Ce掺杂对钒钨钛催化剂脱硝性能的影响
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东南大学能源与环境学院 能源热转换及其过程测控教育部重点实验室

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X511

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江苏省科技成果转化专项资金项目(BA2022073);清洁高效燃煤发电与污染控制国家重点实验室开放课题(D2022FK076)


Effect of CeO2 addition on DeNOx performance of V-W-Ti catalyst
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1.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education,School of Energy and Environment,Southeast University;2.Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education,School of Energy and Environment,Southeast University

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    摘要:

    对钒钨钛(V-W-Ti)催化剂进行Ce掺杂改性制备了CexV1W7/Ti(x%为CeO2负载量),通过XRD、TEM、FTIR、XPS等表征其结构和元素组成,通过NH3/NO-TPD表征NH3和NO在催化剂表面的吸附强弱分布,并测试不同CeO2负载量下催化剂的脱硝性能,最后经密度泛函理论(DFT )计算探究催化剂的失活机理。结果表明,负载CeO2增加了催化剂表面化学吸附氧的比例和Br?nsted酸性位点,但也减少了催化剂表面V4+的比例和Lewis酸性位点;适当CeO2负载量能显著提高钒钨钛催化剂的中低温活性,但负载量过多会降低催化剂的高温活性,CeO2负载量为1% (以催化剂质量分数为基准)的钒钨钛催化剂(Ce1V1W7/Ti)表现最佳,其在全温度(260~400 ℃)段的脱硝活性均优于改性前,在260 ℃,空速为6×104 h-1的反应条件下,NOx脱除率从79.0 1%增加至99.19%,在含有H2O、SO2的气氛中,其NOx脱除率从58.33%升至74.55%。Ce掺杂降低了催化剂表面的氧空位形成能,改变了催化剂表面的酸位强弱,强化了SO2在催化剂表面的吸附,SO2中毒后的催化剂表面会沉积硫酸铵盐,在H2O的协同作用下,Ce掺杂后催化剂表面更易沉积硫酸铵盐,这是催化剂失活的主要原因。

    Abstract:

    CeO2 modification was carried out on V-W-Ti catalyst, and the denitration performance of the catalyst was tested with different levels of CeO2 addition. The results showed that the addition of CeO2 could improve the medium and low temperature activities of the catalyst significantly, but too much loading would reduce the high temperature activity of the catalyst. Overall, V-W-Ti catalyst containing 1% of CeO2 in the mass of the catalyst showed the best performance. Its denitrification activity was better than that of the unmodified catalyst across the entire temperature range. Under reaction conditions of 260 ℃ and GHSV of 60000 h-1, its NOx removal efficiency increased from 79.01% to 99.19%. In an atmosphere containing H2O and SO2, its NOx removal efficiency increased from 58.33% to 74.55%. The catalyst with different CeO2 additions were characterized by XRD, N2 adsorption-desorption, XPS, NH3 temperature programmed desorption (NH3-TPD), and FTIR, which showed that the CeO2 addition increased the proportion of adsorbed oxygen and Br?nsted acidic sites on the catalyst surface , but it also decreased the proportion of V4+ and Lewis acidic sites on the surface, so CeO2 addition has different effects on the denitrification activity of V-W-Ti catalyst at low and high temperatures. DFT calculation results show that Ce doping reduces the formation energy for the oxygen vacancy on the catalyst surface, changes the acidity of the catalyst surface and enhances the adsorption of SO2 on the catalyst.

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陈宏,仲兆平,周峻伍. Ce掺杂对钒钨钛催化剂脱硝性能的影响[J].精细化工,2024,41(7):

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  • 收稿日期:2023-08-13
  • 最后修改日期:2023-10-10
  • 录用日期:2023-09-19
  • 在线发布日期: 2024-07-11
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