JP2015510450A - 耐塩素性に優れた高流量水処理分離膜 - Google Patents
耐塩素性に優れた高流量水処理分離膜 Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000926 separation method Methods 0.000 title claims abstract description 94
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title description 12
- 239000000460 chlorine Substances 0.000 title description 12
- 229910052801 chlorine Inorganic materials 0.000 title description 12
- 239000004952 Polyamide Substances 0.000 claims abstract description 78
- 229920002647 polyamide Polymers 0.000 claims abstract description 78
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 26
- 125000003368 amide group Chemical group 0.000 claims abstract description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 129
- 150000001412 amines Chemical class 0.000 claims description 64
- 239000007864 aqueous solution Substances 0.000 claims description 60
- -1 acyl halide compound Chemical class 0.000 claims description 50
- 238000012695 Interfacial polymerization Methods 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 130
- 238000000034 method Methods 0.000 description 40
- 150000003839 salts Chemical class 0.000 description 30
- 230000003746 surface roughness Effects 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000001223 reverse osmosis Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920002492 poly(sulfone) Polymers 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000012466 permeate Substances 0.000 description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 150000001266 acyl halides Chemical class 0.000 description 7
- 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 7
- 238000011156 evaluation Methods 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 238000004566 IR spectroscopy Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229940018564 m-phenylenediamine Drugs 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910019093 NaOCl Inorganic materials 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
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- 230000000704 physical effect Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-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
- HHSBHVJQXZLIRW-UHFFFAOYSA-N 3-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CN(C)C1=CC=CC(N)=C1 HHSBHVJQXZLIRW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)(C1)C2C34C5C1=CC5C3CCCC24 Chemical compound CC(*)(C1)C2C34C5C1=CC5C3CCCC24 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229940066771 systemic antihistamines piperazine derivative Drugs 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
- 238000000108 ultra-filtration Methods 0.000 description 1
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Abstract
Description
0.25R≦v×Δt≦0.75R …[式1]
R'≦D≦3/16(R2h) …[式2]
DMF(N,N−ジメチルホルムアミド)溶液に18重量%のポリスルホン固形分を入れて80℃〜85℃において12時間以上溶かすことで、均一の液相を得た。この溶液をポリエステル材質の厚さ95〜100μmを有する不織布上に厚さ45〜50μmでキャストして多孔性ポリスルホン支持体を形成した。
有機溶液の滴下体積を液滴当たり0.05mlとし、多孔性支持体の移動方向に0.34回/secの周期で液滴を滴下した点を除いては、実施例1と同一方法で水処理分離膜を製造した。
有機溶液の滴下体積を液滴当たり0.1mlとし、多孔性支持体の移動方向に0.17回/secの周期で液滴を滴下した点を除いては、実施例1と同一方法で水処理分離膜を製造した。
有機溶液の滴下体積を液滴当たり0.2mlとし、多孔性支持体の移動方向に0.09回/secの周期で液滴を滴下した点を除いては、実施例1と同一方法で水処理分離膜を製造した。
多孔性支持体1m2当たり200mlの有機溶液を滴下し、有機溶液の滴下体積を液滴当たり0.02mlにして滴下した点を除いては、実施例1と同一方法で水処理分離膜を製造した。
多孔性支持体1m2当たり200mlの有機溶液を滴下し、有機溶液の滴下体積を液滴当たり0.1mlにして滴下した点を除いては、実施例2と同一方法で水処理分離膜を製造した。
多孔性支持体1m2当たり200mlの有機溶液を滴下し、有機溶液の滴下体積を液滴当たり0.2mlにして滴下した点を除いては、実施例3と同一方法で水処理分離膜を製造した。
多孔性支持体1m2当たり200mlの有機溶液を滴下し、有機溶液の滴下体積を液滴当たり0.4mlにして滴下した点を除いては、実施例4と同一方法で水処理分離膜を製造した。
アミン水溶液層が形成された多孔性支持体の移動速度を2m/minとし、多孔性支持体1m2当たり200mlの有機溶液を滴下した点を除いては、実施例3と同一にして実験を行った。
アミン水溶液層が形成された多孔性支持体の移動速度を2m/minとし、多孔性支持体1m2当たり200mlの有機溶液を滴下した点を除いては、実施例4と同一にして実験を行った。
DMF(N,N−ジメチルホルムアミド)溶液に18重量%のポリスルホン固形分を入れて80℃〜85℃において12時間以上溶かすことで、均一な液相を得た。この溶液をポリエステル材質の厚さ95〜100μmの不織布上に厚さ45〜50μmでキャストして多孔性ポリスルホン支持体を形成した。
有機溶液の滴下体積を液滴当たり0.01mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.02mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.03mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.05mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.07mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.1mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり0.15mlとし、その他の条件は実施例11と同一にして実験を行った。
有機溶液の滴下体積を液滴当たり2.0mlとし、その他の条件は実施例11と同一にして実験を行った。
DMF(N,N−ジメチルホルムアミド)溶液に18重量%のポリスルホン固形分を入れて80℃〜85℃において12時間溶かして均一な液相を得た。この溶液をポリエステル材質の厚さ95〜100μmの不織布上に厚さ45〜50μmでキャストして多孔性ポリスルホン支持体を形成した。
上記実施例1〜19及び比較例によって製造された逆浸透膜の初期塩除去率及び初期透過流量を800psiの圧力下において測定した。初期塩除去率及び初期透過流量は25℃において32,000ppmの塩化ナトリウム水溶液を4500mL/minの流量で供給しながら測定した。膜の評価に用いられた逆浸透膜セル装置は、平板型透過セル、高圧ポンプ、貯蔵槽及び冷却装置を備える。また、平板型透過セルの構造は、クロスフロー(cross−flow)方式で、有効透過面積は28cm2である。次に、洗浄された逆浸透分離膜を透過セルに設置した後、評価装備の安定化のために、3次蒸留水を用いて約1時間の予備運転を十分に行った。その後、32,000ppmの塩化ナトリウム水溶液に交替して圧力及び透過流量が正常状態に達するまで約1時間の装備運転を行った後、10分の間に透過される水の量を測定して流量を計算し、伝導度メーター(Conductivity Meter)を用いて透過前後の塩濃度を分析して塩除去率を計算した。塩除去率は以下のような式によって測定され、測定結果は下記表1に示した通りである。
実施例2、実施例14及び比較例によって製造された逆浸透膜を評価した。32,000ppmのNaCl水溶液及び2,000ppmのNaOClを含有する混合水溶液を用いて800psiにおける初期塩除去率及び初期透過流量を測定した後、6時間経過後及び12時間経過後の塩除去率及び初期透過流量を測定した。測定結果は表2に示した通りである。
実施例14、実施例15、実施例17及び比較例によって製造された水処理分離膜で5μm×5μmのサイズを有する試料を製作し、AFM(Digital Instruments Nanoscope V MMAFM−8 Multimode)を用いて試料全体のサイズに対して粗度分析(Roughness Analysis)を行い、Ra値を測定した。測定結果は表3に示した通りである。
実施例2及び比較例によって製造された水処理分離膜を5cm×5cmのサイズに裁断し、試料を製作した後、上記試料をHCl溶液に入れて酸処理した。次に、ATR(Ge)FT−IR装置のFTS7000(製造社:Varian)を用いて、上記のように処理された試料の表面において横及び縦5mmの間隔でIRデータを測定し、アミド基と結合したC=O二重結合のピーク高さに対するカルボキシ基のC=O二重結合のピーク高さの比を計算し、計算された値の最小値及び最大値を確認した。結果は下記表4に示した通りである。
20 滴下手段
30 移動手段
40 乾燥手段
50 アミン水溶液層が形成された多孔性支持体
130、130a、130b 有機溶液の液滴
132 アシルハライド化合物
134 臨界領域
上記実施例1〜19及び比較例によって製造された逆浸透膜の初期塩除去率及び初期透過流量を800psiの圧力下において測定した。初期塩除去率及び初期透過流量は25℃において32,000ppmの塩化ナトリウム水溶液を4500mL/minの流量で供給しながら測定した。膜の評価に用いられた逆浸透膜セル装置は、平板型透過セル、高圧ポンプ、貯蔵槽及び冷却装置を備える。また、平板型透過セルの構造は、クロスフロー(cross−flow)方式で、有効透過面積は28cm2である。次に、洗浄された逆浸透分離膜を透過セルに設置した後、評価装備の安定化のために、3次蒸留水を用いて約1時間の予備運転を十分に行った。その後、32,000ppmの塩化ナトリウム水溶液に交替して圧力及び透過流量が正常状態に達するまで約1時間の装備運転を行った後、10分の間に透過される水の量を測定して流量を計算し、伝導度メーター(Conductivity Meter)を用いて透過前後の塩濃度を分析して塩除去率を計算した。測定結果は下記表1に示した通りである。
Claims (9)
- 多孔性支持体上にポリアミド活性層が形成され、
前記ポリアミド活性層を酸処理した後、フーリエ変換赤外線分光器(FTIR)を用いて測定したアミド基と結合したC=O二重結合(−CONH−)のピーク高さに対するカルボキシ基のC=O二重結合(−COOH)のピーク高さの比の最小値に対する最大値の比が1.2〜4である、水処理分離膜。 - 前記ポリアミド活性層は、アミン水溶液層上にアシルハライド化合物が含有された有機溶液の液滴を滴下して形成され、
前記滴下された液滴が平坦化してアミン化合物との界面重合度が高い中心部、及びアミン化合物との界面重合度が低い臨界領域が形成される、請求項1に記載の水処理分離膜。 - 前記最小値は、前記中心部におけるアミド基と結合したC=O二重結合(−CONH−)のピーク高さに対するカルボキシ基のC=O二重結合(−COOH)のピーク高さの比であり、
前記最大値は、前記臨界領域におけるアミド基と結合したC=O二重結合(−CONH−)のピーク高さに対するカルボキシ基のC=O二重結合(−COOH)のピーク高さの比である、請求項2に記載の水処理分離膜。 - 前記アミド基と結合したC=O二重結合(−CONH−)のピーク高さに対するカルボキシ基のC=O二重結合(−COOH)のピーク高さの比の最小値は0.05〜0.07である、請求項1に記載の水処理分離膜。
- 前記アミド基と結合したC=O二重結合(−CONH−)のピーク高さに対するカルボキシ基のC=O二重結合(−COOH)のピーク高さの比の最大値は0.17〜0.19である、請求項1に記載の水処理分離膜。
- 前記酸処理は、前記ポリアミド活性層を塩酸水溶液に入れて行われる、請求項1に記載の水処理分離膜。
- 前記ポリアミド活性層の表面の算術平均粗度(Ra)は60nm〜100nmである、請求項1に記載の水処理分離膜。
- 請求項1〜7のいずれか一項に記載の水処理分離膜を少なくとも一つ以上含む、水処理モジュール。
- 請求項8の水処理モジュールを少なくとも一つ以上含む、水処理装置。
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JP2001286741A (ja) * | 2000-04-04 | 2001-10-16 | Toray Ind Inc | 逆浸透複合膜およびその製造方法 |
JP2009006315A (ja) * | 2007-05-30 | 2009-01-15 | Toray Ind Inc | 複合半透膜の製造方法 |
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