Comparative analysis of copper extraction from leachate of Cu-Cd residues by cyclone electrowinning

doi:10.16085/j.issn.1000-6613.2020-1177

Abstract

Abstract:

A process for copper extraction using cyclone electrowinning technology was carried out, based on the composition characteristics of the oxidation acid leaching solution of copper-cadmium residues. The effects of different cyclone electrowinning processes on the relevant technical parameters and impurity ions migration behavior in the electrowinning process were investigated. The advantages and disadvantages of different electrowinning processes were analyzed. The results show that the concentration of copper ion in the solution can be reduced from 44.14g/L to 1.42g/L by one-stage cyclone electrowinning. While, the end-point copper ion concentration in the solution can be reduced from 1.42g/L to less than 0.5g/L by segmented cyclone electrowinning. Additionally, the electrodeposition efficiency of copper ions on the cathode can be increased from 96.78% to 99.20% with the current efficiency increased from 90.52% to 98.49%. When the concentration of copper ion was reduced to 10g/L or less, the co-deposition of impurity ions and copper in the cathode is obvious. The gloss and morphology quality of the cathode copper products obtained by the segmented cyclone electrowinning process are better. Compared with one-stage cyclone electrowinning, the segmented cyclone electrowinning process has the advantages of high current efficiency, low energy consumption, and better product quality, etc.

Key words: leachate of copper-cadmium residues, cyclone electrowinning, segmented electrowinning, current efficiency, copper

摘要：

针对湿法炼锌副产物铜镉渣氧化酸浸液成分特点，采用旋流电积工艺回收其中的金属铜。研究了不同旋流电积工艺对电积过程中相关技术参数及杂质离子迁移规律的影响，并对不同电积工艺的优缺点进行了对比分析。结果表明：一段旋流电积可使溶液中铜离子浓度从44.14g/L降低到1.42g/L，而分段旋流电积可使溶液中终点铜离子浓度从1.42g/L继续降低至0.5g/L以下，溶液中铜离子在阴极上的电沉积率可从96.78%提高到99.20%，阴极电流效率可从90.52%提高到98.49%。当溶液中铜离子浓度降低到10g/L左右及以下时，杂质离子在阴极与铜发生共沉积现象逐渐明显，分段旋流电积得到的阴极铜产品光泽度及形貌质量较一段电积更好。与一段旋流电积工艺相比，分段旋流电积工艺具有电流效率高、能耗低、产品质量好等优点。

关键词: 铜镉渣酸浸液, 旋流电积, 分段电积, 电流效率, 金属铜

CLC Number:

GU Likun, XU Hong’ao, LI Bo, WEI Yonggang. Comparative analysis of copper extraction from leachate of Cu-Cd residues by cyclone electrowinning[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2900-2908.

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.

Figures/Tables 17

元素	质量分数/%
Cu	34.81
Zn	4.01
Cd	2.45
Pb	19.91
Fe	0.30
Mn	0.12

元素	质量浓度/g·L^-1
Cu	42.27
Zn	2.98
Cd	3.35
Fe	0.11
Ni	0.37
Co	0.068
Mn	0.14

金属	$φ$ ⁰/V
Cu²⁺/Cu	0.34
Zn²⁺/Zn	-0.76
Cd²⁺/Cd	-0.40
Fe²⁺/Fe	-0.44
Fe³⁺/Fe²⁺	0.77
Ni²⁺/Ni	-0.23
Co²⁺/Co	-0.28
Mn²⁺/Mn	-1.18

金属	$φ$ ⁰/V
Cu²⁺/Cu	0.34
Zn²⁺/Zn	-0.76
Cd²⁺/Cd	-0.40
Fe²⁺/Fe	-0.44
Fe³⁺/Fe²⁺	0.77
Ni²⁺/Ni	-0.23
Co²⁺/Co	-0.28
Mn²⁺/Mn	-1.18

工艺

初始Cu²⁺浓度/g·L^-1

终点Cu²⁺浓度/g·L^-1

初始H⁺

浓度/g·L^-1

终点H⁺

浓度/g·L^-1

Cu²⁺电

沉积率/%

工艺	槽电压/V	电流效率/%	能耗/kW·h·kg^-1
一段旋流电积	3.3	90.52	3.07
两段旋流电积	2.6、2.9	98.01、89.72	2.24、2.73
三段旋流电积	2.6、3.2、3.1	98.49、98.46、52.90	2.23、2.74、4.94

项目	Cu	Zn	Cd	Fe
电积前液	44.51	2.58	3.25.	0.14
电积后液	1.42	2.54	3.17	0.11

项目	Cu	Zn	Cd	Fe
电积前液	42.27	2.98	3.35	0.11
Ⅰ段电积后液	12.14	2.94	3.35	0.11
Ⅱ段电积后液	0.34	2.60	3.22	0.097

项目	Cu	Zn	Cd	Fe
电积前液	43.61	2.73	3.23	0.12
Ⅰ段电积后液	19.42	2.73	3.22	0.12
Ⅱ段电积后液	4.93	2.69	3.22	0.12
Ⅲ段电积后液	0.40	2.65	3.21	0.11

References 27

1	冶玉花, 张昱琛. 铜镉渣生产镉绵的工业实践[J]. 中国有色冶金, 2014, 43(4): 32-34.
	YE Yuhua, ZHANG Yuchen. Industrial practice of cadmium sponge production with copper and cadmium slag[J]. China Nonferrous Metallurgy, 2014, 43(4): 32-34.
2	易宗娓, 何作顺. 镉污染与痛痛病[J]. 职业与健康, 2014, 30(17): 2511-2513.
	YI Zongwei, HE Zuoshun. Cadmium pollution and itai-itai disease[J]. Occup and Health, 2014, 30(17): 2511-2513.
3	卢国俭, 朱英杰, 欧阳春. 铜镉渣综合利用研究[J]. 无机盐工业, 2014, 46(7): 63-66.
	LU Guojian, ZHU Yingjie, OUYANG Chun. Comprehensive utilization of copper/cadmium residue[J]. Inorganic Chemicals Industry, 2014, 46(7): 63-66.
4	蒋国林. 某厂利用铜镉渣提取精镉的工艺设计[J]. 湖南有色金属, 2015, 31(2): 39-42, 53.
	JIANG Guolin. Process design for cadmium from copper-cadmium slag[J]. Hunan Nonferrous Metals, 2015, 31(2): 39-42, 53.
5	MOATS M S. Will lead-based anodes ever be replaced in aqueous electrowinning?[J]. JOM, 2008, 60(10): 46-49.
6	TREASURE P A. Electrolytic zinc recovery in the EMEW cell[M]Recycling of Metals and Engineercd Materials. Hoboken, NJ, USA:John Wiley & Sons, Inc. 2013: 185-191.
7	郭学益, 石文堂, 李栋, 等. 采用旋流电积技术从电镀污泥中回收铜和镍[J]. 中国有色金属学报, 2010, 20(12): 2425-2430.
	GUO Xueyi, SHI Wentang, LI Dong, et al. Recovery of copper and nickel from electroplating sludge by cyclone electrowinning[J].The Chinese Journal of Nonferrous Metals, 2010, 20(12): 2425-2430.
8	郭学益, 姚标, 李晓静, 等. 水钴矿中选择性提取铜和钴的新工艺[J]. 中国有色金属学报, 2012, 22(6): 1778-1784.
	GUO Xueyi, YAO Biao, LI Xiaojing, et al. Novel process of selective extraction of copper and cobalt from heterogenite[J]. The Chinese Journal of Nonferrous Metals, 2012, 22(6): 1778-1784.
9	纪仲光, 王巍, 徐政, 等. 旋流电解提取铜冶炼污泥模拟浸出液中有价金属研究[J]. 稀有金属, 2015, 39(9): 847-853.
	JI Zhongguang，WANG Wei，XU Zheng，et al. Extracting of valuable metal in simulated leaching solution of sludge from copper smelting process with cyclone electrowinning[J]. Chinese Journal of Rare Metals, 2015, 39(9): 847-853.
10	WANG S J. Novel electrowinning technologies: the treatment and recovery of metals from liquid effluents[J]. The Journal of The Minerals, Metals & Materials Society, 2008, 60(10): 41-45.
11	王功强, 何桂荣. 旋流电积技术在铜陵有色稀贵分公司阳极泥浸出分铜液电积中的应用[J]. 有色金属工程, 2015, 5(6): 32-35, 73.
	WANG Gongqiang, HE Guirong. Application of cyclone electrolysis technology in copper electrowinning from anode mud leaching solution of Tongling nonferrous rare branch[J]. Nonferrous Metals Engineering, 2015, 5(6): 32-35, 73.
12	赵丽萍. 比较传统电积脱铜和旋流电解脱铜工艺的优劣[J]. 中国化工贸易, 2015(2): 170.
	ZHAO Liping. Compare the advantages and disadvantages of traditional electrowinning and cyclone electroeinning processes[J]. China Chemical Trade, 2015(2): 170.
13	成应向, 刘喜珍, 漆燕, 等. 有色冶炼铜镉渣中镉的提取工艺研究[J]. 环境工程, 2012, 30(S2): 331-334.
	CHENG Yingxiang, LIU Xizhen, QI Yan, et al. Process research of extracting cadmium from non-ferrous copper and cadmium slag[J]. Environmental Engineering, 2012, 30(S2): 331-334.
14	戴江洪, 李龙, 李若贵, 等. 从净液渣中回收铜的生产实践及其改进[J]. 中国有色冶金, 2011, 40(6): 49-52.
	DAI Jianghong, LI Long, LI Ruogui, et al. Practice and modification of Cu&Cd recovery from purification slag[J]. China Nonferrous Metallurgy, 2011, 40(6): 49-52.
15	森维, 孙红燕, 彭林, 等. 从铜镉渣中回收锌、镉、铜试验研究[J]. 湿法冶金, 2015, 34(1): 29-31.
	Wei SEN, SUN Hongyan, PENG Lin, et al. Recovery of zinc, cadmium and copper from copper-cadmium residue[J]. Hydrometallurgy of China, 2015, 34(1): 29-31.
16	汤顺贤, 陈科彤, 万宁, 等. 从铜镉渣中提取海绵镉的试验研究[J]. 矿冶, 2014, 23(5): 65-68.
	TANG Shunxian, CHEN Ketong, WAN Ning, et al. Study on extraction of sponge cadmium from copper cadmium slag[J]. Mining and Metallurgy, 2014, 23(5): 65-68.
17	SILVA J E, SOARES D, PAIVA A P, et al. Leaching behaviour of a galvanic sludge in sulphuric acid and ammoniacal media[J]. Journal of Hazardous Materials, 2005, 121(1/2/3): 195-202.
18	LI M, ZHANG Y, WANG X H, et al. Extraction of copper, zinc and cadmium from copper-cadmium-bearing slag by oxidative acid leaching process[J]. Rare Metals, 2016.DOI: 10.1007/s12598-016-0759-7.
19	刘海洋, 颜文斌, 石爱华, 等.从铜镉渣中析出铜锌镉的氧化氨浸工艺[J]. 吉首大学学报(自然科学版), 2010, 31(2): 97-100.
	LIU Haiyang, YAN Wenbin, SHI Aihua, et al. Research on leaching process of copper, zinc and cadmium from copper-cadmium slag[J]. Journal of Jishou University (Natural Science Edition), 2010, 31(2): 97-100.
20	史利芳. 铜镉渣中Cu、Zn、Cd、Co分离行为研究[D]. 沈阳: 东北大学, 2012.
	SHI Lifang. Research on the separation behavior of Cu、Zn、Cd、Co in Cu-Cd residues[D]. Shenyang: Northeastern University, 2012.
21	王书民, 张国春. 商洛炼锌厂废渣回收与处理(ⅴ)——铜渣中铜、锌、镉的萃取分离[J]. 商洛师范专科学校学报, 2004, 18(4): 29-31, 34.
	WANG Shumin, ZHANG Guochun. Waste recycling and treatment in Shangluo Smeltery(V)—Separating copper、zinc、cadmium、from copper-waste[J]. Journal of Shangluo Teachers College, 2004, 18(4): 29-31, 34.
22	吕志林, 李仕雄, 周开敏, 等. 铜镉渣制备高品位镉饼的探索[J]. 云南冶金, 2015, 44(6): 31-36.
	Zhilin LYU，LI Shixiong，ZHOU Kaimin，et al. The exploration on high grade cadmium cake preparation by copper and cadmium sediment[J]. Yunnan Metallurgy, 2015, 44(6): 31-36.
23	杨建广, 雷杰, 彭思尧, 等. 从铜镉渣浸出液中电加强置换提取镉[J]. 中国有色金属学报, 2015, 25(8): 2268-2275.
	YANG Jianguang, LEI Jie, PENG Siyao, et al. Extraction of cadmium from leaching solution of Cu-Cd slag through electrically enhanced replacement process[J]. The Chinese Journal of Nonferrous Metals, 2015, 25(8): 2268-2275.
24	孙明生. 利用湿法净化铜渣制取硫酸铜的生产实践[J]. 中国有色冶金, 2009, 38(6): 20-22.
	SUN Mingsheng. Production practice of using hydro-purification copper slag to prepare copper sulfate[J]. China Nonferrous Metallurgy, 2009, 38(6): 20-22
25	袁城. 旋流电积技术从铜镉渣中综合回收金属的试验研究[D]. 赣州: 江西理工大学, 2013.
	YUAN Cheng. Study on comprehensive recovery of metals from copper and cadmium slag by cyclone electrowinning Technology[D]. Ganzhou: Jiangxi University of Science and Technology, 2013.
26	翟秀静. 重金属冶金学[M]. 北京: 冶金工业出版社, 2011: 78-80.
	ZHAI Xiujing. Metallurgy of heavy metals[M]. Beijing: Metallurgical Industry Press, 2011: 78-80.
27	XU H A, LI B, WEI Y G, et al. Extracting of copper from simulated leaching solution of copper-cadmium residues by cyclone electrowinning technology[J]. Hydrometallurgy, 2020, 194: 105298-105306.

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