CN104387340A - Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine - Google Patents
Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine Download PDFInfo
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- CN104387340A CN104387340A CN201410675113.1A CN201410675113A CN104387340A CN 104387340 A CN104387340 A CN 104387340A CN 201410675113 A CN201410675113 A CN 201410675113A CN 104387340 A CN104387340 A CN 104387340A
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing N-methyl piperazine and a catalyst of N-methyl piperazine. The method comprises the following steps: filling the catalyst in a single-pipe type or multiple-pipe type fixed bed reactor, maintaining the temperature of the fixed bed reactor to 120-280 DEG C by utilizing a preheater, and maintaining hydrogen pressure to 1.0-10.0 MPa; introducing mixed liquor of diethanol amine and methylamine to the fixed bed reactor to vaporize at a high temperature to form a mixed gas, and sufficiently contacting and cyclizing the mixed gas with the catalyst to form N-methyl piperazine; and preparing the catalyst by adopting an impregnation method or coprecipitation extruded strip method. By utilizing the method, the diethanol amine and the methylamine are used as raw materials to be subjected to selective catalytic cyclization to prepare N-methyl piperazine and the catalyst of N-methyl piperazine in the single-pipe type or multiple-pipe type fixed bed reactor, and the preparation cost is low.
Description
Technical field
The invention belongs to chemical material technical field, relate to a kind of method preparing N methyl piperazine and catalyzer thereof.
Background technology
N methyl piperazine is a kind of important organic chemical industry's intermediate, has a wide range of applications at chemical fields such as medicine, agricultural chemicals, plastics, rubber.At field of medicaments, N methyl piperazine is the intermediate of extensive pedigree antibiotic Ofloxacine USP 23 of new generation and leoponex, is mainly used in synthesis third generation carbostyril family antibacterial drugs such as Ofloxacine USP 23, levofloxacin, fleroxacin, Pefloxacin, Lip river and closes husky star, rufloxacin etc.Be that raw material can also synthesizing anti-AIDS pharmaceutical, antirheumatic can be used as the important intermediate of sterilant with N methyl piperazine.In addition, N methyl piperazine is also widely used as from the mixture of hydrocarbon, extract aromatic hydrocarbons selective solvent and tensio-active agent, is also widely used in the macromolecular material such as plastics and rubber.
At present, industrial production N methyl piperazine is raw material mainly with piperazine and formaldehyde greatly, is that catalyzer carries out periodical operation and obtains, or carries out Leuckart-Wallach Reactive Synthesis by piperazine and formaldehyde, formic acid in autoclave with Ranny-Ni.The main drawback of these methods is that raw materials cost is expensive, product yield and selectivity lower, working pressure is high.For this reason, the present invention to intend with diethanolamine cheap and easy to get and methylamine, for raw material, passing through fixed-bed reactor, through selective catalysis cyclization, realize the continuous prodution of N methyl piperazine, to reduce product cost, simplify production technique, improve yield and the selectivity of N methyl piperazine.
Summary of the invention
The object of the present invention is to provide a kind of novel method preparing N methyl piperazine and catalyzer thereof, solve and existingly prepare N methyl piperazine and catalyzer thereof with piperazine and formaldehyde for raw material, be that catalyzer is prepared with Ranny-Ni in autoclave, cost is high.
The technical solution adopted in the present invention is carried out according to following steps:
Step 1: by catalyst loading in single hose or multi-tubular fixed-bed reactor, the loadings of catalyzer accounts for 30 ~ 50% of fixed-bed reactor volume;
Step 2: fixed bed reaction actuator temperature is maintained 120 ~ 280 DEG C with preheater, the hydrogen gas cylinder be connected with fixed-bed reactor provides hydrogen, and hydrogen pressure maintains 1.0 ~ 10.0MPa;
Step 3: be that diethanolamine and the methylamine mixed solution of 1:1 ~ 10 passes into fixed-bed reactor by volume pump from fixed-bed reactor upper end opening for feed by mol ratio, mixed solution flow velocity is 50 ~ 800mL/h, two kinds of raw material liqs enter after fixed-bed reactor through volume pump, can vaporize under the high temperature conditions, form gas mixture, gas mixture fully contacts cyclization with catalyzer, forms N methyl piperazine;
Step 4: send into collector to the N methyl piperazine obtained in step 3 after condenser, after gas-liquid separation, concentrated, rectifying obtains highly purified N methyl piperazine.
Wherein, catalyzer adopts any one method preparation in following two kinds of methods:
One is pickling process: by the nitrate aqueous solution of catalytic active component and carrier impregnation, flood after 10 ~ 20 hours and filter, drying 8 ~ 16 hours under 120 ~ 150 DEG C of conditions, then roasting 3 ~ 6 hours in the retort furnace of 300 ~ 400 DEG C, be cooled to after room temperature until it, carry out second time with carrier to flood, 10 ~ 20 hours, after filtration under 120 ~ 150 DEG C of conditions dry 8 ~ 16 hours, finally in the retort furnace of 500 ~ 700 DEG C, roasting obtains the catalyzer of oxidisability for 4 ~ 6 hours, and described carrier is shaping γ-Al
2o
3, molecular sieve, shaping silica gel, shaping diatomite, shaping metal oxide;
One is co-precipitation extrusion method: by complete to precipitation for the aqueous solution mechanical stirring of the nitrate aqueous solution of catalytic active component and coprecipitator, this process keeps bath temperature to be 60 ~ 90 DEG C, solution ph is 7.0 ~ 8.0, temperature is kept to continue stirring 1 ~ 2 hour, filter, washing leaching cake is to neutral, and detect to without nitrate ion, filter cake is dry 10-20 hour under 100 ~ 130 DEG C of conditions, then filter cake is pulverized, join mass concentration be 2% dust technology and pseudo-boehmite uniform mixture in, pseudo-boehmite and 2% the mass ratio of dust technology be 1:1.6 ~ 2.2, stir, grinding, strip is extruded into extrusion device, dry 10-20 hour under 100 ~ 130 DEG C of conditions, after even intercept, in the retort furnace of 400 ~ 700 DEG C, roasting obtains the catalyzer of oxidisability for 4 ~ 6 hours, coprecipitator is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt.
Further, the solvent of described diethanolamine and methylamine mixed solution is one or more in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane.
Further, the nitrate of described catalyst activity component refers to and comprises main catalytic component cupric nitrate or chromium nitrate, auxiliary catalyst component nitrate and other component nitrate, main catalytic component, auxiliary catalyst component and other component metals nitrate can not repeat, auxiliary catalyst component metal nitrate refers to the one in iron nitrate, zinc nitrate, and other component metals nitrate is a kind of compound, the mixture of two kinds of compounds or the mixture of multiple compounds in manganous nitrate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Further, in described pickling process, the weight percent of catalyst activity component and carrier is: main catalytic component: 17 ~ 35%, auxiliary catalyst component: 0 ~ 5%, other catalyst component: 0 ~ 5%, carrier: 55 ~ 80%, catalyst activity component and vehicle weight per-cent summation are 100%.
The invention has the beneficial effects as follows that in single hose or multi-tubular fixed-bed reactor, prepare N methyl piperazine and catalyzer thereof through selective catalysis cyclization, cost of manufacture is low with diethanolamine and methylamine for raw material.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Reaction process of the present invention can schematically as follows:
The present invention prepares the method for N methyl piperazine, comprises following steps:
Step 1: by catalyst loading in single hose or multi-tubular fixed-bed reactor, the loadings of catalyzer accounts for 30 ~ 50% of fixed-bed reactor volume.
Step 2: preheater can the electric heater of selection standard temperature controllable, and with preheater, fixed bed reaction actuator temperature is maintained 120 ~ 280 DEG C, the hydrogen gas cylinder be connected with fixed-bed reactor provides hydrogen, and hydrogen pressure maintains 1.0 ~ 10.0MPa;
Step 3: be that diethanolamine and the methylamine mixed solution of 1:1 ~ 10 passes into fixed-bed reactor by volume pump from fixed-bed reactor upper end opening for feed by mol ratio, mixed solution flow velocity is 50 ~ 800mL/h, two kinds of raw material liqs enter after fixed-bed reactor through volume pump, can vaporize under the high temperature conditions, form gas mixture, gas mixture fully contacts cyclization with catalyzer, forms N methyl piperazine.
Step 4: enter collector to the N methyl piperazine product obtained in step 3 after condenser, after gas-liquid separation, concentrated, rectifying obtains highly purified N methyl piperazine.
The solvent of described diethanolamine and methylamine mixed solution is one or more in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane.
The method of described Kaolinite Preparation of Catalyst, can adopt two kinds of method preparations:
One is pickling process: by the nitrate aqueous solution of catalytic active component and carrier impregnation, flood after 10 ~ 20 hours and filter, drying 8 ~ 16 hours under 120 ~ 150 DEG C of conditions, then roasting 3 ~ 6 hours in the retort furnace of 300 ~ 400 DEG C, be cooled to after room temperature until it, carry out second time with carrier and flood, 10 ~ 20 hours, after filtration under 120 ~ 150 DEG C of conditions dry 8 ~ 16 hours, finally in the retort furnace of 500 ~ 700 DEG C roasting 4 ~ 6 hours the catalyzer of oxidisability.
Described carrier is shaping γ-Al
2o
3, molecular sieve, shaping silica gel, shaping diatomite, shaping metal oxide.
One is co-precipitation extrusion method: by complete to precipitation for the aqueous solution mechanical stirring of the nitrate aqueous solution of catalytic active component and coprecipitator, this process keeps bath temperature to be 60 ~ 90 DEG C, solution ph is 7.0 ~ 8.0, temperature is kept to continue stirring 1 ~ 2 hour, filter, washing leaching cake is to neutral, and detect to without nitrate ion, filter cake is dry 10-20 hour under 100 ~ 130 DEG C of conditions, then filter cake is pulverized, join mass concentration be 2% dust technology and pseudo-boehmite uniform mixture in, pseudo-boehmite and 2% the mass ratio of dust technology be 1:1.6 ~ 2.2, stir, grinding, strip is extruded into extrusion device, dry 10-20 hour under 100 ~ 130 DEG C of conditions, after even intercept, in the retort furnace of 400 ~ 700 DEG C, roasting obtains the catalyzer of oxidisability for 4 ~ 6 hours.
Described coprecipitator is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt.
The nitrate of the catalyst activity component of above-mentioned two kinds of methods refers to and comprises main catalytic component cupric nitrate or chromium nitrate, auxiliary catalyst component nitrate and other component nitrate, main catalytic component, auxiliary catalyst component and other component metals nitrate can not repeat, auxiliary catalyst component metal nitrate refers to the one in iron nitrate, zinc nitrate, and other component metals nitrate is a kind of compound, the mixture of two kinds of compounds or the mixture of multiple compounds in manganous nitrate, nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES.
Described catalyst activity component and the weight percent of carrier are: main catalytic component: 17 ~ 35%, auxiliary catalyst component: 0 ~ 5%, other catalyst component: 0 ~ 5%, carrier: 55 ~ 80%, catalyst activity component and vehicle weight per-cent summation are 100%.
The invention has the advantages that:
1. the quality product prepared by meets industrial goods first grade standard, and the content of N methyl piperazine is not less than 99%;
2. the catalyst selectivity prepared by is good, and the life-span is long;
3. technique is simple, is applicable to industrialization continuous seepage;
4. cost is low, good in economic efficiency.
The present invention will be described to enumerate specific embodiment below.
The synthesis of embodiment 1, N methyl piperazine: it is 20mm that 30.0g oxidized form solid supported catalyst is seated in diameter, and length is in the fixed-bed reactor of 100cm, the loading height of beds is 40cm.Catalyst in reactor keeps facing hydrogen state and having hydrogen stream to pass through, and is warming up to 350 DEG C, reduces 6 hours with this understanding, makes catalyzer have activity.Then be cooled to 220 DEG C, hydrogen pressure rises to 8MPa, and be that the diethanolamine of 3:1 and the Isosorbide-5-Nitrae-dioxane mixed solution of methylamine are pressed into fixed-bed reactor from upper end through preheater by mol ratio, mixed solution flow velocity is 60mL/h.Reaction product flows into collector from fixed-bed reactor lower end, through cooling, is separated to obtain product mixture.Product mixture is 74.6% through gas chromatographic analysis per pass conversion, selectivity 83%.Obtain product N methyl piperazine after rectifying, gas chromatographic analysis purity is 99.2%.
Extrusion method: the preparation method (Cr-Fe-Mn/ γ-Al of oxidized form solid supported catalyst catalyzer
2o
3=30:4.5:2.5/63).
The above is only to better embodiment of the present invention, not any pro forma restriction is done to the present invention, every any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all belong in the scope of technical solution of the present invention.
Claims (4)
1. prepare a method for N methyl piperazine and catalyzer thereof, it is characterized in that carrying out according to following steps:
Step 1: by catalyst loading in single hose or multi-tubular fixed-bed reactor, the loadings of catalyzer accounts for 30 ~ 50% of fixed-bed reactor volume;
Step 2: fixed bed reaction actuator temperature is maintained 120 ~ 280 DEG C with preheater, the hydrogen gas cylinder be connected with fixed-bed reactor provides hydrogen, and hydrogen pressure maintains 1.0 ~ 10.0MPa;
Step 3: be that diethanolamine and the methylamine mixed solution of 1:1 ~ 10 passes into fixed-bed reactor by volume pump from fixed-bed reactor upper end opening for feed by mol ratio, mixed solution flow velocity is 50 ~ 800mL/h, two kinds of raw material liqs enter after fixed-bed reactor through volume pump, can vaporize under the high temperature conditions, form gas mixture, gas mixture fully contacts cyclization with catalyzer, forms N methyl piperazine;
Step 4: after condenser, collector is sent into the N methyl piperazine obtained in step 3, after gas-liquid separation, concentrated, rectifying obtains highly purified N methyl piperazine;
Wherein, catalyzer adopts any one method preparation in following two kinds of methods:
One is pickling process: by the nitrate aqueous solution of catalytic active component and carrier impregnation, flood after 10 ~ 20 hours and filter, drying 8 ~ 16 hours under 120 ~ 150 DEG C of conditions, then roasting 3 ~ 6 hours in the retort furnace of 300 ~ 400 DEG C, be cooled to after room temperature until it, carry out second time with carrier to flood, 10 ~ 20 hours, after filtration under 120 ~ 150 DEG C of conditions dry 8 ~ 16 hours, finally in the retort furnace of 500 ~ 700 DEG C, roasting obtains the catalyzer of oxidisability for 4 ~ 6 hours, and described carrier is shaping γ-Al
2o
3, molecular sieve, shaping silica gel, shaping diatomite, shaping metal oxide;
One is co-precipitation extrusion method: by complete to precipitation for the aqueous solution mechanical stirring of the nitrate aqueous solution of catalytic active component and coprecipitator, this process keeps bath temperature to be 60 ~ 90 DEG C, solution ph is 7.0 ~ 8.0, temperature is kept to continue stirring 1 ~ 2 hour, filter, washing leaching cake is to neutral, and detect to without nitrate ion, filter cake is dry 10-20 hour under 100 ~ 130 DEG C of conditions, then filter cake is pulverized, join mass concentration be 2% dust technology and pseudo-boehmite uniform mixture in, pseudo-boehmite and 2% the mass ratio of dust technology be 1:1.6 ~ 2.2, stir, grinding, strip is extruded into extrusion device, dry 10-20 hour under 100 ~ 130 DEG C of conditions, after even intercept, in the retort furnace of 400 ~ 700 DEG C, roasting obtains the catalyzer of oxidisability for 4 ~ 6 hours, coprecipitator is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, volatile salt.
2. according to the method preparing N methyl piperazine and catalyzer thereof a kind of described in claim 1, it is characterized in that: the solvent of described diethanolamine and methylamine mixed solution is one or more in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane.
3. according to the method preparing N methyl piperazine and catalyzer thereof a kind of described in claim 1, it is characterized in that: the nitrate of described catalyst activity component refers to and comprises main catalytic component cupric nitrate or chromium nitrate, auxiliary catalyst component nitrate and other component nitrate, main catalytic component, auxiliary catalyst component and other component metals nitrate can not repeat, auxiliary catalyst component metal nitrate refers to iron nitrate, one in zinc nitrate, other component metals nitrate is manganous nitrate, nickelous nitrate, a kind of compound in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, the mixture of two kinds of compounds or the mixture of multiple compounds.
4. according to the method preparing N methyl piperazine and catalyzer thereof a kind of described in claim 1, it is characterized in that: in described pickling process, the weight percent of catalyst activity component and carrier is: main catalytic component: 17 ~ 35%, auxiliary catalyst component: 0 ~ 5%, other catalyst component: 0 ~ 5%, carrier: 55 ~ 80%, catalyst activity component and vehicle weight per-cent summation are 100%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888844A (en) * | 2015-06-04 | 2015-09-09 | 西安近代化学研究所 | Preparation method of piperazine synthesis catalyst |
| CN105601588A (en) * | 2015-11-17 | 2016-05-25 | 江西科技师范大学 | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production |
| CN105837457A (en) * | 2016-03-30 | 2016-08-10 | 河北华茂伟业科技有限公司 | Method for synthesizing bis(dimethylaminoethyl)ether under catalysis of metal catalyst |
| CN106984343A (en) * | 2017-03-20 | 2017-07-28 | 钦州学院 | A kind of catalyst for being used for N β AEEAs synthesizing piperazines and N methyl piperazines and preparation method thereof |
| CN110841648A (en) * | 2019-11-19 | 2020-02-28 | 中国石油化工股份有限公司 | Supported catalyst for N, N-dimethyl-1,3-propane diamine and preparation and application thereof |
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| CN1634896A (en) * | 2003-12-30 | 2005-07-06 | 天津大学 | Method for continuous synthesis of piperazine compounds by fixed bed |
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| CN1634896A (en) * | 2003-12-30 | 2005-07-06 | 天津大学 | Method for continuous synthesis of piperazine compounds by fixed bed |
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| K NAGAIAH ET AL.: "Catalytic synthesis of N-methylpiperazine from diethanolamine and methylamine by cyclodehydration reaction", 《INDIAN JOURNAL OF CHEMICAL TECHNOLOGY》 * |
| K. NAGAIAH ET AL.: "Intermolecular Cyclization of Diethanolamine and Methylamine to N-Methylpiperazine over Zeolites", 《JOURNAL OF CATALYSIS》 * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888844A (en) * | 2015-06-04 | 2015-09-09 | 西安近代化学研究所 | Preparation method of piperazine synthesis catalyst |
| CN104888844B (en) * | 2015-06-04 | 2017-07-04 | 西安近代化学研究所 | A kind of method for preparing catalyst of synthesizing piperazine |
| CN105601588A (en) * | 2015-11-17 | 2016-05-25 | 江西科技师范大学 | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production |
| CN105837457A (en) * | 2016-03-30 | 2016-08-10 | 河北华茂伟业科技有限公司 | Method for synthesizing bis(dimethylaminoethyl)ether under catalysis of metal catalyst |
| CN105837457B (en) * | 2016-03-30 | 2019-04-16 | 河北华茂伟业科技有限公司 | The method that applied metal catalyst synthesizes bis- (dimethylaminoethyl) ethers |
| CN106984343A (en) * | 2017-03-20 | 2017-07-28 | 钦州学院 | A kind of catalyst for being used for N β AEEAs synthesizing piperazines and N methyl piperazines and preparation method thereof |
| CN106984343B (en) * | 2017-03-20 | 2019-08-13 | 钦州学院 | It is a kind of for N- beta-hydroxyethyl ethylenediamine synthesizing piperazine and catalyst of N methyl piperazine and preparation method thereof |
| CN110841648A (en) * | 2019-11-19 | 2020-02-28 | 中国石油化工股份有限公司 | Supported catalyst for N, N-dimethyl-1,3-propane diamine and preparation and application thereof |
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| Publication number | Publication date |
|---|---|
| CN104387340B (en) | 2017-07-07 |
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