CN104496939B - A kind of catalytic hydrogenation prepares the method for piperazine or alkyl piperazine - Google Patents
A kind of catalytic hydrogenation prepares the method for piperazine or alkyl piperazine Download PDFInfo
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- CN104496939B CN104496939B CN201410709452.7A CN201410709452A CN104496939B CN 104496939 B CN104496939 B CN 104496939B CN 201410709452 A CN201410709452 A CN 201410709452A CN 104496939 B CN104496939 B CN 104496939B
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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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- 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
- C07D295/027—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 containing only one hetero ring
-
- 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
- C07D295/027—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 containing only one hetero ring
- C07D295/03—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 containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a kind of method that catalytic hydrogenation prepares piperazine or alkyl piperazine, including: raw material dihydroxy ethyl piperazine or/and hydroxyethyl piperazine carries out catalytic hydrogenation reaction under catalyst action, post processing obtains piperazine or/and alkyl piperazine；In described catalyst, active component is one or more in Cu, Ni, Co.The present invention uses dihydroxy ethyl piperazine or hydroxyethyl piperazine to be raw material, prepares piperazine or alkyl piperazine by catalytic hydrogenation, it is provided that a brand-new piperazine or the synthesis technique of alkyl piperazine；Can be realized containing dihydroxy ethyl piperazine or hydroxyethyl piperazine waste liquid or the recycling of by-product by the method simultaneously；It addition, the separation of alkyl piperazine in product can be realized by existing method, further increase the value of product, reduce preparation cost.
Description
Technical field
The invention belongs to industrial chemicals preparing technical field, be specifically related to one and utilize dihydroxy ethyl piperazine
The method that piperazine or hydroxyethyl piperazine catalytic hydrogenation prepare piperazine or alkyl piperazine.
Background technology
Piperazine is important medicine intermediate and fine chemical material, and its purposes is quite varied.In recent years,
Both at home and abroad its synthesis technique has been carried out in-depth study in a large number.At present, anhydrous piperazine is synthesized both at home and abroad
The raw material of piperazine is mainly ethanolamine, N-beta-hydroxyethyl ethylenediamine, polyethylene polyamine etc., and reaction needs
High temperature, high pressure, and with the presence of catalyst and NH3、H2For operating under the reaction condition of atmosphere, and produce
Product yield is low, and by-product is more, and product separates the factors such as difficulty and limits the industrial metaplasia of piperazine
Produce.
The method preparing piperazine of report mainly has at present:
The first: application publication number is that the patent documentation of CN 102304101 A discloses a kind of piperazine
With N-alkyl piperazine joint production process, including: N-beta-hydroxyethyl ethylenediamine is dissolved in carbon number is
In the primary alconol of 1～7, under a hydrogen atmosphere, piperazine and N-alkyl piperidine are generated through catalyst reaction
The mixture of piperazine.The method uses N-beta-hydroxyethyl ethylenediamine to be raw material.
The second: application publication number is that the patent documentation of CN 102952096 A discloses and a kind of nothing
The preparation method of water piperazine, uses hydrogenation reactor, is dissolved in organic solvent by Iminodiacetonitrile 1,1'-Imidodiacetonitrile,
It is 70～110 DEG C in reaction temperature, under conditions of reaction pressure is 1～10Mpa, urges at support type
Carry out being hydrogenated with-ring-closure reaction with hydrogen in the presence of agent, the purified Piperazine anhydrous that obtains of reactant liquor, simultaneously
The a part of polyamines polyene of by-product；Described loaded catalyst comprises active component, auxiliary element and acid
Property carrier, wherein, active component is one or more in Fe, Co, Ni, Ru or Rh, excellent
Select Co and/or Ni, on the basis of carrier quality, active component be carrier quality 10～
60wt%, auxiliary element is the 0～10wt% of carrier quality.The method employing Iminodiacetonitrile 1,1'-Imidodiacetonitrile is
Raw material.
Document (piperazine synthesis and refined summary, Yali Zhu, river, the 1st phase in 2002,14-16
Page) also disclose several method preparing piperazine: (1) uses 2-chloroethyl alcohol to be Material synthesis piperazine
Method；(2) ethylene glycol, the method for ethylenediamine synthesizing piperazine are used；(3) monoethanolamine synthesizing piperazine
Method；(4) vapor phase method synthesizing piperazine, etc..
There is presently no and utilize dihydroxy ethyl piperazine or hydroxyethyl piperazine catalytic hydrogenation to prepare piperazine or first
The document report of base piperazine.
Summary of the invention
The invention provides one utilizes dihydroxy ethyl piperazine or hydroxyethyl piperazine catalytic hydrogenation to prepare piperazine
Piperazine or the method for alkyl piperazine, can obtain piperazine or the alkyl piperazine of high yield by the method, with
Time by separating further, the alkyl piperazine of available high value.
One utilizes dihydroxy ethyl piperazine or hydroxyethyl piperazine catalytic hydrogenation to prepare piperazine or alkyl piperazine
Method, including: raw material dihydroxy ethyl piperazine is or/and hydroxyethyl piperazine is urged under catalyst action
Changing hydrogenation reaction, post processing obtains piperazine or/and alkyl piperazine；
In described catalyst, active component is one or more in Cu, Ni, Co；Carrier is
γ-Al2O3、SiO2, kieselguhr, HZSM；
Above-mentioned course of reaction is as follows:
In above formula, described R can be methyl, ethyl, propyl group, isopropyl etc..
Described raw material dihydroxy ethyl piperazine, or/and hydroxyethyl piperazine, can use technical-pure grade, it is possible to adopt
With the waste liquid produced in commercial production or by-product etc., it is achieved dihydroxy ethyl in waste liquid or by-product
Piperazine is or/and the recovery of hydroxyethyl piperazine.
As preferably, in catalyst, the mass percentage content of described active component be 10%～
40%；The lowest abundant reduction being unfavorable for raw material of catalyst active component content, content is the highest, can increase
Adding preparation cost, as further preferably, the mass percentage content of described active component is
30%～40%, during it is demonstrated experimentally that use the catalyst of this composition, in the material after process, purpose
The mass percentage content of product is more than 80%.
As preferably, described active component is preferably at least one in Cu, Ni, select this two
When planting active component, in the material after process, the mass percentage content of purpose product is higher.Enter one
Preferably, described active component is preferably Ni to step, when using this technical scheme, in the material after process,
The mass percentage content of purpose product is more than 90%.
As preferably, described carrier is preferably γ-Al2O3、HZSM。
The reaction of the present invention is typically carried out in fixed-bed tube reactor, can realize continuous prodution.
As preferably, raw material uses the form of solution to add, the solvent of employing be water, methanol, ethanol, two
In oxygen six ring, diglycol dimethyl ether, diglycol, diglycol diethyl ether etc.
One or more.Use water, dioxane, diglycol dimethyl ether, diglycol,
When diglycol diethyl ether etc. are as solvent, the product obtained is substantially piperazine.Employing methanol,
When ethanol is solvent, containing some N methyl piperazine or NEP in the product obtained,
Both products are worth higher, can be separated by existing method, further increase product
Profit value.So, as preferably, described solvent is the one or two kinds of in methanol, ethanol.
In above-mentioned solution, as preferably, the mass percent concentration scope of described raw material be 10%～
90%；As further preferably, the mass percent concentration scope of described raw material is 30%～90%,
Further it is preferably 30%～50%.
In catalytic hydrogenation reaction, Hydrogen Vapor Pressure scope is 1Mpa～6Mpa, and pressure is the lowest is unfavorable for C-N
Fracture, reduce the content of target product, pressure is the highest, is unfavorable for control of industrialization, increases preparation
Cost, as further preferably, Hydrogen Vapor Pressure scope is 4Mpa～5Mpa.
In catalytic hydrogenation reaction, reaction temperature is generally 150 DEG C～300 DEG C, and same temperature is the lowest unfavorable
In the fracture of C-N, reducing the content of target product, temperature is the highest, is unfavorable for control of industrialization；Make
For further preferably, reaction temperature is 200 DEG C～300 DEG C.
When using the tubular reactor of fixed bed, feed flow rate is it is generally required to according to fixed bed pipe reaction
The amount of the specification of device and the catalyst of filling determines, is the fixed bed of 50g for catalyst loading
Tubular reactor, described feed flow rate is 0.3mL/min～3.0mL/min, more preferably
0.8mL/min～1.5mL/min.
Catalyst in the present invention can use existing method to prepare, two kinds of such as conventional methods
For:
One, the sedimentation method: prepare a certain amount of metal-nitrate solutions and precipitant solution, the two is same
Time be added drop-wise in the container equipped with a certain amount of water, be stirred well to precipitation completely after filter, wash with water to
Neutrality, filter cake is pulverized after drying in an oven, is mixed with carrier, add appropriate binding agent, fully
Stirring, grinding, then shape by extrusion device extrusion, be placed in 110～120 DEG C of drying in baking oven, finally
High-temperature roasting 3～i.e. obtain required oxidation catalyst in 6 hours in Muffle furnace.
Two, pressed disc method: prepare a certain amount of metal-nitrate solutions and precipitant solution, the two is same
Time be added drop-wise in the container equipped with a certain amount of water and carrier, be sufficiently stirred for, make precipitation be deposited directly to load
On body, precipitation completely after, be washed with water to neutrality, then filter, filter cake dry in an oven after powder
Broken, high-temperature roasting 3～6 hours in Muffle furnace, then by finely ground for gained material, add appropriate
Binding agent, in tablet machine lower sheeting molding, the bulk catalyst that gained is bigger is size-reduced, screening and
Obtain appropriately sized catalyst, can use after reduction.
Compared with prior art, beneficial effects of the present invention is embodied in:
The present invention uses dihydroxy ethyl piperazine or hydroxyethyl piperazine to be raw material, prepares piperazine by catalytic hydrogenation
Piperazine or alkyl piperazine, it is provided that a brand-new piperazine or the synthesis technique of alkyl piperazine；Can lead to simultaneously
Cross the method to realize containing dihydroxy ethyl piperazine or hydroxyethyl piperazine waste liquid or the recovery of by-product
Utilize；It addition, the separation of alkyl piperazine in product can be realized by existing method, improve further
The value of product, reduces preparation cost.
The catalyst that the present invention uses can use commercial products, it is possible to prepares voluntarily, and preparation method
Simply, use cost is low.
The method preparing piperazine or alkyl piperazine by catalytic hydrogenation of the present invention, integrated artistic is simple,
Be suitable to industrialized production.
Detailed description of the invention
Below by embodiment, the present invention is further described, but is not used in the restriction present invention；
The catalyst used in embodiment, can use following two method to prepare the (quality with main composition
Degree is explanation as a example by 40%, and catalyst of other compositions can use identical method to prepare):
1, co-precipitation:
With catalyst n i30/γ-Al2O3As a example by: by 59.46g Ni (NO3)2·6H2O is dissolved in 400mL and goes
In ionized water, it is made into nitrate solution.By 24.67g Na2CO3It is dissolved in 400mL deionized water and joining
Become precipitant.Then under 70 DEG C of water-bath Quick mechanical stirrings, by nitrate solution with precipitant simultaneously
It is added dropwise in the beaker equipped with 400mL deionized water, maintains pH value between 7～8, precipitated
Aging 1h after complete, filters, is washed with deionized by filter cake to neutrality, by filter cake 110 DEG C of drying
6h.Mix with 32.94g boehmite and 60mL 2% dust technology after filter cake is pulverized, fully stir
Mix, grind.Then shape by homemade extrusion device extrusion, be placed in baking oven after 110 DEG C of abundant drying,
500 DEG C of roasting 4h it are to slowly warm up in Muffle furnace.Before use, catalyst is cut into 3～5mm
After length, at 320 DEG C, with obtaining required catalyst after hydrogen reducing 4h, (mass percent of main composition contains
Amount is 40%).
2, pressed disc method
As a example by catalyst n i/HZSM-5, by 59.46g Ni (NO3)2·6H2O is dissolved in 400mL and goes
In ionized water, it is made into nitrate solution.By 24.67g Na2CO3It is dissolved in 400mL deionized water and joining
Become precipitant.Then under 70 DEG C of water-bath Quick mechanical stirrings, by nitrate solution with precipitant simultaneously
It is added dropwise in the beaker equipped with 200mL deionized water and 28gHZSM-5, maintains pH value 7～8
Between, precipitation completely after aging 1h, filter, filter cake is washed with deionized to without nitrate anion from
Son, dries 6h by filter cake at 110 DEG C, is then to slowly warm up to 500 DEG C of roasting 4h in Muffle furnace.
Finally by finely ground for roasting afterproduct, in tablet machine lower sheeting molding, and gained bulk catalyst is pulverized,
Screening, obtains the granule of 20～40 mesh, with obtaining required catalyst after hydrogen reducing 4h at 320 DEG C
(mass percentage content of main composition is 40%).
Embodiment 1:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 180 DEG C, hydrogen
Atmospheric pressure 2.0Mpa, at Co/ γ-Al2O3(mass percentage content of the Co of main composition is 35%,
50g) it is catalyst, in tubular reactor, is passed through dihydroxy ethyl piperazine with the flow velocity of 1.5ml/min
40% aqueous solution, in the reactant liquor finally given, piperazine content is 15.7%.
Embodiment 2:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Cu/ γ-Al2O3(mass percentage content of the Cu of main composition is 40%,
50g) it is catalyst, in tubular reactor, is passed through hydroxyethyl piperazine with the flow velocity of 1.0ml/min
40% methanol solution, in the reactant liquor finally given, the content of diethylenediamine compound is 81.4% (wherein
The content of piperazine is 68.7%, and the content of N methyl piperazine is 12.7%), use rectification method, can be by it
In the N methyl piperazine of high value separate, improve the value of product further.
Embodiment 3:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 250 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Cu/ γ-Al2O3(mass percentage content of the Cu of main composition is 40%,
50g) it is catalyst, in tubular reactor, is passed through dihydroxy ethyl piperazine with the flow velocity of 0.8ml/min
40% methanol solution, in the reactant liquor finally given, diethylenediamine compound content is 87.4% (wherein piperazine
The content of piperazine is 73.5%, and the content of N methyl piperazine is 13.9%), use rectification method, can be by wherein
The N methyl piperazine of high value separate, improve the value of product further.
Embodiment 4:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 40%,
50g) it is catalyst, in tubular reactor, is passed through hydroxyethyl piperazine with the flow velocity of 0.8ml/min
40% methanol solution, in the reactant liquor finally given, diethylenediamine compound content is 95.6% (wherein piperazine
The content of piperazine is 79.6%, and the content of N methyl piperazine is 16.0%), use rectification method, can be by wherein
The N methyl piperazine of high value separate, improve the value of product further.
Embodiment 5:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 35%,
50g) it is catalyst, in tubular reactor, is passed through dihydroxy ethyl piperazine with the flow velocity of 0.8ml/min
40% methanol solution, in the reactant liquor finally given, diethylenediamine compound content is 91.1% (wherein piperazine
The content of piperazine is 74.9%, and the content of N methyl piperazine is 16.2%), use rectification method, can be by wherein
The N methyl piperazine of high value separate, improve the value of product further.
Embodiment 6:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 40%,
50g) be catalyst, with the flow velocity of 0.8ml/min be passed through in tubular reactor dihydroxy ethyl piperazine and
40% methanol solution (dihydroxy ethyl piperazine and hydroxyethyl piperazine mol ratio are 1:1) of hydroxyethyl piperazine,
In the reactant liquor finally given, diethylenediamine compound content is 93.1%.(wherein the content of piperazine is
77.9%, the content of N methyl piperazine is 15.2%), use rectification method, can be by high value therein
N methyl piperazine is separated, and improves the value of product further.
Embodiment 7:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 35%,
50g) be catalyst, with the flow velocity of 0.8ml/min be passed through in tubular reactor dihydroxy ethyl piperazine and
40% ethanol solution (dihydroxy ethyl piperazine and hydroxyethyl piperazine mol ratio are 1:1) of hydroxyethyl piperazine,
In the reactant liquor finally given, diethylenediamine compound content is 92.8%.(wherein the content of piperazine is
72.3%, the content of NEP is 20.5%), use rectification method, can be by high value therein
NEP is separated, and improves the value of product further.
Embodiment 8:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 30%,
50g) it is catalyst, in tubular reactor, is passed through dihydroxy ethyl piperazine with the flow velocity of 0.8ml/min
40% methanol solution, in the reactant liquor finally given, diethylenediamine compound content is 84.7%.(wherein piperazine
The content of piperazine is 71.7%, and the content of N methyl piperazine is 13.0%), use rectification method, can be by wherein
The N methyl piperazine of high value separate, improve the value of product further.
Embodiment 9:
Carrying out in the tubular reactor of fixed bed, the temperature in fixed bed reaction region is 200 DEG C, hydrogen
Atmospheric pressure 4.0Mpa, at Ni/ γ-Al2O3(mass percentage content of the Ni of main composition is 40%,
50g) it is catalyst, in tubular reactor, is passed through dihydroxy ethyl piperazine with the flow velocity of 0.8ml/min
40% methanol solution, in the reactant liquor finally given, diethylenediamine compound content is 94.8%.(wherein piperazine
The content of piperazine is 79.4%, and the content of N methyl piperazine is 15.4%), use rectification method, can be by wherein
The N methyl piperazine of high value separate, improve the value of product further.
Claims (7)
1. the method that catalytic hydrogenation prepares piperazine or alkyl piperazine, including: raw material dihydroxy ethyl piperazine or/and hydroxyethyl piperazine carries out catalytic hydrogenation reaction under catalyst action, post processing obtains piperazine or/and alkyl piperazine；
In described catalyst, active component is one or more in Cu, Ni, Co；
The mass percentage content of described active component is 10%～40%；
Hydrogen Vapor Pressure scope is 1Mpa～6Mpa；Reaction temperature is 150 DEG C～300 DEG C；
Described alkyl piperazine is N methyl piperazine, NEP.
Catalytic hydrogenation the most according to claim 1 prepares the method for piperazine or alkyl piperazine, it is characterised in that the mass percentage content of described active component is 30%～40%.
Catalytic hydrogenation the most according to claim 1 prepares the method for piperazine or alkyl piperazine, it is characterised in that described active component is at least one in Cu, Ni.
Catalytic hydrogenation the most according to claim 1 prepares the method for piperazine or alkyl piperazine, it is characterised in that described catalyst is carried catalyst, and carrier is γ-Al2O3、SiO2, kieselguhr, one or more in HZSM.
5. the method preparing piperazine or alkyl piperazine according to the catalytic hydrogenation described in claim 1-4 any claim, it is characterised in that described catalytic hydrogenation reaction is carried out in fixed-bed tube reactor.
Catalytic hydrogenation the most according to claim 5 prepares the method for piperazine or alkyl piperazine, it is characterized in that, raw material uses the form of solution to add in fixed-bed tube reactor, and the solvent of employing is one or more in water, methanol, ethanol, dioxane, diglycol dimethyl ether, diglycol, diglycol diethyl ether.
Catalytic hydrogenation the most according to claim 6 prepares the method for piperazine or alkyl piperazine, it is characterised in that in solution, and the mass percent concentration scope of raw material is 10%～90%.
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| CN110343077A (en) * | 2019-07-12 | 2019-10-18 | 四川久凌制药科技有限公司 | A kind of 1- benzyl homopiperazine alkane separation method |
| CN114436993B (en) * | 2020-11-05 | 2023-10-13 | 中国石油化工股份有限公司 | Process for the preparation of piperazine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582904A (en) * | 1982-05-24 | 1986-04-15 | Air Products And Chemicals, Inc. | Amine production via condensation reactions using rare earth metal hydrogen phosphates as catalysts |
| 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 |
| CN102952096A (en) * | 2011-08-17 | 2013-03-06 | 烟台万华聚氨酯股份有限公司 | Anhydrous piperazine preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3132062B2 (en) * | 1991-07-02 | 2001-02-05 | 東ソー株式会社 | Process for producing triethylenediamines and piperazines |
| JP3132061B2 (en) * | 1991-07-02 | 2001-02-05 | 東ソー株式会社 | Process for producing triethylenediamines and piperazines |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582904A (en) * | 1982-05-24 | 1986-04-15 | Air Products And Chemicals, Inc. | Amine production via condensation reactions using rare earth metal hydrogen phosphates as catalysts |
| 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 |
| CN102952096A (en) * | 2011-08-17 | 2013-03-06 | 烟台万华聚氨酯股份有限公司 | Anhydrous piperazine preparation method |
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