氯化氢对锑铈基催化剂在NH3-SCR反应中的促进作用及其机理研究

doi:10.1016/S1872-2067(24)60155-5

催化学报 ›› 2025, Vol. 68: 376-385.DOI: 10.1016/S1872-2067(24)60155-5

氯化氢对锑铈基催化剂在NH₃-SCR反应中的促进作用及其机理研究

刘彩霞^a, 黄朝俊^b, 范柏余^c, 张岩^a, 房莉静^a, 王雨禾^a, 刘庆岭^a^,^*(), 王卫超^d, 陈延国^e, 张亚伟^e, 刘建成^f, 董芳^b, 张子印^g

^a天津大学环境科学与工程学院, 室内空气环境质量控制重点实验室, 先进内燃机全国重点实验室, 天津 300350
^b招商局海洋装备研究院有限公司, 广东深圳 518000
^c中国汽车技术研究中心有限公司, 中国汽车战略与政策研究中心, 天津 300300
^d南开大学环境科学与工程学院, 天津市环境修复与污染防治重点实验室, 天津 300350
^e天津泰达股份有限公司, 天津 300350
^f天津大学建筑工程学院, 天津 300072
^g廊坊市北辰创业树脂材料股份有限公司, 大气多污染物控制及治理新材料工程研究中心, 河北省树脂新材料技术创新中心, 河北廊坊 065000

收稿日期:2024-09-03 接受日期:2024-09-24 出版日期:2025-01-18 发布日期:2025-01-02
通讯作者: * 电子信箱: liuql@tju.edu.cn (刘庆岭).
基金资助:
国家重点研发计划项目(2022YFB3504100);国家重点研发计划项目(2022YFB3504102);河北省重大科技成果转化基金支持项目(2021004012A);河北省重大科技成果转化基金支持项目(22281401Z);国家自然科学基金(22276133);国家自然科学基金(22076136)

An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH₃-SCR reaction

Caixia Liu^a, Chaojun Huang^b, Baiyu Fan^c, Yan Zhang^a, Lijing Fang^a, Yuhe Wang^a, Qingling Liu^a^,^*(), Weichao Wang^d, Yanguo Chen^e, Yawei Zhang^e, Jiancheng Liu^f, Fang Dong^b, Ziyin Zhang^g

^aTianjin Key Laboratory of Indoor Air Environmental Quality Control, School of Environmental Science and Technology and State Key Laboratory of Engines, Tianjin University, Tianjin 300350, China
^bChina Merchants Marine and Offshore Research Institute CO., LTD., Shenzhen 518000, Guangdong, China
^cChina Automotive Strategy and Policy Research Center, China Automotive Technology and Research Center Co., Ltd, Tianjin 300300, China
^dTianjin Key Laboratory of Environmental Remediation & Pollution Control, MOE Key Laboratory of Pollution Processes and Environmental Criteria, College of Environmental Science and Engineering, Nankai University, Tianjin 300350, China
^eTianjin TEDA Co., Ltd., Tianjin 300350, China
^fSchool of Civil Engineering, Tianjin University, Tianjin 300072, China
^gNew Catalytic Materials Engineering Research Center for Air Pollutant Control, Hebei province New Resin Material Technology Innovation Center, Langfang City Beichen Entrepreneurship Resin Materials Incorporated Co., Ltd., Langfang 065000, Hebei, China

Received:2024-09-03 Accepted:2024-09-24 Online:2025-01-18 Published:2025-01-02
Contact: * E-mail: liuql@tju.edu.cn (Q. Liu).
Supported by:
National Key R&D Program of China(2022YFB3504100);National Key R&D Program of China(2022YFB3504102);Hebei Province Major Scientific and Technological Achievement Transformation Fund(2021004012A);Hebei Province Major Scientific and Technological Achievement Transformation Fund(22281401Z);National Natural Science Foundation of China(22276133);National Natural Science Foundation of China(22076136)

摘要/Abstract

摘要：

经济的快速发展和城市化进程的加快导致生活垃圾急剧增加. 为应对该挑战, 垃圾焚烧技术因其显著的减量效果而被广泛应用. 然而, 垃圾焚烧技术会产生氮氧化物等二次污染物, 这些污染物需要进行有效处理. 氨选择性催化还原(NH₃-SCR)技术是目前应用最为广泛的脱硝技术, 但垃圾焚烧产生的酸性气体HCl会导致催化剂失活. 因此, 深入研究HCl对NH₃-SCR反应机理的影响, 对于设计高效脱硝催化剂具有重要意义. 本文制备出SbCe催化剂, 并对其进行性能研究, 旨在开发应用于垃圾焚烧发电厂低温脱硝活性好、抗酸性气体和水中毒能力优异的催化剂.
本文设计制备了一种双金属复合氧化物SbCeO_x催化剂, 并研究NH₃-SCR活性, 以评估HCl对反应机理的影响. 结合表征技术和密度泛函理论(DFT)计算, 探讨了催化剂的理化性质与其催化性能之间的关系, 深入研究了HCl对SbCeO_x催化剂NH₃-SCR反应机理的影响. 结果表明, 在HCl毒化过程中, HCl与吸附氧和表面晶格氧发生反应, 导致HCl在催化剂表面诱导生成的氯酸盐物种, 显著提高了催化剂的低温活性, 在155 °C时NO转化率提高了30%. 同时, 高温下N₂选择性也得到明显改善, 在405 °C时NO转化率提高了17%. 研究结果和DFT结果均证实, 氯酸盐物种在Ce位点形成, 该过程中晶格氧被消耗, 促进了氧空位的产生, 提高了催化剂表面氧的交换能力. 此外, 氯酸盐物种还增强了NH₃在Ce位点的吸附, 促进了Sb-OH的形成, 并减少了OH在这些位点的竞争性吸附. 吸附的NH₃随后与残余的晶格氧反应, 在Ce位点上形成酰胺(-NH₂)中间体, 同时在Sb位点上产生额外的氧空位和羟基. 酰胺中间体进一步与NO反应形成关键的[NH₂NO]中间体, 这些中间体最终分解生成N₂. 值得关注的是, 与未进行HCl气体毒化相比, 氯酸盐物种的存在增强了NH₃的吸附和活化, 这对于后续催化反应至关重要. 实验结果表明, HCl处理促进了Sb³⁺-OH物种的生成, 气态NO也可以被氧化生成NO₂. 生成的NO₂随后与Brönsted酸位上的NH₄⁺物种反应, 它能够与NH₃发生反应生成Sb³⁺-O-NH₄⁺, 提高催化剂表面Brönsted酸位点的酸性, 促进Brönsted酸位点配位NH₄⁺物种与NO₂反应生成N₂和H₂O, 从而显著提升了SbCe催化剂的N₂选择性. 该发现与原位红外光谱和NH₃程序升温脱附结果一致, 进一步证实了Brönsted酸位的酸度是NH₃吸附的主要驱动力.
综上, 本研究揭示了HCl对NH₃-SCR反应机理的影响, 为设计抗HCl中毒的高效脱硝催化剂提供了新思路. 未来研究可进一步探索不同酸性气体对催化剂性能的影响, 开发更加高效、稳定的脱硝催化剂, 为垃圾焚烧电厂的氮氧化物控制提供技术支持.

关键词: NH₃选择性催化还原, 氯酸盐物种, SbCe催化剂, 密度泛函理论, 氯化氢

Abstract:

Understanding the influence of HCl on the NH₃-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts. The formation of chlorate species on the surface of the synthesized SbCeO_x catalyst, induced by HCl, significantly enhances low-temperature activity, as evidenced by a 30% increase in NO conversion at 155 °C. Furthermore, it improves N₂ selectivity at high temperatures, with a notable 17% increase observed at 405 °C. Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites. This formation facilitates the creation of oxygen vacancies, boosting the oxygen exchange capacity. It also increases NH₃ adsorption at the Ce sites, promotes the formation of Sb-OH, and reduces competitive OH adsorption on these sites. Notably, compared with the reaction mechanism without HCl, the presence of chlorate species enhances NH₃ adsorption and activation, which is vital for subsequent catalytic reactions.

Key words: NH₃-selective catalytic reduction, Chlorate species, SbCeO_x catalyst, Density functional theory, HCl

刘彩霞, 黄朝俊, 范柏余, 张岩, 房莉静, 王雨禾, 刘庆岭, 王卫超, 陈延国, 张亚伟, 刘建成, 董芳, 张子印. 氯化氢对锑铈基催化剂在NH₃-SCR反应中的促进作用及其机理研究[J]. 催化学报, 2025, 68: 376-385.

Caixia Liu, Chaojun Huang, Baiyu Fan, Yan Zhang, Lijing Fang, Yuhe Wang, Qingling Liu, Weichao Wang, Yanguo Chen, Yawei Zhang, Jiancheng Liu, Fang Dong, Ziyin Zhang. An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH₃-SCR reaction[J]. Chinese Journal of Catalysis, 2025, 68: 376-385.

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Fig. 1. SCR performance of the SbCe catalyst before and after HCl treatment. SCR activity (a) and N2 selectivity (b) of catalysts with different Sb:Ce ratios. SCR activity (c) and N2 selectivity (d) of Sb:Ce = 1.3:1 catalyst after HCl treatment.

Fig. 2. (a) XRD patterns of the SbCe catalyst at three distinct temperatures(180, 280, and 380 °C) before and after HCl treatment. (b) SbCe-280 element mappings. SbCe-ori (c-e) and SbCe-280 (f-h) TEM pictures.

Table 1 The porosity results of SbCe catalysts with or without HCl treatment.

Sample	BET specific surface area (m²/g)	Pore volume (cm³/g)	Average pore size (nm)
SbCe-ori	49.8	0.05	5.10
SbCe-180	55.6	0.07	4.92
SbCe-280	51.4	0.05	4.11
SbCe-380	52.2	0.09	6.33

Fig. 3. XPS spectrum of SbCe catalyst before and after HCl treatment at different temperatures: Cl 2p (a), O 1s (b), Ce 3d (c), and Sb 3d (d).

Fig. 4. NH3-TPD profiles (a) and H2-TPR profiles (b) of the SbCe catalyst before and after HCl treatment at different temperatures.

Fig. 5. DRIFTS experimental results of the NH3-SCR reaction at different temperatures for SbCe-ori and SbCe-280 catalysts. (a) SbCe-ori catalyst. (b) SbCe-280 catalyst. Reaction gas flow rate: 100 mL/min; Reaction conditions: [NO] = [NH3] = 500 ppm, [O2] = 10%, N2 balance. GHSV: 60000 h-1.

Fig. 6. The optimized configurations of CeO2 and SbCe catalysts and the PDOS diagram of O 2p orbitals. (a) Optimized model structure of the CeO2 catalyst. (b) Optimized model structure of the SbCe catalyst. (c) Structure of CeO2 catalyst after forming oxygen vacancies. (d) Structure of the SbCe catalyst after forming oxygen vacancies. (e) Structure of the SbCe catalyst after adsorbing HCl. (f) Structure of the SbCe catalyst with oxygen vacancies formed after HCl adsorption. (g) Structure of the SbCe catalyst after adsorbing ClO3-. (h) Structure of the SbCe catalysts with oxygen vacancies formed after ClO?- adsorption. (i) PDOS diagram of O 2p orbitals.

Fig. 7. Adsorption configuration of NH3 and OH on the SbCe catalyst. (a) Structure of the SbCe catalyst adsorbing NH3 at the Ce site. (b) Structure of the SbCe catalyst adsorbing NH3 at the Sb site. (c) Structure of the SbCe-ClO3 catalyst adsorbing NH3 at Ce site. (d) Structure of the SbCe-ClO3 catalyst adsorbing NH? at the Sb site. (e) Structure of the SbCe catalyst adsorbing OH at the Ce site. (f) Structure of the SbCe catalyst adsorbing OH at the Sb site. (g) Structure of the SbCe-ClO3 catalyst adsorbing OH at the Ce site. (h) Structure of the SbCe-ClO3 catalyst of adsorbing OH at the Sb site.

Scheme 1. Schematic illustration of activity and selectivity promoted over the SbCe catalyst.

参考文献

[1]	N. R. Jaegers, J. K. Lai, Y. He, E. Walter, D. A. Dixon, M. Vasiliu, Y. Chen, C. Wang, M. Y. Hu, K. T. Mueller, I. E. Wachs, Y. Wang, J. Z. Hu, Angew. Chem. Int. Ed., 2019, 58, 12609-12616.
[2]	F. Göltl, P. Sautet, I. Hermans, Angew. Chem. Int. Ed., 2015, 54, 7799-7804.
[3]	X. Mou, B. Zhang, Y. Li, L. Yao, X. Wei, D. S. Su, W. Shen, Angew. Chem. Int. Ed., 2012, 51, 2989-2993.
[4]	P. G. Smirniotis, D. A. Peña, B. S. Uphade, Angew. Chem. Int. Ed., 2001, 40, 2479-2482.
[5]	P. Forzatti, I. Nova, E. Tronconi, Angew. Chem. Int. Ed., 2009, 48, 8366-8368.
[6]	Y. Jiang, M. Lu, S. Liu, C. Bao, G. Liang, C. Lai, W. Shi, S. Ma, RSC Adv., 2018, 8, 17677-17684.
[7]	N. Yang, R. Guo, W. Pan, Q. Chen, Q. Wang, C. Lu, S. Wang, Appl. Surf. Sci., 2016, 378, 513-518.
[8]	A. Lanza, L. Zheng, R. Matarrese, L. Lietti, J. D. Grunwaldt, S. A. Clave, J. Collier, A. Beretta, Chem. Eng. J., 2021, 416, 128933.
[9]	H. Chang, J. Li, W. Su, Y. Shao, J. Hao, Chem. Commun., 2014, 50, 10031-10034.
[10]	L. Lisi, G. Lasorella, S. Malloggi, G. Russo, Appl. Catal. B, 2004, 50, 251-258.
[11]	Q. Wang, F. Lin, J. Zhou, J. Zhang, J. Jin, Appl. Catal. A, 2020, 605, 117801.
[12]	F. Gao, X. Tang, H. Yi, S. Zhao, J. Wang, T. Gu, Appl. Surf. Sci., 2019, 466, 411-424.
[13]	S. Martins, J. B. Fernandes, S. C. Mojumdar, J. Therm. Anal. Calori., 2015, 119, 831-835.
[14]	J. Liu, G. Li, Y. Zhang, X. Liu, Y. Wang, Y. Li, Appl. Surf. Sci., 2017, 401, 7-16.
[15]	Y. Hao, Y. Wang, T. Zhang, Y. Liu, Q. Y. Fan, Y. Jiang, Y. Gao, Z. Mao, X. Gu, S. Zeng, Appl. Catal. B, 2024, 340, 123254.
[16]	X. Jia, H. Liu, Y. Zhang, W. Chen, Q. Tong, G. Piao, C. Sun, L. Dong, J. Colloid Interface Sci., 2021, 581, 427-441.
[17]	H. Xu, Y. Wang, Y. Cao, Z. Fang, T. Lin, M. Gong, Y. Chen, Chem. Eng. J., 2014, 240, 62-73.
[18]	L. He, Y. Zhang, Y. Zang, C. Liu, W. Wang, R. Han, N. Ji, S. Zhang, Q. Liu, ACS Catal., 2021, 11, 14224-14236.
[19]	X. Liu, K. Zhou, L. Wang, B. Wang, Y. Li, J. Am. Chem. Soc., 2009, 131, 3140-3141.
[20]	M. S. Maqbool, A. K. Pullur, H. P. Ha, Appl. Catal. B, 2014, 152-153, 28-37.
[21]	H. Wang, Z. Qu, H. Xie, N. Maeda, L. Miao, Z. Wang, J. Catal., 2016, 338, 56-67.
[22]	Z. Hao, Z. Shen, Y. Li, H. Wang, L. Zheng, R. Wang, G. Liu, S. Zhan, Angew. Chem. Int. Ed., 2019, 58, 6351-6356.
[23]	R. Guo, X. Sun, J. Liu, W. Pan, M. Li, S. Liu, P. Sun, S. Liu,, Appl. Catal. A, 2018, 558, 1-8.
[24]	C. Xu, J. Liu, Z. Zhao, F. Yu, K. Cheng, Y. Wei, A. Duan, G. Jiang, J. Environ. Sci., 2015, 31, 74-80.
[25]	A. Marberger, D. Ferri, M. Elsener, O. Kröcher, Angew. Chem. Int. Ed., 2016, 55, 11989-11994.
[26]	Z. Wang, R. Guo, X. Shi, W. Pan, J. Liu, X. Sun, S. Liu, X. Liu, H. Qin, Appl. Surf. Sci., 2019, 475, 334-341.
[27]	Z. Wang, X. Li, R. Shi, React. Kinet. Mech. Catal., 2019, 127, 437-447.
[28]	H. Chitsazi, N. Zhang, L. Li, X. Liu, R. Wu, J. He, L. Song, H. He, J. Rare Earths, 2021, 39, 526-531.
[29]	X. Zhao, S. Ma, Z. Li, F. Yuan, X. Niu, Y. Zhu, Chem. Eng. J., 2020, 392, 123801.

氯化氢对锑铈基催化剂在NH₃-SCR反应中的促进作用及其机理研究

An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH₃-SCR reaction

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