Determining flux-limiting mechanism of hydrogen permeation through palladium membrane by n value.

Pd film has been endowed with the hydrogen selective permeation capability and widely used for hydrogen separation via a series of complex processes. Clarifying the exact relationship between permeating mechanism and hydrogen pressure exponent (n) is of great significance to optimize the purification performance, adequate exploration toward which is nevertheless insufficient. In this work, Pd membrane-based hydrogen permeation was divided into seven steps according to the "dissociation-diffusion" principle. The effect of each step on permeation flux with and without considering external mass transfer process was quantified by mathematical and physical models, in which the relationship between n value and the flux-limiting mechanism was deeply analyzed. The calculation suggested that desorption-limiting mechanism acting as leading role would result in n value to be 0, while external mass transfer dominating the permeation would make n value to be 1. When n value was between 0 and 0.5, desorption and diffusion processes would impose combined impact on the permeation (ignoring external mass transfer) and desorption might have more weight as n approaching to 0. On the other hand, taking external mass transfer into account, desorption-limiting and external mass transfer-limiting mechanism would work together as 0 < n < 1. The closer n approaching to 1, the more significant of external mass transfer mechanism. In addition, the influences of Pd film thickness, ΔP variation and mass transfer coefficient on n value were also elucidated systematically. [Display omitted] • Pd membrane-based hydrogen permeation was divided into seven steps according to the "dissociation-diffusion" principle. • The effect of each step on permeation flux was quantified by mathematical and physical models. • The relationship between n value and the flux-limiting mechanism was deeply analyzed. • Effect of external mass transfer process on flux-limiting mechanism was displayed. [ABSTRACT FROM AUTHOR]