Sulfuric Acid Leaching of Heavy Rare Earth Elements (HREEs) from Indonesian Zircon Tailing
Corresponding email: bayupetrus@ugm.ac.id
Published at : 16 Oct 2020
Volume : IJtech
Vol 11, No 4 (2020)
DOI : https://doi.org/10.14716/ijtech.v11i4.4037
Trisnawati, I., Prameswara, G., Mulyono, P., Prasetya, A., Petrus, H.T.B.M., 2020. Sulfuric Acid Leaching of Heavy Rare Earth Elements (HREEs) from Indonesian Zircon Tailing. International Journal of Technology. Volume 11(4), pp. 804-816
| Iga Trisnawati | 1. Sustainable Mineral Processing Research Group, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No.2, Yogyakarta 55281, Indonesia 2. Center for Acce |
| Gyan Prameswara | Sustainable Mineral Processing Research Group, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No.2, Yogyakarta 55281, Indonesia |
| Panut Mulyono | Sustainable Mineral Processing Research Group, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No.2, Yogyakarta 55281, Indonesia |
| Agus Prasetya | 1. Sustainable Mineral Processing Research Group, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No.2, Yogyakarta 55281, Indonesia 2. Unconventional |
| Himawan Tri Bayu Murti Petrus | 1. Sustainable Mineral Processing Research Group, Department of Chemical Engineering, Faculty of Engineering, Universitas Gadjah Mada, Jl. Grafika No.2, Yogyakarta 55281, Indonesia 2. Unconventional |
Solid pollution has been an issue
in mineral processing for decade. One of these pollutants is zircon sand mining
waste (zircon tailing). Due to the concentration of rare earth minerals in
zircon tailing and the increasing demand of REE in advanced technologies,
studying zircon tailing as a potential source of REE had become an interest for
us. Our experiments consisted of mineral characterization and an alkaline
fusion process, followed by a leaching process. The characterization process
was carried out to obtain actual information from zircon tailing samples. This
process showed total rare earth elements (REEs) content of 58.62%, at 9%, 1%,
1.2%, 1.7%, and 1.5% for Y, Gd, Er, Dy, and Yb, respectively. A sieving process
was carried out since it was known that most heavy rare earth elements (HREEs)
content occurs at a larger size. The alkaline fusion process was applied with
an intent to break the phosphate bonds present in the REE-carrying minerals
(xenotime and monazite) and convert phosphate bonds to hydroxide bonds in rare
earth metals. During the alkaline fusion process, as much as 75%, 66.45%, and
60% of the phosphate, silica, and zirconium, respectively, were reduced. The
leaching process was carried out in a flat-bottom three-neck flask. The optimum
point of leaching experiments occurs at 0.5 M H2SO4,
60°C, and a solid-to-liquid (S/L) ratio of 10 g/100 mL. In these conditions, as
much as 89%, 99%, 94%, 92%, and 90% of Y, Gd, Er, Dy, and Yb, respectively,
were recovered as an HREEs2-(SO4)3 product
solution.
Acid leaching; Alkaline fusion; Rare earth elements; Zircon tailing
The issue of decreasing
environmental quality has been an increasing concern recently (Hudson-Edwards and Dold, 2015; Kusrini et al., 2018a,
2018b; Reichl et al., 2018). All fields are affected by
this problem—the mining sector included, which leaves waste as a result of
mining activities (Durucan et al., 2006; Aznar-Sánchez et al., 2018). This waste has not been
treated to reduce environmental pollution, such as tailings from the zircon
mining in Indonesia. This tailing waste contains several important elements
that are useful for advanced technology and can potentially be extracted from mining waste
treatment. Some of these elements are “heavy rare earth elements” (HREEs) (Harjanto et al.,
2013, Hamzah et al., 2018).
Rare earth elements (REEs) are all elements
in lanthanides, totaling 17 elements, including scandium and yttrium. The REEs
are divided into two groups, based on atomic weight: the light rare earth
elements, which are lanthanum through europium (atomic numbers 57–63), and the
heavy rare earth elements, which are gadolinium through lutetium (atomic
numbers 64–71). Yttrium (atomic number 39), though light, is included among the
heavy REEs group due to its common chemical and physical affiliations with the
heavy REEs in nature (Qi, 2018). These
elements have chemical and physical properties in common, and they are useful
for many advanced technologies, such as superconductors, magnets, and catalysts
(Habashi, 1992; Gupta and Krishnamurthy, 2005;
Kusrini et al., 2018a; Machmudah et al., 2019). Usually, the separation
process cannot be carried out directly to obtain oxides or pure elements from
rare earth minerals due to their similarity (El
Hady et al., 2016; Kusrini et al., 2018b).
The existence of rare earth metals (REMs) is
not as rare as their name suggests. The presence of cerium (Ce), praseodymium
(Pr), samarium (Sm), and Yttrium (Y) is even more extensive than precious
metals (gold [Au], silver [Ag], and platinum [Pt]) in the earth’s crust (Lide, 2004). Even at the end of 2018, rare earth
oxide production reached more than 150,000 metric tons, but its occurrence in
mineable deposits is limited (King, 2013; Haxel et
al., 2014; Gambogi, 2019). Therefore, to meet the increasing global
demand for REMs, efficient extraction technology from secondary sources is
needed.
There are several ways to extract rare earth
metals from their carrier minerals, such as direct leaching using sulfuric acid
at temperatures of 155–230°C, alkali cracking using a sodium hydroxide solution
at 140°C, roasting using sodium carbonate at 900°C, and alkaline fusion using
flakes of sodium hydroxide at 400–500°C. The disadvantages of the above
extraction processes are: (1) for the direct leaching process using sulfuric
acid, the formation of REE double
sulfate cannot be avoided, so it will affect the refining process of REEs, and
during this process, the phosphate that binds to the monazite cannot be
separated immediately; (2) consumption of sodium hydroxide is too high in the
cracking process using sodium hydroxide (REE / NaOH = 1/21); and (3) high
energy requirements are prohibitive in the roasting process using sodium
carbonate (Sadri et al., 2017). Another
process for extracting rare earth elements is the alkaline fusion process. This
process is carried out by reacting rare earth minerals with alkali in order to
get REE-(OH)3, while the phosphate turns into a Na3PO4
byproduct. The two products can be separated by washing them with water.
REE-(OH)3 remains in the solid phase while Na3PO4
dissolves. The alkaline fusion process was chosen for our experiments because
it offers several advantages. The main advantage is that the alkaline fusion
process can break the phosphate bonds in xenotime and monazite and break the
silica matrix to make the leaching process more effective (Biswas et al., 2010; Dai et al., 2014; Tang et al.,
2019). Furthermore, rare earth hydroxide (REE-[OH]3) products
easily occur through this process. Another advantage is that Na3PO4
can be purified as a byproduct. These conditions are needed to enhance the
effectiveness of leaching. The leaching process is performed to dissolve the
rare earth element, which ensues at a pH below 3.5 (Amer
et al., 2013; Kumari et al., 2015).
In
this experiment, HREEs were extracted from Indonesian zircon tailings. The
purpose of this research was to determine the optimum conditions for the
leaching of HREEs from alkaline fusion products (HREEs-[OH]3).
Pretreatment was carried out through an alkaline fusion process to break the
phosphate bonds in HREE (monazite and xenotime) carrier minerals. Then, the
leaching process was carried out using sulfuric acid under various leaching
conditions.
The process of leaching HREEs was investigated through several
parameters, and the optimum conditions were identified. Sample characterization
was carried out through the process of sieving and analyzing the composition of
the sample using XRF. The pretreatment process was carried out to increase the
recovery of HREEs. The pretreatment process includes alkaline fusion and
leaching using deionized water. The alkaline fusion process of tailing zircon
was completed in three hours at a temperature of 450°C and tailings at an NaOH
ratio of 1:1 (wt/wt). In addition, recovery phosphate increased following the
pretreatment processes of alkaline fusion, characterized by a 73.57% reduction
in phosphate binding to HREEs, followed by the leaching process performed to dissolve
HREEs-(OH)3 into a solution of HREEs2-(SO4)3.
The optimum leaching conditions in this experiment occurred at concentrations
of 2 M H2SO4, 60°C, an S/L ratio of 10 g/100 mL, and 150
rpm during 60 minutes. Under these conditions, HREEs were recovered at as much
as 89%, 99%, 94%, 92%, and 90% for Y, Gd, Er, Dy, and Yb, respectively. This
experiment is expected to serve as a treatment solution for tailings from
zircon sand mining activities and as an alternative solution for processing
HREEs from secondary sources.
The
authors are grateful to Universitas Gadjah Mada for supporting this research
and also to PSTA–BATAN, Indonesia, for the analytical instruments used to
complete this study. In addition, one of the authors, Iga Trisnawati, appreciates
financial support from Beasiswa Saintek Kemenristek/BRIN.
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