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Патент USA US2122110

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June 28, 1938.
’ 2,122,111@
J. F. o-LIN ET Al.
HALOGENATION OF ALIPHATIC ALCOHOLS
Filed March 8, 1937
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Patented June 2%, i938
2.122,11@ ,
UNITED STATES
.
OFFICE
2,122,110
~
HALoGENArIoN or AmrnA'rrc aLconoLs
John F. Olin and George E. Hinds, Grosse lle,
Mich., assignors to The Sharples Solvents Cor
poration, Philadelphia, Pa., a corporation of
Delaware
Application March 8, 1937, Serial No. 129,545
15 claims.
The present invention pertains to the art of
chlorination and was conceived in connection
with research on the problem of converting alco
hols into corresponding chlorides by reacting the
5 alcohols with hydrogen chloride. The invention
is particularly concerned with the development
of a technique by which yields may be improved
and separation problems minimized in connec
tion with operations of this character.
In the practice of a process of this character,
it is common practice to bubble gaseous hydrogen
chloride through a body of the heated alcohol.
In order to obtain a high yield of the chlorinated
product it is necessary to pass'a molecular ex
(Cl. 26d-162)
'
.
An‘important feature of the invention consists
in the nature of the gaseous mixturewith which
the alcohol is treated in the reactor II. This
material is obtained in accordance with the pre
ferred embodiment of the invention in the fol
lowing manner:
A body of mixed pentanes of the character de
scribed in the patent to Ayres 1,831,474’is chlo
rinated in accordance'with the procedure de
scribed in that patent. Thus, the pentanes and 10
chlorine are passed into confiuence in vapor
phase into a conduit I2 and are passed together
through a heated reactor I3 to produce a mix
ture of amyl chlorides. This mixture is cooled
at I0 and is fractionated in the rectifying column 15
Iii to separate the amyl chlorides from unreacted
cess ~of hydrogen chloride through the reactor,
and unreacted hydrogen chloride must, of course,
be separated from the chlorinated reaction prod ~ hydrocarbon and hydrogen chloride. The mix
uct'and water formed in the reaction. Objects ture of unreacted/hydrocarbon and hydrogen
of the invention have been to conduct the chloride is passed. to condenser I6 where the
bulk of pentanes is condensed and refluxed to
20 chlorination step and the ensuing step of separa
tion in such a manner as to improve upon the the column I5. Hydrogen chloride containing a
efllciency of the separation attained as compared substantial proportion of pentanes is passed from
to that attained in prior art processes. To this condenser it to reactor II. A part of the mix
ture of these materials passing from the con
end, features of the invention relate to intro
duction of a low boiling hydrocarbon together denser i6 may be passed to the reactor II and
another part to a separating chamber I'I in which>
with the hydrogen chloride into the chlorinat
water is passed in counter-current direction with
ing reaction and the maintenance of a hydro
respect to the mixture of hydrogen chloride and
carbon reflux in connection with the fractiona
tion of hydrogen chloride from the resultants of pentane and thus absorbs the hydrogen chloride
as indicated'in the flow sheet and described in
30 the reaction. Anotherfeature of the invention
the above mentioned Ayres patent with respect
consists in the utilization in the chlorination re
to the absorber 24 of‘that patent. The mixture
action of a mixture of a hydrocarbon and hy
drogen chloride resulting from the chlorination of hydrogen chloride and pentane discussed
above is passed in vapor phase through the re
of other `hydrocarbon material.
actor II and this reactor is maintained at a
The
invention
will
be
best
understood
by
ref
35
erence to the attached flow-sheet, in which the temperature of approximately 100° C. during the
course of the reaction. The hydrogen chloride
single figure constitutes a diagrammatic illus
tration of the_performance of the steps of the reacts with the butyl alcohol in accordance with
process.
40
c:
'
-
The invention was conceived in connection
with research upon the problem of converting
butyl alcohol into butyl chloride by bubbling
hydrogen chloride through a body of butyl alco
hol maintained in the liquid phase. It will
45 therefore be described with reference to that
problem although the details of the invention
have a much wider application than this specific
operation as will'be pointed out hereafter.
A body of butyl alcohol is first .passed from
50 the container I0 to a reactor II. This body 'of
alcohol is treated with hydrogen chloride by
bubbling the gaseous hydrogen chloride through
the body of liquid alcohol from the reactor II
while heating that alcohol to a temperature of
55 approximately 100° C.
20
25
30
35
the following equation:
40
A vapor phase mixture consisting of butyl alco
hol, butyl chloride, water, pentane and hydrogen
chloride passes from the reactor I I tothe column
IB. A condenser I9 is maintained at a tempera 45
ture between 78 »and 80° C. thus allowing butyl
chloride, pentane and hydrogen chloride and
some butyl alcohol to be passed overhead while
effecting a reflux of most of the butyl alcohol and
water.
,
'
t
50
A mixture containing butyl chloride, pentane,
hydrogen chloride and a small amount of water
and butyl alcohol passes overhead to'column 20.
Gases are passed from thisy column to a highly
eiiicient condenser 2l maintained at a suiiiciently 55
2
2,122,110
10W temperature to obtain a reflux of the pen
tane. A further quantity of pentane or other
low boiling hydrocarbon may also be introduced
into the top of the column 2| to obtain a larger
volume of refluxed material.
Alternatively, pure
hydrogen chloride may be used in the chlorina
tion reaction in reactor ll in case reflux hydro
carbon is introduced into the top of column 2l.
The'eifect of the maintenance of the reflux of'
10 a low boiling hydrocarbon such as pentane in
the column 2D is to prevent the passage of butyl
chloride with hydrogen chloride through the con
denser 2l. A very emcient separation of these
two constituents is thus obtained and a mixture
15 of pentane, butyl alcohol, butyl _chloride and
water containing a small amount of hydrogen'
chloride falls to the receiver 22. This mixture
separates into a lower aqueous phase containing
butyl alcohol, butyl chloride and water and an
20 upper phase containing pentane and butyl chlo
ride. The mixture of pentane and butyl chlo
ride may be returned to the reactor Il, with or '
without further puriñcation, as indicated in the
flow sheet.
25
It will be noted from the above description
that the use of a mixture of pentane with hy
drogen chloride in the reactor Il and the .main
tenance of a hydrocarbon reñux in condenser
2| enable us to obtain a degree of separation of
30
the chlorinated .reaction product from the hy
drogen chloride passing from the process which
could not be otherwise obtained.
The mixture of hydrogen chloride and pentane
passing upwardly from condenser 2l is passed
35 to the hydrogen chloride absorption step I l of
the pentane chlorination process together with
the saine mixture of pentane and hydrogen chlo
ride which may pass directly from the condenser
I6 to the water absorption step il.
40
While the invention has been described specifi
cally with reference to chlorination of butyl al
cohol and uses of pentane in connection with
such chlorination, it will be understood that it
may be applied to the halogenation of any a1
contacting an alcohol under reaction conditions
with a mixture of hydrogen halide and a hydro
carbon compound that will not substantially
enter the reaction and having a boiling point
lower than the desired halogen derivative and 6
thereafter separating hydrogen halide from the
hydrocarbon halide by fractionation while main-taining a reflux of the low boiling hydrocarbon.
4. A process of producing a halogen deriva
tive of a saturated aliphatic hydrocarbon com 10
pound comprising contacting a hydroxy deriva
tive of the hydrocarbon compound under .reac
tion conditions with a mixture of hydrogen halide
and a hydrocarbon compound that will not sub
stantially enter the reaction and having a boil 15
ing point lower than the desired halogen deriva
tive and thereafter separating hydrogen halide
from the hydrocarbon halide by fractionation
while maintaining a reflux of the low boiling
hydrocarbon.
20
5. A process of producing a halogen derivative
ofa hydrocarbon compound comprising passing
a vapor phase mixture of hydrogen halide and a
saturated hydrocarbon compound having a boil
ing point lower than the desired halogen deriva 25
tive through a body of an alcohol in liquid phase
under reaction >conditions and thereafter sep
arating hydrogen halide from the hydrocarbon
halide by fractionation while maintaining a re
ñux of the low boiling- hydrocarbon.
30
6. A process of producing a halogen derivative
of a hydrocarbon compound comprising passing
a vapor phase mixture of hydrogen halide and a
saturated aliphatic hydrocarbon compound hav
ing a boiling point lower than the desired halo
gen derivative through a body of an alcohol in
liquid phase under reaction conditions and there
after separating hydrogen halide from the hydro
carbon halide by fractionation while maintaining
a reflux of the 10W boiling hydrocarbon.
7. A process of producing a halogen derivative
of a hydrocarbon compound comprising halogen
-ating a second hydrocarbon compound having a
boiling point .lower than the boiling point of the
desired halogen derivative, removing the hydro
and a hydrocarbon having a, boiling point sub
carbon halide resulting'from halogenation of said
. stantially lower than the halide to be produced. second hydrocarbon compound from unreacted
sun further modincanons wi11 be obvious to l hydrocarbon and hydrogen halide resulting from
those skilled in the art and we do not wish to be the halogenation of said second hydrocarbon50 limited except by the scope of the subjoined compound, thereafter contacting an alcohol under
claims.
reaction conditions with the mixture of hydrogen
’ ' We claim:
halide and said second hydrocarbon compound
45 cohol by means of a mixture of hydrogen halide
1. A process of producing a halogen deriva
tive of a hydrocarbon compound comprising
55 contacting an alcohol under reaction conditions
with a mixture of hydrogen halide and a satu
rated hydrocarbon compound having a boiling
point lower than the desired halogen derivative
and thereafter separating hydrogen halide from
60 the hydrocarbon halide by fractionation while
maintaining a reflux of the low boiling hydro
carbon.
2. A process of producing a halogen derivative of a saturated aliphatic hydrocarbon corn
65 pound comprising contacting a hydroxy deriva
tive of the hydrocarbon compound under reac
tion conditions with a mixture of hydrogen halide
and a saturated hydrocarbon compound having
a boiling point lower than the desired halogen
70 derivative and thereafter separating hydrogen
halide from the hydrocarbon halide by fraction
ation while maintaining a reflux of the low boil
ing hydrocarbon.
3. A process of producing a halogen deriva
75 tive of a hydrocarbon compound comprising
produced as the result of thefractionation of
hydrocarbon halide of said second hydrocarbon
compound from the reaction mixture resulting
from the halogenation thereof and thereafter
separating by fractionation hydrogen halide from
the hydrocarbon halide resulting from the halo
genation of said alcohol while maintaining a
reflux of the second hydrocarbon compound, said 60
second hydrocarbon compound being one that .
will not substantially enter into the reaction with
the hydrogen halide.
` 8. A process of producing a halogen derivative
of a hydrocarbon compound comprising halo 65
genating a second hydrocarbon compound having
a boiling point lower than the boiling point of
the desired halogen derivative, removing the
hydrocarbon halide resulting from halogenation
of said second hydrocarbon compound from un 70
reacted hydrocarbon and hydrocarbon halide re
sulting from the halogenation of said second
hydrocarbon compound, thereafter passing a
vapor phase mixture of the hydrogen halide and
second hydrocarbon compound produced as the 75
3
2,122,110
result of the fractionation of hydrocarbon halide
from said second hydrocarbon compound through
a body of an alcohol in liquid phase under re
action conditions and thereafter separating by
fractionation hydrogen halide from the hydro
carbon halide resulting from reaction of hydro
gen halide with the alcohol while maintaining a
reflux of the second hydrocarbon compound, said
second hydrocarbon compound being one that
10 will not substantially enter into the reaction with
the hydrogen halide.
9. A process of producing a halogen derivative
of a hydrocarbon compound comprising halogen
ating a second hydrocarbon compound having a
boiling point lower than the boiling point of the
desired halogen derivative, removing the hydro
carbon halide resulting from halogenation of said
second hydrocarbon compound'from unreacted
hydrocarbon and hydrogen halide resulting from
20 the halogenation of said second hydrocarbon
compound, thereafter contacting an alcohol under
reaction conditions with the mixture of hydro
gen halide and said second. hydrocarbon corn
pound produced as the result of the fractionation
25 of hydrocarbon halide of said second hydrocar
bon compound from the reaction mixture result
ing from the -halogenation thereof, thereafter
separating by fractionation hydrogen halide from
the hydrocarbon halide resulting from 'the halo
genation of said alcohol while maintaining a
reflux of the second hydrocarbon compound,
said second hydrocarbon compound being one
that will not substantially enter into the reaction
with the hydrogen halide, passing the mixture of
85 _hydrogen halide and said second hydrocarbon
compound resulting from fractionation of the
halide of said first hydrocarbon compound’there
from into confluence with a mixture of said sec
ond hydrocarbon compound and hydrogen halide
resulting from the removal of hydrocarbon halide
from the reaction mixture resulting from halo
genation of said second hydrocarbon compound,
and passing the mixture resulting from said con
iiuence into contact with water to effect absorp
,
46 tion of hydrogen halide therefrom.
10. A process of producing a halogen derivativ
of butane comprising -halogenating pentane, re
moving amyl halide from the unreacted pentane
and hydrogen halide resulting from the halogen
ation of said pentane, thereafter contacting butyl
alcohol under reaction conditions with the mix
ture of hydrogen halide and pentane produced as
the result of the fractionation of amyl halide
from the reaction mixture resulting from the
halogenation of said pentane and thereafter sep
arating by fractionation hydrogen halide from
the butyl halide resulting from. the halogenation
of said butyl alcohol while maintaining a reflux
of pentane.
ll. The process of producing butyl halide com
prising halogenating pentane. removing amyl
halide resulting from halogenatlon ot said pen
tane from unreacted pentane `and hydrogen I
halide resulting from said halogenation, there
after passing a vapor phase mixture of hydrogen
halide and pentane produced as the result of the
fractionation, of amyl halide from said pentane
through a body of butyl alcohol in liquid phase
under reaction conditions and thereafter sepa
rating by fractionation hydrogen halide from the .
butyl halide resulting from reaction of hydrogen
halide upon said butyl alcohol while maintaining
a reñux of pentane.
12. A process of producing a halogen derivative
of a hydrocarbon compound comprising contact
ing an alcohol under reaction conditions with
hydrogen halide, and thereafter separating 15
hydrogen halide from the hydrocarbon halide
produced by reaction of hydrogen halide upon
said alcohol while maintaining a reflux of a
hydrocarbon that will not substantially enter the
reaction and having a boiling point lower than 20
said hydrocarbon halide.
~
13. A'process of producing a halogen derivative`
of a hydrocarbon compound comprising passing
hydrogen halide in vapor phase through a body
of an alcohol in liquid phase under reaction con 25
ditions and thereafter separating hydrogen
halide from the hydrocarbon halide produced as
the result of reaction of said hydrogen halide
upon said alcohol by fractionation while main
taining a reflux of a hydrocarbon compound that 30
will not substantially enter the reaction and hav
ing a boiling point lower than said hydrocarbon
halide.
'
'
14. A process of producing a halogen derivative
of a hydrocarbon compound comprising contact 35
ing an alcohol under reaction conditions with a
mixture of hydrogen halide and a saturated
hydrocarbon compound having a boiling point
lower than the desired halogen derivative and
thereafter separating hydrogen halideV from the 40
hydrocarbon halide by fractionation while main
taining a reflux of the low boiling hydrocarbon
>introduced with said hydrogen halide and of a
further quantity of a hydrocarbon compound
that will not substantially enter the reaction and 45
having a boiling point lower than that of the
hydrocarbon halide produced, said further quan
tity of hydrocarbon compound being separately
introduced into the fractionating operation.
l5. A process of producing a halogen derivative 50
of a hydrocarbon compound comprising contact
ing an alcohol under reaction conditions with
hydrogen halide and4 thereafter> separating `by
fractionation hydrogen halide from the hydro
carbon halide produced as the result of reaction 55
of said hydrogen halide upon the alcohol while
introducing into the fractionating operation a
reñux of a hydrocarbon-that will not substantially
enter the reaction and having a boiling point"
lower than said -hydrocarbon halide.
JOHN F. OLIN.
GEORGE E. HINDS.
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