中间层为聚吡咯的复合电极深度处理焦化废水

doi:10.16085/j.issn.1000-6613.2019-1987

摘要/Abstract

摘要：

电催化技术深度处理焦化废水仍受极板导电性和催化活性制约而无法广泛应用。本文在以掺杂锑的二氧化锡的钛网（Ti/SnO₂-Sb）为底层、以掺杂铈的二氧化铅（PbO₂-Ce）为顶层的二维结构之间插入良好导电性的非离子型高聚化合物聚吡咯（PPy），形成具有三维结构的Ti/SnO₂-Sb/PPy/PbO₂-Ce电极能够增加电流效率，提高催化活性。分别通过X射线衍射图谱、高分辨率透射电子显微镜、X射线光电子能谱和热重分析来表征电极的结构、元素的化学状态和热稳定性，通过线性扫描伏安法和循环伏安法测试电极的电化学表面行为。分析表明，铈的掺杂使极板羟基自由基（·OH）产生量有较大增幅；PPy中间层的插入增强了电极热稳定性，使电流效率提升至7.55%。电化学分析表明Ti/SnO₂-Sb/PPy/PbO₂-Ce电极具有较高的活性表面积和析氧电位。为使极板达到最佳应用条件，通过响应面法得到一组预测优化参数：电流密度161.18A/m²，电解质浓度5.90g/L，极板间距1.58cm，初始pH为9.05。在最优条件下，对焦化废水的降解效率达到90.47%，能耗为0.787kW·h/g，并据此对可能得催化氧化原理提供预测。

关键词: 电化学, 焦化废水, 二氧化铅电极, 响应面法, 环境, 催化

Abstract:

The advanced treatment of coking wastewater by electrocatalytic technology is still limited by the insufficient conductivity and catalytic activity of the plates and cannot be widely used. Nonconductive polypyrrole (PPy) with good conductivity was inserted into the two-dimensional structure with antimony-doped tin dioxide (Ti/SnO₂-Sb) as the bottom layer and cerium-doped lead dioxide (PbO₂-Ce) as the top layer, to form a three-dimensional Ti/SnO₂-Sb/PPy/PbO₂-Ce electrode that can increase the current efficiency and improve the catalytic activity. The structure of the electrode, the chemical state of the element, and the thermal stability were characterized by X-ray diffraction patterns, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis, respectively. Electrochemical surface behavior of the electrodes was tested by linear scanning voltammetry and cyclic voltammetry. The analysis showed that the doping of cerium significantly increased the amount of hydroxyl radicals (·OH) on the plate and the insertion of PPy into the intermediate layer improved the electrode’s thermal stability and increased the current efficiency to 7.55%. Electrochemical analysis showed that the Ti/SnO₂-Sb/PPy/PbO₂-Ce electrode had high active surface area and oxygen evolution potential. In order to achieve the best performance for the plates, a set of optimal operation parameters were predicted by using the response surface method as current density 161.18A/m², electrolyte concentration 5.90g/L, plate spacing 1.58cm, and initial pH 9.05. Under the optimal conditions, the degradation efficiency of coking wastewater reached 90.47%, and the energy consumption was 0.787kW·h/g. Based on the results, the possible catalytic oxidation principles was provided.

Key words: electrochemistry, coking wastewater, PbO₂ electrode, response surface method, environment, catalysis

中图分类号:

X703.1

杨丙衡, 安路阳, 张立涛, 宋迪慧, 刘合鑫. 中间层为聚吡咯的复合电极深度处理焦化废水[J]. 化工进展, 2020, 39(10): 4256-4267.

Bingheng YANG, Luyang AN, Litao ZHANG, Dihui SONG, Hexin LIU. Treatment of coking wastewater with composite electrode with PPy as middle layer[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4256-4267.

参考文献

1	孙怡, 于利亮, 黄浩斌, 等. 高级氧化技术处理难降解有机废水的研发趋势及实用化进展[J]. 化工学报, 2017, 68(5): 1743-1756.
1	SUN Yi, YU Liliang, HUANG Haobin, et al. Development trend and practical progress of advanced oxidation technology for refractory organic wastewater treatment[J]. CIESC Journal, 2017, 68(5): 1743-1756.
2	安路阳, 刘睿, 王钟欧, 等. 含酚废水离心萃取脱酚技术研究[J]. 环境工程, 2016, 34(S1): 62-65, 150.
2	AN Luyang, LIU Rui, WANG Zhongou, et al. Study on centrifugal extraction of phenolic wastewater[J]. Environmental Engineering, 2016, 34(S1): 62-65, 150.
3	宋迪慧, 安路阳, 张立涛, 等. 响应曲面法优化电化学耦合体系预处理焦化废水[J]. 化工学报, 2018, 69(9): 4001-4011.
3	SONG Dihui, AN Luyang, ZHANG Litao, et al. Optimization of electrochemical coupling system for pretreatment of coking wastewater by response surface method[J]. CIESC Journal, 2018, 69(9): 4001-4011.
4	DING J, SONG D H, LIU X S, et al. Iron species-impregnated granular activated carbon as modified particle electrodes applied in benzothiazole adsorption and electrocatalytic degradation[J]. Journal of Harbin Institute of Technology, 2017, 24(3): 39-49.
5	WU X H, ZHANG Y, WU G M, et al. Simulation and optimization of a coking wastewater biological treatment process by activated sludge models(ASM)[J]. Journal of Environmental Management, 2016, 165(1): 235-242.
6	丁杰, 宋昭, 宋迪慧, 等. 三维电催化处理苯并噻唑反应器结构优化[J]. 化工进展, 2017, 36(1): 91-99.
6	DING Jie, SONG Zhao, SONG Dihui, et al. Structural optimization of benzothiazole reactor treated with three-dimensional electrocatalysis[J]. Chemical Industry and Engineering Progress, 2017, 36(1): 91-99.
7	HE Y P, LIN H B, GUO Z C, et al. Recent developments and advances in boron-doped diamond electrodes for electrochemical oxidation of organic pollutants[J]. Sep. Purif. Technol., 2019, 212(1/2): 802-821.
8	FAJARDO A S, MARTINS R C, SILVA D R, et al. Electrochemical abatement of amaranth dye solutions using individual or an assembling of flow cells with Ti/Pt and Ti/Pt-SnSb anodes[J]. Sep. Purif. Technol., 2017, 179(9): 194-203.
9	CERCADO-QUEZADA B, DELIA M L, BERGEL A. Electrochemical micro-structuring of graphite felt electrodes for accelerated formation of electroactive biofilms on microbial anodes[J]. Electrochem. Commun., 2011, 13(4): 440-443.
10	XU L, LI M, XU W. Preparation and characterization of Ti/SnO₂-Sb electrode with copper nanorods for AR73 removal[J]. Electrochim Acta, 2015, 166(6): 64-72.
11	LIN L, MENG X Y, LI Q Y, et al. Crittenden, electrochemical oxidation of microcystis aeruginosa using a Ti/RuO₂ anode: contributions of electrochemically generated chlorines and hydrogen peroxide[J]. Environ. Sci. Pollut. R, 2018, 25(8/9): 27924-27934.
12	LIN H, NIU J F, DING S Y, et al. Electrochemical degradation of perfluorooctanoic acid (PFOA) by Ti/SnO₂-Sb, Ti/SnO₂-Sb/PbO₂and Ti/SnO₂-Sb/MnO₂ anodes[J]. Water Res., 2012, 46 (2): 2281-2289.
13	LIU B, WANG S, WANG C Y, et al. Surface morphology and electrochemical properties of RuO₂-doped Ti/IrO₂-ZrO₂ anodes for oxygen evolution reaction[J]. J. Alloy. Compd., 2019, 778 (4): 593-602.
14	ZHANG W L, LIN H B, KONG H S,et al. Preparation and characterization of lead dioxide electrode with three-dimensional porous titanium substrate for electrochemical energy storage[J]. Electrochim Acta, 2014, 139(3): 209-216.
15	MARKOU V, KONTOGIANNI M C, FRONTISTIS Z, et al. Electrochemical treatment of biologically pre-treated dairy wastewater using dimensionally stable anodes[J]. J. Environ. Manage, 2017, 202 (7): 217-224.
16	LI X L, SHAO D, XU H, et al. Fabrication of a stable Ti/TiO(x)Hy/Sb-SnO₂ anode for aniline degradation in different electrolytes[J]. Chemical Engineering Journal, 2016, 285(3)： 1-10.
17	ZHANG W L, KONG H S, LIN H B, et al. Fabrication, characterization and electrocatalytic application of a lead dioxide electrode with porous titanium substrate[J]. J. Alloy. Compd., 2015, 650 (9) 705-711.
18	徐鹏飞. 氧化铈微纳结构的调控与性能研究[D]. 北京：北京科技大学, 2015.
18	XU Pengfei. Study on the regulation and properties of cerium oxide micro-nano structure[D]. Beijing：University of Science & Technology Beijing, 2015.
19	胡诗迁. 聚吡咯导电水凝胶的制备及其生物医学应用研究[D]. 广州：华南理工大学, 2019.
19	HU Shiqian. Preparation and biomedical application of polypyrrole conductive hydrogels[D]. Guangzhou: South China University of Technology, 2019.
20	付思晗. 聚吡咯/部分还原氧化石墨烯复合材料作为锂/钾离子电池正极材料[D]. 广州：华南理工大学, 2019.
20	FU Sihan. Polypyrrole/partially reduced go composites are used as anode materials for lithium/potassium ion batteries[D]. Guangzhou: South China University of Technology, 2019.
21	CAO J L, WU Z C, LI H X, et al. Inactivation of PbO₂ anodes during oxygen evolution in sulfuric acid solution[J]. Acta Physico-Chimica Sinica, 2007, 23(10): 1515-1519.
22	熊传溪, 闻荻江. 高分子原位复合材料的研究进展[J]. 材料开发与应用, 1999, 14(1): 35-38.
22	XIONG Chuanxi, WEN Dijiang. Research progress of polymer in-situ composites[J]. Development and Application of Materials, 1999,14(1):35-38.
23	RAMOS P, ELENA R R, JESUS G, et al. Understanding the photocatalytic properties of the Pt/CeO_x/TiO₂ systems: structural effects on the electronic and optic properties[J]. ChemPhysChem, 2019, 47(3): 239-257.
24	LYU J H, HAN H B, WU Q, et al. Enhancement of the eletrocatalytic oxidation of dyeing wastewater (reactive brilliant biue KN-R) over the Ce-modified Ti-PbO₂ eletrode with surface hydrophobicity[J]. Journal of Solid State Electrochemistry, 2019, 23(3): 847-859.
25	PER-OLOF L, ARNE A, Oxides of copper, ceria promoted copper, manganese and copper manganese on Al2O3 for the combustion of CO, ethyl acetate and ethanol[J]. Applied Catalysis B: Environmental,2000, 24(3/4): 175-192.
26	王勋华, 周琦, 张蓉, 等. Ti/CeO₂-PTFE-PbO₂电极的制备及其电催化氧化性能[J]. 化工学报, 2010, 61(5): 1190-1195.
26	WANG Xunhua, ZHOU Qi, ZHANG Rong, et al. Preparation of Ti/ CEO₂-PTFE-PBO₂ electrode and its electrocatalytic oxidation performance [J]. CIESC Journal, 2010, 61(5): 1190-1195.
27	YIN Z, ZHENG Y M, WANG H, et al. Engineering interface with one-dimensional Co₃O₄ nanostructure in catalytic membrane electrode: toward an advanced electrocatalyst for alcohol oxidation[J]. ACS Nano, 2017, 11(12): 12365-12377.
28	LYU J H, HAN H B, WU Q, et al. Fabrication of Ti/black TiO₂-PbO₂micro/nanostructures with tunable hydrophobic/hydrophilic characteristics and their photoelectrocatalytic performance[J]. Journal of Solid State Electrochemistry, 2019, 23: 847-859.
29	周键, 关文学, 王三反, 等. Ti/IrO₂+MnO₂电极在酸性溶液中的电化学活性表面积[J]. 化工进展, 2019, 38(8): 3782-3787.
29	ZHOU Jian, GUAN Wenxue, WANG Sanfan, et al. Electrochemical active surface area of Ti/IrO₂+MnO₂ electrode in acidic solution [J]. Chemical Industry and Engineering Progress, 2019, 38(8): 3782-3787.
30	GRUPIONI A A F, ARASHIRO E, LASSAIL T A F. Voltammetric characterization of an iridium oxide-based system: the pseudocapacitive nature of the Ir_0.3Mn_0.7O₂ electrode[J]. Electrochimica Acta, 2003, 48(4): 407- 418.
31	XIA Y J, DAI Q Z. Electrochemical degradation of antibiotic levofloxacin by PbO₂ electrode: kinetics, energy demands and reaction pathways[J]. Chemosphere, 2018, 205(11): 215-222
32	ARDIZZONE S, FREGONARA G, TRASATTI S. Inner and outer active surface of RuO₂ electrodes[J]. Electrochimica Acta, 1990, 35(1): 263-267.
33	DING H Y, FENG Y J, LIU J F, Preparation and properties of Ti/SnO2-Sb₂O₅ electrodes by electrodeposition[J]. Journal of the American Chemical Society,2007, 61(27): 4920-4923.
34	FENG Y J, YANG L S, LIU J F, et al. Electrochemical technologies for wastewater treatment and resource reclamation[J]. Environ. Sci.: Water Res. Technol., 2016, 2(6): 800-831.
35	PER-OLOF L, ARNE A. Oxides of copper, ceria promoted copper, manganese and copper manganese on Al₂O₃ for the combustion of CO, ethyl acetate and ethanol[J]. Applied Catalysis B: Environmental, 2000, 24(3/4): 175-192.
36	CAO M H, HU C W, PENG G, et al. Selected-control synthesis of PbO₂ and Pb₃O₄ single-crystalline nanorodsn[J]. Journal of the American Chemical Society, 2003, 125(17): 4982- 4983.
37	WANG C, YIN L, XU Z C, et al. Electrochemical degradation of enrofloxacin by lead dioxide anode: kinetics, mechanism and toxicity evaluation[J]. Chemical Engineering Journal, 2017, 326 (11): 911-920.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	郑谦, 官修帅, 靳山彪, 张长明, 张小超. 铈锆固溶体Ce_0.25Zr_0.75O₂光热协同催化CO₂与甲醇合成DMC[J]. 化工进展, 2023, 42(S1): 319-327.
[6]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[7]	张杰, 白忠波, 冯宝鑫, 彭肖林, 任伟伟, 张菁丽, 刘二勇. PEG及其复合添加剂对电解铜箔后处理的影响[J]. 化工进展, 2023, 42(S1): 374-381.
[8]	王正坤, 黎四芳. 双子表面活性剂癸炔二醇的绿色合成[J]. 化工进展, 2023, 42(S1): 400-410.
[9]	高雨飞, 鲁金凤. 非均相催化臭氧氧化作用机理研究进展[J]. 化工进展, 2023, 42(S1): 430-438.
[10]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[11]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[12]	许友好, 王维, 鲁波娜, 徐惠, 何鸣元. 中国炼油创新技术MIP的开发策略及启示[J]. 化工进展, 2023, 42(9): 4465-4470.
[13]	耿源泽, 周俊虎, 张天佑, 朱晓宇, 杨卫娟. 部分填充床燃烧器中庚烷均相/异相耦合燃烧[J]. 化工进展, 2023, 42(9): 4514-4521.
[14]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[15]	王晋刚, 张剑波, 唐雪娇, 刘金鹏, 鞠美庭. 机动车尾气脱硝催化剂Cu-SSZ-13的改性研究进展[J]. 化工进展, 2023, 42(9): 4636-4648.