Journal of Environmental Chemical Engineering 10 (2022) 108000

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Journal of Environmental Chemical Engineering

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Recovery of rare earth elements from spent NiMH batteries using subcritical
water extraction with citric acid
Jason Constantine a, Jenni Lie a, b, Jhy-Chern Liu a, *
a
Department of Chemical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106, Taiwan
b
Department of Chemical Engineering, Widia Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia

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

Editor: Apostolos Giannis Spent nickel-metal hydride (NiMH) batteries contain high concentrations of rare earth elements (REEs), nickel
(Ni), and cobalt (Co). Subcritical water extraction (SWE) process with citric acid as the leaching reagent was
Keywords: applied to spent NiMH batteries. The effects of acid concentration, solid to liquid ratio (S/L), reaction time, and
Citric acid reaction temperature were examined. Leaching efficiency increased with increasing acid concentration, reaction
Nickel metal hydride (NiMH) batteries
time and temperature, and decreased as S/L increased. Total of 90.85% of lanthanum (La), 88.84% of cerium
Rare earth elements (REEs)
(Ce), 90.85% of neodymium (Nd), 90.70% of Ni, and 91.62% of Co were leached out using 2.0 N of citric acid, S/
Recovery
Selective precipitation L of 10 g/L, at 150 ◦ C in 5 min. Selective precipitation of REEs was induced by the addition of diluted waste
Subcritical water extraction (SWE) phosphoric acid (H3PO4) to the leaching solutions. At [H3PO4]:[REEs] of 10:1, pH 2.0, and 65 ◦ C, 99.3% of La,
98.8% of Ce, and 99.0% of Nd were precipitated, which correspond to overall recovery of 90.2% of La, 87.8% of
Ce, and 89.8% of Nd. The results showed that SWE using citric acid followed by selective precipitation with
H3PO4 could effectively recover REEs from spent NiMH batteries.

1. Introduction
Nickel metal hydride (NiMH) batteries are commonly used in hybrid
electrical vehicles (HEV), mobile phones, and laptops. However, NiMH
batteries are gradually replaced by lithium-ion batteries, thus, higher
amount of spent NiMH batteries are generated [1,2]. The NiMH battery,
known for low toxicity and high energy density, is generally composed
of a cathode made of nickel hydroxide (Ni(OH)2), an anode made of a
hydrogen storage alloy based on misch metal (mainly rare earth ele­
ments, REEs) [3–5]. Typical composition of NiMH is 36–42% of Ni,
3–5% of Co and 5–25% rare earth elements (REEs), such as lanthanum
(La), cerium (Ce), and neodymium (Nd) [6]. Reuse and recycling of
spent NiMH batteries is an important issue since it will result in lowest
environmental impacts on CO2 emission, resource depletion, and
non-renewable energy demand as analyzed by life cycle assessment [2].
Meanwhile, spent NiMH batteries are regarded as one of the most
promising secondary sources of REEs for sustainable utilization [7,8].
Due to their unique properties, REEs have been widely used in
various high-technology industries, such as green energy of wind tur­
bines and solar panels, electrical and electronics such as batteries and
fluorescent lamps, and catalysts for petroleum refining [9]. Therefore,
REEs are called the “vitamins of modern industry” because they are
essential components in all high-tech products [10,11]. Considering the
demand and supply gap for REEs, there is therefore a need to adopt the
sustainable approach of the circular economy system [12]. To ensure
sustainable utilization of REEs, development of recovery technology
from secondary sources is essential.
The recycling of spent batteries can be conducted via pyrometal­
lurgical and hydrometallurgical process, however, the hydrometallurgy
is more preferable due to the milder conditions, higher selectivity and
sensitivity [13]. Meshram et al. obtained leaching efficiency 98% of Nd
and 89% of Ce from mixed cathode and anode of spent NiMH batteries
using 2 M of H2SO4 solution as leaching agent at 75 ◦ C, S/L of 100 g/L,
for 2 h [6]. The leaching of REEs from spent NiMH batteries was opti­
mized by varying experimental parameters, such as H2SO4 concentra­
tion (1–4 M), solid to liquid ratio (S/L of 25–200 g/L), at 90 ◦ C for 4 h
[1]. Oxidative leaching using H2SO4, H2O2, and Na2S2O8 enhanced Ni
leaching from mixed batteries including NiMH batteries and induced
NaLa(SO4)2 precipitation [14]. Both laboratory tests and pilot trials
were conducted using H2SO4 to recover Ni, Co, and REEs from spent
NiMH batteries [15]. The recent study showed that about 100% leaching
efficiency of Ni and La could be obtained using 10 M of formic acid, S/L

* Corresponding author.
E-mail address: liu1958@mail.ntust.edu.tw (J.-C. Liu).

https://doi.org/10.1016/j.jece.2022.108000
Received 1 April 2022; Received in revised form 20 May 2022; Accepted 26 May 2022
Available online 3 June 2022
2213-3437/© 2022 Published by Elsevier Ltd.
J. Constantine et al.
Table 1
Elemental composition in spent NiMH batteries by XRF analysis.
Element Ni Mn Zn La
Wt (%) 53.80 10.24 7.77 7.05
Element Cl Fe Si Al
Wt (%) 1.40 1.14 0.46 0.31
of 100 g/L, at 40 ◦ C for 3 h [16]. Glucose and its bio-oxidation products
were used for leach of REEs from spent NiMH and high efficiency was
found at pH 3.0 [17]. Organic acid is known as green lixiviant which is
biodegradable, has no harmful gas emission and less risk of corrosion of
the operational equipment, some organic acids also give the selective
leaching of valuable metals present in waste batteries [18].
Leaching of valuable metals from spent NiMH batteries required
concentrated mineral acids and it is time consuming [12]. Minimizing
acid concentration, as well as heating time could reduce cost and make
the extraction of REEs feasible at a larger scale [19]. Subcritical water
extraction (SWE) is a process which involves water in a temperature
range of 100–374 ◦ C and pressure of 1–22.1 MPa where mass transfer
and extraction rate are enhanced as a result of decreased dielectric
constant (ϵ), surface tension, and viscosity [20]. SWE was very effective
in leaching out 99.85% of Ni, 91.72% of Co, 96.26% of La, 85.75% of
Nd, and 84.37% of Ce using 0.5 N HCl, S/L of 20 g/L, 100 ◦ C for 5 min
[21]. It has been applied to leaching of yttrium (Y) and europium (Eu)
from waste cathode-ray tube (CRT) phosphor [22]. Compared with
conventional extraction method that required long reaction time and
concentrated acid solution, SWE could potentially be an alternative,
green method.
The chemical precipitation of REEs using common precipitants such
as sulfate, carbonate, fluoride, phosphate, and oxalate was reviewed,
and it was found that pH of the system has a profound effect [23].
Typical hydrometallurgical process of REEs recycling consists of acid
leaching, solvent extraction, and followed by oxalate precipitation [24,
25]. Dilute phosphoric acid was adopted in the current study since the
separation of REEs from heavy metals could occur at relatively low pH
when in the presence of phosphate [26]. The separation of REEs from
heavy metals via selective precipitation of REEs has been demonstrated
on recovery of La, Ce, and Nd in acid leaching solution of spent NiMH
batteries [27].
This study aimed to investigate leaching of REEs (La, Ce, and Nd), Ni,
and Co from spent NiMH batteries utilizing SWE and organic acids.
Important parameters such as acid concentration, S/L, temperature and
reaction time were examined. The subsequent separation of REEs (La,
Ce, and Nd) from Ni and Co was then assessed by the addition of waste
phosphoric acid (H3PO4) from the semiconductor manufacturer. Effects
of pH value, molar ratio of phosphate to REEs ([H3PO4]:[REEs]), and
temperature were investigated.
2. Materials and methods
2.1. Materials
The mixed cathode and anode of spent NiMH battery powder was
provided by Yen-Long Renewable Technology Co., Ltd, Kaohsiung,
Taiwan. The spent batteries were discharged in the salt solution,
crushed, dried at 110 ◦ C, and sieved with 140 mesh (particle size <105
µm) for experiments. The powder sample was characterized by X-ray
fluorescence (XRF, SEA6000VX, HSFinder). Results show that Ni has the
highest content (53.80%), followed by Mn (10.24%), Zn (7.77%), Co
(6.10%), and REEs, including La (7.05%), Ce (2.58%) and Nd (1.66%)
(Table 1). This study focused on the leaching of the most valuable metals
in spent NiMH batteries, including Ni, Co, La, Ce and Nd. The crystal
structure of the metal compounds in the batteries powder was assessed
by X-ray powder diffraction (XRD, D2 Phaser, Bruker), and the phase
identification was analyzed by evaluating the intensity of each peak
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Journal of Environmental Chemical Engineering 10 (2022) 108000
Co K Ce Cd Nd
6.10 4.45 2.58 1.85 1.66
P Ca Y S Dy
0.22 0.23 0.18 0.17 0.10
with Diffrac.Eva V.4.3 and the diffraction patterns of crystalline phases
were identified according to Powder Diffraction Files (PDF) and Crys­
tallography Open Database (COD). Fig. 1a shows the major crystalline
phases were the metal hydroxide group, such as nickel hydroxide (Ni
(OH)2, JCPDS #73-1520), metal oxide group, such as cobalt oxide (CoO,
JCPDS #78-0431), and metal alloy group, such as lanthanum nickel
(LaNi5, JCPDS #65-3777), cerium cobalt (Ce5Co19, JCPDS #65-2150),
neodymium nickel (Nd2Ni7, JCPDS #22-0735), and cerium nickel
(Ce2Ni7, JCPDS #20-0042). Field-emission scanning electron micro­
scope and energy dispersive X-ray spectroscopy (FESEM-EDX, JSM-
6390LV, JEOL) analysis showed that the spent NiMH batteries powder
had an irregular particle shape and varying particle size (Fig. 1b). The
EDX results in Fig. 1c support the XRF data that Ni was of highest
content and REEs (La, Ce and Nd) existed in the spent NiMH batteries.
Therefore, results of both XRD and FESEM-EDX analysis confirmed the
presence of valuable metals and REEs in significant concentrations.
Hydrochloric acid (HCl, 37%, Honeywell) and nitric acid (HNO3,
65%, Pancreac) were used for aqua regia digestion process to determine
the total metal contents of spent NiMH batteries (NIEA S321.63B,
Taiwan). The leaching solution from aqua regia digestion was filtered,
diluted and analyzed by inductively coupled plasma optical emission
spectrometry (ICP-OES, iCap 7000, Thermo). Main metal content of
spent NiMH batteries included Ni (383.36 mg/kg), La (82.12 mg/kg),
Mn (72.32 mg/kg), Co (47.09 mg/kg), Zn (38.64 mg/kg), Ce
(25.88 mg/kg), Nd (21.99 mg/kg), Cd (13.80 mg/kg), Al (12.02 mg/
kg), K (11.04 mg/kg), Fe (4.45 mg/kg), and Cu (2.48 mg/kg). These
concentrations were used as the basis for assessing leaching efficiency.
The average dissolution of the spent NiMH batteries powder was 96.61%
by weight. To confirm a complete metal extraction by the aqua regia
method, the solid residue was assessed by XRD. Fig. 1a shows that only
graphite still existed as the inert compound in the residue. This result
suggested that a complete metal digestion was achieved.
Acetic acid glacial (CH3COOH, purity>99.7%, Fisher), citric acid
monohydrate (C6H8O7⋅H2O, Merck), 1-hydroxyethane-1,1-diphos­
phonic acid (etidronic acid, C2H8O7P2, 4.2 mol/L), and L-ascorbic acid
(C6H8O6, purity>99.0%, Tokyo Chemical Industry) were used as the
leaching agent. Waste phosphoric acid (H3PO4) from the semiconductor
manufacturer with the concentration about 15 M was supplied by Mega
Union Co., Ltd, Taoyuan, Taiwan. The standard solutions of each metals
with the purity > 99.9% for inductively coupled plasma (ICP) analysis
were purchased from Merck. All chemicals were used directly without
any further purification.
2.2. Leaching by SWE
Valuable metal leaching was conducted in a bench-scale subcritical
water reactor made by stainless steel (SS 316). The spent NiMH batteries
powder was mixed with organic acid solutions at certain concentration
of acid and solid in a glass chamber, the mixture then was put into the
SWE reactor which was equipped with an external electric heater, a
pressure gauge, a thermocouple (K-type), a lid with screws [22]. The
reactor was sealed and closed tightly, and the pressurization of the
rector was achieved by introducing N2 gas until reaching the pre-set
initial pressure of 10 kg/cm2. The mixture was heated to desired tem­
perature (100, 125, and 150 ◦ C), which took ca. 30 min. The mixture
temperature was then maintained for certain reaction time (5, 15 and
30 min), and afterward, SWE reactor was cooled down to about 60 ◦ C by
cold water circulation. The mixture was filtered with 0.22 µm
J. Constantine et al. Journal of Environmental Chemical Engineering 10 (2022) 108000

Fig. 1. a) The XRD pattern of spent NiMH batteries powder and aqua regia residue, b) SEM image, and c) EDX result of spent NiMH batteries.

3
J. Constantine et al.
Fig. 2. Effects of organic acid type on the leaching efficiency of valuable metals
with 1.0 N of citric acid, S/L of 20 g/L, 100 ◦ C for 5 min.
membrane to separate the leaching residue and solution. The metal
concentration in the leaching solutions was analyzed using ICP-OES,
while the leaching residue was dried at 60 ◦ C for 24 h and then char­
acterized using XRD and FESEM-EDX. Leaching experiments were in
triplicates and the average value was taken.
2.3. Selective precipitation
The selective precipitation experiment was conducted by the addi­
tion of diluted waste H3PO4 to the leaching solution of SWE. The effects
of molar ratio, [H3PO4]:[REEs], pH, and temperature were investigated.
Nitric acid (HNO3) and sodium hydroxide (NaOH) were used to adjust
the pH of the solution. The diluted H3PO4 solution was added to the
solution and stirred at 200 rpm for 8 h to let the reaction reach equi­
librium, followed by settling for 3 h. The suspension was separated by
vacuum filtration. The supernatant was analyzed by ICP-OES while the
precipitate was dried at 60 ◦ C for 24 h in the oven and analyzed XRD.
For comparison, the computer software PHREEQC was used to predict
equilibrium conditions.
3. Results and discussions
3.1. Leaching of valuable metals by SWE
Four types of organic acid were used in the leaching of metals from
spent NiMH batteries, including acetic acid, ascorbic acid, citric acid,
Fig. 3. Effects of a) acid concentration on SWE with S/L of 20 g/L, and b) solid to liquid ratio (S/L) on SWE with 2.0 N of citric acid, 100 ◦ C for 5 min.
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Journal of Environmental Chemical Engineering 10 (2022) 108000
and 1-hydroxyethane-1,1-diphosphonic acid (etidronic acid). Acetic
acid is a monoprotic acid which has a pKa value of 4.77 [28]. Ascorbic
acid is a diprotic acid that dissociates and releases two protons (pKa1 =
4.14 and pKa2 = 11.53) [29]. Citric acid is a triprotic acid with disso­
ciation constants of pKa1 = 3.13, pKa2 = 4.78, and pKa3 = 6.43 [30].
Etidronic acid has four acid dissociations constant, pKa1 = 1.35, pKa2
= 2.80, pKa3 = 7.01, and pKa4 = 11.10 [31]. Experiments were con­
ducted using 1.0 N of acid, S/L of 20 g/L, 100 ◦ C, initial pressure of
10 kg/cm2, and reaction time of 5 min. The initial pH of acetic acid,
ascorbic acid, citric acid, and etidronic acid solution was 1.88, 1.89, 1,
73, and 1.04, respectively, which illustrated the order of acid strength.
The final pH (after leaching) of acetic acid, ascorbic acid, citric acid, and
etidronic acid solution was 3.64 ± 0.01, 3.45 ± 0.04, 2.65 ± 0.02, and
1.31 ± 0.04, respectively. Leaching results are shown in Fig. 2, and it
revealed that etidronic acid showed the highest leaching efficiency fol­
lowed by citric acid, acetic acid, while ascorbic acid resulted in the
lowest leaching efficiency. The highest leaching efficiency reached
90.8% of Ni, 89.4% of Co, 49.4% of La, 32.8% of Ce, and 37.3% of Nd.
From the pKa value of the acids, etidronic acid provided the highest
acidity among all four acids. Since spent NiMH battery sample contained
a significant amount of metal hydroxides, hydrogen ions (acidity) were
required in their dissolution process. Etidronic acid had the drawbacks
of more expensive and as a synthetic compound. Citric acid could result
in the second highest leaching efficiency, 63.8% of Ni, 55.6% of Co,
41.6% of La, 32.8% of Ce and 39.7% of Nd. It provided relatively high
acidity, and it is a ubiquitous natural acid which has a stronger complex
formation potential. Therefore, citric acid was chosen as the leaching
agent for further experiments. The dissolution reactions can be
expressed as the following equations:
Ni(OH)2(s) + 2H+(aq) = Ni2+(aq) + 2H2O(l) (1)
CoO(s) + 2H+(aq) = Co2+(aq) + H2O(l) (2)
LaNi5(s) + 13H+(aq) + 3.25O2(aq) = La3+(aq) + 5Ni2+(aq) + 6.5H2O(l)(3)
Ce5Co19(s) + 53H+(aq) + 13.25O2(aq) = 5Ce3+(aq) + 19Co2+(aq) +
26.5H2O(l) (4)
Nd2Ni7(s) + 20H+(aq) + 5O2(aq) = 2Nd3+(aq) + 7Ni2+(aq) + 10H2O(l)(5)
Ce2Ni7(s) + 20H+(aq) + 5O2(aq) = 2Ce3+(aq) + 7Ni2+(aq) + 10H2O(l) (6)
Effects of acid concentration were investigated using citric acid with
concentration of 1.0, 1.5, and 2.0 N. Experiments were carried out at
100 ◦ C, initial pressure of 10 kg/cm2, reaction time of 5 min, and S/L of
20 g/L. As shown in Fig. 3a, initial pH for the acid concentration of 1.0,
1.5, and 2.0 N was 1.73, 1.63, and 1.52, respectively, while the final pH
was 2.68 ± 0.01, 2.40 ± 0.01, and 2.22 ± 0.07. The leaching efficiency
of Ni, Co, La, Ce, and Nd slightly increased from 63.8%, 55.6%, 41.6%,
J. Constantine et al. Journal of Environmental Chemical Engineering 10 (2022) 108000

Fig. 4. Effects of a) temperature on SWE with 2.0 N of citric acid, S/L of 10 g/L, for 5 min, and b) reaction time on SWE with 2.0 N of citric acid, S/L of 10 g/
L, 100 ◦ C.

32.8%, and 39.7–65.5%, 60.3%, 50.9%, 43.2%, and 52.5%, respec­

tively, when the concentration of citric acid increased from 1.0 N to
2.0 N. It confirmed that concentration of hydrogen ions (H+) in the
leaching solution plays the important role in the dissolution of valuable
metals from spent NiMH batteries [1]. The insignificant change of
leaching efficiency of valuable metals by increasing the acid concen­
tration may be because citric acid is a weak acid, as evidenced by the
limited difference between initial and final pH values of solutions at
each concentration. The leaching of REEs from spent NiMH batteries, at
348 K, 100 g/L for 120 min, increased gradually with an increase in the
acid concentration till 2 M H2SO4. With further increase in the acid
concentration, the leaching efficiency of all metals remained almost
constant [6]. When using 1–4 M H2SO4 for waste NiMH batteries,
leaching of Al, Co, Fe, Mn, Ni, and Zn was consistent irrespective of
H2SO4 concentration variation, while leaching of Ce, La and Nd
decreased gradually owing to the precipitation of REE sulfates [1]. It was
found that HCl performed better than H2SO4 and HNO3 in SWE for spent
NiMH batteries, and the leaching efficiency increased with HCl con­
centration [27].
Effects of solid to liquid ratio (S/L) was studied under the value of 10,
Fig. 5. FTIR spectra of (A) 2.0 N of citric acid and (B) 2.0 N of citric acid after
20, and 30 g/L. Citric acid of 2.0 N, initial pressure of 10 kg/cm2, re­
subject to subcritical water condition.
action time of 5 min, reaction temperature of 100 ◦ C were chosen. The
initial pH of each experiment was 1.52. From Fig. 3b, it was apparent
leaching efficiency decreased with increasing S/L. The leaching effi­ system pressure increased to 14.3 ± 0.6, 16.7 ± 0.3, and 20.0 kg/cm2,
ciency decreased significantly from 71.1% to 31.50% of Ni, 68.9–28.8% respectively. The leaching efficiency increased with increasing temper­
of Co, 61.6–23.5% of La, 57.0–21.2% of Ce, and 65.2–23.2% of Nd as S/ ature as it increased from 71.1% to 90.7% for Ni, 68.7$ to 91.6% for Co,
L increased from 10 to 30 g/L. At a higher S/L, the concentration of the 61.6–90.8% of La, 60.0–88.8% of Ce, and 65.2–95.3% of Nd, respec­
metal oxide, metal hydroxide, and alloys in the system increased, and tively, as temperature increased from 100 to 150 ◦ C. The behavior
the acidity provided by 2 N of citric acid became insufficient. It was observed in this study was in agreement with previous studies using
evidenced by the higher final pH of the system, as the final pH for S/L of conventional acid leaching for recovery of REEs from spent NiMH bat­
10, 20, and 30 g/L was 1.98 ± 0.01, 2.15 ± 0.03, and 2.28 ± 0.01, teries [6]. One of the advantages of SWE is the enhanced self-ionization
respectively. The higher the pH value of solution, the lower the disso­ of water molecules, and higher concentrations of H3O+ and hydroxide
lution of metals in the system. Thus, the overall leaching efficiency of (OH–) [20]. The surface tension, viscosity, and dielectric constant of
metals decreased as S/L became higher. At higher S/L, insufficient acidic water are reduced at subcritical conditions as temperature increases,
lixiviant increased the viscosity of the slurry which resulted in decreased and consequently higher solubility and higher diffusivity [32]. The
mass transfer effect and low dissolution of the REMs in the solution [6]. penetration of the solvent to the sample matrix could be enhanced and
When S/L varied in the range of 25–200 g/L at a constant 4 M H2SO4 results in higher mass transfer of target metals to the solvent [20]. The
acid concentration, the leaching of metals increased as S/L increased behavior observed in this study was in agreement with previous studies
[1]. When solid concentration increased from 10 g/ L to 40 g/L, the SWE that temperature plays an important role in the SWE efficiency of REEs
leaching efficiency using 0.25 N HCl decreased significantly from 100% from waste NiMH batteries [21].
to 16.7% for Ni, 100–35.0% for Co, 97.5–29.5% for La, 98.4–33.8% for Effects of reaction time (5, 15, and 30 min) on the leaching efficiency
Nd, and 65.5–5.7% for Ce of spent NiMH batteries at 100 ◦ C [21]. was studied using 2.0 N citric acid, S/L of 10 g/L, at 100 ◦ C. Results in
The effects of temperature on leaching efficiency of metals were Fig. 4b revealed that leaching efficiency of the target metals increased
examined and results are shown in Fig. 4a. The SWE process was carried slightly at prolonged reaction time and 76.7% of Ni, 75.1% of Co, 71.1%
out under 100, 125, and 150 ◦ C, respectively, using 2.0 N of citric acid, of La, 71.6% of Ce, and 75.8% of Nd were leached out within 30 min.
S/L of 10 g/L, initial pressure of 10 kg/cm2, and reaction time of 5 min. There was no significant change of dissolution of the metals by pro­
When the temperature of the system reached 100, 125, and 150 ◦ C, the longing the reaction time, implying that SWE was a quick process. It was

5
J. Constantine et al.
Fig. 6. The species distribution of a) La, b) Ce, c) Nd, d) Ni, and e) Co as predicted by PHREEQC at 25 ◦ C, [H3PO4]:[REEs] of 10:1.
noted that it took ca. 30 min in heating the reactor to designated tem­
perature and the leaching process could already proceed in the period.
The decomposition of citric acid was assessed by Fourier transform
infrared spectrometer (FTIR, Tracer-100, Shimadzu) to observe if there
was a change of citric acid compound in the subcritical conditions.
Spectra of 2 N citric acid before and after subject to subcritical water
condition at 150 ◦ C for 5 min were compared. Fig. 5 shows that
decomposition of citric acid in subcritical condition at 150 ◦ C did not
occur since the FTIR spectra of citric acid before and after SWE showed
– O bond at wavelength of 1720.24 cm− 1
the characteristic peaks of C–
and C-OH at 1216.16 cm− 1, and both existed at similar concentration.
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Journal of Environmental Chemical Engineering 10 (2022) 108000
3.2. Recovery of REEs
In the current study, the recovery of REEs was carried out using se­
lective precipitation of REEs by adding phosphoric acid (H3PO4) as the
precipitation agent at low pH range [27,33]. Simulation by PHREEQC
shows that at molar ratio of [H3PO4]:[REEs] of 5:1, Ni forms strong
complexes with citrate (Cit3-), such as NiH2Cit+, NiHCit, NiCit-, and
would not form any precipitates at the pH< 5.0 (Fig. 6a). Cobalt forms
complexes with (Cit3-), such as CoH2Cit+, CoHCit, CoCit-, and does not
form Co3(PO4)2(s) until pH> 3.50 (Fig. 6b), while the insoluble REE
(PO4) precipitates start to form at pH 1.0, and became dominant at
J. Constantine et al.
Fig. 7. Effects of a) [H3PO4]:[REEs], b) pH value of leaching solution, c) precipitation temperature on the recovery of REEs, and d) XRD pattern of recovery products.
pH> 2.0 (Fig. 6a–c). It indicated that the selective precipitation of REEs
by adding H3PO4 was feasible at the pH range of 1.0–3.0. Experimental
results at [H3PO4]:[REEs] of 5:1 were different from simulation that
only 25.9% of La, 32.8% of Ce, and 16.5% of Nd were recovered as REE
(PO4) precipitates (Fig. 7a). It could be due to the formation of com­
plexes between La, Ce, and Nd with citrate, a potential ligand. Forma­
tion of REEs-citrate complexes rendered REE(PO4) precipitation difficult
under acidic conditions as predicted. At [H3PO4]:[REEs] of 10:1 and pH
1.92, the recovery of REEs increased to 82.8% of La, 88.2% of Ce, and
71.7% of Nd, while precipitation of Ni and Co were found to be 0.8% 1%
and 3.8%, respectively. Compared with prediction, the recovery of REEs
in the form of REE(PO4) precipitates, 99.6% of La, 97.1% of Ce, and
98.3% of Nd, was lower.
Effects of pH were studied under pH of 1.0, 1.5, 2.0, 2.5, and 3.0 with
[H3PO4]:[REEs] of 10:1, at 25 ◦ C. The REEs precipitation was observed
in the solution at pH 1.03, with precipitation of 16.7% of La, 21.6% of
Ce, and 20.8% of Nd (Fig. 7b). When the pH of the solution increased to
1.92, the highest REEs recovery was found of 82.8% of La, 88.2% of Ce,
and 71.7% of Nd. As the pH further increased to 2.54 and 2.99, REEs
precipitation gradually decreased and deviated from the prediction.
Effects of temperature on REEs recovery from leaching solution with
[H3PO4]:[REEs] of 10:1, pH 2.00, and reaction time of 8 h were inves­
tigated under the temperature of 25, 45, and 65 ◦ C. Results showed that
precipitation of REEs became higher as temperature increased, and
99.3% of La, 98.8% of Ce, and 99.0% of Nd was precipitated (Fig. 7c). It
could be because the solubility of LaPO4 and NdPO4 decrease with
increasing temperature in the range of 100–250 ◦ C [34]. This could be
considered an advantage since the leaching solutions of SWE was at high
temperature. The XRD results (Fig. 7d) confirmed that the major re­
covery products were LaPO4.0.5 H2O, CePO4⋅H2O, and NdPO4.2 H2O at
[PO3-
4 ]:[REEs] of 10:1, pH 2, and 65 C. It proved the effective and se­
◦
lective recovery of REEs from spent NiMH batteries using citric acid as
7
Journal of Environmental Chemical Engineering 10 (2022) 108000
the leaching solution and waste phosphoric acid as the precipitation
agent.
In summary, REEs, Ni and Co could be effectively leached out by
SWE using 2.0 N citric acid at 150 ◦ C within 5–30 min, an operating
condition relatively modest. Advantages of the leaching part include no
need of strong mineral acids, high-temperature pretreatment, and long
reaction time. In addition, waste phosphoric acid was utilized for se­
lective precipitation to recover REEs from the leaching solutions under
favorable conditions of pH, molar ratio, and temperature. It has been
pointed out that, though having the lowest environmental impact, reuse
and recycling process of waste NiMH batteries still consume consider­
able amount of energy and resource [2]. Thus, the current study
demonstrated an alternative green process for recovery of REEs, Ni, and
Co from spent NiMH batteries.
4. Conclusions
Leaching of valuable metals, such as REEs (La, Ce, and Nd), Ni, and
Co from spent NiMH batteries was examined using subcritical water
extraction (SWE). Although etidronic acid performed the best among
four types of acid, citric acid was chosen considering it is a common
organic acid that provides enough acidity, and could form metal-citrate
complexes that assisted in the leaching of Rees, Ni and Co from spent
NiMH batteries. When using 2.0 N citric acid, S/L of 10 g/L, reaction
time of 5 min, and 150 ◦ C in SWE, 90.85% of La, 88.84% of Ce, 90.85%
of Nd, 90.70% of Ni, and 91.62% of Co was leached out. The addition of
diluted waste H3PO4 to the SWE leaching solution induced highly se­
lective precipitation of La, Ce, and Nd. Recovery of 99.31% of La,
98.75% of Ce, and 99.05% of Nd in REE(PO4) was found, as confirmed
by XRD at [H3PO4]:[REEs] of 10:1, pH 2.00, and 65 ◦ C. The process
consisting of SWE using 2 0 N citric acid, followed by selective precip­
itation using diluted waste H3PO4 could be carried out under modest
J. Constantine et al.
temperature (<150 ◦ C), within relatively short reaction time
(5–30 min). Thus, it could be an alternative process to support the sus­
tainable utilization of REEs, Ni and Co.
CRediT authorship contribution statement
Jason Constantine: Data curation, Instrumental analysis, Software
simulation. Jenni Lie: Data curation, Instrumental analysis, Software
simulation, Writing – original, Involved in responses to reviewers’
comments. Jhy-Chern Liu: Conceptualization, Methodology, Supervi­
sion, Writing of manuscript and in charge of responses to reviewers’
comments.
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
Authors acknowledge the finanacial of support from the Ministry of
Science and Technology, Taiwan through grant: MOST-109-2221-E-011-
083.
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