CN115364866B - 一种Ni-M@NiO-Al2O3催化剂及其制备和应用 - Google Patents
一种Ni-M@NiO-Al2O3催化剂及其制备和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 67
- 229910018062 Ni-M Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- -1 phthalic acid ester Chemical class 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 241000257465 Echinoidea Species 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 239000000706 filtrate Substances 0.000 description 25
- 229910000510 noble metal Inorganic materials 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004811 liquid chromatography Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 241000282414 Homo sapiens Species 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 4
- 229960001826 dimethylphthalate Drugs 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- SDERSPLNEZLKSY-UHFFFAOYSA-N cyclohexane;formic acid Chemical compound OC=O.OC=O.C1CCCCC1 SDERSPLNEZLKSY-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JLVWYWVLMFVCDI-UHFFFAOYSA-N diethyl benzene-1,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC)=C1 JLVWYWVLMFVCDI-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
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- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- 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
- B01J23/83—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 rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
本发明提供了一种Ni‑M@NiO‑Al2O3催化剂及其制备和应用,其特征在于其特征在于Ni为活性组分,助活性组分M为过渡金属W、Cr、Zr、Co、La或Ce中的一种,NiO和无定形Al2O3作为载体,催化剂形貌为多孔球形海胆状;所述的催化剂采用NiMAl‑LDHs作为前驱体,通过直接热还原得到Ni‑M/NiO‑Al2O3催化剂。将催化剂用于催化苯二甲酸酯加氢制备环己烷二甲酸酯,底物苯二甲酸酯的转化率高,目标产物环己烷二甲酸酯的选择性较高。本方法制备的Ni‑M/NiO‑Al2O3催化剂具有高活性、催化剂易分离、价格低廉等优点,具有良好的工业应用前景。
Description
技术领域
本发明涉及一种催化剂及其制备和应用,尤其涉及一种Ni-M@NiO-Al2O3催化剂及其制备和在催化苯二甲酸酯合成环己烷二甲酸酯中的应用。
背景技术
芳香族羧酸酯是塑料制品重要的原材料之一,其中邻苯二甲酸酯类、对苯二甲酸酯类主要用作聚酯纤维、医药用品以及包装领域等的生产;均苯四甲酸酯类主要用于合成医药及聚酰亚胺薄膜等。但芳香族羧酸酯中含有苯环官能团,它很容易渗透进入人体。邻苯二甲酸酯可以从塑料产品内扩散到外部环境,通过呼吸道、消化道和皮肤进入人体,引起细胞癌变,对人体生殖有毒害作用。邻苯二甲酸酯类增塑剂的巨大危害,逐渐引起了广大公众的广泛关注。随着人类环保和安全意识不断提高,“绿色化学”这一概念应运而生,世界各国已经采取了相应对的措施来限制邻苯二甲酸酯类增塑剂的使用。因此,需要对芳香族羧酸酯中的苯环官能团氢化处理,开发出更加环保的生产原材料。苯环官能团的加氢催化反应,具有原子经济性、无污染、易分离、可持续应用等优点,在化工生产中逐渐受到重视。苯二甲酸二甲酯工业上催化加氢一般采用负载型贵金属催化剂,贵金属催化剂具有较高的加氢活性以及选择性,但存在着催化剂成本高、回收过程复杂及不利于工业化的进一步发展等缺点。非贵金属价格低廉,储量丰富,且具有较好的催化加氢选择性,有望取代当前商用贵金属催化剂,所以,现在研究的关注点大多在非贵金属基催化剂。但传统负载型催化剂常采用浸渍法制备,浸渍法在反应过程中易受到溶剂化效应等因素的影响,造成金属颗粒团聚长大以及溶脱,导致催化剂的反应活性和使用寿命较差。
德国专利2823165阐述了在负载型Ni,Ru,Rh或Pd催化剂,用于苯二甲酸二甲酯加氢反应,在70~250℃,3~20MPa条件下加氢转化为相应的脂肪酸二甲酸二甲酯。美国U.SCO7C67/303(2006010)介绍了一种DOP高压釜间歇式氢化方法其反应压力达到12MPa,反应温度230℃,贵金属催化剂用量高达20%,DOP中苯环被加氢转化为环己烷,转化率不到90%。中国专利CN102658182采用非贵金属Ni作为活性组分,P作为助剂负载与Al2O3载体上,并用于邻苯二甲酸酯类加氢反应。但其反应压力最高达到了30Mpa,反应温度也高达200℃。
综合现有技术,苯二甲酸酯加氢合成环己烷二甲酸酯目前催化剂都采用贵金属Rh、Pd、Pt、Ru等作为活性组分,且催化剂用量较大,不利于工业化生产。因此,需要设计和开发更加利于工业化生产的非贵金属催化剂。
发明内容
本发明的一个目的在于改进现有技术存在的问题与不足提供一种Ni-M@NiO-Al2O3催化剂,本发明另一个目的在于提供上述催化剂的制备方法,本发明还有一个目的在于提供上述催化剂在催化苯二甲酸酯合成环己烷二甲酸酯的应用。
本发明的技术方案为:一种Ni-M@NiO-Al2O3催化剂,其特征在于Ni为活性组分,助活性组分M为过渡金属W、Cr、Zr、Co、La或Ce中的一种,NiO和无定形Al2O3作为载体,催化剂形貌为多孔球形海胆状;其中NiO与Al2O3的摩尔比为(0.25~1):1,活性组分Ni与Al2O3的摩尔比为(1.5~4):1,助活性组分M与Al2O3的摩尔比为(0.1~0.5):1。
本发明还提供了一种制备上述的Ni-M@NiO-Al2O3催化剂的方法,其具体操作步骤为:
(1)NiMAl-LDHs前驱体的制备:分别称取镍、铝和助活性组分M的金属盐配成水溶液A,氢氧化钠、碳酸钠和尿素配成水溶液B;先在容器中加入水,滴加水溶液B调节溶液pH值为碱性,然后将水溶液A、B同时滴入,维持pH值不变直至水溶液A滴完,然后将剩余水溶液B滴完,继续搅拌,随后水热,冷却,过滤,洗涤,干燥,得到NiMAl-LDHs前驱体;
(2)Ni-M@NiO-Al2O3催化剂的制备:将NiMAl-LDHs前驱体在氢氮混合气氛下直接热还原得到Ni-M@NiO-Al2O3催化剂。
优选步骤(1)水溶液A中镍、铝和助活性组分M的金属盐的摩尔比为1:(0.4~1):(0.05~0.25);水溶液A中金属Ni2+、Al3+和Mn+的浓度为C(Ni2+)+C(Al3+)+C(Mn+)=0.4~0.7mol/L;水溶液B中氢氧化钠、碳酸钠和尿素浓度分别为:C(NaOH)=0.5~1mol/L,C(Na2CO3)=0.2~0.5mol/L,C(CO(NH2)2)=0.2~0.5mol/L;pH为9~11,继续搅拌的时间为2~4h,水热反应温度为100~150℃,水热反应时间为12~36h。
优选步骤(1)中的镍金属盐为氯化镍、硝酸镍或硫酸镍中的任一种;铝金属盐为氯化铝、硝酸铝或硫酸铝中的任一种;助活性组分M的金属盐为偏钨酸铵、仲钨酸铵、硝酸铬、硝酸锆、硝酸钴、硝酸镧或硝酸铈中的任一种。
优选步骤(2)中氢氮混合气氛中氢气体积分数为10~20%,流速为60~100mL/min;直接热还原温度为400~700℃,升温速率为2~10℃/min,热还原时间为2~5h。
本发明还提供了一种上述的Ni-M@NiO-Al2O3催化剂在催化苯二甲酸酯合成环己烷二甲酸酯中的应用。其特征在于在反应釜中依次加入制备的Ni-M@NiO-Al2O3催化剂、苯二甲酸酯和溶剂,使用氢气置换釜内空气后,充压、升温至反应温度后开始反应,反应结束后利用离心分离出催化剂。
优选上述原料苯二甲酸酯与Ni-M@NiO-Al2O3催化剂的质量比为1:(0.15~0.30),原料与溶剂的质量比为1:(5~15);反应温度为120~150℃,反应时间3~6h,氢气压力为5~8MPa。
优选上述的溶剂为甲醇、乙醇、异丙醇、乙酸乙酯或DMF中的一种或几种。
与现有技术相比,本发明的有益效果主要体现在:
(1)本发明所提供的Ni-M/NiO-Al2O3催化剂合成方法具有设备简单、操作方便、条件温和、且利用硝酸盐及尿素制备水滑石,通过直接热还原能有效降低活性金属的团聚形成多孔的球形海胆状结构等优点,工艺过程对环境友好,有利于规模化生产。
(2)本发明所提供的Ni-M/NiO-Al2O3催化剂为非贵金属催化剂,与现有贵金属催化剂相比,降低了生产成本,更有利于工业化生产。
(3)本发明所提供的Ni-M/NiO-Al2O3催化剂用于催化苯二甲酸酯合成环己烷二甲酸酯,具有较高的转化率和选择性。
附图说明
图1是实施例1制备的NiWAl-LDHs前驱体及还原后Ni-W/NiO-Al2O3的XRD图谱;
图2是实施例1制备的Ni-W/NiO-Al2O3的SEM图谱。
具体实施方式
以下用实施例对本发明作更详细的描述。这些实施例仅是对本发明最佳实施方式的描述,并不对本发明的保护范围有任何限制。
实施例1
步骤1:将Ni(NO3)2·6H2O、Al(NO3)3·9H2O与H28N6O41W12三种盐按Ni/Al/W摩尔比为1:0.5:0.1,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(W3+)=0.6mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=0.7mol/L,C(Na2CO3)=0.3mol/L,C(CO(NH2)2)=0.3mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL去离子水溶液于三口瓶中,先在容器中加入水,滴加水溶液B调节溶液pH值为pH为10,然后将水溶液A、B同时滴入,维持pH值10直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌2h。随后将此溶液转移至水热釜中,120℃下加热晶化24h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiWAl-LDHs前体。
步骤2:将上述所得的NiWAl-LDHs样品置于管式炉中,用氢气体积分数为10%的氢氮混合气体吹扫30min,在流速为60mL/min的流速下,以5℃/min升温速率升温至600℃,保持3h,热还原,得到Ni-W/NiO-Al2O3催化剂,记为Ni-W/NiO-Al2O3-1,其中NiO与Al2O3的摩尔比为0.4:1,活性组分Ni与Al2O3的摩尔比为3.6:1,助活性组分M与Al2O3的摩尔比为0.4:1。
Ni-W/NiO-Al2O3-1催化剂XRD表征如图1所示,从该XRD图可以看出合成的NiWAl-LDHs前驱体呈均匀的层状结构,为标准的水滑石结构。焙烧还原后的Ni-W/NiO-Al2O3-1催化剂样品在37°,43°和63°处有特征峰,结果证明了该催化剂形成了含Al3+的NiO相,在44°,52°和76°处出现了还原态的Ni单质,而Al2O3以无定形的形式出现,未观察到W的对应特征衍射峰,说明W在催化剂中分散均匀。Ni-W/NiO-Al2O3-1催化剂的SEM表征如图2所示,从该SEM图可以看出所制备的Ni-W/NiO-Al2O3-1催化剂的形貌为多空的球形海胆状。
实施例2
步骤1:将无水Ni(NO3)2·6H2O、AlCl3与(NH4)10W12O41·5H2O三种盐溶液按Ni/Al/W摩尔比为1:0.5:0.05,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(W3+)=0.4mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=0.6mol/L,C(Na2CO3)=0.25mol/L,C(CO(NH2)2)=0.3mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为11,然后将水溶液A、B同时滴入,维持pH值为11直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌3h。随后将此溶液转移至水热釜中,150℃下加热晶化12h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiWAl-LDHs前体。
步骤2:将上述所得的NiWAl-LDHs样品置于管式炉中,用氢气体积分数为10%的氢氮混合气体吹扫30min,在流速为80mL/min的流速下,以3℃/min升温速率升温至600℃,保持4h,热还原,得到Ni-W/NiO-Al2O3催化剂,记为Ni-W/NiO-Al2O3-2,其中NiO与Al2O3的摩尔比为0.4:1,活性组分Ni与Al2O3的摩尔比为3.6:1,助活性组分M与Al2O3的摩尔比为0.2:1。
实施例3
步骤1:将NiCl2·6H2O、Al(NO3)3·9H2O与Cr(NO3)3·9H2O三种盐溶液按Ni/Al/Cr摩尔比为1:0.4:0.05,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(Cr3 +)=0.7mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=1.0mol/L,C(Na2CO3)=0.2mol/L,C(CO(NH2)2)=0.5mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为10,然后将水溶液A、B同时滴入,维持pH值为10直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌4h。随后将此溶液转移至水热釜中,130℃下加热晶化36h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiCrAl-LDHs前体。
步骤2:将上述所得的NiCrAl-LDHs样品置于管式炉中,用氢气体积分数为10%的氢氮混合气体吹扫30min,在流速为100mL/min的流速下,以10℃/min升温速率升温至700℃,保持2h,热还原,得到Ni-Cr/NiO-Al2O3催化剂,记为Ni-Cr/NiO-Al2O3-3,其中NiO与Al2O3的摩尔比为1:1,活性组分Ni与Al2O3的摩尔比为4:1,助活性组分M与Al2O3的摩尔比为0.25:1。
实施例4
步骤1:将NiSO4·6H2O、Al(NO3)3·9H2O与Zr(NO3)4·5H2O三种盐溶液按Ni/Al/Zr摩尔比为1:0.4:0.1,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(Zr4 +)=0.5mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=0.5mol/L,C(Na2CO3)=0.5mol/L,C(CO(NH2)2)=0.5mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为9,然后将水溶液A、B同时滴入,维持pH值为9直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌2h。随后将此溶液转移至水热釜中,150℃下加热晶化12h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiZrAl-LDHs前体。
步骤2:将上述所得的NiZrAl-LDHs样品置于管式炉中,用氢气体积分数为20%的氢氮混合气体吹扫30min,在流速为100mL/min的流速下,以5℃/min升温速率升温至700℃,保持2h,热还原,得到Ni-Zr/NiO-Al2O3催化剂,记为Ni-Zr/NiO-Al2O3-4,其中NiO与Al2O3的摩尔比为1:1,活性组分Ni与Al2O3的摩尔比为4:1,助活性组分M与Al2O3的摩尔比为0.5:1。
实施例5
步骤1:将Ni(NO3)2·6H2O、Al2(SO4)3·18H2O与La(NO3)3·6H2O三种盐溶液按Ni/Al/Cu摩尔比为1:0.8:0.2,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3 +)+C(La3+)=0.6mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=1mol/L,C(Na2CO3)=0.3mol/L,C(CO(NH2)2)=0.4mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为9,然后将水溶液A、B同时滴入,维持pH值为9直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌2h。随后将此溶液转移至水热釜中,100℃下加热晶化24h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiLaAl-LDHs前体。
步骤2:将上述所得的NiLaAl-LDHs样品置于管式炉中,用氢气体积分数为20%的氢氮混合气体吹扫30min,在流速为60mL/min的流速下,以2℃/min升温速率升温至700℃,保持5h,热还原,得到Ni-La/NiO-Al2O3催化剂,记为Ni-La/NiO-Al2O3-5,其中NiO与Al2O3的摩尔比为0.25:1,活性组分Ni与Al2O3的摩尔比为2.25:1,助活性组分M与Al2O3的摩尔比为0.5:1。
实施例6
步骤1:将Ni(NO3)2·6H2O、Al(NO3)3·9H2O与Co(NO3)2·6H2O三种盐溶液按Ni/Al/Co摩尔比为1:1:0.25,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(Co2+)=0.5mol/L的水溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=0.6mol/L,C(Na2CO3)=0.5mol/L,C(CO(NH2)2)=0.2mol/L,加入到75mL去离子水中溶解,配制成水溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为10,然后将水溶液A、B同时滴入,维持pH值为10直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌3h。随后将此溶液转移至水热釜中,100℃下加热晶化36h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiCoAl-LDHs前体。
步骤2:将上述所得的NiCoAl-LDHs样品置于管式炉中,用氢气体积分数为10%的氢氮混合气体吹扫30min,在流速为80mL/min的流速下,以10℃/min升温速率升温至500℃,保持3h,热还原,得到Ni-Co/NiO-Al2O3催化剂,记为Ni-Co/NiO-Al2O3-6,其中NiO与Al2O3的摩尔比为0.3:1,活性组分Ni与Al2O3的摩尔比为1.7:1,助活性组分M与Al2O3的摩尔比为0.5:1。
实施例7
步骤1:将Ni(NO3)2·6H2O、AlCl3与Ce(NO3)3·6H2O三种盐溶液按Ni/Al/Zn摩尔比为1:1:0.05,加入到75mL去离子水中进行溶解,配制成浓度为C(Ni2+)+C(Al3+)+C(Ce3+)=0.6mol/L的溶液A。再将氢氧化钠、碳酸钠及尿素按C(NaOH)=1mol/L,C(Na2CO3)=0.5mol/L,C(CO(NH2)2)=0.2mol/L,加入到75mL去离子水中溶解,配制成溶液B。取50mL的去离子水溶液于三口瓶中,滴加水溶液B调节溶液pH值为10,然后将水溶液A、B同时滴入,维持pH值为10直至水溶液A滴加完毕,随后将剩余水溶液B全部滴加完毕,继续搅拌4h。随后将此溶液转移至水热釜中,120℃下加热晶化36h,过滤并用去离子水洗涤至滤液为中性,干燥12h,玛瑙研钵中研磨制备得到高分散的NiCeAl-LDHs前体。
步骤2:将上述所得的NiCeAl-LDHs样品置于管式炉中,用氢气体积分数为10%的氢氮混合气体吹扫30min,在流速为60mL/min的流速下,以5℃/min升温速率升温至400℃,保持4h,热还原,得到Ni-Ce/NiO-Al2O3催化剂,记为Ni-Ce/NiO-Al2O3-7,其中NiO与Al2O3的摩尔比为0.5:1,活性组分Ni与Al2O3的摩尔比为1.5:1,助活性组分M与Al2O3的摩尔比为0.1:1。
以Ni-M/NiO-Al2O3为催化剂催化苯二甲酸酯合成环己烷二甲酸酯:
应用例1
依次称取0.40g邻苯二甲酸二甲酯原料,0.10gNi-W/NiO-Al2O3-1催化剂和4.00g异丙醇溶剂,即原料与催化剂质量比为1:0.25,原料质量与溶剂质量比为1:10,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为7MPa,调节搅拌速度为600r/min,升高温度至反应温度130℃,开始反应,反应4h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为99.60%,选择性为99.45%。
应用例2
依次称取0.20g邻苯二甲酸二甲酯原料,0.03gNi-W/NiO-Al2O3-2催化剂和3.00g异丙醇溶剂,即原料与催化剂质量比为1:0.15,原料质量与溶剂质量比为1:15,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为8MPa,调节搅拌速度为600r/min,升高温度至反应温度140℃,开始反应,反应4h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为98.81%,选择性为98.10%。
应用例3
依次称取0.40g邻苯二甲酸二乙酯原料,0.08gNi-Cr/NiO-Al2O3-3催化剂和4.00g乙酸乙酯溶剂,即原料与催化剂质量比为1:0.2,原料质量与溶剂质量比为1:10,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为5MPa,调节搅拌速度为600r/min,升高温度至反应温度150℃,开始反应,反应6h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为98.22%,选择性为96.21%。
应用例4
依次称取0.30g间苯二甲酸二甲酯原料,0.09gNi-Zr/NiO-Al2O3-4催化剂和2.25g甲醇溶剂,即原料与催化剂质量比为1:0.3,原料质量与溶剂质量比为1:7.5,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为5MPa,调节搅拌速度为600r/min,升高温度至反应温度120℃,开始反应,反应5h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为99.25%,选择性为98.62%。
应用例5
依次称取0.50g间苯二甲酸二乙酯原料,0.10gNi-La/NiO-Al2O3-5催化剂和2.50g甲醇溶剂,即原料与催化剂质量比为1:0.2,原料质量与溶剂质量比为1:5,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为6MPa,调节搅拌速度为600r/min,升高温度至反应温度140℃,开始反应,反应5h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为98.66%,选择性为97.26%。
应用例6
依次称取0.10g对苯二甲酸二甲酯原料,0.015gNi-Co/NiO-Al2O3-6催化剂和1.50g乙醇溶剂,即原料与催化剂质量比为1:0.15,原料质量与溶剂质量比为1:15,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为8MPa,调节搅拌速度为600r/min,升高温度至反应温度120℃,开始反应,反应6h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为99.41%,选择性为97.22%。
应用例7
依次称取0.4g对苯二甲酸二辛酯原料,0.1gNi-Ce/NiO-Al2O3-7催化剂和3.00gDMF溶剂,即原料与催化剂质量比为1:0.25,原料质量与溶剂质量比为1:7.5,加入高压反应釜中,使用氢气置换反应釜内空气3次,向反应釜中充入氢气至压力为7MPa,调节搅拌速度为600r/min,升高温度至反应温度130℃,开始反应,反应3h,反应结束后利用离心分离出催化剂。对反应得到的液体进行液相色谱分析,转化率为99.35%,选择性为96.51%。
应用例实验结果如表1
表1应用例实验结果表
Claims (8)
1.一种Ni-M@NiO-Al2O3催化剂,其特征在于Ni为活性组分,助活性组分M为过渡金属W、Cr、Zr、Co、La或Ce中的一种,NiO和无定形Al2O3作为载体,催化剂形貌为多孔球形海胆状;其中NiO与Al2O3的摩尔比为(0.25~1):1,活性组分Ni与Al2O3的摩尔比为(1.5~4):1,助活性组分M与Al2O3的摩尔比为(0.1~0.5):1;由以下方法制备得到,其具体步骤为:
(1)NiMAl-LDHs前驱体的制备:分别称取镍、铝和助活性组分M的金属盐配成水溶液A,氢氧化钠、碳酸钠和尿素配成水溶液B;先在容器中加入水,滴加水溶液B调节溶液pH值为碱性,然后将水溶液A、B同时滴入,维持pH值不变直至水溶液A滴完,然后将剩余水溶液B滴完,继续搅拌,随后水热,冷却,过滤,洗涤,干燥,得到NiMAl-LDHs前驱体;
(2)Ni-M@NiO-Al2O3催化剂的制备:将NiMAl-LDHs前驱体在氢氮混合气氛下直接热还原得到Ni-M@NiO-Al2O3催化剂。
2.根据权利要求1所述的Ni-M@NiO-Al2O3催化剂,其特征在于步骤(1)水溶液A中镍、铝和助活性组分M的金属盐的摩尔比为1:(0.4~1):(0.05~0.25);水溶液A中金属Ni2+、Al3+和Mn+的浓度为C(Ni2+)+C(Al3+)+C(Mn+)=0.4~0.7mol/L;水溶液B中氢氧化钠、碳酸钠和尿素浓度分别为:C(NaOH)=0.5~1mol/L,C(Na2CO3)=0.2~0.5mol/L,C(CO(NH2)2)=0.2~0.5mol/L;滴加水溶液B调节溶液pH值为9~11,继续搅拌的时间为2~4h,水热反应温度为100~150℃,水热反应时间为12~36h。
3.根据权利要求1所述的Ni-M@NiO-Al2O3催化剂,其特征在于步骤(1)中的镍金属盐为氯化镍、硝酸镍或硫酸镍中的任一种;铝金属盐为氯化铝、硝酸铝或硫酸铝中的任一种;助活性组分M的金属盐为偏钨酸铵、仲钨酸铵、硝酸铬、硝酸锆、硝酸钴、硝酸镧或硝酸铈中的任一种。
4.根据权利要求1所述的Ni-M@NiO-Al2O3催化剂,其特征在于步骤(2)中氢氮混合气氛中氢气体积分数为10~20%,流速为60~100mL/min;直接热还原温度为400~700℃,升温速率为2~10℃/min,热还原时间为2~5h。
5.一种如权利要求1所述的Ni-M@NiO-Al2O3催化剂在催化苯二甲酸酯合成环己烷二甲酸酯中的应用。
6.根据权利要求5所述的应用,其特征在于在反应釜中依次加入制备的Ni-M@NiO-Al2O3催化剂、苯二甲酸酯和溶剂,使用氢气置换釜内空气后,充压、升温至反应温度后开始反应,反应结束后利用离心分离出催化剂。
7.根据权利要求6所述的应用,其特征在于原料苯二甲酸酯与Ni-M@NiO-Al2O3催化剂的质量比为1:(0.15~0.30),原料与溶剂的质量比为1:(5~15);反应温度为120~150℃,反应时间3~6h,氢气压力为5~8MPa。
8.根据权利要求6所述的应用,其特征在于所述的溶剂为甲醇、乙醇、异丙醇、乙酸乙酯或DMF中的一种或几种。
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