EP0813906A2 - Process for converting an organic compound in presence of a supported ruthenium catalyst - Google Patents

Abstract

Organic compounds are reacted in presence of a catalyst containing 0.01-30 wt% ruthenium (Ru) as active metal, possibly together with sub-group I, VII or VIII metal(s), on a support (I) with an average pore diameter (PD) of at least 50 nm and a BET surface of not more than 30 m<2>/g, in which the ratio of active metal surface to support surface is less than 0.05. Also claimed are supported catalysts as above.

Description

The present invention relates to a method for implementing a organic compound in the presence of a catalyst that acts as an active metal Ruthenium and optionally one or more other metals from I., VII. Or VIII. Subgroup of the periodic table, applied to a macroporous carrier.

In one embodiment, the present invention relates to a process for reacting, preferably hydrogenating, an aromatic compound in which at least one hydroxyl group is bonded to an aromatic nucleus, preferably in addition to the at least one hydroxyl group, at least one, optionally substituted, C _1-10 alkyl group and / or at least one C _1-10 alkoxy group is bonded to an aromatic nucleus. Furthermore, monoalkyl-substituted phenols are preferably used in the process according to the invention.

The mono- or polynuclear aromatic compounds are in Presence of the catalyst described herein preferably to the corresponding ones Cycloaliphatic compounds hydrogenated, the hydroxyl group preserved.  

Cycloaliphatic alcohols, especially alkylcyclohexanols, are important Intermediate products for the manufacture of various fragrances, pharmaceuticals and other fine organic chemicals. By catalytic hydrogenation of the corresponding aromatic precursors are the above cycloaliphatic Alcohols easily accessible.

The process of alkylcyclohexanols by catalytic hydrogenation of the corresponding It is known to produce alkylphenols. The hydrogenation of Alkylphenols to the corresponding alkylcyclohexanols in the presence of Hydrogenation catalysts, especially supported catalysts, has been described many times.

Metallic rhodium, rhodium-platinum, Rhodium-ruthenium alloys as well as ruthenium, palladium or Nickel used on catalyst supports. As a catalyst support Carbon, barium carbonate and especially aluminum oxide are used.

PL 137 526 describes the hydrogenation of p-tert-butylphenol to p-tert-butylcyclohexanol using a nickel catalyst.

DE-A-34 01 343 and EP 0 141 054 describe a process for the preparation of 2- and 4-tert-butylcyclohexanol from 2- and 4-tert-butylphenol by catalytic hydrogenation. The hydrogenation is carried out in two stages, a palladium catalyst on an Al ₂ O ₃ carrier being used in the first stage and a ruthenium catalyst on an Al ₂ O ₃ carrier in the second stage. The metal content on the carrier is 0.1 to 5% by weight. The carriers are not further specified. The product is recycled at a pressure of 300 bar and the cis-tert-butylphenols are preferably obtained, with 0.1 to 0.5% of by-products being obtained.

US 2,927,127 describes a process for the preparation of p-tert-butylcyclohexanol and esters thereof by catalytic hydrogenation of p-tert-butylphenol. 5% rhodium on carbon are used as catalysts, 5% palladium on barium carbonate and 5% ruthenium on carbon used. When using ruthenium on carbon, it was used a pressure of 70 to 120 bar and a temperature of 74 to 93 ° C worked. 66% cis isomer was obtained as the hydrogenation product.

DE-A-29 09 663 describes a process for the preparation of cis-alkylcyclohexanols by catalytic hydrogenation of the corresponding alkylphenols. Ruthenium on an Al ₂ O _{3 support was} used as the catalyst. It was operated at pressures of 40, 60 or 80 bar. The product obtained was predominantly cis-alkylcyclohexanols, with 0.1 to 1% of alkylbenzenes being obtained as a by-product.

In a further embodiment, the present invention relates to a process for the reaction, preferably hydrogenation, of an aromatic compound in which at least one amino group is bonded to an aromatic nucleus, preferably at least one, optionally substituted, C _{1-10 in} addition to the at least one amino group Alkyl group and / or at least one C _1-10 alkoxy group is bonded to an aromatic nucleus. Monoallyl-substituted amines are particularly preferably used.

The mono- or polynuclear aromatic compounds are in Presence of the catalyst described herein preferably to the corresponding ones Cycloaliphatic compounds hydrogenated, the amino group preserved.

Cycloaliphatic amines, especially optionally substituted cyclohexylamines and dicyclohexylamines find use in the manufacture of   Anti-aging agents for rubbers and plastics, as anti-corrosion agents as well as precursors for crop protection agents and textile auxiliaries. Cycloaliphatic diamines are also used in the production of polyamide and Polyurethane resins used and continue to be used as Hardener for epoxy resins.

It is known to cycloaliphatic amines by catalytic hydrogenation of the to produce corresponding mono- or polynuclear aromatic amines. The Hydrogenation of aromatic amines to the corresponding cycloaliphatic Amines in the presence of hydrogenation catalysts, in particular Supported catalysts have been described many times.

Raney cobalt with basic additives, for example, are used as catalysts (JP 43/3180), nickel catalysts (US 4,914,239, DE 80 55 18), rhodium catalysts (BE 73 93 76, JP 70 19 901, JP 72 35 424), and palladium catalysts (US 3,520,928, EP 501 265, EP 53 818, JP 59/196 843) used. The majority, however, become catalysts containing ruthenium used.

DE 21 32 547 describes a process for hydrogenating mononuclear or polynuclear aromatic diamines to the corresponding cycloaliphatic Amines known in the presence of a suspended ruthenium catalyst is performed.

EP 67 058 describes a process for the preparation of cyclohexylamine by catalytic hydrogenation of the corresponding aromatic amine described. As a catalyst, ruthenium metal is finely divided Form used on activated aluminum pellets. After four returns the catalyst began to lose its effectiveness.  

EP 324 984 relates to a method for producing a mixture from optionally substituted cyclohexylamine and optionally substituted Dicyclohexylamine by hydrogenation of optionally substituted Aniline using a ruthenium and palladium on a support containing catalyst, which also has an alkaline reaction Contains alkali metal compound as a modifier. A similar one in principle The process is described in EP 501 265, where the catalyst contains niobic acid, tantalic acid or a mixture of both as modifiers.

No. 2,606,925 describes a process for the preparation of an aminocyclohexyl compound by hydrogenating an appropriate aromatic compound described, a ruthenium catalyst, the active catalytic Component is selected from elemental ruthenium, ruthenium oxides, Ruthenium salts in which the ruthenium is in the anion or in the cation is available. As the examples of this procedure show, there too the catalyst is prepared in a separate step and dried and after longer drying time introduced into the reaction vessel.

Another process for the preparation of cyclohexylamine is described in US 2,822,392, with the main focus of this patent the use of a special reactor in which the aniline and the Hydrogen as starting products in countercurrent with each other for reaction brought, is directed.

US 3,636,108 and US 3,697,449 relate to catalytic hydrogenation aromatic nitrogen containing compound using a Ruthenium catalyst, which also has an alkali metal compound as a modifier includes.  

Common to all of the processes described above is the use of mesoporous supports with BET surfaces which are typically between 50 and over 1000 m ² / g in order to achieve a high activity of the catalyst.

It has also been found to be particularly useful in the hydrogenation with a rhodium-containing one Catalyst, in addition to the high price of the catalyst, as a disadvantage proved that it is not uncommon for larger amounts of these reactions Alkylbenzenes as well as other, unidentifiable compounds, which the hydrogenation are formed as decomposition or by-products, occurred. These by-products make processing and cleaning more difficult of the reaction product especially when e.g. Alkylcyclohexanols as Fragrances or to be used for the production of fragrances. Furthermore, the activity of many of the methods described above decreases used catalysts quickly, especially when the Hydrogenation to accelerate the reaction rate at higher Reaction temperatures is carried out.

In a further embodiment, the present invention relates to a Process for the implementation, preferably hydrogenation, of polymers with hydrogenatable groups, preferably with nitrile groups using the Macroporous ruthenium-containing catalyst described herein.

Process for the hydrogenation of polymers which have at least one hydrogenatable Unity are known per se. A group of polymers that particularly intensive in the past as starting materials in processes for hydrogenation of polymers have been used, have nitrile groups Polymers. These are also preferred in the process according to the invention used, the corresponding amine groups containing polymers be preserved.  

The polymers with amine groups obtained in this process can for example as a branching agent, crosslinking agent or complexing agent are used, being the preferred fields of application for such Polymers e.g. paper manufacture, detergent industry, adhesives and Cosmetics are to be mentioned.

For the reduction of polymers containing nitrile groups to polymers, containing amine groups have been numerous in the past described by systems, whereby in addition to the reduction with complex Metal hydrides, as described, for example, in German patents DE 1 226 303 and DE 2 905 671 are also described, the hydrogenation with hydrogen is to be mentioned.

The latter is much cheaper and, in contrast to reduction, is required with complex metal hydrides only catalytic amounts of a metal-containing Component, which has both economic and environmental benefits brings with it.

Hydrogenation with hydrogen has been both homogeneous in the past catalyzed as well as heterogeneously catalyzed.

The homogeneous catalysis is chemically elegant, but the catalyst separation is much more complex than with heterogeneous catalysis. Especially at Catalytic processes on polymers is the use of a homogeneous Disadvantageous catalyst, since a distillative separation of the polymeric product from the catalyst is not possible. If you look at the polymeric product separate from the homogeneous catalyst by crystallization or precipitation wants, this requires repeated crystallization, since inclusions of the catalyst are unavoidable, resulting in extended response times and longer Costs.  

Problems with catalyst separation occur with the heterogeneous catalytic Reaction management not on. The previously known heterogeneous catalytic Processes for the hydrogenation of polymers containing nitrile groups, mostly using metal fixed bed catalysts according to Raney lead however often only to unsatisfactory sales and selectivities.

No. 2,456,428 describes the hydrogenation of polyacrylonitrile, polymethacrylonitrile and similar polymers. After hydrogenation in the presence of Raney nickel as a catalyst must be unreacted polymer before be further processed. The implementation described there has therefore not gone completely; those to be achieved with this procedure Yields are bad.

According to US 3,122,526, the hydrogenation of cyanoethylated polyacrylonitrile using Raney nickel as a catalyst also a moderate yield of the corresponding amine of below Receive 10%.

US 2,585,583 describes the hydrogenation of copolymers from butadiene and acrylonitrile or methacrylonitrile over suspension hydrogenation catalysts. The No. 2,647,146 describes the hydrogenation of butadiene oligomers with nitrile end groups using a mixture of two suspension catalysts (Pd on coal and Ni on diatomaceous earth). According to these two procedures the catalysts used there must each be filtered off Reaction solution are separated.

In summary, it can be stated that the hydrogenation of Polymers containing nitrile groups to polymers containing amine groups contain, although it is known, good yields of the amine groups So far, however, polymers have only been used using suspension catalysts   have been achieved. These have to be filtered from the reaction solution can be separated and can not be used in a fixed bed reactor will.

A catalyst consisting of a macroporous support material on which a metal of subgroup VIII of the periodic table is applied, the used for the hydrogenation of carbon-carbon double bonds can be described in US 5,110,779. Ninety percent of the Carrier existing pores of the catalyst described there have a diameter of more than 100 nm. The ratio of Surfaces from metal to carrier are 0.07 to 0.75: 1. Doing so in the context of this patent specification in particular on the large surface of the Metal in relation to the carrier, and stated as surprising, since such a catalyst still has a high activity.

Furthermore, the present invention relates in particular to a method for Implementation, preferably hydrogenation, of an organic compound which has at least one C = O group, such as. B. a ketone, aldehyde, a Carboxylic acid or a derivative thereof, or a mixture of two or more from that.

Accordingly, it was an object of the present invention to provide a process for the implementation, preferably hydrogenation, of a organic compound as defined in the introduction, with very high yields or almost complete sales can be achieved.

Another object of the invention is to provide such Process, with only a minimal proportion of by-products or decomposition products during the hydrogenation.  

Furthermore, it should be possible to run the process under high catalyst loads and long downtimes with an extremely high turn-over number, the corresponding hydrogenation products in high yield and high purity can be obtained.

One or more of the above objects are achieved by a process for reacting an organic compound in the presence of a catalyst which, as the active metal ruthenium, alone or together with at least one metal of subgroup I, VII or VIII of the Periodic Table, applied to a support, comprises, the carrier having an average pore diameter of at least 50 nm and a surface BET of at most 30 m ² / g and the amount of active metal being 0.01 to 30 wt .-%, based on the total weight of the catalyst, characterized that the ratio of the surfaces of the active metal and the catalyst support is <0.05.

The above tasks as well as other tasks, if any by processes for hydrogenation as described in the subclaims are solved. A particular advantage of the method according to the invention is that very good results when using only low metal contents can be achieved in the catalyst.

Furthermore, the method according to the invention exhibits high turn-over numbers high catalyst load and over long catalyst life. The catalyst load is the space / time yield of the process, i.e. the amount of reactant reacted per unit of time and per amount present catalyst. Service life means the time or the amount of reacted educt that a catalyst copes with without losing its properties lose and without significantly changing the product properties.  

In addition, the present invention relates to the catalyst defined herein per se, ie a catalyst which comprises ruthenium as the active metal, alone or together with at least one metal of subgroup I, VII or VIII, applied to a support, the support has an average pore diameter of at least 50 nm and a BET surface area of at most 30 m ² / g and the amount of active metal is 0.01 to 30% by weight, based on the total weight of the catalyst, the ratio of the surfaces of the active metal and the catalyst support is <0.05.

LINKS

The term "organic compound" as used in the context of the present Invention used includes all organic compounds that can be implemented catalytically, especially those involving hydrogen groups to be treated, e.g. C-C double or C-C triple bonds, exhibit. It includes both low molecular weight organic compounds as well as polymers. "Low molecular weight organic compounds" are compounds with a molecular weight of less than 500. The The term "polymer" is defined as meaning that it contains molecules with a Molecular weight greater than about 500.

The present invention relates in particular to a method for implementation an organic compound in the presence of a catalyst as herein defined, the reaction being a hydrogenation, dehydrogenation, hydrogenolysis, aminating hydrogenation or dehalogenation, more preferably one Is hydrogenation.  

In particular, organic compounds can be used which have one or more of the following structural units: C = C C≡C C = N C≡N C = O C = S ―NO ₂

The process according to the invention is particularly suitable for the implementation, preferably hydrogenation, an organic compound that is selected from the group consisting of an aromatic compound in which at least a hydroxyl group is attached to an aromatic nucleus, one aromatic compound in which at least one amino group is attached to one aromatic nucleus is bound, a ketone, an aldehyde, a carboxylic acid or a derivative thereof, a polymer that has at least one C-C double bond has, a polymer having at least one C = O group has, a polymer having at least one C≡N group, and a mixture of two or more of them.

Organic can also be used in the process according to the invention Connections are implemented, such as units of different structures defined above, e.g. organic compounds that have both C-C multiple bonds   as well as carbonyl groups, as part of the the catalysts used in the process are capable are to implement one of the two groups selectively, preferably to hydrogenate, i.e. hydrogenation of these groups from about 90 to 100% to be achieved while at the same time the other groups less than 25% and generally in a range from 0 to approximately 7% implemented, preferably hydrogenated. In general first the C-C multiple bonds and then the C = O groups implemented or hydrogenated.

The term "aromatic compound containing at least one hydroxyl group is bound to an aromatic nucleus "or" aromatic compound, in the at least one amino group to an aromatic nucleus "is all connections that are a unit of the following

Structure (I) have: wherein R represents a hydroxyl or an amino group.

If aromatic compounds are used in the process according to the invention in which at least one hydroxyl group and furthermore at least one optionally substituted C _1-10 alkyl radical and / or alkoxy radical are bonded to an aromatic nucleus, this can, depending on the reaction conditions (temperature, solvent) Isomer ratio obtained from cis to trans-configured products can be varied within a wide range. Furthermore, the compounds obtained can be processed further without further purification steps. The formation of alkylbenzenes is practically completely avoided.

Like the compounds described above, in which at least one hydroxyl group is bonded to an aromatic nucleus, aromatic compounds in which at least one amino group is bonded to an aromatic nucleus can also be hydrogenated with high selectivity to the corresponding cycloaliphatic compounds in the process according to the invention are, wherein for the amines additionally substituted with a C _1-10 alkyl radical and / or alkoxy radical with respect to the ratio of the cis and trans isomers, what has been said above applies.

In particular, the formation of Deamination products, such as cyclohexanes or partially hydrogenated Dimerization products such as phenylcyclohexylamines, practically completely avoided.

In detail, the following can be carried out within the scope of the method according to the invention Connections are implemented:

Aromatic compounds containing at least one hydroxyl group an aromatic core is bound

With the process according to the invention, aromatic compounds in which at least one hydroxyl group and preferably furthermore at least one optionally substituted C _1-10 -alkyl radical and / or alkoxy radical are bonded to an aromatic nucleus can be reacted, preferably to the corresponding cycloaliphatic compounds, and also hydrogenated Mixtures of two or more of these compounds can be used.

The aromatic compounds can be mononuclear or polynuclear aromatic compounds. The aromatic compounds contain at least one hydroxyl group which is bonded to an aromatic nucleus, the simplest compound of this group being phenol. The aromatic compounds preferably have one hydroxyl group per aromatic nucleus. The aromatic compounds on the aromatic nucleus or aromatic nuclei can be substituted by one or more alkyl and / or alkoxy radicals, preferably C _1-10 alkyl and / or alkoxy radicals, particularly preferably C _1-10 alkyl radicals, in particular methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl radicals; among the alkoxy radicals, the C _1-8 alkoxy radicals, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy radicals, are preferred. The aromatic nucleus or the aromatic nuclei as well as the alkyl and alkoxy residues can optionally be substituted by halogen atoms, in particular fluorine atoms, or have other suitable inert substituents.

The compounds which can be reacted, preferably hydrogenated, according to the invention preferably have at least one, preferably one to four, in particular one C _1-10 -alkyl radical which is preferably located on the same aromatic nucleus as the at least one hydroxyl group. Preferred compounds are (mono) alkylphenols, where the alkyl radical can be in the o, m or p position to the hydroxyl group. Trans-alkylphenols, also referred to as 4-alkylphenols, are particularly preferred, the alkyl radical preferably having 1 to 10 carbon atoms and in particular being a tert-butyl radical. 4-tert-butylphenol is preferred. Polynuclear aromatic compounds which can be used according to the invention are, for example, β-naphthol and α-naphthol.

The aromatic compounds in which at least one hydroxyl group and preferably also at least one optionally substituted C _1-10 -alkyl radical and / or alkoxy radical are bonded to an aromatic nucleus can also have several aromatic nuclei which are linked via an alkylene radical, preferably a methylene group . The linking alkylene group, preferably methylene group, can have one or more alkyl substituents, which can be C _1-20 alkyl radicals and preferably C _1-10 alkyl radicals, particularly preferred are methyl, ethyl, propyl, isopropyl, butyl or tert-butyl radicals.

Each of the aromatic nuclei can have at least one hydroxyl group bound included. Examples of such compounds are bisphenols, which are described in 4-position linked via an alkylene radical, preferably a methylene radical are.

A particularly preferred reaction in the process according to the invention is a phenol substituted by a C _1-10 -alkyl radical, preferably a C _1-6 -alkyl radical, the alkyl radical optionally being substituted by an aromatic radical, or mixtures of two or more of these compounds.

In a further preferred embodiment of this process, p-tert-butylphenol, Bis (p-hydroxyphenyl) dimethyl methane or a mixture of it implemented.

Aromatic compounds containing at least one amino group an aromatic core is bound

With the method according to the invention, aromatic compounds in which at least one amino group is bonded to an aromatic nucleus can also be reacted, preferably hydrogenated to the corresponding cycloaliphatic compounds, mixtures of two or more of these compounds also being able to be used. The aromatic compounds can be mononuclear or polynuclear aromatic compounds. The aromatic compounds contain at least one amino group which is bonded to an aromatic nucleus. The aromatic compounds are preferably aromatic amines or diamines. The aromatic compounds on the aromatic nucleus or the aromatic cores or on the amino group can be substituted by one or more alkyl and / or alkoxy radicals, preferably C _1-20 alkyl radicals, in particular methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, tert-butyl residues; among the alkoxy radicals, the C _1-8 alkoxy radicals, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy radicals, are preferred. The aromatic nucleus or the aromatic nuclei as well as the alkyl and alkoxy residues can optionally be substituted by halogen atoms, in particular fluorine atoms, or have other suitable inert substituents.

The aromatic compound, in which at least one amino group is bonded to an aromatic nucleus, can also have several aromatic nuclei which are linked via an alkylene group, preferably a methylene group. The linking alkylene group, preferably methylene group, may have one or more alkyl substituents, which may be C _1-20 alkyl radicals and preferably C _1-10 alkyl radicals, particularly preferably methyl, ethyl, propyl, isopropyl, butyl, sec .-Butyl or tert-butyl radicals.

The amino group bonded to the aromatic nucleus can also by one or two of the alkyl radicals described above may be substituted.  

Particularly preferred compounds are aniline, naphthylamine, diaminobenzenes, Diaminotoluenes and bis-p-aminophenylmethane or mixtures thereof.

Compounds containing C = O groups

With the method according to the invention can contain C = O groups Compounds, in particular aldehydes, ketones, carboxylic acids and their Derivatives such as Carboxylic acid esters, carboxylic acid halides and carboxylic acid anhydrides and mixtures of two or more of the above compounds implemented, in particular hydrogenated.

In particular, aldehydes and ketones, preferably those with 1 to 20 carbon atoms, e.g. Formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, phenylacetaldehyde, Acrolein, crotonaldehyde, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-toluoaldehyde, Salicylaldehyde, anisaldehyde, vanillin, cinnamaldehyde, acetone, Methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclohexanone, Isophorone, methyl isobutyl ketone, mesityl oxide, acetophenone, propiophenone, Benzophenone, benzalacetone, dibenzalacetone, benzalacetophenone, Glycol aldehyde, glyceraldehyde, glyoxal, 2,3-butanedione, 2,4-pentanedione, 2,5-hexanedione, Terephthalaldehyde, glutardialdehyde, diethyl ketone, methyl vinyl ketone, Acetylacetone, 2-ethylhexanal or mixtures of two or more of it used.

There are also polyketones, e.g. Ethylene / CO copolymers for Commitment.

Carbonsäuren, wie z.B. Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Isobuttersäure, n-Valeriansäure, Trimethylessigsäure ("Pivalinsäure"), Capronsäure, Önanthsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Acrylsäure, Methacrylsäure, Ölsäure, Elaidinsäure, Linolsäure, Linolensäure, Cyclohexancarbonsäure, Benzoesäure, Phenylessigsäure, o-Toluylsäure, m-Toluylsäure, p-Toluylsäure, o-Chlorbenzoesäure, p-Chlorbenzoesäure, o-Nitrobenzoesäure, p-Nitrobenzoesäure, Salicylsäure, p-Hydroxybenzoesäure, Anthranilsäure, p-Aminobenzoesäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure, Sebacinsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure;

Carbonsäurehalogenide, wie z.B. die Chloride oder Bromide der oben genannten Carbonsäuren, insbesondere Acetylchlorid oder -bromid, Stearylchlorid oder -bromid und Benzoylchlorid oder -bromid, die insbesondere dehalogeniert werden;

Carbonsäureester, wie z.B. die C₁-C₁₀-Alkylester der oben genannten Carbonsäuren, insbesondere Methylformiat, Essigester, Buttersäurebutylester, Terephthalsäuredimethylester, Adipinsäuredimethylester, (Meth)acrylsäuremethylester, Butyrolacton, Caprolacton und Polycarbonsäureester, wie z.B. Polyacryl- und Polymethacrylsäureester und deren Copolymere und Polyester, wie z.B. Polymethylmethacrylat, wobei hier insbesondere Hydrogenolysen, also die Umsetzung von Estern zu den entsprechenden Säuren und Alkoholen, durchgeführt werden;

Carbonsäureanhydride, wie z.B. die Anhydride der oben genannten Carbonsäuren, insbesondere Essigsäureanhydrid, Propionsäureanhydrid, Benzoesäureanhydrid und Maleinsäureanhydrid.

Carbonsäureamide, wie z.B. Formamid, Acetamid, Propionamid, Stearamid, Terephthalsäureamid.

Ferner können auch Hydroxycarbonsäuren, wie z.B. Milch-, Äpfel-, Wein- oder Zitronensäure, oder Aminosäuren, wie z.B. Glycin, Alanin, Prolin und Arginin, umgesetzt werden.

Furthermore, carboxylic acids and derivatives thereof can be reacted, with those having 1 to 20 carbon atoms being preferred. To be mentioned in detail:

Carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, n-valeric acid, trimethyl acetic acid ("pivalic acid"), caproic acid, oenanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, elaoleic acid, oleic acid, oleic acid , Linolenic acid, cyclohexane carboxylic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, p-oxalic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid;

Carboxylic acid halides, such as the chlorides or bromides of the above-mentioned carboxylic acids, in particular acetyl chloride or bromide, stearyl chloride or bromide and benzoyl chloride or bromide, which are in particular dehalogenated;

Carboxylic acid esters, such as the C ₁ -C ₁₀ -alkyl esters of the abovementioned carboxylic acids, in particular methyl formate, ethyl acetate, butyric acid butyl ester, dimethyl terephthalate, dimethyl adipate, methyl (meth) acrylate, butyrolactone, caprolactone and polycarboxylic acid esters, such as, for example, polyacrylic acid and polyester and their copolymers of polyacrylic acid and polymethacrylate , such as polymethyl methacrylate, in particular hydrogenolysis, ie the conversion of esters to the corresponding acids and alcohols, being carried out here;

Carboxylic anhydrides, such as, for example, the anhydrides of the above-mentioned carboxylic acids, in particular acetic anhydride, propionic anhydride, benzoic anhydride and maleic anhydride.

Carboxamides such as formamide, acetamide, propionamide, stearamide, terephthalic acid amide.

Hydroxycarboxylic acids such as lactic, malic, tartaric or citric acid or amino acids such as glycine, alanine, proline and arginine can also be reacted.

Nitriles

Furthermore, nitriles, preferably aliphatic and aromatic mono- and dinitriles, e.g. Acetonitrile, propionitrile, butyronitrile, Stearonitrile, isocrotonitrile, 3-butenenitrile, propynitrile, 3-butynitrile, 2,3-butadiene nitrile, 2,4-pentadiene nitrile, 3-hexene-1,6-dinitrile, chloroacetonitrile, Trichloroacetonitrile, lactic acid nitrile, phenol acetonitrile, 2-chlorobenzonitrile, 2,6-dichlorobenzonitrile, isophthalonitrile and terephthalic dinitrile, in particular of aliphatic α, ω-dinitriles, e.g. Succinonitrile, Glutaronitrile, adiponitrile, pimelonitrile and corkonitrile, or aminonitriles, e.g. 4-aminobutanoic acid nitrile, 5-aminopentanoic acid nitrile, 6-aminohexanoic acid nitrile, 7-aminoheptanoic acid nitrile and 8-aminooctanoic acid nitrile.

die Hydrierung von aromatischen Verbindungen, wie z.B. Benzol, Toluolen, Xylolen, Naphthalinen sowie substituierten Derivaten davon, zu den entsprechenden alicyclischen Verbindungen; die Hydrierung von Alkenen oder Alkinen, wie z.B. Ethylen, Propylen, 1-, 2-Buten, 1-, 2-, 3- und 4-Octen, Butadien und Hexatrien zu den entsprechenden Alkanen; die Hydrierung von Nitroalkanen, wie z.B. Nitroethan, Nitromethan, Nitropropan und 1,1-Dinitroethan zu den entsprechenden Aminen;

die Hydrierung von Iminen, wie z.B. Chinoniminen, Ketiminen, Keteniminen oder aliphatischen Iminen, wie z.B. Propanimin, Hexanimin; die Dehalogenierung von Halogenatome enthaltenden organischen Verbindungen, insbesondere von aromatischen halogenhaltigen Verbindungen, wie z.B. Chlor- und Brombenzol, Brom- und Chlortoluolen sowie Chlor- und Bromxylolen, wobei dort auch jeweils mit mehreren Halogenatomen substituierte Verbindungen eingesetzt werden können; die aminierende Hydrierung von z.B. Alkoholen, wie z.B. Vinylalkohol.

The following reactions can also be carried out with the method according to the invention:

the hydrogenation of aromatic compounds, such as benzene, toluenes, xylenes, naphthalenes and substituted derivatives thereof, to give the corresponding alicyclic compounds; the hydrogenation of alkenes or alkynes, such as ethylene, propylene, 1-, 2-butene, 1-, 2-, 3- and 4-octene, butadiene and hexatriene to the corresponding alkanes; the hydrogenation of nitroalkanes, such as nitroethane, nitromethane, nitropropane and 1,1-dinitroethane to the corresponding amines;

the hydrogenation of imines such as quinone imines, ketimines, ketenimines or aliphatic imines such as propanimine, hexanimine; the dehalogenation of organic compounds containing halogen atoms, in particular aromatic halogen-containing compounds, such as, for example, chloro- and bromobenzene, bromo- and chlorotoluenes as well as chloro- and bromoxylenes, it also being possible to use compounds substituted with several halogen atoms there; the aminating hydrogenation of, for example, alcohols, such as, for example, vinyl alcohol.

Furthermore, oximes can be implemented using the method according to the invention or produce secondary amines from ketones and primary amines.

Polymers

The catalysts of the invention can also be used for hydrogenations, dehydrogenations, Hydrogenolysis, aminating hydrogenation and dehalogenation of large molecules, preferably polymers.

Accordingly, the present invention also relates to a method for implementation of a polymer that has at least one catalytically convertible group has, in the presence of the catalyst described above, the Hydrogenation of polymers containing C = O groups, e.g. polyester of dicarboxylic acids, unsaturated monocarboxylic acids, e.g. Poly (meth) acrylates, Olefin / CO copolymers or polyketones, and the hydrogenation polymers containing nitrile groups, e.g. Styrene-butadiene copolymers,   Acrylonitrile copolymers, and the aminating hydrogenation of Polyvinyl alcohols and polyketones is preferred.

In particular, the present invention relates to a process for hydrogenation a polymer which has at least one C = O group, or one Polymer that has at least one C≡N group in the presence of above catalyst.

The term "polymer, which is at least one catalytically convertible unit "stands for all polymers which have such units, in particular for polymers, the units of the following structures (I) to (VIII) as defined above for the monomeric compounds, or a Have halogen atom. It goes without saying that this is in question standing polymers contain the respective unit at least once and or within the polymer implemented according to the invention several units of two or more of structures (I) to (VIII) are located can.

The average molecular weight of those to be implemented in the process according to the invention Polymers is generally about 500 to about 500,000, preferably about 1,000 to about 100,000, and more preferably about 1,000 to about 50,000, but polymers can also be used higher molecular weight up to one or several million implemented will.

Polymere mit C―C-Doppelbindungen, wie z.B. Polybutadiene, wie z.B. Poly(2,3-dimethylbutadien), Polyisopren, Polyacetylene und Polycyclopenta- und -hexadiene; Polymere mit C―C-Dreifachbindungen, wie z.B. Polydiacetylene; Polymere mit aromatischen Gruppen, wie z.B. Polystyrol, Acrylnitril-Butadien-Styrol-Terpolymere und Styrol-Acrylnitril-Copolymere; Polymere mit C―N-Dreifachbindungen, wie z.B. Polyacrylnitril, Polyacrylnitril-Copolymere mit z.B. Vinylchlorid, Vinylidenchlorid, Vinylacetat oder (Meth)acrylsäureestern oder Gemischen aus zwei oder mehr davon als Comonomere; Polymere mit C―O-Doppelbindungen, wie z.B. Polyester, Polyacrylamide, Polyacrylsäuren, Polyharnstoffe und Polyketone; Polymere mit C―S-Doppelbindungen, wie z. B. Polysulfone und Polyethersulfone; halogenhaltige Polymere, wie z.B. Polyvinylchlorid und Polyvinylidenchlorid; sowie Nitrogruppen enthaltende Polymere, die durch Nitrierung von z.B. Polyolefinen durch polymeranaloge Umsetzung erhalten werden können.

The following may be mentioned as examples of preferably hydrogenatable polymers which can be implemented in the process according to the invention:

Polymers with C ― C double bonds, such as polybutadienes such as poly (2,3-dimethylbutadiene), polyisoprene, polyacetylenes and polycyclopenta- and hexadienes; Polymers with C ― C triple bonds, such as polydiacetylenes; Polymers with aromatic groups, such as polystyrene, acrylonitrile-butadiene-styrene terpolymers and styrene-acrylonitrile copolymers; Polymers with C ― N triple bonds, such as polyacrylonitrile, polyacrylonitrile copolymers with, for example, vinyl chloride, vinylidene chloride, vinyl acetate or (meth) acrylic acid esters or mixtures of two or more thereof as comonomers; Polymers with C ― O double bonds, such as polyesters, polyacrylamides, polyacrylic acids, polyureas and polyketones; Polymers with C ― S double bonds, such as. B. polysulfones and polyether sulfones; halogen-containing polymers, such as polyvinyl chloride and polyvinylidene chloride; and polymers containing nitro groups, which can be obtained by nitration of, for example, polyolefins by polymer-analogous reaction.

Examples of those preferably used in the context of the present invention Polymers include polyisoprene, polybutadiene, ethylene / CO copolymers, Propylene / CO copolymers, polymethyl (meth) acrylate, polyterephthalates, polyadipates, Styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, acrylonitrile-styrene-butadiene copolymers, Styrene-isoprene-styrene triblock copolymers, Styrene-butadiene-styrene triblock copolymers and styrene-butadiene-styrene star block copolymers a.

In general, the starting materials used are completely converted. However, the reaction, preferably hydrogenation, can also be carried out in such a way that only one type of, for example, hydrogenatable groups is hydrogenated by a suitable choice of temperature, for example H ₂ pressure and H ₂ amount, while the other type of hydrogenatable groups is not hydrogenated .

The process according to the invention is particularly suitable for the implementation, preferably hydrogenation, of polymers, the units of different structures, as defined above, e.g. Polymers that have both C-C multiple bonds   as well as C = O groups and / or C≡N groups, since the catalysts used in the process according to the invention are able to selectively implement the C-C multiple bonds first, i.e. to achieve an implementation of these groups of approximately 90 to 100%, while initially the C = O and / or C≡N groups at the same time less than 25% and generally in a range from 0 to approximately 7% implemented, e.g. be hydrogenated.

After completion of the reaction of the C-C multiple bonds present in the polymers it is of course possible by further supply of hydrogen also the remaining unsaturated ones present in the polymer Groups such as C = O groups, to be implemented almost quantitatively, e.g. to hydrogenate.

The method according to the invention can be used for both isolated and be used for living polymers.

CATALYSTS

The catalysts used according to the invention can be produced industrially are by applying ruthenium and optionally at least one Metal of the I., VII. Or VIII. Subgroup of the periodic table, the is different from Ru on a suitable support.

The application can be carried out by soaking the carrier in aqueous metal salt solutions, such as aqueous ruthenium salt solutions, by spraying on corresponding Metal salt solutions on the support or by other suitable methods can be achieved. As ruthenium salts for the preparation of the ruthenium salt solutions as well as metal salts of subgroups I, VII or VIII   of the periodic table are the nitrates, nitrosyl nitrates, halides, Carbonates, carboxylates, acetylacetonates, chloro complexes, nitro complexes or amine complexes of the corresponding metals, the nitrates and Nitrosyl nitrates are preferred.

In the case of catalysts which, in addition to ruthenium, contain other metals as active metal included on the carrier, the metal salts or metal salt solutions can be applied simultaneously or in succession.

The coated or soaked with the ruthenium salt or metal salt solution Carriers are then, preferably at temperatures between 100 ° C and 150 ° C, dried and optionally at temperatures between 200 ° C and 600 ° C, preferably between 350 ° C and 450 ° C calcined. With separate impregnation, the catalyst is after each Soaking step dried and optionally calcined as described above. The The order in which the active components are soaked is free selectable.

The coated, dried and optionally calcined carriers are then activated by treatment in a gas stream containing free hydrogen at temperatures between approximately 30 ° C. and approximately 600 ° C., preferably between approximately 150 ° C. and approximately 450 ° C. The gas stream preferably consists of 50 to 100% by volume of H ₂ and 0 to 50% by volume of N ₂ .

If one or more other metals of I., VII. or VIII. Subgroup of the periodic table applied to the carrier, so are preferably platinum, copper, rhenium, cobalt and nickel or Mixtures of two or more of them are used.  

The ruthenium or metal salt solution is applied in such an amount or the carrier applied that the total active metal content, respectively based on the total weight of the catalyst, about 0.01 to about 30% by weight, preferably about 0.01 to about 5% by weight preferably about 0.01 to about 1% by weight, and especially about Is 0.05 to about 1% by weight.

The total metal surface area on the catalyst is preferably approximately 0.01 to approximately 10 m ² / g, more preferably approximately 0.05 to approximately 5 m ² / g and in particular approximately 0.05 to approximately 3 m ² / g of the catalyst. The metal surface is by means of the by J. LeMaitre et al. in "Characterization of Heterogenous Catalysts", ed. Francis Delanney, Marcel Dekker, New York 1984, pp. 310-324.

In the catalyst used in the invention, the ratio is Surfaces of the active metal / metals and the catalyst carrier less than about 0.05, with the lower limit being about 0.0005.

CARRIER

The support materials which can be used to prepare the catalysts used according to the invention are those which are macroporous and have an average pore diameter of at least about 50 nm, preferably at least about 100 nm, in particular at least about 500 nm, and their surface area according to BET at most about 30 m ² / g , preferably at most about 15 m ² / g, more preferably at most about 10 m ² / g, in particular at most about 5 m ² / g and more preferably at most about 3 m ² / g. More specifically, the mean pore diameter of the carrier is preferably about 100 nm to about 200 µm, more preferably about 500 nm to about 50 µm. The surface area of the carrier is preferably approximately 0.2 to approximately 15 m ² / g, more preferably approximately 0.5 to approximately 10 m ² / g, in particular approximately 0.5 to approximately 5 m ² / g and further preferably approximately 0, 5 to about 3 m ² / g.

The term "macroporous" is used in the context of the present invention as defined in Pure Applied Chem. 45 , p. 79 (1976), namely as pores whose diameter is above 50 nm.

The surface of the support is determined by the BET method by N ₂ adsorption, in particular in accordance with DIN 66131. The average pore diameter and the pore size distribution are determined by mercury porosymmetry, in particular in accordance with DIN 66133.

The pore size distribution of the support can preferably be approximately bimodal be, the pore diameter distribution with maxima at about 600 nm and about 20 µm in bimodal distribution is a special embodiment of the invention.

A carrier with a surface area of 1.75 m ² / g is further preferred which has this bimodal distribution of the pore diameter. The pore volume of this preferred carrier is preferably about 0.53 ml / g.

Activated carbon, for example, can be used as the macroporous carrier metal, Silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, Magnesium oxide, zinc oxide or mixtures of two or more thereof, wherein Alumina and zirconia are preferably used.  

The catalysts used according to the invention show a high reactivity (high turn-over number), selectivity and service life. Using the invention The catalysts used in the hydrogenation are the hydrogenation products obtained in high yield and purity, with one subsequent cleaning is unnecessary.

In the hydrogenation of an aromatic compound in which at least one Hydroxyl group is attached to an aromatic nucleus, in particular in the hydrogenation of 4-alkyl- or 4-alkoxy-substituted phenols, as described above, predominantly trans-cycloaliphatic Receive connections. The proportion of trans-cycloaliphatic compounds is at least 60% according to an embodiment of the invention, preferably at least 65%. The turnover is practically quantitative Residual aromatic part is preferably less than 0.01% by weight, based on the total amount of product. The hydrogenation product obtained can in one preferred embodiment of the present invention thus directly Further processing can be supplied without having to be cleaned.

SOLVENT OR THINNER

In the process according to the invention, the reaction can, preferably Hydrogenation, in the absence of a solvent or diluent be carried out, i.e. it is not necessary to implement in solution perform.

The melt of a polymer can also be reacted directly.

However, a solvent or diluent is preferably used. Any suitable solvent or   Diluents are used. The selection is not critical. For example, the solvents or diluents can also be low Contain amounts of water.

In the reaction, preferably hydrogenation, of an aromatic compound, in the at least one hydroxyl group on an aromatic nucleus examples of suitable solvents or diluents the following one:

Straight chain or cyclic ethers such as tetrahydrofuran or Dioxane and aliphatic alcohols in which the alkyl radical is preferably 1 has up to 10 carbon atoms, in particular 3 to 6 carbon atoms.

Examples of alcohols which can preferably be used are i-propanol, n-butanol and i-butanol and n-hexanol.

Mixtures of these or other solvents or diluents can can also be used.

In the reaction, preferably hydrogenation, of an aromatic compound, in the at least one amino group to an aromatic nucleus examples of suitable solvents or diluents the following one:

Straight chain or cyclic ethers such as tetrahydrofuran or Dioxane, and ammonia and mono- or dialkylamines in which the Alkyl radical preferably has 1 to 3 carbon atoms, e.g. Methyl-, Ethyl, propylamine or the corresponding dialkylamines.  

Mixtures of these or other solvents or diluents can can also be used.

In both of the above embodiments, the amount of the solvent or diluent used is not particularly limited and can be chosen as required, but such quantities are preferred to a 10 to 70 wt .-% solution of the hydrogenation the intended connection.

This is particularly preferred in the context of the method according to the invention in the implementation, preferably hydrogenation, formed this process Product used as a solvent, optionally alongside other solution or Thinners. In this case, part of the procedure formed product the to be reacted, preferably to be hydrogenated, Compounds are added. Based on the weight of implementation, preferably hydrogenation, provided aromatic compounds is preferably 1 to 30 times, particularly preferably 5 to 20 times, in particular 5 to 10 times the amount of the reaction product as Solvent or diluent added.

This also applies to the other compounds which can be implemented according to the invention Said above, although there are no restrictions regarding the solution and Thinners exist.

Kohlenwasserstoffe, wie z.B. Hexan, Cyclohexan, Methylcyclohexan, Heptan, Octan, Toluol, Xylol usw., und geradkettige oder cyclische Ether, wie z.B. Tetrahydrofuran, Dioxan, Dibutylether, Methyl-tert.-Butylether usw,. Ketone, wie z.B. Methylethylketon und Aceton, Ester, wie z.B. Ethylacetat, oder Amide, wie z.B. DMF und N-Methylpyrrolidon.

In the reaction, preferably hydrogenation, of polymers, examples of suitable solvents or diluents include the following:

Hydrocarbons such as hexane, cyclohexane, methylcyclohexane, heptane, octane, toluene, xylene etc., and straight chain or cyclic ethers such as tetrahydrofuran, dioxane, dibutyl ether, methyl tert-butyl ether, etc. Ketones such as methyl ethyl ketone and acetone, esters such as ethyl acetate or amides such as DMF and N-methyl pyrrolidone.

Cyclohexane, toluene or THF are preferably used. Mixtures this and other solvents and diluents can also be used will.

If the polymer was obtained by solution polymerization, the the resulting polymer-containing solution directly for reaction in inventive methods are used.

The amount of solvent or diluent used is in the range of the method according to the invention is not particularly limited and can be chosen as required, but such quantities preferred are 1 to 70%, preferably 1 to 40% by weight, Solution of the polymer intended for implementation.

IMPLEMENTATION

The reaction is described below using the example of a hydrogenation, where - provided dehydration or oxidation is carried out should - instead of hydrogen or hydrogen-containing gases gaseous Hydrocarbons or oxygen-containing gases among those described below Conditions can be used.

The hydrogenation is carried out at suitable pressures and temperatures. Pressures above approximately 2 × 10 ⁶ Pa, preferably above approximately 5 × 10 ⁶ Pa, in particular from approximately 1 × 10 ⁷ to approximately 3 × 10 ⁷ Pa, are preferred. Preferred temperatures range from about 30 to about 250 ° C, preferably from about 100 to about 220 ° C, and most preferably from about 150 ° C to about 200 ° C.

The hydrogenation process can be continuous or in the manner of a batch process be performed. In the continuous process, one can Part of the hydrogenation product leaving the reactor to the reactor feed be fed before the reactor. Such an amount of the Reactor leaving hydrogenation product recycled as a solvent that the proportions given in the subsection "solvents and diluents" can be achieved. The remaining amount of hydrogenation product is withdrawn.

With continuous process control, the amount for hydrogenation is provided connection or connections preferably about 0.05 to about 3 kg per liter of catalyst per hour, more preferably about 0.1 to about 1 kg per liter of catalyst per hour.

Any gases can be used as hydrogenation gases, the free hydrogen contain and no harmful amounts of catalyst poisons, such as for example, CO. For example, reformer exhaust gases can be used will. Pure hydrogen is preferably used as the hydrogenation gas.

Depending on the reaction conditions, in the case of the phenols and amines additionally substituted by at least one optionally substituted C _1-10 - and / or alkoxy radical, depending on the reaction conditions (temperature, solvent), the isomer ratio of cis to trans-configured products obtained can be in a wide range can be varied.

If an aromatic compound in the at least one amino group an aromatic nucleus is bound by means of the catalyst according to the invention To be hydrogenated, the hydrogenation can also in the presence of Ammonia: or dialkylamines, for example methylamine, ethylamine, Propylamine or dimethylamine, diethylamine or dipropylamine performed will. Suitable amounts of ammonia or mono- or Dialkylamine used, preferably at about 0.5 to about 50 Parts by weight, particularly preferably from about 1 to about 20 parts by weight, each based on 100 parts by weight of the hydrogenation provided connection or connections. Particularly preferred anhydrous ammonia or anhydrous amines are used.

Air or pure oxygen is generally used for oxidation. The hydrocarbons commonly used for dehydrogenation, especially methane or natural gas used.

The invention is described below with the aid of a few exemplary embodiments explained in more detail, with examples 1 to 4 relating to the hydrogenation of a aromatic compound in which at least one hydroxyl group is attached to one aromatic nucleus is related. Examples 5 to 7 relate on the hydrogenation of an aromatic compound in which at least one Amino group is bound to an aromatic nucleus. Examples 8 to 12 relate to the reaction of compounds containing C = O groups, Examples 13 and 14 relate to the reaction of polymers.  

EXAMPLES Preparation of the catalyst 1

A macroporous aluminum oxide support in the form of 3 to 6 mm pellets, which had a BET surface area of 10 m ² / g, a pore volume of 0.45 ml / g and a pore diameter of 210 nm, was washed with an aqueous ruthenium (III) nitrate solution soaked. The volume of solution taken up by the carrier corresponded approximately to the pore volume of the carrier used.

The support impregnated with the ruthenium (III) nitrate solution was then dried at 120 ° C. and reduced at 200 ° C. in a stream of hydrogen. The catalyst produced in this way contained 0.5% by weight of ruthenium, based on the total weight of the catalyst, and had a ruthenium surface area of 0.5 m ² / g, which could be determined by H ₂ pulse chemisorption (Pulschemisorp 2700, 35 ° C. ) was determined. The ratio of the active metal to the carrier surface was 0.05.

EXAMPLE 1

• 99,9% cis,trans-4-tert.-Butylcyclohexanol
• < 0,01% p-tert.-Butylphenol

A 50% by weight solution of p-tert-butylphenol in THF was prepared. Then 2500 g / h of this solution with hydrogen at 180 ° C and a total pressure of 2.6 · 10 ⁷ Pa were passed through a flow-through reactor which was filled with 3.2 l of the Ru catalyst described above. After the solvent had been distilled off, the hydrogenation product had the following composition:

• 99.9% cis, trans-4-tert-butylcyclohexanol
• <0.01% p-tert-butylphenol

EXAMPLE 2

• 99,8% cis,trans-4-tert.-Butylcyclohexanol
• < 0,01% p-tert.-Butylphenol

The hydrogenation was carried out in the same manner as described in Example 1, but 3500 g of the 50% by weight p-tert-butylphenol solution in THF were passed through the reactor at 200 ° C. After the solvent had been distilled off, the hydrogenation product had the following composition:

• 99.8% cis, trans-4-tert-butylcyclohexanol
• <0.01% p-tert-butylphenol

EXAMPLE 3

• 67,5% trans-4-tert.-Butylcyclohexanol
• 32,4% cis-4-tert.-Butylcyclohexanol
• < 0,01% p-tert.-Butylphenol

The hydrogenation was carried out in the same manner as indicated in Example 1, but a 50% by weight solution of p-tert-butylphenol in i-butanol was used. After the solvent had been distilled off, the hydrogenation product had the following composition:

• 67.5% trans-4-tert-butylcyclohexanol
• 32.4% cis-4-tert-butylcyclohexanol
• <0.01% p-tert-butylphenol

EXAMPLE 4

2 kg of a solution of 50% by weight bisphenol A in THF and 500 ml of the macroporous catalyst from Example 1 (0.4% by weight Ru on Al ₂ O ₃ ) were placed in a catalyst basket in a 3.5 l autoclave given. The mixture was then hydrogenated discontinuously at 150 ° C. and 2 × 10 ⁷ Pa for five hours. The conversion to the desired cycloaliphatic diol isomer mixture was quantitative and the residual aromatic content was less than 0.01%.

EXAMPLE 5

1.2 l of the catalyst prepared as described above were introduced into an electrically heatable flow reactor. The hydrogenation of aniline was then started at 2 × 10 ⁷ Pa and 160 ° C. without prior activation. The hydrogenation was carried out continuously in the bottoms mode, part of the hydrogenation discharge being recirculated via a circulation pump and mixed with the feedstock upstream of the reactor. Based on the amount of aniline, ten times the amount of hydrogenation product was added as a solvent. 500 to 600 l of H ₂ / h were released at the top of the separator. The amount of aniline fed continuously to the reactor corresponded to a catalyst load of 1.0 kg / lx h.

Depending on the reaction temperatures, the following product compositions resulted under stationary reaction conditions: Temperature (° C) CHA (%) DCHA (%) Aniline (%) Cyclohexane + Cyclohexene (%) 160 99.1 0.45 0.10 0.04 180 97.0 2.75 0.06 0.06 200 95.9 3.9 - 0.09

EXAMPLE 6

The hydrogenation was carried out as described in Example 5, but ammonia was metered in continuously in addition anhydrous. Based on 100% by weight of aniline, 10 parts by weight of ammonia were added. Depending on the reaction temperatures, the following product compositions resulted under stationary reaction conditions: Temperature (° C) CHA (%) DCHA (%) Aniline (%) Cyclohexane + Cyclohexene (%) 180 99.3 0.08 - 0.07 200 98.4 0.8 - 0.09

EXAMPLE 7

2 kg of a solution of 50% by weight of toluenediamine (2,4-; 2,6-diaminotoluene isomer mixture) in THF and 500 ml of the catalyst described above were placed in a 3.5 l autoclave. The mixture was then hydrogenated discontinuously at 150 ° C. and 2 × 10 ⁷ Pa for five hours. The conversion to the desired cycloaliphatic diamine isomer mixture was quantitative and the residual aromatic content was less than 0.01%.

EXAMPLE 8

3 l of catalyst 1 were introduced into a tubular reactor (l = 2500 mm, Katalysator = 45 mm), the reactor was filled with n-butanol and heated to 180 ° C. at 3 · 10 ⁶ Pa (30 bar) hydrogen pressure. An amount of 1 kg / h of n-butyraldehyde was then continuously fed into the reactor at a circulation rate of 50 l / h. The reaction product obtained was colorless and free of ruthenium.

The gas chromatographic evaluation showed a conversion of 99.4% and a selectivity for n-butanol of 99.7%, based in each case on the amount of n-butyraldehyde used.

EXAMPLE 9

3 l of catalyst 1 and 700 g of one were placed in a 3.5 l autoclave Ethylene / CO copolymers (Mw = 5,000, CO content 35%), dissolved in 1,300 g THF, filled.

The mixture was then hydrogenated at 180 ° C. and 2 × 10 ⁷ Pa (200 bar) hydrogen pressure for 5 h. The conversion to the desired polyalcohol was 93%, based on the amount of the copolymer used.

EXAMPLE 10

3 l of catalyst 1 were used in a 3.5 l autoclave and 2,000 g of benzaldehyde were introduced. The mixture was then hydrogenated at 180 ° C. and 2 × 10 ⁷ Pa (200 bar) hydrogen pressure for 10 h. The conversion to the desired cyclohexylmethanol was 100% with a selectivity of 96.2%, based in each case on the amount of benzaldehyde used.

EXAMPLE 11

3 l of catalyst 1 were used in a 3.5 l autoclave and 2,000 g of 2-ethylhexanal were introduced. The mixture was then hydrogenated at 180 ° C. and 2 × 10 ⁷ Pa (200 bar) hydrogen pressure for 10 h. The conversion to the desired 2-ethylhexanol was 100% with a selectivity of 97.2%, in each case based on the amount of 2-ethylhexanal used.

EXAMPLE 12

100 ml of dimethyl adipate were reacted in the presence of catalyst 1 in a 0.3 l stirred autoclave. The mixture was stirred at a hydrogen pressure of 2 · 10 ⁷ Pa (200 bar) and a temperature of 220 ° C for 12 h. Gas chromatographic analysis of the reaction discharge showed a conversion of 98% and a hexanediol yield of 91%, based in each case on the amount of dimethyl adipate used.

EXAMPLE 13 Preparation of catalyst 2

A macroporous alumina carrier in the form of 3-6 mm pellets, which had a surface area of 10 m ² / g, determined by the BET method, a pore volume of 0.45 ml / g and a pore diameter of 0.21 μm, was found impregnated with an aqueous ruthenium (III) nitrate solution. The volume of solution taken up by the carrier corresponded approximately to the pore volume of the carrier used.

The support impregnated with ruthenium (III) nitrate solution was then dried at 120 ° C. and reduced at 200 ° C. in a hydrogen stream. The catalyst produced in this way contained 0.3% by weight of ruthenium, based on the total weight of the catalyst, and had a ruthenium surface area of 0.4 m ² / g, determined by H ₂ pulse chemisorption (pulse chemisorp 2700, 35 ° C). The ratio of the metal to the carrier surface was 0.04.

Hydrogenation

100 g of a 15% by weight solution of an acrylonitrile-butadiene copolymer with 18% by weight of acrylonitrile and an average molecular weight of 3000 in THF, 60 ml of ammonia and 15 g of catalyst 2 were placed in a 300 ml pressure autoclave. The mixture was then hydrogenated discontinuously at 180 ° C. and 2.5 × 10 ⁷ Pa (250 bar) for 12 hours. The tetrahydrofuran present was distilled off from the polymer.

The nitrile conversion was 92%. There was no molecular weight loss.

EXAMPLE 14 Preparation of catalyst 3

A macroporous alumina carrier in the form of 3-6 mm pellets, which had a surface area of 10 m ² / g, determined by the BET method, a pore volume of 0.45 ml / g and a pore diameter of 0.21 μm, was found impregnated with an aqueous ruthenium (III) nitrate solution. The volume of solution taken up by the carrier corresponded approximately to the pore volume of the carrier used.

Subsequently, supports impregnated with the ruthenium (III) nitrate solution were dried at 120 ° C. and reduced at 200 ° C. in a hydrogen stream. The catalyst prepared in this way contained 0.2% by weight of ruthenium, based on the total weight of the catalyst, and had a ruthenium surface area of 0.3 m ² / g, determined by H ₂ pulse chemisorption (pulse chemisorp 2700, 35 ° C). The ratio of the metal to the carrier surface was 0.03.

Hydrogenation

100 g of a 15% by weight solution of an acrylonitrile-putadiene co-polymer with 18% by weight of acrylonitrile and an average molecular weight of 3000 in THF, 60 ml of ammonia and 15 g of catalyst 3 were placed in a 300 ml pressure autoclave. The mixture was then hydrogenated discontinuously at 180 ° C. and 2.5 × 10 ⁷ Pa (250 bar) for 12 hours. The tetrahydrofuran present was distilled off from the polymer.

The nitrile conversion was 90%. There was no molecular weight loss.

Claims (10)

A process for reacting an organic compound in the presence of a catalyst which comprises ruthenium as the active metal, alone or together with at least one metal from subgroup I, VII or VIII of the Periodic Table, applied to a support, the support having an average pore diameter of at least 50 nm and a surface BET of at most 30 m ² / g and the amount of active metal is 0.01 to 30 wt .-%, based on the total weight of the catalyst, characterized in that the ratio of the surfaces of the active metal and Catalyst support is <0.05. A method according to claim 1, characterized in that the at least a metal of subgroup I, VII or VIII of the periodic table Platinum, copper, rhenium, cobalt, nickel or a mixture of is two or more of them. A method according to claim 1 or 2, characterized in that the carrier has a BET surface area of at most 15 m ² / g. Method according to one of claims 1 to 3, characterized in that that the content of the active metal 0.01 to 1 wt .-%, based on the Total weight of the catalyst.   Method according to one of the preceding claims, characterized in that that the average pore diameter of the carrier is at least 100 nm. Method according to one of the preceding claims, characterized in that that the carrier activated carbon, silicon carbide, aluminum oxide, Silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide or is a mixture of two or more of them. Method according to one of the preceding claims, characterized in that that the reaction involves hydrogenation, dehydrogenation, hydrogenolysis, is aminating hydrogenation or dehalogenation. Method according to one of the preceding claims, characterized in that that the organic compound is selected from the Group consisting of an aromatic compound in which at least a hydroxyl group is attached to an aromatic nucleus, one aromatic compound in which at least one amino group is attached to one aromatic nucleus is bound, a ketone, an aldehyde, one Carboxylic acid or a derivative thereof, a polymer that at least has a C-C double bond, a polymer containing at least one C = O group, a polymer that has at least one C-N triple bond and a mixture of two or more thereof. Method according to one of the preceding claims, characterized in that that the reaction in the presence of a solvent or diluent is carried out. Catalyst comprising ruthenium as the active metal, alone or together with at least one metal of subgroup I, VII or VIII of the Periodic Table, applied to a support, the support having an average pore diameter of at least 50 nm and a BET surface area of at most 30 m ² / g and the amount of active metal is 0.01 to 30 wt .-%, based on the total weight of the catalyst, characterized in that the ratio of the surfaces of the active metal and the catalyst support is <0.05.