Journal of Cleaner Production 218 (2019) 425e437

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Recovery of critical materials from mine tailings: A comparative study

of the solvent extraction of rare earths using acidic, solvating and
mixed extractant systems
Cristian Tunsu a, *, Yannick Menard b, Dag Øistein Eriksen c, Christian Ekberg a,
Martina Petranikova a
a €teborg,
Chalmers University of Technology, Department of Chemistry and Chemical Engineering, Nuclear Chemistry and Industrial Materials Recycling, Go
Sweden
b
French Geological Survey, Water, Environment and Ecotechnologies Division, Orl
eans, France
c
Primus.inter.pares AS, Oslo, Norway

a r t i c l e i n f o a b s t r a c t

Article history: Our society heavily depends on the availability of raw materials. Technology metals such as rare earth
Received 10 August 2018 elements (REEs) are vital in many applications. Because their virgin mining and production is constrained
Received in revised form by a multitude of factors, future exploitation of secondary sources is strongly considered. Tailings from
25 January 2019
past and present mining activities are important sources of REEs and other critical raw materials, e.g.,
Accepted 28 January 2019
tungsten and phosphate. The possibility of processing such tailings was thoroughly investigated in the
Available online 29 January 2019
ENVIREE European Project (2015e2018). In this paper, we assess the use of solvent extraction to recover
REEs from tailings originating from New Kankberg (Sweden) and Covas (Portugal). Extraction of REEs
Keywords:
Tailings
from common mineral acid solutions was carried out using solvating (Cyanex 923 and TODGA) and acidic
Urban mining extractants (DEHPA and Cyanex 572). Extraction was studied in the presence of high amounts of phos-
Critical metals phate, iron and copper in solution. This was to identify bottlenecks in the separation process and ways to
Rare earth elements mitigate them. While copper and phosphate didn't pose significant issues, iron was co-extracted with the
Solvent extraction REEs in several systems, e.g., DEHPA e sulfuric acid. Co-extraction was reduced by using a blended
DEHPA e Cyanex 923 organic phase. At the same time, the extraction efficiency of REEs improved.
Control of the contact time between the aqueous and organic phase, and selective stripping were also
used to effectively mitigate the extraction of iron.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction meet the Paris Agreement requirements, production of rechargeable

Excessive exploitation of Earth's natural deposits to extract raw
materials is a major concern. The speed at which deposits are
depleted has accelerated with the start of the industrial era. Pres-
ently, there is a high demand for specific raw materials, notably
speciality metals for sustainable applications and hi-tech
(European Commission, 2011; US Department of Energy, 2011).
Rare earth elements (REEs) are needed in, among others,
rechargeable batteries, electric transportation, wind turbines and
low-energy lighting. This makes them highly desirable for the
transition towards a low-carbon economy. It was estimated that, to
* Corresponding author.
E-mail address: tunsu@chalmers.se (C. Tunsu).
batteries will significantly increase the already high demand for
lithium, cobalt, nickel and REEs (Hodgkinson and Smith, 2018). The
preponderant production in China, tight dependency of industri-
alized countries on imports, geo-political factors, high specificity
and wide variety of applications led to the critical status of REEs (US
Department of Energy, 2011; European Commission, 2017).
There is a very tight connection between REEs prices, supply and
demand, and this was most evident in the beginning of the current
decade. The so-called rare earth crisis, fuelled by geo-political fac-
tors and by the export quotas imposed by China, greatly affected
the price of all REEs. Since the long-term growth of numerous in-
dustries depends on the ability to secure stable and diverse sources
of speciality metals (Hatch, 2012), this placed focus on finding
alternative sources, primary and secondary sources being both
considered. Previous mines such as Mountain Pass re-opened

https://doi.org/10.1016/j.jclepro.2019.01.312
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
426 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
briefly, and a significant amount of research was aimed at recovery
of REEs from end-of-life electronics and other secondary streams
(urban mining) (Binnemans et al., 2013a, 2013b; Ferron and Henry,
2015; Tunsu et al., 2015; Xie et al., 2014). In the aftermath of the
crisis, the prices of all REEs fell significantly. These events high-
lighted the cyclic nature of supply and demand for speciality metals
with extremely localized and controlled production. Moreover, it
articulated that society cannot solely rely on virgin mining and, in
the context of a circular economy (Kirchherr et al., 2017), effective
recycling and processing of secondary sources is a must. Unless
recycling rates increase dramatically and population growth is
curbed, many resources can become scarce this century
(Ragnarsdo ttir et al., 2012; Sverdrup and Ragnarsdo ttir, 2014a). As
the World's population increases, there is need to improve the ef-
ficiencies and yields in the recycling and production chains to
reduce net consumption per capita and conserve resources
(Sverdrup and Ragnarsdo ttir, 2014b).
Virgin production of REEs is associated with numerous envi-
ronmental drawbacks. Local ecosystems are negatively affected by
the large amounts of secondary wastes generated during mining of
REEs, including waste gas containing dust concentrate, hydrofluoric
acid, sulphur dioxide and sulphuric acid, acidic wastewater and
radioactive residues (Hurst, 2010). This made the argument for
urban mining stronger, pointing out notable advantages: the
presence of desirable metals in a smaller volume, in more
concentrated form, less mobilization of harmful compounds,
reduction of landfill areas and land reclamation for existing land-
fills. In addition, the contribution of secondary sources to the
available supply of REEs will continue to increase in the future
(Guyonnet et al., 2015) and can be a responsible sourcing strategy
for critical metals (Wall et al., 2017). End-of-life electronics,
metallurgical slags, phosphogypsum, and mine tailings have been
acknowledged as secondary sources of REEs and other valuable
compounds (Binnemans et al., 2013a, 2013b; Ferron and Henry,
2015; Tunsu et al., 2015; Mueller et al., 2015; Innocenzi et al.,
2014; Jha et al., 2016; Tan et al., 2015). Investigations performed
in the Baltic Region have shown that fine-grained fractions of
excavated waste, including clay and colloidal matter, contain sig-
nificant amounts of potentially valuable metals, including REEs
(Burlakovs et al., 2018). Despite efforts, the current recycling rates
of REEs remain extremely low, below 1% (European Commission,
2017; UN Environment Programme, 2011), partly due to the sig-
nificant aforementioned price decreases and lack of governmental
policies. In recent years, there has been extensive research on the
recovery of REEs from permanent magnets, nickel-metal hydride
batteries and fluorescent lamps. In contrast, detailed studies of the
recovery of REEs from mine tailings are lacking. While the REEs
content in tailings can be lower than in electronics, their processing
may be worthwhile if environmental benefits are also considered
or imposed, e.g., remediation of mining sites and land reclamation.
Governmental regulations can play a pivotal role in closing material
loops (Machacek et al., 2017). In addition, exploitation of tailings
does not depend on an effective collection-transportation-sorting
scheme, which is required for end-of-life products containing
REEs; the recyclable material is simply available on site.
The present study focuses on aspects related to the hydromet-
allurgical recovery of REEs found in tailings from past and present
mining operations in Europe, an important topic scarcely covered in
literature. This was investigated in the ENVIREE Project
(2015e2018), which screened various locations across Europe and
South Africa to find secondary sources of REEs and assess the po-
tential to recover contained strategic metals. Here, we look at
tailings from two sites, New Kankberg (Sweden) and Covas
(Portugal). These were selected on the basis of material availability,
amount, mineral composition, REE content and former processing
techniques that produced the tailings. Aspects about the miner-
alogy and beneficiation of samples are discussed but emphasis is
placed on the solvent extraction of REEs in the presence of high
amounts of interfering anions and cations, phosphate, iron and
copper, which are encountered in such streams. The study thor-
oughly compares extraction of trace (mg/L) and g/L amounts of
REEs from common mineral acid solutions (nitric, hydrochloric and
sulfuric) with various solvating (Cyanex 923 and tetraoctyl digylcol
amide) and acidic extractants (bis-(2-ethylhexyl)phosphoric acid
and Cyanex 572). We report on the use of mixed organic phases
containing two or more commercial extractants (bis-(2-ethylhexyl)
phosphoric acid Cyanex 923 and/or methyltrioctylammonium
chloride) as method to minimize co-extraction of iron from com-
plex mixtures and improve extraction of trace REEs.
2. Background
Past processing methods for REE ores were not very efficient
(Binnemans et al., 2013b). In addition, targeted mining of non-REEs
ignored REEs, even if present in the ore. This has led to dumping
and accumulation of significant amounts of REE-containing tailings
close to mines and processing plants. In the ENVIREE Project, a high
number of such sites were initially identified in the Czech Republic,
South Africa, Sweden, Poland and Portugal. Tailings from New
Krankberg (Sweden) and Covas (Portugal) contain REEs but also
other materials presently considered critical in the European Union,
e.g., tungsten and phosphate.
The New Kankberg tailings originate from gold and tellurium
production. These are deposited together with tailings from other
sulphide ores in a pond which is around 5 km wide and 10 km long.
Roughly 700 million tons tailings has so far been stored and around
1300 million tons more is planned to be stored until 2045. The main
mineralogy includes quartz, muscovite, kaolinite and K-feldspar.
This material has the highest concentration of REEs among the
other European tailings investigated in this project. Mineralogic
data revealed the presence of phosphates as monazite and apatite,
and minor amounts of xenotime and berlinite. Most of the REEs is
present in monazite, thus light REEs predominate (lanthanum,
cerium and neodymium). QEMSCAN analysis on representative
samples showed that monazite is for 40% associated with other
minerals and has a free surface that totals 55%. Phosphate and REEs
are present in all size class of the tailings; a slight increase in
content was observed in the classes below 40 mm. The Covas tail-
ings originate from past underground mining of tungsten (scheelite
and minor wolframite), which occurred for 30 years after the sec-
ond half of the twentieth century. The mineralogy also includes
muscovite, quartz, kaolinite, chlinochlore, K-feldspar and some
heavy magnetic minerals (hematite, chalcopyrite, ferberite and
arsenopyrite). The deposit consists of 1e3 m thick lenticular skarn
levels hosted by schists. The skarn levels are constituted essentially
by zones of massif sulphides with associated wolframite, scheelite
and ferberite pseudomorphs after scheelite. Additional information
Fig. 1. Bench-scale beneficiation of New Kankberg tailings (a) and Covas tailings (b).
 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
about the REEs content and bench-scale beneficiation of the tailings
are given in Fig. 1 and are further discussed in section 4.1.
Due to this mineralogy, hydrometallurgy is required to reclaim
the REEs. Pyrometallurgical processing in electric arc furnaces or
non-ferrous smelters will divert the REEs to the slag phase, hin-
dering their recovery (Frohlich et al., 2017). Typical hydrometal-
lurgical steps include leaching, followed by separation of metal ions
in the resulting leachate using precipitation, solvent extraction or a
combination of these. For Covas tailings, selective leaching of
tungsten and REEs is possible. Tungsten in scheelite and wolframite
is not easily dissolved with acidic solutions. Leaching of tungsten
can be done with base solutions, in which the REEs will dissolve. To
leach the REEs, acidic conditions are needed. Alkaline cracking and
acid baking can be used to modify the mineralogy and facilitate
easier dissolution of REEs in weak acidic solutions; such processes
have recently been reviewed (Sadri et al., 2017). For solutions
containing two or more REEs, precipitation will give a mixed
product due to the similar chemical behaviour of these elements.
This is not desirable if individual separation is wanted, or if
concentrated impurities in solution can precipitate alongside REEs
(low product purity). Solvent extraction allows for the recovery of
individual REEs with high purities from chemically-complex feeds.
Separation involves the transfer of metal ions from the aqueous
leachate to an immiscible organic phase, which contains one or
more selective extractants (Nash, 1999). Individual separation is
possible due to the small differences in ionic radii (the lanthanide
contraction), which affects the strength of cation-anion, ion-dipole
and ion-induced dipole interactions of REE ions. Heavier REEs
create stronger complexes than lighter ones, facilitating their sep-
aration. The metals extracted are recovered from the organic phase
using a similar process, called stripping or back-extraction.
Amines, e.g., Aliquat 336 and Alamine 336, are the most
promising extractants for separation of tungsten from alkaline
media (Nguyen and Lee, 2016). For REEs, a variety of solvent
extraction reagents is available. Extensive research on the separa-
tion of REEs has been performed in the nuclear field, starting with
the second half of the last decade. This aimed at separating f-block
elements from other constituents in spent nuclear fuel (group
actinide-lanthanide extraction), and at separating f-block REEs
from actinides (Nash, 1993, 1999; Nash and Jensen, 2001; Nilsson
and Nash, 2007; Lumetta et al., 2014). Research was also carried
out for non-nuclear applications and, to date, various compounds
have been suggested for individual or group separation of REEs.
Examples are: bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex
272) (Swain and Otu, 2011), Cyanex 925 (Li et al., 2007), Cyanex 923
(Gupta et al., 2003), Cyanex 572 (Wang et al., 2015), bis-(2-
ethylhexyl)phosphoric acid (DEHPA) and 2-ethylhexylphosphonic
acid mono-2-ethylhexyl ester (HEHEHP) (Morais and Ciminelli,
2004; Xu et al., 1992), tetraoctyl digylcol amide (TODGA)
(Apichaibukol et al., 2004; Narbutt et al., 2015) and multidentate
diamides (Narita et al., 2004a, 2004b), polyamides bearing tetra-
butylmalonamide functional groups (Tyumentsev et al., 2016) and
various ionic liquid systems (Rout and Binnemans, 2014; Rout et al.,
2014; Sun and Waters, 2014; Yang et al., 2012). In recent years,
several reviews on the separation of REEs have been published
(Binnemans et al., 2013a, 2013b; Ferron and Henry, 2015; Tunsu
et al., 2015; Xie et al., 2014; Innocenzi et al., 2014; Jha et al., 2016;
Tan et al., 2015; Kolarik, 2012; Kubota et al., 2012; Yoon et al.,
2016). These discuss the mechanisms of extraction and potential
applications for urban mining. For REEs, three type of extractants
are typically mentioned: solvating (Cyanex 923, TODGA, tributyl
phosphate), acidic (DEHPA, HEHEHP, Cyanex 272, Cyanex 572) and
ion-pair (Aliquat 336, Trihexyl(tetradecyl)phosphonium chloride
and other ionic liquids). Solvating extractants extract metal ions
according to Equation (1). The metal ions in the aqueous phase
427
(Mzþ) form complexes with the counter-ions present (X). The
remaining coordination sites are occupied by water. Due to their
water content, these complexes have very low distribution co-
efficients in, e.g., a hydrocarbon. In the presence of a solvating
extractant (B), the water molecules are replaced by extractant
molecules. More lipophilic complexes are formed, which are
extracted into the organic phase. Acidic extractants extract REE ions
according to Equation (2). Since protons are involved in the equi-
librium reaction, distribution is pH-dependent. Extraction of REEs
is favoured by increases in pH and the opposite process (stripping)
is favoured at high acidity. Most commonly, ion-pair extraction
involves an anion exchange mechanism between anionic metal
complexes and one or more large organic cations (Equation (3)).
Mzþ (aq) þ z X (aq) þbB (org) 4 MXzBb (org) (1)
REE3þ (aq) þ 3 (HA)2 (org) 4 REE(HA2)3 (org) þ 3 Hþ (aq) (2)
where (HA)2 is the dimer form of the extractant.
MLx
n (aq) þ x QL (org) 4 QxMLn (org) þ x L (aq) (3)
Consensus is that acidic extractants such as DEHPA and HEHEHP
are the industrial standard for individual REEs separation. They
allow for separation factors of approximately 2.5 between adjacent
REEs, highest among traditional extractants. Separation of REEs
with high purity is, however, not an easy task. Tenths of counter-
current separation stages are sometimes needed to isolate adja-
cent members of the group. Chemically-complex streams pose
additional challenges. Their efficient processing can be reagent-
intensive and can generate significant amounts of secondary
wastes. This is especially the case for selective extraction of trace
REEs from solutions with high contents of interfering species. Iron,
a common constituent in ores and tailings, is problematic due to its
high extractability by many of the aforementioned conventional
reagents, notably DEHPA, Cyanex 923 and Cyanex 272. Tailoring
more selective extraction processes is, therefore, very important in
the extractive metallurgy of REEs, especially for low-grade feeds. In
this paper, we look at the extraction of iron, copper, phosphate and
REEs from common mineral acids, using acidic and solvating re-
agents. We propose an extraction process with mixed conventional
acidic and solvating reagents (DEHPA and Cyanex 923), coupled
with selective stripping. This minimizes co-extraction of iron from
solutions with low amounts of REEs and significantly higher iron
and copper content, while enhancing distribution of REEs.
3. Experimental
3.1. Beneficiation of tailings
Two barrels of 250 L containing tailings from New Kankberg
were emptied in a stirred tank and homogenized. Bench-scale
beneficiation was carried out using phosphate flotation and mag-
netic separation. Flotation was done in a 2.5 L Denver flotation cell
in batches of approx. 1 kg. The stirring speed was 1500 rpm and the
solid concentration was 40%. Pulp conditioning included depres-
sant (water glass), collector (Resinoline BD2) and frother (poly-
propylene glycol). Operating parameters are given in Fig. 1.
Following flotation, the concentrate (a mix of phosphates, apatite
and monazite) was further enriched using magnetic separation
(apatite is non-magnetic while monazite is paramagnetic). This was
done in a BoxMag High Intensity Magnetic Separation batch cell
using tenths of grams of sample. Two stages, the first at magnetic
intensity of 4000 G followed by a scavenging step at 15000 G,
produced a concentrate enriched in REEs and phosphate.
428 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437

One ton of Covas tailings with particle size distribution between
0 and 30 mm was dried and screened (2 mm) to remove coarser
particles. The coarser particles were crushed to below 2 mm and
mixed with the sample after screening, followed by grinding to
below 100 mm. Multi gravimetric concentration followed by mag-
netic separation was used for beneficiation. A wet shaking table
with a deck surface area of 0.8 m2 was used. The feed was diluted
with water (25e30% w/w solid). The shaking pulse rate was 500
pulses/min and the stroke length 10 mm. Wet magnetic separation
followed. Rare earths were recovered at intensities of magnetic
field in the range 900e14 000 G.
3.2. Hydrometallurgical separation of REEs
1 min for Cyanex 923, 45 min for TODGA, and 30 min for DEHPA
and Cyanex 572. After mixing, the vials were centrifuged to assure
complete phase separation. Extraction with DEHPA and Cyanex 572
was also carried out at higher pH. For this, the pH of the aqueous
feeds was increased with sodium hydroxide. Stripping of Cyanex
923 organic phases after extraction was done with 1.6 mol/L hy-
drochloric acid and 4 mol/L nitric acid solutions, respectively.
Mass balance was used to calculate the distribution ratios (D)
and percentage extracted (%E), according to Equations (4) and (5),
respectively.
Ci  Cf
D¼ (4)
Cf

3.2.1. Feeds, screening of extractants and typical bench-scale
extraction procedure
Screening was first carried out to find suitable extractants to
separate REEs from model solutions also containing major impu-
rities found in acidic tailing leachates. Six aqueous feeds were
investigated, as follows (Table 1): i) nitric, hydrochloric and sulfuric
acid solutions meant to resemble Covas leachates (over 10 g/L iron
and copper as impurities, and about a hundred ppm REEs), and ii)
nitric, hydrochloric and sulfuric acid solutions meant to resemble
New Kankberg leachates (gram amounts of REEs, and 10 g/L
phosphate).
The feeds were prepared by dissolving appropriate metal com-
pounds into each acid: iron, copper and REE nitrates in nitric acid;
iron, copper and REE chlorides in hydrochloric acid; and iron sul-
fate, copper sulfate and REE oxides and sulfates in sulfuric acid. The
amounts of REEs in solution were selected assuming a solid-to-
liquid ratio of approx. 1:5 w/v during leaching of beneficiated
fractions and approx. 80% leaching efficiency. Sodium phosphate
was added in the New Kankberg feeds. The copper in the com-
pounds used was in oxidation state II. The REEs and iron were in
oxidation state III. The stock acid solutions used were of analytical
grade purity or higher. Pure water (MilliQ, Millipore, >18 MU/cm)
was used as diluent.
Cyanex 923 (93%, Cytec), TODGA (prepared in-house), DEHPA
(97%, Sigma-Aldrich) and Cyanex 572 (Cytec) were the extractants
screened. They were dissolved in kerosene with low aromatic
content (Solvent 70, Statoil) to obtain the following concentrations:
0.59 mol/L and 1.18 mol/L Cyanex 923, 0.1 mol/L TODGA, 1 mol/L
DEHPA and 1 mol/L Cyanex 572. All commercial organic com-
pounds were used as supplied, without further purification.
Bench-scale extraction was carried out in glass vials (3.5 mL,
46  13  0.8 mm) secured with lids. Phase mixing was achieved
using a thermostatic shaking machine set to 1500 vibrations per
minute (vpm), at 21 ± 1  C. Unless stated otherwise, the organ-
ic:aqueous (O:A) phase ratios were 1:1. The mixing times were:
Ci  Cf
%E ¼ 100 (5)
Ci
where Ci and Cf are the metal concentrations in the aqueous phase
before and after extraction, respectively.
Elemental quantification was carried out with Inductively
Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) (iCAP
6500, Thermo Fischer) and Inductively Coupled Plasma-Mass
Spectrometry (ICP-MS) (iCAP Q, Thermo Fischer).
3.2.2. Extraction with acidic extractants from covas sulphate model
solution
The influence of the aqueous pH and phase contact time was
further investigated for the Covas sulfate e 1 mol/L DEHPA system.
The model solution was partly neutralized with solid sodium hy-
droxide to produce feeds with similar metal content but different
pH, in the range 0.2e4. Extraction tests were done for 30 min using
the aforementioned procedure. A similar test was also carried out
with 1 mol/L Cyanex 572. The effect of time on the extraction with
1 M DEHPA was investigated using model solution with initial pH
1.65. Extraction was carried out in a similar manner using several
different phase contact times. To investigate stripping, aqueous
solution with initial pH 1.65 was manually shaken for 1 min with
1 mol/L DEHPA (O:A 1:1). After 7 min resting, the organic phase was
isolated. Organic aliquots were stripped with 0.5 mol/L citric acid,
and with hydrochloric and nitric acid solutions of various concen-
trations (1 mol/L, 2 mol/L, 4 mol/L and 6 mol/L, respectively).
Stripping was done using O:A ratios 1:1, for 30 min, at 1500 vpm
and 21  C.
3.2.2.1. Minimizing co-extraction of iron by blending DEHPA with
other extractants. Extraction of metal ions from Covas sulfate so-
lution was studied using DEHPA and several organic phases con-
sisting of DEHPA blended with Cyanex 923 and/or
methyltrioctylammonium chloride (Aliquat 336). Their

Table 1
Aqueous feeds investigated.

Ionic specie/others Sample type, acid media and metal content (mg/L)

Covas New Kankberg

HNO3 media HCl media H2SO4 media HNO3 media HCl media H2SO4 media
3þ
Ce 41 39 41 810 730 750
Nd3þ 23 21 22 480 400 470
La3þ 21 23 17 460 430 460
Dy3þ 6 5 6 100 90 105
Fe3þ 9980 9980 9000
Cu2þ 1010 9975 1000
(PO4)3- 9550 9080 9670
Acid (mol/L) 1 0.4 1 1 0.92 1
Measured pH 0 0.4 0 0.2 0.1 0.1
 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437 429

Table 2 a magnetic intensity of 4000 G. A scavenging step at 15000 G fol-

The DEHPA e Cyanex 923 organic phases tested with the Covas sulfuric acid model lowed. This led to a concentrate with 17.5% of the initial phosphate
feed.
content (monazite mainly) and 37.5% of the initial REEs. The
Extractant and concentration Volumetric composition (% vol.) phosphate content increased from 0.17% to 2.5%. The REE content
(mol/L) increased from 170 ppm to 5000 ppm for cerium,
DEHPA Cyanex 923 90 ppme2800 ppm for lanthanum and 70e2300 ppm for
0.5 0 15 %vol. DEHPA neodymium.
0.5 0.117 15 %vol. DEHPA, 5 %vol. Cyanex 923 In grinded Covas tailings, the REEs and tungsten were mainly
0.5 0.235 15 %vol. DEHPA, 10 %vol. Cyanex 923 found in fine particles, 63 mm and smaller. Flotation was not effi-
0.5 0.47 15 %vol. DEHPA, 20 %vol. Cyanex 923
cient to recover the REEs and phosphate, regardless of operating
0.5 0.705 15 %vol. DEHPA, 30 %vol. Cyanex 923
1 0 30 %vol. DEHPA conditions. This is mainly due to the presence of calcite (14%),
1 0.117 30 %vol. DEHPA, 5 %vol. Cyanex 923 which hindered the process. The presence of scheelite and
1 0.235 30 %vol. DEHPA, 10 %vol. Cyanex 923 wolframite, together with other heavy magnetic minerals (hema-
1 0.47 30 %vol. DEHPA, 20 %vol. Cyanex 923 tite, chalcopyrite, ferberite and arsenopyrite), suggest that a com-
1 0.705 30 %vol. DEHPA, 30 %vol. Cyanex 923
bination of gravity and magnetic separation can be used for
beneficiation. It was noted down that REEs followed hematite and
other iron oxides (ferberite) or sulfides (chalcopyrite and arseno-
composition is given in Fig. 10. Extraction was carried out from pyrite). Because these minerals and scheelite are heavy, they were
solution partly neutralized with solid sodium hydroxide to pH 2. easily recoverable using gravimetric techniques. The recovery
The extraction conditions were: O:A 1:1, 2.5 min contact time, 1500 yields obtained with gravity separation were high. Rare earths re-
vpm and 21  C. The DEHPA e Cyanex 923 organic system was covery exceeded 70%. For tungsten, recovery was 50%. The con-
further investigated with the phases in Table 2. Extraction was centration factor for REEs was 5.5 and for tungsten 2.5 (Fig. 1b). The
carried out from the aforementioned aqueous solution using O:A technique could be implemented on site, with very low CAPEX and
ratios 1:1, 1 min contact time, 1500 vpm and 21  C. A mixed 1 mol/L OPEX; the only requirements are water and power supply. Mag-
DEHPA and 0.235 mol/L Cyanex 923 solution in kerosene was netic separation allowed further concentration of REEs (8 times
further tested on an aqueous feed with lower pH (initial pH 1.2). more compared to the initial material) and tungsten (12.6 times
This was done using similar experimental conditions and at more). The final recovery of REEs was 55%. For tungsten, this was
different O:A ratios, in the range 1:4e4:1. 35%.

3.2.2.2. Extraction in mixer-settlers. A solution containing 1 mol/L
DEHPA and 0.235 mol/L Cyanex 923 in kerosene was used as
organic phase. 2 %vol. 1-nonanol was preventively added to this as
third phase inhibitor. A new batch of Covas sulfate model solution
was prepared, in which the concentration of dysprosium was
double compared to that in Table 1. The acidity was lower, as the
compounds were dissolved in approx. 0.1 mol/L sulfuric acid solu-
tion. Part of this feed was used as prepared (initial pH 1.19). The
other part was pre-neutralized to pH 1.95 using solid sodium hy-
droxide. This was done to assess extraction at slightly higher pH.
The two feeds were separately pumped in a mixer-settler counter-
current cascade with 5 extraction stages. The O:A ratio was 1:3 and
the mixing speed in each chamber was 1000 rpm. The flow rates for
the organic and aqueous solutions were 2 mL/min and 6 mL/min,
respectively. The aqueous phases in each settling chamber were
sampled after the system reached steady state. Their pH was
measured and their metal content was determined using ICP-MS.
Mass balance was used to estimate the percentages extracted
(Equation (2)).
4. Results and discussions
4.1. Beneficiation of tailings
Bench-scale beneficiation of New Kankberg tailings was carried
out using phosphate flotation and magnetic separation. A diagram
of the process, together with the recovery yields and concentra-
tions of REEs are presented in Fig. 1a.
Flotation consisted of one rougher step, two scavenging steps
and one to two washing steps. Phosphate recovery reached 70%,
with a concentration factor of 10. Rare earths recovery reached 50%,
with a concentration factor of 9. The concentrate containing a mix
of phosphates (apatite and monazite) was further enriched using
two-stage magnetic separation. This exploited the differences in
magnetism of apatite and monazite: monazite is paramagnetic
while apatite is non-magnetic. The first stage was carried out using
4.2. Separation of REEs from New Kankberg and Covas model
leachates
The above results show that iron and tungsten are major con-
stituents in Covas concentrates; for New Kankberg, phosphate is
concentrated during beneficiation. Tungsten was not regarded as
problematic since effective leaching of REEs requires acidic condi-
tions. Acid dissolution of tungsten from scheelite and wolframite is
expected to be low. Tungsten can be selectively dissolved using
basic solutions, then further recovered using solvent extraction
with amines (Nguyen and Lee, 2016). On the other hand, iron and
copper will be effectively leached from the iron oxides and sul-
phides by mineral acids.
The focus was to assess how extraction and separation of REEs is
influenced by the nature of the aqueous media (nitric, hydrochloric
or sulfuric acid) and by impurities. We chose simple model solu-
tions to have precise control over the composition of the aqueous
solutions, and the amount and nature of impurities, e.g., oxidation
state and counter-ions present. This facilitated an easier and better
understanding of the extraction chemistry, and allowed for good
comparison between the different extraction systems tested. For
Covas, the extraction behaviour of trace REEs was studied in the
presence of significantly higher amounts of iron and copper. For
New Kankberg, phosphate will be a major anionic impurity in so-
lution and may influence distribution of REEs. The model solutions
in Table 1 were investigated. A low aqueous pH was chosen to
assure the stability of the elemental ions in solution. All Covas so-
lutions were stable after storage for 3 months at ambient condi-
tions. The hydrochloric and nitric acid New Kankberg solutions
were also stable. Precipitation occurred in the New Kankberg sul-
furic acid solution after a few weeks. Addition of concentrated
sulfuric acid did not dissolve the pale pink precipitate formed.
Analysis of the solution after one month showed significant de-
creases of the cerium, neodymium and lanthanum concentrations.
The values were 20e25% of the initial concentrations in Table 1. The
concentrations of dysprosium and phosphorous were similar to
430 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437

their original values. Precipitation occurred due to formation of low

soluble double sulfate salts between light REEs and sodium, present
in solution from the addition of sodium phosphate (Equation (6)).

2 REE3þ (aq) þ 2 Naþ (aq) þ 4 SO2

4 (aq) þ n H2O (aq)/ REE2(-
SO4)3$Na2SO4$nH2O (s) (6)

It was possible to increase the pH of the Covas solutions above 2

without precipitation and the resulting solutions were stable in
time. For New Kankberg, precipitation become an issue above pH
0.5e1. This was most preeminent in sulfuric acid media due to
formation of double sulfate salts.

4.2.1. Screening of solvating extractants

Cyanex 923, a commercially available mixture of four tri-
alkylphosphine oxides (Dziwinski and Szymanowski, 1998), and
TODGA were screened. Cyanex 923 extracts iron but this is signif-
icantly slower compared to extraction of REEs. A past study (Tunsu
et al., 2014), using a different aqueous system, showed that
extraction of REEs from nitrated media reached equilibrium in less
than 1 min. Iron was extracted over much longer time, with lower
distribution ratios in the beginning. A short phase contact time can
achieve partial separation of REEs from iron. In addition, selective
stripping is possible. Based on these observations, extraction with
Cyanex 923 was done here for 1 min. Two Cyanex 923 solutions
were tested: 0.59 mol/L (approx. 25 %vol.) and 1.18 mol/L (50 %vol.).
The distribution ratios of elements are given in Fig. 2.
Satisfactory extraction of REEs was only achieved from nitric acid
media. Iron was not significantly extracted due to the short phase
contact time. Phosphate ions showed noticeable extraction from
hydrochloric and sulfuric acid but less from nitric acid. This may be
due to the ability of Cyanex 923 to extract protons (Alguacil and
Lopez, 1996; Ansari et al., 2004), according to Equation (7).
Competing effects between REEs and phosphate are likely respon-
sible for the lower extraction of the latter from nitric acid. It is
possible to extract phosphate with Cyanex 923, of importance as this
is currently a critical raw material (European Commission, 2017).

x Hþ (aq) þ x X (aq) þyB (org) 4 yB∙xHX (org) (7)

where X is an anion in solution (phosphate or other) and B the

extractant.
As expected, the distribution ratios of REEs increased with
increasing atomic number, a consequence of the lanthanide
contraction (Peppard et al., 1969). Extraction selectivity for indi-
vidual REEs was, however, not achieved. A large number of sepa-
ration/stripping stages will be needed to separate adjacent REEs
from each other. Increasing the extractant concentration led to
increased extraction, also expected, as the equilibrium in Equation
(1) is pushed towards formation of extractable complexes. Strip-
ping of Cyanex 923 after extraction from nitric acid media was
effectively carried out with acidic solutions (Fig. 3). Hydrochloric
acid can be used to selectively strip REEs from co-extracted iron, as
detailed in (Tunsu et al., 2014).
Similar to Cyanex 923, TODGA showed very good extraction of
REEs from nitric acid. Heavy REEs (dysprosium) were also extracted
from hydrochloric acid, notably from Covas model solution (Fig. 4).
Extraction from sulfuric acid was not satisfactory. A clear advantage
of TODGA is the extraction selectivity over iron, copper and phos- Fig. 2. Distribution ratios of elements with 0.59 mol/L and 1.18 mol/L Cyanex 923 in
kerosene. Extraction conditions: O:A 1:1, 1 min phase contact time at 1500 vpm, 21  C.
phorus, regardless of acid media. Calculations using mass balance for a single sample replicate. Distribution ratios
To conclude, extraction of REEs with solvating extractants was calculated to be below 0.01 or above 100 are reported as 0.01 and 100, respectively.
most effective from nitric acid. The REEs were well extracted even in Distribution ratios calculated to be between 0.01 and 0.05 are reported as 0.05.
the presence of over 9 g/L phosphate. Generally, extraction of REEs
from the acids tested decreased in the order: nitric acid, hydrochloric
acid, sulfuric acid. The last gave unsatisfactory extraction regardless
 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
Fig. 3. Distribution ratios for stripping of Cyanex 923 previously contacted with New
Kankberg and Covas nitric acid feeds (see Fig. 2). Stripping conditions: 1.6 mol/L hy-
drochloric acid or 4 mol/L nitric acid, O:A 1:1, 30 min phase contact time, 1500 vpm
and 21  C. Calculations using mass balance for a single sample replicate. Distribution
ratios calculated to be above 100 are reported as 100.
of feed. Extraction of acid is possible (Equation (7)). Cyanex 923 e
nitric acid complexes of the type 2:1, 1:1 and 1:2 can form,
depending on the initial extractant and acid concentrations (Ansari
et al., 2004). Extraction of acid leads to an increase in aqueous pH,
which can affect the stability of the system, e.g., the aforementioned
precipitation for New Kankberg sulfuric acid solution. This, however,
did not occur under the conditions tested here.
4.2.2. Screening of acidic extractants
Bis-2-ethylhexyl phosphoric acid (DEHPA) and Cyanex 572 were
screened. Two tests were carried out: one with the original aqueous
feeds and one at slightly higher pH, where these solutions were
partly neutralized with sodium hydroxide. The distribution ratios
with DEHPA are presented in Fig. 5.
Dysprosium was effectively extracted and could be separated
from lighter REEs without any pH increase. This is advantageous, as
heavier REEs are much desired and are more expensive than lighter
ones. In all cases, iron was extracted with the REEs. Copper and
phosphate extraction was not significant, regardless of feed or pH
tested. Selective stripping of REEs from iron was possible with nitric
acid or diluted hydrochloric acid, and this will be discussed later.
The extraction of REEs from the acids tested decreased in the order:
nitric acid, hydrochloric acid, sulfuric acid. In contrast with the
solvating extractants tested, DEHPA extracted REEs from sulfuric
acid. Due to economic considerations (sulfuric acid is plentiful and
cheap, and DEHPA is commercially available), this system was
further investigated. This will be discussed in the next section.
The distribution ratios with Cyanex 572 are presented in Fig. 6.
Compared to DEHPA, extraction of REEs was not as effective. Iron
was extracted in all cases. A 1.6 mol/L hydrochloric solution didn't
manage to selectively strip REEs from iron. Nitric acid was, how-
ever, able to selectively recover the REEs.
It was concluded that acidic extractants are suitable for extrac-
tion of REEs from sulfuric acid, where solvating reagents failed.
DEHPA was preferred due to better distribution of REEs at low pH
(stability of the New Kankberg sulfate solution at high pH was a
concern). Selective stripping of REEs with hydrochloric acid was
possible. In contrast with solvating reagents, extraction of phos-
phate was not evident; this allows for higher product purity. Co-
extraction of iron is a main concern, as this will also affect the
loading capacity of the organic phase. The Covas sulfuric acid e
DEHPA system was further investigated to get a better picture of the
extraction process and to find effective ways to mitigate co-
extraction of iron.
4.2.3. Extraction of REEs from covas sulfuric acid model solution
with acidic extractants
4.2.3.1. pH dependency. The Covas sulfuric acid solution was partly
neutralized with solid sodium hydroxide. This was preferred over
431
sodium hydroxide solution to prevent significant volume changes,
which would affect the metal concentration. This allowed prepa-
ration of aqueous feeds with similar metal content and different
pH. The effect of equilibrium pH on the extraction with 1 mol/L
DEHPA is presented in Fig. 7.
Iron was well extracted and its distribution increased with
increasing pH. Copper was not significantly extracted across the pH
range investigated. Dysprosium could be selectively recovered from
the other REEs at pH 0, which did not require any addition of so-
dium hydroxide. At this pH, iron was extracted. Further recovery of
the other REEs required an equilibrium pH above 1. Neodymium
and cerium were extracted first, followed by lanthanum at higher
pH. The results showed good selectivity between heavy and light
REEs but not much between cerium and neodymium. Extraction
with 1 mol/L Cyanex 572 was investigated in a similar manner.
During extraction, all aqueous feeds with an initial pH above 1.3 led
to formation of third phases and had to be discarded. No third
phase modifiers were used in this study. Extraction of REEs from
the aqueous phases with initial pH lower than 1.3 was very poor.
Only minor amounts of dysprosium were extracted as the pH
increased. Iron was the only metal ion which was effectively
extracted. Between 25 and 65% of the iron was extracted across the
pH range in which third phase didn't occur. Extraction with Cyanex
572 was not investigated further.
4.2.3.2. The extraction behaviour of metal ions in time in the DEHPA
system. To study the extraction behaviour of metal ions in time, the
Covas sulfate feed was partly neutralized with solid sodium hy-
droxide to pH 1.65. Aliquots of this solution were contacted with
1 mol/L DEHPA for 1e60 min. The results are presented in Fig. 8.
Extraction of iron occurred slowly and did do reach equilibrium
during the investigated time. About 90% of the iron was extracted in
1 h. The pH in the aqueous phase changes during the slow uptake of
iron due to the liberation of protons by the extractant (similar to
Equation (2)) and this affects the distribution of REEs in time
(Fig. 7). Initially, due to higher pH, the light REEs were also
extracted. As iron continued extracting (continuously lowering the
aqueous pH), these REEs were back-extracted in the aqueous phase.
Dysprosium was the only REEs not significantly affected. This is
explained by its effective extraction, even at low pH. Nonetheless,
minor amounts of dysprosium were back-extracted as extraction of
iron tended towards equilibrium. Iron co-extraction can be reduced
by maintaining a short phase contact time. Similar behaviour was
also reported for centrifugal extraction of REEs from wet-process
phosphoric acid (Wang et al., 2011). The non-equilibrium extrac-
tion is, in this case, a simple option to increase the REEs/iron sep-
aration factors. This also mitigates the pH decrease, allowing better
extraction of lighter REEs.
4.2.3.3. Stripping of metal ions extracted with DEHPA.
Stripping of 1 mol/L DEHPA previously contacted with Covas sul-
furic acid solution (pH after extraction 1.15) was done with 0.5 mol/
L citric acid, and with 1e6 mol/L hydrochloric and nitric acid
(Fig. 9). Light REEs were easiest to strip, as they form weaker
complexes due to their larger ionic radius. Citric acid performed
very poorly. Over 75% of the cerium and 85% of the neodymium
were recovered in one step with the 1 mol/L acidic solutions.
Satisfactory recovery of dysprosium required increased acidity.
There weren't significant differences between the performance of
the two mineral acids. Iron was not striped in significant amounts
by nitric acid. The same was observed for diluted hydrochloric acid.
Minor stripping of copper was observed. The amount of copper
initially extracted by DEHPA was, however, low, about 1.5%.
432 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
Fig. 4. Distribution ratios of elements with 0.1 mol/L TODGA. Extraction conditions: O:A 1:1, 45 min phase contact time at 1500 vpm, 21  C. Calculations using mass balance for a
single sample replicate. Distribution ratios calculated to be below 0.01 or above 100 are reported as 0.01 and 100, respectively. Distribution ratios calculated to be between 0.01 and
0.05 are reported as 0.05.
4.2.3.4. Minimizing co-extraction of iron by blending DEHPA with
other extractants. Prior investigations showed that co-extraction of
iron with DEHPA can be minimized by maintaining a short contact
time between the aqueous and the organic phases. Nonetheless,
some iron will be extracted. For high amounts of iron in solution, as
is the case for the tailings investigated here, a small extractable
fraction can still be problematic for separating mg/L amounts of
REEs with high purity. Although selective stripping of REEs is
possible, minimizing iron co-extraction simplifies the separation
process, allows for higher purity of REEs and produces less sec-
ondary wastes. The premise tested here was that extraction of iron
could be reduced by mixing DEHPA with Cyanex 923 and/or Aliquat
336. The distribution ratios for several such systems are given in
Fig. 10. Here, the mixing time was set to 2.5 min to extract some of
the iron and be able to compare the efficiency of different organic
blends.
Halving the concentration of DEHPA led to an expected decrease
in the extraction efficiency of all metal ions. Addition of Aliquat 336
significantly supressed extraction. Dysprosium was still extracted
but its distribution ratios were much lower compared to DEHPA
alone. By using organic phases consisting of DEHPA, Cyanex 923
and kerosene only, iron co-extraction was reduced. At the same
time, the distribution of REEs increased. This positive outcome led
to further investigations of the DEHPA e Cyanex 923 system.
Several compositions were tested (Table 2) to see how much Cya-
nex 923 is needed to supress co-extraction of iron without signif-
icantly affecting the distribution of REEs. The mixing time was
reduced to 1 min to further minimize co-extraction of iron. The
results are presented in Fig. 11.
The distribution ratios of iron decreased with increasing the
concentration of Cyanex 923 in the organic phase. Increasing the
concentration of Cyanex 923 past 0.235 mol/L (10 %vol.) also led to
decreased distribution of all REEs. It was previously noted that
Cyanex 923 alone did not extract REEs from sulfuric acid media
(Fig. 2).
Extraction was further studied with 1 mol/L DEHPA þ0.235 mol/
L Cyanex 923 at O:A ratios in the range 4:1e1:4 (Fig. 12). Based on
the observations, it was decided to select an O:A ratio of 1:3 for a
mixer-settler separation trial. Co-extraction of iron was minimal at
this phase ratio, while extraction of REEs was satisfactory. Using
less organic phase is beneficial, as it leads less consumption and
losses of chemicals, and less secondary wastes. This is due to higher
metal load in the organic phase compared to extraction at higher
O:A ratio, and lower volumes of stripping solution needed.
4.2.3.5. Extraction in mixer-settlers. Extraction of REEs from Covas
sulfuric acid model solutions was studied in a counter-current
mixer-settler system comprising five extraction stages. The
organic phase consisted of a mix of 1 mol/L DEHPA and 0.235 mol/L
Cyanex 923 in kerosene. Two aqueous feeds were tested, one with
an initial pH of 1.19 and one with a pH of 1.95. The extraction
behaviour of iron and REEs is shown in Fig. 13.
Extraction of dysprosium from both feeds was very effective.
Three extraction stages were sufficient to recover most of the
dysprosium. At lower pH (Fig. 13a), extraction of the other REEs was
not significant in the first three stages but started to become
noticeable afterwards. Co-extraction of iron was around 8% in the
first three stages and reached 18% in the last stage. Upon increasing
the pH of the starting solution to 1.95, extraction of all REEs
improved (Fig. 13b). Less iron was co-extracted here, likely due to
competition with the REEs. The extraction efficiency increased in
the order: lanthanum, cerium, neodymium, dysprosium. The last
one was effectively recovered in the first two stages. At the same
time, co-extraction of the other REEs was more preeminent
compared to the first feed. A complete separation of cerium and
neodymium will require a large number of extraction and stripping
stages. Their extraction occurred concomitantly and the differences
in extraction percentages at a given pH were not significant to allow
good selectivity. Lanthanum, on the other hand, was less extracted
and its complete separation will require a lower number of
extraction/stripping stages.
4.2.4. Potential processing of New Kankberg and Covas leachates
The most desirable REE in the New Kankberg and Covas feeds is
dysprosium but this is present in lowest amounts. Nevertheless,
although lanthanum and cerium have lower market value, they are
now regarded as the most critical REEs for the European Union
(European Commission, 2017). These are used together with neo-
dymium as mischmetal alloy in nickel metal hydride (NiMH)
rechargeable batteries. These have important applications in the
automotive industry, specifically hybrid vehicles and buses.
The pH of the aqueous feed needs to be above 1 to get satis-
factory extraction of lighter REEs with DEHPA. This was not possible
for the New Kankberg sulfuric acid model solution due to precipi-
tation. For this reason, separation was studied in mixer-settlers
with Covas solution. For the New Kankberg sulfuric acid model
solution, which contained significantly higher amounts of REEs, no
copper and no iron, precipitation at higher pH is an option. This did
not significantly affect the solubility of dysprosium and phosphate.
The light REEs can be recovered as a group and used for mischmetal
production after subsequent treatment. Cerium, lanthanum and
neodymium in the New Kankberg sulfate solution were easily
 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437 433

Fig. 5. Distribution ratios of elements with 1 mol/L DEHPA. Extraction conditions: O:A
1:1, 30 min phase contact time at 1500 vpm, 21  C. Calculations using mass balance for
a single sample replicate. Distribution ratios calculated to be below 0.01 or above 100
are reported as 0.01 and 100, respectively. Distribution ratios calculated to be between
0.01 and 0.05 are reported as 0.05. Data for the New Kankberg sulfuric acid solution at
higher pH was omitted due to precipitation.
Fig. 6. Distribution ratios of elements upon extraction with 1 mol/L Cyanex 572.
Extraction conditions: O:A 1:1, 30 min phase contact time at 1500 vpm, 21  C. Calcu-
lations using mass balance for a single sample replicate. Distribution ratios calculated
to be below 0.01 or above 100 are reported as 0.01 and 100, respectively. Distribution
ratios calculated to be between 0.01 and 0.05 are reported as 0.05. Data for the New
Kankberg nitric and sulfuric acid solutions at higher pH was omitted due to
precipitation.
434 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437

Fig. 7. Extraction as a function of pH in the Covas sulfuric acid e 1 mol/L DEHPA

system. Extraction conditions: O:A 1:1, 30 min phase contact time, 1500 vpm, 21  C.
Calculations using mass balance for a single sample replicate.

Fig. 9. Striping of metal ions after extraction of metal ions from Covas sulfuric acid
model solution (initial pH 1.65) with 1 mol/L DEHPA. Striping conditions: O:A 1:1,
30 min phase contact time, 1500 vpm, 21  C. Copper data for the 6 mol/L systems not
available. Calculations using mass balance for a triplicate test.

Fig. 8. Extraction of metal ions as a function of time for the Covas sulfuric acid e
1 mol/L DEHPA system. Extraction conditions: initial aqueous pH 1.65, O:A 1:1, 1500
vpm, 21  C. Calculations using mass balance for a triplicate test.

recovered as double sulfate salts at pH 1 upon adding sodium

hydroxide.
For Covas, dysprosium can be extracted at low pH with mixtures
of DEHPA and Cyanex 923; selective stripping from any co-
extracted iron is easy. The organic and stripping solutions can be
run in a loop so that dysprosium is concentrated in a small volume.
This REE can be subsequently precipitated as oxalate (Equation (8))
and afterwards converted to oxide via thermal treatment (Equation
(9)).
Fig. 10. Distribution ratios of elements with various blended organic phases. Extrac-
tion conditions: initial aqueous pH 2, O:A 1:1, 2.5 min phase contact time at 1500 vpm,
2 REE3þ(aq) þ 3 C2O2
4 (aq) / REE2(C2O4)3 (s) (8) 21  C. Calculations using mass balance for a triplicate test. Distribution ratios calcu-
lated to be below 0.01 or above 100 are reported as 0.01 and 100, respectively. Dis-
2 REE2(C2O4)3 (s) þ 3 O2 (g) / 2 REE2O3 (s) þ 12 CO2 (g) (9) tribution ratios calculated to be between 0.01 and 0.05 are reported as 0.05.

The Covas model solution after solvent extraction of dysprosium

can be selectively extracted with copper-specific reagents, e.g.,
contains copper, most of the iron, and the other three REEs. Copper
commercial LIX or Acorga extractants (Szymanowski, 1993). The
 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
Fig. 11. Extraction of metal ions from Covas sulfuric acid model solution with mixed
DEHPA e Cyanex 923. Extraction conditions: initial aqueous pH 2, O:A 1:1, 1 min phase
contact time, 1500 vpm, 21  C. Calculations using mass balance for a triplicate test.
Fig. 12. Extraction percentages of metal ions with 1 mol/L DEHPA þ0.235 mol/L Cya-
nex 923 at different O:A ratios. Aqueous phase: Covas sulfuric acid solution partly
neutralized to pH 1.2. Extraction conditions: 1 min phase contact time at 1500 vpm,
21  C. Calculations using mass balance for a single test.
Fig. 13. Extraction of metal ions from Covas sulfuric acid model solutions with a mix of
1 mol/L DEHPA and 0.235 mol/L Cyanex 923 in kerosene. Extraction conditions: O:A
1:3, 1000 rpm mixing speed, 21  C, 2 mL/min organic, 6 mL/min aqueous, initial
aqueous pH: 1.19 (a) and 1.95 (b). Calculations using mass balance.
remaining REEs can be recovered at higher pH using solvent
extraction. Given the lower concentration of REEs in the feed, it
may be practical to recover lanthanum, cerium and neodymium as
a group for mischmetal production. This avoids the numerous
solvent extraction and stripping stages needed to achieve individ-
ual separation. Alternatively, selective precipitation is an option;
there is a lot of research on this topic due to the high interest in
recovering REEs from REE-iron permanent magnet leachates
(Ferron and Henry, 2015; Tunsu et al., 2018). A flowsheet to process
Covas-type sulfuric acid leachate, which comprises the steps
435
Fig. 14. Potential options to process Covas-type sulfuric acid feed.
mentioned above, is presented in Fig. 14. A combination of lower
O:A ratio for extraction and higher O:A ratio for stripping can be
used to overcome for the lower concentration of REEs in the feed.
This can be coupled with re-circulation of the feeds to further
enrich the REE content in solution and minimize the amounts of
iron. We tested stripping of metals from a mixed 1 mol/L DEHPA
and 0.235 mol/L Cyanex 923 organic solution. Stripping was done
with 2 mol/L nitric acid solution at O:A ratio 10:1. In one stage, 40%
of the extracted lanthanum, 20% of the cerium, 15% of the neo-
dymium and 1% of the dysprosium were back-extracted. The
stripping efficiency of iron was low, 0.1% of the extracted amount.
Stripping of the organic after the mixer-settler experiment (the
aqueous feed with initial pH 1.95) with 2 mol/L nitric acid solution
at O:A 10:1 gave a solution containing 200 mg/L REEs and 3 mg/L
iron.
5. Conclusions
Tailings from past and current mining activities can be potential
sources of critical raw materials. In the ENVIREE Project, various
European and South African sites were screened to find suitable
materials for urban mining. Samples from New Kankberg (Sweden)
and Covas (Portugal) contained not only REEs but also other critical
elements such as phosphate and tungsten. The former had the
highest content of REEs among the investigated European sites,
over 10 g/kg after beneficiation. The contents of tungsten in the
latter reached 24 g/kg after beneficiation with gravimetric tech-
niques and magnetic separation. Using gravity separation, the REEs
in Covas tailings were concentrated 5.5 times (recovery above 70%)
and tungsten was concentrated 2.5 times (50% recovery). This can
be easily implemented on-site and requires mainly water and po-
wer, which translates into very low CAPEX and OPEX. Tungsten can
be selectively leached from the contained REEs using basic solu-
tions, followed by acidic leaching of REEs. Nonetheless, the high
amounts of iron, phosphate and copper in such tailings can be
problematic in the hydrometallurgical recovery of REEs. They are
leached alongside REEs and can negatively affect the effectivity of
subsequent solvent extraction processing.
This study assesses how solvent extraction separation of REEs
from simple model leachates is affected by high amounts of phos-
phate, iron and copper ions. We wanted to see how extraction of
REEs with solvating (Cyanex 923, TODGA) and acidic extractants
(DEHPA and Cyanex 572) is affected for various common mineral
acids. The goal was to find mitigation paths for eventual hindrances
during separation of REEs. In general, extraction of REEs from
different acids decreased in the order: nitric acid, hydrochloric acid,
sulfuric acid. Solvating extractants gave satisfactory results in nitric
436 C. Tunsu et al. / Journal of Cleaner Production 218 (2019) 425e437
acid media but showed limited potential in other acids. Acidic
extractants were able to extract REEs from all acids, a notable
economic advantage for sulfuric acid leachates. Selectivity was
significantly better with acidic extractants, which allowed for
easier recovery of individual REEs. Extraction of REEs was not
hindered by the high amounts of phosphate in solution. Phosphate
extraction was possible with Cyanex 923. Copper didn't interfere
with the recovery of REEs. Iron, on the other hand, was extracted
together with the REEs in most systems, negatively affecting
selectivity. Extraction of iron occurred much slower in time. A low
phase contact time is recommended as first mitigation method, e.g.,
extraction at non-equilibrium conditions. Aside from pH control,
co-extraction of iron with DEHPA can be reduced by blending the
extractant with Cyanex 923. A mixed 1 mol/L DEHPA and
0.235 mol/L Cyanex 923 solution in kerosene notably reduced the
amounts of iron extracted and led to increased extraction efficiency
of all REEs. Selective striping of REEs from iron was possible with
nitric acid or diluted hydrochloric acid. Extraction of REEs from
Covas sulfuric acid model leachate was tested with the aforemen-
tioned organic phase in a counter-current mixer-settler system
comprising 5 separation stages. It was possible to completely and
selectively recover dysprosium from the other REEs at low pH.
Further recovery of neodymium, cerium and lanthanum was done
at higher pH. While lanthanum can be isolated from cerium and
neodymium, individual separation of these two REEs is more
difficult. They can be recovered easier as a group and used for
production of mischmetal.
Acknowledgements
ERA-MIN and VINNOVA, Sweden, are acknowledged for finan-
cial support (project 2014-06227). ADEME, France, is also
acknowledge for financial support (decision 1402C0142). Boliden
AB, Sweden, is acknowledged for supplying samples. The authors
would like to thank Nils-Johan Bolin for his input.
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