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An experimental investigation is presented on Ti (Ⅳ) extraction from acidic sulfate solutions using trialkylphosphine oxide (TRPO) in dodecane as an extractant.The effects of H2SO4 concentration, TRPO concentration and phase ratio O/A on the phase behavior and extraction behavior of the system were studied.The splitting of a system from biphasic to tfiphasic is observed.The third phase appears at different aqueous H2SO4 concentrations with varying initial TRPO concentrations and the volume of the middle phase increases as the volume of TRPO added increases.