A general and robust approach for defining and solving microkinetic catalytic systems. Issue 1 (30th September 2014)

• Record Type: Journal Article
• Authors: Gusmão, Gabriel S.; Christopher, Phillip
• Is Part Of: AIChE journal. Volume 61:Issue 1(2015:Jan.)
• Page Start: 188
• Page End: 199
• Publication Date: 2014-09-30
• Subjects: Chemical engineering -- Periodicals; Génie chimique -- Périodiques; 660.28
• DOI: 10.1002/aic.14627
• Languages: English
• ISSNs: 0001-1541

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>Recent approaches for the rational design of heterogeneous catalysts have relied on first‐principles‐based microkinetic modeling to efficiently screen large phase spaces of catalytic materials for optimal activity and selectivity. Microkinetic modeling allows the calculation of catalytic rate and selectivity under a given set of conditions without a priori assumptions of rate or selectivity controlling steps by simultaneously solving nonlinear algebraic equations comprising species mass balances bound by the pseudo steady‐state approximation. We introduce a general approach to define and solve microkinetic systems that relies solely on its stoichiometric matrix and kinetic parameters of considered reaction steps. Our approach relies on linearization of the microkinetic system, enabling analytical calculation of system derivatives for use in quasi‐Newton solution schemes that exhibit excellent robustness and efficiency with minimal dependence on initial conditions. © 2014 American Institute of Chemical Engineers <italic>AIChE J</italic>, 61: 188–199, 2015</p> </abstract>