A novel separation process for detoxifying cadmium-containing residues arising from zinc hydrometallurgical processes has been developed. The solution of sulfuric acid and ammonium citrate ((NH4)(3)C6H5O7) is used as the lixiviant to partially extract copper and other metals from the residue at room temperature. Copper in the leachate is recovered by solvent extraction (SX) with LIX 973. Cobalt in the raffinate from the copper SX process is recovered by precipitation with alpha-nitroso-beta-naphthol. Zinc remaining in the solution, at high concentrations, is further separated from cadmium by solvent extraction with P204 (di(2-ethylhexly)phosphoric acid, D2EHPA). The results show that around 50% of the copper and virtually all the zinc, cadmium and cobalt in the residue can be leached under the experimental conditions used here. Virtually all dissolved copper and cobalt can be recovered in the subsequent solvent extraction and precipitation processes. The presence of (NH4)(3)C6H5O7 could significantly facilitate the extraction of zinc by D2EHPA. More than 97% of the dissolved zinc can be recovered through a two-stage counter current solvent extraction process. After separating copper, cobalt and zinc, cadmium can easily be recovered from the solution either by cementation with zinc powder or by electrowinning, while the purified solution can be recycled back to the leaching process. (C) 2014 Elsevier Ltd. All rights reserved.