United States Patent [191 [111 49 060 ,460

Smalley et al. [45] Nov. 29, 1977

[54] FROM FOREIGN PATENT DOCUMENTS

1,959,211 6/1970 Germany ........................ .. 260/652 P
[75] Inventors: $23,233:; Primary ExaminerDelbert E. Gantz
- Assistant Examiner-J. Thierstein
gmdyopadhyay Camlnus Attorney, Agent, or FirmGerhard H. Fuchs
_ _ _ _ _ [57] ABSTRACT

[73] Asslgnee: Col-Wuhan Moms Process is provided for removal of chloroprenes as

p ' ' impurities from ethylene dichloride streams formed in
_ the production of vinyl chloride by the thermal crack
[21] APPI N" 5804,77 ing of ethylene dichloride. The ethylene dichloride
- , stream is subjected to distillation in a distillation zone to
[22] Flled' May 22 1975 which free chlorine gas is introduced, thereby chlori
[51] Int. 01.2 ............................................ .. C07C 17/38 Hating the chbmprenes mumbled therein and ?rming
[52] U s C1. ............................ .. 203/29- 260/652 P- higher bi1i11g h1IarbnS as reatin Pmducts- Th6
' ' " ' ' 203/31 higher boiling chlorocarbons, together with ethylene
[58] Field of Search ............... 260/652 P 654 s dichlmide, may be Iemmed as bttms and Passed t *1
203/29 31 71 second distillation zone for separation of ethylene di
chloride from the higher boilingv impurities, thereby
[56] References Cited producing a substantially pure ethylene dichloride
U S PATENT DOCUMENTS which may be recycled to the cracking step.
2,748,176 5/1976 Morris ........ ..; ................. .. 260/652 P 6 Claims, N0 Drawings
 4,060,460
1 2
erally results in an ethylene dichloride feed substantially
REMOVAL OF CHLOROPRENES FROM free of the undesired impurities, distillation in the ?rst
ETHYLENE DICHLORIDE column, herein termed the lights column, to remove
the low boiling impurities results in a distillate which
contains some ethylene dichloride (typically 30 to 60
BACKGROUND OF THE INVENTION weight percent ethylene dichloride) in addition to the
1. Field of the Invention undesired low boiling impurities such as the chloro
This invention relates to a process for removing chlo prenes. Since in an industrial process discarding this
roprenes from an ethylene dichloride stream containing distillate would result in a substantial loss of ethylene
the same and more particularly to a process for remov dichloride, it is necessary to recycle at least a portion of
ing the chloroprenes by chlorination to higher boiling this distillate for more complete recovery of the ethyl
chlorocarbons. ene dichloride content thereof. Thus, the bulk of the
2. Description of the prior Art lights column condensate is typically returned as reflux
The process of cracking ethylene dichloride (i.e., to the lights column, a small purge stream being gener
1,2-dichloroethane) to form vinyl chloride and hydro ally withdrawn to prevent buildup of the low boilers in
gen chloride is a well known method of producing vinyl the system.
chloride monomer which ?nds wide use in industry in However, such a scheme results in a purge stream
the preparation of polyvinyl chloride. Generally, only a from the lights column condensate which may contain
portion of the ethylene dichloride fed to the cracking up to about 30 weight percent of the chloroprenes,
furnace is converted to vinyl chloride. The remainder, 20 thereby presenting a serious waste disposal problem.
typically from about 30-70 weight percent of the ethyl Moreover, the chloroprenes present in the condensate
ene dichloride feed, passes through the furnace unre can undergo spontaneous polymerization even at room
acted and must be recycled for most ef?cient operation. temperature, forming high molecular weight, rubber
The ethylene dichloride/vinyl chloride product stream like polymers which are insoluble in the organic me
exiting the cracking furnace, which generally contains 25 dium and which tend to foul the lights column and
from about 19 to 44 weight percent vinyl chloride and thereby increase the down-time for column cleaning.
from 11 to 26 weight percent hydrogen chloride, is This spontaneous chloroprenes polymerization is cata
typically passed to a series of distillation columns, lyzed by the decomposition of polymeric peroxides
wherein hydrogen chloride and vinyl chloride are indi which are formed upon reaction of chloroprene with air
vidually recovered in succeeding distillations. The 30 above temperatures of about 0 C. Thus, it is highly
crude ethylene dichloride stream which results as bot desirable to remove this potential source of column
toms from the column in which vinyl chloride is col fouling and waste disposal problems.
lected at the head may then be recovered for recycle to' While processes such as those disclosed in Great
the cracking furnace for production of additional vinyl Britain Pat. No. 1,323,038 (1973) and U.S. Pat. No.
chloride. 35 3,696,015 (P. Wirtz et a1. 1972) have been developed for
However, recovery of the unreacted ethylene dichlo the removal of chloroprenes either prior to or after
ride from the crude ethylene dichloride stream is made removal of low boiling impurities from the ethylene
more complicated by the presence of impurities which dichloride recycle stream, no process has been devel
are produced in the cracking step. Of these impurities, oped which would avoid the substantial costs due to
the chloroprenes, are one of the major undesired 40 increased equipment requirements which result from
reaction by-products, and typically comprise up to l or such prior art processes.
more weight percent of the crude ethylene dichloride
SUMMARY OF THE PRESENT INVENTION
recycle stream. As used herein, the terms chloro
prenes and chloroprene impurities are intended to In accordance with the present invention, an im
include chloroprene (i.e. 2-chloro-l,3-butadiene) and 45 proved process for removing chloroprenes from an
alpha~chloroprene (i.e. l-chloro-l,3-butadiene). Other ethylene dichloride stream containing the same is pro
impurities which the crude ethylene dichloride stream vided which comprises passing the ethylene dichloride
may contain include such compounds as l,l-dichloroe stream to a distillation zone, introducing free chlorine
thane, ethyl chloride and benzene. gas into the distillation zone and distilling the ethylene
The presence of such impurities in an ethylene di 50 dichloride stream under conditions suf?cient to chlori
chloride stream recycled to the cracking furnace is nate at least a portion of said chloroprenes. The distil
undesirable since some of these impurities, such as the late may be condensed and a portion of the condensate
chloroprenes, have been shown to increase the rate of recycled as re?ux to the distillation zone. A mixture
coke formation in the coils of the cracking furnace, containing ethylene dichloride in addition to the chlori
thereby requiring more frequent decoking of these 55 nation reaction products, as well as other impurities
coils, resulting in a loss of vinyl chloride monomer boiling at temperatures higher than ethylene dichloride,
production due to equipment downtime. Thus, it is is recovered as distilled bottoms and may be passed to a
desired to purify the crude ethylene dichloride stream. second distillation zone wherein the ethylene dichloride
Typically, such puri?cation is undertaken by subjecting is recovered as distillate, thereby removing said ethyl
this ethylene dichloride stream to a series of distilla ene dichloride from the higher boiling impurities. The
tions. In the ?rst distillation, it is attempted to remove substantially pure ethylene dichloride thereby obtained
those impurities which boil at temperatures lower than may then be recycled to a cracking furnace for produc
tion of vinyl chloride monomer.
that of ethylene dichloride (83.5 C. at 1 atm.) thereby
resulting in a distilled bottoms containing the majority The process of the present invention has been found
65 to result in ef?cient conversion of the chloroprenes
of the ethylene dichloride together with high boiling
impurities. These bottoms may be passed to a second content of the ethylene dichloride recycle feed stream
distillation zone wherein the ethylene dichloride is re to high boiling chlorocarbons (herein termed chloro
moved as distillate. While this puri?cation scheme gen prene reaction products), which are believed to com
 4,060,460
3 4
prise higher boiling trichlorobutenes, e.g. 1,2,4-tri could otherwise be employed in the chlorination of the
chloro-2-butene. These higher boiling impurities are chloroprenes. Thus, it is desired to promote the addition
recovered from the lights column together with the reaction wherein higher boiling trichlorobutenes may
ethylene dichloride as distilled bottoms and may be be formed, while at the same time avoiding promotion
ef?ciently separated therefrom in a subsequent distilla of the substitution reaction, wherein hydrogen chloride
tion step. Thus, the present invention operates to sub is formed as by-product. The temperature of the chlo
stantially reduce the chloroprenes content of the distil rine-containing gas introduced to the distillation zone is
lates in the lights column, thereby resulting in a distillate not critical.
condensate which is substantially free of said chloro The chlorine-containing gas introduced to the distil
prenes and which may be recycled to the distillation lation zone in accordance with the present invention
zone for more ef?cient recovery of the ethylene dichlo may be obtained from a variety of sources, for example,
ride content thereof. Further, the process of the present by electrolytic decomposition of sodium chloride, and
invention substantially reduces the waste disposal prob thus may also contain other gases such as hydrogen,
lem associated with purged lights column condensate oxygen and carbon dioxide in amounts up to about 10
streams containing substantial quantities of chloro volume percent. For most ef?cient operation, however,
prenes. Moreover, it has been found that the distillate the chlorine gas preferably contains at least 95 volume
condensate so produced may be marketed as a source of percent chlorine. The chlorine gas preferably contains
chlorine as well as its ethylene content, and thus ?nds less than about 100 ppm, and most preferably less than
use in the preparation of industrial organic solvents. 50 ppm, water vapor to avoid corrosion problems en
20
DETAILED DESCRIPTION OF THE countered due to adsorption by the water of residual
INVENTION HCl in the distillation zone.
For most ef?cient operation, it has been found that
As mentioned above, the ethylene dichloride stream
obtained from the cracking of ethylene dichloride in the chlorine should be introduced to the distillation zone at
production of vinyl chloride, is fed (after treatment for a point where the quantity of liquid above the chlorine
25
recovery of vinyl chloride and hydrogen chloride) to feed point is sufficient to allow substantially complete
the lights column for removal therefrom of impurities chlorination (i.e. chlorination of at least about 80 weight
which boil at a temperature lower than that of ethylene percent, and most preferably at least about 90 weight
dichloride. As used herein, the term crude ethylene percent, of chloroprenes in the ethylene dichloride
dichloride stream is intended to refer to the process 30 stream) of the chloroprenes contained in the feed
stream containing ethylene dichloride and impurities stream. Where the distillation zone comprises a distilla
which is obtained following treatment of the EDC tion column, chlorine should, therefore, be introduced
stream exiting the cracking furnace for recovery of to the column at a point where the liquid hold-up above
VCM and HCl therefrom. While the composition of the the chlorine feed point is sufficient to allow substan
crude ethylene dichloride stream may vary widely, it 35 tially complete chlorination of the chloroprenes. The
typically contains from about 80 to 98 weight percent determination of the chlorine feed point in a given distil
ethylene dichloride; and from about 0.05 to 6 weight lation column can be determined by conventional meth
percent chloroprenes. In addition, the ethylene dichlo ods, and will of course vary depending upon the tem
ride stream may also contain from about 2 to 20 weight perature of distillation. Thus, for example, under steady
percent of other impurities, such as l,l-dichloroethane, 40 state conditions in a distillation column operating at an
ethyl chloride, benzene and any residual vinyl chloride effective average temperature of from about 60 to 70
and hydrogen chloride not removed in previous recov C., the minimum liquid hold-up above the chlorine feed
ery steps. point which would allow substantially complete chlori
The mass ?ow rate of the ethylene dichloride stream nation of the maximum quantity of chloroprenes in the
which is passed to the distillation zone is not critical and 45 ethylene dichloride feed is given by the expression:
may vary widely depending on the capacity of the dis
tillation apparatus, the purity of the feed stream with
respect to ethylene dichloride and other factors. The
chlorine may be introduced to the distillation zone as a wherein r=0.523 hour-1 and is a rate constant calcu- ,
elemental chlorine-containing gas and may be intro lated where the rate of chlorination of chloroprenes is
duced either batchwise, semi-continuously or continu just limited by the chlorine addition rate, and wherein
ously and at a wide variety of ?ow rates. However, the Hm," is the minimum liquid hold-up in pounds and Cm,
elemental chlorine-containing gas is generally intro is the mass rate of ?ow of chloroprenes (i.e. chloroprene
duced to the distillation zone at a mass ?ow rate which and alpha-chloroprene) introduced into the distillation
is not greater than 80 percent, preferably 56 to 72 per zone with the ethylene dichloride stream.
cent, and most preferably 60 to 68 percent, of the mass Of course, the actual hold-up in the distillation zone
flow rate of the chloroprenes fed to the distillation zone between the chlorine feed point and the highest liquid
via the ethylene dichloride stream. While the chlorine level in the distillation zone may be calculated by stan
containing gas may be introduced to the distillation dard methods. For example, where a distillation column
zone at a mass ?ow rate which exceeds 80 percent of the 60 is employed, the actual liquid hold-up (Ham!) between
mass ?ow rate of chloroprenes fed to the distillation the selected chlorine feed point and the top of the col
zone, this results in unreacted chlorine and tends to umn may be calculated as follows:
promote the substitution reaction of the chlorine and
chloroprenes to form 1,4-chlorination products such as
l,4-dichloro-1,3-butadiene, in addition to hydrogen 65
chloride. The production of hydrogen chloride is unde wherein t is the number of trays between the chlorine
sirable since its presence leads to corrosion in the equip feed pointand the top of the column, A,is the area of a
ment and also consumes additional chlorine which tray, A, is the effective area of a tray, h is the average
 5
4,060,460 6
depth of liquid on each tray and d is the average density a a Table'I
of the liquid on each tray. . Grams . 7 Weight
The effective average temperature of the distillation BBC 7 Chlorine Reaction Ratio Gms.
Mix- '- Reaction Feed Rate Time 'CIZ/Gm.
zone may vary widely, depending on the pressure em Ex. ture Temp. (grams/min.) I (min) Chloroprenes
ployed in the column, the overhead composition de l. 248 6065' C 0.42 165 . 0.76
sired and'other factors, but is generally from about 60" '2
3
248.5
249
61-65 C
6l~65 C .
' 0.63
, 0.82
120
90
0.83
0.81
to about 80 C., and preferably about 65 to 75C. The 4 I 252 679-70I C 1.25 42 0.57
pressure in the distillation zone is not critical to the
present invention, and one atmosphere of pressure has
been found to be quite satisfactory although pressures EXAMPLES 5-6
above or below atmospheric may also be employed. V The procedure of Example 1 is repeated employing
Overhead vapors produced in the distillation zone are an ethylene dichoride stream comprising 89weight
withdrawn therefrom and passed to a cohdensingiappa percent ethylene dichloride, 4.0 weight percent alpha
ratus, (e.g. a re?ux condenser) wherein the vapors are 15 chloroprene, and 6.6 weight percent chloroprene, i.e.
condensed. This condensate may berecycled reflux 10.6 weight percent total vchloroprenes, yielding the
to the distillation zone. Typically, the distillation is data set forth Table II below: '
operated close to total re?ux, that is with as much as 99
Grams
, g . Table II Weight
.,
weight percent and more of distillate produced in the 20
condensate is recycled as re?ux to the distillation zone. EDC Chlorine Reaction Ratio Gms.
Mix- Reaction Feed Rate Time ClZ/Gm.
The balance of the distillate may be withdrawn and Ex. ture Temp. (grams/min.) (min.) chloroprenes
discarded or sold as a source of chlorine and/or C1 and 5 253 61-66 C 0.21 90 0.70
C2 hydrocarbons for preparation of industrial chlori 6 250 59-06 C 0.42 60 0.95
nated solvents. 25
The distilled bottoms withdrawn from the distillation The rate of chlorination of the chloroprenes present
zone in which chorination is effected by the process of in the distillation zone may be accelerated by providing
the present invention generally contains up to 99 weight therein a source of radiation in the visible and/or ultra
percent ethylene dichloride and not greater than about violet spectrum. The effective spectrum extends from
10 weight percent, and preferably not greater than about 4785A in the visible region to about 2500A in the
about 5v weight percent, impurities (such as the tri high ultraviolet. Thus, these chlorinations may be car
ried out with incandescent or ?uorescent lighting.
chlorobutenes formed by chlorination of chloroprenes)
However, such radiation is not required in that the
boiling at temperatures higher than the ethylene dichlo present invention has been found to effect chlorination
ride. This withdrawn bottoms may be passed to a sec 35 of the chloroprenes in the substantial absence of light.
ond distillation zone for separation of ethylene dichlo Although certain preferred embodiments of the in
ride from the higher boiling impurities by conventional vention have been disclosed for the purpose of illustra
distillation, and the substantially pure ethylene dichlo tion, it will be evident to one skilled in the art that
ride thereby obtained may be passed to a cracking fur various changes and modi?cations may be made therein
nace for production of vinyl chloride. without departing from the scope and spirit of the in
The process of the present invention may be further vention.
illustrated by reference to the following examples: We claim:
1. In a process for recovering ethylene dichloride
EXAMPLES 1-4 from an impure ethylene dichloride stream containing
To a 1,000 ml. round-bottom glass ?ask equipped (i) impurities boiling at a temperature lower than the
with a re?ux condenser, thermometer and magnetic boiling point of ethylene dichloride and consisting at
least in part of a chloroprene-impurity selected from the
stirrer, is introduced a desired quantity of an ethylene group consisting of chloroprene, alpha-chloroprene and
dichloride stream comprising 63 weight percent ethyl mixtures thereof, and (ii) impurities boiling at a temper
ene dichloride, 25.2 weight percent chloroprene and 50 ature higher than the boiling point of ethylene dichlo
11.4 weight percent alpha-chloroprene (i.e. 36.6 weight ride, wherein
percent total chloroprenes). The ?ask containing the a. said impure ethylene dichloride stream is passed to
ethylene dichoride mixture is maintained at the desired a ?rst distillation zone and distilled therein under
temperature by immersion of the reaction ?ask in a conditions sufficient to provide (1) ?rst distillate
heated water bath. Chlorine gas is sparged to the ?ask, 55 containing said lower boiling impurities and (2)
and the ?ask operated with continuous stirring under ?rst bottoms containing ethylene dichloride to
conditions of total re?ux. The non-condensables are gether with said higher boiling impurities, and
passed through a suck-back trap and then through two . said ?rst bottoms is passed to a second distillation
successive caustic scrubbers. The ?rst scrubber contains zone and distilled therein under conditions suffi
125 ml. of an 0.1 aqueous NaOI-I solution together with
cient to provide (1) second distillate containing
ethylene dichloride and (2) second bottoms con
125 ml. water, and the second scrubber contains 125 m1. taining said higher boiling impurities, the improve
of an 1.0N aqueous NaOH solution together with 125 ment which comprises chlorinating at least the
ml. water. Light is excluded from the reaction vessel. portion of said chloroprene-impurity by introduc
By analysis of periodic samples drawn from the liquid 65 ing into said ?rst distillation zone, during the distil
present in the reaction vessel, it is determined that sub lation of ethylene dichloride therein, a gas contain
stantially all of the chloroprenes have been chlorinated ing elemental chlorine, thereby producing chloro
at the times indicated in Table I below: prene reaction products having a boiling point
 4,060,460
7 8
higher than the boiling point of ethylene dichlo substantially complete chlorination of said chloro
ride, and withdrawing said chloroprene reaction prenes.
5. The process according to claim 4 wherein the
products with said ?rst bottoms for passage to a distillation in said ?rst distillation zone is effected at a
second distillation zone. temperature of from about 60 to 70C. and wherein the
2. The process according to claim 1 wherein said amount of liquid in said ?rst distillation zone above the
impure ethylene dichloride stream contains from about point at which the gas containing elemental chlorine is
80 to 98 weight percent ethylene dichloride and from introduced is at least that amount of liquid, de?ned as
about 0.05 to 6 weight percent chloroprenes. Hm, determined according to the expression:
10
3. The process according to claim 1 wherein said min =
impure ethylene dichloride stream is distilled in said
?rst distillation zone at a temperature of from about 60 wherein Cm, is the maximum mass flow rate of said
to 80 C. chloroprene-impurity introduced into said ?rst distilla
tion zone with said impure ethylene dichloride stream.
4. The process according to claim 1 wherein said gas 15 6. The process according to claim 1 wherein at least
containing elemental chlorine is introduced into said a portion of said ?rst distillate is recycled to said ?rst
?rst distillation zone at a point in said zone to provide a distillation zone.
a a 4: t a
quantity of liquid above said point suf?cient to allow
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