Chapter 3 PVC Production

Technological Institute of the Philippines
363 P. Casal St., Quiapo, Manila

VCM-BASED PVC PRODUCTION
PROJECT
Engr. Michael Francis Sy
Agoncillo, Michaela Andrea
Antonio, Carl Brian
Calimbas, Bea Mariz
Doton, Ephraim John
Gamurot, Ele Jon
Munoz, Aurea
Tejio, Carissa Jane
Villanueva, Joseph
CH32FB1 CHEM 302 March 22, 2017
VCM-BASED PVC PRODUCTION 1

I. SUMMARY
I-A. Vinyl – Chloride Monomer Production
i. Selection Process
The two main materials which are used in the production of VCM are acetylene and
ethylene. The high energy requirement of producing acetylene from calcium carbide became a
huge drawback for the production of VCM. Ethylene, however, became more commercially
available by the 1950’s which led to the development of processes to produce VCM from
ethylene and chlorine. Although the manufacturing of VCM from acetylene is a relatively simple
single-stage process, the cost of acetylene is high. Today, 90 % of the world’s VCM production is
based on ethylene.
ii. Process Description
VCM production can be separated into five main parts. (1) direct chlorination of ethylene
to form EDC, (2) oxychlorination of ethylene with recycled HCl and oxygen to from EDC, (3)
purification of EDC, (4) thermal cracking of EDC to form VCM and HCl, and (5) purification of
VCM.
a. Direct Chlorination of Ethylene
The process starts by feeding ethylene and chlorine into a direct chlorination reactor. This
reactor uses FeCl3 as a catalyst. An electrophilic addition mechanism is used by the catalytic
reaction. The reactions are shown below:
FeCl3 + Cl2 ↔ FeCl4-Cl+ Eqn. 1

FeCl4-Cl+ + CH2CH2 → FeCl3 + ClCH2CH2Cl Eqn. 2
In this reactor, the FeCl3 catalyst polarizes the chlorine gas. The resulting polarized
chlorine molecule then acts as an electrophilic reagent resulting to the binding of a Cl - to the

double bond of ethylene. A 99.9% conversion can be achieved with EDC selectivity at 99.4%.
The main by-products of the reaction is 1, 1, 2-trichloroethane. Its formation can be inhibited by
the addition of pure oxygen in the chlorine feed with a ratio of 0.5%. HCl is also formed as a by-
product but only on small amounts.
The direct chlorination of ethylene is highly exothermic (∆H = -180 kJ/mol). The reaction
can be operated either at low temperature for low by-product generation or high temperatures for
heat recycling. Direct chlorination of ethylene is usually operated at temperatures of 50-70˚C and
at pressures of 4-5 atmospheres. The reactor can also be operated at higher pressures to raise the
boiling point of EDC. This results to a more efficient heat transfer while keeping the products in
the liquid phase.
b. Oxychlorination of Ethylene
The process starts by feeding ethylene with HCl rich waste gas and oxygen in a
oxychlorination reactor to produce EDC and water. The reactor uses CuCl 2 as a catalyst. The
oxychlorination reaction is made up of a series of reactions with the final reaction is shown
below:
CH2CH2 + 2HCl + 1/2 O2 → ClCH2CH2Cl + H2O Eqn. 3
Along with EDC and water, trace amounts of by-products are formed in the reactor.
These by-products are trichloroethylene (TCE), acetylene, trichloroacetaldehyde (chloral),
carbon tetrachloride (CCl4), methyl chloride, chloroform, chloroprene, vinyl acetylene, and
dichloromethane. The common reactor effluent stream usually contains 47 mol % EDC, 47 mol
% H2O, 5 mol% CO2, and trace amounts of oxygen, HCl, ethylene, and various chlorinated
hydrocarbons.
Ethylene oxychlorination is normally conducted at temperatures of 225-325 ˚C and at

pressures of 1-15 atmospheres. The oxychlorination reaction is highly exothermic (∆H = -239

kJ/mol). Either a fixed-bed or fluidized-bed reactor can be used in oxychlorination. The
fluidized-bed reactors are capable of better temperature control due to the intermixing of the
reactants and catalyst. In a fixed-bed reactor, the catalyst is packed in tubes which may result to
hotspots as the catalyst migrates along with the direction of flow. Heavy concentrations of
catalyst in one area may accelerate the reaction rate and the resulting heat may cause an increase
in by-product formation. Oxychlorination is less efficient compared to direct chlorination due to
the significant formation of water and carbon oxides. The resulting stream from oxychlorination
is first passed through a caustic scrubber and flash column to remove any impurities before
purification of EDC
c. Purification of EDC
The EDC coming from the direct chlorination, oxychlorination, and recycle stream are
combined and passed through a series of purification stages. It is important that the EDC used in
cracking is highly pure, at least 99.5% in order to prevent any fouling in the reactor. Moisture in
the stream must be also removed in order to prevent corrosion in the equipment.
The EDC feed is first washed with water in a wash tower. This removes the majority of
water produced by the oxychlorination reaction. Any remaining traces of FeCl 3 can also be
removed by washing with water since FeCl 3 is highly soluble in water. The FeCl 3 can then be
removed by adsorption on activated carbon. The EDC is then further purified by two distillation
columns. The first column is referred to as the lights column. This removes water and low
boiling point impurities. The bottoms from the lights column are combined with the pyrolysis
feed purge and fed into the second column. The second column which is referred to as the
heavies column. The pure EDC coming from the overhead of the heavies column is then fed into
the cracking unit.

d. Thermal Cracking of EDC
Vinyl chloride is produced by the pyrolysis of EDC. In this reaction, hydrogen and
chlorine is separated from the EDC resulting to the formation of vinyl chloride and HCl at about
a one to one molar ratio. Most of the by-products produced are hydrocarbons.
ClCH2CH2Cl → CH2=CHCl + HCl Eqn. 4

Product conversion rates are usually kept around 50-60%. This is done in order to
minimize by-product formation. An increase in conversion decreases the selectivity of vinyl
chloride production. One way to increase conversion while maintaining high selectivity is to
allow a small amount of 1200 ppm CCl 4 to enter with the feed. This results to an increase in free
chlorine radical formation which increases overall conversion to 60% and vinyl chloride
selectivity of 98.4%. Vinyl chloride selectivity at 99.9% can be achieved at 54% conversion
without any CCl4 present in the feed.
This process is done in a fuel heated cracking furnace which usually operates at
temperatures of 450-650˚C and pressures of 20-30 atmospheres. High operating pressures result
to increased yield, fewer by-product formation, and easier separation of VC from the unreacted
EDC and by-products. The effluent from the reactor must be quenched quickly to avoid coke and
heavy tar formation. The resulting stream is then flashed in two separate flash drums to flash the
effluent.
e. Purification of VCM
The resulting product stream coming from the cracking unit is passed through two
distillation columns which separates the HCl and VCM. The first column is referred to as the
HCl column. This distills the HCl mixture into a pure overhead product which is then recycled
and fed into the oxychlorination reactor. The bottoms product of the HCl column is fed to the
second column which is referred to as the VCM column. This column produces a 99.9%
overhead VCM product. The bottoms of the VCM column is then recycled to the lights column
for re-purification and recycle use.

II – A. Process Flow Diagram

III - A. Process Description in VCM Production

i. R101: Direct Chlorination Reactor
A 99.9% conversion can be achieved with EDC selectivity at 99.4%. The main by-
products of the reaction is 1, 1, 2-trichloroethane. HCl is also formed as a by-product but only on
small amounts.
Reactions:
FeCl3 + Cl2 ↔ FeCl4-Cl+
FeCl4-Cl+ + CH2CH2 → FeCl3 + ClCH2CH2Cl

ii. R102: Oxychlorination Reactor
EDC, water, and trace amounts of by-products are formed in the reactor. These by-
products are trichloroethylene (TCE), acetylene, trichloroacetaldehyde (chloral), carbon
tetrachloride (CCl4), methyl chloride, chloroform, chloroprene, vinyl acetylene, and
dichloromethane. The common reactor effluent stream usually contains 47 mol % EDC, 47 mol
% H2O, 5 mol% CO2, and trace amounts of oxygen, HCl, ethylene, and various chlorinated
hydrocarbons.
Catalyst: CuCl2
Reaction:
CH2CH2 + 2HCl + 1/2 O2 → ClCH2CH2Cl + H2O

iii. C101: Caustic Scrubber
Scrubber or washer is used to remove solid and liquid particulate from the flow stream. It
is commonly used to remove pollutants from the product stream. The resulting product stream
from the two chlorination reactors are fed into a caustic scrubber utilizing HCl to remove any
amount of CuCl2 that may have been mixed with the product stream

iv. C102: Flash Column
Flash distillation is where a liquid mixture feed is pumped into a heater in order to raise
the temperature and enthalpy of the mixture, the pressure is then lowered thus making the
mixture partially vaporize. Once the volume of the mixture becomes larger, the liquid and vapor
separates. Used to remove impurities from EDC before further purification

v. C103: Lights Column
Distillation is a common separation process where the differences in volatility are

exploited with the application and removal of heat. Used to remove water and low boiling point
impurities. The bottoms from the lights column are combined with the pyrolysis feed purge and
fed into the second column.

vi. C104: Heavies Column
Like C103, C104 is a distillation column and referred to as the heavies column. The pure
EDC, at least 99.5% coming from the overhead of the heavies column is then fed into the
cracking unit.

vii. F101: Cracking Furnace
Product conversion rates are usually kept around 50-60% in order to minimize by-product
formation. An increase in conversion decreases the selectivity of vinyl chloride production. Vinyl
chloride selectivity at 99.9% can be achieved at 54% conversion. This process is done in a fuel
heated cracking furnace which usually operates at temperatures of 450-650˚C and pressures of
20-30 atmospheres. High operating pressures result to increased yield, fewer by-product
formation, and easier separation of VC from the unreacted EDC and by-products.
Reaction:
ClCH2CH2Cl → CH2=CHCl + HCl

viii. C105: HCl Column
Like C103 and C104, C105 is a distillation column and referred to as the HCl column,
this distills the HCl mixture into a pure overhead product which is then recycled and fed into the
oxychlorination reactor. The bottoms product of the HCl column is fed to the second column

ix. C106: VCM Column
Like C103, C104 and C105, C106 is a distillation column and referred to as the VCM
column, this column produces a 99.9% overhead VCM product. The bottoms of the VCM
column is then recycled to the lights column for re-purification and recycle use.
x. T104: VCM Tank
The VCM tank serves as the holding tank of the raw VCM which was produced in the
monomer plant. The tank is insulated and pressurized to be able to liquefy the VCM. The storage
conditions in tank is kept at 27 psig and 15 C. The VCM is then charged into the autoclave under
pressurized conditions.

I-B. PVC Polymerization Process

i. Selection Process
There are two common processes of polymerization: the emulsion method and the
suspension method.
One of the major disadvantages of emulsion polymerization is the difficulty in

coagulating and separating the polymer from the latex. Very fine precipitates are often obtained
which filter slowly, making removal of coagulating salts and initiator residues slow, expensive,
and incomplete. On the other hand, suspension polymerization can overcome some of the
difficulties encounter in the emulsion process and at the same time produce a granular product
directly. As in emulsion polymerization, there are a dispersed phase and a dispersion medium.
The principal difference is in the average particle size of the dispersed phase. The monomeric
particles are much larger and no emulsion exists but instead there is obtained a simple physical
suspension of polymerizing drops or beads which will coalesce rapidly upon cessation of
agitation.
ii. Process Description

The raw material for the PVC production is vinyl chloride monomer. The PVC
production process starts as the VCM, demineralized water polymerization reactors. The
polymerization reaction is initiated with the thermal decomposition of the peroxide catalyst
which results to the formation of the radicals. In order to promote the formation of VCM droplets
within the reactor stirring is employed. The average diameter of the droplets are around 30-
40µm. To stabilize the droplets from coalescence, protective colloids are introduced to the
reactor which provides as the protective layer. The polymerization reaction is initiated with the
thermal decomposition of the peroxide catalyst which is fed to reactor that results to the
formation of PVC. This reaction is under atmospheric pressure with a temperature range 40-
60°C.

The polymer is swollen by 27wt% of VCM in order to form a coherent gel. As the
polymerization progresses, due to lack of mobility of the growing chain, chain termination is
hindered. However, monomer starvation reduces the reaction rate. The product of the reaction
enters the stripping tank where unreacted VCM is recovered and after refining is recycled to be
used as raw material for a new batch of production. The PVC obtained from the reaction is
suspended in water as micro particles with an average diameter of 50-250µm. This slurry
discharge enters the centrifuged then a fluidized-bed dryer in order to dehydrate and dry the
PVC. Screening of the PVC in order to match the particle size is done which produces the PVC
in the form of white powder.
II-B. Process Flow Diagram

III – B. Equipment Description

i. R103: Autoclave
This subsection presents the reactions happening in the autoclave. The reactions
enumerated are the steps in the polymerization of the vinyl chloride monomer (VCM).
1. Initiation Monomer:
R+ H 2 C=CHCl RC H 2 CHCl Eqn. 5
→
2. Propagation:
RC H 2 CHCl +n H 2 C=CHCl R (C H 2 CHCl)n C H 2 CHCl Eqn. 6
→
3. Chain Transfer to monomer:

CH 2 CHCl+ H 2 C=CHCl CH 2 CH 2 Cl+ H 2 C=CCl
→

CH =CHCl+ H 3 CCHCl Eqn. 7
→
4.Termination: 2 CH 2 CHCl CH 2 CHClClHC CH 2

→
CH 2 CH 2 Cl+ CH =CHCl
→
CH 2 CHCl+ R CH 2 CHClR Eqn. 8

→
The pure vinyl chloride from the storage tanks is pumped to the polymerization autoclave
fitted with cooling jacket and stirrer. Vinyl chloride monomer is polymerized in water and
maintained in suspension under agitation. The monomer is mixed with demineralized water
usually in the ratio of 2 parts of water with 1 part of monomer. The water does not take part in
the reaction, it is there only to act as the suspension medium. A small amount of catalyst and
initiator are also added to hasten the reaction and to produce free radicals that catalyse the
polymerization of VCM to PVC. Polyviniyl alcohol which is the suspension agent, usually 0.5%
of the VCM charged and benzoyl peroxide which is the catalyst, also at 0.5% of the VCM
charged.
The sealed autoclave is then agitated vigorously (200-300rev/min) and the temperature is
raised to about 60C. As the temperature is raised, the initiator molecules dissociate and start the
polymerization process. Normally, the pressure in the autoclave will be in between of 130-
180psig.
The reaction is highly exothermic and so a major design feature involves removing the
heat fast enough to keep the reaction at constant temperature. In addition, VCM vapour is
produced so that the vessel, which is sealed, develops pressures up to 100 psig. Once filled the
reactor is sealed and the contents are agitated until the reaction is about 90-95% complete. This
typically takes 5-8 hours.

ii. C107: Stripping Tank
Slurry containing around 3% of monomer is fed to the top of a vertical column under
vacuum, while steam enters at the bottom of the column, passing upwards to heat the slurry and
carry the monomer with it. The steam is used to heat the slurry of polymer in water to between
80C and 110C, and to act as the carrier for the monomer.
The residual unreacted VCM along with the steam are stripped out by the vacuum pump
and goes in to the Gas Holder.

iii. T105: Gas Holder
Most of the steam is automatically condense in this tank since it is under normal
condition. The gaseous phase of the VCM is collected and then compressed and liquified then
goes into the crude VCM Storage tank.
iv. T106: Crude VCM Storage Tank
This tank serves as a storage of VCM with some traces of water. The crude VCM is then
pumped into a purification column.

v. C108: VCM Purification Column
The crude VCM is purified to 99.9% VCM to be able to meet the composition of the
starting VCM. It is then stored into a tank.
vi. T107: Recovered VCM Storage Tank

The recycled VCM serves as the holding tank of the unreacted VCM from the
polymerization reaction which is ready to be recycled and charged back as raw material in the
autoclave.
vii. T108: Slurry Tank
After being produced in the reactor, the polymer along with impurities such as unreacted
monomer and water are what composes the product stream. This mixture is sent to a stripping (or
dump) tank for purification. As the stripping or flashing is employed to the mixture, the
monomer is separated from the main product stream of polymer and water.
The desired product stream (as opposed to the recycle monomer stream) coming from the
stripping tank is composed mainly of the polymer and water. The composition of the mixture is
approximately 32% PVC and 68% water. This slurry from the stripping tank is then pumped to
the slurry storage tank. This tank consists of an agitator in order to prevent the separation of the
polymer particles. Furthermore, a recirculation loop is installed at the exit pump depending on
how many batches can be processed by the slurry tanks capacity. This allows for a, somewhat,

continuous flow for the succeeding the sub-processes. Before undergoing the next processes,
quality-control tests are recommended to be conducted.
viii. S101: Centrifuge
From the slurry (or blend) tank, the stream is then passed through a centrifuge to separate
it into water solution and wet PVC solids. In this stage, much of the water content of the mixture
is removed and the wet PVC solids exiting are containing 20-25% water. The feed enters through
the axis of the horizontally configured conical centrifuge. The bowl rotates at a speed of around
500 rpm. In addition, the centrifuge has a plow mechanism in which the rotation speed is less
than that of the bowl but towards the same direction. The centrifuge is operated as continuously
as possible.

ix. D101: Fluidized Bed Dryer
PVC: 99.5%
H2O: 0.5%
After obtaining wet PVC solids from the centrifuge, the polymer resins are dried using a
fluidized bed dryer. Other commonly utilized drying equipment for suspension polymerization
products include rotary and dryers. Heated air flows upward in a two-chamber fluidized bed
dryer as the wet PVC solids pass downwards. However, it must be noted that operation of the
dryer should not exceed a temperature of 65 C due to the possible degradation of the polymer.
The PVC resins flowing out of the dryer has a moisture content of around 0.2% which can be
considered as having an excellent quality.
The source of heated air utilized for the fluidized bed drier is a finned-tube heat
exchanger designed to heat air flowing at a velocity of 200 ft/s to 300 F which can then heat the
solids up to 136 F. Furthermore, a cyclone separator is added to the setup to recover PVC
particles in the outgoing air stream.

x. S102: Screen
Coarse resins
Desired PVC Resins
Upon drying the PVC resins, the product stream then enters a screening stage. This is
done to ensure the uniformity in size of the final product and also serves as a quality control step
undergone in order to remove undesired resin sizes. The average particle sizes peak at around 60-
140 mesh. Common standards, as mentioned by .. (), state that there should not be any trace of
particles with sizes of 40 mesh and larger in product while only a maximum of 2% for 200 mesh
and smaller. Aside from the quality of the final product, a problem may arise in the bulk flow of
the resins, especially in the case of having 5% or more of 200+ mesh resins. In addtition, larger
resin sizes may have negative effects in the plasticization processes consequently undergone by
the polymer. Meanwhile, for the specific application of piping, the desired range of particle size
is around 95% 60-200 mesh. This is due to flowability requirements of the resins as well as its
possible effect to the porosity of the pipes’ cross section.

xi. T109: PVC Storage Tank
After screening, the PVC resins, which are already of desired size and quality, are finally
stored in silos. The resins are transported using pneumatic conveyors. PVC resin is often
supplied in powder form and long term storage is possible since the material is resistant to
oxidation and degradation. Around 80% of the resin product is dispatched to customers in bulk
road tankers. The remainder is packed into bags in the warehouse before dispatch.


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Chapter 3 PVC Production

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Technological Institute of the Philippines

363 P. Casal St., Quiapo, Manila

Engr. Michael Francis Sy

Agoncillo, Michaela Andrea

Antonio, Carl Brian

Calimbas, Bea Mariz

Doton, Ephraim John

Gamurot, Ele Jon

Tejio, Carissa Jane

CH32FB1 CHEM 302 March 22, 2017

VCM-BASED PVC PRODUCTION 1

ii. Process Description

a. Direct Chlorination of Ethylene

FeCl3 + Cl2 ↔ FeCl4-Cl+ Eqn. 1

VCM-BASED PVC PRODUCTION 2

CH2CH2 + 2HCl + 1/2 O2 → ClCH2CH2Cl + H2O Eqn. 3

Ethylene oxychlorination is normally conducted at temperatures of 225-325 ˚C and at

VCM-BASED PVC PRODUCTION 3

VCM-BASED PVC PRODUCTION 4

ClCH2CH2Cl → CH2=CHCl + HCl Eqn. 4

VCM-BASED PVC PRODUCTION 5

II – A. Process Flow Diagram

VCM-BASED PVC PRODUCTION 6

III - A. Process Description in VCM Production

VCM-BASED PVC PRODUCTION 7

ii. R102: Oxychlorination Reactor

VCM-BASED PVC PRODUCTION 8

iii. C101: Caustic Scrubber

VCM-BASED PVC PRODUCTION 9

iv. C102: Flash Column

VCM-BASED PVC PRODUCTION 10

v. C103: Lights Column

Distillation is a common separation process where the differences in volatility are

VCM-BASED PVC PRODUCTION 11

vi. C104: Heavies Column

VCM-BASED PVC PRODUCTION 12

vii. F101: Cracking Furnace

VCM-BASED PVC PRODUCTION 13

viii. C105: HCl Column

VCM-BASED PVC PRODUCTION 14

ix. C106: VCM Column

x. T104: VCM Tank

VCM-BASED PVC PRODUCTION 15

I-B. PVC Polymerization Process

One of the major disadvantages of emulsion polymerization is the difficulty in

ii. Process Description

VCM-BASED PVC PRODUCTION 16

II-B. Process Flow Diagram

VCM-BASED PVC PRODUCTION 17

III – B. Equipment Description

3. Chain Transfer to monomer:

VCM-BASED PVC PRODUCTION 18

4.Termination: 2 CH 2 CHCl CH 2 CHClClHC CH 2

CH 2 CHCl+ R CH 2 CHClR Eqn. 8

VCM-BASED PVC PRODUCTION 19

ii. C107: Stripping Tank

VCM-BASED PVC PRODUCTION 20

iii. T105: Gas Holder

iv. T106: Crude VCM Storage Tank

VCM-BASED PVC PRODUCTION 21

v. C108: VCM Purification Column

vi. T107: Recovered VCM Storage Tank

VCM-BASED PVC PRODUCTION 22

vii. T108: Slurry Tank