CN109516527B - 一种连续流电化学过滤系统及其在降解氨氮废水中的应用 - Google Patents
一种连续流电化学过滤系统及其在降解氨氮废水中的应用 Download PDFInfo
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Abstract
本发明公开了一种连续流电化学过滤系统及其在降解氨氮废水中的应用。所述连续流电化学过滤系统包括阳极与阴极，其特征在于，所述阳极采用Ti4O7薄膜，阴极采用Pd/Cu改性的Ni泡沫，阳极、阴极相对一侧的表面各设有一层PTFE基底膜，且阳极的一侧为进水口，阴极的一侧为出水口，出水口处设有Ag/AgCl参比电极；阳极、阴极分别通过一集流体与电源的正极、负极连接。本发明采用了膜分离与电化学技术相结合的改进方法，并以一种连续流操作方式进行。在这种体系中，对流强化传质可显著增强目标污染物分子向膜表面活性位点的传递过程，具有易控制和可放大等优点，有望实现工程应用。
Description
技术领域
本发明涉及一种基于Ti4O7阳极的连续流电化学过滤系统及其在降解氨氮废水中的应用，属于水处理技术领域。
背景技术
随着经济的快速发展和生活水平的日益提高，致使含氮化合物的排放量急剧增加，氨氮已经给我国的水体环境带来了巨大的压力，引起社会各界的普遍关注。氨氮浓度过高时，会消耗水中大量的氧气，造成水体的富营养化和水生生物的死亡，同时对人体健康也有不利影响。目前国内外广泛采用的氨氮废水处理技术包括离子交换法、折点加氯法、生物法、和光催化法等。例如，离子交换法可采用具有阳离子交换能力的树脂或其他材料，对氨氮废水进行高效处理，但技术成本偏高。生物法则可通过硝化和反硝化作用将氨氮转化为氮气，但是需要对碳源进行精准调控，以维持恒定的C/N比。因此，发展高效、低耗、环保的氨氮降解新技术，对缓解日益严峻的环境压力有着重要的现实意义。
目前，电化学高级氧化技术因为其环保高效的特点成为人们研究的新热点，有望解决氨氮污染的难题。电化学高级氧化技术可以分为电化学直接氧化和间接氧化，电化学直接氧化过程是靠电子转移来实现，而间接氧化过程是通过活性自由基氧化来实现有机污染物的降解。前人将电化学应用于氨氮废水处理已有诸多有益的尝试。例如，Ji等设计了一种新型太阳光驱动的光电催化氯自由基反应系统，利用WO3阳极对可见光响应特性，在光照条件下产生光穴，将[Cl-]氧化为Cl·，从而对氨氮进行降解(Water Res.,2017,125,512-519)。尽管氨氮去除效率有所提高，但由于传质过程具有扩散限制，限制了上述系统的实际应用。此外，氨氮氧化会产生一定量的硝态氮和亚硝态氮，导致脱氮的不完全。
此外，Liu等的研究表明电化学过滤体系的传质速率比传统序批式体系提升了6倍(J.Phys.Chem.C,2012,116,374-383)。Zhang等的研究表明该阴极对硝态氮的去除速率是Pt阴极的33倍(Environ.Sci.Technol.,2018,52,1413-1420)。
发明内容
本发明所要解决的技术问题是：现有氨氮废水在处理过程中脱氮不完全的问题。
为了解决上述问题，本发明提供了一种连续流电化学过滤系统，包括阳极与阴极，其特征在于，所述阳极采用Ti4O7薄膜，阴极采用Pd/Cu改性的Ni泡沫，阳极、阴极相对一侧的表面各设有一层PTFE基底膜，且阳极的一侧为进水口，阴极的一侧为出水口，出水口处设有Ag/AgCl参比电极；阳极、阴极分别通过一集流体与电源的正极、负极连接。
优选地，所述Ti4O7薄膜的制备方法为：将Ti4O7置于容器中，在水中超声1h使之分散均匀；将得到的分散液抽滤到PTFE基底膜上，制成Ti4O7薄膜。
优选地，所述Pd/Cu改性的Ni泡沫的制备方法为：将Ni泡沫依次浸没在浓度0.1M的硫酸、丙酮、去离子水中各超声10-30min去除表面氧化物；将氯化钯、五水合硫酸铜、盐酸溶液置于容器混合均匀，得到混合液；在三电极系统中，将作为工作电极的Ni泡沫、作为对电极的Pt，以及作为参比电极的饱和Ag/AgCl电极共同浸入混合液中，在应用电位为-1.0Vvs.Ag/AgCl的条件下进行电沉积实验，沉积完成后即得Pd/Cu改性的Ni泡沫。
更优选地，所述氯化钯的浓度为2mM，五水合硫酸铜的浓度为4mM，盐酸溶液的浓度为0.1M，三者的体积比为1：1：1。
优选地，所述集流体采用Ti棒。
本发明还提供了一种上述连续流电化学过滤系统在降解氨氮废水中的应用。
优选地，将硫酸铵溶液导入所述连续流电化学过滤系统；然后，控制阳极的电势范围为1～3V vs.Ag/AgCl，pH值的范围为1～12，[Cl-]初始浓度的范围为0.01～1.0mol/L。
优选地，所述硫酸铵溶液的流速为1～10mL/min。
优选地，所述[Cl-]在阳极被氧化生成氯自由基，即Cl·，Cl·选择性地与NH4+反应生成氮气，阳极的副产物进一步在阴极选择性还原为N2。
更优选地，所述阳极的副产物为NO3 -和NO2 -中的至少一种。
本发明采用了膜分离与电化学技术相结合的改进方法，并以一种连续流操作方式进行。在这种体系中，对流强化传质可显著增强目标污染物分子向膜表面活性位点的传递过程，具有易控制和可放大等优点，有望实现工程应用。
本发明采用真空抽滤技术制得Ti4O7薄膜，采用电沉积技术制得的高选择性的阴极改性Ni泡沫，在辅助电场作用下，将氨氮快速高效地转换为氮气，进而实现氨氮废水的高效处理。与现有技术相比，本发明的有益效果在于：
1、该Ti4O7薄膜的制备原料简单易得、制备周期较短、制备条件温和，原料和制备的成本都较低；
2、该Ti4O7薄膜具有高析氧电位，在用于电化学反应中呈现出极强的耐腐蚀和极强的稳定性；
3、在适当的外部电位的作用下，原位阳极氧化[Cl-]可有效且持续地产生Cl·，这些产生的Cl·可选择性地与NH4 +反应生成N2，阳极副反应产生的NO3 -和NO2 -可进一步在选择性阴极还原为N2，阳极和阴极的高孔隙率和对流增强了氨氮的传质和转化性能。
附图说明
图1为本发明提供的连续流电化学过滤系统的示意图；
图2为氨氮废水在三种模式下进行电氧化过滤实验的降解效果图。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。
实施例1-3提供的连续流电化学过滤系统如图1所示，其包括阳极2与阴极4，所述阳极2采用Ti4O7薄膜，阴极4采用Pd/Cu改性的Ni泡沫，阳极2、阴极4相对一侧的表面各设有一层PTFE基底膜3，且阳极2的一侧为进水口1，阴极4的一侧为出水口7，出水口7处设有Ag/AgCl参比电极6；阳极2、阴极4分别通过一集流体5与电源的正极、负极连接。所述集流体5采用Ti棒。
实施例1
取50mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，Ti4O7薄膜过薄。取150mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约30kΩ，电阻过大。取100mg Ti4O7加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约10kΩ，电阻过大。取100mg Ti4O7和5mg酸化CNT加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上，冷冻干燥后测电阻约100Ω，导电性很好，将制备好的Ti4O7薄膜在电化学过滤器中做阳极。
取氯化钯(2mM)、五水合硫酸铜(4mM)、盐酸(0.1M)各100mL于同一烧杯中超声15min使其混合均匀；在三电极系统中，采用Ni泡沫为工作电极、Pt为对电极，以及饱和Ag/AgCl为参比电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，将制备好的Pd/Cu改性Ni泡沫在电化学过滤器中做阴极。
实施例2
取100mg Ti4O7和5mg酸化CNT加入50mL超纯水，探头超声1h，将分散均匀的Ti4O7抽滤到PTFE支撑膜上。将制备好的Ti4O7薄膜在电化学过滤器中做阳极。
取氯化钯(2mM)、五水合硫酸铜(4mM)、盐酸(0.1M)各100mL于同一烧杯中超声15min使其混合均匀；在三电极系统中，采用Ni泡沫为工作电极、Pt为对电极，以及饱和Ag/AgCl为参比电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，将制备好的Pd/Cu改性Ni泡沫在电化学过滤器中做阴极。
控制阳极电势在1.5V vs.Ag/AgCl，pH为7，Cl-的初始浓度在0.1mol/L，控制流速从1到4mL/min，氨氮去除率从87％上升到大于99％。
实施例3
阳极Ti4O7薄膜和阴极Pd/Cu改性Ni泡沫制备方法与实施例2相同。加入0.175g氯化钠的30mL氨氮废水通过电化学过滤装置后回到原来的烧杯中，然后又重新进入过滤装置进行循环过滤；加入0.175g氯化钠的30mL氨氮废水通过电化学过滤装置后滴入新的烧杯中，做单次过滤实验；加入0.175g氯化钠的30mL氨氮废水进行batch实验。控制阳极电势在2.5Vvs.Ag/AgCl，pH为7，[Cl-]的初始浓度在0.1mol/L。如图2所示，反应1.5h后单次过滤实验的氨氮去除率为11.8％，batch实验的氨氮去除率为63.6％，循环过滤实验的氨氮去除率大于99.9％。
Claims (5)
1.一种用于降解氨氮废水的连续流电化学过滤系统，包括阳极(2)与阴极(4)，其特征在于，所述阳极(2)采用Ti4O7薄膜，阴极(4)采用Pd/Cu改性的Ni泡沫，阳极(2)、阴极(4)相对一侧的表面各设有一层PTFE基底膜(3)，且阳极(2)的一侧为进水口(1)，阴极(4)的一侧为出水口(7)，出水口(7)处设有Ag/AgCl参比电极(6)；阳极(2)、阴极(4)分别通过一集流体(5)与电源的正极、负极连接；所述Pd/Cu改性的Ni泡沫的制备方法为：将Ni泡沫依次浸没在浓度0.1M的硫酸、丙酮、去离子水中各超声10-30min去除表面氧化物；将氯化钯、五水合硫酸铜、盐酸溶液置于容器混合均匀，得到混合液；在三电极系统中，将作为工作电极的Ni泡沫、作为对电极的Pt，以及作为参比电极的饱和Ag/AgCl电极共同浸入混合液中，在应用电位为-1.0V vs.Ag/AgCl的条件下进行电沉积实验，沉积完成后即得Pd/Cu改性的Ni泡沫；所述氯化钯的浓度为2mM，五水合硫酸铜的浓度为4mM，盐酸溶液的浓度为0.1M，三者的体积比为1：1：1；
所述Ti4O7薄膜的制备方法为：将Ti4O7置于容器中，在水中超声1h使之分散均匀；将得到的分散液抽滤到PTFE基底膜(3)上，制成Ti4O7薄膜。
2.如权利要求1所述的连续流电化学过滤系统，其特征在于，所述集流体(5)采用Ti棒。
3.一种权利要求1或2所述的连续流电化学过滤系统在降解氨氮废水中的应用，其特征在于，将硫酸铵溶液导入所述连续流电化学过滤系统；然后，控制阳极的电势范围为1～3Vvs.Ag/AgCl，pH值的范围为1～12，[Cl-]初始浓度的范围为0.01～1.0mol/L；所述[Cl-]在阳极被氧化生成氯自由基，即Cl·，Cl·选择性地与NH4 +反应生成氮气，阳极的副产物进一步在阴极选择性还原为N2。
4.如权利要求3所述的连续流电化学过滤系统在降解氨氮废水中的应用，其特征在于，所述硫酸铵溶液的流速为1～10mL/min。
5.如权利要求3所述的连续流电化学过滤系统在降解氨氮废水中的应用，其特征在于，所述阳极的副产物为NO3 -和NO2 -中的至少一种。
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