化工进展 ›› 2015, Vol. 34 ›› Issue (12): 4248-4253.DOI: 10.16085/j.issn.1000-6613.2015.12.018

• 工业催化 • 上一篇    下一篇

富铈Ce1-xLaxO2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. 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
  • 收稿日期:2015-03-06 修回日期:2015-04-23 出版日期:2015-12-05 发布日期:2015-12-05
  • 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。

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

XU Shu1,2, FEI Zhaoyang1,2, CHEN Xian2, TANG Jihai2, CUI Mifen2, QIAO Xu1,2   

  1. 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

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Ce1-xLaxO2(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:Ce1-xLaxO2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。Ce1-xLaxO2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Ce1-xLaxO2(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,Ce0.8La0.2O2催化剂上氯甲烷选择性最高为52%。在体相氧物种更活泼的Ce0.7La0.3O2和Ce0.5La0.5O2上产物中CO的选择性显著上升,Ce0.5La0.5O2催化剂上CO选择性高达48%。稳定性测试表明Ce0.8La0.2O2催化剂具有良好的稳定性。

关键词: 甲烷, 活化, 氧化, Ce1-xLaxO2, 氧氯化, 氯甲烷

Abstract: A series of Ce1-xLaxO2(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 Ce1-xLaxO2 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 Ce1-xLaxO2(x<0.3) and the highest selectivity of chloromethane (52%) could be obtained over Ce0.8La0.2O2. A significant increase of CO selectivity was found over Ce0.7La0.3O2 and Ce0.5La0.5O2 as they had more active bulk oxygen species,and Ce0.5La0.5O2 showed the highest selectivity of CO (48%). The long-term stability test showed that Ce0.8La0.2O2 catalyst had a good stability.

Key words: methane, activation, oxidation, Ce1-xLaxO2, oxy-chlorination, methyl chloride

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