Co掺杂铁基氧化物吸附剂燃煤烟气脱汞实验研究

王永兴; 黄亚继; 董璐; 袁琦; 丁守一; 程好强; 王圣; 段钰锋

Co掺杂铁基氧化物吸附剂燃煤烟气脱汞实验研究

王永兴¹,
黄亚继^1, ,,
董璐¹,
袁琦^{1, 2},
丁守一¹,
程好强¹,
王圣³,
段钰锋¹

1.
东南大学能源热转换及其过程测控教育部重点实验室, 江苏南京 210096
2.
光大环保技术研究院, 江苏南京 210000
3.
国电环境保护研究院, 江苏南京 210031

基金项目:

国家重点研发计划 2016YFC0201105

详细信息

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2020-04-20
- 修回日期: 2020-06-19
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-07-10

Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent

1.
Key Laboratory of Energy Thermal Conversion and Control of the Ministry of Education, Southeast University, Nanjing 210096, China
2.
Everbright Environmental Protection Technology Research Institute, Nanjing 210000, China
3.
China State Power Environmental Protection Research Institute, Nanjing 210031, China

Funds:

the National Key Research and Development Projec 2016YFC0201105

More Information

Corresponding author: HUANG Ya-ji, Tel:13851997665, E-mail:heyyj@seu.edu.cn

摘要

摘要: 使用柠檬酸法制备了Co掺杂的铁基氧化物（FeCo）吸附剂，通过固定床脱汞实验装置系统考察了FeCo吸附剂的脱汞性能，并利用比表面积（BET）、X射线衍射（XRD）、H₂-程序升温还原（H₂-TPR）、傅里叶红外光谱（FT-IR）、X射线光电子能谱（XPS）等表征手段分析吸附剂的物理化学特性。结果表明，α-Fe₂O₃中掺入Co后，比表面积、孔结构特性均得到改善，且氧化还原性能也相应提升；FeCo吸附剂在200-250℃获得最高约97%的脱汞效率；烟气中O₂和NO的存在有助于FeCo吸附剂对Hg⁰的脱除，而SO₂和H₂O则抑制FeCo吸附剂对Hg⁰的脱除，同时NO能削弱SO₂对FeCo脱汞的抑制作用。在脱汞过程中，FeCo吸附剂表面的活性组分Fe³⁺、Co³⁺和O^*均消耗，参与了Hg⁰氧化反应，且吸附剂表面生成了HgO。在含SO₂气氛中进行脱汞反应后，FeCo吸附剂表面发生硫酸盐化，从而削弱了吸附剂的脱汞性能，汞在吸附剂表面以HgO和HgSO₄形式存在。
- 汞 /
- 铁 /
- 钴 /
- 燃煤烟气
Abstract: In this paper, the citric acid method was used to prepare the Co-doped iron-based oxide sorbent. The mercury removal performance of the FeCo sorbent was investigated by a fixed-bed mercury removal experimental device system, and the characterization methods of the specific surface area (BET), X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR), Fourier infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were performed to analyze the physical and chemical characteristics of the sorbent. The results of the study indicate that the specific surface area and pore structure characteristics are improved after the addition of Co into α -Fe₂O₃, and the redox performance of α -Fe₂O₃ is also improved. The maximum mercury removal efficiency of FeCo sorbent is obtained at 200-250 ℃ at the value of about 97%. The presence of O₂ and NO in the gas benefits the removal of Hg⁰ over FeCo sorbent, while SO₂ and H₂O inhibit the removal of Hg⁰ over FeCo sorbent. The presence of NO can weaken the inhibitory effect of SO₂ on mercury removal performance over FeCo. During the mercury removal process, the active components Fe³⁺, Co³⁺, and O^* on the surface of the FeCo sorbent are consumed, particitate in the Hg⁰ oxidation process, and HgO is formed on the surface of the sorbent. After the mercury removal reaction in the atmosphere containing SO₂, the sulfation of the sorbent surface is occurred, which weakens the mercury removal performance of the adsorbent.
- mercury /
- iron /
- cobalt /
- coal-fired flue gas

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图 1 固定床脱汞实验装置示意图

Figure 1 Fixed bed system of mercury adsorption test

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图 2 载体和催化剂的XRD谱图

Figure 2 XRD patterns of the supports and catalysts

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图 3 样品的N₂吸附-脱附曲线

Figure 3 N₂ adsorption-desorption curves of the samples

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图 4 样品的H₂-TPR谱图

Figure 4 H₂-TPR profiles of the samples

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图 5 新鲜吸附剂表面Fe 2p (a)、Co 2p (b)和O 1s (c)的XPS谱图

Figure 5 Fe 2p (a), Co 2p (b), and O 1s (c) XPS profiles of the fresh sorbents

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图 6 α-Fe₂O₃掺杂不同金属对Hg⁰脱除性能的影响(反应工况：N₂+5%O₂)

Figure 6 Effect of different metals doping on Hg⁰ removal performance over α-Fe₂O₃ (reaction condition: N₂+5%O₂)

: α-Fe₂O₃; : FeCo; : FeCu; : FeMn; : FeCr

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图 7 O₂对FeCo吸附剂Hg⁰脱除性能的影响(反应工况：200℃)

Figure 7 Effect of O₂ on Hg⁰ removal performance over FeCo sorbent (reaction condition: 200℃)

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图 8 NO对FeCo吸附剂Hg⁰脱除性能的影响(反应工况：200℃)

Figure 8 Effect of NO on Hg⁰ removal performance over FeCo sorbent (reaction condition: 200℃)

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图 9 SO₂对FeCo吸附剂Hg⁰脱除性能的影响(反应工况：200℃)

Figure 9 Effect of SO₂ on Hg⁰ removal performance over FeCo sorbent (reaction condition: 200℃)

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图 10 H₂O对FeCo吸附剂Hg⁰脱除性能的影响(反应工况：200℃)

Figure 10 Effect of H₂O on Hg⁰ removal performance over FeCo sorbent (reaction condition: 200℃)

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图 11 反应后吸附剂表面Fe 2p (a)、Co 2p (b)和O 1s (c)的XPS谱图

Figure 11 Fe 2p (a), Co 2p (b), and O 1s (c) XPS profiles of the spent sorbents

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图 12 FeCo-S表面S 2p (a)和Hg 4f (c)及FeCo-O表面Hg 4f (b) XPS谱图

Figure 12 S 2p (a) and Hg 4f (c) XPS profiles of the FeCo-S, and Hg 4f (b) XPS profiles of the FeCo-O sorbent

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表 1 样品的BET表征

Table 1 BET results of the samples

Sample	A_BET/(m²·g^-1)	v_t/(cm³·g^-1)	d_ave/nm
α-Fe₂O₃	24.57	0.19	26.52
FeCo	30.46	0.21	20.59
Co₃O₄	21.38	0.18	29.83

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表 2 样品表面原子摩尔含量

Table 2 Mole content of the atoms on the surface of samples Samples

Sample	Fe 2p /%		Co 2p /%		O 1s /%
Sample	Fe²⁺/Fe^T	Fe³⁺/Fe^T	Co³⁺/Co^T	Co²⁺/Co^T	O_L/O^T	O^*/O^T
Fresh FeCo	37.2	62.8	47.2	52.8	50.7	49.3
FeCo-O	49.1	50.9	56.3	43.7	57.2	42.3
FeCo-S	41.3	58.7	51.6	48.4	53.4	46.2
Fe^T represents Fe²⁺+Fe³⁺, Co^T represents Co²⁺+Co³⁺, O^T represents O_L +O^*

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