WO2010005859A2

WO2010005859A2 - Processes for hydrogenating aromatic amines

Info

Publication number: WO2010005859A2
Application number: PCT/US2009/049477
Authority: WO
Inventors: Tse-Chong Wu; Mario Lozanov
Original assignee: Albemarle Corporation
Priority date: 2008-07-07
Filing date: 2009-07-02
Publication date: 2010-01-14
Also published as: WO2010005859A3

Abstract

A process for the reaction of an organic compound in the presence of a catalyst comprising, as active metal, ruthenium, rhodium or palladium, alone or together with at least one Group Ib, VI Ib, or VIIIb metal in an amount of from 0.01 to 30 wt %, based on the total weight of the catalyst, applied to a support, wherein from 0 to 10% of the pore volume of the support comprises macropores having a pore diameter in the range of from 50 nm to 10,000 nm and from 90 to 100% of the pore volume of the support comprises mesopores having a pore diameter in the range of from 2 nm to less than 50 nm, the sum of said pore volumes being 100%.

Description

C

BACKGROUND

[0001] The present invention relates to a process for reacting an organic compound in the presence of a catalyst which comprises ruthenium, rhodium or palladium and optionally one or more further Group Ib, VIIb, or VIIIb metals, applied to a porous support, as active metal(s).

[0002] Several patents and publications describe such methods, e.g., US 6,388,149,

US 6,248,924, US 5,773,657, and US 7,030,052, to name a few.

[0003] In spite of all of the published methods, there is a need for improved methods, especially those that provide improved yield and activity.

THE INVENTION

[0004] This invention meets the above-described needs by providing processes for the reaction, e.g., hydrogenation, of an organic compound in the presence of a catalyst comprising, as active metal, ruthenium, rhodium or palladium, either alone or together with at least one Group Ib, VIIb, or VIIIb metal in an amount of from 0.01 to 30 wt %, based on the total weight of the catalyst, applied to a support, wherein from 0 to 10% of the pore volume of the support comprises macropores having a pore diameter in the range of from 50 nm to 10,000 nm and from 90 to 100% of the pore volume of the support comprises mesopores having a pore diameter in the range of from 2 to 50 nm, the sum of said pore volumes being 100%.

[0005] The present invention also relates to processes for the reaction, e.g., hydrogenation, of polymers containing C - C multiple bonds in the presence of a catalyst comprising, as active metal, ruthenium, rhodium or palladium, either alone or together with at least one Group Ib, VIIb, or VIIIb metal in an amount of from 0.01 to 30 wt %, based on the total weight of the catalyst, applied to a support, wherein the catalyst is characterized in that from 0 to 10% of the pore volume of the support comprises macropores having a pore diameter in the range of from 50 nm to 10,000 nm and from 90 to 100% of the pore volume of the support comprises mesopores having a pore diameter in the range of from 2 to 50 nm, the sum of said pore volumes being , , . . catalysts comprising, as active metal, ruthenium, rhodium or palladium, either alone or together with at least one Group Ib, VIIb, or VIIIb metal in an amount of from 0,01 to 30 wt %, based on the total weight of the catalyst, applied to a support, wherein the catalyst is characterized in that from 0 to 10% of the pore volume of the support comprises macropores having a pore diameter in the range of from 50 nm to 10,000 and from 90 to 100% of the pore volume of the support comprises mesopores having a pore diameter in the range of from 2 to 50 nm, the sum of said pore volumes being 100%.

ORGANIC COMPOUNDS

[0007] The term "organic compound" as used within the present invention comprises all organic compounds including low molecular weight (monomeric) and polymeric organic compounds which may be catalytically reacted, e.g., those which exhibit groups which are treatable with hydrogen, such as C C groups or C=C groups. This term comprises low molecular weight organic compounds as well as polymers. "Low molecular weight organic compounds" are compounds having a molecular weight of below 500. The term "polymer" is defined as relating to molecules having a molecular weight of higher than about 500.

[0008] The present invention relates to processes for reacting an organic compound in the present of a catalyst as defined herein, wherein the reaction is a hydrogenation, dehydrogenation, hydrogenolysis, aminating hydrogenation or dehalogenation.

[0009] Organic compounds having one or more of the following structural units may be used.

C=C (I)

C≡C (II)

—s (VII)

-NO₂ (VIII)

[0010] Processes of this invention are suitable for reacting, e.g. hydrogenating, an organic compound which is selected from an aromatic compound in which at least one hydroxyl group is bonded to an aromatic ring, an aromatic compound in which at least one amino group is bonded to an aromatic ring, a ketone, an aldehyde, a carboxylic acid or a derivative thereof, a polymer comprising at least one C=C group, a polymer comprising at least one C=^O group, a polymer comprising at least one C=N group, or a mixture of two or more thereof.

[0011] Within processes of this invention, organic compounds comprising units of different structures, as defined herein, may be reacted, such as organic compounds which exhibit C - C multiple bonds and carbonyl groups, since the catalysts used within processes of this invention are capable to first selectively hydrogenate one of the two groups, i.e., to achieve a hydrogenation of these groups from about 90 to 100%, while at first the other groups are reacted, e.g., hydrogenated, to an extent of less than 25% and in general 0 to about 7%. Generally, first the C - C multiple bond and subsequently the C=O group are reacted, e.g. hydrogenated, respectively. [0012] The term "aromatic compound in which at least one hydroxyl group is bonded to an aromatic ring" or "aromatic compound in which at least one amino group is bonded to an aromatic ring" means all compounds which have a unit of the structure:

where R is a hydroxyl group or an amino group.

[0013] If, in processes of the present invention, use is made of aromatic compounds in which at least one hydroxyl group and also at least one unsubstituted or substituted C-₁ - Cio alkyl radical and/or C₁ - Cio alkoxy radical is bonded to an aromatic ring, the resulting isomer ra io o cis o rans pro uc s can e varie wi in a wide range, depending on the reaction conditions (temperature, solvent, etc.).

[0014] Like the above-described compounds in which at least one hydroxy! group is bonded to an aromatic ring, aromatic compounds in which at least one amino group is bonded to an aromatic ring can also be hydrogenated by processes of the present invention to give the corresponding cycloaliphatic compounds with high selectivity. For the amines additionally substituted by a Ci - C₁₀ alkyl radical and/or Ci - C-io alkoxy radical, what has been said above regarding the ratio of the cis and trans isomers also applies.

[0015] Use of processes of this invention can significantly minimize formation of deamination products such as cyclohexanes or partially hydrogenated dimerization products such as phenylcyclohexyiamines.

[0016] The following compounds may be reacted with the process of the invention: aromatic compounds in which at least one hydroxyl group is bonded to an aromatic ring; aromatic compounds in which at least one amino group is bonded to an aromatic ring; or compounds comprising C- C groups.

Aromatic Compounds in Which at Least One Hydroxyl Group is Bonded to an Aromatic Ring

[0017] Aromatic compounds in which at least one hydroxyl group and, optionally, also at least one unsubstituted or substituted C₁ - Cio alkyl radical and/or alkoxy radical is bonded to an aromatic ring can be reacted, e.g., hydrogenated, by means of the processes of the present invention to give the corresponding cycloaliphatic compounds, with it also being possible to use mixtures of two or more of these compounds. The aromatic compounds used can be monocyclic or polycyclic aromatic compounds. The aromatic compounds contain at least one hydroxyl group bonded to an aromatic ring; the simplest compound of this group is phenol. The aromatic compounds can have one hydroxyl group per aromatic ring and can be substituted on the aromatic ring or rings by one or more alkyl and/or alkoxy radicals, e.g., Ci - Cio alkyl and/or alkoxy radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl radicals and/or Ci - Cs alkoxy radicals such as the methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy radicals. The aromatic ring or rings and also the alkyl and alkoxy radicals may be unsubstituted or substituted by halogen atoms, e.g., fluorine atoms, or other suitable inert substituents. mj in processes o is inven ion, e compoun s w ic can be reac e , e.g., hydrogenated, can have at least one, e.g., from one to four, e.g., one, Ci - Cioalkyl radical which is located on the same aromatic ring as the hydroxyl group or groups. Suitable compounds include (mono)alkylphenols, where the alkyl radical can be in the o-, m- or p- position relative to the hydroxyl group. Suitable compounds also include p-alkylphenols, also known as 4-alkylphenols, where the alkyl radical has from 1 to 10 carbon atoms and can be a tert-butyl radical, e.g., a 4-tert-butylphenol. Polycyclic aromatic compounds which can be used according to the present invention are, for example, β-naphthol and α-naphthol.

[0019] The aromatic compounds in which at least one hydroxyl group and, optionally, also at least one unsubstituted or substituted Ci - Cio alkyl radical and/or alkoxy radical is bonded to an aromatic ring can also have a plurality of aromatic rings which are linked via an alkylene radical, e.g., a methylene group. The alkylene group, e.g., methylene group, which forms the linkage can have one or more alkyl substituents which can be Ci - C₂o alkyl radicals, e.g., Ci - Cio alkyl radicals, including, e.g., methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.

[0020] In these compounds, each of the aromatic rings can bear at least one bonded hydroxyl group. Examples of such compounds are bisphenols, which are linked in the 4-position via an alkylene radical, e.g., a methylene radical.

[0021] In processes of the present invention, a phenol can be reacted, wherein the phenol is substituted by a Ci - Cio alkyl radical, or a Ci - CQ alkyl radical, where the alkyl radical may be unsubstituted or substituted by an aromatic radical, or mixtures of two or more of these compounds.

[0022] Further, in processes of this invention, p-tert-butylphenol, bis(p-hydroxyphenyl)dimethylmethane or a mixture thereof can be reacted.

Aromatic Compounds in Which at Least One Amino Group is Bonded to an Aromatic Ring

[0023] Processes of this invention also enable aromatic compounds in which at least one amino group is bonded to an aromatic ring to be reacted, e.g., hydrogenated, to give the corresponding cycloaliphatic compounds, with mixtures of two or more of these compounds also being able to be used. The aromatic compounds can be monocyclic or polycyclic aromatic compounds. The aromatic compounds can contain at least one amino group which is bonded to an aromatic ring. The aromatic compounds can be .. . , . ... . .. aromatic amines or diamines and can e substitute on the aromatic ring or rings or on the amino group by one or more alkyl and/or alkoxy radicals, e.g., Ci - C₂₀ alkyl radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl radicals. Useful alkoxy radicals include Ci - Cs alkoxy radicals such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy radicals. The aromatic ring or rings and also the alkyl and alkoxy radicals can be unsubstituted or substituted by halogen atoms, e.g., fluorine atoms, or other suitable inert substituents. [0024] The aromatic compound in which at least one amino group is bonded to an aromatic ring can also have a plurality of aromatic rings which are linked via an alkylene group, e.g., a methylene group. The alkylene group, e.g., methylene group, which forms the linkage can bear one or more alkyl substituents which can be Ci - C-20 alkyl radicals, including Ci - C₁₀ aikyi radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl.

[0025] The amino group bonded to the aromatic ring may be unsubstituted or substituted by one or two of the above-described alkyl radicals. [0026] Suitable compounds are aniline, naphthylamine, diaminobenzenes, diaminotoluenes and bis-(p-aminophenyl)methane, 4,4'-diamino-3,3'- dimethyldiphenylmethane, or mixtures thereof.

Compounds Comprising C=O Groups

[0027] Within processes of the invention it is also possible to react, e.g., to hydrogenate, compounds comprising C=O groups, i.e., aldehydes, ketones, carboxylic acids and their derivatives, such as carboxylic acid esters, carboxylic acid halides and carboxylic anhydrides, and mixtures of two or more of said compounds. [0028] Aldehydes and ketones, e.g., those having 1 to 20 C atoms, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, valeraldehyde, caproaldehyde, heptaldehyde, phenylacetaldehyde, acrolein, crotonaldehyde, benzaldehyde, o-, m-, p-tolualdehyde, salicylic aldehyde, anisaldehyde, vanillin, cinnamic aldehyde, 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, glyoxal, 2,3-butanedione, , -penτaneαιone, , - exane one, terep t a a e y e, g u ara dehyde, diethy e one, methyl vinyl ketone, 2-ethylhexanal, or mixtures of two or more thereof, may be used.

[0029] Furthermore, also polyketones, such as copolymers of ethylene and CO can be used.

[0030] Furthermore, carboxylic acids and derivatives thereof, e.g., those having 1 to

20 C atoms may be reacted.

[0031] Carboxylic acids suitable for use in this invention include formic acid, acetic acid, propanoic acid, butanoic acid, iso-butanoic acid, n-valeric acid, pivalic acid, caproic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, methacrylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, benzoic acid, phenylacetic acid, o-, m, p-toluic acid, o-, p-chlorobenzoic acid, o-, p-nitrobenzoic acid, salicylic acid, p-hydroxybenzoic acid, anthranilic acid, p-aminobenzoic acid, 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, teraphthalic acid, and mixtures of two or more thereof.

[0032] Carboxylic acid halides suitable for use in this invention include the chlorides and bromides of the above-mentioned carboxylic acids, e.g., acetyl chloride or bromide, stearic acid chloride or bromide and benzoic acid chloride or bromide, which are dehalogenated.

[0033] Carboxylic acid esters suitable for use in this invention include the Ci - Cio alkyl esters of the above-mentioned carboxylic acids, e.g., methyl formate, acetic acid ester, butanoic acid butyl ester, dimethyl terephthalate, dimethyl adipate, methyl methacrylate, butyrolactone, caprolactone and polycarboxylic acid esters, such as polyacrylic and polymethacrylic acid esters and copolymers and polyesters thereof, such as poly(methyl methacrylates); these esters can be hydrogenated, i.e. the esters can be converted to the corresponding acids and alcohols.

[0034] Carboxylic anhydrides suitable for use in this invention include anhydrides of the above-mentioned carboxylic acids, e.g., acetic acid anhydride, propanoic acid anhydride, benzoic acid anhydride and maleic anhydride.

[0035] Carboxylic acid amides suitable for use in this invention include amides of the above-mentioned carboxylic acids, such as formamide, acetamide, propionic amide, stearamide and terephthalamide. 36J Additiona y, ydroxy car oxy c ac s, suc as act c ac d, mal c ac , ta ar c acid or citric acid, or amino acids, such as glycine, alanine, proline and arginine may be reacted in processes of this invention.

NITRILES

[0037] Furthermore, also useful in this invention are nitriles, e.g., aliphatic or aromatic mono or dinitriles, such as acetonitrile, propionitrile, butyronitrile, stearonitrile, 3-butenenitrile, 2,3-butadienenitrile, 2,4-pentadienenitrile, 3-hexene-1 ,6-dinitrile, chloracetonitrile, trichloracetonitrile, 2-hydroxypropionitrile, phenylacetonitrile, 2-chlorbenzonitrile, 2,6-dichlorobenzonitrile, isophthalonitrile, e.g., aliphatic alpha, omega-dinitriles, such as succinonitrile, glutaronithle, adiponitrile, pimelonitrile and suberonitrile or aminonitriles, such as 4-aminobutyronitrile, 5-aminopentanenitrile, 6-aminohexanenitrile, 7-aminoheptanenitrile and 8-aminooctanenitrile. [0038] Furthermore, within processes according to this invention, certain reactions as described below may be carried out.

[0039] Reactions that may be carried out within processes according to this invention include: the hydrogenation of aromatic compounds, such as benzene, toluenes, xylenes, naphthalenes and substituted derivatives thereof, leading to the corresponding alicylic compounds; the hydrogenation of alkenes or alkynes, such as ethylene, propylene, 1-, 2-butene, 1-, 2-, 3- and 4-octene, butadiene, and hexatriene leading to the corresponding alkanes; the hydrogenation of nitroalkanes, such as nitroethane, nitromethane, nitropropane and 1 ,1-dinitroethane leading to the corresponding amines; the hydrogenation of imines, such as quinone imines, ketimines, ketene imines or aliphatic imines, such as propanimine, hexanimine; the dehalogenation or organic compounds which contain halogen atoms, e.g., of aromatic halogen-containing compounds, such as chloro- and bromobenzene, bromo- and chlorotoluenes and chloro- and bromo xylenes, also including compounds with more than one halogen atoms substituted; the aminating hydrogenation of alcohols, such as vinyl alcohol. [0040] Furthermore, within processes of this invention oximes may be reacted or secondary amines may be prepared starting from ketones and primary amines.

POLYMERS

[0041] Catalysts according to this invention may be also used for the hydrogenation, e yαrogenation, ydrogeno ysis, am nat ng hy rogenat on an dehalogenation o large molecules, e.g., of polymers.

[0042] Accordingly, the present invention also relates to processes for reacting a polymer comprising at least one catalytically reactable group in the presence of the above identified catalysts, wherein the hydrogenation of polymers comprising C=O groups, such as polyesters of dicarboxylic acids, unsaturated monocarboxylic acids, such as polymethacrylates, olefin/CO copolymers or polyketones, and the hydrogenation of polymers comprising nitrile groups, such as copolymers of styrene and butadiene, or copolymers of acrylonitrile, and the aminating hydrogenolysis of polyvinylalcohols and polyketones may occur in the presence of the above-mentioned catalysts.

[0043] The present invention relates to processes for the hydrogenation of a polymer comprising at least one C=O group or a polymer comprising at least one C=N group.

[0044] The term "polymer comprising at least one catalytically reactable group" relates to all polymers comprising such groups, e.g., to polymers comprising units having the structures (I) to (VIII), as defined above with respect to the monomeric compounds, or a halogen atom. Needless to say that the referenced polymers comprise the respective unit at least once and that also one or more units of two or more of said structures may be present in the polymer reacted according to the invention. [0045] The average molecular weight of the polymers to be reacted within processes of this invention is generally about 500 to about 500000, or about 1000 to about 100000 or about 1000 to about 50000. It is, however, possible to also react polymers having a higher molecular weight of up to one or several millions. If polymers comprising at least one C - C multiple bond, i.e. polymers comprising repeating units of the above defined structures (I) and (II) are reacted, these generally exhibit a weight average molecular weight of from about 5000 to about 1000000, or from about 50000 to about 500000, or from about 150000 to about 500000.

[0046] Useful polymers include (i) those containing olefinic double bonds, (ii) those containing diene units, and (iii) copolymers containing vinylaromatic units and diene units. Catalysts of this invention comprise ruthenium, rhodium or palladium as the active metal. It has to be noted in this respect that besides Ru, Rh or Pd, also the herein defined Group Ib, VIIb, or VIIIb metals, which are of course different from Ru, Rh an Pd, respective y, may e use .

[0047] Common diene units include all conventional polyunsaturated monomers containing from three to twelve carbon atoms, e.g., butadiene.

[0048] Copolymers to be hydrogenated may contain recurring units in random, block, or tapered distribution.

[0049] Aromatic monomers which may be present in the polymers to be hydrogenated in the process of the invention include monovinyl-substituted and polyvinyl-substituted aromatic compounds, e.g., styrene, alpha-methylstyrene, acrylonitrile, methacrylonitrile, and divinylbenzene. Furthermore, mixtures of vinylaromatic and/or diolefin monomers, optionally together with conventional olefinic monomers, can be present in the polymers to be hydrogenated. [0050] As examples for polymers which are to be reacted, e.g., hydrogenated, with the process of the invention, the following are mentioned: polymers having C — C groups, e.g. polybutadienes, such as poly(2,3-dimethylbutadiene), polyisoprene, polyacetylenes and polycyclopentadiene and hexadiene; polymers having C=C groups, such as polydiacetylenes; polymers having aromatic groups, such as polystyrene, terpolymers of acrylonitrile, butadiene and styrene, and copolymers of styrene and acrylonitrile; polymers having C^≡N groups, such as polyacrylonitrile, polyacrylonitrile-copolymers with e.g. vinyl chloride, vinylidene chloride, vinyl acetate or methacrylic acid esters or mixtures of two or more thereof as comonomers; polymers having C=C groups, such as polyesters, polyacrylamides, poly(acrylic acids), polyurea and polyketones; polymers having C^=S groups, such as polysulfones and polyethersulfones; halogen-containing polymers, such as polyvinyl chloride) and poly(vinylidene chloride); and polymers containing nitro groups, which may be obtained by nitration of, e.g., polyolefins by means of polymer analogous reactions. [0051] Examples for polymers being useful within the present invention include polyisoprene, polybutadiene, ethylene/CO copolymers, propylene/CO copolymers, poly(methyi methacrylate), polyterephthalate, polyadipate, styrene-butadiene- copolymers, acrylonitriie-butadiene-copolymers, acrylonitrile-styrene-copolymers, styrene-isoprene-styrene-triblockcopolymers, styrene-butadiene-styrene- triblockcopolymers and styrene-butadiene-styrene-starblockcopolymers. [0052] Generally, a complete reaction of the introduced educts is achieved. However, the reaction, e.g., hydrogenation, may be also carried out in such a way that by suitably c oosing tempera ure, ₂ pressure an ₂ amoun , on y se ec e groups o e hydrogenated may be reacted, while other kinds of groups to be hydrogenated are not hydrogenated, as will be familiar to those skilled in the art given the teachings of this disclosure.

[0053] Processes of this invention are suitable for reacting, e.g., hydrogenating, polymers comprising units of different structures, as defined above, e.g. a polymer comprising C - C multiple bonds and C¹¹^© groups and/or C=N groups, since the catalyst of the present invention is capable to first selectively react the C - C multiple bond, e.g. to achieve a hydrogenation of these groups of about 90 to 100%, while at the same time the C=O groups and/or C==N groups are reacted, e.g. hydrogenated to an extent of less than 25% and in general 0 to about 7%.

[0054] Furthermore, processes of this invention are suitable for the hydrogenation of polymers of high molecular weight and containing both C - C multiple bonds and aromatic groups, since the catalysts used in the process of the invention are capable of achieving hydrogenation of the C - C multiple bonds, e.g. ethylenically unsaturated regions, to an extent of from 90 to 100%, while the aromatic regions are hydrogenated to an extent of less than 25% and generally to an extent of from 0% to 7%.

[0055] After finishing this reaction, e.g., hydrogenation of the C — C multiple bonds, it is of course possible to nearly quantitatively react, e.g., hydrogenate, the other unsaturated groups being present in the polymer, e.g. C — O groups by further introducing hydrogen.

[0056] The processes of this invention may be used for already isolated and existing polymers.

CATALYSTS

[0057] Catalysts useful in processes of this invention may be prepared on an industrial scale by applying ruthenium, rhodium or palladium and, optionally, at least one Group Ib, VIIb, or VIIIb metal to a suitable support. Application may be effected by impregnating the support material with an aqueous metal salt solution, such as a solution of a ruthenium, rhodium or palladium salt, by spraying an appropriate metal salt solution on to the support, or by any other suitable method. Suitable ruthenium, rhodium or palladium salts for the preparation of the ruthenium, rhodium and palladium salt solutions, and suitable salts of the said Group Ib, VIIb, and VIIIb metals are the ni raxes, nnrosyi ni ra es, a i es, car ona es, car oxy a es, ace y acetona es, c orine complexes, nitrito complexes, or amine complexes of said metals, the nitrates and nitrosyl nitrates being useful.

[0058] In the case of catalysts that contain other metals in addition to ruthenium, rhodium or palladium, the metal salts or metal salt solutions can be applied simultaneously or successively.

[0059] The supports coated or impregnated with the solution of ruthenium salt, rhodium salt, or palladium salt and, optionally, another metal salt are then dried, e.g., at temperatures from 100⁰C to 150⁰C. If desired, these supports can be calcined at temperatures ranging from 200⁰C to 600⁰C, or from 350°C to 450⁰C. The coated supports can then be activated by treatment in a stream of gas containing free hydrogen at temperatures ranging from 3O⁰C to 600⁰C, or from 15O⁰C to 45O⁰C. The stream of gas can comprise or consist of from 50 to 100 vol% of H₂ and from 0 to 50 vol% of N₂.

[0060] If one or more Group Ib, VIIb, or VIiIb metals are to be applied to the support in addition to ruthenium, rhodium or palladium, and if the said application thereof is to take place successively, the support can be dried and, optionally, calcined between each application or impregnation, the drying temperature ranging from 100°C to 15O⁰C and the calcining temperature being from 200⁰C to 600⁰C. The order in which the metal salt solutions are applied is arbitrary.

[0061] If one or more Group Ib, VIIb, or VIIIb metals are to be applied to the support in addition to ruthenium, rhodium or palladium, it is desirable to use platinum, copper, rhenium, cobalt, nickel, or mixtures thereof.

[0062] The solution of ruthenium salt, rhodium salt, palladium salt, or other metal salt can be applied to the support(s) at such a rate that the content of active metal is from

0.01 to 30 wt %, or from 0.01 to 10 wt % and more can be from 0.01 to 5 wt %, based on the total weight of the catalyst, of ruthenium, rhodium or palladium and optionally of one or more Group Ib, VIIb, or VIIIb metals applied to the support.

[0063] The total metal surface area on the catalyst can be from 0.01 to 10 m²/g, or from 0.05 to 5 m²/g, or from 0.05 to 3 m²/g of catalyst. The metal surface area can be determined by the chemisorption method, as described in J. Lemaitre et al in

"Characterization of Heterogeneous Catalysts", Ed. Francis Delannay, Marcel Dekker,

New York (1984), pp 300 - 324.

[0064] In catalysts used in processes of this invention, the ratio of the surface area of a east one active me a o a o e ca a ys suppor can e ess an a ou . : , or less than about 0.1 :1 , or about 0.05:1 or less, the lower limit being about 0.0005:1.

SUPPORTS

[0065] The support materials used for the preparation of the catalysts to be used in processes of this invention possess macropores and mesopores. The term

"macropores" denotes pores having a diameter of from 50 nm to 10,000 nm; while the term "mesopores" relates to pores having a diameter of from 2.0 nm to less than 50 nm, and the term "micropores" denotes pores having a diameter less than 2.0 nm. See, e.g., Pure Applied Chem. 45, pp 71 et sec, particularly page 79 (1976).

[0066] The supports used in the present invention can have a pore distribution made up as follows: from 0% to about 10%, or from about 1 % to about 10%, or from about

2% to about 8%, or from about 5% to about 7% of the pore volume comprises macropores having pore diameters ranging from about 50 nm to about 10,000 nm, while about 90% to 100%, or from about 92% to 100%, or from about 92% to about

98%, or from about 93% to about 97% of the pore volume comprises mesopores having pore diameters ranging from 2 to less than 50 nm, the sum of the pore volumes being

100%.

[0067] The surface area of the support can be from about 50 m²/g to about 300 m²/g, or from about 100 m²/g to about 200 m²/g of support material.

[0068] The surface area of the support can be determined by the BET method by N₂ absorption, as will be known to those skilled in the art. Determination of the average pore diameter and the distribution of pore sizes can be carried out by N₂ absorption, as will be known to those skilled in the art.

[0069] Although, generally, all known catalyst support materials can be used, provided they have the pore size distribution defined above, it is desirable to use activated charcoal, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide, or mixtures thereof.

[0070] The catalysts used in the present invention can provide high reactivity (a high turnover index), selectivity, and a long on-stream time. When the catalysts proposed in the present invention are used for hydrogenation applications, the hydrogenation products can be obtained in high yield and purity. When powder/granule forms of the catalysts are used, the particle diameter size distribution can be from 1 micron to 500 microns, from 10 microns to 250 microns, or from 25 microns to 100 microns. SOLVENTS OR DILUENTS

[0071] In processes of this invention, the reaction, e.g., hydrogenation, can be carried out in the absence of a solvent or diluent, i.e. it is not necessary to carry out the reaction in solution.

[0072] It is also possible to directly react the polymer in its melt.

[0073] Desirably, however a solvent or diluent is used. The solvents or diluents used can be any suitable solvents or diluents. The choice thereof is not critical. For example, the solvents or diluents can contain small amounts of water, if desired.

[0074] In the reaction, e.g., hydrogenation, of an aromatic compound in which at least one hydroxyl group is attached to an aromatic core, examples of suitable solvents or diluents include the following: straight-chain or cyclic ethers, such as tetrahydrofuran or dioxane, and also aliphatic alcohols in which the alkyl radical exhibits from 1 to 10 carbon atoms or from 3 to 6 carbon atoms.

[0075] Examples of alcohols to be used are isopropanol, n-butanol, isobutanol and n-hexanol. Mixtures of these or other solvents or diluents may also be used.

[0076] In the reaction, e.g., hydrogenation, of an aromatic compound in which at least one amino group is attached to an aromatic core, examples of suitable solvents or diluents include the following: straight-chain or cyclic ethers, such as tetrahydrofuran

("THF"), 2-methyl THF or dioxane, other hydrocarbons, secondary and tertiary alcohols, and also ammonia and monoalkylamines or dialkylamines in which the alkyl radical exhibits from 1 to 3 carbon atoms, such as methylamine, ethylamine, or propylamine, or the corresponding dialkylamines, Mixtures of these or other solvents or diluents may also be used.

[0077] The amount of the solvent or diluent used is not subject to particular restrictions and can be freely selected as required. For example, those amounts which produce a 10 to 70 wt% strength solution of the compound to be hydrogenated can be used.

[0078] When carrying out a process of this invention it is desired that the product that is formed in the reaction, e.g., in hydrogenation, of this process, be used as solvent, optionally, together with other solvents or diluents. For example, a portion of the product that is formed in the process can be mixed with the compounds to be reacted, e.g., hydrogenated. The weight of hydrogenation product admixed as solvent or diluent can De TΓOΠΓI I IO mes, or rom o mes, or rom o imes the weig o e aromatic compounds to be reacted, e.g., hydrogenated.

[0079] The above may also be applied for the other compounds which are reacted according to the invention. Also in this respect, those skilled in the art will be familiar with selection of suitable solvents and diluents, given the teachings of this disclosure.

[0080] In the reaction 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 esters, such as tetrahydrofuran, dioxane, dibutylether, methyl-tert-butylether, etc., ketones, such as methyl ethyl ketone and acetone, esters, such as ethylacetate, or amides, such as DMF and N-methylpyrrolidone.

[0081] Cyclohexane, toluene or THF may be used. Mixtures of these and other solvents and diluents may also be used.

[0082] If the polymer was obtained by solution polymerization, it is also possible to directly react the obtained solution comprising the polymer within processes according to this invention.

[0083] The amount of the used solvent or diluent is not particularly limited within processes according to this invention and may be freely chosen according to demand by those skilled in the art. However, such amounts are desirable which lead to a solution comprising 1 to 70, or 1 to 40 wt% of the polymer to be reacted.

REACTION

[0084] In the following, the reaction is described by means of a hydrogenation as an example wherein, in case a dehydrogenation or an oxidation is carried out, instead of hydrogen or hydrogen-containing gases, gaseous hydrocarbons or oxygen-containing gases may be used under the below-described conditions.

[0085] The hydrogenation is carried out at suitable pressures and temperatures.

Pressures above about 2x10⁶ Pa, e.g., pressures from about 5x10⁶ Pa to about 3x10⁷

Pa can be used. Temperatures can range from about 30⁰C to about 25O⁰C, or from about 100⁰C to about 200°C, or from about 15O⁰C to about 200⁰C.

[0086] The hydrogenation process can be carried out continuously or batchwise.

When the process is carried out continuously, a portion of the hydrogenation product leaving the reactor can be added the reactor feed upstream of the reactor. A portion of the hydrogenation product leaving the reactor can be recycled as solvent, such that the proportions given un er e ea ing o ven s or i uen s are a aine . e remaining amount of hydrogenation product can be retrieved. [0087] When the process is carried out continuously, the feed rate of the compound(s) to be hydrogenated can be from about 0.05 to about 3 kg per liter of catalyst per hour and can be from about 0.1 to about 1 kg per liter of catalyst per hour. [0088] The hydrogenating gases used can be arbitrary gases containing free hydrogen and exhibiting no harmful amounts of catalyst poisons, such as CO. For example, reformer exhaust gases can be used. Pure hydrogen can be used as the hydrogenating gas.

[0089] In the case of phenols and amines additionally substituted by at least one optionally substituted Ci - Ci₀ and/or alkoxy radical, the isomer ratio of cis-configured to trans-configured products obtained can be varied over a wide range by varying the reaction conditions (temperature, solvents, etc.).

[0090] If an aromatic compound in which at least one amino group is attached to an aromatic core is to be hydrogenated using catalyst(s) of this invention, the hydrogenation can also be carried out in the presence of ammonia or dialkylamines, for example methylamine, ethylamine, propylamine or dimethylamine, diethylamine or dipropylamine. Suitable amounts of ammonia or monoalkylamine or dialkylamine can be used, e.g., from about 0.5 to about 50 parts by weight, or from about 1 to about 20 parts by weight, based, in each case, on 100 parts by weight of the compound(s) to be hydrogenated. Anhydrous ammonia or anhydrous amines can be suitably used. [0091] For oxidations, air or pure oxygen can be used. For dehydrogenations, hydrocarbons, e.g., methane or natural gas, can be used.

EXAMPLES

[0092] The following example is illustrative of the principles of this invention. It is understood that this invention is not limited to any one specific embodiment exemplified herein, whether in the examples or the remainder of this patent application. [0093] MMDA (4,4'-diamino-3,3'-dimethyldiphenylmethane) (45g), 5wt% ruthenium on alumina (2.Og), and 2-methyltetrahydrofuran (MeTHF, 105g) were charged to a 300-mL autoclave (Hastelloy C, baffle, gas-entrainment impeller) in a dry box. The autoclave was assembled in the dry box and was then removed from the dry box. The autoclave was sealed and then set up in the hood. The autoclave was purged with hydrogen to remove me resiαua a r an n trogen. was en e w compressed hydrogen o 646 psig. The reaction mixture was heated to 185 ⁰C and the hydrogen pressure was adjusted at about 1000 psig. Agitation speed was around 600 rpm. The reaction mixture was kept at 1000 psig, 185 ⁰C for 3 hours. It was then cooled and hydrogen pressure was released. The autoclave was brought into the dry box and the reaction mixture was transferred to a flask (152g). GC analysis of an aliquot indicated complete conversion. The reaction mixture was filtered thru a medium-fritted funnel by suction in the dry box to give 147.8g of filtrate. The wet cake was washed with MeTHF and then dried under vacuum to give1.98g of black powder. This recycled catalyst was used in the next reaction. The filtrate was stripped by rotary evaporation at 30 mm and about 45 ⁰C to remove the bulk of solvent (97.9g). GC and GC/MS analyses of the distillate showed no decomposition of MeTHF. The crude product (49.5g) contained about 85% of MACM isomers by GC wt% analyses. GC area% analysis showed seven major isomers in 41.1 %, 36.2%, 6.9%, 10%, 4.6%, 0.2%, and 0.9%.

[0094] It is to be understood that the reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to being combined with or coming into contact with another substance referred to by chemical name or chemical type (e.g., another reactant, a solvent, or etc.). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting combination or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemical reaction or in forming a combination to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense ("comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any, which occur in situ as a reaction is conducted is what the claim is intended to cover. Thus the fact that a substance, component or ingredient may have lost its original identity through a chemical reaction or rans orma ion ur ng e course o con ac ng, com n ng, en ng or m x ng operations, if conducted in accordance with this disclosure and with the application of common sense and the ordinary skill of a chemist, is thus wholly immaterial for an accurate understanding and appreciation of the true meaning and substance of this disclosure and the claims thereof. As will be familiar to those skilled in the art, the terms "combined", "combining", and the like as used herein mean that the components that are "combined" or that one is "combining" are put into a container with each other. Likewise a "combination" of components means the components having been put together in a container.

[0095] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims below.

Claims

AIIVIdWhat is claimed is:

1. A process for preparing an organic compound by catalytic hydrogenation, which process comprises

reacting an organic compound in the presence of a catalyst;

said organic compound being selected from (i) an aromatic compound in which at least one hydroxyl group is bonded to an aromatic ring, (ii) an aromatic compound in which at least one amino group is bonded to an aromatic ring, (iii) a ketone, (iv) an aldehyde, (v) a carboxylic acid or a derivative thereof, (vi) a polymer comprising at least one C=C group, (vii) a polymer comprising at least one C^^Ogroup, (viii) a polymer comprising at least one C^≡N group, and (ix) a mixture of two or more of (i) - (viii);

said catalyst comprising ruthenium, rhodium, or palladium, and optionally at least one Group Ib, VIIb or VIIIb metal, in an amount of from 0.01 to 30 wt %, based on the total weight of the catalyst;

wherein from 0 to 10% of the pores volumes of the catalyst support comprises macropores having a pore diameter of from 50 nm to 10,000 nm; and wherein from 90 to 100% of the pore volumes of the catalyst support comprises mesopores having a pore diameter of from 2 nm to less than 50 nm, the sum of said pore volumes being 100%.

2. The process of claim 1 in which the Group Ib, VIIb and VIIIb metal is selected from platinum, cobalt, copper, rhenium and nickel, or a mixture of two or more of these metals.

3. The process of claim 1 in which the catalyst support is selected from activated charcoal, silicon carbide, aluminum oxide, silicon dioxide, titanium dioxide, zirconium αioxi e, magnesium oxi e an zinc oxi e, or a mix ure o wo or more thereof.

4. The process of claim 1 in which the reaction is carried out in the presence of a solvent or diluent.

5. The process of claim 1 in which the organic compound is an aromatic compound in which at least one amino group is bonded to an aromatic ring.

6. The process of claim 1 in which the organic compound is an aromatic compound in which at least one hydroxyl group is bonded to an aromatic ring.