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Thermal treatment for the separation of phosphate and recovery of rare earth
metals (REMs) from Korean monazite

Article  in  Journal of Industrial and Engineering Chemistry · January 2015

DOI: 10.1016/j.jiec.2014.03.039

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 Journal of Industrial and Engineering Chemistry 21 (2015) 696–703

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Thermal treatment for the separation of phosphate and recovery of

rare earth metals (REMs) from Korean monazite
Archana Kumari a, Rekha Panda a, Manis Kumar Jha a, Jin Young Lee b,**,
J. Rajesh Kumar b, Vinay Kumar a,*
a
Metal Extraction and Forming Division, CSIR-National Metallurgical Laboratory (CSIR-NML), Jamshedpur 831 007, India
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), 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: Systematic study for thermal decomposition of monazite to remove phosphate as a valuable product
Received 21 January 2014 using Na2CO3 and NaOH roasting processes to validate the TG/DTA studies is reported here. Monazite in
Accepted 20 March 2014 1:1 wt. ratio with Na2CO3 and NaOH requires a temperature of 900 8C and 400 8C, respectively, for
Available online 27 March 2014
120 min in order to achieve complete conversion of rare earth phosphate into its oxides. The roasted
mass was washed, dried and leached in 6 M HCl for 2 h, pulp density 30 g/L at 80 8C which results in
Keywords: >90% REMs recovery. Leach liquor generated will be further processed by solvent extraction and
Korean monazite
precipitation processes.
Roasting
Phosphorus
ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
TG/DTA reserved.
Rare earth metals (REMs)
HCl

1. Introduction minerals, bastnasite, monazite and xenotime contain significant

percentage of REMs along with other metallic constituents like
Rare earth elements (REEs) are group of 15 lanthanide metals titanium, thorium, zirconium, etc. [6]. Although located throughout
including yttrium and scandium. Due to their particular spectro- the world, REMs deposits are present in few countries like China,
scopic and magnetic properties, REMs are increasingly establishing Australia, India, Malaysia, Russia, etc. with China being the leading
themselves as crucial industrial materials with unique applications world producer [4]. China, which controls 97% of world trade in
in numerous fields, such as permanent magnet, electronics, super- REMs, has imposed restriction on its export, thus, consistently
conductors, medical and nuclear technologies [1]. REEs possess some escalating the global demand of REMs. As a result, the supply is
unique properties of unsaturated 4f electronic structure which expected to exceed by 40,000 t annually for several years [1]. Hence,
enable them to be used for luminescence, magnetism and electronics it is obligatory to exploit indigenous resources and expand
[2]. The uses of REEs in terms of economic value are shown in Fig. 1 technologies to meet the future necessities of REs.
[3]. REEs do not occur naturally as metallic element but exist in a Monazite, the second most important RE phosphate mineral,
wide range of carbonate, oxide, phosphate and silicate minerals as generally contains 70% oxides of REMs comprising high content
trivalent cations, which are moderately available in hard rock and of Ce and La along with remarkable presence of Nd, Pr and Sm [7,8].
placer deposits of the earth’s crust. The approximate content of rare In India, monazite is the main RE mineral along with other heavy
earth oxide (REOs) in some of these minerals mentioned above is minerals viz. ilmenite, rutile, zircon, etc. According to the
shown in Table 1 [4,5]. Among the most renowned rare earth (RE) information provided to the Rajya Sabha by V. Narayansamy
(Minister of State for Personnel, Public Grievances and Pensions),
the estimated reserve of monazite in India has increased from 1.25
* Corresponding author at: CSIR-National Metallurgical Laboratory, Metal
to 11.93 million tons from 2009 to 2013. Fig. 2 shows the presence
Extraction and Forming Division, Burmamines, Jamshedpur, Jharkhand 831007, of monazite reserves in different states of India [9]. Monazite by
India. Tel.: +91 6572345285; fax: +91 657 2345213. virtue of being rich in REMs is very important from research point
** Corresponding author at: Korea Institute of Geoscience and Mineral Resources of view in order to solve the restraint forced by Chinese
(KIGAM), Daejeon 305-350, South Korea. Tel.: +82 42 868 3648; fax: +82 42 868
Government on its export. Chemically, monazite is very stable
3418.
E-mail addresses: jinlee@kigam.re.kr (J.Y. Lee),
and is attacked by strong hot acid, transforming the phosphate ion
vkumar@nmlindia.org (V. Kumar). to di-hydrogen phosphate salt and phosphoric acid, leaving all the

http://dx.doi.org/10.1016/j.jiec.2014.03.039
1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
[(Fig._1)TD$IG] [(Fig._2)TD$IG]
A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703 697

Fig. 1. Applications of rare earth metals (REMs).

Fig. 2. Amount of monazite reserves found in different states of India.

metal ions as water soluble salts which destroy the phosphate
matrix present in the mineral [2]. However, metallurgical
processing of monazite, results in the formation of various 1400 8C for 2 h removed 98% of phosphorus [14]. CaO in CaO–CaCl–
phosphides, which causes pulverization of RE complexes. There- CaCl2 has ability to decompose monazite in temperature range of
fore, it is essential to remove phosphorus from the ore, which is 610 to 700 8C as follows [15]:
very difficult to decompose even at a high temperature due to their
high thermal stability and hereby its dephosphorization is 3CaO þ 2REPO4 ! RE2 O3 þ Ca3 ðPO4 Þ2 (1)
unfeasible [10]. But typical approaches have been developed to
recuperate phosphate ion present in the mineral as a valuable REEs recovery from monazite was investigated using Na2CO3 at
product which is mainly used as fertilizer in agricultural sector temperature of 1173 K in both reducing and sulphidizing
[11]. environment. REEs are extracted from water leached residue that
Various studies to separate REMs from monazite minerals have selectively leaches the oxysulphide phase formed with 3.5 wt.%
been reported using leaching, precipitation, solvent extraction and hydrochloric acid [16]. As far as recovery of RE from monazite
ion exchange methods. But before individual separation of these through leaching process is concerned, various studies have been
metals, the removal of phosphate is necessary. Several researchers observed. Pressure leaching, electrogenerated chlorine leaching
reported the thermal decomposition of monazite using different and concentrated sulphuric acid leaching were performed to
reagents. The influence of NaCl–CaCl2 on thermal decomposition of investigate the leaching behaviour of monazite concentrate at
REPO4 with CaO was tested with TG–DTA experiment which shows various temperature ranges [17]. Extraction of REEs from monazite
79% decomposition when NaCl–CaCl2 mixture was 10%, roasting mineral is studied using NaOH fusion [18]. Recently, the RE
temperature 750 8C and 1 h time [12]. The recovery of REs by concentrate obtained from Korea was first dephosphorised with
reduction leaching using SO2 followed by ammonium chloride 50% NaOH (w/v) at 170 8C and 100 g/L pulp density in 4 h and the
roasting of the residual solid and leaching to recover Mn and Pb as a leaching kinetics was found to follow the chemical reaction
by-product was also explained [13]. The dephosphorization controlled model. Further, the rare earth hydroxide (REHs) left
behaviour of monazite concentrate with charred coal at high after alkaline leaching in autoclave was dissolved in 6 N HCl at
temperatures was studied, where roasting of monazite pellets at 90 8C, 60 g/L pulp density for 2 h to recover 95% REMs [19].
Metallurgical processing of monazite have also been reported
which includes the Indian Rare Earth process where monazite is
Table 1
dissolved in 65–70% NaOH and is processed at high temperature of
Different minerals containing rare earth oxides
(REOs). 980–1190 8C. In the process of chlorination, monazite is mixed
with charcoal and heated at 900 8C [17,20].
Minerals REO (%)
Present paper is focused on the development of an effective
Carbonate process for the separation of phosphate and recovery of REMs from
Bastnasite 75 monazite. Systematic studies for thermal decomposition of Korean
Parisite 61
monazite for phosphate removal using soda roasting followed by
Synchysite 51
Cebaite 32 water leaching is discussed. Additionally, acid leaching of the
Phosphate roasted mass is also studied. The leach liquor generated will be
Apatite 19 further processed by solvent extraction technique and from the
Monazite 65
pure solutions, metal/salts could be obtained using electrowin-
Xenotime 61
Florencite 32
ning, evaporation, crystallization, precipitation processes etc.
Silicate
Gadolinite 60 2. Materials and methods
Allanite 38
Kainosite 38
2.1. Material
Britholite 32
Oxide
Fergusonite 53 Korean monazite used as raw material for the experimental
Loparite 30 purpose is obtained from various grades of Iron ores like hematite
Euxenite 24
or magnetite and varies in particle size ranging from +48 to
Brannerite 9
325 mesh. Particle size analysis of the original sample shows that
[(Fig._3)TD$IG]
698 A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703

Table 2
Chemical composition of the Korean monazite.

Chemical components Composition (%)

La 13.4
Ce 24.1
Pr 2.4
Nd 7.3
Sm 1.1
Eu 0.05
Gd 0.6
Y 0.58
PO43 29.44
TREO Balance

well as NaOH at different experimental conditions. In order to

validate the TG/DTA results showing phosphate removal, the
Fig. 3. Screen analysis of Korean monazite. monazite concentrate was thermally treated/roasted with Na2CO3
and NaOH, individually. Roasting of the mixed sample was done at
major amount of monazite contains particle of size ranging different temperatures as per the experimental requirement in a
between 100 and 250 mesh (BSS) as presented in Fig. 3. Further, platinum crucible using Muffle furnace. After roasting for a given
this monazite concentrate was processed without any size time, the sample was taken out from the furnace and cooled down
reduction. As per the established process developed at NML, the to room temperature for further analysis. The crucible containing
chemical analysis of Korean monazite was performed using nitric the mixed sample was weighed before as well as after roasting, in
acid with hydrogen fluoride followed by sulfuric acid fuming order to study the loss/gain in weight of the sample. The roasted
constituting 60% REOs containing 13.4% La, 24.1% Ce, 1.1% Sm, mass was leached in hot distilled water for 60 min in order to
7.3% Nd and 2.4% Pr. The phosphate content was found to be 29.44% dissolve the phosphate ion in solution. The slurry was filtered and
in the form of P2O5 (Table 2). the cake produced was dried at 90 8C to get REOs. These
The composition of constituent includes major and minor beneficiated REOs left were further leached in HCl in a 100 mL
oxides. The XRD analysis of the monazite sample was performed, pyrex reactor fitted with a reflux condenser in order to avert
using Bruker AXS D8 instrument running at 0.2 s/step that showed evaporation at high temperature and magnetic stirrer was used for
various diffraction peaks of LaPO4, CePO4, NdPO4, etc. along with constant agitation. After each set of experiment, the REMs
P2O5 as the main peak (Fig. 4). The chemical reagent, sodium concentration in residue, left after acid leaching was further
carbonate (Na2CO3) used was of AR Grade supplied by S.D. Fine- determined. Satisfactory mass balance was obtained with a
Chem Ltd., Mumbai, India while sodium hydroxide (NaOH) and all maximum deviation in the range of 2%. The leach liquor generated
other acids used were Merck products (Merck, Mumbai, India) and will be then pumped to solvent extraction section as a feed solution
were used without any further purification. Aqueous sample/ for the extraction and separation of REMs.
solutions were made in distilled water.
2.3. Analytical procedure
2.2. Method
TG/DTA studies were performed using Thermo gravimetric
The TG–DTA studies for the decomposition of phosphate analyzer (Linseis STA PT 1600, Germany). The content of
[(Fig._4)TD$IG]
present in Korean monazite were carried out using Na2CO3 as phosphorus was determined by Inductively Coupled Plasma
P2O5, LaPO4, SmPO4, ThPO4

700
CePO4, PrPO4, PmPO4,

DyPO4, HoPO4, ThPO4

600
LaPO4, GdPO4

NdPO4, TbPO4, U3O8, Na2CO3

P2O5, YbPO4, U3O8, Na2CO3
CePO4, U3O8

500
P4O7, GdPO4, ThPO4

CePO4, GdPO4

EuPO4, DyPO4, TmPO4, U3O8

PmPO4,
P4O7, TbPO4, U3O8
NdPO4, TbPO4
CePO4
Lin (Counts)

P4O7, P2O5

400
CePO4, PrPO4, PmPO4

CePO4, NdPO4, EuPO4

LaPO4, ThPO4

CePO4, ErPO4

300
TmPO4,
U3O8

ThPO4
NdPO4

U3O8
YbPO4

U3O8

200

100

0
13 20 30 40 50 60 70 80 90
2-Theta - Scale

Fig. 4. XRD of Korean monazite concentrate.

[(Fig._5)TD$IG] A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703 699

Fig. 5. Optical properties of Korean monazite as observed under petrological microscope.

(ICP-OES) [VISTA-PMX, CCD Simultaneous; Make Australia] as well 3.2. TG/DTA studies
as Ion Chromatography [Metrohm, Switzerland]. Leach liquor
containing dissolved REMs was also analysed using ICP-OES. The TG–DTA studies for phosphate decomposition from Korean
monazite were carried out at different experimental conditions
3. Results and discussion using Thermo gravimetric analyzer. Monazite and Na2CO3 was
taken in 1:1 wt. ratio and the temperature was set at 1000 8C,
The recuperation of REMs from Korean monazite is reduced running at the rate 10 8C/min for 100 min. In Fig. 6, a downward
owing to the presence of phosphate ions which hinders the peak was observed on DTA curve between 750 and 850 8C which
reaction due to the formation of various phosphide complexes. practically shows that the decomposition starts after 700 8C and an
Therefore, it is essential to eradicate phosphate before RE endothermic reaction was noticed. The first loss in weight was
dissolution. To eliminate phosphorus and in order to validate observed in the TG curve at 100 8C which point towards the
TG/DTA studies, monazite mineral was thermally treated with formation of metasilicate that is further converted to metadisi-
different sodium reagents at various conditions. Comparative licate when Na2CO3 reacts with SiO2 present in the monazite at
studies of Na2CO3 and NaOH roasting were performed, where the 700 8C accompanied by the removal of equivalent amount of CO2
latter reagent proved to be better in view of energy conservation. (Eq. (2)) [21].
Studies for the roasting of monazite with Na2CO3 as well as NaOH
individually, in their stoichiometric proportion is discussed below Na2 CO3ðsÞ þ SiO2 ! Na2 O  SiO2ðsÞ þ CO2ðgÞ (2)
which results in the disintegration of RE phosphate to constituent’s
oxides at elevated temperatures. Different reagent concentrations SiO2ðsÞ þ Na2 O  SiO2ðsÞ ! Na2 O  2SiO2ðsÞ (3)
were primarily used to recover its suitable amount obligatory for
complete phosphate removal. Various other parameters were also Almost 37 to 40% mass loss was observed during this test. But,
studied for making this process, a suitable route for phosphate when NaOH was mixed with monazite in ratio 1:1 at 250 8C,
removal. running at the rate 10 8C/min for 25 min, a downward peak was
observed on DTA curve between 200 and 250 8C indicating the
3.1. Mineralogical characterization of Korean monazite decomposition reaction of RE with NaOH that starts after 150 8C
and requires energy i.e. an endothermic reaction is noticed (Fig. 7).
The identification and characterization of Korean monazite The TG curve shows almost 17.5 wt.% loss during first stage of the
were investigated using an optical microscope, commonly known [(Fig._6)TD$IG]
reaction between 150 and 200 8C whereas 20 wt.% loss was
as optical petrological microscope, designed to identify minerals
and rocks in thin sections based on their optical properties. The
photographs taken under the microscope are presented in Fig. 5.
Along with monazite, the presence of zircon, Ilmenite and
silimenite were also observed. Under thin section, monazite was
represented by crystal faces of pale yellow colour with high
refractive index and is pleochroic i.e. it looks like concentric circles.
Colourless long slender crystals, with a cross-fracture, or diamond-
shaped cross section possessing elongation with high refractive
index are the silimenite particles. Ilmenite is black and opaque
when viewed by reflected light. Zircon has high refractive index
like monazite but does not show pleochroism and possesses an
intense black border. After recognizing the presence of various
minerals in the sample, it was spread uniformly over a flat modal
plate having numbered grid in order to obtain the percentage of
minerals present. This method is known as modal analysis which
depicts that the sample contains <70% monazite and 30% other
minerals. Fig. 6. TG–DTA curves of decomposition of Korean monazite using Na2CO3.
[(Fig._7)TD$IG]
700 [(Fig._9)TD$IG]
A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703

100

Leaching of Phosphate (%)

80

60

NaOH roasting
40 Na2CO3 roasting

20

0
0 200 400 600 800 1000 1200
Roasting Temperature (°C)

Fig. 9. Effect of roasting temperature on monazite using different reagent

[reagent:monazite ratio = 1:1, roasting time = 120 min].

Fig. 7. TG–DTA curves of decomposition of Korean monazite using NaOH between

200 and 250 8C. anhydrous Na2CO3 and roasted at high temperature to break the
phosphate bond. At 1:10 wt. ratio of Na2CO3 and monazite, only
3.42% phosphate was removed which increases to 91.73% at
observed in second stage between 200 and 250 8C. However, the
7:10 wt. ratio in 120 min. For complete removal, 1:1 wt. ratio was
decomposition behaviour of monazite with NaOH between 250
required (Fig. 10).
and 300 8C was also observed under similar conditions and an
As far as the effect of roasting time is concerned, it was noticed
endothermic reaction was observed with a mass loss of about 23 to
that the percentage of phosphate removal increases from 95.74% to
30% as shown in Fig. 8.
97.36% as the roasting time increases from 60 to 90 min, while
99.99% phosphate removal was observed in 120 min (Fig. 11). Thus,
3.3. Roasting of Korean monazite using sodium carbonate (Na2CO3)
the efficiency of dephosphorization increases with increase in the
amount of Na2CO3, roasting time and temperature. Fig. 12 shows the
In order to validate the TG/DTA studies, Na2CO3 was mixed with
XRD study of the REOs concentrate left after Na2CO3 roasting. The
monazite in 1:1 wt. ratio and roasted at high temperatures. It was
major diffraction peaks of REOs for the roasted mass (leached in
found that at 600 8C and 700 8C, the rate of dephosphorization
water) was free from P2O5 peaks. Once equilibrium stage was
reaches to 2.16% and 12.81%, respectively, in 120 min indicating
reached further increment in these parameters was not required.
the vital role of temperature on the rate of reaction. At 850 8C,
decomposition was prominent showing 95% phosphate removal
3.4. Roasting of Korean monazite using sodium hydroxide (NaOH)
while at 900 8C and above, complete removal was noticed (Fig. 9).
This might be due to the melting point of Na2CO3 that is 851 8C
After analyzing the results of Na2CO3 roasting, dephosphoriza-
after which the decomposition speeds up. The RE phosphate
tion was also carried out using NaOH. The effect of various process
mineral breakdown to its constituent oxide according to the
parameters such as NaOH concentration, roasting temperature,
equation given below:
etc. was studied. The monazite mineral disintegrates as:

2REPO4 þ 3Na2 CO3 ! RE2 O3 þ 2Na3 PO4 þ 3CO2 (4) REPO4 þ 3NaOH ! REðOHÞ3 þ Na3 PO4 (5)

In order to observe the effect of reagent concentration, Similarly, for this process, 1:1 wt. ratio of monazite and NaOH
monazite was thoroughly mixed with different amount of was loaded into the furnace and roasted at different temperatures
[(Fig._8)TD$IG] [(Fig._10)TD$IG]
100
20 1

10 0
Leaching of Phosphate (%)

80
0 -1

-2
-10
60
-3
-20
ΔT

-4
Δm

-30 DTA 40
-5
TG Sodium Carbonate at 850oC
-40
-6 Sodium Hydroxide at 300oC
-50 20
-7
-60 -8
0
-70 -9 0 0.5 1 1.5 2 2.5
0 100 200 300 400 500
Temperature(ºC) Reagent/ Monazite Ratio

Fig. 8. TG–DTA curves of decomposition of Korean monazite using NaOH between Fig. 10. Effect of reagent concentration on monazite roasting [roasting
250 and 300 8C. time = 120 min]
[(Fig._1)TD$IG] A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703 701

100 Table 3
Leaching of Phosphate (%) Chemical analysis of the mixed REO concentrate left after
95 Na2CO3 roasting.

Chemical components Composition (%)

90
La 13.85
Ce 24.25
85 Pr 2.56
Phosphate Leached
Nd 7.01
80 Sm 1.16
Eu 0.06
75 Gd 0.57
Y 0.56
70 PO43 12.36
0 20 40 60 80 100 120 140
Roasting Time (min)
dephosphorization is possible at 400 8C while roasting with
Fig. 11. Effect of roasting time on monazite [monazite = 10 g, sodium
carbonate = 10 g, roasting temperature = 900 8C].
Na2CO3 requires 900 8C under similar experimental conditions.

3.5. Leaching studies for REMs dissolution from the roasted

ranging from 250 8C to 450 8C for 120 min. The result presented in concentrate
Fig. 9 shows that at 250 8C only 38.77% of phosphate was removed
that increases up to 99% at 400 8C, which might be due to the Water washed monazite concentrate left after Na2CO3 roasting
melting point of NaOH i.e. 351 8C. As far as the effect of NaOH obtained from different experiments were dried, mixed and
concentration is concerned, the results show that leaching further passed through the hydrometallurgical process of acid
percentage increases from 38.55 to 85.21% as wt. ratio of NaOH leaching using dilute HCl in a three necked pyrex reactor fitted
to monazite increases from 1:5 to 4:5 (Fig. 10). For complete with a condenser. The reaction is presented below:
removal of phosphate, 1:1 wt. ratio was considered optimum and
is similar to the ratio required in case of Na2CO3 roasting. RE2 O3 þ 6HCl ! 2RECl3 þ 3H2 O (6)
The roasted mass was cooled down to room temperature and
weighed for further analysis. In case of NaOH roasting, an increase The chemical composition of REOs left after Na2CO3 roasting
in weight was observed due to the evolution of water, however, a were analysed (Table 3). The effects of HCl concentration, pulp
decrease in weight was noticed during Na2CO3 roasting due to loss density, temperature and time on the leaching of REEs were
in the form of CO2 as shown in Eq. (4). Further, the roasted mass investigated which is discussed below.
was dissolved in hot distilled water for 60 min resulting in the
dissolution of Na3PO4 formed. The solution of Na3PO4 was 3.5.1. Effect of acid concentration
separated from the insoluble REOs by filtration and concentrated Acid concentration has pronounced effect on metal extraction
to crystallize out its salt as a product. Satisfactory mass balance and is one of the essential factors to be studied for optimizing the
was obtained for each set of the experiment. From both the condition for REs dissolution. The leaching rate of REEs was studied
roasting process, it was concluded that NaOH roasting is more by varying HCl concentration in the range 1–6 M at 90 8C for 2 h
[(Fig._12)TD$IG]
energy efficient as compared to Na2CO3, as complete maintaining pulp density 60 g/L. The percentage leaching of REMs
Nd2O3, Pm2O3, Eu2O3, Sm2O3

Nd2O3, Pr2O3, Pm2O3, Gd2O3, UO3, Yb3O4, (NaPO3)6

La2O3, Pm2O=, UO3, (NaPO3)6, Tb2O3, Yb3O4

800

700
CeO2, Eu2O3, Gd2O3, Tm2O3, Yb3O4

Pr2O3, Pm2O3, Sm2O3, Eu2O3, Ho2O3, Tb2O3, Er2O3

Sm2O3, Eu2O3, ThO2, Er2O3, Ho2O3, (NaPO3)6

CeO2, Nd2O3, Sm2O3, Ho2O3, Tb2O3, Tm2O3

600

500
Lin (Counts)

Pm2O3, Eu2O3, Tb2O3, Er2O3

400
Pr2O3, UO3, Tb2O3

300
Pr2O3, Eu2O3

200

100

0
10 20 30 40 50 60 70 80 90
2-Theta - Scale

Fig. 12. XRD of the roasted mass after water leaching [monazite = 10 g, sodium carbonate = 10 g, roasting temperature = 900 8C, roasting time = 120 min].
[(Fig._13)TD$IG]
702 [(Fig._15)TD$IG]
A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703

70 70
La Ce
Leaching of Rare Earth Metals (%)

Leaching of Rare Earth Metals (%)

60 Nd Pr 60

Sm
50 50

40 40

30 30

20 20
La Ce
Nd Sm
10 10 Pr

0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6
Acid Concentration (M) Time (h)

Fig. 13. Effect of acid concentration on leaching of REMs from soda beneficiated Fig. 15. Effect of time on leaching of REMs from soda beneficiated REOs [HCl = 6 M,
REOs [temperature = 90 8C, time = 2 h, pulp density = 60 g/L]. temperature = 90 8C, pulp density = 30 g/L].

[(Fig._14)TD$IG]
90 La Ce 3.5.3. Effect of leaching time and temperature
Nd Pr
The effect of leaching time on REMs recovery is illustrated in
80 Sm
Leaching of Rare Earth Metals (%)

Fig. 15. Leaching of trivalent lanthanides increases slightly, as the

70 leaching time increases from 1 to 5 h at 90 8C using 6 M HCl and
30 g/L pulp density. Thus, 2 h leaching time was sufficient for REMs
60
dissolution. Further increase in time shows a very small rise in
50 percentage dissolution of these metals.
The dissolution of metals is also affected by varying the
40
temperature of the solution. On increasing the temperature from
30 25 to 90 8C using 6 M HCl for 2 h at a pulp density of 30 g/L the
leaching of REMs also increases as shown in Fig. 16. Dissolution of
20
La increases from 15.78 to 54.19%, Ce from 1.76 to 21.51%, Nd
10 from 20.55 to 35.44%, Sm from 22.53 to 62.91% and Pr from 21.13
to 60.09%. Maximum dissolution was obtained at 90 8C as
0 reaction of REMs with HCl is promoted at higher temperature.
0 20 40 60 80 100 120
But only slight increase in percentage leaching is observed when
Pulp Density (g/L)
temperature increases from 80 to 90 8C. Thus, 80 8C was
Fig. 14. Effect of pulp density on leaching of REMs from soda beneficiated REOs considered suitable for the recovery of REMs. As the reactions
[HCl = 6 M, temperature = 90 8C, time = 2 h]. are exothermic it may proceed in opposite direction if the
temperature is too high. Thus, 90% REMs was recovered on
dissolving the REO concentrate left (containing negligible
increases on an average as the acid concentration increases from 1 amount of phosphate) after Na2CO3 roasting at optimized
to 6 M as shown in Fig. 13 where La increases from 23.19 to 54.19%, condition as shown in Fig. 17.
Ce from 7.21 to 21.51%, Nd from 22.39 to 35.88%, Pr from 34.39 to [(Fig._16)TD$IG]
60.09% and Sm from 38.64 to 62.91%. The dissolution of Ce is 70
comparatively less with respect to other REMs which remain in +3
state, Ce changes to +4 state as it comes in contact with acid. Thus, La Ce
Leaching of Rare Earth Metals (%)

60
6 M HCl was considered effective for the dissolution of REMs. Nd Sm
Pr
50
3.5.2. Effect of pulp density
In order to obtain a high leaching efficiency, it is necessary to
40
determine proper ratio of solid to liquid as metal dissolution is also
dependent on pulp density which increases the available surface
30
area per unit volume of the solution. Hence, more metal is
recovered within specific time. Smaller the ratio of solid to liquid,
20
greater is the recovery of REMs at constant HCl concentration of
6 M, 2 h time and 90 8C (Fig. 14) as the concentration of hydrogen
10
ion may be high enough to dissolve these metals. The extraction
rate of these metals was found inversely proportional to pulp
density. The percentage leaching decreases from 60.23 to 31.42% 0
0 20 40 60 80 100
for La, 25.03 to 11.5% for Ce, 47.99 to 28.3% for Nd, 63.71 to 49.77%
Temperature (°C)
for Pr and from 71.11 to 50.08% for Sm as the pulp density increases
from 10 to 100 g/L. Thus, pulp density of 30 g/L was determined to Fig. 16. Effect of temperature on leaching of REMs from soda beneficiated REOs
be optimum for maximum leaching of REMs. [HCl = 6 M, time = 2 h, pulp density = 30 g/L].
[(Fig._17)TD$IG] A. Kumari et al. / Journal of Industrial and Engineering Chemistry 21 (2015) 696–703 703

for 2 h using 6 M HCl, maintaining the pulp density 30 g/L and

temperature 80 8C which resulted in >90% dissolution of REs as
shown in Fig. 18.

4. Conclusion

Several studies have been investigated for the removal of

phosphate either thermally or by dissolution processes [14–20].
But present investigation shows systematic scientific studies
explaining that roasting with NaOH is more effective than Na2CO3
for complete dephosphorization as it requires less energy of about
400 8C for 120 min, taking 1:1 wt. ratio of the reagent to monazite.
Na3PO4 was obtained as a product by evaporating the solution
obtained after dissolution of the roasted mass in water. The
insoluble REOs concentrate left after roasting was dried and
leached at 80 8C with 6 M HCl for 2 h maintaining pulp density of
30 g/L which results in >90% REMs recovery. Leach liquor
Fig. 17. Percentage leaching of REMs from soda beneficiated REOs [HCl = 6 M, containing REs will be further processed using solvent extraction
temperature = 80 8C, time = 2 h, pulp density = 30 g/L].
[(Fig._18)TD$IG] technique for selective separation of REMs using different organic
solvents. From the pure solutions, metal/salts could be obtained by
evaporation, crystallization/precipitation processes, etc. Fig. 19
shows the complete proposed process flow sheet for the separation
of phosphate and recovery of REMs from Korean monazite.

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 Geoscience & Mineral Resources (KIGAM),
South Korea for the financial support. We would also like to
acknowledge the financial support provided under the R & D
Convergence Program of MSIP (Ministry of Science, ICT and Future
Planning) and ISTK (Korea Research Council for Industrial Science
and Technology) of Republic of Korea (Grant B551179-11-01-00).

Fig. 18. Percentage leaching of REMs from alkaline beneficiated REOs [HCl = 6 M,
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