CN1323134C - Method for cracking hydrocarbon oil - Google Patents
Method for cracking hydrocarbon oil Download PDFInfo
- Publication number
- CN1323134C CN1323134C CNB2004100009500A CN200410000950A CN1323134C CN 1323134 C CN1323134 C CN 1323134C CN B2004100009500 A CNB2004100009500 A CN B2004100009500A CN 200410000950 A CN200410000950 A CN 200410000950A CN 1323134 C CN1323134 C CN 1323134C
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- reaction
- reaction zone
- weight
- aluminum oxide
- reactor
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- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 76
- 238000005336 cracking Methods 0.000 title claims abstract description 67
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 237
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 239000002808 molecular sieve Substances 0.000 claims abstract description 49
- 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 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 34
- 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 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 239000010457 zeolite Substances 0.000 claims description 80
- 229910021536 Zeolite Inorganic materials 0.000 claims description 77
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 73
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000011069 regeneration method Methods 0.000 claims description 37
- 230000008929 regeneration Effects 0.000 claims description 31
- -1 polynite Chemical compound 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 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
- 238000010517 secondary reaction Methods 0.000 claims description 9
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 5
- 241000269350 Anura Species 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 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
- 229910052624 sepiolite Inorganic materials 0.000 claims description 3
- 235000019355 sepiolite Nutrition 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
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 59
- 239000003502 gasoline Substances 0.000 abstract description 36
- 239000002283 diesel fuel Substances 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 23
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 description 39
- 239000007789 gas Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 30
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 30
- 239000004411 aluminium Substances 0.000 description 26
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 17
- 230000035939 shock Effects 0.000 description 17
- 150000004684 trihydrates Chemical class 0.000 description 17
- 229910052761 rare earth metal Inorganic materials 0.000 description 16
- 150000002910 rare earth metals Chemical class 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 14
- 238000000926 separation method Methods 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 13
- 238000004523 catalytic cracking Methods 0.000 description 13
- 229910052809 inorganic oxide Inorganic materials 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 239000010703 silicon Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 4
- 235000019289 ammonium phosphates Nutrition 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 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 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 3
- 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 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
- 101710194948 Protein phosphatase PhpP Proteins 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
- 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
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- 239000002184 metal Substances 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
- 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 description 2
- 239000011591 potassium Substances 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 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
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
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- 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
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
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- 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
- 239000010913 used oil Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for cracking hydrocarbon oil, which comprises the following steps: in a reactor comprising two reaction zones, contacting the hydrocarbon oil with a cracking catalyst for a first reaction and a second reaction, separating reaction products and the catalyst, and regenerating the catalyst for reuse. The cracking catalyst contains aluminum oxide or molecular sieves 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. The catalyst also contains phosphorus. 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 sieves, 0 to 75 wt% of the clay, and 0.1 to 8 wt% of the phosphorus measured by P2O5. The reaction temperature of the first reaction zone is from 450 to 650 DEG C, reaction pressure is from 0.1 to 0.5MPa, and catalyst-oil ratio is from 1 to 30; the reaction temperature of the second reaction zone is from 430 to 550 DEG C, reaction pressure is from 0.1 to 0.5MPa, and catalyst-oil ratio is from 1 to 30. The method not only has relatively high heavy oil cracking capacity, but also notably increases the quality of gasoline, diesel oil and liquefied gas in cracked products.
Description
Technical field
The invention relates to a kind of cracking method for hydrocarbon oil.
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 the x-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 and use the cracking method of this catalyzer to have stronger heavy oil cracking ability and lightweight oil selectivity preferably, but but can not reduce olefin content in gasoline, improve the catalytic cracking diesel oil quality, can not improve the content of low-carbon alkene and Trimethylmethane in the liquefied gas.
CN1078094C discloses a kind of riser reactor that is used for fluid catalytic cracking, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, second reaction zone of first reaction zone, enlarged-diameter, the outlet area of reduced are connected with one section level pipe at the outlet area end.It is different with the processing condition of second reaction zone that this reactor both can satisfy first reaction zone, can make stock oil of different nature carry out the segmentation cracking again.
CN1076751C discloses a kind of catalysis conversion method of producing Trimethylmethane and being rich in isoparaffin gasoline, the stock oil that comprises preheating enters in the reactor that comprises 2 reaction zones, in the presence of water vapor, contact with the cracking catalyst of heat, carry out once and secondary reaction, reaction conditions comprises that the temperature of first reaction zone is 530-620 ℃, reaction times is 0.5-2 second, the temperature of second reaction zone is 460-530 ℃, reaction times is 2-30 second, reaction product isolated, reclaimable catalyst enters revivifier behind stripping, recycle after burning.
Summary of the invention
The purpose of this invention is to provide a kind of new stronger heavy oil cracking ability that has, and the olefin(e) centent of gasoline is lower, diesel quality is higher, and has the cracking method for hydrocarbon oil of 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, produced special synergistic effect, used this cracking catalyst and adopt the cracking method of the reactor that comprises two reaction zones not only to have stronger cracking ability, simultaneously, can significantly improve the gasoline in the cracked product, the quality of diesel oil and liquefied gas.
Method provided by the invention is included in the reactor that comprises two reaction zones, hydrocarbon ils is contacted with a kind of cracking catalyst, carry out once and secondary reaction, reaction product isolated and catalyzer, with catalyst regeneration, catalyst recirculation after the regeneration is used, described cracking catalyst contains aluminum oxide and molecular sieve, contain or do not contain clay, wherein, described aluminum oxide is η-aluminum oxide and/or x-aluminum oxide, or the mixture of η-aluminum oxide and/or x-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus, is benchmark with the catalyzer total amount, and the content of η-aluminum oxide and/or x-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 %; The first reaction zone temperature of reaction is 450-650 ℃, and reaction pressure is the 0.1-0.5 MPa, and agent-oil ratio is 1-30; The second reaction zone temperature of reaction is 430-550 ℃, and reaction pressure is the 0.1-0.5 MPa, and agent-oil ratio is 1-30.
Method provided by the invention not only has higher heavy oil cracking ability, 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.
Description of drawings
Fig. 1 and 2 is the schematic flow sheet of method provided by the invention.
Embodiment
According to method provided by the invention, described catalyzer contains aluminum oxide and molecular sieve, contain or do not contain clay, wherein, described aluminum oxide is η-aluminum oxide and/or x-aluminum oxide, or the mixture of η-aluminum oxide and/or x-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 x-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
2Meter, the content of phosphorus is 0.1-8 weight %.Under the preferable case, the content of η-aluminum oxide and/or x-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.
Described catalyzer 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 %.
Described Preparation of catalysts method 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 x-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or x-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 the η-aluminum oxide of weight % and/or x-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 %.
The described aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide can be any in catalyst preparation process, can form the aluminum compound of η-aluminum oxide and/or x-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 the η-aluminum oxide of 0.5-50 weight % and/or x-aluminum oxide, 0-50 weight %, and the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
2Meter, the phosphorus of 0.1-8 weight %.Under the preferable case, the consumption of each component makes η-aluminum oxide and/or the x-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 and/or water glass, and 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.
Described reactor can be one of reactor that has two reaction zones, or has the combination between two reactors of a reaction zone.For example, described reactor can be one of the riser reactor that comprises two reaction zones, fixed-bed reactor, fluidized-bed reactor, moving-burden bed reactor, or comprise one or both the combination of two reactors among the riser reactor, fixed-bed reactor, fluidized-bed reactor, moving-burden bed reactor of a reaction zone, wherein, riser reactor, fixed-bed reactor, fluidized-bed reactor or the moving-burden bed reactor that comprises a reaction zone respectively is a reaction zone.
Preferred reactor is the combination between riser reactor or two riser reactors, as comprise two reaction zones reducing riser reactor (as the disclosed riser reactor that is used for fluid catalytic cracking of CN1078094C), comprise the common riser reactor of two reaction zones or comprise the combination of two common riser reactors of a reaction zone.
According to method provided by the invention, the first reaction zone temperature of reaction is 450-650 ℃, is preferably 480-600 ℃, and reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, and agent-oil ratio is 1-30, is preferably 2-15; The second reaction zone temperature of reaction is 430-550 ℃, is preferably 450-530 ℃, and reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, and agent-oil ratio is 1-30, is preferably 2-15.
Here, agent-oil ratio is the internal circulating load and the weight ratio that enters the hydrocarbon ils of riser reactor in the unit time of the catalyzer of riser reactor in the unit time, or catalyzer and weight ratio by the preceding hydrocarbon ils of the unreacted of this catalyzer in fixed-bed reactor, fluidized-bed reactor or the moving-burden bed reactor.For the riser reactor with two reaction zones, because the reactant flow of second reaction zone is the reaction product and the mixture of catalysts of first reaction zone basically, therefore, the agent-oil ratio of first reaction zone and second reaction zone is basic identical.And for the fixed-bed reactor that comprise two reaction zones, fluidized-bed reactor or moving-burden bed reactor, the fixed-bed reactor that perhaps comprise a reaction zone, fluidized-bed reactor, moving-burden bed reactor, riser reactor itself or combine between them comprise two reaction zone reactors, can be by amount of regulating catalyzer in the beds or the amount that enters the catalyzer of each riser reactor, regulate the agent-oil ratio of first reaction zone and second reaction zone, therefore, for the fixed-bed reactor that comprise two reaction zones, fluidized-bed reactor or moving-burden bed reactor, the fixed-bed reactor that perhaps comprise a reaction zone, fluidized-bed reactor, moving-burden bed reactor, riser reactor itself or combine between them comprise two reaction zone reactors, the agent-oil ratio of first reaction zone and second reaction zone can be the same or different.
For fixed bed, fluidized-bed and moving-burden bed reactor, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 450-650 ℃, is preferably 480-600 ℃, and reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, and weight hourly space velocity is 1-40 hour
-1, be preferably 2-30 hour
-1, agent-oil ratio is 1-30, is preferably 2-15, more preferably 3-10; The cracking reaction condition of second reaction zone comprises that temperature of reaction is 430-550 ℃, is preferably 450-530 ℃, and reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, and weight hourly space velocity is 1-40 hour
-1, be preferably 2-30 hour
-1, agent-oil ratio is 1-30, is preferably 2-15, more preferably 3-10.Here, weight hourly space velocity is for per hour entering the weight ratio of the hydrocarbon ils and the catalyzer in the first or second reaction zone bed of reactive system.
According to method provided by the invention, when described reactor is riser reactor, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 450-650 ℃, be preferably 480-600 ℃, reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, reaction times is 0.4-3.5 second, be preferably 0.5-3 second, agent-oil ratio is 1-30, is preferably 2-15; The second reaction zone temperature of reaction is 430-550 ℃, is preferably 450-530 ℃, and reaction pressure is the 0.1-0.5 MPa, is preferably the 0.1-0.3 MPa, and the reaction times is 2-30 second, is preferably 3-15 second, and agent-oil ratio is 1-30, is preferably 2-15.
The condition of riser reactor outlet area is conventional condition, and these conditions comprise that temperature is 400-550 ℃, are preferably 420-530 ℃, and be 0.1-3 second duration of contact, is preferably 0.1-2 second.The condition of riser reactor outlet area is conventionally known to one of skill in the art.
The cracking reaction condition of each reaction zone can adopt conventional method to adjust, as the temperature of regulating a certain reaction zone beds by heating installation, interchanger is set before the reaction zone of needs, regulate the catalyzer that enters respective reaction zones temperature, regulate hydrocarbon ils feeding temperature, inject the cold shock agent at first reaction zone of riser reactor and the combining site of second reaction zone.Regulate hydrocarbon oil feed speed and come adjusting reaction time.
In order to suppress the cracking and the heat cracking reaction excessively of riser tube outlet area, can take gas-solid sharp separation or add the method for cold shock agent (being called terminator here) in the junction of riser reactor second reaction zone and outlet area, the temperature of riser reactor outlet area is reduced.The method of the method for gas-solid sharp separation and adding cold shock agent is conventionally known to one of skill in the art, and the method for gas-solid sharp separation is referring to EP163978, EP139392, EP564678, US5104517, US5308474.The method that adds the cold shock agent is referring to US5089235, EP593823.
Described interchanger and cold shock agent (terminator) are conventionally known to one of skill in the art.Described interchanger can be tube and shell heat exchanger, plate-type heat exchanger, floating coiler heat exhanger and/or hot-blast heater.Described cold shock agent (terminator) can be selected from one or more in raw gasline, gasoline, diesel oil, separation column turning oil, the water.
When cracking case was riser reactor, method provided by the invention can directly utilize existing reaction-regeneration system to finish.The variety of way of described existing reaction-regeneration system is conventionally known to one of skill in the art, and existing reaction-regeneration system as described can be different with the arrangement of revivifier according to settling vessel and same high block form, height block form or coaxial-type reaction-regeneration system that divide.Wherein, riser reactor can be deep into the settling vessel from settling vessel, stripping stage center, also can be the peripheral hardware riser reactor.Wherein said riser reactor comprises any type of riser tube feed nozzle, mixing temperature control techniques, reaction terminating facility etc." residual oil complete processing ", (Li Chunnian writes the 282-338 page or leaf, Sinopec press published in 2002) existing catalytic cracking reaction-regeneration system rapidly is summarized, as the ROCC-V process unit, full grand celebration vacuum residue catalytic (VR-RFCC) process unit, the residual oil fluid catalytic cracking RFCC device of U.S. Dao Daer (Total) company of two-stage regeneration, the atmospheric residue of the employing two-stage regeneration that A Xilan (Ashland) company and UOP develop jointly transforms the RCC process unit, the FCC process unit that burns the pot type highly efficient regeneration of UOP, the mobile type riser reactor catalytic cracking unit that the riser reactor that flexicracking (Flexicracking IIIR) technology of Exxon (Exxon) company relates to combines with bed reactor, one section reverse-flow regenerating unit and super positive flow pattern FCC process unit that heavy oil cracking (HOC) technology of Kellogg (Kellogg) company relates to.Described reaction-regeneration system is not limited to above-mentioned giving an example.
Described revivifier can be single hop regeneration or two-stage regeneration.Described single hop regeneration can be regeneration of turbulent bed single hop or the regeneration of fast bed single hop.Described two-stage regeneration can be the turbulent bed two-stage regeneration, burn jar the two-stage regeneration, fast bed two-stage regeneration or the tubular type that constitute jointly with conventional turbulent bed regenerates.Described turbulent bed two-stage regeneration can be two device adverse current two-stage regenerations, two device cross-flow two-stage regeneration.Described burn jar the two-stage regeneration that constitutes jointly with conventional turbulent bed can be prepositionly burn a jar two-stage regeneration, postposition is burnt a jar two-stage regeneration.Heat collector or external warmer in described revivifier can have as required.Heat collector can be horizontally disposed or vertically arranged bed spiral coil cooling tube in described.Described external warmer can be upflowing, downflow system, back-mixing formula or Pneumatic-control type external warmer." residual oil complete processing ", 282-338 page or leaf (Li Chunnian writes, and Sinopec press published in 2002) is also summed up revivifier.
According to specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 1.Described reactor is the disclosed riser reactor that is used for fluid catalytic cracking of CN1078094C, this reactor vertically is followed successively by second reaction zone of co-axial each other pre lift zone, first reaction zone, enlarged-diameter, the outlet area of reduced from bottom to up, is connected with one section level pipe at the outlet area end.Under the preferable case, the diameter of first reaction zone of this reactor and the ratio of pre lift zone diameter are 1-1.2, and the ratio of the diameter of second reaction zone and first reaction zone diameter is 1.5-5.0, and the ratio of the diameter of outlet area and first reaction zone diameter is 0.8-1.5; The height of pre lift zone accounts for the 5-20% of total reactor height, the height of first reaction zone accounts for the 10-30% of total reactor height, the height of second reaction zone accounts for the 30-60% of total reactor height, the height of outlet area accounts for the 0-20% of total reactor height, first reaction zone and the second reaction zone combining site are round table-like, its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is the 30-80 degree, second reaction zone and outlet area combining site also are round table-like, its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is the 45-85 degree.
From the catalyzer after the regeneration of revivifier 1 or from catalyzer after the regeneration of revivifier 1 and the pre lift zone 5 that enters riser reactor through pipeline 4 from the mixture of the live catalyst of storage tank 3 through pipeline 2, described catalyzer is advanced into first reaction zone 9 of riser reactor under the pre-lifting water vapour from pipeline 6 drives, simultaneously, from the hydrocarbon ils after the preheating of pipeline 7 with from the atomized water vapor mixing of pipeline 8, enter first reaction zone 9 of riser reactor, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carry out a cracking reaction, inject the cold shock agent from pipeline 11 in the junction of first reaction zone 9 and second reaction zone 10, reactant flow with continue to go upward to second reaction zone 10 after the cold shock agent mixes, carry out secondary reaction.Logistics behind the secondary reaction continues up, by outlet area 12, through level pipe 13, enters the settling vessel 14 of separation system, and the cyclonic separator in the settling vessel 14 separates catalyzer with crackate.In order to suppress the cracking and the heat cracking reaction excessively in riser tube exit, can take gas-solid sharp separation or, add terminators through pipeline 15 in the junction of the outlet area 12 and second reaction zone 10, reduce the temperature of reactant flow.Isolated catalyzer enters the stripper 16 of separation system, with water vapor counter current contact from pipeline 17, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 18 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 1 regeneration through inclined tube 19 to be generated.
According to another one specific embodiment of the present invention, method provided by the invention can be undertaken by flow process shown in Figure 2.Three flow processs shown in Figure 2 are identical with flow process shown in Figure 1, be described reactor be the common riser reactor that comprises two reaction zones.
Wherein, described common riser reactor can be any common riser reactor, first reaction zone is lower part of riser reaction zone, second reaction zone is upper part of riser reaction zone, pre lift zone accounts for the 5-20% of riser reaction zone total length, the length of first reaction zone accounts for the 10-30% of riser reaction zone total length, and the length of second reaction zone accounts for the 30-60% of riser reaction zone total length, and outlet area accounts for the 0-20% of riser reaction zone total length.
The effect of atomized water steam is to make the hydrocarbon ils atomizing effect better, makes hydrocarbon ils and catalyst mix more even.The effect that is used as the water vapor of pre-lifting medium is that catalyzer is quickened, and forms density uniform catalyst piston flow at pre lift zone.Described atomized water steam and the pre-consumption that promotes water vapor are conventionally known to one of skill in the art, in general, water-oil ratio is 0.03-0.3, be preferably 0.05-0.15, here, water-oil ratio be enter in the unit time reactor as the pre-water vapour that promotes medium and atomized water steam and the weight ratio that enters the hydrocarbon ils of reactor in the unit time.Wherein, promoting water vapor in advance can be with other pre-medium that promotes, as in refinery dry gas, light paraffins, the light olefin one or more, or one or more and the gas mixture replacement of water vapor in them.
The effect of water stripping steam is that the oil gas that is full of between the granules of catalyst and in the particle hole is cemented out, and improves the oil product productive rate.The consumption that is used for steam stripped water vapor is conventionally known to one of skill in the art.In general, the consumption that is used for steam stripped water vapor accounts for the 0.1-0.8 weight % of catalyst recirculation amount, is preferably 0.2-0.4 weight %.
In revivifier 1, the regenerative process of catalyzer is under oxygen-containing atmosphere, and the process of carbon deposit in the burn off catalyzer, this process are conventionally known to one of skill in the art.Described oxygen containing atmosphere can be oxygen or any mixed gas that contains oxygen, and oxygen-containing atmosphere commonly used is an air.Described regeneration temperature is conventionally known to one of skill in the art, and in general, described regeneration temperature is 600-770 ℃, preferred 650-730 ℃.
Because catalyzer has the little amount of catalyst loss after circulation after a while, therefore, the effect of storage tank 3 is to be used for catalyzer regular or that irregular postreaction consumed.
Method provided by the invention is suitable for various hydrocarbon ils are carried out catalytic cracking to produce high-quality gasoline, diesel oil and liquefied gas.Described hydrocarbon ils is selected from oil and various cut thereof, be preferably oil and boiling point greater than 330 ℃ petroleum fractions, as normal pressure residual oil, vacuum residuum, decompressed wax oil, the normal pressure wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the gelatin liquefaction product one or more.
The following examples will the present invention will be further described.
In the example, unless stated otherwise, 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 80 weight % of polynite (Hubei Zhong Xiang county iron ore factory product), the phosphorated compound is chemical pure (Beijing chemical reagents corporation product), and 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: exchange is 1 hour under the temperature of solid ammonium chloride weight ratio=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 1.31 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 molecular sieve (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 molecular sieve (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
20 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.Used revivifier is the preposition jar two-stage regeneration device that burns; The consumption that is used for steam stripped water vapor accounts for about 0.4 weight % of catalyst recirculation amount.Because in all examples, the agent-oil ratio of first reaction zone and second reaction zone is all basic identical, therefore, given agent-oil ratio all is agent-oil ratios of first reaction zone or second reaction zone in the example.
Example 1-6
Following example illustrates method catalyst system therefor provided by the invention and preparation method thereof.
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
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.Drying 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 x 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.Drying temperature, maturing temperature and time list in the table 5.Reference catalyst CB
2Composition list in the table 6.
Example 7
This example illustrates method catalyst system therefor provided by the invention and preparation method thereof.
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
7Catalyzer C
7Composition list in the table 6.。
Example 8
This example illustrates method catalyst system therefor provided by the invention and preparation method thereof.
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
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+ |
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 degree 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 9-11
Following example illustrates method provided by the invention.
Carry out catalytic cracking according to 1# stock oil shown in the flow process his-and-hers watches 7 shown in Figure 1.Catalyst system therefor is respectively the catalyzer C of example 1-3 preparation
1-C
3Described reactor is the disclosed reducing riser reactor of CN1078094C, the height of reactor is 4000 millimeters, the height of pre lift zone 5 is 500 millimeters, interior diameter is 12 millimeters, the height of first reaction zone 9 is 1200 millimeters, the height of second reaction zone 10 is 1550 millimeters, the interior diameter of first reaction zone 9 is 14 millimeters, the interior diameter of second reaction zone 10 is 22 millimeters, the interior diameter of outlet area 12 is 14 millimeters, highly be 750 millimeters, the combining site of first reaction zone 9 and second reaction zone 10 is round table-like, and its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is 60 degree, second reaction zone 10 also is round table-like with the combining site of outlet area 12, and its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is 60 degree.
Enter the pre lift zone 5 of riser reactor through pipeline 2 from the catalyzer after the regeneration of revivifier 1, described catalyzer is advanced into first reaction zone 9 of riser reactor under the pre-lifting water vapour from pipeline 6 drives, simultaneously, from the hydrocarbon ils after the preheating of pipeline 7 with from the atomized water vapor mixing of pipeline 8, enter first reaction zone 9 of riser reactor, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carry out a cracking reaction, inject the cold shock agent from pipeline 11 in the junction of first reaction zone 9 and second reaction zone 10, the cold shock agent is that boiling range is 121-250 ℃ a normal temperature raw gasline, the consumption of cold shock agent makes reactant flow be reduced to the listed temperature of table 8 in the temperature of reaction of second reaction zone 10, reactant flow with continue to go upward to second reaction zone 10 after the cold shock agent mixes, carry out secondary reaction.In the junction of the outlet area 12 and second reaction zone 10, add terminator through pipeline 15, terminator is that boiling range is 121-250 ℃ a normal temperature raw gasline, the consumption of terminator makes reactant flow be reduced to the listed temperature of table 8 in the temperature of outlet area 12.Logistics behind the secondary reaction mixes the back continuation with terminator up, by outlet area 12, through level pipe 13, enters the settling vessel 14 of separation system, and the cyclonic separator in the settling vessel 14 separates catalyzer with crackate.Isolated catalyzer enters the stripper 16 of separation system, with water vapor counter current contact from pipeline 17, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 18 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 1 through inclined tube 19 to be generated, and in revivifier 1, reclaimable catalyst contacts with air, removes the carbon deposit in the catalyzer.Operational condition is listed in the table 8, and reaction result is listed in the table 9.
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 cracking method of reference catalyst is used in following Comparative Examples explanation.
The method of pressing example 9 is carried out catalytic cracking to same stock oil under same condition, that different is the reference catalyst CB that catalyst system therefor is respectively Comparative Examples 1 and Comparative Examples 2 preparations
1And CB
2, operational condition is listed in the table 8, and reaction result is listed in the table 9.
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, ℃ |
243 294 316 395 429 473 |
Table 8
| Example number | 9 | Comparative Examples 3 | Comparative Examples 4 | 10 | 11 | |
| The catalyzer numbering | C 1 | CB 1 | CB 2 | C 2 | C 3 | |
| Temperature, ℃ | First reaction zone 9 | 550 | 550 | 550 | 490 | 510 |
| Second reaction zone 10 | 530 | 530 | 530 | 475 | 485 | |
| |
510 | 510 | 510 | 465 | 470 | |
| Pressure, MPa | First reaction zone 9 | 0.18 | 0.18 | 0.18 | 0.13 | 0.12 |
| Second reaction zone 10 | 0.15 | 0.15 | 0.15 | 0.10 | 0.10 | |
| Reaction times, second | First reaction zone 9 | 1.0 | 1.0 | 1.0 | 2.5 | 0.5 |
| Second reaction zone 10 | 4.0 | 4.0 | 4.0 | 4.5 | 4.5 | |
| |
0.5 | 0.5 | 0.5 | 1.0 | 0.2 | |
| Agent-oil ratio | 5.0 | 5.0 | 5.0 | 5.5 | 6.0 | |
| Temperature in the revivifier 1, ℃ | 690 | 690 | 690 | 670 | 680 | |
| Water-oil ratio | 0.08 | 0.08 | 0.08 | 0.06 | 0.1 | |
Table 9
| Example number | 9 | Comparative Examples 3 | Comparative Examples 4 | 10 | 11 |
| The catalyzer numbering | C 1 | CB 1 | CB 2 | C 2 | C 3 |
| Transformation efficiency, weight % | 84.9 | 77.4 | 76.5 | 85.8 | 82.9 |
| Total liquid is received weight % | 87.0 | 78.2 | 76.8 | 88.2 | 83.0 |
| Product is formed, weight % | |||||
| Dry gas | 1.7 | 2.1 | 2.7 | 1.5 | 2.1 |
| Liquefied gas | 25.9 | 22.0 | 21.8 | 29.6 | 32.0 |
| Gasoline | 51.1 | 46.5 | 44.9 | 48.2 | 42.5 |
| Diesel oil | 10.1 | 9.7 | 10.1 | 10.4 | 8.5 |
| Coke | 6.3 | 6.8 | 7.1 | 6.5 | 6.3 |
| Unconverted heavy oil | 5.0 | 12.9 | 13.4 | 3.8 | 8.6 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 21.4 30.9 34.4 | 25.7 28.8 31.1 | 26.0 26.5 29.0 | 17.5 31.6 37.2 | 23.2 24.9 32.2 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 872 51.8 42.6 | 922 27.2 28.5 | 925 26.7 28.2 | 870 51.8 43.5 | 876 51.2 40.5 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 9.2 8.1 5.9 | 7.0 5.6 4.2 | 7.4 4.8 4.7 | 9.7 8.5 6.8 | 11.2 11.4 4.9 |
Example 12-13
Following example illustrates method provided by the invention.
By example 9 described methods stock oil is carried out catalytic cracking, different is, raw materials used oil is 2# stock oil shown in the table 10, and catalyst system therefor is C
4-C
5Described reactor is the disclosed reducing riser reactor of CN1078094C.The total height of this reactor is 15 meters, the height of pre lift zone is 1.5 meters, diameter is 0.25 meter, the height of first reaction zone 9 is 4 meters, the diameter of first reaction zone 9 is 0.25 meter, the height of second reaction zone 14 is 6.5 meters, the diameter of second reaction zone 14 is 0.5 meter, the diameter of outlet area is 0.25 meter, the outlet area height is 3 meters, the apex angle of the profile isosceles trapezoid of first reaction zone and the second reaction zone combining site is 45 degree, and the base angle β of the profile isosceles trapezoid of second reaction zone and outlet area combining site is 45 degree, and terminator is a water.Operational condition is listed in the table 11, and reaction result is listed in the table 12.
Table 10
| 2# stock oil | Long residuum |
| 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, ℃ | 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, ℃ |
283 350 374 432 477 511 |
| Characterization factor | 12.3 |
Table 11
| |
12 | 13 | |
| The catalyzer numbering | C 4 | C 5 | |
| Temperature, ℃ | First reaction zone 9 | 510 | 475 |
| Second reaction zone 10 | 500 | 450 | |
| |
485 | 450 | |
| Pressure, MPa | First reaction zone 9 | 0.19 | 0.14 |
| Second reaction zone 10 | 0.16 | 0.10 | |
| Reaction times, second | First reaction zone 9 | 1.0 | 1.8 |
| Second reaction zone 10 | 4.5 | 5.5 | |
| |
0.6 | 0.8 | |
| Agent-oil ratio | 8.5 | 11.0 | |
| Temperature in the revivifier 1, ℃ | 695 | 675 | |
| Water-oil ratio | 0.08 | 0.07 | |
Table 12
| |
12 | 13 |
| The catalyzer numbering | C 4 | C 5 |
| Transformation efficiency, weight % | 82.5 | 85.3 |
| Total liquid is received weight % | 87.0 | 87.9 |
| Product is formed, weight % | ||
| Dry gas | 2.1 | 1.7 |
| Liquefied gas | 28.9 | 28.5 |
| Gasoline | 45.8 | 49.6 |
| Diesel oil | 12.3 | 9.8 |
| Coke | 5.7 | 5.5 |
| Unconverted heavy oil | 5.2 | 4.9 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 24.2 28.4 29.2 | 19.2 31.5 32.4 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 879 50.2 40.0 | 870 51.4 43.0 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 8.4 9.2 6.5 | 9.5 7.9 7.2 |
Example 14
Following example illustrates method provided by the invention.
Carry out catalytic cracking according to 2# stock oil shown in the flow process his-and-hers watches 10 shown in Figure 2.Catalyst system therefor is the catalyzer C of example 6 preparations
6Described reactor is common riser reactor, and the height of reactor is 4000 millimeters, is followed successively by pre lift zone 5, first reaction zone 9, second reaction zone 10 and outlet area 12 from top to bottom.The height of pre lift zone 5 is 500 millimeters, interior diameter is 14 millimeters, the height of first reaction zone 9 is 1200 millimeters, the height of second reaction zone 10 is 1550 millimeters, the interior diameter of first reaction zone 9 and second reaction zone 10 is 20 millimeters, the interior diameter of outlet area 12 is 14 millimeters, highly is 750 millimeters.
From the catalyzer after the regeneration of revivifier 1 with enter the pre lift zone 5 of riser reactor through pipeline 2 from the mixture of the live catalyst of storage tank 3 (live catalyst is 3 weight % of regeneration rear catalyst) through pipeline 4, described catalyzer is up under the pre-lifting water vapour from pipeline 6 drives, enter first reaction zone 9 of riser reactor, simultaneously, from the hydrocarbon ils after the preheating of pipeline 7 with from the atomized water vapor mixing of pipeline 8, enter first reaction zone 9 of riser reactor, in first reaction zone 9, described hydrocarbon ils contacts with catalyzer, carry out a cracking reaction, inject the cold shock agent in the junction of first reaction zone 9 and second reaction zone 10 (is 1700 millimeters places apart from the riser reactor bottom level) from pipeline 11, the cold shock agent is that boiling range is 121-221 ℃ a gasoline, the consumption of cold shock agent makes the temperature of reaction of second reaction zone 10 be reduced to the listed temperature of table 13, reactant flow with continue to go upward to second reaction zone 10 after the cold shock agent mixes, carry out secondary reaction.Logistics behind the secondary reaction continues up, by outlet area 12, through level pipe 13, enters the settling vessel 14 of separation system, and the cyclonic separator in the settling vessel 14 separates catalyzer with crackate.Isolated catalyzer enters the stripper 16 of separation system, with water vapor counter current contact from pipeline 17, stripping goes out remaining crackate on the catalyzer, obtain reclaimable catalyst, isolated crackate and stripped product are mixed the back from pipeline 18 discharges, continue to isolate various fractions in separation system.Reclaimable catalyst enters revivifier 1 through inclined tube 19 to be generated, and in revivifier 1, reclaimable catalyst contacts with air, removes the carbon deposit in the catalyzer.Operational condition is listed in the table 13, and reaction result is listed in the table 14.
Table 13
| |
14 | |
| The catalyzer numbering | C 6 | |
| Temperature, ℃ | First reaction zone 9 | 490 |
| Second reaction zone 10 | 465 | |
| |
465 | |
| Pressure, MPa | First reaction zone 9 | 0.12 |
| Second reaction zone 10 | 0.10 | |
| Reaction times, second | First reaction zone 9 | 1.2 |
| Second reaction zone 10 | 11.0 | |
| |
0.5 | |
| Agent-oil ratio | 6.0 | |
| Temperature in the revivifier 1, ℃ | 680 | |
| Water-oil ratio | 0.15 | |
Table 14
| |
14 |
| The catalyzer numbering | C 6 |
| Transformation efficiency, weight % | 83.8 |
| Total liquid is received weight % | 87.7 |
| Product is formed, weight % | |
| Dry gas | 2.0 |
| Liquefied gas | 29.2 |
| Gasoline | 46.7 |
| Diesel oil | 11.8 |
| Coke | 5.7 |
| Unconverted heavy oil | 4.6 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 21.8 30.4 31.0 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 875 51.2 41.7 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 10.2 7.8 7.7 |
Example 15-16
Following example illustrates method provided by the invention.
Carry out catalytic cracking by 1# stock oil shown in the example 9 described method his-and-hers watches 7.Different is that catalyst system therefor is respectively the catalyzer C of example 7-8 preparation
7-C
8, the cold shock agent is that boiling range is 221-343 ℃ a diesel oil, does not add terminator, and operational condition is listed in the table 15, and reaction result is listed in the table 16.
Table 15
| |
15 | 16 | |
| The catalyzer numbering | C 7 | C 8 | |
| Temperature, ℃ | First reaction zone 9 | 500 | 480 |
| Second reaction zone 10 | 480 | 455 | |
| |
480 | 455 | |
| Pressure, MPa | First reaction zone 9 | 0.20 | 0.16 |
| Second reaction zone 10 | 0.15 | 0.12 | |
| Reaction times, second | First reaction zone 9 | 1.5 | 1.2 |
| Second reaction zone 10 | 4.5 | 4.0 | |
| |
0.2 | 0.3 | |
| Agent-oil ratio | 4.0 | 4.0 | |
| Temperature in the revivifier 1, ℃ | 700 | 670 | |
| Water-oil ratio | 0.06 | 0.07 | |
Table 16
| |
15 | 16 |
| The catalyzer numbering | C 7 | C 8 |
| Transformation efficiency, weight % | 82.8 | 83.2 |
| Total liquid is received weight % | 84.2 | 87.1 |
| Product is formed, weight % | ||
| Dry gas | 2.7 | 2.4 |
| Liquefied gas | 27.2 | 28.8 |
| Gasoline | 45.5 | 48.1 |
| Diesel oil | 11.5 | 10.2 |
| Coke | 7.4 | 3.9 |
| Unconverted heavy oil | 5.7 | 6.6 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 23.9 27.6 30.1 | 22.5 31.2 28.2 |
| Diesel oil character density (20 ℃), kilogram/rice 3Aniline point, ℃ cetane index | 878 50.6 40.2 | 873 51.5 41.2 |
| Liquefied gas character propylene content, weight % butene content, weight % Trimethylmethane content, weight % | 8.7 7.2 6.8 | 9.8 7.8 7.5 |
Result from above-mentioned table as can be seen, compare with the cracking method that uses reference catalyst, use method provided by the invention, 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, method provided by the invention not only has higher cracking ability, and, improved the gasoline in the cracked product significantly, the quality of diesel oil and liquefied gas.
Claims (14)
1. cracking method for hydrocarbon oil, this method is included in the reactor that comprises two reaction zones, hydrocarbon ils is contacted with a kind of cracking catalyst, carry out once and secondary reaction, reaction product isolated and catalyzer, with catalyst regeneration, catalyst recirculation after the regeneration is used, and described cracking catalyst contains aluminum oxide and molecular sieve, contains 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, and 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 %; The first reaction zone temperature of reaction is 450-650 ℃, and reaction pressure is the 0.1-0.5 MPa, and agent-oil ratio is 1-30; The second reaction zone temperature of reaction is 430-550 ℃, and reaction pressure is the 0.1-0.5 MPa, and agent-oil ratio is 1-30.
2. method according to claim 1 is characterized in that, 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 %.
3. method 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. method 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. method 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. method according to claim 4 is characterized in that described mesopore zeolite is selected from one or more in the zeolite with MFI structure.
7. method 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.
8. method 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.
9. method according to claim 1 is characterized in that, the first reaction zone temperature of reaction is 480-600 ℃, and reaction pressure is the 0.1-0.3 MPa, and agent-oil ratio is 2-15; The second reaction zone temperature of reaction is 450-530 ℃, and reaction pressure is the 0.1-0.3 MPa, and agent-oil ratio is 2-15.
10. method according to claim 1 is characterized in that, described reactor is a riser reactor, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 450-650 ℃, reaction pressure is the 0.1-0.5 MPa, and the reaction times is 0.4-3.5 second, and agent-oil ratio is 1-30; The second reaction zone temperature of reaction is 430-550 ℃, and reaction pressure is the 0.1-0.5 MPa, and the reaction times is 2-30 second; Agent-oil ratio is 1-30.
11. method according to claim 10 is characterized in that, the cracking reaction condition of first reaction zone comprises that temperature of reaction is 480-600 ℃, and reaction pressure is the 0.1-0.3 MPa, and the reaction times is 0.5-3 second, and agent-oil ratio is 2-15; The second reaction zone temperature of reaction is 450-530 ℃, and reaction pressure is the 0.1-0.3 MPa, and the reaction times is 3-15 second; Agent-oil ratio is 2-15.
12. method according to claim 10, it is characterized in that, described riser reactor is the riser reactor that is used for fluid catalytic cracking, this reactor vertically is followed successively by co-axial each other pre lift zone from bottom to up, first reaction zone, second reaction zone of enlarged-diameter, the outlet area of reduced, be connected with one section level pipe at the outlet area end, the diameter of first reaction zone of described reactor and the ratio of pre lift zone diameter are 1-1.2, the ratio of the diameter of second reaction zone and first reaction zone diameter is 1.5-5.0, and the ratio of the diameter of outlet area and first reaction zone diameter is 0.8-1.5; The height of pre lift zone accounts for the 5-20% of total reactor height, the height of first reaction zone accounts for the 10-30% of total reactor height, the height of second reaction zone accounts for the 30-60% of total reactor height, the height of outlet area accounts for the 0-20% of total reactor height, first reaction zone and the second reaction zone combining site are round table-like, its profile is that isosceles are trapezoidal, the apex angle of isosceles trapezoid is the 30-80 degree, second reaction zone and outlet area combining site also are round table-like, its profile is that isosceles are trapezoidal, and the base angle β of isosceles trapezoid is the 45-85 degree.
13. method according to claim 10, it is characterized in that, described riser reactor is the common riser reactor that comprises two reaction zones, first reaction zone of this reactor is lower part of riser reaction zone, second reaction zone is upper part of riser reaction zone, pre lift zone accounts for the 5-20% of riser reaction zone total length, the length of first reaction zone accounts for the 10-30% of riser reaction zone total length, the length of second reaction zone accounts for the 30-60% of riser reaction zone total length, and outlet area accounts for the 0-20% of riser reaction zone total length.
14. method according to claim 1 is characterized in that, described hydrocarbon ils is selected from oil and boiling point greater than 330 ℃ petroleum fractions.
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| JP5840840B2 (en) | 2007-12-20 | 2016-01-06 | 中国石油化工股▲分▼有限公司 | An improved integrated method for hydrogenating and catalytically cracking hydrocarbon oils |
| CN101531918B (en) * | 2008-12-22 | 2013-12-11 | 洛阳瑞泽石化工程有限公司 | Method for improving liquid hydrocarbon yield of catalytic cracking and catalyst thereof |
| CN102443423B (en) * | 2010-10-12 | 2014-03-26 | 中国石油化工股份有限公司 | Petroleum hydrocarbon catalytic conversion method for high output of ethylene, propylene and light aromatic hydrocarbons |
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
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| 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 |
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