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Патент USA US2121368

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2,121,368
Patented June 21, 1938
UNITED STATES ‘PATENT
OFF-ICE
2,121,368
PROCESS OF CATALYTICALLY HYDROGEN
ATING‘ METAL SALTS .OF HIGH MOLECU
LAR NONAROMATIC CARBOXYLIC ACIDS
Georg Schiller, Mannheim, Germany, assignor to'
I. G. Farbenindustrie Aktiengesellschaft,
Frankfort-on-the-Main, Germany
No Drawing. Application November 14, 1936, Se
rial No. 110,848. In Germany July 2'7, 1934'
10 Claims. (Cl. 260-456)
This application is a continuation-impart of ‘ their esters, such as oils, fats, waxes or resins,
lactones, or anhydrides with basic reacting sub
stances derived from the said di- or trivalent
25th,‘ 1935, which relates to a new process of cata
lytically hydrogenating salts of. high-molecular metals, such as calcium oxide, magnesium oxide
and the like or mixtures of these basic reacting
5 ‘non-aromatic carboxylic acids or materials con
_
taining the same, such as neutralizedioindation substances.
It is also possible to carry out the present proc
products of high-molecular non-aromatic hydro
ess by mixing the carboxylic acids or the starting
‘I have now ‘found that valuable alcohols (are ‘ material containing acids with the aforesaid
obtained by treating salts of di- or trivalent basic reacting substances and heating the mix
10 metals of non-aromatic carboxylic acids‘ contain 1 ture tolthe temperature as it is required for the
ing at least 8 carbon atoms in the, molecule or hydrogenation, whereby the saponi?cation takes
place. Generally the soaps to be hydrogenated
materials containing the same at elevated tem
Preferably the ‘
peratures under superatmospheric' pressure with‘ are present in the liquid state.
a gas essentially comprising hydrogen in the soaps are employed in form of solutions or sus
presence of a hydrogenation catalyst comprising , pensions. _ Suitable solvents are for example par- ticularly the high-molecular aliphatic alcohols,
‘essentially a metal selected from the group con
such as dodecyl alcohol or hexadecyl alcohol and
sisting of nickel, cobalt and copper.
_
'
Suitable initial materials are salts of such di-‘ so on. Also the hydrogenation product obtained
in the present process may be employed as sol
20 or trivalent metals which possess an‘ atomic vent. Furthermore dioxane, high-molecular
weight below 150. For example salts of calcium,
strontium, barium, magnesium, zinc, ‘cadmium or para?inic hydrocarbons and high-molecular
aluminium and non-aromatic carboxylic acids ethers may be employed as solvents or suspending
containing at least 8 carbon atoms in the mole,
A suitable method for preparing catalysts‘for
cule, such *' as lauric, 'palmitic, stearic, oleic,vv
ricinoleic, linoleic acid or montanic, abietic or use in the present process consists in intimately
humic acid or the mixtures of acids obtainable by mixing the metals (Ni, Co and/or Cu) with a
saponifying vegetable or animal fats and oils, basic reacting metal oxide or oxides, both com
such as coconut oil, palm kernel oil, soy bean oil, ponents being advantageously in the form of 30
powders. Another suitable method of pro
0 train oil. Furthermore the oxidation products ‘?ne
from high-molecular non-aromatic hydrocarbons ducin'g'the catalysts consists in precipitating to
the U. S. application SerINo. 33,127, ?led July
carbons.
I
'
‘
agents.
saponified with basic reacting, compounds derived
from ,di- and trivalent metals can be employed.
Preferably oxidation products are suitable which
5 are'obtained by oxidizing hard para?in wax, soft
paraffin wax, higher molecular non-aromatic
'
.
,
gether insoluble compounds, for example carbon
ates, of these two components from solutions con
taining water-soluble compounds thereof and
drying the precipitates, if desired, after washing.
If the hydrogenating component is present in the
catalyst ‘in the oxidic form, it is reduced before
of coals, tars, mineral oils ‘and the like, ‘in the a or at the beginning of ‘the treatment. The said
petroleum hydrocarbons, hydrogenation products
liquid phase at elevated temperature, preferably ' copper, cobalt or nickel'catalysts may preferably.
be activated by the addition of di?lcultly reducible
between 100° and 200° C. by means of gases com
prising oxygen, such as air, oxygen, nitrous gases - metal oxides particularly metal oxides of heavy
or nitric acid or the like, if desired, in the ,pres-M metals, such as manganese oxide, chromium
ence of catalysts, such as manganesepalmitate,
sodium carbonate-manganese stearate, vsodium
oxide, vanadic acid, tungstic acid and the like.
A further method of preparing the catalysts
45 palfnitateealuminium palmitate etc. Instead of‘ consists in introducing the basic reacting metal
into solutions or melts of nickel, cobalt or
the said salts of high-molecular non-aromatic oxides
copper salts decomposable at elevated temper
carbcxylic acids as such, the salts of raw mixtures
containing the acids, for example, the crude re-,
action mixtures originating from the oxidation
~50 of high-molecular non-aromatic hydrocarbons
which besides the acids may contain'hydrocar
> bons, ketones, aldehydes and the like, can serve
as initial materials. The aforesaid salts from di
to trivalent metals can also be obtained by
55 ‘saponifying higher molecular organic acids or _
‘
atures, for example the nitrates, formates and
acetates of the said metals. Any other methods
of producing activated catalysts may also be em 50
ployed. Instead of using nickel or cobalt or cop
per several of these metals may be employed
together and instead of using one basic metal
oxide'several compounds of this type may be ap
plied. Also it may be advantageous to precipitate
v 2
2,121,368
the catalysts on carriers, for example, on dia
tomaceous earth, asbestos, bleaching earth, or
other substances having a large surface area.
The hydrogenation may be carried out, for ex
ample, by passing the materials to be reduced
over solidly arranged catalysts in the presence of
hydrogen or by dispersing the finely divided cata
lysts in the starting materials and passing hydro
gen through the dispersion. ‘Dispersions of the
10 said kind may be allowed to trickle down through
a reaction tower contai ing filler bodies, such as
Raschig rings, hydroge being led through the
tower, preferably in an upward direction.
The catalysts are very readily dispersable in the
15 initial materials which fact is perhaps due to their
relatively low specific gravity. The hydrogena
tion may be carried out at temperatures between
150° to 350° 0., preferably 'between 200° and
300° C. It is- advantageous to employ pressures
sisting of copper, magnesium oxide and chromium
oxide with a content of 30 per‘ cent of metallic
copper, the product is treated with hydrogen at
270° C. under a pressure of 200 atmospheres.
After separating the catalyst a hydrogenation
product is-obtained which is practically free from
acid and which has the following characteris
tics:—
Acid number ____________________________ __
Saponification number.._..__l__.._v _________ __-_
3
6
10
, Hydroxyl number _______________________ __ 157
" The product, besides alcohols, as essential con
stituent only contains unaltered paraffin wax
which originates from the initial material.
15
Example 3
Fatty acids obtained by saponi?cation of coco
nut oil are distilled and then converted into soap
treating with an equivalent: amount of cal;
above 10 atmospheres, generally pressures from 'by
cium oxide and magnesium oxide (1:1) in a pasty '
about 100 to about 300 atmospheres are suitable.
By the process as described the carboxylic groups
contained in the initial material are completely
form.
50 parts of this soap are dissolved in 50
parts of dodecyl alcohol while heating at 100° C.
or partially converted into‘the-CI-hOH-qroups. ‘ To this solution 4 parts of the catalyst as men
in Example 2 are added. The soaps are
If in the initial material besides the carboxylic tioned
then treated with hydrogen at 290° C. under a 25
groups other reducible groups are present, such pressure
of 200 atmospheres. A-hydrogenation
as carbonyl groups, the latter are also reduced product is obtained‘ which consists practically
to alcohol groups. '
completely of high molecular aliphatic alcohols
According to the present process the aforesaid having
the following characteristics:
initial'materials, particularly the salts of oxida
tion products of para?ln wax, petroleum and the
like can be readily converted into the correspond
ing alcohols even while employing relatively small
amounts of hydrogenating metals, for example
from 1 to 2 per cent reckoned on the weight of
the initial material. The products obtained may
be employed as valuable intermediates for exam
ple in the production of assistants for the textile
and related industries.
'
The following examples will further illustrate
the nature of this invention, but the invention is
not restricted to these examples. The parts and
percentages are by weight.
-
'100 parts of palmitic acid are neutralized with 8
parts of magnesium voxide and the soap formed is
hydrogenated for 3 hours in a stirring-autoclave
at 270° C., under a hydrogen-pressure of 260 at
mospheres in the presence of 6 parts of a copper
zinc oxide-manganese oxide-catalyst precipitated
on diatomaceous earth and containing 20 per cent
The product is freed from the cata
' of copper.
lyst; it has the following characteristics:
1
Saponiflcation number _________ __' _____ __-__ 37,
lHydroxyl number _______________________ __ 197
Carbonyl number"; ____________________ __
0
If the palmitic acid is not neutralized with mag
nesium oxide but otherwise treated under ‘the
same conditions as indicated above, the product
obtained has the following characteristics:
Acid number__l_'_____y____ _______________ __
42'
Baponiflcation number_________-_ _____ _..‘..___ 1;)?
'
'
In the. unsaponifiab e
Hydroxyl number" 216 matter which amounts
Carbonyl number__
3
3
Saponiflcation number_____ _'.. ___________ __
8
30
Hydroxyl number _______________________ __ 236
I What I claim is:
1. The process of producing alcohols by cata 86
lytic hydrogenation of materials containing a
substantial amount of a salt of from a di"- to a
trivalent metal, of a non-aromatic carboxylic
acid containing at least 8 carbon atoms in the
molecule which consists in treating the said 40
materials at a temperature above 150° C.'under
a pressure above 10 atmospheres with a gas es
sentially comprising hydrogenin the presence
Example 1
Acid number _____ -1 ______________ __v_______ -
Acid number ___________________________ __
to 48.6 per cent
Example 2
100 parts of an oxidation product from soft
parafiin wax having an acid number of 56 and a
of a hydrogenation catalyst comprising essen
tially a metal selected from the group consist
ing of nickel, cobalt and copper.
2. The process of producing alcohols by cata
lytic hydrogenation of materials containing a
substantial amount of a salt of from a di- to a
trivalent metal, of a non-aromatic carboxylic 50
acid containing at least 8 carbon atoms in the
molecule which consists in treating the said ma
terials at a temperature between 150° and 350°
C. under a pressure above 10 atmospheres with a
,. gas essentially comprising hydrogen in the pres 55
ence of a hydrogenation catalyst comprising es- /
sentially a metal selected from the’group con
sisting of nickel, cobalt and copper.
3. The process of producing alcohols by cata
lytic hydrogenation of materials containing a 6.0
substantial amount of a salt of from a di- to a
trivalent metal, of a non-aromatic carboxylic
acid containing at least 8 carbon atoms in the
molecule which consists in treating the said ma
terials at a temperature between 150° and 350° 65
C. and under a pressure of from about 10 to
about 300 atmospheres with a gas essentially
comprising hydrogen in the presence of a hydro
genation catalyst comprising essentially a metal
selected from ‘the group'lconsisting of nickel,
cobalt and copper.
'1'; i’;
70
'
4. 'I'he‘pr'ocess of producing alcohols by cata
saponification number of 137 are heated together lytic hydrogenationjof ‘materials containing a
withlO parts of zinc oxide for about one hour at
75 100° C. After adding 4 parts of a catalyst-eon . substantial amount ‘of a salt of from a di- to a
trivalent metal, .d a non-aromatic carboxyliv 76
3
2,121,868
catalyst comprising essentially a metal selected
from the ‘group consisting of nickel, cobalt and
acid containing at least 8 carbon atoms in the
molecule which consists in treating the said ma
terials at a temperature between 200° and 300°
copper.
,
'
a
8. The process of producing alcohols by cata-'
C. and under‘a pressure of from about ‘100 to‘ lytic,
hydrogenation of materials containing a
5 about 300 atmospheres with a gas essentially
substantial amount of a salt of from- a di- to a‘
comprising hydrogen in the presence of a hydro
genation catalyst comprising essentially a metal trivalent metal, of a non-aromatic carboxylic‘
obtained by the catalytic oxidation of high
selected from the group consisting of nickel, acid
molecular non-aromatic hydrocarbons which .
cobalt and copper. ~
consists in treating the said materials ‘at a_tem-' 10
10 "5. The process of producing alcohols by cata
above 150° C. under a pressure above
lytic hydrogenation of materials containing “a perature
10 atmospheres with a gas essentially comprising
substantial amount of a salt of from a di- to a
hydrogen in ‘the presence of a hydrogenation
catalyst comprising essentially a metal selected
trivalent metal, of a non-aromatic carboxylic
acid containing at least 8 carbon atoms in ‘the
15 molecule which consists in treating the said ma
terials at a temperature between 200° and 300°
C. and under
pressure of from about 100 to
about 300 atm spheres with a gas essentially
comprising hydrogen in the presence of a hydro
20 genation catalyst comprising essentially a metal
from the group consisting of nickel, cobalt and
copper.
'
_
substantial‘ amount of non-aromatic carboxylic
acids containing at least 8 carbon atoms in the
molecule, which consists in saponifying the said
materials with a basic reacting substance de
rived from a di- to a trivalent metal andtreat
cobalt‘and copper activated by adding a ‘diffi
’
'
lytic hydrogenation of materials containing a
selected from the group consisting of nickel,
cultly reducible metal oxide.
,
_ 9. The process of producing alcohols by cata
_
ing the saponi?ed product at a temperature
6. The process of producing alcohols‘ by cata
25 lytic hydrogenation of materials containing a
‘above 150° C. under a pressure above 10 atmos
pheres with a gas essentially {comprising hy
substantial amount of a salt of from a di-- to a
dro gen in the presence of a hydrogenation catalyst‘
comprising essentially a metal selected from the
\ trivalent metal, of a non-aromatic carboxylic
acid containing ,at least .8 carbon atoms in the
group consisting of nickel, cobalt and copper‘,
molecule which consists intreating the said ma‘
30 terials at a temperature between 200° and 300°
. 10. The process of producing alcohols by cataé 30
,lytic hydrogenation of materials containing non
‘
C. and under a pressure of.from, about 100 to
carboxylic acids-containing‘ at least 8
about 200_ atmospheres with atgas essentially. aromatic
carbon atoms in" the molecule, which comprises i»
comprisinghydrogen in the presence of_ a hydro
the oxidation‘ products of high
genation catalyst comprising essentially a metal saponifying
molecular ‘non-aromatic hydrocarbons, with a 35
35’ selected from the group consisting of 'nickel, basic reacting substance derived‘ from a di- to a
cobalt and copper activated with chromium trivalent metal and treating the saponified prod
uct'at a temperature between 200° and 300° C.
7. The process of producing alcohols by cata
‘under a pressure from about 100 to 200 at
lytic hydrogenation of materials containing'a and
mospheres with a gas essentially comprising hy
40 substantialv amount of a salt '0! Home di- to a‘ drogen in the presence of a hydrogenation
trivalent metal,_ of a iatty'acid containing at
‘ catalyst comprising essentially a metal selected ~
least 8' carbonatoms in the molecule which con
from the grou consisting of nickel, cobalt and
. slsts in treating the said materials at a tem
oiride.
,
'
l
a
perature above. 150° C. under a pressure above
45 10 atmospheres with a gas essentially comprising
hydrogen .in the presence of a hydrogenation
.
copper.
Gnome SCHILLER.
-
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