CN104364242A - Piperazine preparation method - Google Patents
Piperazine preparation method Download PDFInfo
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- CN104364242A CN104364242A CN201380029522.8A CN201380029522A CN104364242A CN 104364242 A CN104364242 A CN 104364242A CN 201380029522 A CN201380029522 A CN 201380029522A CN 104364242 A CN104364242 A CN 104364242A
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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
- C07C209/04—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
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- 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
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Abstract
Method for preparing piperazine of formula I by reacting diethanolamine (DEOA) of formula II with ammonia in the presence of hydrogen and a metal-containing supported catalyst. Before the catalyst is reduced with hydrogen, the catalytically active mass of the catalyst contains oxygen-containing aluminum, copper, nickel and cobalt compounds and 0.2 to 5.0 wt.% oxygen-containing tin compounds calculated as SnO, and the reaction is carried out in the liquid phase at an absolute pressure ranging from 160 to 220 bar, at a temperature ranging from 180 to 220 DEG C, ammonia is used at a molar ratio ranging from 5 to 25 in relation to the DEOA used in the process, the method being carried out in the presence of 0.2 to 9.0 wt.% hydrogen relative to the total amount of DEOA and ammonia used in the process.
Description
Describe
The present invention relates to the method for the piperazine of a kind of preparation formula I,
The diethanolamine (DEOA) of its Chinese style II
React under the existence of the metallic catalyzer of hydrogen and load with ammonia.
Piperazine especially as intermediate for the preparation of fuel dope (US 3,275,554 A; DE 21 25039 A and DE 36 11 230 A), tensio-active agent, medicine and crop production compositions; for the stiffening agent of epoxy resin; for the catalyzer of urethane, for the preparation of the intermediate of quaternary ammonium compound, softening agent; corrosion inhibitor; synthetic resins, ion-exchanger, textile auxiliaries; dyestuff, vulcanization accelerator and/or emulsifying agent.
((Huntsman Petrochemical Corp.) relates to the specific catalyzer containing Cu/Ni/Zr/Sn of use by the method for alcohol amination to WO03/051508A1, wherein in one embodiment, Zr (capable see page 4 10-16) is replaced containing Cr.The catalyzer oxygen-freeization aluminium described in this application and not containing cobalt.
What WO2008/006750 A1 (BASF AG) related to specific Pb, Bi, Sn, Sb and/or In doping is reacting by primary alconol or secondary alcohol, aldehyde and/or ketone and hydrogen and ammonia, primary amine or secondary amine the purposes prepared in the method for amine containing the catalyzer of zirconium dioxide, copper, nickel and cobalt and they.Do not mention alumina supporter.
WO2009/080507 A1 (BASF SE) relate to that specific Sn and Co adulterate containing zirconium dioxide, the catalyzer of copper and mickel and they reacting by primary alconol or secondary alcohol, aldehyde and/or ketone and hydrogen and ammonia, primary amine or secondary amine the purposes prepared in the method for amine.Do not mention alumina supporter.
What WO2009/080506 A1 (BASF SE) related to specific Pb, Bi, Sn, Mo, Sb and/or P doping is reacting by primary alconol or secondary alcohol, aldehyde and/or ketone and hydrogen and ammonia, primary amine or secondary amine the purposes prepared in the method for amine containing the catalyzer of zirconium dioxide, nickel and iron and they.Do not mention alumina supporter.Preferably, catalyzer is not containing Cu and containing Co.
WO2009/080508 A1 (BASF SE) relates to the purposes prepared in the reaction by primary alconol or secondary alcohol, aldehyde and/or ketone and hydrogen and ammonia, primary amine or secondary amine containing the catalyzer of zirconium dioxide, copper, nickel, cobalt and iron and they in the method for amine of specific Pb, Bi, Sn and/or Sb doping.Do not mention alumina supporter.
WO2011/067199 A1 (BASF SE) relates to the catalyzer of specifically salic, copper, nickel, cobalt and tin and they are preparing the purposes in the method for amine by primary alconol or secondary alcohol, aldehyde and/or ketone.Broadly describe in the 22nd page of the 28th row and prepare piperazine from DEOA and ammonia.
WO2011/157710 A1 (BASF SE) relates to the method preparing specific Cyclic methyl tertiary amine, wherein be selected from 1, amino alcohol and the methyl alcohol of 4-amino butanol, 1,5-aminopentanol, aminodiglycol (ADG) or amino ethyl ethanolamine react in the liquid phase at elevated temperatures under the existence of the heterogeneous catalyst of cupric.
WO2012/049101 A1 (BASF SE) relates to the method preparing specific cyclic tertiary amine, wherein be selected from 1, the amino alcohol of 4-amino butanol, 1,5-aminopentanol, aminodiglycol (ADG) or amino ethyl ethanolamine and specific primary alconol or secondary alcohol react in the liquid phase at elevated temperatures under the existence of the heterogeneous catalyst of cupric.
CN 102 304 101A (Shaoxing Xingxin Chem.Co., Ltd.) describes and prepares piperazine and N-alkylpiperazine simultaneously, wherein N-hydroxyethyl-1，2-diaminoethane and C
1-7primary alconol reacts under the existence of metal catalyst.
DE198 59 776A1 (BASF AG) relates to use catalyzer moulded product and carries out specific amination method, and described catalyzer moulded product contains oxygenatedchemicals and the metallic copper of titanium and copper.
The object of the invention is to improve at present for the preparation of the economic feasibility of the method for formula I piperazine, and overcome one or more shortcomings of prior art.This object is the condition finding to set up in a simple manner decoupled at technical elements, and makes it possible to carry out described method when high conversion, high yield, space-time yield (STY), the high mechanical stability simultaneously with catalyzer moulded product and selectivity and low " risk out of control ".
[space-time yield is by " amount/(catalyst volume ● time) of product " ((kg/ (l
cat.● h)) and/or " amount/(reactor volume ● time) of product " (kg/ (l
reactor● h) represent].
Therefore, found the method for the piperazine of a kind of preparation formula I,
The diethanolamine (DEOA) of its Chinese style II
React under the existence of the metallic catalyzer of hydrogen and load with ammonia, the wherein oxygenatedchemicals of the catalytic active substance of catalyzer containing aluminium, copper, nickel and cobalt before it is with hydrogen reducing, and the oxygenatedchemicals of the tin containing 0.2-5.0 % by weight, calculate as SnO, and this reaction carries out at the temperature of the absolute pressure of 160-220 bar, 180-220 DEG C in the liquid phase, wherein use the mol ratio between ammonia and DEOA to be 5-25, and this reaction is carried out under the existence of the hydrogen of the 0.2-9.0 % by weight of the total amount based on DEOA used and ammonia.
Especially, in above-mentioned amination method, use such catalyzer, its catalytic active substance contained before it is with hydrogen reducing:
The oxygenatedchemicals of the aluminium of 15-80 % by weight, as Al
2o
3calculate,
The oxygenatedchemicals of the copper of 1-20 % by weight, calculates as CuO,
The oxygenatedchemicals of the nickel of 5-35 % by weight, calculates as NiO,
The oxygenatedchemicals of the cobalt of 5-35 % by weight, calculates as CoO, and
The oxygenatedchemicals of the tin of 0.2-5.0 % by weight, calculates as SnO.
This method can be carried out continuously or discontinuously.Preferred continuous processing.
In recycle gas operation, raw material (DEOA, ammonia) evaporates in recycle gas stream, and pass into reactor in a gaseous form.
Raw material (DEOA, ammonia) also as aqueous solution evaporate, and can pass into catalyst bed together with recycle gas stream.
Preferred reactor is tubular reactor.The suitable reactor with recycle gas stream such as can see Ullmann industrial chemistry encyclopaedia (Ullmann ' s Encyclopedia ofIndustrial Chemistry), 5th edition, B 4 volume, 199-238 page, " fixed-bed reactor ").
Or this reaction is advantageously carried out in bundled tube reactor or in single material flow device.
In single material flow device, the tubular reactor for carrying out reacting can comprise multiple (the such as 2 or 3) tubular reactor be linked in sequence.Optionally, here can advantageously in the middle of introduce charging (comprising DEOA and/or ammonia and/or hydrogen) and/or recycle gas and/or the reactor discharging from downstream reactor.
The amount of recycle gas is preferably 40-1500m
3(under atmospheric pressure)/[m
3catalyzer (bed volume) h], especially 60-750m
3(under atmospheric pressure)/[m
3catalyzer (bed volume) h], particularly preferably 100-400m
3(under atmospheric pressure)/[m
3catalyzer (bed volume) h].(normal atmosphere=1 bar is absolute).
Recycle gas contains the H of preferably at least 10 volume %, particularly 50-100 volume %, very special 80-100 volume %
2.
In the methods of the invention, catalyzer preferably uses with the catalyst mode be only made up of catalytic active substance and optional shaping assistant (such as graphite or stearic acid), if catalyzer is used as moulded product, namely no longer contains the adjoint material of other catalytic activity.
In this respect, oxide carrier material aluminum oxide (Al
2o
3) be regarded as belonging to catalytic active substance.
These catalyzer are by adding reaction vessel to use by the catalytic active substance of grind into powder, or by by catalytic active substance grinding, mix with shaping assistant, shaping and place after thermal treatment and use in the reactor, the form of catalyzer moulded product, such as, as sheet stock, pearl, ring, extrudate (such as line material).
In each case, except as otherwise noted, the concentration data (% by weight) of catalyst component to represent after its finished heat treatment and at its catalytic active substance with the finished catalyst before hydrogen reducing.
The catalytic active substance of catalyzer is defined as the summation of catalytic active component and said catalyst carrier material after its finished heat treatment and before it is with hydrogen reducing, and contains following composition substantially: aluminum oxide (Al
2o
3), the oxygenatedchemicals of copper, nickel and cobalt, and the oxygenatedchemicals of tin.
The summation normally 70-100 % by weight of the composition of above-mentioned catalytic active substance, preferred 80-100 % by weight, particularly preferably 90-100 % by weight, particularly >95 % by weight, very particularly preferably >98 % by weight, especially >99 % by weight, such as particularly preferably 100 % by weight.
Catalytic active substance according to catalyzer that is of the present invention and that use in the methods of the invention can contain one or more elements (oxidation state 0) or its inorganic or organic compound in addition, and it is selected from IA to the VIA race of the periodic table of elements and IB to VIIB race and VIII.
The example of these elements and compound thereof is: transition metal, such as Mn and MnO
2, W and Tungsten oxide 99.999, Ta and tantalum oxide, Nb and niobium oxides or niobium oxalate, V and vanadium oxide and vanadium base pyrophosphate salt; Lanthanon, such as Ce and CeO
2or Pr and Pr
2o
3; Alkaline earth metal oxide, such as SrO; Alkaline earth metal carbonate, such as MgCO
3, CaCO
3and BaCO
3; Boron oxide (B
2o
3).
Preferably, according to the catalytic active substance not rhenium-containing of catalyzer that is of the present invention and that use in the methods of the invention, not containing ruthenium, not iron content, and/or not containing zinc, in each case neither the form of metal (oxidation state=0) neither the form (oxidation state ≠ 0) of ion, it especially not oxidised form.
Preferably, according to catalytic active substance not argentiferous and/or the molybdenum of catalyzer that is of the present invention and that use in the methods of the invention, in each case neither the form of metal (oxidation state=0) neither the form (oxidation state ≠ 0) of ion, it especially not oxidised form.
In an especially preferred embodiment, according to the catalytic active substance of catalyzer that is of the present invention and that use in the methods of the invention not containing other catalytic active component, neither the form of element (oxidation state=0) neither the form (oxidation state ≠ 0) of ion.
In an especially preferred embodiment, catalytic active substance is not with other metal or metallic compound doping.But, from the routine of the METAL EXTRACTION of Cu, Co, Ni and Sn with trace elements not included within the scope of this.
Preferably, the oxygenatedchemicals of the not siliceous and/or zirconium of the catalytic active substance of catalyzer.
Preferably, the oxygenatedchemicals of the catalytic active substance of catalyzer not titaniferous and/or chromium.
Before with hydrogen reducing, the catalytic active substance of catalyzer contains the oxygenatedchemicals of the tin of 0.2-5.0 % by weight, calculates, particularly 0.4-4.0 % by weight, more especially 0.6-3.0 % by weight as SnO, is particularly preferably 0.7-2.5 % by weight.
Before with hydrogen reducing, the catalytic active substance of catalyzer contains the oxygenatedchemicals of the cobalt of 5.0-35 % by weight, calculates, particularly 10-30 % by weight, more especially 12-28 % by weight, very particularly 15-25 % by weight as CoO.
Before with hydrogen reducing, the catalytic active substance of catalyzer also preferably contains:
The oxygenatedchemicals of 15-80 % by weight, particularly 30-70 % by weight, the more especially aluminium of 35-65 % by weight, in each case as Al
2o
3calculate,
The oxygenatedchemicals of 1-20 % by weight, particularly 2-18 % by weight, the more especially copper of 5-15 % by weight, calculates as CuO in each case, and
The oxygenatedchemicals of 5-35 % by weight, particularly 10-30 % by weight, more especially 12-28 % by weight, the very particularly nickel of 15-25 % by weight, calculates as NiO in each case.
Mol ratio between nickel and copper is preferably greater than 1, more preferably greater than 1.2, particularly preferred in the scope of 1.8-8.5.
According to the BET surface-area (ISO9277:1995) of catalyzer that is of the present invention and that use in the methods of the invention preferably at 30-250m
2in the scope of/g, particularly 90-200m
2/ g, more especially 130-190m
2/ g (in each case with hydrogen reducing before).These scopes are 400-600 DEG C particularly by the calcining temperature during catalyst preparing to realize, particularly 420-550 DEG C (vide infra).
Various method may be used for preparing the catalyzer used in the methods of the invention.These catalyzer such as can carry out granulation by the pulverulent mixture of other salt of oxyhydroxide, carbonate, oxide compound and/or component and water, are extruded by the material obtained in this way subsequently and heat (thermal treatment) and obtain.
In order to prepare catalyzer of the present invention, preferably use intermediate processing.Therefore, such as, catalyzer can by nickel, cobalt, copper and tin component from the salt brine solution alkali containing these elements the slurries of the oxygenatedchemicals of the aluminium of microsolubility exist, carry out co-precipitation and the throw out of gained is carried out washing subsequently, dry and calcining and obtaining.As the oxygenatedchemicals of the aluminium of microsolubility, such as aluminum oxide, hydrated alumina, aluminum phosphate, aluminum borate and pure aluminium silicate can be used.The slurries of microsolubility aluminum compound can be prepared by being suspended in water with vigorous stirring by the particulate powders of these compounds.These slurries obtain advantageous by being settled out microsolubility aluminum compound with alkali from aluminum saline solution.
Preferably, catalyzer of the present invention is prepared via the co-precipitation (mixed precipitation) of its components all.For this purpose, the salt brine solution containing catalyst component advantageously mixes at elevated temperatures with moisture alkali and stirs, and such as sodium carbonate, sodium hydroxide, salt of wormwood or potassium hydroxide, until precipitated.Also can operate with the alkali of alkali-free metal, such as ammonia, volatile salt, bicarbonate of ammonia, ammonium carbamate, ammonium oxalate, propanedioic acid ammonium, urotropine, urea etc.The type of used salt is not generally crucial; Therefore use this operation, the water-soluble of salt is important, is that it is excellent water-soluble to have for needed for these higher concentration salts solutions of preparation for a standard of salt.It is apparent that when selecting the salt of each component, naturally will only select such salt, its negatively charged ion does not have interference effect, no matter be by causing unwanted precipitation or being prevented by compound action or hinder precipitation.
The throw out obtained in these precipitin reaction is being generally chemically uneven, and oxide compound, oxide hydrate, oxyhydroxide, carbonate and the mixture that is insoluble and basic salt containing metal used.About sedimentary filterability, prove advantageously to carry out aging, that is, make their after precipitation, leave standstill regular hour, when optionally at elevated temperatures or at the same time air being passed through.
The throw out obtained by these intermediate processings is processed to form catalyzer of the present invention in a conventional manner further.First, throw out washs.Time via washing procedure and the temperature via washing water and consumption, can affect the alkali metal content that (inorganic) alkali that may be used as precipitation agent provide.Generally speaking, the temperature extending washing time or raising washing water will reduce alkali-metal content.After wash, the material of precipitation is generally dry at 80-200 DEG C, and preferred 100-150 DEG C, calcines subsequently.Calcining is generally carried out at the temperature of 300-800 DEG C, preferred 400-600 DEG C, particularly 420-550 DEG C.
Catalyzer of the present invention also can pass through impregnated alumina (Al
2o
3) preparation, this such as exists with the form of powder or moulded product, such as extrudate, sheet stock, pearl or ring.
Aluminum oxide such as uses with amorphous, γ, θ and/or δ form, uses, preferably use with unbodied form as oxygen base aluminium hydroxide (boehmite).
Moulded product can conventionally be prepared.
Dipping also conventionally carries out, for example, see A.B.Stiles, catalyst preparing-laboratory and industrial production process (Catalyst Manufacture-Laboratory and CommercialPreparations), Marcel Dekker, New York (1983), by applying in one or more impregnation stage by corresponding metal salt solution in each case, the metallic salts wherein used is corresponding nitrate, acetate or muriate in this way.This composition is dry after immersion, optionally calcines.
Dipping can carry out according to so-called " just wetting " method, wherein aluminum oxide according to the impregnated solution-wet of its water absorptive capacity to saturation point at the most.But dipping also can carry out in supernatant solution.
When multistage impregnation technology, between each impregnation steps, advantageously carry out dry and optional calcination operation.When relatively large metal being applied on aluminum oxide, multistage dipping is particularly advantageous.
In order to use metal component to aluminum oxide, dipping can carry out with all metal-salts simultaneously, or carries out in succession according to any order with independent metal-salt.
Subsequently, carry out drying by the catalyzer of dipping preparation, preferably also calcine, such as, in the above-mentioned calcination temperature range mentioned.
After calcining, regulate catalyzer carefully, no matter be such as, by grinding or mix with shaping assistant such as graphite or stearic acid after milling and reach the particle diameter of restriction, it being made moulded product with press compression, sheet stock, then heat-treat.Thermal treatment temp in this case preferably corresponds to the temperature during calcining.
The catalyzer prepared in this way contains the catalytically-active metals of the form of mixtures of its oxygenatedchemicals, namely especially as oxide compound and mixed oxide.
The catalyzer such as above prepared stores, and optionally processes as it is.Before being used as catalyzer, they carry out pre-reduction usually.But they also can use when not having pre-reduction, then they can reduce under hydrogenating amination condition with the oxygen existed in the reactor in this case.
For pre-reduction, catalyzer first exposes the time of such as 12-20 hour at preferred 150-200 DEG C in nitrogen/hydrogen atmosphere, processes about 24 hours in addition subsequently at preferred 200-400 DEG C in hydrogen atmosphere.In the process of this pre-reduction, the metal oxygen-containing compound of the part existed in the catalyst is reduced into corresponding metal, this means that these metals exist with the activity form of catalyzer together with dissimilar oxygen compound.
The inventive method is preferably carried out continuously, and catalyzer preferably as fixed bed arrangement in the reactor.In this respect, be possible via stationary catalyst bed stream up or down.
The consumption of ammonia is 5-25 molar weight doubly, and preferred 8-23 times molar weight, is more preferably 9-22 times of molar weight, especially 10-21 times of molar weight, especially 11-20 times of molar weight, such as 12-19 times of molar weight, uses gauge in each case based on DEOA.
Ammonia can use as the aqueous solution, particularly the aqueous solution of 30-90 % by weight concentration.Preferably do not use other solvent (pressurized gas, purity is 95-100 % by weight concentration especially).
Raw material DEOA preferably uses as the aqueous solution, the particularly aqueous solution of 75-95 % by weight concentration, the such as aqueous solution of 80 % by weight.
Preferably, the exhausted air quantity of process is 1-800 cubic meter (stp)/(catalyzer cubic meter ● h), especially 2-200 cubic meter (stp)/(catalyzer cubic meter ● h).
[volume of cubic meter (stp)=change into standard temperature and pressure (STP) condition (20 DEG C, 1 bar is absolute)]
Catalyst body volume data always represents cumulative volume.
The amination reaction of the primary alcohol group of raw material DEOA carries out in the liquid phase.Preferably, fixed-bed process carries out in the liquid phase.
When operating in the liquid phase, raw material (DEOA, ammonia) is preferably side by side passed through in the liquid phase under the pressure of 16.0-22.0MPa (160-220 bar), preferred 17.0-22.0MPa, more preferably 18.0-21.0MPa, more preferred 19.0-20.0MPa, temperature is 180-220 DEG C, particularly 185-215 DEG C, preferred 190-210 DEG C, especially 190-205 DEG C, comprise hydrogen via catalyzer, it is usually located in fixed-bed reactor, and described reactor is preferably from indirect heating.Here, trickle mode and liquid phase mode are possible.The little hourly space velocity of catalyzer is generally that 0.3-0.8, the preferably DEOA/ of 0.4-0.7, particularly preferably 0.5-0.6kg often rise catalyzer (bed volume) and (DEOA calculates as 100% concentration) per hour.Optionally, raw material can with suitable solvent cut, such as water, tetrahydrofuran (THF), two
alkane, N-Methyl pyrrolidone or glycol dimethyl ether.Be even heated before reactant is introduced into reaction vessel easily, be preferably heated to temperature of reaction.
React and carry out under the hydrogen of 0.2-9.0 % by weight exists, particularly under the hydrogen of 0.25-7.0 % by weight exists, again particularly under the hydrogen of 0.3-6.5 % by weight exists, very particularly under the hydrogen of 0.4-6.0 % by weight exists, in each case based on the total amount of DEOA used and ammonia.
Pressure in reaction vessel produces from the summation of ammonia, DEOA and the reaction product formed and the optional common solvent dividing potential drop at said temperatures used, and described pressure is in the reactor elevated to required reaction pressure conveniently by injection hydrogen.
In the liquid phase when operate continuously, excess of ammonia can circulate together with hydrogen.
If catalyzer is as fixed bed arrangement, then can advantageously catalyzer moulded product be mixed with inert filler in the reactor for reaction preference, namely " dilution " they.Proportion of filler in these catalyst preparing can be 20-80 parts by volume, particularly 30-60 parts by volume, especially 40-50 parts by volume.
The reaction water that formed in reaction process (in each case 1 moles/mole reacted alcohol radical) does not generally have detrimental action for transforming degree, speed of reaction, selectivity and catalyst life, so easily only removing during reaction product aftertreatment, such as, by distillation.
After reacting, discharging decompresses easily, and therefrom remove excessive hydrogen and the optional excessive amination reagent existed, the crude reaction product obtained is purified, such as, by classification rectifying.Suitable post-treating method is for example, see EP 1 312 600A and EP 1 312 599A (being all BASFAG).Excess of ammonia and hydrogen advantageously return to reaction zone again.This is equally applicable to the DEOA of any non-complete reaction.
The aftertreatment of reaction product is preferably as follows to be carried out:
From reaction product by distillation:
I () first isolates unreacted ammonia from top,
(ii) from top portion from water outlet,
(iii) from top portion from go out optional exist there is by product (low boilers) more lower boiling than process products I,
(iv) from top portion from going out process products piperazine (I), and having of optionally existing is retained in bottom than the more high boiling by product of process products I (high boiling product) and the optional unreacted DEOA (II) existed.
In the reaction process of the inventive method, the amino ethyl ethanolamine (AEEA) of formula III can be formed as by product:
So, particularly by distillation,
V the unreacted DEOA (II) optionally existed and/or the optional formula III amino ethyl ethanolamine as by product existed, from the bottom of step I v, are separated from top and turn back to reaction by ().
To separate in step I and there is 90-99.9 % by weight, the preferably ammonia of 95-99.9 % by weight purity and preferably turn back in reaction, the ammonia be separated of a part can be removed in each case, particularly remove the ammonia be separated of 1-30 % by weight, more preferably remove the ammonia be separated of 2-20 % by weight.
In a specific embodiment, the present invention relates to one and prepare piperazine, 1,2-quadrol (EDA), diethylenetriamine (N-(2-amino-ethyl)-1,2-quadrol, DETA) and the multi-stage method of the integration of N-(2-amino-ethyl) thanomin (AEEA), wherein
-(step of reaction 1=R1) is in the first step of reaction, oxyethane (EO) and ammonia are obtained by reacting the product containing monoethanolamine (MEOA), diethanolamine (DEOA) and trolamine (TEOA) continuously
-(distillation stage 1=D1) goes out thanomin MEOA, DEOA and TEOA by fractionation by distillation,
The MEOA separated in D1 partially or completely, preferably fully reacts continuously under the existence of amination catalysis with ammonia by-(step of reaction 2=R2) in the second step of reaction, and
The DEOA separated in D1 partially or completely, preferably fully reacts according to the method described above with ammonia by-(step of reaction 3=R3) in the 3rd step of reaction.
Preferably, in the first step of reaction, oxyethane (EO) and ammonia react under the existence of the water as catalyzer.
Especially, the water produced in distillation stage 1 (D1) and/or ammonia turn back in the first step of reaction (R1).
The amination catalysis used in the second step of reaction 2 (R2) is preferably the heterogeneous catalyst of cupric, be more preferably the heterogeneous catalyst containing Cu and Ni, particularly containing the heterogeneous catalyst of Cu and Ni and Co, the Cu/Ni/Co/Al very particularly described in DE 19 53 263A (BASF AG)
2o
3catalyzer.
In addition, in another embodiment, in the second step of reaction 2 (R2), the heterogeneous catalyst containing Cu and Ln is preferably used, the Cu/Ln/Al especially described in WO2010/115759A (BASF AG)
2o
3catalyzer.
In step of reaction 3, particularly preferably wherein DEOA be transformed at least 95%, the technique of particularly 98-100%.
Preferably, isolated the ammonia (distillation stage 2=D2) of existence from the reaction product of step of reaction 2 by distillation.The ammonia be separated advantageously turns back to step of reaction 2.
Preferred again, isolated the ammonia (distillation stage 3=D3) of existence from the reaction product of step of reaction 3 by distillation.The ammonia be separated advantageously turns back to step of reaction 3.
The two kinds of reaction product retained after isolating ammonia preferably merge, and go out piperazine, EDA, DETA and AEEA and the optional MEOA (distillation stage 4=D4) existed by distillation from the product separation merged.
In distillation stage 4 (D4), the optional MEOA existed advantageously turns back in the second step of reaction (R2).
Therefore, Fig. 1 schematically illustrate a selected a particularly preferred embodiment of integral method.
Or, preferably the reaction product from two step of reaction R2 and R3 is merged, the ammonia (distillation stage 3=D3) going out to exist from merging product separation by distillation, then goes out piperazine, EDA, DETA and AEEA and the optional MEOA (distilling stage 4=D4) existed by fractionation by distillation.
The ammonia separated in the distillation stage 3 advantageously turns back in step of reaction 2 and/or 3.
In distillation stage 4 (D4), the optional MEOA produced advantageously turns back in the second step of reaction 2 (R2).
Therefore, Fig. 2 shows the schema of another particularly preferred embodiment of integral method.
All pressure datas represent absolute pressure.
All ppm data representations are based on quality meter.
Embodiment
1. Kaolinite Preparation of Catalyst A [=embodiment 4] in WO2011/067199A (BASF SE)
The aqueous solution of the nickelous nitrate containing 3.9 % by weight Ni, 3.9 % by weight Co, 1.9 % by weight Cu, 5.5 % by weight Al2O3 and 0.5 % by weight Sn, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, aluminum nitrate and tin chloride (II) is precipitated simultaneously in stirred vessel in the constant stream with 20 % by weight concentration aqueous sodium carbonates at 65-70 DEG C, makes the pH value with glass electrode detects remain 5.7.After precipitation, air is blown into 1 hour, then the pH value sodium carbonate solution of this solution is adjusted to 7.4.The suspension of gained filters, filter cake with full demineralized water until the specific conductivity of filtrate is about 20mS.Then, filter cake is dry at the temperature of 150 DEG C in the drying chamber.The hydroxide/carbon hydrochlorate mixture obtained in this way is then at the temperature lower calcination 4 hours of 500 DEG C.Catalystic material mixes with the graphite of 3 % by weight subsequently, and is shaped to the pellet of 3x3mm.The pellet obtained in this way reduces at least 12 hours in hydrogen at the temperature of 280-300 DEG C.As-reduced catalyzer at room temperature carries out passivation in the air of dilution, and (air has O
2content is no more than in the nitrogen of 5 volume %).The catalyzer obtained in this way has the composition shown in following Table I.
Table I
| Catalyzer *) | Ni | Co | Cu | Sn | BET**) | Carrier |
| ％ | ％ | ％ | ％ | m 2/g | ||
| Catalyst A | 18.6 | 17.3 | 10.6 | 1.1 | 187 | Al 2O 3 |
*) catalyzer composition, % by weight; All the other surpluses reaching 100 % by weight are carriers
**)ISO 9277：1995
2.DEOA and the reaction of ammonia in the tubular reactor of operate continuously
Have 14mm interior diameter, center install thermopair and 1000ml cumulative volume heating tubular reactor in, under-filled granulated glass sphere bed (250ml), fill the as-reduced catalyst A of 500ml at top, last rest part is filled with granulated glass sphere again.Before reactions, catalyzer under atmospheric pressure at the highest 280 DEG C with Hydrogen activation 24 hours (25 l (stp)/h) (volumes of the liter of l (stp)=at standard temperature and pressure=be converted to standard temperature and pressure (STP) condition (20 DEG C, 1 bar is absolute)).The DEOA (80% concentration of aqueous solution) of the specified quantitative described in following Table II, ammonia and hydrogen are measured from bottom to top and passes through reactor.Reactor is maintained at about the temperature of 185-200 DEG C and the total pressure of 190 bar or 200 bar.Selective reaction temperature is to make to reach the DEOA transformation efficiency being greater than 90%.The mixture leaving reactor carries out cooling and unziping to normal atmosphere.In the different time, extract sample from reaction mixture, and use gas chromatographic analysis.For this reason, use " RTX-5 amine " GC post that length is 30m, temperature program(me) was: 70 DEG C/5 minutes, be heated to 280 DEG C with the speed of 5 DEG C/min, at 280 DEG C/10 minutes.
Experimental result can see table II.
Aftertreatment can be carried out preferably by following five steps:
1) first isolate unreacted ammonia and make its Returning reactor, optionally from the ammonia of a top of tower removing part,
2) water outlet is separated,
3) lower boiling accessory constituent is isolated,
4) from top purification distillation piperazine (I), isolate high boiling point accessory constituent via bottom simultaneously,
5) optionally a part of high boiling point accessory constituent is turned back in reaction, especially diethanolamine, N-(2-amino-ethyl) thanomin (AEEA), N-(2-amino-ethyl) ethane-1,2-diamines (diethylenetriamine, DETA).
3. prepare piperazine, 1，2-diaminoethane (EDA), diethylenetriamine (DETA) and N-(2-amino-ethyl) thanomin (AEEA) (according to Fig. 1).
The reaction water of EO and NH3 carries out homogeneous catalysis, and this carries out continuously (step of reaction 1) when NH3:EO mol ratio (MR) is 10.
In the process, the EO of 100mol/h produces the TEOA (weight ratio is 62:29:9=MEOA:DEOA:TEOA) of DEOA and 5.4mol/h of MEOA, 18.7mol/h of 46.5mol/h.
Thanomin is by fractionation by distillation (distillation stage 1).
The MEOA of whole amount in step of reaction 2 in the reactor at the Cu/Ni/Co/Al according to DE 19 53263A (BASF AG)
2o
3react under the existence of catalyzer, wherein according to page 5 embodiment 1 with NH
3(NH
3: MEOA mol ratio=8:1) based on NH
3under existing with 0.5 % by weight hydrogen of MEOA total amount, at 190 DEG C and 0.6kg MEOA/ (l
cat.h) react under the little hourly space velocity of catalyzer, obtain ethylene amines (especially PIP, EDA, DETA, AEEA).Excessive NH
3separate in distillation stage D2 and return R2.
The DEOA of whole amount in step of reaction 3 in the reactor at Cu/Ni/Co/Sn/Al
2o
3under the existence of catalyst A (see above) as described in embodiment 2A with NH
3reaction (Table II), obtains ethylene amines (especially PIP, EDA, DETA, AEEA).Excessive NH
3separate in distillation stage D3 and return R3.
Product from the distillation stage 2 and 3 combines, and goes out ethylene amines (distillation stage 4) by fractionation by distillation.Unreacted MEOA turns back to R2.In the process by step of reaction 1 formed whole amount thanomin MEOA and DEOA (see above, the DEOA of MEOA and 18.7mol/h of 46.5mol/h) reaction and the total material separated in the distillation stage 1 be:
-from the EDA of the MEOA:28.83mol/h of 46.5mol/h, the AEEA of DETA and 2.33mol/h of the PIP of 3.26mol/h, 2.56mol/h.
-from the PIP of the DEOA:12.9mol/h of 18.7mol/h, the AEEA of the DETA of the EDA of 2.5mol/h, 0.4mol/h, 0.7mol/h.
-from the EO of 100mol/h altogether: the TEOA of AEEA and 5.4mol/h of the DETA of the PIP of the EDA of 31.1mol/h, 16.1mol/h, 3.0mol/h, 3.1mol/h.
Piperazine productive rate based on EO meter is 16.1 % by mole, and higher than prior art (see Fig. 3, the schematic diagram about the embodiment from prior art):
PIP productive rate in EP 75940B2 is 3.6 % by mole, and wherein in the embodiment of 10-11 page, the EO (the 10th page of the 18th hurdle the 38th row) of 220mol/h obtains the piperazine (the 11st page of the 20th hurdle the 34th row) of 8mol/h; PIP productive rate in WO06/114417A2 is 5 % by mole, and wherein in the 9th page of embodiment that 30-40 is capable 2, the EO of 61g/h (1.39mol/h) obtains the piperazine of 6g/h (0.07mol/h).
Claims (34)
1. a method for the piperazine of preparation formula I,
The diethanolamine (DEOA) of its Chinese style II
React under the existence of the metallic catalyzer of hydrogen and load with ammonia, the wherein oxygenatedchemicals of the catalytic active substance of catalyzer containing aluminium, copper, nickel and cobalt before it is with hydrogen reducing, and the oxygenatedchemicals of the tin containing 0.2-5.0 % by weight, calculate as SnO, and this reaction carries out at the temperature of the absolute pressure of 160-220 bar, 180-220 DEG C in the liquid phase, wherein use the mol ratio between ammonia and DEOA to be 5-25, and this reaction carries out under the existence of the hydrogen of 0.2-9.0 % by weight in the total amount based on DEOA used and ammonia.
2. method according to claim 1, wherein the oxygenatedchemicals of the tin of the catalytic active substance of catalyzer containing 0.4-4.0 % by weight before it is with hydrogen reducing, calculates as SnO.
3. method according to claim 1, wherein the oxygenatedchemicals of the tin of the catalytic active substance of catalyzer containing 0.6-3.0 % by weight before it is with hydrogen reducing, calculates as SnO.
4. the method any one of aforementioned claim, wherein the oxygenatedchemicals of the cobalt of the catalytic active substance of catalyzer containing 5.0-35 % by weight before it is with hydrogen reducing, calculates as CoO.
5. the method any one of aforementioned claim, wherein the oxygenatedchemicals of the cobalt of the catalytic active substance of catalyzer containing 10-30 % by weight before it is with hydrogen reducing, calculates as CoO.
6. the method any one of aforementioned claim, wherein the catalytic active substance of catalyzer contained before it is with hydrogen reducing:
The oxygenatedchemicals of the aluminium of 15-80 % by weight, as Al
2o
3calculate,
The oxygenatedchemicals of the copper of 1.0-20 % by weight, calculates as CuO, and
The oxygenatedchemicals of the nickel of 5.0-35 % by weight, calculates as NiO.
7. method as claimed in one of claims 1-5, wherein the catalytic active substance of catalyzer contained before it is with hydrogen reducing:
The oxygenatedchemicals of the aluminium of 30-70 % by weight, as Al
2o
3calculate,
The oxygenatedchemicals of the copper of 2.0-18 % by weight, calculates as CuO, and
The oxygenatedchemicals of the nickel of 10-30 % by weight, calculates as NiO.
8. the method any one of aforementioned claim, wherein in the catalyst, the mol ratio between nickel and copper is greater than 1.
9. the method any one of aforementioned claim, the wherein catalytic active substance of catalyzer not rhenium-containing and/or ruthenium.
10. the method any one of aforementioned claim, the wherein catalytic active substance of catalyzer not iron content and/or zinc.
11. methods any one of aforementioned claim, the wherein oxygenatedchemicals of the catalytic active substance of catalyzer not siliceous and/or zirconium and/or titanium.
12. methods any one of aforementioned claim, wherein the BET surface-area (ISO 9277:1995) of catalyzer is at 30-250m
2in the scope of/g.
13. methods any one of aforementioned claim, wherein react and carry out at the temperature of 185-215 DEG C.
14. methods any one of aforementioned claim, wherein react and carry out under the absolute pressure of 170-210 bar.
15. methods any one of aforementioned claim, wherein the consumption of ammonia is 8-23 molar weight doubly, uses gauge based on DEOA.
16. methods any one of aforementioned claim, wherein react and carry out under the existence of the hydrogen of 0.25-7.0 % by weight, based on the total amount of DEOA used and ammonia.
17. methods any one of aforementioned claim, wherein catalyzer as fixed bed arrangement in the reactor.
18. methods any one of aforementioned claim, wherein this method is carried out continuously.
19. according to the method for last item claim, and wherein this reaction is carried out in tubular reactor.
20. methods any one of aforementioned two claims, wherein this reaction is carried out according to recycle gas pattern.
21. methods any one of aforementioned claim, wherein DEOA uses as the aqueous solution.
22. methods any one of aforementioned claim, wherein ammonia uses as the aqueous solution.
23. methods any one of aforementioned claim, wherein this reaction is at the DEOA/ (l of 0.3-0.8kg
cath) carry out under the little hourly space velocity of catalyzer.
24. methods any one of aforementioned claim, wherein from the reaction product of described reaction by distillation:
I () first isolates unreacted ammonia from top,
(ii) from top portion from water outlet,
(iii) from top portion from go out optional exist there is by product more lower boiling than process products I,
(iv) from top portion from going out process products piperazine (I), and having of optionally existing is retained in bottom than the more high boiling by product of process products I and the optional unreacted DEOA (II) existed.
25. according to the method for last item claim, wherein by distillation:
V the amino ethyl ethanolamine (AEEA) of the unreacted DEOA (II) optionally existed and/or the optional formula III as by product existed, from the bottom of step I v, is separated from top and turns back to reaction by ():
26. methods any one of front two claims, wherein will separate in step I and the ammonia with 90-99.9 % by weight purity turns back in reaction.
27. 1 kinds of multi-stage methods preparing the integration of piperazine, 1，2-diaminoethane (EDA), diethylenetriamine (DETA) and N-(2-amino-ethyl) thanomin (AEEA), wherein
-(step of reaction 1=R1) is in the first step of reaction, oxyethane (EO) and ammonia are obtained by reacting the product containing monoethanolamine (MEOA), diethanolamine (DEOA) and trolamine (TEOA) continuously
-(distillation stage 1=D1) goes out thanomin MEOA, DEOA and TEOA by fractionation by distillation,
The MEOA separated in D1 reacts continuously under the existence of amination catalysis with ammonia by-(step of reaction 2=R2) in the second step of reaction, and
The DEOA separated in D1 reacts according to the method any one of aforementioned claim with ammonia by-(step of reaction 3=R3) in the 3rd step of reaction.
28. according to the method for last item claim, and wherein in the first step of reaction, oxyethane (EO) and ammonia react under the existence of the water as catalyzer.
29. methods any one of front two claims, the water wherein produced in distillation stage 1 (D1) and/or the ammonia of generation turn back in the first step of reaction (R1).
30. methods any one of first three items claim, wherein
-(distillation stage 2=D2) isolates the ammonia of existence from the reaction product of step of reaction 2 by distillation.
31. methods any one of front four claims, wherein
-(distillation stage 3=D3) isolates the ammonia of existence from the reaction product of step of reaction 3 by distillation.
32. methods any one of front two claims, the two kinds of reaction product wherein retained after isolating ammonia merge, and from the product merged
-(distillation stage 4=D4) goes out piperazine, EDA, DETA and AEEA and the optional MEOA existed by fractionation by distillation.
33. methods any one of claim 27-29, wherein the reaction product of step of reaction R2 and R3 merges, and from the product merged
The ammonia that-(distillation stage 3=D3) goes out to exist by fractionation by distillation, and
-(distillation stage 4=D4) goes out piperazine, EDA, DETA and AEEA and the optional MEOA existed by fractionation by distillation.
34. methods any one of front two claims, wherein in each case in distillation stage 4 (D4), turn back to the second step of reaction (R2) by the MEOA optionally produced.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12171084 | 2012-06-06 | ||
| EP12171084.2 | 2012-06-06 | ||
| PCT/EP2013/061104 WO2013182468A1 (en) | 2012-06-06 | 2013-05-29 | Piperazine preparation method |
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|---|---|
| CN104364242A true CN104364242A (en) | 2015-02-18 |
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|---|---|---|---|
| CN201380029522.8A Pending CN104364242A (en) | 2012-06-06 | 2013-05-29 | Piperazine preparation method |
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| Country | Link |
|---|---|
| EP (1) | EP2858978A1 (en) |
| JP (1) | JP2015525214A (en) |
| CN (1) | CN104364242A (en) |
| IN (1) | IN2014DN09263A (en) |
| WO (1) | WO2013182468A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925341A (en) * | 2020-08-11 | 2020-11-13 | 山东达民化工股份有限公司 | Preparation method of piperazine |
| CN114195738A (en) * | 2021-12-27 | 2022-03-18 | 江苏康恒化工有限公司 | Solvent-free piperazine synthesis method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014009292A1 (en) * | 2012-07-13 | 2014-01-16 | Basf Se | Method for producing pyrollidine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400539A (en) * | 1981-09-30 | 1983-08-23 | Union Carbide Corporation | Process for the manufacture of ethylenediamine |
| WO2006114417A2 (en) * | 2005-04-26 | 2006-11-02 | Basf Aktiengesellschaft | Method for the production of ethyleneamines |
| CN101489980A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN101489673A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN101489979A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| US20110137030A1 (en) * | 2009-12-03 | 2011-06-09 | Basf Se | Catalyst and process for preparing an amine |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL296139A (en) | 1963-08-02 | |||
| BE757840A (en) | 1969-10-23 | 1971-04-22 | Basf Ag | PROCESS FOR PREPARING AMINES FROM ALCOHOLS |
| NL169595C (en) | 1970-05-21 | 1982-08-02 | Shell Int Research | PROCESS FOR PREPARING AMINS AND LUBRICATING OILS AND LIQUID ENGINE FUELS CONTAINING THESE. |
| DE3611230A1 (en) | 1986-04-04 | 1987-10-08 | Basf Ag | POLYBUTYL AND POLYISOBUTYLAMINE, METHOD FOR THE PRODUCTION THEREOF AND THE FUEL AND LUBRICANT COMPOSITIONS CONTAINING THE SAME |
| DE19859776B4 (en) | 1998-12-23 | 2008-06-19 | Basf Se | Process for the preparation of amines |
| DE10153411A1 (en) | 2001-10-30 | 2003-05-15 | Basf Ag | Process for the separation of water-containing raw amine mixtures from the amine synthesis |
| DE10153410A1 (en) | 2001-10-30 | 2003-05-15 | Basf Ag | Process for the separation of water-containing raw amine mixtures from the amine synthesis |
| US7196033B2 (en) | 2001-12-14 | 2007-03-27 | Huntsman Petrochemical Corporation | Advances in amination catalysis |
| CN101903095B (en) | 2007-12-21 | 2013-07-10 | 巴斯夫欧洲公司 | Method for producing an amine |
| WO2009080508A1 (en) | 2007-12-21 | 2009-07-02 | Basf Se | Method for producing an amine |
| WO2009080506A1 (en) | 2007-12-21 | 2009-07-02 | Basf Se | Method for producing an amine |
| JP5693561B2 (en) | 2009-04-08 | 2015-04-01 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing 1,6-hexanediol by hydrogenation of oligo- and polyesters |
| HUE026565T2 (en) | 2010-06-15 | 2016-06-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
| CN103189365B (en) | 2010-10-14 | 2015-01-07 | 巴斯夫欧洲公司 | Method for producing a cyclic tertiary amine |
| CN102304101A (en) | 2011-05-26 | 2012-01-04 | 绍兴兴欣化工有限公司 | Process for coproducing piperazine and N-alkyl piperazine |
-
2013
- 2013-05-29 CN CN201380029522.8A patent/CN104364242A/en active Pending
- 2013-05-29 WO PCT/EP2013/061104 patent/WO2013182468A1/en active Application Filing
- 2013-05-29 EP EP13725699.6A patent/EP2858978A1/en not_active Withdrawn
- 2013-05-29 JP JP2015515480A patent/JP2015525214A/en not_active Withdrawn
- 2013-05-29 IN IN9263DEN2014 patent/IN2014DN09263A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400539A (en) * | 1981-09-30 | 1983-08-23 | Union Carbide Corporation | Process for the manufacture of ethylenediamine |
| WO2006114417A2 (en) * | 2005-04-26 | 2006-11-02 | Basf Aktiengesellschaft | Method for the production of ethyleneamines |
| CN101489980A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN101489673A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| CN101489979A (en) * | 2006-07-14 | 2009-07-22 | 巴斯夫欧洲公司 | Method for producing an amine |
| US20110137030A1 (en) * | 2009-12-03 | 2011-06-09 | Basf Se | Catalyst and process for preparing an amine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111925341A (en) * | 2020-08-11 | 2020-11-13 | 山东达民化工股份有限公司 | Preparation method of piperazine |
| CN114195738A (en) * | 2021-12-27 | 2022-03-18 | 江苏康恒化工有限公司 | Solvent-free piperazine synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| IN2014DN09263A (en) | 2015-07-10 |
| WO2013182468A1 (en) | 2013-12-12 |
| JP2015525214A (en) | 2015-09-03 |
| EP2858978A1 (en) | 2015-04-15 |
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