Browsing by Subject "single event"
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Item Conversion of methanol to light olefins on SAPO-34: kinetic modeling and reactor design(Texas A&M University, 2005-02-17) Al Wahabi, Saeed M. H.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.Item Fundamental kinetic modeling of the catalytic reforming process(Texas A&M University, 2007-04-25) Sotelo-Boyas, RogelioIn this work, a fundamental kinetic model for the catalytic reforming process has been developed. The complex network of elementary steps and molecular reactions occurring in catalytic reforming has been generated through a computer algorithm characterizing the various species by vectors and Boolean relation matrices. The algorithm is based on the fundamental chemistry occurring on both acid and metal sites of the catalyst. Rates are expressed for each of the elementary steps involved in the transformation of the intermediates. The Hougen-Watson approach is used to express the rates of the molecular reactions occurring on the metal sites of the catalyst. The single event approach is used to account for the effect of structure of reactant and activated complex on the rate coefficients of the elementary steps occurring on the acid sites. This approach recognizes that even if the number of elementary steps is very large they belong to a very limited number of types, and therefore it is possible to express the kinetics of elementary steps by a reduced number of parameters. In addition, the single event approach leads to rate coefficients that are independent of the feedstock, due to their fundamental chemical nature. The total number of parameters at isothermal conditions is 45. To estimate these parameters, an objective function based upon the sum of squares of the residuals was minimized through the Marquardt algorithm. Intraparticle mass transport limitations and deactivation of the catalyst by coke formation are considered in the model. Both the Wilke and the Stefan-Maxwell approaches were used to calculate the concentration gradients inside of the particle. The heterogeneous kinetic model was applied in the simulation of the process for typical industrial conditions for both axial and radial flow fixed bed reactors. The influence of the main process variables on the octane number and reformate volume was investigated and optimal conditions were obtained. Additional aspects studied with the kinetic model are the reduction of aromatics, mainly benzene. The results from the simulations agree with the typical performance found in the industrial process.