International Journal of Mineral Processing 159 (2017) 715

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International Journal of Mineral Processing

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Hydrometallurgical digestion and leaching of Iranian monazite

concentrate containing rare earth elements Th, Ce, La and Nd
Farzaneh Sadri a, Fereshteh Rashchi a,, Ahmad Amini b
a
School of Metallurgy and Materials Engineering, University College of Engineering, University of Tehran, PO Box 11155/4563, Tehran, Iran
b
Geological Survey of Iran, Tehran, Iran

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

Article history: Rare earth elements (REEs) have an ever-increasing variety of applications in modern technology. In the present
Received 3 April 2016 work, the possibility of extraction of rare earth elements cerium (Ce), lanthanum (La), neodymium (Nd) and tho-
Received in revised form 11 November 2016 rium (Th) from a monazite concentrate containing 25% rare earth elements' oxide was investigated. In this re-
Accepted 13 December 2016
gard, the acidic digestion and leaching step, and their effective parameters were studied in detail using design
Available online 16 December 2016
of experiment (DOE) which hadn't been investigated before. The optimum conditions for the performed exper-
Keywords:
iments in acidic digestion step were: temperature of 225 C, time of 3.5 h and sulfuric acid to concentrate weight
Monazite ratio (L/S) of 2.5. Using these conditions, the recovery of 92.34%, 91.44%, 92.1% and 88.94% were obtained for ce-
Rare earth elements (REEs) rium, lanthanum, neodymium and thorium, respectively. In leaching step, the optimum conditions were: tem-
Digestion perature of 75 C, time of 15 h and water to digested mass weight ratio of 7.5. Using these conditions, recovery
Design of experiment of 88.47%, 89.45%, 87.35% and 82.19% were obtained for rare earth elements cerium, lanthanum, neodymium
and thorium, respectively. In precipitation step, rare earths' oxalates were precipitated from the leach liquor
using oxalic acid. Then, the precipitate was calcined in a furnace at 800 C for 1 h and nally, a mixture of rare
earth elements' oxides with a purity of about 84% was obtained.
2016 Elsevier B.V. All rights reserved.

1. Introduction obtained liquor, which is used for the separation/purication process.

Nowadays, the rare earth elements' (REEs) applications in industry;
such as, permanent magnets, superconductors, glass polishing, and la-
sers (Kim and Osseo-Asare, 2012, Abreu and Morais, 2014) are increas-
ing. Thus, separation and purication of different rare earth elements
from their sources have become very important. Principal sources of
REEs are bastnasite (LnFCO3), monazite (Ln, Th) PO4 and xenotime (Y,
Ln) PO4 (Cotton, 2006; Panda et al., 2012; Abreu and Morais, 2014). Lan-
thanides (Ln) belong to the REEs' group and due to the similarities be-
tween these elements, the separation process is very difcult. For
instance, all of them adopt 3+ oxidation states in aqueous solution
and the further separation will be difcult (Cotton, 2006).
There are different ways to separate the lanthanides from each other
in solutions: chemical separation, fractional crystallization, ion-ex-
change and solvent extraction. Among them only solvent extraction is
used on a commercial scale. In all of these methods, a digestion and
leaching process should be done in advance. These two steps are very
important because they control the concentration of REEs in the
Corresponding author.
E-mail address: rashchi@ut.ac.ir (F. Rashchi).
The digestion process is performed in two main paths: acidic with sulfu-
ric acid and basic with sodium hydroxide (Gupta, 1990, Kim and
Osseo-Asare, 2012). This step is then followed by a leaching process.
Monazite lattice is made of strong bonds between REEs and oxygen
and therefore, they are not soluble in water. In acidic digestion process,
these strong bindings are broken and soluble REEs' sulfates are formed.
The following reactions occur during the digestion process (Gupta,
1990):
2REPO4 s 3H2 SO4 RE2 SO4 3 s 6H 2PO3
4 1
Th3 PO4 4 s 6H2 SO4 3ThSO4 2 s 12H 4PO3 2
4
ThSiO4 2H2 SO4 ThSO4 2 SiO2 2H2 O 3
Ce3 PO4 4s 6H2 SO4 3CeSO4 2s 12H 4PO3
4 4
The reactions show that the dry gray digested mass is mainly
consisted of sulfate salts of REEs and Th. In the leaching step, the REES
sulfates are dissolved in water; however, some of the impurities and
unreacted monazite which consists of REEs phosphates and also insolu-
ble compounds which were produced in the digestion process such as

http://dx.doi.org/10.1016/j.minpro.2016.12.003
0301-7516/ 2016 Elsevier B.V. All rights reserved.
8 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715
thorium pyrophosphate remain as a precipitate. The following reactions
occur in the leaching step (Gupta, 1990):
RE2 SO4 3 :nH2 Os 2RE3 3SO2
4 nH2 O
ThSO4 2s Th
4
2SO2
4
CeSO4 2 s Ce4 2SO2
4 7
Studies about the solvent extraction of REEs have been extensively
carried out (Jorjani and Shahbazi, in press; Banda et al., 2012; Panda et
al., 2012; Lee et al., 2005; El-Nadi, 2012; Ablihash et al., 2014). However,
researches on the digestion and leaching step are infrequent.
The aim of present research is to investigate the optimum conditions
of digestion and leaching of the solid residue from digestion process of
the monazite concentrate using design of experiment. The parameters
evaluated for optimum conditions of both digestion and leaching were
time, temperature and liquid to solid ratio (L/S). To separate rare earths
from the leach liquor, precipitation was performed by means of oxalic
acid. Finally, a mixture of rare earth elements' oxides was acquired.
2. Materials and methods
2.1. Materials
The monazite concentrate sample was provided kindly by the Geo-
logical Survey of Iran. The feed of the monazite concentrate was from
monazite placer deposits in Marvast, Yazd (central Iran). Microscopic
studies showed that the monazite concentrate accumulates in the ne
size fraction (b 2 mm). The sample used in this study was taken directly
from the 02 mm size fraction. Sulfuric acid with a purity of 9395%
(Merck) was used in both digestion and leaching experiments. Oxalic
Fig. 1. A schematic owsheet of the procedure which was applied in this work in order to produce a mixture of REOs.
acid with the purity of 99.6% was used in the precipitation step. De-ion-
ized water was used in all experiments.
5 2.2. Methods
6 Fig. 1 shows a suggested owsheet displaying the process. As it can
be seen the process of extraction of valuable metal species from mona-
zite includes three stages: acidic digestion, leaching and precipitation.
The monazite concentrate is subjected to grinding followed by acidic di-
gestion using sulfuric acid. The digested mass (produced in the diges-
tion stage, sulfate cake containing REEs) is leached with deionized
water followed by ltration. The leach liquor is precipitated by oxalic
acid followed by ltration. The residue is calcined and a precipitate con-
taining a mixture of rare earth oxides (REOs) is produced. In this
owsheet oxalic acid was used to precipitate the REE oxalates from
the leach solution to obtain a more concentrated rare earth elements
concentrate with a higher selectivity than previous researches (Jorjani
and Shahbazi, in press). Besides, by oxalic acid precipitation, the impu-
rities entering to the latter solvent extraction process will be eliminated.
2.2.1. Digestion experiments
In order to investigate the optimum conditions of digestion step, cer-
tain amount of sulfuric acid was heated in a Pyrex beaker on a heater.
After reaching the required temperature (based on the designed condi-
tions in Table 1), 3 g of the monazite concentrate was added to the sul-
furic acid in the beaker. A mechanical stirrer was used to agitate the
mixture for a specic time. Then, the digested sample was left in air
until dried and a dry gray solid residue or the digested mass was ob-
tained. Afterwards, the digested mass was re-leached with deionized
water in the xed leaching parameters of liquid to solid ratio of 10:1
for 15 h in the room temperature. Then, the leach liquor was ltered
with a centrifuge (EDA-20, Hettich, Germany) and nally, the leach li-
quor and the precipitate were analyzed with ICP.
 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715 9

Table 1 2.4. Mineralogical examinations

Experimental matrix for the digestion process.

Temperature Time L/S Th rec. Ce rec. La rec. Nd rec. The monazite concentrate was divided into homogeneous, small size
Std Run (C) (hr) (mL/g) (%) (%) (%) (%) fractions using a rife separator. The sample was wet screened to pro-
1 2 200 1.0 1.00 78.89 87.07 88.12 87.73 duce three size fractions of 180 + 125 m, 125 + 53 m and
2 5 200 3.5 1.75 83.36 91.95 92.13 92.54 53 m (+ 80270 mesh). Thin sections were prepared for all three
3 8 200 6.0 2.50 88.50 92.80 92.28 92.53 size fractions by cementing a thin slice of the concentrate to glass as
4 6 225 1.0 1.75 84.34 90.11 90.28 90.21
well as polished sections. A cover slip was cemented on top of the con-
5 7 225 3.5 2.50 87.97 93.00 92.44 92.86
6 3 225 6.0 1.00 12.71 80.16 81.33 80.10 centrate (Espiari et al., 2006). Transmitted light microscopy (MEIGI-
7 4 250 1.0 2.50 82.07 90.68 90.89 90.21 Japan) was performed to examine minerals that transmitted light in
8 1 250 3.5 1.00 49.24 85.52 85.96 85.73 the thin sections. These minerals included most of the gangue or metal-
9 9 250 6.0 1.75 23.07 83.12 83.49 83.42 lic-free minerals. Since the degree of freedom of monazite particles in all
size fractions were the same, only the sample with coarser size fraction
of 180 + 125 m was statistically investigated using point counting
method (Goins, 2004).
2.2.2. Leaching experiments
Certain amount of the monazite concentrate was digested under the 2.5. Design of experiments
obtained optimum conditions of the digestion step. In the next step, the
optimum conditions for leaching of this digested mass were investigat- The design of experiment method was used to study the effect of dif-
ed. Deionized water was used in all the leaching experiments. The ferent parameters: time, temperature and liquid to solid (L/S) ratio on
leaching experiments were performed in a batch Pyrex reactor. A hot- the digestion process of the concentrate and leaching recovery of Th,
plate equipped with a magnetic stirrer was used to agitate the suspen- Ce, La and Nd from the digested mass. The independent variables A, B
sion at a predetermined temperature. Five grams of the digested mass and C represent temperature (C), time (hr) and L/S ratio, respectively.
(produced in the digestion stage) was transferred into specic amount The range of parameters studied for digestion process was: digestion
of deionized water based on the designed conditions in Table 2. After time (t): 1, 3.5 and 6 h; temperature (T): 200, 225 and 250 C and sulfu-
completing the leaching time, the pregnant leach liquor which ric acid to monazite concentrate weight ratio: 1, 1.75 and 2.5 (Gupta,
contained the dissolved REEs (Th, Ce, La and Nd) was ltered and dilut- 1990; Habashi, 1997; Kim and Osseo-Asare, 2012). For the leaching pro-
ed with deionized water. cess, the range of parameters studied was: leaching time (t): 5, 10 and
15 h; temperature (T): 25, 50 and 75 C and liquid to solid product
weight ratio: 5, 7.5 and 10 (Gupta, 1990; Habashi, 1997; Kim and
2.2.3. Precipitation experiments Osseo-Asare, 2012). The recovery percentage in each experiment was
To precipitate the rare earth elements' oxalate, oxalic acid 10% was calculated as below:
used. The ratio of oxalic acid to leach liquor was 1:1 and the leaching
time was 30 min. A white solid containing rare earth elements' oxalate Cc Cs
%recovery  100 8
precipitated from the leach liquor while adding oxalic acid. It was then Cc
calcined at 800 C in a furnace for 1 h and rare earth elements' oxides
were obtained. X-ray uorescence spectroscopy (XRF) analysis was per- where Cc is the concentration of the element in the primary concentrate
formed on the oxides. and Cs is the concentration of element in the ltrate residue of leaching.
In order to determine effects of the independent variables on the di-
gestion and leaching process a Taguchi design consisting of 9 runs was
2.3. Analysis performed. The magnitude of the interaction between the independent
variables and the response was obtained via the ANOVA statistical tech-
Monazite concentrate chemical analysis was performed using induc- nique. This statistical tool is required to test the signicance and ade-
tively coupled plasma optical emission spectrometry (ICP-OES (Varian- quacy of the model. The mean squares (MS) are obtained as: MS =
735-ES, Australia)) and X-ray uorescence (Philips PW240, Nether- SS/DF, where: SS = sum of squares (SS) of each variation source and
land). Microscopic analysis of polished and thin sections were also per- DF = the respective degrees of freedom (DF). The Fischer variation
formed (MEIGI, Japan). The X-ray diffraction (XRD) pattern was ratio (F-value) is a statistically valid measure of how well the factors de-
obtained with a D4-Bruker X-ray diffractometer (Germany) using cop- scribe the variation in the data about its mean. It can be calculated from
per ( = 1.54 ) radiation in step modes between 4 and 70. ANOVA as: F-value = MS (due to the model variation)/MS (due to error
variance). Normally, the data has some variations around its mean
value; the greater the F-value from unity, the more acceptable is this
variation. The parameter levels and response values (Th, Ce, La and Nd
Table 2 recovery) are given in Tables 1 and 2 (the ANOVA tables are not
Experimental matrix for the leaching process. shown). The samples were analyzed to determine the Th, Ce, La and
Temperature Time L/S Th rec. Ce rec. La rec. Nd rec. Nd contents using ICP-OES. The DESIGN EXPERT 7.0.1 trial version
Std Run (C) (hr) (mL/g) (%) (%) (%) (%) (State-Ease Inc., Minneapolis, MN, USA) software was utilized for re-
1 8 25 5 5.0 51.28 80.07 82.09 82.24
gression and graphical analysis of the obtained data.
2 2 25 10 7.5 51.16 76.42 78.07 80.11
3 5 25 15 10.0 49.06 63.89 66.57 69.46 3. Results and discussion
4 1 50 5 7.5 49.26 62.08 65.05 67.73
5 4 50 10 10.0 48.38 80.77 82.13 83.73
3.1. Characterization of the monazite concentrate
6 7 50 15 5.0 56.24 73.08 75.60 77.48
7 6 75 5 10.0 55.88 63.05 66.05 69.08
8 3 75 10 5.0 63.99 43.39 49.50 55.74 Fig. 2 illustrates the XRD pattern of the monazite concentrate. It sug-
9 9 75 15 7.5 72.36 80.43 82.13 84.16 gests that the major mineral phases in the concentrate are monazite
10 10 75 15 10.0 73.91 81.27 84.76 86.03 (consisting of La, Ce and Nd compounds), quartz and augelite
11 11 25 5 5.0 49.87 77.24 78.02 80.41
(Al2(PO)4(OH)3). Table 3 displays the XRF results. It shows that the
10 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715

Fig. 2. X-ray diffraction (XRD) pattern of monazite concentrate.

dominant compositions of the used concentrate are hematite (Fe2O3)
and silica (SiO2), the concentrate is made of 25% rare earth oxides and
75% impurities. Table 4 demonstrates the ICP-OES results. As it is
shown, the monazite concentrate contains 14.16% Ce, 6.48% La and 6%
Nd.
Microscopic analysis of the polished and thin sections conrmed the
existence of liberated grains of hematite, gray monazite and rarely mag-
netite and quartz. The identication basis of hematite, monazite and
quartz is shown in Table 5. This analysis provided useful information
concerning the liberation of the minerals, especially monazite, which
is N 97% liberated and could complicate the digestion and leaching pro-
cess if it was involved in other grains. Hematite grains are also liberated
and only b15% of them are involved in quartz gangue. Fig. 3 shows lib-
erated grains of monazite and hematite in all size fractions of the con-
centrate and Fig. 4 illustrates quartz and magnetite present as a minor
phase. Microscopic analysis (polished and thin sections) was used to
calculate the relative amounts of the components of the concentrate.
Monazite (69%) was the dominant phase but there was also 31%
hematite.
Nd recovery 88:372:24A2:02B 3:67C 11
where, A, B and C represent temperature, time and L/S ratio, respective-
ly. These equations reveal the L/S to be the most effective and time as
the less effective inuencing parameters, respectively. It is also clear
that time and temperature have negative effect on the digestion
process.
3.2.2. Effective parameters in digestion process
It should be mentioned that the effects of parameters on both diges-
tion and leaching processes are the same for Ce, La and Nd, as discussed
in Sections 2.2.1 and 2.2.2. Therefore, in order to summarize the results,
only the effect of parameters on digestion and leaching of Ce, as repre-
sentative of the lanthanides studied, is given here. The effect of Ce is
compared with Th as the actinide investigated. The effects of digestion
parameters on Ce and Th recovery are shown as perturbation diagrams
in Fig. 5.

3.2. Digestion process 3.2.2.1. Effect of temperature. As shown in Fig. 5, temperature has a neg-
ative effect on the digestion process and its effect is much more negative
3.2.1. Model tting and analysis of variance (ANOVA) on Th than on Ce. This is due to the fact that Th as an actinide has a
The results of the ANOVA test for Th, Ce, La and Nd were performed
by DX7 program. The main effects of the variables were calculated at the
Table 4
95% condence level. Using the experimental results, analysis of vari- ICP-OES results for Monazite concentrate.
ance and tting, the linear response models were determined by
Element Cd Co Cr Cs Cu
ANOVA. The models for Ce, La and Nd recovery are given below:
ppm 4.94 151.00 49.65 43.88 446.00
Element Dy Er Ga Ge Hf
Ce recovery 88:272:08A1:97B 3:95C 9 ppm 888.00 98.83 374.00 9.39 44.09
Element Hg Ho In Li Lu
La recovery 88:552:03A2:03B 3:37C 10 ppm 7.88 825.00 16.97 24.09 5.60
Element Mo Nb Ni Pb Rb
ppm 31.11 33.95 301.00 1338.00 46.84
Table 3 Element S Sb Sc Se Sn
XRF results for the Monazite concentrate. ppm 583.00 0.86 31.42 2.84 12.96
Element Sr Ta Tb Te Tl
Composition SiO2 Fe2O3 Al2O3 MgO CaO Na2O K2O ppm 583.00 17.03 4.64 2.64 97.16
% 23.6 27.2 1.4 0.7 1.1 0.4 0.4 Element Tm (ppm) Yb (ppm) Y Ti Sm
Composition SO3 P2O5 SrO ZrO2 TiO2 As2O3 Y2O3 % 3.21 14.85 0.35 0.19 0.54
% 0.2 12.2 0.1 b0.1 0.7 0.1 0.2 Element Pr P Mn Gd Eu
Composition La2O3 CeO2 Nd2O3 Pr2O3 PbO ThO2 LOI % 2.10 7.18 0.46 0.93 0.20
% 6.3 10.1 6.6 1.5 0.1 0.2 3.9 Element Ce La Nd Th Fe2O3
% 14.16 6.47 6.03 0.13 25.10
Loss of ignition.
 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715 11

Table 5
Identication basis of available phases in the concentrate (Anthony et al., 2011).

Mineral Crystal system Unit cell Cleavage Optical properties Mohs scale hardness

Hematite Trigonal a = 5.038(2) Parting on {0001} & {1011g Uniaxial () 56

c = 13.772(12) due to twinning
Z=6
Monazite Monoclinic; a = 6.7902(10) {100}, distinct Biaxial (+) 55.5
Metamict if Th-rich b = 7.0203(6) {010}, poor
c = 6.4674(7) Parting on {001} or {111}
Z=4
= 103.38(1)
Quartz Hexagonal a = 4.9135(4) Rarely observable, poor on Uniaxial (+) 7, variable by direction
c = 5.4050(2) {1101}, {0111}, {1010} and form
Z=3

different chemical behavior from the other three elements which are
lanthanide.
There are some reasons for the negative effect of temperature on di-
gestion process. First, at temperatures higher than 200 C, which is
needed for monazite digestion, insoluble thorium pyrophosphate is
formed (especially near 300 C) (Gupta, 1990; Panda et al., 2014). In ad-
dition, it has been reported in literature that the digested residue should
not be dried completely, since the formation of insoluble compounds in-
creases in higher temperatures (Gupta, 1990; Hu and Qi, 2014) which
will decrease digestion recovery. Second, because the digestion step is
not conducted in vaccum and the system is exposed to the air,
increasing the temperature increases sulfuric acid evaporation rate,
therefore, the contact time between liquid (sulfuric acid) and solid
(monazite concentrate) which is the time that the reaction happens,
decreases.
3.2.2.2. Effect of time. Fig. 6 illustrates the effect of digestion time on the
recovery of Ce and Th. It shows that increasing the digestion time from 1
to 3.5 h increases the Ce, La and Nd recovery; however, Th recovery de-
creases by increasing the digestion time up to 6 h the recovery for all el-
ements decreases. In general, based on Fig. 5, time is a desirable factor in
the digestion process, since increasing the digestion time creates more

Fig. 3. Liberated grains of monazite and hematite, polished section.

12 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715

Fig. 4. Grains of quartz and magnetite, thin section.

broken bonds and results in a higher recovery (Gupta, 1990; Habashi,
1997). In addition, longer time means more chance of reaction happen-
ing and more broken bonds occurrence, therefore, the digestion recov-
ery increases.
In these experiments, a different trend was investigated for longer
digestion times (N3.5 h); in other words, time had a negative effect on
the digestion recovery at longer time periods. It can happen because
the experiments were done in laboratory scale and in this scale, a
much lower amount of chemical substances were used which made
the acid evaporation quicker than industrial scale, therefore, the
digested mass dried faster and as a result, the favorable reactions
stopped sooner. It means that in a longer time at a laboratory scale, pro-
ducing the insoluble compounds, unfavorable reactions and reverse

Fig. 5. Perturbation diagram of digestion parameters for Ce and Th: A. temperature, B. time
and C. L/S ratio. Fig. 6. Effect of digestion time on the recovery of a. Ce and b. Th.
 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715 13

reactions are more possible because of a high temperature and it can af-
fect the positive impact of time on the process and reduce digestion re-
covery. In general, digestion time should not be longer than what is
needed for the process in any scale.

3.2.2.3. Effect of L/S. Fig. 5 implies that raising the L/S ratio improves the
recovery of the rare earths since the possibility of effective contacts be-
tween the solid and liquid increases, and that is because of the presence
of excess acid in the reaction medium. Moreover, mixing of the diges-
tion system in the presence of the liquid phase removes the solid prod-
ucts formed on the particles and also increases the contacts between the
solid and liquid phases. On the other hand, in higher L/S ratio, the evap-
oration of sulfuric acid and the drying of solid product occur in a longer
time. As a result, there is more time for the reaction, more bonds will be
broken and less insoluble products are produced.

3.2.3. Optimum condition

According to Table 1, experiments 7 and 8 (standards 3 and 5) re-
sulted in the highest digestion recovery for all the four elements and
the results were quite similar in both experiments, therefore, the
more economical experiment (in laboratory scale) was chosen.
Concerning that L/S ratio is equal in both experiments, the optimum
condition should be chosen according to the time and temperature.
The higher temperature was used in experiment 7 but the longer time
was used in experiment 8. Therefore, less energy is consumed in exper-
iment 7 since an amount of energy is required to reach the temperature
and another amount of energy is needed to supply the heat loss of the
system to keep the system in the desired temperature for a specic
time; this part is the main part of energy consumption by the system
which is less in experiment 7 because of the shorter time which is need-
ed. Therefore, it seems that the energy consumption in order to main-
tain the desired temperature in experiment 7 is less than experiment
8. Hence, the optimum condition in the digestion process is proposed
to be: temperature of 225 C, time of 3.5 h and L/S ratio of 2.5. This op-
timum condition was used to produce a dry gray solid residue which
was the feed in the leaching experiments.

3.3. Leaching process
3.3.1. Model tting and analysis of variance (ANOVA)
The results of the ANOVA test for Th, Ce, La and Nd were performed
by DX7 program. The main effects of the variables were calculated at the
95% condence level. Using the experimental results, analysis of vari-
ance and tting, the 2Fi response models were determined by ANOVA.
The models for Ce, La, Nd and Th recovery are given below:
Th recovery 55:29 6:79A
Ce recovery 69:255:59A 8:29B 7:19C 10:65AB
12:51AC
La recovery 71:914:84A 7:44B 6:10C 9:68AB 11:18AC 14
Nd recovery 74:423:80A 6:68B 5:52C 8:76AB 9:35AC 15
where A, B and C are temperature (C), time (hr) and L/S ratio, respec-
tively. According to the analysis of variance and the above equations,
there are two interactions between parameters and Taguchi method
may have errors in recognizing the interactions, therefore, in order to
make sure of the accuracy of the interactions, the Taguchi design was
augmented to D-optimal design and two experiments were added. Ex-
periments 10 and 11 in Table 2 show the results of these two experi-
ments. Models from D-optimal design also show the interactions
between parameters, therefore, it can be concluded that the Taguchi de-
sign shows the interactions correctly. The equations reveal the time as
the most effective and temperature as the less effective inuencing
Fig. 7. Perturbation diagram of leaching parameters for Ce and Th: A. temperature, B. time
and C. L/S ratio.
parameters, respectively. It is also clear that temperature has a negative
effect on the leaching process. The analysis of variance and the above
equations present that the only effective parameter on Th leaching re-
covery is temperature.
3.3.2. Effect of parameters on leaching process
12
3.3.2.1. Effect of temperature. Fig. 7 shows the perturbation diagrams of
the leaching parameters effect on Th and Ce recovery. It is shown in
13 this gure that temperature has a negative effect on Ce recovery
(same for La and Nd, see Section 3.2.2). It is worth mentioning that in
order to leach the monazite concentrate, the hydration energy of
metal cation (Ce or Th) should be greater than the energy required to
break the cation- phosphate bonding. The latter also includes the kinetic
energy of the ions. The higher the difference between the hydration en-
ergy and the energy required to break the cation- phosphate bonding,
the better the monazite leaching (Gupta, 1990; Panda et al., 2014;
Kumari et al., 2014). In the case of Ce, this difference decreases with in-
crease in the temperature. In addition, Fig. 7 shows that temperature
has a positive effect on the recovery of Th, suggesting that in the case
of thorium, increasing the temperature increases the above mentioned
energy difference which results in better progress of the leaching
process.
3.3.2.2. Effect of time. Fig. 7 implies that leaching time is desirable for in-
creasing Ce, La and Nd recovery; since longer leaching time or longer
14 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715

contact time between the particles and the leach liquor creates more
dissolving of the rare earth compounds in water. Over time, the dense
solid product of the digestion stage begins to disrupt and the rare
earth ions enter the leach liquor. In longer times, the disruption and dis-
solution increases. Kim et al. (2014) and Kumari et al. (2014) showed
the same result in their research.

3.3.2.3. Effect of L/S ratio. According to Fig. 7, raising the L/S ratio im-
proves the recovery of the rare earths as a consequence of increasing
the solid and liquid interfaces, where the reaction between solid and liq-
uid is expected to occur. The disruption of the solid product occurs while
leaching, and the new interfaces need more liquid to react with. Also, in-
creasing the L/S ratio causes the solution to become saturated later and
these all increase the leaching recovery. Kumari et al. (2014) revealed
Fig. 9. Interaction between L/S ratio and temperature in leaching of Ce.
the same result in their work.

3.3.2.4. Interaction between temperature and time. Fig. 8 illustrates the in-
positive effect, lower L/S illustrates a negative effect, thus, negative ef-
teraction between temperature and time in the leaching recovery of Ce
fects are stronger and recovery decreases. Generally, it can be concluded
(the same for La and Nd, see Section 3.2.2). In this gure two trends
that when both L/S ratio and time are in their maximum limit, temper-
could be seen. One for shorter leaching time of 5 h, where by increasing
ature acts as a parameter with the positive impact.
the temperature the leaching recovery of Ce, La and Nd decreased. How-
ever, at longer leaching time of 15 h, increasing the temperature in-
3.3.3. Optimum conditions
creased the recovery of Ce, La and Nd. This can be attributed to the
According to Table 2, experiment 9 has the highest leaching recovery
fact that in shorter leaching time the dense dry digested mass is not
for all four elements. Therefore, the optimum conditions in leaching
disrupted completely. As a result, the reaction surface between solid
process would be: temperature of 75 C, time of 15 h and L/S ratio of
and liquid becomes smaller and the penetration of the solution is less
7.5. Using the results of digestion and leaching process, the overall re-
likely possible. In contrast when the leaching time is longer the residue
covery is calculated for all four elements in the optimum conditions
is disrupted. Feng et al. (2013) and Kim et al. (2014) studied rare earth
which are shown in Table 6.
elements' leaching and showed that leaching is diffusion controlled.
Therefore, in shorter leaching time that the solid residue is still dense,
3.4. Precipitation experiments
the penetration occurs harder; thus, the leaching reaction is less likely
to happen.
Chemical precipitation by oxalic acid was used to separate the REEs
High temperature has two effects, rst, it provides the activation en-
from the leach liquor. Adding oxalic acid to the leach liquor containing
ergy of the reaction and facilitates the leaching reaction. Second, as
rare earth ions (RE), produces a white RE oxalate precipitate according
mentioned before (see Section 3.3.2.1), increase in temperature de-
to the following reaction:
creases the difference between the hydration energy and the energy re-
quired to break the Ce-phosphate bonding; thus, the monazite leaching
recovery decreases. In a longer leaching time, because of the disruption RE2 SO4 3 3H2 C2 O4 RE2 C2 O4 3 3H2 SO4 16
of solid residue, the diffusion occurs faster and thus, the leaching reac-
tion becomes faster and the recovery increases. In fact, temperature where RE is Th, Ce, La or Nd. However, oxalate complexes of impurities
has a positive and a negative effect and its impact is determined by such as Si, Al, Mg, Fe, Ca, S and P remain in solution at this stage, in
other parameters. pH 0.92. The RE oxalate precipitate was calcined at 800 C for 1 h and
a mixture of RE oxides was obtained. At this temperature, RE oxalates
3.3.2.5. Interaction between temperature and L/S ratio. Fig. 9 illustrates the react with oxygen to form RE oxides (REO) and releasing CO2 according
interaction between temperature and L/S in the leaching of Ce (the to the following reaction:
same for La and Nd, see Section 3.2.2). It is clear that this interaction af-
fects the leaching system so that in lower L/S ratio, increasing the tem-
2RE2 C2 O4 3 3O2 2RE2 O3 s 6CO2 17
perature decreases the leaching recovery since both parameters are not
in favour of increasing recovery; temperature has a negative and a
Table 7 shows the XRF result for the REO mixture. It indicates that
REOs of Th, Ce, La and Nd had a signicant increase compared to the pri-
mary concentrate (25% REO) and their amounts in the nal concentrate
were 0.8, 32.6, 20.2 and 17.5%, respectively. Percentage of total REOs in
the nal concentrate was 84% which demonstrates that a large amount
of impurities, such as Fe, Si, Al and P, were removed during the applied
processes and ca. 3.36 times improvement in the grade was achieved.

Table 6
Overall recovery of digestion and leaching process.

Digestion recovery (%) Leaching recovery (%)

(t = 3.5 h, T = 225 C, (t = 15 h, T = 75 C, Overall
Element L/S = 2.5) L/S = 7.5) recovery (%)

Ce 93.00 80.43 74.80

La 92.44 82.13 75.92
Nd 92.86 84.16 78.15
Th 87.97 72.36 63.65
Fig. 8. Interaction between time and temperature in leaching of Ce.
 F. Sadri et al. / International Journal of Mineral Processing 159 (2017) 715 15

Table 7 Acknowledgments
XRF results for the nal REO mixture.

Composition SiO2 Fe2O3 Al2O3 MgO CaO SO3 P2O5 The authors wish to express their gratitude to The Geological Survey
% 3.7 2.7 0.7 1.5 1.4 3.7 1.5 of Iran for providing the Monazite concentrate. Many thanks are also ex-
Composition La2O3 CeO2 Pr2O3 ThO2 Nd2O3 Y2O3 L.O.I. tended to Ms. Aazam Kavusi from The Geological Survey of Iran for her
% 20.2 32.6 12.2 0.8 17.5 0.6 0.6
kind efforts in analyzing the ICP samples throughout the project.
Loss of ignition.

4. Conclusions
A Monazite concentrate containing 14.16% Ce, 6.48% La and 6% Nd
was digested by sulfuric acid to increase the solubility of Ce, La and
Nd.
Effect of the digestion and leaching parameters: time, temperature
and L/S ratio in REEs recovery were investigated for the rst time
using Taguchi method.
In digestion process, increasing temperature from 200 to 250 C had
negative effect on this process while increasing L/S ratio improved
the recovery of the rare earth elements.
Increasing the digestion time from 1 to 3.5 h resulted in increasing
Ce, La and Nd recovery; however, Th recovery had a decreasing
trend. Increasing digestion time up to 6 h caused decreasing recov-
ery for all elements.
The optimum condition for the digestion process was temperature
of 225 C, time of 3.5 h and L/S ratio of 2.5. Under this condition,
the recoveries of 93, 92.44, 92.86 and 87.97% were obtained for Ce,
La, Nd and Th, respectively.
In the leaching process, time and L/S ratio had positive effects on
the recovery of Ce, La and Nd. Temperature had a negative effect
on the recovery of Ce, La and Nd but a positive effect on the
recovery of Th. The interaction between temperature and time
and also temperature and L/S showed a positive effect on the
leaching process.
The optimum leaching condition was found to be leaching time of
15 h, temperature of 75 C and L/S of 7.5. Under this condition, the
recovery of 80.43%, 82.13%, 84.16% and 72.36% was obtained for
Ce, La, Nd and Th, respectively.
The grade of the primary concentrate (containing 25% REO) was
increased ca. 3.36 times and ca. 59% of the impurities were re-
moved to produce a REE concentrate containing 84% REO.
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