Aug.

25, 1959

J. W. COLTON

2,901,407

HYDROGEN CHLORIDE PURIFICATION

Filed July 31, 1957

20

PARTIAL
CONDENSIE; SYSTEM

X l5
'

FIRST

SEPARATION
ZONE

SECOND
SEPARATION

l5

)6

ZONE

:IO
REBOILER
|I

INVENTOR.
John W. Colion

Unite. States Patent O?Fice

2,901,407
Patented Aug. 25, 1959

2
more concentrated with respect to hydrogen chloride than

said original contaminated aqueous hydrochloric acid

solution is removed'through line 6 by pump 7 to a

2,901,407

second separation zone 8 maintained at a pressure higher

than that maintained in said ?rst separation zone. An
aqueous hydrochloric acid solution of azeotropic con
John White Colton, Pelham Manor, N.Y., assignor, by
mesne assignments, to Scienti?c Design Company, Inc.,
centration is removed through line 9 from said second
a corporation of Delaware
.
separation zone. A portion 10 is recycled to reboiler 11,
and back to the separation zone. The remaining por
Application July 31, 1957, Serial No. 675,422
tion is removed through line 12 as liquid effluent 13 and
may be used elsewhere in the process, for example, as
6 Claims. (Cl. 20242)
a scrubbing medium.
Vapor e?iuent of hydrogen chloride and water is re
moved from separation zone 8 through line 14. A por
This invention relates to hydrogen chloride puri?ca 15 tion of this stream is introduced through line 15 into
tion, particularly by separation. More particularly, this
said ?rst separation zone sul?cient to effect said sep
invention relates to a process for the manufacture of
aration in said ?rst zone, i.e. supply means to effect sep
anhydrous hydrogen chloride having economic advan4

HYDROGEN CHLORIDE PURIFICATION

tages over the prior art.

'

aration. The remaining portion of said vapor e?iuent

is passed through line 16 into a partial condenser sys

I It is the object of the present invention to provide a 20

tem 17, which consists of a ?rst condenser operated with
process for the puri?cation of hydrogen chloride where

in substantial savings are. realized in both capital and

operating

costs.

"

cooling water and a second condenser operated with

refrigeration.

An aqueous hydrochloric acid solution

which is separated in the ?rst condenser is returned to

said second separation zone by line 18. Line 19 re

In a preferred embodiment the invention comprises a

cyclic process for the puri?cation of a contaminated 25
moves the desired substantially anhydrous hydrogen
aqueous hydrochloric acid solution which comprises the
chloride product 20 from the refrigerated condenser.
steps of: passing said aqueous solution into a ?rst separa
Condensate from the refrigerated condenser is returned
tion zone, removing from said separation zone as separate
to the second separation zone through line 18.
streams hydrogen chloride vapor containing said con~
It will be apparent from a reading of the foregoing
taminants and an aqueous hydrochloric acid e?luent 30
disclosure
that the described process produces palticular
more concentrated with respect to hydrogen chloride
technical advantages over the prior art. For example,
than said contaminated aqueous hydrochloric acid solu
in the prior art method two reboilers are required, one
tion, passing said effluent into a second separation zone
for each of the separation zones whereas when operat
maintained at a pressure higher than that maintained in
ing according to the process of this invention only one
said ?rst separation zone, removing from said second 35 reboiler
is necessary, in the second separation zone. The
separation zone as separate streams an aqueous hydro~
economic advantageof this reboiler reduction can be
chloric acid solution of azeotropic concentration and: a
seen when the total utilities, steam and cooling water,
vapor ef?uent of hydrogen chloride and water, introduc
are assumed constant, for under these circumstances the
ing a portion of said vapor eliluent into said ?rst sep
prior
art requires 60 percent more theoretical plates
aration zone su?icient to effect said separation in said 40
than
the
instant process, thereby increasing capital costs.
?rst zone, separating the remaining portion of said vapor
Further, operating according to the prior art a 25 C.
e?luent into substantially anhydrous hydrogen chloride
and aqueous hydrochloric acid solution.

higher operating temperature is required at the bottom

of the ?rst separation zone thereby increasing the op
erating and maintenance difficulties which are inherent

The contaminants contained in the aqueous hydro

chloric acid feed consist generally of chlorine and chloro 45 when operating apparatus such as distillation columns
carbons such as carbon tetrachloride, perchloroethylene,
and pumps with aqueous hydrochloric acid at elevated
methylene chloride, methyl chloride, and chloroform.
temperatures.
The key contaminant is usually the least volatile con
In another comparison, the packed height of the sec
taminant in the aqueous hydrochloric acid solution and
ond separation zone or hydrogen chloride stripper is
it is the most difficult one to strip to the desired product 50 assumed the same in both the prior art and the process

speci?cation.

The invention has particular applicabilityto aqueous

hydrochloric acid solutions obtained in the course of,

of this invention. Under these circumstances the prior

art method requires 20 percent more steam and 130

percent greater condenser load; in addition, the vapor

thermal chlorination of aliphatic hydrocarbons and in
ef?uent is less concentrated.
which processes there are produced aqueous hydrochloric 55
In still another comparison, the hydrogen chloride
acid solutions by virtue of the use of aqueous media for
stripper reboiler heat duty is assumed the same. Under
dissolving the hydrogen chloride byproduct. These
these circumstances the prior art requires 25 percent
aqueous solutions contain such contaminants as set forth
more steam, 180 percent more condenser load, and the
above.
The following detailed description taken in conjunction 60 concentration of the overhead hydrogen chloride vapor
is approximately 18 percent lower.
with the accompanying drawing will show that the puri
Thus, it is apparent from a reading of the foregoing
?cation art has been technically advanced according to
the process of this invention.
disclosure that the present invention provides a process
The drawing is a diagrammatic illustration of one
for the puri?cation of hydrogen chloride wherein sub
embodiment of the process of the instant invention.
65 stantial savings are realized in both capital and operating
costs.
Referring now to the drawing in detail: a contaminated
aqueous hydrochloric acid solution 1 is fed through line
The minimum volume of vapor ef?uent that is required
2 to a ?rst separation zone 3, maintained at approxi-
to be returned to the ?rst separation zone is expressed by

mately atmospheric pressure. Hydrogen chloride con

taining said contaminants 4 is removed as overhead vapor

through line 5. An aqueous hydrochloric acid effluent

the following equation: .

'

2,901,407
3

all such variations and modi?cations except as do not

come within the scope of the appended claims.
I claim:
1. In a cyclic process for the puri?cation of a con

V=vo1ume of stripping vapor (mols)

L=volume of liquid (mols)

at equilibrium of hey contaminant

taminated aqueous hydrochloric acid solution, the steps

of: passing said aqueous solution into a ?rst separation
zone, removing from said separation zone as separate

where

streams hydrogen chloride containing said contaminants

y is the concentration of key, component in the vapor

phase (mole fraction)

the art and it is intended to include within the invention

where

10 and an aqueous hydrochloric acid effluent more concen

'

x is the concentration of key component in the liquid

phase (mole fraction)

trated with respect to hydrogen chloride than said orig

inal contaminated aqueous hydrochloric acid solution,

passing said e?iuent into a second separation zone main

The key contaminant is the most difficult one to strip
tained at a pressure higher than that maintained in said
to a speci?cation concentration, and is usually the least 15 ?rst separation zone, removing from said second separa
volatile contaminant in the aqueous hydrochloric acid
tion zone as separate streams an aqueous hydrochloric
solution.
acid solution of azeotropic concentration and a vapor
The maximum volume of vapor e?'luent that is returned
e?luent of hydrogen chloride and water, introducing a
to the ?rst separation zone is controlled by the economics
portion of said vapor efliuent into said ?rst separation
of the process and generally will not exceed 60 percent 20 zone suf?cient to effect said separation in'said ?rst zone,
ofthe vapor e?iuent. A range of about 5 to 40 percent
separating the remaining portion of said vapor e?luent
has been found to give satisfactory results, while 15 to
into anhydrous hydrogen chloride and aqueous hydro
30 percent is preferred.
chloric acid solution.
The following example is illustrative of the present in
2. The process according to claim 1 wherein the pres
vention but is not to be construed as limitative thereof.
25 sure of said second separation zone is maintained between
Example
about one and three atmospheres absolute.
3. In a cyclic process for the puri?cation of a con
An aqueous hydrogen chloride solution containing
taminated aqueous hydrochloric acid solution, the steps
about 33 percent hydrogen chloride and small amounts
of: passing said aqueous solution into a ?rst stripping
of contaminants resulting from quenching the reactor
stream of a propane/propylene chlorinator process for 30 zone, removing from said stripping zone as separate

the production of perchloroethylene and/ or carbon tetra

chloride is fed to a stripping column maintained at a

pressure in the range 700 to 1,000 mm. of Hg and at
59 to 71 C. The vapor effluent from this column is
a stream of hydrogen chloride containing about 5 per 35

cent water and the contaminants.

The liquid effluent

streams hydrogen chloride containing said contaminants

and an aqueous hydrochloric acid efliuent more concen

trated with respect to hydrogen chloride than said con

taminated aqueous hydrochloric acid solution, passing said
e?luent into a second stripping zone maintained at a pres

sure higher than that maintained in said ?rst stripping

zone, removing from said second stripping zone as sep

from said column is a 37 percent aqueous solution of
arate streams an aqueous hydrochloric acid solution of
hydrogen chloride and is fed to a second stripping column
azeotropic concentration and a vapor e?luent of hydrogen
maintained at a pressure in the range 1,500 to 2,000 mm.
Hg and at 84 to 135 C. The liquid e?luent of the 40 chloride and water, introducing a portion of said vapor
effluent into said ?rst stripping zone su?icient to effect
second column consists of an aqueous hydrochloric acid

of about 21 percent hydrogen chloride content, which is

near the azeotropic concentration. An approximately
25 percent portion of the vapor e?iuent from this second
stripping column is returned to the ?rst stripping column. 45

said separation in said ?rst stripping zone, separating the

remaining portion of said vapor effluent into substantially
anhydrous hydrogen chloride and aqueous hydrochloric
acid solution and returning this aqueous hydrochloric acid

solution to said second stripping zone.

4. The process according to claim 3 wherein the pres
sure of said second stripping zone is maintained between
about one and three atmospheres absolute.
ping column and substantially anhydrous hydrogen chlo
5. In a cyclic process for the puri?cation of a contam
ride is recovered as product from the refrigerated con 50

The remaining portion is passed to the partial condenser

system where aqueous hydrogen chloride is returned, after

leaving the cooling water condenser, to the second strip
denser.

inated aqueous hydrochloric acid solution, the steps of:

passing said aqueous solution into a ?rst stripping zone,

It will be realized that the portion of the vapor effluent
removing from said stripping zone as separate streams
returned to the ?rst stripping column, rather than the
hydrogen chloride containing said contaminants and an
approximately 25 percent set forth above, can be varied
widely, such as for example, the range generally will not 55 aqueous hydrochloric acid ef?uent more concentrated
with respect to hydrogen chloride than said contaminated
exceed 60 percent and 5 to 40 percent for satisfactory

operation.

aqueous hydrochloric acid solution, passing said ef?uent

The desired operating pressure of the ?rst separation

zone is about 0.9 atmosphere to about 1.5 atmospheres

higher than that maintained in said ?rst stripping zone,

that maintained in said ?rst separation zone and is gen

erally between about one and three atmospheres. Low.

tropic concentration and a vapor effluent of hydrogen

chloride and water, introducing less than about 60 per
cent of said vapor effluent into said ?rst stripping Zone,

into a second stripping zone maintained at a pressure

removing from said second stripping zone as separate

with atmospheric pressure being preferred. The second 60 streams
an aqueous hydrochloric acid solution of azeo
separation zone is maintained at a pressure higher than

pressures require recycling large volumes of the azeotrope

separating the remaining portion of said vapor e?iuent;

mixture and increase the steam consumption. The upper 65 into substantially anhydrous hydrogen chloride and
pressure limit is governed by materials of construction
aqueous hydrochloric acid solution.
and the economics of operation. A preferred operating
6. In a cyclic process for the puri?cation of a con
range is about 10,to 20 p.s.i.g.
taminated aqueous hydrochloric acid solution, the steps
By means of the foregoing procedure it is possible to
passing said aqueous solution into a ?rst stripping
separate substantially anhydrous hydrogen chloride free 70 of:
zone, removing from said stripping zone as separate
of such objectionable contaminants as chlorine and chlo
streams hydrogen chloride containing said contaminants
rocarbons such as carbon tetrachloride, perchloroethylene,

methylene chloride, methyl chloride and chloroform.

and an aqueous hydrochloric acid e?luent more concen

trated with respect to hydrogen chloride than said con

In view of the foregoing disclosures, variations and
modi?cations thereof will be apparent to one skilled in 75 taminated aqueous hydrochloric acid solution, passing

2,901,407

said et?uent into a second stripping zone maintained at a

References Cited in the ?le of this patent

pressure higher than that maintained in said ?rst stripping

UNITED STATES PATENTS

zone, removing from said second stripping zone as sep

arate streams an aqueous hydrochloric acid solution of

2366361

asmclm et a1" ---------- -- Jan 2' 1945

azeotropic concentration and a vapor eifluent of hydrogen 5

2730194

oh ers at al' ------- --~ Jan' 10 1956

chloride and water, introducing from about 15 to 30%

of said vapor e?iuent into said ?rst stripping zone, sep

OTHER REFERENCES

varating the remaining portion of said vapor e??uent into

substantially anhydrous hydrogen chloride and aqueous

Bl'llmballgh 6? al-i Synthesis and Recovery of Hydro

gen Chloride Gas," Industrial and Engineering Chem

hydrochloric acid solution,

10 istry, vol. 41, October 1949, pp. 2165-2167.