CN102711967A - 纳米孔半渗透隔膜及其制造方法 - Google Patents
纳米孔半渗透隔膜及其制造方法 Download PDFInfo
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Abstract
过滤器包括具有在其内形成的多个纳米通道的隔膜。通过自组装在限定纳米通道的表面上沉积官能化的纳米颗粒，从而降低所述隔膜的最终直径。还提供了制造和使用所述过滤器的方法。
Description
背景技术
本发明涉及半渗透隔膜，更具体地涉及纳米孔隔膜及其制造方法和将其用于脱盐和其它工艺的方法。
水脱盐可以考虑两种方法。用于水脱盐的两种基本方法包括反渗透和蒸馏。蒸馏方法要求将流体水转化成蒸气相并从所述蒸气冷凝水。这一方法的成本相当高，且要求显著大的能量使用。反渗透方法利用在盐化液体上的压力，以强制水分子通过半渗透隔膜。这一方法具有相对低的能耗速率。
使用反渗透脱盐的比(每单位所生产的可饮用水)能量已经从二十世纪八十年代的超过10kWh/m3下降到低于4kWh/m3，接近理论最小要求能量0.7kWh/m3。为了改进反渗透方法的技术水平，具有均匀的孔分布和更加可渗透的分离层的新型隔膜可潜在地维持或改进盐排斥，同时增加反渗透方法中的流通量。用于有效脱盐的隔膜的孔大小为约10纳米或更小。用于实现这些尺寸的目前的方法是相当复杂的、高成本的和耗时的。一种方法使用可商购的阳极化氧化铝膜，其具有直径为10－200nm或更大的纳米通道的平行阵列。为了使孔径变窄，通过化学气相沉积、原子层沉积或物理气相沉积将表面荷电的材料沉积在纳米通道开口处。或者，在入口开口处通过原子层沉积形成氧化物层。要求多次通过以实现所需的厚度和孔径。为了获得适合于脱盐的所需直径，这些方法是耗时的、复杂的和相对成本高的。而且，目前的方法仅使纳米通道的入口开口变窄。
因此，本领域需要开口小于10nm的改进的隔膜，其中该方法对于生产目的来说是有效的且经济上可行的。
发明概述
本文公开的是过滤器，过滤器系统，和制造用于所述过滤器的纳米孔隔膜的方法。在一个实施方案中，过滤器包含具有在其内形成的多个纳米通道的多孔隔膜，其中所述纳米通道包含氧化物表面且具有第一直径；和官能化纳米颗粒的自组装膜，其中所述官能化纳米颗粒包含纳米颗粒和布置在其上的有机配体，该有机配体具有至少一个能与所述氧化物表面反应的官能团，其中所述自组装膜将所述第一直径降低到第二直径。
过滤器系统包含为在压力下接收电解质溶液而构造的第一体积；和通过具有在其内形成的多个纳米通道的隔膜而与第一体积隔离的第二体积，所述纳米通道包括第一直径和连接到所述纳米通道表面上的纳米颗粒的自组装单层，其中所述自组装单层给过滤器系统提供第二直径，所述第二直径小于所述第一直径，和其中所述第二直径有效防止电解质溶液内的离子传输通过所述隔膜。
制造过滤器的方法包括使多孔隔膜材料内的每一纳米通道的直径变窄，这包括将官能化纳米颗粒的自组装单层连接到每一纳米通道的内表面上，其中每一官能化的纳米颗粒包含纳米颗粒和连接到纳米颗粒上的有机配体，所述有机配体包含有效地与内表面反应并在内表面上形成纳米颗粒的自组装单层的至少一个官能团。
附图简要说明
本公开将在以下参考下述附图对优选实施方案的说明中提供细节，其中：
图1是沿纳米管道或纳米通道的纵轴所取的、通过一个隔膜的截面图，其显示根据一个示例性实施方案的纳米通道；
图2是图1的隔膜的顶视图，其显示根据一个示例性实施方案的纳米通道；
图3是描绘根据一个示例性实施方案的脱盐系统的方框图；
图4示意性图示了用于从电解质流体中过滤离子的一个示例性工艺流程图。
详细说明
根据本发明，公开了一种新型半渗透纳米孔隔膜和形成该隔膜的方法。所述半渗透隔膜包括具有确定直径的平行纳米通道阵列的多孔隔膜，其中所述纳米通道的限定流体通路的内表面与官能化纳米颗粒通过自组装反应，以使该直径进一步变窄。在一个实施方案中，选择官能化纳米颗粒的尺寸，以使多孔隔膜纳米通道的直径变窄到有效阻断离子传输通过所述流体通路的尺寸，从而起到离子过滤器的作用。与现有技术的方法不同，本发明的制造隔膜的方法简单，有效，且商业上可行。
所述半渗透隔膜由多孔隔膜材料形成，所述多孔隔膜材料包括直径通常为约20－约300nm的纳米通道的平行阵列。可以使用公知的方法，通过电解钝化(passivation)金属膜，例如阳极化，制造所述多孔隔膜材料。例如，不同厚度的多孔阳极化氧化铝膜是可商购的，或者可以通过在本领域公知的各种反应条件下在草酸、硫酸、铬酸和/或磷酸中阳极化铝膜来制备。采用反复的阳极化-蚀刻循环，可以通过自组织制备高度有序的直的纳米通道。示例性的方法被公开于以下文章中：Wang等人，“Nanowire and Nanotube Syntheses ThroughSelf-assembled Nanoporous AAO Templates”；O.Jessensky等人，“Self-Organized formation of hexagonal pore arrays in anodicalumina”,Appl.Phys.Lett.,72,(1998),p.1173；和G.Sklar等人，“Pulsed deposition into AAO templates for CVD growth ofcarbon nanotube arrays”,Nanotechnology,16(2005)1265-1271。这些方法可以被用于通过阳极氧化方法在铝膜内形成高长径比的平行纳米通道。尽管具体地提到阳极化的氧化铝，但本发明不打算局限于此。其它隔膜材料也被想到。
所述多孔隔膜材料可以被形成在片材中并切割到合适的大小，或者可以被形成在或包括在预先确定尺寸的面板中。对于脱盐应用来说，所述多孔隔膜材料是具有20－30nm的纳米通道直径的多孔隔膜。用官能化的纳米颗粒的溶液处理多孔隔膜材料，其中官能化的纳米颗粒的特定官能团被选择以与氧化物表面反应。以这种方式，可以在纳米通道的内表面上形成自组装的官能化纳米颗粒的一个单层，且与现有技术不同，所述官能化纳米颗粒的单层可以覆盖从入口开口到出口开口的整个表面。取决于多孔隔膜材料的起始直径，可以选择官能化的纳米颗粒，使得在装饰限定纳米通道的内表面之后，相对的纳米颗粒之间的距离在一些实施方案中小于20nm，在其它实施方案中小于10nm，和在其它实施方案中小于约5nm。对于脱盐来说，由所述隔膜提供的最终孔径为2－3nm。可以通过仔细选择纳米颗粒的粒度和配体有效地控制最终直径。以这种方式，所述隔膜和它随后作为过滤器的用途可以按照给定的应用调节。对于脱盐工艺来说，所述过滤器可以被用于反渗透应用中，其中所有离子被有效地阻断，使得仅仅水流经所述纳米通道。然而，其它物理或化学方法可以采用本发明的原理。
本文中使用的术语“纳米颗粒”通常是指具有至少一个小于100的维度的任何纳米材料。纳米颗粒可以是或者可以不是结晶性的。合适的纳米颗粒不打算被限制到任何特定的材料，只要纳米颗粒可以用有机配体官能化即可，所述有机配体具有对表面多孔隔膜材料具有反应性，例如对氧化物表面具有反应性且对它们被布置在其中的环境呈惰性的端基。在一个实施方案中，纳米颗粒材料不赋予表面电荷。在其它实施方案中，纳米颗粒是表面荷电的。示例性的纳米颗粒包括金属，例如铜，金，铁，银等；金属氧化物，例如二氧化钛，氧化铝，二氧化硅，氧化锌，二氧化锆等；半导体材料；等等。应当注意，鉴于它们的固有的成本，半导体纳米颗粒通常较不优选。纳米颗粒的粒度通常在2－20nm的范围内，取决于多孔隔膜材料内纳米通道的直径，但是更小或者更大的粒度可以被使用，取决于特定的应用。
通过用有机配体涂布纳米颗粒来官能化所述纳米颗粒。所述有机配体包括至少一个官能团，该官能团的反应性足以将所述纳米颗粒连接(例如形成共价键或离子键)到在隔膜内最初形成的纳米通道的内表面上。合适的有机配体包括但不限于包括诸如异羟肟酸，羧酸，膦酸，联吡啶，三联吡啶，酞菁之类端基或包含前述端基中至少之一的组合的化合物。芳族化合物的一个具体实例是具有异羟肟酸尾基的芳基重氮鎓盐。其它实例包括具有膦酸端基的重氮鎓盐，并且对于氧化物纳米颗粒，人们可以使用双官能的有机化合物，例如二膦酸，二异羟肟酸，或具有羧酸或异羟肟酸端基的膦酸。
以下的路线I提供了用于将有机配体连接到金属纳米颗粒上的一个示例性方法。
官能化的纳米颗粒
在这一路线中，x是阴离子，m是二价连接，n是1－500的整数，和Z是对纳米通道表面具有反应性的官能团。在金属纳米颗粒上的所述一个或多个起始配体中的一个或多个可以与双官能的有机分子交换，如某些应用中可能希望的那样。
图1示意性图示了通常用参考标记10表示的半渗透隔膜的截面图。半渗透隔膜10包括多孔隔膜材料16，该多孔隔膜材料16包括平行纳米孔或纳米通道14的阵列12。所述纳米孔的直径通常为大于20nm到200nm。在限定所述纳米通道14的内表面上安置纳米颗粒18的单层，从而降低孔径到小于10nm。对于脱盐应用来说，孔径被降低到小于约3nm。以这种方式，在盐水中的大的电解质离子如钠和氯离子被有效地阻止传输通过隔膜10。
参考图2，说明性地显示了观察平行纳米通道14的阵列12的顶视图。每一纳米通道14包括官能化纳米颗粒18的自组装的单层。可以制造具有约3nm的最终直径的用于脱盐应用的装置或隔膜10。其它尺寸也是可能的，且可依据应用而使用。
作为实例，所述隔膜材料是具有约20－约30nm的孔径的阳极化氧化铝。所述纳米通道的氧化物表面与溶液内提供的有机配体涂布的纳米颗粒的端基反应，以有效地使最终直径变窄，使得相对的纳米颗粒的距离为约3nm。
参考图3，脱盐装置100包括具有平行纳米通道和官能化纳米颗粒的自组装单层的大阵列的一个或多个半渗透隔膜或过滤器102。所述隔膜102可以被构建在格栅、网状物或其它结构元件110上，以获得强度。隔膜102的纳米通道阵列将在第一存储处或容器内的流体体积104如含盐水溶液与第二体积106隔离，钠和氯离子没有渗透到所述第二体积106中，因此形成脱盐水。可以施加压力P到含盐侧上，以增加水分子通过隔膜102的纳米孔/纳米通道阵列的渗透。混合器或其它扰动装置120可以用于搅拌体积104内的水。
可以使用压力调节器装置112来维持压力P，以确保脱盐系统100的合适功能。或者，可以构造一种容器，以利用流体体积或容器104中的水柱的高度或者通过其它方式来提供工作压力P。
可以延伸图3中描述的实施方案，以包括串联的多个隔膜，从而进一步改善所述过滤。在一个实施方案中，可以使用不同的过滤段，其中在每一段中控制压力，以确保每一段都有效地行使其功能。这可以包括增加或降低在每一段的流体的中间压力。
一个连续的实施方案可以包括用于在不同尺寸下过滤的另外的隔膜102’和段116。例如，在第一体积104中的海水可以首先通过中间过滤器(102)，该中间过滤器阻断一些但并非所有离子。然后可以使用具有不同的纳米通道直径并且因此阻断不同的浓度的第二段过滤器102’。
尽管已经描述了水的脱盐作为说明性的实例，但其它流体可以按照本发明的原理过滤。有利地，可以提供一种脱盐系统，其是被动的(不要求动力源)，且可以被用作便宜的脱盐系统，紧急脱盐系统(例如在救生艇上)等。
参考图4，显示了按照本发明的原理使用过滤器的一个说明性方法的流程图。在方块250中，用电解质溶液充满第一体积。这一体积优选被混合或不断地补充。在方块252中，施加低于压力阈值的压力到在第一体积中的电解质溶液上。在方块254中，所述电解质溶液的流体进入通过隔膜与第一体积隔开的第二体积内。所述隔膜具有如上所述的在其内形成的多个纳米通道。在第二体积中的流体是脱盐的或部分脱盐的。可以添加另外的段。
尽管已经描述了用于脱盐的纳米孔半渗透隔膜的优选实施方案(它们意图是说明性的而不是限制性的)，应该注意到，改变和变化可以由本领域技术人员按照上述教导做出。因此，应该明白，可以在所公开的特定实施方案中做出改变，这些改变在所附权利要求所描绘的发明的范围内。尽管已经如此描述了本发明的各个方面，考虑到专利法所要求的细节和特性，由专利特许证要求和希望保护的内容在所附权利要求中阐述。
Claims (20)
1.过滤器，它包含：
具有在其内形成的多个纳米通道的多孔隔膜，其中所述纳米通道包括氧化物表面且具有第一直径；和
官能化纳米颗粒的自组装膜，其中所述官能化纳米颗粒包含纳米颗粒和布置在其上的有机配体，该有机配体具有至少一个能与所述氧化物表面反应的官能团，其中所述自组装膜将所述第一直径降低到第二直径。
2.权利要求1中所述的过滤器，其中所述隔膜包含铝，和所述纳米颗粒通过使用阳极氧化铝形成。
3.权利要求1中所述的过滤器，其中所述纳米通道包括在约10nm和200nm之间的第一直径。
4.权利要求1中所述的过滤器，其中所述第二直径为约2－3nm。
5.权利要求4中所述的过滤器，其中所述纳米颗粒具有有效排斥正离子的表面电荷。
6.权利要求4中所述的过滤器，其中所述纳米颗粒具有有效排斥负离子的表面电荷。
7.权利要求4中所述的过滤器，其中所述纳米颗粒具有中性电荷。
8.权利要求1中所述的过滤器，其中所述电解质溶液包括海水，和所述第二直径为2nm－3nm。
9.过滤器系统，它包含：
为在压力下接收电解质溶液而构造的第一体积；和
通过具有在其内形成的多个纳米通道的隔膜而与第一体积隔离的第二体积，所述纳米通道包括第一直径和连接到所述纳米通道表面上的纳米颗粒的自组装单层，其中所述自组装单层给过滤器系统提供第二直径，所述第二直径小于所述第一直径，和其中所述第二直径有效防止电解质溶液内的离子穿过所述隔膜传输。
10.权利要求9中所述的过滤器系统，还包含为调节第一体积的压力而构造的压力调节器。
11.权利要求9中所述的过滤器系统，还包含为支持所述隔膜抗压而构造的支撑结构。
12.权利要求9中所述的过滤器系统，还包含为混合在第一体积内的流体而构造的混合器。
13.权利要求9中所述的过滤器系统，还包含顺序排列以过滤所述电解质流体和过滤过的电解质流体的多个隔膜。
14.权利要求1中所述的过滤器系统，其中所述隔膜包含铝，并且所述纳米通道通过阳极化形成，从而在纳米通道的表面上形成氧化物。
15.权利要求1中所述的过滤器，其中所述纳米通道包括在约20nm和30nm之间的第一直径，和其中所述第二直径为约2－3nm。
16.权利要求1中所述的过滤器，其中所述电解质溶液包括海水，和所述第二直径为2nm－3nm。
17.制造过滤器的方法，该方法包括:
使多孔隔膜材料内的每一纳米通道的直径变窄，这包括将官能化纳米颗粒的自组装单层连接到每一纳米通道的内表面上，其中每一官能化的纳米颗粒包含纳米颗粒和连接到所述纳米颗粒上的有机配体，所述有机配体包含有效地与内表面反应并在内表面上形成纳米颗粒的自组装单层的至少一个官能团。
18.权利要求17中所述的方法，其中所述多孔隔膜材料包含多孔阳极氧化铝材料，和所述至少一个官能团对该氧化物具有反应性。
19.权利要求17中所述的方法，其中所述多孔隔膜材料通过在酸中使铝膜阳极化而形成，所述酸选自草酸，硫酸，铬酸，磷酸和它们的组合。
20.权利要求17中所述的方法，其中所述多孔隔膜材料的每一纳米通道具有20nm－40nm的直径，和连接到纳米通道内表面上的所述官能化纳米颗粒给过滤器提供2nm－3nm的直径。
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- 2011-01-10 JP JP2012548201A patent/JP5426038B2/ja not_active Expired - Fee Related
- 2011-01-10 WO PCT/US2011/020653 patent/WO2011087978A1/en active Application Filing
- 2011-01-10 EP EP11733229.6A patent/EP2523748B1/en active Active
- 2011-01-10 KR KR1020127019288A patent/KR101442365B1/ko not_active IP Right Cessation
- 2011-01-10 CN CN201180005759.3A patent/CN102711967B/zh not_active Expired - Fee Related
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| US9782727B2 (en) | 2014-07-14 | 2017-10-10 | International Business Machines Corporation | Filtration membranes with functionalized star polymers |
| US10906007B2 (en) | 2014-07-14 | 2021-02-02 | International Business Machines Corporation | Filtration membranes with functionalized star polymers |
| WO2016132249A1 (en) * | 2015-02-16 | 2016-08-25 | International Business Machines Corporation | Thin film composite forward osmosis membranes with performance enhancing layers |
| GB2548029A (en) * | 2015-02-16 | 2017-09-06 | Ibm | Thin film composite forward osmosis membranes with performance enhancing layers |
| GB2548029B (en) * | 2015-02-16 | 2018-01-10 | Ibm | Thin film composite forward osmosis membranes with performance enhancing layers |
| US9931598B2 (en) | 2015-02-16 | 2018-04-03 | International Business Machines Corporation | Anti-fouling coatings with star polymers for filtration membranes |
| US10005042B2 (en) | 2015-02-16 | 2018-06-26 | International Business Machines Corporation | Thin film composite forward osmosis membranes with performance enhancing layers |
| US10654002B2 (en) | 2015-02-16 | 2020-05-19 | International Business Machines Corporation | Thin film composite forward osmosis membranes with performance enhancing layers |
| US10695724B2 (en) | 2015-02-16 | 2020-06-30 | International Business Machines Corporation | Anti-fouling coatings with star polymers for filtration membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2786121A1 (en) | 2011-07-21 |
| WO2011087978A1 (en) | 2011-07-21 |
| EP2523748A4 (en) | 2017-03-01 |
| KR20120123057A (ko) | 2012-11-07 |
| JP2013517113A (ja) | 2013-05-16 |
| EP2523748B1 (en) | 2022-10-12 |
| EP2523748A1 (en) | 2012-11-21 |
| JP5426038B2 (ja) | 2014-02-26 |
| US20110168560A1 (en) | 2011-07-14 |
| KR101442365B1 (ko) | 2014-09-17 |
| CN102711967B (zh) | 2014-07-16 |
| US8297449B2 (en) | 2012-10-30 |
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