Sept. 24,1957 A. .1.

cHERNlAvsKY 2,807,656
ETHYL CHLORIDE PRODUCTION
-Filed Jan. 28. 1957 2 Sheets-Sheet 1

INVENTOR: /f
AL ANDER J. CHERNIAVSKY
BY= .M
HIS AGENT
Sept. 24, 1957 A. J- CHERNIAVSKY 2,807,656
ETHYL CHLORIDE PRODUCTION
Filed Jan. 28,! 1957 2 shets-sheet 2

H E

j AU
INVENTORI
ALEXAN ER J CHERNIAVSKY

BY HIS AGENT
M
United States Patent O M' CC 2,807,656
Patented Sept. 24, 1957

1 2
to the system is introduced according to a so-called split
feed arrangement, i. e., a feed rich in ethylene is charged
to the hydrochlorinating zone while a feed rich in ethane
2,807,656 is `charged to a ch'lorinating zone.
ETHYL cHLoRmE PRODUCTION Operation of the process according to either embodi
ment is characterized by the hydrochlorination of ethyl
Alexander J. Cherniavsky, San Francisco, Calif., assigner ene in admixture with substantial quantities of ethane,
to Shell Development Company, New York, N. Y., a
corporation of Delaware with the aid of hydrogen chloride formed within the sys
tern, followed by chlorination of residual ethane. The
Application January 28, 1_957, Serial No. 636,680 10 latter step produces reaction products comprising said
hydrogen chloride formed within -the systemi and at
13 Claims. (Cl. 260-662) least in the case of split-feed operation, unreacted ethane.
The hydrogen chloride, together with the unreacted eth
ane when present, is passed to the hydrochlorination step
This invention relates to the production of ethyl chlo 15 where it is admixed with make-up feed containing ethyl- 'y
ride from norm-ally gaseous hydrocarbons comprising ene.
ethylene. The invention relates more particularly to the Referring to Figure I of the drawings, normally gase
production of ethyl chloride from normally gaseous` hy ous hydrocarbons comprising ethylene and ethane ema
drocarbons comprising ethylene and ethane without the nating from any suitable source are forced through valved
need of hydrogen chloride from an outside source. 20 line 10, provided with heat exchanging means, such as
This appli-cation is a continuation-in-part of applica indirect heat exchanger 11, into a hydrochlorinating zone.
tions Serial No. 489,063, iiled February 18, 1955, and The hydrochlorinating zone may comprise any suitable
Serial No. 580,819, filed April 26, 1956, now abandoned. type of apparatus enabling subjection of ethylene to ethyl
Ethyl chloride is of importance because of its -applica ene hydrochlorinating conditions therein. In the draw
tion as starting or intermediate material in the production 25 ing the hydrochlorinating zone is depicted by a reaction
of valuable chemical derivatives. A potential source of chamber 12. Hydrogen chloride, emanating from withinv
starting material for the manufacture of this compound the system as described more fully below, is forced
comprises the ethylene-containing mixtures as obtained through line 13 into line 10 leading to chamber 12.
in relatively large quantities in commercial scale treat Within chamber 12 the normally gaseous hydrocarbon
ment, refining and conversion of petroleum hydrocarbons. 30 charge is subjected to conditions resulting in the inter
Readily available ethylene-containing hydrocarbon mix action of hydrogen chloride with ethylene with the forma
tures generally comprise this olefin in admixture with tion of ethyl chloride. The addition hydrochlon'nation
other hydrocarbons comprising ethane. Initial separa of ethylene is preferably carried out under conditions at
tion of a relatively pure ethylene before proceeding to which no substantial interaction of ethane with hydrogen
the production of ethyl chloride therefrom increases con 35 chloride takes place. Suitable ethylene hydrochlorinating
siderably the process steps involved and consequently the conditions comprise, for example, those obtained with the
cost of the ethyl chloride thereby produced. Subjecting aid of a suitable olefin hydrochlorinating catalyst. Thus,
the available mixtures substantially as such to conditions the ethylene-containing charge may be contacted within
comprising olefin hydrochlorination by methods disclosed chamber 12 with a hydrochlorination catalyst comprising,
heretofore often entails diiiiculties millitating against etli 4.0 for example, zinc chloride, optionally upon a suitable
cient operation of the process. Not an inconsiderable porous support material, at a temperature of, for example,
part of such diiliculties and high cost of operation are di from `about 20 to about 300 C., and preferably from '
rectly attributable to reliance upon hydrogen chloride about 150 to about 250 C., at a' superatmospheric pres
from an outside source as a charge material. sure ranging, for example, from slightly above atmos
It is an object of the present invention to provide an pheric to about 750 lbs., and preferably from about 75
improved process enabling the more efficient production to about 3.00 lbs. p. s. i. g.- A promoter, such as, for
of ethyl chloride from normally gaseous hydrocarbons example, a member of the group consisting of the divalent
comprising ethylene and ethane. metals such as copper, lithium, antimony, magnesium,
Another object of the invention is the provision of an calcium, bismuth and theV like, is preferably added to the '
improved process enabling the more eicient conversion 50 catalyst.
of normally gaseous hydrocarbons comprising ethylene Under the above-defined hydrochlorinating conditions,
and ethane to ethyl chloride without the need of hydrogen ethane is substantially inert and ethylene will react with
chloride from an outside source. hydrogen chloride with the formation of reaction prod
A more specific object of the invention is the provision ucts consisting essentially of ethyl chloride and unreacted
55
of an improved process enabling the more eflicient pro ethane containing a minimum of by-products. High con
duction of ethyl chloride from normally gaseous hydro versions, based on the hydrogen chloride present, are
carbons Icomprising ethylene and ethane wherein ethylene readily obtained over extended periods of continuous
is subjected to hydrochlorinating conditions in the >pres operation. The process of the inventionfis, however, in
ence of hydrogen chloride produced within the system. no wise limited to the maintenance of any specific hydro
Other objects and advantages of the present invention 60
chlorinating conditions within chamber 12 and other
will become apparent from the following detailed descrip suitable hydrochlorinating conditions enabling the addi
tion thereof made with reference to the attached drawings tion of hydrogen chloride to the ethylene may be resorted
wherein: to within the scope of the invention.
Figure I represents a more or less diagrammatic ele Other suitable catalyst which may be employed in
vational view of a form of apparatus suitable for carry carrying out the ethylene hydrochlorination in the vapor
ing out the process of the invention according to one phase in chamber 12 comprise the chlorides of the tri
embodiment thereof, where make-up feed to the system valent metals, such as, for example, aluminum chloride,
is introduced as a mixture comprising ethylene and ethane bismuth chloride, antimony chloride, iron chloride, vana
into a hydrochlorinating zone, and dium chloride, and their oxychlorides, optionally sup
Figure Il represents a modified form of apparatus suit 70 ported upon solid support material. Suitable liquid phase
able for carrying out the process of the invention accord hydrochlorinating conditions comprise the use of a
ing to another embodiment thereof, where make-up charge catalyst' such as, for example, aluminum chloride, bismuth
 2,807,656
3 4
chloride or iron chloride, optionally dissolves in a suit through line 41 into line 37 leading to chamber 40.
able solvent such as an alkyl chloride, for example, ethyl Means for controlling the temperature of the chlorine
chloride, at a temperature below about 60 C. and at a charge, such as, for example, a heat exchanger 42, is pro
pressure sufficiently high to maintain at least a substan vided to enable the heating or cooling of chlorine entering
tial part of the reactants in the liquid phase. the system.
Temperatures in chamber 12 are maintained within the A particular advantage of the invention resides in the
desired range with the aid of suitable means, such as, for ability to send to the chlorinating zone the effluent stream
example, heat exchanger 11, and optionally by other leaving chamber 12 after removal of substantially only
means not shown in the drawing, enabling the addition or ethyl chloride therefrom. If desired,` however, com
withdrawal of heat from reactants and from the reac 10 ponents which may at times be present, such as, chlo
tion zone. . .
rinated hydrocarbon by-products, residual ethylene, etc.,
Hydrochlorinating conditions maintained within cham may be removed in part or entirety from the charge to the
ber 12 may vary considerably within the scope of the chlorinating zone within the scope of the invention.
invention. Thus hydrochlorinating conditions enabling a Thus, the charge to the chlorinating zone may, if desired,
high conversion of ethylene to the desired ethyl chloride subjected to one or more such steps as, for example,
may be employed. When hydrochlorinating conditions adsorption, solvent extraction, distillation, extractive dis
resulting in `the substantially complete conversion of tillation, scrubbing, etc.
ethylene to ethyl chloride, with a relatively complete Within chamber 40, the normally gaseous hydrocarbon
utilization of hydrogen chloride introduced into the cham stream comprising ethane emanating from chamber 12,
ber 12`are employed, the mol ratio of ethane to ethylene is subjected to substitutive ethane chlorinating conditions
in `the `make-up normally gaseous hydrocarbon charge resulting in the interaction of ethane and chlorine with the
introduced into the system from an outside source through formation of reaction products comprising ethyl chloride
valved line `10, is preferably maintained at a value of and hydrogen chloride. The invention is in no Wise
about at least 1, for example, from about 1:1 to about limited to the use of any specic substitutive ethane
1.5: l. Higher or lower ratios of ethane to ethylene in the chlorinating conditions Within chamber 40 and any condi
charge may, however, be employed within the scope of tions may be employed therein resulting in the conversion
the invention. The methane content of the charge is pref of ethane to reaction products comprising ethyl chloride
erably maintained at a minimum, for example, below and hydrogen chloride. The contents of chamber 40 may
about one mol percent. be subjected to thermal substitutive ethane chlorinating
A feed fractionation zone is provided to enable adjust 30 conditions, for example, at a temperature above about
ment of the compositionof the normally gaseous hydro 225 C., but below the temperature at which any substan
carbon feed introduced as make-up into the system. Such tial formation of undesired by~products is encountered,
a feed` fractionation zone may comprise, for example, a preferably in the range of from about 275 C. to about
column 15.` At least a part of the feed introduced into 525 C. and at a pressure ranging, for example, from
the systemthrough valved line 10, may be by-passed about atmospheric to about 300 p. s. i. g. Particularly
through `valved line 16 into column 15. Within column `preferred is the temperature range of from about 375 to
15 the normally gaseous hydrocarbon feed is subjected about 475 C., at a pressure of from about atmospheric
to fractionating conditions resulting in the formation of a to about l0() p. s. i. g. Under these conditions, interaction
vapor overhead containing at least a substantial amount of ethane with chlorine will take place with the formation
of the methane originally present in the charge to result 40 of reaction `products consisting essentially of ethyl
in` a liquid bottoms fraction containing less than about chloride and hydrogen chloride in the absence of sub
one mol percent methane. Sufficient two carbon~contain* stantial formation of undesired by-products. lt is to be
ing hydrocarbons may be taken overhead in column 15 to understood, however, that the invention is in no wise
control the mol ratio of ethane to ethylene in the liquid limited to the use of any `specific substitutive ethane chlorin~
bottoms. 45 .ating conditions in chamber 40. Any suitable chlorinat
Liquid bottoms comprising ethylene and ethane are ing conditions in either vapor or liquid state, with or
taken from column 15 and forced through valved line without catalysts, with fixed or lluidized catalyst bed,
18, into line 10 leading to chamber 12. . which are capable of resulting in the conversion of the
Efuence from chamber 12, consisting essentially of ethane to reaction products comprising ethyl chloride and
ethyl chloride and unreacted ethane is passed through ' hydrogen chloride may be maintained in the ethane
line 20 to suitable product separating means. Within the chlorinating zone depicted by chamber 40, within the
product `separating means; ethyl chloride is separated scope of the present invention.
from the reaction products as a final product. The prod Introduction of chlorine into chamber 40, through lines
uct separating means may comprise, for example, a 41 and 37, is preferably controlled to result in substan
column 21. Within column 21, a vapor fraction compris- ' tially complete utilization of the chlorine within the cham
ing unreacted ethane is separated from a liquid fraction ber 40. The rate of chlorine introduction into chamber
comprising ethyl chloride. The liquid fraction is elimi 40 is preferably controlled to result in a mol ratio of
nated from column 21 by means of valved line 22. chlorine to ethane in the range of from about 1:2 to
Vapors consisting essentially of unreacted ethane are about 1:6, and still more preferably, from about 1:3 to
taken overhead from column 21, through line 23 provided 60 about 1:4.
with condenser 24, leading into accumulator 25.` Liquid Desired temperature conditions are maintained in
consisting essentially of ethane is passed from accumula chamber 40 by control of the temperature of the ethane
tor 25 through lines 26, and line 27 provided with cooler containing charge and the chlorine charge by means of
28, into the `upper part of column 21 as reflux. A nor heat exchangers 35 and 42, respectively. Other means
mally gaseous stream consisting essentially `of ethane is not shown in the drawing may be provided for the with
taken from accumulator 25 and passed through lines 29, drawal of heat from, or the introduction of heat into,
30 and 37 into a chlorinating zone. Suitable means for chamber 40. A valved line 36 is provided enabling the
controlling the temperature of the normally gaseous by-passing of indirect exchanger 35.
stream flowing through Vline 30, for example, an indirect Eflluence from chamber 40 will comprise ethyl chloride
heat exchanger 35, is positioned in line 30. The chlorinat 70 and hydrogen chloride and may contain ethane in an
mg zone may comprise any suitable apparatus enabling amount which will depend upon composition of the speci~
subjection of the ethane to substitutive chlorinating` con fic charge to chamber 40 and the specific conditions main
ditions. `In the drawing, the chlorinating zone is depicted tained therein. Since ethylene is not substantially affected
by chamber 40. under the preferred chlorinating conditions recited above
Chlorine `emanating from an outside source is forced 75 this olefin will be present in the eluence from chamber
 2,807,656
` f 6
4'() if present in the charge thereto. By-products, con duced into hydrochlorination reaction chamber 12 where`
sisting essentially of chlorinated C2 hydrocarbons other in it is contacted with a catalyst consisting of copper
than ethyl chloride, will generally be present in only chloride-promoted zinc chloride on a porous aluminous
minor amounts. At least a part of the effluence leaving support (Celite) at a temperature of 175 C.,'a pressure
chamber 40 is passed to the hydrochlorinating chamber of 250 p. s. i. 1g. land a thoughput rate of l lb. of feed/hr]
12. Eluence consisting essentially of ethane chlorina l.8 lbs. of catalyst. Ethyl chloride is separated in frac
tion reaction products comprising ethyl chloride and tionator 21 from the e?fluence from the hydrochlorina
hydrogen chloride are passed from chamber 40, through tion reaction chamber and discharged from the- system
lines 45 and 47, into line 13 which discharges into line at 22. A 90% conversion of ethylene with a 99.5% yield
10 leading into chamber 12. A cooling means, such as, 10 of ethyl chloride on ethylene converted is obtained. The
.for example, a heat exchanger 46, is provided in line 45 hydrochlorination reaction chamber effluent remaining
to enable the removal of at least a part of the heat of re after separating ethyl chloride therefrom contains 91.9%
action from the stream flowing through the line 45. ethane and 2.8% ethylene, the balance consisting essen
Although reactor efuent emanating from chamber 40 tially of normally gaseous hydrocarbons other than ethane
may be passed in part, or entirety, directly to hydrochlo 15 `and ethylene, residual hydrogen chloride and ethyl chlo
rinating chamber 12, it is preferably iirst freed of at least ride. A portion of the hydrochlorination reaction eu
a part of its ethyl chloride content. At least a part of ence remaining after separating ethyl chloride therefrom
the eiiluence from chamber 40 is preferably passed is continuously bled from the system at 29 in controlled
through valved line 45 into a product separating Zone amount to maintain the desired feed composition to the
wherein ethyl chloride is separated as a final product. 20 respective reaction chambers. 3.2% of the hydrochlorin
The product separating zone may comprise, for example, ation chamber `efliuence is thus bled continuously from
a column 50. Within column 50, eflluence from cham the system and the remainder introduced through lines
ber 40 is subjected to fractionation `to separate a vapor 30 and 37 into chlorinationA reaction chamber 40. Chlo-`
fraction comprising hydrogen chloride from a liquid frac rine from a source outside the system is introduced con
tion comprising ethyl chloride. The liquid fraction is 25 tinuously through line 41 into the chlorination reaction
separated from column 50 through valved line 51. ` chamber in an amount equal to 71% by weight of the
The vapor fraction, consisting essentially of hydrogen ethane charged thereto. Within the chlorination reaction
chloride and any unreacted hydrocarbons lower boiling chamber the ethane-containing charge thereto is subjected
than ethyl chloride which may be present such as ethane to thermal ethane chlorinating conditions at 425 C., a
and ethylene, is withdrawn from column 50 through line 30 pressure of 80 p. s. i. g, with a contact time of about 3
52, provided with cooler 53, discharging into an accumu seconds. Complete -chlorine conversion is attained in
lator 54.. Liquid is taken from -accumulator 54 and the chlorination reaction chamber. Ethyl chloride is
passed through valved lines-55 and 56 to the top of separated from the eiiuence from the chlorination reac
column 50 as reflux. Line 56 is provided with suitable tion chamber by fractionation in column 50 and elimi
cooling means, such as a cooler 57. A normally gaseous 35 nated at 51. The chlorination reaction chamber eflluence
stream comprising hydrogen chloride, and unreacted remaining after separating ethyl chloride therefrom con
ethane and ethylene if these unreacted hydrocarbons are taining 56% ethane, 2.7% ethylene, 31.5% hydrogen
present in the effluence from chamber 40, is taken chloride, the balance consisting essentially of normally
from accumulator 54 and passed through lines 58 and 13 gaseous hydrocarbons other than ethane and ethylene and
into line 10 discharging into chamber 12. Hydrogen 40 residual ethyl chloride, is passed through lines 52 and 13
chloride emanating from chlorinating chamber 40 thus and used as the hydrogen chloride-containing recycle
provides the hydrogen chloride utilized in effecting the stream combined with the fresh normally gaseous hydro
ethylene hydrochlorination in chamber 12. When start carbon charge to the hydrochlorination reaction chamber
ing up the process, normally gaseous hydrocarbon charge as described above. A total yield of 94.6% isl thus ob
may be cycled through the system to produce the required 45 tained based on total ethylene and ethane in the charge
initial amount of hydrogen chloride. An initial amount tov the system converted. All percentage gures em
ofhydrogen chloride, produced, for example, in a previous ployed in the foregoing example are weight percent.
completed cycle of operation, may be introduced into Another embodiment or modification of the present
chamber 12 by suitable means not shown in the drawing invention is illustrated in Figure II of the drawings and
for starting up the process. 50 employs the so-called split-feed manner of operation.
To aid in maintaining optimum conditions, a portion This procedure is especially advantageous when there
of the product streams may be bled from the system are available two sources of supply, one rich in ethylene
through one or more of the valved lines 26, 29, 55 and and the other rich in ethane.
58. Referring to Figure II of the drawings,fan ethane
EXAMPLE I 55 containing normally gaseous hydrocarbon stream, for ex
As an example of operation of the process according ample, an ethane-rich normally gaseous hydrocarbon
to the embodiment of Figure I, ethyl chloride is produced fraction containing, for example, at least 50%, and pref
from chlorine and a normally gaseous hydrocarbon mix erably at least 75% by weight of ethane, the rest of the
ture consisting essentially of ethane and ethylene in a charge consisting essentially of ethylene >and other nor
continuous process by continuously charging a normally 60 mally lgaseoushydrocarbons, obtained from an outside
gaseous mixture containing 52% ethane and 47% ethyl source, is forced through line 110 into> suitable preheat
ene, the balance consisting of other normally gaseous ing means such as, for example, an externally heated
hydrocarbons and hydrogen, into the system. The nor coil 111 positioned in furnace 116. Additional quantities
mally gaseous mixture is charged through'line 10 and is of ethane are supplied to feed line 110 through line 151
admixed with a recycle stream from line 13, consisting 65 and comprise reaction products containing ethane de
essentially of hydrogen chloride, ethylene, ethane and rived from the hydrochlorination step in a manner to be
containing minor amounts of other normally gaseous described. From heating coil 111, the preheated ethane
hydrocarbons and some residual ethyl chloride, emanat rich hydrocarbon stream is passed through line 114 into
ing from the ethane chlorination step of the process as a suitable chlorinating zone. The chlorinating zone may
described below. The resulting admixture, containing 70 comprise any suitable apparatus enabling subjection of the
55% ethane, 17% ethylene and 22% hydrogen chloride, ethane content of the charge thereto to substitutive
the balance consisting essentially of normally gaseous chlorinating conditions. In the drawing the chlorinating
hydrocarbons other than ethane and ethylene, hydrogen zone is depicted by chamber 115. Chlorine emanating
and ethyl chloride, obtained by mixing the fresh normally from an outside source is forced through line 117 into
gaseous hydrocarbon feed and recycle stream, is intro 75 line 114 leading to chamber 115. l .
 2,807,656
7 . 8 l
Within chamber 115, the normally gaseous hydrocar are subjected to conditions resulting `in the interaction
bon stream comprising ethane is subjected to substitutive of hydrogen chloride with ethylene with the formation
chlorinating conditions which will result in the interac ofethyl chloride. The addition hydrochlorination of
tion of ethane and chlorine with the formation of re `ethylene is preferably carried out under conditions at
action products comprising ethyl chloride and hydrogen 5 which no substantial interaction of ethane with hydrogen
chloride,together with unreacted ethane. The invention chloride takes place. Suitable ethylene hydrochlorinating
is in no wise limited to the use of any specific substitutive conditions comprise, for example, those described in con
ethane chlorinating conditions within chamber 115 and any nection with operationy according to the embodiment of
conditions may be employed therein resulting in the con Figure I. Under such conditions ethane is >substantially
version of 4ethane to reaction products comprising ethyl inert and ethylene will react with hydrogen chloride with
chloride and hydrogen chloride. . Particularly preferred the formation of reaction products consisting essentially
chlorinating conditions are described in connection with of ethyl chloride `and unreacted ethane containing a mini
Figure I, and the same or similar conditions may be em mum of by-products. High conversions, based on the
ployed in' operating according to the present embodiment. hydrogen chloride present, are readily obtained over
'Efuence from chamber 115 will comprise ethyl chlo 15 extended periods of continuous operation.
ride and hydrogen chloride, together with unreacted ethane The process of the invention is, however, in no wise
in an amount which will depend upon composition of the limited to the maintenance of any specific Aethylene hydro
specific charge to chamber` 115 and the specific condi chlorinating conditions within chamber 135 and other
tions maintained therein.` Since ethylene is not sub suitable hydrochlorinating conditions enabling the addi
stantially affected under the preferred chlorinating condi tion of hydrogen chloride to the ethylene may be resorted
tions recited above, this oleiin will be present in the to within the scope of the invention. The hydrochlorina-`
efiluence from chamber 115 when` present in the charge tion may be carried out in liquid, vapor or mixed phase,
thereto. By-products, consisting essentially of chlorinated all as described in connection with the embodiment oi'
C2 hydrocarbons other than ethyl chloride, will generally Figure I. v
be present in only minor amounts. Temperatures in chamber 135 are maintained within
Although reactor efuence emanating from chamber the desired range with the aid of suitable means such as,
115 may be passed in part, or entirety, directly to the for example, heat exchanger 137, and optionally by other
hydrochlorinatiug zone of the process described herein means not shown in the drawing, enabling the addition
below, it is preferably tirst freed of at least a part of its or withdrawal of heat from reactants and from the reac
ethyl chloride content. At least a part of the effluence tion zone. The desired pressure conditions within cham
from chamber 115 `is preferably passed through line 11S ber 135 are maintained with the aid of suitable means
into a product separating zone wherein ethyl chloride is such as, for example, a compressor 138 and optionally
separated as a final product. The product separating zone other means not shown in the drawing. When the pres
may comprise, for example, a column 120. A cooling sures maintained in chamber 135 are substantially below
means such as, for example, a heat exchanger 119, is those within chamber 115, it is to be understood that
provided in line 118 to enable the removal of at least a compressor 138 may be by-passed by conventional by-pass
part of the, heat of reaction from the stream flowing means not shown in the drawing.
through the line 118. Within column 120, etiiuence Etiiuence from chamber 155, consisting essentially of
from chamber 115 is subjected to fractionation to sepa ethyl chloride .and unreacted ethane, and which may con
40 tain hydrogen chloride in amounts governed by the spe
rate a vapor fraction comprising hydrogen chloride and
ethane from a liquid fraction comprising ethyl chloride. citic hydrochlorinating conditions employed, is passed
The ethyl chloride-containing liquid fraction is withdrawn through line 139 to suitable product separating means.
from `column 120 vthrough valved line 122 as a final Within the product separating means, ethyl chloride is
product. separated from the reaction products as a final product.
The vapor fraction, consisting essentially of hydrogen The product separating means may comprise, for ex
chloride and any unreacted hydrocarbons lower boiling ample, a column 146. Within column 140, a vapor frac
than ethyl chloride which may be present such as ethane tion comprising unreacted ethane is separated from a liq
and ethylene, is withdrawn from column 120 through uid fraction comprising ethyl chloride. The liquid frac
line 123, provided with cooler 124, discharging into an tion comprising ethyl chloride is eliminated from column
accumulator 125. Liquid condensate is taken from ac 140 by means of valved line 142 leading into line 122
cumulator 125 `and passed through valved lines126 and and eliminated from the system as a nal product.
127 to the top of column 120 as reiiux. Line 127 is The vapor fraction consisting essentially of unreacted
provided with suitable cooling means such as a cooler 128. ethane, and any normally gaseous materials comprising
A normally gaseous stream comprising hydrogen chlo ethylene, chlorine, hydrogen chloride, inert gases, chlo
ride and unreacted ethane is taken from accumulator 125 rinated hydrocarbon byproducts, etc., present in the ef
`and passed through `lines 130 and 131 into a hydro fluent stream from chamber 135 is taken overhead from
chlorinating zone. The hydrochlorinating zone may com column 14), through line 143, provided with condenser
prise any suitable type of apparatus enabling subjection 144, leading into accumulator 145. Liquid condensate
of ethylene to ethylene hydrochlorinating conditions consisting essentially of ethane is passed from accumu
therein. ln the drawing, the hydrochlorinating zone is 60 lator 145 through valved lines 147 and 148 provided with
depicted by a recation chamber 135. cooler 149, into the upper part of column 140 as reflux.
Normally gaseous hydrocarbons comprising ethylene, A normally gaseous stream consisting essentially of
preferably an ethylene-rich normally gaseous hydrocarbon ethane and which may comprise ethylene, chlorine, hy
stream, for example, a C2 hydrocarbon fraction contain drogen chloride, inert gases, chlorinated hydrocarbon
ing at least about 50% and preferably at least 75% by by-productsfetc., present in the etuent stream from
weight of ethylene, the rest of the fraction consisting chamber 135, is taken from accumulator 145 and recycled
to chamber 115 through valved lines 150 and 151, dis
essentially of ethane and other normally gaseous hydro charging into line 110.
carbons is taken from an outside source and forced A particular advantage of the invention according to
throughiline 136 into line 131 leading to chamber 135. the aspect of Figure II, is directly attributable to the dis
The charge to chamber 135 will thus comprise ethylene covery of the ability to recycle directly to the chlorinat
taken from an `outside source in addition to hydrogen ing zone the eiiluent stream leaving chamber 135 after
chloride and unreacted .ethane emanating from within the removal of substantially only crude ethyl chloride there
system through lines 130 and 131. from. However, the removal therefrom, in part or en
Within chamber 135, normally gaseous hydrocarbons 75 tirety of certain components such as chlorinated by
 2,807,656
10
products, etc., should this be desired, may be carried out hydrocarbons, other than the C2 hydrocarbons enter the
within the scope of the invention. Thus, the stream re system through line 110 and are combined with 55 67 parts
cycling through line 51 to the charge to the chlorinat of chlorine introduced at 117, and 6429 parts of a re
ing zone may, if desired, be subjected to one or more cycle stream from line 151 obtained within the system
such steps as, for example, adsorption, solvent extraction, as described below andthe composition of which is given
distillation, extractive distillation, scrubbing,_etc. in the column A of the following Table I. The result
A compressor 152 is provided to enable the forcing of ing mixture is introduced in continuous stream into the
the recycle stream from accumulator 145 through lines chlorination reactor 115 and therein subjected to thermal
150 and 151 into line 110 when the pressure in line 110 selective ethane chlorinating conditions at 420 C., a
exceeds that in accumulator 145. This is the case, for pressure of 80 p. s. i. g. and a contact time of about 3
example, when the pressure within chamber 135 is sub seconds. The etfluence from the chlorination reactor,
stantially below that in chamber 115. Thus, the above having the composition in column B of Table I is
dened permissible liquid, or mixed, phase hydrochlori quenched and introduced through line 118 into a first
nating conditions comprises the use of pressures which product separating zone 120. In the first product sepa
may be substantially below pressures within the above 15 rating zone, a liquid> fraction consisting of crude ethyl
defined pressure range suitably maintained Within cham chloride is separated by fractionation from a vapor frac
ber 115. tion containing the remainder of the chlorination reactor
To avoid the building up of undesirable by-products efluence. The liquid fraction, consisting of the crude
or inert gases to excessive amounts within the system, a ethyl chloride, is eliminated from the system through line
portion of the steam owing through valved line 150 is 20 122 as a finished product. The vapor fraction from the
eliminated periodically, or continuously, in controlled rst separating zone is passed through lines 123 and 131
amount from the system. By thus returning the greater and combined with 21584 parts of an ethylene-rich nor
part of the effluence from accumulator 145 to the chlo mally gaseous hydrocarbon fraction, introduced from an
rinating zone, and bleeding only a limited controlled outside source through line 136, and containing 1949 parts
amount from the system, loss of C2 hydrocarbons and 25 of ethylene, 174 parts of ethane and 35 parts of hydro
of hydrogen chloride is reduced to a minimum. The dis carbons other than C2. The resulting mixture, having the
covery that the eiiiuence from accumulator 145 may thus composition indicated in column C of Table I, is intro
be recycled to the chlorinating zone without loss of duced in continuous stream into the hydrochlorination re
efficiency enables the building up of undesired by-prod action chamber 135 wherein it is contacted in the vapor
ucts to a relatively high concentration in the recycle 30 phase with a catalyst consisting essentially of copper
stream owing through lines 150 and 151. Since the chloride-promoted zinc chloride on a porous aluminous
bleed eliminated through valved line 150 from the sys support (Celite), at a temperature of 193 C., a pressure
tem is concentrated with respect to by-products and un of 250 p. s. i. g. and a throughput rate of one pound of
Wanted inert gases, this represents in turn an additional feed/hr./ 1.8 bbls. of catalyst. Efliuence from the hydro
reduction in loss of C2 hydrocarbons and hydrogen chlo 35 chlorinating Ireactor having the composition indicated in
ride over that encountered in the absence of such a re the column D of the following Table I is passed continu
cycling operation. ously through line 139 into second product separating
As pointed out hereinbefore, the composition of the Vzone 140 wherein a liquid fraction, consisting of crude
ethylene-rich stream introduced into the system through ethyl chloride, is separated from a vapor fraction consist
line 136 and that of the ethane-rich stream introduced 40 ing of the remaining components of the hydrochlorination
through line 110 may vary considerably within the scope reactor eiuence stream. The liquid fraction, consisting
of the invention. Thus, they may consist essentially of of crude ethyl chloride, separated in the second separat
pure ethylene and ethane, respectively, or comprise mix ing zone is eliminated from the system through line 142
tures of ethylene and ethane in varying amounts. Al as a nal product. With the exception of 328 parts of
though an advantage of the invention resides in its flex 45 bleed, consisting of 12 parts of ethylene, 289 parts of
ibility of operation, enabling its application to ethylene ethane, 14 parts of hydrocarbons other than C2, and 13
and ethane streams as generally available, feed fraction parts of miscellaneous by-products,`the remainder of the
ating means, not shown in the drawing, may be re vapor fraction -separated in the second product separating
sorted to to adjust the composition of the ethylene and/ or zone is employed as the recycle through line 151 which
ethane streams charged to the system within the scope 50 is combined with the ethane-rich feed charged to the
of the invention. Such feed fractionation may be re chlorination reactor referred to hereinbefore. In this con
sorted to to aid in obtaining the preferred ratio of eth tinuous operation, there are obtained 9876 parts of crude
ylene to ethane in the total charge to the system. The ethyl chloride containing 9041 parts of ethyl chloride
feed fractionation, when employed, is preferably- con and 835 parts of other chlorinated products.
trolled to maintain the methane charged to the system 55
at a minimum, for example, below about one mole per Table I
cent. Comprised withinthe scope of the invention is [Composition in parts by weight.]
the recycling of a portion of the eluence from the chlo
rination and/or Yhydrochlorination zone directly to the A B C D
respective reaction zone from which the eifluence ema 60
nates to aid in maintaining the desired operating condi Ethylene _______ _ _ 232 498 2, 447 244
Ethane _________ ._ _ 5, 550 5, 665 5, 839 5, 839
tions therein. Hydrocarbons othe h 251 256 291 265
Ethyl chloride ____________ __ __ 59 4, 059 812 5, 853
EXAMPLE II Chlor'mated lay-products ___________ __ 97 816 134 250
HCl _______________________________ _ _ 240 3, 181 3, 181 253
As an example of operation of the process in accord 65 Total ________________________ __ 6, 429 14, 475 12, 704 12, 704
ance with the embodiment of Figure II, ethyl chloride is
produced from chlorine, ethane-rich normally gaseous hy
drocarbon stream and an ethylene-rich normally gaseous EXAMPLE III
hydrocarbon stream in a continuous, completely inte As a further example an operation according to the
grated process comprising a vapor phase ethane chlorina 70 embodiment of Figure Il, ethyl chloride is produced from
tion step and a Vapor phase hydrochlorination step as fol chlorine, ethane-rich normally gaseous hydrocarbon
lows: All figures used throughout the example are in terms stream and an ethylene-rich normally gaseous hydrocar
of parts per weight per unit time. 2479 parts of an bon stream n continuous, completely integrated process
ethane-rich fraction containing 221 parts of ethylene, l comprising a vapor phase ethane chlorination step and a
2241`1parts of ethane and 17 parts of normally gaseous 75 liquid phase ethylene hydrochlorination step as follows:
 11 . , . . . 12
All figures used throughout the example are in parts by I claim as my invention:
weight per unit time.` 2535 parts of an ethane-rich frac 1. The process for the production of ethyl chloride
tion containing 225 parts ethylene, 2291 parts of ethane from a mixture of normally gaseous hydrocarbons con
and 18 parts of hydrocarbons other than Czs are intro sisting essentially of ethylene and ethane which comprises,
duced through line 110 and combined with 5758 parts of subjecting said mixture to ethylene hydrochlorinating con
chlorine and 10,308 parts of recycle stream from line ditions with the aid of hydrogen chloride obtained within
151 obtained within the system as described below and the system thereby forming hydrochlorination products
the composition of which is indicated in column A of the comprising ethyl chloride and unreacted ethane, separat
following Table ll.` The resulting mixture is introduced ing unreacted ethane from said hydrochlorination re
as a continuous stream into chlorination reactor 115 and action products, substtutively chlorinating said separated
therein subjected to thermal selective ethane chlorinating unreacted ethane thereby forming chlorination products
conditions at 420 C., a pressure of 80 p. s. i. g. and a comprising ethyl chloride and hydrogen chloride, sepa
contact time of about 3 seconds. The entire eluence rating hydrogen chloride from said chlorination products,
from the chlorination reactor having the composition in and passing at least a part of said separated hydrogen
dicated in column B of the following Table ll is quenched chloride to said hydrochlorination.
and introduced through line 118 into first product sepa 2. The process for the production of ethyl chloride
rating zone 120 wherein a liquid fraction, consisting of from a mixture of normally gaseous hydrocarbons con
crude ethyl chloride, is separated from a vapor fraction sisting essentially of ethylene and `ethane which comprises,
consisting of the remainder of the chlorination reactor subjecting said mixture to ethylene hydrochlorinating con
eluence. The vapor fraction is passed through lines 123 ditions in a hydrochlorinating zone with the aid of hydro
and 131 and combined with 2228 parts of an ethylene gen chloride obtained within the system, thereby reacting
rich normally gaseous hydrocarbon fraction containing ethylene with hydrogen chloride with the formation of
2013 parts of ethylene, 180 parts of ethane and 35 parts reaction products comprising ethyl chloride and unreacted
of hydrocarbons other than Czs introduced through line ethane, subjecting at least a part of said unreacted ethane
1.36. The resulting mixture having the composition in to substitutive ethane chlorinating conditions in a chlo
dicated in column C of the following Table Il` is intlo rinating zone, thereby reacting ethane with chlorine with
duced as a continuous stream into hydrochlorination `re the formation of reaction products comprising ethyl chlo
actor 135 and therein subjected to ethylene hydrochlori ride and hydrogen chloride in said chlorinating zone, and
nation conditions by contact with a liquid medium con passing at least a part of said reaction products from said
taining iron chloride (ferric chloride) dissolved in ethyl 30 chlorinating zone to said hydrochlorinating zone.
chloride, at a'temperature of 49 C. and a pressure of 3. The process for the production of ethyl chloride
225 pfs. i. g. Eluence from the hydrochlorinator re from normally gaseous hydrocarbons comprising ethylene
actor having the composition indicated in the column D and ethane which comprises, subjecting said normally
of the following Table Hi is passed through line 139 and gaseous hydrocarbons to ethylene hydrochlorinating con
subjected to fractionation in the second product separat 35 ditions with the aid of hydrogen chloride formed within
ing zone 140 wherein a liquid fraction consisting of crude the system in a hydrochlorinating zone, thereby reacting
ethyl chloride is separated from a vapor fraction consist ethylene with hydrogen chloride `with the formation of
ing of the remainder of the hydrochlorination reactor ef reaction products comprising ethyl chloride and unreacted
fluence. With the exception of 524 parts of bleed stream, ethane in said hydrochlorinating zone, passing at least a
containing S8 parts of ethylene, 298 parts of ethane, 14 40 part of said unreacted ethane from said hydrochlorinat
parts of other hydrocarbons and 125 parts of miscellane ing zone into a chlorinating zone, introducing chlorine into
ous try-products, which are eliminated from the system said .chlorinating zone, subjecting said unreacted ethane
as bleed, the remainder of the vapor fraction is passed to substitutive chlorinating conditions in said chlorinat
through line 151 and employed as the recycle stream , ing zone, thereby reacting ethane with chlorine with the
combined with the ethane-rich normally gaseous hydro formation of reaction products comprising ethyl chloride
carbon feed charged to the chlorination reactor as de 45 and hydrogen chloride in said chlorinating zone, and
scribed hereinabove. In this continuous operation the passing at least a part of said hydrogen chloride from said
combined liquid fractions, consisting of crude ethyl chlo chlorinating zone to said hydrochlorinating zone to be
ride, separated in the rst and second product separating used therein as said hydrogen chloride obtained `within
zones resulted in the obtaining of 9997 parts of crude the system. `
ethyl chloride, 904,1 parts of which was ethyl chloride 50 4. The process in accordance with claim 3 wherein the
and 956 parts of other chlorinated by-products. mol ratio of ethane to ethylene in said normally gaseous
Table Il hydrocarbons subjected to said hydrochlorination is at
[Composition in parts by weight.] least about 1.
5. The process in accordance with claim 3 wherein the
A B C D methane content of said normally gaseous hydrocarbons
subjected to said hydrochlorination is below about 1 mol
percent. '
Ethylene __________________________ _. 1, 709 1, 980 3, 993 1, 797
Ethane ____________________________ __
Hydrocarbons other than Cgs. .
5,765
262
5, 883
268
6, 063
303
6, 063
276
6. The process for the production of ethyl chloride
Ethyl chloride ........ ._ 58 4, 098 819 5,820 from normally gaseous hydrocarbons comprising ethylene
Chlorinated luy-products 103 924 153 288 60 and ethane which comprises, subjecting said normally gas
HCl 5, 448 5, 448 2, 535
eous hydrocarbons to vapor phase catalytic ethylene 'hy
Total ........................ ._ 10, 308 18, 601 16, 779 16, 779 drochlorinating conditions in a hydrochlorinating zone
ywith the aid of hydrogen chloride formed within the sys
lt is seen that the process of the invention according tem, thereby reacting ethylene with hydrogen chloride
to either embodiment thus provides an eicient and highly with the formation of reaction products comprising ethyl
flexible process enabling the substantially complete con chloride and unreacted ethane in said hydrochlorinating
version of the C2 contentA of available ethylene and ethane zone, passing at least a .part of said unreacted ethane from
streams or ethane-ethylene mixtures to desired ethyl chlo said hydrochlorinating zone into a chlorinating zone, in
ride without need for hydrogen chloride from an external troducing chlorine into said chlorinating zone, subjecting
source and with a minimum of loss of charge material. 70 said unreacted ethane to thermal substitutive chlorinating
For 'the purpose of simplicity all parts of apparatus not conditions in said chlorinating Zone, thereby reacting
essential to a complete understanding of the invention ethane with chlorine with the formation of reaction prod
such as, for example, pumps, valves, accumulators, com ucts comprising ethyl chloride and hydrogen chloride in
pressors and the like, have been omitted from the fore said chlorinating zone, and passing` at least a part of said
going detailed description of the invention. 75 hydrogen chloride from said chlorinating zone to said
 2,807,656
13 14
hydrochlorinating zone to :be used therein as said hydro tem, thereby reacting ethylene 'with hydrogen chloride
gen chloride obtained within the system. With the formati-on of hydrochlorination products com
7. The process in .accordance with claim 6 wherein said prising ethyl chloride and unreacted ethane -in said hydro
ethylene hydrochlorination is elected in the presence of chlorinating zone, separating unreacted ethane from said
a catalyst comprising zinc chloride. 5 hydrochlorination products, substitut-ively chlorinating
8. The process in accordance with claim 6 wherein said said separated unreacted ethane at a temperature of at
_thermal substitutive ethane chlorination is efected at a least about 225 C., thereby forming chlorination prod
temperature above about 225 C. ucts comprising ethyl chloride and hydrogen chloride,
9. The process for the .production of ethyl chloride Aseparating hydrogen chloride from said chlorination prod
from normally gaseous hydrocarbons comprising ethylene 10 ucts, and introducing at least a part of said hydrogen
and ethane which comprises, subjecting said normally -gas chloride into said hydrochlorinating zone to be used there
eous hydrocarbons to ethylene hydrochlorinating condi in as said hydrogen chloride obtained within the system.
tions ina hydrochlorinating zone with the aid of hydrogen 11. The process in accordance with claim 10 wherein
:chloride formed within the system, thereby reacting ethyl the mol ratio of ethane to ethylene in said normally gase
ene with hydrogen chloride with the formation of hydro 15 ous hydrocarbons introduced into said hydrochlorinating
chlorination products comprising `ethyl chloride and un zone is 'at least about l.
reacted ethane in said hydrochlorinating zone, separating 12. The process in accordance with claim 3 wherein
unreacted ethane from said 'hydrochlorination products, a mixture comprising ethylene and ethane is introduced
substitutively chlorinating said separated unreacted ethane, as fresh feed to the system into the hydrochlorinating zone
thereby forming chlorination products comprising ethyl 20 along with reaction products including hydrogen chloride
chloride and hydrogen chloride, separating hydrogen chlo from the chlorinating zone.
ride from said chlorination products, and introducing `at 13. The process in accordance with claim 3 wherein
least a part of said hydrogen chloride into said hydro ethane as fresh feed to the system is introduced into the
chlorinating zone to be used therein as said hydrogen chlorinating zone along with reaction products including
chloride obtained within the system. 25 unreacted ethane from the hydrochlorinating zone, -'and
10. The process for the production of ethyl chloride wherein ethylene as fresh feed to the system is introduced
from normally gaseous hydrocarbons comprising ethylene into the hydrochlorinating zone along with reaction prod
and yethane which comprises, subjecting said normally gas ucts including unreacted ethane and 4hydrogen chloride
eous hydrocarbons to ethylene hydrochlorinating condi from the chlorinating zone.
tions in the vapor phase in a hydrochlorinating zone in 30
the presence -of a catalyst comprising zinc chloride and No references cited.
with the aid of hydrogen chloride formed Within the sys