CN116351470A - Preparation method of heterogeneous catalyst for transesterification reaction - Google Patents
Preparation method of heterogeneous catalyst for transesterification reaction Download PDFInfo
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- CN116351470A CN116351470A CN202310198347.0A CN202310198347A CN116351470A CN 116351470 A CN116351470 A CN 116351470A CN 202310198347 A CN202310198347 A CN 202310198347A CN 116351470 A CN116351470 A CN 116351470A
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- resin
- oxalate
- acetate
- ethanol
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- 238000005809 transesterification reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 217
- 229920005989 resin Polymers 0.000 claims abstract description 217
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 186
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 230000008961 swelling Effects 0.000 claims abstract description 17
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 15
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 10
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims abstract description 6
- WRHHVVPVKLLPFT-UHFFFAOYSA-N 2-o-ethyl 1-o-methyl oxalate Chemical compound CCOC(=O)C(=O)OC WRHHVVPVKLLPFT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 50
- -1 alkyl oxalate Chemical compound 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 17
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 8
- 239000001639 calcium acetate Substances 0.000 claims description 8
- 235000011092 calcium acetate Nutrition 0.000 claims description 8
- 229960005147 calcium acetate Drugs 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 235000011056 potassium acetate Nutrition 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 7
- 235000011285 magnesium acetate Nutrition 0.000 claims description 7
- 239000011654 magnesium acetate Substances 0.000 claims description 7
- 229940069446 magnesium acetate Drugs 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- CZTUASLUYCFZKL-UHFFFAOYSA-N 2-o-butyl 1-o-methyl oxalate Chemical compound CCCCOC(=O)C(=O)OC CZTUASLUYCFZKL-UHFFFAOYSA-N 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 79
- 239000003054 catalyst Substances 0.000 abstract description 77
- 238000001914 filtration Methods 0.000 abstract description 58
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 40
- 238000005406 washing Methods 0.000 abstract description 29
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 abstract description 16
- 150000003901 oxalic acid esters Chemical group 0.000 abstract description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003456 ion exchange resin Substances 0.000 abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 62
- 238000005303 weighing Methods 0.000 description 43
- 239000002245 particle Substances 0.000 description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 239000002243 precursor Substances 0.000 description 21
- 238000001291 vacuum drying Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000002386 leaching Methods 0.000 description 13
- 239000002585 base Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000005956 quaternization reaction Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 4
- YVWNBNDYTKPZFP-UHFFFAOYSA-N 2-oxo-2-phenoxyacetic acid Chemical compound OC(=O)C(=O)OC1=CC=CC=C1 YVWNBNDYTKPZFP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LJCNULUFLCOAKC-UHFFFAOYSA-N 1-o-methyl 2-o-phenyl oxalate Chemical compound COC(=O)C(=O)OC1=CC=CC=C1 LJCNULUFLCOAKC-UHFFFAOYSA-N 0.000 description 1
- RYLRGNGCJUEKEM-UHFFFAOYSA-N C1CCCCC1.C1(=CC=CC=C1)C(=O)C Chemical compound C1CCCCC1.C1(=CC=CC=C1)C(=O)C RYLRGNGCJUEKEM-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ULOZDEVJRTYKFE-UHFFFAOYSA-N diphenyl oxalate Chemical compound C=1C=CC=CC=1OC(=O)C(=O)OC1=CC=CC=C1 ULOZDEVJRTYKFE-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- 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
- B01J31/08—Ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a heterogeneous catalyst for transesterification, which comprises the steps of drying and dehydrating conventional ion exchange resin containing chloridion and polymerized styrene and divinylbenzene, and swelling in alcohol solution to obtain a resin matrix; the resin matrix is mixed with a modifier containing acetate and ethanol solution to react, and the efficient heterogeneous catalyst for oxalate exchange reaction is obtained after filtration, washing and drying. The catalyst is near neutral anion exchange resin with acetate as a key active group, and has the advantages of high efficiency, stability, difficult inactivation, easy separation from a reaction system and the like in catalyzing dimethyl oxalate and ethanol or butanol to synthesize methyl ethyl oxalate, diethyl oxalate and dibutyl oxalate.
Description
Technical Field
The invention belongs to the technical field of catalysis in chemical industry, and particularly relates to a preparation method of a heterogeneous catalyst for transesterification.
Background
Ethylene glycol consumption in China is dominant in Asia and is the largest ethylene glycol consumption market worldwide. With the rapid development of the coal chemical industry, the technology of preparing ethylene glycol from synthesis gas by dimethyl oxalate (DMO) has been rapidly developed. The homogenization competition of the domestic coal-to-ethylene glycol technology is serious, so that the overall operation rate of the coal-to-ethylene glycol is lower than 30%, the price of the ethylene glycol is continuously low, the price of the ethylene glycol is reduced to 3700 yuan/ton at present, and the profitability of the coal-to-ethylene glycol technology is greatly weakened. Therefore, there is an urgent need to widen the downstream industry of ethylene glycol, develop a synthesis process for designing a downstream product with high added value by taking DMO as a platform compound, develop a coal-to-ethylene glycol industrial chain with multiple ends, and make development of a large amount of downstream ethylene glycol or a product with high added value unnecessary.
Alkyl oxalate is an important organic chemical raw material, and is widely used for preparing various dyes, medicines, important solvents, extractants and various intermediates. Can carry out various condensation reactions with fatty acid esters, cyclohexane acetophenone, amino alcohols and a plurality of heterocyclic compounds. The oxalic acid alkyl ester can be hydrolyzed to prepare oxalic acid, and the oxalic acid is widely used in national defense, electronics, medicine, materials, agriculture, light industry, chemical industry and other industries; the alkyl oxalate can be further hydrogenated to prepare ethylene glycol which is used for producing synthetic fibers, unsaturated polyester resin and plastic films in large quantity, and is also used for adhesives, solvents and plasticizers in fine chemical engineering; the oxalic acid alkyl ester can be ammonified by normal pressure ammonification to produce high-quality slow-release high-efficiency fertilizer oxamide, and is used in the agricultural field. Industrially, the synthesis method of the oxalic acid alkyl ester mainly comprises two main types of traditional oxalic acid esterification method and carbon monoxide oxidative coupling method. Among them, oxalic acid esterification is a technique introduced and optimized from abroad in the 50 th century, and the reaction thereof needs to consume a large amount of oxalic acid, is easy to generate side reaction, has the defects of serious corrosiveness and easy environmental pollution to equipment, and is difficult to meet the requirements of modern industrial development. The oxidative coupling method of carbon monoxide is a novel technology discovered by Stein wand et al in the mid-sixties and adopts PdCl 2 -CuCl 2 Redox catalysts, which are extremely susceptible to poisoning and deactivation, limit the large-scale application of the process. The method for preparing the alkyl oxalate by the transesterification method has simple process, can realize that the corresponding alkyl oxalate product can be obtained in one step, and is a high added value route for preparing the alkyl oxalate.
In the process of preparing alkyl oxalate by the transesterification method, the catalyst is a key for determining whether the reaction is successful or not. Patent CN 1583254A discloses a molybdenum oxide catalyst for synthesizing phenyl oxalate by transesterification and a preparation method thereof, and the catalyst for synthesizing phenyl oxalate by transesterification is obtained by adopting a slurry impregnation method through the steps of preparing molybdenum trioxide slurry, grinding a carrier, mixing with the slurry, impregnating, drying and the like. Patent CN 1986517A discloses a method for synthesizing methyl phenyl oxalate and diphenyl oxalate by catalyzing with composite carrier supported metal oxide, which uses titanium dioxide as carrier and metal oxide as active component, thus realizing the preparation of composite carrier supported metal oxide catalyst and successfully using in transesterification reaction to prepare phenyl oxalate. Patent CN 111672493A discloses an alkaline mesoporous catalyst, a preparation method and application thereof, and realizes the preparation of mesoporous magnesium oxide catalyst with large specific surface, large aperture, high alkali content and middle alkali center. The patents CN 109081779A, CN 112279762A, CN 112279763A, CN 112279762A, CN 114292182A and CN 112961057A all disclose processes for preparing alkyl oxalate by transesterification, and the processes all adopt catalysts in the early stage of alkyl oxalate synthesis to promote transesterification, however, the catalytic activity and selectivity of alkyl oxalate achieved at present are different from those of large-scale industrial production, and the difficulty of separating the catalyst from the system is accompanied, so that further development of a catalyst system with good catalytic activity, higher selectivity, convenient preparation and easy separation is still needed.
The ion exchange resin is a polymer compound with functional groups (active groups for exchanging ions), a network structure and insolubility. Generally spherical particles, and pore structures are divided into two types, namely gel type and macroporous type, and have two main types of cation exchange resins belonging to acidity and anion exchange resins belonging to alkalinity. In organic synthesis, acid and alkali are commonly used as catalysts for esterification, hydrolysis, transesterification, hydration and other reactions. The ion exchange resin can be used to replace inorganic acid and alkali, and the reaction can be carried out similarly, and the advantages are more. If the resin can be repeatedly used, the product is easy to separate, the reactor can not be corroded, the environment is not polluted, the reaction is easy to control, and the like. However, the strong-alkaline ion exchange resin is extremely easy to deactivate when catalyzing the oxalate exchange reaction, and the efficiency is low when catalyzing the oxalate exchange reaction by the strong-acid resin, so that the development of the ion exchange with high activity and high stability simultaneously has challenges.
Disclosure of Invention
According to one aspect of the application, a preparation method of a heterogeneous catalyst for transesterification is provided, and aiming at the phenomena that a strong-alkaline anion exchange resin is easy to deactivate and a strong-acid cation exchange resin is low in catalytic efficiency in the process of synthesizing oxalic ester, the application provides a preparation method of a near-neutral anion exchange resin taking acetate as a key active group, and the synthesized heterogeneous anion exchange resin has the advantages of high efficiency, stability, difficult deactivation, easiness in separation from a reaction system and the like in catalyzing dimethyl oxalate and ethanol or butanol to synthesize methyl oxalate, diethyl oxalate and dibutyl oxalate.
The application adopts the following technical scheme:
a method for preparing a heterogeneous catalyst for transesterification reactions, comprising the steps of:
s1, placing exchange resin containing chloride ions in alcohol for swelling to obtain a resin matrix;
s2, mixing the resin matrix obtained in the step S1 with a modifier containing acetate and a solvent, and reacting to obtain the heterogeneous catalyst for transesterification.
Optionally, the chloride ion-containing exchange resin is a chloride ion-containing exchange resin which is dried at 100-120 ℃ for 5-10 hours.
Optionally, the exchange resin containing chloride ions is prepared by the following preparation method:
placing the strong-alkaline anion exchange resin in hydrochloric acid, and stirring and reacting for 1-5h to obtain the exchange resin containing chloride ions;
the concentration of the hydrochloric acid is 0.1-0.6 mol/L;
the alkali content of the strong-alkali anion exchange resin is 10-30wt%.
The alkali content in the strong base anion exchange resin is selected from any value of 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, or a range between any two.
Optionally, the exchange resin containing chloride ions is prepared by the following preparation method: and placing the strong-alkali anion exchange resin in hydrochloric acid, and stirring and reacting for 1-5h to weak acidity to obtain the exchange resin containing chloride ions.
The active group in the strong alkaline anion exchange resin is hydroxyl.
Optionally, washing the product after the stirring reaction with water, washing with ethanol, filtering and drying to obtain the exchange resin containing chloride ions.
Optionally, the content of chloride ions in the chloride ion-containing exchange resin is 20-40 wt%
Alternatively, the chloride ion content of the chloride ion-containing exchange resin is selected from any of 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, or a range therebetween.
Optionally, the molar ratio of the acetate to the chloride ions in the exchange resin containing the chloride ions is 1-3:1.
Optionally, the molar ratio of acetate to chloride in the chloride ion-containing exchange resin is selected from any of 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, or a range of values therebetween.
Optionally, the weight ratio of the ethanol to the exchange resin containing the chloride ions is 2-4:1.
Optionally, the weight ratio of the acetate to the solvent is 1:10-30.
Optionally, the weight ratio of acetate to solvent is any value selected from 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1:24, 1:26, 1:28, 1:30, or a range of values therebetween.
Optionally, the weight ratio of the ethanol to the chloride ion-containing exchange resin is selected from any of 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, or a range of values therebetween.
Optionally, in the step S2, the reaction conditions are as follows: stirring for 10-15 h at 20-30 ℃.
Optionally, the acetate is at least one selected from potassium acetate, sodium acetate, magnesium acetate, calcium acetate, zinc acetate, copper acetate and manganese acetate.
Optionally, the chloride ion-containing exchange resin is selected from at least one of a strongly basic anion resin containing chloride ions, a weakly basic anion resin containing chloride ions, and a transformation of an anion resin containing chloride ions.
Optionally, the solvent is selected from at least one of methanol, ethanol, and water.
Optionally, the step S2 further comprises the steps of washing the product with water and alcohol after the reaction, and then vacuum drying at 70-90 ℃ for 5-12 hours to obtain the heterogeneous catalyst for transesterification.
Optionally, the step S2 further comprises the steps of washing the product with water for 2-3 times, washing with alcohol for 2-3 times, filtering, and then drying in vacuum at 70-90 ℃ for 5-12 hours to obtain the heterogeneous catalyst for transesterification.
According to another aspect of the present application, there is provided the use of a heterogeneous catalyst for transesterification prepared according to the preparation method described above in the directional synthesis of alkyl oxalate by transesterification.
Optionally, the transesterification reaction comprises a reaction of catalyzing at least one raw material of alcohol compounds and ester compounds to perform transesterification with oxalic ester to synthesize alkyl oxalate by using a heterogeneous catalyst for transesterification.
Optionally, the alcohol compound is at least one selected from ethanol and butanol.
Optionally, the ester compound is at least one selected from dimethyl oxalate, diethyl oxalate and dibutyl oxalate.
Optionally, the alkyl oxalate is at least one selected from diethyl oxalate, methyl ethyl oxalate, dibutyl oxalate and methyl butyl oxalate.
Optionally, the weight ratio of the heterogeneous catalyst for transesterification to the oxalate is 0.001-0.1:1.
Optionally, the weight ratio of the heterogeneous catalyst for the transesterification reaction to the oxalic ester is 0.04-0.06:1.
Alternatively, the transesterification conditions are: the reaction temperature is 60-140 ℃, and the reaction pressure is 10-50 KPa.
Alternatively, the reaction temperature in the condition of the transesterification reaction is selected from any value in 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ or a range value between any two.
The beneficial effects that this application can produce include:
the preparation method of the heterogeneous catalyst for the transesterification reaction has the advantages of no roasting in the preparation process, simple process, good comprehensive performance of the catalyst, environmental protection, easiness in separation of a reaction system and the like, and is a novel catalyst for synthesizing the alkyl oxalate by a transesterification method.
Description of the embodiments
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
Wherein, the solvents of methanol and ethanol are all commercial analytical pure solvents, and the purity is more than or equal to 99.5 percent.
The exchange resins containing chloride ions are commercially available and can be prepared as follows:
weighing commercial strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali density is 0.25 mmol/g), and placing the commercial strong-base anion exchange resin in a drying oven for drying, wherein the required drying temperature is 100-120 ℃, and the required drying time is 5-10 h, so as to obtain the dried resin; weighing the dry resin, placing the dry resin in HCl solution with a certain concentration, and fully stirring the dry resin to be slightly acidic at room temperature, wherein the stirring time is 1-5h, and the solubility of the used hydrochloric acid solution is 0.05-0.2 mol/L; and then washing with water, washing with ethanol, filtering, drying and the like to obtain the chloridized exchange resin containing chloride ions.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 11.61 g potassium acetate and 155 g ethanol solution, respectively adding into a beaker, stirring until the potassium acetate and the 155 g ethanol solution are completely dissolved, and preparing a potassium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 11.66 g, placing the wet resin into a vacuum drying oven, drying the wet resin in the vacuum drying oven at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin h, and standing the wet resin to obtain the modified resin catalyst of 9.05 g at the room temperature, wherein the catalyst is named as catalyst No. 1.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 17.82 g calcium acetate and 500 g ethanol solution, respectively adding into a beaker, stirring until the calcium acetate and the 500 g ethanol solution are completely dissolved, and preparing a calcium acetate modifier solution B with a certain concentration; mixing the solution A1 and the solution B completely and stirring the mixture continuously at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 8.76 g, placing the wet resin in a vacuum drying oven, drying the wet resin in the vacuum drying oven at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin h, and standing the resin catalyst at the room temperature to obtain the modified resin catalyst of 6.75 g, wherein the catalyst is named as catalyst No. 2.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 9.24 g sodium acetate and 130 g ethanol solution, respectively adding into a beaker, stirring until the sodium acetate and the ethanol solution are completely dissolved, and preparing sodium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 11.10 g, placing the wet resin into a vacuum drying oven, drying the wet resin in the vacuum drying oven at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin h, and standing the wet resin to obtain the modified resin catalyst of 8.61 g at the room temperature, wherein the catalyst is named as catalyst No. 3.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 24.16 g magnesium acetate and 339 g ethanol solution, respectively adding into a beaker, stirring until the magnesium acetate and the 339 g ethanol solution are completely dissolved, and preparing magnesium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 11.37 g, placing the wet resin into a vacuum drying oven, drying the wet resin in the vacuum drying oven at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin h, and standing the wet resin to obtain the modified resin catalyst of 8.53 g at the room temperature, wherein the catalyst is named as catalyst No. 4.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 20.67 and g zinc acetate and 290 and g ethanol solution, respectively adding into a beaker, and stirring until the zinc acetate and the 290 and g ethanol solution are completely dissolved to prepare zinc acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 10.69 g, placing the wet resin in a vacuum drying oven, drying the wet resin in the vacuum drying oven at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin at the drying temperature of 12h, and standing the resin catalyst at the room temperature to obtain the modified resin catalyst of 8.29 g, wherein the catalyst is named as catalyst No. 5.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 22.5 g copper acetate and 315 g ethanol solution, respectively adding into a beaker, stirring until the copper acetate and the 315 g ethanol solution are completely dissolved, and preparing a copper acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 10.86 g, placing the wet resin in a vacuum drying oven, drying the wet resin at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin at the drying temperature of 12h, and standing the wet resin at the room temperature to obtain the modified resin catalyst of 8.43 g, wherein the catalyst is named as catalyst No. 6.
Examples
Weighing 40.28 g anion exchange resin (the mature commercial preparation method is that divinylbenzene and styrene are polymerized and then chlorinated and then quaternized, the market brand is many, but the structure is basically consistent, the influence on oxalate exchange reaction is small), drying 10h at 115 ℃ to obtain 22.99 g dehydrated resin matrix, wherein the content of chloride ions in the dehydrated resin matrix is 20wt%; weighing 10 g of dried resin, swelling the resin in 31 g of ethanol solution for 2h to obtain a swollen resin matrix A1; weighing 19.5 g manganese acetate and 273 g ethanol solution, respectively adding into a beaker, stirring until the manganese acetate and the 273 g ethanol solution are completely dissolved, and preparing manganese acetate modifier solution B with a certain concentration; thoroughly mixing the solution A1 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture to obtain wet resin 10.35 g, placing the wet resin in a vacuum drying oven, drying the wet resin at the drying pressure of 0.08 MPa and the drying temperature of 70 ℃, drying the resin at the drying temperature of 12h, and standing the wet resin at the room temperature to obtain the modified resin catalyst of 8.02 g, wherein the catalyst is named as catalyst No. 7.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, suction filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby.
Weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 13.27 g potassium acetate and 319 g ethanol solution, respectively adding into a beaker, stirring until the potassium acetate and the 319 g ethanol solution are completely dissolved, and preparing a potassium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A2 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by using 200 g deionized water, dissolving the water-washed resin particles by using 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the mixture at the drying temperature of 12h, and standing the mixture at room temperature to obtain the 10.21 g modified resin catalyst which is named as catalyst No. 8.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 21.39 g calcium acetate and 514 g ethanol solution, respectively adding into a beaker, stirring until the calcium acetate and the 514 g ethanol solution are completely dissolved, and preparing a calcium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A2 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by using 200 g deionized water, dissolving the water-washed resin particles by using 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the mixture at the drying temperature of 12h, and standing the mixture at the room temperature to obtain the 7.47 g modified resin catalyst which is named as catalyst No. 9.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 11.09 g sodium acetate and 267 g ethanol solution, respectively adding into a beaker, stirring until the sodium acetate and the 267 g ethanol solution are completely dissolved, and preparing sodium acetate modifier solution B with a certain concentration; thoroughly mixing the solution A2 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the dried mixture at the drying temperature of 12h, and standing the mixture at the room temperature to obtain the resin catalyst of which the modified resin particles are 9.67 g, wherein the catalyst is named as catalyst number 10.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 28.97 g magnesium acetate and 696 g ethanol solution, respectively adding into a beaker, stirring to dissolve completely, and preparing into magnesium acetate modifier solution B with certain concentration; thoroughly mixing the solution A2 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by using 200 g deionized water, dissolving the water-washed resin particles by using 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the dried mixture at the drying temperature of 12h, and standing the mixture at the room temperature to obtain the resin catalyst of which the temperature is 9.92 g, wherein the resin catalyst is named as catalyst No. 11.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 24.81 and g zinc acetate 596 and g ethanol solutions, respectively adding the ethanol solutions into a beaker, and stirring until the ethanol solutions are completely dissolved to prepare zinc acetate modifier solution B with a certain concentration; thoroughly mixing the solution A2 and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by adopting 200 g deionized water, dissolving the water-washed resin particles by adopting 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the dried mixture at the drying temperature of 12h, and standing the mixture at the room temperature to obtain the resin catalyst of 9.89 g modified resin, and the catalyst is named as catalyst No. 12.
Examples
40g of a strongly basic anion exchange resin (a common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization, active groups are hydroxyl, and the alkali content is 10 wt%) is weighed and placed in 600 mL of 0.4 mol/L HCl solution, and the mixture is fully stirred at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 26.97 g copper acetate and 648 g ethanol solution, respectively adding into a beaker, stirring until the copper acetate and the 648 g ethanol solution are completely dissolved, and preparing a copper acetate modifier solution B with a certain concentration; completely mixing the solution A and the solution B, and fully mixing and stirring for 24 hours at room temperature; and then washing with ethanol for 6-8 times, each time for 5min, filtering, placing into a vacuum drying oven, drying at 80 ℃ and 0.08 MPa for 12h, standing at room temperature to obtain a resin catalyst modified by 10.07 and g, and naming the resin catalyst as catalyst No. 13.
Examples
Weighing 40g strong-base anion exchange resin (common commercial resin obtained by polymerization of vinyl benzene and styrene and then quaternization reaction, active groups are hydroxyl, and the alkali content is 10 wt%) and placing the resin in 600 mL of 0.4 mol/L HCl solution, and fully stirring the resin at room temperature for 5h to weak acidity; filtering, washing with ethanol for 2 times, filtering to obtain resin precursor containing chloride ions, and placing in a dryer for standby;
weighing 12 g the resin precursor, swelling the resin precursor in 33 g ethanol solution for 2h to obtain a swelled resin matrix A2; weighing 23.41 g manganese acetate and 562 g ethanol solution, respectively adding into a beaker, stirring until the manganese acetate and the 562 g ethanol solution are completely dissolved, and preparing manganese acetate modifier solution B with a certain concentration; thoroughly mixing the solution A and the solution B and continuously stirring at room temperature for 10 h; and then filtering the modified resin particles, leaching the modified resin particles by using 200 g deionized water, dissolving the water-washed resin particles by using 150 g ethanol, stirring the mixture at room temperature for 30 min, filtering the mixture, repeating the ethanol washing operation for 3 times, filtering the mixture, placing the mixture in a vacuum drying oven, drying the mixture at the drying pressure of 0.08 MPa and the drying temperature of 80 ℃, drying the dried mixture at the drying temperature of 12h, and standing the mixture at the room temperature to obtain the 9.46 g modified resin catalyst which is named as catalyst No. 14.
The catalyst prepared in examples 1 to 14 above was used for the directional synthesis of alkyl oxalate by transesterification, and the evaluation method of the reaction performance was as follows: 100g of dimethyl oxalate (DMO) and 235g of ethanol were charged into a 1L reaction rectifying column, the mixture was stirred sufficiently, the temperature was raised to 80℃and 5g of a catalyst was charged, the reflux ratio was set at 3:1, the reaction was carried out at a reaction temperature of 80℃for 5: 5h, the reaction pressure was 45KPa, and the catalyst performance was examined, and the results are shown in Table 1.
TABLE 1 reactivity of catalysts obtained in examples 1 to 14 for the catalytic directional synthesis of alkyl oxalate
| Experiment number | t/min | X DMO (%) | S MEO (%) | S DEO (%) | Y MEO (%) | Y DEO (%) |
| Catalyst No. 1 | 180 | 94.92 | 5.40 | 94.60 | 5.13 | 89.79 |
| Catalyst No. 2 | 300 | 84.88 | 16.11 | 83.89 | 13.67 | 71.21 |
| Catalyst No. 3 | 180 | 94.85 | 6.40 | 93.60 | 6.07 | 88.78 |
| Catalyst No. 4 | 180 | 93.97 | 5.27 | 94.73 | 4.95 | 89.02 |
| Catalyst No. 5 | 180 | 91.35 | 8.85 | 91.15 | 8.08 | 83.27 |
| Catalyst No. 6 | 180 | 92.85 | 7.38 | 92.62 | 6.85 | 86.00 |
| Catalyst No. 7 | 300 | 88.46 | 10.71 | 89.29 | 9.47 | 78.99 |
| Catalyst No. 8 | 180 | 98.88 | 1.35 | 98.65 | 1.33 | 97.55 |
| Catalyst No. 9 | 300 | 87.17 | 11.73 | 88.27 | 10.23 | 76.94 |
| Catalyst No. 10 | 180 | 94.72 | 6.44 | 93.56 | 6.10 | 88.62 |
| Catalyst No. 11 | 180 | 97.12 | 2.08 | 97.92 | 2.02 | 95.10 |
| Catalyst No. 12 | 180 | 96.85 | 3.34 | 96.66 | 3.23 | 93.62 |
| Catalyst No. 13 | 180 | 98.58 | 2.63 | 97.37 | 2.59 | 95.99 |
| Catalyst No. 14 | 300 | 92.57 | 8.57 | 91.43 | 7.93 | 84.64 |
The catalyst prepared in example 8 was selected and used for the directional synthesis of alkyl oxalate by transesterification, and the reaction performance evaluation method was as follows: in a 1L reaction rectifying column, 100g of dimethyl oxalate and 377g of butanol were charged, stirred sufficiently, heated to 120℃and charged with 5g of a catalyst, the reflux ratio was set at 5:1, the reaction was carried out at a reaction temperature of 120℃under a reaction pressure of 20KPa, and the catalyst performance was examined, and the results are shown in Table 2.
TABLE 2 reactivity of the catalysts obtained in example 8 for the catalytic directed synthesis of alkyl oxalate at different catalytic times
| t/min | X DMO (%) | S MBO (%) | S DBO (%) | Y MBO (%) | Y DBO (%) |
| 5 | 25.94 | 39.51 | 60.49 | 10.25 | 15.69 |
| 30 | 64.91 | 36.41 | 63.59 | 23.63 | 41.28 |
| 60 | 77.37 | 33.85 | 66.15 | 26.19 | 51.18 |
| 120 | 86.11 | 28.98 | 71.02 | 24.96 | 61.15 |
| 180 | 89.12 | 25.24 | 74.76 | 22.49 | 66.63 |
| 300 | 91.10 | 14.03 | 85.97 | 12.78 | 78.32 |
In the above table, X represents conversion, S represents selectivity, and Y represents yield; DMO is dimethyl oxalate, MBO is methyl butyl oxalate, DBO is dibutyl oxalate.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. A process for the preparation of a heterogeneous catalyst for transesterification reactions, comprising the steps of:
s1, placing exchange resin containing chloride ions in ethanol for swelling to obtain a resin matrix;
s2, mixing the resin matrix obtained in the step S1 with a modifier containing acetate and a solvent, and reacting to obtain the heterogeneous catalyst for transesterification.
2. The preparation method according to claim 1, wherein the chloride ion-containing exchange resin is obtained by the following preparation method:
placing the strong-alkaline anion exchange resin in hydrochloric acid, and stirring and reacting for 1-5h to obtain the exchange resin containing chloride ions;
the concentration of the hydrochloric acid is 0.1-0.6 mol/L;
the alkali content of the strong-alkali anion exchange resin is 10-30wt%.
3. The method according to claim 1, wherein the content of chloride ions in the chloride ion-containing exchange resin is 20 to 40wt%.
4. The preparation method according to claim 1, wherein the molar ratio of acetate to chloride ions in the chloride ion-containing exchange resin is 1-3:1;
the weight ratio of the acetate to the solvent is 1:10-30;
preferably, in the step S1, the weight ratio of the ethanol to the exchange resin containing chloride ions is 2-4:1.
5. The method according to claim 1, wherein in the step S2, the reaction conditions are as follows: stirring for 10-15 h at 20-30 ℃.
6. The method according to claim 1, wherein the acetate is at least one selected from the group consisting of potassium acetate, sodium acetate, magnesium acetate, calcium acetate, zinc acetate, copper acetate, and manganese acetate;
preferably, the chloride ion-containing exchange resin is selected from at least one of a strongly basic anion resin containing chloride ions, a weakly basic anion resin containing chloride ions, and a transformation of an anion resin containing chloride ions.
7. The method according to claim 1, wherein the solvent is at least one selected from the group consisting of methanol, ethanol, and water.
8. The application of the heterogeneous catalyst for transesterification, which is prepared by the preparation method according to any one of claims 1-7, in the directional synthesis of alkyl oxalate through transesterification.
9. The use according to claim 8, wherein the transesterification reaction comprises a reaction for transesterifying at least one of the alcohol compound and the ester compound with an oxalic ester to synthesize an alkyl oxalate using a heterogeneous catalyst for transesterification;
preferably, the alcohol compound is at least one selected from ethanol and butanol;
preferably, the ester compound is at least one selected from dimethyl oxalate, diethyl oxalate and dibutyl oxalate;
preferably, the alkyl oxalate is at least one selected from diethyl oxalate, methyl ethyl oxalate, dibutyl oxalate and methyl butyl oxalate.
10. The use according to claim 8, wherein the weight ratio of heterogeneous catalyst for transesterification to oxalate is 0.001-0.1:1;
preferably, the transesterification reaction conditions are: the reaction temperature is 60-140 ℃, and the reaction pressure is 10-50 KPa.
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