Solvent extraction with organophosphorus extractants has potential as a low-cost method for efficient Mo recovery for acidic leaching solutions. However, improved selectivity is required to obtain high-purity Mo products. In this study, various acidic organophosphorus extractants were compared, and 2-ethylhexylphosphonic acid mono-(2-ethylhexyl) ester (P507) was found to be optimal for efficient Mo extraction and Fe separation from acidic leaching solutions. Under the optimized conditions (40 vol% P507, 3:1 organic/aqueous, 20 °C, 5 min), the Mo and Fe extraction efficiencies reached 98.1 % and 35.2 %, respectively, with a separation factor of 90.1. The Mo/Fe separation efficiency was further improved using a two-stage countercurrent extraction method. The Mo extraction efficiency was attributed to coordination bonds (P = O → Mo) formed between Mo(VI) oxycations and P507 dimers, as well as covalent bonds (P O Mo) formed by substituting the hydrogen ions in P507. Increasing the H 2 SO 4 concentration in the leaching solution gradually transformed MoO 2 2+ into Mo 2 O 5 2+ dimers, which formed MoO 2 (HA 2 ) 2 and Mo 2 O 5 (HA 2 ) 2 metal complexes during the extraction process. HCl scrubbing of the loaded organic phase effectively removed Fe. For subsequent ammonia stripping of the HCl-scrubbed organic phase, the optimal ammonia concentration was 1.25 mol/L. Further increasing the ammonia concentration promoted the saponification reaction of ammonia with P507, thereby reducing the Mo stripping efficiency. In summary, using multistage countercurrent extraction, increasing the H 2 SO 4 concentration in the leaching solution, and scrubbing the loaded organic phase with HCl facilitate efficient Mo/Fe separation, providing a feasible approach for the preparation of high-purity ammonium molybdate with broad application prospects.
Wanjun Guo,Zhi-Qiang Wang,Shuang Xiang,Yaxuan Jing,Xiaohui Liu,Yong Guo,Xue-Qing Gong,Yanqin Wang
ABSTRACT Owing to the wide application of primary amines, their selective production via reductive amination has become a crucial research topic. Various metal-supported catalysts (Pt, Ru, Rh, Ir, Co, Ni, etc. ) have been investigated, and metallic species have been recognized as active sites in recent years. Herein, we reveal for the first time that CoO species containing oxygen vacancies within a core-shell-structured Co@CoO catalyst accelerate the ammonolysis of Schiff bases, key intermediates in reductive amination, through NH 3 dissociation to hydride-like NH 2 δ – species, delivering an excellent reductive amination performance. The catalyst is highly stable and was utilized in 10 catalytic cycles for the amination of biomass-derived cyclopentanone (CPO) to cyclopentylamine (CPA) without deactivation. Various computational models in combination with spectroscopic measurements indicated that this catalyst not only drives the dissociation of H 2 to the active H δ – species, but also enables the homolytic cleavage of NH 3 to NH 2 δ – . D 2 isotopic tracing experiments provided further evidence of the direct involvement of hydride-like NH 2 δ – species in Schiff base ammonolysis. Theoretical calculations verified the stable co-adsorption of H δ – and NH 2 δ – , which allows the Schiff base to move freely on the surface of the CoO shell and participate extensively in molecular collisions, resulting in exceptional catalytic activity. This is the first study that demonstrates the potential of metal oxide catalysts for the production of primary amines via reductive amination.
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