[0001] The present invention relates to a process for the preparation of vinyl chloride
by the dehydrochlorination of mixtures of isomeric dichloroethanes.
[0002] It is known that vinyl chloride can be produced by the pyrolytic dehydrochlorination
of 1,2-dichloroethane. The process involves the passing of 1,2-dichloroethane through
a small diameter reaction tube in which it is heated to elevated temperatures to bring
about the dehydrochlorination thereof. In contrast to this, it has not hitherto been
possible to convert the isomeric 1,1-dichloroethane, which is a by-product of the
pyrolysis of 1,2-dichlorethane, into vinyl chloride in economic yields. Published
data indicate that 1,1-dichloroethane pyrolyses very much more slowly than 1,2-dichloroethane
and hence it has always been considered desirable to separate the two isomers prior
to pyrolysis.
[0003] It has now been found that mixtures of these isomers can be pyrolysed without impairing
the quality or yield of vinyl chloride monomer produced by regulating the concentration
of the two isomers in the mixture being pyrolysed.
[0004] Accordingly the present invention is a process for producing vinyl chloride comprising
pyrolysing at elevated temperature 1,2-dichloroethane mixed with between 0.1 and 10%
by weight of 1,1-dichloroethane.
[0005] The above reaction may be carried out in conventional tubular reactors as normally
employed for the pyrolysis of 1,2-dichloroethane. The pyrolysis of mixtures of 1,1-dichloroethane
and 1,2-dichloroethane in the specified range of concentrations significantly increases
the conversion of 1,1-dichloroethane from about 20% (for the pure isomey) to above
90% (when present in the isomeric mixtures). Both below and above this range the conversion
of the 1,2-isomer is depressed relatively. The amount of the 1,1-dichloroethane in
the isomeric mixture being pyrolysed is preferably between 1 and 8%. The 1,1-isomer
may be mixed with the pyrolysis feed prior to the introduction thereof into the reaction
zone. Alternatively it may be incorporated in the pyrolysis feed in the reaction zone
itself at the time of pyrolysis.
[0006] The pyrolysis of the isomeric mixtures may be carried out in packed or unpacked tubular
reactors. Where packed reactors are used they may suitably be packed with ceramic
spheres.
[0007] The pyrolysis of the isomeric mixture of dichloroethanes according to the present
invention is suitably carried out at a temperature of between 450° and 550°C, preferably
between 500° and 535°
C.
[0008] The pyrolysis of the isomeric mixture of dichloroethanes may be carried out at sub-atmospheric,
atmospheric or super-atmospheric pressures. It is, however, preferred to use super-atmospheric
pressure, preferably below 500 psig.
[0009] The pyrolysis of the isomeric mixture of dichloroethanes may be carried out in a
continuous manner.
[0010] The advantages of the present invention are illustrated with reference to the.following
Examples.
EXAMPLES
[0011] The apparatus, run at atmospheric pressure, consisted of feed reservoir, metering
pump, vaporiser, cracker tube, coolers, organic product receiver, hydrogen chloride
scrubbing column, scrub liquor reservoir and wet gas meter. There was also a nitrogen
diluent/ carrier feed applied to the vaporiser inlet.
[0012] Feedstocks comprising pure 1,2-dichloroethane (1,2-EDC), 1,2-dichloroethane with
up to 10 per cent by weight of 1,1-dichloroethane (1,1-DCE) and also pure (98.2% by
weight) 1,1-DCE were pyrolysed at a peak temperature of 500°C and a contact time of
4.5 seconds under conditions found to give a 50 per cent by weight conversion of pure
1,2-dichloroetliane.
[0013] Analysis of feedstock, organic condensate, scrub liquor and vent gas were used to
calculate the conversions tabulated below.

1. A process for producing vinyl chloride comprising pyrolysing at elevated temperature
1,2-dichloroethane mixed with between 0.1 and 10% by weight of 1,1-dichloroethane.
2. A process according to claim 1 wherein the amount of 1,1-diehloroethane in the
isomeric mixture being pyrolysed is between 1 and 8% by weight.
3. A process according to claim 1 or claim 2 wherein the pyrolysis of the isomeric
mixture of dichloroethanes is carried out at a temperature between 450°C and 550°C
4. A process according to claim 3 wherein the pyrolysis of the isomeric mixture of
dichloroethanes is carried out at a temperature between 500 and 535°C.
5. A process according to any of the preceding claims wherein the pyrolysis of the
isomeric mixture of dichloroethanes is carried out at superatmospheric pressures.
6. A process according to claim 5 wherein the superatmospheric pressure is below 500
psig.
7. A process according to any of the preceding claims wherein the pyrolysis of the
isomeric mixture of dichloroethanes is carried out in a continuous manner.
8. A process for producing vinyl chloride according to claim 1 as hereinbefore described
with reference to the Examples.
9. Vinyl chloride whenever produced by a process according to any of the preceding
claims.