EP3080081A1 - Procédé d'hydrogénation de 4,4'-méthylènedianiline - Google Patents

Procédé d'hydrogénation de 4,4'-méthylènedianiline

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Publication number
EP3080081A1
EP3080081A1 EP14809408.9A EP14809408A EP3080081A1 EP 3080081 A1 EP3080081 A1 EP 3080081A1 EP 14809408 A EP14809408 A EP 14809408A EP 3080081 A1 EP3080081 A1 EP 3080081A1
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EP
European Patent Office
Prior art keywords
weight
catalyst
present
cis
trans
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP14809408.9A
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German (de)
English (en)
Inventor
Andreas Weickgenannt
Bernd Bastian SCHAACK
Barbara Wucher
Alexander Panchenko
Frank Hettche
Martin Bock
Aik Meam TAN
Kirsten Dahmen
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BASF SE
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BASF SE
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Priority to EP14809408.9A priority Critical patent/EP3080081A1/fr
Publication of EP3080081A1 publication Critical patent/EP3080081A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
    • C07C211/36—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the hydrogenation of 4,4'-methylenedianiline (MDA) and / or polymer MDA with hydrogen in the presence of a catalyst, wherein the catalyst comprises ruthenium on a zirconium oxide catalyst.
  • Carrier material contains, as well as the use of a catalyst containing ruthenium on a zirconium oxide support material for the hydrogenation of 4,4'-methylenedianiline (MDA) and / or polymer MDA.
  • WO 2009/153123 A1 discloses a continuous process and a reactor for the hydrogenation of organic compounds in a multiphase system in the presence of a homogeneous or heterogeneous catalyst, the process being carried out in two stages.
  • Heterogeneous catalysts for example comprising noble metals such as platinum, palladium, ruthenium and rhodium or other transition metals such as molybdenum, tungsten and chromium, are disclosed as possible catalysts according to this document. These heterogeneous catalysts can be present on support materials.
  • Corresponding support materials are, for example, carbon, aluminum oxide, silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or mixtures of these support materials.
  • an MDA melt was hydrogenated in the presence of a suspended ruthenated (R) (IV) hydrate catalyst.
  • R suspended ruthenated
  • Embodiments for the hydrogenation of MDA in the presence of Ru, supported on zirconium oxide, are not included in the application.
  • the substrates used in this process are preferably aromatic compounds containing amino substituents, for example MDA, polymer MDA, aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, o-phenylenediamine, etc.
  • the heterogeneous catalysts are used in suspension.
  • DE 19533718 A1 discloses a process for the hydrogenation of aromatic compounds in which at least one amino group is attached to an aromatic nucleus.
  • a heterogeneous catalyst comprising ruthenium and optionally at least one metal of the I, VII or VIII subgroup can be used.
  • the carrier material used is, for example, aluminum oxide, silicon dioxide, titanium dioxide or zirconium dioxide, preferably aluminum dioxide or zirconium dioxide.
  • only a catalyst containing ruthenium on the support material alumina, but not zirconia.
  • EP 1337331 B1 discloses a process for the catalytic hydrogenation of aromatic or heteroaromatic amines, characterized in that the active metal is ruthenium and the catalyst contains at least one further metal of the subgroup I, VII or VIII and these are applied to a support material, that is a BET (N2) surface of less than 10 m 2 / g.
  • aromatic compounds for example, 4,4'-MDA and isomers thereof are used.
  • EP 01 1 1238 B1 discloses a process for the catalytic hydrogenation of 4,4'-MDA, characterized in that the hydrogenation in the presence of ruthenium on a support material and in the presence of 65 to 700% by weight, based on the amount of ruthenium, of a moderating Compound is selected which is selected from the group of nitrates and sulfates of alkali metals and nitrates of alkaline earth metals. Such an additive is not knowingly added in the process of the invention.
  • EP 1366812 B1 discloses a process for the hydrogenation of an aromatic amine, in which ruthenium is carried out on a support material in the presence of the active metal.
  • the method is characterized in that the BET surface area of the carrier material used is in the range from greater than 30 m 2 / g to less than 70 m 2 / g.
  • support materials there are disclosed, inter alia, alumina, silica, titania and zirconia. In the examples, only aluminum oxide is used as the carrier material, but not zirconium oxide.
  • WO 201 1/003899 A1 discloses a process for the hydrogenation of organic compounds, for example aromatic compounds.
  • a heterogeneous catalyst containing noble metals such as platinum, palladium, ruthenium, osmium, iridium and rhodium or other transition metals can be used.
  • support materials for example, alumina, silica, titania and activated carbon, but not zirconia.
  • WO2009 / 090179 A2 discloses a process for the preparation of cycloaliphatic amines by hydrogenation of the corresponding aromatic compounds.
  • a ruthenium-containing catalyst is used in the form of a suspension to which suspended inorganic additives are added.
  • These additives include, but are not limited to, zirconia.
  • the additive does not serve as a carrier material in this case, since the ruthenium is not applied to this before use in the hydrogenation.
  • Polymer MDA is known per se to the person skilled in the art.
  • the person skilled in the art understands oligomeric or polymeric addition products of 4,4'-methylenedianiline, for example containing 2 to 100, in particular 3 to 7, repeating units 4,4'-methylenedianiline.
  • the hydrogenation according to the invention from the polymer MDA used the corresponding nuclear-hydrogenated oligomers or polymers.
  • the corresponding trans, trans, cis-trans or cis, cis isomers can be obtained for each individual 4,4'-methylenedianiline unit.
  • the process according to the invention preferably gives a corresponding oligomeric or polymeric kerhydrogenated compound which has the smallest possible proportion of trans, trans repeat units.
  • the object of the present invention is therefore to provide a process for the hydrogenation of 4,4'-methylenedianiline to 4,4'-diaminocyclohexylmethane and / or of polymer MDA to give the corresponding ring-hydrogenated compound in which a catalyst is used which, on the one hand has a particularly high activity over a long period of time, so that a high conversion can be achieved over a long period, and further a product mixture, d. H.
  • the present invention is characterized by using a catalyst containing ruthenium on a zirconia support material to hydrogenate 4,4'-methylenedianiline to 4,4'-diaminocyclohexylmethane and / or polymer MDA to the corresponding core-hydrogenated compound , wherein the trans, trans isomer of the desired compound is present in a small proportion.
  • 4,4'-methylene dianiline can be used in pure form. It is also possible according to the invention that the 4,4'-methylenedianiline used in addition to the desired isomer also 2,4'-methylenedianiline (II)
  • 4,4'-methylenedianiline is ring hydrogenated, d. H. the corresponding isomeric dicyclohexyl derivatives are obtained.
  • the individual isomers of 4,4'-diaminocyclohexylmethane, d. H. Trans, trans-4,4'-diaminocyclohexylmethane (IIIa), cis, trans-4,4'-diaminocyclohexylmethane (Illb) and cis, cis-4,4'-diaminocyclohexylmethane (Nie) are shown below.
  • the process according to the invention preferably gives a product which, without further purification of the reactor output, contains the trans, trans isomer in an amount of less than 25% by weight, preferably less than 23% by weight, in each case based on the total amount of the product obtained, the remaining portion being attributable to the cis, trans and / or cis, cis isomers, and optionally to hydrogenation products of 2,4'-methylenedianiline.
  • the product obtained is a mixture containing the isomers of 4,4'-diaminodicyclohexylmethane, the trans, trans isomer being present in an amount of 10 to 30% by weight, preferably 10 to 26% by weight. -%, the cis, trans isomer in an amount of 30 to 55 wt .-%, preferably 40 to 55 wt .-%, and the cis, cis isomer in an amount of 10 to 50 wt .-%, preferably 25 to 40 wt .-%, each based on the total amount of all present isomers, are present, the sum of the present isomers always 100 wt .-% results.
  • a mixture of corresponding oligomeric or polymeric, ring-hydrogenated compounds is obtained starting from polymer MDA, containing as repeat units the isomers of 4,4'-diaminodicyclohexylmethane, the repeat units being the trans, trans isomer in an amount of 10 to 30 wt .-%, preferably 10 to 26 wt .-%, the cis, trans isomer in an amount of 30 to 55 wt .-%, preferably 40 to 55 wt .-%, and cis, cis-isomer in an amount of 10 to 50 wt .-%, preferably 25 to 40 wt .-%, each based on the total amount of all present isomeric repeating units, present, wherein the sum of the present isomers always 100 wt .-% results.
  • the proportions of the individual isomers contained in the product obtained according to the invention can be determined by analytical methods known to those skilled in the art.
  • a preferred analytical method is the gas chromatography (GC) known to those skilled in the art.
  • a product preferably obtained according to the invention with the abovementioned low proportions of trans, trans isomer has a melting point of less than 40 ° C., preferably less than 30 ° C., more preferably less than 22 ° C.
  • a preferred lower limit for the melting point is, for example, 0 ° C.
  • the process according to the invention can generally be carried out continuously or batchwise.
  • the present invention relates to the process according to the invention, wherein it is carried out continuously.
  • the process according to the invention can generally be carried out in suspension or in a fixed bed.
  • the present invention therefore preferably relates to the process according to the invention, wherein it is carried out in suspension or in a fixed bed.
  • the hydrogenation can be carried out for example in a stirred tank or stirred autoclave, a loop reactor, a jet loop reactor, a bubble column or a fixed bed reactor with Umpumpniklauf.
  • the discontinuous hydrogenation is carried out in a stirred tank or stirred autoclave.
  • the hydrogenation is usually carried out in a continuously operated stirred tank reactor, a continuously operated loop reactor, a continuously operated jet loop reactor, a continuously operated bubble column or a continuously operated fixed bed reactor with Umpumpniklauf or a stirred tank cascade.
  • the process is preferably carried out in trickle-bed reactors or in flooded mode according to the fixed-bed procedure, for example according to WO 2008/015135 A1.
  • the hydrogen can be passed both in cocurrent with the solution of the reactant to be hydrogenated and in countercurrent over the catalyst.
  • Suitable apparatus for carrying out hydrogenation on the catalyst fluidized bed and on the fixed catalyst bed are known in the art, e.g. from Ullmanns Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 13, p. 135 ff., and P.N. Rylander, "Hydrogenation and Dehydrogenation” in Ullmann's Encyclopaedia of Industrial Chemistry, 5th ed. on CD-ROM.
  • an after-reaction of the hydrogenation can take place gene.
  • the hydrogenation can be passed after the hydrogenation process in the gas phase or in the liquid phase in the straight or recirculated passage through one or more downstream reactors.
  • the reactor can be operated in liquid-phase hydrogenation in trickle mode or operated flooded.
  • the reactor is filled with the catalyst according to the invention or with another catalyst known to the person skilled in the art.
  • Suitable reactors for carrying out the process according to the invention in suspension operation are known per se to the person skilled in the art, for example stirred tanks or bubble columns. According to the invention, it is also possible to work in a cascade of several suspension reactors connected in series, for example in a stirred tank cascade or a bubble column cascade, for example with at least three respective reactors connected in series.
  • the process according to the invention is generally carried out at a pressure of 50 to 500 bar, preferably at a pressure of 60 to 300 bar.
  • the present invention therefore preferably relates to the process according to the invention, wherein it is carried out at a pressure of 60 to 300 bar.
  • the process pressure is preferably determined by the hydrogen partial pressure.
  • the present invention therefore particularly preferably relates to the process according to the invention, wherein it is carried out at a hydrogen pressure of 50 to 500 bar, preferably 60 to 300 bar.
  • the process is generally carried out at a temperature of 30 to 280 ° C, preferably at a temperature of 60 to 250 ° C.
  • the process according to the present invention is carried out in a fixed bed, it is preferably carried out at a temperature of 50 to 190 ° C, preferably 70 to 120 ° C.
  • the present invention therefore preferably relates to the process according to the invention, wherein it is carried out in a fixed bed at a temperature of 50 to 190.degree. C., preferably 70 to 120.degree.
  • the process according to the present invention is carried out in suspension, it is preferably carried out at a temperature of 50 to 190 ° C, preferably 100 to 140 ° C.
  • the present invention therefore preferably relates to the process according to the invention, wherein it is carried out in suspension at a temperature of 50 to 190.degree. C., preferably 100 to 140.degree.
  • hydrogen is used as the hydrogenating agent.
  • the hydrogen used as hydrogenating agent is used in a preferred embodiment in excess, based on the compound to be hydrogenated.
  • hydrogen as the hydrogenating agent in a 1.01 to 10 times, preferably 1.05 to 10 times, more preferably 1 to 10 times, particularly preferably 1.01 to 5 times, for example 1.1 - Used up to 5 times, stoichiometric excess.
  • the hydrogen used can be recycled as cycle gas in the reaction.
  • technically pure hydrogen is used.
  • “technically pure” is understood as meaning a content of hydrogen of at least 99.0% by weight, preferably at least 99.5% by weight.
  • the hydrogen can also be used in the form of a gas containing hydrogen.
  • a gas containing hydrogen for example, mixtures containing gases and inert gases such as nitrogen, helium, neon, argon, ammonia and / or carbon dioxide are possible.
  • reformer effluents, refinery gases, etc. can be used as the hydrogen-containing gases.
  • These hydrogen-containing gases have a hydrogen content of, for example, 10 to 100 wt .-%, preferably 50 to 100 wt .-%, on.
  • the process according to the invention can generally be carried out in the presence or in the absence of at least one solvent. Most preferably, the process is carried out in an organic solvent. In a further preferred embodiment, the process according to the invention is carried out in substance, i. H. as a melt in the absence of a solvent.
  • solvents are, for example, selected from the group consisting of alcohols, such as isopropanol, isobutanol or t-butanol, ethers, such as diethyl ether, glycol dimethyl ether (diglyme), glycol dipropyl ether (proglyme), dioxane or tetrahydrofuran, and mixtures thereof.
  • alcohols such as isopropanol, isobutanol or t-butanol
  • ethers such as diethyl ether, glycol dimethyl ether (diglyme), glycol dipropyl ether (proglyme), dioxane or tetrahydrofuran, and mixtures thereof.
  • dioxane or proglyme is referred to as Solvent used.
  • methyl diaminocyclohexan is used.
  • the product formed in the reaction ie 4,4'-diaminocyclohexylmethane, in particular an isomer mixture according to the invention comprising trans, trans-4,4'-diaminocyclohexylmethane, cis, trans-4,4'-diaminocyclohexylmethane and cis, cis-4,4'-diaminocyclohexylmethane, or the low boilers formed, for example 4-aminocyclohexylmethylcyclohexane used as solvent.
  • the process according to the invention is carried out in the presence of a solvent, this is generally used in an amount such that a 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, is used. -% solution of provided for the hydrogenation organic compounds is present.
  • ruthenium is used as the catalyst on a zirconium oxide support material.
  • Corresponding catalysts can be prepared by known methods such as impregnation, for example described in AB Stiles, Catalyst Manufacture-Laboratory and Commercial Preparations, Marcel Dekker, New York, 1983, or precipitation or precipitation, for example as described in EP 1 106,600, page 4, and AB Stiles, Catalyst Manufacture, Marcel Dekker Inc., 1983, page 15.
  • the procedure can be such that suitable compounds of ruthenium, for example ruthenium salts, are applied to the support material zirconium oxide in the form of extrudates, pellets or spheres, for example with diameters of about 1.5 to 10 mm. Subsequently, generally at a temperature of 80 to 180 ° C, for example 120 ° C, dried and calcined at a temperature of 180 to 450 ° C, for example 180 ° C, both steps can also be carried out simultaneously.
  • Suitable ruthenium salts for application are, for example, selected from the group consisting of ruthenium acetate, acetylacetonate, chloride, nitrosyl nitrate and mixtures thereof.
  • a correspondingly prepared catalyst is basically available after drying for the use according to the invention. However, it is preferably activated before its use, particularly preferably after arrangement in the reactor provided for the hydrogenation according to the invention, by treatment with hydrogen at a temperature of for example 150 to 400 ° C.
  • ruthenium is preferably present in a total amount of 0.05 to 15 wt.% Or more than 15 to 20 wt.%, Ie 0.05 to 20 wt.%, Preferably 0.05 to 12 wt .-% or more than 12 to 15 wt .-%, ie 0.05 to 15 wt .-%, particularly preferably 0.1 to 1 1 wt .-% or more than 1 1 to 15 wt .-% , ie 0.1 to 15 wt .-%, each based on the total weight of the catalyst before.
  • the carrier material zirconium oxide (ZrO.sub.2) is preferably present in monoclinic, tetracogenic, cubic, amorphous phase or a mixed phase, particularly preferably in monoclinic, tetragonal or a mixed phase of these modifications.
  • the present invention therefore preferably relates to the process according to the invention, wherein the zirconium oxide support material is present in monoclinic, tetragonal, cubic, amorphous phase or a mixed phase of these modifications. More preferably, the present invention relates to the method according to the invention, wherein the zirconium oxide support material is present in monoclinic, tetragonal, cubic, amorphous phase or a mixed phase of these modifications.
  • the zirconium oxide support material preferably before application of ruthenium, preferably has a BET surface area of 30 to 300 m 2 / g, preferably 35 to 250 m 2 / g, particularly preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, in each case determined by nitrogen sorption according to DIN 66131.
  • the zirconium oxide support material preferably before the application of the ruthenium, preferably has a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.9 cm 3 / g, in each case determined by mercury porosimetry according to DIN 66133.
  • the zirconium oxide support material of the catalyst according to the invention which is used in suspension, preferably before applying the ruthenium, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.5 to 1, 0 cm 3 / g, especially preferably 0.7 to 0.9 cm 3 / g, each determined by mercury porosimetry according to DIN 66133.
  • the zirconium oxide support material of the catalyst according to the invention which is used in a fixed bed, preferably before applying the ruthenium, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.6 cm 3 / g , particularly preferably 0.1 to 0.5 cm 3 / g, in each case determined by mercury porosimetry according to DIN 66,133th
  • the zirconium oxide support material has a tamped density, preferably before application of the ruthenium, of 500 to 2000 kg / m 3 , preferably 600 to 1800 kg / m 3 , particularly preferably 700 to 1750 kg / m 3 , in each case determined in one Stampfvolumeter STAV2003 the company JEL, where 2000 times was tamped.
  • the zirconium oxide support material preferably before the application of the ruthenium, has a BET surface area of 30 to 300 m 2 / g, preferably 35 to 250 m 2 / g, particularly preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, in each case determined by nitrogen sorption, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.8 cm 3 / g, especially preferably 0.1 to 0.7 cm 3 / g, each determined by mercury porosimetry and a tamped density of 500 to 2000 kg / m 3 , preferably 600 to 1750 kg / m 3 , more preferably 700 to 1500 kg / m 3 , each determined in a tamping volumeter STAV2003 the company JEL, wherein 2000 times was tamped on.
  • the present invention therefore preferably relates to the process according to the invention, wherein the zirconium oxide support material, preferably before application of the ruthenium, has a BET surface area of 30 to 300 m 2 / g, preferably 35 to 250 m 2 / g, particularly preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, in each case determined by nitrogen sorption, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0, 8 cm 3 / g, more preferably 0.1 to 0.7 cm 3 / g, each determined by mercury porosimetry and a tamped density of 500 to 2000 kg / m 3 , preferably 600 to 1800 kg / m 3 , more preferably 700 to 1500 kg / m 3 , each determined in a tamping volumeter STAV2003 the company JEL, wherein 2000 times was tamped, comprising.
  • the zirconium oxide support material preferably before application of the ruthenium, has a monoclinic or tetragonal modification (or a mixture of both), a BET surface area of 30 to 300 m 2 / g, preferably 35 to 250 m 2 / g, particularly preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, in each case determined by nitrogen sorption, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.8 cm 3 / g, particularly preferably 0.1 to 0.7 cm 3 / g, each determined by mercury porosimetry and a tamped density of 500 to 2000 kg / m 3 , preferably 600 to 1800 kg / m 3 , more preferably 700 to 1500 kg / m 3 , each determined in a tamping volumeter STAV2003 the company JEL, wherein 2000 times was ta
  • the present invention therefore preferably relates to the process according to the invention, wherein the zirconium oxide support material, preferably before application of the ruthenium, is a monoclinic or tetragonal modification (or a mixture of both), a BET surface area of 30 to 300 m 2 / g, preferably 35 to 250 m 2 / g, particularly preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, in each case determined by nitrogen sorption, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.8 cm 3 / g, particularly preferably 0.1 to 0.7 cm 3 / g, each determined by mercury porosimetry and a tamped density of 500 to 2000 kg / m 3 , preferably 600 to 1800 kg / m 3 , more preferably 700 to 1500 kg / m 3 , each determined in a tamping volume STAV2003
  • the zirconium oxide support material of the catalyst used in the fixed bed has a pore size distribution in which more than 50% of the pores present are covered by mesopores with a diameter of 2 nm to 50 nm, and the rest by 100% by macropores with a diameter> 50 nm are formed.
  • the present invention therefore preferably relates to the process according to the invention, characterized in that the zirconium oxide support material of the catalyst used in the fixed bed has a pore size distribution in which more than 50% of the pores present are covered by mesopores with a diameter of 2 nm to 50 nm, and the remainder being 100% formed by macropores having a diameter> 50 nm.
  • the zirconium oxide support material of the catalyst used in suspension preferably has a pore size distribution in which more than 40% of the pores present are macropores with a diameter of> 50 nm, and the remainder 100% by mesopores with a diameter of 2 nm 50 nm are formed.
  • the present invention therefore preferably relates to the process according to the invention, characterized in that the zirconium oxide support material of the catalyst used in suspension has a pore size distribution in which more than 40% of the pores present are macropores with a diameter of> 50 nm, and the remainder 100% are formed by mesopores with a diameter of 2 nm to 50 nm.
  • the present invention preferably relates to the process according to the invention, wherein the catalyst has a BET surface area of 30 to 300 m 2 / g, preferably 50 to 90 m 2 / g or more than 90 to 100 m 2 / g, ie 50 to 100 m 2 / g, a pore volume of 0.1 to 1 cm 3 / g, preferably 0.1 to 0.9 cm 3 / g, and a tamped density of 500 to 2000 kg / m 3 , preferably 700 to 1750 kg / m 3 , having.
  • the present invention also relates to the inventive method, wherein the catalyst used in the fixed bed has a pore size distribution in which more than 50% of the pores present by mesopores with a diameter of 2 nm to 50 nm, and the rest to 100% by macropores with a diameter> 50 nm are formed.
  • the present invention also relates to the process according to the invention, wherein the catalyst used in suspension has a pore size distribution in which more than 40% of the pores present by macropores with a diameter of> 50 nm, and the rest to 100% by mesopores with a diameter from 2 nm to 50 nm.
  • the catalyst used according to the invention contains the catalytically active metal ruthenium, more preferably over the entire support material, i. distributed over the entire diameter of a carrier particle, d. H.
  • the catalytically active ruthenium is substantially homogeneous throughout the support material, i. over the entire diameter of a Stromermaterialteilchens, distributed before.
  • a catalyst loading of from 0.01 to 2 kg, preferably from 0.01 to 1 kg, more preferably from 0.02 to 0.6 kg, very preferably from 0.02 to 0.2 kg of organic , compound to be hydrogenated per liter of catalyst per hour.
  • a small change, if appropriate during the process according to the invention, of the proportion of desired product obtained by an optionally changing activity of the catalyst over particularly long reaction periods can be compensated for by a slight adjustment of the reaction temperature or of the other parameters.
  • the optionally changing proportions of the desired product can be monitored by the analysis of the reaction mixture. This analysis can be carried out by methods known to those skilled in the art, for example gas chromatography (GC).
  • GC gas chromatography
  • the process according to the invention can generally be carried out until a suitable conversion has been achieved. If the process according to the invention is carried out continuously, the reaction time corresponds to the residence time of the reaction mixture in the continuously operated reactor. According to the invention, the reaction time is preferably 10 to 400 minutes.
  • the present invention therefore preferably relates to the process according to the invention, wherein the reaction time is 10 to 400 min.
  • the hydrogenation mixtures obtained according to the invention can be purified by the process according to the invention, for example by distillation.
  • Optionally present in the reaction effluent catalyst can be removed prior to distillation, for example by a solid-liquid T rennung, such as filtration, sedimentation or centrifugation. Solvent and unreacted starting materials can be recycled to the process.
  • the products desired according to the invention are obtained after successful workup, for example by distillation, in a purity of at least 99% by weight. In general, these compounds can be used in this purity for all further processing processes.
  • the process according to the invention it is possible to obtain the desired product with a small proportion of the trans, trans isomer.
  • the desired isomer distribution is achieved by the hydrogenation per se, and that the isomer distribution does not have to be changed in an optional work-up by distillation to separate off solvent, unreacted educt and optionally formed by-products.
  • the present invention also relates to the use of a catalyst comprising ruthenium on a zirconia support material for the hydrogenation of 4,4'-methylenedianiline (MDA) to a mixture containing the isomers of 4,4'-diaminodicyclohexylmethane, the trans, trans isomer in an amount of 10 to 30 wt .-%, preferably 10 to 26 wt .-%, the cis, trans isomer in an amount of 30 to 55 wt .-%, preferably 40 to 55 wt .-%, and cis, cis-isomer in an amount of 10 to 50 wt .-%, preferably 25 to 40 wt .-%, each based on the total amount of all present isomers, is present ,, wherein the sum of the present isomers each 100 wt.
  • MDA 4,4'-methylenedianiline
  • the trans, trans isomer in an amount of 10 to 30 wt .-%, preferably 10 to 26 wt .-%
  • the cis, trans isomer in e iner amount of 30 to 55 wt .-%, preferably 40 to 55 wt .-%
  • the cis, cis isomer in an amount of 10 to 50 wt .-%, preferably 25 to 40 wt .-%, each based to the total amount of all isomers present, the sum of the present isomers in each case 100 wt .-% results.
  • the present invention relates to the use of a catalyst comprising ruthenium on a zirconium oxide support material for the hydrogenation of 4,4'-methylenedianiline (MDA) to a mixture containing the isomers of 4,4'-diaminodicyclohexylmethane and / or of polymer MDA corresponding oligomeric or polymeric, ring-hydrogenated compounds having a melting point of less than 40 ° C, preferably less than 30 ° C, more preferably less than 22 ° C.
  • a preferred lower limit for the melting point is 0 ° C.
  • the cycloaliphatic amines obtainable by the process according to the invention can be used as synthesis components for the preparation of surfactants, pharmaceutical and plant protection agents, stabilizers, light stabilizers, polymers, polyamides, isocyanates, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, Synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators, emulsifiers and / or be used as starting substances for the production of ureas and polyureas.
  • the hydrogenation products of bis (4-aminophenyl) methane (MDA) can be used as a monomer for polyamides.
  • MDA bis (4-aminophenyl) methane
  • the present invention therefore furthermore also relates to the use of a mixture comprising the isomers of 4,4'-diaminodicyclohexylmethane, where the trans, trans isomer is present in an amount of 10 to 30% by weight, preferably 10 to 26% by weight.
  • the cis, trans isomer in an amount of 30 to 55% by weight, preferably 40 to 55% by weight
  • the cis, cis isomer in an amount of 10 to 50% by weight, preferably 25 to 40 wt .-%, in each case based on the total amount of all present isomers, are present, the sum of the present isomers always 100 wt .-% results, as synthesis blocks for the production of surfactants, pharmaceutical and plant protection agents, stabilizers, sunscreens , Polymers, polyamides, isocyanates, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators, emulsifier ores and / or as starting substances for the production of ureas and polyureas.
  • the extrudates are dried at 120 ° C for 16 h in a convection oven and then calcined in a muffle furnace for 2 h at 180 ° C.
  • the catalyst is then first reduced for 2 h at 200 ° C. (4 l / h of H 2 ; 40 l / h of N 2 ) and with a mixture of 10% by volume of air and 90% by volume of N 2 for 1 h at room temperature passivated.
  • the active composition thus prepared contains 1% by weight of Ru and 99% by weight of zirconium oxide.
  • the powder is then dried at 120 ° C in a convection oven for 16 h and calcined for 2 h at 200 ° C under air. Then the powder in the rotary kiln is first purged with 40 l / h of N 2 for 20 min and then reduced within 90 min (3 l / h of hydrogen and 53 l / h of nitrogen). After cooling to room temperature, the hydrogen is turned off and rinsed with about 60 l / h of nitrogen. For passivation, initially 60 l / h of nitrogen and 1 l / h of air are added and then the amount of air is slowly increased to 10 l / h (oil / h of nitrogen). Care must be taken that the catalyst does not heat above 35 ° C.
  • the active composition thus prepared contains 10 wt .-% Ru and 90 wt .-% ZrÜ2.
  • the catalyst produced in this way has the following characteristics: tamped density is 1.13 kg / L, the pore volume (Hg porosimetry) is 0.32 mL / g, the BET surface area is 75 m 2 / g, the pore distribution is as follows: 0% mesopores (2-50 nm), 100% macropores (> 50 nm).
  • Example 1 Suspension procedure, testing of different catalysts A defined amount of the catalyst (150 mg) was introduced into a 10 ml autoclave with 7 ml of a 9% strength by weight solution of 4,4'-methylenedianiline (MDA) in dioxane given. The reaction mixture is then heated under 140 bar hydrogen pressure with stirring to the appropriate reaction temperature and over 180 minutes constant held. Thereafter, the solution is cooled to room temperature and the autoclave is vented to atmospheric pressure. The analysis of the reaction mixture by GC chromatography, the method is given below. The results are shown in Table 1.
  • MDA 4,4'-methylenedianiline
  • the preparation of the catalysts was carried out analogously to the preparation of the catalyst according to the invention using appropriate metal salts / carrier.
  • Example 2 Suspension procedure, testing of different ZrO 2 carrier materials
  • a defined amount of the catalyst (10% Ru on ZrO 2 , 150 mg) was mixed with 7 ml of a 9% strength by weight solution of 4,4'-methylenedianiline (MDA) in Dioxane in an autoclave with a volume of 10 ml.
  • MDA 4,4'-methylenedianiline
  • the reaction mixture is then heated under 140 bar hydrogen pressure with stirring to 120 ° C and kept constant over 180 minutes. Thereafter, the solution is cooled to room temperature and the autoclave is vented to atmospheric pressure.
  • the analysis of the reaction mixture by GC chromatography, the method is given below. The results are shown in Table 2.
  • the preparation of the catalysts was carried out analogously to the preparation of the catalyst according to the invention using appropriate carriers. Table 2
  • the examples show that a low BET surface area leads to a decrease in selectivity and conversion and that a high BET surface area is advantageous.
  • PACM means 4,4'-diaminodicyclohexylmethane
  • Table 3 show that at a reaction temperature of 120 ° C, the product PACM is obtained with the aid of the catalyst according to the invention in the isomer ratio according to the invention. From 140 ° C., the isomer ratio of the product changes in such a way that the proportion of the trans, trans isomer increases significantly.
  • PACM means 4,4'-diaminodicyclohexylmethane
  • Example 4 Driving in a fixed bed
  • PACM means 4,4'-diaminodicyclohexylmethane
  • Example 5 Driving in a fixed bed
  • PACM means 4,4'-diaminodicyclohexylmethane Analysis by gas chromatography:

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Abstract

La présente invention concerne un procédé d'hydrogénation de 4,4'‑méthylènedianiline et/ou de MDA polymère avec de l'hydrogène en présence d'un catalyseur qui contient du ruthénium sur un matériau support à base d'oxyde de zirconium. L'invention concerne en outre l'utilisation d'un catalyseur contenant du ruthénium sur un matériau support à base d'oxyde de zirconium pour hydrogéner de la 4,4'‑méthylènedianiline et/ou de la MDA polymère.
EP14809408.9A 2013-12-11 2014-12-10 Procédé d'hydrogénation de 4,4'-méthylènedianiline Withdrawn EP3080081A1 (fr)

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EP13196584.0A EP2883863B1 (fr) 2013-12-11 2013-12-11 Procédé de preparation de 4,4'-dimethylaniline
PCT/EP2014/077120 WO2015086638A1 (fr) 2013-12-11 2014-12-10 Procédé d'hydrogénation de 4,4'-méthylènedianiline
EP14809408.9A EP3080081A1 (fr) 2013-12-11 2014-12-10 Procédé d'hydrogénation de 4,4'-méthylènedianiline

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CN108440311B (zh) * 2018-03-29 2020-11-20 万华化学集团股份有限公司 一种加氢制备二氨基二环己基甲烷的方法
CN109535007A (zh) * 2018-11-07 2019-03-29 万华化学集团股份有限公司 一种二氨基二环己基甲烷同分异构体分离方法
CN109851508B (zh) * 2018-12-25 2022-01-07 万华化学集团股份有限公司 合成低反反异构体含量和低焦油含量h12mda的方法
US11964259B2 (en) 2019-12-31 2024-04-23 Industrial Technology Research Institute Catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives and method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives using the same

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DE2132547C2 (de) * 1971-06-30 1982-11-11 Basf Ag, 6700 Ludwigshafen Verfahren zur Hydrierung ein- oder mehrkerniger aromatischer Diamine zu den entsprechenden cycloaliphatischen Aminen
US4448995A (en) 1982-12-13 1984-05-15 Mobay Chemical Corporation Catalytic hydrogenation of di(4-aminophenyl)methane
DE19533718A1 (de) 1995-09-12 1997-03-13 Basf Ag Verfahren zur Hydrierung von aromatischen Verbindungen, in denen mindestens eine Aminogruppe an einen aromatischen Kern gebunden ist
EP1106600B1 (fr) 1999-12-06 2004-08-04 Basf Aktiengesellschaft Procédé pour la préparation d'amines
DE10054347A1 (de) 2000-11-02 2002-05-08 Degussa Verfahren zur katalytischen Hydrierung organischer Verbindungen und Trägerkatalysatoren hierfür
EP1366812B1 (fr) 2002-05-31 2009-02-18 Evonik Degussa GmbH Catalyseur supporté à base de ruthenium et procédé d'hydrogénation d'amines aromatiques en présence de tel catalyseur
DE10261193A1 (de) * 2002-12-20 2004-07-01 Basf Ag Verfahren zur Herstellung eines Armins
JP5044649B2 (ja) 2006-07-31 2012-10-10 ビーエーエスエフ ソシエタス・ヨーロピア フタレートを環水素化するためのルテニウム触媒を再生する方法
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WO2009090179A2 (fr) * 2008-01-18 2009-07-23 Basf Se Procédé pour produire des amines cycloaliphatiques
WO2009153123A1 (fr) * 2008-05-27 2009-12-23 Basf Se Procédé continu et réacteur d'hydrogénation de composés organiques
CN102549262B (zh) * 2009-07-09 2014-12-24 巴斯夫欧洲公司 传送流体的方法
CN102093227B (zh) * 2011-01-07 2013-08-07 烟台万华聚氨酯股份有限公司 生产低的反-反异构体含量的4,4’-二氨基二环己基甲烷的方法

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WO2015086638A1 (fr) 2015-06-18
KR20160097259A (ko) 2016-08-17
JP2017504588A (ja) 2017-02-09
HUE035346T2 (en) 2018-05-02
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CN106029638A (zh) 2016-10-12

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