United States Patent (19) 11 Patent Number: 4,849,562

Buhs et al. 45 Date of Patent: Jul. 18, 1989

54 PROCESS FOR PRODUCING ETHYLENE 1483831 8/1977 United Kingdom ................ 570/243
DCHILORDE 1505912 4/1978 United Kingdom .
75) Inventors: Christoph Buhs, Stade, Fed. Rep. of OTHER PUBLICATIONS
Germany; Eberhard Dreher, CA102:168665U.
Midland, Mich.: Garnet E. Ullmanns Enzyklopedie der technischen Chemie, 5th
McConchie, Stade, Fed. Rep. of Edition, pp. 266-271.
Germany Kirk-Othermer's Encyclopedia of Chemical Technol
(73) Assignee: The Dow Chemical Company, ogy, Third Edition, vol. 5, p. 715.
Midland, Mich. Primary Examiner-Howard T. Mars
21 Appl. No.: 240,463 Attorney, Agent, or Firm-A. Cooper Ancona
22 Filed: Aug. 26, 1988 57 ABSTRACT
The oxychlorination process for producing ethylene
Related U.S. Application Data dichloride is carried out by reacting ethylene with hy
drogen chloride and oxygen in an oxychlorination reac
63 Continuation of Ser. No. 137,540, Dec. 23, 1987. tor. Thereby, ethyl chloride and perhaps vinyl chloride
(30) Foreign Application Priority Data are produced as by-products. The effluent from the
Jan. 3, 1987 DE Fed. Rep. of Germany ....... 3700132 reactor is at least fractionated into an ethylene dichlo
ride-rich fraction (I) and an ethyl chloride-rich fraction
5l Int. Cl." ..................... C07C 17/156; CO7C 17/38 (II) so that fraction (I) contains less than 50 percent of
52 U.S. C. .................................... 570/241; 570/243; the total weight of ethyl chloride produced in step (a)
570/244; 570/245; 570/262; 585/315; 585/142 and the sum of the weight of ethylene dichloride and
58) Field of Search ............... 570/241, 243, 244, 245, vinyl chloride in fraction (II) is less than 30 percent of
570/262; 585/315, 642 the weight of ethyl chloride in fraction (II). The ethyl
56 References Cited chloride-rich fraction (II) is subjected to a cracking
reaction in the presence or absence of an inert diluent
U.S. PATENT DOCUMENTS wherein ethyl chloride is converted into ethylene and
3,184,515 5/1965 Penner et al. . hydrogen chloride in the presence of a catalyst. The
3,800,001 3/1974 Prescott et al. . total weight of ethylene dichloride and vinyl chloride is
4,347,391 8/1982 Campbell. less than 5 percent, based on the combined weight of
ethyl chloride and any inert diluent.
FOREIGN PATENT DOCUMENTS
0.005655 4/1981 European Pat. Off. . 20 Claims, 1 Drawing Sheet
U.S. Patent Jul.18, 1989 4,849,562
 4,849,562 2
1.
It has been found that the problem of by-products
PROCESS FOR PRODUCING ETHYLENE disposal can be reduced by separating ethylene dichlo
OCHLORDE ride and ethyl chloride (which is one of the main by
products in the oxychlorination process) and then con
CROSS-REFERENCE TO RELATED verting ethyl chloride to ethylene and hydrogen chlo
APPLICATION ride in the presence of a catalyst.
This is a continuation, of application Ser. No. 137,540 SUMMARY OF THE INVENTION
filed Dec. 23, 1987.
10
The present invention is an oxychlorination process
BACKGROUND OF THE INVENTION for producing ethylene dichloride by
The present invention relates to a process for produc (a) reacting ethylene with hydrogen chloride and
ing ethylene dichloride. More specifically, it relates to oxygen in the presence of an oxychlorination cata
an oxychlorination process in which ethylene is reacted lyst in an oxychlorination reactor, whereby ethyl
with hydrogen chloride and oxygen in the presence of a 15 chloride or both ethyl chloride and vinyl chloride
catalyst. are produced as byproducts
1,2-dichloroethane (ethylene dichloride) is used ex which process is characterised in that it comprises the
tensively for producing vinyl chloride. further steps of
Accordingly, intensive research has been made by (b) dividing, in one or more steps, the effluent from
those skilled in the art relating to the production of 20 the oxychlorination reactor into at least (i) an eth
1,2-dichloroethane. A process which is widely used in ylene dichloride-rich fraction (I) and (ii) an ethyl
industry is the oxychlorination process in which ethyl chloride-rich fraction (II) in such a fashion that
ene is reacted with oxygen and hydrogen chloride in the fraction (I) contains less than 50 percent of the total
presence of a catalyst such as copper dichloride. Exten weight of ethyl chloride produced in step (a) and
sive patent literature exists relating to the catalysts in 25 the sum of the weight of ethylene dichloride and
the process and to the process technologies which, vinyl chloride in fraction (II) is less than 30 percent
among others, try to maximise yield of ethylene dichlo of the weight of ethyl chloride in fraction (II) and
ride. The by-products from existing processes are usu (c) subjecting fraction (II) to a cracking process in the
ally burnt and hydrogen chloride is recovered. Al presence or absence of an inert diluent whereby fraction
though the yield of ethylene dichloride is quite high, 30
generally between 90 and 97 percent, depending on the (II) contains less than 5 percent ethylene dichloride and
process type and conditions, the incineration of the vinyl chloride based on the combined weight of ethyl
by-products in large scale production is a problem for chloride and inert diluent in fraction (II) prior to crack
the environment. ing, the cracking process is carried out in the presence
European Patent No. 0 005 655 suggests oxidative 35 of a cracking catalyst in a cracking reactor and ethyl
destruction of the by-products using a catalyst contain chloride is converted into ethylene and hydrogen chlo
ing platinum or iridium on a support of alumina having ride.
the eta crystallographic structure to improve the incin From Kirk-Othmer "Encyclopedia of Chemical
eration process. Technology” 3rd edition, 1979, vol. 5, page 715, G. M.
However, incineration of the by-products remains Schwab and H. Noiler, z.Eletrochem, 58, 762 (1954)
uneconomical and efforts are necessary in order to keep and A. Heinzelmann et al., J. Monatsh. Chemie 102,
the pollution of the environment to a low level. 1750 (1971) it is generally known that ethyl chloride is
In European patent application 0 132 971 an oxy decomposited to ethylene and hydrogen chloride at
chlorination process is disclosed wherein hydrogen about 300° C. in the presence of certain cracking cata
chloride gas and oxygen are reacted with an unsatu 45 lysts. However, these references do not suggest any
rated organic compound. Chlorine containing organic where to use a cracking step in the oxychlorination
residues are combusted in an oxygen-rich flame process. The skilled artisans have concentrated on in
whereby hydrogen chloride is produced which is recy cineration methods for disposing of the by-products in
cled to the oxychlorination process. However, this pro the oxychlorination process.
cess is rather inconvenient because a high combustion 50 Surprisingly, it has been found that a good conver
temperature of more than 2000 C. is required to ensure sion rate of ethyl chloride to ethylene can be achieved
complete destruction of the residues. European patent in the process of the present invention and that uncon
application 0 132971 discloses that steps must be taken verted ethylene from the oxychlorination step (a) does
to avoid corrosion of the chamber material in the pres not substantially affect the conversion rate in step (c).
ence of hydrogen chloride. 55
The oxychlorination process of the present invention
In the German Auslegeschrift DE-AS-2400 417 it is is useful for producing ethylene dichloride on a large
suggested to adsorb the by-products of the oxychlorina
tion process partially on activated carbon and to burn scale. The process of the present invention allows a
the nonadsorbed by-products such as ethylene at a tem substantial saving of ethylene which is used as raw
perature between 500 C. to 2000' C. The adsorbed material but which is expensive. By the present inven
impurities such as ethylene dichloride and ethyl chlo tion the yield of produced ethylene dichloride, based on
ride are then desorbed with vapour. the amount of ethylene consumed, can be increased by
However, a careful separation of vapour and chlori 1 to 2 percent. Depending on the process conditions,
nated by-products is required after the desorption step even 1.5 to 2 percent yield increase can be achieved.
in order to avoid pollution of water. 65
BRIEF DESCRIPTION OF THE DRAWING
Accordingly, it would be desirable to overcome these
disadvantages of known oxychlorination processes for The drawing illustrates a flow sheet of one embodi
producing ethylene dichloride. ment of process of the present invention.
 4,849,562
3 4
DETALED DESCRIPTION OF THE than 150° C. and a pressure of 1 to 5 bar. The amount of
INVENTION Process step (a) is well known in the ethyl chloride produced in the oxychlorination step a)
literature. A general description of the oxychlorination depends of course on the reaction conditions. In gen
reaction is published in ULLMANNS Enzyklopedie eral, it is between 1 to 3 percent, based on the weight of
der technischen Chemie, 4th Edition, volume 9, pages produced ethylene dichloride.
428 to 431. A preferred process step (a) is described in In process step (b) the effluent from the oxychlorina
U.S. Pat. No. 3,184,515. tion reactor, from which excess hydrogen chloride
preferably has been separated, is divided in one or more
Ethylene is reacted with hydrogen chloride and oxy steps into at least (i) an ethylene dichloride-rich fraction
gen in the presence of a oxychlorination catalyst. The 10 (I) and (ii) an ethyl chloride-rich fraction (II). Preferred
typical molar ratios of hydrogen chloride:oxygen:ethy fractionation steps are described in more detail below
lene used in industry are from 1.8 to 3 moles, preferably with respect to the drawing.
from 1.9 to 2.4 moles hydrogen chloride and from 0.4 to In order to reach a substantial process improvement,
0.7 moles, preferably from 0.5 to 0.6 moles oxygen per the ethylene dichloride-rich fraction (I) should contain
mole ethylene. Ethylene may originate from hydrocar 15 less than 50 percent, preferably less than 30 percent,
bon cracking facilities and may contain usual impurities more preferably less than 20 percent of the total weight
such as methane, ethane and other hydrocarbons. of ethyl chloride which has been produced in step (a).
The oxychlorination step (a) may be carried out in Less efficient fractionation is possible but renders the
liquid phase in which the catalyst is dissolved. In a process uneconomically. At least 50 percent, preferably
liquid phase reaction the temperature is preferably from 20at least 70 percent, most preferably at least 80 percent of
150° C. to 200 C., more preferably from 170° C. to 190° the total weight of ethyl chloride produced in step (a) is
C. and the pressure is preferably from 13 to 22 bar, more subjected to cracking step (c).
preferably from 15 to 20 bar. In the ethyl chloride-rich fraction (II), the total
However, a gaseous phase oxychlorination is pre amount of ethylene dichloride and vinyl chloride
ferred for the purpose of the present invention. In gen 25 (which is often produced as a by-product in oxychlori
eral, the temperature in the gaseous phase oxychlorina nation) is less than 30 percent, preferably less than 10
tion process is from 200 C., preferably from 210 C. percent and more preferably less than 5 percent, based
and more preferably from 230 C. and up to 450° C., on the weight of ethyl chloride.
preferably up to 350° C. and more preferably up to 280 In general, the presence of ethylene dichloride or
C. In general, the pressure is from 1 bar, preferably 30
from 2 bar and more preferably from 3 bar, up to 10 bar, vinyl chloride decreases the lifetime of the catalyst in
preferably to 8 bar, more preferably to 7 bar. cracking step (c), however the presence of unreacted
Useful oxychlorination catalysts for the purpose of ethylene does not significantly affect the cracking step
the present invention are also known. A preferred cata (c). For example, the ethyl chloride-rich fraction (II)
lyst is copper(II) chloride. Copper(II) chloride can be 35 may contain an ethyl chloride/ethylene molar ratio of
used together with alkali or alkaline earth metal chlo 1:1 to 5:1 without significant impact on the cracking
rides, for example potassium chloride. The copper chlo reaction. The ethyl chloride-rich fraction (II) is then fed
ride catalyst can be deposited on a conventional carrier to a cracking reactor.
material such as high surface aluminum oxides, prefera It is preferred to carry out cracking step (c) in the
bly gamma-alumina, silica, celite or zeolites. presence of an inert diluent. It has been found that the
Well known reactor types are useful for the purpose lifetime of the catalyst and the conversion of ethyl chlo
of the present invention, such as fixed bed reactors or ride can be increased in the presence of an inert diluent
fluidised bed reactors. such as nitrogen. The molar ratio between the inert
Since the oxychlorination reaction is highly exother diluent and ethyl chloride is preferably from 0.25:1,
mic, efficient temperature control is necessary. In the 45 more preferably from 0.5:1, most preferably from
gas phase reaction, it is preferred to dilute the reactive 0.75:1, up to 30:1, preferably up to 20:1, more preferably
gases with one or more inert gases such as nitrogen. up to 15:1. The combined amount of ethylene dichloride
Dilution may also be achieved by using air as the oxy and vinyl chloride in the fraction (II) is less than 5
gen source in the oxychlorination process. When using weight percent, preferably less than 4 weight percent
air in a continuous oxychlorination process, excess ni 50 and more preferably less than 3 weight percent, based
trogen is removed from the reactor in order to avoid a on the combined weight of ethyl chloride and any inert
pressure build up. Preferably, the oxychlorination pro diluent present in the fraction (II). If the combined
cess is carried out by continuously feeding oxygen into amount of ethylene dichloride and vinyl chloride in
the reactor and by diluting it with nitrogen which is fraction (II) is more than 5 percent of the ethyl chloride
continuously recycled into the oxychlorination reactor 55 weight in fraction (II), a diluent has to be added.
after the reaction. The cracking reaction (c) is carried out at a suitable
The mixture produced in the oxychlorination reactor pressure and temperature. The cracking reaction (c) is
is removed from the reactor and preferably cooled to a generally carried out at a temperature between 150 C.,
temperature of less than 200 C., more preferably to a preferably between 200 C., most preferably between
temperature between 20' C. and 160' C., preferably at a 60 250 C., and 450° C., preferably 350° C., most preferably
pressure of from 1 to 10 bar, more preferably from 2 to 320 C. The conversion of ethyl chloride increases with
8 bar. It is advisable to remove residual amounts of increasing temperature. Depending on the temperature
unreacted hydrogen chloride from the mixture pro in the reactor, a pressure preferably between 1 and 8
duced in the oxychlorination reactor, for example by bar, more preferably between 1 and 5 bar, most prefera
washing it with hot water, a hot alkaline solution such 65 bly between 1 and 3 bar is maintained. The conversion
as aqueous sodium hydroxide or with both. The wash of ethyl chloride to ethylene and hydrogen chloride
ing of hydrogen chloride is preferably carried out at a increases with decreasing pressure, but vacuum opera
temperature of less than 200 C., more preferably less tion is inconvenient in large scale cracking reactors.
 4,849,562 6
5
The preferred residence time of ethyl chloride in the preferably from 30° C. to 100° C. The pressure in the
cracking reactor depends on several factors such as fractionation equipment B1 is preferably from 1 bar to
temperature and desired conversion rate. In general, a 10 bar, more preferably from 2 bar to 8 bar.
suitable residence time is from 2 sec., preferably from 3 Gas fraction 6 contains mainly the inert diluent(s),
sec., more preferably from 5 sec. and up to 120 sec., carbon dioxide, carbon monoxide, non-converted ethyl
preferably up to 60 sec., more preferably up to 45 sec. ene and impurities. Preferably, gas fraction 6 is recycled
Reasonable conversion rates are achievable at a resi to the oxychlorination reactor A.
dence time of 30 sec. or less. The liquid fraction 5 consists mainly of 1,2-dichloroe
Useful cracking catalysts for process step (c) are thane but also contains the major by-product ethyl chlo
those which are generally known for cracking hydro O ride and minor amounts of other by-products such as
carbons, for example zeolite and silicalite catalysts. vinyl chloride, water and/or trichloromethane, and of
Preferred catalysts are aluminum oxide in various con unconverted ethylene.
figurations, of which gamma-alumina is preferred. In a second fractionation equipment B2, liquid frac
Gamma-alumina which has a surface area between 10 tion 5 is separate in a fractionation step (b2) into a 1,2-
m2/g, preferably between 50 m2/g, more preferably 15 dichloroethane fraction 8 and a by-product fraction 7,
between 100 m2/g and 350 m2/g, preferably 320 m2/g, preferably by distillation. The temperature of the distil
more preferably 250 m2/g is preferred. It has been lation is preferably from 30° C. to 180° C., more prefera
found that gamma-alumina which has a surface area bly from 40° C. to 140 C., and the distillation is prefera
between 50 m2/g and 250 m2/g and correspondingly a bly carried out at a pressure of from 1 bar to 10 bar,
relatively large pore diameter, and which contains low 20 more preferably from 2 bar to 8 bar.
levels of impurities such as Na2O and SiO2, is relatively 1,2-Dichloroethane fraction 8 contains crude 1,2-
insensitive to reactant feed impurities such as ethylene dichloroethane (ethylene dichloride) and can be further
dichloride and vinyl chloride. Only a few by-products purified in a known manner. Fraction 8 has preferably a
are produced in the cracking reaction (c) when using temperature of 30° C. to 150° C. and a pressure of 1 to
these reaction catalysts. Preferably, the average pore 25 8 bar. The by-product fraction 7 contains mainly ethyl
diameter of the gamma-alumina is 3 to 30 nm, more chloride and ethylene dichloride as well as by-products
preferably 6 to 20 nm. The level of impurities, such as such as water, vinyl chloride and perhaps trichloro
Na2O and SiO2, is preferably less than 15,000 ppm, methane and non-converted ethylene. Fraction 7 pref.
more preferably less than 10,000 ppm, most preferably erably has a temperature of 20 C. to 100 C. and a
less than 1,000 ppm, based on the weight of gamma 30 pressure of 1 to 8 bar.
alumina. It is possible to feed by-product fraction 7 directly
The effluent from the cracking reactor contains into the cracking reactor C in which ethyl chloride is
mainly ethylene and hydrogen chloride, inert diluent, if converted into ethylene and hydrogen chloride as de
present, and minor amounts of impurities such as non scribed above. In such a case, fraction 7 is preferably
converted ethyl chloride. This effluent mixture can be 35 preheated to a temperature of from 150 C. to 450° C.,
treated as described below with reference to the draw more preferably of from 200° C. to 350° C. at a pressure
1ng. of from 1 to 8 bar. However, it is preferred to subject
One preferred embodiment of the invention is ex fraction 7 to further fractionation steps in order to pro
plained in detail with reference to the drawing. In re long the life of the catalyst in cracking step (c). It is
spect to said drawing, via lines 1, 2, 3 ethylene, hydro evident that the usefulness of the fractionation steps (b3)
gen chloride and oxygen are fed to the oxychlorination and (b4) described below depends on the efficiency of
reactor A in which ethylene is converted to 1,2- the fractionation step (b2).
dichloroethane (ethylene dichloride) as described above In fractionation step (b3) fraction 7 is further fraction
(process step a). The temperature of ethylene, hydrogen ated into a fraction 9 which contains at least the major
chloride and oxygen to be fed is preferably from 180 to 45 portion of 1,2-dichloroethane and trichloromethane
400° C., more preferably from 200 to 380° C. The pres which might remain in fraction 7 after the fractionation
sure in lines 1, 2 and 3 is preferably from 1 to 10 bar, step (b2) and into a fraction 10 which consists mainly of
more preferably from 2 to 8 bar. Nitrogen is generally ethyl chloride and minor amounts of by-products ethyl
used as an inert diluent for the reaction and is fed to the ene, water and vinyl chloride.
oxychlorination reactor A in the amount desired. 50 The fractionation step (b3) in fractionation equipment
The effluent 4 from the oxychlorination reactor A is (B3) is preferably carried out by distillation. The tem
preferably cooled and excess hydrogen chloride is pref. perature of the distillation is preferably between 30° C.
erably removed from the effluent as described above and 180° C., more preferably between 50° C. and 150
with respect to the oxychlorination step (a). The efflu C. and the distillation is preferably carried out at a pres
ent 4 then contains 1,2-dichloroethane and by-products. 55 sure between 1 bar and 10 bar, more preferably between
The main by-product is ethyl chloride. Other by-pro 2 bar and 8 bar. Fraction 9 preferably has a temperature
ducts which are ordinarily found in effluent 4 are water, of 90° C. to 170° C., more preferably of 100° C. to 160'
carbon dioxide, carbon monoxide and vinyl chloride. C. and a pressure of from 1 to 8 bar, preferably of 2 bar
The effluent 4 further contains unreacted ethylene and to 7 bar. Fraction 10 preferably has a temperature of 40
any inert diluent. It may also contain trichloromethane C. to 100° C., more preferably of 50° C. to 80° C. and
and minor amounts of other impurities. preferably a pressure of 1 to 8 bar, more preferably of 1
The effluent 4 from the oxychlorination reactor A is bar to 7 bar.
separated, preferably by condensation, into a gas frac Fraction 10 can be fed into cracking reactor C. In
tion 6 and a liquid fraction 5. The fractionation (B1) is such a case fraction 10 is preferably preheated to a
carried out in fractionation equipment B1, preferably in 65 temperature of from 150° C. to 450° C., more preferably
a condenser. The temperature in the fractionation of from 200° C. to 350° C. at a pressure of from 1 to 8
equipment B1, in the gas fraction 6 and in the liquid bar. However, it is preferred to subject fraction 10 to a
fraction 5 is preferably from 20° C. to 120° C., more further fractionation step (b4) in the fractionation equip
 4,849,562
7 8
ment B4 in order to avoid corrosion problems in the EXAMPLE 1.
cracking reactor (C).
In fractionation equipment B4, fraction 10 is sepa A gas stream consisting of 40.9 percent ethyl chlo
rated into a liquid water phase 11, a liquid ethyl chloride ride, 16.6 percent ethylene, 1.9 percent vinyl chloride,
phase 12 and a gaseous ethyl chloride phase i3. 0.6 percent ethylene dichloride and 40 percent nitrogen
The pressure in fractionation equipment B4 is prefer is fed to a cracking reactor C. The gas stream corre
ably from 1 to 8 bar, most preferably from 1 bar to 7 bar. sponds to the combined streams 14 and 15 in the draw
The temperature is preferably from 20° C. to 100° C., ing. The gas stream is preheated to 250 C. The reactor
more preferably from 30° C. to 90° C. The separation of is surrounded by a heat exchange jacket to maintain a
O temperature of 275 C. inside the reactor. The catalyst is
the three phases is preferably carried out by means of gamma-alumina with a surface area of about 190 m2/g
gravity settling. and is arranged as a fixed bed. The pressure in the reac
The liquid water phase 11 is removed from fraction tor is maintained at 1.8 to 2 bar. The average residence
ation equipment B4. It preferably has a temperature of time of the flowing gas stream in the cracking reactor is
20 C. to 100° C. and a pressure of 1 to 8 bar. The liquid 15 15 seconds.
ethyl chloride phase 12 which preferably has a tempera Cracking reactor C is operated for about 100 days.
ture of 20° C. to 100 C. and a pressure of 1 to 8 bar, is The initial ethyl chloride conversion rate is 62.7%.
sent to a vaporizer. This stream is combined with the EXAMPLE 2
gaseous ethyl chloride phase 13 from fractionation
equipment B4. The gaseous ethyl chloride phase prefer In order to evaluate the influence of vinyl chloride
ably has a temperature of 20° C. to 100 C. and a pres and ethylene dichloride on the catalyst used in cracking
sure of 1 to 8 bar. The combined ethyl chloride stream reaction (c) a gas steam consisting of 26.7 mol percent
14 consists mainly of ethyl chloride. The ethyl chloride ethyl chloride, 24 mol percent ethylene, 47.2 mol per
stream 14 may also contain residual amounts of ethylene cent nitrogen, 2.0 mol percent vinyl chloride and 0.1
and vinyl chloride. The amount of vinyl chloride should
25 mol percent ethylene dichloride is fed to the same
not exceed the limit stated above.
cracking reactor C as in Example 1. The temperature,
It is to be understood that use of the fractionation
the residence time and the pressure are the same as in
Example 1. Gamma-alumina having a surface area of
steps (b1) to (b4) described with reference to the draw about 200 m2/g and a level of impurities (Na2O and
ing is only one preferred embodiment of the fraction 30 SiO2) of less than 1,000 ppm is used as a catalyst. After
ation step (b) of the effluent 4 from the oxychlorination having operated the cracking reactor for about 100
reactor A. It is not critical how fractionation step (b) is days, the ethyl chloride conversion rate is reduced to
carried out, however the ethyl chloride stream 14 about 50 percent of its initial rate.
should contain less than 30 weight percent ethylene EXAMPLE 3
dichloride and vinyl chloride (total amount), based on 35
the weight of ethyl chloride. Example 2 is repeated, however gamma-alumina hav
The ethyl chloride stream 14 is then brought into the ing a surface area of about 300 m2/g and a level of
cracking reactor C. Preferably, it is diluted with an inert impurities (Na2O and SiO2) of about 10,000 ppm is used
diluent 15 such as nitrogen. The ethyl chloride stream as a catalyst. After having operated the cracking reac
14 and the inert diluent are preferably preheated to a tor for about 25 days, the ethyl chloride conversion rate
temperature of from 150° C. to 450° C., more preferably is reduced to about 65 percent of its initial rate.
of from 200 C. to 350° C. at a pressure of from 1 to 8 EXAMPLE 4
bar. The cracking reaction (c) is carried out as described Example 3 is repeated, however the gas feed stream
above. 45 consists of 27.2 mol percent ethyl chloride, 24.5 mol
The effluent 16 from the cracking reactor C contains percent ethylene and 48.3 mol percent nitrogen. After
mainly ethylene, hydrogen chloride, inert diluent and 50 days, the ethyl chloride conversion rate is reduced to
minor amounts of by-products such as uncracked ethyl about 65 percent of its initial rate.
chloride. Hydrogen chloride is preferably separated EXAMPLE 5
from effluent 16, for example by adsorption of hydro 50
gen chloride in washing equipment. Hydrogen chloride Example 2 is repeated, however the average resi
can be recovered as aqueous hydrochloric acid or it can dence time of the flowing gas stream in the cracking
be neutralised. reactor is 30 seconds. After having operated the crack
Preferably, effluent 16 from the cracking reactor C is ing reactor for about 100 days, the ethyl chloride con
then recycled to the oxychlorination step (a), most pref 55 version rate is reduced to about 70 percent of its initial
erably after having separated unreacted ethyl chloride rate.
from effluent 16. Ethylene can be recycled to the oxy EXAMPLES 6 to 21
chlorination step (a) or to another reaction in which To evaluate the influence of the temperature, the
ethylene is consumed, for example for producing ethyl pressure and the residence time on the ethyl chloride
ene dichloride via direct chlorination of ethylene, for conversion rate, a gas stream consisting of about 27 mol
example as described in U.S. Pat. No. 4,347,39. percent ethyl chloride (EtCl), about 24 mol percent
The oxychlorination process described herein is pref. ethylene (C2H4) and about 49 mol percent nitrogen (N2)
erably a continuous process. is heated to 250 C. This stream simulates a stream ob
The present invention is further explained in the fol 65 tained in the oxychlorination step (a) and in fractionat
lowing examples which illustrate the invention but are ing step (b). The cracking reaction (c) takes place in a
not intended to restrict it. All parts and percentages are reactor into which the gas stream is continuously fed.
by weight unless otherwise specified. The results are set forth in Table I.
 9
4,849,562 10
TABLE I
Residence Ethyl chloride
T Pressure time Feed (molar ratios) Products (molar ratios) - conversion rate
Example ("C.) (bar) (seconds) C2H4 EtO N2 C2H4. Etc. N2 (%)
6 262 1 5 168 187 3.45 1.83 1.23 3.45 34.
7 262 1 10 1.19 1.32 2.44 1.84 0.66 2.44 50.3
8 262 1. 15 0.59 0.66 1.29 1.07 0.23 1.29 65.9
9 273 1. 5 1.68 1.87 3.45 2.17 1.04 3.45 38.1
10 273 10 1.17 1.30 2.39 1.89 0.56 2.39 57.1
11 273 5 0.39 0.43 0.80 0.77 0.14 0.80 68.1
12 282 5 1.68 .87 3.45 2.39 0.88 3.45 S2.9
13 282 O 1.42 .58 2.92 2.63 0.61 2.92 61.4
4. 282 is 0.62 0.59 1.23 1.09 0.17 1.23 76.0
15 290 1 5 1. 1.25 2.30 .98 0.32 2.30 740
16 290 1. 10 0.56 0.62 1.14 1.14 0.12 1.4 80.
17 290 1 15 0.37 0.4 0.76 0.72 0.07 0.76 82.7
18 282 2 15 0.71 0.79 1.46 1.23 0.32 1.46 60.0
19 282 3 15 1.16 1.28 2.38 1.57 0.52 2.38 58.2
20 282 4. 15 .23 1.36 2.52 1.79 0.65 2.52 52.7
21 282 5 15 1.53 .71 3.15 2.19 0.95 3.15 44.6

20 7. The process of claim 1 wherein water is removed

from the ethyl chloride-rich fraction (II) before carry
ing out step (c).
What is claimed is: 8. The process of claim 1 wherein ethylene obtained
1. An oxychlorination process for producing ethylene in step (c) is recycled to process step (a).
dichloride by 25 9. The process of claim 1 wherein the cracking cata
(a) reacting ethylene with hydrogen chloride and lyst used in step (c) is aluminum oxide.
oxygen in the presence of an oxychlorination cata 10. The process of claim 9 wherein the catalyst is
lyst in an oxychlorination reactor, whereby ethyl gamma-alumina having a surface area between about 10
chloride or both ethyl chloride and vinyl chloride m2/g and about 350 m2/g.
are produced as by-products which process com 30 11. The process of claim 10 wherein the catalyst is
prises the further steps of gamma-alumina having a surface area between about 50
(b) dividing, in one or more steps, the effluent from m2/g and about 250 m2/g.
the oxychlorination reactor into at least (i) an eth 12. The process of claim 10 wherein step (c) is carried
ylene dichloride-rich fraction (I) and (ii) an ethyl out in the presence of nitrogen.
chloride-rich fraction (II) in such a fashion that 35 13. The process of claim 10 wherein the ethyl chlo
fraction (I) contains less than about 50 percent of ride-rich fraction (II) is once or twice distilled at a tem
the total weight of ethyl chloride produced in step perature between about 30° C. and about 180° C. at a
(a) and the sum of the weight of ethylene dichlo pressure between about 1 and about 10 bar before carry
ride and vinyl chloride in fraction (II) is less than ing out step (c).
about 30 percent of the weight of ethyl chloride in 14. The process of claim 10 wherein water is removed
fraction (II) and from the ethyl chloride-rich fraction (II) before carry
(c) subjecting fraction (II) to a cracking process in the ing out step (c).
presence or absence of an inert diluent whereby 15. The process of claim 10 wherein ethylene ob
fraction (II) contains less than about 5 percent tained in step (c) is recycled to process step (a).
ethylene dichloride and vinyl chloride, based on 45 16. The process of claim 1 wherein step (c) is carried
the combined weight of ethyl chloride and inert out at a temperature between about 250° C. and about
diluent in fraction (II) prior to cracking, the crack 320 C., at a pressure between about 1 and about 8 bar
ing process being carried out in the presence of a and in the presence of nitrogen, the residence time of
cracking catalyst in a cracking reactor wherein ethyl chloride in the cracking reactor is from about 5 to
ethyl chloride is converted into ethylene and hy 50 about 60 seconds and the cracking catalyst used in step
drogen chloride. (c) is aluminum oxide.
2. The process of claim 1 wherein step (c) is carried 17. The process of claim 16 wherein the catalyst is
out at a temperature between about 250 C. and about gamma-alumina having a surface are between about 10
320 C. m2/g and about 350 m2/g.
3. The process of claim 1 wherein step (c) is carried 55 18. The process of claim 17 wherein the catalyst is
out at a pressure between about 1 and about 8 bar. gamma-alumnia having a surface area between about 50
4. The process of claim 1 wherein the residence time m2/g and about 250 m2/g.
of ethyl chloride in the cracking reactor is from about 5 19. The process of claim 18 wherein the ethyl chlo
to about 60 seconds. ride-rich fraction (II) is once or twice distilled at a tem
5. The process of claim 1 wherein step (c) is carried 60 perature between about 30° C. and about 180° C. at a
out in the presence of nitrogen. pressure between about 1 and about 10 bar before carry
6. The process of claim 1 wherein the ethyl chloride ing out step (c).
rich fraction (II) is once or twice distilled at a tempera 20. The process of claim 18 wherein water is removed
ture between about 30° C. and about 180° C. at a pres from the ethyl chloride-rich fraction (II) before carry
sure between about 1 and about 10 bar before carrying 65 ing out step (c). k k k
out step (c).