改性钒铈基催化剂催化氧化烟气中邻二甲苯

doi:10.16085/j.issn.1000-6613.2019-1031

摘要/Abstract

摘要：

燃煤过程中产生微量VOCs随烟气排放将导致大气污染。本文以Mn、Fe、Co、Cu对钒铈钛（Ce-V₂O₅/TiO₂）催化剂进行改性，并研究催化剂对烟气中典型VOCs中的邻二甲苯氧化脱除行为。研究结果表明，Mn、Fe改性分别在低温段和中高温段有效提高Ce-V₂O₅/TiO₂催化剂对烟气中邻二甲苯的催化氧化效率。烟气中的水蒸气、SO₂、NH₃、NO对催化氧化有不同的抑制程度，其中NH₃对催化效率抑制作用最强。不同改性催化剂对烟气组分反应不同，Fe改性Ce-V₂O₅/TiO₂催化剂抗烟气复杂组分中抗毒性最强。表征结果表明，Fe改性的Ce-V₂O₅/TiO₂催化剂表面积高、氧化还原性强，具有高催化活性与较强抗中毒性，可能成为一种针对燃煤烟气中有机污染物高效脱除的有潜力的催化剂材料。

关键词: 煤燃烧, 邻二甲苯, 催化, 氧化, 烟气组分

Abstract:

VOCs emission occurs in the process of coal combustion and would lead to air pollution. In this work, Mn, Fe, Co, and Cu modified Ce-V₂O₅/TiO₂ catalysts were prepared and their catalytic behavior ino-xylene removal from flue gas were investigated. The experimental results indicated that Mn modified and Fe modified Ce-V₂O₅/TiO₂catalysts exhibited superioro-xylene removal efficiencies at low and high temperature ranges, respectively. Besides, the effects of complex flue gas components on the catalytic activities were investigated. The results indicated that all components in the flue gas including H₂O, SO₂, NH₃ and NO lead to reduce the catalysts efficiency, and the strongest inhibition occured when NH₃ was added in the flue gas. Different modified catalysts reacted differently for the flue gas components. The Fe-modified Ce-V₂O₅/TiO₂ catalyst had the strongest anti-toxicity. Characterization results indicated that Fe-modified Ce-V₂O₅/TiO₂ catalyst had the high surface area and strong redox property, which made it had the highest catalytic activity and strongest anti-poisoning property. Fe modified Ce-V₂O₅/TiO₂ catalyst had the potential to be used in industrial for VOCs removal from coal combustion flue gas.

Key words: coal combustion, o-xylene, catalysis, oxidation, flue gas components

中图分类号:

X511

王玉亭,石其其,张铭洋,张笑,沈伯雄. 改性钒铈基催化剂催化氧化烟气中邻二甲苯[J]. 化工进展, 2020, 39(3): 1167-1173.

Yuting WANG,Qiqi SHI,Mingyang ZHANG,Xiao ZHANG,Boxiong SHEN. Modified of V/Ce based catalyst for catalytic oxidation ofo-xylene in flue gas[J]. Chemical Industry and Engineering Progress, 2020, 39(3): 1167-1173.

图/表 12

图1 邻二甲苯脱除实验台架1—质量流量计；2—混气瓶；3—三通阀；4—加热反应室

图2 催化剂催化氧化邻二甲苯的效率[vN2=160mL/min，vO2=10mL/min，邻二甲苯体积分数为20μL/L(即94.79mg/m3)，GHSV=60000h-1]

图3 催化剂在含H2O烟气中催化氧化邻二甲苯的效率[T=250℃，vN2=160mL/min，vO2=10mL/min，邻二甲苯体积分数为20μL/L(即94.79mg/m3)，GHSV=60000h-1]

图4 催化剂在含SO2烟气中催化氧化邻二甲苯的效率[T=250℃，vN2=160mL/min，vO2=10mL/min，SO2体积分数为1000μL/L(即2859.82mg/m3)，邻二甲苯体积分数为20μL/L即94.79mg/m3，GHSV=60000h-1]

图5 催化剂在含NO烟气中催化氧化邻二甲苯的效率[T=250℃，vN2=160mL/min，vO2=10mL/min，NO体积分数为50μL/L(即66.96mg/m3)，邻二甲苯体积分数为20μL/L(即94.79mg/m3)，GHSV=60000h-1]

图6 催化剂在含NH3烟气中催化氧化邻二甲苯的效率[T=250℃，vN2=160mL/min，vO2=10mL/min，NH3体积分数为50μL/L(即38.01mg/m3)，邻二甲苯体积分数为20μL/L(即94.79mg/m3)，GHSV=60000h-1]

图7 催化剂在SO2烟气中长时间催化氧化邻二甲苯效率[T=250℃，vN2=160mL/min，vO2=10mL/min，邻二甲苯体积分数为20μL/L(即94.79mg/m3)，SO2体积分数为1000μL/L(即2859.82mg/m3)，GHSV=60000h-1]

表1 催化剂比表面积及孔结构特性

催化剂	比表面积/m²·g^-1	孔体积/cm³·g^-1	孔径/nm
10Ce-V₂O₅/TiO₂	107.07	0.38	14.54
4Mn6Ce-V₂O₅/TiO₂	134.45	0.43	12.88
4Fe6Ce-V₂O₅/TiO₂	175.43	0.49	11.32

图8 催化剂孔径分布

图9 催化剂的XRD谱图

图10 催化剂的H2-TPR谱图

图11 催化剂的NH3-TPD谱图

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