CN112473732B - Catalytic cracking catalyst for producing propylene and preparation method and application method thereof - Google Patents
Catalytic cracking catalyst for producing propylene and preparation method and application method thereof Download PDFInfo
- Publication number
- CN112473732B CN112473732B CN201910933546.5A CN201910933546A CN112473732B CN 112473732 B CN112473732 B CN 112473732B CN 201910933546 A CN201910933546 A CN 201910933546A CN 112473732 B CN112473732 B CN 112473732B
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- China
- Prior art keywords
- zirconium
- molecular sieve
- composite sol
- catalytic cracking
- aluminum composite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title abstract description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 119
- 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 119
- 239000002131 composite material Substances 0.000 claims abstract description 94
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 18
- 239000011707 mineral Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000004537 pulping Methods 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 47
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000004094 surface-active agent Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- -1 polyoxyethylene-8-octyl phenyl ether Polymers 0.000 claims description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 230000020477 pH reduction Effects 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 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 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 10
- 239000000194 fatty acid Substances 0.000 claims description 10
- 229930195729 fatty acid Natural products 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 229950008882 polysorbate Drugs 0.000 claims description 4
- 229920000136 polysorbate Polymers 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 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
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000004684 trihydrates Chemical class 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013504 Triton X-100 Substances 0.000 description 5
- 229920004890 Triton X-100 Polymers 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 4
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 229910052621 halloysite Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 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 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940092782 bentonite Drugs 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention belongs to the technical field of catalytic cracking catalysts, and discloses a catalytic cracking catalyst for producing propylene, a preparation method and an application method thereof. The catalyst comprises: natural minerals, zirconium aluminum composite sol, other inorganic oxide binders, Y-type molecular sieves and MFI structure molecular sieves. The preparation method of the catalyst comprises the steps of mixing and pulping an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, zirconium-aluminum sol and other inorganic oxide binders, and spray drying. The catalyst has good strength and high activity, is used for hydrocarbon oil catalytic cracking, and has higher raw material conversion rate and higher propylene yield.
Description
Technical Field
The invention belongs to the technical field of catalytic cracking catalysts, and relates to catalytic cracking for producing propylene, a preparation method and an application method thereof.
Background
Ethylene, propylene, butylene and other low-carbon olefins are indispensable chemical raw materials, and can be used for synthesizing resins, fibers, rubber and the like. Propylene is an important raw material for manufacturing petrochemical products, and is mainly used for producing chemical products such as polypropylene, acrylonitrile, propylene oxide and the like. At present, propylene is mainly derived from byproducts of ethylene production by thermal cracking at home and abroad, the second largest source of propylene is the FCC unit, which provides about 30% of the demand, and in the united states, half of the demand for propylene by petrochemical products. Thus, the substantial production of propylene by FCC is an effective and efficient way to meet the growing demand.
At present, most of catalytic cracking catalysts adopt alumina sol and peptized pseudo-boehmite as binders, so that the activity of a matrix is low and the selectivity is poor.
CN102211039B provides a catalytic cracking catalyst and a preparation method thereof, comprising mixing and pulping a molecular sieve, zirconia powder and an aluminum binder, adding zirconia powder into the slurry for pulping, adjusting the pH of the slurry to 2-5 with an inorganic acid, and then spray-drying, wherein the zirconia powder is prepared by mixing an aqueous solution of zirconium salt with ammonia water. The catalyst prepared by the method has good wear resistance, high crystallinity and strong capability of resisting calcium pollution, is used for cracking calcium-containing hydrocarbon oil, and has high propylene yield. But propylene selectivity is not high.
Disclosure of Invention
The technical problem to be explained in the invention is to provide a catalytic cracking catalyst for producing propylene and a preparation method thereof, wherein the catalyst has higher propylene selectivity than the existing Y-type molecular sieve and MFI structure molecular sieve.
The invention provides a catalytic cracking catalyst and a method for preparing the same, wherein the catalyst comprises the following components in dry basis:
(a) 12 to 65 weight percent of natural minerals,
(b) 10 to 60 weight percent of zirconium-aluminum composite sol,
(c) 22 wt% to 75 wt% of a Y-type molecular sieve and an MFI structure molecular sieve, wherein the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 1:10 to 10:1, and
(d) 3 wt% to 20 wt% of other inorganic oxide binders;
in the zirconium-aluminum composite sol, the content of aluminum element is 1-10 wt% and the content of zirconium element is 0.5-10 wt%, the composite sol is dried at 100 ℃ for 6 hours, and then baked at 600 ℃ for 6 hours to obtain a solid, wherein zirconium dioxide exists in a monoclinic phase and tetragonal phase form in the solid.
The other inorganic oxide binders are those used in the art other than zirconium aluminum composite sols.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps:
(1) Preparing zirconium-aluminum composite sol;
(2) Mixing and pulping an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, the zirconium-aluminum composite sol and other inorganic oxide binders, and spray drying.
The preparation method of the zirconium-aluminum composite sol comprises the following steps: acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant, and water; the conditions of the acidification hydrolysis include: the temperature is 10-100deg.C, and the time is 0.2-5h.
The invention further provides a catalytic cracking method, which comprises the step of carrying out contact reaction on hydrocarbon oil and the catalytic cracking catalyst provided by the invention or the catalytic cracking catalyst prepared by the catalyst preparation method provided by the invention under the condition of catalytic cracking.
The hydrocarbon oils are, for example: one or more of vacuum residuum, atmospheric residuum, vacuum gas oil, atmospheric gas oil, coker gas oil and hydro-modified oil.
The catalytic cracking conditions include: the reaction temperature is 500-650 ℃, the reaction time is 0.5-10 seconds, the weight ratio of the catalyst to the fuel oil is 5-40, diluent gas can be introduced in the reaction process, and the weight ratio of the diluent gas to the raw materials is preferably 0.1-1:1. The diluent gas may be, for example, water vapor.
The catalytic cracking catalyst provided by the invention has good wear resistance, can have higher propylene selectivity than the existing cracking catalyst containing Y and MFI structure zeolite, and can also have higher cracking activity and/or higher low-carbon olefin yield and/or higher liquefied gas yield and/or higher catalytic cracking propylene yield.
The catalytic cracking method provided by the invention has higher propylene selectivity, higher conversion rate, higher propylene yield, higher low-carbon olefin yield or higher liquefied gas yield.
The specific embodiment is as follows:
the catalytic cracking catalyst provided by the invention comprises a zirconium-aluminum composite sol, wherein the content of aluminum element in the zirconium-aluminum composite sol is 1-10 wt%, the content of zirconium element is 0.5-10 wt%, the zirconium-aluminum composite sol is dried at 100 ℃ for 6 hours, and then monoclinic phase zirconium dioxide and tetragonal phase zirconium dioxide exist in a solid obtained by roasting at 600 ℃ for 6 hours. Preferably, the content of aluminum element is 2-6 wt%, and the content of zirconium element is 1-6 wt%; it is further preferable that the content of the aluminum element is 4.5 to 6% by weight, and the content of the zirconium element is 1.2 to 2.2, for example, 1.4 to 2.1% by weight or 1.8 to 2.2% by weight.
Preferably, the weight ratio of aluminum element to zirconium element in the zirconium-aluminum composite sol is (0.3-6): 1, more preferably (0.5 to 5): 1, more preferably (1-4): 1, most preferably (2.2-3.9): 1 is, for example, (2.2-3.1): 1.
the element content in the zirconium-aluminum composite sol can be measured by ICP-OES inductively coupled plasma-atomic emission spectrometry, see GB/T30902-2014.
Preferably, the pH of the zirconium aluminum composite sol is in the range of 0.5 to 5, more preferably 1 to 4, for example 2 to 3, still more preferably 2.2 to 2.6.
According to a preferred embodiment of the present invention, the zirconium aluminum composite sol is dried at 100 ℃ for 6 hours and then calcined at 600 ℃ for 6 hours to obtain a solid having an XRD pattern with diffraction peaks at 28 DEG + -0.5 DEG, 31.4 DEG + -0.5 DEG and 30.3 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG for 2 theta. Wherein, the diffraction peaks at 28 DEG + -0.5 DEG, 31.4 DEG + -0.5 DEG correspond to monoclinic phase zirconium dioxide, and the diffraction peaks at 30.3 DEG + -0.5 DEG, 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG correspond to tetragonal phase zirconium dioxide. In a preferred embodiment, the XRD pattern of the solid has diffraction peaks at 46 DEG + -0.5 DEG, 66.6 DEG + -0.5 DEG for 2 theta. The diffraction peak at this point corresponds to the diffraction peak of gamma-alumina.
According to the catalytic cracking catalyst provided by the invention, preferably, the zirconium-aluminum composite sol further contains a surfactant, wherein the content of the surfactant is 0.5-10 wt% of the content of aluminum element, and further preferably 0.5-2 wt%, such as 0.5-1.5 wt% or 1-1.5 wt% of the content of aluminum element. The surfactant may be an ionic surfactant or a nonionic surfactant, and is not particularly limited in the present invention, and is preferably selected from the group consisting of nonionic surfactants, more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, sucrose triethanolamine soap ester and sucrose polyol ester, still more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether and polysorbate, and most preferably polyoxyethylene-8-octylphenyl ether. The embodiment containing the surfactant is more beneficial to improving the dispersibility of the zirconium-aluminum composite sol, and is more beneficial to improving the hydrothermal stability and the abrasion strength of the catalytic cracking catalyst.
According to the invention, the composite sol also contains water. The water content is in an equilibrium amount, for example 80-95 wt.%, or 85-90 wt.%.
The zirconium-aluminum composite sol contains zirconium-aluminum colloid particles, wherein the particle size of the zirconium-aluminum colloid particles is 15-50nm, and the particle size of the colloid particles is preferably 15-25nm, for example, about 20nm. The colloidal particle size can be measured by transmission electron microscopy characterization.
The weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve of the catalytic cracking catalyst provided by the invention is 1:10-10:1, for example, the weight ratio can be 1: 10-2: 1 or greater than 2:1 and less than 3:1 (noted as greater than 2:1 to less than 3:1) or greater than 3:1 to 5:1 or greater than 5:1 to 8:1 or greater than 8:1 to 10:1 or 2:10 to 9:1 or 2.5:10 to less than 3:1 or greater than 3:1 to 10:1 or 3.5:10 to 7:1. in one embodiment, the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is preferably 0.2:1 to 2.9:1 or 0.25 to 2.9:1 or 0.3:1-2.8:1 or 1:3-2.8:1 or 0.3:1-2:1 or 1:3-3:2, in this way, higher propylene yields and higher propylene selectivities are possible.
Preferably, the catalytic cracking catalyst comprises:
a) 15-60 wt%, e.g. 20-55 wt% or 25-50 wt% natural minerals on a dry basis;
b) 10-40 wt%, e.g., 15-35 wt%, or 10-30 wt%, or 20-30 wt%, of the zirconium-aluminum composite sol on a dry basis;
c) 25 wt% to 60 wt%, e.g., 20 wt% to 50 wt% or 25 wt% to 45 wt% of Y-type molecular sieve and MFI structure molecular sieve on a dry basis; the weight ratio of the Y-type molecular sieve to the MFI-structure molecular sieve is preferably 0.3:1-2.9:1 or 1:3-2.8:1 or 0.3:1-2:1 or 1:3-3:2; and
d) 3 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, of other inorganic oxide binders on a dry basis.
In the catalyst cracking catalyst provided by the invention, the natural mineral substances are one or more of kaolin, halloysite, montmorillonite, kieselguhr, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite.
The invention provides a catalystIn the catalyst for catalyst cracking, the Y-type molecular sieve is REY, REHY, REUSY, USY, for example, by gas phase chemical method (SiCl 4 Al-removing and Si-supplementing method), liquid phase chemical method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon compensation) or other methods (such as acid dealumination, complexation dealumination) or a mixture of various modified Y zeolite or the Y zeolite.
In the catalyst cracking catalyst provided by the invention, the MFI structure molecular sieve (MFI molecular sieve for short) comprises at least one of a rare earth-containing MFI structure molecular sieve, a phosphorus-containing MFI structure molecular sieve, an iron-containing MFI structure molecular sieve and a phosphorus-containing and transition metal-containing MFI structure molecular sieve, and the transition metal is one or more of RE, fe, cu, zn, mn, co, ni, sn, ti. Preferably, the MFI structure molecular sieve is a rare earth-containing molecular sieve and/or a phosphorus-and rare earth-containing MFI molecular sieve and/or a phosphorus-and iron-containing MFI structure molecular sieve. More preferably, the MFI structure molecular sieve is a rare earth-containing MFI molecular sieve and/or a phosphorus and rare earth-containing MFI structure molecular sieve, and the Y-type molecular sieve is preferably a USY molecular sieve, for example, a DASY molecular sieve, where the DASY may or may not contain a rare earth element. The MFI structure molecular sieve is, for example, a ZSM-5 molecular sieve.
In the catalytic cracking catalyst provided by the invention, the other inorganic oxide binders comprise one or more of inorganic oxides or composite oxides with binding functions, such as silica sol, alumina sol, silica-alumina gel, acidified pseudo-boehmite, phosphoalumina gel and the like.
According to the preparation method of the catalyst provided by the invention, in one embodiment, the preparation method of the zirconium-aluminum composite sol comprises the following steps:
acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant, and water; the conditions of the acidification hydrolysis include: the temperature is 10-100deg.C, and the time is 0.2-5h. Preferably, the conditions of the acidification hydrolysis comprise: the temperature is 10-60 ℃, the time is 0.5-2h, more preferably, the temperature is 20-45 ℃ and the time is 0.5-1h.
In the method for producing a zirconium-modified composite sol of the present invention, the specific manner of obtaining the mixture is not particularly limited, but in order to further improve the properties of the obtained zirconium-aluminum composite sol, it is preferable to mix an alumina precursor, a zirconium dioxide precursor, an acid and water to obtain a first mixture, and then add a surfactant to the first mixture to obtain the mixture. The present invention is not particularly limited in the embodiment of obtaining the first mixture, and for example, an alumina precursor and a zirconia precursor may be mixed with an acid solution, respectively, and then the two may be mixed to obtain the first mixture; the alumina precursor and the zirconia precursor can be added into the acid solution under the stirring condition; it is also possible to mix the alumina precursor with the acid solution and then add the aqueous solution of the zirconia precursor. Preferably, the acid is used in an amount such that the pH of the first mixture is from 0.5 to 5, more preferably from 1 to 4.
According to the preparation method of the zirconium-aluminum composite sol, preferably, the aluminum oxide precursor and the zirconium dioxide precursor are used in an amount such that the content of aluminum element in the prepared zirconium-aluminum composite sol is 1-10 wt%, more preferably, the content of aluminum element is 2-6 wt%, still more preferably, the content of aluminum element is 4.5-6 wt%; the content of the zirconium element is 0.5 to 10% by weight, more preferably 1 to 6% by weight, still more preferably 1.2 to 2.2% by weight, for example 1.4 to 2.0% by weight.
Preferably, in the method for preparing the zirconium-modified composite sol, the surfactant is used in an amount such that the content of the surfactant in the prepared zirconium-aluminum composite sol is 0.5 to 10 wt%, for example, 0.5 to 2 wt%, and more preferably 0.5 to 1.5 wt%, for example, 1 to 1.5 wt%, of the content of the aluminum element.
According to the present invention, in the zirconium-modified composite sol preparation method, the alumina precursor refers to an aluminum-containing substance that can exist in the form of aluminum oxide by calcination after the acidification hydrolysis treatment. Preferably, the alumina precursor is selected from at least one of SB powder, pseudo-boehmite, alumina trihydrate, boehmite, alumina sol and amorphous aluminum hydroxide, more preferably SB powder and/or pseudo-boehmite.
According to the present invention, in the method for preparing a zirconium-modified composite sol, the zirconium dioxide precursor refers to a zirconium-containing substance which can exist in the form of zirconium dioxide by calcination after the acidification hydrolysis treatment. Preferably, the zirconium dioxide precursor is at least one selected from zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium sulfate, hydrous zirconium oxide and amorphous zirconium dioxide, more preferably zirconium tetrachloride and/or zirconium oxychloride.
In the method for preparing the zirconium-modified composite sol, the acid can be at least one selected from inorganic acid and organic acid dissolved in water, preferably at least one selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid, and most preferably hydrochloric acid.
The zirconium-modified composite sol preparation method according to the present invention, wherein the kind of the surfactant is as described above, and for example, the surfactant is at least one selected from polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester, and polyol sucrose ester.
According to a preferred embodiment of the zirconium modified composite sol preparation method of the present invention, the acidification hydrolysis is performed under stirring. The stirring method is the existing method, the stirring condition is not particularly limited, and in one embodiment, the stirring speed can be 100-200r/min.
The invention relates to a preparation method of zirconium-modified composite sol, which comprises the following steps: adding an alumina precursor to the acid solution, dispersing for 10-60min, preferably in a homogenizer, then adding an aqueous solution of a zirconium dioxide precursor thereto, dispersing for 10-60min, preferably in a homogenizer, to obtain a first mixture; a surfactant is added to the first mixture to effect acidic hydrolysis.
According to the preparation method of the zirconium-modified composite sol, in one embodiment B, the method comprises the following steps: adding an alumina precursor and a zirconia precursor into the acid solution under stirring, and continuing stirring for 10-60min to obtain a first mixture; a surfactant is added to the first mixture to effect acidic hydrolysis.
According to the preparation method of the zirconium-modified composite sol, the acidified hydrolysis product is the zirconium-aluminum composite sol, and can be directly used for preparing a catalyst. Preferably, the method further comprises: the product of the acid hydrolysis is reacted under ultrasonic conditions (herein referred to as sonication). The product obtained after ultrasonic treatment is used for preparing the catalyst.
According to the preparation method of the zirconium-modified composite sol, a preferred embodiment of the invention, the method further comprises: and (3) reacting the product obtained by acidification and hydrolysis under ultrasonic conditions. By adopting the preferred embodiment, the reaction time is more favorable to be shortened, the particle size distribution of the colloidal particles is more uniform, and the prepared composite sol is more favorable to improve the abrasion strength of the catalyst when the composite sol is used for the catalytic cracking catalyst.
According to a preferred embodiment of the present invention, the conditions under which the reaction is carried out under ultrasonic conditions include: the temperature is 10 to 100deg.C, more preferably 10 to 60deg.C, for example 10 to 50deg.C, still more preferably 20 to 45deg.C, for 0.1 to 5 hours, still more preferably 0.1 to 3 hours, still more preferably 0.5 to 2 hours. The ultrasound may be water bath ultrasound or oil bath ultrasound, preferably water bath ultrasound. Preferably, the frequency of the ultrasound is 35-200KHz, more preferably 50-150KHz, and even more preferably 50-100KHz. For example, 35KHz, 50KHz, 80KHz, 100KHz can be used. The invention has wider power selection range for the ultrasonic wave, and can select proper power according to the quality of the ultrasonic processed material, for example, in the invention, 1kg of the ultrasonic processed material is processed by the ultrasonic wave, and the power of the ultrasonic wave can be 200-600W.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of mixing and pulping an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, water, zirconium-aluminum composite sol and other inorganic oxide binders to form catalyst slurry, and then spray drying. Preferably, the zirconium-aluminum composite sol is added finally in the mixing process, so that the pH value of the slurry is stable, and the molecular sieve is protected. For example, MFI structure molecular sieves, Y-type molecular sieves, natural minerals, water, and other inorganic oxide binders may be first slurried and then added to the zirconium aluminum composite sol to form a catalyst slurry.
According to the preparation method of the catalytic cracking catalyst, the total weight of dry basis of an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, zirconium-aluminum composite sol and other inorganic oxide binders is 100 parts by weight, wherein the natural minerals account for 12-65 parts by weight, the zirconium-aluminum composite sol accounts for 10-60 parts by weight, the Y-type molecular sieve and the MFI structure molecular sieve account for 22-75 parts by weight, the other inorganic oxide binders account for 3-20 parts by weight, and the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 1:10-10:1. Preferably, the natural mineral accounts for 20 to 55 parts by weight, the zirconium aluminum composite sol accounts for 10 to 40 parts by weight, such as 15 to 35 parts by weight, the Y-type molecular sieve and the MFI structure molecular sieve account for 25 to 60 parts by weight, such as 25 to 50 parts by weight, the other inorganic oxide binder accounts for 3 to 20 parts by weight, such as 5 to 15 parts by weight, and the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 0.25:1 to 2.9:1 or 0.3:1-2:1.
The natural minerals of the present invention are clay raw materials well known to those skilled in the art, and common clay types may be used in the present invention, and for the present invention, it is preferable that the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, quasi-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present invention, the clay is preferably one or more of sepiolite, kaolin and halloysite, and further preferably kaolin. The other inorganic oxide binder is one or more of aluminum sol, silica sol, acidified pseudo-boehmite, silica alumina sol and phosphorus alumina sol, and is more preferably aluminum sol.
In the present invention, the molecular sieve is a molecular sieve raw material well known in the art, and all kinds of molecular sieves commonly used in the art can be used in the present invention, and for the present invention, the Y-type molecular sieve is REY, REHY, REUSY, USY preferably prepared by a gas phase chemical method (SiCl 4 Al-removing and Si-supplementing method) and liquid phase meltingLearning method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon supplement method) and other methods.
The MFI structure molecular sieve (MFI molecular sieve for short) comprises at least one of an MFI structure molecular sieve containing rare earth, an MFI structure molecular sieve containing phosphorus, an MFI structure molecular sieve containing iron and an MFI structure molecular sieve containing phosphorus and transition metal, wherein the transition metal is one or more of RE, fe, cu, zn, mn, co, ni, sn, ti. Preferably, the MFI structure molecular sieve is a rare earth-containing molecular sieve and/or a phosphorus-and rare earth-containing MFI molecular sieve and/or a phosphorus-and iron-containing MFI structure molecular sieve. More preferably, the MFI structure molecular sieve is a phosphorus-and rare earth-containing MFI structure molecular sieve and/or a rare earth-containing MFI structure molecular sieve, and the Y-type molecular sieve is a DASY molecular sieve.
The MFI molecular sieve containing phosphorus and/or transition metal may be commercially available or prepared according to a conventional method, for example, the rare earth-containing MFI molecular sieve may be obtained by subjecting a hydrogen-type MFI zeolite or a sodium-type MFI molecular sieve to ion exchange with a rare earth salt solution or a solution of a rare earth salt and an inorganic ammonium salt, followed by filtration, washing, and calcination at 300 to 700 ℃ under a 0 to 100% steam atmosphere, to obtain a rare earth-modified MFI molecular sieve, and the sodium oxide content in the obtained rare earth-modified MFI molecular sieve (also referred to as MFI zeolite) is preferably not higher than 0.5 wt%, for example not higher than 0.2 wt%. The phosphorus may be introduced by impregnation.
According to the method for producing a catalytic cracking catalyst of the present invention, the solid content of the catalyst slurry is preferably 20% by weight or more, and more preferably 20 to 40% by weight.
According to a preferred embodiment of the present invention, the molecular sieve is present in the catalyst slurry in an amount of from 10 to 50 wt%, preferably from 25 to 45 wt%, based on the dry weight of the catalyst slurry; the clay content is 10-50 wt%, preferably 25-45 wt%; the content of the zirconium-aluminum composite sol is 6 to 35 wt%, preferably 10 to 30 wt% or 10 to 25 wt%, based on dry basis, of the aluminum sol (based on Al 2 O 3 Calculated as such) is 3 to 20 wt.%, preferably 5 to 15 wt.%.
According to the method for preparing the catalytic cracking catalyst of the present invention, it is preferable that spray drying is followed by calcination. The calcination method is an existing method, for example, the calcination temperature is 400-600 ℃ and the calcination time is 0.5-4 hours, preferably 1-3 hours.
In one embodiment, the preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps: pulping natural minerals and water, adding part of other inorganic oxide binders, and stirring to obtain slurry A; and pulping the Y-type molecular sieve and the MFI structure molecular sieve with water to obtain molecular sieve slurry, mixing the slurry A with the molecular sieve slurry, finally adding the rest of other inorganic oxide binders and zirconium-aluminum composite sol, pulping and stirring to obtain catalyst slurry, spray-drying the catalyst slurry, and roasting the obtained catalyst microspheres at the temperature of 450-550 ℃ for 1-3 hours, such as at the temperature of 500 ℃ for 2 hours, thereby obtaining the catalytic cracking catalyst. Wherein in one manner the amount of said other inorganic oxide binder in slurry a is from 10 to 30 wt%, e.g. from 20 to 30 wt%, based on the total amount of said other inorganic oxide binder, on a dry basis.
The present invention will be described in detail by examples.
The composition of the zirconium-aluminum composite sol was analyzed by ICP-OES method.
The raw materials used in the catalyst preparation were as follows:
SB powder: commercially available from Sasol, germany, 75% by weight solids;
pseudo-boehmite: commercially available from Shandong aluminum company, 74% by weight solids;
zirconium oxychloride: commercially available from Aldrich company, analytically pure, 98.5%;
zirconium tetrachloride: commercial from Beijing chemical plant, inc., analytical grade, 98%;
triton X-100: polyoxyethylene-8-octylphenyl ether, commercially available from the dow company, usa, analytically pure, 99%;
kaolin: the solid content was 75% by weight, produced by chinese kaolin limited (su zhou);
DASY molecular sieves: qilu division of China petrochemical catalystCompany product, rare earth content of 2.3 wt%, silicon to aluminum ratio (SiO 2 /Al 2 O 3 ) 6, crystallinity 65%; crystallinity 77%, sodium oxide content 0.2% by weight, rare earth content (in RE 2 O 3 Meter) 2.0 wt-%).
ZRP-1 molecular sieve, silicon-aluminum ratio of 30, crystallinity of 60%, sodium oxide content of 0.2% by weight, rare earth content (RE 2 O 3 Calculated as) 2.0 wt%, P 2 O 5 The content of (3.02 wt%). The product of Qilu division company.
Aluminum sol: produced by Shandong aluminum factory, the solid content is 21 weight percent.
Preparation of zirconium aluminum composite sol example 1
(1) 440g of deionized water is added into a beaker, 140g of SB powder is then added, 21g of hydrochloric acid is slowly added, and the mixture is dispersed in a homogenizer for 30min; to another beaker was added 337g of water followed by 52g of zirconium oxychloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 20min to obtain a first mixture; to the first mixture was added 0.8g of the surfactant triton X-100, and the mixture was stirred at 20℃for 30min at a rotational speed of 150r/min. Sol 1 was obtained.
(2) The sol is put into an ultrasonic water bath, and reacts for 120min at the reaction temperature of 30 ℃ under the frequency of 50KHz and the power of 280W, thus obtaining the zirconium-aluminum composite sol A1.
The zirconium aluminum composite sol A1 is dried at 100 ℃ for 6 hours, and then is baked at 600 ℃ for 6 hours, so that the XRD pattern of the obtained solid has diffraction peaks at the positions of 28 degrees and 31 degrees of 2 theta and at the positions of 30 degrees, 35 degrees, 50 degrees, 60 degrees, 46 degrees and 67 degrees of 2 theta; peaks at 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG for 2 theta correspond to ZrO 2 The peaks at 2 theta of 30.3 DEG + -0.5, 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG correspond to ZrO 2 Tetragonal phase(s); the peak correspondence is gamma-Al at 46 deg. + -0.5 deg. and 66.6 deg. + -0.5 deg. for 2 theta 2 O 3 . The average particle diameter was 20nm. The composition and properties of A1 are shown in Table 1.
Preparation example 2 of zirconium aluminum composite sol
(1) Adding 440g of deionized water into a beaker, then adding 142g of pseudo-boehmite powder, dispersing for 30min in a homogenizer, and slowly adding 21g of hydrochloric acid to obtain a first mixture A; to another beaker was added 337g of water followed by 52g of zirconium oxychloride to give a second mixture B; mixture B was slowly poured into mixture A, then 0.8g of surfactant triton X-100 was added and stirred at room temperature for 30min.
(2) And (3) placing the reaction product into an ultrasonic water bath, and reacting for 120min at the reaction temperature of 30 ℃ under the frequency of 50KHz and the power of 280W to obtain the zirconium-aluminum composite sol A2. The zirconium aluminum composite sol A2 is dried at 100 ℃ for 6 hours, and then is baked at 600 ℃ for 6 hours, so that the XRD pattern of the obtained solid has diffraction peaks at 29 degrees and 31 degrees of 2 theta and at 30 degrees, 35 degrees, 50 degrees, 60 degrees, 46 degrees and 67 degrees of 2 theta; peaks at 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG for 2 theta correspond to ZrO 2 The peaks at 2 theta of 30.3 DEG + -0.5, 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG correspond to ZrO 2 Tetragonal phase(s); the peak correspondence is gamma-Al at 46 deg. + -0.5 deg. and 66.6 deg. + -0.5 deg. for 2 theta 2 O 3 . The average particle diameter was 20nm. The composition and properties of A2 are shown in Table 1.
Preparation example 3 of zirconium aluminum composite sol
(1) Preparing zirconium-aluminum composite sol:
500g of deionized water is added into a beaker, 126g of SB powder is then added, 17.4g of hydrochloric acid is slowly added, and the mixture is dispersed in a homogenizer for 30 minutes; to another beaker was added 370g of water followed by 76g of zirconium oxychloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 20min to obtain a first mixture; to the first mixture was added 0.7g of the surfactant triton X-100, and the mixture was stirred at 20℃for 30min at a rotational speed of 150r/min.
(2) And (3) placing the reaction product in the step (1) into an ultrasonic water bath, and reacting for 120min at the reaction temperature of 20 ℃ under the frequency of 50KHz and the power of 280W to obtain the zirconium-aluminum composite sol. Designated as A3.
The zirconium aluminum composite sol A3 is dried at 100 ℃ for 6 hours, and then is baked at 600 ℃ for 6 hours, so that the XRD pattern of the obtained solid has diffraction peaks at 29 degrees and 31 degrees of 2 theta and at 30 degrees, 35 degrees, 50 degrees, 60 degrees, 46 degrees and 67 degrees of 2 theta; peaks at 28 DEG + -0.5 DEG and 31.4 DEG + -0.5 DEG for 2 theta correspond to ZrO 2 Is 30.3 DEG + -0.5 in 2 theta,Peaks at 35 DEG + -0.5 DEG, 50 DEG + -0.5 DEG, 60 DEG + -0.5 DEG correspond to ZrO 2 Tetragonal phase(s); the peak correspondence is gamma-Al at 46 deg. + -0.5 deg. and 66.6 deg. + -0.5 deg. for 2 theta 2 O 3 . The average particle diameter was 20nm. The composition and properties of A3 are shown in Table 1.
Preparation example 4 of zirconium aluminum composite sol
(1) 500g of deionized water is added into a beaker, 126g of SB powder is then added, 17.4g of hydrochloric acid is slowly added, and the mixture is dispersed in a homogenizer for 30 minutes; to another beaker was added 370g of water followed by 55g of zirconium tetrachloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 20min to obtain a first mixture; to the first mixture was added 0.7g of the surfactant triton X-100, and the mixture was stirred at 20℃for 30min at a rotational speed of 150r/min.
(2) And (3) placing the reaction product in the step (1) into an ultrasonic water bath, and reacting for 60min at the reaction temperature of 35 ℃ under the frequency of 50KHz and the power of 280W to obtain the zirconium-aluminum composite sol A4.
The obtained zirconium-aluminum composite sol A4 was analyzed and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol A4 at 100 ℃ for 6 hours, roasting at 600 ℃ for 6 hours to obtain a solid, performing XRD analysis on the solid, wherein the XRD spectrum is similar to the graph of A3, and monoclinic zirconium and tetragonal ZrO exist on the XRD spectrum 2 And gamma-Al 2 O 3 Is a diffraction peak of (2).
The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol A4 is uniform and is about 20nm.
TABLE 1
Catalyst preparation example 1:
firstly, 200g of kaolin is pulped to obtain slurry with the solid content of 40 weight percent, and 74g of alumina sol (called as alumina sol 1) is added for pulping; 118g (solid content 85 wt%) of DASY molecular sieve and 100g (solid content 75 wt%) of ZRP-1 molecular sieve are taken, added with water and pulped, and dispersed by a homogenizer to obtain molecular sieve slurry with solid content of 35 wt%; the kaolin slurry and the molecular sieve slurry are mixed and stirred, 164g of aluminum sol (called aluminum sol 2) is added, and finally zirconium aluminum composite sol A1 is added, and the mixture is stirred for 30min in a homogenizing way. The catalyst slurry was spray dried and the resulting catalyst microspheres were calcined at 500 ℃ for 2 hours to give the catalytic cracking catalyst C1, the pore volume and attrition index are shown in table 2.
Catalyst preparation examples 2-7,
catalyst preparation example 1 was followed to prepare a catalyst, the zirconium-aluminum composite sol used was different, the ratio of DASY molecular sieve to ZRP-1 molecular sieve was different, and the composition and physical and chemical properties of the catalyst were shown in Table 2.
The contents of the components in the catalyst composition in Table 2 are weight percent on a dry basis, calculated from the amounts charged.
TABLE 2
Catalyst preparation comparative example 1
(1) Alumina sol: 772g deionized water was added to the beaker, then 167g SB powder was added, dispersed in a homogenizer for 30min, and 22g hydrochloric acid was added for acidification to give alumina sol designated as D1.
Catalyst preparation comparative example 1:
catalyst was prepared according to the method of catalyst preparation example 1, except that sol D1 of comparative example 1 was used, to obtain comparative catalyst DB1. The composition of the catalyst is shown in Table 2.
Catalyst preparation comparative example 2
792g of deionized water was added to the beaker, 240g of zirconium tetrachloride was slowly added under stirring (rotation speed: 150 r/min), and then 110g of aqueous ammonia (25 wt%) was added, followed by dispersion in a homogenizer for 30 minutes, to obtain zirconium sol D2.
A catalyst was prepared according to the method of comparative example 1, except that sol D2 of comparative example 2 was used.
Catalyst preparation comparative example 3:
a catalyst was prepared according to the method of comparative example 1 except that D2 was used instead of part D1, where D1 (in Al): d2 The weight ratio (in Zr) is the ratio of the weight of aluminum to the weight of zirconium of A1.
Catalyst preparation comparative example 4
Taking 120g of DASY molecular sieve and 120g of ZRP-1 molecular sieve, separately adding water for pulping, dispersing by a homogenizer to obtain molecular sieve slurry with the solid content of 35 weight percent, and simultaneously adding 5g of zirconia powder (prepared by the method of the example 3 of CN 102211039B); pulping 200g of kaolin to obtain slurry with the solid content of 40%, and adding 74g of aluminum sol for pulping; the kaolin slurry and the molecular sieve slurry were mixed and stirred, 164g of alumina sol and D1 of comparative example 1 sol were then added, and finally 20g of zirconia powder was added and stirred homogeneously for 30min. The catalyst slurry was spray-dried, and the resulting catalyst microspheres were calcined at 500℃for 2 hours to obtain a catalytic cracking catalyst DB4.
Catalyst preparation comparative example 5
Catalysts were prepared as in comparative example 1, except that the formulation levels were varied.
Characterization of the catalyst:
the pore volume (pore volume) and attrition index of the catalyst were measured by the methods RIPP28-90 and RIPP29-90 in petrochemical analysis methods, RIPP test methods (Yang Cui, scientific Press, 1990). The results are shown in Table 2.
Catalyst evaluation:
the catalyst was deactivated by 100% steam aging at 800℃for 8 hours. The evaluation was carried out on the fixed fluidized bed micro-reverse ACE, wherein the raw oil was a hydrogenated modified oil (composition and physical properties are shown in Table 3), and the evaluation conditions were: the reaction temperature is 580 ℃, the agent-oil ratio (weight) is 6, and the weight hourly space velocity is 16h -1 . The results are shown in Table 4.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield
Low olefin selectivity = propylene yield + ethylene yield
Propylene hydrocarbon selectivity = propylene yield/LPG yield x 100%
TABLE 3 Table 3
| Project | Raw oil |
| Density (20 ℃), g/cm 3 | 0.9334 |
| Refraction (70 ℃ C.) | 1.5061 |
| Four components, m% | |
| Saturated hydrocarbons | 55.6 |
| Aromatic hydrocarbons | 30 |
| Colloid | 14.4 |
| Asphaltenes | <0.1 |
| Freezing point, DEG C | 34 |
| Metal content, ppm | |
| Ca | 3.9 |
| Fe | 1.1 |
| Mg | <0.1 |
| Na | 0.9 |
| Ni | 3.1 |
| Pb | <0.1 |
| V | 0.5 |
| C m％ | 86.88 |
| H m％ | 11.94 |
| S m％ | 0.7 |
| Carbon residue m% | 1.77 |
| H m％ | 11.94 |
TABLE 4 Table 4
As can be seen from Table 4, the catalytic cracking catalyst provided by the invention has the advantages of significantly smaller attrition index, better attrition strength (i.e. high strength), larger pore volume, further improved conversion rate, increased low-carbon olefin yield, higher propylene yield and higher propylene selectivity in the heavy oil catalytic cracking reaction.
Claims (31)
1. A catalytic cracking catalyst comprising, on a dry weight basis, the catalyst:
a) 12 to 65% by weight of natural minerals on a dry basis,
b) 10 to 60 weight percent of zirconium-aluminum composite sol based on dry basis,
c) 22-75 wt% of Y-type molecular sieve and MFI structure molecular sieve on a dry basis; the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 1:10-10:1; and
d) 3% to 20% by weight, on a dry basis, of other inorganic oxide binders;
in the zirconium-aluminum composite sol, the content of aluminum element is 1-10 wt%, the content of zirconium element is 0.5-10 wt%, the pH value of the zirconium-aluminum composite sol is 0.5-5, the composite sol is dried at 100 ℃ for 6 hours, and then baked at 600 ℃ for 6 hours, wherein zirconium dioxide exists in monoclinic phase and tetragonal phase forms in the obtained solid; the zirconium-aluminum composite sol contains a surfactant, wherein the content of the surfactant is 0.5-10% by weight of the content of aluminum element; the surfactant is at least one selected from polyoxyethylene-8-octyl phenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester and polyol sucrose ester;
the preparation method of the catalytic cracking catalyst comprises the following steps: (1) preparing zirconium-aluminum composite sol: acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant, and water; the conditions of the acidification hydrolysis include: the temperature is 10-100 ℃ and the time is 0.2-5h; (2) Mixing and pulping an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, zirconium-aluminum composite sol and other inorganic oxide binders, and spray drying.
2. The catalytic cracking catalyst of claim 1, wherein the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 0.2:1-2.9:1.
3. the catalytic cracking catalyst of claim 2, wherein the weight ratio of the Y-type molecular sieve to the MFI structure molecular sieve is 0.3:1-2:1.
4. the catalytic cracking catalyst of claim 1, wherein the natural minerals comprise one or more of kaolin, montmorillonite, diatomaceous earth, attapulgite, sepiolite, hydrotalcite, bentonite, and rectorite; the Y-type molecular sieve is one or more of REY, REHY, REUSY, USY; the MFI structure molecular sieve comprises at least one of a rare earth-containing MFI structure molecular sieve, a phosphorus-containing MFI structure molecular sieve, an iron-containing MFI structure molecular sieve and a phosphorus-containing and transition metal-containing MFI structure molecular sieve; the other inorganic oxide binder comprises one or more of silica sol, alumina sol, acidified pseudo-boehmite, silica-alumina gel and phosphoalumina gel.
5. The catalytic cracking catalyst of claim 1, wherein the MFI structure molecular sieve is a rare earth-containing MFI molecular sieve and/or a phosphorus-and rare earth-containing MFI structure molecular sieve.
6. The catalytic cracking catalyst of claim 1, wherein the solid has an XRD pattern with diffraction peaks at 28 ° ± 0.5 °, 31.4 ° ± 0.5 ° 2Θ and at 30.3 ° ± 0.5, 35 ° ± 0.5 °, 50 ° ± 0.5 °, 60 ° ± 0.5 °; in the XRD pattern of the solid, diffraction peaks exist at the positions of 46 DEG + -0.5 DEG and 66.6 DEG + -0.5 DEG of 2 theta.
7. The catalytic cracking catalyst according to claim 1, wherein the content of aluminum element in the zirconium-aluminum composite sol is 2 to 6 wt%, and the content of zirconium element is 1 to 6 wt%;
the weight ratio of aluminum element to zirconium element in the zirconium-aluminum composite sol is (0.3-6): 1.
8. the catalytic cracking catalyst according to claim 7, wherein the weight ratio of aluminum element to zirconium element in the zirconium-aluminum composite sol is (1-4): 1.
9. the catalytic cracking catalyst according to claim 8, wherein the weight ratio of aluminum element to zirconium element in the zirconium-aluminum composite sol is (2.2-3.9): 1.
10. the catalytic cracking catalyst of claim 1, wherein the zirconium aluminum composite sol has a pH of 1-4.
11. The catalytic cracking catalyst of claim 10, wherein the pH of the zirconium aluminum composite sol is 2.2-2.6.
12. The catalytic cracking catalyst according to claim 1, wherein the content of the surfactant in the zirconium aluminum composite sol is 0.5-2 wt% of the content of aluminum element.
13. The catalytic cracking catalyst of claim 12, wherein the surfactant is present in the zirconium aluminum composite sol in an amount of 1-1.5 wt% of the elemental aluminum content.
14. The catalytic cracking catalyst of any one of claims 1-13, wherein the catalytic cracking catalyst comprises:
a) 20-55 wt% natural minerals on a dry basis;
b) 10% -40% of zirconium-aluminum composite sol based on dry basis;
c) 25% -60% of Y-type molecular sieve and MFI structure molecular sieve based on dry basis;
d) 3% -20% of other inorganic oxide binders on a dry basis.
15. The catalytic cracking catalyst of claim 14, wherein the catalytic cracking catalyst comprises 15-35% zirconium aluminum composite sol on a dry basis.
16. A method of preparing the catalytic cracking catalyst of claim 1, comprising: (1) preparing zirconium-aluminum composite sol: acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant, and water; the conditions of the acidification hydrolysis include: the temperature is 10-100 ℃ and the time is 0.2-5h; (2) Mixing and pulping an MFI structure molecular sieve, a Y-type molecular sieve, natural minerals, zirconium-aluminum composite sol and other inorganic oxide binders, and spray drying.
17. The preparation method according to claim 16, wherein in the preparation method of the zirconium aluminum composite sol, the condition of acidification hydrolysis comprises: the temperature is 10-60 ℃; the time is 0.5-2h.
18. The preparation method according to claim 17, wherein in the preparation method of the zirconium aluminum composite sol, conditions of acidification and hydrolysis: the temperature is 20-45 ℃ and the time is 0.5-1h.
19. The production method according to claim 16, wherein the alumina precursor and the zirconia precursor are used in such an amount that the content of the aluminum element in the produced zirconium-aluminum composite sol is 1 to 10% by weight and the content of the zirconium element is 0.5 to 10% by weight;
the amount of the surfactant is such that the content of the surfactant in the prepared zirconium-aluminum composite sol is 0.5-10 wt% of the content of aluminum element.
20. The preparation method according to claim 19, wherein the content of aluminum element in the prepared zirconium-aluminum composite sol is 2-6 wt% and the content of zirconium element is 1-6 wt%.
21. The preparation method according to claim 19, wherein the content of the surfactant in the zirconium-aluminum composite sol is 0.5 to 1.5% by weight of the content of aluminum element.
22. The preparation method of claim 16, wherein the zirconium aluminum composite sol preparation method comprises: mixing an alumina precursor, a zirconia precursor, an acid and water to obtain a first mixture, and then adding a surfactant to the first mixture to obtain a second mixture; the acid is used in an amount such that the pH of the first mixture is between 0.5 and 5.
23. The method of claim 22, wherein the acid is used in an amount such that the pH of the first mixture is 1-4.
24. The preparation method according to any one of claims 16 to 23, wherein the zirconium aluminum composite sol preparation method further comprises: the product obtained by acidification and hydrolysis is reacted under the ultrasonic condition; the conditions under which the reaction is carried out under ultrasonic conditions include: the temperature is 10-100 ℃; the time is 0.1-5h; the frequency of the ultrasonic wave is 35-200kHz.
25. The method of claim 24, wherein the reaction is carried out at a temperature of 10-60 ℃ under ultrasonic conditions.
26. The method of claim 25, wherein the reaction is carried out at a temperature of 20-45 ℃ under ultrasonic conditions.
27. The method of claim 24, wherein the reaction is performed under ultrasonic conditions for a period of time ranging from 0.1 to 3 hours.
28. The method of claim 27, wherein the reaction is performed under ultrasonic conditions for a period of time ranging from 0.5 to 2 hours.
29. The production method according to claim 16, wherein the alumina precursor is at least one selected from pseudo-boehmite, alumina trihydrate, boehmite, alumina sol and amorphous aluminum hydroxide; the zirconium dioxide precursor is at least one selected from zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconium oxide and amorphous zirconium dioxide; the acid is at least one selected from hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
30. The method of claim 16, wherein the mixing of step (2) and the zirconium aluminum composite sol are added last.
31. A catalytic cracking process comprising the step of contacting a hydrocarbon oil with the catalyst of any one of claims 1 to 15 or the catalytic cracking catalyst obtained by the process of any one of claims 16 to 30.
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