CN113769746A - Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof - Google Patents
Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof Download PDFInfo
- Publication number
- CN113769746A CN113769746A CN202111006502.1A CN202111006502A CN113769746A CN 113769746 A CN113769746 A CN 113769746A CN 202111006502 A CN202111006502 A CN 202111006502A CN 113769746 A CN113769746 A CN 113769746A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- selectivity
- reaction
- doped
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 187
- 238000003756 stirring Methods 0.000 claims abstract description 109
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002576 ketones Chemical class 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 112
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 81
- 239000001301 oxygen Substances 0.000 claims description 81
- 229910052760 oxygen Inorganic materials 0.000 claims description 81
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 72
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 24
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- 125000002091 cationic group Chemical group 0.000 claims description 18
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 claims description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004914 cyclooctane Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 2
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 claims description 2
- -1 cycloalkyl alcohol Chemical compound 0.000 abstract description 50
- 150000003839 salts Chemical class 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 10
- 230000002194 synthesizing effect Effects 0.000 abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 117
- 239000011541 reaction mixture Substances 0.000 description 113
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 84
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 78
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 78
- 239000000243 solution Substances 0.000 description 78
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 72
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 50
- 150000002978 peroxides Chemical class 0.000 description 44
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 41
- 239000004810 polytetrafluoroethylene Substances 0.000 description 41
- 229910001220 stainless steel Inorganic materials 0.000 description 41
- 239000010935 stainless steel Substances 0.000 description 41
- 239000005711 Benzoic acid Substances 0.000 description 39
- 235000010233 benzoic acid Nutrition 0.000 description 39
- 239000005457 ice water Substances 0.000 description 39
- 238000004811 liquid chromatography Methods 0.000 description 39
- 239000002904 solvent Substances 0.000 description 39
- 238000004458 analytical method Methods 0.000 description 38
- 238000004817 gas chromatography Methods 0.000 description 38
- 238000005406 washing Methods 0.000 description 38
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 37
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 37
- 239000001361 adipic acid Substances 0.000 description 36
- 235000011037 adipic acid Nutrition 0.000 description 36
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 35
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 34
- 238000001291 vacuum drying Methods 0.000 description 32
- 239000000463 material Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 20
- 238000001914 filtration Methods 0.000 description 18
- 150000001768 cations Chemical class 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 16
- 238000002386 leaching Methods 0.000 description 16
- 238000003828 vacuum filtration Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SXVPOSFURRDKBO-UHFFFAOYSA-N Cyclododecanone Chemical compound O=C1CCCCCCCCCCC1 SXVPOSFURRDKBO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- SFVWPXMPRCIVOK-UHFFFAOYSA-N cyclododecanol Chemical compound OC1CCCCCCCCCCC1 SFVWPXMPRCIVOK-UHFFFAOYSA-N 0.000 description 1
- QCRFMSUKWRQZEM-UHFFFAOYSA-N cycloheptanol Chemical compound OC1CCCCCC1 QCRFMSUKWRQZEM-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GPHZOCJETVZYTP-UHFFFAOYSA-N hydroperoxycyclododecane Chemical compound OOC1CCCCCCCCCCC1 GPHZOCJETVZYTP-UHFFFAOYSA-N 0.000 description 1
- GRLDKEKHXHSXQW-UHFFFAOYSA-N hydroperoxycycloheptane Chemical compound OOC1CCCCCC1 GRLDKEKHXHSXQW-UHFFFAOYSA-N 0.000 description 1
- DTMZBUVZQPKYDT-UHFFFAOYSA-N hydroperoxycyclooctane Chemical compound OOC1CCCCCCC1 DTMZBUVZQPKYDT-UHFFFAOYSA-N 0.000 description 1
- VGGFAUSJLGBJRZ-UHFFFAOYSA-N hydroperoxycyclopentane Chemical compound OOC1CCCC1 VGGFAUSJLGBJRZ-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to Co (II) and Ni (II) doped montmorillonite, a preparation method thereof and application thereof in synthesizing cycloalkanol and cycloalkanone by catalytic oxidation of cycloalkane, belonging to the field of industrial catalysis and fine organic synthesis. The method comprises the following steps: dispersing montmorillonite in mixed aqueous solution of Co (II) salt and Ni (II) salt (total amount is 30.0mmol), stirring and loading metal ions, collecting solid, performing high temperature treatment, and performing post-treatment to obtain Co (II) and Ni (II) doped montmorillonite. The obtained Co (II) and Ni (II) doped montmorillonite is applied to catalyzing cyclane to obtain products of cycloalkyl alcohol and cycloalkyl ketone. The catalytic reaction has the advantages of high selectivity of the naphthenic base alcohol and the naphthenic base ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Description
Technical Field
The invention relates to Co (II) and Ni (II) doped montmorillonite, a preparation method thereof and application thereof in synthesizing cycloalkanol and cycloalkanone by catalytic oxidation of cycloalkane, belonging to the field of industrial catalysis and fine organic synthesis.
Background
Catalytic oxidation of cycloalkane is an important conversion process in chemical industry, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important intermediates in fine chemical industry, and are widely used in synthesis of fine chemical products such as pesticides, medicines, dyes, surfactants, resins, and the like, especially production of polyamide fiber nylon-6 and nylon-66. At present, the catalytic oxidation of cycloalkanes is industrially carried out mainly by homogeneous Co2+Or Mn2+As catalyst, oxygen (O)2) As an oxidizing agent, at 150 ℃ to 170 ℃, there are major problems of high reaction temperature, low oxidation efficiency, poor selectivity of the target product, increased conversion rate of the reaction which consumes the selectivity of the partially oxidized product, and in particular, difficulty in suppressing the generation of aliphatic diacid (Applied catalysts a, General 2019,575: 120-; catalysis Communications 2019,132: 105809; applied Catalysis A, General 2021,609: 117904; ). The main sources of the above problems are: (1) at present, O is industrially used2Oxidized cycloalkanes undergo mainly a disordered radical diffusion history; (2) the intermediate product is oxidized, and the naphthenic base hydrogen peroxide is converted to the target oxidation product of the naphthenic alcohol and the cycloalkanone through a free radical thermal decomposition path, so that the uncontrollable property of a reaction system is increased, and the selectivity of the naphthenic alcohol and the naphthenic ketone is reduced; (3) oxidizing the intermediate product, wherein the oxidizing property of the naphthenic base hydrogen peroxide is not fully utilized; (4) of cycloalkanols and cycloalkanonesThe activity is higher than that of the substrate cycloparaffin. Thus, O is effectively controlled2The disordered diffusion of free radicals in the process of catalytically oxidizing cycloalkane, the catalytic conversion and oxidation of intermediate product cycloalkyl peroxide and the oxidation of new cycloalkane by using the oxidation of the intermediate product cycloalkyl peroxide are beneficial to the improvement of the catalytic oxidation selectivity of cycloalkane and the improvement of the oxidation efficiency, and the method is a novel process improvement with great application significance in the field of catalytic oxidation of cycloalkane in industry.
Montmorillonite (MT) is smectite clay (including calcium-based, sodium-based and magnesium-based smectite clay) which is prepared by dispersion, purification and compounding, has a special lamellar structure and a cation exchange function, can be modified on the surface of an interlayer, has a good porous structure, is widely applied to the industry of high polymer materials, and can improve the physical properties of the materials, such as impact resistance, fatigue resistance, gas barrier property and the like (Li Feng, preparation and characterization of a montmorillonite load material type catalyst [ J ] application chemical industry 2015,44(06): 1088-. At present, no relevant report of applying the catalyst to catalytic oxidation reaction of cycloalkane exists.
Disclosure of Invention
The invention aims to provide Co (II) and Ni (II) doped montmorillonite, a preparation method thereof and application thereof in synthesizing naphthenic alcohol and naphthenic ketone by catalytic oxidation of cycloalkane. According to the invention, metal ions are immobilized in a montmorillonite lamellar porous structure by taking montmorillonite as a precursor through cation exchange, and a metal loading material is prepared through high-temperature treatment, so that metal active centers can be effectively dispersed, the catalytic active centers are highly dispersed, and the catalytic efficiency is further improved. In addition, bimetal Co (II) and Ni (II) are introduced into the material, so that the catalytic conversion of oxidation intermediate product naphthenic base peroxide in the catalytic oxidation process of cycloalkane is controlled, the conversion of the naphthenic base peroxide to cycloalkanol cycloalkanone is promoted, and the conversion rate of reactants is further improved by relay catalysis of bimetal active centers. The Co (II) and Ni (II) doped montmorillonite material provided by the invention not only has the advantages of bimetallic active center, high catalytic efficiency, good selectivity and the like, but also has simple preparation method and low cost. The provided catalytic oxidation method for cycloalkanes has the advantages of high selectivity of cycloalkanol and cycloalkanone, low reaction temperature, few byproducts and the like, and is a high-efficiency, feasible and safe method for synthesizing cycloalkanol and cycloalkanone by selective catalytic oxidation of cycloalkanes.
The technical scheme adopted by the invention for solving the technical problems is as follows:
one of the purposes of the invention is to provide a preparation method of Co (II) and Ni (II) doped montmorillonite, which comprises the following steps:
(1) preparing a mixed salt solution containing Co (II), Ni (II) and Co (II) element donors and Ni (II) element donors;
(2) adding montmorillonite into the mixed salt solution and stirring for a certain time to carry out metal loading on the montmorillonite;
(3) after the metal loading is finished, collecting the solid, carrying out high-temperature treatment on the solid in a protective atmosphere, and carrying out post-treatment to obtain Co (II) and Ni (II) doped montmorillonite.
Preferably, in the step (1), the co (ii) donor is one or more of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride, the cobalt acetate includes anhydrous cobalt acetate and a hydrate corresponding to cobalt acetate (e.g. cobalt acetate tetrahydrate), the cobalt nitrate includes anhydrous cobalt nitrate and a hydrate corresponding to cobalt nitrate (e.g. cobalt nitrate hexahydrate), the cobalt sulfate includes anhydrous cobalt sulfate and a hydrate corresponding to cobalt sulfate (e.g. cobalt sulfate heptahydrate), and the cobalt chloride includes anhydrous cobalt chloride and a hydrate corresponding to cobalt chloride (e.g. cobalt chloride hexahydrate), and more preferably, the anhydrous cobalt chloride.
Preferably, in the step (1), the ni (ii) element donor is one or more of nickel acetate, nickel nitrate, nickel sulfate and nickel chloride, the nickel acetate includes anhydrous nickel acetate and hydrates corresponding to nickel acetate (such as nickel acetate tetrahydrate), the nickel nitrate includes anhydrous nickel nitrate and hydrates corresponding to nickel nitrate (such as nickel nitrate hexahydrate), the nickel sulfate includes anhydrous nickel sulfate and hydrates corresponding to nickel sulfate (such as nickel sulfate heptahydrate), and the nickel chloride includes anhydrous nickel chloride and hydrates corresponding to nickel chloride (such as nickel chloride hexahydrate), and more preferably, the anhydrous nickel chloride.
Preferably, the total concentration of the metal ions (Me: Co and Ni) in the mixed salt solution in the step (1) is 0.2 mol/L-1.0 mol/L.
Preferably, the molar ratio of Co (II) and Ni (II) in the mixed salt solution in the step (1) is 1.0: 0.1-2.0, and more preferably 1.0: 0.5-1.5.
Preferably, the ratio of the amount of exchangeable cationic substances in the montmorillonite in the step (2) to the total amount of metal ions (Me: Co, Ni) in the mixed salt solution is 1.0: 0.1-5.0, and more preferably 1.0: 3.0.
Preferably, the metal loading stirring time in the step (2) is 1.0-20.0 h, and more preferably 5.0-15.0 h; the stirring temperature is 0-80 ℃.
Preferably, the solid is collected by filtration and water washing after the metal loading in the step (3), and more preferably, drying is further included.
Preferably, the protective atmosphere in step (3) is one or more of nitrogen, argon and helium.
Preferably, the high-temperature treatment temperature in the step (3) is 100-800 ℃, and more preferably 400-800 ℃; the high-temperature treatment time is 1.0-10.0 h, and more preferably 1.0-5.0 h.
Preferably, the post-treatment in the step (3) comprises the conventional steps of acid washing, water washing, drying and the like.
Preferably, the acid washing is performed by stirring and washing with hydrochloric acid, the concentration of the hydrochloric acid is 0.5-10.0 mol/L, more preferably 0.5-5.0 mol/L, and the acid washing time is 1.0-10.0 h.
Preferably, the pH value is 3.0-8.0 after washing with acid and suction filtration.
Preferably, the drying is vacuum drying at a temperature of 80 ℃.
Another object of the present invention is to provide a Co (II) prepared by the above-mentioned preparation method&Ni (II) doped montmorillonite; more preferably, said Co (II)&The carrier of the Ni (II) -doped montmorillonite is ion exchange modified montmorillonite, and the active components are metal Co, Ni, Co (II)&The average thickness of the Ni (II) -doped montmorillonite wafer is less than 25nm, and the specific surface area is 50-300 m2A pore volume of 0.1-0.5 cm3The pore size distribution is 0.5-25 nm, and the loading capacity of metal Co and Ni is 10-40%.
The invention also aims to provide application of the Co (II) and Ni (II) doped montmorillonite prepared in the preparation of cycloalkanol and cycloalkanone by catalytic oxidation of cycloalkane.
Preferably, the application method comprises the following steps:
adding Co (II) and Ni (II) doped montmorillonite and cyclane into a reaction kettle, stirring and heating to a preset temperature under a sealed condition, introducing an oxidant, stirring for catalytic reaction, and obtaining the product of naphthenic alcohol and naphthenic ketone after the reaction is finished.
Preferably, the reaction kettle is a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container.
Preferably, the cycloalkane is at least one of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane or a mixture of two or more of them in any proportion.
Preferably, the ratio of the mass (g) of the Co (II) and Ni (II) doped montmorillonite to the mass (mol) of the naphthenic hydrocarbon is 1: 10000-1: 5, preferably 1: 200-1: 10.
Preferably, the preset temperature is 80-160 ℃.
Preferably, the catalytic reaction temperature is 90-150 ℃, and more preferably 100-130 ℃; the catalytic reaction pressure is 0.1-2.0 MPa, and more preferably 0.6-1.2 MPa; the stirring speed is 600-1200 rpm, and more preferably 800-1000 rpm.
Preferably, the oxidant is oxygen, air or a mixture thereof in any proportion.
Preferably, the reaction solution further comprises post-treatment after the reaction; more preferably, the post-treatment method comprises distilling, decompressing, rectifying and recrystallizing the crude product of the reaction liquid to obtain the purified oxidation products of the naphthenic alcohol and the naphthenic ketone; more preferably, the method further comprises the following steps: after the reaction, triphenylphosphine (PPh) was added to the reaction solution3And the using amount is 3 percent of the amount of the cyclane substance, and the generated peroxide is reduced by stirring for 30min at room temperature (15-40 ℃).
Preferably, the specific reaction method of the catalytic reaction is as follows:
in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, dispersing Co (II) and Ni (II) doped montmorillonite (0.01-10 percent, g/mol) in cycloparaffin, sealing a reaction system, heating to 80-160 ℃ under stirring, introducing an oxidant (0.1-2.0 MPa), keeping the set temperature and pressure, stirring for reaction for 2.0-24.0 h, and carrying out post-treatment on reaction liquid to obtain the product of cycloalkyl alcohol and cycloalkyl ketone.
The method for analyzing the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of the reaction liquid by triphenylphosphine is sampled and analyzed. Diluting with acetone as solvent, performing gas chromatography with toluene as internal standard, and calculating conversion rate of cycloalkane and selectivity of cycloalkyl alcohol, cycloalkyl ketone and peroxide; and (4) performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid.
The invention uses Co (II)&Ni (II) is doped with montmorillonite to construct a bimetallic relay catalytic system for synergistically catalyzing O2The method for synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the cycloalkane not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the catalytic conversion of the oxidation intermediate product naphthenic hydrogen peroxide, greatly improves the selectivity of the target product naphthenic alcohol and naphthenic ketone, reduces the generation of byproducts, reduces the emission of environmental pollutants, and meets the practical requirements of the chemical industry on energy conservation and emission reduction at present. The invention not only provides a high-efficiency bimetallic catalytic material, but also provides a method for synthesizing naphthenic alcohol and naphthenic ketone by efficiently and selectively oxidizing naphthenic C-H bonds, and the method has certain reference value for efficiently preparing alcohol and ketone compounds by selectively oxidizing and catalyzing other hydrocarbon C-H bonds.
The invention has the following beneficial effects: the Co (II) and Ni (II) doped montmorillonite is simple to prepare, low in cost and easy to industrially apply. The method for synthesizing the naphthenic alcohol and the naphthenic ketone by catalyzing and oxidizing the naphthenic hydrocarbon with the catalytic material has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of the naphthenic hydroperoxide is low, and the safety coefficient is high. The invention provides a high-efficiency, feasible and safe method for synthesizing naphthenic alcohol and naphthenic ketone by selective catalytic oxidation of naphthenic hydrocarbon.
Detailed Description
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
Examples 1 to 16 are examples of the synthesis of Co (II) and Ni (II) doped montmorillonite.
Examples 17 to 50 are examples of the use of the material in the catalytic oxidation of cycloalkanes.
Examples 51 to 54 are comparative experimental cases of catalytic oxidation of cycloalkanes.
Example 55 is an experiment for amplifying Co (II) and Ni (II) doped montmorillonite catalyzed oxidation of cycloalkane.
Example 1
2.5968g (20.00mmol) of anhydrous cobalt chloride and 1.2960g (10.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 700 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 12.3196g of Co (II)&Ni (II) doped montmorillonite MT1.0：2.0：1.0700-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:2.0:1.0,700 is the high temperature treatment temperature, 2.0 is the high temperature treatment time).
Example 2
2.5920g (20.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 700 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL diluted hydrochloric acid (2.0mol/L), stirringWashing for 6.0h, then carrying out vacuum filtration, leaching with 2X 50mL deionized water until the pH value is 5.0-6.0, and carrying out vacuum drying to obtain 13.1983g of Co (II)&Ni (II) doped montmorillonite MT-01.0：2.0：1.0700-2.0 (the ratio of the amounts of exchangeable cations, Ni, Cu species is 1.0:2.0:1.0,700 for high temperature treatment temperature and 2.0 for high temperature treatment time).
Example 3
1.2984g (10.00mmol) of anhydrous cobalt chloride, 1.2960g (10.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 700 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 13.1876g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0700-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni, Cu species is 1.0:1.0:1.0:1.0,700 for high temperature treatment temperature and 2.0 for high temperature treatment time).
Example 4
1.9476g (15.00mmol) of anhydrous cobalt chloride and 1.9440g (15.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 700 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 13.0126g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.5：1.5700-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:1.5:1.5,700 for high temperature treatment temperature and 2.0 for high temperature treatment time).
Example 5
1.2984g (10.00mmol) of anhydrous cobalt chloride and 2.5920g (20.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 700 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 12.3196g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：2.0700-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:1.0:2.0,700 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 6
2.5968g (20.00mmol) of anhydrous cobalt chloride and 1.2960g (10.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 400 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 15.1325g of Co (II)&Ni (II) doped montmorillonite MT1.0：2.0：1.0400-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:2.0:1.0,400 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 7
2.5968g (20.00mmol) of anhydrous cobalt chloride and 1.2960g (10.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 500 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, then decompressing, filtering, leaching with 2X 50mL of deionized water until the pH value is 5.0-6.0, and drying in vacuum to obtain 14.2319g of Co (II)&Ni (II) doped montmorillonite MT1.0：2.0：1.0500-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:2.0:1.0,500 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 8
2.5968g (20.00mmol) of anhydrous cobalt chloride and 1.2960g (10.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 900 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 11.6794g of Co (II)&Ni (II) doped montmorillonite MT1.0：2.0：1.0900-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:2.0:1.0,900 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 9
2.5920g (20.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 500 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 13.0125g of Co (II)&Ni (II) doped montmorillonite MT-01.0：2.0：1.0500-2.0 (the ratio of the amounts of exchangeable cations, Ni, Cu species is 1.0:2.0:1.0,500 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 10
Get 2.59Dissolving 20g (20.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride in 100mL of distilled water, stirring on a magnetic stirrer for 30min, adding 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) after the salt is completely dissolved, and stirring on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 900 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 10.8764g of Co (II)&Ni (II) doped montmorillonite MT-01.0：2.0：1.0900-2.0 (the ratio of the amounts of exchangeable cations, Ni, Cu species is 1.0:2.0:1.0,900 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 11
1.2984g (10.00mmol) of anhydrous cobalt chloride, 1.2960g (10.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 500 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 15.3754g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0500-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni, Cu species is 1.0:1.0:1.0:1.0,500 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 12
1.2984g (10.00mmol) of anhydrous cobalt chloride, 1.2960g (10.00mmol) of anhydrous nickel chloride and 1.3445g (10.00mmol) of anhydrous copper chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 900 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 11.2798g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0900-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni, Cu species is 1.0:1.0:1.0:1.0,900 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 13
1.9476g (15.00mmol) of anhydrous cobalt chloride and 1.9440g (15.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 500 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 14.5786g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.5：1.5500-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:1.5:1.5,500 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 14
1.9476g (15.00mmol) of anhydrous cobalt chloride and 1.9440g (15.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 900 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 12.1248g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.5：1.5900-2.0 (the ratio of the amounts of exchangeable cations, Co and Ni species is 1.0:1.5:1.5,900 at the high temperature treatment temperature, 2.0 at the high temperature treatment timeM).
Example 15
1.2984g (10.00mmol) of anhydrous cobalt chloride and 2.5920g (20.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 500 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 14.5867g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：2.0500-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:1.0:2.0,500 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 16
1.2984g (10.00mmol) of anhydrous cobalt chloride and 2.5920g (20.00mmol) of anhydrous nickel chloride are dissolved in 100mL of distilled water, stirred on a magnetic stirrer for 30min, after the salt is completely dissolved, 20.0g of montmorillonite (the amount of exchangeable cationic substances is 10mmol) is added, and stirred on the magnetic stirrer for 5.0 h. Standing for 30min, filtering, washing with water, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2High-temperature treatment is carried out for 2.0h at 900 ℃ under the atmosphere. Dispersing the obtained montmorillonite load material in 50.0mL of dilute hydrochloric acid (2.0mol/L), stirring, washing for 6.0h, performing vacuum filtration, leaching with 2 x 50mL of deionized water until the pH value is 5.0-6.0, and performing vacuum drying to obtain 11.6325g of Co (II)&Ni (II) doped montmorillonite MT1.0：1.0：2.0900-2.0 (the ratio of the amounts of exchangeable cations, Co, Ni species is 1.0:1.0:2.0,900 for the high temperature treatment temperature and 2.0 for the high temperature treatment time).
Example 17
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. Stirring and reacting at 120 ℃ and 1.00MPa oxygen pressure at 800rpm8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 7.57%, the cyclohexanol selectivity is 45.32%, the cyclohexanone selectivity is 49.31%, the cyclohexyl hydroperoxide selectivity is 2.84%, the adipic acid selectivity is 2.27%, and the glutaric acid selectivity is 0.26%.
Example 18
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 14.0280g (200mmol) cyclopentane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 5.96%, the selectivity for cyclopentanol was 12.56%, the selectivity for cyclopentanone was 49.32%, the selectivity for cyclopentyl hydroperoxide was 11.95%, the selectivity for glutaric acid was 24.38%, and the selectivity for succinic acid was 1.79%.
Example 19
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0060g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 was dispersed in 19.6380g (200mmol) of cycloheptane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice-water, and 1.3115g (5.00mmol) of triphenylphosphine was added to the reaction mixture(PPh3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 25.32%, the selectivity of cycloheptanol is 8.94%, the selectivity of cycloheptanone is 67.31%, the selectivity of cycloheptyl hydroperoxide is 18.94%, the selectivity of pimelic acid is 3.56%, and the selectivity of adipic acid is 1.25%.
Example 20
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0060g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 22.4440g (200mmol) of cyclooctane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclooctane is 26.73 percent, the selectivity of cyclooctanol is 33.52 percent, the selectivity of cyclooctanone is 49.97 percent, the selectivity of cyclooctyl hydrogen peroxide is 13.78 percent, the selectivity of suberic acid is 2.11 percent, and the selectivity of pimelic acid is 0.62 percent.
Example 21
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0060g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 was dispersed in 33.6640g (200mmol) of cyclododecane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Using acetone as solvent, and mixingThe reaction mixture was taken to 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 31.85%, the selectivity for cyclododecanol was 18.23%, the selectivity for cyclododecanone was 49.26%, and the selectivity for cyclododecyl hydroperoxide was 32.51%, and the formation of dodecanoic acid and undecanoic acid was not detected.
Example 22
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 2 was charged&Ni (II) doped montmorillonite MT-01.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 3.23%, the cyclohexanol selectivity was 38.68%, the cyclohexanone selectivity was 41.42%, the cyclohexyl hydroperoxide selectivity was 12.83%, the adipic acid selectivity was 4.28%, and the glutaric acid selectivity was 2.79%.
Example 23
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 3 was charged&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed and subjected to gas phase chromatography using toluene as an internal standardCarrying out chromatographic analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 5.06%, cyclohexanol selectivity 43.08%, cyclohexanone selectivity 45.69%, cyclohexyl hydroperoxide selectivity 5.51%, adipic acid selectivity 4.27%, glutaric acid selectivity 1.45%.
Example 24
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 4 was charged&Ni (II) doped montmorillonite MT1.0：1.5：1.5-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.01%, the cyclohexanol selectivity is 43.62%, the cyclohexanone selectivity is 44.87%, the cyclohexyl hydroperoxide selectivity is 4.56%, the adipic acid selectivity is 5.90%, and the glutaric acid selectivity is 1.05%.
Example 25
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 5 was charged&Ni (II) doped montmorillonite MT1.0：1.0：2.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane reactorThe conversion rate is 4.23%, the selectivity for cyclohexanol is 42.81%, the selectivity for cyclohexanone is 43.72%, the selectivity for cyclohexyl hydroperoxide is 7.65%, the selectivity for adipic acid is 4.84%, and the selectivity for glutaric acid is 0.98%.
Example 26
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 6 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-400-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.59%, cyclohexanol selectivity 43.88%, cyclohexanone selectivity 45.86%, cyclohexyl hydroperoxide selectivity 5.08%, adipic acid selectivity 3.79%, glutaric acid selectivity 1.39%.
Example 27
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 7 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-500-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.52%, cyclohexanol selectivity 43.29%, cyclohexanone selectivity 44.54%, cyclohexyl hydroperoxide selectivity5.09%, adipic acid selectivity 5.75%, glutaric acid selectivity 1.33%.
Example 28
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 8 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-900-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.24%, the cyclohexanol selectivity is 44.18%, the cyclohexanone selectivity is 45.22%, the cyclohexyl hydroperoxide selectivity is 4.31%, the adipic acid selectivity is 5.32%, and the glutaric acid selectivity is 0.97%.
Example 29
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 9 was charged&Ni (II) doped montmorillonite MT-01.0：2.0：1.0-500-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.48%, the cyclohexanol selectivity is 40.37%, the cyclohexanone selectivity is 42.32%, the cyclohexyl hydroperoxide selectivity is 10.62%, the adipic acid selectivity is 5.46%, and the glutaric acid selectivity is 1.23%.
Example 30
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 10 was charged&Ni (II) doped montmorillonite MT-01.0：2.0：1.0-900-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.46%, cyclohexanol selectivity 40.71%, cyclohexanone selectivity 43.26%, cyclohexyl hydroperoxide selectivity 8.32%, adipic acid selectivity 6.45%, glutaric acid selectivity 1.26%.
Example 31
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 11 was charged&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0-500-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.66%, cyclohexanol selectivity 43.17%, cyclohexanone selectivity 45.16%, cyclohexyl hydroperoxide selectivity 5.62%, adipic acid selectivity 4.68%, glutaric acid selectivity 1.37%.
Example 32
Stainless steel with polytetrafluoroethylene liner at 100mLIn a steel autoclave, 0.0100g of Co (II) synthesized in example 12 was charged&Ni (II) doped montmorillonite MT1.0：1.0：1.0:1.0-900-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.81%, cyclohexanol selectivity 42.75%, cyclohexanone selectivity 46.03%, cyclohexyl hydroperoxide selectivity 4.31%, adipic acid selectivity 5.62%, glutaric acid selectivity 1.29%.
Example 33
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 13 was charged&Ni (II) doped montmorillonite MT1.0：1.5：1.5-500-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 5.45%, cyclohexanol selectivity 42.54%, cyclohexanone selectivity 46.02%, cyclohexyl hydroperoxide selectivity 5.31%, adipic acid selectivity 5.12%, and glutaric acid selectivity 1.01%.
Example 34
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 14 was charged&Ni (II) doped montmorillonite MT1.0：1.5：1.5-900-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.02%, cyclohexanol selectivity 42.78%, cyclohexanone selectivity 45.19%, cyclohexyl hydroperoxide selectivity 6.62%, adipic acid selectivity 4.79%, glutaric acid selectivity 0.62%.
Example 35
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 15 was charged&Ni (II) doped montmorillonite MT1.0：1.0：2.0-500-2.0 are dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.83%, cyclohexanol selectivity 43.19%, cyclohexanone selectivity 45.16%, cyclohexyl hydroperoxide selectivity 6.32%, adipic acid selectivity 4.28%, glutaric acid selectivity 1.05%.
Example 36
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 16 was charged&Ni (II) doped montmorillonite MT1.0：1.0：2.0-900-2.0 g of the reaction mixture are dispersed in 16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, and the temperature is raised to the temperature by stirringOxygen was introduced at 120 ℃ to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.95%, cyclohexanol selectivity 43.58%, cyclohexanone selectivity 46.21%, cyclohexyl hydroperoxide selectivity 5.48%, adipic acid selectivity 4.21%, glutaric acid selectivity 0.52%.
Example 37
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0010g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.14%, cyclohexanol selectivity 35.87%, cyclohexanone selectivity 40.62%, cyclohexyl hydroperoxide selectivity 16.28%, adipic acid selectivity 5.37%, glutaric acid selectivity 1.86%.
Example 38
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.0050g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After the reaction is finishedAfter completion, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.11%, the cyclohexanol selectivity is 36.83%, the cyclohexanone selectivity is 42.32%, the cyclohexyl hydroperoxide selectivity is 15.01%, the adipic acid selectivity is 4.61%, and the glutaric acid selectivity is 1.23%.
Example 39
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0150g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.51%, cyclohexanol selectivity 43.45%, cyclohexanone selectivity 46.24%, cyclohexyl hydroperoxide selectivity 5.66%, adipic acid selectivity 4.07%, glutaric acid selectivity 0.58%.
Example 40
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0200g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 80 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.07%, the cyclohexanol selectivity is 42.89%, the cyclohexanone selectivity is 43.13%, the cyclohexyl hydroperoxide selectivity is 8.12%, the adipic acid selectivity is 5.15%, and the glutaric acid selectivity is 0.71%.
EXAMPLE 41
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 100 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 80 ℃ under 1.00MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.48%, cyclohexanol selectivity 39.53%, cyclohexanone selectivity 42.26%, cyclohexyl hydroperoxide selectivity 14.51%, adipic acid selectivity 2.94%, glutaric acid selectivity 0.76%.
Example 42
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 140 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Using acetone as solvent, and determining the obtained reaction mixtureThe volume is 100 mL. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion rate 5.02%, cyclohexanol selectivity 40.44%, cyclohexanone selectivity 43.09%, cyclohexyl hydroperoxide selectivity 11.04%, adipic acid selectivity 4.05%, and glutaric acid selectivity 1.38%.
Example 43
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 0.80 MPa. The reaction was stirred at 800rpm for 8.0h at 140 ℃ under 0.80MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.01%, the cyclohexanol selectivity is 40.65%, the cyclohexanone selectivity is 45.19%, the cyclohexyl hydroperoxide selectivity is 5.86%, the adipic acid selectivity is 5.79%, and the glutaric acid selectivity is 2.51%.
Example 44
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.20 MPa. Stirring and reacting at 120 ℃ and 0.80MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; transferring 10mL of the obtained solutionThe solution was analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 6.74%, the cyclohexanol selectivity was 43.71%, the cyclohexanone selectivity was 48.32%, the cyclohexyl hydroperoxide selectivity was 2.83%, the adipic acid selectivity was 4.01%, and the glutaric acid selectivity was 1.13%.
Example 45
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 4.0h at 120 ℃ under 1.20MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate was 6.87%, the cyclohexanol selectivity was 44.62%, the cyclohexanone selectivity was 47.73%, the cyclohexyl hydroperoxide selectivity was 3.49%, the adipic acid selectivity was 3.61%, and the glutaric acid selectivity was 0.55%.
Example 46
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 4.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.83%, cyclohexanol selection42.24% in selectivity to cyclohexanone, 44.25% in selectivity to cyclohexyl hydroperoxide, 8.76% in selectivity to adipic acid, 3.94% in selectivity to glutaric acid, and 0.81% in selectivity to glutaric acid.
Example 47
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. Stirring and reacting at 120 ℃ and 1.00MPa oxygen pressure for 6.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.31%, cyclohexanol selectivity 43.46%, cyclohexanone selectivity 44.73%, cyclohexyl hydroperoxide selectivity 6.36%, adipic acid selectivity 3.91%, glutaric acid selectivity 1.54%.
Example 48
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 10.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.79%, cyclohexanol selectivity 43.94%, cyclohexanone selectivity 47.26%, cyclohexyl hydroperoxide selectivity 4.02%, adipic acid selectivity4.15 percent and glutaric acid selectivity of 0.63 percent.
Example 49
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 16.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 7.15%, cyclohexanol selectivity 45.15%, cyclohexanone selectivity 46.37%, cyclohexyl hydroperoxide selectivity 3.89%, adipic acid selectivity 3.77%, glutaric acid selectivity 0.82%.
Example 50
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner bladder, 0.0100g of Co (II) synthesized in example 1 was charged&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 24.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.94%, the cyclohexanol selectivity is 42.97%, the cyclohexanone selectivity is 48.32%, the cyclohexyl hydroperoxide selectivity is 1.85%, the adipic acid selectivity is 5.39%, and the glutaric acid selectivity is 1.47%.
Example 51 (comparative experiment)
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of montmorillonite is dispersed in 16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 0.04%, cyclohexanol selectivity 10.03%, cyclohexanone selectivity 20.78%, cyclohexyl hydroperoxide selectivity 69.19%, no formation of adipic acid and glutaric acid was detected.
Example 52 (comparative experiment)
0.0100g of anhydrous cobalt chloride is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.58%, cyclohexanol selectivity 28.38%, cyclohexanone selectivity 19.96%, cyclohexyl hydroperoxide selectivity 50.31%, adipic acid selectivity 1.24%, glutaric acid selectivity 0.11%.
Example 53 (comparative experiment)
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of anhydrous nickel chloride is dispersed in 16.8320g (200mmol) of cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.83%, no formation of cyclohexanol was detected, cyclohexanone selectivity 8.79%, cyclohexyl hydroperoxide selectivity 91.21%, no formation of adipic acid was detected, and no formation of glutaric acid was detected.
Example 54 (comparative experiment)
0.0050g of anhydrous cobalt chloride and 0.0050g of anhydrous nickel chloride were dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, the autoclave was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.22%, cyclohexanol selectivity 20.52%, cyclohexanone selectivity 10.40%, cyclohexyl hydroperoxide selectivity 68.19%, adipic acid selectivity 0.89%, and no formation of glutaric acid was detected.
Example 55 (amplification experiment)
In a 1L stainless steel autoclave having a polytetrafluoroethylene inner liner, 0.1000g of Co (II)&Ni (II) doped montmorillonite MT1.0：2.0：1.0-700-2.0 is dispersed in 168.3200g (2.0mol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.00 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.00MPa of oxygen pressure. After the reaction was completed, the mixture was cooled to room temperature with ice water, and added to the reaction mixture131.15g (500.00mmol) of triphenylphosphine (PPh)3) The resulting peroxide was reduced by stirring at room temperature for 50 min. Distilling, recovering 155.97g of cyclohexane, and ensuring the conversion rate to be 7.32%; vacuum rectification is carried out to obtain 5.32g of cyclohexanol, the selectivity is 44.25 percent, the selectivity is 5.99g of cyclohexanone, the selectivity is 48.67 percent, recrystallization is carried out to obtain 0.47g of adipic acid, the selectivity is 3.86 percent, the glutaric acid is 0.023g, and the selectivity is 0.19 percent.
The above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A preparation method of Co (II) and Ni (II) doped montmorillonite is characterized by comprising the following steps:
(1) preparing a mixed salt solution containing Co (II), Ni (II) and Co (II) element donors and Ni (II) element donors;
(2) adding montmorillonite into the mixed salt solution and stirring for metal loading;
(3) after the metal loading is finished, collecting the solid, carrying out high-temperature treatment on the solid in a protective atmosphere, and carrying out post-treatment to obtain Co (II) and Ni (II) doped montmorillonite.
2. The method for preparing Co (II) (Ni (II)) doped montmorillonite as claimed in claim 1, wherein the Co (II) element donor is one or more of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride; the Ni (II) element donor is one or more of nickel acetate, nickel nitrate, nickel sulfate and nickel chloride.
3. The method for preparing Co (II) (Ni (II)) doped montmorillonite as claimed in claim 1, wherein the molar ratio of Co (II) to Ni (II) in the mixed salt solution in the step (1) is 1.0: 0.1-2.0.
4. The method for preparing Co- (II) Ni (II) doped montmorillonite as claimed in claim 1, wherein the ratio of the amount of exchangeable cationic substances in montmorillonite in step (2) to the total amount of metal ions in the mixed salt solution is 1.0: 0.1-5.0.
5. The method for preparing Co- (II) Ni (II) doped montmorillonite as claimed in claim 1, wherein the high temperature treatment temperature in the step (3) is 100-800 ℃.
6. Co (II) and Ni (II) doped montmorillonite, characterized in that the Co (II) and Ni (II) doped montmorillonite is Co (II) and Ni (II) doped montmorillonite prepared by the preparation method of Co (II) and Ni (II) doped montmorillonite of any one of claims 1 to 5.
7. The application of Co (II) and Ni (II) doped montmorillonite in catalytic oxidation of cycloalkane, which is characterized in that the application comprises the following steps:
co (II) and Ni (II) doped montmorillonite and cyclane are stirred and heated to a preset temperature under a sealed condition, an oxidant is introduced, and then the mixture is stirred and catalyzed to react, so that the product naphthenic alcohol and naphthenic ketone is obtained after the reaction is finished.
8. The use of Co (II) (Ni (II)) doped montmorillonite in catalytic oxidation of cycloalkane according to claim 7, wherein the cycloalkane is one or a mixture of more than two of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane in any proportion; the oxidant is oxygen, air or a mixture of the oxygen and the air in any proportion.
9. The application of Co (II) Ni (II) doped montmorillonite in catalytic oxidation of cycloalkane as claimed in claim 7, wherein the ratio of the mass of Co (II) Ni (II) doped montmorillonite to the mass of cycloalkane is 1: 10000-1: 5.
10. The Co (II) of claim 7&The application of Ni (II) doped montmorillonite in catalytic oxidation of cycloalkane is characterized in that the preset temperature is 80-160 DEG C○C; the catalytic reaction conditions are thatThe temperature is 90-150 DEG C○C, the reaction pressure is 0.1-2.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006502.1A CN113769746A (en) | 2021-08-30 | 2021-08-30 | Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111006502.1A CN113769746A (en) | 2021-08-30 | 2021-08-30 | Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113769746A true CN113769746A (en) | 2021-12-10 |
Family
ID=78839933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111006502.1A Pending CN113769746A (en) | 2021-08-30 | 2021-08-30 | Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113769746A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63303936A (en) * | 1987-06-03 | 1988-12-12 | Mitsubishi Kasei Corp | Production of cyclohexanol and cyclohexanone |
| CN101045673A (en) * | 2005-03-31 | 2007-10-03 | 住友化学株式会社 | Method for producing cycloalkanol and/or cycloalkanone |
| CN101204662A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Cyclohexane liquid-phase oxidation nanometer catalyst and preparation thereof |
| CN102266779A (en) * | 2011-05-30 | 2011-12-07 | 陕西师范大学 | Ion exchange montmorillonoid carrying cobalt catalyst and preparation method and application thereof |
| CN104148077A (en) * | 2014-09-01 | 2014-11-19 | 常熟昊虞电子信息科技有限公司 | Preparation method for nickel cobalt/montmorillonite catalyst |
-
2021
- 2021-08-30 CN CN202111006502.1A patent/CN113769746A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63303936A (en) * | 1987-06-03 | 1988-12-12 | Mitsubishi Kasei Corp | Production of cyclohexanol and cyclohexanone |
| CN101045673A (en) * | 2005-03-31 | 2007-10-03 | 住友化学株式会社 | Method for producing cycloalkanol and/or cycloalkanone |
| CN101204662A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | Cyclohexane liquid-phase oxidation nanometer catalyst and preparation thereof |
| CN102266779A (en) * | 2011-05-30 | 2011-12-07 | 陕西师范大学 | Ion exchange montmorillonoid carrying cobalt catalyst and preparation method and application thereof |
| CN104148077A (en) * | 2014-09-01 | 2014-11-19 | 常熟昊虞电子信息科技有限公司 | Preparation method for nickel cobalt/montmorillonite catalyst |
Non-Patent Citations (1)
| Title |
|---|
| W. TRAKARNPRUK ET AL.: ""Iron supported clay as catalysts for oxidation of cyclooctane"", 《J MATER SCI》, vol. 41, 28 March 2006 (2006-03-28), pages 2 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110563555A (en) | Method for oxidizing cycloparaffin through synergetic catalysis of cobalt (II)/zinc (II) porphyrin salt | |
| US11420991B2 (en) | Confined porphyrin Co(II) and preparation method and application thereof | |
| CN112090449B (en) | Bimetal central metalloporphyrin as well as preparation method and application thereof | |
| CN111018673A (en) | Method for catalytic oxidation of cycloparaffin by limited porphyrin Co (II) | |
| CN112047810A (en) | Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222(Co & Zn) | |
| CN113649073A (en) | Method for catalytic oxidation of cycloparaffin by metalloporphyrin bimetallic center 2D MOFs | |
| Ni et al. | Binary catalytic systems constructed by porphyrin cobalts (II) with confining nano-region and Zn (OAc) 2 for oxygenation of cycloalkanes with O2 in relay mode | |
| CN112094178A (en) | Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-222(Co & Cu) | |
| CN112094179A (en) | Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-224(Co & Cu) | |
| CN112094180A (en) | Method for catalytic oxidation of cycloalkane by bimetallic porphyrin MOFs PCN-224(Co & Zn) | |
| CN110590504A (en) | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/copper (II) salt | |
| CN110590503A (en) | Method for preparing cycloalkanol and cycloalkanone by using cobalt (II) salt/copper (II) salt to synergistically catalyze selective oxidation of cycloalkane by molecular oxygen | |
| CN110563550A (en) | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt | |
| CN112076787A (en) | Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-222(Co)/Zn (II) salt | |
| CN113603564B (en) | Method for catalytically oxidizing cycloalkane by using trimetal center (Co & Cu & Zn) 2D MOFs/ultraviolet light | |
| CN111943808A (en) | Method for oxidizing cycloalkane under concerted catalysis of metalloporphyrin MOFs PCN-224(Mn)/Zn (II) salt | |
| US20230069145A1 (en) | Plant leaves-derived carbon material doped with two metals and preparation and use thereof | |
| CN113769746A (en) | Co (II) and Ni (II) doped montmorillonite and preparation method and application thereof | |
| TW200948768A (en) | Method for producing carbonyl compound | |
| EP2986585B1 (en) | Cycloalkane oxidation catalysts and method to produce alcohols and ketones | |
| TWI436973B (en) | Liquid-phase oxidation method for hydrocarbons | |
| CN113683619B (en) | Metalloporphyrin trimetallic center 2D MOFs and preparation method and application thereof | |
| CN112108186A (en) | Method for oxidizing cycloalkane under synergetic catalysis of metalloporphyrin MOFs PCN-224(Co)/Cu (II) salt | |
| CN1305829C (en) | Selective oxidation process of cyclohexane to prepare cyclohexanone | |
| CN111675599A (en) | Method for catalyzing and oxidizing aromatic benzyl tertiary C-H bond into tertiary alcohol by metalloporphyrin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |