CN113908828B - Bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, and preparation method and application thereof - Google Patents
Bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, and preparation method and application thereof Download PDFInfo
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims abstract description 36
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 23
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 155
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 108
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 37
- 238000004817 gas chromatography Methods 0.000 description 34
- 238000007789 sealing Methods 0.000 description 34
- 150000002118 epoxides Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- NYEWDMNOXFGGDX-UHFFFAOYSA-N 2-chlorocyclohexan-1-ol Chemical compound OC1CCCCC1Cl NYEWDMNOXFGGDX-UHFFFAOYSA-N 0.000 description 2
- 241001292396 Cirrhitidae Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention belongs to the technical field of heterogeneous catalysts, and relates to a bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, a preparation method and application thereof. The bismuth molybdate catalyst is obtained by crystallizing a mixed aqueous solution of bismuth nitrate and ammonium molybdate in a hydrothermal kettle with a polytetrafluoroethylene lining, and then washing and drying the mixture. The bismuth molybdate catalytic material is firstly applied to multiphase catalytic reaction of cyclohexene catalytic oxidation of cyclohexene oxide, bismuth nitrate is used as a precursor in an aqueous solution system, ammonium molybdate is used as a molybdenum source and no other surfactant exists, bismuth molybdate prepared by a hydrothermal method can be used as an efficient catalyst of cyclohexene catalytic oxidation, cyclohexene is specifically used as a substrate, acetonitrile is used as a reaction solvent, a hydrogen peroxide solution is used as an oxidant, the conversion rate of cyclohexene can be up to 77.0%, and the selectivity of cyclohexene oxide can be up to 83.6%.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysts, and particularly relates to a bismuth molybdate catalyst for preparing cyclohexene oxide by cyclohexene epoxidation, a preparation method and application thereof.
Background
The selective oxidation of cyclohexene is a very important catalytic reaction process in the chemical industry. The epoxide epoxy cyclohexane is an important organic chemical intermediate, and further can generate chemical substances with higher added value, such as epoxy resin curing agents, plasticizers, novel acarid pesticides and the like, and plays an important role in the fields of chemical industry, pesticides and the like. With the continued development of the use of epoxycyclohexane, the demand for epoxycyclohexane has also increased rapidly. Currently, the production methods of epoxycyclohexane mainly include chlorohydrin method, halcon method and peracid method. Among them, the traditional chlorohydrin method is dominant, but has the disadvantages of more byproducts, high energy consumption, serious equipment corrosion, and serious environmental pollution, and generates a large amount of chlorine-containing wastewater. The Halcon method has overlarge investment, complex production process and market influence on co-products; the peracid method requires the use of expensive peroxy acid, has high raw material cost and has potential safety hazard. The research of new cyclohexene epoxidation path and the development of new catalyst are of great significance in both theoretical research and industrial application.
According to the related reports, there are methods for recovering a small amount of epoxy cyclohexane from byproducts of the technological process of preparing cyclohexanone and cyclohexanol by oxidizing cyclohexane at home and abroad. The patent CN1128143C adopts hydrochloric acid to convert the byproducts into 2-chlorocyclohexanol, then separates low boiling point substances, and then reacts the 2-chlorocyclohexanol with alkali to obtain the epoxycyclohexane product. CN1106784a was separated from cyclohexane oxidation off-cuts by distillation to give epoxycyclohexane. However, these two methods have limited application range and cannot meet the market development requirements.
With the gradual maturity of the technology for preparing cyclohexene by benzene selective hydrogenation, the technology for preparing cyclohexene oxide by cyclohexene catalytic epoxidation is focused on a selective epoxidation catalyst, because the molecule contains one unsaturated C=C double bond and a plurality of active alpha-H, and various oxidation products can be generated. It is well known that a catalytic oxidation system composed of titanium silicalite (TS-1) and hydrogen peroxide has very good catalytic activity and epoxide selectivity in propylene epoxidation reaction, and the byproduct is water, is an environment-friendly catalyst, and solves the problems of complex operation, harsh conditions, environmental pollution and the like in the traditional process. The successful application of the catalyst in industrial production is known as a milestone in the field of zeolite catalytic oxidation. However, when the system is applied to the process of preparing the cyclohexene oxide by oxidizing the cyclohexene, the defects of lower cyclohexene conversion rate, lower target product yield and the like still exist.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the bismuth molybdate catalyst for preparing the cyclohexene oxide by cyclohexene epoxidation, and the preparation method and application thereof. The bismuth molybdate catalyst is prepared from bismuth nitrate and ammonium molybdate serving as raw materials through a hydrothermal method, and has high catalytic activity and selectivity for cyclohexene epoxidation.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
the preparation method of the bismuth molybdate catalyst for preparing the cyclohexene oxide by cyclohexene epoxidation comprises the following steps: crystallizing the mixed aqueous solution of bismuth nitrate and ammonium molybdate in a hydrothermal kettle with a polytetrafluoroethylene lining, and then washing and drying to obtain the bismuth molybdate catalyst, which is named Bi 2 MoO 6 。
Further, the preparation method of the mixed aqueous solution of bismuth nitrate and ammonium molybdate comprises the following steps: bismuth nitrate is dissolved in distilled water to obtain bismuth precursor solution, and then ammonium molybdate is added, and fully stirred and mixed.
Further, the specific washing method is to obtain Bi 2 MoO 6 The samples were washed three times with distilled water and absolute ethanol, respectively, and then suction filtered using a vacuum pump.
Further, the drying temperature was 100℃and the drying time was 8 hours.
The bismuth molybdate catalyst prepared by the method is used for preparing the cyclohexene oxide by selectively catalyzing cyclohexene epoxidation.
The method specifically comprises the following steps:
weighing a set amount of bismuth molybdate catalyst in a reaction tube, then adding a solvent, a reactant cyclohexene and an oxidant hydrogen peroxide solution, and completing an epoxidation catalytic reaction at a reaction temperature to prepare the cyclohexene oxide.
In the technical proposal, the dosage of the hydrogen peroxide solution is 0.2 to 0.5ml H 2 O 2 Cyclohexene/ml, preferably 0.3ml H 2 O 2 Cyclohexene/ml.
Further, the solvent is any one or more of ethanol, methanol, acetonitrile, dimethyl sulfoxide and N, N-dimethylformamide, preferably acetonitrile;
further, the olefin epoxidation reaction conditions were: the reaction temperature is 50-70 ℃ and the reaction time is 0.5-3 h. More preferably, the olefin epoxidation reaction conditions are: the reaction temperature is 60 ℃ and the reaction time is 2 hours.
Further, the amount of bismuth molybdate catalyst is 0.1 to 1.5g/ml cyclohexene. Preferably, the bismuth molybdate catalyst is used in an amount of 1.0g/ml cyclohexene.
Compared with the prior art, the invention has the following beneficial effects: the bismuth molybdate catalytic material is firstly applied to multiphase catalytic reaction of cyclohexene catalytic oxidation of cyclohexene oxide, bismuth nitrate in the aqueous solution system is used as a precursor, ammonium molybdate is used as a molybdenum source, and bismuth molybdate prepared by a hydrothermal method can be used as an efficient catalyst of cyclohexene catalytic oxidation reaction in the absence of other surfactants. In the process of preparing cyclohexene by using the bismuth molybdate in the epoxidation catalysis of cyclohexane, cyclohexene is used as a substrate, acetonitrile is used as a reaction solvent, a hydrogen peroxide solution is used as an oxidant, the conversion rate of cyclohexene can be up to 77.0%, and the selectivity of cyclohexene oxide can be up to 83.6%.
Drawings
FIG. 1 is an XRD diffraction pattern of BMO-1, BMO-2 and BMO-3 catalytic materials synthesized in examples of the invention.
FIG. 2 shows the apparent morphology of bismuth molybdate catalytic materials (from left to right: BMO-1, BMO-2, BMO-3) prepared by different synthesis methods.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
for catalytic reaction data analysis, the reaction solution was analyzed on an Agilent 7890B gas chromatograph equipped with a hydrogen ion flame detector and an HP-5 capillary column. Quantitative determination is carried out by a peak area normalization method, and evaluation indexes such as conversion rate of reactants, selectivity of products and the like are calculated on the basis of the quantitative determination.
In the invention, the calculation formula of cyclohexene conversion rate is as follows:
the selectivity of the epoxycyclohexane is calculated as follows:
the yield of epoxycyclohexane is calculated as follows:
Y=xxSix100%(3)
x is the conversion of cyclohexene, S i For selectivity to product cyclohexene oxide, w 0 For the initial mass fraction of cyclohexene added, w 1 Is the mass fraction (mol) of unreacted cyclohexene, w i The mass fraction of the cyclohexene oxide is the product.
The preparation method of the bismuth molybdate catalyst suitable for efficiently catalyzing cyclohexene epoxidation reaction comprises the following steps: dissolving bismuth precursor in distilled water to obtain bismuth precursor solution, adding ammonium molybdate, fully stirring, transferring the mixed solution into a hydrothermal kettle with polytetrafluoroethylene lining for crystallization, and washing and drying to obtain bismuth molybdate catalyst. The invention will be further illustrated with reference to the following specific examples, which are not intended to limit the same.
EXAMPLES 1-3 Synthesis of different bismuth molybdate materials
Example 1: 1.214g Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml of distilled water, and 0.22g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Adding O into the solution, stirring thoroughly, and Bi(NO 3 ) 3 ·5H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The molar ratio of O is 14:1, transferring the mixed solution into a hydrothermal kettle with a polytetrafluoroethylene lining, carrying out static reaction for 8 hours at 160 ℃, cooling to room temperature, washing with distilled water and absolute ethyl alcohol for three times respectively, carrying out suction filtration by a vacuum pump, and finally placing a sample obtained by suction filtration in a 100 ℃ oven for drying for 12 hours to obtain a yellow powder solid bismuth molybdate catalytic material, wherein the yellow powder solid bismuth molybdate catalytic material is marked as BMO-1.
Example 2: 0.72g Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml of ethylene glycol, and 0.18g of Na was weighed 2 MoO 4 ·2H 2 Adding O into the above solution, stirring thoroughly, adding Bi (NO 3 ) 3 ·5H 2 O and Na 2 MoO 4 ·2H 2 The molar ratio of O is 2:1, transferring the mixed solution into a hydrothermal kettle with polytetrafluoroethylene lining, carrying out static reaction for 8 hours at 160 ℃, cooling to room temperature, washing with distilled water and absolute ethyl alcohol for three times respectively, carrying out suction filtration by a vacuum pump, and finally placing a sample obtained by suction filtration in a 100 ℃ oven for drying for 12 hours to obtain a yellow powder solid bismuth molybdate material, and marking as BMO-2.
Example 3: 3.7g Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 20ml of distilled water, and 0.66g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 1.2g cetyl ammonium bromide (CTAB) surfactant, and Bi (NO) 3 ) 3 ·5H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The molar ratio of O is 14:1, transferring the mixed solution into a hydrothermal kettle with polytetrafluoroethylene lining, carrying out static reaction for 8 hours at 160 ℃, cooling to room temperature, washing with distilled water and absolute ethyl alcohol for three times respectively, carrying out suction filtration by a vacuum pump, and finally placing a sample obtained by suction filtration in a 100 ℃ oven for drying for 12 hours to obtain a yellow powder solid bismuth molybdate material, and marking as BMO-3.
FIG. 1 shows the synthesis of bismuth molybdate by the method of examples 1-3XRD pattern, typical diffraction peaks at 2θ=27.98 °, 32.30 °, 46.60 °, 55.34 ° for all materials, with pure orthorhombic gamma-Bi 2 MoO 6 The characteristic peaks of crystals (JCPDS 21-0102) are identical. The diffraction intensity of BMO-1 was significantly higher than BMO-2 and BMO-3, indicating that the crystallinity of BMO-1 was relatively high.
Examples 1-3 SEM photographs of the synthesized bismuth molybdate are shown in fig. 2. Three bismuth molybdates were randomly assembled from a number of nanoplatelets, but with a slight difference in thickness and size. The thickness of the nano-sheets of the BMO-1 sample is slightly larger than that of the BMO-3 sample, and the particle size of the BMO-2 is smaller than that of the BMO-1 and BMO-3 samples with the nano-sheets being similar in size.
EXAMPLES 4-6 different bismuth molybdate catalytic Properties
The prepared bismuth molybdate catalyst is subjected to catalytic epoxidation performance evaluation, and the specific process is as follows: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of bismuth molybdate catalyst, and after sealing, setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 4: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 5: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-2 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 6: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-3 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 4-6 are summarized in Table 1, which shows that catalyst BMO-1 has higher catalytic activity and epoxide yield.
Table 1: examples 4-6 catalyst Performance test results
EXAMPLES 7-13 oxidant screening
Example 7: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 20.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 8: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 25.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 9: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 10: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 35.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 11: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 50.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 12: to a reaction tube having a volume of 10mL, 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene as a reactant, and 0.1mL of t-butyl hydroperoxide (TBHP) solution were sequentially added, and finally 0.1g of BMO-1 catalyst was added, and after sealing, the reaction temperature was set to 60℃and the reaction time to 2 hours under stirring. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 13: in a reaction tube with a volume of 10mL, 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of di-tert-butyl peroxide are sequentially added, and finally 0.1g of BMO-1 catalyst is added, and after sealing, the reaction temperature is set to be 60 ℃ and the reaction time is set to be 2h under a stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 7-13 are summarized in Table 2, and it is clear from the Table that the catalyst BMO-1 has higher catalytic activity and epoxide yield in a hydrogen peroxide solution with a mass concentration of 30.0%.
Table 2: examples 7-13 catalyst Performance test results
Examples 14-19 screening for reaction temperatures
Example 14: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 40 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 15: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 50 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 16: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 55 ℃ and the reaction time to 2h under a stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 17: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 18: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 65 ℃ and the reaction time to 2h under a stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 19: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 70 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 14-19 are summarized in Table 3, which shows that catalyst BMO-1 has higher catalytic activity and epoxide yield at 60 ℃.
Table 3: results of catalyst Performance test of examples 14-19
Examples 20-25 screening for reaction time
Example 20: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ and the reaction time to 0.5h under the stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 21: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 1h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 22: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ and the reaction time to 1.5h under the stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 23: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 24: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ and the reaction time to 2.5h under the stirring state. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 25: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 3h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 20-25 are summarized in Table 4, which shows that catalyst BMO-1 has higher catalytic activity and epoxide yield at a reaction time of 2 hours.
Table 4: examples 20 to 25 catalyst Performance test results
Examples 26 to 30 screening of reaction solvents
Example 26: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of ethanol solvent, 0.1mL of reactant cyclohexene and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 27: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of methanol solvent, 0.1mL of reactant cyclohexene and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 28: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of dimethyl sulfoxide solvent, 0.1mL of reactant cyclohexene and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion rate, the selectivity and the yield are analyzed by adopting gas chromatography
Example 29: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of N, N-dimethylformamide solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion rate, the selectivity and the yield are analyzed by adopting gas chromatography
Example 30: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 26-30 are summarized in Table 5, which shows that catalyst BMO-1 has higher catalytic activity and epoxide yield in acetonitrile solvent.
Table 5: results of catalyst Performance test examples 26-30
Examples 31-36 screening for catalyst amounts
Example 31: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.01g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion rate, the selectivity and the yield are analyzed by adopting gas chromatography
Example 32: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.05g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion rate, the selectivity and the yield are analyzed by adopting gas chromatography
Example 33: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.075g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 34: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.1g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 35: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.125g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
Example 36: in a reaction tube with the volume of 10mL, sequentially adding 1.0mL of acetonitrile solvent, 0.1mL of cyclohexene reactant and 0.1mL of hydrogen peroxide solution with the mass concentration of 30.0%, finally adding 0.15g of BMO-1 catalyst, sealing, and setting the reaction temperature to 60 ℃ under a stirring state, wherein the reaction time is 2h. After the reaction is completed, the conversion, selectivity and yield are analyzed by gas chromatography.
The results of the catalytic performance of examples 31-36 are summarized in Table 6, which shows that the catalyst BMO-1 used in an amount of 0.1g has a high catalytic activity and epoxide yield.
Table 6: results of catalyst Performance test examples 31-36
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (3)
1. A method for preparing cyclohexene oxide by cyclohexene epoxidation is characterized by comprising the following steps: the method comprises the following steps:
weighing a set amount of bismuth molybdate catalyst in a reaction tube, then adding solvent acetonitrile, reactant cyclohexene and oxidant hydrogen peroxide solution, and completing epoxidation catalytic reaction at the reaction temperature to prepare the epoxycyclohexane;
the dosage of the hydrogen peroxide solution is 0.2-0.5 mLH 2 O 2 cyclohexene/mL;
the reaction temperature is 50-70 ℃ and the reaction time is 0.5-3 h;
the dosage of the bismuth molybdate catalyst is 0.1-1.5g/mL cyclohexene;
the preparation method of the bismuth molybdate comprises the following steps: crystallizing the mixed aqueous solution of bismuth nitrate and ammonium molybdate in a hydrothermal kettle with a polytetrafluoroethylene lining, and then washing and drying to obtain the bismuth molybdate catalyst, which is named Bi 2 MoO 6 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of bismuth nitrate to ammonium molybdate is 14:1.
2. the method for preparing cyclohexene oxide by cyclohexene epoxidation according to claim 1, wherein: the washing method is to obtain Bi 2 MoO 6 Washing the sample for three times by using distilled water and absolute ethyl alcohol respectively, and then carrying out suction filtration by using a vacuum pump;
and/or the drying temperature is 100 ℃ and the drying time is 8 hours.
3. The method for preparing cyclohexene oxide by cyclohexene epoxidation according to claim 1, wherein: the hydrogen peroxide solution was used in an amount of 0.3mL H 2 O 2 cyclohexene/mL;
and/or, the olefin epoxidation reaction conditions are: the reaction temperature is 60 ℃ and the reaction time is 2 hours;
and/or the bismuth molybdate catalyst is used in an amount of 1.0g/mL cyclohexene.
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CN108993581A (en) * | 2018-07-13 | 2018-12-14 | 浙江大学 | Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application |
CN111217771A (en) * | 2020-02-15 | 2020-06-02 | 中山大学惠州研究院 | Method for directly epoxidizing propylene and molecular oxygen |
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CN108993581A (en) * | 2018-07-13 | 2018-12-14 | 浙江大学 | Load type metal polyoxy hydrochlorate hybrid catalyst and its preparation method and application |
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