CN104387340B - A kind of method for preparing N methyl piperazines and its catalyst - Google Patents

A kind of method for preparing N methyl piperazines and its catalyst Download PDF

Info

Publication number
CN104387340B
CN104387340B CN201410675113.1A CN201410675113A CN104387340B CN 104387340 B CN104387340 B CN 104387340B CN 201410675113 A CN201410675113 A CN 201410675113A CN 104387340 B CN104387340 B CN 104387340B
Authority
CN
China
Prior art keywords
catalyst
nitrate
component
fixed bed
hours
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410675113.1A
Other languages
Chinese (zh)
Other versions
CN104387340A (en
Inventor
黄双平
王晓季
王高鹏
林爽杰
张志滨
冷晓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangxi Science and Technology Normal University
Original Assignee
Jiangxi Science and Technology Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangxi Science and Technology Normal University filed Critical Jiangxi Science and Technology Normal University
Priority to CN201410675113.1A priority Critical patent/CN104387340B/en
Publication of CN104387340A publication Critical patent/CN104387340A/en
Application granted granted Critical
Publication of CN104387340B publication Critical patent/CN104387340B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • 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
    • 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
    • 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

Abstract

The invention discloses a kind of method for preparing N methyl piperazines and its catalyst, by Catalyst packing in single hose or multi-tubular fixed-bed reactor, fixed bed reactors temperature is maintained 120~280 DEG C with preheater, Hydrogen Vapor Pressure maintains 1.0~10.0MPa；Diethanol amine and methylamine mixed liquor are passed through in fixed bed reactors, high-temperature evaporation, form gaseous mixture, gaseous mixture is fully contacted cyclization with catalyst, forms N methyl piperazines；Catalyst is prepared using infusion process or co-precipitation extrusion method.The beneficial effects of the invention are as follows with diethanol amine and methylamine as raw material, in single hose or multi-tubular fixed-bed reactor, chosen property catalyzed cyclization prepares N methyl piperazines and its catalyst, low manufacture cost.

Description

A kind of method for preparing N methyl piperazine and its catalyst
Technical field
The invention belongs to chemical material technical field, it is related to a kind of method for preparing N methyl piperazine and its catalyst.
Background technology
N methyl piperazine is a kind of important organic chemical industry's intermediate, in chemical fields such as medicine, agricultural chemicals, plastics, rubber Have a wide range of applications.In field of medicaments, in N methyl piperazine extensive pedigree antibiotic Ofloxacin of new generation and Clozapine Mesosome, is mainly used in synthesis third generation carbostyril family antibacterial drugs such as Ofloxacin, lavo-ofloxacin, fleraxacin, training fluorine husky Star, Lip river close husky star, Rufloxacin etc..Can be with synthesizing anti-AIDS pharmaceutical, antirheumatic simultaneously by raw material of N methyl piperazine Can be used as the important intermediate of insecticide.In addition, N methyl piperazine is also widely used as being extracted from the mixture of hydrocarbon the choosing of aromatic hydrocarbons Selecting property solvent and surfactant, are also widely used in plastics and rubber Polymer material.
At present, industrial production N methyl piperazine is most with piperazine and formaldehyde as raw material, with Ranny-Ni in autoclave It is obtained for catalyst carries out intermittently operated, or Leuckart-Wallach is carried out by piperazine and formaldehyde, formic acid and is synthesized.This The major defect of a little methods is expensive cost of material, and product yield and selectivity are relatively low, and operating pressure is high.Therefore, of the invention Intend with diethanol amine and methylamine cheap and easy to get as raw material, by fixed bed reactors, chosen property catalyzed cyclization realizes N- first The continuous prodution of base piperazine, to reduce product cost, simplifies production technology, improves the yield and selectivity of N methyl piperazine.
The content of the invention
It is an object of the invention to provide a kind of new method for preparing N methyl piperazine and its catalyst, solve existing N methyl piperazine and its catalyst are prepared with piperazine and formaldehyde as raw material, with Ranny-Ni as catalyst system in autoclave It is standby, high cost.
The technical solution adopted in the present invention is to follow the steps below：
Step 1：By Catalyst packing in single hose or multi-tubular fixed-bed reactor, the loadings of catalyst account for fixation The 30~50% of bed reactor volume；
Step 2：Fixed bed reactors temperature is maintained 120~280 DEG C with preheater, is connected with fixed bed reactors Hydrogen gas cylinder hydrogen is provided, Hydrogen Vapor Pressure maintains 1.0~10.0MPa；
Step 3：It is 1 by mol ratio:1~10 diethanol amine and methylamine mixed liquor is by measuring pump from fixed bed reactors Upper end charging aperture is passed through in fixed bed reactors, and mixing flow velocity is 50~800mL/h, and two kinds of raw material liqs enter through measuring pump After fixed bed reactors, can vaporize under the high temperature conditions, form gaseous mixture, gaseous mixture is fully contacted cyclization with catalyst, is formed N methyl piperazine；
Step 4：Send into collector after the condensed device of N methyl piperazine to being obtained in step 3, through gas-liquid separation after, it is dense Contracting, rectifying obtains the N methyl piperazine of high-purity.
Wherein, catalyst is prepared using any one method in following two methods：
One kind is infusion process：By the nitrate aqueous solution and carrier impregnation of catalytic active component, dipping is after 10~20 hours Filtering, dries 8~16 hours under the conditions of 120~150 DEG C, then in 300~400 DEG C of Muffle kiln roasting 3~6 hours, After it is cooled to room temperature, second dipping is carried out with carrier, 10~20 hours, filtering was dried under the conditions of 120~150 DEG C 8~16 hours, finally 500~700 DEG C of Muffle kiln roasting 4~6 hours oxidisability catalyst, the carrier is into γ-the Al of type2O3, molecular sieve, shaping silica gel, shaping diatomite, shaping metal oxide；
One kind is co-precipitation extrusion method：By the aqueous solution machinery of the nitrate aqueous solution of catalytic active component and coprecipitator Stirring is complete to precipitating, and it is 60~90 DEG C that this process keeps bath temperature, and solution ph is 7.0~8.0, and keeping temperature continues to stir Mix 1~2 hour, filter, washing filter cake to neutrality, and detect that filter cake is in 100~130 DEG C of conditions to without nitrate ion Under dry 10-20 hours, then filter cake is crushed, be added to the uniform of dust technology that mass concentration is 2% and boehmite In mixture, the mass ratio of boehmite and 2% dust technology is 1:1.6~2.2, stirring, grinding is extruded into bar with extrusion device Shape, dries 10-20 hours under the conditions of 100~130 DEG C, and the Muffle kiln roasting 4~6 after uniform intercept at 400~700 DEG C is small When obtain the catalyst of oxidisability, coprecipitator is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate.
Further, the solvent of described diethanol amine and methylamine mixed liquor is in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane One or more.
Further, the nitrate of the catalyst activity component refers to including main catalytic component copper nitrate or chromic nitrate, Auxiliary catalyst component nitrate and other component nitrate, main catalytic component, auxiliary catalyst component and other component metals nitrate are not Can repeat, auxiliary catalyst component metal nitrate refers to the one kind in ferric nitrate, zinc nitrate, and other component metals nitrate are nitre The mixture of a kind of compound in sour manganese, nickel nitrate, cobalt nitrate, the mixture of two kinds of compounds or multiple compounds.
Further, in the infusion process, the percentage by weight of catalyst activity component and carrier is：Main catalytic component：17 ~35%, auxiliary catalyst component：0~5%, other catalyst components：0~5%, carrier：55~80%, catalyst activity component and load Body weight percentage summation is 100%.
The beneficial effects of the invention are as follows with diethanol amine and methylamine as raw material, in single hose or multi-tubular fixed-bed reactor In, chosen property catalyzed cyclization prepares N methyl piperazine and its catalyst, low manufacture cost.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Course of reaction of the present invention can be schematically as follows：
The method that the present invention prepares N methyl piperazine, comprises the steps of：
Step 1：By Catalyst packing in single hose or multi-tubular fixed-bed reactor, the loadings of catalyst account for fixation The 30~50% of bed reactor volume.
Step 2：Preheater can select the electric heater of standard controllable temperature, be maintained fixed bed reactors temperature with preheater At 120~280 DEG C, the hydrogen gas cylinder that is connected with fixed bed reactors provides hydrogen, and Hydrogen Vapor Pressure maintains 1.0~ 10.0MPa；
Step 3：It is 1 by mol ratio:1~10 diethanol amine and methylamine mixed liquor is by measuring pump from fixed bed reactors Upper end charging aperture is passed through in fixed bed reactors, and mixing flow velocity is 50~800mL/h, and two kinds of raw material liqs enter through measuring pump After fixed bed reactors, can vaporize under the high temperature conditions, form gaseous mixture, gaseous mixture is fully contacted cyclization with catalyst, is formed N methyl piperazine.
Step 4：To entering collector after the condensed device of N methyl piperazine product that is obtained in step 3, through gas-liquid separation after, Concentration, rectifying obtains the N methyl piperazine of high-purity.
Described diethanol amine and the solvent of methylamine mixed liquor are the one kind or several in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane Kind.
The method for preparing catalyst, can be prepared using two methods：
One kind is infusion process：By the nitrate aqueous solution and carrier impregnation of catalytic active component, dipping is after 10~20 hours Filtering, dries 8~16 hours under the conditions of 120~150 DEG C, then in 300~400 DEG C of Muffle kiln roasting 3~6 hours, After it is cooled to room temperature, second dipping is carried out with carrier, 10~20 hours, filtering was dried under the conditions of 120~150 DEG C 8~16 hours, finally 500~700 DEG C of Muffle kiln roasting 4~6 hours oxidisability catalyst.
The carrier is the γ-Al of shaping2O3, molecular sieve, shaping silica gel, shaping diatomite, shaping metal oxidation Thing.
One kind is co-precipitation extrusion method：By the aqueous solution machinery of the nitrate aqueous solution of catalytic active component and coprecipitator Stirring is complete to precipitating, and it is 60~90 DEG C that this process keeps bath temperature, and solution ph is 7.0~8.0, and keeping temperature continues to stir Mix 1~2 hour, filter, washing filter cake to neutrality, and detect that filter cake is in 100~130 DEG C of conditions to without nitrate ion Under dry 10-20 hours, then filter cake is crushed, be added to the uniform of dust technology that mass concentration is 2% and boehmite In mixture, the mass ratio of boehmite and 2% dust technology is 1:1.6~2.2, stirring, grinding is extruded into bar with extrusion device Shape, dries 10-20 hours under the conditions of 100~130 DEG C, and the Muffle kiln roasting 4~6 after uniform intercept at 400~700 DEG C is small When obtain the catalyst of oxidisability.
The coprecipitator is NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate.
The nitrate of the catalyst activity component of above two method refers to including main catalytic component copper nitrate or nitric acid Chromium, 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 kind in ferric nitrate, zinc nitrate, and other component metals nitrate are The mixture of a kind of compound in manganese nitrate, nickel nitrate, cobalt nitrate, the mixture of two kinds of compounds or multiple compounds.
Described catalyst activity component and the percentage by weight of carrier are：Main catalytic component：17~35%, auxiliary catalysis group Point：0~5%, other catalyst components：0~5%, carrier：55~80%, catalyst activity component and vehicle weight percentage are total Be 100%.
The advantage of the invention is that：
1. the product quality prepared by meets industrial goods primes standard, and the content of N methyl piperazine is not less than 99%；
2. the catalyst choice prepared by is good, long lifespan；
3. process is simple, it is adaptable to the continuous production of industrialization；
4. low cost, good in economic efficiency.
Specific embodiment is set forth below, and the present invention will be described.
The synthesis of embodiment 1, N methyl piperazine：30.0g oxidized form solid supported catalysts are seated in a diameter of 20mm, Length is in the fixed bed reactors of 100cm, the filling of beds is highly 40cm.Catalyst in reactor keeps facing hydrogen State simultaneously has hydrogen stream to pass through, and is warming up to 350 DEG C, reduces 6 hours with this understanding, makes catalyst active.Then lower the temperature To 220 DEG C, Hydrogen Vapor Pressure rises to 8MPa, is 3 by mol ratio:1 diethanol amine and the 1,4- dioxane mixed liquor warp of methylamine From upper end press-in fixed bed reactors, mixing flow velocity is 60mL/h to preheater.Product is from fixed bed reactors lower end Collector is flowed into, product mixture is cooled and separated to obtain.Product mixture is through gas chromatographic analysis conversion per pass 74.6%, selectivity 83%.Product N methyl piperazine is obtained after rectifying, gas chromatographic analysis purity is 99.2%.
Extrusion method：Preparation method (Cr-Fe-Mn/ γ-the Al of oxidized form solid supported catalyst catalyst2O3=30:4.5: 2.5/63)。
The above is only, to better embodiment of the invention, any formal limit not to be made to the present invention System, every any simple modification made to embodiment of above according to technical spirit of the invention, equivalent variations and modification, Belong in the range of technical solution of the present invention.

Claims (1)

1. a kind of method for preparing N- methyl piperazines, it is characterised in that follow the steps below：
Step 1：By Catalyst packing in single hose or multi-tubular fixed-bed reactor, the loadings of catalyst account for fixed bed The 30~50% of reactor volume；
Step 2：Fixed bed reactors temperature is maintained 120~280 DEG C with preheater, is connected with fixed bed reactors The hydrogen gas cylinder for connecing provides hydrogen, and Hydrogen Vapor Pressure maintains 1.0~10.0MPa；
Step 3：It is 1 by mol ratio:1~10 diethanol amine and methylamine mixed liquor is anti-from fixed bed by measuring pump Device upper end charging aperture is answered to be passed through in fixed bed reactors, mixing flow velocity is 50~800mL/h, and two kinds of raw material liqs are through meter After amount pump enters fixed bed reactors, can vaporize under the high temperature conditions, form gaseous mixture, gaseous mixture is fully contacted ring with catalyst Close, form N- methyl piperazines；
Step 4：To sending into collector after the condensed device of N- methyl piperazines that is obtained in step 3, through gas-liquid separation after, Concentration, rectifying obtains the N- methyl piperazines of high-purity；
Wherein, catalyst is prepared using following methods：Infusion process：The nitrate aqueous solution of catalytic active component and carrier are soaked Stain, dipping is filtered after 10~20 hours, is dried 8~16 hours under the conditions of 120~150 DEG C, then 300 ~400 DEG C of Muffle kiln roasting 3~6 hours, after it is cooled to room temperature, second dipping, 10 is carried out with carrier ~20 hours, filtering was dried 8~16 hours under the conditions of 120~150 DEG C, finally at 500~700 DEG C Muffle kiln roasting obtains the catalyst of oxidisability for 4~6 hours, and the carrier is the γ-Al of shaping2O3, molecular sieve, shaping Silica gel, shaping diatomite；
The nitrate of the catalyst activity component refers to main catalytic component copper nitrate or chromic nitrate, auxiliary catalyst component nitrate And other component nitrate, main catalytic component, auxiliary catalyst component and other component metals nitrate can not repeatedly, auxiliary catalyst component Metal nitrate refers to the one kind in ferric nitrate, zinc nitrate, and other component metals nitrate are manganese nitrate, nickel nitrate, nitric acid The mixture of a kind of compound in cobalt, the mixture of two kinds of compounds or multiple compounds；
Described diethanol amine and the solvent of methylamine mixed liquor are one or more in water, methyl alcohol, benzene, Isosorbide-5-Nitrae-dioxane；
In the infusion process, the percentage by weight of catalyst activity component and carrier is：Main catalytic component：17~35%, Auxiliary catalyst component：0~5% and be 0, other catalyst components：0~5% and be 0, carrier：55~80%, catalysis Agent active component and vehicle weight percentage summation are 100%.
CN201410675113.1A 2014-11-21 2014-11-21 A kind of method for preparing N methyl piperazines and its catalyst Expired - Fee Related CN104387340B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410675113.1A CN104387340B (en) 2014-11-21 2014-11-21 A kind of method for preparing N methyl piperazines and its catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410675113.1A CN104387340B (en) 2014-11-21 2014-11-21 A kind of method for preparing N methyl piperazines and its catalyst

Publications (2)

Publication Number Publication Date
CN104387340A CN104387340A (en) 2015-03-04
CN104387340B true CN104387340B (en) 2017-07-07

Family

ID=52605316

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410675113.1A Expired - Fee Related CN104387340B (en) 2014-11-21 2014-11-21 A kind of method for preparing N methyl piperazines and its catalyst

Country Status (1)

Country Link
CN (1) CN104387340B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105601588B (en) * 2015-11-17 2018-06-29 江西科技师范大学 The synthetic method of N- hydroxyethyl piperazine coproduction piperazines
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
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
CN110841648B (en) * 2019-11-19 2023-03-03 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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1634896A (en) * 2003-12-30 2005-07-06 天津大学 Method for continuous synthesis of piperazine compounds by fixed bed

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1634896A (en) * 2003-12-30 2005-07-06 天津大学 Method for continuous synthesis of piperazine compounds by fixed bed

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Catalytic synthesis of N-methylpiperazine from diethanolamine and methylamine by cyclodehydration reaction;K Nagaiah et al.;《Indian Journal of Chemical Technology》;19941130;第1卷;第359-360页 *
Intermolecular Cyclization of Diethanolamine and Methylamine to N-Methylpiperazine over Zeolites;K. Nagaiah et al.;《Journal of Catalysis》;19941231;第147卷;第349-351页 *
气-固相催化环合N-甲基哌嗪的研究;王李平等;《江西科技师范大学学报》;20131231(第6期);第11页1.1、1.3、2.1 *
醇催化胺化反应的研究;白国义;《中国博士学位论文全文数据库 工程科技I辑》;20030915;第21页第2-4段 *

Also Published As

Publication number Publication date
CN104387340A (en) 2015-03-04

Similar Documents

Publication Publication Date Title
CN104387340B (en) A kind of method for preparing N methyl piperazines and its catalyst
CN102432565B (en) Method for preparing 2-hydroxyethylpiperazine
CN104447209A (en) Method for preparing cyclohexanol by catalyzing by base metal catalyst
CN104190391B (en) A kind of catalyst and the purposes in preparing thymol method thereof
CN105601588B (en) The synthetic method of N- hydroxyethyl piperazine coproduction piperazines
EP3042719B1 (en) Use of a catalyst for fixed bed aniline rectification residue recycling
CN101049562A (en) Catalyst for preparing halogeno anilin through catalytic hydrogenation of halogeno nitrobenzene and preparation method
CN105153058A (en) Synthetic method of benzotriazoles compound
CN103143381B (en) Carbon nitride material immobilized heteropolyacid catalyst and olefin epoxy synthesizing method
CN104557562A (en) Method for producing N,N,N',N'- tetramethylethylenediamine by virtue of direct catalytic amination of dimethylethanolamine
CN108067213B (en) catalyst for resource utilization of aniline rectification residues and preparation method thereof
CN108273507B (en) Method for reducing nitrile compound by catalytic hydrogenation
CN104557564B (en) Preparation method of phenylmethylamine
CN105294541B (en) The synthetic method of 2,2,6,6 tetramethyl piperidines
CN101914042A (en) Preparation method of nicarbazin midbody 4,4'- binitro sym-diphenylurea
CN111170840B (en) Application of supported bifunctional catalyst in preparation of 3-acetyl propanol from furfural
Muller et al. Raney cobalt: an effective and recyclable catalyst for the Pauson–Khand reaction
CN102993131B (en) Method for utilizing o-chlorocyclohexanol to prepare cyclohexene oxide by cyclization
CN109622031A (en) The preparation method of 2- hydroxyphosphonoacetic acid zirconium and its application in furfuryl alcohol synthesis
CN103331160A (en) Preparation method of high-dispersion copper-based catalyst based on non-precious metal
CN104130210B (en) The preparation method of N-methylmorpholine
CN102633648B (en) Preparation method of n-butylamine
CN101463016A (en) Method for synthesizing 2,6-dimethyl piperazine
CN110152661A (en) A kind of nitrobenzene compounds hydrogenation synthesis amino benzenes compounds nanometer Au-CeO2(cube) catalyst
CN106866583B (en) A kind of preparation method of two (2- ethoxy) piperazines

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170707

Termination date: 20171121