JP6595606B2 - オレフィンを製造するための触媒及びプロセス - Google Patents
オレフィンを製造するための触媒及びプロセス Download PDFInfo
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- JP6595606B2 JP6595606B2 JP2017540252A JP2017540252A JP6595606B2 JP 6595606 B2 JP6595606 B2 JP 6595606B2 JP 2017540252 A JP2017540252 A JP 2017540252A JP 2017540252 A JP2017540252 A JP 2017540252A JP 6595606 B2 JP6595606 B2 JP 6595606B2
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- Prior art keywords
- metathesis catalyst
- zeolite
- layered double
- catalyst
- weight
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims description 87
- 150000001336 alkenes Chemical class 0.000 title claims description 35
- 238000000034 method Methods 0.000 title description 12
- 230000008569 process Effects 0.000 title description 8
- 238000005649 metathesis reaction Methods 0.000 claims description 58
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- 239000010457 zeolite Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 26
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- 150000003624 transition metals Chemical class 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 150000001450 anions Chemical class 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 38
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 18
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005865 alkene metathesis reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-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
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005686 cross metathesis reaction Methods 0.000 description 1
- -1 cyclic olefins Chemical class 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910021474 group 7 element Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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
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- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
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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
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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
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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
- B01J23/32—Manganese, technetium or rhenium
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- 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
- B01J29/163—X-type faujasite
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- 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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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Description
[My+ 1−xM’z+ x(OH)2]a+(Ar−)n・b(H2O)
式中
Mは第1の金属であり;
M’は第2の金属であり;
Aはアニオンであり;
xは、好ましくは0.1〜0.9の範囲の数値であり;
yは、好ましくは1又は2に等しい第1の金属の電荷数であり;
zは、好ましくは3又は4に等しい第2の金属の電荷数であり;
aは、x、y及びzによって決まり、好ましくはa=(1−x)y+xz−2であり;
rは、アニオンの電荷数であり;
nは、a及びrによって決まり、好ましくはn=a/rであり;
bは、好ましくは0〜10の範囲の水分子の数である。
シリカ担体上の9重量% WO3を含むメタセシス触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
シリカ担体上の9重量% WO3とMg−Al−CO3層状複水酸化物とを重量で10:1の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
95重量%のシリカ及び5重量%のY−ゼオライトを含む担体上の9重量% WO3とMg−Al−CO3層状複水酸化物とを重量で10:1の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
95重量%のシリカ及び5重量%のY−ゼオライトを含む担体上の9重量% WO3とMg−Al−CO3層状複水酸化物とを重量で10:0.5の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
95重量%のシリカ及び5重量%のY−ゼオライトを含む担体上の9重量% WO3とMg−Al−CO3層状複水酸化物とを重量で1:1の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
95重量%のシリカ及び5重量%のY−ゼオライトを含む担体上の9重量% WO3とCa−Al−CO3層状複水酸化物とを重量で10:1の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エテン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
95重量%のシリカ及び5重量%のY−ゼオライトを含む担体上の9重量% WO3と酸化マグネシウムとを重量で1:1の比で物理的に混合することによってメタセシス触媒を得た。触媒を管反応器に充填した。エタン及び2−ブテンを含む供給流を、1.4hr−1の時間あたりの重量空間速度(WHSV)で反応器に供給し、触媒床を、350℃及び22bar(ゲージ)になるよう制御した。
本願発明には以下の態様が含まれる。
項1.
a)元素周期表の第VIA族及び第VIIA族から選択される遷移金属;
b)無機担体;
c)0.1〜60重量部のゼオライト;及び
d)0.1〜80重量部の層状複水酸化物
を含む、メタセシス触媒。
項2.
前記遷移金属が、モリブデン、タングステン及びレニウムから選択される、項1に記載のメタセシス触媒。
項3.
1〜15重量部の前記遷移金属を含む、項1又は2に記載のメタセシス触媒。
項4.
前記無機担体が、シリカ、アルミナ、チタニア、ジルコニア及びこれらの混合物から選択され、好ましくはシリカである、項1から3のいずれかに記載のメタセシス触媒。
項5.
前記ゼオライトが、ZSM−5、X−ゼオライト、Y−ゼオライト、β−ゼオライト、MCM−22、フェリエライト及びこれらの混合物、好ましくはZSM−5、Y−ゼオライト及びフェリエライトから選択される、項1から4のいずれかに記載のメタセシス触媒。
項6.
0.5〜30重量部、好ましくは1〜20重量部のゼオライトを含む、項1から5のいずれかに記載のメタセシス触媒。
項7.
前記層状複水酸化物が、Li、Ca、Mg、Mn、Fe、Co、Ni、Cu、Zn及びこれらの混合物から選択され、好ましくはCa及び/又はMgである第1の金属を含む、項1から6のいずれかに記載のメタセシス触媒。
項8.
前記層状複水酸化物が、Al、Ga、In、Mn、Fe、Co、Cr、Ni、V、Ti、Zr、Y及びこれらの混合物から選択され、好ましくはAlである第2の金属を含む、項1から7のいずれかに記載のメタセシス触媒。
項9.
前記層状複水酸化物が、クロライド、ブロマイド、カーボネート、ビカーボネート、水素ホスフェート、二水素ホスフェート、ニトリト、ボレート、ナイトレート、サルフェート、ホスフェート、ヒドロキシド、フルオリド、ヨージド及びこれらの混合物、好ましくはカーボネート及びナイトレートから選択されるアニオンを含む、項1から8のいずれかに記載のメタセシス触媒。
項10.
0.5〜50重量部、好ましくは1〜30重量部の前記層状複水酸化物を含む、項1から9のいずれかに記載のメタセシス触媒。
項11.
前記メタセシス触媒が:
a)無機担体とゼオライトを混合して、これらの混合物を得る工程;
b)前記無機担体及び前記ゼオライトの前記混合物上に遷移金属を堆積させて、堆積混合物を得る工程;及び
c)前記堆積混合物と前記層状複水酸化物を混合して、前記メタセシス触媒を得る工程
を含む調製プロセスにより得ることができる、項1から10のいずれかに記載のメタセシス触媒。
項12.
前記調製プロセスが、工程c)において前記層状複水酸化物と混合する前に、前記堆積混合物を乾燥及び/又はか焼する工程をさらに含む、項11に記載のメタセシス触媒。
項13.
オレフィンを含む供給流を、項1から12のいずれかに記載のメタセシス触媒と接触させる工程を含む、オレフィン製造プロセス。
項14.
前記供給流が、C2直鎖オレフィン、C3直鎖オレフィン、C4直鎖オレフィン、C5直鎖オレフィン、C6直鎖オレフィン及びこれらの混合物からなる群から選択される直鎖オレフィンを含む、項13に記載のオレフィン製造プロセス。
Claims (10)
- a)1〜15重量%の、元素周期表の第VIA族及び第VIIA族から選択される遷移金属;
b)無機担体;
c)0.1〜30重量%のゼオライト;及び
d)0.5〜50重量%の層状複水酸化物
を含む、メタセシス触媒であって、
前記遷移金属が、モリブデン、タングステン及びレニウムから選択され、前記無機担体が、シリカ、アルミナ、チタニア、ジルコニア及びこれらの混合物から選択される、メタセシス触媒。 - 前記無機担体がシリカである、請求項1に記載のメタセシス触媒。
- 前記ゼオライトが、ZSM−5、X−ゼオライト、Y−ゼオライト、β−ゼオライト、MCM−22、フェリエライト及びこれらの混合物から選択される、請求項1又は2に記載のメタセシス触媒。
- 前記層状複水酸化物が、Li、Ca、Mg、Mn、Fe、Co、Ni、Cu、Zn及びこれらの混合物から選択される第1の金属を含む、請求項1から3のいずれかに記載のメタセシス触媒。
- 前記層状複水酸化物が、Al、Ga、In、Mn、Fe、Co、Cr、Ni、V、Ti、Zr、Y及びこれらの混合物から選択される第2の金属を含む、請求項1から4のいずれかに記載のメタセシス触媒。
- 前記層状複水酸化物が、クロライド、ブロマイド、カーボネート、ビカーボネート、水素ホスフェート、二水素ホスフェート、ニトリト、ボレート、ナイトレート、サルフェート、ホスフェート、ヒドロキシド、フルオリド、ヨージド及びこれらの混合物から選択されるアニオンを含む、請求項1から5のいずれかに記載のメタセシス触媒。
- a)無機担体とゼオライトを混合して、これらの混合物を得る工程;
b)前記無機担体及び前記ゼオライトの前記混合物上に遷移金属を堆積させて、堆積混合物を得る工程;及び
c)前記堆積混合物と前記層状複水酸化物を混合して、前記メタセシス触媒を得る工程
を含む、請求項1から6のいずれかに記載のメタセシス触媒の調製方法。 - 前記工程c)において前記層状複水酸化物と混合する前に、前記堆積混合物を乾燥及び/又はか焼する工程をさらに含む、請求項7に記載の調製方法。
- オレフィンを含む供給流を、請求項1から6のいずれかに記載のメタセシス触媒と接触させる工程を含む、オレフィン製造プロセス。
- 前記供給流が、C2直鎖オレフィン、C3直鎖オレフィン、C4直鎖オレフィン、C5直鎖オレフィン、C6直鎖オレフィン及びこれらの混合物からなる群から選択される直鎖オレフィンを含む、請求項9に記載のオレフィン製造プロセス。
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BRPI0918229A2 (pt) | 2008-09-04 | 2016-03-01 | Basf Corp E Basf Ag | isomerizacao de olefina e catalisador de metatese |
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TW201627067A (zh) | 2016-08-01 |
CN107438482A (zh) | 2017-12-05 |
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US10457616B2 (en) | 2019-10-29 |
KR102498318B1 (ko) | 2023-02-10 |
SG11201706042VA (en) | 2017-09-28 |
KR20170109557A (ko) | 2017-09-29 |
SA517381924B1 (ar) | 2021-03-31 |
SG10201809287VA (en) | 2018-11-29 |
TWI651128B (zh) | 2019-02-21 |
US20170305816A1 (en) | 2017-10-26 |
CN107438482B (zh) | 2021-05-25 |
WO2016120423A1 (en) | 2016-08-04 |
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