CN106669779B - 一种中油型加氢裂化催化剂及其制备方法 - Google Patents
一种中油型加氢裂化催化剂及其制备方法 Download PDFInfo
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- CN106669779B CN106669779B CN201510750183.3A CN201510750183A CN106669779B CN 106669779 B CN106669779 B CN 106669779B CN 201510750183 A CN201510750183 A CN 201510750183A CN 106669779 B CN106669779 B CN 106669779B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002808 molecular sieve Substances 0.000 claims abstract description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000003921 oil Substances 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 102000040350 B family Human genes 0.000 claims abstract description 13
- 108091072128 B family Proteins 0.000 claims abstract description 13
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 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 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 229920005749 polyurethane resin Polymers 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000002101 lytic effect Effects 0.000 abstract description 5
- 238000004898 kneading Methods 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004925 Acrylic resin Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 239000000908 ammonium hydroxide Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005906 dihydroxylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/635—0.5-1.0 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
本发明公开一种中油型加氢裂化催化剂及其制备方法,以无定型硅铝和改性Y分子筛为载体,以ⅥB族和Ⅷ族金属为加氢组分,以ⅣB族金属为助剂;按重量含量计,无定形硅铝占催化剂总量的25~50%,改性Y分子筛占催化剂总量的15~40%;ⅥB族金属氧化物占15~25%;Ⅷ族金属氧化物占3~8%,ⅣB族金属氧化物占1~10%;催化剂中孔径为10~20nm的孔占总孔容的5%~15%,BET表面积是320~600m2/g,孔容是0.40~0.6ml/g,所述催化剂采用混捏法或共溶胶法制备。该催化剂对原料适应性强,具有较高的裂解活性和加氢活性,适合用于以生产中间馏分油为主要目的产品的一段串联工艺过程。
Description
技术领域
本发明涉及一种中油型加氢裂化催化剂及其制备方法,该催化剂适合用于处理劣质重油多产中间馏分油。
背景技术
由于原油不断变劣、变重,进口高硫原油大幅度增加,以及炼厂为提高经济效益,开始普遍采用原油减压深拔技术,使得减压馏分油的干点由原来的520℃提高到了600℃左右,其密度越来越大、馏程越来越高、所含烃分子的分子量越来越大、结构也越来越复杂、硫氮等杂质含量也越来越多,大大增加了加氢裂化的难度,这些对加氢裂化技术以及加氢裂化催化剂都提出了更高的要求。对于有重质馏分油大尺码分子参与的催化反应,大孔径的孔对催化活性的影响不容忽视,在相同的反应条件下,催化剂体相的孔愈大,反应物扩散阻力愈小,对催化活性愈有利;催化剂中存在大孔有利于降低反应物的扩散阻力,从而提高催化活性,而且随着反应分子的尺码增加,其影响更为显著。催化剂中存在大孔有利于降低生成物的扩散阻力,从而提高催化剂的选择性。由于微孔分子筛孔径较小,反应原料中直径较大的分子很难扩散到分子筛孔道内部,而且较小的孔道结构还影响反应后产物分子的快速扩散溢出,从而导致过度裂化,降低液体产品收率。孔径在2~50nm 介孔分子筛的出现为解决该问题提供了新思路。但由于介孔分子筛孔壁无定形,其酸性和水热稳定性较微孔分子筛要差很多,这大大限制了其作为催化材料在石油化工行业中的应用。因此要求我们研制的催化剂的酸性应有利于提高催化剂的活性并减少过度裂解发生的可能性;催化剂的孔结构有利于反应物、生成物的扩散以提高反应速率并尽量避免二次裂解。
CN00123131.6公开了一种中油型加氢裂化催化剂,它以无定形硅铝为主载体,载体中含有改性Y分子筛,催化剂的质量组成和物化性质为:WO3 22.0%,NiO9.0%,ZrO2 7.0%,SiO2 33.0%,Al2O329.0%,比表面积260m2/g,孔容0.36ml/g。改性Y分子筛占催化剂总重量的7.0%,改性分子筛SiO2/Al2O3摩尔比为17,相对结晶度93%,比表面积800m2/g,>1.7×10-10m的孔占总孔的45%。该催化剂主要应用于多产中间馏分油的工艺过程,然而由于该分子筛用量少,导致催化剂的活性不高,这就要求提高加氢裂化反应温度,使得分子筛的热裂化趋势增强而抑制了加氢反应,使催化剂的中油选择性提高不明显,产品质量也受影响。
CN1253988A公开了一种采用共胶法制备的多产中油的加氢裂化催化剂,该催化剂含按CN96119840.0方法制备的改性Y分子筛,其重量组成为:WO3 23.0%,NiO9.0%,ZrO27.0%,SiO2 30.0%,Al2O3余量,它的比表面积290m2/g,孔容0.37ml/g。该催化剂所选用的改性Y分子筛酸量高(Ci=0.9~1.1mmol/g),催化剂活性好,但中油选择性不好。
US5,190,903公开了一种用于中油型加氢裂化催化剂的低酸度沸石,目的在于提高催化剂的中油选择性,其特点是使用了一种NH4—TPD酸度最好小于1.5mmol/g的低酸度改性Y沸石,SiO2/Al2O3摩尔比小于6,晶胞参数为2.420~ 2.440nm,该专利所涉及沸石的主要制备特点是对水热处理后的低钠沸石进行干式焙烧脱羟基,脱羟基温度426℃以上。用该沸石作为酸性裂解组分制备的加氢裂化催化剂处理一种VGO,转化率控制在85%时,反应温度高达405~425℃,中油选择性只有55~63%,催化剂的中油选择性并不好。
CN1766051A公开了一种高活性中油型加氢裂化催化剂,该催化剂采用共胶法制备,以经过特殊改性的Y型分子筛为酸性组分,催化剂的组成为:WO3 22.0%,NiO 9.0%,ZrO27.0%,SiO2 33%,Al2O3 29%,其中分子筛含量为20.0 %,比表面积240m2/g,孔容0.34ml/g。催化剂的裂解活性高,中油选择性好,耐氮能力也不错,但是经过特殊改性的Y分子筛以ZL96119840.0报导的改性Y型分子筛为原料,在700~800℃、0.3~0.5MPa的条件下水热处理20~30小时,改性流程长,能耗高,生产周期长,生产效率低。
发明内容
针对现有技术的不足,本发明提供一种中油型加氢裂化催化剂及其制备方法。该催化剂对原料适应性强,具有较高的裂解活性和加氢活性,适合用于以生产中间馏分油为主要目的产品的一段串联工艺过程。
一种中油型加氢裂化催化剂,以无定型硅铝和改性Y分子筛为载体,以ⅥB族和Ⅷ族金属为加氢组分,以ⅣB族金属为助剂;按重量含量计,无定形硅铝占催化剂总量的25~50%,改性Y分子筛占催化剂总量的15~40%;ⅥB族金属氧化物占15~25%;Ⅷ族金属氧化物占3~8%,ⅣB族金属氧化物占1~10%;催化剂中孔径为10~20nm的孔占总孔容的5%~15%,BET表面积是320~600m2/g,孔容是0.40~0.6ml/g,所述改性Y分子筛性质如下:SiO2/Al2O3=10~15(摩尔比),Na2O≤0.15wt%,晶胞常数为2.426~2.432nm,比表面积750~ 850m2/g,孔容0.45~0.55ml/g,红外酸度Ci=0.48~0.58mmol/g,大于2nm二次孔为≥50%,优选大于2nm的二次孔为50-65%,水吸附量(25℃ P/P0=0.1)为2.5~5.5wt%。
本发明催化剂中,所述ⅥB族金属氧化物为氧化钼和/或氧化钨,ⅣB族金属氧化物为氧化镍和/或氧化钴,ⅣB族金属氧化物为氧化锆和/或氧化钛。
一种中油型加氢裂化催化剂的制备方法,采用混捏法或共溶胶法制备,优选采用共溶胶法制备。所述共溶胶法制备过程包括如下步骤:
(1)将配制好的硅源、铝源、加氢金属和助剂金属的盐溶液按要求混合,加入沉淀剂制得凝胶状混合物;
(2)向步骤(1)制备的凝胶状混合物中加入改性Y沸石和水溶性树脂进行高温老化;
(3)老化后的浆液进行过滤、洗涤、干燥、成型、焙烧制得加氢裂化催化剂。
本发明中油型加氢裂化催化剂的具体制备过程如下:配制含有硅源、铝源、加氢金属的盐溶液、助剂金属的盐溶液,按催化剂配比计量,将各溶液加入成胶罐中;将混合溶液升温至55~70℃,加入沉淀剂进行成胶,加入沉淀剂的量以控制浆液的pH=7.5~8.5为准,制成凝胶状的混合物;然后加入改性Y沸石和水溶性树脂,改性Y沸石的加入量占最终催化剂总重量的15~40%,水溶性树脂的加入量为沉淀浆液质量的1%~8%,优选2%~5%,将系统的温度升至110~150℃,老化1~6小时,老化pH值7.5~8.5,老化时间为1.0~6.0小时;老化后的浆液降温、过滤、洗涤,然后在105~120℃干燥脱水至干基大于60wt%,碾压、挤条成型在550~660℃焙烧2~5小时制得中油型加氢裂化催化剂。
本发明方法中,所述的加氢金属为ⅥB族和Ⅷ族金属,助剂金属为ⅣB族金属。优选的加入方式为首先将硅源、铝源、ⅣB族金属盐溶液、助剂金属的盐溶液混合,然后滴加沉淀剂,当溶液的pH到达5-5.5时停止滴加,加入ⅥB族金属氧化物,最后继续滴加沉淀剂至pH7.5~8.5。上述的加入方式能够提高催化剂的活性。
上述方法中,所述的硅源为硅溶胶、水玻璃、白炭黑中一种或多种,优选水玻璃。所述的铝源为铝酸钠、硫酸铝、氯化铝、硝酸铝中的一种或多种,优选氯化铝。加氢金属的盐为偏钨酸铵、钨酸钠、钼酸铵、钼酸钠、硝酸镍、氯化镍、硝酸钴、硫酸钴(CoSO4·7H2O)中的一种或多种,助剂金属的盐为氧氯化锆(ZrOCI2·8H2O)、四氯化钛(TiCl4)中的一种或多种。所述的沉淀剂为NaOH水溶液、氨水溶液、碳酸铵水溶液的至少一种,优选氨水溶液。
上述方法中,所述的水溶性树脂包括但不限于水溶性聚丙烯酸树脂、水溶性聚氨酯树脂、水溶性环氧树脂、水溶性酚醛树脂中的一种或几种,优选水溶性聚丙烯酸树脂。水溶性树脂可以采用市售商品或者按照现有技术进行自制。
上述方法中,改性Y分子筛通过对常规Y分子筛进行水热脱铝和化学脱铝制得。改性后的Y分子筛性质如下:SiO2/Al2O3=10~15(摩尔比),Na2O≤0.15wt%,晶胞常数为2.426~2.432nm,比表面积750~ 850m2/g,孔容0.45~0.55ml/g,红外酸度Ci=0.48~0.58mmol/g,大于2nm二次孔为≥50%,优选大于2nm的二次孔为50-65%,水吸附量(25℃ P/P0=0.1)为2.5~5.5wt%。
上述方法中,优选采用pH为7.5-8.5的醋酸铵溶液对过滤后的物料进行洗涤,洗涤至钠质量含量小于0.1m%。采用醋酸铵溶液洗涤能够提高催化剂的活性。
本发明提供的催化剂具有如下优点:以无定形硅铝作为载体承载活性物质,可使活性组分分散在载体表面上,提高单位质量活性组分的催化效率,无定形硅铝既是加氢金属的载体,又是裂解组分供给体。
本发明的催化剂在共沉淀后加入改性Y沸石和水溶性树脂进行高温老化,可以获得较大的孔容、较高的比表面、10~20nm的集中孔分布,使改性Y沸石组分和无定型硅铝分散均匀,从而提高酸性组分的利用率,提高反应速率并尽量避免二次裂解,使催化剂获得较高裂解活性以及高的中油选择性。
本发明催化剂适合用于以生产中间馏分油为主要目的产品的一段串联工艺过程在处理减压馏分油时,对原料适应性强,显现出催化剂对原料油适应性强,同时具有较高的裂解活性、优良的中油选择性。
具体实施方式
本发明实施例中所用的改性Y分子筛是按中国专利CN1053429C中实例3描述的方法制备的,具体的制备过程如下:①将2.0kg NaY沸石(SiO2/Al2O3=5.1,Na2O=11.3%相对结晶度93%,晶胞常数2.468nm,干基50w%)加到16升浓度为3M的硝酸铵溶液中,在150℃下搅拌离子交换0.5小时,共离子交换12次,得到Na2O含量为0.17%的Y沸石,烘干;②将上述烘干燥的Y沸石放入高压旋转炉中,700℃,0.01MPa,100%水蒸气压力下焙烧4小时;③取水热处理后的产物400g,放入浓度为0.4M的4升盐酸溶液中,处理2小时,过滤、洗涤至中性,烘干得到改性Y沸石。其物化性质为:SiO2/Al2O3=13,Na2O=0.10%,晶胞常数2.428nm,比表面积783m2/g,红外酸度Ci=0.53mmol/g,大于2nm二次孔为56%,水吸附量(25℃ P/P0=0.1)为4w%。
实施例中采用的聚丙烯酸树脂是按中国专利CN101935447B中实施例1的方法制备的,具体制备过程如下:先将分子量为600 的聚乙二醇750 克与聚乙烯吡咯烷酮250 克混合,保持温度为25~30℃,搅拌,待其完全溶解后得到溶液,取该溶液20 毫升与透明脲醛树脂液80 毫升混合成胶液,按胶液100 毫升总体积的10% 加入凝固剂冰醋酸即10 毫升,充分搅拌并用中控泵抽气2~5 分钟至无大量气泡产生,静置待表面再无气泡即得水溶性树脂。
下面通过实施例对本发明做进一步说明。但本发明的范围不只限于这些实施例的范围,以下百分比如无特殊说明均为质量百分比。
实例1
本发明方法制备的催化剂A,催化剂重量组成为:WO3 15.0%,NiO 5.0%,ZrO2 4.5%,无定型硅铝45.5%,改性Y分子筛含量为30.0 %。
具体制备过程如下:
(1)配制含WO3浓度为75g/L 的钨酸钠溶液;
(2)分别配制含NiO浓度为150g/L 的氯化镍溶液、含ZrO2浓度为150g/L 的氧氯化锆溶液、含Al2O3浓度为100g/L 的氯化铝溶液,3种溶液混合并加去离子稀释;
(3)配制含SiO2浓度为75g/L 的水玻璃溶液,在搅拌条件下将水玻璃加入(2)中;
(4)将(3)加热至50℃,在搅拌条件下滴加10%的氨水进行成胶,待浆液pH到达5.2时停止滴加氨水;
(5)在搅拌条件下将(1)加入(4)中,继续滴加10wt%的氨水至浆液pH到达8.0;
(6)浆液升温的同时加入研细的改性Y分子筛[SiO2/Al2O3=13,Na2O=0.10%,晶胞常数2.428nm,比表面积783m2/g,红外酸度Ci=0.53mmol/g,大于2nm二次孔为56%,水吸附量(25℃ P/P0=0.1)为4w%]、聚丙烯酸树脂,聚丙烯酸树脂加入量为沉淀浆液质量的2%,进行充分混合;
(7)将系统温度升至120±2℃,控制pH值8.0±0.1,老化4小时;
(8) 浆液进行降温过滤,滤饼用pH=8.0的醋酸铵溶液洗涤至钠含量小于0.1m%;
(9) 滤饼在105~120℃干燥脱水至干基大于60%,碾压、挤条成型;最后在650℃焙烧3小时制得本发明加氢裂化催化剂成品A,催化剂的比表面积426m2/g,孔容0.48ml/g,孔径为10~20nm的孔占总孔容的12%。
实例2
本发明方法制备的催化剂B,催化剂重量组成为:WO3 25.5%,NiO 5.0%,ZrO2 4.5%,无定型硅铝50%,改性Y分子筛含量为15.0 %。
具体制备过程如下:
(1)配制含WO3浓度为75g/L 的钨酸钠溶液;
(2)分别配制含NiO浓度为150g/L 的氯化镍溶液、含ZrO2浓度为150g/L 的氧氯化锆溶液、含Al2O3浓度为100g/L 的氯化铝溶液,3种溶液混合并加去离子稀释;
(3)配制含SiO2浓度为75g/L 的水玻璃溶液,在搅拌条件下将水玻璃加入(2)中;
(4)将(3)加热至50℃,在搅拌条件下滴加10wt%的氨水进行成胶,待浆液pH到达5.2时停止滴加氨水;
(5)在搅拌条件下将(1)加入(4)中,继续滴加10wt%的氨水至浆液pH到达8.0;
(6)浆液升温的同时加入研细的改性Y分子筛[SiO2/Al2O3=13,Na2O=0.10%,晶胞常数2.428nm,比表面积783m2/g,红外酸度Ci=0.53mmol/g,大于2nm二次孔为56%,水吸附量(25℃ P/P0=0.1)为4w%]、聚丙烯酸树脂,聚丙烯酸树脂加入量为沉淀浆液质量的5%,进行充分混合;
(7)将系统温度升至120±2℃,控制pH值8.0±0.1,老化4小时;
(8) 浆液进行降温过滤,滤饼用pH=8.0的醋酸铵溶液洗涤至钠含量小于0.1m%;
(9) 滤饼在105~120℃干燥脱水至干基大于60%,碾压、挤条成型;最后在650℃焙烧3小时制得本发明加氢裂化催化剂成品B,催化剂的比表面积429m2/g,孔容0.48ml/g,孔径为10~20nm的孔占总孔容的13%。
实例3
本发明方法制备的催化剂C,制备方法同实例1,催化剂的加氢组分由W换成Mo,组成相同,其中改性Y分子筛[SiO2/ Al2O3=15,Na2O=0.10%,晶胞常数2.428nm,比表面积743m2/g,红外酸度Ci=0.48mmol/g,大于2nm二次孔为60%,水吸附量(25℃ P/P0= 0.1)为4w%]。催化剂的比表面积423m2/g,孔容0.49ml/g,孔径为10~20nm的孔占总孔容的12%。
比较例1
催化剂组成同实施例1,不同之处在于制备过程中不加入聚丙烯酸树脂,制得参比催化剂D。
比较例2
催化剂组成同实施例1,不同之处在于制备过程中将高温老化过程改为常规的温度老化,老化温度为80℃(低于100℃)。制得参比催化剂F
实例4
本实例介绍催化剂的性能评价结果。实验在小型加氢裂化试验装置上进行,本发明催化剂A、B、C和参比催化剂D、F反应性能评价采用一段串联(原料先通过加氢精制催化剂床层脱除其中的有机氮,然后通过加氢裂化催化剂)一次通过流程,以胜利VGO为原料,性质列于表1。催化剂与参比剂的评价结果在表2中列出。
从表中的评价数据可以看出:本发明的催化剂在相同的工况条件下,用于处理劣质的原料油时,加氢裂化活性优于参比催化剂D和F,中油选择性好于参比催化剂D和F。
表1
表2
Claims (11)
1.一种中油型加氢裂化催化剂的制备方法,其特征在于:其采用共溶胶法制备,过程包括如下步骤:
(1)将配制好的硅源、铝源、加氢金属和助剂金属的盐溶液按要求混合,加入沉淀剂制得凝胶状混合物,所述的加氢金属为ⅥB族和Ⅷ族金属,助剂金属为ⅣB族金属;
(2)向步骤(1)制备的凝胶状混合物中加入改性Y分子筛和水溶性树脂进行高温老化,所述高温老化的温度为110~150℃;
(3)老化后的浆液进行过滤、洗涤、干燥、成型、焙烧制得加氢裂化催化剂;
其中,步骤(2)所述的水溶性树脂为水溶性聚丙烯酸树脂、水溶性聚氨酯树脂、水溶性环氧树脂、水溶性酚醛树脂中的一种或几种;
所制备的加氢裂化催化剂是以无定型硅铝和改性Y分子筛为载体,以ⅥB族和Ⅷ族金属为加氢组分,以ⅣB族金属为助剂;按重量含量计,无定形硅铝占催化剂总量的25%~50%,改性Y分子筛占催化剂总量的15%~40%;ⅥB族金属氧化物占15%~25%;Ⅷ族金属氧化物占3%~8%,ⅣB族金属氧化物占1%~10%;催化剂中孔径为10~20nm的孔占总孔容的5%~15%,BET表面积是320~600m2/g,孔容是0.40~0.6ml/g,所述改性Y分子筛性质如下:SiO2/Al2O3摩尔比为10~15,Na2O≤0.15wt%,晶胞常数为2.426~2.432nm,比表面积750~ 850m2/g,孔容0.45~0.55ml/g,红外酸度Ci=0.48~0.58mmol/g,大于2nm二次孔为≥50%,25℃ P/P0=0.1时水吸附量为2.5wt%~5.5wt%。
2.根据权利要求1所述的方法,其特征在于:所述ⅥB族金属氧化物为氧化钼和/或氧化钨,ⅣB族金属氧化物为氧化镍和/或氧化钴,ⅣB族金属氧化物为氧化锆和/或氧化钛。
3.根据权利要求1所述的方法,其特征在于:具体制备过程如下:配制含有硅源、铝源、加氢金属的盐溶液、助剂金属的盐溶液,按催化剂配比计量,将各溶液加入成胶罐中;将混合溶液升温至55~70℃,加入沉淀剂进行成胶,加入沉淀剂的量以控制浆液的pH=7.5~8.5为准,制成凝胶状的混合物;然后加入改性Y分子筛和水溶性树脂,改性Y分子筛的加入量占最终催化剂总重量的15%~40%,水溶性树脂的加入量为沉淀浆液质量的1%~8%,将系统的温度升至110~150℃,老化1~6小时,老化pH值7.5~8.5,老化时间为1.0~6.0小时;老化后的浆液降温、过滤、洗涤,然后在105~120℃干燥脱水至干基大于60wt%,碾压、挤条成型在550~660℃焙烧2~5小时制得中油型加氢裂化催化剂。
4.根据权利要求1所述的方法,其特征在于:首先将硅源、铝源、ⅣB族金属盐溶液、助剂金属的盐溶液混合,然后滴加沉淀剂,当溶液的pH到达5-5.5时停止滴加,加入ⅥB族金属氧化物,最后继续滴加沉淀剂至pH7.5~8.5。
5.根据权利要求3所述的方法,其特征在于:所述的硅源为硅溶胶、水玻璃、白炭黑中一种或多种。
6.根据权利要求3所述的方法,其特征在于:所述的铝源为铝酸钠、硫酸铝、氯化铝、硝酸铝中的一种或多种。
7.根据权利要求3所述的方法,其特征在于:加氢金属的盐为偏钨酸铵、钨酸钠、钼酸铵、钼酸钠、硝酸镍、氯化镍、硝酸钴、硫酸钴中的一种或多种,助剂金属的盐为氧氯化锆、四氯化钛中的一种或多种。
8.根据权利要求3所述的方法,其特征在于:所述的沉淀剂为NaOH水溶液、氨水溶液、碳酸铵水溶液中的至少一种。
9.根据权利要求1所述的方法,其特征在于:改性Y分子筛通过对常规Y分子筛进行水热脱铝和化学脱铝制得,改性后的Y分子筛性质如下:SiO2/Al2O3摩尔比为10~15,Na2O≤0.15wt%,晶胞常数为2.426~2.432nm,比表面积750~ 850m2/g,孔容0.45~0.55ml/g,红外酸度Ci=0.48~0.58mmol/g,大于2nm二次孔为≥50%,25℃ P/P0=0.1时水吸附量为2.5wt%~5.5wt%。
10.根据权利要求1所述的方法,其特征在于:采用pH为7.5-8.5的醋酸铵溶液对过滤后的物料进行洗涤,洗涤至钠质量含量小于0.1%。
11.一种中油型加氢裂化催化剂,其特征在于:采用权利要求1-10任一所述的方法制备。
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