CN109772326A - A kind of catalyst for synthesizing fluorenone and its preparation method and application - Google Patents
A kind of catalyst for synthesizing fluorenone and its preparation method and application Download PDFInfo
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- CN109772326A CN109772326A CN201910196205.4A CN201910196205A CN109772326A CN 109772326 A CN109772326 A CN 109772326A CN 201910196205 A CN201910196205 A CN 201910196205A CN 109772326 A CN109772326 A CN 109772326A
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- Prior art keywords
- fluorenone
- catalyst
- solution
- synthesizing
- reaction
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005751 Copper oxide Substances 0.000 claims abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 23
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-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
- 150000003839 salts Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- QJWQYOHBMUQHGZ-UHFFFAOYSA-N ethanol;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound CCO.OC(=O)CC(O)(C(O)=O)CC(O)=O QJWQYOHBMUQHGZ-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 150000002220 fluorenes Chemical class 0.000 description 35
- 238000007254 oxidation reaction Methods 0.000 description 22
- 239000000047 product Substances 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000008246 gaseous mixture Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229940011182 cobalt acetate Drugs 0.000 description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- BBGVVPLPLBJJLS-UHFFFAOYSA-N copper ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] BBGVVPLPLBJJLS-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- -1 peroxide Chemical compound 0.000 description 3
- BKXAWQXZFFNQHY-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-] BKXAWQXZFFNQHY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VTWKXBJHBHYJBI-SOFGYWHQSA-N (ne)-n-benzylidenehydroxylamine Chemical compound O\N=C\C1=CC=CC=C1 VTWKXBJHBHYJBI-SOFGYWHQSA-N 0.000 description 1
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical group [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- CSAPYPPGLHWJKX-UHFFFAOYSA-N 9h-fluorene;hydrate Chemical class O.C1=CC=C2CC3=CC=CC=C3C2=C1 CSAPYPPGLHWJKX-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- NMEZJSDUZQOPFE-UHFFFAOYSA-N Cyclohex-1-enecarboxylic acid Chemical compound OC(=O)C1=CCCCC1 NMEZJSDUZQOPFE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003005 anticarcinogenic agent Substances 0.000 description 1
- 229940124976 antitubercular drug Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000036461 convulsion Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种合成芴酮的催化剂及其制备方法和应用，属于催化剂技术领域，所述催化剂的活性组分及其质量百分比含量为：四氧化三钴的质量百分比含量为0‑100%，氧化铜的质量百分比含量为0‑100%，四氧化三钴与氧化铜的质量百分比含量之和为100%，通过溶胶凝胶法或者凝胶法制备合成芴酮的催化剂。本发明制备的合成芴酮的催化剂具有成本低、转化率高、选择性高、反应条件温和、稳定性好，反应物易于分离的优点。The invention relates to a catalyst for synthesizing fluorenone, a preparation method and application thereof, and belongs to the technical field of catalysts. The active component of the catalyst and its mass percentage content are as follows: the mass percentage content of cobalt tetroxide is 0-100%, and the content of copper oxide The mass percentage content is 0-100%, the sum of the mass percentage content of cobalt tetroxide and copper oxide is 100%, and the catalyst for synthesizing fluorenone is prepared by a sol-gel method or a gel method. The catalyst for synthesizing fluorenone prepared by the invention has the advantages of low cost, high conversion rate, high selectivity, mild reaction conditions, good stability and easy separation of reactants.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to be it is a kind of synthesize Fluorenone catalyst and preparation method thereof
And application.
Background technique
Fluorenone, molecular formula C13H8O, molecular weight 180.20, be in yellow orthorhombic body, 81-85 DEG C of fusing point, boiling point 341
DEG C, it is not soluble in water, the organic solvents such as alcohol, ether can be dissolved in, are a kind of important fine chemicals raw materials.It is as intermediate in height
The fields such as molecule, dyestuff, medicine, pesticide, optical material have and its important application.In the field of polymers, Fluorenone can be with phenol
Condensation generates bisphenol fluorene, and the fluorene structured thermal stability with higher of bis-phenol is widely used in heat proof material, separation membrane material
Deng, while bisphenol fluorene is also used for the high molecular materials such as epoxy resin, polycarbonate, polymethyl methacrylate (organic glass)
Additive.In dye industry, Fluorenone can be used for synthesizing aromatic diamines dyestuff.Fluorenone can also be used as medicine intermediate, use
Include a variety of drugs such as anticarcinogen, anti-tubercular drug, convulsion relieving agent in synthesis.Pesticide production in, Fluorenone be used to synthesize herbicide,
Insecticide and plant growth regulator etc..
Fluorenone synthesis can be divided into non-fluorene Material synthesis Fluorenone by the difference of raw material and fluorenes oxidation prepares Fluorenone.Non-fluorene raw material closes
It include with diphenic acid, 2,2 '-two lithium biphenyl, benzaldoxime and iodobenzene, 1- cyclohexene -1- carboxylic acid and benzene etc. for original at Fluorenone
Material reacts synthesis Fluorenone by one or more steps.Cost of material used in non-fluorene Material synthesis Fluorenone is higher, partial catalyst
Using noble metal active component, product is complicated, and Part Methods need multistep to complete, and is not suitable for large-scale production Fluorenone.Compared to
Fluorenone is prepared with non-fluorene raw material, fluorenes oxidation prepares Fluorenone raw material and is easy to get, and reaction process is simple, it is only necessary to step oxidation.Fluorenes oxidation system
The technique of standby Fluorenone can be divided into gaseous oxidation and the big reaction system of liquid phase oxidation two.Fluorenes gaseous oxidation prepares Fluorenone using gas-solid
Heterogeneous catalysis system, reaction carry out in fixed bed, and fluorenes is gasified by high temperature and is mixed with oxygen/air, with gaseous
By solid catalyst bed, fluorenes occurs oxidation reaction and obtains Fluorenone form.The method realizes continuous operation, but reaction temperature
Height, and the high requirements on the equipment, the easy coking of process.Liquid phase oxidation reaction temperature is relatively low, is usually made with water or organic solvent
Solvent, oxidant and catalyst are existed simultaneously in system, and common oxidant includes that peroxide, hypervalent iodine compounds etc. are solid
The gaseous oxidizers such as state/liquid oxidizer and air, oxygen.Compared to the liquid/solids oxygen such as peroxide, hypervalent iodine compounds
Agent, the cleaning of the gaseous oxidizers such as air, oxygen is cheap, is easily isolated, with the obvious advantage.Hu Xin etc. is empty using Industrial fluorene as raw material
Gas is oxidant, and potassium hydroxide is catalyst, and pyridine is that solvent has carried out the research that fluorenes oxidation prepares Fluorenone, and the yield of Fluorenone is big
In 98%.For Zhou Jianrong etc. using NaOH as catalyst, dimethyl sulfoxide is solvent, and industrial oxygen is oxidizing content greater than 85%
Industrial fluorene, the conversion ratio of fluorenes are greater than 99%, and the yield of Fluorenone is greater than 96%.Zhao Ming etc. has investigated potassium hydroxide, potassium carbonate, hydroxide
Fluorenes oxidation prepares the performance of Fluorenone on the difference base catalyst such as sodium, sodium carbonate, has studied catalyst amount, solvent type, oxygen
Influence of the factors such as flow, reaction temperature to catalytic perfomance.The result shows that oxygen is oxidation when using NaOH as catalyst
When agent, the conversion ratio of fluorenes is up to 99% or more, and Fluorenone yield is 95% or more.Wang etc. is aoxidized by catalyst of potassium tert-butoxide
Benzyl c h bond prepares ketone, and when using fluorenes as raw material, potassium tert-butoxide is catalyst, and phase transfer catalyst is added simultaneously in reaction system
18- crown- 6, solvent are n,N-Dimethylformamide, and under oxygen pressure 1atm, the yield of Fluorenone reaches 94%.The above liquid phase oxidation
Fado uses alkali catalyst, is also easy to produce alkaline waste liquor, is unfavorable for environmental protection, and part reaction process is since lye and fluorenes are respectively in water phase
With organic phase, also need to promote reaction to carry out using phase transfer catalyst.In addition to using alkali catalyst, there are also part researchs to use
Acid imide substance is as catalyst, and wherein Ishii etc. is with efficient electron carrier n-Hydroxyphthalimide (NHPI)
It for catalyst, is reacted by oxidant of molecular oxygen, the yield of Fluorenone is up to 80%.Miao etc. is with N- hydroxyl phthalyl
Imines and ferric nitrate are catalyst, and oxygen is the oxidation of oxidizer catalytic fluorenes, and the yield of Fluorenone has reached 90%.But such is catalyzed
Agent is homogeneous catalyst, and the separation of post catalyst reaction is difficult, increases the complexity of operation.In addition there are use noble metal living
The reaction system of property component catalyst, such as Majumdar are prepared for Au nano particle-poly-dopamine (Pda)-oxygen reduction fossil
Black alkene (rGO) ternary nano composite material, using 1mmol fluorenes as raw material, Au-Pda-rGO catalyst (Au load capacity is 2wt%) is used
Amount is 0.02g, while the n-Hydroxyphthalimide of 10mol% is added, and 5mL acetonitrile is solvent, O2Pressure is 10bar, is stirred
Rate 1000rpm is mixed, after reaction carries out 15h at 60 DEG C, the conversion ratio of fluorenes is 89.4%, and the selectivity of Fluorenone reaches 97.6%,
Noble metal is as active component although catalytic activity with higher, but it is expensive, causes catalyst higher cost, no
Conducive to the control of production cost.
Summary of the invention
The object of the present invention is to provide a kind of inexpensive, selectivity height, high conversion rate, reaction conditions relatively mildly, stability
It is good, using oxygen as the heterogeneous catalysis and preparation method and application of the fluorenes oxidative synthesis Fluorenone of oxidant.
Catalyst of the invention is aoxidized by the composition metal that active component cobaltosic oxide or copper oxide or both form
Object, consisting of the mass content of cobaltosic oxide is 0-100%, the mass content of copper oxide is 0-100%.
Catalyst preparation of the invention is as follows:
1, the catalyst of synthesis Fluorenone is prepared using sol-gal process: firstly, by cobalt and/or copper according to the active group in catalyst
The precursor ethanol solution or aqueous solution for dividing mass percent to prepare 5-60wt%, while the citric acid ethyl alcohol for preparing 5-60wt% is molten
The volume ratio of liquid or aqueous solution, citric acid solution and precursor solution is 0.5-5, by prepared citric acid ethanol solution or water
Solution is slowly added into prepared precursor ethanol solution or aqueous solution under the conditions of 10-60 DEG C, persistently stirs 2-24h；
Secondly, by the mixed solution of citric acid ethanol solution or aqueous solution and precursor ethanol solution or aqueous solution in 50-90 DEG C of condition
Obtained solid is dried 2-24h by lower stirring, solvent evaporated under the conditions of 50-150 DEG C；Finally, under the conditions of 300-800 DEG C
1-10h is calcined, the catalyst of synthesis Fluorenone is obtained.
Further, the soluble-salt of the metal is acetate or nitrate.
2, the catalyst of synthesis Fluorenone is prepared using the precipitation method:
Firstly, cobalt and copper to be prepared into the soluble-salt of metal respectively；Secondly, according to active component and its quality in catalyst
Degree prepares the precursor water solution of 1-50wt% respectively, while preparing the precipitating reagent aqueous solution of 1-50wt%, by forerunner
Body aqueous solution is slowly added into sky beaker simultaneously under the conditions of 20-80 DEG C, and the pH value that mixed solution is controlled in adding procedure is
7-13, the completely rear aging 1-24h of solution precipitating to be mixed；Again, product that aging obtains is washed with deionized to noresidue
K+Or Na+Until detection, then by obtained product under the conditions of 50-150 DEG C dry 2-24h；Finally, in 300-800 DEG C of condition
Lower calcining 1-10h obtains the catalyst of synthesis Fluorenone.
Further, the soluble-salt of the metal is acetate, chloride, sulfate or nitrate.
Further, the precipitating reagent is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or carbonic acid
Hydrogen potassium.
The application of the catalyst of the synthesis Fluorenone prepared in the present invention is as follows:
Reaction condition are as follows: the fluorenes that mass percentage content is 0.01-50wt% is dissolved in solvent, catalyst is added into solvent,
The mass ratio of catalyst and Fluorenone is 1:0.001-0.5, and atmosphere catalysis is reacted, initial gas pressure 0.1-6MPa, instead
Answering temperature is 60-180 DEG C, reaction time 0.5-24h.
Further, the solvent is acetonitrile, hexamethylene or cyclohexanone.
Further, the catalysis reaction gas atmosphere is the mixing that the oxygen content such as air, oxygen, ozone are 5-100%
Gas.
Further, the oxygen content is including nitrogen or argon gas in the gaseous mixture of 5-100%.
Compared with the prior art, the invention has the following advantages:
1) catalyst preparation process is simple and easy, there is good stability, and repeat performance is excellent；
2) catalyst performance is excellent, as heterogeneous catalysis, easily separates with product, it is easy to accomplish industry amplification；
3) reaction raw materials are cheap and easy to get, product yield high, almost no coupling product, and synthesis process economy is significant；
4) reaction process is simple, easily operated.
Specific embodiment
Embodiment 1:
The cobalt nitrate ethanol solution for preparing 60wt%, by the citric acid ethanol solution of 5wt% (with cobalt nitrate ethanol solution at 60 DEG C
Volume ratio is 5) to be slowly added to, and is kept stirring in the process, continues stirring after dripping at 60 DEG C for 24 hours, then by solution in 90
It is stirred at DEG C, solvent evaporated, for 24 hours, 800 DEG C of calcining 10h obtain cobaltosic oxide catalysis to obtained product for drying at 150 DEG C
Agent.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
50wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.5) is added, oxygen, initial pressure are filled with into reaction kettle
6MPa reacts for 24 hours at 180 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 76%.
Embodiment 2:
The copper nitrate ethanol solution for preparing 5wt%, by the citric acid ethanol solution of 5wt% (with copper nitrate ethanol solution at 10 DEG C
Volume ratio is 0.5) to be slowly added to, and is kept stirring in the process, continues to stir 2h at 10 DEG C after dripping, then by solution in 50
It is stirred at DEG C, solvent evaporated, obtained product dry 2h, 300 DEG C of calcining 1h at 50 DEG C obtain copper oxide catalyst.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
0.01wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.001) is added, oxygen is filled with into reaction kettle, it is initial to press
Power 0.1MPa reacts 0.5h at 60 DEG C.Through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtain fluorenes
Ketone yield is 37%.
Embodiment 3:
Prepare the cobalt nitrate and copper nitrate ethanol solution of 30wt%, the molar ratio of cobalt and copper is 1:1, by the lemon of 30wt% at 35 DEG C
Sour ethanol solution (being 2.5 with the volume ratio of cobalt nitrate and copper nitrate ethanol solution) is slowly added to, and is kept stirring, is added dropwise in the process
Continue to stir 12h at 35 DEG C after complete, then stir solution at 70 DEG C, solvent evaporated, obtained product is done at 100 DEG C
Dry 12h, 550 DEG C of calcining 6h, obtains cobalt copper composite oxide catalysts.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 93%.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 93%.
Embodiment 4:
In addition to using the aqueous solution of metal salt to replace the ethanol solution of metal salt, with embodiment 3, obtaining Fluorenone yield is for other
91%。
Embodiment 5:
In addition to the ethanol solution of metal salt replaces cobalt nitrate and copper nitrate using cobalt acetate and copper acetate, other are obtained with embodiment 3
It is 89% to Fluorenone yield.
Embodiment 6:
In addition to using acetonitrile that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 3, obtaining Fluorenone yield is 78% for other.
Embodiment 7:
In addition to using cyclohexanone that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 3, obtaining Fluorenone yield is 91% for other.
Embodiment 8:
In addition to being filled with ozone in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is 95% for other.
Embodiment 9:
In addition to being filled with air in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is 67% for other.
Embodiment 10:
In addition to being filled with 5% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is for other
28%。
Embodiment 11:
In addition to being filled with 50% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 3, obtaining Fluorenone yield is for other
79%。
Embodiment 12:
In addition to being filled with 5% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 3, obtaining Fluorenone yield is for other
29%。
Embodiment 13:
In addition to being filled with 50% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 3, obtaining Fluorenone yield is for other
79%。
Embodiment 14:
Copper acetate is configured to the aqueous solution of 1wt%, the sodium hydrate aqueous solution of 1%wt is prepared, is added drop-wise to empty burning simultaneously at 20 DEG C
In cup, the pH value of control process is 7, and aging 1h, is then washed with deionized to the Na of noresidue after precipitating completely+Detection is
Only, the product obtained finally calcines 1h at 300 DEG C, obtains copper oxide catalyst in 50 DEG C of dry 2h.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
0.01wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.001) is added, oxygen is filled with into reaction kettle, it is initial to press
Power 0.1MPa reacts 0.5h at 60 DEG C.Through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtain fluorenes
Ketone yield is 34%.
Embodiment 15:
Cobalt acetate is configured to the aqueous solution of 50wt%, the sodium hydrate aqueous solution of 50%wt is prepared, is added drop-wise to sky simultaneously at 80 DEG C
In beaker, the pH value of control process is 13, and aging for 24 hours, is then washed with deionized to the Na of noresidue after precipitating completely+Inspection
Until out, obtained product is dried for 24 hours at 150 DEG C, is finally calcined 1h at 800 DEG C, is obtained cobaltosic oxide catalyst.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
50wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.5) is added, oxygen, initial pressure are filled with into reaction kettle
6MPa reacts for 24 hours at 180 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 69%.
Embodiment 16:
Cobalt acetate and copper acetate be configured to the aqueous solution of 25wt%, the molar ratio of cobalt and copper is 1:1, prepares the hydroxide of 25%wt
Sodium water solution is added drop-wise in sky beaker simultaneously at 50 DEG C, and the pH value of control process is 10, and aging 12h, is then used after precipitating completely
Deionized water is washed to the Na of noresidue+Until detection, obtained product is finally calcined at 550 DEG C in 100 DEG C of dry 12h
6h obtains cobalt copper composite oxide catalysts.
Fluorenes oxidation reaction carries out in stainless steel cauldron, and reaction condition is as follows: fluorenes is dissolved in hexamethylene that (mass fraction is
25wt%), a certain amount of catalyst (mass ratio with Fluorenone is 0.3) is added, oxygen, initial pressure are filled with into reaction kettle
3MPa reacts 12h at 120 DEG C.It through being centrifugated after reaction, is then formed with gas chromatographic analysis product, obtains Fluorenone receipts
Rate is 88%.
Embodiment 17:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobalt nitrate and copper nitrate, other are obtained with embodiment 15
It is 90% to Fluorenone yield.
Embodiment 18:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobalt chloride and copper chloride, other are obtained with embodiment 15
It is 85% to Fluorenone yield.
Embodiment 19:
In addition to the aqueous solution of metal salt replaces cobalt acetate and copper acetate using cobaltous sulfate and copper sulphate, other are obtained with embodiment 15
It is 86% to Fluorenone yield.
Embodiment 20:
Except use sodium carbonate replace sodium hydroxide as precipitating reagent in addition to, with embodiment 15, obtaining Fluorenone yield is 89% for other.
Embodiment 21:
Except use sodium bicarbonate replace sodium hydroxide as precipitating reagent in addition to, with embodiment 15, obtaining Fluorenone yield is 88% for other.
Embodiment 22:
Except using potassium hydroxide to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other same embodiments
15, obtaining Fluorenone yield is 85%.
Embodiment 23:
Except using potassium carbonate to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other with embodiment 15,
Obtaining Fluorenone yield is 87%.
Embodiment 24:
Except using saleratus to replace sodium hydroxide as precipitating reagent, wash to the K of noresidue+Detection is outer, other same embodiments
15, obtaining Fluorenone yield is 87%.
Embodiment 25:
In addition to using acetonitrile that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 15, obtaining Fluorenone yield is 74% for other.
Embodiment 26:
In addition to using cyclohexanone that hexamethylene dissolution fluorenes is replaced to be reacted, with embodiment 15, obtaining Fluorenone yield is 85% for other.
Embodiment 27:
In addition to being filled with ozone in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is 90% for other.
Embodiment 28:
In addition to being filled with air in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is 61% for other.
Embodiment 29:
In addition to being filled with 5% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is for other
22%。
Embodiment 30:
In addition to being filled with 50% oxygen/nitrogen gaseous mixture in reaction kettle instead of oxygen, with embodiment 15, obtaining Fluorenone yield is for other
73%。
Embodiment 31:
In addition to being filled with 5% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 15, obtaining Fluorenone yield is for other
22%。
Embodiment 32:
In addition to being filled with 50% oxygen/argon gaseous mixture in reaction kettle instead of air, with embodiment 15, obtaining Fluorenone yield is for other
74%。
In conclusion fluorenes oxidation reaction is under the effect of the catalyst, Fluorenone yield is higher, process reaction with higher
Activity and selectivity, by-product are few.Through document and patent retrieval, the report of similar reaction process was not met, belongs to innovative work
Make.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
It is familiar with those skilled in the art in the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of, should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801858A (en) * | 2019-10-29 | 2020-02-18 | 中国科学院山西煤炭化学研究所 | A kind of catalyst for catalyzing the oxidation of benzyl compound to prepare carbonyl compound and its preparation method and application |
| CN110961113A (en) * | 2019-12-16 | 2020-04-07 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing carbonyl compound by catalyzing benzyl compound oxidation, preparation method and application thereof |
| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN102069005A (en) * | 2010-11-22 | 2011-05-25 | 天津市职业大学 | Catalyst for synthesizing vanillin by using a glyoxylic acid method and a one-pot method and preparation method thereof |
| CN104368343A (en) * | 2014-09-26 | 2015-02-25 | 中南民族大学 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst with controllable mono-dispersed particles |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN105536799A (en) * | 2016-03-01 | 2016-05-04 | 重庆工商大学 | Preparation method and application of nanometer Co3O4 catalyst |
| CN107159224A (en) * | 2017-07-01 | 2017-09-15 | 北京石油化工学院 | A kind of nitrous oxide catalytic decomposition industrial catalyst and preparation method and application |
| CN107537495A (en) * | 2017-09-22 | 2018-01-05 | 太原理工大学 | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst |
| CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
-
2019
- 2019-03-15 CN CN201910196205.4A patent/CN109772326B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376638A (en) * | 2002-04-22 | 2002-10-30 | 戴振华 | Process for preparing Co3O4 |
| CN102069005A (en) * | 2010-11-22 | 2011-05-25 | 天津市职业大学 | Catalyst for synthesizing vanillin by using a glyoxylic acid method and a one-pot method and preparation method thereof |
| CN102000576A (en) * | 2010-11-30 | 2011-04-06 | 复旦大学 | Catalyst for toluene exhaust gas catalytic combustion and preparation method thereof |
| CN105381800A (en) * | 2014-09-09 | 2016-03-09 | 中国科学院大连化学物理研究所 | Non-noble metal oxide combustion catalyst, and preparation method and use thereof |
| CN104368343A (en) * | 2014-09-26 | 2015-02-25 | 中南民族大学 | Preparation method of cobalt-based Fischer-Tropsch synthesis catalyst with controllable mono-dispersed particles |
| CN105271440A (en) * | 2015-09-29 | 2016-01-27 | 曲阜师范大学 | Structured octahedral nanometer cobaltosic oxide, and preparation method and application thereof |
| CN105523578A (en) * | 2016-02-04 | 2016-04-27 | 新疆维吾尔自治区分析测试研究院 | Nanometer copper oxide with controllable morphology as well as preparation method and application of nanometer copper oxide |
| CN105536799A (en) * | 2016-03-01 | 2016-05-04 | 重庆工商大学 | Preparation method and application of nanometer Co3O4 catalyst |
| CN107159224A (en) * | 2017-07-01 | 2017-09-15 | 北京石油化工学院 | A kind of nitrous oxide catalytic decomposition industrial catalyst and preparation method and application |
| CN107537495A (en) * | 2017-09-22 | 2018-01-05 | 太原理工大学 | A kind of preparation method and application of synthesis gas ethanol Cu Co catalyst |
| CN108671923A (en) * | 2018-05-10 | 2018-10-19 | 宁波大学 | Cu oxide/cobalt/cobalt oxide catalyst with core-casing structure and preparation method thereof for electrolysis water |
Non-Patent Citations (1)
| Title |
|---|
| 雷涛，等: "纳米氧化铜粉体的制备及应用研究进展", 《化工进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801858A (en) * | 2019-10-29 | 2020-02-18 | 中国科学院山西煤炭化学研究所 | A kind of catalyst for catalyzing the oxidation of benzyl compound to prepare carbonyl compound and its preparation method and application |
| CN110961113A (en) * | 2019-12-16 | 2020-04-07 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing carbonyl compound by catalyzing benzyl compound oxidation, preparation method and application thereof |
| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
| CN112473676B (en) * | 2021-01-13 | 2022-12-13 | 山西博荟源化工科技有限公司 | Multi-element oxide catalyst for preparing fluorenone by oxidation of fluorene, preparation method and application |
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