电解锰阳极泥中战略金属回收技术进展

王鹏星; 刘兵兵; 黄艳芳; 孙虎; 韩桂洪

doi:10.13779/j.cnki.issn1001-0076.2022.03.008

电解锰阳极泥中战略金属回收技术进展

郑州大学化工学院, 河南郑州 450001

基金项目:
国家自然科学基金(51904273、U2004215)

详细信息

作者简介: 王鹏星(1996-), 男, 河南洛阳人, 主要从事矿物资源加工、冶金过程强化研究

通讯作者: 刘兵兵(1989-), 男, 湖北襄阳人, 博士, 副教授, 主要从事矿物资源加工、冶金过程强化研究, E-mail: liubingbing@zzu.edu.cn; 韩桂洪(1981-), 男, 河北昌黎人, 博士, 教授, 主要从事矿物资源加工、冶金过程强化研究, E-mail: hanguihong@zzu.edu.cn

中图分类号: TD98;TF80;X757

收稿日期: 2022-03-10

刊出日期: 2022-06-25

Review on the Strategic Metals Recovery from Electrolytic Manganese Anode Slime (EMAS)

School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

More Information

Corresponding authors: LIU Bingbing, liubingbing@zzu.edu.cn ; HAN Guihong, hanguihong@zzu.edu.cn

Received Date: 10 March 2022

Publish Date: 25 June 2022

摘要

摘要:
电解锰行业每年产生7.5~12万t的锰阳极泥固废, 其矿物组成与结构复杂, 有价金属组分多、含量高, 综合利用难度大, 目前大部分厂家廉价销售或大量堆存, 造成了严重的资源浪费和环境污染。文章分析了阳极泥的产生机理和资源特点, 综述了阳极泥中主要有价战略金属元素Mn、Pb、Sn、Se的分离回收技术, 对比了还原浸出法、焙烧浸出法、碱熔—浸出法等阳极泥处理方法的优缺点, 提出了硫转化综合回收锰铅锡硒新思路, 可为电解锰阳极泥固废的资源化利用提供技术参考。
- 电解锰阳极泥 /
- 锰 /
- 铅 /
- 硒 /
- 锡 /
- 焙烧 /
- 浸出
Abstract:
75 000-120 000 tons of electrolytic manganese anode slime (EMAS) are produced in the electrolytic manganese industry every year. The EMAS has high content of strategic metals, complex mineral compositions and complicated structure, and thus the comprehensive utilization is difficult. At present, most manufacturers sell the EMAS cheaply or take the stockpiling disposal, causing serious waste of resources and environmental pollution. This paper analyzed the production mechanism and resource characteristics of the EMAS, and also summarized the separation and recovery technologies of the valuable metals including Mn, Pb, Sn, and Se from the EMAS. The advantages and disadvantages of the reduction leaching method, roasting-leaching method, and alkali melting-leaching method were reviewed and compared. This paper puts forward a novel technique solution for the comprehensive recovery of Mn, Pb, Sn, and Se by sulfur conversion, which can provide technical reference for utilization of EMAS.
- electrolytic manganese anode slime /
- manganese /
- lead /
- tin /
- selenium /
- roasting /
- leaching

HTML全文

图 1 电解锰流程

Figure 1.

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图 2 电解锰阳极泥原料分析：(a), (b)光学显微镜；(c), (d)SEM；(e)XRD^[64]

Figure 2.

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图 3 不同还原剂与MnO₂反应的ΔG^θ-T关系

Figure 3.

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图 4 SnO₂转化过程中反应的ΔG^θ-T关系

Figure 4.

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图 5 反应流程示意图

Figure 5.

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图 6 不同pH下锰锡离子形态分布图

Figure 6.

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表 1 典型电解锰阳极泥主要化学成分 /%

Table 1. Chemical constituents of the typical electrolytic manganese anode slime

Mn	(NH₄)₂SO₄	Fe	CaO	Pb	MgO	Sn	Se
40~50	5~10	0.1~6	0.1~6	3~6	0.1~6	0.1~0.5	0.1~0.4

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表 2 不同还原剂与MnO₂的反应方程式以及对应的ΔG^θ-T方程式

Table 2. Reactions of different reducing agents and MnO₂ and corresponding ΔG^θ-T equations

编号	反应方程式	ΔG^θ-T/(kJ·mol^-1)	自发反应温度范围/K
(1)	11MnO₂+2FeS₂=11MnO+Fe₂O₃+4SO₂(g)	ΔG_T^θ=-170.92-1.026T	自发反应
(2)	15MnO₂+2FeS₂+14H₂SO₄=15MnSO₄+Fe₂(SO₄)₃+14H₂O	ΔG^θT=-2918.36-0.014T	自发反应
(3)	2MnO₂+SO₂(g)=Mn₂O₃+SO₃(l)	ΔG_T^θ=-15.01+0.018T	T＜834
(4)	3MnO₂+2SO₂(g)=Mn₃O₄+2SO₃(l)	ΔG_T^θ=-22.22+0.049T	T＜453
(5)	MnO₂+SO₂(g)=MnSO₄	ΔG_T^θ=-240.98+0.177T	T＜1361
(6)	3MnO₂+2Fe+6H₂SO₄=3MnSO₄+Fe₂(SO₄)₃+6H₂O	ΔG_T^θ=-1020.13+0.047T	自发反应

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表 3 电解锰阳极泥中锰铅分离方法

Table 3. Separation methods of manganese and lead from electrolytic manganese anode slime

分离方法	基本原理	优点	缺点
无机还原浸出法	采用低价硫化物将Mn⁴⁺还原为Mn²⁺进入溶液，铅富集于渣中	锰浸出率高，操作简单	产生酸性废水和废渣，产生SO₂和H₂S气体
有机还原浸出法	利用有机物的还原性将锰还原为低价进入溶液，铅不发生反应	锰铅分离效果好，原料价格低廉，易获得	操作复杂，反应周期长
固态焙烧浸出法(空气气氛)	高温焙烧活化，乙酸铵浸出铅，锰则不发生反应	铅浸出率高，操作简单	能耗高，反应时间长
固态焙烧浸出法(还原气氛)	利用还原性气体还原锰和铅，硫酸浸出后，固液分离	分离效果好，反应周期短	能耗高，会产生二次污染
碱熔浸出法	高温下碱溶液与MnO₂反应生成锰酸根进入溶液，铅不发生反应，锰酸盐经还原得到初级二氧化锰	产品收率高，分离效果好	操作复杂，能耗高

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表 4 SnO₂转化过程中发生的主要反应^[73]及对应的ΔG^θ-T方程式

Table 4. Main chemical reactions^[73] during the conversion of SnO₂and corresponding ΔG^θ-Tequations

编号	反应方程式	ΔG^θ-T/(kJ·mol^-1)	自发反应温度范围/K
(32)	SnO₂+C=SnO+CO(g)	ΔG^θ-T=188.98-0.196T	T＞964
(33)	SnO₂+2C=Sn+2CO(g)	ΔG^θ-T=359.06-0.384T	T＞935
(34)	2SnO₂+C=2SnO+CO₂(g)	ΔG^θ-T=206.00-0.216T	T＞954
(35)	SnO₂+C=Sn+CO₂(g)	ΔG^θ-T=187.10-0.208T	T＞900
(36)	FeS₂=FeS+0.5S₂(g)	ΔG^θ-T=140.15-0.138T	T＞1 016
(37)	SnO+FeS=FeO+SnS(g)	ΔG^θ-T=211.46-0.149T	T＞1 419
(38)	2Sn+S₂=2SnS(g)	ΔG^θ-T=74.53-0.112T	T＞665

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