Selective Extraction of Zirconium from Sulfuric Acid Solutions at High Concentration with Trioctylamine (TOA)

Zirconium (Zr) and hafnium (Hf) are very important in nuclear and high-temperature applications, but their similar physical and chemical properties bring great challenges to separation. The current extraction methods have defects, such as low efficiency at high metal concentration. In this article, a zirconium (Zr)/hafnium (Hf) solvent extractive separation from sulfuric acid solutions using trioctylamine (TOA) as the extractant was researched at room temperature. The aqueous solution is prepared using zirconium sulfate (containing Hf), and the concentration of metal ions (Zr4+ and Hf4+) was about 1.096 mol·L−1. The effects of the aqueous acidity, the concentration of TOA, the contacting time, and the organic to aqueous O/A ratio on the separation of Zr and Hf were investigated. It is observed that the Zr can be extracted in the organic phase selectively, and the optimal conditions were: TOA concentration of 40 vol%, organic to aqueous O/A ratio of 3, contacting time of 5 min. Under these conditions, the single-stage extraction rate of Zr is 61.23%, while the Hf is almost not extracted. The mechanism of Zr extraction by TOA was studied through the saturation capacity and slope methods. Based on the results, it is believed that the structure of the extracted complex may be [R3NH]2[Zr(SO4)3]. This study provides a new approach for the development of industrialized Zr-Hf separation.