Diffusion of gaseous products through a particle surface layer in a fluidized bed reactor

Abstract

This paper examines a solid conversion process during hydrolysis and decomposition of cupric chloride in a thermochemical copper–chlorine (Cu–Cl) cycle of hydrogen production. Reaction rate constants and the time required for complete solid conversion are determined by a shrinking-core model. Diffusion of gaseous reactant occurs through a film surrounding the particle, after which the reactant penetrates and diffuses through a layer of ash to the surface of the unreacted core. The shrinking-core model for spherical particles predicts the reaction of gaseous reactant with solid at the particle surface, and diffusion of gaseous products through the ash, back to the exterior surface of the solid. The hydrolysis reaction is also analyzed with respect to chemical equilibrium conversion and required heat input. Effects of varying operating parameters are examined, including the temperature, pressure, excess steam, inert gas and hydrogen chloride (HCl) in the steam. At a temperature of 375 °C, complete conversion of CuCl 2 can be achieved by controlling the excess steam, operating pressure and inert gas supply. Addition of HCl in the steam supply increases the excess steam requirement for conversion of cupric chloride solid, and the upper limit for HCl concentration increases with temperature and inert gas composition. The addition of inert gas may also reduce the excess steam requirement, thereby reducing the heat requirement. These new results have valuable utility for equipment scale-up in the thermochemical Cu–Cl cycle of hydrogen production.