Pressure leach of β-spodumene with carbonic acid: Weak acid process for extraction of lithium

Mahmoud F. Alhadad; Hans C. Oskierski; Johannes Chischi; Gamini Senanayake; Bernhard Schulz; Alexandra A. Suvorova; Sarah E.M. Gain; Bogdan Z. Dlugogorski

doi:10.1016/j.mineng.2023.108398

Pressure leach of β-spodumene with carbonic acid: Weak acid process for extraction of lithium

Mahmoud F. Alhadad, Hans C. Oskierski, Johannes Chischi, Gamini Senanayake, Bernhard Schulz, Alexandra A. Suvorova, Sarah E.M. Gain, Bogdan Z. Dlugogorski

Energy and Resources Institute

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Abstract

This contribution develops a process for recovering lithium from β-spodumene by sequential pressure leach with solutions of carbonic acid, as a replacement for digestion of β-spodumene with concentrated sulfuric acid. Six sequential steps, each operated at 200 °C and 100 bar for 1 h, retrieve 75 % of lithium from the initial feed material. This compares with a 12.6 % Li recovery from a single-stage (batch) operation. We develop both the thermodynamic and mass-transfer models of the leach process and argue that the lithium extraction is mass-transfer controlled. The underlying mechanism involves: (i) near-instantaneous ion exchange between H⁺ for Li⁺ at the onset of the digestion; (ii) direct formation of amorphous Li-depleted rinds; (iii) precipitation of secondary minerals, boehmite (AlO(OH)) and skin-forming amorphous silica (SiO₂), the latter only in the batch operation; (iv) counter-current diffusion of H⁺ and Li⁺ through the surface layer (surface layer = depleted sublayer + precipitation sublayer); (v) dissolution of the surface layer at the solid-solution interface, through the reactions with water. The evidence comes from the near-proportionality between the lithium recovery and mass of dissolved β-spodumene, no detection of keatite-HAlSi₂O₆, particle morphology, precipitation of amorphous skins of SiO₂ decorated with boehmite specks observed by electron microscopy and predicted from thermodynamic modelling as well as from a mass-transfer analysis of the Li-recovery rates. Direct observations confirm the existence of a three-phase reacting system, as predicted from thermodynamic calculations, with the absence of a supercritical fluid phase. Lithium recoveries, of at least 28 % in a single step, are attainable, but only for long contact time of 48 h. Digestion lasting hundreds of hours is needed for the batch process to reach Li extraction corresponding to that of the sequential leach. The challenges for industrial implementation of the process comprise recycling of large amounts of water, avoiding the precipitation of silica that forms rinds, accelerating the hydrolysis of Li-depleted sublayer, concentrating the dilute solutions of Li⁺ and overcoming hesitance of industry to consider high-pressure treatment.

Original language	English
Article number	108398
Pages (from-to)	1-17
Number of pages	17
Journal	Minerals Engineering
Volume	204
DOIs	https://doi.org/10.1016/j.mineng.2023.108398
Publication status	Published - Dec 2023

Bibliographical note

Funding Information:
The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana . H.C.O. and G.S. acknowledge Murdoch University’s R&I Seed Grant 2021.

Funding Information:
The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana. H.C.O. and G.S. acknowledge Murdoch University's R&I Seed Grant 2021.

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© 2023 The Author(s)

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@article{3ad392c5c35641d489bc84eea1f18cd9,

title = "Pressure leach of β-spodumene with carbonic acid: Weak acid process for extraction of lithium",

abstract = "This contribution develops a process for recovering lithium from β-spodumene by sequential pressure leach with solutions of carbonic acid, as a replacement for digestion of β-spodumene with concentrated sulfuric acid. Six sequential steps, each operated at 200 °C and 100 bar for 1 h, retrieve 75 \% of lithium from the initial feed material. This compares with a 12.6 \% Li recovery from a single-stage (batch) operation. We develop both the thermodynamic and mass-transfer models of the leach process and argue that the lithium extraction is mass-transfer controlled. The underlying mechanism involves: (i) near-instantaneous ion exchange between H+ for Li+ at the onset of the digestion; (ii) direct formation of amorphous Li-depleted rinds; (iii) precipitation of secondary minerals, boehmite (AlO(OH)) and skin-forming amorphous silica (SiO2), the latter only in the batch operation; (iv) counter-current diffusion of H+ and Li+ through the surface layer (surface layer = depleted sublayer + precipitation sublayer); (v) dissolution of the surface layer at the solid-solution interface, through the reactions with water. The evidence comes from the near-proportionality between the lithium recovery and mass of dissolved β-spodumene, no detection of keatite-HAlSi2O6, particle morphology, precipitation of amorphous skins of SiO2 decorated with boehmite specks observed by electron microscopy and predicted from thermodynamic modelling as well as from a mass-transfer analysis of the Li-recovery rates. Direct observations confirm the existence of a three-phase reacting system, as predicted from thermodynamic calculations, with the absence of a supercritical fluid phase. Lithium recoveries, of at least 28 \% in a single step, are attainable, but only for long contact time of 48 h. Digestion lasting hundreds of hours is needed for the batch process to reach Li extraction corresponding to that of the sequential leach. The challenges for industrial implementation of the process comprise recycling of large amounts of water, avoiding the precipitation of silica that forms rinds, accelerating the hydrolysis of Li-depleted sublayer, concentrating the dilute solutions of Li+ and overcoming hesitance of industry to consider high-pressure treatment.",

keywords = "Carbonic acid process, Dissolution-precipitation mechanism, Lithium bicarbonate, Mass-transfer limitation, Pressure leach of spodumene, Weak acid process",

author = "Alhadad, \{Mahmoud F.\} and Oskierski, \{Hans C.\} and Johannes Chischi and Gamini Senanayake and Bernhard Schulz and Suvorova, \{Alexandra A.\} and Gain, \{Sarah E.M.\} and Dlugogorski, \{Bogdan Z.\}",

note = "Funding Information: The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana . H.C.O. and G.S. acknowledge Murdoch University{\textquoteright}s R\&I Seed Grant 2021. Funding Information: The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana. H.C.O. and G.S. acknowledge Murdoch University's R\&I Seed Grant 2021. Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = dec,

doi = "10.1016/j.mineng.2023.108398",

language = "English",

volume = "204",

pages = "1--17",

journal = "Minerals Engineering",

issn = "0892-6875",

publisher = "Elsevier",

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TY - JOUR

T1 - Pressure leach of β-spodumene with carbonic acid

T2 - Weak acid process for extraction of lithium

AU - Alhadad, Mahmoud F.

AU - Oskierski, Hans C.

AU - Chischi, Johannes

AU - Senanayake, Gamini

AU - Schulz, Bernhard

AU - Suvorova, Alexandra A.

AU - Gain, Sarah E.M.

AU - Dlugogorski, Bogdan Z.

N1 - Funding Information: The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana . H.C.O. and G.S. acknowledge Murdoch University’s R&I Seed Grant 2021. Funding Information: The authors would like to express their appreciation to Talison Lithium Pty Ltd for providing the spodumene concentrate. We are grateful to Professor Martin Bertau, of Institute of Chemical Technology of TU Bergakademie Freiberg for very useful discussions. We are also grateful for the analytical support from Ms Sabine Gilbricht during analysis at the Geometallurgy Laboratory at TU Bergakademie Freiberg. The authors acknowledge the facilities and scientific and technical assistance provided by Microscopy Australia at The University of Western Australia's Centre for Microscopy, Characterisation and Analysis, a facility financed by the University, State, and Commonwealth Governments. M.F.A. thanks Tianqi Lithium Kwinana and Murdoch University for providing a postgraduate scholarship. B.Z.D. H.C.O. and G.S. acknowledge financial support from Tianqi Lithium Kwinana. H.C.O. and G.S. acknowledge Murdoch University's R&I Seed Grant 2021. Publisher Copyright: © 2023 The Author(s)

PY - 2023/12

Y1 - 2023/12

N2 - This contribution develops a process for recovering lithium from β-spodumene by sequential pressure leach with solutions of carbonic acid, as a replacement for digestion of β-spodumene with concentrated sulfuric acid. Six sequential steps, each operated at 200 °C and 100 bar for 1 h, retrieve 75 % of lithium from the initial feed material. This compares with a 12.6 % Li recovery from a single-stage (batch) operation. We develop both the thermodynamic and mass-transfer models of the leach process and argue that the lithium extraction is mass-transfer controlled. The underlying mechanism involves: (i) near-instantaneous ion exchange between H+ for Li+ at the onset of the digestion; (ii) direct formation of amorphous Li-depleted rinds; (iii) precipitation of secondary minerals, boehmite (AlO(OH)) and skin-forming amorphous silica (SiO2), the latter only in the batch operation; (iv) counter-current diffusion of H+ and Li+ through the surface layer (surface layer = depleted sublayer + precipitation sublayer); (v) dissolution of the surface layer at the solid-solution interface, through the reactions with water. The evidence comes from the near-proportionality between the lithium recovery and mass of dissolved β-spodumene, no detection of keatite-HAlSi2O6, particle morphology, precipitation of amorphous skins of SiO2 decorated with boehmite specks observed by electron microscopy and predicted from thermodynamic modelling as well as from a mass-transfer analysis of the Li-recovery rates. Direct observations confirm the existence of a three-phase reacting system, as predicted from thermodynamic calculations, with the absence of a supercritical fluid phase. Lithium recoveries, of at least 28 % in a single step, are attainable, but only for long contact time of 48 h. Digestion lasting hundreds of hours is needed for the batch process to reach Li extraction corresponding to that of the sequential leach. The challenges for industrial implementation of the process comprise recycling of large amounts of water, avoiding the precipitation of silica that forms rinds, accelerating the hydrolysis of Li-depleted sublayer, concentrating the dilute solutions of Li+ and overcoming hesitance of industry to consider high-pressure treatment.

AB - This contribution develops a process for recovering lithium from β-spodumene by sequential pressure leach with solutions of carbonic acid, as a replacement for digestion of β-spodumene with concentrated sulfuric acid. Six sequential steps, each operated at 200 °C and 100 bar for 1 h, retrieve 75 % of lithium from the initial feed material. This compares with a 12.6 % Li recovery from a single-stage (batch) operation. We develop both the thermodynamic and mass-transfer models of the leach process and argue that the lithium extraction is mass-transfer controlled. The underlying mechanism involves: (i) near-instantaneous ion exchange between H+ for Li+ at the onset of the digestion; (ii) direct formation of amorphous Li-depleted rinds; (iii) precipitation of secondary minerals, boehmite (AlO(OH)) and skin-forming amorphous silica (SiO2), the latter only in the batch operation; (iv) counter-current diffusion of H+ and Li+ through the surface layer (surface layer = depleted sublayer + precipitation sublayer); (v) dissolution of the surface layer at the solid-solution interface, through the reactions with water. The evidence comes from the near-proportionality between the lithium recovery and mass of dissolved β-spodumene, no detection of keatite-HAlSi2O6, particle morphology, precipitation of amorphous skins of SiO2 decorated with boehmite specks observed by electron microscopy and predicted from thermodynamic modelling as well as from a mass-transfer analysis of the Li-recovery rates. Direct observations confirm the existence of a three-phase reacting system, as predicted from thermodynamic calculations, with the absence of a supercritical fluid phase. Lithium recoveries, of at least 28 % in a single step, are attainable, but only for long contact time of 48 h. Digestion lasting hundreds of hours is needed for the batch process to reach Li extraction corresponding to that of the sequential leach. The challenges for industrial implementation of the process comprise recycling of large amounts of water, avoiding the precipitation of silica that forms rinds, accelerating the hydrolysis of Li-depleted sublayer, concentrating the dilute solutions of Li+ and overcoming hesitance of industry to consider high-pressure treatment.

KW - Carbonic acid process

KW - Dissolution-precipitation mechanism

KW - Lithium bicarbonate

KW - Mass-transfer limitation

KW - Pressure leach of spodumene

KW - Weak acid process

UR - https://www.scopus.com/pages/publications/85172304110

U2 - 10.1016/j.mineng.2023.108398

DO - 10.1016/j.mineng.2023.108398

M3 - Article

AN - SCOPUS:85172304110

SN - 0892-6875

VL - 204

SP - 1

EP - 17

JO - Minerals Engineering

JF - Minerals Engineering

M1 - 108398

ER -

Pressure leach of β-spodumene with carbonic acid: Weak acid process for extraction of lithium

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