陶瓷基PbO<sub>2</sub>电极的制备及其处理Ni-EDTA络合废水

doi:10.19965/j.cnki.iwt.2020-1230

摘要/Abstract

摘要：

采用化学沉积-电沉积法的方法制备了陶瓷/α-PbO₂、陶瓷/α-PbO₂/β-PbO₂、陶瓷/α-PbO₂/β-PbO₂-PTFE电极，采用扫描电子显微镜（SEM）、X-射线衍射（XRD）、线性扫描伏安（LSV）和电极加速寿命等方法对电极进行表征及化学性能测试。分别以这3种电极作为阳极，电化学氧化Ni-EDTA，同时阴极电沉积回收镍。实验结果表明，陶瓷/α-PbO₂/β-PbO₂-PTFE比其他2种电极具有更高的电氧化破络能力，在Ni-EDTA初始质量浓度为100 mg/L、电流密度为30 mA/cm²，pH=3.1下电氧化180 min后，Ni-EDTA去除率可达96.2%，阴极镍元素回收率达17.9%。

关键词: 电氧化, Ni-EDTA, 陶瓷基PbO₂电极, 镍回收

Abstract:

The ceramic/α-PbO₂, ceramic/α-PbO₂/β-PbO₂, and ceramic/α-PbO₂/β-PbO₂-PTFE were prepared by chemical deposition-electrodeposition methods and characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), linear sweep voltammetry(LSV) and accelerated lifetime tests. The simultaneous decomplexation of Ni-EDTA and electrodeposition recovery of nickel metal were attempted in a combined electrooxidation-electrodeposition reactor with these three PbO₂ electrodes and polished titanium cathode. The results showed that the ceramic/α-PbO₂/β-PbO₂-PTFE electrode had a higher oxidation breaking ability than the other two electrodes. The removal efficiencies of Ni-EDTA and the recovery ratios Ni element were determined to be 96.2% and over 17.9% respectively under the conditions of current density 30 mA/cm², pH 3.10, initial Ni-EDTA mass concentration 100 mg/L, and reaction time 180 min.

Key words: electrochemical oxidation, Ni-EDTA, ceramic/PbO₂ anode, nickel recovery

中图分类号:

X703.1

徐小凤,卓琼芳,陈中颖,任秀文,刘静静,邱永福,李衍亮,谢水波. 陶瓷基PbO₂电极的制备及其处理Ni-EDTA络合废水[J]. 工业水处理, 2021, 41(9): 60-68.

Xiaofeng Xu,Qiongfang Zhuo,Zhongying Chen,Xiuwen Ren,Jingjing Liu,Yongfu Qiu,Yanliang Li,Shuibo Xie. Preparation of a ceramic-based lead dioxide electrode and its application in treatment of Ni-EDTA complex wastewater[J]. Industrial Water Treatment, 2021, 41(9): 60-68.

https://www.iwt.cn/CN/Y2021/V41/I9/60

图/表 14

图1 陶瓷/α-PbO₂（a）、陶瓷/α-PbO₂/β-PbO₂（b）、陶瓷/α-PbO₂/β-PbO₂-PTFE（c）的SEM

Fig.1 SEM images of ceramic/α-PbO₂(a), ceramic/α-PbO₂/β-PbO₂(b) and ceramic/α-PbO₂/β-PbO₂-PTFE(c)

图2 3种PbO₂电极的XRD

Fig.2 XRD patterns of three PbO₂ electrodes

图3 PbO₂电极的LSV曲线

Fig.3 Polarization curves of PbO₂ electrodes

图4 陶瓷/α-PbO₂（a）、陶瓷/α-PbO₂/β-PbO₂（b）、陶瓷/α-PbO₂/β-PbO₂-PTFE（c）体系的荧光强度随时间变化及30 min电化学反应后不同电极的荧光强度（d）

Fig.4 Variation curves of fluorescence intensity at different times on ceramic/α-PbO₂, ceramic/α-PbO₂/β-PbO₂, ceramic/α-PbO₂/β-PbO₂-PTFE electrodes and the fluorescence intensity on different electrodes after electrolysis of 30 min

图5 电极加速寿命曲线

Fig.5 Electrode accelerated life curve

图6 陶瓷/α-PbO₂/β-PbO₂（a）、陶瓷/α-PbO₂/β-PbO₂-PTFE（b）电极加速寿命测试后的SEM

Fig.6 SEM spectra of ceramic/α-PbO₂/β-PbO₂ and ceramic/α-PbO₂/β-PbO₂-PTFE electrodes after accelerated life tests

图7 不同电极对Ni-EDTA络合废水处理效果

Fig.7 Effect of the different electrodes on treatment of Ni-EDTA complex wastewater

表1 不同电极去除Ni-EDTA的反应动力学参数

Table 1 Degradation kinetics constant of Ni-EDTA removal in different electrodes

阳极种类	去除率/%	R²	反应速率常数/min^-1
陶瓷/α-PbO₂	85.33	0.964 4	0.011 6
陶瓷/α-PbO₂/β-PbO₂	88.26	0.957 5	0.012 2
陶瓷/α-PbO₂/β-PbO₂-PTFE	94.88	0.961 3	0.016 2

图8 电流密度对Ni-EDTA络合废水处理效果的影响

Fig.8 Effect of current density on treatment of Ni-EDTA complex wastewater

图9 pH对Ni-EDTA络合废水处理效果的影响
（a）不同pH下Ni-EDTA剩余浓度随时间的变化；（b）不同pH下阴极镍元素回收率随时间的变化；（c）不同pH下阴极附近溶液pH随时间的变化；（d）Ni-EDTA在不同pH下的存在形态

Fig.9 Effect of pH on treatment of Ni-EDTA complex wastewater

图10 Ni-EDTA初始质量浓度对Ni-EDTA络合废水处理效果的影响

Fig.10 Effect of initial Ni-EDTA concentration on treatment of Ni-EDTA complex wastewater

图11 TBA对Ni-EDTA络合废水处理效果的影响

Fig.11 Effect of TBA on treatment of Ni-EDTA complex wastewater

图12 陶瓷/α-PbO₂/β-PbO₂-PTFE电极电氧化Ni-EDTA及阴极镍元素沉积机理

Fig.12 Mechanisms of Ni-EDTA removal and Ni²⁺ deposition in the electrochemical system with a ceramic/α-PbO₂/β-PbO₂-PTFE anode

图13 不同时间Ni-EDTA降解的UV-Vis

Fig.13 UV-Vis spectra of Ni-EDTA degradation solution at different electrolysis times

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