CN105597558B - 一种具有催化降解功能的复合纳滤膜及其制备方法、应用 - Google Patents
一种具有催化降解功能的复合纳滤膜及其制备方法、应用 Download PDFInfo
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Abstract
本发明公开了一种具有催化降解功能的复合纳滤膜，支撑膜内生成有通过原位合成制备的并且具有催化性能的金属氧化物，其制备方法及应用。通过原位合成的方法在纳滤膜的微孔中生成金属氧化物催化剂，从而得到具有催化功能的复合纳滤膜，其能够有效地降解废水中难以降解的有机物，从而也减少了大分子有机物堵塞膜孔而导致的膜污染现象。本发明的催化功能化纳滤膜在不调节pH，25℃的条件下对浓度为25ppm的苯酚的截留率达到75%以上，并且同时能降解大部分污染物，降解率能达到80%以上，降解产物经测定为小分子酸类。
Description
技术领域
本发明涉及具有催化降解功能的复合纳滤膜，用于生产这种膜的方法以及其用途。在环境技术背景下，这些复合膜用于废水处理。
背景技术
目前的膜分离技术包括微滤、超滤、纳滤以及反渗透等，这些分离技术可以归类为机械分离法。这些分离机制由不同的膜结构支配，通过直径小于待分离颗粒的直径的膜孔来进行分离。微滤、超滤和纳滤膜的孔径大约在1nm至20μm之间。
上述膜分离技术用于在压力下处理液体，进液在一定压力下过膜，大的杂质或有机物分子及离子能被截留，渗透液达到排放或饮用标准。
其中纳滤膜和反渗透膜大多数是通过界面聚合方法制得的芳香聚酰胺复合膜，膜上的荷电基团多为负电荷，如羧基、酰胺基，带磺酸基的聚砜为底膜的纳滤膜。纳滤膜的最大应用领域是饮用水软化和有机物的脱除。纳滤的分离范围处理超滤和反渗透之间，纳滤膜绝大数呈多层疏松结构，截留的分子量在200道尔顿以上。
从已有的技术来说，金属氧化物对有机物的的氧化降解效果明显，彻底的降解氧化过程能将有机物（例如酚类物质)变成二氧化碳和水。
金属氧化物的催化性能是根据氧化物表面形成的氧物种，大致可以分为以下三类：第一类，具有较多供电子中心而使吸附具有较多电荷呈O-形式，属于此类的过渡金属氧化物（如NiO、MnO、CoO、Co3O4等）往往增加氧化度；第二类，供电子中心的浓度较低，吸附氧带有较少的负电荷而呈O2 -形式，属于此种类型的过渡金属氧化物主要有ZnO、SnO2、V2O5和分散在抗磁性物质上低价过渡金属氧化物以及与绝缘物质形成的固溶体（如CoO-MgO，MnO-MgO）等；第三类：不吸附氧并具有盐特征的混合物，其中氧与高价氧化态的过渡金属中心离子形成具有确定结构的阴离子，主要有MoO3、WO3、NbO3和一些铝酸盐、钨酸盐以及含有钼、钨的杂多化合物，在这些氧化物上，碳氢化合物主要发生选择性氧化。
以上所提到的金属氧化物氧化降解的条件是各异的。
发明内容
本发明的一个目的是提供一种基于某些金属氧化物具有的催化氧化性能的水处理膜，在废水处理的过程中，不仅起到简单的物理筛分截留作用，更是可以通过化学法将难以降解的有机物氧化降解的高性能复合纳滤膜。具体技术方案如下：
具有催化降解功能的复合纳滤膜，支撑膜内生成有通过原位合成制备的并且具有催化性能的金属氧化物。
进一步的，所述支撑膜是由无机或有机材料组成的，所述支撑膜的的孔径是1nm至1μm。
进一步的，所述金属氧化物包括氧化锰（二氧化锰，四氧化三锰），二氧化镍，二氧化铜，氧化铁。
进一步的，所述金属氧化物尺寸在几百纳米到几微米之间，并且形貌多样，包括花状，针状，颗粒状，棒状，片状等。
进一步的，所述复合纳滤膜根据金属氧化物的催化性能在不同条件下，催化降解的效果各异。
进一步的，所述纳滤膜具有吸附有机物性能和具有催化降解有机污染物的性能。
具有催化降解功能的复合纳滤膜的制备方法，反复将反应溶液注入支撑膜内，反应物在膜壁上的微孔内在温度范围60-100℃内反应得到金属氧化物催化剂。
具有催化降解功能的复合纳滤膜，在对酚类物质催化降解的应用。
本发明通过原位合成的方法在纳滤膜的微孔中生成金属氧化物催化剂，从而得到具有催化功能的复合纳滤膜，其能够有效地降解废水中难以降解的有机物，从而也减少了大分子有机物堵塞膜孔而导致的膜污染现象。苯酚是最小分子量的酚类物质，其大部分同系物分子量均小于500道尔顿。并且根据已有的研究，在pH=11，25℃条件下的纳滤膜对苯酚的截留率达到75%以上，而本发明的催化功能化纳滤膜在不调节pH，25℃的条件下对浓度为25ppm的苯酚的截留率达到75%以上，并且同时能降解大部分污染物，降解率能达到80%以上，降解产物经测定为小分子酸类。
附图说明
图1（a）、（b）、（c）、（d）是在聚四氟乙烯微滤膜孔中原位合成的不同形貌氧化物粒子图；
图2是一定通量下氧化锰/PTFE复合纳滤膜对苯酚的降解效率图；
图3是不同苯酚起始浓度下氧化锰/PTFE 复合纳滤膜降解效率变化图；
图4是对氨基苯酚及对氨基苯酚渗透液的紫外光谱图；
图5是对氨基苯酚原溶液及对氨基苯酚渗透液的高效液相图谱。
具体实施方式
下面结合附图对本发明作进一步说明。
本发明将选择催化条件简单，易操作的金属氧化物，如氧化锰作为催化剂并通过原位合成的方法制得具有催化性能的复合纳滤膜。
氧化锰催化剂的原位制备工艺是本发明的关键，选择适合的反应溶液，确定其浓度及比例，然后在常温常压下，反复在膜壁的微孔中原位合成目标金属氧化物。根据已有的研究，同样的原料经过不同的制备工艺将得到不同的价态或不同尺寸形貌的催化剂，而催化剂的价态和形貌都是影响催化效率的重要因素。
以金属氧化物氧化锰为例，根据已有的研究表明：Mn3O4，α-Mn2O3，β-MnO2三种氧化锰催化活性比较：Mn3O4 > α-MnO2 > α-Mn2O3 > β-MnO2。
氧化锰的尺寸形貌也将影响其催化性能。例如同一价态的不同形貌的金属氧化物氧化锰。分别通过方法一，以高锰酸钾溶液和硫酸锰溶液为原料经过搅拌和水热法160℃的高温合成；方法二，以高锰酸钾溶液和硫酸溶液为原料，经过搅拌在水浴60℃的条件下合成；方法三，以高锰酸钾和葡萄糖作为原料，在水热法120℃的条件下合成。分别形成棒状，花瓣状和哑铃状的氧化锰，其比表面积分别为53.1 m2/g，30 m2/g，113.5 m2/g。对浓度为1000 ppm的甲苯溶液进行降解，在甲苯和氧气摩尔比为1:400条件下，氧化锰可以将甲苯的完全催化降解成CO2和H2O。由此表明，在氧气充足的情况下，二氧化锰的催化能力显著。
本发明基于聚四氟乙烯中空纤维膜（PTFE HFMs）优异的疏水性能和超强的耐酸碱性以及抗氧化耐老化性能而选其作为制备该复合膜的首选基膜。在60-100℃的温度范围内，选用硫酸锰溶液和高锰酸钾溶液作为反应溶液在基膜微孔中合成得到氧化锰粒子。
通过原位合成的方法在PTFE 中空纤维膜的膜孔中合成氧化锰粒子，根据扫描电镜的结果，发现形成了颗粒直径在100nm至3μm之间的氧化锰，并且其形貌随反应条件的变化而呈现出粒子、棒、片和花瓣状。如图1(a)、(b)、(c)、(d)所示。其中图（a）为棒状氧化锰；图（b）为花状氧化锰；图（c）为絮状氧化锰；图（d）为片状氧化锰。
以氧化锰作为金属氧化物催化剂在聚四氟乙烯中空纤维膜上原位合成复合纳滤膜，以苯酚溶液作为进液，通过控制膜的通量和苯酚的起始浓度对该复合膜进行催化性能检测。如图2所示，显示在通量为0.5-5 L/（m2·h）时苯酚进液经上述复合膜过滤并催化降解后，渗透液中苯酚的降解率随时间的趋势图。
氧化锰作为催化剂降解有机物过程中通过添加一些氧化剂，例如过氧化氢，过一硫酸氢钾等可以增强其催化降解性能。本发明中复合膜催化测试中通过添加浓度为0.1-0.5 mmol/L的过一硫酸氢钾(PMS)来促进苯酚的降解。过一硫酸氢钾具有非常强大而有效的非氯氧化能力，使用和处理过程符合安全和环保要求。同时，实施中通过设置苯酚进液不同的初始浓度如100ppm,75ppm,50ppm,25ppm，测试其催化效果。发现氧化锰/纳滤复合膜对起始浓度为25ppm的苯酚溶液的降解效率最好且持久。图3是不同初始浓度进液经本发明的复合纳滤膜过滤并催化后，渗透液的降解率与时间的趋势图。
以对氨基苯酚为进液，测试上述复合纳滤膜对其他酚类的催化效果。对氨基苯酚是一种重要的工业原料，在制药工业和染料工业有着广泛的应用。利用紫外可见分光光度计和高效液相色谱仪测试降解效果和产物的成分。结果显示氧化锰/PTFE复合纳滤膜对对氨基苯酚的降解明显，降解产物主要是小分子酸类物质，反映了该复合膜能深入的降解对氨基苯酚，渗透液的紫外光谱和高效液相图谱如图4和5所示。
如图4所示对氨基苯酚水溶液的紫外特征出峰位置分别为226nm,195nm,经过该功能性纳滤膜后得到的紫外特征出峰位置为215nm,初步可以推测对氨基苯酚溶液中的所含物质发生了改变。
高效液相色谱仪进行测试了降解产物成分，根据图5，对氨基苯酚原溶液和经过该功能性纳滤膜的对氨基苯酚的渗透溶液的保留时间发生了改变，对氨基苯酚溶液原样在保留时间为1.25 min, 1.80 min, 2.24 min处有色谱峰,而四组对氨基苯酚渗透液的图谱在保留时间为1.25 min, 1.40 min, 1.57 min, 2.24 min处有色谱峰。通过液相图谱分析可知，1.25min是草酸（oxalic acid)的出峰位置，1.57min处为顺丁烯二酸(maleic acid)，1.80min为反丁烯二酸(fumaric acid)，2.24min 是对苯醌(P-benzoquinone)。可见对氨基苯酚溶液经过该功能性纳滤膜后发生了显著的降解,说明该功能性复合纳滤膜能够降解对氨基苯酚，降解产物为小分子酸类。
Claims (1)
1.一种具有催化降解功能的复合纳滤膜的制备方法，该具有催化降解功能的复合纳滤膜的支撑膜内生成有通过原位合成制备的并且具有催化性能的金属氧化物，其特征在于：反复将反应溶液注入支撑膜内，反应物在膜壁上的微孔内在温度范围60-100℃内反应得到金属氧化物催化剂。
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