物理化学学报2023，Vol.39Issue(4)：76-84,9.DOI:10.3866/PKU.WHXB202206034
钾对CuSO4/TiO2脱硝催化剂的失活效应
Effect of Potassium on the Performance of a CuSO4/TiO2 Catalyst Used in the Selective Catalytic Reduction of NOx by NH3
摘要
Abstract
Owing to its renewability,abundance,and low environmental impact,biomass is considered to be a viable eco-friendly fuel.Various biofuel-fired power plants have been built worldwide to reduce carbon emissions.Potassium(K)is a typical impurity in the flue gas from biofuel combustion that can deactivate the catalyst used in the selective catalytic reduction of NOx by ammonia(NH3-SCR).CuSO4/TiO2,with excellent sulfur dioxide tolerance,is thought to be a promising vanadium-free catalyst for NH3-SCR;however,the influence of K on the CuSO4/TiO2 catalyst is still unknown.Therefore,in this study,the effect of K on the NH3-SCR performance of CuSO4/TiO2 were investigated and compared with the effect on the performance of the commercial V2O5-WO3/TiO2(VWTi)catalyst.K-poisoned catalysts were prepared via wet impregnation using potassium acetate as the K source.Nitrogen(N2)adsorption-desorption,X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),NH3-temperature programmed desorption(NH3-TPD),H2-temperature programmed reduction(H2-TPR),and in situ diffuse reflectance infrared Fourier-transform spectroscopy(in situ DRIFTS)were used to characterize the prepared catalysts.The NOx conversion over CuSO4/TiO2 with 1.0％(w)K was 92.1％(at 350℃),which was higher than the conversion(75.1％)achieved over the commercial VWTi catalyst with the same K content.The XRD,XPS,and H2-TPR results suggested that K reacted with the CuSO4 in the CuSO4/TiO2 catalyst to form CuO and K2SO4.The presence of CuO enhanced the oxidation of NH3 to N2O,NO,and NO2 during NH3-SCR,thereby decreasing the NOx conversion and N2 selectivity over CuSO4/TiO2.Moreover,based on the results from NH3-TPD and in situ DRIFTS of NH3 adsorption,it can be concluded that the Bransted acid sites(S-OH)were poisoned by K,which restrained the adsorption of NH3 on CuSO4/TiO2.Additionally,the high K content altered the pore structure of the catalyst,leading to a decrease in the specific surface area.However,according to the in situ DRIFTS results,NH3-SCR over K-poisoned CuSO4/TiO2 still followed the Eley-Rideal mechanism:First,NH3 was adsorbed on the Lewis and Br?nsted acid sites of the catalyst,and then gaseous NO and O2 reacted with the adsorbed NH3/NH4 on the acid sites,resulting in the formation of N2 and H2O.Notably,the abundance of acid sites and surface-adsorbed oxygen species on CuSO4/TiO2 could be the main reason for its higher resistance to K-poisoning.In conclusion,our current findings suggested that CuSO4/TiO2 might be a suitable NH3-SCR catalyst for use in the flue gas streams from biofuel-fired power plants.关键词
NH3-SCR催化剂/氮氧化物/Brønsted酸性位/氧化铜/生物质电厂Key words
NH3-SCR catalysts/NOx/Brønsted acid sites/CuO/Biofuel-fired power plants分类
化学化工引用本文复制引用
于艳科,耿梦荞,魏德胜,何炽..钾对CuSO4/TiO2脱硝催化剂的失活效应[J].物理化学学报,2023,39(4):76-84,9.基金项目
The project was supported by the National Natural Science Foundation of China(21906127,21876139,21922606),General Financial Grant from the China Postdoctoral Science Foundation(2021M692550),K.C.Wong Education Foundation and Instrumental Analysis Center of Xi'an Jiaotong University.国家自然科学基金(21906127,21876139,21922606),中国博士后科学基金(2021M692550),王宽诚教育基金会和西安交通大学分析测试中心资助 （21906127,21876139,21922606）
