负载Mn的Fe基MOFs脱汞剂烟气脱汞研究

张晓奇; 沈伯雄; 张笑; 陈叮叮

负载Mn的Fe基MOFs脱汞剂烟气脱汞研究

河北工业大学能源与环境工程学院, 天津 300401

基金项目:

国家重点研发计划 2018YFB0605101

天津市自然科学重点基金 18JCZDJC39800

天津科技重大专项 18ZXSZSF00040

天津市科普项目 18KPXMSF00080

唐山市科技项目 18130211A

河北省自然科学基金 E2018202180

详细信息

通讯作者:
SHEN Bo-xiong, E-mail:shenboxiong0722@sina.com

中图分类号: X511
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- 被引次数: 0
出版历程
- 收稿日期: 2018-07-26
- 修回日期: 2018-10-30
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-01-10

Study on the mercury removal using Mn loaded Fe-based MOFs

School of Energy and Environment Engineering, Hebei University of Technology, Tianjin 300401, China

Funds:

the National Important Research and Development Plan 2018YFB0605101

Key Fund of Tianjin 18JCZDJC39800

the Project of Science and Technology of Tianjin 18ZXSZSF00040

Tianjin Science Popularization Project 18KPXMSF00080

the Project of Science and Technology of Tangshan 18130211A

Fund of Hebei Province E2018202180

摘要

摘要: 基于Fe基金属有机骨架（MOFS）作为载体，采用浸渍法制备了负载6% Mn的Mn/MIL-100（Fe）脱汞剂。在模拟烟气中，搭建固定床研究了Mn/MIF-100（Fe）脱除单质汞（Hg⁰）性能。采用X射线衍射分析（XRD）、X射线电子能谱（XPS）、N₂吸附-脱附（BET）和热重分析（TGA）对材料进行表征。研究表明，Mn/MIF-100（Fe）脱除单质汞（Hg⁰）效率较高，在250℃，空速（GHSV）为180000h^-1时，脱汞（Hg⁰）效率达82%以上。Mn/MIF-100（Fe）主要的脱汞机理是催化氧化，Mn的负载促进了汞的吸附，并随着烟气温度的提高，单质汞的氧化效率逐渐提高。O₂和NO促进汞的脱除，SO₂和NH₃抑制汞的脱除。Mn/MIL-100（Fe）整体上对复杂烟气的适应能力强。
- Fe基金属有机骨架 /
- 脱汞剂 /
- 吸附 /
- 氧化
Abstract: The Mn/MIL-100 (Fe) mercury removal agent loaded with 6% Mn was prepared by impregnation method using Fe-based metal organic framework (MOFs) as the support. A set of fixed bed reactor apparatus was installed and used to study the performance of Mn/MIF-100(Fe) to remove elemental mercury (Hg⁰) in the simulated flue gas. The materials were characterized by XRD, XPS, BET and TGA. The results showed that Mn/MIF-100 (Fe) had high efficiency in removing elemental mercury (Hg⁰). When the GHSV was 180000 h^-1 at 250℃, the mercury removal (Hg⁰) efficiency was above 82%. The main mercury removal mechanism of Mn/MIF-100 (Fe) was oxidation, and the loading of Mn promoted the adsorption of mercury. With the increase of flue gas temperature, the oxidation efficiency of elemental mercury was gradually increased. O₂ and NO promoted the removal of mercury while SO₂ and NH₃ inhibited the removal of mercury. Mn/MIL-100(Fe) had a strong adaptability to the complex flue gas as a whole.
- Fe based MOFs /
- adsorbent for mercury /
- adsorption /
- oxidation

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图 1 烟气脱汞系统示意图

Figure 1 Diagrammatic sketch of the removal of Hg⁰ in simulative flue gas

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图 2 催化剂的吸附-脱附等温线

Figure 2 Adsorption desorption isotherms of the catalysts

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图 3 催化剂的BJH孔径分布图

Figure 3 BJH pore size distribution curves of catalysts

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图 4 不同煅烧温度下脱汞剂的XRD谱图

Figure 4 XRD pattern of the catalysts calcined at different temperatures

◆: Mn₃O₄; ◇: Mn₂O₃; ●: Fe₂O₃

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图 5 脱汞剂Mn 2p_3/2的XPS谱图

Figure 5 Mn 2p_3/2 XPS spectra of the catalysts

(a): Mn/MIL-100 (Fe) catalyst; (b): Mn/Fe₂O₃ catalyst

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图 6 脱汞剂Fe 2p_3/2的XPS谱图

Figure 6 Fe 2p_3/2 XPS spectra of the catalysts

(a): Mn/MIL-100 (Fe) catalyst; (b): Mn/Fe₂O₃ catalyst

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图 7 脱汞剂O 1s的XPS谱图

Figure 7 O 1s XPS spectra of the catalysts

(a): Mn/MIL-100 (Fe) catalyst; (b): Mn/Fe₂O₃ catalyst

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图 8 脱汞剂对Hg⁰脱除效率的影响(1 h)

Figure 8 Hg⁰ removal efficiency of the catalysts (1 h)

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图 9 脱汞剂对氧化吸附效率的影响

Figure 9 The oxidation and adsorption efficiency of Hg⁰ of the catalysts

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图 10 不同氧浓度对脱汞效率的影响

Figure 10 Effect of O₂ concentration on mercury removal efficiency

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图 11 烟气中其他气体成分对脱汞效率的影响

Figure 11 Effects of other gas components in flue gas on mercury removal efficiency

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表 1 脱汞剂的比表面积、孔容和孔径

Table 1 Specific surface area, pore volume and pore diameter ofthe catalysts

Sample	BET surface area A/(cm²·g^-1)	Pore volume v/(cm³·g^-1)	Average pore diameter d/nm
MIL-100(Fe)	1223.3	0.66	2.17
Mn/MIL-100(Fe)	141.8	0.29	8.31
Mn/Fe₂O₃	7.6	0.0007	0.04

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表 2 催化剂金属离子各价态变换

Table 2 Percentage of valence state of each ion in the catalysts

Catalyst		Percentagew/%
Catalyst		Mn²⁺/Mn^x+	Mn³⁺/ Mn^x+	Mn⁴⁺/Mn^x+	Fe²⁺/ Fe^x+	Fe³⁺/Fe^x+	O_Ⅰ/(O_Ⅰ+ O_Ⅱ)	O_Ⅱ/(O_Ⅰ+ O_Ⅱ)
Mn/ MIL-100(Fe)	fresh used	6.12 6.24	67.72 63.76	26.16 30	42.2 39.8	57.80 60.03	77.44 67.73	22.56 32.27
Mn/Fe₂O₃	fresh used	- -	32.34 50.60	67.66 49.40	36.34 39.97	63.36 60.03	62.02 60.28	37.98 39.71
Mn^x+: Mn²⁺+Mn³⁺+Mn⁴⁺; Fe^x+: Fe²⁺+Fe³⁺

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