DE1232950B - Process for the production of unsaturated alcohols by catalytic hydrogenation of unsaturated fatty acids and / or unsaturated fatty acid esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

jf GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

53/02

C07c

German class: 12 ο -19/03

Number: 1232 950

File number: K 52034IV b / 12 ο

Note eldetag: February 5, 1964

Opened on: January 26, 1967

Following a proposal, new catalysts were produced in a manner not claimed here. Of the Catalyst is a Raney copper-cadmium catalyst, which is made from a ternary alloy with about 30 to 60 percent by weight aluminum and the remainder copper and cadmium was produced. The cadmium content is about 4 to 15 weight percent of the balance and the copper content is about 96 to 85 weight percent the rest. The catalyst is for the production of Λ, / 9-unsaturated alcohols by hydrogenation «, / ^ - unsaturated aldehydes and by hydrogenation a, /? - unsaturated ketones (see the published documents of the Belgian patent 623 031).

It has now been found that this catalyst also has good effectiveness and selectivity in the Production of unsaturated higher aliphatic alcohols by hydrogenation of the corresponding unsaturated Fatty acids or unsaturated fatty acid esters and has a longer lifespan.

The invention relates to a process for the preparation of unsaturated alcohols by catalytic Hydrogenation of unsaturated fatty acids and / or unsaturated fatty acid esters, which is characterized is that the hydrogenation is carried out in the presence of a catalyst which consists of an activated, ternary alloy of the Raney type consists essentially of aluminum, cadmium and Contains copper, with 4 to 15 percent by weight of the sum of the weight of copper and cadmium Cadmium and aluminum is less than about 60 percent by weight of the catalyst.

The catalyst is prepared in a manner not claimed here that one with the formation of a molten ternary alloy is a mixture of aluminum, copper and cadmium which melts Contains 30 to 60 percent by weight aluminum and the remainder copper and cadmium, the proportion of Cadmium in the balance 4 to 15 percent by weight makes up that one cools down quickly and then the alloy pulverized, the finely crushed alloy treated with an aqueous alkali solution, washed with water and removed the resulting Raney copper-cadmium catalyst. A catalyst is obtained which is suitable for the hydrogenation process of the invention. The catalyst is highly selective. the The selectivity of the catalysts and the yield of unsaturated alcohol can be improved by additional treatment can be increased. This treatment involves heating the catalyst to a temperature of 250 to 350 ° C under a stream of hydrogen gas or in an inert atmosphere.

Process for the production of unsaturated
Alcohols by catalytic hydrogenation
unsaturated fatty acids and / or
unsaturated fatty acid ester

Applicant:

Kyowa Hakko Kogyo Co., Ltd., Tokyo

Representative:

Dr.-Ing. H. Ruschke, patent attorney,

Berlin 33, Auguste-Viktoria-Str. 65

Named as inventor:

Shiro Kudo,

Seiichi Yada,

Takayoshi Yamauchi, Sakai-shi (Japan)

Claimed priority:

Japan 7 June 1963 (29 271)

The catalyst obtained is a Raney copper-cadmium catalyst, which has a high degree of selectivity. It consists essentially of 1 to weight percent aluminum and a remainder of cadmium and copper, with cadmium making up 4 to 15 weight percent of the remainder. The surface area of the catalysts is about 5 to 70 m ² / g.

The preferred catalyst is made from a ternary alloy which is 40 to 50 percent by weight Contains aluminum, 3 to 7 percent by weight cadmium and 43 to 57 percent by weight copper. The production of unsaturated higher aliphatic alcohols by hydrogenation of fatty acids or fatty acid esters with unsaturated groups has been described by Sauer and A d k i η s in »J. At the. Chem. Soc ", Vol. 59, p. 1 (1937), and the unsaturated higher aüphatic alcohols were from unsaturated Obtained fatty acid esters using mixed metal oxide catalysts. The catalyst was in a large amount (about 50 percent by weight, based on the starting material) was applied and the reaction time required was 7 to 11 hours. The most in-depth investigations using metals other than copper as catalysts come from Komori,

609 759/427

3 4

the effectiveness of various mixed metal desirable side reactions, such as the dehydrate dioxide catalysts compared and observed that ization or polymerization of the reaction compound zinc-chromium oxide ("Kogyo Kagaku Zasshi", Vol. 41, nenten, whereby the reaction yield is noticeably lowered p. 419 [1938]) and iron-chromium oxide ("Kogyo Kagaku. Likewise, the use of a Zasshi ", Vol. 43, p. 910 [1940] J) particularly effective large amount of catalyst, based on weight Catalysts are. Sasazaki realized that one of the reactants was zinc powder from the industrial stand for this type of hydrogenation also effective point out disadvantageous. In addition, they are metallist ("NihonNogei Kagaku Kaishi", Vol. 15, p. 531 [1939]), oxide catalysts or those applied to supports and K ο b a s h i et al. stated that zinc-aluminum catalysts were difficult to produce from the reaction products Oxides and iron-zinc oxides are excellent cata- lysts to separate when they are in liquid form in reactions represent sators ("Kogyo Kagaku Kaishi", Vol. 54, phase with catalyst suspension can be used. P. 581 [1951]). Metal soap catalysts appear to have lower reactivity

With regard to the binary zinc-chromium catalysts allow tion temperatures and lower quantities

Except for Komori, many results have been found on catalyst, but these are catalysts

is difficult to reuse in British Patent 806,619,15.

"Masloboyno-Zhirovaya Prom.", Vol. 25, No. 10, p. 25 The Raney copper-cadmium catalyst enables

(1959), and »Tr. Vses. After that. - Issled. Inst. Light the production of unsaturated higher aliphatic

Zhirov ", No. 20, p. 216 (1960). More information on table alcohols in high yields and one

binary zinc-vanadium and cadmium-vanadium- short time at reaction temperatures from 250 to

Catalysts can be found in German patent 20 280 ° C, even though the catalyst is in reaction

font 865 741. in the liquid phase with catalyst suspension in a

With recent catalysts, it is, however, emergency small amount of 3 to 5 ° / _0, based agile, when the reaction in the liquid phase with weight of the reaction components, is used in the. Catalyst suspension takes place, reaction temperature also decreases the activity of the catalyst by using temperatures from 300 to 330 ° C with additional repeated use, which is shown in Example 5 Licher application of catalyst amounts in the range, also the catalyst is when using about 10 to 20 ° / _0, based on the weight of, suspension in a liquid phase reaction with a catalyst-reactant from the reaction product with the utmost

According to Japanese Patent Specification 136,030, ease becomes separable (see Example 6).
for the production of unsaturated higher aliphatic 30 r · 1 1

Alcohols from unsaturated fatty acids or their example 1

Esters used a catalyst, which is copper. In an electric furnace, a graphite crucible is used

contains. The catalyst is on a support material, heated to about 700 ° C. 180 g of a binary aluminum

such as diatomaceous earth, and copper and copper alloy (weight ratio 1: 1)

Cadmium is melted in the crucible by alkali treatment of the mine. Then be under

Ralsic acid salts converted into the form of hydroxides thorough stirring of the contents of 20 g of a binary

and the product washed and dried. As a cadmium-copper alloy (weight ratio 1: 1)

Example of the use of a copper chromite in the crucible. The resulting alloy

The catalyst described in combination with cadmium is emptied onto a floor while stirring. Immediately

Lauer et al. the reduction of Egyptian 40, the resulting alloy becomes rapidly with water

Cottonseed oil is ^{cooled at 350 0} C using and to a grain size of 6400 to

10 ° / ₀ of a cadmium-modified copper chromite crushed 10,000 fairytale per square centimeter. the

catalyst ("Österr. former newspaper", vol. 56, p. 255 resulting alloy has the following weight

[1955]). percentage composition (Cu: Cd: Al) 50.0:

Moreno et al. performed this type of Hy- 45 5.0: 45.0. 10 g of the alloy grains thus obtained

dry out at 265 ° C using 10% with 1000 g of 10 ° / ₀ iger aqueous sodium hydroxide

Treated copper chromite catalyst in combination with solution at 3O ⁰ C for 15 minutes. After

3.75% cadmium carbonate ("Grasas y Aceites" [Se- alkali treatment has most aluminum

ville, Spain], Vol. 9, p. 60 [1958]). The Dutch carved out.

Patent 83,379 describes the preparation of un- 50 After treatment, the alkali liquid saturated higher aliphatic alcohols from the discarded and the catalyst grains thus obtained corresponding unsaturated fatty acids in reaction is washed with water until the washing water until neutral tion temperatures of 280 to 300 ⁰ C under Ver - is. The catalyst obtained has the following use of a catalyst containing 60 to 90% copper soap and 40 to 40% composition (percent by weight Cu: Cd: Al) 10% cadmium soap. Except 55 88.0: 8.8: 3.2 and a surface area of 25.0 m ² / g. A quartz tube is filled with the catalyst grains of higher aliphatic alcohols made from unsaturated fatty acids and heated ^{to 300 ° C. for 3 hours in a hydrogen stream by using the said copper.}

Cadmium Soap Catalyst Detailed Results 3g of the above catalyst becomes 100g

Investigations in “Chim. et Ind. (Paris) «, Vol. 83, 60 methyl oleate (iodine number 89.1, saponification number 192.3,

P. 875 (1960), published. Acid number 0) given. The resulting mixture is

When carrying out this type of hydrogenation in a shaking autoclave using a solid catalyst, an internal volume of 11. The autoclave is 120 mi high and a large amount of catalyst, at 260 ° C under an initial hydrogen pressure based on the weight of the reactants, 65 of 120 kg / cm ² shaken at 20 ^° C. and cooled is required. The reaction of fatty acids or fatty acid- The reaction product has an iodine number of 72.8, esters with unsaturated groups at high temperatures, however, an acid number of 54.1 and a hydroxyl number of temperatures necessarily causes un- 160.0.

I 232

Example 2

5 g of the catalyst obtained by the process of Example 1 are added to 100 g of butyl oleate (iodine number 77.2, saponification number 170.1, acid number 0.8). The mixture obtained is shaken in the autoclave of Example 1 at 260 ^° C. for 150 minutes under an initial hydrogen pressure of 130 kg / cm ^a at 20 ^° C. and then cooled. The reaction product has an iodine number of 75.0, an acid number of 55.2 and a hydroxyl number of 155.0.

Example 3

The activity of the present Raney catalyst against butyl oleate is with that of a binary

Copper-cadmium catalyst on a diatomaceous earth carrier compared. The results are in Table 1 reproduced.

The binary copper-cadmium catalyst applied to a diatomaceous earth carrier is produced in the usual way, ie by dissolving given amounts of copper nitrate and cadmium nitrate in water to form an aqueous solution, simultaneous precipitation of copper hydroxide and cadmium hydroxide from the aqueous solution by using Sodium hydroxide, mixing the hydroxides with a carrier, drying the resulting mixture at 110 to 115 ^° C., calcining the dried mixture in air at 400 ^° C. for 4 hours and then reducing the calcined mixture for 3 hours at 300 ^° C.

Tabel

Butyl oleate: analytical values = iodine number: 77.2; Saponification value: 170.1;
Acid number: 0.8; Amount added: 100 g.

catalyst

Amount of catalyst

Reaction temperature

reaction time

Initial water

fabric printing

at 26 ° C

kg / cm ²

Analytical values
of the reaction product

Iodine number

Acid number

Hydroxyl number

Binary catalyst produced by the precipitation method (composition by weight Cu: Cd: diatomaceous earth = 53.3: 18.7: 28.0)

Raney catalyst according to
example 1

10

10

260

260

150

150

100

100

86.9

75.4

165.1

57.8

40.3
153.1

The Autoüdav used was the same as in the example Example 4

Hydrogenated methyl ester made from rice oil. The reaction conditions used and those obtained Using the reaction products obtained in Example 1, Table 2 shows all catalysts oleic acid, olive oil and 40 respectively were collected.

Tabel

feed
description
and analytical values admitted
lot
G Kataly
sator amount
S. Reaction
temperature
⁰ C Reaction
Time
Min. Initial water
fabric printing
at 20 ^° C
kg / cm ² Anal
Rea
iodine
number ytic W
ctionsprc
acid
number erte des
duktes
Hydroxyl
number Oleic acid
Iodine number 71.2
Saponification number ... 206.4
Acid number 205 ^ 4
olive oil
Iodine number 78.7
Saponification number ... 192.1
Acid number 2.5
Rice oil methyl ester
Iodine number 122.4
Saponification number ... 189.4
Acid number 0 100
100
100 8th
10
5 280
260
250 180
150
100 130
120
120 74.6
71.5
78.1 55.0
87.2
61.3 155.6
120.9
149.2

The autoclave used is the same as in the example

Example 5 5 g of the catalyst obtained according to Example 1 The present Raney catalyst can be repeated 65 g to 100 g of methyl oleate (iodine number 89.1, used. Test results are given in Table 3, soap number 192.3, acid number 0). The received reproduced. The experiment was as follows throughput mixture is conducted in the autoclave of Example 1 at: 26O ⁰ C for 100 minutes under an initial

hydrogen pressure of 100 kg / cm ^a at 20 ^r C implemented. After the reaction, the catalyst is separated off from the reaction mixture and the autoclave is reloaded with the catalyst used and a fresh sample (100 g) of methyl oleate. The above reaction is repeated under the specified conditions. The same measures are then repeated a total of five times. All reaction conditions are the same after the second time as the first time.

Table 3

Repeated
use

Once .

Twice

3 times

Four times

Five times

Analytical values of the
Reaction product
Iodine number! Acid number \ hydroxyl number

73.2
74.0
73.1
72.4
74.0

49.6
51.7
50.3
52.0
53.8

162.0
159.1
160.8
156.3
155.1

Example 6

In order to check the extent of the separation of the catalyst from the reaction product, the Reaction product (obtained with the aid of the catalyst repeated three times according to Example 5, used) from the autoclave

stirred removed and again for 2 minutes at 50 ⁰ C after interruption of stirring and decanting the supernatant. The amount of catalyst contained in the supernatant is 0.1 g; ie, 98 ° / ₀ of the total amount (5 g catalyst) present in the reaction product can very easily be removed simply by decanting.

Claims (1)

Claim: Process for the preparation of unsaturated alcohols by catalytic hydrogenation of unsaturated alcohols Fatty acids and / or unsaturated fatty acid esters, characterized in that that the hydrogenation is carried out in the presence of a catalyst which consists of an activated The Raney-type ternary alloy consists essentially of aluminum, cadmium and copper contains, with cadmium 4 to 15 percent by weight of the sum of the weight of copper and cadmium and aluminum is less than about 60 percent by weight of the catalyst. Considered publications:
Swiss Patent No. 220 742;
British Patent No. 806,619;
Houben - Weyl, "Methods of Organic Chemistry", Vol. IV / 2, p. 171 (1955). 609 759/427 1.67 ® Bundesdruckerei Berlin