CN118079896A - Tungsten bismuth composite oxide catalyst, preparation and application - Google Patents
Tungsten bismuth composite oxide catalyst, preparation and application Download PDFInfo
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- CN118079896A CN118079896A CN202211503300.2A CN202211503300A CN118079896A CN 118079896 A CN118079896 A CN 118079896A CN 202211503300 A CN202211503300 A CN 202211503300A CN 118079896 A CN118079896 A CN 118079896A
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- bismuth
- composite oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 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 description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- 239000010937 tungsten Substances 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000006104 solid solution Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 238000004809 thin layer chromatography Methods 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 18
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- WNMOIVFBJXRXSY-UHFFFAOYSA-N 5-(hydroxyamino)-5-oxopentanoic acid Chemical compound ONC(=O)CCCC(O)=O WNMOIVFBJXRXSY-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920002415 Pluronic P-123 Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical compound C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 description 1
- VZJFPIXCMVSTID-UHFFFAOYSA-N 2-ethoxy-3,4-dihydro-2h-pyran Chemical compound CCOC1CCC=CO1 VZJFPIXCMVSTID-UHFFFAOYSA-N 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- SFXFPRFVFALOCV-UHFFFAOYSA-N silicon;tetraethyl silicate Chemical compound [Si].CCO[Si](OCC)(OCC)OCC SFXFPRFVFALOCV-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 vinyl diethyl ether Chemical compound 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a tungsten bismuth composite oxide catalyst for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and a preparation method for preparing glutaraldehyde by using the catalyst. The catalyst has good stability, can still keep higher mechanical strength and chemical stability in the long-time reaction process, and has the advantages of simple preparation method, low raw material cost, easy expansion of preparation scale and the like. The catalyst of the invention is used in the reaction for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, has the advantages of high conversion rate of 1, 2-cyclopentane epoxide, good glutaraldehyde selectivity, high yield, good catalyst stability, easy separation and the like, and has remarkable industrial application value.
Description
Technical Field
The invention relates to the field of solid-liquid heterogeneous catalytic reaction, in particular to a high-efficiency catalyst for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and a preparation method for producing glutaraldehyde by using the catalyst.
Background
Glutaraldehyde (GA for short), colorless or pale yellow oily liquid with pungent smell, is easily dissolved in water and ethanol, is dissolved in benzene, is nonflammable and nonvolatile, and is unstable in air. Can be oxidized by air at normal temperature, and is easy to undergo condensation, polymerization and other reactions. It is an important saturated straight-chain aliphatic dialdehyde, is an important fine chemical product and intermediate, and has the functions of crosslinking and solidifying protein. Is a high-efficiency low-toxicity sterilizing disinfectant, an excellent leather tanning agent, a color kinescope film hardening agent and an organic synthetic agent, and is widely applied to the fields of biomedical engineering, cell immunology, biochemistry, leather chemistry, histochemistry, microorganism industry, environmental protection and the like.
The existing glutaraldehyde preparation methods mainly comprise a pyridine method, a pyran method, a pentanediol oxidation method, a glutaric acid reduction method, a cyclopentene oxidation method and the like. The earliest method for industrial production is a pyridine method, wherein pyridine is reduced to dihydropyridine, hydroxylamine is used for treatment to obtain glutaric oxime, and finally sodium nitrite and hydrochloric acid are used for converting the glutaric oxime to glutaraldehyde, so that the conversion rate of the method reaches 90%, and the yield is less than 50%. The method has the defects of high raw material consumption, high cost, high pollution, poor product quality and the like, and is eliminated. The pyran method is to synthesize 2-ethoxy-3, 4-dihydropyran by taking acrolein and vinyl diethyl ether as raw materials in a cyclic manner, and then to hydrolyze and open the ring to glutaraldehyde, and has the defects of high raw material cost, long process route and low product yield (for example, patent CN 102066302A). The pentanediol oxidation method has the disadvantages of low control of oxidation depth, low yield, high raw material shortage cost and the like of oxidation reaction although the reaction route is short, so that industrialization is difficult to realize. The glutaric acid method uses the by-product glutaric acid in the adipic acid production process as raw material, palladium as catalyst and tertiary first as auxiliary agent to reduce the glutaric acid into glutaraldehyde, the yield is 55-88%. Compared with the existing pyran method, the cost of the method can be reduced by 20%, but the method has the problem of short service life of the catalyst at present.
The cyclopentene oxidation method is a method which is studied more nowadays and is also a synthetic route with the most development prospect at present. The route for synthesizing glutaraldehyde by catalytic oxidation of cyclopentene mainly comprises an ozone oxidation method, an oxide oxidation method, a cyclopentyl vicinal diol oxidation method, an air oxidation method, a hydrogen peroxide oxidation method and the like, wherein the oxidant is hydrogen peroxide, and has the advantages of low cost, sufficient raw material supply, clean process, short route, mild condition and the like, and has wide development prospect. The process of oxidizing cyclopentene under hydrogen peroxide to synthesize glutaraldehyde is that cyclopentene first reacts to produce 1, 2-epoxycyclopentane, and then the 1, 2-epoxycyclopentane is converted into beta-hydroxycyclopentyl hydroperoxide intermediate product, and beta-hydroxycyclopentyl hydroperoxide is rearranged to glutaraldehyde. The catalysts currently used for this reaction are typically molybdenum-based compounds, tungsten-based compounds, heteropolyacids, complex metal oxides, tungsten-based molecular sieve catalysts which support the active components onto mesoporous molecular sieves, and the like.
In view of the ease of catalyst separation, current research on tungsten-based supported catalysts and tungsten-based molecular sieve catalysts is receiving extensive attention from the scholars. Chinese patent CN1425498 provides a tungsten-containing catalyst loaded by TiO2 microsphere as a carrier through closed crystallization, and the glutaraldehyde yield is up to 69.4 and 60.3 percent at the minimum. Chinese patent CN1680032a discloses a synthesis method of tungsten-based molecular sieve catalyst for preparing glutaraldehyde by selectively catalyzing and oxidizing cyclopentene with hydrogen peroxide as oxidant, which is prepared by introducing active tungsten source in situ into synthesized all-silicon mesoporous molecular sieve skeleton. The yield of the target product glutaraldehyde is 56.9-75.1%, the selectivity of glutaraldehyde is 73.5-82%, the catalytic effect is general, and the activity and selectivity of the catalyst are required to be improved. The template agent TPABr is added in the preparation of the CN110372483A catalyst, the highest yield of glutaraldehyde which is the target product is 87.1 percent, the selectivity of glutaraldehyde is 87.1 percent, the catalytic activity is improved, but the stability of the catalyst is poor, and the activity of the catalyst is obviously reduced after three times of catalyst circulation. Based on the two patents, the patent CN113813986A extends the method of introducing active tungsten source in situ in the skeleton of the full-silicon mesoporous molecular sieve, uses Pluronic P123 triblock polymer E020P070E020 as a template agent, adopts a method of low-temperature long-time crystallization (68-74 h) to prepare a catalyst precursor, and further obtains the tungsten-based molecular sieve catalyst. CN114426468A adopts a three-stage experiment, uses tungsten-based multi-phase catalysts W-SBA-15 (the mass fraction of WO3 is 20-25%, 15-20% and 10-15%) with different acid intensities, and controls the reaction process by adjusting the addition amount of hydrogen peroxide and the concentration of hydrogen peroxide on the surface of the catalyst, thereby improving the reaction selectivity, the conversion rate of cyclopentene is more than 98%, and the glutaraldehyde yield is more than 80%. The method also has the problems of poor stability and high cost of the catalyst of the patent CN 113813986A.
In conclusion, glutaraldehyde is used as an important chemical intermediate and chemical raw material, and the production of glutaraldehyde is always limited by the process conditions and the inefficiency of the catalytic method, so that the yield is not improved in a large scale all the time. The development of an excellent catalyst and an optimal preparation method for preparing glutaraldehyde have very important significance for the development of glutaraldehyde industry and downstream products.
Aiming at the problems of the prior glutaraldehyde preparation system: 1) The heterogeneous catalyst for preparing glutaraldehyde by directly catalyzing and oxidizing cyclopentene has the problems of poor selectivity, low yield, poor stability and the like. 2) There are few reports of preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide. The invention provides a catalyst for preparing glutaraldehyde by catalytic oxidation of a product of olefin epoxidation, namely 1, 2-cyclopentane epoxide, serving as a raw material and a use method thereof, aiming at overcoming the defects of the prior art based on the achievements of the research group in catalyzing olefin epoxidation by using a heterogeneous phase transfer catalyst for years.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a tungsten-bismuth composite oxide catalyst for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide serving as a raw material and a preparation method for producing glutaraldehyde by using the catalyst. The catalyst has good stability, can still keep higher mechanical strength and chemical stability in the long-time reaction process, and has the advantages of simple preparation method, low raw material cost, easy expansion of preparation scale and the like. The catalyst of the invention is used in the reaction for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, has the advantages of high conversion rate of 1, 2-cyclopentane epoxide, good glutaraldehyde selectivity, high yield, good catalyst stability, easy separation and the like, and has remarkable industrial application value.
The tungsten bismuth composite oxide catalyst has the following advantages:
(1) The catalyst is prepared without adding a surfactant (TPABr or Pluronic P123 triblock polymer) in the process, and without a low-temperature long-time crystallization process and without an expensive tetraethyl orthosilicate silicon source. The catalyst has low cost and simple preparation process.
(2) The catalyst is used for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, the conversion rate of the 1, 2-cyclopentane epoxide is more than 94%, and the selectivity of glutaraldehyde is 96% at most.
(3) The molar ratio of hydrogen peroxide to 1, 2-cyclopentane is 1-1.5, preferably 1.1-1.3. The problem of product separation caused by the large excessive use of hydrogen peroxide is avoided. (for example, although the yield of glutaraldehyde in CN113813986A is 89.1% at the highest, the molar ratio of hydrogen peroxide to cyclopentene in the catalytic system is 2:1, and the separation process of excessive hydrogen peroxide has exploded, so that 1 equivalent of calcium hydroxide is needed to be added for removing hydrogen peroxide in the post-treatment
(4) The tungsten-bismuth composite oxide catalyst has good stability, can be recycled for 10 times, and has good catalyst activity and selectivity which are basically unchanged.
The technical proposal of the invention
The preparation method of the tungsten-bismuth composite oxide catalyst comprises the following steps:
(1) Uniformly mixing a precursor of Al 2O3, an aqueous solution of a precursor of SiO 2 and MgO and a dilute nitric acid solution containing bismuth nitrate (the mass concentration range of bismuth nitrate is 10% -50%), and stirring and curing for 2-24 hours at 0-80 ℃ to obtain a uniform colloid solution;
(2) Dropwise adding the prepared sodium tungstate aqueous solution into the colloid solution obtained in the step (1), continuously stirring and aging for 5-24 hours at 20-80 ℃, and spray-drying the obtained solid solution suspension at 200-300 ℃ to obtain a catalyst precursor;
The catalyst precursor is heated or baked at constant temperature of 300-750 deg.c, preferably 400-650 deg.c for 2-20 hr, preferably 2-8 hr.
The precursor of SiO 2 is one or more than two of silica sol, 60-400 mesh (preferably 200-300 mesh) column chromatography silica gel and thin layer chromatography silica gel;
the precursor of MgO is one or more than two of magnesium salts such as magnesium nitrate, magnesium chloride, magnesium hydroxide or magnesium oxide;
The precursor of Al 2O3 is one or more than two of aluminum salts such as aluminum hydroxide, aluminum nitrate or aluminum trichloride;
the adding amount of nitric acid in the step (1) is to keep the pH range of the colloidal solution obtained in the step (1) to be 0.1-3;
In the dilute nitric acid solution containing bismuth nitrate in a certain amount, wherein the mass concentration of bismuth nitrate is 10-50%;
The addition amount of deionized water in the system is required to satisfy the mass fraction of the solid content in the solid solution suspension obtained in the step (2) of 5% -45%, preferably 10% -30%.
The tungsten-bismuth composite oxide catalyst is a silica-based composition containing silica, magnesia, alumina, bismuth oxide and tungsten oxide, and contains silicon in the range of 42 to 80 mol%, magnesium in the range of 4 to 30 mol%, aluminum in the range of 5.5 to 28 mol%, bismuth in the range of 6 to 30 mol% and tungsten in the range of 4.5 to 35 mol% relative to the total molar amount of silicon, magnesium, aluminum, bismuth and tungsten.
The spray drying temperature of the solid solution suspension is 200-320 ℃, preferably 250-300 ℃;
The roasting atmosphere of the catalyst precursor is one or more than two of hydrogen, oxygen, air, nitrogen or argon and the like, and roasting is preferably performed in an air atmosphere; the heating mode can be programmed heating or constant temperature, the temperature is 300-750 ℃, preferably 400-650 ℃, and the roasting time is 2-20h, preferably 2-8h.
The tungsten bismuth composite oxide catalyst prepared by the preparation method is prepared.
The tungsten bismuth composite oxide catalyst is applied to the preparation of glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide.
The tungsten-bismuth composite oxide catalyst is used for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and comprises the following steps: mixing the tungsten-bismuth composite oxide catalyst with a reaction solvent, adding 1, 2-epoxy cyclopentane, adding hydrogen peroxide solution, and preparing glutaraldehyde through catalytic oxidation reaction.
The addition amount of the tungsten-bismuth composite oxide catalyst is 1-10 percent, preferably 1-5 percent of the mass of the 1, 2-cyclopentane epoxide
The molar ratio of hydrogen peroxide to 1, 2-cyclopentane is 1-1.5, preferably 1.1-1.3.
The volume to mass ratio of the solvent to the 1, 2-cyclopentane epoxide is 1.5-8:1 (mL: g), preferably 2-4:1 (mL: g).
The reaction temperature is 25-80 ℃, preferably 25-50 ℃, and the reaction time is 2-12 hours, preferably 2-6 hours;
the reaction solvent is one or more of isopropanol, tertiary amyl alcohol, tertiary butyl alcohol, ethylene glycol monomethyl ether and ethylene glycol.
The catalyst has good stability, can still keep higher mechanical strength and chemical stability in the long-time reaction process, and has the advantages of simple preparation method, low raw material cost, easy expansion of preparation scale and the like. The catalyst of the invention is used in the reaction for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, has the advantages of high conversion rate of 1, 2-cyclopentane epoxide, good glutaraldehyde selectivity, high yield, good catalyst stability, easy separation and the like, and has remarkable industrial application value.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1
(1) In a 250mL round bottom flask, 10g of 30% silica sol (ph=4), 3.0g of aluminum nitrate nonahydrate, 1.96g of magnesium hydroxide and a nitric acid solution containing 4.0g of bismuth nitrate (composed of 3g of concentrated nitric acid with a mass concentration of 65% and 10mL of deionized water and 4.0g of bismuth nitrate), 60mL of deionized water were sequentially added, and the mixture was uniformly mixed, and stirred and aged at 50 ℃ for 20 hours to obtain a uniform colloidal solution (pH range of 1.20).
(2) And (3) dropwise adding a sodium tungstate aqueous solution (prepared from 5.0g of sodium tungstate and 10mL of deionized water) into the colloid solution obtained in the step (1), continuously stirring and aging for 12 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 15.8%) at 270-280 ℃ to obtain a catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 550 ℃ at the speed of 2.5 ℃/min at the beginning of 300 ℃, and the temperature is kept for 3 hours at 550 ℃. Naturally cooling to obtain the SiO 2-MgO-Al2O3-Bi2O3-WO3 -1 (element mol ratio Si: mg: al: W=42.07: 28.32:6.74:8.54: 14.34) tungsten bismuth composite oxide catalyst A.
Example 2
(1) In a 250mL round bottom flask, 10g of 30% silica sol (ph=4), 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a nitric acid solution containing 6.7g of bismuth nitrate (composed of 3g of concentrated nitric acid with a mass concentration of 65% and 20mL of deionized water and 6.7g of bismuth nitrate), 40mL of deionized water were sequentially added, and uniformly mixed, and the mixture was stirred and aged at 60 ℃ for 20 hours to obtain a uniform colloidal solution (pH range of 1.05).
(2) And (3) dropwise adding an aqueous solution of sodium tungstate (prepared from 2.5g of sodium tungstate and 5mL of deionized water) into the colloidal solution obtained in the step (1), continuously stirring and aging for 10 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 18.0%) at 260-270 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 600 ℃ at the speed of 5 ℃/min at the beginning of 300 ℃, and the temperature is kept for 6 hours at 600 ℃. Naturally cooling to obtain the SiO 2-MgO-Al2O3-Bi2O3-WO3 -2 (element mol ratio Si: mg: al: W=54.63:8.75:8.75:18.56:9.31) tungsten bismuth composite oxide catalyst B.
Example 3
(1) In a 250mL round bottom flask, 3g of 200-300 mesh silica gel, 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a nitric acid solution containing 6.7g of bismuth nitrate (composed of 3g of concentrated nitric acid with a mass concentration of 65% and 20mL of deionized water and 6.7g of bismuth nitrate), 50mL of deionized water were sequentially added, uniformly mixed, and the mixture was stirred and cured at 65℃for 24 hours to obtain a uniform colloidal solution (pH range: 1.45).
(2) And (3) dropwise adding an aqueous solution of sodium tungstate (prepared from 2.5g of sodium tungstate and 5mL of deionized water) into the colloidal solution obtained in the step (1), continuously stirring and aging for 20 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 18.0%) at 260-270 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 600 ℃ at the speed of 10 ℃/min at the beginning of 300 ℃, and the temperature is kept for 4 hours at 600 ℃. Naturally cooling to obtain SiO 2-MgO-Al2O3-Bi2O3-WO3 -3 (element mol ratio Si: mg: al: W=54.63:8.75:8.75:18.56:9.31) tungsten bismuth composite oxide catalyst C.
Example 4
(1) In a 250mL round bottom flask, 20g of 30% silica sol (ph=4), 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a nitric acid solution containing 3.35g of bismuth nitrate (composed of 5g of concentrated nitric acid with a mass concentration of 65% and 10mL of deionized water and 3.35g of bismuth nitrate) were sequentially added, 30mL of deionized water was uniformly mixed, and the mixture was stirred and aged at 40 ℃ for 20 hours to obtain a uniform colloidal solution (pH range of 0.55).
(2) And (3) dropwise adding an aqueous solution of sodium tungstate (prepared from 3.76g of sodium tungstate and 8mL of deionized water) into the colloidal solution obtained in the step (1), continuously stirring and aging for 10 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 21.3%) at 260-270 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 700 ℃ at the speed of 8 ℃/min at the beginning of 300 ℃, and the temperature is kept for 5 hours at 700 ℃. Naturally cooling to obtain the SiO 2-MgO-Al2O3-Bi2O3-WO3 -4 (element mol ratio Si: mg: al: W=72.82: 5.83:6.18: 9.33) tungsten bismuth composite oxide catalyst D.
Comparative example 1
(1) To a 100mL round bottom flask, 20g of 30% silica sol (ph=4), 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a dilute nitric acid solution (composed of 5g of 65% strength by mass concentrated nitric acid and 10mL of deionized water) were sequentially added, 30mL of deionized water was uniformly mixed, and the mixture was stirred and aged at 40 ℃ for 20 hours to obtain a uniform colloidal solution. (pH range 0.45)
(2) And (3) dropwise adding an aqueous solution of sodium tungstate (prepared from 3.76g of sodium tungstate and 8mL of deionized water) into the colloidal solution obtained in the step (1), continuously stirring and aging for 10 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 18.10%) at 260-270 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 600 ℃ at the speed of 2.5 ℃/min at the beginning of 300 ℃, and the temperature is kept for 3 hours at 600 ℃. After natural cooling, a tungsten-based composite oxide catalyst D1 of SiO 2-MgO-Al2O3-WO3 -comparative example 1Cat (elemental molar ratio Si: mg: al: w=77.62:6.21:6.22:9.95) was obtained.
Comparative example 2
(1) In a 250mL round bottom flask, 20g of 30% silica sol (ph=4), 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a nitric acid solution containing 3.35g of bismuth nitrate (composed of 5g of concentrated nitric acid with a mass concentration of 65% and 10mL of deionized water and 3.35g of bismuth nitrate) were sequentially added, 30mL of deionized water was uniformly mixed, and the mixture was stirred and aged at 40 ℃ for 20 hours to obtain a uniform colloidal solution (pH range of 0.55).
(2) And (3) dropwise adding a sodium tungstate aqueous solution (prepared from 1.2g of sodium tungstate and 8mL of deionized water) into the colloid solution obtained in the step (1), continuously stirring and aging for 10 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 18.9%) at 260-270 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 3 hours at 300 ℃, the temperature is raised to 600 ℃ at the speed of 2.5 ℃/min at the beginning of 300 ℃, and the temperature is kept for 3 hours at 600 ℃. After natural cooling, a SiO 2-MgO-Al2O3-Bi2O3-WO3 -comparative example 2 Cat.(molar ratio of elements Si: mg: al: W=77.76:6.23:6.23:6.60:3.18) tungsten bismuth composite oxide catalyst D2 was obtained.
Example 5
(1) In a 100mL round bottom flask, 20g of 30% silica sol (ph=2), 3.0g of aluminum nitrate nonahydrate, 2.05g of magnesium nitrate hexahydrate and a nitric acid solution containing 3.35g of bismuth nitrate (composed of 2.5g of concentrated nitric acid with a mass concentration of 65% and 5mL of deionized water and 3.35g of bismuth nitrate), 10mL of deionized water were sequentially added, uniformly mixed, and the mixture was stirred and aged at 80 ℃ for 20 hours to obtain a uniform colloidal solution (pH range of 0.95).
(2) And (3) dropwise adding an aqueous solution of sodium tungstate (prepared from 3.76g of sodium tungstate and 8mL of deionized water) into the colloidal solution obtained in the step (1), continuously stirring and aging for 10 hours at 50 ℃, and spray-drying the obtained solid solution suspension (with the solid content of 31.5%) at the temperature of 250-260 ℃ to obtain the catalyst precursor. The solid is placed in a tube furnace, programmed to be heated and roasted under nitrogen, the temperature is raised to 300 ℃ at the speed of 2.25 ℃/min at the beginning of 30 ℃, the temperature is kept for 5 hours at 300 ℃, the temperature is raised to 500 ℃ at the speed of 2.5 ℃/min at the beginning of 300 ℃, and the temperature is kept for 5 hours at 500 ℃. Naturally cooling to obtain the SiO 2-MgO-Al2O3-Bi2O3-WO3 -5 (element mol ratio Si: mg: al: W=72.82: 5.83:6.18: 9.33) tungsten bismuth composite oxide catalyst E.
Example 6
Application example of tungsten bismuth composite oxide catalyst in preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide:
0.2g of the tungsten-bismuth composite oxide catalyst of the above examples and comparative examples is added into a 150mL three-necked flask, solvent tert-butyl alcohol (30 mL) is added, the mixture is uniformly mixed under stirring, 10g of 1, 2-cyclopentane is then added, 8.9g of 50% hydrogen peroxide is slowly added dropwise at the reaction temperature of 35 ℃, the dropwise addition reaction time is controlled to be 120min, and the temperature of the reaction system is maintained to be 35+/-3 ℃ in the dropwise addition process. After the completion of the dropwise addition, the reaction was continued at 35℃for 6 hours, and the result of the reaction was determined by gas chromatography. The experimental results are shown in the following table:
Example 7
Application example of tungsten bismuth composite oxide catalyst in preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide: influence of solvent
0.15G of the tungsten-bismuth composite oxide catalyst B of the example 2 is added into a 150mL three-necked flask, a solvent (30 mL) is added, the mixture is uniformly mixed under stirring, 10g of 1, 2-cyclopentane is added, 8.9g of 50% hydrogen peroxide is slowly added dropwise at the reaction temperature of 50 ℃, the dropwise addition reaction time is controlled to be 120min, and the temperature of a reaction system is maintained to be 50+/-3 ℃ in the dropwise addition process. After the completion of the dropwise addition, the reaction was continued at 50℃for 6 hours, and the result of the reaction was determined by gas chromatography. The experimental results are shown in the following table:
Example 8
Application example of tungsten bismuth composite oxide catalyst in preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide: catalyst dosage
0.25G of the tungsten-bismuth composite oxide catalyst B of the example 2 is added into a 150mL three-necked flask, a tertiary butanol solvent (30 mL) is added, the mixture is uniformly mixed under stirring, 10g of 1, 2-epoxy cyclopentane is added, 8.9g of 50% hydrogen peroxide is slowly added dropwise at the reaction temperature of 30 ℃, the dropwise addition reaction time is controlled to be 120min, and the temperature of a reaction system is maintained to be 30+/-3 ℃ in the dropwise addition process. After the completion of the dropwise addition, the reaction was continued at 30℃for 8 hours, and the result of the reaction was determined by gas chromatography. The experimental results are shown in the following table:
Example 9
Application example of tungsten bismuth composite oxide catalyst in preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide: cyclic reaction
0.25G of the tungsten-bismuth composite oxide catalyst B of the example 2 is added into a 150mL three-necked flask, a tertiary butanol solvent (40 mL) is added, the mixture is uniformly mixed under stirring, 10g of 1, 2-epoxy cyclopentane is added, 8.9g of 50% hydrogen peroxide is slowly added dropwise at the reaction temperature of 40 ℃, the dropwise addition reaction time is controlled to be 120min, and the temperature of a reaction system is maintained to be 40+/-3 ℃ in the dropwise addition process. After the completion of the dropwise addition, the reaction was continued at 40℃for 8 hours, and the result of the reaction was determined by gas chromatography.
Catalyst recycling post-treatment method: after the reaction, the reaction solution is cooled to room temperature, the tungsten-bismuth composite oxide catalyst B is filtered, washed three times with 5mL of tertiary butanol, and dried in vacuum at 40 ℃ for 5 hours, and is directly used for the next circulation reaction.
The experimental results are shown in the following table:
From the above table, the catalyst can still maintain good catalytic activity after 10 times of circulation, and the corresponding yield of the catalyst is 88.5%, which indicates that the catalyst has good phase stability and can still maintain high mechanical strength and chemical stability in the long-time reaction process.
Claims (10)
1. The preparation method of the tungsten-bismuth composite oxide catalyst is characterized by comprising the following steps of:
(1) Uniformly mixing a precursor of Al 2O3, an aqueous solution of a precursor of SiO 2 and MgO and a dilute nitric acid solution containing bismuth nitrate (the mass concentration range of bismuth nitrate is 10% -50%), and stirring and curing for 2-24 hours at 0-80 ℃ to obtain a uniform colloid solution;
(2) Dropwise adding the prepared sodium tungstate aqueous solution into the colloid solution obtained in the step (1), continuously stirring and aging for 5-24 hours at 20-80 ℃, and spray-drying the obtained solid solution suspension at 200-300 ℃ to obtain a catalyst precursor;
The catalyst precursor is heated or baked at constant temperature of 300-750 deg.c, preferably 400-650 deg.c for 2-20 hr, preferably 2-8 hr.
2. The preparation method according to claim 1, wherein the precursor of SiO 2 is selected from one or more of silica sol, 60-400 mesh (preferably 200-300 mesh) column chromatography silica gel, and thin layer chromatography silica gel;
the precursor of MgO is one or more than two of magnesium salts such as magnesium nitrate, magnesium chloride, magnesium hydroxide or magnesium oxide;
The precursor of Al 2O3 is one or more than two of aluminum salts such as aluminum hydroxide, aluminum nitrate or aluminum trichloride.
3. The method for producing a tungsten bismuth composite oxide catalyst as claimed in claim 1, characterized in that,
The adding amount of nitric acid in the step (1) is to keep the pH range of the colloidal solution obtained in the step (1) to be 0.1-3;
In the dilute nitric acid solution containing bismuth nitrate in a certain amount, wherein the mass concentration of bismuth nitrate is 10-50%;
The addition amount of deionized water in the system is required to satisfy the mass fraction of the solid content in the solid solution suspension obtained in the step (2) of 5% -45%, preferably 10% -30%.
4. The production method according to claim 1, wherein the tungsten-bismuth composite oxide catalyst is a silica-based composition containing silica, magnesia, alumina, bismuth oxide and tungsten oxide, and contains silicon in a range of 42 to 80 mol%, magnesium in a range of 4 to 30 mol%, aluminum in a range of 5.5 to 28 mol%, bismuth in a range of 6 to 30 mol%, and tungsten in a range of 4.5 to 35 mol% with respect to the total molar amount of silicon, magnesium, aluminum, bismuth and tungsten.
5. The method according to claim 1, wherein,
The spray drying temperature of the solid solution suspension is 200-320 ℃, preferably 250-300 ℃;
The roasting atmosphere of the catalyst precursor is one or more than two of hydrogen, oxygen, air, nitrogen or argon and the like, and roasting is preferably performed in an air atmosphere; the heating mode can be programmed heating or constant temperature, the temperature is 300-750 ℃, preferably 400-650 ℃, and the roasting time is 2-20h, preferably 2-8h.
6. A tungsten bismuth composite oxide catalyst prepared by the preparation method of any one of claims 1 to 5.
7. Use of the tungsten bismuth composite oxide catalyst as claimed in claim 6 in the preparation of glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide.
8. The use according to claim 7, wherein the tungsten bismuth composite oxide catalyst is used for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and comprises the following steps: mixing the tungsten-bismuth composite oxide catalyst with a reaction solvent, adding 1, 2-epoxy cyclopentane, adding hydrogen peroxide solution, and preparing glutaraldehyde through catalytic oxidation reaction.
9. Use according to claim 7 or 8, characterized in that:
The addition amount of the tungsten-bismuth composite oxide catalyst is 1-10 percent, preferably 1-5 percent of the mass of the 1, 2-cyclopentane epoxide
The molar ratio of hydrogen peroxide to 1, 2-cyclopentane is 1-1.5, preferably 1.1-1.3.
The volume to mass ratio of the solvent to the 1, 2-cyclopentane epoxide is 1.5-8:1 (mL: g), preferably 2-4:1 (mL: g).
10. Use according to claim 7 or 8, characterized in that the reaction temperature is 25-80 ℃, preferably 25-50 ℃, for a reaction time of 2-12 hours, preferably 2-6 hours; the reaction solvent is one or more of isopropanol, tertiary amyl alcohol, tertiary butyl alcohol, ethylene glycol monomethyl ether and ethylene glycol.
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