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July 19, 193s.
>
R. H. MCKEE
.
2,124,426
METHOD 0F GONTINUOUSLY SEPARATING UNSATURATED HYDROGARBON
GASES FROM SATURATED HYDROCARBON GASES
Filed Jan. 26. 1955
2 Sheets-Sheet l
‘l 1.
ATTORNEY.
2,124,426
July 19,1938.
. ,
R. H_YMQKEE
METHOD OF CONTINUOUSLY SEPARATING UNSATURATED HYDROCARBON
GASES FROM SATURATED HYDROCARBON GASES
Filed Jan. 26, 1935
2 Shee‘lìS-Shee‘l’l 2
ma PH H. _Ms/f5.5
BY Q
ATTORNEY,
Patented July i9, 193s
.
i‘v2,124,426'
_ UNITED sTATEs PATENT OFFICE
METHOD OF CONTINUOUSLY SEPARATING
UNSATURATED
HYDROCARBON , GASES
FROM SATURATED HYDROCARBON GASES
vRalph H. McKee, New York, N. Y., assignor'to
Cesare Barbieri, New York, N. Y.
- Application January 26, 1935, Serial No. 3,674
'
14 claims.
(01260-162)
The present invention relates to an improved
method of continuously separating unsaturated
aliphatic hydrocarbon gases from saturated'
aliphatic hydrocarbon gases, especially gases pro
duced in petroleum -and similar cracking pro
Y
It is also within the contemplation of the in
vention to provide a continuous method of sepa
rating unsaturated aliphatic hydrocarbons from
saturated aliphatic hydrocarbon gases in a simple
' apparatus, in which halogens are prevented from
cedures.
It is well known that heretofore various methods
have been used to separate unsaturated hydro
carbons from lsaturated hydrocarbon gases.
The more important methods involved liquefac- ,
dissolving in the manufactured alkylene halide.`
The invention also contemplates the provision
of a method of’separating unsaturated hydro
carbons from saturated hydrocarbons which is
l susceptible to heat control and which prevents
tion and the use of high pressures and low tem ' the attainment of excessive temperatures detri
peratures to liquefy certain of theconstituents ì ,mental to high efiiciency and high yields.
of the gas mixture and to permit their separa- ` 'ï It is a further object 4of the invention to pro
tion. One of the outstanding systems of this -ífvide a continuous method which is economical,
15. type was the so-called Linde process. As is well>
hich is commercial, and which can be carried
known, this. process has many disadvantages, of
ntopractice on an industrial scale with a mini
which may be mentioned the high initial in
'um production of products formed from satu
vestment required for an installation capable of ¿, `-`rated hydrocarbons by the action of free halogens.
separating unsaturated hydrocarbons from satu
“Other objects and» advantages of the invention
rated hydrocarbon gases on an industrial scale._ .will become apparent from the following descrip 20
Moreover, the necessity for using high pressures> `tion of preferred procedures >taken in conjunc
and low temperatures required the expenditure of
large amounts‘of ,energy and involved high oper
ating costs and high maintenance expenses.
Various methods were proposed to replace the4
liquefaction systems. Of these proposals, the
sulfuric acid method may be mentioned as prob
ably the most important. In this method, sul
furic acid was used to> react chemically with the
30 unsaturated hydrocarbons. In practice, com
plicated side reactions occurred as well as poly
merization. Duc to the complications of the
process and the corrosive nature of sulfuric acid
and the ineiîìcient yields and recoveries, the sul
furic -acid process lhas not been able to replace
the so-called Linde liquefaction system which has
tion
with
the
accompanying - drawings,
in
Which:
-Fig. 1 depicts diagrammatically apparatus
adapted to carrying the present process into prac
y tice;
-Fig. 2 is similar to Fig. l oi modiñed apparatus;
-
and>
_
.
-Fig. 3 illustrates a ñow slieet'of the present
process in conjunction with speciñc agents, gases,
etc.
The present invention contemplates the con
tinuous treatment of an acidifìed solution of a
aliphatic hydrocarbons from saturated aliphatic
halide with gaseous chlorine in excess of stoi
chiometric quantity to liberate bromine and to
form bromine chloride (BrCl) `and with a gas
-containing saturated and unsaturated hydro
carbone to effect substantially complete halogen- .
ation of the unsaturated hydrocarbons without
halogenating saturated hydrocarbons to any ap 40
preciable extent. The treated gases are subjected
to absorption and adsorption whereby gaseous
bromine and hydrocarbon halides are recovered
for re-use and for consolidation and the residual
gas containing practically all of the saturated 45
hydrocarbons is in an unaffected condition. In
carrying the invention into practice, it is pre
ferred to flow a strong or concentrated salt solu
tion of a halide of an alkali or alkaline earth
metal (e. g. sodium bromide) practically con
hydrocarbon gases which can be carried into
tinuously through a saturator, preferably in the
probably been the -most important industrially.
Although various procedures have been sug
gesteld to replace prior systems, none, as far as
I am aware, has been provided> which is- _wholly
satisfactory and acceptable. in industrial prac
tice.
I have discovered an improved procedure of
continuously separating unsaturated i rom satu
4. rated hydrocarbons which overcomes the disad
vantages of the prior art and which is very simple
_to carry into practice without uninfected by
'products and'loss of halogens.
It is an object of the invention to provide a
continuous method of separating unsaturated
practice industrially at substantially normal pres
sures and temperatures with increased yields and
„1 in with recovery of alkylene halides from exit gases.
form of a tower. A stream of chlorine gas and a
stream of unsaturated and saturated hydrocar
bon gas are flowed practically continuously and 55
2
2,124,426
countercurrent to said stream of salt solution.
The gas streams preferably are introduced into
the solution at about the same region and about
simultaneously with each other. For best prac
tical results, a small amount of unsaturated and
saturated hydrocarbon gas is introduced into
the solution at the bottom of the tower adjacent
to the outlet from which the halogenated product
is withdrawn and the hydrocarbon gas is also
solution or liquor, conventional methods may be
utilized.
Referring more particularly to Fig. 1, the refer
ence character T designates an elongated vertical
tower preferably provided with a water jacket.
'Through inlet i, a salt solution of a halide of
an alkali’metal is introduced into the tower
and is caused to ñow downward. Chlorine gas
is added to the solution via inlet 2 and is per
introduced into the solution in the upper part of
the tower but below the inlet for the halide salt
mitted to flow upward countercurrent to the
solution. By regulating the amount of chlorine
to the chlorine gas inlet is a second inlet 3 for
gas admitted to an excess< of stoichiometric quan
tities, bromine is liberated in amounts exceeding
15 yits normal solubility in water and in amounts
causing the formation of bromine chloride. In
this manner, a large amount of halogen is present
and the halogenation of the unsaturated hydro
carbons is effected readily and efficiently where
20 by practically all of the unsaturated hydrocar
bons are halogenated and the saturated hydro
carbons remain unaffected. By conducting the
foregoing operations in the dark, the possibility
of halogenating saturated hydrocarbons is re
25 duced and practically eliminated.
For guiding
those skilled in the art in regulating the addition
of chlorine gas to the acidified salt solution, the
addition is continued until the bromine is liber
ated and the brownish colored bromine solution
30 is rendered colorless thereby assuring the use of
chlorine in excess of stoichiometric quantity and
the setting free from the alkali or alkaline earth
metal of substantially all of the bromine and Athe
formation of bromine chloride. In this manner,
35 an amount of bromine may be provided in the
solution in excess of amounts provided heretofore.
The heat liberated in the aforesaid reactions can
be readily controlled due to the fact that a rela
tively large amount of water is present in the
40 solution in the tower and due to the use of a
cooling jacket (not shown in figures) contain
ing cooling water surrounding the tower.
The used or treated gas is washed with an
alkaline solution, preferably a caustic soda solu
tion
to recover bromine, chlorine and other halo
45
gens. After being washed thoroughly, the gas is
ì passed through an adsorbent, such as activated
carbon, to remove hydrocarbon halides which
can be subsequently recovered from the carbon
as by steaming. The bromine thus recovered can
50
be reused and the -adsorbed hydrocarbon halides
can be merged with the halogenated product.
`The waste salt solution or liquor comprises es
sentially a sodium chloride solution containing
55 some ethylene bromhydrin, chlorhydrin, etc.
For the purpose of recovering the bromhydrin,
etc., the waste liquor is run into a large wooden
separating tank from which the product is col
lected and removed. To the residual liquor, acid
is added until a pH of about 3 is obtained if the
liquor is not already acid to this extent. The
acidiñed liquor is heated to a temperature of
approximately 80° C. By permitting the by
products, such as ethylene bromhydrin, ethylene
65 chlorhydrin, etc., to stand in the tank, they are
converted by hydrolysis into glycol, hydrobromic
acid, hydrochloric acid, etc. After hydrolysis
is about complete, a small amount of chlorine
can be run into the tank where it will react
with hydrobrornic acid to liberate bromine. By
blowing air into the tank, bromine can be re
moved and can be recovered in an alkaline solu
tion, such as a sodium carbonate solution. The
recovered bromine can be returned to the system
75 for reuse, For recovering the glycol from the salt
downwardv ñowing solution.
Closely adjacent '
-the introduction of unsaturated and saturated
hydrocarbon gases which rise upward simultane
ously with and contiguous to the chlorine. By 15
regulating the chlorine in excess of stoichiometric
quantity, ~amounts of bromine may be dissolved
in excess of solubility amounts and bromine
chloride may be formed. Due to the presence
of such excessive amounts of bromine and of 20
bromine chloride, the lhalogenation of. the un
saturated hydrocarbons is very efficient. As the
hydrocarbon gases closely follow the stream of
chlorine, the unsaturated hydrocarbons are pres
ent at practically the’ instant the bromine is 25
liberated and the bromine chloride is formed.
The halogenated hydrocarbons are liquid and
fall to the bottom ofthe tower. At the bottom,
the halogenated product is removed by means of
an outlet 4 together with the salt solution or 30
liquor.
Closely adjacent to the bottom of the
tower, an auxiliary gas inlet 5 is provided for
the introduction of hydrocarbon gases to the
solution. By adding gas in the region of the out
let any free halogen will react with unsaturated 35
hydrocarbons and will prevent the discharge of
free halogens with the product -and with the
waste solution. In the upper part of the tower
and below salt solution inlet i, a second auxiliary
inlet 6 is provided for hydrocarbon gases. This
auxiliary gas stream contacts with free halogens. 40
-In this mannen'unsaturated hydrocarbons re
act with the free halogens and remove them
from the rising gases. By controlling the amount
of auxiliary gas, practically all of the free halo
gens may be used and halogenated product may 45
be produced.
At the top of the tower, a gas outlet 1 is
located for the Withdrawal of the treated or used
gases. Due to the partial vapor pressure of the
halogenated hydrocarbons, the vapor of these 50
halogenated products may be present in the exit
gases. In addition, the gases may contain some
unused free halogens. The exit gases contain
ingv some free halogens and some hydrocarbon
halides are passed through a washer 8 and are
washed with an alkaline solution, such as a
caustic soda solution. In this washing operation,
practically all of the free halogens-are absorbed
and are recovered as a halide or halate. From
the alkali Washer 8, the gases pass through an 60
adsorber 9 containing activated carbon which
adsorbs halogenated hydrocarbons and residual
free halogens. To recover the halogenated hy
drocarbons and the halogens, the activated car
bon is steamed.
A second adsorber l0 is pro
vided for use while the ñrst adsorber is being
steamed. After the adsorption treatment, the
exit gases are practically wholly of a saturated
character substantially devoid of unsaturated 70
hydrocarbons, free halogens, and halogenated hy
drocarbons. The treated exit gases may be
passed to a gas holder (not shown) for light, heat
power, and other uses.
In some instances, it may be desirable to use 75
3
A» 2,124,426
two towers instead of one tower. A two tower
saturated hydrocarbons. Some- free halogens
(bromine, chlorine and bromine chloride) and
system is illustrated in Fig. 2 wherein the refer
ence characters T-I and T-'-2 designate the the vapors of the hydrocarbon halides (ethylene
first and second towers, respectively. In the ñrst bromide, etc.) may also be present in the un
used or exit gas. This gas is first Washed with
tower T--I, an inlet I is provided for a salt solu
an alkaline solution, such as caustic soda solu
tion of a halide of an alkali metal from the sec
tion, etc., to remove and recover the free halo
ond tower. Through a gas inlet .3, the unsat
gens for reuse.
From the washer, the gas is
urated and saturated hydrocarbons are intro
duced into the ñrst tower. The solution and the
10 product are removed from the tower via an out
'carbon which will adsorb and recover hydro
Il. At the top of tower T-‘2, a gas outlet l5 is
provided from which the exit gases go to washerV
may be used, shipped, etc. The salt solution con
passed through an adsorber containing activated
10
let I. Above the outlet and in the bottom of> carbon halides. In the event any free halogens
the tower is an auxiliary gas inlet 5. At the top `are still present, they will likewise beadsorbed.
of the 'first tower, a gas outlet 1 is providedrto In practice, the following types _of adsorbent ma
convey the exit gases to the second tower T--2. terial may be used: activated carbons,.silica gels,
In the second tower, an inlet Il is located in or zirconia gels, but of these, activated carbons 15'
15
are preferred.
the upper part to introduce the fresh salt (NaBr)
From the tower, the solution is withdrawn vla _
solution. Into the salt solution, exit or used
an automatic decanter which separates the prod
hydrocarbon gas from .the iirst tower is intro
duced via gas inlet I 2l in the lower part of‘ the uct and the salt solution. 'I'he product may then
be subjected to distillation and separated into its 20
20 tower T-2. An auxiliary gas inlet I3 is like
components. After distillation, the distilled
wise incorporated in the lower part of the sec
ond tower and positioned above'al liquor outlet products, such as ethylene brom-chloride, ethyl
ene-dibromide, proplyene brom-chloride, etc.,
taining principally sodium chloride and ethylene 25
bromhydrin and chlorhydrin is withdrawn to a
25 l. After passingv through the washer, the exit
gases are conducted to either the adsorber 9 or
,
wooden tank in which it is acidiñed with some
For the purpose of giving those skilled in the
art a better understanding of the invention, the
cheap acid like sulfuric acid, etc., to a pH of about
3. By acidifylng the solution, glycol [C2H4(0H)zl
adsorber I0.
30 following specific illustrative example will be
and hydrobromic acid are formed.
Bromine may 30
given in conjunction with Fig. 3.
About 20. to about 40 parts by weight of sodi
be liberated from this acid by passing chlorine
gas through the solution and may be removed by
" um bromide are added to about 100 parts by blowing air through the solution. The air carry
weight of water to form a strong or concentrated ' ing the bromine may then be conducted to the
In some instances a more
alkali absorber orwasher where it will be con 35
or less saturated salt solution is used. Chlorine -verted into sodium bromide which can be re
gas is added to the strong salt solution in excess used. The residual aqueous salt solution con
taining glycol may be treated for the recovery of
of stolchiometric quantities. In other words, suf
.
ilcient chlorine is added to convert and liberate theglycol.
40 substantially all of the bromide in the salt solu
40
I claim:
~
tion into free bromine and to combine with said
1. The method of continuously separating un
free bromine to form bromine chloride. By this. saturated hydrocarbons from saturated hydro
treatment, the usual brown color of a bromine
carbon gases and isolating substantially pure sat
containing solution disappears. This is in con
urated hydrocarbons practically devoid of unsat
45 trast to prior procedures in which brown bromine
urated hydrocarbons which comprises establish
35 halide salt solution.
containing solutions were utilized.
50
55
60
65
70
75
,
. ing an acid solution of sodium bromide, continu
The strong salt solution or liquor containing ously passing chlorine gas through said solution
sodium chloride and bromine chloride is cooled - in amounts in excess of stoichiometric quantities
to about 10° C. or 20° C. and is added to a satura
to liberate bromine from the bromide in said solu
tor, preferably a darkened and water- jacketed tion and to form bromine chloride, continuously 50
tower of the type described hereinabove. contacting a gas containing saturated and un
Through the solution unsaturated and saturated saturated hydrocarbon gases with said solution
hydrocarbon gas is introduced, preferably whilst moving to cause said unsaturated hydro
through a perforated plate or body of porcelain, carbons to react with said bromine chloride to
earthenware, “Filtros’.’, or fritted glass or other form brom-Chlor hydrocarbons, continuously re 55
solid having an abundance of small pores. ' The
moving said brom-chlor hydrocarbons from the
gas passes upwardly and countercurrent to the solution to facilitate the recovery of hydrocarbon
downward flowing solution. Although any gas halide, continuously passing the unreacted gas>
containing unsaturated hydrocarbons' may' be through an alkali washer for the recovery of
used, satisfactory results have been obtained with free halogens, and continuously bringing the re 60
gas -from petroleum vapor phase crackingv sys
sidual gas into contact with an adsorbent mate
tems which contains principally saturated hydro
rial for the absorption of halogenated hydrocar
carbons and unsaturated hydrocarbons including bons and for the isolation of substantially pure ,
ethylene, propylene, butylene, amylene, acetylene, saturated hydrocarbons practically devoid of un
methyl acetylene or alkylenes, etc. In the tower saturated hydrocarbons.
65
the unsaturated hydrocarbons are halogenated.
2. The method of continuously separating un
saturated hydrocarbons from saturated hydro
Thus, ethylene- is halogenated to ethylene brom
carbon gases and isolating substantially pure sat
chloride or ethylene dichloride or ethylene d_i
urated hydrocarbons practically devoid of unsat
bromide and acetylene to acetylene dibromide di
chloride or other acetylene tetrahalide. If the urated hydrocarbons which comprises establish 70.
aqueous solution is dilute, substantial amounts of ing a flowing solution containing about 10 to _
ethylene bromhydrin or ethylene chlorhydrin will .about 20 parts by weight of sodium bromide and
about 100 parts by weight of water, continuously
be formed by the addition ofthe hydrolyzed hal
passing chlorine gas through said solution in
ide (HOBr or HOCl) to the ethylene. The re
malning or unused gas consists principally of amounts in excess of stoichiometric quantities t0 75
4
3,124,426
liberate bromine from the bromide in said solu
tion and to form bromine chloride, cooling said
solution to about 10° C. to about 20° C., continu
ouslyÍ contacting a gas containing saturated and
unsaturated hydrocarbon gases with said flowing
solution to cause said unsaturated hydrocarbons
to react with said bromine chloride to form brom
chlor hydrocarbons, continuously removing said
brom-chlor hydrocarbons from the solution to fa
10 cilitate the recovery of hydrocarbon halide, con
bringing a gas containing unsaturated and satu
rated hydrocarbons in contact with said flowing
solution to cause unsaturated hydrocarbons to
react with free halogens including said bromine
chloride and to form halogenated hydrocarbons,
separating said halogenated hydrocarbons from
said solution, continuously passing the unreacted
gas through an alkali solution for the absorp
tion of free halogens, and continuously bringing
tinuously passing the unreacted gas through an
residual gas into contact with adsorbent mate
rial for the recovery of halogenated hydrocar
alkali washer for the absorption of free halogens,
and bringing the residual gas into contact with
bons and for the isolation of substantially pure
saturated hydrocarbons practically devoid of un
an adsorbent material for the recovery of halo
saturated hydrocarbons.`
15 genated hydrocarbons" and for the isolation of
substantially pure saturated hydrocarbons prac
tically devoid of unsaturated hydrocarbons.
3. The method of continuously separating un
saturated hydrocarbons from >saturated hydro
20 carbon gases and forming substituted derivatives
of saturated hydrocarbons from unsaturated
constituents which comprises establishing a solu
tion of sodium bromide, continuously passing
chlorine gas through said solution in amounts in
25 excess of stoichiometric quantities to liberate
bromine from the bromide in said solution and to
form bromine chloride, continuously contacting a
gas containing saturated and unsaturated hydro
carbon gases with said solution whilst flowing to
10
'
6. The method of continuously separating un
saturated hydrocarbons írom saturated hydro
carbon gases and isolating substantially pure
15
saturated hydrocarbons practically devoid of un
saturated hydrocarbons which comprises estab
lishing a downward flowing solution containing 20
sodium bromide, continuously controlling the
temperature of said solution to about 10° C. to
about 20° C., continuously passing chlorine gas
upward through said flowing solution in amounts
in excess of stoichiometric quantities to liberate 25
bromine from the bromide of said flowing solu
tion and to form bromine chloride, continuously
bringing a gas containing unsaturated and satu
rated hydrocarbons in contact with said flowing
solution to cause -unsaturated hydrocarbons to 30
30 cause said unsaturated hydrocarbons to react
with said bromine chloride to form brom-chlor _ react with free halogens including said bromine
hydrocarbons, continuously removing said brom
chlor hydrocarbons from the solution to facilitate
the recovery of hydrocarbon halide, acidifying the
residual solution to a pH of about 3 and heating
said solution to about 80° C. to effect hydrolysis
of any hydrins to glycols.
4. The method of continuously separating un
saturated hydrocarbons from saturated hydro
40 carbon gases and isolating substantially pure sat
urated hydrocarbons practically devoid of un
saturated hydrocarbons which comprises estab
lishing a downward flowing solution containing
sodium bromide, continuously passing chlorine
gas upward through said flowing solution in
amounts in excess of stoichiometric quantities to
liberate bromine from the bromide of said flowing
solution and to form bromine chloride, continuously bringing a gas containing unsaturated and
50 saturated hydrocarbons in contact with said flow
ing solution to cause unsaturated hydrocarbons
to react with free halogens including said bro
mine chloride and to form halogenated hydro
carbons, continuously separating said halogen
55
ated hydrocarbons from said flowing solution,
continuously passing the unreacted gas through
an alkali solution for the absorption of free halo
_ gens, and continuously bringing residual gas into
contact with adsorbent material for the recovery
60 of halogenated hydrocarbons and for the isola
tion of substantially pure saturated hydrocarbons
practically devoid of unsaturated hydrocarbons.
5. The method of continuously separating un
saturated hydrocarbons from saturated hydro
carbon gases and isolating substantially pure
saturated hydrocarbons practically devoid of un
saturated hydrocarbons which comprises estab
lishing a downward ñowing solution containing
about 10 to 40 parts by weight of sodium bro
70 mide and about 100 parts by weight of water,
continuously passing chlorine gas upward
chloride and to form halogenated hydrocarbons,
,continuously separating said halogenated hydro
f'carbons from said flowing solution, continuously
passing the unreacted gas through an alkali solu
tion for the absorption of free halogens, and con
tinuously bringing residual gas into contact with
adsorbent material for the recovery of halogen
ated hydrocarbons and for the isolation of sub
stantially pure saturated hydrocarbons prac 40
tically devoid of unsaturated hydrocarbons.
7. 'I'he method> of continuously separating un
saturated hydrocarbons from saturated hydro
carbons gases and forming substituted deriva
tives of saturated hydrocarbons from unsatu
rated constituents which comprises establishing
a downward flowing solution containingy sodium
bromide, continuously passing chlorine gas up
ward through said solution in amounts in ex
cess of stoichiometric quantities to liberate bro
mine from the bromide of said solution and to
form bromine chloride, continuously bringing a
gas containing unsaturated and saturated hydro
carbons in contact with said flowing solution to
cause unsaturated hydrocarbons to react with
free halogens including said bromine chloride
and to form halogenated hydrocarbons, continu
ously separating said halogenated hydrocarbons
fromv said solution, acidifying the solution to a
pH of about 3 and heating to about 80° C. to
cause the hydrolysis of hydrins to glycols.
8. The method of continuously separating un
saturated hydrocarbons from saturated hydrocar
bon gases and forming substituted derivatives of
saturated hydrocarbons from unsaturated con 65
stituents which comprises establishing a down
ward flowing solution containing sodium bromide,
continuously passing chlorine gas upward through
said solution in amounts in excess of stoichio
metric quantities to liberate bromine from the
bromide of said solution and to form bromine
chloride, continuously bringing a gas containing
through said flowing solution in amounts in ex
cess of stoichiometric quantities to liberate bro - unsaturated and saturated hydrocarbons in con
mine from the bromide of said flowing solution tact with said flowing solution to cause unsatu
75 and to form bromine chloride, continuously
35
rated hydrocarbons to react with free halogens
5
, 2,124,426
including said bromine chloride '4 and to form
halogenated hydrocarbons, continuously separat
ing said halogenated hydrocarbons from said
' solution,.acidifying the solution to a pH of about
3 and heating to about 80° C. to cause the hy
drolysis of hydrins to glycols, chlorlnating the
solution to liberate bromine, continuously blow
to the lower part of the second tower and per
mitting said gas to flow upward whereby resid- ‘
ual amounts of unsaturated hydrocarbons and
halogens including chlorine react in the presence
of sodium bromide to vform halogenated hydro
carbons, continuously passing unreacted gases
through an alkali solution for the absorption of
ing air through said solution to remover bromine - free halogens, and continuously contacting resid
ual gases with adsorbent material for recovery
of halogenated hydrocarbons, and to isolate prac 10
10 an alkali solution to recover the bromine.
tically pure saturated hydrocarbons substantially
9. The method of continuously separating un
devoid-of unsaturated hydrocarbons.
,
saturated hydrocarbons from saturated hydro
ll. The improvement in the continuous method
carbon gases and isolating substantially pure
of halogenatlng hydrocarbons and of isolating
saturated hydrocarbons practically devoid of un
therefrom, continuously passing said air through
saturated hydrocarbons which _comprises estab
15
lishing a column of downward flowing solution
containing sodium bromide, continuously intro
ducing chlorine gas into the said solution in the
lower part of said column to liberate bromine
20 from the bromide from said solution `and to form
bromine chloride, continuously contacting said
flowing solution with a gas containing unsatu
rated and saturated hydrocarbons in regions con
taining said bromine chloride to cause a conver
25 sion of said unsaturated hydrocarbons to halo
genated hydrocarbons, continuously admitting
`practically pure saturated hydrocarbons substan
tially devoid of unsaturated hydrocarbons which
comprises establishing adownward ñowing column
of an acidiñed solution saturated to sodium bro- `
mide, continuously passing chlorine gas upward at
a rate sumcient to liberate more than all the bro 20
mine from the bromide of said solution and to
form bromine chloride, continuously introduc
/ing a gas `containing unsaturated and saturated
hydrocarbons into the lower part of said column
and flowing the gas upward to permit reac
tion of free halogens including bromine chloride
small amounts of said gas in the lower and upper lwith unsaturated hydrocarbons to form halo
parts of saidv column to react with free halogens, genated hydrocarbons, continuously admitting a
continuously separating said halogenated hydro
30 carbons from said solution, continuously passing
the unreacted gas through an alkali solution for
the absorption of free halogens, and continuous
as
ly bringing the residual gas into contact with ad
sorbent material for the recovery of halogenated
-hydrocarbons and for the isolation of substan
tially pure saturated hydrocarbons practically
devoid of unsaturated hydrocarbons.
10. The method of continuously separating
'unsaturated hydrocarbons from saturated hydro
40 carbon gases and isolating vsubstantially pure
saturated hydrocarbons practically devoid of un
saturated hydrocarbons which comprises estab
lishing two columns of a. downward flowing solu
tion containing sodium bromide, continuously
45 introducing a fresh solution of sodium bromide
into the upper part of the second column, con
tinuously introducing chlorine in excess of
stoichiometric amounts in the lower part of the
ilrst column to liberate bromine from the bro
mide and to form bromine chloride, continuously
passing gas containing unsaturated hydrocar
bons from saturated hydrocarbon gases counter
current to said flowing solution in the iirst column
to cause the formation of halogenated hydro
carbons from unsaturated hydrocarbons, con
tinuously _separating the halogenated hydrocar
' bons from said solution, continuously conveying
» the unreacted gas from the top of the iirst column
small amount of gas near the bottom of and in
4the upper part of said column to cause reaction
of free halogens and unsaturated hydrocarbons
whereby the free halogens are reduced to a
negligible amount, and continuously 'removing
the halogenated hydrocarbons from the said solu
tion, and isolating practically pure saturated
hydrocarbons substantially devoid of unsaturated
hydrocarbons.
`
12. The continuous method of making alkylene
bromchlorides which comprises contacting a
stream of hydrocarbons containing alkylene and l
saturated hydrocarbons with a solution of
nascent bromine chloride in an aqueous solution
of alkali metal halide.
13. The method of continuously making alkyl
ene bromchluorides which comprises contacting a 45
stream of hydrocarbons containing alkylene and
saturated hydrocarbons with a moving solution
of nascent bromine chloride in an acidifled
aqueous solution of alkali metal halide.
14. The method of continuosly making alkyl 50
ene bromchlorides which comprises contacting a
stream of hydrocarbons containing alkylene and
saturated hydrocarbons with a flowing solution
of nascent bromine chloride having a bromine
content above 4% in an aqueous solution oi.' 55
alkali metalv halide.
'
RALPH H. MCKEE.
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