Xie 2014

Minerals Engineering 56 (2014) 1028
Contents lists available at ScienceDirect
Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng
A critical review on solvent extraction of rare earths from aqueous

solutions q
Feng Xie a,, Ting An Zhang a, David Dreisinger b, Fiona Doyle c
a
School of Materials and Metallurgy, Northeastern University, 3-11 Wenhua Road, Shenyang 110004, China
Department of Materials Engineering, University of British Columbia, 309-6350 Stores Road, Vancouver, BC V6T 1Z4, Canada
c
Department of Materials Science and Engineering, University of California, Berkeley, 210 Hearst Mining Building, Berkeley, CA 94720, United States
b
a r t i c l e
i n f o
Article history:
Received 2 September 2013
Accepted 22 October 2013
Available online 15 November 2013
Keywords:
Rare earths
Solvent extraction
Process conguration
a b s t r a c t
Rare earth elements have unique physicochemical properties that make them essential elements in many
high-tech components. Bastnesite (La, Ce)FCO3, monazite, (Ce, La, Y, Th)PO4, and xenotime, YPO4, are the
main commercial sources of rare earths. Rare earth minerals are usually beneciated by otation or gravity or magnetic processes to produce concentrates that are subsequently leached with aqueous inorganic
acids, such as HCl, H2SO4, or HNO3. After ltration or counter current decantation (CCD), solvent extraction is usually used to separate individual rare earths or produce mixed rare earth solutions or compounds. Rare earth producers follow similar principles and schemes when selecting specic solvent
extraction routes. The use of cation exchangers, solvation extractants, and anion exchangers, for separating rare earths has been extensively studied. The choice of extractants and aqueous solutions is inuenced by both cost considerations and requirements of technical performance. Commercially, D2EHPA,
HEHEHP, Versatic 10, TBP, and Aliquat 336 have been widely used in rare earth solvent extraction processes. Up to hundreds of stages of mixers and settlers may be assembled together to achieve the necessary separations. This paper reviews the chemistry of different solvent extractants and typical
congurations for rare earth separations.
2013 The Authors. Published by Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1.
Rare earths ores. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2.
Technological applications of rare earths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3.
Primary rare earth extraction process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Solvent extraction separation of rare earths. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Cation exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Carboxylic acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2.
Organophosphorous acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Chelating extractant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Solvation extractant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Anion exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Synergistic solvent extraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Process engineering and equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Molycorp-bastnesite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Rhne-poulenc monazite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.3.
AS Megonxenotime. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.4.
Mintekapatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.5.
Industrial processes in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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q
This is an open-access article distributed under the terms of the Creative Commons Attribution-NonCommercial-No Derivative Works License, which permits noncommercial use, distribution, and reproduction in any medium, provided the original author and source are credited.
Corresponding author. Tel.: +86 24 8368 7729.
E-mail address: xief@smm.neu.edu.cn (F. Xie).
0892-6875/$ - see front matter 2013 The Authors. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.10.021
F. Xie et al. / Minerals Engineering 56 (2014) 1028
4.
3.1.6.
Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Process simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
20
22
26
26
26
been adsorbed onto the surfaces of clay minerals such as kaolin,

feldspar and mica (Liu, 2008; Chi and Tian, 2007; Yang et al.,
2008; Wang, 2009).
1.1. Rare earths ores

The term rare earths was originally used to designate the lanthanoids in row 3 of the periodic table which includes oxides of
scandium (Sc, 21), yttrium (Y, 39), lanthanum (La, 57) and the 14
elements following lanthanum in the periodic table of elements,
i.e. from cerium (Ce, 58) to lutetium (Lu, 71) inclusive. More recently, the term rare earths has been used to designate the elements themselves. Scandium and yttrium tend to occur in the
same ore deposits as the lanthanoids and exhibit similar chemical
properties (Jones et al., 1996; Wang et al., 2011). The term rare
earth is a misnomer; they are relatively abundant in the Earths
crust, however, they are typically dispersed and only rarely occur
in concentrated and economically exploitable mineral deposits.
Rare earth mines have operated in South Africa, India, and Brazil
in the 1950s, but from the 1960s to the 1980s, the largest global
producer was a mine in Mountain Pass, California. In the 1990s,
China began large scale production and exported cheaper rare
earths. Other producers were unable to compete economically,
and began closing in the 1990s, with the Mountain Pass mine shutting down in 2002 (Tse, 2011). Consequently, China is currently the
worlds largest producer of rare earth elements, providing more
than 95% of the worlds total supply from its mines in Inner Mongolia (Chen, 2010). The world reserves and production of rare
earths are summarized in Table 1 (U.S. Geological Survey 2011).
There are a wide variety rare earth minerals known, but notably
the mined minerals are bastnesite (La, Ce)FCO3, monazite, (Ce, La,
Y, Th)PO4, and xenotime, YPO4 (Clark, 1984; Jordens et al., 2013).
Bastnesite deposits in China and the United States constitute the
largest percentage of the worlds rare earth resources. Notable
occurrences include the carbonatite-hosted bastnesite deposit at
Mountain Pass, California, several bastnesite deposits in Sichuan
Province, China, and the massive deposit at Bayan Obo, Inner Mongolia, China. Monazite deposits in Australia, Brazil, China, India,
Malaysia, South Africa, Sri Lanka, Thailand, and the United States
constitute the second largest segment. Apatite, cheralite, eudialyte,
loparite, phosphorites, secondary monazite, spent uranium solutions, and xenotime make up the remaining resources. There are
also ion-adsorbed rare earth deposits, widely distributed in southern China formed through weathering were the rare earths have
Table 1
Global rare earth mine production and reserves (after U.S. Geological Survey, 2011).
Mine production,
metric ton
United States
Australia
Brazil
China
Common wealth of Independent
States
India
Malaysia
Other countries
World total
11
2009
2010
550
129,000
550
130,000
2700
350
2700
350
132,600
133,600
Reserves, metric
ton
13,000,000
1,600,000
48,000
55,000,000
19,000,000
3,100,000
30,000
22,000,000
113,778,000
1.2. Technological applications of rare earths

Rare earth metals and their compounds are in demand, and are
often crucial for, a broad and rapidly expanding range of applications that rely upon their chemical, catalytic, electrical, magnetic,
and optical properties. Rare earths are widely used for traditional
sectors including metallurgy, petroleum, textiles, and agriculture.
As indicated in Table 2 (Commercial Applications for Rare Earth
Technology, Http://reitausa.org), they are also becoming uniquely
indispensable and critical in many high-tech industry such as hybrid cars, wind turbines, and compact uorescent lights, at screen
televisions, mobile phones, disc drives, and defense technologies
(Song and Hong, 2010a,b). Different rare earths are needed to supply the required functionality in these applications. In some cases,
a single rare earth element may be required, such as La for nickelmetal hydride batteries, but other applications require a mixture of
rare earths, for example Nd and Pr for rare earth magnets and Eu
(or Tb) and Y for rare earth phosphors.
Rare earth-containing permanent magnets are alloys of rare
earth elements and transition metals such as iron, nickel, and cobalt. Samarium-cobalt magnets were rst developed in the 1970s
(Liu et al., 2006). However, due to their higher cost and weaker
magnetic eld strength, these magnets are now used less than neodymium magnets, unless their higher Curie point is needed. Neodymium permanent magnets, a tetragonal alloy of neodymium,
iron, and boron (Nd2Fe14B), have been used in a wide range of
applications requiring a high energy product and high coercive
force (Brown et al., 2002). Neodymium can be replaced by praseodymium and up to 5% cerium in high energy product magnets
(Doyle et al., 2000; Benz et al., 2000). The addition of terbium
and dysprosium can enhance the coercivity of NdFeB sintered
magnets (Hu et al., 2008; Xu et al., 2011).
Rare earths phosphors are widely used in high efciency lighting, at display screens, plasma screens, and liquid crystal screens
due to their unique luminescent properties (Ronda et al., 1988;
Nazarov and Noh, 2010; Rapaport and Miliez, 2006; Ye et al.,
2011). Unlike transition metal ions, the spectral position of the
emission lines of rare earths is almost independent of the host lattice. Rare earth ions such as Tb3+ and Eu3+ emit at frequencies that
enable high lumen efcacies and a good quality of white light (Liu
and Chen, 2007; Tu et al., 2011). Replacement of some of the rare
earth cations of a crystalline rare earth phosphor by ions of another
rare earth element activates the phosphor, achieving a high degree
of uorescence. For example, terbium-activated gadolinium oxysulphide (Gd2O2S:Tb) gives a maximum uorescence when about
0.3% of the gadolinium atoms have been replaced by terbium. Commercial plasma screens have used yttrium tantalates activated by
thulium (YTaO4:Tm) or niobium (YTaO4:Nb) (Fauchera et al.,
2002; Karsu et al., 2011).
1.3. Primary rare earth extraction process
As highlighted above, bastnesite, monazite, and xenotime are
the main rare earth minerals of commercial importance. Typical
12
Table 2
Some commercial applications of rare earths (after http://www.reitausa.org/).
Application
Rare earth (RE) technology
Enabling functionality
RE elements
required
Hybrids, plug-In, and electric Vehicles
RE permanent magnets
Nd, Pr, Dy, Tb
Wind and hydro power generation
Computer Disc Drives; Cordless Power

tools
Medical imaging MRI
Electric traction drives replacing or supplementing

internal combustion engines
Gearless generators for better reliability and online
performance
Compact, light weight and powerful motors
Produce magnetic eld
X-ray imaging
Handheld wire-less devices
RE phosphors
RE permanent magnets;
High energy efciency

Compact, light weight and powerful motors;
Flat screen display

Catalytic converters and other emission
reduction technologies
Fiber optics
Ni Metal Hydride Batteries
RE phosphors
Ability to oxidize CO and ozone to CO2 and O2
Capacitors with high energy density
Rare earth- doped ceramic, tantalum and

other types of capacitors
Unique luminescent properties

Signicantly less expensive than Pt metal group
alternatives
Signal amplication
Proven and cost effective compared to Li ion battery
alternatives
High energy density compared to conventional
capacitors
RE doped optical bers

Energy storage
compositions for these minerals are shown in Table 3 (there may

be signicant compositional variations depending on sources)
(U.S. Bureau of Mines, 1985). Various processing routes have been
developed to recover rare earths. After mining and comminution,
ore is beneciated by otation, magnetic or gravity methods to
produce rare earth concentrates, which then undergo hydrometallurgical processing to recover rare earth metals or compounds
(Gupta and Krishnamurthy, 2005).
Bastnesite concentrates are relatively straightforward to treat
(Huang et al., 2005). In order to reduce the acid consumption, bastnesite concentrates are typically roasted to decompose the carbonate minerals before leaching with either hydrochloric or sulfuric
acid. Cerium comprises about half of the rare earth content within
bastnasite, so removing it prior to solvent extraction dramatically
reduces the solvent extraction capacity for selective separation of
individual rare earth elements. To minimize the separation costs
cerium could be oxidized to CeO2 during roasting which will not
dissolve readily in acidic lixiviants so would report to the leach residue from which it could be recovered separately. Hydrochloric
acid may promote reduction of Ce(IV) and hence, incomplete separation of Ce(III) from the other trivalent lanthanides, Ln(III). Alternatively after leaching all the rare earths, cerium could be oxidized
in the aqueous phase to precipitate it and then be recovered by ltration. For example, Ce(OH)4 was precipitated at the Thorium
Table 3
Rare earth contents of principal minerals as percentage of total rare earth oxide
(Mineral Facts and Problems, 1985).
Oxide
Y2O3
La2O3
CeO2
Pr6O11
Nd2O3
Sm2O3
Eu2O3
Gd2O3
Tb2O3
Dy2O3
Ho2O3
Er2O3
Tm2O3
Yb2O3
Lu2O3
Total
Bastnesite
(California)
Monazite
(Australia)
0.1
32.0
49.0
4.4
13.5
0.5
0.1
0.3
2.1
23.0
45.5
5.0
18.0
3.5
0.1
1.8
0.1
1.0
100.0
100.0
Xenotime
(Malaysia)
60.8
0.5
5.0
0.7
2.2
1.9
0.2
4.0
1.0
8.7
2.1
5.4
0.9
6.2
0.4
100.0
Nd, Pr
Nd, Pr, Dy, Tb
Nd, Pr, Dy, Tb,
Y, Eu, Tb
Nd, Pr, Dy, Tb,
Y, Eu
Y, Eu, Tb, Gd, Ce
Ce, La
Y, Eu, Tb, Er
La
Various rare
earths
plant using ammonium carbonate and ammonium persulfate

(Huang et al., 2005). In some cases, sodium hypochlorite is also
used to oxidize dissolved Ce(III).
At Baotou, the largest producer of rare earths in China, the bastnesite concentrates contain a small amount of monazite. Fig. 1
shows the leaching process used for Baotou rare earth concentrates, which has been designated to be exible and to accommodate different concentrates. The process starts with roasting with
concentrated sulfuric acid at >300 C (Huang et al., 2006) to crack
the monazite. The rare earth sulfates formed during this process
are then leached with water, and excess acid is neutralized with
magnesia and ltered. The leach solution then proceeds to solvent
extraction, alternatively a mixed rare earth chloride (for electrolysis to misch metal) could be produced by precipitation with ammonium carbonate, followed by dissolution with HCl and
crystallization. Unfortunately, the radioactive element, thorium,
is precipitated and reports to the leach residue. It cannot be recovered economically, resulting in both loss of the valuable thorium
and potential environment hazards. HF and sulfur dioxide report
to the off-gas from roasting. Large amounts of water or alkaline
solutions are needed to remove them, resulting in large volumes
of acidic efuents.
The roasting process has been modied, for example by adding
MgO or CaO and NaCl to stabilize uorine in the leaching residue
instead of releasing it to the waste gas phase (Wang and Liu,
1996; Wu et al., 2002a,b, 2004b; Li et al., 2004). Bastnesite has also
been roasted with ammonium chloride, which decomposes into
gaseous HCl that forms rare earth chlorides, which are readily leached with hot water (Chi et al., 2004). Another variant involves
heating concentrate with sulfuric acid at 40180 C for two to four
hours before roasting at 150330 C (Hu, 1998). This suppresses
decomposition of sulfuric acid, resulting in a relatively high fraction of HF in the gas phase; this can be recovered as solid NH4F
by reacting with (NH4)2CO3 in the off-gas pipe. In some plants,
the bastnesite concentrates are rst digested with concentrated
NaOH to decompose carbonates and then leached with hydrochloric acid to produce mixed rare earth chlorides (Gupta and Krishnamurthy, 2005; Xu et al., 2012). The disadvantages of this process
include high alkaline consumption and the radioactive thorium
reporting to both the leachate and the residue, which hampers
subsequent recovery.
Monazite and xenotime concentrates can be leached either by
sulfuric acid or by sodium hydroxide at elevated temperature to
decompose the orthophosphate lattice. The sodium hydroxide
treatment is preferred in most commercial extraction plants because it better separates phosphate from the rare earth (Alex
et al., 1998). The ion-adsorption type rare earth ores are usually
leached directly with inorganic acid, either in dumps or in situ,
resulting in dissolution of most of rare earths in acidic solutions
(Zuo et al., 2007; Qiu et al., 2008).
Regardless of the original rare earth mineral or the precise
leaching process, the leach solution will usually contain dissolved
impurities such as iron, which are removed by precipitation before
proceeding to solvent extraction to separate the rare earths.
factor, commonly used to quantitatively describe solvent extraction. The distribution coefcient of a metal ion, M, DM (sometimes
designated as K), particularly in earlier literature, is given by:
DM
M
K
M
where M is the molar concentration of M in the organic phase and

[M] is the concentration in the aqueous phase. The separation factor
of two different metal ions, M1 and M2, bM1/M2, is dened as:
bM1=M2
2. Solvent extraction separation of rare earths
Solvent extraction producer starts by separating different
groups of rare earths from the leachate. Depending on the process,
some primary rare earths producers may choose to sell intermediate, mixed products, or perform different downstream separations
to produce individual rare earth salts or oxides. Individual rare
earths are difcult to separate from each other, due to their similar
physical and chemical properties. Separation processes based on
ion-exchange and solvent extraction techniques have thus been
developed to produce high purity single rare earth solutions or
compounds. Before the advent of industrial scale solvent extraction
in the 1960s, ion exchange technology was the only practical way
to separate the rare earths in large quantities (Jamrack, 1963; Kumar, 1994; Reddy et al., 2009). Nowadays, ion exchange is only
used to obtain small quantities of high purity rare earth product
for electronics or analytical applications (Taniguchi and Doty,
1989). Solvent extraction is generally accepted as the most appropriate commercial technology for separating rare earths due to the
need to be able to handle larger volumes of dilute pregnant liquors
(Peppard et al., 1953, 1957a,b; Peppard and Wason, 1961; Brown
and Sherrington, 1979; Sherrington, 1983).
Solvent extraction processes for separation and purication of
rare earths have been reviewed during the 1990s (Zhu, 1991; Reddy et al., 1995). Table 4 summarizes commercial extractants reported in the literature for rare earth solvent extraction (Ritcey
and Ashbrook, 1984; Rydberg et al., 2004). All three major classes
of extractant, namely, cation exchangers (or acidic extractants),
solvation extractants (or neutral extractants), and anion exchangers (or basic extractants), have been utilized for separating rare
earths. Some chelating extractants have also been suggested for
rare earth separations.
Before considering the different types of extractant, it is useful
to dene two terms, the distribution coefcient and the separation
DM1
DM2
2.1. Cation exchangers

The overall extraction of rare earth elements from aqueous
media by cation exchange extractants in their acidic form can generally be expressed as (Peppard et al., 1958):
Ln3 3HA LnA3 3H
Ln3 3H2 A2 LnHA2 3 3H
Here H2A2 refers to the dimeric form of the organic acid. From
inspection of Eqs. (3), (4), it is evident that the extraction of rare
earths with cation exchangers is promoted by increasing the aqueous phase pH, while the stripping process, which reverses the
extraction reaction, is promoted by increasing the acidity of the
aqueous stripping solution.
Two different classes of cation exchangers are use for rare earth
separations, namely carboxylic or fatty acids, and organic derivatives of phosphorous acids.
2.1.1. Carboxylic acids
The use of different carboxylic acids, including naphthenic acids
and Versatic acids, for extracting rare earth metal ions has been reported (Bauer and Lindstrom, 1964; Korpusov et al., 1974). The
Roasting with concentrated H2SO4

Off-gas
Calcined concentrate
water
leaching
MgO
Neutralization/precipitation/filtration
Solvent extraction for separation

of individual rare earth
where Ln denotes any rare earth, A denotes the organic anion, and
overscoring denotes species present in the organic phase. Generally
the process is more complicated then expressed in Eq. (3) where the
acidic extractants are usually aggregated as dimmers or larger oligomers in non-polar organic solutions, which lowers their polarity,
and the rare earth complexes formed upon extraction may contain
undissociated organic acid. Thus a more accurate depiction of the
extraction reaction is (Mason et al., 1978):
Rare earth concentrate (50% wt REO)
leachate
13
residue
Precipitation with ammonium carbonate and
dissolution with HCl to produce mixed rare earth
Fig. 1. Schematic leaching process used for Baotou rare earth concentrates (after Huang et al., 2006).
14
Table 4
Some commercial extractants for rare earth solvent extraction (after Ritcey and Ashbrook, 1984; Rydberg et al., 2004).
Reagents class
Structure
1, Cation exchangers
Carboxylic acids
R1
Extractants
Versatic acids:
R1 + R2 = C7, Versatic 10;
R1 + R2 = C6C8, Versatic 911
CH3
C
R2
COOH
R2
R1
(CH2)nCOOH
R3
Phosphorous acids
Naphthenic acids:
R1-R4: varied alkyl groups
R4
Phosphoric acids:
R1 = R2 = C4H9CH(C2H5)CH2O, di-2-ethylhexylphosphoric acid (D2EHPA)
Phosphonic acids:
R1 = C4H9CH(C2H5)CH2O, R2 = C4H9CH(C2H5)CH2, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester
(EHEHPA, HEHEHP, P507, PC88A)
Phosphinic acids:
R1 = R2 = C4H9CH(C2H5)CH2, di-2-ethylhexylphosphinic acid (P229)
R1 = R2 = CH3(CH2)3CH2CH(CH3)CH2, di-2,4,4-trimethylpentylphosphinic acid (Cyanex 272)
R1
P
R2
OH
R1
Monothiophosphorous acids
R1 = R2 = CH3(CH2)3CH2CH(CH3)CH2, di-2,4,4-trimethylpentyl-monothiophosphinic acid (Cyanex 302)
P
R2
OH
R1
Dithiophosphorous acids
R1 = R2 = CH3(CH2)3CH2CH(CH3)CH2, di-2,4,4-trimethylpentyl-dithiophosphinic acid (Cyanex 301)
P
SH
R2
2, Chelating
exchangers
b-diketones:
R1 = R-C6H5, R2 = CH3(CH2)5, R: unknown side alkyl, (LIX 54)
O
R1 C CH2 C R2
O
3, Solvating
extractants
R1
P
R3
R2
4, Anion exchanger
RNH2
Phosphorous ester:
R1 = R2 = R3 = CH2(CH2)2CH2O, tri-n-butyl-phosphate (TBP)
R1 = R2 = CH2(CH2)2CH2O, R3 = CH2(CH2)2CH2, dibutylbutylphosphonate (DBBP)
Phosphine oxides:
R1 = R2 = R3 = CH2(CH2)6CH2, tri-n-octylphosphine oxide (TOPO, Cyanex 921)
Primary amines
R = (CH3)3C(CH)2C(CH3)2)4 (Primene JMT, N1923)
Quaternary amines:
R1 = R2 = R3 = C8C10 mixture (Aliquat 336, Adogen 464)
RNH2
CH3 Cl
R1
N
R2
R3
extraction behavior of yttrium differs for these reagents; yttrium is

extracted by Versatic 10 with the middle rare earths (La < Ce < Nd < Gd < Y < Ho < Yb) whereas it is extracted by naphthenic
acid with the light rare earths (La < Ce < Y < Nd < Gd < Ho < Yb)
(Preston and du Preez, 1990). Zheng et al. (1991) noted that the
behavior of Y is correlated with the acidity of the extractant, while
du Preez and Preston (1992) attributed the changing order to steric
hindrance caused by the structure of the carboxylic acids and the
atomic number of rare earth metal ions. With straight chain and
non-hindered acids the behavior of yttrium most closely resembles
that of light lanthanides (e.g., Ce, or Pr), while for the sterically hindered acids the behavior of yttrium most closely resembles that of
middle lanthanides (e.g., Gd or Tb).
Naphthenic acid has been widely used for separating yttrium
from lanthanides in China (Li et al., 1994). However, the extractant
composition changes with use and its high solubility in water lead
to signicant reagent losses (Li, 1995). Alternatively, the novel carboxylic acids, such as sec-nonylphenoxy acetic acid (CA-100) and
sec-octylphenoxy acetic acid (CA-12), developed in China, have
much lower aqueous solubilities than naphthenic acids. A study

on the extraction of trivalent lanthanides (Sc, Y, Ln) and divalent
transition metal ions (Cu, Zn, Ni, Mn, Cd, Co) from acidic chloride
solutions with CA-100 in heptane indicated that CA-100 can extract rare earth ions at lower pH values than Versatic 10. The
extraction behavior of yttrium with CA-100 most closely resembled that of the heavy lanthanides (Wang et al., 2002; Li et al.,
2007a; Li et al., 2007b; Li et al., 2007c). The extraction behavior
of trivalent rare earths using cekanoic, neo-heptanoic, and some
2-bromo alkanoic acids has also been investigated (Preston,
1994; Xu et al., 2003; Singh et al., 2006). It was suggested that
the introduction of the 2-bromo substitute in an alkanoic acid
structure lowers the pKa values, enabling the substitute acids to
be effective extractants at lower pH than the parent compounds.
2.1.2. Organophosphorous acids
Various kinds of acidic organophosphorous extractants have
been used in rare-earth separation processes, with D2EHPA (or
HDEHP, di(2-ethylhexyl) phosphoric acid) and HEHEHP (or EHEH-
PA, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl) are the

main solvents widely used. Peppard et al. (1957a,b) noted that
the distribution coefcients of rare earth ions at tracer concentrations between D2EHPA in toluene and aqueous chloride solutions
had an inverse third-power dependency on the HCl concentration
in the aqueous phase and a third-power dependency on the
D2EHPA concentration in the organic phase. This indicates that
only one of the acid groups in a D2EHPA dimmer in the organic
phase dissociates and participates in the extraction reaction (following Eq. (4)). Gels formed in the organic phase at high metal
loadings and low acidities, which is undesirable because of the
associated viscosity and phase separation problems (Ferraro and
Peppard, 1963).
The selectivity order for extracting rare earths from 0.5 M HCl
solution with 0.75 M D2EHPA in toluene was Lu > Yb > Tm > Tb > Eu > Pm > Pr > Ce > La (Fig. 2) (Peppard and Wason, 1961), with
the log of the distribution coefcient (called log K by Peppard et al.
(1957a,b)) increasing linearly with the atomic number, Z, of the
rare earth. The average separation factor of two adjacent rare earth
elements was 2.5. Yttrium was extracted between Tb and Tm in
this solvent extraction system, corresponding to an articial atomic number 67.6. The extraction of the lanthanide elements with
D2EHPA in toluene was similar for perchloric acid solutions (Piece
and Peck, 1963), but poorer in nitrate media (Reddy et al., 1995). It
should be pointed out that although the distribution coefcients of
rare earths generally increase with increasing atomic number, the
precise separation factors depend on the acidity of the aqueous
phase and nature of the anion.
In 1965, Molycorp demonstrated the large scale application of
D2EHPA for pre-concentrating europium to around 15% from rare
earth chloride feed derived from bastnesite, containing about
0.1% Eu2O3 (Kruesi and Schiff, 1968). Preston and du Preez
(1996) pre-concentrated europium from chloride containing
0.22 0.01 M total rare earths (%: Eu 93, Sm 3, Nd 2, Ce 1, Pr 0.5
and Gd 0.5) using 0.4 M D2EHPA in xylene; 99.98% Eu solutions
were obtained in a single extraction stage at pH 2.7. 1 M D2EHPA
Log K
-1
-2
-3
-4
57
59
61
63
65
67
69
71
Z
Fig. 2. Plot of Log K (Log D) as a function of atomic number (Z) (0.75 M HDEHP in
toluene and 0.5 M HCl; Tracer concentrations of rare earths) (after Peppard et al.,
1957a,b).
15
was used to separate a 99.8% La2O3 product from didymium chloride solution (feed containing 45% La2O3, 35% Nd2O3, 10% Pr6O11
and 5% Sm2O3) (Nair and Smutz, 1967). Two multistage countercurrent extraction circuits were needed; the rst, 12 stage cascade
concentrated La in the rafnate, and the second, 14 stage cascade
provided further purication. The overall recovery of La was 60%.
Preston et al. (1996a,b,c) described a continuous solvent extraction process for separating the middle (Sm, Eu, Gd, and Tb) and the
light rare earth fractions (La, Ce, Pr, and Nd) from a nitrate feed.
The middle rare earths were rst extracted into a 15% v/v of
D2EHPA in Shellsol AB in an 8 stage counter-current circuit, followed by scrubbing with 1 mol/L HNO3 in 24 stages, and stripping
with 1.5 mol/L HCl in 68 stages. Residual rare earths in the organic phase (mainly Dy, with some Tb and Gd) were removed in a secondary stripping circuit using 2.5 mol/L HCl in four stages. Over
1000 L of feed liquor was processed in two continuous countercurrent trials lasting a total of 630 h. From feed containing Sm:
3.5 g/L, Gd: 2.4 g/L, Eu: 0.8 g/L, and Nd: 20 g/L (together with 4 to
8 g/L each of the lighter rare earths), strip liquors containing Sm:
35 g/L, Gd: 20 g/L, and Eu: 8 g/L were obtained with neodymium
(5 g/L) as the main impurity. The recoveries of the middle rare
earths to the strip liquors were relatively high (95100%), whereas
losses of the light rare earths were low (< 4%). D2EHPA has also
been used to separate Sm, Eu, and Gd from the other rare earths
in a mixed nitrate-chloride leachate from monazite (Rabie, 2007).
D2EHPA can extract rare earth at low pH values, but because
the equilibrium of Eqs. (1) and (2) lies strongly to the right it is difcult to strip the loaded metals. Thus, other acidic organophosphorus extractants have been widely examined for rare earth solvent
extraction. Benedetto et al. (1995) reported that DS5834 (Zeneca
Specialties, with a formulation similar to M2EHPA, mono-2-ethylhexyl phosphoric acid) could effectively extract Ga, In, Sm, and Gd
from acidic media but was neither selective for Sm and Gd, nor
effective for the separating these metals. The reagent HEHEHP,
marketed variously as PC-88A, SME 418, Ionquest 801 and P-507,
has gained more popularity for rare earth separations because rare
earths can be stripped at lower acidities than from D2EHPA (Reddy
et al., 1995). In addition, HEHEHP can be more heavily loaded with
rare earth than D2EHPA before the onset of saturation effects,
which increases the extraction efciency. The extraction of rare
earths with HEHEHP follows Eq. (1), with the extraction order
from chloride and nitrate media of La < Ce < Pr < Nd < Sm < Eu < Gd < Tb < Dy (Y) < Ho < Er < Tm < Yb < Lu (Sato, 1989).
A process developed by Daihachi for separating rare earths using
HEHEHP has been applied in commercial separation plants in Baotou, China (Zhu, 1991). Fontana and Pietrilli (2009) also suggested
the use of HEHEHP for recovering rare earths resulted from spent
NiMnH batteries.
Some di-alkyl phosphinic acids have also been investigated for
rare earth separation, although only Cyanex 272 (bis(2,4,4-trimethylpentyl) phosphinic acid) has been used commercially (Kolarik
and Pankova, 1966; Li and Frieser, 1986; Banda et al., 2012). Sabbot
and Rollat (1985) described the preparation of pure Yb2O3 (99.3%)
from a mixture of ytterbium and lutetium oxides (Yb2O3 = 87.5%,
Lu2O3 = 12.5%) using 1 mol/L Cyanex 272 in kerosene. Saleh et al.
(2002) investigated the extraction of La(III) by Cyanex 272 in toluene from acidic nitrate-acetato media and suggested the formation
of La(Ac)2A.3HA (Ac denotes acetate ion and HA denotes the acidic
form of Cyanex 272) in the organic phase at low La loading and
LaA3 at higher loading. Studies on the extraction of samarium from
chloride solutions with Cyanex 272 indicated that the extracted
species was Sm(OH)A2.2HA (El-Hefny et al., 2010). Studies on the
extraction of La, Pr, Eu, Ho and Yb into chloroform solutions containing dicyclohexylphosphinic acid (DCHPA) showed that the
extraction selectivity of DCHPA was inferior to that of other di-alkyl phosphinic acids, presumably because the cyclohexyl groups in
16
DCHPA sterically hinder chelate formation (Cecconie and Frieser,

1989).
2.2. Chelating extractant
As hydrogen ion donors, chelating extractants extract metals by
a cation ion exchange mechanism similar to Eq. (1), but but the
resulting organic complexes are stabilized by the organic anion
coordinating the central cation in at least two positions (Hudson,
1982): Chelating extractants have been examined for extracting
europium from nitrate solutions and cerium(III) and lanthanum(III) from chloride solutions, but performed unfavorably compared with acidic extractants (Urbanski et al., 1996; Arichi et al.,
2006).
2.3. Solvation extractant
Several types of solvation extractants have been used for rare
earth separations. Peppard et al. (1957a,b) investigated the extraction of trivalent rare earths from chloride and nitrate solutions
with TBP (tributylphosphate). The extractability of the lanthanides
with TBP increased with increasing atomic number, but the distribution coefcients were much lower in chloride solutions than in
nitric media. Concentrated nitric systems were promising for separating rare earths lighter than samarium. Rare earths heavier than
samarium could not be separated effectively in nitric systems. The
rare earths in neutral nitrato complexes are coordinated by
the phosphoryl group of TBP, yielding an extractable complex.
The overall reaction can be expressed as:
Ln3 3NO3 3TBP LnNO3 3 TBP3
although there would be few simple Ln3+ cations in solution at the

ionic strengths needed for effective extraction. Later work of Peppard et al. (1966) examined the inuence of extraction conditions on
the equilibrium constant of reaction 5 to infer the composition of
the complexes formed under different conditions (Peppard et al.,
1957a,b). Lu et al. (1998) studying the solvent extraction of Ce(IV)
and Th (IV) from sulfate solutions with Cyanex 923 in n-hexane,
found the extraction of Ce(IV) to be insensitive to acidity, while
the extraction of Th(IV) increased with the aqueous acidity. A third
phase formed at H2SO4 > 5 mol/L. The extraction of Ce(IV) and
Th(IV) from sulfate media with Cyanex 923 can be represented by
the reaction:
2
M4 SO2
4 2HSO4 2B MSO4 HSO4 2 2B
where M represents Ce or Th and B denotes Cyanex 923. The extraction of trivalent lanthanides and yttrium from nitrate medium with
Cyanes 925 in heptane was suggested to follow the reaction (Li
et al., 2007a,b,c):
M4 3NO3 2B MNO3 2 2B
where M and B represent the metal and Cyanex 925, respectively.

During the 1960s, Thorium Limited in the United Kingdom used
TBP to separate light rare earths in nitrate media (Sherrington,
1966). This process was operated batchwise with total reux; on
attaining steady state, the process was stopped and products of different composition were withdrawn from different stages. This
conguration is costly compared to continuous processing and
not amenable to scale up. Preston et al. (1996a,b,c) described a pilot-scale process for recovering a mixed rare-earth oxide product
from calcium sulfate hemihydrate sludge generated during the
manufacture of phosphoric acid from apatite mined at Phalaborwa,
South Africa. Rare earths were recovered from leach liquor
containing 1.0 M nitric acid and 0.5 M calcium nitrate by adding

2.5 M ammonium nitrate and extracting into 33% v/v DBBP (dibutyl butylphosphonate) in Shellsol 2325. The organic phase was
stripped with water to yield a solution of rare earth nitrates from
which the mixed rare earth oxide was recovered by adding oxalic
acid and calcining the precipitate. Later work examined using
TBP (15% in Shellsol K diluent) to selectively extract cerium(IV)
from the rare earth nitrate feed (Preston et al., 1996b). The organic
phase was stripped by reducing the cerium(IV) with dilute hydrogen peroxide in two stages, giving solutions containing up to 90 g/L
of cerium(III).
2.4. Anion exchangers
Anion exchangers extract metal ions as anionic complexes, and
hence are only effective in the presence of strong anionic ligands.
Early work indicated that the separation factors for adjacent rare
earths with primary or tertiary amines were poor in chloride media
but were more promising in sulfate media. (Rice and Stone, 1962;
Bauer, 1966). El-Yamani and Shabana (El-Yamani and Shabana,
1985) suggested that the extraction of lanthanum(III) from sulfate
solutions with Primene JMT (tri-alkyl methylamine) was extracted
with the following reactions:
2RNH2 H2 SO4 RNH3 2 SO4
2
2LaSO4 3
3 3RNH3 2 SO4 2RNH3 3 LaSO43 3SO4
where RNH2 denotes the Primene JMT in the organic phase. Y(III)
was found to behave similarly (Desouky et al., 2009). Quaternary
ammonium salts such as tri-octyl methylammonium nitrate (Aliquat 336) have proved promising for separating rare earths. The
extraction reaction can be simply represented as (Hsu et al., 1980;
Huang et al., 1986):
Ln3 3NO3 xR4 N NO3 n LnNO3 xnR4 N NO3
10
where Ln denotes the rare earth ion and R4 N NO

3 the quaternary
ammonium nitrate salt (Cerna et al. (1992) suggested a more complicated reaction). These reagents are strong-base anion exchangers
and require lower concentrations of salting out reagents than
amines. Chelation with EDTA improved the extraction and separation of rare earth pairs. In nitrate media Aliquat 336 extracts light
rare earths more readily than the heavier ones. This behavior contrasts that of most of cation exchange and solvating extractants,
for which the extraction of the rare earth metals increases steadily
with increasing atomic number. Hence, quaternary ammonium
salts provide a means of removing light rare earths from process
solutions.
Yttrium is anomalous, behaving as a heavy rare earth in nitrate
media and as a light in thiocyanate media. This has been utilized
for treating xenotime, which contains 60% Y2O3 (Table 2). Xenotime concentrate was leached with HNO3 and lighter rare earths
were extracted with Aliquat 336 in an aromatic diluent. Yttrium
and the heavy rare earths remained in the aqueous phase. Yttrium
was then extracted by Aliquat 336 from a thiocyanate solution,
yielding 99.99% Y2O3, while other heavy rare earths remained in
the rafnate (Gaudernack, 1973). Lu et al. (1989) isolated >99%
Nd2O3 from didymium nitrate solution (83% Nd, 15% Pr and 2%
other rare earths) with 95% Nd recovery using Aliquat 336 in a
45-stage extraction. Preston (1996) described a solvent-extraction
process for recovering neodymium oxide (95% Nd2O3) from light
rare earth nitrate solution using 0.50 M solution of Aliquat 336 nitrate in Shellsol AB.
2.5. Synergistic solvent extraction

Numerous types of synergistic solvent extraction systems for
extracting and separating rare earths have been reported, including
mixtures of acidic extractants (e.g., carboxylic or organophosphorus acids), mixture of neutral extractants (e.g. TBP and TOPO),
and combinations of these (Santhi et al., 1991; Wang et al., 2006;
Tian et al., 2012; Tian et al., 2013; Tong et al., 2013). Preston and
du Preez (1994) examined the effect of the addition of a series of
tri-alkyl phosphates (RO)3PO, di-alkyl alkylphosphonates (RO)2RPO, alkyl di-alkylphosphinates (RO)R2PO, and tri-alkylphosphine
oxides R3PO on the extraction of the trivalent lanthanides and yttrium from chloride media by DIPSA (3,5-di-isopropylsalicylic
acid). Synergistic effects were observed with all mixtures, albeit
to different extents. For the series of compounds with R = n-butyl,
the synergistic effect increased in the order (RO)3PS < (RO)3PO < (RO)2RPO < (RO)R2PO < R3PO. The synergistic effects were
greater for lutetium(III) than for lanthanum(III) (the separation
across the lanthanide series increased). Mixtures of DIPSA and
TIBPO (tri-isobutyl phosphine oxide) gave somewhat better separation factors between the light and the middle lanthanides
(bSm/Nd = 3.0) than Versatic 10 acid alone (bSm/Nd = 2.6). Separation
factors were comparable to those with the latter extractant
between the heavy lanthanides (thulium to lutetium). The authors
suggested that the extracted rare earth complexes had a composition of LnA3L2 (where HA represents carboxylic acid and L the neutral organophosphorous compound) and the synergism resulted
from the replacement of some or all the undissociated carboxylic
acid molecular (see Eq. (4)) (Preston and du Preez, 1995).
Comparison of the effects of some bi-functional ligands containing C@O, P@O or S@O groups upon the extraction of trivalent rare
earth metals from chloride media by DIPSA in xylene indicated that
the shifts generally increased in the order S@O < C@O < P@O for
comparable ligands. The synergistic effect produced by the addition of a given bi-functional compound generally decreased across
the lanthanide series (La to Lu), attributed to steric hindrance effect
(Preston and du Preez, 1998). Reddy et al. (1999) reported that
La(III) and Nd(III) were extracted from nitrate solution by Cyanex
301 (HA) and Cyanex 923 (L) as LnA2.NO3.L, while Eu(III), Y(III)
and heavier rare earths were extracted as LnA3.HA.2L (Reddy
et al., 1999). Tri-alkylphosphine oxide signicantly enhanced both
the extraction efciencies and selectivities, especially between yttrium and heavier lanthanides. Zhang et al. (2008) reported studies
of the solvent extraction of cerium(IV) and uoride from sulfate
solutions using a mixture of Cyanex 923 and D2EHPA in n-heptane
and Ce(III) was not extracted by the mixture.
For binary acid extractant systems, Ying et al. (2005) examined
the extraction of Yb3+ from chloride solution with Cyanex 272,
P507 (HEHEHP), and their mixtures in n-heptane. The extraction
of Yb3+ was higher with the mixture than with Cyanex272 or
P507 alone. A synergistic effect was observed on the separation
of Yb/Tm and Lu/Yb, but not for Tm/Er, Er/Ho, and Ho/Dy. Zhang
et al. (2007) investigated the extraction of trivalent La, Nd, Sm,
and Gd from sulfate media by a mixture of D2EHPA and HEHEHP.
A synergistic effect was observed for the extraction of all four metals at pH = 2.0. Li et al. (2007) also reported that the separation factor for Sm and Nd was signicantly increased using a mixture of
D2EHPA (40% v/v) and HEHEHP (60% v/v).
Sun et al. (2006) examined the synergistic extraction of trivalent Sc, Y, La, Gd, and Yb from chloride media using a mixture of
Cyanex 272 and sec-nonylphenoxy acetic acid (CA-100) in n-heptane. The separation factor for Yb and Y was much higher than that
with CA-100 alone. The extraction of rare earth elements from
chloride media by mixtures of CA100 with Cyanex 301 or Cyanex
302 was studied by Tong et al. (2009). In the CA100 + Cyanex
301 system, the synergistic enhancement coefcients decreased
17
with increasing atomic number of lanthanoids, but the separation

factors between Y and all the lanthanoids were enhanced. Jia et al.
(2009) reported that the separation factors of all adjacent trivalent
rare earths were better in a mixture of sec-octylphenoxy acetic
acid (CA12) and Cyanex301 in n-heptane than in Cyanex 301 alone.
3. Process engineering and equipment
Although there is an extensive literature on rare earth solvent
extraction chemistry and equilibriums, as discussed above, far less
is known on the engineering details of rare earth separations. From
the limited open literature, rare earth producers appear to follow
similar approaches (Gupta and Krishnamurthy, 2005). There is often a need for a primary separation of rare earths from impurities
in the original leach solution, along with concentration. D2EHPA
has been widely used for primary separation because the distribution coefcients of the rare earth elements as a group differ markedly from those of typical impurities in leach liquors. D2EHPA is
also suitable for concentrating the rare earth elements from dilute,
acidic solutions.
In general, rare earths are separated in the trivalent state. They
are usually separated into two, three or sometimes four groups,
followed by precipitation or subsequent separation of individual
rare earth. Preferential separation of yttrium is desirable, and cerium and europium are often separated initially on the basis of different valance states (Ce4+ and Eu2+).
The extractants and aqueous anion are generally selected considering both cost and technical requirements, and the impact on
the process conguration (McGill, 1997). For example, cationic
exchangers usually offer higher selectivity on rare earth ions compared to neutral and anionic exchangers. However, the reactive
chemical requirement is greater with cation exchangers, because
base is required to drive extraction, and acid is required for selectively washing the organic phase. In contrast, with solvation
extractants and anion exchangers the reactive chemical requirement is lower. Thus there is a trade-off between selectivity (which
lowers the number of stages, and hence capital and chemical
inventory costs) and the operating costs.
3.1. Congurations
Rare earth solvent extraction processes are generally classied
as primary separations, which aim to separate rare earth elements
from other elements (which is relatively straightforward, and comparable with other solvent extraction processes in hydrometallurgical operations), and secondary separations, which produce single
or mixed (typically 2 or 3) rare earth products from the mixed rare
earth stream produced by primary separations. The latter is often
much more challenging, particularly when producing a single, pure
rare earth, because of the chemical similarity of the rare earths. As
mentioned above, D2EHPA has been widely used in primary separation processes because the distribution coefcients for the rare
earth elements with D2EHPA are markedly different from those
of other elements in the aqueous solution (leach liquor). D2EHPA
is also suitable for concentrating the rare earth elements from dilute solutions because of the high distribution coefcients.
A plant producing multiple single rare earth products may contain hundreds of stages of mixers and settlers. A classic countercurrent ow scheme for a simple solvent extraction circuit is shown in
Fig. 3. The aqueous stream leaving the nth mixer settler would be
pumped to the (n 1)th mixer settler, while the organic phase
(which is ideally in equilibrium with the aqueous phase leaving
the nth stage) would be pumped to the (n + 1)th mixer settler. This
arrangement may also be used for simple rare earth separations,
e.g., the primary separation of rare earths from impurities. How-
18
organic feed
organic product
n-1
n+1
n+m
aqueous feed
aqueous raffinate
Fig. 3. Simplied countercurrent solvent extraction circuit.
ever, there is fundamental shortcoming with this conguration if

one wishes to separate rare earths from a mixed feed. Consider
an operation using a cation exchange extractant or a solvating
extractant, for which the heavier rare earths have a stronger afnity for the organic extractant phase than have the lighter ones. Iif
mixed aqueous feed were introduced into one end of a bank of
mixer settlers, the organic phase leaving the other end would be
somewhat enriched in heavy rare earths, but there would still be
an appreciable amount of light rare earths in this stream, because
of the low separation factors. This shortcoming is addressed by
introducing the mixed aqueous feed near the middle of the bank
of mixer settlers, as shown in Fig. 4. A different aqueous stream
is admitted into the end (the (n + m)th stage) to allow an appropriate number of stages for the light rare earth to be scrubbed from
the organic phase back into the aqueous phase. This scrub solution
may exit the process midway, or may continue on with the aqueous feed. To minimize the dilution of rare earth concentrations
caused by the introduction of the barren aqueous scrub and the organic phase, reux is sometimes used; some of the light rare earths
from the aqueous rafnate are loaded back into the organic phase
entering the rst mixer settler, and some heavy rare earths are
stripped from the organic product and added to the aqueous scrub
(Fig. 5). When operating under reux, the mass transfer occurring
at each stage becomes an exchange of different rare earths, according to their afnity for an extractant, as exemplied below for a liquid cation exchange extractant.
LaA3 Ce3 CeA3 La3
11
Reux minimizes dilution and also reduces the number of stages

need to achieve an effective separation. Nevertheless, many separation stages are typically needed to obtain pure product. Most banks
of mixer settlers are set up to make a single separation between two
adjacent rare earths, but some congurations have three or more
product streams. Various processes for rare earths separation from
concentrates/ore and aqueous solutions have been summarized in
detail by Gupta and Krishnamurthy (2005). Some typical applications and process owsheets for solvent extraction separation of
rare earths used in practice are listed below.
3.1.1. Molycorp-bastnesite
Fig. 6 shows the schematic owsheet for the Molycorp process,
used to extract europium oxide from the leachate of Mountain Pass
bastnesite (Gupta and Krishnamurthy, 2005). A chloride solution
(100 g/L REO) containing all the rare earth except Ce is generated
by calcination and leaching with HCl solution. Two steps of solvent
extraction with D2EHPA were applied. The chloride solution was
rst contacted with 10% v/v D2EHPA in kerosene, and the extraction was performed in ve stages of mixers and settlers under conditions that split the rare earths with Sm and all heavier rare
earths reporting to the D2EHPA solution, and Nd and all lighter elements reporting to the rafnate (this is designated in Fig. 6 by
(Nd/Sm) in the rst solvent extraction stage). There are two
organic feed
organic product
aqueous raffinate
n-1
n+1
n+m
aqueous feed
aqueous feed Optional scrub exit
Fig. 4. Simplied conguration of countercurrent solvent extraction circuit with optional scrub exit.
organic feed
Partial
reflux
organic product
aqueous raffinate
aqueous feed
n+1
n+m
Partial
reflux
aqueous scrub
Fig. 5. Simplied conguration of countercurrent solvent extraction circuit with reux.
19
Bastnesite concentrate (60% REO)

Calcination
Conc. HCl
Leaching
Residue for Ce recovery
Other REs, Fe
10% D2EHPA
Solvent extraction (Nd/Sm)/stripping

Sm, Eu, Fe
Soda ash
Iron Precipitation
Raffinate (for recovery of

La, Ce, Pr, Nd)
Iron precipitate
Sm, Eu
10% D2EHPA
Solvent extraction(Sm/Eu)/stripping
Raffinate fed to the

first SX circuit
Eu(3) Chloride solution

Zinc amalgam
Reduction
H2SO4
Precipitation
EuSO4 solution for producing Eu2O3
Fig. 6. Molycorp process for producing europium oxide from the bastnesite concentrate (after Gupta and Krishnamurthy, 2005).
engineering reasons for splitting the rare earths in this way initially. The rst is that it is relatively easy to separate Nd and Sm
since they are consecutive elements in any natural rare earth minerals, but are not consecutive elements on the periodic table and
the intermediate rare earth element, promethium, does not occur
in nature. Thus their separation factor is typically double that of
any other consecutive rare earth pair. The second reason is that,
referring back to Table 3, it is apparent that Sm and the heavier
rare earths account for only a very small proportion of the rare
earths in bastnesite. Thus they can be removed using a small volume of D2EHPA solution, and the resulting rare earth mixture
can be further processed using much smaller mixer settlers, leaving La, Pr, and Nd (the bulk of the rare earths in the concentrate)
in the aqueous rafnate. These were precipitated with ammonium
and sodium hydrogen sulde and further processed in much larger-scale equipment. More than 98% of europium in the solution
was extracted.
The loaded organic (containing 98% of the Eu from the leach liquor) was stripped with 4 mol/L HCl. The iron in the strip solution
was precipitated through neutralization to pH 3.5, and the claried
Eu-bearing solution proceeded to a second solvent extraction circuit, also using 10% D2EHPA in kerosene and ve stages of mixers
and settlers. Europium and other heavy rare earths were loaded in
the organic phase, with the light rare earths remaining in the rafnate, which were returned to the rst solvent extraction circuit.
The europium (and other rare earths) were stripped from the
loaded D2EHPA with 5 mol/L HCl solution and the strip liquor
was passed through a column of zinc amalgam to reduce Eu(III)
to Eu(II). Sulfuric acid was added to precipitate europium sulfate,
which was then calcined to produce pure Eu2O3 (99.99%). After
europium recovery, the strip solution still contained Sm, Y, and
other heavy rare earths. Gadolinium was extracted with D2EHPA
in a 10-stage extraction circuit followed by a 5-stage scrub. The
rafnate was neutralized with soda ash to precipitate Sm and the
heavy rare earths.
3.1.2. Rhne-poulenc monazite
Rhne-Poulenc had the capability of producing all the rare
earth elements at a purity of >99.999% almost entirely by solvent
extraction (McGill, 1997). A schematic owsheet of the process is

shown in Fig. 7. Monazite concentrate was rst digested with
NaOH. The rare earths reported to the solid residue as hydroxides,
which after ltration were dissolved in HCl or HNO3. After
clarication, the resulting solution proceeded to a series of solvent extraction circuits to produce individual rare earth oxides.
Chloride media were used to prepare a mixture of rare earth
compounds, such as dehydrated rare earth chlorides, which were
used to produce misch metal. Nitrate media were used to produce
individual rare earth oxides, e.g., in the rst separation circuit,
lanthanum (99.9995% La2O3) remained in the aqueous phase
while a mixture of Ce, Pr, Nd, Sm, etc. was loaded into the organic
phase. Similarly, CeO2 (>99.5%) was separated from Pr, Nd, Sm, Eu,
etc., after removing lanthanum. Various extractants, including
carboxylic acids, organophosphorous acids, neutral organophosphorous compounds, and quaternary amines have been used in
these separation processes. Rhne-Poulenc could also produce
high-purity individual rare earth oxides from bastnesite or
euxenite. The Rhne-Poulenc solvent extraction process has been
regarded as the standard for all industrial producers (Bautista,
1995).
3.1.3. AS Megonxenotime
AS Megon developed a process for producing high-purity yttrium oxide starting from the xenotime concentrates (Gaudernack, 1973). The schematic owsheet is shown in Fig. 8. The
solvent extraction circuit consisted of a selective extraction by
D2EHPA followed by three scrubbing and stripping units. The
light rare earths (La, Ce, Pr and partial Nd) and impurities including Fe2+ ions remained in the rafnate. The extracted yttrium and
other rare earths were separated into three groups by selective
washing. Yttrium nitrate solution was fed to the second circuit
using the nitrate of tri-capryl methylamine as the extractant.
The lighter rare earths (La, Ce, Pr, Nd and Gd, Tb, Er) were
extracted while Y, Tm, Yb, and Lu remained in the rafnate,
which was fed to the third solvent extraction circuit, which used
tri-capryl methylamine-NH4SCN to produce high-purity yttrium
oxide.
20
Monazite
NaOH
Digestion/Filtration
RE-Th hydroxide
HCl
Na3PO4
solution
HNO3
Dissolution
Dissolution
Separation
non-RE/RE/Th
Separation
non-RE/RE/Th
Separation, La-Nd/Sm-Lu
RE chlorides
RE fluorides
Conversion
Cl-/NO3La2O3, 99.995%
Separation, La/Ce, Pr, Nd
CeO2, 99.5%
Separation, Ce/Pr, Nd, Sm
Polishing agent
Separation, Pr, Nd/Sm, Eu, Gd
RE carbonates
Anhydrous RE chlorides
Mischmetal
Pr6O11, 96%
Didymium
Separation, Pr/Nd
Separation, Sm, Eu/Gd-Lu
Nd2O3, 96%
Sm2O3, 96%
Separation, Sm/Eu
Gd2O3, 99.99%
Tb4O7, 99.9%
Eu2O3, 99.99%
Y2O3, 99.99%
Fig. 7. Rhone-Poulenc liquidliquid extraction process for separation of the rare earth elements (after McGill, 1997).
3.1.4. Mintekapatite
Rare earths have been recovered from the calcium sulfate
sludge generated during the production of phosphoric from apatite
at Phaleborwa (Preston et al., 1996b). Fig. 9 shows the schematic
owsheet for the pilot plant. The sludge was leached with dilute
nitric acid solution containing calcium nitrate. Rare earths were
extracted from the leachate with TBP (40% v/v in Shellsol 2325).
The rafnate was recycled back to leaching after removing entrained organic solvent. The loaded organic solution was stripped
with water to yield a mixed rare earth nitrate aqueous solution
that was treated with ammonia and oxalic acid to precipitate a
mixed rare earth oxalate. This was calcined to give a mixed rare
earth oxide (8994% purity). The rare earth oxide contained considerable amount of the middle rare earths, particularly Nd, Sm,
Eu, and Ga. In subsequent pilot tests, TBP, HDEHP and Aliquat
336 were used to produce different rare earth products from the
mixed oxides.
3.1.5. Industrial processes in China
The Shanghai Yue Long Chemical Plant, was reported to treat
monazite concentrates in a process similar to the Rhne-Poulenc
process (Zhang et al., 1982). The simplied owsheet of this plant
is shown in Fig. 10. After digesting the monazite in NaOH, ltration
and leaching of the residue with HCl, the resulting rare earth chloride solution was extracted with D2EHPA and the rare earths were
split into three groups, from which mixed and pure oxides, carbonate, or chlorides were produced. The ion-adsorption type rare earth
ores are rst leached with HCl or H2SO4. Cation exchange extractants, such as HEHHP and naphthenic acid, are frequently used to
extract rare earths elements from the leachate, since these ores
have high levels of heavy rare earths, which have a strong afnity
for acidic extractants. Individual rare earth compounds (oxides or
chlorides) can be produced through controlled stripping (Huang

et al., 2005, 2006).
For bastnesite ore, which is the main rare earth resource in China, the ore or concentrates are typically roasted with H2SO4, followed by leaching with water or dilute sulfuric acid. Rare earths
are recovered from the leachate by solvent extraction with P204
(D2EHPA). Preferential stripping is used to divide the rare earths
into two groups, La-Nd and Sm-Gd (the concentration of heavier
rare earths is usually small); these can be further separated into
individual rare earth elements if desired (Huang et al., 2006). To reduce reagent consumption, modied separation processes have
been tested at pilot plant scale. One approach used P204 or P507
to extract Th and most of Ce rst, then the rafnate containing
the remaining rare earths underwent further solvent extraction
steps to separate individual rare earth compounds (Fig. 11) (Huang
et al., 2006). The F, Th, and Ce(IV) were selectively stripped from
the organic phase. Another approach used Cyanex 923 to separate
Ce(IV) from the leachate rst. The rafnate containing other rare
earths then underwent solvent extraction with N1923 (a primary
amine) to separate Th (Fig. 12) (Lu et al., 1998). Individual rare
earth compounds were produced from the Th-free rafnate in a
third solvent extraction circuit.
3.1.6. Miscellaneous
Doyle et al. (2000) developed a novel solvent extraction conguration capable of producing a mixed CePrNd product (for magnet production) and pure Nd oxide simultaneously, with exibility
to alter the relative proportions according to market conditions.
The schematic owsheet for this process is shown in Fig. 13. Rare
earth chloride solution generated by leaching oxide with HCl
underwent solvent extraction with P507 in kerosene. In the rst
solvent extraction circuit, Sm and all heavier rare earths along with
21
Xenotime
H2SO4; H2O
Residue
Digestion/dissolution/filtration
RE sulfate solution, 20 g/L REO
4-stage
extraction
30% D2EHPA in Shellsol

4-stage selective
scrubbing
8-stage selective
scrubbing
1.5 M HNO3
6 M HNO3
NdSm(GdTb)
LaCePr(Nd),
Fe2+, and other
impurities
4-stage stripping
YbLu(Th)
0.5 M H2SO4
NH3
Yttrium nitrate solution, 75% Y2O3/REO; 6 M NH4NO3
26-stage extraction
40% quaternary amine in Solvesso 50
6-stage scrubbing
3-stage stripping
1.75 M NH4NO3
NH4SCN
Gd-Er
Dilute
HNO3
Yttrium nitrate solution, 95% Y2O3/REO;

4,9 M NH4NO3; 0.1 M NH4SCN
26-stage extraction
6-stage scrubbing
Y2O3, 99.999%;
Yb<2.5 ppm;
Er< 3ppm;
Others <1pm
Solvent treatment
8-stage stripping
NH4SCN
TmYbLu
0.5 M NH4NO3;
0.1M NH4SCN
Dilute
HNO3
Fig. 8. AS Megon process for high-purity yttrium oxide (after Gaudernack, 1973).
Phalaborwa apatite ore

Phosphoric acid manufacturing process
Calcium sulfate sludge
H2O
washing
Washed sluge
Washing solution
Ca(NO3)2, HNO3
residue
Leaching/filtration
40% v/v TBP in Shellsol 2325
Leahate (REO 8-24 g/L; 1M HNO3, 3 M Ca(NO3)2
5-stage extraction
Raffinate
Sheellsol
2325
washing
Washed raffinate
6-stage-stripping
Strip liquor (REO 45-60 g/L)

Organic to
Sheellsol
2325 tank
Precipitation
Water
NH3, oxalic acid
Mixed rare earth oxalate

Calcination in rotary kiln
Mixed rare earth oxalate (89-94% purity)
Fig. 9. Schematic owsheet of the pilot plant for recovering rare earths from the phosphoric acid plant residue at Phalaborwa (after Preston et al., 1997).
22
Monazite
NaOH
Na3PO4
solution
Digestion/Filtration
(RE, Th, U) hydroxide

HCl
Dissolution/Filtration
RECl3 solution
(Th, U) sludge
Dissolution
Solvent extraction
La, Ce, Pr, Nd
Sm, Eu, Gd
Solvent extraction
REO
Solvent extraction
Y2O3
La2O3
Polishing agent
Pr6O11
RE carbonates
Solvent extraction
Nd2O3
Gd2O3
Tb4O7
CeO2
Sm2O3
Dy2O2
RE Chorides
CeCl3
Th(NO3)4
ThO2
phosphors
Solvent extraction
Solvent extraction
Solvent extraction
Eu2O3
RE fluorides
Malten salt electrolysis
Tb, Lu
Lu2O3
U3O8
(NH4)2U2O7
Radioactive waste
treatment
Mischmetal
Fig. 10. Simplied owsheet of the Shanghai Yue Long Chemical Plant (after Zhang et al., 1982).
Y, were loaded into the organic phase. The rafnate containing Nd

and lighter rare earths underwent a second solvent extraction with
P507 in kerosene. Through controlling the number of stages and reux ratios, Pr and Nd and part of thel Ce were extracted into the
organic phase, with the balance of Ce, and all the La remaining in
the aqueous phase from which a marketable lanthanum product
were produced. The loaded organic phase underwent selective
stripping to produce high-purity neodymium oxide and a mixture
of Ce, Pr, and Nd oxides.
Huang et al. (2008) used a synergistic extraction system to produce different rare earth products from rare earth sulfate solutions
resulting from leaching of bastnesite concentrates (Fig. 14). The
non-saponied organic phase was used directly to extract rare
earths from their sulfate or chloride solutions and by controlling
operation conditions, as many as ve (or more) commercial rare
earth products could be produced simultaneously.
3.2. Process simulation

Process development, analysis, control and optimization of rare
earth solvent extraction are complex tasks. Computer simulation
program for monitoring or optimizing the rare earth solvent
extraction process requires a reliable model for the extraction
equilibrium. However, very few models for describing the relevant
equilibrium between rare earth elements and different extraction
systems have appeared in the open literature, and these are usually
only applicable to a limited and specic range of conditions. This
probably reects the similarities of the lanthanides, their propensity for interactions make it difcult to predict their behaviors in
various extraction systems. Therefore, little progress has been
made with regard to the development of a general approach for
modeling rare earth solvent extraction systems.
The reported programs for simulating rare earth solvent extraction processes usually consider countercurrent circuits, due to
their ubiquity. Stage-wise calculations offer efciency and exibility (Sharp and Smutz 1965; Sebenik et al., 1966). Most are based on
the McCabeThiele method (Thiele and Geddes, 1933; McCabe
et al., 2005). The technique was originally developed for graphical
analysis of binary distillation, and later applied to liquidliquid
separation processes, especially for solvent extraction systems
involving only one extractable species (Zhu, 1991; Rydberg et al.,
2004). Considering an n-stage counter-current circuit separating
the metal ion from an aqueous solution by solvent extraction,
the aqueous stream leaving the ith mixer settler would be pumped
to the (i1)th mixer settler while the organic phase would be
pumped to the (i + 1)th mixer settler (i = 1, 2, . . ., n) (Fig. 15).
The symbols in Fig. 15 are dened as follows:
Mn1 : the molar concentration of metal ion in the aqueous
feed;
Mn : the molar concentration of metal ion in organic product;
[M]i+1: the molar concentration of metal ion in the aqueous
solution fed to the ith mixer settler;
Mi : the concentration of metal ion in organic phase leaving the
ith mixer settler;
[M]i: the concentration of metal ion in the aqueous solution
leaving the ith mixer settler;
Mi1 : the concentration of metal ion in organic phase fed to the
ith mixer settler;
[M]1: the molar concentration of metal ion in the aqueous
rafnate;
M0 : the molar concentration of metal ion in the organic feed.
Assuming that the two phases are totally immiscible, and
dening:
23

Calcination
H2SO4
Residue
Leaching/filtration
sulfate solution containing (RE, F, Th)

P204 or P507
Solvent extraction
Raffinate (RE sulfate solution)
Loaded organic
Selective stripping F
Fluoride for recovery
Selective stripping Ce
CeO2, 99% -99.99%
Solvent extraction
Individual RE compounds
stripping Th
ThO2, 99% -99.99%

Fig. 11. Simplied owsheet for separating RE, F, Th by solvent extraction with P204 (after Huang et al., 2006).

Calcination
H2SO4
Leaching/filtration
Residue
sulfate solution containing (RE, F, Th)

Cyanex 923
Solvent extraction
Raffinate (contaning RE, Th)
Loaded organic
Selective stripping F
Solvent extraction
Flouride for recovery
stripping Ce
Raffinate
CeO2, 99% -99.99%
Solvent extraction
Individual RE compounds
N1923 (primary amine)
Loaded organic
stripping Th
ThO2, 99% -99.99%
Fig. 12. Simplied owsheet for separating RE, F, Th by solvent extraction with Cyanex 923 (after Lu et al., 1998).
VA: the ow rate of the aqueous phase;

VO: the ow rate of the aqueous phase;
The mass balance for metal ion in the ith stage can be expressed
as:
V A Mi1 Mi V O Mi Mi1
12
If the extraction equilibria are known, either through theoretical calculations or experimentally, the theoretical number of stage
required can be calculated by solving the mass balance equations
for all stages if the concentrations of metal ion in the aqueous feed
and in the rafnate, and the ow rates of the organic and aqueous
phases are known. The concentrations of metal ion in the two
phases in different mixer settlers can thus be calculated stage by
stage. Fig. 16 shows a McCabeThiele diagram for a 3-stage solvent
24
Ce-free RE sulfate solution

P507
Sm, Gd, Eu for market
Solvent extraction, La(Ce)PrNd/Sm
P507
Solvent extraction, La(Ce)Pr/Nd
Raffinate (La-Ce for market)
Loaded organic
High-purity Nd2O3
Selective strip, (Ce)Pr/Nd
(Ce, Pr, Nd) oxides

Fig. 13. Simplied owsheet for solvent extraction process for producing low-cost permanent magnet feed (after Doyle et al., 2000).
RE sulfate feed solution

Mixed extractants
aqueous scrub
(H2SO4 or HCl)
Multi-stage mixers settlers
La
LaCe
PrNd
SmEuGd
Heavy REs (heavier than Gd)
Fig. 14. Simplied conguration of countercurrent separation of rare earths to produce various rare earths products by solvent extraction.
Fig. 15. Schematic diagrams for simple n-stage countercurrent solvent extraction circuit.
extraction circuit. The equilibrium line OA shows the extraction

isotherm for the desired metal ion. The line BC is an operating
line which is straight with a gradient equal to the ratio of the
aqueous and organic ow rates (VA/VO). The points on this line reect the composition of crossing streams in each stage, i. e., ([M]i+1,
Mi ) for all values of i (i = 1, 2, 3, 4). The molar concentration of metal in the organic feed, M0 , is taken to be zero in this gure,
although it need not be so in practice. When an aqueous feed (with
a molar concentration of [M]4) enters the 3rd stage mixer-settler,
the composition of the organic phase crossing the stream will
be M3 . The composition of the aqueous phase leaving stage-3
([M]3) is determined by the point on the equilibrium line with an
organic concentration of M3 (specically, the point ([M]3, M3 ).
The of the organic stream that crosses the aqueous stream leaving
stage 3 is then obtained from the operating line, as shown graphically on Fig. 16. This allows calculation of the composition of the
rafnate, [M]1. Alternatively, the number of stages needed to attain
specic stream compositions can be obtained graphically. A similar
method can be used to calculate the number of stages needed for
the stripping circuit and the corresponding metal concentration
in the different streams. An equilibrium line for stripping should

be determined or dened rst; this differs from that for extraction
because the chemical composition of the aqueous phase will differ,
for example, having a different pH in the case of cation or anion exchange extractants, or a different concentration of ligands in the
case of a solvating extractant.
A simple case occasionally encountered in rare earth solvent
extraction processes is a linear equilibrium line through the origin (OA in Fig. 17), corresponding to a constant distribution coefcient (DM) for metal extraction in all stages. Thus:
Mi DM Mi
i 1; 2; . . . n
13
Since the operating line, BC, in Fig. 17 has a gradient of VA/VO as dened in Eq. (12), then:
M1 DM M1
14
M1 M0
VA
M2 M 1 V O
15
25
Dening the extraction factor, EM, as:
EM DM V O =V A
20
Eq. (19) can be expressed as:

Mn1 M1 1 EM E2M . . . EnM
21
or:
Mn1 M1
En1
M 1
EM 1
22
Eq. (22) is known as the Kremser equation (Kremser, 1930). Its consequences have been discussed widely and it has been illustrated in
various forms (Klinkenberg, 1951). This equation can applied to any
aqueous streams situated an integral number of stages along the
mixer settler, not just to streams leaving the mixer-settler circuit.
The composition of the organic phase leaving any stage can be obtained by combining Eqs. (14), (22), and (23):
Mn DM M1
Fig. 16. Schematic McCabeThiele diagrams for countercurrent solvent extraction
process.
Fig. 17. Schematic diagram for countercurrent stagewise solvent extraction with a
constant distribution coefcient.
Assuming M0 0 (no metal in the organic feed) gives:
M1
VA
M2 M1 V O
16
Combining Eqs. (14) and (16):

VO
M2 M1 1 DM
VA
17
Similarly, one can obtain:
M3 M1 1 DM
Mn1 M1

2 !
VO
VO
DM
VA
VA

2

n !
VO
VO
VO
1 DM
DM
DM
VA
VA
VA
18
19
EnM 1
EM 1
23
The theoretical number of stages required and the metal concentration in relevant streams can be determined from Eq. (22) if
the metal concentration in the feed and rafnate are dened and
the extraction factor is known. Similar equations can be developed
for stripping if there are linear stripping equilibrium and operating
lines (constant stripping factor and constant ratio of aqueous to organic ow rate) (Jamrack, 1963).
However rare earths are seldom extracted in systems containing single rare earths. The solvent extraction system chemistry is
usually controlled to make the distribution coefcient of the desired element(s) much higher than that of the unwanted elements.
Even so, some extraction of these undesired elements is usually
unavoidable. In these circumstances, as shown in Fig. 4, a scrubbing circuit is commonly employed to wash impurities from the
organic before it leaves the extraction circuit. Graphical methods
such as the McCabeThiele diagram become unmanageable for
analyzing several extractable species, each of which has their
own equilibrium line, and each of which may displace or be displaced by other species in the organic phase. In this case, a large
number of extraction, scrubbing, and stripping stages may be required to obtain desired product.
Algebraic equations have been developed from the Kremser and
mass balance equations to calculate the theoretical number of
stages for a countercurrent circuit for separating two rare earth
elements by solvent extraction, assuming constant distribution
coefcients for rare earths in the extraction and scrubbing circuits
(Xu, 1978). Constant distribution coefcients would not be expected in typical solvent extraction circuits, because the exchange
of species between the aqueous and organic phases changes the
chemistry of each stream. However, in rare earth circuits where
one rare earth is often being exchanged with another (see Eq.
(11)), the chemistry may be much more stable so this assumption
becomes more realistic. The separation factors for rare earths are
frequently fairly constant throughout a given circuit (Voit, 1988).
As a result, the distribution coefcients of each lanthanide can be
deduced if the distribution coefcient of one has been determined.
Typically, separation factors depend only on the type of selected
extractant and to a lesser degree on the anionic species in the
aqueous phase. Given that the assumption of constant stream volumes incorporated in the Kremser equation is usually valid, the
equations derived above can be solved computationally to analyze
and simulate rare earth solvent extraction circuits.
Voit (1988) developed a simple simulation program for producing 99.5% Nd2O3 from a mixed rare earth chloride feed (La, Pr, and
26
Nd) using HEHEHPA for extraction, scrubbing and stripping sections. The Kremser equation was used to calculate the separation
occurring in each section of the circuit. Using same equation, Reddy et al. (1992) developed a modied simulation program for an
integrated rare earth solvent extraction circuit. Distribution coefcient data for key rare earth elements were tabulated for different
initial acidity and metal ion concentrations, based on operating
conditions. The use of average separation factors was suggested
for non-constant distribution coefcients (Zhong, 2008). Further
studies have considered the separation of multi-rare earth elements with two or more outlets/products in a single countercurrent circuit (Ding et al., 2003; Wu et al., 2004a,b). A simulation
system has been combined with on-line EDXRF analysis to monitor
the steady or dynamic performance of stage-wise processes (Wenli
et al., 2000; Jia et al., 2001; Jia et al., 2004). The latter authors
claimed that their model was especially useful when there was
no more than one intermediate feed point and the distribution ratio of the component involved was constant. The detail of the calculation method followed was not reported.
4. Summary
Rare earth elements have unique properties and are becoming
essential in many high-technology applications. China is currently
the worlds largest producer of rare earth elements providing more
than 95% of the worlds total supply. Various rare earth minerals
have been identied, of which bastnesite (La, Ce)FCO3, monazite,
(Ce, La, Y, Th)PO4, and xenotime, YPO4, are the most main minerals
commercially targeted. Rare earth minerals are usually concentrated by otation, magnetic or gravity methods to produce concentrates that undergo hydrometallurgical processing to recover
rare earth metals or compounds. Rare earth concentrates or calcine
residue are typically leached with an inorganic acid, such as HCl,
H2SO4, or HNO3.
After solution purication, separation processes based on solvent extraction techniques are used to yield individual rare earths
or mixed rare earth solutions or compounds. Rare earth producers
usually follow almost identical principles or schemes when selecting solvent extraction circuits to separate rare earths from each
other. Usually trivalent rare earths are separated into two or more
groups, followed by subsequent separation of individual rare
earths and preferential separation of yttrium if possible. The choice
of extractants and aqueous solution conditions is inuenced both
by cost considerations and technical requirements, such as selectivity. The use of cation exchangers, solvation extractants, and anion exchangers, for separating rare earths has been extensively
studied. Commercially, D2EHPA, HEHEHP, Versatic 10, TBP, and
Aliquat 336 are widely used commercially to separate rare earth
elements.
Up to hundreds of stages of mixers and settlers may be assembled together to separate all the individual rare earths in a feedstock. Typical congurations for rare earth solvent extraction
circuit have been reviewed. Traditional graphical methods for
simulating solvent extraction circuits, such as McCabeThiele diagrams, have limited practical application for rare earth solvent
extraction circuits. However, more promising computational approaches based on the Kremser and mass balance equations have
been developed and are continually being developed which better
predicts the complex chemical interactions.
Acknowledgement
One of the authors, Ting An Zhang, appreciates the nancial
support of Ministry of Science and Technology of P. R. China
(973 Program, 2012CBA01205 and Science and Technology Supporting Program, 2012BAE01B02).
References
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Minerals Engineering 56 (2014) 1028

Contents lists available at ScienceDirect

A critical review on solvent extraction of rare earths from aqueous

F. Xie et al. / Minerals Engineering 56 (2014) 1028

been adsorbed onto the surfaces of clay minerals such as kaolin,

1.1. Rare earths ores

1.2. Technological applications of rare earths

F. Xie et al. / Minerals Engineering 56 (2014) 1028

Rare earth (RE) technology

Hybrids, plug-In, and electric Vehicles

Nd, Pr, Dy, Tb

Wind and hydro power generation

Computer Disc Drives; Cordless Power

Electric traction drives replacing or supplementing

Produce magnetic eld

High energy efciency

Flat screen display

Capacitors with high energy density

Rare earth- doped ceramic, tantalum and

Unique luminescent properties

RE doped optical bers

compositions for these minerals are shown in Table 3 (there may

plant using ammonium carbonate and ammonium persulfate

F. Xie et al. / Minerals Engineering 56 (2014) 1028

where M is the molar concentration of M in the organic phase and

2.1. Cation exchangers

Ln3 3HA LnA3 3H

Ln3 3H2 A2 LnHA2 3 3H

Roasting with concentrated H2SO4

Solvent extraction for separation

Rare earth concentrate (50% wt REO)

F. Xie et al. / Minerals Engineering 56 (2014) 1028

extraction behavior of yttrium differs for these reagents; yttrium is

much lower aqueous solubilities than naphthenic acids. A study

F. Xie et al. / Minerals Engineering 56 (2014) 1028

PA, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl) are the

F. Xie et al. / Minerals Engineering 56 (2014) 1028

DCHPA sterically hinder chelate formation (Cecconie and Frieser,

Ln3 3NO3 3TBP LnNO3 3 TBP3

although there would be few simple Ln3+ cations in solution at the

where M and B represent the metal and Cyanex 925, respectively.

containing 1.0 M nitric acid and 0.5 M calcium nitrate by adding

2RNH2 H2 SO4 RNH3 2 SO4

Ln3 3NO3 xR4 N NO3 n LnNO3  xnR4 N NO3

where Ln denotes the rare earth ion and R4 N NO

F. Xie et al. / Minerals Engineering 56 (2014) 1028

2.5. Synergistic solvent extraction

with increasing atomic number of lanthanoids, but the separation

F. Xie et al. / Minerals Engineering 56 (2014) 1028

ever, there is fundamental shortcoming with this conguration if

LaA3 Ce3 CeA3 La3

Reux minimizes dilution and also reduces the number of stages

Fig. 5. Simplied conguration of countercurrent solvent extraction circuit with reux.

F. Xie et al. / Minerals Engineering 56 (2014) 1028

Bastnesite concentrate (60% REO)

Residue for Ce recovery

Solvent extraction (Nd/Sm)/stripping

Raffinate (for recovery of

Raffinate fed to the

Eu(3) Chloride solution

extraction (McGill, 1997). A schematic owsheet of the process is

F. Xie et al. / Minerals Engineering 56 (2014) 1028

Separation, La/Ce, Pr, Nd

Separation, Ce/Pr, Nd, Sm

Ln3 3NO3 xR4 N NO3 n LnNO3 xnR4 N NO3