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Патент USA US2094297

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Patented Sept. 28,~ 1937
- 2,094,297
“UNITED STATES PATENT OFFICE
2,094,297
MANUFACTURE OF CONDENSATION PROD
UCTS FROM ALIPHATIG ORGANIC COM
POUNDS
Walter Philip Joshua, London, and Herbert Mug
‘gleton Stanley, Great Bookham, England, and
Otto Fuchs andWilhelm Querfurth, (Constance,
'. Baden, Germany, and John Blair Dymock,
Gheam, England, assignors to Deutsche Gold
und Silber Scheideanstalt vormals Roessle
Frankfort-on-the-Main, Germany
.
No Drawing. Application October 26; 1932, Se
rial No. 639,734. In Great Britain October 26,
1931
-
.
13 Claims.
(Cl. 260-106)
creases the activity and the life of the catalyst.
' The present invention relates to the manufac
ture of valuable condensation products from the Suitable amounts of hydrogen are from one half
oxygenated derivatives of‘ the para?ln series of mol. hydrogen to three or more mols hydrogen
for each mol. of aliphatic compound. '
hydrocarbons and specifically relates to the pro
The conversion can be carried out at temper
5 duction of alcohols, esters and other valuable de
atures between 150 and 400", C. and. increased .
rivatives of higher molecular weight from alde
hydes such ‘as acetaldehyde, also from alcohols pressure may be used although we prefer to use
such as methyl alcohol, ethyl alcohol or propyl atmospheric pressure except when treating re
alcohol, and from esters of the aforementioned - action mixtures containing appreciable amounts
of a higher alcohol such as butyl alcohol in which 10
10 alcohols such as’ethyl acetate by catalytic treat
case the use of moderate pressures up to ?fty at
ment in the presence of hydrogen.
mospheres is advantageous.
In so far as the use of alcohols as initial ma
As examples of the metal oxides ‘of feeble basic
terial is concerned it has already been proposed
action which can be used may be mentioned
to convert such alcohols into higher alcohols and
alumina, uranium oxide, thoria and so forth, and 15
as catalytic metals can be mentioned copper,
15 other valuable products by the use of a catalyst
20
consisting of a metal oxide having a dehydrating
e?ect such as alumina in conjunction with a
nickel, silver, chromium and cobalt.
metal such as copper or silver known to have a
oxides having a basic reaction are calcium oxide,
hydrogenating action.
barium oxide, strontium oxide, magnesia and
'
Suitable
In carrying out the manufacture according to ' lithia. By the passage of a mixture of acetalde
hyde and hydrogen, for instance, over a catalyst
the present invention we use catalysts which con
sist of 'a di?icultly reducible oxide or mixture of consisting of alumina and copper, there may be
2,0
obtained considerable quantities of higher esters
and higher alcohols, and substantially the whole
oxides having only feeble or no basic action and
being stable at the prevailing temperature, to
to have a hydrogenating or dehydrogenating ac
of the acetaldehyde unconverted into the afore
said higher products is recovered without decom
tion and not exceeding in quantity ten per cent
position.
by weight of the complete catalyst. The metal
We have also found that by altering the pro
portions of metal oxide and catalytic‘metal in the
25 gether with a metal or mixture of metals known
or metals may be taken in their metallic state
-
catalyst, the course of the reaction can be in?u
30/and be admixed as such 'or the oxide or oxides
may be used, it being understood that owing'to
‘the use of hydrogen as hereinbefore mentioned
25
30
enced so that either higher yields of alcohols and
the like can be produced, or the conversion can
be directed towards the production of larger pro
will rapidly be reduced. We may also use, as an 3 portions of esters and so forth. It is essential,
addition in the catalyst, oxides having a basic however, that the proportion of catalytic metal 35
react-ion,'but we prefer to limit the ‘amount of should not exceed ten per cent by weight of the
'
these basic oxides so that the proportion present total catalyst.
After the catalytic conversion the products of
is always less than the proportion of the other
catalytic constituents, particularly when lower the reaction may be condensed and separated,
alcohols such as methyl and ethyl alcohols are‘ or partially condensed and recirculated over the 40
catalyst. The unconverted starting material may
used as starting material. We’ have found, how
be recirculated over the catalyst alone or together
ever, that when the materials to be treated con
tain a substantial proportion of a higher alcohol with any of the products of the reaction.
The following are‘ examples of the manner in
such for example as butyl alcohol, as would be
the case for instancewhen re-treating part of which the invention may be carried into e?ect 45
and the results obtained:—
the products from the treatment of a lower al
I .and as hereinafter described the oxide or oxides
35
40
45
>
cohol, it is. preferable to employ a. catalyst con
taining larger amounts of the basic oxide. The
catalyst may be used on carriers, such as pumice
to
or other‘inert material.
»
Example I
'
The catalyst'employed contained in an elec
trically heated tube of anysuitable material such 50
According to the present invention it is essen
tial that hydrogen should be added to the reac
as aluminium was composed as follows:
tion mixture as it has been found that improved -
Alumina ______________ _'___; __________ ..r. 100
technical results are obtained ‘by this addition;
Calcium oxide ___________ ____ ___________ __
6
and, moreover, the addition of hydrogen’ in
Copper.
1.5
Parts by weight
’
55
2
2,094,297
A mixture of acetaldehyde and hydrogen in the
It is to be observed that the amount of basic
proportion of 1 mol. acetaldehyde to 1.5 mol.
hydrogen was passed over the catalyst at a'rate
oxide is considerably greater in this example
of 40 litres per hour (calculated as hydrogen) per
are here treating a mixture of alcohols including
litre of catalyst at atmospheric pressure and a
a higher alcohol as hereinbefore mentioned. Ac
temperature of 260° C. '
'
.
than in the previous example; this is because we '
tually the mixture consisted of methyl alcohol,
butyl alcohol and hydrogen in the proportion of
4.6 mols methyl alcohol, 2 mols butyl alcohol and
2 mols hydrogen. This mixture was passed over
the catalyst at a pressure oi.’ about 30 atmospheres 10
l
The condensation products obtained (in addi-v
tion to unchanged acetaldehyde and hydrogen
and a small amount of ethyl alcohol) were as
10
follows:--—
_
~
'
and a temperature of 350° C.
Parts by weight
Butyl acetate
The condensation products obtained (in addi
tion to unchanged components and small
93
Butyl butyrate ________ __l___' ___________ __ 11.5
Butyl alcohol __________________________ _._ 20.2
amounts of acetaldehyde, butyraldehyde and es- .
ters of formic acid) were as follows:- ‘
15 Alcohols higher than butyl alcohol ______ __ 10.5
Example II
~
>
The catalyst was composed as follows:
‘
20
Alcohols of higher boiling point especially ‘
Parts by weight
Alumina ___
Barium
__
_
_
heptyl alcohol _______________________ __
100
oxide. ____________ _; ____ _'_ ____ __
Copper
1.5
ble to take the mixed products resulting from any
5.6
Butyl butyrate
Butyl alcohol
initial conversion of a lower alcohol into a higher
alcohol and re-treat it according to the present
invention for the further conversion into higher 30
5.3
15.5
Alcohols higher than butyl ‘alcohol; ____ __
7
8.3
alcohols.
‘
40
Alumina ___________ __- ______ __. ________ __
er alcohol into a higher alcohol or to take either
component of such a product and to mix it with
a. fresh quantity of an alcoholand subject that 35
.
6
Copper
1.5
____ __
The treatment beingv the same as in Examples
I and 11 the condensation products were as fol
‘
»
"
Parts by weight
Butyl
acetate _____ _.. ___________________ __
6.6
45 Butyl butyrate _________________________ __
8.6
vButyl
alcohol __________________________ __ 17.9
Alcohols higher than butyl alcohol ______ __ 10.5
Example IV
50
i
'
Copper
55
mixture of ethyl alcohol, butyl alcohol and hydro
gen in the proportion of 1 mol. ethyl alcohol,
0.6 mol. butyl alcohol and 1.5 mol. hydrogen was
treated at 258° C. at atmospheric pressure.
The condensation products obtained were as
45
follows:—
Parts by weight
Hexyl alcohol (both normal hexyl alcohol
16.1
50
Higher boiling point alcohols including decyl
Alumina ____________________ __‘_________ __
'
Example VI
Using the same catalyst as in Example V a
and diethyl carbincarbinol) ___________ __ 50.5
Parts by weight
oxide
invention.
Octyl alcohol ..
' The catalyst was composed as follows:—
Calcium
mixture to treatment according to the present
100
Magnesium oxide ______________________ __
lows:—
Similarly it is‘ possible to take the
mixed product of any initial conversion of a low- ‘
Example III
The catalyst was composed as follows:Parts by weight
35
20
. considerable quantities. It is for example possi
Parts by weight
Butyl acetate_____' _____________________ __
480
This example shows that by using a mixture
of alcohols including a higher alcohol together
with‘ methyl alcohol, the higher alcohols with a
boiling point of over 120° C. can be obtained in 25
6
____
The treatment being the same as in Example I,
the condensation products were as follows:—
30
I Parts by weight
Amyl alcohol"; _______________________ __ 1078
Hexyl alcohoL; ____ __-_ ___________ __‘___.._
82
100
__
6
__
2
A mixture of ethyl alcohol and hydrogen in
the proportion of. 1 mol. ethyl alcohol to 2 mols
hydrogen was passed ‘over the catalyst at the same
alcohol, and ethers of higher alcohols_..__ 20.0
Example VII
Using the same catalyst as in Examples V and
VI but a temperature of 320° C. and a pressure
of 30 atmospheres the mixture treated was in
the proportion of 3 mols ethyl alcohol, 1.8 mols .
rate,. temperature and pressure as in Examples ' butyl alcohol and 2 mols hydrogen.
60
I, II, and III.
.
-
4
The condensation products obtained were as
follows‘z-
'
Parts by weight
Butyl acetate
12.7
" 3.0
65 Butyl butyrate
Butyl alcohol
Y
14,0
Alcohols higher than butyl alcohol _______ __ 6.0
Example V‘
336
Octyl alcohol
47
Higher boiling point alcohols including decyl
alcohol and ethers of higher alcohols_..___' 318 65
This example shows the advantage of using a
moderate super-atmospheric pressure when treat
e
Wherever the use of elevated pressure is not
expressly set forth, the. examples were carried
»
,
Parts by weight
Magnesium oxide ________________________ _.. 89
Alumina
Copper oxide
Hexyl alcohol ‘
ing mixed alcohols.
The catalyst employed was composed as fol
lows:—
75
Parts by weight
p
'
70
The condensation products obtained were as 60
follows:-—
-
'
a
8
__..
3
10'
out by passing the vapors in admixture with hy- I
drogenv at atmospheric pressure. ‘By the term
"oxygenated derivative of hydrocarbons oi.’ the
para?ln series” used in the following claims, we 75
3
2,094,297
mean alcohols, aldehydes and aliphatic esters.
What we claim is:—
1. The process of producing valuable conden
sation products from the lower aliphatic monohy- -
dric alcohol esters of the lower fatty acids com
prising subjecting said esters in conjunction with
hydrogen to the action of a mixed catalyst, com
prising essentially a compound taken from a
quantity 10% by weight of the complete catalyst I
and an alkali earth metal oxide the reaction tem
perature ranging from about 150° C._ to about
450° C.
.
6. The processrof producing valuable condensa
tion products from the lower aliphatic mono
hydric alcohol esters of the lower fatty acids com
prising subjecting said esters in conjunction with
hydrogen to the action of a mixed catalyst, com
' group consisting of alumina, uranium oxide,
prising essentially a dehydrating metal oxide 10
10 thoria, beryllium-oxide and zirconium oxide in , which will be stable in the reaction in admixture
admixture with a substance taken from a group
' consisting of copper, nickel, silver, chromium,
‘cadmium, zinc, tin, manganese and cobalt and
/'the“oxides thereof, said substance not exceeding
15 in quantity 10% by weight of the complete cata
lyst and in admixture with an alkali earth metal
oxide and the reaction temperature ranging from ‘
about 150° C. to about 450° C.
2. The process of producing valuable conden
20 sation products from the lower aliphatic monohy
dric alcohol esters‘ of the lower fatty acids com
with a hydrogenating metal oxide not exceeding‘
in quantity 10% by weight of the complete cata
lyst and an alkali earth metal oxide the reaction
temperature ranging from about 150° C. to about 15
450° C.
-
7; The process of producing valuable condenSa-i
tion products, from the lower aliphatic mono
hydric alcohol esters of the lower fatty acids com
prising subjecting said esters in conjunction with. 20
hydrogen to the action of a mixed catalyst, com;
prising essentially a dehydrating metal oxide
prising subjecting said esters in conjunction with which will be stable in the reaction with a hydro--v
hydrogen to the action of a mixed catalyst, com- , genating metal not exceeding in quantity 10% by '
prising essentially a compound taken from a weight of the complete catalyst and with mag
group consisting of alumina, uranium oxide, nesia the reaction temperature, ranging from
thoria, beryllium oxide and zirconium oxide in about 150° C. to about 450° C.
admixture with a substance taken from a group
8. _ The process of producing valuable condensa-v
consisting of copper, nickel, silver, chromium, tion
products from the lower aliphatic mono
cadmium,- zinc, tin, manganese and cobalt and hydric alcohol esters ofv the lower fatty acids 30'
the oxides thereof, said substance notexceeding comprising subjecting said ‘esters in conjunction
in quantity 10% by weight of the complete cat
with hydrogen to the action of a mixed catalyst,
alyst and in admixture with magnesia and the comprising essentially a dehydrating metal oxide
reaction temperature ranging from about 150° C. which will» be stable in the reaction with a hydro
to about 450° C.
genating metal oxide not exceeding in quantity
r 3. The process of producing valuable conden
sation products from the lower aliphatic monohy
dric alcohol esters of the lower fatty acids com
prising subjecting said esters in conjunction with
hydrogen to the action of a mixed catalyst, com
40 prising essentially a compound taken from a
group consisting of alumina, uranium oxide,
thoria, beryllium oxide ‘and zirconium oxide in
10% by weight of the complete catalyst and with
magnesia, the reaction temperature ranging from
about 150° C. to about 450° C.
9. The process of producing valuable condensa
tion products from the lower aliphatic mono
40
hydric alcohol esters of the lower fatty acids com?
prising subjecting said esters in conjunction with
hydrogen to the action of a mixed catalyst, com
admixture with a substance taken from a group prising essentially a dehydrating metal oxide
consisting of copper, nickel, silver, chromium, which will be stable in the reaction with a hydro 45
45 cadmium, zinc, tin, manganese and cobalt and
genating metal not exceeding in quantity 10% by
the oxides thereof, said substance not exceeding weight of the complete catalyst and with barium ‘
in quantity 10% by weight of the complete cat
oxide, the reaction temperature ranging from
alyst and in admixture with barium oxide and the ‘about 150° C. to about 450° C.
reaction temperature ranging from about 150° C.
10. The process of producing valuable con 50
50 to about 450° C.
densation products from ethyl acetate comprising
4. The process of producing valuable conden
subjecting said ethyl acetate in conjunction with
sation products from the lower aliphatic monohy
hydrogen to the action of a mixed catalyst com
drlc alcohol esters of the lower fatty acids com
prising essentially a compound taken from a
prising subjecting said esters in conjunction with ‘group consisting of alumina, uranium oxide,
55 hydrogen to the action of a mixed catalyst, com
thoria, beryllium oxide and zirconium oxide in
prising essentially a compound taken from a
group consisting of alumina, uranium oxide,
thoria, beryllium oxide and zirconium oxide in
admixture with a ‘substance taken from a group
consisting of copper, nickel, silver, chromium,
cadmium, zinc, tin, manganese and cobalt and the
oxides
thereof, said substance not exceeding in
60 consisting of copper, nickel, silver, chromium,
quantity 10% by weight of the complete catalyst
cadmium, zinc, tin, manganese and cobalt and and in admixture with magnesia and the reaction
the oxides thereof, said substance not exceeding _ temperature ranging from about 150°.- C. to abou
in quantity 10% by weight of the complete cat
450° C.
' “
alyst and in admixture with calcium oxide and
11. The process of producing valuable con 65
admixture with a substance taken from a group
65
the reaction temperature ranging from about
densation products from ethyl acetate comprising
150° C. to about 450° C.
5. The process of producing valuable con
subjecting said ethyl acetate in conjunction with .
hydrogen to the action of a mixed catalyst com
densation products .from' the lower aliphatic‘ prising essentially a dehydrating "metal oxide
monohydric alcohol esters of the lower. fatty acids
70 comprising subjecting said esters in conjunction
I with hydrogen to the action of a mixed catalyst,
comprising essentially a dehydrating metal oxide
which will be stable in the reaction in admixture
75 with a'- hydrogenating metal not exceeding in
which will be stable in the reaction in admixture 70
with a hydrogenating metal oxide not exceeding
in quantity 10% by weight of the complete cata
lyst and an alkali earth metal oxide, the reaction
temperature ranging from about 150° C. to about
4 0° C.
'
75
2,094,297
12. The process of producing valuable conden
sation products from ethyl acetate comprising
subjecting said ethyl acetate in conjunction with
subjecting said'ethyl acetate in conjunction with
hydrogen to the action of a mixed catalyst, com
prising essentially a dehydrating metal oxide
hydrogen to the action of a mixed catalyst, com
prising essentially a. dehydrating metal oxide
which will be‘ stable in the reaction with a hydro
which will be stable-in the reaction in admixture
with a - hydrogenating metal not exceeding in
weight of the complete catalyst and with mag
quantity 10% by weight of the complete catalyst
and an alkali earth metal oxide, the reaction tem
perature ranging from about 150° C. to about
10 450°
C.
13. The process of producing valuable con
densation products from ethyl acetate comprising
genating metal not exceeding in quantity 10% by
nesia, the reaction temperature ranging from
about 150° C. to about 450° C.
.
WALTER PHILIP JOSHUA.
HERBERT M. STANLEY.
, O'I'I‘O FUCHS.
WILHEIM QUERFURTH.
JOHN BLAIR DYMOCK.
5
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