Mechanistic insights into the co-recovery of nickel and iron via integrated carbon mineralization of serpentinized peridotite by harnessing organic ligands

Abstract

The rising need to produce a decarbonized supply chain of energy critical metals with inherent carbon mineralization motivates advances in accelerating novel chemical pathways in a mechanistically-informed manner. In this study, the mechanisms underlying co-recovery of energy critical metals and carbon mineralization by harnessing organic ligands are uncovered by investigating the influence of chemical and mineral heterogeneity, along with the morphological transformations of minerals during carbon mineralization. Serpentinized peridotite is selected as the feedstock, and disodium EDTA dihydrate (Na₂H₂EDTA·2H₂O) is used as the organic ligand for metal recovery. Nickel extraction efficiency of ∼80% and carbon mineralization efficiency of ∼73% is achieved at a partial pressure of CO₂ of 50 bars, reaction temperature of 185 °C, and 10 hours of reaction time in 2 M NaHCO₃ and 0.1 M Na₂H₂EDTA·2H₂O. Extensive magnesite formation is evidence of the carbon mineralization of serpentine and olivine. An in-depth investigation of the chemo-morphological evolution of the CO₂–fluid–mineral system during carbon mineralization reveals several critical stages. These stages encompass the initial incongruent dissolution of serpentine resulting in a Si-rich amorphous layer acting as a diffusion barrier for Mg²⁺ ions, subsequent exfoliation of the silica layer to expose unreacted olivine, and the concurrent formation of magnesite. Organic ligands such as Na₂H₂EDTA·2H₂O aid the dissolution and formation of magnesite crystals. The organic ligand exhibits higher stability for Ni-complex ions than the corresponding divalent metal carbonate. The buffered environment also facilitates concurrent mineral dissolution and carbonate formation. These two factors contribute to the efficient co-recovery of nickel with inherent carbon mineralization to produce magnesium carbonate. These studies provide fundamental insights into the mechanisms underlying the co-recovery of energy critical metals with inherent carbon mineralization which unlocks the value of earth abundant silicate resources for the sustainable recovery of energy critical metals and carbon management.