CN114425442B - Catalyst for synthesizing alkylene carbonate and preparation method and application thereof - Google Patents
Catalyst for synthesizing alkylene carbonate and preparation method and application thereof Download PDFInfo
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- CN114425442B CN114425442B CN202011091097.3A CN202011091097A CN114425442B CN 114425442 B CN114425442 B CN 114425442B CN 202011091097 A CN202011091097 A CN 202011091097A CN 114425442 B CN114425442 B CN 114425442B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- -1 alkylene carbonate Chemical compound 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 125000004193 piperazinyl group Chemical group 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 43
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 239000000460 chlorine Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920005990 polystyrene resin Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 2
- IHPYMWDTONKSCO-UHFFFAOYSA-N 2,2'-piperazine-1,4-diylbisethanesulfonic acid Chemical compound OS(=O)(=O)CCN1CCN(CCS(O)(=O)=O)CC1 IHPYMWDTONKSCO-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- LGDNSGSJKBIVFG-UHFFFAOYSA-N n,n-dimethyl-2-piperazin-1-ylethanamine Chemical compound CN(C)CCN1CCNCC1 LGDNSGSJKBIVFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 238000005406 washing Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002608 ionic liquid Chemical group 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a catalyst for synthesizing alkylene carbonate, which is a supported piperazine catalyst, and an active center component is piperazine units. The invention also provides a preparation method of the catalyst for synthesizing alkylene carbonate, which comprises the following steps: the catalyst is prepared by mixing and reacting a carrier, an active center component precursor and an organic solvent. The catalyst of the invention is used for synthesizing alkylene carbonate, and has the characteristics of small catalyst dosage, high activity and high selectivity.
Description
Technical Field
The invention relates to the technical field of preparation of alkylene carbonate, in particular to a catalyst for synthesizing alkylene carbonate, a preparation method and application thereof.
Background
Alkylene carbonates such as ethylene carbonate and propylene carbonate are an organic chemical raw material having a wide range of uses, and are widely used as solvents and diluents in industry. Ethylene carbonate can be used as solvent in textile, printing, polymer synthesis and electrochemistry, and can also be used as raw material of cosmetics and medicines and intermediate of corresponding dihydric alcohol.
Alkylene carbonates are generally prepared industrially by reacting carbon dioxide with the corresponding alkylene oxide in the presence of a catalyst. Many catalysts have been found to have catalytic effects on this reaction, such as transition metal complexes, main group element complexes, quaternary ammonium salts, quaternary phosphonium salts and alkali metal salts, ionic liquids, supercritical carbon dioxide, and like catalytic systems.
Kim et al investigated the effect of homogeneous catalytic systems of zinc halide with 1-alkyl-3-methyl-imidazolium halide and phosphine-containing ligands on the reaction of carbon dioxide with alkylene oxides (Angew. Chem. Int. Ed.39 (2000) 4096-4098, chem. Eur. J.9 (2003) 678-686, J. Catalyst. 232 (2005) 80-84). After the reaction, the homogeneous catalyst needs to be separated from the product, and the alkylene carbonate can be severely decomposed by separating the product from the homogeneous catalyst by distillation.
Disclosure of Invention
In order to solve the problems of low catalyst activity and low selectivity in the prior art, a catalyst for synthesizing alkylene carbonate, a preparation method and application thereof are provided. The catalyst is used in the process of synthesizing alkylene carbonate, and has the characteristics of small catalyst dosage, high activity and high selectivity.
The first aspect of the invention provides a catalyst for synthesizing alkylene carbonate, which is a supported piperazine catalyst and has the following structural general formula:
A-CH 2 -C 4 H 10 RN 2 + X - ；
wherein the active center component in the catalyst is piperazine unit, and the part in the structural general formula is:
-C 4 H 10 RN 2 + ；
r is hydrogen, methyl, ethyl, propyl, butyl, aryl, nonyl or hexadecyl;
x is selected from fluorine, chlorine, bromine, iodine, acetate, formate, hydrogen oxalate, methyl, ethyl, propyl or butyl;
a is a catalyst carrier.
In the above technical scheme, the carrier A in the catalyst is one or more of polymer, oxide and molecular sieve. Wherein the high polymer can be at least one selected from chloromethylated polystyrene resin, chloromethylated polyacrylic resin and chloromethylated phenolic resin; the oxide may be at least one selected from alumina and the like; the molecular sieve may be selected from at least one of the group consisting of silica-alumina molecular sieves.
In the technical scheme, the mass content of the active center component in the catalyst is 0.1-50%, preferably 20-45%, and more preferably 36-45%.
In the above technical scheme, in the structural general formula of the catalyst, R is preferably hydrogen, methyl, ethyl, propyl or butyl, and X is preferably chlorine, bromine, iodine, methyl, ethyl, propyl or butyl.
The second aspect of the present invention provides a method for preparing the above catalyst for synthesizing alkylene carbonate, comprising: the catalyst is prepared by mixing and reacting a carrier, an active center component precursor and an organic solvent.
In the technical scheme, the preparation method of the catalyst for synthesizing alkylene carbonate specifically comprises the following steps:
(1) Dispersing a carrier in a solvent to obtain a mixed material;
(2) Adding an active center component precursor into the mixed material obtained in the step (1) to react;
(3) And (3) filtering the reaction solution obtained in the step (2), and drying to obtain the catalyst.
In the technical scheme, the carrier in the catalyst is one or more of high polymer, oxide and molecular sieve.
In the above technical scheme, preferably, the mass content of the active center component in the catalyst is 0.1% -50%, and preferably 1% -40%.
In the above technical scheme, the solvent in the step (1) is one or more of toluene, methanol, ethanol, N-propanol, N-butanol, isobutanol, tert-butanol, toluene, dichloromethane, chloroform, N-dimethylformamide and N, N-dimethylacetamide.
In the above technical scheme, the active center component precursor in the step (2) may be dissolved in a solvent, and then added into a reaction system, where the solvent may be one or more of toluene, methanol, ethanol, N-propanol, N-butanol, isobutanol, tert-butanol, toluene, dichloromethane, chloroform, N-dimethylformamide, and N, N-dimethylacetamide.
In the above technical scheme, preferably, the mass ratio of the carrier, the solvent and the active center component precursor is 1:1-10:0.1-5.
In the above technical scheme, preferably, the active center component precursor in the preparation step is one or more of piperazine unit-containing compounds, preferably one or more of piperazine, 1-methylpiperazine, 2-methylpiperazine, N-ethylpiperazine, piperazine-N, N' - (2-ethanesulfonic acid), 1- (2-dimethylaminoethyl) piperazine and N, N-dimethylpiperazine.
In the technical scheme, the reaction conditions of the step (2) are as follows: the reaction temperature is 10-200 ℃, the reaction pressure is 0.1-10.0 megapascals, and the reaction time is 1-24 hours.
In the above technical solution, the apparatus for mixing and reacting is not limited, and may be any apparatus capable of implementing mixing or reacting existing in the art, for example, the apparatus for mixing and reacting may be a reactor or a reaction kettle.
In the above technical solution, the filtering and drying in the step (3) is not limited, and any existing filtering and drying method can be used. The drying temperature is preferably 60-150 deg.c, and the drying temperature is exemplified as 100 deg.c in the embodiment of the present invention, but the present invention is not limited thereto. The drying time is not particularly limited as long as the solvent can be removed, and those skilled in the art can appropriately select the drying time according to the actual situation.
In the above-mentioned technical scheme, in the step (3), the filtered solid may or may not be washed, and preferably the washing is performed. In the present invention, the washing in the step (3) is not limited as long as the purpose of washing can be achieved.
The third aspect of the invention also provides a method for preparing alkylene carbonate by using alkylene oxide and carbon dioxide, which takes alkylene oxide and carbon dioxide as raw materials and contacts and reacts with the catalyst in the first aspect or the second aspect to obtain alkylene carbonate.
In the above technical scheme, the alkylene oxide is preferably ethylene oxide, and the alkylene carbonate is ethylene carbonate.
In the technical scheme, the reaction temperature is 60-180 ℃; and/or the reaction pressure is 0.1-10.0 MPa; and/or the reaction time is 1-24h; and/or the mass ratio of the catalyst to the alkylene oxide is 0.001 to 0.1:1.
the catalyst for synthesizing the alkylene carbonate provided by the invention adopts the novel supported piperazine catalyst, the active sites are uniformly dispersed, the coordination capacity of the active center component and the carrier is strong, the active center component is not easy to run off, the catalyst is used for synthesizing the alkylene carbonate, particularly for synthesizing the ethylene carbonate, the catalyst has the advantages of outstanding high activity and high selectivity, and the catalyst is easy to separate in a reaction system. Particularly, the ethylene oxide conversion rate can reach 98.5 percent and the ethylene carbonate selectivity can reach 99.8 percent after the reaction is carried out for 5 hours under the conditions of 120 ℃ and 6MPa, thereby obtaining remarkable technical effects.
The preparation method provided by the invention has the advantages of simple route, good product selectivity and environmental friendliness.
Detailed Description
The technical scheme of the invention is further illustrated by examples below, but the protection scope of the invention is not limited by the examples. In the invention, the weight percent is the mass fraction.
In the invention, C EO Represents the conversion of ethylene oxide, S EC Representing the selectivity of ethylene carbonate.
[ example 1 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 80 ℃, 100g of piperazine is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S1 is obtained, wherein R is hydrogen, and X is chlorine.
[ example 2 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 80 ℃, 100g of 1-methylpiperazine is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S2 is obtained, wherein R in the structural formula is methyl, and X is chlorine.
[ example 3 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 80 ℃, 100g of N-ethylpiperazine is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S3 is obtained, wherein R is ethyl, and X is chlorine.
[ example 4 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 100 ℃, 100g of 1-methylpiperazine is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S4 is obtained, wherein R in the structural formula is methyl, and X is chlorine.
[ example 5 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of toluene solution, the mixture is stirred and heated to 80 ℃, 100g of 1-methylpiperazine is added for reaction for 7 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S5 is obtained, wherein R in the structural formula is methyl, and X is chlorine.
[ example 6 ]
100g of chloromethylated polystyrene resin is taken and dispersed in 200ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 80 ℃, 80g of 1-methylpiperazine is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water and drying overnight, and the catalyst S6 is obtained, wherein R in the structural formula is methyl, and X is chlorine.
Comparative example 1
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, stirred and heated to 80 ℃, 100g of imidazole is added, after reaction is carried out for 5 hours, the reaction is cooled to room temperature, after filtering to obtain a solid sample, washing with excessive ethanol, washing with water, and drying overnight, thus obtaining the catalyst C1.
Comparative example 2
100g of chloromethylated polystyrene resin is taken and dispersed in 400ml of N, N-dimethylformamide solution, the mixture is stirred and heated to 80 ℃, 100g of 1-methylimidazole is added, the reaction is cooled to room temperature after 5 hours of reaction, the solid sample is obtained after filtration, and the catalyst C2 is obtained after washing with excessive ethanol, washing with water and drying overnight.
[ example 7 ]
The catalyst samples prepared in examples 1-6 above were used for the reaction of ethylene oxide and carbon dioxide, respectively, under the following conditions: under the protection of inert gas, 50.0 g of ethylene oxide and 2.0 g of catalyst are added into a 300 ml autoclave, and 1.0MPa of CO is filled 2 Heating to 120deg.C, and charging CO 2 Maintaining the reaction pressure at 3.0MPa, taking a liquid sample after reacting for 5 hours, analyzing on a chromatograph, and measuring the conversion rate C of the ethylene oxide EO And ethylene carbonate Selectivity S EC The specific results are shown in Table 1.
[ comparative example 3 ]
The catalysts of comparative examples 1 to 2 were used in evaluating the reaction, respectively, by changing the catalyst samples used as compared with example 7, and the catalytic reaction of ethylene oxide and carbon dioxide was performed under the same reaction conditions as those of [ example 7 ], and the obtained reaction results are shown in Table 1.
Table 1 catalytic properties of the catalysts obtained in examples and comparative examples
Claims (8)
1. The catalyst for synthesizing alkylene carbonate is a supported piperazine catalyst and has the following structural general formula:
A-CH 2 -C 4 H 10 RN 2 + X - ；
wherein the active center component in the catalyst is piperazine unit, and the part in the structural general formula is:
-C 4 H 10 RN 2 + ；
r is hydrogen, methyl, ethyl, propyl, butyl, aryl, nonyl or hexadecyl;
x is selected from fluorine, chlorine, bromine, iodine, acetate, formate, hydrogen oxalate, methyl, ethyl, propyl or butyl;
a is a catalyst carrier;
the carrier A in the catalyst is a high polymer; wherein the high polymer is at least one of chloromethylated polystyrene resin, chloromethylated polyacrylic resin and chloromethylated phenolic resin;
the mass content of the active center component in the catalyst is 0.1% -50%.
2. The catalyst according to claim 1, wherein in the structural general formula of the catalyst, R is hydrogen, methyl, ethyl, propyl or butyl, and X is chlorine, bromine, iodine, methyl, ethyl, propyl or butyl.
3. The method for preparing a catalyst for synthesizing alkylene carbonate according to any one of claims 1 to 2, comprising: the catalyst is prepared by mixing and reacting a carrier, an active center component precursor and an organic solvent; the active center component precursor is one or more of piperazine unit-containing compounds.
4. The method according to claim 3, wherein the method for preparing the catalyst for synthesizing alkylene carbonate comprises:
(1) Dispersing a carrier in a solvent to obtain a mixed material;
(2) Adding an active center component precursor into the mixed material obtained in the step (1) to react;
(3) And (3) filtering the reaction solution obtained in the step (2), and drying to obtain the catalyst.
5. The method according to claim 3 or 4, wherein the active center component precursor in the preparation step is one or more of piperazine, 1-methylpiperazine, 2-methylpiperazine, N-ethylpiperazine, piperazine-N, N' - (2-ethanesulfonic acid), 1- (2-dimethylaminoethyl) piperazine, and N, N-dimethylpiperazine.
6. The method according to claim 4, wherein the mass ratio of the carrier, the solvent, and the active center component precursor is 1:1 to 10:0.1 to 5; the reaction conditions of the step (2) are as follows: the reaction temperature is 10-200 ℃, the reaction pressure is 0.1-10.0 megapascals, and the reaction time is 1-24 hours.
7. A method for preparing alkylene carbonate by using alkylene oxide and carbon dioxide as raw materials, and contacting and reacting the alkylene oxide and the carbon dioxide with the catalyst of any one of claims 1-2 or the catalyst prepared by the preparation method of any one of claims 3-6 to obtain the alkylene carbonate.
8. The method according to claim 7, wherein the reaction temperature is 60 to 180 ℃; and/or the reaction pressure is 0.1-10.0 MPa; and/or the reaction time is 1-24h; and/or the mass ratio of the catalyst to the alkylene oxide is 0.001 to 0.1:1.
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