WO2003042158A1 - Procede pour la production de mono-isopropylamine - Google Patents

Procede pour la production de mono-isopropylamine Download PDF

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Publication number
WO2003042158A1
WO2003042158A1 PCT/EP2002/012803 EP0212803W WO03042158A1 WO 2003042158 A1 WO2003042158 A1 WO 2003042158A1 EP 0212803 W EP0212803 W EP 0212803W WO 03042158 A1 WO03042158 A1 WO 03042158A1
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Prior art keywords
hydroamination
mipa
hydrogenation
weight
catalyst
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PCT/EP2002/012803
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German (de)
English (en)
Inventor
Frank Funke
Ulrich Steinbrenner
Ralf Böhling
Peter Rudolf
Klaus Breuer
Hartmut Hibst
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Basf Aktiengesellschaft
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Priority to EP02796546A priority Critical patent/EP1448511A1/fr
Publication of WO2003042158A1 publication Critical patent/WO2003042158A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/64—Preparation of compounds containing amino groups bound to a carbon skeleton by disproportionation

Definitions

  • the present invention relates to a process for the preparation of monoisopropylamine (MIPA; (CH 3 ) CHNH 2 ).
  • MIPA is an important organic intermediate product that is required, among other things, as a preliminary product for the production of crop protection products.
  • MIPA is manufactured in industry by aminating hydrogenation of isopropanol or acetone with ammonia over catalysts.
  • EP-Al-1 106 601 (BASF AG) describes the preparation of MIPA by reacting acetone with ammonia and with hydrogen at elevated temperature and pressure in the presence of a specific catalyst which contains Cu, Ni and Co.
  • MIPA can also be made by amination of isopropanol.
  • DE-A-19 53 263 (BASF AG) relates to the use of certain Co, Ni and Cu-containing catalysts for the production of amines from alcohols.
  • EP-Al-1 106 601, page 2, lines 10-42 For the discussion of the further prior art for the amination of acetone or isopropanol to MIPA, reference is made here to EP-Al-1 106 601, page 2, lines 10-42.
  • a disadvantage of the processes for producing MIPA starting from acetone or isopropanol is that these starting materials are relatively expensive.
  • C3 building blocks other than acetone such as e.g. can be achieved by using propene, propadiene or propyne.
  • Propene, propadiene and propyne are available in relatively large quantities at locations with hydrocracking technology (strea cracker).
  • Preferred catalysts for the hydroamination stage are alkali metal dialkylamides and zeolites (claim 10).
  • Examples here are the copper salt-catalyzed reactions according to BE 637 033 (BASF AG), alkali metal hydroxide-catalyzed
  • EP-Al-982 293 discloses a process for the preparation of imines and / or enamines by addition of ammonia, primary amines or secondary amines to acetylenes and / or allenes, by carrying out the reaction in the gas phase at elevated temperature in the presence performed by an amorphous and / or crystalline zinc and / or cadmium silicate-containing heterogeneous catalyst (claim 1).
  • ammonia can be used as a starting material in this process, but alkylamines and cycloalkylamines are preferred.
  • Acetylene and methyl acetylene (propyne) are preferred as alkynes which can be used (page 3, line 58).
  • the reaction of MIPA with propyne and subsequent hydrogenation leads to N, N-diisopropylamine (DIPA) using this process.
  • the object of the present invention was to find an improved, economical process for producing MIPA in good yield and selectivity while overcoming the disadvantages of the prior art.
  • MIPA monoisopropylamine
  • the propyne and / or propadiene used in the process according to the invention is preferably used in the form of an appropriately propyne and / or propadiene-containing C3 cut, as can be obtained, for example, from a steam cracker.
  • this mixture can also be enriched with propyne beforehand.
  • the following table shows the typical composition of a usable, propyne and propadiene-containing, propene-enriched C3 section.
  • the method according to the invention can be carried out as follows.
  • propyne and / or propadiene is reacted with MIPA under hydroaminating conditions.
  • acetone imine (CH 3 ) 2 C (H) -N C (CH 3 ) 2 .
  • This first hydroamination step is very particularly preferably carried out in the presence of a catalyst, in particular a heterogeneous catalyst.
  • the reaction of monoisopropylamine with propyne and / or propadiene is preferably carried out in the gas phase, for example on a fixed bed or fluidized bed, generally at temperatures from 100 to 370 ° C., absolute pressures from 0.1 to 50 bar, (all pressures based on the sum the partial pressures of the educts), especially at normal pressure.
  • Monoisopropylamine (MIPA) with propyne and / or propadiene is generally in the molar ratio of amine to [alkyne + diene] from 0.01 to 100, particularly 0.2 to 10, preferably 0.3 to 5, in particular 0.7 to 2 , 0, implemented.
  • Unreacted or excess MIPA can be separated from the reaction mixture obtained (e.g. by distillation) and returned to the hydroamination reaction.
  • An amorphous and / or crystalline zinc and / or cadmium silicate-containing heterogeneous catalyst is particularly preferably used as the hydroamination catalyst.
  • Such catalysts are e.g. in EP-A-887 330, EP-A-887 331 and EP-A-982 293 (all BASF AG).
  • catalysts containing zinc and / or cadmium silicate preference is given to those selected from the groups (a), (b) and (c) explained below:
  • e means the values 0 to the sum of 2a + 2c
  • the ratio a / c is 1 to 3.5
  • f / a is 0 to 200.
  • X-ray amorphous zinc silicate or cadmium silicate catalysts are obtained, for example, by loading amorphous silica with a zinc salt or cadmium salt and shaping the catalyst by a thermal treatment.
  • the Si0 carrier is at least predominantly amorphous, has a BET surface area between 10 and 1500 m 2 / g, preferably 100 to 500 m 2 / g, a water absorption capacity of 0.1 to 2 ml / g, preferably 0.7 to 1.3 ml / g, and can be used as a powder or as a finished molded article.
  • the carrier can also be calcined before impregnation. However, the carrier is preferably not calcined.
  • a zinc-soluble or cadmium compound is a compound that is soluble in a suitable solvent.
  • Zinc (II) salts which are soluble in water or aqueous ammonia or alcohols, preferably lower alcohols and whose decomposition temperature is below 400 ° C. to 500 ° C. are preferably used.
  • An ammoniacal zinc (II) acetate solution is particularly preferably used for the impregnation. In some cases, it has proven advantageous to carry out the loading with zinc in several successive impregnation steps. Such impregnation processes are known in the art and are known to the person skilled in the art (see also below).
  • the catalyst can be brought into the desired shape by shaping (e.g. by mixing, kneading and extruding or tableting).
  • pore formers can also be added during the shaping (e.g. superabsorbents such as Lutexal® P (BASF AG, Ludwigshafen) or Walocel® (methyl cellulose / synthetic resin combination; Wolff, Walsrode)).
  • superabsorbents such as Lutexal® P (BASF AG, Ludwigshafen) or Walocel® (methyl cellulose / synthetic resin combination; Wolff, Walsrode)
  • another carrier for example Al 2 0 3
  • R organic radical, for example C 1 -C 8 -alkyl
  • the zinc or cadmium loading can vary within wide limits. Typical values for an uncalcined precatalyst which was prepared by impregnating an SiO 2 support with a zinc salt or cadmium salt are, for example, between 1 and 60% by weight of Zn or Cd, preferably between 7 and 30% by weight, in particular between 10 and 25% by weight (each calculated as ZnO or CdO).
  • the precatalyst can also be doped with compounds of other elements, preferably with alkali, alkaline earth or transition metals.
  • the catalytically active component can be doped with up to 80, preferably up to 50 and in particular up to 20 mole percent with further metals, selected from group (A) consisting of beryllium, magnesium, calcium, strontium, barium, Manganese, iron, cobalt, nickel and copper, and group (B), consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) being partially zinc or cadmium and the elements of the group (B) partially replace silicon.
  • group (A) consisting of beryllium, magnesium, calcium, strontium, barium, Manganese, iron, cobalt, nickel and copper
  • group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) being partially zinc or cadmium and the elements of the group (B) partially replace silicon.
  • the precatalyst can then be calcined at a temperature of at most 600 ° C., preferably between 80 and 400 ° C., in air or under an inert gas. Calcination between 120 and 325 ° C. in air is particularly preferred.
  • a formation is generally carried out in which - especially on the surface of the catalyst - the actual active phase formed.
  • This solid-state reaction is promoted by the presence of water, alcohols, preferably lower alcohols (such as C 1 -C 4 alcohols), carboxylic acids, preferably lower carboxylic acids (such as C 1 -C 4 carboxylic acids), ammonia or amines, and is therefore expediently heated by heating the Precatalyst carried out at a temperature between 50 and 400 ° C in an aqueous atmosphere containing alcohol and / or amine.
  • the reaction is preferably carried out between 100 and 350 ° C. in an aqueous gas mixture containing methanol and / or ethylamine. It is particularly preferred to carry out the reaction between 120 and 300 ° C. with an amine-containing gas mixture directly in the reactor in which the reaction of the propyne and / or propadiene with the MIPA is to take place later.
  • the corresponding mercury silicates can be produced in the same way, but are less technically and ecologically less suitable.
  • Standard methods were used to characterize the catalyst samples (fresh as well as removal samples).
  • the measured BET surface area is typically between 10 and 800 m 2 / g. Catalysts with BET surface areas between 100 and 400 m 2 / g are preferred.
  • the samples were examined in detail by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). With both structure-elucidating methods no long-range order in the sense of a crystalline structure can be detected, all samples were amorphous. The distribution of the zinc over the carrier was examined on corresponding sections in the electron microscope and in the microsensor. All samples show, even after removal, that the catalyst has a largely homogeneous element distribution and contains little or no crystalline ZnO.
  • Catalysts dried at room temperature have a C / Zn ratio of 3.5-4. After calcination at 200-250 ° C (optimal temperature), the C / Zn ratio is between 1 and 2. At higher temperatures, the C / Zn ratio drops even further, as does the catalytic activity of the catalysts formed from it. After calcination at 500 ° C (24 hours), the C / Zn ratio in the precatalyst is 0.02. No active catalyst can be formed from this. Since the decomposition of the zinc acetate on the precatalyst is relatively slow, it can be exposed to even higher temperatures for a short time without the catalytic activity being completely lost.
  • Hemimorphite is a zinc silicate of the formula ZnSi 0 (OH) 2 »H 2 0.
  • heterogeneous catalysts are suitable for the reaction according to the invention which contain at least predominantly zinc silicate with the structure of the hemimorphite of the formula Zn 4 Si as an active component 2 0 (OH) _ 2y O y * xH0, where x and y each represent values from 0 to 1.
  • hemimorphite The production of hemimorphite is known from the literature. It can take place under normal conditions or hydrothermal conditions. A hemimorphite is preferably used as it is obtained according to the information in EP-A-887 330 (BASF AG).
  • an X-ray amorphous product with improved catalytic properties can be obtained with shorter reaction times than is required for the precursor for the production of a crystalline hemimorphite.
  • an aqueous suspension or solution of an alkali or alkaline earth silicate with an aqueous solution of a zinc salt is added a) Temperatures from 20 ° C, preferably 50 ° C, to the boiling point of the resulting aqueous suspension
  • the essentially X-ray amorphous zinc silicate thus obtainable contains Zn 2+ , Si + and 0 2 "ions; the compound can also contain OH ions and water of hydration.
  • the Zn / Si atomic ratio is 0.3 to 5 , preferably 1 to 2.7, in particular 2 to 2.3.
  • the amorphous zinc silicate precipitation catalyst to be used according to the invention can also be doped with up to 80, preferably up to 50, and in particular up to 20 mol%, with further metals selected from group (A) consisting of beryllium, magnesium, calcium , Strontium, barium, manganese, iron, cobalt, nickel, copper, cadmium and mercury and group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) being partly zinc and the elements of group (B) partially replace silicon in the imorphite structure.
  • group (A) consisting of beryllium, magnesium, calcium , Strontium, barium, manganese, iron, cobalt, nickel, copper, cadmium and mercury
  • group (B) consisting of titanium, zirconium, hafnium, germanium, tin and lead, the elements of group (A) being partly zinc and the elements of group (B) partially replace silicon in the i
  • the reaction of isopropylamine with propyne and / or propadiene takes place in the presence of the heterogeneously present catalyst containing zinc and / or cadmium silicate in the gas phase either over a fixed bed or in a fluidized bed at temperatures from 100 to 370 ° C., preferably 150 to 320 ° C. , and in particular 180 to 280 ° C and absolute pressures of 0.1 to 50 bar, preferably 0.8 to 20 bar, and particularly preferably 0.9 to 10 bar (all pressures based on the sum of the partial pressures of the starting materials), in particular at normal pressure.
  • Suitable reactors are, for example, fixed bed reactors (tube bundle, shaft furnace) or autoclaves with a catalyst basket. If necessary, the reaction mixture can be diluted with inert gases such as nitrogen, argon, low molecular weight alkanes or olefins for reasons of operational safety and better heat dissipation.
  • inert gases such as nitrogen, argon, low molecular weight alkanes or olefins for reasons of operational safety and better heat dissipation.
  • Isopropylamine (MIPA) with propyne and / or propadiene is generally in a molar ratio of amine to [alkyne + diene] from 0.01 to 100, particularly 0.2 to 10, preferably 0.3 to 5, in particular 0.7 to 2 , 0, implemented.
  • Unreacted or excess MIPA can be separated from the reaction mixture obtained (e.g. by distillation) and returned to the hydroamination reaction.
  • the shaped bodies of the catalyst are selected such that they have a space-time yield - in particular because of a possible diffusion limitation, which of course also affects the selectivities and the catalyst life can - and pressure loss in the reactor results in an economic optimum.
  • the catalyst is preferably in the form of strands of 1 to 5 mm in diameter, tablets of 5 ⁇ 5 ⁇ 5 mm to 1 ⁇ 1 ⁇ 1 mm, in the form of rib strands, asterisks or chips of a similar size.
  • the catalyst can be regenerated. This can be done in the hydroamination reactor or outside in special equipment.
  • the regeneration can be carried out by heating in a reducing, for example hydrogen or CO-containing, inert, for example N 2 , C0 or the noble gases, or oxidizing, for example 0-containing, atmosphere.
  • the oxidizing atmosphere is preferred, particularly preferably air or mixtures of air and nitrogen.
  • Regeneration takes place at temperatures from 150 ° C to 1000 ° C, preferably 350 ° C to 600 ° C.
  • the catalyst can also be carried out by treatment with H 2 0 at temperatures from 20 ° C. to 350 ° C., so-called steaming, or by rinsing with suitable solvents such as MIPA, DIPA, NMP, THF, sulfolane, DMF, NH 3 or toluene ,
  • suitable solvents such as MIPA, DIPA, NMP, THF, sulfolane, DMF, NH 3 or toluene .
  • H0 at temperatures of 20 ° C to 350 ° C before removal to remove toxic or organic adsorbates.
  • Used and regenerated catalyst can now be reused directly for the catalysis, or it can be appropriately returned to the catalyst production, for example in the Impregnation with the active component, eg Zn salt solution, or in the carrier production.
  • the hydroamination product (s) obtained in the first process step is then reacted with ammonia under transalkylating conditions and under hydrogenating conditions.
  • this reaction can be carried out a) with ammonia under transalkylating conditions and b) under hydrogenating conditions in two corresponding separate steps, the sequence of which is arbitrary.
  • one step after the other, in any sequence are the hydrogenation and dehydrogenation catalysts mentioned below for the reaction with ammonia under transalkylating conditions, generally at temperatures from 80 to 400 ° C., suitable.
  • the hydrogenation and dehydrogenation catalysts mentioned below are also suitable as catalysts, generally at temperatures from 80 to 400 ° C.
  • the hydroamination product (s) obtained in the first process stage is / are then preferably reacted in the second process stage in the presence of ammonia, hydrogen and a transalkylating hydrogenation or dehydrogenation catalyst, generally at temperatures from 80 to 400 ° C.
  • the reaction discharge from the first process stage can, as a rule after the catalyst has been separated off, be used directly in the second process stage.
  • the hydrogenation and dehydrogenation catalysts are catalysts which, as catalytically active constituents, are elements selected from the group consisting of copper, silver, gold, iron, cobalt, nickel, rhenium, ruthenium, rhodium, palladium, osmium, iridium, platinum, chromium, molybdenum and tungsten , in each case in metallic form (oxidation level 0) or in the form of compounds such as oxides, the under the process conditions are reduced to the corresponding metal, contain, particularly suitable.
  • the catalytically active components copper, silver, gold, iron, cobalt, nickel, rhenium, ruthenium, rhodium, palladium, osmium, iridium, platinum, chromium, molybdenum and / or tungsten are generally in total from 0.1 to 80% by weight .-%, preferably 0.1 to 70 wt .-%, particularly preferably 0.1 to 60 wt .-%, calculated as metal in the oxidation state 0, contained in the catalytically active mass of the catalyst.
  • Catalysts are preferred which contain, as catalytically active constituents, elements selected from the group of copper, silver, cobalt, nickel, ruthenium, rhodium, palladium, platinum, chromium and molybdenum, in particular selected from the group copper, cobalt,
  • Nickel each in metallic form (oxidation level 0) or in the form of compounds such as Oxides, which are reduced to the corresponding metal under the process conditions, contain.
  • catalysts which contain the catalytically active constituents copper, silver, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and / or platinum and a support material, preferably selected from the group consisting of aluminum oxide, zirconium dioxide and titanium dioxide. Contain carbon and / or oxygen-containing compounds of silicon.
  • the catalytically active composition of these catalysts preferably used in the process according to the invention contains the catalytically active constituents copper, silver, iron, cobalt, nickel,
  • Ruthenium, rhodium, palladium, osmium, iridium and / or platinum generally in total in amounts of 0.1 to 80% by weight, preferably 0.1 to 70% by weight, particularly preferably 0.1 to 60% by weight %, calculated as metal in oxidation state 0.
  • the catalytically active composition of these preferred catalysts contains the support materials aluminum oxide (Al 2 0 3 ), zirconium dioxide (Zr0), titanium dioxide (Ti0 2 ), carbon and / or oxygen-containing compounds of silicon, calculated as Si0, generally in total in amounts of 20 to
  • Catalysts with the active components Cu, Co, Ni and / or Pd, in particular Cu, Co and / or Ni, are particularly preferred. These can be used as full contacts or as supported catalysts.
  • Cu-containing catalysts are very particularly preferred which, as was recognized according to the invention, are more selective because of their comparatively low formation of ethane or methane compared to noble metal catalysts.
  • Examples are copper alloys, metallic copper, e.g. in the form of copper network, and Cu catalysts with a Cu content of 2 to 70% by weight of Cu, calculated as CuO, on a support, preferably with 10 to 55% by weight of Cu, calculated as CuO, on a support ,
  • Carrier material can preferably be aluminum oxide (A1 2 0 3 ), zirconium dioxide (Zr0), titanium dioxide (Ti0), carbon and / or oxygen-containing compounds of silicon (Si0 2 ).
  • catalysts disclosed in EP-A-382 049 whose catalytically active composition before treatment with hydrogen can be 20 to 85% by weight, preferably 70 to 80% by weight, ZrO 2 , 1 to 30% by weight, preferably 1 to 10 wt .-%, CuO, and each 1 to 40 wt .-%, preferably 5 to 20 wt .-%, contains CoO and NiO, for example those in loc. cit.
  • catalysts described on page 6 with the composition 76% by weight of Zr, calculated as Zr0 2 , 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as NiO, can be used in the process according to the invention.
  • the catalysts disclosed in EP-A-963 975 whose catalytically active composition before treatment with hydrogen, 22 to 40% by weight of ZrO 2 ,
  • catalysts disclosed in EP-A-514 692 in the process according to the invention are preferred from 2: 1 to 5: 1, and contains zirconium and / or aluminum oxide, especially those described in loc. cit. on page 3, lines 20 to 30, disclosed catalysts whose catalytically active composition before treatment with hydrogen 20 to 80, in particular 40 to 70,% by weight of A1 2 0 3 and / or Zr0 2 , 1 to 30% by weight % CuO, 1 to 30 wt .-% NiO and 1 to 30 wt .-% CoO can be used.
  • Catalysts disclosed in DE-A-19 53 263 can preferably contain cobalt, nickel and copper and aluminum oxide and / or silicon dioxide with a metal content of 5 to 80% by weight, in particular 10 to 30% by weight, based on the total Catalyst, the catalysts, calculated on the metal content, containing 70 to 95% by weight of a mixture of cobalt and nickel and 5 to 30% by weight of copper, and the weight ratio of cobalt to nickel being 4: 1 to 1: 4, in particular 2: 1 to 1: 2,
  • the catalysts disclosed in EP-A-696 572 the catalytically active composition of which before reduction with hydrogen is 20 to 85% by weight of Zr0, 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, 30 to 70% by weight.
  • % of oxygen-containing compounds of nickel, calculated as NiO, 0.1 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as M0O 3 , and 0 to 10% by weight of oxygen-containing compounds of aluminum and / or manganese, calculated as A10 3 or Mn0 contains, for example, that in loc. cit., page 8, disclosed catalyst with the composition 31.5% by weight of ZrO 2 , 50% by weight of NiO, 17% by weight of CuO and 1.5% by weight of Mo0 3 ,
  • the catalysts of the general formula M x Mg y (Si0) «nH0 disclosed in EP-A-284 919 where M is a divalent, reducible metal atom from the group Cu, Fe, Co and Ni, x and y numbers which together form the Can reach a value of 1.5, and n after drying, expressed in% by weight, is between 0 and 80, for example that in loc. cit catalyst described in the example containing 35% CuO, 9% MgO and 38% SiO 2 and the catalyst described in EP-A-863 140 on page 3 containing 45 to 47% by weight CuO,
  • Magnesium silicate composed of approximately 15 to 17% by weight of MgO and 35 to 36 % By weight Si0 2 , approximately 0.9% by weight Cr 2 0 3 , approximately 1% by weight BaO and approximately 0.6% by weight ZnO,
  • Example 1 disclosed copper-containing precipitation catalyst, which is prepared by treating a solution of copper nitrate and aluminum nitrate with sodium bicarbonate and then washing, drying and tempering the precipitate, and
  • the supported catalysts disclosed in WO 95/32171 and EP-A-816 350 containing 5 to 50, preferably 15 to 40,% by weight of copper, calculated as CuO, 50 to 95, preferably 60 to 85,% by weight of silicon, calculated as Si0, 0 to 20% by weight of magnesium, calculated as MgO, 0 to 5% by weight of barium, calculated as BaO, 0 to 5% by weight of zinc, calculated as ZnO, and 0 to 5% by weight % Chromium, calculated as Cr0 3 , in each case based on the total weight of the calcined catalyst, for example the catalyst disclosed in EP-A-816 350, page 5, comprising 30% by weight CuO and 70% by weight Si0,
  • the hydrogenation or dehydrogenation catalysts used as transalkylation catalyst and hydrogenation catalyst in the process according to the invention can be prepared by the processes described in the prior art and some of them can also be obtained commercially.
  • a metal salt solution in one or more impregnation stages to a prefabricated inorganic carrier.
  • the carrier is dried and, if necessary, calcined. al)
  • the impregnation can be carried out according to the so-called "incipient wetness" method, in which the carrier is moistened with the impregnation solution to a maximum of saturation in accordance with its water absorption capacity.
  • the impregnation can also take place in the supernatant solution.
  • the inorganic carrier material is preferably used in the impregnation as a preformed mass, for example as a powder, balls, strands or tablets. Use as a powder is particularly preferred.
  • Concentrated aqueous ammonia is preferably used as the solvent of the metal salts.
  • promoters can be carried out in one step analogously to al) by impregnation with a corresponding metal-containing impregnation solution, e.g. copper, cobalt and / or nickel-containing impregnation solution, and promoter-containing impregnation solution or multi-stage analog a2) by alternating impregnation with metal-containing impregnation solution and promoter-containing impregnation solution.
  • a metal-containing impregnation solution e.g. copper, cobalt and / or nickel-containing impregnation solution, and promoter-containing impregnation solution or multi-stage analog a2
  • Precipitation of a metal salt solution onto a prefabricated, inert inorganic carrier is present as a powder in an aqueous suspension.
  • a metal salt solution preferably with soda solution
  • An aqueous suspension of the carrier material is used as a template.
  • the precipitation catalyst can be produced in a two-stage process. In a first stage, a powder is produced and dried in accordance with the information from a). This powder is transferred into an aqueous suspension and used as a template equivalent to that described in embodiment (i).
  • promoters can be carried out in one step analogously to bl) by precipitation of a metal-containing solution or in several stages analogously to b2) by successive precipitation of a metal-containing solution Solution and promoter-based solution take place.
  • the individual precipitations can follow one another directly or can be separated by a washing process and / or drying process and / or calcining process.
  • metal (I) and / or metal (II) salts soluble in the solvents used in the application for example sulfates, nitrates, chlorides, carbonates, acetates, oxalates or ammonium, can be used as starting substances for a) and / or b) Complexes can be used.
  • Metal carbonates are particularly preferably used for processes according to a), and metal nitrate for processes according to b).
  • Precipitated precipitates resulting from a) or b) are filtered in a conventional manner and preferably washed free of alkali.
  • a promoter component in a suitable form into the filtered and optionally washed precipitate.
  • suitable forms are, for example, inorganic salts or complexes or organic compounds.
  • Both the end products from a) and those from b) are dried at temperatures from 50 to 150 ° C, preferably at 100 to 140 ° C, and if necessary subsequently, e.g. over a period of 2 hours, at a higher temperature, i.e. generally 200 to 400 ° C, especially at 200 to 220 ° C, annealed.
  • a promoter component in a suitable form both after drying and after tempering.
  • suitable forms are, for example, inorganic salts or complexes or organic compounds.
  • the introduction is expediently carried out by intensive mixing, kneading and / or compacting, it also being possible, if appropriate, to add liquids, for example water or alcohols.
  • a further drying and / or tempering step is expediently carried out. When added in the dry state, however, this can also be omitted if necessary.
  • the dried powder described above is preferably shaped into tablets or similar shaped articles.
  • Graphite preferably in a proportion of 3% by weight, based on the weight of the dried powder, is added as a tabletting aid for the shaping process.
  • the tablet tablets are annealed, preferably for 2 hours, at 300 to 600 ° C, in particular at 330 to 350 ° C.
  • this particular process for tableting allows the powder to be shaped into tablets particularly easily and provides very chemically and mechanically stable catalysts.
  • a promoter component in a suitable form into the shaped tablets.
  • suitable forms are, for example, solutions of inorganic salts or complexes or organic compounds.
  • After introduction it is expedient to dry again at temperatures of 50 to 150 ° C., preferably 100 to 140 ° C.
  • an annealing preferably for about 2 hours, can take place at 300 to 600 ° C, in particular at 330 to 350 ° C.
  • the reaction in the second process stage takes place under transalkylating and simultaneously hydrogenating conditions in the presence of hydrogen and ammonia and a transalkylating hydrogenation or dehydrogenation catalyst.
  • the degree of conversion of the hydroamination products from the first stage of the process into MIPA depends on the amount of ammonia used. For a large proportion of MIPA in the process product, an excess of ammonia based on the hydroamination product (s) should be selected
  • the procedure is preferably that the product or product mixture from the first process stage, or that by working up the first
  • Process stage / s obtained product amine (s) is / are continuously passed over the transalkylation / hydrogenation catalyst or is batchwise transalkylated and hydrogenated in the presence of the transalkylation / hydrogenation catalyst.
  • the catalyst is installed in a tube reactor or tube bundle reactor.
  • the catalyst can optionally be reduced beforehand with hydrogen, but it can also be started up directly in the presence of the starting material / starting material mixture to be reacted and hydrogen.
  • the absolute hydrogen pressure in the second process stage can be chosen between 0 bar and 300 bar, preferably between 1 and 250 bar. In the case of a reaction in the gas phase, the absolute pressure is generally from 1 to 70 bar.
  • the absolute pressure is generally 70 to 250 bar.
  • the temperature in the second process stage is generally from 80 to 400 ° C., in particular from 100 to 350 ° C., preferably from 120 to 250 ° C., very particularly preferably from 150 to 230 ° C.
  • thermodynamic equilibrium is established between the alkylamines according to the process and ammonia.
  • the loading of the catalyst with the starting material can be between 0.05 and 2 kg amine per liter of catalyst and per hour (kg / l »h), preferably between 0.1 and 1 kg / l * h, particularly preferably between 0.2 and 0.6 kg / l «h.
  • the molar ratio of the transalkylation partner ⁇ ammonia: [N-isopropyl-N-isopropenyl-amine + N-isopropyl-acetonimine] is generally in the range from 0.5 to 50, particularly in the range from> 1 to 20, very particularly in Range from 2 to 5.
  • the catalyst can be introduced together with the starting material for the second process stage and the desired amount of the ammonia can be added. Then it is heated to the desired temperature (see above).
  • the processing of the product obtained in the second stage of the process, which contains MIPA can be carried out by customary methods, e.g. Distillation or rectification, which may be carried out in several stages.
  • the boiling point of MIPA is 33 to 34 ° C at normal pressure.
  • Part of the MIPA produced can be recycled to the first stage of the process for the hydroamination of propyne and / or propadiene.
  • Propyne (10 1 / h) was reacted at normal pressure together with NH 3 (likewise 10 1 / h) and nitrogen (5 1 / h) in a tubular reactor at 230 ° C. over 60 ml of the amorphous zinc silicate as in Example 1.
  • the reactor discharge was condensed and examined by gas chromatography. The conversion was ⁇ 10%, whereby the desired isopropenyl laminate could only be detected in small quantities.
  • pyridine derivatives with selectivities ⁇ 10% could be detected.
  • Example 3 (Implementation of the Reaction Discharge from Example 1 (Transalkylation / Hydrogenation))
  • a hydrogenation catalyst (10% by weight of CoO, 10% by weight of NiO and 4% by weight of CuO on Al 2 O 3) according to DE-A-19 was placed in a continuously operated laboratory apparatus (60 ml tubular reactor) without recirculation 53 263) installed and started without activation at 65 bar hydrogen pressure.
  • the load of 0.2 kg / l »h (kg of starting material per liter of catalyst and per hour) was left constant:
  • N-isopropyl-propenylamine from Example 1
  • 10 ml of ammonia (liquid) and 20 bar of hydrogen were injected into a 0.3 l autoclave.
  • the temperature was brought to 200 ° C. and hydrogen was injected to 200 bar;
  • the reaction was carried out at 200 ° C. and 200 bar for 12 h.
  • the reactor contents were relaxed in 350 g of water via a frit.
  • a discharge was obtained which consisted exclusively of MIPA (90% by weight), DIPA (9.7% by weight) and traces of N-isopropyl-1-propenylamine and n-propylamine.

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  • Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un procédé pour la production de mono-isopropylamine (MIPA), selon lequel on fait réagir du propyne ou du propadiène avec de la MIPA dans des conditions d'hydroamination. On fait ensuite réagir le ou les produits d'hydroamination obtenus avec de l'ammoniac dans des conditions de transalkylation et d'hydrogénation.
PCT/EP2002/012803 2001-11-17 2002-11-15 Procede pour la production de mono-isopropylamine WO2003042158A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP02796546A EP1448511A1 (fr) 2001-11-17 2002-11-15 Procede pour la production de mono-isopropylamine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10156685.9 2001-11-17
DE2001156685 DE10156685A1 (de) 2001-11-17 2001-11-17 Verfahren zur Herstellung von Monoisopropylamin

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WO2003042158A1 true WO2003042158A1 (fr) 2003-05-22

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EP (1) EP1448511A1 (fr)
DE (1) DE10156685A1 (fr)
WO (1) WO2003042158A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0982293A1 (fr) * 1998-08-14 2000-03-01 Basf Aktiengesellschaft Procédé de préparation d'imines et d'ènamines ainsi qu'éventuellement leur hydrogénation en amines
EP1106601A1 (fr) * 1999-12-06 2001-06-13 Basf Aktiengesellschaft Procédé pour la préparation de la mono-isopropylamine
WO2001085667A1 (fr) * 2000-05-12 2001-11-15 Duslo, A.S. Šal'a Procede de preparation d'amines aliphatiques
WO2002000597A2 (fr) * 2000-06-28 2002-01-03 Basf Aktiengesellschaft Procede de production d'alkylamines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0982293A1 (fr) * 1998-08-14 2000-03-01 Basf Aktiengesellschaft Procédé de préparation d'imines et d'ènamines ainsi qu'éventuellement leur hydrogénation en amines
EP1106601A1 (fr) * 1999-12-06 2001-06-13 Basf Aktiengesellschaft Procédé pour la préparation de la mono-isopropylamine
WO2001085667A1 (fr) * 2000-05-12 2001-11-15 Duslo, A.S. Šal'a Procede de preparation d'amines aliphatiques
WO2002000597A2 (fr) * 2000-06-28 2002-01-03 Basf Aktiengesellschaft Procede de production d'alkylamines

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DE10156685A1 (de) 2003-05-28

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