CN107774274A - 一种加氢脱硫催化剂及制备方法 - Google Patents
一种加氢脱硫催化剂及制备方法 Download PDFInfo
- Publication number
- CN107774274A CN107774274A CN201610767886.1A CN201610767886A CN107774274A CN 107774274 A CN107774274 A CN 107774274A CN 201610767886 A CN201610767886 A CN 201610767886A CN 107774274 A CN107774274 A CN 107774274A
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- Prior art keywords
- carrier
- catalyst
- dry
- roasting
- salt
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000009938 salting Methods 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 235000015424 sodium Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 230000008859 change 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 16
- 229910017604 nitric acid Inorganic materials 0.000 description 16
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000003643 water by type Substances 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 8
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 7
- 229910017313 Mo—Co Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910016556 Al2(MoO4)3 Inorganic materials 0.000 description 1
- 229910016550 Al2(WO4)3 Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- -1 nitric acid molybdenum ammonium Chemical compound 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide 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
- B01J23/005—Spinels
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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
-
- 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
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
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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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—Zinc, cadmium or mercury
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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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- 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
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明公开了一种加氢脱硫催化剂及制备方法。该催化剂以AlxMyNzO3±δ复合氧化物为载体,其中M选择La、Ce、Sm或Gd中的一种或几种,N选自Mn、Fe、Zn中的一种或几种,0≤δ≤0.5,x=1‑2,y=0.2‑0.8,z=0.1‑0.4,加氢活性组分为VIB族金属和VIII族金属。制备方法如下:(1)将M盐溶解到去离子水中,调节pH值得到M盐溶液;(2)将含铝碱性溶液和含铝酸性溶液并流加到M盐溶液中,沉淀完成后加入N盐,并调节pH值在8.5‑9.0,老化过滤洗涤,干燥得到干胶,然后经成型、干燥和焙烧,得到载体;(3)然后再将加氢活性组分负载到载体上,经干燥、焙烧,得到柴油深度加氢脱硫催化剂。本发明催化剂具有良好的加氢脱硫能力和抗积炭能力,可以应用于直柴、催柴和焦柴或其混合油的加氢脱硫过程。
Description
技术领域
本发明属于加氢脱硫技术领域,具体地涉及一种柴油深度加氢脱硫催化剂及制备方法。
背景技术
柴油中的硫在燃烧过程中会产生大量的SOx气体,造成严重的环境污染问题。世界各国开始对柴油中的硫含量做出越来越严格的规定,欧盟国家柴油质量实施欧Ⅴ标准,硫含量小于10ppm,美国柴油质量要求硫含量小于15ppm,我国柴油开始实施国四标准,硫含量小于50ppm,同时在加快国五标准(硫含量小于10ppm)的实施。柴油中硫的脱除在工业上常用方法是加氢脱硫,即含硫化合物与氢气在催化剂的作用下反应生成H2S而被脱除。
目前,常用的柴油加氢脱硫催化剂主要是以改性氧化铝为载体,以Mo、W、Co、Ni的金属硫化物为活性组分。随着各国规定柴油中的硫含量越来越低,而原料油的性质越来越差,传统常用的加氢脱硫催化剂不能满足其要求。载体在催化剂加氢脱硫过程中起到至关重要的作用,研究者们通过改性载体来提高催化剂的HDS活性。
CN103551162A公开了一种柴油加氢脱硫脱氮催化剂及其制备方法,采用Al2O3-SiO2-ZrO2-TiO2为载体,磷为助剂,镍、钴、钼和钨为活性组分制备的催化剂。柴油加氢脱硫后,产品油中的硫含量在30-60ppm之间。但是,在催化剂制备过程中需要多次浸渍,增加了催化剂的成本。
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发明内容
针对现有技术的不足,本发明提供了一种加氢脱硫催化剂及制备方法。本发明催化剂具有良好的加氢脱硫能力和抗积炭能力,可以应用于直柴、催柴和焦柴或其混合油的加氢脱硫过程。
本发明的加氢脱硫催化剂,包括载体和加氢活性组分,载体为AlxMyNzO3±δ复合氧化物,其中M选择La、Ce、Sm或Gd中的一种或几种,N选自Mn、Fe、Zn中的一种或几种,0≤δ≤0.5,x=1-2,优选1.4-1.9,y=0.2-0.8,z=0.1-0.4;载体比表面积为300-350m2/g,孔容为0.7-0.8cm3/g,平均孔径为8-12nm,机械强度为100-200N/cm;加氢活性组分为VIB族金属和VIII族金属,其中VIB族金属优选Mo和/或W,VIII族金属优选Co和/或Ni,以氧化物计,VIB族金属占催化剂总重量的2.0-30%,VIII族金属占催化剂总重量的0.1-10%,余量为载体。
本发明的加氢脱硫催化剂的制备方法,包括如下内容:(1)将M盐溶解到去离子水中,调节pH值到8.5-9.0,得到M盐溶液;(2)将含铝碱性溶液和含铝酸性溶液并流加到M盐溶液中,沉淀完成后加入N盐,并调节pH值在8.5-9.0,老化过滤洗涤,干燥得到干胶,然后经成型、干燥和焙烧,得到载体;(3)然后再将加氢活性组分负载到载体上,经干燥、焙烧,得到柴油深度加氢脱硫催化剂。
其中步骤(1)所述具体过程是:将M盐溶解到去离子水中,加热至60-90℃并剧烈搅拌,用氨水、尿素、碳酸氢铵或氢氧化钠中的至少一种调节pH值到8.5-9.0,继续搅拌反应30-90min;其中M盐是M的硝酸盐、氯化物或醋酸盐中的一种,M盐溶液的浓度以摩尔浓度计为0.1-0.4mol/L。其中M选择La、Ce、Sm或Gd中的一种或几种。
步骤(2)所述的含铝碱性溶液是偏铝酸钠溶液,浓度为0.1-0.5 mol/L,含铝酸性溶液是氯化铝、硫酸铝或硝酸铝中的一种,浓度为0.1-0.5 mol/L;沉淀反应条件为:反应温度在60-90℃,优选80℃,pH值为8-11,优选9-10;老化反应条件为:老化温度为60-90℃,优选70~80℃,老化时间为30-90min,老化pH值为8.0-9.0。
步骤(2)所述的N盐是N的硝酸盐、硫酸盐、氯化物、磷酸盐或醋酸盐中的一种或几种,N选自Mn、Fe、Zn中的一种或几种。
步骤(2)所述的成型过程中,可以根据需要加入常规的成型助剂,比如胶溶剂、助挤剂等中的一种或多种。所述的胶溶剂为盐酸、硝酸、硫酸、乙酸、草酸等中一种或几种,所述的助挤剂是指有利于挤压成型的物质,如田菁粉、炭黑、石墨粉、柠檬酸等中的一种或几种,助挤剂的用量占总物料干基的1wt%~10wt%。
步骤(2)所述的干燥条件为:100-150℃干燥3-6h,所述的焙烧条件为:500-800℃焙烧3-6h。
步骤(3)所述的加氢活性组分负载过程采用常规的浸渍法,浸渍过程为本领域技术人员熟知,其中加氢活性组分溶液的配制一般是将硝酸钴或和硝酸镍和硝酸钼铵或和硝酸钨溶解到硝酸或氨水中,向其中添加柠檬酸或柠檬酸铵络合剂配制成浸渍液。
步骤(3)所述的干燥条件为:在100-120℃干燥3-6h,所述的焙烧条件为在300-500℃下焙烧3-6h。
本发明的加氢脱硫催化剂可以应用于馏分油的加氢脱硫反应,尤其适用于直柴、催柴和焦柴或其混合油的加氢脱硫反应。
本发明通过在沉淀中和反应后加入过渡金属元素(N),N盐会富集在氢氧化铝颗粒表面,同时载体中的镧系稀土元素(M)能够有效的抑制过渡金属元素向载体内部的扩散,促使过渡金属元素均匀的分布在载体的表面,经过后续的干燥和焙烧过程,会在氧化铝表面生成一层过渡金属氧化物保护层,能有效的阻碍氧化铝与活性金属Co或/和Ni和Mo或/和W之间反应生成Co(Ni)Al2O4、Al2(MoO4)3和Al2(WO4)3,有效减弱了活性金属元素与Al2O3之间的相互作用。同时,过渡金属元素与Al2O3在较高的温度下会反应生成NAl2O4尖晶石,NAl2O4尖晶石的生成能够提高载体的孔径和机械强度,有利于大分子含硫反应物的进入,提高催化剂的加氢脱硫活性。本发明催化剂中的镧系稀土元素和过渡金属元素,一方面能够提高催化剂的稳定性,提高催化剂的寿命;另一方面能够减弱活性金属与载体之间的相互作用,增大载体的平均孔径和机械强度,提高催化剂的活性。
具体实施方式
下面通过实施例对本发明作进一步的阐述,但不局限于实例。
实施例1
将74.21g的Ce(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,反应90min后降温至70℃,然后将69.04g的Fe(NO3)3·9H2O加入,并用氨水调节pH值在8-9,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)和120g去离子水,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体Al1.8Ce0.1Fe0.1O3.05,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的 Al1.8Ce0.1Fe0.1O3.05载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中110℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂A,其性质见表2。
实施例2
将131.48g的Ce(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,反应90min后降温至70℃,然后将122.33g的Fe(NO3)3·9H2O加入,并用氨水调节pH值在8-9,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)和120g去离子水,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体Al1.6Ce0.2Fe0.2O3.1,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的Al1.6Ce0.2Fe0.2O3.1载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中120℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂B,其性质见表2。
实施例3
将222.32g的Ce(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9之间,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,反应90min后降温至70℃,然后将103.42g的Fe(NO3)3·9H2O加入,并用氨水调节pH值在8-9,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)和120g去离子水,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体Al1.4Ce0.4Fe0.2O3.2,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的Al1.4Ce0.4Fe0.2O3.2载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中120℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂C,其性质见表2。
实施例4
将131.03g的La(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9之间,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,反应90min后降温至70℃,然后将90.02g的Zn(NO3)2·6H2O加入,并用氨水调节pH值在8-9,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)和120g去离子水,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体Al1.6La0.2Zn0.2O3,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的Al1.6La0.2Zn0.2O3载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中120℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂D,其性质见表2。
实施例5
将132.41g的La(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9之间,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,反应90min后降温至70℃,然后将88.99g的Co(NO3)2·6H2O加入,并用氨水调节pH值在8-9,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)和120g去离子水,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体Al1.6La0.2Co0.2O3,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的Al1.6La0.2Co0.2O3载体,放到浸渍Mo-Co溶液中浸渍3小时,然后将浸渍条置于烘箱中120℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂E,其性质见表2。
对比例1
将74.21g的Ce(NO3)3·6H2O 溶解到1000ml去离子水中,加热至60℃搅拌30min,向溶液中添加氨水调节pH在8.5-9,继续搅拌反应30min。将偏铝酸钠和氯化铝并流滴加到上述溶液中,反应温度控制在80℃,pH控制在9-10,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)、120g去离子水和69.04g的Fe(NO3)3·9H2O,在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h,得到载体“Al1.8Ce0.1Fe0.1O3.05”,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的 “Al1.8Ce0.1Fe0.1O3.05”载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中110℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂F,其性质见表2。
对比例2
将偏铝酸钠和氯化铝并流滴加到1000mL去离子水中,反应温度控制在80℃,pH控制在9-10,搅拌反应30min,然后过滤洗涤,将滤饼在120℃干燥3h。将制备的干胶加田菁粉7g、草酸12g及20ml硝酸(硝酸浓度是30wt%)、120g去离子水和在捏合机中捏合均匀,在挤条机中挤压成型,挤压成直径1.5mm三叶草型,再在110℃干燥3h,在700℃焙烧3h得Al2O3载体。将74.21g的Ce(NO3)3·6H2O 和69.04g的Fe(NO3)3·9H2O溶解到200ml去离子水中,完全溶解后浸渍到Al2O3载体中,然后在110℃干燥3h,600℃焙烧3h,得到载体“Al1.8Ce0.1Fe0.1O3.05对比例2”,其性质见表1。
将319.1g的Co(NO3)2·6H2O溶解到250mL的去离子水中,溶解后向其中添加金属离子总摩尔数1.2倍的柠檬酸铵,加热溶解,待完全溶解后,冷却至室温,向其中添加443.4g的(NH4)6Mo7O24·4H2O,用氨水调解至钼酸铵完全溶解,用1000mL容量瓶定容。
取120g的 “Al1.8Ce0.1Fe0.1O3.05”载体,等体积浸渍Mo-Co溶液,然后将浸渍条置于烘箱中110℃干燥3h,在马弗炉中450℃焙烧3h,得到催化剂G,其性质见表2。
表1
*采用工业上生产Co-Mo/Al2O3催化剂的载体。
表2
*采用工业上生产Co-Mo/Al2O3催化剂的载体。
实施例6
本实例说明本发明提供的催化剂对于柴油的加氢脱硫反应性能。
采用的评价原料油是由中石化某炼厂提供的高硫高氮劣质混合油。该原料油是由直馏柴油、催化柴油、焦化柴油混合而成。
采用200mL的固定床加氢装置分别对催化剂A、B、C、D、E和参比剂进行加氢反应性能评价。
催化剂的预硫化条件:使用含3wt%CS2的航煤,以空速1.0h-1,氢油体积比500:1,在5.0MPa的操作压力下,对催化剂进行预硫化。
预硫化过程如下所示:在120℃下进预硫化油,进油2h后,恒温硫化2h,以15℃/h升温至150℃,恒温硫化4h,以6℃/h升温至230℃,恒温硫化10h,以6℃/h升温至290℃,恒温硫化6h,以10℃/h升温至340℃,恒温硫化6h,最后自然降温至200℃,预硫化结束。
评价反应条件为:操作压力5.0MPa,反应温度350℃,氢油体积比400:1,体积空速是1.0h-1。评价结果见表3
与参比剂进行比较,说明本发明的催化剂的加氢脱硫活性。
表3
表3中的评价结果可以说明,本发明提高的催化剂在用于高硫高氮劣质混合油的加氢脱硫反应时,在压力5.0MPa,反应温度350℃,氢油体积比400:1,体积空速是1.0h-1的工艺条件下,达到了较高的脱硫性能,同时也具有较高脱氮性能。
在中试装置上,对加氢脱硫活性较高的催化剂D进行长期的寿命考察,结果发现在催化剂D在运行500小时后,产品中的硫、氮含量没有增加,装置的压降、反应温度没有很大的变化,说明催化剂具有很好的抗积碳、抗中毒能力,具有较好的稳定性。
Claims (10)
1.一种加氢脱硫催化剂,包括载体和加氢活性组分,其特征在于:载体为AlxMyNzO3±δ复合氧化物,其中M选择La、Ce、Sm或Gd中的一种或几种,N选自Mn、Fe、Zn中的一种或几种,0≤δ≤0.5,x =1-2,y=0.2-0.8,z=0.1-0.4;载体比表面积为300-350m2/g,孔容为0.7-0.8cm3/g,平均孔径为8-12nm,机械强度为100-200N/cm;加氢活性组分为VIB族金属和VIII族金属,以氧化物计,VIB族金属占催化剂总重量的2.0-30%,VIII族金属占催化剂总重量的0.1-10%,余量为载体。
2.一种权利要求1所述的加氢脱硫催化剂的制备方法,其特征在于包括如下内容:(1)将M盐溶解到去离子水中,调节pH值到8.5-9.0,得到M盐溶液;(2)将含铝碱性溶液和含铝酸性溶液并流加到M盐溶液中,沉淀完成后加入N盐,并调节pH值在8.5-9.0,老化过滤洗涤,干燥得到干胶,然后经成型、干燥和焙烧,得到载体;(3)然后再将加氢活性组分负载到载体上,经干燥、焙烧,得到柴油深度加氢脱硫催化剂。
3.按照权利要求2所述的方法,其特征在于:其中步骤(1)所述具体过程是:将M盐溶解到去离子水中,加热至60-90℃并剧烈搅拌,用氨水、尿素、碳酸氢铵或氢氧化钠中的至少一种调节pH值到8.5-9.0,继续搅拌反应30-90min;其中M盐是M的硝酸盐、氯化物或醋酸盐中的一种,M盐溶液的浓度以摩尔浓度计为0.1-0.4mol/L;其中M选择La、Ce、Sm或Gd中的一种或几种。
4.按照权利要求2所述的方法,其特征在于:步骤(2)所述的含铝碱性溶液是偏铝酸钠溶液,浓度为0.1-0.5 mol/L;含铝酸性溶液是氯化铝、硫酸铝或硝酸铝中的一种,浓度为0.1-0.5 mol/L。
5.按照权利要求2所述的方法,其特征在于:沉淀反应条件为:反应温度在60-90℃,pH值为8-11。
6.按照权利要求2所述的方法,其特征在于:老化反应条件为:老化温度为60-90℃,老化时间为30-90min,老化pH值为8.0-9.0。
7.按照权利要求2所述的方法,其特征在于:步骤(2)所述的N盐是N的硝酸盐、硫酸盐、氯化物、磷酸盐或醋酸盐中的一种或几种,N选自Mn、Fe、Zn中的一种或几种。
8.按照权利要求2所述的方法,其特征在于:步骤(2)所述的干燥条件为:100-150℃干燥3-6h,所述的焙烧条件为:500-800℃焙烧3-6h。
9.按照权利要求2所述的方法,其特征在于:步骤(3)所述的干燥条件为:在100-120℃干燥3-6h,所述的焙烧条件为在300-500℃下焙烧3-6h。
10.一种权利要求1所述的加氢脱硫催化剂应用于馏分油的加氢脱硫反应。
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