CN106475109B - 超高活性加氢催化剂的制备方法 - Google Patents
超高活性加氢催化剂的制备方法 Download PDFInfo
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- CN106475109B CN106475109B CN201610842531.4A CN201610842531A CN106475109B CN 106475109 B CN106475109 B CN 106475109B CN 201610842531 A CN201610842531 A CN 201610842531A CN 106475109 B CN106475109 B CN 106475109B
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- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000470 constituent Substances 0.000 claims abstract description 19
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002671 adjuvant Substances 0.000 claims abstract description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 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 abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 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 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 abstract description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002803 maceration Methods 0.000 description 19
- 229910001868 water Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 229940010552 ammonium molybdate Drugs 0.000 description 10
- 235000018660 ammonium molybdate Nutrition 0.000 description 10
- 239000011609 ammonium molybdate Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000001802 infusion Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 210000003850 cellular structure Anatomy 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100503316 Artemisia spiciformis FDS-1 gene Proteins 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FBAZCZFUGZHBMZ-UHFFFAOYSA-O [NH4+].[Ni].[O-][N+]([O-])=O Chemical compound [NH4+].[Ni].[O-][N+]([O-])=O FBAZCZFUGZHBMZ-UHFFFAOYSA-O 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/617—500-1000 m2/g
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- B01J35/638—Pore volume more than 1.0 ml/g
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- 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
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- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种超高活性加氢催化剂的制备方法,包括以下步骤:将铝源改性剂沉积于载体上;将金属、有机络合剂和去离子水混合;将混合后的产物浸渍到沉积有铝源改性剂的载体上;将浸渍有混合后的产物的载体干燥后焙烧;其中,金属主组分为ⅥB族的Mo和/或W,助剂组分为Ⅷ族的Co和/或Ni;铝源改性剂为异丙醇铝、氯化铝和硝酸铝中的一种或多种的组合物;沉积有铝源改性剂的载体的孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%。本发明提供的超高活性加氢催化剂的制备方法,通过增大金属负载量使催化剂活性显著提高的同时,使催化剂具有较好的孔结构和较大的比表面积;并且简化催化剂的制备流程,降低高金属含量的加氢催化剂的制备成本。
Description
技术领域
本发明涉及石油化工技术领域,具体涉及一种超高活性加氢催化剂的制备方法。
背景技术
近年来,随着人们对环境质量的日益重视以及环保意识的提高,在世界范围内对于车用燃料特别是车用柴油硫含量和十六烷值生产提出了更高的要求,国V和国VI柴油质量指标要求车用柴油中硫含量需要超低硫化(<10μg/g),国V和国VI标准车用柴油的十六烷值分别要大于51和53,要提高柴油的十六烷值需要深度加氢脱除芳烃。目前,加氢过程是实现这一目标的最有效途径,而高性能加氢催化剂是其中的关键。
对于加氢处理催化剂制备的研究和开发一直是近年来的研究热点,现有加氢催化剂主要采用浸渍法制备,即采用活性浸渍溶液直接浸渍在催化剂载体的孔道内。但受制于载体γ-Al2O3孔容和颗粒堆积密度限制,采用金属溶液浸渍法制备的加氢催化剂具有较好的孔道结构和较大的比表面积,但活性金属的负载量为25-35wt%左右;这样制备的催化剂若再增大负载量,活性金属会堵塞催化剂孔道,从而使催化剂的比表面积下降,催化剂活性降低。
然而,催化剂在具有一定孔道结构的情况下,提高金属负载量是一种有效提高加氢催化剂的活性的方法。因此,目前亟需一种能在提高金属负载量,且简化催化剂的制备流程,从而降低高金属含量的加氢催化剂的制备成本的催化剂制备方法。
发明内容
针对现有技术中的缺陷,本发明旨在提供一种超高活性加氢催化剂的制备方法,以通过增大金属负载量使催化剂活性显著提高,且简化催化剂的制备流程,降低高金属含量的加氢催化剂的制备成本。
为此,本发明提供一种超高活性加氢催化剂的制备方法,包括以下步骤:将铝源改性剂沉积于载体上;将金属、有机络合剂和去离子水混合;将混合后的产物浸渍到沉积有铝源改性剂的载体上;将浸渍有混合后的产物的载体干燥后焙烧;其中,金属包括主组分和助剂组分;主组分为ⅥB族的Mo和/或W,助剂组分为Ⅷ族的Co和/或Ni;铝源改性剂为异丙醇铝、氯化铝和硝酸铝中的一种或多种的组合物;浸渍的方式为等体积浸渍法,浸渍次数为2-3次;沉积有铝源改性剂的载体的孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%。
将铝源改性剂沉积于载体上,利用铝源改性剂与载体结合后的特殊性质,制备出孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%的载体;将金属、有机络合剂和去离子水混合,得到本发明制备超高活性加氢催化剂所需的浸渍液;将浸渍液浸渍到沉积有铝源改性剂的载体上,有机络合剂的存在可以提高金属在载体表面上的分散效果,从而减弱金属主组分Mo和/或W与载体的相互作用,减弱助剂Co和/或Ni的硫化,提高金属主组分Mo和/或W的硫化程度,使活性相的结构和形态发生变化,形成更多的Ⅱ型活性中心等方式提高其加氢活性;将浸渍有混合后的产物的载体干燥后焙烧;最终在得到超高活性加氢催化剂的同时,使催化剂具有好的孔结构和大的比表面积。传统的通过浸渍法制备加氢催化剂时,催化剂的活性金属负载量仅为25-35wt%左右;提高金属负载量作为一种有效提高加氢催化剂的活性的方法,采用传统浸渍法提高活性金属的负载量时,过多的活性金属会堵塞催化剂的孔道,导致催化剂的比表面积下降、扩散性变差,从而使得催化剂的活性下降;非负载型催化剂虽在一定程度上能提高金属负载量,但其制备出的催化剂孔径分布弥散、孔容较小、比表面积低,活性并不能令人满意。然而,采用本发明提供的超高活性加氢催化剂的制备方法,通过铝源改性剂的加入制备出具有孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%的载体,进而制备出具有超高活性加氢催化剂,从而大大提高加氢催化剂的活性。同时,本发明提供的制备方法的流程简单,大大降低了超高活性加氢催化剂的制备成本。
也就是说,本发明提供的超高活性加氢催化剂的制备方法,通过增大金属负载量使催化剂活性显著提高的同时,使催化剂具有较好的孔结构和较大的比表面积;并且简化催化剂的制备流程,降低高金属含量的加氢催化剂的制备成本。
在本发明的进一步实施方式中,主组分为Mo和W,且Ni(Co)/(Mo+W)原子比为0.5-2.5,Mo/W原子比为0.5-6,Ni/有机络合剂的摩尔比为0.5-2.0。
在本发明的进一步实施方式中,载体为二氧化硅载体,二氧化硅载体与铝源改性剂的Si/Al原子比为5~25。
在本发明的进一步实施方式中,有机络合剂为柠檬酸、苹果酸和乙二胺四乙酸中的一种或多种的组合物。
在本发明的进一步实施方式中,主组分的Mo为三氧化钼、七钼酸铵和四钼酸铵中的一种或多种的组合物;主组分的W为三氧化钨、偏钨酸铵和钨酸中的一种或多种的组合物;助剂组分的Ni为氧化镍、氢氧化镍、硝酸镍、乙酸镍、碱式碳酸镍和碳酸镍中的一种或多种的组合物;助剂组分的Co为氧化钴、乙酸钴、氢氧化钴和碳酸钴中的一种或多种的组合物。
在本发明的进一步实施方式中,将浸渍有混合后的产物的载体干燥后焙烧具体为:将浸渍有混合后的产物的载体在80-200℃下干燥4~12h后,在300-550℃下焙烧2~6h。
在本发明的进一步实施方式中,干燥的温度为100~150℃,干燥的时间为6~8h;焙烧的温度为400~500℃,焙烧的时间为3~5h;焙烧过程中的升温速率为2℃/min。
在本发明的进一步实施方式中,焙烧后的产物的孔容为0.2~0.5ml/g,5~10nm孔孔径比例大于50%,比表面积为150~350m2/g。
在本发明的进一步实施方式中,催化剂的负载量按活性金属氧化物的质量为标准来计算,焙烧后的产物的金属质量负载量大于60%。
附图说明
图1为本发明实施例中的超高活性加氢催化剂的制备方法的流程图。
具体实施方式
下面将结合附图对本发明技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚的说明本发明的技术方案,因此只作为实例,而不能以此来限制本发明的保护范围。
图1为本发明实施例中的超高活性加氢催化剂的制备方法的流程图,如图1所示,本发明提供的超高活性加氢催化剂的制备方法,包括以下步骤:
S101:将铝源改性剂沉积于载体上。其中,铝源改性剂为异丙醇铝、氯化铝和硝酸铝中的一种或多种的组合物;载体为二氧化硅载体,二氧化硅载体与铝源改性剂的Si/Al原子比为5~25。
S102:将金属、有机络合剂和去离子水混合。其中,金属包括主组分和助剂组分;主组分为ⅥB族的Mo和/或W,助剂组分为Ⅷ族的Co和/或Ni;铝源改性剂为异丙醇铝、氯化铝和硝酸铝中的一种或多种的组合物;主组分优选为Mo和W,且Ni(Co)/(Mo+W)原子比为0.5-2.5,Mo/W原子比为0.5-6,Ni/有机络合剂的摩尔比为0.5-2.0;主组分的Mo为三氧化钼、七钼酸铵和四钼酸铵中的一种或多种的组合物;主组分的W为三氧化钨、偏钨酸铵和钨酸中的一种或多种的组合物;助剂组分的Ni为氧化镍、氢氧化镍、硝酸镍、乙酸镍、碱式碳酸镍和碳酸镍中的一种或多种的组合物;助剂组分的Co为氧化钴、乙酸钴、氢氧化钴和碳酸钴中的一种或多种的组合物;有机络合剂为柠檬酸、苹果酸和乙二胺四乙酸中的一种或多种的组合物。
将铝源改性剂沉积于载体上,利用铝源改性剂与载体结合后的特殊性质,制备出孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%的载体。将Mo和/或W、Co和/或Ni、有机络合剂和去离子水按照Ni(Co)/(Mo+W)原子比为0.5-2.5,Mo/W原子比为0.5-6,Ni/有机络合剂的摩尔比为0.5-2.0的比例混合,从而得到本发明制备高金属含量加氢催化剂所需的浸渍液。
S103:将混合后的产物浸渍到沉积有铝源改性剂的载体上。其中,沉积有铝源改性剂的载体的孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%;浸渍的方式为等体积浸渍法,浸渍次数为2-3次。
将浸渍液浸渍到沉积有铝源改性剂的载体上,有机络合剂的存在可以提高金属在载体表面上的分散效果,从而减弱金属主组分Mo和/或W与载体的相互作用,减弱助剂Co和/或Ni的硫化,提高金属主组分Mo和/或W的硫化程度,使活性相的结构和形态发生变化,形成更多的Ⅱ型活性中心等方式提高其加氢活性。Si/Al原子比为5~25,可以使沉积有铝源改性剂的载体孔容和比表面积更理想,更能制备出本发明所需的高金属含量的加氢催化剂。采用等体积浸渍法浸渍2-3次,可以使浸渍液中有效成分更充分的浸渍到载体中,从而制备出各方面性能更好的催化剂。
S104:将浸渍有混合后的产物的载体干燥后焙烧。其中,将浸渍有混合后的产物的载体干燥后焙烧具体为:将浸渍有混合后的产物的载体在80-200℃下干燥4~12h后,在300-550℃下焙烧2~6h;干燥的温度优选为100~150℃,干燥的时间优选为6~8h;焙烧的温度优选为400~500℃,焙烧的时间优选为3~5h;焙烧过程中的升温速率为2℃/min;焙烧后的产物的孔容为0.2~0.5ml/g,5~10nm孔孔径比例大于50%,比表面积为150~350m2/g;催化剂的负载量按活性金属氧化物的质量为标准来计算,焙烧后的产物的金属质量负载量大于60%。
将浸渍有混合后的产物的载体干燥后焙烧;最终在得到超高活性加氢催化剂的同时,使催化剂具有好的孔结构和大的比表面积。传统的通过浸渍法制备加氢催化剂时,催化剂的活性金属负载量仅为25-35wt%左右;提高金属负载量作为一种有效提高加氢催化剂的活性的方法,采用传统浸渍法提高活性金属的负载量时,过多的活性金属会堵塞催化剂的孔道,导致催化剂的比表面积下降、扩散性变差,从而使得催化剂的活性下降;非负载型催化剂虽在一定程度上能提高金属负载量,但其制备出的催化剂孔径分布弥散、孔容较小、比表面积低,活性并不能令人满意。然而,采用本发明提供的超高活性加氢催化剂的制备方法,通过铝源改性剂的加入制备出具有孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%的载体,进而制备出具有超高活性加氢催化剂,从而大大提高加氢催化剂的活性。同时,本发明提供的制备方法的流程简单,大大降低了超高活性加氢催化剂的制备成本。
下面结合具体实施方式进行说明:
实施例一
称取50g大孔容SiO2置于烧杯中,加入500ml正己烷,然后称取11.3g异丙醇铝,Si/Al=15,在搅拌下用少量正己烷溶解后加到烧杯中;再加入1500ml正己烷,室温下继续搅拌24小时。过滤,使用大量正己烷洗涤,137℃干燥7h,再以2℃/min速率升温至530℃焙烧5h得到铝源改性的二氧化硅载体,记为S-1。
称取50g大孔容SiO2置于烧杯中,加入500ml无水乙醇,然后称取7.4g无水氯化铝,Si/Al=5,在搅拌下用少量无水乙醇溶解后加到烧杯中;再加入1500ml无水乙醇,室温下继续搅拌24小时。过滤,使用大量无水乙醇洗涤,137℃干燥7h,再以2℃/min速率升温至530℃焙烧5h得到铝源改性的二氧化硅载体,记为S-2。
另外,根据实施例一得到的载体S-1和载体S-2,制备本发明的催化剂,也具体存在以下实施方式:
实施例二
称取417.5g乙酸镍(C4H6NiO4·6H2O),192.5g钼酸铵((NH4)6Mo7O24·4H2O),144.5g偏钨酸铵((NH4)6H2W12O40·XH2O)以及176.4g柠檬酸(C6H8O7·H2O)。先将硝酸镍用适量的水溶解,加入柠檬酸至全部溶解后加入钼酸铵和偏钨酸铵,60℃下继续搅拌至完全溶解配成NiMoW共浸渍液。最后将溶液定容到700ml,标记为浸渍液A。
测量载体S-1的吸水率为1.8ml/g,称取100g载体,从浸渍液A中取200ml浸渍液,采用等体积浸渍法制备中间催化剂,浸渍完成后,100℃干燥6小时,450℃焙烧4h(升温速率为2℃/min),制得中间催化剂(活性金属负载量为52wt%)。再次测量其吸水率为0.7ml/g,在浸渍液A中取80ml浸渍液定容到145ml。再以同样的浸渍、干燥、焙烧步骤制得催化剂B1。
其中,定容的体积V满足V=θm;其中,θ为载体的吸水率,单位为mL/g,m为载体的质量,单位为g。活性金属负载量为(MoO3+WO3+NiO,以氧化物的质量分数计)为60wt%。其中,Ni/(Mo+W)=1,Mo:W=1:1,Ni/柠檬酸=1.5。
同时,采用两次等体积浸渍的方法制备具有相同金属负载量的催化剂,催化剂命名为B2。
首先测量大孔容载体SiO2的吸水率为2.0ml/g。称取100g载体SiO2,从浸渍液A中取200ml浸渍液,采用等体积浸渍法制备中间催化剂,浸渍完成后,100℃干燥6小时,450℃焙烧4h(升温速率为2℃/min),制得中间催化剂(活性金属负载量为52wt%)。再次测量其吸水率为0.7ml/g,在浸渍液A中取145ml浸渍液。再以同样的浸渍、干燥、焙烧步骤制得催化剂B2。其中活性金属负载量为(MoO3+WO3+NiO,以氧化物的质量分数计)为65wt%。其中,Ni/(Mo+W)=1,Mo:W=1:1,Ni/柠檬酸=1.5。
实施例三
测量载体S-1的吸水率为1.9ml/g,称取100g载体,205.2g乙酸钴(C4H6CoO4·6H2O),72.8g钼酸铵((NH4)6Mo7O24·4H2O),101.6g偏钨酸铵((NH4)6H2W12O40·XH2O)以及115.4g柠檬酸(C6H8O7·H2O)。先将乙酸钴用适量的水溶解,加入柠檬酸至全部溶解后加入钼酸铵和偏钨酸铵,60℃下继续搅拌至完全溶解配成CoMoW共浸渍液。最后将溶液定容到400ml。从浸渍液A中取200ml浸渍液,采用等体积浸渍法制备中间催化剂,浸渍完成后,100℃干燥6小时,450℃焙烧4h,升温速率为2℃/min,制得中间催化剂(活性金属负载量为52wt%)。再次测量其吸水率为0.7ml/g,在浸渍液A中取145ml浸渍液。再以同样的浸渍、干燥、焙烧步骤制得催化剂C。
其中,活性金属负载量为(MoO3+WO3+CoO,以氧化物的质量分数计)为65wt%。其中,Co/(Mo+W)=1,Mo:W=1:1,Co/柠檬酸=1.5。
另外,为了进一步凸显本发明提供的超高活性加氢催化剂的制备方法的优势,采用现有技术中的方法制备对比例中的催化剂,进行以下对比实验:
对比例一
中国石油大学(华东)CNPC催化重点实验室开发的负载型FDS-1催化剂,作为对比催化剂D1。其中活性金属负载量以氧化物计,MoO3含量为21%-23%,NiO含量为3.8%-4.2%,P2O5含量为3.0-5.0%。
对比例二
按照现有技术制备NiMoW非负载型催化剂:称取66g硝酸镍,20g钼酸铵,36g偏钨酸铵加入到600ml去离子水中,置于磁力搅拌器上,在搅拌的情况下加入9g四乙基溴化铵,加氨水(浓度为25%)调节溶液PH值为9,将混合液置于合成反应釜中,在60℃密闭条件下水热合成9小时,然后冷却、过滤、洗涤,得到滤饼,然后将滤饼在160℃下干燥4小时。得到对比催化剂D2。
对比例三
按照另一现有技术制备NiMoW非负载型催化剂:称取24g氯化镍、28g偏钨酸铵溶解在300ml去离子水中,配制成酸性溶液A;称取18g偏铝酸钠溶解在300ml去离子水中,配成碱性溶液B。将溶液A加入反应罐中,恒温45℃,在搅拌的情况下,再加入90ml溶液B,控制浆液PH值为9.5,然后通入CO2气体,浓度为40v%,成胶温度45℃,反应罐内浆液pH值为7.5,重复上述操作2次,成胶结束时控制反应浆液pH值为7.5,老化2小时。然后过滤,滤饼加入360ml去离子水和7.4g三氧化钼,打浆搅拌均匀,过滤,滤饼在100℃下干燥4小时,然后挤条,洗涤,湿条在120℃干燥4小时,在500℃下焙烧4小时,得到对比催化剂D3。
另外,采用本发明提供的制备方法,选用未添加铝源改性剂的大孔容载体SiO2制备催化剂,具体也存在以下实施方式:
测量大孔容载体SiO2的吸水率为2.0ml/g。称取100g载体SiO2,119.3g硝酸镍(Ni(NO3)2·6H2O),36.2g钼酸铵((NH4)6Mo7O24·4H2O),50.5g偏钨酸铵((NH4)6H2W12O40·XH2O)以及57.4g柠檬酸(C6H8O7·H2O)。先将硝酸镍用适量的水溶解,加入柠檬酸至全部溶解后加入钼酸铵和偏钨酸铵,60℃下继续搅拌至完全溶解配成NiMoW共浸渍液,最后将溶液定容到200ml。采用等体积浸渍法制备催化剂(仅浸渍1次),浸渍完成后,100℃干燥6小时,450℃焙烧4h(升温速率为2℃/min),制得催化剂A1。
其中,活性金属负载量为(MoO3+WO3+NiO,以氧化物的质量分数计)为52wt%。其中,Ni/(Mo+W)=1,Mo:W=1:1,Ni/柠檬酸=1.5。
同时,采用两次等体积浸渍的方法制备具有相同金属负载量的催化剂,催化剂命名为A2。
首先测量大孔容载体SiO2的吸水率为2.0ml/g。称取100g载体SiO2,119.3g硝酸镍(Ni(NO3)2·6H2O),36.2g钼酸铵((NH4)6Mo7O24·4H2O),50.5g偏钨酸铵((NH4)6H2W12O40·XH2O)以及57.4g柠檬酸(C6H8O7·H2O)。先将硝酸镍用适量的水溶解,加入柠檬酸至全部溶解后加入钼酸铵和偏钨酸铵,60℃下继续搅拌至完全溶解配成NiMoW共浸渍液,最后将溶液定容到200ml。取150ml浸渍液定容至200ml,采用等体积浸渍法制备中间催化剂,浸渍完成后,100℃干燥6小时,450℃焙烧4h(升温速率为2℃/min),制得中间催化剂(活性金属负载量为45wt%)。再次测量吸水率为0.9ml/g,将所剩50ml浸渍液定容到160ml。再以同样的浸渍、干燥、焙烧步骤制得催化剂A2。其中活性金属负载量为(MoO3+WO3+NiO,以氧化物的质量分数计)为52wt%。其中,Ni/(Mo+W)=1,Mo:W=1:1,Ni/柠檬酸=1.5。
另外,对本发明各实施例得到的催化剂性质进行系统评价:
一、对A1-A2、B1-B2、C以及D1-D3进行低温液氮吸附分析,以考察各催化剂的平均孔径、孔容、比表面积等性质。
实验采用美国Micromeritics ASAP 2010全自动比表面积及孔隙度分析仪测定催化剂的孔结构。测定催化剂孔结构时将吸附温度设为-196℃,相对压力p/p0设为0~0.995。物质的吸/脱附等温线由氮气在待测物质表面吸附量随压力变化情况做出,进而通过BET方法计算样品的BET比表面积,BJH方法计算样品的孔容,BJH孔径是通过低温N2吸脱附曲线中的脱附支计算得到的。结果如表1所示。
表1载体和催化剂物理性质表
通过表1可以看出,以大孔容SiO2以及用铝源改性的SiO2为载体制备的高金属负载量催化剂具有较大的孔容、比表面积,孔径集中分布于5~10nm。
对比B1、B2、C与D1发现,超高活性加氢催化剂的比表面积比常规负载型催化剂比表面积大,说明在负载量大幅度增大的情况下,该方法制备的催化剂仍有很好的孔结构性质。对比B2、C、D2和D3发现,超高活性加氢催化剂的孔容和比表面积均远大于非负载型催化剂,具有较好的孔结构和较大比表面积。对比B1、B2和A1、A2发现,在载体中引入铝源改性剂后,活性金属负载量明显变大。
二、对A1-A2、B1-B2、C以及D1-D3进行加氢活性评价。
催化剂的活性评价在100ml高压加氢微反装置中进行,催化剂在评价前先经预硫化、活性稳定过程。催化剂的评价条件为总压6MPa,氢油比300:1,反应温度340℃、空速2.0h-1。活性评价试验所用的原料油性质如表2所示。
实施例和对比例的催化剂的活性结果如表3所示。通过分析加氢后油品的硫含量和密度来比较催化剂的加氢脱硫活性和催化剂加氢饱和活性。通过对比A1、A2及B1、B2发现,在载体中引入铝源改性剂后,超高活性加氢催化剂负载量增大,且反应活性大幅度增大。对比B2与D1发现,超高金属负载量NiMoW/SiO2催化剂比常规负载型催化剂的反应活性高,这是因为该超高活性加氢催化剂既兼具了负载型催化剂良好的孔道结构,又有高的活性位密度。对比B2与D1、D2发现,高金属负载量NiMoW/SiO2催化剂比该试验中的非负载型催化剂具有更高的加氢和脱硫活性;即本发明制备的超高活性加氢催化剂既保证了高的活性位密度,又克服了非负载型催化剂孔径分布弥散、孔容较小、比表面积较低的缺点。
表2实验柴油原料的性质
表3活性评价结果
当然,除了实施例一和实施例三列举的情况,其他金属主组分、助剂组分、载体、有机络合剂、Ni(Co)/(Mo+W)的原子比、Mo/W的原子比、Ni/有机络合剂的摩尔比、干燥温度和时间、焙烧温度和时间以及浸渍次数也是可以的。只是在实施例一和实施例三列举的情况下,催化剂在具有高的金属负载量的同时,催化活性更高,孔结构和比表面积更好。
本发明提供的超高活性加氢催化剂的制备方法,通过增大金属负载量使催化剂活性显著提高的同时,使催化剂具有较好的孔结构和较大的比表面积;并且简化催化剂的制备流程,降低高金属含量的加氢催化剂的制备成本。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例,可以理解的是,上述实施例是示例性的,不能理解为对本发明的限制,本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。
Claims (6)
1.一种超高活性加氢催化剂的制备方法,其特征在于,包括以下步骤:
将铝源改性剂沉积于载体上;
将金属、有机络合剂和去离子水混合;
将混合后的产物浸渍到沉积有铝源改性剂的载体上;
将浸渍有混合后的产物的载体干燥后焙烧;
其中,
所述金属包括主组分和助剂组分;
所述主组分为ⅥB族的Mo和W,所述助剂组分为Ⅷ族的Co或Ni;所述铝源改性剂为异丙醇铝、氯化铝和硝酸铝中的一种或多种的组合物;
所述浸渍的方式为等体积浸渍法,浸渍次数为2-3次;
所述沉积有铝源改性剂的载体的孔容为2.0~4.0ml/g,比表面积为450~1000㎡/g,10~25nm孔孔径所占比例大于50%;Ni/(Mo+W)原子比或Co/(Mo+W)原子比为0.5-2.5;Mo/W原子比为0.5-6,Ni/有机络合剂的摩尔比为0.5-2.0;所述载体为二氧化硅载体,所述二氧化硅载体与所述铝源改性剂的Si/Al原子比为5~25;催化剂的负载量按活性金属氧化物的质量为标准来计算,所述焙烧后的产物的金属质量负载量大于60%。
2.根据权利要求1所述的超高活性加氢催化剂的制备方法,其特征在于,
所述有机络合剂为柠檬酸、苹果酸和乙二胺四乙酸中的一种或多种的组合物。
3.根据权利要求1所述的超高活性加氢催化剂的制备方法,其特征在于,
所述主组分的Mo为三氧化钼、七钼酸铵和四钼酸铵中的一种或多种的组合物;
所述主组分的W为三氧化钨、偏钨酸铵和钨酸中的一种或多种的组合物;
所述助剂组分的Ni为氧化镍、氢氧化镍、硝酸镍、乙酸镍、碱式碳酸镍和碳酸镍中的一种或多种的组合物;
所述助剂组分的Co为氧化钴、乙酸钴、氢氧化钴和碳酸钴中的一种或多种的组合物。
4.根据权利要求1所述的超高活性加氢催化剂的制备方法,其特征在于,
所述将浸渍有混合后的产物的载体干燥后焙烧具体为:
将浸渍有混合后的产物的载体在80-200℃下干燥4~12h后,在300-550℃下焙烧2~6h。
5.根据权利要求4所述的超高活性加氢催化剂的制备方法,其特征在于,
所述干燥的温度为100~150℃,干燥的时间为6~8h;
所述焙烧的温度为400~500℃,焙烧的时间为3~5h;焙烧过程中的升温速率为2℃/min。
6.根据权利要求1-5任一项所述的超高活性加氢催化剂的制备方法,其特征在于,
所述焙烧后的产物的孔容为0.2~0.5ml/g,5~10nm孔孔径比例大于50%,比表面积为150~350m2/g。
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