The controlling role of atmosphere in dawsonite versus gibbsite precipitation from tetrahedral aluminate species

Dembowski, Mateusz; Loring, John S.; Bowden, Mark E.; Reynolds, Jacob G.; Graham, Trent R.; Rosso, Kevin M.; Pearce, Carolyn I.

doi:10.1039/d1dt02081a

The controlling role of atmosphere in dawsonite versus gibbsite precipitation from tetrahedral aluminate species

Journal Article · Fri Sep 03 00:00:00 EDT 2021 · Dalton Transactions

DOI:https://doi.org/10.1039/d1dt02081a· OSTI ID:1820089

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Washington River Protection Solutions, LLC, Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

In highly alkaline solution, aluminum speciates as the tetrahedrally coordinated aluminate monomer, Al (OH)₄^- and/or dimer Al₂O(OH)₆^2-, yet precipitates as octahedrally coordinated gibbsite (Al(OH)₃). This tetrahedral to octahedral transformation governs Al precipitation, which is crucial to worldwide aluminum (Al) production, and to the retrieval and processing of Al-containing caustic high-level radioactive wastes. Despite its significance, the transformation pathway remains unknown. Here we explore the roles of atmospheric water and carbon dioxide in mediating the transformation of the tetrahedrally coordinated potassium aluminate dimer salt (K₂Al₂O(OH)₆) to gibbsite versus potassium dawsonite (KAl(CO₃)(OH)₂). A combination of in situ attenuated total reflection infrared spectroscopy, ex situ micro X-ray diffraction, and multivariate curve resolution-alternating least squares chemometrics analysis reveals that humidity plays a key role in the transformation by limiting the amount of alkalinity neutralization by dissolved CO₂. Lower humidity favors higher alkalinity and incorporation of carbonate species in the final Al product to form KAl(CO₃)(OH)₂. Higher humidity enables more acid generation that destabilizes dawsonite and favors gibbsite as the solubility limiting phase. This indicates that the transition from tetra- to octahedrally coordinated Al does not have to occur in bulk solution, as has often been hypothesized, but may instead occur in thin water films present on mineral surfaces in humid environments. Our findings suggest that phase selection can be controlled by humidity, which could enable new pathways to Al transformations useful to the Al processing industry, as well as improved understanding of phases that appear in caustic Al-bearing solutions exposed to atmospheric conditions.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 89233218CNA000001; AC05-76RL01830

OSTI ID:: 1820089

Alternate ID(s):: OSTI ID: 1818827
OSTI ID: 1829716

Report Number(s):: LA-UR--21-27257

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 38 Vol. 50; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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