TW201927408A - 離子交換膜、脫離子裝置及脫離子裝置之運作方法 - Google Patents
離子交換膜、脫離子裝置及脫離子裝置之運作方法 Download PDFInfo
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- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
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Abstract
一種離子交換膜，其官能基具有3級胺基、2級胺基及1級胺基之至少1種。使用此離子交換膜之脫離子裝置。以及運作此脫離子裝置的方法，其特徵係具有藉由鹼溶液洗淨離子交換膜之工序。
Description
本發明係關於，離子交換膜、使用此離子交換膜之脫離子裝置及此脫離子裝置之運作方法。
離子交換膜被利用於海水濃縮、地下鹹水之脫鹽或硝酸態氮的除去、食品製造工序之鹽分除去或醫藥品的有效成分的濃縮等。作為使用離子交換膜的脫離子裝置，有電氣透析、擴散透析、電氣脫離子裝置等。
離子交換膜一般具有苯乙烯-二乙烯基苯系之母體。在陽離子交換膜，使用具有磺基者，在陰離子交換膜使用具有4級銨基者。此外，還有對1價與2價的離子選擇性、或者使支撐層儘可能薄之低阻力膜等，做為工業用離子分離膜相當有用。
在離子分離，食品或醫藥品領域等亦有不少除了鹽類以外還要求含有機物的脫鹽的場合。此外，於製水領域，亦有尋求包含天然水中的有機物的脫鹽的事例。有不少被處理液中的有機物引起膜的有機污染之事例。這是帶有電荷的巨大分子附著於具相反符號的交換基之離子交換膜而產生的。這樣的污染會引起脫離子裝置的脫鹽率降低，電壓上升等不良情況。特別是有機物多具有陰離子性，陰離子交換膜的有機污染變成問題的事例很多。
離子交換膜的有機污染，並不是僅在電氣透析、擴散透析、逆電氣透析等特定裝置或處理方法上才發生的問題，只要是使用離子交換膜的裝置，都有發生問題的可能性。特別是被處理水的前處理不夠充分的場合，容易產生有機污染。
作為抑制有機污染導致離子交換膜的事故的方法，被提出了阻止有機物離子往膜的內部侵入的方法，與讓巨大的有機物離子也透過膜的方法。促進膜之透過的場合，考慮選擇更為鬆散的母體構造。但是，鬆散的構造的母體使承擔離子分離性的阻止率降低的可能性很高。
作為阻止有機物離子往膜的內部侵入之離子交換膜，於專利文獻1，記載著往離子交換膜表層導入磺酸基的陰離子交換膜。然而，由於被形成在膜的表層部的相反荷電層，使離子交換膜的電阻(膜電阻)顯著增大。
於專利文獻2記載一種耐有機污染膜，係於多孔性膜之貫通孔內充填離子交換樹脂，該離子交換樹脂在較孔的最表面更陷沒處露出。但是，這樣的膜的製造必須要高度且繁瑣的製造技術，膜的製造成本很高。
於專利文獻3，記載著具有聚伸烷基二醇鏈的聚醚化合物被固定化於膜表面或膜內部之離子交換膜。應該是藉由聚醚化合物存在於離子交換膜的表面或內部，巨大有機物離子等變得難以直接與離子交換基接觸，所以抑制巨大有機物離子等之往離子交換膜的吸附，結果，提高耐有機污染性。然而，一般認為即使有機物離子的接觸頻率減少，有機物離子一旦吸附於陰離子交換膜之離子交換基之後，會變得不易再生，所以期待具有更高的耐有機污染性之離子交換膜。
[專利文獻1]日本特開昭48-57893號公報 [專利文獻2]日本特開2001-157823號公報 [專利文獻3]日本特開2003-82130號公報
如前所述，欲防止有機物離子往膜內侵入之從前的離子交換膜，有某些短處，不能充分滿足需求。
本發明係為了解決這樣的課題而完成的，目的在於提供耐有機污染性優異可以安定地進行脫離子處理之離子交換膜與脫離子裝置，與其運作方法。
本發明之離子交換膜，其官能基具有3級胺基、2級胺基及1級胺基之至少1種。官能基之至少70%為3級胺基、2級胺基及1級胺基之中的至少1種為佳。
本發明之脫離子裝置，使用相關於本發明之離子交換膜。
本發明之脫離子裝置之運作方法，係此脫離子裝置的運作方法，特徵係具有藉由鹼溶液洗淨離子交換膜之工序。
在本發明之一態樣，被處理液含有機物，被處理液之E260(UV260nm的吸光度)為0.03以上。 [發明之效果]
富里酸(fulvic acid)等有機物，通常帶負電，所以對於官能基具有3級胺基、2級胺基及1級胺基之至少1種之本發明的離子交換膜，會因此電荷的靜電作用而吸附。4級銨基與1～3級胺基相比正電荷大，所以有機物的吸附力為4級銨基比1～3級胺基還要強固。本發明之離子交換膜，具有吸附力弱的1～3級胺基，所以用鹼液之洗淨效果很高。
此外，4級銨基總是帶正電。與這樣的4級銨基相比，具有3級胺基、2級胺基及1級胺基之至少1種之本發明的離子交換膜，對於胺基保有的非共用電子對若無某種正離子來配位就不會呈現正電荷性，富里酸這樣呈現陰離子性的有機物之吸附很少。
由於這樣，本發明之離子交換膜甚少發生有機物之障礙。
本發明之離子交換膜，官能基具有3級胺基、2級胺基及1級胺基之至少1種。這些胺基之取代基，例示甲基、乙基、丁基等，但異丙基這樣立體且體積大的取代基阻礙往交換基之離子接觸所以不佳。此外，相對於離子交換膜的重量之官能基的數量越多越好，高分子鏈以10～30m mol/g程度為佳。
本發明之離子交換膜，可以舉出把官能基具有3級胺基、2級胺基及1級胺基之至少1種的聚合物擔持於多孔質膜基材之膜，使該聚合物與基材聚合物混合而製膜之膜，或者是在多孔質膜基材直接導入前述官能基者。具有3級胺基、2級胺基及1級胺基之至少1種的聚合物之重量平均分子量為1000～100000程度之水溶性材料為佳。
製造本發明之離子交換膜，例示了使具有3級胺基、2級胺基及1級胺基之至少1種的聚合物之水溶液讓多孔質支撐體浸漬，水洗後使其乾燥的方法，但不限定於此。
又，具有1～3級胺基的離子交換膜之製造方法，亦可為粉碎弱鹼性陰離子交換樹脂混入高分子膜中的方法。在此場合，弱鹼性陰離子交換樹脂，通常係以3級胺基為主的離子交換樹脂，但幾乎都是在樹脂內部有4級銨基，由耐污染性的觀點來看，以使用使會引起有機物的強吸附之4級銨基不存在於樹脂內之完全3級胺基的弱鹼性陰離子交換樹脂為佳。
此外，作為具有1～3級胺基的離子交換膜之其他製造方法，亦可採用藉由接枝聚合(graft polymerization)等直接把官能基導入高分子膜的方法。
本發明之離子交換膜，可以用此構成電氣透析裝置、電氣脫離子裝置、擴散透析裝置、逆電氣透析裝置等。圖1係使用由此離子交換膜構成的陰離子交換膜之電氣脫離子裝置之示意剖面圖。
此電氣透析裝置，在陽極與陰極間，分別中介著電極室及雙極膜BPM，使氧室、陰離子交換膜AM、脫鹽室、陽離子交換膜CM、鹼室，以陽極側為酸室，陰極側為鹼室的方式設置。被處理水中的陰離子X-
及陽離子Y+
分別透過陰離子膜AM或陽離子膜CM移動至酸室或鹼室，由脫鹽室得到脫鹽水，同時由酸室得酸溶液，由鹼室得鹼溶液。
又，一般已知有機物污染導致的膜性能降低藉著鹼液洗淨而回復。於本發明，在離子交換膜被有機物污染的場合，以pH9～14之氫氧化鈉水溶液等鹼液來洗淨為佳。 [實施例]
以下，說明比較例及實施例。
[比較例1] 製作了依照雙極膜((股)Astom製造BP1-E)、陽離子交換膜((股)Astom製造CMX)、陰離子交換膜((股)Astom製造AHA)、雙極膜((股)Astom製造BP1-E)之順序層積膜而構成圖1所示的5室(負電極室、鹼室、脫鹽室、酸室、正電極室)之電氣透析裝置。各室的厚度為酸室1mm、脫鹽室1mm、鹼室1mm。各室的容積為酸室5.4mL、脫鹽室5.4 mL、鹼室5.4mL。
正負之各電極室，使0.5mol/L之氫氧化鈉水溶液以100mL/min之流速通液，於脫鹽室、鹼室、酸室以5mL/min之流速使被處理液通液。
原水(被處理液)，係添加氯化鈉100mg/L與作為有機污染物質之加拿大富里酸(Canadian Fulvic Acid) ((股)PIC-BIO製造)而調製者。此原水的導電率為38mS/m，TOC為8.2mg/L。此原水之E260(260nm之紫外線吸光度)為3，1/100之稀釋液的E260為0.03。
以50V之定電壓運作，進行2小時之處理，處理液的導電率由最初的0.3mS/m，以約0.0125mS/min的速度上升。2小時之後的處理水的導電率為約1.6mS/m。每1日的導電率上升速度為0.0125mS/m×60min×24小時=18mS/日。即便此速度為1/100，每1日導電率上升0.18mS，經過4日後也會超過1mS/m。
一般而言有機污染導致的膜性能降低藉著鹼液洗淨而回復。在此，僅對脫鹽室通水以超純水置換之後，使調整為pH12的氫氧化鈉水溶液以5mL/min流速通液120分鐘。通液後以超純水清洗，確認清洗液的pH成為中性之後再開始處理。結果，處理液之導電率為0.8mS/m，無法回復到初期的0.3mS/m。此外，處理水的導電率其後以0.013mS/min之速度，亦即與污染前同等的速度上升。
[實施例1] 使具有1級～3級胺基的分子量70000、樹脂成分濃度30重量百分比之次乙亞胺聚合物水溶液(日本觸媒(股)製造，商品名Epomin P-1000)浸漬於5A濾紙，乾燥1晚。將此濾紙浸漬於2%戊二醛(glutaraldehyde)水溶液，使反應1晚。將此濾紙由液中取出水洗之後，使浸漬於3重量百分比之次乙亞胺聚合物水溶液(日本觸媒(股)製造，商品名Epomin P-1000)，使反應2小時，水洗乾燥，製造了離子交換膜。
除了將此離子交換膜用於陰離子交換膜，還使各條件與前述比較例1相同進行了通液試驗，處理液的導電率如圖3所示，由最初的0.21mS/m，以約0.0008 mS/min之速度上升。2小時之後的處理水的導電率為0.34 mS/m。
處理水的導電率之上升速度為比較例1的5%，可以大幅抑制有機污染導致的性能降低，而且可得良好的水質之處理水。
接著，與比較例1同樣地僅對脫鹽室通水以超純水置換之後，使調整為pH12的氫氧化鈉水溶液以5mL/min流速通液120分鐘。通液後以超純水清洗，確認清洗液的pH成為中性之後再開始處理，處理水的導電率為0.18mS/m，回復到與初期的0.21mS/m相同的水質。處理水的導電率，如圖3所示，確認了同樣以0.0008mS/min之速度上升。結果，確認了藉由鹼洗淨，可以使性能回復到與新膜同等水準。
以上使用特定的形態詳細地說明了本發明，但對於發明所屬技術領域中具有通常知識者而言顯然可以在沒有脫離本發明的意圖與範圍的前提下進行種種的變更。 本申請案係根據2017年12月7日提出申請的日本專利申請案特願2017-235318而主張優先權，在此藉由引用而援用其所有內容。
圖1係顯示電氣透析裝置之一例之示意剖面圖。 圖2係顯示比較例的結果之圖。 圖3係顯示實施例的結果之圖。
Claims (5)
- 一種離子交換膜，其特徵為 作為官能基具有3級胺基、2級胺基及1級胺基之至少1種。
- 如申請專利範圍第1項之離子交換膜，其中 前述官能基之至少70%為1～3級胺基。
- 一種脫離子裝置，其特徵為 使用申請專利範圍第1或2項之離子交換膜。
- 一種申請專利範圍第3項之脫離子裝置之運作方法，其特徵為： 具有藉由鹼溶液洗淨離子交換膜之工序。
- 如申請專利範圍第4項之脫離子裝置之運作方法，其中 被處理液含有有機物，被處理液之E260為0.03以上。
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