TWI694862B - 複分解反應催化劑及使用彼之製程 - Google Patents
複分解反應催化劑及使用彼之製程 Download PDFInfo
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- TWI694862B TWI694862B TW104135215A TW104135215A TWI694862B TW I694862 B TWI694862 B TW I694862B TW 104135215 A TW104135215 A TW 104135215A TW 104135215 A TW104135215 A TW 104135215A TW I694862 B TWI694862 B TW I694862B
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- Prior art keywords
- catalyst
- zeolite
- olefin
- weight
- feed stream
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 17
- 238000005649 metathesis reaction Methods 0.000 title description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 49
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000005865 alkene metathesis reaction Methods 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000011368 organic material Substances 0.000 claims abstract description 10
- 239000011147 inorganic material Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 39
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 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 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000004685 tetrahydrates Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 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
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 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
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B01J35/19—
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- 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
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
-
- 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
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
本發明係關於一種催化劑,其係包含至少一種選自VIA族及VIIA族金屬之過渡金屬以及一載體,該載體含有沸石與至少一種其他無機或有機材料的混合物,基於載體總重,該沸石之量為0.1至60重量%,其中該至少一種其他無機或有機材料係選自二氧化矽、二氧化鈦、二氧化鋯、及活性碳,較佳二氧化矽;以及關於一種利用該催化劑的烯烴複分解反應製程。
Description
本發明係關於一種複分解反應催化劑(metathesis catalyst),以及一種使用該催化劑的烯烴複分解反應製程。
烯烴複分解反應,亦稱作烯烴歧化(dismutation)及不均化(disproportionation),為具有高度實踐利益的反應。該反應通常涉及烯類片段藉由烯烴中碳-碳雙鍵的剪切而重新分配。藉由催化此反應,碳-碳鍵對可以統計方式重組而將簡單分子轉換成具有理想性質的分子。
已發展多種催化劑以改進複分解反應的催化效能。
舉例而言,美國專利申請公開第2010/0145126 A2號描述一種含有在載體上的過渡金屬的催化劑,與含有在載體上的IA、IIA、IIB、或IIIA族金屬的共催化劑混合,用於藉由複分解反應製造烯烴的製程。該反應必須在氫存在下進行,其為昂貴的進料且需要非常小心地處理。此外,氫的存在導致發生副反應的氫化反應,且導致丙烯選擇性的下降。
此外,S.Huang等人(分子催化期刊A:化學物(Journal of Molecular Catalysis A:Chemical)226(2005),61-68)及H.Liu等人(天然氣化學期刊(Journal of Natural Gas Chemistry)
18(2009),331-336)研究使用在氧化鋁-沸石載體上的氧化鎢作為烯烴複分解催化劑,且S.Liu等人(天然氣化學期刊19(2010),482-486)及S.Huang等人(應用催化A:總論(Applied Catalysis A:General)404(2011),113-119)研究使用在氧化鋁-沸石載體上的氧化鉬。彼等解釋將沸石加入氧化鋁載體中可增加催化劑的布氏酸性(Brönsted acidity),導致改進了乙烯與丁烯之複分解反應產生丙烯的轉換率與選擇性。然而,由於焦炭物種(coke species)的累積,這些催化劑承受快速的去活化。
因此,本發明之一目的在於藉由提供一種催化劑及使用彼之製程克服先前技術的缺陷,其顯示良好催化效率,尤其是烯烴複分解反應中改進的選擇性及催化劑穩定性。
前述目的係由一種催化劑達成,該催化劑包含至少一種選自VIA族及VIIA族金屬之過渡金屬以及一載體,該載體含有沸石與至少一種其他無機或有機材料的混合物,基於載體總重,該沸石之量為0.1至60重量%,其中該至少一種其他無機或有機材料係選自二氧化矽、二氧化鈦、二氧化鋯、及活性碳,較佳二氧化矽。
用語「VIA族及VIIA族金屬」係指元素週期表中第VIA族及VIIA族,包括鉻、鉬、鎢、錳、鎝、錸。在一較佳實施態樣中,該至少一種過渡金屬係選自錸、鉬、及鎢,更佳為鎢。
根據本發明,催化劑中使用的過渡金屬依據所需的
催化活性,其用量可相當廣泛。較佳地,基於該催化劑總重,該催化劑包含1至12重量%之該過渡金屬(以金屬元素計),更佳5至10重量%。
過渡金屬組分可以金屬元素及/或一或多種金屬化合物存在,例如氧化物、氫化物、或硫化物;較佳為氧化物。並且,該過渡金屬可為零價或任何更高的氧化態。
用語「沸石」係指鋁矽酸鹽的一個特殊群組。這些沸石呈現SiO4及AlO4四面體的網格,其中鋁原子與矽原子藉由共享氧原子而在三維網格中交聯。在該網格中,氧原子對鋁原子和矽原子總數的比值可等於2。網格展現負電子價,其典型藉由於晶體中包含例如金屬、鹼金屬、鹼土金屬、或氫等陽離子而平衡。
可用於本發明的沸石包括大型、中等、及小型孔隙尺寸的沸石,且可為天然存在或合成的。該等沸石的實例包括結構類型為FAU、FER、MWW、MOR、BEA、LTL、MFI的沸石及其任意組合。該等命名的細節可見於純應用化學(PureAppl.Chem)73(2),pp.381-394,2001所刊載的IUPAC推薦2001(IUPAC Recommendations 2001)。
在本發明中,沸石較佳選自ZSM-5、鎂鹼沸石(Ferrierite)、X-沸石、Y-沸石、β-沸石、及MCM-22,較佳鎂鹼沸石、X-沸石或Y-沸石,更佳Y-沸石。
亦較佳地,沸石的氧化矽對氧化鋁的莫耳比值在2至500之範圍,較佳10至200,更佳12至20,最佳14至18。
添加到載體的沸石量影響催化劑的效能。太少量的沸石無法對轉換率及選擇性提供顯著的改進。另一方面,太大量
的沸石可能導致相對低的催化穩定性。
較佳地,基於該載體總重,該載體包含0.1至30重量%之該沸石,較佳0.5至20重量%,更佳1至10重量%,最佳4至8重量%。
在某些實施態樣中,該至少一種其他無機或有機材料可為二氧化矽的奈米晶體或奈米顆粒,其尺寸為1奈米至100奈米範圍。
催化劑亦可含有適當用量的至少一種鑭系金屬,以增進催化劑的效果。本發明中,鑭系金屬係指元素週期表中的鑭系。其包括任何化學上相關聯之具有原子序57至71的元素,亦稱作稀土族或稀土元素。在一實施態樣中,該至少一種鑭系金屬選自鑭、鈰、錯、釹、釤、及釓,較佳為鑭。該至少一種鑭系金屬的存在可對於烯烴複分解催化劑的活性及選擇性具有利效果。
本發明催化劑可更與任何適合的黏結劑混合,並藉由擠製或其他適合的方法形成任何理想形狀,例如球型、擠製物、粒狀、或環狀。
本發明催化劑可藉由多種技術製備。在一實施態樣中,本發明催化劑可藉由以下步驟製備:a)將適當用量的沸石與至少一種其他無機或有機材料混合;b)將步驟a)所獲得的產物與至少一種過渡金屬化合物及至少一種溶劑接觸;以及c)乾燥及/或煅燒步驟b)所獲得的產物。
較佳地,該混合藉由物理混合進行。更詳細而言,混合藉由將固體形式的沸石和固體形式的至少一種其他無機或有
機材料以經計算的重量比放在一起,之後以攪拌或搖動將其混合直到獲得實質均勻的混合物。
較佳地,使用於步驟a)的沸石選自HY-沸石、NaY-沸石及NH4Y-沸石,較佳HY-沸石。
此外,步驟a)中的至少一種其他無機或有機材料亦較佳為矽膠。
將所製備的載體與過渡金屬化合物之溶液接觸的方法可廣泛選自多種已知的技術,例如,浸漬、共沉澱、初始濕潤(incipient wetness)及離子交換。在某些實施態樣中,步驟b)的接觸較佳藉由浸漬技術進行。
本發明的過渡金屬化合物有多種可能選擇,例如過渡金屬之氧化物、鹵化物、硫酸鹽、硝酸鹽、鹽類或硫化物。該至少一種過渡金屬化合物較佳為四水合偏鎢酸銨(ammonium metatungsten tetrahydrate)。
本發明所選用溶劑可為任何適合的溶劑,其可溶解或分散所選擇的金屬化合物,例如含氧溶劑(oxygenated solvent)及烴類溶劑。舉例而言,溶劑可選自水、甲醇、乙醇及己烷。溶劑較佳為水。
在步驟a)與b)之後,可進行乾燥以移除任何多餘的液體。可使用本領域人士已知的任何方法,例如烘箱乾燥、流動劇烈的任何乾燥氣體流通過欲乾燥物體等。乾燥步驟的時間可於數分鐘至數小時之間變動。較佳地,其應以至少足以使部分或全部的多餘液體被移除的時間進行。典型地,在較高溫度下需要較短時間,反之亦然。乾燥較佳於2至24小時期間進行。
乾燥的溫度範圍可由室溫至任何較高溫度,其能夠在催化劑載體及催化劑中存在的金屬化合物不發生轉化或變性的情況下蒸發液體。乾燥較佳在20℃至200℃溫度進行。
乾燥可於任何在用於乾燥的條件下不與催化劑或催化劑中組分反應的氣體之氣氛中進行,例如,空氣、氮、氬、甲烷及氫。乾燥較佳於空氣或氮中進行。
必要時,在製備步驟的步驟a)及b)後可進行煅燒。煅燒包含在適合熱分解及移除金屬化合物的可揮發部分的氣氛中,於控制條件下處理所製備的催化劑。可揮發部分係指化合物的陰離子配位體部分,其可分解為氣體化合物。煅燒較佳在200℃至800℃溫度進行。煅燒亦較佳在1至24小時期間進行,較佳5至10小時。
在煅燒步驟中,可存在惰性氣體、氧化氣體、還原氣體及其任意組合,以創造適當的氣氛。在一特定實施態樣中,煅燒於空氣中進行。
本發明之目的亦由一種烯烴複分解反應製程達成,該製程包括:a)提供本發明催化劑;b)視需要活化步驟a)之催化劑;以及c)將步驟a)或b)之催化劑與一烯烴進料流接觸。
該進料流可於與本發明催化劑接觸前或同時視需要與共催化劑接觸,例如,烯烴異構催化劑。異構催化劑可對烯烴複分解製程有利,因為其促進進料流中活性較低的組分轉變為活性較高的組分。舉例而言,異構催化劑促進1-丁烯轉化為2-丁烯,
其於製造丙烯的烯烴複分解中活性較高。對於烯烴異構化具活性的催化劑為已知種類,且可與本發明催化劑以多種不同形式結合。對此,可參考美國專利第4,575,575號、美國專利第5,120,894號、美國專利申請公開第2011/0077444A1號、及分子催化期刊(Journal of Molecular Catalysis)28(1995)117-131。
本發明催化劑可在與進料流接觸前先有益地被活化。在一實施態樣中,本發明催化劑藉由包含於200℃至700℃之溫度處理該催化劑的方法活化。活化方法一般涉及在經控制的氣氛下將催化劑加熱到提高的溫度一段時間,其足以活化催化劑。舉例而言,可用於本發明的活化方法可參考美國專利第4,575,575號、歐洲專利申請公開第2151424A1號、美國專利申請公開第2010/0167911A1號、及應用催化A:總論(Applied Catalysis A:General)255(2003)133-142。
將催化劑與進料流接觸較佳包含將固態催化劑與氣態進料流接觸。
所使用的反應溫度可基於使用的催化劑及進料而改變。較佳地,將催化劑與進料流接觸於200℃至600℃溫度進行,更佳250℃至550℃,最佳350℃至450℃。
在催化劑與進料流接觸的壓力可廣泛改變。舉例而言,可使用1大氣壓至60大氣壓的壓力,較佳20大氣壓至40大氣壓。
在催化劑與進料流接觸時,基於溫度、壓力及其他數項因子,可選擇0.01小時-1至200小時-1,較佳0.05小時-1至100小時-1的WHSV以獲得合理的產率。用語「WHSV」係指每小
時之重量空間速度(Weight Hourly Space Velocity)。其可由進料流的質量流速除以反應中使用催化劑重量計算而得。
對本發明而言,進料流可為一或更多種烴類物流,包含至少一些不飽和分子,例如芳香族、環狀、二烯烴或烯烴。較佳地,進料流為C2至C5烴類物流,包含至少一些不飽和分子。更佳地,進料流包含烯烴,其選自以下所組成之群組:C2烯烴、C3烯烴、C4烯烴、C5烯烴、及其混合物。
在一實施態樣中,進料流包含至少一第一烯烴及至少一第二烯烴。較佳地,該第一烯烴及該第二烯烴係選自乙烯及2-丁烯、或乙烯及2-戊烯,較佳乙烯及2-丁烯。
或是,製程在步驟c)之後更包含一再生步驟。
當本發明催化劑用於反應製程中且因催化劑表面累積毒化物質、焦炭、碳及/或聚合物而失去活性時,其可進行再生。在再生製程中,沉積於催化劑表面的毒化物質、焦炭、碳及/或聚合物實質上被移除。控制再生步驟的條件,使得可達成另人滿意的焦炭移除程度,而孔隙結構、活性位置及其他原本的催化功能並不被過分地改變或毀壞。可用於本發明催化劑的再生製程之實例可見於應用催化A:總論255(2003)133-142、美國專利申請公開第2010/0167911A1號、及美國專利第4,522,936號。
令人驚訝地,發現本發明催化劑及本發明製程可於烯烴複分解反應中提供高產率、高選擇性、以及高催化穩定性。
實施例
以下實施例將僅用於例示本發明。其並非以任何方式限制本發明的範疇。可在不背離後附申請專利範圍所揭露的本
發明範疇之下,做出多種改變及修改。
實施例1(催化劑製備)
製備根據本發明之催化劑:首先將90重量%矽膠與10重量%HY-沸石物理地混合,然後浸漬一含有預先計算用量的四水合偏鎢酸銨之水溶液於該矽膠與HY-沸石之混合物。所獲得的混合物,於烘箱中以110℃乾燥整夜(overnight)前,先於周圍空氣下放置2小時。最終的乾燥混合物呈現白色固體狀。接下來,白色固體混合物在空氣中於500℃下煅燒8小時,以獲得可用於複分解反應中的最終催化劑。
實施例2(轉化率與選擇性測試)
將催化劑樣品用於轉化率與選擇性測試。樣品包括:樣品A包含在載體上的氧化鎢,載體包含90重量%氧化矽及10重量%Y-沸石的混合物,樣品B包含在氧化矽載體上的氧化鎢,以及樣品C包含在經0.5重量%鑭改質的氧化矽載體上的氧化鎢,其中樣品A至C皆含有相同量的氧化鎢。
樣品A、樣品B及樣品C在測試前先加以處理:將3公克催化劑承載於反應器中,並在氮氣流中將催化劑加熱至500℃歷時1小時。之後,在催化劑混合物上於350℃進行乙烯與包含1-丁烯、2-丁烯、異丁烯、及其他石蠟烴(paraffins)的其他進料流的複分解反應。
反應流出物被送至GC-FID(Agilent)以測量其化學組成。所測量的反應流出物組成用於計算丁烯轉化率及丙烯選擇
性。丁烯轉化百分率由反應中被轉化的1-丁烯及2-丁烯重量,除以進料流中1-丁烯及2-丁烯重量,再乘以一百而計算。並且,丙烯選擇百分率係由反應產生的丙烯重量,除以反應產生的所有產物重量,再乘以一百而計算。其結果如表1所示。
*SOR=起動時(反應開始起算2小時)
**EOR=停止時(反應開始起算24小時)
如以上結果所示,樣品A,其為根據本發明之催化劑,相較於樣品B及C,提供了較高丁烯轉化率及較高丙烯選擇性。此外,樣品A的催化穩定性相較於其他樣品,確實顯示由SOR到EOR時下降較少的轉化率與選擇性。
實施例3:載體中沸石含量及沸石Si/Al比的效應
載體上包含固定量氧化鎢,且載體包含二氧化係及Y-沸石的催化劑樣品係由Y-沸石與數種不同氧化矽與氧化鋁比值,且以載體中含不同Y-沸石用量進行製備。該等樣品於實施例2反應條件測試。此測試結果如表2所示。
不佳的丁烯轉化率意謂進料流中少於30重量%的丁烯在反應中被消耗。中等的丁烯轉化率意謂進料流中30至60重量%的丁烯在反應中被消耗。並且,優良的丁烯轉化率意謂進料流中多於60重量%的丁烯在反應中被消耗。
不佳的丙烯選擇性意謂由反應中產生的丙烯少於總產物的30重量%。中等的丙烯選擇性意謂由反應中產生的丙烯為總產物的30至60重量%。並且,優良的丙烯選擇性意謂由反應中產生的丙烯多於總產物的60重量%。
不佳的催化穩定性意謂丁烯轉化率於起動時到停止時降低了超過60%。中等的催化穩定性意謂丁烯轉化率於起動時到停止時降低了20至60%。並且,優良的催化穩定性意謂丁烯轉化率於起動時到停止時降低了少於20%。
表2中所示的結果可證實,在氧化矽載體中加入沸石在烯烴複分解反應的轉化率、選擇性、及催化劑穩定性具有有利效果。此外,亦可見應謹慎選擇所添加的沸石用量及性質,以達到最佳結果。
以上描述及申請專利範圍所揭露的特徵,可分別或以任何組合形成實現本發明不同形式的材料。
實踐本發明的最佳模式如以上【實施方式】所描述。
Claims (11)
- 一種催化劑,其係包含至少一種選自VIA族及VIIA族金屬之過渡金屬以及一載體,該載體含有沸石與至少一種其他無機或有機材料的混合物,基於載體總重,該沸石之量為0.1至60重量%,其中該至少一種其他無機或有機材料係選自二氧化矽、二氧化鈦、二氧化鋯、及活性碳,其中該沸石之氧化矽與氧化鋁比值係於10至200之範圍。
- 如請求項1所述之催化劑,其中該至少一種過渡金屬係選自錸、鉬、及鎢。
- 如請求項1或2所述之催化劑,其中,基於該催化劑總重,該催化劑係包含1至12重量%之該至少一種過渡金屬(以金屬元素計)。
- 如請求項1所述之催化劑,其中該沸石係選自ZSM-5、鎂鹼沸石(Ferrierite)、X-沸石、Y-沸石、β-沸石、及MCM-22。
- 如請求項1所述之催化劑,其中基於該載體總重,該載體係包含0.1至30重量%之該沸石。
- 如請求項1所述之催化劑,其中該催化劑係包含一鑭系金屬。
- 一種烯烴複分解反應(olefin metathesis reaction)製程,其係包含以下步驟:a)提供一如請求項1所述之催化劑;b)視需要活化步驟a)之催化劑;以及c)將步驟a)或b)之催化劑與一烯烴進料流接觸,其中該進料流係包含至少一第一烯烴及至少一第二烯烴。
- 如請求項7所述之製程,其中活化該催化劑係包含於200℃至700℃之溫度處理該催化劑。
- 如請求項7或8所述之製程,其中將該催化劑與進料流接觸係於200℃至600℃之溫度進行。
- 如請求項7所述之製程,其中該第一烯烴及該第二烯烴係選自乙烯及2-丁烯、或乙烯及2-戊烯。
- 如請求項7所述之製程,其中該製程在步驟c)之後更包含一再生步驟。
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