CN110799259A - 用于油/水分离的多层膜 - Google Patents

用于油/水分离的多层膜 Download PDF

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CN110799259A
CN110799259A CN201780089295.6A CN201780089295A CN110799259A CN 110799259 A CN110799259 A CN 110799259A CN 201780089295 A CN201780089295 A CN 201780089295A CN 110799259 A CN110799259 A CN 110799259A
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oil
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water separation
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刘兆阳
汪馗
贾亚普拉卡什·萨特哈西瓦姆
德玛·艾尔-马斯里
尼达尔·希拉尔
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Qatar Foundation for Education Science and Community Development
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Abstract

用于分离油和水的多层膜100包括多孔的顶层110、多孔的底层110和位于顶层110和底层120之间的颗粒状中间层120，该中间层120是疏水的并且适合于吸附油，例如可能通过顶层110的痕量油。顶层110和底层130是亲水性和疏油性的。然而，除了重力之外，所述膜100不要求在所述油/水混合物上施加任何外部压力以驱动穿过膜100的油/水混合物W分离，该分离可以由真空或其他类型的外部压力驱动。

Description

用于油/水分离的多层膜
技术领域
本发明涉及水过滤，具体地，涉及一种过滤膜以从水中分离出油。
背景技术
石油工业面临着各种各样的挑战，这些调整涉及从水中有效地提取石油，以及从城市污水中提取油脂。传统的分离设备和方法，如重力分离、撇渣、溶气气浮、离心和水力旋流器，要么成本太高、环境不友好、能源密集，和/要么分离效率低。例如，液体化学分散剂容易造成二次环境污染，而且固体吸附剂的吸附性受其吸附能力的限制，造成额外的废物用于清除。水力旋流器在油/水分离过程中通常需要较高的能量输入。
考虑到滤膜处理后出水水质好和相对简单的操作过程，过滤膜作为一项有前途的分离各种油/水混合物的技术已引起较多的关注。但是，传统的过滤膜仍然面临膜污染高、油/水分离不完全、能耗高和制造成本高等问题。此外，因为它们的相转化法制备工艺往往导致相对的小孔径，这些传统的过滤膜通常渗透通量低。因此，对于处理大量的含油废水，研制高渗透通量、低污染和高分离效率的新型滤膜是关键和迫切需要的。
因此，一种解决前述问题的油/水分离膜是理想的。
发明内容
所述用于从水中分离油的多层膜可以包括一个或多个多孔顶层、一个或多个多孔底层、和一个中间层，所述中间层在所述一个或多个顶层和所述一个或多个底层之间包含一种颗粒状材料，所述中间层是疏水性的。所述顶层和底层可以由亲水性和疏油性的机织物或非机织物制成。所述中间层的颗粒状材料可以包括疏水性或亲水性粉末。所述一个或多个顶层保持油，特别是非乳化油，并且允许水通过。所述中间的颗粒层吸附可以通过所述顶层的痕量油并且允许水通过。所述一个或多个底层为中间层和整个膜提供机械支承/强度。虽然除了重力之外所述膜不需要任何外部压力用于过滤穿过膜的油/水混合物，但是该过滤可以由真空或其它类型的外部压力驱动。
在进一步审阅下述说明和附图时本发明的这些特征和其它特征将变得容易理解。
附图说明
图1示出了根据本发明的一种用于油水分离的三层膜的分解图。
图2示出了根据本发明与所述用于油水分离的三层膜的顶层接触的油水混合物。
图3为根据本发明分离油水混合物的水下视图。
图4是用乳化的油/水混合物(10％油v/v)测试水的渗透通量(J，L/m2H)和废油率(oil rejection rate)(％)的曲线图。
除非另有说明，在所有附图中相同的参考符号一致地表示相应的特征。
具体实施方式
参照图1至图4，总体上示出了一种多层膜100，该多层膜100设置为从油/水混合物W(诸如乳化油/水混合物)中的水中分离油。在所示的实施方案中，该多层膜100是一种三层膜。在本文中，术语“膜”指的是一种半透性材料，当在膜100上或膜100内保留油时该半选择性材料选择性地允许水通过。正因如此，膜100功能类似于过滤介质，以通过选择性地允许水从膜100的一侧通过至膜100的另一侧来进行油水分离。需要注意的是，100膜既可以是平板膜，也可以是管状膜。
膜100包括具有多个孔115的顶层110、具有多个孔135的底层130和位于顶层110和底层130之间的中间颗粒层120，该中间层120是疏水性的并且适于吸附油，诸如通过顶层110的痕量油。顶层110和底层130具有亲水性和疏油性的纤维。然而，除了重力之外，膜100不需要在油/水混合物W上施加任何外部压力来驱动油/水混合物W穿过膜100的过滤，该过滤可以由真空或其他类型的外部压力驱动。
顶层110被配置为从油/水混合物W中保留一定量的油并且允许水通过(图2)，或者从膜100的顶层110渗透。顶层110能够保留油/水混合物w中的全部或部分油。顶层110能够保留至少1微米大小的非乳化油和乳化油。需要注意的是，顶层110的纤维的表面性能可以是本质上亲水性的，也可以是由疏水性的变为亲水性的，例如在疏水性材料的纤维表面涂覆亲水性涂层。该涂层材料的亲水性和水下疏油性能够使水流经顶层同时阻止油/水混合物W中的油渗透到顶层110。膜100的顶层110可以由任何合适的材料制成，诸如机织物或非机织物材料。例如，顶层110可以包括微米级尺寸的聚合物织物以及，任选地，合适的无机颗粒，诸如纳米级尺寸的无机颗粒。顶层110可以是任何合适的厚度，例如在1微米到1000微米之间的范围。
顶层110的亲水性和水下疏油性可以使顶层110较少地遭受油污染。顶层110的织物结构由于其大孔径(例如1微米以上)还能够提供高的水渗透通量，同时提供高的机械强度。但是，需要注意的是，顶层110的大孔径并不能有效地保留油/水混合物W中的所有油，即尺寸小于1微米的乳化油。
中间层120包括颗粒材料，诸如固体粉末。该固体粉末可以是尺寸小于100微米且表面积大于10平方米/克的粉末。中间层120的厚度可以是1微米到5000微米。例如，中间层120能够由0.5克的颗粒状活性炭经诸如玻璃棒(未显示)铺展在尺寸为5cm×5cm的中间层120表面而形成。用于形成中间层120的颗粒材料适合于吸附可能通过顶层110的微量油，例如乳化油。正因如此，中间层120能够帮助膜100获得高的废油率(图4)。中间层120能够通过类似于传统泡沫材料的毛细管力来吸收油。
位于中间层120下面的底层130可以包含多孔的亲水性材料。这种材料可以是机织物，也可以是非机织物。中间层120可以有任何合适的厚度，例如从大约1微米到大约1000微米。底层130的多孔材料115可以包含任何合适的材料，如微米级的聚合物织物，以及，任选地，合适的无机颗粒，例如纳米级无机颗粒。底层130的主要功能将是为中间层120提供机械支撑，同时加固整个膜100。
任选地，包括编织网，以便向底层130提供更高的机械强度，而同时地保持通过膜100的高渗透通量。需要注意的是，与顶层110的纤维类似，用于底层130的该纤维的表面性能要么是本质上亲水性的要么从疏水性变成亲水性，例如采用亲水性涂覆技术涂覆疏水性材料的纤维表面。
膜100可以通过多种方式形成。例如，膜100的顶层110和膜110的底层130都可以通过首先在100mL的醋酸溶液中溶解大约2克的壳聚糖(该壳聚糖脱乙酰度为15％)(即，95.0％-80.0％)以形成壳聚糖溶液(2wt％)制备而成。接下来，搅拌该壳聚糖溶液大约24小时，例如在磁力搅拌器的平板上。然后，可以在10mL的去离子(DI)水中溶解大约0.1克的聚乙烯醇(低分子量，PVA)，诸如在大约95℃下在烧杯中溶解大约24小时以制备一种PVA溶液(1wt％)。将大约10mL的PVA溶液添加到100mL的壳聚糖溶液中，例如，在磁力搅拌下，以形成一种复合溶液。接下来，可以向该复合溶液中添加1克二氧化钛(TiO2)纳米颗粒(20nm)，诸如在磁力搅拌下，以将该纳米颗粒更好地均匀分散在该溶液中。然后，可以对该复合溶液进行超声波处理，以去除气泡并形成涂覆溶液。
接下来，可以采用刮刀法将涂覆溶液浇注在所述顶层110和底层120两者的织物上。例如，该涂覆溶液可以倾倒在多孔棉织物115、135的表面上。玻璃棒(未显示)可用于手动地在织物表面上滚动，并去除层110、130每层的织物表面任何多余的涂覆溶液。通过使用玻璃棒将约0.5克颗粒状活性炭均匀地铺在底层表面能够形成膜层。一旦中间层120被放置在顶层110和底层130之间，就可以吹干膜100。
通过采用Rame-hart精密接触角测定仪(Rame-hart precision contact anglegoniometers)测量膜100的水接触角和水下油接触角表征膜100的表面润湿性能。膜100被固定在两个玻璃管之间，其中膜100的顶层110面朝上。将油/水混合物W(10％油v/v)在3000rpm以下涡旋振荡30秒，制备油/水混合物W。然后将油/水混合物W倒在膜100的顶层110上，如图2所示。如图2中所示，在膜100的顶层110上的水接触角W是大约0°，这表明膜100的顶层110是超亲水性的，并且有利于让水通过拒绝石油通过。如图3中所示，在膜100的顶层110上的水下油(柴油)接触角是大约150°，这进一步证明膜100的顶层110是水下超疏油性的，并且易于从膜100上排斥油O。由重力作用下油/水混合物W分离。
分离后，将收集的水去除以进行有含量分析。采用Jorin颗粒分析仪(Jorin'sParticle Analyzer)(Jorin Ltd.，Sandhurst,U.K.)测定分离后收集的水的油浓度。在图4中示出了该性能测试结果。膜100的水渗透通量为980J,L/m2H，其远高于其他商用微滤膜和超滤膜，废油率达到大约99.9％。
通过操作，在油/水分离过程中，油水混合物W首先接触膜100的顶层110。油/水混合物W中的水将渗透并流经膜100的顶层110层，而油/水混合物W中的油则保留在膜100上或膜100内。当水通过顶层110时，任何可以通过顶层110的油都会被中间层120保留，而水则通过第三层130。正如上文所述，分离过程可以由重力驱动，也可以由真空或压力驱动。
应当理解的是，本发明不限于上述实施方案，但包括所附权利要求范围内的任何和所有实施方案。

Claims (12)

1.一种用于油水分离的多层膜，其中，所述膜包括：
顶层，其具有多个孔，所述顶层是亲水性和疏油性的；
底层，其具有多个孔，所述底层是亲水性和疏油性的；以及
中间颗粒层，其在所述顶层和所述底层之间，所述中间层是疏水的并且适用于吸附油。
2.根据权利要求1所述的用于油水分离的多层膜，其中，所述顶层和所述底层中至少一个包括机织物。
3.根据权利要求1所述的用于油水分离的多层膜，其中，所述顶层和所述底层中至少一个包括非机织物。
4.根据权利要求1所述的用于油水分离的多层膜，其中，所述中间层包括固体粉末。
5.根据权利要求4所述的用于油水分离的多层膜，其中，所述固体粉末包括颗粒状活性炭。
6.根据权利要求4所述的用于油水分离的多层膜，其中，所述固体粉末的粒径尺寸小于100微米。
7.根据权利要求4所述的用于油水分离的多层膜，其中，所述固体粉末包括大于10m2/克的表面积。
8.根据权利要求1所述的用于油水分离的多层膜，其中，所述底层在其上进一步包括编织网。
9.根据权利要求1所述的用于油水分离的多层膜，其中，所述顶层包括多个孔径大于1微米的孔。
10.根据权利要求1所述的用于油水分离的多层膜，其中，所述顶层的厚度为大约1微米至大约1000微米。
11.根据权利要求1所述的用于油水分离的多层膜，其中，所述中间层的厚度为大约1微米至大约5000微米。
12.根据权利要求1所述的用于油水分离的多层膜，其中，所述底层的厚度为大约1微米至大约1000微米。
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