超临界水热合成过渡金属改性铈基催化剂应用于CO-SCR脱硝研究

doi:10.1016/S1872-2067(17)63008-0

催化学报 ›› 2018, Vol. 39 ›› Issue (4): 728-735.DOI: 10.1016/S1872-2067(17)63008-0

超临界水热合成过渡金属改性铈基催化剂应用于CO-SCR脱硝研究

戴晓霞^a, 蒋威宇^a, 王望龙^a, 翁小乐^a,b, 尚媛^a, 薛烨辉^a, 吴忠标^a,b

a 浙江大学环境与资源学院, 污染环境修复与生态健康教育部重点实验室, 浙江杭州 310058;
b 浙江省工业锅炉炉窑烟气污染控制工程技术研究中心, 浙江杭州 310058

收稿日期:2017-11-29 修回日期:2017-12-26 出版日期:2018-04-18 发布日期:2018-04-08
通讯作者: 翁小乐
基金资助:
国家重点研发计划（2016YFC0204100）；国家自然科学基金（51478418）；浙江省重点科技创新团队（2013TD07）.

Supercritical water syntheses of transition metal-doped CeO₂nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study

Xiaoxia Dai^a, Weiyu Jiang^a, Wanglong Wang^a, Xiaole Weng^a,b, Yuan Shang^a, Yehui Xue^a, Zhongbiao Wu^a,b

a Ministry of Education Key Laboratory of Environment Remediation and Ecological Health, College of Environmental and Resource and Sciences, Zhejiang University, Hangzhou 310058, Zhejiang, China;
b Zhejiang Provincial Engineering Research Centre of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310058, Zhejiang, China

Received:2017-11-29 Revised:2017-12-26 Online:2018-04-18 Published:2018-04-08
Contact: 10.1016/S1872-2067(17)63008-0
Supported by:
This work was supported by the National Key Research & Development Program of China (2016YFC0204100), National Natural Science Foundation of China (51478418),, and the Program for Zhejiang Leading Team of S&T Innovation (2013TD07).

摘要/Abstract

摘要：

氮氧化物（NO_x）作为煤炭燃烧过程主要污染物之一，可直接或间接引起如光化学烟雾、酸沉降、平流层臭氧损耗和全球气候变化等大气环境污染问题.NO_x的选择性催化还原技术（SCR）被认为是目前处理固定源NO_x的最有效方法之一.由于燃煤工业锅炉烟气中还有1%~3%的CO，远高于NO_x的0.02%~0.04%，因此，以CO为还原剂进行CO-SCR脱硝具有现实意义，它可在反应过程中同时消除CO和NO两种有害气体，但对催化剂的活性及抗毒性提出更高要求.CeO₂作为一种常用的稀土材料，因具有良好的储放氧能力而广泛应用于SCR反应中.过渡金属改性可进一步改善CeO₂的物化性能，从而可能达到CO-SCR的应用要求.
本文利用超临界水热技术合成了MO_x-CeO₂（M=Co，Fe，Cu）固溶体催化剂，并利用X射线衍射（XRD），氢气程序升温还原（H₂-TPR），傅里叶变换原位红外（DRFTIR）等探究了催化剂在CO-SCR反应中的催化活性与作用机制.
CO-SCR反应活性测试表明，CuO-CeO₂催化剂活性明显优于FeO_x-CeO₂和CoO_x-CeO₂催化剂，在126℃ NO去除率即可达到90%；其N₂选择性也可在179℃时达到90%.为了进一步探究MO_x-CeO₂（M=Co，Fe，Cu）催化剂的CO-SCR反应途径，本文随后进行了系列原位DRFTIR实验，发现NO在三种催化剂表面均能被高效吸附，其吸附态中间产物主要为双齿硝酸根，桥式硝酸根，桥式硝基和亚硝酰基等.另外，在CuO-CeO₂催化剂表面还存有螯合硝基和单齿硝酸根.CO在催化剂表面主要以CO_x，碳酸根和羧酸根等形式存在.值得注意的是，在CuO-CeO₂表面，CO因吸附于Cu⁺而形成Cu⁺-CO，在2100 cm^-1左右形成明显的特征峰.当催化剂表面吸附CO至饱和后再通入NO发现，CO的吸附特征峰逐渐被NO的特征吸附峰取代；而当NO被吸附至饱和后再通入CO，NO的特征峰则不出现明显变化.这表明NO和CO在催化剂表面存在竞争吸附，NO可能优先于CO吸附在催化剂表面.当NO和CO同时通入红外反应仓时发现，在CoO_x-CeO₂和FeO_x-CeO₂催化剂表面只观察到NO的吸附峰，而在CuO-CeO₂催化剂表面观察到Cu⁺-CO的特征峰，说明在CO-SCR反应过程中，CO可以在Cu⁺表面被有效吸附，其与吸附于CeO₂表面的NO物种反应生成N₂和CO₂，遵循Langmuir-Hinshelwood反应机理.而在CoO_x-CeO₂和FeO_x-CeO₂催化剂表面，因NO的竞争吸附，使得二者主要遵循Eley-Rideal反应机理.

关键词: 超临界水, 氮氧化物, CO, 选择催化还原, 傅里叶变换原位红外光谱, CeO₂

Abstract:

In the present study, we synthesized CeO₂ catalysts doped with various transition metals (M=Co, Fe, or Cu) using a supercritical water hydrothermal route, which led to the incorporation of the metal ions in the CeO₂ lattice, forming solid solutions. The catalysts were then used for the selective catalytic reduction (SCR) of NO by CO. The Cu-doped catalyst exhibited the highest SCR activity; it had a T₅₀ (i.e., 50% NO conversion) of only 83℃ and a T₉₀ (i.e., 90% NO conversion) of 126℃. Such an activity was also higher than in many state-of-the-art catalysts. In situ diffuse reflectance Fourier transform infrared spectroscopy suggested that the MO_x-CeO₂ catalysts (M=Co and Fe) mainly followed an Eley-Rideal reaction mechanism for CO-SCR. In contrast, a Langmuir-Hinshelwood SCR reaction mechanism occurred in CuO-CeO₂ owing to the presence of Cu⁺ species, which ensured effective adsorption of CO. This explains why CuO-CeO₂ exhibited the highest activity with regard to the SCR of NO by CO.

Key words: Supercritical water, Nitrogen oxides, CO, Selective catalytic reduction, Diffuse reflectance Fourier transform infrared spectroscopy, CeO₂

戴晓霞, 蒋威宇, 王望龙, 翁小乐, 尚媛, 薛烨辉, 吴忠标. 超临界水热合成过渡金属改性铈基催化剂应用于CO-SCR脱硝研究[J]. 催化学报, 2018, 39(4): 728-735.

Xiaoxia Dai, Weiyu Jiang, Wanglong Wang, Xiaole Weng, Yuan Shang, Yehui Xue, Zhongbiao Wu. Supercritical water syntheses of transition metal-doped CeO₂nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study[J]. Chinese Journal of Catalysis, 2018, 39(4): 728-735.

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超临界水热合成过渡金属改性铈基催化剂应用于CO-SCR脱硝研究

Supercritical water syntheses of transition metal-doped CeO₂nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study

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超临界水热合成过渡金属改性铈基催化剂应用于CO-SCR脱硝研究

Supercritical water syntheses of transition metal-doped CeO2nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study

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Supercritical water syntheses of transition metal-doped CeO₂nano-catalysts for selective catalytic reduction of NO by CO: An in situ diffuse reflectance Fourier transform infrared spectroscopy study