CN107774275B - Preparation method of hydrogenation catalyst - Google Patents
Preparation method of hydrogenation catalyst Download PDFInfo
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- CN107774275B CN107774275B CN201610767708.9A CN201610767708A CN107774275B CN 107774275 B CN107774275 B CN 107774275B CN 201610767708 A CN201610767708 A CN 201610767708A CN 107774275 B CN107774275 B CN 107774275B
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- alumina powder
- acid
- organic
- modified alumina
- modified
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005470 impregnation Methods 0.000 claims abstract description 28
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 10
- 239000002283 diesel fuel Substances 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 85
- 239000000843 powder Substances 0.000 claims description 76
- 238000001035 drying Methods 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- -1 VIB group metals Chemical class 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 150000002772 monosaccharides Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000001384 succinic acid Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000008139 complexing agent Substances 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 description 47
- 239000000243 solution Substances 0.000 description 27
- 239000011148 porous material Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 241000219782 Sesbania Species 0.000 description 8
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation method of a hydrogenation catalyst. In the method, part of active metal components and organic acid complexing agents are introduced in the carrier forming process, the carrier is formed through a certain roasting treatment procedure, and then the subsequent active metal impregnation step is carried out to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the method has the advantages of uniform dispersion of active metals, simple and easy preparation method, and is particularly suitable for ultra-deep hydrodesulfurization reaction of diesel oil.
Description
Technical Field
The invention relates to a preparation method of a hydrogenation catalyst, in particular to a preparation method of a catalyst suitable for ultra-deep hydrodesulfurization of diesel oil.
Background
Because the crude oil production in the world is getting heavier and the demand for clean oil products is increasing at present, the hydrodesulfurization technology of petroleum fractions plays an increasingly important role in the process of producing clean oil products, and the requirement for high activity of hydrogenation catalysts is increasing day by day.
For ultra-deep hydrodesulfurization catalysts, the II-type active center theory of Co-Mo-S and Ni-Mo-S has been widely accepted by various large research and development organizations, and a novel high-activity hydrotreating catalyst is developed based on the II-type active center theory. The main improvement schemes comprise the selection of a carrier, the application of an additive, the complexation of an impregnation liquid, the vulcanization process, the adjustment of metal components and the like. Meanwhile, the preparation mode of the catalyst is also an important method for improving the effective number and dispersion of the II-type active centers.
CN1938087B, US7737071B2 and EP1733787A1 disclose a method for preparing a hydrogenation catalyst, which comprises impregnating a carrier with a solution containing a group VIB metal compound, a phosphorus-containing component, a group VIII metal compound and an organic acid, followed by drying at a temperature of 200 ℃ or less ~ obtain the catalyst, wherein the content of C derived from the organic acid in the catalyst is 2% ~ 14%.
EP0870003B2 describes a process for the preparation of a hydrogenation catalyst comprising impregnating a support with a solution comprising a compound of a group VIB metal, a compound of a group VIII metal and an organic alcohol and/or a sugar, followed by drying at a temperature of 200 ℃ or less ~ obtain a catalyst in which the C content originating from the organic alcohol and/or the sugar is 2% ~ 10%.
CN201210409660.6 discloses a distillate oil hydrotreating catalyst, which is prepared by using alumina as a carrier, at least one VIB group metal and at least one VIII group metal as hydrogenation active metals, wherein the weight ratio of the VIII group metal/(VIB group metal + VIII group metal) calculated by oxides is 0.30 ~ 0.55, the catalyst contains an organic compound, the content of the organic compound in the catalyst is 1.0 ~ 1.8wt% based on the weight of C, the organic compound is derived from organic acid and organic alcohol and/or organic sugar, a small amount of two organic compounds are added into the catalyst, and the hydrogenation activity of the catalyst is improved by adopting a higher ratio of VIII/(VIB + VIII).
In the method for preparing the catalyst, the active metal components are added after the carrier is formed by adopting a mode of impregnation liquid containing an organic auxiliary agent, and the ultra-deep hydrodesulfurization catalyst needs higher active metal content, so that the content of an auxiliary agent to be added in the impregnation liquid is higher, the viscosity of the impregnation liquid is higher, the dispersion of the active metal is not facilitated, and the preparation difficulty is higher or even the industrial preparation cannot be realized. Meanwhile, the addition of a large amount of organic acid causes a loss of the pore structure of the carrier, and a decrease in the lateral pressure strength of the catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a hydrogenation catalyst. In the method, part of active metal components and organic acid complexing agents are introduced in the carrier forming process, the carrier is formed through a certain roasting treatment procedure, and then the subsequent active metal impregnation step is carried out. The active metal is introduced in several times, so that the impregnating solution has proper organic assistant content, low viscosity, easy preparation process and high hydrogenation catalyst content.
The preparation method of the hydrogenation catalyst comprises the following steps:
(1) respectively preparing an impregnation solution I and an impregnation solution II, wherein the impregnation solution I is prepared by a VIII group metal ~ containing compound, an organic acid and water, and the impregnation solution II is prepared by a VIB group metal ~ containing compound, an organic alcohol and/or an organic sugar and water, wherein the molar ratio of the addition amount of the organic acid to the VIII group metal is 0.01 ~ 2.0 (preferably 0.25 ~ 1.75) in terms of carbon content, and the molar ratio of the organic alcohol and/or the organic sugar to the VIB group metal is 0.01 ~ 2.0 (preferably 0.25 ~ 1.75) in terms of carbon content;
(2) Taking a certain amount of macroporous alumina powder, drying after saturating the impregnation solution I, and then roasting in an inert atmosphere to obtain modified macroporous alumina powder;
(3) Uniformly mixing the modified macroporous alumina powder and the small-pore alumina powder obtained in the step (2) according to a certain proportion, adding an extrusion aid, mixing a peptizing agent and water to form a plastic body, and carrying out kneading, molding, drying and roasting to obtain an alumina carrier;
(4) And (4) saturating and dipping the alumina carrier prepared in the step (3) by using a dipping solution II, and drying to obtain the distillate oil hydrogenation catalyst.
in the method, the organic acid in the step (1) is selected from at least one of organic acids with the carbon number of 2 ~ 10, preferably one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, malonic acid and succinic acid, the organic alcohol is selected from one or more of fatty alcohols with the carbon number of 2 ~ 10, preferably one or more of ethylene glycol, propylene glycol, glycerol, isopropanol, triethylene glycol, 2' ~ imino ~ diethanol, amino ~ triethanol, diethylene glycol, dipropylene glycol, trimethylene glycol, triethylene glycol, tributylene glycol and tetraethylene glycol, and the organic sugar is selected from at least one of monosaccharide with the carbon number of 2 ~ 16 and disaccharide, preferably one or more of sucrose, glucose, fructose, galactose, lactose and maltose.
in the method, the macroporous alumina powder in the step (2) can be a commercial product or prepared according to a conventional method in the field, the concentration of the impregnation liquid I is determined by the water absorption of the alumina powder and the composition content of the catalyst metal, the inert gas is nitrogen or rare gas, the roasting temperature is 200 ~ 650 ℃, preferably 250 ~ 550 ℃, and the roasting time is 1 ~ 5 hours.
in the method, the small% ~ pore alumina powder in the step (3) is a commercial product or is prepared according to a conventional method in the field, the mass of the small% ~ pore alumina powder accounts for 5% ~ 35% of the total mass of the alumina powder (the sum of the large% ~ pore alumina powder and the small% ~ pore alumina powder, the same applies below), the extrusion aid is one or more of methyl cellulose, sesbania powder, starch and polyvinyl alcohol, the addition amount is 1% ~ 5% of the total mass of the alumina powder, the peptizing agent is one or more of dilute nitric acid, dilute phosphoric acid and silicic acid, the addition amount is 1% ~ 5% of the total mass of the alumina powder, the kneading, forming, drying and roasting are carried out by adopting a conventional method in the field, the drying condition is that the temperature is not higher than 130 ℃, preferably 90% ~ 120 ℃, the drying time is 1% ~ 24 hours, and the roasting condition is that the temperature is not higher than 800 ℃, preferably 450% ~ 750 ℃, and the roasting time is 2% ~ 10 hours.
in the method, the concentration of the impregnation liquid II in the step (4) is determined by the water absorption of the carrier and the composition content of the catalyst metal, the drying temperature is not higher than 200 ℃, preferably 110 ~ 150 ℃, and the drying time is 1 ~ 8 h.
in the method, the catalyst contains at least one VIB group metal and at least one VIII group metal as hydrogenation active metals, the weight content of the hydrogenation active metals in terms of oxides is ~ 50%, preferably 10-40% on the basis of the weight of the catalyst, wherein the VIB group metal is preferably Mo and/or W, the VIII group metal is preferably Ni and/or Co, and the weight ratio of the VIII group metal/(VIB group metal + VIII group metal) in terms of oxides (abbreviated as VIII/(VIB + VIII) weight ratio in the invention) is 0.01-0.70.
compared with the prior art, the preparation method of the hydrogenation catalyst provided by the invention has the following advantages:
(1) the method adopts fractional impregnation to prepare the VIB group metal salt and the VIII group metal salt into impregnation liquid respectively, compared with bimetallic impregnation, the content of metal components and organic auxiliary agents in the impregnation liquid is reduced, the viscosity and acidity of the impregnation liquid are effectively reduced, and therefore the pore channels of the alumina carrier are prevented from being excessively damaged in the impregnation process.
(2) The reduction of the concentration of metal ions in the impregnation liquid and the respective impregnation of different metals reduce the competitive adsorption effect between metals, improve the diffusion effect of metal salt molecules and facilitate the uniform dispersion of active metals.
(3) Active metal and organic auxiliary agents are pre-impregnated in the macroporous alumina powder, an Al-C graphitized carbon precursor is formed in an inert gas protection roasting mode, and Co/Ni aluminum spinel is prevented from being formed in the roasting process. Meanwhile, the Al-C graphitized carbon precursor can ensure that alumina large channels are not acidified and damaged by a peptizing agent in the kneading and forming process, so that the catalyst channels are larger and smooth.
The hydrogenation catalyst of the invention is suitable for the hydrogenation treatment of fractions such as liquefied gas, gasoline, kerosene, diesel oil, wax oil and the like, and is particularly suitable for a diesel oil ultra-deep hydrogenation process.
Detailed Description
The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention. The macroporous alumina powder used in the examples is 418 powder for market, and the small-pore alumina powder is SB powder for market. Example 1
100g of macroporous alumina powder (dry basis 85) is placed in a rolling pot, under the condition of rotation, 80ml of aqueous solution containing 18.5g of cobalt nitrate and 1.1g of citric acid is sprayed into the macroporous alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 3 hours, after the drying is carried out for 3 hours at the temperature of 110 ℃, the rolling pot is placed in an atmosphere furnace for roasting for 2 hours, the protective gas is nitrogen, and the roasting temperature is 300 ℃.
And (3) taking out the modified macroporous alumina powder, uniformly mixing with 20g of small-pore alumina powder (dry basis 75), adding 2g of sesbania powder, 25g of 10% phosphoric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 25.4g of ammonium heptamolybdate and 3.2g of glycerol into the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying for 4 hours at 130 ℃ to obtain the finished product of the catalyst A.
Example 2
100g of macroporous alumina powder (dry basis 85) is placed in a rolling pot, under the condition of rotation, 80ml of aqueous solution containing 18.5g of cobalt nitrate and 3.0g of oxalic acid is sprayed into the macroporous alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 3 hours, after the drying is carried out for 3 hours at the temperature of 110 ℃, the rolling pot is placed in an atmosphere furnace for roasting for 2 hours, the protective gas is nitrogen, and the roasting temperature is 350 ℃.
And (3) taking out the modified macroporous alumina powder and 20g of small-pore alumina powder (dry basis 75), uniformly mixing, adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 25.4g of ammonium heptamolybdate and 4.5g of glycol into the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying at 130 ℃ for 4 hours to obtain the finished catalyst B.
Example 3
100g of macroporous alumina powder (dry basis 85) is placed in a rolling pot, under the condition of rotation, 80ml of aqueous solution containing 18.5g of nickel nitrate and 3.5g of tartaric acid is sprayed into the macroporous alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 3 hours, after the drying is carried out for 3 hours at the temperature of 110 ℃, the rolling pot is placed in an atmosphere furnace for roasting for 2 hours, the protective gas is nitrogen, and the roasting temperature is 400 ℃.
And (3) taking out the modified macroporous alumina powder and 20g of small-pore alumina powder (dry basis 75), uniformly mixing, adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 25.4g of ammonium heptamolybdate and 3g of triethylene glycol into the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying for 4 hours at 130 ℃ to obtain the finished catalyst C.
Example 4
100g of macroporous alumina powder (dry basis 85) is placed in a rolling pot, under the condition of rotation, 80ml of aqueous solution containing 18.5g of nickel nitrate and 2.0g of glutaric acid is sprayed into the macroporous alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 3 hours, after the drying is carried out for 3 hours at the temperature of 110 ℃, the rolling pot is placed in an atmosphere furnace for roasting for 2 hours, the protective gas is nitrogen, and the roasting temperature is 400 ℃.
And (3) taking out the modified macroporous alumina powder and 20g of small-pore alumina powder (dry basis 75), uniformly mixing, then adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 2.5g of ammonium heptamolybdate, 20.5g of ammonium metatungstate and 4.2g of glucose into the rolling pot in an atomizing mode under the rotating condition, continuously rotating the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying at 120 ℃ for 4 hours to obtain the finished catalyst D.
Comparative example 1
Uniformly mixing 100g of macroporous alumina powder (dry basis 85) and 20g of small-pore alumina powder (dry basis 75), then adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
100g of the alumina carrier prepared by the method is placed in a rolling pot, under the rotating condition, 80ml of aqueous solution containing 25.4g of ammonium heptamolybdate, 18.5g of cobalt nitrate and 3g of triethylene glycol is sprayed into the alumina carrier in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the rolling pot is placed for 3 hours, and the drying is carried out for 5 hours at the temperature of 120 ℃, so that the finished catalyst E is prepared.
Comparative example 2
100g of the alumina carrier prepared by the method of comparative example 1 was placed in a tumbler, 80ml of an aqueous solution containing 25.4g of ammonium heptamolybdate, 18.5g of cobalt nitrate, 1.1g of citric acid and 4.5g of ethylene glycol was sprayed into the alumina carrier in the tumbler in an atomizing manner under a rotating condition, and after the solution was sprayed, the tumbler was rotated for 30 minutes, and then left to stand for 3 hours, and dried at 120 ℃ for 5 hours, to obtain a finished catalyst F.
Comparative example 3
100g of macroporous alumina powder (dry basis 85) and 20g of small-pore alumina powder (dry basis 75) are placed in a rolling pot to be uniformly mixed, under the condition of rotation, 80ml of aqueous solution containing 18.5g of cobalt nitrate and 1.1g of citric acid is sprayed into the alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the solution is placed for 3 hours, dried at the temperature of 110 ℃ for 3 hours, and then roasted at the temperature of 400 ℃ for 2 hours.
Adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water into the mixed alumina powder prepared in the step, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 25.4G of ammonium heptamolybdate and 3.2G of glycerol into the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying for 4 hours at 130 ℃ to obtain the finished product of the catalyst G.
Comparative example 4
100g of macroporous alumina powder (dry basis 85) is placed in a rolling pot, under the rotating condition, 80ml of aqueous solution containing 18.5g of nickel nitrate and 3.5g of tartaric acid is sprayed into the macroporous alumina powder in the rolling pot in an atomizing mode, after the solution is sprayed, the rolling pot is rotated for 30 minutes, then the solution is placed for 3 hours, and after the solution is dried for 3 hours at 110 ℃, the solution is placed in a muffle furnace for roasting for 2 hours at 400 ℃.
and (3) taking out the modified macroporous alumina powder and 20g of small-pore alumina powder (dry basis 75), uniformly mixing, adding 2g of sesbania powder, 20g of 10% nitric acid and 90ml of deionized water, kneading, molding, drying at 110 ℃ for 4h, and roasting at 550 ℃ for 3h to obtain the alumina carrier.
Putting the obtained alumina carrier into a rolling pot, spraying 60ml of aqueous solution containing 25.4g of ammonium heptamolybdate and 4.2g of glucose into the rolling pot in an atomization mode under the rotation condition, continuing to rotate in the rolling pot for 30 minutes after the solution is sprayed, then standing for 3 hours, and drying at 130 ℃ for 4 hours to obtain the finished catalyst H.
The physicochemical properties of each catalyst are shown in Table 1.
TABLE 1 Main physicochemical Properties of the catalyst
The catalyst evaluation was carried out on a 100ml small scale hydrogenation unit, and the catalyst was presulfided prior to the activity evaluation. The evaluation process conditions of the catalyst are that the pressure is 4.0 MPa, and the liquid hourly volume space velocity is 2.0h-1The volume ratio of hydrogen to oil is 300:1, and the reaction temperature is 360 ℃. Activity evaluation the properties of the raw oil are shown in Table 2, and the results of activity evaluation are shown in Table 3.
Table 2 properties of the feedstock.
Table 3 results of activity evaluation.
From the evaluation results, the catalyst prepared by the method of the present invention had better desulfurization and denitrification activities.
Claims (9)
1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps of (1) preparing an impregnation solution I and an impregnation solution II respectively, wherein the impregnation solution I is prepared by preparing a compound containing VIII group metals, organic acid and water, the impregnation solution II is prepared by preparing water and at least one of VIB group metals, organic alcohol and organic sugar, the organic acid is at least one of organic acids with the carbon number of 2 ~ 10, the organic alcohol is at least one of aliphatic alcohols with the carbon number of 2 ~ 10, the organic sugar is at least one of monosaccharides and disaccharides with the carbon number of 2 ~ 16, a certain amount of macroporous alumina powder is taken, the impregnation solution I is dried, the alumina powder is roasted in an inert atmosphere to obtain a modified alumina oxide powder, the modified alumina powder is obtained by mixing the modified macroporous oxide powder with modified alumina powder (3), the modified alumina powder is obtained by mixing the modified alumina powder with modified alumina powder (2), the modified macroporous oxide powder with the modified alumina powder (2 ~ 16), the modified alumina powder is dried after being dried, the modified alumina powder is obtained by adding a modified macroporous oxide, the modified alumina powder is dried after being dried in the inert impregnation solution I, the inert atmosphere, the modified alumina powder is prepared by mixing step of the modified alumina powder, the modified alumina powder is dried after the modified alumina powder is added in the step of the modified alumina powder, the.
2. The method of claim 1, wherein: the organic acid in the step (1) is one or more of citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, malonic acid and succinic acid.
3. The method of claim 1, wherein: the organic alcohol in the step (1) is one or more of ethylene glycol, propylene glycol, glycerol, isopropanol, triethylene glycol, 2' -iminodiethanol, aminotriethanol and tetraethylene glycol.
4. The method of claim 1, wherein: the organic sugar in the step (1) is one or more of sucrose, glucose, fructose, galactose, lactose and maltose.
5. the method of claim 1, wherein the mass of the small-hole alumina powder in the step (3) accounts for ~ 35% of the total mass of the alumina powder, the extrusion aid is one or more of methyl cellulose, sesbania powder, starch and polyvinyl alcohol, the addition amount of the extrusion aid is 1-5% of the total mass of the alumina powder, and the peptizing agent is one or more of dilute nitric acid, dilute phosphoric acid and silicic acid, and the addition amount of the peptizing agent is 1-5% of the total mass of the alumina powder.
6. the method according to claim 1, wherein the drying temperature in the step (3) is 90 ~ 120 ℃, the drying time is 1 ~ 24 hours, the roasting temperature is 450 ~ 750 ℃, and the roasting time is 2 ~ 10 hours.
7. the method according to claim 1, wherein the concentration of the impregnation liquid II in the step (4) is determined by the water absorption of the carrier and the composition content of the catalyst metal, the drying temperature is not higher than 200 ℃, and the drying time is 1 ~ 8 h.
8. the hydrogenation catalyst prepared by the method of any one of claims 1 ~ 7, wherein the catalyst comprises at least one group VIB metal and at least one group VIII metal as hydrogenation active metals, and the weight content of the hydrogenation active metals calculated by oxides is 8% ~ 50% based on the weight of the catalyst, wherein the group VIB metal is Mo and/or W, the group VIII metal is Ni and/or Co, and the weight ratio of the group VIII metal/(the group VIB metal + the group VIII metal) calculated by oxides is 0.01 ~ 0.70.
9. use of a hydrogenation catalyst prepared according ~ any one of claims 1 ~ 7 in the hydroprocessing of liquefied gas, gasoline, kerosene, diesel oil, wax oil fractions.
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