloroethane (EDC) pyrolysis. This consumption of HCl is the main advantage of using the
balanced process. The main reactions in the production of VCM are:

2
 Direct chlorination CH2CH2 + Cl2 → ClCH2CH2Cl (EDC)

Oxychlorination CH2CH2 + 2 HCl + ½ O2 → ClCH2CH2Cl + H2O

EDC pyrolysis 2 ClCH2CH2Cl → 2 CH2CHCl + 2 HCl

Overall reaction 2 CH2CH2 + Cl2 + ½ O2 → 2 CH2CHCl + H2O

2. PROCESS PLANT AND EQUIPMENT DESIGN

2.1 Process outline

The five main processes used in the production of VCM are include: direct chlorination of
ethylene to form EDC, oxychlorination of ethylene to form EDC from recycled HCl and
oxygen, purification of EDC, thermal cracking of EDC to form VCM and HCl, and
purification of VCM:

1. Direct chlorination of ethylene to 1,2-dichloroethane (EDC)

It occurs rapidly at temperatures greater than 6555C up to about 20055C in liquid EDC with a solid
AlCl3 catalyst. Pressure must be equal to or greater than the vapour pressure of EDC at the
reaction temperature. Conversion of reactants is essentially 100 percent and conversion to
EDC is above to 99.5 percent.

2. Oxychlorination of ethylene to 1,2-dichloroethane (EDC)

This occurs rapidly at temperatures in the range of 220 to 3005C over a CuCl2 catalyst on a
solid. Pressures of 250 to 1500kPa absolute are typical. HCl must contain <10ppm H20. Air
or oxygen can be used as the O2 source. With air, conversion of ethylene is 94 to 99 percent,
HCl is 98 to 99+ percent, and conversion to EDC is 94 to 99 percent. With O2 results are
similar and the conversion to EDC from ethylene is about 90 to 92 percent. The EDC from
this reaction is not as pure as that from the direct chlorination, and purification is required
before its use in pyrolysis. It must be cooled rapidly to avoid product loss.

3. Pyrolysis of 1,2-dichloroethane to vinyl chloride

This nonanalytic thermal reaction takes place in the range of 475 to 5255C and 1.5 to 3.1 MPa
absolute. Conversion of EDC to vinyl chloride is more than 99 percent. Increasing conversion
decreases selectivity. It must be cooled rapidly to avoid product loss.

3
2.2 Process Flow Diagram (PFD)

PFD of Vinyl Chloride Production

4
 2.3 Conditions of reactor

REACTOR 1 Temperature 183°C

Pressure 1.0 MPa

CSTR to PFR

REACTOR 2 Temperature 500°C

Pressure 2.0 MPa

PFR

REACTOR 3 Temperature 260°C

Pressure 1.0 MPa

PFR to CSTR

2.4 Process of Vinyl Chloride Production (Process plant)

BLOCK DIAGRAM VINYL CHLORIDE PRODUCTION

2.4.1 Chlorination

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The three principle reactions of the path are direct chlorination, pyrolysis, oxychlorination and
require distinctly different conditions, so each must be conducted in a separator. The raw
material feed for the ethylene chlorination reactor R-1 are ethylene and chlorine, the product
is 1, 2-dichloroethane (EDC). The stoichiometric amount of each feed is shown. This reaction
is catalysed by solid AlCl3 and takes place in liquid EDC. Each of the feeds is considered
undergo pre-processing. The commercial form of each of feed is sufficiently pure for
introduction into the reactor. Introducing the feeds at their storage conditions (chlorine is
usually stored as liquid) absorb some of the heat of the reaction and reduces the need of
preheating of the feeds. Therefore, no pre-processing is necessary for these two feed streams.

The simple mass balance to produce 0.5 kg mol of EDC requires 0.5 kg mol each of ethylene
and chlorine as feed to reactor r-1. Because mass transfer of the gaseous reactant is rate-
limiting, it is important to obtain active dispersion of the gases onto the liquid EDC. This is
usually performed with a sparger, utilizing a multiple heat of reaction requires that heat be
removed rapidly. Since the reaction takes place in a liquid EDC phase, one option is to
circulate the EDC through an external heat exchanger. Another option is allowing part of the
EDC to vaporize and then remove the heat in a condenser. Because of the high heat-transfer
rates generally associated with phase changes, an external condenser is selected as shown in
the block diagram flow.

The higher the temperature, the less heat that must be added in R-2 and the more likely it is
that the heat of condensation can be used for other purposes in the process. In this case, the
approximate midpoint of the pressure range is selected, namely, a pressure of 1 MPa, giving a
corresponding temperature of 183 degrees Celsius.

The conversion of both reactants to EDC is reported to be greater than 99.5 %. Therefore, no
recycle of reactants to R-1 is necessary also no pre-processing of the EDC feed to the
pyrolysis reactor R-2 is required because of the high purity of the product from reactor R-1.
Since the direct chlorination reaction is exothermic, heat must be removed from the reactor, as
shown by the Q arrow leaving the reactor.
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 2.4.2 Pyrolysis

As the EDC produced by direct chlorination has a purity of 99.5 percent, indicating that a
purification step is not required, thus separation step is unnecessary. The EDC from reactor R-
1 must be heated around 475 to 525 degree Celsius and the endothermic heat of pyrolysis
must be added to reactor R-2. A pressure in the range of 1.5 to 3.0 MPa is recommended.
Thus reactor 2 is being operated at 500 degrees Celsius and pressure 2 MPa. The pyrolysis
reaction is thermally driven, and no catalyst is required. Because of the high temperature, a
heat source such as combustion is called for. This in turn suggests that a process heat furnace
be used in which the EDC within the tubes flows essentially counter current to the combustion
gases of the furnace.

The product leaving the furnace must be cooled very quickly to stop the thermal
decomposition of the vinyl chloride. This type of rapid quenching is often accomplished by
spraying in cool, volatile liquid into the vapour that is to be cooled. A liquid process
component, either EDC or VC, should be used so that a contaminant is not added to the
system. The liquid must be cooled in a separate heat exchanger and recirculate to the quench
spray. The limitation of the liquid quench is that much of the liquid vaporizes into the product
stream and subsequently must be separated. Another way is to use a transfer-line heat
exchanger located in the effluent line immediately downstream from the reactor. Although the
liquid spray provides a faster quench, the in line exchanger allows greater opportunity for heat
recovery. For these reasons, an inline heat exchanger is chosen to quench the R-2 effluent.
Once the effluent has been cooled to a temperature of about 250 degrees Celsius to quench the
reactions, it may or may not need to be condensed before further processing. E-2 is designed
as a cooler-condenser.

The product stream from the pyrolysis includes VC, HCL EDC and impurities that mostly
boil at higher temperatures, designated as heavy ends. Because of their substantially different
7
volatilities, distillation is required for separating the HCL, VC and EDC. The distillation train
T-1 in the block diagram flow accomplishes this task. The vinyl chloride is a final product and
can be produced with sufficient purity for polymerization purposes by proper design of the
separation train. The EDC is not sufficient purity to be returned directly to the pyrolysis
reactor and must receive further treatment to remove the heavy ends before being recycled to
R-2.

2.4.3 Oxychlorination

Ethylene and oxygen along with the HCL from distillation train T-1 re fed to R-3, the
oxychlorination reactor, the oxygen maybe in the form of air or enriched (100 percent)
oxygen. Air is relatively inexpensive while enriched oxygen has a moderate cost relative to
the cost of the other raw materials. The advantage of using enriched oxygen is that the
quantity of the vent gas streams is significantly reduced. This results in a corresponding
decrease in the amount of chlorinated hydrocarbons and ethylene in the vent gas that must be
treated and thereby provides a substantial reduction in treatment difficulty and cost. The
oxychlorination reaction is partial oxidation that occurs on a solid-supported CuCl2 catalyst.
The reactor therefore must contain the catalyst and allow the reactant gases to flow through
the catalyst structure and directly contact the catalyst. The reaction is highly exothermic; the
reactor must be capable of high rates of heat removal. Since the reaction should be
approximately isothermal, midrange temperature is selected. The pressure will be
approximately 20 to 40 kPa lower than the pressure in the distillation train, or approximately
1 MPa. (Temperature of 260 degrees Celsius and 1MPa pressure for R-3).

The typical reactor arrangement is either a fluidized bed or packed bed of the catalyst. The
packed bed reactor resembles a shell and tube heat exchanger with the catalyst particles and
reactant gas in the tubes and cooling medium on the shell side. Because the flow in the tubes
of the packed bed reactor is essentially plug flow, there is a tendency for temperature

8
gradients and hot spots to occur, which can adversely affect the conversion to VC. One way to
solve this problem is to have multiple reactors in the series with the oxygen feed split among
the reactors. The shell-and-tube packed bed with distributed catalyst loading is selected,
primarily because of the division of this reaction between two reactors, one of which must be
in tubes to supply the heat required for a distillation column reboiler. In fact, it would be
possible to have on fluidized-bed and one packed-bed reactor, or just one fluidized- bed
reactor. Thus, packed bed oxycholorination reactor is used.

The product stream from the oxychlorination reactor(s) is a gas containing EDC and water,
plus small amounts of ethylene and HCL. The gas is cooled, condensing the EDC and water
while bulk of the ethylene and HCL remains in the gas phase, as does some EDC (far less is
enriched oxygen rather than air used). It is especially important to reduce the water
concentration in the EDC to < 10 ppm, to reduce corrosion of downstream equipment. This
product stream goes to a separation tank S-2, which provides sufficient holdup time that the
steam may separate into a gas phase, a water phase and an EDC phase, the gas phase is vented
for further treatment, the water phase is drawn off and sent to treatment and the EDC goes to
the distillation train T-2. The latter removes the light ends (including more water) and heavy
ends which go to treatment.

In further information research, Figure A shows the reactant consumption and 11 product
generation versus reactor tube length. These values are determined by the reactor model.
Table A presents the numerical results from the oxychlorination reactor model.

9
Figure A

Table A

10
 3. MATERIAL BALANCE IN VINYL CHLORIDE PRODUCTION
PLANT
3.1Overview of the material balances.

According to the feasible reaction network for the balanced production of vinyl chloride,
it is highly likely that any of the plausible flowsheets would incorporate three reacting units,
each followed by a separating unit. The three reacting units are designated as R-1 for carrying
out reaction r1, R-2 for reaction r2 and R-3 for reaction r3. The corresponding three separating
units are designated as S-1, S-2 and S-3, respectively.

The output from reacting unit R-3 for pyrolyzing diethylene chloride (C 2H4Cl2) to yield
vinyl chloride (C2H3Cl) contains a substantial amount of unreacted C2H4Cl2 besides traces
amounts of by- products. The equilibrium of the pyrolysis reaction does not favor its
completion. So, it is logical to purify C2H4Cl2 to be recycled to the inlet of R-3 from S-3
together with C2H4Cl2 from R-1 and R-2. This is accomplished by locating S-1 behind S-2.
The latter removes H2O, HCl and traces amounts of excess O 2 from the main stream of
C2H4Cl2 and becomes suitable at feed to S-1.

Table 4.3 presents the compositions of the input streams and output streams from each
operating unit with flow rates of components in these streams similar to those observed in
industrial production.

The mass balances around each operating unit are based on a production rate of
4535kg/h of vinyl chloride. The mass balanced have been computed from stream composition
data also reported in the literature based on the production of 1 kg mol of vinyl chloride. The
computations for the mass balances have been carried out to four to six decimal places to
ensure the inclusion of all trace components. Such knowledge is important from the
standpoint of emission control and pollution prevention. But, for estimating the capacities or
sizes of processing equipment and reactors in the operating units, such computational
specificity generally is not necessary. For completeness the included mass balance solution
tables meet these computational precision levels.

11
Table 4.3 Compositions of the input streams to and the output streams from plausible
operating units of the balanced process to manufacture vinyl chloride in terms of the
flow rates

Material stream Material species

Designation Type Component Flow rate

kg mol/h kg/h

R-1 (direct chlorinating unit)

S01 input Cl2 38.32224 2720.87904

total 38.32224 2720.87904

S02 input C2H4 38.68514 1083.18392

total 38.68514 1083.18392

S04 output/ (input) C2H4 0.3629 10.1612

C2H4Cl2 37.81418 3743.60382

C2H3Cl3/Cl2 trace

total 38.18912 3754.6930

R-2 (oxychlorinating unit)

S02 input C2H4 34.91098 977.5074

total 34.91098 977.5074

S03 input O2 17.49178 559.737

total 17.49178 559.737

S12 (output)/input HCl 72.58 2649.17

total 72.58 2649.17

S05 (output)/input C2H4Cl2 34.8384 3449.002

HCl 2.75804 100.6685

H2O 34.8384 627.0912

CO2/C2H4/O2 trace

total 72.54371 4180.094

S-2 (ethylene dichloride washing unit)

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S05 (output)/input C2H4Cl2 34.8384 3449.002

HCl 2.75804 100.6685

H2O 34.8384 627.0912

C2H4/CO2/O2 trace

total 72.5437 4180.094

S06 output/(input) C2H4 0.07258 2.03224

C2H4Cl2 34.8384 3449.002

O2/CO2 trace

total 34.9328 3451.87

S07 output HCl 2.75804 100.6685

H2O 34.8384 627.0912

O2 trace

total 37.611 728.2242

M-1 (mixing unit)

S04 (output)/input C2H4 0.3629 10.1612

Cl2 0.01089 0.77297

C2H4Cl2 37.8142 3743.604

C2H3Cl3 0.00116 0.155031

total 38.1891 3754.693

S06 (output)/input C2H4 0.07258 2.03224

C2H4Cl2 34.8384 3449.002

O2 0.01016 0.325158

CO2 0.01016 0.510963

total 39.9328 3451.87

13
S13 (output)/input C2H4 0.00051 0.014226

C2H4Cl2 48.6286 4814.231

C2H2/C4H6/C2H2/Cl2 trace

total 48.6312 4814.37

S08 (output)/input C2H4 0.50806 14.22568

Cl2 0.01089 0.772977

C2H4Cl2 121.281 12006.84

O2 0.01016 0.325158

CO2 0.01016 0.510963

C2H3Cl3 0.00116 0.155031

C2H2/C4H6/C2H2/Cl2 trace

total 121.825 12022.95

S-1 (ethylene dichloride purifying unit)

S08 (output)/input C2H4 0.50806 14.22568

C2H4Cl2 121.28118 12006.836

Cl2/O2/CO2/C2H3Cl3/

C2H2,C4H6,C2H2Cl2 trace

total 121.82517 12022.951

S09 output C2H4 0.50806 14.22568

C2H4Cl2 0.07258 7.18542

O2 trace

CO2 trace

C2H2,C4H6,C2H2Cl2 trace

total 0.6045189 22.371406

S10 output/(input) C2H4Cl2 121.2086 11999.651

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 C2H4 trace

total 121.2091 11999.666

R-3 (ethylene dichlorine pyrolyzing unit)

S10 (output)/input C2H4Cl2 121.2086 11999.651

C2H4 trace

total 121.2091 11999.666

S11 output/(input) C2H4Cl2 48.6286 4814.2314

HCl 72.58 2649.17

C2H3Cl 72.58 4536.25

C2H4/C2H2,C4H6,

C2H2Cl2 trace

total 193.79121 11999.79

S-3 (vinyl chloride purifying unit)

S11 (output)/input C2H4Cl2 48.6286 4814.2314

HCl 72.58 2649.17

C2H3Cl 72.58 4536.25

C2H4/C2H2,C4H6,C2H2Cl2 trace

total 193.79121 1199.790

S12 output/(input) HCl 72.58 2649.17

total 72.58 2649.17

S13 output/(input) C2H4Cl2 48.6286 4814.2314

C2H4/C2H2,C4H6,C2H2Cl2 trace

48.631213 4814.3698

total

S14 output C2H3Cl 72.58 4536.25

total 72.58 4536.25

15
 In general, each plausible operating unit, whose incorporation into the flowsheet is
determined at the initial stage of process synthesis, may consist of two or more units of
processing equipment and/or reactors, as mentioned at the outset. This naturally leads to the
second stage, where the network structures of the operating units are determined separately
and independently with their output and input conditions already established through earlier
literature searches. The available information is given below.

Separating unit S-1

The separating unit for purifying ethylene dichloride requires two types of distillation
columns: S-11 for removing the light residues or impurities and S-12 for removing the heavy
residues or impurities.

Separating unit S-3

The separating unit for purifying desired product consists of two distillation columns: S-31
for removing the HCl that is to be recycled and S-32 for separating the vinyl chloride from the
ethylene dichloride that is to be recycled. The mass balances around the four separators S-11,
S-12, S-31 and S-32 are listed in Table 4.5.

Table 4.5 Flow rate of the input streams and output streams for the separation units

Material stream Material species

Designation Type Component Flow rate

kg mol/h kg/h

S-11 (lights column)

S08 (output)/inpu C2H4 0.50806 14.22568

t
C2H4Cl2 121.28118 12006.8368

Cl2/O2/CO2/C2H3Cl3 trace

C2H2,C4H6,C2H2Cl2 trace

total 121.825167 12022.95081

S091 output/ O2 0.0101612 0.3251584

(input)
CO2 0.0116128 0.5109632

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 C2H2,C4H6,C2H2Cl2 0.00210482 0.1241844

total 0.02387882 0.9603060

S15 output/ C2H4 0.50806 14.22568

(input)
C2H4Cl2 121.28116 12006.83682

Cl2/C2H3Cl3 trace

total 121.801288 12021.99050

S-12 (heavies column)

S15 (output)/inpu C2H4 0.50806 14.22568

t
C2H4Cl2 121.28118 12006.83682

Cl2/C2H3Cl3 trace

total 121.801288 12021.99050

S092 output C2H4 0.50806 14.22568

Cl2 trace

C2H4Cl2 trace

C2H3Cl3 trace

total 0.5926883 22.3391079

S10 output/ C2H4Cl2 121.2086 11999.6514

(input) total 121.2086 11999.6514

S-31 (HCl column)

S-11 (output)/inpu C2H4Cl2 48.6286 4814.2314

t
HCl 72.58 2649.17

C2H3Cl 72.58 4536.25

C2H4/C2H2,C4H6,

C2H2Cl2 trace

total

17
S16 output/ C2H4Cl2 48.6286 4814.2314
(input)
C2H3Cl 72.58 4536.25

C2H4/C2H2,C4H6,

C2H2Cl2 trace

total 121.2112129 9350.6198101

S12 output/ HCl 72.58 2649.17

(input) total 72.58 2649.17

S-32 (vinyl chloride monomer column)

S16 (output)/inpu C2H4Cl2 48.6286 4814.2314

t
C2H3Cl 72.58 4536.25

C2H4/C2H2,C4H6,

C2H2Cl2 trace

total 121.211212 9350.619810

S13 output/ C2H4Cl2 48.6286 4814.2314

(input)
C2H4/C2H2,C4H6, 0.0021048 0.1241844

C2H2Cl2 trace

total 48.6312129 4814.36981

S14 output C2H3Cl 72.58 4536.25

total 72.58 4536.25

In carrying out the structural flowsheet optimization of a novel process or for

extensively renovating an existing process to alter its capacity, these linear constraints usually
appear as inequalities. These inequalities indicate that the amount of any material produced
must be equal to or more than the amount consumed, the amount of any desired product
produced must be equal to or more than the amount specified and the amount of any raw
material consumed must be equal to or less than the amount available.

In exploring the structural optimality of the existing vinyl chloride process flowsheet,
the flow rates are known for the materials into and out of each operating unit in a
18
combinatorically feasible flowsheet. The production and consumption rates of every material
can be calculated from these flow rates, thereby rendering possible the verification of the
balance between the two. If necessary, the input and output flow rates of the materials for
some operating units are proportionally varied to achieve the balancing. The data and
information pertaining to the performance of operating units might have been obtained from
different sources. Based on the flow rate data in Table 4.3 and 4,5 for production of 4535kg/h
of vinyl chloride, it can be readily confirmed computationally that the mass balances are
satisfied by all the materials involved, thus indicating that the combinatorically feasible
flowsheet is indeed feasible. It is also structurally optimal since no other feasible flowsheets
exist. The sizes of the operating units are estimated either from their optimal performance data
that may be available or by optimizing their performances as functions of the operating
conditions that are continuous variables, on the basis of mathematical models developed for
the units.

3.2 Detail Material Balance in Vinyl Chloride Productions

(Next Page)

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20
INPUT PROCESS OUTPUT
14.23kg/hC₂H₄ 4814.23kg/h C₂H₄Cl₂
10.16kg/hC₂H₄
0.77kg/h Cl₂
0.77kg/h Cl₂
12006.84kg/h C₂H₄Cl₂
3743.60kg/h
Direct chlorinating unit C₂H₄Cl₂ 0.16kg/h C₂H₃Cl₃
2720.88 kg/h of Cl2 Mixing unit 0.33kg/h O₂ Ethlene dichloride
0.16kg/h C₂H₃Cl₃
purifying unit 14.23kg/hC₂H₄
1083.18 kg/h of C₂H₄ 0.51kg/h CO₂
17.19kg/h C₂H₄Cl₂

3449.00kg/h ofC2H₄Cl₂
3449.00kg/h C2H₄Cl₂
Oxychlorinating unit 2.032kg/h of C₂H₄
100.67kg/h HCl 11999.65kg/hC₂H₄
977.51 kg/h of C₂H₄ 0.33 kg/h of O₂
627.091kg/h of H₂O
0.51kg/h CO₂ 4814.23kg/h of
599.74 kg/h of O₂
C2H₄Cl₂
Vinyl chloride purifying
Ethylene dichloride pyrolzing 2649.17kg/h of unit
Ethylene dichloride
unit HCl 4536.25kg/h
washing unit
of C₂H₃Cl 4536.25kg/h C₂H₃Cl

100.67kg/h of HCl

627.09 kg/h of H₂O

Table 4.1: Composition of the input streams to the output streams to manufacture vinyl chloride in term of flowrate
INPUT PROCESS OUTPUT
10.16kg/hC₂H₄ 14.23kg/hC₂H₄

0.77kg/h Cl₂ 0.77kg/h Cl₂ 0.33kg/h O₂

Direct chlorinating unit Mixing unit
3743.60kg/h 12006.84kg/h C₂H₄Cl₂ 0.51kg/hCo₂

Light column

14.23kg/h C₂H₄

3449.00kg/h ofC2H₄Cl₂ 12006.84kg/h C₂H₄Cl₂

3449.00kg/h C2H₄Cl₂
14.23kg/h C₂H₄
Oxychlorinating unit 2.032kg/h of C₂H₄ Heavies column
100.67kg/h HCl
977.51 kg/h of C₂H₄ 0.33 kg/h of O₂ 4536.25kg/h
627.091kg/h of H₂O Vinyl Chloride
C₂H₃Cl
0.51kg/h CO₂ 11999.65kg/h C₂H₄Cl₂ monomer column
599.74 kg/h of O₂
4814.23.84kg/h
C₂H₄Cl₂ 12006.84kg/h C₂H₄Cl₂ 4536.25kg/h C₂H₃Cl
Ethylene dichloride Pryolysis reactor
washing unit
2649.17kg/h HCl

4536.25kg/h C₂H₃Cl
HCL Column
4814.23kg/h C₂H₄Cl₂
100.67kg/h of HCl

627.09 kg/h of H₂O

Table 4.2: Flowrate of the input streams and output streams for the separation unit
 4. MODIFICATION PLANNING IN VINYL VHLORIDE
PRODUCTION PLANT

4.1 Dividing Wall Distillation

The chemical processing industry certainly doesn’t lack challenges

today. Rapidly escalating capital costs and high energy prices are the new
reality. Many studies indicate that separations consume 50% to 70% of the
capital and energy of a traditional chemical process. Therefore, seeking
improvements in this area clearly should receive a high priority. Distillation
is a very important unit operation in chemical process industries which
comprises 95% of all separation processes. Distillation accounts for more
than 50% of the plant operating cost. Energy consumption can be reduced
by optimizing operating parameters in the column (Mustapha et al., 2007).
One of the more effective methods of reducing both the capital and energy
costs of separations units is installation of dividing wall columns (DWC)
where appropriate. While results, of course, vary, a DWC typically can cut
capital and energy costs by approximately 30% compared to a traditional
two-column system (Pendergast et al., 2008).

In dividing wall column (DWC) working of two columns takes place in

the single shell using a wall. It helps to save both energy and capital. A
DWC is a distillation column that has a vertical partition wall in the central
section. The column may contain either trays or packing. The feed side of
the two compartments acts as the pre-fractionator and the product side as
the main column. In the case of a sharp split, a DWC can be used to
produce three pure products from a single tower. A DWC can handle more
than three components. There may be components lighter than the light
component A that’s in the overhead product, and components heavier
than the heavy component C that’s in the bottom product. In recent time,
DWC is installed successfully by BASF, ExxonMobil and Dow at various
locations (Pendergast et al., 2008).

Energy saving achieved for various processes is in the range of 25-

50%. (Slade et al., 2006). DWC operates as a single unit by replacing two
or three columns hence it is better from the first law prospective. Suphanit
et al. (2007) applied exergy analysis to DWC to determine addition or
rejection of heat at a particular stage of BTX column. Minimum driving
force profile is used to identify suitable locations by dividing the column.
Exergy loss in the column can be reduced up to 8.2% by allowing heat
transfer across the wall of the column.

Sections in dividing wall column (Sumiju Plant Engineering Co.,

Ltd, 2010)

4.1.1 Significant of Dividing Wall Distillation (DWC)

DWC is very appealing to the chemical industry as it can separate three

or more components in a single distillation tower, thereby eliminating the
need for a second unit, hence saving the cost of building two columns and
cutting operating costs by using a single condenser and reboiler. In fact,
using dividing-wall columns can save up to 30% in the capital invested and
up to 40% in the energy costs (Kiss et al., 2007). Compared to
conventional distillation arrangements, DWC offers the following benefits:

 High purity for all three product streams reached in only one column.
 High thermodynamic efficiency due to reduced remixing effects.
 Lower energy consumption compared to conventional (in-) direct
separation sequences.
 Small footprint due to reduced number of equipment units.
 Lower capital investment due to the integrated design.

4.1.2 Exergy Analysis of Petrochemical Process (Vinyl chloride

production)

Petrochemicals are basic building blocks for most of the products in

today’s world. The fraction obtained from the refinery is used as raw
material for petrochemical complex. Vinyl chloride is produced using
ethylene and chlorine. In the first step 1-2 dichloroethane (EDC) is
produced by reacting both reactants. Exergy loss in the VC plant is divided
into five types (Graveland and Gisolf, 1998):

1. Internal losses (Units and equipment’s)

2. External losses (emission to environment)
3. Utility generation losses
4. Primary Energy losses (Primary fuel consumption)
5. Cumulative exergy losses (Production process leading from natural
resources to final product)

Figure Exergy balance of vinyl chloride monomer by Chemical

Bandwidth Study, (2004) shows exergy balance of vinyl chloride monomer
plant. Only 15% of the input exergy is transformed into work. Exergy
destruction can be reduced by replacing the quench tower by an Organic
Rankine cycle and the production of electricity by using the heat of
cracking reaction gas.

The improving sequence of distillation and direct compression of EDC

vapor’s instead of condensation before sending to cracking furnace will
also improve exergy efficiency. The adiabatic compressor can be used to
compress vapors leaving the top of the EDC purifying column and vapors
are used to heat up the bottom product in the reboiler (Araújo, 2007). The
irreversibility rate distribution for the original and modified column with
the compressor at different temperature differences is shown in figure
Irreversibility rate distribution in VCM unit by Araújo et al., (2007). Reboiler
irreversibility increases marginally for temperature difference more than
283.15 K and becomes almost double at a difference of 303.15 K.
Irreversibility in the condenser is reduced substantially in the new
configuration than original configuration and it improves the
thermodynamic efficiency of the column.
 Exergy balance of vinyl chloride monomer (Chemical Bandwidth Study,

2004)

Irreversibility rate distribution in VCM unit (Araújo et al., 2007)

4.2 Waste water treatment.

The water stream from the water wash drum needs to be treated before it can be
disposed. The contaminants of this water stream can be seen in Table C. The EPA enforces
strict regulations for release into the environment. However, the costs associated with
obtaining water will be reduced by treating the stream and recycling it back to the system.

Table B

All of the chemicals can be removed from the water by adsorption, aeration (air
stripping), or by boiling. Since the water is being recycled back to the system the only feasible
solution is using adsorption. The EPA considers liquid phase granular activated carbon
adsorption the best available control technology. Activated carbon adsorption is often favored
because it has the following characteristics:

• The ability to remove more than 99% of contaminants.

• Simple design and operation.

• No waste by-products requiring costly disposal.

• Safe process that has the ability to operate at low pressure and temperature with minimal
toxic gases and dangerous chemicals.
 Figure B

The system was designed to remove 100% of the contaminants. When the carbon has
reached the saturation point (19 days), it will need to be regenerated. Therefore, carbon
regeneration column will be installed (see Figure B). Thermal regeneration is the process of
removing adsorbed contaminants in carbon, using thermal desorption and high temperature
treatment. The 3 major variables involved are furnace temperature, residence time and carbon
loading. Residence time can be changed by varying the rabble arm speed. Hearths 1-2, seen in
figure A, (200-450 o F) are included for water evaporation and physical desorption of VOCs.
Hearth 3 (400-1000 o F) is included for the pyrolysis of non VOCs and carbonization of
residue. Hearths 4 and 6 (1000-1800 o F) are included for uniform distribution of temperature.
Hearth 5 (1600- 1800 o F) is the hearth in which activation occurs.

Calculations for Carbon Adsorption Tower

Equations for the design of activated carbon adsorption tower

1. Minimum amount of carbon in the mass bed

X = amount of carbon adsorbed (mg)

M = mass of carbon (g)
c = equilibrium concentration in solution after desorption (mg/L)
K = Freundlich constant
n = Freundlich number

2. Volume of the granular activated carbon bed

×.85 = AD M V
V = Volume of granulated activated carbon bed (ft3)
AD = Apparent density of carbon (lb/ft3)
M = Mass of carbon (lbs)
 3. Equilibrium saturation (maximum usable life of the carbon)
MR M L D × =
D = Equilibrium saturation (days)
M = Mass of carbon bed (lbs)
L = Loading (lb organic/lb carbon)
MR = Mass flow rate of contaminants (lbs/day)
4. Hydraulic loading
A VF HL =
HL = Hydraulic loading (gpm/ft2)
VF = Volumetric flow rate of water (gpm)
A = Area (ft2)
5. Superficial contact time
VF V CT =
CT = Superficial contact time (min)
V = Volume (gallons)
VF = Volumetric flow rate (gpm)

Table C

The activated carbon treatment system was designed using design equations above. The
results for the column are shown in Table C.

4.3 ADDITION OF CARBON TETRACHLORIDE (BY PRODUCT OF

OXYCHLORINATION) INTO PYROLYSIS REACTOR.

It is very difficult to verify the formation and amount of byproducts. Also it is very difficult to
obtain kinetics parameters of the reactions involved. Using the kinetic data and conversion of
EDC data, the cracking furnace was modeled and then a conversion reactor was used in the
Pro II process simulation.

Conversion of EDC is maintained at 50-55%. Operating the furnace at a higher

conversion decreased the selectivity to vinyl chloride. One way to increase conversion while
maintaining high selectivity is to allow a small amount, 1200 ppm of carbon tetrachloride
(CCl4), a oxychlorination by-product, to enter with the feed. This increases free chlorine
radical formation, which increases conversion to 60%. The Pro II simulation determined a
selectivity of vinyl chloride to 98.8% at a conversion of 60%. This corresponds well to
literature values of 99.9% selectivity at 54% conversion with no CCl4 present in feed. The
effluent from the reactor must be quenched quickly to avoid coke formation and heavy tar
formation. Re-circulating liquid streams quenches the reactor effluent. Next, two separate
flash drums are needed to flash the effluent. From this the effluent will now be ready for vinyl
chloride purification. Figure 5 presents the process flow diagram for the EDC cracking and
quench sections of the vinyl chloride plant.

5. CONCLUSION

Environmental friendliness requires that the design go beyond the minimum

Environmental Protection Agency (EPA) compliance regulations while maintaining plant
profitability. Plant safety includes addressing deviations from normal operation that may have
adverse effects on employees or the surrounding community. The increase in demand for
polyvinyl chloride (PVC) results in an increase in the demand for vinyl chloride monomer
(VCM). By studying the demand over the past ten years, the future demand was estimated
using a forecasting analysis method. The forecasting method uses three different fits to predict
the future demand: a linear fit, an assumption of 5% increase per year, and an exponential fit.
From an average of the three trends, it was found that the demand of the vinyl chloride
monomer could be estimated to be approximately 4.1 billion pounds per year within the next
three years, 6.4 billion pounds per year in five years, and 10.5 billion pounds per year in the
next eight years. A major focus of the design is to maximize safety and minimize
environmental impact while maintaining profitability.

As the improvement is planned on the Vinyl Chloride production plant, we can ensure that
the equipment and operating cost saving are potentially achievable. The capital cost is also
minimized by using analyser. Also, the electricity generates from the turbine is then reuse as
secondary source of power to heat the furnace. Iinstead of wasting away the energy, we used
back the energy to reduce the cost to heat the furnace. Lastly, by using ddistillation
columns through cyclic distillation technology, we can reducee capital
costs for construction of new and reconstruction of existing facilities;
reducing energy consumption for separation processes; improving the
quality and increasing the yield of final products. A major focus of the design is to
maximize safety and minimize environmental impact while maintaining profitability.

6. REFERENCES

I. Jeremy Dry, Vinyl Chloride Production, University of Oklahoma. Retrieved from,

https://www.icis.com/resources/news/2007/11/07/9076569/vinyl-chloride-
monomer-vcm-production-and-manufacturing-process/

II. Jeremy Dry, Bryce Lawson, Phuong Le, Israel Osisanya, Deepa Patel, Anecia
Shelton Capstone Design Project- University of Oklahoma - Spring 2003
http://www.ou.edu/class/che-design/a-design/projects-2003/VINYL
%20CHLORIDE%20PRODUCTION-original.pdf

III. Analysis in Vinyl Chloride (VCM) Production Process. (2017, April 12).
Retrieved March 21, 2018, from
 http://aai.solutions/documents/AA_AN030_Analysis-in-VCM-Production-
Process.pdf

IV. Araújo, A. B., Brito, R. P. and Vasconcelos, L. S. (2007) 'Exergetic

analysis of distillation processes-A case study', Energy, Vol. 32,
pp. 1185-1193.
V. Chemical Bandwidth Study, Exergy Analysis: A Powerful Tool for
Identifying Process Inefficiencies in the U.S. Chemical Industry
(2004)
http://www1.eere.energy.gov/manufacturing/resources/chemicals
/pdfs/ chemical_bandwidth_report.pdf (Accessed 1 February
2012)
VI. Graveland, A. J. G. G. and Gisolf, E. (1998) 'Exergy analysis: An
efficient tool for process optimization and understanding.
Demonstrated on the vinyl-chloride plant of Akzo Nobel',
Computers & Chemical Engineering, Vol. 22, pp. S545-S552.
VII. Kiss A, Pragt H, van Strien C (2007) Computer aided chemical
engineering. In: 17th European Symposium on Computer Aided
Process Engineering, vol 24, Elsevier, Amsterdam, pp 467–472.
doi:10.1016/S1570-7946(07)80101-5.
VIII. Mustapha, D., Sabria, T. and Fatima, O. (2007) 'Distillation of a
Complex Mixture. Part II: Performance Analysis of a Distillation
Column Using Exergy', Entropy, vol. 9, pp 137-151.

IX. Vinyl Chloride Production / http://www.ou.edu/class/che-design/a-

design/projects-2003/VINYL%20CHLORIDE%20PRODUCTION-original.pdf /
Retrieved on 12 April 2018.