Extraction of Cerium, Lanthanum,

and Neodymium from Alluvial Gold

Mining Waste from the Bagre-Nechí
Mining District in Colombia

Luver Echeverry-Vargas, Néstor Ricardo Rojas-Reyes,

and Luz Marina Ocampo-Carmona

Abstract The objective of this paper was to evaluate the extraction of cerium,
lanthanum, and neodymium by exploring different leaching conditions with
hydrochloric acid and sulfuric acid from a dephosphorized monazite concentrate
obtained from alluvial gold mining waste from the Bagre-Nechí mining district in
Colombia. The highest element extraction yields are achieved with H2SO4 as the
leaching medium versus HCl at all evaluated concentration, time, and temperature
conditions. The addition of 10% (v/v) H2O2 was found to increase rare-earth disso-
lution up to 93% in the H2SO4 medium. Thermodynamic analysis indicates that
H2SO4 solutions show a higher capacity to solubilize REEs as opposed to HCl
solutions, thus supporting the experimental results.

Keywords Rare-earth elements · Monazite · Hydrometallurgy · Mining waste

Introduction

Rare-earth elements (REEs) are a group of chemical elements comprising all

lanthanides, yttrium, and scandium. They are often divided into two categories: light
rare-earth elements (LREEs), comprising La, Ce, Nd, and Pr, and heavy rare-earth
elements (HREEs), ranging from Sm to Lu, Sc, and Y [1]. Due to their particular
spectroscopic and magnetic properties, REEs play a significant role in the global
economy because of their importance in numerous fields of advanced materials
science; therefore, the industrial demand for them has increased significantly [2].

L. Echeverry-Vargas (B) · L. M. Ocampo-Carmona

Departamento de Materiales y Minerales, Universidad Nacional de Colombia, Calle 75 N. 79 A,
050034 Sede Medellín, Colombia
e-mail: ljecheverryv@unal.edu.co
L. M. Ocampo-Carmona
e-mail: lmocampo@unal.edu.co
L. Echeverry-Vargas · N. R. Rojas-Reyes
Instituto de Minerales CIMEX, Universidad Nacional de Colombia, Calle 75 N. 79 A, 050034
Sede Medellín, Colombia
e-mail: nrrojasr@unal.edu.co

© The Minerals, Metals & Materials Society 2022 17

T. Ouchi et al. (eds), Rare Metal Technology 2022, The Minerals, Metals
& Materials Series, https://doi.org/10.1007/978-3-030-92662-5_2
18 L. Echeverry-Vargas et al.

In nature, REEs do not occur in their elemental state or as individual rare-earth

compounds. REEs dispersed in the earth’s crust occur as mixtures in many rock
formations such as basalts, granites, gneiss, shales, and silicate rocks [3]. Their strong
affinity for oxygen causes them to be found mainly as trivalent cations in carbonates,
oxides, phosphates, and silicates [4]. Approximately 95% of all the world’s rare-earth
resources occur in only three minerals: monazite ((Ce, La, Nd) PO4 ), bastnasite ((Ce,
La, Y) CO3 F), and xenotime ((Y, Yb) PO4 ). Therefore, these minerals are the main
sources for REE extraction [5]. In monazite, the rare-earth oxide (REO) content
ranges from 35 to 71%, while in xenotime and bastnasite it ranges from 52 to 54%
and from 70 to 74%, respectively [6–8].
Research conducted in the region of the Bagre-Nechí mining district in Colombia
indicates that this alluvial gold deposit contains mineral resources with the poten-
tial to be used to obtain REEs in the tailings of mining operations [9, 10]. The
sustainability issue associated with mining activities in this area poses responsibility
challenges to the mining areas, which should be geared towards the establishment of
new technologies and processes that enable the recovery of resources from the waste
produced, particularly the recovery of the monazite present in mining waste, in order
to obtain REEs. In this regard, detailed studies of REE recovery from mine tailings
produced at this site are needed. Although the REE content in tailings may be lower
than in primary sources, their processing can be justified if environmental benefits
are considered, e.g., mine site remediation and soil restoration. In addition, tailing
mining does not rely on an effective collection, transportation, and sorting scheme;
recyclable material is simply available on-site [11].
The objective of this paper is to study different conditions of REE dissolution with
HCl and H2 SO4 from a dephosphorized rare-earth concentrate obtained from alluvial
gold mining waste from the Bagre-Nechí mining district in Colombia. The leaching
conditions evaluated include acid concentration, process temperature, treatment time,
and the effect of hydrogen peroxide on REE recovery. In addition, a thermodynamic
analysis of the products formed in the leaching process was carried out by drawing
species distribution diagrams.

Materials and Methods

Materials

In this paper, a dephosphorized rare-earth concentrate previously obtained by physi-

cally concentrating monazite from residual sands from alluvial gold mining was used
as raw material. The monazite concentrate was subjected to an alkaline dephospho-
rization process followed by water rinsing, filtering, and drying. The reagents used
in this work were analytical grade and their solutions were prepared with distilled
water.
Extraction of Cerium, Lanthanum, and Neodymium … 19

Table 1 Evaluated leaching conditions

Variable Condition
Acid concentration, M 0.5 1 2 3 4
Time, min 15 30 60 90 120
Temperature, °C 30 40 50 60 70 80

Leaching Tests

The rare-earth concentrate was subjected to leaching processes in HCl and H2 SO4
solutions at different concentrations, temperatures, and treatment times, as shown in
Table 1, in order to evaluate the effect of these variables on the leaching yield of rare-
earth elements. The leachates were conducted in a three-hole Pyrex reactor equipped
with a reflux condenser, constant agitation was maintained using a mechanical stirrer,
and the slurry density was kept constant at 30 g/L. In all experiments, undissolved
impurities remained as residue. Lanthanum, cerium, and neodymium contents present
in the acid leach solutions were analyzed using a PerkinElmer Optima 8300 model
ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometer).

Results and Discussion

Effect of Acid Concentration

The effect of HCl and H2 SO4 concentration within the 0.5–4.0 M range on the
extraction of La, Ce, and Nd was studied. Temperature was kept constant at 80 °C,
leaching time at 90 min, and slurry density at 30 g/L, as shown in Fig. 1a, b. From
these figures, it can be noted that increasing the concentration of HCl and H2 SO4
enhances the elements’ extraction efficiency, suggesting that acid is the limiting
reagent in the leaching reaction. When the concentration of HCl changes from 0.5
to 4.0 M, the extraction of Ce increases from 1.5 to 30.4%, that of Nd from 23.3 to
48.1%, and that of La from 55.6 to 77.5%. On the other hand, when the concentration
of H2 SO4 is changed from 0.5 to 4.0 M, the extraction efficiency of Ce increases
from 8.5 to 80.4%, that of Nd from 26.3 to 83.6%, and that of La rises from 62.3 to
91.2%. In all cases, it is evident that the extraction efficiency of La, Ce, and Nd is
higher in H2 SO4 than in HCl, and the extraction of La is higher, followed by that of
Nd, with Ce in the last place.
The lower extraction yield for cerium is possibly due to the fact that Ce is oxidized
from its trivalent to a tetravalent state (Ce3+ to Ce4+ ) during the roasting process and
exists as CeO2 [12]. In this case, CeO2 is poorly soluble at low concentrations of
HCl and H2 SO4 (0.5 M); a higher oxidation state in Ce favors the dissolution of La
and Nd [13]. The results indicate that the oxidation capacity of CeO2 improves with
20 L. Echeverry-Vargas et al.

(a) (b)

Fig. 1 Effect of a HCl and b H2 SO4 concentration on leaching of La, Nd, and Ce from treated
monazite

the increase of hydrogen ion concentration due to the increase in acid concentration.
This leads to the formation of soluble compounds.

Effect of Temperature

In general, the dissolution of any metallic element is affected by the leaching temper-
ature because the dissolution reaction is an endothermic process [14]. In this paper,
experiments were conducted to evaluate the leaching behavior of La, Ce, and Nd
in HCl and H2 SO4 in a temperature range from 30 to 80 °C, keeping the leaching
time constant at 90 min, the concentration of HCl and H2 SO4 at 2.0 M, and the
slurry density at 30 g/L. As seen in Fig. 2a, b, the extraction efficiency of La, Ce,
and Nd increases when the leaching temperature is raised. The results indicate that
increasing the temperature from 30 to 80 °C in HCl leaching increases Ce extrac-
tion efficiency from 1.0 to 9.3%, Nd extraction increases from 22.4 to 35.6%, and
that of La increases from 51.2 to 73.2%. When the same evaluation is performed in
H2 SO4 leaching, it is observed that Ce extraction increases from 5.2 to 34.3%, Nd
extraction efficiency increases from 22.7 to 61.1%, and that of La increases from
49.8 to 85.1%. The results show that, in all cases, the extraction of La, Ce, and Nd
has a higher efficiency in sulfuric acid than in hydrochloric acid. Furthermore, in all
scenarios, the order of extraction is Ce < Nd < La.
Extraction of Cerium, Lanthanum, and Neodymium … 21

(a) (b)

Fig. 2 Effect of temperature on leaching of La, Nd, and Ce from treated monazite with a HCl and
b H2 SO4

Effect of Time

In this paper, the effect of leaching time on the recovery of La, Ce, and Nd was
evaluated, varying the time between 15 and 120 min. The concentration of HCl and
H2 SO4 was kept constant at 2.0 M, the leaching temperature at 80 °C, and the slurry
density at 30 g/L. Figure 3a, b shows that increasing the leaching time in aqueous
HCl solution increases the extraction of Ce (from 5.1 to 10.4%), Nd (from 28.1
to 37.3%), and La (from 59.8 to 75.4%), while increasing the leaching time in the

(a) (b)

Fig. 3 Effect of leaching time on dissolution of La, Nd, and Ce from treated monazite with a HCl
and b H2 SO4
22 L. Echeverry-Vargas et al.

(a) (b)

Fig. 4 Effect of hydrogen peroxide on leaching of La, Nd, and Ce from treated monazite with a
HCl and b H2 SO4

H2 SO4 medium increases the recovery of Ce (from 26.3 to 49.4%), Nd (from 44.3 to
65.2%), and La (from 72.5 to 90.4%). Leaching times longer than 120 min in HCl and
H2 SO4 solutions had no significant effect on these elements’ extraction efficiency.

Effect of the Addition of Hydrogen Peroxide (H2 O2 )

Hydrogen peroxide (H2 O2 ) is widely used in hydrometallurgical processes due to

its oxidizing characteristics [15–18]. In addition, it is considered one of the cleanest
and most versatile chemicals, and is widely used in the industry [19, 20]. In acidic
solutions, H2 O2 is one of the strongest oxidants known. The oxidizing capacity of
hydrogen peroxide is so strong that it is considered a highly reactive oxygen species
[21].
The effect of H2 O2 concentration on the extraction of La, Ce, and Nd was inves-
tigated by keeping the hydrogen peroxide ratio at 10% (v/v) in solution, the HCl
and H2 SO4 concentration at 2.0 M, the leaching temperature at 80 °C, and the slurry
density at 30 g/L. The results are presented in Fig. 4, b. The extraction of these
elements in HCl solution yields a Ce recovery of 48.7%, Nd recovery of 65.8%, and
La recovery of 86.9%. When the action of hydrogen peroxide was evaluated in an
aqueous H2 SO4 solution, a Ce extraction efficiency of 92.6% was found, as well as
90.6% for Nd and 95.8% for La.

Thermodynamic Analysis for LREE Leaching

The monazite used in this study was subjected to a roasting process in condi-
tions where it eliminated phosphate; therefore, when performing the thermodynamic
analysis, PO4 3− was excluded from the system. The LREEs present in the treated
Extraction of Cerium, Lanthanum, and Neodymium … 23

monazite, such as lanthanum, cerium, and neodymium in their oxidation state, exhibit
a strong tendency to form complex ions with strong acids such as HCl and H2 SO4 ,
as reported in several papers [22–24]. The results indicate that, under the leaching
conditions evaluated, the order of extraction of the elements of interest is as follows:
Ce < Nd < La. It can also be seen that higher extractions of these elements are achieved
with H2 SO4 as opposed to HCl. To further investigate the leaching reactions of these
elements in the dephosphorized monazite product, distribution diagrams of La, Ce,
and Nd in HCl and H2 SO4 were plotted, as shown in Figs. 5 and 6, respectively.
The diagrams for these systems were made using MEDUSA® software and supple-
mented with the Hydra database, using the values of the critical stability constants
reported in the NIST database.
The species distribution diagrams for La3+ , Ce3+ , and Nd3+ ions—the concen-
trations of these species were calculated from the chemical assay—in 2.0 M
hydrochloric acid aqueous solution—characteristic concentration of the leaching
experiments carried out in this work—are shown in Fig. 5. In this system, Ce is
leached in its trivalent form (Ce3+ ) and subsequently forms two soluble complexes
with the chloride ion (CeCl2+ and CeCl2 + ) at pH values below 4.0. A similar result
occurs for La and Nd, where these species leach in their trivalent form (La3+ and
Nd3+ ) and then form species with Cl− (LaCl2+ , LaCl2 + , NdCl2 + and NdCl2+ ) at
pH values below 8.0 for lanthanum and 7.0 for neodymium.
According to the species formation diagrams, the leaching capacity of Ce is
comparatively higher than that of La and Nd at pH < 4. Under these conditions,
cerium is found mostly as CeCl2 + . However, experimental data indicate that the

Fig. 5 Distribution diagrams of species for Ce3+ , La3+ , and Nd3+ as a function of pH in the Cl−
system at 25 °C with the following concentrations: 2.0 M Cl− , 0.01 M La3+ , 0.007 M Ce3+ , and
0.008 M Nd3+
24 L. Echeverry-Vargas et al.

Fig. 6 Distribution diagrams of species for La3+ , Ce3+ , and Nd3+ as a function of pH in the SO4 2−
system at 25 °C with the following concentrations: 2.0 M SO4 2− , 0.02 M La3+ , 0.02 M Ce3+ , and
0.01 M Nd3+

recovery of Ce is lower than that of the other elements. As noted above, the possible
reason for cerium’s low leachability is that it is oxidized to its tetravalent state (Ce4+ )
by roasting, forming cerium dioxide (CeO2 ), which is poorly soluble.
Figure 6 corresponds to the species distribution diagrams for the La-SO4 -H2 O,
Nd-SO4 -H2 O, and Ce-SO4 -H2 O systems for 2.0 M sulfuric acid concentration. The
concentration of the elements of interest was determined by chemical assays. These
diagrams show that lanthanum tends to form LaSO4 + and La(SO4)2 − complexes
at pH < 9. Neodymium forms NdSO4 + and Nd(SO4)2 − complexes up to pH 8. In
the case of cerium, CeSO4 + and Ce(SO4)2 − complexes are formed at pH < 5. As
mentioned above, Ce forms cerium dioxide (CeO2 ) due to the conditions to which
the monazite was subjected, resulting in the low solubility of cerium, which is the
reason for this element to have the lowest extraction yields and for the impossibility
to contrast the results with the leaching capacity indicated in the species distribution
diagrams.

Conclusions

• A higher extraction yield of the elements Ce, La, and Nd was achieved with sulfuric
acid as a leaching medium versus hydrochloric acid in all evaluated concentration,
time, and temperature conditions.
Extraction of Cerium, Lanthanum, and Neodymium … 25

• In all leaching scenarios evaluated, the order of extraction was Ce < Nd < La.
• The addition of 10% (v/v) hydrogen peroxide increases the dissolution of rare
earths up to 93% in the H2 SO4 medium.
• The thermodynamic analysis indicates that H2 SO4 solutions exhibit a higher
capacity to solubilize REEs as compared to HCl solutions, thus supporting the
experimental results.
• Due to the dephosphorization conditions of monazite, Ce formed cerium dioxide
(CeO2 ), which is poorly soluble and, therefore, makes it impossible to contrast the
extraction of Ce with the information provided by the species formation diagrams.

Acknowledgements The authors wish to thank the Colombian Ministry of Science for the financial
support granted to the Project “Recovery of rare earth elements from minerals present in black sands,
residue from alluvial gold mining in El Bagre-Antioquia,” code 110180863804 within Call for
Projects 808 of 2018 - CFP for Science, Technology and Innovation projects and their contribution
to the country’s challenges. And to the company Mineros Aluvial S.A.S BIC for the donation of
the residual sands from alluvial gold mining.

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