WO2012152821A1 - Catalyseurs pour l'hydrogénation d'amine aromatique - Google Patents

Catalyseurs pour l'hydrogénation d'amine aromatique Download PDF

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WO2012152821A1
WO2012152821A1 PCT/EP2012/058521 EP2012058521W WO2012152821A1 WO 2012152821 A1 WO2012152821 A1 WO 2012152821A1 EP 2012058521 W EP2012058521 W EP 2012058521W WO 2012152821 A1 WO2012152821 A1 WO 2012152821A1
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catalyst
preparation
range
catalysts
hydrogenation
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PCT/EP2012/058521
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German (de)
English (en)
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Lucia KÖNIGSMANN
Thomas Heidemann
Martin Bock
Joachim Pfeffinger
Benjamin Koch
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Basf Se
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • 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
    • 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 Ru-containing catalyst, and a process for its preparation, which includes the steps impregnation, drying, calcination and reduction.
  • the present application relates to a process for the hydrogenation of organic substances in the presence of catalysts according to the invention or prepared according to the invention, and to a process for the preparation of secondary products of cycloaliphatic amines prepared according to the invention.
  • the hydrogenation of aromatic compounds is often carried out in the presence of catalysts containing ruthenium as the active metal.
  • Ru can be used in the form of supported or unsupported catalysts.
  • DE-OS-2132547 describes a process for the hydrogenation of aromatic compounds to give the corresponding cycloaliphatic compounds.
  • an unsupported catalyst based on oxide hydrates of Ru is used for hydrogenation.
  • the catalyst is prepared by precipitation from an aqueous solution of a Ru salt by addition of alkali metal hydroxide.
  • the Ru oxide hydrate thus obtained can be used directly in the process or subjected to drying before use.
  • the catalyst is present as a powder having particle sizes in the range from 4 to 6 nm, the Ru being present in the obtained dry powder as ruthenium (IV) oxide hydrate with about 50% by weight of Ru.
  • No. 3,864,361 describes the preparation of 2,5-dimethlypyrrolidone by reduction of 2,5-dimethylpyrrole in the presence of finely divided, unsupported RuU.sub.2.
  • the catalyst is removed after completion of the hydrogenation by filtration.
  • the separation of the Ru catalyst can be improved by the addition of Al2O3 as a filter aid.
  • WO 2009/090179 discloses the hydrogenation of aromatic amines in the presence of unsupported Ru catalysts to which an inorganic additive is added during the reaction in order to reduce the agglomeration tendency of the catalysts.
  • Supported Ru catalysts are disclosed, for example, in US Pat. No. 5,981,801, EP 1366812, EP 0813906, EP 0814098 or DE 101 28 242.
  • US 5,981,801 describes supported Ru catalysts on activated carbon, calcium carbonate, ceria, alumina, zirconia, titania or silica. To increase the reaction rate and to reduce side reactions, the catalyst is pretreated before use in the reaction with oxygen.
  • EP 1366812 discloses a process for the hydrogenation of an aromatic amine, for example methylenedianiline (MDA), in the presence of a supported Ru catalyst.
  • MDA methylenedianiline
  • the carrier material is called S1O2.
  • the support material according to the invention has a BET surface area of 30 m 2 / g to 70 m 2 / g.
  • EP 0813905 likewise describes the hydrogenation of aromatic amines in the presence of supported Ru catalysts.
  • carrier uaSi02 is called.
  • the BET surface area is only a maximum of 30 m 2 / g.
  • the hydrogenation of aromatic amines is also disclosed in EP 0814098.
  • active metal Ru can be used alone or together with other active metals.
  • the support material for example S1O2, has a BET surface area of 50 to 500 m 2 / g, preferably 200 to 350 m 2 / g.
  • the hydrogenation of organic compounds is carried out in the presence of a catalyst containing as active metal Ru alone or together with other active metals, wherein the active metals are applied to a support material based on amorphous silicon dioxide.
  • Ru is applied to the support in the form of an aqueous solution of a halogen-free Ru compound, in particular Ru nitrosyl nitrate, and the solid thus obtained is subsequently dried at a temperature below 200 ° C. and subsequently reduced.
  • the object of the present invention was to provide improved catalysts for the hydrogenation of aromatic compounds.
  • catalysts should be provided which have high activity.
  • Another object of the present invention was to provide calcined catalysts or catalyst precursors which have only a low heat of reaction during the reduction. This allows a safe implementation of the reduction and allows the production of Ru catalysts with a high Ru dispersity and high activity.
  • the object of the present invention was achieved by a
  • the catalysts used in the process for the hydrogenation of aromatic compounds contain Ru.
  • the catalyst may optionally contain at least one further metal of the I, VII or VIII subgroup of the periodic table.
  • the catalyst preferably contains, as further metal, the group I, VII or VIII of the Periodic Table Pd or Pt.
  • the molar ratio of Ru to the other metals of the I, VII or VIII subgroup of the Periodic Table is 100: 0 to 100: 20, more preferably 100: 0 to 100: 10, most preferably 100: 0.0001 to 100: 5, and more preferably 100: 0.001 to 100: 1.
  • ruthenium is used alone as the active metal.
  • the catalysts used in the process of hydrogenating aromatic compounds further contain a support material containing silica (S1O2).
  • Support materials based on silicon dioxide are familiar to the person skilled in the art and are commercially available (see, for example, OW Flörke, "Silica” in Ullmann's Encyclopaedia of Industrial Chemistry, 5th ed., On CD-ROM) They may have been both of natural origin and artificially produced.
  • Examples of support materials based on silica are kieselguhr, silica gels, fumed silica and precipitated silica.
  • the catalysts contain silica gels as support materials.
  • the support material may optionally contain other support materials, such as Al 2 O 3, MgO, CaO, TIO 2, ZrC 2, Fe 2 O 3 or alkali metal oxide.
  • the proportion of S1O2 on the carrier material is preferably in the range from 75 to 100% by weight, particularly preferably in the range from 90 to 100% by weight, very particularly preferably in the range from 95 to 99.9% by weight and particularly preferably 99 to 99.8% by weight. Based on the carrier material used.
  • S1O2 is the sole carrier material.
  • pulverulent carrier material is used in the process according to the invention for the hydrogenation of aromatic compounds.
  • the support material used preferably has an average particle size distribution (PGV) of 0.1 to 1000 ⁇ , more preferably 1 to 500 ⁇ and particularly preferably 2 to 200 ⁇ on.
  • PSV average particle size distribution
  • the average particle diameter d 50 is preferably in the range from 1 to 50 ⁇ m, particularly preferably in the range from 5 to 40 ⁇ m, and very particularly preferably in the range from 10 to 30 ⁇ m.
  • the determination of the PGV takes place by means of laser diffraction according to ISO 13320.
  • the support materials preferably have a mercury porosity (DIN 66133) in the range from 0.5 to 500 ml / g, particularly preferably 1 to 300 ml / g and very particularly preferably 1.5 to 200 ml / g.
  • the average pore diameter is preferably in the range from 10 to 200 nm, particularly preferably in the range from 20 to 100 nm and very particularly preferably in the range from 25 to 50 nm.
  • the surface of the carrier material is preferably from 50 to 500 m 2 / g, more preferably 100 to 350 m 2 / g and in particular 100 to 250 m 2 / g of the carrier.
  • the surface of the support is determined by the BET method by N 2 adsorption, in particular according to DIN 66131.
  • the average pore diameter and the size distribution are determined by Hg porosymmetry, in particular according to DIN 66133.
  • the support material can be used in the form of shaped bodies in the process according to the invention, which are obtainable, for example, by extrusion, extrusion or tableting and which, for example, take the form of spheres, tablets, cylinders, strands, rings or hollow cylinders. Stars and the like may have.
  • the dimensions of these shaped bodies preferably range from 1 mm to 25 mm. Catalyst strands with strand diameters of 2 to 5 mm and strand lengths of 2 to 25 mm are also preferably used.
  • the catalysts used in the process according to the invention can be obtained by a) one or more treatment of the support material with an aqueous solution of Ru-nitrosyl nitrate and drying of the treated support material at a temperature below 250 ° C, then b) treatment of the treated in step a) support material with an oxygen-containing gas (calcination) in a temperature range from 100 to 250 ° C, and then c) reducing the catalyst precursor obtained in step b) with hydrogen at a temperature in the range of 100 to 250 ° C.
  • the support material is first treated with an aqueous solution of Ru-nitrosyl nitrate in such a way that the desired amount of ruthenium is taken up by the support material. This step will also be referred to as potions.
  • the treatment or impregnation of the carrier material can take place in different ways. For example, spray or rinse the support material with the Ru-nitrosyl nitrate solution or suspend the support material in the Ru-nitrosyl nitrate solution. For example, it is possible to suspend the support material in the aqueous solution of Ru-nitrosyl nitrate and to filter off the aqueous supernatant after a certain time. On the amount of liquid absorbed and the ruthenium concentration of the solution then the ruthenium content of the catalyst can be controlled in a simple manner.
  • the impregnation of the carrier material can also be carried out, for example, by treating the carrier with a defined amount of the aqueous solution of Ru-nitrosyl nitrate, which corresponds to the maximum amount of liquid that can absorb the carrier material.
  • aqueous solution of Ru-nitrosyl nitrate which corresponds to the maximum amount of liquid that can absorb the carrier material.
  • Suitable apparatuses for this purpose are those commonly used for mixing liquids and solids (see, for example, Vauck, Müller “Grundoperationen chemischermaschinestechnik", 10th edition, Deutscher Verlag for the plastics industry, Leipzig, 1994, p. 405ff.), For example suitable tumble dryers, Tumbling drums, drum mixers, paddle mixers and the like.
  • Monolithic carriers are usually rinsed with the aqueous solutions of Ru-nitrosyl nitrate.
  • aqueous here denotes water and mixtures of water with up to 50% by volume, preferably not more than 30% by volume and in particular not more than 10% by volume of one or more water-miscible organic solvents, eg Mixtures of water with C 1 -C 4 alkanols such as methanol, ethanol, n- or isopropanol Frequently, water is used as the sole solvent
  • the aqueous solvent is frequently also used, for example, as a halogen-free acid, for example nitric acid, sulfuric acid or acetic acid, to stabilize the Ru
  • concentration of Ru-nitrosyl nitrate in the aqueous solutions naturally depends on the amount of Ru Nitrosylnitrats and the absorption capacity of the carrier material for the aqueous solution and is usually in the range of 0.1 to 20 wt .-%.
  • the treated support material After the treatment of the support material with the aqueous Ru-nitrosyl nitrate solution, the treated support material is usually separated from supernatant liquid and dried.
  • the drying takes place in the temperature range of less than 250 ° C, more preferably less than 200 ° C and most preferably less than 150 ° C.
  • drying in the temperature range from 100 to 150 ° C., in particular preferably in the range from 110 to 130 ° C.
  • the drying of the treated with the Ru-nitrosyl nitrate carrier material is usually carried out under atmospheric pressure and to promote the drying, a reduced pressure can be applied. Frequently, to promote drying, a gas stream will be passed over or through the material to be dried, e.g. Air or nitrogen.
  • the drying time naturally depends on the desired degree of drying and the drying temperature and is usually in the range of 2 hours to 30 hours, preferably in the range of 4 to 15 hours.
  • the drying of the treated support material is performed so far that the content of water or of volatile solvent constituents prior to reduction ii) less than 5 wt .-% and in particular not more than 2 wt .-%, particularly preferably not more than 1 wt .-%, based on the total weight of the solid.
  • the stated proportions by weight relate to the weight loss of the solid, determined at a temperature of 300 ° C a pressure of 1 bar and a duration of 10 min.
  • the drying is preferably carried out by moving the support material treated with the Ru-nitrosyl nitrate solution, for example by drying the solid in a rotary kiln or a rotary kiln. In this way, the activity of the catalysts according to the invention can be further increased.
  • the treatment of the carrier material with an aqueous solution of Ru-nitrosyl nitrate and the subsequent drying can be repeated if larger amounts of Ru are to be applied to the carrier material.
  • the treated catalyst support according to the invention is brought into contact with an oxygen-containing gas (calcination).
  • the oxygen content of the oxygen-containing gas is preferably 0.1 to 25% by volume, more preferably 0.5 to 21% by volume and most preferably 2 to 5% by volume.
  • Particular preference is given to using air as the oxygen-containing gas.
  • mixtures of oxygen, inert gases (eg nitrogen or argon), hydrogen oxide (water vapor) and / or air can be used.
  • the temperature in the calcination is in the range of 100 to 250 ° C, more preferably in the range of 150 to 250 ° C and most preferably in the range of 150 to 180 ° C.
  • the duration of the calcination is preferably 0.5 to 10 hours, more preferably 1 to 5 hours, and most preferably 2 to 4 hours.
  • the calcination can be carried out batchwise, for example in a shaft furnace, tray furnace, muffle furnace, heating cabinet or in a fluidized bed reactor or continuously, for example in a rotary kiln, belt calcination furnace or rotary kiln.
  • a so-called catalyst precursor is generally present in which Ru is present at least partially in the form of its oxygen-containing compounds, in particular as oxides, hydroxides and / or hydrated oxides.
  • ruthenium after calcination, 50 mol% or more, more preferably 75 mol% or more, and most preferably 90 mol% or more of ruthenium is in the form of its oxygen-containing compounds.
  • the Ru after calcination is substantially completely in the form of its oxygen-containing compounds.
  • the catalyst precursor preferably has, after the last drying or calcining step, a nitrogen content in the range from 1.0 to 3 wt.%, Preferably 1.2 to 2.5 wt.% And very particularly preferably 1.3 to 2 wt. %, based on the catalyst precursor.
  • the determination of the nitrogen content is carried out according to DIN 51732.
  • the catalyst precursor After the last drying or calcining step, the catalyst precursor has a water content of preferably less than 1% by weight, more preferably less than 0.1% by weight, and most preferably less than 0.01% by weight.
  • the conversion of the catalyst precursor into its catalytically active form takes place by reduction of the catalyst precursor.
  • the treated and calcined carrier material is brought with hydrogen or a mixture of hydrogen and an inert gas.
  • the hydrogen partial pressure is preferably in the range of 0.2 bar to 1, 5 bar.
  • the reduction of the catalyst precursor preferably takes place at normal hydrogen pressure in the hydrogen stream.
  • the reduction is carried out by moving the catalyst precursor, for example, by reducing the catalyst precursor in a rotary kiln or rotary kiln. In this way, the activity of the catalysts according to the invention can be further increased.
  • the reduction is carried out at a temperature in the range of 100 to 250 ° C, preferably in the range of 150 to 230 ° C and more preferably in the range of 180 to 220 ° C.
  • the content of ruthenium of the reduced catalyst is preferably 4% by weight or more, more preferably 6% by weight or more, still more preferably 7% by weight or more, and particularly preferably 8% by weight or more.
  • the proportion of Ru is preferably in the range of 4 to 30 wt .-%, particularly preferably 4 to 20 wt .-%, most preferably 6 to 15 wt .-% and in particular 7 to 12 wt .-% based on the total weight of the reduced catalyst.
  • ruthenium atoms In the reduced catalyst, 95 mol% or more, particularly preferably 98 mol% or more, very particularly preferably 99 mol% or more of the ruthenium atoms have an oxidation number of 0. In a particularly preferred embodiment, essentially all ruthenium atoms have the oxidation number O.
  • the catalyst according to the invention preferably has a Ru dispersity (measured according to DIN 66136) in the range from 5 to 50%, particularly preferably 10 to 30% and very particularly preferably 15 to 25%.
  • the resulting catalyst can be passivated to improve handleability, e.g. by briefly charging the catalyst with an oxygen-containing gas, e.g. Air, but preferably treated with an inert gas mixture containing 1 to 10 vol .-% oxygen.
  • an oxygen-containing gas e.g. Air
  • an inert gas mixture containing 1 to 10 vol .-% oxygen.
  • Aromatic compounds which can be hydrogenated to cycloaliphatic amines are used in the process according to the invention.
  • Aromatic compounds that can be hydrogenated to cycloaliphatic amines are usually mono- or polynuclear aromatic compounds containing one or more nitrogen-containing substituents.
  • aromatic compounds having one or more nitrogen-containing substituents are used in which the nitrogen atom of the nitrogen-containing tigen substituent is attached directly to the aromatic rings (N-substituted aromatic compounds).
  • aromatic mono-, di- or polyamines are used, which can be hydrogenated to the corresponding cycloaliphatic amines.
  • Suitable aromatic amines are mono- or polynuclear aromatic compounds having one or more amine groups, for example: aromatic monoamines, such as aniline, the isomeric toluidines, the isomeric xylidines,
  • aromatic diamines such as the isomeric phenylenediamines, the isomeric tolylenediamines, the isomeric diaminonaphthalenes, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3 ', 5,5'-tetramethyl diphenylmethane and
  • aromatic polyamines such as polymer MDA (polymethylene-polyphenyl-amine).
  • aromatic compounds which can be hydrogenated to cycloaliphatic amines it is also possible to use aromatics having nitro, nitrile and urethane groups as substituents on the aromatic ring,
  • aromatic compounds having nitro groups as substituents such as nitrobenzene, nitrotoluene, di-nitrobenzene, dinitrotoluene and the isomeric nitroanilines; aromatic compounds with nitrile groups as Substiutenten, such as benzonitrile, toluonitrile or. o-aminobenzonitrile; or aromatic compounds having urethane groups as substituents, such as
  • dialkyl urethanes consisting of 4,4'-methylene diphenyl diisocyanate, 2,4'-methylene diphenyl diisocyanate or 2,2'-methylene diphenyl diisocyanate and aliphatic alcohols, such as C1-C6 alcohols, in particular n -Butanol are formed,
  • dialkylurethanes which are formed from tolylene-2,4-diisocyanate or tolylene-2,6-diisocyanate and aliphatic alcohols, such as C 1 -C 6 -alcohols, in particular n-butanol,
  • dialkylurethanes which are formed from polymeric diphenylmethane diisocyanate and aliphatic alcohols, such as C 1 -C 6 -alcohols, in particular n-butanol,
  • dialkylurethanes which are formed from 2,4-phenylenediisocyanate or 2,6-phenylenediisocyanate and aliphatic alcohols, such as C 1 -C 6 -alcohols, in particular n-butanol, or the dialkylurethanes which consist of 1, 5-naphthylenediidocyanate and aliphatic alcohols, such as C1-C6 alcohols, in particular n-butanol are formed.
  • the aromatic compounds may have no further substituents in addition to the substituents which can be hydrogenated to amine groups, or they may bear one or more further substituents, for example alkyl, cycloalkyl, aryl, heteroaryl, halogen, haloalkyl, silyl , Hydroxy, alkoxy, aryloxy, carboxy or alkoxycarbonyl substituents.
  • Aromatic amines such as the abovementioned aromatic mono-, di- and / or polyamines, are preferably used in the process. Particularly preferred is polymer MDA, aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4 , 4'-diamino-3,3 ', 5,5'-tetramethyl-diphenylmethane and / or 4,4'-diaminodiphenylmethane used in the process.
  • polymer MDA aniline
  • 2,4-diaminotoluene 2,6-diaminotoluene
  • o-phenylenediamine m-phenylenediamine
  • p-phenylenediamine 4,4
  • aromatic compounds which can be hydrogenated to the corresponding cycloaliphatic amines are used which contain by-products.
  • by-products are examples of such by-products.
  • Hydrochlorides of the aromatic starting amines or higher boiling aromatic by-products are those components which have a higher boiling point than the aromatic starting compounds to be hydrogenated to the cycloaliphatic products.
  • the chlorine content of the aromatic compounds which can be hydrogenated to the corresponding cycloaliphatic amines is preferably 1 ppm or more, preferably 10 ppm to 10,000 ppm and more preferably 20 ppm to 1000 ppm, the chlorine content usually being according to DIN V 51408 Part 2 is determined.
  • the content of higher-boiling aromatic compounds in the starting compounds is generally 1 wt .-% and more, preferably 2 to 20 wt .-% and particularly preferably 2 to 10 wt .-%, wherein the content of higher-boiling aromatic compounds by Laboratory distillation according to ASTM D 5236-03 at a pressure of 1 mbar and a temperature up to 260 ° C is determined.
  • a hydrogen-containing gas is used.
  • the hydrogen is generally used technically pure.
  • the hydrogen can also be used in the form of a hydrogen-containing gas, ie in admixtures with other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide.
  • reformer effluents, refinery gases, etc. may be used as the hydrogen-containing gases if and as far as these gases do not contain contact poisons for the Ru-containing catalysts such as CO.
  • the preparation of the aromatic amines is carried out in the presence of the Ru-containing catalysts according to the invention described above.
  • the hydrogenation can be carried out batchwise or continuously.
  • 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 reactor with pumped circulation.
  • 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 reactor with pumped circulation or a stirred tank cascade.
  • the process according to the invention is generally carried out at a pressure of 50-350 bar, preferably a pressure of 150 to 250 bar is used.
  • the process is carried out at a temperature in the range between 30 and 280 ° C, wherein the temperature range of 120 to 260 ° C is particularly preferred.
  • the hydrogenation can be carried out with or without solvent.
  • the solvents used are alcohols, such as isopropanol, isobutanol or t-butanol, or ethers, such as diethyl ether, glycol dimethyl ether, dioxane or tetrahydrofuran.
  • Suitable solvents are also mixtures of the abovementioned solvents.
  • Preferred solvents are isopropanol, isobutanol and / or t-butanol. Particular preference is given to using the final product formed during the reaction as the solvent.
  • the solvent is usually used in such an amount as to obtain 10 to 50% (wt.%), Preferably 15 to 40%, particularly preferably 20 to 30%, solutions of the aromatic compounds intended for hydrogenation.
  • Particularly advantageous for the continuous implementation of the method is to use the resulting end product in the reaction as a solvent.
  • the Ru-containing catalyst is preferably used as a suspension of the catalyst in the liquid starting materials or solvents used.
  • the Ru catalyst is usually added directly into the hydrogenation reactor, either as a dry powder or as a water-moist filter cake.
  • the Ru catalyst is mixed with a solvent, the liquid starting material or liquid reaction discharge to form a suspension, which is then mixed by means of suitable metering pumps can be supplied to the reactor.
  • this catalyst suspension is usually fed continuously to the hydrogenation reactor.
  • the reaction mixture from the hydrogenation is usually purified.
  • the purification of the reaction mixture is usually carried out by rectification or distillation.
  • the inorganic additive and the heterogeneous Ru-containing catalyst can be removed before the distillation, for example by a solid-liquid T, such as filtration, sedimentation or centrifugation.
  • Solvent and unreacted starting materials can be recycled to the process.
  • cycloaliphatic amines obtainable by the process according to the invention can be used as synthesis building block for the preparation of surfactants, pharmaceutical and plant protection agents, stabilizers, light stabilizers, polymers, 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 materials for the production of ureas and polyureas are particularly useful as starting materials for the production of ureas and polyureas.
  • cyclohexylamine obtainable by the hydrogenation of aniline, can be used as a corrosion inhibitor or vulcanization accelerator.
  • the present invention also relates to a process for the preparation of surfactants, pharmaceutical and plant protection agents, stabilizers, light stabilizers, polymers, 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 as starting materials for the production of ureas and polyureas, characterized in that in a first stage cycloaliphatic amines are prepared by a Vefahren according to claim 8, and obtained in the first stage cycloaliphatic amines for the preparation of surfactants, pharmaceutical and pesticides, stabilizers, light stabilizers, polymers, isocyanates, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, W oak, corrosion inhibitors, synthetic resins, i
  • the present invention it has been possible to provide catalysts for the hydrogenation of aromatic compounds which have a high activity.
  • the reduction of the catalyst precursor according to the invention to the actual catalyst only a small evolution of heat is formed. This makes it possible to safely carry out the reduction of the catalyst precursor.
  • the catalyst precursors according to the invention have a high rutile dispersancy and enable the preparation of catalysts with high activity.
  • the process according to the invention generally has a high space-time yield.
  • the method usually ensures a stable operation.
  • the supported catalysts can be separated from the reaction mixture and reused in the process.
  • Ru-nitrosylnitrate solution 107.87 g Ru-nitrosylnitrate solution were diluted with distilled H2O in a graduated cylinder to 1 16 ml volume of solution. 100 g of carrier (Sipernat D120 from Evonik) were placed in a trough drum, then the impregnating solution was quartered and added to the carrier. After impregnation was dried at 120 ° C for 16h. After drying, the catalyst contained 3.2% N.
  • the catalyst was calcined at 180 ° C for 3 h. Elemental analysis of the calcined catalyst precursor revealed an N content of 1.5%.
  • the catalyst precursor was reduced and passivated.
  • the impregnation process and drying were carried out analogously to regulation 1 .1.
  • the catalyst was calcined at 300 ° C. for 3 h (elemental analysis N content ⁇ 0.5%). Subsequently, the calcined catalyst precursor was reduced and passivated.
  • the properties of the catalysts are shown in Table 1. Ru dispersity, Ru surface area, pore volume, BET surface area, Ru content, and Ru crystallite size were measured after reduction. Only the N content was determined before the reduction, after the last drying or calcination step.
  • the catalyst was prepared analogously to the procedure described for DE10128242 for "catalyst A.” After drying, the IS content was 0.9%.
  • the catalyst was run as described in experiment 2.1 .1.

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  • Materials Engineering (AREA)
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Abstract

L'invention concerne un catalyseur renfermant 4% en poids de ruthénium (Ru) ou plus, et un matériau support renfermant du dioxyde de silicium, caractérisé en ce que la teneur en azote du catalyseur, après son dernier séchage ou calcination, se situe dans une plage de 1 à 3% en poids, ainsi que son précurseur de catalyseur. L'invention a également pour objet un procédé de production d'un catalyseur au ruthénium, comprenant les étapes suivantes : imprégnation, séchage, calcination et réduction. L'invention concerne en outre un procédé d'hydrogénation de substances organiques, en présence de catalyseurs selon l'invention ou de catalyseurs produits conformément à l'invention, ainsi qu'un procédé de production de produits dérivés, à partir d'amines cycloaliphatiques produites conformément à l'invention.
PCT/EP2012/058521 2011-05-11 2012-05-09 Catalyseurs pour l'hydrogénation d'amine aromatique WO2012152821A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015057313A1 (fr) * 2013-10-18 2015-04-23 Exxonmobil Chemical Patents Inc. Catalyseur d'hydrogénation, son procédé de préparation et son utilisation

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2132547A1 (de) 1971-06-30 1973-01-18 Basf Ag Verfahren zur hydrierung aromatischer verbindungen zu den entsprechenden cycloaliphaten
US3864361A (en) 1973-02-15 1975-02-04 Diamond Shamrock Corp Stereospecific hydrogenation process using unsupported RuO{HD 2 {B catalyst
WO1993016971A1 (fr) * 1992-02-26 1993-09-02 Catalytica, Inc. Procede et catalyseur permettant d'hydrogener partiellement des composes aromatiques et produire des cyclo-olefines
EP0813905A2 (fr) 1996-06-19 1997-12-29 Haarmann & Reimer Gmbh Produit déshydratant contenant un parfum
EP0813906A2 (fr) 1996-06-19 1997-12-29 Basf Aktiengesellschaft Méthode de conversion d'un composé organique en présence d'un catalyseur à base de ruthénium
EP0814098A2 (fr) 1996-06-19 1997-12-29 Basf Aktiengesellschaft Procédé de conversion d'un composé organique en présence d'un catalyseur supporté en ruthénium
US5981801A (en) 1997-10-07 1999-11-09 Korea Institute Of Science And Technology Hydrogenation of aromatic diamines
DE10128242A1 (de) 2001-06-11 2002-12-12 Basf Ag Verfahren zur Hydrierung organischer Verbindungen
EP1366812A1 (fr) 2002-05-31 2003-12-03 Degussa AG Procédé d'hydrogénation d'amines aromatiques en présence de catalyseurs supportés à base de ruthenium
WO2004046076A2 (fr) * 2002-11-20 2004-06-03 Exxonmobil Research And Engineering Company Procedes d'hydrogenation
WO2004052813A1 (fr) * 2002-12-11 2004-06-24 Basf Aktiengesellschaft Prodede de production en continu d'alcools de sucre
WO2009090179A2 (fr) 2008-01-18 2009-07-23 Basf Se Procédé pour produire des amines cycloaliphatiques

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2132547A1 (de) 1971-06-30 1973-01-18 Basf Ag Verfahren zur hydrierung aromatischer verbindungen zu den entsprechenden cycloaliphaten
US3864361A (en) 1973-02-15 1975-02-04 Diamond Shamrock Corp Stereospecific hydrogenation process using unsupported RuO{HD 2 {B catalyst
WO1993016971A1 (fr) * 1992-02-26 1993-09-02 Catalytica, Inc. Procede et catalyseur permettant d'hydrogener partiellement des composes aromatiques et produire des cyclo-olefines
EP0813905A2 (fr) 1996-06-19 1997-12-29 Haarmann & Reimer Gmbh Produit déshydratant contenant un parfum
EP0813906A2 (fr) 1996-06-19 1997-12-29 Basf Aktiengesellschaft Méthode de conversion d'un composé organique en présence d'un catalyseur à base de ruthénium
EP0814098A2 (fr) 1996-06-19 1997-12-29 Basf Aktiengesellschaft Procédé de conversion d'un composé organique en présence d'un catalyseur supporté en ruthénium
US5981801A (en) 1997-10-07 1999-11-09 Korea Institute Of Science And Technology Hydrogenation of aromatic diamines
DE10128242A1 (de) 2001-06-11 2002-12-12 Basf Ag Verfahren zur Hydrierung organischer Verbindungen
EP1366812A1 (fr) 2002-05-31 2003-12-03 Degussa AG Procédé d'hydrogénation d'amines aromatiques en présence de catalyseurs supportés à base de ruthenium
WO2004046076A2 (fr) * 2002-11-20 2004-06-03 Exxonmobil Research And Engineering Company Procedes d'hydrogenation
WO2004052813A1 (fr) * 2002-12-11 2004-06-24 Basf Aktiengesellschaft Prodede de production en continu d'alcools de sucre
WO2009090179A2 (fr) 2008-01-18 2009-07-23 Basf Se Procédé pour produire des amines cycloaliphatiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VAUCK, MÜLLER: "Grundoperationen chemischer Verfahrenstechnik", 1994, DEUTSCHER VERLAG FÜR DIE KUNSTSTOFFINDUSTRIE, pages: 405

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015057313A1 (fr) * 2013-10-18 2015-04-23 Exxonmobil Chemical Patents Inc. Catalyseur d'hydrogénation, son procédé de préparation et son utilisation
US10130938B2 (en) 2013-10-18 2018-11-20 Exxonmobil Chemical Patents Inc. Hydrogenation catalyst, its method of preparation and use
US10518248B2 (en) 2013-10-18 2019-12-31 Exxonmobil Chemical Patents Inc. Hydrogenation catalyst, its method of preparation and use

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