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PRODUCTION OF VINYL CHLORIDE FROM

ETHYLENE DICHLORIDE BY PYROLYSIS

Aspen Model Documentation

Index
• Process Summary

• About This Process

• Process Definition

• Process Conditions

• Physical Property Models and Data

• Chemistry/Kinetics

• Key Parameters

• Selected Simulation Results:


Blocks
Streams

• References

PEP Process Module 1 20 Sep 1999


Process Summary

This Aspen Plus model simulates the production of vinyl chloride monomer (VCM) from ethylene
dichloride (EDC) by pyrolysis. The process is based on the dehydrochlorination of EDC in a gas-phase
reaction. Our evaluation of this process is based on a production capacity of 500 million lb/yr (227,000 metric
ton/yr) of VCM at 0.9 stream factor. The process consists of the dehydrochlorination and VCM recovery
sections. Results from the Aspen Plus simulation shows that the purity of VCM obtained is 99.97%. By-
products contains 77.8wt% EDC, at 4,575 lb/hr. Other gaseous by-product from the HCl column is obtained at
37,240 lb/hr, 99.8% HCl mass purity.

PEP Process Module 2 20 Sep 1999


About This Process

Previously, the dehydrochlorination process is carried out in a liquid phase with alkali. Today, gas-phase
dehydrochlorination is used exclusively: thermal (favored method) and catalytic (infrequent; e.g. SBA process,
Wacker process). The manufacture of VCM from EDC involves cracking of the EDC, and subsequent cooling
and rectification of the reaction product mixture. Deposits of carbon black and coke in the reaction furnace
often require a shutdown of the furnace at intervals of some months for decoking operations. The formation of
by-products is partly attributable to the fact that attempts have been made to use very pure EDC. Another cause
is that the reaction products are thermally unstable at the required high temperature and undergo decomposition
to carbon in a series of further reactions. Selectivity to VCM is favored by high flow rate, exact temperature
control, careful purification of EDC, and limitation of conversion of EDC. A recent Hoeschst patent (643035)
permits the exact measurement of the conversion rate, thus effects a more reliable suppression of by-product
formation. The important aspects of the process are discussed below.

Feeds
The feed should be pure EDC. Impurities increase coking, and thereby shorten the operating time between
decokings. A high purity feed may also minimize the formation of troublesome impurities in the product and
simplify the recovery procedures. The desired minimum purity often quoted is 99.5% (Industrial Organic
Chemistry, 1993). One analysis given in a patent is shown in Table 1 (481370).
Table 1. EDC FEED COMPOSITION
Components Percent
1,2-EDC 99.51
Vinyl chloride 0.1
Benzene 0.159
Ethyl chloride 0.004
1,2-Dichloroethylene 0.014
2-Chlorobutadiene-1,3 0.034
l,l-Dichloroethane 0.052
Carbon tetrachloride 0.044
Chloroform 0.011
1,1,2-Trichloroethylene 0.044
l,l,P-Trichloroethane 0.004
Ethylene chlorohydrin 0.002
Unknown 0.053

One U.S. plant uses 99.8% EDC (private communication). However, a patent (643007) advocates the
addition 0.001-5% by weight of trichloroacetyl chloride to reduce the cleavage temperature of EDC at the same
conversion or increase conversion at the same cleavage temperature, and at the same time reduce by-products
formation. A Hoeschst patent (643023) uses 250 ppm of benzotrichloride to increase VCM yield; another
patent (643068) uses hexachloroacetone at a weight ratio of promoter to EDC in the range from about
0.00001:1 to about 0.01:1also to increase VCM yield. Patent 643094 advocates the addition of

PEP Process Module 3 20 Sep 1999


carbontetrachloride (0.1-0.15% by weight of carbontetrachloride based on EDC), while limiting the
trichloromethane content to less than 200 ppm.

Reactor
Pyrolysis of EDC in the gaseous phase is the most widely used industrial process for the production of
VCM. According to this process, the reactor is a direct-fired tubular furnace (643032, 643005). Some of the
tubes are made of Inconel, when fuel oil is burned. Stainless steel 316 can be used exclusively when the fuel is
natural gas, provided precaution is taken on shut-down, to guard against the entry of moisture into a reactor
containing HCl gas. It has now unexpectedly been determined that EDC can be heated to an elevated
temperature by intimately admixing it with a very hot fluid or solid particles (643032). This markedly differs
from the process in which liquid EDC is heated in the tubes of a reactor furnace.

Heat Recovery
Some patents advocate the recovery of heat from the reaction product by indirect cooling to generate
steam, to preheat the feed, or to preheat air needed in the furnace (643013, 643005, 643087, 643077, and
643089). Patent 643087 also applies partial utilization of the heat content of the flue gases from the pyrolysis
furnace firing to preheat liquid EDC almost to its boiling point, utilizing the flue gas waste heat to generate
steam. A patent (643003) applies direct cooling of the pyrolysis product immediately after leaving the
pyrolysis step down to about 150-2500C, recovering the vapors from the head of the quench column, and
indirectly cooling the same by heat exchange to at least its condensation point, thereby recovering some
thermal energy. Such procedures, however, causes tar formation and plugging; it is not practiced in
commercial operations. A recent Tosoh Corp. patent (643013) endeavors to minimize the problem by careful
cooling. Another patent (481370) applies indirect and then direct cooling, with the intention to avoid an
essential portion of the equipment and machinery required for purely direct cooling where large quantity of
recycle coolant is required.

Nevertheless, quenching the product mixture with cold EDC or cooled, condensed portions of the reaction
mixture, and recycling the EDC back to the dehydrogenation step after separation of the VCM by distillation is
the procedure commonly used (643076, Industrial Organic Chemistry, 1993). The disadvantage of this method,
however, is the high-energy demand for pumping the recycle flow of reaction product and the complete loss of
the heat supplied to the reaction furnace (481370).

Separation
The product from the reactor is mainly VCM, HCl, and unreacted EDC, conversion being generally 50%-
65%. These are often separated according to their relative volatility; HCl is first separated, and then VCM.
VCM thus recovered is degassed to remove residual HC1. The above procedure (US 3,843,736) is the one
generally followed. Separation by freezing or adsorption is not used commercially.

PEP Process Module 4 20 Sep 1999


However, the known process is disadvantageous if the VCM fed to the degassing zone still contains small
amounts of water unavoidably introduced during interruptions in operation. In practice, therefore, the
degassing zone is then operated in such a way that the water is separated off via the bottom of the degassing
column, together with HCl, for which purpose the towers filled with sodium hydroxide is required. If this
separation is not carried out, water would be circulated together with the recycled EDC and cause corrosion.
Patent 643033 states that the towers filled with sodium hydroxide can be omitted if the degassing column is
operated in such a way that the major part of the water is taken off at the top and removed, advantageously by
drying.

Purification of VCM
Several patents aim at removing butadiene from VCM (90616, 90303, 481106, 481206, 481208).
References 90560, 90591, and 311728 also deal with removal of butadiene from the reaction product, before
the separation of VCM. However, it seems that if the feed to the reactor is 99.8% or purer EDC, the VCM
produced contains butadiene in an amount below 8 ppm, which is allowable for polymerization. Another
possible impurity in VCM is HCl. The conventional way to remove HCl is by degassing, followed by a caustic
treatment or contacting with zinc (481110) to remove residual HCl. Reference 90617 suggests a method using
an alcohol treatment, and distillation.

Purification of EDC
EDC separated from VCM contains numerous impurities, as discussed under the section on chemistry.
Trichloroethane, perchloroethane, perchloroethylene, and polychlorinated C-4 compounds are separated as
heavy ends. Ethyl chloride, methyl chloride, chloroform, carbon tetrachloride, l,l-dichloroethane, and
dichloroethylene (cis and trans) are separated as light ends. Trichloroethylene itself boils at a higher
temperature than EDC does but it forms a minimum boiling point azeotrope with EDC (normal bp 82.1°C,
EDC bp 83.7°C) and is extremely difficult to separate from EDC. To minimize the accumulation of
trichloroethylene in the recycled EDC, one has to allow some EDC to go into the light ends, together with the
azeotrope of trichloroethane/EDC. Chloroprene, which if accumulated in large amounts may polymerize and
lead to plugging. It seems that if high purity EDC is used, chloroprene does not accumulate to a troublesome
degree. Both the light ends and heavy ends contain EDC and can be used as feed for making chlorinated
solvents. In an integrated operation, the light ends may be added to the chlorination unit, where dichlorinated
compounds and trichloroethylene convert to trichloroethane and perchlorinated compounds and become heavy
ends. If there are not such outlets, the light ends and heavy ends have to be incinerated.

PEP Process Module 5 20 Sep 1999


Process Definition

The Aspen Plus model simulate the steady-state production of VCM from EDC. The process is based on
the dehydrochlorination of EDC in a gas-phase reaction. Our evaluation of this process is based on a
production capacity of 500 million lb/yr (227,000 metric ton/yr) of VCM at 0.9 stream factor. The design bases
and assumptions are summarized in the following section.

In the Aspen model, Radfrac models are used to represent the distillation columns. Due to insufficient
kinetics information, Aspen Plus RYIELD reactor models are used to represent R-101A and B. The reactor is
considered to have two valid phases; vapor and liquid phases.

Purified ethylene dichloride is preheated and vaporized by steam in vaporizer E-101. EDC vapor is heated
to decomposition in the tubes of furnace R-101, where about 60% are converted to vinyl chloride. The
conditions are controlled at 930F and 210-230 psig. The reaction gas emerging from the furnace flows to
quenching tower, C-101, where the gas temperature is reduced to 287F. In cooler E-102 most of the EDC is
condensed. The bottom stream from C-101 is filtered to remove carbon and tars, and recycled to the top of the
column.

Condensate and gases from E-102 are fed to hydrogen chloride fractionating column C-102. The
overhead from the hydrogen chloride fractionating column is hydrogen chloride gas, which is available for use
in hydrochlorination or other uses. The bottom product from C-102 is fractionated in VCM column C-103.
Vinyl chloride recovered from C-103 contains about 300-500 ppm hydrogen chloride. In degassing column C-
107, HCl together with some VCM is removed and recycled to C-102. Vinyl chloride from the bottom of C-
107 still contains about 10 ppm HCl, which is removed by contacting with solid caustic soda pellets in V-112.
When the caustic soda is used up, V-112 is flushed with water. Vinyl chloride thus obtained has an acidity
below 0.1 ppm.

The bottom product from C-103 is unconverted EDC with impurities. It is pumped to column C-104,
where light ends, together with some EDC are removed as a distillate to column C-108, where light ends are
then removed as a distillate. The bottom product from C-104 is pumped to heavy ends column C-105. The
distillate is EDC with a purity of 99.9% or higher. The bottom product from C-105 is further distilled in
vacuum column C-106 to recover more EDC, which is recycled to the pyrolysis furnace R-101.

PEP Process Module 6 20 Sep 1999


Process Conditions
Table 2 provides the list of important blocks, design bases and assumptions for the process:

TABLE 2. VCM FROM EDC BY PYROLYSIS DESIGN BASES AND ASSUMPTIONS


Capacity: 500 million lb/yr (227,000 t/yr)
VCM at 0.90 stream factor

References Industrial Organic Chemistry (1993), 643076, 643003,


643087

Reactor
Reactor temperature (0C) 930°F (5000C)
Reactor pressure (psig) 210-230 psig
EDC Conversion (%) 60
Selectivity to VCM (%) 99

Column internals
C-101, Quenching Column Sieve trays
No design spec

C-102 HCl Column Valve trays


Design specs:
99.99mol % recovery of HCl in the overhead.
Design variables:
Bottom to feed ratio.

C-103 VCM Column Valve trays


Design spec:
99.7 mass % recovery of VCM in the overhead.
99.7 mass % recovery of EDC in the bottoms.
Design variable:
Bottom to feed ratio.
Reflux ratio.

C-104 Light Ends Column Valve trays


Operation specs:
Distillate to Feed ratio=0.3
Reflux Ratio=5
No design spec
C-105 Heavy Ends Column Valve trays
Operation specs:
Bottom to Feed ratio=0.1
Reflux Ratio=3
Design specs:
98 mol % recovery of EDC in the overhead.
Design variables:
Bottom to feed ratio.
C-106 Vacuum Column Sieve trays
Operation specs:
Bottom to Feed ratio=0.015
Reflux Ratio=2
No design spec

PEP Process Module 7 20 Sep 1999


C-107 Degassing Column Valve trays
Operation specs:
Distillate rate=3321 lb/hr
Reflux Ratio=3
Design specs:
98 mol % recovery of VCM in the bottoms.
Design variables:
Distillate rate.

C-108 EDC Recovery Column Valve trays


Operation specs:
Bottom to Feed ratio=0.965
Reflux Ratio=3
No design spec

PEP Process Module 8 20 Sep 1999


Physical Property Methods and Data

The Aspen Plus simulation uses the NRTL-RK physical property method. The NRTL model can describe
VLE and LLE of strongly nonideal solutions. The NRTL model requires binary parameters. Many binary
parameters for VLE and LLE, from literature and from regression of experimental data, are included in the
ASPEN PLUS databanks.

Separate data sets can be used for the NRTL binary parameters to model properties or equilibria at
different conditions. The NRTL model can also handle any combination of polar and non-polar compounds, up
to very strong non-ideality. Parameters should be fitted in the temperature, pressure, and composition range of
operation. No component should be close to its critical temperature.

PEP Process Module 9 20 Sep 1999


Chemistry/Kinetics
Reactors

Ethylene dichloride decomposes on heating, to vinyl chloride and hydrogen chloride:


C 2 H 4Cl 2 → C 2 H3Cl + HCl
ΔH r = 16.66 kcal/gmol (endothermic)

The mechanism is a thermal chain reaction, initiated by a chlorine free-radical that splits from C2H4Cl2 on
heating. (PEP Report 5, pp. 17-18.) Numerous by-products such as trichloroethane, tetrachloroethane,
pentachloroethane, perchloroethane, dichloroethylene, trichloroethylene, and perchloroethylene are formed
through chlorination and dehydrochlorination.

Cl
CH 2 = CHCl ⎯⎯→ CHCl 2 − CH 2Cl
↓Δ
CHCl = CHCl + HCl
↓ Cl
CHCl2 − CH 2Cl
↓Δ
CCl 2 = CHCl + HCl
↓ Cl
CCl3 − CHCl2
↓Δ
CCl 2 = CCl 2 + HCl
↓ Cl
CCl3 − CCl3

1,1-Dichloroethane may form from vinyl chloride and HCl (481104):


C 2 H 3Cl + HCl ⇔ CH 3CHCl 2

Small amounts of coke and acetylene are formed:

2C2 H 4Cl2 → C2 H 4 + 4HCl + 2C


2C2 H 4 → 2CH 4 + 2C
C2 H 3Cl → HCl + C2 H 2

Other impurities also found in the cracking product are benzene, hydrogen, ethylene, chloroprene,
butadiene, polychlorinated C-4 compounds, methyl chloride, chloroform, carbon tetrachloride, ethyl chloride,
and polymeric solid.

The decomposition to vinyl chloride is accelerated by the presence of a small amount of initiator such as
tetrachloride or chlorine, but it is inhibited by ethylene olefins or impurities such as ethylene chlorohydrin
(481322). Oxygen also accelerates the decomposition, but leads more to the formation of by-products.

PEP Process Module 10 20 Sep 1999


Catalytic cracking at 300-4000C on pumice (SiO2, Al2O3, alkalis) or on charcoal, impregnated with BaCl2 or
ZnCl2, has not found more widespread application due to the limited life of catalysts.

The yields used to model the RYIELD reactor R-101A and B in the Aspen Plus model are as follow:

Components Yields Per Unit Mass of Non-Inert Feed


(Not normalized)
H2 9
HCl 37,165
ACETYLE 26
ETHYL-01 33
VCM 63,634
1,2-B-01 0.49
CIS-1-01 42
CHLORPR 82
Benzene 99
EDC 66,187
TRICH-01 49
1,1,2-01 304
TETRA-01 94
P-TER-01 185
Carbon 251

PEP Process Module 11 20 Sep 1999


References
Reference Earliest Reaction Reaction Residence EDC Selectivity
Number Date Catalyst Feed Temperature Pressure Time Conversion to VCM
(Patent) Assignee Shown (°C) (psia) (seconds) (%) (mol%)

481370 Link, G., et al. 7/17/80 None EDC 480-560 203-348 4 55 N/A
(US 4,324,932)

The hot gas mixture leaving the reaction furnace is cooled to the inlet temperature of the column in which HCl is separated from the products of
the thermal cracking of EDC. Within the range of 560-490oC and 220-120oC, one or more cooling stages are applied through which the reaction
gas mixture passes at high flow velocity, the cooling device being preferably a single-tube cooler. Starting from about 220oC, a liquid
substantially consisting of EDC may be added intermittently. The heat transferred to the coolant in the stages of indirect cooling is preferably
reused within the VCM manufacturing process, utilizing valuable thermal energy that is lost through purely direct cooling.

643093 Tosoh Corp., 11/25/87 None EDC 500 338 58.8 N/A
(US 4,960,963) Shinnayo N/A

There is a heat exchange between a high temperature cracked gas produced and the EDC to be introduced into the pyrolysis furnace. The cracked
gas is cooled down to 180-350oC, and with the flow rate of the cracked gas being equal to or more than 5 m/s but less than 20 m/s, preferably 9.2-
13.8 m/s. As a result, the pressure drop in the heat exchanger in which EDC introduced in the pyrolysis furnace is preheated and evaporated is
minimized. Coke formation is also reduced.

643035 Hoeschst 2/8/95 None EDC N/A N/A N/A 60 N/A


(US 5,545,780) Aktiengesellschaft
The patent describes the determination of the conversion rate in the preparation of VCM by thermal cracking of EDC by measuring the absorption
of high-energy radiation, pressure, and temperature of the gases issuing from the cracking furnace. The objective is to keep the conversion rate as
constant as possible, and as a result, suppress the formation of by-products, in particular, coke formation, which in turn leads to considerably
increased service lives of the entire plant.

643023 Hoeschst 10/9/92 None EDC 300-600 145-580 N/A 76 N/A


(US 5,210,345) Aktiengesellschaft
An addition of benzotrichloride produces a significantly higher yield of VCM in the thermal cleavage of EDC. For example, 250 ppm of
benzotrichloride increases the VCM yield from 52% (feed EDC without additive) to about 76%.

643068 PPG Industries, 6/25/84 None EDC 500 26-305 0.1-30 62-64 N/A
(US 4,584,420) Inc.
The patent describes the use of a compound with chemical formula CX3COCX3, wherein each X is independently chloro or bromo, as a pyrolysis
promoter in the pyrolysis of EDC to VCM. Hexachloroacetone is the particularly preferred promoter. The promoter is introduced at a weight
ratio of promoter to EDC in the range from about 0.00001:1 to about 0.01:1, to increase VCM yield.

643033 Hoeschst 12/7/94 None EDC 450-650 118-588 N/A N/A N/A
(US 5,507,920) Aktiengesellschaft
The patent describes the three distillation stages used in the preparation of VCM by pyrolysis of EDC. The first step involves the distillation of
HCl, then VCM and finally entrained HCl with VCM. If in the last stage, entrained water is not drawn off via the bottom, it is re-circulated with
the top product to the first stage and causes corrosion. Removal of water at the top of the third distillation stage by drying with molecular sieve or
silica gel prevents the corrosion. The dried mixture of VCM and HCl is then re-circulated back into the first distillation zone.

643032 Elf Atochem S.A. 4/21/93 None EDC 662 22 0.089 77 95.5
(US 5,488,190)
VCM is prepared by intimately contacting, in the absence of steam, a feedstream of EDC with a flow of fluid or solid particulates heated to such
elevated temperature and for such small period of time, i.e. 0.01-0.5 second, as to transfer a dehydrochlorinating amount of thermal energy to the
EDC and thereby ultrapyrolyzing EDC into VCM and HCl.

643007 Hoeschst 8/6/84 None EDC 350-550 145-580 4-40 50-60 N/A
(US Aktiengesellschaft
4,851,597)

PEP Process Module 27 20 Sep 1999


The patent describes the addition of 0.001-5% by weight of trichloroacetyl chloride or a compound which contains 3 carbon atoms and, for each
carbon atom bonded to the latter, 0-1 hydrogen atom, is added to it. The compounds are added into liquid EDC before thermal decomposition.
The advantage of the invention is to make it possible to reduce the cleavage temperature of EDC at the same conversion or increase conversion at
the same cleavage temperature, at the same time reduce by-products formation.

643005 Snamprogetti, 7/24/78 None EDC 450-550 N/A N/A N/A N/A
(US 4,843,182) S.p.A.
The invention relates to a process for the production of VCM by starting from EDC is heated without being vaporized in the convective section of
the oven. It is then vaporized by indirect heat exchange with air or another fluid, which is heated in its turn by the heat of the cracking products
leaving the oven. EDC, as vapor is then introduced into the radiant section of the oven, whereby it undergoes cracking to give VCM.

643003 Wacker-Chemie 4/7/88 None EDC 512 181 N/A 60 N/A


(US 4,822,932) GmbH
The patent describes a method in the production of VCM by pyrolysis of EDC, with multiple stage cooling and distillation to separate the reaction
product, and recycle the unreacted EDC to the pyrolysis step. This method applies direct cooling of the reaction product immediately after leaving
the pyrolysis step, within 1 second from a temperature of 480-540oC down to 150-250oC. The cooled product is charged into a quench column,
recovering the vapors from the head of the quench column, and indirectly cooling the same by heat exchange to at least its condensation point.
The heat exchange media could be (a) EDC to be fed to the pyrolysis unit, (b) air used as combustion air to fire the pyrolysis unit, (c) the sump of
the HCl column, (d) liquid HCl to be evaporated, and (e) water to dissipate heat. This invention partially recovers the energy expended from the
pyrolysis and avoids large pressure loss in the heat exchanger.

643089 Hoeschst 10/8/87 None EDC 533 537 N/A 65 96


(US 4,798,914) Aktiengesellschaft
Hot product gas leaving the cracking furnace heat liquid EDC in a first container to almost its boiling point, and the EDC is transferred into a
second container in which it is partly evaporated under a lower pressure than the first container. The evaporated EDC is fed into the cracking
furnace and the non-evaporated EDC is fed back into the first container. By supplying pre-warmed EDC into the second container, the amount of
product evaporated therein is replaced, the pre-warming being regulated by the level of the liquid EDC in the second container. The pre-warming
of the EDC can take place in the convection zone of the furnace or by steam, which has been heated in the convection zone of the furnace. The
process provides higher cracking conversions and more favorable energy utilization.

643087 Wacker- 7/16/87 None EDC 507 145-522 N/A 61.2 99


(US 4,788,357) Chemie GmbH
EDC is thermally cracked with partial utilization of the heat content of the flue gases from the pyrolysis furnace firing to preheat liquid EDC
almost to its boiling temperature, utilizing the flue gas waste heat to generate steam. The pyrolysis gas mix is cooled in several stages. HCl is
separated from the pyrolysis gas mix in a HCl column and VCM is separated from the gas mix in a VCM column. It is an object of this invention
to increase flue gas temperature in combination with another measure so that the heat recovery is economically feasible.

643094 Wacker-Chemie 10/27/86 None EDC 497 145-232 10-15 64 N/A


(US 4,746,759) GmbH
This patent describes a process for the preparation of VCM from EDC wherein 0.10-0.15% by weight of CCl4 based on EDC, is used as a
promoter and the CHCl3 content is limited to less than 200 ppm. Before being fed to the cracking zone, EDC is brought almost to the boiling point
at 15-31 bar, and then expanded to 10-16 bar. The EDC vapors is flashed and the fraction which remained as liquid is vaporized externally. The
combined EDC gas streams are then fed into the cracking furnace. The energy required for cracking is already supplied in the first 75-85% of the
reaction zone, whereby a conversion of 60-70% is obtained at residence time from 10-25 seconds. The exit temperature of the reaction zone is
485-510oC. It is an object of the invention to substantially reduce the specific consumption of utilities for the process steps of purifying
unconverted EDC and vaporizing purified EDC in the cracking furnace.

643076 BASF 10/9/84 None EDC 450-500 218 N/A N/A N/A
(US 4,720,599) Aktiengesellschaft
The patent describes a process for the preparation of VCM by vaporizing liquid EDC, thermally cracking the EDC and cooling the hot reaction
mixture by means of cooled and condensed portions of the reaction mixture. A defined amount of the EDC is taken off as liquid in or downstream
of the vaporizer and mixed with a defined amount of the cooled liquid portion of the reaction mixture. The mixture is distilled and the constituents
taken off the top of the distillation column are recycled to the liquid EDC upstream of the vaporizer. The constituents taken off the bottom of the
distillation column are worked up by distillation. The objective of this invention is to reduce the losses of useful products.

643077 Snamprogetti 8/15/86 None EDC 450-550 N/A N/A N/A N/A
(US 4,721,604) S.p.A.
The patent describes the thermal cracking furnace for the production of VCM from EDC. EDC is heated, without being vaporized, in the
convective section of an oven. It is then vaporized by indirect heat exchange with air or another fluid, which is heated in its turn by exploiting the

PEP Process Module 28 20 Sep 1999


heat of the cracking products leaving the oven. EDC vapor is introduced into the radiant section of the oven, wherein it undergoes cracking and
forms VCM. The enthalpy of the products is thus recovered.

643074 Stauffer Chemical 12/8/82 None EDC 185 157 N/A N/A N/A
(US 4,665,243) Company
The energy requirements for preparing VCM can be reduced by a process, which includes the steps of purifying by distillation EDC, compressing
EDC vapor from the distillation column to a temperature and pressure sufficient for direct feed to a pyrolysis furnace. Up to 80% of the heat
presently used after distillation and before pyrolysis can be saved. The compressor can be any mechanical compressor that is adapted for gas
compression; insulated and provided with proper temperature control means such as heating fluids in a jacket to prevent condensation. Further
heating can also be applied beyond the compressor and before the pyrolysis furnace if necessary.

643071 PPG 11/23/84 None EDC 517 116-174 3-15 60 99


(US 4,590,318) Industries, Inc.
In the pyrolysis of EDC to VCM, the stream removed from the furnace is introduced to essentially unheated conduit means. Pyrolysis promoter is
introduced to the stream in the conduit means and sensible heat of the stream is utilized in the conduit means to pyrolyze further amounts of EDC
and to increase the yield of VCM. Molecular chlorine is the preferred promoter. The promoter preferably, is introduced to the stream at a weight
rate ratio of the promoter to the stream from about 0.001:1 to about 0.0015:1. The residence time of the stream in the conduit means range from
about 0.15-2 seconds.

Report by: Noni Lim


September 20, 1999

PEP Process Module 29 20 Sep 1999