CN1660968A - Catalyst possessing effect of desulfurization for Cracking hydrocarbon and preparation method - Google Patents
Catalyst possessing effect of desulfurization for Cracking hydrocarbon and preparation method Download PDFInfo
- Publication number
- CN1660968A CN1660968A CN 200410004478 CN200410004478A CN1660968A CN 1660968 A CN1660968 A CN 1660968A CN 200410004478 CN200410004478 CN 200410004478 CN 200410004478 A CN200410004478 A CN 200410004478A CN 1660968 A CN1660968 A CN 1660968A
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- Prior art keywords
- compound
- weight
- zeolite
- molecular sieve
- metal
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000005336 cracking Methods 0.000 title claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 26
- 238000006477 desulfuration reaction Methods 0.000 title description 8
- 230000023556 desulfurization Effects 0.000 title description 8
- 230000000694 effects Effects 0.000 title description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 115
- 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 115
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 26
- 239000004927 clay Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims description 133
- 239000010457 zeolite Substances 0.000 claims description 105
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 103
- 229910021536 Zeolite Inorganic materials 0.000 claims description 100
- 229910052751 metal Inorganic materials 0.000 claims description 96
- 239000002184 metal Substances 0.000 claims description 96
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 54
- 239000011248 coating agent Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 54
- 229910052720 vanadium Inorganic materials 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 239000005995 Aluminium silicate Substances 0.000 claims description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims description 26
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229910000765 intermetallic Inorganic materials 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 20
- 150000002602 lanthanoids Chemical class 0.000 claims description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 19
- -1 polynite Chemical compound 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052716 thallium Inorganic materials 0.000 claims description 8
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003682 vanadium compounds Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 7
- 238000001935 peptisation Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010953 base metal Substances 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 150000003755 zirconium compounds Chemical class 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 238000000637 aluminium metallisation Methods 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003009 desulfurizing effect Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 32
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 26
- 239000003502 gasoline Substances 0.000 description 26
- 229910002651 NO3 Inorganic materials 0.000 description 25
- 239000003921 oil Substances 0.000 description 22
- 229910052717 sulfur Inorganic materials 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 238000004523 catalytic cracking Methods 0.000 description 14
- 239000005864 Sulphur Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 9
- 239000002841 Lewis acid Substances 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910001038 basic metal oxide Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 229910052914 metal silicate Inorganic materials 0.000 description 2
- 239000002063 nanoring Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
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Landscapes
- Catalysts (AREA)
Abstract
A hydrocarbon cracking catalyst with desulfurizing action is prepared from a molecular sieve composition, refractory inorganic oxide, and clay or not. Said molecular composition is composed of molecular sieve and the coated layer prepared from alumina and metallic component.
Description
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof, more particularly, is about a kind of hydrocarbon cracking catalyzer with desulfidation and preparation method thereof.
Background technology
In recent years, for the consideration of environmental protection, worldwide, the requirement of oil fuel standard is improved constantly.With China is example, and State Quality Supervision Bureau had formulated " motor spirit objectionable impurities control criterion " in 1999, and according to the requirement of this standard, the sulphur content of gasoline product should be less than 800ppm.In fact, the sulphur of gasoline product more than 90% comes from FCC gasoline, and on the other hand, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is increasing, and therefore, the sulphur content that reduces in the FCC gasoline is most important to producing clean gasoline.
At present, can be by stock oil be carried out the hydrogenation pre-treatment, or FCC gasoline carried out making with extra care behind the hydrogenation reach the purpose that reduces the FCC sulfur in gasoline.Yet these two kinds of method investments are big, and the process cost height also can cause the loss of gasoline octane rating.
In the FCC riser tube, by the method for catalytic cracking, it is the most attractive technological approaches economically that the sulphur original position is removed.For reaching this purpose, need in catalytic cracking process, add promotor with desulfurizing function, perhaps use the cracking catalyst that has desulfurizing function, contains the desulfurization component.
US6,036,847 and patent families EP0,798,362A2 discloses a kind of fluidized catalytic cracking of hydrocarbons method, wherein, and under the condition of described hydrocarbon feed hydrogenation outside not existing, a zone of cracking by cracking, and all particles that comprise granules of catalyst wherein, contain another particle constantly in cracking hydrocarbon district and a catalyst regeneration zones circulation in all particles, this particle has the activity of the cracking hydrocarbon ils lower than granules of catalyst, and described activity is benchmark with the fresh granules.This particle is made up of the inorganic oxide of titanium oxide and a kind of non-oxide titanium basically.The inorganic oxide of described non-oxide titanium contains a kind of Lewis acid, this Lewis acid is selected from following element and compound composition thereof one group: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and germanium, described Lewis acid loads on the aluminum oxide.Because use this auxiliary agent that contains titanium oxide, crackate FCC sulfur in gasoline content is reduced.
US5,376,608 disclose a kind of cracking catalyst composition with desulfidation, said composition contains (A) and is dispersed in zeolite/molecular sieve in a kind of inorganic oxide matrix, (b) contain the alumina component of Lewis acid, this alumina component contains the Lewis acid of 1-50 weight %, and described Lewis acid is selected to load on and contains nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and the element of gallium and a group of oxide compound on the aluminum oxide.
WO 99/49001A1 discloses a kind of composition that reduces sulphur content in the hydrocarbon component, said composition contains a kind of houghite (hydrotalcite) material, this material is with a kind of Lewis acid dipping, can also contain a kind of FCC catalyzer in the said composition. described Lewis acid comprises transition metal, particularly the element of zinc, copper, nickel, cobalt, iron and manganese and compound.
WO 01/21733A1 discloses a kind of in the presence of heat regeneration cracking catalyst, contains the catalyst cracking method of organosulfur compound hydrocarbon raw material, and described catalyzer contains a kind of component that reduces The product sulfur, this component contains a kind of oxidation state greater than zero metal component, and described metal component comprises the 3rd cycle of the periodic table of elements, VB family, VIIB family, VIII family, IIB family, the metallic compound of IVA family or complex compound, as vanadium, zinc, iron, cobalt, the metallic compound of manganese and gallium or complex compound.The component of described reduction The product sulfur comprises that pore structure contains the molecular sieve of above-mentioned metal component, also comprises being dispersed in the support of the catalyst optional position, as the above-mentioned metal component in the porous oxide carrier.
WO 01/21732A1 discloses a kind of method that reduces sulphur content in the cracking petroleum fraction, this method is included in the temperature of raising and a kind of cracking catalyst and a kind of catalyzer that reduces the product sulphur content and exists down, with the petroleum fractions catalytic cracking, obtain having liquid crackate than low sulfur content.Wherein, the catalyzer of described reduction product sulphur content contains a kind of non-molecular sieve carrier of vanadium that contains, and described non-molecular sieve carrier can be the organic or inorganic carrier, preferred carrier is amorphous or the para-crystal inorganic oxide, as aluminum oxide, silicon oxide, clay or their mixture.
CN1281887A discloses a kind of method that reduces catalytic cracking gasoline cut sulphur content, and this method is included in high temperature and the product desulfurization catalyst exists down, catalytic cracking gasoline feedstock fraction, the liquid cracked product of preparation low sulfur content.This desulfurization catalyst contains the porous molecular screen that metal ingredient is contained in a kind of cavernous structure inside.Described porous molecular screen can be a large pore zeolite, and promptly orifice diameter is at least the zeolite of 0.7 nanometer, as y-type zeolite, rare earth Y type zeolite (REY), ultrastable Y (USY), L zeolite, Beta zeolite, mordenite, ZSM-18 zeolite.Described molecular sieve also can be a mesopore zeolite, be orifice diameter for greater than 0.56 zeolite, as Pentasil zeolite, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite less than 0.7 nanometer.Described molecular sieve can also be a non-zeolite molecular sieve, as the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate.Titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, aluminosilicophosphate silicoaluminophosphates (SAPO molecular sieve), gallium germanate (gallogermanates) and their combination.
CN1261618A discloses a kind of sulfur method of catalytic cracking gasoline cut, this method is included under the existence of high temperature, cracking catalyst and product desulfurization catalyst, to contain the petroleum cut catalytic cracking of organosulfur compound, produce the liquid crackate of low sulfur content.Described product desulfurization catalyst contains a kind of porous molecular screen, this molecular sieve contains first metal component and second metal component, first metal component is positioned at Molecular Sieve Pore inside and oxidation state greater than zero, and second metal component comprises at least a rare earth element that is positioned at Molecular Sieve Pore inside.Described first kind of metal component is selected from periodic table of elements period 4 and IIB, VB, IIIA, the metal, particularly vanadium of VIII family, zinc, iron, gallium.
CN1356374A discloses a kind of catalytic cracking catalyst that reduces the content of sulfur in gasoline function that has, and it is mainly by zeolitic material, rare earth material with have than the metal oxide of large specific surface etc. and form.Its preparation method is comprehensively to adopt pickling process and coprecipitation method.This catalyzer is to have more highly acid zeolitic material as catalyzer cracking activity component, adopt dipping, roasting method that the form of rare earth with oxide compound is dispersed on the acid zeolite, to stroke the metal hydroxides uniform mixing that stone and co-precipitation make again, and then wash, dry, roasting and pulverizing.Described metal hydroxides can be one or more of Cu, Zn, Fe, A1, As, Hg, Ni, Zr, Sn, La, Ce, Pr, Nd, Sm, Ga and Ti.
CN1356379A discloses a kind of sweetening additive of sulphur content in the coke that can reduce simultaneously on gasoline and the catalyzer.It is mainly by zeolitic material, rare earth material, alkali or alkaline earth metal oxide with have metal oxide than large specific surface etc. and form.Its preparation method is comprehensively to adopt pickling process and coprecipitation method.This catalyzer is to serve as to suppress sulfide condensation green coke constituent element with basic metal or alkaline earth metal oxide.This catalyzer is still to have more highly acid zeolitic material as catalyzer cracking activity component, adopt dipping, roasting method that the form of rare earth with oxide compound is dispersed on the acid zeolite, the metal hydroxides uniform mixing that zeolite and co-precipitation are made again, and then wash, dry, roasting and pulverizing, adopt dipping, roasting method that basic metal or alkaline earth metal oxide are dispersed on the above-mentioned zeolite at last.Described metal hydroxides can be one or more of Cu, Zn, Fe, Al, As, Hg, Ni, Zr, Sn, La, Ce, Pr, Nd, Sm, Ga and Ti.
Above-mentioned cracking catalyst with desulfidation has certain desulfurization performance, and still, this class catalyst desulfurizing activity is not high enough.The particularly existing cracking catalyst that contains vanadium with desulfidation, because the aging and regenerative process of catalyzer is all carried out under high temperature and moisture vapor condition, under such condition, contained vanadium easily forms the liquid vanadic acid in the catalyzer, it is external and run off that formed liquid vanadic acid is understood outflow catalyst on the one hand, also can corrode the skeleton of contained molecular sieve in the catalyzer on the other hand, make the skeleton structure avalanche of molecular sieve, thereby the desulphurizing activated and cracking activity of cracking catalyst is all reduced rapidly.
CN1388220A discloses a kind of combination of molecular sieve with desulfidation, and said composition is made up of as the molecular sieve of catalyst and cracking of hydrocarbon active ingredient and the coating oxidation thing that is covered in this molecular sieve surface of 2-20 weight 80-98 weight %'s; The chemical constitution expression formula of wherein said coating oxidation thing is designated as with the mol ratio of oxide compound: aZnObTiO2Al
2O
3Wherein a is 0-2; B is 0-2; A and b are not 0 simultaneously.This catalyzer contains the coating of aluminum oxide, zinc and titanium, and the stability of molecular sieve is improved, and is still, desulphurizing activated still not high enough.
Summary of the invention
The purpose of this invention is to provide a kind of new, have hydrocarbon cracking catalyzer than high desulfurization activity and preparation method thereof.
The present inventor finds, adopt specific to be different from the described coat composed combination of molecular sieve of CN1388220A as active ingredient, the hydrocarbon cracking catalyzer that obtains has higher desulphurizing activated, particularly, when the metal component in the described coating contains vanadium, desulphurizing activated higher.
Catalyzer provided by the invention contains a kind of combination of molecular sieve and heat-resistant inorganic oxide, contain or argillaceous not, wherein, described combination of molecular sieve contains molecular sieve and is covered in the coating on this molecular sieve surface, with described combination of molecular sieve is benchmark, the content of molecular sieve is 75-99 weight %, and the content of coating is 1-25 weight %; Described coating contains aluminum oxide and metal component, is benchmark with the total amount of described coating, and the content of aluminum oxide is 50-95 weight %, and in oxide compound, the content of described metal component is 5-50 weight %; Described metal component is selected from one or more in the non-aluminum metal of IIIA family, IVA family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal and the rare earth metal.
Preparation of catalysts method provided by the invention comprises and will contain combination of molecular sieve, heat-resistant inorganic oxide and/or its precursor and water, contain or slurry dried not argillaceous, wherein, the preparation method of described combination of molecular sieve is included in a kind of hydration aluminum oxide that contains, add a kind of acid in the compound of metal component and the slurries of water, make partially hydrated at least aluminum oxide peptization, obtain a kind of colloid, the colloid that obtains is mixed with molecular sieve and roasting, the compound of described metal component is selected from the non-aluminum metallization compound of IIIA family, IVA family metallic compound, IVB family metallic compound, VB family metallic compound, the group vib metallic compound, VIIB family metallic compound, in VIII family non-noble metal compound and the rare earth compound one or more, described hydrated aluminum oxide, the compound of metal component, the consumption of water and acid makes in the described coating and contains, total amount with described coating is a benchmark, the aluminum oxide of 50-95 weight % and in oxide compound, the metal component of 5-50 weight %, the consumption of described colloid and molecular sieve makes in the combination of molecular sieve that obtains and contains, with described combination of molecular sieve is benchmark, the coating of the molecular sieve of 75-99 weight % and 1-25 weight %.
Catalyzer provided by the invention has higher desulphurizing activated, show, first, compare with the cracking catalyst of the non-coating molecule screen composition that contains conventional ion-exchange, dipping and mechanical mixing preparation, catalyzer provided by the invention has higher desulphurizing activated, particularly, when the metal component in the described coating contains vanadium, the introducing of coating can prevent that vanadium from moving to the interior to the molecule sieve aperture and move, corrode the skeleton of molecular sieve, compare with containing the cracking catalyst that non-coating contains the combination of molecular sieve of vanadium, desulphurizing activated raising is more remarkable.The second, to compare with the cracking catalyst that contains the disclosed combination of molecular sieve of CN1388220A, catalyzer provided by the invention also has higher desulphurizing activated.
Embodiment
The catalyzer that provides according to this aspect, the content of described combination of molecular sieve, heat-resistant inorganic oxide and clay is the content of these component routines in the cracking catalyst, in general, with the catalyzer total amount is benchmark, the content of described combination of molecular sieve is 5-90 weight %, the content of heat-resistant inorganic oxide is 5-70 weight %, and the content of clay is 0-70 weight %; Under the preferable case, the content of described combination of molecular sieve is 10-75 weight %, and the content of heat-resistant inorganic oxide is 10-55 weight %, and the content of clay is 0-60 weight %.
With described combination of molecular sieve is benchmark, and the content of molecular sieve is 75-99 weight %, is preferably 80-99 weight %, and the content of coating is 1-25 weight, is preferably 1-20 weight %.
Total amount with described coating is a benchmark, and the content of aluminum oxide is 50-95 weight %, is preferably 60-90 weight %, and in oxide compound, the content of described metal component is 5-50 weight %, is preferably 10-40 weight %.
Under the preferable case, described metal component is selected from one or more in gallium, indium, thallium, germanium, tin, lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal.Wherein, the lanthanide rare metal is selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium, preferred lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.
According to embodiment preferred of the present invention, described metal component is selected from one or more the mixture in vanadium or vanadium and titanium, zirconium, iron, the lanthanide rare metal, total amount with coating is a benchmark, the content of aluminum oxide is 60-90 weight %, in oxide compound, the content of vanadium is 10-40 weight %, and the content of one or more in titanium, zirconium, iron, the lanthanide rare metal is 0-30 weight %.
According to another one embodiment preferred of the present invention, described metal component is selected from one or more the mixture in vanadium or vanadium and zirconium, iron, titanium, the rare earth metal, described coating also contains alkaline-earth metal, total amount with coating is a benchmark, the content of aluminum oxide is 60-90 weight %, and in oxide compound, the content of vanadium is 10-40 weight %, the content of the mixture of one or more in titanium, zirconium, iron, the lanthanide rare metal is 0-30 weight %, and the content of alkaline-earth metal is 0-30 weight %.Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, preferably magnesium and/or calcium.
The non-aluminum metal of IIIA family, IVA family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal, rare earth metal and alkaline-earth metal can be with its all cpds separately, as the state existence of oxide compound, salt in catalyzer provided by the invention.Also can form the compound that contains above-mentioned metal component more than two kinds between each metal component.
Described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.These zeolites and molecular sieve are conventionally known to one of skill in the art.
Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the zeolite that the disclosed phosphorated of CN1194181A has the MFI structure) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.
Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integrated silicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, aluminosilicophosphate silicoaluminophosphates (SAPO molecular sieve), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.
Under the preferable case, described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of cracking catalyst matrix and binder component one or more, as in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, the boron oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, the titanium oxide one or more, more preferably aluminum oxide.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is a kaolin.These clays are conventionally known to one of skill in the art.
According to method provided by the invention, described combination of molecular sieve, heat-resistant inorganic oxide and/or its precursor and the water of containing, contain or slurries not argillaceous in, each components contents makes in the final catalyzer and contains, total amount with catalyzer is a benchmark, the described combination of molecular sieve of 5-90 weight %, the heat-resistant inorganic oxide of 5-70 weight %, the clay of 0-70 weight %; Under the preferable case, each components contents makes in the final catalyzer and contains, and is benchmark with the total amount of catalyzer, the described combination of molecular sieve of 10-75 weight %, the heat-resistant inorganic oxide of 10-55 weight %, the clay of 0-60 weight %.
The precursor of described heat-resistant inorganic oxide refers in described catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminum oxide can be selected from hydrated aluminum oxide and/or aluminium colloidal sol; Described hydrated aluminum oxide is selected from one or more in boehmite (boehmite), false boehmite (pseudo-boehmite), the hibbsite.The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of silicon sol and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of other heat-resistant inorganic oxide can be selected from its oxyhydroxide, as the oxyhydroxide of zirconium, titanium, in the boric acid one or more.Preferred hydrated aluminum oxide of the precursor of described heat-resistant inorganic oxide and/or aluminium colloidal sol.
Described combination of molecular sieve, heat-resistant inorganic oxide and/or its precursor and the water of containing, contain or the drying means and the condition of slurries argillaceous are not conventionally known to one of skill in the art, for example, the exsiccant method can be dry, oven dry, forced air drying or spraying drying, preferably spray drying.The exsiccant temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.
In the preparation of described combination of molecular sieve, described hydrated aluminum oxide is selected from one or more in the various hydrated aluminum oxides, as in boehmite (boehmite), false boehmite (pseudo-boehmite), hibbsite, amorphous hydroted alumina, the aluminium colloidal sol one or more.
The compound of described metal component is selected from one or more in the water-soluble and water-insoluble compound of described metal component.
For example, the non-aluminum metal of IIIA family, IVA family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal, rare earth compound can be selected from one or more in the halogenide, nitrate, vitriol, phosphoric acid salt, carbonate, oxyhydroxide, oxide compound, organic acid salt of these metals.
Under the preferable case, described metallic compound is selected from the compound of compound, the nickel of compound, the cobalt of compound, the iron of compound, the tungsten of compound, the molybdenum of compound, the chromium of compound, the tantalum of compound, the niobium of compound, the vanadium of compound, the hafnium of compound, the zirconium of the compound of compound, the tin of compound, the germanium of compound, the thallium of compound, the indium of gallium, plumbous compound, titanium, in the lanthanide rare metallic compound one or more.
More under the preferable case, the compound of described metal component is selected from one or more the mixture in vanadium compound or vanadium compound and titanium compound, zirconium compounds, iron cpd, the lanthanide rare metallic compound, the consumption of each component makes in the composition and contains, total amount with coating is a benchmark, the aluminum oxide of 60-90 weight %, in oxide compound, the vanadium of 10-40 weight %, one or more in the titanium of 0-30 weight %, zirconium, iron, the lanthanide rare metal.
Another one is more under the preferable case, the compound of described metal component is selected from vanadium compound or vanadium compound and titanium compound, zirconium compounds, iron cpd, the mixture of one or more in the lanthanide rare metallic compound, also adopt in described slurries and add alkaline earth metal compounds, perhaps alkaline earth metal compounds and the colloid blended method that obtains are introduced alkaline-earth metal, the consumption of each component makes in the composition and contains, total amount with coating is a benchmark, the aluminum oxide of 60-90 weight %, in oxide compound, the vanadium of 10-40 weight %, the titanium of 0-30 weight %, zirconium, iron, in the lanthanide rare metal one or more and in oxide compound, the alkaline-earth metal of 0-30 weight %.
The compound of described gallium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of gallium; The compound of indium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of indium; The compound of thallium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of thallium; The compound of germanium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound, germanate of germanium; The compound of tin is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of tin; Plumbous compound is preferably one or more in plumbous halogenide, nitrate, oxyhydroxide, the oxide compound; The compound of titanium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of titanium; The compound of zirconium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of zirconium; The compound of hafnium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of hafnium; The compound of vanadium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound, vanadate, metavanadate of vanadium; The compound of niobium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of niobium; The compound of tantalum is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of tantalum; The compound of chromium is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound, chromic salt of chromium; The compound of molybdenum is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound, molybdate salt of molybdenum; The compound of tungsten is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound, tungstate, metatungstate of tungsten; The compound of iron is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of iron; The compound of cobalt is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of cobalt; The compound of nickel is preferably one or more in the halogenide, nitrate, oxyhydroxide, oxide compound of nickel; The lanthanide rare metallic compound is preferably halogenide, nitrate, oxyhydroxide, the oxide compound of lanthanum, the halogenide of cerium, nitrate, oxyhydroxide, oxide compound, halogenide, nitrate, oxyhydroxide, the oxide compound of the halogenide of lanthanum rich norium, nitrate, oxyhydroxide, oxide compound or cerium-rich mischmetal metal.
Described alkaline earth metal compound can be selected from one or more in the water-soluble and water-insoluble compound of alkaline-earth metal, as in the halogenide of alkaline-earth metal, nitrate, vitriol, phosphoric acid salt, carbonate, oxyhydroxide, oxide compound, the organic acid salt one or more, be preferably in the halogenide, nitrate, oxyhydroxide, oxide compound of beryllium, magnesium, calcium, strontium, barium one or more.
Described acid is selected from one or more in water-soluble mineral acid and the organic acid, is preferably hydrochloric acid, nitric acid, phosphoric acid, carbonatoms and is in the carboxylic acid of 1-10 one or more.In order to make described hydrated aluminum oxide to the small part peptization, the consumption of acid makes the colloidal pH value that obtains for 1-3, is preferably 1.5-2.5.For the ease of on molecular sieve, forming described coating, it is 5-20 weight % that the compound of hydrated aluminum oxide, metal component, the consumption of water make the colloidal solid content that obtains, and make in the described coating and contain, total amount with described coating is a benchmark, the aluminum oxide of 50-95 weight % and in oxide compound, the metal component of 5-50 weight %.Under the preferable case, making the colloidal solid content that obtains is 10-15 weight %, and makes in the described coating and contain, and is benchmark with the total amount of described coating, the aluminum oxide of 60-90 weight % and in oxide compound, the metal component of 10-40 weight %.
The consumption of described colloid and molecular sieve makes in the combination of molecular sieve that obtains and contains, and is benchmark with described combination of molecular sieve, 75-99 weight %, molecular sieve and the 1-25 weight % of preferred 80-99 weight %, the coating of preferred 1-20 weight %.
The temperature of described roasting is 400-1200 ℃, is preferably 600-900 ℃, and roasting time is at least 0.5 hour, is preferably 0.5-100 hour, more preferred 1-10 hour.The atmosphere of described roasting can be any atmosphere, as air, water vapour or inert atmosphere.
Catalyzer provided by the invention can be used as Primary Catalysts or as sulfur prodegradant with other cracking catalyst, hydrocarbon oil containing surphur is carried out catalytic cracking.These hydrocarbon ils are selected from sulfur-bearing oil and various cut thereof, particularly sulfur-bearing oil and boiling point thereof are greater than 330 ℃ cut, as long residuum, vacuum residuum, the decompressed wax oil of sulfur-bearing, normal pressure wax oil, straight-run gas oil, propane is light/heavy one or more in de-oiling and the wax tailings.
No matter catalyzer provided by the invention is as Primary Catalysts or auxiliary agent, and the condition of its use is the reaction conditions of general cracking hydrocarbon process routine, is 400-700 ℃ as temperature of reaction, is preferably 450-600 ℃, and the agent weight of oil is preferably 2-15 than for 1-20.
The following examples will the present invention will be further described.
In the example, REY is the y-type zeolite that contains rare earth, and the Shandong catalyst plant is produced, and rare earth oxide content is 18 weight %, and wherein, lanthanum trioxide content is 5.6 weight %, and cerium oxide content is 9.9 weight %, and other rare earth oxide content is 2.5 weight %, Na
2O content is 1.7 weight %, lattice constant 2.465 nanometers; The ZSM-5 zeolite is a kind of zeolite with MFI structure, and the Lanzhou catalyst plant is produced, SiO
2With Al
2O
3Mol ratio is 60; REUSY is a kind of overstable gamma zeolite that contains rare earth, and the Chang Ling catalyst plant is produced, and rare earth oxide content is 10.6 weight %, and wherein, lanthanum trioxide content is 3.4 weight %, and cerium oxide content is 5.9 weight %, and other rare earth oxide content is 1.3 weight %, Na
2O content is 2.0 weight %, and lattice constant is 2.461 nanometers; USY is a kind of overstable gamma zeolite, and the Chang Ling catalyst plant is produced, and lattice constant is 2.451 nanometers; The ZRP-1 zeolite is a kind of zeolite with MFI structure of phosphorous and rare earth, and the Chang Ling catalyst plant is produced, SiO
2With Al
2O
3Mol ratio is 60, with P
2O
5Meter, phosphorus content is 2.7 weight %, and rare earth oxide content is 1.5 weight %, and wherein, lanthanum trioxide content is 0.47 weight %, and cerium oxide content is weight 0.80%, other rare earth oxide content is 0.23 weight %; The lattice constant of HY zeolite is 2.465 nanometers, Na
2O content is 0.5 weight %, and the Chang Ling catalyst plant is produced; The SiO of Beta zeolite
2With Al
2O
3Mol ratio is 60, Na
2O content is 0.2 weight %, and the Chang Ling catalyst plant is produced; The alumina content of used pseudo-boehmite is 61 weight %, and Shandong Aluminum Plant produces; The alumina content of aluminium colloidal sol is 21.5 weight %, and Shandong Aluminum Plant produces; Kaolinic solid content is 76 weight %, and kaolin company in Suzhou produces; The solid content of polynite is 95 weight %, and Zhejiang Feng Hong clay chemical industry company limited produces; Used metal component compound and alkaline earth metal compound are chemical pure.
Embodiment 1-2
Following example illustrates contained combination of molecular sieve of catalyzer provided by the invention and preparation method thereof.
1. magnesium nitrate is dissolved in the deionized water, make the magnesium nitrate solution that concentration is 50 weight %, be that the ammoniacal liquor of 25 weight % transfers to 8.0 with system pH and makes it to form precipitation under agitation with concentration, filter, be not detected to there being nitrate ion, must contain the magnesium hydroxide filter cake of MgO39 weight % with deionized water wash.
2. respectively with after different metal component compounds and pseudo-boehmite, deionized water mixing and stirring, obtain a kind of slurries, in slurries, add acid, continue to stir 3 hours, make the pseudo-boehmite peptization, mix with the magnesium hydroxide filter cake that contains MgO39 weight % then, obtain a kind of colloid.
3. the colloid that obtains is mixed with molecular sieve, roasting obtains combination of molecular sieve Z1-Z2.
Table 1 has provided the kind of metal component compound and consumption, the consumption of pseudo-boehmite, the consumption that contains the magnesium hydroxide filter cake of MgO39 weight %, the consumption of deionized water.Table 2 has provided kind, colloidal pH value and the colloidal solid content of used acid.Table 3 has provided colloidal consumption, the kind of molecular sieve and the temperature and time of consumption and roasting.Table 4 has provided the composition of coating.Table 5 has provided the composition of combination of molecular sieve Z1-Z2.The composition of described colloidal solid content, coating and the composition of combination of molecular sieve are by calculating.
Example 3
This example illustrates contained combination of molecular sieve of catalyzer provided by the invention and preparation method thereof.
1. with after metal component compound, Calcium Chloride Powder Anhydrous, pseudo-boehmite and deionized water mixing and stirring, obtain a kind of slurries, in slurries, add acid, continue to stir 3 hours, make the pseudo-boehmite peptization, obtain a kind of colloid.
2. the colloid that obtains is mixed with molecular sieve, roasting obtains combination of molecular sieve Z3 provided by the invention.
Table 1 has provided the kind of metal component compound and consumption, the consumption of pseudo-boehmite, the consumption of Calcium Chloride Powder Anhydrous, the consumption of deionized water.Table 2 has provided kind, colloidal pH value and the colloidal solid content of used acid.Table 3 has provided colloidal consumption, the kind of molecular sieve and the temperature and time of consumption and roasting.Table 4 has provided the composition of coating.Table 5 has provided the composition of combination of molecular sieve Z3.
Example 4-9
Following example illustrates contained combination of molecular sieve of catalyzer provided by the invention and preparation method thereof.
1. with after metal component compound, pseudo-boehmite and deionized water mixing and stirring, obtain a kind of slurries, in slurries, add acid, continue to stir 2 hours, make the pseudo-boehmite peptization obtain a kind of colloid.
2. the colloid that obtains is mixed with molecular sieve, roasting obtains combination of molecular sieve Z4-Z9.
Table 1 has provided the kind of metal component compound and consumption, the consumption of pseudo-boehmite, the consumption of deionized water.Table 2 has provided kind, colloidal pH value and the colloidal solid content of used acid.Table 3 has provided colloidal consumption, the kind of molecular sieve and the temperature and time of consumption and roasting.Table 4 has provided the composition of coating.Table 5 has provided the composition of combination of molecular sieve Z4-Z9.The composition of described colloidal solid content, coating and the composition of combination of molecular sieve are by calculating.
Table 1
| Example number | The kind of metal component compound and consumption | The consumption of pseudo-boehmite, gram | The kind of alkali metal compound and consumption | The consumption of deionized water, gram |
| 1 ? | Ammonium meta-vanadate, 12.8 grams | 131 | The magnesium hydroxide filter cake that contains MgO39 weight %, 25.6 grams | 402 |
| 2 | Ammonium meta-vanadate, 32.1 grams, REClx, 14.7 grams * | 98.4 | The magnesium hydroxide filter cake that contains MgO39 weight %, 12.8 grams | 402 |
| 3 | Ammonium meta-vanadate, 19.3 grams | 115 | Calcium Chloride Powder Anhydrous, 29.7 grams | 585 |
| 4 ? | Ammonium meta-vanadate, 25.7 grams, ZrOCl 2, 14.5 grams | 115 ? | - | 468 |
| 5 | Ammonium meta-vanadate, 12.9 grams, Fe 2(N0 3) 3, 9.32 grams | 139 | - | 569 |
| 6 | Ammonium meta-vanadate, 32.1 grams, LaCl 3, 24.8 grams | 98.4 | - | 402 |
| 7 | GaCl 3, 56.4 grams | 114.8 | - | 469 |
| 8 | SnCl 2, 51.9 grams | 114.8 | - | 469 |
| 9 | Ammonium metawolframate, 32.7 grams | 114.8 | - | 469 |
*(REClx is a mixed rare earth chlorides, and per 100 gram REClx can change into mixed rare-earth oxide 67.8 grams, and per 100 gram rare earth oxides contain lanthanum trioxide 31 grams, cerium oxide 53 grams, other rare-earth oxide 16 grams).
Table 2
| Example number | The kind of acid | Colloidal pH value | The colloidal solid content, weight % |
| 1 | Concentration is the hydrochloric acid of 36 weight % | 2.2 | 15 |
| 2 | Concentration is the hydrochloric acid of 36 weight % | 2.0 | 12 |
| 3 | Concentration is rare nitric acid of 60 weight % | 1.6 | 10 |
| 4 | Concentration is the hydrochloric acid of 36 weight % | 1.8 | 12 |
| 5 | Concentration is the phosphoric acid of 85 weight % | 1.8 | 12 |
| 6 | Concentration is the hydrochloric acid of 36 weight % | 1.6 | 12 |
| 7 | Concentration is the acetate of 98 weight % | 2.0 | 12 |
| 8 | Concentration is the hydrochloric acid of 36 weight % | 2.1 | 12 |
| 9 | Concentration is the hydrochloric acid of 36 weight % | 1.8 | 12 |
Table 3
| Example number | The colloidal consumption, gram | The kind of molecular sieve and consumption | Maturing temperature, ℃ | Roasting time, hour |
| 1 | 100 | REY, 85 grams | 750 | 6 |
| 2 | 83.3 | REY, 85 grams, ZSM-5,5 grams | 800 | 4 |
| 3 | 100 | REHY, 90 grams | 850 | 1.5 |
| 4 | 66.7 | REUSY, 92 grams | 700 | 8 |
| 5 | 41.7 | USY, 95 grams | 900 | 1 |
| 6 | 16.7 | USY, 93 grams, ZRP-1,5 grams | 800 | 2 |
| 7 | 100 | HY, 78 grams, Beta zeolite, 10 grams | 650 | 10 |
| 8 | 50 | USY, 84 grams, ZSM-5,10 grams | 700 | 5 |
| 9 | 33.3 | REY, 96 grams | 650 | 4 |
Table 4
| Example number | Metal species and in the metal content of oxide compound, weight % | Alkali-metal kind and in the alkali metal content of oxide compound, weight % | Alumina content, weight % |
| 1 | V，10 | Mg，10 | 80 |
| 2 | V，25；RE，10 | Mg，5 | 60 |
| 3 | V，15 | Ca，15 | 70 |
| 4 | V，20；Zr，10 | - | 70 |
| 5 | V，10；Fe，5 | - | 85 |
| 6 | V，25；La，15 | - | 60 |
| 7 | Ga，30 | - | 70 |
| 8 | Sn，30 | - | 70 |
| 9 | W，30 | - | 70 |
Table 5
| Example number | The combination of molecular sieve numbering | Molecular sieve content, weight % | Coating levels, weight % |
| 1 | Z1 | 85 | 15 |
| 2 | Z2 | 90 | 10 |
| 3 | Z3 | 90 | 10 |
| 4 | Z4 | 92 | 8 |
| 5 | Z5 | 95 | 5 |
| 6 | Z6 | 98 | 2 |
| 7 | Z7 | 88 | 12 |
| 8 | Z8 | 94 | 6 |
| 9 | Z9 | 96 | 4 |
Comparative Examples 1
This Comparative Examples illustrates non-coating reference combination of molecular sieve and preparation method thereof.
Contain V with 50 grams
2O
53.0 the ammonium metavanadate aqueous solution of weight % dipping 97 gram examples 3 described REHY zeolites, 120 ℃ of oven dry, the calcium chloride water dipping that contains calcium oxide 3.0 weight % again with 50 grams again 850 ℃ roasting temperature 1.5 hours, obtains containing the reference combination of molecular sieve ZB1 of vanadium and calcium.The content of vanadium and calcium is identical with Z3 among the ZB1.
Comparative Examples 2
This Comparative Examples illustrates non-coating reference combination of molecular sieve and preparation method thereof.
1. contain V with 250 grams
2O
53.0 the ammonium metavanadate aqueous solution of weight % dipping 450 gram examples 3 described REHY zeolites, 120 ℃ of oven dry restrain the calcium chloride water dipping that contains calcium oxide weight 3.0 weight % with 250 again, and 120 ℃ of dryings obtain a kind of REHY zeolite that contains vanadium and calcium.
2. with after 57.4 gram pseudo-boehmites and deionized water mixing and stirring, obtain a kind of slurries, adding concentration in slurries is rare nitric acid of 60 weight %, continues to stir 3 hours, makes the pseudo-boehmite peptization, obtains a kind of colloid.
3. the whole REHY zeolites that contain vanadium and calcium with this Comparative Examples (1) preparation mix with whole colloids that this Comparative Examples (2) prepares, and press example 3 described condition roastings, obtain reference combination of molecular sieve ZB2.The content of vanadium, calcium, aluminum oxide and molecular sieve is identical with Z3 among the ZB2.
Comparative Examples 3
This Comparative Examples illustrates non-coating reference combination of molecular sieve and preparation method thereof.
With 60 gram V
2O
5Content is the ammonium metavanadate aqueous solution dipping 114.8 gram pseudo-boehmites of 25 weight %, 120 ℃ of oven dry, restrain the calcium chloride water that contains calcium oxide weight 30 weight % with 50 again and flood the pseudo-boehmite that contains vanadium that obtains,, obtain containing the aluminum oxide of vanadium and calcium 850 ℃ of roastings 1.5 hours.This aluminum oxide that contains vanadium and calcium is formed identical with the described coating of Z3.
With 90 gram REHY zeolites and the above-mentioned aluminum oxide physical mixed that contains vanadium and calcium that obtains of 10 grams, obtain reference combination of molecular sieve ZB4, the content of vanadium, calcium, aluminum oxide and molecular sieve is identical with Z3 among the ZB4.
Comparative Examples 4
Disclosed combination of molecular sieve of this Comparative Examples explanation CN1388220A and preparation method thereof.
Method by example among the CN1388220A 2 prepares combination of molecular sieve, obtains reference combination of molecular sieve ZB4, and ZB4 contains coating and the molecular sieve with example 3 same amount, described coating consist of ZnO40.8 weight %, TiO
28.4 weight % and Al
2O
350.8 weight %.
Embodiment 10-18
Following example illustrates Catalysts and its preparation method provided by the invention.
With combination of molecular sieve, deionized water, pseudo-boehmite and/or the aluminium colloidal sol of example 1-9 preparation, also have the clay making beating sometimes respectively, drying is broken into the particle of 20-150 micron then, obtains containing cracking catalyst C1-C9 provided by the invention.Table 6 has provided kind and the consumption and the spray-dired temperature of combination of molecular sieve, deionized water, pseudo-boehmite, aluminium colloidal sol, clay, and table 7 has provided the composition of C1-C9.
Comparative Examples 5-8
Following Comparative Examples reference catalyst and preparation method thereof.
Method by example 12 prepares cracking catalyst, and different is to replace Z3 with ZB1, ZB2, ZB3 and ZB4 respectively, obtains reference catalyst CB1, CB2, CB3 and CB4.Table 7 has provided the composition of CB1, CB2, CB3 and CB4.
Table 6
| Example number | The catalyzer numbering | Combination of molecular sieve kind and consumption | The kind of clay and consumption, gram | The pseudo-boehmite consumption, gram | Aluminium colloidal sol consumption, gram | The deionized water consumption, gram | The spraying drying temperature, ℃ |
| 10 | C1 | Z1,50 grams | Kaolin, 23.7 | 32.8 | 55.8 | 238 | 275 |
| 11 | C2 | Z2,40 grams | Kaolin, 32.9 | 41.0 | 46.5 | 240 | 250 |
| 12 | C3 | Z3,55 grams | Kaolin, 13.2 | 32.8 | 69.8 | 229 | 300 |
| Comparative Examples 5 | CB1 | ZB1,55 grams | Kaolin, 13.2 | 32.8 | 69.8 | 229 | 300 |
| Comparative Examples 6 | CB2 | ZB2,55 grams | Kaolin, 13.2 | 32.8 | 69.8 | 229 | 300 |
| Comparative Examples 7 | CB3 | ZB3,55 grams | Kaolin, 13.2 | 32.8 | 69.8 | 229 | 300 |
| Comparative Examples 8 | CB4 | ZB4,55 grams | Kaolin, 13.2 | 32.8 | 69.8 | 229 | 300 |
| 13 | C4 | Z4,30 grams | Kaolin, 44.7 | 49.2 | 27.9 | 248 | 230 |
| 14 | C5 | Z5,60 grams | 0 | 32.8 | 93.0 | 214 | 320 |
| 15 | C6 | Z6,65 grams | Kaolin, 19.7 | 0.0 | 93.0 | 222 | 320 |
| 16 | C7 | Z7,15 grams | Polynite, 52.6 | 49.2 | 23.3 | 260 | 200 |
| 17 | C8 | Z8,25 grams | Kaolin, 38.2 | 65.6 | 27.9 | 243 | 150 |
| 18 | C9 | Z9,35 grams | Kaolin, 28.9 | 57.4 | 37.2 | 241 | 190 |
Table 7
| Example number | The catalyzer numbering | Combination of molecular sieve kind and content, weight % | The kind of clay and content, weight % | Alumina content, weight % |
| 10 | C1 | Z1，50 | Kaolin, 18 | ??32 |
| 11 | C2 | Z2，40 | Kaolin, 25 | ??35 |
| 12 | C3 | Z3，55 | Kaolin, 10 | ??35 |
| Comparative Examples 5 | CB1 | ZB1，55 | Kaolin, 10 | ??35 |
| Comparative Examples 6 | CB2 | ZB2，55 | Kaolin, 10 | ??35 |
| Comparative Examples 7 | CB3 | ZB3，55 | Kaolin, 10 | ??35 |
| Comparative Examples 8 | CB4 | ZB4，55 | Kaolin, 10 | ??35 |
| 13 | C4 | Z4，30 | Kaolin, 34 | ??36 |
| 14 | C5 | Z5，60 | 0 | ??40 |
| 15 | C6 | Z6，65 | Kaolin, 15 | ??20 |
| 16 | C7 | Z7，15 | Polynite, 50 | ??35 |
| 17 | C8 | Z8，25 | Kaolin, 29 | ??46 |
| 18 | C9 | Z9，35 | Kaolin, 22 | ??43 |
Embodiment 19-27
Following example illustrates the catalytic performance of catalyzer provided by the invention.
With catalyzer C1-C9 at 800 ℃, wore out 8 hours with 100% water vapour, on small fixed flowing bed, with the sulphur content shown in the catalyzer C1-C9 catalytic cracking table 8 after aging is the long residuum of 1.39 weight % and the mixing oil of decompressed wax oil, the catalyzer loading amount is 120 grams, and reaction conditions is shown among the 9-11 with the results are shown in.Wherein, the sulphur content of gasoline adopts micro-coulometric determination.
Comparative Examples 9-12
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 21 is carried out catalytic cracking to same stock oil, and different is, catalyst system therefor is respectively CB1, CB2, CB3 and CB4, reaction conditions and the results are shown in Table 9.
Table 8
| The stock oil title | The mixing oil of long residuum and decompressed wax oil |
| Density, gram per centimeter 3 | ????0.9057 |
| Viscosity, millimeter 2/ second (80 ℃) | ????11.60 |
| Carbon residue, weight % | ????＜0.02 |
| Stable hydrocarbon, weight % aromatic hydrocarbons, weight % colloid, weight % bituminous matter, weight % | ????66.3 ????27.2 ????6.5 ????0 |
| C, weight % H, weight % S, weight % N, weight % | ????85.97 ????12.39 ????1.39 ????0.10 |
| Boiling range, ℃ IBP 30% 50% 70% 95% | ? ????294 ????419 ????444 ????470 ????522 |
Table 9
| Example number | ??21 | Comparative Examples 9 | Comparative Examples 10 | Comparative Examples 11 | Comparative Examples 12 |
| Catalyzer | ??C3 | ??CB1 | ??CB2 | ??CB3 | ??CB4 |
| Temperature of reaction, ℃ | ??500 | ??500 | ??500 | ??500 | ??500 |
| Agent weight of oil ratio | ??3.0 | ??3.0 | ??3.0 | ??3.0 | ??3.0 |
| Weight hourly space velocity, hour -1 | ??20 | ??20 | ??20 | ??20 | ??20 |
| Transformation efficiency, weight % | ??78.8 | ??12.9 | ??14.7 | ??79.6 | ??78.5 |
| Product is formed, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | ? ??2.5 ??12.8 ??57.9 ??15.9 ??5.3 ??5.6 | ? ??0.4 ??2.2 ??9.1 ??2.1 ??85.0 ??1.2 | ? ??0.6 ??2.1 ??10.6 ??2.8 ??82.5 ??1.4 | ? ??2.0 ??13.2 ??59.2 ??15.0 ??5.4 ??5.2 | ? ??2.3 ??12.6 ??58.2 ??16.0 ??5.5 ??5.4 |
| Content of sulfur in gasoline, micrograms per litre | ??158 | ??906 | ??878 | ??485 | ??346 |
Table 10
| Implement numbering | ????19 | ????20 | ????22 | ????23 |
| Catalyzer | ????C1 | ????C2 | ????C4 | ????C5 |
| Temperature of reaction, ℃ | ????520 | ????520 | ????460 | ????460 |
| Agent weight of oil ratio | ????3.0 | ????2.0 | ????3.5 | ????4.0 |
| Weight hourly space velocity, hour -1 | ????15 | ????10 | ????20 | ????20 |
| Transformation efficiency, weight % | ????79.1 | ????74.5 | ????70.6 | ????75.4 |
| Product is formed, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | ? ????2.4 ????13.1 ????58.8 ????15.5 ????5.4 ????4.8 | ? ????2.8 ????13.6 ????53.5 ????19.7 ????5.8 ????4.6 | ? ????1.8 ????12.8 ????51.4 ????23.3 ????6.1 ????4.6 | ? ????2.1 ????13.2 ????55.2 ????18.9 ????5.7 ????4.9 |
| Content of sulfur in gasoline, micrograms per litre | ????167 | ????140 | ????219 | ????233 |
Table 11
| Implement numbering | ????24 | ????25 | ????26 | ??27 |
| Catalyzer | ????C6 | ????C7 | ????C8 | ??C9 |
| Temperature of reaction, ℃ | ????500 | ????540 | ????480 | ??520 |
| Agent weight of oil ratio | ????2.5 | ????10.0 | ????7.5 | ??4.5 |
| Weight hourly space velocity, hour -1 | ????10 | ????15 | ????18 | ??12 |
| Transformation efficiency, weight % | ????83.0 | ????78.3 | ????75.2 | ??74.7 |
| Product is formed, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | ? ????2.6 ????13.9 ????60.4 ????11.8 ????5.2 ????6.1 | ? ????2.8 ????14.4 ????54 ????13.9 ????7.8 ????7.1 | ? ????2.4 ????14.6 ????51.7 ????16.7 ????8.1 ????6.5 | ? ??2.3 ??13.2 ??54.1 ??19.7 ??5.6 ??5.1 |
| Content of sulfur in gasoline, micrograms per litre | ????162 | ????314 | ????335 | ??375 |
From the result of table 9 as can be seen, compare the desulphurizing activated obvious raising of catalyzer provided by the invention with the cracking catalyst of the reference combination of molecular sieve that contains same amount.It is higher desulphurizing activated that the result of table 10-11 shows that equally catalyzer provided by the invention has.
Example 28-36
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Method by example 21 is carried out catalytic cracking to same stock oil, different is, catalyst system therefor is respectively uses 100% water vapour, at 800 ℃ of catalyst mixtures of aging 8 hours, this catalyst mixture (being designated as X1-X9) contains industrial cracking catalyst and the catalyzer C1-C9 that the industrial trade mark is CC-20D respectively.Catalyst mixture, reaction conditions is shown among the 12-13 with the results are shown in.
Wherein, X1 is the mixture of 90 weight %CC-20D and 10 weight %C1, X2 is the mixture of 85 weight %CC-20D and 15 weight %C2, X3 is the mixture of 80 weight %CC-20D and 20 weight %C3, X4 is the mixture of 75 weight %CC-20D and 25 weight %C4, X5 is the mixture of 95 weight %CC-20D and 5 weight %C5, X6 is the mixture of 70 weight %CC-20D and 30 weight %C6, X7 is the mixture of 60 weight %CC-20D and 40 weight %C7, X8 is the mixture of 65 weight %CC-20D and 35 weight %C8, and X9 is the mixture of 65 weight %CC-20D and 35 weight %C9.
Comparative Examples 13
The situation of commercial catalysts CC-20D is only used in following Comparative Examples explanation.
Method by example 21 is carried out catalytic cracking to same stock oil, and different is, catalyst system therefor is the industrial cracking catalyst of CC-20D for use 100% water vapour at 800 ℃ of industrial trades mark of aging 8 hours, and reaction conditions is with the results are shown in Table 13.
Table 12
| Implement numbering | ????28 | ????29 | ????30 | ??31 | ??32 |
| Catalyst mixture | ????X1 | ????X2 | ????X3 | ??X4 | ??X5 |
| Temperature of reaction, ℃ | ????500 | ????540 | ????500 | ??480 | ??520 |
| Agent weight of oil ratio | ????2.5 | ????3.0 | ????3.0 | ??3.5 | ??4.5 |
| Weight hourly space velocity, hour -1 | ????10 | ????15 | ????20 | ??18 | ??12 |
| Transformation efficiency, weight % | ????75.2 | ????75.8 | ????76.0 | ??73.4 | ??78.5 |
| Product is formed, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | ? ????2.4 ????12.9 ????55.0 ????19.6 ????5.2 ????4.9 | ? ????2.6 ????13.2 ????55.2 ????18.8 ????5.4 ????4.8 | ? ????2.5 ????13.5 ????54.9 ????18.6 ????5.4 ????5.1 | ? ??2.1 ??12.5 ??54.2 ??21.3 ??5.3 ??4.6 | ? ??2.7 ??13.3 ??57.1 ??15.8 ??5.7 ??5.4 |
| Content of sulfur in gasoline, micrograms per litre | ????204 | ????186 | ????197 | ??229 | ??380 |
Table 13
| Implement numbering | ????33 | ??34 | ????35 | ????36 | Comparative Examples 13 |
| Catalyst mixture | ????X6 | ??X7 | ????X8 | ????X9 | ?CC-20D |
| Temperature of reaction, ℃ | ????520 | ??520 | ????460 | ????480 | ?500 |
| Agent weight of oil ratio | ????3.0 | ??4.0 | ????4.5 | ????4.0 | ?3.0 |
| Weight hourly space velocity, hour -1 | ????15 | ??10 | ????15 | ????20 | ?20 |
| Transformation efficiency, weight % | ????79.6 | ??78.4 | ????76.7 | ????79.2 | ?74.9 |
| Product is formed, weight % dry gas liquefied gas gasoline, diesel heavy oil coke | ? ????3.0 ????13.4 ????58.1 ????15.2 ????5.2 ????5.1 | ? ??3.1 ??13.6 ??56 ??14.8 ??6.8 ??5.7 | ? ????2.8 ????13 ????55.1 ????16.9 ????6.4 ????5.8 | ? ????3.2 ????13.7 ????56.1 ????16.3 ????4.5 ????6.2 | ? ?2.7 ?12.9 ?54.6 ?19.4 ?5.7 ?4.7 |
| Content of sulfur in gasoline, micrograms per litre | ????172 | ??367 | ????372 | ????325 | ?836 |
From the result of table 12-13 as can be seen, catalyzer provided by the invention is used as desulfurizing assistant agent, can reduce the sulphur content in the gasoline significantly, and the composition structure of crackate not caused obvious influence.
Claims (22)
1. hydrocarbon cracking catalyzer with desulfidation, this catalyzer contains a kind of combination of molecular sieve and heat-resistant inorganic oxide, contain or argillaceous not, it is characterized in that, described combination of molecular sieve contains molecular sieve and is covered in the coating on this molecular sieve surface, with described combination of molecular sieve is benchmark, and the content of molecular sieve is 75-99 weight %, and the content of coating is 1-25 weight %; Described coating contains aluminum oxide and metal component, is benchmark with the total amount of described coating, and the content of aluminum oxide is 50-95 weight %, and in oxide compound, the content of described metal component is 5-50 weight %; Described metal component is selected from one or more in the non-aluminum metal of IIIA family, IVA family metal, IVB family metal, VB family metal, group vib metal, VIIB family metal, VIII family base metal and the rare earth metal.
2. catalyzer according to claim 1 is characterized in that, is benchmark with the catalyzer total amount, and the content of described combination of molecular sieve is 5-90 weight %, and the content of heat-resistant inorganic oxide is 5-70 weight %, and the content of clay is 0-70 weight %.
3. catalyzer according to claim 2 is characterized in that, is benchmark with the catalyzer total amount, and the content of described combination of molecular sieve is 10-75 weight %, and the content of heat-resistant inorganic oxide is 10-55 weight %, and the content of clay is 0-60 weight %.
4. according to any described catalyzer among the claim 1-3, it is characterized in that, is benchmark with described combination of molecular sieve, and the content of molecular sieve is 80-99 weight %, and the content of coating is 1-20 weight %.
5. catalyzer according to claim 1 is characterized in that, is benchmark with the total amount of described coating, and the content of aluminum oxide is 60-90 weight %, and in oxide compound, the content of described metal component is 10-40 weight %.
6. according to claim 1 or 5 described catalyzer, it is characterized in that described metal component is selected from one or more in gallium, indium, thallium, germanium, tin, lead, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, iron, cobalt, nickel, the lanthanide rare metal.
7. catalyzer according to claim 6, it is characterized in that, described metal component is selected from one or more the mixture in vanadium or vanadium and titanium, zirconium, iron, the lanthanide rare metal, total amount with coating is a benchmark, the content of aluminum oxide is 60-90 weight %, in oxide compound, the content of vanadium is 10-40 weight %, and the content of one or more in titanium, zirconium, iron, the lanthanide rare metal is 0-30 weight %.
8. catalyzer according to claim 6, it is characterized in that, described metal component is selected from one or more the mixture in vanadium or vanadium and zirconium, iron, titanium, the rare earth metal, described coating also contains alkaline-earth metal, is benchmark with the total amount of coating, and the content of aluminum oxide is 60-90 weight %, in oxide compound, the content of vanadium is 10-40 weight %, and the content of one or more in titanium, zirconium, iron, the lanthanide rare metal is 0-30 weight %, and the content of alkaline-earth metal is 0-30 weight %.
9. catalyzer according to claim 8 is characterized in that described alkaline-earth metal is selected from magnesium and/or calcium.
10. catalyzer according to claim 1 is characterized in that, described molecular screening is from as the zeolite of active component of cracking catalyst and in the non-zeolite molecular sieve one or more.
11. catalyzer according to claim 10 is characterized in that, described zeolite is selected from one or more in large pore zeolite and the mesopore zeolite.
12. catalyzer according to claim 11 is characterized in that, described large pore zeolite is selected from one or more in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite.
13. catalyzer according to claim 11, it is characterized in that, described mesopore zeolite is selected from as having the zeolite of MFI structure, one or more in the zeolite with MFI structure of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite.
14. catalyzer according to claim 10, it is characterized in that described molecular screening one or more in the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, zeolite, phosphorous and/or rare earth with MFI structure.
15. catalyzer according to claim 1 is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, the boron oxide.
16. catalyzer according to claim 11 is characterized in that, described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
17. claim 1 Preparation of catalysts method, this method comprises and will contain combination of molecular sieve, heat-resistant inorganic oxide and/or its precursor and water, contain or slurry dried not argillaceous, it is characterized in that, the preparation method of described combination of molecular sieve is included in a kind of hydration aluminum oxide that contains, add a kind of acid in the compound of metal component and the slurries of water, make partially hydrated at least aluminum oxide peptization, obtain a kind of colloid, the colloid that obtains is mixed with molecular sieve and roasting, the compound of described metal component is selected from the non-aluminum metallization compound of IIIA family, IVA family metallic compound, IVB family metallic compound, VB family metallic compound, the group vib metallic compound, VIIB family metallic compound, in VIII family non-noble metal compound and the rare earth compound one or more, described hydrated aluminum oxide, the compound of metal component, the consumption of water and acid makes in the described coating and contains, total amount with described coating is a benchmark, the aluminum oxide of 50-95 weight % and in oxide compound, the metal component of 5-50 weight %, the consumption of described colloid and molecular sieve makes in the combination of molecular sieve that obtains and contains, with described combination of molecular sieve is benchmark, the coating of the molecular sieve of 75-99 weight % and 1-25 weight %.
18. method according to claim 17, it is characterized in that described metallic compound is selected from the compound of compound, the nickel of compound, the cobalt of compound, the iron of compound, the tungsten of compound, the molybdenum of compound, the chromium of compound, the tantalum of compound, the niobium of compound, the vanadium of compound, the hafnium of compound, the zirconium of the compound of compound, the tin of compound, the germanium of compound, the thallium of compound, the indium of gallium, plumbous compound, titanium, in the lanthanide rare metallic compound one or more.
19. method according to claim 18, it is characterized in that, the compound of described metal component is selected from one or more the mixture in vanadium compound or vanadium compound and titanium compound, zirconium compounds, iron cpd, the lanthanide rare metallic compound, the consumption of each component makes in the composition and contains, total amount with coating is a benchmark, and the aluminum oxide of 60-90 weight % is in oxide compound, the vanadium of 10-40 weight %, one or more in the titanium of 0-30 weight %, zirconium, iron, the lanthanide rare metal.
20. method according to claim 18, it is characterized in that, the compound of described metal component is selected from vanadium compound or vanadium compound and titanium compound, zirconium compounds, iron cpd, the mixture of one or more in the lanthanide rare metallic compound, also adopt in described slurries and add alkaline earth metal compounds, perhaps alkaline earth metal compounds and the colloid blended method that obtains are introduced alkaline earth metal compound, the consumption of each component makes in the composition and contains, total amount with coating is a benchmark, the aluminum oxide of 60-90 weight %, in oxide compound, the vanadium of 10-40 weight %, the titanium of 0-30 weight %, zirconium, iron, in the lanthanide rare metal one or more and in oxide compound, the alkaline-earth metal of 0-30 weight %.
21. method according to claim 17 is characterized in that, described acid is selected from one or more in the carboxylate salt that hydrochloric acid, nitric acid, phosphoric acid, carbonatoms are 1-10, and it is 1-3 that the consumption of acid makes the colloidal pH value that obtains.
22. method according to claim 17 is characterized in that, the temperature of described roasting is 400-1200 ℃, and roasting time is at least 0.5 hour.
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| CN105478154A (en) * | 2015-12-14 | 2016-04-13 | 夏百庆 | Catalyst for high-activity fluidized bed |
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| JPH11300208A (en) * | 1998-04-21 | 1999-11-02 | Idemitsu Kosan Co Ltd | Catalytically cracking catalyst |
| US20020153283A1 (en) * | 1998-12-28 | 2002-10-24 | Arthur W Chester | Gasoline sulfur reduction in fluid catalytic cracking |
| CN1216691C (en) * | 2001-05-30 | 2005-08-31 | 中国石油化工股份有限公司 | Molecular sieve composition with desulfurizing function and its prepn |
| CN1165376C (en) * | 2001-06-29 | 2004-09-08 | 中国石油化工股份有限公司 | Faujasite molecular sieve composition and its preparing process |
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| CN105478154A (en) * | 2015-12-14 | 2016-04-13 | 夏百庆 | Catalyst for high-activity fluidized bed |
| CN105478154B (en) * | 2015-12-14 | 2019-09-03 | 中石化南京催化剂有限公司 | One kind being used for the agent of high activity fluid catalytic |
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