CN114560765A - Method for industrially producing crotonic acid by using microchannel reactor - Google Patents
Method for industrially producing crotonic acid by using microchannel reactor Download PDFInfo
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- CN114560765A CN114560765A CN202210195936.9A CN202210195936A CN114560765A CN 114560765 A CN114560765 A CN 114560765A CN 202210195936 A CN202210195936 A CN 202210195936A CN 114560765 A CN114560765 A CN 114560765A
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- crotonic acid
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 title claims abstract description 73
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 52
- 230000008569 process Effects 0.000 claims abstract description 38
- 238000002425 crystallisation Methods 0.000 claims abstract description 37
- 230000008025 crystallization Effects 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 29
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims abstract description 25
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 25
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 23
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 23
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000011069 regeneration method Methods 0.000 claims abstract description 14
- 230000008929 regeneration Effects 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 8
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- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 62
- 239000013078 crystal Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000012452 mother liquor Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 14
- 239000010413 mother solution Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- -1 ferrophosphorus Chemical compound 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008213 purified water Substances 0.000 claims description 2
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- 239000011949 solid catalyst Substances 0.000 description 5
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- 238000009825 accumulation Methods 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 239000003225 biodiesel Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for industrially producing crotonic acid by adopting a micro-channel reactor, and relates to the technical field of chemical production of crotonic acid. The method comprises the steps of mixing and preheating crotonaldehyde, a catalyst and an initiator according to a certain proportion by adopting a silicon carbide ceramic plate type micro-channel reactor, simultaneously introducing a gaseous oxidant into the reactor, injecting a mixed solution into the micro-channel reactor for reaction by a metering pump when the pressure in the reactor reaches 0.6-2.0 MPa, allowing the material to stay for 8-30 min, and performing material oxidation, crude product crystallization, crude product fine washing, fine product crystallization, drying granulation, catalyst regeneration and other processes to obtain a finished product of the crotonic acid, wherein the one-time yield of the product can reach 60%, and the application yield can reach 95%. The method has the advantages of good mass transfer and heat transfer effects, short oxidation reaction time, high product yield, high safety degree, few process steps, recyclable catalyst, low production cost, recyclable raw materials in each step, high reaction speed, low energy consumption of wastewater and the like.
Description
Technical Field
The invention relates to the technical field of chemical production of crotonic acid, in particular to a method for industrially producing crotonic acid by adopting a micro-channel reactor.
Background
Crotonic acid is an important chemical intermediate, and is widely applied to a plurality of fields such as medicines, pesticides, dyes, spices, photosensitive chemicals, polymer catalysts, biodiesel additives and the like.
The existing preparation methods of crotonic acid are mainly divided into two types: non-catalytic oxidation production and catalytic oxidation production. (1) Non-catalytic oxidation production: patent documents with publication numbers CN1396148 and CN101979371A respectively disclose methods for preparing crotonic acid without any catalyst oxidation, and the calculation of data in examples in the patent document with publication number CN1396148 shows that the utilization rate of crotonaldehyde is only about 20 ± 2%. (2) And (3) catalytic oxidation production: the catalyst preparation process in the patent document of publication No. CN101003473A is cumbersome; the catalyst used in CA595170A is dissolved in a solvent and cannot be recovered; the method disclosed in CN101003472A relates to the problem of heavy metal contamination; the crotonic acid production method by the catalytic oxidation method mentioned in other related publications has the defects of high production cost, harsh production conditions, complex subsequent treatment process, toxic solvent, high product yield and the like, and seriously restricts the development of the production process.
The production method of crotonic acid belongs to an oxidation process, is one of critical and supervised dangerous processes, adopts the traditional production method of a kettle reactor, and buries potential safety hazards for the whole production process due to the defects of more interfaces, poor material quality, large kettle volume and the like of the kettle reactor.
Microchannel reactors were originally referred to as a small tubular reactor for catalyst evaluation and kinetic studies. With the progress of science and technology, the microchannel reactor is gradually applied to various aspects in the chemical field, particularly a gas-liquid-solid three-phase catalytic microreactor, and more particularly, a necessary device preferred by a plurality of chemical research institutions and production enterprises due to the unique advantages of large specific surface area (10-500 times that of a conventional reactor), good heat conducting property, high mass transfer speed, small liquid holdup, high safety, high raw material utilization rate, few side reactions, capability of being amplified in the same stage and the like.
At present, relevant papers and patent reports for producing crotonic acid by oxidizing crotonaldehyde by using a microchannel reactor are not available in China, and the field is still in a blank stage.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for industrially producing crotonic acid by adopting a microchannel reactor, which has the advantages of good mass transfer and heat transfer effects, short oxidation reaction time, high product yield, high safety degree, few process steps, recyclable catalyst, low production cost, recyclable raw materials in each step, high reaction speed, low energy consumption of wastewater and the like.
In order to realize the technical purpose, the invention adopts the following scheme:
a method for industrially producing crotonic acid by using a microchannel reactor comprises the following steps: the method comprises the following steps of material oxidation process, crude product crystallization process, crude product fine washing process, fine product crystallization process, drying granulation process and catalyst regeneration process:
s1, material oxidation process: mixing crotonaldehyde, a catalyst and an initiator according to the weight ratio of 1: 0.005-0.025: 0.1-0.3, injecting the mixture into a preheating kettle, and preheating to 30-35 ℃ to obtain a mixed solution; simultaneously introducing a gaseous oxidant into the silicon carbide ceramic microchannel reactor; when the pressure of a gaseous oxidant in the silicon carbide ceramic microchannel reactor reaches 0.6-2.0 MPa, injecting the mixed solution into a silicon carbide plate-type microchannel reactor by using a metering pump for reaction to obtain a primary oxidation reaction solution;
s2, crude crystallization: filtering the primary oxidation reaction liquid to separate out a solid catalyst, and enabling the catalyst to enter a catalyst recycling and regenerating process flow; carrying out gas-liquid separation on the primary oxidation reaction liquid with the catalyst separated out under the heat preservation condition of 55-60 ℃ to obtain gas and oxidation reaction liquid, collecting the gas for later use, injecting the oxidation reaction liquid into a first crystallization kettle for crystallization at 3-7 ℃, filtering to obtain crude crotonic acid crystals and a mother liquor I, recovering the mother liquor I into a material recovery tank, and introducing the crude crotonic acid crystals into a crude product fine washing process;
s3, fine washing of crude products: heating the solvent A to 25-45 ℃, dissolving a crotonic acid crude product crystal in the solvent A, wherein the weight ratio of the crotonic acid crude product crystal to the solvent A is 1: 0.5-2.0, filtering to remove impurities after dissolving, performing oil-water separation to obtain a crotonic acid mixed solution and a mother solution II, recovering the mother solution II into a material recovery tank, and enabling the crotonic acid mixed solution to enter a fine product crystallization process;
s4, fine crystal: injecting the crotonic acid mixed solution into a second crystallization kettle, crystallizing at 3-7 ℃, filtering and separating to obtain mother liquor III and fine crystals, collecting the mother liquor III for later use, and drying and granulating the fine crystals;
s5, drying and granulating: fine product crystallization rotary granulation is carried out under the protection of nitrogen, and meanwhile, high-temperature blast blowing and drying are carried out on the granulated product to obtain a pure product of crotonic acid;
s6, catalyst regeneration: and (3) washing and regenerating the waste catalyst separated from the S2 by using a solvent B, and blowing and drying the washed and regenerated catalyst by using high-temperature nitrogen.
The preferred scheme of the invention is as follows:
the silicon carbide ceramic microchannel reactor is a plate-type microchannel reactor made of silicon carbide ceramic, the preferred equipment model is gold C1-300-8 type, a core-type microchannel structure is arranged in the reactor, the inner diameter of a channel is 1.6-2.2 mm, the flow rate of a material is 800-1000 ml/min, the temperature of a reactor jacket is 50-95 ℃, the inlet pressure of a gaseous oxidant is 0.6-2.0 MPa, and the outlet pressure of the material is 0.1-0.3 MPa.
The catalyst is copper acetate (Cu (Ac)2) Cobalt acetate (Co (Ac))2) Manganese acetate (Mn (Ac))2) Activated alumina (Al)2O3) Orthophosphoric acid (H)3PO4) Manganese dioxide (MnO)2) Phosphomolybdic acid (H)3[P(Mo3O10)4]) Phosphoric acid (H)3[Fe(PO4)2]) Iron phosphomolybdate (Fe (PMo)12O40) One or more than two of the catalyst, wherein the catalyst is nano-scale particles, the particle size is 200-500 nm, and the dosage of the catalyst is 0.5-2.5% of the mass of the substrate crotonaldehyde. Preferably, the catalyst is a composite catalyst composed of cobalt acetate, active alumina and iron phosphomolybdate according to the weight ratio of 1:1: 1.
The initiator is acetonitrile (C)2H3N), dimethylformamide (C)3H7NO), dimethylacetamide (C)4H9NO), and the amount of the initiator is 10.0-30.0% of the mass of the crotonaldehyde serving as the substrate. Preferably, the initiator is a composite initiator consisting of acetonitrile, dimethylformamide and dimethylacetamide according to a weight ratio of 1:1: 2.
The gaseous oxidant is air N2+O2Oxygen O2One or two of them; according to O2The amount of the gaseous oxidant is 22.0-45.0% of the mass of the crotonaldehyde serving as the substrate by mole weight calculation. Preferably, the gaseous oxidant is a mixture of oxygen and air, and the amount of the gaseous oxidant is the amount of O in the gaseous oxidant2Morphology by molar weight) of 22 to 45% by mass of crotonaldehyde.
The reaction temperature in the silicon carbide microchannel reactor in S1 is 60-95 ℃, and the material retention time is 10-20 min.
And S2, collecting the gas which is obtained as excessive gaseous oxidant into a material storage tank for pre-oxidation treatment of the material.
The solvent A in S3 is purified water (H)2O), diethyl ether (C)4H10O), isopropyl ether (C)6H14O), petroleum ether (30-60 ℃, 60-90 ℃, 90-120 ℃), n-pentane (C)5H12) Isooctane (C)8H18) One or more than two of the above; the dosage of the solvent A is 50-200% of the crystallization quality of the crude product of crotonic acid. Preferably, the solvent A is prepared by compounding petroleum ether (60-90 ℃), n-pentane and isooctane according to the weight ratio of 3:1: 1.
And in the S5, the drying temperature is 45-60 ℃, and the drying time is 2-4 hours.
And (3) recovering the mother liquor I and the mother liquor II to a crotonaldehyde material recovery tank, and injecting the liquid in the material recovery tank into the silicon carbide ceramic microchannel reactor for reutilization. The mother liquor III contains a certain content of crotonic acid, and is recycled to the solvent A recycling tank.
The solvent B in S6 is acetone C3H6O, Cyclohexanone C6H10O, diethyl ketone C5H10One or more than two of O; preferably, the solvent B is prepared by compounding acetone, cyclohexanone and diethyl ketone according to the weight ratio of 1:2: 2. The using amount of the solvent B is 100-200% of the mass of the catalyst, the washing times of the catalyst are 2-3 times, and the regenerated catalyst obtained after washing is dried and purged for 15-30 min under the protection of nitrogen at 120 ℃.
The catalyst can be repeatedly used for 3-5 times after regeneration.
The pure crotonic acid obtained in S5 is colorless needle-like or prismatic crystal with melting point of 71.4-71.6 deg.C, and is granulated to form white spherical crystal, and gas chromatography analysis shows that the content of crotonic acid is more than 99.90%.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the silicon carbide ceramic plate type microchannel reactor to oxidize the crotonaldehyde, fully utilizes the unique structure and reaction mode of the microchannel reactor to ensure that materials and oxidant fully react under the assistance of the catalyst, can strictly control the intensity of the reaction, effectively avoid the cost rise caused by the accumulation of a large amount of side reactions and byproducts, and simultaneously can avoid potential safety hazards and safety accidents caused by the energy accumulation in the oxidation process due to too much fed materials on the premise of obviously shortening the reaction time and improving the efficiency, thereby fundamentally realizing the safe and controllable production of the industrialized oxidation reaction on the basis of improving the reaction rate.
2. The S1 oxidation process does not use any solvent, improves the utilization rate of the raw material crotonaldehyde by using the composite catalyst, realizes that the material can be directly recycled without treatment, and has the advantages of simple catalyst recovery and regeneration process, obvious reduction of the production cost and great reduction of the discharge of waste water and waste liquid because the solvent raw material is not used.
3. The S1 oxidation process does not use any solvent, avoids the solvent participating in the oxidation reaction to generate unknown substances, and simultaneously avoids the problem that the target product is polluted by toxic substances caused by the fact that the crotonic acid is attached to the solvent.
4. Compared with the prior art, the method does not need water treatment and reduced pressure distillation on the oxidation liquid, saves water resources, avoids large-scale discharge of sewage, reduces production steps and reduces production cost.
5. The solvent used in the purification process can effectively improve the purification rate, can be recycled, and realizes zero emission of pollutants while improving the productivity.
6. The materials generated in each process link can be recycled and reused, the utilization rate of the substrate fed for the first time can reach 50-70%, the utilization rate of the recycled and reused materials fed for the second time can reach 90-95%, and the utilization rate of the raw material crotonaldehyde is basically more than 90%.
7. The production method has the advantages of mild and controllable reaction conditions, low oxidation temperature and few byproducts, and after the materials are recycled and reused, the materials are influenced by the double effects of 'catalyst type selection' and 'reversible reaction balance factor', and various byproducts cannot generate superposition effect, so that large-scale and continuous production is realized.
8. The production method has the advantages of good mass transfer and heat transfer effects, short oxidation reaction time, high product yield, high safety degree, few process steps, recyclable catalyst, low production cost, recyclable raw materials in each step, high reaction speed, low energy consumption of wastewater and the like.
Drawings
FIG. 1 is a flow chart of a process for industrially producing crotonic acid by using a microchannel reactor according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention, but the present invention is not limited thereto.
The technical scheme of the invention is designed based on the following principle:
(1) the production process is safe and controllable; (2) the catalyst has'd with holes', and has good capability of carrying and releasing oxygen; (3) the solvent A has the characteristics of high-temperature crotonic acid solubility and low-temperature crotonic acid solubility; (4) the solvent A hardly remains and belongs to a micro-toxic substance; (5) the solvent B has the characteristic of washing the regenerated catalyst; (6) the catalyst can not be ionized, and the introduction of metal ions and the pollution to a finished product can not be caused; (7) the initiator can obviously improve the activity of the catalyst and solvate metal cations; (8) materials generated by each process can be recycled and reused, and no waste is generated; (9) the production process is simple and the production cost is low.
To achieve the above object, the present invention is designed based on the following principle:
(1) band theory and "d band holes": the energy band theory shows that the catalyst can give higher catalytic activity when the energy value of the'd band hole' is approximately equal to the chemical adsorption energy value generated when the electron is required to transfer and coordinate with the reactant molecule. In addition, different metals have different numbers of d electrons, different chemisorption abilities and different catalytic performances, and the more the number of d electrons not bound to the d-vacancy track is, the more chemisorption is likely to occur. The 3d layer of Fe has 6 electrons, the 3d layer of Co has 7 electrons, the 6d layer of Mo has 5 electrons, and all the d-layer electrons do not reach saturation (the number of saturated d-layer electrons is 10), so that the oxygen carrying and releasing capacity of the material is very strong.
(2) "solvation effect" of the initiator: the aprotic polar solvent can enable cations, particularly metal cations to generate a solvation effect in a catalytic reaction, improve the catalytic activity of the metal ions, reduce the energy of a transition state, reduce the activation energy of an oxidation reaction and greatly accelerate the reaction speed.
(3) Selection of crude purification solvent: when the crude product is purified by recrystallization, the choice of solvent is very important. First, a solvent in which the solubility of the solute is very high at around the boiling point of the solvent and the solubility of the solute is very low at low temperature and in which the phenomenon of liquefaction and stratification of the solute does not occur is preferable; secondly, for substances containing hydroxyl, carboxyl and amino groups and having a melting point not too high (< 100 ℃), oxygen-containing solvents are not selected as much as possible in order to avoid the problem that hydrogen bonds are generated between the solute and the solvent, and the solute is difficult to precipitate.
Based on the above two points, and aiming at the characteristics that crotonic acid contains hydroxyl, carboxyl, is soluble in water, can be ionized, and contains double bonds and alkyl groups, low-toxicity or slightly-toxicity non-polar non-oxygen containing petroleum ether and alkane compounds specified in pharmacopoeia are selected as the most suitable purification solvents.
(4) Selection of a catalyst regeneration method: typical conventional catalyst regeneration methods include both calcination and solvent processes. The solvent method is more suitable because the calcination method easily causes the ash and residue on the surface of the catalyst. When the catalyst regeneration solvent is selected, various reaction materials attached to the surface of the catalyst can be dissolved, and various physicochemical reactions (including dissolution, ionization, decomposition and the like) with the catalyst cannot be generated at the same time. Since cobalt acetate, alumina and iron phosphomolybdate can be dissolved in alcohols, esters and ethers, it is most suitable to select ketones as the catalyst regeneration solvent.
Example 1
A method for industrially producing crotonic acid by adopting a micro-channel reactor comprises the following steps:
s1, material oxidation process: cobalt acetate, active alumina and iron phosphomolybdate form a composite catalyst according to the weight ratio of 1:1:1, and acetonitrile, dimethylformamide and dimethylacetamide are selected as an initiator to form a composite initiator according to the weight ratio of 1:1: 2. Introducing a gaseous oxidant into the silicon carbide ceramic plate type micro-channel reactor, wherein the gaseous oxidant is oxygen and air, and the dosage of the gaseous oxidant (according to O)2Calculated by mole weight of the form) is 25 +/-2% of the mass of the crotonaldehyde, when the pressure in the silicon carbide ceramic plate type microchannel reactor reaches 1.6MPa, the crotonaldehyde, the catalyst and the initiator (weight ratio is 1:0.015: 0.15) are mixed and preheated to 30-35 ℃, and then the mixture is injected into the microchannel reactor through a metering pump, the material flow rate is 800 +/-10 ml/min, the material outlet pressure is 0.15 +/-0.02 MPa, the reaction temperature is 70 ℃, and the material retention time is 20min, so that the primary oxidation reaction liquid is obtained.
S2, a crude product crystallization process: carrying out gas-liquid separation on the primary oxidation reaction liquid after filtering to remove the solid catalyst under the heat preservation condition of 55-60 ℃ (liquid from a liquid outlet of the microchannel reactor flows downwards, and gas can be automatically collected at the upper layer) to obtain gas and oxidation reaction liquid; and injecting the oxidation reaction solution into a first crystallization kettle for crystallization at the low temperature of 5 +/-1 ℃ to obtain crude crotonic acid crystals and a mother solution I, and recovering the mother solution I into a material recovery tank.
S3, a crude product fine washing process: selecting petroleum ether (60-90 ℃), n-pentane and isooctane to form a composite solvent A according to the weight ratio of 3:1:1, heating the composite solvent A to 35 +/-2 ℃, dissolving the crude crotonic acid crystals according to the weight ratio of the solvent A to the crude crotonic acid crystals =1.5:1, filtering to remove impurities, performing oil-water separation to obtain a mixed crotonic acid solution and a mother liquor II, and recovering the mother liquor II to a material recovery tank.
S4, fine product crystallization process: and (3) placing the crotonic acid mixed solution in a second crystallization kettle, crystallizing at the low temperature of 5 +/-1 ℃, and filtering and separating to obtain a mother solution III and fine crystals.
S5, drying and granulating: and (3) carrying out fine crystal rotary granulation under the protection of nitrogen, and simultaneously carrying out high-temperature blowing, blowing and drying at the drying temperature of 55 +/-2 ℃ for 3 +/-0.2 hours.
S6, catalyst regeneration process: selecting acetone, cyclohexanone and diethyl ketone according to a weight ratio of 1:2:2 to form a composite solvent B, wherein the using amount of the composite solvent B is 100% of the weight of the catalyst, washing times are 1-2 times, and after washing and filtering, drying and purging at 120 ℃ for 20min under the protection of nitrogen.
Example 2
A method for industrially producing crotonic acid by adopting a micro-channel reactor comprises the following steps:
s1, material oxidation process: cobalt acetate, active alumina and iron phosphomolybdate form a composite catalyst according to the weight ratio of 1:1:1, and acetonitrile, dimethylformamide and dimethylacetamide are selected as an initiator to form a composite initiator according to the weight ratio of 1:1: 2. Introducing a gaseous oxidant (air + oxygen) into the silicon carbide ceramic plate type microchannel reactor, wherein the dosage of the oxygen oxidant (according to O)2Calculated by the mole weight of the form) is 30 +/-2 percent of the mass of the crotonaldehyde, when the pressure in the silicon carbide ceramic plate type microchannel reactor reaches 0.8MPa, the crotonaldehyde, the catalyst and the initiator (the weight ratio is 1:0.01: 0.30) are mixed and preheated to 30-35 ℃, and then the mixture is injected into the microchannel reactor through a metering pump, the flow rate of the material is 900 +/-10 ml/min, the pressure at a material outlet is 0.20 +/-0.02 MPa, the reaction temperature is 60 ℃, and the retention time of the material is 12min, so that the primary oxidation reaction liquid is obtained.
S2, a crude product crystallization process: carrying out gas-liquid separation on the primary oxidation reaction liquid after the solid catalyst is removed by filtration under the heat preservation condition of 55-60 ℃ to obtain gas and oxidation reaction liquid; and injecting the oxidation reaction solution into a first crystallization kettle for crystallization at the low temperature of 5 +/-1 ℃ to obtain crude crotonic acid crystals and a mother solution I, and recovering the mother solution I into a material recovery tank.
S3, a crude product fine washing process: selecting petroleum ether (60-90 ℃), n-pentane and isooctane to form a composite solvent A according to the weight ratio of 3:1:1, heating the composite solvent A to 40 +/-2 ℃, dissolving the crude crotonic acid crystals according to the weight ratio of the solvent A to the crude crotonic acid crystals =0.75:1, filtering to remove impurities, performing oil-water separation to obtain a mixed crotonic acid solution and a mother liquor II, and recovering the mother liquor II to a material recovery tank.
S4, fine product crystallization process: and (3) placing the crotonic acid mixed solution in a second crystallization kettle, crystallizing at the low temperature of 5 +/-1 ℃, and filtering and separating to obtain a mother solution III and fine crystals.
S5, drying and granulating: and (3) carrying out rotary granulation on the fine crystals under the protection of nitrogen, and simultaneously carrying out high-temperature blowing, blowing and drying at the drying temperature of 50 +/-2 ℃ for 3 +/-0.2 hours.
S6, catalyst regeneration process: and selecting acetone, cyclohexanone and diethyl ketone to form a composite solvent B according to the weight ratio of 1:2:2, wherein the dosage of the composite solvent B is 150% of the weight of the catalyst, the washing times are 1-2 times, and after the washing is finished and the filtration is carried out, drying and purging are carried out for 20min at 120 ℃ under the protection of nitrogen.
Example 3
A method for industrially producing crotonic acid by adopting a micro-channel reactor comprises the following steps:
s1, material oxidation process: cobalt acetate, active alumina and iron phosphomolybdate form a composite catalyst according to the weight ratio of 1:1:1, and acetonitrile, dimethylformamide and dimethylacetamide are selected as an initiator to form a composite initiator according to the weight ratio of 1:1: 2. Introducing a gaseous oxidant (air and oxygen) into the silicon carbide ceramic plate type microchannel reactor, wherein the dosage of the gaseous oxidant (according to O)2Calculated by mole weight of the form) is 35 +/-2 percent of the mass of the crotonaldehyde, when the pressure in the silicon carbide ceramic plate type microchannel reactor reaches 1.8MPa, the crotonaldehyde, the catalyst and the initiator (weight ratio is 1:0.015: 0.20) are mixed and preheated, and then are injected into the microchannel reactor through a metering pump, the material flow rate is 1000 +/-10 ml/min, the material outlet pressure is 0.10 +/-0.02 MPa, the reaction temperature is 95 ℃, and the material residence time is 18min, so that the primary oxidation reaction liquid is obtained.
S2, a crude product crystallization process: carrying out gas-liquid separation on the primary oxidation reaction liquid after filtering to remove the solid catalyst under the heat preservation condition of 55-60 ℃ to obtain gas and oxidation reaction liquid; injecting the oxidation reaction liquid into a first crystallization kettle for crystallization at the low temperature of 5 +/-1 ℃ to obtain crude crotonic acid crystals and a mother liquor I, and recovering the mother liquor I into a material recovery tank.
S3, a crude product fine washing process: selecting petroleum ether (60-90 ℃), n-pentane and isooctane to form a composite solvent A according to the weight ratio of 3:1:1, heating the composite solvent A to 30 +/-2 ℃, dissolving the crude crotonic acid crystals according to the weight ratio of the solvent A to the crude crotonic acid crystals =1:1, filtering to remove impurities and insoluble substances, performing oil-water separation to obtain a mixed crotonic acid solution and a mother liquor II, and recovering the mother liquor II to a material recovery tank.
S4, fine product crystallization process: and (3) placing the crotonic acid mixed solution in a second crystallization kettle, crystallizing at the low temperature of 5 +/-1 ℃, and filtering and separating to obtain a mother solution III and fine crystals.
S5, drying and granulating: and (3) carrying out rotary granulation on the fine crystals under the protection of nitrogen, and simultaneously carrying out high-temperature blowing, blowing and drying at the drying temperature of 55 +/-2 ℃ for 2.5 +/-0.2 hours.
S6, catalyst regeneration process: and selecting acetone, cyclohexanone and diethyl ketone to form a composite solvent B according to the weight ratio of 1:2:2, wherein the dosage of the composite solvent B is 150% of the weight of the catalyst, the washing times are 1-2 times, and after the washing is finished and the filtration is carried out, drying and purging are carried out for 25min at 120 ℃ under the protection of nitrogen.
Example 4
A method for industrially producing crotonic acid by adopting a micro-channel reactor comprises the following steps:
s1, material oxidation process: cobalt acetate, active alumina and iron phosphomolybdate form a composite catalyst according to the weight ratio of 1:1:1, and acetonitrile, dimethylformamide and dimethylacetamide are selected as an initiator to form a composite initiator according to the weight ratio of 1:1: 2. Introducing a gaseous oxidant into the silicon carbide ceramic plate type micro-channel reactor, wherein the dosage of the gaseous oxidant is determined according to O2Calculated by mole weight of the form) is 40 +/-2 percent of the mass of the crotonaldehyde, when the pressure in the silicon carbide ceramic plate type microchannel reactor reaches 1.6MPa, the crotonaldehyde, the catalyst and the initiator (the weight ratio is 1:0.025: 0.25) are mixed and preheated, and then are injected into the microchannel reactor through a metering pump, the material flow rate is 900 +/-10 ml/min, and the material outlet pressure is 0.25 plus or minus 0.02MPa, the reaction temperature is 90 ℃, and the material retention time is 15min, so as to obtain the primary oxidation reaction liquid.
S2, a crude product crystallization process: carrying out gas-liquid separation on the primary oxidation reaction liquid after the solid catalyst is removed by filtration under the heat preservation condition of 55-60 ℃ to obtain gas and oxidation reaction liquid; and injecting the oxidation reaction solution into a first crystallization kettle for crystallization at the low temperature of 5 +/-1 ℃ to obtain crude crotonic acid crystals and a mother solution I, and recovering the mother solution I into a material recovery tank.
S3, a crude product fine washing process: selecting petroleum ether (60-90 ℃), n-pentane and isooctane to form a composite solvent A according to the weight ratio of 3:1:1, heating the composite solvent A to 45 +/-2 ℃, dissolving the crude crotonic acid crystals according to the weight ratio of the solvent A to the crude crotonic acid crystals =1.25:1, filtering to remove impurities and insoluble substances, performing oil-water separation to obtain a mixed crotonic acid solution and a mother liquor II, and recycling the mother liquor II to a material recycling tank.
S4, fine product crystallization process: and (3) placing the crotonic acid mixed solution in a second crystallization kettle, crystallizing at the low temperature of 5 +/-1 ℃, and filtering and separating to obtain a mother solution III and fine crystals.
S5, drying and granulating: and (3) carrying out rotary granulation on the fine crystals under the protection of nitrogen, and simultaneously carrying out high-temperature blowing, blowing and drying at the drying temperature of 60 +/-2 ℃ for 3.5 +/-0.2 hours.
S6, catalyst regeneration process: selecting acetone, cyclohexanone and diethyl ketone to form a composite solvent B according to the weight ratio of 1:2:2, wherein the dosage of the composite solvent B is 200% of the weight of the catalyst, the washing times are 1-2 times, and after the washing is finished and the filtration is carried out, drying and purging are carried out for 15min at 120 ℃ under the protection of nitrogen.
The primary raw material input weight, the primary finished product weight, the primary raw material utilization rate, the raw material input weight after mechanical application, the finished product weight after mechanical application, the raw material utilization rate after mechanical application, the physical and chemical properties of the finished product and the like of the embodiment are shown in the following table.
The table shows that the utilization rate of the raw material of the crotonaldehyde obtained by the method provided by the invention reaches more than 55%, the utilization rate of the mechanically applied raw material reaches more than 92% after the intermediate product is utilized, the utilization rate of the raw material is obviously improved, and higher economic benefit is brought to the industrial production of the crotonic acid.
The silicon carbide ceramic microchannel reactor with the single plate liquid holdup of only 500ml is adopted for large-scale industrialized crotonic acid production, which is the first initiative in China, and the process has the advantages of good mass transfer and heat transfer effects, short oxidation reaction time, high product yield, high safety degree, few process steps, recyclable catalyst, low production cost, recyclable raw materials in all the steps, high reaction speed, low energy consumption of wastewater and the like.
Finally, it is noted that: the above-mentioned list is only the preferred embodiment of the present invention, and naturally those skilled in the art can make modifications and variations to the present invention, which should be considered as the protection scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.
Claims (10)
1. A method for industrially producing crotonic acid by adopting a microchannel reactor is characterized by comprising the following steps:
s1, oxidizing materials: mixing crotonaldehyde, a catalyst and an initiator according to the weight ratio of 1: 0.005-0.025: 0.1-0.3, and injecting into a preheating kettle for preheating to obtain a mixed solution; simultaneously introducing a gaseous oxidant into the silicon carbide ceramic microchannel reactor; when the pressure in the silicon carbide ceramic microchannel reactor reaches 0.6-2.0 MPa, injecting the mixed solution into a silicon carbide plate type microchannel reactor by using a metering pump for reaction to obtain a primary oxidation reaction solution;
s2, crude crystallization: carrying out gas-liquid separation on the primary oxidation reaction liquid at the temperature of 55-60 ℃ to obtain gas and oxidation reaction liquid, collecting the gas for later use, injecting the oxidation reaction liquid into a first crystallization kettle for crystallization at the temperature of 3-7 ℃ to obtain crude crotonic acid crystals and mother liquor I, and collecting the mother liquor I for later use;
s3, fine washing of crude products: heating the solvent A to 25-45 ℃, dissolving the crotonic acid crude product crystals in the solvent A, wherein the weight ratio of the crotonic acid crude product crystals to the solvent A is 1: 0.5-2.0, removing impurities after dissolving, separating to obtain a crotonic acid mixed solution and a mother solution II, and collecting the mother solution II for later use;
s4, fine crystal: injecting the crotonic acid mixed solution into a second crystallization kettle, crystallizing at 3-7 ℃, filtering and separating mother liquor III and fine crystals, and collecting the mother liquor III for later use;
s5, drying and granulating: carrying out fine product crystallization, rotary granulation and blowing and drying under the protection of nitrogen to obtain a pure crotonic acid product;
s6, catalyst regeneration: and (3) washing and regenerating the catalyst by using the solvent B, and blowing and drying the washed and regenerated catalyst by using nitrogen.
2. The method for industrially producing crotonic acid by using the microchannel reactor as claimed in claim 1, wherein the silicon carbide ceramic microchannel reactor is a plate microchannel reactor, the inner diameter of the channel is 1.6 to 2.2mm, the material flow rate is 800 to 1000ml/min, the temperature of the reactor jacket is 50 to 95 ℃, the inlet pressure of the gaseous oxidant is 0.6 to 2.0MPa, and the outlet pressure of the material is 0.1 to 0.3 MPa.
3. The method for industrially producing crotonic acid by using microchannel reactor as claimed in claim 1, wherein the catalyst is one or more than two of copper acetate, cobalt acetate, manganese acetate, activated alumina, orthophosphoric acid, manganese dioxide, phosphomolybdic acid, ferrophosphorus, iron phosphomolybdate; the particle size of the catalyst is 200-500 nm, and the dosage of the catalyst is 0.5-2.5% of the mass of the substrate crotonaldehyde.
4. The method for industrially producing crotonic acid by using microchannel reactor as claimed in claim 1, wherein the initiator is one or more of acetonitrile, dimethylformamide and dimethylacetamide, and the amount of the initiator is 10.0-30.0% by mass of crotonaldehyde as substrate.
5. The method of claim 1, wherein the gaseous oxidant is one or both of air and oxygen; according to O2In a form ofCalculated by molar weight, the dosage of the gaseous oxidant is 22.0-45.0% of the mass of the crotonaldehyde serving as the substrate.
6. The method for industrially producing crotonic acid by using the microchannel reactor as claimed in claim 1, wherein the reaction temperature in the silicon carbide microchannel reactor in S1 is 60-95 ℃ and the material residence time is 10-20 min.
7. The method for industrially producing crotonic acid by using microchannel reactor as claimed in claim 1, wherein the solvent A in S3 is one or more selected from purified water, diethyl ether, isopropyl ether, petroleum ether, n-pentane and isooctane; the dosage of the solvent A is 50-200% of the crystallization quality of the crude crotonic acid product.
8. The method for industrially producing crotonic acid by using microchannel reactor as claimed in claim 1, wherein the drying temperature in S5 is 45-60 ℃ and the drying time is 2-4 hours.
9. The process of claim 1, wherein mother liquor I and mother liquor II are recycled to the material recovery tank, and mother liquor III is recycled to the solvent A storage tank.
10. The method for industrially producing crotonic acid by using microchannel reactor as claimed in claim 1, wherein solvent B in S6 is one or more of acetone, cyclohexanone, and diethyl ketone; the using amount of the solvent B is 100-200% of the mass of the catalyst, the washing times of the catalyst are 2-3 times, and the regenerated catalyst obtained after washing is dried and swept for 15-30 min under the protection of nitrogen at 120 ℃.
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| CN115722154A (en) * | 2022-11-17 | 2023-03-03 | 安徽中山化工有限公司 | Crotonic acid production system and technology |
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Application publication date: 20220531 Assignee: GUANGXI JINMAO BIOCHEMICAL CO.,LTD. Assignor: GUANGXI JINYUAN BIOCHEMICAL INDUSTRIAL Co.,Ltd. Contract record no.: X2023980051718 Denomination of invention: A method for industrial production of crotonic acid using microchannel reactors Granted publication date: 20230908 License type: Common License Record date: 20231211 |