Kumar I 2015

Minerals Engineering 79 (2015) 102115
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
b
Metal Extraction and Forming Division, CSIR-National Metallurgical Laboratory, Jamshedpur 831007, India
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
Article history:
Received 25 February 2015
Revised 8 May 2015
Accepted 10 May 2015
Keywords:
Monazite
Rare earth metals (REMs)
Mineral beneciation
Leaching
Solvent extraction
a b s t r a c t
The escalating demand of rare earth metals (REMs) in various applications and their continuous depleting
ores have laid emphasis to produce metals from their complex resources by developing energy efcient
and eco-friendly processes. Present review reports the commercial processes based on pyrohydro or
hybrid techniques as well as systematic research for process development to recover rare earth from
monazite. The salient ndings on mining and physical beneciation of different beach sand deposits containing monazite are reviewed. Monazite concentrate obtained are processed under different condition of
time, temperature and concentration using acidic or alkaline solution. They are usually processed using
thermal treatment followed by REMs recovery under optimized conditions of leaching and their extraction via solvent extraction, precipitation, etc. to produce salts/concentrate of REMs from the leached solution. The processes developed to recover REMs are reviewed and recommendations are made in respect
to various methodologies and objectives.
2015 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Processing of different minerals to obtain monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Mining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Physical beneficiation of monazite minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Gravity separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
Electrostatic and magnetic separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Processing of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Direct leaching of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.
Direct leaching with acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.1. Leaching in sulfuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.2. Leaching in sulfuric acid after mechanochemical treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.3. Leaching in nitric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.4. Leaching of hydrous oxide cake of beach sand monazite in nitric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.5. Leaching in hydrochloric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.1.6. Comparison of leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.
Direct leaching in alkali . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.2.1. Leaching of RE concentrate of monazite in ammonium carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Pre-treatment of monazite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Leaching of monazite concentrate after pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Overview of the leaching technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.
Processing of leach solution by solvent extraction (SX) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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/ 2015 Elsevier Ltd. All rights reserved.
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A. Kumari et al. / Minerals Engineering 79 (2015) 102115
4.
3.6.
Recovery of REs from the leach solution by precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.7.
Environmental aspects of monazite processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Rare earth metals (REMs) are group of 15 elements of the lanthanide series including Sc and Y, which are mainly classied 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, uorescent
lights, metal alloys, critical military applications and in the manufacturing 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 escalating 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 deciency 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 earths 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 minerals of carbonates, oxides, phosphates and silicates as trivalent
cations. Table 2 presents few of these minerals with the approximate percentage of RE oxide content (Hedrick, 2004; Kumari
et al., 2013). In most deposits, REEs can be recovered as the primary product or as a co-products/by-products of certain other
minerals. These RE minerals are located throughout the world,
113
113
113
113
113
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 policy of Chinese government has drastically reduced the export of
REMs causing increase in the REs 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: bastnasite, 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 rst discovered as a novel exogenous ore in Jiangxi province 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 processing 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 412% ThO2, 2030% Ce2O3, and 1040% 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 pyrohydro or hybrid techniques, consisting of direct leach or pretreatment
followed by leaching in acidic/alkaline solutions. The systematic
research and various ow-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, availability, metal content, engineering feasibility, transportation, government norms, etc. The mining and processing of rare earth
Table 1
Abundance of rare earth elements in earths crust.
Fig. 1. Global estimated demand for total RE oxides in 2011.
Elements
Atomic number
Abundance (ppm)
Lanthanum
Cerium
Praseodymium
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Holmium
Erbium
Thulium
Ytterbium
Lutetium
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
30
60
6.7
27
1018
5.3
1.3
4.0
0.7
3.8
0.8
2.1
0.3
2.0
0.4
104
Table 2
RE oxides present in rare earth minerals.
Carbonate
Mineral
REO (%)
Bastnaesite (Ce, La)(CO3)F

75
Parisite Ca(Ce, La)2(CO3)3F2

61
Synchysite Ca(Ce, LA)(CO3)2F

51
Cebaite Ba3Ce2(CO3)5F2
32
Phosphate
Mineral
REO (%)
Apatite Ca5(PO4)3(F, Cl, OH)

19
Monazite (Ce, La, Nd, Th)PO4

65
Xenotime YPO4
61
Florencite CeAl3(PO4)2(OH)6
32
Silicate
Mineral
REO (%)
Gadolinite (Ce, La, Nd,

Y)2Fe2+Be2Si2O10
60
Allanite (Ce, Ca, Y)2(Al,

Fe3+)3(SiO4)3OH
38
Kainosite Ca2(Y,
Ce)2Si4O12CO3H2O
38
Britholite (Ce, Ca)5(SiO4,

PO4)3(OH, F)
32
Oxide
Mineral
Fergusonite (Ce, La, Nd)NbO4
REO (%)
53
Loparite (Ce, La, Na, Ca, Sr)(Ti,

Nb)O3
30
Euxenite (Y, Ca, Ce, U, Th)(Nb, Ta,

Ti)2O6
24
Brannerite (U, Ca, Y, Ce)(Ti,

Fe)2O6
9
Table 3
Rare earth contents of major and potential source of monazite minerals. (Percentage of total rare-earth oxide).
Rare earth
elements
Cerium
Lanthanum
Neodymium
Praseodymium
Samarium
Europium
Gadolinium
Terbium
Dysprosium
Erbium
Yttrium
Holmium
Thulium
Ytterbium
Lutetium
TOTAL
Monazite
North Capel, West
Australia
North Stradbroke Island, Queensland,

Australia
Green Cove
Springs, USA
Nangang,
Guangdong, China
East Coast,
Brazil
Mount Weld,
Australia
46.00
23.90
17.40
5.00
2.53
.0530
1.49
.0350
.7000
.2000
2.40
.0530
Trace
.1000
Trace
100.00
45.80
21.50
18.60
5.30
3.10
.8000
1.80
.3000
0.6000
.2000
2.50
.1000
Trace
.1000
.0100
100.00
43.70
17.50
17.50
5.00
4.90
.1600
6.60
.2600
.9000
Trace
3.20
.1100
Trace
.2100
Trace
100.00
42.70
23.00
17.00
4.10
3.00
.1000
2.00
.7000
.8000
.3000
2.40
.1200
Trace
2.40
.1400
100.00
47.00
24.00
18.50
4.50
3.00
.1000
1.00
.1000
.4000
.1000
1.40
Trace
Trace
.0200
ND
100.00
51.00
26.00
15.00
4.00
1.80
.4000
1.00
.1000
.2000
.2000
Trace
.1000
Trace
.1000
Trace
100.00
ND not detected.
minerals is complicated, costly and there is potential for negative

effects on the environment (Hurst, 2010). Mines are the major
source for the release of three major contaminants: radionuclides,
rare earth elements, and dust and metal. Each of these contaminants escapes have different detrimental effects on the environment. The details of the mining and physical beneciation of the
monazite containing minerals to produce monazite concentrate
are discussed below.
2.1. Mining
Mining involves removing mineralized rock containing RE
deposits from ground through open-pit or underground methods.
Open pit operations are performed by the worlds largest RE mines,
Bayan Obo in China and Mountain Pass in United States using
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,
2005). However, underground room and pillar mining are conducted where REs are recovered as by-product (Jackson and
Christiansen, 1993). Placers sands are under water/affected by a
high water table and are mined by dredges. Proper steps for the
treatment of a placer monazite concentrate by dredging are also
reported Bucket wheel units are used to mine the shallower sands,
while bucket line and suction dredges are used for mining deeper
material (Panigrahi, 2013). A degree of initial concentration is
usually performed at the dredge site itself. The material is then
transported as slurry through a pipeline to the beneciation plant.
Table 4
Selected rare earth companies and their primary mines.
Company
Country
Primary mines
Molycorp, Inc.
United
States
Australia
Canada
Australia
Australia
United
States
Canada
Mountain Pass
Australia
Kvanefjeld
Canada
Canada
Canada
Canada
Strange Lake (B Zone)

Norra Karr
Kutessay II
Bokan (Dotson)
Lynas Corporation, Ltd.

Avalon Rare Metals, Inc.
Alkaline Resources, Ltd.
Arafura Resources, Ltd.
Rare Element Resources, Ltd.
Great Western Minerals Group,
Ltd.
Greenland Minerals and Energy,
Ltd.
Quest Rare Minerals, Ltd.
Tasman Metals, Ltd.
Stans Energy Corp.
Ucore Rare Metals, Inc.
Mount Weld
Nechalacho (Thor Lake)
Dubbo
Nolans Bore
Bear Lodge (Bull Hill
Zone)
Steenkampskraal
Some of the selected RE companies in various countries and their

mines are shown in Table 4 (Jordens et al., 2013).
The future of strategic natural resources, Mission 2016 proposes
that unfettered mining has probability to release harmful substances of radionuclides, acids, uorides, etc. into the environment
due to overtopping/collapsing of tailing dams. Open pit mining
exposes radioactive elements due to crushing of hard rocks while
the underground mining has potential for tunnel collapsing and
land subsidence. However, mining by in situ and heap leaching
has environmental and safety advantages over conventional mining but the release of toxic uids used to dissolve the ore bodies
105
affect the ecosystem as well as human population. About 9600

12,000 cubic meters of toxic gases are released for each ton of
REEs produced with nearly 75 cubic meters of acidic waste water
and one ton of radioactive waste residue. Government enforces
regulations on companies and use technology to reduce the damage due to mining by establishing safeguards before operations
proceeds. Ion-absorbing Type Rare Earths Ore mining is also present which causes series of environmental problems (Liu et al.,
2013).
2.2. Physical beneciation of monazite minerals
In placer deposits, monazite occurs as a minor constituent while
the major minerals are ilmenite, rutile, zircon, and quartz.
Monazite is a REthorium phosphate, in which high content of a
naturally occurring radioactive element presents a negative aspect
of mining and processing (Kul et al., 2008). As a result, it is mined
as heavy-mineral sand from Aeolian beach and recovered as a
by-product during processing of ilmenite, rutile, zircon and cassiterite. Monazite is found in Manavalakurichi, Pulmoddai deposit,
Orissa and Chavara deposits as well as REs division at Aluva in
India (Gupta and Krishnamurthy, 2005). Indian Rare Earth
Limited
presents
the
mineralogical
composition
of
Manavalakurichi deposit which was found to contain 10.7 wt% of
monazite, which is almost 3000 tons while the RE deposit at
Aluva treat about 3600 tons of monazite (Peravadhanulu, 1979).
The beach sands of Manavalakurichi and Pulmoddai were not
pre-concentrated but directly put in for separation into its constituents using electrostatic and magnetic methods. Beneciation
processes of beach sand minerals probably vary from location to
location depending on their mineralogical and chemical
composition.
International Atomic Energy Agency reported that the heavy
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
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
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 monazite and is electrostatically separated from ilmenite due to its
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
enables easy separation. Similarly, if rutile and zircon are
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
purity of monazite concentrate is upgraded to 98% using
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,
otation, electrostatic separation or magnetic processes (Jordens
et al., 2013, 2014).
Biswas, 2008; Pavez and Peres, 1994). Beneciation by otation

had also been developed for Indian monazite. Fatty acid and
hydroxamate otation are the principle techniques explored but
more research into beneciation techniques are required to successfully start production once again at Mountain Pass. For selective otation, monazite gangue materials, zircon and rutile,
require depressant like sodium silicate, sodium sulde and sodium
oxalate (Pavez and Peres, 1993a,b; 1994). Combined physical and
otation methods have been used for recuperation of monazite
concentrate from ne heavy mineral beach sand deposits (Ferron
et al., 1991) which is not possible in case of gravity separation.
However, the otation knowledge regarding monazite needs more
exploration as the physico-chemical characteristics of monazite is
not conrmed.
2.2.2. Gravity separation
Gravity separation process is commonly utilized in rare earth
minerals (mostly in monazite beneciation) as they have relatively
large specic gravities and are typically associated with gangue
material, primarily silicates that are signicantly less dense
(Ferron et al., 1991). A design was presented by Moustafa and
Abdelfattah in 2010 to concentrate monazite from Egyptian beach
sands containing 30 wt.% valuable heavy minerals. Wet gravity
separation was used initially to discard low specic gravity gangue
and then low intensity magnetic separation to discard any ferromagnetic minerals without removing paramagnetic monazite. A
chain of gravity, magnetic and electrostatic separations were further applied where rutile was removed after electrostatic separation followed by the removal of diamagnetic zircon from the
paramagnetic monazite by magnetic separation to exploit different
properties of the monazite, zircon and rutile minerals and produce
the nal concentrate (Moustafa and Abdelfattah, 2010).
Beneciation of a beach placer sand deposit from Malawi is
Ore
CRUSHING/ GRINDING
CONCENTRATION
(Flotation)
Salt
ROASTING/ CRACKING
(Eg. Pug roast or Salt roast)
LEACHING
FILTRATION
Acid or Caustic
Acid/ Alkali
Solution
Residue
Liquor
STABILIZATION
PURIFICATION
2.2.1. Flotation
Bulk heavy mineral concentrate are also produced from ne
grained beach sand deposits by otation using fatty acid or
phosphoric acid esters as collectors depending upon the ease of
desorption prior to separation (Ferron et al., 1991). Monazite
otation using sodium oleate as collector, as well as the effect of
sodium metasilicate and sodium sulphide on the oatability of m
onazitezirconrutile and its characteristics has also been investigated (Cheng et al., 1993; Pavez and Peres, 1993a,b; Dixit and
PRECIPITATION/
SOLVENT EXTRACTION
Raffinate or
Barren Liquor
RE salts
Fig. 2. Flow-sheet of a rare earth processing.
106
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
otation has been employed between the rougher and cleaner
otation circuits for efcient 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 successfully completed on Turkish and Australian deposits where it
was found that the rare-earth minerals were concentrated into
very ne particles. To overcome this, either grinding steps were
modied to prevent excess ne generation or multi-gravity separator was employed to recover ultrane 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 carbonates to oxides, thus increasing the mineral density and susceptibility to gravity separation.
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 beneciated concentrate are leached in a suitable lixiviant 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
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 minerals with similar specic 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 behavior of Egyptian beach monazite with the electrostatic eld 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 occupying 4f sub-shell and these electrons have magnetic moments which
do not cancel out, resulting in a material with some degree of magnetism (Jordens et al., 2013). Magnetic separation, is a method
commonly used in rare earth mineral beneciation to eradicate
highly magnetic gangue or to concentrate the desired paramagnetic REE bearing minerals such as monazite or xenotime (Gupta
and Krishnamurthy, 2005). Beneciation of monazite from beach
sand mineral, involves gravity separation along with magnetic separators 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 oxidation 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 beneciation for obtaining monazite concentrate. The beneciated product is then chemically
treated with acidic or alkaline reagents under the different conditions to leach out the desired REEs in the solution. Alternately, the
undesired constituents are removed by chemical treatment to produce concentrated REEs product. SGS Minerals Services presents a
process ow-sheet for the processing of RE as given in Fig. 2.
As monazite is chemically and thermally stable concentrate in

the form of crystalline phosphate mineral, it is difcult 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):
2REPO4s 3H2 SO4 RE2 SO4 3s 6H 2PO3

4
The process is used in United States for the selective solubilisation 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 200230 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 beneciated 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
107
Ground Monazite
Conc. H2SO4
LEACHING
Residue
FILTRATION
Monazite Sulfate Solution
Oxalic acid
PRECIPITATION
Oxalate Precipitate
Th, RE
Oxalate Supernatant
U, PO43-, SO42Octyl Pyro Phosphoric
Acid (OPPA)
CALCINATION
Extract Phase U
FeSO4
HF
Oxides of RE (Ce IV), Th

PRECIPITATION
HNO3
LEACHING
Precipitate, UF4
Monazite Nitrate
Solution
SOLVENT EXTRACTION
Aqueous Raffinate
RE, except Ce
Tributyl Phosphate (TBP)
Organic Extract
Ce(IV), Th
STRIPPING
Aqueous, Ce(III)
NaNO2 Solution
Organic, Th
H2O
Aqueous Th Solution
Fig. 3. Flow-sheet for the processing of monazite sand by digesting in sulfuric acid.
Table 5
The chemical composition of the ores of Tomtor and Chuktukon deposits.
Elements (oxide form)
REEO including Y2O3

Nb2O5
TiO2
Al2O3
P2O5
Fe2O3
MnO2
CaO
SrO
BaO
SiO2
SO3
CO2
Contents %, (mass)
Tomtor deposits
Chuktukon deposits
10.2
6.7
5.0
17.1
16.0
12
2.6
3.8
3.2
3.8
0.5
1.5
7.1
0.5
0.9
4.9
4.8
51.4
12.4
0.9
0.4
2.5
4.8
85% or more. Also, the yields of Ce and Pr were respectively

about 20% and 70% remain un-dissolved since they are changed
into oxide forms according to the reaction given below (3)
(Iijima et al., 1993; Zhang and Lincoln; 1994).
REPO4 3NaOH REOH3 Na3 PO4
4CeOH3 O2 22n 3H2 O 4CeO2 nH2 O
Pr forms rst Pr(OH)3 and then Pr6O11 nH2O in the milled powder. These oxides are not easily dissolved in dilute H2SO4 solutions
(Zhang and Saito, 1998). These rare earth oxides are mostly dissolved above 5 N acid concentration. Thus, mechanochemical
milling plays a signicant role in achieving high recovery of REEs
from the leaching of the milled powder at room temperature.
3.1.1.3. Leaching in nitric acid. Different researchers used nitric
acid for the dissolution of monazite and other associated metals
from apatites (phosphorites) containing monazite (Aly and
Mohammed, 1999; Jorjani et al., 2011; Konvisar et al., 1991). The
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
HNO3 with HF and HClO4 in ratio 3:1.5:0.5 in a Teon vessel for
24 h at 80 C. Recently, Kuzmin et al. in 2012 used the nitric acid
to leach out the metals from the ground RE ore of 74 lm size
(Chuktukon deposits, East Siberia, Russia) containing 37% REOs
108
Ore
MILLING
Ground Ore
HNO3
AUTOCLAVE LEACHING
Circulating HNO3
Cake (to Nb concentrate

production)
FILTRATION
Leaching Solution
HNO3
Production
Na2CO3
Nitrate Solution
PRECIPITATION
THERMAL DECOMPOSITION
Precipitate for processing to
recover REMs
Vapour gas
mixture
-MnO2 (Pyrolusite)
Fig. 4. Schematic ow-sheet for the breakdown of the Chuktukon rare earth ore.
in the phosphate form (monazite, turnerite, orensite), FeMn

oxides and 0.51% Nb oxide (chalcolamprite) (Table 5) in a
rotating autoclaves. The leaching reactions of monazite and
orensite with nitric acid are given below:

LnPO4s 3HNO3l ! Ln3
l 3NO3l H3 PO4l
LnPO4s 5=8Fe2 O3s 3HNO3l

! LnNO3 3l 1=4Fe5 PO4 4 OH3 2H2 Os 17=8H2 O
MnNO3 21 ! MnO2s # 2NO2g "
5
6
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 8790% is
obtained during leaching in autoclave in the temperature range of
180220 C of the ground ore. The slurry is ltered to separate cake
containing niobium concentrate for subsequent processing to
produce niobium. The ltrate 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 0.31.5%
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
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 complexes 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
Aliquat-336 molecule. Sodium carbonate (1 M) stripped uranium
efciently from alkaline medium. Based on these results, uranium
was puried from the leach solutions by extraction with
Aliquat-336 diluted in kerosene with purity not less than 99%.
A modied ow 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 reductionprecipitation 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 nitrichydrochloric 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 monaziteUThalkaline cakehydrochloric acid solution as
109
Monazite
GRINDING
Ground Ore (mesh size: 200-270; 130g)
LEACHING
Filtrate
(Na3PO4 & excess NaOH)
50% NaOH, 140C,
FILTRATION
Precipitate
(Hydrous oxide of U, Th and REEs)
Na2CO3, NaOH, H2O2,

60C
SEVERAL WASHING
FILTRATION
Precipitate; Th + REEs
Filtrate (Uranium Tricarbonate)

5% Vol. of Aliquat-336
DILUTION
STRIPPING
ACIDIFICATION
Water
Na2CO3 (1M)
HNO3
and concentration of sulfuric acid could accelerate the dissolution

of monazite concentrate.
But these acidic investigations have encountered a signicant
drawback where the phosphate ions are lost by strong hot acid
attack. During acid dissolution, the phosphate ions get converted
to phosphoric acid (a weak acid) which remains in solution as
triprotic acid, having three ionizable hydrogen atoms which are
sequentially lost and thus, the phosphate ions.
3.1.2. Direct leaching in alkali
Alkali treatment is used commercially for monazite dissolution
using caustic soda where the phosphate content of the ore is recovered as a marketable by-product, trisodium phosphate. Different
authors (Krumholz, 1957; Meerson, 1957; Farah, 1965) reported
the use of caustic soda at high temperature and pressure to dissolve the phosphate ion of the monazite. In India, at Indian Rare
Earths Ltd (IREL), 30004000 tonnes of monazite per year are processed using the caustic soda for the decomposition of monazite
sands (Gupta and Krishnamurthy, 2005). The caustic soda process
is also followed for the monazite treatment in the different plants
established in Malaysia, France and U.S. (Sulaiman, 1991; Gupta
and Krishnamurthy, 2005; de Rohden et al., 1950). Mackey in
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
and Rochedo reported different processing steps for the treatment
of monazite at the Santo Amaro mill (USAM), Brazil as presented in
Fig. 6.
Meerson in 1957 investigated complete extraction of mineral in
two stages by decomposing monazite in heated ball mill using
Uranyl Nitrate
PRECIPITATION
Monazite 85-95%
pure
Ammonia
MAGNETIC
SEPARATION
Uranium
Fig. 5. Modied ow-sheet of alkaline digestion, leaching and extraction of
uranium from Egyptian monazite.
Light fraction
Monazite 99%
feed. DMHMP (Dimethylheptylmethylphosphonate) and TBP

were taken as the extractants diluted in kerosene. It was found
that when DMHMP or TBP is used alone for extracting Th from
low hydrochloric acid concentration (1.52.0 N), the extraction
percentage of Th is only 12%.
ALKALINE
DIGESTION
FILTRATION
3.1.1.6. Comparison of leaching processes. Different investigations

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

monazite
Monazite from East
Siberia
Monazite
Hydrochloric
acid
Nitric acid
Dissolution of Eu from Egyptian black sand monazite in HCl followed by its separation using
combined chemical reductionprecipitation techniques was used
REs ore of East Siberia possessing monazite containing 37% REOs is leached in HNO3
Rabie (2007)
Nitric acid
Gupta et al. (2002)
Brazilian monazite
Sulfuric acid
Egyptian Monazite
Sulfuric acid
Monazite
Sulfuric acid
Bald Mountain
monazite
concentrate
Monazite concentrate
Sulfuric acid
Monazite sand
Sulfuric acid
Monazite sand
Sulfuric acid
Indian monazite
Sodium
hydroxide
Monazite sand was digested in concentrated HNO3 with HF and HClO4 in a tefon vessel for 24 h at
80 C. After complete evaporation to dryness, the mass was dissolved in 5 M HNO3
Monazite was leached in H2SO4, the pH of sulfate solution is adjusted and oxalate anions are added.
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
Complete U, Th and RE were separated from Egyptian monazite after H2SO4 leaching process where
mineral was digested by 98% H2SO4 and dissolved in cold water (1:20) then precipitated with
ammonia (1:1) solution
Acid digestion of monazite with 98% sulfuric acid at 200230 C, yield a grey colored metal sulfate
solid product which dissolves in cold water, ltered and neutralized to separate REEs and Th
Monazite concentrate was decomposed by conventional sulfuric acid cure treatment and the leach
liquor was processed by SX to yield 99% ThO2 product. Th rafnate was further processed for the
recovery of RE oxide product
Pressure leaching, electrogenerated chlorine leaching and sulfuric acid leaching were tested, among
which concentrated sulfuric acid leaching system, results in 99% leaching of La and Nd at 2208 C
Monazite was digested in 93% H2SO4 for 4 h at 210 C results in 99% digestion if sands are ground to
at least 95%65 mesh before digesting
Monazite sand is digested at 200220 C with 9396% H2SO4 and the product was dissolved in water.
The resulting liquor was treated by various methods to recover and separate Th, REs, and U products
The Indian Rare Earths Ltd. plant situated at always in Kerala, uses four major stages to attack
monazite by NaOH at 140 C to recover REs
Brazilian monazite
Sodium
hydroxide
Sodium
hydroxide
Monazite
Monazite
Australian monazite
Egyptian monazite
Monazite
Korean monazite
Sulfuric acid
Sodium
hydroxide
Sodium
hydroxide
Sodium
hydroxide
Sodium
hydroxide
Sodium
hydroxide
Egyptian monazite
Sodium
hydroxide
Egyptian monazite
Sodium
hydroxide
Monazite
Sodium
hydroxide
Sodium
hydroxide
Sodium
hydroxide
Monazite
Monazite from
Moemeik Myitsone
Area
Hongcheon monazite
Sodium
hydroxide
Sodium hydroxide was added to monazite and the aqueous tri-sodium phosphate was separated
from a solid phase, a hydroxide cake, by ltration. The cake was then leached in HCl for REE recovery
Monazite concentrates was leached with caustic soda solution at 130 C in ball mill for complete
extraction of mineral without pulverization, consuming half of caustic soda originally required for
decomposition
Monazite digestion using 70% NaOH solution under pressure for 2 h at 150 C results in the formation
of insoluble RE and Th hydroxides
Processing of Australian monazite concentrate using 80% w/v NaOH at 140 C for 3 h having wt ratio
of NaOH:monazite of 1.5:1 resulted in the extraction of 98% REs
Complete alkaline leaching of Egyptian monazite was attained at 150 C and 175 C within 2.5 and
1 h respectively in ball mill autoclaves, where grinding and leaching takes place simultaneously
The alkali decomposition of monazite with hot concentrated 5075% NaOH proceeds as was carried
out at 150 C in an autoclave
50% NaOH (w/v) solubilizes 99.99% phosphate of Korean monazite, at 170 C, 100 g/L pulp density in
4 h. Kinetics of phosphate leaching tted well with model chemical reaction control i.e. 1 (1 X)
1/2 = kct, Ea = 73.65 kJ/mole
Hydrous oxide cake of monazite was prepared by digesting it in 50% NaOH for 4 h at 140 C followed
by leaching with alkaline carbonate solutions. This cake was dissolved in 4 M HNO3 for further
extraction of Th using Aliquat 336 in kerosene
10 g monazite was treated with 50 wt.% of NaOH solution and boiled for 4 h at 140 C. Solution was
diluted up to 20 wt.% NaOH concentration and boiled again for 1 h and ltered at 80 C. U is easily
separated after Na2CO3 leaching of the residue obtained
Monazite was digested in caustic soda to crack the phosphate matrix and then leached in acid to
dissolve rare earth along with radium
Monazite is treated with 6070% NaOH at 120150 C and after ltration Na3PO4 is separated from
RE hydroxide
Monazite was slowly added to NaOH solution and heated to 140 C for 3 h. The mixture was then
diluted with distilled water at 105 C for 1 h. The slurry was ltered at 80 C to keep caustic soda and
trisodium phosphate in solution
90% RE oxide was obtained by NaOH hot digestion using NaOH/TREO mole ratio of 15 at 140 C and
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 eld separation, milling, alkaline treatment, trisodic phosphate ltration and Th U cake ltration. The
alkali decomposition of monazite with hot concentrated 5075%
NaOH was carried out at 150 C in an autoclave (Habashi, 1997).
REPO4 s 3NaOH REOH3s 3Na PO3

4
Direct leaching of REMs from Korean monazite concentrate

(containing 50% REOs, 29.44% PO3
and around 20% trace rare
4
earth oxides (TREOs)) using 50% NaOH (w/v) at 170 C for 4 h
Kuzmin et al. (2012)
Welt et al. (1958)
Rabie et al. (2013)
Kim and Osseo Asare

(2012)
Borrowman and
Rosenbaum (1962)
Shin et al. (2012)
Barghusen and
Smutz (1958)
Borrowman and
Rosenbaum (1962)
Gupta and
Krishnamurthy
(2005)
Lauria and Rochedo
(2005)
Meerson (1957)
Mackey (1986)
Gupta and
Krishnamurthy
(2005)
Abdel-Rehim (2002)
Habashi (1997)
Panda et al. (2014)
Ali et al. (2007)
El-Nadi et al. (2005)
Hart and Levins

(1988)
Kim and OsseoAsare (2012)
Soe et al. (2008)
Kim et al. (2010)
keeping pulp density 100 g/L is also reported where the kinetics
of phosphate leaching tted 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 recommended for separation and purication 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
111

Table 7
Summary of leaching technologies used with monazite to produce rare earth elements.
Different processes
Yield of
REE (%)
Remarks
Status
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
Cerium cannot be leached if manganese is present. Thorium is leached together with rare earth
elements. Sodium tri-phosphate (Na3SO4) is a marketable byproduct
Outdated
Fine grinding is not required. Thorium remains in the residue as ThO2. No problem of
manganese is observed
In use
(i)
(ii)
(iii)
(i)
Digestion in hot 6070% NaOH

Washing residue with hot water
Leach with mineral acid of choice
Heat under reducing and sulphidizing atmosphere with CaCl2 and
CaCO3
(ii) Leach with 3% HCl
98
89
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 1030 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 nally as oxide having 81% Y2O3.
In use
decomposition of monazite and mixed rare earth concentrate by

TG/DTA method with CaOCaClCaCl2 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 700750 C is increased
on addition of NaClCaCl2. 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 roastleach 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 hydrochloric 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

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 uorine 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 NaClCaCl2
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 CaONaClCaCl2. They also studied the
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 efciency 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
Monazite
CHEMICAL DIGESTION
Ce-REMOVAL
Rare Earth Cake
1 HCl: 1HNO3
LEACHING
Leach Liquor
D2EHPA
Aqueous Raffinate
(Major Rare Earths)
EXTRACTION
pH 1.0
Organic
Major (Middle+Heavy) REEs + Minor LREEs
STRIPPING
Solution pH 0.8
Organic (Major Heavy REEs)
Strip Solution
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
and around 20% trace rare earth oxides (TREOs)) obtained from
the Korea was rst 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 primary production of rare earth elements. A review on most of the
currently prevailing leaching technologies for rare earth production is needed which is essential for signicant 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
of leaching technologies used with monazite to produce rare earth
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)
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 nitrichydrochloric 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 rafnate. The loaded Th and U were stripped with HCl
solution. The process was validated in continuous mode using MSU
of four and ve 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 4050% TBP/kerosene
extractant concentration, 1.52 M oxalic acid concentration as a
precipitant for thorium (extracted with uranium), 4560 min
stirring time and temperature was 4050 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
efcient 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 purication of the RE
by precipitation as rare earth and sodium double sulfate
[NaRE(SO4)2 xH2O] followed by its conversion into REhydroxide
(RE(OH)3) through metathetic reaction and recovery of cerium.
The cerium is then puried 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 ow 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
ow-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 ow-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, uorides, 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 hydrometallurgical processes are concern, either acids or alkali are used, which
releases toxic uids 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 beneciation
followed by hydrometallurgical treatment using acidic and alkaline
solutions, the following conclusions can be made.
Combined physical and otation methods viz. gravimetric,
electrostatic or magnetic separation processes have been used
for the recuperation of monazite concentrate from ne heavy
mineral beach sand deposits where standard gravity methods
are not very efcient for ner size range and thus, otation
method is useful.
The beneciated monazite ore is usually processed following
hydrometallurgical and sometimes pyrometallurgical operations 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 puried by precipitation/solvent
extraction process.
The development of modern and lucrative technologies in eld
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 nancial support. We
would also like to acknowledge the nancial 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).
References
Abdel-Rehim, A.M., 2002. An innovative method for processing Egyptian monazite.
Hydrometallurgy 67, 917.
Abreu, R.D., Morais, C.A., 2010. Purication of rare earth element from monazite
sulfuric acid leach liquor and the production of high purity ceric oxide. Miner.
Eng. 23, 536540.
114
Akkurt, S., Topkaya, Y., Ozbayoglu, G., 1993. Extraction of rare earths from a Turkish
ore. Physicochem. Probl. Miner. Process. 27, 6876.
Ali, A.M.I., El-Nadi, Y.A., Daoud, J.A., Aly, H.F., 2007. Recovery of thorium (IV) from
leached monazite solutions using counter-current extraction. Int. Jr. Miner.
Process. 81, 217223.
Aly, M.M., Mohammed, N.A., 1999. Recovery of lanthanides from Abu Tartur
phosphate rock, Egypt. Hydrometallurgy 52 (2), 199206.
Amaral, J.C.B.S., Morais, C.A., 2010. Thorium and uranium extraction from rare earth
elements in monazite sulfuric acid liquor through solvent extraction. Miner.
Eng. 23 (6), 498503.
Anwar, Y.M., Abdel-Rehim, A.M., 1970. Extraction of thorium from Egyptian
monazite. Bull. Fac. Sci. Alex. Univ. 10, 152171.
Aplan, F.F., 1988. The processing of rare earth minerals, rare earths. In: Bautista,
R.G., Wong, M.M. (Eds.), The Minerals. Metals and Materials Society,
Warrendale, PA, pp. 1534.
Barghusen, J., Smutz, M., 1958. Processing of monazite sands. Ind. & Engg. Chem. 50
(12), 17541755.
Bautista, R.G., Wong, M.M., 1989. Rare earths: extraction, preparation and
applications. In: Proceedings of a Symposium on Rare Earths: Extraction,
Preparation and Applications sponsored by the TMS Reactive Metals
Committee, TMS Annual Meeting, Las Vegas, Nevada.
Borrowman, S.R., Rosenbaum, J.B., 1962. Recovery of Thorium From a Wyoming Ore.
U.S. Dept. of the Interior, Bureau of Mines, Washington.
Bunus, F.T., Dumitrescu, R., 1992. Simultaneous extraction of rare earth elements
and uranium from phosphoric acid. Hydrometallurgy 28, 331338.
Castilloux, R., 2014, Rare earth market outlook: supply, demand and pricing from
2014 to 2020, Adamas Intelligence, Critical metals and mineral research.
Cheng, T.W., Holtham, P.N., Tran, T., 1993. Froth otation of monazite and xenotime.
Miner. Eng. 6 (4), 341351.
Chi, R., Xu, S., Zhu, G., Xu, J., Qiu, X., 2001. Beneciation of rare earth ore in China. In:
Light Metals 2001: Technical Sessions at the 130th TMS Annual Meeting. TMS
Aluminum Committee, New Orleans, pp. 11591165.
Cole, H., 1988. Rare earths in Alaska. In: Proceedings of Ofce of the Governors
Alaska Science and Engineering, Advisory Commission Symposium, Fairbanks,
Alaska.
Crouse, D.J., Brown, K.B., 1959a. Recovery of Thorium, Uranium, and Rare Earths
from Monazite Sulfate Liquors by the Amine Extraction (Amex) Process. Union
Carbide Corporation for the U.S. Atomic energy commission.
Crouse, D.J., Brown, K.B., 1959b. The amex process for extracting thorium ores with
alkyl amines. Ind. Engg. Chem. 51 (12), 14611464.
Cuthbert, F.L., 1958. Thorium Production Technology, US Atomic Energy
Commission. Addison-Wesley.
Cuthbertson, R.E., 1952. Froth Flotation of Monazite from Heavy Gravity Minerals,
Ofce, U.S.P., 2610738 (pp. 13).
de Rohden, C., Seine, N., Peltier, M., 1950. Treatment of monazite, US 2783125 A.
de Vasconcellos, M.E., da Rocha, S.M.R., Pedreira, W.R., da S.Queiroz, C.A., Abrao, A.,
2006. Enrichment of yttrium from rare earth concentrate by ammonium
carbonate leaching and peroxide precipitation. Jr. Alloys Comp. 418, 200203.
Dixit, S.G., Biswas, A.K., 2008. Minerals beneciation pH dependence of the
otation and adsorption properties of some beach sand minerals. AIME Trans.
Dong, Z., Jinwen, D., 1895. Separation process for U, Th, Fe and rare earth elements
in monazite by extraction with DMHMP and TBP. In: Guangxian, X., Jenei, X.
(Eds.), New Frontiers in Rare Earth Science and Applications. Academic Press
Inc., Orlando, FL, USA, p. 497.
Doyle, F.M., Duyvesteyn, S., 1992. Aqueous processing of minerals, metals and
materials. Jr. Met. 45 (4), 4654.
El-Nadi, Y.A., 1996. Extraction of Uranium from Alkaline Medium by Organic
Extractants. MS thesis, Cairo University.
El-Nadi, Y.A., Daoud, J.A., Aly, H.F., 2005. Modied leaching and extraction of
uranium from hydrous oxide cake of Egyptian monazite. Int. Jr. Miner. Process.
76, 101110.
Farah, M.Y., 1965. Reactor grade uranium from Egyptian monazite by newer
techniques. In: Proceeding of International Conference of Peaceful Uses of
Atomic Energy, Geneva, vol. 12, pp. 147156.
Fatherly, N., ONeill, M., Glemza, A., 2008. Formerly used sites remedial action
program (FUSRAP) W.R. Grace Feasibility Study (FS) Alternative Development
Process Challenges and Successes, WM Conference, Phoenix, AZ.
Fernelius, W.C., 1946. Inorganic Syntheses, rst ed. McGraw-Hill Inc., New York,
USA, pp. 3843 (vol. II).
Ferron, C.J., Bulatovic, S.M., Salter, R.S., 1991. Beneciation of rare earth oxide
mineral. Mater. Sci. Forum, 251270.
Franken, K.M., 1995. A roastleach process for extraction of rare earths from
complex monazitexenotime concentrates. Sep. Sci. Technol. 30 (79), 1941
1949.
Gupta, C.K., Krishnamurthy, N., 2005. Extractive Metallurgy of Rare Earths. CRC
Press, NY, USA.
Gupta, B., Malik, P., Deep, A., 2002. Extraction of uranium, thorium, and lanthanides
using Cyanex-923: their separations and recovery from monazite. J. Radioanal.
Nucl. Chem. 251 (3), 451456.
Guy, P.J., Bruckard, W.J., Vaisey, M.J., 2000. Beneciation of Mt weld rare earth
oxides by gravity concentration, otation, and magnetic separation. In: Seventh
Mill Operators Conference. AusIMM, Kalgoorlie, pp. 197205.
Habashi, F., 1997. Handbook of Extractive Metallurgy, vol. III. Wiley-VCH,
Weinheim, Germany.
Habashi, F., 1999. Textbook of Hydrometallurgy. Gordon and Breach Science, New
York.
Hart, K.P., Levins, D.M., 1988. Management of wastes from the processing of rare
earth minerals, In: Chemeca 88 (16th: 1988: Sydney, N.S.W.). Chemeca 88:
Australias Bicentennial International Conference for the Process Industries;
Preprints of Papers. Barton, ACT: Institution of Engineers, Australia, 1988: 8288,
National conference publication (Institution of Engineers, Australia); no. 88/16.
Hatch, G.P., 2012. Dynamics in the global market for rare earths. Elements 8.
Hedrick, J.B., 2001. Rare Earths, U.S. Geological Survey Minerals Year Book.
Hedrick, J.B., 2004. U.S. Geological Survey 983 National Center, Reston, VA 20192,
Indiana.
Hilal, O.M., Kiwan, A.M., 1968. Extraction of uranium from monazite after
separation of thorium and rare earths. Indian Jr. Technol. 6 (1), 1719.
Houot, R., Cuif, J.P., Mottot, Y., Samama, J.C., 1991. Recovery of rare earth minerals
with emphasis on otation process. In: Siribumrungsukha, et al. (Eds.),
Proceedings of International Conference on Rare Earth Minerals and Minerals
for Electronic Uses, Sot&la University, Thailand, pp. 30l324.
Hurst, C.A., 2010. Chinas Ace in the Hole Rare Earth Elements, ndupress.ndu.edu,
issue 59, 4th quarter 2010a/JFQ, pp. 121126.
Hussein, A.E.M., 2011. Successive uranium and thorium adsorption from Egyptian
monazite by solvent impregnated foam. J. Radioanal. Nucl. Chem. 289, 321329.
Iijima, T., Kato, K., Kuno, T., Okuwaki, A., Umetsu, Y., Okabe, T., 1993. Cerium
concentrates and mixed rare earth chloride by the oxidative decomposition of
bastnasite in molten sodium hydroxide. Ind. Engg. Chem. Res. 32, 733737.
Jackson, W.D., Christiansen, G., 1993. International Strategic Minerals Inventory
Summary ReportRare-Earth Oxides. U.S. Geological Survey Circular 930-N
(pp. 68).
Jordens, A., Cheng, Y.P., Waters, K.E., 2013. A review of the beneciation of rare
earth element bearing minerals. Miner. Eng. 41, 97114.
Jordens, A., Sheridan, R.S., Rowson, N.A., Waters, K.E., 2014. Processing a rare earth
mineral deposit using gravity and magnetic separation. Miner. Eng. 62, 918.
Jorjani, E., Bagherieh, A.H., Chelgani, S.C., 2011. Rare earth elements leaching from
Chadormalu apatite concentrate: laboratory studies and regression predictions.
Kor. Jr. Chem. Eng. 28, 557562.
Kaplan, G.E., 1960. Thorium, Its Ore Resources, Chemistry and Technology. Atom
Publish, Moscow.
Kim, E., Osseo-Asare, K., 2012. Aqueous stability of thorium and rare earth metals in
monazite hydrometallurgy: Eh-pH diagrams for the systems Th, Ce, La, Nd
(PO4)(SO4)H2O at 25 C. Hydrometallurgy 113114, 6778.
Kim, J., Yoon, H., Kim, S., Kim, C., Lee, J., 2004. Caustic soda decomposition and
leaching of monazite in Hong-Cheon area deposit. J. Kor. Inst. Resour. Recycl. 13
(4), 1116.
Kim, W., Bae, I., Chae, S., Shin, H., 2009. Mechanochemical decomposition of
monazite to assist the extraction of rare earth elements. Jr. Alloys Comp. 486,
610614.
Kim, S., Lee, J., Kim, C., Yoon, H., Kim, J., 2010. NaOH decomposition and
hydrochloric acid leaching of monazite by hot digestion method. Jr. Korean
Inst. Resour. Recycl. 19 (6), 7076.
Konvisar, L.V., Elkhatib, N.M., Kleshchnev, N.F., Lut, A.U., Berezutskaya, N.L., 1991.
Investigation of the processes of nitric-acid decomposition of Syrian phosphates
Izvestiya Vysshikh Uchebnykh Zavedenii. Khimiya I Khimicheskaya
Tekhnologiya 34, 9699.
Krumholz, P., 1957. Brazilian practice for monazite treatment. Rare Earth, Bombay.
Kul, M., Topkaya, Y., Karakaya, I., 2008. Rare earth double sulfates from preconcentrated bastnasite. Hydrometallurgy 93, 129135.
Kumari, A., Jha, M.K., Hait, J., Sahu, S.K., Kumar, V., 2013. Processing of Korean
monazite concentrate for the recovery of rare earth metals (REMs). Jr. Ind.
Chem. Soc. 90, 21052110.
Kuzmin, V.I., Pashkov, G.L., Lomaev, V.G., Voskresenskaya, E.N., Kuzmina, V.N., 2012.
Combined approaches for comprehensive processing of rare earth metal ores.
Hydrometallurgy 129130, 16.
Lauria, D.C., Rochedo, E.R.R., 2005. The legacy of monazite processing in Brazil.
Radiat. Prot. Dosim. 114 (4), 546550.
Liu, S., Wang, H., Song, J., Fan, X., Tian, M., 2013. Dynamic variation of vegetation
fraction for ion-absorbing type rare earths ore in south china based on landsat
datacase study of longnnan rare earths mines. Geo-Inf. Resour. Manage.
Sustain. Ecosyst. Commun. Comput. Inf. Sci. 399, 354362.
Mackey, T.S., 1986. Recent Developments in USA, Rare earth Technology. In:
Proceedings of a Symposium, Society of Mineral Engineering, Littleton,
Colorado.
Meerson, G.A., 1957. Alkaline leaching of monazite. J. Atom. Energy 3 (9), 259264.
Mitchell, C.J., Yusof, M.A., 1993. Beneciation and appraisal of a beach placer sand
deposit from Malawi.
Moustafa, M.I., Abdelfattah, N.A., 2010. Physical and chemical beneciation of the
Egyptian beach monazite. Resour. Geol. 60 (3), 288299.
Ney, C.L.V., Tauhata, L., Oliveira Filho, D.S., 1992. Dose equivalent estimate of
works in a Brazilian monazite sand plant. In: International Congress of the
International Radiation Protection Association (IRPA8), Montreal, Quebec,
Canada. pp. 670672.
Osman, A., 1998. Solvent extraction study on uranium and thorium from sulphuric
acid solution and its technological application. M.Sc. Thesis, Zagazig University.
Ozbayoglu, G., Umit Atalay, M., 2000. Beneciation of bastnaesite by a multi-gravity
separator. Jr. Alloys Comp. 303304, 520523.
Panda, R., Kumari, A., Jha, M.K., Hait, J., Kumar, V., Lee, J.Y., Kumar, J.R., 2014.
Leaching of rare earth metals from Korean monazite. Jr. Ind. Engg. Chem. 20,
20352042.
Pandey, B.D., 2011. Rare metals extraction from non-ferrous resources in India:
Present status and prospects of R&D. In: Mankhand, T.R., Majumdar, Abhilash, S.

(Eds), 15th International Conference on Non-ferrous Metals, Hotel Oberoi
Grand, Kolkata.
Panigrahi, S.P., 2013. Critical review of beach sand mining in India with particular
reference to chhatrapur sand complex (oscom) in odisha a case study.
Department of Mining Engineering National Institute of Technology, Rourkela
769008.
Parker, J.G., Baroch, C.T., 1971. The rare-earth elements, yttrium, and thorium: a
materials survey, U.S. Bureau of Mines Information Circular 8476, 92,
Washington.
Pavez, O., Peres, A.E.C., 1993a. Flotation of monazitezirconrutile with sodium
oleate and hydroxamates. XVIII International Mineral Processing Congress,
Sydney 4, 10071012.
Pavez, O., Peres, A.E.C., 1993b. Effect of sodium metasilicate and sodium sulphide on
the oatability of monazitezirconrutile with oleate and hydroxamates.
Miner. Eng. 6 (1), 6978.
Pavez, O., Peres, A.E.C., 1994. Technical note bench scale otation of a Brazilian
monazite ore. Miner. Eng. 7 (12), 15611564.
Peelman, S., Sun, Z.H., Sietsma, J., Yang, Y., 2014. Leaching of rare earth elements:
past and present. In: 1st European Rare Earth Resources Conference, ERES2014,
Milos, pp. 446456.
Peng-fei, X., Yan-zan, Z., Gan-feng, T., Jing, G., 2010. High temperature
dephosphorization behavior of monazite concentrates with charred coal.
Trans. Nonferrous Met. Soc. China 20, 23922396.
Peravadhanulu, A., 1979. Benef. Beach Sands, 272275.
Pilkington, E.S., Wylie, A.W., 1947. Rare earth and thorium compounds from
monazite. Jr. Soc. Chern. Ind. (Lond.) 66, 387394.
Rabie, K.A., 2007. A group separation and purication of Sm, Eu and Gd from
Egyptian beach monazite mineral using solvent extraction. Hydrometallurgy
85, 8186.
Rabie, K.A., Abdel-Wahaab, S.M., Mahmoud, K.F., Hussein, A.E.M., Abd El-Fatah,
A.I.L., 2013. Monaziteuranium separation and purication applying oxalic
nitrateTBP extraction. Arab. Jr. Nucl. Sci. Appl. 46 (1), 3042.
Rajagopalan, P.R., 1957. High-pressure hydrometallurgy of uranium and thorium.
Indian Miner. Jr. 5 (4), 11.
Shin, H.Y., Park, H., Yoo, K.K., 2012. The effect of temperature on the leaching of
monazite obtained from heavy mineral sands. Geosyst. Eng. 15 (2), 118122.
115
Shuchen, S., Zhiying, W., Xue, B., Bo, G., Wenyuan, W., Ganfeng, T., 2007. Inuence of
NaClCaCl2 on decomposing REPO4 with CaO. Jr. Rare Earths 25 (6), 779782.
Sinyaver, B.V., 1966. Autoclave processes in nonferrous metallurgy, metallurgy of
nonferrous metals and gold. Nonfer. Met. Inf., 171185
Soe, N.N., Shwe, L.T., Lwin, K.T., 2008. World academy of science. Eng. Technol. 46,
142145.
Sulaiman, M.Y., 1991. An overview of the rare-earth mineral processing industry in
Malaysia. Mater. Sci. Forum 7072, 389.
Thompson, W., Lombard, A., Santiago, E., Singh, A., 2011. Mineralogical studies in
assisting beneciation of rare earth element minerals from carbonatite
deposits. In: Proceedings of 10th International Congress for Applied
Mineralogy (ICAM), Trondheim, Norway, pp 665672 (ISBN-13: 978827385-139-0).
Welt, M.A., Smutz, M., 1960. Processing methods of monazite sands. Jr. Met. 19,
321328.
Welt, M.A., Brooklyn, N.Y., Smutz, M., 1958. Method of processing monazite sand.
Patent No. 2,849,286.
Wenyuan, W., Xue, B., Zhiying, W., Shuchen, S., Ganfeng, T., 2007. Reaction process
of monazite and bastnaesite mixed rare earth minerals calcined by CaONaCl
CaCl2. Trans. Nonferrous Met. Soc. China 17 (4), 864868.
Xue, B., Jianli, C., Zhihua, Z., Shaohua, Y., Yao, L., Fengyun, Z., Wenyuan, W., 2010.
Kinetics of mixed rare earths minerals decomposed by CaO with NaClCaCl2
melting salt. Jr. Rare Earth 28, 8690.
Yanhui, X., Haijiao, L., Zhijun, M., Jianguo, C., Wenyi, Z., Liangcai, L., 2012.
Decomposition of bastnasite and monazite mixed rare earth minerals calcined
by alkali liquid. Jr. Rare Earths 30 (2), 155158.
Zelikman, A.N., 1963. Metallurgy of Rare Earths Thorium and Uranium.
Metallurgizdat, Moscow.
Zhang, J., Edwards, C., 2012. A review of rare earth mineral processing technology.
In: 44th Annual Meeting of the Canadian Mineral Processors. CIM, Ottawa, pp.
79102.
Zhang, J., Lincoln, F.J., 1994. The decomposition of monazite by mechanical milling
with calcium oxide and calcium chloride. Jr. Alloys Comp. 205, 6975.
Zhang, Q., Saito, F., 1998. Non-thermal process for extracting rare earths from
bastnaesite by means of mechanochemical treatment. Hydrometallurgy 47,
231241.

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Minerals Engineering 79 (2015) 102115

Contents lists available at ScienceDirect

Process development to recover rare earth metals from monazite

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

with usually large deposits occurring in few countries like China,

Fig. 1. Global estimated demand for total RE oxides in 2011.

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

Bastnaesite (Ce, La)(CO3)F

Parisite Ca(Ce, La)2(CO3)3F2

Synchysite Ca(Ce, LA)(CO3)2F

Apatite Ca5(PO4)3(F, Cl, OH)

Monazite (Ce, La, Nd, Th)PO4

Gadolinite (Ce, La, Nd,

Allanite (Ce, Ca, Y)2(Al,

Britholite (Ce, Ca)5(SiO4,

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,

North Stradbroke Island, Queensland,

minerals is complicated, costly and there is potential for negative

Strange Lake (B Zone)

Lynas Corporation, Ltd.

Some of the selected RE companies in various countries and their

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

affect the ecosystem as well as human population. About 9600

Biswas, 2008; Pavez and Peres, 1994). Beneciation by otation

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

reported where gravity separation process via a shaking table was

3. Processing of monazite concentrate

2.2.3. Electrostatic and magnetic separation

As monazite is chemically and thermally stable concentrate in

2REPO4s 3H2 SO4 RE2 SO4 3s 6H 2PO3

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

Oxides of RE (Ce IV), Th

Tributyl Phosphate (TBP)

REEO including Y2O3

85% or more. Also, the yields of Ce and Pr were respectively

REPO4 3NaOH REOH3 Na3 PO4

4CeOH3 O2 22n 3H2 O 4CeO2 nH2 O

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

Cake (to Nb concentrate

in the phosphate form (monazite, turnerite, orensite), FeMn

LnPO4s 5=8Fe2 O3s 3HNO3l

During the leaching, the iron and phosphorus remained in the

obtained from the ground monazite. After carbonate leaching, the

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

50% NaOH, 140C,

Na2CO3, NaOH, H2O2,

Filtrate (Uranium Tricarbonate)

and concentration of sulfuric acid could accelerate the dissolution

feed. DMHMP (Dimethylheptylmethylphosphonate) and TBP

3.1.1.6. Comparison of leaching processes. Different investigations

A. Kumari et al. / Minerals Engineering 79 (2015) 102115

Salient features of the process

Egyptian black sand

Gupta et al. (2002)

REPO4 s 3NaOH REOH3s 3Na PO3

Direct leaching of REMs from Korean monazite concentrate

Kuzmin et al. (2012)

Welt et al. (1958)

Rabie et al. (2013)

Kim and Osseo Asare

4CeOH3 O2 22n 3H2 O 4CeO2 nH2 O