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 Minerals Engineering 79 (2015) 102–115

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Process development to recover rare earth metals from monazite

mineral: A review
Archana Kumari a, Rekha Panda a, Manis Kumar Jha a,⇑, J. Rajesh Kumar b, Jin Young Lee b,⇑
a
Metal Extraction and Forming Division, CSIR-National Metallurgical Laboratory, Jamshedpur 831007, India
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources, Daejeon 305-350, South Korea

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

Article history: The escalating demand of rare earth metals (REMs) in various applications and their continuous depleting
Received 25 February 2015 ores have laid emphasis to produce metals from their complex resources by developing energy efficient
Revised 8 May 2015 and eco-friendly processes. Present review reports the commercial processes based on pyro–hydro or
Accepted 10 May 2015
hybrid techniques as well as systematic research for process development to recover rare earth from
Available online 9 June 2015
monazite. The salient findings on mining and physical beneficiation of different beach sand deposits con-
taining monazite are reviewed. Monazite concentrate obtained are processed under different condition of
Keywords:
time, temperature and concentration using acidic or alkaline solution. They are usually processed using
Monazite
Rare earth metals (REMs)
thermal treatment followed by REMs recovery under optimized conditions of leaching and their extrac-
Mineral beneficiation tion via solvent extraction, precipitation, etc. to produce salts/concentrate of REMs from the leached solu-
Leaching tion. The processes developed to recover REMs are reviewed and recommendations are made in respect
Solvent extraction to various methodologies and objectives.
Ó 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2. Processing of different minerals to obtain monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
2.1. Mining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
2.2. Physical beneficiation of monazite minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.2.1. Flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.2.2. Gravity separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.2.3. Electrostatic and magnetic separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3. Processing of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1. Direct leaching of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.1. Direct leaching with acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.1.1. Leaching in sulfuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.1.2. Leaching in sulfuric acid after mechanochemical treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.1.3. Leaching in nitric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.1.1.4. Leaching of hydrous oxide cake of beach sand monazite in nitric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.1.1.5. Leaching in hydrochloric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.1.1.6. Comparison of leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.2. Direct leaching in alkali . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.1.2.1. Leaching of RE concentrate of monazite in ammonium carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.2. Pre-treatment of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.3. Leaching of monazite concentrate after pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.4. Overview of the leaching technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
3.5. Processing of leach solution by solvent extraction (SX) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

⇑ Corresponding authors. Fax: +91 657 2345213 (M.K. Jha), +82 42 8683418
(J.Y. Lee).
E-mail addresses: mkjha@nmlindia.org (M.K. Jha), jinlee@kigam.re.kr (J.Y. Lee).

http://dx.doi.org/10.1016/j.mineng.2015.05.003
0892-6875/Ó 2015 Elsevier Ltd. All rights reserved.
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115 103

3.6. Recovery of REs from the leach solution by precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

3.7. Environmental aspects of monazite processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

1. Introduction
Rare earth metals (REMs) are group of 15 elements of the lan-
thanide series including Sc and Y, which are mainly classified into
two groups based on their ionic radius; light rare earth elements
(LREEs) from La to Sm and heavy rare earth elements (HREEs) from
Eu to Lu. These metals possess similar physiochemical properties
and universally originate in the same mineral assemblies. The
meticulous spectroscopic and magnetic properties of REMs enables
them to play imperative role from industrial to advanced material
sciences including hybrid and electric automobiles, fluorescent
lights, metal alloys, critical military applications and in the manu-
facturing of high intensity magnets, electrical assemblies, etc. (Kim
and Osseo-Asare, 2012). The USGS mineral commodity survey of
2015 reported the global reserves of rare earth elements (REEs)
to be 130 million tons in 2014. The global demand for rare earth
oxides is estimated to grow from 120,148 tons in 2014 to
150,766 tons in 2020 at a CAGR of 3.9% driven largely due to esca-
lating demand of some particular RE oxide (Castilloux, 2014).
However, it was previously estimated that the demand will exceed
200,000 tons in 2014 but REEs demand surpassed 200,000 tons per
year, with an exceeding supply of 40,000 tons annually for several
years (Panda et al., 2014). This deficiency affects the global market
of REMs. As a result, the world immediately needs fresh, enduring
supply of REEs to meet its requirement. Hatch in 2012 presented
the global estimates of demand for total rare earth oxides in
2011 as presented in Fig. 1.
According to EPA, United States Environmental Protection
Agency, 2012, the abundance of REEs in earth’s crust shows that
lanthanides with lower atomic numbers are more abundant than
one with higher atomic numbers as presented in Table 1. They
do not occur as metallic elements but exists in wide range of min-
erals of carbonates, oxides, phosphates and silicates as trivalent
cations. Table 2 presents few of these minerals with the approxi-
mate percentage of RE oxide content (Hedrick, 2004; Kumari
et al., 2013). In most deposits, REEs can be recovered as the pri-
mary product or as a co-products/by-products of certain other
minerals. These RE minerals are located throughout the world,
with usually large deposits occurring in few countries like China,
Australia, India, Malaysia, Russia, etc. Although the escalating need
of REEs is principally met by import from China but the recent pol-
icy of Chinese government has drastically reduced the export of
REMs causing increase in the RE’s price and making it vital for
other countries to expand its capability to obtain REEs resources.
Among 250 recognized REEs minerals, only three are considered
to be the major ore that is most viable for REMs extraction: bastn-
asite, monazite and xenotime. However, weathered crust
elution-deposited rare earth ores commonly known as
ion-adsorbed rare earth ore is also feasible for RE recovery. These
ores were first discovered as a novel exogenous ore in Jiangxi pro-
vince of China in 1969 and have widespread distribution, rich
reserves, low radioactivity, complete RE partitioning and is rich
in middle and heavy rare earth. The details of RE sources, their pro-
cessing and applications have been made by different authors and
are evident from the papers presented in different proceedings
(Cole, 1988). Among these minerals, monazite is a common beach
sand mineral present in acidic igneous rocks and vein deposits
mainly containing 4–12% ThO2, 20–30% Ce2O3, and 10–40% La2O3
(Thompson et al., 2011). The potential sources of monazite mineral
are presented in Table 3 (Hedrick, 2001). The resource estimates of
monazite in inland placer deposits stands at 10.21 million tons in
2005. India holds only 3% of the world reserves as compared to
36% by China and 13% by USA (Pandey, 2011).
The present paper reports different processes, with particular
focus on the recuperation of REMs from monazite using pyro–hy-
dro or hybrid techniques, consisting of direct leach or pretreatment
followed by leaching in acidic/alkaline solutions. The systematic
research and various flow-sheets developed to recover REEs under
the different condition of time, temperature, concentration etc.
from monazite have also been discussed and reviewed.
2. Processing of different minerals to obtain monazite
concentrate
The treatment of any mineral depends on its mineralogy, avail-
ability, metal content, engineering feasibility, transportation, gov-
ernment norms, etc. The mining and processing of rare earth

Table 1
Abundance of rare earth elements in earth’s crust.

Elements Atomic number Abundance (ppm)

Lanthanum 57 30
Cerium 58 60
Praseodymium 59 6.7
Neodymium 60 27
Promethium 61 1018
Samarium 62 5.3
Europium 63 1.3
Gadolinium 64 4.0
Terbium 65 0.7
Dysprosium 66 3.8
Holmium 67 0.8
Erbium 68 2.1
Thulium 69 0.3
Ytterbium 70 2.0
Lutetium 71 0.4
Fig. 1. Global estimated demand for total RE oxides in 2011.
104 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115

Table 2
RE oxides present in rare earth minerals.

Carbonate Mineral Bastnaesite (Ce, La)(CO3)F Parisite Ca(Ce, La)2(CO3)3F2 Synchysite Ca(Ce, LA)(CO3)2F Cebaite Ba3Ce2(CO3)5F2
REO (%) 75 61 51 32
Phosphate Mineral Apatite Ca5(PO4)3(F, Cl, OH) Monazite (Ce, La, Nd, Th)PO4 Xenotime YPO4 Florencite CeAl3(PO4)2(OH)6
REO (%) 19 65 61 32
Silicate Mineral Gadolinite (Ce, La, Nd, Allanite (Ce, Ca, Y)2(Al, Kainosite Ca2(Y, Britholite (Ce, Ca)5(SiO4,
Y)2Fe2+Be2Si2O10 Fe3+)3(SiO4)3OH Ce)2Si4O12CO3H2O PO4)3(OH, F)
REO (%) 60 38 38 32
Oxide Mineral Fergusonite (Ce, La, Nd)NbO4 Loparite (Ce, La, Na, Ca, Sr)(Ti, Euxenite (Y, Ca, Ce, U, Th)(Nb, Ta, Brannerite (U, Ca, Y, Ce)(Ti,
Nb)O3 Ti)2O6 Fe)2O6
REO (%) 53 30 24 9

Table 3
Rare earth contents of major and potential source of monazite minerals. (Percentage of total rare-earth oxide).

Rare earth Monazite

elements
North Capel, West North Stradbroke Island, Queensland, Green Cove Nangang, East Coast, Mount Weld,
Australia Australia Springs, USA Guangdong, China Brazil Australia
Cerium 46.00 45.80 43.70 42.70 47.00 51.00
Lanthanum 23.90 21.50 17.50 23.00 24.00 26.00
Neodymium 17.40 18.60 17.50 17.00 18.50 15.00
Praseodymium 5.00 5.30 5.00 4.10 4.50 4.00
Samarium 2.53 3.10 4.90 3.00 3.00 1.80
Europium .0530 .8000 .1600 .1000 .1000 .4000
Gadolinium 1.49 1.80 6.60 2.00 1.00 1.00
Terbium .0350 .3000 .2600 .7000 .1000 .1000
Dysprosium .7000 0.6000 .9000 .8000 .4000 .2000
Erbium .2000 .2000 Trace .3000 .1000 .2000
Yttrium 2.40 2.50 3.20 2.40 1.40 Trace
Holmium .0530 .1000 .1100 .1200 Trace .1000
Thulium Trace Trace Trace Trace Trace Trace
Ytterbium .1000 .1000 .2100 2.40 .0200 .1000
Lutetium Trace .0100 Trace .1400 ND Trace
TOTAL 100.00 100.00 100.00 100.00 100.00 100.00

ND – not detected.

minerals is complicated, costly and there is potential for negative Table 4

Selected rare earth companies and their primary mines.
effects on the environment (Hurst, 2010). Mines are the major
source for the release of three major contaminants: radionuclides, Company Country Primary mines
rare earth elements, and dust and metal. Each of these contami- Molycorp, Inc. United Mountain Pass
nants escapes have different detrimental effects on the environ- States
ment. The details of the mining and physical beneficiation of the Lynas Corporation, Ltd. Australia Mount Weld
Avalon Rare Metals, Inc. Canada Nechalacho (Thor Lake)
monazite containing minerals to produce monazite concentrate Alkaline Resources, Ltd. Australia Dubbo
are discussed below. Arafura Resources, Ltd. Australia Nolans Bore
Rare Element Resources, Ltd. United Bear Lodge (Bull Hill
States Zone)
Great Western Minerals Group, Canada Steenkampskraal
2.1. Mining
Ltd.
Greenland Minerals and Energy, Australia Kvanefjeld
Mining involves removing mineralized rock containing RE Ltd.
deposits from ground through open-pit or underground methods. Quest Rare Minerals, Ltd. Canada Strange Lake (B Zone)
Open pit operations are performed by the world’s largest RE mines, Tasman Metals, Ltd. Canada Norra Karr
Stans Energy Corp. Canada Kutessay II
Bayan Obo in China and Mountain Pass in United States using Ucore Rare Metals, Inc. Canada Bokan (Dotson)
processes of standard drilling, blasting, loading, and dragging to
the mill procedures. Various open pit excavation methods, such
as scrapers, front-end loaders, shovels, and draglines, are used for
mining where water is not accessible (Gupta and Krishnamurthy, Some of the selected RE companies in various countries and their
2005). However, underground room and pillar mining are con- mines are shown in Table 4 (Jordens et al., 2013).
ducted where REs are recovered as by-product (Jackson and The future of strategic natural resources, Mission 2016 proposes
Christiansen, 1993). Placers sands are under water/affected by a that unfettered mining has probability to release harmful sub-
high water table and are mined by dredges. Proper steps for the stances of radionuclides, acids, fluorides, etc. into the environment
treatment of a placer monazite concentrate by dredging are also due to overtopping/collapsing of tailing dams. Open pit mining
reported Bucket wheel units are used to mine the shallower sands, exposes radioactive elements due to crushing of hard rocks while
while bucket line and suction dredges are used for mining deeper the underground mining has potential for tunnel collapsing and
material (Panigrahi, 2013). A degree of initial concentration is land subsidence. However, mining by in situ and heap leaching
usually performed at the dredge site itself. The material is then has environmental and safety advantages over conventional min-
transported as slurry through a pipeline to the beneficiation plant. ing but the release of toxic fluids used to dissolve the ore bodies
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115 105

affect the ecosystem as well as human population. About 9600– Biswas, 2008; Pavez and Peres, 1994). Beneficiation by flotation
12,000 cubic meters of toxic gases are released for each ton of had also been developed for Indian monazite. Fatty acid and
REEs produced with nearly 75 cubic meters of acidic waste water hydroxamate flotation are the principle techniques explored but
and one ton of radioactive waste residue. Government enforces more research into beneficiation techniques are required to suc-
regulations on companies and use technology to reduce the dam- cessfully start production once again at Mountain Pass. For selec-
age due to mining by establishing safeguards before operations tive flotation, monazite gangue materials, zircon and rutile,
proceeds. Ion-absorbing Type Rare Earths Ore mining is also pre- require depressant like sodium silicate, sodium sulfide and sodium
sent which causes series of environmental problems (Liu et al., oxalate (Pavez and Peres, 1993a,b; 1994). Combined physical and
2013). flotation methods have been used for recuperation of monazite
concentrate from fine heavy mineral beach sand deposits (Ferron
2.2. Physical beneficiation of monazite minerals et al., 1991) which is not possible in case of gravity separation.
However, the flotation knowledge regarding monazite needs more
In placer deposits, monazite occurs as a minor constituent while exploration as the physico-chemical characteristics of monazite is
the major minerals are ilmenite, rutile, zircon, and quartz. not confirmed.
Monazite is a RE–thorium phosphate, in which high content of a
naturally occurring radioactive element presents a negative aspect
2.2.2. Gravity separation
of mining and processing (Kul et al., 2008). As a result, it is mined
Gravity separation process is commonly utilized in rare earth
as heavy-mineral sand from Aeolian beach and recovered as a
minerals (mostly in monazite beneficiation) as they have relatively
by-product during processing of ilmenite, rutile, zircon and cassi-
large specific gravities and are typically associated with gangue
terite. Monazite is found in Manavalakurichi, Pulmoddai deposit,
material, primarily silicates that are significantly less dense
Orissa and Chavara deposits as well as REs division at Aluva in
(Ferron et al., 1991). A design was presented by Moustafa and
India (Gupta and Krishnamurthy, 2005). Indian Rare Earth
Abdelfattah in 2010 to concentrate monazite from Egyptian beach
Limited presents the mineralogical composition of
sands containing 30 wt.% valuable heavy minerals. Wet gravity
Manavalakurichi deposit which was found to contain 10.7 wt% of
separation was used initially to discard low specific gravity gangue
monazite, which is almost 3000 tons while the RE deposit at
and then low intensity magnetic separation to discard any ferro-
Aluva treat about 3600 tons of monazite (Peravadhanulu, 1979).
magnetic minerals without removing paramagnetic monazite. A
The beach sands of Manavalakurichi and Pulmoddai were not
chain of gravity, magnetic and electrostatic separations were fur-
pre-concentrated but directly put in for separation into its con-
ther applied where rutile was removed after electrostatic separa-
stituents using electrostatic and magnetic methods. Beneficiation
tion followed by the removal of diamagnetic zircon from the
processes of beach sand minerals probably vary from location to
paramagnetic monazite by magnetic separation to exploit different
location depending on their mineralogical and chemical
properties of the monazite, zircon and rutile minerals and produce
composition.
the final concentrate (Moustafa and Abdelfattah, 2010).
International Atomic Energy Agency reported that the heavy
Beneficiation of a beach placer sand deposit from Malawi is
minerals are initially separated from the gangue’ minerals using
wet separation techniques relying on density differences and
this process is referred to as primary separation removing up
Ore
to 90% of the gangue minerals. Further, secondary separation
process was applied to the heavy-mineral concentrate involving
magnetic and electrostatic separators. The higher iron content of
CRUSHING/ GRINDING
ilmenite gives it a higher magnetic susceptibility than the rest,
allowing it to be magnetically separated from other minerals
early in the process. Xenotime is sturdily magnetic than mon-
CONCENTRATION
azite and is electrostatically separated from ilmenite due to its
(Flotation)
poor electrical conductivity. However, the existence of leucoxene
in ilmenite hinders the separation of monazite. But roasting at
600 °C converts free hematite in leucoxene into magnetite and
Salt ROASTING/ CRACKING Acid or Caustic
enables easy separation. Similarly, if rutile and zircon are (Eg. Pug roast or Salt roast)
present, higher electrical conductivity of the former separate it
from latter. Further, non-magnetic zircon is separated from the
magnetic monazite. If monazite is chemically processed, the LEACHING
Acid/ Alkali
purity of monazite concentrate is upgraded to 98% using Solution
magnetic separation, otherwise the purity stream may be as
low as 30%. Thus, monazite or other minerals are separated
and concentrated after coarse grinding via gravity separation, FILTRATION Residue
flotation, electrostatic separation or magnetic processes (Jordens Liquor
et al., 2013, 2014). STABILIZATION
PURIFICATION
2.2.1. Flotation
Bulk heavy mineral concentrate are also produced from fine
grained beach sand deposits by flotation using fatty acid or
PRECIPITATION/ Raffinate or
phosphoric acid esters as collectors depending upon the ease of SOLVENT EXTRACTION Barren Liquor
desorption prior to separation (Ferron et al., 1991). Monazite
flotation using sodium oleate as collector, as well as the effect of
sodium metasilicate and sodium sulphide on the floatability of m RE salts
onazite–zircon–rutile and its characteristics has also been investi-
gated (Cheng et al., 1993; Pavez and Peres, 1993a,b; Dixit and Fig. 2. Flow-sheet of a rare earth processing.
106 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115
reported where gravity separation process via a shaking table was
used to remove quartz and feldspar. Further, Mitchell and Yusof
used carpco high intensity induced-roll magnetic separator to
obtain magnetic and non-magnetic products. In China, mainly at
Bayan Obo, gravity separation process in combination of froth
flotation has been employed between the rougher and cleaner
flotation circuits for efficient separation of monazite and bastnasite
from the iron-bearing and silicate gangue material (Chi et al., 2001;
Jordens et al., 2013). Lab-scale gravity separations have been suc-
cessfully completed on Turkish and Australian deposits where it
was found that the rare-earth minerals were concentrated into
very fine particles. To overcome this, either grinding steps were
modified to prevent excess fine generation or multi-gravity separa-
tor was employed to recover ultrafine particles (Guy et al., 2000;
Ozbayoglu and Umit Atalay, 2000). Roasting operation prior to
gravity separation was investigated by Kasey in 1956, where rare
earth carbonates ore were roasted at 1000 °C, converting carbon-
ates to oxides, thus increasing the mineral density and susceptibil-
ity to gravity separation.
2.2.3. Electrostatic and magnetic separation
Separation of different materials on basis of their conductivity is
achieved by electrostatic separation technique, which are only
used when alternative processing techniques will not be adequate.
In the rare earth mineral processing, use of electrostatic separation
is in the severance of monazite and xenotime from gangue miner-
als with similar specific gravity and magnetic properties (Ferron
et al., 1991; Zhang and Edwards, 2012). When xenotime (much
more paramagnetic than monazite) is concentrated with ilmenite
after magnetic separation of heavy mineral sands it may be
removed from the ilmenite via electrostatic separation, as ilmenite
is conductive but xenotime is not (Jordens et al., 2013). The behav-
ior of Egyptian beach monazite with the electrostatic field setting
of the roll-type electrostatic separator was studied (Moustafa and
Abdelfattah, 2010). But the requirement of completely dry feed
material is the major drawback of this technique preventing it to
be applied on industrial scale.
Rare earth elements generally have a series of electrons occupy-
ing 4f sub-shell and these electrons have magnetic moments which
do not cancel out, resulting in a material with some degree of mag-
netism (Jordens et al., 2013). Magnetic separation, is a method
commonly used in rare earth mineral beneficiation to eradicate
highly magnetic gangue or to concentrate the desired paramag-
netic REE bearing minerals such as monazite or xenotime (Gupta
and Krishnamurthy, 2005). Beneficiation of monazite from beach
sand mineral, involves gravity separation along with magnetic sep-
arators to eliminate strongly magnetic minerals such as magnetite
and are also used to separate paramagnetic monazite from
non-magnetic heavy mineral gangue material such as zircon and
rutile (Ferron et al., 1991; Jordens et al., 2013). Ito et al., in 1991
predicted the magnetic susceptibilities of rare earth minerals and
did not found any changes in magnetic behavior for different oxi-
dation states of these elements.
Coarse heavy mineral sand of Congolone Mozambique, Zircon
Rutile Ltd of Australia, (Ferron et al., 1991) Cable Sands Pty Ltd
plants (Houot et al., 1991), the Climax Co. mine of Amax (Aplan,
1988; Cuthbertson, 1952), the Porter Bros. dry plant (Bautista
and Wong, 1989) are some of the industries in different countries
commercially practising mineral beneficiation for obtaining mon-
azite concentrate. The beneficiated product is then chemically
treated with acidic or alkaline reagents under the different condi-
tions to leach out the desired REEs in the solution. Alternately, the
undesired constituents are removed by chemical treatment to pro-
duce concentrated REEs product. SGS Minerals Services presents a
process flow-sheet for the processing of RE as given in Fig. 2.
3. Processing of monazite concentrate
As the monazite contains rare earth metals along with other
metallic values, their recovery is carried out from such materials
by pyro/hydrometallurgical processes consisting of heat treatment
followed by leaching, precipitation, solvent extraction, etc. The
physically beneficiated concentrate are leached in a suitable lixi-
viant acidic or alkaline solutions directly or after heat treatment
to dissolve the metallic values (Akkurt et al., 1993; Fatherly et al.,
2008). The formation of different complexes of REs during the
leaching under the different condition of Eh-pH in the sulfate
solution was also investigated (Kim and Osseo-Asare, 2012). The
studies have been carried out by different authors for the recovery
of REMs from various resources available in different countries
which are evident from the various papers appearing in journals,
proceedings and patents. The metals from the leach solution are
removed or concentrated by the precipitation, solvent extraction,
ion exchange, electrolysis, etc. to produce the desired salt or metals.
3.1. Direct leaching of monazite concentrate
As monazite is chemically and thermally stable concentrate in
the form of crystalline phosphate mineral, it is difficult to dissolve
such material in acids or alkali. It requires a suitable condition to
leach out the complex materials/metals present in the monazite
using acidic or alkaline solutions.
3.1.1. Direct leaching with acids
Different authors studied the direct leaching of monazite sand
using acidic solutions of sulfuric, hydrochloric and nitric acids
under the different experimental conditions to dissolve the REEs
or undesired components to get concentrate.
3.1.1.1. Leaching in sulfuric acid. The sulfuric acid has been used
most extensively for the leaching of monazite, where the sulfate
(SO2
4 ) ion of H2SO4 acts as a ligand which reacts with RE at high
temperature as follows (Fernelius, 1946; Barghusen and Smutz,
1958; Borrowman and Rosenbaum, 1962):
2REPO4ðsÞ þ 3H2 SO4 ¼ ðREÞ2 ðSO4 Þ3ðsÞ þ 6Hþ þ 2PO3
4 ð1Þ
The process is used in United States for the selective solubilisa-
tion of either Th or REs from monazite under controlled conditions
on industrial scale (Parker and Baroch, 1971). Fernelius et al. in
1946 as well as Kim and Osseo Asare in 2012 used 98% sulfuric acid
to leach out monazite at 200–230 °C which was subsequently
neutralized to separate REEs and Th. Pilkington and Wylie in
1947 reported for the recovery of RE by the precipitation of the rare
earth double sulfate. The process consists of digestion of monazite
in sulfuric acid followed by precipitation of REs with oxalate anions
under controlled pH from the sulfate solution (Fig. 3) (Welt et al.,
1958). The oxalate precipitate containing Th and RE oxides are
dissolved in nitric acid followed by selective extraction of REMs
with tributyl phosphate from the nitrate solution.
3.1.1.2. Leaching in sulfuric acid after mechanochemical
treatment. Kim et al. in 2009 reported the sulfuric acid leaching
after mechanochemical treatment of beneficiated monazite
(212 lm size) obtained from the beach sand deposit of Malaysia
(in wt% 20.5 Ce, 8.5 La, 6.9 Nd, 1.4 Pr, 0.7 Sm, 0.5 Gd, 0.8 Y and
11.4P) with sodium hydroxide at room temperature. The formation
of RE hydroxides and sodium phosphate was found to be complete
within 120 min grinding according to the reaction (2) and about
92.3% P was removed by washing. Subsequent leaching carried
out of the washed product with 0.05 N sulfuric acid solution
enabled to improve the yield of each of La, Nd and Sm to around
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115 107

Ground Monazite
Conc. H2SO4

LEACHING

Residue FILTRATION

Monazite Sulfate Solution

PRECIPITATION Oxalic acid

Oxalate Supernatant Oxalate Precipitate

U, PO43-, SO42- Th, RE
Octyl Pyro Phosphoric
Acid (OPPA) CALCINATION
Extract Phase U
FeSO4
HF Oxides of RE (Ce IV), Th
PRECIPITATION
LEACHING HNO3

Precipitate, UF4
Monazite Nitrate
Solution

SOLVENT EXTRACTION Tributyl Phosphate (TBP)

Aqueous Raffinate Organic Extract

RE, except Ce Ce(IV), Th

NaNO2 Solution
STRIPPING

H2O
Aqueous, Ce(III) Organic, Th

Aqueous Th Solution

Fig. 3. Flow-sheet for the processing of monazite sand by digesting in sulfuric acid.

Table 5 REPO4 þ 3NaOH ¼ REðOHÞ3 þ Na3 PO4 ð2Þ

The chemical composition of the ores of Tomtor and Chuktukon deposits.

Elements (oxide form) Contents %, (mass)

4CeðOHÞ3 þ O2 þ 2ð2n  3ÞH2 O ¼ 4½CeO2  nH2 O ð3Þ
Tomtor deposits Chuktukon deposits Pr forms first Pr(OH)3 and then Pr6O11  nH2O in the milled pow-
REEO including Y2O3 10.2 7.1 der. These oxides are not easily dissolved in dilute H2SO4 solutions
Nb2O5 6.7 0.5 (Zhang and Saito, 1998). These rare earth oxides are mostly dis-
TiO2 5.0 0.9 solved above 5 N acid concentration. Thus, mechanochemical
Al2O3 17.1 4.9
milling plays a significant role in achieving high recovery of REEs
P2O5 16.0 4.8
Fe2O3 12 51.4 from the leaching of the milled powder at room temperature.
MnO2 – 12.4
CaO 2.6 0.9 3.1.1.3. Leaching in nitric acid. Different researchers used nitric
SrO 3.8 0.4
acid for the dissolution of monazite and other associated metals
BaO 3.2 2.5
SiO2 3.8 4.8 from apatites (phosphorites) containing monazite (Aly and
SO3 0.5 – Mohammed, 1999; Jorjani et al., 2011; Konvisar et al., 1991). The
CO2 1.5 – nitric acid is more effective for leaching REEs from phosphorites
than sulfuric acid (Bunus and Dumitrescu, 1992). Gupta et al. in
2002 reported the dissolution of monazite sand in concentrated
85% or more. Also, the yields of Ce and Pr were respectively HNO3 with HF and HClO4 in ratio 3:1.5:0.5 in a Teflon vessel for
about 20% and 70% remain un-dissolved since they are changed 24 h at 80 °C. Recently, Kuzmin et al. in 2012 used the nitric acid
into oxide forms according to the reaction given below (3) to leach out the metals from the ground RE ore of 74 lm size
(Iijima et al., 1993; Zhang and Lincoln; 1994). (Chuktukon deposits, East Siberia, Russia) containing 3–7% REOs
108 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115
Ore
MILLING
Ground Ore
HNO3 AUTOCLAVE LEACHING
FILTRATION
Leaching Solution
Na2CO3 PRECIPITATION
Precipitate for processing to
recover REMs
Fig. 4. Schematic flow-sheet for the breakdown of the Chuktukon rare earth ore.
in the phosphate form (monazite, turnerite, florensite), Fe–Mn
oxides and 0.5–1% Nb oxide (chalcolamprite) (Table 5) in a
rotating autoclaves. The leaching reactions of monazite and
florensite with nitric acid are given below:
LnPO4ðsÞ þ 3HNO3ðlÞ ! Ln3þ 
ðlÞ þ 3NO3ðlÞ þ H3 PO4ðlÞ
LnPO4ðsÞ þ 5=8Fe2 O3ðsÞ þ 3HNO3ðlÞ
! LnðNO3 Þ3ðlÞ þ 1=4Fe5 ðPO4 Þ4 ðOHÞ3  2H2 OðsÞ þ 17=8H2 O
MnðNO3 Þ2ð1Þ ! MnO2ðsÞ # þ2NO2ðgÞ "
During the leaching, the iron and phosphorus remained in the
residue due to the formation of complex hydroxy ferric phosphates
which are poorly soluble in nitric acid. REEs recovery of 87–90% is
obtained during leaching in autoclave in the temperature range of
180–220 °C of the ground ore. The slurry is filtered to separate cake
containing niobium concentrate for subsequent processing to
produce niobium. The filtrate is treated with sodium carbonate
to precipitate REMs concentrate for subsequent treatment to
produce rare earth salts and manganese is also recovered as
pyrolusite as shown in Fig. 4 (Kuzmin et al., 2012).
3.1.1.4. Leaching of hydrous oxide cake of beach sand monazite in
nitric acid. In 2005, El-Nadi et al. used nitric acid as lixiviant to
leach out REEs from the hydrous oxide cake of Egyptian beach sand
containing 15% heavy minerals (monazite, ilmenite, rutile,
magnetite, zircon) collected from Demietta and Rosetta, Egypt after
uranium recovery by alkali treatment. It contained 0.3–1.5%
monazite which has been found to assay 26.5% Ce2O3, 34.3% other
RE2O3, 5.9% ThO2, 0.44% U3O8 (Osman, 1998). Initially, the ground
sample of 16.81 lm was treated with NaOH to dissolve sodium
phosphate followed by alkaline carbonate at 60 °C in order to
separate uranium selectively by forming tricarbonato complex
leaving thorium and RE elements as insoluble hydrous oxides
(El-Nadi et al., 2005; 1996). A recovery of 83% uranium was
Circulating HNO3
Cake (to Nb concentrate
production)
HNO3
Production
Nitrate Solution
THERMAL DECOMPOSITION Vapour gas
mixture
β-MnO2 (Pyrolusite)
obtained from the ground monazite. After carbonate leaching, the
precipitate was treated with nitric acid three times with heating
to dissolve the hydroxides (hydrous oxides) of the elements.
Studies have been made for the extraction of uranium by
solvent extraction which showed that tricarbonato uranium com-
ð4Þ plexes are selectively extracted by Aliquat-336 diluted in kerosene
from alkaline leach solution. The studies has shown that the
extraction was increased when the alkalinity (pH) decreased and
the main extracted species is [R2UO2 (CO3)2], where R refers to
ð5Þ
Aliquat-336 molecule. Sodium carbonate (1 M) stripped uranium
efficiently from alkaline medium. Based on these results, uranium
ð6Þ was purified from the leach solutions by extraction with
Aliquat-336 diluted in kerosene with purity not less than 99%.
A modified flow chart of the alkaline digestion, leaching, and
extraction of uranium from Egyptian monazite is presented in
Fig. 5 (El-Nadi et al., 2005).
3.1.1.5. Leaching in hydrochloric acid. In 2007, Rabie reported the
dissolution of Eu from middle RE concentrate of Egyptian black
sand monazite in HCl followed by its separation using combined
chemical reduction- precipitation techniques. A batch process
was developed to separate Sm, Eu, and Gd from the lanthanide
hydrous oxide cake produced from monazite mineral after
Ce-separation based on extraction by di-2-ethylhexylphosphoric
acid/kerosene from nitric–hydrochloric acid mixture. Different acid
solutions with different pH values for stripping were utilized and a
concentrate containing 98% of Sm, Eu and Gd as a group was
obtained with 78% recovery. Kumari et al. in 2013 studied two step
leaching of Korean monazite using diluted HCl at moderate
temperature for 2 h and pulp density < 100 g/L resulting in only
25% REMs dissolution. The concentrate left after phosphate
removal was leached in 6 N HCl at 90 °C for 2 h maintaining
60 g/L pulp density resulting in 90% REMs recovery (Panda et al.,
2014). Dong and Jinwen in 1985 investigated the separation
process of extracting U, Fe, Th and REEs under low acidity using
a monazite–U–Th–alkaline cake–hydrochloric acid solution as
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115 109

Monazite and concentration of sulfuric acid could accelerate the dissolution

of monazite concentrate.
But these acidic investigations have encountered a significant
GRINDING
drawback where the phosphate ions are lost by strong hot acid
attack. During acid dissolution, the phosphate ions get converted
Ground Ore (mesh size: 200-270; 130g) to phosphoric acid (a weak acid) which remains in solution as
triprotic acid, having three ionizable hydrogen atoms which are
LEACHING 50% NaOH, 140°C,
sequentially lost and thus, the phosphate ions.

3.1.2. Direct leaching in alkali

Filtrate
(Na3PO4 & excess NaOH)
FILTRATION Alkali treatment is used commercially for monazite dissolution
using caustic soda where the phosphate content of the ore is recov-
Precipitate
(Hydrous oxide of U, Th and REEs)
ered as a marketable by-product, trisodium phosphate. Different
authors (Krumholz, 1957; Meerson, 1957; Farah, 1965) reported
SEVERAL WASHING
the use of caustic soda at high temperature and pressure to dis-
Na2CO3, NaOH, H2O2,
60°C solve the phosphate ion of the monazite. In India, at Indian Rare
Earths Ltd (IREL), 3000–4000 tonnes of monazite per year are pro-
cessed using the caustic soda for the decomposition of monazite
FILTRATION Precipitate; Th + REEs sands (Gupta and Krishnamurthy, 2005). The caustic soda process
is also followed for the monazite treatment in the different plants
Filtrate (Uranium Tricarbonate)
established in Malaysia, France and U.S. (Sulaiman, 1991; Gupta
and Krishnamurthy, 2005; de Rohden et al., 1950). Mackey in
5% Vol. of Aliquat-336 DILUTION Water
1986 and in 1988, Hart and Levins treated the monazite using
70% NaOH under pressure for 2 h at 150 °C to produce insoluble
RE and Th hydroxides for subsequent processing. In 2005, Lauria
STRIPPING Na2CO3 (1M)
and Rochedo reported different processing steps for the treatment
of monazite at the Santo Amaro mill (USAM), Brazil as presented in
Fig. 6.
ACIDIFICATION HNO3
Meerson in 1957 investigated complete extraction of mineral in
two stages by decomposing monazite in heated ball mill using
Uranyl Nitrate

Monazite 85-95%
PRECIPITATION Ammonia pure

Uranium MAGNETIC
SEPARATION
Fig. 5. Modified flow-sheet of alkaline digestion, leaching and extraction of
uranium from Egyptian monazite.

Monazite 99% Light fraction

feed. DMHMP (Dimethylheptyl–methylphosphonate) and TBP
were taken as the extractants diluted in kerosene. It was found ALKALINE
that when DMHMP or TBP is used alone for extracting Th from DIGESTION
low hydrochloric acid concentration (1.5–2.0 N), the extraction
percentage of Th is only 1–2%.
FILTRATION

3.1.1.6. Comparison of leaching processes. Different investigations

are also done to compare the leaching processes at various condi- Phosphate solution Hydroxide cake
tions. Shin et al. in 2012 compared the leaching processes with Th, U, Ra, REE
temperature viz. the pressure leaching, electrogenerated chlorine
leaching and high concentration sulfate leaching using the NEUTRALISATION
monazite concentrate (45 lm size) containing 23.5% CeO2, 11.4%
La2O3, 8.72% Nd2O3 and 2.54% Pr6O11. The pressure leaching tested
FILTRATION
at 5 atm and 220 °C showed the increase in concentrations of Ce
and La with increasing sulfuric acid concentration from
0.01 mol/L to 1 mol/L. In the electrogenerated chlorine leaching
system, the concentration of La was found to decrease with Cake II Th & U Chloride solution
hydroxide Ra, REE
increasing temperature from 30 °C to 70 °C, due to decrease in
solubility of chlorine with increasing temperature. In the concen-
trated sulfuric acid leaching system, the leaching ratios of La and REE Chloride PRECIPITATION
Nd was found to increase to over 99% with increasing temperature
to 220 °C. The higher metal concentration of Ce, La and Nd are
Mesothorium cake
obtained in the concentrated sulfuric acid leaching system Ba(Ra)SO4
than in the pressure leaching and the electrogenerated chlorine
leaching system. This result suggests that higher temperature Fig. 6. Basic steps for chemical processing of monazite at USAM.
110 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115

Table 6
Direct leaching processes of different monazite concentrate using acid or alkali to recover REMs.

Source material Medium Salient features of the process Reference

Egyptian black sand Hydrochloric Dissolution of Eu from Egyptian black sand monazite in HCl followed by its separation using Rabie (2007)
monazite acid combined chemical reduction–precipitation techniques was used
Monazite from East Nitric acid REs ore of East Siberia possessing monazite containing 3–7% REOs is leached in HNO3 Kuzmin et al. (2012)
Siberia
Monazite Nitric acid Monazite sand was digested in concentrated HNO3 with HF and HClO4 in a tefflon vessel for 24 h at Gupta et al. (2002)
80 °C. After complete evaporation to dryness, the mass was dissolved in 5 M HNO3
Brazilian monazite Sulfuric acid Monazite was leached in H2SO4, the pH of sulfate solution is adjusted and oxalate anions are added. Welt et al. (1958)
The oxalate precipitate is separated, dried and calcined to their oxides. Th and REOs are dissolved in
HNO3, and contacted with TBP for selective extraction of REMs
Egyptian Monazite Sulfuric acid Complete U, Th and RE were separated from Egyptian monazite after H2SO4 leaching process where Rabie et al. (2013)
mineral was digested by 98% H2SO4 and dissolved in cold water (1:20) then precipitated with
ammonia (1:1) solution
Monazite Sulfuric acid Acid digestion of monazite with 98% sulfuric acid at 200–230 °C, yield a grey colored metal sulfate Kim and Osseo Asare
solid product which dissolves in cold water, filtered and neutralized to separate REEs and Th (2012)
Bald Mountain Sulfuric acid Monazite concentrate was decomposed by conventional sulfuric acid cure treatment and the leach Borrowman and
monazite liquor was processed by SX to yield 99% ThO2 product. Th raffinate was further processed for the Rosenbaum (1962)
concentrate recovery of RE oxide product
Monazite concentrate Sulfuric acid Pressure leaching, electrogenerated chlorine leaching and sulfuric acid leaching were tested, among Shin et al. (2012)
which concentrated sulfuric acid leaching system, results in 99% leaching of La and Nd at 2208 °C
Monazite sand Sulfuric acid Monazite was digested in 93% H2SO4 for 4 h at 210 °C results in 99% digestion if sands are ground to Barghusen and
at least 95%–65 mesh before digesting Smutz (1958)
Monazite sand Sulfuric acid Monazite sand is digested at 200–220 °C with 93–96% H2SO4 and the product was dissolved in water. Borrowman and
The resulting liquor was treated by various methods to recover and separate Th, REs, and U products Rosenbaum (1962)
Indian monazite Sodium The Indian Rare Earths Ltd. plant situated at always in Kerala, uses four major stages to attack Gupta and
hydroxide monazite by NaOH at 140 °C to recover REs Krishnamurthy
(2005)
Brazilian monazite Sodium Sodium hydroxide was added to monazite and the aqueous tri-sodium phosphate was separated Lauria and Rochedo
hydroxide from a solid phase, a hydroxide cake, by filtration. The cake was then leached in HCl for REE recovery (2005)
Monazite Sodium Monazite concentrates was leached with caustic soda solution at 130 °C in ball mill for complete Meerson (1957)
hydroxide extraction of mineral without pulverization, consuming half of caustic soda originally required for
decomposition
Monazite Sodium Monazite digestion using 70% NaOH solution under pressure for 2 h at 150 °C results in the formation Mackey (1986)
hydroxide of insoluble RE and Th hydroxides
Australian monazite Sodium Processing of Australian monazite concentrate using 80% w/v NaOH at 140 °C for 3 h having wt ratio Gupta and
hydroxide of NaOH:monazite of 1.5:1 resulted in the extraction of 98% REs Krishnamurthy
(2005)
Egyptian monazite Sodium Complete alkaline leaching of Egyptian monazite was attained at 150 °C and 175 °C within 2.5 and Abdel-Rehim (2002)
hydroxide 1 h respectively in ball mill autoclaves, where grinding and leaching takes place simultaneously
Monazite Sodium The alkali decomposition of monazite with hot concentrated 50–75% NaOH proceeds as was carried Habashi (1997)
hydroxide out at 150 °C in an autoclave
Korean monazite Sodium 50% NaOH (w/v) solubilizes 99.99% phosphate of Korean monazite, at 170 °C, 100 g/L pulp density in Panda et al. (2014)
hydroxide 4 h. Kinetics of phosphate leaching fitted well with model ‘‘chemical reaction control’’ i.e. 1  (1  X)
1/2 = kct, Ea = 73.65 kJ/mole
Egyptian monazite Sodium Hydrous oxide cake of monazite was prepared by digesting it in 50% NaOH for 4 h at 140 °C followed Ali et al. (2007)
hydroxide by leaching with alkaline carbonate solutions. This cake was dissolved in 4 M HNO3 for further
extraction of Th using Aliquat 336 in kerosene
Egyptian monazite Sodium 10 g monazite was treated with 50 wt.% of NaOH solution and boiled for 4 h at 140 °C. Solution was El-Nadi et al. (2005)
hydroxide diluted up to 20 wt.% NaOH concentration and boiled again for 1 h and filtered at 80 °C. U is easily
separated after Na2CO3 leaching of the residue obtained
Monazite Sodium Monazite was digested in caustic soda to crack the phosphate matrix and then leached in acid to Hart and Levins
hydroxide dissolve rare earth along with radium (1988)
Monazite Sodium Monazite is treated with 60–70% NaOH at 120–150 °C and after filtration Na3PO4 is separated from Kim and Osseo-
hydroxide RE hydroxide Asare (2012)
Monazite from Sodium Monazite was slowly added to NaOH solution and heated to 140 °C for 3 h. The mixture was then Soe et al. (2008)
Moemeik Myitsone hydroxide diluted with distilled water at 105 °C for 1 h. The slurry was filtered at 80 °C to keep caustic soda and
Area trisodium phosphate in solution
Hongcheon monazite Sodium 90% RE oxide was obtained by NaOH hot digestion using NaOH/TREO mole ratio of 15 at 140 °C and Kim et al. (2010)
hydroxide 2 h time. REO obtained was further dissolved in HCl

caustic soda solution. Ney et al. reported that the Brazilian industry
processes monazite at high temperature ranging from 140 to
200 °C for effective decomposition using the sequence of
operations of: magnetic field separation, milling, alkaline treat-
ment, trisodic phosphate filtration and Th U cake filtration. The
alkali decomposition of monazite with hot concentrated 50–75%
NaOH was carried out at 150 °C in an autoclave (Habashi, 1997).
REðPO4 ÞðsÞ þ 3NaOH ¼ REðOHÞ3ðsÞ þ 3Naþ þ PO3
4 ð7Þ
Direct leaching of REMs from Korean monazite concentrate
(containing 50% REOs, 29.44% PO3
4 and around 20% trace rare
earth oxides (TREOs)) using 50% NaOH (w/v) at 170 °C for 4 h
keeping pulp density 100 g/L is also reported where the kinetics
of phosphate leaching fitted well with model ‘‘chemical reaction
control’’ i.e. 1  (1  X)1/2 = kct with activation energy of
25.44 kJ/mole (Panda et al., 2014). Ali et al. in 2007 recovered Th
from Egyptian monazite sand after alkaline dissolution followed
by leaching with alkaline carbonate solution. The studies were
made by different authors to improve the processes from various
complex ores/concentrates. An economic method was recom-
mended for separation and purification of thorium and uranium
from the hydrous oxide cake concentrate obtained from Egyptian
monazite sands by alkali treatment of the mineral (Lauria and
Rochedo, 2005). The study for the extraction of lanthanum oxide
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115
Table 7
Summary of leaching technologies used with monazite to produce rare earth elements.
Different processes Yield of Remarks
REE (%)
Digestion in hot H2SO4 – Process conditions determine whether light rare earths are only leached or along with light rare
earths, heavy rare earth elements as well as thorium are also leached. This process yields no
pure product
(i) Digestion in hot 60–70% NaOH 98 Cerium cannot be leached if manganese is present. Thorium is leached together with rare earth
(ii) Washing residue with hot water elements. Sodium tri-phosphate (Na3SO4) is a marketable byproduct
(iii) Leach with mineral acid of choice
(i) Heat under reducing and sulphidiz- 89 Fine grinding is not required. Thorium remains in the residue as ThO2. No problem of
ing atmosphere with CaCl2 and manganese is observed
CaCO3
(ii) Leach with 3% HCl
from monazite concentrate was also carried out using NaOH
(Soe et al., 2008). Kim and Osseo-Asare in 2012; El-Nadi et al. in
2005 as well as Kim et al. in 2010 reported the hydrometallurgical
processing of monazite by optimizing leaching conditions for the
dissolution of monazite for RE recovery by hot digestion method
using NaOH. Several methods are used for industrial processing
of monazite to extract lanthanides (Anwar and Abdel-Rehim,
1970; Doyle and Duyvesteyn, 1992; Cuthbert, 1958; Kaplan,
1960; Rajagopalan, 1957; Zelikman, 1963; Sinyaver, 1966; Hilal
and Kiwan, 1968; Habashi, 1999). An innovative method for
processing Egyptian monazite by alkaline leaching in ball mill
autoclaves was studied, where grinding and leaching of monazite
take place simultaneously. Leaching was followed by selective
separation of Th and U from lanthanides (Abdel-Rehim, 2002).
The salient features of different processes for monazite processing
using direct leaching with acid and alkali are shown in Table 6.
3.1.2.1. Leaching of RE concentrate of monazite in ammonium
carbonate. In 2006, de Vasconcellos et al. studied REE concentrate
(analysis in (%): Y2O3 2.4, Dy2O3 0.6, Gd2O3 2.7, CeO2 2.5, Nd2O3
33.2, La2O3 40.3, Sm2O3 4.1 and Pr6O11 7.5) produced industrially
from the chemical treatment of monazite sand in Sao Paulo,
Brazil to enrich yttrium by leaching and precipitation process.
The yttrium concentrate was treated with 200 g/L ammonium
carbonate for 10–30 min at room temperature to dissolve yttrium
along with other REEs. Subsequently, cerium, praseodymium and
neodymium were selectively precipitated using hydrogen peroxide
from the leach solution leaving yttrium in the solution. Yttrium
was then recovered from the carbonate solution as the oxalate
and finally as oxide having 81% Y2O3.
3.2. Pre-treatment of monazite concentrate
In order to improve the recovery of REEs from the monazite,
the material is pre-treated before leaching in suitable
lixiviants. Several literatures have been reported related to the
pre-treatment of monazite with alkali for subsequent processing
(Panda et al., 2014; Franken, 1995). The concentrates are usually
calcined at varying temperature with alkali in a rotary tubular
electric furnace. Yanhui et al. in 2012 reported the calcination
temperature on decomposition of rare earth, oxidation of cerium,
removal of fluorine and phosphorous etc. The decomposition of
rare earth and the oxidation of cerium were found to be 95.8%
and 93.7%, respectively above 300 °C. In 2004, Kim et al. found
the decomposition of monazite concentrate with NaOH at 460 °C
and NaOH/TREO mole ratio of 6. Shuchen et al. in 2007 obtained
79% decomposition of REPO4 with CaO when 10% of NaCl–CaCl2
used at roasting temperature of 150 °C in 1 h. In 2007, Wen-yuan
et al. reported the calcinations of monazite and mixed rare
earth minerals with CaO–NaCl–CaCl2. They also studied the
111
Status
Outdated
In use
In use
decomposition of monazite and mixed rare earth concentrate by
TG/DTA method with CaO–CaCl–CaCl2 at 700 °C for 1 h. Xue et al.
in 2010 reported that the intensity of the peak during TG/DTA
studies of monazite decomposed by CaO at 700–750 °C is increased
on addition of NaCl–CaCl2. In 2010, Peng-fei et al. removed 98%
phosphorus from the monazite pellets when the mixture of
monazite, charred coal roasted at 1400 °C for 2 h.
A roast–leach process has been reported for the extraction of
rare earth from complex monazite concentrates using sulfuric acid
and other leaching agents at the Pea Ridge iron mine in Sullivan
(Franken, 1995). In this process, the RE phosphate of the ore is
converted to its oxide, which eliminated hazardous processing
steps currently in practice. The cerium present in the ore is
selectively solubilized with 265 g/L sulfuric from the roasted mass
at 427 °C. Subsequently, the neodymium and lanthanum can be
leached with 88 g/L sulfuric acid after roasting at 500 °C. Finally,
neodymium, praseodymium and yttrium are solubilized at a
roasting temperature of 871 °C and a sulfuric acid concentration
of 265 g/L. Alternative leaching media, such as thiourea, sulfuric
acid-doped thiourea mixtures, ammonium thiosulfate, nitric acid
and hydrochloric acid have also been investigated with ultrasonic
agitation. With ultrasonics agitation, hydrochloric acid proved to
be the best leaching medium. The best roasting temperatures for
selective solubilization remained the same with 64 g/L hydrochlo-
ric acid. Kim et al. in 2009 also reported the sulfuric acid leaching
after mechanochemical treatment of monazite with sodium
hydroxide at room temperature. The optimum time for the milling
of the mixture for mechanochemical activation for the formation of
RE hydroxides and sodium phosphate is about 120 min.
3.3. Leaching of monazite concentrate after pre-treatment
Apart from the conventional direct leaching of concentrate in
acid or alkali, several studies have been done on monazite leaching
after pre-treatment which may improve recovery of REOs by
consuming less acid and eliminating hazardous steps generally
practiced. In 2011, Hussein reported that the hydroxide cake
obtained from alkaline processing of monazite is leached with
HCl at 80 °C. To determine the efficiency of monazite leaching,
the hydroxide cake obtained by alkaline processing is leached in
10% HCl at 80 °C for 30 min (Abdel-Rehim, 2002). Franken in
1995 used HCl after roasting monazite (Pea Ridge iron mine,
Sullivan) for the solubilisation of phosphate. The NaOH hot
digestion product was leached in 6 N HCl for 2 h and pulp density
of 15%, yielding 90% RE (Kim and Osseo-Asare, 2012). The
decomposed monazite concentrate of Hong-Cheon area was
leached in 8 N HCl at 80 °C for 2 h with 10% pulp density leading
to 90% recovery of REMs (Kim et al., 2004). The precipitated
hydrous oxide cake produced by alkaline dissolution of Egyptian
monazite was washed with a solution containing 40 vol.% 1 M
112 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115

Monazite

CHEMICAL DIGESTION

Ce-REMOVAL

Rare Earth Cake

LEACHING 1 HCl: 1HNO3

Leach Liquor

D2EHPA EXTRACTION pH 1.0

Organic
Aqueous Raffinate Major (Middle+Heavy) REEs + Minor LREEs
(Major Rare Earths)

STRIPPING Solution pH 0.8

Strip Solution Organic (Major Heavy REEs)

Major Middle REE + Minor LREEs

PRECIPITATION &
REDISSOLUTION

D2EHPA RE-EXTRACTION pH 1.0

Organic (Major Middle REEs)

RE-STRIPPING pH 0.7

Aqueous
Sm-Gd-Eu Concentrate [98% purity, 78% Recovery]

Fig. 7. Flow-sheet illustrating the successive extraction and stripping stages to separate middle rare earth concentrate.

Na2CO3, 50 vol.% 1 M NaOH and 10% H2O2 for uranium removal.
The cake left was further dissolved in 4 M HNO3 (Ali et al., 2007).
Alkali cake obtained after the calcinations of rare earth concentrate
in the rotary tubular electric furnace was mixed with HCl (6 mol/L)
at 90 °C with agitation for 30 min (Yanhui et al., 2012). Recently,
the rare earth concentrate (containing 50% REOs, 29.44% PO3 4 of leaching technologies used with monazite to produce rare earth
and around 20% trace rare earth oxides (TREOs)) obtained from
the Korea was first dephosphorised with 50% NaOH (w/v) at
170 °C and 100 g/L pulp density in 4 h (Panda et al., 2014). The
kinetics of leaching for the dephosphorization was found to follow
the chemical reaction controlled model. Further, Panda et al. in
2014 also investigated that the rare earth hydroxide (REHs) left
after alkaline leaching in autoclave was further dissolved in 6 N
HCl at 90 °C, 60 g/L pulp density for 2 h to recover 95% REMs.
3.4. Overview of the leaching technologies
Monazite is among the main rare earth minerals used in the pri-
mary production of rare earth elements. A review on most of the
currently prevailing leaching technologies for rare earth produc-
tion is needed which is essential for significant investigations on
rare earth metal extraction from various resources. A variety of
technologies have been proposed which are still in the stage of
research. In order to improve the possibilities of rare earth
elements extraction from different resources, a concise overview
of the leaching technologies used in primary rare earth production,
both past and present, is necessary. Table 7 presents the summary
elements (Peelman et al., 2014).
3.5. Processing of leach solution by solvent extraction (SX)
Different authors used SX process for the extraction of metals
from the leach solution of monazite to extract the valuable to
produce REEs. Recovery of thorium, uranium, and rare earths from
monazite sulfate liquors by the amine extraction (amex) process
was also reported (Crouse and Brown, 1959a, 1959b). The
monazite concentrate from the Wyoming ore was reported be
decomposed by the sulfuric acid-curing followed by SX to separate
Th and REEs (Borrowman and Rosenbaum, 1962). In 1960, Welt
and Smutz used tributylamine (TBA) and di-n-octylamine (DOA)
solvents for the recovery of uranium and thorium from Egyptian
monazite sulfate leach liquor. Gupta et al. in 2002 reported the
use of Cyanex 923 for uranium, thorium and lanthanides (Ce, Y)
 A. Kumari et al. / Minerals Engineering 79 (2015) 102–115
from the digested leach solution of monazite in HNO3 with HF and
HClO4. In 2007, Rabie et al. used di-2-ethylhexylphosphoric acid in
kerosene for the separation of Sm, Eu, and Gd in nitric–hydrochlo-
ric acid mixed solution obtained from the lanthanide hydrous
oxide cake produced from monazite mineral of the Egyptian beach
black sand deposits after Ce-separation. Under the optimised SX
condition, a concentrate containing 98% of Sm, Eu, and Gd as a
group was obtained with a 78% recovery (Fig. 7).
Amaral and Morais in 2010 used the mixed extractant of
Primene JM-T and Alamine 336 in kerosene for the selective
extraction of Th and U from the sulfate leach solution of monazite.
The solvent extracted almost total Th and U leaving only 0.001 g/L
metals in the raffinate. The loaded Th and U were stripped with HCl
solution. The process was validated in continuous mode using MSU
of four and five stages of extraction and stripping stages. In 2013,
Rabie et al. reported the possibility of extracting completely,
uranium by using tri-butyl phosphate (TBP) as an extractant from
leach liquor produced after sulfuric acid monazite digestion. The
stripping was carried out with cold water. After selecting the best
conditions for the process, which was 40–50% TBP/kerosene
extractant concentration, 1.5–2 M oxalic acid concentration as a
precipitant for thorium (extracted with uranium), 45–60 min
stirring time and temperature was 40–50 °C. A loaded stripping
solution containing 0.1986 g of U3O8 from the starting 0.21 g with
more than 99% purity and 99.3% recovery was obtained.
3.6. Recovery of REs from the leach solution by precipitation
Abreu and Morais in 2010 reported the development of an
efficient and relatively simple process to obtain high grade CeO2
from sulfuric acid leach liquor obtained through acid digestion
of monazite. The process step consists of purification of the RE
by precipitation as rare earth and sodium double sulfate
[NaRE(SO4)2  xH2O] followed by its conversion into RE–hydroxide
(RE(OH)3) through metathetic reaction and recovery of cerium.
The cerium is then purified from the mixture of ceric hydroxide
and manganese dioxide precipitate through dissolution of the solid
with HCl and precipitation of the cerium through the addition of
oxalic acid (H2C2O4) or ammonium hydroxide (NH4OH) solution.
The precipitate is calcined to get 99.5% pure CeO2 with recovery
yield greater than 98%.
The flow sheets provided are reported to be feasible. However,
the cost of the processes depend on various factors viz. cost of
raw materials, availability of high grade ore, chemicals, land,
infrastructure, global demand and supply. Some of the process
flow-sheets are of bench scale studies and others are commercial
scale process. The commercial scale processes are well proved as
plants are running. Bench scale flow-sheets are also required for
the scale-up studies for testing of feasibility/commercialization.
3.7. Environmental aspects of monazite processing
Any chemical process used to recover metals from different
resources effects the environment directly or indirectly. However,
mining of primary ores also effect the whole ecosystem as mining
has possibility to liberate detrimental substances of radionuclides,
acids, fluorides, etc. due to overtopping/collapsing of tailing dams.
Thus, government enforces regulations on companies and use
technology to reduce the damage due to mining by establishing
safeguards before operations proceeds. As far as hydrometallurgi-
cal processes are concern, either acids or alkali are used, which
releases toxic fluids and gases. But all this detrimental effects can
be controlled by expanding various technologies viz. scrubbing of
toxic gases released using different reagents or regenerating the
acidic solution for further use, etc. But, overall, to avoid the effects
on the ecosystem due to mining and processing of primary
113
resources, RE recovery from secondary resource recycling would
be a great opportunity to secure REEs and save the environment.
4. Conclusions
Based on the above review, the recovery of REMs from its
mineral monazite has been made by physical beneficiation
followed by hydrometallurgical treatment using acidic and alkaline
solutions, the following conclusions can be made.
 Combined physical and flotation methods viz. gravimetric,
electrostatic or magnetic separation processes have been used
for the recuperation of monazite concentrate from fine heavy
mineral beach sand deposits where standard gravity methods
are not very efficient for finer size range and thus, flotation
method is useful.
 The beneficiated monazite ore is usually processed following
hydrometallurgical and sometimes pyrometallurgical opera-
tions to recover REMs. However, several literatures have been
reported related to the pre-treatment study of monazite
concentrate.
 The use of sulfuric acid in various industries for processing
monazite results in the loss of phosphoric acid content, low
solubility of the sulfates formed, poor separation of Th and
REs and high cost of maintenance. The drawbacks of the acidic
process make the alkaline (NaOH) treatment acceptable from
industrial point of view.
 Apart from the conventional method of direct leaching of
monazite concentrate in acid or alkali, several studies have been
done on monazite leaching after pre- treatment processes
which may increase the percentage yield of REOs by consuming
less acid and will also eliminates some costly and hazardous
processing steps generally practiced.
 The leach solution containing REEs and other metals such as Th
or U obtained could be further purified by precipitation/solvent
extraction process.
 The development of modern and lucrative technologies in field
of primary processing is mandatory to utilize indigenous
resources but in order to avoid the effects on the ecosystem
due to mining and processing of primary resources, RE recovery
from secondary resource recycling would be a great opportunity
to secure REEs and save the environmental. The expansion in
these prevailing technologies will meet the future necessities
of REs in a variety of applications.
Acknowledgements
This paper is based on the joint collaborative research work
carried out between CSIR-National Metallurgical Laboratory
(CSIR-NML), Jamshedpur, India and Korea Institute of
Geosciences & Mineral Resources (KIGAM), South Korea. Authors
are thankful to the Korea Institute of Geosciences & Mineral
Resources (KIGAM), South Korea for the financial support. We
would also like to acknowledge the financial support provided
under the R & D Convergence Program of MSIP (Ministry of
Science, ICT and Future Planning) and NST (National Research
Council of Science and Technology) of Republic of Korea (Grant
B551179-11-01-00).
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