Minerals Engineering 139 (2019) 105865

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Minerals Engineering
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Selective cerium removal by thermal treatment of mixed rare earth oxalates T

or carbonates obtained from non-purified rare earth sulphate liquor
Ruberlan Gomes Silvaa, , Carlos Antonio Moraisb, Éder Domingos Oliveirac
⁎

a
VALE Mineral Development Centre, Rodovia BR 381, Km 450, Distrito Industrial Simão da Cunha, CEP 33040-900 Santa Luzia, MG, Brazil
b
Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN), Av. Presidente Antônio Carlos, 6627, Pampulha, CEP 30123-970 Belo Horizonte, MG, Brazil
c
Department of Chemical Engineering, Universidade Federal de Minas Gerais (UFMG), Av. Presidente Antônio Carlos, 6677, Pampulha, CEP 31270-901 Belo Horizonte,
MG, Brazil

ARTICLE INFO ABSTRACT

Keywords: One of the world́s most abundant of all the rare earth elements (REE) is cerium. It represents about 50 wt% of
Cerium removal total REE content in the main rare earth minerals used industrially (monazite and bastnaesite). However, cerium
Rare earth element is not a valuable product if compared with the other REE. In the most current pyro-hydrometallurgical processes
Thermal treatment routes, a high amount of cerium goes to the rare earth liquor, incurring in high operational and capital costs in
Hydrochloric acid leaching
the solvent extraction step used in the separation of each individual rare earth element. In this context, this study
evaluates the use of thermal treatment for rare earth oxalates and carbonates and also hydrochloric acid leaching
of calcination products for selective separation of cerium from other REE. This investigation also sheds light on
the mechanisms involved in the processes proposed. For this purpose, mixed rare earth and cerium oxalates, also
mixed rare earth and cerium carbonates were used as precursors. The mixed rare earth salts used in the ex-
periments were generated from a non-purified rare earth sulphate liquor. The results indicated that the minimum
required temperature to fully decompose the mixed rare earth oxalates, cerium oxalate, mixed rare earth car-
bonates and cerium carbonate to their respective rare earth oxides (REE2O3) or CeO2, was 1100 °C, with 1 h of
residence time. In the experiments carried out with mixed rare earth oxalates, Ce3+ was not fully oxidized to
Ce4+, it formed a mixture of Ce2O3 and CeO2 represented by Ce4O7, which was completely dissolved in the
hydrochloric acid solution (37 wt%). Therefore, in such case, cerium was not selectively removed from the mixed
rare earth oxalates by thermal treatment and hydrochloric acid leaching. On the other hand, the Ce3+ presented
in the composition of the pure cerium oxalate or carbonate was fully oxidized to Ce4+ (CeO2) under the same
condition of calcination. As expected, CeO2 was not dissolved by the hydrochloric acid solution (37 wt%). It was
concluded that mixed rare earth carbonates generated Ce0.60Nd0.40O1.80 (Ce1-xNdxO2-x/2, x = 0.40) when cal-
cined under the same condition. This crystalline structure was not also dissolved by hydrochloric acid solution
(37 wt%). As a result, a process flowsheet was proposed to remove cerium selectively from a rare earth ore.

1. Introduction than other commonly exploited elements but they are not concentrated
enough to make them easily exploitable (Jar et al., 2016). Currently,
Rare earth elements (REE) include the 15 elements of the lanthanide well over 250 rare earth minerals have been recognized, however in
group from lanthanum to lutetium, coupled with chemically similar most of them the concentration of rare earth is very low, ranging from
yttrium and infrequently scandium. These elements are split into three 10 to 300 ppm (Zhang and Edwards, 2012). Only three minerals are
sub-groups: light rare earth elements (LREE (La, Ce, Pr and Nd)), SEG extensively used in the production of rare earth products, namely
elements (Sm, Eu, Gd) and then the heavy rare earth elements (HREE bastnasite (REECO3F), monazite (REEPO4) and xenotime (YPO4)
(Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y)) (Wang et al., 2017; Silva et al., (Kanazawa and Kamitani, 2005).
2019a). The normal oxidation state of the lanthanides is 3+, but some REE and their alloys are used in many ways, such as in memory
can either be reduced to 2+, such as Eu, or oxidized to 4+, such as Ce storage devices, rechargeable batteries, mobile phones, catalytic con-
(Donohue, 1979; Abrão, 1994). verters, magnets, fluorescent bulbs and so on (Krishnamurthy and
Rare earth elements are relatively more abundant in the earth́s crust Gupta, 2004). Currently, the strongest magnet available belongs to

⁎
Corresponding author.
E-mail addresses: ruberlan.silva@vale.com (R.G. Silva), cmorais@cdtn.br (C.A. Morais), eder@deq.ufmg.br (É.D. Oliveira).

https://doi.org/10.1016/j.mineng.2019.105865
Received 27 April 2019; Received in revised form 5 July 2019; Accepted 7 July 2019
Available online 10 July 2019
0892-6875/ © 2019 Elsevier Ltd. All rights reserved.
R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

NdFeB magnet family and it is composed of 30–40 wt% of REE Considering the pure precursors, the oxidation of Ce3+– Ce4+ occurs
(15–30 wt% of it is Nd) and 60–70 wt% of other elements (50–70 wt% during calcination under different air temperatures, according to the
of its content is Fe alongside ∼ 1 wt% of B) (Onal et al., 2015). An in- reactions shown in Eq. (1), Eq. (2) and Eq. (3). For hydroxide pre-
crease in demand of more than 700% for Nd and 2600% for Dy for the cursors, oxidation takes place at low temperature (< 150 °C), for car-
next 25 years has been forecast, due to the development of the elec- bonate precursors, it occurs in a temperature range of 200–400 °C
tronic vehicles and wind energy industries (Alonso et al., 2012; Bauer (Krishnamurthy and Gupta, 2004), and for oxalate precursors the total
et al., 2010). More specifically, cerium oxide (CeO2) have numerous decomposition and oxidation occurs in the range of 250–450 °C (Zhai
applications in catalysts, cosmetics, ceramic, oxygen gas sensors, solid et al., 2007). In all the conditions described above, the CeO2 formed has
oxide fuel and fluorescent materials (Zhai et al., 2007; Li et al., 2018). little solubility in hydrochloric acid solution.
Currently, China supplies about 94% of the world́s REE demand, with
4Ce(OH)3(s) + O2(g) + 2H2O(l) → 4Ce(OH)4(s) (or 4CeO2·2H2O) (1)
the remainder produced in Russia, Estonia, USA, India, Malaysia and
Brazil (Zhanheng, 2011). Ce2(CO3)3(s) + 1/2O2(g) → 2CeO2(s) + 3CO2(g) (2)
LREE minerals are classified as ‘cerium group’ minerals because
they contain approximately 50 wt% of cerium oxide. Bastnasite and Ce2(C2O4)3(s) → 2CeO2(s) + 2CO2(g) + 4CO(g) (3)
monazite are included in the ‘cerium group’, leading to an over- A recent study of the solubilization of mixed rare earth oxides by acid
production of cerium (McNeice and Ghanreman, 2018). The CeO2/ solutions (HNO3, HCl and H2SO4) has been undertaken by Horlait et al.
REE2O3 (Rare Earth Oxides) mass ratio is approximately 50 wt% for (2012). The rare earth oxides obtained from the respective oxalates cal-
bastnasite and 45–50 wt% in the case of monazite (Dan et al., 2014; Li cined at 1000 °C were represented by Ce1-xLnxO2-x/2, where Ln is any REE,
et al., 2018). Additionally, cerium removal is usually the first step in except Ce. The results indicated that solubilization is strongly dependent
REE purification, as the largest mass fraction of the concentrate lowers on the content of Ln in the crystalline structure formed after calcination.
the throughput of the subsequent steps (McNeice and Ghanreman, For Ln = Nd and x = 0.10, only 4% of the solid was dissolved after
2018; Xie et al., 2014). The low cerium content may be obtained by the 4 weeks; for Ln = Nd and x = 0.34, 54% was dissolved after 4 weeks and
follow-up acid dissolution process, which is favourable in the sub- for Ln = Nd and x = 0.59, the complete dissolution was achieved within
sequent extraction of rare earth elements (Yanhui et al., 2012). Several only a few hours. The experiments were carried out in pairs (La-Ce, Nd-Ce,
studies have been undertaken into the separation of cerium from other Sm-Ce, Eu-Ce, Gd-Ce, Dy-Ce, Er-Ce and Yb-Ce), rather than with a mixture
rare earth elements. of all rare earth elements, similar to the technique which is proposed in
The standard redox potential of Ce4+/Ce3+ is about 1.28 V in an this work. The current study evaluates these aspects with experiments
HCl medium (Yu et al., 2006). Hence strong oxidants such as persulfate carried out with mixed rare earth oxalates and mixed rare earth carbo-
(2.1 V), potassium permanganate (1.7 V), bromate, ozone (2.2 V), nates, each one containing the following mass ratios: La/REE = 18–27 wt
chlorine (1.4 V) and hypochlorite (1.6 V) have been used in the oxi- %, Ce/REE = 47–50 wt%, Pr/REE = 5.3–5.8 wt%, Nd/REE = 17–23 wt%
dation of cerium. Electrolysis is another technique which was studied and other rare earth oxides/REE = 3.6–3.9 wt%.
by several researchers. The aforementioned reagents and methods are In terms of processing, three precipitating agents, namely, oxalic
costly and the process is not helped by the generation of by-products acid, ammonium/sodium hydroxide or ammonium/sodium bicarbo-
that can impair the performance of the process. It can also require nate/carbonate, are typically applied in the production of rare earth
additional steps to separate it from the cerium thereby compromising concentrates (Lucas et al., 2015; Silva et al., 2019b). More specifically,
the project economics. oxalic acid is used in the precipitation of high purity products, whereas
Abreu and Morais (2010) processed monazite through a series of hydroxides and carbonates are used to precipitate products demanding
steps before achieving a chloride solution. The Ce3+ was then oxidized less rigorous purity. The choice of the agent depends on the physical
to Ce4+ with the use of potassium permanganate. The optimum pH characteristics required in the application of the final product (Lucas
found was around 3, where both Ce recovery and purity were 99%. et al., 2015). Recently, there has been an increasing interest in the
More than 30% of stoichiometric dosage of permanganate was needed. processing of lower grade ores which are not readily amenable to
MnO2 was co-precipitated with CeO2 so that the product reached 69 wt beneficiation and impurity separation of REE (Anvia et al., 2013).
% CeO2 and 14 wt% MnO2. This solid was re-dissolved in HCl and the Nevertheless, purity and quality are factors that impact the final
Ce re-precipitated as hydroxide or oxalate, yielding CeO2 and MnO2 price of the rare earth products (Abreu and Morais, 2010; Morais and
with purities of 99.0% and 99.5%, respectively. Ciminelli, 2004; Silva et al., 2019b; Panda el al., 2016). However, the
Additionally, Goode (2018) listed several methods that could be solvent extraction step is required to individually separate each REE
applied in the selective removal of cerium from a mixture of rare earth dissolved in either nitric or hydrochloric acid and the presence of dis-
elements, including separation techniques based on the oxidation of solved impurities can result in emulsification of the extractants, causing
Ce3+ in a solution and by thermal treatment of rare earth hydroxides, in a negative impact on the purity of the final product (Ru'an et al., 1995).
order to get Ce4+. The use of ozone (O3), sodium hypochlorite (NaOCl), There are few studies in the literature aiming at elucidating the
potassium permanganate (KMnO4), hydrogen peroxide (H2O2), elec- mechanism involving in the thermal oxidation of the cerium present in
trolytic oxidation and photochemical oxidation were also evaluated. the composition of a mixed rare earth oxalates. In this context, this
The oxidation of cerium by blowing air onto a slurry of rare earth study addresses the use of thermal treatment, XRD patterns and hy-
hydroxides attained has the lowest cost (Krishnamurthy and Gupta, drochloric acid leaching to selectively separate Ce from other rare earth
2004; Lucas et al., 2015). The oxidization of Ce3+ in a basic condition, elements and then shed light on the mechanisms involving in the
such as rare earth hydroxides (REE(OH)3) in contact with hot air, is well thermal processes. Finally, a process flow sheet with a mass balance was
known by the state-of-art (Krishnamurthy and Gupta, 2004; Lucas et al., proposed to remove cerium selectively from any other rare earth ele-
2015). During the drying operation of the mixed rare earth hydroxides, ment present in a rare earth ore.
Ce3+ is oxidized and converted into hydrate CeO2·xH2O (Ce4+).
In the same way, cerium is separated from bastnasite (REECO3F)
through roasting. In the Molycorp process operated in the 1960 s at 2. Material and methods
Mountain Pass, the bastnasite concentrate was roasted in air at 620 °C in
order to eliminate carbon dioxide and oxidize the Ce3+ to Ce4+ (Harrah, 2.1. Reagents and analytical methods
1967; Krishnamurthy and Gupta, 2004). The calcined was leached with
hydrochloric acid, leaving Ce4+ in the residue, thus producing a leaching 2.1.1. Reagents
solution containing approximately 100 g/L of REE2O3. HCl 37 wt% analytical reagent (A. R.), CeO2 A. R. (99.9 wt%),

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Table 1 calcination products comprised the following steps:

Reagents used in this study.
Reagent Information • Weighing of approximately 50 g of the calcination product in a
beaker;
HCl
CeO2
Hydrochloric acid 37 wt% from ANIDROL
Cerium (IV) oxide 99.9 wt% purity from MERCK
• Adding about 65 wt% of distilled water (about 33 g) and dispersing
the calcination product in order to form a paste.
• Transferring the paste to a round-bottom flask connected to a
Ce2(C2O4)3·xH2O Cerium oxalate hydrated 99.9 wt% purity from ALDRICH
Ce2(CO3)3·xH2O Cerium carbonate hydrated 99.9 wt% purity from ALDRICH
heating mantle attached to a top condenser;
• Adding a HCl solution 37 wt% slowly until the pulp reached 25 wt%
Ce2(CO3)3·xH2O A.R. (99.9 wt%) and Ce2(C2O4)3·xH2O A. R. (99.9 wt%) of the calcination product and 75 wt% of HCl solution (37 wt%);
were used as reagents in this study (see Table 1). • Maintaining the heating at 90 °C (Yanhui et al., 2012) and stirring
Mixed rare earth oxalates and carbonates were obtained from a the pulp at a speed fast enough to keep the solids in suspension for
purified rare earth sulphate liquor generated in the processing of a rare 4 h;
earth ore with monazite as the main REE carrier (Berni et al., 2013; • Addition of about 200 mL of distilled water in order to dilute the
Teixeira and Silva, 2015; Testa et al, 2016; Silva et al., 2018a; Silva pulp;
et al., 2018b; Silva et al., 2019a; Silva et al., 2019b; Teixeira et al., • Stirring for about 30 min at a speed fast enough to maintain the
2019). The REE components were precipitated from the sulphate liquor solids in suspension. Heating is not necessary in this step;
by using oxalic acid and sodium carbonate as reagents. • Filtering the pulp, in order to generate the filtrate I and the wet cake
(not washed);
2.1.2. Analytical methods • Washing the cake preparing a pulp containing 25 wt% of not washed
The concentrations of aluminium, iron, phosphorus, sulfur, lan- wet cake and 75 wt% of distilled water. Stirring for about 30 min at
thanum, praseodymium, neodymium and samarium in the liquid sam- a speed fast enough to maintain the solids in suspension;
ples were determined by a Varian VISTA-PRO ICP-OES (Inductively • Filtering the pulp in order to generate the filtrate II and the washed
Coupled Plasma – Optical Emission Spectrometry). Other rare earth wet cake.
elements and impurities were determined by a PerkinElmer NexION • Mixing filtrate I with filtrate II. The rare earth hydrochloric liquor
300D ICP-MS (Inductively Coupled Plasma Mass Spectrometry). ICP-MS was generated. A sample of the liquor was assayed;
was used to measure low concentration with higher accuracy. The • Drying the washed wet cake at 75 °C until it reaches a constant
content of the elements in the solid samples were determined according weight. A sample of the dry cake was assayed.
to the analytical methods described in Table 2. In addition, the solids
samples were put into an oven and dried at 75 °C for 4 h, cooled to room Considering a mean molecular weight of 141 g/mol for REE, the
temperature (20 °C) and then pulverized to 95 wt% below 74 µm. stoichiometric ratio HCl/REE2O3 is 0.66 wt/wt. In all experiments, the
The pH and redox potential measurements were performed with a mass ratio HCl/REE2O3 of 1.12 wt/wt was applied, which means an
Mettler Toledo M400, using a reference electrode InPro3250SG/325/ excess of 70% of the HCl added.
Pt10. Dried samples for X-ray diffraction were ground to < 74 µm and
analyzed in a PANalytical X'PERT PRO MPD with θ/θ geometry and Cu 3. Results and discussion
anode under 2000 W and 60 kV. The thermogravimetric and differential
thermogravimetric analysis (TG/DTA) were carried out in a Netzsch 3.1. Thermal analysis
STA 449F3 in the temperature range of 20–1200 °C under a 10 °C/min
rate and static air, using alumina crucible. 3.1.1. Mixed rare earth oxalates and pure cerium oxalate
Fig. 1(a)–(c) respectively show the thermogravimetry (TG), differ-
ential thermogravimetry (DTG) and differential thermal analysis (DTA)
2.2. Procedures curves obtained by the thermal treatment of the mixed rare earth ox-
alates and pure cerium oxalate.
2.2.1. Calcination According to Fig. 1(a) and (b), it can be seen that the weight loss
The procedure used in calcination experiments comprised the fol- process can be divided into three steps:
lowing steps:

• Weighing of approximately 100 g of precursor. A container made of • The first step, which occurred at temperatures from 65 °C to 125 °C
owed to the dehydration of both products. The weight losses in both
zirconite was used, its height was approximately 10 cm, to prevent products were about 8 wt%. No free water occurred in the mixed
any mass losses during thermal decomposition; rare earth oxalates, since this sample was dried at 60 °C before the
• Calcination in different temperatures (450 °C, 700 °C and 1100 °C) thermal analysis. According to this weight loss, the precursors can
and residence times (1 h and 4 h); be classified as REE2(C2O4)3·2.7H2O and Ce2(C2O4)3·2.6H2O A mean
• Cooling of the calcination products to room temperature (20 °C); molecular weight of 141 g.mol−1 was used to represent the REE.
• Weighing of the final mass and assaying the calcination products. This value was explained in Section 3.2 of the current study. The
reactions occurring in this step are shown in Eq. (4) and Eq. (5).
2.2.2. Hydrochloric acid leaching
The procedure used in hydrochloric acid leaching experiments of REE2(C2O4)3·2·.7H2O(s) → REE2(C2O4)3(s) + 2·.7H2O(g) (4)

Table 2
Methods used in the chemical analyses of solid samples.
Elements Procedures

REE Fusion with Li2B4O7 or H2O2, cooling and dilution in 2% (vol/vol) nitric acid and reading in ICP-MS
Na Digestion with HNO3 and HF and reading in ICP-OES
S, Ca, Mg, Fe, Al, P, Mn Fusion with Na2CO3 and Na2B4O7, dilution to 67% (vol/vol) hydrochloric acid and reading in ICP-OES.
S, C Direct combustion and infrared spectrometry (solid sample)

3
R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

100 1
90

80
-1
70

DTG (kg/ºC)
60
TG (%)

50 -3
40

30
-5
20
Mixed rare earth oxalates Mixed rare earth oxalates
10 Pure cerium oxalate
Pure cerium oxalate
0 -7
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Temperature (°C) Temperature (°C)
(a) (b)
2.0
Exothermic
1.5
DTA (µV/mg)

1.0

0.5

0.0

-0.5 Mixed rare earth oxalates

Pure cerium oxalate
-1.0
0 200 400 600 800 1000 1200

Temperature (°C)
(c)
Fig. 1. (a) TG curves (b) DTG curves (derivative of TG curve) and (c) DTA curves of mixed rare earth oxalates and pure cerium oxalate as precursors.

against 455 °C) to decompose completely. This could be explained

Ce2(C2O4)3·2·.6H2O(s) → Ce2(C2O4)3(s) + 2·.6H2O(g) (5)
by the presence of other rare earth elements in the composition of
mixed rare earth oxalates. The weight losses for each product
• The second step took place from 125 °C to 200 °C, due to the partial reached the same value (30 wt%) in this step. The total weight loss
observed was 51 wt%. Not considering the weight losses relating to
decomposition of both products. It was assumed that mixed rare
earth oxalates/carbonates or cerium oxalate/carbonate were formed dehydration (8 wt%), the total weight losses of the anhydrous mixed
in this phase, according to the reactions shown in Eq. (6) and Eq. (7) rare earth or pure cerium oxalates were about 43 wt%. This value is
(Ubaldini et al., 2008). In this step, the weight losses in each product close to what was expected to cause the complete thermal decom-
were the same (13 wt%). position of the anhydrous pure cerium oxalate (approximately 40 wt
%). According to the TG analysis, the composition of the mixed rare
REE2(C2O4)3(s) → REE2(C2O4)5/2(CO3)1/2(s) + 0.5CO(g) (6) earth oxalates was 49 wt% of crystalline structure to be defined in
Ce2(C2O4)3(s) → Ce2(C2O4)5/2(CO3)1/2(s) + 0.5CO(g) (7) this study, 43 wt% of CO2 and 8 wt% of H2O. The composition of the
pure cerium oxalate was 49 wt% of CeO2, 43 wt% of CO2 and 8 wt%
of H2O. The reactions that took place in this step are shown in Eq.
• The third step occurred from 300 °C to 455 °C in the pure cerium (8) and Eq. (9).
oxalate and from 400 °C to 580 °C in the case of the mixed rare earth
oxalates, due to the formation of crystalline structures, likely CeO2, REE2(C2O4)3(s) + 3/2O2(g) → REE2O3(s) + 6CO2(g) (8)
a structure between Ce2O3 and CeO2, or a component such as Ce1- Ce2(C2O4)3(s) + 2O2 → 2CeO2(s) + 6CO2(g) (9)
3+
xLnxO2-x/2, where Ln is any rare earth elements cation (REE ), with
exception of Ce. The crystalline structure formed was addressed
later. After 455 °C, for pure cerium oxalate, and after 580 °C for According to Fig. 1(c), both products showed endothermic events oc-
mixed rare earth oxalates, the weights no longer varied, which in- curring between 90 °C and 160 °C, this may occured due to dehydration
dicated that the salts have fully decomposed. It was observed that and partial thermal decomposition of the precursors. Additionally, an
the mixed rare earth oxalates require high temperatures (580 °C exothermic event started at 300 °C in both products, it finished at 400 °C
when the precursor was the mixed rare earth oxalates and at 425 °C

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

100 2
90
1
80

70 0

DTG (kg/ºC)
TG (%)

60
-1
50
40 -2

30
-3
20
Mixed rare earth carbonates Mixed rare earth carbonates
10 -4
Pure cerium carbonate
Pure cerium carbonate
0
-5
0 200 400 600 800 1000 1200
0 200 400 600 800 1000 1200
Temperature (°C) Temperature (°C)
(a) (b)

2.0

1.5 Exothermic
1.0
Mixed rare earth carbonates
0.5 Pure cerium carbonate
DTA (µV/mg)

0.0

-0.5

-1.0

-1.5

-2.0

-2.5

-3.0
0 200 400 600 800 1000 1200
Temperature (°C)
(c)
Fig. 2. (a) TG curves, (b) DTG curves and (c) DTA curves of mixed rare earth carbonates and pure cerium carbonate as precursors.

when the precursor was the pure cerium oxalate. attributed to free water loss and 11 wt% happened due to the
Different to what was observed, another exothermic event occurred crystallization water loss. Free water was not observed as these
with the mixed rare earth oxalates, starting at 400 °C and finishing at samples were also dried prior to the thermal analysis similar to the
775 °C. This could mean that there was a formation of a different oxalates in Section 3.1.1. Considering these weight losses, the pre-
crystalline structure in the range 400–775 °C when the mixed rare earth cursors can be shown as REE2(CO3)3·1.4H2O and Ce2(CO3)3·3.2H2O,
oxalates were thermally decomposed. The XRD patterns of the calci- respectively. The reactions that occurred in this step are shown in
nation products and the results of the hydrochloric leaching experi- the Eq. (10) and Eq. (11).
ments are expected to complement these behaviours, and also elucidate
REE2(CO3)3·1.4H2O(s) → REE2(CO3)3(s) + 1.4H2O(g) (10)
the difference in the results of cerium removals from both calcination
products. Ce2(CO3)3·3.2H2O(s) → Ce2(CO3)3(s) + 3.2H2O(g) (11)

3.1.2. Mixed rare earth carbonates and pure cerium carbonate

Fig. 2(a)–(c) show respectively the TG, DTG and DTA curves ob- • The second step occurred from 160 °C to 600 °C due to the decom-
tained by thermal treatment of mixed rare earth carbonates and pure position of the anhydrous mixed rare earth carbonates or anhydrous
cerium carbonate as precursors. cerium carbonate and the formation of a crystalline structure,
According to the curves shown in Fig. 2(a) and (b), it can be seen probably CeO2, a structure between Ce2O3 and CeO2 or a component
that the process of weight loss can be divided into two steps: such as Ce1-xLnxO2-x/2. The crystalline structure formed was dis-
cussed further in this study. For values above 600 °C, the weights no
• The first step, from 70 °C to 160 °C it can be attributed to dehy- longer did not show any variation, which indicated the salts have
decomposed completely. The weight loss in each product was the
dration of each product and also the formation of the anhydrous
mixed rare earth carbonates or anhydrous cerium carbonate. The same (24 wt%) in this step. The total weight loss was 29 wt%, when
weight loss in the mixed rare earth carbonates was about 5 wt% and the precursor was mixed rare earth oxalates and 40 wt%, when the
in the case of pure cerium carbonate it assigned 16 wt%. From the precursor was pure cerium oxalate.
total weight loss of 16 wt% with pure cerium carbonate, 5 wt% was
Not considering the weight loss attributed to dehydration, which

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

ones was 16 wt% when the precursor was the pure cerium oxalate, the REE2(C2O4)3·xH2O(s) + 3H2SO4(aq) (14)
total weight loss of anhydrous pure cerium carbonate was about 24 wt
REE2(SO4)3(aq) + 3Na2CO3(aq) + xH2O(l) → RE-
%. This value was similar to what was expected for the thermal de-
E2(CO3)3·xH2O(s) + 3Na2SO4(aq) (15)
composition of the anhydrous pure cerium carbonate (approximately
25 wt%). According to the TG analysis, the composition of the mixed REE2(SO4)3(aq) + Na2SO4(aq) → 2NaREE(SO4)2(s) (16)
rare earth carbonates was 71 wt% of a crystalline structure to be de-
fined in this study, 24 wt% of CO2 and 5 wt% of H2O. The composition According to what was expected, there was no a significant variation in
of the pure cerium carbonate was 60 wt% of CeO2, 24 wt% of CO2 and the mass ratios of individual rare earth elements/REE (i.e. La/REE, Ce/
16 wt% of H2O (5 wt% of free water and 11 wt% of crystallization REE, etc.) in the mixed rare earth oxalates and carbonates. The sum of
water). The reactions that occurred in this step are shown in Eq. (12) the mass ratios of La/REE, Ce/REE, Pr/REE and Nd/REE is above 96 wt
and Eq. (13). % in both cases, while the mass ratio for Ce/REE being about 48.9 wt%.
Considering the individual mass ratios of both products and the re-
REE2(CO3)3(s) → REE2O3(s) + 3CO2(g) (12) spective molecular weight of each rare earth element, the molecular
weight of the REE is about 141 g.mol−1. This value just justify the use
Ce2(CO3)3(s) + 1/2O2 → 2CeO2(s) + 3CO2(g) (13)
of 141 g.mol−1 in the estimation of the amount of the crystallization
Fig. 2(c) depicts an exothermic event starting at 145 °C with pure water molecules in their respective compositions in Section 3.1.1 of this
cerium carbonate, which was not displayed in the case of mixed rare study.
earth carbonate. On the contrary, the mixed rare earth carbonated
showed an endothermic reaction at 825 °C, while the pure cerium
3.3. Calcination experiments
carbonate showed the same at 1100 °C. The XRD patterns of calcination
product and the results of the hydrochloric acid leaching experiments
3.3.1. Mixed rare earth oxalates
will allow an understanding of these behaviours.
Table 5 shows the results obtained in the calcination experiments
with mixed rare earth oxalates.
3.2. Chemical analyses of mixed rare earth oxalates and carbonates It can be observed that there was a complete thermal decomposition
of the mixed rare earth oxalates in the muffle at 1100 °C and 1 h of
The Table 3 presents the composition of the mixed rare earth ox- residence time. An incomplete calcination is also observed given the
alates or carbonates used in this study, whereas Table 4 shows the in- carbon content existing in the product after thermal treatment.
dividual REE mass ratios for both products. Under these conditions, the weight losses stabilized at 52 wt%,
It is possible to see that the mixed rare earth oxalates contain lower value very close to figures observed in the thermogravimetric analysis
REE2O3 and sulphate content, whereas the mixed rare earth carbonates (51 wt%). As expected, the REE2O3 and impurities content increased
presented a higher sulphate, Fe2O3, Al2O3, MnO2 and Na2O content. alongside rose with temperature and residence time. Additionally, there
The amount of crystallization water in their compositions complied was no significant variation in the La/REE, Ce/REE, Nd/REE e Pr/REE
with what was determined in their thermogravimetric analysis. mass ratios in the calcination products, when compared with the ones
The total amount of impurities was about 0.20 wt% in the mixed in the mixed rare earth oxalates (see Table 4).
rare earth oxalates and 2.25 wt% in the mixed rare earth carbonates. Fig. 3 shows X-ray diffraction analysis (XRD) of CeO2 A.R. 99.9 wt
The main impurity presented in the mixed rare earth oxalates is sul- %, mixed rare earth oxalates and samples obtained in a muffle, at dif-
phate (0.19 wt%), perhaps due to the coprecipitation of some sulphate ferent temperatures (450 °C, 700 °C and 1100 °C) and residence time of
salts, where the main impurities in the mixed rare earth carbonates are 1 h, whereas Fig. 4 presents the XRD patterns of the calcination pro-
sulphates (1.45 wt%), iron oxide (0.13 wt%), aluminium oxide (0.12 wt ducts generated at the same temperatures, but with a residence time of
%), manganese oxide (0.46 wt%) and sodium oxide (0.08 wt%). A low 4 h.
purity mixed rare earth carbonate occured due to the coprecipitation of The Fig. 3 and Fig. 4 suggest that the crystallinity increases along-
some sulphate salts or hydroxides containing Mn, Fe and Al, and the side a rise in the calcination temperature and residence time, with
formation of sodium and rare earth double sulphate or NaREE(SO4)2 peaks becoming stronger and sharper gradually. The peaks of calcina-
(Morais et al., 2010; Silva et al., 2018b; Silva et al., 2019a). During the tion products are unlikely to correspond to the peaks of CeO2 A.R.
precipitation of REE with oxalic acid, sulfuric acid was generated, re- 99.9 wt%.
sulting in the fall in the pH of the filtrate to pH ∼ 1.4, whereas when
the REE was precipitated with sodium carbonate, the pH of the filtrate
3.3.2. Pure cerium oxalate
rose (pH ∼ 6.5) due to the formation of basic character salt (Na2SO4). A
Table 6 presents the results obtained in the calcination experiments
rise in pH favours the hydrolysis of some ions, such as, Fe3+ and Al3+
carried out with pure cerium oxalate.
ions, causing their precipitation (Silva et al., 2018a).
It can be observed that there was a complete thermal decomposition
The reaction that represents the precipitation of REE with oxalic
of the pure cerium oxalate in the muffle only at 1100 °C and 1 h of
acid and the formation of mixed rare earth oxalates is shown in Eq.
residence time. Under this condition, the weight losses were 48 wt%,
(14), whereas the reactions presented in the Eq. (15) and Eq. (16), show
value close to figures found in the thermogravimetric analysis (51 wt
the precipitation of REE with sodium carbonate and sodium sulphate,
%). Again, an incomplete calcination was also observed by the carbon
with the respective formation of mixed rare earth carbonates and so-
content in the product obtained after thermal treatment at temperatures
dium and rare earth double sulphate.
of 450 °C and 700 °C. As expected, the CeO2 and impurities content
REE2(SO4)3(aq) + 3C2H2O4(aq) + xH2O(l) → increased as temperature and time of calcination rose. Fig. 5 shows XRD

Table 3
Chemical compositions of mixed rare earth oxalates or carbonates (wt%).
Type of mixed rare earth REE2O3 REE C Sulphate Fe2O3 Al2O3 CaO MgO MnO2 P2O5 Na2O Water (*)

Oxalates 53.8 44.7 12.1 0.19 < 0.11 < 0.03 < 0.68 < 0.09 < 0.03 < 0.05 < 0.05 8.03
Carbonates 68.3 56.9 6.20 1.45 0.13 0.12 < 0.68 < 0.09 0.46 < 0.05 0.08 5.00

(*) Crystallization water.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Table 4
Individual rare earth elements mass ratios in the composition of mixed rare earth oxalates or carbonates (wt%).
Type of mixed rare earth La/REE Ce/REE Pr/REE Nd/REE Sm/REE Eu/REE Gd/REE Tb/REE

Oxalates 18.0 49.7 5.84 22.3 1.96 0.35 1.03 0.10

Carbonates 19.0 48.1 5.38 23.5 1.87 0.34 0.98 0.09

Type of mixed rare earth Dy/REE Ho/REE Er/REE Tm/REE Yb/REE Lu/REE Y/REE Sc/REE

Oxalates 0.15 0.02 0.03 0.010 0.007 0.010 0.45 0.001

Carbonates 0.15 0.02 0.02 0.010 0.007 0.010 0.43 0.001

Table 5 composition. Considering the initial carbon content (see Table 3), the
Results of calcination experiments with mixed rare earth oxalates. mean calcination efficiency was about 99.5%. The mean weight losses
Temperature (°C) 450 700 1100
stabilize in 31 wt%, having its value close to figures found in the
Time (h) 1 4 1 4 1 4 thermogravimetric analysis (29 wt%). The mean REE2O3 and impurities
Calcination products (g) 67.4 50.3 50.3 47.9 47.9 47.8 content were 88.1 wt% and 11.8 wt%, respectively. As expected, there
Weight loss (wt%) 33 50 50 52 52 52 was no significant variation in the La/REE, Ce/REE, Nd/REE and Pr/
Chemical composition of calcination products (wt%) REE mass ratios in comparison with values verified in the mixed rare
earth carbonates (see Table 4). Fig. 6 shows XRD patterns of CeO2 A.R.
REE2O3 66.8 90.9 94.7 97.2 97.7 98.0
99.9 wt%, mixed rare earth carbonates and calcination product ob-
REE 55.7 75.7 78.9 81.0 81.4 81.7
Carbon 6.75 1.98 0.98 0.04 < 0.03 < 0.03 tained in a muffle at temperature of 1100 °C and 1 h of residence time.
Impurities 0.59 0.76 0.75 0.80 0.82 0.81 From Fig. 6, it can be seen that the peaks of the calcination product
Mass ratios (wt%) seem are unlikely correspond to the peak of CeO2.

La/REE 18.2 18.0 17.9 18.1 18.0 18.0

3.3.4. Pure cerium carbonate
Ce/REE 49.5 49.9 49.7 49.4 49.9 49.7
Pr/REE 5.59 5.65 6.02 6.08 5.65 6.03 Table 8 presents the results obtained in the calcination experiments
Nd/REE 22.6 22.3 22.2 22.3 22.3 22.3 carried out with pure cerium carbonate.
Others rare earth elements (*) 4.14 4.12 4.16 4.06 4.12 4.05 It can be observed that there was a complete thermal decomposition
of the pure cerium carbonate in a muffle at 1100 °C and 1 h of residence
(*): Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.
time. Under such condition, the weight losses were 43 wt%, value close
to what was found in the thermogravimetric analysis (40 wt%). Again,
patterns of samples obtained in the muffle in different temperatures
an incomplete calcination was also observed given the presence of re-
(450 °C, 700 °C and 1100 °C) and residence time of 1 h.
sidual carbon in the calcination products obtained at 450 °C and 700 °C.
It can be seen that the crystallinity increases as calcination tem-
As expected, the CeO2 content increases as temperature and time of
perature rises, with peaks becoming stronger and sharper gradually.
calcination rose.
Additionally, the peaks of calcination the products are likely to corre-
Fig. 7 shows XRD patterns of CeO2 A. R. 99.9 wt%, pure cerium
spond to the peaks of CeO2.
carbonate and samples obtained in a muffle in different temperatures
(450 °C, 700 °C and 1100 °C) and residence time of 1 h.
3.3.3. Mixed rare earth carbonates From Fig. 7, it is possible to see that there was not a complete de-
Table 7 shows the results of two calcination experiments with mixed composition of pure cerium carbonate in a muffle at temperature of
rare earth carbonates carried out at 1100 °C and 1 h of residence time. 450°c and 700 °C, however, full decomposition occurs in the tempera-
The complete thermal decomposition of the mixed rare earth car- ture of 1100 °C and 1 h of residence time because the peaks of the
bonates was not observed due to the presence of carbon in their calcination products and CeO2 are similar.

Fig. 3. XRD patterns of CeO2 A.R. 99.9 wt%, mixed rare earth oxalates and calcination products obtained using the mixed rare earth oxalates as precursor at different
temperatures and residence time of 1 h.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Fig. 4. XRD patterns of CeO2 A.R. 99.9 wt%, mixed rare earth oxalates and calcination products obtained using the mixed rare earth oxalates as precursor at different
temperatures and residence time of 4 h.

Table 6 According to Fig. 8, it is observed that the crystalline structures

Results of calcination experiments with pure cerium oxalate. formed by the calcination of pure cerium oxalate and pure cerium
Temperature (°C) 450 700 1100
carbonate were CeO2, with peaks corresponding CeO2 A.R peaks. On
Time (h) 1 the other hand, different crystalline structures are formed when mixed
Calcination products (g) 61.9 53.9 52.2 rare earth oxalates or carbonates were calcined under the same con-
Weight loss (wt%) 38 46 48 dition. A crystalline structure formed between Ce2O3 (Ce3+) and CeO2
Chemical composition of calcination products (wt%) (Ce4+), represented by Ce4O7 with valence +3.5 (Ce3.5+), when the
mixed rare earth oxalates were calcinated, and Ce0.60Nd0.40O1.80 (Ce1-
CeO2 82.6 99.1 99.8
xNdxO2-x/2, x = 0.40) was formed when the mixed rare earth carbonates
Ce 67.3 80.7 81.2
Carbon 4.68 0.19 < 0.03 were calcinated.
Other elements 0.19 0.23 0.24 The present study unveils the identification of the crystalline
structure Ce4O7, which is a great breakthrough, which complements the
endothermic transformation that triggered at 400 °C, as illustrated in
3.4. XRD patterns comparison Fig. 1(c). However, the formation of Ce0.60Nd0.40O1.80 as a crystal
structure, was previously identified by Horlait et al. (2012). According
Fig. 8 shows XRD patterns (30° to 70° 2Theta) of CeO2 A.R. and of to Horlait et al. (2012), a crystal structure with x = 0.40, Ce1-xNdxO2-x/
the products obtained by calcination in muffle at 1100 °C and residence 2, has low solubility in mineral acids such as sulfuric, hydrochloric and
time of 1 h of pure cerium oxalate, pure cerium carbonate, mixed rare nitric acids.
earth oxalates and mixed rare earth carbonates as precursors.

Fig. 5. XRD patterns of CeO2 A.R, pure cerium oxalate and calcination products obtained with pure cerium oxalate as precursor at different temperatures and
residence time of 1 h.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Table 7 Table 8
Results of calcination experiments with mixed rare earth carbonates. Results of calcination experiments with pure cerium carbonate.
Temperature (°C) 1100 Temperature (°C) 450 700 1100
Time (h) 1 Time (h) 1
Calcination products (g) 69.1 68.9 Calcination products (g) 58.5 57.0 57.5
Weight loss (wt%) 31.1 31.4 Weight loss (wt%) 41 43 43

Chemical composition of calcination products (wt%) Chemical composition of calcination products (wt%)

REE2O3 90.1 86.1 CeO3 99.3 99.6 100.0

REE 75.1 71.7 Ce 80.9 81.1 81.1
Carbon 0.04 0.02 Carbon 0.15 0.08 < 0.03
Impurities (*) 9.78 13.8 Other elements 0.15 0.12 0.00

Mass ratios (wt%)

La/REE 18.9 19.1 HCl(aq) → HCl(g) (20)

Ce/REE 47.3 49.0
Pr/REE 5.52 5.24 It is possible to see that the Ce4+ ions are reduced by the Cl− ions,
Nd/REE 24.3 22.7 forming Ce3+ ions and liberating gas chlorine (Cl2). The mean REE and
Others rare earth elements/REEs (**) 3.97 3.89 chloride concentration in the rare earth hydrochloric liquor were re-
spectively (159 ± 11) g/L and (110 ± 3) g/L. The mean HCl loss
(*) Main impurity is sulphate (9.05 wt% and 12.3 wt%, respectively)
through vaporization was about 40%. In an industrial scale, this
(**): Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc.
amount of HCl lost must be recovered and returned to the process.
Apart from what was observed in the first experiment, all the rare earth
3.5. Hydrochloric acid leaching experiments
elements were dissolved and the mass ratio Ce/REE in all liquors re-
mained the same as observed in the respective calcination products (see
3.5.1. Calcination products from mixed rare earth oxalates
Table 5).
Table 9 shows the results of the hydrochloric leaching experiments
carried out with the calcination products obtained from mixed rare
earth oxalates calcined at different temperatures and residence times.
3.5.2. Calcination products from pure cerium oxalate
The only experiment in which the calcination product was not to-
Table 10 presents the results of hydrochloric leaching experiments
tally solubilized by a hydrochloric acid solution was the one having a
carried out with the calcination products obtained from pure cerium
high carbon content (6.75 wt%). This occurred due to the incomplete
oxalates in different temperatures and residence time of 1 h.
calcination at a temperature of 450 °C and residence time of 1 h.
The first experiment could not be completed as it foamed heavily
Residual rare earth oxalates do not react with mineral acids such as
due to the presence of rare earth oxy/carbonate in the composition of
nitric, sulfuric and hydrochloric acid (Abrão, 1994).
the respective calcination product. The foam resulted from an in-
Due to the formation of Ce4O7 (49 wt% of Ce2O3 and 51 wt% of
complete calcination of the pure cerium oxalate in a muffle at 450 °C
CeO2), the reactions involved in the dissolution of the calcination
and residence time of 1 h.
products can be explained by Eq. (17) and Eq. (18), whereas the dis-
A low cerium and chloride concentration in the cerium hydrochloric
solution of other rare earth oxides, is represented by Eq. (19). Part of
liquors can be observed, indicating that the cerium was not extracted
HCl in excess is lost through vaporization (Eq. (20)).
from the respective calcination products.
Ce2O3(s) + 6HCl(aq) → 2CeCl3(aq) + 3H2O(l) (17) Apart from the results observed in the first experiment, the differ-
ence in the REE concentration of rare earth hydrochloric liquors
CeO2(s) + 4HCl(aq) → CeCl3(aq) + 1/2Cl2(g) + 2H2O(l) (18)
(4.67 g/L of Ce at 700 °C/1h and 0.44 g/L of Ce at 1100 °C/1h) occured
REE2O3(s) + 6HCl(aq) → 2REECl3(aq) + 3H2O(l) (19) due to the different cerium extractions of the respective calcination
products. Only 4.27% and 0.41% of total mass of cerium fed in the

Fig. 6. XRD patterns of CeO2 A.R. 99.9 wt%, mixed rare earth carbonates and calcination product obtained with mixed rare earth carbonates as precursor at 1100 °C
and residence time of 1 h.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Fig. 7. XRD patterns of CeO2 A.R. 99.9 wt%, pure cerium carbonate and calcination products obtained with pure cerium carbonate as precursor at different
temperatures and residence time of 1 h.

Fig. 8. XRD patterns of CeO2 A.R. 99.9 wt% and calcination products obtained from pure cerium oxalate, pure cerium carbonate, mixed rare earth oxalates and mixed
rare earth carbonates as precursors in muffle at temperature of 1100 °C and residence time of 1 h (30° to 70° 2Theta).

respective calcination products were extracted by the HCl solution. fed in the calcination products, respectively in the first and in the
Additionally, the mean cerium and chloride concentrations in the second experiments, were extracted. A very low mass ratio of Ce/REE
cerium hydrochloric liquor were (2.55 ± 2.99) g/L and can be observed in the liquor (mean value of 6.4 kg/kg) in comparison
(11.1 ± 3.9) g/L. The mean HCl loss by vaporization was about 92%. with the same mass ratio observed in the calcination products (Ce/
As expected, the loss of HCl in these experiments was higher than ones REE ∼ 48 wt/wt) (see Table 7).
verified in the experiments carried out with calcination products from The mean REE and chloride concentrations in the rare earth hy-
the mixed rare earth oxalates. This took place because the only rare drochloric liquor were respectively (58.5 ± 5.9) g/L and
earth element in pure cerium oxalate is cerium, which oxidizes easily to (48.1 ± 10.0) g/L. The mean HCl loss during the experiment was
Ce4+ and becomes insoluble in the HCl solution, remaining HCl free about 64%. As expected, less HCl was lost in these experiments if
(not reacted) in the solution to be vaporized. compared to HCl losses checked in the experiments carried out with
calcination products from mixed rare earth oxalates (40% of HCl losses)
3.5.3. Calcination products from mixed rare earth carbonates and pure cerium oxalate (92% of HCl losses). This occurred because
Table 11 shows the results of the hydrochloric leaching experiments these calcination products contain lower amounts of cerium oxidized
carried out with the calcination products obtained from mixed rare (Ce4+) than the calcinations product obtained from the pure cerium
earth carbonates at temperature of 1100 °C and residence time of 1 h. oxalate, whereas assaying more cerium oxidized than the calcination
In both experiments, the calcination products were not fully solu- products generated when the precursor was the mixed rare earth ox-
bilized by the hydrochloric acid solution and only 9% and 4% of cerium alates.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Table 9
Results of hydrochloric leaching experiments carried out with calcination products obtained from mixed rare earth oxalates in different temperatures and residence
times.
Temperature of calcination (°C) 450 700 1100
Residence time of calcination (h) 1 4 1 4 1 4
Calcination product mass (g) 67.4 50.3 50.3 47.9 47.9 47.8
REE content in calcination product (wt%) 55.7 75.7 78.9 81.0 81.4 81.7
HCl 37 wt% mass (g) 202.18 150.84 150.84 143.62 163.06 143.20
Dilution water mass (g) 145.00 110.00 155.00 145.00 137.00 135.00
Washing water mass (g) 225.00 44.97 55.79 37.50 55.78 34.95
Dry cake mass (g) 39.87 0 0 0 0 0
REE content in dry cake (wt%) 44.24 – – – – –
Rare earth hydrochloric liquor mass (g) 556.36 338.73 403.24 367.51 383.26 344.93
Rare earth hydrochloric liquor density at 20 °C (g/cm3) 1.080 1.235 1.233 1.242 1.234 1.256
REE concentration in rare earth hydrochloric liquor (g/L) 38.31 139.05 145.49 157.32 151.42 166.85
Chloride concentration in rare earth hydrochloric liquor (g/L) 50.65 108.96 108.75 109.71 105.66 115.04

Chemical composition of rare earth hydrochloric liquor (g/L)

La 6.55 25.3 26.7 28.9 27.6 30.3

Ce 21.2 70.2 74.4 80.5 75.7 84.5
Pr 1.53 8.27 8.59 9.27 9.27 9.89
Nd 7.80 28.9 29.7 32.2 32.3 34.8
Other rare earth elements 1.26 6.45 6.12 6.62 6.38 7.03

Mass ratios in the rare earth hydrochloric liquor (wt/wt)

La/REE 17.1 18.2 18.4 18.3 18.4 18.2

Ce/REE 55.3 50.5 51.1 51.1 50.4 50.9
Pr/REE 4.00 5.95 5.91 5.89 5.98 5.93
Nd/REE 20.4 20.8 20.4 20.5 21.1 20.8

Table 10 Table 11
Results of hydrochloric leaching experiments carried out with calcination Results of hydrochloric leaching experiments carried out with calcination
products obtained from pure cerium oxalate in different temperatures and re- products obtained from mixed rare earth carbonates at temperatures of 1100 °C
sidence time of 1 h. and residence time of 1 h.
Temperature of calcination (°C) 450 700 1100 Temperature of calcination (°C) 1100
Residence time of calcination (h) 1 Residence time of calcination (h) 1
Calcination product mass (g) 61.85 53.92 52.17 Calcination product mass (g) 69.05 50.00
Ce content in calcination product (wt%) 67.30 80.69 81.24 REE content in calcination product (wt%) 75.07 71.74
HCl 37 wt% mass (g) 185.59 161.77 156.99 HCl 37 wt% mass (g) 205.82 150.00
Dilution water mass (g) 30.44 67.00 55.00 Dilution water mass (g) 163.77 180.00
Washing water mass (g) – 189.57 198.45 Washing water mass (g) 217.37 165.25
Dry cake mass (g) – 51.50 51.85 Dry cake mass (g) 23.50 33.00
Ce content in dry cake (wt%) – 80.91 81.42 REE content in dry cake (wt%) 98.9 99.2
Cerium hydrochloric liquor mass (g) – 415.08 394.73 Rare earth hydrochloric liquor mass (g) 597.64 445.07
Cerium hydrochloric liquor density at 20 °C (g/cm3) – 1.042 1.010 Rare earth hydrochloric liquor density at 20 °C (g/cm3) 1.123 1.074
Ce concentration in cerium hydrochloric liquor (g/L) – 4.67 0.44 REE concentration in rare earth hydrochloric liquor (g/L) 62.67 54.40
Chloride concentration in cerium hydrochloric liquor – 13.76 8.27 Chloride concentration in rare earth hydrochloric liquor (g/L) 55.25 41.17
(g/L)
Chemical composition of rare earth hydrochloric liquor (g/L)

La 37.2 29.9
3.5.4. Calcination products from pure cerium carbonate Ce 5.45 2.23
Table 12 shows the results of hydrochloric leaching experiments Pr 4.74 4.71
carried out with the calcination products obtained from pure cerium Nd 12.2 13.6
Other rare earth elements 3.14 3.98
carbonates in different temperatures and residence time of 1 h.
A decrease in the cerium and chloride concentrations in the cerium Mass ratios in the rare earth hydrochloric liquor (wt%)

hydrochloric liquors is noticeable when there was an increase in tem- La/REE 59.5 54.9
perature in the calcination experiments. Ce/REE 8.69 4.10
The difference in the cerium concentration in the cerium hydro- Pr/REE 7.56 8.66
chloric liquors (from 57.3 g/L of Ce at 450 °C/1h to 0.91 g/L of Ce at Nd/REE 19.5 25.0
1100 °C/1 h) occured due to the different cerium extractions presented
by the respective calcination products. The extraction was respectively
calcination products having the pure cerium oxalate a precursor (92%
45.7%, 18.1%, and 0.92% of cerium in the first (450 °C/1 h), second
of HCl losses), however more HCl was expected to be lost if compared
(700 °C/1 h) and third (1100 °C/1 h) experiments. These results show
with the results of experiments carried out with calcination products
that a temperature of 1100 °C and a residence time of 1 h in a muffle
having the mixed rare earth oxalates (40% of HCl losses) or carbonates
was capable of transfering 99% of the cerium fed into the calcination
(64% of HCl losses) as precursors.
product.
Additionally, the HCl losses were 43 wt% in first, 77 wt% in the
second and 98 wt% in the third experiment, which is feasible since the 3.5.5. Results comparison
HCl did not react with cerium is lost by vaporization. Fig. 9 consolidates all results obtained in the hydrochloric leaching
The same amount of HCl was expected to be lost in these experi- experiments with mixed rare earth oxalates, pure cerium oxalate, mixed
ments, in comparison with the results of experiments carried out with rare earth carbonates and pure cerium carbonate.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Table 12 3.6. Designed process route

Results of hydrochloric leaching experiments carried out with calcination
products obtained from pure cerium carbonate in different temperatures and Fig. 10 shows a block diagram with a mass balance of the amount of
residence time of 1 h. REE2O3 in each step for a proposed process route for a selective removal
Temperature of calcination (°C) 450 700 1100 of cerium from the rare earth ore and also the production of high purity
Residence time of calcination (h) 1 1 1 cerium oxide (CeO2·xH2O) and mixed rare earth carbonates assigning
Calcination product mass (g) 58.54 57.01 57.50 low cerium content (REE2(CO3)3·xH2O). Another option is to feed the
Ce content in calcination product (wt%) 80.89 81.08 81.10
poor cerium hydrochloric liquor in a solvent extraction (SX) unit to
HCl 37 wt% mass (g) 175.62 171.04 172.50
Dilution water mass (g) 72.00 83.00 50.00 separate individually the rare earth elements.
Washing water mass (g) 171.11 229.95 239.25 The process route proposed comprises the following steps: (I) rare
Dry cake mass (g) 31.50 46.31 55.00 earth ore beneficiation (Testa et al., 2016), (II) rare earth extraction
Ce content in dry cake (wt%) 81.4 81.4 81.4
that encompasses sulphation, pyrolysis, cooling and water leaching
Cerium hydrochloric liquor mass (g) 412.86 464.45 458.99
Cerium hydrochloric liquor density at 20 °C (g/cm3) 1.096 1.036 1.009 (Berni et al., 2013; Teixeira and Silva, 2015; Silva et al., 2018a; Teixeira
Ce concentration in cerium hydrochloric liquor (g/L) 57.27 18.59 0.91 et al., 2019), (III) purification rare earth sulphate liquor in two con-
Chloride concentration in cerium hydrochloric liquor 95.98 31.85 2.39 secutive steps, first with limestone with up pH up to 3.5 and second
(g/L) with lime with pH up to pH 5.0 (Silva et al., 2012; Fernando et al.,
2018; Silva et al., 2018a; Silva et al., 2018b; Silva et al., 2019a), (IV)
REE precipitation as mixed rare earth oxalates, (V) calcined to obtain
The highest cerium extractions and cerium and chloride con-
the mixed rare earth oxides (REE2O3) and cerium as Ce4O7 (soluble in
centrations in the hydrochloric liquors and also the lowest HCl losses
HCl 37 wt% solution), (VI) hydrochloric acid leaching as to dissolve all
were observed in the experiments carried out with calcination products
rare earth elements, including cerium, (VII) REE precipitation as mixed
obtained when mixed rare earth oxalates were used as precursor. On
rare earth carbonates, (VIII) calcination in order to produce the mixed
the other hand, the lowest cerium extractions and cerium and chloride
rare earth oxides and cerium as Ce0.60Nd0.40O1.80 (insoluble in HCl
concentration in the hydrochloric liquors were noticed in the experi-
37 wt% solution), (IX) hydrochloric acid leaching to dissolve others rare
ments done with calcination products generated with pure cerium ox-
earth elements, with the exception of cerium, (X) filtration to separate
alate, mixed rare earth carbonates and pure cerium carbonate. The
CeO2·xH2O from poor cerium hydrochloric liquor and finally (XI) REE
highest HCl losses occurred in the experiments using pure cerium ox-
precipitation as mixed rare earth carbonates with a low cerium content.
alate and pure cerium carbonate as precursors, whereas intermediate
All the REE2O3 content was expressed in dry basis. For a production
HCl losses were observed in the experiments with mixed rare earth
of 1000 kg REE2O3, being 491 kg of REE2O3 as cerium oxides (95 wt%
carbonates.
of CeO2·xH2O + 5 wt% of other rare earth oxides) and 509 kg as mixed

100% 180
Ce concentration in hydrochloric liquor (g/L)

150
80%

120
Ce extraction

60%
90
40%
60

20% 30

0% 0
450ºC/4h 700ºC/1h 700ºC/4h 1,100ºC/1h 1,100ºC/4h 450ºC/4h 700ºC/1h 700ºC/4h 1,100ºC/1h 1,100ºC/4h
Calcination condition in muffle Calcination condition in muffle
Mixed rare earth oxalates Pure cerium oxalate Mixed rare earth oxalates Pure cerium oxalate
Mixed rare earth carbonates Pure cerium carbonate Mixed rare earth carbonates Pure cerium carbonate

(a) (b)
140 100%
Cl concentration in hydrochloric liquor (g/L)

120
80%
100
HCl losses (%)

80 60%

60
40%

40
20%
20

0 0%
450ºC/4h 700ºC/1h 700ºC/4h 1,100ºC/1h 1,100ºC/4h 450ºC/4h 700ºC/1h 700ºC/4h 1,100ºC/1h 1,100ºC/4h
Calcination condition in muffle
Calcination condition in muffle
Mixed rare earth oxalates Pure cerium oxalate Mixed rare earth oxalates Pure cerium oxalate
Mixed rare earth carbonates Pure cerium carbonate Mixed rare earth carbonates Pure cerium carbonate
(c) (d)

Fig. 9. Consolidation of all results obtained in hydrochloric leaching experiments with mixed rare earth oxalates, pure cerium oxalate, mixed rare earth carbonates
and pure cerium carbonate.

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

Rare earth ore

1934 kg REE 2O3

Water I Beneficiation Residue I to be disposed (>74 µm)

1341 kg REE 2O3 Beneficiated rare earth ore (<74 µm)

Sulphation/Pyrolysis/
Sulphuric acid 98% w/w Gases I to be treated
Cooling

Sulphated rare earth ore

Water II Leaching I Residue II to be disposed

1073 kg REE 2O3 Non-purified rare earth sulphate liquor

Purification I
Limestone pulp Residue III to be disposed
pH 3.5

1042 kg REE 2O3 Partially purified rare earth sulphate liquor

Purification II
Lime pulp Residue IV to be disposed
pH 5.0

1000 kg REE 2O3 Purified rare earth sulphate liquor

Oxalic acid solution REE precipitation I Effluent liquid I to be treated

Mixed rare earth oxalates (REE2(C2O4)3.xH2O) NaOH

solution
Calcination I Gases II to be treated

Mixed rare earth oxides (REE2O3) Clean

Cl2 gas Cl2
Ce as Ce4O7 Gas (Cl2 and HCl) gas I
recovery
HCl
Hydrochloric acid solution Leaching II
recovery I
Water III
HCl solution
Rare earth hydrochloric liquor
Effluent liquid II to be treated
Sodium carbonate solution I REE precipitation II Effluent liquid III to be treated

1000 kg REE 2O3 Mixed rare earth carbonates (REE2(CO3)3.xH2O)

Calcination II Gases III to be treated

Mixed rare earth oxides (REE2O3)

Ce as Ce0.60Nd0.40O1.80
Gas (CO2 and HCl) Clean gas II
HCl
Hydrochloric acid solution Leaching III
recovery II
Water IV
HCl solution
Poor cerium hydrochloric liquor + CeO 2.xH2O solid 1000 kg REE 2O3

Reagents Cerium oxide

Water V Filtration Drying 491 kg REE 2O3
CeO2.xH2O
Effluent or Poor cerium hydrochloric liquor
liquid IV to SX
be treated or
Sodium
LaCl 3 carbonate REE precipitation III Effluent liquid V to be treated
solution II
NdCl3 ...... 509 kg REE 2O3

Mixed rare earth carbonates with a low Ce

PrCl3
LuCl 3 content (REE2(CO3)3.xH2O)

Fig. 10. Block of diagram with a mass balance to REE2O3 for a proposed process route to remove cerium selectively from rare earth ore and to produce high purity
cerium oxide and mixed rare earth carbonates with a low cerium content.

rare earth carbonates with a low Ce content, the outcome was 1934 kg REE2O3. According to Testa et al., 2016, it seems to be consistent be-
of REE2O3 in the rare earth ore (3.09 wt% of REE2O3). About 1341 kg of cause 70.0% of the feed mass is rejected and the loss is only 30.7% of
REE2O3 was in the beneficiated rare earth ore (7.11 wt% of REE2O3), the REE2O3 fed in the rare earth ore using a single beneficiation process
1073 kg of REE2O3 in the non-purified rare earth sulphate liquor route encompassing scrubbing, screening, crushing, milling, disliming
(5.22 g/L of REE2O3), 1042 kg of REE2O3 in the partially purified rare with cyclones, filtration and drying. Additionally, 80% of REE2O3 was
earth sulphate liquor (5.07 g/L of REE2O3) and 1000 kg of REE2O3 in attained in the extraction step (sulphation/pyrolysis/cooling and water
the partially purified rare earth sulphate liquor (4.87 g/L of REE2O3). leaching) and of 93.2% was recovered in the purification steps (being
A REE2O3 recovery of 69.3% and a mass recovery of 30 wt% was 97.1% with limestone and 96.0% with lime). No REE2O3 losses oc-
assumed in the beneficiation step, which means that for a feed of curred in the steps: REE precipitation, calcination and hydrochloric
1000 kg of rare earth ore containing 30.9 kg of REE2O3, the yield was of leaching. Therefore, the total REE2O3 recovery was 51.7%
300 kg of beneficiated rare earth ore (< 74 µm) containing 21.4 kg of (51.7% = (1000/1934 × 100) or 51.7% = (69.3% × 80.0% × 93.2%).

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R.G. Silva, et al. Minerals Engineering 139 (2019) 105865

The mass ratio CeO2/REE2O3 in the purified rare earth sulphate li- 5. Ackowledgements
quor was 49.5 wt%, amounting to 495 kg of CeO2 in the liquor
(49.5% × 1000 kg of REE2O3). It was considered that the recovery was The authors would like to thank Vale S.A. especially Patrice
94% of cerium from this liquor and 5% of other rare earth elements Mazzoni, Cássia Souza and Keila Gonçalves for authorizing the pub-
(except cerium) coprecipitating together with cerium, which results in lication of this work. The authors are also thankful to technicians at
the recovery of 465 kg of CeO2 and 26 kg of other rare earth elements, Vale Mineral Development Centre, especially to Wagner Soares, Daiene
totalling 491 kg of REE2O3 in the cerium oxide (CeO2·xH2O). Santos, Márcio Jacob and Kelly Fonseca, who were dutifully engaged in
The remaining REE2O3, amounting to 509 kg, in the hydrochloric this study. We would also like to thank Ricardo Terra and Julius
liquor, can be precipitated as mixed rare earth carbonates Martins for proofreading the paper. Éder Oliveira and Carlos Morais
(REE2(CO3)3·1.4H2O), when Na2CO3 is used as a reagent. The product acknowledge the support from CNPq (Conselho Nacional de
obtained had a REE2O3 content assigning 58.0 wt% and 99.9% of Desenvolvimento Científico e Tecnológico, Brazil), CAPES
purity. The REE2(CO3)3·1.4H2O will be of high purity and could feed (Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Brazil)
the downstream steps, such as hydrochloric acid leaching and solvent and FAPEMIG (Fundação de Amparo à Pesquisa de Minas Gerais,
extraction (SX) or ion exchange (IX), to separate each REE individually. Brazil).
In order to recover chlorine in the gas generated in the hydrochloric
leaching of mixed rare earth oxides, having as precursor the mixed References
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