Conversion of methanol to light olefins on SAPO-34 kinetic modeling and reactor design.

摘要

In this work, the reaction scheme of the MTO process was written in terms of elementary steps and generated by means of a computer algorithm characterizing the various species by vectors and Boolean relation matrices. The number of rate parameters is very large. To reduce this number the rate parameters related to the steps on the acid sites of the catalyst were modeled in terms of transition state theory and statistical thermodynamics. Use was made of the single event concept to account for the effect of structure of reactant and activated complex on the frequency factor of the rate coefficient of an elementary step. The Evans-Polanyi relation was also utilized to account for the effect of the structure on the change in enthalpy. The structure was determined by means of quantum chemical software.; The number of rate parameters of the complete reaction scheme to be determined from experimental data is thus reduced from 726 to 30. Their values were obtained from the experimental data of Abraha by means of a genetic algorithm involving the Levenberg-Marquardt algorithm and combined with sequential quadratic programming. The retained model yields an excellent fit of the experimental data. All the parameters satisfy the statistical tests as well as the rules of carbenium ion chemistry. The kinetic model also reproduces the experimental data of Marchi and Froment, also obtained on SAPO-34. Another set of their data was used to introduce the deactivation of the catalyst into the kinetic equations.; This detailed kinetic model was used to investigate the influence of the operating conditions on the product distribution in a multi-bed adiabatic reactor with plug flow. It was further inserted into riser and fluidized bed reactor models to study the conceptual design of an MTO reactor, accounting for the strong exothermicity of the process. Multi-bed adiabatic and fluidized bed technologies show good potential for the industrial process for the conversion of methanol into olefins.