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Патент USA US2109004

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Feb. 22, 1938.
‘
F. M. ARCHIBALD Er AL
2,109,004
SECONDARY ALCOHOL PRODUCTION
1
Filed Aug-12, 195a
\
I
HYDROCARBON
OUTLET
‘
23
(-9
-
_
§
ACID 072 WATER ly/ILET
Ricrcmt ACAD- L/NE_/ '
I l5;\
‘
OLEFIN
’
OUTLET
I
ETHER OUTLET
OLEFIN .BxsAiE/wq‘
fix/0120:4230”
’
INLET
@
'
25c vcus
.
A c 1.0 (.avs
Patented Feb. 22, 1938 I
I
UNITED ‘STATES PATENT OFFICE
2,109,004
} _
SECONDARY iiLoonoL PRODUCTION
Francis M. Archibald, Elizabeth, and Helmuth G.
Schneider, Roselle, N. J., assignors to Standard
Alcohol Company
Application August 12,1936, Serial No. 95,578
v '7 Claims.
(Cl. 260-156)
This invention relates to an improved process
carry out the process of the invention andindi
for producing an alcohol directly from an ole?n
oates the ?ow of materials.
and relates more particularly to a catalytic
process for producing an alcohol from an ole?n
5 containing two to ?ve carbon atoms. It may
likewise be used to produce alcohol from an ole-
‘
'
Referring to the drawing, numeral | repre
sents an absorption .tower. This tower is pro
vided with acid plates 2 or other means whereby 5
good contact of the catalytic material and the
?n containing up to seven carbon atoms or more, . ole?nic material is obtained.
The catalytic
It is known that ole?ns may be reacted with
catalytic materials to form reactive acid liquors,
10 the reactive acid liquors diluted, hydrolyzed and
distilled to obtain alcohols. The catalytic material generally used is sulfuric acid, though other
catalytic materials have been used, for example,
material preferably used according to this in
vention is an aqueous solution of sulfuric acid
of 50 to 70% concentration when propylene is 10
the ole?n being reaoted- Higher concentrations
of aqueous sulfuric acid up to 84% and lower
concentrations to 1% may be used with propylene
. phosphDriC acid, hydrochloric acid, acetic acm
l5 and other acids, and also aqueous solution of
salts such as zinc chloride, aluminum chloride,
etc., of the concentrations at which they are capable of forming reactive acid liquors.
and the other ole?ns. While aqueous sulfuric
aeidisthe preferred Catalyst. other aqueous solu- 15
tions of catalytic material may be used, for 6X
ample, aqueous solutions of phosphoric acid, hy
It has been found that ole?ns on reacting with
20 catalytic materials of de?nite concentration and
etc. It is not necessary to use the diluted sulfuric
acid as such in'the absorption tower as reactive 20
temperatures form alkyl sulfates, alcohols and
ethers directly. It has been shown in c'opending application, Serial No. 83,894, “Production of
ethers directly from ole?ns", ?led June 6, 1936,
25 by H. G. Schneider, that after certain amounts of
alkyl sulfates, alcohols and ethers are formed,
the reaction reaches an equilibrium, If the
,ethers thereby produced are removed and the
amount of others in the acid solutions maintained
30 at low concentration, the equilibrium is disturbed.
Substantially all of the oleiins thereafter passed
into the ole?n acid liquor are converted into
ethers if .the ethers are removed continuously as
they are formed,
35
According to this invention, it has been found
that alcohol is formed directly when an ole?n is
contacted with an aqueous hydrating catalyst of
ammtehcncentmtion, and at, certain temperatures and pressures, and after the alcohol is sepa40' rated from the catalytic material the catalytic
material reacts with more of the ole?n added to
- form more alcohols.
Ether is also formed which
may be Separated from the catalytic material to_
gether with the alcohol. The preferred method
45 of separating the alcohol
or a mixture of- alcohol
_
and ether from the catalytic material is by steam
stripping
o?t.without
th damthough
f they mayS be
1 distilled
t
6 a
on 0 Steam‘
0 V9“ extrac 1011 may
50 also beLuSBd-
»
,
The invention will be more fully understood on
drochloric acid, zinc chloride, aluminum chloride,
acid liquor diluted to below 84%, preferably about
50% to 70%, may be used- The aqueous catalytic
material is maintained at substantially the same
concentration throughout the process.
_
The ole?n, or mixture of ole?nS, if mixture of 2
di?'erent» alcohols is ‘to be made, substantially
pure or in a hydrocarbon mixture containing the
desired ole?n OI‘ OlB?IlS, lS'péiSSBd into the‘bottom
of absorption tower l by means of pipe 3- This
ole?n is passed into the bottom of the absorption 30
tower I under a partial pressure of the ole?n
of at least 2 Pounds per square inch- Pressures
of 40 to 200 01' more pounds Del‘ Square inch Par
tlal pressure of the ole?n are preferred though
higher and lower pressures may be used. It is 35
not necessary that the ole?n be in Vapor Phase
as Ole?n in the liquid Phase may also be used to
produce alcohol according to this invention.
The ole?n passes upwardly through the ab
sorption tOWeT I through the aqueous Sulfuric 40
acid layers on the acid plates 2- on layers may be
maintained on the top of the aqueous catalytic
acid layers if desired in order to obtain better con
tact of. the mild and the ole?n‘ An outlet pipe
a prmflded wlth
5 removes.the
unrefacted
materials.
The valve
aqueous
catalytic material
is 45
passed/into the abior tion tower l thmu h i
- ° downward
p
g pab
pe
6 and while
flowing
through the
sorption tower is contacted with the ole?n mate
rial. The aqueous catalytic material with the 50
reaction products in solution is passed ‘ through"
reading the following description with reference
pipe 1 into the Stripping tower a, The absorption
to the accompanying drawingThe drawing shows a diagrammatic view in
tower is maintained at a temperature of 30° C. '
or higher by means of coil 9 or other heat con
55 sectional elevation of an apparatus adapted to
trolling means. The preferred temperature when 55
2
2, 1 09,004
isopropyl alcohol is being produced is about 80° inherent novelty as
to 130° C. ‘ By the use of these temperatures, permits.
pressures, ‘and catalytic concentration all of the
We claim:
ole?ns present are reacted in one pass.
_
'
distilling temperature of the alcohol and ether
and the concentration of the acid controlled.
10 The vapors of ‘alcohol and ether are removed
through outlet I‘! and fractionated in tower is
if desired, condensed and passed to storage.
‘
at the same time avoiding any dilution or con
centration of the sulfuric acid so that it is of
15 absorption tower i, by means of pipe 3 though
both alcohol and ether may be passed to storage.
The separated sulfuric acid in stripping tower 8.
is withdrawn through line it and passed ‘by
means of pump l8 into pipe 6 and thereby into v
spray outlet is not used to remove the alcohol
and ether and at the same time to maintain the
acid at the desired concentration; water is added
to the acid as it enters pipe 5 before it is re-'
.
of the alcohol and ether that-are in solution and
The separated ether is preferably recycled back
into the ole?n material that is passed into the
when the open steam
a
1. A process for manufacturing an alcohol from
an ole?n which comprises contacting an ole?n
with an aqueous solution of sulfuric acid, of 1%
to 84% concentration and under a partial initial
pressure of the ole?n above 2 lbs. per square inch,
and a hydration temperature above 30‘? 0., sep
arating the aqueous solution of sulfuric acid, .10
stripping the aqueous solution by means of steam
Stripping tower 8 is provided with a. steam coil
in and also an open steam spray outlet H,
whereby the temperature may be raised to the
20 the absorption tower i.
bmadlyasthepnorart
constant concentration and recontacting the
residual aqueous solution of sulfuric acid of 1 to
84% concentration with another portion of the
15
ole?n to further manufacture more of the alcohol.
2. A process for manufacturing isopropyl alco
hol from propylene according to claim 1, in which
the ether is recirculated with the aqueous solu
tion of sulfuric acid.
-
3. A process for manufacturing isopropyl al
cohol
from propylene which comprises continu
2.5 turned to the absorption tower i through pipe ously passing
propylene countercurrently to an
i3 provided with valve M. The acid is used con
aqueous solution of sulfuric acid of about 50 to
tinuously, being recycled to the absorption tower 70% concentration whereby a substantial amount
' after the alcohol and ether are stripped out, of isopropyl alcohol is formed directly and is in
30. though it may be necessary to add small amounts solution in the aqueous solution of sulfuric acid,
of the acid and water through pipe is provided continuously withdrawing the aqueous sulfuric 30
with valve ill to maintain the desired volume due acid with the isopropyl alcohol in solution, con
to slight losses, and also to maintain the desired tinuously separating the isopropyl alcohol from
‘ concentration.
the aqueous sulfuric acid while maintaining the
The following table shows the yields of iso
aqueous sulfuric acid at the same concentration
propyl alcohol and isopropyl ether obtained on of about 50 to 70% and continuously recycling
reacting propylene and aqueous sulfuric acid of the aqueous sulfuric acid countercurrently with
different concentrations and at different temper
atures and pressure over various lengths of time:
40
,
0 oncen-
tration of
sulfuric.
‘
my“ 0!, _
Tem
mm ' " ' "
Pam“! Tim9
pressure
01 pro-
9°?‘
d used .' Wax acid,
.45
_
Products per
8mm lgs.
'
mtg-l0ofaciii-Ill‘
of cone
ylene,
'
-‘
-
‘
“1
o
alcohol other
'
a. A‘ process for manufacturing isopropyl al- -
cohol from propylene according to claim 3 in
which pressure of 40 to 269 pounds per square
inch and temperature of 60“ to 130° 6. are main
tained.
tact
rh hours M01 of Mel.
.
more of the propylene.
.
5. A process for manufacturing an alcohol from
an ole?n comprising contacting an ole?n with an
acid liquor that had been prepared by contacting 45
an ole?n with concentrated sulfuric acid and di
Percent
.50
55
f 60
° 0.
_
55
Oil present.-..-
110
.
190
1 4
1. 37
0. 193
55
Oil present--_.
110
'
190
2
1. 51
0.311
65
Oil present-....
110
190
4%
1. 79
0. B8
60
60
60
Oil present...
Oil present--Oil present....
100
100
100
190
191)
190
1_ .
4%
1.54
1. 73
1. 96
0.191
0. 343
0. 670
60
60
No oil present.
No 011 present.
100
' 100
._ 190
‘100
4%
1. l5
1. 94
0. 150
0. 72
60
60
60
60
Oil present---Oil present._.Oil present....
Oil present..-
90'
90
90
100
170
170
170
90
2
4%
1. 42
1. 716
1. 986
1. 110
0. 088
0. 204
0. 32¢
0. 115
60
Oil present._..-
100
60
70
70
01] present._.__
Oil present._-_
Oil present.-.-
100
100
100
90 -
90
190
100
1
2
1. 330
0:218
4}‘
.1. 390
1. 670
1. 600
0. 286
0. 463
0. 575
Alternately a second absorption tower may be
provided into which the ether and oleflns sep
may be used in this absorption tower. The set
urated acid from the?rst absorption tower may
65
be used that is by being passed in countercurrent
relation to the ether and ole?n to obtain super
saturated solution.
70
.
_
.
The foregoing description is merely illustrative
and various changes and alternative arrange
ments may be made. It is not the intention to
limit the process to the exact temperatures, pres
sures and acid concentrations that are given but
' to limit it within the scope of the appended
75 claims, in which it is my intention to claim all
iuted to a concentration less than ‘29%, whereby
an alkyl ester,v alcohol and ether are formed di
rectly, separating the alcohol from the aqueous
solution of the hydrating catalyst while substan
tially maintaining the concentra‘don of the hy
drating catalyst constant and contacting more of
the ole?n with the aqueous solution of the hy
drating catalyst.v
6. A process for manufacturing an alcohol from 55
an ole?n which comprises passing a mixture of
hydrocarbons containing clenns in counter-cur
rent relation to an aqueous solution of sulfuric
acid of less than 70% concentration whereby sub
stantially complete removal of the ole?n from the
hydrocarbon mixture is obtained and an alkyl'
- ester, alcohol and ether are formed directly, sep
arating the alcohol, ether and an ole?n from the
aqueous solution of sulfuric acid while maintain- "
ing the concentration of the sulfuric acid sub
stantially constant and contacting ‘more of the
hydrocarbon mixture containing olefin together
with the said ether and olefin that had been sep
arated with the‘ aqueous solution of sulfuric acid
to form alcohols.
‘ v 7. A process for manufacturing an alcohol from
70
an ole?n which comprises contacting an olefin
together with oil with an aqueous solution of
sulfuric acid of 1% to 84% concentration and
under a partial initial pressure of the olefin above Yrs
escapee
2 lbs. per square inch, and a hydration tember
ature above 30° 0., separating the aqueous solu
tion of sulfuric acid, stripping the aqueous solu
tion by means of steam of the alcohol and other
'
recontacting the residual aqueous solution of sui
furic acid of 1 to 84% concentration with an
other portion of the ole?n to further manufacture
more of the alcohoL-
'
-
-
that are in solution and. at the same time avoid
ing any dilution or concentration of the'sulfuric
acid so that it is of constant concentration and.
3
CIS M. ARCHIBAID,
Zt-il; ‘ '
-
G. SCHNEIDER.
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