CN105579422A - 甲醇转化方法 - Google Patents
甲醇转化方法 Download PDFInfo
- Publication number
- CN105579422A CN105579422A CN201480052283.2A CN201480052283A CN105579422A CN 105579422 A CN105579422 A CN 105579422A CN 201480052283 A CN201480052283 A CN 201480052283A CN 105579422 A CN105579422 A CN 105579422A
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- CN
- China
- Prior art keywords
- metal oxide
- molecular sieve
- zeolite
- alkaline metal
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004519 manufacturing process Methods 0.000 title description 8
- 229910001220 stainless steel Inorganic materials 0.000 title 2
- 239000010935 stainless steel Substances 0.000 title 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 187
- 238000000034 method Methods 0.000 claims abstract description 81
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- 239000010457 zeolite Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 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 43
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000006069 physical mixture Substances 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 37
- 150000004706 metal oxides Chemical class 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 150000002430 hydrocarbons Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
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- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 3
- 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 claims description 3
- 229910052676 chabazite Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 239000011246 composite particle Substances 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 13
- 239000003502 gasoline Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910001038 basic metal oxide Inorganic materials 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
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- 229910004298 SiO 2 Inorganic materials 0.000 description 4
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910017090 AlO 2 Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- 239000004411 aluminium Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
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- 238000005243 fluidization Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 238000011084 recovery Methods 0.000 description 3
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- 229960001866 silicon dioxide Drugs 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
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- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- 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
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Abstract
一种甲醇转化方法,所述甲醇转化方法包括:使包含甲醇和任选的二甲醚或其它含氧化合物的进料流与催化剂接触,以通过减少焦炭形成的发生而提供延长的催化剂循环寿命,所述催化剂包含分子筛和碱性金属氧化物的物理混合物,所述分子筛优选为中孔径或小孔径沸石诸如MFI沸石。所述方法可以应用于甲醇到汽油(MTG)、甲醇到馏出物(MOD)、甲醇到烯烃(MTQ)、甲醇到化学品(MTC)和组合方法诸如MTO/OCP方法。
Description
技术领域
本发明涉及如下方法,该方法用于将甲醇或甲醇与二甲醚的混合物转化为用作燃料混合原料或用作石油化学品进料的烃化学品诸如低碳烯烃、汽油、馏出物和芳族化合物。
背景技术
通常通过催化或蒸汽裂化方法由石油原料生产烯烃。这些裂化方法尤其是蒸汽裂化从各种烃原料生产一种或多种低碳烯烃诸如乙烯和/或丙烯。乙烯和丙烯是在制造塑料和其它化合物的各种方法中有用的重要商品石油化学品。随着石油原油成本的增加,含氧化合物(oxygenate)尤其是醇类已经用于转化为各种烃化学品,包括低碳烯烃诸如乙烯和丙烯、汽油和馏出物(distillate)沸程的烃类。有许多可用于制造含氧化合物的技术,包括来自天然气的合成气、石油液体或包括煤、再生塑料、城市废物或任何其它有机材料的碳质材料的发酵或反应。通常,合成气的生产涉及主要是甲烷的天然气与氧源生成氢、一氧化碳和/或二氧化碳的燃烧反应。其它已知的合成气生产方法包括常规的蒸汽重整、自热重整或这些方法的组合。
通常在甲醇反应器中,在非均相催化剂的存在下,由氢气、一氧化碳和/或二氧化碳的催化反应合成甲醇,甲醇为用于低碳烯烃生产的优选醇。例如,在一种合成方法中,在水冷管式甲醇反应器中使用铜/锌氧化物催化剂生产甲醇。将包含甲醇的原料转化为一种或多种烯烃、主要是乙烯和/或丙烯的优选方法通常使原料与分子筛催化剂组合物接触。
各种商业化方法已经发展为使用这些和相关的技术。埃克森美孚MTG(甲醇到汽油)方法(MTG)开发于二十世纪七十年代并且首先在固定床方法中使该技术商业化,流化床方法后来被发展用于流化床应用,扩展至烯烃(MTO方法)和化学品(MTC方法)的生产。包括UOP和道达尔(Total)的其它公司在这一领域也很活跃:在甲醇到烯烃(MTO):商业化催化方法的发展(MethanoltoOlefins(MTO):DevelopmentofaCommercialCatalyticProcess),SimonR.Bare,先进的表征(AdvancedCharacterization),UOPLLC,非均相催化研究的现代方法,FHI讲座,2007年11月30日(2007UOPLLC,版权所有)中给出了甲醇转化技术的有用的总结。
由UOP和道达尔联合开发的MTO/OCP方法(甲醇到烯烃/烯烃裂化方法)将MTO方法和烯烃裂化方法组合,以通过经低聚化-裂化和烷基化的在甲醇存在下的重排来转化在C4~C8范围烯烃中的较重的烯烃,从而形成用于聚合成为聚乙烯和聚丙烯的富含较轻烯烃(额外的乙烯和丙烯)的产物。如在美国专利8450548(Karim)中,甲醇通过改性的沸石催化剂转化为芳族化合物也是已知的。
基本甲醇转化方法技术的这些变体依赖于甲醇或其主要的脱水产物二甲醚通过分子筛向烃类的转化。有许多不同类型的将含氧化合物原料转化为一种或多种烯烃和其它烃类的已知分子筛。例如,美国专利5367100描述了使用沸石ZSM-5将甲醇转化为一种或多种烯烃;美国专利4062905论述了使用结晶硅铝酸盐沸石例如T型沸石(ZeoliteT)、ZK5、毛沸石和菱沸石将甲醇和其它含氧化合物转化为乙烯和丙烯;美国专利4079095描述了使用ZSM-34将甲醇转化为烃产物诸如乙烯和丙烯;以及美国专利4310440描述了使用常常指定为AlPO4的结晶磷酸铝由醇生产一种或多种低碳烯烃。描述通过沸石分子筛催化剂的甲醇转化的许多其它专利例如为US4049573(硼或镁改性的中孔沸石)、US4547602(使用中孔径沸石的两阶段方法)、US5367100(利用磷、稀土改性的ZSM-5催化剂)、US6372949(一维中孔径沸石催化剂)、US6740790(使用曝光指数(exporeindex)至少为1.0的催化剂原料的SAPO催化剂)、US6743747(SAPO催化剂,优选SAPO-340)、EP083160(利用镁氧化物锰氧化物或镁氧化物和铂氧化物改性的小孔径沸石)、US2006/0025644(催化剂包含分子筛和至少一种金属氧化物,所述金属氧化物在100℃下具有金属氧化物的至少0.03mg/m2的二氧化碳摄取);US2007/0244000(金属氧化物和分子筛的两组分催化剂,其用于甲醇转化,然后通过分子筛形成烯烃)、WO98/29370(包含镧系元素、锕系元素、钪、钇、第4族金属或第5族金属的小孔非沸石分子筛)。
通常,将分子筛形成为分子筛催化剂组合物以提高它们在商业转化方法中的耐久性。通过将分子筛与通常为黏土或金属氧化物的基质材料和/或粘合剂结合形成这些分子筛催化剂组合物。然而,这些粘合剂和基质材料通常仅用来向催化剂组合物提供期望的物理特性,提供进料分子到分子筛和从分子筛移除产物的通路,且对分子筛的转化和选择性具有很少影响或没有影响。因此期望有改进的分子筛催化剂组合物,其具有更好的转化率、提高的烯烃选择性和更长的寿命。
所述方法的商业实践通常涉及固定床反应器的使用。随着焦炭在催化剂中的积累,固定床反应器中的催化剂钝化。不用深究反应机理的具体细节,已知甲醇的使用或存在可增加焦炭形成的速率。钝化的催化剂需要氧化再生以烧掉累积的焦炭。通过从反应器中移除催化剂并在再生器单元中烧掉焦炭,或者通过将反应器与甲醇进料隔离并在适当的控制条件下引入空气以烧掉焦炭,可实现再生。在再生之后,将再生的催化剂再引入甲醇转化过程中,或更通常地,将床放回甲醇转化的生产线。因此期望具有更长的催化剂寿命。催化剂寿命越长,进行再生的频率就越低,这导致方法的较少投资。
发明内容
现在我们已经发现,通过利用沸石的甲醇转化催化剂与碱性金属氧化物助催化剂的混合物形成催化剂,可以显著增加催化剂的循环寿命。实现了催化剂循环寿命的提高,而且没有显著影响对期望的一种或多种烃类产物的反应选择性。
根据本发明的甲醇转化方法包括:使包含甲醇和任选的二甲醚或其它含氧化合物的进料流与催化剂接触,所述催化剂包含分子筛和碱性金属氧化物的物理混合物,所述分子筛可以为沸石诸如MFI沸石。
可以用于该目的的合适碱性金属氧化物助催化剂包括镁氧化物、钙氧化物和其它碱土金属氧化物以及稀土元素的氧化物,所述稀土元素包括铈、镧系金属和化学性质相似的元素钪和钇,其中钇是优选的。可以将金属氧化物负载在多孔载体例如另一种金属氧化物的多孔载体上。这种选择是有利的,以提高一种或多种活性金属氧化物的分散性,从而制造更大量可用于捕获甲醛的活性位点,甲醛在最终使催化剂钝化的焦炭的形成中充当前体。
优选的分子筛材料沸石是小孔径或中孔径沸石,优选由MFI结构的沸石例示的中孔(10元环)沸石诸如ZSM-5和ZSM-11;小孔(8元环)沸石诸如菱沸石、毛沸石、沸石4A,但也可以使用非沸石分子筛诸如磷酸硅铝分子筛(SAPO)和磷酸铝分子筛(ALPO)。
附图说明
附图的唯一图是显示ZSM-5和ZSM-5/氧化钇的甲醇到汽油(MTG)反应的转化曲线的图,如下所述。
具体实施方式
通过如下实现甲醇或甲醇/DME混合物向烯烃、汽油和其它烃类的转化:使含甲醇的进料与烯烃形成催化剂接触,从而形成期望的烃产物,特别是乙烯和丙烯,但也可以为高级烯烃,诸如丁烷、己烷或辛烷或汽油或馏出物沸程的烃类。用于转化含氧化合物原料的方法优选为连续流化床方法以使与反应放热有关的问题最小化,但不排除优选使用再循环或进料稀释剂带走反应热的固定床操作。
本催化剂体系对于其中将甲醇与二甲醚或其它含氧化合物的混合物的甲醇转化为烃类的各种反应都是有用的。通常,已经将这些反应方案分类为甲醇到汽油(MTG),甲醇到烯烃(MTO),甲醇到化学品(MTC)(由于烯烃是主要的和期望的产物,所以实际上是甲醇到烯烃),甲醇到芳族化合物(MTA),和组合方法,诸如上述的MTO/OCP方法,以及通过将甲醇到烯烃(MTO)和美孚烯烃到汽油和馏出物方法(MOGD)组合来生产汽油和馏出物的组合方法,或者甚至是如US4678645中所述的通过将MTO和美孚烯烃到汽油、馏出物和润滑油方法(MOGDL)组合的润滑油生产的组合方法。通过选择适当的根据经验确定的操作参数,可以根据操作者的需要改变产物。
所述反应方法可以在各种催化反应器如混合反应器、循环流化床反应器、提升管反应器等中进行,所述混合反应器具有结合在一起的密相床或固定床反应区和/或快速流化床反应区。合适的常规反应器类型在例如美国专利4076796和6287522(双提升管),和流化工程(FluidizationEngineering),D.Kunii和O.Levenspiel,RobertE.Krieger出版公司,纽约,N.Y.1977中进行描述。
一种优选的反应器类型为提升管反应器。这些反应器类型通常在如下中进行描述:提升管反应器、流化和流体-粒子体系(RiserReactor,FluidizationandFluid-ParticleSystems),第48~59页,F.A.Zenz和D.F.Othmo,Reinhold出版公司,N.Y.,1960和美国专利6166282(快速流化床反应器)。
在所述转化方法中采用的、特别是在反应器内的平均反应温度通常为约250℃至约600℃。优选反应器中的平均反应温度为约250℃至约500℃;更优选为约300℃至约500℃。在转化方法中采用的、特别是在反应器内的压力不是至关重要的。反应压力基于其中不包括任何稀释剂的原料的分压。通常,在方法中采用的反应压力在约0.1kPaa至约5Mpaa、优选约5kPaa至约1Mpaa、最优选约20kPaa至约500kPaa的范围内。
在流化床方法中,将重时空速(WHSV)维持在足以保持催化剂组合物在反应器内处于流化态的水平,所述重时空速被定义为,相对于单位重量的反应区中分子筛催化剂组合物中的分子筛,每小时到反应区的不包括任何稀释剂的进料的总重量。通常,WHSV的范围为约1小时-1至约5000小时-1,优选约2小时-1至约3000小时-1,更优选约5小时-1至约1500小时-1,最优选约10小时-1至约1000小时-1。在一个优选的实施方式中,WHSV大于20小时-1,优选用于转化包含甲醇和二甲醚的进料的WHSV在约20小时-1至约300小时-1的范围。包含反应器内的稀释剂和反应产物的进料的表观气速(SGV)优选足以使反应器的反应区内的分子筛催化剂组合物流化。方法中的、特别是反应器体系内的、更特别是提升管反应器内的SGV至少为每秒0.1米(米/秒),优选大于0.5米/秒,更优选大于1米/秒,甚至更优选大于2米/秒,还甚至更优选大于3米/秒,最优选大于4米/秒。可以根据本领域的教导和所使用的这些反应及方法设备的经验,由技术工程师选择要在本方法中使用的具体反应参数。
将产物和其它气体从反应器中取出并使其通过回收体系。在本发明中可以使用在将一种或多种烯烃与其它气体成分分离和从其它气体成分提纯一种或多种烯烃中有用的任何常规回收体系、技术和/或顺序。回收体系的实例包括各种分离、分馏和/或精馏塔、柱和分离器及其它相关设备的一种或多种或组合;所述其它相关设备例如为各种冷凝器、热交换器、制冷体系或冷冻机列(chilltrain)、压缩机、分离罐或釜、泵等。
用于甲醇转化反应的催化剂为选定的分子筛、优选沸石和碱性金属氧化物的物理混合物。如上所述,优选的沸石是由MFI结构的沸石例示的中孔径沸石诸如ZSM-5和ZSM-11,和小孔径沸石诸如毛沸石、沸石4A和CHA及ITE结构类型的沸石;其它结构的沸石尚未被证明是有效的且因此是不优选的。也可以使用非沸石分子筛诸如SAPO和ALPO,优选小孔筛诸如SAPO-18和SAPO-34。沸石应具有至少10:1、优选至少50:1、100:1或更高的二氧化硅:氧化铝比率,以使其能够耐受在甲醇脱水反应期间释放的高温蒸汽的钝化作用。可以使用200:1、500:1或者甚至更高的比率(但是有一些给予期望活性的结构铝(structuralaluminum))。沸石应至少部分地为H形。沸石晶体尺寸在小于0.05微米至5微米的范围内,优选的范围在0.5和2微米之间;晶体可以以更大的团聚体存在。
也可发现非沸石分子筛作为催化剂是有效的。非沸石分子筛包括磷酸硅铝分子筛(SAPO)和磷酸铝分子筛(ALPO)、它们的材料和混合物,优选SAPO。将小孔非沸石分子筛定义为具有小于约0.5nm的孔径。通常,合适催化剂的孔径范围为约0.35nm至约0.5nm,优选约0.40nm至约0.50nm,最优选约0.43nm至约0.50nm。
已经证明非沸石材料对各种类型的转化方法都具有催化性质。非沸石分子筛为复杂的三维结晶结构,其包括AlO2或SiO2或者AlO2和SiO2两者及第三金属氧化物。由结晶网络形成的间隙空间或通道使非沸石能够被用作分子筛,所述分子筛在烃进料或产物的很多种转化方法中作为化学反应的催化剂和催化剂载体。
SAPO具有PO2 +AlO2 -和SiO2四面体单元的三维微孔晶体框架结构。化学组成(无水的)为:mR:(SixALyPz)O2;其中“R”表示存在于晶内孔隙体系中的至少一种有机模版剂;“m”表示每摩尔(SixALyPz)O2存在的“R”的摩尔且具有0至0.3的值,最大值在每种情况下取决于模版剂的分子尺寸和所涉及的特定SAPO种类的孔隙体系的可用空隙体积,且“x”、“y”和“z”分别表示硅、铝和磷的摩尔分数。代表性的小孔SAPO为SAPO-17、SAPO-18、SAPO-34、SAPO-44、SAPO-56及其它。在升高的温度下可以将“R”除去。
ALPO具有PO2 +和AlO2 -四面体单元的三维微孔晶体框架结构。化学组成(无水的)为:
mR:(AlyPz)O2
其中“R”表示存在于晶内孔隙体系中的至少一种有机模版剂;“m”表示每摩尔(AlyPz)O2存在的“R”的摩尔且具有0至0.3的值,最大值在每种情况下取决于模版剂的分子尺寸和所涉及的特定SAPO种类的孔隙体系的可用空隙体积,且“y”和“z”分别表示铝和磷的摩尔分数。在升高的温度下可以将“R”除去。
通过包括但不限于在自生压力下于升高温度下的水热合成法的任一种标准合成方法可以实现原位制造催化剂的方法。代表性的前体包括但不限于作为铝源的氧化铝、三甲醇铝和三乙醇铝。正磷酸、磷酸三甲酯和磷酸三乙酯为通常使用的磷前体的实例。胶态二氧化硅、二氧化硅溶胶、四甲氧基硅和四乙氧基硅为通常使用的二氧化碳前体的实例。在合成方法中常用的模版包括例如四甲基氢氧化铵和四乙基氢氧化铵。根据需要对得到的催化剂混合物进行搅拌。在一些情况下,不需要搅拌,可以将混合物静置足以允许期望水平的并入的时间。最后通过常规方法将催化剂产物过滤,任选地进行洗涤、干燥和煅烧。
碱性金属氧化物通过影响甲醇转化的化学过程而起沸石用助催化剂的作用。其主要通过如下方式而在焦炭形成中进行干预:捕获焦炭前体诸如甲醛,从而降低焦炭选择性,减缓或缓和焦炭形成并具有减少的焦炭形成,内在地生成更有活性的甲醇转化催化剂。
与沸石联合使用的金属氧化物助催化剂为具有碱性特性的金属氧化物,其中有碱土金属的氧化物诸如氧化钙和氧化镁。包括铈、镧系金属和化学性质相似的元素钪和钇的稀土元素的氧化物中的碱性金属氧化物是优选的,其中氧化钇是优选的。碱性金属氧化物本身可以被负载在多孔无机负载材料诸如多孔无机氧化物或氧化物的混合物上,优选性质为碱性或中性的一种,从而不引起任何不期望的竞争反应。载体的作用是提高一种或多种活性金属氧化物的分散性,使得更大量的活性位点可用于捕获甲醛,并且为了这一目的,高分散性和高表面积是期望的属性。合适的多孔金属氧化物载体包括二氧化锆(ZrO2)、二氧化钛(TiO2)、二氧化硅(SiO2)、二氧化铈(CeO2)、氧化镁(MgO)、单水方解石或非酸性氧化铝。相对于活性碱性金属氧化物,载体的量应为约50重量百分比,且更低的量是优选的,例如5、10、20或25重量百分比是非常合适的,以便优化活性金属氧化物的量;在各种情况下,将根据载体的表面积和孔隙率以及其使活性氧化物分散接近筛的能力来选择载体的量。负载的活性金属氧化物的具体实例为5~10重量百分比的La2O3/ZrO2。
为了本目的,重要的是使用碱性金属氧化物和沸石的物理混合物,而不是将金属并入沸石结构或者沸石的内部孔隙结构中。由于这一原因,通过与沸石的离子交换或通过也导致交换的在挤出催化剂上的湿浸渍来添加金属氧化物成分对于本目的而言是不合适的。物理混合物可以包含混合但松散的混合物,或更便利地是氧化物和沸石与可能的维持挤出粒子的凝聚性的粘合剂诸如粘土的挤出物。利用金属氧化物和沸石以分开的(separate)粒子的方式设计(envisage)分开式(separate)粒子催化剂体系,特别是在其中与粘合剂结合的挤出催化剂有利于耐磨耗性的移动床或流化床操作中如此。当使用粘合剂时,沸石成分和碱性金属氧化物成分可以为分开的粒子或结合为单一的(single)粒子催化剂。粘合剂应选择为非酸性的,并且如果是分开式粒子催化剂体系,则在移动床操作中的粒子可以在0.5~2cm的尺寸范围中,并且流化床操作的粒子在该技术的常规尺寸范围中,通常为10至100微米,50至100微米是优选的。
沸石对金属氧化物的重量比通常为50:50至90:10,但是取决于选择的反应条件,该范围之外的变化也可以是允许的。
实施例1~2
使用MTG方法示例本发明。本研究中使用的MTG催化剂为Si/Al比为280的ZeolystTMHZSM-5。实施例1为使用HZSM-5作为催化剂的对照实验;实施例2使用HZSM-5和Y2O3(80:20w/w)的催化剂组合物。
对于实施例2,使用研钵和研杵将HZSM-5与氧化钇粉末紧密混合以形成在完成的催化剂组合物中具有按重量计为80:20的百分比组成(HZSM-5:钇氧化物)的催化剂组合物。
使用石英微流TEOM反应器(锥形元件振荡微量天平反应器)进行MTG实验。通常,将大约10mg的催化剂与25mg的100微米石英沙混合。将催化剂装进反应器中。使反应器温度增加至400℃同时使催化剂在He流下(45ml/分钟),允许等待大约40分钟使温度稳定。在400WHSV和170kPag(25磅/平方英寸(psig))下以84微升/分钟将甲醇引入催化剂中,同时通过16-环ValcoTM阀门对流出物进行取样。通常,对样品进行分析以获得加权的平均选择性。通过配备有火焰离子化检测器的在线气相色谱仪(HewlettPackard6890)对收集的流出物样品进行分析。使用的色谱柱为Q-柱。
基于下式对来自两次运行的加权平均产率进行计算:
x1*y1+(x2-x1)*y2+(x3-x2)*(y2+y3)/2+(x4-X3)*(y3+Y4)/2+...,
其中xi和yi分别为产率和g甲醇进料/g筛。
通过对除甲醇和DME之外的产率数据进行标准化来计算选择性。
通过由以下等式所定义的寿命增加指数(LEI)对催化剂寿命延长的定量进行确定:
其中在相同条件下在相同方法中的催化剂或催化剂组合物的寿命为直到经由催化剂组合物的原料的转化降至某一确定水平例如1%以下时每克催化剂组合物处理的原料的累积量。
实施例1和2的结果总结在下表1中,其中指定符号C1、C2=、C2°、C3=、C3°、C4s、C5-7s和芳族化合物类分别是指甲烷、乙烯、乙烷、丙烯、丙烷、丁烯和丁烷、包含五到七个碳的非芳族化合物类和芳族化合物类。“其它”是H2、CO和焦炭选择性的总和。
表1
HZSM-5和HZSM-5/Y2O3的寿命增加指数的总结
(1)CMCPS每克筛转化的累积甲醇(g甲醇/g催化剂HZSM-5),为在单个循环中的催化剂寿命的度量。
HZSM-5催化剂(实施例1)的寿命被测定为312克转化的甲醇/g筛。
HZSM-5/Y2O3催化剂组合物(实施例2)的寿命被测定为462.3g转化的甲醇/g筛。
催化剂组合物的LEI为1.5。换而言之,作为引入氧化钇的结果,在所述甲醇转化方法中的催化剂寿命存在50%的增加。
附图比较单独的HZSM-5和HZSM-5/Y2O3的转化曲线。要注意的是,包含Y2O3的催化剂组合物通常具有相当或更高的活性。在运行即将结束时尤其是这样。
Claims (20)
1.一种甲醇转化方法,所述甲醇转化方法包括:使包含甲醇的进料流与催化剂在甲醇转化条件下接触以形成烃产物,所述催化剂包含分子筛和碱性金属氧化物的物理混合物。
2.根据权利要求1所述的方法,其中所述分子筛包含选自MFI或MEL沸石的中孔径沸石。
3.根据权利要求2所述的方法,其中所述中孔径沸石为ZSM-5或ZSM-11。
4.根据权利要求1所述的方法,其中所述分子筛包含小孔径沸石。
5.根据权利要求1所述的方法,其中所述分子筛包含菱沸石。
6.根据前述权利要求中的任一项所述的方法,其中所述碱性金属氧化物为镧系金属的氧化物。
7.根据权利要求1~5中的任一项所述的方法,其中所述碱性金属氧化物为镁、钙、铈或钪的氧化物。
8.根据权利要求1~5中的任一项所述的方法,其中所述碱性金属氧化物为氧化钇。
9.根据权利要求1~3和5~8中的任一项所述的方法,其中所述分子筛以所述中孔径沸石对所述碱性金属氧化物为50:50至90:10的重量比包含中孔沸石。
10.根据权利要求9所述的方法,其中所述中孔径沸石对所述碱性金属氧化物的重量比为60:40至80:20。
11.根据前述权利要求中的任一项所述的方法,其中所述催化剂为在同一粒子中一起包含所述分子筛和所述碱性金属氧化物的复合粒子催化剂。
12.根据权利要求11所述的方法,其中所述复合粒子催化剂在同一挤出物粒子中包含所述分子筛和所述碱性金属氧化物一起的挤出物。
13.根据权利要求1~10中的任一项所述的方法,其中所述催化剂为在分开的粒子中包含所述分子筛和所述碱性金属氧化物的分开式粒子催化剂体系。
14.根据权利要求13所述的方法,其中所述分开式粒子催化剂包含所述分子筛的挤出物和所述碱性金属氧化物的挤出物作为分开的挤出物粒子。
15.根据前述权利要求中的任一项所述的方法,其中将所述催化剂保持在固定床中。
16.根据权利要求1~14中的任一项所述的方法,所述方法作为移动床方法运作。
17.根据权利要求1~14中的任一项所述的方法,所述方法作为流化床方法运作。
18.根据前述权利要求中的任一项所述的方法,其中所述进料流包含甲醇和另一种含氧化合物。
19.根据前述权利要求中的任一项所述的方法,其中所述进料流包含甲醇和二甲醚。
20.根据前述权利要求中的任一项所述的方法,其中所述烃产物包含烯烃或芳族化合物。
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2013
- 2013-10-04 US US14/046,548 patent/US20150099913A1/en not_active Abandoned
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2014
- 2014-10-01 WO PCT/US2014/058547 patent/WO2015050939A1/en active Application Filing
- 2014-10-01 EP EP14790862.8A patent/EP3052461A1/en not_active Withdrawn
- 2014-10-01 CN CN201480052283.2A patent/CN105579422A/zh active Pending
- 2014-10-01 CA CA2921861A patent/CA2921861A1/en not_active Abandoned
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WO2013091335A1 (zh) * | 2011-12-19 | 2013-06-27 | 中国科学院大连化学物理研究所 | 甲醇和/或二甲醚制取乙烯丙烯的催化剂、其制法及应用 |
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CN105056989A (zh) * | 2015-07-24 | 2015-11-18 | 麦森能源科技有限公司 | 用于甲醇制汽油的催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
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CA2921861A1 (en) | 2015-04-09 |
US20150099913A1 (en) | 2015-04-09 |
WO2015050939A1 (en) | 2015-04-09 |
EP3052461A1 (en) | 2016-08-10 |
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