CN1325608C - 烃催化裂化制备烯烃的方法 - Google Patents
烃催化裂化制备烯烃的方法 Download PDFInfo
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- CN1325608C CN1325608C CNB2003801022224A CN200380102222A CN1325608C CN 1325608 C CN1325608 C CN 1325608C CN B2003801022224 A CNB2003801022224 A CN B2003801022224A CN 200380102222 A CN200380102222 A CN 200380102222A CN 1325608 C CN1325608 C CN 1325608C
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- zeolite
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- manganese
- catalytic cracking
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 26
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000011572 manganese Substances 0.000 claims abstract description 51
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 49
- 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 49
- 239000010457 zeolite Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- -1 ethylene, propylene Chemical group 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 13
- 229910052746 lanthanum Inorganic materials 0.000 description 11
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 230000002688 persistence Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005216 hydrothermal crystallization 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
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012159 carrier gas Substances 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- VWDWKYIASSYTQR-YTBWXGASSA-N sodium;dioxido(oxo)azanium Chemical compound [Na+].[O-][15N+]([O-])=O VWDWKYIASSYTQR-YTBWXGASSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- 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
- 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
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种催化裂化烃原料制备烯烃的方法,其中使用含有稀土元素及含锰和锆中至少一种的五元环型沸石作为催化剂。利用这种催化剂,可以在比常规方法低的温度下使气态或液态烃成分催化裂化,并能抑制如芳烃或重质的副产物生成。可以以选择性高产率和长时间稳定性制备轻质烯烃如乙烯、丙烯等。
Description
技术领域
本发明涉及烃催化裂化制备烯烃的一种方法,更具体地,本发明涉及采用特殊催化剂通过烃催化裂化制备轻质烯烃,主要是乙烯和丙烯。
背景技术
轻质烯烃如乙烯、丙烯等是制备各种化工产物的重要原料。一般地,在蒸汽存在下于外部加热式管式炉中,采用气态烃原料如乙烷、丙烷、丁烷等或液态烃原料如石脑油等热分解制备轻质烯烃是广泛应用的方法。然而,为提高烯烃的产量,需要将温度提高到800℃或更高,设备必须采用昂贵的材质,热分解方法在经济上是不利的。
因此,采用催化剂催化裂化烃的多种方法不断被研究。其中,有应用固体酸特别是五元环(penta-sil)型沸石如ZSM-5的许多实施例报道。由于它具有在500-700℃反应温度下,乙烯和丙烯的产率较高(分别为约10-30wt%)的优点。
例如,已公开的采用具有特殊酸度和酸强度的ZSM-5型催化剂的催化裂解方法(例如参见日本待审专利申请特许公开号Hei 3-504737和Hei 6-346062)和采用含有过渡金属如铜、钴等的ZSM-5型催化剂的催化裂解方法(例如参见日本待审专利申请特许公开号Hei 2-1413和Hei 2-184638)。此外,公开的还有采用含有稀土元素的ZSM-5型催化剂的催化裂解方法(例如参见美国专利申请5,232,675和5,380,690、欧洲专利727404、日本待审专利申请特许公开号Hei11-180902和Hei11-253807)。在反应中采用这些沸石催化剂的问题主要是反应中烃的过度分解和氢的析出反应产生的碳(焦)粘附在催化剂上,引起催化活性降低。因此采用流化床反应装置连续再生(例如参见美国专利申请5,232,675和5,380,690和欧洲专利727404)或者在大量蒸汽存在下反应(例如参见日本待审专利申请特许公开号Hei11-180902和Hei 11-253807)是必须的。但是,为再生引入的蒸汽或碳的燃烧产生的高温蒸汽会引起沸石晶格脱铝,从而导致催化活性的永久丧失。因此,为了使这些沸石催化剂在工业化中能长时间使用,改善沸石的水热稳定性是必须的。
沸石水热稳定性主要靠自身的晶型或者SiO2/Al2O3的配比增大来改性。例如,据报道高硅型的沸石SiO2/Al2O3摩尔比为10或以上具有出众的耐热性(参见“Studies in surface Science and Catalysis”,1996,105卷,p.1549)。但是,这些催化剂缺乏在工业化条件下长时间使用的持久性。因此多种改良方法被研究。
例如,含有过渡金属如Fe、Cu、Co、Ni、Cr、Mn等,并含有钾或铯的具有高水热稳定性的ZSM-5型沸石是不能用作裂化催化剂的,因为它含有碱金属钾和铯等(例如参见日本待审专利申请特许公开号Hei 4-50115、Hei 4-55310、Hei 4-78443和Hei 4-78444)并且因为酸的强度太弱。虽然有文献报道含有Mn的ZSM-5型催化剂能改善水热稳定性,但催化裂化的催化活性不明显(参见“Studies in SurfaceScience and Catalysis”,1996,105卷,p.1549)。此外,虽然日本待审专利申请特许公开号Hei 8-299166公开了含有Mn和/或Re的ZSM-5型催化剂用于烃催化裂化反应,但对持久性未做说明,由于产生过多的芳烃副产物而使烯烃选择性仅有40%或更小。
此外,虽然采用包含沸石和分散在无机基体中的Mn的催化剂的流化催化裂化方法已被公开。但其目的是制备汽油,同时认为沸石中含Mn是不利的,因为汽油的辛烷值降低了(例如参见日本待审专利申请特许公开号Hei 8-299166,Hei 4-300210)。而且,虽然美国专利号4,956,075公开了采用经锰和稀土元素改性的大孔径(Y型)沸石催化剂催化裂化方法可获得高辛烷值的汽油,但是不仅乙烯和丙烯几乎没有得到,而且对持久性也没说明。
采用其它改性剂,例如Zr等,对沸石的水热稳定性的改善也已公开,然而是在约400℃相对低的温度下研究的。并且关于稀土元素的结合影响以及在烯烃制备中应用是否有效未作出清楚的说明(例如参见日本待审专利申请特许公开号Hei 3-505844)。
综上所述,尚未建立任何具有高产率且催化活性长时间稳定的制备烯烃的烃催化裂化方法。
发明内容
本发明的目的是提供一种通过烃催化裂化制备烯烃的方法,该方法在比传统方法温度低且抑制副产物如芳烃或重质烃的条件下催化裂化气态或液态烃原料,能以高选择性产率和长时间稳定性制备轻质烯烃诸如乙烯、丙烯。
本发明达到上述指标是大量研究的结果。发现含有稀土元素和锰和/或锆的沸石能改善催化剂的水热稳定性,并且本发明通过烃催化裂化反应可以高产率获得烯烃,而且催化活性长时间稳定。
也就是说,本发明提供:
(1)一种催化裂化烃原料制备烯烃的方法,其特征在于采用含有稀土元素及含有锰和锆中至少一种的五元环型沸石作为催化剂。
(2)按上面(1)制备烯烃的方法,所述催化剂中稀土元素的含量以与沸石中铝的原子比表示为0.4-20。
(3)按上面(1)制备烯烃的方法,所述催化剂中锰和锆的总含量以与沸石中铝的摩尔比表示为0.1-20。
(4)按上面(1)制备烯烃的方法,所述催化剂还含有0.1%-5mol%的磷。
(5)按上面(1)制备烯烃的方法,所述催化剂沸石中Si02/Al2O3的摩尔比为25-800。
(6)按上面(1)制备烯烃的方法,所述催化反应在蒸汽存下进行。
本发明优选实施方案
本发明中气态或液态烃在常温常压下可用作烃原料。一般使用具有2-30个碳原子的链烷烃,优选是2-20个碳原子,或烃原料中链烷烃占主要成分(至少10wt%)。典型的烃原料包括链烷烃如乙烷、丙烷、丁烷、戊烷、己烷等,或轻质烃馏分如石脑油、轻油等。而且原料组分不一定限制在饱和烃,可扩展到含有不饱和键组分的化合物。
本发明的催化剂基本上由含有稀土元素、锰和/或锆的五元环型沸石组成。ZSM-5和/或ZSM-11优选用作沸石。沸石中SiO2/Al2O3的摩尔比为25-800,较好的为40-600,而80-300更优选。
虽然任何稀土元素都可以用,但优选的稀土元素包括镧、铈、镨、钕、钐、钆、镝等,每种稀土元素可以单独使用也可以两种或多种结合使用。稀土元素对催化剂的改性是通过各种盐来进行的,例如:醋酸盐、硝酸盐、卤化物、硫酸盐、碳酸盐或者醇盐、乙酰丙酮酸盐(acetylacetonato)等。采用离子交换法、浸渍法、水热结晶法或其它方法。
为了显示出主催化剂的特性,在稀土元素之外,锰和锆不管是其中一种还是两种都必须包含到催化剂中。沸石中锰和/或锆的添加可以通过离子交换方法、浸渍法、水热结晶法或者其它方法进行,各自采用不种化合物。稀土元素、锰和锆在沸石中的改性次序没有特殊规定,但是,在锰和锆改性后再进行稀土元素的改性可以是优选的。
稀土元素、锰和/或锆负载主催化剂沸石上或包含于主催化剂沸石内是非常重要的,并且仅靠物理作用将沸石与稀土元素、锰和/或锆化合物(氧化物等)结合,主催化剂并不会表现所述效果。
本发明的催化剂中,稀土元素的含量以与沸石中铝的原子比表达为0.4-20,优选为0.6-5,更优选为1-3。当含量小于0.4时,副产物如重焦炭或者芳烃化合物会增加,当含量超过20时,催化活性会失去且烯烃产率下降。锰和/或锆的含量为二者总摩尔量与沸石中铝摩尔量比0.1-20,优选为0.5-10,更优选为1-5。当含量小于上述值时,热稳定性会下降。如果太大,催化剂活性会失去。稀土元素、锰和/或锆的共同作用可以加强催化剂的持久性和抑制副产物的生成,仅靠锰和/或锆改性而无稀土元素会降低水热稳定性同时副产物增多。
本发明催化剂的构造可以是任何粉末、成型固体等等,没有特别规定。而且这些催化剂可含有除沸石、稀土元素、锰和/或锆外的其它组分如碱元素、碱土元素、过渡金属、贵金属、卤素、磷、粘合剂等。催化剂可以与填料如硅、铝、氧化镁或者石英砂等结合。
对于本发明采用的催化裂化反应方式没有特别规定,然而催化裂化反应可以通过将烃原料输入催化层进行,其中催化剂装填在某种类型的反应器中如固定床、移动床、流化床等。在这种情况下,烃原料可用氮气、氢气、氦气、蒸汽等稀释。
反应温度为350-780℃,优选为500-750℃,更优选为600-700℃。虽然催化裂化反应可以在超过780℃下进行,但甲烷和焦炭的生成会加剧。反之,若温度低于350℃,由于没有足够的活性烯烃的单通产率将下降。
反应压力可采用常压、减压或者加压进行,但通常采用常压或微压操作。
在上述条件下,本发明可以低温高产率将烃原料分解生产轻质烯烃如乙烯、丙烯等。
下列实施例详细解释本发明,但本发明并不局限于这些实施例。
实施例
实施例1
4克粉末状质子型ZSM-5沸石浸渍到含有硫酸锰的水溶液(用60ml去离子水溶解0.62克MnSO4·5H2O制得)中,相应于沸石中铝的等分子量,其量为2.6毫摩尔。溶液在40℃下搅拌两小时。质子型ZSM-5与沸石的SiO2/Al2O3比通过荧光X射线分析为50,比表面为380m2/g,粒径在150μm或更小。产生的浆液在40-60℃减压下搅拌蒸发除湿2小时,而后得到白色粉末。将粉末在120℃空气中干燥8小时后,用4小时加热马弗炉至600℃,接着600℃下焙烧5小时。然后,焙烧的粉末被粉碎,进一步浸渍在含有0.4克镧的水溶液(用60ml去离子水溶解0.99g醋酸镧1.5水合物制得),以同样方式干燥和焙烧后地负载锰,最后获得灰白色固体。灰白色固体在研体中进一步磨碎,得到的粉末通过150μm的筛子,筛分后的粉末称为La-Mn/HZSM-5催化剂。镧和锰的含量以与沸石中铝的原子比表示分别为1.1和1.0。
随后,制得的催化剂经高温蒸汽处理后催化活性通过正己烷的脉冲分解反应(pulse decomposition reaction of n-hexane)进行评价。
也就是说,由实施例1制得的La-Mn/HZSM-5催化剂经压缩、粉碎、筛分和成型得到直径约1mm的粒状催化剂,将1g催化剂装入管式固定床反应器中,通氮和蒸汽于700℃下进行高温蒸汽处理24小时(蒸汽分压40千帕)。高温蒸汽处理结束后,反应器中通入氮气,催化层温度设置在500℃,实施正己烷脉冲分解反应。以氮气为载气,流量75cm3/min,正己烷出口转化率可以通过向反应器注入一股正己烷来测量(注入量1μl)。
结果列于表1,另外,将未改性的HZSM-5经相同的处理后评价结果也列于表1用于对比。
实施例2
用镧和锆改性的HZSM-5催化剂(La-Zr/HZSM-5催化剂)以与实施例1相近的方式制备,区别在于含硫酸锰的水溶液被溶有2.6毫摩尔的硝酸氧锆溶液所代替(用60ml去离子水溶解0.69克ZrO(NO3)2·2H2O制得)。镧和锆的含量以与沸石中的铝原子比表示分别为1.1和1.0。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表1。
实施例3
用镧、锰和锆改性的HZSM-5催化剂(La-Mn-Zr/HZSM-5催化剂)以与实施例1相近的方式制备,区别在于含硫酸锰的水溶液被溶有1.95毫摩尔的硫酸锰和0.65毫摩尔的硝酸氧锆溶液所代替(用60ml去离子水溶解0.47克MnSO4·5H2O和0.174克ZrO(NO3)2·2H2O制得)。镧和(Mn+Zr)的含量以与沸石中的铝原子比表示分别为1.1和1.0(Mn+Zr)。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表1。
实施例4
取4g实施例1制得的粉末催化剂(La-Mn/HZSM-5催化剂)注入磷酸氢二铵水溶液中(用60ml去离子水溶解0.68g磷酸氢二铵制得),所得溶液在40℃下搅拌2小时,所得浆液在40-60℃搅拌下减压蒸发除湿2小时,得到灰白色粉末。所得粉末在120℃空气中干燥8小时后,在马弗炉中4小时加热到600℃,然后在600℃下焙烧5小时。灰白色粉末在研体中进一步磨碎,得到粉末通过150μm的筛子,筛分后的粉末称为P-La-Mn/HZSM-5催化剂。镧、锰和磷的含量以与沸石中铝的原子比表示分别为1.1、1.0和1.1。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表1。
实施例5
P-La-Zr/HZSM-5催化剂以与实施例4相近方式制备,区别在于La-Mn/HZSM-5催化剂被实施例2中的La-Zr/HZSM-5催化剂取代。La、Zr和P含量以与沸石中铝的原子比表示分别为1.1、1.0、1.1。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表1。
对比例1
由实施例1得到的粉末状质子型ZSM-5沸石(SiO2/Al2O3比率:50),取4g用量,注入到含有0.4g镧的水溶液中(0.99克乙酸镧1.5水合物溶解在60毫升去离子水中制得),所得到的溶液于40℃的温度下搅拌2小时。所得泥浆在40-60℃的温度下减压搅拌,蒸发除湿2个小时,得到白色的粉末。将所得粉末在空气中120℃下干燥8个小时,粉末在马弗炉中4小时内加热到600℃,然后600℃下焙烧5小时。将白色固体进一步用研钵碾碎,再用150μm的筛子过滤所得的粉末,筛分而得的粉末命名为La/HZSM-5催化剂。La含量以与沸石中铝的原子比表示为1.1。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表2。
对比例2
负载磷的P-La/HZSM-5催化剂以与实施例4相近的方式制备,区别在于使用4g由对比例1制得La/HZSM-5。La和P含量以与沸石中铝的原子比表示为1.1。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表2。
对比例3
4g实施例1使用的粉末状质子型ZSM-5沸石(SiO2/Al2O3比率:50),注入到含有2.6毫摩尔硫酸锰的水溶液中(60毫升去离子水溶解0.62克MnSO4·5H2O制得),其相应于沸石中含有的铝的等分子量,所得溶液在40℃下搅拌2小时。得到浆液在40℃-60℃下、减压搅拌蒸发除湿2个小时,得到白色粉末。将粉末在空气中120℃下干燥8小时,粉末放入马弗炉中4小时内加热到600℃,然后600℃下焙烧5小时。白色固体进一步用研钵碾碎,用150μm筛子筛分得到的粉末称为Mn/HZSM-5催化剂。Mn含量以与沸石中铝的原子比表示为1.0。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表2。
对比例4
用锆改性的HZSM-5催化剂(Zr/HZSM-5催化剂)以与实施例3相近的方式制备,区别在于含硫酸锰的水溶液被2.6毫摩尔硝酸氧锆水溶液(60毫升去离子水溶解0.69克ZrO(NO3)2·2H2O制得)代替。Zr含量以与沸石中铝的原子比表示为1.0。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表2。
对比例5
负载磷的P-Mn/HZSM-5催化剂以与实施例4相近的方式制备,区别在于使用4g由对比例3制得的Mn/HZSM-5。Mn和P得含量以与沸石中的铝原子比表示分别为1.0和1.1。
该催化剂经高温蒸汽处理后的正己烷脉冲分解反应结果列于表2。
表1
催化剂 | 正己烷转化率(%) | |
未改性 | HZSM-5 | 4.2 |
实施例1 | La-Mn/HZSM-5 | 15.5 |
实施例2 | La-Zr/HZSM-5 | 12.2 |
实施例3 | La-Mn-Zr/HZSM-5 | 15.0 |
实施例4 | P-La-Mn/HZSM-5 | 16.0 |
实施例5 | P-La-Zr/HZSM-5 | 12.5 |
表2
催化剂 | 正己烷转化率(%) | |
对比例1 | La/HZSM-5 | 4.5 |
对比例2 | P-La/HZSM-5 | 5.2 |
对比例3 | Mn/HZSM-5 | 6.5 |
对比例4 | Zr/HZSM-5 | 5.5 |
对比例5 | P-Mn/HZSM-5 | 6.8 |
通过表1和表2比较,可以明显看出,本发明实施例中制得的催化剂在高温蒸汽处理后,催化活性显著强于未改性的催化剂及对比例中催化剂。
实施例6
在实施例1中制得的La-Mn/HZSM-5催化剂被压缩、碾碎、过筛和成型制成直径1mm的颗粒催化剂。取1g催化剂装入内径10mm的不锈钢反应管(具有外径3mm的热电偶内插管)中。催化层高度为30mm。催化层顶部和底部都填了一层石英砂。当空气以40cm3/min(0℃、转化为1atm,下同)的流率进入固定床反应器,催化层的温度上升到650℃,将催化层原样预处理1小时。预处理后,高温水热条件下进行正丁烷催化裂化反应,催化层温度保持650℃,原料正丁烷、氮气和蒸汽的进料流率分别为3.0cm3/min、30cm3/min和0.5g/h。
反应产物用气相色谱分析,产物产率和原料转化率的值分别由下式计算:
产物产率(wt%)=(各组分的质量/原料总质量)×100
原料转化率(%)=(1-未反应原料的质量/原料总质量)×100反应结果列于表3。
实施例7和实施例8
实施例7和实施例8的正丁烷催化裂化反应以与实施例6相近的方式进行,区别在于分别使用实施例2制得的La-Zr/HZSM-5催化剂或者实施例4制得的P-La-Mn/HZSM-5催化剂。
反应结果列于表3。
对比例6和对比例7
对比例6和对比例7的正丁烷催化裂化反应以与实施例6相近的方式进行,区别在于分别使用实施例2制得的P-La/HZSM-5催化剂,或者实施例3制得的Mn/HZSM-5催化剂。
反应结果列于表4。
在表3和表4中Y代表产物产率。
表3
实施例6 | 实施例7 | 实施例8 | |||||
催化剂 | La-Mn/HZSM-5 | La-Zr/HZSM-5 | P-La-Mn/HZSM-5 | ||||
原料 | 正丁烷 | 正丁烷 | 正丁烷 | ||||
温度(℃) | 650 | 650 | 650 | ||||
反应时间(hrs) | 2 | 50 | 2 | 50 | 2 | 50 | |
原料转化率(%) | 94.9 | 91.5 | 96.3 | 92.7 | 93.8 | 90.2 | |
Y(wt%) | 乙烯 | 39.0 | 34.9 | 34.8 | 31.0 | 37.3 | 36.0 |
丙烯 | 14.8 | 14.5 | 21.4 | 22.0 | 14.7 | 15.3 | |
丁烯 | 0.6 | 0.6 | 2.6 | 4.1 | 0.5 | 2.1 | |
芳烃 | 5.2 | 6.2 | 2.8 | 2.7 | 4.0 | 2.4 | |
甲烷 | 16.3 | 15.2 | 13.7 | 13.0 | 15.8 | 15.2 | |
乙烷 | 14.3 | 12.9 | 13.9 | 13.4 | 13.3 | 13.2 | |
丙烷 | 1.0 | 2.2 | 1.2 | 1.3 | 1.1 | 1.1 | |
异丁烷 | 0.7 | 0.9 | 0.3 | 0.3 | 1.0 | 1.3 | |
C5+、焦炭 | 2.2 | 2.1 | 2.8 | 1.3 | 2.0 | 2.1 | |
CO | 0.6 | 2.1 | 1.2 | 1.1 | 4.2 | 1.6 | |
CO2 | 0 | 0.9 | 0.3 | 0.3 | 4.3 | 0.8 |
表4
对比例6 | 对比例7 | ||||
催化剂 | P-La/HZSM-5 | Mn/HZSM-5 | |||
原料 | 正丁烷 | 正丁烷 | |||
温度(℃) | 650 | 650 | |||
反应时间(hrs) | 2 | 50 | 2 | 50 | |
原料转化率(%) | 96.0 | 64.6 | 80.4 | 54.6 | |
Y(wt%) | 乙烯 | 38.9 | 22.2 | 23.2 | 17.7 |
丙烯 | 18.3 | 15.8 | 16.6 | 12.4 | |
丁烯 | 2.2 | 3.2 | 1.7 | 2.4 | |
芳烃 | 2.5 | 0 | 0.7 | 0 | |
甲烷 | 14.5 | 9.8 | 18.8 | 10.4 | |
乙烷 | 13.9 | 9.3 | 12.6 | 7.9 | |
丙烷 | 1.1 | 1.4 | 1.0 | 0.4 | |
异丁烷 | 1.5 | 2.3 | 1.1 | 1.7 | |
C5+、焦炭 | 0.9 | 0.1 | 0.8 | 0.1 | |
CO | 2.3 | 0.5 | 4.4 | 1.8 | |
CO2 | 1.1 | 0 | 6.7 | 2.1 |
通过表3和表4比较,可以明显看出,使用对比例中制得的催化剂,在延长使用时间的情况下,显著降低了转化率和烯烃产率,并且长时间操作下耐久力减弱。而另一方面,本发明的实施例中制得的催化剂,可以在长时间保持高的转化率和烯烃产率。
工业实用性
根据本发明,以气态的或液态的碳氢化合物作为原料,轻质烯烃如乙烯、丙烯等可以在50%或更高的产率下长时间稳定制备,并能抑制副产物如芳香烃或重质成分生成。而且,烯烃制备可以在比常规裂化方法至少低100℃下经济有利地进行。
Claims (6)
1.一种催化裂化烃原料制备烯烃的方法,其特征在于,于350-780℃的温度下使用含有稀土元素及锰或锆中至少一种的五元环型沸石作为催化剂。
2.如权利要求1的烯烃制备方法,其中所述催化剂中所述稀土元素的含量以与沸石中铝的原子比表示为0.4-20。
3.如权利要求1的烯烃制备方法,其中所述催化剂中锰和锆的总含量以与沸石中铝的摩尔比表示为0.1-20。
4.如权利要求1的烯烃制备方法,其中所述催化剂还包含0.1-5mol%的磷。
5.如权利要求1的烯烃制备方法,其中所述催化剂沸石中SiO2/Al2O3的摩尔比为25-800。
6.如权利要求1的烯烃制备方法,其中催化反应在蒸汽存在下进行。
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