Selective Recovery of Molybdenum over Nickel and Cobalt from Simulated Secondary Sources Using Bifunctional Ionic Liquid [TOA][Cy272]

利用双功能离子液体 [TOA][Cy272] 从模拟二次源中选择性回收钼(相对于镍和钴)

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Abstract

The growing demand for ultra-low sulfur fuels has intensified interest in recovering strategic metals from the large volumes of hazardous hydrodesulfurization catalysts that are discarded yearly. This work evaluates a task-specific ionic liquid, tri-n-octylammonium bis(2-,4-,4-trimethylpentyl)-phosphinate [TOA][Cy272], synthesized by the acid-base neutralization of tri-n-octylamine and Cyanex 272. FT-IR spectroscopy confirmed complete proton transfer and the formation of a stable ion pair. Liquid-liquid extraction tests were conducted with synthetic Co-Ni-Mo solutions (0.1-2.5 g/L each), a varying ionic liquid concentration (10-50 vol%), pH (1.5-12.5), and organic/aqueous ratio (1:1). At 35 vol% of ionic liquid and pH 2, the extraction efficiency for Mo reached 94%, with separation factors βMo/Ni = 12 and βMo/Co = 7.5; Co and Ni uptake remained ≤15%. Selectivity decreased at higher metal loadings because of ionic liquid saturation, and an excessive ionic liquid amount (>35%) offered no benefit, owing to viscosity-limited mass transfer. Stripping studies showed that 1 M NH(4)OH stripped about 95% Mo, while leaving Co and Ni in the organic phase; conversely, 2 M HCl removed 92-98% of Co and Ni, but <5% Mo. Overall Mo recovery of about 95% was obtained by a two-step extraction/stripping scheme. The results demonstrate that [TOA][Cy272] combines the cation exchange capability of quaternary ammonium ILs with the strong chelating affinity of organophosphinic acids, delivering rapid, selective, and regenerable separation of Mo from mixed-metal leachates and wastewater streams.

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