CN105916573A - 包括纤维素基季铵涂层的复合聚酰胺膜 - Google Patents
包括纤维素基季铵涂层的复合聚酰胺膜 Download PDFInfo
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- CN105916573A CN105916573A CN201580004554.1A CN201580004554A CN105916573A CN 105916573 A CN105916573 A CN 105916573A CN 201580004554 A CN201580004554 A CN 201580004554A CN 105916573 A CN105916573 A CN 105916573A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
一种薄膜复合膜，其包含位于多孔载体与涂层之间的薄膜聚酰胺层，其中所述涂层包含包括多个季铵基团或其盐的纤维素基聚合物。
Description
技术领域
本发明涉及聚酰胺复合膜。
背景技术
复合膜用于多种流体分离。一种类型是“薄膜复合”(TFC)膜，其包括提供于下面的多孔载体上的薄膜区别层。薄膜层可以通过由不混溶溶液依次涂布在载体上的多官能胺(例如间苯二胺)与多官能酰基卤(例如均苯三甲酰氯)单体之间的界面缩聚反应形成。实例描述于US 4277344和US 6878278中。
可以施用聚合物涂层以改变膜的表面性质，例如以改良防垢性。实例描述于以下中：US8025159(包含包括季铵基团的聚苯乙烯、聚乙烯脒、聚乙烯吡啶、聚吡咯和聚乙烯二唑的离子大分子)、US6177011和US8443986(聚乙烯醇)、US2010/0133172(纤维素制品、聚乙烯醇、聚丙烯酸酯、聚氧化乙烯)US8017050(聚多巴胺)、US8002120(聚恶唑啉)，和US6280853、US 6913694、US7918349、US7905361、US7815987、US2011/0220569、US2011/0259817、US2011/0284454、US2011/0284454(聚氧化烯、掺合物和衍生物)。R.Malaisamy等人,《用于单价阴离子的选择性去除、分离和纯化技术的纳米过滤膜的聚电解质改性(Polyelectrolyte Modification of Nanofiltration Membranesfor Selective Removal of Monovalent Anions,Separation and Purification Technology)》77,367-374(2011)描述一种多层涂层，其包含包括聚苯乙烯磺酸盐和聚(二烯丙基二甲基铵)氯化物的交替聚电解质薄膜。也参见T.Ishigami,等人,《反向渗透膜通过经由层叠组装、分离和纯化技术的表面改性的积垢降低(Fouling Reduction of Reverse OsmosisMembrane by Surface Modification via Layer-by-Layer Assembly,Separation andPurification Technology)》99,1-7(2012)，和S.Liu,等人,《聚合物表面改性经由界面聚合对聚合物-蛋白质相互作用的影响(The Effect of Polymer Surface Modification viaInterfacial Polymerization on Polymer-Protein Interaction)》,(2009)www.interscience.wiley.com.。S.Belfer等人,《膜科学杂志(Journal of MembraneScience)》,第139卷,第2期,175-181(1998)描述一种通过将甲基丙烯酸或聚乙二醇甲基丙烯酸酯直接基团地接枝于复合膜的聚酰胺表面上来抑制膜积垢的方法。也参见US7677398。继续探索在最小的通量降低下提供防垢性的耐用涂层。
发明内容
本发明包括一种薄膜复合膜，其包括位于多孔载体与涂层之间的薄膜聚酰胺层，其中涂层包含包括多个季铵基团的纤维素基聚合物。
附图说明
图1是使用如实例部分中所描述的硅酸盐积垢测试的操作通量(GFD)相较于通量损失(GFD)的曲线。
图2是使用如实例部分中所描述的氧化铝积垢测试的操作通量(GFD)相较于通量损失(GFD)的曲线。
具体实施方式
本发明未特别局限于特定类型、构造或形状的复合膜或应用。举例来说，本发明适用于多种应用中所用的平板、管状和中空纤维聚酰胺膜，所述多种应用包括正向渗透(FO)、反向渗透(RO)、纳米过滤(NF)、超滤(UF)、微滤(MF)和压力延迟流体分离。然而，本发明尤其适用于经设计用于RO和NF分离(统称为“超微过滤”)的膜。RO复合膜相对不可渗透几乎全部的溶解盐并且典型地阻挡大于约95％的单价离子盐，如氯化钠。RO复合膜也典型地阻挡大于约95％的无机化合物以及分子量大于约100道尔顿的有机分子。NF复合膜比RO复合膜更可渗透并且典型地阻挡小于约95％的单价离子盐，同时阻挡大于约50％(并且常常大于90％)的二价离子盐，这取决于二价离子的种类。NF复合膜也典型地阻挡在纳米范围中的粒子以及分子量大于约200到500道尔顿的有机分子。
复合聚酰胺膜的实例包括膜技术公司(FilmTec Corporation)FT-30TM型膜，即包含非织造背衬网(例如PET纱布)的底层(背侧)、具有约25-125μm典型厚度的多孔载体的中间层和包含厚度典型地小于约1微米(例如0.01微米到1微米，但更通常约0.01到0.1μm)的薄膜聚酰胺层的顶层(前侧)的平板复合膜。多孔载体典型地是具有一定孔径的聚合材料，所述孔径具有足以准许渗透物基本上不受限制通过的尺寸，但并未大到足以干扰上面形成的薄膜聚酰胺层的桥接。举例来说，载体的孔径优选地在约0.001到0.5μm范围内。多孔载体的非限制性实例包括由以下制成的那些载体：聚砜、聚醚砜、聚酰亚胺、聚酰胺、聚醚酰亚胺、聚丙烯腈、聚(甲基丙烯酸甲酯)、聚乙烯、聚丙烯和多种卤化聚合物，如聚偏二氟乙烯。对于超微过滤应用来说，多孔载体提供强度，但由于其相对较高的孔隙度而几乎无流体流动阻力。
由于其相对较薄，聚酰胺层常常依据其在多孔载体上的涂布覆盖率或负载量加以描述，例如每平方米多孔载体表面积约2到5000mg聚酰胺并且更优选的是约50到500mg/m2。聚酰胺层优选通过多孔载体表面上多官能胺单体(例如间苯二胺(mPD))与多官能酰基卤单体(均苯三甲酰氯(TMC))之间的界面缩聚反应来制备，如US 4277344和US 6878278中所描述。更确切地说，聚酰胺膜层可以通过在多孔载体的至少一个表面上使多官能胺单体与多官能酰基卤单体(其中每一术语打算均指单种物质或多种物质的使用)界面聚合来制备。如本文所用，术语“聚酰胺”是指沿着分子链出现酰胺键(-C(O)NH-)的聚合物。多官能胺和多官能酰基卤单体最常借助于涂布步骤由溶液施用到多孔载体，其中所述多官能胺单体典型地由水基或极性溶液涂布并且所述多官能酰基卤由有机基或非极性溶液涂布。尽管涂布步骤无需遵循特定顺序，但多官能胺单体优选地首先涂布在多孔载体上，随后涂布多官能酰基卤。涂布可以通过喷雾、涂膜、辊涂或经由在其它涂布技术当中使用浸渍罐而实现。可以通过气刀、干燥器、烘箱等从载体去除过量溶液。
多官能胺单体可以呈极性溶液形式施用到多孔载体。极性溶液可以含有约0.1到约10wt％并且更优选约1到约6wt％多官能胺单体。在一组实施例中，极性溶液包括至少2.5wt％(例如2.5到6wt％)多官能胺单体。一旦涂布在多孔载体上，可以任选地去除过量溶液。
多官能酰基卤可以溶解于约0.01到10wt％、优选0.05到3％wt％范围内的非极性溶剂中，并且可以作为连续涂布操作的一部分传递。在多官能胺单体浓度小于3wt％的一组实施例中，多官能酰基卤小于0.3wt％。代表性实例包括合适的非极性溶剂，包括石蜡(例如己烷、环己烷、庚烷、辛烷、十二烷)以及异链烷烃(例如ISOPARTML)。非极性溶液可以包括额外成分，包括共溶剂、相转移剂、增溶剂、络合剂以及除酸剂，其中个别添加剂可以提供多个功能。代表性共溶剂包括：苯、甲苯、二甲苯、均三甲苯、乙苯、二乙二醇二甲醚、环己酮、乙酸乙酯、丁基carbitolTM乙酸酯、月桂酸甲酯和丙酮。代表性除酸剂包括N,N-二异丙基乙胺(DIEA)。非极性溶液还可以包括少量水或其它极性添加剂，但是浓度优选地低于其在非极性溶液中的溶解度极限。
一旦彼此接触，多官能酰基卤和多官能胺单体在其表面界面处反应以形成聚酰胺层或膜。这一层常常被称作聚酰胺“区别层”或“薄膜层”，给复合膜提供其用于使溶质(例如盐)与溶剂(例如水性进料)分离的主要构件。
多官能酰基卤和多官能胺单体的反应时间可以小于一秒，但接触时间典型地在约1到60秒范围内。可以通过空气吹扫或用水冲洗所述膜并且随后在例如约40℃到约120℃的高温下干燥来去除过量溶剂。
复合膜进一步包括位于薄膜聚酰胺层上的涂层(与多孔载体相对)。在一个实施例中，涂层由包含包括多个季铵基团的纤维素基聚合物的溶液施用到聚酰胺层。涂布溶液的施用可以是刚在形成聚酰胺复合膜后实施的连续膜制造工艺的一部分；或可以在产生复合膜后很好地施用，如在一元件中(例如其中纤维素基聚合物添加到加压进料水中，以形成操作期间通过最终元件的涂布溶液)。术语“施用(applying/applied)”打算广泛地描述使纤维素基聚合物与聚酰胺膜的至少一个表面部分接触的种类繁多的方法，如借助于喷雾、气刀涂、辊涂、海绵揩拭、涂布、浸渍、刷涂或任何其它已知方法。一种优选的施用技术是借助于辊式接触涂布机(本领域中有时称作“吻”涂布机)将改性剂的薄涂层施用于聚酰胺膜的外表面的至少一部分上。纤维素基聚合物优选地由水基溶液传递。溶液包含至少0.001、优选至少0.01并且更优选至少0.1重量百分比的纤维素基聚合物，和小于约10并且更优选小于约1重量百分比的纤维素基聚合物。涂布溶液还可以包括其它成分，包括(但不限于)共溶剂和改性剂以及从先前制造步骤“带出”的残余物。纤维素涂层优选覆盖基本上大部分的聚酰胺表面。涂层优选以至少10mg/m2(例如优选5mg/m2到50mg/m2)的覆盖率提供。这一覆盖率约等于0.003μm到0.03μm的优选厚度。
涂层包括用多个季铵基团或其盐官能化的纤维素基聚合物。纤维素基聚合物不受特定限制并且由式1表示，
式1：
其中R1、R2和R3独立地选自：氢、羟烷基、烷基和烷氧基；其中羟烷基、烷氧基和烷基可以包含1到130个碳原子(优选1到6个碳原子)，其可以未被取代或被羟基、羧酸、卤素、烷氧基、羟烷基和烷基(其中羟烷基、烷氧基和烷基可以包含1到30个碳原子)取代。合适的纤维素基聚合物的代表性实例包括纤维素以及酯和醚衍生物，如：乙酸纤维素、三乙酸纤维素、丙酸纤维素、乙酸丙酸纤维素、乙酸丁酸纤维素、硫酸纤维素、甲基纤维素(MC)、乙基纤维素(EC)、乙基甲基纤维素、羟乙基纤维素(HEC)、羟丙基纤维素(HPC)、羟乙基甲基纤维素(HEMC)、羟丙基甲基纤维素(HPMC)和羧甲基纤维素(CMC)。HEC是优选的纤维素基聚合物。至少一部分纤维素重复单元经官能化，使得R1、R2和R3中的至少一个独立地选自由式2表示的季铵官能团。
式2：
其中R4、R5和R6独立地选自烷基和芳基(优选地具有1到12个碳的烷基)，其可以未被取代或被烷基、烷氧基、羟基和卤基取代，并且L是选自烷基、烷氧基、聚烷氧基或芳基的键联基团，其可以未被取代或被以下各项中的至少一者取代：羟基、烷基、烷氧基、卤基和羧酸。优选的键联基团包括包含2到12个碳原子的烷氧基、至少一个醚基，并且其可以未被取代或被一个或多个羟基取代。
具有相对较高的季铵取代的纤维素基聚合物更强有力地静电结合到薄膜聚酰胺层，并且在长期使用后仍保留在聚酰胺层上。此外，更高的季铵取代赋予膜更为正性的电荷，并且降低包括二氧化硅和氧化铝的诸多污垢物的积垢。在一优选实施例中，纤维素基聚合物的季铵取代度(DS)是0.05到1、0.1到0.7，并且更优选0.2到0.6；其中DS值是连接到葡萄糖单元的季铵基团的平均数(最大取代度＝3)。一些葡萄糖重复单元可具有一个以上季铵基团但其它可能不被取代。优选的纤维素基聚合物的Mw是1,000到1,000,000，并且更优选10,000到750,000。优选涂料的具体实例包括均可商购自爱美高公司(Amerchol Corporation)的UCARETM聚合物(INCI名称：聚季铵-10)，如UCARETMJR400；SoftCatTM聚合物(INCI名称：聚季铵-67)，如SoftCatTMSK和SX；和CELLOSIZETM聚合物。
实例
如下制备样品薄膜复合膜。将聚砜载体浇注在二甲基甲酰胺(DMF)中并且随后浸泡在3.1wt％间苯二胺(mPD)水溶液中。接着将所得载体以恒定速度拉出反应台，同时施用一层薄的均一的非极性涂布溶液。非极性涂布溶液包括异链烷烃溶剂(ISOPARL)、0.2wt％均苯三甲酰氯(TMC)、0.03wt％1-羧基-3,5-二氯甲酰基苯和0.22wt％磷酸三丁酯。去除过量的非极性溶液，并且将所得复合膜依序通过水冲洗槽和干燥烘箱，并且随后除对照以外用以下纤维素材料中的一种涂布(16mg/m2)；
◆对照-未涂布
■羧甲基纤维素钠(CMC，WALOCELTMCRT30PA，陶氏沃尔富纤维素事业部(Dow Wolff Cellulosics))，
*羟乙基纤维素(HEC，HEC QP-300，爱美高公司)，和
▲UCARE JR400(季铵取代度＝0.4，爱美高公司)。
如下测试经涂布膜样品。将样品膜置于flatcell设备中，并且使其稳定，同时在70psi和25℃下用纯RO水馈送至少30分钟，其后测量膜的通量。将进料压力增加到120psi并且使其稳定30分钟，之后再测量通量。将进料压力进一步增加到150psi并且使其稳定，之后再测量通量。这些通量值表示操作通量并且按加仑/每平方英尺膜/天(GFD)记录。在这些测量之后，将含有所需量的污垢物的水添加到纯水进料中，以提供20升积垢进料水溶液(参见下文的积垢水制备)。将这种水馈送到flatcell设备，并且在70psi和25℃下使系统稳定/结垢60分钟，其后测量膜的通量。随后，将压力增加到120psi并且在60分钟的稳定后再测量通量。在150psi下再次重复这一步骤。针对每一对应的实验压力(70、120、150psi)，从纯水通量测量值减去积垢水通量测量值，以提供“通量的变化”值。通过绘制“通量的变化”相较于操作通量来比较数据，并且在图1(硅酸盐积垢水)和2(氧化铝积垢水)中说明。
硅酸盐积垢进料水制备：通过将75mg聚乙烯醇(MW＝6,000g/mol，80％已水解，Polysciences,Inc.)和2g二氧化硅(二氧化硅纳米粉末，球形并且多孔的，5-15nm，西格玛奥德里奇(Sigma-Aldrich))添加到锥形烧杯中的200ml水中，来制备硅酸盐分散液，其中将pH值调节到8与9之间。超声处理二氧化硅分散液45分钟。超声处理后，使用磁性搅拌棒连续搅拌分散液，直到将全部内含物添加到flatcell进料水槽中，并且用RO水稀释以达到最终20L体积。
氧化铝积垢进料水制备：通过将75mg聚乙烯醇(MW＝6,000g/mol，80％已水解，Polysciences,Inc.)和2g氧化铝纳米粒子(50nm，Skyspring Nanomaterials,Inc.)添加到锥形烧杯中的200ml水中，来制备氧化铝分散液。其中将pH值调节到8与9之间。超声处理二氧化硅分散液45分钟。超声处理后，使用磁性搅拌棒连续搅拌分散液，直到将全部内含物添加到flatcell进料水槽中，并且用RO水稀释以达到最终20L体积。
Claims (4)
1.一种薄膜复合膜，其包含位于多孔载体与涂层之间的薄膜聚酰胺层，其中所述涂层包含包括多个季铵基团或其盐的纤维素基聚合物。
2.根据权利要求1所述的膜，其中所述纤维素基聚合物的季铵取代度(DS)是0.05到1。
3.根据权利要求1所述的膜，其中所述涂层的覆盖率是至少10mg/m2。
4.根据权利要求1所述的膜，其中所述薄膜聚酰胺层包含多官能胺单体与多官能酰基卤单体的反应产物。
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| CN107469649A (zh) * | 2017-09-05 | 2017-12-15 | 湖南澳维环保科技有限公司 | 一种亲水性抗污染聚酰胺复合反渗透膜及其制备方法 |
| CN107754619A (zh) * | 2017-11-12 | 2018-03-06 | 韦韬 | 一种天然聚电解质纳滤膜的制备方法 |
| CN110290860A (zh) * | 2016-09-12 | 2019-09-27 | 梵特斯技术有限公司 | 与纤维素酯膜共价键合的薄膜及其制备方法 |
| CN113731190A (zh) * | 2021-07-20 | 2021-12-03 | 浙大宁波理工学院 | 一种纳米纤维素层层自组装膜及其制备方法 |
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| EP3431171A1 (en) * | 2017-07-19 | 2019-01-23 | Gambro Lundia AB | Filter membrane and device |
| JP6526894B1 (ja) | 2018-09-20 | 2019-06-05 | 日東電工株式会社 | 分離膜 |
| JP6484748B1 (ja) * | 2018-09-20 | 2019-03-13 | 日東電工株式会社 | 分離膜 |
| JP7027364B2 (ja) | 2019-03-12 | 2022-03-01 | 日東電工株式会社 | 硫酸イオン除去システム及び方法 |
| US11325077B2 (en) * | 2019-10-24 | 2022-05-10 | King Fahd University Of Petroleum And Minerals | Composite membrane containing a polydopamine-poly acyl halide matrix incorporating carbide-derived carbon and methods thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110290860A (zh) * | 2016-09-12 | 2019-09-27 | 梵特斯技术有限公司 | 与纤维素酯膜共价键合的薄膜及其制备方法 |
| CN107469649A (zh) * | 2017-09-05 | 2017-12-15 | 湖南澳维环保科技有限公司 | 一种亲水性抗污染聚酰胺复合反渗透膜及其制备方法 |
| CN107469649B (zh) * | 2017-09-05 | 2021-05-14 | 湖南澳维环保科技有限公司 | 一种亲水性抗污染聚酰胺复合反渗透膜及其制备方法 |
| CN107754619A (zh) * | 2017-11-12 | 2018-03-06 | 韦韬 | 一种天然聚电解质纳滤膜的制备方法 |
| CN107754619B (zh) * | 2017-11-12 | 2020-05-19 | 韦韬 | 一种天然聚电解质纳滤膜的制备方法 |
| CN113731190A (zh) * | 2021-07-20 | 2021-12-03 | 浙大宁波理工学院 | 一种纳米纤维素层层自组装膜及其制备方法 |
| CN113731190B (zh) * | 2021-07-20 | 2024-06-25 | 浙大宁波理工学院 | 一种纳米纤维素层层自组装膜及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20160325239A1 (en) | 2016-11-10 |
| WO2015116508A1 (en) | 2015-08-06 |
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