Cracking EDC

Nearly all commercially made VCM is produced by thermal dehydrochlorination or cracking

of EDC.

C2H4Cl2 → C2H3Cl + HCl

Cracking is an endothermic process (ΔHrxn = 71 kJ/mol EDC consumed) that occurs as a
homogeneous, vapor-phase, first-order, free-radical chain reaction. Commercial EDC
crackers operate at gauge pressures of 1.4-3.0 MPa (200-435 psig) and at temperatures of
475-525°C. EDC conversion per pass is normally maintained at 53-63%, with a residence
time of 2-30 sec. Cracking reaction selectivity to vinyl chloride of >99% can be achieved at
these conditions. Increasing conversion beyond this level gives progressively lower
selectivity to VCM and higher coking rates. High-pressure cracking will also lead to lower
selectivity to VCM, higher byproduct formation, and higher coke formation.

Cracking furnace effluent must be quenched, or cooled rapidly, to keep coking at a minimum.
Therefore, the hot effluent gases are typically quenched and partially condensed by direct
contact with cold EDC in a quench tower. Alternatively, the hot effluent can first be cooled
by heat exchange with cold liquid EDC furnace feed or by vaporizing boiler feed water
(BFW) to produce high-pressure steam in a transfer line exchanger (TLX) prior to entering
the quench tower. This arrangement saves energy by decreasing the amount of fuel needed to
fire the cracking furnace and/or steam needed to vaporize the feed.

EDC Cracking and VCM Purification

Process

Hydrogenation

While EDC cracking is highly selective to VCM, a small fraction is cracked all the way to
acetylene. Since acetylene is close to HCl in volatility, it is separated from the cracking
product along with HCl in the VCM purification process, and ends up in the feed to the
oxychlorination process. Typical concentrations of acetylene in this HCl recycle stream are
1,000-2,000 ppm by volume. If allowed to enter the oxychlorination reactor, the acetylene
would be readily converted to trichloroethylene, perchloroethylene and other heavily
chlorinated by-products, resulting in a significant HCl efficiency loss. Consequently, the HCl
recycle stream is usually passed through a hydrogenation reactor to selectively convert the
acetylene to ethylene, which makes more EDC downstream.

Hydrogenation is generally carried out in a fixed bed reactor packed with catalyst made from
a precious metal on an inert support. Hydrogen is added to the feed in stoichiometric excess
to ensure conversion of acetylene to ethylene. The reaction is temperature dependent, with
lower temperatures being preferable to maximize conversion to ethylene. If the temperature is
too high, a fraction of the acetylene may be further hydrogenated to ethane. Although ethane
is relatively inert to oxychlorination and passes through, exiting with the vent stream, this
represents a loss in terms of hydrogen usage and lost ethylene value. OxyVinyls Super H-2®
catalyst is especially efficient at converting acetylene to ethylene at lower temperatures than
other catalysts. Conversion of acetylene is routinely above 99 percent with a selectivity to
ethylene of more than 70 percent, with a typical catalyst bed run life in excess of 15 years.

Oxychlorination

In oxychlorination, ethylene reacts with anhydrous HCl and either air or pure oxygen in a
heterogeneous catalytic reaction to form EDC and water.

C2H4 + 2 HCl + �O2 ? C2H4Cl2 + H2O

While there are many different commercial oxychlorination processes, in each case the
reaction is carried out in the vapor phase in either a fixed bed or fluid bed reactor containing a
modified Deacon catalyst. Unlike the Deacon process, however, oxychlorination of ethylene
occurs readily at temperatures well below those required for HCl oxidation. The catalyst
typically contains cupric chloride (CuCl2) as the primary active ingredient, impregnated on a
porous support such as alumina, and may also contain numerous additives.

OxyVinyls' patented Oxychlor� 8 catalyst is ideally suited for fluid bed reactor operation.
This sixth-generation catalyst is the result of continuous research and development, which
has led to increased efficiencies and ease of operability. Oxychlor� catalysts are extremely
robust and highly tolerant to process upsets and diverse operating conditions. In addition to
easy operability, the latest generation of catalyst operates at higher temperatures, facilitating
heat removal and higher reactor productivity, along with improved feedstock efficiencies and
reduced catalyst losses.

The oxychlorination reaction is exothermic (?Hrxn = -239 kJ/mol EDC made) and requires
heat removal for temperature control, which is essential for efficient production of EDC.
Higher reactor temperatures lead to more by-products, mainly through increased ethylene
oxidation to carbon oxides and increased EDC cracking. (Cracking of EDC yields VCM, and
subsequent oxychlorination and cracking steps lead progressively to by-products with higher
levels of chlorine substitution.) High temperatures (>300�C) can also deactivate the catalyst
through increased sublimation of CuCl2.

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane,

chloroform, carbon tetrachloride, ethyl chloride, chloral, 2-chloroethanol, all of the
chloroethylene congeners, and higher boiling compounds. Of particular concern is chloral,
because it polymerizes in the presence of strong acids. Chloral must be removed (by caustic
washing) to prevent the formation of solids, which can foul and clog processing equipment
downstream.

Oxychlorination process feed purity can also contribute to by-product formation, although the
problem usually is only with the low levels of acetylene that are normally present in HCl
from the EDC cracking process. Since any acetylene fed to the oxychlorination reactor will
be converted to highly chlorinated C2 products, selective hydrogenation of this acetylene to
ethylene and ethane is widely used as a preventive measure.

Fixed Bed Technology

Fixed bed reactors resemble multi-tube heat exchangers, with the catalyst packed in vertical
alloy tubes held in a tubesheet at top and bottom. Uniform packing of catalysts within the
tubes is important to ensure uniform pressure drop, flow, and residence time through each
tube. Reaction heat is removed by generating steam on the shell side of the reactor, or by
flowing some other heat transfer fluid through it. However, temperature control is more
difficult in a fixed bed than in a fluid bed reactor because localized hot spots can develop in
the tubes. The tendency to develop hot spots can be minimized by packing the reactor tubes
with active catalyst and inert diluent mixtures in proportions that vary along the length of the
tubes, so that there is low catalyst activity at the inlet, but the activity steadily increases to a
maximum at the outlet. Another remedy is to pack the tubes with catalysts having a
progressively higher loading of cupric chloride so as to provide an activity gradient along the
length of the tubes. Multiple reactors in series are also used in fixed bed oxychlorination,
primarily to control heat release by staging the air or oxygen feed. Each successive reactor
may also contain catalyst with a progressively higher loading of cupric chloride. These
methods of staging the air or oxygen feed and of grading the catalyst activity work to flatten
the temperature profile and allow improved temperature control. Compared with the fluid bed
process, fixed bed oxychlorination generally operates at higher temperatures (230-300�C)
and gauge pressures (150-1400 kPa or 22-203 psig).Fixed bed reactors have a finite catalyst
life due to fouling or coking of the catalyst bed, requiring periodic, complete catalyst
replacement.

Fluid Bed Technology

Fluid bed oxychlorination reactors typically are vertical cylindrical vessels equipped with a
support grid and feed sparger system designed to provide good fluidization and feed
distribution. They contain internal cooling coils for heat removal, and use either internal or
external cyclones to minimize catalyst carryover. Fluidization of the catalyst assures intimate
contact between feed and product vapors, catalyst, and heat transfer surfaces, and results in a
uniform temperature within the reactor. Reaction heat is removed by generating steam within
the cooling coils or by passing some other heat transfer medium through them. An operating
temperature of 220-245�C and gauge pressure of 150-500 kPa (22-73 psig) are typical for
oxychlorination with a fluid bed reactor.

While fluid bed oxychlorination reactors are generally well-behaved and operate predictably,
under certain (usually upset) conditions, they are subject to a phenomenon known as
stickiness. This can best be described as catalyst particle agglomeration characterized by
declining fluidization quality and, in severe cases, a slumped or collapsed bed.
Oxychlorination catalyst stickiness is brought on by adverse operating conditions that
promote the formation of dendritic growths of cupric chloride on the surface of individual
catalyst particles, which leads to increasing interparticle interactions and agglomeration. All
fluid bed oxychlorination catalysts normally exhibit some level of catalyst particle
agglomeration/de-agglomeration dynamics, and the severity of stickiness depends on catalyst
characteristics as well as process operating conditions. Stickiness can be largely avoided by
using catalyst formulations that exhibit excellent fluidization characteristics over a wide
range of operating conditions. OxyVinyls' Oxychlor� 8 catalyst is extremely resistant to the
effects of stickiness.

Advantages of OxyVinyls Fluid Bed

Technology
 Indefinite catalyst life. Only small, periodic, on-line, catalyst additions are needed to
maintain the catalyst bed inventory. Compared to a fixed bed reactor system, which
requires a periodic full catalyst charge replacement, catalyst costs are lower for an
OxyVinyls fluid bed reactor system.
 Safe, flexible operations. OxyVinyls technology can operate safely and efficiently
over a wide range of operating rates using a wide range of feedstock qualities.
Because of the fluid bed inherent advantages in processing import HCl streams, such
as by-product HCl from MDI/TDI (Methylene diphenyl diisocyanate/Toluene
diisocyanate) plants, they are the reactor of choice for that configuration. Fixed bed
systems typically require a direct chlorination reactor to recover the high volume of
ethylene in the Oxy purge gas; OxyVinyls fluid bed technology has no such
restrictions.
 Superior heat recovery. Compared to a fixed bed system, an OxyVinyls fluid bed
recovers approximately 9% more heat, due to both the inherent ability of a fluid bed
to transfer heat and the lower gas throughput.
 Lower capital costs. Alloy and other specialized materials are only used where
needed, allowing the use of carbon steel where possible to minimize costs.
 Superior catalyst performance, including high efficiency and outstanding resistance
to stickiness, with the use of Oxychlor� cataly

Oxygen-Based Technology
The use of oxygen instead of air permits operation at lower temperatures and results in
significantly improved operating efficiency and product yield. Ethylene is generally fed in
somewhat larger excess over stoichiometric requirements than in the air-based process. The
reactor effluent is cooled, purified from traces of unconverted HCl, separated from EDC and
water by condensation, recompressed to the reactor inlet pressure, reheated, and ultimately
recycled. This permits lower ethylene conversion per pass through the reactor (giving higher
selectivity to EDC) with an increase in overall ethylene yield.

Another important advantage of oxygen-based oxychlorination over air-based operation is the

drastic reduction in volume of the vent stream. Only a small fraction of the reactor off-gas,
typically 2-5%, is continuously purged to prevent accumulation of impurities such as carbon
oxides, nitrogen, argon and un-reacted light hydrocarbons, which either form in the reactor or
enter the process with the feed streams. In the air-based process, a large vent flow rate is
required because of the nitrogen that enters with the air feed stream. (Nitrogen is actually the
single component with the highest molar feed rate in the air-based process.)

Oxygen-Based Oxychlorination Technology