Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 5300−5308 pubs.acs.org/journal/ascecg

Leaching and Selective Extraction of Indium and Tin from Zinc Flue
Dust Using an Oxalic Acid-Based Deep Eutectic Solvent
Philipp Zürner and Gero Frisch*
Institut für Anorganische Chemie, TU Bergakademie Freiberg, Leipziger Str. 29, 09599 Freiberg, Germany
*
S Supporting Information

ABSTRACT: Deep eutectic solvents have previously been

used as cost-effective and readily available alternatives to
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

conventional ionic liquids. Due to their versatile complexation

properties, they are potential lixiviants for selective metal
processing. In this study, we investigate the leaching behavior
of three choline chloride-based deep eutectic solvents to
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selectively separate indium and tin from an oxide flue dust

material. Ethylene glycol, urea, and oxalic acid dihydrate were
used as hydrogen bond donors in the eutectic mixtures. The
highest leaching yields were observed in the oxalic acid system
Oxaline. A two-step precipitation procedure was developed for
the leachate solution to separate the target metals indium and
tin from the main flue dust components, i.e., iron, zinc, lead,
and copper. This ionometallurgical approach was compared to equivalent leaching experiments using aqueous oxalic acid
solutions and other deep eutectic solvents.
KEYWORDS: Indium, Metallurgical waste, Critical raw material, Recycling, Deep eutectic solvents, Ionic liquids, Oxalic acid

■ INTRODUCTION
Indium and tin are main group elements used for a wide range
of applications in the fields of electronics and optical devices.
Both metals form the well-known and intensively studied
indium tin oxide (ITO), which is used in various thin film
applications due to its optical transparency and electrical
conductivity. Although most indium is used for the production
of ITO, only small amounts of tin are needed for doping.1,2
Tin is mainly used as an alloy constituent in solder, for the
production of chemicals, and for corrosion resistant coatings.3
Tin is readily available, but indium has been listed as a
critical raw material by the European Commission since 2011
due to its supply risk and high economic importance.4 Indium
is primarily produced as a byproduct of pyrometallurgical zinc
production and is hence dependent on zinc demand. The
development of effective recycling strategies and efficient
recovery processes for indium from secondary raw materials
will hence become increasingly important in the near future. A
promising source of indium is pyrometallurgical wastes such as
flue dust from zinc smelters. Previous hydrometallurgical
approaches focused on aqueous acid leaching, cementation, or
electrolytic separation.5−8 A common winning strategy is
leaching of the raw material with sulfuric or hydrochloric acid
and subsequent solvent extraction. However, significant
amounts of iron are often present, which is problematic due
to the inhibiting effect on indium extraction. Iron(III) has to
be chemically removed or reduced using large amounts of
reducing agents. This is cost intensive and produces large
volumes of aqueous waste. After the removal of iron from the
leachate, solvent extraction has successfully been used to
separate indium from the acidic aqueous solutions using
classical extractants in organic solvents9 or ionic liquids
(ILs).10,11 However, conventional ionic liquids can be costly
and difficult to recover.
A more economic approach for the selective extraction of
valuable metals from secondary raw materials could be the
direct digestion of flue dusts in deep eutectic solvents
(DESs).12 These eutectic mixtures of a quaternary ammonium
halide (e.g., choline chloride, ChCl) and a hydrogen bond
donor (HBD), such as urea, ethylene glycol, or carboxylic
acids, showed selective dissolution behavior for various metal
oxides.13−15 Due to their low melting points, DESs can be used
for ionometallurgical processes under mild conditions. Addi-
tionally, they are reported to be readily biodegradable, with
some exceptions depending on the utilized hydrogen bond
donor.16,17 There have been attempts to use eutectic mixtures
of choline chloride with urea and ethylene glycol for processing
of different raw materials, e.g., zinc and lead recovery from
electric arc furnace dust,18−20 extraction of zinc from cupola
furnace dust,21 or ultrasound-assisted copper leaching and
electrodeposition.22 The same DESs have been utilized for
oxidative leaching of sulfidic ores, with the addition of iodine
to separate and electrodeposit noble metals such as silver and
gold.23−25
Received: December 3, 2018
Revised: January 24, 2019
Published: January 25, 2019

© 2019 American Chemical Society 5300 DOI: 10.1021/acssuschemeng.8b06331

ACS Sustainable Chem. Eng. 2019, 7, 5300−5308
ACS Sustainable Chemistry & Engineering
Due to its coordinating properties, oxalic acid is a promising
candidate as a HBD for leaching of oxidic or biological
materials.26 To our knowledge, there has only been limited
research into developing recovery strategies for secondary raw
materials using Oxaline, i.e., a DES made of choline chloride
and oxalic acid.27
In this study, we explore an ionometallurgical approach for
leaching an oxide zinc flue dust with three different DESs to
selectively extract the target metals indium and tin from the
bulk material. Ethaline (ChCl + ethylene glycol, 1:2) and
Reline (ChCl + urea, 1:2) were chosen as the most common
and extensively studied DESs. Oxaline (ChCl + oxalic acid
dihydrate, 1:1) comprises the simplest and cheapest dicarbox-
ylic acid with good metal chelating properties and is therefore
tested as potential lixiviant. Using small-scale lab experiments,
a strategy for the selective separation of the target metals from
the main components of the flue dust matrix, i.e., iron, zinc,
lead, and copper, has been developed. By comparing the results
from the Oxaline system to the corresponding aqueous oxalic
acid system, the potential of this processing method is
evaluated.
■
EXPERIMENTAL PROCEDURES
Choline chloride (≥98.0%) and oxalic acid dihydrate (>99.5%) were
purchased from VWR Chemicals, and ethylene glycol (99%) and urea
(99.5%) were purchased from Grüssing. All chemicals had low trace
metal contents and were used as received without further purification.
The DESs Ethaline and Reline were prepared in sealed glass
containers by mixing choline chloride in a 1:2 molar ratio with
ethylene glycol and urea, respectively. For Oxaline an equimolar ratio
of choline chloride and oxalic acid dihydrate was used. The mixtures
were stored at 50 °C for 24 h and subsequently stirred until a
colorless homogeneous liquid was obtained. To prevent crystallization
of choline chloride, all DESs were stored at 50 °C.
The water content of pure DESs was determined using a
coulometric Karl Fischer titrator C20 (Mettler Toledo). Freshly
prepared Ethaline and Reline were analyzed, and the average water
contents for the different batches were 0.28 ± 0.01% and 0.21 ±
0.03%, respectively. Due to the use of oxalic acid dihydrate, Oxaline
samples had to be diluted with dry methanol (water content: 120 ±
11 mg/kg) prior to titration to ensure samples were within the
specifications of the instrument. The average water content was 14.9
± 0.2% determined from multiple freshly prepared batches.
The processed flue dust was provided by the company “Mineral
Projekt - Gesellschaft fü r Planung und Konstruktion mbH”
(Chemnitz, Germany). The sample originated from a flue dust
dump in Kosovo, and the material was produced during the second
stage of the pyrometallurgical processing of sulfidic ores. Individual
samples of the bulk material where taken from the dump,
accumulated, and sampled according to the procedure guidelines
LAGA PN 98.28 The flue dust was dried and ground with a pestle and
mortar prior to analysis and processing steps.
Analysis of liquid and solid samples were carried out using the
following analytical techniques: XRF, ICP-OES, ICP-MS, XRPD, and
UV−vis. XRF analysis of the flue dust was carried out before the first
and after the last leaching experiment, using a wavelength dispersive
X-ray fluorescence spectrometer (Bruker S8 Tiger) with a rhodium
source. Liquid samples were analyzed using ICP-OES (Thermo
Scientific iCAP 6500 spectrometer) and ICP-MS (Thermo Scientific
XSeries II spectrometer). Solid samples were digested with aqua regia
prior to the measurement. XRPD analyses were carried out using two
powder diffractometers (Bruker D8 Discover and Siemens D5000)
operated with Cu Kα radiation and flat-plate samples. The flue dust
was milled using a planetary ball mill (Retsch PM 100) operated with
a grinding jar of yttrium-stabilized zirconium oxide. Theoretical
powder patterns were calculated from single crystal literature data
using Diamond 4.0 (Crystal Impact). ICSD Collection Codes (Coll
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Code) are listed together with the references in the legends of the
diffractograms. Diffraction patterns were plotted with the square root
of the relative intensity on the vertical axis to emphasize reflections of
minority phases. Absorption spectra were recorded using a high
resolution UV−visible double-beam spectrophotometer (Jasco V-
670).
Leaching experiments were carried out at 50 and 70 °C using a
lixiviant volume of 75 to 200 mL and liquid-to-solid ratios (l/
s) between 10 and 20. Suspensions were stirred in an oven for a
maximum period of 14 days. Samples of 5 to 10 mL were taken after
distinct reaction times, filtered at the corresponding leaching
temperature, and subsequently diluted for ICP-OES analysis using
aqueous HNO3 and HCl solutions. Additionally, samples were diluted
1:10 with deionized water to initiate oxalate precipitation. UV
irradiation of the diluted leachate solutions was carried out using a
125 W high-pressure mercury-vapor lamp (HQV 125, Narva)
emitting at 365 nm. Leaching yields and recovery rates were, unless
stated otherwise, calculated with respect to the total amount of the
respective metal in the dried flue dust. A detailed description of
experimental procedures is given in the Supporting Information (SI).
It was not possible to repeat leaching experiments often enough to
obtain statistically relevant numbers for every single result. Errors of
quantitative metal analysis were hence evaluated as follows. Four
independent Oxaline leaching experiments, carried out under the
same conditions (50 °C, 48 h, 300 rpm), were used for the error
estimation. Cumulative statistical uncertainties were determined for
the single elements and were generally around 5% (Fe: 7%; Zn: 8%;
Pb: 2%; Cu: 6%; In: 6%; Sn: 5%). Additionally, theoretical maximum
errors were calculated by summation of errors of all steps and were
found to be in the same order of magnitude as the statistical errors.
The relative standard deviations of ICP-OES analysis were
significantly lower than these errors and are hence not further
considered. Composition data of the identified solid phases are given
as average values of at least two leaching experiments.
■
RESULTS AND DISCUSSION
Pretreatment and Characterization of the Flue Dust.
Prior to all experiments, 0.3−0.4 kg portions of the flue dust
were dried in an oven at 140 °C for 24 h until the mass
remained constant. On average, this resulted in a mass loss of
22.5%.
Quantitative analysis was carried out using XRF, ICP-OES,
and ICP-MS. XRF results are shown in Table S1. The material
mainly consisted of iron, zinc, and oxygen adding up to 86.6%.
Other components were Pb, Si, Na, S, Mn, Cu, and Al. The
target elements In and Sn were found to be minority
constituents, and these values are associated with a relatively
large experimental error (see Experimental Procedures).
Hence, ICP-OES and ICP-MS analyses were carried out to
confirm the XRF results and to get more accurate
concentrations of the target elements. For both techniques,
concentrations of the main elements were in good agreement
with the XRF data. However, the indium and tin concen-
trations were significantly higher, 284 and 241 mg/kg,
respectively (Table 1). These results were confirmed by later
measurements recorded after the last leaching experiment.
The phase composition was analyzed using XRPD, and the
results are shown in Figure 1.
The main crystalline phase was identified as franklinite, a
zinc ferrite (ZnFe2O4). This explains the high amounts of zinc
and iron in the material. Furthermore, franklinite is known to
substitute Zn or Fe for other elements such as Mn, which is
consistent with the manganese content of 1.6%.29 Other phases
include PbSO4 and Zn2(SiO4). A second zinc-bearing phase
was expected due to the Zn:Fe ratio in the material and is also
consistent with the leaching behavior described below. The
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Table 1. ICP-OES Results of Relevant Metals after
Digestion of Dried Flue Dust Sample with Aqua Regiaa
Element mg/kg
Fe 283,064
Zn 254,157
Pb 29,089
Cu 8054
In 284
Sn 241
a
Given data are average values from independent analyses. The full
list of elements is shown in the Supporting Information (Table S2).
broad reflections at 12.5° and 25.1° are characteristic of
phyllosilicates, e.g., kaolinite,32 but it was not possible to assign
a particular structure.
Regarding the magnetic properties of ferrites, magnetic
separation was attempted to extract the franklinite phase from
the bulk material. However, this was not successful. The
material did show magnetic properties, but no selectivity could
be achieved. Eventually, all material was magnetically removed
from an aqueous flue dust suspension.
Exploratory Leaching Experiments with DESs. Three
deep eutectic solvents, namely Ethaline, Reline, and Oxaline,
were examined as potential leaching agents for the flue dust
and subsequent separation of indium and tin.
To explore the leaching behavior and identify trends in
selectivity, the flue dust was leached in small scale (75 mL)
experiments. A moderate temperature of 50 °C was used to
decrease viscosity but also to avoid solvent decomposition.
Results are compared in Table 2. Cumulative experimental
errors from leaching, dilution, and analysis were estimated to
be around 5% (see Experimental Procedures for details).
Low leaching efficiencies were found for Ethaline and
Reline. Under the given conditions, only lead was dissolved
with higher yields of ca. 40% and 50%, while elements from the
franklinite phase were not significantly leached. Neither indium
nor tin could be detected in the leachate. Zinc was leached
without simultaneous dissolution of iron, which is consistent
with the presence of Zn2(SiO4) as a second zinc-bearing
mineral.
Leaching with Oxaline showed significantly different
leaching behavior. The metal yields were generally above
70%, and due to the high iron and zinc concentrations,
decomposition of the main franklinite phase must be assumed.
After 48 h, the target metals indium and tin were leached with
Figure 1. X-ray diffraction pattern of the dried and milled flue dust. The flat sample was rotated at 15 rpm.29−31
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Table 2. Leaching Yields Using Different DESs at 50 °C for
48 h
Leaching yield (%)
Ethalinea Relinea Oxalineb
Fe <0.1 <0.01 83
Zn 6 14 88
Pb 41 47 93
Cu 3 7 76
In <LODc <LODc 92
Sn 3 2 88
a
Yields calculated from a single experiment. bAverage value of four
independent experiments. cElement concentration below limit of
detection.
yields of 92% and 88%, respectively. As expected, the oxide flue
dust is readily dissolved by the much more acidic DES Oxaline.
Further, oxalate is known to be a good ligand for many di- and
trivalent metal cations. Indium and tin could only be leached
together with large amounts of iron and zinc, suggesting that
both target metals are bound in the franklinite phase, making it
impossible to extract indium and tin selectively during the
leaching step. This is consistent with literature findings, where
tin and indium were successfully substituted in zinc ferrite
crystal structures.33−35
In conclusion, the Oxaline system was the most promising
candidate for target metal extraction. Further experiments
hence focused on Oxaline leaching and comparison to aqueous
analogues. It is important to note that the high concentration
of both oxalic acid and chloride in Oxaline cannot be easily
achieved in aqueous solution.36 The influence of these ligands
on the stability of the relevant metal complexes during the
subsequent separation steps is discussed below.
Oxaline System. Leaching. Due to the favorable proper-
ties of Oxaline and the high leaching yields under mild
conditions, this system was further investigated in lab scale
stirring reactors with respect to leaching time (up to 14 days)
and temperature.
Figure 2 shows the yields and concentrations of the relevant
metals for a typical Oxaline leaching experiment at 50 °C.
As expected, the concentrations of the metals in solution
increased over time, and after 48 h, no further change in
concentration was detected (Figure 2, left). In contrast to the
other metals, lead exhibited very fast leaching kinetics with a
yield above 90% after 1 h (Figure 2, right). This can be
explained by the fast dissolution of the PbSO4 phase in
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Figure 2. Leaching concentrations (left) and yields of the process relevant metals (right) for 48 h leaching experiments of flue dust in Oxaline (V =
200 mL) at 50 °C with a l/s ratio of 10.

Figure 3. Yields of the process relevant metals for 48 h leaching experiments (V = 75 mL) of flue dust in Oxaline at 50 °C (left) and 70 °C (right)
with a l/s ratio of 10.

Oxaline. Data for indium and tin suggest that they dissolve separated using conventional extraction techniques such as
from the same phase, most likely franklinite. The excess of zinc electrowinning or solvent extraction.
compared to iron during the first 8 h of the leaching process Dilution of Leachate: Precipitation of Zn Oxalate Phase.
confirms the existence of another zinc-rich phase that is more Before the first precipitation step, the leachate was filtered
readily dissolved. from residues of the leaching process using pressure filtration
To explore the temperature dependence of the leaching (3 bar Ar) at 50 °C. The filtrate exhibited an intense dark
process, experiments were carried out at 50 and 70 °C green-brown color.
(Figure 3). At temperatures below 50 °C, the viscosity of To initiate precipitation, the Oxaline leachate was diluted
Oxaline severely impeded filtration, and above 80 °C, slow 1:10 with deionized water, and a white precipitate was formed
within 10 min. The solution was stirred for 1 h at room
decomposition of Oxaline was observed. The leaching process
temperature, resulting in a fast settling fine solid and a clear,
was significantly faster at 70 °C; after 8 h, the yields of the
green solution (Figure 4). The solid was filtered, washed with
observed metals were already above 80%, reaching 90 to 100%
after 24 h. For lead, which already exhibited very fast
dissolution kinetics at lower temperatures, the temperature
dependence was less significant. At 50 °C, iron and zinc were
not yet fully dissolved when the indium yield was already close
to 100%. While high yields could be achieved for the target
metals, selectivity was generally poor. Therefore, a further
separation strategy had to be applied to the leachate, which is
discussed in the following sections.
Separation of the main flue dust components from the target
metals could be achieved after Oxaline leaching using two
precipitation steps: first, a zinc-rich oxalate was formed, while
in the second step an iron-rich oxalate could be precipitated.
Indium and tin stayed in solution, probably due to the Figure 4. Dilution of the Oxaline leachate and precipitation of white
formation of stable complexes and can potentially be further zinc oxalate next to the green-colored filtrate.

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Figure 5. X-ray diffraction pattern of the dried zinc oxalate precipitate.37,38
deionized water, and dried at 50 °C overnight. Using XRPD,
the precipitate was identified as ZnC2O4·2H2O with small
amounts of PbC2O4 (Figure 5).15 The solid was subsequently
dissolved in aqua regia and analyzed using ICP-OES. The
precipitate was found to be composed of 90% ZnC2O4·2H2O
and 3.6% PbC2O4. Additionally, the precipitant contained
small amounts of Fe, Mn, Cu (all below 1%), and traces of Ni,
Co, and Cd, which presumably coprecipitated with the main
compounds. With respect to the amounts in the original flue
dust sample, 95% zinc, 65% lead, and 52% copper were
separated in this first precipitation step. Most of the iron
remained in solution, accounting for the green color of the
filtrate. Importantly, no traces of indium or tin could be found
in the precipitate.
Photoinduced Reduction: Precipitation of Fe Oxalate
Phase. When filtrates from the first precipitation step were left
for a prolonged period, slow precipitation of a second, yellow
phase was observed over a period of 35 days. ICP-OES analysis
showed that the majority of those metals which were still in
solution after the first precipitation (mostly iron) had formed
this yellow solid. Only the target metals indium and tin
remained in solution Figure 6.
The second precipitate was filtered, washed with deionized
water, dried at 50 °C, and analyzed using XRPD (Figure 7).
Quantitative analysis was performed as previously described
Figure 6. Diluted Oxaline leaching samples with depleted flue dust
components Zn, Cu, Pb, and Fe after 35 days still containing the
dissolved target metals indium and tin.
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using ICP-OES. FeC2O4·2H2O was identified as the major
solid phase (90% of the material). The lead and zinc content of
the solid was below 1%, and it was not possible to identify
specific solid phases for these metals using X-ray diffraction.
There was no evidence of indium or tin in this second
precipitate as both target metals remained in solution
(Figure 6).
These observations open an interesting possibility for the
selective separation of the target metals. Thus, the driving force
of the slow iron precipitation was investigated. Seed crystals
had no influence on the precipitation process. However, it was
observed that samples stored in different locations in the
laboratory behaved differently. Light was hence considered as a
possible cause for the reaction. Moreover, iron(III) oxalate
complexes are photosensitive and undergo reduction to the
iron(II) oxalate complex [Fe(C2O4)2]2− under the conditions
of this experiment.40−42 This is consistent with the green color
of the solution after the first precipitation and UV−vis
spectroscopic data recorded before and after the second
precipitation step (see Figure S1). Furthermore, no precipitate
was formed in a reference sample that was kept in the dark for
14 days (Table 3).
We conclude that the iron(III) oxalate complexes, formed in
the diluted Oxaline leachate, are reduced by photolysis and
subsequently precipitate as FeC2O4·2H2O in the second
precipitation step.42,43
hν
2Fe(C2O4 )33 − → 2Fe(C2O4 )22 − + C2O24 − + 2CO2 ↑ (1)
Subsequently, an insoluble oxalate is formed.
Fe(C2O4 )22 − + 2H 2O → FeC2O4 ·2H 2O↓ + C2O24 − (2)
This is consistent with findings that solid FeC2O4 is the
predominant species in acidic aqueous solution (pH: 1.6 to
3.2) with oxalate ligands in excess of the amount of iron.41
It has been reported that the rate of reduction of ferric
oxalate to ferrous oxalate and carbon dioxide is proportional to
the light intensity and favored when the solution is oxygen
free.44,45 Therefore, the obtained leachate was subjected to
various conditions, and the resulting solids were analyzed the
same way as described above. Results are displayed in Table 3.
Barely any precipitate formed in the dark reference sample,
and the iron concentration in solution remained at 2570 mg/L.
Natural sunlight caused the iron concentration to decrease
significantly over a longer period. Comparing the air- and
argon-flushed samples suggests that oxidative conditions
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Figure 7. X-ray diffraction pattern of the dried iron oxalate precipitate.39

Table 3. Influence of Experimental Parameters on assisted ferrous oxalate precipitation by addition of Fe metal to
Formation of Iron Oxalate Precipitatea the leachate.46 However, metallic iron addition leads to an
increase in overall iron concentration. Depending on the aim
Dark Sun Air Argon Seeds UV
of the process, UV-induced precipitation may be advantageous
precipitation efficiency 0.8 83.0 70.6 92.3 84.9 92.3
(%) over the method described in the literature because iron is
c(Fe) in solution 2570 363 701 46.9 294 35.9 removed without further addition of chemicals.
(mg/L) A summary of both precipitation steps after leaching at 50
a
The samples originate from an Oxaline leaching experiment, where a and 70 °C is shown in Figure 9.
zinc oxalate precipitate was separated from the solution prior to the Comparison to Aqueous Leaching Experiments with
exposure to different conditions. Dark: dark reference sample (46 Oxalic Acid. To evaluate Oxaline as a lixiviant in comparison
days). Sun: exposed to sunlight (46 days). Air: sample flushed with air to conventional aqueous systems, leaching experiments of the
prior to exposition to sunlight (46 days). Argon: sample flushed with flue dust were carried out using aqueous oxalic acid solutions.
argon prior to exposition to sunlight (46 days). Seeds: sample
containing ferrous oxalate seed crystals and exposed to sunlight (46
The results of selected screening experiments are shown in
days). UV: sample irradiated with a UV lamp (λ = 365 nm) (9 h). Figure 10.
At 50 °C, the oxalic acid concentration has a significant
impede the precipitation process, likely due to competition effect on leaching yields of the relevant metals. Overall, metal
with the photoreduction. Seed crystals did not have a yields are increasing with acid concentration, which can be
significant effect on the rate of precipitation, whereas UV expected due to the oxidic nature of the flue dust. In all
radiation reduced the iron content to 35.9 mg/L within 9 h experiments, it was possible to leach indium and tin from the
(Figure 8). Therefore, photoreduction, and not crystallization material but not at the high yields observed in Oxaline. Like in
Oxaline, this process was accompanied by the dissolution of
iron, again indicating that the target metals are released when
franklinite dissolves. Less zinc was found in the aqueous
leachates, which was surprising as zinc and iron should co-
dissolve from the franklinite phase. XRPD of the leaching
residue showed ZnC2O4·2H2O as a major component,
suggesting that zinc did indeed dissolve but immediately
precipitated as an oxalate (Figure S2). Similar behavior was
observed for copper, which also forms poorly soluble oxalate
phases. Lead sulfate was identified in the solid residue next to
residual franklinite (Figure S2). Therefore, zinc, copper, and
lead are found mainly in the solid residue. Using 30 and 60 g/L
oxalic acid, the leaching yields of zinc, copper, and lead remain
below 7%. An increase in the acid concentration to 90 g/L
resulted in a higher yield for all components, in particular for
Figure 8. Diluted iron(III) oxalate solution (left) and photolysis using In, Sn, Pb, and Fe.
a 125 W UV lamp after 3 h (middle) and 9 h (right). At 70 °C, leaching occurred at a faster rate, but the yields
after 48 h were not substantially different from those at 50 °C.
of FeC2O4·2H2O, seems to be the rate limiting factor. During The biggest deviation could be observed for the 90 g/L oxalic
precipitation, a small increase in pressure was observed in all acid samples after 8 h, where the values for indium, tin, and
sealed glass bottles, except the dark reference. This is iron are 10% to 20% higher compared to the 50 °C series. No
consistent with the formation of CO2 during the reduction temperature-related improvement of the leaching behavior was
of ferric iron.42 observed for the experiment using 30 g/L oxalic acid. The
An alternative method for iron(III) removal was described highest yield for indium (above 90%) was obtained from the
in the literature by Liu et al., who presented an ultrasound- leaching experiment with 90 g/L oxalic acid at 50 and 70 °C;
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Figure 9. Comparison of Oxaline leaching at 50 °C (left) and 70 °C (right) with l/s = 20 and subsequent precipitation of zinc and iron oxalate
precipitates.
Figure 10. Comparison of 48 h flue dust leaching experiments using 30, 60, and 90 g/L oxalic acid (from left to right) at 50 °C (top) and 70 °C
(bottom) with a l/s ratio of 10.
therefore, the results from this series are compared to the
Oxaline process in the following.
While in Oxaline all investigated metals showed high
leaching yields, those of Sn, Cu, Zn, and Pb were low in the
aqueous system. While this could be seen as increased
selectivity, it is not beneficial to a commercial process as
valuable components remain in the leaching residue while
undesired iron readily dissolves.
The photoinduced iron reduction was also tested on the
aqueous oxalic acid system. The 48 h leaching samples were
filtered, diluted with deionized water, and exposed to UV light
for 5 h as described previously. The results (Figure 10) show
that ferric iron can be reduced and precipitated as
FeC2O4·2H2O similar to the Oxaline samples. For the 90 g/
L oxalic acid experiment at 50 and 70 °C, the iron content was
decreased from more than 73% to 2% and 3%, respectively.
This photoreductive precipitation had no major effect on the
concentration of tin. However, indium was coprecipitated,
decreasing the amount of indium in solution by 25% (70 °C)
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and 50% (50 °C). In comparison, the average indium loss
during both precipitation steps in the Oxaline process was only
10%. Indium is known to from stable complexes with chloride,
we hence suspect that the choline chloride component of
Oxaline plays a crucial role in keeping indium in solution.47
■ CONCLUSIONS
Three different DESs were investigated for the leaching and
selective extraction of indium and tin from an oxide flue dust
and compared to experiments in an aqueous oxalic acid
solution. Oxaline was found to be the most efficient lixiviant,
also allowing for the highest selectivity in further separation
steps.
The raw material consisted of franklinite (ZnFe2O4) as the
main crystalline phase, as well as PbSO4 and Zn2(SiO4). High
yields of the target metals were always accompanied by
dissolution of iron and zinc, suggesting that indium and tin are
bound in the franklinite phase. It was therefore not possible to
extract those elements selectively during leaching.
DOI: 10.1021/acssuschemeng.8b06331
ACS Sustainable Chem. Eng. 2019, 7, 5300−5308
ACS Sustainable Chemistry & Engineering
Nevertheless, we were able to show the selective separation
of Zn, Fe, Pb, and Cu from the Oxaline leaching solution using
two subsequent precipitation steps, leaving the target metals In
and Sn in solution. Initially, the Oxaline leachate was diluted
with deionized water, causing formation of a white precipitate
within minutes. The precipitate mainly consisted of
ZnC2O4·2H2O, with small amounts of PbC2O4. The majority
of copper was also separated during this first precipitation. In
the following step, iron was separated without the addition of
chemicals, via photoinduced reduction and subsequent
precipitation of FeC2O4·2H2O. The ideal conditions for the
photolysis reaction were found to be in an oxygen-free
solution, exposed to sunlight for a period of days or subjected
to UV radiation for several hours.
Importantly, indium and tin were not identified as
components in any of the precipitates. The target metals
remained in the solution and are therefore available for
conventional separation techniques such as solvent extraction.
To evaluate the potential of the Oxaline system, equivalent
leaching experiments were conducted using aqueous oxalic
acid solutions.
Key aspects of the DES vs the aqueous system are as follows:
(1) High leaching yields for the target metals indium and tin
were achieved for both systems next to large
concentrations of iron.
(2) Compared to Oxaline, the aqueous system was already
effective at lower oxalate concentrations, but zinc, lead,
and copper remain in the leaching residue.
(3) In the Oxaline process, zinc could be quantitatively
precipitated from the leachate as ZnC2O4·2H2O,
accompanied by copper and lead.
(4) Iron could be separated via photoinduced reduction as
FeC2O4·2H2O in both systems; however, in the aqueous
system, this resulted in significant indium losses.
(5) Tin remained in solution throughout the precipitation
steps, but the leaching yield was significantly better for
Oxaline.
Both systems exhibit high recovery rates for tin, whereas
indium losses were up to 50% during the iron precipitation
step in the aqueous system. We hence believe that the high
chloride concentration of the Oxaline system may have a
significant influence on the stability of indium complexes in
solution, inhibiting coprecipitation with iron. High oxalate and
chloride concentrations of 4.5 mol/L at ambient temperatures
give Oxaline these unique properties. Comparable conditions
for an aqueous system can only be achieved at temperatures
significantly above 50 °C under extremely acidic conditions.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b06331.
Detailed description of experimental procedures, addi-
tional data regarding flue dust composition, additional
UV−vis and XRPD data, and image of pressurized
sample filtration at elevated temperature. (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: frisch@tu-freiberg.de.
5307
Research Article
ORCID
Gero Frisch: 0000-0002-8997-7744
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the ZIM program of
the German Federal Ministry for Economic Affairs and Energy
(Project-ID.: KF 3181702MU4). We also thank Gunther
Pieplow for fruitful discussions and for providing the raw
material, Katharina Strecker for ICP-OES measurements and
making us aware of several pitfalls of this technique, Regina
Moßig and Iris Paschke for XRPD measurements, and Dr. Erik
Mehner and Dr. Nicolai-Alexeji Kummer for recording the
XRF and ICP-MS spectra.
■
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