Catalytic performance of Ce-rich Ce1-xLaxO2 oxides in CH4 oxy-chlorination

doi:10.16085/j.issn.1000-6613.2015.12.018

Chemical Industry and Engineering Progree ›› 2015, Vol. 34 ›› Issue (12): 4248-4253.DOI: 10.16085/j.issn.1000-6613.2015.12.018

• Industrial catalysis • Previous Articles Next Articles

Catalytic performance of Ce-rich Ce_1-xLa_xO₂ oxides in CH₄ oxy-chlorination

XU Shu^1,2, FEI Zhaoyang^1,2, CHEN Xian², TANG Jihai², CUI Mifen², QIAO Xu^1,2

1 State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech. University, Nanjing 210009, Jiangsu, China;
2 College of Chemistry and Chemical Engineering, Nanjing Tech. University, Nanjing 210009, Jiangsu, China

Received:2015-03-06 Revised:2015-04-23 Online:2015-12-05 Published:2015-12-05

富铈Ce_1-xLa_xO₂催化甲烷氧氯化性能

徐术^1,2, 费兆阳^1,2, 陈献², 汤吉海², 崔咪芬², 乔旭^1,2

1 南京工业大学材料化学工程国家重点实验室, 江苏南京 210009;
2 南京工业大学化学化工学院, 江苏南京 210009

通讯作者: 费兆阳,博士。E-mailzhaoyangfei@njtech.edu.cn。
作者简介:徐术(1989—),男,硕士研究生。
基金资助:
国家科技支撑计划(2011BAE18B01)及国家自然科学基金青年基金(21306089)项目。

Abstract

Abstract: A series of Ce_1-xLa_xO₂(x≤0.5) catalysts were prepared by ammonia co-precipitation method and characterized by XRD,N₂ adsorption-desorption,SEM,Raman,H₂-TPR and OSC. Then their catalytic performances in CH₄ oxy-chlorination to chloromethane were investigated. The results showed that the redox properties of Ce_1-xLa_xO₂ changed significantly with the change of the lanthanum content,and there should be a strong link between this change and the conversion and product distribution. More specificly,the surface oxygen species had a remarkable influence on the activities of the catalysts,while advanced oxidation of the generated methane chloride was easily induced by bulk oxygen species. Chloromethane was the main product over Ce_1-xLa_xO₂(x<0.3) and the highest selectivity of chloromethane (52%) could be obtained over Ce_0.8La_0.2O₂. A significant increase of CO selectivity was found over Ce_0.7La_0.3O₂ and Ce_0.5La_0.5O₂ as they had more active bulk oxygen species,and Ce_0.5La_0.5O₂ showed the highest selectivity of CO (48%). The long-term stability test showed that Ce_0.8La_0.2O₂ catalyst had a good stability.

Key words: methane, activation, oxidation, Ce_1-xLa_xO₂, oxy-chlorination, methyl chloride

摘要： 以硝酸铈、硝酸镧为前体,用氨水共沉淀法制备了一系列Ce_1-xLa_xO₂(x≤0.5)催化剂,利用XRD、N₂吸附-脱附、SEM、Raman、H₂-TPR和OSC对催化剂的物理化学性质进行了表征,并考察其在甲烷氧氯化反应中的催化性能。结果表明:Ce_1-xLa_xO₂催化剂的氧化还原性质随着镧含量的变化发生显著改变,并且这一性质的变化与反应的转化率及产物分布具有较强的联系。Ce_1-xLa_xO₂表面氧物种的活泼性对催化剂活性影响显著,而体相氧物种容易将生成的甲烷氯化物深度氧化。在Ce_1-xLa_xO₂(x<0.3)催化剂上表面氧物种起主导作用,氯甲烷为主要反应产物,Ce_0.8La_0.2O₂催化剂上氯甲烷选择性最高为52%。在体相氧物种更活泼的Ce_0.7La_0.3O₂和Ce_0.5La_0.5O₂上产物中CO的选择性显著上升,Ce_0.5La_0.5O₂催化剂上CO选择性高达48%。稳定性测试表明Ce_0.8La_0.2O₂催化剂具有良好的稳定性。

关键词: 甲烷, 活化, 氧化, Ce_1-xLa_xO₂, 氧氯化, 氯甲烷

CLC Number:

O643

XU Shu, FEI Zhaoyang, CHEN Xian, TANG Jihai, CUI Mifen, QIAO Xu. Catalytic performance of Ce-rich Ce_1-xLa_xO₂ oxides in CH₄ oxy-chlorination[J]. Chemical Industry and Engineering Progree, 2015, 34(12): 4248-4253.

徐术, 费兆阳, 陈献, 汤吉海, 崔咪芬, 乔旭. 富铈Ce_1-xLa_xO₂催化甲烷氧氯化性能[J]. 化工进展, 2015, 34(12): 4248-4253.

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Catalytic performance of Ce-rich Ce_1-xLa_xO₂ oxides in CH₄ oxy-chlorination

富铈Ce_1-xLa_xO₂催化甲烷氧氯化性能

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