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在VPO催化剂上丁烷选择氧化的质谱研究

陈标华a; 黄晓峰a; 李成岳a; 梁日忠a; 赵邦蓉b   

  1. a The Key Lab of Science and Technology of Controllable Chemical Reactions, Beijing
    University of Chemical Technology, Beijing 100029, China
    b College of Material Science and Engineering, Beijing University of Chemical Technology,
    Beijing 100029, China
  • 收稿日期:1900-01-01 修回日期:1900-01-01 出版日期:2002-04-28 发布日期:2002-04-28
  • 通讯作者: 陈标华

Mass Spectrometric Studies of Selective Oxidation of n-Butane over a Vanadium Phosphorus
Oxide Catalyst

CHEN Biaohuaa; HUANG Xiaofenga; LI Chengyuea; LIANG Rizhonga; ZHAO Bangrongb   

  1. a The Key Lab of Science and Technology of Controllable Chemical Reactions, Beijing
    University of Chemical Technology, Beijing 100029, China
    b College of Material Science and Engineering, Beijing University of Chemical Technology,
    Beijing 100029, China
  • Received:1900-01-01 Revised:1900-01-01 Online:2002-04-28 Published:2002-04-28
  • Contact: CHEN Biaohua

摘要: The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide
(VPO)catalyst was studied using on-line gas-chromatography combined with mass spectrometry
(GC-MS) and transientresponse technique. The reaction intermediates, butene and furan, were
found in the reaction effluent under nearindustrial feed condition (3% butane+15%O2), while
dihydrofuran was detected at high butane concentration (12%butane, 5%O2). Some
intermediates of MA decomposition were also identified. Detection of these
intermediatesshows that the vanadium phosphorus oxides are able to dehydrogenate butane to
butene, and butene further to formMA. Based on these observations, a modified scheme of
reaction network is proposed. The transient experimentsshow that butane in the gas phase
may directly react with oxygen both on the surface and from the metal oxidelattice, without
a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface
latticeoxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to
deep oxidation, while latticeoxygen leads to selective oxidation.

关键词: n-butane selective oxidation;vanadium phosphorus oxide catalyst;mass spectrometer;reaction in-termediates;transient response

Abstract: The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide
(VPO)catalyst was studied using on-line gas-chromatography combined with mass spectrometry
(GC-MS) and transientresponse technique. The reaction intermediates, butene and furan, were
found in the reaction effluent under nearindustrial feed condition (3% butane+15%O2), while
dihydrofuran was detected at high butane concentration (12%butane, 5%O2). Some
intermediates of MA decomposition were also identified. Detection of these
intermediatesshows that the vanadium phosphorus oxides are able to dehydrogenate butane to
butene, and butene further to formMA. Based on these observations, a modified scheme of
reaction network is proposed. The transient experimentsshow that butane in the gas phase
may directly react with oxygen both on the surface and from the metal oxidelattice, without
a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface
latticeoxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to
deep oxidation, while latticeoxygen leads to selective oxidation.

Key words: n-butane selective oxidation, vanadium phosphorus oxide catalyst, mass spectrometer, reaction in-termediates, transient response