铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺

doi:10.16085/j.issn.1000-6613.2020-1067

摘要/Abstract

摘要：

结合电解锰生产工艺，以氧化锰矿为原料，以电解锰生产过程产生的电解阳极液废水配置烟气脱硫浆液，在其中添加FeSO₄强化电解锰阳极液体系下氧化锰矿烟气脱硫及浸锰能力，探讨铁强化氧化锰矿烟气脱硫和浸锰的工艺条件对烟气SO₂脱除和锰浸出的影响机制。研究发现FeSO₄的加入，通过FeSO₄与MnO₂之间的氧化还原反应以及产物三价铁离子和二价锰离子的协同催化作用，可同时提高锰矿烟气脱硫效率和锰的浸出率。锰矿粒径越小，脱硫及浸锰效率越高。温度升高，氧化锰矿浆液烟气脱硫率逐渐下降，浸锰率则先升高后下降，并在60℃时达到最大。浆液液固比和烟气流量的增大均会导致烟气脱硫率的下降，但会提高氧化锰矿浸锰率。进口SO₂浓度过高会导致脱硫率下降，但更有利于浸锰。采用5级逆流吸收对7%的烟气进行铁离子强化氧化锰浆脱硫，得到最终SO₂出口浓度293μL/L，溶液Mn²⁺浓度为44.72g/L，满足电解要求。铁强化电解锰阳极液体系有效回收利用了电解锰生产废水，不仅集脱硫浸锰工艺为一体，且可实现脱硫和浸锰效率的同时提升，为电解锰行业的清洁生产和资源综合利用提供理论依据和技术参考。

关键词: 烟道气, 浸取, 环境, 脱硫, 氧化锰矿, 铁

Abstract:

In order to remove SO₂ from manganese slag calcination process, and combine with the production features of electrolytic manganese production enterprises, the manganese oxide ore was used as the raw material, and the wastewater anode solution of electrolytic manganese was used to prepare the ore pulp (desulfurizer). The influences of processing parameters and FeSO₄ added on desulfurization and manganese leaching were studied. The results indicated that the introduction of FeSO₄ promoted the Mn leaching via the redox reaction between MnO₂ and FeSO₄, and then, the product (Fe³⁺) and the Mn²⁺ in solution could act as the catalyst to catalyze the desulfurization reaction. The desulfurization activity and the Mn leaching rate increased with the decrease of the ore particle size. With the increase of reaction temperature, the desulfurization activity decreased, and the Mn leaching rate increased at first and then decreased which reached the maximum value at 60℃. When the liquid-solid ratio and the inlet flow rate increases, the desulfurization efficiency decreased, but the Mn leaching rate was enhanced. The 5-stage manganese oxide slurry desulfurization of the 7% flue gas with FeSO₄ added showed that the outlet SO₂ was 293μL/L, and the Mn²⁺ concentration of lixivium was 44.72g/L, which met the requirements of electrolytic manganese. The present flue gas desulfurization system could recycle the wastewater anode solution of electrolytic manganese, and provide a new technology for sulfur dioxide removal from flue gas and Mn extraction form manganese oxide ore simultaneously. The present study provides theoretical basis and technical reference for clean production and comprehensive utilization of resources in electrolytic manganese industry.

Key words: flue gas, leaching, environment, desulfurization, manganese oxide ore, iron

中图分类号:

X701.3

姚露, 辛广智, 杨林, 蒲鹏燕, 江霞, 蒋文举. 铁强化电解锰阳极液体系中氧化锰矿烟气脱硫和锰浸出工艺[J]. 化工进展, 2021, 40(5): 2859-2866.

YAO Lu, XIN Guangzhi, YANG Lin, PU Pengyan, JIANG Xia, JIANG Wenju. Using iron promoted manganese oxide ore for simultaneous flue gas desulfurization and Mn leaching: a process study[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2859-2866.

图/表 10

图1 氧化锰矿外貌和XRD图

图2 锰矿脱硫实验装置①—N2钢瓶；②—O2钢瓶；③—SO2钢瓶；④—质量流量计；⑤—钢瓶减压阀；⑥—气体混合器；⑦—三通阀；⑧—尾气吸收瓶；⑨—SO2采样瓶；⑩—恒温磁力水浴锅；?—冷凝管；?—鼓泡反应器；?—气孔

图3 锰矿粒径对氧化锰矿烟气脱硫率和浸锰率的影响（实验条件：烟气流量2L/min，SO2进口体积分数2%，O2体积分数10%，温度60℃，FeSO4 浓度5g/L，液固比10∶1）

图4 温度对氧化锰矿烟气脱硫率和浸锰率的影响（实验条件：烟气流量2L/min，SO2进口体积分数2%，O2体积分数10%，锰矿粒径200目，Fe2+ 5g/L，液固比10∶1）

图5 液固比对氧化锰矿烟气脱硫率和浸锰率的影响（实验条件：烟气流量2L/min，SO2进口体积分数2%，O2体积分数为10%，锰矿粒径200目，Fe2+ 5g/L，温度为60℃）

图6 烟气流量对氧化锰矿烟气脱硫率和浸锰率的影响（实验条件：液固比10∶1，SO2进口体积分数2%，O2体积分数为10%，锰矿粒径200目，Fe2+ 5g/L，温度为60℃）

图7 进口SO2浓度对氧化锰矿烟气脱硫率和浸锰率的影响（实验条件：液固比10∶1，烟气流量2L/min，O2体积分数为10%，锰矿粒径200目，Fe2+ 5g/L，温度为60℃）

图8 锰渣煅烧烟气脱硫工艺流程

图9 多级脱硫的脱硫率随时间的变化

图10 多级脱硫锰矿渣XRD图

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