CN103687895A - 改善正渗透膜性能的方法 - Google Patents
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Abstract
将薄膜复合(TFC)膜用于正渗透(FO)和压力降低渗透(PRO)方法中。所述膜包括两个层:将背衬层和多孔聚合物基载体组合成一个单层的复合层,和置于所述复合层上的脱除层。本发明的膜对FO方法呈现出高水通量值、耐久、可使用典型的膜生产方法如螺旋缠绕以及板框法容易地生产,且具有足以处理最终膜产品的机械稳定性。
Description
相关申请的交叉引用
本申请要求于2011年7月26日提交的美国临时申请61/511,877的优先权,其全部说明书在此引入以作为参考。
发明领域
本发明涉及用于渗透方法以从水中除去污染物并浓缩和稀释含显著量水的液体的薄膜复合膜。
背景
薄膜复合膜最初开发用于反渗透(RO)工业。这些类型的膜的基本结构由三个层构成:1)用于强度的背衬材料,2)在背衬材料上形成的多孔聚合物基载体,和3)位于多孔载体上的脱除层。水通量为水通过该膜的流速。脱除层也称为选择层。
所述三层膜的厚度通常为约180微米或更高。对RO膜而言,该结构工作良好,这是因为水通量仅取决于脱除层,而不取决于下方的多孔载体。然而,该结构作为正渗透(FO)膜是不理想的,这是因为在FO方法中,水通量由脱除层和两个下层(载体层和背衬层)二者限定。
市售FO膜通常基于三乙酸纤维素(CTA)。CTA基FO膜可具有纺织或无纺背衬材料。纺织背衬膜由于降低的对渗透剂在载体层内迁移的扩散阻隔以及可生产的膜总体厚度而明显优于无纺背衬膜。然而,CTA基FO膜的缺点在于其对pH高度敏感且就水通量角度而言是缓慢的。已报道薄膜复合(TFC)膜获得了比三乙酸纤维素(CTA)膜更高的水通量和更好的脱盐性能。然而,TFC RO膜的常规三层结构由于较厚的无纺背衬层而在FO中不具有高性能。
发明简述
本文描述了用于正渗透(FO)和压力延迟渗透(PRO)方法中的薄膜复合(TFC)膜。所述膜包括两个层:将背衬层和多孔聚合物基载体层组合成一个单层的复合层和置于所述复合层之上的脱除层。本发明的膜对FO方法具有高水通量值、耐久、可使用典型的膜生产方法如螺旋缠绕和板框法容易地生产且具有足以处理最终膜产品的机械稳定性。
发明详述
在RO中,水传输的速率限制步骤是脱除层的质量。然而,在FO方法中,速率限制步骤通常不是脱除层,而是聚合物基载体层(本文也称为聚合物载体层)。由于该独特的差异,FO膜设计与RO膜设计存在根本性的区别。
在RO中,膜通量在很大程度上取决于脱除层的厚度、组成和形貌,因此很少有动机去优化多孔层的性能。然而,在FO方法中,与聚合物载体层接触以及处于其中的渗透剂显著影响了水通量性能。如果致密层多孔层侧上的渗透剂浓度较高,则牵引通过该致密层的水必须置换初始驱动水传输的渗透剂。然而,为了使该方法连续驱动高水通量,渗透剂必须经由多孔层向上游扩散至多孔层。对任何给定的FO膜而言,载体设计在使稳态水通量最大化中起着关键的作用。
本文所公开的提高FO膜水通量性能的方法实施方案具有许多特征,其中一个、多个或全部特征或步骤可用于任何具体实施方案中。在下文描述中,应理解的是可使用其他实施方案,且可对结构和程序进行改变而不偏离本文的范围。出于方便,可使用示例性材料、大小、形状、尺寸等描述各构成部分。然而,本文不限于所述的实例,其他构造也是可能的且处于本发明的教导之内。
本文描述了一种提高正渗透(FO)膜的水通量性能的方法,包括在薄膜复合(TFC)结构中掺入包埋的载体材料从而有助于降低多孔载体层的厚度,同时提供最终膜产品所需的足够机械稳定性。
本文进一步描述了一种包括两个层的TFC膜结构。第一层包括复合载体层单层,其组合了背衬层和多孔聚合物基载体。更特别地,第一层包括组合成一个基本上不可分离的基体的背衬材料和多孔聚合物基载体。本说明书所用的术语“基本上不可分离的基体”意指背衬材料基本上包埋于多孔聚合物基载体材料的基体内,从而使得在正常使用过程中,所述两个组分不能容易地彼此分离。
背衬材料为纺织或无纺织物材料。优选地,其为纺织织物材料。所述材料可由本领域技术人员所已知的用于渗透膜,尤其是RO和/或FO膜中的任何材料制成。通常优选所述织物薄且在该织物的纤维之间具有开放通道。
所述TFC膜结构的第二层为脱除层。更具体地,第二层为置于第一层之上的极薄脱除层。所述置于复合层之上的极薄脱除层为所述膜的允许水通过,但阻止其他物质如盐和有机物的部分。
第二层的材料为本领域技术人员所已知的用于RO、FO和其他渗透膜的脱除层中的那些。
本文还描述了一种形成两层、高水通量、机械稳定的膜的两步方法,其包括在该制备方法期间将载体结构包埋于多孔载体材料内,随后添加用作脱除层的第二薄层。
所述方法形成了高水通量且机械稳定的膜,其中第一复合层通过将背衬材料和多孔聚合物基载体组合成一个不可分离的基体而制备。然后,将极薄的脱除层置于第一复合层之上。其结果是形成两层TFC膜(获得高水通量值的薄且机械稳定的膜)。所述方法制得了与现有技术FO膜相比相对较薄的膜。所述总体上较薄的膜使得内部浓差极化(ICP)最小化且最终获得较高通量的膜。
所述多孔复合载体层起该脱除层的载体作用且包含两种构成要素,即背衬材料和多孔聚合物材料。掺入所述多孔聚合物基体中的背衬优选为纺织物,但可为无纺布。出于如下两个关键理由,相对于无纺背衬材料,优选纺织背衬:纺织背衬获得了具有标准膜生产实践所需的足够机械完整性的膜,且纺织背衬同时由于背衬结构中的固有大孔而使水传输阻力最小化。
为了形成该第一层复合载体结构,可使用浸渍沉淀方法,例如如美国专利3,133,132所述(在此将其全文引入本文)。首先,将膜聚合物材料,特别是亲水性聚合物(例如聚砜(PS)、聚醚砜(PES)、磺化聚砜、磺化聚醚砜及其混合物)溶于水溶性溶剂(例如非水性溶剂,如N-甲基吡咯烷酮等)体系中以形成粘稠溶液。
其次,将该粘稠溶液的薄层计量添加至浇铸鼓表面上,随后将高孔性织物包埋入该粘稠溶液中。该类织物的实例描述于美国专利3,133,132(在此引入以作为参考)中。即,可将所述溶液浇铸于转鼓上和可将开孔织物牵引入该溶液中以使得所述织物包埋入该溶液中。
在短时风干(例如在气刀下)后,然后可将该液态复合膜前体(pre-membrane composite)快速浸入凝聚浴(例如水浴)中以使所述粘稠聚合物溶液固化。所述凝聚浴导致膜组分凝聚并形成合适的膜特性(例如孔隙率、亲水性、非对称性等)。因此,该水接触导致溶液中的聚合物变得不稳定且在表面上极快地沉淀致密聚合物层。该层起阻止水进一步渗入所述溶液中的作用,从而使得该致密层下方的聚合物显著更慢地沉淀并形成围绕包埋织物的疏松多孔基体。
然后,在所有聚合物由粘稠溶液凝聚之后,需要的话可对所述膜进行清洗和热处理。因此,所述浸渍/沉淀方法可形成具粗滤(macrofiltration)、超滤或纳滤尺寸孔的多孔复合载体层。所述复合载体层的孔隙率通过浇铸参数(时间、温度、标准技术等)和选择配制剂组分(溶剂、聚合物材料固体与溶剂溶液之比等)二者而控制。
所述脱除层由亲水性聚合物的薄涂层形成。对将脱除层附加至所述复合载体层之上而言,存在各种选择。可用预成型的聚合物涂覆复合载体层或者可通过原位聚合形成聚合物。可使用的聚合物实例为聚乙烯醇(PVA)、聚丙烯腈、磺化聚砜、磺化聚醚砜、磺化聚醚酮、磺化聚醚醚酮、磺化聚酰亚胺、磺化苯乙烯嵌段共聚物如获自Kraton的那些等以及前述聚合物的混合物。使用预成型聚合物形成脱除层可通过使用各种方式,例如挤出头法、刮刀法或浮涂(float coating)法实现。
或者,聚合物如聚酰胺可在所述复合载体层上原位聚合以形成脱除层。对聚酰胺的原位界面聚合而言,首先将所述复合载体层浸泡于间苯二胺(m-PDA)的水溶液中。使用辊或气刀从表面上移除过量的m-PDA,并将均苯三甲酰氯(TMC)于有机流体如己烷或Isopar G中的溶液施加至所述经胺浸泡的复合载体层的上表面。发生界面聚合,从而在复合载体层上获得薄聚酰胺脱除层。可容易地获得厚度为一(1)微米或更小(例如0.2微米)的涂层。
因此,结果是形成两层TFC膜。其为在FO方法中获得高水通量值的薄且机械结实的膜。
在大多数情况下,较薄的膜是有利的。一般而言,用于形成该膜的背衬材料开孔率越高(即,纤维之间的空间越大),则膜的功能越好。然而,本发明膜的一些应用场合可能需要较厚的膜,而不是较薄的膜。第一层中所用的背衬材料的厚度往往决定了膜的厚度。此外,如果背衬材料自身的厚度波动,则这些波动可通过使所述膜的其余部分更厚而补偿。
优选所述膜的厚度小于约130微米且大于约30微米。然而,大于130微米,如约200微米或者甚至更高的厚度是可能的且对该膜的一些应用而言可能是合乎需要的。优选膜的厚度为约100微米。在一个示例性实施方案中,膜的厚度为约120微米。在两个其他实施方案中,所述膜的厚度各自为80微米和100微米。
任选地,可在第一层中掺入其他组分。例如,在该方法开始时且在浇铸之前,可使如下组分包含于或混入溶于水溶性溶剂的膜聚合物材料的粘稠溶液中:造孔剂(例如用于优化载体层孔隙率的试剂,如聚乙二醇、有机酸、有机酸盐、无机盐、酰胺、聚合物等,如马来酸、柠檬酸、乳酸、氯化锂、溴化锂,聚合物如聚乙烯基吡咯烷酮(PVP)、聚醚砜(PES)、聚苯硫醚(PPS)和前述聚合物的共聚物)、亲水化试剂(例如PVP、聚多巴胺、聚乙烯基吡咯烷酮(PVP)以及聚乙烯基吡咯烷酮的共聚物等)和增强剂(例如用于改善柔韧性并降低脆性的试剂,如甲醇、乙醇、甘油、丙酮和溶剂如DMAc、DMF和DMSO等)。
任选地,一旦形成,则可进一步用亲水化试剂对所得两层TFC膜进行处理以提高水润湿性(使得膜更亲水)。更具体地,可用亲水化试剂在与脱除层相对的第一层表面上涂覆该第一层(即,掺有聚合物基载体的复合层)。可使用的亲水化试剂的实例为聚多巴胺、聚乙烯基吡咯烷酮(PVP)和聚乙烯基吡咯烷酮的共聚物等。
可使用其他任选的膜形成步骤以优化所得膜的性能。例如,可对所述两层膜进一步进行热处理、化学处理(例如,用NaOCl,随后用NaHSO3)和表面改性,如接枝聚乙二醇,从而改善防污性、水通量、盐脱除性、长期性能等。
下文描述了本发明的两层TFC膜的实例。
由表1所给配制剂的浇铸溶液制备微孔聚砜基材。将载体膜的纺织背衬掺入该浇铸溶液的薄层中以赋予生产用的强度和最终应用的耐久性。然后将该复合结构浸入水中,所述水起非溶剂作用且导致由于聚合物沉淀而成膜。
表1
用于形成载体膜的配制剂 | 载体膜-1 | 载体膜-2 | 载体膜-3 | 载体膜-4 |
PSf3500(Solvay)(聚砜),重量% | 17.5 | 17.5 | 17.5 | 17.5 |
PVP(1.3M)(Sigma),重量% | 0.5 | 0.5 | 0.5 | 0.5 |
NMP(Sigma),重量% | 82 | 82 | 82 | 82 |
总计,重量% | 100 | 100 | 100 | 100 |
除表1中所述的之外,可添加至溶液配制剂中的其他任选组分有造孔剂,如聚乙二醇、马来酸、柠檬酸、乳酸、氯化锂、溴化锂、聚合物如PVP、聚醚砜(PES)和聚苯硫醚(PPS)以及前述聚合物的共聚物;表面活性剂,如SLS和SDBS;非溶剂,如水、甲醇、乙醇、甘油、丙酮;和溶剂如DMAc、DMF和DMSO。对本领域技术人员而言,用于制备反渗透膜的宽范围的材料也可用于正渗透膜。
通过界面聚合,使用表2所提供的配制剂在所述膜上沉积包含聚酰胺(PA)薄膜的脱除层,该表也包含与这些配制剂组合使用的工艺变量。
表2
PA涂覆配制剂 | 载体膜-1 | 载体膜-2 | 载体膜-3 |
水相 | |||
m-PD,重量% | 2 | 2 | 2 |
水,重量% | 98 | 98 | 98 |
总计,重量% | 100 | 100 | 100 |
有机相 | |||
TMC,重量% | 0.1 | 0.1 | 0.1 |
己烷,重量% | 99.9 | 99.9 | 99.9 |
总计,重量% | 100 | 100 | 100 |
PA涂覆工艺参数 |
水相浸泡时间,分钟 | 5 | 5 | 10 |
移除过量水相的方法 | 辊 | 辊 | 辊 |
有机相浸泡时间,秒 | 10 | 10 | 10 |
烘箱时间(分钟)/温度(℃) | 无/无 | 45/70 | 无/无 |
一旦制得这些膜,则在FO和PRO两种模式下对其进行测试,数据汇总于表3中。给出了水通量和反向盐传输数据。
表3
两层TFC膜实施方案尤其可用于FO水处理应用中。该应用可包括渗透驱动的水净化和过滤、海水脱盐、污染含水废料流的净化、膜生物反应器等。然而,各实施方案不限于与FO应用相关的用途。相反,任何与FO应用有关的描述均是出于示例本发明公开内容的目的,各实施方案也可以以类似结果用于许多其他应用中。例如,两层TFC膜实施方案也可用于PRO系统中。不同之处在于PRO产生渗透压以驱动涡轮或其他产生能量的设备。全部所需的是切换进料新鲜水(与渗透剂相对)且可将盐水供至外部而非水源(对水处理应用而言)。
Claims (18)
1.一种具有两个层的薄膜复合渗透膜,所述层包括:
(a)复合层,其包含包埋于多孔聚合物基载体中的背衬层;和
(b)置于所述复合层上的脱除层。
2.根据权利要求1的膜,其中所述背衬层为无纺或纺织织物。
3.根据权利要求2的膜,其中所述背衬层为纺织织物。
4.根据权利要求1的膜,其中所述多孔聚合物基载体由亲水性聚合物形成。
5.根据权利要求4的膜,其中所述多孔聚合物基载体由选自聚砜、聚醚砜、磺化聚砜和磺化聚醚砜及其混合物的聚合物形成。
6.根据权利要求4的膜,其中所述复合层具有掺入其中或涂覆于其上的亲水性聚合物,所述亲水性聚合物选自聚乙烯基吡咯烷酮、聚乙烯基吡咯烷酮共聚物、聚多巴胺及其混合物。
7.根据权利要求2的膜,其中所述脱除层为亲水性聚合物。
8.根据权利要求7的膜,其中所述脱除层为选自聚乙烯醇、聚丙烯腈、磺化聚砜、磺化聚醚砜、磺化聚醚酮、磺化聚醚醚酮、磺化聚酰亚胺、磺化苯乙烯嵌段共聚物及其混合物的亲水性聚合物。
9.根据权利要求1的膜,其具有约30微米至约130微米的厚度。
10.一种形成两层薄膜复合膜的方法,其包括:
将背衬材料和多孔聚合物基载体组合成不可分离的基体以形成复合载体层;和
在所述复合载体层上形成脱除层,由此形成所述膜。
11.根据权利要求10的方法,其中所述复合载体层通过将背衬材料包埋入亲水性聚合物的溶液中而形成。
12.根据权利要求11的方法,其中通过将亲水性聚合物的溶液浇铸于转鼓上和将背衬材料牵引进所述溶液中而将所述背衬材料包埋入所述溶液中。
13.根据权利要求11的方法,其中所述亲水性聚合物的溶液进一步包含造孔剂、疏水化试剂或增强剂。
14.根据权利要求11的方法,进一步包括将所述复合载体材料浸入凝聚浴中,然后形成脱除层。
15.根据权利要求10的方法,其中所述脱除层通过挤出头法、刮刀法、浮涂法或者通过在所述复合载体层上原位聚合聚合物而形成。
16.根据权利要求15的方法,其中所述脱除层通过将所述复合载体层浸泡于间苯二胺的溶液中,然后将均苯三甲酰氯于有机流体中的溶液施加至该复合载体层上表面而在所述复合载体层上原位形成。
17.根据权利要求10的方法,进一步包括对所述膜进行选自如下组的处理:热处理、化学处理和表面改性。
18.根据权利要求10的方法,进一步包括用亲水化试剂对所述膜的复合载体层侧进行处理。
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- 2012-07-26 JP JP2014523025A patent/JP2014526964A/ja active Pending
- 2012-07-26 AU AU2012286754A patent/AU2012286754A1/en not_active Abandoned
- 2012-07-26 CN CN201280035467.9A patent/CN103687895A/zh active Pending
- 2012-07-26 WO PCT/US2012/048398 patent/WO2013016574A1/en active Application Filing
- 2012-07-26 US US13/559,472 patent/US20130026091A1/en not_active Abandoned
- 2012-07-26 EP EP12817939.7A patent/EP2736959A4/en not_active Withdrawn
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Cited By (7)
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CN107249719A (zh) * | 2015-02-16 | 2017-10-13 | 国际商业机器公司 | 具有性能增强层的薄膜复合材料正向渗透隔膜 |
CN107249719B (zh) * | 2015-02-16 | 2021-08-17 | 国际商业机器公司 | 具有性能增强层的薄膜复合材料正向渗透隔膜 |
CN107512036A (zh) * | 2016-06-17 | 2017-12-26 | 通用电气公司 | 膜和制备膜的方法 |
CN111513134A (zh) * | 2019-02-03 | 2020-08-11 | 内蒙古蒙牛乳业(集团)股份有限公司 | 一种基于正渗透原理的乳制品制备方法 |
US11148101B2 (en) | 2019-12-25 | 2021-10-19 | National Tsing Hua University | Forward osmosis membrane having high chemical resistance |
TWI744754B (zh) * | 2019-12-25 | 2021-11-01 | 國立清華大學 | 高耐化性之正滲透膜 |
CN112870994A (zh) * | 2020-12-29 | 2021-06-01 | 东北大学 | 一种提高聚丙烯腈正渗透膜耐氯性能的改性方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20140059785A (ko) | 2014-05-16 |
EP2736959A1 (en) | 2014-06-04 |
WO2013016574A1 (en) | 2013-01-31 |
EP2736959A4 (en) | 2015-06-17 |
US20130026091A1 (en) | 2013-01-31 |
JP2014526964A (ja) | 2014-10-09 |
AU2012286754A1 (en) | 2014-02-13 |
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