This study presents the results of a two-stage autoclave processing of a copper–arsenic concentrate. Copper concentrate is an important raw material to produce copper and other metals. However, in some cases, the concentrate may contain increased amounts of arsenic, which makes further processing difficult. Therefore, the development of modern hydrometallurgical methods for processing copper concentrate with a high arsenic content is an urgent task, which could lead to the optimization of the raw material processing process and the improvement of the quality of the concentrate. It has been established that the optimal conditions for the sequential two-stage autoclave processing of copper–arsenic concentrate are: t = 220–225 °C, τoxidation = 20 min, τtot = 90 min, Po2 = 0.4 MPa, and L:S = 10:1, [H2SO4]initial = 40 g/dm3; in this case, 85% of zinc, 44% of iron, and 78% of arsenic, respectively, are extracted into the solution during both stages and the loss of copper was about 0.01%. This is explained by the fact that at the first stage (oxidation) of the autoclave processing of the copper–arsenic concentrate, copper, together with iron, leaches into the solution, and at the second stage (reduction), copper precipitates out of the solution in the form of chalcocite. Copper in the residue after autoclave leaching is in the form of Cu2S, iron is in the form of pyrite (FeS2), and lead is in the form of anglesite (PbSO4), respectively. The obtained micrographs and EDX mappings clearly show no iron arsenates. This confirms that at the oxidative stage of the developed process, arsenic, removed by 78%, remains in the solution. The remaining arsenic is associated with tennantite, indicating the effectiveness of the treatment process in removing arsenic from the copper–arsenic concentrate. A second important observation is the presence of pronounced areas of copper sulfides in the microphotos without iron and arsenic impurities. This confirms that copper is deposited as chalcocite during the reduction phase of the process, which is the desired result.
