In this study, the interaction between gas phase potassium species and kaolin was investigated in a fixed bed reactor equipped with a surface ionization detector, which is capable of detecting alkali metals in gas phase at ppb level. The effects of mass transport, space time, sorbent temperature and concentration of KCl on the rate of potassium adsorption on kaolin were studied in air. Kaolin, mainly composed of kaolinite-Al2Si2O5(OH)(4), was found to be very efficient in removing gaseous alkali species from hot flue gases at fluidized bed combustion temperatures. The removal efficiency increased as temperature was decreased or KCl concentration was increased. The capture of potassium by kaolin was irreversible with formation of both water-soluble and water-insoluble products. Kaolin captured KOH almost as effectively as KCl, but K2SO4 was captured much less effectively than KCl. (C) 2004 Elsevier Ltd. All rights reserved.