CN1323133C - Hydrocarbon cracking catalyst and its preparing method - Google Patents
Hydrocarbon cracking catalyst and its preparing method Download PDFInfo
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- CN1323133C CN1323133C CNB2004100009483A CN200410000948A CN1323133C CN 1323133 C CN1323133 C CN 1323133C CN B2004100009483 A CNB2004100009483 A CN B2004100009483A CN 200410000948 A CN200410000948 A CN 200410000948A CN 1323133 C CN1323133 C CN 1323133C
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- aluminum oxide
- catalyzer
- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000005336 cracking Methods 0.000 title claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 13
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- 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 47
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- 239000011574 phosphorus Substances 0.000 claims abstract description 36
- 239000004927 clay Substances 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims description 85
- 229910021536 Zeolite Inorganic materials 0.000 claims description 82
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 78
- 229910052782 aluminium Inorganic materials 0.000 claims description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- -1 polynite Chemical compound 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 239000004411 aluminium Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 19
- 150000004684 trihydrates Chemical class 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 16
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 15
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 5
- 241000269350 Anura Species 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical group O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims 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 claims description 3
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 3
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- 229910000406 trisodium phosphate 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 2
- 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 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 abstract description 30
- 239000002283 diesel fuel Substances 0.000 abstract description 21
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 27
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 25
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000003921 oil Substances 0.000 description 19
- 229910052761 rare earth metal Inorganic materials 0.000 description 16
- 150000002910 rare earth metals Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052809 inorganic oxide Inorganic materials 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000004523 catalytic cracking Methods 0.000 description 11
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 3
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 101100190464 Caenorhabditis elegans pid-2 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000002063 nanoring Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a hydrocarbon cracking catalyst which comprises aluminum oxide, molecular sieves and phosphorus, and contains or does not contain clay, wherein the aluminum oxide is eta-aluminum oxide and/or chi-aluminum oxide or a mixture of the eta-aluminum oxide and/or the chi-aluminum oxide with gamma-aluminum oxide. Taking the total weight of the catalyst as a reference, the catalyst is prepared from 0.5 to 50 wt% of the eta-aluminum oxide and/or the chi-aluminum oxide, 0 to 50 wt% of the gamma-aluminum oxide, 10 to 70 wt% of the molecular sieve, 0 to 75 wt% of the clay, and 0.1 to 8 wt% of the phosphorous measured by P2O5t. The catalyst not only has high cracking activity, but also obviously increases the quality of gasoline, diesel oil and liquefied gas in cracked products.
Description
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof.
Background technology
The heaviness tendency of catalytically cracked stock is serious day by day, and this just requires cracking catalyst and cracking technology to have stronger cracking ability, to reach the purpose of light oil with high yield (gasoline and diesel oil) and liquefied gas.
For catalytically cracked gasoline, alkene, aromatic hydrocarbons and isoparaffin are the main contributors of octane value, because environmental requirement needs to reduce the FCC olefin content in gasoline.In order to remedy the loss of the gasoline octane rating that causes because of olefin(e) centent decline, need to increase the content of isoparaffin, aromatic hydrocarbons in the gasoline, this just need develop to produce has than low olefin-content the hydrocarbon cracking catalyzer of higher aromatic hydrocarbons and isoparaffin content gasoline and cracking technology.
Meanwhile, the quality of catalytic cracking diesel oil also needs to improve, and the diesel oil aniline point that adopts existing cracking catalyst and technology to obtain is lower, and density is bigger than normal, and cetane value is on the low side.This just need develop has strong heavy oil cracking ability, and, can make the density of diesel oil reduce hydrocarbon cracking catalyzer and cracking technology that aniline point and cetane value improve.
Moreover, low-carbon alkene and Trimethylmethane contained in the liquefied gas that catalytic cracking obtains are basic Organic Chemicals, at present, supply falls short of demand for low-carbon alkene (particularly propylene) and Trimethylmethane, and in the liquefied gas product of existing cracking catalyst and explained hereafter, the low-carbon alkene (particularly propylene) and the content of Trimethylmethane are lower, and therefore, cracking catalyst and the cracking technology that has higher low-carbon alkene (particularly propylene) and Trimethylmethane in the liquefied gas in a kind of crackate also is badly in need of developing in market.
CN1042201C discloses a kind of voluminous C
3-C
5The cracking catalyst of alkene, this catalyzer is by the y-type zeolite of 10-50 weight %, lattice constant≤2.45 nanometers, and 2-40 weight % is selected from P, RE, the ZSM-5 zeolite of H modification, the semi-synthetic carrier of the kaolin of 20-80 weight % and al binder is formed.
CN1055301C discloses the cracking catalyst of a kind of voluminous isomeric olefine and gasoline, this catalyzer is by the composite aluminum base al binder of being made up of according to 1: 9 to 9: 1 weight ratio pseudo-boehmite and aluminium colloidal sol of 5-70 weight %, the molecular sieve of the clay of 5-65 weight % and 23-50 weight % is formed, and described molecular sieve is that the phosphorus content of the y-type zeolite of 15-82 weight % and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring supersiliceous zeolite and/or HZSM-5 zeolite of 0-10 weight %.
CN1072201A discloses a kind of hydrocarbon conversion catalyst of producing stop bracket gasoline and alkene, this catalyzer is by the ZSM-5 of 10-40 weight %, the full synthesis carrier of REY and three kinds of zeolites of high silicon Y and surplus or the semi-synthetic carrier that contains 10-40 weight % silicon and/or al binder are formed, wherein, it is 3-50 weight % that ZSM-5 divides the content of zeolite, the content of REY and the high-silicon Y-Zeolite 12-75 weight % that respectively does for oneself.
CN1085825A discloses a kind of stop bracket gasoline of producing, propylene, the hydrocarbon conversion catalyst of butylene, this catalyzer is by the ZRP zeolite of 10-40 weight %, the full synthesis carrier of REY and three kinds of zeolites of high silicon Y and surplus or the semi-synthetic carrier that contains 10-40 weight % silicon and/or al binder are formed, wherein, the content of ZRP zeolite is 3-50 weight %, the content of REY and the high-silicon Y-Zeolite 12-75 weight % that respectively does for oneself.
CN1325940A discloses a kind of phosphorated hydrocarbon cracking catalyzer, and this catalyzer is by y-type zeolite or y-type zeolite and MFI structural zeolite and/or the Beta zeolite of 10-60 weight %, the clay of 0-75 weight %, and two kinds of aluminum oxide of 10-60 weight % are with P
2O
5Meter, the phosphorus of 0.1-7.0 weight % and with RE
2O
3Meter, the rare earth of 0-20 weight % is formed.Described two kinds of aluminum oxide are respectively from pseudo-boehmite and aluminium colloidal sol.This catalyzer has high ability of residuum conversion, and olefin(e) centent is lower in the product gasoline, still, uses this catalyzer to fail to improve the quality of catalytic cracking diesel oil, can not improve the content of low-carbon alkene and Trimethylmethane in the liquefied gas.
CN1354224A discloses the catalytic cracking catalyst that isoparaffin gasoline, propylene and Trimethylmethane are rich in a kind of production, this catalyzer is by the clay of 0-70 weight %, the molecular sieve of the inorganic oxide of 5-90 weight % and 1-50 weight % is formed, molecular sieve wherein for the silica alumina ratio of (1) 20-75 weight % be 5-15, with RE
2O
3The silica alumina ratio of type-Y high silicon zeolite and (2) the 20-75 weight % of the content of rare earth 8-20 weight % of meter is 16-50, with RE
2O
3The type-Y high silicon zeolite of the content of rare earth 2-7 weight % of meter and the β zeolite of (3) 1-50 weight % or the mixture of mordenite or ZRP zeolite.
Aluminum oxide is the component that cracking catalyst contains usually.In the prior art, aluminum oxide is many from monohydrate alumina and aluminium colloidal sol, wherein, monohydrate alumina comprises boehmite and pseudo-boehmite, in the roasting process of Preparation of Catalyst, boehmite, pseudo-boehmite and aluminium colloidal sol all change gama-alumina into, and the contained aluminum oxide of the described catalyzer of above-mentioned prior art is gama-alumina.
Aluminum oxide can also be from hibbsite.Alumina trihydrate comprises α-alumina trihydrate, β-alumina trihydrate (or claiming surge aluminium stone) and promise diaspore, and in catalyst preparation process, α-alumina trihydrate is transformed into χ-aluminum oxide, and β-alumina trihydrate then is transformed into η-aluminum oxide.The promise diaspore just exists at occurring in nature, still can't obtain by synthetic.CN1388214 discloses a kind of preparation method of fluid cracking catalyst, this method is to contain the cracking catalyst component mixture drying of clay, aluminum oxide and molecular sieve, contains the aluminum oxide from β-alumina trihydrate of 1.5-55 weight % in the described catalyzer.This catalyzer has stronger heavy oil cracking activity and lightweight oil selectivity preferably, but but can not reduce olefin content in gasoline, improves the catalytic cracking diesel oil quality, can not improve the content of low-carbon alkene and Trimethylmethane in the liquefied gas.
Summary of the invention
The purpose of this invention is to provide a kind of new hydrocarbon cracking catalyzer, this catalyzer has stronger heavy oil cracking ability, uses in the cracked product of this catalyzer, and the olefin(e) centent of gasoline is lower, diesel quality is higher, and has higher low-carbon alkene and Trimethylmethane content in the liquefied gas.
In the prior art, though the example of introducing alumina trihydrate in the cracking catalyst preparation is also arranged,, its purpose just improves the cracking ability of cracking catalyst, and to the gasoline in the cracked product, the quality of diesel oil and liquefied gas is influence not.The present inventor is surprised to find that, in cracking catalyst, introduce aluminum oxide and the phosphorus that alumina trihydrate forms simultaneously, the aluminum oxide that forms of β-alumina trihydrate particularly, be η-aluminum oxide and phosphorus, produce special synergistic effect, can not only improve the cracking ability of cracking catalyst, simultaneously, can significantly improve the gasoline in the cracked product, the quality of diesel oil and liquefied gas.
Catalyzer provided by the invention contains aluminum oxide and molecular sieve, contain or do not contain clay, wherein, described aluminum oxide is η-aluminum oxide and/or χ-aluminum oxide, or the mixture of η-aluminum oxide and/or χ-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus, with the catalyzer total amount is benchmark, the content of η-aluminum oxide and/or χ-aluminum oxide is 0.5-50 weight %, the content of gama-alumina is 0-50 weight %, the content of molecular sieve is 10-70 weight %, and the content of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-8 weight %.
Preparation of catalysts method provided by the invention comprises and will contain aluminum compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, wherein, described aluminum compound is the aluminum compound that can form η-aluminum oxide and/or χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, the compound that before roasting, also adds phosphorus, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 η-aluminum oxide of weight % and/or χ-aluminum oxide, the gama-alumina of 0-50 weight %, the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %.
Catalyzer provided by the invention not only has higher cracking activity, and, improved the gasoline in the cracked product significantly, the quality of diesel oil and liquefied gas, show to have lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content in the gasoline, diesel oil has lower density and higher cetane value, the content that has higher low-carbon alkene, particularly propylene and Trimethylmethane in the liquefied gas.
Embodiment
According to catalyzer provided by the invention, under the preferable case, the content of η-aluminum oxide and/or χ-aluminum oxide is 5-45 weight %, and the content of gama-alumina is 0-40 weight %, and the content of molecular sieve is 20-50 weight %, and the content of clay is 0-60 weight %, with P
2O
5Meter, the content of phosphorus is 0.5-6 weight %.
Wherein, 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 non-zeolite 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, Beta zeolite, the mordenite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous, iron and/or rare earth, overstable gamma zeolite, phosphorous, iron 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 of phosphorous, iron and/or rare earth (as the ZSM-5 zeolite of phosphorous, iron and/or rare earth, the zeolite that the disclosed phosphorated of CN1194181A has the MFI structure) 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.Be preferably the SAPO molecular sieve, as in SAPO-11 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve one or more.
Under the preferable case, described molecular screening is from the zeolite with MFI structure of overstable gamma zeolite, the Beta zeolite of the y-type zeolite of y-type zeolite, phosphorous, iron and/or rare earth, overstable gamma zeolite, phosphorous, iron and/or rare earth, the zeolite with MFI structure, phosphorous, iron and/or rare earth, in the SAPO molecular sieve one or more.
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 one or more in kaolin, polynite, diatomite, rectorite, sepiolite, the attapulgite.These clays are conventionally known to one of skill in the art.
Catalyzer provided by the invention can also contain non-oxide aluminium heat-resistant inorganic oxide, described non-oxide aluminium heat-resistant inorganic oxide is selected from as in the non-oxide aluminium heat-resistant inorganic oxide of cracking catalyst matrix one or more, as in silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.In preferred silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, the calcium oxide one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.With the catalyzer total amount is benchmark, and the content of described non-oxide aluminium heat-resistant inorganic oxide is 0-10 weight %, is preferably 0-5 weight %.
According to Preparation of catalysts method provided by the invention, described aluminum compound is the aluminum compound that can form η-aluminum oxide and/or χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina.
The described aluminum compound that can form η-aluminum oxide and/or χ-aluminum oxide can be any in catalyst preparation process, can form the aluminum compound of η-aluminum oxide and/or χ-aluminum oxide, be preferably α-alumina trihydrate and/or β-alumina trihydrate, more preferably β-alumina trihydrate.
The described aluminum compound that can form gama-alumina can be any in catalyst preparation process, can form the aluminum compound of gama-alumina, is preferably boehmite, pseudo-boehmite and/or aluminium colloidal sol.
Described phosphorus compound can add by the arbitrary steps before roasting, as joining aluminum contained compound, molecular sieve and water, contain or slurries not argillaceous in, also can be earlier with aluminum contained compound, molecular sieve and water, contain or slurry dried not argillaceous, introduce phosphorus compound with pickling process again, then roasting.In the catalyzer of the present invention, the content of described phosphorus does not comprise the phosphorus that molecular sieve contained originally.
Described phosphorus compound comprises the compound of various phosphorus, as one or more in phosphoric acid, phosphoric acid salt, phosphorous acid, phosphite, tetra-sodium, pyrophosphate salt, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate, be preferably in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, potassium pyrophosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, Sodium hexametaphosphate 99, the hexa metaphosphoric acid potassium one or more.One or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99 more preferably.
The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the gama-alumina of η-aluminum oxide of 0.5-50 weight % and/or χ-aluminum oxide, 0-50 weight %, and the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %.Under the preferable case, the consumption of each component makes η-aluminum oxide and/or the χ-aluminum oxide that contains 5-45 weight % in the final catalyzer, the gama-alumina of 0-40 weight %, and the molecular sieve of 20-50 weight %, the clay of 0-60 weight % is with P
2O
5Meter, the phosphorus of 0.5-6 weight %.
If also contain non-oxide aluminium inorganic oxide in the catalyzer, can be at described aluminum contained compound, molecular sieve and water, contain or slurries not argillaceous in add described non-oxide aluminium inorganic oxide and/or its precursor.The precursor of described non-oxide aluminium inorganic oxide refers in catalyst preparation process, can form the material of described non-oxide aluminium inorganic oxide, and the precursor of these non-oxide aluminium inorganic oxides is conventionally known to one of skill in the art.Precursor as silicon oxide can be silicon sol, silicon gel and/or water glass, the precursor of amorphous silicon aluminium can be silicon-aluminum sol and/or silica-alumina gel, and the precursor of zirconium white, titanium oxide, boron oxide, alkaline earth metal oxide can be its oxyhydroxide separately.The consumption of described non-oxide aluminium inorganic oxide and/or its precursor makes and contains 0-10 weight % in the catalyzer, the non-oxide aluminium inorganic oxide of preferred 0-5 weight %.
The condition of described drying and roasting is the cracking catalyst drying of routine and the condition of roasting, as the exsiccant temperature is room temperature-200 ℃, be preferably 80-180 ℃, the temperature of roasting is greater than 200 to 750 ℃, be preferably 300-600 ℃, the time of roasting was at least 0.1 hour, was preferably 0.1-10 hour, more preferably 0.3-4 hour.Described drying means can adopt existing various drying means,, dries spraying drying, preferably oven dry or spray-dired method as oven dry.
Catalyzer provided by the invention is applicable to oil and various cut thereof is carried out catalytic cracking, be particularly suitable for oil and boiling point petroleum fractions greater than 330 ℃, as normal pressure residual oil, vacuum residuum, decompressed wax oil, the normal pressure wax oil, straight-run gas oil, propane is light/and heavily one or more in de-oiling and the wax tailings carry out catalytic cracking, to produce premium-type gasoline, diesel oil and liquefied gas.
The working conditions of catalyzer provided by the invention is conventional cracking reaction condition, and in general, described cracking conditions comprises that temperature of reaction is 350-700 ℃, is preferably 400-650 ℃, and agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) is 1-20, is preferably 2-15.
The following examples will the present invention will be further described.
In the example, the alumina content of used β-alumina trihydrate is 64 weight % (research institute of Shandong Aluminium Industrial Corp products); The alumina content of pseudo-boehmite is 62 weight % (Shandong Aluminium Industrial Corp's products); The alumina content of aluminium colloidal sol is 21.6 weight % (Shandong catalyst plant products); The silica content of silicon sol is 12 weight % (Changhong chemical plant, Beijing products); Kaolinic solid content 76 weight % (China Kaolin Co., Ltd's product); The solid content of polynite is 80 weight % (Hubei Zhong Xiang county iron ore factory products); The phosphorated compound is a chemical pure; The SAPO-11 molecular sieve is pressed example 1 described method preparation among the CN1098214C; HY zeolite (Na
2O content is 1.5 weight %, and silica alumina ratio is 5.3) be with NaY zeolite (Na
2O content is 13.5 weight %, and silica alumina ratio is 5.0, and the Shandong catalyst plant is produced), at water: the NaY zeolite: the solid ammonium chloride weight ratio is exchange 1 hour under the temperature of 10: 1: 1 and 80 ℃, filter the back 550 ℃ of roastings 2 hours, by the above-mentioned steps exchange once, filtration and roasting obtain again; The REY zeolite be a kind of y-type zeolite that contains rare earth (content of rare earth oxide is 18.5 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 1.6 weight %, and silica alumina ratio is 5.4, and the Shandong catalyst plant is produced); The REHY zeolite be a kind of y-type zeolite that contains rare earth (content of rare earth oxide is 8.4 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 3.7 weight %, and silica alumina ratio is 5.6, and the Shandong catalyst plant is produced); The MOY zeolite be a kind of phosphorous and rare earth y-type zeolite (content of rare earth oxide is 8.0 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 1.3 weight %, and in element phosphor, phosphorus content is 1.1 weight %, and silica alumina ratio is 5.6, and the Shandong catalyst plant is produced); DASY
0.0Zeolite is a kind of overstable gamma zeolite (Na
2O content is 1.0 weight %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced); DASY
2.0Zeolite be a kind of overstable gamma zeolite that contains rare earth (content of rare earth oxide is 1.8 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 1.2 weight %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced); The ZSM-5 zeolite is a kind of zeolite (Na with MFI structure
2O content is 0.2 weight %, and silica alumina ratio is 60, and the Shandong catalyst plant is produced); The ZRP-1 zeolite is a kind of zeolite (Na with MFI structure of phosphorous and rare earth
2O content 0.1 weight %, silica alumina ratio is 30, the content of rare earth oxide is 1.7 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, in element phosphor, phosphorus content is 1.9 weight %, and the Shandong catalyst plant is produced); ZSP-1 is a kind of zeolite (Na with MFI structure of phosphorous and iron
2O content is 0.1 weight %, and silica alumina ratio is 30, Fe
2O
3Content is 1.5 weight %, and in element phosphor, phosphorus content is 1.2 weight %, and the Shandong catalyst plant is produced); The Na of Beta zeolite
2O content is 3.2 weight %, and silica alumina ratio is 28, and the Shandong catalyst plant is produced.Above-mentioned silica alumina ratio all refers to the mol ratio of silicon oxide and aluminum oxide.
Example 1-6
Following example illustrates Catalysts and its preparation method provided by the invention.
With β-alumina trihydrate or β-alumina trihydrate and pseudo-boehmite, molecular sieve, phosphorus compound and water (also having clay sometimes) mixing making beating, the slurries that obtain are spray dried to particle and the roasting that diameter is the 40-150 micron, obtain catalyzer C provided by the invention
1-C
6The consumption of β-alumina trihydrate and pseudo-boehmite, the kind of clay and consumption, the kind of the kind of molecular sieve and consumption, phosphorus compound and consumption are listed in respectively among the table 1-4.Spray-dired temperature, maturing temperature and time list in the table 5.Catalyzer C
1-C
6Composition list in the table 6.
Comparative Examples 1
This Comparative Examples illustrates not phosphorated reference catalyst and preparation method thereof.
Method by example 1 prepares catalyzer, and different is not add phosphorus compound, and the consumption difference of clay gets reference catalyst CB
1The consumption of β-alumina trihydrate and pseudo-boehmite, the kind of clay and consumption, the kind of molecular sieve and consumption are listed in respectively among the table 1-4.Spray-dired temperature, maturing temperature and time list in the table 5.Reference catalyst CB
1Composition list in the table 6.
Comparative Examples 2
The explanation of this Comparative Examples does not contain reference catalyst of χ or η-aluminum oxide and preparation method thereof.
Method by example 1 prepares catalyzer, and different is to replace β-alumina trihydrate with pseudo-boehmite, obtains reference catalyst CB
2The consumption of pseudo-boehmite, the kind of clay and consumption, the kind of the kind of molecular sieve and consumption, phosphorus compound and consumption are listed in respectively among the table 1-4.Spray-dired temperature, maturing temperature and time list in the table 5.Reference catalyst CB
2Composition list in the table 6.
Example 7
This example illustrates Catalysts and its preparation method provided by the invention.
With 93.8 kilograms of β-alumina trihydrates, 72.6 kilograms of pseudo-boehmites, 54 kilograms of DASY
2.0Molecular sieve, 30 kilograms of ZRP-1 molecular sieves, 6 kilograms of SAPO-11 molecular sieves, 126.3 kilogram kaolin, 50 kilograms of silicon sol and deionized water mix making beating, and the slurries that obtain are spray dried to the particle that diameter is the 40-150 micron under 180 ℃ temperature, with concentration 300 kilograms of the solids (dry basis) behind 303.8 kilograms of impregnation dryings of ammonium dihydrogen phosphate aqueous solution of 1.6 weight %, then, 500 ℃ roasting temperatures 2 hours, obtain catalyzer C provided by the invention
7Catalyzer C
7Composition list in the table 6.
Example 8
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 6 prepares catalyzer, and different is to replace described pseudo-boehmite with 69.4 kilograms of aluminium colloidal sols, obtains catalyzer C provided by the invention
8Catalyzer C
8Composition list in the table 6.
Table 1
| Example number | β-alumina trihydrate consumption, kilogram | Pseudo-boehmite/aluminium colloidal sol consumption, kilogram |
| 1 | 61.7 | - |
| Comparative Examples 1 | 61.7 | - |
| Comparative Examples 2 | - | 63.7 |
| 2 | 8.6 | 41.1 |
| 3 | 56.3 | 35.5 |
| 4 | 68.8 | 37.7 |
| 5 | 4.7 | 3.2 |
| 6 | 39.1 | 24.2 |
Table 2
| Example number | The molecular sieve kind | The molecular sieve consumption, kilogram |
| 1 | REHY | 26 |
| Comparative Examples 1 | REHY | 26 |
| Comparative Examples 2 | REHY | 26 |
| 2 | DASY 0.0+ZSP-1 | 39+10 |
| 3 | HY+ZSM-5 | 17+23 |
| 4 | REY+β | 14+8 |
| 5 | MOY+DASY 2.0+ZRP-1 | 15+19+7 |
| 6 | MOY+ZSM-5 | 25+10 |
Table 3
| Example number | Clay types | The clay consumption, kilogram |
| 1 | Kaolin | 42.1 |
| Comparative Examples 1 | Kaolin | 45.4 |
| Comparative Examples 2 | Kaolin | 42.1 |
| 2 | Kaolin | 19.1 |
| 3 | - | - |
| 4 | Polynite | 12.5 |
| 5 | Kaolin | 67.1 |
| 6 | Kaolin | 31.6 |
Table 4
| Example number | The phosphorus compound kind | The phosphorus compound consumption, kilogram |
| 1 | Secondary ammonium phosphate | 4.7 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Secondary ammonium phosphate | 4.7 |
| 2 | Sodium hexametaphosphate 99 | 7.9 |
| 3 | Ammonium phosphate | 4.2 |
| 4 | Ammonium phosphate | 1.3 |
| 5 | Primary ammonium phosphate | 4.9 |
| 6 | Primary ammonium phosphate | 1.6 |
Table 5
| Example number | Drying temperature, ℃ | Maturing temperature, ℃ | Roasting time, hour |
| 1 | 110 | 500 | 1 |
| Comparative Examples 1 | 110 | 500 | 1 |
| Comparative Examples 2 | 110 | 500 | 1 |
| 2 | 120 | 350 | 3.5 |
| 3 | 120 | 600 | 0.5 |
| 4 | 120 | 450 | 0.8 |
| 5 | 160 | 550 | 1.5 |
| 6 | 90 | 550 | 1.5 |
Table 6
| Example number | The catalyzer numbering | η-alumina content, weight % | Gama-alumina content, weight % | Molecular sieve content, weight % | Clay content, weight % | P 2O 5Content, weight % |
| 1 | C 1 | 39.5 | 0 | 26.0 | 32.0 | 2.5 |
| Comparative Examples 1 | CB 1 | 39.5 | 0 | 26.0 | 34.5 | 0 |
| Comparative Examples 2 | CB 2 | 0 | 39.5 | 26.0 | 32.0 | 2.5 |
| 2 | C 2 | 5.5 | 25.5 | 49.0 | 14.5 | 5.5 |
| 3 | C 3 | 36.0 | 22.0 | 40.0 | 0 | 2.0 |
| 4 | C 4 | 44.0 | 23.4 | 22.0 | 10.0 | 0.6 |
| 5 | C 5 | 3.0 | 2.0 | 41.0 | 51.0 | 3.0 |
| 6 | C 6 | 25.0 | 15.0 | 35.0 | 24.0 | 1.0 |
| 7 | C 7 | 20.0 | 15.0/2.0 * | 30.0 | 32.0 | 1.0 |
| 8 | C 8 | 25.0 | 15.0 | 35.0 | 24.0 | 1.0 |
*2.0 weight % is the content of silicon oxide
Example 9-14
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Respectively with catalyzer C
1-C
6At 800 ℃, wore out 8 hours with 100% water vapour.On miniature fluidized bed reaction, with the catalyzer C after above-mentioned the wearing out
1-C
61# stock oil carries out catalytic cracking shown in the his-and-hers watches 7, and the catalyzer loading amount is 9 grams.Reaction conditions and reaction result are listed in the table 8.
Wherein, transformation efficiency=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield; Total liquid receipts=yield of liquefied gas+yield of gasoline+diesel yield.Gasoline is meant that boiling range is C
5-221 ℃ cut, diesel oil are meant that boiling range is 221-343 ℃ a cut, and liquefied gas is meant C
3-C
4Cut, gas is H
2-C
2Cut.
Comparative Examples 3-4
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 9 wears out to catalyzer, and under same condition, same stock oil is carried out catalytic cracking, and that different is reference catalyst CB1 and the CB2 that catalyst system therefor is respectively Comparative Examples 1 and Comparative Examples 2 preparations, and reaction conditions and reaction result are listed in the table 8.
Table 7
| 1# stock oil | The mixing oil of decompressed wax oil and vacuum residuum |
| Density (20 ℃), gram per centimeter 3 | 0.9044 |
| Refractive power (20 ℃) | 1.5217 |
| Viscosity (100 ℃), millimeter 2/ second | 9.96 |
| Zero pour, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| Elementary composition, weight % C H S N | 85.98 12.86 0.55 0.18 |
| Carbon residue, weight % | 3.0 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | 243 294 316 395 429 473 - |
Table 8
| Example number | 9 | Comparative Examples 3 | Comparative Examples 4 | 10 | 11 | 12 | 13 | 14 |
| The catalyzer numbering | C 1 | CB 1 | CB 2 | C 2 | C 3 | C 4 | C 5 | C 6 |
| Temperature of reaction, ℃ | 510 | 510 | 510 | 460 | 550 | 500 | 480 | 510 |
| Agent-oil ratio | 4.0 | 4.0 | 4.0 | 4.5 | 3.5 | 5 | 6 | 4 |
| Weight hourly space velocity, hour -1 | 16.0 | 16.0 | 16.0 | 15.5 | 18.2 | 14.3 | 12.0 | 16.2 |
| Transformation efficiency, weight % | 72.6 | 70.3 | 69.8 | 78.6 | 74.8 | 72.9 | 77.6 | 75.4 |
| Total liquid is received weight % | 79.9 | 74.0 | 70.9 | 85.6 | 80.1 | 78.9 | 84.4 | 80.9 |
| Product is formed, weight % | ||||||||
| Dry gas | 1.7 | 2.2 | 3.4 | 1.7 | 2.2 | 1.9 | 1.9 | 1.9 |
| Liquefied gas | 18.4 | 17.3 | 16.6 | 25.4 | 32.0 | 23.4 | 21.1 | 23.8 |
| Gasoline | 47.1 | 42.8 | 41.0 | 45.1 | 35.5 | 41.3 | 48.3 | 43.9 |
| Diesel oil | 14.4 | 13.9 | 13.3 | 15.1 | 12.6 | 14.2 | 15.0 | 13.2 |
| Coke | 5.4 | 8.0 | 8.8 | 6.4 | 5.1 | 6.3 | 6.3 | 5.8 |
| Unconverted heavy oil | 13.0 | 15.8 | 16.9 | 6.3 | 13.6 | 12.9 | 7.4 | 11.4 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 34.0 24.8 25.2 | 36.1 23.2 23.5 | 37.0 21.1 22.2 | 28.8 28.6 28.9 | 31.3 24.3 26.5 | 34.8 26.3 24.1 | 29.4 27.9 28.3 | 30.0 27.4 27.6 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 905 31.2 33.4 | 928 25.4 28.0 | 935 18.0 27.0 | 890 41.7 36.0 | 915 29.2 33.2 | 920 28.2 32.2 | 896 41.0 35.5 | 902 32.4 33.9 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 6.5 6.0 4.4 | 5.8 5.6 4.0 | 5.4 5.3 3.9 | 9.2 9.6 5.0 | 12.8 13.5 4.2 | 8.5 9.1 4.3 | 7.3 7.6 4.2 | 7.6 8.0 4.5 |
Example 15-16
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Respectively with catalyzer C
7-C
8At 8100 ℃, wore out 17 hours with 100% water vapour.On the small-sized fluidized bed reaction unit, with the catalyzer C after above-mentioned the wearing out
7-C
82# stock oil carries out catalytic cracking shown in the his-and-hers watches 9, and the catalyzer loading amount is 90 grams.Reaction conditions and reaction result are listed in the table 10.
Table 9
| 2# stock oil density (20 ℃), gram per centimeter 3Carbon residue, weight % refractive power (70 ℃) viscosity (80 ℃), millimeter 2/ second viscosity (100 ℃), millimeter 2/ second condensation point, ℃ aniline point, ℃ | Long residuum |
| 0.8977 5.14 1.4884 23.61 13.72 44 97.7 | |
| Elementary composition, weight % C H S N | 86.89 12.77 0.13 0.21 |
| Four components, weight % stable hydrocarbon aromatic hydrocarbons gum asphalt | 62.7 23.0 12.7 1.6 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 60% | 283 350 374 432 477 511 |
| Characterization factor | 12.3 |
Table 10
| Example number | 15 | 16 |
| The catalyzer numbering | C 7 | C 8 |
| Temperature of reaction, ℃ | 520 | 540 |
| Agent-oil ratio | 5.0 | 4.0 |
| Weight hourly space velocity, hour -1 | 22.5 | 25.0 |
| Transformation efficiency, weight % | 76.7 | 79.5 |
| Total liquid is received weight % | 79.6 | 82.0 |
| Product is formed, weight % | ||
| Dry gas | 2.7 | 2.6 |
| Liquefied gas | 29.7 | 30.9 |
| Gasoline | 37.8 | 40.2 |
| Diesel oil | 12.1 | 10.9 |
| Coke | 6.5 | 5.8 |
| Unconverted heavy oil | 11.2 | 9.6 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 33.0 28.3 29.2 | 31.1 28.9 31.2 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 899 41.2 34.7 | 892 41.4 35.8 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 11.1 7.6 6.4 | 11.6 8.5 6.9 |
From the result of table 8 as can be seen, compare with the use reference catalyst, use catalyzer provided by the invention that same stock oil is carried out catalytic cracking, transformation efficiency and total liquid are received and are significantly improved, and, reduced olefin content in gasoline significantly, improved aromatic hydrocarbons and the isoparaffin content in the gasoline, reduced diesel oil density, improved the aniline point and the cetane value of diesel oil, low-carbon alkene in the liquefied gas (particularly third is rare) and Trimethylmethane content significantly improve.This explanation, catalyzer provided by the invention not only has higher cracking activity, and, improved the gasoline in the cracked product significantly, the quality of diesel oil and liquefied gas.The result of table 10 shows that equally catalyzer provided by the invention has the cracking activity higher than prior art, and, the gasoline in the cracked product, the quality of diesel oil and liquefied gas is higher.
Claims (14)
1. hydrocarbon cracking catalyzer, this catalyzer contains aluminum oxide and molecular sieve, contain or do not contain clay, it is characterized in that, described aluminum oxide is η-aluminum oxide and/or χ-aluminum oxide, or the mixture of η-aluminum oxide and/or χ-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus, with the catalyzer total amount is benchmark, the content of η-aluminum oxide and/or χ-aluminum oxide is 0.5-50 weight %, and the content of gama-alumina is 0-50 weight %, and the content of molecular sieve is 10-70 weight %, the content of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-8 weight %.
2. catalyzer according to claim 1 is characterized in that, the content of η-aluminum oxide and/or χ-aluminum oxide is 5-45 weight %, the content of gama-alumina is 0-40 weight %, the content of molecular sieve is 20-50 weight %, and the content of clay is 0-60 weight %, with P
2O
5Meter, the content of phosphorus is 0.5-6 weight %.
3. catalyzer according to claim 1 and 2 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.
4. catalyzer according to claim 3 is characterized in that described zeolite is selected from one or more in large pore zeolite and the mesopore zeolite.
5. catalyzer according to claim 4 is characterized in that, described large pore zeolite is selected from one or more in faujusite, Beta zeolite, the mordenite.
6. catalyzer according to claim 5 is characterized in that described large pore zeolite is selected from y-type zeolite, one or more in the Beta zeolite.
7. catalyzer according to claim 4 is characterized in that described mesopore zeolite is selected from one or more in the zeolite with MFI structure.
8. catalyzer according to claim 1 and 2 is characterized in that, described molecular screening one or more in y-type zeolite, Beta zeolite, the zeolite with MFI structure, SAPO molecular sieve.
9. catalyzer according to claim 1 and 2 is characterized in that described clay is selected from one or more in kaolin, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
10. claim 1 Preparation of catalysts method, this method comprises and will contain aluminum compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, it is characterized in that, described aluminum compound is the aluminum compound that can form η-aluminum oxide and/or χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, the compound that before roasting, also adds phosphorus, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 η-aluminum oxide of weight % and/or χ-aluminum oxide, the gama-alumina of 0-50 weight %, the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %.
11. method according to claim 10 is characterized in that, the described aluminum compound that can form η-aluminum oxide and/or χ-aluminum oxide is α-alumina trihydrate and/or β-alumina trihydrate; The described aluminum compound that can form gama-alumina is boehmite, pseudo-boehmite and/or aluminium colloidal sol.
12. method according to claim 10 is characterized in that, described phosphorus compound is selected from one or more in phosphoric acid, phosphoric acid salt, phosphorous acid, phosphite, tetra-sodium, pyrophosphate salt, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate.
13. method according to claim 12 is characterized in that, described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99.
14. method according to claim 10, it is characterized in that, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, η-aluminum oxide and/or the χ-aluminum oxide of 5-45 weight %, the gama-alumina of 0-40 weight %, the molecular sieve of 20-50 weight %, the clay of 0-60 weight % is with P
2O
5Meter, the phosphorus of 0.5-6 weight %.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
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| CN1916117B (en) * | 2005-08-17 | 2011-04-06 | 中国石油化工股份有限公司石油化工科学研究院 | Method for cracking hydrocarbon oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057408A (en) * | 1990-06-20 | 1992-01-01 | 中国石油化工总公司石油化工科学研究院 | The catalyst for cracking that contains silica-rich zeolite |
| US5547564A (en) * | 1989-03-02 | 1996-08-20 | W. R. Grace & Co.-Conn. | Catalytic Cracking |
| CN1341697A (en) * | 2000-09-07 | 2002-03-27 | 中国石油化工股份有限公司 | Vanadium-resistant hydrocarbon cracking catalyst and preparation method thereof |
-
2004
- 2004-01-19 CN CNB2004100009483A patent/CN1323133C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547564A (en) * | 1989-03-02 | 1996-08-20 | W. R. Grace & Co.-Conn. | Catalytic Cracking |
| CN1057408A (en) * | 1990-06-20 | 1992-01-01 | 中国石油化工总公司石油化工科学研究院 | The catalyst for cracking that contains silica-rich zeolite |
| CN1341697A (en) * | 2000-09-07 | 2002-03-27 | 中国石油化工股份有限公司 | Vanadium-resistant hydrocarbon cracking catalyst and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
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