Crystallization and Phase Transformations of Aluminum (Oxy)hydroxide Polymorphs in Caustic Aqueous Solution

Zhang, Hailin; Zhang, Xin; Graham, Trenton R.; Pearce, Carolyn I.; Hlushko, Hannah; Laverne, Jay A.; Liu, Lili; Wang, Suyun; Zheng, Shili; Zhang, Yi; Clark, Sue B.; Li, Ping; Wang, Zheming; Rosso, Kevin M.

doi:10.1021/acs.inorgchem.1c01111

Title: Crystallization and Phase Transformations of Aluminum (Oxy)hydroxide Polymorphs in Caustic Aqueous Solution

Journal Article · Mon Jul 05 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c01111· OSTI ID:1810710

Zhang, Hailin ^[1]; Zhang, Xin ^[2];

^[2]; Pearce, Carolyn I. ^[2]; Hlushko, Hannah ^[3]; Laverne, Jay A. ^[3];

^[2]; Wang, Suyun ^[1]; Zheng, Shili ^[4]; Zhang, Yi ^[4]; Clark, Sue B. ^[2]; Li, Ping ^[5];

^[2];

^[2]

UNIVERSITY PROGRAMS
BATTELLE (PACIFIC NW LAB)
University of Notre Dame
Chinese Academy of Sciences
Institute of Process Engineering, Chinese Academy of Sciences

Gibbsite, bayerite, and boehmite are important aluminum (oxy)hydroxide minerals in nature and have been widely deployed in various industrial applications. They are also major components in caustic nuclear wastes stored at various U.S. locations. Knowledge of their crystallization and phase transformation processes contributes to understanding their occurrence and could help optimize waste treatment processes. While it has been reported that partial conversion of bayerite and gibbsite to boehmite occurs in basic solutions at elevated temperatures, systematic studies of factors affecting the phase transformation as well as the underlying reaction mechanisms are non-existent, particularly in highly alkaline solutions. We explored the effects of sodium hydroxide concentrations (0.1~3 M), reaction temperature (60~100 ?) and aluminum concentrations (0.1~1 M) on the crystallization and transformation of these aluminum (oxy)hydroxides. Detailed structural and morphological characterization by X-ray diffraction (XRD), scanning electron microscopy (SEM), and nuclear magnetic resonance (NMR) spectrometry revealed that these processes depend largely on the reaction temperature and the Al/OH- ratio. When 1 = Al/OH- = 2.5, the reactions favor formation of high crystallinity precipitates, whereas at Al/OH- ratio ? 2.5 precipitation ceases unless the Al concentration is higher than 1 M. We identified pseudoboehmite, bayerite and gibbsite as intermediate phases to bayerite, gibbsite and boehmite, respectively, all of which transform via dissolution-reprecipitation. Gibbsite transforms to boehmite in both acidic and weak caustic environments at temperatures above 80 oC. However, a ‘bar-shaped’ gibbsite morphology dominates in highly caustic environments (3 M NaOH). The findings enable a robust basis for selection of various solid phases by tuning the reaction conditions.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1810710

Report Number(s):: PNNL-SA-162038

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 13

Country of Publication:: United States

Language:: English

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