CN104130210B - The preparation method of N-methylmorpholine - Google Patents

The preparation method of N-methylmorpholine Download PDF

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CN104130210B
CN104130210B CN201410309041.9A CN201410309041A CN104130210B CN 104130210 B CN104130210 B CN 104130210B CN 201410309041 A CN201410309041 A CN 201410309041A CN 104130210 B CN104130210 B CN 104130210B
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loaded catalyst
gross weight
methylmorpholine
reaction
preparation
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CN104130210A (en
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张愚
刘金强
冯烈
郑丰平
顾海燕
刘询
王爱艳
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ZHEJIANG JIANYE CHEMICAL CO Ltd
Luoyang Normal University
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ZHEJIANG JIANYE CHEMICAL CO Ltd
Luoyang Normal University
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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
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation method of N-methylmorpholine: using atmospheric fixed bed reactor as reaction unit, loaded catalyst is set in atmospheric fixed bed reactor; With the mixture of morpholine and methyl-formiate for raw material, the mol ratio of described methyl-formiate and morpholine is 0.5 ~ 0.9:1; By the fixed-bed reactor containing loaded catalyst after material gasification, under hydro condition, carry out amination reaction; Reaction pressure is 0.12 ~ 0.19MPa, temperature is 120 ~ 130 DEG C; The volume space velocity V of reaction is 0.05 ~ 0.3g/h/mL; After above-mentioned reaction terminates, after condensation, collect reactant, then after dehydration, rectifying, obtain N-methylmorpholine; The preparation process of loaded catalyst is as follows: utilize metal salt solution and carrier to make loaded catalyst, in described loaded catalyst, metal accounts for 22% ~ 32% of gross weight, and metal-salt is mantoquita and zinc salt.

Description

The preparation method of N-methylmorpholine
Technical field
The present invention relates to a kind of preparation method of organic compound, particularly a kind of organic chemical industry's intermediate---the preparation method of N-methylmorpholine.
Background technology
N-methylmorpholine is a kind of important organic chemical industry's intermediate, is a kind of excellent solvent, emulsifying agent, inhibiter, polyurethane foam catalyzer, also can as pesticide intermediate.Its synthetic method mainly contain with morpholine be raw material N-methylation method, with diethanolamine be raw material cyclization method, with the diethyl acetal cyclization method that is raw material and take ethylene dichloride as the synthetic method etc. of raw material.These methods generally adopt metal catalyst to carry out catalysis, carry out under higher temperature and pressure.And the method for most convenient adopts morpholine to be raw material, different methylating reagents is directly selected to carry out N-methylation reaction.
At present, be that the method for Material synthesis N-methylmorpholine mainly contains following several with morpholine:
1), the USSR (Union of Soviet Socialist Republics) patent SU164234 of 1985, report with morpholine and methyl chloride for N-methylmorpholine prepared by raw material, yield is higher.But this method selects methyl chloride to be methylating reagent, toxicity is comparatively large, and lower boiling needs steel cylinder to store, inconvenient operation; The hydrogenchloride simultaneously generated can with raw material and product salify, consume large, unfriendly to environment;
2), document Syn.Comm, 2002,32 (3), p457-465, report with the method for formaldehyde, oxalic acid and the morpholine synthesis N-methylmorpholine that is raw material.This method per pass conversion is high, reaction conditions is gentle, does not use catalyzer, but releases carbonic acid gas isothermal chamber gas, and Atom economy is poor, wastes more, pollutes large.
3), the US Patent No. 585949 of 1985 proposes to be obtained by reacting N-methylmorpholine with methyl-sulfate and morpholine, and transformation efficiency is high, and raw material is conveniently easy to get.But methyl-sulfate toxicity is very large, and this technique is eliminated gradually now;
4), the German patent DE 2205597 of 1973 proposes, and carry out alkylated reaction with morpholine and methyl alcohol, catalyzer is SiO 2-H 3pO 4, the molar ratio of morpholine and methyl alcohol is 40:60, take flow velocity as the catalyst fluidized bed that the mixing steam of 106g/h is passed into 200mL, and carry out reacting the N-methylmorpholine that can obtain 91% under 160 degree, the transformation efficiency of morpholine reaches 95%.This technique have employed raw material cheap and easy to get, but the technical requirements of fluidized-bed process is higher, and operation easier is large, very high to the intensity of catalyzer, wear resistance, particle diameter and life requirements in industrial production.The pilot fluidized-bed such for N-methylmorpholine is produced very not applicable.
5), document " chemistry with bonding ", 2007,29 (1), p66-67, reporting with methylcarbonate is that methylating reagent carries out methylation reaction to morpholine.This reaction without the need to carrying out under catalyzer existent condition, but can only be used for still reaction, and by-product carbinol can not make full use of, and Atom economy is poor, is not suitable for large-scale commercial production.
6), invention " a kind of synthetic method of N-methylmorpholine " (contriver: Chen Xinzhi etc.) of 200710069194.0 propose with methyl alcohol to be methylating reagent, and morpholine and methyl alcohol are Cu/Ni/Co/Al by catalyzer 2o 3bed, and the yield of 85% can be reached.The method is to document 4) described method innovates, but due to problems such as production cost are higher, therefore still has larger room for improvement.
Visible, existing method is only suitable for laboratory small-scale production, and any one method is not suitable for scale operation.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of cost is low, yield is high, be easy to the preparation method of industrialized N-methylmorpholine.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of N-methylmorpholine: using fixed-bed reactor (atmospheric fixed bed reactor) as reaction unit, loaded catalyst is set in fixed-bed reactor (atmospheric fixed bed reactor); With the mixture of morpholine and methyl-formiate for raw material, the mol ratio of described methyl-formiate and morpholine is 0.5 ~ 0.9:1; By the fixed-bed reactor containing loaded catalyst after material gasification, under hydro condition, carry out amination reaction; Reaction pressure is 0.12 ~ 0.19MPa, temperature is 120 ~ 130 DEG C; The volume space velocity V of reaction is 0.05 ~ 0.3g/h/mL; After above-mentioned reaction terminates, after condensation, collect reactant, then after dehydration, rectifying, obtain N-methylmorpholine;
The preparation process of described loaded catalyst is as follows: utilize metal salt solution and carrier to make loaded catalyst, in described loaded catalyst, metal accounts for 22% ~ 32% of gross weight, and metal-salt is mantoquita and zinc salt.
Remarks illustrate: volume space velocity V refers to: by the quality of the reactant of per volume of catalyst in the unit time; That is, the raw material after gasification carries out amination reaction with the air speed of 0.05 ~ 0.3g/h/mL loaded catalyst and loaded catalyst.
Improvement as the preparation method of N-methylmorpholine of the present invention: described carrier is through the pretreated gama-alumina of phosphoric acid; Copper account for gross weight 15% ~ 25%, zinc accounts for 7% ~ 17% of gross weight.
Further improvement as the preparation method of N-methylmorpholine of the present invention: the preparation method of described loaded catalyst is: metal salt solution and carrier are flooded through (successively through 2 times) successively, after dry, calcination steps loaded catalyst.
The preparation process of loaded catalyst of the present invention specifically comprises:
1), by the nitrate of each component be proportionally dissolved in distilled water, be settled to desired concn, with the ratio of 1.2mL solution/1g carrier, by the pretreated γ of phosphoric acid-Al 2o 3be immersed in the solution configured, flood 36 hours; Filter, obtain filtrate and catalyzer;
2), by step 1) catalyzer of gained under agitation in 60 DEG C of dryings 2 hours, then put into retort furnace with 90 DEG C, 140 DEG C, 280 DEG C each roastings 3 hours, then Temperature fall (to room temperature);
3), by step 2) catalyzer of gained puts into step 1) the filtrate dipping of gained 24 hours, filter;
4), by step 3) filter the catalyzer of gained under agitation in 60 DEG C of dryings 2 hours, then put into retort furnace with 150 DEG C of roastings 2 hours, with 400 ~ 500 DEG C of roastings 4 hours; Then Temperature fall (to room temperature), obtains required loaded catalyst.
In invention, the preparation method through the pretreated gama-alumina of phosphoric acid is:
By commercially available γ-Al 2o 3be the H of 5% by volumetric concentration 3pO 4solution is in 40 ~ 50 DEG C of immersion treatment 30-60 minute, then after leaching drying, 400 DEG C of roastings 2 hours, 750 DEG C of roastings were after 6 hours, for subsequent use.
According to the method described above, the loaded catalyst that obtained following 3 kinds of loaded catalysts (as shown in table 1) are preferentially selected for the present invention.
Table 1
The synthetic method of N-methylmorpholine of the present invention, for the method 6 of informing in " background technology ", has following advantage:
Although 1, methyl-formiate is suitable with methanol prices, is that methylating reagent can significantly reduce consumption with methyl-formiate, there is larger cost advantage.
2, zinc salt has larger price advantage relative to nickel salt, significantly can reduce production cost.
3, in the present invention, reaction pressure and temperature of reaction are all remarkable in method 6, therefore, require low, not only can reduce costs, also have the technical superiority being beneficial to commercial scale production reaction unit.
In sum, the preparation method of N-methylmorpholine of the present invention, reaction conditions is gentle, and production cost is low, and equipment serialization is good, easy handling and realize industrialization.With the N-methylmorpholine that preparation method of the present invention produces, product purity is higher, and can reach the yield of 90%.
Embodiment
The preparation method of embodiment 1, a kind of N-methylmorpholine, carries out following steps successively:
1), loaded catalyst is prepared:
A), by commercially available γ-Al 2o 3be the H of 5% by volumetric concentration 3pO 4solution was in 40 ~ 50 DEG C of immersion treatment 60 minutes, then after leaching drying, 400 DEG C of roastings 2 hours, 750 DEG C of roastings, after 6 hours, obtained the γ-Al after process 2o 3, for subsequent use.
B), in 28.1g cupric nitrate and 13.3g zinc nitrate solid (not containing crystal water), add distilled water be settled to 50mL, after cupric nitrate and zinc nitrate dissolve, obtain 50mL metal salt solution for subsequent use.
With 1.2mL metal salt solution/1.0g γ-Al 2o 3the ratio of carrier, by the γ-Al after above-mentioned process 2o 3be immersed in the solution configured, flood after 36 hours; Filter, obtain filtrate and catalyzer.
C), by the catalyzer of gained after above-mentioned filtration under agitation in 60 DEG C of dryings 2 hours, retort furnace is put into 90 DEG C, 140 DEG C, 280 DEG C each roastings 3 hours, then Temperature fall.
D), by the catalyzer of above-mentioned Temperature fall gained immerse step b) gained filtrate in 24 hours, refilter.
E), by steps d) catalyzer of gained under agitation in 60 DEG C of dryings 2 hours, then in retort furnace successively: 150 DEG C of roastings 2 hours, 400 ~ 500 DEG C of roastings 4 hours; Then Temperature fall, obtains required particulate supported type catalyzer, is wherein about 15% (W/W) containing Cu, is about 7% (W/W) containing Zn, and the form being oxide compound exists.
2), head tank is placed in as raw material using after the methyl-formiate of mol ratio 0.5:1 and morpholine mixing, the above-mentioned catalyzer of 80mL is loaded in the tubular fixed-bed reactor of capacity 100mL, heater voltage is regulated to make temperature of reaction control at 130 DEG C after facing hydrogen activation, by in head tank mixture vaporization (140 DEG C) after through reactor head, jointly enter reactor with hydrogen to carry out facing hydrogen amination, hydrogen pressure is regulated to make reactor pressure remain on 0.19Mpa, raw material enters catalyst bed reaction with the air speed of 0.2g/h/mL catalyzer, product is collected in liquid form after condensation, carry out after collecting the product of q.s analyzing and being separated.
3) sample, getting collection carries out gas chromatographic analysis, product in 500mL flask, add water-retaining agent dewater after atmospheric distillation, the cut collecting 115 ~ 116 DEG C is product, continuing to collect 128 DEG C of cuts is raw material, and after adding methyl-formiate, circulation is reacted again.
The product obtained carries out gas chromatographic analysis, and content is 98%, and after a collection of feedstock circulation utilizes, product yield (relative to the molar yield of morpholine, lower same) can reach 90%.
The preparation method of embodiment 2, a kind of N-methylmorpholine:
In step 2) in, the mol ratio of morpholine and methyl-formiate changes 1:0.9 into, and temperature of reaction controls at 120 DEG C, and regulate hydrogen pressure to make reactor pressure remain on 0.15Mpa, raw material enters catalyst bed reaction with the air speed of 0.3g/h/mL catalyzer.All the other are all equal to embodiment 1.
It is 90% that the product of gained carries out gas chromatographic analysis content, and product yield is 95%.
The preparation method of embodiment 3, a kind of N-methylmorpholine:
In step 2) in, the mol ratio of morpholine and methyl-formiate makes 1:0.7 into, and temperature of reaction controls at 125 DEG C, and regulate hydrogen pressure to make reactor pressure remain on 0.12MPa, raw material enters catalyst bed reaction with the air speed of 0.1g/h/mL catalyzer.All the other are all equal to embodiment 1.
It is 97% that products obtained therefrom carries out gas chromatographic analysis content, and product yield is 93%.
The preparation method of embodiment 4, a kind of N-methylmorpholine, carries out following steps successively:
1), loaded catalyst is prepared:
A), by commercially available γ-Al 2o 3be the H of 5% by volumetric concentration 3pO 4solution was in 40 ~ 50 DEG C of immersion treatment 30 minutes, then after leaching drying, 400 DEG C of roastings 2 hours, 750 DEG C of roastings, after 6 hours, obtained the γ-Al after process 2o 3, for subsequent use.
B), in 47.4g cupric nitrate and 13.2g zinc nitrate solid (not containing crystal water), add distilled water be settled to 50mL, obtained 50mL metal salt solution is for subsequent use.With 1.2mL metal salt solution/1.0g γ-Al 2o 3the ratio of carrier, by the γ-Al after above-mentioned process 2o 3be immersed in the solution configured, flood after 36 hours; Filter, obtain filtrate and catalyzer.
C), by the catalyzer of gained after above-mentioned filtration under agitation in 60 DEG C of dryings 2 hours, retort furnace is put into 90 DEG C, 140 DEG C, 280 DEG C each roastings 3 hours, then Temperature fall.
D), by the catalyzer of above-mentioned Temperature fall gained immerse step b) gained filtrate in 24 hours, refilter.
E), by steps d) catalyzer of gained under agitation in 60 DEG C of dryings 2 hours, then in retort furnace successively: 150 DEG C of roastings 2 hours, 400 ~ 500 DEG C of roastings 4 hours; Then Temperature fall, obtains required particulate supported type catalyzer, is wherein about 25% (W/W) containing Cu, is about 7% (W/W) containing Zn, and the form being oxide compound exists.
All the other steps are with embodiment 1.
It is 95% that the product of gained carries out gas chromatographic analysis content, and product yield is 93%.
The preparation method of embodiment 5, a kind of N-methylmorpholine, carries out following steps successively:
1), loaded catalyst is prepared:
A), by commercially available γ-Al 2o 3be the H of 5% by volumetric concentration 3pO 4solution was in 40 ~ 50 DEG C of immersion treatment 45 minutes, then after leaching drying, 400 DEG C of roastings 2 hours, 750 DEG C of roastings, after 6 hours, obtained the γ-Al after process 2o 3, for subsequent use.
B), in 28.2g cupric nitrate and 32.2 zinc nitrate solids (not containing crystal water), add distilled water be settled to 50mL, obtained 50mL metal salt solution is for subsequent use.With 1.2mL metal salt solution/1.0g γ-Al 2o 3the ratio of carrier, by the γ-Al after above-mentioned process 2o 3be immersed in the solution configured, flood after 36 hours; Filter, obtain filtrate and catalyzer.
C), by the catalyzer of gained after above-mentioned filtration under agitation in 60 DEG C of dryings 2 hours, retort furnace is put into 90 DEG C, 140 DEG C, 280 DEG C each roastings 3 hours, then Temperature fall.
D), by the catalyzer of above-mentioned Temperature fall gained immerse step b) gained filtrate in 24 hours, refilter.
E), by steps d) catalyzer of gained under agitation in 60 DEG C of dryings 2 hours, then in retort furnace successively: 150 DEG C of roastings 2 hours, 400 ~ 500 DEG C of roastings 4 hours; Then Temperature fall, obtains required particulate supported type catalyzer, is wherein about 15% (W/W) containing Cu, is about 17% (W/W) containing Zn, and the form being oxide compound exists.
All the other steps are with embodiment 1.
It is 95% that the product of gained carries out gas chromatographic analysis content, and product yield is 95%.
Comparative example 1-1, the loaded catalyst in embodiment 5 to be modified as follows:
Make raw material " zinc nitrate " into nickelous nitrate, and change consumption accordingly, thus make in the catalyzer of final gained, be wherein about 15% (W/W) containing Cu, be about 17% (W/W) containing Ni, the form being oxide compound exists.
Gained catalyzer is called catalyst A, and substitute the catalyzer of former embodiment 5 with the catalyst A of above-mentioned gained, all the other contents are with embodiment 5.
It is 85% that the product of gained carries out gas chromatographic analysis content, and product yield is 54%.
Comparative example 1-2, the loaded catalyst in embodiment 5 to be modified as follows:
Make raw material " zinc nitrate " into Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and change consumption accordingly, thus make in the catalyzer of final gained, be wherein about 15% (W/W) containing Cu, be about 17% (W/W) containing Co, the form being oxide compound exists.
Gained catalyzer is called catalyst B, and substitute the catalyzer of former embodiment 5 with the catalyst B of above-mentioned gained, all the other contents are with embodiment 5.
It is 83% that the product of gained carries out gas chromatographic analysis content, and product yield is 48%.
Comparative example 2, the loaded catalyst in embodiment 5 to be modified as follows:
Raw material cupric nitrate is done corresponding change to the consumption of zinc nitrate, thus makes in the catalyzer of final gained, be about 30% (W/W) containing Cu, be about 17% (W/W) containing Zn, the form being oxide compound exists.
Gained catalyzer is called catalyzer C, and substitute the catalyzer of former embodiment 5 with the catalyzer C of above-mentioned gained, all the other contents are with embodiment 5.
It is 93% that the product of gained carries out gas chromatographic analysis content, and product yield is 88%.
Comparative example 3, make " methyl alcohol: morpholine " in the embodiment 3 of documents 6 (that is, patent 200710069194.0) into 0.9:1 by 1:1; Make temperature of reaction into 130 DEG C by 200 DEG C, make pressure into 0.19Mpa by 0.2MPa, volume space velocity V0.1g/h/mL is constant, and all the other are with the embodiment 3 of documents 6.Ultimate yield is only 74%.
Finally, note also that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had, the distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should protection scope of the present invention be thought.

Claims (3)

  1. The preparation method of 1.N-methylmorpholine, is characterized in that: using fixed-bed reactor as reaction unit, in fixed-bed reactor, arrange loaded catalyst; With the mixture of morpholine and methyl-formiate for raw material, the mol ratio of described methyl-formiate and morpholine is 0.5 ~ 0.9:1; By the fixed-bed reactor containing loaded catalyst after material gasification, under hydro condition, carry out amination reaction; Reaction pressure is 0.12 ~ 0.19MPa, temperature is 120 ~ 130 DEG C; The volume space velocity V of reaction is 0.05 ~ 0.3g/h/mL; After above-mentioned reaction terminates, after condensation, collect reactant, then after dehydration, rectifying, obtain N-methylmorpholine;
    The preparation process of described loaded catalyst is as follows: utilize metal salt solution and carrier to make loaded catalyst, in described loaded catalyst, metal accounts for 22% ~ 32% of gross weight, and metal-salt is mantoquita and zinc salt; Described carrier is through the pretreated gama-alumina of phosphoric acid; Copper account for gross weight 15% ~ 25%, zinc accounts for 7% ~ 17% of gross weight.
  2. 2. the preparation method of N-methylmorpholine according to claim 1, is characterized in that: the preparation method of described loaded catalyst is: by metal salt solution and carrier successively through flooding, after dry, calcination steps, obtain loaded catalyst.
  3. 3. the preparation method of N-methylmorpholine according to claim 1 and 2, is characterized in that: described loaded catalyst be following any one:
    Copper account for gross weight 15%, zinc accounts for 7% of gross weight;
    Copper account for gross weight 25%, zinc accounts for 7% of gross weight;
    Copper account for gross weight 15%, zinc accounts for 17% of gross weight.
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CN110773175A (en) * 2019-11-07 2020-02-11 江苏美思德化学股份有限公司 Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine
CN112851598B (en) * 2021-01-27 2024-01-23 安徽昊源化工集团有限公司 Continuous production method for synthesizing N-methylmorpholine by using morpholine and methanol as catalyst

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Publication number Priority date Publication date Assignee Title
CN101066955A (en) * 2007-06-05 2007-11-07 浙江大学 Synthesis proces sof N-methyl morpholine

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