CN106587280B - 协同处理有机废液和重金属废液并产电的光电化学方法和装置 - Google Patents

协同处理有机废液和重金属废液并产电的光电化学方法和装置 Download PDF

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CN106587280B
CN106587280B CN201610995252.1A CN201610995252A CN106587280B CN 106587280 B CN106587280 B CN 106587280B CN 201610995252 A CN201610995252 A CN 201610995252A CN 106587280 B CN106587280 B CN 106587280B
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陈庆云
刘晓河
尹思琪
王云海
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Abstract

本发明公开了一种协同处理有机废液和重金属废液并产电的光电化学装置，该发明采用光电极做阳极，和阴极组成光电化学池，阴极和阳极室用离子交换膜分隔，将有机废液充入阳极室，而重金属废液充入阴极室；在光照条件下，有机废液在阳极被光催化氧化，释放出电子和质子，电子经外电路转移到阴极，而质子通过电解质转移到阴极室；阴极室重金属废液中的重金属离子被外电路转移来的电子还原；系统同时实现了阳极室有机废液处理和阴极室的重金属废液处理，并向外电路输出了电能；该废液处理方法具有成本低廉、高效、易于工业化操作等特点，具有潜在的应用价值。

Description

协同处理有机废液和重金属废液并产电的光电化学方法和 装置
技术领域
本发明属于环境保护水处理领域，具体涉及一种协同处理有机废液和重金属废液并产电的光电化学方法和装置。
背景技术
有机废液广泛存在于工业生产、日常生活排放等领域，主要污染物为有机化合物，显示较高的COD浓度。目前对此类废水的处理技术通常包括生物氧化法、絮凝沉淀法、吸附、电催化氧化、化学氧化等。其中光催化氧化技术仅仅依靠光照射，在光催化剂作用下产生氧化能力很强的自由基，可以将有机废液中的有机物进行无选择氧化分解。相比于传统方法具有效率高，无需额外添加化学试剂、较少产生二次污染物等优点。在光催化氧化技术中，也有通过组装光电化学池实现阳极光催化氧化有机物，而阴极则往往是氧气还原为水或者产生氢气。
冶金、电镀、采矿等行业产生大量含重金属离子的废液。废液中的重金属离子对环境具有极强的危害性，该类废液通常通过化学沉淀或电渗析、反渗透等技术从废水中去除，产生的沉淀副产物或者浓缩液也容易产生二次污染。重金属废液中的重金属离子通常具有较强的氧化能力，可以被还原为低价金属或者金属单质进行回收。也有通过电解还原技术将重金属离子还原回收的，但该技术需要消耗大量的电能。
发明目的
本发明的目的在于提供一种高效、简便的协同处理有机废液和重金属废液并产电的光电化学方法和装置，使处理后的废水中污染物浓度大幅降低，同时回收重金属资源和电能。
为达到上述目的，本发明的装置包括采用光电极材料制成的光阳极和阴极组成的光电化学池，且光阳极和阴极之间采用离子交换膜分隔成用于处理有机废液的阳极室和用于处理重金属废液的阴极室，阳极室侧面由透光的玻璃或石英玻璃构建。
所述的光阳极采用具有光催化活性的光催化剂负载在ITO导电玻璃基底上或钛、铂、不锈钢金属基底上制成。
所述的具有光催化活性的光催化剂为二氧化钛、三氧化钨、三氧化二铁、钒酸铋、氧化亚铜、铁酸钙或硫化镉
所述的阴极采用石墨、玻璃碳、碳纤维、钛、铜或不锈钢导电材料。
本发明光电化学方法如下：将有机废液充入阳极室、重金属废液充入阴极室，在光照条件下，光阳极上产生具有氧化性的羟基自由基和空穴，将有机物氧化成二氧化碳，同时释放电子和质子，在电位差作用下，电子经外电路传导到阴极，产生电能，而质子则通过电解质转移到阴极室，阴极液中的重金属离子接受转移到阴极上的电子被还原，以低价态或单质形式被回收。
所述的有机废液为含有农药、农药中间体、医药、医药中间体、染料、染料中间体、化工产品、焦化产物或生活污水的废水。
所述的重金属废液为含有金、银、铜、镍、铬、镉、铅、钴的游离金属离子或者络合态的金属离子的废水，或含有有机或无机的络合剂。
本发明利用光电化学反应实现重金属废液中重金属离子的还原和有机废液中有机物的氧化处理，实现重金属废液和有机废液协同处理及产电，处理后的废水中污染物浓度大幅降低，同时回收重金属资源和电能。通过本发明的实施，在只有光照射的条件下，可以实现有机废物和重金属废液的高效快速处理，同时回收重金属资源并产生电能。
附图说明
图1是本发明的装置示意图。
图2是本发明以亚甲基蓝和六价铬为模拟有机废液和重金属废液协同处理的效果图。
图3是六价铬还原和亚甲基蓝氧化的光电化学池上200欧姆外阻两端的电压随时间的变化图。
具体实施方式
参见图1，本发明包括采用光电极材料制成的光阳极1和阴极2组成的光电化学池，且阳极1和阴极2之间采用离子交换膜3分隔成用于处理有机废液的阳极室4和用于处理重金属废液的阴极室5。其中光阳极1采用二氧化钛、三氧化钨、三氧化二铁、钒酸铋、氧化亚铜、铁酸钙或硫化镉等具有光催化活性的光催化剂负载在ITO导电玻璃基底上或钛、铂、不锈钢金属基底上制成，阳极室4侧面由透光的玻璃或石英玻璃6构建，具有透光性，从而保证光线能直接照射到光阳极1上。阴极2采用石墨、玻璃碳、碳纤维、钛、铜或不锈钢导电材料。
本发明协同处理有机废液和重金属废液并产电的光电化学方法如下：将有机废液充入阳极室4、重金属废液充入阴极室5，在光照条件下，光阳极1上产生具有氧化性的羟基自由基和空穴，将有机物氧化成二氧化碳，同时释放电子和质子，在电位差作用下，电子经外电路传导到阴极2，产生电能，而质子则通过电解质转移到阴极室5，阴极液中的重金属离子接受转移到阴极2上的电子被还原，以低价态或单质形式被回收。
本发明的有机废液为含有农药、农药中间体、医药、医药中间体、染料、染料中间体、化工产品、焦化产物或生活污水的废水；重金属废液为含有金、银、铜、镍、铬、镉、铅、钴的游离金属离子或者络合态的金属离子的废水，或含有有机或无机的络合剂。
以下是本发明的一个实施例：以3cm2的钛片负载TiO2纳米管为光阳极，3cm2的石墨毡为阴极，20mg/L的亚甲基蓝33mL为阳极液，2000mg/L六价铬Cr(VI)26mL为阴极液，0.5mol/L的硫酸钠为辅助电解质，以双极膜分隔阴极液和阳极液，外加200欧姆的负载。在氙灯模拟太阳光照射阳极条件下，亚甲基蓝被迅速降解，六价铬被还原为三价铬，其浓度随时间的变化如图2所示。外电阻两端的电压如图3所示。实验结果显示，经过6h反应，甲基蓝浓度基本降为零，而六价铬浓度降低至63mg/L，去除率达到97％。同时在反应时间内，电阻两端的电压从0.22V逐渐降低至44mV，期间产电1.23J。

Claims (5)

1.一种协同处理有机废液和重金属废液并产电的光电化学方法，采用的装置包括采用光电极材料制成的光阳极(1)和阴极(2)组成的光电化学池，且光阳极(1)和阴极(2)之间采用双极膜分隔成用于处理有机废液的阳极室(4)和用于处理重金属废液的阴极室(5)，阳极室(4)侧面由透光的玻璃或石英玻璃(6)构建，其特征在于：
将有机废液充入阳极室(4)、重金属废液充入阴极室(5)，在光照条件下，光阳极(1)上产生具有氧化性的羟基自由基和空穴，将有机物氧化成二氧化碳，同时释放电子和质子，在电位差作用下，电子经外电路传导到阴极(2)，产生电能，而质子则通过电解质转移到阴极室(5)，阴极液中的重金属离子接受转移到阴极(2)上的电子被还原，以低价态或单质形式被回收，其中，所述的重金属废液为含有金、银、铜、镍、镉、铅、钴的游离金属离子或者络合态的金属离子的废水。
2.根据权利要求1所述的协同处理有机废液和重金属废液并产电的光电化学方法，其特征在于：所述的有机废液为含有农药、农药中间体、医药、医药中间体、染料、染料中间体、化工产品、焦化产物或生活污水的废水。
3.根据权利要求1所述的协同处理有机废液和重金属废液并产电的光电化学方法，其特征在于：所述的光阳极(1)采用具有光催化活性的光催化剂负载在ITO导电玻璃基底上或钛、铂、不锈钢金属基底上制成。
4.根据权利要求2所述的协同处理有机废液和重金属废液并产电的光电化学方法，其特征在于：所述的具有光催化活性的光催化剂为二氧化钛、三氧化钨、三氧化二铁、钒酸铋、氧化亚铜、铁酸钙或硫化镉。
5.根据权利要求1所述的协同处理有机废液和重金属废液并产电的光电化学方法，其特征在于：所述的阴极(2)采用石墨、玻璃碳、碳纤维、钛、铜或不锈钢导电材料。
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