JP2009066462A - Method for preparing composite membrane - Google Patents
Method for preparing composite membrane Download PDFInfo
- Publication number
- JP2009066462A JP2009066462A JP2005377758A JP2005377758A JP2009066462A JP 2009066462 A JP2009066462 A JP 2009066462A JP 2005377758 A JP2005377758 A JP 2005377758A JP 2005377758 A JP2005377758 A JP 2005377758A JP 2009066462 A JP2009066462 A JP 2009066462A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- porous support
- composite membrane
- membrane
- binder
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000010457 zeolite Substances 0.000 claims abstract description 137
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 134
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 134
- 238000000926 separation method Methods 0.000 claims abstract description 64
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 239000013081 microcrystal Substances 0.000 claims abstract description 35
- 238000005373 pervaporation Methods 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 229910001868 water Inorganic materials 0.000 claims description 41
- 229920000620 organic polymer Polymers 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 239000011147 inorganic material Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000004907 flux Effects 0.000 abstract description 21
- 239000007788 liquid Substances 0.000 abstract description 13
- 229920002521 macromolecule Polymers 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 52
- 239000006185 dispersion Substances 0.000 description 15
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 14
- 229910052753 mercury Inorganic materials 0.000 description 14
- 239000011148 porous material Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- -1 polyethylene Polymers 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 235000019353 potassium silicate Nutrition 0.000 description 9
- 239000012510 hollow fiber Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004695 Polyether sulfone Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920006393 polyether sulfone Polymers 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 108010063955 thrombin receptor peptide (42-47) Proteins 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- HHAPGMVKBLELOE-UHFFFAOYSA-N 2-(2-methylpropoxy)ethanol Chemical compound CC(C)COCCO HHAPGMVKBLELOE-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride 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
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 235000012239 silicon dioxide Nutrition 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
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
- B01D61/3621—Pervaporation comprising multiple pervaporation steps
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
-
- 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
- B01D69/1216—Three or more layers
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、分子ふるい機能を有するゼオライトの結晶からなる層が、中空円筒状の多孔質支持体上に形成された複合膜の製造方法、該製造方法によって得られた複合膜および該複合膜を用いて液体、気体、またはそれらの混合物から特定の成分をパーベーパレーション法又はベーパーパーミエーション法により分離する物質分離方法に関する。 The present invention relates to a method for producing a composite membrane in which a layer of zeolite crystals having a molecular sieving function is formed on a hollow cylindrical porous support, a composite membrane obtained by the production method, and the composite membrane. The present invention relates to a material separation method for separating a specific component from a liquid, a gas, or a mixture thereof by a pervaporation method or a vapor permeation method.
水および有機物が均一に混合した溶液から、水または有機物を選択的に分離する方法としては、蒸留による方法が広く使われている。エタノール、イソプロパノール、ブタノール等は、水との混合により、一定濃度以上では共沸状態となるために、通常の蒸留法で分離することができず、ベンゼンのような有害なエントレーナーを使用した共沸蒸留法を用いる必要がある。 As a method for selectively separating water or organic substances from a solution in which water and organic substances are uniformly mixed, a distillation method is widely used. Ethanol, isopropanol, butanol, etc. become azeotropic at a certain concentration or higher by mixing with water, so they cannot be separated by a normal distillation method, and they are shared using a harmful entrainer such as benzene. It is necessary to use boiling distillation.
共沸蒸留法は、このように有害な第３成分が必要となることに加えて、エネルギーコストも高くなるため、近年これに代わる分離方法としてパーベーパレーション又はベーパーパーミエーションによる分離方法が注目されており、ゼオライト膜を用いた分離膜が高い特性を示すことが知られている。
特に、多孔質支持体上に形成した親水性のＡ型ゼオライトの膜を用いたパーベーパレーションによる脱水では、温度７５℃、エタノール９０重量％の水溶液において、透過流束Ｑ＝２．１５ｋｇ／ｍ２ｈ、分離係数αが１００００以上という、極めて高い分離性能が得られている（特許文献１参照）。
In addition to the need for such a harmful third component, the azeotropic distillation method also increases the energy cost. Therefore, in recent years, a separation method using pervaporation or vapor permeation has attracted attention as an alternative separation method. It is known that a separation membrane using a zeolite membrane exhibits high characteristics.
In particular, in dehydration by pervaporation using a hydrophilic A-type zeolite membrane formed on a porous support, the permeation flux Q = 2.15 kg / m in an aqueous solution at a temperature of 75 ° C. and 90% by weight of ethanol. An extremely high separation performance of 2 h and a separation coefficient α of 10,000 or more is obtained (see Patent Document 1).
多孔質支持体上にゼオライト結晶からなる層を形成する製膜方法としては、多孔質支持体にゼオライトの種結晶を付与してから水熱合成により結晶成長させる方法(例えば、非特許文献１参照)、直接水熱合成によって結晶を成長させる方法(特許文献２)、ゼオライトの原料となるゲルを多孔質支持体上に塗布した後、スチーム処理によって製膜するドライゲル法(特許文献３)、等が挙げられる。これらの製膜法の中でも種結晶を支持体に付与してから水熱合成する、いわゆる種結晶法は欠陥のない緻密なゼオライト結晶による膜を製膜する方法として、実用上特に有効である（特許文献１及び４）。 As a film forming method for forming a layer composed of zeolite crystals on a porous support, a method of crystal growth by hydrothermal synthesis after applying zeolite seed crystals to the porous support (see, for example, Non-Patent Document 1) ), A method of growing crystals by direct hydrothermal synthesis (Patent Document 2), a dry gel method (Patent Document 3) in which a gel as a raw material of zeolite is applied on a porous support and then formed into a film by steam treatment, etc. Is mentioned. Among these film-forming methods, the so-called seed crystal method, in which a seed crystal is applied to a support and then hydrothermally synthesized, is particularly effective in practice as a method for forming a film of dense zeolite crystals having no defects ( Patent Documents 1 and 4).
しかしながら、種結晶法においては、種となる結晶を支持体上に均一に適切な量を付与することが重要な要素となり、種の支持体表面での分散状態が不均一であると欠陥のないゼオライト結晶膜が得られず、高い分離性能が得られない。このため、同様の種結晶を用いた方法で製膜したＡ型ゼオライトであっても、特許文献１の脱水性能を再現しない報告が多くなされている(例えば、非特許文献２−４参照)。 However, in the seed crystal method, it is an important factor to uniformly apply an appropriate amount of the seed crystal on the support, and there is no defect if the dispersion state of the seed support surface is uneven. A zeolite crystal membrane cannot be obtained, and high separation performance cannot be obtained. For this reason, even if it is A type zeolite formed into a film by the method using the same seed crystal, many reports which do not reproduce the dehydration performance of patent document 1 are made (for example, refer nonpatent literature 2-4).
また工業的に実用化されている種結晶による製膜法であっても、種結晶の支持体表面への付与状態を制御することは容易ではない。例えば特許文献１では支持体に種を擦り付ける方法を用い、特許文献４では支持体を種分散水溶液に浸漬することにより、特許文献５では種分散水溶液を多孔質支持体表面に刷毛塗りすることにより、それぞれ種結晶を付与させている。しかしながらこれらの方法を用いても、種の支持体への付与状態の制御は完全ではなく、更に種結晶はファンデルワールス力やゼータ電位のような凝集力によって支持体表面に固定されているため（非特許文献５）、振動や接触による部分的な脱離を完全に抑制することは困難であった。このため、水熱合成によって得られた膜に欠陥が存在したり、また種量が過剰な部分には非結晶成分が混在し分離機能が十分に発現されないなど、不良品の発生を十分に押さえることは極めて難しかった。 Moreover, even if it is the film forming method by the seed crystal currently industrially put into practical use, it is not easy to control the application state of the seed crystal to the support surface. For example, Patent Document 1 uses a method of rubbing seeds on a support, Patent Document 4 immerses the support in a seed dispersion aqueous solution, and Patent Document 5 brushes the seed dispersion aqueous solution on the surface of the porous support. , Each of which is provided with a seed crystal. However, even if these methods are used, the control of the state of application of the seed to the support is not complete, and the seed crystal is fixed to the support surface by a cohesive force such as van der Waals force or zeta potential. (Non-Patent Document 5) It was difficult to completely suppress partial detachment due to vibration or contact. For this reason, there are defects in the membrane obtained by hydrothermal synthesis, and the generation of defective products is sufficiently suppressed, such as the presence of non-crystalline components in the excessive amount of seeds and the separation function is not fully expressed. It was extremely difficult.
種結晶を支持体表面に固定するために、結合剤を用いてゼオライト微結晶を多孔質支持体表面に担持させる方法として、水ガラスまたはシリカゾルを結合剤として用いる方法が開示されている（特許文献６）。しかしながら、水ガラスまたはシリカゾルは塗膜性が低いため、ゼオライト微結晶を多孔質支持体表面に均一かつ強固に担持することは容易ではない。更に、水ガラスまたはシリカゾルの溶媒は水あるいは多量の水を含む有機溶媒に限定されるため、これらを結合剤としてゼオライト微結晶を担持できる多孔質支持体は、アルミナのような親水性の高い材料よりなる支持体に限定される。
このように、支持体表面に欠陥や非結晶成分の混在がなく、均一に製膜されたゼオライト結晶膜を、高い収率で得ることはこれまで容易ではなかった。
In order to fix the seed crystal on the surface of the support, a method using water glass or silica sol as a binder is disclosed as a method for supporting zeolite microcrystals on the surface of a porous support using a binder (Patent Document). 6). However, since water glass or silica sol has low coating properties, it is not easy to support zeolite fine crystals uniformly and firmly on the surface of the porous support. Furthermore, since the solvent of water glass or silica sol is limited to water or an organic solvent containing a large amount of water, a porous support capable of supporting zeolite microcrystals using these as a binder is a highly hydrophilic material such as alumina. It is limited to the support which consists of.
As described above, it has not been easy to obtain a zeolite crystal membrane with a high yield without uniform defects and non-crystalline components on the surface of the support.
本発明は、ゼオライト結晶膜からなる、高分離係数および高透過流束を有する分離膜、特に、パーベーパレーション法又はベーパーパーミエーション法により、共沸混合物から所望の成分を分離するのに好適な複合膜及びそれを高収率で製造する方法を提供することを目的とする。
また、本発明は、この複合膜を用いて混合液体、特に、共沸混合物から所望の成分を分離する方法を提供することを目的とする。
The present invention is a separation membrane having a high separation factor and a high permeation flux composed of a zeolite crystal membrane, and particularly suitable for separating a desired component from an azeotrope by a pervaporation method or a vapor permeation method. It is an object of the present invention to provide a composite membrane and a method for producing it with high yield.
Another object of the present invention is to provide a method for separating a desired component from a mixed liquid, particularly an azeotropic mixture, using the composite membrane.
従来の種結晶法により支持体上にゼオライト結晶膜を形成する場合、擦りつけあるいは浸漬などの方法により、支持体表面に種を付与し、その後に水熱合成によりゼオライト結晶膜を製膜する。この際、種の付与が不均一、付与量が不適切、また付与後の種の脱離などがあると欠陥が生じやすく、この結果、分離性能の低下や製膜収率の低下が生じると考えられる。
これに対し、本発明者らは、有機高分子を結合剤として中空円筒状の多孔質支持体表面に種結晶となるゼオライト微結晶を付与した後、水熱合成を施すことにより、極めて高い収率で、しかも簡便に、分離性能の高いゼオライト結晶膜を有する複合膜が得られることを見出し、本発明を完成させるに至った。
すなわち、本発明は以下のとおりである。
When a zeolite crystal film is formed on a support by a conventional seed crystal method, seeds are applied to the support surface by a method such as rubbing or dipping, and then a zeolite crystal film is formed by hydrothermal synthesis. At this time, if the seed application is uneven, the application amount is inappropriate, and there is a detachment of the seed after application, defects are likely to occur, resulting in a decrease in separation performance and a decrease in film formation yield. Conceivable.
On the other hand, the present inventors applied a hydrothermal synthesis after applying zeolite microcrystals as seed crystals on the surface of a hollow cylindrical porous support using an organic polymer as a binder, and thereby achieving an extremely high yield. The present inventors have found that a composite membrane having a zeolite crystal membrane with high separation performance can be obtained easily and easily.
That is, the present invention is as follows.
（１）有機高分子を結合剤として、表面にゼオライト微結晶を付与した多孔質支持体を、ゼオライトの原料を含む合成液に接触させ、水熱合成を施すことにより、多孔質支持体の内表面あるいは外表面の少なくとも一方の表面にゼオライト結晶膜を形成することを特徴とする複合膜の製造方法。
（２）多孔質支持体がセラミックスまたは金属から選ばれる無機物からなることを特徴とする、上記（１）記載の複合膜の製造方法。
（３）多孔質支持体が有機高分子からなることを特徴とする、上記（１）記載の複合膜の製造方法。
（４）ゼオライト結晶膜がＡ型、Ｘ型、Ｙ型、Ｔ型、Ｌ型、ＺＳＭ類、ソーダライト類、モルデナイト類およびシリカライト類から選ばれた一種からなることを特徴とする上記（１）記載の複合膜の製造方法。
（５）上記（１）〜（４）に記載の製造方法によって得られた複合膜。
（６）ゼオライト結晶膜が親水性ゼオライトからなることを特徴とする上記（５）記載の複合膜。
（７）ゼオライト結晶膜が疎水性ゼオライトからなることを特徴とする上記（５）記載の複合膜。
（８）上記（５）〜（７）に記載の複合膜を用いてパーベーパレーション法又はベーパーパーミエーション法によって２種以上の成分からなる混合溶液又は混合気体から少なくとも１種の成分を分離する物質分離方法。
（９）水と有機物からなる混合溶液から少なくとも１種の成分を分離することを特徴とする上記（８）記載の物質分離方法。
（１０）２種以上の有機物からなる混合溶液から少なくとも１種の成分を分離することを特徴とする上記（８）記載の物質分離方法。
(1) A porous support having an organic polymer as a binder and zeolite microcrystals on the surface is brought into contact with a synthesis liquid containing a zeolite raw material, and hydrothermal synthesis is performed. A method for producing a composite membrane, comprising forming a zeolite crystal membrane on at least one of a surface and an outer surface.
(2) The method for producing a composite film as described in (1) above, wherein the porous support is made of an inorganic material selected from ceramics and metals.
(3) The method for producing a composite membrane as described in (1) above, wherein the porous support is composed of an organic polymer.
(4) The above-mentioned (1) characterized in that the zeolite crystal film is made of one selected from A-type, X-type, Y-type, T-type, L-type, ZSMs, sodalites, mordenites and silicalites. ) Described above.
(5) A composite membrane obtained by the production method according to the above (1) to (4).
(6) The composite membrane according to (5) above, wherein the zeolite crystal membrane is made of hydrophilic zeolite.
(7) The composite membrane as described in (5) above, wherein the zeolite crystal membrane comprises a hydrophobic zeolite.
(8) Using the composite membrane described in (5) to (7) above, at least one component is separated from a mixed solution or mixed gas composed of two or more components by a pervaporation method or a vapor permeation method. Substance separation method.
(9) The substance separation method as described in (8) above, wherein at least one component is separated from a mixed solution comprising water and an organic substance.
(10) The method for separating substances according to (8) above, wherein at least one component is separated from a mixed solution composed of two or more organic substances.
本発明の複合膜の製造方法によると、均一で欠陥や非結晶成分が極めて少ないゼオライト結晶膜を高収率で製造することができる。また、本発明の複合膜の製造方法によって得られた複合膜は、透過流束、分離係数が高い上に、ゼオライト結晶膜と多孔質支持体との密着性にも優れる。これを用いると、多分野で、かつ、広範囲の用途において、分離係数および透過流束が高く、コンパクトで処理能力が高い分離用モジュールが可能となる。その結果、蒸留法に代わる、反応プロセス等から得られる混合物の経済的な分離が可能である。
特に、本発明の複合膜は、水と有機化合物とからなる共沸混合物からパーベーパレーション法によって選択的に所望の成分を分離するのに好適である。
According to the method for producing a composite membrane of the present invention, a zeolite crystal membrane that is uniform and has extremely few defects and amorphous components can be produced in a high yield. In addition, the composite membrane obtained by the method for producing a composite membrane of the present invention has a high permeation flux and separation factor, and is excellent in adhesion between the zeolite crystal membrane and the porous support. When this is used, a separation module having a high separation factor and a high permeation flux, a compact size and a high processing capacity can be used in various fields and in a wide range of applications. As a result, it is possible to economically separate the mixture obtained from the reaction process or the like instead of the distillation method.
In particular, the composite membrane of the present invention is suitable for selectively separating desired components from an azeotropic mixture composed of water and an organic compound by a pervaporation method.
以下に本発明を詳細に説明する。
本発明の複合膜の製造方法によって得られる複合膜は、有機高分子を結合剤として、表面にゼオライト微結晶を付与した多孔質支持体の、内表面あるいは外表面の少なくとも一方の表面に、ゼオライトの結晶膜が形成された構造である。
ゼオライト結晶膜は、多孔質支持体表面に有機高分子を結合剤としてゼオライト結晶の微粒子を付与したものを、ゼオライト結晶膜の原料となる合成液に接触させ、水熱合成を施すことにより形成する。ゼオライト微結晶が有機高分子を結合剤として多孔質支持体表面に均一かつ強固に担持されていることにより、欠陥のないゼオライト結晶膜の形成が容易かつ高い収率で行われるのみならず、得られたゼオライト結晶膜を用いてパーベーパレーション法又はベーパーパーミエーション法による分離を行った際の分離係数並びに透過流束も向上する。
The present invention is described in detail below.
The composite membrane obtained by the method for producing a composite membrane of the present invention comprises an organic polymer as a binder and a zeolite on at least one of the inner surface and the outer surface of a porous support provided with zeolite crystallites on the surface. The crystal film is formed.
Zeolite crystal membranes are formed by contacting the surface of a porous support with an organic polymer as a binder and fine particles of zeolite crystals in contact with a synthesis solution used as a raw material for the zeolite crystal membrane, and hydrothermal synthesis. . Zeolite microcrystals are supported uniformly and firmly on the surface of the porous support using organic polymer as a binder, so that the formation of a defect-free zeolite crystal film can be performed easily and in high yield. The separation coefficient and permeation flux when the permeation method or the vapor permeation method is used for the obtained zeolite crystal membrane are also improved.
多孔質支持体の表面に担持させるゼオライト微結晶の寸法は、多孔質支持体表面での均一分散性、接着強度の観点から、０．０１μｍ以上、１０μｍ以下であることが好ましく、より好ましくは０．０１μｍ以上、５μｍ以下である。
ゼオライト微結晶としては、Ａ型、Ｘ型、Ｙ型、Ｔ型、Ｌ型、ＺＳＭ類、ソーダライト類、モルデナイト類、シリカライト類等を用いることができるが、その表面に形成するゼオライト結晶膜と同じ種類のゼオライトを選択する。
欠陥のないゼオライト結晶膜を形成するという観点から、ゼオライト結晶膜が形成される多孔質支持体の表面には、水熱合成を施す前の状態で、表面の１％以上の面積をゼオライト微結晶が占めていることが望ましい。ゼオライト微結晶が表面を占める面積の割合に上限はない。
The size of the zeolite crystallites supported on the surface of the porous support is preferably 0.01 μm or more and 10 μm or less, more preferably 0, from the viewpoint of uniform dispersibility and adhesive strength on the surface of the porous support. .01 μm or more and 5 μm or less.
As zeolite fine crystals, A-type, X-type, Y-type, T-type, L-type, ZSMs, sodalites, mordenites, silicalites, etc. can be used, but the zeolite crystal film formed on the surface thereof Select the same type of zeolite.
From the viewpoint of forming a defect-free zeolite crystal film, the surface of the porous support on which the zeolite crystal film is formed has a surface area of 1% or more of the surface of the microporous zeolite before hydrothermal synthesis. Is desirable. There is no upper limit to the ratio of the area occupied by the zeolite microcrystals.
本発明に用いられる多孔質支持体は、中空円筒状即ち、中空糸状、管状であり、さらにレンコン状、ハニカム状の形状のものも含まれる。多孔質支持体の大きさは特に限定されないが、例えば中空糸状並びに管状の場合、外径は０．５ｍｍから１０ｃｍの範囲が好ましく、壁の厚さは、０．０５ｍｍから２ｃｍの範囲が好ましい。 The porous support used in the present invention has a hollow cylindrical shape, that is, a hollow fiber shape and a tubular shape, and also includes a lotus root shape and a honeycomb shape. The size of the porous support is not particularly limited. For example, in the case of a hollow fiber shape and a tubular shape, the outer diameter is preferably in the range of 0.5 mm to 10 cm, and the wall thickness is preferably in the range of 0.05 mm to 2 cm.
本発明の複合膜に用いられる多孔質支持体の空孔率は、複合膜の透過流束の観点から１０％以上、多孔質支持体の材質にもよるが、機械的強度の観点から、９９％以下が好ましい。より好ましくは３０％以上９５％以下、最も好ましくは４０％以上９０％以下である。
多孔質支持体の細孔径は、パーベーパレーション又はベーパーパーミエーションによって分離する分子の移動が阻害され、透過流束が減少しない大きさが必要である。具体的には、平均細孔径は、透過流束の観点から１０ｎｍ以上、ゼオライト結晶膜の均一性の観点から５μｍ以下であることが好ましい。より好ましくは５０ｎｍ以上、２μｍ以下である。
The porosity of the porous support used in the composite membrane of the present invention is 10% or more from the viewpoint of the permeation flux of the composite membrane. Depending on the material of the porous support, it is 99 from the viewpoint of mechanical strength. % Or less is preferable. More preferably, it is 30% or more and 95% or less, and most preferably 40% or more and 90% or less.
The pore size of the porous support needs to be large enough to prevent the permeation flux from decreasing because the movement of molecules separated by pervaporation or vapor permeation is inhibited. Specifically, the average pore diameter is preferably 10 nm or more from the viewpoint of permeation flux and 5 μm or less from the viewpoint of the uniformity of the zeolite crystal membrane. More preferably, it is 50 nm or more and 2 μm or less.
多孔質支持体の原料は、アルミナ、ムライト、シリカ、ジルコニア、ベントナイト、コージェライト、シリコンナイトライド、シリコンカーバイド、ガラスなどのセラミックス、ステンレス、アルミニウム、などの金属といった無機物、ポリスルホン、ポリエーテルスルホン、ポリビニリデンフロライド、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリエステル、ポリカーボネート、ポリエーテルケトン、シリコーン、セルロース及びその誘導体、更にこれらのポリマーを含む共重合体などの有機高分子、が用いられる。 The raw material of the porous support is alumina, mullite, silica, zirconia, bentonite, cordierite, silicon nitride, silicon carbide, ceramics such as glass, inorganic materials such as metals such as stainless steel, aluminum, polysulfone, polyethersulfone, poly Vinylidene fluoride, polyethylene, polypropylene, polyamide, polyimide, polyester, polycarbonate, polyetherketone, silicone, cellulose and derivatives thereof, and organic polymers such as copolymers containing these polymers are used.
これらのうち円筒状の多孔体を形成でき、細孔径、空孔率の制御が容易な原料としては、アルミナ、ムライト、ベントナイト、コージェライトなどのセラミックス、ポリスルホン、ポリエーテルスルホン、ポリビニリデンフロライド、ポリエチレン、ポリアクリロニトリルなどの有機高分子、が好ましい。また、有機高分子とセラミックスの複合物として得られる多孔質支持体も好ましく用いることができる。更に結晶膜を形成するゼオライトと同じ種類のゼオライト微結晶と有機高分子とを混合して得られる、複合多孔体も好ましい支持体として用いることができる。 Among these, cylindrical porous bodies can be formed, and raw materials that can easily control the pore diameter and porosity include ceramics such as alumina, mullite, bentonite, cordierite, polysulfone, polyethersulfone, polyvinylidene fluoride, Organic polymers such as polyethylene and polyacrylonitrile are preferred. A porous support obtained as a composite of an organic polymer and a ceramic can also be preferably used. Furthermore, a composite porous body obtained by mixing a zeolite fine crystal of the same kind as the zeolite forming the crystal film and an organic polymer can also be used as a preferred support.
多孔質支持体として無機材料を用いる場合、表面にゼオライト微結晶を担持させる、結合剤となる有機高分子は、広い範囲の材質が選択できる。代表的なものとしては、ポリビニルブチラール、ポリエチレングリコール、ポリプロピレングリコール、ポリスチレン、ポリアクリル酸エステル、ポリメチルメタクリレート、ポリビニルアルコール、ポリスルホン、ポリエーテルスルホン、ポリビニリデンフロライド、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリエステル、ポリカーボネート、ポリエーテルケトン、セルロース及びその誘導体、更にこれらのポリマーを含む共重合体が挙げられる。これらのポリマーの中でも特に一般的な溶剤に溶解しやすく、塗膜性が良好なものとして、ポリビニルブチラール、ポリエチレングリコール、ポリプロピレングリコール、ポリスチレン、ポリアクリル酸エステル、ポリメチルメタクリレート、ポリビニルアルコールが好ましい。
多孔質支持体として無機材料を用いる場合、無機物は有機溶媒によって溶解されることはないので、結合剤として用いる有機高分子は上記の任意の有機高分子を、溶媒はその有機高分子を溶解させるものであれば任意の溶媒を選択することができる。
When an inorganic material is used as the porous support, a wide range of materials can be selected for the organic polymer serving as a binder that supports zeolite fine crystals on the surface. Typical examples include polyvinyl butyral, polyethylene glycol, polypropylene glycol, polystyrene, polyacrylic ester, polymethyl methacrylate, polyvinyl alcohol, polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, polypropylene, polyamide, polyimide, polyester. , Polycarbonate, polyetherketone, cellulose and derivatives thereof, and copolymers containing these polymers. Among these polymers, polyvinyl butyral, polyethylene glycol, polypropylene glycol, polystyrene, polyacrylic acid ester, polymethyl methacrylate, and polyvinyl alcohol are preferable because they are particularly easily dissolved in common solvents and have good coating properties.
When an inorganic material is used as the porous support, since the inorganic substance is not dissolved by the organic solvent, the organic polymer used as the binder dissolves any of the above organic polymers, and the solvent dissolves the organic polymer. Any solvent can be selected as long as it is one.
一方、多孔質支持体として有機高分子を用いる場合は、結合剤とその溶媒の選択が重要となる。即ち、結合剤である有機高分子の溶媒が、支持体である有機高分子を溶解させないような、支持体、結合剤、溶剤を選択する必要がある。従って、多孔質支持体としてポリスルホン、ポリエーテルスルホン、ポリビニリデンフロライド、ポリエチレン、ポリアクリロニトリルなどの有機高分子よりなるものを用いる場合、結合剤として用いることができる有機高分子は、ポリビニルブチラール、ポリエチレングリコール、ポリプロピレングリコールが好ましい。また、これらの溶媒としては、メタノール、エタノール、2-プロパノール、1-ブタノール、メトキシプロパノール、エチレングリコール、1-5ペンタンジオール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルテーテル、エチレングリコールジメチルエーテル、２-ブトキシエタノール、エチレングリコールモノイソブチルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノヘキシルエーテルが好ましく用いられる。さらに、結合剤有機高分子としてポリビニルアルコール、その溶剤として水、あるいはアルカリ性水溶液の組み合わせも、支持体である有機高分子を溶解しない組み合わせとして用いられる。 On the other hand, when an organic polymer is used as the porous support, the selection of the binder and its solvent is important. That is, it is necessary to select a support, a binder, and a solvent so that the organic polymer solvent as the binder does not dissolve the organic polymer as the support. Accordingly, when a porous support made of an organic polymer such as polysulfone, polyethersulfone, polyvinylidene fluoride, polyethylene, or polyacrylonitrile is used, the organic polymer that can be used as a binder is polyvinyl butyral, polyethylene, or the like. Glycol and polypropylene glycol are preferred. These solvents include methanol, ethanol, 2-propanol, 1-butanol, methoxypropanol, ethylene glycol, 1-5 pentanediol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, 2-butoxy. Ethanol, ethylene glycol monoisobutyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monohexyl ether are preferably used. Furthermore, a combination of polyvinyl alcohol as the binder organic polymer, water as the solvent, or an alkaline aqueous solution is also used as a combination that does not dissolve the organic polymer as the support.
有機高分子を用いて多孔質支持体表面にゼオライト微結晶を担持させる方法としては、有機高分子とその溶媒との溶液にゼオライト微結晶を分散させた分散溶液を調合し、これに多孔質支持体を浸漬した後に引上げ、乾燥することによって行うことが好ましい。また、分散溶液を刷毛などによって多孔質支持体表面に直接塗布、乾燥することによって、ゼオライト微結晶を支持体表面に担持させることもできる。 As a method for supporting zeolite microcrystals on the surface of a porous support using an organic polymer, a dispersion solution in which zeolite microcrystals are dispersed in a solution of an organic polymer and its solvent is prepared, and this is supported by a porous support. It is preferable to carry out by pulling up after the body is immersed and drying. Alternatively, the zeolite microcrystals can be supported on the surface of the support by directly applying the dispersion solution to the surface of the porous support with a brush or the like and drying.
有機高分子を結合剤として用いることにより、ゼオライト微結晶は多孔質支持体表面に強固に固定されるため、凝集力によって固定する従来の担持法に比べて、種結晶を担持してから水熱合成を施すまでの支持体の取り扱いが極めて容易になる。即ち、凝集力によって種を担持した場合には、水熱合成を施す前に表面に触れたり、衝撃を加えたりすると種は部分的に剥離しやすく、また合成液内の対流などによって種となるゼオライト微結晶が支持体から脱離することもあるため、水熱合成後に得られる結晶膜の緻密性が低下する傾向がある。 By using an organic polymer as a binder, zeolite microcrystals are firmly fixed to the surface of the porous support. Therefore, compared to the conventional support method in which the zeolite crystal is fixed by cohesion, hydrothermal Handling of the support until synthesis is performed becomes extremely easy. That is, when seeds are supported by cohesive force, the seeds are easily detached when touching the surface or applying an impact prior to hydrothermal synthesis, and become seeds by convection in the synthesis solution. Since zeolite microcrystals may be detached from the support, the denseness of the crystal film obtained after hydrothermal synthesis tends to decrease.
これに対して、有機高分子を結合剤として用いることにより、水熱合成前及び水熱合成中の種の脱離を抑制するため、緻密な結晶膜の成膜が容易となり、分離性能の高いゼオライト結晶膜が高収率で得られる。
結合剤として水ガラス、シリカゾルといった無機結合剤を用いる場合に対して、本発明の有機高分子を結合剤として用いる場合は、結合剤の溶媒として有機溶剤を用いることができるため、親水性の支持体だけでなく、ポリスルホン、ポリビニリデンフロライド、ポリエチレンのような疎水性の高い支持体にも容易にしかも均一に種を担持させることができる。
In contrast, the use of an organic polymer as a binder suppresses the elimination of species before and during hydrothermal synthesis, thereby facilitating the formation of a dense crystal film and high separation performance. A zeolite crystal membrane is obtained in high yield.
When the organic polymer of the present invention is used as a binder in contrast to the case where an inorganic binder such as water glass or silica sol is used as a binder, an organic solvent can be used as a solvent for the binder, so that hydrophilic support is provided. The seeds can be easily and uniformly supported not only on the body but also on a highly hydrophobic support such as polysulfone, polyvinylidene fluoride, and polyethylene.
本発明の複合膜は、多孔質支持体の表面にゼオライト結晶からなる層が形成されている。ゼオライト結晶は、粒界を形成して緻密にパッキングして、中空円筒状の多孔質支持体表面に層を形成している。
ゼオライトとしては、各種親水性ゼオライト、疎水性ゼオライトを用いることができる。親水性ゼオライトとしては、Ａ型、Ｘ型、Ｙ型、Ｔ型、Ｌ型が、疎水性ゼオライトとしては、ＺＳＭ類、ソーダライト類、モルデナイト類、シリカライト類がそれぞれ挙げられる。また、これらがアルカリ金属またはアルカリ土類金属を含む場合、それを他の金属イオンで置き換えた各種ゼオライト等も用いることができる。
In the composite membrane of the present invention, a layer made of zeolite crystals is formed on the surface of the porous support. Zeolite crystals form grain boundaries and are packed densely to form a layer on the surface of a hollow cylindrical porous support.
As the zeolite, various hydrophilic zeolites and hydrophobic zeolites can be used. Examples of the hydrophilic zeolite include A type, X type, Y type, T type, and L type, and examples of the hydrophobic zeolite include ZSMs, sodalites, mordenites, and silicalites. Moreover, when these contain an alkali metal or alkaline-earth metal, the various zeolite etc. which replaced it with the other metal ion can also be used.
ゼオライト結晶膜を形成する結晶の寸法は、分離性能と透過流束がともに低下するのを防ぐ上で、０．０１μｍから１０μｍの範囲にあることが好ましく、より好ましくは０．１μｍから５μｍである。
ゼオライト層の厚みは、分離性能の観点から０．１μｍ以上、透過流束の観点から５０μｍ以下であることが好ましく、より好ましくは０．５μｍから３０μｍである。
本発明の複合膜におけるゼオライト結晶膜は、本発明の多孔質支持体を、ゼオライトの原料を含む合成液に接触させ、適当な条件で水熱合成を施すことにより形成される。
The size of the crystals forming the zeolite crystal membrane is preferably in the range of 0.01 μm to 10 μm, more preferably 0.1 μm to 5 μm, in order to prevent both the separation performance and the permeation flux from decreasing. .
The thickness of the zeolite layer is preferably 0.1 μm or more from the viewpoint of separation performance and 50 μm or less from the viewpoint of permeation flux, and more preferably 0.5 μm to 30 μm.
The zeolite crystal membrane in the composite membrane of the present invention is formed by bringing the porous support of the present invention into contact with a synthesis solution containing a zeolite raw material and hydrothermal synthesis under appropriate conditions.
ゼオライトの原料となるシリカ成分としては、ケイ酸ナトリウム、水ガラス、コロイダルシリカ、二酸化珪素、アルコキシシランの加水分解物等を用いることができる。ゼオライトの原料となるアルミナ成分としては、アルミン酸ナトリウム、水酸化アルミニウム、硝酸アルミニウム、塩化アルミニウム、ベーマイト等を用いることができる。また、水熱合成時のアルカリ性を発現しかつ、ゼオライトを形成するナトリウムの原料としては、水酸化ナトリウムが用いられる。必要に応じてカルシウム酸化物成分として、水酸化カルシウム、酸化カルシウム、硝酸カルシウム、塩化カルシウム等、マグネシウム酸化物成分として、水酸化マグネシウム、酸化マグネシウム、硝酸マグネシウム、塩化マグネシウム等、バリウム酸化物成分として、硝酸バリウム、塩化バリウム、水酸化バリウム等が用いられる。 As a silica component used as a raw material of zeolite, sodium silicate, water glass, colloidal silica, silicon dioxide, a hydrolyzate of alkoxysilane, or the like can be used. As an alumina component used as a raw material for zeolite, sodium aluminate, aluminum hydroxide, aluminum nitrate, aluminum chloride, boehmite and the like can be used. Further, sodium hydroxide is used as a raw material of sodium that exhibits alkalinity during hydrothermal synthesis and forms zeolite. As required calcium oxide component, calcium hydroxide, calcium oxide, calcium nitrate, calcium chloride, etc., magnesium oxide component, magnesium hydroxide, magnesium oxide, magnesium nitrate, magnesium chloride, etc., as barium oxide component, Barium nitrate, barium chloride, barium hydroxide and the like are used.
水熱合成においては、上記のゼオライトの原料を含む合成液をオートクレーブのような密閉できる容器に入れ、ここに有機高分子を結合剤としてゼオライト微結晶を付与した多孔質支持体を浸漬し、適度な温度並びに時間合成させてゼオライト結晶膜を多孔質支持体表面に形成する。この際、多孔質支持体の外表面にのみゼオライト結晶膜を形成する際には、円筒状である多孔質支持体の両端の開口部を封止するなどして合成液が内表面に接触しないようにした上で、合成液に浸漬する。また、多孔質支持体の内表面にのみゼオライト結晶膜を形成する際には、外表面をテフロン（登録商標）シールなどで被覆して、合成液の外表面への接触を遮断し、円筒状である多孔質支持体の内部に合成液を充填して、支持体を合成液に浸漬し、適度な温度並びに時間を与えて合成させる、あるいは多孔質支持体の内部に温度を制御した合成液を循環させるなどの方法によりゼオライト結晶膜を形成する。 In hydrothermal synthesis, a synthetic solution containing the above-mentioned zeolite raw material is placed in a container that can be sealed such as an autoclave, and a porous support to which zeolite microcrystals are added using an organic polymer as a binder is immersed therein. The zeolite crystal membrane is formed on the surface of the porous support by synthesizing at a suitable temperature and time. At this time, when forming the zeolite crystal film only on the outer surface of the porous support, the synthetic solution does not contact the inner surface by sealing the openings at both ends of the cylindrical porous support. After so doing, it is immersed in the synthesis solution. In addition, when forming a zeolite crystal film only on the inner surface of the porous support, the outer surface is covered with a Teflon (registered trademark) seal or the like to block the contact of the synthetic solution with the outer surface, and the cylindrical shape The synthetic liquid is filled with a synthetic liquid in the porous support, and the support is immersed in the synthetic liquid and synthesized at an appropriate temperature and time, or the temperature is controlled inside the porous support. A zeolite crystal film is formed by a method such as circulating the gas.
本発明の複合膜を用いて、パーベーパレーション法によって２種以上の液体の混合溶液から少なくとも１種の液体を分離することができる。
混合溶液としては、水と有機物との混合溶液、２種以上の有機物の混合溶液が好適に用いられる。
水および有機物を含む混合溶液からパーベーパレーション法によって水または有機物を選択的に分離する場合、例えば、発酵によって得られるエタノールと水を含む混合溶液からエタノールまたは水を選択的に分離するには、従来、蒸留が一般的な分離方法であった。しかし、発酵により得られるエタノールと水の混合物は多量の水を含むために、蒸留によって分離濃縮するためには、多量のエネルギーが必要となる。
このような場合に、本発明の複合膜を用いると、ゼオライトの種類を適宜選択することにより、パーベーパレーション法によって水と有機物の混合物から、目的物のみを選択的に、しかも少ないエネルギーの使用で分離することが可能となる。
Using the composite membrane of the present invention, at least one liquid can be separated from a mixed solution of two or more liquids by a pervaporation method.
As the mixed solution, a mixed solution of water and an organic material and a mixed solution of two or more organic materials are preferably used.
In the case of selectively separating water or organic matter from a mixed solution containing water and organic matter by pervaporation, for example, in order to selectively separate ethanol or water from a mixed solution containing ethanol and water obtained by fermentation, Traditionally, distillation has been a common separation method. However, since the mixture of ethanol and water obtained by fermentation contains a large amount of water, a large amount of energy is required for separation and concentration by distillation.
In such a case, when the composite membrane of the present invention is used, by selectively selecting the type of zeolite, the pervaporation method is used to selectively select only the target product from the water and organic matter, and use less energy. It becomes possible to separate with.
水のみを選択的に分離する場合には、ゼオライトの種類として、Ａ型、Ｘ型、Ｔ型等の親水性ゼオライトを使用する。一方、エタノールを選択的に分離する場合には、ＺＳＭ類、シリカライト類等の疎水性ゼオライトを用いて分離することができる。上記以外の混合物の場合にも、種類と目的によって、最適なゼオライトを選択すればよい。
２種以上の有機物の混合溶液を分離する例としては、アセトン、メチルエチルケトンなどのケトン類、四塩化炭素、トリクロロエチレンなどのハロゲン化炭化水素、ベンゼン、シクロヘキサンなどの芳香族類と、メタノール、エタノール、プロパノールなどのアルコール類との混合溶液から、アルコール類を抽出する例が挙げられる。
When only water is selectively separated, hydrophilic zeolites such as A type, X type, and T type are used as the type of zeolite. On the other hand, when ethanol is selectively separated, it can be separated using hydrophobic zeolite such as ZSMs and silicalites. In the case of a mixture other than the above, an optimum zeolite may be selected depending on the type and purpose.
Examples of separating a mixed solution of two or more organic substances include ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as carbon tetrachloride and trichloroethylene, aromatics such as benzene and cyclohexane, methanol, ethanol, and propanol. Examples of extracting alcohols from a mixed solution with alcohols such as
以下、実施例によって本発明を具体的に説明する。
本発明において、多孔質支持体の平均細孔径、並びに空孔率はMicromeritics社製ポアサイザ９３２０ポロシメータを用いた水銀圧入法によって測定した。測定においては、セル容積約６ｃｍ３、ステム体積０．４ｃｍ３のセルを用いて、圧力０ＭＰａ〜２０６．８ＭＰａの範囲で水銀を圧入した。測定に用いる多孔質支持体は、測定前に１５０℃のオーブン中に4時間保持して乾燥させ、デシケータ中にて室温にまで冷却した後に測定に供した。また、測定セルに充填するサンプル量は全水銀圧入容積が０．１ｃｃ〜０．３ｃｃの範囲になるように調整し、本測定においては０．１ｇ〜０．５ｇを用いた。
Hereinafter, the present invention will be described specifically by way of examples.
In the present invention, the average pore diameter and the porosity of the porous support were measured by a mercury intrusion method using a pore sizer 9320 porosimeter manufactured by Micromeritics. In the measurement, mercury was injected in a pressure range of 0 MPa to 206.8 MPa using a cell having a cell volume of about 6 cm 3 and a stem volume of 0.4 cm 3 . The porous support used for the measurement was dried by holding it in an oven at 150 ° C. for 4 hours before the measurement, and after cooling to room temperature in a desiccator. Moreover, the sample amount with which the measurement cell was filled was adjusted so that the total mercury intrusion volume was in the range of 0.1 cc to 0.3 cc, and 0.1 g to 0.5 g was used in this measurement.
（１）多孔質支持体の平均細孔径
水銀圧入法において、圧入する際の圧力と、その圧力で水銀が浸入する細孔径の関係は、次の式（１）のＷａｓｈｂｕｒｎの式によって表される。
(1) Average pore diameter of porous support In the mercury intrusion method, the relationship between the pressure at the time of press-in and the pore diameter at which mercury enters at that pressure is expressed by the Washburn formula of the following formula (1). .
Ｄ＝多孔質支持体の細孔径
Ｐ＝水銀を圧入する際の圧力
γ＝水銀の表面張力（４８０ｄｙｎｅ／ｃｍ）
θ＝水銀と細孔壁面の接触角（ここでは１３０°）
D = pore diameter of porous support P = pressure when mercury is injected γ = surface tension of mercury (480 dyne / cm)
θ = contact angle between mercury and pore wall (130 ° here)
上式により、圧入圧力Ｐと細孔径Ｄの関係が求められる。圧入圧力Ｐとそれまでに圧入された水銀量は測定により示されるので、上記の関係式から多孔質支持体の体積平均による平均細孔径を求めることができる。 From the above equation, the relationship between the press-fit pressure P and the pore diameter D is obtained. Since the press-fitting pressure P and the amount of mercury that has been press-fitted up to that point are shown by measurement, the average pore diameter based on the volume average of the porous support can be obtained from the above relational expression.
（２）多孔質支持体の空孔率
測定セル内の多孔質支持体サンプルの体積は、測定セルにサンプルと水銀を注入した状態での圧力印加前のセル内でのサンプルと水銀の体積の総和と、注入した水銀の体積の差として求められる。多孔質支持体の空孔率は測定圧力範囲の最高圧力まで水銀を圧入した際の全水銀圧入量に対応する体積に対する、その測定に用いた多孔質支持体サンプルの体積の比として求められる。
(2) Porosity of porous support The volume of the porous support sample in the measurement cell is the volume of the sample and mercury in the cell before pressure application in the state where the sample and mercury are injected into the measurement cell. It is calculated as the difference between the total and the volume of injected mercury. The porosity of the porous support is determined as the ratio of the volume of the porous support sample used for the measurement to the volume corresponding to the total mercury intrusion when mercury is injected up to the maximum pressure in the measurement pressure range.
（３）エネルギー分散型Ｘ線分光法（ＥＤＳ）
水熱合成前後の複合膜中の有機結合剤の存在分布は、堀場製作所製ＥＭＡＸ−７０００を用いたエネルギー分散型Ｘ線分光法（ＥＤＳ）によるマッピングにより求めた。測定において、電子線加速電圧は１５ｋＶ、作動距離１２ｍｍ、ビーム電流０．４ｎＡの条件で電子線を照射し、炭素原子の特性Ｘ線を検知することにより、マッピングを行った。
(3) Energy dispersive X-ray spectroscopy (EDS)
The presence distribution of the organic binder in the composite film before and after hydrothermal synthesis was determined by mapping by energy dispersive X-ray spectroscopy (EDS) using EMAX-7000 manufactured by Horiba. In the measurement, mapping was performed by irradiating an electron beam under conditions of an electron beam acceleration voltage of 15 kV, a working distance of 12 mm, and a beam current of 0.4 nA, and detecting characteristic X-rays of carbon atoms.
［実施例１］
（ゼオライト微結晶分散溶液の作製）
結合剤としてポリビニルブチラール３００（和光純薬製、平均重合度２００−４００）０．４ｇ、メトキシプロパノール１９．８ｇを混合し、結合剤が完全に溶解した後、Ａ型ゼオライト微結晶（水澤化学社製シルトン−Ｂ、粒径０.８μｍ）０．４ｇを加え、十分に攪拌することにより、ゼオライト微結晶分散溶液を作製した。
[Example 1]
(Preparation of zeolite microcrystal dispersion solution)
As a binder, 0.4 g of polyvinyl butyral 300 (manufactured by Wako Pure Chemical Industries, average polymerization degree 200-400) and 19.8 g of methoxypropanol were mixed, and after the binder was completely dissolved, A type zeolite fine crystals (Mizusawa Chemical Co., Ltd.) A zeolite microcrystal dispersion solution was prepared by adding 0.4 g (Silton-B manufactured, particle size: 0.8 μm) and stirring sufficiently.
（ゼオライト微結晶の多孔質支持体への担持）
外径１．２ｍｍ、膜厚０．２ｍｍ、平均細孔径０．２５μｍ、空孔率４８％のアルミナ粒子の焼結によって得られたアルミナ多孔質支持体の両端を封止した後、ゼオライト微結晶分散溶液に１０秒間浸漬した。引上げ後、６０℃空気雰囲気下において１時間乾燥させることにより、アルミナ多孔質支持体表面に、結合剤によってゼオライト微結晶を担持させた。担持させたゼオライト微結晶は支持体に衝撃を加えても脱離することなく、また指で擦っても脱離しなかった。
図1に得られたゼオライト微結晶を担持させた支持体の断面電子顕微鏡（ＳＥＭ）像並びに、エネルギー分散型Ｘ線分光法（ＥＤＳ）により観測される断面における炭素の存在分布を示す。ＳＥＭ像より多孔質支持体表面にゼオライト微結晶が付与されていることが示される。またＥＤＳ像においては結合剤を構成する炭素原子が存在する部分が白く示されており、このＥＤＳ法により得られた像から、ゼオライト微結晶の周辺に炭素が偏在しており、ゼオライト微結晶が有機高分子によって相互に支持体表面に結合されていることが示される。
(Supporting zeolite microcrystals on a porous support)
After sealing both ends of an alumina porous support obtained by sintering alumina particles having an outer diameter of 1.2 mm, a film thickness of 0.2 mm, an average pore diameter of 0.25 μm, and a porosity of 48%, zeolite fine crystals It was immersed in the dispersion solution for 10 seconds. After pulling up, it was dried in an air atmosphere at 60 ° C. for 1 hour, whereby zeolite fine crystals were supported on the surface of the porous alumina support by a binder. The supported zeolite microcrystals were not detached even when an impact was applied to the support, and were not detached even when rubbed with a finger.
FIG. 1 shows a cross-sectional electron microscope (SEM) image of the support on which the zeolite microcrystals obtained are supported and the carbon distribution in the cross section observed by energy dispersive X-ray spectroscopy (EDS). From the SEM image, it is shown that zeolite microcrystals are imparted to the surface of the porous support. Further, in the EDS image, the portion where the carbon atoms constituting the binder are present is shown in white. From the image obtained by this EDS method, carbon is unevenly distributed around the zeolite microcrystal, and the zeolite microcrystal is It is shown that they are bound to the support surface by the organic polymer.
（ゼオライト結晶膜の形成）
長さ１０ｃｍの上記の多孔質支持体を用意し、水熱合成法により多孔質支持体表面に、Ａ型ゼオライト結晶からなる層を形成させた。合成液は水、ケイ酸ナトリウム、アルミン酸ナトリウムおよび水酸化ナトリウムを、Ｎａ２Ｏ：ＳｉＯ２：Ａｌ２Ｏ３：Ｈ２Ｏ＝２：２：１：１２５のモル比に配合したスラリーを用い、このスラリーを入れたテフロン（登録商標）製の容器に、上記の多孔質支持体を浸漬して、この容器をオートクレーブに入れ、１００℃で３時間１５分、水熱合成反応を行った。
反応後、多孔質支持体を取り出し、十分水洗した後、６０℃で３時間乾燥させた。乾燥後の多孔質支持体の断面を電子顕微鏡により観察したところ、合成液に接触した側の表面に厚さ約５μｍの結晶膜が生成しており、これを広角Ｘ線回折によって解析した結果、Ａ型ゼオライト結晶による緻密な層が形成されていることが確認された。この結晶膜を形成しているＡ型ゼオライトの結晶の寸法は、電子顕微鏡による表面観察の結果、２〜３μｍであった。
(Formation of zeolite crystal film)
The above porous support having a length of 10 cm was prepared, and a layer made of A-type zeolite crystals was formed on the surface of the porous support by a hydrothermal synthesis method. The synthesis solution used was a slurry in which water, sodium silicate, sodium aluminate and sodium hydroxide were mixed in a molar ratio of Na 2 O: SiO 2 : Al 2 O 3 : H 2 O = 2: 2: 1: 125. The porous support was immersed in a Teflon (registered trademark) container containing the slurry, and the container was placed in an autoclave and subjected to a hydrothermal synthesis reaction at 100 ° C. for 3 hours and 15 minutes.
After the reaction, the porous support was taken out, sufficiently washed with water, and dried at 60 ° C. for 3 hours. When the cross section of the porous support after drying was observed with an electron microscope, a crystal film having a thickness of about 5 μm was formed on the surface in contact with the synthesis solution. As a result of analyzing this by wide-angle X-ray diffraction, It was confirmed that a dense layer of A-type zeolite crystals was formed. As a result of surface observation with an electron microscope, the size of crystals of the A-type zeolite forming this crystal film was 2 to 3 μm.
図２に得られた支持体上のゼオライト緻密膜の断面ＳＥＭ像並びに、ＥＤＳ法により観測される断面における炭素の存在分布を示す。ＥＤＳ法により得られた像から、炭素はゼオライト緻密膜の表層に分散して存在しており、水熱合成後、結合剤として用いた有機高分子は主にゼオライト緻密膜の表面に偏在していることが示される。なお、このゼオライト緻密膜表面に存在する結合剤は、以下に述べるパーベーパレーションによる脱水試験の間に流出してなくなることもあるが、分離性能には影響を及ぼさない。 FIG. 2 shows a cross-sectional SEM image of the dense zeolite membrane on the obtained support and the carbon distribution in the cross-section observed by the EDS method. From the image obtained by the EDS method, carbon is dispersed in the surface layer of the dense zeolite membrane, and after hydrothermal synthesis, the organic polymer used as the binder is mainly distributed on the surface of the dense zeolite membrane. Is shown. Note that the binder present on the surface of the dense zeolite membrane may flow out during the dehydration test by pervaporation described below, but does not affect the separation performance.
（パーベーパレーションによる脱水試験）
このようにして得られた複合膜を２０本用意し、両端をシリコン樹脂で固着し、片側を密閉してモジュールを作製した。
このモジュールを用いて、パーベーパレーション法によってエタノール水溶液から水を選択的に分離する試験を行った。図３にこの試験に用いたモジュールによる分離装置の模式図を示す。モジュール５の内部にエタノール９０重量％の水溶液を７５℃の温度で循環することにより供給し、モジュール５内の多孔質支持体の内側を真空ポンプ１によって減圧して、各複合膜の外表面から中空内部に、エタノール水溶液中の水を透過させた。複合膜を透過して分離された水は真空ライン２を通過して、液体窒素によって冷却されたトラップ３に集めた。真空ライン２の間には真空計４を設置している。図中でトラップ６は真空ポンプから油が逆流した場合に、ここで捕捉するために設置した。
(Dehydration test by pervaporation)
Twenty composite films thus obtained were prepared, both ends were fixed with silicon resin, and one side was sealed to produce a module.
Using this module, a test for selectively separating water from an aqueous ethanol solution by a pervaporation method was performed. FIG. 3 shows a schematic diagram of a separation apparatus using modules used in this test. An aqueous solution of 90% by weight of ethanol is supplied by circulating in the module 5 at a temperature of 75 ° C., and the inside of the porous support in the module 5 is depressurized by the vacuum pump 1 so that the outer surface of each composite membrane is removed. Water in an ethanol aqueous solution was allowed to permeate through the hollow interior. The water separated through the composite membrane passed through the vacuum line 2 and was collected in a trap 3 cooled by liquid nitrogen. A vacuum gauge 4 is installed between the vacuum lines 2. In the figure, a trap 6 is installed to capture oil when it flows backward from the vacuum pump.
冷却トラップ３中の水の重量を測定し、膜の単位面積、単位時間当たりの透過量を求めることにより透過流束（Ｑ）を求めた。トラップされた水に含まれるエタノール濃度をガスクロマトグラフィーを用いて測定することにより、分離係数（α）を求めた。具体的には、供給側のエタノールと水の重量濃度をそれぞれ、Ｘ１重量％、Ｘ２重量％とし、トラップ中の透過側のエタノールと水の濃度をそれぞれ、Ｙ１重量％、Ｙ２重量％とすると、分離係数(α)は下記の式（２）によって計算される。
α＝（Ｘ１／Ｘ２）／（Ｙ１／Ｙ２） ・・・（２）
２０本の複合膜より得られたモジュールを用いて、エタノール９０重量％の水溶液から、７５℃の温度においてパーベーパレーション法によって、水を選択的に抽出する分離実験を行ったところ、水の透過流束（Ｑ）は７．２ｋｇ／ｍ２ｈ、分離係数(α)は１４０００であった。
評価後、モジュールを分解し複合膜について個別に分離実験を行ったところ、２０本中１本のαが９０００であったが、残りの１９本は全て１００００以上の分離係数であった。また、分離係数が１００００以上の複合膜の全ての透過流束は７．０ｋｇ／ｍ２ｈ以上であった。
The weight of water in the cooling trap 3 was measured, and the permeation flux (Q) was determined by determining the permeation amount per unit area and unit time of the membrane. The separation factor (α) was determined by measuring the ethanol concentration contained in the trapped water using gas chromatography. Specifically, the ethanol and water weight concentrations on the supply side are X 1 % by weight and X 2 % by weight, respectively, and the ethanol and water concentrations on the permeate side in the trap are Y 1 % by weight and Y 2 %, respectively. If%, the separation factor (α) is calculated by the following equation (2).
α = (X 1 / X 2 ) / (Y 1 / Y 2 ) (2)
Using a module obtained from 20 composite membranes, a separation experiment was carried out to selectively extract water from an aqueous solution of 90% by weight of ethanol at a temperature of 75 ° C. by a pervaporation method. The flux (Q) was 7.2 kg / m 2 h, and the separation factor (α) was 14000.
After the evaluation, the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, 1 of 20 α was 9,000, and the remaining 19 all had a separation factor of 10,000 or more. Further, all the permeation fluxes of the composite membrane having a separation factor of 10,000 or more were 7.0 kg / m 2 h or more.
［比較例１］
実施例１で用いた多孔質支持体へのゼオライト微結晶の担持方法において、分散液に結合剤であるポリビニルブチラールを添加しない以外は、実施例１と同じ方法で、多孔質支持体上にＡ型ゼオライト結晶膜を形成させた。
これを２０本用いて実施例１と同様にモジュールを作製し、実施例1と同様にエタノール９０重量％水溶液からパーベーパレーション法によって、分離実験を行ったところ、水の透過量（Ｑ）は３．８ｋｇ／ｍ２ｈ、分離係数(α)は９０しかなかった。
評価後、モジュールを分解し複合膜について個別に分離実験を行ったところ、２０本中２本に明確なリークが見られ、１本の分離係数は５０以下であり、２本の分離係数は３００から５００であり、３本の分離係数は１０００から２０００であり、１００００以上の分離係数を示したものは残りの１２本のみであった。これは水熱合成により得られた２０本の複合膜の内、半数以上にゼオライト結晶膜に欠陥を有するものが含まれていることを示している。また、分離係数が１００００以上の複合膜の全ての透過流束は５．０ｋｇ／ｍ２ｈ以下であった。
[Comparative Example 1]
In the method for supporting zeolite microcrystals on the porous support used in Example 1, the same method as in Example 1 was used except that polyvinyl butyral as a binder was not added to the dispersion. Type zeolite crystal film was formed.
Using 20 of these, a module was produced in the same manner as in Example 1, and a separation experiment was performed by pervaporation from an aqueous solution of 90% by weight of ethanol as in Example 1. The amount of water permeation (Q) was The separation factor (α) was only 90 at 3.8 kg / m 2 h.
After the evaluation, the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, a clear leak was observed in two of the twenty membranes. One separation factor was 50 or less, and the two separation factors were 300. The separation factor of 3 was 1000 to 2000, and only the remaining 12 showed a separation factor of 10,000 or more. This indicates that more than half of the 20 composite membranes obtained by hydrothermal synthesis contain a defect in the zeolite crystal membrane. Further, all the permeation fluxes of the composite membrane having a separation factor of 10,000 or more were 5.0 kg / m 2 h or less.
［実施例２］
結合剤としてポリビニルアルコール（クラレ製ポバールＲＳ−１１７）０．４ｇ、水１９．６ｇを混合し、結合剤が完全に溶解した後、Ａ型ゼオライト微粒子（水澤化学社製シルトン−Ｂ、粒径０.８μｍ）０．６ｇを加え、十分に攪拌することにより、ゼオライト微結晶分散溶液を作製した。実施例１で用いた多孔質支持体を水に１０秒間浸漬して支持体の細孔内部に水を含浸させた後、６０℃の空気雰囲気下に３０秒間入れることにより支持体の表面部分のみを乾燥させた。続いて、ゼオライト微結晶分散液に１０秒間浸漬し、引上げ後６０℃空気雰囲気下において１時間乾燥させることにより、多孔質支持体表面に、結合剤によってゼオライト微結晶を担持させた。担持させたゼオライト微結晶は支持体に衝撃を加えても脱離することなく、また指で擦っても脱離しなかった。
これを２０本用いて実施例１と同様にモジュールを作製し、実施例１と同様にエタノール９０重量％水溶液からパーベーパレーション法によって、分離実験を行ったところ、水の透過流束（Ｑ）は７．３ｋｇ／ｍ２ｈ、分離係数（α）は１３０００であった。
評価後、モジュールを分解し複合膜について個別に分離実験を行ったところ、２０本中１本のαが９０００であったが、残りの１９本は全て１００００以上の分離係数であった。また、分離係数が１００００以上の複合膜の全ての透過流束は７．０ｋｇ／ｍ２ｈ以上であった。
[Example 2]
As a binder, 0.4 g of polyvinyl alcohol (Kuraray Poval RS-117) and 19.6 g of water were mixed, and after the binder was completely dissolved, A type zeolite fine particles (Silton-B, Mizusawa Chemical Co., Ltd., particle size 0) (0.8 μm) 0.6 g was added, and the mixture was sufficiently stirred to prepare a zeolite microcrystal dispersion solution. The porous support used in Example 1 was immersed in water for 10 seconds to impregnate the pores of the support with water, and then placed in an air atmosphere at 60 ° C. for 30 seconds, so that only the surface portion of the support was placed. Was dried. Subsequently, the zeolite microcrystal dispersion was immersed in a zeolite microcrystal dispersion for 10 seconds, and after drying, dried in an air atmosphere at 60 ° C. for 1 hour, whereby zeolite microcrystals were supported on the porous support surface by a binder. The supported zeolite microcrystals were not detached even when an impact was applied to the support, and were not detached even when rubbed with a finger.
Using 20 of these, a module was produced in the same manner as in Example 1, and a separation experiment was conducted from a 90 wt% aqueous solution of ethanol by a pervaporation method in the same manner as in Example 1. As a result, the water permeation flux (Q) Was 7.3 kg / m 2 h, and the separation factor (α) was 13000.
After the evaluation, the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, 1 of 20 α was 9,000, and the remaining 19 all had a separation factor of 10,000 or more. Further, all the permeation fluxes of the composite membrane having a separation factor of 10,000 or more were 7.0 kg / m 2 h or more.
［実施例３］
多孔質支持体としてポリビニリデンフロライドよりなる有機中空糸（旭化成ケミカルズ製ＰＶＤＦ−ＴＰ、外径２ｍｍ、膜厚０．３ｍｍ、平均細孔径０．４５μｍ）を用い、実施例１で用いたものと同じ分散液を用いて種となるゼオライト微結晶を担持した。担持させたゼオライト微結晶は支持体に衝撃を加えても脱離することなく、また指で擦っても脱離しなかった。図４にゼオライト微結晶を担持した、有機中空糸のＳＥＭ像を示す。図４よりゼオライト微結晶は多孔質支持体表面に均一に付与されていることが示される。ゼオライト微結晶を担持したこの多孔質支持体を、実施例１と同じ条件で水熱合成を施してＡ型ゼオライト結晶膜を形成させた。得られた複合膜を７５℃に保持した９０重量％のエタノール水溶液に接触させ、中空糸内側を減圧することにより、パーベーパレーション法によって分離実験を行ったところ、水の透過流束（Ｑ）は４．２ｋｇ／ｍ２ｈ、分離係数（α）は１００００であった。
評価後、モジュールを分解し複合膜を個別に分離実験を行ったところ、２０本中３本のαが３０００から５０００の範囲であったが、残りの１７本は全て１００００以上の分離係数であった。また、分離係数が１００００以上の複合膜の全ての透過流束は４．０ｋｇ／ｍ２ｈ以上であった。
[Example 3]
An organic hollow fiber made of polyvinylidene fluoride (PVDF-TP manufactured by Asahi Kasei Chemicals Co., Ltd., outer diameter: 2 mm, film thickness: 0.3 mm, average pore diameter: 0.45 μm) as the porous support is the same as that used in Example 1. Zeolite microcrystals as seeds were supported using the same dispersion. The supported zeolite microcrystals were not detached even when an impact was applied to the support, and were not detached even when rubbed with a finger. FIG. 4 shows an SEM image of an organic hollow fiber carrying zeolite microcrystals. FIG. 4 shows that zeolite microcrystals are uniformly applied to the surface of the porous support. This porous support carrying zeolite fine crystals was hydrothermally synthesized under the same conditions as in Example 1 to form an A-type zeolite crystal membrane. The obtained composite membrane was brought into contact with a 90% by weight ethanol aqueous solution maintained at 75 ° C., and the inside of the hollow fiber was depressurized, and a separation experiment was performed by the pervaporation method. Water permeation flux (Q) Was 4.2 kg / m 2 h, and the separation factor (α) was 10,000.
After the evaluation, the module was disassembled and the composite membrane was individually separated. As a result, 3 out of 20 αs were in the range of 3000 to 5000, but the remaining 17 all had a separation factor of 10,000 or more. It was. Further, all the permeation fluxes of the composite membrane having a separation factor of 10,000 or more were 4.0 kg / m 2 h or more.
［実施例４］
（ベーパーパーミエーションによる脱水試験）
実施例１で作成した複合膜を用いて、ベーパーパーミエーション法によってエタノールと水の蒸気よりなる混合気体から水を選択的に分離する試験を行った。図６にこの試験に用いた分離装置の模式図を示す。
容積１リットルのオートクレーブ７の内部にエタノール９０重量％の水溶液２００ｇを入れ、密閉して１３０℃にまで全体を過熱することにより、オートクレーブ内部をエタノールと水の蒸気による混合気体の雰囲気とした。オートクレーブ内部に設置した複合膜８の内側を真空ポンプ１によって減圧して、複合膜８の外表面から中空内部に、エタノール水溶液中の水を透過させた。複合膜８を透過して分離された水は真空ライン２を通過して、液体窒素によって冷却されたトラップ３に集めた。真空ライン２の間には真空計４を設置している。図中でトラップ６は真空ポンプから油が逆流した場合に、ここで捕捉するために設置した。パーベーパレーション法と同様に冷却トラップ３中の水の重量並びに、トラップされた水に含まれるエタノール濃度から、ベーパーパーミエーション法による透過流束と分離係数を求めた結果、水の透過流束（Ｑ）は１９．２ｋｇ／ｍ２ｈ、分離係数(α)は１６０００であった。
[Example 4]
(Dehydration test by vapor permeation)
Using the composite membrane prepared in Example 1, a test was conducted to selectively separate water from a mixed gas composed of ethanol and water vapor by the vapor permeation method. FIG. 6 shows a schematic diagram of the separation apparatus used in this test.
The autoclave 7 having a volume of 1 liter was charged with 200 g of an aqueous solution of 90% by weight of ethanol, sealed and heated to 130 ° C. to make the autoclave inside a mixed gas atmosphere of ethanol and water vapor. The inside of the composite membrane 8 installed inside the autoclave was decompressed by the vacuum pump 1, and water in the ethanol aqueous solution was permeated from the outer surface of the composite membrane 8 into the hollow interior. The water separated through the composite membrane 8 passed through the vacuum line 2 and collected in the trap 3 cooled by liquid nitrogen. A vacuum gauge 4 is installed between the vacuum lines 2. In the figure, a trap 6 is installed to capture oil when it flows backward from the vacuum pump. Similar to the pervaporation method, the permeation flux and separation factor by the vapor permeation method were determined from the weight of water in the cooling trap 3 and the ethanol concentration contained in the trapped water. Q) was 19.2 kg / m 2 h, and the separation factor (α) was 16000.
［比較例２］
結合剤として水ガラス（和光純薬製、SｉＯ２／Ｎａ２Ｏ＝２．０６〜２．３１（Ｍｏｌ ｒａｔｉｏ））２．０ｇ、水１８．０ｇを混合し、結合剤が完全に溶解した後、Ａ型ゼオライト微結晶（水澤化学社製シルトン−Ｂ、粒径０.８μｍ）０．４ｇを加え、十分に攪拌することにより、ゼオライト微結晶分散溶液を作製した。多孔質支持体として実施例２で用いたものと同じ有機中空糸を用い、両端を封止した後、ゼオライト微結晶分散溶液に１０秒間浸漬し、引上げ後６０℃空気雰囲気下において１時間乾燥させることにより、水ガラス結合剤によってゼオライト微結晶を担持させる処理を行った。図５に上記のようにしてゼオライト微結晶の担持処理を施した、有機中空糸のＳＥＭ像を示す。図５より水ガラスを結合剤として用いた場合には、有機中空糸表面には殆んどゼオライト微結晶が担持されていないことが示される。この多孔質支持体を実施例１と同じ条件で水熱合成を施した後、パーベーパレーション法による分離実験を行ったところ、供給液と透過液の組成に差異はなく、全く分離性能を示さなかった。
評価後、モジュールを分解し複合膜について個別に分離実験を行ったところ、２０本の全てに明確なリークが見られ、分離性能を示したものは１本もなかった。
これらの結果により、混合物から目的物を経済的に分離する方法として、本発明の複合膜を用いると、従来技術に比べて高い処理能力が得られることは明らかである。
[Comparative Example 2]
As a binder water glass (produced by Wako Pure Chemical Industries, Ltd., SiO 2 / Na 2 O = 2.06~2.31 (Mol ratio)) 2.0g, water 18.0g were mixed and after the binder is completely dissolved A zeolite fine crystal dispersion solution was prepared by adding 0.4 g of zeolite A crystallites (Silton-B manufactured by Mizusawa Chemical Co., Ltd., particle size 0.8 μm) and stirring sufficiently. The same organic hollow fiber as that used in Example 2 was used as the porous support, both ends were sealed, immersed in a zeolite microcrystal dispersion for 10 seconds, and then pulled up and dried in an air atmosphere at 60 ° C. for 1 hour. Thus, a treatment for supporting zeolite microcrystals with a water glass binder was performed. FIG. 5 shows an SEM image of the organic hollow fiber that has been subjected to the supporting treatment of zeolite microcrystals as described above. FIG. 5 shows that when water glass is used as a binder, almost no zeolite fine crystals are supported on the surface of the organic hollow fiber. This porous support was subjected to hydrothermal synthesis under the same conditions as in Example 1, and then subjected to a separation experiment by the pervaporation method. As a result, there was no difference in the composition of the feed liquid and the permeate, and the separation performance was completely shown. There wasn't.
After the evaluation, the module was disassembled and a separation experiment was performed individually on the composite membrane. As a result, clear leakage was observed in all of the 20 membranes, and none of them showed separation performance.
From these results, it is clear that when the composite membrane of the present invention is used as a method for economically separating the target product from the mixture, a higher processing capacity can be obtained than in the prior art.
本発明の複合膜は、パーベーパレーション法及びベーパーパーミエーション法により、液体、気体、またはそれらの混合物から特定の成分のみを抽出する分離膜として好適に利用できる。特に、共沸状態となるため、従来の蒸留法では分離できなかった、エタノールと水のような系にも本発明の複合膜を利用することができる。 The composite membrane of the present invention can be suitably used as a separation membrane for extracting only specific components from a liquid, a gas, or a mixture thereof by a pervaporation method and a vapor permeation method. In particular, since it is in an azeotropic state, the composite membrane of the present invention can be used in a system such as ethanol and water that cannot be separated by a conventional distillation method.
１ 真空ポンプ
２ 真空ライン
３ 冷却トラップ
４ 真空計
５ モジュール
６ トラップ
７ オートクレーブ
８ 複合膜
1 vacuum pump 2 vacuum line 3 cooling trap 4 vacuum gauge 5 module 6 trap 7 autoclave 8 composite membrane
Claims (10)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005377758A JP2009066462A (en) | 2005-12-28 | 2005-12-28 | Method for preparing composite membrane |
| TW095129076A TW200724221A (en) | 2005-03-14 | 2006-08-08 | Process for producing composite membrane |
| PCT/JP2006/316250 WO2007077646A1 (en) | 2005-12-28 | 2006-08-18 | Process for producing composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005377758A JP2009066462A (en) | 2005-12-28 | 2005-12-28 | Method for preparing composite membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2009066462A true JP2009066462A (en) | 2009-04-02 |
Family
ID=38228006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005377758A Pending JP2009066462A (en) | 2005-03-14 | 2005-12-28 | Method for preparing composite membrane |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2009066462A (en) |
| WO (1) | WO2007077646A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012236155A (en) * | 2011-05-12 | 2012-12-06 | Hitachi Zosen Corp | Zeolite composite membrane |
| KR20130111052A (en) * | 2012-03-30 | 2013-10-10 | 코오롱인더스트리 주식회사 | Porous membrane and method for manufacturing the same |
| CN105363352A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution |
| CN108786481A (en) * | 2017-09-06 | 2018-11-13 | 史玉成 | The synthesizer of doughnut type T molecular sieve film |
| JP2019503841A (en) * | 2015-11-20 | 2019-02-14 | １９３４６１２ オンタリオ インク．１９３４６１２ Ｏｎｔａｒｉｏ Ｉｎｃ． | Fluid cleaning apparatus, system, and method using silicon carbide membrane |
| CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
| CN113574017A (en) * | 2019-03-25 | 2021-10-29 | 日本碍子株式会社 | Method for producing zeolite membrane complex and zeolite membrane complex |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010115610A (en) * | 2008-11-14 | 2010-05-27 | Sumitomo Electric Ind Ltd | Zeolite composite separation membrane and method for manufacturing the same |
| CN103657436B (en) * | 2013-12-31 | 2016-06-01 | 南京工业大学 | The hollow fiber molecular sieve of a kind of high strength and its preparation method |
| CN106390767A (en) * | 2016-11-08 | 2017-02-15 | 华南理工大学 | Honeycomb ceramic composite membrane and method for preparing same |
| CN108939928B (en) * | 2018-06-29 | 2021-06-04 | 中国石油大学(华东) | Preparation method of mixed matrix membrane with sodalite nanocrystalline as filler |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002537990A (en) * | 1999-03-11 | 2002-11-12 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Crystalline molecular sieve layer and method for producing the same |
| WO2005014481A1 (en) * | 2003-08-06 | 2005-02-17 | Bussan Nanotech Research Institute, Inc. | Method and apparatus for manufacturing zeolite membrane, and zeolite tubular separation membrane provided by the method |
| JP2005074382A (en) * | 2003-09-03 | 2005-03-24 | Mitsui Eng & Shipbuild Co Ltd | Mixture separation membrane and mixture separation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10502609A (en) * | 1994-07-08 | 1998-03-10 | エクソン リサーチ アンド エンジニアリング カンパニー | Zeolite layer with controlled crystal width and preferred orientation grown on growth promoting layer |
-
2005
- 2005-12-28 JP JP2005377758A patent/JP2009066462A/en active Pending
-
2006
- 2006-08-18 WO PCT/JP2006/316250 patent/WO2007077646A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002537990A (en) * | 1999-03-11 | 2002-11-12 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Crystalline molecular sieve layer and method for producing the same |
| WO2005014481A1 (en) * | 2003-08-06 | 2005-02-17 | Bussan Nanotech Research Institute, Inc. | Method and apparatus for manufacturing zeolite membrane, and zeolite tubular separation membrane provided by the method |
| JP2005074382A (en) * | 2003-09-03 | 2005-03-24 | Mitsui Eng & Shipbuild Co Ltd | Mixture separation membrane and mixture separation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012236155A (en) * | 2011-05-12 | 2012-12-06 | Hitachi Zosen Corp | Zeolite composite membrane |
| KR20130111052A (en) * | 2012-03-30 | 2013-10-10 | 코오롱인더스트리 주식회사 | Porous membrane and method for manufacturing the same |
| KR101885255B1 (en) * | 2012-03-30 | 2018-08-03 | 코오롱인더스트리 주식회사 | Porous Membrane and Method for Manufacturing The Same |
| CN105363352A (en) * | 2015-11-14 | 2016-03-02 | 大连理工大学 | Method for synthesizing high acid resistant MOR zeolite molecular sieve membrane from fluorine-containing dilute solution |
| JP2019503841A (en) * | 2015-11-20 | 2019-02-14 | １９３４６１２ オンタリオ インク．１９３４６１２ Ｏｎｔａｒｉｏ Ｉｎｃ． | Fluid cleaning apparatus, system, and method using silicon carbide membrane |
| CN108786481A (en) * | 2017-09-06 | 2018-11-13 | 史玉成 | The synthesizer of doughnut type T molecular sieve film |
| CN113574017A (en) * | 2019-03-25 | 2021-10-29 | 日本碍子株式会社 | Method for producing zeolite membrane complex and zeolite membrane complex |
| CN112870992A (en) * | 2021-01-13 | 2021-06-01 | 同济大学 | Zeolite membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007077646A1 (en) | 2007-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2009066462A (en) | Method for preparing composite membrane | |
| JP6373381B2 (en) | Zeolite membrane, method for producing the same, and separation method using the same | |
| EP3225297B1 (en) | Use of a porous support-cha zeolite membrane composite for separation of a gas mixture | |
| US8258069B2 (en) | Zeolitic separation membrane and process for producing the same | |
| JP6446378B2 (en) | Method for producing a crystalline film of zeolite and / or zeolite-like crystals on a porous substrate | |
| JP5087644B2 (en) | Method for producing ZSM-5 type zeolite membrane | |
| US11666867B2 (en) | Zeolite separation membrane and production method therefor | |
| JP5621965B2 (en) | Alumina composite separation membrane and method for producing the same | |
| US7951738B2 (en) | Process for producing zeolite separation membrane | |
| JP4751996B2 (en) | Method for producing ZSM-5 type zeolite membrane | |
| JP5051816B2 (en) | Philipsite type zeolite composite membrane and method for producing the same | |
| US8263179B2 (en) | Process for producing zeolite separation membrane | |
| JP2007313389A (en) | Marinoite type zeolite composite membrane and its manufacturing method | |
| JP2006320896A (en) | Compound membrane, and its manufacturing method | |
| KR100903952B1 (en) | A method for preparing of hydrophilic zeolite membrane | |
| JP2005074382A (en) | Mixture separation membrane and mixture separation method | |
| JP2010180080A (en) | Method for producing zeolite membrane | |
| JP2008043864A (en) | Zeolite composite membrane and its manufacturing method | |
| JPH1062401A (en) | Filler for liquid chromatography | |
| JP2002249313A (en) | Method for coating with zeolite crystal, substrate coated with the same, method for manufacturing zeolite film, zeolite film and method of separation | |
| JP2016215081A (en) | Hydrophilic zeolite separation membrane and production method of the same | |
| JP4506251B2 (en) | Separation membrane and method for producing separation membrane | |
| JP2013059714A (en) | Method for producing support-zeolite membrane composite | |
| JP2006231123A (en) | Composite membrane | |
| JP2002220225A (en) | Zeolite membrane, method for treating zeolite membrane, aluminium electrolytic capacitor, and separating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20120329 |