CN101912779A - Catalyst for catalytic synthesis of N-methylpyrrolidine and application thereof - Google Patents
Catalyst for catalytic synthesis of N-methylpyrrolidine and application thereof Download PDFInfo
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- CN101912779A CN101912779A CN 201010243886 CN201010243886A CN101912779A CN 101912779 A CN101912779 A CN 101912779A CN 201010243886 CN201010243886 CN 201010243886 CN 201010243886 A CN201010243886 A CN 201010243886A CN 101912779 A CN101912779 A CN 101912779A
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- methylpyrrolidine
- oxolane
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Abstract
The invention relates to technology for synthesizing an intermediate in the medicinal and chemical industry, in particular to a catalyst for catalytic synthesis of N-methylpyrrolidine and a synthesis method thereof. The catalyst consists of a carrier and a catalytic activity component, wherein the carrier is a gamma-Al2O3 or HZSM series molecular sieve; the catalytic activity component is a simple substance of metal M or an oxide thereof; the catalytic activity component accounts for 0.5 to 20 percent of the total weight of the catalyst; and the granular size of the catalyst is 4 to 20 meshes. The catalyst is prepared by a kneading and extruding method or a dipping method. The catalyst has the advantages of simple preparation, low price of raw materials and easy purchase; and when used the catalytic synthesis of N-methylpyrrolidine, the catalyst has the advantages of mild catalytic reaction condition, low three-wastes and no pollution, wherein the conversion rate of tetrahydrofuran is substantially kept over 80 percent and the yield of the N-methylpyrrolidine is substantially kept over 60 percent.
Description
Technical field
The present invention relates to a kind of synthetic technology of intermediate N crassitude of medication chemistry industry, particularly relate to a kind of catalyst and application thereof that is used for catalytic synthesis of N-methylpyrrolidine.
Background technology
The N-crassitude is a kind of medicine that is widely used in, the organic base of chemical industry.Be mainly used in preparation broad-spectrum antibiotic Cefepime and go out bitterly and decide, also can be used as dye stabilizers, anticorrisive agent etc.
The preparation method of existing N-crassitude is more, wherein more representational have following several: first kind is the N-methyl pyrrolidone high pressure catalytic hydrogenation method of U.S. Pat 4892959 report, this method is under copper-chromium or chromium-aluminium catalysis, N-methyl pyrrolidone and hydrogen is synthetic N-crassitude under 150 ℃～300 ℃, 6.9～34.5MPa condition of high voltage, wherein N-methyl pyrrolidone conversion ratio is 85%, and selectivity is 85%.This method is carried out under HTHP, equipment is required high, and danger is bigger, and bigger hydrogen demand amount in the course of reaction makes this method industrialization difficulty increase.Second method is " chemical intermediate ", 2008,08:(19～21) pyrrolidines and the methyl alcohol catalytic synthesis of N-methylpyrrolidine on the H-13X molecular sieve introduced in, this method is at 300 ℃, pyrrolidines: methyl alcohol=1: 3 o'clock, pyrrolidinomethylization obtains the N-crassitude, this method report document is more, and probably about 83% to 91%, the synthetic N-crassitude yield of this method is higher for yield, but, may reach suitability for industrialized production hardly because of influenced by raw material pyrrolidines cost height.The third method is " meticulous and specialty chemicals ", and 2004,12 (10): there is the methylation reaction of pyrrolidines and formaldehyde down in the formic acid of report in 24～25, and this method is carried out under normal pressure, 80 ℃～90 ℃, formic acid catalysis.Reaction is after hcl acidifying, in distillation removal of impurities and the alkali and after obtain crude product N-crassitude, yield is 54% to 92%.The method raw material costliness is not easy to obtain, and consumes more formic acid in the course of reaction, formaldehyde, and hydrochloric acid and NaOH increase cost virtually, have also caused bigger environmental pollution simultaneously.The 4th kind of method is disclosed by 1 among the Chinese patent CN1810787, the nucleophilic substitution cyclization takes place and obtains the N-crassitude in 4-dichloroetane and methylamine under certain pressure, this method is the liquid phase reactor that takes place under 50 ℃～200 ℃, 0.4～4.0Mpa pressure, yield 85.5%.The method accessory substance is a hydrochloric acid, and amount should not reclaim greatly, thereby has increased the weight of environmental pollution, and post-reaction treatment needs a large amount of NaOH to neutralize simultaneously, and cost increases; And there is certain pressure in reaction, equipment is required high.The 5th kind of method is the synthetic N-crassitude of oxolane and methylamine catalytic ammoniation, and this method has bibliographical information, but has certain deficiency.U.S. Pat 5136053 discloses this with cyclic ester and NH
2R ammonification under aluminosilicate catalysis obtains the pyrrolidines that nitrogen replaces, but reaction needed carries out under certain pressure, and ammonia is bigger in the reaction, and between 5～20, the increase of ammonia ratio has not only increased manufacturing cost, has also shortened catalyst life simultaneously; The Journal of Organic Chemistry, 1994,59 (14): research 5 to 6 atom heterocyclic compounds have also been mentioned in synthesizing in 3998～4000, Cr-ZSM-5 (30) but the synthetic N-crassitude of catalyst catalysis oxolane and methylamine ammonification, but in this technical process, the catalyst effect is not high, and the yield of target product only maintains about in the of 48%; " Qufu Normal University's journal ", 2009,35 (1): introduced the reaction of the synthetic N-crassitude of solid superacid as catalyst oxolane and methylamine in 79～81, under the optimum process condition, the yield of N-crassitude is 81.5%, but because of the acidity of solid super-strong acid is strong excessively, cause carbon deposition quantity increase in the course of reaction, catalyst catalytic performance (catalyst life is 400h) and life-span are subjected to certain influence.
Summary of the invention
Purpose of the present invention is at the deficiency in the various synthetic methods of N-crassitude, and a kind of effective catalyst of catalytic synthesis of N-methylpyrrolidine is provided.The down synthetic N-crassitude of this catalyst normal pressure, catalytic performance is good, the reaction condition gentleness, the three wastes are few, are fit to the synthetic N-crassitude of fixed-bed catalytic under the industrialization more.
Technical scheme of the present invention is:
A kind of catalyst that is used for catalytic synthesis of N-methylpyrrolidine, this catalyst is made up of carrier and catalytic active component, and wherein carrier is γ-Al
2O
3Or HZSM series molecular sieve, catalytic active component is simple substance or its oxide of metal M, catalytic active component content is 0.5%～20% of catalyst gross mass; Catalyst particle size is 4 orders～20 orders.
Above each molecular sieve analog of the preferred HZSM of described carrier series;
Described metal M is one or more among Fe, Ni, Co, Cu, Ni, Cr or the Mn;
Catalytic active component is preferably simple substance or the oxide of Fe, Fe/Ni or Co/Ni.
Above the described Preparation of catalysts method that is used for catalytic synthesis of N-methylpyrrolidine, this catalyst is with kneading extrusion method or immersion process for preparing.
Above the described Application of Catalyst that is used for catalytic synthesis of N-methylpyrrolidine: adopt fixed bed reactors, oxolane and methylamine water solution enter reactor after vaporization, wherein methylamine water solution concentration is mass percent 40%, reacts to be 320 ℃～360 ℃ of normal pressure, temperature; Oxolane and methylamine mol ratio are 1: 1～3; Oxolane and methylamine water solution mist are 3500h by the volume space velocity of beds
-1To 7500h
-1, under catalyst action, ammonification obtains the N-crassitude.
During catalyst recited above is used, when the catalyst activity component is simple substance, before reaction with gas space velocity 400h
-1Feed H
2Reduction 3～4h.
Adopt the beneficial effect that technique scheme produced to be: the Preparation of Catalyst of using in the invention is simple, adopts conventional kneading extrusion method or infusion process to get final product; Catalytic active component adopts common metals such as Fe, Fe/Ni or Co/Ni, and carrier and catalytic active component are inexpensive and be easy to buy.Prepared catalyst is used for catalytic synthesis of N-methylpyrrolidine, wherein the oxolane conversion ratio remains on more than 80% substantially, the yield of N-crassitude remains on more than 60% substantially, than The Journal ofOrganic Chemistry, 1994,59 (14): 48% in 3998～4000 are greatly improved; Catalyst continuous operation 720h activity remains unchanged substantially, and than " Qufu Normal University's journal ", 2009,35 (1): catalyst life has had a lot of raisings in 79～81.Catalytic reaction is synthesis under normal pressure, and is less demanding to consersion unit, improved the security of operating process.Accessory substance is water in the catalytic process, and is pollution-free, and the three wastes are few.In sum, the Preparation of Catalyst of using in the invention is simple, and is cheap and easy to get; It is long that catalytic activity is stablized the life-span; Reaction raw materials is cheap and easy to get; Catalytic reaction condition gentleness, the three wastes are few, pollution-free.
The specific embodiment
Below in conjunction with concrete example, the present invention is prepared catalyst is described in detail:
Exemplifying embodiment 1: immersion process for preparing catalyst Fe/Al
2O
3
The heating of 45g ferric nitrate is dissolved in the 1200ml deionized water, adds 1000g ball-type γ-Al
2O
3, stir, dipping spends the night, with 110 ℃ at drying box inner drying 20h, in Muffle furnace, under the air atmosphere 550 ℃ of roasting 5h, promptly get required catalyst, the catalyst size is 4 orders～20 orders; The weight of catalyst consists of Fe
2O
30.9%, Al
2O
399.1%.
Exemplifying embodiment 2: kneading extrusion method prepares catalyst n i/Al
2O
3
The heating of 600g nickel nitrate is dissolved in 1000ml quality percentage composition 1% aqueous solution of nitric acid, adds 1000g γ-Al
2O
3Powder stirs, fully be ground to fully mix, extruded moulding, in 110 ℃ at drying box inner drying 20h, in Muffle furnace, under the air atmosphere 550 ℃ of roasting 5h, promptly get required catalyst, the catalyst size is 4 orders～20 orders; The weight of catalyst consists of NiO 17.2%, Al
2O
382.8%.
Exemplifying embodiment 3: immersion process for preparing catalyst Fe-ZSM-5
The heating of 225g ferric nitrate is dissolved in the 800ml deionized water, add the molecular sieve of 1000g HZSM-5, stir, dipping spends the night, with 110 ℃ at drying box inner drying 20h, in Muffle furnace, under the air atmosphere 550 ℃ of roasting 5h, promptly get required catalyst, the catalyst size is 4 orders～20 orders; The weight of catalyst consists of Fe
2O
34.1%, ZSM-595.9%.
Exemplifying embodiment 4: immersion process for preparing CATALYST Co-Ni/ZSM-11
300g cobalt nitrate, the heating of 75g nickel nitrate are dissolved in the 800ml deionized water, add 1000g HZSM-11, stir, dipping spends the night, with 110 ℃ at drying box inner drying 20h, in Muffle furnace, under the air atmosphere 550 ℃ of roasting 5h, promptly get required catalyst, the catalyst size is 4 orders～20 orders; The weight of catalyst consists of Co
2O
38.7%, NiO 1.4%, ZSM-1189.9%.
Exemplifying embodiment 5: immersion process for preparing catalyst Fe-Ni/ZSM-23
200g ferric nitrate, the heating of 70g nickel nitrate are dissolved in the 800ml deionized water, add 1000g HZSM-23, stir, dipping spends the night, with 110 ℃ at drying box inner drying 20h, in Muffle furnace, under the air atmosphere 550 ℃ of roasting 5h, promptly get required catalyst, the catalyst size is 4 orders～20 orders; The weight of catalyst consists of Fe
2O
34.4%, NiO 2.5%, ZSM-2393.1%.
Below in conjunction with concrete example, the catalyst that the present invention is prepared is applied to catalysis oxolane and the synthetic N-crassitude of methylamine:
Exemplifying embodiment 6:
In fixed bed reactors, add the catalyst 1.0L that adopts exemplifying embodiment 1 preparation, at N
2Be warming up to 310～320 ℃ under the protection, with gas space velocity 4500h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 84%, and N-crassitude yield is 67%.
Exemplifying embodiment 7:
In fixed bed reactors, add the catalyst 1.0L that adopts exemplifying embodiment 1 preparation, at N
2Be warming up to 350～500 ℃ under the protection, with gas space velocity 400h
-1Feed H
2Reduction 3～4h obtains catalyst Fe/Al that simple substance Fe is a catalytic active component
2O
3N
2Be cooled to 310～320 ℃ under the protection, with gas space velocity 4500h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 79%, and N-crassitude yield is 61%.
Exemplifying embodiment 8:
In fixed bed reactors, add the catalyst 1.2L that adopts exemplifying embodiment 2 preparations, at N
2Be warming up to 330～340 ℃ under the protection, with gas space velocity 4800h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 87%, and N-crassitude yield is 69%.
Exemplifying embodiment 9:
In fixed bed reactors, add the catalyst 1.2L that adopts exemplifying embodiment 1 preparation, at N
2Be warming up to 350～500 ℃ under the protection, with gas space velocity 400h
-1Feed H
2Reduction 3～4h, obtaining simple substance Ni is the catalyst n i/Al of catalytic active component
2O
3N
2Be cooled to 330～340 ℃ under the protection, with gas space velocity 4800h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 81%, and N-crassitude yield is 62%.
Exemplifying embodiment 10:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 3 preparations, at N
2Be warming up to 310～320 ℃ under the protection, with gas space velocity 5000h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 85%, and N-crassitude yield is 72%.
Exemplifying embodiment 11:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 3 preparations, at N
2Be warming up to 350～500 ℃ under the protection, with gas space velocity 400h
-1Feed H
2Reduction 3～4h obtains catalyst Fe-ZSM-5 that simple substance Fe is a catalytic active component; At N
2Be cooled to 310～320 ℃ under the protection, with gas space velocity 5000h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 1.5, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of oxolane is 82%, and N-crassitude yield is 70%.
Exemplifying embodiment 12:
In fixed bed reactors, add the catalyst 1.2L that adopts exemplifying embodiment 4 preparations, at N
2Be warming up to 310～320 ℃ under the protection, with gas space velocity 4500h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 2, get reactant liquor through catalytic ammoniation, rectifying gets product N-crassitude.Detect through gc analysis, wherein the conversion ratio of tetra oxygen furyl is 91%, and N-crassitude yield is 87%.
Exemplifying embodiment 13:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 4 preparations, at N
2Be warming up to 330～340 ℃ under the protection, with gas space velocity 5500h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 2, get reactant liquor through catalytic ammoniation, get product N-crassitude after the rectifying.Detect through gc analysis, wherein the conversion ratio of oxolane is 90%, and N-crassitude yield is 88%.
Exemplifying embodiment 14:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 4 preparations, at N
2Be warming up to 330～340 ℃ under the protection, with gas space velocity 5000h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 3, get reactant liquor through catalytic ammoniation, get product N-crassitude after the rectifying.Detect through gc analysis, wherein the conversion ratio of oxolane is 94.5%, and N-crassitude yield is 89%.
Exemplifying embodiment 15:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 4 preparations, at N
2Be warming up to 350～500 ℃ under the protection, with gas space velocity 400h
-1Feed H
2Reduction 3～4h obtains CATALYST Co-Ni/ZSM-11 that simple substance Co, Ni are catalytic active component; N
2Be cooled to 330～340 ℃ under the protection, with gas space velocity 5000h
-1, input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 3, get reactant liquor through catalytic ammoniation, get product N-crassitude after the rectifying.Detect through gc analysis, wherein the conversion ratio of oxolane is 91%, and N-crassitude yield is 86%.
Exemplifying embodiment 16:
In fixed bed reactors, add the catalyst 1.5L that adopts exemplifying embodiment 5 preparations, at N
2Be warming up to 330～340 ℃ under the protection, with gas space velocity 5000h
-1, the mixed liquor of input oxolane and 40% methylamine water solution in fixed bed reactors, wherein oxolane and methylamine mol ratio are 1: 3, get reactant liquor through catalytic ammoniation, get product N-crassitude after the rectifying.Detect through gc analysis, wherein the conversion ratio of oxolane is 93%, and N-crassitude yield is 86%.
Exemplifying embodiment 17:
By above-mentioned exemplifying embodiment 14 selected catalyst and reaction condition, the sampling in 100 hours of every interval detects through gc analysis, and the selectivity of the conversion ratio of oxolane and N-crassitude is investigated catalyst stability and life-span, the results are shown in Table 1.
Table 1: catalyst stability and life experiment result
As can be seen from Table 1, catalyst successive reaction 720h, oxolane conversion ratio and N-crassitude yield significantly do not reduce, so this catalyst activity is stable, catalyst life is long, and this catalyst generates the 720h activity continuously and remains unchanged substantially.
Ball-type, powder γ-Al that the present invention uses
2O
3Being Catalyst Factory, Nankai Univ with the molecular sieve of HZSM series buys.
Claims (7)
1. a catalyst that is used for catalytic synthesis of N-methylpyrrolidine is characterized by this catalyst and is made up of carrier and catalytic active component, and wherein carrier is γ-Al
2O
3Or HZSM series molecular sieve, catalytic active component is simple substance or its oxide of metal M, catalytic active component content is 0.5%～20% of catalyst gross mass; Catalyst particle size is 4 orders～20 orders.
2. the catalyst that is used for catalytic synthesis of N-methylpyrrolidine according to claim 1, it is characterized by described carrier is each molecular sieve analog of HZSM series.
3. the catalyst that is used for catalytic synthesis of N-methylpyrrolidine according to claim 1 is characterized by described metal M and is among Fe, Ni, Co, Cu, Ni, Cr or the Mn one or more.
4. as being used for the catalyst of catalytic synthesis of N-methylpyrrolidine as described in the claim 3, it is characterized by simple substance or oxide that described catalytic active component is Fe, Fe/Ni or Co/Ni.
5. the catalyst that is used for catalytic synthesis of N-methylpyrrolidine according to claim 1 is characterized by the described Preparation of catalysts method that is used for catalytic synthesis of N-methylpyrrolidine, and this catalyst is with kneading extrusion method or immersion process for preparing.
6. the Application of Catalyst that is used for catalytic synthesis of N-methylpyrrolidine according to claim 1, it is characterized by step comprises: adopt fixed bed reactors, oxolane and methylamine water solution enter reactor after vaporization, wherein methylamine water solution concentration is mass percent 40%, reacts to be 320 ℃～360 ℃ of normal pressure, temperature; Oxolane and methylamine mol ratio are 1: 1～3; Oxolane and methylamine water solution mist are 3500h by the volume space velocity of beds
-1To 7500h
-1, under catalyst action, ammonification obtains the N-crassitude.
7. as being used for the Application of Catalyst of catalytic synthesis of N-methylpyrrolidine as described in the claim 6, it is characterized by when the catalyst activity component is simple substance, before reaction with gas space velocity 400h
-1Logical H
2Reduction 3～4h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043772A (en) * | 2012-12-19 | 2013-04-17 | 浙江大学 | Method for selectively carrying out catalytic conversion on monocyclic aromatic in water to obtain small molecule acid |
| CN106496160A (en) * | 2016-10-20 | 2017-03-15 | 安庆市长虹化工有限公司 | A kind of synthesis technique of N methyl nafoxidine |
| CN109111388A (en) * | 2018-10-19 | 2019-01-01 | 江苏清泉化学股份有限公司 | A kind of production method of furans amination preparation pyrroles |
| CN110038576A (en) * | 2019-05-05 | 2019-07-23 | 中国科学院兰州化学物理研究所 | A kind of load type metal catalyst and its preparation method and application |
| CN115232049A (en) * | 2022-07-08 | 2022-10-25 | 滨州裕能化工有限公司 | Method for synthesizing N-hydroxyethyl pyrrolidone from ethylene oxide and 2-pyrrolidone in one step |
| CN115710237A (en) * | 2022-11-08 | 2023-02-24 | 河南中汇电子新材料有限公司 | Preparation process for synthesizing N-methylpyrrolidine by continuous catalytic hydrogenation of NMP |
| CN115722255A (en) * | 2022-10-13 | 2023-03-03 | 浙江衢化氟化学有限公司 | Supported catalyst for producing 1,2, 3-pentachloropropane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892959A (en) * | 1988-04-22 | 1990-01-09 | Texaco Chemical Co. | Method for the production of N-methylpyrrolidine |
| CN1810787A (en) * | 2005-01-25 | 2006-08-02 | 四平市精细化学品有限公司 | Prepn process of methyl pyrrolidine |
-
2010
- 2010-08-03 CN CN2010102438864A patent/CN101912779B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892959A (en) * | 1988-04-22 | 1990-01-09 | Texaco Chemical Co. | Method for the production of N-methylpyrrolidine |
| CN1810787A (en) * | 2005-01-25 | 2006-08-02 | 四平市精细化学品有限公司 | Prepn process of methyl pyrrolidine |
Non-Patent Citations (3)
| Title |
|---|
| 《中国稀土学会第四届学术年会论文集》 20001231 王学中等 负载型ZSM-5催化剂上NO-SCR反应的研究 557-562 1-5 , 2 * |
| 《化工中间体》 20081231 陈永生等 N-甲基吡咯烷的制备研究 19-21 1-7 , 第08期 2 * |
| 《燃料化学学报》 20051031 王雪峰等 Ni基双金属催化剂加氢脱氧性能的研究 612-616 1，3-5 第33卷, 第05期 2 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043772A (en) * | 2012-12-19 | 2013-04-17 | 浙江大学 | Method for selectively carrying out catalytic conversion on monocyclic aromatic in water to obtain small molecule acid |
| CN106496160A (en) * | 2016-10-20 | 2017-03-15 | 安庆市长虹化工有限公司 | A kind of synthesis technique of N methyl nafoxidine |
| CN109111388A (en) * | 2018-10-19 | 2019-01-01 | 江苏清泉化学股份有限公司 | A kind of production method of furans amination preparation pyrroles |
| CN110038576A (en) * | 2019-05-05 | 2019-07-23 | 中国科学院兰州化学物理研究所 | A kind of load type metal catalyst and its preparation method and application |
| CN110038576B (en) * | 2019-05-05 | 2021-09-14 | 中国科学院兰州化学物理研究所 | Supported metal catalyst and preparation method and application thereof |
| CN115232049A (en) * | 2022-07-08 | 2022-10-25 | 滨州裕能化工有限公司 | Method for synthesizing N-hydroxyethyl pyrrolidone from ethylene oxide and 2-pyrrolidone in one step |
| CN115232049B (en) * | 2022-07-08 | 2023-06-20 | 滨州裕能化工有限公司 | Method for synthesizing N-hydroxyethyl pyrrolidone from ethylene oxide and 2-pyrrolidone in one step |
| CN115722255A (en) * | 2022-10-13 | 2023-03-03 | 浙江衢化氟化学有限公司 | Supported catalyst for producing 1,2, 3-pentachloropropane and preparation method and application thereof |
| CN115710237A (en) * | 2022-11-08 | 2023-02-24 | 河南中汇电子新材料有限公司 | Preparation process for synthesizing N-methylpyrrolidine by continuous catalytic hydrogenation of NMP |
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| CN101912779B (en) | 2012-07-04 |
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