CN114394937B - Method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on fixed bed microreactor - Google Patents
Method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on fixed bed microreactor Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 36
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000012530 fluid Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 4
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims description 55
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000006268 reductive amination reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000001308 synthesis method Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 phosphoric acid modified platinum/carbon Chemical class 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings 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
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on a fixed bed microreactor, belonging to the technical field of chemical reaction engineering. Firstly, mixing a substrate solution to be hydrogenated with formaldehyde to obtain a mixed solution, or adding homogeneous acid into the mixed solution, mixing the mixed solution with hydrogen in an inlet micromixer to obtain a gas-liquid mixed fluid, and then continuously completing a heterogeneous hydrogenation process by the gas-liquid mixed fluid through a micro-packed bed one-step method filled with a catalyst. The method utilizes the efficient and excellent mass and heat transfer performance of the micro-reactor, strengthens the gas-liquid and liquid-solid mass transfer in the heterogeneous hydrogenation reaction process, improves the heat transfer capacity of the reactor, can reduce the volume of the reactor and improves the reaction yield. The method can solve the problems of low production efficiency, poor product purity, high device danger in the hydrogenation kettle process, realize continuous and automatic operation of the process, and has the advantages of high yield, good safety and the like.
Description
Technical Field
The invention relates to the technical field of chemical reaction engineering, in particular to a method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on a fixed bed microreactor.
Background
1, 3-dimethyl-2-imidazolidinone (DMI) is a transparent colorless polar aprotic solvent, which has excellent dissolving power to dissolve many organic and inorganic substances with polarity, and is miscible with water in any proportion. Has the characteristics of low toxicity, safety and stability. Is widely applied to the fields of petrochemical industry, medicines, electronic chips and the like. The synthesis method of DMI includes carbon dioxide method, phosgene method, trichloroacetyl chloride method, urea method, and 2-imidazolidone methylation method. At present, the industrial production of DMI mainly takes urea and ethylenediamine as raw materials to synthesize 2-imidazolidinone first, and then N-methylation is carried out on the 2-imidazolidinone to obtain the product DMI. Methylation of 2-imidazolidinone is commonly used in the "formic acid process" and "hydrogenation process". Two production processes for preparing DMI from 2-imidazolidinone are carried out in two steps: firstly, 2-imidazolidone reacts with formaldehyde to generate an intermediate imine, and then the imine is reduced to methyl under the action of hydrogen or formic acid.
The two-step hydrogenation reduction of 2-imidazolidinone to prepare DMI greatly improves the production cleaning effect, but the traditional reaction kettle has high process cost and potential safety hazard problem in the use of a large amount of hydrogen. The continuous hydrogenation and reductive amination using the micro packed bed can reduce the production cost to a certain extent and improve the production efficiency and the safety, but the device is complex and the equipment investment cost is slightly high.
The bifunctional catalyst is modified by sulfuric acid or phosphoric acid on the basis of the hydrogenation catalyst, so that the catalyst can simultaneously complete the preparation of the imine intermediate and the hydrogenation reduction process of the intermediate. The hydrogenation reduction amination process of the 2-imidazolidone is completed in a one-step method in a micro-packed bed reactor by developing a specific bifunctional catalyst, so that the continuity of the process can be realized, the volume of the reactor is reduced, and the production efficiency is further improved. Therefore, the method for producing DMI by heterogeneous hydrogenation reduction amination based on the microreactor technology has important economic, safe and environment-friendly values for reducing the investment of production equipment, improving the process safety and the production capacity and the product purity.
Disclosure of Invention
In view of the above, the invention provides a method for synthesizing 1, 3-dimethyl-2-imidazolidinone by one-step continuous hydrogenation based on a fixed bed microreactor, which utilizes the efficient and excellent mass and heat transfer performance of the microreactor, strengthens the interphase mass and heat transfer capability in the reaction process, can obviously reduce the volume of the reactor, improves the reaction yield, and improves the production efficiency and safety.
The invention provides a method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on a fixed bed microreactor, which comprises the following steps:
(1) Preparing a gas-liquid mixed fluid: the preparation method of the gas-liquid mixed fluid comprises any one of the following two steps:
mixing 2-imidazolidone with a solvent to obtain a substrate solution to be hydrogenated, adding formaldehyde to obtain a mixed solution, and introducing hydrogen to form a gas-liquid mixed fluid;
mixing 2-imidazolidone with a solvent to obtain a substrate solution to be hydrogenated, adding formaldehyde to obtain a mixed solution, adding a homogeneous acid into the mixed solution, stirring at 70-90 ℃ for 2-4 hours, and then introducing hydrogen to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a catalyst, and stays for 1-5 min under the conditions that the temperature is 90-160 ℃ and the pressure is 1.0-3.5MPa, so as to carry out heterogeneous hydrogenation reductive amination reaction;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2) to obtain a 1, 3-dimethyl-2-imidazolidinone solution. The solution is separated and purified to obtain the product 1, 3-dimethyl-2-imidazolone.
Preferably, the solvent in the step (1) is mixed by any one of methanol, ethanol and 1, 3-dimethyl-2-imidazolidinone and deionized water according to a mass ratio of 1:2-1:99.
Preferably, the molar ratio of formaldehyde to 2-imidazolidone in the step (1) is 2.1-3.2:1, and the molar ratio of hydrogen to 2-imidazolidone is 2.5-5:1.
Preferably, the mass concentration of the 2-imidazolidone in the mixed solution in the step (1) is 5-20 wt%.
Preferably, in the method (1), the homogeneous acid is any one of acetic acid, benzoic acid, citric acid, glycolic acid and malonic acid.
Preferably, the molar ratio of the homogeneous acid to the 2-imidazolidone is 0.05-0.1:1.
Preferably, the catalyst in the step (2) is a bifunctional solid particle catalyst or a hydrogenation solid particle catalyst;
when the step (1) adopts the method (1) to prepare the gas-liquid mixed fluid, a bifunctional solid particle catalyst is adopted, wherein the bifunctional solid particle catalyst is any one of palladium/carbon, platinum/carbon, ruthenium/carbon and palladium/aluminum oxide modified by sulfuric acid or phosphoric acid;
when the step (1) adopts the method (2) to prepare the gas-liquid mixed fluid, the hydrogenation solid particle catalyst is adopted ， The hydrogenation solid particle catalyst is any one of palladium/carbon, platinum/carbon, ruthenium/carbon and palladium/alumina.
Preferably, the one-step continuous hydrogenation synthesis method of 1, 3-dimethyl-2-imidazolone adopts a fixed bed micro-reactor for reaction, wherein the fixed bed micro-reactor comprises an inlet micro-mixer, a micro-packed bed connected with the inlet micro-mixer, and a gas-liquid separation device connected with the micro-packed bed.
The preparation of the gas-liquid mixed fluid is carried out in an inlet micromixer, the heterogeneous hydrogenation reductive amination reaction is carried out in a micro-packed bed, and the gas-liquid separation is carried out in a gas-liquid separation device.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on a fixed bed micro-reactor, which adopts a micro-packed bed reactor for reaction, and the micro-packed bed reactor has large gas-liquid-solid three-phase contact area and high mass transfer efficiency, and can reduce the catalyst consumption and the equipment volume; the gas phase and the liquid phase in the micro-packed bed reactor are uniformly distributed, the micro-packed bed has strong heat transfer capability, local excessive hydrogenation is avoided, the occurrence of byproducts is reduced, and the service life of the catalyst is prolonged; the reaction time is accurate and controllable, byproducts can be further reduced, and the selectivity is improved; the reactor has small volume and high safety.
Drawings
FIG. 1 is a schematic diagram of an apparatus for one-step hydroreductive amination in a micro-packed bed reactor according to the present invention;
wherein 1 is an inlet micromixer, 2 is a micro-packed bed, and 3 is a gas-liquid separation device.
Detailed Description
The invention will be further illustrated by the following examples
Example 1
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared from methanol and deionized water according to a mass ratio of 1:2 to obtain a methanol-water solution of the 2-imidazolidinone with a concentration of 5wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, and mixing with hydrogen in an inlet micromixer (a molar ratio of hydrogen to 2-imidazolidinone of 3:1) to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a sulfuric acid modified difunctional palladium/carbon catalyst, the reaction temperature of the micro-packed bed is 140 ℃, the residence time is 2min, and the pressure is 3.5MPa, so that heterogeneous hydrogenation reductive amination reaction is carried out;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 99% and the DMI selectivity is 97.41%.
Example 2
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidone with a solvent, wherein the solvent is a mixture of methanol and deionized water according to a mass ratio of 1:9 to obtain a methanol-water solution of the 2-imidazolidone with a concentration of 10wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidone of 3.2:1, and mixing the mixture with hydrogen (hydrogen to 2-imidazolidone molar ratio of 4:1) at an inlet micromixer to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a phosphoric acid modified difunctional palladium/carbon catalyst, the reaction temperature of the micro-packed bed is 160 ℃, the residence time is 1min, and the pressure is 3.0MPa, so as to carry out heterogeneous hydrogenation reductive amination reaction;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is 100%, and the selectivity of the DMI is 99.84%.
Example 3
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared by DMI and deionized water according to a mass ratio of 1:9 to obtain a DMI-water solution of the 2-imidazolidinone with a concentration of 15wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, and mixing with hydrogen in an inlet micromixer (a molar ratio of hydrogen to 2-imidazolidinone of 3:1) to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a phosphoric acid modified bifunctional palladium/aluminum oxide catalyst, the reaction temperature of the micro-packed bed is 150 ℃, the residence time is 5min, and the pressure is 2.5MPa, so as to carry out heterogeneous hydrogenation reductive amination reaction;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 99%, and the DMI selectivity is 96.82%.
Example 4
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared by DMI and deionized water according to a mass ratio of 1:19 to obtain a DMI-water solution of the 2-imidazolidinone with a concentration of 10wt%, adding formaldehyde according to a molar ratio of formaldehyde to the 2-imidazolidinone of 2.5:1, and mixing with hydrogen in an inlet micromixer (the molar ratio of hydrogen to the 2-imidazolidinone of 2.5:1) to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a phosphoric acid modified platinum/carbon dual-function catalyst, the reaction temperature of the micro-packed bed is 130 ℃, the residence time is 4min, and the pressure is 2.0MPa, so as to carry out heterogeneous hydrogenation reductive amination reaction;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 98%, and the selectivity of the DMI is 95.52%.
Example 5
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared by DMI and deionized water according to a mass ratio of 1:99 to obtain a DMI-water solution of the 2-imidazolidinone with a concentration of 5wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, adding benzoic acid (controlling a molar ratio of benzoic acid to 2-imidazolidinone of 0.05:1), and stirring at 70 ℃ for 4 hours; mixing with hydrogen (molar ratio of hydrogen to 2-imidazolidinone 2.5:1) at an inlet micromixer to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a palladium/carbon catalyst, the reaction temperature of the micro-packed bed is 130 ℃, the residence time is 5min, and the pressure is 3MPa, so that heterogeneous hydrogenation reductive amination reaction is carried out;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 98%, and the selectivity of DMI is 96.84%.
Example 6
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture of DMI and deionized water according to a mass ratio of 1:99 to obtain a DMI-water solution of the 2-imidazolidinone with a concentration of 5wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, adding citric acid (controlling a molar ratio of citric acid to 2-imidazolidinone of 0.1:1), and stirring at 80 ℃ for 3 hours; mixing with hydrogen (molar ratio of hydrogen to 2-imidazolidinone 2.5:1) at an inlet micromixer to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a platinum/carbon catalyst, the reaction temperature of the micro-packed bed is 130 ℃, the residence time is 2min, and the pressure is 3MPa, so that heterogeneous hydrogenation reductive amination reaction is carried out;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 98%, and the selectivity of the DMI is 92.52%.
Example 7
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared from methanol and deionized water according to a mass ratio of 1:9 to obtain a methanol-water solution of the 2-imidazolidinone with a concentration of 10wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, adding malonic acid (controlling a molar ratio of malonic acid to 2-imidazolidinone of 0.05:1), and stirring for 2h at 90 ℃; mixing with hydrogen (molar ratio of hydrogen to 2-imidazolidinone 2.5:1) at an inlet micromixer to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a palladium/carbon catalyst, the reaction temperature of the micro-packed bed is 130 ℃, the residence time is 3min, and the pressure is 3MPa, so that heterogeneous hydrogenation reductive amination reaction is carried out;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 98%, and the selectivity of DMI is 96.84%.
Example 8
A one-step continuous hydrogenation synthesis method for 1, 3-dimethyl-2-imidazolone based on a fixed bed microreactor comprises the following steps:
(1) Mixing 2-imidazolidinone with a solvent, wherein the solvent is a mixture prepared from ethanol and deionized water according to a mass ratio of 1:5 to obtain an ethanol-water solution of the 2-imidazolidinone with a concentration of 5wt%, adding formaldehyde according to a molar ratio of formaldehyde to 2-imidazolidinone of 2.5:1, adding glycolic acid (controlling a molar ratio of glycolic acid to 2-imidazolidinone of 0.05:1), and stirring at 80 ℃ for 4 hours; mixing with hydrogen (molar ratio of hydrogen to 2-imidazolidinone 2.5:1) at an inlet micromixer to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with palladium/alumina catalyst, the reaction temperature of the micro-packed bed is 110 ℃, the residence time is 2min, and the pressure is 3MPa, so that heterogeneous hydrogenation reductive amination reaction is carried out;
(3) And (3) carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2), and analyzing the obtained solution, wherein the conversion rate is more than 98%, and the selectivity of DMI is 91.42%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A method for synthesizing 1, 3-dimethyl-2-imidazolone by one-step continuous hydrogenation based on a fixed bed microreactor, which is characterized by comprising the following steps:
(1) Mixing 2-imidazolidone with a solvent to obtain a substrate solution to be hydrogenated, adding formaldehyde to obtain a mixed solution, and introducing hydrogen to form a gas-liquid mixed fluid;
(2) The gas-liquid mixed fluid obtained in the step (1) flows through a micro-packed bed filled with a catalyst, and stays for 1-5 min under the conditions that the reaction temperature is 90-160 ℃ and the pressure is 1.0-3.5MPa, so as to carry out heterogeneous hydrogenation reductive amination reaction;
(3) Carrying out gas-liquid separation on the gas-liquid mixture obtained in the step (2) to obtain a 1, 3-dimethyl-2-imidazolidinone solution;
adding homogeneous acid into the mixed solution in the step (1), stirring for 2-4 hours at the temperature of 70-90 ℃, and then introducing hydrogen to form a gas-liquid mixed fluid;
the homogeneous acid is any one of acetic acid, benzoic acid, citric acid, glycolic acid and malonic acid;
the catalyst in the step (2) is a hydrogenation solid particle catalyst, and the hydrogenation solid particle catalyst is any one of palladium/carbon, platinum/carbon, ruthenium/carbon and palladium/alumina.
2. The method for synthesizing 1, 3-dimethyl-2-imidazolidinone by one-step continuous hydrogenation based on a fixed bed microreactor according to claim 1, wherein the solvent in the step (1) is methanol, ethanol or any one of 1, 3-dimethyl-2-imidazolidinone and deionized water according to a mass ratio of 1:2-1:99.
3. The method for synthesizing 1, 3-dimethyl-2-imidazolidinone by one-step continuous hydrogenation based on a fixed bed microreactor according to claim 1, wherein the molar ratio of formaldehyde to 2-imidazolidinone in the step (1) is 2.1-3.2:1, and the molar ratio of hydrogen to 2-imidazolidinone is 2.5-5:1.
4. The method for synthesizing 1, 3-dimethyl-2-imidazolidinone by one-step continuous hydrogenation based on a fixed bed microreactor according to claim 1, wherein the mass concentration of 2-imidazolidinone in the mixed solution in the step (1) is 5wt% to 20wt%.
5. The method for synthesizing 1, 3-dimethyl-2-imidazolidinone by continuous hydrogenation based on a fixed bed microreactor one-step method according to claim 1, characterized in that the molar ratio of the homogeneous acid to 2-imidazolidinone is 0.05-0.1:1.
6. The method for synthesizing 1, 3-dimethyl-2-imidazolidinone by one-step continuous hydrogenation based on a fixed bed micro-reactor according to claim 1, wherein the one-step continuous hydrogenation method for synthesizing 1, 3-dimethyl-2-imidazolidinone uses a fixed bed micro-reactor for reaction, and the fixed bed micro-reactor comprises an inlet micro-mixer, a micro-packed bed connected with the inlet micro-mixer, and a gas-liquid separation device connected with the micro-packed bed.
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