When yellow phosphorous tail gas will be used as chemical raw material gas to produce high accessional products such as formate, oxalate, methanol and so on, pretreatment process by its purifying could limit its application. In this paper, two kinds of impregnated activated carbon catalysts and catalytic oxidation reaction for purifying H2S and PH3 contained in tail gas have been studied in laboratory-scale and pilot-plant fixed-bed reactor. The concentration of both H2S and PH3 could be less than 10 mg/m(3) over these two kinds of catalysts. Reaction kinetics for the catalytic oxidation of H2S and PH3 over the mixed catalyst has also been studied on differential reactor, and kinetic model for both Compounds have been formulated, which are subsequently implemented in the modeling of the pilot-plant fixed-bed reactor. A two-dimensional un-steady reaction model which includes both physical adsorption and catalytic reaction process was developed for binary gas mixture purification in fixed-bed. Results from model calculation are reasonably well agreement with the experimental data. It is helpful for a thorough explanation of the observed pilot-plant reactor performance and designing in industrial process. (C) 2007 Elsevier B.V. All rights reserved.