CO偶联--再生循环反应系统的非线性行为研究

CO catalytic coupling to diethyl oxalate and oxalic acid in the gas phase is one of the most important projects in the C1 chemical technology field. It is a complicated system comprising of CO coupling reaction and regeneration of ethyl nitrite. so it was studied by modern nonlinear bifurcation method in this work..The dynamic model of CO coupling reaction and ethyl nitrite regeneration reaction were proposed and dynamic simulation was carried out. The results showed good agreements with the scaling-up experimental data. The results also indicated that the nonlinear characteristics and control of the reaction system could be studied on the basis of the dynamic models and the predigested kinetic equations of mechanism model.The dynamic and nonlinear characteristics of CO coupling reaction were studied primarily by the nonlinear bifurcation analysis on the CO coupling reaction dynamic model. Meantime, the dynamic safe operation regions were proposed on the base of sole variables and dimensionless numbers. When the mass transfer Peclet number Pe1, heat transfer Peclet number Pe2>10, there is only one operated state, and moreover, it is steady. The operated state increased with the decrease of Pe1 and Pe2, and reached to four at most as Pe1=Pe2=1. It can be easily proved that it is propitious to keep state steady with the increase of Pe1, Pe2 and dimensionless heat transfer coefficient β and the decrease of Damk?hler number Da. Additionally lower exit temperature was in favor of keeping state steady..The parametric sensitivity was analyzed based on the ethyl nitrite regeneration reaction dynamic model and the result showed that gas flow rate, pressure and exchanged temperature were sensitive parameters of regeneration reaction. The conversion of NO increased with the increase of pressure and exchanged temperature and the decrease of gas phase flow rate.The dimensionless model was set-up and its nonlinear bifurcation character was analyzed by using the continuation technique. The effect of the dimensionless number on the nonlinear property was studied in detail and the results showed that the dimensionless specific heatα, dimensionless heat transfer coefficientβ, dimensionless heat of reaction B, dimensionless activation energyγand dimensionless exchanged temperature x2C were sensitive parameters of multiple steady states and three multiple steady states could be obtained. Because these dimensionless parameters and Damk?hler number Da were influenced by parameters such as ratio of the liquid to gas flow rates, heat of reaction, heat transfer capability of the reactor, activation energy and exchanged temperature, these were the main sensitive parameters of the multiple steady states..The multiple steady state criteria were derived to predict whether or not the multiple steady states occurred and calculate the multiple steady state region. The numerical method for calculating multiple steady states was given. The interaction between hopf bifurcation and static bifurcation was investigated and five kinds of bifurcation diagrams were derived. Dynamic behavior of the unsteady region in these bifurcation diagrams was investigated.The industrial scale-up and control of of CO coupling-regeneration reaction system will be supported by the dynamic simulation and the nonlinear analysis of the reactions..

利用非线性动力学奇异性理论分析-----氧化碳偶联----再生反应系统的非线性动力学行为芯肯低持锌赡艽嬖诘姆植砝嘈图跋嘤Φ姆植硖跫范ǚ植淼愀浇髦挚赡芊钦判孕形诓问占涠杂Φ那颍佣谎趸寂剂?--再生反应系统在环境友好的原则下确定可操作区域提供理论依据，提出该反应系统的非线性动力学调控方案并进行实验验证。