WO2012133538A1 - イオン交換膜 - Google Patents
イオン交換膜 Download PDFInfo
- Publication number
- WO2012133538A1 WO2012133538A1 PCT/JP2012/058157 JP2012058157W WO2012133538A1 WO 2012133538 A1 WO2012133538 A1 WO 2012133538A1 JP 2012058157 W JP2012058157 W JP 2012058157W WO 2012133538 A1 WO2012133538 A1 WO 2012133538A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion exchange
- membrane
- sheet
- exchange membrane
- porous
- Prior art date
Links
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 52
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 31
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 31
- 239000011148 porous material Substances 0.000 claims abstract description 20
- -1 polyethylene Polymers 0.000 claims description 95
- 239000004698 Polyethylene Substances 0.000 claims description 84
- 229920000573 polyethylene Polymers 0.000 claims description 84
- 239000000203 mixture Substances 0.000 claims description 41
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 abstract description 7
- 239000012528 membrane Substances 0.000 description 62
- 239000000178 monomer Substances 0.000 description 44
- 239000002585 base Substances 0.000 description 30
- 238000005342 ion exchange Methods 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000012267 brine Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 22
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 22
- 238000005341 cation exchange Methods 0.000 description 20
- 239000003011 anion exchange membrane Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 238000005259 measurement Methods 0.000 description 12
- 239000004014 plasticizer Substances 0.000 description 12
- 238000000909 electrodialysis Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000013535 sea water Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011033 desalting Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
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- 229920001179 medium density polyethylene Polymers 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
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- 229920006267 polyester film Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
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- 230000008961 swelling Effects 0.000 description 2
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
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- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
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- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- 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
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/018—Granulation; Incorporation of ion-exchangers in a matrix; Mixing with inert materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
Definitions
- the present invention relates to an ion exchange membrane comprising a porous sheet through which fine pores penetrate as a substrate.
- Ion exchange membranes are used as membranes for electrodialysis used in salt production and desalting processes in the field of food, electrolyte membranes for fuel cells, and for acid recovery from acids containing metal ions generated in the steel industry.
- the membrane is used industrially in many fields such as a diffusion dialysis membrane.
- Such an ion exchange membrane has a structure in which a base sheet having a function as a reinforcing material is provided in an ion exchange resin as a core material, and thereby has a certain membrane strength and membrane shape stability. Has been granted. If there is no core material, the ion exchange resin has a large number of ion exchange groups. Therefore, when immersed in an aqueous electrolyte solution, the ion exchange resin easily swells, resulting in a decrease in strength and a change in form of the ion exchange membrane.
- an ion exchange membrane in which a porous resin sheet is used as the substrate sheet is known.
- the voids in the porous resin sheet as the base material are filled with the ion exchange resin, and as a result, the electrical resistance of the membrane (hereinafter referred to as membrane resistance) is low.
- membrane resistance the electrical resistance of the membrane
- a thin film such as polytetrafluoroethylene or high molecular weight polyethylene resin is generally used, and this thin film is uniaxial or biaxial in order to avoid strength reduction due to porosity. Is stretched.
- Patent Document 1 discloses a cation exchange membrane for salt production containing a porous stretched polyethylene sheet (Hypore manufactured by Asahi Kasei Chemicals Corporation, Cetilla manufactured by Tonen Chemical Nasu Co., Ltd.) as a base sheet.
- a porous stretched polyethylene sheet Hydrophilic polyethylene sheet
- the ion exchange membrane using the porous base sheet as described above has no practical strength despite being stretched because the thickness of the base sheet is thin. It cannot be said that the concentration characteristics when dialyzing are high. Concentration characteristics refer to the relationship between the membrane resistance per unit thickness of the ion exchange membrane and the salt concentration (brine concentration) of concentrated water produced when electrodialysis is performed using the membrane. A membrane that has a low membrane resistance and can obtain a high brine concentration has a high concentration characteristic.
- an object of the present invention is to provide an ion exchange membrane using a porous base sheet, which has further improved concentration characteristics when electrodialyzed. Specifically, it is to provide an ion exchange membrane having a very low membrane resistance per unit thickness and a high brine concentration.
- the present inventors have used an unstretched porous polyethylene sheet as a porous base sheet, compared with the case of using a stretched one.
- the inventors have found a completely unexpected finding that the concentration characteristics are improved, and have completed the present invention.
- an ion exchange membrane comprising a porous unstretched polyethylene sheet having fine pores penetrating an ion exchange resin in the pores.
- the porous unstretched polyethylene sheet preferably has a thickness of 10 to 300 ⁇ m and a porosity of 30 to 80%.
- the ion exchange resin can be obtained by polymerizing a polymerizable composition for forming the ion exchange resin in the pores.
- the porous unstretched polyethylene sheet used as the base sheet is not stretched, its tensile elongation is extremely large compared to the stretched porous polyethylene sheet, and the length direction. Both (MD) and axial direction (TD) tensile elongation is 450% or more.
- the ion exchange membrane of the present invention has greatly improved concentration characteristics as compared with a porous stretched sheet used as a base sheet.
- the ion exchange membrane (cation exchange membrane or anion exchange membrane) of the invention has the following formula: B> 0.006A + 1.7 The condition represented by is satisfied.
- the above equation is an equation obtained from experimental values.
- the equation is a relational expression between the membrane resistance A per unit thickness and the brine concentration B in the seawater concentration test, and is a measure showing the effect in the present invention.
- the ion exchange membrane of the present invention can produce a high concentration of brine compared to the membrane resistance, exhibits excellent concentration characteristics, and is superior to the ion exchange membrane using a porous stretched sheet as a base sheet.
- High brine concentration can be obtained.
- the seawater concentration test means that a cation exchange membrane and an anion exchange membrane are incorporated into a small electrodialysis apparatus (current-carrying membrane area 100 cm 2 ) at 25 ° C. as shown in the examples described later. Seawater is supplied to the desalting chamber and electrodialysis is performed at a current density of 3 A / dm 2 .
- the brine concentration is determined from the Cl ⁇ concentration of the concentrate obtained by the seawater concentration test.
- the thickness of the sheet is reduced by stretching, so there is a limit to adjusting the properties such as mechanical strength by adjusting the thickness,
- the thickness is not limited, and the degree of freedom in adjusting characteristics such as mechanical strength is extremely large.
- FIG. 4 is a diagram showing the relationship between membrane resistance per unit thickness and brine concentration in the ion exchange membranes of Examples 1 to 3 and Comparative Examples 1 to 3.
- the ion exchange membrane of the present invention has the greatest feature in that an unstretched porous polyethylene sheet is used as a base sheet, and penetrates the front and back of this unstretched sheet. The fine pores are filled with an ion exchange resin.
- the thickness and porosity of the unstretched porous polyethylene sheet are preferably within a predetermined range in order to satisfy characteristics such as ion exchange capacity, membrane resistance, dimensional stability, and mechanical strength.
- the thickness is desirably in the range of 10 to 300 ⁇ m, particularly 50 to 250 ⁇ m, and the porosity is desirably 30 to 80%, particularly 40 to 60%.
- the porosity is higher than necessary, the amount of ion exchange resin per unit volume increases, and when used for practical use, the ion exchange resin swells and shrinks and tends to lack dimensional stability and mechanical strength. There is.
- a polyethylene known per se for example, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene or ultrahigh molecular weight polyethylene may be used. It can.
- high density polyethylene, medium density polyethylene, low density polyethylene, and linear low density polyethylene are preferable from the viewpoint of concentration characteristics.
- ultrahigh molecular weight polyethylene is preferred.
- polyethylenes are copolymers (linear copolymer polyethylenes) containing ⁇ -olefin units such as propylene, butene, pentene, hexene, octene and the like in an amount of 4 mol% or less with respect to ethylene units. Also good.
- the ion exchange resin filled in the pores of the porous unstretched polyethylene sheet may be a known one, for example, an ion exchange group that expresses ion exchange capacity in a hydrocarbon-based or fluorine-based resin, specifically, Are those into which a cation exchange group or an anion exchange group has been introduced.
- hydrocarbon resins examples include styrene resins and acrylic resins.
- fluorine material examples include perfluorocarbon resins.
- An ion exchange group is a functional group that can be negatively or positively charged in aqueous solution.
- the cation exchange group include a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group. Generally, a sulfonic acid group that is a strongly acidic group is preferable.
- the anion exchange group include a primary to tertiary amino group, a quaternary ammonium group, a pyridyl group, an imidazole group, and a quaternary pyridinium group. A quaternary pyridinium group is preferred.
- the ion exchange resin having an ion exchange group as described above is appropriately selected depending on the porosity of the base sheet made of the porous unstretched polyethylene sheet described above and the amount of ion exchange groups introduced into the ion exchange resin. It is present in the ion exchange membrane in such an amount that it has an ion exchange capacity (for example, about 1 to 3.5 meq / g ⁇ dry membrane).
- the ion exchange membrane of the present invention having the structure described above is a polymerizable composition for producing a porous unstretched polyethylene sheet and forming an ion exchange resin in the voids (in the pores) of the unstretched sheet.
- An ion exchange membrane precursor is prepared by filling, then the polymerizable composition in the ion exchange membrane precursor is polymerized, and if necessary, ion exchange groups are added to the polymer obtained in the polymerization step. It is manufactured by introducing.
- porous unstretched polyethylene sheet For the production of the porous unstretched polyethylene sheet, the above-mentioned polyethylene for forming the sheet is used.
- a porous unstretched polyethylene sheet is prepared by mixing an additive for forming pores in the polyethylene to prepare a sheet-forming composition, and the sheet-forming composition is unstretched by extrusion molding or the like.
- a sheet can be formed, and then the additive can be removed by extraction with an organic solvent, dissolution with an acid or alkali, or the like.
- the additive for forming the pores is not particularly limited as long as it can be removed from the sheet by extraction with an organic solvent, dissolution with an alkali, or the like, and various additives can be used.
- Additives that can be extracted with an organic solvent are typically plasticizers such as phthalate esters such as dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and dibutyl phthalate, dioctyl adipate, and diisononyl adipate.
- adipic acid ester such as trioctyl phosphate, trimellitic acid ester such as trioctyl trimellitic acid, and organic acid ester such as glyceric acid ester.
- liquid paraffin, solid wax, mineral oil, citrate ester, epoxidized vegetable oil, and the like can also be used as additives that can be extracted with an organic solvent.
- phthalic acid esters particularly dioctyl phthalate (DOP) is preferred.
- DOP dioctyl phthalate
- examples of the additive that can be dissolved in acid or alkali include inorganic powder, specifically, silica, alumina, mica, talc, and the like, and silica is particularly preferable.
- the plasticizer and inorganic powder described above can be used alone or in combination of two or more, respectively, and particularly preferably a combination of a plasticizer and an inorganic powder. That is, the plasticizer is compatible with or dispersed in the above-described polyethylene, and is particularly advantageous for forming pores so as to penetrate the polyethylene sheet.
- the inorganic powder has an appropriate size. This is advantageous for the formation of pores. Therefore, by using both in combination, the size and porosity of the pores penetrating the polyethylene sheet can be easily adjusted to the above-described ranges.
- the plasticizer is used in an amount of 50 to 300 parts by weight, particularly 100 to 200 parts by weight per 100 parts by weight of polyethylene, and the inorganic powder is used in an amount of 30 to 150 parts by weight per 100 parts by weight of polyethylene. It is preferable to blend in polyethylene together with the plasticizer in an amount of parts by weight, especially 50 to 100 parts by weight.
- the plasticizer is removed from the polyethylene sheet by extraction with an organic solvent, and the inorganic powder is removed by dissolving it in an acid or alkali.
- the plasticizer and the inorganic powder are contained in the polyethylene sheet. It is preferable to remove the inorganic powder after first removing the plasticizer. That is, by forming fine pores by removing the plasticizer and then treating with acid or alkali, the acid or alkali penetrates into the inside of the polyethylene sheet through the pores, and as a result, is dispersed inside. This is because the inorganic powder is dissolved and quickly removed.
- the porous polyethylene sheet produced as described above is unstretched, and as already mentioned, its tensile elongation is very large compared to that of the stretched film, and the tensile elongation of MD and TD is high. Both are 450% or more.
- MD refers to the machine direction (winding direction) when the sheet forming composition is extruded
- TD refers to the direction perpendicular to MD.
- the polymerizable composition filled in the voids of the porous unstretched polyethylene sheet prepared as described above is a single monomer having a functional group capable of introducing the above-described ion exchange group (functional group for introducing an exchange group). Or a monomer having an ion exchange group (hereinafter, these monomers may be referred to as “basic monomer components”), a crosslinkable monomer, a polymerization initiator, and the like. It is prepared by mixing these components.
- the monomer having a functional group for introducing an exchange group and the monomer having an ion exchange group may be those conventionally used for producing an ion exchange resin.
- examples of the monomer having a functional group for introducing a cation exchange group include styrene, chloromethylstyrene, vinyltoluene, vinylxylene, ⁇ -methylstyrene, vinylnaphthalene, ⁇ -halogenated styrenes, and the like.
- examples of the monomer having a functional group for introducing an anion exchange group include styrene, vinyl toluene, chloromethyl styrene, vinyl pyridine, vinyl imidazole, ⁇ -methyl styrene, vinyl naphthalene and the like.
- Examples of the monomer having a cation exchange group include sulfonic acid monomers such as ⁇ -halogenated vinyl sulfonic acid, styrene sulfonic acid, and vinyl sulfonic acid, and carboxylic acid monomers such as methacrylic acid, acrylic acid, and maleic anhydride. Examples thereof include monomers, phosphonic acid monomers such as vinyl phosphoric acid, and salts thereof. Examples of the monomer having an anion exchange group include amine monomers such as vinylbenzyltrimethylamine and vinylbenzyltriethylamine, nitrogen-containing heterocyclic monomers such as vinylpyridine and vinylimidazole, and salts thereof. Can be mentioned.
- a target ion exchange membrane can be obtained at the stage where the polymerization step described later is completed.
- a target ion exchange membrane can be obtained by performing the ion exchange group introduction step after the polymerization step.
- the crosslinkable monomer is used for densifying the ion exchange resin and enhancing the swelling inhibiting property, the film strength, and the like.
- the crosslinkable monomer is not particularly limited.
- Such a crosslinkable monomer is generally preferably 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight with respect to 100 parts by weight of the basic monomer component described above.
- a monomer having an ion exchange group in addition to the above-mentioned monomer having a functional group for introducing an exchange group, a monomer having an ion exchange group, and a crosslinkable monomer, other copolymerizable with these monomers as required. These monomers may be added. Examples of such other monomers include styrene, acrylonitrile, methylstyrene, acrolein, methyl vinyl ketone, and vinyl biphenyl.
- polymerization initiator conventionally known polymerization initiators are used without particular limitation. Specifically, octanoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t- Organic peroxide polymerization initiators such as hexyl peroxybenzoate and di-t-butyl peroxide, and azo polymerization initiators such as azobisisobutyronitrile are used.
- a polymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the basic monomer component.
- a matrix resin can be blended with the polymerizable composition containing the above-described various components as necessary.
- matrix resins include ethylene-propylene copolymers, saturated aliphatic hydrocarbon polymers such as polybutylene, styrene polymers such as styrene-butadiene copolymers, nitrile butadiene rubber, hydrogenated nitrile butadiene rubber, Epichlorohydrin rubber, polyvinyl chloride, chlorinated polyethylene rubber or various comonomers such as vinyltoluene, vinylxylene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, ⁇ -halogenated styrene, ⁇ , ⁇ Styrene-based monomers such as, ⁇ '-trihalogenated styrene, monoolefins such as ethylene and butylene, and conjugated diolefins such as
- ком ⁇ онентs are used in such an amount that the viscosity becomes such that the polymerizable composition can be quickly filled and held in the voids of the porous unstretched polyethylene sheet without causing dripping or the like.
- a plasticizer can be blended with the polymerizable composition as necessary in order to impart flexibility of the film-like material after polymerization or to facilitate the introduction of exchange groups.
- phthalates such as dioctyl phthalate and dibutyl phthalate
- adipates such as dioctyl adipate and diisononyl adipate
- epoxides such as styrene oxide
- ethers such as diphenyl ether and dibenzyl ether, etc. Is done.
- the unstretched polyethylene sheet since the polyethylene molecules are not oriented and the molecular arrangement is random, the monomer molecules easily enter the intermolecular gap. Therefore, the affinity between the monomer and the surface of the porous unstretched polyethylene sheet is high, and the adhesion between the formed polymer (ion exchange resin) and the porous unstretched polyethylene sheet as the base sheet is high. Will be obtained. Thus, as a result of ensuring high adhesion between the ion exchange resin and the base material sheet (porous unstretched polyethylene sheet), when electrodialysis is performed using such an ion exchange membrane, a predetermined polarity is obtained.
- Ions anions in the anion exchange membrane and cations in the cation exchange membrane
- the permeation of water molecules and other ions is effectively suppressed (the gap between the ion exchange resin and the base sheet).
- concentration characteristics are improved.
- a stretched resin sheet is used as a porous base sheet, so that high adhesion is ensured between the ion exchange resin and the base sheet. Cannot be obtained, and high adhesion properties cannot be obtained due to insufficient adhesion.
- the porous stretched resin sheet since the resin molecules are oriented and regularly arranged, it is difficult for the monomer molecules to enter the intermolecular gap, and the resulting ion exchange resin and the base material sheet are porous.
- the stretched resin sheet has poor affinity and the adhesion between them is extremely low.
- electrodialysis is performed using this ion exchange membrane, water molecules and other ions are transmitted together with ions of a predetermined polarity, and the concentration characteristics are low.
- the method for filling the void composition of the porous unstretched polyethylene sheet with the polymerizable composition is not particularly limited, but generally a method for immersing the porous unstretched polyethylene sheet in the polymerizable composition or polymerization.
- coating and spraying an adhesive composition to a porous unstretched polyethylene sheet is employ
- the polymerizable composition is contacted with the porous unstretched polyethylene sheet under reduced pressure.
- the filling method can also be adopted.
- the ion exchange membrane precursor obtained by filling the void portion of the porous unstretched polyethylene sheet with the polymerizable composition is subjected to the polymerization step.
- the intended ion exchange membrane can be obtained by completing this step.
- a monomer having a functional group for introducing an exchange group is used as the basic monomer component, it is necessary to introduce an ion exchange group after the completion of this step.
- a method for polymerizing the polymerizable composition after filling the voids of the porous unstretched polyethylene sheet a method of raising the temperature from room temperature under pressure by sandwiching it between films of polyester or the like is generally preferred.
- Such polymerization conditions depend on the type of polymerization initiator, the type of monomer, and the like, and may be appropriately selected and determined from known conditions. Polymerization is possible even at a temperature higher than the melting point of the unstretched polyethylene sheet, but the strength of the obtained ion exchange membrane may be lowered, so the polymerization is performed at a temperature near or lower than the melting point of the unstretched polyethylene sheet. . In general, the range of 40 to 140 ° C. is preferable.
- the polymerization is performed in a state where a part of the unstretched polyethylene sheet is dissolved in the polymerizable composition. As a result, ion exchange with the unstretched polyethylene sheet is performed. The bonding strength with the resin can be increased, and the film strength can be further improved.
- the polymerization can be performed in the air, since the polymerization may be inhibited by oxygen in the air, the polymerization is preferably performed in a nitrogen atmosphere.
- the polymerization time varies depending on the polymerization temperature and the like, but is generally about 30 minutes to 24 hours.
- the ion exchange group is introduced by a method known per se.
- a treatment such as sulfonation, chlorosulfonation, phosphoniumation, hydrolysis and the like.
- an anion exchange membrane it is carried out by treatment such as amination or alkylation.
- the ion exchange membrane produced as described above is composed of an ion exchange resin and a base sheet (porous unstretched polyethylene sheet) in relation to the base sheet being unstretched. Adhesiveness is high, and therefore concentration characteristics are high.
- the thickness of the porous polyethylene sheet Using a micro thickness gauge (type KBN, terminal diameter ⁇ 5 mm, measurement pressure 62.47 kPa) manufactured by Toyo Seiki, measurement was performed at an ambient temperature of 23 ⁇ 2 ° C.
- a micro thickness gauge type KBN, terminal diameter ⁇ 5 mm, measurement pressure 62.47 kPa manufactured by Toyo Seiki
- Porosity (volume ⁇ mass / membrane density) / volume ⁇ 100 The volume was calculated from the sample size and the film thickness, and the film density was calculated from the material density.
- Tensile elongation Based on JIS K7127, it measured about MD and TD sample (FIG. 1) using the tensile testing machine ⁇ Orientec Co., Ltd. tensilon universal testing machine RTG-1210 (trademark) ⁇ . The chuck interval was 50 mm. Tensile elongation (%) is measured by measuring the amount of elongation (mm) until the sample breaks by attaching a contact type extensometer between the marked lines. ) And multiplied by 100. The measurement was performed at a temperature of 23 ⁇ 2 ° C., a chuck pressure of 0.50 MPa, and a tensile speed of 100 mm / min.
- Viscosity average molecular weight Based on ASTM-D4020, the intrinsic viscosity [ ⁇ ] at 135 ° C. in a decalin solvent was determined.
- Membrane resistance An ion exchange membrane is sandwiched in a two-chamber cell having a platinum black electrode, a 0.5 mol / L-NaCl solution is filled on both sides of the ion exchange membrane, and the resistance between the electrodes at 25 ° C. by an AC bridge (frequency 1000 cycles / second). was measured. The membrane resistance was determined from the difference between the interelectrode resistance and the interelectrode resistance when no ion exchange membrane was installed. The ion exchange membrane used for the above measurement was previously equilibrated in a 0.5 mol / L NaCl solution.
- the thickness of the ion exchange membrane After dipping in a 0.5 mol / L-NaCl solution, the surface of the membrane was wiped with a tissue paper, and measurement was performed using a micrometer MED-25PJ (manufactured by Mitutoyo Corporation).
- the cation exchange membranes shown in Examples and Comparative Examples are an anion exchange membrane ACS for salt production (manufactured by Astom Co., Ltd.), and the anion exchange membranes shown in the Examples and Comparative Examples are cation exchange membranes for salt production.
- CIMS manufactured by Astom Co., Ltd.
- each was incorporated into a small electrodialysis apparatus (current-carrying membrane area 100 cm 2 ), and a seawater concentration test was performed.
- seawater was supplied at 25 ° C. with a flow rate of 6 cm / sec in the desalting chamber and a current density of 3 A / dm 2 .
- the Cl ⁇ concentration of the resulting concentrate was taken as the brine concentration.
- porous unstretched polyethylene sheet Various physical properties of the porous unstretched polyethylene sheet were as follows. Thickness: 90 ⁇ m Porosity: 50% Air permeability: 1,150 seconds / 100cc Tensile elongation: MD 590%, TD 941%
- Example 1 82.5 parts by weight of styrene, 17.5 parts by weight of divinylbenzene (purity 57%), 5 parts by weight of dibutyl phthalate, 2 parts by weight of perbutyl O (t-butylperoxy-2-ethylhexanoate, manufactured by NOF Corporation) Were mixed to prepare a polymerizable composition. 500 g of this polymerizable composition is placed in a 1000 ml glass container, and the porous unstretched polyethylene sheet produced in Production Example 1 is immersed therein as a base sheet, and the polymer composition is placed in the pores of the sheet. Filled.
- the membrane was sequentially immersed in 90% sulfuric acid, 60% sulfuric acid and ion exchange water, and further immersed in a 4 mol / L-NaOH aqueous solution for 12 hours and washed with water to obtain a sulfonic acid type cation exchange membrane.
- the obtained cation exchange membrane had an electric resistance of 1.16 ⁇ ⁇ cm 2 , a thickness of 107 ⁇ m, and a brine concentration of 3.22 mol / L.
- Example 1 A cation exchange membrane was obtained in exactly the same manner as in Example 1 except that the porous stretched polyethylene sheet obtained in Production Example 2 was used as a base sheet. Table 1 shows the measurement results of the membrane characteristics of the obtained cation exchange membrane.
- Example 2 and 3 Using the porous unstretched polyethylene sheet obtained in Production Example 1, a cation exchange membrane was obtained in the same manner as in Example 1 except for parts by weight of styrene and DVB (purity 57%) as shown in Table 1. It was. Table 1 shows the measurement results of the membrane characteristics of the obtained cation exchange membrane.
- FIG. 2 shows the relationship between the membrane resistance per unit thickness of the cation exchange membranes obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the brine concentration.
- a polymerizable composition was prepared by mixing 89.5 parts by weight of chloromethylstyrene, 10.5 parts by weight of divinylbenzene (purity 57%), 2 parts by weight of styrene oxide and 4 parts by weight of perbutyl O. 500 g of this polymerizable composition is put into a 1000 ml glass container, and the porous unstretched polyethylene sheet prepared in Production Example 1 is immersed therein as a base sheet, and the polymer composition is filled in the voids of the sheet. did.
- Examples 5 and 6 Using the porous unstretched polyethylene sheet obtained in Production Example 1, as shown in Table 2, except for parts by weight of chloromethylstyrene and DVB (purity 57%), an anion exchange membrane was obtained in the same manner as in Example 4. Got. Table 2 shows the measurement results of the membrane characteristics of the obtained anion exchange membrane.
- FIG. 4 shows the relationship between the thickness and brine concentration for the anion exchange membrane obtained in Comparative Example 7 and the anion exchange membrane obtained in Example 6 and Comparative Example 6 having a membrane composition close to that of Comparative Example 7. .
- the brine concentration does not depend on the thickness of the membrane
- the brine concentration is improved by using an unstretched porous sheet as a base sheet as in Example 6. Is understood.
- the water concentration obtained by electrodialysis is mainly determined by the amount of hydrated water that moves in association with the permeation of ions (generally referred to as electroosmotic water; the larger the electroosmotic water, the lower the water concentration) and the membrane
- the thickness of the membrane strongly affects the permeation of the substance (permeation flux due to diffusion), but in the case of electrodialysis, the potential difference is defined as the driving force. Because of this system, the amount of ion permeation through the membrane does not depend much on the thickness of the membrane and is determined by the amount of electricity.
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Abstract
Description
また、前記イオン交換樹脂は、前記細孔内に該イオン交換樹脂を形成するための重合性組成物を充填しての重合により得られる。
例えば、後述する実施例に示されているように、単位厚さ当りの膜抵抗をA(Ω・cm2/cm)、海水濃縮試験におけるかん水濃度をB(mol/L)とした時、本発明のイオン交換膜(陽イオン交換膜または陰イオン交換膜)は、下記式:
B>0.006A+1.7
で表される条件を満足する。上記式は、実験値から得られた式である。該式は、単位厚さ当りの膜抵抗Aと海水濃縮試験におけるかん水濃度Bの関係式であり、本発明における効果を示す尺度である。かん水濃度Bと右辺との差が大きいほど、効果が大きいことを意味する。即ち、本発明のイオン交換膜は、膜抵抗に比して高濃度のかん水を製造することができ、優れた濃縮特性を示し、多孔性の延伸シートを基材シートとして用いたイオン交換膜よりも高いかん水濃度が得られる。
なお、本発明において海水濃縮試験とは、後述の実施例に示されているように、陽イオン交換膜と陰イオン交換膜を小型電気透析装置(通電膜面積100cm2)に組み込み、25℃で脱塩室に海水を供給し、電流密度3A/dm2で電気透析するこという。また、かん水濃度は、海水濃縮試験により得られた濃縮液のCl-濃度から求める。
本発明のイオン交換膜は、上記で述べたように、未延伸の多孔性ポリエチレンシートを基材シートとして使用している点に最大の特徴を有するものであり、この未延伸シートの表裏を貫通している微細な細孔内にイオン交換樹脂が充填された構造を有している。
イオン交換基は、水溶液中で負又は正の電荷となり得る官能基である。陽イオン交換基としては、スルホン酸基、カルボン酸基、ホスホン酸基等が挙げられ、一般的に、強酸性基であるスルホン酸基が好適である。また、陰イオン交換基としては、1~3級アミノ基、4級アンモニウム基、ピリジル基、イミダゾール基、4級ピリジニウム基等が挙げられ、一般的に、強塩基性である4級アンモニウム基や4級ピリジニウム基が好適である。
上述した構造を有する本発明のイオン交換膜は、多孔性の未延伸ポリエチレンシートを作製し、該未延伸シートの空隙部(細孔内)にイオン交換樹脂を形成するための重合性組成物を充填してイオン交換膜前駆体を作製し、次いで、該イオン交換膜前駆体中の重合性組成物の重合を行い、更に必要に応じて、重合工程で得られた重合体にイオン交換基を導入することにより製造される。
多孔性未延伸ポリエチレンシートの作製には、該シートを形成するための前述したポリエチレンを使用する。多孔性未延伸ポリエチレンシートは、該ポリエチレンに細孔を形成するための添加剤を混合してシート形成用組成物を調製し、このシート形成用組成物の押出成形等によって所定厚さの未延伸シートを成形し、次いで、前記添加剤を、有機溶剤による抽出、酸またはアルカリによる溶解等によって除去することにより作製することができる。
有機溶剤による抽出が可能な添加剤としては、可塑剤が代表的であり、例えば、フタル酸ジオクチル、フタル酸ジイソノニル、フタル酸ジイソデシル、フタル酸ジブチル等のフタル酸エステル、アジピン酸ジオクチル、アジピン酸ジイソノニル等のアジピン酸エステル、リン酸トリオクチル等のリン酸エステル、トリメリット酸トリオクチル等のトリメリット酸エステル、グリセリン酸エステル等の有機酸エステル等が挙げられる。上記以外にも、流動パラフィンや固形ワックスやミネラルオイル、クエン酸エステル、エポキシ化植物油等も有機溶剤により抽出が可能な添加剤として用いることができる。本発明においては、フタル酸エステル、特にフタル酸ジオクチル(DOP)が好ましい。
また、酸またはアルカリに溶解可能な添加剤としては、無機粉末、具体的には、シリカ、アルミナ、マイカ、タルク等を例示することができ、特にシリカが好適である。
上記のようにして作製された多孔性の未延伸ポリエチレンシートの空隙部に充填する重合性組成物は、上述したイオン交換基を導入し得る官能基(交換基導入用官能基)を有する単量体又はイオン交換基を有する単量体(以下、これらの単量体を「基本単量体成分」と呼ぶことがある)、架橋性単量体、重合開始剤等を含有するものであり、これらの成分を混合することにより調製される。
陰イオン交換基導入用官能基を有する単量体としては、スチレン、ビニルトルエン、クロロメチルスチレン、ビニルピリジン、ビニルイミダゾール、α-メチルスチレン、ビニルナフタレン等が挙げられる。
また、陰イオン交換基を有する単量体としては、ビニルベンジルトリメチルアミン、ビニルベンジルトリエチルアミン等のアミン系単量体、ビニルピリジン、ビニルイミダゾール等の含窒素複素環系単量体、それらの塩類などを挙げることができる。
このような架橋性単量体は、一般に、前述した基本単量体成分100重量部に対して、0.1~50重量部が好ましく、さらに好ましくは1~40重量部である。
このような重合開始剤は、基本単量体成分100重量部に対して、0.1~20重量部が好ましく、更に好ましくは0.5~10重量部である。
このようなマトリックス樹脂としては、例えば、エチレン-プロピレン共重合体、ポリブチレン等の飽和脂肪族炭化水素系ポリマー、スチレンーブタジエン共重合体等のスチレン系ポリマー、ニトリルブタジエンゴム、水素添加ニトリルブタジエンゴム、エピクロロヒドリンゴム、ポリ塩化ビニル、塩素化ポリエチレンゴム或いは、これらに、各種のコモノマー(例えばビニルトルエン、ビニルキシレン、クロロスチレン、クロロメチルスチレン、α-メチルスチレン、α-ハロゲン化スチレン、α,β,β´-トリハロゲン化スチレン等のスチレン系モノマーや、エチレン、ブチレン等のモノオレフィンや、ブタジエン、イソプレン等の共役ジオレフィンなど)を共重合させたものなどを使用することができる。
これらのマトリックス樹脂は、重合性組成物が垂れ等を生じることなく、多孔性未延伸ポリエチレンシートの空隙部に速やかに充填保持し得るような粘度となるような量で使用される。
また、重合性組成物には、重合後の膜状物の柔軟性を付与するために、あるいは交換基導入を容易に進めるために、必要に応じて可塑剤を配合することもできる。可塑剤としては、フタル酸ジオクチル、フタル酸ジブチル等のフタル酸エステル、アジピン酸ジオクチル、アジピン酸ジイソノニル等のアジピン酸エステル、スチレンオキサイド等のエポキシ類、ジフェニルエーテル、ジベンジルエーテル等のエーテル類等が使用される。
上記の重合性組成物は、前述した多孔性未延伸ポリエチレンシートの空隙部に充填され、これにより、空隙部に重合性組成物が充填されたイオン交換膜前駆体を得る。
本発明においては、このような未延伸のポリエチレンシートの空隙部に重合性組成物が充填されて重合が行われるため、重合により得られるイオン交換樹脂と基材シートとなる該ポリエチレンシートとの密着性が極めて高く、この結果、このイオン交換膜を用いて電気透析を行った場合、濃縮特性が向上するものと本発明者らは考えている。即ち、未延伸のポリエチレンシートでは、ポリエチレン分子が配向されておらず、分子の配列がランダムとなっているため、分子間間隙に単量体分子が侵入し易いものとなっている。従って、単量体と多孔性未延伸ポリエチレンシートの表面との親和性が高く、形成される重合体(イオン交換樹脂)と基材シートである多孔性未延伸ポリエチレンシートとの間に高い密着性が得られることとなる。このように、イオン交換樹脂と基材シート(多孔性未延伸ポリエチレンシート)との間に高い密着性が確保されている結果、このようなイオン交換膜を用いて電気透析をおこなうと、所定極性のイオン(陰イオン交換膜においてはアニオン、陽イオン交換膜においてはカチオン)は透過するが、水分子や他のイオンの透過が有効に抑制され(イオン交換樹脂と基材シートとの間に空隙部がほとんど存在しない)、濃縮特性が向上するのである。
これに対して、従来公知のイオン交換膜では、多孔性の基材シートとして延伸された樹脂シートが使用されているため、イオン交換樹脂と基材シートとの間に高い密着性を確保することができず、その密着性が不十分であるため、高い濃縮特性を得ることができない。即ち、多孔性の延伸樹脂シートでは樹脂分子が配向されており、規則的に配列されているため、分子間間隙に単量体分子が入り込みにくく、得られるイオン交換樹脂と基材シートである多孔性の延伸樹脂シートとは親和性に乏しく、両者の密着性は極めて低い。この結果、このイオン交換膜を用いて電気透析をおこなった場合、所定極性のイオンと共に水分子や他のイオンの透過を生じてしまい、その濃縮特性は低いものとなってしまうのである。
上記のようにして、多孔性未延伸ポリエチレンシートの空隙部への重合性組成物の充填をおこなって得られるイオン交換膜前駆体は重合工程に供される。基本単量体成分としてイオン交換基を有する単量体が使用されている場合には、この工程の完了により目的とするイオン交換膜が得られる。また、基本単量体成分として、交換基導入用官能基を有する単量体を用いた場合には、この工程の完了後に、イオン交換基の導入が必要となる。
重合は、未延伸ポリエチレンシートの融点よりも高い温度でも可能ではあるが、得られたイオン交換膜の強度が低下することがあるので、未延伸ポリエチレンシートの融点付近かあるいは融点より低い温度でおこなう。一般的には、40~140℃の範囲がよい。即ち、係る温度範囲に加熱して重合を行うことにより、未延伸ポリエチレンシートの一部が重合性組成物中に溶解した状態で重合がおこなわれることとなり、この結果、未延伸ポリエチレンシートとイオン交換樹脂との接合強度を高めることができ、膜強度を一層向上させることができる。
重合は、空気中でおこなうことも可能ではあるが、重合が空気中の酸素により阻害されることがあるので、窒素雰囲気下でおこなうことが望ましい。また、重合時間は、重合温度等によっても異なるが、一般には、30分~24時間程度である。
先に述べたように、重合性組成物中の基本単量体成分として、イオン交換基を有する単量体を用いた場合には、上記の重合工程によりイオン交換樹脂が形成され、この段階で目的とするイオン交換膜が得られるが、基本単量体成分として、交換基導入用官能基を有する単量体を用いた場合には、上記の重合工程で得られる樹脂はイオン交換基を有していないため、重合工程後にイオン交換基の導入を行う必要がある。
なお、実施例、比較例に示す基材シートおよびイオン交換膜の特性は以下の方法により測定した。
東洋精機製の微少測厚器(タイプKBN、端子径Φ5mm、測定圧62.47kPa)を用いて、雰囲気温度23±2℃で測定した。
100mm×100mm角の試料を微多孔膜から切り取り、その体積(mm3)と質量(mg)を求め、それらと膜密度(g/cm3)より、次式を用いて計算した。
気孔率(%)=(体積-質量/膜密度)/体積×100
尚、体積は試料大きさと膜厚より計算し、膜密度は材料密度より計算した。
JIS P-8117に準拠し、ガーレー式透気度計(東洋精器(株)製、G-B2(商標))を用いた。
JIS K7127に準拠し、引張試験機{株式会社オリエンテック社製テンシロン万能試験機 RTG-1210(商標)}を用いて、MD及びTDサンプル(図1)について測定した。チャック間隔を50mmとした。引張伸度(%)は、接触式伸び計を標線間に装着して、サンプルが破断に至るまでの伸び量(mm)を測定し、該伸び量(mm)を標線間距離(20mm)で除して、100を乗じることにより求めた。なお、測定は、温度23±2℃、チャック圧0.50MPa、引張速度100mm/分で行った。
ASTM-D4020に基づき、デカリン溶媒における135℃での極限粘度[η]を求めた。ポリエチレンの粘度平均分子量(Mv)は次式により算出した。
ポリエチレンの場合
[η]=6.77×10-4×Mv0.67
白金黒電極を有する2室セル中にイオン交換膜を挟み、イオン交換膜の両側に0.5mol/L-NaCl溶液を満たし、交流ブリッジ(周波数1000サイクル/秒)により25℃における電極間の抵抗を測定した。該電極間抵抗とイオン交換膜を設置しない場合の電極間抵抗との差により膜抵抗を求めた。上記測定に使用するイオン交換膜は、予め0.5mol/LNaCl溶液中で平衡にしたものを用いた。
0.5mol/L-NaCl溶液に浸漬した後、ティッシュペーパーで膜の表面を拭いてマイクロモメ-タ MED-25PJ(株式会社ミツトヨ社製)を用いて測定した。
次式により算出した。
単位厚さ当りの膜抵抗(Ω・cm2/cm)=膜抵抗(Ω・cm2)/膜の厚さ(cm)
実施例および比較例で示した陽イオン交換膜は、製塩用陰イオン交換膜ACS(株式会社アストム社製)と、実施例および比較例で示した陰イオン交換膜は、製塩用陽イオン交換膜CIMS(株式会社アストム社製)とそれぞれ対にして、小型電気透析装置(通電膜面積100cm2)に組み込み、海水濃縮試験を実施した。濃縮条件は、脱塩室の流速6cm/秒、電流密度3A/dm2として、25℃で海水を供給した。得られた濃縮液のCl-濃度をかん水濃度とした。
製造例1;
粘度平均分子量が100万の超高分子量ポリエチレン19.2重量部、粘度平均分子量が25万の高密度ポリエチレン12.8重量部、フタル酸ジオクチル(DOP)48重量部、微粉シリカ20重量部を混合造粒した後、先端にTダイを装着した二軸押出機にて溶融混練した後に押出し、両側から加熱したロ-ルで圧延し、厚さ110μmのシート状に成形した。該成形物からDOP、微粉シリカを抽出除去し多孔性未延伸ポリエチレンシ-トを作製した。
厚さ;90μm
気孔率:50%
透気度;1,150秒/100cc
引張伸度;MD 590%、TD 941%
製造例2;
製造例1で得られた多孔性未延伸ポリエチレンシートを、120℃でTDに延伸速度10%/秒で2.5倍一軸延伸した後、130℃で熱処理をして多孔性延伸ポリエチレンシートを得た。
この多孔性延伸ポリエチレンシートの各種物性は以下のとおりであった。
厚さ:34μm
気孔率:49%
透気度:96秒/100cc
引張伸度:MD 537%、TD方向 255%
スチレン82.5重量部、ジビニルベンゼン(純度57%)17.5重量部、ジブチルフタレート5重量部、パーブチルO(t-ブチルパーオキシ-2-エチルヘキサノエート 日本油脂株式会社製)2重量部を混合して重合性組成物を調製した。
この重合性組成物500gを1000mlのガラス容器に入れ、ここに基材シートとして製造例1で作製された多孔性未延伸ポリエチレンシートを浸漬して、該シートの細孔内に重合体組成物を充填した。
得られた膜状物を98%濃硫酸と純度90%以上のクロロスルホン酸の1:1(重量比)の混合物中に40℃で60分浸漬した。その後、膜状物を90%硫酸、60%硫酸、イオン交換水に順次浸漬し、さらに4mol/L-NaOH水溶液に12時間浸漬、水洗することによりスルホン酸型陽イオン交換膜を得た。
得られた陽イオン交換膜の電気抵抗は、1.16Ω・cm2、厚さは107μm、かん水濃度は3.22mol/Lであった。
製造例2で得られた多孔性延伸ポリエチレンシートを基材シートとして用いた以外は、実施例1と全く同様にして陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性の測定結果を表1に示す。
製造例1で得られた多孔性未延伸ポリエチレンシートを用いて、表1に示すようにスチレンとDVB(純度57%)の重量部以外は、実施例1と同様にして陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性の測定結果を表1に示す。
製造例2で得られた多孔性延伸ポリエチレンを基材シートとして用いた以外は、実施例2、3と全く同様にして陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性の測定結果を表1に示す。実施例1~3、比較例1~3で得られた陽イオン交換膜の単位厚さ当りの膜抵抗とかん水濃度との関係を図2に示す。
クロロメチルスチレン89.5重量部、ジビニルベンゼン(純度57%)10.5重量部、スチレンオキサイド2重量部、パーブチルO4重量部を混合して重合性組成物を調製した。
この重合性組成物500gを1000mlのガラス容器に入れ、ここに基材シートとして製造例1で作製された多孔性未延伸ポリエチレンシートを浸漬して、該シートの空隙部に重合体組成物を充填した。
上記の重合体組成物を充填した多孔性未延伸ポリエチレンシートを取り出し、100μmのポリエステルフィルムを剥離材としてポリエチレンシートの両側を被覆した後、0.4MPaの窒素加圧下、80℃で5時間、さらにその後90℃で2時間加熱重合した。
得られた膜状物を30%トリメチルアミン水溶液15重量部、水52.5重量部、アセトン22.5重量部の混合物中に30℃で16時間浸漬して、4級アンモニウム型陰イオン交換膜を得た。
得られた陰イオン交換膜の抵抗は、0.88Ω・cm2、膜の厚さは103.5μm、かん水濃度は2.29mol/Lであった。これらの膜特性の結果は表2に示した。
製造例2で作製された多孔性延伸ポリエチレンシートを基材シートとして用いた以外は、実施例4と全く同様にして陰イオン交換膜を得た。得られた陰イオン交換膜の膜特性の測定結果を表2に示す。
製造例1で得られた多孔性未延伸ポリエチレンシートを用いて、表2に示すようにクロロメチルスチレンとDVB(純度57%)の重量部以外は、実施例4と同様にして陰イオン交換膜を得た。得られた陰イオン交換膜の膜特性の測定結果を表2に示す。
製造例2で作製された多孔性延伸ポリエチレンを基材シートとして用いた以外は、実施例5、6と全く同様にして陰イオン交換膜を得た。得られた陰イオン交換膜の膜特性の測定結果を表2に示す。実施例4~6、比較例4~6で得られた陰イオン交換膜の単位厚さ当りの膜抵抗とかん水濃度との関係を図3に示す。
延伸条件を変更した以外は、製造例2と同様にして、以下の多孔性延伸ポリエチレンシートを得た。
厚さ:56μm
気孔率:62%
透気度:116秒/100cc
引張伸度:MD 94%、TD方向 338%
この重合性組成物と上記の多孔性延伸ポリエチレンシートとを用いた以外は、実施例4と同様にして、陰イオン交換膜を得た。
得られた陰イオン交換膜の電気抵抗は、0.59Ω・cm2、厚さは66μm、かん水濃度は1.79mol/Lであった。
比較例7で得られた陰イオン交換膜、及び比較例7に近い膜組成の実施例6、比較例6で得られた陰イオン交換膜について、厚みとかん水濃度との関係を図4に示す。
(a)かん水濃度(濃縮特性)は膜の厚さに依存しないこと、
(b)実施例6のように、未延伸の多孔質シートを基材シートして用いることにより、かん水濃度が向上していること、
が理解される。
電気透析によって得られるかん水濃度は、主としてイオンの膜透過に付随して移動する水和水(電気浸透水と一般に呼ばれていて、電気浸透水が大きいとかん水濃度が低くなる)の量や膜のイオン選択透過性により決まり、これらの性能は膜の厚さに依存するものではなく、膜の構造に大きく影響を受けるものである。即ち、膜ろ過のような圧力差駆動の系では、膜の厚みが物質の膜透過(拡散による透過流束)に強く影響を及ぼすが、電気透析の場合はそれとは異なり、電位差を駆動力とした系のため、イオンの膜透過量は膜厚みにあまり依存せず電気量で決まるものである。
Claims (4)
- 微細な細孔が貫通している多孔性未延伸ポリエチレンシートの該細孔内にイオン交換樹脂が充填されて成るイオン交換膜。
- 前記多孔性未延伸ポリエチレンシートは、厚さが10~300μmであり、気孔率が30~80%である請求項1に記載のイオン交換膜。
- 前記多孔性未延伸ポリエチレンシートは、長さ方向(MD)及び軸方向(TD)の引張伸度がいずれも450%以上である請求項1に記載のイオン交換膜。
- 前記イオン交換樹脂は、前記細孔内に該イオン交換樹脂を形成するための重合性組成物を充填しての重合により得られたものである請求項2に記載のイオン交換膜。
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US14/007,290 US9162185B2 (en) | 2011-03-29 | 2012-03-28 | Ion-exchange membrane |
EP12764720.4A EP2692782A4 (en) | 2011-03-29 | 2012-03-28 | ION EXCHANGE MEMBRANE |
CN201280015358.0A CN103443172B (zh) | 2011-03-29 | 2012-03-28 | 离子交换膜 |
KR1020137025621A KR101840900B1 (ko) | 2011-03-29 | 2012-03-28 | 이온 교환막 |
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