CN110590634A - Production method of 1-acetyl-2-pyrrolidone - Google Patents

Production method of 1-acetyl-2-pyrrolidone Download PDF

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Publication number
CN110590634A
CN110590634A CN201910932794.8A CN201910932794A CN110590634A CN 110590634 A CN110590634 A CN 110590634A CN 201910932794 A CN201910932794 A CN 201910932794A CN 110590634 A CN110590634 A CN 110590634A
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reactor
acetyl
catalyst
temperature
pyrrolidone
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吴彦彬
闫广学
宋国全
吴正岭
肖强
杨理
梁斌
周淑飞
李清霞
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MAIQI CHEMICAL Co Ltd
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MAIQI CHEMICAL Co Ltd
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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

Abstract

The invention discloses a production method of 1-acetyl-2-pyrrolidone, which comprises the following steps: the method comprises the steps of taking 1, 3-propylene glycol, ammonia water, methyl acetate and methyl formate as raw materials, carrying out amination, addition and cyclization reactions in a tubular fixed bed reactor under the action of a copper-based catalyst to obtain a 1-acetyl-2-pyrrolidone crude product, and further purifying to obtain the compound. The catalyst has high catalytic activity, mild reaction conditions and simple and convenient process operation, the yield of the obtained product is more than or equal to 98.4 percent, the selectivity is more than or equal to 99.0 percent, the purity is more than or equal to 99.9 percent, the water content is less than or equal to 40ppm, and the ammonia content is less than or equal to 2ppm, thereby meeting the requirements of fields such as downstream medicine, fine chemical intermediates and the like.

Description

Production method of 1-acetyl-2-pyrrolidone
Technical Field
The invention belongs to the field of production of fine chemical products, and particularly relates to a production method of 1-acetyl-2-pyrrolidone.
Background
1-acetyl-2-pyrrolidone with a molecular weight of 127.4 and a density of 1.15g/cm3The product has a boiling point of 231 ℃, has special smell and higher biological activity, can be used for synthesizing acetylpyrrolidine, acetylpyrrole and the like, is an important starting material in organic synthesis, and is widely applied to the fields of pharmaceutical and chemical industry, fine chemical industry, pesticide and chemical industry, spices and cosmetic additives.
In the prior art, catalysts used for synthesizing pyrrolidone from gamma-butyrolactone amine are generally solid superacid, heteropolyacid or modified molecular sieve, and the like, for example: zhang Shide et al (see literature: Zhang Shide, Lin Feng Zhen et al, Synthesis of 1-cyclohexyl-2-pyrrolidone [ J ]]Fine chemical, 2005, volume 22, phase 9) describes the preparation of N-cyclohexylpyrrolidone from γ -butyrolactone and cyclohexylamine under the action of a phosphoric acid catalyst; zhang Ling Yu et al (see: Zhang Ling Yu, Wang Yun Chuan, etc.), research on the catalytic synthesis of N-phenylpyrrolidone by solid superacid [ J]2017 Vol 39, No. 4) describes the use of fixed bed technology with SO4 2-/MxOyReacting 1, 4-butyrolactone and aniline to synthesize N-phenylpyrrolidone by using a solid super acidic catalyst at the reaction temperature of 300 ℃; deposition to light, etc. (see literature: deposition to light, Zhouyou et al, ZSM-5 molecular sieve gas phase catalytic synthesis of N-methylpyrrolidone [ J)]The petroleum refining and chemical industry, 2013, 44(1), 51 ~ 55) introduced the preparation of N-methylpyrrolidone by using a catalyst compounded by rare earth elements and a ZSM molecular sieve, and the rare earth elements and the ZSM molecular sieveThe prepared composite catalyst is developed by matching with specific raw materials, wherein the raw materials are monomethylamine aqueous solution, the test of preparing N-acetylpyrrolidone by using acetamide and gamma-butyrolactone is duplicated according to the method described in the specification, and the yield is only 36.1%.
The Chinese patent application with publication number CN107474003A discloses a method for continuously synthesizing N-methyl pyrrolidone and N-ethyl pyrrolidone, which is carried out in a microreactor, wherein a gamma-butyrolactone solution and a corresponding alkylamine solution continuously pass through the microreactor to synthesize the N-methyl pyrrolidone and the N-ethyl pyrrolidone, the microreactor comprises a reaction section and a reaction inhibition section, a reaction mixture stays for 1-30 min in the reaction section, the gamma-butyrolactone solution and the corresponding alkylamine solution both use ethylene glycol as solvents, the reaction temperature is 240-300 ℃, the reaction pressure is 1.7-5.2 MPa, the reaction inhibition section temperature is 0-5 ℃, and the yield is more than 90%. The method has the characteristics of short reaction time and high yield, but the requirement on equipment is high when the temperature of 240 ℃ materials is reduced to 0-5 ℃ in a short time, and meanwhile, the micro-reaction is used as a new technology, so that the investment cost is relatively high, the effect is unstable, and the yield is up to over 90% and is only 43.7% at least in the embodiment.
Chinese patent with publication number CN105237456B discloses a method for producing pyrrolidone products, which introduces that 1, 4-butanediol is used as raw material to directly produce pyrrolidone through one-step reaction, and 1, 4-butanediol is converted into pyrrolidone series products in a reaction unit through dehydrogenation-amination reaction by adopting a sectional type reactor and a combined catalyst, wherein the method is completed in two reactors in one reaction unit, the first-stage reaction mainly adopts 1, 4-butanediol dehydrogenation to produce gamma-butyrolactone, the second-stage reaction mainly adopts gamma-butyrolactone amine to compound into pyrrolidone, the reaction temperature of the first-stage reactor is 190-260 ℃, the reaction pressure is 0.5-8.0 MPa, the reaction temperature of the second-stage reactor is 230-290 ℃, and the reaction pressure is 5-15.0 MPa, so a buffer tank is arranged between the first-stage reactor and the second-stage reactor, The booster pump, the filter and the heater are complex in structure, the operation process is complicated, and the safety factor of workers in the operation process is reduced.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for producing 1-acetyl-2-pyrrolidone.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
the method comprises the steps of taking 1, 3-propylene glycol, ammonia water, methyl acetate and methyl formate as raw materials, carrying out amination, addition and cyclization reactions on the 1, 3-propylene glycol, the ammonia, the methyl acetate and the methyl formate in a tubular fixed bed reactor under the action of a copper-based catalyst to generate a 1-acetyl-2-pyrrolidone crude product, and further purifying to obtain a target product 1-acetyl-2-pyrrolidone.
Preferably, the production method comprises the following steps: 1, 3-propylene glycol, ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section for preheating, then sent into a tubular fixed bed reactor, and reacted under the action of a catalyst; and (3) after heat exchange and condensation of the mixed material discharged from the reactor, sending the mixed material into a constant pressure tank, releasing the pressure of the mixed material through a flow-limiting orifice plate, then sending the mixed material into an intermediate storage tank to release the surplus ammonia, returning the collected surplus ammonia into the reaction system again, and separating and purifying the crude product in the intermediate storage tank through a three-stage continuous tower to obtain the product.
Preferably, the molar ratio of the 1, 3-propylene glycol to ammonia in ammonia water to methyl acetate to methyl formate is 1 (1.0 ~ 1.2.2) to (1.0 ~ 1.2.2) to (1.0 ~ 1.2.2), the reaction temperature is 220 ~ 260 ℃, the reaction pressure is 0.5 ~ 5MPa, and the liquid hourly space velocity is 1 ~ 10h-1。
Preferably, the tubular fixed bed reactor consists of an upper section and a lower section, the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is an auto-thermal countercurrent tubular type, the diameter of the upper section reaction tube is 100 ~ 150mm, and the diameter of the lower section reaction tube is 50 ~ 80 mm.
Preferably, the preparation method of the copper-based catalyst comprises the following steps:
(1) mixing copper nitrate, bismuth nitrate anddissolving silver nitrate in deionized water to obtain 1 ~ 2mol/L solution A, adding polyethylene glycol with polymerization degree of 2000 ~ 10000, stirring, reacting at 70 ~ 90 deg.C for 5 ~ 10h to obtain mixed solution B containing Cu/Bi/Ag, and adding nanoscale Fe2O3And TiO2Dispersing the nano-scale carrier in deionized water by using ultrasonic waves to prepare a solution C, dispersing the nano-scale carrier in the deionized water by using ultrasonic waves to prepare a solution D, cocurrently flowing and mixing the solution B, C, D, stirring for 12 ~ 24h, dropwise adding a precipitator to control the end point pH to be 6.5 ~ 7.0.0, standing, filtering, washing, drying a filter cake in vacuum, and roasting for 8 ~ 12h at 500 ~ 600 ℃ to obtain a catalyst;
(2) filling the catalyst obtained in the step (1) into a tubular fixed bed reactor, replacing the reactor with nitrogen, reducing the catalyst with hydrogen, keeping the pressure less than or equal to 0.5MPa, gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient, cooling to 230 ℃ after the reduction of the catalyst is finished, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
Preferably, the carrier in the step (1) is molecular sieve ZSM-5 and/or HZSM-5.
Preferably, the precipitating agent in the step (1) is (NH)4)2CO3、Na2CO3、NaOH、NaHCO3And a urea solution.
Preferably, the chemical components and weight percentages of the catalyst in the step (1) are CuO 25 ~ 35%, TiO 252 5~10%、Fe2O3 3~5%、Ag2O 0.5~2%、Bi2O3 3 ~ 5%, the balance being carrier.
Preferably, the temperature gradient in step (2) is as follows: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
Preferably, the hydrogen concentration of the reactor is less than or equal to 2% at room temperature of ~ 150 ℃, less than or equal to 5% at 150 ~ 200 ℃, and 100% at 220 ℃ after reduction is finished.
The general formula of the reaction process of the invention is as follows:
the invention has the following positive beneficial effects:
1. CuO and Fe in the catalyst of the invention2O3And TiO2A special crystal interface is formed between the iron oxide and the titanium oxide, electrons of the iron oxide and the titanium oxide migrate to the conduction band of the copper oxide through a space charge region of the heterojunction after migrating to the conduction band, the electrons reduce the copper oxide into low-valence copper, the catalytic activity of the low-valence copper is higher, the migration of the electrons is also beneficial to the chemical adsorption and dissociation of C-H bonds between the metal and a carrier interface, the C-O-H, C-H bonds of intermediate product molecules adsorbed on the surface of the catalyst are broken, and H is generated+And combines with the hydroxyl on the surface of the catalyst to generate water. The active components of the elements Bi and Ti can well inhibit atom migration in crystal lattices in the activation process of the catalyst, prevent crystal grains from becoming large and accumulating, enable the active components of the catalyst to be uniformly loaded on a carrier, maintain sufficient pore channels, have good dispersion and prevent agglomeration. Silver in the same main group with copper has the characteristics of mildness and alkalescence, and the addition of Ag element enables Bi to be added2O3And TiO2The crystal in the crystal lattice is refined, the crystallinity of the catalyst is reduced, and the diffraction peak intensity of the catalyst is gradually weakened along with the increase of the doping concentration of Ag, so that the catalyst keeps higher activity. The copper-based catalyst has the advantages that the active ingredients of the copper-based catalyst are synergistic, the yield of the crude 1-acetyl-2-pyrrolidone obtained by the tubular fixed bed reactor is more than or equal to 98.4%, the selectivity is more than or equal to 99.0%, the catalytic activity is high, the reaction time is short, the higher yield is realized without prolonging the reaction time, a plurality of reaction sites in a reaction substrate are inhibited, the side reaction is less, the price is low, the cost is easy to obtain, the toxicity is low, the environment is protected, the efficiency is high, the stability is high, and the large.
2. In the reduction process of the copper-based catalyst, once the reaction starts, water vapor does not play a role in retardation, the concentration of hydrogen and copper oxide mainly influences the reduction speed, the reduction reaction of a precursor of the copper-based catalyst is a strong heat release reaction, temperature runaway is easily generated, the temperature is increased to be not beneficial to proper reduction, the reduction temperature is too high, the crystallite size is increased, the specific surface area is reduced, but the reduction speed of the catalyst can be increased, the reaction time is shortened, the temperature is too low, the reduction speed is slow, the production period of the reactor is influenced, the time of exposing the reduced catalyst in water vapor is prolonged, the repeated opportunity of oxidation-reduction is increased, the activity of the catalyst is reduced, the temperature rise speed, the temperature gradient and the hydrogen concentration are strictly controlled, the temperature rise speed, the temperature gradient and the hydrogen concentration are qualified at the beginning, hydrogen is gradually introduced until the reduction is completed, the temperature rises from room temperature to 120 ℃ gradually, the temperature is kept for 5h, the temperature rises to 150 ℃ again within 5h, the temperature is kept for 5h, the temperature is kept at the temperature to 200 ℃ again, the temperature is kept for 5h, the temperature is kept for 10 ℃ to 280 ℃ again, the temperature to the temperature of 200 ℃ for the temperature, the temperature of 200 ℃ of the temperature of the reactor is kept for 5h, the temperature of the reactor again, the temperature of the reactor is kept for the reactor again, the temperature of the reactor is kept for 5h, the temperature of the reactor is kept for the temperature of the reactor for 5h, the reactor for.
3. According to the invention, the starting raw materials of methyl acetate and methyl formate are reacted, the by-products in the reaction process are methanol and water, the difference between the boiling point of an azeotrope formed by the methanol and the water and the boiling point of the methyl acetate is large, the separation and purification are easy, and the burden on the environment is small; the methanol generated in the reaction process can play a role of a solvent, and the methanol can also take away a part of ammonia in the separation process, so that the content of ammonia in the wastewater is reduced, and the difficulty of subsequent wastewater treatment is reduced.
4. The fixed bed reactor consists of an upper section and a lower section, and the reactorThe upper section of the reactor is a laminar flow tube type, the lower section of the reactor is a self-heating counter-flow type, the upper section of the reactor is a high-pressure tube with a jacket, heat is provided by heat conducting oil, the diameter of the upper section reaction tube is 100 ~ mm, meanwhile, the upper section reaction tube of the reactor is also the jacket of the lower section material of the reactor (the lower section reaction tube is positioned in the upper section reaction tube and is the lower section, see the specific figure 2), the temperature required by the lower section reaction of the reactor is provided by the material coming out of the upper section of the reactor, the self-heating is realized to provide energy required by the reaction, the diameter of the lower section reaction tube is 50 ~ mm, the change of the upper and lower tube diameters improves the flow speed of the lower section, the heat transfer coefficient is increased, the heat exchange area is enlarged, the reaction heat is timely removed, the side reaction in the reaction process is reduced, and the selectivity of the product is improved-1The reaction condition is mild, and the process operation is simple and convenient.
The material from the upper section of the reactor passes through the lower section reaction tube and the upper section reaction tube, the material enters a catalyst bed layer from the bottom of the lower section reaction tube of the reactor in a countercurrent manner, the material flows out of the reactor after reaction, the mixed material from the reactor is sent into a constant pressure tank after heat exchange and condensation, the pressure of the whole system is stabilized by the constant pressure tank, the mixed material enters an intermediate storage tank after being decompressed by a flow-limiting pore plate, the surplus ammonia is discharged, the collected surplus ammonia returns to the reactor again, and the crude product in the intermediate storage tank is separated and purified by a three-stage continuous tower to obtain the product, wherein the purity of the obtained product is more than or equal to 99.9 percent, the water content is less than or equal to 40ppm, the ammonia content is less than or equal to 2ppm, and the product hardly contains free amine.
Drawings
FIG. 1 is a schematic of the temperature gradient of the present invention;
FIG. 2 is a schematic view of the structure of a tubular fixed-bed reactor according to the present invention.
Detailed Description
The invention will be further illustrated with reference to some specific embodiments.
Example 1
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare 1.5mol/L solution A, then adding polyethylene glycol with the polymerization degree of 2000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting for 6 hours at 80 ℃ to obtain mixed solution B containing Cu/Bi/Ag; mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 24h, dropwise adding a precipitator to control the end point pH to be 6.8, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 500 ℃ for 10h to obtain a catalyst;
(2) the catalyst obtained in the step (1) is filled in a tubular fixed bed reactor in advance, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, continuous sampling and analysis are carried out in the reduction process, and H supplement is determined2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 200 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the substrate 1, 3-propylene glycol stays in the tubular fixed bed reactor for 1h, 3000ml of substrate 1, 3-propylene glycol is treated in unit time, the yield of a target product is 98.9%, and the selectivity is 99%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is 99.91%, the water content is 38ppm, and the ammonia content is 2 ppm.
The carrier in the step (1) is ZSM-5.
The precipitator in the step (1) is (NH)4)2CO3And (3) solution.
The catalyst (before reduction) in the step (1) comprises the following chemical components in percentage by weight: 35% of CuO and TiO2 6%、Fe2O3 5%、Ag2O 1%、Bi2O3 3 percent of carrier and the balance.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 2% at room temperature ~ 150 ℃ and 4% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mol ratio of the 1, 3-propylene glycol to ammonia in the ammonia water, the methyl acetate to the methyl formate in the step (3) is 1:1.1: 1.1: 1, the reaction temperature is 220 ℃, the reaction pressure is 0.5MPa, and the liquid hourly space velocity is 1h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 100mm, and the diameter of the lower section reaction tube is 50 mm.
Example 2
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare a 1mol/L solution A, then adding polyethylene glycol with the polymerization degree of 8000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting for 5 hours at the temperature of 90 ℃ to obtain a mixed solution B containing Cu/Bi/Ag;mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 20h, dropwise adding a precipitator to control the end point pH to be 6.7, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 550 ℃ for 8h to obtain a catalyst;
(2) the catalyst obtained in the step (1) is filled in a tubular fixed bed reactor in advance, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, continuous sampling and analysis are carried out in the reduction process, and H supplement is determined2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 160 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the residence time of the substrate 1, 3-propylene glycol in the tubular fixed bed reactor is 0.5h, 6000ml of substrate 1, 3-propylene glycol is treated in unit time, the yield of a target product is 98.5%, and the selectivity is 99.1%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is 99.9%, the water content is 35ppm, and the ammonia content is 1 ppm.
The carrier in the step (1) is HZSM-5.
The precipitant in the step (1) is Na with concentration2CO3And (3) solution.
The catalyst in the step (1) comprises the following chemical components in percentage by weight before reduction: 25% of CuO and TiO2 10%、Fe2O34%、Ag2O 0.5%、Bi2O3 4 percent, and the balance being carrier.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 2% at room temperature ~ 150 ℃ and 4.5% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mol ratio of the 1, 3-propylene glycol to ammonia in the ammonia water, the methyl acetate to the methyl formate in the step (3) is 1:1.0: 1.0: 1.2, the reaction temperature is 240 ℃, the reaction pressure is 1MPa, and the liquid hourly space velocity is 2h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 120mm, and the diameter of the lower section reaction tube is 60 mm.
Example 3
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare 1.5mol/L solution A, then adding polyethylene glycol with the polymerization degree of 6000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting for 8 hours at 80 ℃ to obtain mixed solution B containing Cu/Bi/Ag; mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 24h, dropwise adding a precipitator to control the end point pH to be 7.0, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 550 ℃ for 10h to obtain a catalyst;
(2) subjecting the product obtained in step (1)The catalyst is pre-filled in a tubular fixed bed reactor, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, and continuous sampling analysis is carried out in the reduction process to determine the supplement H2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 180 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the residence time of a substrate 1, 3-propylene glycol in the tubular fixed bed reactor is 0.1h, 30000ml of the substrate 1, 3-propylene glycol is treated in unit time, the yield of a target product is 98.4%, and the selectivity is 99.1%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is 99.93%, the water content is 25ppm, and the ammonia content is 1.3 ppm.
The carrier in the step (1) is molecular sieves ZSM-5 and HZSM-5, and the weight ratio of the molecular sieves ZSM-5 to the HZSM-5 is 1:1.
the precipitator in the step (1) is (NH)4)2CO3And (3) solution.
The catalyst in the step (1) comprises the following chemical components in percentage by weight before reduction: 30% of CuO and TiO2 8%、Fe2O3 4%、Ag2O 1%、Bi2O3 5 percent, and the balance being carrier.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 2% at room temperature ~ 150 ℃ and 5% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mol ratio of the 1, 3-propylene glycol to ammonia in the ammonia water, the methyl acetate to the methyl formate in the step (3) is 1:1.0: 1.2: 1.1, the reaction temperature is 230 ℃, the reaction pressure is 1MPa, and the liquid hourly space velocity is 10h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 120mm, and the diameter of the lower section reaction tube is 60 mm.
Example 4
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare a solution A with the concentration of 1.6mol/L, adding polyethylene glycol with the polymerization degree of 10000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting at 70 ℃ for 10 hours to obtain a mixed solution B containing Cu/Bi/Ag; mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 15h, dropwise adding a precipitator to control the end point pH to be 6.9, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 600 ℃ for 10h to obtain a catalyst;
(2) the catalyst obtained in the step (1) is filled in a tubular fixed bed reactor in advance, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, continuous sampling and analysis are carried out in the reduction process, and H supplement is determined2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole system with nitrogen,maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 180 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the residence time of a substrate 1, 3-propylene glycol in the tubular fixed bed reactor is 0.125h, 24000ml of the substrate 1, 3-propylene glycol is treated in unit time, the yield is 99.0%, and the selectivity is 99.5%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is 99.95%, the water content is 10ppm, and the ammonia content is 1 ppm.
The carrier in the step (1) is molecular sieve HZSM-5.
The precipitator in the step (1) is NaOH solution.
The catalyst in the step (1) comprises the following chemical components in percentage by weight before reduction: 32% of CuO and TiO2 5%、Fe2O33%、Ag2O 1.5%、Bi2O3 4 percent, and the balance being carrier.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 2% at room temperature ~ 150 ℃ and 5% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mole of the 1, 3-propanediol, the ammonia in the ammonia water, the methyl acetate and the methyl formate in the step (3)The molar ratio is 1:1.0: 1.1: 1.1, the reaction temperature is 250 ℃, the reaction pressure is 2MPa, and the liquid hourly space velocity is 8h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 140mm, and the diameter of the lower section reaction tube is 60 mm.
Aiming at example 4, a fatigue test is carried out on the catalyst, and the service life of the catalyst is 8000-10000 h.
Example 5
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare a solution A with the concentration of 2mol/L, adding polyethylene glycol with the polymerization degree of 10000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting for 8 hours at 70 ℃ to obtain a mixed solution B containing Cu/Bi/Ag; mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 12h, dropwise adding a precipitator to control the end point pH to be 6.5, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 600 ℃ for 8h to obtain a catalyst;
(2) the catalyst obtained in the step (1) is filled in a tubular fixed bed reactor in advance, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, continuous sampling and analysis are carried out in the reduction process, and H supplement is determined2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 160 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the residence time of a substrate 1, 3-propylene glycol in the tubular fixed bed reactor is 0.167h, 18000ml of the substrate 1, 3-propylene glycol is treated in unit time, the yield is 98.9%, and the selectivity is 99.2%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is not less than 99.95%, the water content is 25ppm, and the ammonia content is 2 ppm.
The carrier in the step (1) is molecular sieves ZSM-5 and HZSM-5, and the weight ratio of the molecular sieves ZSM-5 to the HZSM-5 is 1:1.
the precipitator in the step (1) is NaHCO3And (3) solution.
The catalyst in the step (1) comprises the following chemical components in percentage by weight before reduction: 28% of CuO and TiO2 10%、Fe2O33%、Ag2O 1.5%、Bi2O33 percent of carrier and the balance.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 1.5% at room temperature of ~ 150 ℃ and 4.5% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mol ratio of the 1, 3-propylene glycol to ammonia in the ammonia water, the methyl acetate to the methyl formate in the step (3) is 1:1.2: 1.2: 1.2, the reaction temperature is 260 ℃, the reaction pressure is 1.5MPa, and the liquid hourly space velocity is 6h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 150mm, and the diameter of the lower section reaction tube is 80 mm.
Example 6
A method for producing 1-acetyl-2-pyrrolidone, comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare 1.2mol/L solution A, then adding polyethylene glycol with the polymerization degree of 6000, stirring, moving to a microwave hydrothermal parallel synthesizer, and reacting for 5 hours at 90 ℃ to obtain mixed solution B containing Cu/Bi/Ag; mixing nano-grade Fe2O3And TiO2Dispersing the mixture in deionized water by using ultrasonic waves to prepare a solution C; dispersing a nanoscale carrier in deionized water by using ultrasonic waves to prepare a solution D; enabling the solution B, C, D to flow in parallel and mix, stirring for 24h, dropwise adding a precipitator to control the end point pH to be 7.0, standing, filtering, washing, drying a filter cake in vacuum, and roasting at 500 ℃ for 12h to obtain a catalyst;
(2) the catalyst obtained in the step (1) is filled in a tubular fixed bed reactor in advance, a nitrogen replacement reactor is adopted, hydrogen is used for reducing the catalyst, the pressure is kept to be less than or equal to 0.5MPa, continuous sampling and analysis are carried out in the reduction process, and H supplement is determined2Gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient until no water vapor exists at the outlet of the reactor, cooling to 230 ℃ after the catalyst is reduced, replacing the whole system with nitrogen, maintaining the pressure and preserving the heat;
(3) 1, 3-propylene glycol, 25% ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section to be preheated to 200 ℃, and then sent into a tubular fixed bed reactor to carry out amination, addition and cyclization reactions, 3000ml of catalyst is filled in the embodiment, the residence time of a substrate 1, 3-propylene glycol in the tubular fixed bed reactor is 0.2h, 15000ml of the substrate 1, 3-propylene glycol is treated in unit time, the yield is 99.0%, and the selectivity is 99.2%;
(4) and (2) after heat exchange and condensation are carried out on the mixture discharged from the reactor, the mixture is sent into a constant pressure tank, the mixture is decompressed through a flow-limiting pore plate and then enters an intermediate storage tank to purge the surplus ammonia, the collected surplus ammonia returns to the reaction system again, and the crude product in the intermediate storage tank is separated and purified through a three-stage continuous tower to obtain the target product 1-acetyl-2-pyrrolidone, wherein the purity is 99.9%, the water content is 40ppm, and the ammonia content is 2 ppm.
The carrier in the step (1) is molecular sieve ZSM-5.
The precipitator in the step (1) is urea solution.
The catalyst in the step (1) comprises the following chemical components in percentage by weight before reduction: 30% of CuO and TiO2 8%、Fe2O34%、Ag2O 2%、Bi2O3 5 percent, and the balance being carrier.
Referring to fig. 1, the temperature gradient in step (2) is: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
The hydrogen concentration in the reactor was 2% at room temperature ~ 150 ℃ and 5% at 150 ~ 200 ℃ and 100% at 220 ℃ until the reduction was complete.
The mol ratio of the 1, 3-propylene glycol to ammonia in the ammonia water, the methyl acetate to the methyl formate in the step (3) is 1:1.1: 1.0: 1.0, the reaction temperature is 220 ℃, the reaction pressure is 5MPa, and the liquid hourly space velocity is 5h-1。
Referring to fig. 2, the tubular fixed bed reactor in step (3) is composed of an upper section and a lower section, wherein the upper section of the reactor is a laminar flow tubular type, the lower section of the reactor is a self-heating countercurrent tubular type, the diameter of the upper section reaction tube is 120mm, and the diameter of the lower section reaction tube is 50 mm.
Comparative example 1
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: the reaction temperature is 200 ℃;
the product yield is 89.2%, the selectivity is 90.2%, the purity is 95.9%, the water content is 102ppm, and the ammonia content is 60 ppm.
Comparative example 2
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: the reaction pressure is 0.4 MPa;
the product yield is 70.8%, the selectivity is 89.7%, the purity is 94.6%, the water content is 80ppm, and the ammonia content is 76 ppm.
Comparative example 3
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: CuO 32%, ZnO5%, Fe2O3 3%、Ag2O 1.5%、Bi2O3 4 percent, and the balance being carrier;
the product yield is 51.6%, the selectivity is 78.3%, the purity is 83.6%, the water content is 250ppm, and the ammonia content is 160 ppm.
Comparative example 4
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: 15% of CuO and TiO in the catalyst composition2 5%、Fe2O3 3%、Ag2O 1.5%、Bi2O3 4 percent, and the balance being carrier;
the product yield is 70.7%, the selectivity is 83.2%, the purity is 95.8%, the water content is 106ppm, and the ammonia content is 50 ppm.
Comparative example 5
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: 40% of CuO and 40% of TiO in the catalyst composition2 5%、Fe2O3 3%、Ag2O 1.5%、Bi2O3 4 percent, and the balance being carrier;
the product yield is 89.9%, the selectivity is 97.0%, the purity is 97.6%, the water content is 80ppm, and the ammonia content is 20 ppm.
Comparative example 6
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: namely: 32% of CuO and TiO2 5%、Fe2O3 3%、Ag2O 1.5%，4% of ZnO, and the balance of carrier;
the product yield is 70.2%, the selectivity is 80.6%, the purity is 92.2%, the water content is 99ppm, and the ammonia content is 40 ppm.
Comparative example 7
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: the upper and lower sections of the reactor have the same structure, the pipe diameter is 140mm, and the liquid hourly space velocity is 6h-1；
The amount of 1, 3-propanediol treated per unit time was 18000ml, the product yield was 92.7%, the selectivity was 95.9%, the purity was 94.2%, the water content was 52ppm, and the ammonia content was 32 ppm.
Comparative example 8
The process for producing 1-acetyl-2-pyrrolidone of this example is substantially the same as that of example 4, and the same points are not repeated, except that: the upper and lower sections of the reactor have the same structure, the pipe diameter is 60mm, and the liquid hourly space velocity is 4h-1；
The amount of 1, 3-propanediol treated per unit time was 12000ml, the yield 90.9%, the selectivity 95.0%, the purity 92.2%, the water content 60ppm, and the ammonia 20 ppm.
The yield of the 1-acetyl-2-pyrrolidone crude product obtained in the embodiments 1 to 8 of the invention is more than or equal to 98.4 percent, the yield is high, the selectivity is more than or equal to 99.0 percent, the selectivity is good, the product is further separated and purified, the purity of the obtained product is more than or equal to 99.9 percent, the water content is less than or equal to 40ppm, the ammonia content is less than or equal to 2ppm, the product almost contains no water and ammonia, and the purity is high; when the reaction conditions, the catalyst composition or the reactor structure are changed in the comparative example, the yield and the selectivity of the crude 1-acetyl-2-pyrrolidone are obviously reduced, the subsequent separation and purification are difficult, and the purity of the obtained product is obviously reduced, especially in the comparative example 3.

Claims (10)

1. A method for producing 1-acetyl-2-pyrrolidone, which is characterized by comprising the following steps:
the method comprises the steps of taking 1, 3-propylene glycol, ammonia water, methyl acetate and methyl formate as raw materials, carrying out amination, addition and cyclization reactions on the 1, 3-propylene glycol, the ammonia, the methyl acetate and the methyl formate in a tubular fixed bed reactor under the action of a copper-based catalyst to generate a 1-acetyl-2-pyrrolidone crude product, and further purifying to obtain a target product 1-acetyl-2-pyrrolidone.
2. A process for the production of 1-acetyl-2-pyrrolidone according to claim 1, comprising the steps of: 1, 3-propylene glycol, ammonia water, methyl acetate and methyl formate are respectively pumped into a pipeline from a feeding buffer tank by a metering pump, mixed by a mixer, sent into a preheating section for preheating, then sent into a tubular fixed bed reactor, and reacted under the action of a catalyst; and (3) after heat exchange and condensation of the mixed material discharged from the reactor, sending the mixed material into a constant pressure tank, releasing the pressure of the mixed material through a flow-limiting orifice plate, then sending the mixed material into an intermediate storage tank to release the surplus ammonia, returning the collected surplus ammonia into the reaction system again, and separating and purifying the crude product in the intermediate storage tank through a three-stage continuous tower to obtain the product.
3. The process for producing 1-acetyl-2-pyrrolidone according to claim 1, wherein the molar ratio of 1, 3-propanediol to ammonia in aqueous ammonia to methyl acetate to methyl formate is 1 (1.0 ~ 1.2.2): 1.0 ~ 1.2.2 ]: 1.0 ~ 1.2.2), the reaction temperature is 220 ~ 260 ℃, the reaction pressure is 0.5 ~ 5MPa, and the liquid hourly space velocity is 1 ~ 10h-1。
4. A process for producing 1-acetyl-2-pyrrolidone according to claim 1, wherein said tubular fixed bed reactor comprises an upper section and a lower section, the upper section of the reactor is a laminar flow tubular type, the lower section is an auto-thermal countercurrent tubular type, the diameter of the upper section is 100 ~ 150mm, and the diameter of the lower section is 50 ~ 80 mm.
5. A process for producing 1-acetyl-2-pyrrolidone according to claim 1, wherein said copper-based catalyst is prepared by a method comprising the steps of:
(1) dissolving copper nitrate, bismuth nitrate and silver nitrate in deionized water to prepare a solution A of 1 ~ 2mol/L, adding polyethylene glycol with the polymerization degree of 2000 ~ 10000, stirring, transferring to a microwave hydrothermal parallel synthesizer, and reacting at 70 ~ 90 ℃ to obtain the product5 ~ 10h to obtain mixed solution B containing Cu/Bi/Ag, and mixing the mixed solution B with nanoscale Fe2O3And TiO2Dispersing the nano-scale carrier in deionized water by using ultrasonic waves to prepare a solution C, dispersing the nano-scale carrier in the deionized water by using ultrasonic waves to prepare a solution D, cocurrently flowing and mixing the solution B, C, D, stirring for 12 ~ 24h, dropwise adding a precipitator to control the end point pH to be 6.5 ~ 7.0.0, standing, filtering, washing, drying a filter cake in vacuum, and roasting for 8 ~ 12h at 500 ~ 600 ℃ to obtain a catalyst;
(2) filling the catalyst obtained in the step (1) into a tubular fixed bed reactor, replacing the reactor with nitrogen, reducing the catalyst with hydrogen, keeping the pressure less than or equal to 0.5MPa, gradually increasing the temperature from room temperature to 280 ℃ according to the temperature gradient, cooling to 230 ℃ after the reduction of the catalyst is finished, replacing the whole reactor with nitrogen, maintaining the pressure, and keeping the temperature for later use.
6. A process for producing 1-acetyl-2-pyrrolidone according to claim 5, wherein the carrier in step (1) is molecular sieve ZSM-5 and/or HZSM-5.
7. A process for producing 1-acetyl-2-pyrrolidone according to claim 5, wherein the precipitant in step (1) is (NH)4)2CO3、Na2CO3、NaOH、NaHCO3And a urea solution.
8. The method for producing 1-acetyl-2-pyrrolidone of claim 5, wherein the chemical components and weight percentages of the catalyst in step (1) are CuO 25 ~ 35%, TiO2 5~10%、Fe2O3 3~5%、Ag2O 0.5~2%、Bi2O3 3 ~ 5%, the balance being carrier.
9. A process for producing 1-acetyl-2-pyrrolidone according to claim 5, wherein the temperature gradient in step (2) is as follows: the whole reactor is replaced by nitrogen to be qualified at the beginning, and then hydrogen is gradually introduced until the reduction is finished; gradually heating from room temperature to 120 ℃ in 10h, and keeping the temperature for 5 h; heating to 150 ℃ again within 5h, and keeping the temperature for 5 h; heating to 200 ℃ again within 10h, and keeping the temperature for 5 h; heating to 280 ℃ again within 10h, and preserving heat for 10 h; and finally, cooling to 230 ℃ within 5h, replacing the whole reactor with nitrogen, maintaining the pressure and preserving the heat.
10. A process for producing 1-acetyl-2-pyrrolidone according to claim 9, wherein said temperature gradient is such that the hydrogen concentration in the reactor is 2% or less at room temperature of ~ 150 ℃, 5% or less at 150 ~ 200 ℃ and 100% hydrogen concentration at 220 ℃ after completion of the reduction.
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