US20140360938A1 - Zeolite membrane composite - Google Patents
Zeolite membrane composite Download PDFInfo
- Publication number
- US20140360938A1 US20140360938A1 US14/467,496 US201414467496A US2014360938A1 US 20140360938 A1 US20140360938 A1 US 20140360938A1 US 201414467496 A US201414467496 A US 201414467496A US 2014360938 A1 US2014360938 A1 US 2014360938A1
- Authority
- US
- United States
- Prior art keywords
- zeolite membrane
- zeolite
- membrane composite
- separation
- membrane
- 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.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 484
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 483
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 452
- 239000010457 zeolite Substances 0.000 title claims abstract description 452
- 239000002131 composite material Substances 0.000 title claims abstract description 215
- 238000000926 separation method Methods 0.000 claims abstract description 184
- 239000000203 mixture Substances 0.000 claims abstract description 144
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 50
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 150
- 229910001868 water Inorganic materials 0.000 claims description 132
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 69
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 49
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- 238000001179 sorption measurement Methods 0.000 claims description 48
- 229910052681 coesite Inorganic materials 0.000 claims description 44
- 229910052906 cristobalite Inorganic materials 0.000 claims description 44
- 229910052682 stishovite Inorganic materials 0.000 claims description 44
- 229910052905 tridymite Inorganic materials 0.000 claims description 44
- 229910052593 corundum Inorganic materials 0.000 claims description 42
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 39
- 239000001569 carbon dioxide Substances 0.000 claims description 32
- 239000011541 reaction mixture Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910018503 SF6 Inorganic materials 0.000 claims description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 3
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007789 gas Substances 0.000 description 159
- 239000013078 crystal Substances 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000000126 substance Substances 0.000 description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 32
- 239000011148 porous material Substances 0.000 description 27
- 150000002894 organic compounds Chemical class 0.000 description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- -1 adheres Chemical compound 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000010304 firing Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229920005597 polymer membrane Polymers 0.000 description 6
- 238000006884 silylation reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241000408939 Atalopedes campestris Species 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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- 239000002808 molecular sieve Substances 0.000 description 3
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- 229910052863 mullite Inorganic materials 0.000 description 3
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- NRNCYVBFPDDJNE-UHFFFAOYSA-N pemoline Chemical compound O1C(N)=NC(=O)C1C1=CC=CC=C1 NRNCYVBFPDDJNE-UHFFFAOYSA-N 0.000 description 3
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- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 239000004115 Sodium Silicate Substances 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
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- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- SYJRVVFAAIUVDH-UHFFFAOYSA-N ipa isopropanol Chemical compound CC(C)O.CC(C)O SYJRVVFAAIUVDH-UHFFFAOYSA-N 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
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- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 125000005372 silanol group Chemical group 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LWRYDHOHXNQTSK-UHFFFAOYSA-N thiophene oxide Chemical compound O=S1C=CC=C1 LWRYDHOHXNQTSK-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B01D—SEPARATION
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- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- B01D53/22—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 diffusion
- B01D2053/221—Devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/24—Use of template or surface directing agents [SDA]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/43—Specific optical properties
Definitions
- the present invention relates to a zeolite membrane composite for use in separation of a specific component from a vapor mixture or a liquid mixture comprising multiple components, in which the zeolite membrane composite comprises a zeolite membrane having certain physical properties and formed on an inorganic porous support, and relates to a separation or concentration method that uses the zeolite membrane composite as a separating means for a vapor mixture or a liquid mixture.
- a membrane separation/concentration method that uses a membrane such as a polymer membrane, a zeolite membrane or the like.
- a polymer membrane for example, a flat membrane, a hollow fiber membrane or the like is excellent in workability but is defective in that the heat resistance thereof is poor.
- a zeolite membrane is generally used for separation and concentration as a zeolite membrane composite having a filmy zeolite formed on a support. Separation and concentration using a membrane of an inorganic material can be carried out in a broader temperature range than that with a polymer membrane, and further the inorganic material membrane is applicable to separation of a mixture that contains an organic compound.
- zeolite As a separation method for a vapor mixture (gas) by the use of a membrane, there has been proposed a method of using a polymer membrane since 1970's.
- a polymer membrane is excellent in workability but is, on the other hand, problematic in that it would deteriorate owing to heat, chemical substances or pressure and the performance thereof worsens.
- various types of inorganic membranes having good chemical resistance, oxidation resistance, heat-resistant stability and pressure resistance.
- zeolite has regular sub-nanometer-order micropores, and therefore, as being able to work as a molecular sieve, zeolite can let specific molecules selectively pass therethrough, and is expected to exhibit high separation performance.
- membrane separation for a mixed gas there is mentioned separation of carbon dioxide and nitrogen, carbon dioxide and methane, hydrogen and hydrocarbon, hydrogen and oxygen, hydrogen and carbon dioxide, nitrogen and hydrogen, paraffin and olefin or the like, as separation of gases to be discharged from thermal power plants, petrochemical industries, etc.
- zeolite membranes usable for gas separation there are known zeolite membranes such as A-type membrane, FAU membrane, MFI membrane, SAPO-34 membrane, DDR membrane, etc.
- A-type zeolite membrane is readily influenced by moisture and could hardly form a membrane with no crystal void, and the separation performance thereof is not high.
- zeolite micropores have a size of from 0.6 to 0.8 nm, and the size is such that two vapor molecules could pass through each zeolite micropore.
- This membrane is suitable for separation of molecules adsorbable to zeolite micropores and those not adsorbable thereto, for example, for separation of carbon dioxide and nitrogen.
- non-adsorbable molecules are difficult to separate and the application range of the membrane is therefore narrow.
- the pore size of MFI membrane is 0.55 nm, or that is, the pore size is somewhat large for separation of vapor molecules and the separation performance of the membrane is not high.
- a separation method for a liquid mixture that uses a zeolite membrane for example, there have been proposed a method of selective permeation of water using an A-type zeolite membrane composite for alcohol concentration (PTL 2), a method of selective permeation of water from a mixed system of alcohol and water by the use of a mordenite-type zeolite membrane composite for alcohol concentration (PTL 3), a method of selective permeation of water from a mixed system of acetic acid and water by the use of a ferrierite-type zeolite membrane composite for separation and concentration of acetic acid (PTL 4), etc.
- PTL 2 A-type zeolite membrane composite for alcohol concentration
- PTL 3 mordenite-type zeolite membrane composite for alcohol concentration
- PTL 4 ferrierite-type zeolite membrane composite for separation and concentration of acetic acid
- DDR DDR
- SAPO-3 NPL 1 that is a CHA-type aluminophosphate having a three-dimensional structure has good separation performance and permeance, but the performance thereof worsens in the presence of water.
- moisture is often contained in a mixed gas in many cases, and SAPO-34 would be often impracticable.
- SSZ-13 (NPL 2) of a CHA-type aluminosilicate that is a membrane for a SUS support is insufficient in point of the separation performance thereof since there exist non-zeolite micropores (defects) in the zeolite membrane, and therefore the carbon dioxide permeance thereof is not also satisfactory.
- practicable separation membranes for vapor mixtures have heretofore been unknown.
- the mordenite-type zeolite membrane composite in PTL 3 and the ferrierite-type zeolite membrane composite in PTL 4 have a small permeation flux and are therefore insufficient in point of the throughput level for practical use.
- the separation performance with the membrane composite may change with the prolongation of the operating time, and therefore using the membrane composite under the condition where an organic acid exists is undesirable.
- the A-type zeolite in PTL 2 does not have acid resistance and waterproofness, and the application range thereof is therefore limited.
- the present inventors have found that, in forming a zeolite membrane on a porous support through hydrothermal synthesis, when a reaction mixture having a specific composition is used, then the crystal orientation of zeolite crystallizing on the support can better therefore providing a dense zeolite membrane that satisfies both sufficient throughput and good separation membrane performance in separation of a mixture of an organic compound and water, and have made previous proposals (WO2010/098473, JP-A 2011-121040, JP-A 2011-121045, JP-A 2011-121854).
- both the throughput and the separation performance can be on a high level; however, especially in separation of a vapor mixture, in general, the amount of throughput is enormous and the necessary membrane area increases, though depending on the process scale. Consequently, for application to vapor mixture separation, the membrane is desired to secure a further increased throughput, or that is, to secure a further increased vapor permeance through the membrane. Also in liquid mixture separation, cost reduction and downsizing of apparatus are desired by further increasing the permeance and reducing the necessary membrane area.
- the present invention addresses an object of providing a zeolite composite membrane which solves the prior-art problems, which is excellent in waterproofness and has high throughput and separation performance, and which has excellent characteristics in separation of a vapor mixture or a liquid mixture.
- the present inventors have assiduously studied for the purpose of solving the above-mentioned problems and, as a result, have found that zeolite of a CHA-type aluminosilicate having certain physical properties can form a zeolite membrane composite that satisfies both sufficient throughput and separation processing performance enough for practical use and is favorable for a separation means for a vapor mixture and a liquid mixture.
- the present invention has been made on the basis of these findings.
- the gist of the invention resides in the following (1) to (19):
- a zeolite membrane composite for use in separation of a highly-permeative component through permeation from a vapor mixture or a liquid mixture comprising multiple components, the zeolite membrane composite comprising an inorganic porous support and a zeolite membrane provided thereon, wherein the zeolite membrane contains zeolite of a CHA-type aluminosilicate having a molar ratio of SiO 2 /Al 2 O 3 of 30 or more and 100 or less.
- a zeolite membrane composite for use in separation of a highly-permeative component through permeation from a vapor mixture or a liquid mixture comprising multiple components, the zeolite membrane composite comprising an inorganic porous support and a zeolite membrane provided thereon, wherein the zeolite membrane contains zeolite of a CHA-type aluminosilicate, and a water adsorption of the zeolite membrane composite at a relative pressure of 0.8, as obtained from a water vapor adsorption isotherm of the zeolite membrane composite, is 2 times or more and 10 times or less a water adsorption thereof at a relative pressure of 0.2.
- a separation or concentration method for a vapor mixture which comprises bringing a vapor mixture containing multiple vapor components into contact with the zeolite membrane composite as stated in any one of the items (1) to (15) to thereby separate a highly-permeative component through permeation from the vapor mixture, or to thereby separate a highly-permeative vapor component through permeation therefrom so as to concentrate a poorly-permeative vapor component.
- the vapor mixture contains at least one component selected from a group consisting of carbon dioxide, hydrogen, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, helium, carbon monoxide, nitrogen monoxide and water.
- a separation or concentration method for a liquid mixture which comprises bringing a liquid mixture containing multiple components into contact with the zeolite membrane composite as stated in any one of the items (1) to (14) and (16) to thereby separate a highly-permeative component through permeation from the liquid mixture, or to thereby separate a highly-permeative component through permeation therefrom so as to concentrate a poorly-permeative component.
- a zeolite membrane composite excellent in chemical resistance, heat-resistant stability, oxidation resistance and pressure resistance, especially securing a large permeation amount therethrough, having a high separation coefficient and high wet heat stability and having an excellent characteristic for separation of a vapor mixture or a liquid mixture.
- zeolite membrane composite of the invention as a separating means for a vapor mixture enables energy-saving, low-cost, high-performance and efficient vapor separation in small plants.
- zeolite membrane composite of the invention as a separating means for a liquid mixture enables energy-saving, low-cost, high-performance and efficient separation of a highly-permeative substance from a liquid mixture containing organic compounds.
- a highly-permeative component may be separated from a vapor mixture or a liquid mixture through permeation and a poorly-permeative vapor may be concentrated, whereby the highly-permeative component may be discharged out of the system and the poorly-permeative component may be concentrated and recovered and whereby the intended component can be separated at a high purity.
- FIG. 1 is a schematic view of an apparatus used in a gas permeation test.
- FIG. 2 is a schematic view of an apparatus for use in gas separation.
- FIG. 3 is a schematic view of an apparatus used in a vapor permeation method.
- FIG. 4 is an XRD pattern of the CHA-type zeolite membrane produced in Example 1.
- FIG. 5 is an XRD pattern of the CHA-type zeolite membrane produced in Example 2.
- FIG. 6 is an XRD pattern of a powdery CHA-type zeolite.
- FIG. 7 is an XRD pattern of the CHA-type zeolite membrane produced in Example 4.
- zeolite membrane composite having a zeolite membrane formed on an inorganic porous support may be referred to as “inorganic porous support-zeolite membrane composite”.
- Inorganic porous support-zeolite membrane composite may be abbreviated as “zeolite membrane composite” or “membrane composite”; “inorganic porous support” may be as “support”; and “zeolite of a CHA-type aluminosilicate” may be as “CHA-type zeolite”.
- the zeolite membrane composite of another aspect of the invention is a zeolite membrane composite for use in separation of a highly-permeative component through permeation from a vapor mixture or a liquid mixture comprising multiple components, wherein the zeolite membrane contains zeolite of a CHA-type aluminosilicate having a molar ratio of SiO 2 /Al 2 O 3 of 30 or more and 100 or less, and is formed on an inorganic porous support.
- the zeolite membrane composite of still another aspect of the invention is a zeolite membrane composite for use in separation of a highly-permeative component through permeation from a vapor mixture or a liquid mixture comprising multiple components, wherein the zeolite membrane contains zeolite of a CHA-type aluminosilicate and is formed on an inorganic porous support, and wherein the water adsorption of the zeolite membrane composite at a relative pressure of 0.8, as obtained from the water vapor adsorption isotherm of the zeolite membrane composite, is 2 times or more and 10 times or less the water adsorption thereof at a relative pressure of 0.2.
- the zeolite membrane composite is, as described above, used as a membrane separating means for separation of a highly-permeative component through penetration from a vapor mixture or a liquid mixture of multiple components.
- the matters relating to the separation or concentration method such as the vapor component, the liquid component, the separation method, the separation performance and others will be described after the details of the zeolite membrane composite are described below.
- the zeolite membrane contains zeolite having specific properties as described above, and the components constituting the zeolite membrane may contain, if desired, an inorganic binder such as silica, alumina or the like, an organic substance such as polymer or the like, as well as a silylating agent to modify the surface of zeolite and others, in addition to zeolite.
- an inorganic binder such as silica, alumina or the like
- an organic substance such as polymer or the like
- silylating agent to modify the surface of zeolite and others, in addition to zeolite.
- the zeolite membrane may partially contain an amorphous component or the like, but preferably, the zeolite membrane is composed of substantially zeolite alone.
- the proportion of the CHA-type aluminosilicate contained in the zeolite membrane is generally at least 10% by volume, preferably at least 30% by volume, more preferably at least 60% by volume, even more preferably at least 80% by volume. Most preferably, the zeolite membrane is comprised of a CHA-type aluminosilicate alone, as excellent in gas permeability and separability.
- the thickness of the zeolite membrane is generally at least 0.1 ⁇ m, preferably at least 0.6 ⁇ m, more preferably at least 1.0 ⁇ m, and is generally at most 100 ⁇ m, preferably at most 60 ⁇ m, more preferably at most 20 ⁇ m.
- the permeation amount may lower; and when too small, then the selectivity may lower and the membrane strength may lower.
- the grain size of zeolite to form the zeolite membrane is not specifically defined; however, when too small, then the grain boundary would increase and the permeation selectivity would be thereby lowered. Consequently, the grain size is generally at least 30 nm, preferably at least 50 nm, more preferably at least 100 nm, and the upper limit thereof is not more than the thickness of the membrane. More preferred is a case where the grain size of zeolite is the same as the thickness of the membrane. When the grain size of zeolite is the same as the thickness of the membrane, then the grain boundary of zeolite could be the smallest.
- the zeolite membrane obtained through hydrothermal synthesis to be mentioned below is preferred since the grain size of zeolite could be the same as the thickness of the membrane.
- the shape of the zeolite membrane is not specifically defined, for which is employable any and every shape including tubular, hollow-fiber, monolithic, honeycomb and the like shapes.
- the size is not also specifically defined.
- the preferred range for practical use thereof is such that the length is 2 cm or more and 200 cm or less, the inner diameter is 0.5 cm or more and 2 cm or less and the thickness is 0.5 mm or more and 4 mm or less.
- the zeolite membrane contains zeolite of a CHA-type aluminosilicate.
- the zeolite to form the zeolite membrane is a CHA-type aluminosilicate.
- the aluminosilicate comprises Si and Al oxides as the main ingredients thereof, and may contain any other element not detracting from the advantageous effects of the invention.
- the molar ratio of SiO 2 /Al 2 O 3 in the aluminosilicate is not specifically defined, but is generally at least 6, preferably at least 10, more preferably at least 20, even more preferably at least 30, still more preferably at least 32, further more preferably at least 35, and especially more preferably at least 40.
- the upper limit is generally the amount of such a level that Al could be an impurity
- the molar ratio of SiO 2 /Al 2 O 3 is generally at most 500, preferably at most 100, more preferably at most 90, even more preferably at most 80, still more preferably at most 70, and most preferably at most 50.
- the denseness of the zeolite membrane may lower and the durability thereof may also lower.
- the molar ratio of SiO 2 /Al 2 O 3 may be adjusted according to the reaction condition of hydrothermal synthesis to be mentioned below.
- the molar ratio of SiO 2 /Al 2 O 3 is a value obtained through scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX). In general, the measurement is attained at an X-ray accelerating voltage of 10 kV to give the information of the membrane alone having a thickness of a few microns.
- CHA-type zeolite is one having a CHA structure as the code to define the structure of zeolite, as stipulated by International Zeolite Association (IZA).
- the zeolite of the type has the same crystal structure as that of natural product, chabazite.
- the CHA-type zeolite has a structure characterized by having three-dimensional micropores composed of at most 8-membered oxygen rings having a diameter of 0.38 ⁇ 0.38 nm, and the structure is characterized by the X-ray diffraction data thereof.
- the framework density (T/nm 3 ) of the CHA-type zeolite is 14.5.
- the molar ratio of SiO 2 /Al 2 O 3 is the same as described above.
- the framework density means the number of the other elements (T elements) than oxygen to constitute the framework per nm 3 (1000 ⁇ 3 ) of zeolite, and the value is determined by the structure of zeolite.
- the relationship between the framework density and the zeolite structure is shown in ATLAS OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition 2001, ELSEVIER.
- the inorganic porous support may be any and every porous inorganic substance having chemical stability in such that zeolite can be crystallized as a membrane on the surface thereof.
- zeolite can be crystallized as a membrane on the surface thereof.
- sintered ceramics of silica, ⁇ -alumina, ⁇ -alumina, mullite, zirconia, titania, yttria, silicon nitride, silicon carbide or the like sintered metals of iron, bronze, stainless or the like, glass, carbon compacts, etc.
- sintered ceramics have an effect of increasing the interfacial adhesiveness through partial zeolitation thereof during membrane production.
- an inorganic porous support containing at least one of alumina, silica and mullite is more preferred since partial zeolitation of the support is easy and since the bonding between the support and zeolite is thereby enhanced and a membrane having high separation capacity is easy to form.
- the shape of the support is not specifically defined so far as the support secures effective separation of a vapor mixture or a liquid mixture.
- the support secures effective separation of a vapor mixture or a liquid mixture.
- a zeolite membrane is formed on the surface of an inorganic porous support, and preferably zeolite is crystallized as a membrane thereon.
- the mean pore size that the support has is not specifically defined, but preferably the pore size of the support is controlled.
- the pore size is generally at least 0.02 ⁇ m, preferably at least 0.05 ⁇ m, more preferably at least 0.1 ⁇ M, and is generally at most 20 ⁇ m, preferably at most 10 ⁇ m, more preferably at most 5 ⁇ m.
- the mean pore size is too small, then the permeation amount would be low; but when too large, then the strength of the support itself would be insufficient and a dense zeolite membrane would be difficult to form on the support.
- the mean pore size of the support may be measured according to a mercury intrusion method.
- the surface of the support may be polished by filing or the like, if desired.
- the surface of the support means the surface part of the support on which a zeolite membrane is formed, and may be any surface area of the support having a different shape, and may also be multiple faces of the support.
- the surface thereof may be any of the outer surface and the inner surface or may also be both surfaces of the inner surface and the outer surface.
- the porosity of the support is not specifically defined, and is not needed to be specifically controlled. In general, the porosity is preferably 20% or more and 60% or less. The porosity governs the permeation flow rate in vapor or liquid separation, and when the porosity is less than the lower limit, then the diffusion of the permeated matter would be interfered with; and when more than the upper limit, then the strength of the support would lower.
- the porosity of the support may be measured according to a mercury intrusion method.
- the zeolite membrane composite is one where zeolite has firmly adhered to the surface of a support or the like and, as the case may be, preferred is one where a part of zeolite has firmly adhered even to the inside of the support.
- zeolite membrane composite for example, preferred is one where zeolite is crystallized as a membrane on the surface of a support of the like through hydrothermal synthesis thereon.
- a zeolite membrane may be attached to the outer surface thereof, or may be to the inner surface thereof, and further, depending on the system to which the membrane composite is applied, the zeolite membrane may be attached to both surfaces of the support.
- the zeolite membrane may be laminated on the surface of a support, or zeolite may be crystallized so as to fill up the pores in the surface layer of the support. In this case, it is important that neither cracks nor continuous micropores exist inside the crystallized membrane layer, and formation of a so-called dense membrane results in improvement of separability.
- peak intensity ratio A is generally less than 0.5, preferably at most 0.45. Not specifically defined, the lower limit is generally at least 0.001.
- peak intensity ratio B is generally at least 2.0, preferably at least 2.1, more preferably at least 2.3, even more preferably at least 2.5.
- the upper limit is generally less than 4.0, preferably at most 3.9, more preferably at most 3.7, even more preferably at most 3.5.
- the X-ray diffraction pattern is drawn through irradiation of the surface to which zeolite mainly adheres, with X-rays from a ray source of CuK ⁇ followed by scanning with a scan axis of ⁇ /2 ⁇ .
- the shape of the sample to be analyzed may be any one of which the surface of the membrane composite having zeolite mainly adhering thereto could be irradiated with X rays, and as one example thereof capable of well expressing the characteristic feature of the membrane composite, preferred is the membrane composite itself just after its production or one prepared by cutting the produced membrane composite into a suitable size that is restricted by apparatus.
- the membrane composite of the type may be analyzed to give the X-ray diffraction pattern thereof, while using an automatic variable slit and while fixing the irradiation width.
- the X-ray diffraction pattern in the case of using an automatic variable slit indicates a pattern with variable to stationary slit correction.
- the typical ratio of the (1,0,0) plane-derived peak intensity to the (2,0, ⁇ 1) plane-derived peak intensity in the CHA-type aluminosilicate zeolite membrane is less than 2.
- the ratio of 2.0 or more and less than 4.0 could mean that the zeolite crystal has grown while aligned in a moderate degree in such a manner that the (1,0,0) plane of the CHA structure to be, for example, rhombohedral setting could be nearly parallel to the surface of the membrane composite.
- growing the zeolite crystal while aligned is advantageous in that a dense membrane having high separation performance can be formed.
- the alignment in a moderate degree means that crystals of which the (1,0,0) planes have aligned nearly parallel to the surface of the membrane composite accounts for a moderate proportion of all crystals, and the proportion is larger than that in a powdery CHA-type aluminosilicate or the like in which the crystals align at random, and is smaller than that in a zeolite membrane of a CHA-aluminosilicate in which the (1,0,0) planes of most crystals have aligned nearly in parallel to the membrane composite surface and of which the peak intensity ratio B is 4 or more.
- the typical peak of the (1,1,1) plane-derived peak intensity to the (2,0, ⁇ 1) plane-derived peak intensity in the CHA-type aluminosilicate zeolite membrane is less than 0.5.
- the ratio of less than 0.5 could mean that the zeolite crystals have poorly grown while aligned in such a manner that the (1,1,1) plane of the CHA structure to be, for example, rhombohedral setting could be nearly parallel to the surface of the membrane composite.
- the zeolite crystals having poorly grown while aligned in that manner mean that the proportion of the zeolite crystals of which the (1,1,1) planes have aligned nearly in parallel to the surface of the membrane composite to all the crystals is small, or that is, the (1,1,1) planes of the crystals face almost at random.
- any of the peak intensity ratio A or B is a value falling within the above-mentioned specific range means that the zeolite crystals have grown while aligned in a moderate degree to thereby provide a dense membrane having high separation performance.
- the dense zeolite membrane in which CHA-type zeolite crystals have grown while aligned in a moderate degree may be attained according to thermal synthesis to give a zeolite membrane, in which, for example, a specific organic template is preferably used and in which K + ions are made to exist in the aqueous reaction mixture, as described below.
- the water adsorption of the zeolite membrane composite at a relative pressure of 0.8 is 2 times or more and 10 times or less the water adsorption thereof at a relative pressure of 0.2.
- the adsorption isotherm is a graph showing the adsorption change relative to pressure at a constant temperature of material.
- the horizontal axis indicates the relative pressure derived by dividing the equilibrium pressure by the saturated vapor pressure (P/P 0 ), which takes a value of from 0 to 1.
- the water (water vapor) adsorption (g/g) of the zeolite composite membrane at a relative pressure of 0.8 and that at a relative pressure 0.2 are referred to as indices.
- the ratio of the water absorption at a relative pressure of 0.8 to the water absorption thereof at a relative pressure of 0.2 is preferably 2 or more and 10 or less, and the value is more preferably 2.1 or more, even more preferably 2.2 or more, and is more preferably 8 or less, even more preferably 5 or less.
- the value is generally correlated with water adsorption to the meso pores in a zeolite membrane, and the larger value means that the hydrophilic meso pore volume tends to be large, while the smaller value means that the hydrophilic meso pore volume tends to be small.
- the membrane of which the value is too large is often a membrane in which a large number of mesopores exist and which therefore has a small density, and accordingly, the membrane of the type tends to be a membrane having low separation performance; while on the other hand, the membrane of which the value is too small is often a membrane in which few mesopores exist and which therefore has a high density, and the membrane of the type tends to be a membrane having high separation performance but having a low permeation amount therethrough.
- the value is 2 or more and 10 or less, then it becomes possible to provide a membrane having good separation performance and having a high permeation amount therethrough.
- the production method for the zeolite membrane is not specifically defined so far as the method realizes formation of the above-mentioned specific zeolite membrane on a support.
- a method of crystallizing zeolite on a support as a membrane thereon (2) a method of firmly fixing zeolite to a support by an inorganic binder, an organic binder or the like, (3) a method of firmly fixing a zeolite-dispersed polymer thereto, (4) a method of firmly fixing zeolite to a support by dipping a support in a slurry of zeolite optionally followed by suction, etc., and any of these methods is employable here.
- a method of crystallizing zeolite on an inorganic porous support as a membrane thereon is not specifically defined.
- Preferred is a method of putting a support into a reaction mixture for hydrothermal synthesis for zeolite production (hereinafter this may be referred to as “aqueous reaction mixture”) followed by direct hydrothermal synthesis to thereby crystallize zeolite on the surface of the support, etc.
- an aqueous reaction mixture of which the composition has been prepared and homogenized is put into a heat-resistant and pressure-tight container such as an autoclave or the like in which a support has been gently fixed therein, then airtightly sealed up and heated for a predetermined period of time.
- a heat-resistant and pressure-tight container such as an autoclave or the like in which a support has been gently fixed therein, then airtightly sealed up and heated for a predetermined period of time.
- aqueous reaction mixture preferred is one containing an Si element source, an Al element source, an alkali source and water, and optionally containing an organic template.
- the Si element source to be used for the aqueous reaction mixture includes, for example, amorphous silica, colloidal silica, silica gel, sodium silicate, amorphous aluminosilicate gel, tetraethoxysilane (TEOS), trimethylethoxysilane, etc.
- the Al element source includes, for example, sodium aluminate, aluminium hydroxide, aluminium sulfate, aluminium nitrate, aluminium oxide, amorphous aluminosilicate gel, etc.
- the mixture may additionally contain any other element source than the Al element source, for example, an element source of Ga, Fe, B, Ti, Zr, Sn, Zn or the like.
- alkali for use in the alkali source is not specifically defined, for which employable are an alkali metal hydroxide and an alkaline earth metal hydroxide.
- the metal species of the metal hydroxide generally includes Na, K, Li, Rb, Cs, Ca, Mg, Sr, Ba, etc. Preferred are Na and K, and more preferred is K. Two or more different types of metal species may be used for the metal hydroxide. Concretely, preferred is a combination of Na and K, or a combination of Li and K.
- alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, etc.
- alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, etc.
- hydroxide ions of counter anions of organic template As the alkali source for use in the aqueous reaction mixture, usable are hydroxide ions of counter anions of organic template to be mentioned next.
- an organic template (structure directing agent) may be used, and preferred here is one synthesized by the use of an organic template. Synthesizing by the use of an organic template increases the ratio of the silicon atom relative to the aluminium atom in the crystallized zeolite and therefore enhances the crystallinity of the zeolite.
- the organic template may be any one capable of forming a desired zeolite membrane.
- One alone or two or more different types of templates may be used here either singly or as combined.
- amines or quaternary ammonium salts are usable as the organic template.
- organic templates described in U.S. Pat. No. 4,544,538 and US Patent Application Publication 2008/0075656.
- cations derived from alicyclic amines such as cations derived from 1-adamantanamine, cations derived from 3-quinacridinal, cations derived from 3-exo-aminonorbornene, etc. Of those, more preferred are cations derived from 1-adamantanamine.
- a cation derived from 1-adamantanamine is used as the organic template here, a CHA-type zeolite capable of forming a dense membrane may crystallize.
- N,N,N-trialkyl-1-adamantanammonium cation is an N,N,N-trialkyl-1-adamantanammonium cation.
- the three alkyl groups of the N,N,N-trialkyl-1-adamantanammonium cation are alkyl groups independent of each other, and are preferably lower alkyl groups, more preferably methyl groups.
- the most preferred compound is N,N,N-trimethyl-1-adamantanammonium cation.
- the cation of the type is accompanied by an anion not causing any harm to the formation of CHA-type zeolite.
- Typical examples of the anion of the type include halide ions such as Cl ⁇ , Br ⁇ , I ⁇ , etc.; as well as hydroxide ion, acetate, sulfate, and carboxylate. Of those, especially preferred for use here is a hydroxide ion, and the halide ion may function as an alkali source as described above.
- N,N,N-trialkylbenzylammonium cations are also usable.
- the alkyl groups are independent of each other, and are preferably lower alkyl groups, more preferably methyl groups.
- the most preferred compound is N,N,N-trimethylbenzylammonium cation.
- the anion accompanied by the cation is the same as above.
- the ratio of the Si element source and the Al element source in the aqueous reaction mixture is generally expressed as the molar ratio of oxides of the respective elements, or that is, as the molar ratio of SiO 2 /Al 2 O 3 .
- the ratio of SiO 2 /Al 2 O 3 is not specifically defined, so far as the ratio could enable formation of zeolite having the above-mentioned ratio of SiO 2 /Al 2 O 3 .
- the ratio is generally at least 5, preferably at least 20, more preferably at least 30, even more preferably at least 40, especially preferably at least 50.
- the upper ratio of the ratio is generally at most 500, preferably at most 200, more preferably at most 150, even more preferably at most 140.
- zeolite of a CHA-type aluminosilicate capable of forming a dense membrane can be crystallized.
- the ratio of the silica source and the organic template in the aqueous reaction mixture is, as the ratio by mol of organic template to SiO 2 (molar ratio of organic template/SiO 2 ), generally at least 0.005, preferably at least 0.01, more preferably at least 0.02, and is generally at most 1, preferably at most 0.4, more preferably at most 0.2.
- a dense zeolite membrane can be formed and, in addition thereto, the formed zeolite has strong acid resistance and Al is hardly released therefrom. Further, under the condition, an especially dense and acid-resistant CHA-type aluminosilicate zeolite can be formed.
- the ratio of Si element source and the metal hydroxide is, as the ratio by mol of M (2/n) O/SiO 2 (wherein M means an alkali metal or an alkaline earth metal, and n indicates the valence thereof, 1 or 2), generally at least 0.02, preferably at least 0.04, more preferably at least 0.05, and is generally at most 0.5, preferably at most 0.4, more preferably at most 0.3.
- the alkali metal to be used contains potassium (K), since a denser and higher crystalline membrane may be formed.
- K potassium
- the molar ratio of K to the total of alkali metals and alkaline earth metals is generally at least 0.01, preferably at least 0.2, more preferably at least 0.3, and the upper limit thereof is generally at most 1.
- the ratio of the Si element source and water is, as the ratio by mol of water to SiO 2 (molar ratio of H 2 O/SiO 2 ), generally at least 10, preferably at least 30, more preferably at least 40, even more preferably at least 50, and is generally at most 1000, preferably at most 500, more preferably at most 200, even more preferably at most 150.
- a dense zeolite membrane When the molar ratios of the substances in the aqueous reaction mixture each fall within the above range, a dense zeolite membrane can be formed.
- the amount of water is especially important in formation of the dense zeolite membrane, and under the condition where the amount of water is larger than that of silica as compared with the ordinary condition in powdery synthesis, a dense membrane can be formed readily.
- the amount of water in synthesis of a powdery CHA-type aluminosilicate zeolite is, as the molar ratio of H 2 O/SiO 2 , from 15 to 50 or so.
- the molar ratio of H 2 O/SiO 2 is increased (to be 50 or more and 1000 or less), or that is, under the condition where the amount of water is large, a zeolite membrane composite having a CHA-type aluminosilicate zeolite crystallized on the surface of a support or the like as a dense membrane thereon and therefore having high separation performance can be obtained.
- zeolite crystallization on a support can be promoted.
- the method of adding a seed crystal is not specifically defined.
- employable here is a method of adding a seed crystal to the aqueous reaction mixture, or a method of attaching a seed crystal onto a support.
- a seed crystal is attached onto a support. Previously attaching a seed crystal onto a support facilitates formation of a dense zeolite membrane having good separation performance.
- the seed crystal to be used here may be any zeolite capable of promoting crystallization.
- the same crystal type as that of the zeolite membrane to be formed is used for efficient crystallization.
- a seed crystal of CHA-type zeolite is preferred.
- the grain size of the seed crystal is preferably smaller, and, if desired, the seed crystal may be ground before use herein.
- the grain size is generally at least 0.5 nm, preferably at least 1 nm, more preferably at least 2 nm, and is generally at most 5 ⁇ m, preferably at most 3 ⁇ m, more preferably at most 2 ⁇ m.
- the method of attaching a seed crystal onto a support is not specifically defined.
- employable here are a dipping method that comprises dispersing a seed crystal in a solvent such as water or the like and then dipping a support in the dispersion to make the seed crystal adhere to the support, and a coating method that comprises mixing a seed crystal with a solvent such as water or the like to give a slurry and then applying the resulting slurry with rubbing onto a support.
- a dipping method that comprises dispersing a seed crystal in a solvent such as water or the like and then dipping a support in the dispersion to make the seed crystal adhere to the support
- a coating method that comprises mixing a seed crystal with a solvent such as water or the like to give a slurry and then applying the resulting slurry with rubbing onto a support.
- Preferred is the dipping method for reproducible production of a membrane composite under control of the seed crystal adhering amount.
- the solvent in which the seed crystal is dispersed is not specifically defined, but water and an alkaline aqueous solution are especially preferred.
- the type of the alkaline aqueous solution is not specifically defined. Preferred are an aqueous sodium hydroxide solution and an aqueous potassium hydroxide solution. These alkali species may be mixed.
- the alkali concentration is not also specifically defined, and may be generally at least 0.0001 mol %, preferably at least 0.002 mol %, more preferably at least 0.001 mol %, even more preferably at least 0.002 mol %. Also generally, the concentration is at most 1 mol %, preferably at most 0.8 mol %, more preferably at most 0.5 mol %, even more preferably at most 0.2 mol %.
- the amount of the seed crystal to be dispersed is not specifically defined. In general, the amount is at least 0.01% by mass relative to the total mass of the dispersion, preferably at least 0.1% by mass, more preferably at most 0.5% by mass, and is generally at most 20% by mass, preferably at most 10% by mass, more preferably at most 5% by mass, even more preferably at most 3% by mass.
- the amount of the seed crystal to be dispersed When the amount of the seed crystal to be dispersed is too small, then the amount of the seed crystal that adheres to the support would be small, and therefore the support would have any partial site where zeolite does not form during hydrothermal synthesis, and there is a probability that a defective membrane may form.
- the amount of the seed crystal in the dispersion is too large, then the seed crystal would go to waste since the amount of the seed crystal to adhere to the support in the dipping method is nearly constant and it is therefore disadvantageous in point of the production cost.
- the amount of the seed crystal to be previously attached to the support is not specifically defined. In terms of mass per m 2 of support, the amount is generally at least 0.01 g, preferably at least 0.05 g, more preferably at least 0.1 g, and is generally at most 100 g, preferably at most 50 g, more preferably at most 10 g, even more preferably at most 8 g.
- the amount of the seed crystal is less than the lower limit, then the crystal would be difficult to form, the membrane growth could be insufficient, and the membrane growth would be ununiform.
- the amount of the seed crystal is more than the upper limit, then the surface roughness would be augmented by the seed crystal, spontaneous nuclei resulting from the seed crystal having dropped from the support would readily grow further and therefore the membrane growth on the support would be thereby interfered with. In any case falling outside the range, a dense zeolite membrane would be difficult to form.
- a zeolite membrane is formed on a support through hydrothermal synthesis
- the method of fixing the support is not specifically defined.
- employable is any configuration of vertical setting or horizontal setting.
- the zeolite membrane may be formed according to a stationary method, or may be formed while the aqueous reaction mixture is stirred.
- the temperature in zeolite membrane formation is generally 100° C. or higher, preferably 120° C. or higher, more preferably 150° C. or higher, and is generally 200° C. or lower, preferably 190° C. or lower, more preferably 180° C. or lower.
- the reaction temperature is too low, then zeolite crystallization would be difficult.
- the reaction temperature is too high, then zeolite of a type different from the type of zeolite in the invention would often form.
- the heating (reaction) time is not specifically defined, but is generally at least 1 hour, preferably at least 5 hours, more preferably at least 10 hours, and is generally at most 10 days, preferably at most 5 days, more preferably at most 3 days, and even more preferably at most 2 days.
- reaction time is too short, then zeolite crystallization would be difficult.
- reaction time is too long, then zeolite of a type different from the type of zeolite in the invention would often form.
- the pressure in zeolite membrane formation is not specifically defined.
- the autogenous pressure to arise in heating the aqueous reaction mixture put in a closed container, within the temperature range would be enough.
- an inert gas such as nitrogen or the like may be added to the container.
- the zeolite membrane composite formed through hydrothermal synthesis is washed with water, then heat-treated and dried.
- the heat treatment means that the zeolite membrane composite is dried by heating it, or the template, if used, is fired.
- the temperature in heat treatment is generally 50° C. or higher, preferably 80° C. or higher, more preferably 100° C. or higher, and is generally 200° C. or lower, preferably 150° C. or lower.
- the temperature is generally 350° C. or higher, preferably 400° C. or higher, more preferably 430° C. or higher, even more preferably 480° C. or higher, and is generally 900° C. or lower, preferably 850° C. or lower, more preferably 800° C. or lower, even more preferably 750° C. or lower.
- the heating time is not specifically defined so far as the zeolite membrane could be fully dried or the template could be fired within the time, but is preferably at least 0.5 hours, more preferably at least 1 time.
- the upper limit is not specifically defined but is generally at most 200 hours, preferably at most 150 hours, more preferably at most 100 hours, even more preferably at most 24 hours.
- the hydrothermal synthesis is carried out in the presence of an organic template
- the organic template is removed, for example, through heat treatment, extraction or the like, preferably through heat treatment, or that is, firing.
- the proportion of the remaining organic template may increase and, if so, the micropores in zeolite would decrease and, as a result, the gas permeation amount in separation and concentration would decrease.
- the firing time may vary depending on the heating speed and the cooling speed, and is not specifically defined so far as the organic template could be fully removed within the time.
- the time is at least 1 hour, more preferably at least 5 hours.
- the upper limit is not specifically defined, and is, for example generally at most 200 hours, preferably at most 150 hours, more preferably at most 100 hours, even more preferably at most 24 hours.
- the firing may be carried out in an air atmosphere, to which, however, oxygen or an inert gas may be added.
- the heating speed in firing is preferably as slow as possible in order that the difference in the coefficient of thermal expansion between the support and zeolite could provide few cracks in the zeolite membrane.
- the heating speed is generally at most 5° C./min, preferably at most 2° C./min, more preferably at most 1° C./min, even more preferably at most 0.5° C./min. In general, the heating speed is at least 0.1° C./min in consideration of operability.
- the cooling speed must also be controlled so as to prevent the zeolite membrane from being cracked. Like the heating speed, the cooling speed is also preferably lower.
- the cooling speed is generally at most 5° C./min, preferably at most 2° C./min, more preferably at most 1° C./min, even more preferably at most 0.5° C./min. In general, the cooling speed is at least 0.1° C./min in consideration of operability.
- the zeolite membrane may be ion-exchanged, or may be silylated.
- the ion exchange is generally carried out after template removal in case where a template is used in synthesis.
- the ion to be exchanged includes proton, alkali metal ions such as Na + , K + , Li + , etc.; Group 2 element ions such as Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ , etc.; ions of transition metals such as Fe, Cu, Zn, Ag, Al, Ga, La, etc. Of those, preferred are proton, Na + , Mg 2+ , and Fe, Al, Ga and La ions.
- the ion exchange may be carried out according to a method where the zeolite membrane is, after fired (when a template is used), treated with an aqueous solution containing an ammonium salt or an exchanging ion such as NH 4 NO 3 , NaNO 3 or the like, or as the case may be, with an acid such as hydrochloric acid or the like, generally at a temperature of from room temperature to 100° C., and then washed with water. Further, if desired, the membrane may be fired at 200° C. to 500° C.
- the zeolite membrane composite is dipped in a solution containing an Si compound. Accordingly, the zeolite membrane surface is modified with the Si compound to thereby get the above-mentioned specific physicochemical properties. For example, surely forming a layer that contains many Si—OH's on the surface of the zeolite membrane could enhance the polarity of the membrane surface and therefore could improve the separation performance of the polar molecules in the membrane. In addition, modifying the zeolite membrane surface with the Si compound can secondarily provide an effect of blocking the fine defects existing in the membrane surface.
- the solvent to be used for the silylation treatment may be water or an organic solvent.
- the solution may be acidic or basic, and in the case, the silylation reaction could be catalyzed by acid or base.
- the silylating agent is preferably an alkoxysilane.
- the treatment temperature may be generally from room temperature to 150° C. or lower, and the treatment may be carried out for from 10 minutes to 30 hours or so, but may be determined depending on the type of the silylating agent and the solvent.
- the air permeation through the heat-treated zeolite membrane composite is generally at least 10 L/(m 2 ⁇ h), preferably at least 20 L/(m 2 ⁇ h), more preferably at least 30 L/(m 2 ⁇ h), even more preferably at least 35 L/(m 2 ⁇ h), still more preferably at least 100 L/(m 2 ⁇ h).
- the upper limit of the permeation is not specifically defined but is preferably at most 1000 L/(m 2 ⁇ h), more preferably at most 800 L/(m 2 ⁇ h), even more preferably at most 700 L/(m 2 ⁇ h).
- the air permeation is the permeation of air [L/(m 2 ⁇ h)] through the zeolite membrane composite which is put under atmospheric pressure and is connected to a vacuum line under 5 kPa inside it, as described in detail in the section of Examples.
- the air permeation is a value that leads to gas permeation.
- Membranes having a large air permeation may have a large gas permeation, but those having a too large air permeation may be often poor in separability.
- the zeolite membrane of the invention has a suitable air permeation as described above, and has a large gas permeation and good separation performance, and in particular, the zeolite membrane has a performance suitable for separation of vapor components.
- the zeolite membrane composite thus produced as above has excellent properties and can be favorably used as a membrane separating means for a vapor mixture or a liquid mixture in the invention.
- the separation or concentration method for a vapor mixture of the invention comprises bringing a vapor mixture of multiple vapor components into contact with the above-mentioned zeolite membrane composite to thereby separate the highly-permeative component through permeation from the vapor mixture, or to thereby separate the highly-permeative vapor component through permeation therefrom so as to concentrate the poorly-permeative vapor component in the mixture.
- One separation function of the zeolite membrane of the invention is separation as a molecular sieve through which vapor molecules having a size or not more than the effective pore size of the zeolite used can be separated from the other vapor molecules smaller than the former.
- the highly-permeative vapor component as referred to in the invention is a vapor component capable of readily passing through the micropores of the zeolite crystal phase of a CHA-type aluminosilicate, and is preferably a vapor component comprising vapor molecules of which the molecular size is smaller than about 0.38 nm or so.
- the effective pore size of zeolite may be controlled by the metal species to be introduced, and also by ion exchange, acid treatment, silylation treatment or the like. By controlling the effective pore size, the separation performance of the membrane can be improved.
- the pore size would be slightly influenced by the atomic diameter of the metal species to be introduced into the zeolite framework.
- a metal of which the atomic diameter is larger than that of silicon, concretely for example, boron (B) or the like is introduced, the pore size could be small; while when a metal having a larger atomic diameter than that of silicon, concretely for example, tin (Sn) or the like is introduced, then the pore size could be large.
- the pore size would also be influenced, as the case may be.
- the effective pore size tends to reduce, while on the other hand, in case of ion exchange with a monovalent ion having a small ionic diameter, the effective pore size could be a value close to the pore size which the CHA structure has. In case of ion exchange with a divalent ion such as calcium, the effective pore size could also be a value close to the pore size which the CHA structure has, depending on the position of the exchange site.
- Silylation treatment could reduce the effective pore size of zeolite.
- Silylation of the terminal silanol in the outer surface further combined with lamination with a silylating layer could reduce the effective pore size of the micropores facing the outer surface of zeolite.
- Still another separation function of the zeolite membrane composite of the invention is to control the adsorption of vapor molecules to the zeolite membrane through control of the surface properties of zeolite. Specifically, by controlling the polarity of zeolite, highly-adsorbable molecules could be made to readily pass through the membrane composite.
- the absorbability of molecules and the pore size of zeolite may be controlled by ion exchange, whereby the permeation performance may also be controlled.
- the desired vapor mixture includes those containing at least one component selected from carbon dioxide, hydrogen, oxygen, nitrogen, methane, ethane, ethylene, propane, propylene, normal butane, isobutane, 1-butene, 2-butene, isobutene, sulfur hexafluoride, helium, carbon monoxide, nitrogen monoxide, water, etc.
- the vapor components having a high permeance are separated through the zeolite membrane composite, while the vapor components having a low permeance are concentrated on the side of the supply gas.
- the vapor mixture contains at least two components of the above-mentioned components.
- the two components are preferably a combination of a component having a high permeance and a component having a low permeance.
- the condition for gas separation varies depending on the gas species and the composition to be targeted and on the membrane performance.
- the temperature is from ⁇ 20 to 300° C., preferably from 0 to 200° C., more preferably from 0 to 150° C.
- the separation at 0 to 25° C. is often at a temperature close to the ambient temperature, and is therefore advantageous in that it does not require any energy for temperature control for the gas to be separated or may require only a small amount of energy.
- a gas highly adsorbable to the zeolite membrane tends to have an increased permeability even at a low temperature, and for the purpose of increasing the permeation thereof, the gas of the type may be cooled in a range of 25° C. or lower and ⁇ 20° C. or higher.
- the pressure of the supply gas may be as such in case where the gas to be separated is under high pressure, but the pressure may be suitably reduced and adjusted to a desired pressure for use herein. In case where the pressure of the gas to be separated is lower than that for use in separation, the pressure may be increased by the use of a compressor or the like.
- the pressure of the supply gas may be generally atmospheric pressure, or may be higher than atmospheric pressure, and is preferably at least 0.1 MPa, more preferably at least 0.11 MPa.
- the upper limit is generally at most 20 MPa, preferably at most 10 MPa, more preferably at most 1 MPa.
- the differential pressure between the gas on the supply side and the gas on the permeation side is generally at most 20 MPa, preferably at most 10 MPa, more preferably at most 5 MPa, even more preferably at most 1 MPa. Also in general, the differential pressure is at least 0.001 MPa, preferably at least 0.01 MPa, more preferably at least 0.02 MPa.
- differential pressure means the difference between the partial pressure of the gas on the supply side and the partial pressure thereof on the permeation side.
- pressure [Pa] indicates absolute pressure.
- the pressure on the permeation side is generally at most 10 MPa, preferably at most 5 MPa, more preferably at most 1 MPa, even more preferably at most 0.5 MPa.
- the lower limit is not also limited, and the pressure may be 0 MPa or more. Under the condition where the pressure is 0 MPa, the separation through the membrane realizes a state where the concentration of a highly-permeative vapor could be the lowest in the poorly-permeative gas.
- the pressure on the permeation side may be set high.
- the flow rate of the supply gas may be such that the supply gas flow can supplement the decrease in the permeating gas and such that the flow rate can secure gas mixing enough to make the concentration of the poorly-permeative gas in the supply gas at around the membrane the same as the concentration of the entire gas. Therefore, depending on the tubular diameter of the separation unit and the separation performance of the membrane, the flow rate is generally at least 0.5 mm/sec, preferably at least 1 mm/sec. The upper limit is not specifically defined, and is generally at most 1 msec, preferably at most 0.5 msec.
- a sweep gas may be used.
- a gas differing from the supply gas is made to flow on the permeation side and the gas having permeated through the membrane is collected by the action of the sweep gas.
- the pressure of the sweep gas is generally atmospheric pressure and is not specifically defined.
- the pressure is at most 20 MPa, more preferably at most 10 MPa, even more preferably at most 1 MPa, and the lower limit thereof is preferably at least 0.09 MPa, more preferably at least 0.1 MPa.
- the sweep gas may be under reduced pressure.
- the flow rate of the sweep gas may be such that the permeated gas could be fully substituted with the sweep gas.
- the flow rate is at least 0.5 mm/sec, preferably at least 1 mm/sec.
- the upper limit is not specifically defined, and may be generally at most 1 m/sec, preferably at most 0.5 m/sec.
- the apparatus for use in gas separation is not specifically defined.
- the membrane is used as incorporated in a module.
- the membrane module may be, for example, an apparatus schematically shown in FIG. 1 or FIG. 2 .
- Also employable here are membrane modules exemplified in, for example, “Gas Separation/Purification Techniques”, published by Toray Research Center, 2007, page 22, etc.
- the membranes may be configured as multiple stages. Specifically, a gas to be separated is applied to a membrane module, and the gas on the non-permeation that has not passed through the membrane is further applied to another membrane module, or the permeated gas may be applied to another membrane module. In the former method, the concentration of the poorly-permeative gas on the non-permeation side may be further increased, and in the latter method, the concentration of the highly-permeative gas in the permeated gas may be further increased.
- the gas pressure may be adjusted by the use of a booster or the like.
- membranes each having different performance may be arranged in individual stages.
- a membrane having high permeation performance may have low separation performance while, on the other hand, a membrane having high separation performance may have low permeation performance.
- the necessary membrane area could be small while the poorly-permeative component that is desired to be concentrated on the non-permeation side would pass through the membrane to move to the permeation side, but on the other hand, in processing the mixture through a membrane having high separation performance, the poorly-permeative component that is desired to be concentrated on the non-permeation side could hardly pass through the membrane to move to the permeation side, but the necessary membrane area may increase.
- the relationship between the necessary membrane area and the permeation amount of the gas to be concentrated could hardly be controlled, but using multiple membranes each having different performance could facilitate the control.
- the membrane to be used is so controlled as to realize the best relation of the suitable membrane area and the permeation amount of the gas to be concentrated, thereby maximizing the advantages as a whole.
- the zeolite membrane composite of the invention is excellent in chemical resistance, oxidation resistance, heat-resistant stability and pressure resistance, exhibits high permeation performance and separation performance, and has performance excellent in durability.
- the zeolite membrane composite shows excellent separation performance for separating inorganic gas and lower hydrocarbon.
- High permeation performance indicates a sufficient throughput and, for example, means that the permeance of a membrane for the vapor component that passes therethrough [mol ⁇ (m 2 ⁇ s ⁇ Pa) ⁇ 1 ] is, for example, when carbon dioxide is made to pass through the membrane at a temperature of 50° C. and under a differential pressure of 0.098 MPa, generally at least 3 ⁇ 10 ⁇ 8 , preferably at least 3 ⁇ 10 ⁇ 7 , more preferably at least 5 ⁇ 10 ⁇ 7 , even more preferably at least 7 ⁇ 10 ⁇ 7 , still more preferably at least 1 ⁇ 10 ⁇ 6 .
- the upper limit is not specifically defined and is generally at most 3 ⁇ 10 ⁇ 4 .
- the permeance [mol ⁇ (m 2 ⁇ s ⁇ Pa) ⁇ 1 ] is, for example, when methane is made to pass through the membrane under the same condition, generally at most 3 ⁇ 10 ⁇ 7 , preferably at most 3 ⁇ 10 ⁇ 8 , more preferably at most 3 ⁇ 10 ⁇ 9 , and ideally, the permeance is 0, but may be on an order of from 10 ⁇ 10 to 10 ⁇ 14 or so for practical use.
- permeance is a value to be obtained by dividing the permeated substance amount by the product of the membrane area, the time and the partial pressure difference between the supply side to which the substance to be permeated is supplied and the permeation side, and the unit thereof is [mol ⁇ (m 2 ⁇ s ⁇ Pa) ⁇ 1 ].
- the value is calculated according to the method described in the section of Examples.
- the selectivity of the zeolite membrane is expressed by an ideal separation coefficient and separation coefficient.
- the ideal separation coefficient and the separation coefficient each are an index that indicates selectivity generally used in membrane separation.
- the ideal separation coefficient is a value to be calculated according to the method described in the section of Examples, and the separation coefficient is a value to be calculated according to the method mentioned below.
- the separation coefficient is calculated according to the following formula (2).
- Q′ 1 and Q′ 2 each indicate the permeation amount [mol ⁇ (m 2 ⁇ s) ⁇ 1 ] of the highly-permeative gas and the poorly-permeative gas, respectively; and P′ 1 and P′ 2 each indicate the partial pressure [Pa] of the highly-permeative gas and the poorly-permeative gas in the supply gas.
- the separation coefficient may also be calculated according to the following formula (3).
- C′ 1 and C′ 2 each indicate the concentration [mol %] of the highly-permeative gas and the poorly-permeative gas in the permeated gas, respectively; and C 1 and C 2 each indicate the concentration [mol %] of the highly-permeative gas and the poorly-permeative gas in the supply gas.
- the ideal separation coefficient is, for example, when carbon dioxide and methane are made to pass through the membrane at a temperature of 50° C. and under a differential pressure of 0.1 MPa, generally at least 10, preferably at least 20, more preferably at least 30, even more preferably at least 40, still more preferably at least 50.
- the upper limit of the ideal separation coefficient is for the case where only carbon dioxide passes through the membrane, and in the case, the ideal separation coefficient reaches an infinite value. In practice, the separation coefficient could be at most 100,000 or so.
- the separation coefficient is, for example, when a 1/1 mixed gas of carbon dioxide and methane is applied for permeation at a temperature of 50° C. and under a differential pressure of 0.098 MPa, generally at least 10, preferably at least 20, more preferably at least 30, even more preferably at least 40, still more preferably at least 50.
- the upper limit of the separation coefficient is for the case where only carbon dioxide passes through the membrane, and in the case, the separation coefficient reaches an infinite value. In practice, the separation coefficient could be at most 100,000 or so.
- the zeolite membrane composite of the invention is, as described above, excellent in chemical resistance, oxidation resistance, heat-resistant stability and durability, exhibits high permeation performance and separation performance, and is excellent in durability.
- the zeolite membrane composite is especially favorably used for gas separation technology to be mentioned below.
- Carbon dioxide separation technology includes removal of carbon dioxide from natural gas, removal of carbon dioxide from landfill gas to be generated in landfilling with organic substances such as household wastes and the like (containing methane about 60%, carbon dioxide about 40%, and minor nitrogen and water vapor), etc.
- Hydrogen separation technology includes hydrogen recovery in petroleum purification industry, hydrogen recovery/purification in various reaction processes in chemical industry (mixture of hydrogen, carbon monoxide, carbon dioxide, hydrocarbon, etc.), production of high-purity hydrogen for fuel cells, etc.
- Production of hydrogen for fuel cells is through water vapor modification reaction of methane, and separation of hydrogen from a mixed gas of H 2 , CO, CH 4 and H 2 O is needed.
- oxygen-rich gas from air for medical use, oxygen-rich air for combustion, etc.
- nitrogen-rich gas from air for antiexplosion, antioxidation, etc.
- water vapor separation demoisturization for precision instruments, etc.
- dissolved gas separation deaeration from water, organic liquids
- organic gas separation organic gas separation, separation of olefins, paraffins in petroleum refining industry, petrochemical industry
- the separation or concentration method for a liquid mixture of the invention comprises bringing a liquid mixture of multiple components into contact with the above-mentioned zeolite membrane composite to thereby separate the highly-permeative component through permeation from the liquid mixture, or to thereby separate the highly-permeative component through permeation therefrom so as to concentrate the poorly-permeative component in the mixture.
- the zeolite membrane composite to be used may be the same as that mentioned above, and preferred embodiments thereof are also the same as above.
- a liquid mixture containing an organic compound is kept in contact with one side of the support side or the zeolite membrane side, whereupon the opposite side is kept under a lower pressure than that on the side with which the mixture is kept in contact, and accordingly, the component that is highly permeative through the zeolite membrane (the substance in the mixture of which the permeability is relatively high) is selectively made to pass through the membrane, or that is, the highly-permeative component is made to pass therethrough as a main component. Consequently, the highly-permeative component (substance) can be separated from the liquid mixture. As a result, the concentration of the specific organic compound in the mixture (the substance in the mixture of which the permeability is relatively low) can be increased, and the specific organic compound can be thereby separated and collected, or concentrated.
- the liquid mixture for separation or concentration may be any and every type of liquid mixture that comprises multiple components capable of being separated or concentrated through the zeolite membrane composite of the invention.
- the liquid mixture is, for example, a mixture of an organic compound and water (hereinafter this may be referred to as “water-containing organic compound”)
- water in general, water is highly permeative through the zeolite membrane, and therefore water is separated from the mixture and the organic compound is concentrated in the original mixture.
- a separation or concentration method that is referred to as a pervaporation method or a vapor permeation method is one embodiment of the method of the invention.
- the pervaporation method is a separation or concentration method that comprises introducing a liquid mixture into the separation membrane directly as it is, and therefore facilitates the process including separation or concentration.
- the vapor permeation method is a separation/concentration method in which a liquid mixture is vaporized and then introduced into the separation membrane, and which therefore enables combined use with a distillation apparatus or is applicable to separation at a higher temperature and a higher pressure.
- a liquid mixture is, after vaporized, introduced into the separation membrane, and therefore in this, the influence of the impurities contained in the supply liquid as well as that of the substance therein to form an associate or an oligomer in a liquid state on the membrane can be reduced.
- the zeolite membrane composite of the invention can be favorably used in any method.
- the separation performance lowers more when the temperature is higher; however, the zeolite membrane composite of the invention can express high separation performance even at a high temperature.
- the liquid mixture is first vaporized and then separated, and therefore, in general, the separation condition is severer than in the pervaporation method, and accordingly, the vapor permeation method requires durability of the membrane composite to be used therein.
- the zeolite membrane composite of the invention has durability enough for separation even under high-temperature condition, and is therefore favorable for the vapor permeation method.
- the zeolite membrane composite of the invention can still exhibit high permeation performance and selectivity even when used for processing a water-containing organic compound having a water content of 20% by mass or more therethrough, and therefore secures performance as a separation membrane excellent in durability.
- the high permeation performance indicates a sufficient amount of throughput, and for example, means that the permeation flux of the substance to pass through the membrane is, when, for example, a mixture of 2-propanol or N-methyl-2-pyrrolidone and water having a water content of 30% by mass is made to penetrate through the membrane at 70° C. and under a pressure difference of 1 atmosphere (1.01 ⁇ 10 5 Pa), at least 1 kg/(m 2 ⁇ hr), preferably at least 3 kg/(m 2 ⁇ hr), more preferably at least 5 kg/(m 2 ⁇ hr).
- the upper limit of the permeation flux is not specifically defined, and may be generally at most 20 kg/(m 2 ⁇ hr), preferably at most 15 kg/(m 2 ⁇ hr).
- Permeance indicates a permeation flux per pressure difference (pressure normalized flux), and is a value to be obtained by dividing the permeated substance amount by the product of the membrane area, the time and the water partial pressure difference.
- the water permeance is generally at least 3 ⁇ 10 ⁇ 7 mol/(m 2 ⁇ s ⁇ Pa), preferably at least 5 ⁇ 10 ⁇ 7 mol/(m 2 ⁇ s ⁇ Pa), more preferably at least 1 ⁇ 10 ⁇ 6 mol/(m 2 ⁇ s ⁇ Pa), even more preferably at least 2 ⁇ 10 ⁇ 6 mol/(m 2 ⁇ s ⁇ Pa).
- the upper limit of the permeance is not specifically defined, and is generally at most 1 ⁇ 10 ⁇ 4 mol/(m 2 ⁇ s ⁇ Pa), preferably at most 5 ⁇ 10 ⁇ 5 mol/(m 2 ⁇ s ⁇ Pa).
- the selectivity is represented by a separation coefficient.
- the separation coefficient is calculated according to the following formula (4) to indicate the selectivity generally used in membrane separation.
- P ⁇ indicates the mass percent concentration of the main component in the permeated liquid
- P ⁇ indicates the mass percent concentration of the accessory component in the permeated liquid
- F ⁇ indicates the mass percent concentration of the component to be the main component in the permeated liquid, in the mixture to be separated
- F ⁇ indicates the mass percent concentration of the component to be the accessory component in the permeated liquid, in the mixture to be separated.
- the separation coefficient is, for example, when a mixture of 2-propanol or N-methyl-2-pyrrolidone and water having a water content of 30% by mass is permeated under a pressure difference of 1 atmospheric pressure (1.01 ⁇ 10 5 Pa) at 70° C., generally at least 1000, preferably at least 4000, more preferably at least 10000, even more preferably at least 20000.
- the upper limit of the separation coefficient is in the case where entirely water only could pass through the membrane, and in the case, the separation coefficient would reach an infinite value, but the separation coefficient is preferably at most 10000000, more preferably at most 1000000.
- the water content thereof is generally at least 20% by mass, preferably at least 30% by mass, more preferably at least 45% by mass, and is generally at most 95% by mass, preferably at most 80% by mass, more preferably at most 70% by mass.
- the substance to pass through the zeolite membrane is generally water.
- the method would be inefficient since the throughput may lower.
- the membrane necessary for concentration would have a large area (in case where the membrane is formed to be tubular, the number of the tubes would increase), and therefore the economic outcomes would decrease.
- the water content of the water-containing organic compound may be previously adjusted according to a suitable water content controlling method.
- the preferred water content is the same as above.
- the water content controlling method may be any per-se known method, including, for example, distillation, pressure swing adsorption (PSA), temperature swing adsorption (TSA), desiccant system, etc.
- water may be further separated from the water-containing organic compound from which water has been separated through the zeolite membrane composite. Accordingly, water may be separated more highly, and the water-containing organic compound may be concentrated more highly.
- the organic compound includes, for example, carboxylic acids such as acetic acid, acrylic acid, propionic acid, formic acid, lactic acid, oxalic acid, benzoic acid, etc.; organic acids such as sulfonic acid, sulfinic acid, barbituric acid, uric acid, phenol, enol, diketone-type compounds, thiophenone, imide, oxime, aromatic sulfonamide, primary and secondary nitro compounds, etc.; alcohols such as methanol, ethanol, isopropanol (2-propanol), etc.; ketones such as acetone, methyl isobutyl ketone, etc.; aldehydes such as acetaldehyde, etc.; ethers such as dioxane, tetrahydrofuran, etc.; amides and other nitrogen-containing organic compounds (N-containing organic compounds) such as dimethylformamide, N-methylpyrrolidone, etc.; esters
- the effect of the zeolite membrane composite is noticeably expressed.
- Preferred is a mixture of a carboxylic acid and water, and a more preferred example is separation of acetic acid from water.
- the organic substance is preferably one having 2 or more carbon atoms, more preferably 3 or more carbon atoms.
- organic compounds containing at least one selected from alcohols, ethers, ketones, aldehydes and amides.
- organic compounds preferred are those having from 2 to 10 carbon atoms, and more preferred are those having from 3 to 8 carbon atoms.
- the organic compound may also be a polymer compound capable of forming a mixture with water (mixed solution).
- the polymer compound includes those having a polar group in the molecule, for example, polyols such as polyethylene glycol, polyvinyl alcohol, etc.; polyamines; polysulfonic acids; polycarboxylic acids such as polyacrylic acid, etc.; polycarboxylic acid esters such as polyacrylic acid esters, etc.; modified polymer compounds prepared by modifying polymers through graft polymerization or the like; copolymerized polymer compounds prepared by copolymerization of a nonpolar monomer such as olefin or the like and a polar monomer having a polar group such as a carboxyl group, etc.
- the water-containing organic compound may be a mixture capable of forming an azeotropic mixture, such as a mixture of water and phenol, and in separation of a mixture that forms an azeotropic mixture, the invention is advantageous in that water can be separated selectively and more efficiently than in separation by distillation.
- a mixture of an alcohol such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol or the like, and water
- a mixture of an ester such as ethyl acetate, ethyl acrylate, methyl methacrylate or the like, and water
- a mixture of a carboxylic acid such as formic acid, isobutyric acid, valeric acid or the like, and water
- a mixture of an aromatic organic substance such as phenol, aniline or the like, and water
- a mixture of a nitrogen-containing compound such as acetonitrile, acrylonitrile or the like, and water, etc.
- the water-containing organic compound may also be a mixture of water and a polymer emulsion.
- the polymer emulsion is a mixture of a surfactant and a polymer that is generally used in adhesives, coating materials, etc.
- the polymer for use in the polymer emulsion includes, for example, thermoplastic resins, such as polyvinyl acetate, polyvinyl alcohol, acrylic resin, polyolefin, olefin-polar monomer copolymer such as ethylene-vinyl alcohol copolymer or the like, polystyrene, polyvinyl ether, polyamide, polyester, cellulose derivative, etc.; thermosetting resins such as urea resin, phenol resin, epoxy resin, polyurethane, etc.; rubbers such as natural rubber, polyisoprene, polychloroprene, butadiene copolymer such as styrene-butadiene copolymer or the like, etc.
- the surfactant herein
- the zeolite membrane composite of the invention has acid resistance, and therefore can be effectively utilized especially for separation of water from a mixture of water and an organic acid such as acetic acid or the like or for separation of water for promoting esterification.
- the separation or concentration method for a liquid mixture of the invention may be carried out by producing a suitable separation or concentration apparatus, for example, the apparatus as schematically shown in FIG. 3 , by the use of the above-mentioned zeolite membrane composite, and introducing a liquid mixture of multiple components into the apparatus.
- the separation or concentration apparatus can be produced by the use of per-se known members.
- the invention is described more concretely, based on the following Examples; however, not overstepping the gist thereof, the invention is not limited by the following Examples.
- the production conditions and the data of the evaluation results in the following Examples have implications of preferred data in a range of the upper limit or the lower limit in the embodiments of the invention, and the preferred range may be one to be defined by the combination of the upper or lower limit and the data in the following Examples or by the combination of the data themselves in the following Examples.
- Apparatus Netherlands PANaltical's X′ PertPro MPD Optical System Specification: Incidence Side: Encapsulated X-ray tube (CuK ⁇ ) Soller Slit (0.04 rad) Divergence Slit (Variable Slit) Stage: XYZ stage Light-Receiving Side: Semiconductor array detector (X′ Celerator) Ni-Filter Soller Slit (0.04 rad) Goniometer Radius: 240 mm Measurement Condition X-ray Output (CuK ⁇ ): 45 kV, 40 mA Scanning Axis: ⁇ /2 ⁇ Scanning Range (2 ⁇ ): 5.0 to 70.0° Measurement Mode: Continuous Reading Width: 0.05° Counting Time: 99.7 sec Automatic Variable Slit (Automatic-DS): 1 mm (irradiation width) Horizontal Diffusion Mask: 10 mm (irradiation width)
- X-ray is applied in the direction vertical to the axial direction of the cylindrical tube.
- Application of X-ray is so controlled that that X-ray could hit mainly on the other line above the surface of the stage, but not on the surface of the stage in the two lines kept in contact with both the cylindrical tubular membrane composite put on the stage and the plane parallel to the surface of the stage, in order to prevent noise and others as much as possible.
- the irradiation width is fixed to be 1 mm by the use of the automatic variable slit, and using Materials Data Inc.'s XRD analysis software, JADE 7.5.2 (Japanese version), the XRD pattern is obtained through variable slit ⁇ fixed slit conversion.
- the entire viewing field (25 ⁇ m ⁇ 18 ⁇ m) is scanned for X-ray quantitative analysis.
- KOFLOC's Model 8300 for N 2 gas with a maximum flow rate of 500 ml/min (as a value at 20° C. and 1 atmospheric pressure).
- Lintec's MM-2100M is used, which is for air with a maximum flow rate of 20 ml/min (as a value at 0° C. and 1 atmospheric pressure).
- the water vapor adsorption isotherm at 35° C. is measured.
- the zeolite membrane composite is previously cut into a suitable size that can be put in the measurement cell. While degassed in vacuum, the sample is heated and dried at 120° C. for 5 hours, and then used for the measurement.
- the air thermostat bath temperature is 50° C.
- the adsorption temperature is 35° C.
- the initial introduction pressure is 3 Torr (4.00 ⁇ 10 2 Pa)
- the saturation vapor pressure is 42.181 Torr (56.237 ⁇ 10 2 Pa)
- the equilibrium time is 500 seconds.
- the single-component gas permeation test is as follows, using an apparatus schematically shown in FIG. 1 .
- the sample gas to be used includes carbon dioxide (purity 99.9%, by Koatsu Gas Kogyo), methane (purity 99.999%, by Japan Fine Products), hydrogen (purity 99.99% or more, generated from HORIBA STEC's hydrogen generator OPGU-2200), nitrogen (purity 99.99%, by Toho Sanso Kogyo), helium (purity 99.99, by Japan Helium Center).
- the cylindrical zeolite membrane composite 1 is installed in a thermostat bath (not shown) while housed in the stainless-made pressure-tight container 2 .
- a temperature controller that enables temperature control of the sample gas is attached to the thermostat bath.
- One end of the cylindrical zeolite membrane composite 1 is sealed up with the columnar end pin 3 .
- the other end is connected to the connection 4 , and the other end of the connection 4 is connected to the pressure-tight container 2 .
- the inside of the cylindrical zeolite membrane composite 1 and the duct 11 for discharging the permeated gas 8 (permeated gas discharging duct) are connected via the connection 4 , and the duct 11 extends outside the pressure-tight container 2 .
- the pressure gauge 5 for measuring the pressure on the supply side of the sample gas is connected to any site to communicate with the pressure-tight container 2 . Every connection secures airtight connection.
- the single-component gas permeation test using the apparatus of FIG. 1 is as follows.
- a sample gas (supply gas 7 ) is supplied between the pressure-tight container 2 and the zeolite membrane composite 1 under a constant pressure, and the permeated gas 8 having passed through the zeolite membrane composite is measured with a flow rate meter (not shown) connected to the duct 11 .
- the single-component gas permeation test may also be carried out, using the apparatus schematically shown in FIG. 2 as follows.
- the cylindrical zeolite membrane composite 1 is installed in a thermostat bath (not shown) while housed in the stainless-made pressure-tight container 2 .
- a temperature controller that enables temperature control of the sample gas is attached to the thermostat bath.
- One end of the cylindrical zeolite membrane composite 1 is sealed up with the columnar end pin 3 .
- the other end is connected to the connection 4 , and the other end of the connection 4 is connected to the pressure-tight container 2 .
- the inside of the cylindrical zeolite membrane composite 1 and the duct 11 for discharging the permeated gas 8 are connected via the connection 4 , and the duct 11 extends outside the pressure-tight container 2 .
- the duct 12 for supplying a sweep gas 9 (sweep gas introducing duct) is inserted into the zeolite membrane composite 1 via the duct 11 .
- the pressure gauge 5 for measuring the pressure on the supply side of the sample gas and the back pressure valve 6 for controlling the pressure on the supply side are connected to any site to communicate with the pressure-tight container 2 . Every connection secures airtight connection.
- the single-component gas permeation test using the apparatus of FIG. 2 is as follows.
- a sample gas (supply gas 7 ) is supplied between the pressure-tight container 2 and the zeolite membrane composite 1 under a constant pressure, and the pressure on the supply side is made constant by the action of the back pressure valve 6 .
- the flow rate of the discharged gas 10 discharged through the duct 11 is measured.
- the system is dried at a temperature not lower than the measurement temperature, and degassed or purged with the supply gas to be used, then the sample temperature and the differential pressure between the side of the supply gas 7 and the side of the permeated gas 8 of the zeolite membrane composite 1 are kept constant, and after the permeated gas flow rate has become stabilized, the flow rate of the sample gas (permeated gas 8 ) having passed through the zeolite membrane composite 1 is measured, from which the gas permeance [mol ⁇ (m 2 ⁇ s ⁇ Pa) ⁇ 1 ] is calculated.
- the pressure in calculating the permeance is the pressure difference (differential pressure) between the supply side and the permeation side of the supply gas.
- Q 1 and Q 2 each indicate the permeation amount [mol ⁇ (m 2 ⁇ s) ⁇ 1 ] of the highly-permeative gas and the poorly-permeative gas, respectively; and P 1 and P 2 each indicate the pressure difference [Pa] between the supply side and the permeation side of the highly-permeative gas and the poorly-permeative gas, respectively.
- FIG. 3 shows an outline view of the apparatus used for vapor permeation.
- the sample liquid 13 to be separated is fed to the vaporizer 15 via the feeding pump 14 , at a predetermined flow rate, and is entirely vaporized by heating in the vaporizer 15 to be a gas to be separated.
- the gas to be separated is introduced into the zeolite membrane composite module 17 in the thermostat bath 16 , and is supplied in the space outside of the zeolite membrane composite.
- the zeolite membrane composite module 17 is constructed by housing the zeolite membrane composite in a housing.
- the inside area of the zeolite membrane composite is depressurized by the vacuum pump 21 so that the pressure difference between the inside area thereof and the gas to be separated could be about 1 atmospheric pressure.
- the internal pressure can be measured with a Pirani gauge though not shown. Owing to the pressure difference, the permeative substance, water in the gas to be separated passes through the zeolite membrane composite. The permeated substance is trapped by the permeated liquid collecting trap 19 , while the substance not trapped by the permeated liquid collecting trap 19 , if any, is trapped by the cold trap 20 . On the other hand, the component not permeated but left in the gas to be separated is liquefied and collected in the collecting trap 18 of liquid to be separated.
- An inorganic porous support-CHA-type zeolite membrane composite was produced through direct hydrothermal synthesis of a CHA-type aluminosilicate zeolite on an inorganic porous support, as described below.
- aluminium hydroxide containing 53.5% by mass of Al 2 O 3 , by Aldrich
- aqueous 1 mol/L-NaOH solution 8.0 g of aqueous 1 mol/L-KOH solution and 115 g of water, and dissolved by stirring to give a transparent solution.
- TMADAOH N,N,N-trimethyl-1-adamantanammonium hydroxide
- a porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was cut into a length of 80 mm, washed with an ultrasonic washing machine, dried and then used here.
- the grain size of the seed crystal was from 2 to 4 ⁇ m or so.
- the seed crystal was dispersed in an aqueous alkali solution of 0.33 mass % NaOH and 0.31% KOH, at about 1% by mass, and the above-mentioned support was dipped in the resulting dispersion for a predetermined period of time, and thereafter dried at 100° C. for 4 hours or more to thereby make the seed crystal adhere to the support. After drying the mass increase was 8.1 g/m 2 .
- the support to which the seed crystal had adhered was dipped in the aqueous reaction mixture put in a Teflon®-made inner cylinder (200 ml), in the vertical direction therein, and the autoclave was sealed up, and while kept static therein, this was heated at 160° C. for 48 hours under autogenous pressure. After a predetermined period of time, this was left cooled and the zeolite membrane composite was taken out of the reaction mixture, then washed and dried at 100° C. for 4 hours or more.
- the membrane composite was fired in air in an electric furnace at 500° C. for 5 hours. In this step, the heating speed and the cooling speed were both 0.5° C./min.
- the membrane thickness as obtained through SEM, was about 10 ⁇ m on average. After firing, one end of the cylindrical membrane composite was sealed up and the other end was connected to a vacuum line so that the inner pressure of the composite was reduced, and using the flow meter attached to the vacuum line, the air permeation amount was measured. The air permeation amount was 413 L/(m 2 ⁇ hr).
- FIG. 4 shows the XRD pattern of the formed zeolite membrane.
- “s” indicates the support-derived peak.
- FIG. 6 shows the XRD pattern of a powdery CHA-type zeolite (zeolite generally referred to as SSZ-13 in U.S. Pat. No. 4,544,538, this is hereinafter referred to as “SSZ-13”).
- SSZ-13 powdery CHA-type zeolite
- the molar ratio of SiO 2 /Al 2 O 3 in the zeolite membrane was 37.2, as measured through SEM-EDX.
- the water adsorption at a relative pressure of 0.8 was 2.2 times the water adsorption at a relative pressure of 0.2.
- the single-component gas permeation test was carried out.
- the zeolite membrane composite was processed as follows. CO 2 as the supply gas 7 was introduced between the pressure-tight container 2 and the zeolite membrane composite 1 at 140° C., and the pressure was kept at about 0.16 MPa. The inner pressure of the cylindrical zeolite membrane composite 1 was kept at 0.098 MPa (atmospheric pressure), and the membrane composite was dried for about 70 minutes. Carbon dioxide, methane, hydrogen, nitrogen and helium were thus tested as the sample gas.
- the pressure on the supply side was made 0.2 MPa, and the supply gas was changed to the sample gas.
- the differential pressure between the side of the supply gas 7 and the side of the permeated gas 8 of the zeolite membrane composite 1 was 0.1 MPa.
- the temperature was made 50° C., and after the temperature became stable, the supply gas was changed to the sample gas.
- the differential pressure between the side of the supply gas 7 and the side of the permeated gas 8 of the zeolite membrane composite 1 was 0.1 MPa.
- the permeance of each gas is shown in Table 1.
- the permeance of carbon dioxide at 50° C. is 1.6 ⁇ 10 ⁇ 6 and is a high value.
- the permeance of hydrogen is 7.3 ⁇ 10 ⁇ 7 and is also a high value.
- the data indicate that the gas permeance through the zeolite membrane composite obtained here is high.
- the ideal separation coefficient ⁇ of carbon dioxide and methane at 50° C. is 73 .
- the mass increase after adhesion of the seed crystal followed by drying was 9.9 g/m 2 .
- the mass of the CHA-type zeolite crystallized on the support which had been obtained from the difference between the mass of the zeolite membrane composite after fired and the mass of the support, was 122 g/m 2 .
- the membrane thickness as obtained through SEM, was about 8 ⁇ m on average.
- FIG. 5 shows the XRD pattern of the formed zeolite membrane.
- “*” indicates the support-derived peak.
- the molar ratio of SiO 2 /Al 2 O 3 in the zeolite membrane was 40.2, as measured through SEM-EDX.
- the water adsorption at a relative pressure of 0.8 was 2.2 times the water adsorption at a relative pressure of 0.2.
- the single-component gas permeation test was carried out.
- the permeance of each gas is shown in Table 2.
- the permeance of carbon dioxide at 50° C. is 2.4 ⁇ 10 ⁇ 6 and is a high value.
- the permeance of hydrogen is 1.0 ⁇ 10 ⁇ 6 and is also a high value.
- the data indicate that the gas permeance through the zeolite membrane composite obtained here is high.
- the ideal separation coefficient ⁇ of carbon dioxide and methane at 50° C. is 60 .
- An inorganic porous support-CHA-type zeolite membrane composite was produced through direct hydrothermal synthesis of a CHA-type zeolite on an inorganic porous support.
- TMADAOH N,N,N-trimethyl-1-adamantanammonium hydroxide
- SACHEM colloidal silica
- a mullite tube PM by Nikkato (outer diameter 12 mm, inner diameter 9 mm) was cut into a length of 80 mm, then the outer surface thereof was smoothed with water-resistant abrasive paper, washed with an ultrasonic washing machine and dried before use here. Prior to hydrothermal synthesis thereon, the support was processed as follows.
- the seed crystal was adhered to the support.
- the mass of the thus-adhering seed crystal was about 3 g/m 2 .
- Example 2 In the same manner as in Example 1, the support to which the seed crystal had been adhered was dipped in the reaction mixture put in a Teflon®-made inner cylinder, in the vertical direction therein, and the autoclave was sealed up, heated at 160° C. for 48 hours under autogenous pressure, then washed and dried.
- the mass of the CHA-type zeolite crystallized on the support which was obtained from the difference between the mass of the membrane composite after fired and the mass of the support, was 109 g/m 2 .
- the XRD peaks of the formed membrane did not show any specific intensity. From this, for example, it is assumed that the formed membrane would not have any orientation to the plane (1,0,0) and the plane (1,1,1) in rhombohedral setting.
- the molar ratio of SiO 2 /Al 2 O 3 did not give any accurate value.
- the detection limit of the molar ratio of SiO 2 /Al 2 O 3 is considered to be 100 or so, and accordingly, it is assumed that the molar ratio of SiO 2 /Al 2 O 3 in the zeolite membrane formed here would be more than 100.
- the water adsorption at a relative pressure of 0.8 as measured through water vapor adsorption isotherm analysis, was 1.9 times the water adsorption at a relative pressure of 0.2.
- the single-component gas permeation test was carried out.
- the permeance of each gas is shown in Table 3.
- the permeance of carbon dioxide at 50° C. is 7.8 ⁇ 10 ⁇ 7 and the permeance of hydrogen is 7.52 ⁇ 10 ⁇ 6 .
- the ideal separation coefficient ⁇ of carbon dioxide and methane at 50° C. is 6.1. It is considered that a dense membrane could not be formed without any orientation therein, and therefore the separation performance of the membrane would be low. In addition, it is considered that, since the membrane is not dense, gas could pass through the defects therein and the permeance through the membrane could be on a relatively high level.
- An inorganic porous support-CHA-type zeolite membrane composite obtained according to the same method as in Example 1 was silylated in the manner mentioned below.
- the zeolite membrane composite was put in a Teflon®-made inner cylinder, as dipped in 121.5 g of desalted water, 2.5 g of tetraethoxysilane and 13.5 g of 1 M sulfuric acid in the vertical direction therein, then the autoclave was sealed up, and heated at 100° C. for 20 hours under autogenous pressure. After a predetermined period of time, this was left cooled and the zeolite membrane composite was taken out and washed with desalted water.
- silylated zeolite membrane composite water was selectively separated through vapor permeation from a mixed solution of water/acetic acid (15/85 wt %).
- the inorganic porous support-CHA-type zeolite membrane composite was set in a thermostat bath at 130° C., and the mixed solution of water/acetic acid was fed into a vaporizer at a flow rate of 0.8 cm 3 /min, wholly vaporized therein and applied to the inorganic porous support-CHA-type zeolite membrane composite.
- the permeation result was as follows.
- the permeation flux was 1.4 kg/m 2 /hr; the separation coefficient was 900, and the water concentration in the permeated liquid was 99.38% by mass.
- the water permeance is 5.8 ⁇ 10 ⁇ 7 mol/m 2 /sec/Pa. From the result, it is understood that the zeolite membrane composite of the invention has a high water permeance and has a high separation coefficient.
- An inorganic porous support-CHA-type zeolite membrane composite was produced through direct hydrothermal synthesis of a CHA-type aluminosilicate zeolite on an inorganic porous support, as described below.
- TMADAOH N,N,N-trimethyl-1-adamantanammonium hydroxide
- a porous alumina tube (outer diameter 12 mm, inner diameter 9 mm) was cut into a length of 400 mm, and the powder formed during cutting was removed by applying compressed air thereto before use herein.
- the seed crystal was dispersed in desalted water at about 1% by mass, in which the support was dipped for a predetermined period of time, and then dried at 100° C. for 4 hours or more to thereby make the seed crystal adhere to the support.
- the adhering amount of the seed crystal after drying was 1.4 g/m 2 .
- Example 2 In the same manner as in Example 1, the support to which the seed crystal had been adhered was dipped in the reaction mixture put in a Teflon®-made inner cylinder, in the vertical direction therein, and the autoclave was sealed up, heated at 160° C. for 48 hours under autogenous pressure, then washed and dried.
- the mass of the CHA-type zeolite crystallized on the support which was obtained from the difference between the mass of the zeolite membrane composite after fired and the mass of the support, was 46 g/m 2 .
- FIG. 7 shows the XRD pattern of the formed zeolite membrane.
- “*” indicates the support-derived peak.
- the water adsorption at a relative pressure of 0.8 was 2.3 times the water adsorption at a relative pressure of 0.2.
- the single-component gas permeation test was carried out.
- the permeance of each gas is shown in Table 4.
- the permeance of carbon dioxide at 50° C. is 2.0 ⁇ 10 ⁇ 6 and is a high value.
- the permeance of hydrogen is 6.6 ⁇ 10 ⁇ 7 and is also a high value.
- the data indicate that the gas permeance through the zeolite membrane composite obtained here is high.
- the ideal separation coefficient ⁇ of carbon dioxide and methane at 50° C. is 126, which also indicates that the zeolite membrane composite obtained here has high separation performance.
- the mass increase after adhesion of the seed crystal followed by drying was 9.1 g/m 2 .
- the mass of the CHA-type zeolite crystallized on the support which had been obtained from the difference between the mass of the zeolite membrane composite after fired and the mass of the support, was 126 g/m 2 .
- the permeance of each gas is shown in Table 5.
- the permeance of carbon dioxide at 50° C. is 7.5 ⁇ 10 ⁇ 7
- the permeance of hydrogen is 1.0 ⁇ 10 ⁇ 6 .
- the ideal separation coefficient ⁇ of carbon dioxide and methane at 50° C. is 88 . It is considered that the separation performance of the membrane composite could be high in some degree owing to orientation to the plane (1,1,1), but on the other hand, the permeance through the membrane composite is low.
- the invention is usable in any industrial field, and is especially preferred for use in the field that requires separation of vapor mixture (gas), for example, in chemical industry plants, purification plants for natural gas, plants of generating biogas from garbage and the like, and for use in the field that requires separation of water from water-containing organic compounds and recovery of organic compounds, for example, in chemical industry plants, fermentation plants, factories for precision electronic components, cell production factories, etc.
- gas vapor mixture
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CN104144739A (zh) | 2014-11-12 |
CN104144739B (zh) | 2017-12-19 |
JP2018075564A (ja) | 2018-05-17 |
JP6107808B2 (ja) | 2017-04-05 |
CN108031300A (zh) | 2018-05-15 |
KR20140130444A (ko) | 2014-11-10 |
US20180339272A1 (en) | 2018-11-29 |
CN108031300B (zh) | 2022-02-08 |
JP6260684B2 (ja) | 2018-01-17 |
EP2818232A4 (en) | 2015-03-11 |
JP2017064716A (ja) | 2017-04-06 |
US12048904B2 (en) | 2024-07-30 |
EP2818232B1 (en) | 2018-08-22 |
JPWO2013125660A1 (ja) | 2015-07-30 |
KR102088147B1 (ko) | 2020-03-12 |
WO2013125660A1 (ja) | 2013-08-29 |
EP2818232A1 (en) | 2014-12-31 |
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