EP2858978A1 - Procédé de production de pipérazine - Google Patents

Procédé de production de pipérazine

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Publication number
EP2858978A1
EP2858978A1 EP13725699.6A EP13725699A EP2858978A1 EP 2858978 A1 EP2858978 A1 EP 2858978A1 EP 13725699 A EP13725699 A EP 13725699A EP 2858978 A1 EP2858978 A1 EP 2858978A1
Authority
EP
European Patent Office
Prior art keywords
reaction
ammonia
catalyst
deoa
distillation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13725699.6A
Other languages
German (de)
English (en)
Inventor
Roland Bou Chedid
Johann-Peter Melder
Ulrich Abel
Roman Dostalek
Nina Challand
Bernd Stein
Michael Jödecke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13725699.6A priority Critical patent/EP2858978A1/fr
Publication of EP2858978A1 publication Critical patent/EP2858978A1/fr
Withdrawn legal-status Critical Current

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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
    • 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 piperazine of the formula I.
  • Piperazine finds inter alia. Use as intermediate in the preparation of fuel additives (US 3,275,554 A, DE 21 25 039 A and DE 36 1 1 230 A), surfactants, pharmaceutical and plant protection agents, hardeners for epoxy resins, catalysts for polyurethanes, intermediates for the preparation of quaternary ammonium compounds, plasticizers, corrosion inhibitors,
  • Synthetic resins Synthetic resins, ion exchangers, textile auxiliaries, dyes, vulcanization accelerators and / or emulsifiers.
  • 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 alcohols, aldehydes and / or ketones with hydrogen and ammonia, a primary or secondary amine.
  • Aluminum oxide carriers are not taught.
  • 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.
  • Aluminum oxide carriers are not taught.
  • 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 Preparation of an amine by reacting a primary or secondary alcohol, aldehyde and / or ketone with hydrogen and ammonia, a primary or secondary amine.
  • Aluminum oxide carriers are not taught.
  • 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.
  • Aluminum oxide carriers are not taught.
  • 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 piperazine from DEOA and ammonia is generally mentioned on page 22, line 28.
  • WO 201/157710 A1 (BASF SE) describes the preparation of certain cyclic tertiary methylamines, wherein an amino alcohol from the group 1, 4-aminobutanol, 1, 5-aminopentanol, aminodiglycol (ADG) or aminoethyl ethanolamine, with methanol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
  • ADG aminodiglycol
  • ADG aminoethyl ethanolamine
  • WO 2012/049101 A1 (BASF SE) relates to a process for preparing certain cyclic tertiary amines by reacting an amino alcohol from the group 1, 4-aminobutanol, 1, 5-aminopentanol, aminodiglycol (ADG) or aminoethyl-ethanolamine, with a reacting certain primary or secondary alcohol at elevated temperature in the presence of a copper-containing heterogeneous catalyst in the liquid phase.
  • ADG aminodiglycol
  • 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 ,
  • catalysts whose catalytically active material before their reduction with hydrogen in the range of
  • oxygen-containing compounds of aluminum calculated as Al 2 O 3
  • oxygen-containing compounds of copper calculated as CuO
  • 0.2 to 5.0 wt .-% oxygen-containing compounds of tin, calculated as SnO, contains, in o. G. Amination used.
  • the process can be carried out continuously or batchwise. Preferred is a continuous driving style.
  • the starting materials (DEOA, ammonia) are evaporated in a circulating gas stream and fed to the reactor in gaseous form.
  • the educts (DEOA, ammonia) 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 a circulating 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 the DEOA and / or ammonia and / or H) and / or circulating gas and / or reactor discharge from a downstream reactor is advantageously possible here.
  • 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.
  • the oxide support alumina (AI2O3) is considered as belonging to the catalytically active mass.
  • 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 composition after grinding, mixing with molding aids, shaping and heat treatment as Katalysatorformkorper- example, as tablets, spheres, rings , 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.
  • the catalytically active mass of the catalyst, after its last heat treatment and before its reduction with hydrogen, is defined as the sum of the masses of the catalytically active constituents and of the abovementioned catalyst support materials and contains essentially the following constituents:
  • Alumina Al 2 O 3
  • oxygenated compounds of copper nickel and cobalt and oxygenated compounds of tin.
  • 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, in particular> 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, 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 MgCOs, CaCOs and BaC0 3 ; Boron oxide (B2O3).
  • 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 P ⁇ C
  • Alkaline earth metal oxides such as SrO
  • Alkaline earth metal carbonates such as MgCOs, CaCOs and Ba
  • the catalytically active material is not doped with other metals or metal compounds.
  • the catalytically active composition of the catalyst preferably contains no oxygen-containing compounds of silicon and / or zirconium.
  • the catalytically active composition of the catalyst preferably contains no oxygen-containing compounds of titanium and / or chromium.
  • the catalytically active material of the catalyst prior to its reduction with hydrogen, contains in the range from 0.2 to 5.0% by weight, in particular in the range from 0.4 to 4.0% by weight, more particularly in the range from 0, 6 to 3.0 wt .-%, more preferably in the range of 0.7 to 2.5 wt .-%, oxygen-containing compounds of tin, calculated as SnO.
  • the catalytically active material of the catalyst preferably contains in the range from 5.0 to 35 wt. , more particularly 15 to 25% by weight, of oxygen-containing compounds of cobalt, calculated as CoO.
  • the catalytically active composition of the catalyst before its reduction with hydrogen further preferably in the range of
  • 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.
  • the BET surface area (ISO 9277: 1995) of the catalysts according to the invention and used in the process according to the invention is preferably in the range from 30 to 250 m 2 / g, especially in the range from 90 to 200 m 2 / g, more particularly in the range from 130 to 190 m 2 / g, (each before reduction with hydrogen). These ranges are achieved in particular by calcining temperatures in the catalyst preparation in the range from 400 to 600 ° C., in particular from 420 to 550 ° C., (see below).
  • Various processes are possible for the preparation of the catalysts used in the process according to the invention. They are obtained, for example, by peptizing powdery mixtures of the hydroxides, carbonates, oxides and / or other salts of the components with water and then extruding and annealing (heat treatment) the mass thus obtained.
  • Precipitation methods are preferably used for the preparation of the catalysts according to the invention. For example, they may be precipitated by coprecipitation of the nickel, cobalt, copper and Sn components from an aqueous salt solution containing these elements by means of bases in the presence of a sparingly soluble oxygen-containing aluminum compound slurry, followed by washing, drying and calcination of the resulting precipitate to be obtained.
  • aluminum oxide, aluminum oxide hydrate, aluminum phosphates, borates and silicates can be used as sparingly soluble, oxygen-containing aluminum compounds.
  • the slurries of the sparingly soluble aluminum compounds can be prepared by suspending fine-grained powders of these compounds in water under vigorous stirring. These slurries are advantageously obtained by precipitating the sparingly soluble aluminum compounds from aqueous aluminum 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.
  • an 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 this procedure mainly depends on the water solubility of the salts, one criterion is their good water solubility, which is 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 inter alia. 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, d. H. 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 material to be felled is generally stored at 80 to 200 ° C, preferential at 100 to 150 ° C, dried and then calcined. The calcination is generally carried out at temperatures between 300 and 800 ° C, preferably at 400 to 600 ° C, in particular at 420 to 550 ° C.
  • the catalysts of the invention can also by impregnation of alumina
  • AI2O3 which is present for example in the form of powder or shaped articles, such as strands, tablets, spheres or rings.
  • the alumina is used, for example, in the amorphous, gamma, theta and / or delta form, as aluminum oxohydroxide (boehmite), preferably in the amorphous 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 aluminum oxide is moistened to the maximum saturation with the impregnation solution in accordance with its water absorption capacity, but the impregnation can also be carried out in supernatant solution.
  • multi-stage impregnation processes it is expedient to dry between individual impregnation steps and optionally to calcine.
  • the multi-step impregnation is advantageous to apply especially when the alumina 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. B. at the above Calciniertemperatur Schemeen.
  • the catalyst is suitably conditioned, whether it is adjusted by grinding to a certain grain size or that it is mixed after its milling with molding aids such as graphite or stearic acid, by means of a press to formings, z.
  • 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, ie in particular as oxides and mixed oxides.
  • the z. B. catalysts prepared as described above are stored as such and possibly 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 initially at preferably 150 to 200 ° C over a period of z. B. 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.
  • part 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 process of the invention 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 ammonia is in the 5- to 25-fold molar amount, preferably 8 to 23 times the molar amount, more preferably 9 to 22 times the molar amount, especially 10 to 21 times the molar amount, in particular in the 1 1 to 20 times the molar amount, eg 12 to 19 times the molar amount, in each case based on the DEOA used.
  • the ammonia can be used as an aqueous solution, especially as a 30 to 90 wt .-% aqueous solution. It is preferably used without further solvent (compressed gas, purity especially 95 to 100 wt .-% strength).
  • the starting material DEOA is preferably used as an aqueous solution, in particular as a 75 to 95% strength by weight aqueous solution, for example 80% strength by weight aqueous solution.
  • Catalyst volume data always refer to the bulk volume.
  • the amination of the primary alcohol groups of the starting material DEOA is carried out in the liquid phase.
  • the fixed bed process is in the liquid phase.
  • the reactants (DEOA, ammonia) are passed on, preferably simultaneously, in the liquid phase at pressures of from 16.0 to 22.0 MPa (160 to 220 bar), preferably from 17.0 to 22.0 MPa preferably 18.0 to 21, 0 MPa, more preferably 19.0 to 20.0 MPa, and temperatures of 180 to 220 ° C, especially 185 to 215 ° C, preferably 190 to 210 ° C, in particular 190 to 205 ° C. , including hydrogen over the catalyst, which is usually located in a preferably heated from the outside fixed bed reactor.
  • the catalyst loading is generally in the range of 0.3 to 0.8, preferably 0.4 to 0.7, more preferably 0.5 to 0.6, kg DEOA per liter of catalyst (bulk volume) and hour (DEOA calculated as 100 % strength).
  • a dilution of the starting materials 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 carried out in the presence of 0.2 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 6.5 wt. % Hydrogen, in particular in the presence of from 0.4 to 6.0% by weight of hydrogen, in each case based on the total amount of DEOA and ammonia used.
  • the pressure in the reaction vessel which results from the sum of the partial pressures of the ammonia, the DEOA and the reaction products formed and optionally the solvent used at the indicated temperatures, is expediently increased by pressurizing hydrogen to the desired reaction pressure. In continuous operation in the liquid phase, the excess ammonia 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 say 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 rate of reaction, the selectivity and the catalyst lifetime 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 ammonia and the hydrogen are advantageously recycled back into the reaction zone. The same applies to the possibly not fully implemented DEOA.
  • a workup of the product of the reaction is preferably configured as follows:
  • step iv optionally present unreacted DEOA (II) and / or optionally present aminoethylethanolamine as a by-product with the formula III separated overhead and recycled to the reaction.
  • step i separated ammonia having a purity of 90 to 99.9 wt .-%, particularly 95 to 99.9 wt .-% is preferably recycled to the reaction, wherein a portion of the separated th ammonia, especially 1 to 30 wt .-% of the separated ammonia, further particularly 2 to 20 wt .-% of the separated ammonia, can be discharged.
  • the invention relates to an integrated, multistage process for the preparation of piperazine, 1,2-ethylenediamine (EDA), diethylenetriamine (N- (2-aminoethyl) -1,2-ethylenediamine, DETA) and N- (2- Aminoethyl) ethanolamine (AEEA), wherein one
  • reaction stage 1 R1 in a first reaction stage ethylene oxide (EO) with ammonia continuously to a product containing monoethanolamine (MEOA), diethanolamine (DEOA) and triethanolamine (TEOA),
  • MEOA monoethanolamine
  • DEOA diethanolamine
  • TEOA triethanolamine
  • distillation stage 1 D1
  • reaction stage 2 R2 in D1 separated MEOA wholly or partially, preferably completely, in a second reaction stage in the presence of an amination catalyst continuously with ammonia and reacted
  • reaction stage 3 R3
  • DEOA separated in D1 completely or partially, preferably completely, in a third reaction stage by the method as described above with ammonia
  • ethylene oxide (EO) is preferably reacted with ammonia in the presence of water as catalyst.
  • As amination catalyst in the second reaction stage (R2) is preferably a Cu-containing heterogeneous catalyst, more preferably a Cu and Ni- containing heterogeneous catalyst, especially a Cu and Ni and Co-containing heterogeneous catalyst, especially the in DE 19 53 263 A (BASF AG) disclosed Cu / Ni / Co / Al 2 0 3 - catalyst used.
  • a Cu-containing heterogeneous catalyst more preferably a Cu and Ni- containing heterogeneous catalyst, especially a Cu and Ni and Co-containing heterogeneous catalyst, especially the in DE 19 53 263 A (BASF AG) disclosed Cu / Ni / Co / Al 2 0 3 - catalyst used.
  • reaction stage 3 Particularly preferred in reaction stage 3 is a procedure in which the DEOA is converted to at least 95%, especially 98 to 100%.
  • distillation stage 2 D2
  • distillation stage 3 D3
  • distillation stage 4 D4
  • distillation stage 4 In the distillation stage 4 (D4) optionally incurred MEOA is advantageously recycled to the second reaction stage (R2).
  • Figure 1 shows schematically a particularly preferred embodiment of the integrated method.
  • FIG. 1 shows schematically a further particularly preferred embodiment of the integrated method.
  • Tin (II) chloride the 3.9 wt .-% Ni, 3.9 wt .-% Co, 1, 9 wt .-% Cu, 5.5 wt .-% Al 2 0 3 and 0.5 wt % Sn, was simultaneously precipitated in a stirrer vessel in a constant stream with a 20% by weight aqueous sodium carbonate solution at a temperature of 65-70 ° C such that the pH of 5.7 measured with a glass electrode was maintained. After the precipitation, air was blown in for 1 hour, after which the pH of the solution was adjusted to 7.4 with sodium carbonate solution. The suspension obtained was filtered and the filter cake was washed with demineralized water until the electrical conductivity of the filtrate was about 20 mS.
  • the filter cake was dried at a temperature of 150 ° C in a drying oven.
  • the hydroxide carbonate mixture obtained in this way was then calcined at a temperature of 500 ° C for 4 hours.
  • the catalyst mass was then mixed with 3 wt .-% graphite and formed into tablets 3x3 mm.
  • the tablets obtained in this way are reduced in hydrogen at a temperature of 280-300 ° C for at least 12 hours.
  • the passivation of the reduced catalyst was carried out at room temperature in dilute air (air in N 2 with a maximum O 2 content of 5% by volume).
  • the catalyst thus obtained had the composition as shown in Table I below.
  • the reactor was maintained at a temperature of about 185 to 200 ° C and a total pressure of 190 or 200 bar.
  • the reaction temperature was chosen so that a DEOA conversion of> 90% was achieved.
  • the mixture leaving the reactor was cooled and vented to atmospheric pressure.
  • samples were taken from the reaction mixture and analyzed by gas chromatography.
  • a 30 m long GC column "RTX-5 Amines” was used, with a temperature program: 70 ° C / 5 min, heating to 280 ° C at a rate of 5 ° C / min, at 280 ° C. /10 mins.
  • the workup may preferably be carried out by the following five steps:
  • reaction stage 1 The reaction of EO with NH3, catalyzed homogeneously with water, was carried out continuously at a NH 3 : EO molar ratio (MV) of 10 (reaction stage 1).
  • the ethanolamines were separated by distillation (distillation stage 1).

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

Abstract

Procédé de production de pipérazine de formule I par mise en réaction de diéthanolamine (DEOA) de formule II avec de l'ammoniac (NH3) en présence d'hydrogène et d'un catalyseur supporté contenant du métal, caractérisé en ce que la masse catalytiquement active du catalyseur contient, avant sa réduction avec de l'hydrogène, des composés oxygénés de l'aluminium, du cuivre, du nickel et du cobalt, et de 0,2 à 5,0 % en poids de composés oxygénés de l'étain, exprimés en SnO, ladite mise en réaction étant conduite dans la phase liquide à une pression absolue de l'ordre de 160 à 220 bars, à une température de l'ordre de 180 à 220°C, avec ajout d'ammoniac dans un rapport molaire à la DEOA employée de 5 à 25, et en présence de 0,2 à 9,0 % en poids d'hydrogène, rapporté à la quantité totale de DEOA et d'ammoniac utilisés.
EP13725699.6A 2012-06-06 2013-05-29 Procédé de production de pipérazine Withdrawn EP2858978A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13725699.6A EP2858978A1 (fr) 2012-06-06 2013-05-29 Procédé de production de pipérazine

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12171084 2012-06-06
EP13725699.6A EP2858978A1 (fr) 2012-06-06 2013-05-29 Procédé de production de pipérazine
PCT/EP2013/061104 WO2013182468A1 (fr) 2012-06-06 2013-05-29 Procédé de production de pipérazine

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EP2858978A1 true EP2858978A1 (fr) 2015-04-15

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EP (1) EP2858978A1 (fr)
JP (1) JP2015525214A (fr)
CN (1) CN104364242A (fr)
IN (1) IN2014DN09263A (fr)
WO (1) WO2013182468A1 (fr)

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JP6261576B2 (ja) * 2012-07-13 2018-01-17 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ピロリジンの製造法
CN111925341B (zh) * 2020-08-11 2021-07-06 山东达民化工股份有限公司 一种哌嗪的制备方法
CN114195738A (zh) * 2021-12-27 2022-03-18 江苏康恒化工有限公司 一种无溶剂合成哌嗪的方法

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CN104364242A (zh) 2015-02-18
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JP2015525214A (ja) 2015-09-03

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