CN116234634A - 用于fcc方法的添加剂 - Google Patents
用于fcc方法的添加剂 Download PDFInfo
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- CN116234634A CN116234634A CN202180065938.XA CN202180065938A CN116234634A CN 116234634 A CN116234634 A CN 116234634A CN 202180065938 A CN202180065938 A CN 202180065938A CN 116234634 A CN116234634 A CN 116234634A
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- additive
- iron
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- zsm
- catalyst
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- 239000000654 additive Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 88
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 229910052742 iron Inorganic materials 0.000 claims abstract description 43
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- 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 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 23
- 239000011574 phosphorus Substances 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 description 65
- 239000010457 zeolite Substances 0.000 description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 25
- 229910021536 Zeolite Inorganic materials 0.000 description 24
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 150000002430 hydrocarbons Chemical class 0.000 description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000005336 cracking Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- -1 propylene Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 150000003009 phosphonic acids Chemical group 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005569 Iron sulphate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 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 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
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Abstract
本发明包括用于使烯烃生产最大化的添加剂。该添加剂包含ZSM‑5分子筛、至少一种无机氧化物和氧化磷。ZSM‑5分子筛在骨架中具有铁，并且添加剂在分子筛骨架中包含至少0.5重量％的铁，以氧化铁测量。该添加剂可用于在FCC方法中使烯烃生产最大化。
Description
技术领域
本发明涉及用于在流体催化裂化方法中使轻质烯烃、特别是丙烯的生产最大化的添加剂。
背景技术
流体催化裂化(“FCC”)方法通过重质烃馏分的裂化产生较轻的有价值产物，诸如汽油、馏出物和C2-C4烯烃和饱和烃。FCC方法可有利地用于丙烯的生产。
FCC方法通常在FCC催化剂的存在下进行。典型的FCC催化剂包括Y沸石，或这些沸石的缺铝形式，诸如脱铝Y、超稳定Y和超疏水Y。沸石可以用稀土金属诸如镧、铈、钕和镨稳定，例如以约0.1重量％至约10重量％的量。用于FCC方法的催化剂为颗粒形式，通常具有20微米至200微米范围内的平均粒度，并在裂化反应器与FCC单元的催化剂再生器之间循环。在反应器中，烃进料与热的再生催化剂接触，再生催化剂在约400℃至700℃，通常500℃至约550℃蒸发和裂化进料。
来自当前FCC方法的产物分布包括多种成分，汽油或柴油是大多数精炼者主要感兴趣的。轻质烯烃和液化石油气(“LPG”)也存在于FCC产物中，并且由于这些产物变得更有价值而越来越受到精炼者的关注。所产生的轻质烯烃可用于许多目的，例如，它们经由硫酸或HF烷基化升级成高质量烷基化物。LPG用于烹饪和/或加热目的。因此，FCC单元的操作者可以根据他们所服务的市场和与在FCC产品中发现的每种组分相关的价值来改变他们的产品的含量。
丙烯是高需求的特定轻质烯烃。它在世界上许多最大和最快增长的合成材料和热塑性塑料中用作原料。精炼者越来越依赖于他们的FCC单元来满足对丙烯的增加的需求，因此随着操作者寻求最大化利润的机会，将传统FCC单元的焦点从运输燃料转移开并且更多地朝向石化原料生产转移。
先前公开的方法教导了石油烃的催化转化方法，特别是由石油烃方法以高收率生产轻质烯烃的催化转化方法。参见例如美国专利号5,997,728和8,658,024以及美国专利申请公开号2005/0020867和2010/0010279。
美国专利申请公开号2009/0134065教导了可流体化的催化剂组合物，其包含五硅链沸石、至少5重量％的磷(以P2O5计)和存在于五硅链沸石骨架外部的至少约1％的氧化铁。
工业设施不断地试图找到生产轻质烯烃的新的和改进的方法，特别是那些也对从他们的FCC单元生产汽油作为主要产物感兴趣的精炼者。因此，希望具有相对于现有添加剂的选择性，以单位LPG为基础提高烯烃选择性(例如丙烯选择性)的添加剂。
申请人已经开发了一种添加剂，与以前在FCC方法中使用的添加剂相比，其使丙烯产量增加约15％。
发明内容
本发明包括用于在流体催化裂化方法中使烯烃生产最大化的添加剂。该添加剂包含ZSM-5分子筛、至少一种无机氧化物和氧化磷。ZSM-5分子筛在骨架中具有铁，并且添加剂在分子筛骨架中包含至少0.5重量％的铁，以氧化铁测量。
附图说明
图1示出了丙烯产量对骨架铁与骨架铝的摩尔比(Fe:Al)的图。
图2示出了丙烯产量对磷与骨架铁和骨架铝的合并量的摩尔比(P:(Fe+Al))的图。
具体实施方式
本发明包括用于在流体催化裂化方法中使烯烃生产最大化的添加剂。该添加剂包含ZSM-5分子筛。ZSM-5分子筛在骨架中具有铁，并且添加剂在分子筛骨架中包含至少0.5重量％的铁，以氧化铁测量。
ZSM-5分子筛在结构的骨架中具有五元环。该骨架包含四面体配位的二氧化硅和氧化铝。ZSM-5分子筛在骨架中也具有铁。在制备ZSM-5的方法中将铁添加到骨架中。“在骨架中”是指铁存在于ZSM-5的结构骨架中，因为它置换了ZSM-5的典型二氧化硅-氧化铝骨架的硅或铝。
添加剂优选地在分子筛骨架中包含1重量％至5重量％铁(以氧化铁测量)，甚至更优选地约1重量％至3重量％铁(以氧化铁测量)。
优选地，在ZSM-5的骨架中铁与铝的摩尔比在0.4至0.67的范围内。
在骨架中包含铁的ZSM-5可以通过任何已知的方式生产。例如，可以以受控方式混合氧化铝、二氧化硅、铁、酸和模板源以制备分子筛凝胶。然后将凝胶在高温下(在自生压力下)结晶一段时间。然后优选通过过滤、洗涤、离子交换和研磨来处理含骨架铁的ZSM-5。
在制备之后，优选地将ZSM-5与所需阳离子进行离子交换以置换所制备的沸石中存在的碱金属。该交换处理使得最终催化剂的碱金属含量降低至小于约0.5重量％，优选地小于约0.1重量％。
该添加剂还包含磷。磷通常用于稳定ZSM-5。
优选地，通过用磷化合物浸渍具有骨架铁的ZSM-5而将磷添加到添加剂中。或者，可将磷添加到除ZSM-5外还含有无机氧化物(和其它可能的组分)的添加剂中。添加剂优选地包含至少约5重量％的磷(以P2O5计)，更优选地至少8重量％，甚至更优选地至少10重量％。
可以使用任何含磷化合物来将磷添加到添加剂中。优选地，含磷化合物将含有能够与氢离子反应的共价或离子成分。合适的含磷化合物包括酸，诸如磷酸、亚磷酸及其盐。其它合适的含磷化合物包括膦、亚磷酸盐、膦酸盐和亚膦酸盐，诸如伯、仲和叔膦，诸如丁基膦；叔膦氧化物诸如氧化三丁基膦；伯和仲膦酸，诸如苯膦酸；膦酸的酯，诸如二乙基膦酸酯、二烷基烷基膦酸酯和烷基二烷基次膦酸酯；三价膦酸类，诸如二乙基三价膦酸；伯、仲和叔亚磷酸盐；以及其酯，诸如单丙基酯、烷基二烷基亚膦酸酯、和二烷基烷基亚膦酸酯。
优选地，ZSM-5骨架中磷与铁和铝的合并量的摩尔比(P:(Fe+Al))在1至1.3的范围内。
除了ZSM-5和磷之外，添加剂还含有一种或多种无机氧化物。无机氧化物优选地为二氧化硅、氧化铝、二氧化硅-氧化铝、氧化钛、氧化锆、磷酸铝等中的一种或多种。无机氧化物优选地不是分子筛。当无机氧化物是磷酸铝时，可以减少添加到添加剂中的磷(与磷酸铝分离)的量。
添加剂优选地还包含一种或多种粘土。优选地粘土包括蒙脱石、高岭土、埃洛石、膨润土、绿坡缕石等。
添加剂优选地包含含骨架铁的ZSM-5，使得ZSM-5占添加剂的25重量％至80重量％，更优选地占添加剂的40重量％至70重量％。
添加剂可通过任何已知的方法制备，包括将含骨架铁的ZSM-5分子筛、磷源、无机氧化物和粘土添加到喷雾干燥器进料浆液中并形成添加剂颗粒。
该添加剂可用于催化裂化烃原料的流体催化裂化方法中，该方法包括使原料在催化裂化条件下在FCC催化剂存在下与添加剂接触。
优选地，催化裂化条件包括使烃原料在约400℃至约700℃的温度下反应。原料的接触通常在包括提升管和反应区段的FCC单元中进行，其中FCC催化剂接触并蒸发烃原料。烃原料优选进入FCC单元的提升管的底部并携带FCC催化剂和添加剂沿提升管向上进入反应器区段中。裂化烃产物离开反应器的顶部，并且FCC催化剂颗粒和添加剂保留在反应器下部中的颗粒床中。
然后将用过的FCC催化剂和添加剂通入FCC单元的再生器中。如本申请中所使用的，术语“再生器”还包括再生器和CO锅炉的组合，特别是当再生器本身在部分燃烧条件下运行时。在再生器中，FCC催化剂上的焦炭以及添加剂在氧气和流化气体的存在下在流化床中被烧掉，所述氧气和流化气体通常通过进入再生器的底部来供应。将再生的FCC催化剂和添加剂从再生器中取出并返回到提升管中以在裂化过程中再利用。
优选地，FCC催化剂和添加剂的循环存量在催化裂化方法中循环，其中该循环存量的约2重量％至约20重量％包含如上所述的添加剂。
用于催化裂化方法的烃原料的范围可以是石油馏出物或残余原料(原始的或部分精炼的)、煤焦油和页岩油、瓦斯油、真空瓦斯油、常压渣油、真空渣油、生物质、焦化瓦斯油、润滑油提取物、加氢裂化塔底产物、野生石脑油、污油等。原料可以含有再循环的烃，诸如已经经受裂化的轻质和重质循环油。优选的原料包括瓦斯油、真空瓦斯油、常压渣油和真空渣油。
添加剂和FCC催化剂可以分别或一起添加到FCC单元中。添加剂优选地但不排他地添加到FCC单元的再生器中。
添加剂和FCC催化剂可通过从料斗、袋或桶手动装载或使用自动添加系统引入FCC单元中，如例如美国专利号5,389,236中所述。为了将添加剂引入FCC单元中，添加剂也可以与FCC催化剂预混合，并作为掺加物引入单元中。或者，添加剂和FCC催化剂可通过单独的注入系统引入FCC单元中。在另一个实施方案中，添加剂可以以不同比率添加至FCC催化剂。例如，为了优化添加剂的添加速率，可以在添加至FCC单元时确定变化的比率。
可使用常规和高苛刻度FCC提升管或下降管裂化条件，或较老类型的FCC流化床反应器裂化条件。裂化反应条件包括约1:1至约30:1的催化剂/油比率和约0.1秒至约360秒的催化剂接触时间，以及约425℃至约750℃的提升管顶部/反应器床温度。
本发明的添加剂可以添加至任何常规的流化床反应器-再生器系统中、添加至沸腾催化剂床系统中、添加至涉及在反应区和再生区之间连续输送或循环催化剂/添加剂的系统中等。在一个实施方案中，该系统是循环床系统。典型的循环床系统是常规的移动床和流化床反应器-再生器系统。这两种循环床系统通常用于烃转化(例如烃裂化)操作。在一个实施方案中，该系统是流化催化剂床反应器-再生器系统。
可用于本文的其它专用提升管-再生器系统包括深度催化裂化(DCC)、毫秒催化裂化(MSCC)、高苛刻度石油化工FCC残油流体催化裂化(RFCC)系统、Superflex、高级催化烯烃等。
本发明的FCC催化剂是指可用于在所有类型的催化裂化条件下操作FCC单元的任何催化剂。任何可商购获得的FCC催化剂可用作FCC催化剂。FCC催化剂可以是100％无定形的，但在一个实施方案中，可以在多孔耐火基质诸如二氧化硅-氧化铝、粘土等中包含一些沸石。沸石通常按重量计为催化剂的约5％至约70％，其余为基质。可使用常规沸石诸如Y沸石，或这些沸石的缺铝形式诸如脱铝Y、超稳定Y和超疏水Y。沸石可用镁或稀土稳定化，例如以约0.1重量％至约10重量％的量。
可用于本文的沸石包括天然沸石和合成沸石两者。
含相对高二氧化硅沸石的催化剂可用于本发明中。它们可以承受通常与焦炭在FCC再生器内完全燃烧成CO2相关的高温。此类催化剂包括通常含有约10％至约70％超稳定Y或稀土超稳定Y的那些。
除了FCC催化剂和本发明的添加剂之外，其它添加剂也可用于本发明的方法中。优选地，可添加这些附加的添加剂以提高辛烷值；捕集金属；促进CO燃烧；减少SOx排放、NOx排放和/或CO排放；促进催化；或减少汽油硫。
与使用不添加铁的ZSM-5或使用含有非骨架铁(通过离子交换、初湿含浸法、喷雾干燥器进料浆料和/或浸渍添加铁)的ZSM-5添加剂的类似方法相比，在FCC方法中使用本发明的添加剂导致轻质烯烃产量增加。
以下实施例仅示出本发明。本领域的技术人员将认识到本发明的实质和权利要求的范围内的许多变型形式。
比较例1：ZSM-5的制备
将水(约42kg)添加至罐中，随后添加溴化四丙基铵模板(TPABr，280g)。然后将水玻璃(72kg；28.9重量％SiO2，8.9重量％Na2O)，硫酸铝(12.5kg；8.2％ Al2O3)和硫酸(4.45kg)同时添加至罐中以维持约9.5的pH。在添加原料后，将凝胶转移到反应器中并在高温(～160℃)下水热结晶直至沸石相对结晶度达到95％或更高(基于标准ZSM-5晶体)。结晶后，洗涤沸石并进行离子交换以除去钠。该沸石称之为沸石1。
实施例2：在骨架中含有铁的本发明沸石的制备
除了将硫酸铁(3.65kg；18.2重量％的Fe2O3)与水玻璃、硫酸铝和硫酸一起添加至罐中外，按照比较例1的规程进行；并且仅使用2.8kg的硫酸。在添加所有原料后，然后将凝胶转移至反应器中并在高温(～160℃)下水热结晶直至沸石相对结晶度大于95％。该沸石称之为沸石2。
表1：沸石1和沸石2的特性如表1所示。
比较例3：含ZSM-5的比较催化剂的制备
将假勃姆石氧化铝(116.3g；78重量％固体)添加至630g的水中，并将混合物混合10分钟。然后添加甲酸(10.9g；90％浓度)并将混合物搅拌1小时。然后将该解胶的氧化铝混合物转移至混合罐中，随后是二氧化硅溶胶(263.8g；41.3重量％固体)、粘土(1177.9g；51.6重量％固体)、沸石1(2335.8g；35.0重量％固体)和85％磷酸(350.5g)。将该浆料搅拌半小时，然后喷雾干燥以形成催化剂3。
实施例4：本发明的催化剂的制备
除了使用1142.8g的粘土(51.6重量％固体)和383.8g的85％磷酸之外，以与实施例3类似的方式通过使用沸石2代替沸石1制备本发明的催化剂B。
比较例5：具有添加的硝酸铁形式的铁的比较催化剂的制备
以与实施例4类似的方式制备催化剂C，除了使用沸石1(2249.8g)代替沸石2并且还将296.2g的硝酸铁(9.8重量％固体)添加到喷雾干燥器进料浆液中。
比较例6：具有添加的氧化铁形式的铁的比较催化剂的制备
以与比较例5类似的方式制备催化剂D，但将29.2g的氧化铁(99.5重量％固体)代替硝酸铁添加到喷雾干燥器进料浆液中。
表2：催化剂A、B、C和D的特性
实施例7：催化剂A-D的测试
将催化剂A-D在732℃下煅烧1小时，然后经受蒸汽去激活。通过在95％蒸汽下在815℃下汽蒸20小时来进行去激活。使用高级裂化评价(ACE)单元进行催化剂测试。使用真空瓦斯油(80％)和常压渣油(20％)的混合物作为进料，将催化剂以4重量％与商业平衡催化剂(Ecat)共混。通过改变进料量(在固定注入速率下)同时保持催化剂量恒定来改变转化率。
活性结果显示在表3中，如在70％的恒定转化率下内插，Δ收率显示在从Ecat值中减去后。
表3：催化剂A-D的测试
如表3中所示，与不含同晶骨架铁的对应比较催化剂A相比，催化剂B同晶骨架铁使丙烯(C3＝)多52.2重量％，并且与浸渍/混合比较催化剂C和D相比，也使C3＝多29.1重量％。
实施例8：具有不同量的骨架铁的沸石的制备
以与实施例2相同的方式制备具有不同的铝和铁比率的沸石，除了所用的铝和/或铁的量。与铝和铁成比例地调节硫酸。
表4：所制备的沸石的特性示于表4中。
实施例9：具有不同量的骨架铁的催化剂的制备
以与实施例4的方法类似的方式将沸石3、4和5分别配制成催化剂E、F和G。它们的特性在表5中示出。
表5：催化剂E-G的特性
实施例10：具有不同量的骨架铁的催化剂的测试
将催化剂B、E、F和G煅烧、蒸汽去激活并以与实施例7类似的方式进行测试。活性结果在表6中示出。
表6：催化剂B、E-G的测试
实施例10的测试结果绘制在图1中，示出骨架铁ZSM-5的最大益处(最高丙烯收率)取决于沸石中骨架铝和铁的比率。
实施例11：具有不同量的磷的催化剂的制备
以与实施例4相同的方式将沸石2(如实施例2中制备)配制成催化剂，但具有不同含量的磷(9.5重量％至13.5重量％P2O5)。差异出自粘土。所制备的催化剂的特性示于表7中。
表7：催化剂H-K的特性
实施例12：具有不同量的磷的催化剂的测试
催化剂B、H、I、J和K以类似于实施例7的方式进行煅烧、去激活和测试。
如表8所示，除了活性对骨架Fe/Al比率的依赖性外，还存在最佳活性所需的其它优化过程。
表8：催化剂B和H-K的测试结果
实施例12的结果绘制在图2中，示出在约1.23的P/(Fe+Al)摩尔比下观察到最大活性(其中Fe和Al是骨架)。
总之，用含有同晶骨架铁的ZSM-5观察到超过50％的附加丙烯，这显著高于以非同晶形式引入铁的情况(阳离子交换或浸渍/混合)。Fe/Al比率和P/(Fe+Al)比率在最大化性能益处中起关键作用。
Claims (9)
1.一种用于在流体催化裂化方法中使烯烃生产最大化的添加剂，所述添加剂包含ZSM-5分子筛、至少一种无机氧化物和氧化磷，其中所述ZSM-5分子筛在骨架中具有铁，并且所述添加剂在所述分子筛骨架中包含至少0.5重量％的铁，以氧化铁测量。
2.根据权利要求1所述的添加剂，其中所述添加剂包含至少5重量％的磷(以P2O5计)。
3.根据权利要求1所述的添加剂，其中所述ZSM-5分子筛包含约1重量％至5重量％的氧化铁。
4.根据权利要求1所述的添加剂，其中所述ZSM-5分子筛具有在0.4至0.67范围内的骨架铁与骨架铝的摩尔比。
5.根据权利要求1所述的添加剂，其中所述添加剂具有在1至1.3范围内的磷与骨架铁和骨架铝的合并量的摩尔比(P:(Fe+Al))。
6.根据权利要求1所述的添加剂，其中所述无机氧化物选自二氧化硅、氧化铝、二氧化硅-氧化铝、氧化钛、氧化锆、磷酸铝以及它们的组合。
7.根据权利要求1所述的添加剂，所述添加剂还包含粘土。
8.根据权利要求1所述的添加剂，其中所述ZSM-5占所述添加剂的25重量％至80重量％。
9.根据权利要求1所述的添加剂，其中所述ZSM-5占所述添加剂的40重量％至70重量％。
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| US5389236A (en) | 1993-04-21 | 1995-02-14 | Bartholic; David B. | Method and apparatus for controlling introduction of catalysts into FCC units |
| US6852214B1 (en) * | 1998-08-31 | 2005-02-08 | Mobil Oil Corporation | Gasoline sulfur reduction in fluid catalytic cracking |
| US6613710B2 (en) * | 2001-09-25 | 2003-09-02 | Indian Oil Corporation Limited | Process for preparation of bi-functional fluid catalytic cracking catalyst composition |
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| US20100010279A1 (en) | 2004-04-02 | 2010-01-14 | Ranjit Kumar | Catalyst Compositions Comprising Metal Phosphate Bound Zeolite and Methods of Using Same to Catalytically Crack Hydrocarbons |
| WO2006069535A1 (fr) | 2004-12-28 | 2006-07-06 | China Petroleum & Chemical Corporation | Catalyseur et procede de craquage d’une huile hydrocarbure |
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