WO2008006750A1 - Verfahren zur herstellung eines amins - Google Patents
Verfahren zur herstellung eines amins Download PDFInfo
- Publication number
- WO2008006750A1 WO2008006750A1 PCT/EP2007/056725 EP2007056725W WO2008006750A1 WO 2008006750 A1 WO2008006750 A1 WO 2008006750A1 EP 2007056725 W EP2007056725 W EP 2007056725W WO 2008006750 A1 WO2008006750 A1 WO 2008006750A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- containing compounds
- catalyst
- calculated
- hydrogen
- Prior art date
Links
- JAEQOSKUYPMJAT-UHFFFAOYSA-N COCCN1CCOCC1 Chemical compound COCCN1CCOCC1 JAEQOSKUYPMJAT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/825—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 gallium, indium or thallium
-
- 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
- B01J23/835—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 germanium, tin or lead
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- 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
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to zirconia and nickel containing catalysts and to a process for producing an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines in the presence of a zirconia and nickel-containing catalyst.
- the process products find inter alia. Use as intermediates in the preparation of fuel additives (US-A-3,275,554, DE-A-21 25 039 and DE-A-36 11 230), surfactants, drugs and crop protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation quaternary ammonium compounds, plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers.
- fuel additives US-A-3,275,554, DE-A-21 25 039 and DE-A-36 11 230
- surfactants drugs and crop protection agents
- hardeners for epoxy resins catalysts for polyurethanes
- intermediates for the preparation quaternary ammonium compounds plasticizers
- corrosion inhibitors synthetic resins
- ion exchangers textile auxiliaries
- dyes dyes
- vulcanization accelerators and / or emulsifiers emuls
- US 4,153,581 (Habermann) relates to the amination of alcohols, aldehydes or ketones by means of specific Co / Cu catalysts containing Fe, Zn and / or Zr.
- US 4,152,353 (Dow) relates to the amination of alcohols, aldehydes or ketones by means of specific Ni / Cu catalysts containing Fe, Zn and / or Zr.
- EP-A1-382 049 discloses catalysts comprising oxygen-containing zirconium, copper, cobalt and nickel compounds and processes for the hydrogenating amination of alcohols.
- the preferred zirconium oxide content of these catalysts is from 70 to 80% by weight (loc.cit: page 2, last paragraph, page 3, 3rd paragraph, examples). Although these catalysts are characterized by a good activity and selectivity, but show improvement in service life.
- EP-A2-514 692 discloses copper, nickel and / or cobalt, zirconium and / or alumina-containing catalysts for the catalytic amination of alcohols in the gas phase with ammonia or primary amines and hydrogen.
- This patent application teaches that in these catalysts, the atomic ratio of nickel to copper must be 0.1 to 1, 0, preferably 0.2 to 0.5 (see loc .. cit .: Example 1), since otherwise in the amination of Alcohols to an increased extent yield-reducing by-products occur (loc cit .: Examples 6 and 12).
- the carrier used is preferably alumina (loc.cit .: Examples 1 to 5 and 7 to 11).
- EP-A1-696 572 and EP-A-697 395 both BASF AG
- nickel, copper, zirconium oxide and molybdenum oxide-containing catalysts for the catalytic amination of alcohols with nitrogen compounds and hydrogen are known. Although high conversions are achieved with these catalysts, by-products can form which disturb the reaction itself or its secondary products.
- EP-A2-905 122 BASF AG describes a process for the preparation of amines from alcohols and nitrogen compounds using a catalyst whose catalytically active composition contains oxygen-containing compounds of zirconium, copper and nickel and no oxygen-containing compounds of cobalt or molybdenum.
- EP-A-1 035 106 (BASF AG) relates to the use of catalysts comprising oxygen-containing compounds of zirconium, copper and nickel for the preparation of amines by aminative hydrogenation of aldehydes or ketones.
- EP-A1-963 975 and EP-A2-1 106 600 (both BASF AG) describe processes for the preparation of amines from alcohols or aldehydes or ketones and nitrogen compounds using a catalyst whose catalytically active composition is 22-40% by weight. (or 22-45 wt .-%) oxygen-containing compounds of zirconium, 1-30 wt .-% oxygen-containing compounds of copper and each 15-50 wt .-% (or 5-50 wt .-%) of oxygen-containing compounds of the Contains nickel and cobalt.
- WO-A-03/076386 and EP-A1-1 431 271 teach catalysts of the above-mentioned. Type for aminations.
- WO-A1-03 / 051508 (Huntsman Petrochemical Corp.) relates to processes for the amination of alcohols using specific Cu / Ni / Zr / Sn-containing catalysts which in another embodiment contain Cr instead of Zr (see page 4, lines 10) - 16).
- European Patent Application No. 06101339.7 of 06.02.06 (BASF AG) describes a process for the preparation of aminodiglycol (ADG) and morpholine by reaction of diethylene glycol (DEG) with ammonia in the presence of a transition metal heterogeneous catalyst, wherein the catalytically active material of the catalyst before the treatment with hydrogen containing oxygen-containing compounds of aluminum and / or zirconium, copper, nickel and cobalt and the shaped catalyst body has specific dimensions.
- DEG diethylene glycol
- the "decarbonylation” is considered in particular as the sum of undesired components (methanol, methoxyethanol, methoxyethylamine, N-methylmorpholine and methoxy-ethyl-morpholine), which according to the reaction network from DEG via methoxyethanol arise:
- aldehydes are used for the amination, this step is omitted.
- the formed or used aldehyde can be aminated by reaction with ammonia or primary or secondary amine with elimination of water and subsequent hydrogenation. This condensation of the aldehyde with the above-mentioned nitrogen compound is presumably catalyzed by acidic centers of the catalyst.
- the aldehyde can also be decarbonylated, ie the aldehyde function is split off as CO.
- Decarbonylation or methanation presumably occurs at a metallic center.
- the CO is hydrogenated on the hydrogenation catalyst to methane, so that the methane formation the extent of Indicating decarbonylation.
- Decarbonylation results in the abovementioned undesired by-products, for example methoxyethanol and / or methoxyethylamine in the abovementioned case.
- the desired condensation of the aldehyde with ammonia or primary or secondary amine and the undesired decarbonylation of the aldehyde are parallel reactions of which the desired condensation is believed to be acid catalyzed, while the undesired decarbonylation is catalyzed by metallic centers.
- Catalysts should be found which are technically easy to prepare and which allow the o.g. Aminations with high conversion, high yield, space-time yields (RZA), selectivity, catalyst life at the same time high mechanical stability of the catalyst molding and lower.
- RZA space-time yields
- the catalysts should have high activity and high chemical and mechanical stability under the reaction conditions.
- a process for producing an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and a nitrogen compound selected from the group consisting of ammonia, primary and secondary amines in the presence of a zirconia and nickel containing catalyst has been found characterized in that the catalytically active material of the catalyst prior to its reduction with hydrogen oxygen-containing compounds of zirconium, copper, nickel and cobalt and oxygen-containing compounds of one or more metals selected from Pb, Bi, Sn, Sb and In contains.
- catalysts which contain oxygen-containing compounds of zirconium, copper, nickel and cobalt and oxygen-containing compounds of one or more metals selected from Pb, Bi, Sn, Sb and In.
- catalysts whose catalytically active material before their reduction with hydrogen in the range of
- oxygen-containing compounds of zirconium calculated as ZrO 2
- ZrO 2 From 10 to 75% by weight of oxygen-containing compounds of zirconium, calculated as ZrO 2, from 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, from 10 to 50% by weight of oxygen-containing compounds of nickel, calculated as NiO, and 10 to 50% by weight of oxygen-containing compounds of cobalt, calculated as CoO, and 0.1 to 10% by weight of oxygen-containing compounds of one or more metals selected from Pb, Bi, Sn, Sb and In, each calculated as PbO, Bi2 ⁇ 3, SnO, Sb2 ⁇ 3 or In2 ⁇ 3, and their use in the above amination, especially in the process for the reaction of DEG with ammonia, found.
- DEG diethylene glycol
- the process can be carried out continuously or discontinuously. Preferred is a continuous driving style.
- the starting materials are targeted, preferably in a circulating gas stream, vaporized and fed to the reactor in gaseous form.
- Suitable amines for a gas-phase synthesis are amines which, because of their boiling points and the boiling points of their educts, can be held in the gas phase within the scope of the process parameters.
- the recycle gas serves to evaporate the reactants and to react as reactants for the amination.
- the starting materials (alcohol, aldehyde and / or ketone, hydrogen and the nitrogen compound) are evaporated in a circulating gas stream and fed to the reactor in gaseous form.
- the educts (alcohol, aldehyde and / or ketone, the nitrogen compound) can also be evaporated as aqueous solutions and passed with the circulating gas stream on the catalyst bed.
- Preferred reactors are tubular reactors. Examples of suitable reactors with recycle gas stream can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. B 4, pages 199-238, "Fixed-Bed Reactors".
- reaction is advantageously carried out in a tube bundle reactor or in a monostane system.
- the tubular reactor in which the reaction takes place can consist of a series connection of several (eg two or three) individual tubular reactors.
- an intermediate feed of feed containing tend educt and / or ammonia and / or H2
- recycle gas and / or reactor discharge from a downstream reactor possible.
- the circulating gas quantity is preferably in the range from 40 to 1500 m 3 (at operating pressure) / [m 3 catalyst (bulk volume) • h], in particular in the range from 100 to 700 m 3 (at operating pressure) / [m 3 catalyst (bulk volume). H].
- the cycle gas preferably contains at least 10, especially 50 to 100, especially 80 to 100, vol.% H 2 .
- the catalysts are preferably used in the form of catalysts which consist only of catalytically active material and optionally a molding aid (such as graphite or stearic acid), if the catalyst is used as a shaped body, ie no further catalytically active impurities contain.
- a molding aid such as graphite or stearic acid
- the oxidic carrier material zirconium dioxide (ZrO 2 ) is considered as belonging to the catalytically active material.
- the catalysts are used in such a way that one introduces the catalytically active, ground to powder mass in the reaction vessel or, that the catalytically active material after grinding, mixing with molding aids, shaping and heat treatment as shaped catalyst body - for example as tablets, spheres, rings, extrudates (eg strands) - arranges in the reactor.
- the concentration data (in wt .-%) of the components of the catalyst are in each case - unless otherwise stated - on the catalytically active composition of the finished catalyst after the last heat treatment and before its reduction with hydrogen.
- the catalytically active mass of the catalyst is defined as the sum of the masses of the catalytically active constituents and the above catalyst support materials and contains essentially the following constituents: zirconium dioxide (ZrO 2 ), oxygen-containing compounds of the Copper, nickel and cobalt and oxygenated compounds of the metals Pb, Bi, Sn, Sb and In.
- the sum of the abovementioned components of the catalytically active composition is usually from 70 to 100% by weight, preferably from 80 to 100% by weight, particularly preferably from 90 to 100% by weight, in particular> 95% by weight, very particularly> 98% by weight, in particular> 99% by weight, for example particularly preferably 100% by weight.
- the catalytically active composition of the catalysts used according to the invention and used in the process of the invention may further comprise one or more elements (oxidation state 0) or their inorganic or organic compounds selected from groups IA to VI A and IB to VII B and VIII of the Periodic Table , contain.
- transition metals such as Re or rhenium oxides, Mn or MnÜ2, W or tungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobium oxalate, V or vanadium oxides or vanadyl pyrophosphate; Lanthanides, such as Ce or CeO 2 or Pr or Pr 2 O 3 ; Alkali metal oxides such as Na 2 O; Alkali metal carbonates such as Na 2 CO 3; Alkaline earth metal oxides, such as SrO; Alkaline earth metal carbonates such as MgC ⁇ 3, CaCO3 and BaCOa; Boron oxide (B2O3).
- the catalytically active composition of the catalysts according to the invention and used in the process according to the invention preferably contains no ruthenium, no iron and / or no zinc.
- the catalytically active mass of the catalyst preferably contains in the range from 0.1 to 10% by weight, in particular in the range from 0.2 to 7% by weight, more particularly in the range from 0.4 to 5% by weight of oxygen-containing compounds of one or more metals selected from Pb, Bi, Sn, Sb and In, each calculated as PbO, Bi 2 O 3 , SnO, Sb 2 O 3 and In 2 O 3, respectively.
- the metal is particularly preferably selected from Pb, Bi and In.
- the catalytically active composition of the catalyst before its reduction with hydrogen further preferably in the range of
- oxygen-containing compounds of zirconium calculated as ZrO 2 , 1 to 30 wt .-%, especially 2 to 25 wt %, more particularly 5 to 15% by weight, of oxygen-containing compounds of copper, calculated as CuO, 10 to 50% by weight, especially 13 to 40% by weight, more particularly 16 to 35% by weight, oxygen-containing compounds of nickel, calculated as NiO, and 10 to 50 wt .-%, particularly 13 to 40 wt .-%, more particularly 16 to 35 wt .-%, oxygen-containing compounds of cobalt, calculated as CoO.
- the molar ratio of nickel to copper is preferably greater than 1, more preferably greater than 1.2, more preferably in the range of 1.8 to 8.5.
- they may be precipitated together by co-precipitation of the nickel, cobalt and copper and doping metal components from an aqueous salt solution containing these elements by means of bases in the presence of a slurry of a sparingly soluble, oxygen-containing zirconium compound followed by washing, drying and calcination of the resulting precipitate to be obtained.
- Zirconium dioxide, zirconium oxide hydrate, zirconium phosphates, borates and silicates can be used, for example, as sparingly soluble, oxygen-containing zirconium compounds.
- the slurries of the sparingly soluble zirconium compounds can be prepared by suspending fine-grained powders of these compounds in water with vigorous stirring.
- these slurries are obtained by precipitating the sparingly soluble zirconium compounds from aqueous zirconium salt solutions by means of bases.
- the catalysts according to the invention are preferably prepared by a co-precipitation (mixed precipitation) of all their components.
- aqueous salt solution containing the catalyst components while heating and while stirring with an aqueous base, for example sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide, until the precipitation is complete.
- alkali metal-free bases such as ammonia, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium oxalate, ammonium malonate, urotropin, urea, etc.
- salts used are generally not critical: since it depends primarily on the water solubility of the salts in this approach, one criterion is their good water solubility required for the preparation of these relatively highly concentrated salt solutions. It is taken for granted that when selecting the salts of the individual components, of course, only salts with such anions are chosen which do not lead to disturbances, either by causing undesired precipitation or by complicating or preventing precipitation by complex formation.
- the precipitates obtained in these precipitation reactions are generally chemically non-uniform and consist i.a. from mixtures of the oxides, oxide hydrates, hydroxides, carbonates and insoluble and basic salts of the metals used. It may prove beneficial for the filterability of the precipitates when they are aged, i. if left for some time after precipitation, possibly in heat or by passing air through it.
- the precipitates obtained by these precipitation processes are further processed to the catalysts of the invention as usual.
- the precipitation is washed. About the duration of the washing process and the temperature and amount of the washing water, the content of alkali metal, which has been supplied by the precipitant possibly used (mineral) base, are influenced. In general, by increasing the washing time or increasing the temperature of the washing water, the content of alkali metal will decrease.
- the material to be precipitated is generally dried at 80 to 200 ° C, preferably at 100 to 150 ° C, and then calcined. The calcination is carried out generally at temperatures between 300 and 800 ° C, preferably at 400 to 600 ° C, in particular at 450 to 550 ° C.
- the catalysts according to the invention can also be prepared by impregnation of zirconium dioxide (ZrO.sub.2), which is present, for example, in the form of powders or shaped articles, such as extrudates, tablets, spheres or rings.
- ZrO.sub.2 zirconium dioxide
- the zirconia is used, for example, in the monoclinic or tetragonal form, preferably in the monoclinic form.
- the impregnation is also carried out by the usual methods, such as. B. A. Stiles, Catalyst Manufacture Laboratory and Commercial Preparations, Marcel Dekker, New York (1983), by applying a respective metal salt solution in one or more impregnation stages, wherein as metal salts z. B. corresponding nitrates, acetates or chlorides can be used.
- the mass is dried after the impregnation and optionally calcined.
- the impregnation can be carried out according to the so-called "incipient wetness” method, in which the zirconium dioxide is moistened according to its water absorption capacity to a maximum of saturation with the impregnation solution.
- the impregnation can also be done in supernatant solution.
- multi-stage impregnation processes it is expedient to dry between individual impregnation steps and optionally to calcine.
- the multi-stage impregnation is advantageous to apply especially when the zirconium dioxide is to be applied with a larger amount of metal.
- the impregnation can take place simultaneously with all metal salts or in any order of the individual metal salts in succession.
- the catalysts prepared by impregnation are dried and preferably also calcined, for example at the above-indicated Calciniertemperatur- areas.
- the catalyst is suitably conditioned, whether it is adjusted by grinding to a certain particle size or that it is mixed after its grinding with molding aids such as graphite or stearic acid, by means of a press to formations, for.
- molding aids such as graphite or stearic acid
- the tempering temperatures preferably correspond to the temperatures during the calcination.
- the catalysts prepared in this way contain the catalytically active metals in the form of a mixture of their oxygen-containing compounds, i. in particular as oxides and mixed oxides.
- Catalysts prepared as described above are stored as such and optionally traded. Before being used as catalysts, they are usually prereduced. However, they can also be used without prereduction, in which case they are reduced under the conditions of the hydrogenating amination by the hydrogen present in the reactor.
- the catalysts are first heated at preferably 150 to 200 ° C for a period of e.g. 12 to 20 hours exposed to a nitrogen-hydrogen atmosphere and then treated for up to about 24 hours at preferably 200 to 400 ° 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 mechanical stability can be determined by measuring the so-called lateral compressive strength.
- the shaped catalyst body for. As the catalyst tablet, between two parallel plates loaded with increasing force, this load z. B. can take place on the shell side of catalyst tablets until a breakage of the catalyst molding occurs.
- the force registered on breakage of the shaped catalyst body is the lateral compressive strength.
- the inventive method is preferably carried out continuously, wherein the catalyst is preferably arranged as a fixed bed in the reactor. Both an inflow of the fixed catalyst bed from above and from below is possible.
- the gas flow is adjusted by temperature, pressure and amount so that even higher-boiling (high-boiling) reaction products remain in the gas phase.
- the aminating agent can be used in stoichiometric, under- or stoichiometric amounts with regard to the alcoholic hydroxyl group or aldehyde group or keto group to be aminated.
- the amine is preferably used in an approximately stoichiometric amount or slightly more than stoichiometric amount per mole of alcoholic hydroxyl group, aldehyde group or keto group to be aminated.
- the amine component (nitrogen compound) is preferably in the 0.90 to 100-fold molar amount, in particular in the 1, 0 to 10-fold molar amount, in each case based on the / used alcohol, aldehyde and / or ketone used.
- ammonia is generally used with a 1.5 to 250-fold, preferably 2 to 100-fold, in particular 2 to 10-fold, molar excess per mole of alcoholic hydroxyl group, aldehyde group or keto group to be reacted. Higher excesses of both ammonia and primary or secondary amines are possible.
- an amount of exhaust gas from 5 to 800 standard cubic meters / h, in particular 20 to 300 standard cubic meters / h, driven.
- the amination of the primary or secondary alcohol groups, aldehyde groups or keto groups of the educt can be carried out in the liquid phase or in the gas phase.
- the fixed bed process is in the gas phase.
- the starting materials are passed simultaneously in the liquid phase at pressures of generally from 5 to 30 MPa (50 to 300 bar), preferably from 5 to 25 MPa, more preferably from 15 to 25 MPa, and temperatures of generally 80 to 350 ° C, especially 100 to 300 ° C, preferably 120 to 270 ° C, more preferably 130 to 250 ° C, in particular 170 to 230 ° C, including hydrogen over the catalyst, the usually located in a preferably heated from the outside fixed bed reactor. It is both a trickle way and a sumping possible.
- the catalyst loading is generally in the range of 0.05 to 5, preferably 0.1 to 2, more preferably 0.2 to 0.6, kg of alcohol, aldehyde or ketone per liter of catalyst (bulk volume) and hour.
- a suitable solvent such as tetrahydrofuran, dioxane, N-methylpyrrolidone or ethylene glycol dimethyl ether. It is expedient to heat the reactants before they are introduced into the reaction vessel, preferably to the reaction temperature.
- the gaseous educts (alcohol, aldehyde or ketone plus ammonia or amine) in a sufficiently large for vaporization gas stream, preferably hydrogen, at pressures of generally 0.1 to 40 MPa (1 to 400 bar ), preferably 0.1 to 10 MPa, more preferably 0.1 to 5 MPa, in the presence of hydrogen passed over the catalyst.
- the temperatures for the amination of alcohols are generally from 80 to 350.degree. C., especially from 100 to 300.degree. yakt 120 to 270 ° C, more preferably 160 to 250 ° C.
- reaction temperatures in the hydrogenating amination of aldehydes and ketones are generally 80 to 350 ° C, especially 90 to 300 ° C, preferably 100 to 250 ° C. It is both an influx of the fixed catalyst bed from above and from below possible.
- the required gas stream is preferably obtained by a cycle gas method.
- the catalyst loading is generally in the range of 0.01 to 2, preferably 0.05 to 0.5, kg of alcohol, aldehyde or ketone per liter of catalyst (bulk volume) and hour.
- the hydrogen is generally fed to the reaction in an amount of from 5 to 400 l, preferably in an amount of from 50 to 200 l per mole of alcohol, aldehyde or ketone component, the liter data in each case being converted to standard conditions (ST .).
- the amination of aldehydes or ketones differs in the implementation of the amination of alcohols in that in the amination of aldehydes and ketones at least stoichiometric amounts of hydrogen must be present.
- the pressure in the reaction vessel which results from the sum of the partial pressures of the aminating agent, of the alcohol, aldehyde or ketone and the reaction products formed and optionally of the solvent used at the indicated temperatures, is expediently increased by pressurizing hydrogen to the desired reaction pressure.
- the excess aminating agent can be recycled along with the hydrogen.
- the catalyst is arranged as a fixed bed, it may be advantageous for the selectivity of the reaction to mix the catalyst form body in the reactor with inert fillers, so to speak to "dilute" them.
- the proportion of fillers in such catalyst preparations may be 20 to 80, especially 30 to 60 and especially 40 to 50 parts by volume.
- reaction water formed in the course of the reaction in each case one mole per mole of reacted alcohol group, aldehyde group or keto group
- the reaction water formed in the course of the reaction generally does not interfere with the degree of conversion, the reaction rate, the selectivity and the catalyst life and is therefore expediently only in the workup of the reaction product removed from this, z. B. distillative.
- the excess hydrogen and the optionally present excess are removed from the reaction effluent.
- schüssige aminating agent removed and the reaction crude product obtained, for example, by a fractional rectification.
- Suitable workup processes are described, for example, in EP-A-1 312 600 and EP-A-1 312 599 (both BASF AG).
- the excess aminating agent and the hydrogen are advantageously recycled back into the reaction zone. The same applies to the possibly not completely reacted alcohol, aldehyde or ketone component.
- Unreacted starting materials and any appropriate by-products can be recycled back into the synthesis. Unreacted starting materials can be re-flowed over the catalyst bed in discontinuous or continuous operation after condensation of the products in the separator in the circulating gas stream.
- Amination agents in the process according to the invention are, in addition to ammonia, primary and secondary amines.
- R 1 , R 2 is hydrogen (H), alkyl, such as C 20 -alkyl, cycloalkyl, such as C 3 -
- alkoxyalkyl such as C 2-3 -alkoxyalkyl
- dialkylaminoalkyl such as C 3-30 -dialkylaminoalkyl
- aryl such as C 7-30 -aralkyl
- alkylaryl such as C 3-30 -alkylaryl, or jointly - (CH 2 ) r X- (CH 2 ) k-,
- R 3 is hydrogen (H), alkyl, such as C 2 o-alkyl, cycloalkyl such as C 3 -
- hydroxyalkyl such as C 1-20 -hydroxyalkyl
- aminoalkyl such as C 1-20 -aminomethyl
- hydroxyalkylaminoalkyl such as C 2-20 -hydroxyalkylaminoalkyl
- alkoxyalkyl such as C 2-30-
- R 2 and R 4 together - (CH 2 ) ⁇ -X- (CH 2 ) m-, R 5 , R 10 is hydrogen (H), alkyl, such as C 1-4 -alkyl, alkylphenyl, such as C7
- R 6 , R 7 , R 8 , R 9 is hydrogen (H), methyl or ethyl
- n is an integer from 1 to 30 and
- j, k, I, m, q is an integer from 1 to 4,
- the process according to the invention is therefore preferably used for the preparation of an amine I application by reacting a primary or secondary alcohol of the formula II
- the starting alcohol may also be an aminoalcohol, e.g. an aminoalcohol according to the formula II.
- the reaction can also be carried out intramolecularly in a corresponding amino alcohol, aminoketone or amino aldehyde.
- the radical R 4 (R 3 ) CH- is therefore formally replaced by a hydrogen atom of the nitrogen compound III by the radical R 4 (R 3 ) CH- with the release of one molar equivalent of water.
- the process according to the invention is also preferably used in the preparation of a cyclic amine of the formula IV
- R 11 and R 12 is hydrogen (H), alkyl, such as C 2 to C o alkyl, cycloalkyl such as C 3 - to C 2 - cycloalkyl, aryl, heteroaryl, aralkyl such as Cz to C2o aralkyl, and Alkyla - Ryl, such as C7 to C20 alkylaryl,
- Z is CH 2 , CHR 5 , oxygen (O), NR 5 or NCH 2 CH 2 OH and
- R 1 , R 6 , R 7 have the meanings given above,
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 hydrogen (H),
- Alkyl such as Ci -2 o alkyl, preferably Ci-14-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n- Pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, Cyclopentylmethyl, n-heptyl, iso-heptyl, cyclohexylmethyl, n -octyl, isooctyl, 2-ethylhexyl, n-decyl, 2-n-propyl-n-heptyl, n-tridecyl, 2-n-butyl-n- nonyl and 3-n-butyl-n-
- Hydroxyalkyl such as C 1-20 -hydroxyalkyl, preferably C 1-8 -hydroxyalkyl, particularly preferably C 1-4 -hydroxyalkyl, such as hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n- propyl, 3-hydroxy-n-propyl and 1- (hydroxymethyl) ethyl,
- Aminoalkyl such as C 1-20 -aminoalkyl, preferably C 1-8 -aminoalkyl, such as aminomethyl, 2-aminoethyl, 2-amino-1, 1-dimethylethyl, 2-amino-n-propyl, 3-amino-n-propyl, 4-amino-n-butyl, 5-amino-n-pentyl, N- (2-aminoethyl) -2-aminoethyl and N- (2-aminoethyl) aminomethyl,
- Hydroxyalkylaminoalkyl such as C2-2o-hydroxyalkylaminoalkyl, preferably C3-8-hydroxyalkylaminoalkyl, such as (2-hydroxyethylamino) methyl, 2- (2-hydroxyethylamino) ethyl and 3- (2-hydroxyethylamino) propyl,
- Alkylaminoalkyl such as C 2-3 -alkylaminoalkyl, preferably C 2-30 -alkylaminoalkyl, particularly preferably C 2-8 -alkylaminoalkyl, such as methylaminomethyl, 2-methylaminoethyl, ethylaminomethyl, 2-ethylaminoethyl and 2- (isopropylamino) ethyl, (R 5 ) HN- (CH 2 ) q ,
- Heteroarylalkyl such as C4-2o-heteroarylalkyl, such as pyrid-2-ylmethyl, furan-2-ylmethyl, pyrrol-3-ylmethyl and imidazol-2-ylmethyl,
- Alkyl heteroaryl such as C 4-2o-alkyl heteroaryl, such as 2-methyl-3-pyridinyl, 4,5-dimethylimidazol-2-yl, 3-methyl-2-furanyl and 5-methyl-2-pyrazinyl,
- Heteroaryls such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, pyrazinyl, pyrrol-3-yl, imidazol-2-yl, 2-furanyl and 3-furanyl,
- Cycloalkyl such as C 3-12 -cycloalkyl, preferably C 3-8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, particularly preferably cyclopentyl and cyclohexyl, Alkoxyalkyl, such as C 2-3 -alkoxyalkyl, preferably C 2-30 -alkoxyalkyl, particularly preferably C 2-8 -alkoxyalkyl, such as methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, 1-methoxyethyl and 2-methoxyethyl, more preferably C 2-4 -alkoxyalkyl,
- Dialkylaminoalkyl such as C3-3o-dialkylaminoalkyl, preferably C3-2o-dialkylaminoalkyl, more preferably C3-io-dialkylaminoalkyl, such as N, N-dimethylaminomethyl, (N, N-dibutylamino) methyl, 2- (N, N-dimethylamino) ethyl , 2- (N, N-diethylamino) ethyl, 2- (N, N-dibutylamino) ethyl, 2- (N, N-di-n-propylamino) ethyl and 2-
- Aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl and 9-anthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl,
- Alkylaryl such as C7-2o-alkylaryl, preferably C7-12-alkylphenyl, such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4 Dimethylphenyl, 3,5-dimethylphenyl, 2,3,4-trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl , 4-ethylphenyl, 2-n-propylphenyl, 3-n-propylphenyl and 4-n-propylphenyl,
- Aralkyl such as C7-2o-aralkyl, preferably C7-12-phenylalkyl, such as benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenylpropyl, 3 -Phenyl-propyl, 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, more preferably benzyl, 1-phenethyl and 2-phenethyl,
- R 3 and R 4 or R 2 and R 4 together form a - (C Hb) IX (C H2) m group, such as - (CH 2 ) 3 -, - (CH 2 J 4 -, - (CH 2 ) S-, - (CH 2 J 6 -, - (CH 2 ) 7 -, - (CH 2 JO- (CH 2 J 2 -, - (CH 2 J-NR 5 - (CH 2 J 2 -, - ( CH 2 J-CH R 5 - (CH 2 ) 2 -, - (CH 2 J 2 -O- (CH 2 J 2 -, - (CH 2 ) 2 -NR 5 - (CH 2 ) 2 -, - ( CH 2 J 2 -
- Alkyl such as Ci -2 o alkyl, preferably Ci- ⁇ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n- Pentyl, isopentyl, sec-pentyl, neo
- Pentyl 1, 2-dimethylpropyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, 2-ethylhexyl, particularly preferably Ci-4-alkyl, or
- R 1 and R 2 together form a - (CH 2 Jj-X- (CH 2 Jk- group such as - (CH 2 J 3 -, - (CH 2 J 4 -, - (CH 2 J 5 -, - (CH 2 J 6 -, - (CH 2 J 7 -, - (CH 2 JO- (CH 2 J 2 -, - (CH 2 ) -NR 5 - (CH 2 ) 2 -, - (CH 2 J-CHR 5 -
- Alkyl preferably C 1-4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl and ethyl, particularly preferably methyl,
- Alkylphenyl preferably C7-4o-alkylphenyl, such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5- Dimethylphenyl, 2-, 3-, 4-nonylphenyl, 2-, 3-, 4-decylphenyl, 2,3-, 2,4-, 2,5-, 3,4-, 3,5-dinonylphenyl, 2, 3-, 2,4-, 2,5-, 3,4- and 3,5-didecylphenyl, especially C7-2o-alkylphenyl,
- Methyl or ethyl preferably methyl
- Alkyl such as C 1 - to C 20 -alkyl
- cycloalkyl such as C 3 - to C 12 -cycloalkyl
- aryl such as C 7 - to C 20 -aralkyl
- alkylaryl such as C 7 - to C 20 -alkylaryl, in each case as above
- N (R 10 ) 2 preferably NH 2 and N (CH 3 ) 2 ,
- C 2-2 O-AI kylaminoa I kyl preferably C 2- i6-alkylaminoalkyl, such as methylaminomethyl, 2- methylaminoethyl, ethylaminomethyl, 2-ethylaminoethyl and 2- (iso- propylamino) ethyl,
- C3- 2 o-dialkylaminoalkyl preferably C3-16 dialkylaminoalkyl such as dimethylamino methyl, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2- (di-n-propylamino) ethyl and 2- (di-iso-propylamino) ethyl,
- JJ an integer from 1 to 4 (1, 2, 3 or 4), preferably 2 and 3, more preferably 2, k, m, q: an integer from 1 to 4 (1, 2, 3 or 4), preferably 2, 3 and 4, more preferably 2 and 3,
- n an integer from 1 to 30, preferably an integer from 1 to 8 (1, 2, 3, 4, 5, 6, 7 or 8), more preferably an integer from 1 to 6.
- alcohols are suitable among the o.g. Prerequisites virtually all primary and secondary alcohols with aliphatic OH function.
- the alcohols can be straight-chain, branched or cyclic. Secondary alcohols are aminated as well as primary alcohols.
- the alcohols may also bear substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, alkenyloxy, alkylamino or dialkylamino groups, or else optionally hydrogenated under the conditions of the hydrogenating amination, for example CC double - or triple bonds.
- polyhydric alcohols are to be aminated, it is possible to obtain control of the reaction conditions in hand, preferably amino alcohols, cyclic amines or multiply aminated products.
- 1,6-diols leads, depending on the choice of reaction conditions, to 1-amino-6-hydroxy, 1,6-diamino compounds or to seven-membered rings with one nitrogen atom (hexamethyleneimines).
- ADG H 2 N-CH 2 CH 2 -O- CH 2 CH 2 -OH
- diaminodiglycol H 2 N-CH 2 CH 2 -O-CH 2 CH 2 -NH 2
- diethanolamine piperazine is correspondingly obtained with particular preference.
- triethanolamine N- (2-hydroxyethyl) piperazine can be obtained.
- alcohols are preferably aminated:
- Particularly preferred alcohols are methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-ethylhexanol, cyclohexanol, fatty alcohols , Ethylene glycol, diethylene glycol (DEG), triethylene glycol (TEG), 2- (2-dimethylaminoethoxy) ethanol, N-methyldiethanolamine and 2- (2-dimethylaminoethoxy) ethanol.
- DEG diethylene glycol
- TEG triethylene glycol
- 2- (2-dimethylaminoethoxy) ethanol N-methyldiethanolamine
- 2- (2-dimethylaminoethoxy) ethanol 2- (2-dimethylaminoethoxy
- Suitable ketones which can be used in the process according to the invention are suitable among the above-mentioned. Prerequisites practically all aliphatic and aromatic ketones.
- the aliphatic ketones may be straight-chain, branched or cyclic, the ketones may contain heteroatoms.
- the ketones may also bear substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, alkenyloxy, alkylamino or dialkylamino groups, or else optionally hydrogenated under the conditions of the hydrogenating amination be CC double or triple bonds. If polyvalent ketones are to be aminated, it is possible to obtain control of the reaction conditions by hand, aminoketones, amino alcohols, cyclic amines or multiply aminated products.
- ketones are preferably hydrogenated aminatively:
- Suitable aldehydes for use in the process according to the invention are suitable among the above-mentioned. Prerequisites virtually all aliphatic and aromatic aldehydes.
- the aliphatic aldehydes may be straight-chain, branched or cyclic, the aldehydes may contain heteroatoms.
- the aldehydes may also bear substituents or contain functional groups which are inert under the conditions of the hydrogenating amination, for example alkoxy, alkenyloxy, alkylamino or dialkylamino groups, or else optionally hydrogenated under the conditions of the hydrogenating amination, for example CC -Double or triple bonds. If multivalent aldehydes or keto aldehydes are to be aminated, then it is possible to obtain control of the reaction conditions in hand, amino alcohols, cyclic amines or multiply aminated products.
- aldehydes are preferably hydrogenated aminatively:
- aminating agents in the hydrogenating amination of alcohols, aldehydes or ketones in the presence of hydrogen both ammonia and primary or secondary, aliphatic or cycloaliphatic or aromatic amines can be used.
- the alcoholic hydroxyl group or the aldehyde group or the keto group is first converted into the primary amino groups (-NH 2).
- the primary amine formed in this way can react with further alcohol or aldehyde or ketone to form the corresponding secondary amine, which in turn reacts with further alcohol or aldehyde or ketone to form the corresponding, preferably symmetrical, tertiary amine.
- primary, secondary or tertiary amines can be prepared in this manner as desired.
- cyclic amines such as pyrrolidines, piperidines, hexamethyleneimines, piperazines and morpholines can be prepared in this way by intramolecular hydrogenating amination.
- primary or secondary amines can be used as aminating agents.
- aminating agents are preferably used for the preparation of unsymmetrically substituted di- or trialkylamines, such as ethyldiisopropylamine and ethyldicyclohexylamine.
- di- or trialkylamines such as ethyldiisopropylamine and ethyldicyclohexylamine.
- mono- and dialkylamines are used as aminating agents: monomethylamine, dimethylamine, monoethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, isopropylethylamine, n-butylamine, di-n-propylamine.
- Amines particularly preferably prepared by the process according to the invention are, for example, morpholine (from monoaminodiglycol), monoaminodiglycol, morpholine and / or 2, 2'-dimorpholinodiethyl ether (DMDEE) (from DEG and ammonia), 6-dimethylaminohexanol-1 (from hexanediol and dimethylamine ( DMA)), triethylamine (from ethanol and diethylamine (DEA)), dimethylethylamine (from ethanol and DMA), N- (C 1-4 -alkyl) morpholine (from DEG and mono (C 1-4 -alkyl) amine), N- (C 1-4 -alkyl) piperidine (from 1,5-pentanediol and mono (C 1-4 -alkyl) amine), piperazine and / or diethylenetriamine (DETA) (from N- (2-aminoethyl) ethanolamine
- Octanol and NH3 1,2-propylenediamine (from 2-hydroxy-propylamine and NH3), 1-diethylamino-4-aminopentane (from 1-diethylamino-4-hydroxypentane and NH3), N, N-di (Ci-4 alkyl) cyclohexylamine (from cyclohexanone and / or cyclohexanol and di (C 1-4 -alkyl) amine), for example N, N-dimethyl-N-cyclohexylamine (DMCHA), polyisobuteneamine (PIBA; with eg n ⁇ 1000) (from polyisobutene aldehyde and NH3), N, N-diisopropyl-N-ethylamine (Hünigbase) (from N, N-diisopropylamine and acetaldehyde), N-methyl-N-isopropylamine (MMIPA) (from Monomethyl
- 4- alkyl) amine 1, 2-ethylenediamine (EDA), monoethanolamine (MEOA), Diethylenetriamine (DETA) and / or piperazine (PIP) (from monoethylene glycol (MEG) and ammonia), 1, 8-diamino-3,6-dioxa-octane and / or 1-amino-8-hydroxy-3,6-dioxa octane (from triethylene glycol (TEG) and ammonia), 1-methoxy-2-propylamine (1-methoxy-isopropylamine, MOIPA) (from 1-methoxy-2-propanol and ammonia), N-cyclododecyl-2,6-dimethylmorpholine (Dodemorph) (from cyclododecanone and / or cyclododecanol and 2,6-dimethylmorpholine), polyetheramine (from appropriate polyether alcohol and ammonia).
- EDA 2-ethylenediamine
- MEOA monoethanolamine
- the polyether alcohols are, for example, polyethylene glycols or polypropylene glycols having a molecular weight in the range from 200 to 5000 g / mol, the corresponding polyetheramines being obtainable, for example, under the trade name PEA D230, D400, D2000, T403 or T5000 from BASF.
- the thus obtained hydroxide-carbonate mixture was then tempered at a temperature of 450 to 500 ° C over a period of 4 hours.
- the catalyst thus prepared had the composition: 28% by weight of NiO, 28% by weight of CoO, 11% by weight of CuO, and 33% by weight of ZrO 2 .
- the catalyst was mixed with 3% by weight of graphite and formed into tablets.
- the oxidic tablets were reduced.
- the reduction was carried out at 280 ° C, the heating rate being 3 ° C / minute. First, it was reduced for 50 minutes with 10% H 2 in N 2 , then 20 minutes with 25% H 2 in N 2 , then 10 minutes with 50% H 2 in N 2 , then 10 minutes with 75% H 2 in N 2 and finally 3 hours with 100% H 2 .
- the percentages are% by volume.
- the passivation of the reduced catalyst was carried out at room temperature in dilute air (air in N 2 with an O 2 content of not more than 5% by volume).
- the catalyst was prepared analogously to catalyst 1. However, the nitrate solution was additionally added lead nitrate.
- the catalyst 2 thus obtained had the composition as shown in Table I. Examples 3 and 4
- the catalysts were prepared analogously to catalyst 1. However, bismuth nitrate was added to the nitrate solution.
- the catalysts 3 and 4 thus obtained had the composition as shown in Table I.
- the catalyst was prepared analogously to catalyst 1. However, the nitrate solution was additionally added indium nitrate. The catalyst 5 thus obtained had the composition as shown in Table I.
- the catalysts were prepared analogously to catalyst 1. However, the nitrate solution was additionally added tin dichloride. The thus obtained catalysts 6 and
- Reaction mixture was fed 34 g of liquid ammonia (2 mol), the autoclave was pressed to 70 bar with hydrogen and heated to 200 ° C. At 200 ° C again 20 bar of hydrogen was injected, the total pressure rose to 180 - 200 bar. The autoclave was run at 200 ° C for 12 hours with stirring. At various times, samples were withdrawn from the reaction mixture and analyzed by GC chromatography. For this purpose, a 30 m long GC column "RTX-5 amines" was used, with a temperature program: 80 ° C / 15 minutes, heating to 290 ° C in 30 minutes, at 290 ° C / 15 minutes the catalysts of Examples 1 to 7 can be found in Table I.
- the respective pure products can be obtained from the hydrous raw materials by rectification under vacuum, atmospheric pressure or elevated pressure according to the known methods.
- the pure products fall either directly in pure form or as an azeotrope with water.
- Water-containing azeotropes can be dehydrated by means of a liquid-liquid extraction with concentrated sodium hydroxide solution before or after the purifying distillation. Distillative dehydration in the presence of an entraining agent by known methods is also possible.
- a dehydration by a separation of the organic and the aqueous phase by known methods is also possible.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/373,825 US8063252B2 (en) | 2006-07-14 | 2007-07-04 | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
JP2009519905A JP5637684B2 (ja) | 2006-07-14 | 2007-07-04 | アミンの製造方法 |
CN200780026682.1A CN101489979B (zh) | 2006-07-14 | 2007-07-04 | 生产胺的方法 |
EP07765787A EP2043996B1 (de) | 2006-07-14 | 2007-07-04 | Verfahren zur herstellung eines amins |
US13/271,038 US8765634B2 (en) | 2006-07-14 | 2011-10-11 | Processes for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06117249 | 2006-07-14 | ||
EP06117249.0 | 2006-07-14 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/373,825 A-371-Of-International US8063252B2 (en) | 2006-07-14 | 2007-07-04 | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US13/271,038 Division US8765634B2 (en) | 2006-07-14 | 2011-10-11 | Processes for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008006750A1 true WO2008006750A1 (de) | 2008-01-17 |
Family
ID=38624021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/056725 WO2008006750A1 (de) | 2006-07-14 | 2007-07-04 | Verfahren zur herstellung eines amins |
Country Status (6)
Country | Link |
---|---|
US (2) | US8063252B2 (de) |
EP (1) | EP2043996B1 (de) |
JP (1) | JP5637684B2 (de) |
CN (1) | CN101489979B (de) |
RU (1) | RU2009104740A (de) |
WO (1) | WO2008006750A1 (de) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009080506A1 (de) | 2007-12-21 | 2009-07-02 | Basf Se | Verfahren zur herstellung eines amins |
US7750189B2 (en) | 2006-07-14 | 2010-07-06 | Basf Se | Method for producing an amine |
US7754922B2 (en) | 2006-07-14 | 2010-07-13 | Basf Se | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US7919655B2 (en) | 2006-07-14 | 2011-04-05 | Basf Se | Method for producing an amine |
WO2011067199A1 (de) | 2009-12-03 | 2011-06-09 | Basf Se | Katalysator und verfahren zur herstellung eines amins |
WO2011067200A1 (de) | 2009-12-03 | 2011-06-09 | Basf Se | Katalysator und verfahren zur herstellung eines amins |
WO2011082994A1 (de) | 2009-12-17 | 2011-07-14 | Basf Se | Umsetzung von glykolaldehyd mit einem aminierungsmittel |
US8063252B2 (en) | 2006-07-14 | 2011-11-22 | Basf Se | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US8268995B2 (en) | 2007-12-21 | 2012-09-18 | Basf Se | Processes for preparing amines and catalysts for use therein |
US8278489B2 (en) | 2007-12-21 | 2012-10-02 | Basf Se | Method for producing an amine |
US8324430B2 (en) | 2007-12-21 | 2012-12-04 | Basf Se | Processes for preparing amines and catalysts for use therein |
WO2013178534A1 (de) | 2012-06-01 | 2013-12-05 | Basf Se | Verfahren zur herstellung eines mono-n-alkyl-piperazins |
WO2013182468A1 (de) | 2012-06-06 | 2013-12-12 | Basf Se | Verfahren zur herstellung von piperazin |
WO2013182465A1 (de) | 2012-06-06 | 2013-12-12 | Basf Se | Verfahren zur herstellung von piperazin |
WO2014009292A1 (de) | 2012-07-13 | 2014-01-16 | Basf Se | Verfahren zur herstellung von pyrrolidin |
US8637668B2 (en) | 2010-06-15 | 2014-01-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
US8884015B2 (en) | 2012-06-01 | 2014-11-11 | Basf Se | Process for the preparation of a mono-N-alkypiperazine |
WO2014184039A1 (de) | 2013-05-16 | 2014-11-20 | Basf Se | Verfahren zur herstellung von n-alkyl-piperazinen |
US8927712B2 (en) | 2012-06-01 | 2015-01-06 | Basf Se | Process for the preparation of a mono-N-alkylpiperazine |
US8933223B2 (en) | 2010-10-14 | 2015-01-13 | Basf Se | Process for preparing a cyclic tertiary amine |
US8981093B2 (en) | 2012-06-06 | 2015-03-17 | Basf Se | Process for preparing piperazine |
US9315479B2 (en) | 2012-07-13 | 2016-04-19 | Basf Se | Process for preparing pyrrolidine |
EP2885269B1 (de) | 2012-08-17 | 2016-09-14 | OXEA GmbH | Kontinuierliches verfahren zur herstellung primärer aliphatischer amine aus aldehyden |
WO2018224315A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2018224321A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2018224316A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2019081283A1 (de) | 2017-10-27 | 2019-05-02 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2019081285A1 (de) | 2017-10-27 | 2019-05-02 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2019105782A1 (de) | 2017-11-30 | 2019-06-06 | Basf Se | Verfahren zur kontinuierlichen herstellung von 1,2-propylendiamin (1,2-pda) und dimethyldiet-hylentriamin (dmdeta) |
WO2020178085A1 (en) | 2019-03-06 | 2020-09-10 | Basf Se | Method for the production of ethyleneamines |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101489673A (zh) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | 生产胺的方法 |
CN101484105B (zh) * | 2006-07-20 | 2012-04-18 | Sca卫生产品股份公司 | 用于形成气流成网吸收芯体的设备和方法 |
CN102895978B (zh) * | 2012-10-19 | 2014-11-12 | 南京信息工程大学 | 一种用于合成多氨基化合物的催化剂及其制备方法与应用 |
CN103480380B (zh) * | 2013-09-03 | 2015-04-22 | 万华化学集团股份有限公司 | 一种用于固定床苯胺精馏残渣资源化利用的催化剂及其制备方法 |
CN104262168B (zh) * | 2014-09-22 | 2017-03-15 | 北京旭阳科技有限公司 | 一种己二胺的制备方法 |
CN112691677B (zh) * | 2019-10-23 | 2024-02-13 | 中国石油化工股份有限公司 | 一种乙醇临氢氨化制备乙胺的催化剂及其制法和应用 |
WO2021174522A1 (en) * | 2020-03-06 | 2021-09-10 | Rhodia Operations | A method for the alkylation of amines |
CN114230469B (zh) * | 2021-12-15 | 2023-03-21 | 中国科学院大连化学物理研究所 | 负载型纳米钌锆锡复合氧化物的合成及在苯甲醛胺化合成苄胺中应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0963975A1 (de) * | 1998-06-12 | 1999-12-15 | Basf Aktiengesellschaft | Verfahren zur Herstellung von Aminen |
WO2003051508A1 (en) * | 2001-12-14 | 2003-06-26 | Huntsman Petrochemical Corporation | Advances in amination catalysis |
Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL137371C (de) | 1963-08-02 | |||
NL169595C (nl) | 1970-05-21 | 1982-08-02 | Shell Int Research | Werkwijze voor de bereiding van aminen en van smeerolien en vloeibare motorbrandstoffen die deze bevatten. |
US3922303A (en) | 1971-02-17 | 1975-11-25 | Dai Ichi Kogyo Seiyaku Co Ltd | Process for the production of tertiary amines having higher alkyl group |
US4152353A (en) | 1977-08-29 | 1979-05-01 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
US4153581A (en) | 1977-09-01 | 1979-05-08 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
US4625030A (en) | 1984-05-23 | 1986-11-25 | Union Carbide Corporation | Potentiated nickel catalysts for amination |
DE3611230A1 (de) | 1986-04-04 | 1987-10-08 | Basf Ag | Polybutyl- und polyisobutylamine, verfahren zu deren herstellung und diese enthaltende kraft- und schmierstoffzusammensetzungen |
DE3903367A1 (de) | 1989-02-04 | 1990-08-16 | Basf Ag | Katalysator und verfahren zur hydrierenden aminierung von alkoholen |
DE4116367A1 (de) | 1991-05-18 | 1992-11-19 | Basf Ag | Verfahren zur herstellung von aminen |
JPH07185346A (ja) * | 1993-12-28 | 1995-07-25 | Tosoh Corp | アルコールのアミノ化触媒 |
DE4428004A1 (de) | 1994-08-08 | 1996-02-15 | Basf Ag | Verfahren zur Herstellung von Aminen |
DE4429547A1 (de) | 1994-08-19 | 1996-02-22 | Basf Ag | Verfahren zur Herstellung von Aminen |
DE19507007A1 (de) | 1995-02-28 | 1996-08-29 | Basf Ag | Katalysatoren für die Aminierung von Alkoholen, Ketonen und Aldehyden |
DE19645047A1 (de) | 1996-10-31 | 1998-05-07 | Basf Ag | Katalysatoren für die Aminierung von Alkylenoxiden, Alkoholen, Aldehyden und Ketonen |
SG70081A1 (en) | 1997-05-14 | 2000-01-25 | Kuraray Co | Process for producing diamines |
DE19742911A1 (de) | 1997-09-29 | 1999-04-01 | Basf Ag | Verfahren zur Herstellung von Aminen |
DE19901198A1 (de) * | 1999-01-14 | 2000-07-20 | Basf Ag | Verfahren zur Herstellung von 2,2'-Dimorpholinodiethylether |
DE19910960A1 (de) * | 1999-03-12 | 2000-09-14 | Basf Ag | Verfahren zur Herstellung von Aminen |
WO2000069804A1 (en) | 1999-05-13 | 2000-11-23 | Symyx Technologies Inc. | Amination of aromatic hydrocarbons and heterocyclic analogs thereof |
DE50007278D1 (de) | 1999-12-06 | 2004-09-09 | Basf Ag | Verfahren zur Herstellung von Aminen |
DE10153410A1 (de) | 2001-10-30 | 2003-05-15 | Basf Ag | Verfahren zur Auftrennung von wasserhaltigen Rohamingemischen aus der Aminsynthese |
DE10153411A1 (de) | 2001-10-30 | 2003-05-15 | Basf Ag | Verfahren zur Auftrennung von wasserhaltigen Rohamingemischen aus der Aminsynthese |
DE10209528A1 (de) * | 2002-03-04 | 2003-09-18 | Basf Ag | Verfahren zur Herstellung von Ethyldimethylamin und Triethylamin |
DE10211101A1 (de) | 2002-03-14 | 2003-09-25 | Basf Ag | Katalysatoren und Verfahren zur Herstellung von Aminen |
DE10261193A1 (de) | 2002-12-20 | 2004-07-01 | Basf Ag | Verfahren zur Herstellung eines Armins |
DE102004062253A1 (de) | 2004-12-23 | 2006-07-06 | Basf Ag | Direktaminierung von Kohlenwasserstoffen |
DE102005047458A1 (de) | 2005-09-30 | 2007-04-12 | Basf Ag | Verfahren zur Herstellung von Aminodiglykol (ADG) und Morpholin |
US8034978B2 (en) | 2006-05-31 | 2011-10-11 | Basf Se | Process for the preparation of an amine |
RU2009104740A (ru) | 2006-07-14 | 2010-08-27 | Басф Се (De) | Способ получения амина |
US7919655B2 (en) | 2006-07-14 | 2011-04-05 | Basf Se | Method for producing an amine |
CN101489673A (zh) | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | 生产胺的方法 |
CN101489982A (zh) | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | 生产胺的方法 |
CN101489981B (zh) | 2006-07-14 | 2013-03-20 | 巴斯夫欧洲公司 | 生产胺的方法 |
ATE553844T1 (de) | 2007-12-21 | 2012-05-15 | Basf Se | Verfahren zur herstellung eines amins |
US8324430B2 (en) | 2007-12-21 | 2012-12-04 | Basf Se | Processes for preparing amines and catalysts for use therein |
CN101903092B (zh) | 2007-12-21 | 2013-03-20 | 巴斯夫欧洲公司 | 生产胺的方法 |
US8278489B2 (en) | 2007-12-21 | 2012-10-02 | Basf Se | Method for producing an amine |
-
2007
- 2007-07-04 RU RU2009104740/04A patent/RU2009104740A/ru not_active Application Discontinuation
- 2007-07-04 CN CN200780026682.1A patent/CN101489979B/zh active Active
- 2007-07-04 WO PCT/EP2007/056725 patent/WO2008006750A1/de active Application Filing
- 2007-07-04 JP JP2009519905A patent/JP5637684B2/ja active Active
- 2007-07-04 EP EP07765787A patent/EP2043996B1/de active Active
- 2007-07-04 US US12/373,825 patent/US8063252B2/en active Active
-
2011
- 2011-10-11 US US13/271,038 patent/US8765634B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0963975A1 (de) * | 1998-06-12 | 1999-12-15 | Basf Aktiengesellschaft | Verfahren zur Herstellung von Aminen |
WO2003051508A1 (en) * | 2001-12-14 | 2003-06-26 | Huntsman Petrochemical Corporation | Advances in amination catalysis |
Cited By (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8063252B2 (en) | 2006-07-14 | 2011-11-22 | Basf Se | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US7750189B2 (en) | 2006-07-14 | 2010-07-06 | Basf Se | Method for producing an amine |
US7754922B2 (en) | 2006-07-14 | 2010-07-13 | Basf Se | Process for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US7919655B2 (en) | 2006-07-14 | 2011-04-05 | Basf Se | Method for producing an amine |
US8765634B2 (en) | 2006-07-14 | 2014-07-01 | Basf Se | Processes for preparing amines and zirconium dioxide- and nickel-containing catalysts for use therein |
US8324430B2 (en) | 2007-12-21 | 2012-12-04 | Basf Se | Processes for preparing amines and catalysts for use therein |
US8268995B2 (en) | 2007-12-21 | 2012-09-18 | Basf Se | Processes for preparing amines and catalysts for use therein |
US8278489B2 (en) | 2007-12-21 | 2012-10-02 | Basf Se | Method for producing an amine |
US8293945B2 (en) | 2007-12-21 | 2012-10-23 | Basf Se | Method for producing an amine |
WO2009080506A1 (de) | 2007-12-21 | 2009-07-02 | Basf Se | Verfahren zur herstellung eines amins |
WO2011067200A1 (de) | 2009-12-03 | 2011-06-09 | Basf Se | Katalysator und verfahren zur herstellung eines amins |
US8318982B2 (en) | 2009-12-03 | 2012-11-27 | Basf Se | Catalyst and process for preparing an amine |
JP2013512871A (ja) * | 2009-12-03 | 2013-04-18 | ビーエーエスエフ ソシエタス・ヨーロピア | アミンの製造のための触媒及びアミンの製造方法 |
JP2013512872A (ja) * | 2009-12-03 | 2013-04-18 | ビーエーエスエフ ソシエタス・ヨーロピア | 触媒及びアミンの製造方法 |
US8487135B2 (en) | 2009-12-03 | 2013-07-16 | Basf Se | Catalyst and process for preparing an amine |
EA021623B1 (ru) * | 2009-12-03 | 2015-07-30 | Басф Се | Катализатор на носителе и способ получения амина |
WO2011067199A1 (de) | 2009-12-03 | 2011-06-09 | Basf Se | Katalysator und verfahren zur herstellung eines amins |
WO2011082994A1 (de) | 2009-12-17 | 2011-07-14 | Basf Se | Umsetzung von glykolaldehyd mit einem aminierungsmittel |
US8637668B2 (en) | 2010-06-15 | 2014-01-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
US8933223B2 (en) | 2010-10-14 | 2015-01-13 | Basf Se | Process for preparing a cyclic tertiary amine |
US8884015B2 (en) | 2012-06-01 | 2014-11-11 | Basf Se | Process for the preparation of a mono-N-alkypiperazine |
US8927712B2 (en) | 2012-06-01 | 2015-01-06 | Basf Se | Process for the preparation of a mono-N-alkylpiperazine |
WO2013178534A1 (de) | 2012-06-01 | 2013-12-05 | Basf Se | Verfahren zur herstellung eines mono-n-alkyl-piperazins |
WO2013182465A1 (de) | 2012-06-06 | 2013-12-12 | Basf Se | Verfahren zur herstellung von piperazin |
WO2013182468A1 (de) | 2012-06-06 | 2013-12-12 | Basf Se | Verfahren zur herstellung von piperazin |
US8981093B2 (en) | 2012-06-06 | 2015-03-17 | Basf Se | Process for preparing piperazine |
WO2014009292A1 (de) | 2012-07-13 | 2014-01-16 | Basf Se | Verfahren zur herstellung von pyrrolidin |
US9315479B2 (en) | 2012-07-13 | 2016-04-19 | Basf Se | Process for preparing pyrrolidine |
EP2885269B1 (de) | 2012-08-17 | 2016-09-14 | OXEA GmbH | Kontinuierliches verfahren zur herstellung primärer aliphatischer amine aus aldehyden |
EP2885269B2 (de) † | 2012-08-17 | 2023-07-26 | OQ Chemicals GmbH | Kontinuierliches verfahren zur herstellung primärer aliphatischer amine aus aldehyden |
WO2014184039A1 (de) | 2013-05-16 | 2014-11-20 | Basf Se | Verfahren zur herstellung von n-alkyl-piperazinen |
WO2018224321A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2018224316A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
US11208373B2 (en) | 2017-06-09 | 2021-12-28 | Basf Se | Method for the production of ethyleneamines |
US11214535B2 (en) | 2017-06-09 | 2022-01-04 | Basf Se | Method for producing ethyleneamines |
WO2018224315A1 (de) | 2017-06-09 | 2018-12-13 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2019081283A1 (de) | 2017-10-27 | 2019-05-02 | Basf Se | Verfahren zur herstellung von ethylenaminen |
WO2019081285A1 (de) | 2017-10-27 | 2019-05-02 | Basf Se | Verfahren zur herstellung von ethylenaminen |
US11021434B2 (en) | 2017-10-27 | 2021-06-01 | Basf Se | Method for producing ethyleneamines |
US11339117B2 (en) | 2017-10-27 | 2022-05-24 | Basf Se | Method for the production of ethyleneamines |
WO2019105782A1 (de) | 2017-11-30 | 2019-06-06 | Basf Se | Verfahren zur kontinuierlichen herstellung von 1,2-propylendiamin (1,2-pda) und dimethyldiet-hylentriamin (dmdeta) |
US11274072B2 (en) | 2017-11-30 | 2022-03-15 | Basf Se | Process for the continuous preparation of 1,2-propylene diamine (1,2-PDA) and dimethyldiethylene triamine (DMDETA) |
WO2020178085A1 (en) | 2019-03-06 | 2020-09-10 | Basf Se | Method for the production of ethyleneamines |
Also Published As
Publication number | Publication date |
---|---|
US20090286977A1 (en) | 2009-11-19 |
US20120035049A1 (en) | 2012-02-09 |
US8765634B2 (en) | 2014-07-01 |
CN101489979A (zh) | 2009-07-22 |
JP2009543831A (ja) | 2009-12-10 |
EP2043996A1 (de) | 2009-04-08 |
RU2009104740A (ru) | 2010-08-27 |
US8063252B2 (en) | 2011-11-22 |
CN101489979B (zh) | 2015-04-08 |
JP5637684B2 (ja) | 2014-12-10 |
EP2043996B1 (de) | 2012-10-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2043996B1 (de) | Verfahren zur herstellung eines amins | |
EP2043997B1 (de) | Verfahren zur herstellung eines amins | |
EP2225027B1 (de) | Verfahren zur herstellung eines amins | |
EP2225029B1 (de) | Verfahren und katalysator zur herstellung eines amins | |
EP2225030B1 (de) | Verfahren zur herstellung eines amins | |
EP2506966B1 (de) | Katalysator und verfahren zur herstellung eines amins | |
EP2061747B1 (de) | Verfahren zur herstellung eines amins | |
EP2506965B1 (de) | Katalysator und verfahren zur herstellung eines amins | |
EP1487573B1 (de) | Katalysatoren und verfahren zur herstellung von aminen | |
EP2346602B1 (de) | Verfahren zur kontinuierlichen herstellung eines amins unter verwendung eines aluminium-kupfer-katalysators | |
WO2008006754A1 (de) | Verfahren zur herstellung eines amins | |
EP2043779A1 (de) | Verfahren zur herstellung eines amins | |
EP2234717A1 (de) | Verfahren zur herstellung eines amins | |
WO2009080514A1 (de) | Verfahren zur herstellung eines amins | |
EP1747187A1 (de) | Verfahren zur kontinuierlichen herstellung eines amins | |
EP2225028A1 (de) | Verfahren zur herstellung eines amins | |
WO2009080515A1 (de) | Verfahren zur herstellung eines amins | |
DE102005029093A1 (de) | Verfahren zur kontinuierlichen Herstellung eines Amins | |
WO2008138833A1 (de) | Verfahren zur herstellung von aminen | |
EP2883862A1 (de) | Verfahren zur Herstellung von Aminen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780026682.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07765787 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2007765787 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009519905 Country of ref document: JP Ref document number: 12373825 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 801/CHENP/2009 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 2009104740 Country of ref document: RU Kind code of ref document: A |