TWI661863B - 多層複合膜 - Google Patents
多層複合膜 Download PDFInfo
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- TWI661863B TWI661863B TW107121273A TW107121273A TWI661863B TW I661863 B TWI661863 B TW I661863B TW 107121273 A TW107121273 A TW 107121273A TW 107121273 A TW107121273 A TW 107121273A TW I661863 B TWI661863 B TW I661863B
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Classifications
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Abstract
一種多層複合膜，基本上由多孔支撐層、無機多孔層、高分子多孔層以及分離層所組成。無機多孔層由無機微粒組成，配置於多孔支撐層上。高分子多孔層配置於無機多孔層上。分離層配置於高分子多孔層上。
Description
本發明是有關於一種水處理技術，特別是有關於一種用於水處理的多層複合膜。
目前而言，多層複合膜已被廣泛應用於水處理，如超過濾、微過濾、逆滲透以及正向滲透等處理結構。
傳統的多層複合膜結構為上層為多孔層，而下層為加強機械強度之加強層，此層可以是織布或是不織布，甚至其他可加強之材料。然而，加強層與其上層之高分子溶液結合時，因黏度等問題，導致製作多孔層所用的高分子溶液下滲到加強層，而在成膜後與加強層形成一阻力大之介面層。所述介面層會使多層複合膜的阻力變大而影響薄膜性能。
這種情況在正向滲透技術中更顯嚴重，由於用於正向滲透的多層複合膜兩側均有液體流動，所以加強層端會有很嚴重的內部濃度極化問題，而阻力大之介面層，會使內部濃度極化問題加劇。
雖然增加製作多孔層所用的高分子溶液黏性，可以防止
其下滲到加強層而形成阻力大的介面層。然而，改變高分子溶液黏度會使製備的薄膜結構較為緻密，且阻力較高，反而降低水的通量。因此，如何在維持水通量的前提下解決高阻力之介面層問題，為正向滲透薄膜之重要課題之一。
本發明提供一種多層複合膜，其可在不減少水通量的情況下，減少介面層的形成而提升薄膜性能。
本發明的一種多層複合膜，基本上由多孔支撐層、無機多孔層、高分子多孔層以及分離層所組成。無機多孔層由無機顆粒所組成，位在多孔支撐層上。高分子多孔層位於無機多孔層上，分離層位於高分子多孔層上。
在本發明的一實施例中，上述多孔支撐層包括織布或不織布。
在本發明的一實施例中，上述多孔支撐層的材料包括聚丙烯(PP)、聚苯二甲酸乙二酯(PET)、聚醯胺(PA)或其衍生物。
在本發明的一實施例中，上述多孔支撐層的厚度為30微米至130微米。
在本發明的一實施例中，上述無機顆粒包括奈米矽粒子、奈米碳管、石墨烯、沸石或其組合。
在本發明的一實施例中，上述無機多孔層的厚度為3微
米至10微米。
在本發明的一實施例中，上述高分子多孔層的材料包括聚丙烯腈(PAN)、聚碸(PSf)、聚醚碸(PES)、聚偏二氟乙烯(PVDF)或其衍生物。
在本發明的一實施例中，上述分離層的材料包括聚醯胺。
基於上述，本發明的多層複合膜在多孔支撐層與高分子多孔層之間配置有無機多孔層，由於無機多孔層是由無機顆粒組成，因此能藉由無機顆粒縮小(卡住)多孔支撐層的孔洞，有助防止成膜過程中高分子溶液下滲，而避免形成高阻力介面層，進而降低內部濃度極化問題。
為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施例，並配合所附圖式作詳細說明如下。
100‧‧‧多層複合膜
102‧‧‧多孔支撐層
102a、102b‧‧‧表面
104‧‧‧無機多孔層
106‧‧‧高分子多孔層
108‧‧‧分離層
110‧‧‧無機顆粒
T1、T2、T3‧‧‧厚度
圖1是依照本發明的一實施例的一種多層複合膜的剖面示意圖。
下文列舉實施例並配合所附圖式來進行詳細地說明，但所提供之實施例並非用以限制本發明所涵蓋的範圍。此外，圖式僅以說明為目的，並未依照原尺寸作圖，且可能放大或縮小不同的膜層來顯示於單一圖式中。
圖1為依照本發明一實施例的多層複合膜的剖面示意圖。
請參照圖1，本實施例的多層複合膜100基本上由一多孔支撐層102、一無機多孔層104、一高分子多孔層106以及一分離層108所組成。多孔支撐層102具有孔洞結構，使其兩端相連通。也就是說，若是溶液從表面102a進入多孔支撐層102，會從另一表面102b離開。多孔支撐層102可以由織布或不織布組成。不織布是由纖維經過高壓或是粘合生產而成的布狀物。多孔支撐層102的材料例如聚丙烯、聚苯二甲酸乙二酯、聚醯胺或其衍生物，但本發明不以此為限。多孔支撐層102可以提升多層複合膜100機械強度，增加多層複合膜100之耐用性。在本實施例中，多孔支撐層102的厚度T1例如在30微米至130微米之間。
請繼續參照圖1，無機多孔層104是配置在多孔支撐層102上。無機多孔層104由無機顆粒110所組成，因此無機顆粒110會落在多孔支撐層102的表面102a且適時地填補多孔支撐層102的孔洞。因此在後續形成高分子多孔層106時，可避免高分子溶液滲入多孔支撐層102而形成高阻力之介面層，而影響薄膜性能。無機多孔層104的無機顆粒110可列舉但不限於奈米矽粒子、奈米碳管(CNT)、石墨烯、沸石或其組合。無機顆粒110之間是以非共價鍵的形式結合，所述非共價鍵如凡得瓦力(van der Waals)。無機多孔層104的厚度T2例如在3微米至10微米之間。若是無機多孔層104的厚度T2小於3微米，無機多孔層104可能無法完整覆蓋多孔支撐層102；若是厚度T2大於10微米，可能
會使阻力變大，不利於水通過薄膜。然而本發明並不限於此，無機多孔層104的製作過程中所使用的溶液濃度也會影響無機多孔層104的成效，如無機顆粒110以奈米碳管為例，可採用0.1wt%以上的CNT溶液，以確保無機多孔層104能覆蓋多孔支撐層102，譬如使用0.1wt%~5wt%的CNT溶液。
請繼續參照圖1，本實施例的高分子多孔層106配置在無機多孔層104之上。同樣地，高分子多孔層106具有多孔結構，並且與無機多孔層104孔洞連通。高分子多孔層106的材料是能產生孔洞且具有黏性，而可被無機多孔層104擋住的，例如聚丙烯腈、聚碸、聚醚碸、聚偏二氟乙烯、其衍生物或上述之組合。高分子多孔層106的厚度T3例如在30微米至60微米之間。而高分子多孔層106能形成立體結構，以固定無機多孔層104，避免其在操作過程中損傷。至於分離層108是位於高分子多孔層106之上，其為無孔的材料層，可以阻隔水中的鹽類粒子。分離層108的材料例如聚醯胺，其可以是由間苯二胺與均苯三甲醯氯聚合而成。
為驗證本發明的功效，以下列舉實驗來進行更進一步的說明。但本發明並不只限於以下的內容。
〈實驗例1〉
首先將基重50g/m2、厚度66微米之不織布固定於玻璃板上，並且配製固含量3wt%之CNT溶液。待CNT溶液分散均勻後，將CNT溶液以52微米之線棒刮塗於不織布表面，隨即置入
50℃烘箱中乾燥15min，待完全乾燥後將之置於室溫冷卻。
配置PAN與N-甲基吡咯烷酮(NMP)高分子溶液12wt%，並且置於50℃烘箱中直至完全溶解，待高分子溶液降至室溫後，以30微米的厚度塗佈於CNT/不織布底材上，隨即進入水中進行相分離。待溶劑完全交換後，於水中取出將其置於2wt%間苯二胺(MPD)水溶液中兩分鐘，並且以0.1wt%均苯三甲醯氯(TMC)溶液反應1分鐘，以形成界面聚合分離層，待完全反應後，所得到的多層複合膜測試前均置於去離子水中。
實驗例1所得到的多層複合膜進行正向滲透效能測試之結果記載於下表1。
〈實驗例2〉
實驗例2中採取與實驗例1中相同的製程。實驗例2與實驗例1的差別在於配製PAN/NMP高分子溶液時，濃度由12wt%改為15wt%。
實驗例2所得到的多層複合膜進行正向滲透效能測試之結果記載於下表1。
〈比較例1〉
採用實驗例1的方式製備多層複合膜，但其中沒有無機多孔層。
比較例1所得到的多層複合膜進行正向滲透效能測試之結果記載於下表1。
〈實驗例3〉
採用與實驗例1中相同的製程。實驗例3與實驗例1的差別在於CNT塗佈溶液中添加1wt%聚乙烯醇高分子，其餘實驗參數皆與實驗例1相同。
從表1可得到本發明的多層複合膜在水通量優於比較例1~2，且逆向溶質通量維持在標準範圍(10以下)。
綜上所述，本發明藉由在多孔支撐層與高分子多孔層之間配置由無機顆粒組成的無機多孔層，因此能藉由無機顆粒縮小(擋住)多孔支撐層的孔洞，有助防止成膜過程中高分子溶液下滲，而達到避免形成高阻力介面層形成的效果，進而降低內部濃度極化問題。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為淮。
Claims (8)
- 一種多層複合膜，基本上由以下膜層所組成：多孔支撐層；無機多孔層，由多數個無機顆粒所組成，位於所述多孔支撐層之上；高分子多孔層，位於所述無機多孔層上；以及分離層，位於所述高分子多孔層上。
- 如申請專利範圍第1項所述的多層複合膜，其中所述多孔支撐層包括織布或不織布。
- 如申請專利範圍第1項所述的多層複合膜，其中所述多孔支撐層的材料包括聚丙烯、聚苯二甲酸乙二酯、聚醯胺或其衍生物。
- 如申請專利範圍第1項所述的多層複合膜，其中所述多孔支撐層的厚度為30微米至130微米。
- 如申請專利範圍第1項所述的多層複合膜，其中所述無機顆粒的材料包括奈米矽粒子、奈米碳管、石墨烯、沸石或其組合。
- 如申請專利範圍第1項所述的多層複合膜，其中所述無機多孔層的厚度為3微米至10微米。
- 如申請專利範圍第1項所述的多層複合膜，其中所述高分子多孔層的材料包括聚丙烯腈、聚碸、聚醚碸、聚偏二氟乙烯或其衍生物。
- 如申請專利範圍第1項所述的多層複合膜，其中所述分離層的材料包括聚醯胺。
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