Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化

doi:10.1016/S1872-2067(14)60270-9

催化学报 ›› 2015, Vol. 36 ›› Issue (3): 290-298.DOI: 10.1016/S1872-2067(14)60270-9

Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化

尚鸿燕^a, 王云^b, 崔亚娟^c, 方瑞梅^a, 胡伟^a, 龚茂初^d, 陈耀强^a,c,d

a 四川大学化学工程学院, 四川成都610065;
b 四川省中自尾气净化有限公司, 四川成都611731;
c 四川大学建筑与环境学院, 四川成都610065;
d 四川大学化学学院, 教育部绿色化学与技术重点实验室, 四川成都610064

收稿日期:2014-10-19 修回日期:2014-12-12 出版日期:2015-02-14 发布日期:2015-02-14
通讯作者: 陈耀强
基金资助:
国家自然科学基金(21173153); 四川省科技厅科技支撑项目(2011GZ0035).

Catalytic performance of Pt-Rh/CeZrYLa+LaAl with stoichiometric natural gas vehicles emissions

Hongyan Shang^a, Yun Wang^b, Yajuan Cui^c, Ruimei Fang^a, Wei Hu^a, Maochu Gong^d, Yaoqiang Chen^a,c,d

a College of Chemical Engineering, Sichuan University, Chengdu 610065, Sichun, China;
b Sichuan Zhongzi Exhaust Gas Cleaning Co., Ltd., Chengdu 611731, Sichuan, China;
c College of Architecture and Environment, Sichuan University, Chengdu 610065, Sichuan, China;
d Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, Sichun, China

Received:2014-10-19 Revised:2014-12-12 Online:2015-02-14 Published:2015-02-14
Supported by:
This work was supported by the National Natural Science Foundation of China (21173153) and the Science and Technology Department of Science and Technology Support Project of Sichuan Province, China (2011GZ0035).

摘要/Abstract

摘要：

采用共沉淀法制备了CeZrYLa+LaAl纳米复合载体, 以三种方法制备了一系列Pt-Rh/CeZrYLa+LaAl催化剂. 对所制样品进行了N₂吸附-脱附、粉末X射线衍射、X射线光电子能谱和H₂程序升温还原的表征. 并考察了三种方法所制得催化剂的理论空燃比天然气汽车尾气净化性能. 结果表明, 三个催化剂的活性顺序为Cat3 ≈ Cat2 > Cat1, 其中Cat3具有最低的CO和NO起燃温度(T₅₀), 分别为114 ℃和149 ℃, 最低的CH₄和CO完全转化温度(T₉₀), 分别为398 ℃和179 ℃, 以及最佳的CH₄和CO温度特性, ΔT (T₉₀-T₅₀)值分别为34 ℃和65 ℃. Cat2具有最低的CH₄起燃温度(342 ℃)和最低的NO完全转化温度(174 ℃). Cat1具有最差的转化活性, 说明物理混合法制备的催化剂(Cat3和Cat2)性能优于共浸渍法制备的催化剂(Cat1). 这是由于物理混合法制备的催化剂, Pt和Rh均匀分散在载体表面, 两者物理接触共同参与CH₄/CO/NO三种污染物的转化. 相反, 共浸渍法制备的催化剂, Pt和Rh之间存在较强的相互作用, 改变了Pt的电子状态, 而且形成了表面Pt富集的Pt-Rh双金属颗粒覆盖了Rh活性位, 从而降低催化活性; 同时, 对于通过物理混合法并进一步添加助剂所制备的Cat3, XRD结果显示助剂Zr⁴⁺进入了铈锆固溶体晶格, 产生晶格缺陷; XPS结果显示Cat3具有最高的Ce³+/Ce比例. 这些都有利于提高催化剂的氧流动性, 从而提高催化剂活性并拓宽空燃比窗口.

关键词: 铂-铑, 纳米复合CeZrYLa+LaAl, 镧-锆-钡助剂, 理论空燃比天然气汽车, 尾气净化

Abstract:

The composite support CeZrYLa+LaAl was prepared by a co-precipitation method, and Pt-Rh bimetallic catalysts were fabricated on this support using different preparation procedures. The catalytic activities of these materials were tested in a gas mixture simulating the exhaust from a stoichiometric natural gas vehicle. The as-prepared catalysts were also characterized by X-ray photoelectron spectroscopy, X-ray diffraction, N₂ adsorption-desorption and H₂-temperature-programmed reduction. It was found that the order of activities for CH₄, CO and NO conversion was Cat3 ≈ Cat2 > Cat1, where Cat3 had the lowest light-off temperature (T₅₀) for CO (114 ℃) and NO (149 ℃), the lowest complete conversion temperature (T₉₀) for CH₄ (398 ℃) and CO (179 ℃), and the lowest ΔT (T₉₀-T₅₀) for CH₄ (34 ℃) and CO (65 ℃). Cat2 showed the lowest T₅₀ for CH₄ (342 ℃), the lowest T₉₀ for NO (174 ℃), and the lowest ΔT for NO (17 ℃). Cat1 had the highest T₅₀ and T₉₀ and the largest ΔT out of all three catalysts. Indicating that Pt-Rh bimetallic catalysts (Cat2 and Cat3) prepared by physically mixing Pt and Rh powders exhibited much better catalytic activity than those (Cat1) prepared by co-impregnation, since homogeneous Pt and Rh sites made a significant contribution to CH₄/CO/NO conversions. In contrast, strong Pt-Rh interactions in the co-impregnation materials affected the oxidation states of Pt, and the Pt-enriched surface blocked active Rh sites. Moreover, Cat3 was prepared by adding additives (La³⁺, Zr⁴⁺ and Ba²⁺) into the physically mixed Pt-Rh catalysts. XRD results demonstrated that the additive cation (Zr⁴⁺) was incorporated into the CeO₂-ZrO₂ lattice, thus creating a higher concentration of defects and improving the O₂-mobility. XPS results showed that the Cat3 had the highest Ce³⁺/Ce ratio, suggesting the presence of a significant quantity of oxygen vacancies and cerium in the Ce³⁺ state. All of these further promoted the three-way catalytic activity and widened the air-to-fuel working-window.

Key words: Platium-rhodium, Nanocomposite CeZrYLa+LaAl, La-Zr-Ba additive, Stoichiometric natural gas vehicle, Exhaust purification

尚鸿燕, 王云, 崔亚娟, 方瑞梅, 胡伟, 龚茂初, 陈耀强. Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化[J]. 催化学报, 2015, 36(3): 290-298.

Hongyan Shang, Yun Wang, Yajuan Cui, Ruimei Fang, Wei Hu, Maochu Gong, Yaoqiang Chen. Catalytic performance of Pt-Rh/CeZrYLa+LaAl with stoichiometric natural gas vehicles emissions[J]. Chinese Journal of Catalysis, 2015, 36(3): 290-298.

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Pt-Rh/CeZrYLa+LaAl催化剂用于理论空燃比天然气汽车尾气净化

Catalytic performance of Pt-Rh/CeZrYLa+LaAl with stoichiometric natural gas vehicles emissions

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