CN110139709A - 烃转化催化剂体系 - Google Patents
烃转化催化剂体系 Download PDFInfo
- Publication number
- CN110139709A CN110139709A CN201780076940.0A CN201780076940A CN110139709A CN 110139709 A CN110139709 A CN 110139709A CN 201780076940 A CN201780076940 A CN 201780076940A CN 110139709 A CN110139709 A CN 110139709A
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- Prior art keywords
- catalyst system
- conversion catalyst
- hydrocarbon conversion
- mixture
- chamber
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 71
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 70
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 34
- 150000001336 alkenes Chemical class 0.000 claims description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- 239000001294 propane Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 7
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 claims 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 238000001354 calcination Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 10
- -1 polyethylene Polymers 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 5
- PSFYVNVZQYWSRW-UHFFFAOYSA-N ethanol;tin Chemical compound [Sn].CCO PSFYVNVZQYWSRW-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 3
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ACBYPCPAMDZRDE-UHFFFAOYSA-N C(C)O.[In].[Pt] Chemical compound C(C)O.[In].[Pt] ACBYPCPAMDZRDE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
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- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229910001051 Magnalium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 230000002730 additional effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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Abstract
本发明涉及烃转化催化剂体系,其包含:第一组合物,其含有在固体载体上的脱氢活性金属;和第二组合物,其含有在无机载体上的过渡金属;以及利用烃转化催化剂体系的烃转化方法。
Description
技术领域
本发明涉及烃转化催化剂体系,该体系可以在将包含饱和烃化合物的烃进料转化成烯烃产物的方法中使用。
背景技术
烯烃,尤其是包括乙烯和丙烯的轻烯烃,是有价值的烃产物。它们可以用于制备各种各样的终产物,其包括环氧乙烷、环氧丙烷、乙苯、丙酮、苯酚、聚乙烯、聚丙烯、其它聚合物、以及其它石化产物。尽管价格随着时间已经波动,但是该行业中的需求仍在不断增长。
为了服务工业需要,许多方法已经用于生产烯烃。然而,从诸如链烷烃(paraffin)的更低价值的原料中生产烯烃通常在经济上更有吸引力。用于将饱和链烷烃转化成烯烃的常规方法是热裂化。这是一种高能耗的方法且产品选择性难以调整和控制。
催化裂化是后来开发的方法。用适当的催化材料(通常是沸石基材料)烃裂化可以在不太苛刻的操作条件下发生。
在本领域中,利用适当的催化剂通过脱氢将饱和链烷烃转化成烯烃(具有相应的碳数)的方法也是已知的。可以在脱氢之后进行适当的复分解步骤,以便最终提供满足最高工业需求的改性烯烃产物分布。
在脱氢和复分解方法中可能会发生不同的副反应,例如乙烯、丙烯或丁烯的(再)氢化,反之乙烯、丙烯或丁烯是乙烷、丙烷或丁烷的脱氢反应的优选终产物。进一步地,在氢的存在下,可能会发生进料(诸如丙烷)的氢解和裂化。因此,氢的开发在进一步使得到的烯烃反应中可能是缺点。
尽管公开了用于生产轻烯烃(诸如乙烯和丙烯)的各种方法,但是仍然需要利用较少价值的链烷烃进料的轻烯烃生产方法,其相对于当前技术具有改进的经济性和/或烯烃收率。
发明内容
本发明涉及一种烃转化催化剂体系,其包括:
a.第一组合物,其包含在固体载体上的脱氢活性金属;和
b.第二组合物,其包含在无机载体上的过渡金属。
本发明还涉及利用烃转化催化剂体系的烃转化方法。
具体实施方式
如上所述,本发明涉及包含第一组合物和第二组合物的烃转化催化剂体系。第一组合物包含在固体载体上的脱氢活性金属。脱氢活性金属是指对于烃脱氢而言有效的一组金属。脱氢是氢从分子中脱离的反应。在一个实施方式中,脱氢活性金属选自由铂、钯、铱、铬及它们的混合物组成的组。在一个优选的实施方式中,脱氢活性金属是铂。脱氢活性金属可以以各种氧化态(包括它们的零价或元素金属形式和诸如氧化物形式的其它氧化态)或可选地以多于一种的单一氧化态来存在。
在一个实施方式中,第一组合物基于第一组合物的总重量含有0.01wt%至25wt%的脱氢活性金属、优选地0.05wt%至20wt%的脱氢活性金属、更优选地0.1wt%至5wt%的脱氢活性金属。
在一个实施方式中,固体载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、氧化镁、氧化钙及它们的混合物。在特定的实施例中,固体载体是至少两种或更多种金属氧化物以各种重量比的混合物。例如,固体载体可以选自由氧化镁和氧化铝的混合物、氧化钙和氧化铝的混合物、和它们的混合物、优选地氧化镁和氧化铝的混合物组成的组。混合金属氧化物固体载体可以作为或衍生自层状双氢氧化物(LDH)(诸如镁-铝LDH或钙-铝LDH)来存在。代表性地,混合金属氧化物固体载体可以优选地通过使层状双氢氧化物(诸如镁-铝或钙-铝层状双氢氧化物)经受600℃至700℃、更优选地600℃至650℃范围内的温度达超过2h、更优选地3h至10h来获得。
用于增强第一组合物的催化活性的额外的活性金属(诸如钾、锡、镧、铟、钇、镱、铼及它们的混合物)也可以存在于第一组合物中。在一个优选的实施方式中,第一组合物进一步包含额外的活性金属,其选自由锡、铟及它们的混合物组成的组。
优选地,第一组合物基于第一组合物的总重量包含0.005wt%至2wt%、更优选地0.01wt%至1wt%的额外的活性金属。
在一个代表性实施方式中,铂是脱氢活性金属,混合的氧化镁-氧化铝是固体载体,并且锡是第一组合物中的额外的活性金属。
脱氢活性金属、固体载体和额外的活性金属可以以第一组合物的通常至少约90重量%、典型地至少约95重量%、经常至少约99重量%的组合量来存在。
烃转化催化剂体系中的第二组合物包含在有机载体上的过渡金属。代表性烯烃复分解活性过渡金属可以包括元素周期表第6族和第7族中的那些金属的任何一种或多种。在一个实施方式中,第二组合物的过渡金属选自钼、钨、铼及它们的混合物。过渡金属可以以各种氧化态(包括它们的零价或元素金属形式和诸如氧化物形式的其它氧化态)或可选地以多于一种的单一氧化态来存在。
过渡金属优选地是钨、更优选地以氧化钨的形式。
在一个实施方式中,无机载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、沸石及它们的混合物、优选地二氧化硅或二氧化硅和沸石的混合物。
优选地,沸石选自ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、镁碱沸石(ferrierite)及它们的混合物、更优选地Y-沸石。
对于第二组合物特别优选的是将过渡金属均匀地或可能非均匀地分散在无机载体上。
在一个代表性实施方式中,第二组合物包含分散在无机载体上的氧化钨,该无机载体包含二氧化硅和沸石的混合物。
在另一个实施方式中,第二组合物进一步包含混合金属氧化物,优选地与分散在无机载体上的过渡金属物理地混合的金属氧化物。第二组合物的混合金属氧化物可以优选地选自氧化镁和氧化铝的混合物和氧化钙和氧化铝的混合物。第二组合物的混合金属氧化物可以作为或衍生自层状双氢氧化物(LDH)(诸如镁-铝LDH或钙-铝LDH)来存在。
在一个实施方式中,第二组合物基于第二组合物的总重量包含1wt%至15wt%的过渡金属、甚至更优选地5wt%至10wt%的过渡金属。
过渡金属、无机载体、和任选的混合金属氧化物可以以第二组合物的通常至少约90重量%、典型地至少约95重量%、经常至少约99重量%的组合量来存在。
在根据本发明的烃转化催化剂体系中,可以提供的是第一组合物不同于第二组合物。同样地,包含在第一组合物中的固体载体可以不同于包含在第二组合物中的无机载体。
在另一个实施方式中,可以提供的是第二组合物不包含脱氢活性金属,具体地第二组合物不包含铂、钯、铱、铬、或它们的混合物。
第一组合物优选地通过在固体载体上负载脱氢活性金属和任选的额外的活性金属的所有元素前体随后进行合适的热处理来制备。
类似地,第二组合物优选地通过在无机载体上负载过渡金属的所有元素前体随后进行合适的热处理来制备。
元素前体是含有所需元素的起始化合物,其可以通过合适的热处理在最终的烃转化催化剂中转化成所需形式的元素。例如,元素前体可以包括这些元素的氧化物、卤化物、醇盐、硝酸盐、碳酸盐、甲酸、草酸盐、胺或氢氧化物。
更优选地,第一组合物通过在固体载体上浸渍、优选地同时共浸渍脱氢活性金属和任选的额外的活性金属的元素前体(其以溶液形式来提供)随后煅烧来制备。煅烧优选地在氧化气氛中来进行,在300℃至800℃范围内的温度下进行1h至24h、甚至更优选地在400℃至600℃范围内的温度下进行2h至10h。
在第二组合物进一步包含如上所述的混合金属氧化物的实施方式中,然后进一步将无机载体上的煅烧过渡金属与选择的混合金属氧化物物理地混合,其中然后进一步将得到的混合物煅烧以获得最终的第二组合物。
还更优选地,第二组合物通过在无机载体上、优选地按顺序地浸渍过渡金属的元素前体(其以溶液形式来提供)然后煅烧来制备。煅烧优选地在氧化气氛中来进行,在300℃至800℃范围内的温度下进行1h至24h、甚至更优选地在400℃至600℃范围内的温度下进行2h至10h。
由上面所述的制备方法得到的第一组合物和第二组合物通常是平均粒径低于800微米的粉末形式。
在一个实施方式中,优选地以从1:10至10:1的第一组合物与第二组合物的重量比,更优选地1:5至5:1,甚至更优选地1:3至3:1,并且甚至更优选1:2至2:1,将第一组合物和第二组合物物理地混合以形成烃转化催化剂体系。
在一个实施方式中,烃转化催化剂体系可以是粉末形式。在另一个实施方式中,烃转化催化剂体系还可以形成为更适合于工业利用的形状,例如丸粒、片剂、挤出物、或球形。
第一组合物和第二组合物的物理混合可以在烃转化催化剂体系成型之前或之后来进行。
在一个实施方式中,将第一组合物和第二组合物分别形成为所需形状,然后将形成为所需形状的第一组合物和形成为所需形状的第二组合物物理地混合以获得烃转化催化剂体系。
在另一个实施方式中,将第一组合物的粉末和第二组合物的粉末物理地混合以获得烃转化催化剂体系,然后可以将得到的烃转化催化剂体系形成为任何所需形状。
在第一组合物、第二组合物、或烃转化催化剂体系的成型中,可以添加粘合材料以促进粉末形成为所需形状。可以使用本领域中已知的任何粘合材料。
在另一个实施方式中,还有可能的是以宏观尺度层形式来提供第一组合物和第二组合物,其中第一组合物和第二组合物在固定床反应器中作为独立层来设置。
本发明的催化剂体系适合于用于烃转化方法中。优选地,烃转化方法包含使烃进料流与烃转化催化剂体系接触。
为了获得烯烃产物,有利的是烃进料流包含链烷烃。在一个实施方式中,烃进料流包含具有2至5个原子的链烷烃。在另一个实施方式中,烃进料流包含选自乙烷、丙烷、丁烷、戊烷及它们的混合物、优选地丙烷、丁烷及它们的混合物的链烷烃,甚至更优选地烃进料流是丙烷。
在连续流动体系的情况下,如上面所述的烃进料流可以指单一进料流或总组合进料流,总组合进料流包括例如其它来源的链烷烃,诸如包含已经从产物中分离的链烷烃进料流的未转化部分的再循环流。烃进料流可以但不一定仅包含链烷烃。例如,进料通常主要包含链烷烃,典型地包含至少约80重量%的烃进料流,并且更经常包含至少约90重量%的烃进料流。
烃转化方法可以在宽范围的操作条件下来操作。然而,一些特定范围的操作条件可以导致较高的烯烃生产选择性。在一个实施方式中,该方法在200℃至800℃、优选地350℃至700℃、甚至更优选地450℃至650℃范围内的温度下来进行。在另一个实施方式中,该方法在0.01巴表压至10巴表压、优选地0.05巴表压至5巴表压范围内的压力下进行。获得烯烃产物的所需收率所需的接触时间取决于若干因素,诸如操作温度、操作压力和催化剂活性。在一个实施方式中,该方法在在0.01hr-1至20hr-1、优选地0.05hr-1至5hr-1范围内的重时空速(WHSV)下来进行。该方法可以分批方式或连续方式来进行。对于商业规模而言,有利的是该方法是连续操作的。连续操作可以用固定床、流化床、或本领域中已知的其它工艺来进行,其中固定床是典型地优选的。
在与烃进料流接触之前,可以任选地对烃转化催化剂体系进行预处理。预处理条件可以包括使催化剂体系与惰性气体、氧化气体、还原气体及它们的混合物在升高的温度(优选地250℃至850℃、更优选地400℃至750℃、甚至更优选地500℃至700℃)下接触。在一个优选的实施方式中,预处理条件包括使催化剂与还原剂(更优选地氢气)在400℃至600℃范围内的温度下接触达大约0.5h至8h。
在操作条件下与烃进料流接触后,一些有毒物质、重质烃和焦炭可以沉积在烃转化催化剂体系的表面上。这通常会影响催化剂的活性随时间逐渐下降。适当的再生可以在使用的烃转化催化剂体系上来进行以回收其至少一些活性。在一个实施方式中,烃转化方法包含再生步骤,其中再生步骤包括在高温下使烃转化催化剂体系与氧化剂接触。应当小心地对再生步骤进行控制以避免过热和破坏催化剂的结构。在一个实施方式中,再生步骤通过使使用的烃转化催化剂体系与氧化剂、优选地氧气或空气在200℃至700℃、优选地300℃至600℃范围内的温度下接触来进行。在没有限制的情况下,可以采用其它已知的再生工艺。
烃转化方法通常进一步包含获得包含至少一种(典型地至少两种)烯烃的产物流。在一个实施方式中,产物流包含两种烯烃,其相对于烃进料流中所包含的链烷烃具有不同的碳数。在一个具体的实施方式中,产物流包含乙烯。
在本发明的烃转化方法的代表性实施例中,烃进料流包含丙烷且产物流包含乙烯和丁烯。
令人惊讶地发现的是当用于烃转化方法时,本发明的烃转化催化剂体系能够将链烷烃、优选地丙烷转化成至少一种(典型地至少两种)具有不同碳数的烯烃、优选地乙烯和丁烯,其相对于现有的(非本发明的)催化剂具有更高的选择性。在一个代表性实施方式中,烃转化方法提供至少20wt%、优选地至少40wt%、更优选地至少60wt%的总烯烃选择性,其中总烯烃选择性由以百分比表示的每次通过所转化的链烷烃除以每次通过所生产的总烯烃产物来确定。
实验结果
在下面的实施例部分中,已经使用根据本发明的烃转化催化剂体系的各种示例性实施方式研究了丙烷向烯烃、优选地乙烯、丙烯和丁烯的转化。
前述说明书和权利要求书中所公开的特点可以(单独地和以其任何组合的方式两者)是用于以其各种形式实现本发明的材料。
催化剂的制备
D1:20wt%铂储备溶液通过将4.98g氯铂酸水合物溶解于19.94g乙醇中来制备。将0.2g的20wt%铂储备溶液再次溶解在5g乙醇中,然后通过起始湿润浸渍法将其填装到5g氧化铝载体上。将所得样品在110℃下干燥过夜,然后在空气中在620℃下煅烧达2h。
D2:20wt%铂储备溶液通过将4.98g氯铂酸水合物溶解于19.94g乙醇中来制备。将0.06g的氯化锡(ii)脱水物溶解于5g乙醇中。然后将0.2g的20wt%铂储备溶液溶解于所得的锡-乙醇溶液中。然后通过起始湿润浸渍法将所得的铂-锡-乙醇溶液填装到5g氧化铝载体上。将所得样品在110℃下干燥过夜,然后在空气中在620℃下煅烧达2h。
D3:20wt%铂储备溶液通过将4.98g氯铂酸水合物溶解于19.94g乙醇中来制备。将0.06g的氯化锡(ii)脱水物溶解于5g乙醇中。然后将0.2g的20wt%铂储备溶液溶解于所得的锡-乙醇溶液中。铝酸镁(MgAlO3)混合氧化物通过在620℃下煅烧LDH达8h来制备。然后通过起始湿润浸渍法将所得的铂-锡-乙醇溶液填装到5g氧化铝载体上。将所得样品在110℃下干燥过夜,然后在空气中在620℃下煅烧达2h。
D4:20wt%铂储备溶液通过将4.98g氯铂酸水合物溶解于19.94g乙醇中来制备。将0.08g的硝酸铟(iii)脱水物溶解于5g乙醇中。然后将0.2g的20wt%铂储备溶液溶解于所得的铟-乙醇溶液中。然后通过起始湿润浸渍法将所得的铂-铟-乙醇溶液填装到5g氧化铝载体上。将所得样品在110℃下干燥过夜,然后在空气中在620℃下煅烧达2h。
D5:20wt%铂储备溶液通过将4.98g氯铂酸水合物溶解于19.94g乙醇中来制备。将0.08g的硝酸铟(iii)脱水物溶解于5g乙醇中。然后将0.2g的20wt%铂储备溶液溶解于所得的铟-乙醇溶液中。铝酸镁(MgAlO3)混合氧化物通过在620℃下煅烧LDH达8h来制备。然后通过起始湿润浸渍法将所得的铂-铟-乙醇溶液填装到5g氧化铝载体上。将所得样品在110℃下干燥过夜,然后在空气中在620℃下煅烧达2h。
M1:将1.072g的偏钨酸铵水合物溶解于13g水中。将所得溶液填装到10g硅胶上。将所得样品在110℃下干燥过夜,然后在550℃下煅烧达8h。
M2:将1.072g的偏钨酸铵水合物溶解于13g水中。将所得溶液填装到9.5g硅胶和5gHY沸石的物理混合物上。然后将所得样品在110℃下干燥过夜,然后在550℃下煅烧达8h。然后将煅烧的样品与1g的镁铝层状双氢氧化物进行物理地混合。
催化剂体系建立和测试条件
测试#1:催化剂体系通过将1.5g的D1催化剂填装到3/4”不锈钢反应器中来建立。催化剂体系然后通过在580℃下将100sccm的空气和100sccm的氮气引入反应器中达30min来进行预处理,然后在580℃下将200sccm的氮气引入反应器中达60min,然后在580℃下将200sccm的氮气和50sccm氢气引入反应器中达30min。然后将催化剂体系冷却至570℃,然后在1个大气压下将30sccm的99.6体积%丙烷反应物引入反应器中以开始反应。
测试#2:催化剂体系通过将1.5g的D1与4g的M1物理地混合然后将混合物填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#3:催化剂体系通过将1.5g的D2催化剂填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#4:催化剂体系通过将1.5g的D2与4.3g的M2物理地混合然后将混合物填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#5:催化剂体系通过将1.5g的D3催化剂填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#6:催化剂体系通过将1.5g的D5与4.3g的M2物理地混合然后将混合物填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#7:催化剂体系通过将1.5g的D3与4.3g的M2物理地混合然后将混合物填装到3/4”不锈钢反应器中来建立。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理。
测试#8:将4.3g的M2填装到3/4”不锈钢反应器中,然后填装1.5g的D5。将一定量的石英棉置于M2与D5之间以分离这两层。对反应器进行定位使得D5催化剂位于床的顶部且M2催化剂位于催化剂体系床的底部。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理,其中所有预处理气体和进料流从催化剂床的顶部到底部向下流动。
测试#9:将4.3g的M2填装到3/4”不锈钢反应器中,然后填装1.5g的D3。将一定量的石英棉置于M2与D5之间以分离这两层。对反应器进行定位使得D3催化剂位于床的顶部且M2催化剂位于催化剂体系床的底部。使用了与测试#1相同的催化剂体系和链烷烃进料流的预处理,其中所有预处理气体和进料流从催化剂床的顶部到底部向下流动。
测试结果显示在表1中。
从测试结果可以看到,由根据本发明的第一组合物(D)和第二组合物(M)的组合制成的催化剂体系,乙烯和丁烯选择性的增加显著增加。
表1
Claims (20)
1.一种烃转化催化剂体系,包含:
a.第一组合物,含有在固体载体上的脱氢活性金属;和
b.第二组合物,含有在无机载体上的过渡金属。
2.根据权利要求1所述的烃转化催化剂体系,其中所述脱氢活性金属选自由铂、钯、铱、铬及它们的混合物组成的组。
3.根据权利要求1所述的烃转化催化剂体系,其中所述脱氢活性金属是铂。
4.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述固体载体选自氧化铝、二氧化硅、二氧化锆、二氧化钛、氧化镁、氧化钙及它们的混合物。
5.根据权利要求4所述的烃转化催化剂体系,其中所述固体载体是选自由混合的氧化镁-氧化铝、混合的氧化钙-氧化铝及它们的混合物组成的组中的至少两种或更多种金属氧化物的混合物。
6.根据权利要求5所述的烃转化催化剂体系,其中所述至少两种或更多种金属氧化物的混合物衍生自层状双氢氧化物。
7.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述第一组合物进一步包含选自由钾、锡、镧、铟、钇、镱、铼及它们的混合物组成的组的额外的活性金属。
8.根据权利要求7所述的烃转化催化剂体系,其中所述额外的活性金属选自由锡、铟及它们的混合物组成的组。
9.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述过渡金属选自由钼、钨、铼及它们的混合物组成的组。
10.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述过渡金属是钨。
11.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述无机载体选自由氧化铝、二氧化硅、二氧化锆、二氧化钛、沸石及它们的混合物组成的组。
12.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述无机载体是二氧化硅或二氧化硅和沸石的混合物。
13.根据权利要求11或12所述的烃转化催化剂体系,其中所述沸石选自由ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、镁碱沸石及它们的混合物组成的组。
14.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述第二组合物进一步包含选自氧化镁和氧化铝的混合物以及氧化钙和氧化铝的混合物的混合的金属氧化物。
15.根据前述权利要求中任一项所述的烃转化催化剂体系,其中所述第一组合物与所述第二组合物的重量比是1:10至10:1。
16.一种烃转化方法,包括使烃进料流与根据前述权利要求中任一项所述的烃转化催化剂体系接触。
17.根据权利要求16所述的烃转化方法,其中所述烃进料流包含选自由乙烷、丙烷、丁烷、戊烷及它们的混合物组成的组的链烷烃。
18.根据权利要求17所述的烃转化方法,其中所述烃进料流是丙烷。
19.根据权利要求16至18中任一项所述的烃转化方法,其中所述烃转化方法在200℃至800℃范围内的温度下进行。
20.根据权利要求16至19中任一项所述的烃转化方法,其中所述方法进一步包括获得包含至少两种烯烃的产物流。
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- 2017-11-30 CN CN201780076940.0A patent/CN110139709A/zh active Pending
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TW201822879A (zh) | 2018-07-01 |
US20200070128A1 (en) | 2020-03-05 |
KR20190088055A (ko) | 2019-07-25 |
WO2018108544A1 (en) | 2018-06-21 |
CA3043870A1 (en) | 2018-06-21 |
US11383225B2 (en) | 2022-07-12 |
EP3554688B1 (en) | 2023-08-16 |
KR102471188B1 (ko) | 2022-11-25 |
EP3554688A1 (en) | 2019-10-23 |
JP2020500711A (ja) | 2020-01-16 |
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