Hydrometallurgy 185 (2019) 149–161

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Understanding the role of natural clay minerals as effective adsorbents and T

alternative source of rare earth elements: Adsorption operative parameters
⁎ ⁎
Aref Alshameria,b,c, , Hongping Heb, , Chen Xina, Jianxi Zhub, Wei Xinghua, Runliang Zhub,
Hailong Wanga
a
School of Environmental and Chemical Engineering, Foshan University, Foshan, Guangdong 528000, China
b
Guangdong Provincial Key Laboratory of Mineral Physics and Materials & Key Laboratory of Mineralogy and Metallogeny, Guangzhou Institute of Geochemistry, Chinese
Academy of Sciences, Guangzhou 510640, PR China
c
Geological Survey and Mineral Resources Board, Ministry of Oil and Minerals, Sana'a, Yemen

A R T I C LE I N FO A B S T R A C T

Keywords: To better understand the influence of structure and surface properties of NCMs towards REE, requires individual
Natural clay minerals research for each NCM. The adsorption/extraction for light (La3+) and heavy (Yb3+) REE of kaolinite (Kao),
Rare earth elements montmorillonite (Mt), muscovite (Ms), illite (Ilt), were systematically investigated and compared. Additionally,
Adsorption all the NCMs were fully characterized by XRD, XRF, XPS, Zeta potential and nitrogen adsorption-desorption
Lanthanides extraction
isotherms to build the relationship between adsorption/extraction mechanism and minerals' property. Our ex-
periments show that the Mt. exhibits highest adsorption and regeneration efficiencies for both La3+ and Yb3+
and decrease in the order of Mt > Ms > Ilt > Kao, while Kao has highest extractions efficiencies for both REE
in the order of Kao > Ilt > Mt > Ms 89% for La3+ and 85% for Yb3+ were achieved from Kao and the lowest
extractions were obtained from Ms. (63% for La3+ and 57% for Yb3+). The lack of Ms. on both reuse and
extraction characteristics is believed to be related to presence of iron oxide associated with Ms. In addition, the
important role of the pH in extraction of REE from NCMs was evidenced, when REE-NCMs come into contact
with the NH4+ solution, the pH is rapidly increased over initial pH solution for both Mt. and Ms., thus leading to
the decrease of the availability of ion-exchangeable REE with NH4+ions. The results illustrated that the structure
and surface properties of NCMs are also the key factors that affect the rare earth leaching, thus identifying the
types of NCMs and associated impurities in clay materials are important, either for getting the best leaching
system or in developing a new one.

1. Introduction (Voßenkaul et al., 2015). Various methods, such as precipitation, fil-

The critical role of rare earth elements (REE) in advanced technol-
ogies leads to their increasing demand from the industry (Kondo and
Kamio, 2002; Ogata et al., 2015 and Tadjarodi et al., 2015). REE have
been used in different sectors such as, nuclear energy, medicine, elec-
tronics, metallurgy, chemical engineering, and computer manu-
facturing. The development of advanced technologies have created in-
creasing demand for REE, China dominates the world potential with
reserves estimated to be over 90% of the global production (Voßenkaul
et al., 2015; Anastopoulos et al., 2016). Therefore, the global emphasis
on identifying new alternate sources of REE to ensure adequate supply
for present and future use is an important issue. As a result, the re-
covery of REE is a significant issue that needs appropriate attention
tration and solvent extraction have been used to recover REE, but these
methods are not economically attractive (Iannicelli-Zubiani et al.,
2015). Among the available methods, adsorption has gained wider at-
tention because it is environment friendly, economically sustainable
and has simple leaching process. However, conventional physical pro-
cessing methods are found to be useless in the enrichment of rare earths
from sources (Iannicelli-Zubiani et al., 2015; Xiao et al., 2016a,b).
Recently, the ion-adsorption clays has the focus of most research
endeavours as an alternative source and the best example of this for-
mation process can be found in Southern China, ion-adsorption clays
account for about 35% of the China's total REE production
(Moldoveanu and Papangelakis, 2013; Yang and Zhang, 2015; Xiao
et al., 2016a,b; Voßenkaul et al., 2015).The ion-adsorption type rare

⁎
Corresponding authors at: Guangdong Provincial Key Laboratory of Mineral Physics and Materials & Key Laboratory of Mineralogy and Metallogeny, Guangzhou
Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, PR China
E-mail addresses: aref_alshmiri@yahoo.com (A. Alshameri), hehp@gig.ac.cn (H. He).

https://doi.org/10.1016/j.hydromet.2019.02.016
Received 20 September 2018; Received in revised form 21 January 2019; Accepted 23 February 2019
Available online 26 February 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
A. Alshameri, et al.
earths ore are generally formed by the tropical weathering of rare earth
rich host rocks (granitic or igneous) (Voßenkaul et al., 2015). During
this process REE ions are mobilized by the transfer into an aqueous
solution which percolates through the weathering body and are ad-
sorbed onto NCMs (Verplanck, 2017).This provides evidence that NCMs
have the ability of adsorbing lanthanide ions released/solubilized
during weathering and ion-adsorption clays commonly contain
0.05–0.2 wt% of rare earth oxides adsorbed onto NCMs (Moldoveanu
and Papangelakis, 2012). Although the NCMs deposits containing ad-
sorbed lanthanides which are of substantially lower grade than other
types of REE mineral resources, but because of their abundance in
surface layers in nature, efficient adsorption properties, easier ionic
exchange of REE, lower cost of mining and processing, NCMs are eco-
nomically- attractive source of rare earths (Moldoveanu and
Papangelakis, 2013). The NCMs are electronegative, saturated with
cations such as Na+, K+, Ca2+, and Mg2+ thereby capable to exchange
cations such as REE to the surface. Previous research showed REE
contained in NCMs were mainly present as physisorbed ions, therefore
easy to recover by a simple ion-exchange procedure (Moldoveanu and
Papangelakis, 2012, 2013). It is thus evident that the adsorption of rare
earth ions on NCMs would have great influence on the mineralization
process and the leaching process of the ion-adsorption type rare earths
ore.
Recently, there has been a significant interest in adsorption of REE
on NCMs (Bradbury and Baeyens, 2002; Coppin et al., 2002; Chen et al.,
2012; Gladysz-Plaska et al., 2014; Iannicelli-Zubiani et al., 2015;
Anastopoulos et al., 2016). Bradbury and Baeyens (2002) and Piasecki
and Sverjensky (2008) both studied REE speciation/distribution on clay
at wide ranges of pH, ionic strength and concluded that most of the
surface-adsorbed lanthanides occur as simple “clay-REE” or as hydro-
lyzed “clay-O-REE2+” species. Up to date, extensive research has been
conducted on the extraction of REE from only kaolinite (Chi, 1989).
Similarly, Moldoveanu and Papangelakis (2012) have reported the re-
covery of REE from two types of clays (yttrium-rich and yttrium-
medium) and they indicate that the XRD pattern of clays are composed
of illite, mica, quartz, and kaolinite as major components. These re-
searches only revealed the behavior of the rare earth in the leaching
process and focused the influence of various leaching agents on re-
covery of rare earth from clays. They did not identify the influence of
structure and surface properties of NCMs on REE extraction mechanism.
In addition, mica group such as muscovite and biotite are major mi-
neralogical components of granite and granodiorite. The granitic
weathered crust elution-deposited rare earth ore is an important re-
source of rare earths, thus the mica group contribute significantly to
radionuclides retardation in the granitic environment (Pan et al., 2017).
Nowadays, the ion-exchangeable phase rare earth is recovered by
in-situ leaching process using (NH4)2SO4 achieving between 80 and
90% REE extraction (Moldoveanu and Papangelakis, 2013; Stoltz,
2017). As a result, 60–90% of the REE are absorbed onto NCMs and can
be recovered by ion-exchange mechanism with monovalent salt solu-
tions (Moldoveanu and Papangelakis, 2013 and Voßenkaul et al.,
2015). The remaining 10–40% are not recovered to date, either because
of the need for more aggressive lixiviant leaching conditions or because
of the need to better understand the effect of the structure and surface
properties of NCMs on extraction mechanism towards REE. There are
clear advantages of NCMs as REE sources. Practically, there is no sys-
tematic study on the influence of structure and properties of different
types of NCMs on their recovery behaviors towards REE under identical
experimental conditions. Additionally, to the best of our knowledge, no
information is yet available on REE desorption/recovery by Micas
(Muscovite, Illite, biotite) have been conducted for REE. However, a
deep insight into the fate of REE and its extraction onto different types
of NCMs is required for a more clear understanding of their mechanism
behavior. In this study, four types of NCMs, namely kaolinite, mon-
tmorillonite, muscovite and illite were investigated and compared for
their adsorption / recovery of REE (light REE La and heavy REE Yb as
150
Hydrometallurgy 185 (2019) 149–161
models).
The objective of this research is to evaluate the influence of different
types of NCMs on their adsorptive/recovery behaviors towards light
and heavy REE. The adsorption/recovery kinetics, adsorption iso-
therms, effects of pH, reuse and extraction of La3+ and Yb3+ from
NCMs were investigated and compared. Moreover, in order to build the
relationship between adsorption mechanism and minerals' property, the
NCMs samples were characterized by the X-ray diffraction (XRD), X-ray
fluorescence (XRF), X-ray photoelectron spectroscopy (XPS) analyses,
Zeta potential and N2 adsorption-desorption isotherms to obtain the
mineralogical and physicochemical parameters. The insights obtained
in this study are value-added utilization of NCMs in the environmental
engineering and as alternative source of REE as well as a vital reference
for the predictive model.
2. Materials and experimental methods
2.1. Materials and chemicals
All NCMs were collected from China, namely kaolinite (Kao) sample
from Maoming, Guangdong province, Calcium montmorillonite (Mt)
sample from Chifeng, Inner Mongolia, illite (Ilt) sample from
Duchuantou, Zhejiang province, Muscovite (Ms) and biotite (Bio)
samples were purchased from Shijiazhuang Chenxing Industry Co., Ltd.
All the chemicals used, such as, lanthanum (LaCl3), ytterbium
(YbCl3.6H2O), nitric acid (HNO3) ammonium sulfate (NH4)2SO4,sodium
hydroxide (NaOH) and hydrochloric acid (HCl), are of analytical grade.
2.2. Preparation for NCMs samples
NCMs were washed with distilled water to remove soluble matter
and then dried in an oven at 80 °C for 24 h. The NCMs were pulverized
and passed through a 0.075 mm sieve.
2.3. Analysis and characterization methods
Powder X-ray diffraction (XRD) experiments were performed be-
tween 2° and 70° (2θ) with a step size of 0.02° and a measuring time of
0.8 s per step using a Bruker D8 Advance diffractometer with Cu-Kα
(λ = 0.154 nm) radiation operating at 40 kV and 40MA and identified
using JCPDS files.
The chemical compositions of the samples were tested by
Netherlands PANalytical PW2424 X-ray fluorescence (XRF) spectro-
scopy. The prepared samples were fused with lithium metabor-
ate–lithium tetraborate flux which also includes an oxidizing agent
(Lithium Nitrate), and then poured into a platinum mould. The re-
sultant disk was in turn analyzed by XRF spectrometry. The XRF ana-
lysis was determined in conjunction with a loss-on-ignition at 1000 °C.
The resulting data from both determinations were combined to produce
the total.
N2 adsorption-desorption isotherms were determined at 77 K on a
Micromeritics ASAP 2020 system (Norcross, USA) at liquid nitrogen
temperature (−196 °C). Before the measurement, the samples were
outgassed at 250 °C for 12 h. The specific surface area (SBET) was cal-
culated using the multiple-point Brunauer-Emmett-Teller (BET)
method.
Zeta potential was conducted by a Malvern Instruments Ltd., UK,
Zetasizer Nano ZS 90. For the zeta potential measurements, 10 mg
(0.01 g) NCM was added into a 50 mL of 20 ppm REE (La3+ or Yb3+)
solution and a magnetic bar was subsequently used for 30 min stirring
time at room temperature. The zeta potential was examined in a range
of 3–6.3 pH. The initial pH was adjusted by different concentrations of
0.1 M, 0.01 M and 0.05 M of HNO3 solution. Quality control was per-
formed by repeating the experiments two times and average data was
reported.
The X-ray photoelectron spectroscopy (XPS) analyses were carried
A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

out with a Thermo Fisher K-Alpha XPS instrument (Thermo Fisher
Scientific, UK) using monochromatic Al Kα X-rays and an electrostatic
hemispherical analyser. The spectra were acquired with 400 μm X-ray
spot size, 100 eV pass energy, 30 eV high resolution scans. The base
vacuum in the analysis chamber was around 10–8 Torr. For all the
studied samples, the Binding Energy (BE) scale was calibrated with
respect to the aliphatic component of C1s peak (BE = 284.8 eV) of the
surface carbonaceous contaminants. Quality control was performed by
repeating the experiments two times and average data was reported.
2.5.1. Effect of lixiviate concentrations on REE leaching
To evaluate the influence of lixiviate concentrations on REE ex-
traction from NCMs, the concentrations of initial NH+ 4 were varied in
the range of 0.2–1.0 mol/L for 1 h.
2.5.2. Effect of contact time on REE leaching
The optimum time required for REE extraction from NCMs were
examined as a function of contact time in the range of 10 min to 60 min
at pH 4.5 and 25 °C.

2.4. Batch adsorption experiments

Chlorides of lanthanum and ytterbium were used for the prepara-
tion of stock solutions (1000 ppm). The stock solution was further di-
luted with distilled water to get the desired concentrations of experi-
mental working solutions. All batch adsorption experiments were
carried out using stopper test tube (50 mL) in a thermostatic shaker
with natural clay mineral/liquid ratio of 0.2 g/20 mL. The mixtures
were shaken in an orbital shaker (IKA KS 4000 ic control) with a con-
stant speed of 200 rpm and temperature of 25 °C for a given time, and
then the adsorbents were separated by centrifuge (cence, H1850). After
that, the concentration of La3+ and Yb3+ in the residual solution was
measured by ICP-MS (Thermo iCAP Q). Quality control testing included
experiments with duplicates.
2.4.1. Adsorption kinetics experiments
The optimum time required for the La3+ and Yb3+ was determined
as a function of contact time in the range of 10 min−24 h of 20 ppm
REE concentration at a fixed pH 4.5 and 25 °C. After the selected con-
tact time, the NCMs were separated from the liquid using a centrifuge
(cence, H1850). The amount of REE captured by the NCMs were de-
termined by measuring the adsorption of REE in solution through
ICP–MS analyses before and after the adsorption experiments. Also, the
solution pH in the range of time was determined.
2.4.2. Adsorption isotherm experiments
The effect of initial La3+ and Yb3+ concentration on the adsorption
capacities of La3+ and Yb3+ in the batch adsorption experiment were
evaluated by varying the concentrations in the range of 10–100 ppm for
Kao, Ilt and Ms. and 10–120 ppm for Mt. with contact time for 2 h.
The adsorption efficiencies (%) for the NCMs and the equilibrium
adsorption capacities (qe) were calculated, respectively by using the
following equations:
(C0 ‐Ce )
Removal efficiency (%) = × 100
C0 (1)
2.5.3. Effect of pH solution on REE leaching
The pH solutions were determined during the contact time to in-
vestigate the pH effect on REE extraction efficiencies. The initial pH
was adjusted by 0.1 M HCl and NaOH solution. The leaching efficiencies
(%) for the four NCMs were calculated by using the following equa-
tions:
(Cl )
Leaching efficiency (%) = × 100
Ct (3)
Cl is the REE concentration in solution (ppm) after the leaching step,
and it was determine by ICP–MS analysis of the liquid phase after se-
paration.
Ct is the amount of REE ion adsorbed by natural clay minerals at
equilibrium.
3. Results and discussion
3.1. Characterization of NCMs
3.1.1. XRD analysis
The XRD patterns of all NCMs are presented in Fig. 1. It shows that
all NCMs are composed almost entirely of natural clay mineral and a
few impurities. XRD shows that Mt. and Kao content minor amounts of
quartz (~5%). On other hand, Ms. has a certain amount of biotite and
quartz (~10%) while Ilt contains Ms. (~5%). Consequently, the high
purity samples of NCMs reaching upwards of 90–95% can potentially
contribute to REE adsorption.
Comparing the XRD pattern of the NCMs before and after adsorption
shows that the structure of the NCMs is remarkably unchanged during
the adsorption experiments (figures not shown), indicating that the
most of the REE are adsorbed/exchanged on the surface of NCMs par-
ticles.

(C0 ‐Ce )V
qe =
M (2)
3+ 3+ 3+
where C0 is the initial La or Yb (ppm), Ce is the equilibrium La or
Yb3+ (ppm), qe is adsorption capacity (mg/g), V is the volume of the
REE solution (L) and M is the mass of natural clay mineral (g).

2.5. Batch leaching of REE from NCMs

Desorption experiments were performed in the same way as ad-

sorption tests, pristine NCMs were contacted with initial La3+ or Yb3+
concentration (20 ppm) and shook for 2 h, and then the NCMs were
separated by centrifugation. The solution was analyzed by ICP-MS and
the desorbed REE was recorded. Re-suspended NCMs were washed once
with deionized water and then desorbed with (NH4)2SO4 concentration
(solid/liquid = 0.2/20 mL by mass). The mixtures were shaken in an
orbital shaker (IKA KS 4000 ic control) with a constant speed of
200 rpm and temperature of 25 °C. The samples referred to as La-NCMs
and Yb-NCMs. Fig. 1. XRD patterns of four NCMs.

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A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Table 1
Chemical composition of pristine NCMs by XRF analysis (wt%).
Oxide Mt Ms NMs Ilt Kao

SiO2 59.02 48.82 50.87 47.46 46.86

Al2O3 16.42 28.79 32.58 36.21 37.15
TFe2O3 4.36 5.40 0.72 0.33 0.75
TiO2 0.27 0.69 0.06 0.60 0.34
MgO 5.41 1.20 0.19 0.18 0.29
Na2O 0.05 0.45 1.61 0.27 0.08
CaO 2.79 0.04 0.32 0.17 0.12
K2O 0.07 9.92 8.23 9.58 0.59
P2O5 0.02 0.01 0.35 0.22 0.06
MnO 0.02 0.01 0.03 < 0.01 < 0.01

Note: NMs: Muscovite with less impurity of Fe2O3.

3.1.2. XRF analysis

The chemical components of the four NCMs are shown in Table 1. It
can be observed in the table that Mt have a higher content of pre-
dominant exchangeable cations of CaO and MgO whereas Ms. and Ilt
Fig. 2. The adsorption/desorption isotherms recorded on four NCMs.
have a higher content of K. However, a certain amount of Fe2O3 and
MgO in Ms. indicting to other associated mineral with Ms. Identify the
associated minerals with Ms. is further investigated in the following Table 3
sections. Specific surface area, pore volume and pore diameter (nm) of NCMs.
NCMs SBET (m2/g) Pore volume (cm3/g) Pore diameter (nm)
3.1.3. Lanthanides adsorbed in pristine NCMs
Mt 68.15 0.100973 5.95809
The contain of lanthanides in pristine NCMs were investigated as
Ms 8.50 0.019282 9.07296
shown in Table 2. It was observed that Kao exhibit highest content of Ilt 10.41 0.018653 7.16930
total lanthanides (0.5 ppm) whereas the content of lanthanides in Mt. Kao 32.39 0.075173 9.28318
are almost absent (0.004). However, the present study focus on light La
and heavy Yb REE as models, thus Table 2 indicates that there is
practically no influence to REE adsorbed on pristine NCMs in our ex- in Fig. 3. Fig. 3 shows the main peaks of elements for each NCM which
periments process. agreement with XRF results (Table. 1). The appearance of La3+ and
Yb3+ peak markedly on the Mt. and Ms. than other NCMs, suggesting
3.1.4. Specific surface area the favorite adsorbed of REE onto the surface of Mt. and Ms. The atomic
The adsorption/desorption isotherms recorded on four NCMs have ratios of Si, Al, O, K, Ca, Fe, La and Yb of NCMs before and after ad-
revealed a characteristic hysteresis loop, which is associated with ca- sorption were listed in Table 4. The Ca2+ is the dominant exchangeable
pillary condensation in the mesopores (Fig. 2).The specific surface area cations of NCMs, which is percent only in Mt., the atomic fraction of Ca
(SSA), total pore volume, and average pore diameter of all NCMs are (349.16 eV) decreased from 1.61% to 0.16% and 0.15% for La3+ and
presented in Table 3. However, the Mt. displays higher SBET and it in- Yb3+, respectively after adsorption process, indicating that REE ad-
crease in the order of Mt > Kao > Ilt > Ms. As is well known, SSA is sorbed onto Mt. may be mainly by ion-exchange with Ca2+. In contrast,
one of the factors that influence the adsorption process. Higher specific the adsorption of REE on Ms. is not only by its surfaces but also REE
surface area of material, implied providing higher adsorption sites for could be attached to occurring Fe-oxides resulting to impurities of iron
contaminant adsorption (Alshameri et al., 2014a). oxide associated with Ms., contributing to REE adsorption process. The
adsorption mechanism of REE onto NCMs is further evaluated and
3.1.5. Surface chemical composition discussed in the following sections.
The surface composition of NCMs were monitored by XPS as shown
3.1.6. Zeta potential
Table 2 The surface charge of NCMs was measured as a function of pH,
The extraction of lanthanides from pristine NCMs (ppm). between pH 3 and pH 6.5 (Fig. 4). It shows that all NCMs surface groups
are mainly negatively charged in the studied pH range. The zeta po-
Ln/NCMs Mt Ms Ilt Kao
tential of NCMs decreases with the increase of pH, indicating a more
La 0.002 0.016 0.001 0.072 negative charge on the NCMs surface. The negatively charged surface
Ce 0.000 0.003 0.003 0.136 contributes to the mineral's ability to adsorb positively charged ions
Pr 0.000 0.000 0.000 0.023 (Alshameria et al., 2018. The negatively charged surfaces can provide
Nd 0.001 0.000 0.003 0.087
Sm 0.000 0.000 0.002 0.021
the driving force for electrostatic interaction with REE3+. Also, the
Eu 0.000 0.000 0.001 0.006 figure shows that Mt. has more negatively charged surface than other
Gd 0.000 0.000 0.005 0.018 NCMs, suggesting that Mt. can be considered as ideal NCM adsorbent
Tb 0.000 0.000 0.001 0.003 for REE from aqueous solutions.
Dy 0.000 0.000 0.003 0.017
Ho 0.000 0.000 0.001 0.004
Er 0.000 0.000 0.001 0.009 3.2. Adsorption characteristics of La3+ and Yb3+ onto NCMs
Tm 0.000 0.000 0.000 0.001
Yb 0.000 0.000 0.001 0.008 3.2.1. Adsorption kinetics
Lu 0.000 0.000 0.000 0.001
As shown in Fig. 5a,b, the adsorption efficiencies of La3+ and Yb3+
Y 0.001 0.000 0.013 0.093
Total REE % 0.004 0.019 0.035 0.499 on all NCMs increase with the increasing contact time and reaches
equilibrium in 30 min for La3+ and Yb3+. Beyond this value, there is no
Ln = Lanthanides. noticeable increase in the adsorption. The results indicate that the

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A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Fig. 3. XPS spectra of NCMs before and after La3+ and Yb3+ adsorption.

Table 4 contacting the NCMs with the La3+ and Yb3+ solution, the pH rapidly
Surface chemical composition of NCMs before and after adsorption REE by XPS increased over initial pH solution for Mt., Ms. and Ilt, except Kao where
analysis. the pH is nearly constant as shown in Fig. 6a,b. The pH then increase
Name/ O Si Al Mg Ca Fe K C La Yb with the increasing contact time and reached a maximum at around
Atomic % 30 min for all NCMs except Kao and remained constant till the end of
the experiment time (Fig. 6a,b), indicating that the adsorbent edge
Mt 55.55 19.09 6.61 1.80 1.61 1.04 – 14.27 – –
carried the negative charge facilitating adsorption of La3+ and Yb3+ on
Mt-La 54.20 20.09 6.61 1.71 0.16 0.94 – 16.29 0.16 –
Mt-Yb 55.32 19.91 6.67 1.93 0.15 0.86 – 14.51 – 0.17
their surface (Gladysz-Plaska et al., 2014 and Iannicelli-Zubiani et al.,
Ms 49.80 14.59 11.28 – – 1.10 3.91 19.33 – – 2015). Therefore, the La3+ and Yb3+ ions in solution are available for
MS-La 52.83 16.11 11.98 – – 1.26 3.55 14.06 0.21 – adsorption and/or ion exchange with the NCMs. The mechanism that
Ms-Yb 53.10 14.79 11.79 – – 1.17 3.27 14.22 – 0.22 influences the adsorption characteristics of NCMs can be explained by
Ilt 55.25 15.62 13.49 – – – 3.36 12.28 – –
cation exchange, surface complex and electrostatic adsorption (Chen
Ilt-La 54.85 16.15 14.19 – – – 3.20 11.61 – –
Ilt-Yb 52.47 15.15 13.47 – – – 3.09 15.02 – – et al., 2012; Wu et al., 2012). It is well know that the main REE species
Kao 58.14 15.45 12.50 – – – – 13.02 – – are form of REE3+, REEOH2+, REE(OH)2+ and REE (OH)3 at different
Kao-La 57.60 15.58 13.08 – – – – 13.74 – – pH values (Chen et al., 2012). When NCMs come into contact with REE
Kao-Yb 57.68 15.40 12.64 – – – – 13.64 – –
solution, the pH quickly increased over initial pH solution, which in-
dicated that cation exchange was a primary mechanism for RE-
E3+species at initial pH 4.5, Na+, K+, Ca2+ and Mg2+ could be ex-
adsorption of REE on NCMs is quite rapid and reaches equilibrium
changed with REE3+ from the aqueous solutions. Since the REE species
within 30 min for all NCMs. This may be attributed to the utilization of
present in the form of REEOH2+, REE(OH)2+, REE (OH)3 at pH > 5
readily available adsorption sites of the NCMs leading to a fast diffusion
(Chen et al., 2012), they are easily to be adsorbed on the negative
and rapid equilibrium attainment. The short time period required to
charged surfaces of NCMs as indicated by zeta potentials (Fig. 4). It is
attain equilibrium suggests an excellent affinity of adsorbent for Ad-
easily for the positive charged REE ions to be adsorbed on the negative
sorbate (Iannicelli-Zubiani et al., 2015; Alshameri et al., 2014b). It has
charged surfaces of NCMs. These species can potentially form onto Mt.
been widely proposed that fast adsorption kinetics play an important
and Ms.(the pH increased over initial pH solution), leading to the in-
role in the efficiency and field deployment of adsorbents.
crease of the adsorption efficiencies of La3+ and Yb3+ when compared
Also, the pH during contact time was evaluated (Fig. 6a,b).When
with those of Kao and Ilt (pH is nearly constant of initial pH) as shown

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A. Alshameri, et al.
Fig. 4. Zeta potential of NCMs as a function of pH, (a) La and (b) Yb.
in Fig. 6.
In fact, there are three kinds of surface charges on NCMs: one is
permanent negative charge (resulting from the structural isomorphous
substitutions), it cannot be changed by external conditions, such as pH,
second one is pH-dependent charge (primarily related to the dissocia-
tion of hydroxyl groups); the third one is net charge, which is equal to
the algebraic sum of positive charge and negative charge (including
permanent charge and pH-dependent charge) on NCMs particles. For
instance, upon contacting the NCMs with the REE solution, the pH ra-
pidly increases with the increasing contact time and reached a max-
imum (Fig. 6a,b). Beyond these pH, there are no obvious increase in the
adsorption efficiencies (Fig. 6a,b), which is an indication that the ad-
sorbent edge carried the negative charge facilitating adsorption of REE
on their surfaces. Since the adsorption mechanism can be explained by
surface complex, cation exchange and electrostatic adsorption. The
hydrolysis of Si–OH or Al–OH which bonds along the NCMs lattices
produces the surface charge. Depending on the silica structure and the
pH of the solution, the net surface charge can be either positive or
negative. In an acidic medium, the net surface charge result in positive
charge formation as described follow:
–SOH + H‐OH → S‐OH+2 + OH− (4)
The positive charge is responsible for preventing REE ions from
Fig. 5. Effect of contact time on La (a) and Yb (b) adsorption onto NCMs.
154
Hydrometallurgy 185 (2019) 149–161
approaching the surface and explains the smaller extent of adsorption at
low pH 3. The competition between the protons and the REE3+ for the
surface sites would result in the lowest adsorption of REE3+ at low pH
as demonstrated by the zeta potentials (Fig. 4). In an alkaline medium,
the NCMs edge becomes more negatively charged favoring REE ad-
sorption, which could be expressed as the following:
− SOH + OH− = −SO− + H2 O (5)
–SO– + REE3 + = ‐S‐O−…REE3 + (6)
Additionally, the pH affects not only the surface of the adsorbent,
but also the degree of ionization and speciation of metal ions in solution
(Aksu and İşoğlu, 2005; Awual et al., 2013). The hydrochemical be-
havior of REE are strongly influenced by their solution speciation.
However, the REE adsorption at pH higher than 6.8 was not considered
due to the possible precipitation in the solution, indicating the hydro-
lysis of the metal ion with the formation of the corresponding insoluble
hydroxide (Palmieri et al., 2002; Zare-Dorabei et al., 2009; Awual et al.,
2013). In contrast, at acidic conditions, REE exist in their trivalent form
and initial hydroxide concentration were negligible and the con-
centration of REE-OH+ was minimal (Kusaka et al., 1998 and Awual
et al., 2013). Beside on our experiments findings and literature data, pH
of 5 was selected for our subsequent investigations in the following
A. Alshameri, et al.
Fig. 6. pH evolution during contact time experiments on La (a) and Yb (b) by NCMs.
adsorption experiments.
In order to optimize the kinetic adsorption data, the pseudo-first
order and pseudo-second-order kinetics models were applied to simu-
late the kinetic adsorption and can be summarized as follows.
The linear equations of pseudo-first, pseudo-second order models
for boundary conditions of qe = 0 at t = 0 and qt = qeat t = teare as
follow:
The pseudo-first order:
ln(q e ‐qt) = lnq e ‐k1t (7)
Pseudo-second order:
t 1 1
= + th = k2q e2
qt k2q e2 qe (8)
where qt is adsorption capacity at time t (mg/g), k1and k2 are constants
of adsorption (1/min) and (g/mg min−1) respectively and h is the rate
of adsorption (mg/g min).
The adsorption kinetics of La3+ and Yb3+ by four NCMs presented
in Fig. 7a and b. The kinetics parameters of pseudo-first and pseudo-
second order models are listed in Table 5.The high correlation coeffi-
cient values (R2) suggest that the kinetics adsorption of La3+ and Yb3+
on NCMs can be described by the pseudo-second order rate equation
very well.
3.2.2. Adsorption isotherms
The equilibrium adsorption capacities as functions of the different
initial concentrations of La3+ and Yb3+ on the four NCMs are presented
in Fig. 8. The adsorption capacities indicated to vary from NCM to NCM
in the order of Mt > Ms > Ilt > Kao for both La3+ and Yb3+. This
result suggests that the increase in the initial concentrations of La3+
and Yb3+ increases the mass transfer driving force of the La3+ and
Yb3+ between the aqueous solution and adsorbent phase, which leads
to an increase in La3+ and Yb3+ adsorption capacities.
In addition, Mt exhibits the highest adsorption capacities of REE
(Fig. 8). This behavior could be related to the high cation exchange
capacity of Mt. relative to other NCMs, significantly contributing to the
high La3+ and Yb3+ adsorption capacities. Meanwhile, the adsorption
capacities increased in the order of La3+ < Yb3+ which was consistent
with the trend of decreasing radii of REE ion, suggesting that REE with
a less ion radius was easier to be adsorbed on the NCMs.
A similar trend was also observed by Wu et al. (2012) who reported
that REE ion with a less ion radius was easier to be adsorbed on the
bentonite. Also the study suggested that with steric hindrance effect,
the oxygen atom carrying negative charge on NCMs, is easier to attract
the REE ions with the smaller ionic radii which lead to the higher
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Hydrometallurgy 185 (2019) 149–161
upload of Yb3+ than that of Eu3+ and La3+. Bonnot-Courtois and
Jaffrezic-Renault (1982) explained this behavior due to the decrease of
the ionic radius with increasing atomic number. Additionally, Coppin
et al. (2002) reported that HREE is more strongly adsorbed on NCMs
than the LREE. This is explained in terms of the surface chemistry of
NCMs with two coexisting types of surface charge; the permanent
structural charge and variable pH-dependent charge could enhance the
adsorption of HREE according to the lanthanide contraction. Moreover,
Olivera Pastor et al. (1988) and Bentouhami et al. (2004) have found
that hydrolysis tendency in the REE series at 25 °C increases with in-
crease of atomic number and contraction of the atomic radius. They
related this to lanthanide adsorption on NCMs in excess of their cation
exchange capacities values.
From the above discussion, it can be concluded that the different
behaviors adsorption of the LREE and HREE on NCMs could be related
to the “lanthanide contraction” in the ionic radii going from light to
heavy REE.
Several equilibrium models have been applied to describe adsorp-
tion isotherm. Two main isotherm models, Langmuir model (LM) and
Freundlich model (FM) were used to describe the experimental results
of La3+ and Yb3+ as follow:
LM adsorption isotherm assumes that adsorption takes place at
specific homogeneous sites within the adsorbent and has found suc-
cessful application for many adsorption processes of monolayer ad-
sorption. The linear form of LM is expressed as:
Ce 1 1
= + Ce
qe Kqmax qmax (9)
where K is Langmuir constant (L/mg) and qmax is Maximum adsorption
capacity (mg/g).
The FM endorses the heterogeneity of the surface and assumes that
the adsorption occurs at sites with different energy of adsorption. It is
described by the following equation:
1
logq e = logkF + logCe
n (10)
1/n
where KF is Freundlich adsorbent capacity (mg/g (L/mg) ) and n is
the reciprocal of reaction order.
The linear plots of the Langmuir and Freundlich adsorption iso-
therm of La3+ and Yb3+ are given in Fig. 9a,b. The values of qmax and K
were calculated from the slope and the intercept of the plot using Eq.
(9), and are listed in Table 6. The Langmuir model has a better fit for
La3+ and Yb3+ adsorption on NCMs (R2 > 0.96) than Freundlich
model, indicating that the adsorption process of La3+ and Yb3+ by the
NCMs are a monolayer adsorption. By analyzing the comparative
A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Fig. 7. Pseudo-first order (a and b), pseudo-second order (c and d) for La (a) and Yb respectively onto NCMs.

Table 5 indicates that Mt. has a high adsorption affinity towards La3+ and
Kinetics parameters for the adsorption of La and Yb onto NCMs. Yb3+.The value of 1/n obtained from the Freundlich isotherm which
Kinetic model Parameters is < 1, indicates that the adsorptions of La3+ and Yb3+ onto NCMs
adsorbents are favorable.
Pseudo –first order K1 (min−1) qe (mg/g) R2
3.3. Leaching of La3+ and Yb3+ adsorbed on NCMs
La (III)
Mt 0.0217 0.7872 0.9423
Ms 0.0172 0.2543 0.9648 Recent findings were reported that REE adsorbed on clays can be
Ilt 0.0205 0.2403 0.9348 easily recovered by an ion-exchange mechanism during leaching with
Kao 0.0182 0.1897 0.9533 monovalent salt solutions under ambient conditions (Moldoveanu and
Yb(III)
Papangelakis, 2012). Therefore, NH4+ was selected as cation of interest
Mt 0.0236 0.8236 0.9318
Ms 0.0928 0.5862 0.8668 in leaching of the four NCMs which are commonly found in ion ad-
Ilt 0.0231 0.5309 0.9153 sorption clays (IAC). Considering the economical and technological
Kao 0.0208 0.4637 0.9606 feasibility to extract REE from four NCMs, the optimum conditions of
lixiviate concentration, contact time and pH of solution were in-
vestigated on La-NCMs and the same conditions were applied for Yb-
Kinetic model Pseudo-second order Parameters
NCMs. The temperature of leaching experiments was fixed at 25 °C to
h (mg/g min) qe (mg/g) R2 minimize lanthanide loss via permanent chemisorption or via hydro-
xide precipitation at higher temperatures according to the literature
La (III) information (Tertre et al., 2006; Moldoveanu and Papangelakis, 2012).
Mt 0.1282 14.786 0.9889
Ms 0.0690 6.8775 0.9679
Ilt 0.0598 2.3228 0.9948 3.3.1. Influence of lixiviate concentration on REE leaching process
Kao 0.0408 1.9935 0.9514 The results of La3+ batch leaching experiments from four NCMs
Yb(III) under different leaching concentration are illustrated in Fig. 10a.The
Mt 0.1500 15.1975 0.9832
leaching efficiencies of La3+ from four NCMs increases with increasing
Ms 0.0795 7.7042 0.9791
Ilt 0.0771 3.1133 0.9805 lixiviate concentration up to 0.5 mol/L and slightly increases with in-
Kao 0.0614 2.0004 0.9926 creasing lixiviate concentration.
Also, the figure shows that the highest extraction efficiency of La3+
was observed from Kao (89%), and followed in the order of Kao﹥Ilt﹥Mt﹥
adsorption of lanthanides by NCMs, it can be observed that Mt. has the
Ms. On the contrary, the results of our adsorption experiments in per-
highest adsorption monolayer capacities for both La3+ and Yb3+ and
vious section showed that the adsorption efficiencies are in the order of
the adsorption capacities for both REE decrease in the following order:
Mt﹥Ms﹥Ilt﹥Kao for both REE. It was inferred that the extraction effi-
Mt > Ms > Ilt > Kao (Table 6).
ciencies could exhibit inverse trend, high adsorption leads to low ex-
Freundlich parameters are given in Table 6. The large value of KF
traction. In fact Ms like Ilt, the exchangeable REE3+in micas (Ms and

156
A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Fig. 8. The experimental isotherms of La (a) and Yb (b) adsorption onto NCMs.

Ilt) are placed mostly on the surface of the edges of the alumino-sillicate
sheets, therefore can be easily recovered by monovalent salt solutions
(concept of ion exchange) than those that are in the interlayer of Mt.
However, lack of Ms. extraction efficiencies could be explained by
the presence of impurities iron oxide associated with Ms (Table.1). This
lack of Ms. extraction characteristics is further evaluated and discussed
in the following sections.
The present results compare with those reported by Moldoveanu
and Papangelakis (2013) who studied leaching concentrations of REE
from clays in the range 0.1–2.5 M of NH4+ and found the extraction
efficiencies to be ~80%. Similarly, Chi (1989), averaged total REE
extractions of 80% during percolation column leaching with 0.15 M
(NH4)2SO4 without elaborating on individual element extractions.
Therefore, the leaching of clays is controlled by diffusion of lixiviant
through the porous solid layer and to the site containing a physically
adsorbed lanthanide as reported by Jun et al. (2010a,b). It seems that
the present 0.5 mol/L leaching concentration would provide enough
over the stoichiometric requirement for monovalent exchange ions.

Fig. 9. The linearized Langmuir (a and b) and Freundlich isotherm (c and d) for La and Yb of four NCMs.

157
A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Table 6 Recent findings (Moldoveanu and Papangelakis, 2013), reported

Constants for equilibrium isotherm models for La and Yb adsorption onto that the increase in pH leaching of REE to higher than 5 led to a de-
NCMs. crease in the extraction levels. Since the REE extraction from NCMs can
Isothermal model Parameters be explained by cation-exchange, it can be thus inferred that, when
REE-NCMs come into contact with the NH4+ solution, the pH quickly
Langmuir model Qmax (mg/g) K(L/mg) R2 increased over initial pH solution to around 5.7 for both Mt. and Ms.,
leading thus to reduce the availability of ion-exchangeable with NH4+
La (III)
Mt 8.0840 1.0266 0.9947 ions. As a result, this maybe is one of the factors that influence the REE
Ms 3.9791 0.2316 0.9903 extraction percentage from Mt. and Ms. when compared with those of
Ilt 1.8566 0.1733 0.9995 Kao and Ilt (pH is nearly constant) as shown in Fig. 10c. In addition, the
Kao 1.6622 0.1375 0.9949
OLI simulation of pH influence (http://www.olisystems.com) on the
Yb(III)
Mt 8.5312 3.8312 0.9997
distribution of main lanthanum species in the sulfate system as shown
Ms 4.2258 0.3161 0.9866 Fig. 10d, indicating that there is no risk of lanthanum precipitation
Ilt 2.1231 0.1890 0.9756 under pH 6. In contrast, a pH below 3 would start to digest the NCMs
Kao 1.7649 0.0757 0.9606 (Moldoveanu and Papangelakis, 2013).
In conclusion, even if the ion-exchange reactions are considered pH-
independent, the permanently chemisorbed surface species start to form
Isothermal model Freundlich model Parameters
on Mt. and Ms. at pH > 5, making thus the control of pH an important
KF (mg/g)/(mg/L)1/n 1/n R2 factor during clays leaching with NH4+ to ensure optimum REE ex-
traction levels.
La (III)
Mt 3.8450 0.2527 0.9188
Ms 2.0353 0.3546 0.9791 3.4. Reuse of NCMs for La3+and Yb3+ adsorption
Ilt 2.0055 0.1651 0.8934
Kao 1.9693 0.3559 0.8959 Regeneration is required for a good adsorbent as this ensures re-
Yb(III) peated use. Adsorption cycles efficiencies of La3+and Yb3+ by four
Mt 4.2335 0.2824 0.8358
Ms 2.3807 0.2839 0.9645
NCMs are shown in Fig. 11a,b. All NCMs regenerated for the adsorption
Ilt 2.1521 0.1919 0.9806 of REE up to five cycles. However, Mt. exhibits highest regeneration,
Kao 2.0067 0.3495 0.9816 the adsorption percentage for La3+and Yb3+ after five cycles were
88.5% and 90.2% respectively. This implies that Mt. displays a smaller
reduction in the adsorption efficiencies among other NCMs and in-
Thus, 0.5 mol/L was selected as the leaching concentration for all NCMs
dicates a very good reusability. Interestingly, although Ms. was initially
and used in the subsequent experiments.
more efficient towards La3+ and Yb3+ adsorption than Ilt and Kao,
after only a single reuse the Ms. becomes less effective than Ilt and Kao
3.3.2. Influence of contact time on REE leaching process (Fig. 11a,b).
As shown in Fig. 10b, the leaching efficiencies of La3+ from NCMs A possible explanation for the mechanism that influences the reuse
were very fast, with < 10 min to reach maximum leaching values. Si- of Ms. could be attributed to presence of iron oxide and biotite (con-
milarly, the study of Moldoveanu and Papangelakis (2013) reported taining Fe in its structure and produce iron oxide as a result of its al-
that the leaching kinetics was very fast with < 5 min. Jun et al. teration) associated with Ms. as illustrated in Table.1 and Fig. 12.
(2010a,b) studied the leaching of REE from the weathered crust-elu- However, REE are attached to occurring Fe-oxides, contributing to REE
tion-deposited ores and reported the kinetics equilibrium to be 8 min adsorption process. The practice of in-situ leaching of the ion-adsorp-
and independent of pH and temperature. Furthermore, Bruque et al. tion type rare earths ore with NH4+ can easily leach most of the rare
(1980) reported that agitated leaching in excess of 1 h led to loss of earth in ion-exchangeable phase but unlike Fe-oxides, which leads to
dissolved REE, likely due to hydrolysis. As process kinetics was found to low regeneration after a single reuse of Ms.
be very fast, this fact can be attributed to an ion exchange mechanism
which is reversible and independent of pH and temperature, thereby 3.5. Leaching REE from NCMs
significantly enhancing the leaching as well (Moldoveanu and
Papangelakis, 2013). Based on our result and literature, 30 min was A comparison for the recovery of adsorbed La3+ and Yb3+ from four
selected for further studies. NCMs is shown in Fig. 13a,b. Individual leaching levels varied from
LREE to HREE on the same NCM with slightly higher extraction for
3.3.3. Influence of pH on REE leaching process Yb3+ than La3+ from all NCMs. Also, it can be observed that the highest
The pH during leaching time was evaluated (Fig. 10c).When con- extraction efficiencies were achieved from Kao (89% for La3+ and 85%
tacting the La-NCMs with the NH4+ solution, the pH rapidly increased for Yb3+) and decreases in the order of Kao > Ilt > Mt > Ms
over initial pH solution to around 5.7 for both Mt. and Ms. whereas the (Fig. 13a,b). However, the REE extraction efficiencies from Ms is in
pH is nearly constant for Ilt and Kao (Fig. 10c). The pH then slightly contrast to the expectation. It was inferred that Ms. like Ilt, adsorbed
increase with the increasing leaching time for Mt. and Ms. and reached REE on their surface, thus are easier to extract from Ms. than those that
a maximum at around 30 min for all NCMs and no significant change till are in the interlayer of Mt.
the end of the experiment time. This indicates that lanthanide in NCMs To verify the effect of iron oxide associated with Ms. in reuse and
are available for desorption and/or ion exchange with NH4+cations extraction of REE, the adsorption/desorption on biotite and muscovite
(Moldoveanu and Papangelakis, 2013). (NMs) (less impurity of Fe2O3) were carried out (Table 1). Nevertheless,
Bradbury and Baeyens (2002) and Tertre et al. (2006) found that the biotite displays a similar trend of Ms. in the reuse and extraction pro-
sorption/recovery of REE are pH-independent due to cation exchange. cess with low REE extraction of ~10–15% than Ms. Also, NMs (with less
Also, studies reported that under acidic and near-neutral pH, REE3+ is impurity of Fe2O3) shows low adsorption and extraction efficiencies
the main REE species while hydroxide complexes become predominant than Ms. and Bio.
at basic pH. Also, the sulfate lanthanides in sulfate systems are im- The leaching process of the REE is a kind of the reversibility of the
portant at acidic and near-neutral pH (Cetiner and Xiong, 2008 and ion-exchange process, it was evident that the cation exchange and ne-
Moldoveanu and Papangelakis, 2013). gatively charged surfaces are the mechanism for REE adsorption. The

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A. Alshameri, et al. Hydrometallurgy 185 (2019) 149–161

Fig. 10. Influence of NH4+concentration (a), contact time (b), pH of solution (c) on La leaching efficiency onto four NCMs and OLI simulation of pH influence of
main lanthanum species (d).

adsorption process could be expressed as the following: –NCM– (Solid) + REE3 +(Solution) → ‐NCM‐…REE3 +(Solid) (12)

NCM‐(Ca2 +, Na+, K+) (Solid) + REE(Solution) → NCM‐REE(Solid) Therefore, the leaching process could be expressed by the following
+ (Ca2 +, Na+, K+)(Solution) (11) ion-exchange reaction:

Fig. 11. Adsorption cycles on La (a) and Yb (b) by NCMs.

159
A. Alshameri, et al.
Fig. 12. Illustration of muscovite mineral with biotite and iron oxide (a and b) and biotite mineral associated with iron oxide (c and d).
NCM‐nREE3 +(Solid) + 3nNH 4+( Solution) → NCM‐3nNH 4+(Solid)
+ nREE3 +(Solution)
The present results of Kao extraction (89% for La3+ and 85% for
Yb3+) and Ms. extraction associated with the iron oxide (63%) com-
pared with those reported by Chi (1989) and more recently
(Moldoveanu and Papangelakis, 2013) whose average total REE ex-
tractions were 80% from clay materials. As a result, this is evident that
the iron oxide associated with Ms. contribute to improve the REE ad-
sorption onto Ms. but cannot be easily recovered by monovalent salt
solutions using the concept of ion exchange (i.e.NH4+).
From the above discussion, it can be concluded that NH4+ is lacking
as a lixiviant cations from NCMs since NCMs are associated with iron
oxide mainly, either with NCM containing iron (i.e. Biotite) and pro-
duce iron oxide resulting to its alteration or natural clay minerals which
always associate with biotite such as muscovite.
Fig. 13. Extraction cycles on La (a) and Yb (b) by NCMs.
Hydrometallurgy 185 (2019) 149–161
It was evident that the structure and surface properties of NCMs
were also the key factors affecting the rare earth leaching. Therefore,
(13) identifying the influence of structure and surface properties mechanism
of types of NCMs and associated impurities in clay materials are so
important, either for selecting a suitable REE leaching or in developing
a new one.
4. Conclusions
This study shows that Mt. exhibits the highest adsorption and re-
generation efficiencies of La3+ and Yb3+ whereas Kao displays the
highest extraction efficiencies for both REE. 89% for La3+ and 85% for
Yb3+ were achieved from Kao while the lowest extractions rate were
obtained from Ms. Characterized by XRD shows that all NCMs are
composed almost entirely of natural clay mineral and a few impurities.
The presence of iron oxide with Ms. found to help enhance REE
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A. Alshameri, et al.
adsorption (REE-Fe-oxides), meanwhile it also influences the reuse and
extraction characteristics of Ms. because REE-Fe-oxides cannot be easily
recovered by monovalent salt solutions using the concept of ion ex-
change i.e. NH4+. The kinetics adsorption and recovery were very fast
and the maximum leaching efficiencies for all NCMs were obtained
within 10 min with 0.5 mol/L NH4+ at pH of 4.5.The adsorption pro-
cess follows the pseudo-second-order kinetic model and the adsorption
isotherms complied well with the Langmuir isotherm model. When
contacting the REE-NCMs with the NH4+ solution, the pH quickly in-
creased over initial pH solution to around 5.7 for both Mt. and Ms. This
maybe also is one of the reasons in decrease the lanthanum extraction
from Mt and Ms when pH increased to 5.7 compared with those of Kao
and Ilt.
The results of this study could help to better understand the me-
chanism that influences the adsorption/ extraction characteristics of the
REE onto NCMs and confirmed that the identification of the types of
NCMs, associate mineral and the impurities in clays material are an
important either for selecting the lixiviate or developing new one.
Additionally, this study confirmed that ion-adsorption clays have sig-
nificant potential as alternative source of REE.
Acknowledgments
This study was financially supported by the team Project of Natural
Science Foundation of Guangdong Province, China (Grant
No.S2013030014241), the CAS/SAFEA International Partnership
Program for Creative Research Teams (Grant No. 20140491534) and
School of Environmental and Chemical Engineering, Foshan University,
Foshan, Guangdong 528000.
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