Rare earth europium recovery using selective metal-organic framework incorporated mixed-matrix membrane

Abstract

Rare-earth elements (REEs) play a crucial role in state-of-the-art technologies and sustainable energy generation. However, conventional production methods of REE often instigate detrimental impacts on environment. Hence, the development of efficient and sustainable hydrometallurgical methods for REE recovery from complex solution has become a crucial research focus. This study investigates a mixed-matrix membrane composed of a highly europium selective metal-organic framework-based adsorbent, Cr-MIL-PMIDA, embedded in sulfonated poly(ether ketone) (SPEK) polymer membrane matrix to preferentially concentrate europium (Eu 3+ ) ions in the presence of other competing cations. The activated membrane notably reduced ionic conductivity for Eu 3+ compared to other multivalent ions. Membrane extraction experiments further confirmed the selective behavior, demonstrating slower diffusion for Eu 3+ compared to Mg 2+ and Zn 2+ cations. Especially, at pH 5, Mg 2 ⁺ and Zn 2 ⁺ recovery was greater than 30%, whereas Eu³⁺ recovery remained lower than 4%. We propose that the strong chemical affinity between the phosphate group and Eu 3+ help partition of the Eu 3+ ions in the membrane phase and inhibit the diffusion and further partitioning of the Eu 3+ ion from bulk solution. Furthermore, we demonstrate the stability of the composite membrane and the embedded MOF particles in aqueous solution for up to 12 days without degradation, attributing it to the robust chemical stability of the MOF structure. • Optimised SPEK-40 offers tenfold higher ionic conductivity than neat SPEK. • Cr-MIL-PMIDA (MOF) loading in SPEK membranes greatly enhanced REE selectivity. • Activated SPEK-40 mitigated Eu³⁺ diffusion more than Mg 2 ⁺ and Zn 2 ⁺. • At pH 5, Mg 2 ⁺ and Zn 2 ⁺ show high recovery (∼30%), Eu³⁺ recovery remain low (∼4%). • XPS revealed Eu 3+ coordination and speciation within the MMM phase.

Topics & Concepts