电解锰渣浆液烟气脱硫性能及机制

doi:10.16085/j.issn.1000-6613.2021-0412

摘要/Abstract

摘要：

电解锰渣是电解锰生产过程中产生的锰矿石酸浸渣，富含锰、铁等活性组分，理论上可催化氧化SO₂实现烟气脱硫，同时脱硫后的电解锰渣可资源化利用，然而目前尚未见电解锰渣矿浆脱硫的研究报道。本文研究了工艺参数对电解锰渣浆液脱除SO₂性能的影响，探究了电解锰渣浆液烟气脱硫的过程机制。结果表明：锰渣粒径为200目（<75μm）、锰渣浆液初始浓度5000mg/L、气体流量400mL/min、进口SO₂体积分数0.20％、反应温度50℃、反应时间180min的条件下，电解锰渣浆液脱硫率最高可达93.87%。脱硫前后电解锰渣XRD、SEM、XPS表征结果表明，MnO₂、MnO、Fe₂O₃等活性组分参与SO₂反应，且浆液中的Mn²⁺、Fe³⁺等过渡金属离子液相催化氧化SO₂生成H₂SO₄，实现烟气脱硫。

关键词: 电解锰渣, 资源化利用, 二氧化硫, 烟气脱硫, 催化氧化

Abstract:

Electrolytic manganese residue (EMR) is the acid leaching slag of manganese ore produced in the production process of electrolytic manganese, which is rich in active components such as manganese and iron. In theory, the use of electrolytic manganese slag slurry for flue gas desulfurization realizes the resource utilization of electrolytic manganese slag while removing SO₂, which promotes the sustainable development of the electrolytic manganese industry. However, there is no research report on the desulphurization of EMR slurry. The influence of process conditions on the efficiency of desulfurization was studied. The experimental results showed that the bestprocess conditions for EMR slurry desulfurization were: EMR particle size was 200 meshes (<75μm), manganese slag slurry concentration was 5000mg/L, the mixed gas flow rate was 400mL/min, imported SO₂ concentration was 0.20%, and the temperature was 50℃. Under these conditions, the highest desulfurization rate at 180min was 93.87%. By analyzing the changes of ore pulp ion concentration and the XRD, SEM, XPS patterns of the products, the performance and mechanism of flue gas desulfurization of EMR slurry were investigated. MnO₂, MnO, Fe₂O₃ underwent redox reactions with SO₂ and formed metal sulfates. SO₂ was catalyzed and oxidized by transition metal ions such as Mn²⁺ and Fe³⁺ in the ore pulp to generated H₂SO₄.

Key words: electrolytic manganese residue, resource utilization, sulfur dioxide, flue gas desulfurization, catalytic oxidation

中图分类号:

X753

聂紫萌, 杨点, 熊玉路, 李英杰, 田森林, 宁平. 电解锰渣浆液烟气脱硫性能及机制[J]. 化工进展, 2022, 41(2): 1063-1072.

NIE Zimeng, YANG Dian, XIONG Yulu, LI Yingjie, TIAN Senlin, NING Ping. Performance and mechanism of electrolytic manganese slag slurry for flue gas desulfurization[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 1063-1072.

图/表 14

表1 电解锰渣的化学成分（质量分数） (%)

Fe₂O₃	SiO₂	TiO₂	Na₂O	MnO	Cr₂O₃	CaO	Al₂O₃	MgO	P₂O₅	SO₃
33.64	18.97	12.82	12.29	7.57	4.83	4.42	1.97	1.41	0.29	0.10

图1 电解锰渣矿浆脱硫实验装置1—N2钢瓶；2—O2钢瓶；3—SO2钢瓶；4—气体质量流量控制器；5—混气瓶；6—玻璃三通阀；7—鼓泡反应器；8—集热式恒温加热磁力搅拌器；9—气体干燥瓶；10—集气袋；11—微电脑烟尘平行采样仪；12—安全瓶；13—尾气吸收瓶

图2 电解锰渣粒径对电解锰渣矿浆烟气脱硫率与浆液pH的影响

图3 电解锰渣粒径对电解锰渣矿浆中铁、锰、硫酸根离子浓度的影响

图4 电解锰渣浆液浓度对电解锰渣矿浆烟气脱硫率与浆液pH的影响

图5 电解锰渣浆液浓度对电解锰渣矿浆中铁、锰、硫酸根离子浓度的影响

图6 混合气气体流量对电解锰渣矿浆烟气脱硫率与浆液pH的影响

图7 混合气气体流量对电解锰渣矿浆中铁、锰、硫酸根离子浓度的影响

图8 SO2初始浓度对电解锰渣矿浆烟气脱硫率与浆液pH的影响

图9 SO2初始浓度对电解锰渣矿浆中铁、锰、硫酸根离子浓度的影响

图10 温度对电解锰渣矿浆烟气脱硫率与浆液pH的影响

图11 温度对电解锰渣矿浆中铁、锰、硫酸根离子浓度的影响

表2 不同时间下脱硫浆液中离子浓度变化 (mg/L)

时间	Mn	Fe	Ca	Al	Co	Cu	Ni	Zn	SO $4 2 -$
0	0.14	0.13	1.52	1.19×10^-2	1.89×10^-2	1.14×10^-3	1.15×10^-3	0.20×10^-2	63.43
60min	2.76	0.71	6.80	3.41	2.05×10^-2	9.43×10^-3	1.94×10^-3	3.08×10^-2	514.86
180min	7.35	4.19	8.65	5.54	2.13×10^-2	12.40×10^-3	4.25×10^-3	2.48×10^-2	1623.43
增长百分比/%	5150	3123.08	469.08	46454.62	12.70	987.72	269.57	1140	2459.40

表2 不同时间下脱硫浆液中离子浓度变化 (mg/L)

时间	Mn	Fe	Ca	Al	Co	Cu	Ni	Zn	SO $4 2 -$
0	0.14	0.13	1.52	1.19×10^-2	1.89×10^-2	1.14×10^-3	1.15×10^-3	0.20×10^-2	63.43
60min	2.76	0.71	6.80	3.41	2.05×10^-2	9.43×10^-3	1.94×10^-3	3.08×10^-2	514.86
180min	7.35	4.19	8.65	5.54	2.13×10^-2	12.40×10^-3	4.25×10^-3	2.48×10^-2	1623.43
增长百分比/%	5150	3123.08	469.08	46454.62	12.70	987.72	269.57	1140	2459.40

图12 不同脱硫时间下电解锰渣及产物的XRD、FTIR及XPS分析

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