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本文利用内循环无梯度反应器,在320～420℃及较宽的各组分分压范围内研究了B-02工业催化剂用于丁烯氧化脱氢反应的本征动力学.按照串-并联反应网络,依据Redox机理、L-H机理和幂函数型规律构想出28个动力学模型;应用模型参数的物理特征、参数估值中的残差平方和相对大小以及非本征参数法筛选模型;采用模式探测法和马垮特法相结合的综合方法进行模型参数估值,从而求得适宜的本征动力学模型.最后对所定动力学模型进行显著性检验,证明该模型对实验数据确有较好的表现力.文中还讨论了水/烯比值对模型参数的影响、丁二烯的阻碍作用及催化剂的选择性等问题.
In this paper, the intrinsic kinetics of the B-02 industrial catalyst for the oxidative dehydrogenation of butene was studied in a non-gradient reactor with internal circulation at 320-420 ℃ and a wide range of partial pressure. Reaction network, 28 kinetic models were constructed based on the Redox mechanism, the LH mechanism and the power function law. The model was selected using the physical characteristics of the model parameters, the residual square sum of the parameter estimates and the extrinsic parameter method. Model detection method and horse collapse method combined method of comprehensive evaluation of model parameters to obtain the appropriate intrinsic dynamics model.Finally, the kinetic model was tested for significant test to prove that the model of the experimental data is indeed good The paper also discussed the effect of water / olefin ratio on the model parameters, the obstruction of butadiene and the selectivity of the catalyst.