Electrolytic Reduction, Precipitation, And Thermal Decomposition Of Uranous Sulfate: A Pathway For Closed Loop Sulfuric Acid Recycle

Electrolytic reduction followed by the addition of sulfuric acid and the application of heat can be used to selectively crystallize uranous sulfate from solution. This approach, when coupled with downstream thermal decomposition, forms the basis of a process for primary uranium recovery and purification where much of the sulfuric acid value can be recovered and recycled. In this process, a purified uranium (VI) leach solution is first electrolytically reduced to uranium (IV) in a membrane electrolysis cell. Sulfuric acid is then added to the solution which, in conjunction with the input of heat, causes the crystallization of uranous sulfate tetrahydrate. The precipitate is then dried and thermally decomposed to U3O8, which releases a mixture of high-purity SO2, SO3, oxygen, and water vapour. This gas can be recovered as sulfuric acid in an existing acid plant, processed through a new wet sulfuric acid process, or absorbed directly into the upstream electrolyte as a substitute for fresh acid in the crystallization step. This process has been shown to be practical, efficient, and cost-effective on the laboratory scale, and could be practiced on the industrial scale using commercially available equipment. This paper focuses on the thermal decomposition process and options for acid recovery.