Solvent-free continuous production method of N-methylpyrrolidine
阅读说明：本技术 一种n-甲基吡咯烷无溶剂连续生产方法 (Solvent-free continuous production method of N-methylpyrrolidine ) 是由 刘庆彬 高鹏翔 刘亚欢 于 2021-10-08 设计创作，主要内容包括：本发明公开了一种N-甲基吡咯烷的无溶剂连续生产方法,包括以下步骤：以N-甲基吡咯烷酮为原料,在H-(2)氛围下,以双金属M-(1)-M-(2)-载体催化剂为催化剂,N-甲基吡咯烷酮与氢气发生氢化反应,得到目标产物N-甲基吡咯烷。本发明生产方法不需要使用任何溶剂,条件温和,副产物只有对环境友好的水,绿色环保,催化剂催化效率高,N-甲基吡咯烷综合收率大于95%,适合工业化生产。(The invention discloses a solvent-free continuous production method of N-methylpyrrolidine, which comprises the following steps: using N-methyl pyrrolidone as raw material in H 2 In an atmosphere, with a bimetal M 1 ‑M 2 The supported catalyst is a catalyst, and the N-methylpyrrolidone and hydrogen are subjected to hydrogenation reaction to obtain the target product N-methylpyrrolidine. The production method provided by the invention does not need any solvent, is mild in condition, has a byproduct only containing water which is environment-friendly, is green and environment-friendly, has high catalytic efficiency of the catalyst, has a comprehensive yield of N-methylpyrrolidine of more than 95%, and is suitable for industrial production.)
1. A solvent-free continuous production method of N-methylpyrrolidine is characterized by comprising the following steps: using N-methyl pyrrolidone as raw material, adding M bimetal1-M2Under the action of a carrier catalyst, carrying out hydrogenation reaction on N-methylpyrrolidone and hydrogen, and purifying to obtain high-purity N-methylpyrrolidone; the catalyst is a bimetal supported catalyst, the reaction temperature is 100-300 ℃, the reaction pressure is 10-100 Bar, and the mass airspeed is 0.1-3 h-1The hydrogen flow rate is 0 to 500 sccm.
2. The method of claim 1Method for producing said bimetal M1-M2Supported catalyst, M1The component is one of Pd, Rh, Ir, Pt and Ru, M2The component is one of V, W, Mo and Re, and the carrier is one or two of inorganic oxide and apatite; in the catalyst M1In an amount of 5 to 20 wt%, M2The mass content of (A) is 0-20 wt%.
3. The production method according to claim 2, characterized in that the inorganic oxide is one of silica, alumina, titania; the apatite is one of fluorapatite, chlorapatite and hydroxyapatite.
4. Production method according to claim 1 or 2, characterized in that said bimetal M1-M2The preparation method of the supported catalyst comprises the following steps:
(1) mixing component M1Salts and component M2The salt compound is dispersed in a solvent to form a solution in which the component M1And component M2The concentration of (A) is 0.001-1 mol/L;
(2) adding a carrier into the solution obtained in the step (1) and uniformly mixing;
(3) stirring the mixture obtained in the step (2) at 0-50 ℃ for 4 h, and removing the solvent to obtain a solid;
(4) drying the solid obtained in the step (3) at 60-120 ℃ for 4-12 h;
(5) and (5) roasting the solid obtained in the step (4) in a muffle furnace at 300-600 ℃ for 2-5 h.
5. The method according to claim 4, characterized in that said component M1And M2The salt compound is one or two of nitrate, acetate, chloride, acetylacetone compound and ammonium salt.
6. The method according to claim 4, wherein the solvent is one or two of water, ethanol, methanol, acetone, and toluene.
7. The production process according to claim 1, characterized in that the hydrogenation of N-methylpyrrolidone is carried out in a fixed bed reactor.
Technical Field
The invention belongs to the technical field of preparation of fine chemical products, and particularly relates to a solvent-free continuous production method of N-methylpyrrolidine.
Background
N-methyl pyrrolidine is an organic amine widely used in medicine and chemical industry, is mainly used for preparing broad-spectrum antibiotics cefepime and tolmetin, and can also be used as a dye, a stabilizer and a repellentA preservative, and the like. N-methylpyrrolidine (NMPD), molecular formula: c5H11N, molecular weight 85.15, boiling point 80.8 ℃, relative density (water is 1) 0.8190 (25 ℃), newly distilled N-methylpyrrolidine is colorless transparent liquid, the easily-received light effect is changed into yellow liquid in the storage process, the liquid is brown for a long time, and NMPD is an organic base, is heterocyclic tertiary amine, has the property of common amine and has certain potential toxicity to human bodies. The structural formula of the N-methyl pyrrolidine is as follows:
many documents describe continuous production of N-methylpyrrolidine, with different catalysts and process conditions, and different activities and selectivities. A Pt/Re/TiO alloy is described in The literature (Jacorien Coetzee, Haresh G. Manyar, Christopher Hardacre, David J. Cole-Hamilton, The First contacts Flow Hydrogenation of Amides to Amines, ChemCatchem, 2013, 5, 2843-one 2847)2A hydrogenation reaction process of N-methyl pyrrolidone by using normal hexane as a solvent as a catalyst. Dissolving N-methylpyrrolidone in N-hexane, wherein the concentration of the N-methylpyrrolidone is 0.67M, the solution enters a reaction tube at the speed of 0.06 mL/min, the reaction temperature is 120 ℃, the hydrogen pressure is 20Bar (the hydrogen flow is 190 mL/min when the pressure is increased), the reaction is carried out for 5 hours, and the yield of the N-methylpyrrolidone is 100%. The liquid flow is increased to 0.12 mL/min in the 6 th hour, and the yield of the N-methyl pyrrolidine is still kept at 100 percent. The method has high yield of the N-methylpyrrolidine, but needs a large amount of solvent, has low reaction efficiency, and needs to remove the solvent after the reaction is finished, so that the cost is increased, and the method is not beneficial to realizing industrial production. The document (Yan Guangzhou, Song nationality, Wubin, Xiaoqiang, Liujun, Yan principle, Zhou Shufei, a production method of N-methylpyrrolidine, CN110240577A, 2019-09-17) synthesizes the catalyst containing Cu and Zn elements, and adopts a tubular reactor, uses N-methylpyrrolidone and hydrogen as raw materials, and uses N-methyldiethanolamine as solvent to continuously produce N-methylpyrrolidine. The mol ratio of N-methyl pyrrolidone to N-methyldiethanolamine to hydrogen is 1:0.5:4, the reaction temperature is 120-180 ℃, and the reaction is carried outThe pressure is 0.1-0.2 MPa, and the liquid hourly space velocity is 0.6-1.2 h-1The conversion rate of N-methyl pyrrolidone can reach 99.2%, and the selectivity is 99%. However, the method needs a large amount of N-methyldiethanolamine as a solvent, N-methylpyrrolidine needs to be rectified and purified after the reaction is finished, and the solvent is used and recycled, so that the industrial cost of the method is increased, and environmental pollution is caused. The literature (Wangyiyou, fixed bed one-step method for continuously synthesizing N-methyl tetrahydropyrrole and process improvement, chemical intermediate 2011, 6, 39-45) uses tetrahydrofuran as a raw material and carries ƴ -Al2O3The method comprises the steps of synthesizing N-methylpyrrolidine through a dehydration reaction with methylamine under catalysis, wherein a horizontal fixed bed reactor is adopted in the route, the inner diameter D of the fixed bed is 1000mm, the net bed height is 3000 mm, the loading amount of a catalyst is 2500Kg, the loading height of a bed layer is 1050 mm, and the tube array diameter is 76 mm, under optimized process conditions, the temperature T of the bed layer is = 330 ℃, the pressure gradient P = 0.2-0.4-0.01 Mpa, N (monomethylamine)/N (tetrahydrofuran) = 1.30, the feeding speed is 550 ml/min, the content of crude product N-methylpyrrolidine can reach 97%, after the crude product is purified by an azeotropic distillation technology, the purity of the product is more than or equal to 99.5%, and the moisture content of the product is more than or equal to 99.5%<0.1 percent. However, in the process conditions, the reaction temperature is high, the loading amount of the catalyst is large, the prices of tetrahydrofuran and methylamine are high, and excessive methylamine needs to be treated after the reaction is finished.
Disclosure of Invention
The invention aims to provide a solvent-free continuous production method of N-methylpyrrolidine, which realizes the solvent-free continuous production of the N-methylpyrrolidine, solves the problems of environmental pollution and high cost caused by using a solvent and difficulty in subsequent treatment of a crude product, improves the production efficiency of the N-methylpyrrolidine, reduces the production cost of the N-methylpyrrolidine, and has the characteristics of environmental friendliness and no pollution because a by-product of the process only contains water.
In order to achieve the purpose, the invention adopts the following technical scheme:
a solvent-free continuous production method of N-methylpyrrolidine comprises the following steps: using N-methyl pyrrolidone as raw material, adding M bimetal1-M2Under the action of a carrier catalyst, carrying out hydrogenation reaction on N-methylpyrrolidone and hydrogen, and purifying to obtain high-purity N-methylpyrrolidone; what is needed isThe reaction temperature is 100-400 ℃, the reaction pressure is 10-100 Bar, and the mass airspeed is 0.1-3 h-1The hydrogen flow rate is 0 to 500 sccm.
Bimetal M in the invention1-M2The supported catalyst is a bimetallic supported catalyst, wherein M is1The component is one of Pd, Rh, Ir, Pt and Ru, M2The component is one of V, W, Mo and Re, and the carrier is one or two of inorganic oxide and apatite; in the catalyst M1In an amount of 5 to 20 wt%, M2The mass content of (A) is 0-20 wt%.
More preferably, the inorganic oxide is one of silicon dioxide, aluminum oxide and titanium dioxide; the apatite is one of fluorapatite, chlorapatite and hydroxyapatite.
The preparation method of the catalyst comprises the following steps:
(1) mixing component M1Salts and component M2The salt compound is dispersed in a solvent to form a solution in which the component M1And component M2The concentration of (A) is 0.001-1 mol/L;
(2) adding a carrier into the solution obtained in the step (1) and uniformly mixing;
(3) stirring the mixture obtained in the step (2) at 0-50 ℃ for 4 h, and removing the solvent to obtain a solid;
(4) drying the solid obtained in the step (3) at 60-120 ℃ for 4-12 h;
(5) and (5) roasting the solid obtained in the step (4) in a muffle furnace at 300-600 ℃ for 2-5 h to obtain a catalyst particle finished product.
Preparation of the catalyst, component M1And M2The salt compound is one or two of nitrate, acetate, chloride, acetylacetone compound or ammonium salt.
According to the preparation method of the catalyst, the solvent is one or two of water, ethanol, methanol, acetone and toluene.
The production method of the invention has the following reaction general formula:
the hydrogenation reaction of the N-methyl pyrrolidone is carried out in a fixed bed reactor, and the fixed bed reactor comprises a liquid advection pump, a gas mass flow meter, a preheater, a reaction tube, a condensation chamber and a product collecting device.
The prepared catalyst is loaded into a reaction tube, N-methyl pyrrolidone enters a fixed bed reactor through a liquid advection pump, and H2The N-methyl pyrrolidone and the hydrogen enter a fixed bed reactor through a gas mass flow meter, the N-methyl pyrrolidone and the hydrogen enter a preheater together for heating, the N-methyl pyrrolidone and the H enter a reaction tube after the N-methyl pyrrolidone and the hydrogen reach a set temperature, and the N-methyl pyrrolidone and the H are reacted under the action of a catalyst2Carrying out hydrogenation reaction to generate N-methylpyrrolidine and water, condensing in a condensing chamber, collecting, extracting, purifying the collected crude product by rectification, extracting the N-methylpyrrolidine from the top of a rectifying tower, wherein the purity of the N-methylpyrrolidine is more than or equal to 99.9%, extracting the unreacted N-methylpyrrolidone from the tower bottom, and reacting in a fixed bed reactor again.
The invention has the following beneficial effects:
1. under the action of a catalyst, N-methylpyrrolidone directly undergoes hydrogenation reaction with hydrogen in the absence of a solvent to generate N-methylpyrrolidone. The reaction is applied to the continuous production of a fixed bed, the production efficiency of the N-methylpyrrolidine is improved, and the method is more suitable for industrial production.
2. Under the action of a catalyst, N-methylpyrrolidone and hydrogen are subjected to hydrogenation reaction to produce N-methylpyrrolidone, and the process conditions are as follows: the reaction temperature is 100-500 ℃, the reaction pressure is 10-100 Bar, and the mass airspeed is 0.1-3 h-1Hydrogen flow of 0-500 sccm, primary conversion rate of N-methylpyrrolidone>80% primary yield of N-methylpyrrolidine>85 percent. After the purification by rectification, the purity of the N-methylpyrrolidine is more than or equal to 99.9 percent, the unreacted N-methylpyrrolidone is extracted from the tower bottom and enters the fixed bed reactor again for reaction, and N-Comprehensive conversion rate of methyl pyrrolidone>98 percent of N-methyl pyrrolidine comprehensive yield>95 percent. The reaction can generate the N-methyl pyrrolidine under lower temperature and pressure under the action of the catalyst, the process condition is mild, the environment is not polluted, the raw materials are cheap and easy to obtain, the catalyst processing capacity is strong, the obtained crude product can be rectified to obtain a high-purity product, and the method has an industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
The reference numerals in the figures illustrate:
BPR, a back pressure valve C, a condensing chamber GB, a pressure reducing valve HE, a heating device LP, a constant flow pump MFC, a mass flow meter P, a pressure sensor PH, a preheater R, a reaction tube SV, a spiral valve T and a thermocouple.
Detailed Description
The following examples serve to illustrate the invention.
Example 1 catalyst preparation
393.3 mg of platinum acetylacetonate, 297.4 mg of ammonium metatungstate and 300 mL of acetone are weighed and put in a round bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, 2.5g of silicon dioxide is weighed and added in the solution, water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110-DEG oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h to obtain a catalyst Pt/W/SiO2Labeled as catalyst # 1.
Example 2 catalyst preparation
393.3 mg of platinum acetylacetonate, 297.4 mg of ammonium metatungstate and 300 mL of acetone are weighed and put in a round bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, 2.5g of titanium dioxide is weighed and added in the solution, water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110-DEG oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h to obtain a catalyst Pt/W/TiO2And labeled as catalyst # 2.
Example 3 catalyst preparation
393.3 mg of platinum acetylacetonate, 297.4 mg of ammonium metatungstate and 300 mL of acetone are weighed and put in a round bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110 ℃ oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h to obtain a catalyst Pt/W/HAP which is marked as a No. 3 catalyst.
Example 4 catalyst preparation
393.3 mg of acetylacetone platinum, 618.0 mg of ammonium molybdate tetrahydrate and 300 mL of acetone are weighed and put in a round bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, then 2.5g of hydroxyapatite is weighed and added in the solution, the water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110 ℃ oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h, so that a catalyst Pt/Mo/HAP is obtained, and the catalyst is marked as a No. 4 catalyst.
Example 5 catalyst preparation
393.3 mg of platinum acetylacetonate, 132.5 mg of vanadyl acetylacetonate and 300 mL of acetone are weighed and put in a round bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110 ℃ oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h to obtain a catalyst Pt/V/HAP, which is marked as a No. 5 catalyst.
Example 6 catalyst preparation
393.3 mg of platinum acetylacetonate, 134.1 mg of ammonium perrhenate and 300 mL of acetone are weighed and put in a round-bottom flask, water bath stirring is carried out at 40 ℃ for 30 min, 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring is carried out at 40 ℃ for a period of time, the solution is put in a 110 ℃ oven to be dried for 10 h, the solution is ground and put in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h, so that a catalyst Pt/Re/HAP is obtained, and the catalyst is marked as a No. 6 catalyst.
Example 7 catalyst preparation
Weighing 449.0 mg of palladium acetate, 618.0 mg of ammonium molybdate tetrahydrate and 300 mL of acetone into a round-bottom flask, stirring in a water bath at 40 ℃ for 30 min, weighing 2.5g of hydroxyapatite, adding into the solution, stirring in a water bath at 40 ℃ for a period of time, putting into a 110 ℃ oven for drying for 10 h, grinding, putting into a muffle furnace, and calcining at 300 ℃ for 3 h to obtain a catalyst Pd/Mo/HAP, wherein the mark is a No. 7 catalyst.
Example 8 catalyst preparation
526.6 mg of rhodium trichloride trihydrate, 618.0 mg of ammonium molybdate tetrahydrate and 300 mL of acetone are weighed and placed in a round bottom flask, water bath stirring at 40 ℃ is carried out for 30 min, 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring at 40 ℃ is carried out for a period of time, the solution is placed in a 110 ℃ oven to be dried for 10 h, the solution is ground and placed in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h, so that a catalyst Rh/Mo/HAP is obtained, and the catalyst Rh/Mo/HAP is marked as an 8# catalyst.
Example 9 catalyst preparation
316.7 mg of iridium chloride hydrate, 618.0 mg of ammonium molybdate tetrahydrate and 300 mL of acetone are weighed and placed in a round bottom flask, water bath stirring at 40 ℃ is carried out for 30 min, then 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring at 40 ℃ is carried out for a period of time, the solution is placed in a 110 ℃ oven to be dried for 10 h, the solution is ground and placed in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h, so that a catalyst Ir/Mo/HAP is obtained, and the catalyst is marked as a No. 9 catalyst.
Example 10 catalyst preparation
450.9 mg of ruthenium trichloride trihydrate, 618.0 mg of ammonium molybdate tetrahydrate and 300 mL of acetone are weighed and placed in a round bottom flask, water bath stirring at 40 ℃ is carried out for 30 min, 2.5g of hydroxyapatite is weighed and added into the solution, the water bath stirring at 40 ℃ is carried out for a period of time, the solution is placed in a 110 ℃ oven to be dried for 10 h, the solution is ground and placed in a muffle furnace, and the solution is calcined at 300 ℃ for 3 h, so that a catalyst Ru/Mo/HAP is obtained, and the catalyst is marked as a No. 10 catalyst.
EXAMPLE 11N-methylpyrrolidine production
Adding 3.0 g of a No. 1 catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>60%。
EXAMPLE 12N-methylpyrrolidine production
Adding 3.0 g of 2# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>75%。
EXAMPLE 13N-methylpyrrolidine production
Adding 3.0 g of 3# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of N-methyl pyrrolidone is 220 ℃, and the reaction is carried outThe pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>80%。
EXAMPLE 14N-methylpyrrolidine production
Adding 3.0 g of 4# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 120 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
Example 15N-methylpyrrolidine production
Adding 3.0 g of 5# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 16N-methylpyrrolidine production
Adding 3.0 g of No. 6 catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
Example 17N-Methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 18N-methylpyrrolidine production
3.0 g of 8# catalyst is added into a fixed bed reactor, the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, the mass space velocity is 1.2 h-1, and the yield of the N-methyl pyrrolidine is more than 85%.
EXAMPLE 19N-methylpyrrolidine production
3.0 g of No. 9 catalyst is added into a fixed bed reactor, the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 20N-methylpyrrolidine production
Adding 3.0 g of 10# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>80%。
Example 21N-Methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 230 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 22N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 250 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>80%。
Example 23N-Methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 50Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 24N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 70 Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 25N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 200 sccm, and the mass space velocity is 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 26N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of N-methyl pyrrolidone is 220 ℃, and the reaction pressure isForce 20Bar, hydrogen flow rate 300 sccm, mass space velocity 1.2 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 27N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 1.5 h-1Yield of N-methylpyrrolidine>70%。
EXAMPLE 28N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 0.9 h-1Yield of N-methylpyrrolidine>85%。
Example 29 production of N-methylpyrrolidine
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 0.4 h-1Yield of N-methylpyrrolidine>85%。
EXAMPLE 30N-methylpyrrolidine production
Adding 3.0 g of 7# catalyst into a fixed bed reactor, wherein the hydrogenation reaction temperature of the N-methyl pyrrolidone is 220 ℃, the reaction pressure is 20Bar, the hydrogen flow rate is 100 sccm, and the mass space velocity is 0.2 h-1Yield of N-methylpyrrolidine>85%。