CN104588083B - A kind of preparation method of hydrocracking catalyst - Google Patents
A kind of preparation method of hydrocracking catalyst Download PDFInfo
- Publication number
- CN104588083B CN104588083B CN201310532053.3A CN201310532053A CN104588083B CN 104588083 B CN104588083 B CN 104588083B CN 201310532053 A CN201310532053 A CN 201310532053A CN 104588083 B CN104588083 B CN 104588083B
- Authority
- CN
- China
- Prior art keywords
- accordance
- catalyst
- aluminum
- weight
- hydrocracking catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 39
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000004033 plastic Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000001879 gelation Methods 0.000 claims description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [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 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 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 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 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
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 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
- 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
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 44
- 239000002184 metal Substances 0.000 abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 35
- 230000000694 effects Effects 0.000 abstract description 19
- 150000002739 metals Chemical class 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 13
- 238000005336 cracking Methods 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 11
- 239000002244 precipitate Substances 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 5
- 235000019353 potassium silicate Nutrition 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 238000000746 purification Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 239000012224 working solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 210000002966 serum Anatomy 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000011959 amorphous silica alumina Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- KXXCZYZSRRVYST-UHFFFAOYSA-N chloric acid;nickel Chemical compound [Ni].OCl(=O)=O KXXCZYZSRRVYST-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 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
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ILXDAXZQNSOSAE-UHFFFAOYSA-N [AlH3].[Cl] Chemical compound [AlH3].[Cl] ILXDAXZQNSOSAE-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- YYCNOHYMCOXPPJ-UHFFFAOYSA-N alumane;nickel Chemical compound [AlH3].[Ni] YYCNOHYMCOXPPJ-UHFFFAOYSA-N 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- -1 carbon ion Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the preparation method of a kind of hydrocracking catalyst.The method prepares nickel, aluminum precipitation thing by using positive addition, cocurrent process prepares tungsten, silicon and aluminum precipitation thing, above two precipitate is mixed, Y type molecular sieve suspension is added after hydrothermal treatment, then catalyst is made, so can control the distribution of different hydrogenation active metals, be conducive to being formed between active metal tungsten, nickel high activity phase, and improve the interaction between active metal and carrier, the hydrogenation activity making the hydrocracking catalyst of gained obtains good coordinating with cracking activity, improves the serviceability of hydrocracking catalyst.
Description
Technical field
The present invention relates to the preparation method of the hydrocracking catalyst of a kind for the treatment of of heavy hydrocarbon class.
Background technology
At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, and intermediate oil demand increases,
Petroleum chemicals upgrading and environmental regulation are more and more strict, heavy oil lighting is all greatly facilitated, and constitutes accelerated development
The very strong driving force of hydrogen addition technology.Hydrocracking technology to be mainly characterized by adaptability to raw material strong, products scheme, purpose product select
Property high, good product quality and added value high, multiple high-quality oil product can be directly produced (such as gasoline, jet fuel, diesel oil, profit
Lubricant base oil etc.) and high-quality industrial chemicals (such as the production raw material such as benzene,toluene,xylene, ethylene).
Being hydrocracked and carry out at elevated pressures, hydrocarbon molecules cracks with hydrogen at catalyst surface and is hydrogenated with
Reaction generates the conversion process of lighter molecule, and the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs simultaneously.Hydro carbons exists
Cracking reaction in hydrocracking process is to carry out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, hydrogenation,
With the generation of hydro carbons isomerization reaction while cracking reaction.Hydrocracking catalyst is made up of hydrogenation component and acidic components
, both add the most by a certain percentage, make hydrogenation and cracking performance reach balance, and its effect is that hydrocarbon mixture is abundant
Hydrogenation, cracking and isomerization orienting response.Therefore, the catalyst that distillate hydrocracking process needs should possess stronger hydrogenation
Active center has moderate acid centre again.
In general, hydrocracking catalyst can be prepared using the following, such as: infusion process, kneading method, beating method, altogether
The sedimentation method, may use ion exchange for noble metal.Infusion process and kneading method are all first carrier and acidic components to be made
After add metal again, and coprecipitated rule is acidic components and metal coprecipitation gets off, and metal loading is unrestricted.
US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing group VIII/
VI B race active metal component is used for bulk phase catalyst of hydrotreating and preparation method thereof.Catalyst metal content can reach
50wt%~100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Above-mentioned catalyst uses coprecipitation method to prepare.US
Hydrocracking catalyst disclosed in 3954671, hydrogenation conversion catalyst disclosed in US 4313817, resistance to disclosed in CN1253988A
The hydrocracking catalyst of nitrogen type fecund intermediate oil, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, this
A little catalyst use coprecipitation method to prepare, and owing to the deposition condition of different hydrogenation active metals is different, cause different hydrogenation
The distribution of active metal is not easily controlled, thus affect between distribution and the different activities metal of different hydrogenation active metals and
Interaction relationship between active metal and carrier, so that hydrogenation activity can not well be coordinated with cracking activity,
Finally affect catalyst is hydrocracked performance.High activity, medium oil type hydrocracking catalyst disclosed in CN101239324A
It is addition precipitant alkalescence ammoniac compounds in the serosity that amorphous silica-alumina, auxiliary agent and active metal are made into, precipitates
Reaction, is subsequently adding molecular sieve suspension and makes.The method also uses coprecipitation method to prepare, however it remains different hydrogenation are lived
Property Metal Distribution, hydrogenation active metals and and carrier between act on the bad problem of harmonious relations.
CN103055923A discloses the preparation method of a kind of hydrocracking catalyst.Use containing hydrogenation active metals acid
Solution, sodium metaaluminate alkaline solution and gas CO2And stream is equipped with plastic in the retort of water purification；It is subsequently adding Y type molecule
The suspension mix homogeneously of sieve, through filtration, dry, molding more scrubbed, dry, roasting prepares hydrocracking catalyst.The party
Method utilizes the releasing of gas in roasting process, improves the pore structure of catalyst and the dispersion of active metal, but not from root
The problem that the active metal distribution solving to produce during precipitation in basis is not easy regulation and control.
Coprecipitation method prepares catalyst technology, uses different coprecipitation mode, Gelation Conditions etc., all can be to different hydrogenation activity gold
Interaction relationship between the distribution and the different hydrogenation active metals that belong to and between hydrogenation active metals and carrier has the biggest
Impact.The coprecipitation method of above-mentioned employing can make the distribution of different hydrogenation active metals be not easily controlled, thus affect different hydrogenation and live
Property metal distribution and different hydrogenation active metals between and active metal and carrier between interaction relationship so that adding
Hydrogen activity can not well be coordinated with cracking, and finally affect catalyst is hydrocracked performance.Therefore, how hydrogenation is regulated and controled
The distribution of active metal, make between hydrogenation active metals component and have between hydrogenation active metals component and carrier suitable
Mating reaction, improves the utilization rate of hydrogenation active metals component, is to improve coprecipitation method to prepare hydrocracking catalyst Hydrogenation
Key.
Summary of the invention
For the deficiencies in the prior art, the invention provides the preparation method of a kind of hydrocracking catalyst.The method changes
The distribution of hydrogenation active metals in kind catalyst, improves the utilization rate of hydrogenation active metals, improve between hydrogenation active metals and
And the cooperation effect between carrier, makes catalyst have higher serviceability.
The preparation method of hydrocracking catalyst of the present invention, including:
(1), preparing the mixed solution A containing Ni, Al component, precipitant is added dropwise to solution A and carries out plastic reaction, generation contains
Nickel, aluminum precipitation thing serosity I；
(2), preparation containing the mixed solution B of W, Si, Al component, precipitant and solution B stream are carried out plastic reaction, generate
Tungstenic, silicon, aluminum precipitation thing serosity II；
(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, the serosity obtained is entered
Row hydrothermal treatment consists, adds the suspension of Y type molecular sieve, stirs after hydrothermal treatment consists；
(4) the material drying that step (3) obtained, molding, washing,
(5) step (4) gained material drying again and roasting, prepares hydrocracking catalyst.
In the inventive method, Y type molecular sieve is usually and adds with the form of molecular sieve suspension, will be ground to by molecular sieve
80 mesh ~ 140 mesh, preferably 100 mesh ~ 120 mesh, then add water and make suspension.Described Y type molecular sieve is conventional being hydrocracked
Y type molecular sieve used by catalyst.
Precipitant described in step (1) or step (2) is sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, hydroxide
One or more in potassium, potassium carbonate, potassium bicarbonate, preferably ammonia.
In step (1) mixed solution A, Ni weight concentration in terms of NiO is 20～80g/L, preferably 30～60g/L, Al
With Al2O3The weight concentration of meter is 60～200g/L, preferably 90～150g/L.In step (2) mixed solution B, W is with WO3Meter
Weight concentration is 50～120g/L, and preferably 70～100g/L, Si is with SiO2Weight concentration is 80～250g/L, preferably 100
～180g/L, Al is with Al2O3The weight concentration of meter is 60～200g/L, preferably 90～150g/L.In preparation mixed solution A
Time, the general nickel source used can be one or more in nickel sulfate, nickel nitrate, basic nickel carbonate, Nickel dichloride., and aluminum source is permissible
For one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..When preparing mixed solution B, the general tungsten used
Source can be one or more in ethyl ammonium metatungstate, ammonium metatungstate；Silicon source can be the one in Ludox, sodium silicate or many
Kind；Aluminum source can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..
In step (1), reaction temperature is 20～90 DEG C, preferably 30～70 DEG C.During cemented into bundles, pH value controls is 6.0 ~
11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
Si, the Al introduced in step (2) counts weight content in the catalyst as 10wt%～80wt% with oxide, preferably
For 20wt%～60wt%, wherein Si accounts for 10wt%～90wt% of Si, Al gross weight in terms of oxide in terms of silicon oxide, preferably
30wt%～80wt%；The Al introduced in step (1) counts weight content in the catalyst as 5wt%～45wt% with oxide, relatively
It is well 10wt%～30wt%.
In step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C.And when flowing plastic, pH value controls is 6.0 ~
11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
In step (1) and step (2), gelling temperature and time can be the same or different.Step (1) and step (2) can
To carry out to carry out during difference simultaneously.
In step (3), the temperature of hydrothermal treatment consists can be 40～220 DEG C, preferably 70～150 DEG C.Hydrothermal treatment consists pressure is
Not less than 1MPa, preferably 1MPa～3MPa.During hydrothermal treatment consists serosity, pH value controls is 6.0 ~ 10.0, preferably 6.5 ~ 9.0.Water
Heat treatment time is 0.5 ~ 30 hour, preferably 1.0 ~ 24 hours.Hydrothermal treatment consists is carried out in airtight environment.
Being dried described in step (4), molding can use this area conventional method to carry out.Described be dried typically 50 ~
200 DEG C are dried 1 ~ 48 hour.In forming process, the shaping assistant of routine, such as peptizer, bonding can be added as required
One or more in agent, extrusion aid etc..Described extrusion aid refers to the most extruded material, as sesbania powder, white carbon black,
One or more in graphite powder, citric acid etc., the consumption of extrusion aid accounts for 1wt%～10wt% of total material butt.
Preferably through washing after step (4) molding, washing is usually and uses deionized water or molten containing decomposable asymmetric choice net salt
Liquid washs, and is washed till neutrality.Decompose salt and can use one or more in ammonium acetate, ammonium chloride, ammonium nitrate etc..
Being dried described in step (5) can use this area normal condition with roasting, as little in being dried 1 ~ 48 at 50 ~ 200 DEG C
Time, 450 ~ 600 DEG C of roastings 1 ~ 24 hour, preferably 2 ~ 8 hours.
In hydrocracking catalyst of the present invention, composition includes hydrogenation active metals component W and Ni, carrier component aluminium oxide and
Amorphous silica-alumina, it is also possible to containing molecular sieve.On the basis of the weight of catalyst, WO3Content be 10wt%～50wt%, preferably
For 15wt%～30wt%, the content of NiO is 1wt%～30wt%, preferably 5wt%～20wt%, W/Ni atomic ratio be 0.05～
1.0, preferably 0.1～0.7, the content of amorphous silica-alumina is 10wt%～80wt%, preferably 20wt%～60wt%, molecular sieve
Content is 0wt%～40wt%, preferably 5wt%～30wt%, and alumina content is 5wt%～45wt%, preferably 10wt%～
30wt%.In amorphous silica-alumina, the content of silicon oxide is 10wt%～90wt%, preferably 30wt%～80wt%, the content of aluminium oxide
For 10wt%～90wt%, preferably 30wt%～80wt%.
The character of catalyst prepared by the inventive method is as follows: specific surface area 250～500m2/ g, pore volume 0.35～
0.70mL/g。
In hydrocracking catalyst of the present invention, it is also possible to containing adjuvant component, described adjuvant component is the IVth B race metal,
IVth B family metal oxide content in hydrocracking catalyst is 1wt%～10wt%.Described IVth B race metal is preferably
Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, during preparation mixed solution A, add the group Han auxiliary agent
The compound divided, i.e. titanium source and/or zirconium source.Titanium source can use one or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., zirconium
Source can use one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..
In hydrocracking catalyst of the present invention, Y type molecular sieve used can use all can be used in prior art to be hydrogenated with
Y type molecular sieve in Cracking catalyst, such as: CN102441411A, CN1508228A, CN101450319A, CN
Y type molecular sieve disclosed in 96119840.0.Y type molecular sieve disclosed in preferred CN102441411A in the present invention, with
The molecular sieve of CN 96119840.0 report is raw material, is 650～800 DEG C in temperature, and pressure is that normal pressure is to 0.3MPa, time
Hydrothermal treatment consists is carried out deep sealumination modified in the condition and range of 20～30 hours, can be containing a small amount of in water vapour during hydrothermal treatment consists
Ammonia, ammonia dividing potential drop is 50 ~ 3000Pa(absolute pressure), it is then 0.5～10.0mol/L in acid concentration, the time is 0.5～20.0 hour,
Temperature is 30～80 DEG C, and acid consumption carries out acid treatment in the condition and range that ratio is 1:1～20:1 of molecular sieve, uses
Mineral acid is hydrochloric acid, sulphuric acid or nitric acid etc., obtains being applicable to the Y type molecular sieve that the present invention uses after hydrothermal treatment consists and acid treatment,
Its character is as follows: the bore dia pore volume more than 1.7nm accounts for more than the 45% of total pore volume, and specific surface area is 750～900m2/ g,
Cell parameter is at 2.423nm～2.545nm, relative crystallinity 95%～110%, SiO2/Al2O3Mol ratio is 7～60.This molecule
Sieving existing high degree of crystallinity, have again low cell parameter, the secondary pore of molecular sieve is many, is conducive to improving raw material and the diffusion of product
Speed, reduces the second pyrolysis of product；Big specific surface area, less acid site number, it is more favorable to raising and is hydrocracked and urges
The intermediate oil selectivity of agent；High silica alumina ratio, major part is the acid centre of moderate strength, and acid site is evenly distributed journey
Degree height, makes this molecular sieve have the strongest nitrogen resistance and the most broken ring ability.The above-mentioned characteristic of this molecular sieve can make catalysis
Agent has the ability of preferable anti-nitride poisoning, good hydrocracking activity when the raw material that directly contact impurity content is high
The stability become reconciled.This catalyst is suitable for single hop once by hydrocracking process, and hydrocracking operation condition is as follows:
Reaction temperature is 300～500 DEG C, more preferably 350～450 DEG C；Pressure is 6～20MPa, more preferably 13～17MPa；Volume during liquid
Air speed is 0.5～3 h-1, preferably 0.8～1.5 h-1；Hydrogen to oil volume ratio is 400～2000:1, preferably 800～1500:1.
The heavy charge scope that catalyst prepared by the inventive method is suitable for is the widest, and they include vacuum gas oil (VGO), coking
The various hydrocarbon ils such as gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking recycle oil, it is also possible to group
Closing and use, raw material is generally containing the hydro carbons that boiling point is 250～550 DEG C, and nitrogen content can be at 50～2500 g/g.
The inventive method uses positive addition, and (the acid sedimentation method i.e. alkaline precipitating agent is added in the metal salt solution of acidity carry out
Precipitation) prepare nickel aluminum mixed sediment, use parallel flow precipitation to prepare tungsten, silicon and aluminum mixed sediment, then after both are mixed,
Hydrothermal treatment, adds Y molecular sieve suspension, makes hydrocracking catalyst.The present invention prepares crystal grain by using positive addition
Relatively large nickel, aluminum precipitation thing, cocurrent process prepares the relatively small tungsten of crystal grain, silicon and aluminum precipitation thing, by above two precipitate
Serosity mixes, and especially mix slurry is carried out hydrothermal treatment consists, is precipitated granule and has good pore structure and pattern, it is possible to
Control the distribution of different hydrogenation active metals, beneficially between active metal tungsten, nickel, form high activity phase, and improve active metal with
Interaction between carrier, makes the hydrogenation activity of the hydrocracking catalyst of gained obtain good coordinating with cracking activity, carries
The serviceability of high hydrocracking catalyst.
The hydrocracking catalyst that the present invention uses preferred Y type molecular sieve to make is particularly suitable as High middle distillate hydrogenation
Cracking catalyst, had both had high hydrogenation cracking activity, had again high middle distillates oil selectivity, the most also had stronger resistance to nitrogen ability
Etc. good serviceability.This catalyst, in single-stage hydrocracking technical process, has liquid yield high, good product quality
Etc. advantage.
Detailed description of the invention
In the present invention, specific surface area and pore volume use low temperature liquid nitrogen physisorphtion, and relative crystallinity and cell parameter are adopted
With x-ray diffraction method, silica alumina ratio uses chemical method, and sodium content uses plasma emission spectrometry, catalyst surface active gold
Belonging to concentration uses chemical analysis electron spectrum (ESCA) to measure.Transmissioning electric mirror determining catalyst surface WS2Density.The present invention
In, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
By containing the nickel chloride solution that NiO is 45g/L 600 milliliters, containing Al2O3The liquor alumini chloridi of 115g/L 450 milliliters, contains
ZrO2120g/L zirconyl chloride solution 100 milliliters, is mixed in NaOH solution tank NaOH 1, adds 800 milliliters of water purification dilutions, is configured to solution
A.WO will be contained3 The ammonium metatungstate of 80g/L 900 milliliters and containing Al2O3 The liquor alumini chloridi of 115g/L 450 milliliters, is mixed in solution
In tank 2, add 800 milliliters of water purification dilutions, add 500 milliliters under agitation containing SiO2Dilute water glass solution of 110g/L,
Configuration solution B.Ammonia under agitation adds solution A, and gelling temperature is maintained at 50 DEG C, at the end of pH value control 7.8, plastic
Time controls at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.1000mL water purification is added in retort, by ammonia and solution
B also flows in addition retort, and gelling temperature is maintained at 50 DEG C, and flows pH value in plastic course of reaction and control 7.8, gelation time
Control at 60 minutes, generate tungstenic, silicon, aluminum precipitation thing serosity II.After above two is mixed containing sediment slurry, slurry pH value control
System, 7.8, is put into autoclave and is carried out hydrothermal treatment consists, and temperature is 120 DEG C, and pressure is 2.5MPa, and hydrothermal treatment consists is after 15 hours, not
In the case of disconnected stirring, the precipitate serosity mixing after hydrothermal treatment consists add account for total catalyst weight 12wt% at hydro-thermal
Reason Modified Zeolite Y suspension (preparing by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is uniformly
It is scattered in the mixed serum that plastic obtains, filters, be dried 10 hours at 80 DEG C, roll, extruded moulding.Wash with water purification under room temperature
Wash.Then it is dried 8 hours at 100 DEG C, 530 DEG C of roastings 4 hours, obtains catalyst A.Catalyst composition and main character are shown in Table 1.
Embodiment 2
According to the method for embodiment 1, by the constituent content proportioning of the catalyst B in table 1, in dissolving tank 1, add nitric acid
Nickel, titanium chloride, aluminum nitrate solution, prepare working solution A, adds aluminum nitrate, ammonium metatungstate and dilute waterglass and join in dissolving tank 2
Working solution B processed, the dilutest waterglass is containing SiO2Dilute water glass solution of 112g/L 480 milliliters.Ammonia is under agitation added
Entering solution A, gelling temperature is maintained at 40 DEG C, at the end of pH value control 8.0, gelation time control at 50 minutes, generate nickeliferous,
Aluminum precipitation thing serosity I.1000mL water purification is added in retort, by ammonia and solution B and flow in addition retort, gelling temperature
Be maintained at 50 DEG C, and flow pH value in plastic course of reaction and control 7.8, gelation time control at 50 minutes, generate tungstenic, silicon,
Aluminum precipitation thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls 7.6, puts into autoclave and carries out water
Heat treatment, temperature is 100 DEG C, and pressure is 1.2MPa, and hydrothermal treatment consists is after 10 hours, in the case of being stirred continuously, at hydro-thermal
Precipitate serosity mixing addition after reason accounts for the hydrothermal treatment Modified Zeolite Y suspension of total catalyst weight 15wt% and (presses
Prepared by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains
In, filter, be dried 10 hours at 80 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 8 hours at 120 DEG C,
600 DEG C of roastings 3 hours, obtain catalyst B.Catalyst composition and main character are shown in Table 1.
Embodiment 3
According to the method for embodiment 1, by the constituent content proportioning of the catalyst C in table 1, in dissolving tank 1, add chlorination
Nickel, liquor alumini chloridi, prepare working solution A, adds aluminum chloride, ammonium molybdate, dilute waterglass preparation working solution in dissolving tank 2
B, the dilutest waterglass is containing SiO2Dilute water glass solution of 120g/L 420 milliliters.Ammonia is under agitation added solution A, becomes
Glue temperature is maintained at 45 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing slurry
Liquid I.Adding in retort equipped with 1200mL water purification, by ammonia and solution B and flow in addition retort, gelling temperature is maintained at 65
DEG C, and flow pH value in plastic course of reaction and control 7.4, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing
Serosity II.After above two being mixed containing sediment slurry, slurry pH value controls 7.8, puts into autoclave and carries out hydrothermal treatment consists, temperature
Degree is 80 DEG C, and pressure is 1.8MPa, and hydrothermal treatment consists is after 20 hours, the precipitation in the case of being stirred continuously, after hydrothermal treatment consists
The mixing addition of thing serosity accounts for the hydrothermal treatment Modified Zeolite Y suspension of total catalyst weight 10wt% and (presses
Prepared by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains
In, filter, be dried 10 hours at 70 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 10 at 100 DEG C little
Time, 550 DEG C of roastings 5 hours, obtain catalyst C.Catalyst composition and main character are shown in Table 1.
Embodiment 4
According to the method for embodiment 1, by the constituent content proportioning of the catalyst D in table 1, in dissolving tank 1, add chlorination
Nickel, zirconium oxychloride, liquor alumini chloridi, preparating acid sex work solution A, in dissolving tank 2, add aluminum chloride, ammonium molybdate, dilute water glass
Glass preparating acid sex work solution B, the dilutest waterglass is containing SiO2Dilute water glass solution of 100g/L 410 milliliters.Ammonia is existed
Adding solution A under stirring, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control at 60 minutes,
Generate nickeliferous, aluminum precipitation thing serosity I.Add in retort equipped with 1200mL water purification, by ammonia and solution B and flow addition retort
In, gelling temperature is maintained at 60 DEG C, and flows pH value in plastic course of reaction and control 7.6, and gelation time control was at 60 minutes, raw
Become tungstenic, silicon, aluminum precipitation thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls, 8.0, to put into height
Pressure still carries out hydrothermal treatment consists, and temperature is 110 DEG C, and pressure is 2.2MPa, and hydrothermal treatment consists is after 5 hours, in the case of being stirred continuously,
Precipitate serosity mixing after hydrothermal treatment consists adds the hydrothermal treatment Modified Zeolite Y accounting for total catalyst weight 18wt%
Suspension (is prepared by CN102441411A embodiment 3), and Y type molecular sieve character is shown in Table 6 so that it is be dispersed in what plastic obtained
In mixed serum, filter, be dried 12 hours at 80 DEG C, roll, extruded moulding.Wash with the Spirit of Mindererus. of pH=8.8 under room temperature
Wash, be then dried 10 hours at 90 DEG C, 530 DEG C of roastings 5 hours, obtain catalyst D.Catalyst composition and main character are shown in Table 1.
Comparative example 1
Preparing according to method disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, and concrete steps are such as
Under:
(1) preparation is containing Al2O3Concentration is the liquor alumini chloridi 900 milliliters of 115g/L, molten containing the Nickel dichloride. that NiO is 45g/L
Liquid 600 milliliters, containing ZrO2120g/L zirconyl chloride solution 100 milliliters, and be mixed in the container of 5 liters, add 2000 millis
Rise water purification dilution；
(2) dilute water glass solution is prepared, containing SiO2The water glass solution of 110g/L 500 milliliters, under agitation will
(2) add in (1)；
(3) ammonia is added under agitation the mixture of (1) and (2) until pH value 5.2；
(4) preparation sodium tungstate solution 900 milliliters, containing WO3For 80g/L, and join under agitation (1)+(2)+
(3) in mixture；
(5) ammonia is continuously added until pH value is 7.8；
(6) whole plastic process should be carried out at 50 DEG C；
(7) mixture stands aging 2.5 hours at 70 DEG C；Add before aging with CN102441411A embodiment 3 preparation
Y type molecular sieve suspension, Y type molecular sieve accounts for the 12% of total catalyst weight, and character is shown in Table 6.
(8) filter, 80 DEG C of oven dryings 10 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters；Under room temperature
Wash with the Spirit of Mindererus. of pH=8.8；Then 100 DEG C of oven dryings 8 hours, 530 DEG C of roastings 4 hours, obtain reference agent E,
Composition and main character are shown in Table 1.
Comparative example 2
Comparative example 2 preparation process uses two steps be cocurrent process plastic and prepare hydrocracking catalyst.Catalyst forms
Form identical with embodiment 1, specifically comprise the following steps that
In dissolving tank 1, add chloric acid nickel, zirconium oxychloride, liquor alumini chloridi, prepare working solution A, add in dissolving tank 2
Entering aluminum chloride, ammonium metatungstate and dilute waterglass preparation working solution B, the dilutest waterglass is containing SiO2Dilute waterglass of 110g/L
Solution 500 milliliters.Just 1000mL water purification adds in retort, by ammonia and solution A and flow in addition retort, and gelling temperature
Being maintained at 50 DEG C, and flow pH value in plastic course of reaction and control 7.8, gelation time control, at 60 minutes, generates nickel-and aluminum-containing and sinks
Shallow lake thing serosity I.Being added in retort by 1000mL water purification, by ammonia and solution B and flow in addition retort, gelling temperature keeps
At 50 DEG C, and flowing pH value in plastic course of reaction and control 7.8, gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum sink
Shallow lake thing serosity II.After above two being mixed containing sediment slurry, slurry pH value controls 7.8, puts into autoclave and carries out at hydro-thermal
Reason, temperature is 120 DEG C, and pressure is 2.5MPa, and hydrothermal treatment consists is after 15 hours, in the case of being stirred continuously, after hydrothermal treatment consists
The mixing of precipitate serosity add and account for the hydrothermal treatment Modified Zeolite Y suspension of total catalyst weight 12wt% and (press
Prepared by CN102441411A embodiment 3), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains
In, filter, be dried 10 hours at 80 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 8 hours at 100 DEG C,
530 DEG C of roastings 4 hours, obtain catalyst F.Catalyst composition and main character are shown in Table 1.
Comparative example 3
Comparative example 3 preparation process uses two steps be positive addition plastic and prepare hydrocracking catalyst.Catalyst forms
Form identical with embodiment 1, specifically comprise the following steps that
In dissolving tank 1, add chloric acid nickel, zirconium oxychloride, chlorine aluminum solutions, prepare working solution A, add in dissolving tank 2
Aluminum chloride, ammonium metatungstate and dilute waterglass preparation working solution B, the dilutest waterglass is containing SiO2Dilute waterglass of 110g/L is molten
Liquid 500 milliliters.Ammonia under agitation adds solution A, and gelling temperature is maintained at 55 DEG C, at the end of pH value control 7.6, plastic
Time controls at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.Ammonia under agitation adds solution B, and gelling temperature keeps
At 50 DEG C, at the end of pH value control 7.8, gelation time control at 60 minutes, tungsten, silicon, aluminum precipitation thing serosity II.By above-mentioned two
Planting after mixing containing sediment slurry, slurry pH value controls 7.8, puts into autoclave and carries out hydrothermal treatment consists, and temperature is 120 DEG C, pressure
For 2.5MPa, hydrothermal treatment consists is after 15 hours, and in the case of being stirred continuously, the precipitate serosity mixing after hydrothermal treatment consists adds
The hydrothermal treatment Modified Zeolite Y suspension accounting for total catalyst weight 12wt% (is made by CN102441411A embodiment 3
Standby), Y type molecular sieve character is shown in Table 6 so that it is be dispersed in the mixed serum that plastic obtains, and filters, and is dried 10 at 80 DEG C little
Time, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 8 hours at 100 DEG C, 530 DEG C of roastings 4 hours, is urged
Agent G, catalyst composition and main character are shown in Table 1.
Embodiment 5
Middle oil type hydrocracking catalyst A, B, D and reference catalyst E, F and G of the present invention are evaluated on midget plant
Result compares.Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h-1, evaluate with former
Material is Iran's VGO heavy distillate, and its main character is shown in Table 4, and table 5 lists evaluation result.
From table 2 and table 3 it can be seen that the reunion of tungsten and nickel particles does not occurs in catalyst prepared by the inventive method, activity
Metal dispersion is uniform, and can be fully contacted.From the data of table 5 can be seen that use the present invention prepare catalyst A, catalyst B,
The activity of catalyst D and middle distillates oil selectivity are better than reference agent, illustrate that active metal is uniformly dispersed, and improve the activity of catalyst
Rate of metal.
Table 1 catalyst composition and character
Table 2 ESCA measures catalyst surface metal relative atomic concentration (mol ratio)
| Catalyst is numbered | A | B | C | D | E | F | G |
| IW/IAl | 0.18 | 0.17 | 0.17 | 0.18 | 0.12 | 0.13 | 0.12 |
| INi/IAl | 0.47 | 0.48 | 0.49 | 0.48 | 0.40 | 0.41 | 0.41 |
Table 3 transmissioning electric mirror determining catalyst surface WS2Density
| Catalyst is numbered | A | B | C | D | E | F | G |
| WS2Density, grain/100nm | 45 | 45 | 46 | 44 | 38 | 38 | 37 |
Table 4 raw oil main character
Table 5 evaluating catalyst result
The character of the modified molecular screen that table 6 the present invention relates to
Claims (19)
1. a preparation method for hydrocracking catalyst, including:
(1), preparation containing the mixed solution A of Ni, Al component, precipitant is added dropwise to solution A and carries out plastic reaction, generate nickeliferous,
Aluminum precipitation thing serosity I；
(2), preparation containing the mixed solution B of W, Si, Al component, precipitant and solution B stream are carried out plastic reaction, generation contains
Tungsten, silicon, aluminum precipitation thing serosity II；
(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, the serosity obtained is carried out water
Heat treatment, adds the suspension of Y type molecular sieve, stirs after hydrothermal treatment consists；
(4) the material drying, obtained by step (3), molding, washing,
(5), step (4) gained material drying again and roasting, prepared hydrocracking catalyst.
The most in accordance with the method for claim 1, it is characterised in that: described Y type molecular sieve is with the shape of molecular sieve suspension
Formula adds, and will be ground to 80 mesh ~ 140 mesh by molecular sieve, then add water and make suspension.
The most in accordance with the method for claim 1, it is characterised in that: the character of described Y type molecular sieve is as follows: bore dia is more than
The pore volume of 1.7nm accounts for more than the 45% of total pore volume, and specific surface area is 750～900m2/ g, cell parameter at 2.423nm～
2.545nm, relative crystallinity 95%～110%, SiO2/Al2O3Mol ratio is 7～60.
The most in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, with the weight of catalyst
On the basis of, WO3Content be 10wt%～50wt%, the content of NiO is 1wt%～30wt%, and W/Ni atomic ratio is 0.05～1.0.
The most in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, with the weight of catalyst
On the basis of, WO3Content be 15wt%～30wt%, the content of NiO is 5wt%～20wt%, and W/Ni atomic ratio is 0.1～0.7.
The most in accordance with the method for claim 1, it is characterised in that: Si, the Al introduced in step (2) is being catalyzed in terms of oxide
Weight content in agent is 20wt%～60wt%, and wherein Si accounts for the 30wt% of Si, Al gross weight in terms of oxide in terms of silicon oxide
～80wt%；The Al introduced in step (1) counts weight content in the catalyst as 10wt%～30wt% with oxide.
The most in accordance with the method for claim 1, it is characterised in that: in described hydrocracking catalyst, the content of Y type molecular sieve
For 5wt%～30wt%.
The most in accordance with the method for claim 1, it is characterised in that: the precipitant described in step (1) or step (2) is carbonic acid
One or more in sodium, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate.
The most in accordance with the method for claim 1, it is characterised in that: the precipitant described in step (1) or step (2) is ammonia
Water.
The most in accordance with the method for claim 1, it is characterised in that: in step (1) mixed solution A, Ni weight in terms of NiO
Concentration is 20～80g/L, and Al is with Al2O3The weight concentration of meter is 60～200g/L；In step (2) mixed solution B, W is with WO3Meter
Weight concentration be 50～120g/L, Si is with SiO2The weight concentration of meter is 80～250g/L, and Al is with Al2O3The weight concentration of meter
It is 60～200g/L.
11. in accordance with the method for claim 1, it is characterised in that: in step (1) mixed solution A, Ni weight in terms of NiO
Concentration is 30～60g/L, and Al is with Al2O3The weight concentration of meter is 90～150g/L；In step (2) mixed solution B, W is with WO3Meter
Weight concentration be 70～100g/L, Si is with SiO2The weight concentration of meter is 100～180g/L, and Al is with Al2O3The weight of meter is dense
Degree is 90～150g/L.
12. in accordance with the method for claim 1, it is characterised in that: when preparing mixed solution A, the nickel source of employing is sulphuric acid
One or more in nickel, nickel nitrate, basic nickel carbonate, Nickel dichloride., aluminum source is aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate
In one or more；Prepare mixed solution B time, the tungsten source of employing be the one in ethyl ammonium metatungstate, ammonium metatungstate or
Several；Silicon source is one or more in Ludox, sodium silicate；Aluminum source is in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate
One or more.
13. in accordance with the method for claim 1, it is characterised in that: in step (1), reaction temperature is 20～90 DEG C, becomes cementing
During bundle, pH value controls is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour；In step (2), reaction temperature is 30～90 DEG C, and
During stream plastic, pH value controls to be 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour.
14. in accordance with the method for claim 1, it is characterised in that: in step (1), reaction temperature is 30～70 DEG C, becomes cementing
During bundle, pH value controls is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour；In step (2), reaction temperature is 40～80 DEG C, and flows
During plastic, pH value controls is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour.
15. in accordance with the method for claim 1, it is characterised in that: in step (3), the temperature of hydrothermal treatment consists is 40～220 DEG C,
Hydrothermal treatment consists pressure is 1MPa～3MPa, and during hydrothermal treatment consists serosity, pH value controls is 6.0 ~ 10.0, hydrothermal conditions is 0.5 ~
30 hours.
16. in accordance with the method for claim 1, it is characterised in that: in step (3), the temperature of hydrothermal treatment consists is 70～150 DEG C,
Hydrothermal treatment consists pressure is 1MPa～3MPa, and during hydrothermal treatment consists serosity, pH value controls is 6.5 ~ 9.0, and hydrothermal conditions is
1.0 ~ 24 hours.
17. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (4): do at 50 ~ 200 DEG C
Dry 1 ~ 48 hour；Being dried described in step (5) is as follows with roasting condition: be dried 1 ~ 48 hour at 50 ~ 200 DEG C, at 450 ~ 600 DEG C
Roasting 1 ~ 24 hour.
18. in accordance with the method for claim 1, it is characterised in that: containing adjuvant component in described hydrocracking catalyst,
Described adjuvant component is Ti and/or Zr, counts the content in hydrocracking catalyst as 1wt%～10wt% with oxide.
19. in accordance with the method for claim 18, it is characterised in that: in hydrocracking catalyst preparation process, in preparation
The compound containing adjuvant component, i.e. titanium source and/or zirconium source is added during mixed solution A；Titanium source use Titanium Nitrate, titanium sulfate,
One or more in titanium chloride, zirconium source uses one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532053.3A CN104588083B (en) | 2013-11-03 | 2013-11-03 | A kind of preparation method of hydrocracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532053.3A CN104588083B (en) | 2013-11-03 | 2013-11-03 | A kind of preparation method of hydrocracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104588083A CN104588083A (en) | 2015-05-06 |
| CN104588083B true CN104588083B (en) | 2016-08-17 |
Family
ID=53114338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310532053.3A Active CN104588083B (en) | 2013-11-03 | 2013-11-03 | A kind of preparation method of hydrocracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104588083B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110038620B (en) * | 2018-01-16 | 2021-12-07 | 中国石油化工股份有限公司 | Process for preparing hydrocracking catalyst |
-
2013
- 2013-11-03 CN CN201310532053.3A patent/CN104588083B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104588083A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104588085B (en) | The method preparing hydrocracking catalyst | |
| CN104588086B (en) | The preparation method of hydrocracking catalyst | |
| CN104588084B (en) | A kind of preparation method of the hydrocracking catalyst containing rare earth | |
| CN104588082B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN106179461B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN102451744B (en) | Preparation method of hydrocracking catalyst | |
| CN103055922B (en) | Preparation method of bulk phase hydrocracking catalyst | |
| CN103055924B (en) | Preparation method of bulk phase hydrocracking catalyst | |
| CN106179467B (en) | A kind of sulfurized hydrogenation Cracking catalyst and preparation method thereof | |
| CN106179462B (en) | A kind of hydrocracking catalyst and preparation method thereof | |
| CN104588120B (en) | Preparation method for hydrocracking catalyst containing heteropoly acid | |
| CN104588081B (en) | The preparation method of the hydrocracking catalyst containing rare earth | |
| CN104588072B (en) | Preparation method for hydrocracking catalyst | |
| CN103055923B (en) | Preparation method of hydrocracking catalyst | |
| CN103055927B (en) | Preparation method of hydrocracking catalyst | |
| CN104588083B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN106179288B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN106179464B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN104588119B (en) | Preparation method for hydrocracking catalyst containing heteropoly acid | |
| CN106179466B (en) | The preparation method of hydrocracking catalyst | |
| CN106179465B (en) | The preparation method of hydrocracking catalyst | |
| CN106179463B (en) | Hydrocracking catalyst and its preparation method | |
| CN106179514B (en) | A kind of hydrocracking catalyst and preparation method thereof containing heteropoly acid | |
| CN106179391B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN103055926B (en) | Preparation method of hydrocracking catalyst composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |