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化学进展 2009, Vol. 21 Issue (0708): 1626-1635 前一篇   后一篇

• 综述与评论 •

氧载体的氧物种直接氧化甲烷制合成气*

代小平**;余长春   

  1. (中国石油大学(北京) CNPC催化重点实验室   |北京 102249)
  • 收稿日期:2008-07-18 修回日期:2008-10-14 出版日期:2009-08-24 发布日期:2009-06-30
  • 通讯作者: 代小平 E-mail:lngcc@cup.edu.cn; daixpcup@126.com
  • 基金资助:

    国家自然科学基金

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Direct Partial Oxidation of Methane to Synthesis Gas Using Oxygen Carriers in the Absence of Gaseous Oxygen

Dai Xiaoping**|Yu Changchun   

  1. (The Key Laboratory of Catalysis, China National Petroleum Corporation, China University of Petroleum-Beijing, Beijing 102249, China)
  • Received:2008-07-18 Revised:2008-10-14 Online:2009-08-24 Published:2009-06-30
  • Contact: Dai Xiaoping E-mail:lngcc@cup.edu.cn; daixpcup@126.com

甲烷部分氧化制合成气由于合成气中n(H2)/n(CO)接近2，可直接用于甲醇合成或烃类F-T合成等后续工业过程而在国内外受到了广泛的关注。利用氧载体的氧物种在无气相氧下直接选择氧化甲烷制合成气是天然气化工利用的新方法，本文介绍了该方法的基本原理、概念工艺和对氧载体的性能要求，对应用于该方法的铈基复合氧化物的掺杂和助剂对选择氧化甲烷性能的影响、钙钛矿氧化物氧载体的氧空穴、氧物种迁移、结构稳定性及其氧物种反应性能进行了阐述和分析，提出了控制载氧体表面状态是获得高合成气选择性的关键，并对该技术今后的研究重点进行了展望。

关键词： 氧载体, 晶格氧, 选择氧化, 甲烷, 合成气

Much attention has been paid to the reactions of the partial oxidation of methane (POM) to the synthesis gas in heterogeneous catalysis due to synthesis gas with a H2/CO ratio of ca. 2, which is suitable for methanol and Fischer-Tropsch synthesis. Direct partial oxidation of methane to synthesis gas using oxygen carriers in the absence of gaseous oxygen is a new technology for the utilization of natural gas. The process principle, process concept, selection and requirements of oxygen carriers are introduced. We summarize the latest progresses in CeO2-based oxygen carriers about dopants and promoters, and perovskite-based oxygen carriers about oxygen ion vacancy, oxygen migration, structural stability, and performance for direct partial oxidation of methane in the absence of gaseous oxygen. The product distribution for POM using oxygen carrier is determined by surface state, which can be optimized by controlling appropriate amounts of replenished lattice oxygen with gaseous oxygen. Moreover, the major problems and research directions in this area are proposed.

Contents
1 Introduction
2 The principle and process concept for methane oxidation using oxygen carrier
3 The reactivity with methane by selective oxidation using lattice oxygen from ceria-based complex oxides
4 Synthesis gas production using perovskite as oxygen carrier by selective oxidation of methane
4.1 Oxygen defection and oxygen nonstoichiometry
4.2 Oxygen ion migration
4.3 Structural stability in a reducing atmosphere
4.4 Reactivity with methane using perovskite as oxygen carrier
5 Mechanism of methane oxidation using oxygen carrier
6 Conclusions

Key words: oxygen carriers, lattice oxygen, partial oxidation, methane, synthesis gas

中图分类号: 

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