CN109789374A - 用于从水中去除或灭活微生物的过滤介质 - Google Patents

用于从水中去除或灭活微生物的过滤介质 Download PDF

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CN109789374A
CN109789374A CN201780058833.5A CN201780058833A CN109789374A CN 109789374 A CN109789374 A CN 109789374A CN 201780058833 A CN201780058833 A CN 201780058833A CN 109789374 A CN109789374 A CN 109789374A
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layer
water
particle
filter medium
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CN109789374B (zh
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董良杰
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Meso Filtration Co
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Abstract

本发明公开了用于去除水中的细菌和/或灭活病毒的一种过滤介质。该介质的实例包括由纤维素纤维制成的两个外层和由填充的陶瓷颗粒制成的内层。本发明还提供了生产该介质的方法。

Description

用于从水中去除或灭活微生物的过滤介质
相关申请的交叉引用
本申请要求于2017年6月11日提交的国际申请号PCT/US2017/036922和2016年9月26日提交的美国临时申请号62/399,485的优先权，其每一个的公开内容通过引用整体并入本文。
发明领域
本发明涉及从流体或空气中除去或灭活微生物的材料、组合物和方法，更具体地说，涉及从水中除去细菌和灭活病毒的材料、组合物和方法。
背景技术
细菌通常存在于供水中，致病菌可能引起伤寒、肠胃炎、传染性肝炎和霍乱等疾病。细菌去除是城市水处理过程的一个重要方面。常用的细菌去除方法包括微滤、超滤、反渗透、紫外线灭菌、化学氧化和消毒，其中化学氧化和消毒是最广泛使用的，臭氧氧化和氯处理是这种方法的代表。
这些现有的细菌处理技术存在各种缺陷。例如，过滤的方法，包括膜过滤、反渗透和超滤，成本昂贵并且需要高压操作。另外，过滤介质的后续处理也很麻烦。
病毒也可存在于水源中。它们和物种有关，人类特定的病毒在人流量很少的环境中往往较少存在。在世界发达地区，由于供水污染导致的病毒爆发很少见。然而，在卫生条件差的发展中国家，未经处理的污水会污染饮用水，病毒仍然构成重大风险。这些地区的病毒感染可以通过国际旅行传播到世界其他地区。
病毒是极小的微生物。大多数病毒物种的大小在0.01-0.3微米之间。为了大规模去除污水和水源中的病毒，通常使用活性污泥、金属离子或石灰凝结或化学消毒。然而，使用任何就地快速过滤装置很难从水中除去病毒。
仍然需要用于从水中去除微生物的新材料和方法，其简单，成本低且具有更好的性能。
发明内容
本发明所公开的主题的目的和优点将在下面的描述中阐述并且显而易见，并将通过实践所公开的发明主题得以了解。通过书面描述及其权利要求以及附图中特别指出的组合物和方法，将实现和获得所公开主题的其他优点。
本发明一般提供一种过滤介质，其包括第一层纤维材料，第二层纤维材料和设置在第一层和第二层之间的第三层。所述第三层包括多孔陶瓷颗粒，其包括直径为约20至约140纳米的孔。
在一些实施方案中，颗粒包含至少一种金属。所述金属可以是零价铁。所述零价铁可以原位沉积在颗粒的孔中。
在一些实施方案中，第一层和第二纤维材料层中的至少一个由纤维素纤维制成。
在一些实施方案中，介质是片状的并且具有约1mm或更小的总厚度。
在一些实施方案中，第三层的颗粒的外径不超过50微米。
在一些实施方案中，介质的基重为100至200克/平方米(gsm)。
在一些实施方案中，介质可有效去除水中的细菌。
在一些实施方案中，当含病毒的水通过介质时，介质可有效灭活水中的病毒。
详述
本文公开了本发明的实施方案，在一些情况下以示例性形式或通过参考一副或多副附图进行公开。然而，特定实施例的任何此类公开内容仅用于说明目的，并不表示本发明的全部范围。
在本发明的一个方面，提供了一种过滤介质。在一些实施方案中，过滤介质有效地从水中除去细菌。在某些实施方案中，过滤介质有效灭活或杀死病毒。介质还可以从水中除去金属离子污染物，例如砷(包括砷酸盐、亚砷酸盐)和铅(Pb)离子。因此，过滤介质可以同时处理水以去除许多种有害物质。此外，过滤介质可以通过重力过滤来实现所有这些功能，即，介质可以是自立的或放置在容器的顶部，并且水从上方通过它并流到其下方的容器。无需真空泵或外部压力；水可以通过重力穿过介质中的层。因此，过滤介质特别适于作为就地使用装置来处理质量可疑的水。
如图1所示，过滤介质100包括由纤维材料制成的第一层110，由纤维材料制成的第二层120，以及设置在第一层110和第二层120之间的第三层120。第三层包括多孔陶瓷颗粒，其直径为约20nm至约140nm的孔。为了方便和说明，第一层110也称为底层，第二层120也称为顶层，第三层130也称为中间层。
底层110和顶层120均可由非织造纤维制成，例如天然纤维素纤维，其可以是棉纤维或衍生自其他植物的纤维。也可以包括合成纤维，例如聚乙烯、聚丙烯、聚酯、聚酰胺、丙烯酸树脂、玻璃纤维等。过滤介质的制造可以通过类似于制造非织造织物的方法完成。例如，可以将例如纸浆形式的纤维素纤维铺在一个表面上，然后将陶瓷颗粒以预定的密度(克/平方米或gsm)铺在纤维素纤维的上面。最后，将另一层纤维素纤维铺在陶瓷颗粒的上面。层状结构在进行热处理(例如通过加热辊)的同时被压实，用于纤维的结合和层的紧密集成，以及用于去除水分。在该过程中陶瓷颗粒可能部分聚集。可以通过微波加热器进一步加热残留水分。成品介质产品是片状的，并且可以像普通纸一样是柔性和可折叠的。顶部和底部纤维层通常是多孔的(孔径为数十或数百微米)，但为介质提供强度和结构完整性。介质可以制成不同的厚度，例如约2mm或更小、约1mm或更小，或甚至更薄。
用于中间层的陶瓷颗粒包括多个直径为20nm至140nm的孔。在一些实施方案中，介质的至少50％的孔具有约20nm至约70nm的直径。在其他实施方案中，介质的至少60％，至少65％，至少70％，至少75％，至少80％，至少85％或至少90％的孔具有20nm至70nm。在一些实施方案中，多个孔中的至少70％具有40nm至约60nm的直径。孔形成开放结构，使得水可以透过介质。如果孔尺寸太大，细菌和病毒等微生物可以自由地通过毛孔而不会被困住或受损。
陶瓷颗粒可以基于氧化铝并含有约90wt％或更多的氧化铝，并且可以进一步包括碳。在一些实施方案中，陶瓷颗粒包括零价铁(或ZVI或Fe(0))。在示例性实施方案中，颗粒可以根据2016年6月12日提交的美国临时申请62/349,022以及2017年6月11日提交的PCT申请PCT/US2017/036922中描述的步骤制备，其公开内容通过引用整体并入本文。简言之，将结构材料(例如含有70wt％或更多氧化铝的粘土材料，例如硅藻土，其可首先脱硅以降低SiO2含量)与碳源材料(例如碳水化合物，比如说糖或者淀粉)和水混合，以获得原始陶瓷颗粒，其含有粘附在主要包含氧化铝的孔壁上的碳(至少其中一些被认为是活性炭)。然后将原始陶瓷颗粒在缺氧气氛或室中加热或烧制以产生多孔颗粒，然后首先与含有Fe2+的溶液接触，然后使还原剂(例如NaBH4或KBH4)与Fe2+在多孔颗粒的孔隙中原位还原为ZVI。含有ZVI的多孔颗粒再次在缺氧气氛中加热，以产生用于中间层的颗粒。这种含ZVI的颗粒能够除去水中的砷酸盐、亚砷酸盐、Pb、Cd、Hg和其他重金属离子。
为了减少微生物通过颗粒间隙逃逸的机会，陶瓷颗粒的尺寸应足够小以确保颗粒的紧密堆积。例如，颗粒的外径可以不超过约50微米(或者颗粒可以通过320目筛网筛分)。在一些实施方案中，颗粒的基重的填充密度可为约50至约300gsm，或约100至约200gsm。当在聚光灯装置中检查时，颗粒应均匀地分布在外纤维层内而没有裂缝或孔。
本发明的过滤介质可有效去除水中的细菌。由于颗粒孔的尺寸通常小于细菌的大小，水中的细菌将被过滤介质拦截，通常在颗粒和纤维层之间的界面处。
此外，当含病毒的水通过重力通过过滤介质时，本发明的过滤介质可有效地灭活或杀死水中的病毒。虽然不希望受任何特定理论的束缚，但据信当病毒小到足以进入陶瓷颗粒的孔隙时，当它通过互连的多孔结构进行迁移时，其保护性包膜或衣壳(蛋白质壳)可能被陶瓷颗粒的锯齿状的内孔表面损坏，导致病毒的遗传物质降解或失去其活性。
以下实施例是为了说明而不是为了限制。
实施例1：中间层颗粒的制备
将通过脱硅处理的来自铝土矿区的硅藻土粉末通过吹气选择和分离，研磨成1200标准目，并与作为碳源的5％淀粉混合。通过添加约12％至约15％纯水(基于原始陶器的重量)将混合物粉末造粒为0.5mm至1.0mm尺寸的生陶颗粒。将由此形成的生陶颗粒在500℃下焙烧3小时，升温速率为2℃/min。将烧制成的介质浸没在2％的FeSO4溶液中15分钟，取出以自然浸出水，然后放入2％的NaBH4溶液中30分钟，在介质的孔内发生零价铁结晶。将ZVI溶液处理过的介质再次在480-500℃的烘箱中焙烧3小时，同时在整个焙烧过程中加氮气保护。然后将处理过的介质冷却至室温并储存以备将来使用。
实施例2：大肠杆菌捕获
含有根据实施例1制备的颗粒的中间层的本发明的片状过滤介质用于过滤含有大肠杆菌的溶液。图2A-2D包括通过过滤介质捕获的大肠杆菌的某些SEM照片。结果表明，细菌通常保留在陶瓷颗粒的边缘，靠近纤维层的界面处(图2D显示了固定在陶瓷颗粒上的分开的大肠杆菌)。据推测，陶瓷颗粒的吸收性能在将细菌保留在其表面上起了作用。
实施例3：去除蜡状芽孢杆菌
将50μl浓度为10,000/ml的蜡状芽孢杆菌溶液加入到500ml无菌蒸馏水中以制备芽孢杆菌原液。用量筒取20ml原液，并用一片本发明的过滤介质过滤。用两片过滤介质过滤另外20ml原液。加入400μL未过滤的杆菌细菌溶液以及400μL两种过滤的溶液并在分开的无菌琼脂平板中铺展。将平板在37℃下孵育24小时。肉眼观察每个平板中的菌落数。发现一片过滤介质已经足够有效地从原液中除去所有蜡状芽孢杆菌。两片过滤介质也从原液中除去100％的杆菌。
实施例4：通过过滤介质杀死病毒
使含有烟草花叶病毒的溶液通过本发明的过滤介质。确定病毒灭活。如图3所示，图3是已通过介质的烟草花叶病毒的SEM照片。可见病毒的包膜沿其长度方向被切开，这显然导致了病毒的消亡。
对本领域技术人员显而易见地是，在不脱离本发明的范围和精神的情况下，可以对本文公开的发明进行各种修改。

Claims (10)

1.一种过滤介质，包括：
第一层纤维材料；
第二层纤维材料；和
设置在第一层和第二层之间的第三层，所述第三层包括多孔陶瓷颗粒，其具有直径为约20nm至约140nm的孔。
2.如权利要求1所述的介质，其中所述颗粒包含至少一种金属。
3.如权利要求2所述的介质，其中所述金属是零价铁。
4.如权利要求3所述的介质，其中所述零价铁原位沉积在所述颗粒的孔中。
5.如权利要求1所述的介质，其中所述第一层和所述第二层纤维材料层中的至少一个包括纤维素纤维。
6.如权利要求1所述的介质，其中所述介质的总厚度为约1mm或更小。
7.如权利要求1所述的介质，其中所述第三层的颗粒的外径不超过50微米。
8.如权利要求1所述的介质，其中所述第三层的填充密度为100至200gsm。
9.如权利要求1-8中任一项所述的介质，其中所述介质可有效去除水中的细菌。
10.如权利要求1-8中任一项所述的介质，其中当含病毒的水通过所述介质时，所述介质可有效灭活水中的病毒。
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