铜镉渣酸浸液旋流电积提铜对比分析

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

摘要/Abstract

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

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

中图分类号:

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.

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.

图/表 17

图1 传统电解技术与旋流电积技术原理图

表1 铜镉渣化学成分分析

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

图2 旋流电积提铜工艺流程

表2 铜镉渣浸出液成分

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

图3 旋流电积实验

图4 旋流电积装置

表3 浸出液中部分金属的标准电极电势

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

表3 浸出液中部分金属的标准电极电势

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

图5 三种不同旋流电积工艺实验条件

图6 分段旋流电积过程

表4 不同旋流电积工艺下浸出液中铜离子电沉积率

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/%

表5 不同旋流电积工艺下的相关技术参数

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

图7 不同旋流电积工艺下铜离子浓度随电积时间的变化趋势

图8 不同旋流电积工艺下氢离子浓度随电积时间的变化趋势

表6 一段旋流电积杂质离子变化趋势 (g·L-1)

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

表7 两段旋流电积杂质离子变化趋势 (g·L-1)

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

表8 三段旋流电积杂质离子变化趋势 (g·L-1)

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

图9 不同旋流电积工艺下的阴极铜产品形貌

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