CN111470948A - Synthesis method of cyclohexanol compound - Google Patents
Synthesis method of cyclohexanol compound Download PDFInfo
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- CN111470948A CN111470948A CN201910062887.XA CN201910062887A CN111470948A CN 111470948 A CN111470948 A CN 111470948A CN 201910062887 A CN201910062887 A CN 201910062887A CN 111470948 A CN111470948 A CN 111470948A
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- earth metal
- alkaline earth
- nickel
- carbon
- catalyst
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- -1 cyclohexanol compound Chemical class 0.000 title claims abstract description 35
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002114 nanocomposite Substances 0.000 claims abstract description 85
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 57
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 52
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
- 150000002989 phenols Chemical class 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- HPXRVTGHNJAIIH-PTQBSOBMSA-N cyclohexanol Chemical class O[13CH]1CCCCC1 HPXRVTGHNJAIIH-PTQBSOBMSA-N 0.000 claims abstract description 14
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 27
- 238000009826 distribution Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000013335 mesoporous material Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- IGIWPHRUBXKMAR-UHFFFAOYSA-N 4-cyclopropylphenol Chemical compound C1=CC(O)=CC=C1C1CC1 IGIWPHRUBXKMAR-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052705 radium Inorganic materials 0.000 claims description 3
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 74
- 238000010438 heat treatment Methods 0.000 description 36
- 239000010410 layer Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 239000004312 hexamethylene tetramine Substances 0.000 description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 8
- 150000002815 nickel Chemical class 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 229940078494 nickel acetate Drugs 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MOISVRZIQDQVPF-RNLVFQAGSA-N (rac)-2,6-dimethylcyclohexanol Natural products C[C@@H]1CCC[C@H](C)[C@@H]1O MOISVRZIQDQVPF-RNLVFQAGSA-N 0.000 description 2
- MOISVRZIQDQVPF-UHFFFAOYSA-N 2,6-dimethylcyclohexan-1-ol Chemical compound CC1CCCC(C)C1O MOISVRZIQDQVPF-UHFFFAOYSA-N 0.000 description 2
- PKRQDIPCUJYFKL-UHFFFAOYSA-N 4-cyclopropylcyclohexan-1-ol Chemical compound C1CC(O)CCC1C1CC1 PKRQDIPCUJYFKL-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method of cyclohexanol compounds, which comprises the following steps: the method comprises the following steps of (1) catalyzing a phenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst; the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles. The method adopts the carbon-coated nickel nanocomposite containing alkaline earth metal as the catalyst, the carbon material and the nickel nanoparticles act synergistically to produce a good catalytic effect, the alkaline earth metal of the shell layer further synergistically improves the catalytic performance of the material, and the catalyst is used for synthesizing the cyclohexanol compounds by hydrogenation reduction of the phenol compounds and has excellent activity, selectivity and safety.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a synthetic method of cyclohexanol compounds.
Background
The cyclohexanol compounds are very important chemical intermediates and have very wide application in the industries of medicine, pesticide, household cosmetics and the like. With the development of coal chemical industry in recent years, a large amount of phenol compounds can be extracted from coal chemical products, and the phenol compounds are used as raw materials to prepare cyclohexanol compounds with high additional values through hydrogenation reaction from the viewpoints of easy acquisition of raw materials and low cost, so that the method has very important economic value.
At present, catalysts for catalyzing hydrogenation reaction of phenol compounds mainly comprise noble metal catalysts such as platinum (Pt), palladium (Pd) and rhodium (Rh). The Pt and Pd noble metal catalysts have the advantages of high catalytic activity, mild reaction conditions and the like, but the noble metal catalysts have high price and cost, and the loss of noble metals has great harm to the environment, so the application of the noble metal catalysts in industrial production is limited. Non-noble metal catalysts, such as nickel, also have a series of problems in practical production application, such as easy agglomeration in the preparation process, easy elution in the catalytic hydrogenation process, poor stability, great potential safety hazard, and the like.
From the above, it is known that the development of a hydrogenation reduction catalyst which is stable in air and has excellent catalytic performance for hydrogenation reduction of phenol compounds to synthesize cyclohexanol compounds is a problem to be solved in the art.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention provides a synthesis method of cyclohexanol compounds, which adopts a carbon-coated nickel nanocomposite containing alkaline-earth metal as a catalyst, wherein the nanocomposite is formed by coating nickel nanoparticles with a graphitized carbon layer containing alkaline-earth metal, nitrogen and oxygen to form a core-shell structure, the carbon material and the nickel nanoparticles play a role in a synergistic manner to generate a good catalytic effect, the alkaline-earth metal of the shell layer further improves the catalytic performance of the material in a synergistic manner, and the cyclohexanol compounds are used for synthesizing cyclohexanol compounds by hydrogenation reduction of phenol compounds and have excellent activity, selectivity and safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing cyclohexanol compounds comprises the following steps:
the method comprises the following steps of (1) catalyzing a phenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
According to an embodiment of the present invention, the benzene ring of the phenol compound further contains a substituent selected from C1-20One or more of alkyl, cycloalkyl and aryl.
According to one embodiment of the present invention, wherein the phenolic compound is selected from one or more of phenol, 2, 6-dimethylphenol and 4-cyclopropylphenol.
According to one embodiment of the present invention, the amount of the catalyst is 1% to 50%, preferably 5% to 30% by mass of the phenolic compound.
According to one embodiment of the present invention, the temperature of the hydrogenation reduction reaction is generally 150 ℃ to 250 ℃.
According to one embodiment of the present invention, wherein the pressure of the hydrogen gas is generally 3MPa to 6 MPa.
According to one embodiment of the present invention, the catalyst and the phenol compound are mixed in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is one or more selected from the group consisting of alcohols, ethers, alkanes and water.
According to one embodiment of the present invention, the reaction time of the hydrogenation reduction is 1 to 12 hours.
According to one embodiment of the present invention, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. Optionally, the nanocomposite is a mesoporous material having two or more mesopore distribution peaks. Optionally, the nanocomposite material has a mesopore distribution peak in a pore size range of 2nm to 7nm and a pore size range of 8nm to 20nm, respectively. Optionally, the mesoporous material has a mesopore volume fraction of greater than 50%, preferably greater than 80%, more preferably greater than 95% of the total pore volume.
According to an embodiment of the invention, wherein the alkaline earth metal content is 0.1 at% to 3 at%, the carbon content is 65 at% to 95 at%, the nickel content is 1 at% to 10 at%, the oxygen content is 1 at% to 20 at%, and the nitrogen content is 1 at% to 10 at%, in atomic percentage.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
According to one embodiment of the present invention, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
According to an embodiment of the present invention, the particle size of the core-shell structure is 1nm to 200nm, preferably 3nm to 100nm, more preferably 4nm to 50 nm.
According to an embodiment of the invention, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).
The invention has the beneficial effects that:
the synthesis method of the cyclohexanol compounds provided by the invention uses the carbon-coated nickel nanocomposite containing alkaline earth metal as the catalyst to carry out hydrogenation reduction on the phenol compounds, and the catalyst material is very stable, does not spontaneously combust, is resistant to oxidation and acid corrosion, has low risk and is suitable for storage and transportation, thereby ensuring the safety of the synthesis process of the cyclohexanol compounds.
The carbon-coated nickel nanocomposite containing alkaline earth metal shows good repeatability, high activity and high selectivity in the reaction of catalytically reducing a phenol compound into a cyclohexanol compound, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of the alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nanocomposite has good catalytic performance; in addition, the nano composite material has stronger magnetism, and can be conveniently used for separating a catalyst by utilizing the magnetism or used for processes such as a magnetic stabilization bed and the like.
Drawings
FIG. 1 is a photograph showing the magnetic properties of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 2 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIG. 3 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 1;
FIGS. 4a and 4b respectively show N of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 12Adsorption-desorption isotherms and BJH pore size distribution curves;
FIG. 5 is a TEM image of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
FIG. 6 is an XRD pattern of an alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2;
fig. 7 is a BJH pore size distribution curve of the alkaline earth metal-containing carbon-coated nickel nanocomposite prepared in preparation example 2.
Detailed Description
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Any terms not directly defined herein should be understood to have meanings associated with them as commonly understood in the art of the present invention. The following terms as used throughout this specification should be understood to have the following meanings unless otherwise indicated.
Term(s) for
The term "alkyl" is defined herein as a straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and the like.
The term "cycloalkyl" is defined herein as an alkyl group connected by single bonds and constituting a ring, such as cyclohexyl.
The term "aryl" is defined herein as a functional group or substituent derived from a simple aromatic ring, such as benzyl.
The term "phenolic compound" refers to a compound formed by substituting at least one hydrogen atom on a benzene ring with a hydroxyl group (-OH);
the term "cyclohexanol compounds" refers to a class of compounds formed by substituting at least one hydrogen atom on cyclohexane by a hydroxyl group (-OH);
the term "graphitized carbon layer" means a carbon structure in which a layered structure is clearly observed under a high-resolution transmission electron microscope, not an amorphous structure, and the interlayer distance is about 0.34 nm. The composite material formed after the graphitized carbon layer is coated with the nickel nano particles is spherical or quasi-spherical.
The term "mesoporous" is defined as a pore having a pore diameter in the range of 2 to 50 nm. Pores with a pore size of less than 2nm are defined as micropores and pores with a pore size of more than 50nm are defined as macropores.
The term "mesoporous material" is defined as a porous material comprising a mesoporous channel structure.
The terms "alkaline earth metal", "nitrogen" and "oxygen" in the "graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen" refer to alkaline earth metal elements, nitrogen elements and oxygen elements, wherein the "alkaline earth metal content" of the nanocomposite refers to the content of the alkaline earth metal elements, the "nitrogen content" refers to the content of the nitrogen elements, the "oxygen content" refers to the content of the oxygen elements, and specifically refers to the content of the alkaline earth metal elements, nitrogen elements and oxygen elements in various forms contained in the formed graphitized carbon layer during the preparation of the carbon-coated nanocomposite, the "alkaline earth metal content" is the total content of all forms of alkaline earth metal elements, the "nitrogen content" is the total content of all forms of nitrogen elements, and the "oxygen content" is the total content of all forms of oxygen elements. The "alkaline earth metal content", "nitrogen content" and "oxygen content" were measured by XPS method.
The term "mesopore distribution peak" refers to a mesopore distribution peak on a pore distribution curve calculated from a desorption curve according to the Barrett-Joyner-Halenda (BJH) method.
The term "TOF" is defined herein as the amount of a reactant converted per unit time by a single active metal atom, and TOF measures the rate at which a catalyst catalyzes a reaction and indicates the intrinsic activity of the catalyst.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are Cu target, K α ray (the wavelength lambda is 0.154nm), tube voltage is 40kV, tube current is 200mA, and scanning speed is 10 degrees (2 theta)/min.
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV.
The X-ray photoelectron spectrum analyzer (XPS) is an ESCA L ab220i-X L type electron spectrum analyzer which is produced by VG scientific company and is provided with Avantage V5.926 software, the X-ray photoelectron spectrum analyzer has the analysis and test conditions that an excitation source is monochromized A1K α X-rays, the power is 330W, and the basic vacuum is 3 × 10 during analysis and test-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.6eV), and the late peak processing software was XPSPEAK.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
In the invention, after the average particle diameter of the metal nanoparticles is divided into peaks by an XRD (X-ray diffraction) pattern, the average particle diameter is calculated according to the Sherle formula: d ═ k γ/(B cos θ) was calculated. Wherein k is Scherrer constant, k is 0.89; b is half-height width; theta is the diffraction angle, unit radian; gamma is the x-ray wavelength, 0.154054 nm.
The invention provides a synthesis method of cyclohexanol compounds, which comprises the following steps:
the method comprises the following steps of (1) catalyzing a phenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst; the chemical reaction equation is illustrated below, where R represents one or more substituents on the phenyl ring or on cyclohexane:
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
In some embodiments, the benzene ring of the phenolic compound further comprises a substituent selected from C1-20One or more of alkyl, cycloalkyl and aryl.
In some embodiments, wherein the phenolic compound comprises, but is not limited to, phenol, 2, 6-dimethylphenol, 4-cyclopropylphenol, and the like.
In some embodiments, the amount of the catalyst is 1% to 50%, preferably 5% to 30% of the mass of the phenolic compound.
In some embodiments, the temperature in which the hydrogenation reduction reaction is carried out is generally in the range of 150 ℃ to 250 ℃.
In some embodiments, the pressure of the hydrogen gas therein is generally from 3MPa to 6 MPa.
In some embodiments, the catalyst is mixed with a phenol compound in a solvent and then subjected to a hydrogenation reduction reaction, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water. Such as water, cyclohexane, and the like.
In some embodiments, the reaction time of the hydrogenation reduction reaction is 1h to 12 h.
According to one embodiment of the present invention, the nanocomposite of the present invention is a composite material composed of "a graphitized carbon layer containing an alkaline earth metal, nitrogen, and oxygen", "nickel nanoparticles tightly coated with (not in contact with) the graphitized carbon layer", and "nickel nanoparticles in a confined region in contact with the outside". The surface of the graphitized carbon layer containing nitrogen and oxygen of the nano composite material has rich defect sites, the carbon material has catalytic activity, and the nickel coated in the graphitized carbon layer has a penetration effect, so that the electronic state of alkaline earth metal loaded on the surface of the graphitized carbon layer is influenced, and a synergistic effect is exerted, so that the nano composite material has better catalytic performance.
In some embodiments, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak. That is, the nano composite material has at least one mesoporous distribution peak on a pore distribution curve obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method. As known to those skilled in the art, mesoporous materials generally have large specific surface areas and relatively regular channel structures, so that the mesoporous materials can play better roles in separation, adsorption and catalytic reactions of macromolecules and can be used as microreactors for limited-domain catalysis. The nano composite material has rich mesoporous structure, so that the nano composite material has higher mass transfer efficiency and more excellent catalytic performance.
In some embodiments, the batch-produced composite has two distribution peaks in the mesoporous range; if a plurality of batches of the composite material are mixed, more distribution peaks can be obtained in the mesoporous range. When the nano composite material has the multilevel mesoporous structure with different aperture ranges, the nano composite material can show more unique performance, and the applicable application range of the multilevel mesoporous structure is wider.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 5nm and 6nm to 15nm, respectively.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous structure has one mesoporous distribution peak in mesoporous ranges of 2nm to 7nm and 8nm to 20nm, respectively.
In some embodiments, the proportion of mesopore volume in the composite material to the total pore volume is greater than 50%, preferably greater than 80%, according to the nanocomposite material of the present invention. In some embodiments, the proportion of mesopore volume to the total pore volume is greater than 90%, and even 100%.
According to the nanocomposite material of the present invention, in some embodiments, the mesoporous volume thereof may be 0.05cm3/g~1.25cm3Per g, also may be 0.10cm3/g~0.30cm3/g。
The nanocomposites according to the invention, in some embodiments, have specific surface areas generally greater than 140m2/g, may be greater than 200m2/g。
The nanocomposites according to the invention, which are not pyrophoric in air, can be stored in air.
According to the nanocomposite material of the present invention, nitrogen and oxygen are doped in the carbon layer. The nitrogen and oxygen contents can be adjusted by additionally introducing oxygen-containing compounds and nitrogen-containing compounds, such as hexamethylenetetramine and polyhydric alcohols in the manufacturing process. The catalytic performance of the carbon layer can be adjusted by adjusting the contents of nitrogen and oxygen in the nano composite material, so that the carbon layer is suitable for catalyzing different reactions.
In some embodiments, the content of elements, in atomic percent, determined using XPS method: the content of the alkaline earth metal is 0.1at percent to 3at percent, preferably 0.2at percent to 2at percent; the carbon content is 65 at% to 95 at%, preferably 74 at% to 91 at%; the nickel content is 0.1 at% to 10 at%, preferably 1 at% to 8 at%; the oxygen content is 1 at% to 20 at%, preferably 5 at% to 15 at%; the nitrogen content is 1 at% to 10 at%, preferably 0.1 at% to 10 at%. More preferably 1 at% to 5 at%.
According to the invention, the sum of the contents of the individual components in the nanocomposite material is 100 at%.
In some embodiments, the graphitized carbon layer has a thickness of 0.3nm to 6.0nm, preferably 0.3nm to 3 nm.
In some embodiments, the core-shell structure has a particle size of 1nm to 200nm, preferably 3 to 100nm, and more preferably 4nm to 50 nm.
In some embodiments, wherein the alkaline earth metal is selected from one or more of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
The invention also provides a preparation method of the nano composite material, which comprises the following steps:
putting nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound into a solvent to be mixed to form a homogeneous solution;
removing the solvent in the homogeneous solution to obtain a precursor;
carrying out primary pyrolysis on the precursor in an inert atmosphere or a reducing atmosphere;
contacting the product after the primary pyrolysis with a solution containing alkaline earth metal, and then drying; and the contact mode comprises the step of immersing the product after the primary pyrolysis in the alkaline earth metal solution, or the step of placing the product after the primary pyrolysis in the alkaline earth metal solution for stirring. The time for dipping or stirring is not suitable to be too long or too short, preferably between 10min and 300min, the temperature is preferably between 0 ℃ and 100 ℃, and the contact reaction is preferably carried out under the condition of stirring. According to the invention, the product of the primary pyrolysis may or may not be filtered after being contacted with the alkaline earth metal-containing solution, and the obtained product is dried.
And putting the dried product in an inert atmosphere for secondary pyrolysis to obtain the carbon-coated nickel nanocomposite containing the alkaline earth metal.
Specifically, the precursor is a water-soluble mixture, which means that nickel salt, polybasic organic carboxylic acid and nitrogen-containing compound are dissolved into a homogeneous solution in water and/or ethanol and other solvents, and then the solvent is directly removed to obtain the nickel-containing precursor. The solvent may be removed by evaporation, and the temperature and process of evaporation of the solvent may be by any available art, for example, spray drying at 80 ℃ to 120 ℃ or drying in an oven.
It should be noted that the polyvalent organic carboxylic acid may be a nitrogen-containing polyvalent organic carboxylic acid or a nitrogen-free polyvalent organic carboxylic acid, and when the polyvalent organic carboxylic acid is a nitrogen-containing polyvalent organic carboxylic acid, the mass of the nitrogen-containing compound may be zero, that is, the nitrogen-containing compound may not be added, and the mass ratio of the mass of the nitrogen element to the mass of the nickel salt and the polyvalent organic carboxylic acid may be within a certain range. In some embodiments, the mass ratio of the nickel salt, the organic polycarboxylic acid and the nitrogen-containing compound is 1: 0.1-100: 0-100, preferably 1: 0.5-5, and more preferably 1: 0.8-2: 1-2.
In some embodiments, the method further comprises mixing the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds except the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and other organic compounds in a solvent such as water, ethanol and the like to form a homogeneous solution, and then removing the solvent to obtain the water-soluble mixture containing nickel. Such other organic compounds include, but are not limited to, organic polyols. In some embodiments, the mass ratio of the nickel salt, the polybasic organic carboxylic acid, the nitrogen-containing compound and the other organic compound is preferably 1: 0.5-10: 0-10, more preferably 1: 1-3: 0-3, that is, the other organic compound may not be added at all.
In some embodiments, the nickel salt is selected from one or more of organic acid salts, carbonates, and basic carbonates of nickel, preferably organic acid salts of nickel without heteroatoms, more preferably acetates of the nickel without heteroatoms, wherein the heteroatoms refer to metal atoms other than the nickel. Nitrogen-containing compounds include, but are not limited to, hexamethylenetetramine.
In some embodiments, the poly-organic carboxylic acid includes, but is not limited to, one or more of citric acid, maleic acid, trimesic acid, terephthalic acid, malic acid, ethylenediaminetetraacetic acid (EDTA), and dipicolinic acid.
In some embodiments, wherein the primary pyrolysis comprises: heating the precursor to a constant temperature section in an inert atmosphere or a reducing atmosphere, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-30 ℃/min, preferably 1-10 ℃/min; the temperature of the constant temperature section is 400-800 ℃, and preferably 500-800 ℃; the constant temperature time is 20min to 600min, preferably 60min to 480 min; the inert atmosphere is nitrogen or argon, and the reducing atmosphere is a mixed gas of an inert gas and hydrogen, for example, a small amount of hydrogen is doped in the inert atmosphere.
In some embodimentsThe alkaline earth metal solution is a solution containing a salt and/or a base of an alkaline earth metal, for example, magnesium chloride (MgCl)2) Solution, magnesium nitrate (Mg (NO)3)2) Solution, calcium chloride (CaCl)2) Solution, calcium nitrate (Ca (NO)3)2) Solution, barium chloride (BaCl)2) Solutions, and the like. The mass ratio of the alkaline earth metal salt and/or alkali to the product after primary pyrolysis is 1: 1-100, preferably 1: 1.5 to 50, preferably 1: 1.5 to 20. When the amount of the alkaline earth metal-containing salt or base is too large, the catalytic performance of the finally formed nanocomposite is affected, and the activity is lowered.
In some embodiments, wherein the secondary pyrolysis comprises: under the inert atmosphere, heating the dried product to a constant temperature section, and keeping the constant temperature in the constant temperature section;
wherein the heating rate is 0.5-10 ℃/min, preferably 2.5-10 ℃/min; the temperature of the constant temperature section is 80-800 ℃, and preferably 300-600 ℃; the constant temperature time is 20 min-600 min; the inert atmosphere is nitrogen or argon.
The carbon-coated nickel nanocomposite is prepared by the method, a method of pyrolyzing a metal-organic framework compound (MOF) serving as a precursor is not adopted, the method needs to prepare a crystalline solid Material (MOF) with a periodic structure in a solvent at high temperature and high pressure, the condition for preparing MOFs is strict, the needed ligand is expensive, and the mass production is difficult; in addition, the composite material prepared by the method has imprecise cladding on the metal particles, and is remarkably different from the nano composite material in structure. The alkaline earth metal contained in the shell layer of the core-shell structure in the nano composite material can generate a synergistic effect with the core nickel nano particles, so that the catalytic performance is more excellent. The method for preparing the nano composite material is convenient for adjusting the nitrogen content and the oxygen content in the graphitized carbon layer in the preparation process, thereby conveniently adjusting the electronic characteristics of the nano composite material so as to be suitable for catalyzing different reactions.
The present invention is described in further detail below by way of specific embodiments in conjunction with the attached drawings, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and do not limit the invention in any way.
Preparation example 1
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of L aqueous solution containing 0.5128g of magnesium nitrate, soaking for 24h, and drying the product at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 50m L/min, heating to 350 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 3h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: 88.68 at% carbon, 1.27 at% nickel, 5.67 at% oxygen, 3.56 at% nitrogen, and 0.82 at% magnesium.
As shown in fig. 1, the nanocomposite was placed in water as a suspension, a magnet was placed on the outside of the container, and after a period of time the nanocomposite was attracted to one side of the magnet, which was seen to be magnetic. The TEM image of the nanocomposite is shown in fig. 2, and it can be seen that a graphitized carbon layer is wrapped on the outer layer of the nickel nanoparticle to form a complete core-shell structure. As shown in fig. 3, the diffraction pattern of this material includes diffraction peaks (2 θ angle 25.9 °) of graphitic carbon and diffraction peaks (2 θ angles 44.37 °, 51.8 ° and 76.4 °) of face-centered cubic (fcc) Ni. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 6.8nm by the scherrer equation.
The BET test showed that the specific surface area of the composite material was 173.4m2Per g, pore volume 0.296cm3Per g, wherein>The mesoporous volume of 2nm is 0.296cm3(ii) in terms of/g, representing 100% of the total pore volume. FIG. 4a is N of the nanocomposite2An adsorption-desorption isotherm is shown in fig. 4b, which is a BJH pore size distribution curve of the nanocomposite, and it can be seen that the composite has two mesopore distribution peaks at 3.90nm and 15.03 nm.
Preparation example 2
(1) Weighing 10g of nickel acetate, 20g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker containing 100m L deionized water, stirring at 80 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the solid precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 150m L/min, heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel material.
(3) Weighing 2g of the carbon-coated nickel material obtained in the step (2), adding 4m of magnesium nitrate L containing 0.8589 into the carbon-coated nickel material, soaking the mixture for 24 hours, and then drying the mixture at 120 ℃.
(4) And (3) placing the dried material obtained in the step (3) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow rate of 70m L/min, heating to 500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the magnesium-containing carbon-coated nickel nanocomposite.
Characterization of the materials:
the atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 82.4 at%, the nickel content was 2.68 at%, the oxygen content was 9.26 at%, the nitrogen content was 4.09 at%, and the magnesium content was 1.57 at%.
From the TEM image (fig. 5) of this material it can be seen that: the outer layer of the nickel nano-particles is wrapped with a graphitized carbon layer to form a complete core-shell structure. Fig. 6 shows an X-ray diffraction pattern of the nanocomposite material in which diffraction peaks corresponding to carbon (25.9 ° 2 θ angle) and fcc Ni (44.5 °, 51.7 ° and 76.4 ° 2 θ angle) and nickel (hcp-Ni) of close-packed cubic structure (41.9 °, 44.4 °, 47.3 ° and 62.4 ° 2 θ angle) exist. The average particle size of the carbon-coated nickel nanoparticles was calculated to be 13.4nm by the scherrer equation.
The BET test shows that the specific surface area of the material is 142m2Per g, pore volume 0.221cm3Per g, wherein>Pore volume of 0.213cm at 2nm3In terms of/g, 96.3% of the total pore volume. Fig. 7 is a BJH pore size distribution curve of the nanocomposite, which has two mesopore distribution peaks at 3.65nm and 9.91 nm.
Comparative preparation example
(1) Weighing 10g of nickel acetate, 10g of citric acid and 20g of hexamethylenetetramine, adding the nickel acetate, the citric acid and the hexamethylenetetramine into a beaker filled with 30m L deionized water, stirring at 70 ℃ to obtain a homogeneous solution, and continuously heating and evaporating to dryness to obtain a solid precursor.
(2) And (2) placing the precursor obtained in the step (1) in a porcelain boat, then placing the porcelain boat in a constant temperature area of a tube furnace, introducing nitrogen with the flow of 100m L/min, heating to 650 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, stopping heating, and cooling to room temperature in the nitrogen atmosphere to obtain the carbon-coated nickel nanocomposite.
The atomic percentage of the elements contained in the nanocomposite material measured by X-ray photoelectron spectroscopy (XPS) is as follows: the carbon content was 90.47 at%, the nickel content was 1.38 at%, the oxygen content was 3.97 at%, and the nitrogen content was 4.18 at%.
Example 1
The composite material obtained in the preparation example 1 is used as a catalyst for the reaction of preparing a target product, namely a cyclohexanol compound by hydrogenating a phenol compound, and the specific experimental steps are as follows:
0.1g of nano-compositeThe material, 1.88g phenol, 100m L water were added to the autoclave and H was added2After 3 times of replacement, the reaction kettle is charged with H2And (3) controlling the pressure in the reaction kettle to be 6MPa, stirring and heating, heating to the preset reaction temperature of 150 ℃, stopping heating after the reaction is carried out for 10 hours, cooling to room temperature, discharging pressure, and opening the reaction kettle to take the product cyclohexanol for chromatographic analysis. The reactant conversion and the target product selectivity were calculated by the following formulas:
conversion-amount of reacted reaction mass/amount of added reaction × 100%
The selectivity is × 100% based on the mass of the target product/mass of the reaction product
After analysis, the phenol conversion was 100% and the cyclohexanol selectivity was 97.4%.
When the reaction proceeded for 300s, a sample was taken and chromatographed to calculate the conversion of the reactant, and TOF of the catalyst was 5.56 × 10, obtained by the formula TOF (amount of reacted reactant species)/(amount of catalytically active metal species 300s)-3s-1。
Example 2
The nano composite material prepared in preparation example 1 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of phenol and 30m of L water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to preset reaction temperature of 180 deg.C, continuously making reaction for 8 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out cyclohexanol product to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain phenol conversion rate of 100%, cyclohexanol selectivity of 99.3% and TOF of 5.41 × 10-3s-1。
Example 3
The nano composite material prepared in preparation example 1 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 0.52g of phenol and 50m of L water were added to a reaction vesselIntroduction of H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 1MPa, stirring and heating, heating to 250 deg.C, continuously making reaction for 10 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out cyclohexanol product to make chromatographic analysis so as to obtain the invented product with conversion rate of reactant, selectivity of product and TOF, respectively, and obtaining phenol conversion rate of 100%, selectivity of cyclohexanol of 99.2% and TOF of 7.12 × 10-3s-1。
Example 4
The nano composite material prepared in preparation example 1 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
0.2g of the nanocomposite, 0.66g of phenol and 50m of L m of cyclohexane were added to a reaction vessel, and H was passed through2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to preset reaction temperature of 180 deg.C, continuously making reaction for 8 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out cyclohexanol product to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using formula shown in example 1 to obtain phenol conversion rate of 100%, cyclohexanol selectivity of 98.8% and TOF of 6.55 × 10-3s-1。
Example 5
The nano composite material prepared in preparation example 1 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.40g of 4-cyclopropylphenol and 30m of L m of water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is controlled to be 3MPa, the temperature is raised by stirring, the temperature is raised to be 180 ℃ at the preset reaction temperature, the heating is stopped after the reaction is continued for 10 hours, the temperature is reduced to room temperature, the pressure is discharged, the reaction kettle is opened, the product 4-cyclopropylcyclohexanol is taken out to carry out chromatographic analysis, the conversion rate of the reactant, the product selectivity and TOF are respectively calculated by the formula shown in example 1, and the conversion rate of the 4-cyclopropylphenol is 100 percent, the selectivity of the 4-cyclopropylcyclohexanol is 99.0 percent, and the TOF is 6.34 × 10-3s-1。
Example 6
The nano composite material prepared in preparation example 1 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 0.37g of 2, 6-dimethylphenol and 30m of L m of water are added into a reaction kettle, and H is introduced2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is controlled to be 3MPa, the temperature is raised by stirring, the temperature is raised to be 180 ℃ at the preset reaction temperature, the heating is stopped after the reaction is continued for 10 hours, the temperature is reduced to room temperature, the pressure is discharged, the reaction kettle is opened, the product 2, 6-dimethylcyclohexanol is taken out to carry out chromatographic analysis, the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in the example 1, and the conversion rate of the 2, 6-dimethylphenol is 100 percent, the selectivity of the 2, 6-dimethylcyclohexanol is 99.1 percent, and the TOF is 6-3s-1。
Example 7
The nano composite material prepared in preparation example 2 is used as a catalyst for a hydrogenation reduction reaction of a phenol compound, and the specific experimental steps are as follows:
adding 0.1g of nano composite material, 0.33g of phenol and 30m of L water into a reaction kettle, and introducing H2After replacing the reaction kettle for 3 times, introducing H again2Making the pressure in the reaction kettle be 3MPa, stirring and heating, heating to preset reaction temperature of 180 deg.C, continuously making reaction for 10 hr, stopping heating, cooling to room temperature, discharging pressure, opening reaction kettle and taking out cyclohexanol product to make chromatographic analysis, and respectively calculating reactant conversion rate, product selectivity and TOF by using the formula shown in example 1 to obtain phenol conversion rate of 100%, cyclohexanol selectivity of 99.5% and TOF of 5.43 × 10-3s-1。
Comparative example
The nano composite material prepared by the comparative preparation example is used for the hydrogenation reduction reaction of the phenol compound as a catalyst, and the specific experimental steps are as follows:
0.1g of the nanocomposite, 1.88g of phenol and 100m of L g of water were added to a reaction vessel, and H was introduced2After replacing the reaction kettle for 3 times, introducing H again2The pressure in the reaction kettle is 6MPa, and the mixture is stirredHeating, heating to a predetermined reaction temperature of 150 ℃, continuously reacting for 10 hours, stopping heating, cooling to room temperature, discharging pressure, opening the reaction kettle, taking out cyclohexanol as a product, and performing chromatographic analysis, wherein the conversion rate of the reactant, the selectivity of the product and the TOF are respectively calculated by the formula shown in example 1, so that the phenol conversion rate is 100%, the selectivity of the cyclohexanol is 95.8%, and the TOF is 3.95 × 10-3s-1。
It can be seen from the above examples and comparative examples that the nanocomposite of the present invention has a good catalytic effect when used as a catalyst for catalyzing a catalytic hydrogenation reaction of a phenol compound, and compared with a catalyst containing no alkaline earth metal, the nanocomposite containing carbon coated nickel containing an alkaline earth metal not only enables the catalytic reaction to have a high conversion rate and a high product selectivity, but also has a higher catalytic reaction rate and a better catalytic performance.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (12)
1. A method for synthesizing cyclohexanol compounds comprises the following steps:
the method comprises the following steps of (1) catalyzing a phenol compound to carry out hydrogenation reduction reaction in a hydrogen atmosphere by taking a carbon-coated nickel nano composite material containing alkaline earth metal as a catalyst;
the nano composite material comprises a core-shell structure with a shell layer and an inner core, wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen, and the inner core is nickel nano particles.
2. The method of claim 1, wherein the phenolic compound further comprises a substituent on the benzene ring, wherein the substituent is selected from C1-20One or more of alkyl, cycloalkyl and aryl.
3. The synthesis method according to claim 1 or 2, wherein the phenolic compound is selected from one or more of phenol, 2, 6-dimethylphenol and 4-cyclopropylphenol.
4. The synthesis process according to claim 1, wherein the catalyst is used in an amount of 1% to 50%, preferably 5% to 30%, based on the mass of the phenolic compound.
5. The synthesis process of claim 1, wherein the temperature of the hydrogenation reduction reaction is from 150 ℃ to 250 ℃.
6. The synthesis process according to claim 1, wherein the pressure of the hydrogen is from 3MPa to 6 MPa.
7. The synthesis method according to claim 1, wherein the catalyst and the phenol compound are mixed in a solvent and then subjected to hydrogenation reduction reaction, wherein the solvent is selected from one or more of alcohols, ethers, alkanes and water.
8. The synthesis method according to any one of claims 1 to 7, wherein the nanocomposite is a mesoporous material having at least one mesopore distribution peak.
9. The method of synthesizing as defined in claim 8 wherein the nanocomposite is a mesoporous material having two or more mesopore distribution peaks.
10. The method of synthesis according to claim 8, wherein the mesoporous material has a proportion of mesopore volume of more than 50%, preferably more than 80%, of the total pore volume.
11. The method of claim 1, wherein the alkaline earth metal comprises 0.1 at% to 3 at%, carbon comprises 65 at% to 95 at%, nickel comprises 0.1 at% to 10 at%, oxygen comprises 1 at% to 20 at%, and nitrogen comprises 1 at% to 10 at%, in terms of atomic percentage.
12. The method of synthesis according to any one of claims 1 to 11, the alkaline earth metal being selected from one or more of beryllium, magnesium, calcium, strontium, barium and radium.
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CN113336624A (en) * | 2021-06-16 | 2021-09-03 | 东北石油大学 | Selective hydrogenation method for phenol on Ni-based catalyst |
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US4203923A (en) * | 1974-11-26 | 1980-05-20 | Allied Chemical Corporation | Method for promotion of phenol hydrogenation |
CN102791668A (en) * | 2009-12-18 | 2012-11-21 | 帝斯曼知识产权资产管理有限公司 | Catalysed phenol hydrogenation |
CN104447209A (en) * | 2014-11-19 | 2015-03-25 | 浙江大学 | Method for preparing cyclohexanol by catalyzing by base metal catalyst |
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US4203923A (en) * | 1974-11-26 | 1980-05-20 | Allied Chemical Corporation | Method for promotion of phenol hydrogenation |
CN102791668A (en) * | 2009-12-18 | 2012-11-21 | 帝斯曼知识产权资产管理有限公司 | Catalysed phenol hydrogenation |
CN104447209A (en) * | 2014-11-19 | 2015-03-25 | 浙江大学 | Method for preparing cyclohexanol by catalyzing by base metal catalyst |
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CN113336624A (en) * | 2021-06-16 | 2021-09-03 | 东北石油大学 | Selective hydrogenation method for phenol on Ni-based catalyst |
CN113336624B (en) * | 2021-06-16 | 2023-08-18 | 东北石油大学 | Method for selectively hydrogenating phenol on Ni-based catalyst |
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