EP1343744A2

EP1343744A2 - Method for producing alcohols by hydrogenating carbonyl compounds

Info

Publication number: EP1343744A2
Application number: EP01988069A
Authority: EP
Inventors: Daniel Ostgard; Monika Berweiler; Stefan Röder
Original assignee: Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2000-12-23
Filing date: 2001-12-21
Publication date: 2003-09-17

Abstract

The invention relates to a method for producing alcohols by catalytically hydrogenating carbonyl compounds with hydrogen or with gases that contain hydrogen in the presence of a hydrogenation catalyst of the Raney type, whereby the catalyst is utilized in the form of hollow bodies. Nickel, cobalt, copper, iron, platinum, palladium or ruthenium are preferably used as catalytically active constituents.

Description

Process for the preparation of alcohols by hydrogenation of carbonyl compounds

The invention is directed to an improved process for the preparation of alcohols from carbonyl compounds, comprising the catalytic hydrogenation of

Carbonyl compounds with hydrogen or hydrogen-containing gases in the presence of a molded _^, the hydrogenation catalyst of the Raney type. The invention includes in particular the production of sugar alcohols. The method allows the use of significantly less

Amounts of catalyst in the production of the alcohols with the same or higher yields than in the previously known methods.

According to this invention, carbonyl compounds are taken to mean all organic compounds which have a C = 0-

Contain grouping, including those compounds that contain a 0 = C-0 grouping. Carbonyl compounds thus mean ketones, aldehydes, carboxylic acids, carboxylates, carboxylic anhydrides, carboxylic esters, carboxamides and carboxylic acid halides.

Alcohols are an extremely important class of substances in organic chemistry. They serve, for example, as starting materials for the production of solvents, surfactants, perfumes, flavors, additives, pharmaceuticals and other organics. In addition, they are of great importance as .Monomers of various plastics. Sugar alcohols are widely used as sugar substitutes, for example.

In the production of alcohols by hydrogenation, carbonyl compounds, Raney catalysts are often preferred because of their good catalytic properties and because they are much easier to produce than supported catalysts. Raney catalysts, which are also called activated metal catalysts, consist of an alloy of at least one catalytically active metal and at least one metal which can be leached out with alkalis. Aluminum is predominantly used for the alloy component which is soluble in alkalis, but other metals such as zinc and silicon can also be used. By adding alkalis to the alloy, the leachable component is released, thereby activating the catalyst.

Numerous inventions for the production of alcohols from carbonyl compounds by catalytic hydrogenation with Raney catalysts are known. Depending on the process, different Raney catalysts, more precisely catalysts with different active metals or metal combinations, are used.

Document EP 0 724 908 describes a process for the preparation of alcohols from carbonyl compounds in which Raney catalysts, the catalytically active component of which is a noble metal, are used as hydrogenation catalysts. The catalysts are used in powder form.

Raney powder catalysts have the disadvantage that they can only be used in a batch process and that they have to be separated from the reaction media after the catalytic reaction. For this reason among other things, it is preferred to manufacture

To carry out alcohols by hydrogenation of carbonyl compounds with the aid of shaped Raney catalysts and, if possible, in a continuous process. For this purpose, fixed bed catalysts are necessary which, in addition to good catalytic activity, must also have sufficient strength for continuous operation.

JP 07206737 A2 describes a further process for the preparation of alcohols by catalytic hydrogenation ⁾ >N> P ¹ P ¹ σ cπ o cπ o Cπ a

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Achieve activities in the special case of hydrogenation of carbonyl compounds.

The invention relates to a process for the preparation of alcohols by catalytic hydrogenation of carbonyl compounds with hydrogen or hydrogen-containing gases in the presence of a shaped hydrogenation catalyst according to Raney, which is characterized in that the Raney catalyst is in the form of hollow bodies. This process has the advantage that alcohols can be produced with the same or higher yields using significantly smaller amounts of catalyst than has been possible up to now in the prior art.

The advantage on which this invention is based is achieved by using Raney catalysts in the form of hollow bodies. The catalysts used in the process according to the invention can be prepared in accordance with the method described in DE 199 33 450.1. According to this method, a mixture of an alloy powder of a catalytically active metal with a leachable metal, preferably aluminum, an organic binder and optionally an inorganic binder, water and promoters is applied to balls which consist of a thermally removable material. Polystyrene foam balls can preferably be used. The application of the mixture containing the metal alloy to the polymer balls can preferably be carried out in a fluidized bed. 0-10% by weight of polyvinyl alcohol and / or 0-3% by weight of glycerol can preferably be used as organic binders. The coated polymer foam balls are then calcined above 300 ° C., preferably in a range from 450 to 1300 ° C., in order to thermally remove the polymer foam and to sinter the metal. This gives the hollow spheres a stable shape. After the calcination, the hollow spherical catalysts are treated with activated basic solutions, preferably alkali or alkaline earth metal hydroxides in water, more preferably aqueous sodium hydroxide solution. The catalysts obtained in this way have bulk densities of between 0.3 and 1.3 kg / l.

For the process according to the invention it is preferred that the hollow Raney catalysts contain nickel, cobalt, copper, iron, platinum, palladium, ruthenium or mixtures of these metals as catalytically active constituents.

Raney catalysts of this type which are activated by leaching aluminum, silicon and / or zinc, in particular aluminum, by means of alkalis are preferably used in the production of alcohols according to the invention.

According to the invention, the process is carried out with catalysts in the form of hollow bodies. It is preferred that the Raney catalyst be in the form of hollow spheres. Hollow balls are usually easy to manufacture and have a high breaking strength.

An important advantage of the process according to the invention is that the Raney catalysts used have a lower bulk density than the Raney catalysts known from the prior art for the hydrogenation of carbonyl compounds. It is advantageous that the bulk density of the Raney catalysts used is in the range from 0.3 g / ml to 1.3 g / ml.

If too large shaped catalyst bodies are used, the starting material to be hydrogenated may not come into sufficient contact with the catalyst. Too small a particle size of the catalytic converters leads to a very large, possibly too large, pressure loss in a continuous mode of operation. Therefore, it is preferred that those used

Shaped catalyst bodies have a diameter in the range of 0.05 to 20 mm.

So that the catalysts used in the process according to the invention have sufficient strength on the one hand and a low bulk density on the other hand, it is preferred that the shaped catalyst bodies used have a shell thickness in the range from 0.05 to 7 mm, preferably 0.1 mm to 5 mm.

The catalyst shells can be impermeable or have a porosity of 0% up to 80% and higher.

In the process according to the invention, hollow-body catalysts which consist of one or more layers can be used. If the shaped catalyst bodies have multiple layers, the

Shaped body dried in the manufacture between the individual coating steps. This is preferably carried out in a fluidized bed at temperatures from 60 to 150 ° C.

It is possible that the shaped catalyst bodies used in the process contain an inorganic binder. The binder enables a greater strength of the hollow catalyst bodies, which is necessary due to their hollow shape. Powders of the metals which are also present as catalytically active constituents in the catalyst alloy are preferably added as binders in the production of the hollow catalyst bodies. However, it is also possible to add other binders, in particular other metals, as binders.

It is often also advantageous that the shaped catalyst bodies used in the process contain no binder. If cobalt catalysts are used according to the invention to produce the alcohols, they are preferably used without a binder. Shaped hollow body Cobalt catalysts have sufficient strength even without added binders.

The catalyst alloy of the catalysts used according to the invention is preferably composed of 20-80% by weight of one or more catalytically active metals and 20-80% by weight of one or more alkali-leachable metals, preferably aluminum. A rapidly or slowly cooled alloy can be used as the catalyst alloy. Rapid cooling means, for example, cooling at a rate of 10 to 10 ⁵ K / s. Cooling media can be various gases or liquids such as water. Slow cooling means methods with lower cooling rates.

Hollow Raney catalysts doped with other metals can be used in the process according to the invention. The doping metals are often referred to as promoters. The doping of Raney catalysts is described, for example, in documents US Pat. No. 4,153,578, DE 21 01 856, DE 21 00 ^' 373 or DE 20 53 799. The cobalt catalyst used can preferably with one or more of the elements from groups 3B to 7B, 8 and 1B of the periodic table, in particular chromium, manganese, iron, vanadium, tantalum, titanium, tungsten, molybdenum, rhenium and / or metals

Platinum group. It is also possible for the cobalt catalyst used to be doped with one or more of the elements from groups 1A, 2A, 2B and / or 3A of the periodic table and / or germanium, tin, lead, antimony or bismuth. The proportion of promoters in the catalyst can preferably be 0-20% by weight. The promoters can already be contained as an alloy component or can only be added at a later time, in particular after activation. During the process according to the invention, the hollow-body Raney catalysts are used in the activated form. The leachable metal present in the non-activated shaped catalyst bodies can be wholly or only partially leached out with alkalis in the activated state.

The process according to the invention can be carried out with hydrogen as the hydrogenation gas or with gas mixtures which contain hydrogen, for example a mixture of hydrogen and carbon monoxide and / or carbon dioxide.

In order to avoid possible poisoning of the catalyst, it is preferred to carry out the process according to the invention with a gas or gas mixture containing at least 95%, preferably at least 99%, hydrogen.

The process allows the production of more or less pure individual substances and also the production of mixtures of different alcohols. In particular in the production of chiral alcohols, for example by hydrogenation of asymmetrically structured ketones, product mixtures can be obtained from different enantiomers or diastereomers.

It is preferred that the hydrogenation be carried out in a fixed bed or suspension reactor in continuous operation. However, the invention also provides that the hydrogenation is carried out in a batch process. With continuous operation, the reactor can be operated in the bottom or trickle bed process, the trickle bed process being preferred.

The process according to the invention can be carried out using ketones, aldehydes, carboxylic acids, carboxylates,

Perform carboxylic acid anhydrides, carboxylic acid esters, carboxylic acid amides and / or carboxylic acid halides. The choice of the suitable starting compound depends, among other things, on the desired product. The output connection must be like this co co to MP ¹ π o Cπ O Cπ O Cπ

p-fluorobenzoic acid, methylbenzoic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phenoxybenzoic acid, cyclohexane carboxylic acid, the methyl and ethyl esters, propaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, benzaldehyde, acaldehyde, benzaldehyde, acaldehyde, acaldehyde, benzaldehyde, acaldehyde, acetic acid, benzaldehyde, acaldehyde, acetic acid, benzaldehyde, acaldehyde, benzaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, benzaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acaldehyde, acetic acid, benzaldehyde , Benzophenone, γ-butyrolactone, ε-caprolactone, maleic anhydride, phthalic anhydride, glucose, xylose, lactose, fructose, 3-hydroxypropionaldehyde.

With the process according to the invention, aliphatic and aromatic alcohols and alcohols with aromatic and aliphatic groups can be produced from the underlying carbonyl compounds. The alcohols can be primary and secondary alcohols. The products can be alcohols with the general formula

R ^ CH-OH

be, where R ¹ and R ^{2 are} independently aliphatic and / or aromatic, unbranched and / or branched, substituted and / or unsubstituted, saturated and / or unsaturated radicals or hydrogen. The alcohols produced according to the invention can be open-chain or alcohols containing alicyclic or aromatic groups.

It is preferred that the product obtained is alcohols having the general formula R ¹ R ² CH-OH, where R ¹ and R ² independently of one another are methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl and / or n-dodecyl radicals and / or radicals of the general formula H ₃ C- (CH ₂ ) _n -, where n is an integer from 11 to 30, or are hydrogen. The starting product is preferably the aldehydes, ketones, carboxylic acids, carboxylates, open-chain esters, in particular the methyl and ethyl esters, and non- or N-alkylated carboxamides.

It is also possible that the radicals R ¹ and / or R ² with one or more radicals from the series F-, Cl-, Br-, I-, N0 ₂ -, NH ₂ -, OH-, CN-, alkyl -, Aryl, alkenyl, alkynyl, 0 = C, HOOC, H ₂ NOC, ROOC, RO with R = alkyl, aryl, alkenyl or alkynyl are substituted.

It is possible that the products obtained are alcohols which contain two or more hydroxyl groups. These can be obtained by hydrogenation of carbonyl compounds which have two or more C 0 groups and optionally already have hydroxyl groups or by hydrogenation of carbonyl compounds which have only one C = 0 group and at least one hydroxyl group.

Likewise preferred is the production of alcohols with the general formula Ar- (CH ₂ ) _m CR ³ H-OH, where Ar is a mononuclear aromatic radical which is not, single, double, triple, quadruple or quintuple substituted or an arbitrarily substituted multinuclear aromatic radical , m is an integer between 0 and 20 and R ^{3 is} a substituted or unsubstituted alkyl, cycloalkyl, aryl, alkenyl or alkynyl radical. Possible substituents of the aromatic radical Ar and / or of the radical R ³ are F-, Cl-, Br-, I-, N0 ₂ -, NH ₂ -, HO-, CN-, alkyl-, especially methyl- and ethyl- , Aryl, alkenyl, alkynyl, 0 = C, HOOC, H ₂ NOC, R ³ OOC and / or RO residues.

Diols of the general formula HO- (CH ₂ ) p-OH are preferred, where p is an integer between 2 and 30, in particular those diols with p = 2, 3, 4, 5, 6, 7 and 8. These are preferred Alcohols from the underlying hydroxyaldehydes, hydroxycarboxylic acids, hydroxycarboxylates, hydroxycarboxamides, hydroxycarboxylic acid esters, dialdehydes, dicarboxylic acids, dicarboxylates containing the same number of carbon atoms, co co ro to P * P ¹ cπ o cπ σ cπ o cπ

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Reaction temperatures are in the range between room temperature and 300 ° C, preferably between 30 ° C and 250 ° C, in particular in the range between 40 ° C and 180 ° C. The catalyst loading can preferably be in a range from 0.05 kg to 5 kg of the compound to be hydrogenated per kg of catalyst per hour. If the process according to the invention is carried out in a batch process, the mass ratio between the catalyst and the carbonyl compound to be hydrogenated is preferably in the range between 0.01 and 1.

According to the invention, the starting compounds for the production of polyols, in particular sugar alcohols, are preferably hydrogenated by the following process: 10 to 70% by weight, preferably 15 to 50% by weight, in particular 40 to 50% by weight. -% owned

Solution of a hydroxyaldehyde or hydroxyketone, preferably a sugar, in demineralized water. The pH is preferably in the range between 3.0 and 12.0. The pH can be adjusted to the desired pH, for example, by adding water-soluble, basic reacting compounds, such as alkali carbonates or ammonia, in aqueous solution or acidic compounds, such as sugar acids, sorbic acid or citric acid. This solution is then hydrogenated.

The polyalcohols can particularly preferably be prepared continuously in a fixed bed process or semi-continuously. The solution to be hydrogenated can be passed through the catalyst bed from above or from below. A cocurrent or countercurrent method can be used in a known manner. The catalyst loads can usually be in the range between 0.05 and 5 kg of carbonyl compound per kg of catalyst per hour.

However, the invention also provides that the hydrogenation in the suspension process or in the batch process in the manner CO ro to H o Cπ O Cπ π

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P- φ P- 3 P a- and others φ d P Φ Φ a P- o X

00 PP ⁴ 3 φ 00 P>ss; Φ tsi Ω 3 Φ a Φ Po a Φ rt 3 a 3- Φ 3 o Φ φ CO Φ 3 d er ao P- φ Φ d rt φ rt φ P- rt P rt P ¹ er d P a ua P o P , Ω Φ 3 ^" o 3 3 d 00

P P- P lO Φ 3 Ω 00 3 od Φ 3 00 Φ er Φ aa P? P- ^ P ¹ o Φ Φ rt

Ω φ o 3 • 3 "rt Hl 3 N and others 00 DJ Φ er Φ Sl φ a cπ 3 co DJ

3 "P Φ Hi ua o 00 er rt P 3 P- 3 Φ P t i P o er rt P? Rt o CO 3" 3 ua - Φ Φ p ω P d P- DJ t σ DJ rt

Ω r a Φ Φ P- a Φ φ <! 3 O: a a Ω Φ o P P 3 O d P- 3 3 00 Φ 3 P- o 00 "DJ P» Φ PT P Ω d a P

Pi Φ 3 rt 00 00 P Φ ia cπ a φ rt d Ω Φ

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P- rt 3 Φ

Preventing caramelization of the starting materials or reducing the formation of by-products.

The process according to the invention for the production of alcohols by catalytic hydrogenation of carbonyl compounds with the aid of hollow Raney catalysts has the following advantages:

The hollow body-shaped Raney catalyst used according to the invention has a significantly lower bulk density than previously used Raney catalysts. As a result, much less catalyst material is required than in the previously known processes.

Despite the significantly smaller amount of catalyst material, the production of alcohols can be carried out with high conversion rates, very good yields and very good space-time yields.

The catalyst used in the process according to the invention has very good strength. This results in very good hydrogenation activity that lasts for a long time.

Application example 1

The catalytic activity of the catalyst of Examples 1-6 during the hydrogenation of glucose to sorbitol was compared. For this purpose, 20 ml of catalyst were placed in a tubular reactor and tested in a trickle phase. The temperature of the reaction became 140 ° C, the concentration of glucose in water became 40% by weight, and the pressure of the reaction became 50 bar. The throughput of hydrogen was 22.5 l / h and the LHSV became 3 h ^-1 . The product mixture was analyzed by HPLC, example 1

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, cast in a crucible, cooled in air, reduced in size and the particle size distribution of the powder was <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approximately 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <65 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This

Suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al pre-coated polystyrene balls while suspended in an upward air stream (nitrogen and other gases can also be used). After coating the

Polystyrene balls with the aforementioned solutions were heated to 500 ° C to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. 20 ml (17.69 grams) of this catalyst were tested in accordance with Application Example 1 and the results of this experiment are shown in Table 1. Tabella 1. The results of Example 1,

Example 2

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, atomized in water and the particle size distribution of the powder became <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in A coating solution was prepared in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, atomized in water and the particle size distribution of the powder became <65 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight

Polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al precoated polystyrene balls while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then in a 20% by weight sodium hydroxide solution for about 1.5 hours 80 ° C activated. The activated hollow spheres obtained had a diameter of approximately 3.7 mm and a shell thickness of approximately 700 μm. 20 ml (13.44 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 2.

Tabella 2. The results of Example 2

Example 3

By suspending 1730 grams of 53% Ni and 47% AI

Alloy powder (This alloy was melted in the induction furnace, atomized in nitrogen and the

Grain size distribution of the powder was <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approx. 2

A coating solution was prepared by weight of polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, atomized in nitrogen and the particle size distribution of the powder became <65 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the above-mentioned polystyrene balls precoated with Ni / Al, while this was carried out in one after air flow directed above (nitrogen and other gases can also be used) were suspended. After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.7 mm and a shell thickness of approximately 700 μm. 20 ml (13.44 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 3.

Tabella 3. The results of Example 3,

• Example 4

A free-flowing, pelletizable catalyst mixture was according to the instructions in EP 0 648 534 AI for a catalyst made of 1000 grams of 50% Ni and 50% Al

Alloy powder (this alloy was melted and water atomized in the induction furnace), 75 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 50 grams of ethylene bis-stearoyla id. Tablets with a diameter of 4 mm and a thickness of 4 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution. 20 ml (28.75 grams) of this catalyst were tested and tested according to use example 1 the results of this experiment are shown in Table 4.

Tabella 4. The results of Example 4.

Example 5

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in air and reduced in size and the particle size distribution of the powder was <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <65 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al precoated polystyrene balls while suspended in an upward air stream (nitrogen and other gases can also be used). After coating the polystyrene balls with the previously mentioned solutions the balls are heated to 500 ° C to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with a sodium molybdate solution and the final Mo content of the catalyst became 0.3%. 20 ml (18.74 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 5.

Tabella 5. The results of Example 5.

Example 6

By suspending 1730 grams of 48.5% Ni, 50.1% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the grain size distribution the powder was <63 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then placed on 1,000 ml polystyrene balls with a

Sprayed on diameter by about 2 mm, while they were suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 gram 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in air, reduced in size and the particle size distribution of the powder was reduced <63 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with an H ₂ Re0 ₄ solution and the Re content of the catalyst at the end became 5%. 20 ml (17.59 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 6.

Tabella 6. The results of Example 6,

Example of use 2

The catalytic activity of the catalyst of Examples 7-18 during the hydrogenation of acetone to isopropanol was compared. For this purpose, 20 ml of catalyst were placed in a tubular reactor and tested in a trickle phase. The temperature of the reaction became 75 ° C, the reaction was carried out with pure acetone and the pressure of the reaction became 5 bar. The throughput of hydrogen was 120 l / h and the LHSV became 4.1 h ^-1 . The product mixture was analyzed by GC.

Example 7

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder was <25 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approximately 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al, while this was in an upward air stream (Nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.7 mm and a shell thickness of approximately 700 μm. 20 ml (19.59 grams) of this catalyst were tested in accordance with Application Example 2 and the results of this experiment are shown in Table 7.

Example 8

20 ml (17.69 grams) of the catalyst from Example 1 were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Example 9

20 ml (13.44 grams) of the catalyst from Example 2 were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Example 10

20 ml (13.44 grams) of the catalyst from Example 3 were tested according to Application Example 2 and the results of this experiment are shown in Table 7. Example 11

By suspending 1730 grams of 48% Ni, 49% Al, 1.3% Cr and 1.0% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in air, reduced in size and the grain size distribution of the powder became < 65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then placed on 1,000 ml polystyrene balls with a

Sprayed on diameter by about 2 mm while they were suspended in an upward air flow. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 48% Ni, 49% Al, 1.3% Cr and 1.0% Fe

Alloy powder (this alloy was melted in an induction furnace, poured into a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <65 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution with a content of approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 6 mm and a shell thickness of approximately 700 μm. 20 ml (9.48 grams) of this catalyst were tested according to Example 2 and the results of this experiment are shown in Table 7.

Example 12

By suspending 1730 grams of 53% Ni and 47% AI

Alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution A coating solution was prepared with a content of approximately 2% by weight of polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al precoated polystyrene balls while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had one Diameter by approx. 4 mm and a jacket thickness by approx. 700 μm. 20 ml (16.59 grams) of this catalyst were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Example 13

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, cast in a crucible, cooled in air, reduced in size and the particle size distribution of the powder was <25 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approximately 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (This alloy was melted in the induction furnace, poured in a crucible, in the

"

Air cooled, reduced in size and the particle size distribution of the powder was <65 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol. This

Polystyrene balls with the aforementioned solutions were heated to 500 ° C to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then in a 20% by weight sodium hydroxide solution activated at 80 ° C. for approx. 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 4 mm and a shell thickness of approximately 700 μm. 20 ml (16.28 grams) of this catalyst were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Example 14

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, cast in a crucible, cooled in air, reduced in size and the particle size distribution of the powder was <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approximately 2% by weight of polyvinyl alcohol

Coating solution prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in air, verkleiniert and the grain size distribution of the ^'powder was <65 microns), 90 gram pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al, while this was in an upward air stream

(Nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then up to Heated at 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 4 mm and a shell thickness of approximately 700 μm. 20 ml (15.86 grams) of this catalyst were tested in accordance with Application Example 2 and the results of this experiment are shown in Table 7.

Example 15

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in air, reduced in size and the particle size distribution of the powder was <65 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approximately 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then 1,000 ml of the aforementioned pre-coated with Ni / Al polystyrene beads sprayed, while these in an upwardly directed flow of air (nitrogen and other gases can also be used) ^'were suspended. After coating the polystyrene balls with the previously mentioned solutions the balls are heated to 500 ° C to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The resulting activated hollow spheres had a diameter of about 4 mm and a shell thickness of ^'ca.700μm. 20 ml (16.19 grams) of this catalyst were tested in accordance with Application Example 2 and the results of this experiment are shown in Table 7.

Example 16

By suspending 1730 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <25 μm), 90 grams pure Nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al precoated polystyrene balls while in an upward stream of air (nitrogen and other gases can also be used) were suspended. After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3 mm and a shell thickness of approximately 700 μm. 20 ml (19.06 grams) of this catalyst was loud

Application example 2 checked and the results of this experiment are shown in Table 7.

Example 17 A free-flowing, pelletizable catalyst mixture was prepared according to the instructions in EP 0 648 534 AI for a catalyst made of 1000 gram 50% Ni and 50% Al alloy powder (this alloy was melted and water atomized in the induction furnace), 75 gram pure nickel powder (99% Ni and d50 = 21 μm) and 50 grams of ethylene bis

Stearoylamide manufactured. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution. 20 ml (35.1 grams) of this catalyst were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Example 18

A free-flowing, pelletizable catalyst mixture was according to the instructions in EP 0 648 534 AI for one Catalyst made of 1000 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in air and reduced in size), 150 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 50 grams of ethylene -Bis-stearoylamide made. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution. 20 ml (42.74 grams) of this catalyst were tested according to Application Example 2 and the results of this experiment are shown in Table 7.

Table 7. The results from the acetone tests

Example of use 3

The catalytic activity of the catalyst of Examples 19 to 21 during the hydrogenation of maleic anhydrides (MSA) to succinic anhydrides (BSA), 1,4-butanediol (BDO), Ga a-butyrolactone (GBL) and tetrahydrofuran (THF) were compared. For this purpose, 40 ml of catalyst were placed in a tubular reactor and tested in a trickle phase. The temperature of the reaction was from 195 to 211 ° C, the content of MSA in the dioxane became 50% by weight and the pressure of the reaction became 70 bar. The throughput of hydrogen was 60 l / h, the WHSV was from 0.116 to 0.467 h ^"1 and the LHSV was from 0.54 to 2.12 h ^{" 1} . The product mixture was analyzed by GC.

Example 19

By suspending 1730 grams of 40% Ni, 58.5% Al, 1.0% Cr and 0.5% Fe alloy powder (this alloy was melted in an induction furnace, poured in a crucible, atomized and reduced in water) and 130 grams pure Nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing approx. 2% by weight of polyvinyl alcohol was prepared as a coating solution. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 40% Ni, 58.5% Al, 1.0% Cr and 0.5% Fe alloy powder Alloy was melted in the induction furnace, poured in a crucible, atomized and reduced in water), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then in a 20 wt .-%

Sodium hydroxide solution activated at 80 ° C for approx. 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with an H ₂ Re0 solution and the Re content of the catalyst became 1% at the end. 40 ml (57.02 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 8.

Tabella 8. The results of Example 19

Example 20 By suspending 1730 grams of 48.5% Ni, 50.1% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the grain size distribution the powder was <63 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in air , reduced and the particle size distribution of the powder was <63 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then in a 20 wt .-%

Sodium hydroxide solution activated at 80 ° C for approx. 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with an H ₂ Re0 ₄ solution and the Re content of the catalyst at the end became 1.5%. 40 ml (37.75 grams) of this catalyst were tested according to Example 3 and the results of this experiment are shown in Table 9.

Tabella 9. The results of Example 20

Example 21

Sprayed on diameter by about 2 mm, while they were suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe

Alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the particle size distribution of the powder became <63 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution with a content of approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while these were suspended in an upward stream of air (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with a H ₂ Re0 solution and the Re content of the catalyst at the end became 5%. 40 ml (37.75 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 10.

Tabella 10. The results of Example 21

Example of use 4

The catalytic activity of the catalyst from the

Examples 22 to 24 during the hydrogenation of

Fatty acid methyl esters to fatty alcohols were compared For this purpose, 72 grams of the catalyst were placed in a basket in an autoclave and tested in a liquid phase. The temperature of the reaction became 200 ° C, the amount of fatty acid methyl esters became 500 ml, the solution was stirred 1000 rpm and the pressure of the

Reaction became 200 bar. The product mixture was analyzed by GC.

Example 22

A free-flowing, pelletizable catalyst mixture was prepared according to the instructions in EP 0 648 534 AI for a catalyst made from 1000 grams of 53% Ni and 47% Al alloy powder (this alloy was melted in an induction furnace, poured in a crucible, cooled in air and reduced in size), 150 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 50 grams of ethylene bis-stearoylamide are produced. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution.

This catalyst was doped with an H ₂ Re0 solution and the Re content of the catalyst became 3% at the end. 72 grams of this catalyst were tested according to Application Example 4 and the results of this experiment are shown in Table 11.

Table 11. The results of Example 22

Example 23

By suspending 1730 grams of 48.5% Ni, 50.1% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the grain size distribution the powder was <63 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in air , reduced and the particle size distribution of the powder was <63 μm), 90 grams of pure nickel powder (99% Ni and d50-21 μm) and 1083 ml of an aqueous solution containing approx. 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used). After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with an H ₂ Re0 solution and the Re content of the catalyst became 3% at the end. 72 grams of this catalyst were tested according to Application Example 4 and the results of this experiment are shown in Table 12.

Table 12. The results of Example 23

Example 23

By suspending 1730 grams of 48.5% Ni, 50.1% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in the air, reduced in size and the grain size distribution the powder was <63 μm) and 130 grams of pure nickel powder (99% Ni and d50 = 21 μm) in 1557 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol, a coating solution was prepared. ^This' suspension was then sprayed mm to 1,000 ml Poylstyrolkugeln having a diameter of about 2, while they were suspended in an upwardly directed air stream. 1 liter of this sphere was further coated with an alloy solution. The solution for the second layer consisted of 1203 grams of 48.5% Ni, 50.5% Al, 0.9% Cr and 0.5% Fe alloy powder (This alloy was melted in the induction furnace, poured in a crucible, cooled in air , reduced and the grain size distribution of the powder was <63 μm), 90 grams of pure nickel powder (99% Ni and d50 = 21 μm) and 1083 ml of an aqueous solution containing about 2% by weight of polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the above-mentioned polystyrene balls precoated with Ni / Al / Cr / Fe, while this was in an upward air stream (nitrogen and other gases can also be used) were suspended. After the polystyrene balls had been coated with the aforementioned solutions, the balls were heated to 500 ° C. in order to burn out the polystyrene. The Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together. The hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours. The activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 μm. This catalyst was doped with an H ₂ Re0 ₄ solution and the Re content of the catalyst at the end became 4.5%. 72 grams of this catalyst were tested according to Application Example 4 and the results of this experiment are shown in Table 13.

Table 13. The results of Example 24

Claims

claims

1. A process for the preparation of alcohols by catalytic hydrogenation of carbonyl compounds with hydrogen or hydrogen-containing gases in the presence of a Raney shaped hydrogenation catalyst, characterized in that the Raney catalyst is used in the form of hollow bodies.

2. The method according to claim 1, characterized in that the hollow Raney catalysts nickel,

Contain cobalt, copper, iron, platinum, palladium, ruthenium or mixtures of these metals as catalytically active constituents.

3. The method according to claim 1 or 2, characterized in that the Raney catalyst is in the form of hollow spheres.

4. The method according to claim 1 or 3, characterized in that the bulk density of the Raney catalysts used is in the range from 0.3 g / ml to 1.3 g / ml.

5. The method according to claim 1 or 4, characterized in that the used

Shaped catalyst bodies have a diameter in the range of 0.05 to 20 mm.

6. The method according to one or more of claims 1 to 6, characterized in that the shaped catalyst bodies used have a shell thickness in the range from 0.05 to 5 mm, preferably 0.1 mm to 5 mm.

7. The method according to one or more of claims 1 to 6, characterized in that the shaped catalyst bodies used in the process contain an inorganic binder.

8. The method according to one or more of claims 1 to 6, characterized in that the shaped catalyst bodies used in the process do not contain a binder.

9. The method according to one or more of claims 1 to

8, characterized in that the cobalt catalyst used with one or more of the elements from groups 3B to 7B, 8 and 1B of the periodic table, in particular chromium, manganese, iron, vanadium, tantalum, titanium, tungsten, molybdenum, rhenium and / or metals the platinum group is endowed.

10. The method according to one or more of claims 1 to

9, characterized in that the cobalt catalyst used with one or more of the elements from groups 1A, 2A, 2B and / or 3A of

Periodic table and / or germanium, tin, lead, antimony or bismuth is doped.

11. The method according to one or more of claims 1 to

10, characterized in that the hydrogenation in a fixed bed or suspension reactor in continuous

Operation is carried out.

12. The method according to one or more of claims 1 to 10, characterized in that one carries out the hydrogenation in a batch process.

13. The method according to one or more of claims 1 to 12, characterized in that the products are alcohols having the general formula R ¹ R ² CH-OH, where R ¹ and R ² independently of one another are aliphatic and / or aromatic, unbranched and / or are branched, substituted and / or unsubstituted, saturated and / or unsaturated radicals or hydrogen.

14. The method according to claim 13, characterized in that the product is alcohols with the general formula R ¹ R ² receives CH-OH, where R ¹ and R ² independently of one another methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl , iso-pentyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl and / or n-dodecyl radicals and / or radicals of the general formula H ₃ C- (CH ₂ ) _n -, where n is an integer from 11 to 30, or are hydrogen.

15. The method according to one or more of claims 13 'and 14, characterized in that the radicals R ¹ and / or R ² with one or more radicals from the series F-, Cl-, Br-, I-, N0 ₂ - , NH ₂ -, OH-, CN-, alkyl-, aryl-, alkenyl-, alkynyl-, 0 = C-, HOOC-, H ₂ NOC-, ROOC-, RO- with R = alkyl-, aryl-, Alkenyl or alkynyl are substituted.

16. The method according to one or more of claims 13 and 14, characterized in that as products

Alcohols containing two or more hydroxyl groups.

17. The method according to claim 13, characterized in that the product obtained is alcohols having the general formula Ar- (CH ₂ ) mCR ³ H-OH, where Ar is a mononuclear aromatic which is not mono-, mono-, polysubstituted, trisubstituted, trisubstituted or quintupled Radical or an arbitrarily substituted polynuclear aromatic radical, m is an integer between 0 and 20 and R ^{3 is} a substituted or unsubstituted alkyl,

Is cycloalkyl, aryl, alkenyl or alkynyl.

18. The method according to claim 16, characterized in that diols of the general formula HO- (CH ₂ ) _p -OH are obtained, where p is an integer between 2 and 30, in particular those diols with p = 2, 3, 4, 5, 6, 7 and

19. The method according to claim 16, characterized in that sugar alcohols are obtained as products.

20. The method according to one or more of claims 1 to 12, characterized in that the products are a sugar alcohols from the hydrogenation of ketose, aldose or a mixture of ketoses and aldoses.

21. The method according to one or more of claims 1 to 12, characterized in that the products is sorbitol from the hydrogenation of dextrose.

22. The method according to one or more of claims 1 to 12, characterized in that the product is sorbitol from the hydrogenation of a mixture of sorbitol and mannitol from fructose.

23. The method according to one or more of claims 1 to 12, characterized in that the product is xylitol from the hydrogenation of xylose.

24. The method according to one or more of claims 1 to 12, characterized in that the product is maltitol from the hydrogenation of maltose.

25. The method according to one or more of claims 1 to 12, characterized in that the products is isomaltite from the hydrogenation of isomaltose.

26. The method according to one or more of claims 1 to 12, characterized in that the product is dulcite from the hydrogenation of galactose.

27. The method according to one or more of claims 1 to 12, characterized in that the products is lactitol from the hydrogenation of lactose.

28. The method according to one or more of claims 1 to 12, characterized in that the product is fatty alcohols from the hydrogenation of fatty acid methyl esters.

9. The method according to one or more of claims 1 to 12, characterized in that the products are BSA, GBL, BDO and / or THF from the hydrogenation of MA.