高浓度含铜电镀废水膜电解处理与回用

doi:10.16085/j.issn.1000-6613.2021-1006

化工进展 ›› 2021, Vol. 40 ›› Issue (S2): 434-442.DOI: 10.16085/j.issn.1000-6613.2021-1006

高浓度含铜电镀废水膜电解处理与回用

周杰¹^,²(), 宋小三¹^,²(), 王三反¹^,²

^1.兰州交通大学环境与市政工程学院，甘肃兰州 730070
^2.寒旱地区水资源综合利用教育部工程中心，甘肃兰州 730070

收稿日期:2021-05-12 修回日期:2021-06-25 出版日期:2021-11-12 发布日期:2021-11-12
通讯作者: 宋小三
作者简介:周杰（1998—），男，硕士研究生，研究方向为电化学水处理。E-mail：841095337@qq.com。
基金资助:
国家自然科学基金(21466019);甘肃省科技计划(20JR10RA228);甘肃省高等学校科研项目(2020A-040)

Recovery and utilization of copper from electroplating wastewater with high concentration by membrane electrolysis

ZHOU Jie¹^,²(), SONG Xiaosan¹^,²(), WANG Sanfan¹^,²

^1.School of Environment and Municipal Engineering, Lanzhou Jiaotong University, Lanzhou 730070, Gansu, China
^2.Engineering Center of Water Resources Comprehensive Utilization, Ministry of Education, Lanzhou 730070, Gansu, China

Received:2021-05-12 Revised:2021-06-25 Online:2021-11-12 Published:2021-11-12
Contact: SONG Xiaosan

摘要/Abstract

摘要：

随着电镀行业的发展，电镀废水排放造成的污染问题一直困扰着研究者。而针对其中高浓度含铜电镀废水少污染、可回收的目标，开发了单膜双室膜电解法处理并回收铜的新工艺，本实验研究了其运行方式、回收效果与机理并对回收的产物进行表征。在一个电解槽内阴阳两极之间放入一张阴离子交换膜，研究了初始Cu²⁺浓度、电流密度、pH、极板间距、温度和添加剂等运行参数对铜回收率和能耗的影响。在Cu²⁺初始浓度50g/L，阴极板电流密度400A/m²，温度40℃，极板间距30mm，阴极室pH=6.5，添加1g/L硝酸铵的最优工况下，测得铜回收率可以达到96.1%，电流效率超过70%，并且反应能耗为5737kWh/t。同时通过表征分析在最佳工艺条件下电解回收的铜，发现其颗粒较小、大小均匀、棱角分明，且其纯度高，具有较高的经济价值。

关键词: 电镀废水, 膜电解, 铜回收, 电流效率

Abstract:

With the development of the electroplating industry, the pollution caused by electroplating wastewater discharge has been bothering us. Aiming to low pollution and recovery of high concentration copper-containing electroplating wastewater, a new process of single-membrane double-chamber membrane electrolysis was developed. In this experiment, the operation mode, recovery effect, and mechanism were studied, and the recovered products were characterized. An anion exchange membrane was placed between anode and cathode in an electrolytic cell. The effects of operating parameters such as initial Cu²⁺ concentration, current density, pH, plate spacing, temperature, and additives on copper's recovery rate and energy consumption were studied. Under the optimal conditions of Cu²⁺ initial concentration of 50g/L, cathode plate current density of 400A/m², the temperature of 30℃, plate spacing of 30mm, cathode chamber pH=6, adding 2g/L ammonium nitrate, the measured copper recovery can reach more than 95%, the current efficiency of more than 70%, and reaction energy consumption of 5300—5400kWh/t. At the same time, it is found that the copper recovered by electrolysis under the best technical conditions has small particles, uniform size, sharp angle, high purity and high economic value.

Key words: electroplating wastewater, membrane electrolysis, copper recovery, current efficiency

中图分类号:

TF792

周杰, 宋小三, 王三反. 高浓度含铜电镀废水膜电解处理与回用[J]. 化工进展, 2021, 40(S2): 434-442.

ZHOU Jie, SONG Xiaosan, WANG Sanfan. Recovery and utilization of copper from electroplating wastewater with high concentration by membrane electrolysis[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 434-442.

图/表 18

表1 废水水质情况

项目	数值
Cu²⁺/mg·L^-1	194
Ni²⁺/mg·L^-1	5.4
Zn²⁺/mg·L^-1	4.4
溶解性总固体/mg·L^-1	56800
pH	2.4
电导率/μS·cm^-1	4.16
化学需氧量/mg·L^-1	1540

图1 实验装置示意图1—直流电源；2—阴极板；3—阴离子交换膜；4—阳极板；5—阴极室；6—阳极室；7—单膜双室电解槽

图2 “单膜双室”电解工艺原理示意图

图3 Cu2+初始浓度对铜回收率和电流效率的影响

图4 Cu2+初始浓度对能耗和槽电压的影响

图5 电流密度对铜回收率和电流效率的影响

图6 电流密度对能耗和槽电压的影响

图7 极板间距对铜回收率和电流效率的影响

图8 极板间距对能耗和槽电压的影响

图9 温度对铜回收率和电流效率的影响

图10 温度对能耗和槽电压的影响

图11 阴极室pH对铜回收率和电流效率的影响

图12 阴极室pH对能耗和槽电压的影响

图13 硝酸铵投加量对铜回收率的影响

表2 硝酸铵对反应能耗及槽电压的影响

硝酸铵浓度/g·L^-1	初始电压/V	末端电压/V	反应总能耗/kWh·t^-1
0	5.19	3.42	5583
1.0	5.26	3.66	5737

图14 电解铜的SEM图

图15 电解铜镀层XRD衍射图谱

图16 Cu-Cu2O镀层XRD衍射图谱

参考文献 22

1	VAŠKELIS A, NORKUS E, JAČIAUSKIENĖ J. Kinetics of electroless copper deposition using cobalt(‍Ⅱ)-ethylenediamine complex compounds as reducing agents[J]. Journal of Applied Electrochemistry, 2002, 32(3): 297-303.
2	崔国峰, 李宁, 黎德育. 化学镀铜在微电子领域中的应用及展望[J]. 电镀与环保, 2003, 23(5): 5-7.
	CUI Guofeng, LI Ning, LI Deyu. Applications and prospects of electroless Cu plating in microelectronic field[J]. Electroplating & Pollution Control, 2003, 23(5): 5-7.
3	XU H, LI Bo, WEI Yonggang, et al. Extracting of copper from simulated leaching solution of copper-cadmium residues by cyclone electrowinning technology[J]. Hydrometallurgy, 2020, 194: 105298.
4	邹勇斌, 龚维辉, 李浩, 等. 电镀废水处理技术的研究[J]. 广东化工, 2014, 41(11): 200-202.
	ZOU Yongbin, GONG Weihui, LI Hao, et al. Research on electroplating wastewater treatment technology[J]. Guangdong Chemical Industry, 2014, 41(11): 200-201.
5	HU Xuewei, HU Yuanwei, CHEN Kai, et al. Treatment of simulation of copper-containing pit wastewater with sulfate-reducing bacteria (SRB) in biofilm reactors[J]. Environmental Earth Sciences, 2016, 75(19): 1-10.
6	DONG Yue, LIU Junfeng, SUI Mingrui, et al. A combined microbial desalination cell and electrodialysis system for copper-containing wastewater treatment and high-salinity-water desalination[J]. Journal of Hazardous Materials, 2017, 321: 307-315.
7	LIU Xuheng, HE Yang, ZHAO Zhongwei, et al. Study on removal of copper from nickel‑copper mixed solution by membrane electrolysis[J]. Hydrometallurgy, 2018, 180: 153-157.
8	TRAN T K, LEU H J, CHIU K F, et al. Electrochemical treatment of heavy metal-containing wastewater with the removal of COD and heavy metal ions[J]. Journal of the Chinese Chemical Society, 2017, 64(5): 493-502.
9	曾淼, 冯凯莉, 叶晨皓, 等. 电解法处理电镀含铜废水的实验研究[J]. 电镀与精饰, 2016, 38(11): 43-46.
	ZENG Miao, FENG Kaili, YE Chenhao, et al. Treatment of copper-containing wastewater by electrolysis method[J]. Plating & Finishing, 2016, 38(11): 43-46.
10	DAEHN K, ALLANORE A. Electrolytic production of copper from chalcopyrite[J]. Current Opinion in Electrochemistry, 2020, 22: 110-119.
11	李韬, 王三反, 周键. 离子膜电解法电沉积回收硫酸镍体系中金属镍的实验研究[J]. 材料导报, 2016, 30(S2): 432-435, 439.
	LI Tao, WANG Sanfan, ZHOU Jian. Experimental study of ion-exchange membrane electrolysis nickel sulfate electrowinning of nickel metal system[J]. Materials Review, 2016, 30(S2): 432-435, 439.
12	范帅. 电镀废水中铜的电沉积回收及其工艺设计[D]. 衡阳: 南华大学, 2015.
	FAN Shuai. Research and design of electrodeposition recovery of copper from electroplating wastewater[D]. Hengyang: University of South China, 2015.
13	SNIEKERS J, GEYSENS P, HOOGERSTRAETE T V, et al. Cobalt(ii) liquid metal salts for high current density electrodeposition of cobalt[J]. Dalton Transactions, 2018, 47(14): 4975-4986.
14	郑凡, 黄炳行, 闭伟宁, 等. 阴离子交换膜无硒电解金属锰工艺及工业可行性探索[J]. 中国锰业, 2016, 34(5): 75-78.
	ZHENG Fan, HUANG Bingxing, BI Weining, et al. A study on non-selenium electrolytic process with anion exchange membrane electrolyzer[J]. China's Manganese Industry, 2016, 34(5): 75-78.
15	SAHU S K, CHMIELOWIEC B, ALLANORE A. Electrolytic extraction of copper, molybdenum and rhenium from molten sulfide electrolyte[J]. Electrochimica Acta, 2017, 243: 382-389.
16	苏亚东. 电沉积对铜晶粒生长的调控及其在电子互连中的应用[D]. 成都: 电子科技大学, 2020.
	SU Yadong. Electrochemical tuning of copper grain growth and its application for electronic interconnection[D]. Chengdu: University of Electronic Science and Technology of China, 2020.
17	KULEYIN A. Recovery of copper ions from industrial wastewater by electrodeposition[J]. International Journal of Electrochemical Science, 2020, 15: 1474-1485.
18	WANG Jiqin, HUANG Zhouman, YANG Deze, et al. A semi-scaled experiment for metals separating and recovering from waste printed circuit boards by slurry electrolysis[J]. Process Safety and Environmental Protection, 2021, 147: 37-44.
19	张昊. 离子膜金属电积生产回收技术及中试研究[D]. 兰州: 兰州交通大学, 2015.
	ZHANG Hao. Research on production recovery process and pilot test from the amberplex metal electrodeposition technology[D]. Lanzhou: Lanzhou Jiatong University, 2015.
20	NEPEL T C D M, COSTA J M, VIEIRA M G A, et al. Copper removal kinetic from electroplating industry wastewater using pulsed electrodeposition technique[J]. Environmental Technology, 2020: 1-9.
21	刘香琳. 电沉积法处理模拟含铜废水及其电结晶行为研究[D]. 鞍山: 辽宁科技大学, 2020.
	LIU Xianglin. Study on treatment of simulated copper-containing wastewater by electrodeposition and its crystallization behavior[D]. Anshan: University of Science and Technology Liaoning, 2020.
22	HABA T, IKEDA K, UOSAKI K. Electrochemical and in situ SERS study of the role of an inhibiting additive in selective electrodeposition of copper in sulfuric acid[J]. Electrochemistry Communications, 2019, 98: 19-22.

[1]	何泽兴, 史成香, 陈志超, 潘伦, 黄振峰, 张香文, 邹吉军. 质子交换膜电解水制氢技术的发展现状及展望[J]. 化工进展, 2021, 40(9): 4762-4773.
[2]	顾利坤, 徐洪傲, 李博, 魏永刚. 铜镉渣酸浸液旋流电积提铜对比分析[J]. 化工进展, 2021, 40(5): 2900-2908.
[3]	刘欢, 何德文, 朱佳. 陶瓷膜短流程工艺处理重金属废水[J]. 化工进展, 2015, 34(09): 3467-3471,3494.
[4]	郭训文，汪晓军，林旭龙. 曝气生物滤池处理含氰废水的启动性能及污染物去除特性[J]. 化工进展, 2013, 32(01): 222-226.
[5]	狄超群，张鹏远，徐联宾，陈建峰. 磁力搅拌下离子液体AlCl3/Et3NHCl恒电流法电沉积铝[J]. 化工进展, 2011, 30(10): 2151-.

高浓度含铜电镀废水膜电解处理与回用

Recovery and utilization of copper from electroplating wastewater with high concentration by membrane electrolysis

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 18

参考文献 22

相关文章 5

编辑推荐

Metrics

本文评价