CN106693982B - 一种汽油加氢催化剂及其制备方法 - Google Patents
一种汽油加氢催化剂及其制备方法 Download PDFInfo
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- CN106693982B CN106693982B CN201510796283.XA CN201510796283A CN106693982B CN 106693982 B CN106693982 B CN 106693982B CN 201510796283 A CN201510796283 A CN 201510796283A CN 106693982 B CN106693982 B CN 106693982B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 239000003502 gasoline Substances 0.000 title claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 23
- 238000005470 impregnation Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 244000275012 Sesbania cannabina Species 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000007598 dipping method Methods 0.000 claims description 39
- 238000002803 maceration Methods 0.000 claims description 23
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 molybdate compound Chemical class 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000012546 transfer Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 7
- 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 7
- 238000001125 extrusion Methods 0.000 claims description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-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 3
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 claims description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 abstract description 18
- 239000010941 cobalt Substances 0.000 abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 15
- 239000011733 molybdenum Substances 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 239000003349 gelling agent Substances 0.000 abstract 1
- 239000005078 molybdenum compound Substances 0.000 abstract 1
- 150000002752 molybdenum compounds Chemical class 0.000 abstract 1
- 150000003658 tungsten compounds Chemical class 0.000 abstract 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011265 semifinished product Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- YYBIUOYMDJXHEP-UHFFFAOYSA-N [Mo].[P].[Ti] Chemical compound [Mo].[P].[Ti] YYBIUOYMDJXHEP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000008161 low-grade oil Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical group [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- B01J23/888—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
-
- 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
-
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- 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
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
本发明公开了一种汽油加氢催化剂及其制备方法,该方法包括如下步骤:(1)将拟薄水铝石和田菁粉混合,再加入成胶剂、去离子水,制得γ‑Al2O3载体;(2)γ‑Al2O3载体与介孔Al2O3混合作为复合载体;(3)配制含钴化合物和助剂的浸渍液,用浸渍法对步骤(2)的复合载体进行浸渍;(4)配制含钼化合物和含镍化合物的浸渍液,浸渍步骤(3)得到的催化剂载体;以及(5)配制含钨化合物的浸渍液,浸渍步骤(4)得到的催化剂载体,干燥并焙烧,从而制得催化剂;该催化剂以γ‑Al2O3和介孔Al2O3为复合载体,以钨、钼、镍、钴为活性组分,还含有助催化活性组分磷。本发明制备的催化剂可用于轻质馏分油加氢处理,具有高的加氢脱硫脱氮和烯烃饱和活性。
Description
技术领域
本发明涉及一种劣质汽油加氢催化剂及其制备方法,更具体地说,是一种关于延迟焦化汽油、热裂化汽油加氢精制降低烯烃和硫、氮含量的加氢催化剂及其制备方法。
背景技术
进入21世纪以来,环保意识的增强加快了全球范围内的车用燃料质量升级步伐,对于清洁燃料的生产提出了越来越严格的要求。2014年底我国实行了硫含量小于50μg/g,烯烃小于25%、芳烃小于35%的国Ⅳ标准,新标准除了对硫含量提出了更高的要求外,更为紧迫的是对于烯烃含量的限制。
催化重整以石脑油馏分为原料,生产“无硫”、低烯烃含量的高辛烷值汽油调和组分和/或高附加值的轻质芳烃,催化重整汽油约占汽油调和组分的14%,因而催化重整是生产清洁汽油不可缺少的重要手段之一。焦化汽油是延迟焦化的馏分油,属于劣质二次加工产品,与直馏汽油相比,硫、氮、烯烃含量高,其氮含量约为直馏汽油的100倍左右,且形态更为复杂,在现有的重整预加氢工艺条件下,难以制备合格的重整原料。为了合理利用炼油企业的延迟焦化汽油,亟需开发一种劣质汽油加氢催化剂,使精制后的汽油适合做重整原料,这样既提高了产品附加值,又扩大了重整汽油原料来源。为此,需要开发具有优异的加氢脱硫、加氢脱氮、烯烃饱和及催化活性稳定的加氢精制催化剂。
加氢精制催化剂一般以氧化铝或氧化铝与氧化硅、氧化硼、氧化锆等复合氧化物为载体,以ⅥB族W、Mo为活性组分元素,以Ⅷ族Co、Ni为助剂组分元素,它们的不同组合,其催化性能各有特点,例如Co-Mo组合具有较强的脱硫活性;Ni-Mo组合和Ni-W组合具有较强的脱氮活性,Ni-W组合具有较强的烯烃和芳烃饱和活性。
ZL2006101036701公开了一种劣质汽油催化加氢精制的方法,其催化剂含氧化铝30~80%、二氧化钛1.0~20%、氧化钼10~25%、氧化钴2~10%、三氧化钨1~7%、三氧化硼0.5~5%和氧化物锶0.1~5%。而氧化锶极易溶于水,发生剧烈反应,危险性高。该专利公开催化剂成分不含氧化镍,因此催化剂烯烃饱和率较低。
USP6042719中描述了一种FCC汽油低温加氢脱硫技术。专利所用催化剂是双功能催化剂,用ⅥB族金属Mo和Ⅷ族金属Co担载在由ZSM-5与Al2O3组成的载体上,ZSM-5/Al2O3=80/20。在较低温度条件下,加氢脱硫率为80wt%~95wt%,但该催化剂存在液收偏低的缺点。
CN100998952A公开了一种用于焦化汽油加氢精制生产化工和重整原料的加氢精制催化剂及其制备方法,该催化剂采用二次共浸渍、二次烘干、焙烧制备而成,用于焦化汽油加氢精制时具有烯烃饱和低温活性好、结焦速度慢等特点,但该催化剂在处理劣质焦化汽油时烯烃饱和率偏低。
CN02116267.0涉及一种汽油加氢催化剂及制备方法和它在脱硫降烯烃中的应用。该发明的催化剂按对催化剂的重量百分比计,其组分包括:含有用量为20wt%~90wt%的包含TiO2组分的载体;A活性组分:Ⅷ族金属氧化物含量为0.1wt%~8.0wt%;B活性组份:ⅥB族金属氧化物的含量为1wt%~13wt%;余量为粘结剂。该发明的催化剂经预硫化后,在较缓和的加氢条件下,处理含硫、烯烃的FCC汽油,表现出很高的加氢脱硫活性和选择性,但该专利催化剂的加氢脱硫活性偏低。
发明内容
本发明的主要目的在于提供一种汽油加氢催化剂及其制备方法,以克服现有技术中催化剂加氢脱硫活性低的缺陷。
本发明的目的是这样实现的,一种汽油加氢催化剂的制备方法,该方法包括如下步骤:
(1)将拟薄水铝石和田菁粉混合,再加入成胶剂、去离子水混捏,然后挤条、干燥、焙烧,制得γ-Al2O3载体;
(2)将步骤(1)得到的γ-Al2O3载体与介孔Al2O3混合作为复合载体,其中,复合载体中γ-Al2O3载体与介孔Al2O3的重量比为1:10~10:1,介孔Al2O3的比表面积为250~350m2/g,孔容为0.2~0.3m3/g,孔径为3~5nm;
(3)配制含钴化合物和含磷助剂的浸渍液,用浸渍法对步骤(2)的复合载体进行浸渍,然后干燥、焙烧,钴原子在载体表面形成单层分散;
(4)配制含钼化合物和含镍化合物的浸渍液,浸渍步骤(3)得到的催化剂载体,干燥并焙烧,形成稳定的钴-钼-镍络合催化活性中心,所述含钼化合物为磷钼酸、钛磷钼络合物和磷钼酸镍络合物所组成群组中的一种或两种;
(5)配制含钨化合物的浸渍液,浸渍步骤(4)得到的催化剂载体,干燥并焙烧,使钨和磷以磷化物形式结合,从而制得催化剂;其中,以催化剂重量为基准,以氧化物计,三氧化钨的含量为8.0%~22.0%,三氧化钼的含量为3.0%~15.0%,氧化镍的含量为1.5%~8.5%,氧化钴的含量为1.5%~8.5%,P2O5的含量为0.5%~3.5%,余量为γ-Al2O3或介孔Al2O3;
其中,步骤(5)中含钨化合物的浸渍液的配制方法为:将H2O2和有机醇滴加到水中,然后加入有机酸,搅拌溶解后,加入偏钨酸铵,煮沸0.2~1.0小时,冷却至室温,将溶液转移到容量瓶中,加水定容得到含钨化合物的浸渍液。
本发明所述的汽油加氢催化剂的制备方法,其中,优选的是,所述拟薄水铝石含硅或不含硅。
本发明所述的汽油加氢催化剂的制备方法,其中,所述含钴化合物优选为碱式碳酸钴和硝酸钴中的一种或两种。
本发明所述的汽油加氢催化剂的制备方法,其中,所述含镍化合物优选为硝酸镍、碱式碳酸镍和磷钼酸镍络合物所组成群组中的一种或两种。
本发明所述的汽油加氢催化剂的制备方法,其中,所述含钨化合物优选为偏钨酸铵。
本发明所述的汽油加氢催化剂的制备方法,其中,所述步骤(3)、步骤(4)和步骤(5)中的浸渍均优选为等体积浸渍或体积过量浸渍。
本发明所述的汽油加氢催化剂的制备方法,其中,优选的是,所述配制含钨化合物浸渍溶液时,所用有机醇为二元有机醇和三元有机醇所组成群组中的一种或几种,所用有机酸为柠檬酸、酒石酸和草酸所组成群组中的一种或几种,所述H2O2、有机醇的物质的量之比为1:2~5:1,所述H2O2和有机酸的物质的量之比为1:10~5:1。
本发明所述的汽油加氢催化剂的制备方法,其中,所述步骤(1)中还优选加入TS分子筛(钛硅分子筛)。
本发明所述的汽油加氢催化剂的制备方法,其中,所述步骤(3)中含磷助剂为磷钼酸、钛磷钼络合物和磷钼酸镍络合物所组成群组中的一种或两种。
本发明还提供了一种汽油加氢催化剂的制备方法制备的汽油加氢催化剂。
本发明所述的汽油加氢催化剂,其中,所述催化剂优选以γ-Al2O3和介孔Al2O3为复合载体,以钨、钼、镍、钴为活性组分,还含有助催化活性组分磷。
本发明所述的汽油加氢催化剂,其中,以催化剂重量为基准,以氧化物计,三氧化钨的含量优选为8.0%~22.0%,三氧化钼的含量优选为3.0%~15.0%,氧化镍的含量优选为1.5%~8.5%,氧化钴的含量优选为1.5%~8.5%,P2O5的含量优选为0.5%~3.5%,余量为γ-Al2O3或介孔Al2O3。
本发明所述的汽油加氢催化剂,其中,所述催化剂的比表面积优选为220m2/g~290m2/g,孔容优选为0.30ml/g~0.55ml/g。
本发明所述的一种汽油加氢催化剂的制备方法,还可以表述如下:
(1)将拟薄水铝石和田菁粉混合,再加入成胶剂、去离子水混捏,然后挤条、干燥、在高温炉中于500℃~800℃下焙烧5h~8h,制得γ-Al2O3载体;
(2)将步骤(1)得到的γ-Al2O3载体与介孔Al2O3混合作为复合载体,其中,复合载体中γ-Al2O3载体与介孔Al2O3的重量比为1:10~10:1,介孔Al2O3的比表面积为250~350m2/g,孔容为0.2~0.3m3/g,孔径为3~5nm;
(3)配制含钴化合物和含磷助剂的浸渍液,用浸渍法对步骤(2)的复合载体进行浸渍,然后干燥、焙烧,钴原子在载体表面形成单层分散;
(4)配制含钼化合物和含镍化合物的浸渍液,浸渍步骤(3)得到的催化剂载体,干燥并焙烧,形成稳定的钴-钼-镍络合催化活性中心,所述含钼化合物为磷钼酸、钛磷钼络合物和磷钼酸镍络合物所组成群组中的一种或两种;以及
(5)配制含钨化合物的浸渍液,浸渍步骤(4)得到的催化剂载体,干燥并焙烧,使钨和磷以磷化物形式结合,从而制得催化剂;
本发明的有益效果:
1、本发明的汽油加氢催化剂的制备方法,以传统γ-Al2O3与介孔Al2O3共同作为载体,强化传质,有利于消除内扩散;
2、以钴元素和含磷助剂配制成浸渍液浸渍载体,经干燥和焙烧后,钴原子在载体表面形成单层分散,钴原子的存在能够减少镍铝尖晶石的形成,有效提高镍的催化活性;磷钼络合物的引入提高了催化活性中心的稳定性,形成稳定的Co-Mo-Ni络合催化活性中心;磷元素先于钨加入载体中,便于钨和磷以磷化物形式结合,提高了钨活性中心稳定性,与之前步骤中负载的镍、钴、钼元素形成协同作用,更好地发挥催化剂的加氢精制活性;
3、以H2O2、C2H5OH、柠檬酸的复配溶液作为分散剂,有利于减弱活性金属与复合载体的相互作用,提高活性金属的分散度;
4、应用本发明制备方法制备的催化剂,催化剂的加氢脱硫和烯烃饱和活性以及活性稳定性有了显著的提高,并且使得在较缓和的工艺条件下加工劣质油品,可达到深度脱硫、脱氮、降烯烃的效果。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
含钼化合物:
本发明中,对含钼化合物通常限定为磷钼酸、钛磷钼络合物和磷钼酸镍络合物所组成群组中的一种或两种,本发明中通过添加磷元素,可以改善活性金属与载体的相互作用力,有利于形成钼的单层分散,提高活性金属利用率。
下面将结合具体实施例对本发明的技术方案进行详细描述。
实施例1
(1)γ-Al2O3载体制备
称取500g的无硅拟薄水铝石粉、30g田菁粉、30g柠檬酸、3~5%的稀硝酸300ml混合均匀,用挤条机挤压成型,120℃干燥4小时,550℃焙烧5小时后,得到γ-Al2O3载体。
(2)取150g步骤(1)得到的γ-Al2O3,与150g介孔Al2O3混合均匀(介孔Al2O3比表面积250~350m2/g,孔容0.2~0.3m3/g,孔径3~5nm),二者的混合物作为复合载体,记作F1。
(3)Co/F1的制备
配制500ml浸渍溶液:称量60g酒石酸加入到400ml去离子水中,搅拌并加热到50℃后,称量23.1g硝酸钴(工业级)和16.3g磷酸二氢铵(工业级)加入到该溶液中,煮沸0.5小时。冷却至室温后,将溶液转移到容量瓶中,加水定容到500ml,得到含钴的浸渍溶液。
称取300g步骤(2)所制备的F1载体,量取230ml上述所配制的含钴和磷的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂半成品。
(4)Co-Mo-Ni/F1催化剂的制备
配制500ml浸渍溶液:称量47.3g柠檬酸加入到300ml水中,搅拌溶解后,称量100g硝酸镍(工业级)和70g磷钼酸(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钼和镍的浸渍溶液。
称取300g步骤(3)所制备的Co/F1催化剂半成品,量取270ml上述所配制的含钼和镍的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂成品。
(5)W-Co-Mo-Ni/F1催化剂的制备
配制500ml浸渍溶液:称量100ml H2O2滴加到300ml水中,再滴加20ml C2H5OH,称量66.5g柠檬酸加入到300ml水中,搅拌溶解后,称量100g偏钨酸铵(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钨的浸渍溶液。
称取200g步骤(3)所制备的Co-Mo-Ni/F1催化剂半成品,量取165ml上述所配制的含钨的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂成品。
实施例2
(1)含TS分子筛的γ-Al2O3载体的制备
称取450g的无硅拟薄水铝石粉、50克TS分子筛、30g田菁粉、30g柠檬酸、3~5%的稀硝酸300ml混合均匀,用挤条机挤压成型,干燥焙烧后,得到含TS分子筛的γ-Al2O3载体,简写成TSA。
(2)取200g步骤(1)得到的TSA,与100g介孔Al2O3混合均匀(比表面积250~350m2/g,孔容0.2~0.3m3/g,孔径3~5nm),二者的混合物作为复合载体,记作F2。
(3)Co/F2的制备
浸渍液制备同实施例1步骤(3)。
称取300g步骤(1)所制备的TSA载体,量取230ml上述所配制的含钴的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂半成品。
(4)Co-Mo-Ni/F2催化剂的制备
浸渍液制备同实施例1步骤(4)。
称取300g步骤(3)所制备的Co/F2催化剂半成品,量取270ml上述所配制的含钼和镍的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂成品。
(5)W-Co-Mo-Ni/F2催化剂的制备
配制500ml浸渍溶液:称量70ml H2O2滴加到300ml水中,滴加20ml C2H5OH滴加到前述溶液,称量66.5g柠檬酸加入到300ml水中,搅拌溶解后,称量100g偏钨酸铵(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钨的浸渍溶液。
称取200g步骤(4)所制备的Co-Mo-Ni/F2催化剂半成品,量取165ml上述所配制的含钨的浸渍溶液,等体积浸渍1h,经干燥焙烧后得到催化剂成品。
实施例3
(1)γ-Al2O3载体的制备
称取300g的含硅拟薄水铝石、40g田菁粉、23g草酸、3~5%的稀硝酸200ml混合均匀,用挤条机挤压成型,烘干焙烧处理后,得到γ-Al2O3载体。
(2)取250g步骤(1)得到的γ-Al2O3,与50g介孔Al2O3混合均匀(比表面积250~350m2/g,孔容0.2~0.3m3/g,孔径3~5nm),二者的混合物作为复合载体,记作F3。
(3)Co/F3的制备
配制500ml浸渍溶液:称量80.0g草酸加入到400ml水中,搅拌并加热到60℃后,称量30g碱式碳酸钴(工业级)和21g磷酸(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钴的浸渍溶液。
称取200g步骤(2)所制备的F3载体,量取100ml所配制的含钴的浸渍溶液,浸渍1h,经干燥、焙烧后,得到催化剂半成品。
(4)Co-Mo-Ni/F3的制备
浸渍液配制同实施例1步骤(4)。
称取200g步骤(3)所制备的Co/F3催化剂半成品,量取150ml上述所配制的含钼和镍的浸渍溶液,浸渍1h,经干燥焙烧后,得到催化剂成品。
(5)W-Co-Mo-Ni/F3催化剂的制备
配制500ml浸渍溶液:称量80ml H2O2滴加到300ml水中,滴加20ml C2H5OH滴加到前述溶液,称量66.5g柠檬酸加入到300ml水中,搅拌溶解后,称量100g偏钨酸铵(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钨的浸渍溶液。
称取200g步骤(4)所制备的Co-Mo-Ni/F3催化剂半成品,量取150ml上述所配制的含钨的浸渍溶液,浸渍养生1h,经干燥焙烧后得到催化剂成品。
对比例1
(1)γ-Al2O3载体的制备
同实施例1步骤(1)。
(2)Co-Mo-Ni/γ-Al2O3催化剂的制备
配制500ml浸渍溶液:称量65.0g柠檬酸加入到400ml水中,搅拌溶解后,称量30g碱式碳酸钴(工业级)和100.0g硝酸镍(工业级)加入到该溶液中,煮沸1.0小时,再将60g磷钼酸(工业级)加入到该溶液中,将溶液定容到500ml。得到含钴、钼、镍的浸渍液。
称取200g步骤(1)所制备的γ-Al2O3载体,量取147ml所配制的含钴、钼、镍的浸渍溶液,浸渍1h,经干燥焙烧后,得到催化剂成品。
对比例2
(1)含TS分子筛的γ-Al2O3载体的制备
同实施例2步骤(1)。
(2)W-Mo-Ni/F2催化剂的制备
配制500ml浸渍溶液:称量65.0g柠檬酸加入到350ml水中,搅拌溶解后,称量30.0g硝酸镍(工业级)加入到该溶液中,煮沸30分钟,再将60g磷钼酸(工业级)加入到该溶液中;再称量100g偏钨酸铵(工业级)加入到该溶液中,继续煮沸1h,待冷却后,将溶液定容到500ml。得到含钨、钼、镍的浸渍液。
称取200g步骤(1)所制备的TSA载体,量取147ml浸渍液,浸渍养生1h,经干燥焙烧后,得到催化剂成品。
对比例3
(1)γ-Al2O3载体的制备
同实施例1步骤(1)。
(2)Co-Mo-Ni/γ-Al2O3催化剂的制备
配制500ml浸渍溶液:称量65.0g柠檬酸加入到400ml水中,搅拌溶解后,称量30g碱式碳酸钴(工业级)和100.0g硝酸镍(工业级)加入到该溶液中,煮沸1.0小时,再将40g钼酸铵(工业级)加入到该溶液中,将溶液定容到500ml。得到含钴、钼、镍的浸渍液。
称取200g步骤(1)所制备的γ-Al2O3载体,量取147ml所配制的含钴、钼、镍的浸渍溶液,浸渍1h,经干燥焙烧后,得到催化剂成品。
对比例4
(1)γ-Al2O3载体的制备
同实施例1步骤(1)
(2)取250g步骤(1)得到的γ-Al2O3,与50g介孔Al2O3混合均匀(比表面积250~350m2/g,孔容0.2~0.3m3/g,孔径3~5nm),二者的混合物作为复合载体,记作F3。
(3)Co/F3的制备
配制500ml浸渍溶液:称量80.0g草酸加入到400ml水中,搅拌并加热到60℃后,称量30g碱式碳酸钴(工业级)和21g磷酸(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含钴的浸渍溶液。
称取200g步骤(2)所制备的F3载体,量取100ml所配制的含钴的浸渍溶液,浸渍1h,经干燥、焙烧后,得到催化剂半成品。
(4)W-Mo-Ni/F3催化剂的制备
配制500ml浸渍溶液:称量80ml H2O2滴加到300ml水中,滴加20ml C2H5OH滴加到前述溶液,称量66.5g柠檬酸加入到300ml水中,搅拌溶解后,称量100g硝酸镍(工业级)和70g磷钼酸(工业级)加入到该溶液中,称量100g偏钨酸铵(工业级)加入到该溶液中,煮沸0.5小时,冷却至室温,将溶液转移到容量瓶中,加水定容到500ml,得到含W-Mo-Ni的浸渍溶液。
称取200g步骤(3)所制备的Co/F3催化剂半成品,量取150ml上述所配制的含W-Mo-Ni的浸渍溶液,浸渍养生1h,经干燥焙烧后得到催化剂成品。
实施例与对比例中各催化剂的物化性质见表1。
表1 实施例与对比例中各催化剂的组成
实施例4
本实施例采用100ml加氢评价装置,以硫、烯烃含量较高的催化汽油、焦化汽油与直馏石脑油混合油(重量比3:3:4)为原料,对催化剂进行单段单剂加氢性能评价,反应条件见表2。
表2 100ml加氢评价条件
评价条件 | 反应温度,℃ | 氢分压,MPa | 体积空速,h<sup>-1</sup> | 氢油体积比 |
控制参数 | 290 | 3.0 | 2.0 | 400:1 |
催化剂的100ml评价结果见表3。
表3 实施例及对比例催化剂活性评价结果
由评价结果可知,以催化汽油、焦化汽油与直馏石脑油混合油(重量比3:3:4)为原料,经实施例1-3中的催化剂加氢处理后,可生产出合格的重整原料。对比例1中,未采用γ-Al2O3与介孔Al2O3共同作为载体,同时没采用复配溶液作为分散剂,且活性金属没有加入钨,其脱硫脱氮以及烯烃饱和性能均差。对比例2中未采用复配溶液作为分散剂,不能有效抑制镍铝尖晶石的形成,影响脱硫氮性能。对比例3中既未采用γ-Al2O3与介孔Al2O3的复合载体,也没采用复配溶液作为分散剂,效果仍旧不理想。对比例4中,只采用两步分步浸渍法,分两步浸渍了含Co和含W-Mo-Ni浸渍液的催化剂,与三步浸渍法比,其脱硫脱氮效果略差,烯烃饱和性能亦有一定程度下降。
本发明的有益效果:
1、本发明的汽油加氢催化剂的制备方法,以传统γ-Al2O3与介孔Al2O3共同作为载体,强化传质,有利于消除内扩散;
2、以钴元素和含磷助剂配制成浸渍液浸渍载体,经干燥和焙烧后,钴原子在载体表面形成单层分散,钴原子的存在能够减少镍铝尖晶石的形成,有效提高镍的催化活性;磷钼络合物的引入提高了催化活性中心的稳定性,形成稳定的Co-Mo-Ni络合催化活性中心;磷元素先于钨加入载体中,便于钨和磷以磷化物形式结合,提高了钨活性中心稳定性,与之前步骤中负载的镍、钴、钼元素形成协同作用,更好地发挥催化剂的加氢精制活性;
3、以H2O2、C2H5OH、柠檬酸的复配溶液作为分散剂,有利于减弱活性金属与复合载体的相互作用,提高活性金属的分散度;
4、应用本发明制备方法制备的催化剂,催化剂的加氢脱硫和烯烃饱和活性以及活性稳定性有了显著的提高,并且使得在较缓和的工艺条件下加工劣质油品,可达到深度脱硫、脱氮、降烯烃的效果。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (9)
1.一种汽油加氢催化剂的制备方法,其特征在于,该方法包括如下步骤:
(1)将拟薄水铝石和田菁粉混合,再加入成胶剂、去离子水混捏,然后挤条、干燥、焙烧,制得γ-Al2O3载体;
(2)将步骤(1)得到的γ-Al2O3载体与介孔Al2O3混合作为复合载体,其中,复合载体中γ-Al2O3载体与介孔Al2O3的重量比为1:10~10:1,介孔Al2O3的比表面积为250~350m2/g,孔容为0.2~0.3m3/g,孔径为3~5nm;
(3)配制含钴化合物和含磷助剂的浸渍液,用浸渍法对步骤(2)的复合载体进行浸渍,然后干燥、焙烧,钴原子在载体表面形成单层分散;
(4)配制含钼化合物和含镍化合物的浸渍液,浸渍步骤(3)得到的催化剂载体,干燥并焙烧,形成稳定的钴-钼-镍络合催化活性中心,所述含钼化合物为磷钼酸和磷钼酸镍络合物所组成群组中的一种或两种;以及
(5)配制含钨化合物的浸渍液,浸渍步骤(4)得到的催化剂载体,干燥并焙烧,使钨和磷以磷化物形式结合,从而制得催化剂;其中,以催化剂重量为基准,以氧化物计,三氧化钨的含量为8.0%~22.0%,三氧化钼的含量为3.0%~15.0%,氧化镍的含量为1.5%~8.5%,氧化钴的含量为1.5%~8.5%,P2O5的含量为0.5%~3.5%,余量为γ-Al2O3和介孔Al2O3;
其中,步骤(5)中含钨化合物的浸渍液的配制方法为:将H2O2和有机醇滴加到水中,然后加入有机酸,搅拌溶解后,加入偏钨酸铵,煮沸0.2~1小时,冷却至室温,将溶液转移到容量瓶中,加水定容得到含钨化合物的浸渍液。
2.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述含钴化合物为碱式碳酸钴和硝酸钴中的一种或两种。
3.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述含镍化合物为硝酸镍、碱式碳酸镍和磷钼酸镍络合物所组成群组中的一种或两种。
4.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述含钨化合物为偏钨酸铵。
5.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述步骤(3)、步骤(4)和步骤(5)中的浸渍均为等体积浸渍或体积过量浸渍。
6.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述配制含钨化合物浸渍溶液时,所用有机醇为二元有机醇和三元有机醇所组成群组中的一种或几种,所用有机酸为柠檬酸、酒石酸和草酸所组成群组中的一种或几种,所述H2O2、有机醇的物质的量之比为1:2~5:1,所述H2O2和有机酸的物质的量之比为1:10~5:1。
7.根据权利要求1所述的汽油加氢催化剂的制备方法,其特征在于,所述步骤(3)中含磷助剂为磷钼酸和磷钼酸镍络合物所组成群组中的一种或两种。
8.权利要求1至6任一项所述的汽油加氢催化剂的制备方法制备的汽油加氢催化剂。
9.根据权利要求8所述的汽油加氢催化剂,其特征在于,所述催化剂的比表面积为220m2/g~290m2/g,孔容为0.30ml/g~0.55ml/g。
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