<p>The industrial process of benzene selective hydrogenation for the preparation of cyclohexene generates spent Ru/ZrO₂ catalysts. Based on the composition of the catalyst, this paper proposes a process of acid leaching to remove Zn, followed by NaHSO₄⋅H₂O roasting and water leaching to remove Zr, and finally employing alkali fusion oxidation distillation for Ru recovery. Firstly, the effects of acid type, liquid–solid ratio, and leaching agent concentration on the leaching ratio of Zn and Ru were investigated. The results showed that acid leaching with 1.0 mol/L H₂SO₄ and 4:1 liquid–solid ratio resulted in 87.24% and 0.05% Zn and Ru leaching ratios, respectively. Then, the influence of the molar ratio of NaHSO₄⋅H₂O to ZrO₂, roasting temperature, and roasting time on the leaching ratio of Zr and Ru during the roasting process was investigated. Under the conditions of a 5:1 molar ratio of NaHSO₄⋅H₂O to ZrO₂, a roasting temperature of 350 °C , and a roasting time of 40 min, the leaching ratios of Zr and Ru were 96.23% and 0.49%, respectively. Finally, the leaching slag was treated with alkali fusion oxidative distillation to recover Ru, with Ru distillation efficiency of more than 97%.</p> Graphical Abstract <p></p>