WO2014184039A1 - Procédé de production de n-alkylpipérazines - Google Patents

Procédé de production de n-alkylpipérazines Download PDF

Info

Publication number
WO2014184039A1
WO2014184039A1 PCT/EP2014/059145 EP2014059145W WO2014184039A1 WO 2014184039 A1 WO2014184039 A1 WO 2014184039A1 EP 2014059145 W EP2014059145 W EP 2014059145W WO 2014184039 A1 WO2014184039 A1 WO 2014184039A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
hydrogen
reaction
ammonia
oxygen
Prior art date
Application number
PCT/EP2014/059145
Other languages
German (de)
English (en)
Inventor
Hendrik De Winne
Roland Bou Chedid
Johann-Peter Melder
Ulrich Abel
Bernd Stein
Roman Dostalek
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2014184039A1 publication Critical patent/WO2014184039A1/fr

Links

Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a process for the preparation of an N-alkyl-piperazine of the formula I.
  • R 1 is hydrogen (H), methyl or ethyl and R 2 is C 1 -C 5 -alkyl
  • the process products find use, inter alia, as intermediates in the preparation of pharmaceutical active substances such as antibiotics.
  • WO 03/051508 A1 (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 ).
  • the catalysts described in this WO application contain no alumina and no cobalt.
  • WO 2008/006750 A1 (BASF AG) relates to certain Pb, Bi, Sn, Sb and / or in-doped, zirconium dioxide, copper, nickel and cobalt-containing catalysts and their use in processes for the preparation of an amine by reacting a primary or secondary alcohol, aldehydes and / or ketones with hydrogen and ammonia, a primary or secondary amine.
  • WO 2009/080507 A1 (BASF SE) relates to certain Sn- and Co-doped, zirconium dioxide, copper and nickel-containing catalysts and their use in processes for preparing an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and ammonia, a primary or secondary amine.
  • WO 2009/080506 A1 (BASF SE) describes certain Pb, Bi, Sn, Mo, Sb and / or P-doped, zirconium dioxide, nickel and iron-containing catalysts and their use in processes for preparing an amine by reacting a primary or secondary Alcohols, aldehydes and / or ketones with hydrogen and ammonia, a primary or secondary amine.
  • the catalysts preferably contain no Cu and no Co.
  • WO 2009/080508 A1 (BASF SE) teaches certain Pb, Bi, Sn and / or Sb-doped, zirconium oxide, copper, nickel, cobalt and iron-containing catalysts and their use in processes for preparing an amine by reaction a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and ammonia, a primary or secondary amine.
  • WO 201 1/067199 A1 (BASF SE) relates to certain catalysts comprising aluminum oxide, copper, nickel, cobalt and tin and their use in processes for the preparation of an amine from a primary or secondary alcohol, aldehyde and / or ketone.
  • the preparation of ⁇ , ⁇ '-dimethyl-piperazine from N-methyldiethanolamine and monomethylamine (MMA) is generally mentioned on page 25, lines 21-22.
  • WO 201 1/157710 A1 and WO 2012/049101 A1 describe the preparation of certain cyclic tertiary methylamines, wherein an aminoalcohol from the group 1, 4-aminobutanol, 1, 5-aminopentanol, aminodiglycol (ADG) or Aminoethyl-ethanolamine, with a certain primary or secondary alcohol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
  • ADG aminodiglycol
  • Aminoethyl-ethanolamine with a certain primary or secondary alcohol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
  • CN 102 101 847 A (Zhangjiagang Tianyou New Materials Techn. Co., Ltd.) describes a two-step synthesis of N-methyl-N- (2-chloroethyl) -piperazine from aminodiglycol (ADG) via N-methyl-piperazine as an intermediate.
  • CN 102 304 101 A (Shaoxing Xingxin Chem. Co., Ltd.) relates to the simultaneous production of piperazine and N-alkylpiperazines by reacting N-hydroxyethyl-1, 2-ethanediamine with primary C-7 alcohols in the presence of metallic catalysts ,
  • EP 382 049 A1 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. The production of u.a. Piperazines of polybasic alcohols are mentioned on page 4, lines 49-50.
  • EP 696 572 A1 (BASF AG) relates to aminating hydrogenations using Zr2 / CuO / NiO / M0O3 catalysts.
  • the preparation of, inter alia, piperazines from polybasic alcohols is mentioned on page 4, lines 39-40.
  • EP 963 975 A1 (BASF AG) describes aminative hydrogenations using ZrO 2 / CuO / NiO / CoO catalysts.
  • EP 446 783 A2 (BASF AG) relates inter alia. the preparation of N-aryl-substituted piperazines by amination of corresponding N, N-di- (2-hydroxyalkyl) -N-aryl-amines.
  • EP 235 651 A1 (BASF AG) teaches a process for the preparation of N-methyl-piperazine from diethanolamine (DEOA) and monomethylamine (MMA) in the presence of metal-containing supported catalysts, in particular Cu-containing catalysts.
  • CN 1 413 991 A (Tianjing Univ.) Describes the reaction of N-beta-hydroxyethyl-ethanediamine (AEEA) and derivatives to piperazines at 120-380 ° C, 0 to 100 bar in the presence of H2 on metal-containing, A Os-supported catalysts , No.
  • AEEA N-beta-hydroxyethyl-ethanediamine
  • 3,907,802 (Henkel & Cie GmbH) describes the reaction of long-chain N-alkylated alkanolamines ("alkyl having 8 to 22 carbon atoms") with NH 3 or monomethylamine (MMA) at 200 to 350 ° C., about 50 to 405 bar , and a molar ratio of 3-30 (NH3 / MEA: alkanolamine) in the presence of H2 to specific Cr-oxide / ZnO or Al oxide / ZnO catalysts
  • the patent application EP 12171084.2 from 06.06.2012 (BASF SE) describes the Reaction of DEOA with NH 3 at 180-230 ° C, 50-300 bar, a molar ratio in the range of 1: 5 to 1:20 in the presence of H2 on a Cu-Ni-Co-Sn / A Os catalyst.
  • R 1 is hydrogen (H), methyl or ethyl and R 2 is C 1 -C 5 -alkyl
  • R 2 with ammonia or a primary amine of the formula H 2 N-R 1 (III) in the presence of hydrogen and a supported, metal-containing catalyst, which is characterized in that the catalytically active mass of the catalyst before its reduction with hydrogen 20 to 85 wt. % oxygen-containing compounds of zirconium, calculated as ZrO2,
  • the radical R 1 is an H atom (hydrogen, H), methyl or ethyl.
  • the radical R 2 is Ci-5-alkyl, preferably Ci-3-alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, particularly preferably methyl or ethyl.
  • the primary amine III is particularly preferably monomethylamine (MMA) or monoethylamine (MEA).
  • MMA monomethylamine
  • MEA monoethylamine
  • Amines of the formula I can preferably be prepared by the process according to the invention
  • amines of the formula I can preferably be prepared by the process according to the invention
  • N, N'-dimethylpiperazine and N-methyl-N'-ethyl-piperazine wherein in the latter compound, the methyl group from MMA used (reaction with N-ethyl-diethanolamine) or alternatively from N-methyl-diethanolamine used (reaction with MEA).
  • the process can be carried out continuously or batchwise. Preferred is a continuous driving style.
  • the starting materials N-substituted DEOA II, ammonia or the primary amine III
  • the starting materials are evaporated in a circulating gas stream and fed to the reactor in gaseous form.
  • the educts (N-substituted DEOA, ammonia or the primary amine III) 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".
  • the reaction is advantageously carried out in a tube bundle reactor or in a monostane system.
  • a tube bundle reactor or in a monostane system.
  • a Monostrangstrom the tubular reactor in which the reaction takes place from a
  • the cycle gas preferably contains at least 10, especially 50 to 100, especially 80 to 100,% by volume of hydrogen (H 2 ).
  • the catalysts are preferably used in the form of catalysts which consist only of catalytically active material and optionally a deformation Auxiliaries (such as graphite or stearic acid), if the catalyst is used as a shaped body, ie, contain no further catalytically active impurities.
  • the oxide carrier zirconium dioxide (ZrO-2) is considered to belong to the catalytically active material.
  • monoclinic, tetragonal or cubic modification is preferred. Particularly preferred is the monoclinic modification.
  • the catalysts are used in such a way that the catalytically active mass ground to powder is introduced into the reaction vessel or that the catalytically active material is treated as a shaped catalyst, for example tablets, spheres, rings, after grinding, mixing with shaping aids, shaping and heat treatment , Extrudates (eg strands) - in the reactor arranges.
  • the concentration data (in% by weight) of the components of the catalyst are in each case, if not stated otherwise, the catalytically active composition of the finished catalyst after its last heat treatment and before its reduction with hydrogen.
  • catalytically active mass of the catalyst is the sum of the masses of the catalytically active constituents and of the above-mentioned composition.
  • Catalyst carrier material defines and contains essentially the following components:
  • ZrO-2 Zirconium dioxide
  • oxygen-containing compounds of copper and nickel and possibly molybdenum The sum of o.
  • Components of the catalytically active composition are usually from 70 to 100% by weight, preferably from 80 to 100% by weight, particularly preferably from 90 to 100% by weight, especially> 95% by weight, very particularly> 98% by weight , in particular> 99 wt .-%, z. B. particularly preferably 100 wt .-%.
  • the catalytically active composition of the catalysts according to the invention and used in the process according to the invention may further contain one or more elements (oxidation state 0) or their inorganic or organic compounds selected from the groups I A to VI A and I B to VII B and VIII of the Periodic Table.
  • Transition metals such as Mn or MnÜ2, Mo or M0O3, 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 P ⁇ C; Alkaline earth metal oxides, such as SrO; Alkaline earth metal carbonates such as MgCO-3, CaCO-3 and BaCO-3; Alkali metal oxides such as Na 2 O, K 2 O; Alkali metal carbonates such as U2CO3, Na2CÜ3 and K2CO3; Boron oxide (B2O3).
  • Mn or MnÜ2, Mo or M0O3, W or tungsten oxides, Ta or tantalum oxides, Nb or niobium oxides or niobium oxalate, V or vanadium oxides or vanadyl pyrophosphate Lanthanides, such
  • the catalytically active composition of the catalyst preferably contains no oxygen-containing compounds of silicon and / or chromium.
  • the catalytically active composition of the catalyst preferably contains no oxygen-containing compounds of titanium and / or of aluminum.
  • the catalytically active material is not doped with other metals or metal compounds.
  • the catalysts can be prepared by known methods, for. B. by precipitation, precipitation, impregnation.
  • Preferred heterogeneous catalysts contain in their catalytically active composition prior to reduction with hydrogen
  • heterogeneous catalysts in the process according to the invention are catalysts disclosed in EP 382 049 A (BASF AG) or correspondingly preparable, their catalytically active composition before treatment with hydrogen
  • the catalytically active composition of which before reduction with hydrogen contains 20 to 85% by weight Zr02, 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 M0O3, and 0 to 10 wt .-% oxygen-containing compounds of aluminum and / or manganese, calculated as AI2O3 or MnÜ2 contains, for example, in loc. Cit., page 8, disclosed catalyst having the composition 31, 5 wt .-% ZrÜ2, 50 wt .-% NiO, 17 wt .-% CuO and 1, 5 wt .-% M0O3.
  • the catalyst is preferably at a temperature in the range of 100 to 500 ° C, especially 150 to 400 ° C, especially 180 to 300 ° C, over a period of at least 25 min., Particularly at least 60 min., A hydrogen containing atmosphere or a hydrogen atmosphere.
  • the period of activation of the catalyst may be up to 1 h, especially up to 12 h, in particular up to 24 h.
  • At least some of the oxygen-containing metal compounds present in the catalysts are reduced to the corresponding metals, so that they are present together with the various oxygen compounds in the active form of the catalyst.
  • 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 primary amine III or the ammonia is preferably in the molar amount of 5 to 50 times, more preferably 10 to 45 times the molar amount, more preferably 20 to 40 times the molar amount, for example, 25 or 30 times molar amount, in each case based on the N-substituted DEOA II used.
  • the primary amine III or the ammonia can be used as an aqueous solution, especially as a 30 to 100% by weight aqueous solution, e.g. 50 to 85 wt .-% aqueous solution used.
  • Monomethylamine and monoethylamine, in particular also originating from a recovery from the reaction product, are preferably also used without further solvent (compressed gas, purity especially 95 to 100% by weight).
  • the N-substituted DEOA II is preferably used as an aqueous solution, especially as a 75 to 99 wt .-% aqueous solution, for example 80 to 90 wt .-% aqueous solution.
  • the amination of the primary alcohol groups of the N-substituted DEOA II is carried out in the liquid phase.
  • the fixed bed process is in the liquid phase.
  • the starting materials are passed (N-substituted DEOA II, primary amine III or ammonia), preferably simultaneously, in the liquid phase at pressures of 16.0 to 24.0 MPa (160 to 240 bar), preferably 17 , 0 to 23.0 MPa, more preferably 18.0 to 22.0 MPa, further preferably 19.0 to 21, 0 MPa, more preferably 19.5 to 20.5 MPa, and temperatures of generally 180 to 230 ° C, especially 180 to 220 ° C, preferably 185 to 210 ° C, in particular 190 to 200 ° C, including hydrogen over the catalyst, which is usually in a preferably heated from outside fixed bed reactor. It is both a trickle way and a sumping possible.
  • the catalyst loading is generally in the range of 0.1 to 1.0, preferably 0.15 to 0.7, more preferably 0.15 to 0.6, more preferably 0.2 to 0.4, kg of N-substituted DEOA II per liter of catalyst (bulk volume) and hour (N-substituted DEOA II calculated as 100% pure).
  • a dilution of the reactants with a suitable solvent such as water, tetrahydrofuran, dioxane, N-methylpyrrolidone or ethylene glycol dimethyl ether, take place. It is expedient to heat the reactants before they are introduced into the reaction vessel, preferably to the reaction temperature.
  • the reaction is preferably carried out at a catalyst loading in the range of 40 to 1500 standard liters of hydrogen / (cat ⁇ hr), especially a catalyst loading in the range of 100 to 1000 standard liters of hydrogen / (1 kton ⁇ hr).
  • Catalyst volume figures always refer to the bulk volume.
  • the reaction is carried out in the presence of 0.1 to 9.0 wt .-% hydrogen, especially in the presence of 0.25 to 7.0 wt .-% hydrogen, more particularly in the presence of 0.3 to 6.0 wt. % Hydrogen, in particular in the presence of from 0.4 to 5.0% by weight of hydrogen, in each case based on the total amount of diethanolamine II used and ammonia or amine III [ie diethanolamine II + (NH 3 or amine III )], carried out.
  • the pressure in the reaction vessel which results from the sum of the partial pressures of the primary amine III or ammonia, of the N-substituted DEOA II and the reaction products formed and optionally of the solvent used at the temperatures indicated, is expediently achieved by pressing on hydrogen increased to the desired reaction pressure.
  • the excess primary amine III can be recycled together with the hydrogen.
  • the catalyst is arranged as a fixed bed, it may be advantageous for the selectivity of the reaction to mix the shaped catalyst bodies 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
  • 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 removed from the reaction product only during the work-up of the reaction product , z. B. distillative.
  • the excess hydrogen and the excess amination agent present, if any, are removed from the reaction effluent and the reaction crude product obtained is purified, for. B. by a fractional rectification. Suitable work-up procedures are for. In EP 1 312 600 A and EP 1 312 599 A (both BASF AG). The excess primary amine and the hydrogen are advantageously returned to the reaction zone. The same applies to the possibly not fully implemented N-substituted DEOA II.
  • a workup of the product of the reaction is preferably configured as follows:
  • step iv optionally present unreacted N-substituted DEOA (II) and / or optionally present Alkylaminoethylethanolamin as a byproduct with the formula IV is removed overhead and recycled to the reaction.
  • step i separated primary amine III or separated ammonia having a purity of 90 to 99.9 wt .-%, particularly 95 to 99.9 wt .-% is preferably recycled to the reaction, more preferably a portion of the separated Amines III or ammonia, especially 1 to 30 wt .-% of the separated amine III or ammonia, further particularly 5 to 25 wt .-% of the separated amine III or ammonia, is discharged.
  • Catalyst A a Cu / Ni / Mo / ZrO 2 catalyst as disclosed in EP 696 572 A1 (BASF AG), was prepared by precipitation, filtration, heat treatment and tableting (6 ⁇ 3 mm tablets). The catalyst had the following composition before its treatment (activation) with hydrogen:
  • NEtPIP monoethylpiperazine (N-ethyl-PIP)
  • DEIPIP diethylpiperazine (N, N'-diethyl-PIP)
  • the workup can preferably be carried out by the following five steps (here by way of example of a reaction of N-methyl-DEOA with ammonia:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'une N‑alkylpipérazine de formule I, dans laquelle R1 désigne hydrogène (H), méthyle ou éthyle et R2 un alkyle en C1 à C5, par mise en réaction d'une diéthanolamine N-substituée de formule II avec de l'ammoniaque ou avec une amine primaire de formule H2N-R1 (III) en présence d'hydrogène et d'un catalyseur supporté contenant un métal, la masse catalytiquement active du catalyseur avant sa réduction par l'hydrogène comprenant de 20 à 85 % en poids de composés de zirconium contenant de l'oxygène, exprimés en ZrO2, de 1 à 30 % en poids de composés de cuivre contenant de l'oxygène, exprimés en CuO, de 14 à 70 % en poids de composés de nickel contenant de l'oxygène, exprimés en NiO, et de 0 à 5 % en poids de composés de molybdène contenant de l'oxygène, exprimés en MoO3. La réaction est effectuée en phase liquide sous une pression absolue dans la plage de 160 à 240 bars et à une température dans la plage de 180 à 230 °C en utilisant de l'ammoniaque ou une amine III primaire selon un rapport molaire de 5 à 50 par rapport à la diéthanolamine II employée et en présence de 0,1 à 9,0 % en poids d'hydrogène, rapporté à la quantité totale de la diéthanolamine II et de l'ammoniaque ou de l'amine III employés.
PCT/EP2014/059145 2013-05-16 2014-05-06 Procédé de production de n-alkylpipérazines WO2014184039A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13167961 2013-05-16
EP13167961.5 2013-05-16

Publications (1)

Publication Number Publication Date
WO2014184039A1 true WO2014184039A1 (fr) 2014-11-20

Family

ID=48366270

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/059145 WO2014184039A1 (fr) 2013-05-16 2014-05-06 Procédé de production de n-alkylpipérazines

Country Status (2)

Country Link
TW (1) TW201509880A (fr)
WO (1) WO2014184039A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557777A (zh) * 2015-01-09 2015-04-29 万华化学集团股份有限公司 一种n-甲基哌嗪的制备方法
US9315479B2 (en) 2012-07-13 2016-04-19 Basf Se Process for preparing pyrrolidine
US10414716B2 (en) 2014-12-12 2019-09-17 Basf Se Process for preparing a polyetheramine
WO2019192903A1 (fr) 2018-04-06 2019-10-10 Basf Se Procédé de préparation d'amines

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907802A (en) 1973-04-02 1975-09-23 Henkel & Cie Gmbh Processes for preparation and use of N-alkylpiperazines
EP0235651A1 (fr) 1986-02-18 1987-09-09 BASF Aktiengesellschaft Procédé pour la préparation de N-méthylpipérazine
EP0382049A1 (fr) 1989-02-04 1990-08-16 BASF Aktiengesellschaft Catalyseur et procédé pour l'hydroamination d'alcools
EP0446783A2 (fr) 1990-03-15 1991-09-18 BASF Aktiengesellschaft Procédé pour la préparation de 2-aminoalkyl-2-hydroxylamines-N-aryl substitués et de pipérazines N-aryl substitués
EP0696572A1 (fr) 1994-08-08 1996-02-14 Basf Aktiengesellschaft Procédé pour la préparation d'amines
EP0963975A1 (fr) 1998-06-12 1999-12-15 Basf Aktiengesellschaft Procédé de préparation d'amines
DE19859776A1 (de) 1998-12-23 2000-06-29 Basf Ag Verfahren zur Herstellung von Aminen
CN1413991A (zh) 2002-10-09 2003-04-30 天津大学 固定床连续合成哌嗪系列化合物的方法
EP1312599A1 (fr) 2001-10-30 2003-05-21 BASF Aktiengesellschaft Procédé de séparation d'un mélange d'amines bruts contenant de l'eau provenant de la synthèse de l'amine
EP1312600A1 (fr) 2001-10-30 2003-05-21 BASF Aktiengesellschaft Procédé de séparation d'un mélange d'amines bruts contenant de l'eau provenant de la synthèse de l'amine
WO2003051508A1 (fr) 2001-12-14 2003-06-26 Huntsman Petrochemical Corporation Ameliorations apportees a des catalyseurs de reaction d'amination
WO2008006750A1 (fr) 2006-07-14 2008-01-17 Basf Se Procédé de production d'une amine
WO2009080508A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2009080507A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2009080506A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2011067199A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
CN102101847A (zh) 2010-12-06 2011-06-22 张家港田由新材料科技有限公司 N-甲基-n′-(2-氯乙基)哌嗪的制备方法
WO2011157710A1 (fr) 2010-06-15 2011-12-22 Basf Se Procédé de production d'une méthylamine tertiaire cyclique
CN102304101A (zh) 2011-05-26 2012-01-04 绍兴兴欣化工有限公司 哌嗪与n-烷基哌嗪联产工艺
WO2012049101A1 (fr) 2010-10-14 2012-04-19 Basf Se Procédé de production d'une amine tertiaire cyclique

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3907802A (en) 1973-04-02 1975-09-23 Henkel & Cie Gmbh Processes for preparation and use of N-alkylpiperazines
EP0235651A1 (fr) 1986-02-18 1987-09-09 BASF Aktiengesellschaft Procédé pour la préparation de N-méthylpipérazine
EP0382049A1 (fr) 1989-02-04 1990-08-16 BASF Aktiengesellschaft Catalyseur et procédé pour l'hydroamination d'alcools
EP0446783A2 (fr) 1990-03-15 1991-09-18 BASF Aktiengesellschaft Procédé pour la préparation de 2-aminoalkyl-2-hydroxylamines-N-aryl substitués et de pipérazines N-aryl substitués
EP0696572A1 (fr) 1994-08-08 1996-02-14 Basf Aktiengesellschaft Procédé pour la préparation d'amines
EP0963975A1 (fr) 1998-06-12 1999-12-15 Basf Aktiengesellschaft Procédé de préparation d'amines
DE19859776A1 (de) 1998-12-23 2000-06-29 Basf Ag Verfahren zur Herstellung von Aminen
EP1312600A1 (fr) 2001-10-30 2003-05-21 BASF Aktiengesellschaft Procédé de séparation d'un mélange d'amines bruts contenant de l'eau provenant de la synthèse de l'amine
EP1312599A1 (fr) 2001-10-30 2003-05-21 BASF Aktiengesellschaft Procédé de séparation d'un mélange d'amines bruts contenant de l'eau provenant de la synthèse de l'amine
WO2003051508A1 (fr) 2001-12-14 2003-06-26 Huntsman Petrochemical Corporation Ameliorations apportees a des catalyseurs de reaction d'amination
CN1413991A (zh) 2002-10-09 2003-04-30 天津大学 固定床连续合成哌嗪系列化合物的方法
WO2008006750A1 (fr) 2006-07-14 2008-01-17 Basf Se Procédé de production d'une amine
WO2009080508A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2009080507A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2009080506A1 (fr) 2007-12-21 2009-07-02 Basf Se Procédé de préparation d'une amine
WO2011067199A1 (fr) 2009-12-03 2011-06-09 Basf Se Catalyseur et procédé de production d'une amine
WO2011157710A1 (fr) 2010-06-15 2011-12-22 Basf Se Procédé de production d'une méthylamine tertiaire cyclique
WO2012049101A1 (fr) 2010-10-14 2012-04-19 Basf Se Procédé de production d'une amine tertiaire cyclique
CN102101847A (zh) 2010-12-06 2011-06-22 张家港田由新材料科技有限公司 N-甲基-n′-(2-氯乙基)哌嗪的制备方法
CN102304101A (zh) 2011-05-26 2012-01-04 绍兴兴欣化工有限公司 哌嗪与n-烷基哌嗪联产工艺

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed.,", vol. B 4, article "Fixed-Bed Reactors", pages: 199 - 238

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9315479B2 (en) 2012-07-13 2016-04-19 Basf Se Process for preparing pyrrolidine
US10414716B2 (en) 2014-12-12 2019-09-17 Basf Se Process for preparing a polyetheramine
CN104557777A (zh) * 2015-01-09 2015-04-29 万华化学集团股份有限公司 一种n-甲基哌嗪的制备方法
CN104557777B (zh) * 2015-01-09 2016-08-31 万华化学集团股份有限公司 一种n-甲基哌嗪的制备方法
WO2019192903A1 (fr) 2018-04-06 2019-10-10 Basf Se Procédé de préparation d'amines
US11390578B2 (en) 2018-04-06 2022-07-19 Basf Se Method for synthesizing amines

Also Published As

Publication number Publication date
TW201509880A (zh) 2015-03-16

Similar Documents

Publication Publication Date Title
EP2029520B1 (fr) Procédé pour produire des éthylèneamines et des éthanolamines à partir de monoéthylèneglycol (meg)
EP2582669B1 (fr) Procédé de production d'une méthylamine tertiaire cyclique
EP2627644B1 (fr) Procédé de production d'une amine tertiaire cyclique
EP1986990B1 (fr) Procédé pour produire des éthylèneamines et des éthanolamines par hydroamination de monoéthylèneglycol et d'ammoniac en présence d'un catalyseur
EP2855443B1 (fr) Procédé de production d'une mono-n-alkyl-pipérazine
DE4325848A1 (de) Verfahren zur Herstellung von N-(2-Hydroxyethyl)-piperazin
EP2185499A1 (fr) Procédé pour produire des amines à partir de glycérine
EP2632909B1 (fr) Procédé de préparation de 1,4-bishydroxyéthyl-pipérazine
WO2014184039A1 (fr) Procédé de production de n-alkylpipérazines
EP2588442B1 (fr) Procédé de production de tri-n-propylamine (tpa)
WO2013075974A1 (fr) Procédé de préparation d'éthylamines et de mono-isopropylamine (mipa)
EP3717448B1 (fr) Procédé de préparation continue de 1,2-propylène diamine (1,2-pda) et de diméthyl diéthylènetriamine (dmdeta)
WO2014184048A1 (fr) Procédé de production de n-alkylpipérazines
EP1971568B1 (fr) Procede de fabrication en continu d'une amine aromatique primaire
EP2855442B1 (fr) Procédé de production d'une mono-n-alkyl-pipérazine
DE102010040427A1 (de) Verfahren zur Herstellung von Mono-n-Octylamin (MOA)
EP2858978A1 (fr) Procédé de production de pipérazine
US20130331574A1 (en) Process for Preparing Piperazine
EP2872494B1 (fr) Procédé de préparation de pyrrolidine
WO2013182465A1 (fr) Procédé de production de pipérazine
EP1899291B1 (fr) Procede de production en continu d'une amine
EP2571845B1 (fr) Procédé de préparation de 2-(2-tert.-butylamino-éthoxy)-éthanol (tert.-butylaminodiglycol, tbadg)

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14722182

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14722182

Country of ref document: EP

Kind code of ref document: A1