Research progress and prospect on electrowinning recovery of lead from spent lead paste

doi:10.16085/j.issn.1000-6613.2024-0123

Abstract

Abstract:

Spent lead-acid battery paste is an important source of secondly lead. Traditional pyrometallurgical process produces lead dust, sulfur dioxide, and smelting lead slag, which brings environmental risk. Therefore, hydrometallurgical process for lead recovery has become a hot research field. Electrowinning process for lead recovery from spent lead paste was reviewed in this paper, including acid leaching-electrodeposition, alkali leaching-electrodeposition, other solvent leaching -electrodeposition, solid-phase electrolysis. The principles, processes, and technical parameters of these processes were discussed in detail. In addition, the key technical parameters of the electrodeposition processes of the current research, such as pretreatment method for spent lead paste, electrolyte, anode by-product, current efficiency, energy consumption, product purity, and morphology regulation etc., were summarized. At the same time, prospects of the electrodeposition technology were provided. The green and environmentally friendly leaching solution or electrolyte, short process flow, low energy consumption, and electrolyte recycling for lead recovery by electrodeposition processes should be focused in the future research.

Key words: spent lead paste, electrowinning, recovery of lead, electrolyte, green and environmentally friendly

摘要：

废铅酸蓄电池铅膏是再生铅的重要来源，传统火法冶炼工艺产生铅尘、二氧化硫及冶炼铅渣，存在一定的环境风险，因此湿法工艺成为了研究的热点。本文聚焦废铅膏湿法回收铅工艺中的电沉积工艺，对酸浸出-电沉积、碱浸出-电沉积、其他溶剂浸出-电沉积、固相电解等工艺进行了综述，对各工艺的原理、过程、技术参数进行了详细分析。此外，本文对当前研究的电沉积回收铅工艺的关键技术点，如废铅膏预处理方式、浸出/电解液体系、阳极副产物、电流效率及电解能耗、产物纯度及形貌调控等进行了总结。同时，本文对电沉积工艺的前景进行了展望，认为浸出/电解液体系绿色环保、工艺流程短、电解能耗低、电解液可以循环利用，是废铅膏电沉积回收铅工艺未来关注和研究的重点。

关键词: 废铅膏, 电沉积, 回收铅, 电解液, 绿色环保

CLC Number:

X705

LI Mingyang, LIANG Jiangbei, LIANG Sha, XIE Weimin, YANG Jiakuan. Research progress and prospect on electrowinning recovery of lead from spent lead paste[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 1042-1052.

李名扬, 梁江北, 梁莎, 谢卫民, 杨家宽. 废铅膏电沉积回收铅技术研究进展与展望[J]. 化工进展, 2025, 44(2): 1042-1052.

Figures/Tables 6

References 54

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方法	典型工艺	浸出溶液/电解液	阳极	阴极	添加剂	铅纯度/%	铅回收率 /%	电解能耗 /kWh·(t Pb)^-1	电流效率/%	参考文献
酸浸出- 电沉积工艺	RSR工艺	H₂SiF₆、HBF₄	石墨基非导电惰性网状材料，表面沉积PbO₂	铅	500mg/L 砷离子	>99.99			96	[23]
	USBM工艺	H₂SiF₆	二氧化铅包覆的钛材料	铅	磷酸盐、动物骨胶、木质素磺酸盐	99.995~ 99.999	92	800	95~97	[24]
	CX-EW工艺（Engitec工艺）	HBF₄	特殊设计的复合阳极材料		骨胶			800		[27-28]
	Placid工艺	HCl-NaCl				99.995	99.5	1300		[29]
		HClO₄	石墨板	铜板	1.0g/L骨胶+1.0g/L木质素磺酸钠	99.9991	98.5	492	>97	[31]
		甲磺酸（MSA）	石墨板	钛板	磷酸	99.99	95.28	598.91	99.31	[35]
碱浸出- 电沉积工艺	AAS工艺	NH₃⋅H₂O- (NH₄)₂SO₄	低碳钢	铅	阳离子聚丙烯酰胺				>95	[38]
		NaOH-KNaC₄H₄O₆			明胶	99.99	98.0	400~500	≥98	[39]
		NaOH	多孔镍泡沫	铜箔		99.9992	99.9	317	99.85	[41]
		NaOH-木糖醇溶液	316不锈钢	316 不锈钢				381.71	99.68	[44]
其他溶剂浸出-电沉积工艺		氯化胆碱-尿素低共熔溶剂	低碳钢片	石墨片				754	85.77	[46]
其他溶剂浸出-电沉积工艺		氯化胆碱-乙二醇低共熔溶剂	低碳钢片	石墨片				673.28	96.06	[47]
固相电解工艺		(NH₄)₂SO₄- NH₃·H₂O	不锈钢	不锈钢		99.89	96.15	493.89	91.68	[48]
		H₂SO₄	不锈钢	铅板		99.7		1800		[49]
		酒石酸钠	钛镀钌铱板材	316L不锈钢板		98.74		1068	91.60	[50]
		(NH₄)₂SO₄	钛基锡锑锰钌涂层阳极材料	铅板栅		95.80	99.46	597	87.63	[51]
		NH₃-NH₄Cl	铱钌涂覆的钛网	不锈钢		98.3		689.4	86.3	[53]
		Na₂SO₄	SnO₂-Sb₂O₅-MnO₂-RuO₂-钛涂层电极	方形铅板		97.29	97.3	818.1	98.5	[54]

方法	典型工艺	浸出溶液/电解液	阳极	阴极	添加剂	铅纯度/%	铅回收率 /%	电解能耗 /kWh·(t Pb)^-1	电流效率/%	参考文献
酸浸出- 电沉积工艺	RSR工艺	H₂SiF₆、HBF₄	石墨基非导电惰性网状材料，表面沉积PbO₂	铅	500mg/L 砷离子	>99.99			96	[23]
	USBM工艺	H₂SiF₆	二氧化铅包覆的钛材料	铅	磷酸盐、动物骨胶、木质素磺酸盐	99.995~ 99.999	92	800	95~97	[24]
	CX-EW工艺（Engitec工艺）	HBF₄	特殊设计的复合阳极材料		骨胶			800		[27-28]
	Placid工艺	HCl-NaCl				99.995	99.5	1300		[29]
		HClO₄	石墨板	铜板	1.0g/L骨胶+1.0g/L木质素磺酸钠	99.9991	98.5	492	>97	[31]
		甲磺酸（MSA）	石墨板	钛板	磷酸	99.99	95.28	598.91	99.31	[35]
碱浸出- 电沉积工艺	AAS工艺	NH₃⋅H₂O- (NH₄)₂SO₄	低碳钢	铅	阳离子聚丙烯酰胺				>95	[38]
		NaOH-KNaC₄H₄O₆			明胶	99.99	98.0	400~500	≥98	[39]
		NaOH	多孔镍泡沫	铜箔		99.9992	99.9	317	99.85	[41]
		NaOH-木糖醇溶液	316不锈钢	316 不锈钢				381.71	99.68	[44]
其他溶剂浸出-电沉积工艺		氯化胆碱-尿素低共熔溶剂	低碳钢片	石墨片				754	85.77	[46]
其他溶剂浸出-电沉积工艺		氯化胆碱-乙二醇低共熔溶剂	低碳钢片	石墨片				673.28	96.06	[47]
固相电解工艺		(NH₄)₂SO₄- NH₃·H₂O	不锈钢	不锈钢		99.89	96.15	493.89	91.68	[48]
		H₂SO₄	不锈钢	铅板		99.7		1800		[49]
		酒石酸钠	钛镀钌铱板材	316L不锈钢板		98.74		1068	91.60	[50]
		(NH₄)₂SO₄	钛基锡锑锰钌涂层阳极材料	铅板栅		95.80	99.46	597	87.63	[51]
		NH₃-NH₄Cl	铱钌涂覆的钛网	不锈钢		98.3		689.4	86.3	[53]
		Na₂SO₄	SnO₂-Sb₂O₅-MnO₂-RuO₂-钛涂层电极	方形铅板		97.29	97.3	818.1	98.5	[54]

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