CN107337266B - 一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法 - Google Patents
一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法 Download PDFInfo
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Abstract
一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法:包括以下步骤:a)将陶瓷中空纤维膜于金属盐前驱体溶液中浸渍并烘干;b)将所述浸渍处理后的膜高温烧结;c)重复上述a)、b)步骤直到指定负载量;d)将上述负载膜于铸膜液中浸渍,并置于非溶剂相中凝胶,形成疏水膜表面。上述中空纤维复合膜用于水和废水的臭氧处理工艺过程,可有效提高臭氧传质速率,污染物降解速率,并解决了催化剂回收困难的问题,可实现反应器体积较小,反应过程能耗较低等效果。
Description
技术领域
本发明涉及一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法,属于水处理领域。
背景技术
臭氧被广泛地应用于水和废水的处理工艺中,如饮用水消毒及废水脱色等。在臭氧氧化工艺中,臭氧与污染物的反应速率以及臭氧传质速率是影响其处理效果的关键因素。
臭氧与污染物的反应过程包括直接反应和间接反应两种方式。其直接反应速率常数一般较低(kD为1.0-103M-1s-1),并且选择性较强,其臭氧利用效率较低,污染物降解速率较慢。在实际应用中,多通过羟基自由基方式的间接反应途径进行,其反应速率常数较高(kD为108-109M-1s-1),没有选择性,可高效降解污染物。常用的间接反应过程有臭氧/过氧化氢、臭氧/紫外线、臭氧/催化剂等体系。基于非均相催化剂的间接反应途径无需额外投加能量和试剂,是一种经济高效的高级氧化方法。所使用的催化剂多为纳米金属氧化物或负载了纳米金属氧化物的多孔材料。纳米金属氧化物的比表面积大,催化效果好,但其易团聚,回收困难,催化剂易损失。而负载型多孔材料无需回收过程或回收过程简单,是一种经济实用的催化剂。
除了臭氧反应速率,臭氧的传质速率对处理效果影响很大。传统的臭氧反应器大多为填料塔、鼓泡塔和喷雾塔等,尤其以由多孔曝气头及深水塔构成的鼓泡反应器最为常见。传统反应器的臭氧传质效率不够高,反应器体积往往较大。此外,传统反应器还易出现液泛、乳液、泡沫和雾沫夹带等问题,这些问题的出现进一步降低了臭氧的传质效率。因而需改进臭氧与水的混合方式,提高其传质速率,减小设备体积,提高其可操作性。
中空纤维膜接触器是一种新型气液接触设备。由于其具备比表面积大、传质速率快、传质过程无气泡产生等优势,已被应用于废水脱氨、烟气二氧化碳捕集、水体供氧等多种气液接触领域。研究表明,经过合理设计,膜接触反应器的体积比同等传质量的鼓泡塔小1-2个数量级。因此,基于中空纤维膜接触反应器的臭氧传质过程有望具有设备体积较小,传质速率较快等优势。
鉴于以上情况,本发明提出一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法。该中空纤维膜具有臭氧催化剂以及臭氧分布器两种功能。该中空纤维膜由陶瓷催化活性层和疏水层两部分组成。活性层为金属氧化物纳米负载的陶瓷颗粒组成,具有催化臭氧氧化活性。疏水层由疏水聚合物组成,为气水分布界面。该发明可同时解决臭氧利用率不够高,催化剂回收困难,臭氧传质效率不够高等多个问题。
发明内容
本发明提出一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法,该中空纤维复合膜由纳米金属氧化物负载的陶瓷颗粒活性层和疏水聚合物层组成,具有臭氧催化氧化和臭氧分布两种功能。
本发明提供的一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法,包括以下步骤:
a)将陶瓷中空纤维膜于金属盐前驱体溶液中浸渍并烘干;
b)将所述浸渍处理后的膜高温烧结;
c)重复上述a)、b)步骤直到指定负载量;
d)将上述负载膜于铸膜液中浸渍,并置于非溶剂相中凝胶,形成疏水膜表面。
优选的,所述陶瓷中空纤维膜为氧化铝、氧化锆、氧化硅、莫来石和堇青石的一种或多种;平均孔径为0.1μm-10μm。
优选的,所述金属盐前驱体溶液为锰、铁、钛、锌等过渡金属的硝酸盐或醋酸盐的一种或多种;其浓度为2wt%-50wt%。
优选的,金属前驱体负载的陶瓷膜烧结温度为300-1500℃;烧结时间为4-48h。
优选的,陶瓷膜的金属负载量为5wt%-15wt%。
优选的,疏水层铸膜液组分为聚合物(5wt%-15wt%),氯化锂(5wt%),N-N二甲基甲酰胺(80wt%-90wt%);非溶剂相为水。
优选的,所述聚合物为耐氧化能力良好的部分氟化聚合物种的一种或多种,包括:聚偏氟乙烯、聚(偏氟乙烯-共聚-六氟丙烯)、聚(偏氟乙烯-共聚-四氟乙烯)、聚(偏氟乙烯-共聚-三氟乙烯)等。
本发明的有益效果是:制备的中空纤维复合膜由活性层和疏水层组成,所述活性层由纳米金属氧化物负载的陶瓷颗粒组成,其比表面积大,催化臭氧效果良好。所述疏水层为聚合物形成,作为气液传质界面。中空纤维膜具有比表面积较大的优点,利用中空纤维复合膜反应器作为臭氧分布器可提高臭氧的体积传质系数,反应器体积较小。同时,基于膜接触反应器的臭氧传质过程无气泡产生,传质过程可有效地避免传统鼓泡反应器传质过程易出现的液泛、泡沫等问题。同时,由于催化活性层的存在,臭氧可被有效地转化为羟基自由基,加速与污染物的反应速率。因此,臭氧的利用效率得以提高,处理的水质也得到提升。此外,由于纳米金属氧化物固化在陶瓷颗粒上,催化剂流失和回收的问题得以解决。基于该中空纤维复合膜的反应器具有臭氧传质和催化臭氧氧化的双重效果。上述中空纤维复合膜接触反应器具有臭氧传质速率较快,臭氧利用率较高,催化剂无需回收,处理水质较好等优势。
附图说明
图1为本发明提出的一种具有催化臭氧氧化功能的中空纤维复合膜的制备流程示意图;
图2为实施例1所述中空纤维复合膜的活性层电镜图;
图3为实施例1所述中空纤维复合膜的疏水层电镜图;
图4为实施例2所述对比氧化实验装置图;
图5为实施例2所述对比氧化效果比较。
附图中,各标号所代表的部件列表如下:
1-1、原陶瓷膜;1-2、浸泡过金属盐前驱体的陶瓷膜;1-3、经烧结后的陶瓷膜;1-4、疏水层-活性层复合膜;4-1、臭氧发生器;4-2、臭氧浓度分析仪;4-3、中空纤维膜组件;4-4、蠕动泵;4-5、原料液罐。
具体实施方式
下面对本发明作进一步详细说明。
实施例1
以下结合附图对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
本发明提出的中空纤维复合膜的制备流程可参见图1.
将氧化铝中空纤维陶瓷膜(外径2mm,内径1mm,平均孔径0.5μm)裁剪为15cm长,在去离子水中超声清洗30min,120℃下干燥;400g上述陶瓷膜于1000ml40wt%硝酸锰水溶液中浸泡4小后取出,于120℃下干燥2h;
将上述中空纤维膜于500℃下烧结24小时,自然冷却后取出,超声清洗后于120℃下烘干2小时;
将100g聚偏氟乙烯树脂,50g氯化锂,850gN-N二甲基乙酰胺,混合搅拌均匀,形成铸膜液;并于真空脱泡30min,待用;
上述中空纤维膜用环氧树脂胶进行封端;将该中空纤维膜投入铸膜液中浸泡1min,后取出,沥干30s,此时,在陶瓷中空纤维膜表面形成一层聚偏氟乙烯铸膜液;
将上述中空纤维膜投入去离子水中,浸泡24h;后取出自然干燥24h,此时,中空纤维膜外表面形成一层聚偏氟乙烯疏水层,得到本发明所述的具有催化臭氧氧化功能的中空纤维复合膜。
对所述中空纤维复合膜进行扫描电镜分析,结果如图2,图3所示。图2为复合膜活性层于1万倍下的电镜图;图3为疏水层断面于2千倍下的电镜图。由图2可见,陶瓷颗粒表面为纳米氧化锰所覆盖,纳米颗粒的直径为100-200nm。由元素分析可知,锰相对负载量为5.4wt%。由X射线衍射分析可知其主要为α-二氧化锰。有图3可知,疏水层具有丰富的孔洞结构,其传质阻力较小。通过接触角测试,中空纤维膜的水接触角由22°-31°提高到95°-106°。而通过孔径测试,可知其泡点为0.6μm,平均孔径为0.12μm。通过LEPw测试,可知其水穿透压力为1.1bar。
由此可见,本发明提供的方法制备的中空纤维复合膜的活性层纳米催化剂负载量较大,比表面积较大,而疏水层疏水性良好,水穿透压力较大,具有较好的可操作性能。
实施例2
本实施例对实施例1所述制备的中空纤维复合膜进行臭氧氧化对比。
依据实施例1的方法制备不含氧化锰纳米颗粒的中空纤维复合膜5根,每根长15cm;
将上述负载/无负载纳米颗粒的中空纤维复合膜制备为膜组件各1支,每只膜组件含膜5根,有效长度8cm;
用如图4所示测试装置进行其氧化效果对比的测试;图中,4-1、臭氧发生器;4-2、臭氧浓度分析仪;4-3、中空纤维膜组件;4-4、蠕动泵;4-5、原料液罐。原料液为100μg/L的硝基苯溶液,溶液pH为1-5.臭氧浓度为30mg/L,臭氧流量为30ml/min,反应时间为15min,反应温度20℃。
对比效果如图5所示,可见催化臭氧体系比单独臭氧体系对硝基苯的降解效果有显著的提升。pH=1时,降解效果由2%提升到13%;pH=3时,降解效果由9%提升到19%;pH=5时,降解效果由50%提升到79%。
由上述实施例可见,纳米金属氧化物负载的中空纤维复合膜反应器对废水的降解有显著的提升,其操作可靠,效果明显。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。。
Claims (5)
1.一种具有催化臭氧氧化功能的中空纤维复合膜的制备方法,包括以下步骤:
a)将陶瓷中空纤维膜于金属盐前驱体溶液中浸渍并烘干;
b)将所述浸渍处理后的膜高温烧结;
c)重复上述a)、b)步骤直到指定负载量;
d)将上述负载膜于铸膜液中浸渍,并置于非溶剂相中凝胶,形成疏水膜表面,所述陶瓷中空纤维膜为氧化铝、氧化锆、氧化硅、莫来石和堇青石的一种或多种,其平均孔径为0.1μm-10μm,所述金属盐前驱体溶液为锰、铁、钛、锌在内的过渡金属的硝酸盐或醋酸盐的一种或多种,其浓度为2wt%-50wt%。
2.根据权利要求1所述方法,其特征在于:烧结温度为300℃-1500℃,烧结时间为4h-48h。
3.根据权利要求1所述方法,其特征在于:金属负载量为5wt%-15wt%。
4.根据权利要求1所述方法,其特征在于:铸膜液组分为聚合物5wt%-15wt%,氯化锂5wt%,N-N二甲基甲酰胺80wt%-90wt%,非溶剂相为水。
5.根据权利要求4所述方法,其特征在于:所述聚合物为耐氧化能力良好的部分氟化聚合物中的一种或多种,包括:聚偏氟乙烯、聚(偏氟乙烯-共聚-六氟丙烯)、聚(偏氟乙烯-共聚-四氟乙烯)、聚(偏氟乙烯-共聚-三氟乙烯)。
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