A comparative study of the use of Caro's acid (peroxymonosulphuric acid) and hydrogen peroxide to oxidize vanadium prior to solvent extraction

CIM Bulletin, Vol. 76, No. 854, 1983
A.J. MATTUS, S.B. MAGID, M.F. LOPEZ Interox America, Deer Park, Texas, D.B. MOBBS, Interox Chemicals Ltd., Widnes, England
Abstract The use of Caro 's acid as a replacement for hydrogen peroxide for the oxidation of vanadium prior to solvent extraction resulted in a 56% reduction in oxidant usage when compared on an equivalent hydrogen peroxide basis. Comparative oxidation tests, using two actual uranium mill raffinates, resulted in premature precipitation of an amorphous ferric vanadate when hydrogen peroxide was used to oxidize one of the raffinates containing a high iron to vanadium ratio. The use of Caro's acid eliminated the precipitation problem, thereby permitting the adjustment of the raffinate pH to a higher, more favourable level prior to solvent extraction.
Potentiometric characterization of the raffinates revealed that vanadium is responsible for the inefficiency of hydrogen peroxide compared with Caro's acid, with the oxidation efficiency of iron being the same for both oxidants. A limiting potential between 720 and 740 mV was observed when using hydrogen peroxide, while, when using Caro's acid, potentials approaching 1200 m V were achievable.
A four-stage, countercurrent extraction performed on the oxidized raffinates did not reveal any operational problems. The extraction efficiency and the extraction coefficient were found to be higher when Caro's acid was used as the oxidant, as opposed to hydrogen peroxide.
Keywords: Solvent extraction, Caro's acid, Hydrogen peroxide, Vanadium, Oxidation, Uranium, Mill raffinates, Redox chemistry.
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