Computational Modelling for extraction
of Lithium from sea water
Presented by
Shivansh Mishra
Under the supervision of
Prof. Tarun Kumar Kundu
Department Of Metallurgical and Materials Engineering
Contents
• Introduction
• Literature Survey
• Research gap
• Future Plan
• References
Introduction
Distribution of global Li end-uses in various applications in 2019 Global lithium production in the years from 2010 to 2025
U.S.G. Survey, Mineral commodity summaries 2020s, Reston, VA, 2020. Advance review on the exploitation of the prominent energy-storage element Lithium. Part II: From sea water and spent lithium ion batteries (LIBs) Pankaj K. Choubey et al 2017 Minerals
Sources of Lithium
Schematic representation of the different sources for the production of lithium Graphical representation of the amount and type of lithium resources based on their physical state
Recent advances in nanomaterial development for lithium ion-sieving technologies Yasin Orooji et al 2022 Desalination A review on lithium recovery using electrochemical capturing systems Sifani Zavahir et al 2021 Desalination
Solar Evaporation
Schematics of the brine evaporation process for Li recovery.
• Wells are drilled to access underground brine deposits and then • Presence of many cations such as Na+, K+, Ca2+, and Mg2+
transferred to evaporation ponds with chloride ions in the brines makes it challenging to
achieve a high purity product main issue in Li precipitation
• Brine remains in the pond until the removal of most liquid water
is the co-precipitation of Mg.
are removed through evaporation
• Inexpensive but impractical in some areas due to need to
• Brine concentrated by solar evaporation to crystallize Na, K and
reinject brine to maintain power production
MgCl2, leaving concentrated solution of LiCl which is further
refined after removal of impurities to get Li 2CO3 or LiOH • Time Consuming as it depends upon climate
• Land Intensive and wastage of water can lead to its scarcity
Lithium recovery from brines: A vital raw material for green energies with a potential environmental impact in its mining and processing Victoria Flexer et al 2018 Science of The Total Environment
Precipitation Advantage:
Low cost
Easy to scale up
Disadvantage:
Energy intensive
Less efficient
Chemicals
reagents used
impacts
environment
(a) Two-stage method and (b) a method involving several steps for recovering Li carbonate from high Mg/Li brines
• Brines with Mg/Li < 8, ‘carbonate precipitation’ is common in which Mg is first precipitated via calcium oxide followed by
the precipitation of Li as Li carbonate achieved by adding sodium carbonate
• Brines with Mg/Li > 8 ‘aluminate precipitation’ (or ‘Mg precipitation’ ) method is employed for Li recovery. In aluminate
precipitation, aluminium chloride is added along with sodium hydroxide to generate aluminium hydroxide which selectively
precipitates Li as Li aluminate (or Li carbonate)
M. Bertau, G. Martin, Integrated direct carbonation process for lithium recovery from primary and secondary resources, in: Materials H. Wang, Y. Zhong, B. Du, Y. Zhao, M. Wang, Recovery of both magnesium and lithium from high Mg/Li ratio brines using a novel process,
Science Forum vol. 959, Trans Tech Publ, 2019 Hydrometallurgy (2018)
Recovery of lithium from brines using precipitation methods in recent studies
Reagents/Precipitant Source Composition Temperature Performance Reference (Year)
(°C)
Sodium carbonate, Salt lake brine Li (0.7–0.9 g/L) and 90 Recovery:>90% J.W. An, et al.
Calcium hydroxide Mg (15–18 g/L) Purity:99.55% (2012)
Na2CO3 Salt lake brine Li+ 0.36 g/L and 80 Recovery:84% Z. Xu, et al.
Mg2+ 0.81g/L Purity:99.6% (2014)
Activated Al-Ca and Synthetic salt Al / Li = 3.5:1 (mole 70 Precipitation Y.-H. Li, et al.
Al-Fe alloys solution ratio), Ca 0.28 g/L, rate:94.6% (2015)
Li+ 0.8 g/L
Aluminum based Salt lake brine Li+(1 g/L) and 90 Precipitation X. Liu, et al.
material Mg2+ (20 g/L) rate:78.3% (2018)
NaOH and Na2CO3 Industrially refined Mg=1.14% Li=3.22% 60 Recovery:>85% C. Quintero, et
solution brine Ca= 0.03% Na=0.04% Purity:99% al.(2019)
K=0.02%
Sodium metasilicate Simulated brine Li+ (2 g/L) and 25 Recovery:86.7% Y. Zhang, et
nanohydrate Mg2+ (60 g/L) al.2019)
Na2HPO4 solution Refined salt lake Mg/ Li =41.1 40 Recovery:93.2% X. Lai, et al.
brine (2020)
Tri-sodium phosphate Dead Seawater Mg(33,310 mg/L) and 40 Recovery:40% A. Alsabbagh, et
brine Li(18 mg/L) al. (2021)
Adsorption
• Li+ is captured by an adsorbent with high Li+ selectivity and desorbed by some solvents, thereby separating Li + from
other coexisting ions
• Adsorption has advantages of simplicity and environmental cleanliness but identifying excellent adsorption materials
with high Li+ selectivity, high adsorption capacity, and reasonable operation stability is still required
On the Structure and Lithium Adsorption Mechanism of Layered H 2TiO3 Rajashekhar Marthi et al 2021ACS Applied materials & interfaces Recent advances in nanomaterial development for lithium ion-sieving technologies Yasin Orooji et al 2022 Desalination
Li recovery by adsorption reported in recent studies
Li source Adsorbent Adsorption capacity Reference (Year)
(mg.g-1)
Salt lake brine Layered H2TiO3 32.7 R. Chitrakar, et al (2014)
Concentrated natural brine Iron-doped Li-Ti oxides 34.8 S. Wang, X. Chen, et al(2018)
Enriched salt lake brine MnO2/PVDF composite 11.06 S. Zandvakili, M. Ranjbar (2018)
Natural brine Li1.33Mn1.67O4 50 F. Ohashi, Y. Tai (2019)
Great Salt lake water LiMn2O4 nanowires/diatomaceous earth 18.6 R. Marthi, Y.R. Smith (2019)
Synthetic salt solution Aluminum-doped-Li manganese oxides 32.6 G. Zhang, et al (2019)
Synthetic salt solution Li+-IIP-Fe3O4@C 22.26 Q. Liang, et al (2020)
Salt lake brine Granular H4Mn5O12 17.2 X. Lai, X. Lai, et al (2020)
Salt lake brine Magnetic Li-Al-LDHs 5.83 J. Chen, S. Lin, J. Yu (2020)
Simulated brine Porous H4Ti5O12 nanofibers 59.1 S. Wei, et al (2020)
Synthetic salt solution Aluminum-based MOF material (MIL-121) 1.25 Q. Wei, et al (2021)
Salt lake brine H2TiO3/ diatomaceous earth 8.25 R. Marthi, Y.R. Smith (2021)
Salt lake brine Li-Al-LDHs 7.27 J. Zhong, S. Lin, J. Yu (2021)
Salt lake brine Granular Li-Al-LDHs/NH4Al3(SO4)2(OH)6 9.16 Q. Luo,R. et al (2021)
Synthetic salt solution Layered H2TiO3 40 Marthi, et al (2021)
Salt lake brine Fluorine-Pillared MOFs 18.8 X. Jiang, et al (2021)
Salt lake brine Titanium based Li-ion sieve powder 19.22 X. Zhu, et al (2021)
Synthetic salt solution Cross-linked poly(N-isopropylacrylamide-co-acryloylamidobenzo-18-crown- 7.21 S. Zhang, et al (2021)
6) functionalized MOF-808
Electrochemical
• Electrochemical methods refers to the insertion and extraction of lithium in lithium-ion batteries via adsorption
materials have been exploited as electrodes, and the insertion or extraction of Li + can be controlled by applying
electric field through controlled potential difference.
• Common electrode materials for lithium extraction can be mainly divided into two types: lithium iron phosphate
(LFP) type and Lithium manganese oxide (LMO) type.
Working principle behind a complete cycle of the lithium recovery: step 1,
lithium capture in brine water; step 2, exchange with recovery solution; step 3, Electrochemical lithium recovery process in LMO-Zn system. (a) Discharging step: lithium ions
lithium release in recovery solution; step 4, exchange with brine water. are selectively captured from the brine water, and zinc oxidation occurs. (b) Charging step:
lithium ions are released into the charging solution, and zinc reduction occurs.
Batteries for lithium recovery from brines Mauro Pasta Energy & Dynamics Energy Environ. Sci., 2012 Electrochemical Lithium Recovery with a LiMn 2O4–Zinc Battery System using Zinc as a Negative Electrode Seongsoo Kim, et al Energy TechnologyVolume 6, Issue 2 ,
Summary of electroactive materials, Li extraction capacity and energy consumption reported in recent studies for Li recovery
from brines using electrochemical methods.
Source Electroactive materials Energy Product purity Extraction References (Year)
consumption (%) capacity (mg.g-1)
(Wh/mol L-1)
Simulated brine LiMn2O4 and Li1-xMn2O4 18 - 22 M.-Y. Zhao, et al
(2017)
Simulated concentrated sea water LiMn2O4 and Li1-xMn2O4 18.6 - 21 M.-Y. Zhao, et al
(2017)
Simulated brine Li1-xNi1/3Co1/3Mn1/3O2 and Ag 2.60 96.4 10.83 C.P. Lawagon, et al
(2018)
Simulated brine Li1-xNi0.5Mn0.5O4 and Ag 1.32 98.14 8.74 C.P. Lawagon, et al
(2019)
Simulated brine λ-MnO2 and Ag 3.07 99 10.1 S. Kim, et al (2019)
Simulated brine LiNi0.038Mo0.012Mn1.95O4 and 7.91 97.2 14.4 X. Zhao, et al (2020)
Ni0.038Mo0.012Mn1.95O4/AC
Simulated brine PPy/Al2O3/LiMn2O4 and AC 1.41 97.37 12.84 X. Zhao, et al (2020)
Simulated brine λ-MnO2 and BiOCl@PPy 1.007 - 10.88 J. Niu, et al (2021)
Salt lake brine LiMn2O4 and Li1-xMn2O4 16 - 15-16 W. Xu, et al (2021)
Simulated brine λ-MnO2/LiMn2O4 and Pt 23.38 - 75.06 Y. Mu, et al (2021)
Electrodialysis
• Electrodialysis (ED) is a dialysis phenomenon in which charged ions in
solution migrate through the ion exchange membrane under an applied
electric field.
• In the presence of an electric potential difference, cations and anions can
directionally migrate through the selective ion exchange membrane with
ion-selective permeability, thereby separating and concentrating ions.
Two mechanisms in ionic-liquid-membrane electrodialysis: (a) Li+ permeating through liquid
ED for removing divalent ions and producing concentrated seawater and Li recovery method using an ionic liquid
membrane and (b) Li+ blocked by liquid membrane.
Development of technology for recovering lithium from seawater by electrodialysis using ionic liquid membrane Tsuyoshi Hoshino Fusion Engineering and Design Novel approaches for lithium extraction from salt-lake brines: A review GuiLiu et al 2019 Hydrometallurgy
Membrane
• Nanostructured membranes (pore size in the range of sub-nanometer
to few nanometers) is used for extracting lithium from brine on the
basis of Donnan exclusion and steric hindrance, which allows only
monovalent ions to pass through and reject multivalent ions (process is
termed as Nanofiltration)
• NF used along with ED improves Lithium recovery
Membrane-based technologies for lithium recovery from water lithium resources: A review XianhuiLi et al 2019 Journal of Membrane
Science
Li separation using membrane-based technologies reported recently
Source Mode of operation Membrane material Performance References (Year)
Synthetic salt solution Nano-Filteration Commercial polyamide Flux: 50 LMH, Mg2+ rejection: 92% Y. Li, et al (2019)
Simulated brine Nano-Filteration Amine functionalized [MimAP][Tf2N] Flux: 37.8 LMH, Mg2+ rejection: 83.8%, Li+ rejection: H. Wu, et al(2020)
modified polyamide 24.4%, Li/Mg selectivity:8.12
Synthetic salt solution Nano-Filteration Polydopamine and polyethylenimine Flux: 21.33, Mg2+ rejection: 86.7%, Li+ rejection: 5.34%, M.A. Ashraf, et al (2020)
composite Li/Mg selectivity:7.15 Mg2+/Li+ reduced from 30 to 4.1
Synthetic salt solution Nano-Filteration 1,2-bis(triethoxysilyl)ethane coated TiO2 Flux: 57 LMH, Mg2+ rejection: 20.3%, Li+ rejection: 74.7% X. Wu, et al (2020)
under the transmembrane pressure at 6 bar
Synthetic salt solution Electrodialysis MOF(ZIF-8)/polypropylene Ion selectivity of K+/Mg2+ =4.49, Na+/Mg2+ =4.0, M. Mohammad, et al (2020)
Li+/Mg2+ =3.87 and Ca2+/ Mg2+ = 1.1
Synthetic salt solution Electrodialysis Mg doped Li manganese oxide Sulfonated Li/Mg selectivity:4.82, Li/K selectivity:3, Li/Na P.P. Sharma, et al (2020)
poly (ether ether ketone) selectivity:2.17 adsorption of lithium =15.2 mg/g
Synthetic brine Nano-Filteration polyethyleneimine grafted polyamide Mg2+ rejection: 92%±3 Li/Mg selectivity: 33.4 stabile for Y. Feng, et al(2022)
162 h filtration at 6 bar and reduced Mg/Li from 50 to 8
Synthetic salt solution Nano-Filteration Diaminoethimidazole bromide modified Flux: 132 LMH, Mg rejection:95.8%, Li+ rejection:55.6% H. Peng, et al(2021)
polyamide stable for 200 h continuous filtration lithium flux = 0.7 mol
m−2 h−1 for Mg2+/Li+ = 20 at 6 bar
Synthetic salt solution Nano-Filteration Cu modified phenylenediamine membrane 16.2 ± 2.7 LMH/bar, Li/Mg selectivity: 8 ± 1.0 L. Wang, et al.(2021)
Synthetic salt solution Nano-Filteration Quaternized bipyridine modified Pure water flux: 96.6 ± 3 LMH, Mg2+ rejection:92% ± 3 Y. Feng, et al (2022)
polyethyleneimine stable for 162 h at 0.6 Mpa reduced Mg/Li from 50 to 8.5
Solvent Extraction
• Solvent extraction (liquid-liquid extraction or chemical extraction)
uses the difference in partition coefficients of Li+ between the liquid
and organic phases to achieve purification or concentration of lithium
resources
• It is mainly used in recovery of Lithium from brine due to its low cost
high product yield in lesser time and reduces water consumption.
Recent advances in nanomaterial development for lithium ion-sieving technologies Yasin Orooji et al 2022 Desalination
By Solvent extraction / liquid-liquid extraction or chemical extraction
Li source Extractant Co-extractant Diluent Extraction References (Year)
efficiency (%)
Salt lake brine TBP - [C4mim][PF6] 90.93 C. Shi, et al (2014)
Salt lake brine TBP NaClO4 [C4mim][PF6] 99.12(3) C. Shi, et al (2015)
Salt lake brine TBP FeCl3 MIBK 98.9(5) W. Xiang, et al (2016)
Salt lake brine N523,TBP FeCl3 Kerosene 96(14) D. Shi, et al (2018)
Simulated brine TBP [Bmim]3PW12O40 Dimethyl 99.23(5) Y. Wang, et al (2019)
phthalate
Simulated brine TBP FeCl3 Diethyl 65.53 Z. Zhou, et al (2020)
succinate
Salt lake brine TBP P507,FeCl3 Kerosene 99.8(3) H. Su, et al (2020)
Simulated brine TBP [OHEMIM][NTf2] - 94.2 W. Zhou, et al (2021)
Simulated brine TBP NaBPh4 CH2ClBr 87.65 Z. Ren, et al (2021)
N523= N,N-bis(2-ethylhexyl)acetamide NaClO₄ = Sodium perchlorate FeCl3 = Ferric chloride [Bmim]3 PW12O40 = (1-butyl 3-methyl imidazolium phosphotungstate) P507=2-Ethylhexylphosphonic acid mono-2-ethylhexyl ester
[Omim]Ntf2= 1-Octyl-3-Methylimidazolium Bis(trifluoromethanesulfonyl)imide NaBPh4 = Sodium tetraphenylborate [Bmim]Bph4 = 1-butyl-3-methylimidazolium tetraphenylboron [N1888][P507] = trialkylmethylammonium di(2-
ethylhexyl)orthophosphinate [C4mim][PF6] =1-butyl-3-methylimidazolium hexafluorophosphate MIBK= methyl isobutyl ketone CH2BrCl / CH2BrCl = Bromochloromethane
Materials for
Lithium Extraction
Organic
adsorbents Inorganic
(Solvent
extraction) adsorbent
materials
Crown ether β-diketone system Ketone system Organophosphorus Ion liquid system Aluminum salt
Lithium-ion sieve
system extractants extractants extractants system extractants extractants adsorbent
Aluminum salt Lithium-aluminum Manganese oxide- Titanium oxide-
adsorbent hydroxides ion sieve ion sieve
H4Ti5O12 (spinel H2TiO3 (layered
structure) structure)
Crown ether chelating system extractants
• When the pore size of the crown ether is close to the cation
diameter, the formed complex exhibits optimal stability
(MACROCYLIC EFFECT)
• Spatial structure and pore size of the crown ether can, be
adjusted by regulating the donor atom type and quantity,
crown ether ring size, and substituent type to improve the
selectivity for certain metal ions
• Introduction of an electron-withdrawing group-modified side
chain on the crown ether ring helps to form a stable complex
between the crown ether and lithium
Separation and purification of lithium by solvent extraction and supported liquid membrane, analysis of their mechanism: a review. Swain B (2016) Journal of Chemical Technology and Biotechnology
β-Diketone system materials
Extraction
system
Organophosphorus acid
• di-2-ethylhexylphosphoric acid
(D2EHPA)
• (bis-2,4,4-trimethylpentyl D2EHPA CYANEX 272
phosphinic acid) cyanex 272
• (ethylhexyl phosphinic acid mono-
2-ethylhexylester) PC-88A
Organophosphorous
PC-88A
Neutral
• Tributyl phosphate (TBP)
• Dibutyl butylphosphonate (DBBP)
• Trioctylphosphine oxide (TOPO)
Neutral Ketones System
• Methyl isobutyl ketone (MIBK)
• Diisobutyl ketone (DIBK)
• Acetophenone
a. TBP, b. DBBP, c. TOPO, d. MIBK, e. DIBK, f. acetophenone
TTA-Thenoyltrifluoroacetone TOPO-Trioctylphosphine oxide PHEN-Phenanthroline
DMP-2,9-Dimethyl-1,10-phenanthroline DBM- Dibenzoylmethane
Separation and purification of lithium by solvent extraction and supported liquid membrane, analysis of their mechanism: a review. Swain B (2016) Journal of Chemical Technology and Biotechnology
Ion liquid system materials
• Ionic liquids are melting salt solvent composed of
anions and cations that exhibit remarkable
performance properties such as
• High thermal stability
• Low volatility
• Low saturated vapor pressure (Negligible)
• Low melting temperature
• Low phase disengagement time (a) [C4mim][PF6] (b) [C4mim][NTf2] (c) [N4444][DEHP] (d) [N4444][BEHP]
(Gray ball: carbon atom, blue ball: nitrogen atom, red ball: oXygen atom, white ball:
• Can increase distribution ratios & selectivity of fluorine atom, yellow ball: sulfur atom, and pink ball: phosphorus atom)
Li+/Mg2+
• Tunable viscosity
• Non-flammability
• Environmentally friendly
• Ionic liquid systems exhibit extraction properties due
to their polyfunctionality, asymmetry, flexibility, and
large ionic size of in the liquid structure
Ionic Liquids for the Selective Solvent Extraction of Lithium from Aqueous Solutions: A Theoretical Selection Using COSMO-
Novel approaches for lithium extraction from salt-lake brines: a review. Liu G, Zhao Z, Ghahreman A (2019) Hydrometallurgy RSFelipe Olea et al 2022 Application of Ionic Liquids in Hydrometallurgy
Summary of Li adsorption capacities reported for hybrid systems in recent years
Source Membrane material Adsorption capacity References
(Year)
Synthetic salt solution Crown ether functionalised Static: 24.25 mg.g-1 D. Sun, et al
GO/PVDF Membrane flux 13.62 mL cm−2 min−1 (2018)
90.9% of maximum adsorption capacity
retained after 10 cycles
Synthetic salt solution Al2O3 supported Li4Mn5O12 Static: 22.9mg.g-1 F. Xue, et al
adsorption capacity of was 60.88% after (2020)
5 adsorption-desorption cycles
Dynamic: 9.74 mg.g-1
uptake reduced by 20 % after 3 adsorption-
desorption cycles
Synthetic brine Sulfonated Polyarylene Static: 20.54mg.g-1 Z. Wang, et al
ether nitrile hollow fiber uptake reduced by 4.3% after 10 (2021)
adsorption-desorption cycles
Synthetic salt solution Crown ether functionaliozed Static: 168.5 mg.g-1 X. Zheng, et al
GO/chitosan/PVA 88.31% adsorption capacity after 5 cycles (2021)
Research gap
• Li+ and Mg2+ have a similar ionic radius and chemical characteristics making it difficult to separate.
• Lithium recovery is known to be easier in brines having low Mg/Li mass ratio due to the relatively
high lithium content. However, an effective separation of Mg and Li from high Mg/Li brines is
more difficult and must follow a strict process at higher relative cost.
• No universal extraction process exists for recovering lithium, because the process is typically
designed according to the brine composition of the salt lake brine, pH, temperature, etc.
• Separation ability or stability can be significantly enhanced by combing separation methods, such
as membrane/ion sieve, membrane/ionic liquid, and adsorption/electrodialysis but they are too
costly to be used practically.
• Environmental concerns.
• Sustainability.
Future Plan
• Designing a molecule/membrane that selectively adsorbs Lithium(Li+) over competing ions
(Mg2+, Ca2+, Na+ and K +) ions by DFT .
• Effect of structure on extraction efficiency.
• Effect of hydration (hydrophobic/ hydrophilic) or effect of different solvent on adsorption
capacity.
• Effect of O/A ratio (organic / aqueous) on adsorption.
• Thermodynamic analysis like interaction energy or binding energy.
• Analysis of reaction mechanism (Path of reaction), determination of intermediate stage.
• Effect of pH on the adsorbing capacity of molecule.
• Calculation of Surface energy.
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