CN111974455A - Catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@PC - Google Patents
Catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@PC Download PDFInfo
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- CN111974455A CN111974455A CN202010822716.5A CN202010822716A CN111974455A CN 111974455 A CN111974455 A CN 111974455A CN 202010822716 A CN202010822716 A CN 202010822716A CN 111974455 A CN111974455 A CN 111974455A
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- pcumo
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- cyclooctene
- cyclododecene
- epoxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 28
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 title claims abstract description 27
- 239000004913 cyclooctene Substances 0.000 title claims abstract description 27
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical class O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 9
- HYPABJGVBDSCIT-UHFFFAOYSA-N cyclododecene Chemical compound C1CCCCCC=CCCCC1 HYPABJGVBDSCIT-UHFFFAOYSA-N 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 239000012265 solid product Substances 0.000 claims 2
- RLNDAEAVPRIWSX-UHFFFAOYSA-N C1CCCCC=CCCCCC1.[O] Chemical compound C1CCCCC=CCCCCC1.[O] RLNDAEAVPRIWSX-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- -1 alkyl hydrogen peroxide Chemical compound 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/613—
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- B01J35/633—
-
- B01J35/647—
-
- 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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
-
- 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
Abstract
The invention discloses a catalyst PCuMo for catalyzing oxidation reaction of cyclooctene and cyclododecene11The preparation method of (1). The method comprises the following steps: copper ion substituted phosphomolybdic acid PCuMo11Preparation of (2) and mixing of PCuMo11Obtaining PCuMo on loaded covalent organic framework material PC11A method of @ PC novel composite material; in addition, the invention uses PCuMo11@ PC is used to catalyze the oxygen epoxidation of cyclooctene and cyclododecene. The method has the characteristics of simple operation, economy, environmental protection, good catalytic performance and the like, and the prepared novel composite material PCuMo11@ PC is a highly efficient and environmentally friendly heterogeneous catalyst for olefin epoxidation.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalytic materials, and particularly relates to a preparation method of covalent organic framework material loaded copper ions for replacing phosphomolybdic acid, and cyclooctene and cyclododecene epoxidation reaction are catalyzed.
Background
The epoxy compound is an important intermediate product with wide application in chemical industry, and is widely applied to the fields of medicines, materials, chemical industry and the like. Olefin epoxidation reaction is a main source for producing epoxy compounds, wherein methods such as a halohydrin method and a peracid method are used for synthesizing the olefin epoxy compounds, but the used oxidant has the problems of environmental pollution, equipment corrosion, complex production, low yield, high energy consumption and the like. To ameliorate the above problems, many emerging catalysts have been developed for olefin epoxidation. CN110433826A utilizes a coprecipitation method to prepare a single-atom gold catalyst for catalyzing the epoxidation reaction of styrene by taking air as an oxidant. Although the catalytic performance is good and the stability is good, the gold is expensive and the energy consumption is high; CN110694676A discloses a mesoporous catalyst of TUD-1 doped with lanthanide metal, which can catalyze C in alkyl hydrogen peroxide solution3-C10An alkene or cycloalkene of (a). The preparation process of the catalyst is complex and takes a long time, which is not beneficial to industrial production.
Heteropolyacids are oxygen-containing polyacid green catalysts composed of heteroatoms (such as P, Si, Fe, Co, etc.) and polyatomic atoms (such as Mo, W, V, Nb, Ta, etc.). Because of the unique acidity, quasi-liquid phase behavior, and multiple functions of heteropoly acids, they are widely regarded by researchers in the field of catalytic research and olefin epoxidation. CN106975522A develops a phosphomolybdotungstic heteropoly acid catalyst and catalyzes olefin epoxidation reaction by taking tert-butyl hydroperoxide as an oxidant, wherein the tert-butyl hydroperoxide pollutes the environment and has higher energy consumption.
The invention utilizes cheap and easily-obtained transition metal copper substituted Keggin type phosphomolybdic heteropoly acid to prepare the olefin epoxidation catalyst PCuMo with excellent performance11@ PC, this catalyst can utilize oxygen direct catalysis cyclooctene and cyclododecene, and the preparation process of catalyst is simple, low in production cost and catalysis process green have popularization and application and worth.
Disclosure of Invention
The invention aims to provide a catalyst which is economic and green, is easy to operate and can catalyze the epoxidation reaction of cyclooctene and cyclododecene by taking oxygen as an oxygen source with high efficiency. The catalyst is a heterogeneous catalytic material obtained by taking a micro-mesoporous covalent organic framework material PC as a carrier and immobilizing copper-substituted phosphomolybdic acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11The preparation method of @ PC is realized by the following steps:
(1) preparation of covalent organic framework material PC: dissolving potassium carbonate, cyanuric chloride and anhydrous piperazine into a 1, 4-dioxane solvent, heating the mixture at constant temperature, decompressing and filtering after the reaction is finished, washing a filter cake by acetone, tetrahydrofuran and dichloromethane, and drying in vacuum to obtain yellow powder PC;
(2) copper ion substituted phosphomolybdic acid PCuMo11The preparation of (1): PMo adjustment by addition of saturated sodium bicarbonate solution12The pH of the solution is 4-5, and then the solution is mixed with CuSO4·5H2Mixing O solution, stirring at constant temperature, standing to remove precipitated sodium sulfate impurity, and collecting PCuMo11A crystal;
(3) catalyst PCuMo11Preparation of @ PC: adding PCuMo into uniformly dispersed PC aqueous solution11Heating and stirring the aqueous solution at constant temperature, filtering, washing and drying in vacuum to obtain the novel composite material PCuMo11@PC。
Preferably, in the above-mentioned catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11The preparation method of @ PC comprises the steps of (1) mixing potassium carbonate, cyanuric chloride and anhydrous piperazine at a constant temperature of 100-.
Preferably, in the above-mentioned catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11The preparation method of @ PC, phosphomolybdic acid and CuSO in step (2)4· 5H2The mass ratio of O is 1 (0.5-3), the stirring temperature is constant at 45-50 deg.C, the time is 30-60min, and phosphomolybdic acid and CuSO are further preferably selected4· 5H2The mass ratio of O is 1:3, the stirring temperature is 50 ℃ at constant temperature, and the time is 60 min.
The beneficial effects of the above technical scheme are: the proper increase of the synthesis temperature and the temperature is beneficial to the increase of the product yield, and the CuSO4· 5H2An increased proportion of O increases the yield of phenyloxirane.
The invention also provides a method for applying the epoxidation reaction of cyclooctene and cyclododecene to the composite material of copper ion substituted phosphomolybdic acid loaded on covalent organic framework material PC, which comprises the following steps:
(1) adding catalyst, acetonitrile, isobutyraldehyde and olefin into a double-neck bottle, and introducing molecular oxygen of 10 mL/min. The olefin is cyclooctene and cyclododecene;
(2) the reaction temperature is 40-70 ℃, after a period of reaction, a proper amount of reaction mixture is taken out, filtered by a filter membrane and subjected to gas chromatography detection.
According to the scheme, compared with the prior art, the catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene is provided11The preparation method of the @ PC composite material and the application of the @ PC composite material in the epoxy epoxidation reaction of cyclooctene and cyclododecene have the following advantages:
(1) in the aspect of catalyst preparation, the prepared raw material is economical and easy to obtain, and the catalytic active substance PCuMo11The price is low and the product is easy to get, and the micro-mesoporous carrier PC has rich nitrogen content, so that the copper-substituted phosphomolybdic acid active substance is more firmly loaded;
(2) in the aspect of catalyzing epoxidation reaction of cyclooctene and cyclododecene, cheap, green and environment-friendly oxygen is used as an oxygen source, the catalytic effect is good, and the prepared novel catalyst has high reactivity and selectivity in the epoxidation reaction of cyclooctene and cyclododecene.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 accompanying drawing is the PCuMo of the invention11@ PC.
FIG. 2 is a schematic view of the PCuMo of the present invention11PC and PCuMo11The XRD pattern of @ PC.
FIG. 3 is a drawing showing (a) PC and (b) PCuMo of the present invention11The nitrogen adsorption desorption curve and the pore size distribution diagram of @ PC, and the relevant data are listed in attached Table 1.
FIG. 4 is a drawing showing PC and PCuMo of the present invention11Surface area, pore size and pore volume of @ PC.
FIG. 5 is a schematic view of the PCuMo of the present invention11@ PC catalyzes the evaluation of cyclooctene and cyclododecene.
Detailed Description
In order to make the invention more clear and complete, the following examples are only some examples of the invention, and all equivalent changes and modifications made by the following examples are included in the scope of the present invention.
Example 1
Adding 20 mg PCuMo into a double-neck bottle11@ PC catalyst, 10 mL acetonitrile, 2 mmol cyclooctene and 6 mmol isobutyraldehyde, introducing 10 mL/min oxygen, and reacting at 60 ℃ for 1 h; a small amount of solution is taken out of the flask, filtered by a filter membrane and subjected to gas chromatography, the conversion rate is 98 percent, and the selectivity is>99%。
Example 2
Adding 20 mg PCuMo into a double-neck bottle11@ PC catalyst, 10 mL acetonitrile, 2 mmol cyclododecene and 6 mmol isobutyraldehyde, introducing 10 mL/min oxygen, and reacting at 60 ℃ for 1 h; a small amount of solution is taken out of the flask, filtered by a filter membrane and subjected to gas chromatography, the conversion rate is 95 percent, and the selectivity is>99%。
In addition, the invention also relates to PCuMo11Raw Material of @ PC and PCuMo11The @ PC catalyst is subjected to infrared spectrum test, XRD (X-ray diffraction) and nitrogen adsorption and desorption curves and pore size distribution, refer to figures 1-3, and figure 1 shows the PCuMo in the invention11The infrared spectrogram of @ PC,in the catalyst PCuMo11In @ PC, the main framework structure of the carrier PC is maintained; FIG. 2 shows PCuMo of the present invention11XRD spectrogram of @ PC and catalyst PCuMo11@ PC maintains the main framework structure of the carrier PC; FIG. 3 and Table 1 show PCuMo of the present invention11Compared with the surface area, the pore diameter and the pore volume of the carrier PC, the surface area, the pore diameter and the pore volume of the catalyst PCuMo11@ PC are all reduced, and the result proves that the PCuMo11Has been loaded onto the carrier PC, while at the same time PCuMo11Has chemical interaction with the carrier PC.
The above description is only a preferred embodiment of the present invention, and the raw materials, the ratio of each component, the preparation method, etc. of the catalyst of the present invention are all within the protection and disclosure of the present invention. Equivalents and modifications by way of example are intended to be included within the scope of the present invention.
Claims (9)
1. Catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@ PC ", characterized by comprising the steps of:
(1) preparation of covalent organic framework material PC: dissolving potassium carbonate, cyanuric chloride and anhydrous piperazine into a 1, 4-dioxane solvent, heating the mixture at constant temperature, decompressing and filtering after the reaction is finished, washing a filter cake by acetone, tetrahydrofuran and dichloromethane, and drying in vacuum to obtain yellow powder PC;
(2) copper ion substituted phosphomolybdic acid PCuMo11The preparation of (1): PMo adjustment by addition of saturated sodium bicarbonate solution12The pH of the solution is 4-5, and then the solution is mixed with CuSO4·5H2Mixing O solution, stirring at constant temperature, standing to remove precipitated sodium sulfate impurity, and collecting PCuMo11A crystal;
(3) catalyst PCuMo11Preparation of @ PC: adding PCuMo into uniformly dispersed PC aqueous solution11Heating and stirring the aqueous solution at constant temperature, filtering, washing and drying in vacuum to obtain the novel composite material PCuMo11@PC。
2. According to claim1 the catalyst PCuMo for catalyzing epoxidation reaction of cyclooctene and cyclododecene11@ PC, characterized by: the mass ratio of potassium carbonate, cyanuric chloride and anhydrous piperazine in step (1) is 6:2: 3.
3. The catalyst PCuMo for catalyzing epoxidation of cyclooctene and cyclododecene according to claim 111@ PC, characterized by: in the step (1), the constant-temperature stirring temperature is 100-.
4. The catalyst PCuMo for catalyzing epoxidation of cyclooctene and cyclododecene according to claim 111@ PC, characterized by: the yield of PC in the step (1) is 70-75%.
5. The catalyst PCuMo for catalyzing epoxidation of cyclooctene and cyclododecene according to claim 111@ PC, characterized by: phosphomolybdic acid and CuSO in step (2)4· 5H2The mass ratio of O is 1 (0.5-3).
6. The catalyst PCuMo for catalyzing epoxidation of cyclooctene and cyclododecene according to claim 111@ PC, characterized by: in the step (2), stirring at constant temperature of 45-50 ℃ for 30-60 min.
7. The catalyst PCuMo for catalyzing epoxidation of cyclooctene and cyclododecene according to claim 111@ PC, characterized by: PCuMo in step (3)11The mass ratio of the PC to the solid is 1 (0.5-5), after the reaction is finished, the mixture is separated by vacuum filtration, the solid product is washed by ethanol and deionized water for 3-5 times, and the solid product is dried in vacuum at 80 ℃ for more than 12 hours.
8. A composite material comprising copper ion-substituted phosphomolybdic acid loaded on covalent organic framework material PC prepared by the method of any one of claims 1 to 7.
9. The composite PCuMo material of claim 8, wherein the covalent organic framework material PC is loaded with copper ion-substituted phosphomolybdic acid11The application of @ PC in the epoxidation reaction of cyclooctene and cyclododecene oxygen is characterized in that: the method comprises the following steps:
(1) adding a composite material, acetonitrile, isobutyraldehyde, cyclooctene or cyclododecene, wherein the composite material is prepared by loading copper ion-substituted phosphomolybdic acid serving as a catalyst onto covalent organic framework material PC, and introducing 10 mL/min molecular oxygen into a double-necked bottle, and reacting for 1h at constant temperature of 40-70 ℃ to obtain a mixture;
(2) the appropriate amount of reaction mixture was removed, filtered through a filter membrane and subjected to gas chromatography.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731454A (en) * | 2021-09-22 | 2021-12-03 | 吉林化工学院 | Preparation and catalytic application of nitrogen-doped carbon composite material loaded with heteropoly acid |
| CN113751068A (en) * | 2021-09-22 | 2021-12-07 | 吉林化工学院 | Supported polyoxometallate material for preparing aniline by nitrobenzene hydrogenation |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES316484A1 (en) * | 1964-08-13 | 1965-11-16 | Halcon International Inc | Procedure for the preparation of olefin oxides. (Machine-translation by Google Translate, not legally binding) |
| JP2008179644A (en) * | 2008-02-05 | 2008-08-07 | Daicel Chem Ind Ltd | Method for producing epoxy compound |
| CN107362829A (en) * | 2016-05-13 | 2017-11-21 | 中国科学院大连化学物理研究所 | Covalent organic frame bimetallic catalyst of support type and its preparation method and application |
| CN109317207A (en) * | 2018-11-02 | 2019-02-12 | 吉林化工学院 | It is a kind of to be efficiently recycled olefin epoxidation catalysts and its preparation method and application |
| CN109317206A (en) * | 2018-10-15 | 2019-02-12 | 吉林化工学院 | A kind of epoxidation of styrene catalyst and its preparation method and application |
-
2020
- 2020-08-17 CN CN202010822716.5A patent/CN111974455A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES316484A1 (en) * | 1964-08-13 | 1965-11-16 | Halcon International Inc | Procedure for the preparation of olefin oxides. (Machine-translation by Google Translate, not legally binding) |
| JP2008179644A (en) * | 2008-02-05 | 2008-08-07 | Daicel Chem Ind Ltd | Method for producing epoxy compound |
| CN107362829A (en) * | 2016-05-13 | 2017-11-21 | 中国科学院大连化学物理研究所 | Covalent organic frame bimetallic catalyst of support type and its preparation method and application |
| CN109317206A (en) * | 2018-10-15 | 2019-02-12 | 吉林化工学院 | A kind of epoxidation of styrene catalyst and its preparation method and application |
| CN109317207A (en) * | 2018-11-02 | 2019-02-12 | 吉林化工学院 | It is a kind of to be efficiently recycled olefin epoxidation catalysts and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| SONG XIAOJING 等: "Epoxidation of olefins with oxygen/isobutyraldehyde over transition-metal-substituted phosphomolybdic acid on SBA-15", 《CATALYSIS TODAY》 * |
| XIWEI HU 等: "Two-dimensional covalent organic frameworks as self-template derived nitrogen-doped carbon nanosheets for eco-friendly metal-free catalysis", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 王静: "咪唑功能化有机—无机杂化材料固载磷钼杂多化合物催化剂的制备及烯烃环氧化性能", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
| 高文秀 等: "分子氧环氧化烯烃多相催化剂PCuMo11/富氮类共价有机骨架材料的制备及应用", 《复合材料学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731454A (en) * | 2021-09-22 | 2021-12-03 | 吉林化工学院 | Preparation and catalytic application of nitrogen-doped carbon composite material loaded with heteropoly acid |
| CN113751068A (en) * | 2021-09-22 | 2021-12-07 | 吉林化工学院 | Supported polyoxometallate material for preparing aniline by nitrobenzene hydrogenation |
| CN113731454B (en) * | 2021-09-22 | 2023-05-05 | 吉林化工学院 | Preparation and catalytic application of heteropolyacid-loaded nitrogen-doped carbon composite material |
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