DE1096878B - Process for the production of highly active mixed carbonate catalysts - Google Patents

Description

It is known that highly active catalysts can be obtained by reducing the decomposition of mixed crystals. These catalysts contain, as active constituents, one or more metals and one or more components which essentially have support properties. Oxides are preferably used for this purpose. Suitable mixed crystals for the preparation of these catalysts are, for. B. the salts of oxalic acid or formic acid. The oxalate mixed crystals are usually produced from the solutions of the nitrates, sulfates or chlorides of the corresponding metals by adding an oxalic acid solution. The formate mixed crystals are generally obtained by crystallizing out the corresponding formate solutions together. The carbonate mixed crystals are of particular interest. However, they are not as easy to obtain as the oxalate and formate mixed crystals, since when the corresponding salt solutions are reacted with soda or potash solution, an inexactly defined carbonate is obtained, which is more or less contaminated by hydroxides that are also formed and therefore generally as basic Carbonate is called. These basic carbonates cause considerable difficulties in their further processing, in particular in filtering and washing out. In addition, the activity of the catalysts which can be prepared therefrom is not entirely satisfactory in every case.

It has now been found that pure carbonate mixed crystals with good filterability are obtained which, after reducing decomposition, give catalysts of extremely high activity when a precipitate is obtained from the suspension of a basic oxide with carrier properties and the solution of one or more salts of one or more catalytically more effective Metals with the same or approximately the same ionic radii as the metal of the carrier was obtained, subjected to a pressure-heat treatment with carbon dioxide. It is advantageous to work in a shaking autoclave at temperatures between 100 and 200 ° C. and at pressures of 10 to 100 atm. In such a treatment, as has been determined by X-rays, pure carbonate solid solutions are formed. As a result of the _{crystal growth occurring during the CO 2} pressure treatment, the pure carbonates settle very quickly, so that they can be filtered or decanted well and therefore easily cleaned.

The cobalt-containing mixed catalysts produced according to the invention have a particularly high activity on. You almost reach the activity of the appropriate Nickel catalysts and thus exceed the activity of the usual cobalt catalysts by about that 5 to 10 times.

It has already been proposed to use the basic contaminated Kar process for the production in a known manner
highly active mixed carbonate catalysts

Applicant:

VEB Leuna-Werke »Walter Ulbricht«,
Leuna (Kr.Merseburg)

Dr. Wolfgang Langenbeck, Rostock,

Dr. Jürgen Welker, Halle / Saale,

Dr. Hans Dreyer, Dr. Dietwart Nehring, Rostock,

and Dr. Richard Mahrwald, Zeitz,

have been named as inventors

carbonate mixed crystals and / or mixed hydroxides to a subsequent pressure treatment with carbonic acid subject, likewise pure carbonate mixed crystals are obtained which, after reducing decomposition, give catalysts of good activity. It has, however showed that these catalysts in terms of their catalytic effectiveness of those according to the present Invention manufactured are exceeded by about 100%. The method according to the invention also provides compared to the one already proposed represents a significant simplification and cheaper.

Compared to the known supported catalysts, which are made from metal oxides of a carrier metal and salts catalytically More effective metals are produced, with the hydroxide of the catalytically active metal on the The mixed carbonate catalysts produced according to the invention have the surface of the carrier oxide deposited catalytic activity improved by an average of 300 to 500%. Furthermore prepares with the The aforementioned known catalysts, the purification of the hydroxides formed difficulties because of the removal washing the last residues of sulfate and other anions that damage contact for several days is required.

example 1

42.15 g NiSO ₄ -7H ₂ O and 24.0 g MgO were dissolved or slurried in 900 ml water.

About half of the precipitate was filtered off with suction after brief stirring, washed until it was free of sulfate and dried. The washed out and dried precipitate contained 20.1% nickel and 19.5% magnesium. An amount of the so treated containing 100 mg of nickel Precipitation was 2.5 hours at 450 ° C a reduced

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ornamental decomposition in a hydrogen stream of acid under a pressure of 50 atm. treated. That

201 / h subject. A catalyst was obtained, and the reaction product obtained was filtered and washed

the 5 ml of cyclohexene at room temperature in 36 minutes and dried. It contained 24.1% nickel, 14.2% magnetic

hydrogenated. sium and 11.8% (theoretical: 12.0%) carbon. One

The remainder of the precipitate was collected in accordance with this 5. ' 100 mg of nickel-containing amount of the thus obtained

Invention 15 hours at 150 ° C with carbonic acid under mixed carbonate was 2.5 hours at 400 ° C in one

a pressure of 80 atm. treated. The obtained hydrogen flow of 201 / h. decomposed in a reducing manner. Of the

The reaction product was filtered, washed, and the catalyst prepared in this way was hydrogenated 5 ml

dries. It contained 17 ^ 4% nickel, 18.8% magnesium cyclohexene at room temperature in 9 minutes,
and 12.68% (theoretical: 12.82%) carbon. An io

Amount of Example 5 thus obtained containing 100 mg of nickel
Mixed carbonate was 2.5 hours at 400 ° C

reducing decomposition in a stream of hydrogen from a precipitate prepared according to Example 3 was 201 / h subject. The prepared in this way according to the invention for 14 hours at 150 ° C. with a carbon catalyst hydrogenated 5 ml of cyclohexene with room acid under a pressure of 25 atm. treated. That temperature in 9 minutes. reaction product obtained was filtered, washed

... and dried. It contained 23.8% nickel, 15.3% ma

For example, magnesium and 12.05% (theoretical: 12.4%) carbon.

23.7 g of NiCl ₂ · 6H ₂ O and 10.0 g of MgO were dissolved or slurried in 600 ml of an amount of the water thus obtained containing 100 mg of nickel. About half of the mixed carbonate was extracted for 2.5 hours at 400 ° C. in a precipitate and after brief stirring, a hydrogen flow rate of 201 / hour. decomposed in a reducing manner. The washed until it is free of chloride and dried. The catalyst prepared in this way, hydrogenated 5 ml, washed and dried precipitate contained 37.5% cyclohexene at room temperature in 10.5 minutes.
Nickel and 17.3% magnesium. An amount of the precipitate thus treated containing 100 mg of nickel was 25 Example 6
2.5 hours at 450 ° C of a reducing decomposition

in a hydrogen flow of 201 / h. subject. A precipitate prepared according to Example 3 was

A catalyst was obtained which, according to the invention, contains 5 ml of cyclohexene for 14 hours at 100 ° C. with carbon

hydrogenated in 31 minutes at room temperature. acid under a pressure of 70 atm. treated. That

The other half of the precipitate was obtained. The reaction product obtained was filtered and washed

according to 14 hours at 150 ° C with carbonic acid and dried. It contained 28.3% nickel, 11.1% ma

a pressure of 80 atm. treated. The obtained magnesium, 9.27% (theoretical: 11.3%) carbon and

The reaction product was filtered, washed and given 1.59% hydrogen. An amount containing 100 mg of nickel

dries. It contained 25.0% nickel, 14.4% magnesium of the mixed carbonate thus obtained was 2.5 hours

and 12.11% (theoretical: 12.21%) carbon. A 35 375 ° C in a hydrogen flow of 201 / h. reduced

The amount of rend thus obtained, containing 100 mg of nickel, is decomposed. The catalyst produced in this way

Mixed carbonate was hydrogenated 5 ml of cyclohexene at room temperature in a gate for 2.5 hours at 375 ° C

Hydrogen flow of 201 / h decomposed in a reducing manner. The 13 minutes

Catalyst hy- Example 7 prepared in the manner described
third 5 ml of cyclohexene at room temperature in 9 ml

grooves. A precipitate prepared according to Example 3 was

Example 3 according to the invention for 14 hours at 200 ° C. with carbonic acid under a pressure of 95 atm. treated. That

27.1 g of NiNO ₃ -OH ₂ O and 10.0 g of MgO were filtered and washed, and the reaction product obtained was filtered

600 ml of water dissolved or slurried. Around 45 and dried. It contained 25.1% nickel, 14.1% ma

Half of the precipitate became, after brief stirring, magnesium and 11.8% (theoretical: 12.1%) carbon,

suctioned off, washed to the point of freedom from nitrates and dried

net. The washed and dried precipitate de-mixed carbonate was 2.5 hours at 375 ° C in a

held 35.2% nickel and 18.1% magnesium. A 100 mg hydrogen flow of 201 / hr. decomposed in a reducing manner. Of the

Amount of the thus treated lower catalyst containing nickel hydrogenated 5 ml

Impact was 2.5 hours at 450 ° C a reducing cyclohexene at room temperature in 8 minutes.
Decomposition in a hydrogen stream of 201 / h.

subject. A catalyst, that of Example 8, was obtained
5 ml of cyclohexene at room temperature in 16 minutes

hydrogenated. 55 28.1 g CoSO ₄ -7H ₂ O and 10.0 g MgO were in

According to the invention, the other half of the precipitate was dissolved or slurried with 600 ml of water. About the after 14 hours at 150 ° C with carbonic acid under half of the precipitate was after brief stirring a pressure of 80 atm. treated. The obtained is filtered off with suction, washed until it is free of sulfate and dried reaction product was filtered, washed and net. The washed and dried precipitate is dehydrated. It contained 22.9% nickel, 16.0% magnesium 60 held 35.1% cobalt and 15.4% magnesium. One 100 mg and 12.97% (theoretical: 13.19%) carbon. An amount of the low-100 thus treated containing cobalt mg of nickel of the resulting impact was 2.5 hours at 450 ° C a reducing Mixed carbonate was 2.5 hours at 375 ° C in a decomposition in a hydrogen stream of 201 / h. Hydrogen flow of 201 / h, decomposed reducing. The subject. A catalyst was obtained which Catalyst prepared in this way hydrogenated 5 ml 65 5 ml cyclohexene at room temperature in 260 minutes Cyclohexene at room temperature in 8 minutes. hydrogenated.

π. . The other half of the precipitate was invented

ΰ example 4 _{according to 14 hours at 15Q} o _c ^ carbonic acid

A precipitate produced according to Example 3 was a pressure of 80 atm. treated. The received according to the invention for 14 hours at 150 ° C with carbon 7 ° reaction product was filtered, washed and

ι uaoο / ο

dries. It contained 27.9% cobalt, 12.26% magnesium and 11.51% (theoretical: 11.75%) carbon. One The amount of mixed carbonate thus obtained containing 100 mg of Co was stirred at 450 ° C. for 2.5 hours in a hydrogen stream from 201 / h decomposed in a reducing manner. The catalyst prepared in the manner described hydrogenated 5 ml of cyclohexene at room temperature in 10 minutes.

Example 9

24.2 g Cu (NOg) ₂ -3H ₂ O and 22.4 g CaO were dissolved or slurried in 600 ml water. After brief stirring, about half of the precipitate was filtered off with suction, washed until it was free of nitrates and dried. The washed and dried precipitate contained 17.5% copper and 30.4% calcium. An amount of the precipitate thus treated containing 200 mg of Cu was subjected to reducing decomposition at 260 ° C. for 2 hours in a hydrogen stream of 201 / hour. subject. A catalyst was obtained which hydrogenated 30 ml of nitrobenzene per hour at 270 ° C. to aniline with a yield of 27%.

The other half of the precipitate was according to the invention for 14 hours at 150 ° C with carbonic acid a pressure of 80 atm. treated. The obtained reaction product was filtered, washed and dried. It contained 17.7% copper, 28.4% calcium and 10.91% (theoretical: 11.10%) carbon. One 200 mg of copper-containing amount of the mixed carbonate thus obtained was for 2 hours at 260 ° C in one Hydrogen flow of 201 / h decomposed in a reducing manner. The catalyst prepared in the manner described hydrogenated at 270 ° C 30 ml of nitrobenzene per hour with 90% yield to aniline.

Claims (2)

Claims. 1. A process for the production of highly active mixed catalysts from the oxide hydrate mixture of a catalytically active and a carrier metal by pressure treatment at elevated temperature and subsequent thermal decomposition in a hydrogen stream, characterized in that a precipitate is used as the oxide hydrate mixture, which consists of the suspension of a basic oxide with carrier properties and the Solution of one or more salts of one or more catalytically active metals with the same or approximately the same ionic radii as the metal of the support has been obtained, and the pressure-heat treatment with carbon dioxide is carried out to form carbonate mixed crystals. 2. The method according to claim 1, characterized in that the treatment with carbon dioxide at Temperatures between 100 and 200 ° C and under pressures of 10 to 100 atm. is carried out. Considered publications:
BuU. Soc. Chim. BeIg., 46, p. 596 (1937);
Ind. And Eng. Chem., 42, p. 299 (1950). Legacy Patents Considered:
German Patent No. 1,054,968.