Journal of Rare Earths 42 (2024) 629e642

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Journal of Rare Earths

journal homepage: http://www.journals.elsevier.com/journal-of-rare-earths

Recent process developments in beneficiation and metallurgy of rare

earths: A review*
Shaokai Cheng a, b, Wenbo Li a, b, *, Yuexin Han a, b, Yongsheng Sun a, b, Peng Gao a, b,
Xiaolong Zhang a, b
a
School of Resources and Civil Engineering, Northeastern University, Shenyang, 110819, China
b
National-local Joint Engineering Research Center of High-efficient Exploitation Technology for Refractory Iron Ore Resources, Shenyang, 110819, China

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

Article history: Rare earth elements (REEs) are irreplaceable materials supporting low-carbon technology and equip-
Received 11 January 2023 ment, and their commercial demand and strategic position are becoming increasingly prominent. With
Received in revised form the continuous depletion of rare earth (RE) resources, developing high-efficiency beneficiation and eco-
7 March 2023
friendly metallurgical processes has attracted widespread attention. This paper reviews the major
Accepted 20 March 2023
Available online 29 March 2023
minerals exploited for RE production and their deposits, as well as the beneficiation and metallurgical
processes of RE minerals. Bastnaesite, monazite, mixed RE ores, and ion-adsorption clays are the main
raw materials in the world to date. RE-bearing ores (except ion-adsorption minerals) are generally
Keywords:
Rare earths
beneficiated by flotation, gravity and magnetic separation techniques. The mainstream metallurgical
Beneficiation processes processes for bastnaesite, monazite and mixed RE concentrates are oxidation roastingeHCl leaching,
Metallurgical processes caustic soda decomposition and high-temperature concentrated sulfuric acid roasting, respectively. Ion-
Cleaner production adsorption clays are directly processed by in situ leachingeprecipitation/solvent extraction. To achieve
the sustainable development of RE resources, it is essential to further explore innovative techniques to
achieve comprehensive utilization and cleaner production.
© 2024 Published by Elsevier B.V. on behalf of Chinese Society of Rare Earths.

1. Introduction commercial demand, HREEs are considered to be the most

economically critical REEs.7
Rare earth elements (REEs) are a group of 17 elements with Due to the unique physical and chemical properties, REEs are
similar atomic structures and chemical properties, composed of extensively used in industry, agriculture and military fields. In in-
lanthanides (La to Lu), scandium (Sc) and yttrium (Y). According to dustry, REEs, known as “vitamins”, are indispensable in new energy
their similarities and differences, these elements are usually batteries, electronic devices and even daily-use headphones.
divided into light rare earth elements (LREEs: La to Eu) and heavy Moreover, adding REEs to iron, copper, nickel and other metals
rare earth elements (HREEs: Gd to Lu and Y).1 The description of greatly improves the performance of the materials.8 REEs are also
REEs properties is present in Table 1.2e5 Except for La, Ce, Gd and Lu used as fertilizers to accelerate the germination and growth of
have 4fne15d16s2 electron configuration, and the other lanthanides plants. Such application is beneficial to crop yield improvements.9
are in4fn6s2 electron configuration.2 Moreover, as the atomic Since REEs have excellent optical, electrical and magnetic proper-
number increases, the lanthanides exhibit a larger-than-expected ties, they can enhance the performance of military weapons and
decrease in atomic or ionic radius (RE3þ), denoted as lanthanide equipment and are considered strategic resources.10,11
contraction.6 Because of the low natural abundance and high The name “rare earths” is misleading because these elements
were initially thought to be rare on Earth. In fact, rare earth (RE)
resources are quite abundant worldwide. According to statistics
* from the United States Geological Survey (USGS), the world's RE
Foundation item: Project supported by the National Key R&D Program of
China (2022YFC2905800, 2021YFC2901000) and the National Natural Science reserves in 2021 were approximately 125 million tons, of which
Foundation of China (52174242, 52130406). China's reserves were 44 million tons, accounting for approxi-
* Corresponding author. School of Resources and Civil Engineering, Northeastern mately 35%, followed by Vietnam, Brazil, Russia and other coun-
University, Shenyang, 110819, China.
tries. China is also the world's largest producer of REEs and
E-mail address: [email protected] (W. Li).

https://doi.org/10.1016/j.jre.2023.03.017
1002-0721/© 2024 Published by Elsevier B.V. on behalf of Chinese Society of Rare Earths.
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

Table 1
Description of REEs properties.

Elements Atomic number Electron configuration Valence Atomic radius (pm) Ionic radius (pm) Abundance in the upper crust (ppm)

RE2þ RE3þ RE4þ

Sc 21 3d14s2 3 160.6 73.2 14

Y 39 4d15s2 3 181 89.3 21
La 57 5d16s2 3 187.7 106.1 31
Ce 58 4f15d16s2 3, 4 182.5 103.4 92.0 63
Pr 59 4f36s2 3, 4 182.8 101.3 90.0 7.1
Nd 60 4f46s2 3 182.1 99.5 27
Pm 61 4f56s2 3 181.0 111.0 97.9 e
Sm 62 4f66s2 2, 3 180.2 109.0 96.4 4.7
Eu 63 4f76s2 2, 3 204.2 95.0 1
Gd 64 4f75d16s2 3 180.2 93.8 4
Tb 65 4f96s2 3, 4 178.2 92.3 84.0 0.7
Dy 66 4f106s2 3 177.3 90.8 84.0 3.9
Ho 67 4f116s2 3 176.6 89.4 0.83
Er 68 4f126s2 3 175.7 94.0 88.1 2.3
Tm 69 4f136s2 3 174.6 93.0 86.9 0.3
Yb 70 4f146s2 2, 3 194.0 85.8 2.2
Lu 71 4f145d16s2 3 173.4 85.0 0.31

dominates the RE industry.12 Detailed statistics are shown in Bastnaesite is generally distributed in carbonatite or carbonatite-
Fig. 1,12 and the major RE deposits are shown in Table 2.13 The RE related RE deposits and is associated with gangue minerals such
production of the world and China in the past decade (Fig. 2) shows as fluorite, dolomite, barite, and quartz.17
that the demand is continuously rising. The Mountain Pass deposit, located in California, USA, is a
famous bastnaesite deposit with an average thickness of 75 m that
dips at an angle of 45 to the southwest.18 This deposit is a
2. Major minerals for RE production and their deposits
carbonatite-related primary magmatic rock enriched with LREEs,
strontium and barium.19,20 Bastnaesite is the major RE mineral with
At present, more than 250 kinds of RE minerals have been
an REO grade of 7.98%, while monazite is present as a minor min-
identified worldwide; Table 3.5,14 shows the common RE-bearing
eral.4,21 The ores also contain approximately 65% calcite and/or
minerals and their formulae. However, the raw materials for RE
dolomite, 20%e25% barite, and other gangue minerals, such as
production are mainly bastnaesite, monazite, and mixed RE ores
strontianite and talc.22 The Mountain Pass deposit was mined for
with bastnaesite and monazite. Ion-adsorption clays are also
RE ores in 1954 by Molycorp (originally Molybdenum Corporation
important resources for extracting REEs.15,16
of America). From the 1960s to the 1990s, this deposit was the most
important RE supply source in the world. Due to the development
2.1. Bastnaesite of China's RE industry and other factors, the mining of the deposit
was stopped from 1998 to 2012 and 2015e2020.5 According to
Bastnaesite is the most common RE mineral and the primary statistics from the USGS, RE production in the USA was 43000 t in
source of LREEs. The content of rare earth oxides (REO) is approx- 2021, most of which came from the Mountain Pass deposits.12
imately 70%, mainly composed of cerium and lanthanum.4 The Maoniuping deposit in China is also a typical RE deposit
containing bastnaesite.23 This deposit is hosted by a hydrothermal
carbonatite-related complex, and the orebodies are mainly in the
form of veins or stockwork. The ores are abundant in LREEs and
have associated elements such as barium, lead, and bismuth.
Moreover, this deposit is unique in that the ores are easy to mine
and beneficiate.19,24 The reported RE reserves comprise 3.17 million
tons REO at an average grade of 2.95 wt%, of which cerium,
lanthanum, praseodymium, and neodymium account for more than
98%.16,25 The RE minerals are primarily bastnaesite with a crystal-
line particle size of approximately 0.1 mm. The gangue minerals are
mainly fluorite and barite with industrial production potential, as
well as quartz and calcite.26 In 2008, Jiangxi Copper Corp. acquired
the mining rights of this deposit and conducted feasibility studies
on the comprehensive utilization of RE and other valuable minerals.
Then, a concentrator with a processing capacity of 4200 t/d was
built in 2016 to produce bastnaesite concentrate.27
In addition, RE deposits such as the Dong Pao deposit in Vietnam
and the Weishan Lake deposit in China provide bastnaesite for RE
production.28

2.2. Monazite

Monazite, another important raw material for RE production, is

Fig. 1. Distribution of global RE reserves and production in 2021. a phosphate mineral containing 20%e30% Ce2O3, 10%e40% La2O3,
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S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

Table 2
Major RE deposits in the world.

Deposits Location RE-bearing mineral(s) Main elements

Bayan Obo China Bastnaesite, parasite, monazite La, Ce, Nd

Mountain Pass USA Bastnaesite LREEs
Mount Weld Australia Apatite, monazite, synchysite, churchite LREEs
Ilimaussaq Denmark Eudialyte, steenstrupine La, Ce, Nd, HREEs
Pilanesberg South Africa Eudialyte Ce, La
Steenkampskraal South Africa Monazite, apatite La, Ce, Nd
Hoidas Lake Canada Apatite, allanite La, Ce, Pr, Nd
Thor Lake Canada Bastnaesite La, Ce, Pr, Nd, HREEs
Strange Lake and Misery Lake Canada Gadolinite, bastnaesite La, Ce, Nd, HREEs
Nolans Bore Australia Apatite, allanite La, Ce, Nd
Norra Ka€rr Sweden Eudialyte La, Ce, Nd, HREEs
Khibina and Lovozero Russia Eudialyte, apatite LREEs, Y, minor HREEs
Nkwombwa Hill Zambia Monazite, bastnaesite LREEs
Kagankunde Malawi Monazite, bastnaesite LREEs
Tundulu Malawi Synchesite, parasite, bastnaesite LREEs
Songwe Malawi Synchesite, apatite LREEs, Nd
Chinese ion-adsorption deposits China Clay minerals La, Nd, HREEs
Maoniuping China Bastnaesite LREEs
Dong Pao Vietnam Bastnaesite, parisite LREEs

Beach sand is the main raw material for producing monazite

concentrate, which is easy to mine and has high economic value.
Monazite is a by-product of extracting ilmenite, rutile, cassiterite,
and zircon from beaches.31 Monazite-rich beaches are mainly
exploited in Australia, India, and Brazil but also in South Africa, the
USA, China, and Malaysia. The 20th century was an era of wide-
spread monazite mining from beaches. However, because the
inefficient utilization of thorium in monazite polluted the envi-
ronment, many countries have banned the exploitation of mona-
zite, resulting in a gradual decrease in production.32e34
The Mount Weld deposit is an RE deposit in Western Australia
containing niobium, tantalum, and phosphate minerals. This de-
posit is a laterite layer 70e130 m thick with an average REO grade
of 9.8 wt% on top of alkaline carbonatite.35 REEs are decomposed
from primary apatite and redeposited as secondary monazite,
which is characterized by relatively low contents of thorium and
uranium. Furthermore, high-value xenotime has been explored in
this deposit.36 The mining and development rights of the Mount
Weld deposit are owned by Lynas, the second largest RE producer
Fig. 2. RE production in the world and China in the past decade.
in the world.37

Table 3
Major RE-bearing minerals and their formulae.

Minerals Formula
2.3. Mixed RE ores with bastnaesite and monazite
Allanite (Y,La,Ca)2(Al,Fe3þ)3(SiO4)3(OH)
Apatite (Ca,La)5(PO4)3(F,Cl,OH)
Bayan Obo, located in Inner Mongolia, China, is considered the
Bastnaesite (La,Y) (CO3)F
Eudialyte Na4(Ca,La)2(Fe2þ,Mn2þ,Y)ZrSi8O22(OH,Cl)2 largest RE deposit in the world. It is also a deposit where bast-
Fergusonite (La,Y)NbO4 naesite and monazite coexist.38 The composition of this deposit is
Limoriite Y2(SiO4) (CO3) traditionally divided into nine lithological units, named H1 to H9.
Kainosite Ca2(Y,La)2Si4O12(CO3)$H2O All units except H8 are mainly composed of meta-sandstones and
Loparite (La,Na,Ca) (Ti,Nb)O3
Monazite (La,Th)PO4
slates, while H8 is dominated by dolomite. REEs coexisting with
Mosandrite (Na,Ca)3Ca3La (Ti,Nb,Zr) (Si2O7)2(O,OH,F)4 iron ore and other minerals are mainly hosted in dolomite. The
Parisite Ca(La)2(CO3)3F2 origin of dolomite is controversial; one view holds that dolomite
Pyrochlore (Ca,Na,La)2Nb2O6(OH,F) evolved from magmatic rocks, while the other holds that dolomite
Rinkite (Rinkolite) (Ca,La)4Na(Na,Ca)2Ti(Si2O7)2(O,F)2
evolved from sedimentary rocks.39e41 This deposit contains 71 el-
Steenstrupine Na14La6Mn2Fe2(Zr,Th) (Si6O18)2(PO4)7$3H2O
Synchysite Ca(La) (CO3)2F ements and more than 170 minerals. The proven resource reserves
Xenotime YPO4 include 35 million tons REO (average grade ¼ 6 wt%), 1400 million
Zircon (Zr,La)SiO4 tons iron ore, 100 million tons fluorite, and 3.2 million tons Nb2O5.
The ratio of bastnaesite to monazite in the deposit is approximately
3:1, and REEs are recycled from iron ore processing tailings.42,43
and 4%e12% ThO2. It is commonly hosted in magmatic rocks or
There are three mining areas in the Bayan Obo deposit. The Main
metamorphic rocks. Unlike bastnaesite, monazite generally in-
Ore Body and West Ore Body were mined by Baotou Iron and Steel
cludes more radioactive elements such as thorium.29,30
Group in 1957, and the West Ore Body was exploited in 2004.5
631
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

2.4. Ion-adsorption clays preconcentrate the Nechalacho RE deposit located in northwest

Canada. The results showed that the valuable minerals can be
Ion-adsorption deposits (weathering crust deposits) are a effectively concentrated by gravity separation even in poorly
unique type of RE deposit with HREEs that are characterized by the liberated conditions. The feasibility of upgrading REEs using gravity
adsorption of RE ions on clays, dominantly kaolinite and halloysite. separation units to recover iron oxide silicate-rich tailings con-
These deposits are weathered granite on the bare ground, with a taining low-grade REO in Australia was studied by Abaka-Wood
thickness of 5e30 m, generally 8e10 m. In addition, REEs can be et al.13
readily extracted without leaching radioactive elements.44,45
Although the REO grade ranges from 0.05 wt% to 0.3 wt%, the 3.2. Magnetic separation
content of HREEs is very high. Therefore, these deposits are
extremely valuable resources.46 Because the formation of these Magnetic separation is applied to recover RE minerals according
deposits requires special geological and climatic conditions, they to the differences in the specific magnetization coefficient between
have been commercially developed only in the south of China and RE and other minerals (nonmagnetic minerals and highly magnetic
Southeast Asia.47 Ion-adsorption type deposits were first explored minerals). It can be used to eliminate highly magnetic minerals or
in Jiangxi Province of China in 1969.48 In 2021, the RE production to concentrate the desired paramagnetic RE minerals. Many types
allocated to ion-adsorption clays in China was 19150 t, and the RE of devices are available, which can be classified into low-intensity
output in Burma was 26000 t; most of the raw materials came from magnetic separators (LIMSs) and high-intensity magnetic separa-
ion-adsorption clays. tors (HIMSs).57
In the beneficiation process of beach sand, ilmenite is removed
3. Beneficiation techniques of RE ores by LIMS separation, and monazite is upgraded by HIMS separation.
In the evaluation and feasibility verification of a placer deposit in
RE ores are generally associated with other minerals, such as North Korea, magnetic separation with different magnetic field
fluorite, barite, and iron-bearing minerals. The content of REO in raw strengths was used to selectively recover monazite/xenotime
ores is low, so metallurgical processes cannot be carried out directly. (magnetic field strength of 800e1120 kA/m) and ilmenite (mag-
According to the differences in specific gravity, magnetism, con- netic field strength of 640 kA/m). Zircon was obtained by additional
ductivity and floatability between RE ores and associated minerals, gravity separation. The results showed that the content of ilmenite
mineral dressing processes are adopted to produce high-grade RE increased from 32.5% to 90.9%, the REO grade of monazite/xen-
minerals. The enriched concentrates usually contain 50 wt%e60 wt% otime reached 45.0%, and the content of zirconium in zircon was
REO, which can reduce the energy consumption and dosage of 42.8%.58
chemical reagents in metallurgical processes. The beneficiation At present, the separation of Bayan Obo ores involves a com-
methods of RE ores mainly include gravity separation, magnetic bined process of magnetic separation and froth flotation. LIMS and
separation, electrostatic separation and froth flotation. Ores are HIMS processes are used to utilize magnetite and haematite from
generally wet in the beneficiation process, but the operation of raw ores, and then RE minerals and fluorite are recovered from the
electrostatic separators requires materials to be dry. Therefore, magnetic separation tailings by sequential flotation. Fig. 3 shows
considerable energy is consumed to drive off all moisture prior to the magnetic separation process, which can successfully separate
electrostatic separation, and the use of electrostatic separation in RE minerals and iron-bearing minerals.55 Wang et al.59 proposed a
industrial production is relatively limited.49,50 In general, the vast stepwise magnetic separation process to preconcentrate iron, RE
majority of beneficiation processes is combination of gravity sepa- minerals, and fluorite minerals from Bayan Obo ores. Their study
ration, magnetic separation, and froth flotation.4

3.1. Gravity separation

The specific gravity of RE minerals is relatively high (2.9e7.2),

while the density of gangue minerals (mainly silicate) is low.
Therefore, gravity separation is an important technique for
concentrating RE minerals.51,52 Extensively used gravity separation
devices include shaking tables, conical separators, and spiral
concentrators.
Gravity separation is commonly applied to extract monazite
from beach sand. Valuable heavy minerals such as ilmenite,
monazite, zircon, and rutile are selectively recovered by related
gravity separators. Then, according to the discrepancies in
magnetism and conductivity of these heavy minerals, monazite
concentrate is obtained via electrostatic separation and magnetic
separation. Moustafa et al.53 successfully extracted monazite
concentrate from Egyptian beaches by this process. Moreover,
Rejith et al.54 used a similar process to obtain ilmenite and by-
products such as monazite, zircon and rutile.
Gravity separation is also used to pre-treat RE-bearing ores. An
example of this approach is in use at Maoniuping, where gravity
separation by shaking tables is employed after grinding and clas-
sifying. The overall grade of the gravity concentrate is 30% REO with
a recovery of 74.5%. Then, bastnaesite concentrate suitable for
metallurgy is obtained by flotation.55 Marion et al.56 proposed the Fig. 3. Magnetic separation flowsheet of RE minerals and iron-bearing minerals in
use of a spiral concentrator and a Knelson concentrator to Bayan Obo.

632
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

adopted the superconducting magnetic separator developed in to the complex composition of RE ores and the different steps
recent years, which can improve the magnetic separation efficiency involved in measuring IEP, there are great differences in IEP values
and simplify the subsequent flotation process. reported in the literature, which range from pH 1.1 to 9.0 for
Ferruginous RE-bearing ores derived from lateritic deposits are monazite and pH 4.6 to 9.5 for bastnaesite.62
generally laborious to be beneficiated by conventional processes
due to the complex texture of the ores. Magnetization roasting
3.3.2. Collectors in flotation
followed by LIMS separation is a potential avenue to concentrate RE
In the flotation of RE minerals, particularly bastnaesite and
minerals. This process can produce an iron-rich magnetic product,
monazite, the typical collectors include hydroxamates, carboxyl-
while RE minerals are enriched in the tailings.60
ates and phosphates. The key difference between these three re-
agents is the atom to which the oxygen atoms are attached (carbon,
3.3. Froth flotation nitrogen and phosphorous, respectively).62,67

Among beneficiation techniques, froth flotation is the most 3.3.2.1. Hydroxamate collectors. Hydroxamates (hydroxamic acids
well-established technique to concentrate RE minerals and can and their salts) are important collectors in the flotation of bast-
process a wide range of fine particle sizes. Due to the difference in naesite and monazite due to their good capture performance.
hydrophilicity between RE minerals and associated minerals, Multiple studies on adsorption mechanisms have shown that
flotation reagents are added to achieve separation. This technique various hydroxyl complexes hydrolysed by RE minerals form stable
has a high utilization rate of RE resources and has been applied to chelates with hydroxamates, which are adsorbed on the surface of
industrial-scale production of ores from Bayan Obo, Mountain Pass minerals.7 In general, the optimum pH of flotation experiments
and Weishan Lake with the process flow charts in Fig. 4.55,61 It is occurs at approximately pH ¼ 9, which is approximately the pKa of
worth mentioning that the flotation feed of Mountain Pass and hydroxamates. At this pH, the hydroxyl complexes on the surface of
Weishan Lake is the raw ore, while the flotation feed of Bayan Obo minerals are mainly RE(OH)2þ and RE(OH)þ 2 . Therefore, these two
is derived from iron ore processing tailings. At present, the focus of complexes play an important role in the interactions between RE
flotation research is the development and application of new minerals and hydroxamates.64,68 Fig. 5 shows the formation of
reagents.62 chelates when hydroxamic acid is used as a collector.7 The RE in
RE(OH)2þ and RE(OH)þ 2 replaces the hydrogen atoms of the
3.3.1. Surface chemistry hydroxyamide groups and forms stable closed-loop chelates with
When minerals liberate ions within water (the processes of carbonyl oxygen atoms. Meanwhile, the formation of new bonds
liberating ions include but are not limited to dissolution, hydration results in breakage of the bonds between REs and water molecules.
and surface group dissociation), the surface of the minerals will
acquire a charge and attract ions with the opposite charge. There-
fore, an electric double layer (EDL) is formed at the solid‒liquid
interface. The potential determining ions in the inner layer of the
EDL affect which ions can bond with minerals.63 In froth flotation,
most flotation reagents are in the ion state in mineral pulp, and the
adsorption of reagents is governed by the EDL. An important
property characterizing the EDL is the isoelectric point (IEP), which
is the pH value where the zeta potential is zero.64 According to the
IEP of a mineral, the sign of the charge on the mineral surface at a
given pH value can be predicted, which is helpful to analyse the
adsorption mechanism of reagents.65 The adsorption of reagents on
the mineral surface mainly occurs through electrostatic attraction,
chemical bonds, hydrogen bonds, and van der Waals forces.66 Due Fig. 5. Formation of chelates when hydroxamic acid is used as a collector.

Fig. 4. Flotation separation flowsheet to enrich RE minerals in Bayan Obo (a), Mountain Pass (b) and Weishan Lake (c).

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S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

Chapleski et al.69 examined five functionalized hydroxamic acid 3.3.2.3. Phosphate collectors. Phosphoric acid-based collectors are
ligands as potential collectors for bastnaesite and developed a potential agents for RE minerals that have been explored in recent
systematic relationship connecting the structure to the adsorption years. The structure of these collectors is shown in Fig. 6 and is
activity. The results could motivate the design of improved flotation different from the structure of phosphonate (CPO(OH)2 or
collectors for RE ores. In the study of the flotation of bastnaesite and CPO(OR)2).67 The adsorption mechanism of phosphoric acid esters
monazite with a benzo-hydroxamate collector, it was found that is believed to be that metal cations (including their hydroxyl
the adsorption of carbonate precipitates and Ca2þ on the mineral complexes, Menþ) replace the hydrogen atoms of PeO groups to
surface reduced the adsorption of the collector. This phenomenon form new compounds. However, the structure of the newly formed
confirms that high-efficiency flotation does not rely solely on the compounds has not been well investigated. Fig. 7 shows the
strength of collectoremineral interactions but rather is highly possible structures of these compounds when organic phosphoric
dependent on the chemistry of the flotation solution.70 Further- acid is used as a collector.74 Jordens et al.73 studied the collection
more, increasing temperature is likely to promote the floatability performance of benzohydroxamic acid, sodium oleate and Flotinor
and selectivity of RE ores. In industry, the flotation of RE minerals is SM15 (a commercial phosphoric acid ester) in the flotation of
carried out at elevated temperatures. In a flotation experiment of bastnaesite. The micro-flotation results showed that all three col-
Bayan Obo RE ores by naphthyl hydroxamic acid, the influence of lectors can successfully recover bastnaesite, but SM15 is the least
temperature on the collection performance was investigated. The selective collector, as it floated both quartz and bastnaesite. The
results indicated that the adsorption stability of bastnaesite and oxygen atoms in phosphoric acid esters are more available than
monazite increased as the temperature increased to the optimum other oxygen atoms to react with metal cations, so the selectivity of
temperature of 75  C, but the adsorption stability of monazite was phosphate ester is generally the lowest. However, compared to the
not as high as that of bastnaesite.71 normal collector concentration when using hydroxamates, excel-
lent flotation of bastnaesite is achieved at a low concentration
3.3.2.2. Carboxylate collectors. Carboxylates, generally represented when using phosphoric acid esters. Relevant literature has
by oleic acid, sodium oleate, tall oils and phthalic acid, are typical confirmed that lauryl phosphate has stronger hydrophobicity and
collectors in industrial practice. Relevant studies have explained better selectivity for bastnaesite at a lower collector concentration
that the adsorption mechanism of carboxylates on the surface of than octyl hydroxamate.78,79 In addition, Liu et al.80 examined the
bastnaesite is chemisorption. Carboxylates react with RE cations selective flotation of bastnaesite from calcite with 2-ethylhexyl
and their hydroxyl complexes to form compounds, which are phosphate and lauryl phosphate. The results suggest that the
adsorbed to the mineral surface.72 Although carboxylates are lower reactivity of 2-ethylhexyl phosphate accounts for the higher
inexpensive compared with hydroxamates, selectivity in flotation is selectivity.
a problem. For this reason, elevated temperatures and various de-
pressants are normally employed to achieve selective separation. 3.3.3. Depressants in flotation
An example of industrial production is the flotation of bastnaesite In flotation, the types of gangue minerals and collectors deter-
from Mountain Pass ores.61 In a flotation experiment of bastnaesite mine the selection of depressants, which mainly consist of sodium
using sodium oleate, the maximum floatability occurred at pH 9,73 silicate, lignin sulfonate, sodium metasilicate, and sodium sul-
while another study reported that the optimum pH value ranged fide.81,82 Sodium silicate, also known as water glass, is employed to
from 4 to 8.74 These different results may be due to differences in depress quartz, silicate minerals, aluminosilicate minerals, etc. At
the origin of the bastnaesite and minor impurities in the samples. Bayan Obo, sodium silicate was identified as an important
Carboxylates are also used in the flotation of monazite. Beach sand depressant to achieve selective separation of RE minerals from
is the main source of monazite, and rutile and zircon are typical gangue with hydroxamate collectors. However, the dosage of so-
gangue minerals in the beneficiation of monazite. Monazite can be dium silicate was large enough (25 kg/t) in the flotation process.
selectively captured using carboxylate collectors and related de- Further research suggested that the combination of sodium silicate
pressants.75 In addition, fatty acids and collectors related to fatty with alum or carboxymethyl cellulose (CMC) could reduce the
acids are used in the flotation of monazite from Mount Weld ores, dosage of depressant, as alum was effective in suppressing barite
but there is no literature reporting the specifics of the flotation and CMC is a common inhibitor of calcite.4,83 In a flotation exper-
process.76 Compared to bastnaesite, the adsorption of collectors on iment of monazite from hematite and quartz mixtures with
monazite surfaces has been reported to occur over a wider pH range hydroxamic acid, a blend of sodium silicate and starch showed
of 3e11. The adsorption mechanisms of monazite are physisorption efficient depression and enhanced the recovery of REO.84 Lignin
at pH 3 and chemisorption in the pH range of 6e9.62 At Bayan Obo, sulfonate was applied to depress calcite, barite, and other gangue
a mixed RE concentrate composed of bastnaesite and monazite is minerals at Mountain Pass. Elevated temperatures were proven not
produced in the mineral dressing process. The metallurgical pro- to influence the depression of lignin sulfonate, but an excessive
cess of this mixed concentrate is quite complex compared with dosage of lignin sulfonate affected the collector performance for
those of bastnaesite or monazite alone. Therefore, on the basis of bastnaesite.85,86 In the flotation of monazite from a system con-
the better collecting capacity of phthalic acid for bastnaesite than taining rutile and zircon, Pavez and Peres87 explored the perfor-
monazite, researchers selectively separated bastnaesite from mance of two depressants (sodium metasilicate and sodium
monazite by froth flotation.77 sulfide), and the results showed that sodium metasilicate is more

Fig. 6. Structure of phosphate collectors. Note: R1, R2 and R3 are alkyl groups or Fig. 7. Structures of the newly formed compound. (a) Covalent bond formation with
hydrogen, but not all of them are hydrogen. the metal cation; (b) Bidentate complex formation; (c) Binuclear complex formation.

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effective than sodium sulfide as a depressant for zircon and rutile. vapour in the air (Eq. (2)). Moreover, most cerium is further
In addition, sodium fluorosilicate, sodium fluoride, and sodium oxidized to ceria (CeO2), accompanied by the formation of cerium
hexametaphosphate can be used as depressants in the flotation of fluoride (CeF3) (Eqs. (3) and (4)).95 The reaction of leaching roasted
RE minerals.62 products with dilute HCl is shown in Eq. (5). During the leaching
procedure, a rare earth chloride (RECl3) solution consisting of non-
3.3.4. Other agents in flotation cerium and a small amount of trivalent cerium is obtained by
There are also many other reagents commonly used in the adjusting the acidity, while CeO2 and rare earth fluorides (REF3)
flotation of RE minerals. Sodium carbonate is used as a pH modifier remain in the residue due to their acid-insoluble nature. Then,
in bastnaesite flotation, and carbonate ions can affect both the pH of caustic conversion is used to convert CeO2 and REF3 into rare earth
pulp and the zeta potential of minerals. In a study of the effect of hydroxides (RE(OH)3) (Eqs. (6) and (7)). After removal of fluorine by
sodium carbonate on the flotation of bastnaesite (in a system washing, cerium-rich RECl3 solution is generated by adding HCl and
composed of bastnaesite, calcite and barite), the barite surface was a relevant reducing agent. Ultimately, high-purity REO products are
converted to barium carbonate as the pH reached 9 by adding so- acquired through neutralization, solvent extraction, precipitation,
dium carbonate, and the surface charge of barite was positive. In and calcination.
this case, the negatively charged depressant, lignin sulfonate, was
more easily adsorbed on the surface of barite.85,88 Oxalic acid (as RECO3 F / REOF þ CO2 [ (1)
both a pH modifier and depressant) and sodium oxalate (as both an
activator and depressant) are reported to enhance the flotation 2REOF þ H2 O / RE2 O3 þHF [ (2)
efficiency of RE minerals. Oxalate anions fix ions produced by the
dissolution of gangue minerals through chelation.4,89 Citric acid
6CeOF þ O2 /4CeO2 þ2CeF3 (3)
and ethylenediamine tetraacetic acid (EDTA) are used to clean
calcium ions from the surface of monazite, which can increase the
recovery of REO.90 EDTA is also considered an effective depressant 2Ce2 O3 þ O2 /4CeO2 (4)
for fluorite in the flotation of bastnaesite.91 In addition, metal salts
(such as lead nitrate, cobalt nitrate, and ferric chloride) may be used 3REOF þ 6HCl / RECl3 þREF3 Y þ 3H2 O (5)
as activators to increase the number of collector adsorption sites,
enhancing the floatability of RE minerals.92 CeO2 þ4NaOH / CeðOHÞ4 Y þ 2Na2 O (6)

4. Metallurgical techniques of RE concentrates

REF3 þ3NaOH / REðOHÞ3 Y þ 3NaF (7)
4.1. Metallurgical techniques of bastnaesite Although the industrial application of this technique has been
realized, there are problems such as a complex procedure, large
At present, the mature industrial process used to extract REEs consumption of acid and alkali, and environmental pollution by
from single bastnaesite concentrates is oxidation roastingeHCl fluorine-bearing waste gas and water. To achieve the greener
leaching-caustic conversion.93,94 and the specific process flow is effective utilization of bastnaesite, a series of new metallurgical
shown in Fig. 8.17,94 Bastnaesite concentrate typically decomposes processes have been developed in recent decades. Fig. 9 shows the
(Eq. (1)) at a roasting temperature of approximately 700  C, and a
small amount of decomposition products can also react with water

Fig. 8. Flowsheet for the processing of bastnaesite by oxidation roastingeHCl leach-

ingecaustic conversion. Fig. 9. Technological flowsheet of cerium oxide enrichment by two-step HCl leaching.

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process of cerium oxide enrichment from bastnaesite by two-step

HCl leaching, which was reported by Chi et al.96 Bastnaesite was NH4 Cl / NH3 [ þ HCl [ (12)
converted to REO by adding sodium carbonate (Na2CO3) during
oxidation roasting, in which most of the cerium existed as CeO2 RE2 O3 þ6HCl / 2RECl3 þ3H2 O (13)
(Eqs. (1), (8) and (9)). After washing with water and first leaching
with dilute HCl, sludge rich in CeO2 was obtained. Then, the sludge
was further leached with concentrated HCl and H2O2 to form
cerium chloride (CeCl3) solution. Cen et al.97 developed a novel 4.2. Metallurgical techniques of monazite
beneficiation-metallurgy combined process based on calcification
roasting (Fig. 10). Bastnaesite was roasted with calcium hydroxide The metallurgical techniques of monazite follow two main
(Ca(OH)2) to form REO and calcium fluoride (CaF2) (Eq. (10)). These paths: acid treatment by sulfuric acid and alkaline decomposition
two techniques can effectively limit the discharge of gaseous by sodium hydroxide. Alkaline decomposition is the preferred in-
fluorine and simplify the metallurgical processing of bastnaesite. In dustrial technique for the processing of high-grade monazite sands,
particular, with the second technique, fluorine can be recovered in while acid treatment is typically used for lower grade ores/
the form of fluorite, realizing the comprehensive utilization of concentrates.100
bastnaesite. In addition, ammonium chloride (NH4Cl) roasting fol- The process of sulfuric acid roastingewater leaching is a tradi-
lowed by hot water leaching is a technique for extracting REEs from tional technique used to extract REEs from monazite (Fig. 11).100 In
bastnaesite.98 However, REF3 (one of the decomposition products this process, monazite is roasted with concentrated sulfuric acid,
during roasting) does not react with NH4Cl, causing a significant and its phosphate structure is destroyed (Eqs. (14) and (15)). Then,
loss of REEs during hot water leaching. Chi et al.99 proposed a novel the leaching solution, including rare earth sulfates (RE2(SO4)3) and
process of fluorine deactivation by adding magnesium oxide (MgO) thorium sulfate (Th(SO4)2), is obtained by leaching in water and
prior to chloride roasting, which can significantly improve the RE filtration. The method of subsequent precipitation varies widely
recovery. In this process, bastnaesite and MgO were roasted at and generally relies on reagents such as sodium hydroxide, oxalic
500  C to deactivate fluorine (Eq. (11)), and the decomposed acid, sodium carbonate or ammonia.29 In the separation process,
products were roasted again with NH4Cl to convert the REO into solvent extraction and ion exchange can be used to separate REEs
water-soluble RECl3 (Eqs. (12) and (13)). As a result, RE recovery and thorium (Th).101 Demol et al.102 examined the effect of sulfuric
increased significantly with a high purity of RE2O3 products. acid roasting temperature (between 200 and 800  C) on leaching
from monazite. It was observed that virtually complete dissolution
2REOF þ Na2 CO3 /RE2 O3 þ2NaF þ CO2 [ (8) of REEs, Th and phosphate was obtained during leaching after
roasting at 250  C. As the roasting temperature increased to 300  C,
the formation of thorium pyrophosphate led to a sharp decrease in
4CeOF þ 2Na2 CO3 þ O2 /4CeO2 þ4NaF þ 2CO2 [ (9)
the extraction of Th and phosphate, but the leaching of REEs
reached nearly 100%. The leaching of REEs, Th and phosphate
2RECO3 F þ CaðOHÞ2 /RE2 O3 þCaF2 þ H2 O [ þ 2CO2 [ (10) decreased in the range of 400e800  C. Kim et al.103 studied the
effect of mechanochemical treatment before sulfuric acid roasting.
2RECO3 F þ MgO / RE2 O3 þMgF2 þ2CO2 [ (11) A mixture of monazite and sodium hydroxide powder was milled to
form sodium phosphate and RE(OH)3. After removing the water-

Fig. 10. Technological flowsheet of calcification roastingegravity separationeHCl Fig. 11. Flowsheet for the processing of monazite by sulfuric acid roastingewater
leaching. leaching.

636
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

soluble sodium phosphate by washing, RE(OH)3 was mostly dis- phosphate with greater economic value than trisodium phosphate.
solved by concentrated sulfuric acid at room temperature. The re- The effects of roasting temperature, roasting time, and weight ratio
sults indicated that mechanochemical milling plays a significant (KOH to monazite) on the extraction of REEs, U, and Th were
role in enhancing the leaching of REEs and that the yield increased investigated. KOH was found to behave similarly to NaOH under the
with increasing milling time. Industrial operations using sulfuric conditions studied, but it is worth noting that the optimal roasting
acid roastingewater leaching face certain problems: the facilities temperature of KOH was 210  C, which was higher than that of
are corroded by sulfuric acid, and phosphorus in monazite cannot NaOH roasting.
be recovered.
REPO4 þ3NaOH/REðOHÞ3 Y þ Na3 PO4 (16)
2REPO4 þ3H2 SO4 /ðREÞ2 ðSO4 Þ3 þ2H3 PO4 (14)
Th3 ðPO4 Þ4 þ12NaOH/3ThðOHÞ4 Y þ 4Na3 PO4 (17)
Th3 ðPO4 Þ4 þ6H2 SO4 /3ThðSO4 Þ2 þ4H3 PO4 (15)
REðOHÞ3 þ3HCl / RECl3 þ3H2 O (18)
Caustic soda decomposition is a mainstream technique where
the phosphorus in monazite can be comprehensively recovered as a
ThðOHÞ4 þ4HCl / ThCl4 þ4H2 O (19)
marketable by-product. The specific process is shown in
Fig. 12.29,104 Sodium hydroxide (NaOH) solution is added to
monazite to form trisodium phosphate (Na3PO4), RE(OH)3 and
thorium hydroxide (Th(OH)4) at an appropriate temperature of
140e160  C (Eqs. (16) and (17)). After filtration and water washing, 4.3. Metallurgical techniques for mixed RE concentrates of
the hydroxide cake with P2O5 concentration <1% is leached in HCl bastnaesite and monazite
at pH 3.5 to obtain a solution including RECl3 and ThCl4 (Eqs. (18)
and (19)). By adjusting the pH in the range of 4e5, Th(OH)4 pre- Mixed concentrates of bastnaesite and monazite are commonly
cipitation can be formed to separate Th. The RECl3 solution is processed by sulfuric acid roastingewater leaching, which is the
further processed by solvent extraction, and REO products can be primary method for the treatment of RE concentrates obtained by
obtained using processes such as electrolysis, evaporation, crys- flotation in Bayan Obo. The sulfuric acid technique used to treat
tallization, and precipitation.29,104,105 This technique can efficiently Bayan Obo mixed RE concentrates was developed in the 1970s. In
utilize REEs from monazite, but the radioactive residue will pollute this process, low-temperature (<300  C) sulfuric acid roasting is
the environment. Even if Th is recovered by extraction technology, adopted (Eqs. (14), (15) and (20)), and then RECl3 mixtures are
there is no large-scale demand in relevant fields at present. Abdel- obtained by water washing, double salt precipitation, trans-
Rehim106 proposed an innovative method of alkaline leaching in a formation with alkali, and selective hydrochloric acid leaching
ball mill autoclave, where grinding and leaching of monazite took (Fig. 13).108 This technique has been replaced due to its disadvan-
place simultaneously. Due to the grinding action of the steel balls, tages of low RE yield, long flowsheet, tedious solid‒liquid transfers,
the hydroxide layer covering the monazite was removed, and and large amount of industrial wastewater.108,109
monazite leaching was intensified and accelerated. Galvin and
Safarzadeh107 reported the alkali roasting of monazite using po- 2RECO3 F þ 3H2 SO4 /RE2 ðSO4 Þ3 þ2HF [ þ 2CO2 [ þ 2H2 O
tassium hydroxide (KOH) in place of NaOH to obtain tripotassium
(20)
At present, 90% of Bayan Obo mixed RE concentrates are roasted
with concentrated sulfuric acid at high temperatures, which is
known as a third-generation sulfuric acid process in China. The
flowsheet is shown in Fig. 14.17 The RE concentrate is roasted in a
rotary kiln at a temperature of >300  C (Eqs. (14), (15) and (20)),
and the formation of water-insoluble thorium pyrophosphate
(ThP2O7) further occurs during roasting (Eqs. (21) and (22)).110
Water leaching followed by neutralization is used to obtain
RE2(SO4)3 solution. Finally, a single RE product is obtained by sol-
vent extraction or a mixed RE carbonate is obtained by precipita-
tion.17,93,109 Compared to other techniques, sulfuric acid roasting at
a high temperature is a mature process with the characteristics of
simple operation and high RE recovery. Moreover, thorium is left in
the residue and will not affect the quality of the RE products. The
disadvantage is that the off-gas containing sulfur dioxide and
hydrogen needs to be absorbed, and the discharge of solid radio-
active waste residue causes great pressure on the environment.55
As a result, multiple studies have focused on developing clean
processes of low-temperature sulfuric acid roasting combined with
highly efficient extractants. When the roasting temperature is
below 300  C, soluble thorium sulfate will be generated, and then
REEs and thorium can be separated by solvent extraction. Lu et al.111
synthesized a 2-ethylhexyl phosphorodiamidate extractant, which
was employed for the separation of thorium from REEs in a nitrate
medium. Dong et al.112 examined three kinds of neutral organo-
phosphorus extractants, and the experimental results indicated
Fig. 12. Flowsheet for the processing of monazite by caustic soda decomposition. that n-octyl phosphate diphenyl possessed excellent performance.
637
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

Fig. 14. Flowsheet for the processing of mixed RE concentrates by high-temperature

sulfuric acid roasting.

Fig. 13. Flowsheet for the processing of mixed RE concentrate by low-temperature

sulfuric acid roasting.

REPO4 þ3NaOH / REðOHÞ3 Y þ Na3 PO4 (24)

Th3 ðPO4 Þ4 þ12NaOH / 3ThðOHÞ4 Y þ 4Na3 PO4 (25)

2H3 PO4 / H4 P2 O7 þ H2 O [ (21)

ThðSO4 Þ2 þ H4 P2 O7 /ThP2 O7 þ2H2 SO4 (22)

4.4. Metallurgical techniques for ion-adsorption RE minerals
Caustic soda decomposition followed by HCl leaching is also
adopted for Bayan Obo mixed RE concentrates, as shown in Ion-adsorption RE minerals are mainly present as ion-
Fig. 15.108 NaOH can convert both bastnaesite and monazite into exchangeable phases adsorbed on clay minerals, which cannot be
RE(OH)3 (Eqs. (23)e(25). This alkaline technique is a relatively clean efficiently recovered by traditional dressing processes such as
smelting process, but it cannot be extensively used in industry for gravity, magnetic, electrostatic, and flotation separation. Since
Bayan Obo RE concentrate due to the restrictions of a low these special ores were discovered in 1969, a series of hydromet-
concentrate grade, expensive NaOH, and the large amount of allurgical techniques have been developed by researchers. Three
wastewater. Li et al.113 proposed that replacing traditional liquid generations of leaching processes, pool leaching, heap leaching and
alkali decomposition with solid NaOH roasting decomposition and the widely used in situ leaching, have been developed successively
raised the reaction temperature to 550  C because of the absence of in China.108 Ion-adsorption RE ores were initially leached in sodium
H2O. During roasting, the by-product Na2CO3 also reacted with chloride (NaCl) solution and subsequently precipitated with oxalic
REPO4 and REFCO3 to form RE2O3. The results of this study have acid (H2C2O4). The large amount of high-concentration NaCl
certain significance for the green extraction of mixed RE concen- wastewater produced in this process caused soil salinization. At
trates. Roasting RE concentrates with NaOHeAl(OH)3 is also an present, the in situ leaching process is extensively used in industry.
effective smelting method. The product Na3AlF6 is obtained Ammonium sulfate ((NH4)2SO4) is generally applied as a leaching
through the treatment of wastewater and can be used as a raw agent to leach REEs, and then a concentrate with an REO content
material for producing aluminium.114 exceeding 90% can be obtained by ammonium bicarbonate
(NH4HCO3) precipitation (Fig. 16).108,115 However, complex
geological conditions easily cause the leakage of leaching solution,
RECO3 F þ 3NaOH / REðOHÞ3 Y þ NaF þ Na2 CO3 (23)
resulting in severe ammonia-nitrogen pollution and high losses of
REEs.116
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tailings had a negative effect on plant growth. Xiao et al.119 further

investigated the effects of compound agents (MgSO4eNH4Cl,
MgSO4eCaCl2, and MgSO4eNH4CleCaCl2) on the leaching effi-
ciency of REEs and plant growth. When the mole ratio of
magnesium-ammonium-calcium was 15:25:60, a relatively good
leaching effect (leaching efficiency above 94%) was obtained
without affecting the growth of plants. Lai et al.120 studied the
leaching behaviour of ion-adsorption RE ores with MgSO4-ascorbic
acid as a compound agent. Since ascorbic acid forms a stable
complex with RE ions, it was used as an auxiliary agent to promote
the leaching of REEs, which could decrease the dosage of MgSO4.
Since leachate contains impurities such as Al3þ, Fe3þ, Ca2þ and
Si4þ, purification is needed. At present, neutralization is a common
impurity removal method in industry. The acidity of the solution is
adjusted to pH 4e5 by adding ammonia or ammonium bicarbonate,
and most of the impurity ions are precipitated in the form of hy-
droxides while RE ions remain in the solution.108 The concentration
of RE ions in purified leachate is low and needs to be enriched by
precipitation. Oxalic acid was initially used to precipitate REEs from
purified leachate. Currently, ammonium bicarbonate (NH4HCO3) is
used as a precipitant due to its low cost, wide availability and high
Fig. 15. Flowsheet for the processing of mixed-type RE concentrate by caustic soda recovery when precipitating REEs. However, the large consumption
decompositioneHCl leaching. of ammonium bicarbonate can lead to severe ammonia-nitrogen
pollution. For this reason, non-ammonia precipitation methods
have gradually attracted attention. Huang et al.121 proposed a
precipitation technique with magnesium oxide (MgO), and a pre-
cipitation efficiency of 99.6% was obtained under the optimal
conditions. Because of the poor solubility of MgO and the genera-
tion of RE2(OH)4SO4, the purity of the RE concentrate was only
85.89 wt%. Yu et al.122 adopted magnesium bicarbonate
(Mg(HCO3)2) as a substitute for NH4HCO3 to precipitate RE ions. The
results indicated that RE ions could be recovered efficiently and
that the filtrate after precipitation could be used to produce a pure
Mg(HCO3)2 solution.
Direct concentration techniques used to obtain an RECl3 solu-
tion without a precipitationecalcination process are also used to
enrich REEs from leaching solution. Chinese researchers have suc-
cessively explored solvent extraction, ion exchange, and liquid
membrane separation methods, but only solvent extraction
methods have been applied to industrial production.46 Solvent
extraction methods realize the enrichment of REEs through the
different extraction capabilities of extractants. Two problems must
be solved for applying solvent extraction in industrial production:
one problem is the dissolution loss of extractants, and the other is
the efficiency of extraction. Some commercial extractants, such as
naphthenic acid, P507, and P204, can be applied to extract REEs from
liquid media. To accommodate low-concentration leaching solu-
tions and improve the extraction efficiency, bubbling extraction
and centrifugal extraction have been developed on the basis of
mixing-settling extraction.123,124

5. Conclusions and recommendations

Fig. 16. Flowsheet for the processing of ion-adsorption RE ores by in situ leaching.
REEs play a crucial role in agriculture, industry, and modern
military. With the development of many high-tech industries, REEs
The development of environmentally friendly leaching agents to have become irreplaceable raw materials to support low-carbon
efficiently collect REEs from ion-adsorption RE ores has received clean technologies and equipment, and their commercial demand
widespread attention. Magnesium sulfate (MgSO4) has been pro- and strategic position are becoming increasingly prominent. This
posed to solve the problem of ammonia-nitrogen pollution. Its paper reviews the major minerals and their deposits that provide
leaching efficiency for REEs is basically the same as that using raw materials for production, as well as the beneficiation and
(NH4)2SO4, and the leaching efficiency of aluminium impurities can metallurgical processes of RE minerals. The schematic diagram is
be reduced.117,118 In a study using MgSO4 as a leaching agent, it was shown in Fig. 17. From the preceding review, the following con-
found that excessive ion-exchangeable magnesium in washing clusions and recommendations are provided.
639
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

Fig. 17. Schematic diagram of RE production.

(1) Of the over 250 RE minerals identified to date, only bast- Declaration of competing interest
naesite, monazite, xenotime and ion-adsorption RE minerals
are extracted commercially. Bayan Obo, Mountain Pass, The authors declare that they have no conflict of interest.
Mount Weld, and ion-adsorption clays are currently promi-
nent deposits supplying REEs. Therefore, it is inevitable that
the exploration and development of new RE deposits will be References
accelerated.
(2) RE ores are generally associated with other minerals, so 1. Cheisson T, Schelter EJ. Rare earth elements: mendeleev's bane, modern
beneficiation processes are essential to adopt. The design of marvels. Science. 2019;363(6426):489.
2. Richard AR, Fan M. Rare earth elements: properties and applications to
innovative processes combining flotation, gravity and mag- methanol synthesis catalysis via hydrogenation of carbon oxides. J Rare Earths.
netic separation is the focus of research. According to the 2018;36(11):1127.
nature of RE ores, rational separators are configured to 3. Kegl T, Kosak A, Lobnik A, Novak Z, Kralj AK, Ban I. Adsorption of rare earth
metals from wastewater by nanomaterials: a review. J Hazard Mater.
comprehensively recover associated resources when 2020;386:121632.
concentrating RE minerals to maximize the utilization of 4. Jordens A, Cheng YP, Waters KE. A review of the beneficiation of rare earth
resources. element bearing minerals. Miner Eng. 2013;41:97.
5. Dushyantha N, Batapola N, Ilankoon IMSK, Rohitha S, Premasiri R,
(3) Froth flotation is the most well-established technique used to
Abeysinghe B, et al. The story of rare earth elements (REEs): occurrences,
concentrate RE minerals, and it can process a wide range of global distribution, genesis, geology, mineralogy and global production. Ore
fine particle sizes. Typical collectors in RE flotation include Geol Rev. 2020;122:103521.
6. Ferru G, Reinhart B, Bera MK, Cruz MOdl, Qiao B, Ellis RJ. The lanthanide
hydroxamates, carboxylates and phosphates, and developing
contraction beyond coordination chemistry. Chem Eur J. 2016;22(20):6899.
new reagents is of great significance to improve the recovery 7. Wanhala AK, Doughty B, Bryantsev VS, Wu L, Mahurin SM, Jansone-Popova S,
of RE concentrates and reduce beneficiation costs. et al. Adsorption mechanism of alkyl hydroxamic acid onto bastnasite:
(4) Metallurgical techniques for treating RE concentrates, such fundamental steps toward rational collector design for rare earth elements.
J Colloid Interface Sci. 2019;553:210.
as oxidation roastingeHCl leaching, caustic soda decompo- 8. Balaram V. Rare earth elements: a review of applications, occurrence, explo-
sition and high-temperature concentrated sulfuric acid ration, analysis, recycling, and environmental impact. Geosci Front.
roasting, are used to process bastnaesite, monazite and 2019;10(4):1285.
9. Xu X, Zhu W, Wang Z, Witkamp G-J. Distributions of rare earths and heavy
mixed RE concentrates, respectively. For ion-adsorption RE metals in field-grown maize after application of rare earth-containing fertil-
minerals, traditional dressing processes are ineffective. REEs izer. Sci Total Environ. 2002;293(1e3):97.
can be directly extracted from deposits by in situ leach- 10. Dutta T, Kim KH, Uchimiya M, Kwon EE, Jeon BH, Deep A, et al. Global demand
for rare earth resources and strategies for green mining. Environ Res.
ingeprecipitation/solvent extraction. 2016;150:182.
(5) In metallurgy, the high consumption of chemical reagents 11. Binnemans K, Jones PT, Blanpain B, Van Gerven T, Yang Y, Walton A, et al.
and pollution formed by three wastes (waste gas, wastewater Recycling of rare earths: a critical review. J Clean Prod. 2013;51:1.
12. United States Geological Survey (USGS). Mineral commodity summaries 2022
and waste residue) are prominent problems. In recent years,
Washington, DC. 2022.
cleaner metallurgical processes have been successfully 13. Abaka-Wood GB, Quast K, Zanin M, Addai-Mensah J, Skinner W. A study of the
developed on the laboratory scale, but more efforts are still feasibility of upgrading rare earth elements minerals from iron-oxide-silicate
rich tailings using Knelson concentrator and Wilfley shaking table. Powder
needed to achieve industrial application. Source control of
Technol. 2019;344:897.
fluorine, comprehensive utilization of thorium, and devel- 14. Dostal J. Rare earth element deposits of alkaline igneous rocks. Resour.
opment of green extractants are important directions for 2017;6(3):34.
optimizing metallurgical processes. 15. Chakhmouradian AR, Wall F. Rare earth elements: minerals, mines, magnets
(and more). Elements. 2012;8(5):333.

640
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

16. Chi R, Li ZJ, Peng C, Zhu GC, Xu SM. Partitioning properties of rare earth ores in 45. Zhao X, Li NB, Huizenga JM, Zhang QB, Yang YY, Yan S, et al. Granitic magma
China. Rare Met. 2005;24(3):205. evolution to magmatic-hydrothermal processes vital to the generation of
17. Cen P, Bian X, Liu Z, Gu M, Wu W, Li B. Extraction of rare earths from bast- HREEs ion-adsorption deposits: constraints from zircon texture, U-Pb
naesite concentrates: a critical review and perspective for the future. Miner geochronology, and geochemistry. Ore Geol Rev. 2022;146:104931.
Eng. 2021;171:107081. 46. He Q, Qiu J, Chen J, Zan M, Xiao Y. Progress in green and efficient enrichment
18. Mariano AN, Mariano A. Rare earth mining and exploration in North America. of rare earth from leaching liquor of ion adsorption type rare earth ores. J Rare
Elements. 2012;8(5):369. Earths. 2022;40(3):353.
19. Wang ZY, Fan HR, Zhou LL, Yang KF, She HD. Carbonatite-related REE de- 47. Takeda O, Okabe TH. Current status on resource and recycling technology for
posits: an overview. Minerals. 2020;10(11):965. rare earths. Metall Mater Trans E. 2014;1(2):160.
20. Castor SB. The Mountain pass rare-earth carbonatite and associated ultra- 48. Li YHM, Zhao WW, Zhou MF. Nature of parent rocks, mineralization styles and
potassic rocks, California. Can Mineral. 2008;46(4):779. ore genesis of regolith-hosted REE deposits in South China: an integrated
21. Smith MP, Moore K, Kavecsa nszki D, Finch AA, Kynicky J, Wall F. From mantle genetic model. J Asian Earth Sci. 2017;148:65.
to critical zone: a review of large and giant sized deposits of the rare earth 49. Higashiyama Y, Asano K. Recent progress in electrostatic separation tech-
elements. Geosci Front. 2016;7(3):315. nology. Part Sci Technol. 1998;16(1):77.
22. Castor SB. Rare earth deposits of North America. Resour Geol. 2008;58(4):337. 50. Cao Y, Wang Z, Wang J, Li G. Study of talcum charging status in parallel plate
23. Zheng X, Liu Y. Mechanisms of element precipitation in carbonatite-related electrostatic separator based on particle trajectory analysis. Plasma Sci Tech-
rare-earth element deposits: evidence from fluid inclusions in the Maoniup- nol. 2018;20(5):054019.
ing deposit, Sichuan Province, southwestern China. Ore Geol Rev. 2019;107: 51. Moscoso-Pinto F, Kim HS. Concentration and recovery of valuable heavy
218. minerals from dredged fine aggregate waste. Minerals. 2021;11(1):49.
24. Weng Q, Yang WB, Niu HC, Li NB, Qu P, Shan Q, et al. BeSreNdePb isotopic 52. McNulty T, Hazen N, Park S. Processing the ores of rare-earth elements. MRS
constraints on the origin of the Maoniuping alkaline syeniteecarbonatite Bull. 2022;47(3):258.
complex, SW China. Ore Geol Rev. 2021;135:104193. 53. Moustafa MI, Abdelfattah NA. Physical and chemical beneficiation of the
25. Liu Y, Hou Z. A synthesis of mineralization styles with an integrated genetic Egyptian beach monazite. Resour Geol. 2010;60(3):288.
model of carbonatite-syenite-hosted REE deposits in the Cenozoic Mianning- 54. Rejith RG, Sundararajan M. Combined magnetic, electrostatic, and gravity
Dechang REE metallogenic belt, the eastern Tibetan Plateau, southwestern separation techniques for recovering strategic heavy minerals from beach
China. J Asian Earth Sci. 2017;137:35. sands. Mar Georesour Geotechnol. 2017;36(8):959.
26. Kong LR, Zhang GR. Ore types and characteristics of melt (fluid) inclusions on 55. Chen Y, He D, Potgieter JH. Development and beneficiation technology of rare
the maoniuping REE deposit mianning, sichuan, China. Appl Mech Mater. earth ores in China. J South Afr Inst Min Metall. 2022;122(3):1.
2014;675:1308. 56. Marion C, Grammatikopoulos T, Rudinsky S, Langlois R, Williams H, Chu P,
27. Qiu XM, Wang CH, Zhen HU, Qiu XY, Li HW. Commercial practice research on et al. A mineralogical investigation into the pre-concentration of the Necha-
pre-concentration technology by magnetic separation for maoniuping RE ore. lacho deposit by gravity separation. Miner Eng. 2018;121:1.
Copper Eng. 2018;25(2):30 (in Chin.). 57. Jordens A, Sheridan RS, Rowson NA, Waters KE. Processing a rare earth
28. Weng ZH, Jowitt SM, Mudd GM, Haque N. A detailed assessment of global rare mineral deposit using gravity and magnetic separation. Miner Eng. 2014;62:9.
earth element resources: opportunities and challenges. Econ Geol. 58. Kim K, Jeong S. Separation of monazite from placer deposit by magnetic
2015;110(8):1925. separation. Minerals. 2019;9(3):149.
29. Kumari A, Panda R, Jha MK, Kumar JR, Lee JY. Process development to recover 59. Wang J, Zu P, Yi S, Cao Z. Preconcentration of iron, rare earth, and fluorite from
rare earth metals from monazite mineral: a review. Miner Eng. 2015;79:102. bayan Obo ore using superconducting magnetic separation. Min Metall Explor.
30. Zhu XK, O'Nions RK. Monazite chemical composition: some implications for 2020;38(2):701.
monazite geochronology. Contrib Mineral Petrol. 1999;137(4):351. 60. Faris N, Ram R, Tardio J, Bhargava S, Pownceby MI. Experimental study into
31. Johnson TE, Clark C, Taylor RJM, Santosh M, Collins AS. Prograde and retro- the beneficiation of a ferruginous rare earth bearing lateritic ore by mag-
grade growth of monazite in migmatites: an example from the Nagercoil netising roasting and magnetic separation. Miner Eng. 2019;137:303.
Block, southern India. Geosci Front. 2015;6(3):373. 61. Pradip Fuerstenau DW. Design and development of novel flotation reagents
32. Veerasamy N, Murugan R, Kasar S, Inoue K, Kavasi N, Balakrishnan S, et al. for the beneficiation of Mountain Pass rare-earth ore. Miner Metall Process.
Geochemical characterization of monazite sands based on rare earth ele- 2013;30(1):1.
ments, thorium and uranium from a natural high background radiation area 62. Marion C, Li R, Waters KE. A review of reagents applied to rare-earth mineral
in Tamil Nadu, India. J Environ Radioact. 2021;232:106565. flotation. Adv Colloid Interface Sci. 2020;279:102142.
33. Wyatt NLP, Costa VC, de Souza JR, Ferde M, Costa FS, Neris JB, et al. Unsu- 63. Kosmulski M. IEP as a parameter characterizing the pH-dependent surface
pervised pattern-recognition and radiological risk assessment applied to the charging of materials other than metal oxides. Adv Colloid Interface Sci.
evaluation of behavior of rare earth elements, Th, and U in monazite sand. 2012;171:77.
Environ Sci Pollut Res Int. 2022;29(55):83417. 64. Pradip Fuerstenau DW. The adsorption of hydroxamate on semi-soluble
34. Corbett MK, Eksteen JJ, Niu XZ, Croue JP, Watkin ELJ. Interactions of phosphate minerals. Part I: adsorption on barite, Calcite and Bastnaesite. Colloids Surf,
solubilising microorganisms with natural rare-earth phosphate minerals: a A. 1983;8(2):103.
study utilizing Western Australian monazite. Bioproc Biosyst Eng. 2017;40(6): 65. Fuerstenau DW. Pradip. Zeta potentials in the flotation of oxide and silicate
929. minerals. Adv Colloid Interface Sci. 2005;114:9.
35. Zhukova IA, Stepanov AS, Jiang S-Y, Murphy D, Mavrogenes J, Allen C, et al. 66. Delgado AV, Gonz alez-Caballero F, Hunter RJ, Koopal LK, Lyklema J. Mea-
Complex REE systematics of carbonatites and weathering products from surement and interpretation of electrokinetic phenomena. J Colloid Interface
uniquely rich Mount Weld REE deposit, Western Australia. Ore Geol Rev. Sci. 2007;309(2):194.
2021;139:104539. 67. Liu W, Wang X, Miller JD. Collector chemistry for bastnaesite flotation e
36. Lottermoser BG. Rare-earth element mineralisation within the Mt. Weld recent developments. Miner Process Extr Metall Rev. 2019;40(6):370.
carbonatite laterite, Western Australia. Lithos. 1990;24(2):151. 68. Sarvaramini A, Azizi D, Larachi F. Hydroxamic acid interactions with solvated
37. Jamaludin H, Lahiri-Dutt K. Could Lynas make a difference in the global po- cerium hydroxides in the flotation of monazite and bastn€ asitedexperiments
litical economy of Rare Earth Elements in future? Resour Pol. 2017;53:267. and DFT study. Appl Surf Sci. 2016;387:986.
38. Yang KF, Fan HR, Santosh M, Hu FF, Wang KY. Mesoproterozoic carbonatitic 69. Chapleski Jr RC, Chowdhury AU, Wanhala AK, Gibson LD, Stamberga DN,
magmatism in the Bayan Obo deposit, Inner Mongolia, North China: con- Jansone-Popova S, et al. Improving rare-earth mineral separation with in-
straints for the mechanism of super accumulation of rare earth elements. Ore sights from molecular recognition: functionalized hydroxamic acid adsorp-
Geol Rev. 2011;40(1):122. tion onto bastnasite and calcite. Langmuir. 2022;38(18):5439.
39. Fan HR, Yang KF, Hu FF, Liu S, Wang KY. The giant Bayan Obo REE-Nb-Fe 70. Espiritu ERL, da Silva GR, Azizi D, Larachi F, Waters KE. The effect of dissolved
deposit, China: controversy and ore genesis. Geosci Front. 2016;7(3):335. mineral species on bastna €site, monazite and dolomite flotation using ben-
40. Yang X, Lai X, Pirajno F, Liu Y, Mingxing L, Sun W. Genesis of the bayan Obo zohydroxamate collector. Colloids Surf, A. 2018;539:319.
Fe-REE-Nb formation in inner Mongolia, North China craton: a perspective 71. Li M, Gao K, Zhang D, Duan H, Ma L, Huang L. The influence of temperature on
review. Precambrian Res. 2017;288:39. rare earth flotation with naphthyl hydroxamic acid. J Rare Earths. 2018;36(1):
41. Kynicky J, Smith MP, Xu C. Diversity of rare earth deposits: the key example of 99.
China. Elementa. 2012;8(5):361. 72. Pavez O, Brandao PRG, Peres AEC. Technical note adsorption of oleate and
42. Xu C, Chi R, Zhang Y, Zhong C, Ruan Y, Lyu R, et al. Process mineralogy of octyl-hydroxamate on to rare-earths minerals. Miner Eng. 1996;9(3):357.
Bayan Obo rare earth ore by MLA. Physicochem Probl Miner Process. 73. Jordens A, Marion C, Kuzmina O, Waters KE. Surface chemistry considerations
2020;56(4):737. in the flotation of bastna €site. Miner Eng. 2014;66:119.
43. Li W, Chen J, Zhou W, Han Y, Shan Y. Effect of bastnaesite as reductant on 74. Espiritu ERL, Naseri S, Waters KE. Surface chemistry and flotation behavior of
hematite reduction during in-situ suspension magnetization roasting of re- dolomite, monazite and bastna €site in the presence of benzohydroxamate,
fractory iron ore under neutral atmosphere. Int J Min Sci Technol. 2022;32(4): sodium oleate and phosphoric acid ester collectors. Colloids Surf, A. 2018;546:
877. 254.
44. Yamaguchi A, Honda T, Tanaka M, Tanaka K, Takahashi Y. Discovery of ion- 75. Pavez O, Peres AEC. Technical note bench scale flotation of a brazilian
adsorption type deposits of rare earth elements (REE) in Southwest Japan monazite ore. Miner Eng. 1994;7(12):1561.
with speciation of REE by extended X-ray absorption fine structure spec- 76. Wen Qi G. Use of the QEM*SEM analysis in flotation testwork on a phosphate
troscopy. Geochem J. 2018;52(5):415. ore containing monazite. Int J Miner Process. 1993;37(1):89.

641
S. Cheng, W. Li, Y. Han et al. Journal of Rare Earths 42 (2024) 629e642

77. Ren J, Song SX, Lopez-Valdivieso A, Lu SC. Selective flotation of bastnaesite 102. Demol J, Ho E, Senanayake G. Sulfuric acid baking and leaching of rare earth
from monazite in rare earth concentrates using potassium alum as depres- elements, thorium and phosphate from a monazite concentrate: effect of bake
sant. Int J Miner Process. 2000;59(3):237. temperature from 200 to 800  C. Hydrometallurgy. 2018;179:254.
78. Liu W, Wang X, Xu H, Miller JD. Lauryl phosphate adsorption in the flotation 103. Kim W, Bae I, Chae S, Shin H. Mechanochemical decomposition of monazite to
of Bastnaesite, (Ce,La)FCO3. J Colloid Interface Sci. 2017;490:825. assist the extraction of rare earth elements. J Alloys Compd. 2009;486(1):610.
79. Liu W, Wang X, Wang Z, Miller JD. Flotation chemistry features in bastnaesite 104. Panda R, Kumari A, Jha MK, Hait J, Kumar V, Rajesh Kumar J, et al. Leaching of
flotation with potassium lauryl phosphate. Miner Eng. 2016;85:17. rare earth metals (REMs) from Korean monazite concentrate. J Ind Eng Chem.
80. Liu W, McDonald LW, Wang X, Miller JD. Bastnaesite flotation chemistry is- 2014;20(4):2035.
sues associated with alkyl phosphate collectors. Miner Eng. 2018;127:286. 105. Sadri F, Nazari AM, Ghahreman A. A review on the cracking, baking and
81. Zhang Y, Anderson C. A comparison of sodium silicate and ammonium leaching processes of rare earth element concentrates. J Rare Earths.
lignosulfonate effects on xenotime and selected gangue mineral micro- 2017;35(8):739.
flotation. Miner Eng. 2017;100:1. 106. Abdel-Rehim AM. An innovative method for processing Egyptian monazite.
82. Abaka-Wood GB, Fosu S, Addai-Mensah J, Skinner W. Flotation recovery of Hydrometallurgy. 2002;67(1):9.
rare earth oxides from hematiteequartz mixture using sodium oleate as a 107. Galvin J, Safarzadeh MS. Decomposition of monazite concentrate in potassium
collector. Miner Eng. 2019;141:105847. hydroxide solution. J Environ Chem Eng. 2018;6(1):1353.
83. Wang CY, Ru CQ, Mioduchowski A. Elastic buckling of multiwall carbon 108. Zhang Z, Jia Q, Liao W. Progress in the separation processes for rare earth
nanotubes under high pressure. J Nanosci Nanotechnol. 2003;3(1):199. resources. In: Bünzli JC, Pecharsky VK, eds. Handbook on the physics and
84. Abaka-Wood GB, Addai-Mensah J, Skinner W. A study of selective flotation chemistry of rare earths. Amsterdam: Elsevier; 2015.
recovery of rare earth oxides from hematite and quartz using hydroxamic acid 109. Demol J, Ho E, Soldenhoff K, Senanayake G. The sulfuric acid bake and leach
as a collector. Adv Powder Technol. 2018;29(8):1886. route for processing of rare earth ores and concentrates: a review. Hydro-
85. Pradip Fuerstenau DW. The role of inorganic and organic reagents in the metallurgy. 2019;188:123.
flotation separation of rare-earth ores. Int J Miner Process. 1991;32(1):1. 110. Wang X, Liu J, Li M, Fan H, Yang Q. Decomposition reaction kinetics of Baotou
86. Houot R, Cuif J-P, Mottot Y, Samama J-C. Recovery of rare earth minerals, with RE concentrate with concentrated sulfuric acid at low temperature. Rare Met.
emphasis on flotation process. Mater Sci Forum. 1991;70:301. 2010;29(2):121.
87. Pavez O, Peres AEC. Effect of sodium metasilicate and sodium sulphide on the 111. Lu Y, Wei H, Zhang Z, Li Y, Wu G, Liao W. Selective extraction and separation
floatability of monazite-zircon-rutile with oleate and hydroxamates. Miner of thorium from rare earths by a phosphorodiamidate extractant. Hydro-
Eng. 1993;6(1):69. metallurgy. 2016;163:192.
88. Fuerstenau DW, Pradip Herrera-Urbina R. The surface chemistry of bastnae- 112. Dong Y, Li S, Su X, Wang Y, Shen Y, Sun X. Separation of thorium from rare
site, barite and calcite in aqueous carbonate solutions. Colloids Surf, A. earths with high-performance diphenyl phosphate extractant. Hydrometal-
1992;68(1):95. lurgy. 2017;171:387.
89. Chehreh Chelgani S, Hart B. Explaining surface interactions for common 113. Li M, Li J, Zhang D, Gao K, Wang H, Xu W, et al. Decomposition of mixed rare
associated gangues of rare earth minerals in response to the oxalic acid. Int J earth concentrate by NaOH roasting and kinetics of hydrochloric acid leaching
Min Sci Technol. 2018;28(2):343. process. J Rare Earths. 2020;38(9):1019.
90. Zhang W, Honaker RQ. Flotation of monazite in the presence of calcite part II: 114. Li J, Li M, Zhang D, Gao K, Xu W, Wang H, et al. Clean production technology of
enhanced separation performance using sodium silicate and EDTA. Miner Eng. Baiyun Obo rare earth concentrate decomposed by Al(OH)3-NaOH. Chem Eng J.
2018;127:318. 2020;382:122790.
91. Cao Z, Cao Y, Qu Q, Zhang J, Mu Y. Separation of bastna €site from fluorite 115. Luo X, Zhang Y, Zhou H, He K, Luo C, Liu Z, et al. Review on the development
using ethylenediamine tetraacetic acid as depressant. Miner Eng. 2019;134: and utilization of ionic rare earth ore. Minerals. 2022;12(5):554.
134. 116. Moldoveanu GA, Papangelakis VG. Recovery of rare earth elements adsorbed
92. Xia L, Hart B, Loshusan B. A Tof-SIMS analysis of the effect of lead nitrate on on clay minerals: II. Leaching with ammonium sulfate. Hydrometallurgy.
rare earth flotation. Miner Eng. 2015;70:119. 2013;131:158.
93. Huang XW, Long ZQ, Wang LS, Feng ZY. Technology development for rare 117. Xiao YF, Chen YY, Feng ZY, Huang XW, Huang L, Long ZQ, et al. Leaching
earth cleaner hydrometallurgy in China. Rare Met. 2015;34(4):215. characteristics of ion-adsorption type rare earths ore with magnesium sulfate.
94. Wang L, Huang X, Yu Y, Zhao L, Wang C, Feng Z, et al. Towards cleaner pro- T Nonferr Metal Soc. 2015;25(11):3784.
duction of rare earth elements from bastnaesite in China. J Clean Prod. 118. Xiao YF, Feng ZY, Huang XW, Huang L, Chen YY, Wang LS, et al. Recovery of
2017;165:231. rare earths from weathered crust elution-deposited rare earth ore without
95. Zhao L, Wang L, Shuai G, Long Z, Cui D, Huang X. Thermal decomposition and ammonia-nitrogen pollution: I. leaching with magnesium sulfate. Hydromet-
oxidation of bastnaesite concentrate in inert and oxidative atmosphere. J Rare allurgy. 2015;153:58.
Earths. 2018;36(7):758. 119. Xiao YF, Feng ZY, Huang XW, Huang L, Chen YY, Liu XS, et al. Recovery of rare
96. Chi R, Li Z, Peng C, Gao H, Xu Z. Preparation of enriched cerium oxide from earth from the ion-adsorption type rare earths ore: II. Compound leaching.
bastnasite with hydrochloric acid by two-step leaching. Metall Mater Trans B. Hydrometallurgy. 2016;163:83.
2006;37(2):155. 120. Lai FG, Gao GH, Huang L, Xiao YF, Yang R, Li KZ. Compound leaching of rare
97. Cen P, Bian X, Wu W. Isoconversional kinetic analysis of decomposition of earth from the ion-adsorption type rare earth ore with magnesium sulfate
bastnaesite concentrates with calcium hydroxide. J Rare Earths. 2020;38(12): and ascorbic acid. Hydrometallurgy. 2018;179:25.
1361. 121. Huang L, Gao G, Wu R, Zhang Q, Lai F, Xiao Y. Non-ammonia enrichment of
98. Zhu G, Chi R, Shi W, Xu Z. Chlorination kinetics of fluorine-fixed rare earth rare earth by magnesium oxide from rare earth leaching liquor in magnesium
concentrate. Miner Eng. 2003;16(7):671. salt system. J Rare Earths. 2019;37(8):886.
99. Chi R, Zhang X, Zhu G, Zhou ZA, Wu Y, Wang C, et al. Recovery of rare earth 122. Yu Z, Wang M, Wang L, Zhao L, Feng Z, Sun X, et al. Preparation of crystalline
from bastnasite by ammonium chloride roasting with fluorine deactivation. mixed rare earth carbonates by Mg(HCO3)2 precipitation method. J Rare
Miner Eng. 2004;17(9):1037. Earths. 2020;38(3):292.
100. Kim E, Osseo-Asare K. Aqueous stability of thorium and rare earth metals in 123. Liu J, Huang K, Wu X, Liu W, Song W, Liu H. Extraction of rare earths using
monazite hydrometallurgy: ehepH diagrams for the systems The, Cee, Lae, bubbling organic liquid membrane with un-saponified P507. Hydrometallurgy.
Nde(PO4)e(SO4)eH2O at 25  C. Hydrometallurgy. 2012;113:67. 2018;175:340.
101. Maharana LN, Nair VR. Production of value added rare earths from monazite 124. Han Y, Chen J, Deng Y, Liu T, Li H, Li D. An innovative technique for the
by solvent extraction. In: San francisco: TMS(the minerals, metals amp; mate- separation of ion-adsorption high yttrium rare earth ore by Er (III)/Tm (III)
rials society) annual meeting. 2005. grouping first. Sep Purif Technol. 2022;280:119929.

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