The present paper is focused on physico-mechanical pre-treatments of spent hydrotreating catalysts aimed at concentration of at least one of the valuable metals contained in such secondary raw material. In particular, dry Ni-Mo and Co-Mo as well as wet Ni-Mo catalysts were used. Flotation, grain size separation and attrition processes were tested. After that, a rods vibrating mill and a ball mill were used to ground the catalysts in order to understand the best mechanical pre-treatment before leaching extraction. The results showed that flotation is not able to concentrate any metals due to the presence of coke or other depressant compounds. The particle size separation produces two fractions enriched in Mo and Co when dry Co-Mo catalyst is used, whereas attrition is not suitable as metals are uniformely distributed in rings' volume. Roasting at 550 degrees C and vibrating grinding are the most suitable pre-treatments able to produce fractions easily leached by NaOH and H(2)SO(4) after grain size separation. (C) 2011 Elsevier B.V. All rights reserved.