钾对CuSO4/TiO2脱硝催化剂的失活效应

doi:10.3866/PKU.WHXB202206034

物理化学学报 >> 2023, Vol. 39 >> Issue (4): 2206034.doi: 10.3866/PKU.WHXB202206034

所属专题：庆祝谢有畅教授九十华诞专刊

钾对CuSO₄/TiO₂脱硝催化剂的失活效应

于艳科¹, 耿梦荞¹, 魏德胜¹, 何炽¹^,²^,³^,*()

¹ 西安交通大学能源与动力工程学院环境科学与工程系, 西安 710049
² 西安交通大学动力工程多相流国家重点实验室, 西安 710049
³ 中国科学院大学挥发性有机物污染控制材料与技术国家工程实验室, 北京 101408

收稿日期:2022-06-22 录用日期:2022-07-13 发布日期:2022-07-18
通讯作者: 何炽 E-mail:chi_he@xjtu.edu.cn
基金资助:
国家自然科学基金(21906127);国家自然科学基金(21876139);国家自然科学基金(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

Effect of Potassium on the Performance of a CuSO₄/TiO₂ Catalyst Used in the Selective Catalytic Reduction of NO_x by NH₃

Yanke Yu¹, Mengqiao Geng¹, Desheng Wei¹, Chi He¹^,²^,³^,*()

¹ Department of Environmental Science and Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China
² State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China
³ National Engineering Laboratory for VOCs Pollution Control Material & Technology, University of Chinese Academy of Sciences, Beijing 101408, China

Received:2022-06-22 Accepted:2022-07-13 Published:2022-07-18
Contact: Chi He E-mail:chi_he@xjtu.edu.cn
Supported by:
the National Natural Science Foundation of China(21906127);the National Natural Science Foundation of China(21876139);the National Natural Science Foundation of China(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

摘要/Abstract

摘要：

为了减少碳排放，在世界各地兴建了越来越多的生物质电厂。钾元素是生物质电厂烟气中的一种典型元素并且可以引起脱硝催化剂的失活。具有优异抗SO₂性能的CuSO₄/TiO₂催化剂被认为是一种有前景的非钒基脱硝催化剂。但是，钾对CuSO₄/TiO₂催化剂的影响仍不清楚。本文研究了钾对CuSO₄/TiO₂催化剂的影响并且与商业V₂O₅-WO₃/TiO₂ (VWTi)催化剂作了比较，采用多种表征方法对催化剂样品进行了表征。钾可以引起CuSO₄/TiO₂和VWTi催化剂的失活，但是CuSO₄/TiO₂催化剂对钾的抵抗能力明显高于商业VWTi催化剂。钾会与CuSO₄/TiO₂催化剂中的CuSO₄发生反应生成CuO和K₂SO₄。CuO的形成会引起催化剂上NO_x转化率和N₂选择性的下降。另外，钾还会与催化剂上的Brønsted酸性位(S-OH)结合从而阻碍NH₃在催化剂表面的吸附。再者，高浓度的钾还会引起催化剂比表面积的下降。值得注意的是，丰富的酸性位和表面吸附氧含量应该是CuSO₄/TiO₂催化剂对钾具有较高抵抗力的原因。本工作的研究结果表明CuSO₄/TiO₂催化剂是一种适用于生物质电厂烟气脱硝的潜在催化剂。

关键词: NH₃-SCR催化剂, 氮氧化物, Br?nsted酸性位, 氧化铜, 生物质电厂

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 NO_x 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 NO_x 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 NO_x 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 Brønsted 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 Brønsted 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.

Key words: NH₃-SCR catalysts, NO_x, Br?nsted acid sites, CuO, biofuel-fired power plants

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), 2206034. doi: 10.3866/PKU.WHXB202206034

Yanke Yu, Mengqiao Geng, Desheng Wei, Chi He. Effect of Potassium on the Performance of a CuSO₄/TiO₂ Catalyst Used in the Selective Catalytic Reduction of NO_x by NH₃[J]. Acta Phys. -Chim. Sin. 2023, 39(4), 2206034. doi: 10.3866/PKU.WHXB202206034

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202206034

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I4/2206034

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Sample	S_BET/(m²∙g⁻¹)	V_p/(cm³∙g⁻¹)	D_p/nm	T_acid/(μmol∙g⁻¹)	O_β/O_t (%)
CuK-0	57.4	0.262	9.12	3673	43.6
CuK-1	56.1	0.259	9.23	2378	36.1
CuK-2	54.6	0.257	9.41	1286	31.2
CuK-4	46.7	0.245	10.49	679	22.9
VWTi	55.5	0.249	8.97	925	19.4
VWTi-K	52.1	0.242	9.29	222	15.1

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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 NO_x by NH₃

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