CN116496196A - Preparation method of N-vinyl pyrrolidone - Google Patents

Preparation method of N-vinyl pyrrolidone Download PDF

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CN116496196A
CN116496196A CN202310396426.2A CN202310396426A CN116496196A CN 116496196 A CN116496196 A CN 116496196A CN 202310396426 A CN202310396426 A CN 202310396426A CN 116496196 A CN116496196 A CN 116496196A
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metal salt
earth metal
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water
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CN116496196B (en
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王宇
陈占
熊俊超
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SHANGHAI YUKING WATER SOLUBLE MATERIAL Tech CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

The invention belongs to the technical field of chemical synthesis, and discloses a preparation method of N-vinyl pyrrolidone. Mixing alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water, adding white carbon black for impregnation, and drying to obtain mixed powder; mixing the mixed powder, kaolin and water, extruding to form strips, drying and calcining to obtain a catalyst; filling the catalyst in a fixed bed reactor, then introducing mixed gas of N-hydroxyethyl pyrrolidone steam, diluent gas and alkaline gas, and carrying out dehydration reaction in the fixed bed reactor to obtain N-vinyl pyrrolidone. The method has high safety and low energy consumption in the synthesis process, and can continuously produce NVP. The addition of the alkaline gas to the mixed gas can reduce carbon deposition on the surface of the dehydration catalyst and improve the selectivity of the dehydration catalyst to NVP. The dehydration catalyst prepared by the invention also has higher NVP selectivity and conversion rate.

Description

Preparation method of N-vinyl pyrrolidone
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of N-vinyl pyrrolidone.
Background
N-vinyl pyrrolidone (NVP) is an important chemical raw material, can be mixed with water, ethanol, diethyl ether and other organic solvents, and is applied to the fields of radiation medical treatment, wooden floor industry, paper or paperboard industry, packaging material, silk screen printing ink industry and the like to improve the physical properties of products. Generally, NVP is commonly used as a monomer for synthesizing polyvinylpyrrolidone (PVP) in industry, and as the application range of PVP is widened, the demand thereof is gradually increased, and the purity and the synthesis cost of the raw material NVP for synthesizing PVP become key points for restricting the wide application of PVP.
At present, methods for synthesizing NVP mainly comprise an acetylene method and a dehydration method. The acetylene method takes 2-pyrrolidone and acetylene as raw materials to carry out the vinylation reaction under the action of an alkali metal catalyst, however, the method has the advantages that the solubility of the acetylene in a liquid phase raw material is low, the reaction rate is generally improved by pressurizing, the acetylene also has the problem of easy explosion under high pressure, the requirement on reaction equipment is high, the potential safety hazard is high, and the environment-friendly and safe production concept advocated at present can not be satisfied. On the basis, in order to solve the safety problem of acetylene, researchers develop a dehydration method, N-hydroxyethyl pyrrolidone is used as a raw material, NVP is prepared through dehydration reaction, the reaction process of the method is safe, but the problem that a dehydration catalyst is easy to deactivate restricts the wide application of the process.
Therefore, how to provide a process for synthesizing NVP in a green, environment-friendly, safe and efficient way has great significance for low-cost synthesis of NVP and wide application of PVP.
Disclosure of Invention
The invention aims to provide a preparation method of N-vinyl pyrrolidone, which solves the problems of low safety, environmental protection and low yield of the existing NVP synthesis process.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Mixing alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water to obtain a precursor solution; dipping white carbon black into a precursor solution, and then drying to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water, extruding and molding to obtain a catalyst precursor; drying and calcining the catalyst precursor to obtain a catalyst;
(3) Filling the catalyst in a fixed bed reactor, then introducing mixed gas of N-hydroxyethyl pyrrolidone steam, diluent gas and alkaline gas, and carrying out dehydration reaction in the fixed bed reactor to obtain N-vinyl pyrrolidone.
Preferably, in the above-mentioned preparation method of an N-vinyl pyrrolidone, the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt in the step (1) are independently nitrate or acetate; the rare earth metal in the rare earth metal salt is one or more of yttrium, lanthanum, cerium, neodymium, samarium and holmium.
Preferably, in the above-mentioned method for preparing N-vinyl pyrrolidone, the molar volume ratio of the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water in the step (1) is 1-2 mmol:0.5 to 1.5mmol:0.1 to 0.2mmol:0.1 to 0.7mmol: 10-20 mL; the molar mass ratio of the alkali metal salt to the white carbon black is 1-2 mmol:0.1 g to 5g.
Preferably, in the above-mentioned preparation method of N-vinyl pyrrolidone, the molar mass ratio of the alkali metal salt in the step (1) to the kaolin in the step (2) is 1 to 2mmol: 1-10 g; the mass volume ratio of the kaolin to the water in the step (2) is 1g: 50-300 mL.
Preferably, in the above method for preparing N-vinyl pyrrolidone, the drying temperature in the step (2) is 100-160 ℃; the drying time is 6-12 h.
Preferably, in the above method for preparing N-vinyl pyrrolidone, the calcining temperature in the step (2) is 400-530 ℃; the calcination time is 3-6 h.
Preferably, in the above method for preparing N-vinyl pyrrolidone, the molar ratio of N-hydroxyethyl pyrrolidone vapor, diluent gas, and alkaline gas in the step (3) is 1 to 7: 4-10: 5 to 20.
Preferably, in the above method for preparing N-vinyl pyrrolidone, the temperature of the dehydration reaction in the step (3) is 320-380 ℃; the pressure of the dehydration reaction is 0.01-0.1 MPa; the gas phase space velocity of the dehydration reaction is 50 to 1000 hours -1 。
Preferably, in the above method for preparing N-vinyl pyrrolidone, the diluent gas in the step (3) is nitrogen, argon or helium; the alkaline gas is ammonia.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses the N-hydroxyethyl pyrrolidone (NHP) dehydration method to prepare the NVP, compared with an acetylene method, the method avoids the problem of easy explosion of acetylene in a high-pressure environment, has high safety and low energy consumption in the synthesis process, and can continuously produce the NVP. In the synthesis process, alkaline gas is added into the mixed gas to reduce carbon deposition on the surface of the dehydration catalyst and improve the selectivity of the dehydration catalyst to NVP. In addition, the dehydration catalyst used in the invention also contains alkali metal oxide, alkaline earth metal oxide, rare earth metal oxide and zirconium oxide, and the activity of the dehydration catalyst is ensured by supplementing the loss of the alkali metal oxide in the reaction process through the alkaline earth metal oxide, and meanwhile, the yield of NVP can be improved by the rare earth metal oxide and the zirconium oxide, so that the dehydration catalyst has higher NVP selectivity and conversion rate.
Detailed Description
The invention provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Mixing alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water to obtain a precursor solution; dipping white carbon black into a precursor solution, and then drying to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water, extruding and molding to obtain a catalyst precursor; drying and calcining the catalyst precursor to obtain a catalyst;
(3) Filling the catalyst in a fixed bed reactor, then introducing mixed gas of N-hydroxyethyl pyrrolidone steam, diluent gas and alkaline gas, and carrying out dehydration reaction in the fixed bed reactor to obtain N-vinyl pyrrolidone.
In the present invention, the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt in the step (1) are independently preferably nitrate or acetate, and more preferably nitrate; the rare earth metal in the rare earth metal salt is preferably one or more of yttrium, lanthanum, cerium, neodymium, samarium and holmium, more preferably one or more of yttrium, lanthanum, neodymium and holmium, and still more preferably yttrium.
In the present invention, the alkali metal in the alkali metal salt in the step (1) is preferably one of sodium, potassium, rubidium and cesium, more preferably one of sodium, rubidium and cesium, and still more preferably cesium.
In the present invention, the alkaline earth metal in the alkaline earth metal salt in the step (1) is preferably one of magnesium, calcium, strontium and barium, more preferably one of magnesium, calcium and strontium, and still more preferably calcium.
In the present invention, the molar volume ratio of the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water in the step (1) is preferably 1 to 2mmol:0.5 to 1.5mmol:0.1 to 0.2mmol:0.1 to 0.7mmol:10 to 20mL, more preferably 1.2 to 1.9mmol:0.7 to 1.2mmol:0.13 to 0.18mmol:0.2 to 0.5mmol:12 to 16mL, more preferably 1.6mmol:0.9mmol:0.17mmol:0.4mmol:14mL; the molar mass ratio of the alkali metal salt to the white carbon black is preferably 1 to 2mmol:0.1 to 5g, more preferably 1.1 to 1.7mmol:0.9 to 3g, more preferably 1.3mmol:2g.
In the present invention, the silica white in the step (1) is preferably precipitated silica or fumed silica, and more preferably precipitated silica.
In the present invention, the time for the impregnation in the step (1) is preferably 30 to 120 minutes, more preferably 42 to 107 minutes, and still more preferably 85 minutes.
In the present invention, the drying temperature in the step (1) is preferably 100 to 120 ℃, more preferably 103 to 116 ℃, and still more preferably 112 ℃; the drying time is preferably 5 to 20 hours, more preferably 8 to 16 hours, and still more preferably 12 hours.
In the present invention, the molar mass ratio of the alkali metal salt in the step (1) to the kaolin in the step (2) is preferably 1 to 2mmol:1 to 10g, more preferably 1.2 to 1.7mmol:3 to 7g, more preferably 1.4mmol:4g; the mass volume ratio of the kaolin to the water in the step (2) is preferably 1g:50 to 300mL, more preferably 1g:90 to 240mL, more preferably 1g:180mL.
In the present invention, the drying temperature in the step (2) is preferably 100 to 160 ℃, more preferably 110 to 150 ℃, and still more preferably 130 ℃; the drying time is preferably 6 to 12 hours, more preferably 7 to 11 hours, and still more preferably 8 hours.
In the present invention, the temperature of calcination in the step (2) is preferably 400 to 530 ℃, more preferably 420 to 510 ℃, and even more preferably 490 ℃; the calcination time is preferably 3 to 6 hours, more preferably 4 to 6 hours, and still more preferably 5 hours; the temperature rise rate of the calcination is preferably 1 to 5℃per minute, more preferably 2 to 4℃per minute, and still more preferably 4℃per minute.
In the present invention, the molar ratio of the N-hydroxyethyl pyrrolidone vapor, the diluent gas, and the alkaline gas in the step (3) is preferably 1 to 7: 4-10: 5 to 20, more preferably 3 to 6:5 to 9:7 to 17, more preferably 4:8:12.
in the present invention, the temperature of the dehydration reaction in the step (3) is preferably 320 to 380 ℃, more preferably 340 to 370 ℃, and even more preferably 360 ℃; the dehydration reaction pressure is preferably 0.01 to 0.1MPa, more preferably 0.04 to 0.09MPa, still more preferably 0.06MPa; the gas phase space velocity of the dehydration reaction is preferably 50 to 1000 hours -1 More preferably 120 to 980h -1 More preferably 400h -1 。
In the present invention, the diluent gas in the step (3) is preferably nitrogen, argon or helium, more preferably argon or helium, and still more preferably argon; the alkaline gas is preferably ammonia.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Potassium nitrate, calcium nitrate, lanthanum nitrate, zirconium nitrate and water are mixed according to a molar volume ratio of 1mmol:0.8mmol:0.17mmol:0.3mmol: mixing 20mL to obtain a precursor solution; dipping fumed silica (the molar mass ratio of potassium nitrate to fumed silica is 1mmol:2 g) in a precursor solution for 50min, and then drying at 120 ℃ for 12h to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water (the molar mass ratio of potassium nitrate to kaolin is 1mmol to 6g, and the mass volume ratio of kaolin to water is 1g to 200 mL), extruding and molding to obtain a catalyst precursor; drying the catalyst precursor at 140 ℃ for 8 hours, and then heating the catalyst precursor from room temperature to 490 ℃ at 3 ℃/min for 5 hours to obtain a catalyst;
(3) Filling a catalyst into a fixed bed reactor, then introducing a mixed gas of N-hydroxyethyl pyrrolidone steam, nitrogen and ammonia (the molar ratio of the N-hydroxyethyl pyrrolidone steam to the nitrogen to the ammonia is 5:7:8), and placing the mixed gas into the fixed bed reactor at the temperature of 350 ℃, the pressure of 0.01MPa and the gas phase space velocity of 900h -1 And (3) carrying out dehydration reaction for 12 hours under the condition of (2) to obtain the N-vinyl pyrrolidone.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 91.3%, the selectivity of NVP was 96.9%, and the yield of NVP was 88.5%.
Example 2
The embodiment provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Cesium nitrate, calcium nitrate, lanthanum nitrate, zirconium nitrate and water are mixed according to a molar volume ratio of 1mmol:0.5mmol:0.1mmol:0.2mmol: mixing 20mL to obtain a precursor solution; dipping fumed silica (the molar mass ratio of cesium nitrate to the fumed silica is 1mmol:3 g) in a precursor solution for 30min, and then drying at 100 ℃ for 10h to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water (the molar mass ratio of cesium nitrate to kaolin is 2mmol to 2g, and the mass volume ratio of kaolin to water is 1g to 100 mL), extruding and molding to obtain a catalyst precursor; drying the catalyst precursor at 120 ℃ for 12 hours, and then heating the catalyst precursor from room temperature to 450 ℃ at 2 ℃/min for 4 hours to obtain a catalyst;
(3) Filling a catalyst into a fixed bed reactor, then introducing a mixed gas of N-hydroxyethyl pyrrolidone steam, nitrogen and ammonia (the molar ratio of the N-hydroxyethyl pyrrolidone steam to the nitrogen to the ammonia is 2:6:12), and placing the mixed gas into the fixed bed reactor at the temperature of 320 ℃ under the pressure of 0.03MPa and the gas phase space velocity of 600h -1 And (3) carrying out dehydration reaction for 12 hours under the condition of (2) to obtain the N-vinyl pyrrolidone.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 89.8%, the selectivity of NVP was 96.7%, and the yield of NVP was 86.8%.
Example 3
The embodiment provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Sodium acetate, calcium nitrate, cerium nitrate, zirconium nitrate and water are mixed according to a molar volume ratio of 2mmol:1.5mmol:0.15mmol:0.6mmol:15mL of the mixture is mixed to obtain a precursor solution; dipping fumed silica (molar mass ratio of sodium acetate to fumed silica is 1.3mmol:4.5 g) in a precursor solution for 40min, and then drying at 120 ℃ for 8h to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water (the molar mass ratio of sodium acetate to kaolin is 1.6mmol to 7g, and the mass volume ratio of kaolin to water is 1g to 200 mL), extruding and molding to obtain a catalyst precursor; drying the catalyst precursor at 150 ℃ for 8 hours, and then heating from room temperature to 510 ℃ at 5 ℃/min for 4 hours to obtain a catalyst;
(3) Filling a catalyst into a fixed bed reactor, then introducing a mixed gas of N-hydroxyethyl pyrrolidone steam, nitrogen and ammonia (the molar ratio of the N-hydroxyethyl pyrrolidone steam to the nitrogen to the ammonia is 6:8:15), and placing the mixed gas into the fixed bed reactor at the temperature of 340 ℃, the pressure of 0.01MPa and the gas phase space velocity of 800h -1 And (3) carrying out dehydration reaction for 12 hours under the condition of (2) to obtain the N-vinyl pyrrolidone.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 92.2%, the selectivity of NVP was 98.6%, and the yield of NVP was 90.9%.
Example 4
The embodiment provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Sodium acetate, calcium nitrate, lanthanum nitrate, zirconium nitrate and water are mixed according to a molar volume ratio of 1.2mmol:1.1mmol:0.1mmol:0.3mmol: mixing 20mL to obtain a precursor solution; dipping fumed silica (the molar mass ratio of sodium acetate to the fumed silica is 2mmol:5 g) in a precursor solution for 80min, and then drying at 120 ℃ for 6h to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water (the molar mass ratio of sodium acetate to kaolin is 1.8mmol to 5g, and the mass volume ratio of kaolin to water is 1g to 200 mL), extruding and molding to obtain a catalyst precursor; drying the catalyst precursor at 160 ℃ for 10 hours, and then heating from room temperature to 450 ℃ at 5 ℃/min for calcination for 5 hours to obtain a catalyst;
(3) Filling a catalyst into a fixed bed reactor, then introducing a mixed gas of N-hydroxyethyl pyrrolidone steam, nitrogen and ammonia (the molar ratio of the N-hydroxyethyl pyrrolidone steam to the nitrogen to the ammonia is 3:10:8), and placing the mixed gas into the fixed bed reactor at the temperature of 330 ℃, the pressure of 0.01MPa and the gas phase space velocity of 800h -1 And (3) carrying out dehydration reaction for 12 hours under the condition of (2) to obtain the N-vinyl pyrrolidone.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 91.8%, the selectivity of NVP was 97.3%, and the yield of NVP was 89.4%.
Example 5
The embodiment provides a preparation method of N-vinyl pyrrolidone, which comprises the following steps:
(1) Potassium nitrate, strontium nitrate, cerium nitrate, zirconium nitrate and water are mixed according to a molar volume ratio of 1.1mmol:1.5mmol:0.2mmol:0.6mmol:18mL of the mixture is mixed to obtain a precursor solution; dipping fumed silica (the molar mass ratio of potassium nitrate to the fumed silica is 1.2mmol:2.7 g) in a precursor solution for 100min, and then drying at 120 ℃ for 10h to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water (the molar mass ratio of potassium nitrate to kaolin is 1.3mmol:7g, and the mass volume ratio of kaolin to water is 1g:150 mL), extruding and molding to obtain a catalyst precursor; drying the catalyst precursor at 150 ℃ for 8 hours, and then heating from room temperature to 460 ℃ at 4 ℃/min for calcination for 4.5 hours to obtain a catalyst;
(3) Filling a catalyst into a fixed bed reactor, then introducing a mixed gas of N-hydroxyethyl pyrrolidone steam, nitrogen and ammonia (the molar ratio of the N-hydroxyethyl pyrrolidone steam to the nitrogen to the ammonia is 6:6:13), and placing the mixed gas into the fixed bed reactor at the temperature of 350 ℃, the pressure of 0.02MPa and the gas phase space velocity of 1000h -1 And (3) carrying out dehydration reaction for 12 hours under the condition of (2) to obtain the N-vinyl pyrrolidone.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 90.4%, the selectivity of NVP was 98.2%, and the yield of NVP was 88.8%.
Comparative example 1
This comparative example provides a process for the preparation of N-vinylpyrrolidone, see in particular example 1, with the difference that in step (1) no calcium nitrate is contained.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, and the conversion of NHP was 86.4%, the selectivity of NVP was 91.7% and the yield of NVP was 79.3%.
Comparative example 2
This comparative example provides a process for the preparation of N-vinylpyrrolidone, with particular reference to example 1, except that in step (1) calcium nitrate and zirconium nitrate are absent.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, and the conversion of NHP was 84.1%, the selectivity of NVP was 86.8% and the yield of NVP was 73%.
Comparative example 3
This comparative example provides a process for the preparation of N-vinylpyrrolidone, with particular reference to example 1, with the difference that the mixture in step (3) does not contain ammonia.
The N-vinylpyrrolidone thus obtained was analyzed by gas chromatography, the conversion of NHP was 82.7%, the selectivity of NVP was 85.5% and the yield of NVP was 70.8%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. A method for preparing N-vinyl pyrrolidone, which is characterized by comprising the following steps:
(1) Mixing alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water to obtain a precursor solution; dipping white carbon black into a precursor solution, and then drying to obtain mixed powder;
(2) Mixing the mixed powder, kaolin and water, extruding and molding to obtain a catalyst precursor; drying and calcining the catalyst precursor to obtain a catalyst;
(3) Filling the catalyst in a fixed bed reactor, then introducing mixed gas of N-hydroxyethyl pyrrolidone steam, diluent gas and alkaline gas, and carrying out dehydration reaction in the fixed bed reactor to obtain N-vinyl pyrrolidone.
2. The method for producing N-vinylpyrrolidone according to claim 1, wherein the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt in the step (1) is independently nitrate or acetate; the rare earth metal in the rare earth metal salt is one or more of yttrium, lanthanum, cerium, neodymium, samarium and holmium.
3. The method for preparing N-vinylpyrrolidone according to claim 2, wherein the molar volume ratio of the alkali metal salt, alkaline earth metal salt, rare earth metal salt, zirconium salt and water in the step (1) is 1 to 2mmol:0.5 to 1.5mmol:0.1 to 0.2mmol:0.1 to 0.7mmol: 10-20 mL; the molar mass ratio of the alkali metal salt to the white carbon black is 1-2 mmol:0.1 g to 5g.
4. A process for the preparation of N-vinylpyrrolidone according to claim 1 or 3, wherein the molar mass ratio of alkali metal salt in step (1) to kaolin in step (2) is from 1 to 2mmol: 1-10 g; the mass volume ratio of the kaolin to the water in the step (2) is 1g: 50-300 mL.
5. The method for producing N-vinylpyrrolidone according to claim 4, wherein the drying temperature in the step (2) is 100 to 160 ℃; the drying time is 6-12 h.
6. The method for producing N-vinylpyrrolidone according to claim 1, 2 or 5, wherein the temperature of calcination in step (2) is 400 to 530 ℃; the calcination time is 3-6 h.
7. The method for producing N-vinylpyrrolidone according to claim 6, wherein the molar ratio of N-hydroxyethylpyrrolidone vapor, diluent gas, and alkaline gas in step (3) is 1 to 7: 4-10: 5 to 20.
8. The method for producing N-vinylpyrrolidone according to claim 1 or 7, wherein the dehydration reaction in the step (3) is carried out at a temperature of 320 to 380 ℃; the pressure of the dehydration reaction is 0.01-0.1 MPa; the gas phase space velocity of the dehydration reaction is 50 to 1000 hours -1 。
9. The method for producing N-vinylpyrrolidone according to claim 7, wherein the diluent gas in the step (3) is nitrogen, argon or helium; the alkaline gas is ammonia.
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