JP6278964B2 - 金属錯体、吸着材、分離材および1,3−ブタジエンの分離方法 - Google Patents
金属錯体、吸着材、分離材および1,3−ブタジエンの分離方法 Download PDFInfo
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- JP6278964B2 JP6278964B2 JP2015528203A JP2015528203A JP6278964B2 JP 6278964 B2 JP6278964 B2 JP 6278964B2 JP 2015528203 A JP2015528203 A JP 2015528203A JP 2015528203 A JP2015528203 A JP 2015528203A JP 6278964 B2 JP6278964 B2 JP 6278964B2
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- butadiene
- carbon atoms
- metal complex
- gas
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 258
- 150000004696 coordination complex Chemical class 0.000 title claims description 94
- 239000000463 material Substances 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 30
- 239000003463 adsorbent Substances 0.000 title claims description 22
- 239000007789 gas Substances 0.000 claims description 113
- 238000001179 sorption measurement Methods 0.000 claims description 88
- 238000000926 separation method Methods 0.000 claims description 85
- -1 dipyridyl compound Chemical class 0.000 claims description 80
- 125000004432 carbon atom Chemical group C* 0.000 claims description 75
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 31
- MGFJDEHFNMWYBD-OWOJBTEDSA-N 4-[(e)-2-pyridin-4-ylethenyl]pyridine Chemical group C=1C=NC=CC=1/C=C/C1=CC=NC=C1 MGFJDEHFNMWYBD-OWOJBTEDSA-N 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 125000005843 halogen group Chemical group 0.000 claims description 23
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 22
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 22
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Chemical group 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000001282 iso-butane Substances 0.000 claims description 11
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- DQRKTVIJNCVZAX-UHFFFAOYSA-N 4-(2-pyridin-4-ylethyl)pyridine Chemical compound C=1C=NC=CC=1CCC1=CC=NC=C1 DQRKTVIJNCVZAX-UHFFFAOYSA-N 0.000 claims description 10
- NBDAHKQJXVLAID-UHFFFAOYSA-N 5-nitroisophthalic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC([N+]([O-])=O)=C1 NBDAHKQJXVLAID-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- UHBAPGWWRFVTFS-UHFFFAOYSA-N 4,4'-dipyridyl disulfide Chemical compound C=1C=NC=CC=1SSC1=CC=NC=C1 UHBAPGWWRFVTFS-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052790 beryllium Inorganic materials 0.000 claims description 7
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 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 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 6
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 6
- DHKSJSQSVHHBPH-UHFFFAOYSA-N 1,2-dipyridin-4-ylethane-1,2-diol Chemical compound C=1C=NC=CC=1C(O)C(O)C1=CC=NC=C1 DHKSJSQSVHHBPH-UHFFFAOYSA-N 0.000 claims description 5
- 125000004442 acylamino group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000006662 (C2-C4) acyloxy group Chemical group 0.000 claims description 4
- OIALIKXMLIAOSN-UHFFFAOYSA-N 2-Propylpyridine Chemical compound CCCC1=CC=CC=N1 OIALIKXMLIAOSN-UHFFFAOYSA-N 0.000 claims description 4
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 22
- 238000003795 desorption Methods 0.000 description 18
- 229910003460 diamond Inorganic materials 0.000 description 17
- 239000010432 diamond Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000001273 butane Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 239000013110 organic ligand Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 4
- 229910004013 NO 2 Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- OGNCVVRIKNGJHQ-UHFFFAOYSA-N 4-(3-pyridin-4-ylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=NC=C1 OGNCVVRIKNGJHQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 3
- 150000002531 isophthalic acids Chemical class 0.000 description 3
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000006606 n-butoxy group Chemical group 0.000 description 3
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
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Classifications
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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Description
下記一般式(I):
ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属のイオンと;
下記一般式(II):
L−Z−L (II)
(式中、Lは
Zは、−CR8R9−CR10R11−(式中、R8、R9、R10およびR11はそれぞれ独立に、水素原子、炭素数1〜4のアルキル基、ヒドロキシ基、またはハロゲン原子のいずれかである)、炭素数3〜4のアルキレン基、−CH=CH−、−C≡C−、−S−S−、−N=N−、−O−CH2−、−NH−CH2−または−NHCO−のいずれかである。)で表されるジピリジル化合物(II)からなる金属錯体であって、
前記ジピリジル化合物(II)として異なる二種以上のジピリジル化合物(II)を含むことを特徴とする金属錯体。
[2]
前記一般式(II)におけるZが−CR8R9−CR10R11−(式中、R8、R9、R10およびR11はそれぞれ独立に水素原子、炭素数1〜4のアルキル基、ヒドロキシ基、またはハロゲン原子のいずれかである)、炭素数3〜4のアルキレン基、−CH=CH−、−S−S−、または−NHCO−のいずれかである[1]に記載の金属錯体。
[3]
前記ジピリジル化合物(II)の組み合わせが、1,2−ジ(4−ピリジル)エチレンと1,2−ジ(4−ピリジル)エタン、1,2−ジ(4−ピリジル)エチレンと1,2−ジ(4−ピリジル)エチレングリコール、1,2−ジ(4−ピリジル)エチレンと4,4’−ジピリジルジスルフィド、または1,2−ジ(4−ピリジル)エチレンと1,3−ジ(4−ピリジル)プロパンのいずれかである、[1]または[2]のいずれかに記載の金属錯体。
[4]
前記ジカルボン酸化合物(I)が、イソフタル酸、5−メチルイソフタル酸および5−ニトロイソフタル酸からなる群より選択される少なくとも一種である[1]〜[3]のいずれかに記載の金属錯体。
[5]
前記金属イオンがコバルトイオン、ニッケルイオンおよび亜鉛イオンからなる群より選択される少なくとも一種である[1]〜[4]のいずれかに記載の金属錯体。
[6]
[1]〜[5]のいずれかに記載の金属錯体を含む吸着材。
[7]
前記吸着材が、二酸化炭素、水素ガス、一酸化炭素、酸素ガス、窒素ガス、炭素数1〜5の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を吸着するための吸着材である[6]に記載の吸着材。
[8]
[1]〜[5]のいずれかに記載の金属錯体を含む分離材。
[9]
前記分離材が、1,3−ブタジエンおよび1,3−ブタジエン以外の炭素数4の炭化水素を含む混合ガスの中から、1,3−ブタジエンを選択的に分離するものである[8]に記載の分離材。
[10]
前記1,3−ブタジエン以外の炭素数4の炭化水素が1−ブテン、イソブテン、trans−2−ブテン、cis−2ブテン、イソブタン、およびn−ブタンからなる群より選択される少なくとも一種である[9]に記載の分離材。
[11]
前記分離材が、二酸化炭素、水素ガス、一酸化炭素、酸素ガス、窒素ガス、炭素数1〜5の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を分離するための分離材である[8]に記載の分離材。
[12]
多孔質支持体と、前記多孔質支持体の表層部に付着した[8]〜[11]のいずれかに記載の分離材を含む分離膜。
[13]
高分子材料と、前記高分子材料に混練分散された[8]〜[11]のいずれかに記載の分離材を含む分離膜。
[14]
ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属の塩と、前記ジカルボン酸化合物(I)と、二種以上の前記ジピリジル化合物(II)とを反応させて、金属錯体を析出させることを含む、[1]に記載の金属錯体の製造方法であって、前記反応中に湿式摩砕を行うことを特徴とする、製造方法。
[15]
1,3−ブタジエンおよび1,3−ブタジエン以外の炭素数4の炭化水素を含む混合ガスを分離材と接触させ、1,3−ブタジエンを前記分離材に選択的に吸着させる吸着工程と、その後、前記分離材に吸着された1,3−ブタジエンを前記分離材から脱着させて、脱離してくる1,3−ブタジエンを捕集する再生工程とを含む、混合ガスから1,3−ブタジエンを分離する方法において、前記分離材が[8]〜[10]のいずれか一項に記載の分離材であることを特徴とする1,3−ブタジエンの分離方法。
本発明の金属錯体は、ジカルボン酸化合物(I)と、特定の金属イオンと、該金属イオンに二座配位可能な有機配位子(II)とからなり、有機配位子(II)が異なる二種類以上のジピリジル化合物(II)であることを特徴とする。
本発明に用いられるジカルボン酸化合物(I)は下記一般式(I):
本発明の分離材に用いられる金属錯体を構成する金属イオンはベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属のイオンである。これらの中でも錯体形成の観点からコバルトイオン、ニッケルイオンおよび亜鉛イオンが好ましく、亜鉛イオンがより好ましい。
本発明に用いられるジピリジル化合物(II)は金属イオンに二座配位可能な有機配位子であり、下記一般式(II)で表される。
L−Z−L (II)
(式中、Lは
Zは、−CR8R9−CR10R11−(式中、R8、R9、R10およびR11はそれぞれ独立に、水素原子、炭素数1〜4のアルキル基、ヒドロキシ基、またはハロゲン原子のいずれかである)、炭素数3〜4のアルキレン基、−CH=CH−、−C≡C−、−S−S−、−N=N−、−O−CH2−、−NH−CH2−または−NHCO−のいずれかである。)
本発明の金属錯体は、ジカルボン酸化合物(I)と、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属の塩と、該金属のイオンに二座配位可能な二種以上のジピリジル化合物(II)とを、常圧下、溶媒中で数分から数日間反応させ、結晶を析出させて製造することができる。例えば、前記金属塩の水溶液または水を含む有機溶媒溶液と、ジカルボン酸化合物(I)および二種以上のジピリジル化合物(II)を含有する有機溶媒溶液とを、常圧下で混合して反応させることにより本発明の金属錯体を得ることができる。
以上のようにして得られる本発明の金属錯体は、金属イオン1つあたり2つのジカルボン酸化合物(I)のカルボキシラートイオンと2つのジピリジル化合物(II)が配位して形成される擬ダイヤモンド骨格が多重に相互貫入した三次元構造を有する。擬ダイヤモンド骨格の構造を図1に、擬ダイヤモンド骨格が三重に相互貫入した三次元構造の模式図を図2に示す。金属錯体は、擬ダイヤモンド骨格が三重に相互貫入した構造を有することが好ましい。
本発明の1,3−ブタジエンおよび1,3−ブタジエン以外の炭素数4の炭化水素を含む混合ガスの中から、1,3−ブタジエンを分離する方法では、分離対象である1,3−ブタジエンを含む混合ガスを本発明の分離材と接触させ、1,3−ブタジエンを前記分離材に選択的に吸着させ、その後、前記分離材に吸着された1,3−ブタジエンを前記分離材から脱着させて、脱離してくる1,3−ブタジエンを捕集する。1,3−ブタジエンの脱着により分離材は再生する。
高圧ガス吸着装置を用いて容量法で測定を行った。このとき、測定に先立って試料を150℃、50Paで6時間乾燥し、吸着水などを除去した。分析条件の詳細を以下に示す。
<分析条件>
装置:日本ベル株式会社製BELSORP(登録商標)−18HT、または日本ベル株式会社製BELSORP(登録商標)−HP
平衡待ち時間:500秒
株式会社リガク製のX線回折装置:マルチフレックスを用いて、回折角(2θ)=3〜50°の範囲を走査速度3°/分で走査し、対称反射法で測定した。単結晶構造からのXRPD回折パターンへの変換には、The Cambridge Crystallographic Data Centre製Mercury(ver2.3)を用いた。
[Zn(NO2ip)(bpe)0.95(bpa)0.05]の合成:
ジルコニア製容器(45mL)に、酸化亜鉛(0.41g,5.0mmol,1eq.)、5−ニトロイソフタル酸(1.07g,5.0mmol,1.0eq.)、1,2−ジ(4−ピリジル)エタン(0.05g,0.03mmol,0.05eq.)、1,2−ジ(4−ピリジル)エチレン(0.87g,0.48mmol,0.95eq.)、蒸留水(5mL)、およびジルコニアボール(3mmφ、25g)を加え、常温(25℃)、400rpmで1時間、反応させながら湿式摩砕(フリッチュ社クラシックラインP−7を使用)した。その後、内容物を桐山漏斗(登録商標)を用いて濾過し、析出した金属錯体をイオン交換水、エタノールの順で洗浄後、乾燥した。金属錯体は白色固体として2.04g(収率:82%)得られた。得られた金属錯体は粉末X線回折パターン測定により、図1および図2に示した擬ダイヤモンド骨格が三重に相互貫入した構造を有する金属錯体であることを確認した。これを「金属錯体1」とする。
反応原料として表1に示した物質と量に変更した以外は実施例1と同様にして金属錯体2〜10および比較金属錯体1を製造した。なお、比較金属錯体1はジピリジル化合物(II)を一種類のみ用いている。
[Zn(NO2ip)(bpe)]の合成:
[Zn(NO2ip)(bpa)]の合成:
100mL水熱容器に5−ニトロイソフタル酸0.21g(1.0mmol)、およびKOH水溶液(0.1M)10mLを入れ溶解させた。さらに、酢酸亜鉛二水和物0.22g(1.0mmol)、1,2−ジ(4−ピリジル)エタン0.19g(1.0mmol)、および蒸留水30mLを加えた。160℃で72時間加熱した後、5℃/hの冷却速度で室温まで冷却した。得られた白色固体を桐山漏斗(登録商標)を用いて濾過し、イオン交換水、エタノールの順で洗浄した。比較金属錯体3として、0.40g(収率:88%)を得た。
典型的な吸着材であるゼオライトとしてゼオライト13X(ユニオン昭和株式会社製)を用いた。
典型的な吸着材であるゼオライトとしてゼオライトNaY(和光純薬工業株式会社製)を用いた。
実施例1〜10、比較例1〜3の金属錯体について25℃における1,3−ブタジエンの吸着等温線を測定した。結果を図4〜6に示す。ジピリジル化合物を二種含む実施例1〜10の金属錯体は比較例1〜3の錯体よりも低圧から1,3−ブタジエンを吸着し始める。よって、本発明の錯体が1,3−ブタジエンの吸着材として優れているのは明らかである。
実施例2の金属錯体2および比較例4のゼオライトについて25℃における1,3−ブタジエン、trans−2−ブテンおよび1−ブテンの吸脱着等温線を測定した。結果をそれぞれ図7および図8に示す。
実施例5の金属錯体5(10.3g)を体積16mL(内径1cm、長さ20cm)のステンレスチューブに充填し、1,3−ブタジエン:1−ブテン:n−ブタン=1:1:1(体積比)の混合ガスを25℃、0.15MPa、空間速度(SV)毎分3.8で5分間流通させた。その後、ガスを止め、ダイヤフラムポンプを用いて5分間かけて真空引きし、錯体に吸着されたガス(=脱着ガス)を回収した。この吸脱着操作を繰返し行い、定常状態に達した後、脱着ガスを分析したところ、1,3−ブタジエン濃度は64体積%であった。これから試算される分離材単位キログラムあたりの1,3−ブタジエン生産性は毎時46Lであった。一方、比較例4のゼオライト(6.8g)を前記ステンレスチューブに充填し、1,3−ブタジエン:1−ブテン:n−ブタン=1:1:1(体積比)の混合ガスを25℃、0.15MPa、空間速度(SV)毎分1.9で4分間流通させた後、ガスを止め、ダイヤフラムポンプを用いて30分間かけて真空引きし、錯体に吸着されたガス(=脱着ガス)を回収した。この吸脱着操作を繰返し行い、定常状態に達した後、脱着ガスを分析したところ、1,3−ブタジエン濃度は41体積%であり、試算される分離材単位キログラムあたりの1,3−ブタジエン生産性は毎時4.6Lであった。このことから、本発明の錯体が1,3−ブタジエン分離材として優れていることは明らかである。
実施例4の金属錯体4および比較例4のゼオライトについて0℃および40℃における1,3−ブタジエンの吸脱着等温線を測定した。結果をそれぞれ図11および図12に示す。
PS1、PS2 製品貯槽
AC1、AC2 吸着塔
P1 真空ポンプ
V1〜V8 バルブ
M 混合ガス
B ブタン、ブテン類が濃縮されたガス
BD 1,3−ブタジエンを主成分とするガス
Claims (15)
- 下記一般式(I):
ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属のイオンと;
下記一般式(II):
L−Z−L (II)
(式中、Lは
Zは、−CR8R9−CR10R11−(式中、R8、R9、R10およびR11はそれぞれ独立に、水素原子、炭素数1〜4のアルキル基、ヒドロキシ基、またはハロゲン原子のいずれかである)、炭素数3〜4のアルキレン基、−CH=CH−、−C≡C−、−S−S−、−N=N−、−O−CH2−、−NH−CH2−または−NHCO−のいずれかである。)で表されるジピリジル化合物(II)からなる金属錯体であって、
前記ジピリジル化合物(II)として異なる二種以上のジピリジル化合物(II)を含むことを特徴とする金属錯体。 - 前記一般式(II)におけるZが−CR8R9−CR10R11−(式中、R8、R9、R10およびR11はそれぞれ独立に水素原子、炭素数1〜4のアルキル基、ヒドロキシ基、またはハロゲン原子のいずれかである)、炭素数3〜4のアルキレン基、−CH=CH−、−S−S−、または−NHCO−のいずれかである請求項1に記載の金属錯体。
- 前記ジピリジル化合物(II)の組み合わせが、1,2−ジ(4−ピリジル)エチレンと1,2−ジ(4−ピリジル)エタン、1,2−ジ(4−ピリジル)エチレンと1,2−ジ(4−ピリジル)エチレングリコール、1,2−ジ(4−ピリジル)エチレンと4,4’−ジピリジルジスルフィド、または1,2−ジ(4−ピリジル)エチレンと1,3−ジ(4−ピリジル)プロパンのいずれかである、請求項1または2のいずれかに記載の金属錯体。
- 前記ジカルボン酸化合物(I)が、イソフタル酸、5−メチルイソフタル酸および5−ニトロイソフタル酸からなる群より選択される少なくとも一種である請求項1〜3のいずれか一項に記載の金属錯体。
- 前記金属イオンがコバルトイオン、ニッケルイオンおよび亜鉛イオンからなる群より選択される少なくとも一種である請求項1〜4のいずれか一項に記載の金属錯体。
- 請求項1〜5のいずれか一項に記載の金属錯体を含む吸着材。
- 前記吸着材が、二酸化炭素、水素ガス、一酸化炭素、酸素ガス、窒素ガス、炭素数1〜5の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を吸着するための吸着材である請求項6に記載の吸着材。
- 請求項1〜5のいずれか一項に記載の金属錯体を含む分離材。
- 前記分離材が、1,3−ブタジエンおよび1,3−ブタジエン以外の炭素数4の炭化水素を含む混合ガスの中から、1,3−ブタジエンを選択的に分離するものである請求項8に記載の分離材。
- 前記1,3−ブタジエン以外の炭素数4の炭化水素が1−ブテン、イソブテン、trans−2−ブテン、cis−2ブテン、イソブタン、およびn−ブタンからなる群より選択される少なくとも一種である請求項9に記載の分離材。
- 前記分離材が、二酸化炭素、水素ガス、一酸化炭素、酸素ガス、窒素ガス、炭素数1〜5の炭化水素、希ガス、硫化水素、アンモニア、硫黄酸化物、窒素酸化物、シロキサン、水蒸気または有機蒸気を分離するための分離材である請求項8に記載の分離材。
- 多孔質支持体と、前記多孔質支持体の表層部に付着した請求項8〜11のいずれか一項に記載の分離材を含む分離膜。
- 高分子材料と、前記高分子材料に混練分散された請求項8〜11のいずれか一項に記載の分離材を含む分離膜。
- ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、バナジウム、クロム、マンガン、鉄、ルテニウム、コバルト、ロジウム、ニッケル、パラジウム、白金、銅、亜鉛、およびカドミウムからなる群より選択される少なくとも一種の金属の塩と、前記ジカルボン酸化合物(I)と、二種以上の前記ジピリジル化合物(II)とを反応させて、金属錯体を析出させることを含む、請求項1に記載の金属錯体の製造方法であって、前記反応中に湿式摩砕を行うことを特徴とする、製造方法。
- 1,3−ブタジエンおよび1,3−ブタジエン以外の炭素数4の炭化水素を含む混合ガスを分離材と接触させ、1,3−ブタジエンを前記分離材に選択的に吸着させる吸着工程と、その後、前記分離材に吸着された1,3−ブタジエンを前記分離材から脱着させて、脱離してくる1,3−ブタジエンを捕集する再生工程とを含む、混合ガスから1,3−ブタジエンを分離する方法において、前記分離材が請求項8〜10のいずれか一項に記載の分離材であることを特徴とする1,3−ブタジエンの分離方法。
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