Abstract: The kinetics of oxidative dehydrogenation of butene to butadiene over B-02 ferrite catalyst has been studied in an internal recirculation gradientless reactor. The experiments were conducted over a wide range of water to olefin ratio, and a large variation in the partial pressures of oxygen, butene, and butadiene. The kinetic models developed were based on a consecutive parallel reaction scheme: butene-butadiene carbon dioxide and were supported by the results obtained. The change in temperature had less effect on the ratio r8/r2. When the partial pressure of butadiene was high, the formation of carbon dioxide from butadiene was much greater than that from butene. A model with best fit was obtained as follows: The model obtained comprises both typical redox expressions and power rate expressions and is shown to be compatible with Mars-Van Krevelen redox mechanism. The model fitted the experimental data at high water/olefin ratio as well as those at very low water/olefin ratio. The effect of butadiene on the reaction rate was investigated through introducing additional butadiene to the fresh butene feed. It was observed that butadiene showed slight inhibition to r1, but hindered the combustion rate of butene to a much greater extent. It was also observed that the selectivity declined much at a high temperature. Low water/olefin ratio greatly enhanced carbon dioxide formation.

摘要： 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.