Desalination 505 (2021) 114983

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Desalination
journal homepage: www.elsevier.com/locate/desal

Li+ adsorption performance and mechanism using lithium/aluminum

layered double hydroxides in low grade brines
Jing Zhong a, b, Sen Lin a, c, *, Jianguo Yu a, c, *
a
National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Technology, Shanghai, 200237, China
b
Engineering Research Center of Salt Lake Resources Process Engineering, Ministry of Education, East China University of Science and Technology, Shanghai, 200237,
China
c
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology,
Shanghai, 200237, China

H I G H L I G H T S

• Li+ adsorption capacity of Li/Al-LDHs can reach to 7.26 mg/g at 303 K.

• Li/Al-LDHs show a high Li+ selectivity with αLi
Mg of 125 in Qarham old brine.
• Mg2+/Li+ ratio decreases from 301.58 in brine to 0.43 in strip by Li/Al-LDHs.

A R T I C L E I N F O A B S T R A C T

Keywords: Lithium/aluminum layered double hydroxides (Li/Al-LDHs) without elution damage, have been regarded as the
Desorption most applicable adsorbents in the industrial lithium extraction from brines, while the low adsorption capacity
Washing and unclear adsorption/desorption mechanism are restraining their lithium extraction performance. In this
Structure stability
study, Li/Al-LDHs with regular two-dimensional hexagonal flats, prepared by a simple coprecipitation method,
Column experiment
Ultrahigh Mg2+/Li+ ratio
demonstrated the highest Li+ adsorption capacity reported of 7.27 mg/g in the Qarhan Salt Lake old brine with
an ultrahigh Mg2+/Li+ ratio at room temperature. Besides, the Li/Al-LDHs had a great adsorption selectivity to
Li+ with the ion selective sequence of Li+ > Na+ > K+ > Ca2+ ≫ Mg2+, and the separation factor between Li+ and
Mg2+ (αLi
Mg) reached up to 125. The adsorption capacity of Li/Al-LDHs exceeded 7.0 mg/g after 12 adsorption-
desorption cycles, showing a great stability on the adsorption performance and crystal structure. In addition,
the adsorption-desorption column experiments manifested that the Li+ adsorbed on the Li/Al-LDHs could be
eluted completely by neutral water and the Mg2+/Li+ ratio in the eluent reduced significantly to <0.43 from
301.58.

1. Introduction
In decade years, the lithium demand faces a strong growth with the
rapid development of the electric car and lithium-ion battery industries.
At present, all commercial lithium productions are mainly acquired from
high grade lithium ores and brines which are the biggest resource (59%)
for lithium occurrence [1]. Lithium extraction from brines has a great
economical and scientific prospect in view of the simple operation and
low cost. However, Li+ in the brines in many areas is accompanied by a
mass of Mg2+ and the ultrahigh Mg2+/Li+ ratio severely obstructs the
effective lithium exploitation on account of the similar ionic radius be­
tween Li+ and Mg2+ [2,3]. As a result, it is essential and challenging to
explore efficient technologies to separate valuable Li+ from these
enormous Mg2+ impurities in low grade brines with high Mg2+/Li+
ratio. Up to now, several methods for lithium recovery from brines,
including membrane process [4], solvent extraction [5,6], adsorption
[7], etc., have been investigated extensively. Among them, adsorption
has been developed rapidly in consideration of the advantages of envi­
ronmental protection and high adsorption selectivity [8].
For now, adsorbents in lithium recovery could be mainly divided into

* Corresponding authors at: National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Tech­
nology, Shanghai, 200237, China.
E-mail addresses: linsen@ecust.edu.cn (S. Lin), jgyu@ecust.edu.cn (J. Yu).

https://doi.org/10.1016/j.desal.2021.114983
Received 31 August 2020; Received in revised form 24 January 2021; Accepted 26 January 2021
Available online 10 February 2021
0011-9164/© 2021 Elsevier B.V. All rights reserved.
J. Zhong et al. Desalination 505 (2021) 114983

three species, including lithium manganese oxides (LMO) [9,10], tita­
nate (LTO) [11] and lithium aluminum layered double hydroxide (Li/Al-
LDHs). According to the comparison of adsorption performances in
Table 1, though the Li+ adsorption capacity of the Li/Al-LDHs is lower
than that of LMO and LTO，the adsorbed Li+ on Li/Al-LDHs could be
easily eluted using neutral deionized water or low ionic strength solu­
tions without dissolution, reflecting the great potential in the industrial
lithium extraction.
Previous studies have verified that the structure of Li/Al-LDHs is
consisted of altered two-dimensional aluminum hydroxide layered plate
linked by hydrogen bonds. Lithium ions fill in octahedral voids of the
packing hydroxide ions while anions and water molecules locate in the
interspace between aluminum hydroxide layers, which could interact
each molecules and ions with hydrogen bond, electrostatic interaction
and van der Waals [22,23]. Due to the characteristic structure of Li/Al-
LDHs, the chemical formula could be expressed as [LimAl2(OH)6]
Clm⋅nH2O (m = 0–1). It has been proven that Li/Al-LDHs sheets are
inclined to stack together and become larger particles ascribe to exten­
sive interlamellar hydrogen bonding networks. Vacancies as Li
brines and offer a credible theoretical direction for the industrial
application of Li/Al-LDHs as Li+ adsorbents.
2. Experimental methods
2.1. Materials and reagents
All chemical reagents used in experiments were purchased from
Sinopharm Chemical Co., Ltd. LiCl, AlCl3 and NaOH were of analytically
pure grade without further purification. Five unary stock solutions with
the concentration of 1 mol/L were prepared by dissolving LiCl⋅H2O,
NaCl, KCl, CaCl2 and MgCl2⋅6H2O in deionized water, respectively. The
selectivity of Li/Al-LDHs among co-existing cations was investigated
through the mixed solutions of Li+:Me = 1:1 (molar ratio, Me = Na+, K+,
Ca2+ and Mg2+) with different concentrations by diluting the stock so­
lution with deionized water. The brine used in experiments was Qarhan
Salt Lake old brine with 0.399 g/L Li+, 1.394 g/L Na+, 0.478 g/L K+,
0.046 g/L Ca2+, 120.330 g/L Mg2+.
+

adsorption sites would appear in Li/Al-LDHs structure by the removal of 2.2. Li/Al-LDHs preparation
Li+ from the components and the adsorption-desorption process can be
described as following formula [24]: According to previous preparation experiments, the aqueous solution
[ ] [ ] with the optimized Li+/Al3+ molar ratio of 1:2 (Fig. S1) was added
xLiCl + Li(m− x) Al2 (OH)6 Cl(m− x) + (n + 1)H2 O⇌ Lim Al2 (OH)6 Clm ⋅nH2 O + H2 O
dropwise into NaOH solution under sonication and stirred at 45 ◦ C
(Fig. S2) until the pH of mixed solution dropped to <8.0. Then the
It has been reported that Li/Al-LDHs with various Li/Al molar ratio
precipitate was washed with deionized water to remove the residual and
could be synthesized following via different procedures including solid-
dried at 60 ◦ C overnight to gain the Li/Al-LDHs adsorbents.
state synthesis [25], coprecipitation [26,27], gel-crystalline synthesis
[28] and hydrothermal method [29]. Nonetheless, the low adsorption
2.3. Adsorption/desorption experiments
capacity is still the bottleneck for the industrial application of Li/Al-
LDHs in lithium recovery from brines shown in Table 1. In addition, it
All adsorption experiments were carried out in a shaking incubator at
is totally vague for the concrete Li+ adsorption-desorption mechanism,
150 rpm with Li/Al-LDHs suspending in conical flasks filled with the old
especially the role of accompanying cations of using Li/Al-LDHs to
brine. The adsorption kinetic experiments were performed with
extract Li+ from low grade brines, hinding the reinforcement for
different dosages of Li/Al-LDHs at 303 K. The adsorption isotherms were
adsorption performances.
studied for 4 h at 303 K, 318 K and 333 K, respectively. The residual
In this work, high-efficiency Li/Al-LDHs were prepared via a simple
cation concentrations in the solution were determined by filtering the
coprecipitation and their physicochemical properties were systemati­
supernatants at given intervals through a 0.22 μm filter membrane
cally investigated by various measurements. Adsorption kinetics, iso­
without any cation loss according to control experiments. The adsorp­
therms and cycling stability of the Li/Al-LDHs were analyzed in Qarhan
tion capacity Qe (mg/g) was determined according Eq. (1).
old brine with ultrahigh Mg2+/Li+ ratio. Then, the Li+ adsorption
mechanism in the low grade brines were analyzed in detail dependent on Qe =
c0 − ce
V (1)
the survey on the specific adsorption and the microstructure variation in m
the Li/Al-LDHs. Finally, the column experiments of granulated Li/Al-
where c0(mg/L) and ce(mg/L) are the initial and residual cation con­
LDHs were conducted to comprehensively evaluate the lithium extrac­
centrations in solution; V (L) is the solution volume; m (g) is the mass of
tion efficiency from low grade brines. We believed the work could
Li/Al-LDHs.
significantly enhance the development of lithium recovery in low grade
The pseudo-first-order model and the pseudo-second-order model
were adopted to describe the adsorption kinetics, which were expressed
Table 1 as Eqs. (2) and (3) [30].
Li+ adsorption performance of different adsorbents. ln(qe1 − qt ) = lnqe1 − k1 ∙t (2)
Adsorbent Li+ adsorption Dissolution Ref
performance t 1 1
= + t (3)
Li1.6Mn1.6O4 37 mg/g in seawater Mn dissolution: 2% [12] qt k2 q2e2 qe2
Li1.6Mn1.6O4 26.93 mg/g in Qarhan Mn dissolution: 1.1–1.8% [13]
old brine where qe1 (mg/g) and qe2 (mg/g) are the Li+ adsorption capacities at
Li4Mn5O12 62.47 mg/g in Urmia Mn dissolution: 1.01–1.15% [14] equilibrium; qt (mg/g) is the lithium adsorption capacity at time of t; k1
Lake
LiMn2O4 29.61 mg/g in Li+-rich Mn dissolution: lower than [15]
and k2 [g/(mg⋅min)] are the adsorption constants.
solution 0.5% Besides, the experimental data were fitted with Langmuir isotherm
Ti doped-LMO 21.9 mg/g in seawater Mn dissolution: 0.70–1.1% [16] model, Freundlich isotherm model and Sips isotherm model expressed as
Li4Ti5O12 59.1 mg/g (highest) in Ti dissolution: 0.5–3% [17] Eqs. (4)–(7), respectively.
Li+-rich solution
Li2TiO3 12.84 mg/g in Li+ adsorption capacity [18] Qmax KL ce
geothermal water dropped 2% in 5 cycles Langmuir isotherm model : qe = (4)
1 + KL c e
Li/Al-LDHs <7 mg/g in brine \ [7]
Li/Al-LDHs 5-6 mg/g in brine [19]
Freundlich isotherm model : lnqe = lnKF + 1/n∙lnce (5)
Li/Al- 3.46–5.83 mg/g in brine [20]
LDHs@Fe3O4
Li/1.25Al-LDHs Li+ recovery rate of 90% \ [21] RL = 1/(1 + KL c0 ) (6)

2
J. Zhong et al.
Qmax KL cm
Sips isotherm model : qe = e
(7)
1 + KL c m
e
where qe (mg/g) and ce (mg/L) are the lithium adsorption capacity and
the lithium concentration at equilibrium, respectively, and the param­
eter Qmax (mg/g) represents the saturated adsorption capacity. KL and KF
(min− 1) are the Langmuir (Sips) and Freundlich model constants. The
parameter n represents the heterogeneity of the adsorbent. Moreover,
the dimensionless constant separation RL is used to explain the main
characteristic of Langmuir isotherm. The parameter m is the Sips model
exponent.
In the co-existing cation effect experiments, the adsorption process
was conducted in the solutions with different initial concentrations of
Li+/Me (Me = Na+, K+, Ca2+ and Mg2+) in a range of 0.05–0.5 mol/L.
The distribution coefficient (Kd) and separation factor (αLi Me ) were
determined by Eqs. (8), (9).
Kd = (c0 − ce )∙V/(ce ∙m) (8)
/ except aluminum, chlorine and oxygen according to the EDS result. The
αLi
Me = Kd,Li Kd,Me (9)
where c0 (mg/L) and ce (mg/L) are the initial and residual cation con­
centrations in solution. V (L) is the solution volume and m (g) is the mass
of Li/Al-LDHs.
The desorption experiments were carried out in sealed flasks with 5 g
of Li/Al-LDHs and agitation at 150 rpm. The effects of dosages (L/S),
temperature and Li+ concentration in the eluent on the structural sta­
bility and desorption performance of Li/Al-LDHs were investigated by
the adsorption-desorption cyclic experiments. The Li+ desorption ca­
pacity was figured according to Eq. (10).
cd − cd0
Qd = V (10)
m porosity. What’s more, the inner structure and surface property of the
where cd0 (mg/L) and cd (mg/L) are the initial and final Li+ concentra­
tion in the eluent; V (L) is the solution volume; m (g) is the mass of Li/Al-
LDHs.
2.4. Bench-scale column experiments
The granulated Li/Al-LDHs with a size of 150 μm was prepared by
using polyvinyl butyral (PVB) according to Zhou’s method to drop the
column pressure [31]. Subsequently, 2.5 g Li/Al-LDHs were filled in the
column (1 cm in inner diameter, 10 cm in height) for lithium extraction
experiments at room temperature. During a complete adsorption-
washing-desorption cycle, the brine was pumped into the column at
flow rate of 0.3 BV/min for adsorption where the bed volume (BV) was
defined as BV = Lπr2. Then deionized water flowed through the column
with a rate of 3.8 BV/min to remove Na+, K+, Ca2+, Mg2+ trapped in the
interparticle space, especially the Mg2+ which would heavily affect the
lithium desorption efficiency. Subsequently, the flow rate of deionized
water was reduced to 0.3 BV/min as eluent for lithium deintercalation.
2.5. Assays
The morphology of Li/Al-LDHs was observed by using a Quanta 250
scanning electron microscope (SEM) and a JEM-2100EX transmission
electron microscopy (TEM) with accelerating voltage of 200 kV and 60
kV, respectively, particularly equipped with an energy dispersive X-Ray
spectroscopy (EDS) to identify the element species. The composition of
Li/Al-LDHs was detected by an inductively coupled plasma optical
emission spectroscopy (ICP-OES) from Simbol Materials, Inc. after being
dissolved by concentrated nitric acid. The crystal structure was analyzed
by a Rigaku D/max 2550 X-ray diffractometer (XRD) with mono­
chromatized Cu-Kα radiation (λ = 1.5405 Å) in the 2θ range of 10–80◦ at
40 kV, 100 mA and a scanning rate of 10◦ /min. Thermogravimetry (TG)
analysis was performed from 20 ◦ C to 610 ◦ C under air flow on a
3
Desalination 505 (2021) 114983
thermogravimetric apparatus (Q600SDT, TA, US). The adsorption
mechanism of Li/Al-LDHs was analyzed preliminarily by X-ray photo­
electron spectroscopy spectrum (XPS, ESCALAB-2, UK) where the
binding energies were referred to C1s peak at 284.8 eV. The Fourier-
transform infrared (FTIR) spectra were carried on a Nicolet 6700 spec­
trometer (ThermoScientific, USA) with samples in KBr pellets and
wavenumber ranging between 400 cm− 1–4000 cm− 1 at 25 ◦ C. The
specific surface area of Li/Al-LDHs was determined by the N2
adsorption-desorption isotherms at 77 K using a micromeritics ASAP-
2010C adsorption apparatus.
3. Result and discussion
3.1. Characterization of Li/Al-LDHs
As shown in the SEM image in Fig. 1a, the as-prepared Li/Al-LDHs
presented regular two-dimensional hexagonal flats clustering to needle/
rose petal-like crystalline. No other element was detected on the surface
HRTEM image in Fig. 1c demonstrated a legible layered structure and
the lattice structure could be clearly identified in Fig. 1d that the pro­
jection of the structure on its (001) plane exhibited hexagonal symmetry
detected by selected area electron diffraction (SAED) patterns. In addi­
tion, the XRD pattern of Li/Al-LDHs with sharp and symmetric peaks at
11.6◦ , 23.1◦ and 20.3◦ shown in Fig. 2a was well matched with that of
LiAl2(OH)7⋅xH2O (JCPDS card No.31-0704) and peaks at (003), (006)
and (009) verified the layered structure of Li/Al-LDHs mentioned
before. Fig. 2b and c gave the N2 adsorption isotherms and the pore size
distribution of the Li/Al-LDHs, respectively, which showed the Li/Al-
LDHs followed Type IV adsorption behaviors, indicating the adsor­
bents were micro-mesoporous lamellar particles with interparticle
adsorbent showed a high specific area of 161 m2/g and average pore size
of 7.14 nm which could be contributed to the fast mass diffusion. Fig. 2d
gave the weight loss and heat flow of the Li/Al-LDHs as functions of
temperature in the range of 20–600 ◦ C. The observed three stages of
weight loss from TG curve which were consistent with three exothermic
peaks in the DSC curve. The peaks before 150 ◦ C and in the range of
150–250 ◦ C resulted from the evaporation of physical adsorbed water
and crystal water, respectively. The peak in the range of 15-250 ◦ C
represented the decomposition of Li/Al-LDHs intoγ-Al2O3. According to
the weight loss of crystal water evaporation (26.9%) and Li/Al molar
ratio, the chemical composition of Li/Al-LDHs was determined as
LiCl⋅5Al(OH)3⋅1.7H2O, which was consistent with above EDS result.
3.2. Adsorption kinetics and isotherms
As shown in Figs. 3 and 4, the lithium adsorption kinetics and iso­
therms of Li/Al-LDHs were investigated with different Li/Al-LDHs dos­
ages to take insight into the Li+ adsorption performance in Qarham Salt
Lake old brine. It could be confirmed from Fig. 3a that all the Li+
adsorption under different Li/Al-LDHs dosages had an analogous trend
and reached equilibrium in 120 min with an unaltered Li+ adsorption
path. The Li+ adsorption capacities with dosages of 60, 30 and 20 mL/g
were 7.27, 7.05, 5.96 mg/g, respectively, reflecting the Li+ adsorption
capacity was positive correlated with Li/Al-LDHs dosage in the brine
and the adsorption capacity in our study was obviously higher than that
reported value listed in Table 2. On the basis of the fitting results shown
in Fig. 3b and Table 3, the pseudo-second-order model (R2 > 0.99)
showed the superiority in the description of the Li+ adsorption process,
reflecting chemisorption would be the controlling step.
The adsorption isotherm curves at temperatures of 303, 318, 333 K
were recorded in Fig. 4. It could be seen the adsorption capacity was
enhanced with increasing temperature, demonstrating that the Li+
adsorption process was an endothermic reaction. In addition, on the
basis of correlation coefficients listed in Table 4, the adsorption
J. Zhong et al. Desalination 505 (2021) 114983

Fig. 1. The morphology images of Li/Al-LDHs: SEM (a), TEM (b), HRTEM (c), SAED (d).

Fig. 2. XRD (a), N2 adsorption/desorption isotherms at 77 K (b), micro-mesoporous size distribution (c), TG (d) of Li/Al-LDHs.

isotherms could be described better by Sips isotherm model, manifesting LDHs in the low grade brine with massive Mg2+.
the inhomogeneous adsorption sites in the Li/Al-LDHs for Li+. The
variation trend of Qmax values along with temperature calculated by Sips
model was in great agreement with that of the Qe in experimental data. 3.3. Ion selectivity
All the RL values <1.0 proved a high-efficient Li+ adsorption by Li/Al-
In view of the complicated composition in low grade brines, it was

4
J. Zhong et al.
Fig. 3. Adsorption kinetics curves (a) and linear fitting for Li+ (b) of Li/Al-LDHs with different dosage (solid line in b: pseudo-first-order model; dash line in b:
pseudo-second-order model).
Fig. 4. Isotherm curves of Li/Al-LDHs at 303 K (a), 318 K (b), 333 K (c).
necessary to investigate the adsorption selectivity of Li/Al-LDHs be­
tween Li+ and competitive cations including Na+, K+, Ca2+ and Mg2+.
To investigate the cation selectivity of Li/Al-LDHs, 5 g of Li/Al-LDHs and
30 mL of different dilute binary solutions included Li+ and Me (Me =
Na+, K+, Ca2+ and Mg2+) were mixed for 4 h at 298 K to determine the
adsorption capacity for Li+ and separation factor αLi Me . It was obviously
observed from Fig. 5 that the Li+ adsorption capacities in different bi­
nary systems were positive correlated with the Li+ concentration. αLi Na
and αLi
K reduced with the increasing Li
+
concentration and finally
5
Desalination 505 (2021) 114983
reached to a plateau gradually, which referred that the Li+ selectivity of
Li/Al-LDHs declined with the enhanced competitive ion concentrations.
In fact, the Na+ concentration and K+ concentration in potassium
extracted old brine was 1.394 g/L (0.06 mol/L) and 0.478 g/L (0.012
mol/L), respectively, where αLi Na and αK were close to 90 and 125,
Li
respectively, manifesting Li/Al-LDHs had high selectivity towards Li+.
Due to barely Ca2+ or Mg2+ were adsorbed, ion selective sequence of Li/
Al-LDHs was regarded as: Li+ > Na+ > K+> > Ca2+/Mg2+.
Besides, the adsorption in a homogeneous solution with the same
concentration of Li+/Na+/K+/Ca2+/Mg2+ was investigated to study the
J. Zhong et al. Desalination 505 (2021) 114983

Table. 2 -OH group of the metal hydroxide layer [37]. Compared with the virgin
Comparison of Li + adsorption performance and selectivity between several adsorbents, the Cl2p3/2 binding energy transformed from 197.46 eV and
works. 197.87 eV to 197.71 eV and 198.09 eV, respectively, which manifested
Authors Li+ adsorption Selectivity Ref
performance

A. D. 2.3 mg/g in 24 h using High selectivity towards Li+ [32] Table. 4

Ryabtsev granulated Li/Al-LDHs from Mg2+, Ca2+ Isotherm model fitting results of Li+ adsorption process by Li/Al-LDHs.
Mariappan 91% of Li+ extraction rate αLi Li
Na =47.8, αK =212
[33] Freundlich
in geothermal brine
Jiang 3.0 mg/g using Li/Al- Li > Na > K > Ca > Mg
+ + + 2+ 2+
[34] T/K Qexp./(mg⋅g− 1) KF 1/n R2 SSE
LDHs with ultrahigh with αLi
Me varying among 4–15 303 7.7579 4.1215 0.1264 0.8077 0.2536
MgCl2 concentration 318 8.1067 4.0732 0.1306 0.9579 0.1227
Chen 5.68 mg/g of Li/Al- Li+ > Na+ > K+, Ca2+ ≫ Mg2+ [35] 333 8.3088 2.6528 0.2204 0.9385 0.1752
LDHs@Fe3O4 in Qarhan with the αLi
Me of 10.22, 35.6,
old brine 35.2, 179.5, respectively, in
old brine Langmuir
This work 7.26 mg/g of Li/Al-LDHs Li+ > Na+ > K+ > Ca2+ ≫ \ T/K Qexp./(mg⋅g− 1) Qmax KL RL R2 SSE
in Qarhan old brine Mg2+ in dilute solution
303 7.7579 7.5718 0.3966 0.0063 0.9009 0.2166
318 8.1067 7.6145 0.6171 0.0040 0.9839 0.1150
competition between Li+ and these co-exist ions. The equilibrium 333 8.3088 7.9802 0.1195 0.0205 0.9240 0.1971

adsorption capacities of Li+/Na+/K+/Ca2+/Mg2+ on Li/Al-LDHs and

2+
Me (Me = Na , K , Ca
αLi + +
and Mg2+) were listed in Table 5. As expected, Sips
the results were constant with the aforementioned conclusion that ion T/K Qexp./(mg⋅g− 1) Qmax KS m R2 SSE
selective sequence of Li/Al-LDHs followed the order of Li+ > Na+ > K+ 303 7.7579 7.9042 0.4956 0.7614 0.9935 0.1334
> Ca2+ ≫ Mg2+ with the αLi Me in a range of 21.79 to 125.33 in the dilute 318 8.1067 9.2696 0.6306 0.4216 0.9934 0.0247
solution exhibiting a higher separation coefficient compared with the 333 8.3088 10.6534 0.2089 0.5180 0.9432 0.1617
work listed in Table 2, which provided a great prospective of application
for lithium extraction from brines with ultrahigh Mg2+/Li+ ratios.
300
3.4. Adsorption mechanism
4
Li+ adsorption capacity(mg/g)

250
Furthermore, FTIR and XPS were applied to analyze the adsorption
Li+/Na+
mechanism of Li/Al-LDHs. Fig. 6 gave the FTIR spectrums of Li/Al-LDHs 2 Li+/K+
before and after Li+ adsorption. The broad and intense adsorption band
200
Li+/Mg2+
at 3500 cm− 1 was recognized as the middle -OH stretching vibration of Li+/Ca2+
the hydroxide. The band at 1600 cm− 1 was considered as the bending 0 Li
Na
150

Li
M
vibration of -OH caused by crystal water. The invariable intensity of Li
K

bands at 535 cm− 1 and 755 cm− 1 which were attributed to the defor­ 100
mation vibration of Al–O6 octahedron and stretching vibration, -2
respectively, indicating the structure stability of Li/Al-LDHs before and 50
after adsorption. Moreover, bands at 941 cm− 1 and 1027 cm− 1 were
-4
assigned to the deformation vibration of Al-OH. Especially, the intensive
0
intensity of band at 941 cm− 1 after adsorption reflected that the -OH
bending variation was caused by the Cl− intercalcation at interlayers
0.0 0.1 0.2 0.3 0.4 0.5
[36]. Li+ concentration(mol/L)
The XPS spectra of the Li/Al-LDHs before and after adsorption were
exhibited in Fig. 7 to unravel the element distribution and surface state Fig. 5. The Li+ adsorption capacities and αLi
Me values with different binary so­
lutions (Li:Me = 1:1, Me = Na+, K+, Ca2+, Mg2+).
of Li/Al-LDHs. Fig. 7a gave the wide scan of XPS spectra of Li/Al-LDHs,
where O1s, C1s, Cl2p and Al2p peaks were observed. Meanwhile the
peaks at 1304.7 eV were attributed to Mg1s which manifested a Table 5
considerable amount of Mg2+ in the brine remained among Li/Al-LDHs Adsorption selectivity of Li/Al-LDHs between Li+ and other cations.
interparticles after adsorption. The Al2p binding energy shifted from
Ions C0 (mmol/L) Ce (mmol/L) Qe (mg/g) Kd (mL/g) αLi
Me
74.00 eV to 74.20 eV after adsorption in Fig. 7b, indicating the occu­
pancy of Li+ into Al–O octahedral vacancies. Fig. 7c and d showed the Li+ 47.74 33.38 1.49 65.78 –
Na+ 49.31 48.44 0.40 2.71 21.79
Cl2p spectra resolutions of Li/Al-LDHs before and after adsorption. The K+ 54.21 53.36 0.51 2.41 24.47
Cl2p spectra could be divided into Cl2p1/2 and Cl2p3/2 indicating that Ca2+ 47.47 46.95 0.30 1.66 39.39
Cl− occupied two distinct positions in Li/Al-LDHs, which were consid­ Mg2+ 51.64 51.48 0.06 0.05 125.33
ered as electrostatic interaction with Li+ and hydrogen-bonds with the

Table 3
Linear fitting results of Li + adsorption process on Li/Al-LDHs.
L/S Qe(exp) mg/g Pseudo-first-order model Pseudo-second-order model

k1 Qe1 mg/g R2 SSE k2 Qe2 mg/g R2 SSE

60 7.27 0.0383 4.4641 0.8317 3.2351 0.0333 7.3533 0.9976 0.7328

30 7.05 0.0222 2.5228 0.8037 1.8916 0.0813 7.0922 0.9995 0.3167
20 5.96 0.0523 2.7057 0.9170 1.9028 0.0668 6.0471 0.9997 0.2434

6
J. Zhong et al. Desalination 505 (2021) 114983

different desorption conditions and subjected to the adsorption once

After adsorption more. The effects of volume, temperature and Li+ concentration in
eluent on Li+ desorption kinetics were illustrated in Fig. 9a–c. It was
observed that the Li+ desorption process could be finished in 45 min
under different desorption conditions and the eluent volume and higher
temperature were positively associated with the Li+ deintercalation
from Li/Al-LDHs. It could be referred that Li+ deintercalation was
restricted by Li+ concentration in eluent at equilibrium combined with
Intensity

Before adsorption the effect of eluent volume and Li+ concentration. In Fig. 9d, Li+ re-
adsorption capacities of Li/Al-LDHs after desorption under different
conditions, had analogous variation with the Li+ desorbed amount.
Especially, except the desorption condition with L/S = 20, Li+ adsorp­
1630 1027
-OH Al-OH 755 tion capacities were all above 7.0 mg/g in residual 11 cycles without any
941 Al-O adsorbent dissolution or sharp decline in capacity which showed a great
Al-OH
3500 535 cycle performance of Li+ extraction and indicated that Li/Al-LDHs were
-OH Al-O
excellent adsorbents for Li+ ion recovery from low grade salt lake brines
4000 3000 2000 1000 with ultrahigh Mg2+/Li+ ratios. Considered with resource and energy
Wavenumber(cm-1) consumption, the saturated adsorbed Li/Al-LDHs would prefer to be
eluted by neutral deionized water with the dosage of L/S = 60 at 298 K.
Fig. 6. FTIR spectrums of Li/Al-LDHs before and after Li+ adsorption.
3.6. Column adsorption-desorption recycle
that more lithium chlorides were intercalated into Li/Al-LDHs and
formed the strong coulombic attraction immediately in consort with the The adsorption breakthrough curves of main cations in the brine
hydrogen-bonds. during column cycle process using the Li/Al-LDHs as adsorbents were
listed in Fig. 10a. The Li+ adsorption reached to saturation at 14 BV
3.5. Desorption and recycle while Na+, K+ adsorption saturated at 1.5 BV already, and barely Ca2+
was adsorbed on Li/Al-LDHs in the column adsorption which manifested
The cyclic regeneration of Li/Al-LDHs was a significant character­ the great Li+ adsorption capacity and high selectivity of Li/Al-LDHs.
istic for industrial application in lithium extraction from the old brine And the breakthrough curve of Mg2+ was not presented in Fig. 10a in
with ultrahigh Mg2+/Li+ ratio. Fig. 8 gave the cyclic schematic of Li/Al- view of the inaccurate measurements by ICP through output solution
LDHs including adsorption, washing and desorption. To obtain the op­ due to the high concentration in Qarhan salt lake old brine. Washing
timum desorption condition, saturated Li/Al-LDHs were eluted under process was adopted to wash away residual impurity ions in the

a b

Cl2p Cl2p

197.46 eV 197.71 eV
197.87 eV 198.09 eV
Intensity
Intensity

2p3/2 199.31 eV 2p3/2

199.06 eV
199.47 eV 199.69 eV
2p1/2 2p1/2
c d

205 200 195 190 205 200 195 190

Binding energy (eV) Binding energy (eV)

Fig. 7. XPS spectra of Li/Al-LDHs: survey spectra (a), Al2p spectra (b), Cl2p spectra before adsorption (c), Cl2p spectra after adsorption (d).

7
J. Zhong et al. Desalination 505 (2021) 114983

Fig. 8. Schematic of the adsorption-washing-desorption cycle of Li/Al-LDHs.

Fig. 9. The effects of L/S ratio (a), temperature (b), initial Li+ concentration (c) on Li+ desorption kinetics curves and the cycle performance (d) of Li/Al-LDHs.

8
J. Zhong et al.
1.0
a 400
0.8
Li+
Ct/C0(%)
Na+
K+
0.6
Ca2+
0.4
0 5 10 15
Bed Volume
Fig. 10. Cation breakthrough (a) and desorption (b) curves of the granulated Li/Al-LDHs packed column for Li+ recovery from old brine.
interparticle volume of the Li/Al-LDHs column after initial loading step.
The cation (Li+, Na+, K+, Ca2+ and Mg2+) concentrations during the
elution step were listed in Fig. 10b. It could be seen that Li+ concen­
tration in eluent was gradually decreased as the Li+ unloaded from the
adsorbents diffusing into water accompanying with the dropping Mg2+
concentration, which was not washed completely and residual in the
interparticle volume of the adsorbent during the washing process. By
contrast, the desorbed amounts of Na+, K+ and Ca2+ escaped from
washing could be neglected. Li+ adsorption capacity of Li/Al-LDHs in
the column at 298 K reached to 6.41 mg/g which had a slight diminution
compared to the capacity in static evaluation. It was worth mentioning
that the Mg2+/Li+ molar ratio sharply declined from 301.58 in old brine
to 0.43 in the strip solution, meanwhile >94% of Na+, K+, Ca2+ and
Mg2+ were removed during the washing stage. In brief, the adsorbed Li+
from brine had been fully desorbed and the recovery rate was 72.2% due
to the Li+ loss in washing.
4. Conclusion
The as-prepared Li/Al-LDHs showed a considerable adsorption
selectivity and capacity for Li+ in Qarham Salt Lake old brine with an
ultrahigh Mg2+/Li+ ratio. Li/Al-LDHs could keep great stability during
the multiple adsorption without any dissolution, revealing a great
prospect for industrialization. Moreover, column experiment results
reflected that the Li/Al-LDHs had a high adsorption capacity of 6.41 mg/
g in dynamic evaluation and the Mg2+/Li+ ratio was sharply declined to
0.43 in the strip solution from 301.58 in the old brine. Our work prove
the prepared Li/Al-LDHs are efficient and environmental friendly for Li+
adsorption, offering a green approach for the lithium extraction from the
low grade brines with ultrahigh Mg2+/Li+ ratio.
CRediT authorship contribution statement
Sen Lin and Jianguo Yu conceived and designed the study. Sen Lin
and Jing Zhong performed the experiments. Sen Lin and Jing Zhong
wrote and revised the paper. Jianguo Yu and Sen Lin reviewed and
edited the manuscript. All authors read and approved the manuscript.
Declaration of competing interest
With great pleasure we submit the manuscript entitled “Li+ adsorp­
tion performance and mechanism using lithium/aluminum layered
double hydroxides as adsorbents: batch and column experiments in the
lithium extraction from ultrahigh Mg2+/Li+ ratio brines” to Desalina­
tion. The authors are Jing Zhong, Sen Lin and Jianguo Yu at National
Engineering Research Center for Integrated Utilization of Salt Lake Re­
sources, East China University of Science and Technology, Shanghai,
200,237, China. No conflict of interest exits in the submission of this
Desalination 505 (2021) 114983
500
Li+ 4
Na+ b
K+
Ca2+ 3
300
Mg2+
CMe(mg/L)
CMg(g/L)
200 2
100 1
0
0
20 0 2 4 6 8
Bed Volume
manuscript, and manuscript is approved by all authors for publication. I
would like to declare on behalf of my co-authors that the work described
was original research that has not been published previously, and not
under consideration for publication elsewhere, in whole or in part. All
the authors listed have approved the manuscript that is enclosed.
Acknowledgement
This work was sponsored by the National Natural Science Founda­
tion of China (21978094, U20A20142), and Major Science and Tech­
nology Projects of Qinghai Province (2019-GX-A7).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.desal.2021.114983.
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