Article

pubs.acs.org/est

Selective Extraction of Rare Earth Elements from Permanent Magnet

Scraps with Membrane Solvent Extraction
Daejin Kim,† Lawrence E. Powell,† Lætitia H. Delmau,‡ Eric S. Peterson,§ Jim Herchenroeder,∥
and Ramesh R. Bhave*
†
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
‡
Nuclear Materials Processing Group, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
§
Center for Advanced Energy Studies, Idaho National Laboratory, Idaho Falls, Idaho 83415, United States
∥
Molycorp Magnequench, Greenwood Village, Colorado 80111, United States
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*
S Supporting Information
Downloaded via IOWA STATE UNIV on January 15, 2019 at 15:56:38 (UTC).

ABSTRACT: The rare earth elements (REEs) such as

neodymium, praseodymium, and dysprosium were successfully
recovered from commercial NdFeB magnets and industrial
scrap magnets via membrane assisted solvent extraction
(MSX). A hollow fiber membrane system was evaluated to
extract REEs in a single step with the feed and strip solutions
circulating continuously through the MSX system. The effects
of several experimental variables on REE extraction such as
flow rate, concentration of REEs in the feed solution,
membrane configuration, and composition of acids were
investigated with the MSX system. A multimembrane module
configuration with REEs dissolved in aqueous nitric acid
solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric
acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were
recovered from the strip solution through precipitation, drying, and annealing steps. The resulting REE oxides were characterized
with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively
recovering pure REEs from the industrial scrap magnets.

■ INTRODUCTION
The world today has hugely benefited from the application of
rare earth elements (REEs) to most high-tech devices such as
cell phones, rechargeable batteries, computers, TV, and
fluorescent lighting.1−3 These REEs are the 15 lanthanides in
the periodic table along with scandium and yttrium. Over 90%
of REEs worldwide are currently being produced in China
which until very recently had restricted REE exports. The rising
REE demand in high-tech devices over the past two decades
resulted in skyrocketing prices of REEs in just a few years.4−7
This motivated the U.S. Department of Energy to launch the
Critical Materials Institute in 2013 in order to tackle the REE
supply challenge, focusing on three different areas such as
diversifying REE supplies, developing REE substitutes, and
recycling REE wastes.8 Among those approaches, this study
focuses on the recovery and recycling of end-of-life REE
products. When compared to REE mining processes, recycling
of REEs from postconsumer products provides significant
environmental benefits with regard to air emissions, ground-
water contamination, soil acidification, eutrophication, and
climate change.2
The recoverable REEs from end-of-life products are (1)
neodymium (Nd), dysprosium (Dy), and praseodymium (Pr)
from NdFeB permanent magnets used in automobiles, mobile
phones, hard disk drives, computers, tablets, electric motors,
and hybrid electric vehicles; (2) europium (Eu), terbium (Tb),
and yttrium (Y) from phosphors in fluorescent lamps, LEDs,
LCD backlights, and plasma screens; and (3) lanthanum (La),
cerium (Ce), Nd, and Pr from nickel metal hydride batteries in
rechargeable batteries, and hybrid electric vehicle batteries.9
Even though there are a variety of end-of-life products available
for REE recovery, the actual REE recovery is currently
estimated to be less than 1% due to low efficiencies and
limitations in recycling processes.10 Therefore, it is pivotal to
develop and improve the effective REE recycling process in
order to widen the reuse of REE-containing end-of-life
products.
Even though commercial REE recycling is presently very
limited, the REEs can be recovered through several processing
technologies such as hydrometallurgy, pyrometallurgy, and gas-
Special Issue: Critical Materials Recovery from Solutions and Wastes
Received: March 25, 2015
Revised: June 22, 2015
Accepted: June 24, 2015
Published: June 24, 2015

© 2015 American Chemical Society 9452 DOI: 10.1021/acs.est.5b01306

Environ. Sci. Technol. 2015, 49, 9452−9459
Environmental Science & Technology
phase extraction. Hydrometallurgy uses strong acid to dissolve
REE-containing end-of-life products and then uses basic
solutions to selectively precipitate the REEs of interest. This
process includes solvent extraction, leaching, and precipitation.
However, this process requires high chemical usage and suffers
from generation of large amounts of chemical waste and low
selectivity due to coextraction of non-REEs.9 The pyrometallur-
gical process utilizes high temperatures to chemically convert
feed materials into the valuable REEs. This process requires
fewer processing steps than the hydrometallurgical route, but it
requires larger energy input and generates larger amounts of
solid waste.9,11 The REE recovery by gas phase extraction route
is based on volatility differences, involving chlorination and
carbochlorination, but corrosive aluminum chloride and
hydrogen chloride gas generated from this process pose serious
environmental and safety hazards.12,13
Membrane assisted solvent extraction (MSX) can provide
another alternative to recover REEs, eliminating the disadvan-
tages of traditional equilibrium-based solvent extraction
processes such as loading, flooding, and third phase
formation.14,15 In the continuous operation mode, separation
in MSX is enhanced under nonequilibrium conditions due to
the maintenance of high driving forces over extended periods of
time compared to equilibrium limited conventional solvent
extraction. While the solvent extraction process carries out
extraction and stripping in two separate steps, MSX combines
both processes in a single step, circulating the feed and strip
solutions continuously without dispersion of different
phases.16,17 Utilizing hollow fiber membrane modules in the
MSX system provides high contact surface area per unit volume
to achieve a high REE extraction rate. In the MSX system, an
organic phase consisting of extractant and organic solvent is
immobilized in the pores of hollow fiber membranes, and the
aqueous feed and strip solutions flow through the lumen and
shell side of hollow fiber modules, respectively, as shown in
Figure S1 (Supporting Information). The organic solvent is
immiscible with very low solubility in aqueous solution which
minimizes extractant and solvent losses.
Acidic extractants are widely used in current industrial
practice, but they suffer from relatively low REE selectivity due
to simultaneous coextraction of other cations such as Fe, Cu,
and Ni.18,19 On the contrary, neutral extractants such as
tetraoctyl diglycol amide (TODGA) and trialkyl phosphine
oxides (Cyanex 923) have shown the capability of selectively
extracting several lanthanides and actinides such as cerium,
europium, uranium, and cesium.20−22 Therefore, we have
utilized neutral extractants, TODGA and Cyanex 923 in this
work. They were evaluated to selectively extract REEs from
permanent magnets in the presence of non-REEs such as Fe, B
and other transition metals (Cu, Ni) used in the outer coating.
The distribution coefficient (D) is the ratio of REE
concentration in the organic phase to that in the aqueous
phase at equilibrium. D values of neodymium extracted by
TODGA and Cyanex 923 were first measured to determine
their relative efficiencies prior to incorporating them in the
membrane supports. The effects of the concentration and flow
rate of the feed solution, membrane configuration, and acid
composition on REE extraction were then systematically
investigated using commercial NdFeB magnets. The MSX
system was also utilized to extract REEs from industrial scrap
magnets. The REEs in the scrap magnets were recovered from
the strip solution in the MSX system by precipitating, filtration,
drying, and annealing steps. The resulting REE oxides were
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characterized by X-ray diffraction (XRD), energy-dispersive X-
ray spectroscopy (EDX), and inductively coupled plasma-
optical emission spectroscopy (ICP-OES).
■ EXPERIMENTAL SECTION
The distribution coefficient of neodymium was determined by
mixing organic phase with the REE-containing aqueous
solution for 2 h, followed by separating aqueous phase from
organic phase. The organic phase is composed of extractants
(TODGA (Marshallton Research) or Cyanex 923 (CYTEC
Industries Inc.)), tributyl phosphate (TBP, Stauffer Chemical
Company) as another extractant, and Isopar L (Isoparaffin,
ExxonMobil Chemical) as solvent. The aqueous phase was
prepared by dissolving permanent magnets, neodymium(Nd)-
iron(Fe)-boron(B) magnets (K&J Magnetics, grade D42) in
1−6 M HNO3 and 3−6 M HCl. The concentration of REEs in
the organic phase was back-calculated from the REE
concentration in the aqueous phase measured by ICP-OES
(IRIS Intrepid II XSP, Thermo Electron Corporation).
Hydrophobic membranes are desirable for the extraction of
REEs because hydrophobicity prevents wetting of the
membrane by aqueous feed solution and also prevents the
displacement of organic phase immobilized in the pores into
the strip solution. For this reason, hydrophobic polypropylene
membrane modules (MicroModule, Membrana, area 100 cm2,
ID: 0.25 mm, number of hollow fibers: 700) were used as
membrane supports. The REE sources for the feed solution
were chosen from three different NdFeB magnets; commercial
NdFeB magnets from (1) K&J Magnetics (Grade D42) and
industrial scrap magnets from (2) Molycorp Magnequench
(Harrodsburg, KY) and (3) Daido Electronics Co. Ltd. (Japan).
The composition of the magnets is shown in Table S1
(Supporting Information). These magnets were dissolved in
concentrated nitric acid or hydrochloric acid for 24 h.
Using the commercial NdFeB magnets, the membrane
assisted solvent extraction was carried out with 2 L feed
solution containing approximately 1000 and 2000 ppm of Nd
and the strip solution of 0.23 or 0.5 L. The molar
concenstration of HNO3 in the feed solution was 6 M and
the strip solution was 0.2 M HNO3. The pores of hollow fibers
in the membrane modules were filled with organic phase
consisting of the TODGA, Isopar L, and TBP in the ratio of
3:4:3, respectively. The shell side of hollow fibers was supplied
with the aqueous strip solution, and the lumen side of the
hollow fibers was fed with the feed solution containing REEs.
Both the feed and strip solutions were simultaneously circulated
throughout the MSX system with peristaltic pumps. The feed
solution was thoroughly mixed with a mixer (Talboys,
TROEMNER, LLC) to maintain uniform concentration. The
pressure on the feed side was maintained at 15 psig and the
strip side was kept at atmospheric pressure. The flow rate of the
feed solution varied from 35 to 105 mL/min to investigate the
effect of flow rate on REE recovery. For ICP analysis, ∼5 mL
samples were collected from both feed and strip solutions over
the duration of the experiment. The effect of membrane
configuration on REE extraction was studied by connecting 8-
membrane modules in series and parallel (Figure S2,
Supporting Information). Experiments with 3 and 6 M
hydrochloric acid were also conducted to study the effect of
acid composition on REE extraction. 0.2 M HCl solution was
used as the strip on shell side of the module.
Upon the optimization of experimental conditions with the
commercial NdFeB magnets, the two industrial scrap magnets
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Figure 1. Distribution coefficient of Nd from NdFeB magnets (D42) with TODGA and Cyanex 923 in (a) HNO3 and (b) HCl.
Figure 2. (a) The elemental concentration of NdFeB magnets in the (a) feed and (b) strip solutions while running the 8-module system in parallel,
(c) the ratio of REEs in the strip to the feed and (d) REE extraction rate (feed: 6 M HNO3, ∼1000 ppm of Nd, strip: 0.2 M HNO3, 0.23 L).
procured from Molycorp Magnequench and Daido Electronics
were utilized to recover REEs with the MSX system. The
extracted REEs in the strip solution from those scrap magnets
were precipitated out with oxalic acid, followed by filtration,
drying at room temperature, and annealing at 750 °C for 2 h.
The resulting REE oxides were characterized by X-ray
diffraction (XRD), energy-dispersive X-ray spectroscopy
(EDX, HITACHI S-4800). The recovered REEs were
redissolved in nitric acids to evaluate the purity of REE oxides
with ICP-OES (IRIS Intrepid II XSP, Thermo Electron
Corporation).
■ RESULTS AND DISCUSSION
The critical requirement in the extraction of REEs with the
MSX system is the incorporation of a selective extractant in
organic phase by impregnation in the pores of hollow fiber
support. We have evaluated two different neutral extractants,
TODGA and Cyanex 923. These were first evaluated to
determine the distribution coefficient of neodymium at various
acid concentrations. Although the distribution coefficient is a
function of temperature, pH, metal ion concentration,
extractant and solvent concentration, the effect of molar acid
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concentration on the distribution coefficient was only
considered in this study.23 Figure 1 shows distribution
coefficients of neodymium from NdFeB magnets (D42)
obtained with TODGA and Cyanex 923 in aqueous HNO3
and HCl solutions. As shown in Figure 1, distribution
coefficient of Nd extracted by TODGA was substantially
greater than that obtained with Cyanex 923 at several different
representative acid concentrations. High D values with
TODGA can be attributed to strong oxygen donor atoms in
TODGA, whereas low D values on Cyanex 923 are likely due to
the low adsorption ability of Cyanex 923 for the REEs.24,25 This
result confirms that TODGA is more suitable than Cyanex 923
for extraction of REEs from NdFeB magnets. Thus, TODGA
was chosen as the preferred extractant in the MSX system to
extract REEs from the permanent magnets in this research.
There are several process variables that can have an effect on
REE recovery in the MSX system, such as REE concentration,
molar concentration of acid, and membrane area. These
variables were investigated in a prior study.26 The molar
concentration of HNO3 in the feed and strip was chosen as 6 M
and 0.2 M, respectively. This was based on favorable values of
distribution coefficient at high acid concentration. The 8-
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Figure 3. Elemental concentration of NdFeB magnets in the (a) feed and (b) strip solutions, and (c) the ratio of REEs in the strip to the feed and
(d) REE extraction rate while running the 8-module system in series for 96 h (feed: 6 M HNO3, 2L; strip: 0.2 M HNO3, 0.5 L).
membrane module system was used to extract REEs. Another
experimental variable that can impact REE extraction is the feed
flow rate. The flow rate of the feed side in the 8-membrane
modules was varied from 35 to 105 mL/min, while keeping all
other experimental conditions constant. Figure S3 (Supporting
Information) shows the effect of flow rate of the feed solution
on REE recovery in the MSX system. As can be seen in
Supporting Information Figure S3, the ratio of REE
concentration in the strip to the feed only slightly decreased
as the feed flow rate increased, suggesting that the extraction
rate is not significantly impacted by the feed flow rate.
Therefore, a feed flow rate of 35 mL/min was selected in the
MSX system for the rest of this study.
The 8-membrane modules were connected in parallel to
enable the feed solution to be evenly distributed into each
membrane module, as shown in the schematic of Figure S2 (a)
(Supporting Information). Figure 2 shows the elemental
composition of (a) the feed (commercial NdFeB magnets
(K&J Magnetics, grade D42)) and (b) the strip solutions while
operating the 8-membrane module system for 55 h. The molar
concentration of nitric acid in the feed and the strip was 6 M
and 0.2 M, respectively. At around 24 h from the start, Nd
concentration in the strip was about 900 ppm and then
decreased slowly as operating time increased, whereas Pr
concentration kept increasing over 55 h. As shown in Figure 2
(c), the Nd concentration ratio in the strip to the feed was >1.0
after a run time of 20 h, and the concentration of Pr in the strip
increased up to 95% of the initial Pr concentration in the feed.
Figure 2 (d) shows extraction rates of Nd and Pr while running
the 8-membrane module system. In both cases, the REE
extraction rates rapidly declined at the beginning of the run
even at high REE concentration, indicating that REE extraction
may be significantly limited by the amount of extractants
available in the pores of hollow fibers. Typically, MSX system
does not experience any fouling issue often caused by the
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accumulation of particulate matter. However, in order to
maintain the desired concentration of extractants in the
membrane pores, the organic phase might need to be
supplemented periodically to achieve long-term stability
(>1000 h). The expected frequency of replenishing extractants
would be once every couple of months.
Figures S4(a) and (b) (Supporting Information) show the
elemental concentration of NdFeB magnets in the feed and
strip solutions when the feed concentration was doubled from
∼1000 ppm to ∼2000 ppm of Nd, while maintaining all other
conditions as shown in Figure 2. It can be seen from
Supporting Information Figure S4(b) that Nd, Dy and Pr
were selectively recovered with no coextraction of non-REEs
such as Fe and B. The other non-REEs such as Cu and Ni used
in the outer coating of the magnets were also undetectable by
ICP-OES. This high selectivity of REEs over non-REEs could
be attributed to the nonequilibrium separation process of
membrane assisted solvent extraction. In this case, REEs are
continuously extracted at high driving forces without
approaching equilibrium where coextraction can occur.
However, as shown in Figure S4(c) (Supporting Information),
the recovery of Nd and Pr with higher concentration of feed
solution (∼2000 ppm of Nd) decreased by about 50%,
indicating that REE extraction through the membrane is not
limited by concentration gradient, but by the amount of
available extractants in the hollow fiber pores. Figure S5
(Supporting Information) shows the extraction results while
running the 8-membrane module system for 96 h with
increased strip volume (0.5 L). All other conditions were
identical to those reported for Supporting Information Figure
S4. The behavior of the Nd, Pr, Dy recovery over time with the
higher strip volume was very similar to that of REEs with the
strip volume of 0.23 L (see Figure S4, Supporting Information).
A small increase in the extraction rate was observed with the
higher strip volume in Supporting Information Figure S5(d)
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Figure 4. Elemental concentration of NdFeB magnets in the (a) feed and (b) strip solutions, and (c) the ratio of REEs in the strip to the feed and
(d) REE extraction rate while running the 8-module system in series for 96 h (feed: 6 M HCl, 2L; strip: 0.2 M HCl, 0.5 L).

Figure 5. Elemental concentration of scrap magnets (Molycorp Magnequench) in the (a) feed and (b) strip solutions, and (c) the ratio of REEs in
the strip to the feed and (d) REE extraction rate while running the 8-module system in series for 100 h (feed: 6 M HNO3, 2L; strip: 0.2 M HNO3,
0.5 L).

compared to the lower strip volume (0.23 L) in Supporting
Information Figure S4(d).
In order to evaluate the influence of membrane module
configuration on REE extraction, the 8-membrane modules
were connected in series as shown in Supporting Information
Figure S2(b). All other extraction conditions were identical to
those reported in Supporting Information Figure S5. Figure
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3(a) and (b) show the concentration of NdFeB magnet
elements in the (a) feed and (b) strip solutions while running
the 8-module system in series for 96 h. The ratio of REE
concentrations in the strip to the feed solution and REE
extraction rates with the 8-modules in series configuration are
shown in Figure 3(c) and (d). The Nd and Pr recoveries with
the 8-membrane modules connected in series were about 20%
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Figure 6. SEM-EDX analysis of REEs recovered from Magnequench scrap magnets by membrane assisted solvent extraction.
higher than that with the 8- modules in parallel. In addition, the
extraction rate for the first 24 h run time was almost double to
that observed for the 8-modules connected in parallel. These
results confirm that the membrane configuration in series
shows better REE extraction performance than the config-
uration where modules are connected in parallel.
The use of hydrochloric acid instead of nitric acid for REE
extraction was evaluated in the MSX system as it is generally
the preferred acid in many traditional precipitation and
extraction technologies for REE recovery. Figure 4(a) and
(b) show the elemental concentration in the feed and strip
solutions while operating the 8-membrane module system
connected in series with 6 M HCl in the feed and 0.2 M HCl in
the strip. Figure 4(c) and (d) show the ratio of REE
concentration in the strip to the feed and REE extraction
rate, respectively. As shown in Figure 4(b) and (c), significant
amounts of Fe and B were coextracted with REEs into the strip
solution. The ratio of Fe concentration in the strip to the feed
in 48 h was about 1.6 which is much higher than that of Nd and
Pr in Figure 4(c). The coextraction of REEs could be attributed
to the formation of tetrachloroanions of non-REEs in the
presence of HCl as described below.27 This mechanism is not
applicable as nitrate anions are not formed that can be
coextracted when nitric acid is used for REE extraction.
2Fe + 6HCl → 2FeCl3 + 3H 2
TODGA + FeCl3 + HCl ↔ TODGA·H+·FeCl−4
3TODGA·H+·FeCl−4 + Nd3 + + 3Cl−
↔ [(TODGA)3 Nd]3 + (FeCl−4 )3 + 3HCl
Figure S6(a) and (b) (Supporting Information) show the
elemental concentration in the feed and strip when 3 M HCl
was used in the feed solution with the 8-membrane modules to
extract REEs from permanent Nd-based magnets. As shown in
Figure S6(b) and (c) (Supporting Information), even though
the ratio of Nd and Pr in the strip to the feed was significantly
higher compared to that with 6 M HCl in the feed, the
coextraction of Fe was still observed resulting in high
concentration of Fe in the strip, unlike when HNO3 was
used in the aqueous solutions. As can be seen from these
results, although HCl is widely used in current industrial
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practice, it would be more desirable to use HNO3 in the MSX
system to recover high purity REEs from the Nd-based
magnets, based on the results obtained in this study. However,
utilizing ionic liquids, such as trihexyl(tetradecyl)phosphonium
chloride, which has shown high distribution ratio for iron over
REEs in HCl, may be an option to post-treat the HCl based
strip solution to recover pure REEs.28
Upon the optimization of the MSX system performance with
commercial NdFeB magnets, the REE recovery from industrial
scrap magnets with membrane assisted solvent extraction was
investigated. The end-of-life scrap magnets were procured from
Molycorp Magnequench, which contains about 30 wt % REEs
(see Supporting Information Table S1). Figure 5 (a) shows the
elemental concentration of the Magnequench scrap magnet
dissolved in 6 M HNO3. The elemental concentrations in the
strip solution and the ratio of REEs in the strip to the feed
while operating the 8-membrane module system are shown in
Figure 5(b) and (c), respectively. The results show that only
REEs such as Nd, Pr, and Dy were selectively extracted from
the scrap magnets into the strip solution with the MSX system,
without any coextraction of non-REEs such as Fe and B. Figure
S7 (Supporting Information) shows the REE extraction results
obtained with the industrial scrap magnets procured from
Daido Electronics. As shown in Supporting Information Figure
S7(b) and (c), only REEs were selectively recovered from
Daido Electronics scrap magnets with the MSX system, and
there was no coextraction of non-REEs in the strip solution
over the 120 h run. These results clearly demonstrate that
membrane assisted solvent extraction is capable of selectively
recovering REEs from industrial scrap magnets.
The REEs extracted into the strip solution from the scrap
magnets were then precipitated with oxalic acid, followed by
filtration, drying, and annealing steps. Figure S8 (Supporting
Information) shows the XRD patterns of resulting REE oxides
recovered from the scrap magnets procured from Molycorp
Magnequench. The majority of peaks shown in the XRD
analysis correspond to the peaks for REE oxides such as Nd2O3
(JCPDS 21−0579) and PrO1.83 (JCPDS 06−0329), indicating
that REE oxides were successfully recovered from industrial
scrap magnets via the MSX system. The purity of recovered
REEs was examined by SEM-EDX analysis, as shown in Figure
6. There is no indication of the presence of iron in the
recovered REE oxides based on the EDX analysis. In addition,
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when the recovered REE oxides were analyzed by the ICP-OES
after being redissolved in the nitric acid solution, only REEs
such as Nd, Pr, and Dy were detected with nondetectable
concentration of non-REEs in the sample. The XRD patterns
for recovered REE oxides from Daido scrap magnets are shown
in Figure S9 (Supporting Information) and their SEM-EDX
analysis are presented in Figure S10 (Supporting Information).
Supporting Information Figures S9 and S10 also demonstrate
that nearly pure REEs were successfully recovered from
different scrap magnets with the MSX system. These results
confirm that the membrane assisted solvent extraction
technology is capable of selectively extracting REEs from
industrial scrap magnets. This is the first comprehensive
research showing the successful demonstration of applying
membrane assisted solvent extraction to REE recovery from
Nd-based scrap magnets.
In comparison, the traditional approaches of utilizing
precipitation result in low recovery and the recovered REE
may contain significant levels of non-REEs such as Fe and
Co.29,30 It is also difficult to dispose of hazardous wastes. The
use of equilibrium-limited solvent extraction would require a
large number of stages to produce highly pure REEs suitable for
reuse. The significant possibility for solvent and extractant
losses due to solubility in highly acidic solutions may also
hinder its application for REE recycling and reuse. The recovery
of REEs in highly pure form is essential to potentially enable its
direct use in REE recycling. There would be a huge cost
advantage if the REE oxides are recovered in nearly pure form
as it would eliminate the need for further purification and
processing prior to reuse. Thus, the application of membrane
assisted solvent extraction to the REE recovery from the scrap
magnets would result in a more environmentally friendly and
cost-effective process compared to the conventional routes such
as precipitation and solvent extraction.
■
ASSOCIATED CONTENT
*
S Supporting Information
Table S1, Figures S1−S10.The Supporting Information is
available free of charge on the ACS Publications website at
DOI: 10.1021/acs.est.5b01306.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: (865)574-6025; e-mail: bhaverr@ornl.gov.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research/work is supported by the Critical Materials
Institute, an Energy Innovation Hub funded by the U.S.
Department of Energy, Office of Energy Efficiency and
Renewable Energy, Advanced Manufacturing Office. We
thank Dr. Huseyin Ucar at ORNL for his assistance in XRD
analysis.
■
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9459 DOI: 10.1021/acs.est.5b01306

Environ. Sci. Technol. 2015, 49, 9452−9459