CN113649013A - Co (II), Zn (II) bimetal doped carbon material and preparation method and application thereof - Google Patents
Co (II), Zn (II) bimetal doped carbon material and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 95
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 219
- 238000003756 stirring Methods 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005406 washing Methods 0.000 claims abstract description 44
- 229920001661 Chitosan Polymers 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000010000 carbonizing Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 84
- 239000001301 oxygen Substances 0.000 claims description 84
- 229910052760 oxygen Inorganic materials 0.000 claims description 84
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 73
- -1 cycloalkyl alcohol Chemical compound 0.000 claims description 47
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 38
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 14
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 12
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 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
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 239000011686 zinc sulphate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 13
- 150000002576 ketones Chemical class 0.000 abstract description 13
- 230000002194 synthesizing effect Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 118
- 239000011541 reaction mixture Substances 0.000 description 116
- 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 79
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 78
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 74
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 72
- 150000002978 peroxides Chemical class 0.000 description 43
- 238000004458 analytical method Methods 0.000 description 41
- 229960004365 benzoic acid Drugs 0.000 description 40
- 238000004817 gas chromatography Methods 0.000 description 40
- 239000005457 ice water Substances 0.000 description 40
- 238000004811 liquid chromatography Methods 0.000 description 40
- 239000002904 solvent Substances 0.000 description 40
- 229910001220 stainless steel Inorganic materials 0.000 description 40
- 239000010935 stainless steel Substances 0.000 description 40
- 239000005711 Benzoic acid Substances 0.000 description 39
- 235000010233 benzoic acid Nutrition 0.000 description 39
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 description 39
- 238000003763 carbonization 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
- 239000001361 adipic acid Substances 0.000 description 37
- 235000011037 adipic acid Nutrition 0.000 description 37
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 37
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 35
- 229910021641 deionized water Inorganic materials 0.000 description 35
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 34
- 239000000126 substance Substances 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 150000003254 radicals Chemical class 0.000 description 22
- 239000011701 zinc Substances 0.000 description 21
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 20
- 229940011182 cobalt acetate Drugs 0.000 description 20
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 20
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 20
- 239000000706 filtrate Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 229910052725 zinc Inorganic materials 0.000 description 18
- 238000002386 leaching Methods 0.000 description 17
- 238000003828 vacuum filtration Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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
- 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
- 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 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
- 150000004676 glycans Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 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
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A Co (II), Zn (II) bimetal doped carbon material is prepared by the following method: dispersing chitosan in a mixed aqueous solution of a Co (II) element donor and a Zn (II) element donor, stirring and loading metal ions at 0-80 ℃ for 1-20 h, then carrying out suction filtration, washing with water, drying, and then carrying out N2Carbonizing at 100-800 ℃ for 1-10 h under the atmosphere, cooling to room temperature, stirring and washing with 0.5-10 mol/L hydrochloric acid water solution for 1-10 h, performing suction filtration, washing with water until the pH value is 3-8, and performing vacuum drying to obtain the modified carbon nano tube; the invention has simple preparation, low cost and easy industrial application; the method for synthesizing the naphthenic alcohol and the naphthenic ketone by catalyzing and oxidizing the cycloalkane 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, and has low content of naphthenic hydroperoxide and high safety factor.
Description
Technical Field
The invention relates to a Co (II), Zn (II) bimetal doped carbon material, 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) Is taken as an oxidant and is carried out at the temperature of 150-170 ℃, and has the main problems of high reaction temperature, low substrate conversion rate and poor selectivity of target products, particularly the generation of aliphatic diacid is difficult to inhibit (Applied Catalysis A, General 2019,575: 120-; catalysis Communications 2019,132: 105809). 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 of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone.
Thus, O is effectively controlled2The free radical diffusion in the process of catalytically oxidizing the cycloalkane and the catalytic conversion of the intermediate product of the oxidation, namely the cycloalkyl hydrogen peroxide, are beneficial to the improvement of the catalytic oxidation selectivity of the cycloalkane, and are a novel process improvement with great application significance in the field of catalytic oxidation of the cycloalkane in industry.
The chitosan is a deacetylated product of chitin, is the only basic aminopolysaccharide existing in a large amount in natural polysaccharide, has rich sources, strong reproducibility, no toxicity and no harm, and has wide and important application value in the fields of agriculture, food and the like. The dissolved chitosan is in a gel state, is an excellent carrier material with high stability and adsorbability, can effectively chelate divalent metal ions, has high stability, realizes high-efficiency dispersion of catalytic active centers, can provide a certain microscopic regional environment for chemical reaction, and improves reaction selectivity (Mahuili Jie, Lihao, Lifang, Zuanpeng, Shendingsi, preparation of chitosan-loaded magnetic nano zero-valent copper and catalytic reduction activity [ J ]. chemical industry environmental protection, 2021,41(03): 342) 349). The carbon material is prepared by carbonizing chitosan serving as a precursor, so that the porous structure of the chitosan can be well reserved, and the catalytic activity center carrier with high specific surface area is formed. In addition, Zn (II) can catalyze the decomposition and conversion of naphthenic base hydrogen peroxide which is an intermediate product of naphthenic hydrocarbon oxidation, prevent the non-selective thermal decomposition and conversion of the naphthenic base hydrogen peroxide and improve the selectivity of catalytic oxidation of the naphthenic hydrocarbon (Catalysis Communications 2019,132: 105809).
Therefore, the invention takes the Co (II), Zn (II) bimetal doped chitosan derived carbon material as the catalyst to catalyze O2The method for selectively synthesizing the naphthenic alcohol and the naphthenic ketone by oxidizing the naphthenic hydrocarbon has the advantages of high selectivity of the naphthenic alcohol and the naphthenic ketone, low reaction temperature, less by-products, small environmental influence and the like, and the method provided by the invention has low content of naphthenic hydroperoxide and high safety factor, and is an efficient, feasible and safe method for selectively catalytically oxidizing the naphthenic hydrocarbon to synthesize the naphthenic alcohol and the naphthenic ketone.
Disclosure of Invention
The invention aims to provide a Co (II), Zn (II) bimetal doped carbon material, a preparation method thereof and application thereof in synthesizing naphthenic alcohol and naphthenic ketone by catalytic oxidation of naphthenic hydrocarbon.
The technical scheme of the invention is as follows:
a Co (II), Zn (II) bimetal doped carbon material is prepared by the following method:
dispersing chitosan in a mixed aqueous solution of a Co (II) element donor and a Zn (II) element donor, stirring and loading metal ions at 0-80 ℃ for 1-20 h, then carrying out suction filtration, washing with water, drying, and then carrying out N2Carbonizing at 100-800 ℃ for 1-10 h under atmosphere, cooling to room temperature (20-30 ℃), stirring and washing with 0.5-10 mol/L hydrochloric acid aqueous solution for 1-10 h, performing suction filtration, washing with water until the pH value is 3-8, and performing vacuum drying to obtain a Co (II) and Zn (II) bimetal doped carbon material;
the Co (II) element donor is Co (CH)3COO)2、Co(NO2)2、CoSO4、CoCl2And a mixture of one or more than two of the hydrate thereof in any proportion, preferably anhydrous Co (CH)3COO)2；
The Zn (II) element donor is Zn (CH)3COO)2、Zn(NO2)2、ZnSO4、ZnCl2And a mixture of one or more than two of the hydrates thereof in any proportion, preferably anhydrous Zn (CH)3COO)2；
The ratio of the amount of glucosamine unit substances to the total amount of Co (II), Zn (II) and the total substances in the chitosan is 4: 0.1-2, preferably 4: 1;
the quantity ratio of the Co (II) and Zn (II) substances is 1: 0.1 to 2, preferably 1: 0.5 to 1.5;
the time for stirring the loaded metal ions is preferably 5-15 h;
the carbonization temperature is preferably 400-800 ℃, and the carbonization time is preferably 1-5 h
The concentration of the hydrochloric acid aqueous solution is preferably 0.5-5 mol/L.
The Co (II), Zn (II) bimetal doped carbon material prepared by the invention can be applied to the reaction of catalyzing and oxidizing cycloalkane to synthesize cycloalkanol and cycloalkanone. The specific application method comprises the following steps:
dispersing Co (II), Zn (II) and bimetal doped carbon materials in cycloalkane, sealing a reaction system, heating to 80-160 ℃ under stirring, introducing an oxidant to 0.1-2 MPa, keeping the set temperature and pressure, stirring for reaction for 2-24 h, and then carrying out post-treatment on reaction liquid to obtain oxidation products, namely cycloalkyl alcohol and cycloalkyl ketone;
the cycloalkane is one or a mixture of more than two of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane and cyclododecane in any proportion;
the mass usage amount of the Co (II), Zn (II) and Zn (II) bimetal doped carbon material is 0.01-10 g/100mol, preferably 0.5-10 g/100mol based on the amount of substances of cyclane;
the preferable reaction temperature is 100-130 ℃, and the preferable reaction pressure is 0.6-1.2 MPa;
the stirring speed is 600-1200 rpm, preferably 800-1000 rpm;
the oxidant is oxygen, air or a mixture of the oxygen and the air in any proportion;
the post-treatment method comprises the following steps: after the reaction, triphenylphosphine (PPh) was added to the reaction solution3The amount of the catalyst is 3 percent of the amount of the cyclane substance, the mixture is stirred for 40min (peroxide generated by reduction) at room temperature, and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product;
the analysis method for the reaction result comprises the following steps: after the reaction is finished, peroxide generated by reduction of reaction liquid by triphenylphosphine is sampled and analyzed, acetone is used as a solvent for dilution, methylbenzene is used as an internal standard for gas chromatography analysis, and the conversion rate of cycloalkane and the selectivity of naphthenic alcohol, naphthenic ketone and peroxide are calculated; and (4) performing liquid chromatography analysis by taking benzoic acid as an internal standard, and calculating the selectivity of the aliphatic diacid.
The invention has the following beneficial effects:
the invention constructs a bimetallic catalytic system by using Co (II), Zn (II) bimetallic doped carbon material to synergistically catalyze O2The oxidation of cyclane to synthesize cycloalkyl alcohol and cycloalkyl ketone not only effectively inhibits the disordered diffusion of free radicals in the oxidation process, but also realizes the oxidationThe catalytic conversion of the intermediate product, namely the naphthenic base hydrogen peroxide, greatly improves the selectivity of the target product, namely the naphthenic alcohol and the 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 high-efficiency and selective oxidation of naphthenic C-H bonds, and the method has certain reference value for high-efficiency preparation of alcohol and ketone compounds by selective catalytic oxidation of other hydrocarbon C-H bonds.
The Co (II) and Zn (II) bimetal doped carbon material has simple preparation and low cost and is easy for industrial application. The method for synthesizing the naphthenic alcohol and the naphthenic ketone by catalyzing and oxidizing the cycloalkane 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 is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
Examples 1 to 18 are the synthesis of bimetallic doped carbon materials of Co (II), Zn (II).
Examples 19 to 53 are examples of catalytic oxidation of cycloalkanes.
Examples 54 to 57 are comparative experiments.
Example 58 is a scale-up experiment.
Example 1
2.2128g (12.50mmol) of anhydrous cobalt acetate and 2.2935g (12.50mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.CAnd (5) drying. N is a radical of2Carbonizing at 700 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon 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 12.1842g of Co (II) and Zn (II) bimetal doped carbon material C4：0.50：0.50700-2.0 (glucosamine units, Co, Zn mass ratio of 8:1, 700 is carbonization temperature, 2.0 is carbonization time).
Example 2
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon 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 13.2413g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33700-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,700 for carbonization temperature, 2.0 for carbonization time).
Example 3
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon 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 12.8795g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60700-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,700 is carbonization temperatureAnd 2.0 is carbonization time).
Example 4
2.2128g (12.50mmol) of anhydrous cobalt acetate and 2.2935g (12.50mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 400 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (1.0mol/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 16.2814g of Co (II) and Zn (II) bimetal doped carbon material C4：0.50：0.50400-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.50:0.50,400 carbonization temperature, 2.0 carbonization time).
Example 5
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 400 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (1.0mol/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 15.7852g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33400-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,400 carbonization temperature, 2.0 carbonization time).
Example 6
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. QuietStanding for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 400 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (1.0mol/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 15.8762g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60400-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,400 for carbonization temperature and 2.0 for carbonization time).
Example 7
2.2128g (12.5mmol) of anhydrous cobalt acetate and 2.2935g (12.5mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 600 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (3.0mol/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 14.4215g of Co (II) and Zn (II) bimetal doped carbon material C4：0.50：0.50600-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.50:0.50,600 carbonization temperature, 2.0 carbonization time).
Example 8
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 600 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (3.0mol/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 14.6427g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33600-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,600 carbonization temperature, 2.0 carbonization time).
Example 9
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 600 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (3.0mol/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 14.1871g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60600-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,600 for carbonization temperature and 2.0 for carbonization time).
Example 10
2.2128g (12.5mmol) of anhydrous cobalt acetate and 2.2935g (12.5mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 800 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (4.0mol/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 10.2845g of Co (II) and Zn (II) bimetal doped carbon material C4：0.50：0.50800-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.50:0.50,800 for carbonization temperature and 2.0 for carbonization time).
Example 11
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water and stirred on a magnetic stirrer for 15min until the salt is completely dissolved16.1180g of chitosan (amount of glucosamine units: 100mmol) were then added and stirred on a magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 800 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (4.0mol/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 11.0128g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33800-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,800 for carbonization temperature and 2.0 for carbonization time).
Example 12
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 800 deg.C for 2.0h under atmosphere. Dispersing the obtained carbon material in 50.0mL of dilute hydrochloric acid (4.0mol/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 10.1358g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60800-2.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,800 for carbonization temperature and 2.0 for carbonization time).
Example 13
2.2128g (12.5mmol) of anhydrous cobalt acetate and 2.2935g (12.5mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 1.0h under atmosphere. The resulting carbon material was dispersed in 50.0mL of dilute hydrochloric acid (2.0mol/L), washed with stirring for 6.0 hours, filtered under reduced pressure, and removed with 2X 50mLLeaching the mixture with ionized water until the pH value is 5.0-6.0, and drying the leached mixture in vacuum to obtain 12.1765g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50700-1.0 (glucosamine units, Co, Zn mass ratio of 4:0.50:0.50,700 for carbonization temperature, 1.0 for carbonization time).
Example 14
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 1.0h under atmosphere. Dispersing the obtained carbon 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 12.7889g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33700-1.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,700 for carbonization temperature, 1.0 for carbonization time).
Example 15
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 1.0h under atmosphere. Dispersing the obtained carbon 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 13.3859g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60700-1.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,700 for carbonization temperature, 1.0 for carbonization time).
Example 16
2.2128g (12.5mmol) of anhydrous cobalt acetate are taken,2.2935g (12.5mmol) of anhydrous zinc acetate is dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, after the salt is completely dissolved, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 3.0h under atmosphere. Dispersing the obtained carbon 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 12.1148g of Co (II) and Zn (II) bimetal doped carbon material C4：0.50：0.50700-3.0 (glucosamine units, Co, Zn mass ratio of 4:0.50:0.50,700 for carbonization temperature, 3.0 for carbonization time).
Example 17
2.9509g (16.67mmol) of anhydrous cobalt acetate and 1.5284g (8.33mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 deg.C for 3.0h under atmosphere. Dispersing the obtained carbon 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 11.7832g of Co (II) and Zn (II) bimetal doped carbon material C4：0.67：0.33700-1.0 (glucosamine units, Co, Zn mass ratio of 4:0.67:0.33,700 for carbonization temperature, 3.0 for carbonization time).
Example 18
1.7702g (10.00mmol) of anhydrous cobalt acetate and 2.7522g (15.00mmol) of anhydrous zinc acetate are dissolved in 250mL of deionized water, stirred on a magnetic stirrer for 15min, 16.1180g of chitosan (the amount of glucosamine unit substance is 100mmol) is added after the salt is completely dissolved, and stirred on the magnetic stirrer for 6.0 h. Standing for 30min, vacuum filtering, washing with 3 × 100mL water for 3 times until the filtrate is clear, drying in the shade at room temperature for 24.0h, and vacuum drying at 80 deg.C. N is a radical of2Carbonizing at 700 ℃ in atmosphere3.0 h. Dispersing the obtained carbon material in 50mL 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 12.8795g of Co (II) and Zn (II) bimetal doped carbon material C4：0.40：0.60700-1.0 (glucosamine units, Co, Zn mass ratio of 4:0.40:0.60,700 for carbonization temperature and 3.0 for carbonization time).
Example 19
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 7.03%, cyclohexanol selectivity 44.27%, cyclohexanone selectivity 49.72%, cyclohexyl hydroperoxide selectivity 2.53%, adipic acid selectivity 3.02%, glutaric acid selectivity 0.46%.
Example 20
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 with benzeneFormic acid was used as an internal standard for liquid chromatography. The conversion rate of cyclopentane was 5.04%, the selectivity for cyclopentanol was 9.45%, the selectivity for cyclopentanone was 48.24%, the selectivity for cyclopentyl hydroperoxide was 12.06%, the selectivity for glutaric acid was 27.62%, and the selectivity for succinic acid was 2.63%.
Example 21
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 (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 cycloheptane is 23.14 percent, the selectivity of cycloheptanol is 9.86 percent, the selectivity of cycloheptanone is 66.59 percent, the selectivity of cycloheptyl hydroperoxide is 20.39 percent, the selectivity of pimelic acid is 2.04 percent, and the selectivity of adipic acid is 1.12 percent.
Example 22
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 27.62 percent, the selectivity of cyclooctanol is 32.41 percent, and the selectivity of cyclooctanone is 50 percent.75 percent, the selectivity of the cyclooctyl hydrogen peroxide is 14.56 percent, the selectivity of the suberic acid is 1.93 percent, and the selectivity of the pimelic acid is 0.35 percent.
Example 23
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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. 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. Cyclododecane conversion 30.26%, cyclododecanol selectivity 18.28%, cyclododecanone selectivity 48.37%, cyclododecyl hydroperoxide selectivity 33.35%, and formation of dodecanoic acid and undecanoic acid was not detected.
Example 24
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.67：0.33-700-2.0 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 6.13%, the cyclohexanol selectivity was 43.22%, the cyclohexanone selectivity was 47.76%, the cyclohexyl hydroperoxide selectivity was 2.16%, the adipic acid selectivity was 5.31%, and the glutaric acid selectivity was 1.55%.
Example 25
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-700-2.0 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 5.85%, the cyclohexanol selectivity is 40.85%, the cyclohexanone selectivity is 45.83%, the cyclohexyl hydroperoxide selectivity is 5.64%, the adipic acid selectivity is 5.67%, and the glutaric acid selectivity is 2.01%.
Example 26
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-400-2.0 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. The cyclohexane conversion rate is 5.61%, the cyclohexanol selectivity is 42.63%, the cyclohexanone selectivity is 44.65%, the cyclohexyl hydroperoxide selectivity is 3.57%, the adipic acid selectivity is 5.79%, and the glutaric acid selectivity is 3.36%.
Example 27
In 100mL stainless steel high pressure reaction with polytetrafluoroethylene inner containerIn a kettle, 0.0060g of Co (II), Zn (II) and bimetal doped carbon material C4：0.67：0.33-400-2.0 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 5.32%, cyclohexanol selectivity 44.51%, cyclohexanone selectivity 45.02%, cyclohexyl hydroperoxide selectivity 4.11%, adipic acid selectivity 5.12%, glutaric acid selectivity 1.24%.
Example 28
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-400-2.0 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 4.89%, cyclohexanol selectivity 45.13%, cyclohexanone selectivity 45.68%, cyclohexyl hydroperoxide selectivity 3.25%, adipic acid selectivity 4.95%, glutaric acid selectivity 0.99%.
Example 29
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-600-2.0 dispersed in 16.8320g (200mmol) of cyclohexaneIn the alkane, the reaction kettle is sealed, stirred and heated to 120 ℃, 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 5.77%, the cyclohexanol selectivity is 41.62%, the cyclohexanone selectivity is 47.83%, the cyclohexyl hydroperoxide selectivity is 2.21%, the adipic acid selectivity is 6.75%, and the glutaric acid selectivity is 1.59%.
Example 30
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.67：0.33-600-2.0 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 43.17%, cyclohexanone selectivity 48.31%, cyclohexyl hydroperoxide selectivity 2.62%, adipic acid selectivity 4.12%, glutaric acid selectivity 1.78%.
Example 31
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-600-2.0 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. 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. Cyclohexane conversion 4.86%, cyclohexanol selectivity 42.58%, cyclohexanone selectivity 45.62%, cyclohexyl hydroperoxide selectivity 1.73%, adipic acid selectivity 7.04%, glutaric acid selectivity 3.03%.
Example 32
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-800-2.0 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 5.71%, cyclohexanol selectivity 44.01%, cyclohexanone selectivity 42.38%, cyclohexyl hydroperoxide selectivity 3.66%, adipic acid selectivity 6.78%, glutaric acid selectivity 3.17%.
Example 33
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.67：0.33-800-2.0 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) At room temperatureThe resulting peroxide was reduced by stirring 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 5.71%, cyclohexanol selectivity 41.85%, cyclohexanone selectivity 49.62%, cyclohexyl hydroperoxide selectivity 1.05%, adipic acid selectivity 6.21%, glutaric acid selectivity 1.27%.
Example 34
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-800-2.0 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 4.88%, cyclohexanol selectivity 42.58%, cyclohexanone selectivity 48.15%, cyclohexyl hydroperoxide selectivity 2.16%, adipic acid selectivity 5.79%, glutaric acid selectivity 1.32%.
Example 35
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-1.0 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 removedTaking methylbenzene as an internal standard to carry out gas chromatography analysis; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.69%, cyclohexanol selectivity 42.55%, cyclohexanone selectivity 47.61%, cyclohexyl hydroperoxide selectivity 3.54%, adipic acid selectivity 5.79%, glutaric acid selectivity 0.51%.
Example 36
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.67：0.33-700-1.0 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 5.33%, cyclohexanol selectivity 40.06%, cyclohexanone selectivity 50.62%, cyclohexyl hydroperoxide selectivity 2.56%, adipic acid selectivity 5.21%, glutaric acid selectivity 1.55%.
Example 37
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-700-1.0 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 4.89%, cyclohexanol selectivity 40.51%, cyclohexanone selectivity 50.02%, cyclohexyl hydroperoxide selectivity 1.07%, adipic acid selectivity 7.27%, glutaric acid selectivity 1.13%.
Example 38
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-3.0 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 5.12%, cyclohexanol selectivity 43.26%, cyclohexanone selectivity 48.46%, cyclohexyl hydroperoxide selectivity 2.14%, adipic acid selectivity 5.38%, glutaric acid selectivity 0.76%.
Example 39
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.67：0.33-700-1.0 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. 4.78 percent of cyclohexane conversion rate, 44.17 percent of cyclohexanol selectivity, 44.85 percent of cyclohexanone selectivity, 2.18 percent of cyclohexyl hydroperoxide selectivity,the selectivity to adipic acid was 7.69% and the selectivity to glutaric acid was 1.11%.
Example 40
0.0060g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.40：0.60-700-1.0 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 4.52%, cyclohexanol selectivity 39.85%, cyclohexanone selectivity 48.67%, cyclohexyl hydroperoxide selectivity 3.76%, adipic acid selectivity 5.89%, glutaric acid selectivity 1.83%.
EXAMPLE 41
0.0050g of Co (II), Zn (II) and bimetallic doped carbon material C in a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 5.01%, the cyclohexanol selectivity is 28.56%, the cyclohexanone selectivity is 40.31%, the cyclohexyl hydroperoxide selectivity is 20.67%, the adipic acid selectivity is 6.89%, and the glutaric acid selectivity is 3.57%.
Example 42
0.0150g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 5.86%, the cyclohexanol selectivity is 33.78%, the cyclohexanone selectivity is 42.51%, the cyclohexyl hydroperoxide selectivity is 14.56%, the adipic acid selectivity is 7.92% and the glutaric acid selectivity is 1.23%.
Example 43
0.0200g of Co (II), Zn (II) and bimetal doped carbon material C in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 5.79%, cyclohexanol selectivity 40.89%, cyclohexanone selectivity 47.28%, cyclohexyl hydroperoxide selectivity 4.59%, adipic acid selectivity 6.45%, glutaric acid selectivity 0.79%.
Example 44
0.0100g of Co (II), Zn (II) and bimetal doped carbon in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner containerMaterial C4：0.50：0.50-700-2.0 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. Cyclohexane conversion 4.99%, cyclohexanol selectivity 38.42%, cyclohexanone selectivity 44.38%, cyclohexyl hydroperoxide selectivity 13.50%, adipic acid selectivity 2.85%, glutaric acid selectivity 0.85%.
Example 45
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 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 5.51%, cyclohexanol selectivity 41.69%, cyclohexanone selectivity 46.52%, cyclohexyl hydroperoxide selectivity 7.24%, adipic acid selectivity 3.11%, glutaric acid selectivity 1.44%.
Example 46
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 is dispersed in 16.8320g (200mmol) cyclohexane, the reaction kettle is sealed, the temperature is raised to 140 ℃ by stirring, and the mixture is introducedOxygen is added 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 5.82%, the cyclohexanol selectivity is 41.25%, the cyclohexanone selectivity is 48.12%, the cyclohexyl hydroperoxide selectivity is 2.34%, the adipic acid selectivity is 6.58% and the glutaric acid selectivity is 1.71%.
Example 47
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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. 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; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 6.38%, the cyclohexanol selectivity is 45.31%, the cyclohexanone selectivity is 47.86%, the cyclohexyl hydroperoxide selectivity is 3.65%, the adipic acid selectivity is 2.33%, and the glutaric acid selectivity is 0.85%.
Example 48
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.20MPa of oxygen pressure. After the reaction is finished, cooling the mixture to room temperature by ice water, and then carrying out the reverse reaction1.3115g (5.00mmol) of triphenylphosphine (PPh) were added to the 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 6.71%, cyclohexanol selectivity 44.61%, cyclohexanone selectivity 48.74%, cyclohexyl hydroperoxide selectivity 2.37%, adipic acid selectivity 3.52%, glutaric acid selectivity 0.76%.
Example 49
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 selectivity 42.83%, cyclohexanone selectivity 46.52%, cyclohexyl hydroperoxide selectivity 5.63%, adipic acid selectivity 4.08%, glutaric acid selectivity 0.94%.
Example 50
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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. With 3CKetone as solvent, and the reaction mixture was made 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 cyclohexane conversion rate is 5.06%, the cyclohexanol selectivity is 42.71%, the cyclohexanone selectivity is 46.75%, the cyclohexyl hydroperoxide selectivity is 5.68%, the adipic acid selectivity is 3.85%, and the glutaric acid selectivity is 1.01%.
Example 51
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 5.87%, cyclohexanol selectivity 42.58%, cyclohexanone selectivity 48.14%, cyclohexyl hydroperoxide selectivity 3.58%, adipic acid selectivity 4.13%, glutaric acid selectivity 1.57%.
Example 52
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 resulting solution was removed and subjected to gas chromatography using toluene as an internal standard(ii) a 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.22%, cyclohexanol selectivity 41.62%, cyclohexanone selectivity 47.89%, cyclohexyl hydroperoxide selectivity 1.14%, adipic acid selectivity 6.17%, glutaric acid selectivity 3.18%.
Example 53
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0100g of Co (II), Zn (II) and bimetal doped carbon material C4：0.50：0.50-700-2.0 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 6.53%, the cyclohexanol selectivity is 40.85%, the cyclohexanone selectivity is 48.03%, the cyclohexyl hydroperoxide selectivity is 1.84%, the adipic acid selectivity is 6.24% and the glutaric acid selectivity is 3.81%.
Example 54 (comparative experiment)
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0060g chitosan 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 0.09%, cyclohexanol selectivity 11.03%, cyclohexanone selectivity 28.62%, cyclohexyl overThe hydrogen oxide selectivity was 60.35% and no formation of adipic acid and glutaric acid was detected.
Example 55 (comparative experiment)
0.0060g of anhydrous cobalt acetate 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. The cyclohexane conversion rate was 3.59%, the cyclohexanol selectivity was 27.79%, the cyclohexanone selectivity was 19.74%, the cyclohexyl hydroperoxide selectivity was 49.51%, the adipic acid selectivity was 2.67%, and the glutaric acid selectivity was 0.29%.
Example 56 (comparative experiment)
0.0060g of anhydrous zinc acetate 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 1.31%, no formation of cyclohexanol was detected, cyclohexanone selectivity 7.67%, cyclohexyl hydroperoxide selectivity 92.33%, no formation of adipic acid was detected, and no formation of glutaric acid was detected.
Example 57 (comparative experiment)
In 100mL with polytetrafluoroethylene0.0030g of anhydrous cobalt acetate and 0.0030g of anhydrous zinc acetate were dispersed in 16.8320g (200mmol) of cyclohexane in a stainless steel autoclave equipped with a bladder, the autoclave was sealed, stirred and heated to 120 ℃ 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. The cyclohexane conversion was 2.52%, the cyclohexanol selectivity was 18.52%, the cyclohexanone selectivity was 10.03%, the cyclohexyl hydroperoxide selectivity was 70.19%, the adipic acid selectivity was 1.26%, and the formation of glutaric acid was not detected.
Example 58 (amplification experiment)
0.0600g of Co (II), Zn (II) and bimetal doped carbon material C in a 1L stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container4：0.50：0.50-700-2.0 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 completion of the reaction, ice water was cooled to room temperature, and 131.15g (500.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 50 min. Distilling, recovering 132.68g of cyclohexane, and obtaining 6.78% of conversion rate; vacuum rectification is carried out to obtain 5.32g of cyclohexanol, the selectivity is 43.32 percent, the selectivity is 6.31g of cyclohexanone, the selectivity is 49.01 percent, and ethyl acetate is recrystallized to obtain 0.28g of adipic acid, the selectivity is 2.74 percent, the glutaric acid is 0.032g, and the selectivity is 0.40 percent.
Claims (8)
1. A Co (II), Zn (II) bimetal doped carbon material is characterized by being prepared by the following method:
dispersing chitosan in a mixed aqueous solution of a Co (II) element donor and a Zn (II) element donor, stirring and loading metal ions at 0-80 ℃ for 1-20 h, then carrying out suction filtration, washing with water, drying, and then carrying out N2Carbonizing at 100-800 ℃ for 1-10 h under atmosphere, cooling to room temperature, stirring and washing with 0.5-10 mol/L hydrochloric acid water solution for 1-10 h, filtering, washing with water until the pH value is 3-8, and drying in vacuum to obtain the Co (II) and Zn (II) bimetal doped carbon material.
2. The Co (II), Zn (II) bimetallic doped carbon material of claim 1, wherein the Co (II) donor is Co (CH)3COO)2、Co(NO2)2、CoSO4、CoCl2And hydrate thereof, and a mixture of two or more of them in any proportion.
3. The Co (II), Zn (II) bimetallic doped carbon material of claim 1, wherein the Zn (II) element donor is Zn (CH)3COO)2、Zn(NO2)2、ZnSO4、ZnCl2And hydrate thereof, and a mixture of two or more of them in any proportion.
4. Co (II), Zn (II) bimetallic doped carbon material according to claim 1, wherein the ratio of the amount of glucosamine unit species in the chitosan to the total amount of Co (II), Zn (II) species is 4: 0.1 to 2.
5. The Co (II), Zn (II) bimetallic doped carbon material of claim 1, wherein the ratio of the amounts of Co (II), Zn (II) and the like is 1: 0.1 to 2.
6. Use of the co (ii), zn (ii) bimetallic doped carbon material of claim 1 in the catalytic oxidation of cycloalkanes to synthesize cycloalkanol and cycloalkanone.
7. The application of claim 6, wherein the method of applying is:
dispersing Co (II), Zn (II) and bimetal doped carbon materials in cycloalkane, sealing a reaction system, heating to 80-160 ℃ under stirring, introducing an oxidant to 0.1-2 MPa, keeping the set temperature and pressure, stirring for reaction for 2-24 h, and then carrying out post-treatment on reaction liquid to obtain oxidation products, namely cycloalkyl alcohol and cycloalkyl ketone;
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.
8. The use according to claim 7, wherein the amount by mass of the Co (II), Zn (II) and/or Bi-metallic doped carbon material is 0.01 to 10g/100mol based on the amount of the cycloalkane.
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| JP2005145977A (en) * | 2003-11-18 | 2005-06-09 | China Petrochemical Corp | Process for catalytically oxidizing olefin and cycloolefin for the purpose of forming enol, olefin ketone, and epoxide |
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| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
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| JP2005145977A (en) * | 2003-11-18 | 2005-06-09 | China Petrochemical Corp | Process for catalytically oxidizing olefin and cycloolefin for the purpose of forming enol, olefin ketone, and epoxide |
| CN111408392A (en) * | 2019-01-08 | 2020-07-14 | 南京理工大学 | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof |
| CN110563550A (en) * | 2019-08-30 | 2019-12-13 | 浙江工业大学 | Method for preparing cycloalkanol and cycloalkanone by catalyzing and oxidizing cycloalkane with double metal cobalt (II) salt/zinc (II) salt |
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