CN103260730B - 支承的中空纤维膜 - Google Patents

支承的中空纤维膜 Download PDF

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CN103260730B
CN103260730B CN201180060384.0A CN201180060384A CN103260730B CN 103260730 B CN103260730 B CN 103260730B CN 201180060384 A CN201180060384 A CN 201180060384A CN 103260730 B CN103260730 B CN 103260730B
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coating
supporting structure
polymer
tubular support
membranous wall
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CN103260730A (zh
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A.帕林卡斯
M.马歇尔
R.邵博
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BL Technology, Inc.
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General Electric Co
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Abstract

一种中空纤维膜通过利用膜涂料覆盖管状支承结构并使膜涂料转化成固体多孔膜壁而制成。任选地，呈圆形针织物的形式的织物增强结构可在支承结构以涂料覆盖之前添加在支承结构周围。增强结构由此变成嵌入在膜壁中。支承结构可能够溶于膜壁的非溶剂(例如水)，并且可从膜移除。可选地，支承结构可为多孔的。多孔支承结构可通过非编织纺织过程、挤出机内的烧结过程或通过挤出与第二成分混合的聚合物而制成。第二成分可为可溶固体或液体、超临界气体，或与第一聚合物不反应的第二聚合物。

Description

支承的中空纤维膜
技术领域
本说明书涉及中空纤维膜、制造中空纤维膜的方法以及用于中空纤维膜的支承结构。
背景技术
下列讨论不承认下面描述的任何内容为公知常识或者能够作为现有技术引用。
美国专利5,472,607描述由编结织物管支承的中空纤维聚合膜。编结管为足够密的并且紧密地编结，使得其在涂覆有膜涂料之前为圆形稳定的。膜聚合物主要位于编结物的外侧。该类型的结构已在当前由GE Water and Process Technologies售卖的ZeeWeed(TM) 500系列膜产品中非常成功地使用。特别地，该类型的支承膜已被证实在使用中为极其耐用的。
发明内容
下列段落意图为向读者介绍接下来的详细描述并且不限制或限定任何要求权利的发明。
发明人已观察到，制成圆形稳定编结支承件所需的丝的数量倾向于导致具有过剩抗拉强度的编结物。编结圆形稳定支承件还为缓慢的过程，典型地以每小时大约20-30米的速度进行。相比之下，涂料涂覆过程可以以高达每分钟20-40米的速度进行，并且因此编结物在其制成时必须卷绕到卷轴上，并且接着在涂覆过程期间被再次取下。减少编结支承件中的丝的数量可降低膜的成本，同时仍提供充足的抗拉强度。然而，利用较少的丝，编结支承件可不为圆形稳定的，并且可在涂覆期间不向膜涂料提供足够的支承。此外，即使在编结物中使用较少的丝，编结速度也仍将大大低于涂覆速度，并且编结和涂覆操作仍不可在同一生产线中组合。
本文中描述了制造中空纤维膜的各种方法，其中，膜涂料挤出到可选地被称为支承件或管状支承件的管状支承结构上。在第一组膜中，管状支承件为多孔的并且保留为完成的膜的一部分。多孔支承结构可例如通过非编织纺织过程、使用挤出机的烧结过程或通过挤出与第二成分混合的聚合物而制成。第二成分可为可溶固体或液体、超临界气体或与第一聚合物不反应的第二聚合物。支承结构支承膜涂料直到涂料固化成膜壁。取决于管状支承件的类型和材料，包括支承结构和膜壁的得到的复合结构可具有比单独利用涂料制成的相同厚度的膜壁更大的抗拉强度。
在第二组膜中，管状支承件被形成在管状支承件上方的织物增强件包围。例如，织物增强件可针织在管状支承件周围。在第二组膜中，管状支承件可在涂料已形成膜壁之后从完成的膜溶解出，从而留下嵌入在膜壁中的织物增强件。可选地，如第一组膜中的多孔支承件可被织物增强件包围并且保留在完成的膜中。管状支承件支承膜涂料直到涂料固化成膜壁。织物增强件相对于单独利用涂料制成的相同厚度的膜壁增大膜的抗拉强度。如果被保留，则管状支承件还可有助于织物强度的增大。任选地，织物增强件可以以与涂料涂覆过程相同的速度并按照涂料涂覆过程针织在管状支承件周围。
附图说明
图1是第一中空纤维膜的示意性截面。
图2是第二中空纤维膜的示意性截面。
图3是涂覆头的截面。
图4是具有围绕其的针织织物增强件的可溶管状支承结构下方的可溶管状支承结构的照片。
图5是在可溶管状支承结构已被洗掉之后的、具有针织织物增强层的使用可溶支承结构制造的中空纤维膜的截面。
具体实施方式
参考图1和图2，通过在管状支承件12上方形成具有外分离层15的膜壁14而制造中空纤维膜10。管状支承件12可为预制的，并且储存在卷轴上直到其将用于制作中空纤维膜10。为了制造中空纤维膜10，当膜涂料18通过模19泵送到管状支承件12上时，管状支承件12被拉动穿过涂覆头16的中心。管状支承件12穿过涂覆头16的中心孔17。中心孔17允许管状支承件穿过模19并且还使管状支承件12相对于模19定心，使得涂料18均匀地施加在管状支承件12的外侧周围。支承件12的柱形表面允许选择涂料涂覆厚度、涂料粘度和其它参数，而不受限于可在单独利用涂料形成膜时使用的值。在从涂覆头16离开之后，管状支承件12和涂料18进入骤冷浴，其中，涂料18转化成多孔固体膜壁14。膜壁14的形成可经由热致相分离(TIPS)或非溶剂诱导相分离(NIPS)过程。分离层15可具有在微过滤范围内或更小的标称微孔大小。
管状支承件12可为多孔的，并且可在使用中保留在完成的中空纤维膜10的内部。管状支承件12可具有比相同厚度的膜壁14高的抗拉强度。因此，复合膜10也可具有比单独利用涂料18制成的相同厚度的膜高的抗拉强度。适合的永久多孔管状支承件12可通过经环形模挤出包括两种主要成分的混合物而制成。第一主要成分为将保留为多孔支承件12的热塑性挤出级聚合物。第二主要成分为能够溶于第一主要成分的非溶剂的相容物质。例如，第一主要成分可为不可溶于水的聚合物，而第二主要成分可为可溶于水的物质，诸如糖、盐、PVA或甘油。第一和第二主要成分选择成使得它们与彼此不反应。作为替代，第一和第二主要成分在挤出之前利用平稳搅动混合，以便在第一主要成分中产生第二主要成分的小颗粒的均质混合物，例如乳剂。混合物通过环形模和任选地又一个外径校准模挤出。挤出的混合物的第一主要成分固化以形成支承件12。管状支承件12放置在第二主要成分的溶剂(例如水)浴中，以使第二主要成分可在浴中被滤出。该过滤步骤可发生在膜壁14形成在支承件12上方之前或之后。如果管状支承件12主要被要求在涂覆期间支承膜涂料18，则第一主要成分可为不昂贵(相对于膜涂料18)的聚合物，诸如聚乙烯(PE)。然而，如果期望更大强度的膜10，则第一主要成分可为更强的聚合物，诸如聚酯(聚对苯二甲酸乙二醇酯，PET)。
可选地，管状支承件12可通过挤出两种不同热塑性材料的混合物而制成。两种材料选择成使得它们不与彼此反应。在第二材料不在第一材料中良好地混合或溶解并且代之以第二材料形成对由第一材料提供的基质的粘附性低的簇状物的意义上，两种材料也为不相容的。例如，一种已知的第二材料为聚甲基戊烯(PMP)。取决于成本还是强度对于完成的膜10而言更重要，第一材料可为例如PE或PET。在挤出管已固化之后，其被拉伸以设定管状支承件12的最终外径并在两种材料之间形成小裂缝。裂缝向管状支承件12提供期望孔隙率。相似的管状支承件12可通过使第一材料与不是聚合物的非溶剂(诸如CaCO3)混合而制成。
作为另外的基于挤出的可选方案，可在市场上买到的过滤管可用于支承件12。具有开间结构的管状支承件12还可从与超临界气体(诸如二氧化碳)混合的聚合物挤出。当混合物从挤出模出来时，压力降低允许超临界气体逸出，从而留下开间结构。挤出的固体管还可机械地或利用一个或更多个脉动激光束冲压出，以形成支承件12。
管状支承件12还可不利用挤出制造。例如，非编织支承件可通过将静电纺成、熔喷或喷吹纤维节段引导到旋转心轴上而制成。心轴为多孔的，其中，其内孔连接于抽吸源，使得半固化的纤维节段收集在心轴上。纤维节段在心轴上完全固化并且彼此结合以形成非编织管。管的一个端部被连续地拉离心轴以形成管状支承件12。任选地，非编织结构可具有足够的密度以增大膜10的强度。支承件12还可利用挤出机由连续烧结过程制成。在该过程中，半熔化聚合物粒子在挤出机中被压在一起并且在压力下烧结，从而以与金属烧结相似的方式推动它们穿过挤出模，但形成管状形状。该管接着用作支承件12。烧结过程不产生具有与非编织支承件一样大的强度的支承件12，但是烧结和非编织技术可按照涂覆过程执行。
参考图2，第二中空纤维膜20具有膜壁14、永久或临时管状支承件12和织物增强件22。织物增强件22优选地嵌入在膜壁14中。在示出的第二膜20中，织物增强件22由单丝或多丝纱线或丝线织成。大体上，针织可比编结更快速地完成，并且要求较不复杂的机器。在示出的织物增强件22中，针织物还设计成产生相对于当前编结的膜支承结构的较疏松结构，并且因此要求比编结膜支承件少的材料。织物增强件22不足以密到独自支承涂料18，并且因此织物增强件22与管状支承件12结合使用。然而，织物增强件22增大得到的膜10的强度。
针织增强件22通过使支承件12穿过针织机同时在支承件12周围的管中针织一个或更多个单丝或多丝24而施加至管状支承件12。针织可以以与关于图3描述的涂料涂覆过程相同的速度进行，因此允许针织按照涂覆进行。在该情况下，管状支承件12可从卷轴拔出，并且直接穿过针织机和涂覆头16(就是说，不再次缠卷)。
可选地，织物增强件22可设置成呈一个或更多个螺旋缠绕件的形式，该一个或更多个螺旋缠绕件通过使支承件12穿过缠绕机而制成。
进一步可选地，织物增强件22可设置成呈丝24的许多短节段的形式。例如，织物增强件可通过将微纤维混合到膜涂料18中而制成。微纤维还可通过在涂料18的表面上喷射斩断、静电纺成或熔喷纤维而施加至半固化膜涂料18的外表面。纤维在其离开涂覆头16时或之后不久喷射到膜涂料18上，使得涂料18可已开始固化，但其还不是固体。
任选地，增强件22中的一个或更多个丝24可被涂覆或为双成分丝24，或者纱线或其它多丝形式的丝24可具有两种或更多种类型的成分单丝。交叉或相邻的丝24可在接触点处彼此固定。例如，丝24可通过热定型、紫外线光、焊接、等离子、树脂或其它粘合剂彼此固定。如果需要，则丝24的材料、被涂覆的丝24的涂层、双成分丝24中的一种或更多种暴露的材料，或多丝中的一个或更多个单丝可选择成适合于选择的固定方法。通过改变丝24的密度，通过决定是否在接触点或交叉点处将丝24固定在一起，以及通过调节丝24之间的接触点或交叉点的密度，可调节织物增强件22的柔性。
支承件12可保留在第二膜20内部。在该情况下，支承件12可通过描述用于第一膜10的方法中的任何一种制成。不管制成永久支承件12的方法，增强件22例如通过为缠绕在支承件12周围的针织物或线缆而形成在支承件12周围。由于支承件12使增强件22保持呈圆形形状并具有期望直径，故可基于膜20的预期用途来选择增强件22的密度。例如，意图用于在饮用水过滤中使用的膜20可具有增强件22，其密度比意图用于在废水中使用的膜20中小。在增强件22放置在支承件12周围之后，组合结构穿过涂覆头16，如关于图3在上面描述的。
如果管状支承件12将不保留在完成的膜20内部，则支承件12由能够溶解在分离层14的非溶剂中的材料制成。例如，支承件12可为可溶于水的。增强件22如以上描述地施加在支承件12周围，并且组合结构如关于图3描述地穿过涂覆头16。支承件12提供了使增强件22的内表面形状保持为管状形状并使组合结构保持定心在涂覆头16中的基础。这协助形成涂料18的均匀涂层和因此一致厚度的膜壁14。
在已形成固体膜壁14之后，支承件12在凝固浴或单独的溶剂中被洗出。增强件22优选为足够疏松的，使得涂料18将已穿透增强件22至支承件12的外表面。至少外丝24或丝24的节段包封在膜壁14中。增强件22还可为非常薄的，使得膜20的外径可为1mm或更小。在支承件12和增强件22中使用的材料的总量可与制造非支承膜所需的孔流体的量相似或小于该量。因此，轻型支承膜22可制造用于与非支承膜相似的价格但是具有增大的强度。来自支承件12的溶解材料可从凝固浴或其它溶剂回收。
利用例如呈可溶于水的管的形式的管状支承件12上方的针织增强件22，在针织期间和在涂覆过程期间施加的张力有助于确保圆形针织增强件22平稳地位于支承件12的表面上。支承件12的壁厚选择成使得支承件12不被完全溶解直到涂料18中的膜材料凝固。因此，虽然丝24可在涂料18施加至支承件12之前彼此固定，但是这不是强制的，这是因为凝固的涂料18足以维持丝在完成的第二膜20中的针织物中的位置。
针织增强件22优选地通过圆形经编针织制成。经编针织物由沿柱形针织物的表面纵向地延伸的多个纱线***(使用单丝或多丝纱线)组成。每个纱线***具有指定针，并且纱线引导元件在形成环的针之间交替。相比之下，纬编针织物由通过由针形成的环互连的一个或更多个纱线***形成。在纬编针织中，相邻的环(针脚(stitch))围绕圆形针织物的纵向轴线沿螺旋形的线延伸。多个形成环(针脚)的针和纱线引导元件关于彼此旋转。纬编针织物提供比经编针织物更接近封闭和柱形的表面，但是使用较多的丝24材料并且在长度上为较不稳定的。虽然纬编材料在其主要用途是支承涂料18的情况下可为更好的，但是在本膜10中，涂料浇铸到管状支承件12上，并且针织物意图增大膜10的强度。经编针织物比纬编针织物更坚硬或在长度上更稳定，并且因此经编针织物优选用于用作增强件12。
图4在图的下部分中示出了通过挤出PVAL而制成的管状支承件的实例。在图4的上部分中，细聚酯多丝纱线(133 dtex f 32)(其中，通过以相邻的针形成环而在4针经编针织机上针织)位于可溶解管状支承件12上方。针距为2.5-3.5mm(2.8-4环/cm)。接着，利用基于PVDF的膜涂料18涂覆组合结构。在涂料形成为固体分离层14之后，支承件12被溶出。得到的膜20的截面在图5中示出。

Claims (11)

1.一种制造中空纤维膜的方法，其包括以下步骤：
a)提供管状支承结构；
b)使所述支承结构穿过圆形经编针织机，以在所述支承结构周围形成呈圆形针织物的形式的织物增强结构；
c)利用膜涂料覆盖所述织物增强结构；
d)使所述膜涂料转化成固体多孔膜壁；以及
e)在步骤d)之后溶解所述管状支承结构。
2.根据权利要求1所述的方法，其特征在于，所述管状支承结构能够溶于水。
3.根据权利要求1所述的方法，其特征在于，所述织物增强结构在张力下形成在所述支承结构周围。
4.根据权利要求1所述的方法，其特征在于，步骤c)包括使所述支承结构和所述增强结构穿过涂覆头的入口，其中，所述入口定心在膜涂料出口内。
5.根据权利要求1所述的方法，其特征在于，步骤b)包括使所述支承结构按照涂覆头穿过所述圆形经编针织机。
6.一种制造中空纤维膜的方法，其包括以下步骤：
a)提供管状支承结构，其中所述支承结构为多孔的；
b)使所述支承结构穿过圆形经编针织机，以在所述支承结构周围形成呈圆形针织物的形式的织物增强结构；
c)利用膜涂料覆盖所述织物增强结构；以及
d)使所述膜涂料转化成固体多孔膜壁，
其中，步骤a)包括挤出热塑性膜聚合物与从由以下组成的组选定的第二材料的混合物：1)超临界气体、2)可溶于水的固体或液体，以及3)与所述膜聚合物不反应的聚合物。
7.根据权利要求6所述的方法，其特征在于，所述支承结构为非编织材料。
8.根据权利要求6所述的方法，其特征在于，步骤a)包括挤出半熔化聚合物粒子。
9.一种制造中空纤维膜的方法，其包括以下步骤：
a)提供多孔管状支承结构；
b)利用膜涂料覆盖所述支承结构；以及
c)使所述膜涂料转化成固体多孔膜壁，
其中，步骤a)包括选自由以下组成的组的步骤：
i) 挤出热塑性膜聚合物与超临界二氧化碳气体的混合物；
ii) 挤出热塑性膜聚合物与可溶于水的固体或液体的混合物；
iii) 挤出热塑性膜聚合物和与所述膜聚合物不反应的第二聚合物的混合物，随后拉伸挤出物以在两种聚合物之间形成裂缝；和
iv) 通过环形模在压力下挤出半熔化聚合物粒子。
10.根据权利要求9所述的方法，其特征在于，所述支承结构为非编织材料。
11.根据权利要求9所述的方法，其特征在于，还包括在步骤a)之后并在步骤b)之前在所述支承结构周围形成呈圆形针织物的形式的织物增强结构的步骤。
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BR112013014393A2 (pt) 2016-09-27
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AR084259A1 (es) 2013-05-02
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