EP1996322A1 - Catalyseurs a base d'oxydes mixtes - Google Patents

Catalyseurs a base d'oxydes mixtes

Info

Publication number
EP1996322A1
EP1996322A1 EP07726607A EP07726607A EP1996322A1 EP 1996322 A1 EP1996322 A1 EP 1996322A1 EP 07726607 A EP07726607 A EP 07726607A EP 07726607 A EP07726607 A EP 07726607A EP 1996322 A1 EP1996322 A1 EP 1996322A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogenation
catalysts
catalyst precursor
preparation
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Withdrawn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
EP07726607A
Other languages
German (de)
English (en)
Inventor
Martin Ernst
Thilo Hahn
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07726607A priority Critical patent/EP1996322A1/fr
Publication of EP1996322A1 publication Critical patent/EP1996322A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
    • C07C2523/04—Alkali metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to catalysts prepared by reduction of catalyst precursors containing a) cobalt and b) one or more elements of the alkali metal group, the alkaline earth metal group, the rare earth element or zinc or mixtures thereof, wherein elements a) and b ) are present at least partly in the form of their mixed oxides. Furthermore, the present invention relates to processes for the preparation of these catalysts and their use for hydrogenation. The present invention also relates to a process for the regeneration of these catalysts.
  • Cobalt catalysts are generally prepared by calcination and reduction of catalyst precursors, such as cobalt hydroxide, cobalt nitrate and cobalt oxide, or in the form of cobalt sponge catalysts (Raney cobalt) in hydrogenation reactions.
  • catalyst precursors such as cobalt hydroxide, cobalt nitrate and cobalt oxide, or in the form of cobalt sponge catalysts (Raney cobalt) in hydrogenation reactions.
  • Cobalt-containing catalysts can furthermore be prepared by reducing cobalt oxide, cobalt hydroxide or cobalt carbonate.
  • catalysts which contain metallic cobalt and / or nickel particles which are obtainable from cobalt and / or nickel oxide particles by contact with hydrogen. According to this disclosure, the content of alkali and / or alkaline earth is advantageously less than 0.1% by weight.
  • EP-B-0742045 describes cobalt catalysts obtained by calcination of the oxides of the elements cobalt (55-98% by weight), phosphorus (0.2 to 15% by weight), manganese (0.2 to 15% by weight) Wt .-%) and alkali (0.05 to 5 wt .-%) and subsequent reduction in the hydrogen stream are produced.
  • Cobalt catalysts obtainable by precipitation of cobalt carbonate from an aqueous solution of a cobalt salt and subsequent reduction with hydrogen are set forth in EP-A-0 322 760.
  • these catalysts may contain 0.25 to 15% by weight, based on the total mass of catalyst, SiO 2, MnO 2, ZrO 2, Al 2 O 3 and MgO in the form of the oxides, hydroxides or oxide hydrates.
  • hydrogenation catalysts which consist of one or more oxides of the elements Fe, Ni, Mn, Cr, Mo, W and P and one or more oxides of the alkali, alkaline earth and the rare earth group are described in EP-BO 445,589. Apparently, the oxides after reduction are partially present as metals.
  • improved hydrogenation catalysts should be provided which offer advantages over conventional processes.
  • metals such as.
  • Another object of the present invention was to find catalysts which allow the hydrogenation of organic compounds under simplified reaction conditions. Thus, catalysts should be found which allow the hydrogenation reaction to be carried out at lower pressures.
  • hydrogenation processes should be accessible, which can be carried out in the absence of water, ammonia and aqueous base.
  • the catalyst is obtainable by using a catalyst precursor comprising 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) at least in part in the form of their mixed oxides, reduced.
  • a mixed oxide is characterized in that the crystal lattice in addition to cobalt and oxygen at least one further element b) from the group alkali or alkaline earth metals or the group of rare earths or zinc.
  • element b) occupy a lattice site (substitution mixed crystal) or an interstitial site (intercalation crystal) instead of cobalt,
  • solid solutions ie continuous series of mixed crystals
  • a mixture of oxides or an oxide mixture differs from the mixed oxide present according to the invention in that in the case of a mixture of oxides or oxides
  • the fact that the mixed oxide according to the invention is present can be detected analytically, for example by means of X-ray diffractometry, in which the crystal structures of the cobalt oxide and of the oxides of the elements b) are present next to one another in comparison with reference spectra in crystallographic databases [ICSD (Inorganic Crystal Structure Database), Bergerhoff et al, University of Bonn (D) or Powder Diffraction File, Berry et al., International Center for Diffraction Data (ICDD), Swarthmore (USA)]
  • the catalyst precursors for the preparation of erfindungsmä touch catalysts we used As explained above, some of them are present as mixed oxide containing cobalt and at least one of the elements b) listed above.
  • the catalyst precursors are partly as mixed oxides of Co and Li, as mixed oxides of Co and Na, as mixed oxides of Co and K, as mixed oxides of Co and Rb, as mixed oxides of Co and Cs, as mixed oxides of Co and Be, as mixed oxides of Co and Mg, as mixed oxides of Co and Ca, as mixed oxides of Co and Sr, as mixed oxides of Co and Ba, as mixed oxides of Co and La, as mixed oxides of Co and Y and as mixed oxides of Co and Zn.
  • the catalyst precursors are present in part as mixed oxides of Co and Li, as mixed oxides of Co and Mg, and as mixed oxides of Co and Zn, and most preferably the catalyst precursors are partly mixed oxides of Co and Li and mixed oxides of Co and Mg in front.
  • the catalyst precursors which are used for the preparation of the catalysts of the invention partly as mixed oxides of Li, Na and Co, as mixed oxides of Li, K and Co, as mixed oxides of Li, Mg and Co, as mixed oxides of Li, Ca and Co, as mixed oxides of Na, Mg and Co, as mixed oxides of K, Mg and Co, as mixed oxides of Na, Ca and Co and as mixed oxides of K, Ca and Co.
  • the catalyst precursor having the empirical formula LiCoO 2 (lithium cobaltite) LiCoO 2 may be in the form of the cryogenic phase (LT -LiCo ⁇ 2), the high-temperature phase (HT-UCOO2) or as a mixture of both.
  • the catalyst precursor used is lithium cobaltite, which is obtained by the recycling of batteries.
  • the catalyst precursors according to the invention are present partly in the form of their mixed oxides. However, the catalyst precursors can also be present exclusively in the form of their mixed oxides.
  • the proportion of cobalt in the catalyst precursor present in the form of mixed oxides is preferably at least 10 mol%, advantageously at least 20 mol% and particularly preferably at least 30 mol%, in each case based on the total cobalt present in the catalyst precursor.
  • the catalyst precursor contains one or more additional components in addition to one or more mixed oxides.
  • additional components elemental oxides may be included.
  • oxides of the elements of the first to fifth main group or oxides of the elements of the third to eighth subgroup may be suitable, in particular oxides of the elements Co, Ni, Cu, Mn, P, Cr, Ag, Fe, Zr, Al, Ti , Li, Na, K, Mg, Ca, Zr, La or Y.
  • the catalyst precursor may contain one or more dopants.
  • Suitable doping elements are the elements of the 3rd to 8th subgroup of the Periodic Table of the Elements (in the version of 03.10.2005 of IUPAC
  • Preferred dopants are Fe, Ni, Cr, Mn, P, Ti, Nb, V, Cu, Ag, Pd, Pt, Rh, Ir, Ru and Au.
  • the doping elements are preferably present in amounts of not more than 10% by weight, for example from 0.1 to 10% by weight, more preferably in amounts of from 1 to 5% by weight, in each case based on the catalyst precursor used.
  • Catalyst precursors can generally be obtained by thermal treatment of the corresponding compounds of cobalt and one or more compounds of the alkali metal group, compounds of the alkaline earth metal group, compounds of the rare earth group or compounds of zinc, for example the nitrates, carbonates, hydroxides, oxides , Acetates, oxalates or citrates.
  • Thermal treatment may be understood, for example, as the fusing or calcination of the above compounds.
  • the thermal treatment of the abovementioned compounds, such as the nitrates, carbonates, hydroxides, oxides can be carried out in air.
  • the thermal treatment, in particular of the carbonates takes place under an inert gas stream. The atmosphere.
  • Suitable inert gases include, for example, nitrogen, carbon dioxide, helium, neon, argon, xenon, krypton or mixtures of said inert gases.
  • nitrogen is suitable.
  • the preparation of the catalyst precursors by thermal treatment of the abovementioned compounds under an inert gas atmosphere has the advantage that the subsequent reduction of the catalyst precursor can be connected directly to the thermal treatment described above. If the catalyst precursor is not prepared under an inert gas atmosphere, an additional inerting step should be carried out prior to reduction. In the inerting step, interfering compounds, such as atmospheric oxygen, which can react with the reducing agent in the reduction, for example by gassing the catalyst precursor with inert gas or by repeated evacuation and venting with inert gas can be removed.
  • Another method of preparing the catalyst precursors is to precipitate water-soluble cobalt compounds and at least one or more of water-soluble alkali compounds, water-soluble alkaline earth compounds, water-soluble rare earth compounds and water-soluble zinc compounds, by adding an alkaline solution and then drying calcination.
  • LiCoO 2 Methods of producing LiCoO 2 are e.g. in Antolini [E. Antolini, Solid State Ionics, 159-171 (2004)] and Fenton et al. [W. M. Fenton, P.A. 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, followed by calcination.
  • LiCoO 2 can also be obtained by the sol-gel method.
  • LiCoO 2 may also be prepared as described by Song et al. [S. W. Song, K.S. Han, M. Yoshimura, Y. Sata, A. Tatsuhiro, Mat. Res. Soc. Proc., 606, 205-210 (2000)], by hydrothermal treatment of cobalt metal with LiOH aqueous solutions.
  • LiCo ⁇ 2 which is obtained by the reprocessing of batteries.
  • a method for recycling or recovering lithium cobaltite from waste batteries can be derived, for example, from CN 1594109. By mechanically opening the battery terie and the extraction of aluminum components with conc. NaOH, a Li-Co ⁇ 2-rich filter cake can be obtained.
  • a washing step or a washing step with subsequent drying may follow before the reduction.
  • the wash step removes impurities, by-products or unreacted starting materials.
  • the catalyst precursor may, as previously described, contain one or more dopants.
  • dopants can be incorporated by the addition of metal complexes and metal salts such as metal carbonates and metal oxides, or the metals themselves in the preparation of the catalyst precursor by fusing together the corresponding oxides or carbonates or mixtures thereof.
  • the dopants can be introduced via a precipitation reaction as water-soluble salts and complexes which are mixed with a precipitation reagent.
  • the catalyst already prepared by the reduction of a catalyst precursor can still be doped in the same way. In this case, the catalyst precursor and / or the catalyst may already be doped with doping elements.
  • the catalyst precursor generally obtained in powder form can be subjected to shaping before the reduction or can be absorbed (supported) on porous and surface-active materials.
  • shaping and carrying Common methods of shaping and carrying are described, for example, in Ullmann [Ullmann's Encyclopedia Electronic Release 2000, Chapter: 'Catalysis and Catalysts', S28-32].
  • suitable substances can be applied to a support and reacted there, the catalyst precursor being formed.
  • the reduction of the catalyst precursor can be carried out in a liquid in which the catalyst precursor is suspended.
  • the reduction in the liquid may be e.g. in a stirred autoclave, a packed bubble column, a circulation reactor or a fixed bed reactor.
  • the reduction can also be carried out dry as a powder in a moving or stationary reduction furnace or in a fixed bed or in a fluidized bed.
  • the reduction of the catalyst precursor is carried out in a liquid in which the catalyst precursor is suspended.
  • suitable liquids for suspending the catalyst precursor are water or organic solvents, for example ethers such as methyl tert-butyl ether, ethyl tert-butyl ether or tetrahydrofuran (THF), alcohols such as methanol, ethanol or isopropanol, hydrocarbons such as hexane, heptane or Raffinatroughe, aromatics such as toluene or amides such as dimethylformamide or dimethylacetamide or lactams, such as N-
  • ethers such as methyl tert-butyl ether, ethyl tert-butyl ether or tetrahydrofuran (THF)
  • alcohols such as methanol,
  • Methylpyrrolidone, N-ethylpryrrolidone, N-methylcaprolactam or N-ethylcaprolactam are also suitable mixtures of the abovementioned solvents.
  • Preferred liquids contain products from the hydrogenation to be carried out. Particular preference is given to liquids which are the product of the hydrogenation to be carried out.
  • the catalyst precursor is suspended in a liquid which contains no water.
  • the temperatures are generally in a range from 50 to 300 ° C, in particular from 100 to 250 ° C, particularly preferably from 120 to 200 ° C.
  • the reduction in suspension is generally carried out at a pressure of 1 to 300 bar, preferably from 10 to 250 bar, more preferably from 30 to 200 bar, wherein the pressure data here and below relate to the absolute measured pressure.
  • Suitable reducing agents are hydrogen or a hydrogen-containing gas or a source of hydride ions.
  • 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.
  • the hydrogen stream can also be recycled as recycle gas into the reduction, possibly mixed with fresh hydrogen and, if appropriate, after removal of water by condensation.
  • the reduction of the dry, usually powdered catalyst precursor can be carried out at elevated temperature in a moving or stationary reduction furnace.
  • the reduction of the catalyst precursor is generally carried out at reduction temperatures of 50 to 600 ° C, in particular from 100 to 500 ° C, particularly preferably from 150 to 400 ° C.
  • the operating pressure is generally from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 10 bar, wherein a stream of hydrogen or a hydrogen-containing stream, as described above still admixing of others Inert gases may be passed through or over the catalyst bed.
  • the hydrogen stream can be recycled as recycle gas in the reduction, optionally mixed with fresh hydrogen and optionally after removal of water by condensation.
  • the reduction is preferably carried out so that the degree of reduction is at least 50%.
  • a comparison is made of the dry-reduced catalyst dry-catalyst-precursor mass decrease, which reduces these samples from room temperature to 900 ° C in a hydrogen-containing gas stream, recording the integral of the mass decrease.
  • a solvent may be supplied to remove the resulting reaction water.
  • the solvent can also be supplied supercritically.
  • Suitable solvents may be the same as those described above for suspending the catalyst.
  • Preferred solvents are ethers such as methyl tert-butyl ether, ethyl tert-butyl ether or tetrahydrofuran, alcohols such as methanol, ethanol or isopropanol, hydrocarbons such as hexane, heptane or Raffinatroughe, aromatics such as toluene or amides such as dimethylformamide or dimethylacetamide or lactams such as N-methylpyrrolidone, N-ethylpyrrolidone , N-methylcaprolactam or N-ethylcaprolactam.
  • ethers such as methyl tert-butyl ether, ethyl tert-butyl ether or tetrahydrofuran
  • alcohols such as methanol, ethanol or isopropanol
  • hydrocarbons such as hexane,
  • Suitable suitable solvents are also suitable mixtures.
  • the above-mentioned reaction conditions for the reduction of the catalyst precursor generally apply, eg for stirred autoclave, fluidized bed or fixed bed process.
  • the catalyst of the invention may also be prepared by reduction with a source of hydride ion in a solvent starting from the catalyst precursor.
  • Suitable hydride ion sources are complex hydrides such as LiAlH 4 or NaBH 4 .
  • Suitable solvents are ethers such as methyl tert-butyl ether, ethyl tert-butyl ether or tetrahydrofuran, hydrocarbons such as hexane, heptane or Raffinatroughe or aromatics such as toluene. Particularly preferred is tetrahydrofuran.
  • Suitable suitable solvents are also suitable mixtures.
  • the reduction of the catalyst precursor may preferably be carried out to a degree of reduction of 50 to 100%.
  • the catalyst may be handled and stored after reduction 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.
  • 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 nitrogen with an oxygen-containing gas stream such as air or a mixture of air with nitrogen, ie provided with a protective oxide layer.
  • catalyst refers hereinafter to a catalyst which has been prepared according to the invention by reduction of the catalyst precursor described or a catalyst which has been passivated as described above after activation with an oxygen-containing gas stream.
  • the storage of the catalyst under inert substances or the passivation of the catalyst allow 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 catalysts of the invention can be used in a process for the hydrogenation of compounds containing at least one unsaturated carbon-carbon, carbon-nitrogen or carbon-oxygen bond or the partial or complete nuclear hydrogenation of compounds containing aromatics.
  • 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 containing at least one or more carboxylic acid ester groups, carboxylic acid groups, aldehyde groups or keto groups which are hydrogenated to alcohols can be hydrogenated. 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. These can be hydrogenated to primary amines.
  • Suitable nitriles are acetonitrile for the preparation of ethylamine, propionitrile for the preparation of propylamine, butyronitrile for the preparation of butylamine, lauronitrile for the preparation of laurylamine, stearyl nitrile for the preparation of stearylamine, N 1 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) and / or amino capronitrile (ACN), 2-methylglutarodinitrile for the preparation of 2-methylglutarodiamine, succinonitrile for the preparation of 1, 4-butanediamine and suberonitrile for the preparation of octamethylenediamine.
  • ADN adi podinitrile
  • HMD hexamethylenediamine
  • ACN amino capronitrile
  • 2-methylglutarodinitrile for the preparation of 2-methylglutarodiamine
  • succinonitrile for the preparation of 1, 4-butanediamine and suberonitrile for the preparation of octamethylenediamine.
  • cyclic nitriles such as isophorone nitrile (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 production of diethylenetriamine
  • Dinitrotoluene is also suitable for the preparation of toluidine diamine
  • nitriles are ⁇ -aminonitriles, for example addition products of alkylamines, alkyldiamines or alkanolamines and acrylonitrile
  • 3- [2-aminoethyl) amino] propionitrile can be converted into 3- (2-aminoethyl) aminopropylamine and 3,3 '- (ethylenediimino) bispropionitrile or 3- [2-] ethylenediamine and acrylonitrile to give the corresponding diamines.
  • (3-Amino-propylamino) ethylamino] -propionitrile to N, N'-bis (3-aminopropyl) ethylenediamine.
  • N, N-dimethylaminopropionitrile DMAPN
  • DMAPA N, N-dimethylaminopropylamine
  • ADN adiponitrile
  • reducing agent hydrogen, a hydrogen-containing gas or a hydride ion source can be used.
  • the hydrogen used for the hydrogenation is generally used in the larger stoichiometric excess of from 1 to 25 times, preferably from 2 to 10 times or stoichiometric amounts. It can be recycled as recycle gas into the reaction.
  • 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.
  • the hydrogenation can also be carried out with a hydride ion source.
  • Suitable hydride ion sources are complex hydrides such as LiAlH 4 or NaBH 4
  • the hydrogenation can be carried out with the addition of ammonia.
  • ammonia is used in molar ratios to the nitrile group in the ratio of 0.5: 1 to 100: 1, preferably 2: 1 to 20: 1.
  • the preferred embodiment is a method in which no ammonia is added.
  • the hydrogenation can be carried out in the presence of a liquid.
  • the liquid may be the same liquid in which, as previously described, the catalyst precursor has been reduced or suspended.
  • Suitable liquids are, for example, C 1 - to C 4 -alcohols, C 1 - to C 12 -dialkyl ethers or cyclic C 4 - to C 12 -ethers, such as tetrahydrofuran or tert-butylmethyl ether. Suitable liquids may also be mixtures of the abovementioned liquids. The liquid may also be the product of the hydrogenation. In a preferred embodiment, the hydrogenation is carried out in an anhydrous liquid.
  • 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.
  • the hydrogenation is carried out directly after the reduction of the catalyst precursor in the same reactor in which the reduction was carried out.
  • the hydrogenation is generally carried out at a pressure of from 1 to 300 bar, in particular from 5 to 200 bar, preferably from 8 to 85 bar and particularly preferably from 10 to 65 bar.
  • 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 40 to 250 ° C, in particular from 60 to 160 ° C, preferably from 70 to 150 ° C, particularly preferably from 80 to 130 ° C.
  • the hydrogenation may be e.g. in the liquid phase in a stirred autoclave, a bubble column, a circulation reactor such as a jet loop or a fixed bed reactor.
  • the catalyst can be separated from the product by methods known to those skilled in the art, for example filtration or settling.
  • 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 Encyclopedia Electronic Release 2000, Chapter: Hydrogenation and Dehydrogenation, S2-3].
  • the hydrogenation is preferably carried out in suspension.
  • the hydrogenation is carried out in the same reaction vessel in which the catalyst precursor is also reduced.
  • the hydrogenation processes can be carried out batchwise, semi-continuously or continuously.
  • the hydrogenation processes are preferably carried out semi-continuously or continuously.
  • 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 carried out at elevated temperature, usually from 20 to 250 ° C. It is also possible to dry the used catalyst and to oxidize air-adhering organic compounds 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 in the regeneration, can be post-doped with a compound of elements b).
  • the post-doping can be carried out in such a way that the catalyst is impregnated or wetted with a water-soluble base of the element b).
  • 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 is also carried out in the absence of water and ammonia ak can be operated, eliminating or simplify process steps for the separation of water and ammonia from the reaction product (distillation).
  • the absence of water and ammonia makes it possible to make better use of the existing reactor volume, since the volume released can be used as an additional reaction volume.
  • catalyst particles of small size and high surface area can be obtained.
  • Catalyst loading is reported as the quotient of product amount and the product of catalyst mass and time.
  • Catalyst load amount of product / (catalyst mass • reaction time)
  • the unit of catalyst loading is given in [kgp domestic product ro / (kg ⁇ at h)] or [gp ro domestic product / (g ⁇ at h)] Toggle.
  • 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 Fcetures, ie the sum of the area below the signals i, multiplied by 100, yields:
  • the area percentages refer to the total area without the area below the DMA signal.
  • ADN adiponitrile
  • HMD hexamethylenediamine
  • Examples 1 and 2 demonstrate the high performance of the catalysts according to the invention, which were prepared from the catalyst precursor LiCoO 2 , over a long period of time. longer period. Furthermore, it could be shown that the Li contained in the precursor stage is not converted by the reduction in a soluble form and discharged in a continuous process. Another advantage evident from the examples is the fact that the catalyst can be activated in standard equipment under mild conditions. The water present at the beginning of the experiment is not required for the activity of the catalysts according to the invention, because it is removed continuously and yet the catalyst remains active.
  • the catalyst (3A) was then used to carry out the tests 3.1 to 3.5 listed in Table 1.
  • Example 3 shows that very different selectivities containing unsaturated carbon-carbon, carbon-nitrogen or carbon-oxygen bonds can be hydrogenated with very good selectivities.
  • Example 4 shows that very different selectivities containing unsaturated carbon-carbon, carbon-nitrogen or carbon-oxygen bonds can be hydrogenated with very good selectivities.
  • Example 4 shows that the catalyst doped with Ni has a lower activity, but a higher selectivity in the hydrogenation of DMAPN than the undoped catalyst from Example 1A).
  • Example 5 and Comparative Example 1 show that the catalyst prepared by reducing a catalyst precursor containing the mixed oxide structure of the present invention has advantages over a catalyst prepared by reducing a catalyst precursor consisting of pure cobalt oxide.
  • the productivity of the catalyst of the present invention was far higher than that of the catalyst made from the pure co-oxide catalyst precursor. Even after 6 h post-hydrogenation time, this catalyst did not yet reach the conversion which had already been achieved after 6 h in the case of LiCoO 2, even though the reduction temperature had been higher by 50 ° C.
  • Powdered magnesium carbonate and cobalt (II) carbonate hydrate (CAS 513-79-1) were intensively mixed in a ratio of 0.5: 1 [mol of Mg: mol of Co] and calcined in air in an oven. This was heated to 400 ° C in 2 h and held this temperature for 2 h.
  • the oxide catalyst precursor thus obtained shows diffraction signals of CoO / MgO mixed crystals and a spinel structure in the XRD (X-ray diffraction).
  • the powder obtained from the cocination (Example 6A) was gassed with a gas stream of 90% by volume of N 2 and 10% by volume of H 2 in a heated nitrogen-inert reduction oven and heated to 300 ° C. over the course of 2 hours, 16 hours reduced at this temperature and then cooled. After cooling, the hydrogen-containing atmosphere was replaced with nitrogen. According to X-ray diffraction (XRD), the resulting reduced catalyst contains predominantly cubic and hexagonal cobalt and CoO / MgO.
  • XRD X-ray diffraction
  • the reduced catalyst (6B) thus obtained was used as described below under 6C).
  • Powdered lithium carbonate (CAS 554-13-2) and cobalt (II) carbonate hydrate (CAS 513-79-1) was mixed in a ratio of 1: 1 [mol Li: mol Co] and mixed in one
  • the catalyst precursor thus obtained had a Li: Co ratio of 1: 1 [mokmol] (from elemental analysis) and a surface area of 34 m 2 / g (BET measurement). From the diffraction lines in the X-ray powder diffractogram (XRD, Cu-K-alpha radiation), it was concluded that the main crystalline component of this catalyst precursor is a LiCoO 2 mixed oxide.
  • the powder obtained from the CaI- cination (Example 7A) was gassed with a gas stream of 90 vol.% N2 and 10 vol.% H2 and heated to 300 ° C within 2 h, 16 h at this temperature reduced and then cooled. After cooling, the hydrogen-containing atmosphere was replaced with nitrogen.
  • the reduced catalyst (7B) thus obtained was used as described under 7C).
  • the passivated catalyst thus obtained was used as described under 7D) and 7E).
  • Example 7B The passivated catalyst from Example 7B was used in the continuous hydrogenation of DMAPN in suspension without preactivation. At a hydrogen pressure of 40 bar and 120 ° C, 2.5 wt.% Catalyst and a load of 1, 2 kg DMAPN / (kg ⁇ afh) was the experiment after 400 h at a constant high DMAPN conversion> 99.9% with consistent high selectivity of 99.5% terminated without signs of deactivation.
  • Example 7 shows that the catalyst can be used completely reduced or passivated, whereby a separate activation of the passivated catalyst before the start of the hydrogenation is not absolutely necessary.
  • Example 7 also shows that the catalyst is also suitable for use in continuous processes.
  • Powdered lithium carbonate (CAS 554-13-2) and cobalt (II) carbonate hydrate (CAS 513-79-1) was intensively mixed in a ratio of 0.8: 1 [mol Li: mol Co] and calcined in air in an oven , This was heated to 400 ° C in 2 h and held this temperature for 2 h. From the diffraction lines of the thus obtained catalyst precursor (8A) in the X-ray powder diffractogram (XRD, Cu-K-alpha radiation), it was concluded that in addition to the main crystalline component, a non-stoichiometric Li x CO (i + ⁇ / 3) ⁇ 2 mixed oxide , there is still some CO3O4 present
  • the catalyst precursor (8A) obtained from the ca ⁇ ination was gassed with a gas stream of 90% by volume N 2 and 10% by volume of H 2 and heated to 300 ° C. within 2 hours, 16 h this temperature is reduced and then cooled. After cooling, the hydrogen atmosphere was replaced with nitrogen.
  • the resulting reduced catalyst (8B) was used as described under C).
  • Example 8 clarifies that catalyst precursors, which for the most part but not exclusively consist of a mixed oxide, are suitable according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne des catalyseurs obtenus par réduction de précurseurs de catalyseurs, contenant a) du cobalt et b) un ou plusieurs éléments du groupe des métaux alcalins, du groupe des métaux alcalino-terreux, du groupe des terres rares ou du zinc ou des mélanges de ces éléments, les éléments a) et b) étant présents au moins en partie sous forme de leurs oxydes mixtes. L'invention concerne également un procédé de fabrication de ces catalyseurs et leur utilisation pour l'hydrogénation de composés organiques insaturés. L'invention concerne également un procédé de régénération de ces catalyseurs par traitement des catalyseurs avec un liquide.
EP07726607A 2006-03-10 2007-03-02 Catalyseurs a base d'oxydes mixtes Withdrawn EP1996322A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07726607A EP1996322A1 (fr) 2006-03-10 2007-03-02 Catalyseurs a base d'oxydes mixtes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06110972 2006-03-10
EP07726607A EP1996322A1 (fr) 2006-03-10 2007-03-02 Catalyseurs a base d'oxydes mixtes
PCT/EP2007/052013 WO2007104663A1 (fr) 2006-03-10 2007-03-02 Catalyseurs a base d'oxydes mixtes

Publications (1)

Publication Number Publication Date
EP1996322A1 true EP1996322A1 (fr) 2008-12-03

Family

ID=37913587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07726607A Withdrawn EP1996322A1 (fr) 2006-03-10 2007-03-02 Catalyseurs a base d'oxydes mixtes

Country Status (6)

Country Link
US (1) US20090149314A1 (fr)
EP (1) EP1996322A1 (fr)
JP (1) JP2009529419A (fr)
CN (1) CN101400442B (fr)
RU (1) RU2434676C9 (fr)
WO (1) WO2007104663A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101842346B (zh) 2007-08-29 2013-05-15 巴斯夫欧洲公司 由糖醇生产胺的方法
RU2480449C2 (ru) * 2007-08-29 2013-04-27 Басф Се Способ получения аминов из глицерина
EP2279164B1 (fr) * 2008-05-13 2012-03-28 Basf Se Procédé de production de 1,3-propanediamines à substitution n,n
US7854222B2 (en) * 2008-06-26 2010-12-21 General Electric Company Pyrocatalytic coatings for heating devices
WO2010026920A1 (fr) * 2008-09-08 2010-03-11 三菱瓦斯化学株式会社 Procédé de production de xylylènediamine
RU2522761C2 (ru) 2008-11-05 2014-07-20 Басф Се Способ получения n, n-замещенных 3-аминопропан-1-олов
JP2012517333A (ja) 2009-02-09 2012-08-02 ビーエーエスエフ ソシエタス・ヨーロピア モノリス触媒の触媒活性を改善する方法
US20110313187A1 (en) 2009-02-09 2011-12-22 Christof Wilhelm Wigbers Method for improving the catalytic activity of monolithic catalysts
US20110313186A1 (en) 2009-02-09 2011-12-22 Basf Se Hydrogenation catalysts, the production and the use thereof
EP2412698B1 (fr) * 2010-07-29 2012-11-21 Basf Se DMAPN ayant une teneur réduite en DGN et procédé de fabrication de DMAPA à partir de DMAPN ayant une teneur réduite en DGN
KR20150036632A (ko) * 2012-07-19 2015-04-07 인비스타 테크놀러지스 에스.에이 알.엘. 수소화 촉매의 재생
RU2495020C1 (ru) * 2012-10-22 2013-10-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) Способ получения 2-(2-амино)алкиладамантанов
US9981904B2 (en) 2014-08-28 2018-05-29 Basf Se Process for preparing primary amines using an unsupported cobalt catalyst
CN113461539B (zh) * 2021-08-02 2023-11-21 江苏扬农化工集团有限公司 一种从氨基腈类有机物制备有机二胺的方法
CN114927760A (zh) * 2022-05-30 2022-08-19 深圳澳睿新能源科技有限公司 含氰基脂肪胺类化合物非水电解液、锂离子电池及其应用

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE758296A (fr) * 1969-11-07 1971-04-01 Rhodiatoce Procede de fabrication d'hexamethylenediamine
US4375003A (en) * 1978-07-13 1983-02-22 Nalco Chemical Company Method for the hydrogenation of nitriles to primary amines
DE3403377A1 (de) * 1984-02-01 1985-08-01 Basf Ag, 6700 Ludwigshafen Geformte katalysatormassen, deren herstellung und verwendung
DE3744507A1 (de) * 1987-12-30 1989-07-13 Hoechst Ag Verfahren zur herstellung von kobaltkatalysatoren
DE4006979A1 (de) * 1990-03-06 1991-09-12 Basf Ag Verfahren zur herstellung von 1,4-alkylendiaminen
US5151543A (en) * 1991-05-31 1992-09-29 E. I. Du Pont De Nemours And Company Selective low pressure hydrogenation of a dinitrile to an aminonitrile
DE4325847A1 (de) * 1993-07-31 1995-02-02 Basf Ag Kobaltkatalysatoren
ES2169169T3 (es) * 1995-05-09 2002-07-01 Basf Ag Catalizadores de cobalto.
US5636437A (en) * 1995-05-12 1997-06-10 Regents Of The University Of California Fabricating solid carbon porous electrodes from powders
DE19630788C1 (de) * 1996-07-31 1997-09-11 Basf Ag Verfahren zur Herstellung von NH¶2¶-Gruppen enthaltenden Verbindungen
US5874625A (en) * 1996-11-04 1999-02-23 Henkel Corporation Process to hydrogenate organic nitriles to primary amines
FR2778661B1 (fr) * 1998-05-15 2000-06-16 Rhone Poulenc Fibres Procede de preparation d'aminonitrile et de diamine
BR9916490A (pt) * 1998-12-22 2001-12-18 Solutia Inc Reator de amina de baixa pressão
US20010022960A1 (en) * 2000-01-12 2001-09-20 Kabushiki Kaisha Toyota Chuo Kenkyusho Hydrogen generating method and hydrogen generating apparatus
GB0011798D0 (en) * 2000-05-16 2000-07-05 Canon Kk Database annotation and retrieval
US6746794B2 (en) * 2001-06-12 2004-06-08 Tech Drive, Inc Thermal runaway inhibitors
DE10152135A1 (de) * 2001-10-23 2003-04-30 Basf Ag Cobalt-Trägerkatalysatoren für Nitrilhydrierungen
JP4421201B2 (ja) * 2002-03-27 2010-02-24 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー 触媒を調製する方法、触媒、および触媒の使用
JP2004031165A (ja) * 2002-06-26 2004-01-29 Sony Corp 非水電解質電池
US6660887B1 (en) * 2002-12-23 2003-12-09 Solutia Inc. Low pressure process for manufacture of 3-dimethylaminopropylamine (DMAPA)
US7314682B2 (en) * 2003-04-24 2008-01-01 Uchicago Argonne, Llc Lithium metal oxide electrodes for lithium batteries

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007104663A1 *

Also Published As

Publication number Publication date
RU2434676C2 (ru) 2011-11-27
WO2007104663A1 (fr) 2007-09-20
RU2008140041A (ru) 2010-04-20
RU2434676C9 (ru) 2012-12-27
CN101400442A (zh) 2009-04-01
US20090149314A1 (en) 2009-06-11
JP2009529419A (ja) 2009-08-20
CN101400442B (zh) 2013-01-09

Similar Documents

Publication Publication Date Title
WO2007104663A1 (fr) Catalyseurs a base d'oxydes mixtes
EP0053818B1 (fr) Procédé pour la préparation de cyclohexylamines par hydrogénation d'amines aromatiques
EP2155386B1 (fr) Procédé pour la préparation d'amines
WO2010089346A2 (fr) Procédé d'amélioration de l'activité catalytique de catalyseurs monolithiques
EP1841530A1 (fr) Amination directe d'hydrocarbures
WO2010089266A2 (fr) Procédé pour améliorer l'activité catalytique de catalyseurs monolithiques
EP2352719B1 (fr) Procédé de fabrication de 3-aminopropan-1-ols n,n-substitués
EP1058677B1 (fr) Procede d'hydrogenation de dinitriles alpha, omega aliphatiques
DE19909177A1 (de) Katalysator zur Hydrierung funktioneller Gruppen und Verfahren zu seiner Herstellung
EP2393591A2 (fr) Catalyseurs d'hydrogénation, préparation et utilisation
EP2046721A1 (fr) Amination directe d'hydrocarbures
EP2279164B1 (fr) Procédé de production de 1,3-propanediamines à substitution n,n
EP0931058B1 (fr) Catalyseurs convenant a la preparation d'alpha, omega-aminonitriles aliphatiques par hydrogenation partielle de dinitriles aliphatiques
JP2871874B2 (ja) １，４−アルキレンジアミンの製法
EP0503347B1 (fr) Procede pour la production d'un mélange contenant des cyclohexylamines éventuellement substituées et des dicyclohexylamines éventuellement substituées par l utilisation d ùn catalyseur à base de palladium /Al2O3.
WO2010012672A2 (fr) Procédé de production de diamines à partir de lactames
DE19636767A1 (de) Verfahren zur Herstellung von aliphatischen alpha, omega-Aminonitrilen
EP3180308B1 (fr) Procédé de préparation de 2,2-difluoroéthylamine
EP0108323A1 (fr) Procédé pour la préparation de cyclohexylamines N-substituées
DE1542392C (de) Verfahren zur Herstellung von Platinmetallkatalysatoren auf basischen Carbonatträgern
EP3004048A1 (fr) Procédé de production d'aminoacides
DE1542392B (de) Verfahren zur Herstellung von Platin metallkatalysatoren auf basischen Carbonat tragern

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20081010

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20181002