蜂窝催化剂上甲醇自热重整制氢的动力学研究

400 ℃～460 ℃，400 h－1～1 600 h－1，O2/CH3OH(mol ratio)=0.10～0.25,H2O/CH3OH (mol ratio) =1.0～1.8下，通过正交实验设计方法，用BSD-2A型内循环无梯度反应器研究了Zn-Cr/CeO2-ZrO2蜂窝催化剂上甲醇自热重整制氢反应的宏观动力学。以甲醇水蒸气重整反应、甲醇分解反应和甲醇完全氧化反应为独立反应进行了研究，得出了幂指数型反应速率表达式,并根据实验结果，利用最小二乘法求解了动力学参数值。F检验表明该动力学模型是高度显著的。该多重反应动力学方程的得出为蜂窝反应器的进一步模拟、优化和设计提供了数据。

Global kinetics for hydrogen production by oxidative steam reforming of methanol

Global kinetics for hydrogen production by oxidative steam reforming of methanol over Zn-Cr/CeO2-ZrO2 catalyst was studied in a BSD-2A gradient-less reactor. The experimental conditions were chosen in the range of temperature 400 ℃～460 ℃, volume space velocity600 h－1~1 600 h－1, O2/CH3OH=0.1~0.25,H2O/CH3OH=1.0~1.8. Experiments were carried out by means of L16 (45) orthogonal design. Steam reforming of methanol, methanol decomposition and methanol total oxidation are treated as independent reactions. A power-type rate model was established, in which the rate of three independent reactions are related with the partial pressure of the reactants and products. Parameters of model were determined by the linear least-square parameter estimation method. The accuracy of the experimental data and kinetics model was proved by F-examination, which fit experimental data well. The activation energy of this study is similar to the models of the literatures. Remarkably, the kinetics of the difficult reaction -methanol total oxidation is also studied and the result is feasible. These kinetics results could then be used for the design and optimization of monolith reactor for hydrogen production.