Hydrometallurgy 226 (2024) 106284

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

Effect of pretreatment methods on the selective leaching of rare earth

elements from NdFeB permanent magnets using deep eutectic solvents
Seojin Heo a, b, Rina Kim a, b, *, Ho-Sung Yoon a, *, Chul-Joo Kim a, Kyeong Woo Chung a, b,
Sujeong Lee a, b
a
Resources Utilization Division, Korea Institute of Geoscience and Mineral Resources, Daejeon, Republic of Korea
b
Resources Engineering, University of Science and Technology, Daejeon, Republic of Korea

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

Keywords: In this study, deep eutectic solvents (DESs) were employed as environmentally friendly alternatives of inorganic
Rare earth elements acid to selectively leach REEs from waste NdFeB magnets. Three DESs were tested, effective for light REE
Deep eutectic solvent leaching, and preliminary experiments were conducted to study the selective leaching of REEs, using synthetic
NdFeB magnet
materials, Nd2O3, Fe, Fe3O4, and Fe2O3. The findings suggest that neodymium and iron should exist as Nd2O3 and
Selective leaching
Fe2O3, respectively, for selective leaching. To enhance the selective leaching of the NdFeB magnet, three pre­
NaOH digestion
treatment methods were applied: oxidative roasting, NaOH digestion, and NaOH digestion-oxidative roasting.
During the oxidative roasting, NdFeO3 was formed, and it hindered REE leaching, achieving the highest REE
leaching efficiency of 22.5% in the guanidine hydrochloride (GUC)-lactic acid (LA) DES. To counteract NdFeO3
formation, the NaOH digestion was introduced, yielding Nd(OH)3 and Fe3O4. These were then converted to
Nd2O3 and Fe2O3 through oxidative roasting. With the NaOH-digested product, selective REE leaching was
achieved solely with the ethylene glycol (EG)-maleic acid (MA) DES, while it was feasible in all three DESs with
the NaOH digestion-oxidative roasting. The EG-MA DES displayed the highest selectivity, with a leaching effi­
ciency of 97.3% Nd and 0.8% Fe. Additionally, the solvent could be reused at least twice, and the leaching ef­
ficiencies of 97% for Nd and 0.7% for Fe were maintained. This selective leaching technique benefits from using
environmentally friendly solvents compared to the traditional inorganic acid leaching and demonstrates high
REE selectivity and solvent reusability, suggesting a novel method for REE recovery via DESs.

1. Introduction praseodymium (Pr), vital for permanent magnets, is projected to triple

Global initiatives aimed at achieving Net Zero to combat climate
change are hastening the shift from petroleum-based energy to cleaner
alternatives. Clean energy accounts for approximately 30% of total
electricity production, projected to rise with solar PV and wind power
supply, reaching 45% by 2030 (IEA, 2022). As the energy production
landscape transforms, there is a growing preference for electric vehicles
over traditional internal combustion engine vehicles, aligning with the
need to curb fossil fuel consumption. This shift foreshadows a surge in
demand for critical minerals, including copper, rare earth elements
(REEs), silicon, and lithium, essential for clean energy technologies.
Estimates suggest that this demand might increase by 2 to 4 times by
2030, driven by the broader adoption of renewables and electric vehi­
cles. The REEs are crucial for producing permanent magnets for electric
vehicle motors and wind turbines. The demand for neodymium (Nd) and
by 2050 with the rapid expansion of wind power generation (IEA, 2022).
However, relying solely on primary resources is untenable in meeting
this escalating demand as natural REE reserves are finite. Moreover,
mining these elements poses challenges, including low ore grade, sig­
nificant environmental repercussions, and radioactive waste by-
products (Chen et al., 2022).
Recycling addresses the supply challenges of REEs and mitigates
environmental and economic concerns (Mudali et al., 2021). Ensuring a
stable mineral supply can be achieved by diversifying secondary re­
sources, including rare earth tailings, industrial waste, magnetic resi­
dues, and electronic waste (Chen et al., 2019). Moreover, recycling
resources from waste diminishes environmental pollution and curtails
the demand for primary resource mining (Mudali et al., 2021). End-of-
life (EoL) permanent magnets, with their rare earth content ranging
from 27 to 32 wt%, serve as excellent secondary sources for the recovery

* Corresponding author at: Resources Utilization Division, Korea Institute of Geoscience and Mineral Resources, Daejeon, Republic of Korea.
E-mail addresses: rkim@kigam.re.kr (R. Kim), hsyoon@kigam.re.kr (H.-S. Yoon).

https://doi.org/10.1016/j.hydromet.2024.106284
Received 10 October 2023; Received in revised form 15 February 2024; Accepted 17 February 2024
Available online 15 March 2024
0304-386X/© 2024 Elsevier B.V. All rights reserved.
S. Heo et al.
of Nd, Tb, and Dy (Zhang et al., 2020).
Conventional hydrometallurgical methods, predominantly used for
recovering REEs from waste permanent magnets, entail significant
chemical consumption and produce large volumes of wastewater (Zhang
et al., 2020). The health, environmental, and safety concerns associated
with the lixiviants in the leaching process are gaining attention,
prompting research into eco-friendly solvent alternatives (DeSimone,
2002). Deep eutectic solvents (DESs), a category of non-aqueous sol­
vents, stand out as environmentally friendly alternatives to conventional
solvents, and they are emerging as promising mediums for metal re­
covery. These solvents comprise eutectic mixtures of Lewis or Brønsted
acids and bases, encompassing diverse anionic and/or cationic species.
Typically, they result from the complexation between a hydrogen bond
donor (HBD) and a hydrogen bond acceptor (HBA). Quaternary
ammonium salts are commonly used as HBA, whereas alcohols, amines,
and organic acids serve as HBD. The charge delocalization stemming
from the hydrogen bonds between HBA and HBD endows DESs with a
melting point lower than their components, enabling them to remain in
liquid state at room temperature (Smith et al., 2014).
The general formula of DESs is Cat+X− zY, where Cat+ refers to any
cation (ammonium, phosphonium, and sulfonium cations) and X is
typically a halide anion functioning as a Lewis base. Y represents Lewis
or Brønsted acids, forming complex anionic species with X− . The vari­
able z indicates the number of Y molecules interacting with the anion
(Smith et al., 2014). The DESs are classified into five types based on the
complexing agent utilized (Table 1) (Smith et al., 2014; Yuan et al.,
2022).
Among the five DES types, type III DESs, also known as natural deep
eutectic solvents (NADESs), excel in solvating diverse transition metal
species, encompassing chlorides and oxides (Smith et al., 2014; Yuan
et al., 2022). These solvents are formulated by mixing HBAs with
naturally derived carboxylic acids, sugars, and amino acids. Therefore,
they are considered green solvents, demonstrating low vapor pressure,
enhanced chemical and electrochemical stability, non-flammability, and
biodegradability; the aforementioned advantages render them suitable
alternatives to conventional solvents such as inorganic acids (Smith
et al., 2014; Yuan et al., 2022). Additionally, their superior dissolution
attributes, stemming from their capability to donate protons or accept
electrons, render them highly versatile. This versatility makes them
suitable for extracting metals for high-purity materials and selectively
recovering metals based on the distinct solubility profiles of various
DESs (Chen et al., 2019; Qin et al., 2020).
There are diverse studies on using DESs in hydrometallurgical pro­
cesses for metal recovery, leveraging their excellent metal extraction
properties. Given their ability to leach metals under gentler conditions
without requiring a reducing agent, numerous studies have focused on
extracting lithium and cobalt from spent lithium-ion batteries (LIBs)
(Wang et al., 2022; Padwal et al. (2022); Jafari et al., 2022; Yan et al.,
2023). Lu et al. (2022) recovered 98.6% and 98.8% of cobalt and
lithium, respectively, from waste LIBs using a DES mixture of choline
chloride (ChCl) and malonic acid. Peeters et al. (2020) utilized a ChCl-
citric acid DES for recovering lithium and cobalt from waste LIBs.
Topçu et al. (2021) recovered copper and silver from anode slime using a
ChCl-urea DES, while Lanaridi et al. (2022) extracted platinum group
metals (Pt, Pd, and Rh) from used automotive catalysts. Additionally,
Table 1
Deep eutectic solvent (DES) types and their general formula.
Type General formula Terms
I Cat X zMeClx
+ −
Me = Zn, Sn, Fe, Al, Ga, In
II Cat+X− zMeClx•yH2O Me = Cr, Co, Cu, Ni, Fe
Z = CONH2, COOH, OH
III Cat+X− zRZ
R = organic radical
IV MeClx + RZ = MeCl+x-1•RZ + MeClx+1 Me = Al, Zn; Z = CONH2, OH
V Composed only of molecular substances –
(Smith et al., 2014; Yuan et al., 2022)
2
Hydrometallurgy 226 (2024) 106284
Zhu et al. (2019) recovered 85.2% of zinc from zinc oxide dust using a
ChCl-urea-ethylene glycol DES and directly employed the resulting so­
lution for electrodeposition.
The DESs have been effectively employed in REE recovery. Chen
et al. (2019) demonstrated that La2O3 and Eu2O3 exhibit significant
solubility in an ethylene glycol-maleic acid DES, enabling their separa­
tion from CeO2 based on solubility differences. Karan et al. (2022)
recovered 85–95% REEs from coal fly ash using ChCl-lactic acid and
ChCl-toluene sulphonic acid monohydrate DESs, marking a 35%
enhancement compared to traditional inorganic acid leaching. Li et al.
(2022) recovered 88.4% of yttrium from yttrium carbonate salts with a
ChCl-urea-malonic acid DES. Yan et al. (2021) observed that while light
REEs were highly soluble in guanidine hydrochloride-lactic DES, heavy
REEs were predominantly insoluble.
Although there are several studies on recovering various metals from
elements from different raw materials or pure chemicals using DESs as
lixiviants, there is limited research on recovering REEs from NdFeB
permanent magnets at the end of life. Riaño et al. (2017) oxidatively
roasted NdFeB magnets at 950 ◦ C for 15 h, completely dissolved the
treated magnets using a ChCl-lactic acid DES (1:2 M ratio), and sepa­
rated individual elements through solvent extraction. Liu et al. (2020)
selectively leached Nd from roasted magnet powders, recovering 99%
pure Nd2O3 using a guanidine hydrochloride-lactic acid DES (1:2 M
ratio); however, the specific leaching efficiency and selectivity for actual
magnets were not detailed in this study. Studies on the leaching or se­
lective leaching of NdFeB permanent magnets with DESs are less
advanced than those using conventional acids or ionic liquids. Current
pretreatment of these magnets is primarily restricted to oxidative
roasting (Yoon et al., 2003; Yoon et al., 2017; Kumari et al., 2018;
Orefice et al., 2018; Orefice et al., 2020). Moreover, there are no
mechanistic studies on leaching behavior related to the mineralogical
characteristics of the magnets. Pretreated NdFeB permanent magnets
display various oxide forms, such as NdFeO3, Nd2O3, Fe3O4, and Fe2O3,
depending on the pretreatment methods and conditions, influencing the
leaching efficiency and REE selectivity in the subsequent leaching pro­
cess. Therefore, we aimed to identify the most suitable pretreatment and
lixiviant for selective leaching, investigating the leaching behavior of Nd
and Fe using different pretreatment methods and three DESs effective for
Nd oxide leaching. Furthermore, we analyzed the mineralogical char­
acteristics of pretreated NdFeB permanent magnets under varied pre­
treatment methods.
2. Materials and methods
2.1. Preparation of DESs
We selected DESs effective for leaching Nd oxide, prioritizing those
with viscosities that facilitate the dispersion of solid powders, such as
NdFeB magnets, REE oxide powder, and Fe oxide powder. These DESs
were prepared by mixing to homogenize under the conditions presented
in Table 2 (Riaño et al., 2017; Chen et al., 2019; Liu et al., 2020).
Guanidine hydrochloride (GUC, SAMCHUN, 98%), choline chloride
(ChCl, SAMCHUN, 99%), and ethylene glycol (EG, DAEJUNG, guaran­
teed grade) were used as HBAs. Lactic acid (LAC, Junsei, guaranteed
grade) and maleic acid (MA, DAEJUNG, extra pure grade) served as
HBDs. The physical properties and pH of the formulated DESs are
detailed in Table 3. Their water content was determined using Karl
Fisher titration (Volumetric KF titrator, V20S, Mettler Toledo), while
viscosity was assessed with a viscometer (LDVD-II + Pro, Brookfield).
We employed hydranal methanol and hydranal composite 5 titrants
from Honeywell for water content analysis. The pH of DESs was
measured with a pH meter (Orion Star A211 pH Benchtop Meter,
Thermo Scientific).
S. Heo et al. Hydrometallurgy 226 (2024) 106284

Table 2
Preparation condition of the deep eutectic solvents.
HBA Molar equivalent HBD Molar equivalent Temperature (◦ C)
a b
GUC (CH5N3⋅HCl) 1 LAC (C3H6O3) 2 70
CC (C5H14NO⋅Cl)c 1 LAC (C3H6O3)b 2 70
EG (C2H6O2)d 4 MA (C4H4O4)e 1 60

(Riaño et al., 2017; Chen et al., 2019; Liu et al., 2020)

a
guanidine hydrochloride
b
lactic acid
c
choline chloride
d
ethylene glycol
e
maleic acid

Table 3
Physical properties and pH of the deep eutectic solvents.
DES Water content (wt%) Viscosity pH
(cp at 20 ◦ C±2 ◦ C)

CC-LAC 10.5 212.4 0.27

GUC-LAC 11.2 133.5 − 0.88
EG-MA 6.51 38.2 0.43

2.2. Materials

The NdFeB permanent magnet scraps used in this study were sourced
from a Korean magnet manufacturer. Initially, the magnets were
crushed using a jaw crusher, and ground via a roll mill and vibrating cup
mill. Subsequently, the magnets were further ground using a shatter box,
Fig. 2. XRD pattern of the NdFeB magnet.
and the particles below 325 mesh (44 μm) was recovered for following
metallurgical tests. The particle size was analyzed by particle size
analyzer (S3500, MICROTRAC). Fig. 1 depicts the particle size distri­
Table 4
bution, with a median diameter (d50) of 17.26 μm, d10 of 8.36 μm, and Chemical composition of the NdFeB permanent magnet.
d90 of 32.57 μm. The X-ray diffraction (XRD) of the raw magnet (Fig. 2)
Element Nd Fe Tb Dy B
revealed its crystal structure as a Nd2Fe14B metal alloy. Table 4 lists the
chemical composition analyzed by inductively coupled plasma optical Content (wt%) 27.9 63.6 0.095 2.95 1.07
emission spectrometer (ICP-OES, Perkin Elmer, Optima 5300DV) and
inductively coupled plasma mass spectrometer (ICP-MS Perkin Elmer,
2.3. Pretreatment
Elan DRC II). The sample was pretreated by the mixed acid decompo­
sition and the alkaline melting methods, and the solution was diluted to
Three pretreatment methods were employed to oxidize NdFeB per­
enable analysis within the linear range of the instrument for the
manent magnets. The initial approach was oxidative roasting, where the
component to be analyzed. The concentration of iron was analyzed using
magnet powder was roasted at 900 ◦ C for 5 h in a muffle furnace in an
ICP-OES, and Nd(III), Dy(III), Tb(III), and B were analyzed by ICP-MS
atmosphere of air. The second technique involved NaOH caustic diges­
(detection limit 0.0025 wt%). The wavelengths used for analysis were
tion. In this process, the magnets were treated in a 50% sodium hy­
259.939 nm for Fe, 142 nm for Nd, 159 nm for Tb, 163 nm for Dy, and
droxide solution (NaOH, DAEJUNG) under conditions of a 1:10 solid/
10 nm for B. The NdFeB magnets predominantly comprised of iron (63.6
liquid (S/L) (w/w) ratio, stirring at 200 rpm, and 145 ◦ C for 5 h without
wt%) and neodymium (27.9 wt%), with minor traces of other REEs,
additional pressure. The final approach combined NaOH digestion with
including terbium and dysprosium (Table 4).
roasting. Post-digestion, the magnet was roasted at 450 ◦ C for 3 h in an
atmosphere of air (Kim et al., 2022). The resulting crystal structure of
the pretreated magnet was assessed using XRD (D8 ADVANCE,
BRUKER). The particle morphology was examined through mineral
liberation analysis (MLA 650F, FEI).

2.4. Leaching

To assess the fundamental leaching properties of DESs, dissolution

Fig. 1. Particle size distribution of the NdFeB permanent magnet.
tests were conducted on Nd2O3 (Alfa Aesar, 99.9%), Fe (Alfa Aesar,
98%), Fe2O3 (Junsei, Chemical pure), and Fe3O4 (DAEJUNG, Extra
grade). A 50 mL glass vial served as the reactor, wherein the solid sample
was introduced at a 1:100 S/L (w/w) ratio to the DESs and leached at
70 ◦ C for 5 h. Ultrasonication was employed using a sonicator (Jeiotech,
UCP-10, 300 W) during leaching to enhance the dispersion of the solid
material. Post leaching, the mixture was centrifuged at 17000 rpm for
20 min and filtered through a glass fiber filter of 0.7 μm, for solid–liquid
separation. The resulting leachate was then diluted in 2% nitric acid,
with metal ion concentrations determined using ICP-OES (Perkin Elmer,

3
S. Heo et al.
Optima 8300). The leaching efficiency (L) was computed using Eq. 1,
with the mean value derived from three experimental repetitions:
ML
L (%) = × 100 (1)
ML + MR
where ML and MR represent the metal masses in the pregnant leach so­
lution (g) and leach residue (g), respectively; ML was calculated by
multiplying the concentration of metal elements (mg/L) and volume (L)
of the pregnant leach solution; MR was calculated by dissolving the leach
residue and converting the dissolved metal concentration into the
weight of metal contained in the residue.
3. Results and discussion
3.1. Preliminary DES leaching results of synthetic materials
The solubility variance of each metal oxide in DESs enables selective
leaching. Gathering such information on the dissolution properties of
these oxides, before the leaching of the substance in different DESs is
crucial. Typically, the composition of NdFeB permanent magnets varies
depending on their intended use. However, Fe and Nd generally remain
dominant, constituting up to 70% and 30%, respectively. The magnets
analyzed in this study mirrored these ratios as shown in Table 4.
Therefore, the leaching behaviors of Nd and Fe solely were examined.
Post oxidative roasting, Nd transforms into Nd2O3. Conversely,
depending on the roasting duration and temperature, Fe can manifest in
various forms, including metallic Fe, Fe3O4, and Fe2O3. The leaching
behavior of Nd and Fe oxides, and metallic Fe using GUC-LAC, CC-LAC,
and EG-MA DESs as lixiviants, are presented in Fig. 3.
Fig. 3 demonstrates that Nd2O3 dissolved in all DESs, unlike Fe3O4
and Fe2O3, because Nd2O3 is more ionic than other metal oxides (Liu
et al., 2020). When a compound is more ionic, it means that there is a
large difference in electronegativity between the two substances, which
means they are more polar. The electronegativity difference between Nd
and O is 2.3, which is larger than the difference between Fe and O of 1.6,
making Nd2O3 more ionic than Fe2O3. Ionic compounds are easily sol­
uble in polar solvents such as DES (Abbott et al., 2006). Most metallic Fe
dissolved in CC-LAC and GUC-LAC DESs, while it completely dissolved
in EG-MA DES. Based on Eq. 2, metallic Fe dissolution in a DES leads to
hydrogen gas evolution, attributed to the hydrogen ion originating from
the organic acid within the DES (Riaño et al., 2017). This gas evolution
can produce foam in the DES owing to its viscosity, hindering solid
sample leaching. Accordingly, CC-LAC, with the highest viscosity,
exhibited the lowest Fe leaching efficiency, while EG-MA, with the
lowest viscosity, dissolved all Fe without foam formation. In DES
leaching, metals can impede the leaching process, necessitating the
conversion of all metals into oxides during pretreatment.
Fe(s) + 2H+ 2+
(DES) ⇌Fe(DES) + H2(g) (2)
Fig. 3. Leaching efficiency of Nd and Fe oxides in different DESs (leaching
condition: 1:100 S/L (w/w) ratio, 70 ◦ C, 5 h).
4
Hydrometallurgy 226 (2024) 106284
In contrast to Nd2O3 and Fe, Fe3O4 and Fe2O3 exhibited variations in
leaching efficiency based on the DES type. Particularly, Fe3O4 displayed
significant disparities. While 99.97% of Fe3O4 dissolved in GUC-LAC
DES, its leaching efficiency was substantially lower in CC-LAC and EG-
MA, registering efficiencies of 21.1% and 0.91%, respectively.
Although Fe2O3 followed a similar pattern, it achieved markedly lower
leaching efficiencies of 6.83% in GUC-LAC, 3.56% in CC-LAC, and
0.48% in EG-MA. The solubility of these metal oxides is intrinsically tied
to the acidity of the DESs. Increased solubility correlates with lower pH
values, as the protons in more acidic DESs serve as oxygen acceptors,
disrupting the bonds between metal and oxygen (Pateli et al., 2020). As
indicated in Table 3, GUC-LAC possesses the most acidic pH of − 0.88,
compared to pH values of 0.27 in CC-LAC and 0.43 in EG-MA, mirroring
the observed leaching patterns for Fe3O4 and Fe2O3.
While the rare earth oxide, Nd2O3, dissolved in all DESs, Fe2O3
consistently exhibited low leaching efficiency. For the selective leaching
of REEs from Fe using DESs, it is beneficial to transform the Nd2Fe14B
magnet alloy into Nd2O3 and Fe2O3. As shown in Fig. 3, Fe3O4 inhibits
selectivity in CC-LAC and GUC-LAC, while EG-MA DES can selectively
leach REEs even in the presence of Fe3O4. Compared to inorganic acid
leaching, this low solubility of Fe oxides positions DESs favorably for
selective REE leaching. Typically, inorganic acid leaching of NdFeB
magnets involves either a strong acid leaching followed by separation or
a weak acid leaching approach (Yang et al., 2017). Unfortunately, Fe2O3
and Fe3O4 completely dissolve with strong acids, necessitating a sub­
sequent pH-controlled separation of REEs from Fe, leading to iron hy­
droxide byproduct generation. Weak acid leaching enables selective
leaching of REEs at a pH range of 3–4, assuming iron is present as Fe2O3,
given its slow dissolution kinetics. However, the presence of Fe3O4
lowers selectivity, as it dissolves in this pH range. Therefore, using DESs
over conventional inorganic acids offers an environmentally friendlier
and cost-effective solution, and also high selectivity of REEs over Fe.
3.2. DES leaching after oxidative roasting of NdFeB permanent magnets
An oxidative roasting pretreatment is typically employed to trans­
form the NdFeB magnet into an oxide form before leaching. As
confirmed in Section 3.1, it is important to convert Nd and Fe into oxide
forms, without remaining Fe metal after roasting. Initially, the magnets
underwent oxidative roasting at 600 ◦ C for 5 h. Typically, roasting a
NdFeB magnet at 600 ◦ C yields Nd2O3 and Fe2O3 crystal structures
(Yoon et al., 2015). However, during the DES (GUC-LAC) leaching of this
roasted product, foaming occurred, suggesting incomplete metal-to-
oxide conversion. A subsequent roast at 900 ◦ C for 5 h was conducted
to achieve full oxidation before leaching in DESs.
Post the oxidative roasting of the NdFeB magnets, the XRD pattern
(Fig. 4) revealed the formation of Fe2O3 and NdFeO3, a combined oxide
of Nd and Fe. As depicted in Fig. 5, the Nd leaching efficiency was subpar
across all DESs, the highest at 22.5% in GUC-LAC. This suggests that
NdFeO3 inhibits REE leaching. The Fe leaching efficiency was also low,
registering at 2.95% in GUC-LAC, 0.64% in CC-LAC, and 0.32% in EG-
MA.
During the oxidative roasting of NdFeB magnets, metal oxides can
form according to Eqs. 3–5 (Parida et al., 2002; Tanvar and Dhawan,
2021).
Nd2 Fe14 B(s) + 1.5O2(g) ⇌12Fe(s) + Fe2 B(s) + Nd2 O3(s) (3)
2Fe(s) + 1.5O2(g) ⇌Fe2 O3(s) (4)
0.5Nd2 O3(s) + Fe(s) + 0.75O2(g) ⇌NdFeO3(s) (5)
Fig. 6 shows the temperature-dependent Gibbs free energy change
(ΔG◦ ) for metal oxides (Nd2O3, Fe2O3, and NdFeO3), scaled per 1 mol of
oxygen (O2) consumed. The calculations using Eq. 6 were based on the
thermodynamic values provided in Table 5, assuming a negligible
temperature dependence of ΔH◦ and ΔS◦ (Wagman, 1982; Parida et al.,
S. Heo et al. Hydrometallurgy 226 (2024) 106284

Fig. 4. XRD pattern of NdFeB magnets after oxidative roasting at 900 ◦ C for 5 h.

Table 5
Thermodynamic data of species shown in Eqs. 3–5.
Species ΔH◦ (kJ mol− 1) S◦ (J mol− 1
K− 1)

O2 0 205.138
Nd 0 71.5
Nd2O3 − 1807.9 158.6
Fe 0 27.28
Fe2O3 − 824.2 87.4
NdFeO3 − 1362.5 123.9

(25 ◦ C, 1 atm) (Wagman, 1982; Parida et al., 2002)

Fig. 5. Leaching efficiency of Nd and Fe after oxidative roasting of NdFeB
magnets (oxidative roasting at 900 ◦ C for 5 h; leaching condition: 1:100 S/L (w/
w) ratio, 70 ◦ C, 5 h).
2002; Firdaus et al., 2018). Given that the Gibbs free energy for con­
verting Fe into Fe2O3 is higher than the energy required for Nd2O3 to
combine with Fe to form NdFeO3 at all temperatures, Fe prioritizes
NdFeO3 formation before Fe2O3. Given the higher Fe content relative to
Nd in NdFeB magnets, the remaining Fe is converted to Fe2O3 (Wagman,
1982). Typically, NdFeO3 and Fe2O3 are formed after oxidative roasting
owing to the characteristic composition of NdFeB magnets, with a 3:7
ratio of Nd to Fe. Moreover, achieving a crystalline form of Nd2O3 and
Fe2O3 without metallic iron is challenging. Therefore, pretreatment is
required to suppress NdFeO3 formation that inhibits REE leaching and
ensures that only oxides of Nd and Fe are present.

3.3. DES leaching after NaOH caustic digestion of the magnets

The NaOH caustic digestion is a pretreatment method for recovering

REEs from monazite (Yu and Chen, 1995). The REEs can be converted
into hydroxides by reacting with a 50% NaOH solution at 140 ◦ C (Yu and
Chen, 1995). When using NaOH digestion for pretreating NdFeB mag­
nets (50% NaOH, 145 ◦ C, 5 h), Nd and Fe are converted into Nd(OH)3
and Fe3O4, respectively, according to Eqs. 7 and 8 (Kim et al., 2022).
Nd(s) + 3H2 O(l) ⇌Nd(OH)3(s) + 1.5H2(g) (7)
Fig. 6. Ellingham diagram for Nd2O3, Fe2O3, and NdFeO3 based on 1 mol of O2
gas consumption.
3Fe(s) + 4H2 O(l) ⇌Fe3 O4(s) + 4H2(g) (8)

2002). Fig. 7 shows the Eh-pH diagram of Nd-H2O and Fe-H2O systems
based on the Nernst equation and thermodynamic data shown in
(6)
◦ ◦ ◦
ΔG = ΔH − TΔS Table 6. According to Fig. 7, Nd is a hydroxide in the alkaline region.
When roasting the NdFeB magnet, decomposition occurs according However, Fe can manifest in various forms in the alkaline region,
to Eq. 3, after which Nd and Fe are converted into oxides. As illustrated including Fe3O4 and Fe2O3. Nevertheless, Fe3O4 is the final product in
in the Ellingham diagram (Fig. 6), the oxidation of Nd to Nd2O3 is NaOH digestion due to the Schikorr reaction, outlining the conversion of
preferred as it possesses the lowest Gibbs free energy. The Nd metal can Fe(II) hydroxide into Fe3O4 (Thompson, 1940). When there is insuffi­
be oxidized to Nd2O3 even at minimal air concentrations (Parida et al., cient oxygen in the solution to facilitate metallic Fe oxidation to Fe(III)
species, Fe in the solution corrodes to Fe(OH)2 according to Eq. 9.

5
S. Heo et al. Hydrometallurgy 226 (2024) 106284

Fig. 7. Eh-pH diagram of Nd-H2O and Fe-H2O systems at 25 ◦ C and 1 atm ([Nd]Tot = 0.2 M, [Fe]Tot = 1.13 M).

Table 6
Thermodynamic data for Nd-H2O and Fe-H2O systems at
25 ◦ C and 1 atm.
1
Species ΔG◦ (kJ mol− K− 1)

H2O − 237.14
OH− − 157.3
Fe2O3 − 742.2
Fe3O4 − 1015.4
HFeO−2 − 377.7
Fe2+ − 78.87
Fe3+ − 4.7
Nd3+ − 671.6
Nd(OH)3 − 1270.14

(Wagman, 1982; Parida et al., 2002)

Subsequently, through the Schikorr reaction, it transforms into the more
stable Fe3O4, as shown in Eq. 10 (Thompson, 1940).
3Fe(s) + 2H2 O(l) ⇌3Fe(OH)2(s) + H2(g)
3Fe(OH)2(s) ⇌Fe3 O4(s) + 2H2 O(l) + H2(g)
In this study, without introducing air or oxygen during digestion, the
Fe metal in the NdFeB magnet was not fully oxidized to Fe(III). As shown
in Fig. 8, XRD analysis post-NaOH digestion revealed that Fe3O4 was
detected as the sole iron species, coexisting with Nd(OH)3.
Fig. 9 demonstrates the Eh-pH diagram of B-Na-H2O systems under
the NaOH digestion conditions. In the alkaline region, boron (B) exists as
the BO−2 ion, suggesting that B can be removed during the NaOH
Fig. 9. Eh-pH diagram of B-Na-H2O system ([B]Tot = 0.99 M, [Na]Tot = 19 M,
145 ◦ C, P = 4.031 bar (the vapor pressure of water at 145 ◦ C)); This Eh-pH
diagram was developed by HSC Chemistry.
(9)
digestion process. In actual practice, the comparison of the content of B
(10) in NdFeB magnets before and after the NaOH digestion indicates that
99.8% of B was removed. This suggests that NaOH digestion can convert
the target metal into a leaching-friendly form while removing
impurities.
Fig. 10 displays the leaching results for NaOH-digested magnets in
various DESs. The leaching efficiency for Nd exceeded 96% across all
DESs, whereas the efficiency for Fe varied with the specific DES. The
leaching trends for Fe mirrored those observed for Fe3O4 in Fig. 3. The

Fig. 10. Leaching efficiency of NaOH-digested NdFeB magnet in different DESs

Fig. 8. XRD pattern of the NdFeB magnet after NaOH caustic digestion at (digested at 145 ◦ C, 1:10 S/L (w/w) ratio for 5 h; leaching conditions: 1:100 S/L
145 ◦ C, 1:10 S/L (w/w) ratio for 5 h. (w/w) ratio, 70 ◦ C, 5 h).

6
S. Heo et al.
CC-LAC and GUC-LAC DESs exhibited low Nd selectivity, with Fe
leaching efficiencies of 75.4% and 96.7%, respectively. Conversely, EG-
MA showcased an Nd leaching efficiency of 96.5% against 1.69% for Fe,
facilitating selective leaching of Nd.
In the NaOH-digested product, Nd existed as a hydroxide. However,
its leaching behavior mirrored that of the oxide, presumably related to
the leaching mechanism of metal oxides in DESs. The leaching process
for metal oxides within DESs typically unfolds in two stages (Yuan et al.,
2022). Initially, the proton from the functional group in the HBD reacts
with the active OH site of the hydrated metal oxide, forming an inter­
mediate species, as demonstrated in Eq. 11. “Bulk –– Me-OH” represents
– leaching compared to oxidative roasting products where REEs are
a hydrated metal oxide with an active OH site, while HX signifies the
HBD of DESs.
Bulk ≡ Me − OH + HX⇌Bulk ≡ Me − OH+
2 ⋯X
n−
(11)
Subsequently, if the metal–ligand complex is more stable than the
metal oxide, the proton disrupts the metal–oxide bond. The deproto­
nated ligand replaces the OH active site, as detailed in Eq. 12 (Yuan
et al., 2022).
Bulk ≡ Me − OH+ n− n−
2 ⋯X ⇌Me − X(DES) + H2 O (12)
Given the dissolution mechanism of metal oxides, the process is
initiated with hydrated metal oxides. This suggests that if metal oxides
dissolve in DESs, their hydroxide counterparts also dissolve in DESs via a
similar mechanism. Therefore, the NaOH-digested sample permitted Nd
leaching, as shown in Fig. 10. Particularly, the preliminary experimental
results (Fig. 3) demonstrate that EG-MA does not dissolve Fe3O4. This
indicates the potential of the selective leaching of Nd from the NaOH
digestion sample, having the crystal form of Nd(OH)3 and Fe3O4.
3.4. DES leaching after the NaOH caustic digestion-roasting of the
magnets
Subsequent to Nd and Fe in the NdFeB magnets being converted to
Nd(OH)3 and Fe3O4 by the preceding NaOH caustic digestion, it is
possible to prevent Nd2O3 and Fe from forming NdFeO3 during the
oxidative roasting process. Therefore, Nd2O3 and Fe2O3 can be derived
as the final products. To convert Nd(OH)3 into an oxide form and Fe3O4
to Fe2O3, the material was roasted at 450 ◦ C, a lower temperature than
typically used for oxidizing NdFeB magnets. The XRD analysis
confirmed the formation of Nd2O3 and Fe2O3 without evidence of
NdFeO3 (Fig. 11). Given the intrinsic properties of NdFeB magnets, the
oxidation reaction progresses from the outer surface to the inner core of
the magnet particle. To mitigate NdFeO3 formation during the lower-
temperature oxidative roasting, the interior of the magnet particle re­
tains its metallic form due to incomplete oxidation. Moreover, a minimal
amount of NdFeO3 might form on the exterior (Firdaus et al., 2018).
However, conducting NaOH digestion before roasting hinders the
Fig. 11. XRD pattern of the NdFeB magnet after NaOH caustic digestion-
oxidative roasting at 450 ◦ C for 3 h.
7
Hydrometallurgy 226 (2024) 106284
formation of NdFeO3 from the reaction between Nd2O3 and Fe. This
ultimately yields Nd2O3 and Fe2O3, as confirmed by the backscattered
electron (BSE) images in Fig. 12. In contrast to the oxidative roasted
product (Fig. 12 (b)), where the particle's exterior is encapsulated by
iron oxide, NaOH caustic digestion pretreatment (Fig. 12 (c)) causes
REEs and Fe phase to separate, with REEs clustering on the particle's
exterior. In addition, cross sections of Fe3O4 with octahedral and cubic
crystal morphology post NaOH caustic digestion can be seen in Fig. 12
(c) (Torres-Gómez et al., 2019). This morphology was maintained even
post-roasting (Fig. 12 (d)), providing a structure more conducive to REEs
encapsulated (Fig. 12 (b)).
Fig. 13 presents the leaching results for the NaOH digested–roasted
magnets in three DESs. Neodymium exhibited a leaching efficiency of
97.2% in GUC-LAC, 97.3% in EG-MA, and a marginally reduced leaching
efficiency of 94.6% in CC-LAC. For Fe, the maximum leaching efficiency
was 12.1% in GUC-LAC, 7.2% in CC-LAC, and a minimum of 0.84% in
EG-MA. This trend aligns with the findings of the preliminary experi­
ment. The BSE images further validate this (Fig. 12 (e)). When compared
to Fig. 12 (d), most REEs, indicated by bright areas, have been leached,
leaving predominantly Fe. Compared to the leaching results from NaOH-
digested magnets (Fig. 10), the Fe leaching efficiency decreased, and Nd
selectivity improved in all DESs owing to Fe3O4 conversion to Fe2O3
during the final oxidative roasting. Although Nd could be selectively
leached from three DESs after the NaOH digestion–roasting, EG-MA DES
demonstrated superior selectivity. Therefore, employing EG-MA as a
lixiviant enabled selective and high Nd leaching after NaOH digestion
and NaOH digestion–roasting pretreatments. The mass balance for the
EG-MA DES leaching process using NaOH digestion-roasted magnet is
shown in Table 7. Furthermore, the detailed mass and elemental analysis
of the overall REE recovery process from NdFeB magnets is presented in
Table S1 of Supplementary data.
For REE selective leaching from NdFeB magnets using DESs, Nd and
Fe must individually exist as oxides. Through NaOH digestion–oxidative
roasting pretreatment, NdFeO3 formation was suppressed, and Nd and
Fe were efficiently converted into Nd2O3 and Fe2O3, respectively.
Therefore, the NaOH digestion–oxidative roasting proved the most
suitable pretreatment method for Nd selective leaching. Among tested,
EG-MA outperformed other DESs, demonstrating superior REE leaching
efficiency and selectivity, low viscosity, and easy handling. This is also
superior to the inorganic acid leaching. Using 0.5 M and 1.0 M hydro­
chloric acid, the leaching efficiencies of 87.4% and 77.5% for Nd and
1.32% and 8.14% for Fe, respectively, were achieved from the NaOH
digestion-roasted product. In order to further separate Nd from Fe, the
double salt precipitation or solvent extraction must be applied to remove
Fe, and the solution after the recovery process cannot be reused (Yoon
et al., 2017; Zhang et al., 2020). Thus, considering the following process
for recycling, DES leaching can be a better option.
3.5. Recycling of DESs
Using EG-MA DES, DES recycling test in the process was performed,
which had the best selective leaching effect of REEs from NaOH
digestion-oxidative roasted NdFeB magnet. Prior to employing the DES
in the second cycle, the REEs leached during the first cycle were
recovered in the form of rare earth oxalate. This recovery was achieved
by adding a stoichiometric amount of oxalic acid in accordance with Eq.
13. The oxalate precipitation was conducted for 2 h at room tempera­
ture, utilizing sonication for dispersion. Following precipitation, the
precipitated solid was separated from the solution, and the separated
liquid, i.e. recycled DES, was used for the second leaching. The leaching-
precipitation process was repeated up to three times.
2REE3+ + 3C2 O2−4 ⇌REE2 (C2 O4 )3 (13)
As depicted in Fig. 14, 97% of Nd was leached during the second
S. Heo et al. Hydrometallurgy 226 (2024) 106284

Fig. 12. Backscattered electron (BSE) images of (a) NdFeB magnet, (b) NdFeB magnets after oxidative roasting at 900 ◦ C, (c) NdFeB magnet after NaOH caustic
digestion at 145 ◦ C, 1:10 S/L ratio for 5 h, (d) NdFeB magnet after NaOH caustic digestion–oxidative roasting at 450 ◦ C for 3 h, (e) leach residue of NaOH caustic
digestion–oxidative roasted NdFeB magnet using EG-MA DES (1:100 S/L (w/w) ratio, 70 ◦ C, 5 h).

Fig. 13. Leaching efficiency of NaOH digestion-oxidative roasted NdFeB Fig. 14. EG-MA DES recycling test results: Nd and Fe leaching efficiency of
magnet in different DESs (digested at 145 ◦ C, 1:10 S/L (w/w) ratio for 5 h; NaOH digestion-oxidative roasted NdFeB magnets.
roasted at 450 ◦ C for 3 h; leaching conditions: 1:100 S/L (w/w) ratio, 70 ◦ C,
5 h).
reuse; however, a noticeable decline in leaching efficiency occurred in
subsequent reuses, with only 82% of Nd leached in the third cycle. This
Table 7
appears to be the effect of the remained oxalic acid in the recycled DES
Mass and elemental balance of the EG-MA leaching process. post-precipitation, despite the addition of a stoichiometric amount of
oxalic acid. Notably, when 1.5 times the stoichiometric amount of oxalic
Sample Yield (wt%) Element (%) Distribution (%)
acid was introduced after the initial leaching, the Nd leaching efficiency
Nd Fe Nd Fe dropped to 52.8% in the second cycle. This suggests that an excess of
Leach Solution 33 55.57 0.0035 97.23 1.12 oxalic acid in EG-MA DES has the potential to impede the leaching of
Leach Residue 67 0.78 21.84 2.77 98.88 REEs in the following cycle. Iron exhibited a consistently low leaching
Calculated feed 100 18.86 43.53 100 100 efficiency of less than 1% across all cycles, enabling selective leaching of
Measured feed 100 19.51 47.86 – –
REEs. Therefore, after leaching the NaOH digestion-roasted NdFeB
permanent magnet, the EG-MA DES could be recycled in the process for
at least two cycles. The recyclability of the DES can be further optimized

8
S. Heo et al. Hydrometallurgy 226 (2024) 106284

by adjusting the amount of oxalic acid appropriately. This observation

aligns with findings from a prior study (Chen et al., 2019). In a
comprehensive view, Fig. 15 presents the completed flow sheet, incor­
porating the DES recycling process.
In addition to the recyclability of the solvent, the cost of DES should
be considered for process scale-up. The international price of ethylene
glycol is 0.47 USD/kg, and that of maleic acid is 1.06 USD/kg (List of
Indexes, 2023). Although these are higher than the price of inorganic
acids (0.14 USD/kg for H2SO4, 0.15 USD for HCl) (List of Indexes, 2023),
DESs are reusable and have more favorable process conditions due to
their higher selectivity of REEs. Furthermore, DESs are cheaper than ILs,
another non-aqueous solvent, and have a lower price compared to the
material obtained as final product of the process, i.e. rare earth oxides,
making it advantageous in terms of process cost when scaling up.

4. Conclusions

In this study, the most suitable DES and pretreatment method for
selective leaching of REEs from waste NdFeB magnets were identified.
Three DESs (GUC-LAC, CC-LAC, and EG-MA) that effectively leach light
rare earth oxides were evaluated. Initially, the solubility of Nd2O3, Fe,
Fe3O4, and Fe2O3 in these DESs was examined to establish suitable
crystallization conditions for selective leaching. The results revealed
that selective leaching was feasible if Nd and Fe were present as Nd2O3
and Fe2O3, respectively. Three pretreatment methods were applied to
convert the NdFeB magnet into these oxides. Through oxidative roast­
ing, a commonly used pretreatment method, the NdFeB alloy primarily
transformed into NdFeO3 and Fe2O3. However, the Nd leaching effi­
ciency was 5.87% in CC-LAC, 22.5% in GUC-LAC, and 7.89% in EG-MA,
indicating poor REE leaching. The formation of NdFeO3 during roasting
inhibited REE leaching, necessitating a pretreatment method to mitigate
NdFeO3 formation. Given that NdFeO3 can be formed by the reaction
between Nd2O3 and metallic Fe, the NaOH caustic digestion process was
introduced before oxidative roasting to convert REE to REE hydroxide.
This process yielded Nd(OH)3 and Fe3O4 through NaOH digestion, fol­
lowed by Nd2O3 and Fe2O3 formation via oxidative roasting at 450 ◦ C for
3 h. The EG-MA DES outperformed other DESs in leaching NaOH-
digested magnets, achieving Nd selective leaching with a leaching effi­
ciency of 96.5% for Nd and 1.69% for Fe. Conversely, leaching the NaOH
digested-roasted magnets enabled selective leaching in all DESs.
Particularly, EG-MA demonstrated superior performance with leaching
efficiencies of 97.3% for Nd and 0.84% for Fe. Hence, in the selective
leaching of REEs from NdFeB magnets using DESs, the EG-MA DES,
characterized by its low viscosity and high selectivity, proved the most
suitable lixiviant. The NaOH digestion or NaOH digestion–roasting
should precede as a pretreatment method to achieve selective leaching
of Nd. In addition, the possibility of solvent reuse was confirmed by
recycling EG-MA DES in the process. This study illuminates the potential
of EG-MA DES as an effective and highly selective lixiviant for the re­
covery of REEs from NdFeB magnets, significantly advancing our
knowledge in this critical area of recycling. These findings invite further
exploration into optimizing the overall process efficiency, scaling up the
approach for industrial applications, and elucidating the environmental
impact to secure a sustainable future.
CRediT authorship contribution statement
Seojin Heo: Writing – original draft, Visualization, Validation, Re­
sources, Methodology, Investigation, Formal analysis, Data curation.
Rina Kim: Writing – review & editing, Visualization, Validation, Su­
pervision, Resources, Methodology, Data curation, Conceptualization.
Ho-Sung Yoon: Writing – review & editing, Supervision, Resources,
Methodology, Conceptualization. Chul-Joo Kim: Writing – review &
editing, Resources, Methodology. Kyeong Woo Chung: Project
administration, Funding acquisition, Conceptualization. Sujeong Lee:
Resources, Project administration, Funding acquisition, Formal analysis,
Fig. 15. Flow sheet of recovery of REE from waste NdFeB magnet utilizing
NaOH digestion-oxidative roasting pretreatment and DES leaching.
Data curation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was supported by the Korea Institute of Energy Technol­
ogy Evaluation and Planning (KETEP) grant funded by the Korea gov­
ernment (MOTIE) (20217510100070, NP2021-037). The authors
extend their gratitude to Mr. Warren Bruckard, Dr. Mark Pownceby, and
Dr. Nebeal Faris from CSIRO Mineral Resources, Australia, for their
advice on the mineralogical analysis.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.hydromet.2024.106284.
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