JP2024007836A - composite semipermeable membrane - Google Patents
composite semipermeable membrane Download PDFInfo
- Publication number
- JP2024007836A JP2024007836A JP2022109187A JP2022109187A JP2024007836A JP 2024007836 A JP2024007836 A JP 2024007836A JP 2022109187 A JP2022109187 A JP 2022109187A JP 2022109187 A JP2022109187 A JP 2022109187A JP 2024007836 A JP2024007836 A JP 2024007836A
- Authority
- JP
- Japan
- Prior art keywords
- composite semipermeable
- semipermeable membrane
- membrane
- water
- porous support
- 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 142
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000926 separation method Methods 0.000 claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000004952 Polyamide Substances 0.000 claims abstract description 33
- 229920002647 polyamide Polymers 0.000 claims abstract description 33
- 239000010409 thin film Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000002346 layers by function Substances 0.000 claims description 52
- 239000010410 layer Substances 0.000 claims description 38
- 239000010408 film Substances 0.000 claims description 19
- 230000035699 permeability Effects 0.000 abstract description 8
- 230000003247 decreasing effect Effects 0.000 abstract 1
- -1 aliphatic amines Chemical class 0.000 description 46
- 239000000243 solution Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 29
- 150000001412 amines Chemical class 0.000 description 26
- 239000002253 acid Substances 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 23
- 150000004820 halides Chemical class 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 22
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 11
- 239000012954 diazonium Substances 0.000 description 10
- 150000001989 diazonium salts Chemical class 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 238000012696 Interfacial polycondensation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 5
- 150000004982 aromatic amines Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 2
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 2
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920012287 polyphenylene sulfone Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 2
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- AMBFNDRKYCJLNH-UHFFFAOYSA-N 1-(3-piperidin-1-ylpropyl)piperidine Chemical compound C1CCCCN1CCCN1CCCCC1 AMBFNDRKYCJLNH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 1
- BFWYZZPDZZGSLJ-UHFFFAOYSA-N 4-(aminomethyl)aniline Chemical compound NCC1=CC=C(N)C=C1 BFWYZZPDZZGSLJ-UHFFFAOYSA-N 0.000 description 1
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006149 azo coupling reaction Methods 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- AKXTUELRIVKQSN-UHFFFAOYSA-N cyclobutane-1,2,3-tricarbonyl chloride Chemical compound ClC(=O)C1CC(C(Cl)=O)C1C(Cl)=O AKXTUELRIVKQSN-UHFFFAOYSA-N 0.000 description 1
- MLCGVCXKDYTMRG-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1 MLCGVCXKDYTMRG-UHFFFAOYSA-N 0.000 description 1
- HIZMBMVNMBMUEE-UHFFFAOYSA-N cyclohexane-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1CC(C(Cl)=O)CC(C(Cl)=O)C1 HIZMBMVNMBMUEE-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- YYLFLXVROAGUFH-UHFFFAOYSA-N cyclopentane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1 YYLFLXVROAGUFH-UHFFFAOYSA-N 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- LSHSZIMRIAJWRM-UHFFFAOYSA-N oxolane-2,3-dicarbonyl chloride Chemical compound ClC(=O)C1CCOC1C(Cl)=O LSHSZIMRIAJWRM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical compound NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
Description
本発明は、液状混合物の選択的分離に有用な複合半透膜に関する。 The present invention relates to composite semipermeable membranes useful for selective separation of liquid mixtures.
混合物の分離に関して、溶媒（例えば水）に溶解した物質（例えば塩類）を除くための技術には様々なものがある。近年、省エネルギーおよび省資源のためのプロセスとして膜分離法の利用が拡大している。 Regarding separation of mixtures, there are various techniques for removing substances (eg, salts) dissolved in a solvent (eg, water). In recent years, the use of membrane separation methods has been expanding as a process for saving energy and resources.
膜分離法に使用される膜には、精密ろ過膜、限外ろ過膜、ナノろ過膜、逆浸透膜などがある。これらの膜は、例えば海水、かん水、有害物を含んだ水などから飲料水を得ること、または工業用超純水の製造、排水処理、有価物の回収などに用いられている。 Membranes used in membrane separation methods include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, and reverse osmosis membranes. These membranes are used, for example, to obtain drinking water from seawater, brackish water, water containing harmful substances, etc., to produce industrial ultrapure water, to treat wastewater, to recover valuable materials, and the like.
特許文献１には、多孔性支持膜と、その上に被覆された架橋ポリアミドからなる分離機能層と有する複合半透膜が、透水性および除去性の高い分離膜として開示されている。分離機能層は多官能性アミンと多官能性酸ハロゲン化物との重縮合反応によって多孔性支持膜上に形成される。
近年、膜運転時の省エネルギー化のニーズが高まっており、複合半透膜の透水性は従来に対しさらに高める必要があるが、膜の透水性を高めるために膜構造を変化させると、それに伴い除去性が低下する問題があった。 In recent years, there has been an increasing need for energy saving during membrane operation, and the water permeability of composite semipermeable membranes needs to be further increased compared to conventional membranes. There was a problem that removability deteriorated.
そこで、本発明は上記に鑑み、除去性能を低下させることなく透水性を高めた複合半透膜を提供することを課題とする。 Therefore, in view of the above, an object of the present invention is to provide a composite semipermeable membrane with improved water permeability without reducing removal performance.
上記課題を解決するための本発明は、以下１～５の構成を包含する。
１．多孔性支持層と該多孔性支持層上に位置する分離機能層を有する複合半透膜であって、前記分離機能層は、架橋ポリアミドを主成分とする薄膜を有し、前記薄膜は下記一般式（１）で表される化合物を含有する複合半透膜。
The present invention for solving the above problems includes
1. A composite semipermeable membrane having a porous support layer and a separation functional layer located on the porous support layer, the separation functional layer having a thin film mainly composed of cross-linked polyamide, and the thin film having the following general properties. A composite semipermeable membrane containing a compound represented by formula (1).
（式（１）中のＲ１は水素原子または炭素数１～８の脂肪族炭化水素基を表す。）
２．前記一般式（１）で表される化合物が、前記薄膜に対して単位膜面積当たり１．０×１０－４ｍｏｌ／ｍ２以上１．０×１０－３ｍｏｌ／ｍ２以下で含有されている、前記１に記載の複合半透膜。
３．前記分離機能層は、前記薄膜により形成された複数の凸部と凹部を備えたひだ構造を有する、前記１または２に記載の複合半透膜。
４．前記凸部の平均高さが１００ｎｍ以上２５０ｎｍ以下である、前記３に記載の複合半透膜。
５．前記分離機能層の表面における水の接触角が４０度以下である、１～４のいずれか１つに記載の複合半透膜。
(R 1 in formula (1) represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.)
2. The compound represented by the general formula (1) is contained in the thin film in an amount of 1.0×10 −4 mol/m 2 or more and 1.0×10 −3 mol/m 2 or less per unit film area. The composite semipermeable membrane according to 1 above.
3. 3. The composite semipermeable membrane according to
4. 3. The composite semipermeable membrane according to 3 above, wherein the average height of the convex portions is 100 nm or more and 250 nm or less.
5. 5. The composite semipermeable membrane according to any one of 1 to 4, wherein the contact angle of water on the surface of the separation functional layer is 40 degrees or less.
本発明の複合半透膜は、該複合半透膜の分離機能層を構成する薄膜に前記一般式（１）で表される化合物を含有することで、被処理水の除去性能を低下させることなく透水性を高めることができる。よって、本発明の複合半透膜は、高除去化、高造水化に効果がある。本発明の複合半透膜は、例えば海水またはかん水の淡水化に好適に用いることができる。 The composite semipermeable membrane of the present invention contains the compound represented by the general formula (1) in the thin film constituting the separation functional layer of the composite semipermeable membrane, thereby reducing the removal performance of water to be treated. water permeability can be increased without Therefore, the composite semipermeable membrane of the present invention is effective in high removal and high water production. The composite semipermeable membrane of the present invention can be suitably used, for example, for desalination of seawater or brine.
（１）複合半透膜
本発明の複合半透膜は、多孔性支持層と、多孔性支持層上に位置する分離機能層とを備える。
(1) Composite Semipermeable Membrane The composite semipermeable membrane of the present invention includes a porous support layer and a separation functional layer located on the porous support layer.
（１－１）分離機能層
複合半透膜の構成要素のうち、実質的に溶質の分離性能を有するのは分離機能層である。
分離機能層は、溶質分離性能に優れ且つ高い造水量を示すことから、架橋ポリアミドを主成分として含有する薄膜（以下、「架橋ポリアミド膜」とも称する。）を有する。分離機能層は、１層の架橋ポリアミド膜からなるものでもよいし、物性の異なる架橋ポリアミド膜を複数層備えていてもよいし、架橋ポリアミド膜以外の溶質分離機能を有する層を備えていてもよい。
(1-1) Separation Functional Layer Among the constituent elements of the composite semipermeable membrane, the separation function layer has substantial solute separation performance.
The separation functional layer has a thin film containing crosslinked polyamide as a main component (hereinafter also referred to as "crosslinked polyamide membrane") because it has excellent solute separation performance and shows a high amount of water production. The separation functional layer may consist of a single layer of crosslinked polyamide membrane, may include multiple layers of crosslinked polyamide membranes with different physical properties, or may include a layer having a solute separation function other than the crosslinked polyamide membrane. good.
なお、本書において「ＸがＹを主成分として含有する」とは、ＹがＸの５０質量％以上を含むことを意味し、好ましくは８０質量％以上、より好ましくは９０質量％以上を含み、ＸがＹのみで構成される場合も含む。 In this document, "X contains Y as a main component" means that Y contains 50% by mass or more of X, preferably 80% by mass or more, more preferably 90% by mass or more, This also includes cases where X is composed of only Y.
架橋ポリアミドは、多官能性アミンと多官能性酸ハロゲン化物との重縮合物である。 Crosslinked polyamide is a polycondensate of a polyfunctional amine and a polyfunctional acid halide.
多官能性アミンとは、一分子中に少なくとも２個の第一級アミノ基および／または第二級アミノ基を有し、そのアミノ基のうち少なくとも１つは第一級アミノ基であるアミンをいう。多官能性アミンとしては、例えば、２個のアミノ基がオルト位またはメタ位、パラ位のいずれかの位置関係でベンゼン環に結合したフェニレンジアミン、キシリレンジアミン、１，３，５－トリアミノベンゼン、１，２，４－トリアミノベンゼン、３，５－ジアミノ安息香酸、３－アミノベンジルアミン、４－アミノベンジルアミンなどの多官能芳香族アミン、エチレンジアミン、プロピレンジアミンなどの脂肪族アミン、１，２－ジアミノシクロヘキサン、１，４－ジアミノシクロヘキサン、４－アミノピペリジン、４－アミノエチルピペラジンなどの脂環式多官能アミン等を挙げることができる。 A polyfunctional amine is an amine that has at least two primary amino groups and/or secondary amino groups in one molecule, and at least one of the amino groups is a primary amino group. say. Examples of polyfunctional amines include phenylenediamine, xylylenediamine, and 1,3,5-triamino in which two amino groups are bonded to a benzene ring at the ortho, meta, or para positions. Polyfunctional aromatic amines such as benzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid, 3-aminobenzylamine, 4-aminobenzylamine, aliphatic amines such as ethylenediamine, propylenediamine, 1 Examples include alicyclic polyfunctional amines such as , 2-diaminocyclohexane, 1,4-diaminocyclohexane, 4-aminopiperidine, and 4-aminoethylpiperazine.
なかでも、膜の選択分離性および透過性、耐熱性を考慮すると、多官能性アミンは、一分子中に２～４個の第一級アミノ基および／または第二級アミノ基を有する多官能芳香族アミンであることが好ましい。このような多官能芳香族アミンとしては、例えば、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、１，３，５－トリアミノベンゼン等が好適に用いられる。なかでも、入手の容易性または取り扱いのしやすさから、ｍ－フェニレンジアミン（以下、ｍ－ＰＤＡと記す）を用いることがより好ましい。 Among them, considering the selective separation, permeability, and heat resistance of the membrane, polyfunctional amines have 2 to 4 primary amino groups and/or secondary amino groups in one molecule. Preferably it is an aromatic amine. As such polyfunctional aromatic amines, for example, m-phenylenediamine, p-phenylenediamine, 1,3,5-triaminobenzene, etc. are preferably used. Among these, it is more preferable to use m-phenylenediamine (hereinafter referred to as m-PDA) because of its ease of availability and ease of handling.
これらの多官能性アミンは、単独で用いても、２種以上を同時に用いてもよい。２種以上を同時に用いる場合、上記アミン同士を組み合わせてもよく、上記アミンと、一分子中に少なくとも２個の第二級アミノ基を有するアミンとを組み合わせてもよい。一分子中に少なくとも２個の第二級アミノ基を有するアミンとして、例えば、ピペラジン、１，３－ビスピペリジルプロパン等を挙げることができる。 These polyfunctional amines may be used alone or in combination of two or more. When two or more types are used simultaneously, the above amines may be combined with each other, or the above amine may be combined with an amine having at least two secondary amino groups in one molecule. Examples of amines having at least two secondary amino groups in one molecule include piperazine and 1,3-bispiperidylpropane.
多官能性酸ハロゲン化物とは、一分子中に少なくとも２個のハロゲン化カルボニル基を有する酸ハロゲン化物をいう。例えば、３官能酸ハロゲン化物としては、例えば、トリメシン酸クロリド、１，３，５－シクロヘキサントリカルボン酸トリクロリド、１，２，４－シクロブタントリカルボン酸トリクロリドなどを挙げることができる。 The polyfunctional acid halide refers to an acid halide having at least two halogenated carbonyl groups in one molecule. For example, examples of the trifunctional acid halide include trimesic acid chloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, and 1,2,4-cyclobutanetricarboxylic acid trichloride.
２官能酸ハロゲン化物としては、例えば、ビフェニルジカルボン酸ジクロリド、アゾベンゼンジカルボン酸ジクロリド、テレフタル酸クロリド、イソフタル酸クロリド、ナフタレンジカルボン酸クロリドなどの芳香族２官能酸ハロゲン化物、アジポイルクロリド、セバコイルクロリドなどの脂肪族２官能酸ハロゲン化物、シクロペンタンジカルボン酸ジクロリド、シクロヘキサンジカルボン酸ジクロリド、テトラヒドロフランジカルボン酸ジクロリドなどの脂環式２官能酸ハロゲン化物等を挙げることができる。 Examples of difunctional acid halides include aromatic difunctional acid halides such as biphenyldicarboxylic acid dichloride, azobenzenedicarboxylic acid dichloride, terephthalic acid chloride, isophthalic acid chloride, and naphthalenedicarboxylic acid chloride, adipoyl chloride, and sebacoyl chloride. Examples include aliphatic bifunctional acid halides such as cyclopentanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
多官能性アミンとの反応性を考慮すると、多官能性酸ハロゲン化物は多官能性酸塩化物であることが好ましく、また、膜の選択分離性、耐熱性を考慮すると、一分子中に２～４個の塩化カルボニル基を有する多官能性芳香族酸塩化物であることがより好ましい。なかでも、入手の容易性または取り扱いのしやすさの観点から、トリメシン酸クロリド（以下、ＴＭＣと記す）を用いるとさらに好ましい。これらの多官能性酸ハロゲン化物は、単独で用いても、２種以上を同時に用いてもよい。 Considering the reactivity with polyfunctional amines, the polyfunctional acid halide is preferably a polyfunctional acid chloride, and considering the selective separation property and heat resistance of the membrane, it is preferable that the polyfunctional acid halide contains 2 More preferably, it is a polyfunctional aromatic acid chloride having ~4 carbonyl chloride groups. Among these, it is more preferable to use trimesic acid chloride (hereinafter referred to as TMC) from the viewpoint of ease of availability or ease of handling. These polyfunctional acid halides may be used alone or in combination of two or more.
本発明の複合半透膜は、架橋ポリアミド膜に下記式（１）で表される化合物（以下、「Ｎ置換マレイミド化合物（１）とも称する。）を含有する。 The composite semipermeable membrane of the present invention contains a compound represented by the following formula (1) (hereinafter also referred to as "N-substituted maleimide compound (1))" in a crosslinked polyamide membrane.
（式（１）中のＲ１は水素原子または炭素数１～８の脂肪族炭化水素基を表す。） (R 1 in formula (1) represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms.)
一般式（１）における炭素数１～８の脂肪族炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基等の炭素数１～８のアルキル基が挙げられる。化合物の立体障害の観点から、式（１）中のＲ１は、水素原子または炭素数１～６のアルキル基がより好ましく、水素原子または炭素数１～４のアルキル基がさらに好ましい。 Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms in general formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, and hexyl group. Examples include alkyl groups having 1 to 8 carbon atoms. From the viewpoint of steric hindrance of the compound, R 1 in formula (1) is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
前記一般式（１）で表される化合物としては、具体的に、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－プロピルマレイミド、Ｎ－ｉ－プロピルマレイミド、Ｎ－ブチルマレイミド、Ｎ－ｉ－ブチルマレイミド、Ｎ－ｔ－ブチルマレイミド等が挙げられる。 Specific examples of the compound represented by the general formula (1) include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Ni-propylmaleimide, N-butylmaleimide, Ni-butyl Examples include maleimide and Nt-butylmaleimide.
本発明者らは、架橋ポリアミド膜の内部にＮ置換マレイミド化合物（１）が含有されることで、一部のＮ置換マレイミド化合物（１）は、Ｎ置換マレイミド化合物（１）の片側カルボニル基が架橋ポリアミド膜中のポリアミドの官能基と水素結合し、反対側のカルボニル基が架橋ポリアミド膜中の水と水素結合を示し、これにより水透過の連通性が向上し高い造水性を有し、また、別の一部のＮ置換マレイミド化合物（１）は、Ｎ置換マレイミド化合物（１）の両側カルボニル基がポリアミド主鎖の官能基と水素結合を示すことで、ポリマーの高次構造の安定性が向上し、除去性が向上することを見出した。 The present inventors discovered that by containing the N-substituted maleimide compound (1) inside the crosslinked polyamide membrane, some of the N-substituted maleimide compounds (1) have a carbonyl group on one side of the N-substituted maleimide compound (1). It forms a hydrogen bond with the polyamide functional group in the cross-linked polyamide membrane, and the carbonyl group on the opposite side forms a hydrogen bond with the water in the cross-linked polyamide membrane, which improves water permeation connectivity and has high water-forming properties. Another part of the N-substituted maleimide compound (1) is that the carbonyl groups on both sides of the N-substituted maleimide compound (1) exhibit hydrogen bonds with the functional groups of the polyamide main chain, thereby increasing the stability of the higher-order structure of the polymer. It has been found that the removability is improved.
架橋ポリアミド膜におけるＮ置換マレイミド化合物（１）の含有を検出する方法としては特に限定されないが、例えばガスクロマトグラフィー質量分析法を利用して検出する方法がある。例えば、複合半透膜１００ｃｍ２を切り抜き、５０ｍＬのエタノール中に８時間浸漬させＮ置換マレイミド化合物（１）を抽出する。抽出させた成分をあらかじめ検量線を得たガスクロマトグラフィーで測定し、膜面積当たりのＮ置換マレイミド化合物（１）の物質量を算出することができる。 Although the method for detecting the content of the N-substituted maleimide compound (1) in the crosslinked polyamide membrane is not particularly limited, for example, there is a method of detecting the content using gas chromatography mass spectrometry. For example, a 100 cm 2 composite semipermeable membrane is cut out and immersed in 50 mL of ethanol for 8 hours to extract the N-substituted maleimide compound (1). The extracted components are measured by gas chromatography with a calibration curve obtained in advance, and the amount of the N-substituted maleimide compound (1) per membrane area can be calculated.
Ｎ置換マレイミド化合物（１）の含有量は、架橋ポリアミド膜に対して、単位膜面積当たり１．０×１０－４ｍｏｌ／ｍ２以上１．０×１０－３ｍｏｌ／ｍ２以下の範囲であるのが好ましい。Ｎ置換マレイミド化合物（１）の含有量が前記範囲であると、上記した本発明の効果が顕著に得られる。Ｎ置換マレイミド化合物（１）の含有量は、下限は２．０×１０－４ｍｏｌ／ｍ２以上であるのがより好ましく、３．０×１０－４ｍｏｌ／ｍ２以上がさらに好ましく、また、上限は９．０×１０－４ｍｏｌ／ｍ２以下であるのがより好ましく、８．０×１０－４ｍｏｌ／ｍ２以下がさらに好ましい。 The content of the N-substituted maleimide compound (1) is in the range of 1.0×10 −4 mol/m 2 or more and 1.0×10 −3 mol/m 2 or less per unit membrane area with respect to the crosslinked polyamide membrane. It is preferable to have one. When the content of the N-substituted maleimide compound (1) is within the above range, the effects of the present invention described above can be significantly obtained. The lower limit of the content of the N-substituted maleimide compound (1) is more preferably 2.0×10 −4 mol/m 2 or more, further preferably 3.0×10 −4 mol/m 2 or more, and The upper limit is more preferably 9.0×10 −4 mol/m 2 or less, and even more preferably 8.0×10 −4 mol/m 2 or less.
分離機能層は、前記架橋ポリアミド膜により形成された複数の凸部と凹部を備えたひだ構造を有することが好ましい。このひだ構造においては、薄膜である架橋ポリアミド膜により凹部と凸部とが繰り返される。分離機能層がひだ構造を有することで、機能層の表面積が大きくなり、造水量が向上する。 Preferably, the separation functional layer has a pleated structure including a plurality of convex portions and concave portions formed by the crosslinked polyamide membrane. In this pleated structure, concave portions and convex portions are repeated due to the thin crosslinked polyamide film. Since the separation functional layer has a pleated structure, the surface area of the functional layer increases and the amount of water produced increases.
ここで、凸部とは、１０点平均面粗さの５分の１以上の高さを有する凸部である。
１０点平均面粗さは、次のように算出される。まず電子顕微鏡により、膜面に垂直な方向の断面を観察する。観察倍率は１０，０００～１００，０００倍が好ましい。得られた断面画像には、図１に示すように、分離機能層１の表面が、凸部と凹部が連続的に繰り返されるひだ構造の曲線として表れる。この曲線について、ＪＩＳ Ｂ ０６０１（ＩＳＯ４２８７：１９９７）に基づき定義される粗さ曲線を求める。なお、平均線とは、ＩＳＯ４２８７：１９９７に基づき定義される直線であり、測定長さにおいて、平均線と粗さ曲線とで囲まれる領域の面積の合計が平均線の上下で等しくなるように描かれる直線である。
Here, the convex portion is a convex portion having a height of one-fifth or more of the 10-point average surface roughness.
The 10-point average surface roughness is calculated as follows. First, a cross section perpendicular to the film surface is observed using an electron microscope. The observation magnification is preferably 10,000 to 100,000 times. In the obtained cross-sectional image, as shown in FIG. 1, the surface of the separation
この抜取り部分の平均線から、粗さ曲線の最も高い山頂から５番目までの山頂の標高（Ｈ1～５）の絶対値の平均値と、最も低い谷底から５番目までの谷底の標高（Ｄ１～５）の絶対値の平均値との和を求め、この値をマイクロメートル（ｎｍ）で表したものが１０点平均面粗さである。なお、平均線とは、ＩＳＯ４２８７：１９９７に基づき定義される直線であり、測定長さにおいて、平均線と粗さ曲線とで囲まれる領域の面積の合計が平均線の上下で等しくなるように描かれる直線である。 From the average line of this sampled part, the average value of the absolute value of the elevation of the fifth peak from the highest peak of the roughness curve (H1 to 5) and the elevation of the fifth valley bottom from the lowest valley bottom (D1 to 5) The sum of the absolute values and the average value is calculated, and this value expressed in micrometers (nm) is the 10-point average surface roughness. Note that the average line is a straight line defined based on ISO4287:1997, and is drawn so that the total area of the area surrounded by the average line and the roughness curve is equal above and below the average line in the measurement length. It is a straight line.
分離機能層の断面は、走査型電子顕微鏡または透過型電子顕微鏡により観察できる。例えば走査型電子顕微鏡で観察するのであれば、複合半透膜サンプルに白金、白金－パラジウムまたは四酸化ルテニウム、好ましくは四酸化ルテニウムを薄くコーティングして３～６ｋＶの加速電圧で高分解能電界放射型走査電子顕微鏡（ＵＨＲ－ＦＥ－ＳＥＭ）を用いて観察する。高分解能電界放射型走査電子顕微鏡は、日立製Ｓ－９００型電子顕微鏡などが使用できる。観察倍率は５，０００～１００，０００倍が好ましく、凸部の高さを求めるには１０，０００～５０，０００倍が好ましい。得られた電子顕微鏡写真において、観察倍率を考慮して、凸部の高さをスケールなどで直接測定することができる。 The cross section of the separation functional layer can be observed using a scanning electron microscope or a transmission electron microscope. For example, when observing with a scanning electron microscope, a composite semipermeable membrane sample is thinly coated with platinum, platinum-palladium, or ruthenium tetroxide, preferably ruthenium tetroxide, and a high-resolution field emission type is applied at an accelerating voltage of 3 to 6 kV. Observe using a scanning electron microscope (UHR-FE-SEM). As a high-resolution field emission scanning electron microscope, a Hitachi S-900 model electron microscope or the like can be used. The observation magnification is preferably 5,000 to 100,000 times, and 10,000 to 50,000 times is preferable for determining the height of the convex portion. In the obtained electron micrograph, the height of the convex portion can be directly measured with a scale or the like, taking into account the observation magnification.
本発明における分離機能層薄膜の凸部高さの中間値は高い造水性と強度を両立するために前述の方法により測定される各断面における平均高さが１００ｎｍ以上２５０ｎｍ以下であることが好ましい。凸部の平均高さが前記範囲であると造水性と強度の両立を最大化できる。凸部の平均高さは、下限値が１２０ｎｍ以上であるのがより好ましく、１５０ｎｍ以上がさらに好ましく、また上限値は２４０ｎｍ以下であるのがより好ましく、２１０ｎｍ以下がさらに好ましい。 The median height of the convex portions of the separation functional layer thin film in the present invention is preferably 100 nm or more and 250 nm or less, as measured by the above-mentioned method, in order to achieve both high water-forming properties and strength. When the average height of the convex portions is within the above range, both water generation performance and strength can be maximized. The lower limit of the average height of the convex portions is more preferably 120 nm or more, even more preferably 150 nm or more, and the upper limit is more preferably 240 nm or less, even more preferably 210 nm or less.
本発明において、架橋ポリアミド膜の厚み（以下、「薄膜厚み」とも称する。）は、十分な分離性能および透過水量を得るために、８～２０ｎｍの範囲内であるのが好ましく、より好ましくは９～１３ｎｍの範囲内である。 In the present invention, the thickness of the crosslinked polyamide membrane (hereinafter also referred to as "thin film thickness") is preferably within the range of 8 to 20 nm, more preferably 9 nm, in order to obtain sufficient separation performance and amount of permeated water. ~13 nm.
薄膜厚みは、透過型電子顕微鏡（ＴＥＭ）でひだ構造の断面を撮影し、断面写真を画像解析ソフトに読み込んで解析を行うことで測定できる。具体的には、分離機能層の断面のＴＥＭ画像において、架橋ポリアミド膜で形成される凸部のうちから任意の５個を選定する。１つの凸部において、その凸部の頂点から高さの９割までの領域の中の１０点で架橋ポリアミド膜の厚みを測定する。こうして得られた計５０点の厚みから算出される相加平均値が「薄膜厚み」である。 The thickness of the thin film can be measured by photographing a cross section of the pleat structure using a transmission electron microscope (TEM), and loading the cross-sectional photograph into image analysis software for analysis. Specifically, in the TEM image of the cross section of the separation functional layer, five arbitrary convex portions are selected from among the convex portions formed of the crosslinked polyamide membrane. In one convex part, the thickness of the crosslinked polyamide film is measured at 10 points in the area from the apex of the convex part to 90% of the height. The arithmetic mean value calculated from the total thickness of 50 points thus obtained is the "thin film thickness."
本発明において、分離機能層の表面における水の接触角は４０度以下であるのが好ましい。ここでの接触角とは静的接触角を指し、分離機能層表面の濡れやすさ、親水性を意味し、接触角が小さいほど親水性が高いことを意味する。 In the present invention, the contact angle of water on the surface of the separation functional layer is preferably 40 degrees or less. The contact angle here refers to the static contact angle, and means the wettability and hydrophilicity of the surface of the separation functional layer, and the smaller the contact angle, the higher the hydrophilicity.
図２に示すように、水２を分離機能層１の表面に滴下すると水２は表面張力で丸くなり、「ヤングの式」と呼ばれる、式（２）が成り立つ。
γＳ＝γＬｃｏｓθ＋γＳＬ （２）
ここでγＳは分離機能層の表面張力、γＬは水の表面張力、γＳＬは分離機能層と水の界面張力である。この式を満たすときの水の接線と分離機能層表面のなす角θを接触角という。
As shown in FIG. 2, when
γ S = γ L cos θ + γ SL (2)
Here, γ S is the surface tension of the separation functional layer, γ L is the surface tension of water, and γ SL is the interfacial tension between the separation functional layer and water. The angle θ between the tangent to water and the surface of the separation functional layer when this formula is satisfied is called the contact angle.
接触角は時間の経過と共に徐々に小さい値へと変化する。水の分離機能層表面への着滴から接触角を測定するまでの時間は２５秒以内であり、好ましくは１５秒以内である。 The contact angle gradually changes to a smaller value with the passage of time. The time from when water drops onto the surface of the separation functional layer until the contact angle is measured is within 25 seconds, preferably within 15 seconds.
分離機能層の表面における水の接触角が４０度以下であるということは、分離機能層が高い親水性を有することを意味する。本発明者らは鋭意検討の結果、表面親水性が高い程水の連通性が高く、分離機能層の表面における水の接触角が４０度以下において、Ｎ置換マレイミド化合物（１）を分離機能層中に含むことで高造水化の効果が顕著であることを見出した。接触角は３５度以下であるのがより好ましい。 The fact that the contact angle of water on the surface of the separation functional layer is 40 degrees or less means that the separation functional layer has high hydrophilicity. As a result of intensive studies, the present inventors found that the higher the surface hydrophilicity, the higher the water communication. It has been found that the effect of high water production is remarkable by including it in the water. More preferably, the contact angle is 35 degrees or less.
（１－２）多孔性支持層
多孔性支持層は分離機能層形成の足場となり、それ自体は実質的にイオン等の分離性能を有さない。
(1-2) Porous support layer The porous support layer serves as a scaffold for forming the separation functional layer, and itself does not substantially have the ability to separate ions, etc.
多孔性支持層における孔のサイズや分布は特に限定されないが、例えば、均一で微細な孔、あるいは分離機能層が形成される側の表面からもう一方の面まで徐々に大きな微細孔をもち、かつ、分離機能層が形成される側の表面における微細孔の大きさが０．１ｎｍ以上１００ｎｍ以下であるような多孔性支持層が好ましい。 The size and distribution of the pores in the porous support layer are not particularly limited, but for example, the porous support layer may have uniform and fine pores, or have fine pores that gradually become larger from the surface on which the separation functional layer is formed to the other surface, and It is preferable to use a porous support layer in which the size of micropores on the surface on which the separation functional layer is formed is 0.1 nm or more and 100 nm or less.
多孔性支持層は、例えばポリエステル及び芳香族ポリアミドから選ばれる少なくとも一種からなる布帛である基材上に高分子重合体を流延することで、得ることができる。なお、以降、基材上に多孔性支持層が形成された構成について「支持膜」と称する場合がある。 The porous support layer can be obtained, for example, by casting a high molecular weight polymer onto a base material that is a fabric made of at least one selected from polyester and aromatic polyamide. Note that hereinafter, a structure in which a porous support layer is formed on a base material may be referred to as a "support film."
多孔性支持層の素材にはポリスルホン、ポリエーテルスルホン、ポリアミド、ポリエステル、セルロース系ポリマー、ビニルポリマー、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホン、ポリフェニレンスルホン、ポリフェニレンオキシドなどのホモポリマーあるいはコポリマーを単独であるいはブレンドして使用することができる。ここでセルロース系ポリマーとしては酢酸セルロース、硝酸セルロースなど、ビニルポリマーとしてはポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリアクリロニトリルなどが使用できる。なかでも、多孔性支持層の素材としてはポリスルホン、ポリアミド、ポリエステル、酢酸セルロース、硝酸セルロース、ポリ塩化ビニル、ポリアクリロニトリル、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホンなどのホモポリマー又はコポリマーが好ましい。多孔性支持層の素材としては、より好ましくは酢酸セルロース、ポリスルホン、ポリフェニレンスルフィドスルホン、又はポリフェニレンスルホンが挙げられ、さらに、これらの素材の中では化学的、機械的、熱的に安定性が高く、成型が容易であることからポリスルホンが一般的に好ましく使用される。 The material for the porous support layer includes homopolymers or copolymers such as polysulfone, polyethersulfone, polyamide, polyester, cellulose polymer, vinyl polymer, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfone, and polyphenylene oxide, either singly or in a blend. can be used. Here, as the cellulose polymer, cellulose acetate, cellulose nitrate, etc. can be used, and as the vinyl polymer, polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, etc. can be used. Among these, preferred materials for the porous support layer include homopolymers or copolymers such as polysulfone, polyamide, polyester, cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile, polyphenylene sulfide, and polyphenylene sulfide sulfone. More preferably, the material for the porous support layer includes cellulose acetate, polysulfone, polyphenylene sulfide sulfone, or polyphenylene sulfone, and among these materials, the material is highly stable chemically, mechanically, and thermally. Polysulfone is generally preferred because it is easy to mold.
例えば、ポリスルホンのＮ，Ｎ－ジメチルホルムアミド（以下、ＤＭＦという。）溶液を、密に織ったポリエステル布あるいはポリエステル不織布の上に一定の厚さに流延し、それを水中で湿式凝固させることによって、表面の大部分が直径数１０ｎｍ以下の微細な孔を有した支持膜を得ることができる。 For example, by casting a solution of polysulfone in N,N-dimethylformamide (hereinafter referred to as DMF) onto a tightly woven polyester cloth or polyester non-woven cloth to a certain thickness, and then wet-coagulating it in water. , it is possible to obtain a support film in which most of the surface has fine pores with a diameter of several tens of nanometers or less.
上記の支持膜の厚みは、得られる複合半透膜の強度及びそれをエレメントにしたときの充填密度に影響を与える。支持膜の厚みは、十分な機械的強度及び充填密度を得るためには、３０μｍ以上３００μｍ以下の範囲内にあることが好ましく、より好ましくは１００μｍ以上２２０μｍ以下の範囲内である。 The thickness of the support membrane mentioned above affects the strength of the composite semipermeable membrane obtained and the packing density when it is made into an element. In order to obtain sufficient mechanical strength and packing density, the thickness of the support film is preferably in the range of 30 μm or more and 300 μm or less, more preferably 100 μm or more and 220 μm or less.
多孔性支持層の形態は、走査型電子顕微鏡や透過型電子顕微鏡、原子間顕微鏡により観察できる。例えば走査型電子顕微鏡で観察するのであれば、基材から多孔性支持層を剥がした後、これを凍結割断法で切断して断面観察のサンプルとする。このサンプルに白金又は白金－パラジウム又は四塩化ルテニウム、好ましくは四塩化ルテニウムを薄くコーティングして３～１５ｋＶの加速電圧で高分解能電界放射型走査電子顕微鏡（ＵＨＲ－ＦＥ－ＳＥＭ）によって観察する。高分解能電界放射型走査電子顕微鏡は、株式会社日立製作所製Ｓ－９００型電子顕微鏡などが使用できる。 The morphology of the porous support layer can be observed using a scanning electron microscope, a transmission electron microscope, or an atomic microscope. For example, in the case of observation using a scanning electron microscope, the porous support layer is peeled off from the base material and then cut by a freeze-fracture method to obtain a sample for cross-sectional observation. The sample is thinly coated with platinum or platinum-palladium or ruthenium tetrachloride, preferably ruthenium tetrachloride, and observed using a high-resolution field emission scanning electron microscope (UHR-FE-SEM) at an accelerating voltage of 3 to 15 kV. As a high-resolution field emission scanning electron microscope, an S-900 model electron microscope manufactured by Hitachi, Ltd. can be used.
多孔性支持層の厚みは、２０μｍ以上１００μｍ以下の範囲内にあることが好ましい。多孔性支持層の厚みが２０μｍ以上であることで、良好な耐圧性が得られると共に、欠点のない均一な支持膜を得ることができるので、このような多孔性支持層を備える複合半透膜は、良好な塩除去性能を示すことができる。多孔性支持層の厚みが１００μｍを超えると、製造時の未反応物質の残存量が増加し、それにより透過水量が低下するとともに、耐薬品性が低下する場合がある。 The thickness of the porous support layer is preferably in the range of 20 μm or more and 100 μm or less. When the thickness of the porous support layer is 20 μm or more, good pressure resistance can be obtained and a uniform support membrane without defects can be obtained, so a composite semipermeable membrane having such a porous support layer can show good salt removal performance. If the thickness of the porous support layer exceeds 100 μm, the amount of unreacted substances remaining during production increases, which may reduce the amount of permeated water and reduce chemical resistance.
（２）製造方法
（２－１）多孔性支持層の形成工程
多孔性支持層の形成工程は、基材に高分子溶液を塗布する工程及び溶液を塗布した前記基材を凝固浴に浸漬させて高分子を凝固させる工程を含む。
(2) Manufacturing method (2-1) Step of forming a porous support layer The step of forming a porous support layer includes a step of applying a polymer solution to a base material, and a step of immersing the base material coated with the solution in a coagulation bath. The method includes a step of coagulating the polymer.
基材に高分子溶液を塗布する工程において、高分子溶液は、多孔性支持層の成分である高分子を、その高分子の良溶媒に溶解して調製する。 In the step of applying the polymer solution to the substrate, the polymer solution is prepared by dissolving a polymer, which is a component of the porous support layer, in a good solvent for the polymer.
高分子溶液塗布時の高分子溶液の温度は、高分子としてポリスルホンを用いる場合、１０℃以上６０℃以下であることが好ましい。高分子溶液の温度がこの範囲内であれば、高分子が析出することがなく、高分子溶液が基材の繊維間にまで充分含浸したのち固化される。その結果、アンカー効果により多孔性支持層が基材に強固に接合し、良好な支持膜を得ることができる。なお、高分子溶液の好ましい温度範囲は、用いる高分子の種類や、所望の溶液粘度などによって適宜調整することができる。 When polysulfone is used as the polymer, the temperature of the polymer solution during application of the polymer solution is preferably 10° C. or more and 60° C. or less. If the temperature of the polymer solution is within this range, the polymer will not precipitate, and the polymer solution will solidify after sufficiently impregnating between the fibers of the base material. As a result, the porous support layer is firmly bonded to the base material due to the anchor effect, and a good support film can be obtained. Note that the preferred temperature range of the polymer solution can be adjusted as appropriate depending on the type of polymer used, the desired solution viscosity, and the like.
基材上に高分子溶液を塗布した後、凝固浴に浸漬させるまでの時間は、０．１秒以上５秒以下であることが好ましい。凝固浴に浸漬するまでの時間がこの範囲であれば、高分子を含む有機溶媒溶液が基材の繊維間にまで充分含浸したのち固化される。なお、凝固浴に浸漬するまでの時間の好ましい範囲は、用いる高分子溶液の種類や、所望の溶液粘度などによって適宜調整することができる。 The time from when the polymer solution is applied to the substrate until it is immersed in the coagulation bath is preferably 0.1 seconds or more and 5 seconds or less. If the time until immersion in the coagulation bath is within this range, the organic solvent solution containing the polymer will sufficiently impregnate between the fibers of the base material and then solidify. Note that the preferred range of time until immersion in the coagulation bath can be adjusted as appropriate depending on the type of polymer solution used, desired solution viscosity, and the like.
凝固浴としては、一般的には水が使われるが、多孔性支持層の成分である高分子を溶解しないものであればよく、特に限定されない。凝固浴の組成によって得られる支持膜の膜形態が変化し、それによって得られる複合半透膜も変化する。凝固浴の温度は、－２０℃以上１００℃以下が好ましく、さらに好ましくは１０℃以上５０℃以下である。凝固浴の温度がこの範囲以内であれば、熱運動による凝固浴面の振動が激しくならず、膜形成後の膜表面の平滑性が保たれる。また温度がこの範囲内であれば凝固速度が適当で、製膜性が良好である。 Water is generally used as the coagulation bath, but it is not particularly limited as long as it does not dissolve the polymer that is a component of the porous support layer. Depending on the composition of the coagulation bath, the morphology of the support membrane obtained changes, and thereby the composite semipermeable membrane obtained also changes. The temperature of the coagulation bath is preferably -20°C or more and 100°C or less, more preferably 10°C or more and 50°C or less. If the temperature of the coagulation bath is within this range, the surface of the coagulation bath will not vibrate violently due to thermal motion, and the smoothness of the film surface after film formation will be maintained. Moreover, if the temperature is within this range, the solidification rate will be appropriate and the film forming property will be good.
次に、このようにして得られた支持膜を、膜中に残存する溶媒を除去するために熱水洗浄する。このときの熱水の温度は４０℃以上１００℃以下が好ましく、さらに好ましくは６０℃以上９５℃以下である。この範囲内であれば、支持膜の収縮度が大きくならず、透過水量が良好である。また、温度がこの範囲内であれば洗浄効果が十分である。 Next, the support membrane thus obtained is washed with hot water to remove the solvent remaining in the membrane. The temperature of the hot water at this time is preferably 40°C or more and 100°C or less, more preferably 60°C or more and 95°C or less. Within this range, the degree of shrinkage of the support membrane will not increase and the amount of permeated water will be good. Moreover, if the temperature is within this range, the cleaning effect will be sufficient.
（２－２）分離機能層の形成工程
次に、複合半透膜を構成する分離機能層の形成工程を説明する。本発明の分離機能層の形成工程は、多官能性アミンを含有する水溶液（水層）と、多官能性酸ハロゲン化物を有機溶媒（有機層）に溶解した溶液とを用い、前記基材及び前記多孔性支持層を含む支持膜の表面で界面重縮合を行う。
(2-2) Formation process of separation functional layer Next, the formation process of the separation functional layer constituting the composite semipermeable membrane will be explained. The step of forming the separation functional layer of the present invention uses an aqueous solution (aqueous layer) containing a polyfunctional amine and a solution in which a polyfunctional acid halide is dissolved in an organic solvent (organic layer). Interfacial polycondensation is performed on the surface of the support membrane including the porous support layer.
本発明者らによる鋭意検討の結果、上記の界面重縮合によって架橋ポリアミドを含む分離機能層を形成する工程に際し、前記一般式（１）で表される化合物（Ｎ置換マレイミド化合物（１））の存在下で前記界面重縮合を行うことで、Ｎ置換マレイミド化合物（１）が分離機能層中に存在し、ポリアミドの官能基との高い親和性を有する複合半透膜が得られることを見出した。 As a result of intensive studies by the present inventors, it was found that the compound represented by the general formula (1) (N-substituted maleimide compound (1)) was It has been found that by performing the interfacial polycondensation in the presence of N-substituted maleimide compound (1), a composite semipermeable membrane can be obtained in which the N-substituted maleimide compound (1) is present in the separation functional layer and has high affinity with the functional groups of polyamide. .
Ｎ置換マレイミド化合物（１）の存在下で前記界面重縮合を行う方法は、例えば、前記多孔性支持層にＮ置換マレイミド化合物（１）を含ませる方法、水層にＮ置換マレイミド化合物（１）を含ませる方法、有機層にＮ置換マレイミド化合物（１）を含ませる方法等があるが、アミンとの過剰な親和による重合反応阻害または副反応を防ぐため、有機層にＮ置換マレイミド化合物（１）を含ませる方法が好ましい。 The method of performing the interfacial polycondensation in the presence of the N-substituted maleimide compound (1) includes, for example, a method of including the N-substituted maleimide compound (1) in the porous support layer, and a method of including the N-substituted maleimide compound (1) in the aqueous layer. However, in order to prevent polymerization reaction inhibition or side reactions due to excessive affinity with amines, N-substituted maleimide compound (1) may be included in the organic layer. ) is preferred.
Ｎ置換マレイミド化合物（１）の濃度は、用いる化合物の種類により適宜決定されるが、具体的には、０．０１～１０質量％の範囲内にあると好ましく、０．０３～１質量％の範囲内であるとさらに好ましい。濃度が上記範囲にあることで、重合反応が過剰に阻害されること無く、分離機能層中でのポリアミドの官能基との親和性を十分有することができる。 The concentration of the N-substituted maleimide compound (1) is appropriately determined depending on the type of compound used, but specifically, it is preferably within the range of 0.01 to 10% by mass, and 0.03 to 1% by mass. More preferably, it is within this range. When the concentration is within the above range, the polymerization reaction is not excessively inhibited, and sufficient affinity with the functional groups of the polyamide in the separation functional layer can be achieved.
上記界面重縮合を多孔性支持層上で行うために、まず、上述の多官能性アミン水溶液を多孔性支持膜に接触させる。接触は、多孔性支持膜の表面上に均一にかつ連続的に行うことが好ましい。具体的には、例えば、多官能性アミン水溶液を多孔性支持膜に塗布する方法、コーティングする方法、または多孔性支持膜を多官能性アミン水溶液に浸漬する方法等を挙げることができる。多孔性支持膜と多官能性アミン水溶液との接触時間は、１～１０分間の範囲内であることが好ましく、１～３分間の範囲内であるとさらに好ましい。 In order to perform the above-mentioned interfacial polycondensation on the porous support layer, first, the above-mentioned polyfunctional amine aqueous solution is brought into contact with the porous support membrane. The contact is preferably carried out uniformly and continuously over the surface of the porous support membrane. Specifically, examples include a method of applying a polyfunctional amine aqueous solution to the porous support membrane, a coating method, a method of immersing the porous support membrane in a polyfunctional amine aqueous solution, and the like. The contact time between the porous support membrane and the polyfunctional amine aqueous solution is preferably within the range of 1 to 10 minutes, more preferably within the range of 1 to 3 minutes.
多官能性アミン水溶液を多孔性支持膜に接触させた後は、膜上に液滴が残らないように十分に液切りする。十分に液切りすることで、膜形成後に液滴残存部分が膜欠点となって膜性能が低下することを防ぐことができる。液切りの方法としては、例えば、特開平２－７８４２８号公報に記載されているように、多官能性アミン水溶液接触後の多孔性支持膜を垂直方向に把持して過剰の水溶液を自然流下させる方法、またはエアーノズルから窒素などの気流を吹き付け、強制的に液切りする方法などを用いることができる。また、液切り後、膜面を乾燥させて水溶液の水分を一部除去することもできる。 After the polyfunctional amine aqueous solution is brought into contact with the porous support membrane, the liquid is sufficiently drained so that no droplets remain on the membrane. By sufficiently draining the liquid, it is possible to prevent the remaining portion of the droplet after film formation from becoming a film defect and reducing the film performance. As a method of draining the liquid, for example, as described in JP-A-2-78428, the porous support membrane after contact with the polyfunctional amine aqueous solution is gripped vertically and the excess aqueous solution is allowed to flow down by gravity. Alternatively, a method of forcibly draining the liquid by blowing an air stream of nitrogen or the like from an air nozzle can be used. Further, after draining, the membrane surface can be dried to remove some of the water in the aqueous solution.
次いで、多官能性アミン水溶液接触後の多孔性支持膜に、多官能性酸ハロゲン化物を含む有機溶媒溶液を接触させ、界面重縮合により架橋ポリアミド分離機能層の骨格を形成させる。 Next, the porous support membrane that has been contacted with the polyfunctional amine aqueous solution is brought into contact with an organic solvent solution containing a polyfunctional acid halide to form a skeleton of the crosslinked polyamide separation functional layer through interfacial polycondensation.
有機溶媒溶液中の多官能性酸ハロゲン化物の濃度は、０．０１～１０質量％の範囲内であると好ましく、０．０２～２．０質量％の範囲内であるとさらに好ましい。多官能性酸ハロゲン化物の濃度を０．０１質量％以上とすることで十分な反応速度が得られ、また、１０質量％以下とすることで副反応の発生を抑制することができるためである。さらに、この有機溶媒溶液にＤＭＦのようなアシル化触媒を含有させると、界面重縮合が促進され、さらに好ましい。 The concentration of the polyfunctional acid halide in the organic solvent solution is preferably within the range of 0.01 to 10% by mass, more preferably within the range of 0.02 to 2.0% by mass. This is because a sufficient reaction rate can be obtained by setting the concentration of the polyfunctional acid halide to 0.01% by mass or more, and the occurrence of side reactions can be suppressed by setting it to 10% by mass or less. . Furthermore, it is more preferable to include an acylation catalyst such as DMF in this organic solvent solution, since interfacial polycondensation is promoted.
有機溶媒は、水と非混和性であり、かつ多官能性酸ハロゲン化物を溶解し、多孔性支持膜を破壊しないものが好ましく、多官能性アミン化合物および多官能性酸ハロゲン化物に対して不活性であるものであればよい。好ましい例として、ｎ－ヘキサン、ｎ－オクタン、ｎ－デカンなどの炭化水素化合物が挙げられる。 The organic solvent is preferably one that is immiscible with water, dissolves the polyfunctional acid halide, does not destroy the porous support membrane, and is immiscible with polyfunctional amine compounds and polyfunctional acid halides. Any active material may be used. Preferred examples include hydrocarbon compounds such as n-hexane, n-octane, and n-decane.
多官能性酸ハロゲン化物の有機溶媒溶液の多官能性アミン化合物水溶液相への接触の方法は、上記の多官能性アミン水溶液の多孔性支持膜への被覆方法と同様に行えばよい。特に、多孔性支持層上に溶液を塗布する方法、多孔性支持層を溶液でコーティングする方法が好適である。 The method for contacting the organic solvent solution of the polyfunctional acid halide with the polyfunctional amine compound aqueous solution phase may be carried out in the same manner as the method for coating the porous support membrane with the polyfunctional amine aqueous solution described above. Particularly suitable are a method of applying a solution onto a porous support layer and a method of coating a porous support layer with a solution.
多官能性アミン水溶液と多官能性酸ハロゲン化物溶液とを接触させた直後の膜面の温度は２５～６０℃の範囲内であることが好ましく、３０～５０℃の範囲内であるとさらに好ましい。温度が２５℃未満では、分離機能層の凸部が大きくならず、透過流束の低下につながり、温度が６０℃より高温では、除去率が低下する傾向があるためである。多官能性アミン水溶液と多官能性酸ハロゲン化物溶液とを接触させた直後の膜面の温度を２５～６０℃の範囲内にすることにより、多孔性支持膜１μｍ長さあたりの分離機能層の実長を２μｍ以上５μｍ以下にすることができ、高い透過流束と塩除去率を得ることができる。 The temperature of the membrane surface immediately after contacting the polyfunctional amine aqueous solution and the polyfunctional acid halide solution is preferably within the range of 25 to 60 °C, more preferably within the range of 30 to 50 °C. . This is because if the temperature is less than 25°C, the convex portions of the separation functional layer will not become large, leading to a decrease in permeation flux, and if the temperature is higher than 60°C, the removal rate will tend to decrease. By keeping the temperature of the membrane surface within the range of 25 to 60°C immediately after contacting the polyfunctional amine aqueous solution and the polyfunctional acid halide solution, the number of separation functional layers per 1 μm length of the porous support membrane can be increased. The actual length can be set to 2 μm or more and 5 μm or less, and high permeation flux and salt removal rate can be obtained.
温度付与方法は、多孔性支持膜を加温してもよく、加温した多官能性酸ハロゲン化物の有機溶媒溶液を接触させてもよい。多官能性アミン水溶液と多官能性酸ハロゲン化物溶液とを接触させた直後の膜面の温度は、放射温度計のような非接触型温度計により測定することができる。 As for the temperature application method, the porous support membrane may be heated, or a heated solution of a polyfunctional acid halide in an organic solvent may be brought into contact with the porous support membrane. The temperature of the membrane surface immediately after the polyfunctional amine aqueous solution and the polyfunctional acid halide solution are brought into contact can be measured with a non-contact thermometer such as a radiation thermometer.
上述したように、多官能性酸ハロゲン化物の有機溶媒溶液を接触させて界面重縮合を行い、多孔性支持膜上に架橋ポリアミドを含む分離機能層を形成したあとは、余剰の溶媒を液切りするとよい。液切りの方法は、例えば、膜を垂直方向に把持して過剰の有機溶媒を自然流下して除去する方法を用いることができる。この場合、垂直方向に把持する時間としては、１～５分の間にあることが好ましく、１～３分間であるとより好ましい。短すぎると分離機能層が完全に形成せず、長すぎると有機溶媒が過乾燥となり欠点が発生しやすく、性能低下を起こしやすい。 As mentioned above, after contacting an organic solvent solution of a polyfunctional acid halide to perform interfacial polycondensation and forming a separation functional layer containing crosslinked polyamide on a porous support membrane, excess solvent is drained off. It's good to do that. As a method for draining the liquid, for example, a method can be used in which the membrane is held vertically and the excess organic solvent is removed by gravity. In this case, the time for vertical gripping is preferably between 1 and 5 minutes, more preferably between 1 and 3 minutes. If it is too short, the separation functional layer will not be completely formed, and if it is too long, the organic solvent will be overdried, which will likely cause defects and cause performance deterioration.
（２－３）その他の処理
上記方法により得られた複合半透膜は、膜内部の残存モノマーの除去や架橋ポリアミド膜の高次構造の安定化の観点から、熱水処理する工程などを行うのが好ましい。これにより、複合半透膜の除去性能および透水性を向上させることができる。熱水処理は、好ましくは５０～１５０℃、より好ましくは７０～１３０℃で、好ましくは１秒～１０分間、より好ましくは１分～８分間処理を行う。
(2-3) Other treatments The composite semipermeable membrane obtained by the above method is subjected to a process such as hot water treatment in order to remove residual monomers inside the membrane and stabilize the higher-order structure of the crosslinked polyamide membrane. is preferable. Thereby, the removal performance and water permeability of the composite semipermeable membrane can be improved. The hot water treatment is preferably carried out at 50 to 150°C, more preferably 70 to 130°C, and preferably for 1 second to 10 minutes, more preferably 1 minute to 8 minutes.
また、本発明で得られる複合半透膜は、熱水処理後に分離機能層上の第一級アミノ基と反応してジアゾニウム塩またはその誘導体を生成する化合物（Ｉ）と接触させ、その後前記化合物（Ｉ）との反応性をもつ水溶性化合物（ＩＩ）を接触させる工程を含むことにより、塩除去率をさらに向上させることができる。 Further, the composite semipermeable membrane obtained in the present invention is brought into contact with the compound (I) that reacts with the primary amino group on the separation functional layer to produce a diazonium salt or a derivative thereof after hot water treatment, and then the compound By including the step of bringing into contact a water-soluble compound (II) that is reactive with (I), the salt removal rate can be further improved.
接触させる第一級アミノ基と反応してジアゾニウム塩またはその誘導体を生成する化合物（Ｉ）としては、亜硝酸およびその塩、ニトロシル化合物などの水溶液が挙げられる。亜硝酸またはニトロシル化合物の水溶液は気体を発生して分解しやすいので、例えば、亜硝酸塩と酸性溶液との反応によって亜硝酸を逐次生成するのが好ましい。 Examples of the compound (I) that reacts with the primary amino group to be contacted to produce a diazonium salt or a derivative thereof include aqueous solutions of nitrous acid and its salts, nitrosyl compounds, and the like. Since an aqueous solution of nitrous acid or a nitrosyl compound is likely to generate gas and decompose, it is preferable to sequentially generate nitrous acid, for example, by reacting nitrite with an acidic solution.
一般に、亜硝酸塩は水素イオンと反応して亜硝酸（ＨＮＯ２）を生成するが、水溶液のｐＨが７以下、好ましくは５以下、さらに好ましくは４以下で効率よく生成する。中でも、取り扱いの簡便性から水溶液中で塩酸または硫酸と反応させた亜硝酸ナトリウムの水溶液が特に好ましい。 Generally, nitrite reacts with hydrogen ions to produce nitrous acid (HNO 2 ), which is efficiently produced when the pH of the aqueous solution is 7 or less, preferably 5 or less, more preferably 4 or less. Among these, an aqueous solution of sodium nitrite reacted with hydrochloric acid or sulfuric acid in an aqueous solution is particularly preferred for ease of handling.
前記第一級アミノ基と反応してジアゾニウム塩またはその誘導体を生成する化合物（Ｉ）、例えば亜硝酸ナトリウムの濃度は、好ましくは０．０１～１質量％の範囲である。この範囲であると十分なジアゾニウム塩またはその誘導体を生成する効果が得られ、溶液の取扱いも容易である。 The concentration of compound (I), such as sodium nitrite, which reacts with the primary amino group to produce a diazonium salt or a derivative thereof, is preferably in the range of 0.01 to 1% by mass. Within this range, a sufficient amount of diazonium salt or its derivative can be produced, and the solution can be easily handled.
該化合物の温度は１５℃～４５℃が好ましい。この範囲だと反応に時間がかかり過ぎることもなく、亜硝酸の分解が早過ぎず取り扱いが容易である。 The temperature of the compound is preferably 15°C to 45°C. Within this range, the reaction does not take too long, and nitrous acid does not decompose too quickly, making it easy to handle.
該化合物との接触時間は、ジアゾニウム塩および／またはその誘導体が生成する時間であればよく、高濃度では短時間で処理が可能であるが、低濃度であると長時間必要である。そのため、上記濃度の溶液では１０分間以内であることが好ましく、３分間以内であることがより好ましい。 The contact time with the compound may be as long as it takes for the diazonium salt and/or its derivative to be produced; at high concentrations, the treatment can be carried out in a short period of time, but at low concentrations, a long period of time is required. Therefore, for a solution having the above concentration, the heating time is preferably within 10 minutes, and more preferably within 3 minutes.
また、接触させる方法は特に限定されず、該化合物の溶液を塗布（コーティング）しても、該化合物の溶液に該複合半透膜を浸漬させてもよい。該化合物を溶かす溶媒は該化合物が溶解し、該複合半透膜が侵食されなければ、いかなる溶媒を用いてもかまわない。また、溶液には、第一級アミノ基と試薬との反応を妨害しないものであれば、界面活性剤または酸性化合物、アルカリ性化合物などが含まれていてもよい。 Further, the method of contacting is not particularly limited, and the composite semipermeable membrane may be applied (coated) with a solution of the compound or immersed in a solution of the compound. Any solvent may be used to dissolve the compound as long as it dissolves the compound and does not erode the composite semipermeable membrane. Further, the solution may contain a surfactant, an acidic compound, an alkaline compound, etc. as long as they do not interfere with the reaction between the primary amino group and the reagent.
次に、ジアゾニウム塩またはその誘導体が生成した複合半透膜を、ジアゾニウム塩またはその誘導体と反応する水溶性化合物（ＩＩ）と接触させる。ここでジアゾニウム塩またはその誘導体と反応する水溶性化合物（ＩＩ）とは、塩化物イオン、臭化物イオン、シアン化物イオン、ヨウ化物イオン、フッ化ホウ素酸、次亜リン酸、亜硫酸水素ナトリウム、亜硫酸イオン、芳香族アミン、フェノール類、硫化水素、チオシアン酸等が挙げられる。 Next, the composite semipermeable membrane produced from the diazonium salt or its derivative is brought into contact with the water-soluble compound (II) that reacts with the diazonium salt or its derivative. The water-soluble compounds (II) that react with diazonium salts or derivatives thereof include chloride ions, bromide ions, cyanide ions, iodide ions, fluoroboric acid, hypophosphorous acid, sodium bisulfite, and sulfite ions. , aromatic amines, phenols, hydrogen sulfide, thiocyanic acid, etc.
亜硫酸水素ナトリウム、および亜硫酸イオンと反応させると瞬時に置換反応が起こり、アミノ基がスルホ基に置換される。また、芳香族アミン、フェノール類と接触させることでジアゾカップリング反応が起こり膜面に芳香族を導入することが可能となる。これらの化合物は単一で用いてもよく、複数混合させて用いてもよく、異なる化合物に複数回接触させてもよい。接触させる化合物として、好ましくは亜硫酸水素ナトリウム、および亜硫酸イオンである。 When reacted with sodium bisulfite and sulfite ions, a substitution reaction occurs instantly, and the amino group is replaced with a sulfo group. In addition, when brought into contact with aromatic amines and phenols, a diazo coupling reaction occurs, making it possible to introduce aromatics onto the membrane surface. These compounds may be used alone, or may be used in combination, or may be contacted with different compounds multiple times. Preferred compounds to be contacted are sodium bisulfite and sulfite ions.
ジアゾニウム塩またはその誘導体と反応する水溶性化合物（ＩＩ）と接触させる濃度と時間は、目的の効果を得るために適宜調節することができる。 The concentration and time of contact with the water-soluble compound (II) that reacts with the diazonium salt or its derivative can be adjusted as appropriate to obtain the desired effect.
ジアゾニウム塩またはその誘導体と反応する水溶性化合物（ＩＩ）と接触させる温度は１０～９０℃が好ましい。この温度範囲であると反応が進みやすく、一方ポリマーの収縮による透過水量の低下も起こらない。 The temperature at which the mixture is brought into contact with the water-soluble compound (II) that reacts with the diazonium salt or its derivative is preferably 10 to 90°C. Within this temperature range, the reaction progresses easily, and at the same time, the amount of permeated water does not decrease due to shrinkage of the polymer.
（３）複合半透膜の利用
本発明の実施形態に係る複合半透膜は、プラスチックネットなどの原水流路材と、トリコットなどの透過水流路材と、必要に応じて耐圧性を高めるためのフィルムと共に、多数の孔を穿設した筒状の集水管の周りに巻回され、スパイラル型の複合半透膜エレメントとして好適に用いられる。さらに、このエレメントを直列又は並列に接続して圧力容器に収納した複合半透膜モジュールとすることもできる。
(3) Utilization of composite semipermeable membrane The composite semipermeable membrane according to the embodiment of the present invention uses a raw water channel material such as a plastic net, a permeated water channel material such as tricot, and, if necessary, to increase pressure resistance. It is wound together with the film around a cylindrical water collecting pipe with a large number of holes, and is suitably used as a spiral-type composite semipermeable membrane element. Furthermore, a composite semipermeable membrane module can be obtained in which these elements are connected in series or in parallel and housed in a pressure vessel.
また、上記の複合半透膜やそのエレメント、モジュールは、それらに原水を供給するポンプや、その原水を前処理する装置などと組み合わせて、流体分離装置を構成することができる。この分離装置を用いることにより、原水を飲料水などの透過水と膜を透過しなかった濃縮水とに分離して、目的に合った水を得ることができる。 Further, the above-described composite semipermeable membrane, its elements, and modules can be combined with a pump that supplies raw water, a device that pre-treats the raw water, etc. to configure a fluid separation device. By using this separation device, raw water can be separated into permeated water such as drinking water and concentrated water that has not passed through the membrane, and water suitable for the purpose can be obtained.
流体分離装置の操作圧力は高い方が塩除去率は向上するが、運転に必要なエネルギーも増加すること、また、複合半透膜の耐久性を考慮すると、複合半透膜に被処理水を透過する際の操作圧力は０．１ＭＰａ以上１０ＭＰａ以下が好ましい。供給水温度は高くなると塩除去率が低下するが、低くなるに従い膜透過流束も減少するので、５℃以上４５℃以下が好ましい。また、供給水ｐＨは、高くなると海水などの高塩濃度の供給水の場合、マグネシウムなどのスケールが発生する恐れがあり、また、高ｐＨ運転による膜の劣化が懸念されるため、中性領域での運転が好ましい。 The higher the operating pressure of the fluid separation device, the better the salt removal rate, but the energy required for operation also increases.Also, considering the durability of the composite semipermeable membrane, it is necessary to The operating pressure during permeation is preferably 0.1 MPa or more and 10 MPa or less. As the feed water temperature increases, the salt removal rate decreases, but as the temperature decreases, the membrane permeation flux also decreases, so it is preferably 5° C. or more and 45° C. or less. In addition, when the pH of the feed water becomes high, scales such as magnesium may occur in feed water with a high salt concentration such as seawater, and there is a concern that membrane deterioration due to high pH operation may occur. It is preferable to drive at
本発明の複合半透膜を用いたモジュールは、非イオン性物質の分離性が高いことも特徴であるため、例えば半導体製造に用いる超純水製造プロセスのような極微量な有機物やケイ酸塩を含む原水から超純水を製造する場合に、特に好適にプロセスに導入することができる。 The module using the composite semipermeable membrane of the present invention is also characterized by its high ability to separate nonionic substances, so it can be used for example in ultrapure water production processes used in semiconductor manufacturing, such as extremely small amounts of organic substances and silicates. It can be particularly suitably introduced into the process when producing ultrapure water from raw water containing.
本発明の実施形態に係る複合半透膜によって処理される原水としては、例えば海水、かん水、排水等の５００ｍｇ／Ｌ～１００ｇ／ＬのＴＤＳ（Ｔｏｔａｌ Ｄｉｓｓｏｌｖｅｄ Ｓｏｌｉｄｓ：総溶解固形分）および０．１ｍｇ／Ｌ～１０００ｍｇ／Ｌの非イオン性物質を含有する液状混合物が挙げられる。一般に、ＴＤＳは総溶解固形分量を指し、「質量÷体積」あるいは「質量比」で表される。定義によれば、０．４５ミクロンのフィルターで濾過した溶液を３９．５～４０．５℃の温度で蒸発させた残留物の重さから算出できるが、より簡便には実用塩分（Ｓ）から換算する。 The raw water to be treated by the composite semipermeable membrane according to the embodiment of the present invention includes, for example, seawater, brine, waste water, etc. with TDS (Total Dissolved Solids) of 500 mg/L to 100 g/L and 0.1 mg. Examples include liquid mixtures containing nonionic substances from 1000 mg/L to 1000 mg/L. Generally, TDS refers to the total amount of dissolved solids and is expressed as "mass divided by volume" or "mass ratio". According to the definition, it can be calculated from the weight of the residue obtained by evaporating a solution filtered through a 0.45 micron filter at a temperature of 39.5 to 40.5°C, but more simply, it can be calculated from the practical salinity (S). Convert.
以下実施例をもって本発明をさらに具体的に説明する。ただし、本発明はこれにより限定されるものではない。 The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited thereto.
［１．特性の測定］
（ＮａＣｌ除去率、Ｓｉ除去率）
複合半透膜に、温度２５℃、ｐＨ７、塩化ナトリウム濃度５００ｐｐｍ、メタケイ酸ナトリウム１００ｐｐｍに調整した評価水を操作圧力０．７５ＭＰａで供給して膜ろ過処理を行なった。供給水及び透過水の電気伝導度を東亜電波工業株式会社製電気伝導度計で測定して、それぞれの実用塩分、すなわちＮａＣｌ濃度を得た。こうして得られたＮａＣｌ濃度及び下記式に基づいて、ＮａＣｌ除去率を算出した。ここで、塩化ナトリウム濃度（ｐｐｍ）は質量基準の濃度を意味する。
ＮａＣｌ除去率（％）＝１００×｛１－（透過水中のＮａＣｌ濃度／供給水中のＮａＣｌ濃度）｝
また、供給水及び透過水のＳｉ濃度をＩＣＰ発光分析装置（Ａｇｉｌｅｎｔ社製５１１０ＶＤＶ）で測定し、次の式からＳｉ除去率を求めた。
Ｓｉ除去率（％）＝１００×｛１－（透過水中のＳｉ濃度／供給水中のＳｉ濃度）｝
[1. Measurement of characteristics]
(NaCl removal rate, Si removal rate)
Membrane filtration treatment was performed by supplying evaluation water adjusted to a temperature of 25° C., a pH of 7, a sodium chloride concentration of 500 ppm, and a sodium metasilicate concentration of 100 ppm to the composite semipermeable membrane at an operating pressure of 0.75 MPa. The electrical conductivity of the feed water and permeated water was measured using an electrical conductivity meter manufactured by Toa Denpa Kogyo Co., Ltd. to obtain the practical salinity, that is, the NaCl concentration of each. Based on the NaCl concentration thus obtained and the following formula, the NaCl removal rate was calculated. Here, the sodium chloride concentration (ppm) means the concentration on a mass basis.
NaCl removal rate (%) = 100 x {1-(NaCl concentration in permeate water/NaCl concentration in feed water)}
Further, the Si concentration of the feed water and the permeated water was measured using an ICP emission spectrometer (5110VDV manufactured by Agilent), and the Si removal rate was determined from the following formula.
Si removal rate (%) = 100 x {1-(Si concentration in permeated water/Si concentration in feed water)}
（透過水量）
前項の試験において、供給水（ＮａＣｌ水溶液）の膜透過水量を測定し、膜面１平方メートル当たり、１日の透水量（立方メートル）に換算した値を膜透過流束（ｍ３／ｍ２／日）とした。
(permeated water amount)
In the test described in the previous section, the amount of water permeated through the membrane of the feed water (NaCl aqueous solution) was measured, and the value converted to the amount of water permeated per day (cubic meters) per square meter of membrane surface was calculated as the membrane permeation flux (m 3 /m 2 /day). ).
（膜中の一般式（１）で表される化合物の検出）
複合半透膜を１０ｃｍ×１０ｃｍに切り出し、エタノール５０ｍＬに８時間浸漬した。エタノールに抽出された成分をあらかじめ検量線を得たガスクロマトグラフ質量分析計（島津製作所社製 ＧＣＭＳ－ＱＰ２０１０）で測定し、ポリアミド分離機能層内の一般式（１）で表される化合物の重量を測定した。次いで、以下の式から、ポリアミド分離機能層内の単位膜面積当たりの化合物密度を求めた。ここで、膜面積は、上記で切り出した複合半透膜の面積としている。
化合物密度（ｍｏｌ／ｍ２）＝化合物重量／（化合物分子量×膜面積）
(Detection of compound represented by general formula (1) in membrane)
The composite semipermeable membrane was cut into a size of 10 cm x 10 cm and immersed in 50 mL of ethanol for 8 hours. The components extracted in ethanol were measured using a gas chromatograph mass spectrometer (GCMS-QP2010 manufactured by Shimadzu Corporation) with a calibration curve obtained in advance, and the weight of the compound represented by general formula (1) in the polyamide separation functional layer was determined. It was measured. Next, the compound density per unit membrane area in the polyamide separation functional layer was determined from the following formula. Here, the membrane area is the area of the composite semipermeable membrane cut out above.
Compound density (mol/m 2 ) = compound weight / (compound molecular weight x membrane area)
（分離機能層における凸部の高さ）
複合半透膜をエポキシ樹脂で包埋し、断面観察を容易にするためＯｓＯ４で染色して、これをウルトラミクロトームで切断し超薄切片を１０個作製した。得られた超薄切片について、透過型電子顕微鏡（ＴＥＭ）を用いて断面写真を撮影した。観察時の加速電圧は１００ｋＶであり、観察倍率は１０，０００倍であった。
得られた断面写真について、スケールを用いて、支持膜の膜面方向の幅２．０μｍの領域における凸部の数を測定し、上述した方法で１０点平均面粗さを算出した。この１０点平均面粗さに基づいて、１０点平均面粗さの５分の１以上の高さを有する部分を凸部として、断面写真中の全ての凸部の高さをスケールで測定し、凸部の平均高さを求めた。
(Height of convex portion in separation functional layer)
The composite semipermeable membrane was embedded in epoxy resin, stained with OsO 4 to facilitate cross-sectional observation, and cut with an ultramicrotome to prepare 10 ultrathin sections. A cross-sectional photograph was taken of the obtained ultra-thin section using a transmission electron microscope (TEM). The acceleration voltage during observation was 100 kV, and the observation magnification was 10,000 times.
Regarding the obtained cross-sectional photograph, the number of convex portions in a region having a width of 2.0 μm in the film surface direction of the support film was measured using a scale, and the 10-point average surface roughness was calculated using the method described above. Based on this 10-point average surface roughness, measure the heights of all the convexities in the cross-sectional photograph using a scale, with the part having a height of 1/5 or more of the 10-point average surface roughness as a convex part. , the average height of the protrusions was determined.
（接触角）
協和界面科学社製Ｄｒｏｐ Ｍａｓｔｅｒ ＤＭ５００を用いて、θ／２法にて静的接触角をコンピュータでの画像解析により自動算出した。なお、液適量は１．５μｌとし、蒸留水の分離機能層上への着滴開始から１０秒後に接触角を測定した。
(contact angle)
The static contact angle was automatically calculated by image analysis on a computer using the θ/2 method using Drop Master DM500 manufactured by Kyowa Interface Science. The appropriate amount of liquid was 1.5 μl, and the contact angle was measured 10 seconds after the start of dropping distilled water onto the separation functional layer.
［２．複合半透膜の作製］
（比較例１）
長繊維からなるポリエステル不織布（通気度２．０ｃｃ／ｃｍ２／ｓｅｃ）上にポリスルホンの１５．０質量％ＤＭＦ溶液を２５℃の条件下でキャストし、ただちに純水中に浸漬して５分間放置することによって、多孔性支持層の厚みが４０μｍである支持膜を作製した。次に、この支持膜を２．０質量％のｍ－ＰＤＡ水溶液に浸漬した後、余分な水溶液を除去し、さらに濃度が０．１０質量％となるようにＴＭＣを溶解したｎ－デカン溶液を多孔性支持層の表面が完全に濡れるように３００ｍＬ／ｍ２塗布した。次に膜から余分な溶液を除去するために、膜を垂直にして液切りを行って、送風機を使い２５℃の空気を吹き付けて乾燥させた後、４０℃の純水で洗浄して、比較例１の架橋ポリアミド膜を備えた複合半透膜を得た。
[2. Preparation of composite semipermeable membrane]
(Comparative example 1)
A 15.0% by mass DMF solution of polysulfone was cast on a polyester nonwoven fabric (air permeability 2.0cc/cm 2 /sec) consisting of long fibers at 25°C, and immediately immersed in pure water and left for 5 minutes. By doing so, a support membrane having a porous support layer having a thickness of 40 μm was produced. Next, this support film was immersed in a 2.0% by mass m-PDA aqueous solution, the excess aqueous solution was removed, and an n-decane solution in which TMC was dissolved was added to a concentration of 0.10% by mass. 300 mL/m 2 was applied so that the surface of the porous support layer was completely wetted. Next, in order to remove excess solution from the membrane, the membrane was held vertically to drain the liquid, and after drying by blowing air at 25℃ using a blower, it was washed with pure water at 40℃ and compared. A composite semipermeable membrane comprising the crosslinked polyamide membrane of Example 1 was obtained.
（比較例２）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にε－カプロラクタム０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Comparative example 2)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of ε-caprolactam was added to 25 ml of a 25° C. n-decane solution containing 0.10% by mass of TMC.
（比較例３）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にピメリン酸０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Comparative example 3)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of pimelic acid was added to 25 ml of an n-decane solution at 25° C. containing 0.10% by mass of TMC.
（比較例４）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にスベリン酸０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Comparative example 4)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of suberic acid was added to 25 ml of an n-decane solution at 25° C. containing 0.10% by mass of TMC.
（実施例１）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にＮ－メチルマレイミド０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Example 1)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of N-methylmaleimide was added to 25 ml of a 25° C. n-decane solution containing 0.10% by mass of TMC.
（実施例２）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にＮ－メチルマレイミド１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Example 2)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 10% by mass of N-methylmaleimide was added to 25 ml of an n-decane solution at 25° C. containing 0.10% by mass of TMC.
（実施例３）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にＮ－エチルマレイミド０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Example 3)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of N-ethylmaleimide was added to 25 ml of a 25° C. n-decane solution containing 0.10% by mass of TMC.
（実施例４）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にＮ－プロピルマレイミド０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Example 4)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of N-propylmaleimide was added to 25 ml of a 25° C. n-decane solution containing 0.10% by mass of TMC.
（実施例５）
ＴＭＣ０．１０質量％を含む２５℃のｎ－デカン溶液２５ｍｌ中にＮ－ブチルマレイミド０．１０質量％を加えたこと以外は比較例１と同様の方法で複合半透膜を得た。
(Example 5)
A composite semipermeable membrane was obtained in the same manner as in Comparative Example 1, except that 0.10% by mass of N-butylmaleimide was added to 25 ml of a 25° C. n-decane solution containing 0.10% by mass of TMC.
比較例、実施例によって得られた膜の構造と性能はそれぞれ表１に示す通りであった。 The structures and performances of the membranes obtained in Comparative Examples and Examples are shown in Table 1.
実施例１～５の複合半透膜は、比較例１～４の複合半透膜と比較して、高い除去率を維持しつつ、高い透過水量が得られた。このことから、本発明の複合半透膜は高い造水性能と除去率を両立する膜であることが分かった。 Compared to the composite semipermeable membranes of Comparative Examples 1 to 4, the composite semipermeable membranes of Examples 1 to 5 maintained a high removal rate and obtained a high amount of permeated water. From this, it was found that the composite semipermeable membrane of the present invention is a membrane that achieves both high water generation performance and removal rate.
１：分離機能層
２：水
1: Separation functional layer 2: Water
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022109187A JP2024007836A (en) | 2022-07-06 | 2022-07-06 | composite semipermeable membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022109187A JP2024007836A (en) | 2022-07-06 | 2022-07-06 | composite semipermeable membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2024007836A true JP2024007836A (en) | 2024-01-19 |
Family
ID=89544497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2022109187A Pending JP2024007836A (en) | 2022-07-06 | 2022-07-06 | composite semipermeable membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2024007836A (en) |
-
2022
- 2022-07-06 JP JP2022109187A patent/JP2024007836A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5741431B2 (en) | Composite semipermeable membrane and method for producing the same | |
| JP5895838B2 (en) | Separation membrane element and method for producing composite semipermeable membrane | |
| JP5978998B2 (en) | Composite semipermeable membrane, composite semipermeable membrane element, and method for producing composite semipermeable membrane | |
| JP6402627B2 (en) | Composite semipermeable membrane | |
| WO2016002821A1 (en) | Composite semipermeable membrane | |
| JP2011078980A (en) | Composite semipermeable membrane and manufacturing method of the same | |
| JP5923793B2 (en) | Highly permeable reverse osmosis membrane containing carbodiimide compound and method for producing the same | |
| US20170120201A1 (en) | Composite semipermeable membrane | |
| WO2014133133A1 (en) | Composite semipermeable membrane | |
| KR102497473B1 (en) | composite semi-permeable membrane | |
| WO2016052427A1 (en) | Composite semipermeable membrane and method for producing same, and spiral separation membrane element | |
| JP5177056B2 (en) | Composite semipermeable membrane | |
| JP2017213501A (en) | Composite semipermeable membrane and method for producing composite semipermeable membrane | |
| JPH10165789A (en) | Manufacture of dry composite reverse-osmosis membrane | |
| JP6702181B2 (en) | Composite semipermeable membrane | |
| JP7342528B2 (en) | Composite semipermeable membrane and method for manufacturing composite semipermeable membrane | |
| JP2009262089A (en) | Manufacturing method of composite semi-permeable membrane | |
| JPH10165790A (en) | Manufacture of composite reverse-osmosis membrane | |
| JP2024007836A (en) | composite semipermeable membrane | |
| JP5062136B2 (en) | Manufacturing method of composite semipermeable membrane | |
| JP6511808B2 (en) | Composite semipermeable membrane | |
| WO2024048695A1 (en) | Composite semipermeable membrane and method for producing composite semipermeable membrane | |
| JP2008259983A (en) | Manufacturing method of dry composite semi-permeable membrane | |
| WO2023048288A1 (en) | Composite semipermeable membrane | |
| WO2023234415A1 (en) | Composite semipermeable membrane and method for producing same |