Mn-Fe复合氧化物脱除燃煤烟气中砷、硒的实验研究

黄玉林; 邢佳颖; 王春波; 张月

doi:10.19906/j.cnki.JFCT.2022037

Mn-Fe复合氧化物脱除燃煤烟气中砷、硒的实验研究

doi: 10.19906/j.cnki.JFCT.2022037

华北电力大学动力工程系, 河北省低碳高效发电技术重点实验室, 河北保定 071003

基金项目: 国家重点研发计划（2020YFB0606301）和国家自然科学基金（51976059）资助

详细信息

通讯作者:
E-mail: 120192102130@ncepu.edu.cn

中图分类号: X773
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出版历程
- 收稿日期: 2022-03-25
- 修回日期: 2022-04-26
- 录用日期: 2022-04-27
- 网络出版日期: 2022-05-05
- 刊出日期: 2022-11-30

Experimental study on adsorption of arsenic and selenium in coal fired flue gas by Mn-Fe binary oxide

Department of Energy Power & Mechanical Engineering, North China Electric Power University, Hebei Key Laboratory of Low Carbon and High Efficiency Power Generation Technology, Baoding 071003, China

Funds: The project was supported by the National Key R&D Program of China (2020YFB0606301) and National Natural Science Foundation of China (51976059)

摘要

摘要: 采用共沉淀法制备了一系列Mn-Fe复合氧化物，研究了物质的量比和温度对气相砷、硒吸附的影响，考察了As₂O₃和SeO₂双组分气体的同时吸附特性，对吸附产物中砷、硒的稳定性进行测定。结果表明，As₂O₃和SeO₂在Mn-Fe复合氧化物表面的吸附量随Mn含量增加呈先增大后减小的趋势，当Mn/Fe物质的量比为1∶1时吸附量达到最大；两者的最佳吸附温度分别为750和600 ℃；双组分气体同时吸附时，两者存在竞争作用，Mn-Fe复合氧化物会优先吸附As₂O₃，SeO₂的吸附受到抑制；此外，预吸附的SeO₂会增强临近原子吸附活性，促进As₂O₃的吸附；吸附后的Mn-Fe复合氧化物浸出液中砷和硒的质量浓度均低于控制限值，在随粉煤灰进行资源化利用（如作为混凝土成分、水泥原料等）过程中不会产生二次污染。
- Mn-Fe复合氧化物 /
- 吸附剂 /
- 砷 /
- 硒 /
- 同时吸附
Abstract: A series of Mn-Fe binary oxides with different molar ratios were synthesized by coprecipitation method, and their adsorption behaviors of gaseous arsenic and selenium in flue gas at different temperature were investigated. The simultaneous adsorption characteristics of As₂O₃ and SeO₂ on Mn-Fe binary oxide were studied. To avoid secondary pollution for adsorbent utilization, As/Se leaching properties in Mn-Fe binary oxides were evaluated. Results show that the adsorption capacity of As₂O₃ and SeO₂ on the Mn-Fe binary oxides increases firstly and then decreases with the increasing Mn content. The adsorption capacity reaches the maximum when the molar ratio is 1∶1. The optimum adsorption temperatures of As₂O₃ and SeO₂ are 750 and 600 ℃, respectively. During the process for As₂O₃ and SeO₂ adsorption on Mn-Fe binary oxide simultaneously, Mn-Fe binary oxides preferentially adsorb As₂O₃, while SeO₂ is inhibited. In addition, the pre-adsorption SeO₂ can enhance the adsorption activities of adjacent atoms, which is beneficial for As₂O₃ adsorption. The concentration of arsenic and selenium in the leaching solution of spent Mn-Fe binary oxide is far lower than the control limit, which will be no secondary pollution in the process of utilization with fly ash.
- Mn-Fe binary oxide /
- adsorbent /
- arsenic /
- selenium /
- simultaneous adsorption

HTML全文

FIG. 1993. FIG. 1993.

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图 1 固定床吸附反应实验装置示意图

Figure 1 Fixed bed adsorption reaction experimental device

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图 2 吸附剂的XRD谱图

Figure 2 XRD patterns of adsorbents

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图 3 不同Mn/Fe物质的量比对吸附性能的影响

Figure 3 Effect of Mn/Fe molar ratio on adsorption properties

(a): Actual adsorption capacity；(b): Theoretical adsorption capacity

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图 4 吸附温度对Mn-Fe复合氧化物吸附性能的影响

Figure 4 Effect of temperature on adsorption properties of Mn-Fe binary oxides

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图 5 新鲜及不同吸附温度下Mn-Fe复合氧化物的SEM照片

Figure 5 SEM images of Mn-Fe binary oxides at fresh and different adsorption temperatures

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图 6 As₂O₃和SeO₂双组分气体同时吸附特性

Figure 6 Simultaneous adsorption characteristics of As₂O₃ and SeO₂

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图 7 预吸附As₂O₃/SeO₂对另一种组分吸附的影响

Figure 7 Effect of pre-adsorption of As₂O₃/SeO₂ on adsorption of another component

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图 8 Mn-Fe复合氧化物对As₂O₃/SeO₂的选择性吸附能力

Figure 8 Selective adsorption capacity of Mn-Fe binary oxide for As₂O₃/SeO₂

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表 1 吸附剂的元素含量、比表面积和孔结构参数

Table 1 Contents of Mn and Fe elements, specific surface area and pore structure parameters of adsorbents

Mn/Fe (mole ratio)	Mn/%	Fe/%	Surface area/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Pore diameter/ nm
Fe₂O₃	0.00	100.00	16.37	0.11	22.10
0.25∶1	20.54	79.46	201.31	0.37	5.94
0.5∶1	35.39	64.61	160.06	0.32	6.28
1∶1	51.52	48.48	117.13	0.30	9.37
2∶1	69.41	30.59	76.48	0.25	11.68
Mn₃O₄	100.00	0.00	19.02	0.13	20.71

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表 2 Mn-Fe复合氧化物中砷和硒的浸出特性

Table 2 Leaching characteristics of As and Se on spent Mn-Fe binary oxide

Leached As/Se	Separate		Simultaneous
Leached As/Se	As	Se	As	Se
Amount /(mg·L⁻¹)	0.0216	0.1078	0.0126	0.0525
Proportion /%	0.271	2.372	0.114	1.733

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