Treatment of copper-arsenic polymetallic acidic wastewater by sulfide precipitation: A review

doi:10.16085/j.issn.1000-6613.2024-1061

Abstract

Abstract:

In the smelting of non-ferrous metals and the recycling of secondary resources, a significant amount of copper-arsenic polymetallic acidic wastewater is produced. The inefficient separation of valuable metals from arsenic is the key factor restricting its resource utilization. The sulfide precipitation method has been widely studied due to its excellent selectivity. However, the sulfide separation behavior among different metal ions still lacks systematic research. This paper provided a comprehensive review of the selective sulfide precipitation of metal ions, focusing on aspects such as wastewater sources, operational factors, and types of sulfur sources. Firstly, the sources of copper-arsenic polymetallic acidic wastewater were introduced, and the methods of wastewater generation under different processes were elucidated. The current application status of the sulfide precipitation method in the separation of copper-arsenic polymetallic systems was analyzed, with an emphasis on the principles of sulfide precipitation and the main factors affecting sulfide separation efficiency, revealing the intrinsic rules of selective sulfide separation. Finally, the development and application of various sulfide agents were reviewed and discussed, with a particular focus on the application and mechanism research status of inorganic insoluble iron sulfides in the copper-arsenic polymetallic sulfide precipitation process. Additionally, suggestions and prospects for the development of agents and control methods for the sulfide process in different wastewater systems were proposed. This paper preliminarily established the intrinsic relationship between sulfide precipitation and the selective separation of metal ions, providing more precise parameter guidance and strategy optimization for treating copper-arsenic polymetallic acidic wastewater.

Key words: copper-arsenic polymetallic acid wastewater, sulfide precipitation method, sulfurizing reagent, copper-arsenic separation, resource utilization

摘要：

有色冶炼和二次资源回收中会产生大量铜砷多金属酸性废水，其中有价金属与砷之间难以高效分离是制约其资源化利用的关键。本文从废水来源、操作因素以及硫源类型等方面对金属离子的选择性硫化沉淀进行了全面的综述。首先介绍铜砷多金属酸性废水的来源，阐明了不同工艺下废水的产生方式；围绕硫化沉淀法在铜砷多金属分离中的运用现状，着重介绍和分析了硫化沉淀法的原理及影响硫化分离效果的主要因素，揭示了选择性硫化分离中的内在规律；最后讨论并梳理了不同硫化药剂的开发及应用情况，重点讨论了铁硫化物在铜砷多金属硫化沉淀过程中的应用及其机理研究的现状，并对不同废水体系下药剂开发和硫化过程的调控手段提出了建议和展望。本文初步建立了硫化沉淀与金属离子选择性分离间的内在联系，为处理铜砷多金属酸性废水提供了更精准的参数指导和策略优化。

关键词: 铜砷多金属酸性废水, 硫化沉淀法, 硫化剂, 铜砷分离, 资源利用

CLC Number:

TD982

HONG Kai, FAN Huan, TIAN Jia, ZHANG Xingfei. Treatment of copper-arsenic polymetallic acidic wastewater by sulfide precipitation: A review[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5301-5314.

洪凯, 樊欢, 田佳, 张荥斐. 硫化沉淀法处理铜砷多金属酸性废水研究进展[J]. 化工进展, 2025, 44(9): 5301-5314.

Figures/Tables 12

References 71

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反应式	活度积
反应式	298K	323K	373K
Ag₂S ⇌ 2Ag⁺+S^2-	49.14	45.37	39.70
Bi₂S₃ ⇌ 2Bi³⁺+3S^2-	104.05	98.37	90.58
CdS ⇌ Cd²⁺+S^2-	27.19	25.70	23.73
CoS ⇌ Co²⁺+S^2-	19.74	18.94	18.1
CuS ⇌ Cu²⁺+S^2-	35.85	33.76	30.85
Cu₂S ⇌ 2Cu⁺+S^2-	47.64	44.13	38.89
FeS ⇌ Fe²⁺+S^2-	16.47	15.75	15.17
HgS ⇌ Hg²⁺+S^2-	52.7	49.1	43.9
NiS ⇌ Ni²⁺+S^2-	21.03	20.19	19.26
MnS ⇌ Mn²⁺+S^2-	12.95	12.59	12.4
PbS ⇌ Pb²⁺+S^2-	28.06	26.28	23.89
SnS ⇌ Sn²⁺+S^2-	27.53	26.04	24.08
ZnS ⇌ Zn²⁺+S^2-	23.10	22.07	20.83

反应式	活度积
反应式	298K	323K	373K
Ag₂S ⇌ 2Ag⁺+S^2-	49.14	45.37	39.70
Bi₂S₃ ⇌ 2Bi³⁺+3S^2-	104.05	98.37	90.58
CdS ⇌ Cd²⁺+S^2-	27.19	25.70	23.73
CoS ⇌ Co²⁺+S^2-	19.74	18.94	18.1
CuS ⇌ Cu²⁺+S^2-	35.85	33.76	30.85
Cu₂S ⇌ 2Cu⁺+S^2-	47.64	44.13	38.89
FeS ⇌ Fe²⁺+S^2-	16.47	15.75	15.17
HgS ⇌ Hg²⁺+S^2-	52.7	49.1	43.9
NiS ⇌ Ni²⁺+S^2-	21.03	20.19	19.26
MnS ⇌ Mn²⁺+S^2-	12.95	12.59	12.4
PbS ⇌ Pb²⁺+S^2-	28.06	26.28	23.89
SnS ⇌ Sn²⁺+S^2-	27.53	26.04	24.08
ZnS ⇌ Zn²⁺+S^2-	23.10	22.07	20.83

硫源类型	描述	优点	缺点
无机可溶	采用Na₂S、NaHS、(NH₄)₂S和Na₂S₂O₃等化学可溶剂作为水溶沉淀剂连续或间歇进行	1.成本低，原料来源广； 2.反应速度快； 3.易于操作	1.硫离子局部浓度过高； 2.反应效率低，需要过量使用； 3.形成胶状产物，难以过滤； 4.H₂S的二次污染
无机难溶	CaS、FeS、ZnS、MnS和P₂S₅化学难溶性材料以固体或悬浮液的形式引入	1.降低溶液的过饱和水平； 2.提高产物颗粒大小； 3.有效控制H₂S逸出	1.反应速度慢，适用性有限； 2.表面易被涂覆，反应效率低； 3.反应效率靠外场和环境影响； 4.引入其他金属阳离子
有机可溶	有机硫源中含有有机基团中的硫原子，在溶液中可水解或发生氧化反应，释放出硫离子	1.与无机难溶剂相比，具有更好的溶解度； 2.不同的官能团提高选择性； 3.反应条件温和，用量低	1.成本高，合成工艺复杂； 2.可能会残留危险或有毒的有机物，如CS₂； 3.金属-有机配合物在环境中容易分解，金属被重新释放
气体	指能提供硫离子的气体化合物。最常用的是H₂S，它能溶解于溶液中，与金属离子形成硫化物沉淀	1.高纯度和高效率； 2.不引入其他金属阳离子	1.剧毒气体，易造成安全事故； 2.需要特殊的硫化设备； 3.严格的管理制度和储存、运输和使用的限制
生物硫化	通过硫酸盐还原菌利用废水中的单质硫、废硫酸或硫酸盐生产H₂S	1.工艺环保，适应性广； 2.具有高稳定性和可持续性	1.需要较长的反应时间； 2.对环境温度、水质、微生物种类的选择要求高； 3.操作难度高

硫源类型	描述	优点	缺点
无机可溶	采用Na₂S、NaHS、(NH₄)₂S和Na₂S₂O₃等化学可溶剂作为水溶沉淀剂连续或间歇进行	1.成本低，原料来源广； 2.反应速度快； 3.易于操作	1.硫离子局部浓度过高； 2.反应效率低，需要过量使用； 3.形成胶状产物，难以过滤； 4.H₂S的二次污染
无机难溶	CaS、FeS、ZnS、MnS和P₂S₅化学难溶性材料以固体或悬浮液的形式引入	1.降低溶液的过饱和水平； 2.提高产物颗粒大小； 3.有效控制H₂S逸出	1.反应速度慢，适用性有限； 2.表面易被涂覆，反应效率低； 3.反应效率靠外场和环境影响； 4.引入其他金属阳离子
有机可溶	有机硫源中含有有机基团中的硫原子，在溶液中可水解或发生氧化反应，释放出硫离子	1.与无机难溶剂相比，具有更好的溶解度； 2.不同的官能团提高选择性； 3.反应条件温和，用量低	1.成本高，合成工艺复杂； 2.可能会残留危险或有毒的有机物，如CS₂； 3.金属-有机配合物在环境中容易分解，金属被重新释放
气体	指能提供硫离子的气体化合物。最常用的是H₂S，它能溶解于溶液中，与金属离子形成硫化物沉淀	1.高纯度和高效率； 2.不引入其他金属阳离子	1.剧毒气体，易造成安全事故； 2.需要特殊的硫化设备； 3.严格的管理制度和储存、运输和使用的限制
生物硫化	通过硫酸盐还原菌利用废水中的单质硫、废硫酸或硫酸盐生产H₂S	1.工艺环保，适应性广； 2.具有高稳定性和可持续性	1.需要较长的反应时间； 2.对环境温度、水质、微生物种类的选择要求高； 3.操作难度高