화학공학소재연구정보센터
Chemical Engineering Science, Vol.65, No.2, 680-691, 2010
Dynamic shear in continuous-flow rotating-disk catalytic reactors with stress-sensitive kinetics based on Curie's theorem in non-equilibrium thermodynamics
Stress-sensitive response is simulated in a modified parallel-disk reactor that implements steady and unidirectional dynamic shear in the creeping flow regime. Reactants chemisorb on the surface of the rotating plate, and catalytic sites are replenished from the bulk fluid via radial and tangential flow accompanied by transverse diffusion in the z-direction toward the active surface. Chemical reaction is enhanced by viscous shear at the interface between the bulk fluid and the rotating plate. This heterogeneous catalytic rotational reactor is modeled via radial convection and axial diffusion with angular symmetry in cylindrical coordinates. The reaction/diffusion boundary condition on the surface of the rotating plate accounts for stress-sensitive reactant consumption via the zr- and z Theta-elements of the velocity gradient tensor at the catalytic surface. Linear transport laws in chemically reactive systems that obey Curie's theorem predict the existence of cross-phenomena between scalar reaction rates and the magnitude of the second-rank velocity gradient tensor, selecting only those elements of del v experienced by reactants that are chemisorbed on the surface of the rotating plate. Stress sensitivity via the formalism of irreversible thermodynamics introduces a zeroth-order contribution to heterogeneous consumption rates that must be quenched when reactants or active vacant sites are not present on the surface of the rotating plate. Rotating-disk reactor simulations are presented for simple 1st-order, simple 2nd-order, and complex heterogeneous stress-free kinetics, where the latter considers Langmuir-type dissociative adsorption of one of the reactants. Accurate design of rotating-disk reactors must consider stress-sensitivity when the shear-rate-based Damkohler number (i.e., ratio of the stress-dependent zeroth-order consumption rate relative to the rate of reactant diffusion toward the active surface) is greater than its threshold value which increases at higher stress-free Damkohler numbers. Modulated rotation of the catalytically active plate demonstrates that these rotating-disk reactors must operate above a threshold for the stress-sensitive Damkohler number, identified under steady shear conditions, before dynamic shear has a distinguishable effect on reactor performance. (C) 2009 Elsevier Ltd. All rights reserved.