JP6265287B1 - 選択性透過膜、その製造方法及び水処理方法 - Google Patents
選択性透過膜、その製造方法及び水処理方法 Download PDFInfo
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- JP6265287B1 JP6265287B1 JP2017028152A JP2017028152A JP6265287B1 JP 6265287 B1 JP6265287 B1 JP 6265287B1 JP 2017028152 A JP2017028152 A JP 2017028152A JP 2017028152 A JP2017028152 A JP 2017028152A JP 6265287 B1 JP6265287 B1 JP 6265287B1
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Abstract
Description
本発明の水処理方法は、本発明の選択性透過膜を用いることを特徴とする。
この支持膜としては、多孔質体の表面に交互積層(LBL)法によりカチオン性高分子とアニオン性高分子とを交互に被覆させたものを用いることができる。LBL法は、カチオン性高分子とアニオン性高分子を高分子間の静電相互作用を用いて交互に吸着、積層することで、層の厚さをnmレベルで制御可能な手法であり、透過流束と耐圧性を変化させることができる。
この支持膜上に形成する脂質膜としては、リン脂質二分子膜が好ましい。支持膜表面にリン脂質二分子膜を形成させる方法としては、ラングミュア−ブロジェット法、リポソーム融合法が挙げられる。リポソーム融合法では、上記のようにして得られた支持膜を、膜表面と反対の電荷を有する脂質を含むリポソームの分散液に浸漬させることで、静電的相互作用により支持膜上に形成される。
以下の実施例及び比較例では、多孔質体(膜本体)として、セルロース混合エステル膜(直径25mm、孔径0.05μm、ミリポア社製)を用いた。
カチオン性高分子としてポリジアリルジメチルアンモニウムクロリド(PDADMAC、平均分子量40万〜50万、シグマアルドリッチ)、アニオン性高分子としてポリスチレンスルホン酸ナトリウム(PSS、平均分子量20万、シグマアルドリッチ)を用いた。
<比較例1に用いる支持膜>
まず、上記多孔質体(膜本体)を真空プラズマ装置(YHS−R、魁半導体社製)を用いて1分間処理した。プラズマ処理した膜本体を1g/LのPDADMAC(ポリジアリルジメチルアンモニウムクロリド)水溶液に5分間浸漬し、純水で1分間洗浄した(0.5層膜)。次に、1g/LのPSS(ポリスチレンスルホン酸ナトリウム)水溶液に5分間浸漬し、純水で1分間洗浄した(1.0層膜)。更に、1g/LのPDADMAC水溶液に5分間浸漬し、純水で1分間洗浄した(1.5層膜)。得られた膜を、10mmol/Lの硫酸マグネシウム水溶液に1時間浸漬し、純水で洗浄し、リン脂質層を形成させる膜として用いた。
上記1.5層膜を形成した後、さらに上記のPDADMACとPSSの製膜を交互に行い、最表面がカチオン性の積層膜3.5層膜を有する支持膜を得た。
<リン脂質>
アニオン性リン脂質として、1−パルミトイル−2−オレイル−sn−グリセロ−3−ホスホ−(1’−rac−グリセロール)(ナトリウム塩)(POPG、日油)を用いた。中性リン脂質として1−パルミトイル−2−オレイル−sn−グリセロ−3−ホスホコリン(POPC、日油)を用いた。
チャネル物質としては、グラミシジンA(GA、シグマアルドリッチ)を用いた。
POPCとPOPGを7:3のモル比でクロロホルムに溶解し(合計の濃度95mol%)、この溶液にトリフルオロエタノールに溶解したGAをGA濃度がリン脂質に対して5mol%になるように混合し、エバポレーターにより有機溶媒を蒸発させ、容器内に残存した乾燥脂質薄膜に純水を添加し、45℃で水和させることで、リポソーム分散液を調製した。得られたリポソーム分散液は、液体窒素と45℃の湯浴に交互に浸漬操作を5回繰り返す凍結融解法により、粒成長させた。リポソーム分散液は孔径0.1μmのポリカーボネートトラックエッチング膜(Nucrepore、GEヘルスケア)を用い、押し出し整粒し、脂質濃度が0.4mmol/Lになるよう純水で希釈してリポソーム分散液を調製した。
このリポソーム分散液中に、上記の膜本体を40℃で2時間浸漬させることで、膜本体にリン脂質を吸着させた。その後、純水で洗浄することにより、膜本体に余分に吸着したリン脂質を剥がし、POPC/POPG被覆膜を製膜して選択性透過膜を製造した。
図1,2に示す平膜試験装置を用いて膜の耐圧性を評価した。
脱塩率=1−透過液の電導度/濃縮液の電導度
上記比較例用支持膜(被覆膜1.5層)に上記方法によりリン脂質二分子層を形成し、選択性透過膜を製造した。
上記実施例用支持膜(被覆膜3.5層)に上記方法によりリン脂質二分子層を形成し、選択性透過膜を製造した。
リン脂質二分子層を形成させる際、POPCとPOPGを3:7のモル比で調製したリポソーム分散液に浸漬させたこと以外は実施例1と同様にして、選択性透過膜を製造した。
実施例1と同様にリン脂質二分子層を形成後、pH9.0の水酸化ナトリウム水溶液を用いて膜表面を洗浄し(アルカリ洗浄)、選択性透過膜を製造した。
Claims (5)
- 選択的透過性を有した支持膜と、該支持膜の表面に形成された、チャネル物質を含有する脂質膜とを有する選択性透過膜において、
該支持膜が圧力0.1MPaにおいて20L/(m2・h)以上の透過流束と1%〜20%の脱塩性能を有する支持膜であり、
該支持膜が多孔質体と、該多孔質体を被覆する荷電性高分子層とを有し、
該荷電性高分子層は、交互に形成されたカチオン性高分子層とアニオン性高分子層とを有する交互被覆層よりなり、
該交互被覆層の層数が2〜4であり、
前記多孔質体がMF膜又はUF膜であることを特徴とする選択性透過膜。 - 0.1MPaにおいて1L/(m2・h)以上の透過流束と90%以上の脱塩性能を有することを特徴とする請求項1に記載の選択性透過膜。
- 前記チャネル物質が、グラミシジン、アムモテリシンB、及びこれらの誘導体よりなる群から選ばれた少なくとも1つであることを特徴とする請求項1又は2に記載の選択性透過膜。
- 請求項1〜3のいずれか1項に記載の選択性透過膜を製造する方法であって、前記支持膜上に前記脂質膜を形成する工程と、余分な脂質を酸又はアルカリで除去する工程とを有する選択性透過膜の製造方法。
- 請求項1〜3のいずれか1項に記載の選択性透過膜を用いて被処理水を膜分離処理する工程を有する水処理方法。
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US16/484,543 US20200055000A1 (en) | 2017-02-17 | 2017-08-08 | Permselective membrane and method for producing the same, and method for treating water |
PCT/JP2017/028721 WO2018150608A1 (ja) | 2017-02-17 | 2017-08-08 | 選択性透過膜、その製造方法及び水処理方法 |
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SG11201907340VA SG11201907340VA (en) | 2017-02-17 | 2017-08-08 | Permselective membrane and method for producing the same, and method for treating water |
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CN111871234A (zh) * | 2020-07-13 | 2020-11-03 | 广东溢达纺织有限公司 | 一种疏松纳滤膜及其制备方法和应用 |
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US20200055000A1 (en) | 2020-02-20 |
JP2018130703A (ja) | 2018-08-23 |
CN110382094A (zh) | 2019-10-25 |
US20220193619A1 (en) | 2022-06-23 |
SG11201907340VA (en) | 2019-09-27 |
KR102329019B1 (ko) | 2021-11-18 |
WO2018150608A1 (ja) | 2018-08-23 |
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