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Minerals Engineering 79 (2015) 102115

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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 efcient
Revised 8 May 2015 and eco-friendly processes. Present review reports the commercial processes based on pyrohydro 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 ndings on mining and physical beneciation 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 beneciation 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.
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/ 2015 Elsevier Ltd. All rights reserved.
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 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 with usually large deposits occurring in few countries like China,
Australia, India, Malaysia, Russia, etc. Although the escalating need
Rare earth metals (REMs) are group of 15 elements of the lan- of REEs is principally met by import from China but the recent pol-
thanide series including Sc and Y, which are mainly classied into icy of Chinese government has drastically reduced the export of
two groups based on their ionic radius; light rare earth elements REMs causing increase in the REs price and making it vital for
(LREEs) from La to Sm and heavy rare earth elements (HREEs) from other countries to expand its capability to obtain REEs resources.
Eu to Lu. These metals possess similar physiochemical properties Among 250 recognized REEs minerals, only three are considered
and universally originate in the same mineral assemblies. The to be the major ore that is most viable for REMs extraction: bastn-
meticulous spectroscopic and magnetic properties of REMs enables asite, monazite and xenotime. However, weathered crust
them to play imperative role from industrial to advanced material elution-deposited rare earth ores commonly known as
sciences including hybrid and electric automobiles, uorescent ion-adsorbed rare earth ore is also feasible for RE recovery. These
lights, metal alloys, critical military applications and in the manu- ores were rst discovered as a novel exogenous ore in Jiangxi pro-
facturing of high intensity magnets, electrical assemblies, etc. (Kim vince of China in 1969 and have widespread distribution, rich
and Osseo-Asare, 2012). The USGS mineral commodity survey of reserves, low radioactivity, complete RE partitioning and is rich
2015 reported the global reserves of rare earth elements (REEs) in middle and heavy rare earth. The details of RE sources, their pro-
to be 130 million tons in 2014. The global demand for rare earth cessing and applications have been made by different authors and
oxides is estimated to grow from 120,148 tons in 2014 to are evident from the papers presented in different proceedings
150,766 tons in 2020 at a CAGR of 3.9% driven largely due to esca- (Cole, 1988). Among these minerals, monazite is a common beach
lating demand of some particular RE oxide (Castilloux, 2014). sand mineral present in acidic igneous rocks and vein deposits
However, it was previously estimated that the demand will exceed mainly containing 412% ThO2, 2030% Ce2O3, and 1040% La2O3
200,000 tons in 2014 but REEs demand surpassed 200,000 tons per (Thompson et al., 2011). The potential sources of monazite mineral
year, with an exceeding supply of 40,000 tons annually for several are presented in Table 3 (Hedrick, 2001). The resource estimates of
years (Panda et al., 2014). This deciency affects the global market monazite in inland placer deposits stands at 10.21 million tons in
of REMs. As a result, the world immediately needs fresh, enduring 2005. India holds only 3% of the world reserves as compared to
supply of REEs to meet its requirement. Hatch in 2012 presented 36% by China and 13% by USA (Pandey, 2011).
the global estimates of demand for total rare earth oxides in The present paper reports different processes, with particular
2011 as presented in Fig. 1. focus on the recuperation of REMs from monazite using pyrohy-
According to EPA, United States Environmental Protection dro or hybrid techniques, consisting of direct leach or pretreatment
Agency, 2012, the abundance of REEs in earths crust shows that followed by leaching in acidic/alkaline solutions. The systematic
lanthanides with lower atomic numbers are more abundant than research and various ow-sheets developed to recover REEs under
one with higher atomic numbers as presented in Table 1. They the different condition of time, temperature, concentration etc.
do not occur as metallic elements but exists in wide range of min- from monazite have also been discussed and reviewed.
erals of carbonates, oxides, phosphates and silicates as trivalent
cations. Table 2 presents few of these minerals with the approxi- 2. Processing of different minerals to obtain monazite
mate percentage of RE oxide content (Hedrick, 2004; Kumari concentrate
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 The treatment of any mineral depends on its mineralogy, avail-
minerals. These RE minerals are located throughout the world, 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 earths 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) 102115

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 beneciation 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 worlds 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, uorides, 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 beneciation plant. ing but the release of toxic uids used to dissolve the ore bodies
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 105

affect the ecosystem as well as human population. About 9600 Biswas, 2008; Pavez and Peres, 1994). Beneciation by otation
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 otation are the principle techniques explored but
and one ton of radioactive waste residue. Government enforces more research into beneciation 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 otation, monazite gangue materials, zircon and rutile,
proceeds. Ion-absorbing Type Rare Earths Ore mining is also pre- require depressant like sodium silicate, sodium sulde and sodium
sent which causes series of environmental problems (Liu et al., oxalate (Pavez and Peres, 1993a,b; 1994). Combined physical and
2013). otation methods have been used for recuperation of monazite
concentrate from ne heavy mineral beach sand deposits (Ferron
2.2. Physical beneciation of monazite minerals et al., 1991) which is not possible in case of gravity separation.
However, the otation 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 conrmed.
Monazite is a REthorium 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 beneciation) as they have relatively
by-product during processing of ilmenite, rutile, zircon and cassi-
large specic gravities and are typically associated with gangue
terite. Monazite is found in Manavalakurichi, Pulmoddai deposit,
material, primarily silicates that are signicantly 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 specic 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. Beneciation
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 nal concentrate (Moustafa and Abdelfattah, 2010).
International Atomic Energy Agency reported that the heavy
Beneciation 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
otation, 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 ne
grained beach sand deposits by otation 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
otation using sodium oleate as collector, as well as the effect of
sodium metasilicate and sodium sulphide on the oatability of m RE salts
onazitezirconrutile 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) 102115

reported where gravity separation process via a shaking table was 3. Processing of monazite concentrate
used to remove quartz and feldspar. Further, Mitchell and Yusof
used carpco high intensity induced-roll magnetic separator to As the monazite contains rare earth metals along with other
obtain magnetic and non-magnetic products. In China, mainly at metallic values, their recovery is carried out from such materials
Bayan Obo, gravity separation process in combination of froth by pyro/hydrometallurgical processes consisting of heat treatment
otation has been employed between the rougher and cleaner followed by leaching, precipitation, solvent extraction, etc. The
otation circuits for efcient separation of monazite and bastnasite physically beneciated concentrate are leached in a suitable lixi-
from the iron-bearing and silicate gangue material (Chi et al., 2001; viant acidic or alkaline solutions directly or after heat treatment
Jordens et al., 2013). Lab-scale gravity separations have been suc- to dissolve the metallic values (Akkurt et al., 1993; Fatherly et al.,
cessfully completed on Turkish and Australian deposits where it 2008). The formation of different complexes of REs during the
was found that the rare-earth minerals were concentrated into leaching under the different condition of Eh-pH in the sulfate
very ne particles. To overcome this, either grinding steps were solution was also investigated (Kim and Osseo-Asare, 2012). The
modied to prevent excess ne generation or multi-gravity separa- studies have been carried out by different authors for the recovery
tor was employed to recover ultrane particles (Guy et al., 2000; of REMs from various resources available in different countries
Ozbayoglu and Umit Atalay, 2000). Roasting operation prior to which are evident from the various papers appearing in journals,
gravity separation was investigated by Kasey in 1956, where rare proceedings and patents. The metals from the leach solution are
earth carbonates ore were roasted at 1000 C, converting carbon- removed or concentrated by the precipitation, solvent extraction,
ates to oxides, thus increasing the mineral density and susceptibil- ion exchange, electrolysis, etc. to produce the desired salt or metals.
ity to gravity separation.
3.1. Direct leaching of monazite concentrate

2.2.3. Electrostatic and magnetic separation As monazite is chemically and thermally stable concentrate in
Separation of different materials on basis of their conductivity is the form of crystalline phosphate mineral, it is difcult to dissolve
achieved by electrostatic separation technique, which are only such material in acids or alkali. It requires a suitable condition to
used when alternative processing techniques will not be adequate. leach out the complex materials/metals present in the monazite
In the rare earth mineral processing, use of electrostatic separation using acidic or alkaline solutions.
is in the severance of monazite and xenotime from gangue miner-
als with similar specic gravity and magnetic properties (Ferron 3.1.1. Direct leaching with acids
et al., 1991; Zhang and Edwards, 2012). When xenotime (much Different authors studied the direct leaching of monazite sand
more paramagnetic than monazite) is concentrated with ilmenite using acidic solutions of sulfuric, hydrochloric and nitric acids
after magnetic separation of heavy mineral sands it may be under the different experimental conditions to dissolve the REEs
removed from the ilmenite via electrostatic separation, as ilmenite or undesired components to get concentrate.
is conductive but xenotime is not (Jordens et al., 2013). The behav-
ior of Egyptian beach monazite with the electrostatic eld setting
3.1.1.1. Leaching in sulfuric acid. The sulfuric acid has been used
of the roll-type electrostatic separator was studied (Moustafa and
most extensively for the leaching of monazite, where the sulfate
Abdelfattah, 2010). But the requirement of completely dry feed
(SO2
4 ) ion of H2SO4 acts as a ligand which reacts with RE at high
material is the major drawback of this technique preventing it to
temperature as follows (Fernelius, 1946; Barghusen and Smutz,
be applied on industrial scale.
1958; Borrowman and Rosenbaum, 1962):
Rare earth elements generally have a series of electrons occupy-
ing 4f sub-shell and these electrons have magnetic moments which 2REPO4s 3H2 SO4 RE2 SO4 3s 6H 2PO3
4 1
do not cancel out, resulting in a material with some degree of mag-
netism (Jordens et al., 2013). Magnetic separation, is a method The process is used in United States for the selective solubilisa-
commonly used in rare earth mineral beneciation to eradicate tion of either Th or REs from monazite under controlled conditions
highly magnetic gangue or to concentrate the desired paramag- on industrial scale (Parker and Baroch, 1971). Fernelius et al. in
netic REE bearing minerals such as monazite or xenotime (Gupta 1946 as well as Kim and Osseo Asare in 2012 used 98% sulfuric acid
and Krishnamurthy, 2005). Beneciation of monazite from beach to leach out monazite at 200230 C which was subsequently
sand mineral, involves gravity separation along with magnetic sep- neutralized to separate REEs and Th. Pilkington and Wylie in
arators to eliminate strongly magnetic minerals such as magnetite 1947 reported for the recovery of RE by the precipitation of the rare
and are also used to separate paramagnetic monazite from earth double sulfate. The process consists of digestion of monazite
non-magnetic heavy mineral gangue material such as zircon and in sulfuric acid followed by precipitation of REs with oxalate anions
rutile (Ferron et al., 1991; Jordens et al., 2013). Ito et al., in 1991 under controlled pH from the sulfate solution (Fig. 3) (Welt et al.,
predicted the magnetic susceptibilities of rare earth minerals and 1958). The oxalate precipitate containing Th and RE oxides are
did not found any changes in magnetic behavior for different oxi- dissolved in nitric acid followed by selective extraction of REMs
dation states of these elements. with tributyl phosphate from the nitrate solution.
Coarse heavy mineral sand of Congolone Mozambique, Zircon
Rutile Ltd of Australia, (Ferron et al., 1991) Cable Sands Pty Ltd 3.1.1.2. Leaching in sulfuric acid after mechanochemical
plants (Houot et al., 1991), the Climax Co. mine of Amax (Aplan, treatment. Kim et al. in 2009 reported the sulfuric acid leaching
1988; Cuthbertson, 1952), the Porter Bros. dry plant (Bautista after mechanochemical treatment of beneciated monazite
and Wong, 1989) are some of the industries in different countries (212 lm size) obtained from the beach sand deposit of Malaysia
commercially practising mineral beneciation for obtaining mon- (in wt% 20.5 Ce, 8.5 La, 6.9 Nd, 1.4 Pr, 0.7 Sm, 0.5 Gd, 0.8 Y and
azite concentrate. The beneciated product is then chemically 11.4P) with sodium hydroxide at room temperature. The formation
treated with acidic or alkaline reagents under the different condi- of RE hydroxides and sodium phosphate was found to be complete
tions to leach out the desired REEs in the solution. Alternately, the within 120 min grinding according to the reaction (2) and about
undesired constituents are removed by chemical treatment to pro- 92.3% P was removed by washing. Subsequent leaching carried
duce concentrated REEs product. SGS Minerals Services presents a out of the washed product with 0.05 N sulfuric acid solution
process ow-sheet for the processing of RE as given in Fig. 2. enabled to improve the yield of each of La, Nd and Sm to around
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 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 3NaOH REOH3 Na3 PO4 2


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

Elements (oxide form) Contents %, (mass)


4CeOH3 O2 22n  3H2 O 4CeO2  nH2 O 3
Tomtor deposits Chuktukon deposits Pr forms rst 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 signicant 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 Teon 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 37% REOs
108 A. Kumari et al. / Minerals Engineering 79 (2015) 102115

Ore

MILLING

Ground Ore

Circulating HNO3
HNO3 AUTOCLAVE LEACHING

FILTRATION Cake (to Nb concentrate


production)

Leaching Solution
HNO3
Production
Na2CO3 PRECIPITATION Nitrate Solution

THERMAL DECOMPOSITION Vapour gas


mixture
Precipitate for processing to
recover REMs
-MnO2 (Pyrolusite)

Fig. 4. Schematic ow-sheet for the breakdown of the Chuktukon rare earth ore.

in the phosphate form (monazite, turnerite, orensite), FeMn obtained from the ground monazite. After carbonate leaching, the
oxides and 0.51% Nb oxide (chalcolamprite) (Table 5) in a precipitate was treated with nitric acid three times with heating
rotating autoclaves. The leaching reactions of monazite and to dissolve the hydroxides (hydrous oxides) of the elements.
orensite with nitric acid are given below: Studies have been made for the extraction of uranium by
solvent extraction which showed that tricarbonato uranium com-
LnPO4s 3HNO3l ! Ln3 
l 3NO3l H3 PO4l 4 plexes are selectively extracted by Aliquat-336 diluted in kerosene
from alkaline leach solution. The studies has shown that the
LnPO4s 5=8Fe2 O3s 3HNO3l extraction was increased when the alkalinity (pH) decreased and
the main extracted species is [R2UO2 (CO3)2], where R refers to
! LnNO3 3l 1=4Fe5 PO4 4 OH3  2H2 Os 17=8H2 O 5
Aliquat-336 molecule. Sodium carbonate (1 M) stripped uranium
efciently from alkaline medium. Based on these results, uranium
MnNO3 21 ! MnO2s # 2NO2g " 6 was puried from the leach solutions by extraction with
During the leaching, the iron and phosphorus remained in the Aliquat-336 diluted in kerosene with purity not less than 99%.
residue due to the formation of complex hydroxy ferric phosphates A modied ow chart of the alkaline digestion, leaching, and
which are poorly soluble in nitric acid. REEs recovery of 8790% is extraction of uranium from Egyptian monazite is presented in
obtained during leaching in autoclave in the temperature range of Fig. 5 (El-Nadi et al., 2005).
180220 C of the ground ore. The slurry is ltered to separate cake
containing niobium concentrate for subsequent processing to 3.1.1.5. Leaching in hydrochloric acid. In 2007, Rabie reported the
produce niobium. The ltrate is treated with sodium carbonate dissolution of Eu from middle RE concentrate of Egyptian black
to precipitate REMs concentrate for subsequent treatment to sand monazite in HCl followed by its separation using combined
produce rare earth salts and manganese is also recovered as chemical reduction- precipitation techniques. A batch process
pyrolusite as shown in Fig. 4 (Kuzmin et al., 2012). was developed to separate Sm, Eu, and Gd from the lanthanide
hydrous oxide cake produced from monazite mineral after
3.1.1.4. Leaching of hydrous oxide cake of beach sand monazite in Ce-separation based on extraction by di-2-ethylhexylphosphoric
nitric acid. In 2005, El-Nadi et al. used nitric acid as lixiviant to acid/kerosene from nitrichydrochloric acid mixture. Different acid
leach out REEs from the hydrous oxide cake of Egyptian beach sand solutions with different pH values for stripping were utilized and a
containing 15% heavy minerals (monazite, ilmenite, rutile, concentrate containing 98% of Sm, Eu and Gd as a group was
magnetite, zircon) collected from Demietta and Rosetta, Egypt after obtained with 78% recovery. Kumari et al. in 2013 studied two step
uranium recovery by alkali treatment. It contained 0.31.5% leaching of Korean monazite using diluted HCl at moderate
monazite which has been found to assay 26.5% Ce2O3, 34.3% other temperature for 2 h and pulp density < 100 g/L resulting in only
RE2O3, 5.9% ThO2, 0.44% U3O8 (Osman, 1998). Initially, the ground 25% REMs dissolution. The concentrate left after phosphate
sample of 16.81 lm was treated with NaOH to dissolve sodium removal was leached in 6 N HCl at 90 C for 2 h maintaining
phosphate followed by alkaline carbonate at 60 C in order to 60 g/L pulp density resulting in 90% REMs recovery (Panda et al.,
separate uranium selectively by forming tricarbonato complex 2014). Dong and Jinwen in 1985 investigated the separation
leaving thorium and RE elements as insoluble hydrous oxides process of extracting U, Fe, Th and REEs under low acidity using
(El-Nadi et al., 2005; 1996). A recovery of 83% uranium was a monaziteUThalkaline cakehydrochloric acid solution as
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 109

Monazite and concentration of sulfuric acid could accelerate the dissolution


of monazite concentrate.
But these acidic investigations have encountered a signicant
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, 140C,
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,
60C solve the phosphate ion of the monazite. In India, at Indian Rare
Earths Ltd (IREL), 30004000 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. Modied ow-sheet of alkaline digestion, leaching and extraction of
uranium from Egyptian monazite.

Monazite 99% Light fraction


feed. DMHMP (Dimethylheptylmethylphosphonate) 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 (1.52.0 N), the extraction
percentage of Th is only 12%.
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) 102115

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 reductionprecipitation techniques was used
Monazite from East Nitric acid REs ore of East Siberia possessing monazite containing 37% 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 tefon 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 200230 C, yield a grey colored metal sulfate Kim and Osseo Asare
solid product which dissolves in cold water, ltered 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 rafnate 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 200220 C with 9396% 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 ltration. 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 5075% 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 tted 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 ltered 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 6070% NaOH at 120150 C and after ltration 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 ltered 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 keeping pulp density 100 g/L is also reported where the kinetics
processes monazite at high temperature ranging from 140 to of phosphate leaching tted well with model chemical reaction
200 C for effective decomposition using the sequence of control i.e. 1  (1  X)1/2 = kct with activation energy of
operations of: magnetic eld separation, milling, alkaline treat- 25.44 kJ/mole (Panda et al., 2014). Ali et al. in 2007 recovered Th
ment, trisodic phosphate ltration and Th U cake ltration. The from Egyptian monazite sand after alkaline dissolution followed
alkali decomposition of monazite with hot concentrated 5075% by leaching with alkaline carbonate solution. The studies were
NaOH was carried out at 150 C in an autoclave (Habashi, 1997). made by different authors to improve the processes from various
complex ores/concentrates. An economic method was recom-
REPO4 s 3NaOH REOH3s 3Na PO3
4 7
mended for separation and purication of thorium and uranium
Direct leaching of REMs from Korean monazite concentrate from the hydrous oxide cake concentrate obtained from Egyptian
(containing 50% REOs, 29.44% PO3
4 and around 20% trace rare monazite sands by alkali treatment of the mineral (Lauria and
earth oxides (TREOs)) using 50% NaOH (w/v) at 170 C for 4 h Rochedo, 2005). The study for the extraction of lanthanum oxide
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 111

Table 7
Summary of leaching technologies used with monazite to produce rare earth elements.

Different processes Yield of Remarks Status


REE (%)
Digestion in hot H2SO4 Process conditions determine whether light rare earths are only leached or along with light rare Outdated
earths, heavy rare earth elements as well as thorium are also leached. This process yields no
pure product
(i) Digestion in hot 6070% NaOH 98 Cerium cannot be leached if manganese is present. Thorium is leached together with rare earth In use
(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 In use
ing atmosphere with CaCl2 and manganese is observed
CaCO3
(ii) Leach with 3% HCl

from monazite concentrate was also carried out using NaOH decomposition of monazite and mixed rare earth concentrate by
(Soe et al., 2008). Kim and Osseo-Asare in 2012; El-Nadi et al. in TG/DTA method with CaOCaClCaCl2 at 700 C for 1 h. Xue et al.
2005 as well as Kim et al. in 2010 reported the hydrometallurgical in 2010 reported that the intensity of the peak during TG/DTA
processing of monazite by optimizing leaching conditions for the studies of monazite decomposed by CaO at 700750 C is increased
dissolution of monazite for RE recovery by hot digestion method on addition of NaClCaCl2. In 2010, Peng-fei et al. removed 98%
using NaOH. Several methods are used for industrial processing phosphorus from the monazite pellets when the mixture of
of monazite to extract lanthanides (Anwar and Abdel-Rehim, monazite, charred coal roasted at 1400 C for 2 h.
1970; Doyle and Duyvesteyn, 1992; Cuthbert, 1958; Kaplan, A roastleach process has been reported for the extraction of
1960; Rajagopalan, 1957; Zelikman, 1963; Sinyaver, 1966; Hilal rare earth from complex monazite concentrates using sulfuric acid
and Kiwan, 1968; Habashi, 1999). An innovative method for and other leaching agents at the Pea Ridge iron mine in Sullivan
processing Egyptian monazite by alkaline leaching in ball mill (Franken, 1995). In this process, the RE phosphate of the ore is
autoclaves was studied, where grinding and leaching of monazite converted to its oxide, which eliminated hazardous processing
take place simultaneously. Leaching was followed by selective steps currently in practice. The cerium present in the ore is
separation of Th and U from lanthanides (Abdel-Rehim, 2002). selectively solubilized with 265 g/L sulfuric from the roasted mass
The salient features of different processes for monazite processing at 427 C. Subsequently, the neodymium and lanthanum can be
using direct leaching with acid and alkali are shown in Table 6. 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
3.1.2.1. Leaching of RE concentrate of monazite in ammonium
of 265 g/L. Alternative leaching media, such as thiourea, sulfuric
carbonate. In 2006, de Vasconcellos et al. studied REE concentrate
acid-doped thiourea mixtures, ammonium thiosulfate, nitric acid
(analysis in (%): Y2O3 2.4, Dy2O3 0.6, Gd2O3 2.7, CeO2 2.5, Nd2O3
and hydrochloric acid have also been investigated with ultrasonic
33.2, La2O3 40.3, Sm2O3 4.1 and Pr6O11 7.5) produced industrially
agitation. With ultrasonics agitation, hydrochloric acid proved to
from the chemical treatment of monazite sand in Sao Paulo,
be the best leaching medium. The best roasting temperatures for
Brazil to enrich yttrium by leaching and precipitation process.
selective solubilization remained the same with 64 g/L hydrochlo-
The yttrium concentrate was treated with 200 g/L ammonium
ric acid. Kim et al. in 2009 also reported the sulfuric acid leaching
carbonate for 1030 min at room temperature to dissolve yttrium
after mechanochemical treatment of monazite with sodium
along with other REEs. Subsequently, cerium, praseodymium and
hydroxide at room temperature. The optimum time for the milling
neodymium were selectively precipitated using hydrogen peroxide
of the mixture for mechanochemical activation for the formation of
from the leach solution leaving yttrium in the solution. Yttrium
RE hydroxides and sodium phosphate is about 120 min.
was then recovered from the carbonate solution as the oxalate
and nally as oxide having 81% Y2O3.
3.3. Leaching of monazite concentrate after pre-treatment
3.2. Pre-treatment of monazite concentrate
Apart from the conventional direct leaching of concentrate in
In order to improve the recovery of REEs from the monazite, acid or alkali, several studies have been done on monazite leaching
the material is pre-treated before leaching in suitable after pre-treatment which may improve recovery of REOs by
lixiviants. Several literatures have been reported related to the consuming less acid and eliminating hazardous steps generally
pre-treatment of monazite with alkali for subsequent processing practiced. In 2011, Hussein reported that the hydroxide cake
(Panda et al., 2014; Franken, 1995). The concentrates are usually obtained from alkaline processing of monazite is leached with
calcined at varying temperature with alkali in a rotary tubular HCl at 80 C. To determine the efciency of monazite leaching,
electric furnace. Yanhui et al. in 2012 reported the calcination the hydroxide cake obtained by alkaline processing is leached in
temperature on decomposition of rare earth, oxidation of cerium, 10% HCl at 80 C for 30 min (Abdel-Rehim, 2002). Franken in
removal of uorine and phosphorous etc. The decomposition of 1995 used HCl after roasting monazite (Pea Ridge iron mine,
rare earth and the oxidation of cerium were found to be 95.8% Sullivan) for the solubilisation of phosphate. The NaOH hot
and 93.7%, respectively above 300 C. In 2004, Kim et al. found digestion product was leached in 6 N HCl for 2 h and pulp density
the decomposition of monazite concentrate with NaOH at 460 C of 15%, yielding 90% RE (Kim and Osseo-Asare, 2012). The
and NaOH/TREO mole ratio of 6. Shuchen et al. in 2007 obtained decomposed monazite concentrate of Hong-Cheon area was
79% decomposition of REPO4 with CaO when 10% of NaClCaCl2 leached in 8 N HCl at 80 C for 2 h with 10% pulp density leading
used at roasting temperature of 150 C in 1 h. In 2007, Wen-yuan to 90% recovery of REMs (Kim et al., 2004). The precipitated
et al. reported the calcinations of monazite and mixed rare hydrous oxide cake produced by alkaline dissolution of Egyptian
earth minerals with CaONaClCaCl2. They also studied the monazite was washed with a solution containing 40 vol.% 1 M
112 A. Kumari et al. / Minerals Engineering 79 (2015) 102115

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. technologies have been proposed which are still in the stage of
The cake left was further dissolved in 4 M HNO3 (Ali et al., 2007). research. In order to improve the possibilities of rare earth
Alkali cake obtained after the calcinations of rare earth concentrate elements extraction from different resources, a concise overview
in the rotary tubular electric furnace was mixed with HCl (6 mol/L) of the leaching technologies used in primary rare earth production,
at 90 C with agitation for 30 min (Yanhui et al., 2012). Recently, both past and present, is necessary. Table 7 presents the summary
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 elements (Peelman et al., 2014).
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 3.5. Processing of leach solution by solvent extraction (SX)
kinetics of leaching for the dephosphorization was found to follow
the chemical reaction controlled model. Further, Panda et al. in Different authors used SX process for the extraction of metals
2014 also investigated that the rare earth hydroxide (REHs) left from the leach solution of monazite to extract the valuable to
after alkaline leaching in autoclave was further dissolved in 6 N produce REEs. Recovery of thorium, uranium, and rare earths from
HCl at 90 C, 60 g/L pulp density for 2 h to recover 95% REMs. monazite sulfate liquors by the amine extraction (amex) process
was also reported (Crouse and Brown, 1959a, 1959b). The
3.4. Overview of the leaching technologies monazite concentrate from the Wyoming ore was reported be
decomposed by the sulfuric acid-curing followed by SX to separate
Monazite is among the main rare earth minerals used in the pri- Th and REEs (Borrowman and Rosenbaum, 1962). In 1960, Welt
mary production of rare earth elements. A review on most of the and Smutz used tributylamine (TBA) and di-n-octylamine (DOA)
currently prevailing leaching technologies for rare earth produc- solvents for the recovery of uranium and thorium from Egyptian
tion is needed which is essential for signicant investigations on monazite sulfate leach liquor. Gupta et al. in 2002 reported the
rare earth metal extraction from various resources. A variety of use of Cyanex 923 for uranium, thorium and lanthanides (Ce, Y)
A. Kumari et al. / Minerals Engineering 79 (2015) 102115 113

from the digested leach solution of monazite in HNO3 with HF and resources, RE recovery from secondary resource recycling would
HClO4. In 2007, Rabie et al. used di-2-ethylhexylphosphoric acid in be a great opportunity to secure REEs and save the environment.
kerosene for the separation of Sm, Eu, and Gd in nitrichydrochlo-
ric acid mixed solution obtained from the lanthanide hydrous 4. Conclusions
oxide cake produced from monazite mineral of the Egyptian beach
black sand deposits after Ce-separation. Under the optimised SX Based on the above review, the recovery of REMs from its
condition, a concentrate containing 98% of Sm, Eu, and Gd as a mineral monazite has been made by physical beneciation
group was obtained with a 78% recovery (Fig. 7). followed by hydrometallurgical treatment using acidic and alkaline
Amaral and Morais in 2010 used the mixed extractant of solutions, the following conclusions can be made.
Primene JM-T and Alamine 336 in kerosene for the selective
extraction of Th and U from the sulfate leach solution of monazite.  Combined physical and otation methods viz. gravimetric,
The solvent extracted almost total Th and U leaving only 0.001 g/L electrostatic or magnetic separation processes have been used
metals in the rafnate. The loaded Th and U were stripped with HCl for the recuperation of monazite concentrate from ne heavy
solution. The process was validated in continuous mode using MSU mineral beach sand deposits where standard gravity methods
of four and ve stages of extraction and stripping stages. In 2013, are not very efcient for ner size range and thus, otation
Rabie et al. reported the possibility of extracting completely, method is useful.
uranium by using tri-butyl phosphate (TBP) as an extractant from  The beneciated monazite ore is usually processed following
leach liquor produced after sulfuric acid monazite digestion. The hydrometallurgical and sometimes pyrometallurgical opera-
stripping was carried out with cold water. After selecting the best tions to recover REMs. However, several literatures have been
conditions for the process, which was 4050% TBP/kerosene reported related to the pre-treatment study of monazite
extractant concentration, 1.52 M oxalic acid concentration as a concentrate.
precipitant for thorium (extracted with uranium), 4560 min  The use of sulfuric acid in various industries for processing
stirring time and temperature was 4050 C. A loaded stripping monazite results in the loss of phosphoric acid content, low
solution containing 0.1986 g of U3O8 from the starting 0.21 g with solubility of the sulfates formed, poor separation of Th and
more than 99% purity and 99.3% recovery was obtained. REs and high cost of maintenance. The drawbacks of the acidic
process make the alkaline (NaOH) treatment acceptable from
3.6. Recovery of REs from the leach solution by precipitation industrial point of view.
 Apart from the conventional method of direct leaching of
Abreu and Morais in 2010 reported the development of an monazite concentrate in acid or alkali, several studies have been
efcient and relatively simple process to obtain high grade CeO2 done on monazite leaching after pre- treatment processes
from sulfuric acid leach liquor obtained through acid digestion which may increase the percentage yield of REOs by consuming
of monazite. The process step consists of purication of the RE less acid and will also eliminates some costly and hazardous
by precipitation as rare earth and sodium double sulfate processing steps generally practiced.
[NaRE(SO4)2  xH2O] followed by its conversion into REhydroxide  The leach solution containing REEs and other metals such as Th
(RE(OH)3) through metathetic reaction and recovery of cerium. or U obtained could be further puried by precipitation/solvent
The cerium is then puried from the mixture of ceric hydroxide extraction process.
and manganese dioxide precipitate through dissolution of the solid  The development of modern and lucrative technologies in eld
with HCl and precipitation of the cerium through the addition of of primary processing is mandatory to utilize indigenous
oxalic acid (H2C2O4) or ammonium hydroxide (NH4OH) solution. resources but in order to avoid the effects on the ecosystem
The precipitate is calcined to get 99.5% pure CeO2 with recovery due to mining and processing of primary resources, RE recovery
yield greater than 98%. from secondary resource recycling would be a great opportunity
The ow sheets provided are reported to be feasible. However, to secure REEs and save the environmental. The expansion in
the cost of the processes depend on various factors viz. cost of these prevailing technologies will meet the future necessities
raw materials, availability of high grade ore, chemicals, land, of REs in a variety of applications.
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 Acknowledgements
plants are running. Bench scale ow-sheets are also required for
the scale-up studies for testing of feasibility/commercialization. This paper is based on the joint collaborative research work
carried out between CSIR-National Metallurgical Laboratory
3.7. Environmental aspects of monazite processing (CSIR-NML), Jamshedpur, India and Korea Institute of
Geosciences & Mineral Resources (KIGAM), South Korea. Authors
Any chemical process used to recover metals from different are thankful to the Korea Institute of Geosciences & Mineral
resources effects the environment directly or indirectly. However, Resources (KIGAM), South Korea for the nancial support. We
mining of primary ores also effect the whole ecosystem as mining would also like to acknowledge the nancial support provided
has possibility to liberate detrimental substances of radionuclides, under the R & D Convergence Program of MSIP (Ministry of
acids, uorides, etc. due to overtopping/collapsing of tailing dams. Science, ICT and Future Planning) and NST (National Research
Thus, government enforces regulations on companies and use Council of Science and Technology) of Republic of Korea (Grant
technology to reduce the damage due to mining by establishing B551179-11-01-00).
safeguards before operations proceeds. As far as hydrometallurgi-
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