EP2393591A2 - Catalyseurs d'hydrogénation, préparation et utilisation - Google Patents

Catalyseurs d'hydrogénation, préparation et utilisation

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Publication number
EP2393591A2
EP2393591A2 EP10701552A EP10701552A EP2393591A2 EP 2393591 A2 EP2393591 A2 EP 2393591A2 EP 10701552 A EP10701552 A EP 10701552A EP 10701552 A EP10701552 A EP 10701552A EP 2393591 A2 EP2393591 A2 EP 2393591A2
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EP
European Patent Office
Prior art keywords
catalyst
suspension
catalysts
compounds
hydrogenation
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.)
Withdrawn
Application number
EP10701552A
Other languages
German (de)
English (en)
Inventor
Christof Wilhelm Wigbers
Jochen Steiner
Martin Ernst
Bram Willem Hoffer
Ekkehard Schwab
Johann-Peter Melder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10701552A priority Critical patent/EP2393591A2/fr
Publication of EP2393591A2 publication Critical patent/EP2393591A2/fr
Withdrawn legal-status Critical Current

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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/11—Diaminopropanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/12—1,6-Diaminohexanes
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to catalysts and processes for their preparation, wherein the catalysts are obtainable by bringing a monolithic catalyst support in contact with a suspension containing one or more sparingly or sparingly soluble compounds of the elements selected from the group consisting of the elements cobalt, nickel and copper.
  • the invention further relates to the use of the catalyst according to the invention in a process for the hydrogenation of organic substances, in particular for the hydrogenation of nitriles and a process for the hydrogenation of organic compounds, characterized in that a catalyst according to the invention is used in the process.
  • the preparation of amines by hydrogenation of nitriles is usually carried out in the presence of catalysts containing the elements Cu, Ni and Co.
  • nitrile hydrogenation the formation of secondary amino acids is a frequent side reaction.
  • ammonia see Ullman's Encyclopedia of Industrial Chemistry, 6th Edition, Vol. 2, p. 385.
  • to effectively reduce the formation of secondary amines larger amounts of ammonia are required.
  • the handling of ammonia is also technically complicated, since the storage, handling and implementation must be carried out at high pressure.
  • WO 2007/104663 mixed oxide catalysts in particular Li-Co ⁇ 2, described in which the alkali metal atoms are incorporated in the crystal lattice.
  • the catalysts are generally used as full-contact catalysts, ie, that the catalyst consists almost entirely of catalytically active material. Carrying out the hydrogenation in said The prior art is generally in suspension. This means that the catalysts must be separated from the reaction mixture by filtration after completion of the reaction.
  • WO 2007/02841 1 gives an overview of the preparation of supported catalysts of the Raney type. It is stated here that these catalysts have several disadvantages, i.a. their low mechanical resistance, their relatively low activity and their complex production. Supported Raney catalysts with improved properties are to be achieved according to the disclosure of WO 2007/028411 by coating substrates with nickel / aluminum, cobalt / aluminum or copper / aluminum alloys. The catalysts thus prepared are activated by dissolving all or part of the aluminum with a base.
  • WO 2006/079850 Another approach for the preparation of supported catalysts which are to be suitable for the nitrile hydrogenation is described in WO 2006/079850. These catalysts are obtained by applying metals to a patterned monolith, the deposition being accomplished by impregnation of the monolith with a solution in which the metal is in the form of an ammine complex.
  • the catalysts prepared in this way are, according to the disclosure, suitable for a number of chemical reactions, i.a. is also called the hydrogenation of nitriles.
  • WO 2006/079850 does not constitute an executable disclosure because it does not give details, instructions or experiments on this type of reaction.
  • improved hydrogenation catalysts should be provided which offer advantages over conventional processes.
  • metals such as.
  • Aluminates, which form from the dissolved aluminum under basic conditions, namely as solid residues can lead to blockages and deposits and cause the decomposition of desired product.
  • Another object of the present invention was to find catalysts which enable the hydrogenation, in particular the hydrogenation of nitriles, under simplified reaction conditions. Thus catalysts should be found which allow to carry out the hydrogenation reaction in the absence of ammonia.
  • the handling of ammonia is technically complicated, since the storage, handling and implementation must be carried out at high pressure.
  • catalysts should be found which can be fixedly arranged in the hydrogenation reactor and therefore a technically complicated separation can be avoided, as required for example in the hydrogenation in suspension.
  • the catalysts should therefore have a high mechanical strength and a show little abrasion.
  • the preparation of these catalysts should also be technically easy to implement and the catalysts should be easy to handle.
  • Another object was to provide catalysts in which the catalytically active material is applied to a catalyst support. Compared with catalysts, which consist predominantly of the catalytically active material, so-called full contact catalysts, the cost of materials for supported catalysts are generally lower than in full contact catalysts. As a result, the efficiency of the process can be increased.
  • catalysts containing one or more elements selected from the group consisting of cobalt, nickel and copper which are obtainable by contacting a monolithic catalyst support with a suspension containing one or more insoluble or sparingly soluble compounds of the elements selected from the group of elements cobalt, nickel and copper.
  • the catalyst of the invention contains one or more elements selected from the group consisting of cobalt, nickel and copper.
  • the catalyst contains cobalt or nickel, and in a preferred embodiment, the catalyst contains cobalt.
  • the catalyst may optionally contain one or more dopants.
  • the doping elements are preferably selected from the elements of the 3rd to 8th
  • Preferred dopants are Fe, Ni, Cr, Mo, Mn, P, Ti, Nb, V, Cu, Ag, Pd, Pt, Rh, Ir, Ru and Au.
  • the molar ratio of Co, Cu and Ni atoms to atoms of the doping elements is preferably 10: 1 to 100000: 1, preferably 20: 1 to 10000: 1 and particularly preferably 50: 1 to 1000: 1.
  • the term "catalytically active components" for the elements Cu, Co, Ni, and the aforementioned doping elements ie the elements of the 3rd to 8th subgroup and the 3rd, 4th and 5th main group of the Periodic Table of the Elements, used.
  • the molar ratio of the atoms of the components of the active composition to one another can be determined by known methods of elemental analysis, for example atomic absorption spectrometry (AAS), atomic emission spectrometry (AES), X-ray fluorescence analysis (RFA) or ICP-OES (Inductively Coupled Plasma Optical E- mission Spectrometry).
  • AS atomic absorption spectrometry
  • AES atomic emission spectrometry
  • RMA X-ray fluorescence analysis
  • ICP-OES Inductively Coupled Plasma Optical E- mission Spectrometry
  • the molar ratio of the atoms of the components of the active mass to one another can also be determined mathematically, for example by determining the weights of the compounds used, which contain the components of the active composition, and the proportions of the atoms of the components of the active composition are determined on the basis of the known stoichiometry of the compounds used, so that the atomic ratio of the weights and the stoichiometric formula of the compound used can be calculated.
  • the stoichiometric formula of the compounds used can also be determined experimentally, for example by one or more of the above methods.
  • the catalysts of the invention are prepared by contacting a monolithic catalyst support with a suspension containing one or more sparingly or sparingly soluble compounds of elements selected from the group consisting of cobalt, nickel and copper.
  • monolithic catalyst carrier shaped articles formed into a body containing a plurality of continuous (or interconnected) channels through which the reactants and products are transported by flow / convection.
  • the term “monolithic catalyst support” is understood to mean not only the “classical” shaped bodies with parallel, radially non-interconnected channels, but also shaped bodies in the form of foams, sponges or the like with three-dimensional connections within the shaped body.
  • the term “monolithic catalyst support” also includes moldings with crossflow channels.
  • the number of channels in the monolithic catalyst support per Ouadratinch which is also referred to as "cell-density" or “cells per square inch (cspi)” is preferably from 5 to 2000 cpsi, more preferably from 25 to 1000 cpsi, in particular Preferably, from 250 to 900 cspi and most preferably from 400 to 900 cspi.
  • Monolithic catalyst supports generally contain ceramics, metals or carbon as catalyst framework materials, the catalyst framework material referred to as the materials from which the monolithic catalyst support is predominantly constructed.
  • Preferred catalyst framework materials are ceramic materials, such as aluminum oxides, in particular gamma or delta aluminas, alpha-aluminum oxides, silicon dioxide, kieselguhr, titanium dioxide, zirconium dioxide, cerium dioxide, magnesium oxide, and mixtures thereof.
  • Particularly preferred catalyst frameworks are ceramic materials, such as kaolinite and MuIMt, which are oxide mixtures of SiO 2 and Al 2 O 3 in the ratio of about 2: 3, and beryllium oxide, silicon carbide, boron nitride or boron carbide.
  • the catalyst framework material is cordierite.
  • Cordierite materials and variants based thereon are magnesium aluminum silicates which are formed directly during the sintering of soapstone or talcum with additions of clay, kaolin, chamotte, corundum and MuMt.
  • the simplified approximation and composition of pure ceramic cordierite is approx. 14% MgO, 35% Al2O3 and 51% SiO2 (Source: www.keramik notion.de).
  • the monolithic catalyst supports may be of any size.
  • the dimensions of the monolithic catalyst supports are preferably between 1 cm and 10 m, preferably between 10 cm and 5 m, and very particularly preferably between 20 cm and 100 cm.
  • the monolithic catalyst supports may also be modularly constructed from individual monolithic catalyst supports in which small monolithic catalyst supports are assembled into larger units (e.g., bonded).
  • Monolithic catalyst supports are also commercially available, for example under the trade name Corning Celcor® from Corning and under the trade name HoneyCeram® from NGK Insulators Ltd.
  • the monolithic catalyst support is brought into contact with a suspension which contains one or more insoluble or sparingly soluble compounds of the elements selected from the group consisting of the elements cobalt, nickel and copper.
  • a suspension which contains one or more sparingly or sparingly soluble compounds of the catalytically active components is referred to below as "coating.”
  • the catalysts obtainable by the coating process according to the invention have, compared to the catalysts known from the prior art, in which Co, Cu and / or Ni in the form of soluble compound are applied by impregnation, improved properties.
  • gels containing the catalytically active components are also counted among the difficultly insoluble compounds.
  • the suspension may additionally contain one or more soluble compounds of the catalytic active components.
  • the liquid in which the insoluble or sparingly soluble compounds of the catalytically active components or their gels are suspended together with the monolithic catalyst support is preferably water, nitriles, amines, ethers, such as tetrahydrofuran or dioxane, amides, such as N, N Dimethylformamide or N, N-dimethylacetamide. Particular preference is given to using water as liquid.
  • nitriles are used as the liquid, the nitrile is preferably used, which is to be hydrogenated later with the catalyst according to the invention.
  • amines such amines are preferably used as liquids, which are formed as a product in a subsequent hydrogenation.
  • the insoluble or sparingly soluble compounds of the catalytically active components are preferably oxygen-containing compounds of the catalytically active components, such as their oxides, mixed oxides or hydroxides or mixtures thereof.
  • the elements Cu and / or Ni and / or Co are preferably used in the form of their insoluble oxides or hydroxides or mixed oxides.
  • difficultly or insoluble oxides or oxide mixtures, mixed oxides or mixtures of oxides or mixed oxides which contain both Cu and / or Co and / or Ni and optionally one or more doping elements
  • mixed oxides such as the oxide mixtures disclosed in the patent application with the application designation PCT / EP2007 / 052013, which prior to the reduction with hydrogen a) cobalt and b) one or more elements of the alkali metal group, the alkaline earth metal group, the rare earth group or zinc or mixtures thereof, wherein the elements a) and b) are present at least partly in the form of their mixed oxides, for example LiCo ⁇ 2, or
  • EP-A-963 975 disclosed oxide mixtures, prior to reduction with hydrogen 22 to 40 wt .-% ZrO 2 , 1 to 30 wt .-% oxygen-containing compounds of copper, calculated as CuO, 15 to 50 wt .-% oxygen-containing Compounds of nickel, calculated as NiO, wherein the molar Ni: Cu ratio is greater than 1, 15 to 50 wt .-% oxygen-containing compounds of cobalt, calculated as CoO, 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as Al 2 O 3 or MnO 2 , and contains no oxygen-containing compounds of molybdenum, for example, the in loc.
  • Copper-containing oxide mixtures disclosed in DE-A-2445303 eg the copper-containing precipitation catalyst disclosed in Example 1, which is prepared by treating a solution of copper nitrate and aluminum nitrate with sodium bicarbonate followed by washing, drying and tempering of the precipitate and a composition of about 53 wt % Of CuO and about 47% by weight of Al 2 O 3 , or
  • WO 2006005505 and WO 2006005506 disclosed oxide mixtures containing copper oxide (with a proportion in the range of 50 ⁇ x ⁇ 80, preferably 55 ⁇ x ⁇ 75 wt .-%), alumina (with a proportion in the range of 15 ⁇ y ⁇ 35, preferably 20 ⁇ y ⁇ 30% by weight) and lanthanum oxide (in the range of
  • the insoluble or sparingly soluble compound of the catalytically active components is LiCoO 2 .
  • Process for the preparation of LiCo ⁇ 2 be z. In Antolini (E. Antolini, Solid State Ionics, 159-171 (2004)) and Fenton et al. (WM Fenton, PA Huppert, Sheet Metal Industries, 25 (1948), 2255-2259).
  • LiCoO 2 can be prepared by thermal treatment of the corresponding lithium and cobalt compounds, such as nitrates, carbonates, hydroxides, oxides, acetates, citrates or oxalates.
  • LiCoO 2 can be precipitated by precipitating water-soluble lithium and cobalt salts by adding an alkaline solution and then calcining. LiCoO 2 can also be obtained by the sol-gel method.
  • LiCoO 2 may also be prepared as described by Song et al. (SW Song, KS Han, M. Yoshimura, Y. Sata, A. Tatsuhiro, Mat. Res. Soc., Symp., Proc, 606, 205-210 (2000)) by hydrothermal treatment of cobalt metal with aqueous LiOH solutions become.
  • the suspension of the sparingly or sparingly soluble compounds of the catalytically active components is obtained by "precipitation" by precipitating compounds of the catalytically active components which are soluble in the abovementioned liquid by addition of a precipitant
  • catalytically active components are soluble metal salts, such as the hydroxides, sulfates, carbonates, oxalates, nitrates, acetates or chlorides of the catalytically active components
  • the precipitation can also be effected with other suitable soluble compounds of the corresponding elements / or Co and / or Ni are preferably used in the form of their soluble carbonates, chlorides or nitrates.
  • the soluble compounds are precipitated by addition of a precipitant as sparingly or insoluble, basic salts.
  • the precipitants used are preferably bases, in particular mineral bases, such as alkali metal bases.
  • Examples of precipitants are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.
  • ammonium salts for example ammonium halides, ammonium carbonate, ammonium hydroxide or ammonium carboxylates.
  • the precipitation may for example be up to 70 0 C, carried out at temperatures of 20 to 100 0 C, particularly 30 to 90 0 C, especially at 50th
  • the precipitates obtained in the precipitation are generally chemically nonuniform and generally contain mixtures of the oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals used.
  • the suspension is prepared by adding the catalytically active components in particulate form, for example as a powder be added to the liquid.
  • the catalytically active components in particulate form used are the above-mentioned, preferred and particularly preferred sparingly soluble or insoluble oxides or oxide mixtures, mixed oxides or mixtures of oxides or mixed oxides which contain both Cu and / or Co and / or Ni and optionally one or more Contain dopants.
  • the catalytically active components in particulate form are preferably obtained by spray drying, for example, in which a suspension obtained by precipitation is spray-dried.
  • the particles present in suspension, the insoluble or sparingly soluble compounds of the catalytically active components preferably have an average particle diameter of 0.001 to 1000 .mu.m, more preferably 1 to 500 .mu.m, particularly preferably from 10 to 100 .mu.m and very particularly preferably from 20 to 80 ⁇ m. Particles of this size allow a homogeneous coating and lead to catalysts that have high activity and mechanical resistance.
  • the suspension is generally dispersed intensively, wherein the dispersion is preferably carried out by intensive stirring or by ultrasound.
  • the dispersion can preferably also be carried out by continuously pumping the suspension over.
  • the concentration of insoluble or sparingly soluble compounds of Cu, Ni and Co is 1 to 50 wt .-%, preferably 5 to 25 wt .-% and particularly preferably 10 to 20 wt .-%, each based on the mass of the liquid used ,
  • the coating of the monolithic catalyst support takes place in which the monolithic catalyst support is brought into contact with the non-soluble or sparingly soluble compounds of the catalytically active components which are in suspension.
  • the monolithic catalyst support Before contacting, the monolithic catalyst support is preferably dried.
  • the drying is usually carried out at 100 to 200 0 C for a period of 1 to 48 hours.
  • the coating of the monolithic catalyst support is preferably carried out in which the suspension is prepared before contacting the monolithic catalyst support and the monolithic catalyst support is brought into contact with the suspension already prepared.
  • the monolithic catalyst support is preferably contacted with the suspension in which the monolithic catalyst support is immersed in the suspension or in which the suspension is continuously pumped over the monolithic catalyst support. In a particularly preferred embodiment, the monolithic catalyst support is immersed in the suspension.
  • the suspension is aspirated through the channels of the monolithic catalyst support during the immersion, so that the suspension can penetrate for the most part completely into the channels of the monolith.
  • the suction of the suspension can be carried out, for example, by generating a negative pressure at one end of the monolithic catalyst support and immersing the monolithic catalyst support in the suspension with the other end, the suspension being sucked.
  • the coating of the monolithic catalyst support can also take place in that the monolithic catalyst support is already suspended in the liquid and the suspension is prepared “in situ” in the liquid by "precipitation".
  • the insoluble or sparingly soluble compounds of the catalytically active components are precipitated directly onto the monolithic catalyst support.
  • the monoliths are usually so long with the suspension by e.g. Dipping brought into contact until a complete and homogeneous coating of the catalyst support is ensured.
  • the suspension is dispersed during the contacting of the monolithic catalyst support, so that the particles can penetrate as far as possible completely into the channels of the monolith and a homogeneous coating is achieved.
  • the suspension can be removed, for example, by decantation, dripping, filtration or filtration.
  • the suspension is preferably removed by creating an overpressure on one end of the monolithic catalyst support and pressing the excess suspension out of the channels.
  • the overpressure can be done, for example, by blowing compressed air into the channels.
  • the coated monolithic catalyst support is usually dried and calcined.
  • the drying is usually carried out at temperatures of 80 to 200 0 C, preferably 100 to 150 0 C.
  • the calcination is generally carried out at temperatures of 300 to 800 ° C, preferably 400 to 600 0 C, particularly preferably 450 to 550 ° C. ,
  • the contacting of the monolithic catalyst support with the suspension may be repeated one or more times.
  • a binder applied to the monolithic catalyst support before and / or during the coating of the monolithic catalyst support with the catalytically active component Nenten a binder applied to the monolithic catalyst support.
  • a binder By applying a binder on the monolithic catalyst support, the intrinsic surface can be increased, thereby more active mass can be applied, whereby the catalytic activity of the catalysts is increased.
  • the binders used are preferably aluminum oxides, in particular gamma or delta
  • Particularly preferred binders are aluminum oxides, in particular gamma or delta aluminas, alpha-aluminum oxides, silicon dioxide or magnesium oxide, and mixtures thereof.
  • the application of the binder is preferably carried out by coating the monolithic catalyst support.
  • the monolithic catalyst carrier is usually contacted with a suspension (liquid containing binder) containing the binder.
  • concentration of the binder in the suspension is preferably 0.5 to 25
  • Wt .-% particularly preferably 1 to 15 wt .-% and most preferably 1 to 5 wt .-%, based on the liquid used.
  • the liquids mentioned above are used.
  • the suspension will be prepared by adding the binder in particulate form, for example as a powder to the liquid.
  • the particles of the binder present in suspension preferably have an average particle diameter of from 0.001 to 1000 .mu.m, more preferably from 1 to 500 .mu.m, more preferably from 10 to 100 .mu.m, and most preferably from 20 to 80 .mu.m.
  • the suspension is generally dispersed intensively, wherein the dispersion is preferably carried out by intensive stirring or by ultrasound.
  • the dispersion can preferably also be carried out by continuously pumping the suspension over.
  • the coating of the monolithic catalyst support takes place in which the monolithic catalyst support is brought into contact with the suspension binder.
  • the coating of the monolithic catalyst support with binder is preferably carried out in which the suspension is prepared before contacting the monolithic catalyst support and the monolithic catalyst support is brought into contact with the suspension already prepared.
  • the monolithic catalyst support is preferably contacted with the suspension in which the monolithic catalyst support is immersed in the suspension or in which the suspension is continuously pumped over the monolithic catalyst support. In a particularly preferred embodiment, the monolithic catalyst support is immersed in the suspension.
  • the suspension is aspirated through the channels of the monolithic catalyst support during the immersion, so that the suspension can penetrate for the most part completely into the channels of the monolith.
  • the suction of the suspension can be carried out, for example, by generating a negative pressure at one end of the monolithic catalyst support and immersing the monolithic catalyst support in the suspension with the other end, the suspension being sucked. After contacting, the excess of suspension is removed.
  • the suspension can be removed, for example, by decantation, dripping, filtration or filtration.
  • the suspension is preferably removed by creating an overpressure on one end of the monolithic catalyst support and pressing the excess suspension out of the channels. The overpressure can be done, for example, by blowing compressed air into the channels.
  • the coated monolithic catalyst support is usually dried and calcined.
  • the drying is usually carried out at temperatures of 80 to 200 0 C, preferably 100 to 150 0 C.
  • the calcination is generally carried out at temperatures of 300 to 800 ° C, preferably 400 to 600 0 C, particularly preferably 450 to 550 ° C. ,
  • the contacting of the monolithic catalyst support with the suspension containing the binder may be repeated one or more times. If the application of the catalytically active components is effected by coating, then the coating of the monolithic catalyst support with binder can take place before the coating of the catalytically active components.
  • the coating of the monolithic catalyst support with binder takes place simultaneously with the coating with catalytically active components, in which a suspension is used for the coating, which in addition to the non-soluble or sparingly soluble components of the catalytically active components in addition binders in particulate Contains form.
  • the monolithic catalyst support and / or binder are contacted with an acid prior to and / or during the application of the binder.
  • an acid By treating the monolithic catalyst support and / or the binder with acid, the specific surface of the monolith can be further increased and the adhesion between monolithic catalyst support and binder improved, whereby the mechanical resistance and the catalytic activity of the catalysts of the invention is increased .
  • the acids used are preferably organic acids, such as formic acid or acetic acid.
  • the acid is preferably added directly to the suspension of binder and liquid.
  • concentration of the acid in the liquid is preferably 0.1 to 5 wt .-%, preferably 0.5 to 3 wt .-%, particularly preferably 1 to 2 wt .-%, each based on the mass of the liquid used.
  • the catalysts of the invention contain one or more elements selected from the group of alkali metals, alkaline earth metals and rare earth metals.
  • Preferred elements of the group of alkali metals are Li, Na, K, Rb and Cs, more preferably Li, Na, K and Cs, in particular Li, Na and K.
  • Preferred elements of the group of alkaline earth metals are Be, Mg, Ca, Sr and Barium, more preferably Mg and Ca.
  • Preferred elements of the rare earth group are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, particularly preferably Sc, Y, La and Ce.
  • the catalyst contains Ni, in a particularly preferred embodiment the catalyst contains Na as the alkali metal. Further preferred combinations are Ni and Li, Ni and K, as well as Ni and Cs.
  • the catalyst contains Co
  • the catalyst contains Li as alkali metal.
  • Further preferred combinations are Co and Na, Co and K, as well as Co and Cs.
  • the molar ratio of Cu, Co and Ni atoms to atoms of the elements of the alkali, alkaline earth and rare earth metals in the catalyst is preferably 0.1: 1 to 10000: 1, preferably 0.5: 1 to 1000: 1 and more preferably 0.5: 1 to 500: 1.
  • the molar ratio of Cu, Co and Ni atoms to atoms of the elements of the alkali, alkaline earth and rare earth metals in the catalyst is less than 300: 1, preferably less than 100: 1 in particular preferred less than 50: 1, and most preferably less than 25: 1.
  • the application of the elements of the alkali, alkaline earth and rare earth metals can be carried out by carrying out the coating in the presence of one or more of these elements or a soluble or insoluble compound of these elements.
  • the application of the elements of the alkali, alkaline earth and rare earth metals to the catalyst takes place by mixing the coated monolithic catalyst supports with a soluble compound of one or more of the elements of the alkali, alkaline earth and rare earth metals. pregnated.
  • the impregnation (also "impregnation") of the coated monolithic catalyst support can be carried out by the usual methods, for example by applying a soluble compound of one or more of the elements of alkali, alkaline earth and rare earth metals in one or more impregnation stages.
  • the elements of the alkali, alkaline earth and rare earth metals are preferably used in the form of their soluble hydroxides, preferably LiOH, KOH, NaOH, CsOH, Ca (OH) 2 or Mg (0H) 2.
  • the impregnation is typically carried out in a liquid in which the soluble compounds of the elements of the alkali, alkaline earth and rare earth metals are dissolved.
  • the liquid used is preferably water, nitriles, amines, ethers, such as tetrahydrofuran or dioxane, amides, such as N, N-dimethylformamide or N, N-dimethylacetamide. Particular preference is given to using water as liquid.
  • nitriles are used as the liquid, the nitrile is preferably used, which is to be hydrogenated later with the catalyst according to the invention.
  • amines such amines are preferably used as liquids, which are formed as a product in a subsequent hydrogenation.
  • the concentration of the soluble compounds of the alkali, alkaline earth and rare earth metals is generally 0.1 to 25 wt .-%, preferably 0.5 to 20 wt .-%, in particular preferably 1 to 15 wt .-% and very particularly preferably 5 to 10 wt .-%, each based on the mass of the liquid used.
  • the impregnation is preferably carried out by immersing the monolithic catalyst support in the liquid containing the dissolved compounds of the elements of alkali, alkaline earth and rare earth metals (impregnation solution).
  • the impregnation solution is aspirated through the channels of the monolithic catalyst support during the immersion, so that the impregnation solution can penetrate for the most part completely into the channels of the monolith.
  • the impregnation of the impregnation solution can be carried out, for example, by generating a negative pressure at one end of the monolithic catalyst support and immersing the monolithic catalyst support with the other end in the impregnation solution, the impregnation solution being sucked.
  • the impregnation can also be carried out by the so-called "incipient wetness method", in which the monolithic catalyst support is moistened to a maximum saturation with the impregnation solution in accordance with its absorption capacity.
  • the impregnation can also be done in supernatant solution.
  • the impregnated monolithic catalyst support is usually separated from the impregnation solution.
  • the separation of the impregnation solution can be carried out, for example, by decantation, dripping, filtration or filtration.
  • the impregnation solution is preferably removed by creating an overpressure on one end of the monolithic catalyst support and forcing the excess impregnation solution out of the channels.
  • the overpressure can be generated for example by blowing compressed air into the channels.
  • the impregnated monolithic catalyst support is preferably dried and calcined.
  • the drying is usually carried out at temperatures of 80 to 200 0 C, preferably 100 to 150 0 C.
  • the calcination is generally carried out at temperatures of 300 to 800 ° C, preferably 400 to 600 0 C, particularly preferably 450 to 550 ° C. ,
  • the impregnation takes place in one or more stages.
  • the multi-stage impregnation is advantageous to apply when the monolithic catalyst support is to be applied in larger quantities with elements of alkali, alkaline earth and rare earth metals.
  • the monolithic catalysts obtained according to the invention generally contain, after calcination, the catalytically active components in the form of a mixture of their oxygen-containing compounds, i. in particular as oxides, mixed oxides and / or hydroxides.
  • the catalysts prepared in this way can be stored as such.
  • the catalysts according to the invention are as a rule prereduced by treatment with hydrogen after calcination or conditioning. However, they can also be used without prereduction in the process, wherein they are then reduced under the conditions of hydrogenation by the hydrogen present in the reactor, wherein the catalyst is usually brought in situ in its catalytically active form.
  • the catalysts are generally first exposed at 150 to 200 0 C over a period of 12 to 20 hours a nitrogen-hydrogen atmosphere and then treated for up to about 24 hours at 200 to 400 0 C in a hydrogen atmosphere.
  • a portion of the oxygen-containing metal compounds present in the catalysts is reduced to the corresponding metals, so that they are present together with the various oxygen compounds in the active form of the catalyst.
  • the prereduction of the catalyst is carried out in the same reactor in which the hydrogenation process according to the invention is subsequently carried out.
  • the catalyst thus formed may be handled and stored after prereduction under an inert gas such as nitrogen, or under an inert liquid, for example an alcohol, water or the product of the particular reaction for which the catalyst is employed.
  • the catalyst can also be passivated with a nitrogen-containing gas stream such as air or a mixture of air with nitrogen after prereduction, ie provided with a protective oxide layer.
  • a nitrogen-containing gas stream such as air or a mixture of air with nitrogen after prereduction, ie provided with a protective oxide layer.
  • the storage of the catalysts under inert substances or the passivation of the catalyst enable uncomplicated and safe handling and storage of the catalyst. If appropriate, the catalyst must then be freed of the inert liquid before the actual reaction or the passivation layer z. B. be lifted by treatment with hydrogen or a gas containing hydrogen.
  • the catalyst can be freed from the inert liquid or passivation layer before starting the hydrogenation. This happens, for example, by treatment with hydrogen or a gas containing hydrogen.
  • catalyst precursors may also be used in the process without prereduction, as described above, in which case they are reduced under the hydrogenation conditions by the hydrogen present in the reactor, with the catalyst usually forming in situ in its active form.
  • the catalysts according to the invention can be used in a process for the hydrogenation of compounds (educts) which contain at least one unsaturated carbon-carbon, carbon-nitrogen or carbon-oxygen bond.
  • Suitable compounds are generally compounds which contain at least one or more carboxylic acid amide groups, nitrile groups, imine groups, enamine groups, azine groups or oxime groups which are hydrogenated to give amines. Furthermore, in the process according to the invention, compounds which contain at least one or more carboxylic acid ester groups, carboxylic acid groups, aldehyde groups or keto groups can be hydrogenated to alcohols.
  • Suitable compounds are also aromatics, which can be converted to unsaturated or saturated carbo-or heterocycles.
  • Particularly suitable compounds which can be used in the process according to the invention are organic nitrile compounds, imines and organic oxides. These can be hydrogenated to primary amines.
  • nitriles are used in the process according to the invention.
  • These may be, for example, the hydrogenation of aliphatic mono- and dinitriles having 1 to 30 carbon atoms, cycloaliphatic mono and dinitriles having 6 to 20 carbon atoms. Furthermore, alpha- and beta-amino nitriles or alkoxynitriles.
  • Suitable nitriles are for. Acetonitrile for the production of ethylamine, propionitrile for the preparation of propylamine, butyronitrile for the preparation of butylamine, lauronitrile for the production of laurylamine, stearyl nitrile for the preparation of stearylamine, N, N
  • DMAPN Dimethylaminopropionitrile
  • DMAPA N, N-dimethylaminopropylamine
  • benzonitrile for the preparation of benzylamine.
  • Suitable dinitriles are adi podinitrile (ADN) for the preparation of hexamethylenediamine (HMD) or HMD and 6-aminocapronitrile (ACN), 2-methylglutarodinitrile for the preparation of 2-methylglutarodiamine, succinonitrile for the preparation of 1, 4-butanediamine and Korkkla- redinitrile for the preparation of octamethylenediamine.
  • ADN adi podinitrile
  • HMD hexamethylenediamine
  • ACN 6-aminocapronitrile
  • 2-methylglutarodinitrile for the preparation of 2-methylglutarodiamine
  • succinonitrile for the preparation of 1, 4-butanediamine
  • Korkklaklaklad Redinitrile for the preparation of octamethylened
  • cyclic nitriles such as isophorone nitrile imine (isophorone nitrile) for the preparation of isophorone diamine and isophthalonitrile for the preparation of meta-xylylenediamine.
  • ⁇ -aminonitriles and ⁇ -aminonitriles such as aminopropionitrile for the preparation of 1, 3-diaminopropane or ⁇ -aminonitriles, such as aminocapronitrile for the preparation of hexamethylenediamine.
  • nitriles such as iminodiacetonitrile for the preparation of diethylenetriamine
  • suitable nitriles are ⁇ -aminonitriles, for example addition products of alkylamines, alkyldiamines or alkanolamines to acrylonitrile
  • 3- [2-aminoethyl] amino] propionitrile can be added to 3- (3-aminoethyl) aminopropylamine and 3,3'- (ethylenediimino) bispropionitrile and 3- [2- (amino-propylamino) ethylamino] -propionitrile, respectively N, N'-bis (3-aminopropyl) ethylenediamine.
  • N N-dimethylaminopropionitrile
  • DMAPA N-dimethylaminopropylamine
  • ADN adiponitrile
  • HMD hexamethylenediamine
  • 6-ACN 6-aminocapronitrile
  • Isophorone diamine used in the process of the invention.
  • hydrogen or a gas containing hydrogen may be used.
  • the hydrogen is generally used technically pure.
  • the hydrogen may also be in the form of a hydrogen-containing gas, i. in admixtures with other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide are used.
  • inert gases such as nitrogen, helium, neon, argon or carbon dioxide are used.
  • reformer effluents, refinery gases, etc. can be used as the hydrogen-containing gases if and to the extent that these gases do not contain any contact poisons for the hydrogenation catalysts used, for example CO.
  • pure hydrogen or essentially pure hydrogen in the process, for example hydrogen having a content of more than 99% by weight of hydrogen, preferably more than 99.9% by weight of hydrogen, particularly preferably more than 99.99 Wt .-% hydrogen, in particular more than 99.999 wt .-% hydrogen.
  • the molar ratio of hydrogen to the compound used as starting material is generally 1: 1 to 25: 1, preferably 2: 1 to 10: 1.
  • the hydrogen can be recycled as cycle gas in the reaction.
  • the hydrogenation can be carried out with the addition of ammonia.
  • Ammonia is usually present in molar ratios to the nitrile group in the ratio of 0.5: 1 to 100: 1, preferably 2: 1 to 20: 1 used.
  • the preferred embodiment is a method in which no ammonia is added.
  • the reaction can be carried out in bulk or in a liquid.
  • the hydrogenation is preferably carried out in the presence of a liquid.
  • Suitable liquids are, for example, C1 to C4 alcohols, such as methanol or ethanol, C4 to C12 dialkyl ethers, such as diethyl ether or tert-butyl methyl ether, or cyclic C4 to C12 ethers, such as tetrahydrofuran or dioxane. Suitable liquids may also be mixtures of the abovementioned liquids. The liquid may also be the product of the hydrogenation.
  • the reaction can also be carried out in the presence of water.
  • the water content should not be more than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight, based on the mass of the liquid used, in order to leach and / or wash off the compounds to avoid the alkali, alkaline earth and / or rare earth metals as far as possible.
  • the hydrogenation is generally carried out at a pressure of 1 to 150 bar, in particular from 5 to 120 bar, preferably from 8 to 85 bar and particularly preferably from 10 to 65 bar. Preferably, the hydrogenation is carried out at a pressure of less than 65 bar as a low pressure method.
  • the temperature is usually in a range of 25 to 300 0 C, in particular from 50 to 200 0 C, preferably from 70 to 150 0 C, particularly preferably from 80 to 130 0 C.
  • the hydrogenation process according to the invention can be carried out continuously, batchwise or semi-continuously. Preference is given to hydrogenating semi-continuously or continuously.
  • Suitable reactors are thus both stirred tank reactors and tubular reactors.
  • Typical reactors are, for example, high-pressure stirred tank reactors, autoclaves, fixed bed reactors, fluidized bed reactors, moving beds, circulating fluidized beds, continuously stirred vessels, bubble reactors, circulation reactors, such as jet loop reactors, etc., in each case for the desired reaction conditions (such as temperature, pressure and residence time).
  • suitable reactor is used.
  • the reactors can each be used as a single reactor, as a series of individual reactors and / or in the form of two or more parallel reactors.
  • the reactors can be operated in an AB driving style (alternating driving style).
  • the process according to the invention can be carried out as a batch reaction, semi-continuous reaction or continuous reaction.
  • the specific reactor construction and the execution of the reaction can, depending on the hydrogenation process to be carried out, the state of aggregation of vary hydrogenating starting product, the required reaction times and the nature of the catalyst used.
  • the hydrogenation process of the present invention is carried out continuously in a high pressure stirred tank reactor, a bubble column, a recycle reactor such as a jet loop reactor or a fixed bed reactor in which the catalyst is fixed, i. is arranged in the form of a fixed catalyst bed performed. It can be hydrogenated in bottoms or trickle, preferably in the upflow mode. Working in the swamp mode is technically easier.
  • the advantages of the catalysts of the invention are particularly effective, since the catalysts of the invention have a high mechanical stability and thus long service life, whereby they are suitable for continuously operated process.
  • the hydrogenation of nitriles is carried out continuously in the liquid phase with fixed catalyst in a stirred autoclave, a bubble acid, a circulation reactor such as a jet loop or a fixed bed reactor.
  • the catalyst loading in continuous operation is typically from 0.01 to 10, preferably from 0.2 to 7, particularly preferably from 0.5 to 5 kg of starting material per liter of catalyst per hour.
  • a suspension of educt and catalyst is introduced into the reactor.
  • the suspension of starting material and catalyst must be well mixed with hydrogen, e.g. through a turbine stirrer in an autoclave.
  • the suspended catalyst material can be introduced by conventional techniques and separated again (sedimentation, centrifugation, cake filtration, cross-flow filtration).
  • the catalyst can be used one or more times.
  • the catalyst concentration is advantageously 0.1 to 50 wt .-%, preferably 0.5 to 40 wt .-%, particularly preferably 1 to 30 wt .-%, in particular 5 to 20 wt .-%, each based on the total weight of Suspension consisting of educt and catalyst.
  • a dilution of the reactants can be carried out with a suitable, inert solvent.
  • the residence time in the process according to the invention when carried out in a batch process is generally from 15 minutes to 72 hours, preferably from 60 minutes to 24 hours, more preferably from 2 hours to 10 hours.
  • the hydrogenation in the gas phase can be carried out in a fixed bed reactor or a fluidized bed reactor.
  • Common reactors for carrying out hydrogenation reactions are described, for example, in Ullmann's Encyclopaedia [Ullmann's Encyclopaedia]. Mann's Encyclopedia Electronic Release 2000, Chapter: Hydrogenation and Dehydrogenation, pp. 2 - 3].
  • the activity and / or selectivity of the catalysts according to the invention can decrease with increasing service life. Accordingly, a process for the regeneration of the catalysts according to the invention was found, in which the catalyst is treated with a liquid.
  • the treatment of the catalyst with a liquid should lead to the removal of any adhering compounds which block active sites of the catalyst.
  • the treatment of the catalyst with a liquid can be carried out by stirring the catalyst in a liquid or by washing the catalyst in the liquid, after treatment, the liquid can be separated by filtration or decanting together with the detached impurities from the catalyst.
  • Suitable liquids are generally the product of the hydrogenation, water or an organic solvent, preferably ethers, alcohols or amides.
  • the treatment of the catalyst with liquid can take place in the presence of hydrogen or of a gas containing hydrogen.
  • This regeneration can be usually from 20 to 250 0 C, carried out at elevated temperature. It is also possible to dry the used catalyst and oxidize adhering organic compounds with air to volatile compounds such as CO2. Before further use of the catalyst in the hydrogenation of this must be activated after oxidation, as a rule, as described above.
  • the catalyst can be brought into contact with a soluble compound of the catalytically active components.
  • the contacting can be carried out in such a way that the catalyst is impregnated or moistened with a water-soluble compound of the catalytically active component.
  • the compound of the catalytically active components is a compound of a doping element or a compound of the metals of the alkali, alkaline earth or rare earth metals.
  • An advantage of the invention is that the use of the catalyst according to the invention reduces the apparatus and investment requirements as well as the operating costs for plants in hydrogenation processes.
  • the investment costs increase with increasing operating pressure and the use of solvents and additives.
  • the hydrogenation process according to the invention can also be operated in the absence of water and ammonia, process steps for separating off the water and ammonia from the reaction product (distillation) are omitted or simplified. Due to the absence of water and ammonia, the existing reactor volume can lumen can be used better because the volume released can be used as an additional reaction volume.
  • the catalysts of the invention also allow the hydrogenation, in particular the hydrogenation of nitriles, under simplified reaction conditions, since the hydrogenation of nitriles can be carried out in the absence of ammonia.
  • the catalysts provided by this invention show numerous advantages over conventional catalysts of the prior art. So the leaching of metals, such. As aluminum in the case of skeletal catalysts or alkaline promoters such as lithium, which leads to a diminishing stability and deactivation of the catalyst, largely avoided. In particular, the formation of aluminates, which occurs in conventional Raney catalysts by dissolving out the aluminum under basic conditions, is avoided, so that these aluminates do not constitute a source for the formation of solid residues, which lead to blockages and deposits and the decomposition of value propositions. you can do it.
  • the catalysts according to the invention can also be fixedly arranged in the hydrogenation reactor, so that no technically complicated separation of the catalysts must be carried out at the end of the reaction, as required for example in the preparation in suspension.
  • the catalysts also have a high mechanical strength and show low abrasion. Furthermore, the formation of undesired by-products, in particular the formation of secondary amines from nitriles, is reduced, so that the target products are obtained in high yield and selectivity.
  • the production of these catalysts is also technically easy to implement. Furthermore, the catalysts according to the invention are easy to handle.
  • Another advantage of the catalysts according to the invention is that the catalytically active material is applied to a catalyst support. Compared with catalysts, which consist predominantly of the catalytically active material, so-called full contact catalysts, the cost of materials for supported catalysts are generally lower than in full contact catalysts. This further increases the economic efficiency of the process.
  • the catalyst loading is given as the quotient of educt amount in the feed and the product of catalyst volume and time.
  • Catalyst load educt amount / (volume of catalyst • reaction time).
  • the volume of the catalyst corresponds to the volume that would be taken up by a solid cylinder, the one identical to the catalyst (monolith)
  • the reactor is usually completely filled with the monolithic catalyst.
  • the unit of catalyst loading is given in [kg-product / (lh)].
  • the yield of product A (P) results from the area percent of the product signal.
  • the area percent F% (i) of a starting material (F% (E)), product (F% (P)), a by-product (F% (N)) or quite generally a substance i (F% (i)), is the quotient of the area F (i) below the signal of the substance i and the total area FTotal, ie the sum of the area below the signals i, multiplied by 100, yields:
  • the selectivity of the starting material S (E) is calculated as the quotient of product yield A (P) and reactant conversion U (E):
  • Example 1 cordierite monoliths (Celcor®) from Corning, but can also be obtained with comparable monoliths (for example HoneyCeram® from NGK Insulators).
  • Example 1 cordierite monoliths (Celcor®) from Corning, but can also be obtained with comparable monoliths (for example HoneyCeram® from NGK Insulators).
  • Example 1 Comparative monoliths (for example HoneyCeram® from NGK Insulators).
  • the monolithic catalyst support was coated with an oxide mixture according to EP-B1-636409.
  • the oxide mixture can according to the provision specified therein 55 to 98 wt .-% cobalt, 0.2 to 15 wt .-% phosphorus, 0.2 to 15 wt .-% manganese and 0.2 to 5 wt .-% alkali ( calculated as oxide).
  • the exact composition of the oxide mixture used is given in the respective examples.
  • Cordierite monoliths from Corning in the form of structured shaped bodies (round, 20 ⁇ 50 mm) and 400 cpsi were used as the monolithic catalyst support.
  • the monolithic catalyst support was dried at 120 ° C. for 10 hours.
  • Cordierite monoliths from Corning were used as monolithic catalyst supports in the form of structured moldings (round, 18 ⁇ 50 mm) and 900 cpsi.
  • the monolithic catalyst support was dried at 120 ° C for 10 hours.
  • the dry monolith was immersed in the suspension, blown with compressed air and dried on a hot air blower at about 140 0 C ( ⁇ 10 0 C). These steps were repeated for a total of 6 dives. Subsequently, the monolith was calcined at 500 ° C. for 3 hours.
  • the obtained catalyst precursor had an average cobalt content of 14.5% by weight (indicated as metallic cobalt).
  • the molar ratio of Co atoms to Na atoms in the catalyst was 125: 1.
  • Cordierite monoliths from Corning in the form of structured moldings (round, 18 ⁇ 50 mm) and 900 cpsi were used as the monolithic catalyst support.
  • the monolithic catalyst support was dried at 120 ° C. for 10 hours.
  • the dry monolith was immersed in the suspension, blown with compressed air and dried on a hot air blower at about 140 0 C ( ⁇ 10 0 C). These steps were repeated for a total of 6 dives. Then, the monolith was calcined for 3 STUN to 500 0 C.
  • the catalyst precursor had an average cobalt content of 30.5% by weight (reported as metallic cobalt) and lithium of 3.7% by weight (reported as metallic lithium).
  • the molar ratio of Co atoms to Li atoms in the catalyst was 1: 1
  • a cobalt hexaammine solution was prepared by dissolving 634 g of ammonium carbonate in 1709 ml of ammonia solution (33% NH3). Subsequently, 528 g of cobalt (II) carbonate hydrate were added in portions. The solution was filtered to separate insoluble matters. The solution obtained had a redox potential -248mV, the cobalt content was 4 wt .-%.
  • cordierite monoliths (Celcor®) from Corning were used in the form of structured moldings (round, 9.5 x 20 mm) and 400 cpsi.
  • the monolithic catalyst support was dried at 120 ° C. for 10 hours.
  • gamma-alumina In a template, 7.9 g of gamma-alumina (Pural SB from Sasol) were etched with 2.4 g of formic acid. 256 g of gamma-alumina (D10-10, BASF SE) was mixed with the etched gamma-alumina and added to the cobalt hexaammine solution.
  • the dry monolith was immersed in the suspension thus prepared, blown with compressed air and dried on a hot air blower at about 140 0 C ( ⁇ 10 0 C). These steps were repeated for a total of 4 dives. Then, the Mo nolith 2 hours at 105 0 C was dried in a drying cabinet and calcined at 280 0 C for 4 hours.
  • the catalyst precursor had an average cobalt content of 1.0% by weight (reported as metallic cobalt).
  • cordierite monoliths from Corning were used in the form of structured moldings (round, 9.5 x 20 mm) and 400 cpsi.
  • the monolithic catalyst support was dried at 120 ° C. for 10 hours.
  • the dry monolith was immersed in the suspension, blown with compressed air and dried on a hot air blower at about 140 ° C ( ⁇ 10 ° C). These steps were repeated for a total of 5 dives. Subsequently, the monolith was 10
  • Catalyst precursor had an average nickel content of 8.6 wt% (reported as metallic nickel).
  • the molar ratio of Co atoms to Na atoms in the catalyst was 730: 1
  • a catalyst precursor prepared according to Example 1a was reduced for 10 hours at 300 ° C. with a mixture of 90% hydrogen and 10% nitrogen and then passivated with air at room temperature. The passivated monolith strands were then drilled in 1 liter bores Mounted so that the holes were completely filled by the monolith strands.
  • the holder with the monoliths was placed in a 160 ml Parr autoclave (hte) - with magnetically coupled disc stirrer (stirrer speed 1000 revolutions / minute), electric heating, internal temperature measurement and hydrogen supply via iterative differential pressure Dosage - built-in.
  • the activation of the passivated catalyst was carried out before the nitrile hydrogenation at 150 ° C / 100 bar for a period of 12 hours with hydrogen while stirring the monolithic catalysts in THF.
  • Example 5a The holder with the activated cobalt monolith catalysts (13 wt .-% cobalt) was removed from the autoclave and rinsed with THF.
  • the fixture was installed in the reactor without further treatment.
  • the support was stored for 30 minutes at room temperature in an aqueous, 0.85 molar solution of the alkali hydroxides LiOH, NaOH, KOH or CsOH (Examples 5b to 5e), the monolithic catalysts being completely wetted with the solution (impregnation).
  • the hydrogenation was carried out in a bubble column containing a catalyst prepared according to Example 1a, 1b or Example 2 catalyst in a stacked form, in the upflow mode.
  • the hydrogenation was separated in a phase separation vessel in the gas and liquid phases.
  • the liquid phase was discharged and quantitatively analyzed by GC analysis. 99.2% to 99.9% of the liquid phase was recycled to the bubble column along with the fresh DMAPN and the fresh hydrogen.
  • Example 1 a prepared catalyst (1 1 monoliths 20.4 x 50 mm, 1 monolith 20.4 x 18.5 mm) for 18 hours at 120 0 C and 60 bar in THF reduced with hydrogen.
  • the THF was drained and the apparatus (bubble column + catalyst) was then purged with 800 ml of a 2% by weight aqueous LiOH solution for 60 minutes at room temperature. Subsequently, the aqueous solution was drained and it was rinsed twice for 10 minutes each with 800 ml of tetrahydrofuran. Then, DMAPN was continuously run into the THF filled reactor.
  • the hydrogenation of 3-dimethylaminopropionitrile (DMAPN) to 3- dimethylaminopropylamine (DMAPA) was for 500 hours in the upflow mode in the absence of ammonia at 120 0 C, a pressure range of 30 to 50 bar and a WHSV of 0.26 kg / L h DMAPN up to 0.4 kg / L • h DMAPN operated.
  • the DMAPN conversion was complete, the DMAPA yield was 99.0 to 99.7%.
  • the proportion of bis-DMAPA was accordingly less than 1%.
  • Catalyst precursor prepared according to Example 1b was reduced as in Example 6a, treated with lithium hydroxide solution and then rinsed with tetrahydrofuran.
  • the hydrogenation of DMAPN was carried out in the apparatus described in Example 6a. She was operated for 300 hours in the absence of ammonia at 120 0 C in the upflow mode, a pressure range of 30 to 50 bar and a WHSV of 0.26 kg / L • h DMAPN. The DMAPN conversion was complete, the DMAPA yield was> 99.8%.
  • the passivated catalyst precursor prepared according to Example 2 starting from cordierite, gamma-aluminum oxide and LiCoO 2 was activated in the bubble column at 130 0 C and 50 bar for 18 hours with hydrogen. Then without washing or other aftertreatment of the monolith DMAPN was continuously pumped at 120 0 C and 50 bar in the upflow mode in the absence of ammonia in the reactor.
  • the WHSV was 0.26 kg / L • h DMAPN. These conditions were maintained for 75 hours. In this time, the conversion was complete, the yield was 99.9%. These values remained constant even after lowering the pressure to 30 bar for the next 50 hours. In the following 200 hours under otherwise constant conditions, the WHSV was gradually increased from 0.26 kg / L • h DMAPN to 1.
  • Example 2 For the hydrogenation of suberonitrile to octamethylenediamine a prepared analogously to Example 2, coated with LiCoÜ2 monolith catalyst was used. Cordierite from Corning was used as a monolithic catalyst support in the form of structured moldings (round, 18 ⁇ 50 mm) and 400 cpsi. The cobalt content of the monolith strands was 24 to 29 wt .-%, the lithium content 2 to 4 wt .-%. The catalyst precursor was reduced for 10 hours at 300 0 C with a mixture of 90% hydrogen and 10% nitrogen and then passivated with air at room temperature. The passivated monolith strands were then incorporated into 1 1 holes provided a holder, so that the Holes were completely filled by the monolith strands.
  • the holder with the monoliths was placed in a 160 ml Parr autoclave (hte) - with magnetically coupled disc stirrer (stirrer speed 1000 revolutions / minute), electric heating, internal temperature measurement and hydrogen supply via iterative differential pressure Dosage - built-in.
  • the activation of the passivated catalyst was carried out before the nitrile hydrogenation at 150 ° C / 100 bar for 12 hours with hydrogen while stirring the monolithic catalysts in THF.
  • the autoclave 1 monolith catalyst strands were installed, 43 g of cork dinitrile and 43 g of methanol filled. Hydrogenation was for 3 hours at 100 0 C and 65 bar.
  • the gas chromatographic analysis of the hydrogenation yielded an octamethylene diamine selectivity of 95.9% with a suberic acid conversion of 99.4%.
  • a catalyst precursor prepared according to Example 3 was reduced for 10 hours at 300 ° C. with a mixture of 90% hydrogen and 10% nitrogen and then passivated with air at room temperature.
  • the passivated monolith strands were then holes of a holder provided in 1 liter installed so that the holes were completely filled by the monolith strands.
  • the holder with the monoliths was placed in a 160 ml Parr autoclave (hte) - with magnetically coupled disc stirrer (stirrer speed 1000 revolutions / minute), electric heating, internal temperature measurement and hydrogen supply via iterative differential pressure Dosage - built-in.
  • the activation of the passivated catalyst was carried out before the nitrile hydrogenation at 150 ° C / 100 bar for 12 hours with hydrogen while stirring the monolithic catalysts in THF.
  • the holder with the activated cobalt monolith catalysts (1 wt .-% cobalt) was removed from the autoclave and rinsed with THF.
  • the support was then either incorporated into the reactor without further treatment (Example 8a) or stored for 30 minutes at room temperature in an aqueous, 0.065 molar or 0.85 molar solution of the alkali hydroxide LiOH (Example 8b or Example 8c) monolithic catalysts were completely wetted with the solution (imticiangntechnik).
  • Example 5 Analogously to Example 5, a NiO-coated monolith catalyst prepared according to Example 4 was used for the conversion of DMAPN to DMAPA under otherwise unchanged reaction conditions. Unlike Example 5, the reaction was carried out for 6 hours.
  • the holder with the activated nickel monolith catalysts (8.6 wt .-% nickel) was removed from the autoclave and rinsed with THF.
  • the support was then either incorporated into the reactor without further treatment (Example 9a) or stored for 30 minutes at room temperature in an aqueous 0.85 molar solution of the alkali hydroxide LiOH (Example 9b), the monolithic catalysts being completely wetted with the solution ( Impregnation).
  • the results are shown in Table 3.

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Abstract

L'invention concerne des catalyseurs et des procédés de préparation de ceux-ci, les catalyseurs pouvant être obtenus par mise en contact d'un support de catalyseur monolithique avec une suspension contenant un ou plusieurs composés, insolubles ou peu solubles, des éléments choisis dans le groupe des éléments cobalt, nickel et cuivre. L'invention concerne également l'utilisation du catalyseur selon l'invention dans un procédé d'hydrogénation de substances organiques, notamment d'hydrogénation de nitriles, et un procédé d'hydrogénation de composés organiques, caractérisé en ce qu'il fait intervenir un catalyseur selon l'invention.
EP10701552A 2009-02-09 2010-02-01 Catalyseurs d'hydrogénation, préparation et utilisation Withdrawn EP2393591A2 (fr)

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US8710269B2 (en) 2010-07-29 2014-04-29 Basf Se DMAPN having a low DGN content and a process for preparing DMAPA having a low DGN content
US8933223B2 (en) 2010-10-14 2015-01-13 Basf Se Process for preparing a cyclic tertiary amine
CN104364243B (zh) 2012-06-01 2017-03-08 巴斯夫欧洲公司 生产单‑n‑烷基哌嗪的方法
US8884015B2 (en) 2012-06-01 2014-11-11 Basf Se Process for the preparation of a mono-N-alkypiperazine
US8981093B2 (en) 2012-06-06 2015-03-17 Basf Se Process for preparing piperazine
CN103664638B (zh) * 2013-12-31 2016-04-13 张锦碧 一种异佛尔酮二胺的简易制备方法
JP2019532059A (ja) * 2016-09-23 2019-11-07 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Ｃｏの存在下およびモノリシック触媒成形体を含む触媒固定床の存在下で有機化合物を水素化する方法
WO2018114777A1 (fr) * 2016-12-19 2018-06-28 F. Hoffmann-La Roche Ag Catalyseurs à base de biopolymères contenant de l'azote, leur préparation et leurs utilisations dans des procédés d'hydrogénation, déshalogénation réductrice et oxydation
CN106784898B (zh) * 2017-03-03 2019-10-18 北京化工大学 一种锂钴氧化物与碳黑共混型催化剂及其制备方法和应用
WO2020069972A1 (fr) 2018-10-02 2020-04-09 Basf Se Processus pour mettre en oeuvre des réactions chimiques en phase fluide en présence de films comprenant des particules de catalyseur
EP3865210A1 (fr) * 2020-02-14 2021-08-18 BASF Corporation Catalyseur d'hydrogénation à base de nickel sur support d'aluminium et silicium, son précurseur, leurs procédés de préparation, et procédé d'hydrogénation de résines pétrochimiques utilisant ce catalyseur
CN114380699B (zh) * 2022-01-26 2023-07-04 山东新和成维生素有限公司 一种合成异佛尔酮二胺的方法、催化剂及其制备方法
CN115869960A (zh) * 2022-12-16 2023-03-31 南京红宝丽醇胺化学有限公司 一种Ni-Co-Ce-Cr催化剂及其制备方法与应用

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US20110313186A1 (en) 2011-12-22

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