The expanded bed characteristics of 75–103μm fluoride‐modified zirconia (FmZr) particles synthesized by a fed batch oil emulsion process were investigated. These particles are distinguished from commercially available expanded‐bed adsorbents by virtue of their high density (2.8 g/cc) and the mixed mode protein retention mechanism which allows for the retention of both cationic and anionic proteins. The linear velocity versus bed porosity data agree with the Richardson–Zaki relationship with the terminal velocity in infinite medium of 2858.4 cm/h and a bed expansion index of 5.1. Residence time distribution (RTD) studies and bovine serum albumin (BSA) adsorption studies were performed as a function of the height of the settled bed to the column diameter (H:D) ratio and degree of bed expansion with superficial velocities of 440 to 870 cm/h. The settled bed, a 2× expanded bed, and a 3× expanded bed were studied for the H:D ratios of 1:1, 2:1, and 3:1. The dynamic binding capacity (DBC) at 5% breakthrough was low (2–8 mg BSA/mL settled bed) and was independent of the H:D ratio or the degree of bed expansion. The saturation DBC was 32.3 ± 7.0 mg BSA/mL settled bed. The adsorption–desorption kinetics and intraparticle diffusion for protein adsorption on FmZr (38–75 μm) were investigated by studying the packed bed RTD and BSA adsorption as a function of temperature and flow rate. The data show that the adsorption–desorption kinetics along with intraparticle diffusion significantly influence protein adsorption on FmZr. Low residence times (∼0.8 min) of BSA result in a DBC at 5% breakthrough which is 3.5‐fold lower compared to that at 6‐fold higher protein residence time. At low linear velocity (45 cm/h) the breakthrough curve is nearly symmetrical and becomes asymmetrical and more dispersed at higher linear velocity (270 cm/h) due to the influence of slow adsorption–desorption kinetics and intraparticle diffusion.© 1998 John Wiley & Sons, Inc. Bioeng 60: 333–340, 1998.