WO2010005859A2 - Procédés d'hydrogénation d'amines aromatiques - Google Patents

Procédés d'hydrogénation d'amines aromatiques Download PDF

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Publication number
WO2010005859A2
WO2010005859A2 PCT/US2009/049477 US2009049477W WO2010005859A2 WO 2010005859 A2 WO2010005859 A2 WO 2010005859A2 US 2009049477 W US2009049477 W US 2009049477W WO 2010005859 A2 WO2010005859 A2 WO 2010005859A2
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group
aromatic
acid
catalyst
bonded
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PCT/US2009/049477
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English (en)
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WO2010005859A3 (fr
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Tse-Chong Wu
Mario Lozanov
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Albemarle Corporation
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Publication of WO2010005859A3 publication Critical patent/WO2010005859A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/02—Reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • 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).
  • 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).
  • 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%.
  • 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 %
  • 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 , , .
  • a catalyst comprising, as active metal, ruthenium, rhodium or palladium, either alone or together with at least one Group Ib, VIIb, or VIIIb metal
  • 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%.
  • 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.
  • polymer is defined as relating to molecules having a molecular weight of higher than about 500.
  • 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.
  • 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:
  • R is a hydroxyl group or an amino group.
  • 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.
  • 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.
  • amines additionally substituted by a Ci - C 10 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.
  • 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 and, optionally, also at least one unsubstituted or substituted C 1 - 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.
  • 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
  • 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.
  • halogen atoms e.g., fluorine atoms, or other suitable inert substituents.
  • 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, ⁇ -naphthol and ⁇ -naphthol.
  • 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 - C 2 o alkyl radicals, e.g., Ci - Cio alkyl radicals, including, e.g., methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.
  • alkyl substituents which can be Ci - C 2 o alkyl radicals, e.g., Ci - Cio alkyl radicals, including, e.g., methyl, ethyl, propyl, isopropyl, butyl or tert-butyl.
  • 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.
  • a phenol in processes of the present invention, 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.
  • 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 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 - C 20 alkyl radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl radicals.
  • 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.
  • halogen atoms e.g., fluorine atoms, or other suitable inert substituents.
  • 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 - C 10 aikyi radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl.
  • alkyl substituents which can be Ci - C-20 alkyl radicals, including Ci - C 10 aikyi radicals, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl or tert-butyl.
  • the amino group bonded to the aromatic ring may be unsubstituted or substituted by one or two of the above-described alkyl radicals.
  • Suitable compounds are aniline, naphthylamine, diaminobenzenes, diaminotoluenes and bis-(p-aminophenyl)methane, 4,4'-diamino-3,3'- dimethyldiphenylmethane, or mixtures thereof.
  • 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, be
  • polyketones such as copolymers of ethylene and CO can be used.
  • carboxylic acids and derivatives thereof e.g., those having 1 to
  • 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
  • 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.
  • 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.
  • carboxylic acids e.g., methyl formate, acetic acid ester, butanoic acid butyl ester, dimethyl terephthalate, dimethyl adipate, methyl methacrylate, butyrolactone, caprolactone
  • polycarboxylic acid esters such as polyacrylic and
  • 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.
  • 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 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-aminohex
  • 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
  • Catalysts according to this invention may be also used for the hydrogenation, e y ⁇ rogenation, ydrogeno ysis, am nat ng hy rogenat on an dehalogenation o large molecules, e.g., of polymers.
  • nitrile groups such as copolymers of
  • 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.
  • 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.
  • 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.
  • 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 .
  • Common diene units include all conventional polyunsaturated monomers containing from three to twelve carbon atoms, e.g., butadiene.
  • Copolymers to be hydrogenated may contain recurring units in random, block, or tapered distribution.
  • 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.
  • 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.
  • reaction e.g., hydrogenation
  • the reaction 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.
  • 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%.
  • 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.
  • metal salts or metal salt solutions can be applied simultaneously or successively.
  • 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 100 0 C to 150 0 C. If desired, these supports can be calcined at temperatures ranging from 200 0 C to 600 0 C, or from 350°C to 450 0 C.
  • the coated supports can then be activated by treatment in a stream of gas containing free hydrogen at temperatures ranging from 3O 0 C to 600 0 C, or from 15O 0 C to 45O 0 C.
  • the stream of gas can comprise or consist of from 50 to 100 vol% of H 2 and from 0 to 50 vol% of N 2 .
  • the support can be dried and, optionally, calcined between each application or impregnation, the drying temperature ranging from 100°C to 15O 0 C and the calcining temperature being from 200 0 C to 600 0 C.
  • the order in which the metal salt solutions are applied is arbitrary.
  • 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.
  • 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.
  • the total metal surface area on the catalyst can be from 0.01 to 10 m 2 /g, or from 0.05 to 5 m 2 /g, or from 0.05 to 3 m 2 /g of catalyst.
  • the metal surface area can be determined by the chemisorption method, as described in J. Lemaitre et al in
  • 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.
  • the support materials used for the preparation of the catalysts to be used in processes of this invention possess macropores and mesopores.
  • 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).
  • 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
  • pore volume 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
  • the surface area of the support can be from about 50 m 2 /g to about 300 m 2 /g, or from about 100 m 2 /g to about 200 m 2 /g of support material.
  • the surface area of the support can be determined by the BET method by N 2 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 N 2 absorption, as will be known to those skilled in the art.
  • 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.
  • the catalysts used in the present invention can provide high reactivity (a high turnover index), selectivity, and a long on-stream time.
  • the catalysts proposed in the present invention are used for hydrogenation applications, the hydrogenation products can be obtained in high yield and purity.
  • 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.
  • the reaction e.g., hydrogenation
  • the reaction 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.
  • a solvent or diluent is used.
  • the solvents or diluents used can be any suitable solvents or diluents. The choice thereof is not critical.
  • the solvents or diluents can contain small amounts of water, if desired.
  • 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.
  • alcohols to be used are isopropanol, n-butanol, isobutanol and n-hexanol. Mixtures of these or other solvents or diluents may also be used.
  • solvents or diluents include the following: straight-chain or cyclic ethers, such as tetrahydrofuran
  • THF 2-methyl THF or dioxane
  • other hydrocarbons such as methylamine, ethylamine, or propylamine, or the corresponding dialkylamines
  • Mixtures of these or other solvents or diluents may also be used.
  • 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.
  • 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.
  • 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 T ⁇ O ⁇ I I IO mes, or rom o mes, or rom o imes the weig o e aromatic compounds to be reacted, e.g., hydrogenated.
  • 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.
  • hydrocarbons such as hexane, cyclohexane, methylcyclohexane, heptane, octane, toluene, xylene, etc.
  • straight-chain or cyclic esters such as tetrahydrofuran, dioxane, di
  • Cyclohexane, toluene or THF may be used. Mixtures of these and other solvents and diluents may also be used.
  • 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 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.
  • the hydrogenation is carried out at suitable pressures and temperatures.
  • Pressures above about 2x10 6 Pa e.g., pressures from about 5x10 6 Pa to about 3x10 7
  • Pa can be used. Temperatures can range from about 30 0 C to about 25O 0 C, or from about 100 0 C to about 200°C, or from about 15O 0 C to about 200 0 C.
  • the hydrogenation process can be carried out continuously or batchwise.
  • 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.
  • 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.
  • 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.).
  • 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.
  • 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.
  • For oxidations air or pure oxygen can be used.
  • hydrocarbons e.g., methane or natural gas, can be used.
  • the autoclave was sealed and then set up in the hood.
  • the autoclave was purged with hydrogen to remove me resi ⁇ ua a r an n trogen. was en e w compressed hydrogen o 646 psig.
  • the reaction mixture was heated to 185 0 C 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 0 C 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 0 C 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%.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de réaction d'un composé organique en présence d'un catalyseur appliqué à un support comprenant, à titre de métal actif, du ruthénium, du rhodium ou du palladium, seul ou en mélange avec au moins un métal du Groupe Ib, VIIb, ou VIIIb en une quantité de 0,01 à 30 % en poids, sur la base du poids total du catalyseur. De 0 à 10 % du volume de pores dudit support comprennent des macropores ayant un diamètre de pore dans la plage de 50 à 10 000 nm et de 90 à 100 % du volume de pores dudit support comprennent des mésopores ayant un diamètre de pore dans la plage de 2 à moins de 50 nm, la somme desdits volumes de pores étant égale à 100 %.
PCT/US2009/049477 2008-07-07 2009-07-02 Procédés d'hydrogénation d'amines aromatiques WO2010005859A2 (fr)

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CN102030657A (zh) * 2010-11-25 2011-04-27 浙江台州清泉医药化工有限公司 一种3,3′-二甲基-4,4′-二氨基二环己基甲烷的合成方法
EP2883864A1 (fr) * 2013-12-11 2015-06-17 Basf Se Procédé d'hydrogénisation de composés aromatiques
US9840574B2 (en) 2014-05-16 2017-12-12 Kraton Polymers U.S. Llc Branched broad MWD conjugated diene polymer
CN113042043A (zh) * 2021-03-24 2021-06-29 内蒙古瑞翔拓创新材料有限公司 钌基加氢催化剂、钌基加氢催化剂水溶液及制备方法和应用

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GB1368449A (en) * 1970-09-17 1974-09-25 Bayer Ag Preparation of cyclohexanone by selective vapour
DE19604791A1 (de) * 1996-02-09 1997-08-14 Basf Ag Verfahren zur Hydrierung von aromatischen Verbindungen, in denen mindestens eine Hydroxylgruppe an einen aromatischen Kern gebunden ist
US20010000035A1 (en) * 1996-06-19 2001-03-15 Thomas Ruhl Process for reacting an organic compound in the presence of a supported ruthenium catalyst
CN1830560A (zh) * 2005-03-11 2006-09-13 石油大学(北京) 大孔加氢催化剂及其制备方法
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DE2059938A1 (de) * 1969-12-12 1971-07-08 Leuna Werke Veb Verfahren zur Herstellung von Cyclohexanon durch katalytische Hydrierung von Phenol
GB1368449A (en) * 1970-09-17 1974-09-25 Bayer Ag Preparation of cyclohexanone by selective vapour
DE19604791A1 (de) * 1996-02-09 1997-08-14 Basf Ag Verfahren zur Hydrierung von aromatischen Verbindungen, in denen mindestens eine Hydroxylgruppe an einen aromatischen Kern gebunden ist
US20010000035A1 (en) * 1996-06-19 2001-03-15 Thomas Ruhl Process for reacting an organic compound in the presence of a supported ruthenium catalyst
CN1830560A (zh) * 2005-03-11 2006-09-13 石油大学(北京) 大孔加氢催化剂及其制备方法
WO2007085463A1 (fr) * 2006-01-26 2007-08-02 Universita Di Pisa Procede de fabrication de catalyseurs metalliques nanostructures et leur utilisation dans des reactions catalytiques

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Publication number Priority date Publication date Assignee Title
CN102030657A (zh) * 2010-11-25 2011-04-27 浙江台州清泉医药化工有限公司 一种3,3′-二甲基-4,4′-二氨基二环己基甲烷的合成方法
EP2883864A1 (fr) * 2013-12-11 2015-06-17 Basf Se Procédé d'hydrogénisation de composés aromatiques
WO2015086639A3 (fr) * 2013-12-11 2015-07-30 Basf Se Procédé pour l'hydrogénation de composés aromatiques
CN105992756A (zh) * 2013-12-11 2016-10-05 巴斯夫欧洲公司 氢化芳族化合物的方法
CN105992756B (zh) * 2013-12-11 2018-09-21 巴斯夫欧洲公司 氢化芳族化合物的方法
US10329237B2 (en) 2013-12-11 2019-06-25 Basf Se Method for hydrogenating aromatic compounds
US9840574B2 (en) 2014-05-16 2017-12-12 Kraton Polymers U.S. Llc Branched broad MWD conjugated diene polymer
CN113042043A (zh) * 2021-03-24 2021-06-29 内蒙古瑞翔拓创新材料有限公司 钌基加氢催化剂、钌基加氢催化剂水溶液及制备方法和应用

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