CN111278543B - 加湿膜用聚苯砜中空纤维膜的制造方法 - Google Patents
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Abstract
所获得的中空纤维膜的透水性高,在用作加湿膜的情况下在供给湿度与加湿量之间呈现线性关系,因而可有效地用作燃料电池用的加湿膜等。此聚苯砜中空纤维膜的制造方法不仅能够提供抑制了随着加湿膜的运转而发生的亲水性高分子的偏析和/或交联、且抑制了随着运转而发生的加湿性能降低的加湿膜,而且能够制造透水性高、在用作经交联的加湿膜时在水蒸气的供给湿度与加湿量之间呈现线性关系的加湿膜用聚苯砜中空纤维膜。
Description
技术领域
本发明涉及加湿膜用聚苯砜中空纤维膜(polyphenyl sulfone hollow fibermembrane)的制造方法。更详细而言,涉及有效地用于燃料电池等中的加湿膜用聚苯砜中空纤维膜的制造方法。
背景技术
在固态高分子型燃料电池中,将氢等燃料气体以及氧等氧化剂气体加湿而供给的装置是必需的。作为用于将这样的气体进行加湿的装置,使用利用了水蒸气透过膜的装置,特别是经常使用中空纤维膜方式。该方式不仅无需维修,而且具有驱动不需要电源等许多优点。其成为如下的系统:例如,通过从膜的外侧流动包含水蒸气的气体,使得该气体中的水蒸气选择性地朝向中空纤维膜的内侧通过,从而将通过中空纤维膜的中空部分的气体进行加湿。
燃料电池的电解质膜在水分含量少的状态下运转时,有可能发生发电效率的降低和/或催化剂的劣化,因而为了该水分管理而使用加湿器。因此,在燃料电池用的加湿器方面,利用加湿器仅将从燃料电池排放出的水分回收,从而将水分再次返回向燃料电池,因而作为加湿器,优选加湿量与所供给的水分量成比例地增加的加湿器。
但是,以往的加湿膜存在如下问题,即,供给水分的气氛的湿度(水分量)与加湿量的关系从线性关系向下侧大大偏离,在运转条件发生了变化时,水分管理变难。另外出现如下现象:对加湿膜供给100℃以上的干燥空气时,则因膜中含有的亲水性高分子的偏析和/或交联反应的进行,导致加湿性能降低。
若随着这样的使用而发生性能降低时,则考虑到性能降低程度,需要使用初期性能高的加湿器,但是该加湿器有可能在初期运转时在堆叠体(stack)内产生结露(堵塞(plugging))。
在专利文献1中,提出了通过使用交联剂将膜中的亲水性高分子进行交联而得到的水蒸气透过膜。然而,在使用这样的交联剂的情况下,在抑制在供给100℃以上的干燥空气时的加湿性能降低方面存在问题,也存在由交联剂导致污染的担忧。
本申请人提出了一种水蒸气透过膜,其通过在由聚醚酰亚胺构成的多孔质支承体上将亲水性高分子以薄膜的形态涂布之后进行交联从而得到(专利文献2)。但是,聚醚酰亚胺在耐水解性方面存在问题,例如,有时会因在温度80℃、相对湿度100%这样的气氛中使用加湿膜而导致水解。
本申请人进一步提出了一种由多孔质聚苯砜中空纤维膜形成的水蒸气透过膜,所述多孔质聚苯砜中空纤维膜是通过以水为芯液、将包含聚苯砜树脂以及亲水性聚乙烯吡咯烷酮的水溶性有机溶剂溶液的纺纱原液进行干湿式纺纱而获得的(专利文献3~4)。其中,在专利文献4中,通过相对于聚苯砜树脂100重量份而使用5~30重量份的亲水性聚乙烯吡咯烷酮,从而起到如下的效果:例如,即使设置于约80~140℃这样的高温度条件下且相对湿度(RH)为0~30%这样的低湿度条件下的气氛中进行使用,也能够抑制水蒸气透过性、拉伸断裂强度、拉伸断裂伸长率等这样的膜性能的降低。
在这些专利文献中,没有着眼于供给湿度与加湿量的关系,在其说明书中没有发现任何记载。
现有技术文献
专利文献
专利文献1:日本特开2002-100384号公报
专利文献2:日本特开2002-257388号公报
专利文献3:日本特开2004-290751号公报
专利文献4:日本特开2006-255502号公报
发明内容
发明所要解决的课题
本发明的目的在于提供一种加湿膜用聚苯砜中空纤维膜的制造方法,所述加湿膜用聚苯砜中空纤维膜的透水性高,在用作加湿膜的情况下在供给湿度与加湿量之间呈现线性关系。
用于解决课题的技术手段
上述本发明的目的通过将中空纤维状的膜在160~180℃加热5~12小时进行交联处理从而实现,所述中空纤维状的膜使用包含聚苯砜、亲水性聚乙烯吡咯烷酮以及水溶性有机溶剂溶液的纺纱原液并通过湿式纺纱法或者干湿式纺纱法、优选通过干湿式纺纱法从而获得。
发明的效果
本发明的聚苯砜中空纤维膜的制造方法获得了下述优异的技术效果,即,不仅能够提供抑制了随着加湿膜运转而发生的亲水性高分子的偏析和/或交联、且抑制了随着运转而发生的加湿性能降低的加湿膜,而且能够制造透水性高、且在用作经交联的加湿膜时在水蒸气的供给湿度与加湿量之间呈现线性关系的加湿膜用聚苯砜中空纤维膜。所获得的中空纤维膜可有效地用作燃料电池用的加湿膜等。
附图说明
图1是表示在实施例(●)以及比较例1(■)中获得的聚苯砜中空纤维膜的、Wet-In相对湿度与初期水蒸气透过系数的关系的图。
图2是表示在实施例(●)以及比较例1(■)中获得的聚苯砜中空纤维膜的、Wet-In相对湿度与初期加湿性能比率的关系的图。
具体实施方式
聚苯砜具有以下所示的重复单元、即具有亚联苯基,不具有异亚丙基(isopropylidene),实际上可直接使用市售品、例如Solvay Specialty Polymers公司制品等。
对于将聚苯砜作为制膜成分的纺纱原液,可以通过在聚苯砜中配合亲水性聚乙烯吡咯烷酮的水溶性有机溶剂而制备。作为水溶性有机溶剂,可以使用二甲基乙酰胺[DMAc]、二甲基甲酰胺[DMF]、N-甲基-2-吡咯烷酮[NMP]、二甲基亚砜[DMSO]等非质子性极性溶剂。
纺纱原液可采用如下配合比例,即,聚苯砜占约17~23重量%、优选占约19~22重量%,显现亲水性的各种分子量的聚乙烯吡咯烷酮占约8~20重量%、优选占约11~18重量%。以比上述少的比例使用亲水性聚乙烯吡咯烷酮时,则水蒸气透过性变低,而另一方面以比上述多的比例使用时,则制膜溶液变得不稳定并且变得无法纺纱。
使用该纺纱原液而进行的聚苯砜中空纤维膜的制膜,通过湿式纺纱法或者干湿式纺纱法进行,优选通过干湿式纺纱法进行。此时,作为芯液,使用水、水与水溶性有机溶剂、具体而言使用与上述非质子性极性溶剂的混合溶剂等。经纺纱而得到的中空纤维状物,在由水代表的水性凝固浴(凝胶化浴)中凝固后,在121℃的加压水中清洗约0.5小时以上、优选清洗约1~5小时左右,接着在约160~180℃、优选165~175℃的恒温槽中进行约5~12小时、优选6~10小时的加热处理。加热温度比上述低时和/或加热时间比上述短时,无法获得所期望的加湿性能。
实施例
接着,利用实施例说明本发明。
实施例
(1)使用水作为芯液,通过干湿式纺纱法,将包含聚苯砜(Solvay SpecialtyPolymers公司制品RADEL R-5000)20重量份、亲水性聚乙烯吡咯烷酮(ISP公司制品K-30G)15重量份以及二甲基乙酰胺65重量份的在室温下均匀的纺纱原液,从双重环状喷嘴喷出至水凝固浴中,其后在121℃的加压水中清洗1小时,然后在170℃的恒温槽中加热8小时,进行交联处理,从而获得了外径1.0mm、内径0.7mm、孔径2.2nm的多孔质聚苯砜中空纤维膜。此处,孔径表示使用Seika Digital Image Corporation制品纳米孔径分布测定仪(nano-perm-porometer)测定出的、基于孔的个数基准的Knudsen扩散平均直径。
将所获得的中空纤维膜插入于内径4mm的SUS管微型组件(mini-module),使用环氧树脂将微型组件两端进行封端,以中空纤维膜的有效长度为170mm的方式制作测定用中空纤维膜组件。以线速度13m/秒,将温度80℃、相对湿度2%的干燥空气从中空纤维膜组件的一个端部供给至中空纤维膜的中空部分,同时以线速度3m/秒将温度80℃的水蒸气供给至中空纤维膜外表面。此处,将供给的水蒸气的相对湿度设为20%、40%、60%、80%或90%,求出了从中空纤维外侧朝向内侧的水分透过量。通过将该水分透过量除以中空纤维内侧表面积以及水蒸气分压差(中空纤维内侧与外侧的分压差),从而算出水蒸气透过系数(速度)。
比较例1
在实施例中,将经干湿式纺纱而得到的膜在121℃的加压水中清洗1小时,然后在40℃的恒温槽中加热8小时,获得了外径1.0mm、内径0.7mm、孔径2.4nm的多孔质聚苯砜中空纤维膜。使用此多孔质聚苯砜中空纤维膜,进行了同样的微型组件的制作。
比较例2
在实施例中,将经干湿式纺纱而得到的膜在121℃的0.1%过硫酸铵水溶液中交联1小时,然后在40℃的恒温槽中加热8小时,获得了外径1.0mm、内径0.7mm、孔径2.4nm的多孔质聚苯砜中空纤维膜。使用此多孔质聚苯砜中空纤维膜,进行了同样的微型组件的制作。
将在实施例和比较例1中获得的膜分别在加热为130℃的恒温槽内放置了120小时,然后使用其同样地制作微型组件,以线速度13m/秒,将温度80℃、相对湿度2%的干燥空气从中空纤维膜组件的一个端部供给至中空纤维膜的中空部分,同时以线速度3m/秒将温度80℃、相对湿度90~20%的水蒸气供给于中空纤维膜外表面,测定出水蒸气透过系数。
将所获得的Wet-In相对湿度与水蒸气透过系数的关系,示于下表以及将其进行图示而得到的图1中,另外,将Wet-In相对湿度与加湿性能比率(将相对湿度90%下的水蒸气透过系数设为100%的情况下的比率)的关系,示于下表以及将其进行图示而得到的图2中。
表
另外,在将使用了加热处理前的多孔质聚苯砜中空纤维膜的微型组件在相对湿度90%下的水蒸气透过系数设为100%的情况下,关于130℃、120小时后的加湿性能,实施例为100%,而于此相对,在比较例1~2中分别为85%。
Claims (4)
1.一种加湿膜用聚苯砜中空纤维膜的制造方法,其特征在于,
将中空纤维状的膜在121℃的加压水中清洗0.5小时以上,然后在160~180℃加热5~12小时,进行交联处理,
所述中空纤维状的膜使用包含聚苯砜、亲水性聚乙烯吡咯烷酮以及水溶性有机溶剂溶液的纺纱原液并通过湿式纺纱法或者干湿式纺纱法而获得。
2.根据权利要求1所述的加湿膜用聚苯砜中空纤维膜的制造方法,其中,所述聚苯砜中空纤维膜被用作燃料电池用的加湿膜。
3.一种通过权利要求1所述的方法制备的加湿膜用聚苯砜中空纤维膜,其被用作经交联的加湿膜的情况下,在水蒸气的供给湿度与加湿量之间呈现线性关系。
4.根据权利要求3所述的加湿膜用聚苯砜中空纤维膜,其用于燃料电池。
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63258954A (ja) * | 1987-04-17 | 1988-10-26 | Toray Ind Inc | ポリフエニレンスルフイド組成物 |
JPH0549884A (ja) * | 1991-08-21 | 1993-03-02 | Toray Ind Inc | ポリフエニレンスルフイドスルフオン中空糸膜およびその製造方法 |
US5340480A (en) * | 1992-04-29 | 1994-08-23 | Kuraray Co., Ltd. | Polysulfone-based hollow fiber membrane and process for manufacturing the same |
JPH0739735A (ja) * | 1993-08-02 | 1995-02-10 | Toray Ind Inc | ポリフェニレンスルホン系中空糸膜およびその製造方法 |
JPH10272343A (ja) * | 1997-01-28 | 1998-10-13 | Toray Ind Inc | ポリフェニレンスルホン系多孔質膜およびその製造方法 |
DE19817376A1 (de) * | 1998-04-18 | 1999-10-21 | Univ Stuttgart Lehrstuhl Und I | Säure-Base-Polymerblends und ihre Verwendung in Membranprozessen |
JP2004290751A (ja) * | 2003-03-26 | 2004-10-21 | Nok Corp | 水蒸気透過膜の製造法 |
CN1625436A (zh) * | 2002-09-09 | 2005-06-08 | Nok株式会社 | 聚间苯二甲酰间苯二胺多孔中空纤维膜的制造方法 |
JP2005193194A (ja) * | 2004-01-09 | 2005-07-21 | Kuraray Co Ltd | ポリフェニルスルホン多孔膜およびその製造方法 |
JP2006255502A (ja) * | 2005-03-15 | 2006-09-28 | Nok Corp | 多孔質ポリフェニルスルホン樹脂中空糸膜の製造法 |
CN101203554A (zh) * | 2005-06-20 | 2008-06-18 | 西门子水技术公司 | 聚合物膜的交联处理 |
CN101227965A (zh) * | 2005-06-09 | 2008-07-23 | 门布拉内有限公司 | 具有改进的过滤性能的微滤膜 |
JP2011067812A (ja) * | 2009-08-24 | 2011-04-07 | Toray Ind Inc | 水蒸気透過膜、中空糸膜および加湿装置 |
JP5906665B2 (ja) * | 2011-10-28 | 2016-04-20 | Nok株式会社 | 多孔質膜の製造方法 |
WO2017043233A1 (ja) * | 2015-09-07 | 2017-03-16 | Nok株式会社 | 非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01139812A (ja) * | 1987-11-24 | 1989-06-01 | Toray Ind Inc | ポリパラフェニレンスルフィドのフラッシュ紡糸方法 |
JP2810173B2 (ja) * | 1989-12-20 | 1998-10-15 | 三井鉱山株式会社 | 炭素繊維補強セメント系複合材料の製造方法 |
JP2002100384A (ja) | 2000-09-22 | 2002-04-05 | Asahi Kasei Corp | 燃料電池およびこれに用いられる水蒸気透過膜 |
JP2002257388A (ja) | 2001-02-28 | 2002-09-11 | Nok Corp | 水蒸気透過膜およびその使用方法 |
JP4013791B2 (ja) * | 2003-03-04 | 2007-11-28 | Nok株式会社 | ポリエーテルイミド系樹脂多孔質中空糸膜 |
JP5160015B2 (ja) * | 2003-10-29 | 2013-03-13 | 東レ株式会社 | 水処理用分離膜 |
JP6222625B2 (ja) * | 2012-02-16 | 2017-11-01 | 富士フイルム株式会社 | 複合型分離膜、それを用いた分離膜モジュール |
EP3071318A1 (en) * | 2013-11-22 | 2016-09-28 | Basf Se | Polymeric antifouling additives for membranes |
JP6190714B2 (ja) * | 2013-12-16 | 2017-08-30 | 旭化成メディカル株式会社 | 中空糸膜型血液浄化装置 |
US20170036169A1 (en) * | 2014-05-01 | 2017-02-09 | Sabic Global Technologies B.V. | Asymmetric poly(phenylene ether) co-polymer membrane, separation module thereof and methods of making |
JP6997314B2 (ja) * | 2018-06-26 | 2022-02-04 | Nok株式会社 | 加湿用多孔質中空糸膜の製造法 |
-
2018
- 2018-09-20 CA CA3078177A patent/CA3078177A1/en active Pending
- 2018-09-20 EP EP18870949.7A patent/EP3702021A4/en active Pending
- 2018-09-20 WO PCT/JP2018/034724 patent/WO2019082562A1/ja unknown
- 2018-09-20 KR KR1020207013987A patent/KR102377158B1/ko active IP Right Grant
- 2018-09-20 JP JP2019549951A patent/JP6964680B2/ja active Active
- 2018-09-20 US US16/756,146 patent/US20200298186A1/en not_active Abandoned
- 2018-09-20 CN CN201880069177.3A patent/CN111278543B/zh active Active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63258954A (ja) * | 1987-04-17 | 1988-10-26 | Toray Ind Inc | ポリフエニレンスルフイド組成物 |
JPH0549884A (ja) * | 1991-08-21 | 1993-03-02 | Toray Ind Inc | ポリフエニレンスルフイドスルフオン中空糸膜およびその製造方法 |
US5340480A (en) * | 1992-04-29 | 1994-08-23 | Kuraray Co., Ltd. | Polysulfone-based hollow fiber membrane and process for manufacturing the same |
JPH0739735A (ja) * | 1993-08-02 | 1995-02-10 | Toray Ind Inc | ポリフェニレンスルホン系中空糸膜およびその製造方法 |
JPH10272343A (ja) * | 1997-01-28 | 1998-10-13 | Toray Ind Inc | ポリフェニレンスルホン系多孔質膜およびその製造方法 |
DE19817376A1 (de) * | 1998-04-18 | 1999-10-21 | Univ Stuttgart Lehrstuhl Und I | Säure-Base-Polymerblends und ihre Verwendung in Membranprozessen |
CN1625436A (zh) * | 2002-09-09 | 2005-06-08 | Nok株式会社 | 聚间苯二甲酰间苯二胺多孔中空纤维膜的制造方法 |
JP2004290751A (ja) * | 2003-03-26 | 2004-10-21 | Nok Corp | 水蒸気透過膜の製造法 |
JP2005193194A (ja) * | 2004-01-09 | 2005-07-21 | Kuraray Co Ltd | ポリフェニルスルホン多孔膜およびその製造方法 |
JP2006255502A (ja) * | 2005-03-15 | 2006-09-28 | Nok Corp | 多孔質ポリフェニルスルホン樹脂中空糸膜の製造法 |
CN101227965A (zh) * | 2005-06-09 | 2008-07-23 | 门布拉内有限公司 | 具有改进的过滤性能的微滤膜 |
CN101203554A (zh) * | 2005-06-20 | 2008-06-18 | 西门子水技术公司 | 聚合物膜的交联处理 |
JP2011067812A (ja) * | 2009-08-24 | 2011-04-07 | Toray Ind Inc | 水蒸気透過膜、中空糸膜および加湿装置 |
JP5906665B2 (ja) * | 2011-10-28 | 2016-04-20 | Nok株式会社 | 多孔質膜の製造方法 |
WO2017043233A1 (ja) * | 2015-09-07 | 2017-03-16 | Nok株式会社 | 非溶剤誘起相分離法用製膜原液およびこれを用いた多孔質中空糸膜の製造方法 |
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