二甲醚氧化反应的热力学分析  

Thermodynamic Analysis for the Oxidation of Dimethyl Ether

作　　者：孙明[1] 余林[1] 余倩[1] 郝志峰[1] 李永峰[1] 

机构地区：[1]广东工业大学轻工化工学院,广州510006

出　　处：《天然气化工—C1化学与化工》2008年第2期33-37,46,共6页Natural Gas Chemical Industry

基　　金：广东省自然科学基金团队项目(04205301);广东省高等学校自然科学研究重点项目(06Z011);广东省科技计划项目(2005B10201053);广州市科技计划项目(2006J1-C0501);新进科技研究基金(XJ200604)

摘　　要：用Benson基团贡献法估算了甲缩醛和乙二醇二甲醚的标准生成热△fHθm、标准熵Sθm和摩尔等压热容Cp,m。计算了不同温度下的二甲醚部分氧化和完全氧化反应的标准摩尔焓变△rHm、吉布斯自由能变△rGm和反应平衡常数K,分析了各热力学参数与其温度之间的关系,考察了反应压力和原料气配比对二甲醚平衡转化率的影响,同时把计算结果与二甲醚在VOx-SnO2/MgO选择氧化的实验数据进行了对比分析,为二甲醚部分催化氧化反应合成乙二醇二甲醚、甲缩醛以及完全氧化的反应提供了理论依据。The standard enthalpy of formation and thermal capacity of dimethoxymethane （DMM） and 1,2-dimethoxyethane （DMET）as a result of dimethyl ether （DME） oxidation were calculated by Benson group contribution. The molar enthalpy changes, the Gibbs free energies and the equilibrium constants of the selective oxidation and total oxidation of DME were calculated as a function of temperature. The effect of pressure and the DME/O2 molar ratio in source gas on DME equilibrium conversion were calculated as well, and the results were compared with the experimental data from the selective oxidation of DME over VOx-SnO2/MgO catalyst. This provides a thermodynamic basis for the synthesis of high added-value products such as DMM and DMET from DMEr and for the total oxidation, namely catalytic combustion, of DME.

关 键 词：二甲醚 甲缩醛 乙二醇二甲醚 基团贡献法 热力学 

分 类 号：TQ225[化学工程—有机化工]