United States Patent (19) (11) 3,983,180

Habata et al. (45) Sept. 28, 1976

(54) PROCESS FOR PREPARING METHYL
CHLORIDE Primary Examiner-Delbert E. Gantz
75 Inventors: Kiichi Habata, Annaka; Shozo Assistant Examiner-Joseph A. Boska
Tanaka, Osaka, Hitoyuki Araki, Attorney, Agent, or Firm-Toren, McGeady and
Annaka, all of Japan Stanger
73) Assignee: Shinetsu Chemical Company,
Tokyo, Japan 57 ABSTRACT
22 Filed: Oct. 2, 1974 A process for preparing methyl chloride by reacting
(2) Appl. No.: 511,208 hydrogen chloride with methanol in the liquid-phase
non-catalytic reaction, employing a reaction system
30 Foreign Application Priority Data comprising a reactor and two distillation columns,
each being operated under a different pressure, to
Oct. 6, 1973 Japan.............................. 48-12723 greatly increase the space time yield and the conver
sion of hydrogen chloride and methanol, and at the
(52) U.S. C. 260/657 same time to reduce the production of dimethyl ether
51 Int. Cl........................................... C07C 17/00 as a byproduct. The raw materials used may be either
58) Field of Search.................. . . . . . . . . . . . . . . . . . . . 260/657 gaseous or liquid; they may contain a large amount of
(56) References Cited water or gases insoluble in water. By this process, hy
drogen chloride gas and diluted hydrochloric acid that
UNITED STATES PATENTS are produced as a byproduct or waste in various
2,153,170 4/1939 Buc et al............................. 260/657 chemical processes can be effectively utilized.
2,244,629 6/1941 Livak et al.......................... 260/657
FOREIGN PATENTS OR APPLICATIONS 3 Claims, 1 Drawing Figure
691,295 7/1964 Canada............................... 260/657
U.S. Patent Sept. 28, 1976 3,983,180
 1
3,983,180 2
to the pressures. If hydrogen chloride is subjected to
PROCESS FOR PREPARING METHYL CHLORIDE reaction with methanol until its concentration becomes
FIELD OF THE INVENTION
lower than the azeotropic composition in the reactor,
the reaction mixture discharged from the reactor can
The present invention relates to be process for pre be separated into hydrochloric acid of the above-men
paring methyl chloride from hydrogen chloride and tioned nearly azeotropic composition, nearly pure
methanol. methanol and nearly pure water by means of recover
DESCRIPTION OF THE PRIOR ART ing facilities composed of, for example, two distillation
columns. Consequently, the former two substances can
Various reports have been made public on the meth 10 be recycled to the reactor and the latter can be dis
ods for preparing methyl chloride by reacting hydrogen charged out of the reaction system to, thereby attain a
chloride with methanol. Typical methods commercially high conversion. However, the concentration of hydro
employed at present are: (1) the vaporphase catalytic gen chloride in the reactor, in this case, is lower than
method in which hydrogen chloride is reacted with 15 the azeotropic composition, so that the reaction rate is
methanol in vapor phase in the presence of a catalyst, low and the reactor is required to have a large volume.
such as, alumina, (2) the liquid-pahse catalytic method Further, when the reaction is carried out in such a
in which hydrogen chloride is reacted with methanol in manner as to make the concentration of hydrochloric
liquid phase in the presence of a catalyst, such as, zinc acid in the reactor higher than the azeotropic composi
chloride, and (3) the liquid-phase non-catalytic tion, it proceeds at a high rate, and the volume of the
method in which hydrogen chloride is reacted with 20 reactor can be made small, guaranteeing a high space
methanol in liquid phase in the absence of any catalyst. time yield. But, in this case where the concentration of
All these methods have not been freed from any hydrogen chloride is higher than the azeotropic compo
drawbacks. For example, speaking of the vapor-phase sition, only part of the hydrogen chloride and methanol
catalytic method, it is carried out at a high tempera to be recycled to the reactor can be separated by an
ture, say, from 300 to 450°C and, consequently, di 25 ordinary distillation from the reaction mixture dis
methyl ether is formed as a byproduct in a greater charged from the reactor, and water can not be sepa
amount than in the other two methods. In addition, the rated as pure water, but separated as hydrochloric acid
catalyst used is required to be replaced or regenerated, of a nearly azeotropic composition. Therefore, in order
and as to the raw materials, hydrogen chloride must be to discharge water out of the reaction system, the hy
in the gaseous anhydrous or a nearly anhydrous state 30 drochloric acid of a nearly azeotropic composition is
and methanol must be in the gaseous state. discharged at the sacrifice of a large amount of hydro
Speaking next of the liquid-phase catalytic method, it gen chloride. Consequently, it is impossible to obtain a
is carried out at a higher temperature compared to the high conversion by this method. In order to prepare
liquid-phase non-catalytic method. Due to operation at 35 methyl chloride at a high space time yield and a high
such a high temperature and the use of a catalyst, di conversion from hydrogen chloride and methanol by
methyl ether is produced in a greater amount than in the liquid-phase non-catalytic method, firstly, the con
the liquid-phase non-catalytic method. Moreover, centration of hydrogen chloride in the reactor should
water contained in the raw materials and water gener be maintained higher than the azeotropic composition
ated by the reaction have to be removed by evapora 40 and, secondly, special recovery facilities should be
tion. Sometimes, more heat is required than in the provided for separating the reaction mixture above the
other methods. In order to recover the unreacted hy azeotropic composition with respect to hydrogen chlor
drogen chloride and methanol vaporized along with the ide into hydrogen chloride, methanol and water, and
water, some additional facilities are required. for recycling the former two substances back to the
Next, according to the conventional liquid-phase 45 reactor and discharging the latter out of the system.
non-catalytic method, in which less dimethyl ether is In one of the means to separate hydrochloric acid
formed than in any of the other two methods, the rate above azeotropic composition into hydrogen chloride
of the reaction between hydrogen chloride and metha and water, an electrolyte, such as, calcium chloride or
nol is so low that a large reaction space is required, and sulfuric acid is added for the purpose of lowering the
in order to increase the conversion, the provision of 50 azeotropic composition of hydrochloric acid. When
facilities for recovering any unreacted hydrogen chlor hydrochloric acid above the azeotropic composition is
ide and methanol becomes indispensable. distilled with addition of the aqueous solution of such
The conventional liquid-phase non-catalytic method an electrolyte, vapor rich in hydrogen chloride and an
will be described in detail in the following. In order to aqueous solution of the electrolyte containing hydro
attain a high space time yield and a high conversion by 55 gen chloride in very low concentration are obtained.
the method of this type, the reaction rate is enhanced Water is evaporated from the electrolyte solution and
by increasing the concentration of the reactants in the condensed to be discharged as water containing little
reaction mixture in a reactor and, at the same time, the hydrogen chloride. Consequently, a combination of a
unreacted reactants coming out of the reactor accom reactor, in which the concentration of hydrogen chlor
panied by the reaction product are separated from the 60 ide is maintained above, the azeotropic composition,
product by means of recovering facilities, such as, dis and recovery facilities comprising an azeotropic distil
tillation columns and are recycled to the reactor. One lation column utilizing the above electrolyte is required
should bear in mind when practicing the liquid-phase for the preparation of methyl chloride by the liquid
non-catalytic method for the preparation of methyl phase non-catalytic method with a high space time
chloride from hydrogen chloride and methanol that, in 65 yield and a high conversion. However, this process is
the binary system of hydrogen chloride and water or in not always advantageous, because in order to keep the
the ternary system of hydrogen chloride, water and concentration of hydrogen chloride above the azeo
methanol, there exists the maximum boiling point azeo tropic composition and the temperature of the reactor
trope with the azeotropic compositions corresponding at a point sufficient to give a satisfactory reaction rate,
 3
3,983,180 4
a pressurized reactor vessel should be employed. When a. withdrawing part of the reaction mixture from the
an azeotropic distillation column, into which an elec reactor,
trolyte as mentioned above is added, is operated at the b. introducing the reaction mixture thus withdrawn
atmospheric pressure, the vapor rich in hydrogen into the first distillation column,
chloride and methanol, obtained at the column top, c. collecting from the top of the first distillation col
should be pressurized by a pump after having been umn vapor richer in hydrogen chloride and metha
liquefied by condensation or absorption, or should be nol than the reaction mixture in the reactor,
directly pressurized by use of a compressor before it is d. recycling the vapor thus collected to the reactor,
recycled into the reactor vessel kept in pressurized e. withdrawing from the bottom of the first distilla
State. O tion column a mixture lower in hydrogen chloride
When the former method, i.e., pressurization after and methanol concentrations than the reaction
liquefaction, is employed, losses in thermal energy and mixture contained in the reactor,
cooling capacity are unavoidable since the vapor once f. discharging from the top of the second distillation
formed by the heat in put in the azeotropic distillation column water contained in the raw materials and
column is liquefied to be recycled to the reactor and 5 water generated during the reaction,
there heated again up to the appropriate reaction tem g. withdrawing from the bottom of the second distil
perature. Therefore, the method is disadvantageous in lation column a mixture richer in hydrogen chlor
comparison with the liquid-phase catalytic method in ide than the mixture in the bottom of the first distill
which the reaction and the azeotropic distillation take lation column,
place simultaneously in one reactor vessel with less 20 h. recycling the mixture thus withdrawn to the first
consumption of thermal energy and cooling capacity. distillation column or to the reactor, and
The direct compression method is also disadvantageous i. collecting methyl chloride formed in the reactor
because of the requirement of a corrosion-resistant from its top.
compressor as well as the problems caused by the con BRIEF DESCRIPTION OF THE DRAWING
densation of the vapor. 25
Alternatively, the azeotropic distillation column may In the accompanying drawing, the single FIGURE is
be kept at a higher pressure than the reactor so that the one form of flowsheet embodying the invention.
vapor collected from the top of the distillation column DESCRIPTION OF THE PREFERRED
may be recycled directly to the reactor by means of EMBODIMENT
some devices such as a sparger. But, the azeotropic 30
distillation column in which a concentrated solution of Referring now more particularly to the drawing, the
the electrolyte is boiled is operated at a temperature process of the invention will be described hereinafter.
high enough to boil the solution under high pressure, When the raw materials are gaseous, they are intro
the temperature becoming even higher by 10° to 50°C duced into reactor 4 by means of conduit 1 and sparger
by the presence of the electrolyte than it otherwise 35 3, while, when they are liquid, they are introduced into
would. reactor 4 by means of conduit 2. Reactor 4 contains a
OBJECTS OF THE INVENTION reaction mixture composed of hydrochloric acid and
methanol in which the concentration of hydrogen
An object of the present invention is to improve the chloride is above the azeotropic composition so that
liquid-phase non-catalytic method so as to provide a 40 the reaction may be carried out at a high rate, and a
more reasonable and economical process for preparing high space time yield may be guaranteed. The reaction
methyl chloride from hydrogen chloride and methanol. mixture in reactor 4 is maintained at 90°C or above, so
Another object of the present invention is to provide a as to able to attain a sufficient reaction rate, and at a
process in which the conversion of hydrogen chloride pressure above atmospheric pressure, preferably in the
and methanol and the space time yield are remarkably 45 range between 1 and 3 kg/cm'G, so as to prevent the
increased and the production of dimethyl ether as a evaporation of hydrogen chloride and methanol.
byproduct is much reduced by employing a reaction Methyl chloride formed is collected from the top of
system composed of a reactor and two distillation col reactor 4 by means of first absorption column 5, con
umns, those composing units being operated under duit 6, and second absorption column 38.
different pressures. Still another object of the present 50 For the purpose of discharging water contained in the
invention is to provide a process in which hydrogen raw materials and generated during the reaction, part
chloride gas and diluted hydrochloric acid produced as of the reaction mixture in reactor 4 is withdrawn by
a byproduct or waste in various other chemical pro means of conduit 7, cooler 8, pump 10 and conduit 12,
cesses can be effectively utilized. while the level of the liquid surface in reactor 4 is kept
55 constant by means of valve 13. Then, through conduit
SUMMARY OF THE INVENTION
14, the withdrawn mixture is sent to first distillation
According to the present invention, a process for column 15. The pressure in first distillation column 15
preparing methyl chloride by reacting hydrogen chlor is a little higher than that of reactor 4 or, higher exactly
ide with methanol in the absence of any catalysts in by 0.1 - 1 kg/cm'G. The difference can be more than 1
liquid phase is carried out with a reaction system com 60
kg/cm'G, but any such difference is not a requirement.
prising (1) a reactor maintained at pressure higher than Vapor richer in hydrogen chloride and methanol than
the atmospheric pressure and supplied with a reaction the reaction mixture in reactor 4 is collected from the
mixture consisting of hydrogen chloride and methanol, top of first distillation column 15 and then recycled to
(2) a first distillation column maintained at pressure reactor 4 through conduit 16 and sparger 3, while from
higher than that of the reactor and (3) a second distilla 65 the bottom of first distillation column 15 by way of
tion column maintained at a pressure lower than that of conduit 19 hydrochloric acid is taken out which is
the first distillation column, the process comprising the nearly of the azeotropic composition under the pres
steps of sure of first distillation column 15, and contains little
 S
3,983,180 6
methanol. The hydrochloric acid thus taken out from and contains little methanol, is collected through valve
first distillation column 15 is sent by means of pump 20, 36, cooled by cooler 43, and introduced through con
conduits 21 and 22, and valve 23 to second distillation duit 37 into second absorber 38 as the absorption me
column 24, which is kept at a lower pressure than first dium, where it can absorb a small amount of hydrogen
distill column 15. The azeotropic composition of hy chloride and methanol accompanied by methyl chlor
drochloric acid varies according to the pressure under ide introduced through conduit 6. The mixture en
which it is placed. The higher is the pressure, the lower riched in hydrogen chloride and methanol can be intro
is the hydrogen chloride concentration in the azeo duced once more into first distillation column 15
tropic mixture. Therefore, if there is a proper differ through conduit 40, pump 41 and conduits 42 and 14.
ence in pressure between first distillation column 15 O Reboilers 17 and 31 are for first and second distillation
and second distillation column 24, hydrochloric acid columns 15 and 24, respectively.
withdrawn from the bottom of first distillation column In the conventional liquid-phase non-catalytic
15 and sent to second distillation column 24 would be method where hydrogen chloride is an aqueous solu
lower in hydrogen chloride concentration than the tion while methanol is liquid, the reactor is endother
azeotropic composition under the pressure inside sec 15
mic, requiring heat, whereas in the case of the reactor
ond distillation column 24. Consequently, when proper of the present invention, the vapor coming out of the
refluxing is carried out in second distillation column top of first distillation column 15 with a large amount
24, water containing only a small amount of hydrogen of heat content provided by reboiler 17 is introduced
chloride is discharged through the top of the column. into reactor 4, and latent heat from the condesation
The pressure of second distillation column 24 must be 20 and absorption of the vapor serves as the heat of reac
lower than that of first distillation column 15. In an tion, so that the reactor is always exothermic and must
ordinary operation, it is advisable that the pressure of be cooled. Therefore, part of the reaction mixture con
second distillation column 24 should be from 10 to 500 tained in reactor 4 is collected by means of conduit 7,
mmHg (absolute). cooler 8, pump 10 and conduit 11, so as to be cooled
It should be noted that the hydrochloric acid with 25 and recycled to first absorber 5, installed on top of
drawn from the bottom of first distillation column 15 reactor 4 for the purpose of controlling the reaction
contains little methanol, so that the water discharged temperature. At the same time, hydrogen chloride and
from the top of second distillation column 24 contains methanol accompanied by methyl chloride formed in
little methanol. reactor 4 can be absorbed in absorber 5 by the reaction
A condenser 25 is installed for the purpose of reflux 30 mixture circulating from the reactor as the absorption
ing or distilling out the vapor from the top of second medium, and recycled to reactor 4. When hydrogen
distillation column 24, and vacuum pump 30 for reduc chloride employed as the raw material is hydrochloric
ing, when necessary, the pressure of second distillation acid of low concentration, it is advisable to supply it to
column 24. From the bottom of the second distillation second distillation column 24 by means of conduit 45,
column 24 is obtained hydrochloric acid, which is 35 pump 46 and valve 47, instead of to reactor 4. As a
nearly of the azeotropic composition under the pres matter of course, the raw material hydrochloric acid or
sure of the column. hydrogen chloride gas may be introduced at various
The reaction system must be designed and operated positions other than the second distillation column 24
so that the mixture kept in the bottom of first distilla-. into the reaction system depending on its concentra
tion column 15 is made lower in hydrogen chloride 40 tion.
concentration than those in reactor 4 and in the bottom As will be clear from the following examples that the
of second distillation column 24. The hydrochloric acid method of the present invention guarantees a high
from the bottom of second distillation column 24 is space time yield and a high conversion regardless of the
recycled to first distillation column 15 by means of raw materials being gaseous or liquid, even when a
conduit 33, pump 24 and conduits 35 and 14. 45 large quantity of water is contained therein. What is
Further, the process of the invention can find ways better, according to the process of the invention, is that
thereby to reuse any hydrogen chloride produced as a the production of dimethyl ether as a byproduct is
byproduct or waste in various other chemical processes much less than by the conventional vapor-phase or
involving the manufacture of chloromethanes and sili liquid-phase catalytic methods.
cones. Part or whole of the relatively diluted hydro 50 EXAMPLE
chloric acid from the bottom of second distillation
column 24 is introduced by way of valve 48 into an A mixture of commercially available concentrated
apparatus denoted by 49 which functions as an ab hydrochloric acid, methanol and water in a ratio of
sorber in one case and into which waste hydrogen 10:1:5 by weight was introduced into reactor 4 and the
chloride from other chemical plants is introduced, and 55 bottom of first distillation column 15. The mixture in
the hydrochloric acid enriched in hydrogen, chloride. is the bottom of first distillation column 15 was evapo
supplied to reactor 4 by way of conduit 50, valve 52 rated in reboiler 17 by heat provided by heating me
and conduit 2. In particular, in the manufacture of dium 18.
silicones, apparatus 49 also serves as a hydrolyzer for The vapor from the top of first distillation column 15
organochlorosilanes, in which the organochlorosilanes 60 was sent to reactor 4. The reaction mixture withdrawn
are hydrolyzed to liberate hydrogen chloride and to from reactor 4 was cooled in cooler 8 by cooling water
consume water contained in the dilute hydrochloric 9, and then the cooled mixture was recycled through
acid, advantageously resulting in reduction in the quan pump 10 and conduit 11 so that all the vapor coming
tity of the water discharged from second distillation out of the top of first distillation column 15 was ab
column 24. 65 sorbed and liquefied in reactor 4 and absorber 5 by the
Part of the mixture in the bottom of first distillation recycling mixture to be sent back to first distillation
column 15, which mixture is lower, in hydrogen chlor column 15 through conduit 12, valve 13, and conduit
ide concentration than that contained in the reactor 4 14. The pressure inside reactor 4 was maintained at 2
 3,983,180
7 8
kg/cm'G by the help of nitrogen gas introduced EXAMPLE 4
through conduit 1. As a result, a mixture containing
18.2 percent by weight of hydrogen chloride and 0.05 In the same procedure as in Example 1, 1,000 g/hour
percent by weight of methanol was obtained from the of gaseous methanol was introduced through conduit 1
bottom of first distillation column 15. 5 instead of 1,000 g/hour of liquid methanol introduced
Part of the mixture in the bottom of first distillation through conduit 2. The results are shown in the same
column 15 was withdrawn by means of conduit 19, table.
pump 20, conduit 21, and valve 36. After the mixture
thus withdrawn was cooled in cooler 43 by cooling 10 Example No. 2 3 4
water 44, it was sent to second absorber 38, and then State of hydrogen Anhy Anhy
recycled to first distillation column 15 by means of chloride as used drous Aqueous Aqueous drous
solution solution gas
conduit 40, pump 41 and conduits 42 and 14. Concentration of
gas
On the other hand, a mixture of commercially avail hydrogen chloride,
able concentrated hydrochloric acid and water in a 15 % by weight 99.5< 35 15 99.5C
ratio of 1:1 by weight was introduced into second distil State of methanol
lation column 24. While the pressure of the column was as used Liquid Liquid Liquid Gas
kept at 160 mmHg (absolute) by means of vacuum Concentration of
pump 30, heating medium 32 was passed through re methanol, 9% by
boiler 31 and cooling water through a condenser 25 so 20 weight 99.3K 99.3K 99.3 < 99.3C
that the batch-wise distillation was carried out. The Amount of hydrogen
refluxing mixture to the column proved to consist of chloride supplied,
g/hour 140 3260 7600 140
water containing 0.5 percent by weight of hydrogen
chloride, and that in the bottom of the column proved Amount of hydrogen
25 chloride supplied,
to consist of hydrochloric acid containing 22 percent calculated as
by weight of hydrogen chloride. anhydrous gas,
g/hour 140 140 140 140
Into the system in which a steady state had been
established as described above with the total refluxing Amount of methanol,
g/hour 1000 1000 000 1000
in second distillation column 24 and between first dis 30
tillation column and reactor 4 were supplied 1,000 Reaction tempera
ture, C 05 05 105 05
g/hour of methanol in the liquid state and 1,140 g/hour
of anhydrous hydrogen chloride gas through conduit 2 . Pressure of the first
distillation column,
and conduit 1, respectively. The temperature in reactor kg/sq.cmG 2 2 2 2
4 was maintained constantly at 105°C, at which the 35
Pressure of the
hightest efficiency of the process was to be obtained, by second distillation
controlling the circulating flow through conduit 11. column, mmHg (abso
lute) 160 160 160 160
Part of the mixture from the bottom of first distillation
column 15 was sent to second distillation column 24, Production rate of
methyl chloride,
while the level of the liquid surface in the bottom of 40 g/hour 1560 1550 1550 1560
first distillation column 15 was kept constant by means Conversion of:
of valve 23, and the mixture in the bottom of second Hydrogen chloride,% 99 98 98 99
distillation column 24 was withdrawn approximately at Methanol, 9% 99 98 98 99
a constant rate and sent back to first distillation column 45 Dimethyl ether pro
15 by means of pump 34 and conduits 35 and 14. In the duced as byproduct,
based on the weight
meantime, water condensed in condenser 25 was dis of methyl chloride
charged through conduit 28, while the level of the produced, % by weight 0.2 0. 0.1 0.2
liquid surface in the bottom of column 24 was kept Space time yield,
constant. The results are shown in the table to be set 50 kg/cu.m. per hour" 50 130 25 150
forth at the end of this series of examples. "Spacctinc yicld expresscd as kg of mcthyl chloridc produccd per cubic mcter of
the reactor volumcpcr hour of thc reaction time.
EXAMPLE 2
In the same procedure in Example 1, 3,260 g/hour of What is claimed is:
commercially available concentrated hydrochloric acid 55 1. In a process for preparing methyl chloride by re
was introduced into the system through conduit 2 in acting a reaction mixture of hydrogen chloride with
stead of 1,140 g/hour of anhydrous hydrogen chloride methanol in the absence of any catalysts in liquid phase,
gas introduced through conduit 1. The results are the improvement which consist essentially of:
shown in the same table. a. reacting the reaction mixture in a reactor main
EXAMPLE 3 60 tained at a pressure in the range from 1 to 3
kg/cm'G;
In the same procedure as in Example 1, 7,600 g/hour b. withdrawing a part of the reaction mixture from
of diluted hydrochloric acid containing 15 percent by the reactor;
weight of hydrogen chloride was introduced into sec c, introducing a first portion of said withdrawn part
ond distillation column 24 by means of conduit 45, 65 of the reaction mixture to a first separate distilla
pump 46 and valve 47, instead of 1,140 g/hour of anhy tion column which is maintained at a pressure
drous hydrogen chloride gas introduced through con which is at least 0.1 kg/cm’G higher than the pres
duit 1. The results are shown in the same table. sure of the reactor;
 3,983,180 10
d. collecting from the top of the first distillation col i. recycling the mixture thus withdrawn to the first
umn a vapor which is richer in hydrogen chloride distillation column or to the reactor;
and methanol than the reaction mixture; j. passing a second and remaining portion of the with
e. recycling the collected vapor from step (d) to the drawn part from step (b) through an absorber and
reactor,
5 into the reactor while concurrently withdrawing
f, withdrawing from the bottom of the first distillation methyl chloride formed in the reactor from its top
column a mixture which is lower in hydrogen chlor and passing the methyl chloride through said ab
ide and methanol concentration than the reaction sorber in counter current flow to said remaining
mixture and introducing a part of mixture to a 10 portionanol
to absorb the hydrogen chloride and meth
from the methyl chloride, and then collecting
second separate distillation column which is main the methyl chloride.
tained at a pressure from 10 to 500 mmHg abso 2. The process of claim 1 wherein the collected
lute; methyl chloride is passed into a second absorber in
g. discharging from the top of the second distillation counter current flow with the mixture from the bottom
column water contained in the hydrogen chloride 15 of the first distillation column which acts as an absorp
and methanol and water generated during the reac tion medium.
tion; 3. The process of claim 1 wherein hydrochloric acid
h. withdrawing from the bottom of the second distil which is more dilute than the azeotropic composition at
lation column a mixture richer in hydrogen chlor the pressure of the first distillation column is first intro
ide than the mixture in the bottom of the first distil- 20 duced into the second distillation column.
k sk ck ck sk
lation column;

25

30

35

40

45

50

55

60

65 -