Waste Management 96 (2019) 181–189

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Indium and tin recovery from waste LCD panels using citrate
as a complexing agent
Adrián López-Yáñez a, Alejandro Alonso b, Alejandra Vengoechea-Pimienta c,
Jorge Ramírez-Muñoz a,⇑
a
Departamento de Energía, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, Azcapotzalco, 02200 CDMX, Mexico
b
CONACYT, Universidad Autónoma Metropolitana-Azcapotzalco, Av. San Pablo 180, Col. Reynosa Tamaulipas, Azcapotzalco, 02200 CDMX, Mexico
c
Grupo de investigación GISA, Universidad de La Guajira, Facultad de Ingeniería, Km 5 vía a Maicao, Riohacha, La Guajira, Colombia

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

Article history: In this work, an environmentally-friendly leaching process for the recovery of indium (In) and tin (Sn)
Received 21 September 2018 from LCD panel waste was investigated. Easily degradable citrates (C6H5O3
7 ), i.e., sodium citrate and
Revised 7 July 2019 citric acid, were used as complexing agents. The morphology and composition of the species present in
Accepted 20 July 2019
the LCD powder before and after the leaching processes were characterized by scanning electron micro-
scopy (SEM) and energy dispersive spectroscopy (EDS). The concentrations of In, Sn, and iron (Fe) present
in the leachate were determined by atomic absorption spectrometry (AAS). The necessary thermody-
Keywords:
namic conditions for achieving substantial In recovery were established by using MEDUSA software.
LCD panel
Indium recovery
The optimal process conditions were determined experimentally by varying the initial citrate concentra-
Indium tin oxide tion as well as by using reducing or oxidizing media, respectively hydrazine (N2H4) or hydrogen peroxide
Citrate (H2O2). It was found that using N2H4 in a citrate solution as a reducing agent enhances the leaching effi-
Alternate leaching agents ciency. However, high concentrations of Sn and Fe with respect to In were found in the LCD powder.
Therefore, a pretreatment processes to first remove the excess of Sn and Fe, which compete with In for
the citrate, was implemented. Leaching with 1 M citrate, 0.2 M N2H4, at pH = 5, using sodium hydroxide
(NaOH) at solid:liquid (S:L) ratio of 20 g∙L
1, yielded a remarkably high In recovery of 98.9% after 16.6 h.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction natural sources is around 10 to 20 mg/kg, while Dodbiba et al.

The current demand for commodities with scientific and tech-
nological interest, e.g., water, petroleum products and rare metals,
has fostered the exploration of new territories to obtain them, but
also has led to the development of new methodologies that allow
the recovery of materials from waste and, at the same time,
decrease pollutant emissions (Yang et al., 2008). Many novel elec-
tronic devices employ rare materials for their operation. Some of
them of technological relevance, are heavy or precious metals,
among them gold, silver, platinum, palladium, selenium, indium,
and also others of more general use, such as iron, copper, alu-
minum, zinc and tin.
Many of these devices become obsolete in a short time, gener-
ating abundant electronic waste (Cui and Zhang, 2008). LCD flat
screens have drawn interest among the scientific community due
to its high contents of In of around 200 ± 50 mg/kg (Yang et al.,
2013). In contrast, according to Park et al. (2009), In content from
⇑ Corresponding author.
E-mail address: jrm@azc.uam.mx (J. Ramírez-Muñoz).
(2012) reported variations between 1 and 100 mg/kg. Therefore,
waste LCD flat screens represent an important source of Indium.
In LCD screens this metal is found in the form of oxide together
with Sn, in a semiconducting material known as ITO (indium tin
oxide), that corresponds to the TCO (transparent conduction oxide)
layer, i.e., the transparent electrode. Thus, ITO is widely used in the
production of LCD panels, computer monitors and mobile device
screens (Lin et al., 2009; Savvilotidou et al., 2014; Hsieh et al.,
2009; Park et al., 2009).
Since the ITO film on LCD panels cannot be removed mechani-
cally, it is necessary to disassemble the screens and recover In by
using metallurgical processes such as pyrometallurgy, biometal-
lurgy and hydrometallurgy.
Pyrometallurgical processing consists in the recovery or extrac-
tion of metals of interest using incineration, melting in blast fur-
naces, slagging, sintering, melting and reactions in a gaseous
phase at high temperatures (Cui and Zhang, 2008; Itoh and
Maruyama, 2011; Wang et al., 2013). Biometallurgical processing
has awoken interest in recent years and is one of the most promis-
ing technologies for recovering metallic species. This technique is

https://doi.org/10.1016/j.wasman.2019.07.030
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
182 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189
divided into two main areas, namely bioleaching, and biosorption.
Bioleaching has been successfully applied in the recovery of metals
from metallic sulfides, which are the main minerals that carry most
of the base and precious metals, through the use of bacteria-
assisted reactions. On the other hand, biosorption is a passive
physical-chemical interaction between the solid surface and
microorganisms and ions in solution, in which living or dead
microorganisms can be used. Many microorganisms, including
algae, bacteria, yeast and fungi, are known to act as biosorbents
of heavy and precious metals. Biometallurgical extraction of metals
such as Co, Mo, Ni, Pb, and Zn from sulfur minerals is technically
feasible. However, at present only copper and gold are produced
industrially in significant proportions with this technique (Cui
and Zhang, 2008; Itoh and Maruyama, 2011).
Other types of recovery processes of In from LCD panels are
through chloride volatilization, where recovery of In from In2O3
is enhanced when the molar ratio Cl/In in nitrogen (N2) and air
atmospheres increase (Park et al., 2009). Hasegawa et al. (2013a)
developed a new process for the recovery of In using aminopoly-
carboxylate chelants (APC) as the extractant. In another work,
Hasegawa et al. (2013b) proposed a solid phase extraction (SPE)
gel, known as molecular recognition technology (MRT), which is
claimed to have selectivity in binding the analyte of interest even
in highly-concentrated matrix solutions. Yoshida et al. (2014)
recovered In from LCD panel waste using subcritical water at var-
ious temperatures and reaction times.
Another well-stablished method commonly used to enrich
metallic oxides from mineral sources, e.g., lead, zinc and copper
oxide minerals, is froth flotation (Feng et al., 2017; Feng et al.,
2018; Feng et al., 2019). In this method, a sulfidizing reagent
(e.g., Na2S, H2S) is used to condition the mineral surface for the
concentration of sulfide species, which improve the mineral floata-
bility in comparison with metal oxide minerals (Feng et al., 2017).
It is necessary to clarify that this is only a concentration stage
inside the hydrometallurgy or pyrometallurgy processes.
On the other hand, the hydrometallurgical processing consists
of the acid or alkaline leaching of the solid material. In particular
cyanide and thiosulfate are systems used in silver and gold leach-
ing, and ammonia is employed in some cases for the solubilization
of copper, just to mention two examples.
After the leaching and its corresponding liquid-solid separation,
the pregnant solution is subjected to separation and purification
procedures such as precipitation of impurities, solvent extraction,
adsorption and ion exchange, in order to isolate and concentrate
the metals of interest. The main reagents used in this process are
mainly sulfuric acid, hydrochloric acid and nitric acid (Hsieh
et al., 2009; Li et al., 2011; Li et al., 2009; Yang et al., 2013; Yang
et al., 2014).
In the aforementioned studies, the use of inorganic acids for the
leaching process is common. However, some authors have shown
that it is possible to recover metals from waste lithium-ion batter-
ies using organic acids, instead of mineral acids. For instance, Li
et al. (2010a, 2010b) recovered Li and Co from lithium-ion battery
employing DL-malic acid and a mixture of citric acid (C6H8O7) and
H2O2 as leaching agents. Their results show a highly efficient
recovery of these metals. Nayaka et al. (2015) recovered Li and
Co using an aqueous mixture of C6H8O7 (chelating agent) and
ascorbic acid (reductant) and the dissolution proceeded with a
reductive-complexing mechanism. Li et al. (2015), by using suc-
cinic acid as a leaching agent in the presence of H2O2 recovered
Li and Co from spent lithium-ion batteries. On this basis, the aim
of the present work consists in studying the use of an organic acid
(citrate) for recovering In from LCD waste.
Using an organic complexing agent, e.g., citrate, represents sig-
nificant advantages with respect to using ubiquitous mineral acids,
such as sulfuric acid (H2SO4). For instance, no special construction
materials with a higher level of resistance to corrosion (e.g., stain-
less steel Grade 316) are necessary for the process equipment, and
in addition, it is an environmentally friendly recovery processes (Li
et al., 2010a; 2010b). Other advantages of using organic acids are
lower operating costs and easier separation of the metal of interest
(in this case In). To the best of the authors’ knowledge, there are no
previous studies where the citrate has been used for In recovery
from LCD waste.
The aim of this study is to employ a hydrometallurgical process
for the recovery of In and Sn from LCD screens using citrate from
two sources: sodium citrate (Na3C6H5O7) and citric acid. With this
purpose, the paper is organized as follows: Section 2 contains the
description of LCD screen disassembly process and further pulver-
ization of LCD waste. It also contains the description of the exper-
imental setup for the leaching, and the scanning electron
microscopy (SEM) and energy dispersive spectroscopy (EDS) anal-
yses performed on the solids after leaching. Section 3 is divided
into five parts: In Section 3.1, the total contents of In, Sn and Fe
in the batch LCD powder was determined by using aqua regia
digestion method. In Section 3.2, the composition of the LCD pow-
der was determined before the leaching by SEM and EDS analyses.
In Section 3.3 a thermodynamic study of the equilibrium of species
in the leaching systems with predominance zone diagrams (PZD) is
carried out. In Section 3.4, different experimental setups for leach-
ing of In from LCD-powder are shown. In Section 3.5, the composi-
tion of the LCD powder was determined by SEM-EDS after leaching.
Finally, in Section 4 the relevant conclusions are laid down.
2. Materials and methods
The experimental procedure consisted of three main stages. In
the first one, the flat screens were taken apart and the LCD panels
obtained were milled and sieved. After that, the resulting powder
was put in contact with the leaching solutions, and samples were
taken during the leaching stage. Finally, once the leaching was
over, solids were separated by filtration, then dried and analyzed
by SEM. In Sections 2.1–2.3, a more detailed explanation of the
methodology can be found.
It is important to emphasize that a previous study, based on
solution thermodynamics was performed in order to determine
the composition of the leaching solutions. For this purpose, the
open source software MEDUSA (Puigdomenech, 2004) was used
to obtain the phase diagrams of the chemical systems
In3+-C6H5O3
2+ 3
3+ 3

7 , Sn -C6H5O7 and Fe -C6H5O7 in sulfuric or nitric
acid media and in presence or absence of phosphate ions.
2.1. Disassembly and pulverization
Waste LCD flat screens were disassembled, and the polarizing
plastic film was removed from the glass substrate using a heat
gun. After that, the separated glass sheets were milled using a
tooth disc mill (12.5 cm diameter) and thereafter with an agate
mortar until a fine powder was obtained. This solid was sieved
and just one fraction (
74+44 lm) was used in further experi-
ments. The particle size chosen is frequently used in industrial
leaching, as it ensures an acceptable homogeneity in the solid
batch and at the same time avoiding excessive energy consump-
tion during milling.
2.2. Leaching
The leaching was carried out in a beaker with an overhead stir-
rer (CaframoÓ). Firstly, 250 mL of solution was put in the beaker;
then 5 g of LCD powder sample was added, and the leaching began.
In all experiments, the leaching slurry was agitated at 450 rpm. At
 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189
pre-stablished times (see Figs. 3–5), 2 mL of leaching slurry was
sampled and filtered for analysis of In, Sn and Fe contents in an
atomic absorption spectrometer (SpectraA 220FS). In order to cor-
roborate the reliability of the results, each leaching reaction was
performed at least twice, and average (with their corresponding
standard deviation bars) values are reported.
All experiments were carried out at normal room temperature
and ambient pressure (25 °C and 1 atm, respectively). The pH of
the solutions were set to 5, adjusted with sulfuric or nitric acid
(HNO3) when the citrate source was Na3C6H5O7, and with NaOH
when C6H8O7 was used. Citrate (99%, Meyer) concentration used
during the tests were 0.25, 0.5, 0.75, and 1 M, and the solid-to-
liquid ratio used in all reactions was 0.02 g/mL.
On the other hand, two additional sets of experiments were per-
formed. In the first one, a reducing media was introduced using
0.2 M N2H4 (64–65%, Sigma-Aldrich, N2H4), while in the second
set, 1.5 M H2O2 (29–32%, Merck, H2O2) was used as an oxidizing
agent.
2.3. SEM analysis
The morphology of the LCD powder materials before and after
leaching was characterized by SEM and EDS (Zeiss, model VP
1050). The back-scattering electron detector (BSE) was used in
the study of LCD powder at 15 kV and a working distance of
7.9 mm for each sample.
3. Results and discussion
3.1. Amount of In, Sn and Fe in the batch LCD powder
The concentration of chemical species of interest in the LCD
powder batch was determined by an aqua regia digestion method.
The results obtained show that the average concentration of Fe was
6491.2 (±260.4) mg/kg , which is in a much higher proportion than
the average concentration of In and Sn of 149 (±5.3) and 1392.1
(±76.3) mg/kg, respectively. Li et al. (2011) reported the ratio of
In to Sn to be about 9:1. However, the results obtained in this work
point to the opposite, i.e., the ratio is 1:9. At present we have no
explanation for this discrepancy, but the results presented were
confirmed with three experiments, ensuring their reliability.
3.2. Composition of the LCD powder by SEM
SEM and EDS were respectively used to determine the morphol-
ogy of the milled particles and to determine the presence of atomic
species in the LCD powder batch. In the analysis performed over
the ground material, the presence of In, Al, Si, Ca, and Mg was
determined and values of 10.8, 17.2, 55.8, 14.6, and 1.6, in weight
percent [(w/w)%] were respectively obtained. Yang et al. (2014)
reported the presence of Sn and Fe in LCD waste panels, therefore,
their presence was also investigated in this work.
An SEM micrograph of the LCD powder is shown in Fig. 1. Here,
the structure of the In-carrying particles is depicted; however, as
mentioned earlier, Sn and Fe were not detected prior to the leach-
ing process. This can be due to the species not being present at the
surface of the particles, but rather in the innermost layers. On the
other hand, a homogeneous distribution of similarly-shaped parti-
cles can be observed.
3.3. Predominance zone diagrams (PZD) for the equilibrium of species
in citrate leaching systems
In this work, the equilibrium constants of chemical species were
investigated in order to build the PZD by means of the MEDUSA
183
Fig. 1. Micrograph of LCD powder before leaching process obtained by SEM.
software (Puigdomenech, 2004), which is based on the algorithm
reported by Eriksson (1979). This method takes into account all
the thermodynamic equilibria in which the components take part.
Then, it calculates the Gibbs free energy for each reaction in a mesh
constructed with the concentration changes of two given compo-
nents. The algorithm then assigns the predominance to the specie
that was formed with the free energy minimum for each point in
the mesh, from where a two-dimensional diagram results.
Manzurola et al. (1989) carried out a study of the formation of
complexes using the hydroxycarboxylic, citric, tartaric and malic
acids as binders with In, Fe, Cu and Al. They reported the following
log(K) values for the formation constants of the coordination com-
pounds: log(KML) = 7.3 and log(K ML 2 ) = 11.72 for In, log(KML) = 8
and log(K ML 2 ) = 20.1 for Fe, where M = {In3+, Sn2+, Fe3+} and
L = C6H5O3
7 . On the other hand, Smith (1965) presented a study
of the formation of Sn complexes using citric and tartaric acids
and reported values of log(KML) = 7.3 and log(K ML 2 ) = 12.8.
It is evident that Fe has the highest species formation constant,
followed by Sn, and In, with the lowest value. This means that
In-citrate complexes, are the less thermodynamically stable in
comparison with Fe-citrate and Sn-citrate, leading to a difficult In
recovery, as Fe and Sn are stronger consumers of citrate.
The Pourbaix-type diagrams of Fig. 2 for the In3+-C6H5O3
7 ,
2+
Sn -C6H5O3
7 and Fe3+-C6H5O3
7 systems were constructed with
the species formation constants indicated above, in addition to
data already existing in the MEDUSA database, called HYDRA.
These diagrams produce information about thermodynamically
favorable conditions for the predominance of different species,
which may exist in the leaching system. In the diagrams shown
in Fig. 2a and b it is observed that pH values ranging from 3 to
6.5 favor the formation of In complexes of interest.
However, in Fig. 2c, d, e, and f, it is observed that the area of
complex formation of Sn and Fe is much larger, in both cases, than
the In-citrate region, in sulfuric or nitric acid media. On the other
hand, if we observe in Fig. 2f, where HNO3 is used, it is clear that
the area of complex formation for soluble Fe is smaller, due to
the larger zone where solid Fe2O3 exists, which favors the objec-
tives of this work. In order to enlarge the zone where iron forms
solid complexes, an additive was added; the diagrams of Fig. 2g
and h are presented for leaching systems in presence of phosphate
(PO3
4 ), which is a ligand capable of precipitating iron. Despite that
the precipitation of Fe phosphate was achieved, also the InPO4
solid phase was formed. Therefore, it can be expected that the
extraction of Fe and Sn will be larger with respect to the extraction
or complexation of In. Furthermore, the concentration of indium in
184 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189

Fig. 2. Pourbaix-type diagrams for (a) In3+-C6H5O3
2
3+ 3
2+ 3
2
2+ 3
3+ 3

7 with SO4 , (b) In -C6H5O7 with NO3 , (c) Sn -C6H5O7 with SO4 , (d) Sn -C6H5O7 with NO3 , (e) Fe -C6H5O7 with


SO2
3+ 3
3+ 3
3
3+ 3
3

4 , (f) Fe -C6H5O7 with NO3 (cr = crystalline species), (g) In -C6H5O7 with PO4 , and (h) Fe -C6H5O7 with PO4 .
 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189 185

solid state with respect to Sn and Fe is much lower, as was evident
when compositions were determined after the acid digestion (see
Section 3.1).
The proper conditions to carry out the reactions were obtained
from the Pourbaix-type diagrams. At pH = 5, the In-citrate complex
formation is favored, therefore, this value was chosen for the ensu-
ing experiments.
3.4. LCD powder leaching using citrate as a complexing agent
In this work, Na3C6H5O7, instead of a mineral acid, was pro-
posed as a complexing agent, as it is regularly used in the extrac-
tion of heavy metals from minerals and electronic waste. On the
other hand, the use of an organic ligand allows the design of
environmentally-friendly processes, besides considerable savings
in capital costs of equipment, as these reagents are less corrosive
and produce no toxic vapors. Furthermore, only a few works have
been reported in the literature employing organic acids for the
extraction of metal species of interest.
In general, an oxidizing or reducing agent is needed in the
leaching stages in order to solubilize the metals of interest due
to an oxidation number change. In this case, as In is present in
LCD panels with its higher oxidation state, as an oxide (In2O3), in
the first leaching tests N2H4 was used as a reducing agent.
Fig. 3 a shows the recovery rates for In, Sn and Fe as a function
of the reaction time. It is observed that 43% of In was recovered
after 9 h of reaction and Sn presents a similar rate. On the other
hand, Fe presents a higher (92%) recovery rate than those of In
and Sn, just as the thermodynamic study predicted (Fig. 2a, c and
e). In this recovery process, a solution with 1 M Na3C6H5O7 reaches
pH = 9, then H2SO4 was added in order to adjust the solution to
pH = 5 and locate it inside the theoretical window where thermo-
dynamic diagrams predict that In and Sn are soluble.
On the other hand, the recovery rates shown in Fig. 3b were
obtained in the presence of HNO3 instead of H2SO4. It is seen that
the recovery of In significantly decreases in comparison with sulfu-
ric acid media (data shown in Fig. 3a), reaching only 12% after 6 h
of reaction. The amount of soluble Sn remained at 33%, however,
the removal of Fe(III) was significantly favored with HNO3, increas-
ing its dissolution rate to 98% in just 6 h of reaction, after that, its
concentration remained unchanged.
As mentioned earlier, in Fig. 3a and b, N2H4 was used to gener-
ate a reducing media to favor the solubilization of In2O3 and SnO2,
releasing In from the solid matrix. It is to be noted that despite the
fact that In(III) is soluble in water owing to its complexation with
citrate, Sn(IV) is not. The presence of N2H4 favors the reaction out-
lined in Eq. (1), where Sn(IV) is reduced to Sn(II), which forms com-
plexes with the leaching agent (see Fig. 2c and d).
2SnO2 þ N2 H4 ! 2SnO þ 2H2 O þ N2 ð1Þ
However, it is possible that the LCD glass structure contains
some reduced phases, such as metallic iron or aluminum, which
can prevent In solubilization, by promoting a cementation reaction.
Therefore, it was deemed convenient to establish an oxidation

100
Recovery (In)
Recovery (Sn)
Recovery (Fe)
80

60
Recovery (%)

40

20

0
0 100 200 300 400 500 600 700
Time (min)
a)
100
100

80
80 (In) (In)
(Sn) (Sn)
(Fe) (Fe)
Recovery (%)

60
Recovery (%)

60

40
40

20
20

0
0 200 400 600 800 0 200 400 600 800
Time (min) Time (min)
b) c)
Fig. 3. Recovery of In, Sn and Fe. Reaction conditions: 1 M of Na3C6H5O7, (a) 0.2 M of N2H4, H2SO4 (pH = 5), (b) 0.2 M of N2H4, HNO3 (pH = 5), and (c) 1.5 M of H2O2, HNO3
(pH = 5).
186 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189

medium, i.e., H2O2, in order to avoid the undesired redox reaction.
Profiles of recovery rates of chemical species are shown in Fig. 3c,
where H2O2 was used to investigate if an oxidizing medium
improves the recovery of indium. In this case, HNO3 was also used
to adjust pH. It was observed that the recovery rate of the analyzed
species (In, Sn and Fe) decreased considerably in comparison with
the reducing media tested before. The standard deviation bars for
the experimental leaching tests are also shown.
In Fig. 4 a and b the results of the recovery rates of In and Sn are
shown, where C6H8O7 instead of Na3C6H5O7 was employed as a
complexing agent, with three different concentrations, 0.25, 0.5
and 1 M. As C6H8O7 pH solution in the employed concentration is
around 1.6, a 7 M NaOH solution was used to adjust the pH to a
value of 5, and N2H4 was added to favor a reducing medium. There-
fore, in this media, no other anion was present in the solution. This
is the main difference between the use of C6H8O7 or Na3C6H5O7
(free of sulfates and nitrates), in which sulfuric or nitric acids need
to be added to attain pH = 5, incorporating sulfates or nitrates to
these solutions.
It was observed that, unlike the results shown in Fig. 3a, the
recovery of In and Sn was not maintained at a stable level, although
the extraction of Sn increased considerably. It is important to note
that In and Sn recovery rates increase as citrate concentration
grows, but seems to be limited by the solubility of Fe, because this
ion also forms complexes with citrate, limiting its available
amount for In and Sn citrates. This might be an explanation for
the rises and fall of In and Sn concentrations observed in Figs. 3c
and 4. In spite of this, Fe concentration in solution appears to be
in turn limited in the presence of sulfates, probably due to the
complexation between Fe(III)/Fe(II) and SO2
4 .
In order to test this hypothesis, a first experiment, to limit iron
solubilization, and a second one, with pretreatment to eliminate
iron prior to leaching stage, were performed, and the results are
shown in Figs. 4 and 5; the discussion can be found below.
In another set of experiments, phosphate was added in trying to
keep iron in a different complex than citrate, because its stability
constant seems high enough for such purpose. Recovery of In, Sn
and Fe with the presence of phosphates in the leaching system
was tested. The experimental results (see the figure in the
supplementary material section), showed no improvement in the
amount of indium leached. Due to these two facts that agree with
the thermodynamic diagrams shown in Fig. 2g and h: (a) indium
forms a solid specie with phosphate; (b) iron phosphate complexes
are mostly soluble, and seemingly do not compete with the iron

100 100
0.25 M
0.5 M
80 1M 80
In recovery (%)

Sn recovery (%)

60 60

40 40

20 20 0.25 M
0.5 M
1M

0
0
0 200 400 600 800
0 200 400 600 800
Time (min) Time (min)
a) b)
Fig. 4. Recovery (a) In and (b) Sn. Reaction conditions: 0.25, 0.5 and 1 M of C6H8O7, 0.2 M of N2H4 and NaOH (pH = 5).

100 100
(In)
(In) (Sn)
(Sn) (Fe)
80 80
(Fe)

60
Recovery (%)

60
Recovery (%)

40 40

20 20

0
0
0 10 20 30 40
0 200 400 600 800 1000 1200
a) Time (min)
b) Time (min)

Fig. 5. Reaction conditions: (a) Pretreatment using H2SO4 for pH = 1, LCD-powder = 5.5117 g; and (b) leaching using LCD-powder = 5.2637 g recovered from pretreatment,
1 M-C6H8O7, 0.2 M-N2H4 and NaOH for pH = 5.
 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189 187

citrate ones. These lead to high consumption of citrate in the iron
complexes, limiting its availability to form indium complexes.
Finally, a pretreatment of the LCD powder using H2SO4 was car-
ried out in order to eliminate the Fe excess, which has a thermody-
namic advantage and competes with In for the C6H8O7 during the
leaching stage. The results can be seen in Fig. 5.
A sulfuric acid pretreatment was carried out for 40 min and, as
is evident from Fig. 5a, 66% of Fe was removed at a rate of
4323.1 mg/kg of the solid. In contrast, the percentage of In and
Sn were only 14.3% and 16.2%, respectively. However, concentra-
tions of 2168.1 mg/kg of Fe and 1166.6 mg/kg of Sn were still pre-
sent in the LCD-powder, which, comparing to the concentration of
In (127.7 mg/kg) after pretreatment, is still high. On the other
hand, Fig. 5b shows the results of the leaching of the solid recov-
ered from the pretreatment. It is observed that the recovery of In
(98.7%) was considerably greater, and competes with the recovery
of Fe (98.6%) and Sn (63.2%). The percentages of overall recovery (%
OR) of In, Sn and Fe calculated from the following expression
½M L2 L1
S1
þ ½MSL43 L3
% OR ¼  100 M ¼ fIn; Sn; Feg ð2Þ
½M S1
are shown in Fig. 6, for which total recoveries of 98.9, 69.1 and
99.5% can be respectively established. L and S are the volume of
leach solution (mL) and the amount of LCD powder (g). Additional
details regarding the notation of Eq. (2) are included in Fig. 6.
Despite the remarkable improvement obtained with H2SO4 pre-
treatment on which some amount of In goes into solution, a pre-
treatment where Fe is solubilized, while maintaining indium in
the solid phase in the presence of phosphate ions, is proposed for

Fig. 6. Pretreatment and leaching process for recovery of In, Sn and Fe.

Table 1
Composition of LCD powder determined by SEM-EDS after leaching process.

Species Citrate concentration

%(w/w) 0.25 M 0.5 M 0.75 M 1M
In 49.65 5.95 8.45 1.02
Sn 0 0 0 91.82
Fe 0 9.88 1.79 1.46
Al 8.94 13.66 17.35 0.92
Si 31.66 49.42 57.04 3.14
Ca 8.71 19.31 13.20 1.09
Mn 0 0 0 0.15
Mg 1.05 1.78 2.18 0.09
Ni 0 0 0 0.31
188 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189
Fig. 7. Micrographs of LCD powder after leaching process obtained by SEM. Reaction conditions: (a) 0.25, (b) 0.5, (c) 0.75 and (d) 1 M of Na3C6H5O7, 0.2 M of N2H4 and H2SO4
(pH = 5).
future works. Once the solid is almost Fe-free, In can be recovered
based on the procedure described in this work.
3.5. Composition of the LCD powder after leaching determined by EDS
The LCD powder was also analyzed with EDS after leaching with
different Na3C6H5O7 concentrations. It was possible to determine
the presence of Sn and Fe, as well as some other atomic species,
like Ni and Mn, when leaching at concentrations of 1 M citrate.
Table 1 shows the weight composition of the samples analyzed.
3.6. SEM-determined morphology of LCD powder after leaching
Fig. 7 shows the corresponding SEM images of the LCD powder
morphology after leaching. As expected, it was found that In tends
to lodge more frequently in particle agglomerates and Fe tends to
be present in larger particles. These was not observed in untreated
materials (see Fig. 1), supporting the conclusion that one of the
effect of leaching is the modification of the particle surface. In
the results obtained by the analysis of composition and morphol-
ogy, it is observed that when increasing the concentration of
citrate, corrosion is favored, and therefore, the species contained
in the solid matrix are exposed and their extraction is facilitated.
4. Conclusions
An environmentally-friendly hydrometallurgical process for the
recovery of In and Sn from LCD panel waste was investigated by
using citrate as a complexing agent from two sources: sodium
citrate and citric acid.
It was found citrate is able to leach In from LCD wastes; how-
ever, Fe and Sn turn out to be large consumers of the ligand, due
to their metallic species-citrate formation constants. Fe has a
higher formation constant than Sn, and In has the lowest value,
which means that it has lower thermodynamic stability in the
leaching system.
In order to improve In recovery through the proposed leaching
system, a pretreatment was carried out in order to remove the
excess Fe present in the LCD powder before leaching, and, in turn,
produced greater availability of citrate for In recovery. Particle
morphology and presence of metallic species in the LCD powder,
before and after the leaching, were analyzed by SEM-EDS. The
results obtained suggested that In tends to lodge more frequently
in particle agglomerates, whereas Fe tends to be present in larger
particles. This, alongside with the thermodynamic results shown
here, could also be responsible for the higher Fe recovery with
respect to indium. In this sense, breaking the agglomerates where
In seems to be in greater proportion, could lead to an improvement
in its recovery, and this could be performed in situ during the
leaching stage by using mixing systems equipped with high shear
impellers.
According to the results obtained in this work, and after iron
removal pretreatment, it is possible to recover around 99% of In
from LCD screen powder using citrate as a complexing agent.
Finally, a better pretreatment, where In remains in solid phase
while Fe goes into solution, merits further investigation. This pre-
treatment could include gravimetric and flotation stages in order
to obtain a concentrate before leaching.
 A. López-Yáñez et al. / Waste Management 96 (2019) 181–189
Acknowledgments
ALY would like to thanks Universidad Autónoma Metropolitana
(Mexico) for his academic scholarship.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2019.07.030.
References
Cui, J., Zhang, L., 2008. Metallurgical recovery of metals from electronic waste: A
review. J. Hazard. Mater. 158, 228–256. https://doi.org/10.1016/j.
jhazmat.2008.02.001.
Dodbiba, G., Nagai, H., Wang, L.P., Okaya, K., Fujita, T., 2012. Leaching of indium
from obsolete liquid crystal displays: Comparing grinding with electrical
disintegration in context of LCA. Waste Manage. 32, 1937–1944. https://doi.
org/10.1016/j.wasman.2012.05.016.
Eriksson, G., 1979. An algorithm for the computation of aqueous multicomponent,
multiphase equilibria. Comput. Techn. Optim. 112, 375–383. https://doi.org/
10.1016/S0003-2670(01)85035-2.
Feng, Q., Wen, S., Deng, J., Zhao, W., 2017. Combined DFT and XPS investigation of
enhanced adsorption of sulfide species onto cerussite by surface modification
with chloride. Appl. Surf. Sci. 425, 8–15. https://doi.org/10.1016/j.
apsusc.2017.07.017.
Feng, Q., Zhao, W., Wen, S., 2018. Surface modification of malachite with
ethanediamine and its effect on sulfidization flotation. Appl. Surf. Sci. 436,
823–831. https://doi.org/10.1016/j.apsusc.2017.12.113.
Feng, Q., Wen, S., Baia, X., Chang, W., Cuic, C., Zhao, W., 2019. Surface modification of
smithsonite with ammonia to enhance the formation of sulfidization products
and its response to flotation. Miner. Eng. 137, 1–9. https://doi.org/10.1016/j.
apsusc.2017.12.113.
Hasegawa, H., Rahman, I.M.M., Egawa, Y., Sawai, H., Begum, Z.A., Maki, T., Mizutani,
S., 2013a. Recovery of indium from end-of-life liquid-crystal display panels
using aminopolycarboxylate chelants with the aid of mechanochemical
treatment. Microchem. J. 106, 289–294. https://doi.org/10.1016/j.
microc.2012.08.010.
Hasegawa, H., Rahman, I.M.M., Umehara, Y., Sawai, H., Maki, T., Furusho, Y.,
Mizutani, S., 2013b. Selective recovery of indium from the etching waste
solution of the flat-panel display fabrication process. Microchem. J. 110, 133–
139. https://doi.org/10.1016/j.microc.-2013.03.005.
Hsieh, S.J., Chen, C.C., Say, Wen C., 2009. Process for recovery of indium from ITO
scraps and metallurgic microstructures. Mater. Sci. Eng., B 158, 82–87. https://
doi.org/10.1016/j.mseb.2009.01.019.
Itoh, S., Maruyama, K., 2011. Recoveries of metallic indium and tin from ITO by
means of pyrometallurgy. High Temp. Mater. Proc. 30, 317–322. https://doi.org/
10.1515/htmp.2011.051.
Li, J., Gao, S., Duan, H., Liu, L., 2009. Recovery of valuable materials from waste liquid
crystal display panel. Waste Manage. 29, 2033–2039. https://doi.org/10.1016/j.
wasman.-2008.12.013.
189
Lin, K.L., Chang, W.K., Chang, T.H., Lee, C.H., Lin, C.H., 2009. Recycling thin film
transistor liquid crystal display (TFT-LCD) waste glass produced as glass–
ceramics. J. Cleaner Prod. 17, 1499–1503. https://doi.org/10.1016/j.
jclepro.2009.05.012.
Li, Y., Liu, Z., Li, Q., Liu, Z., Li, Z., 2011. Recovery of indium from used indium–tin
oxide (ITO) targets. Hydrometallurgy 105, 207–212. https://doi.org/10.1016/j.
hydromet.2010.09.006.
Li, L., Ge, J., Chen, R., Wu, F., Chen, S., Zhang, X., 2010a. Environmental friendly
leaching reagent for cobalt and lithium recovery from spent lithium-ion
batteries. Waste Manage. 30, 2615–2621. https://doi.org/10.1016/j.
wasman.2010.08.008.
Li, L., Ge, J., Wu, F., Chena, R., Chen, S., Wu, B., 2010b. Recovery of cobalt and lithium
from spent lithium ion batteries using organic citric acid as leachant. J. Hazard.
Mater. 176, 288–293. https://doi.org/10.1016/j.jhazmat.2009.11.026.
Li, L., Qu, W., Zhang, X., Lu, J., Chen, R., Wu, F., Amine, K., 2015. Succinic acid-based
leaching system: A sustainable process for recovery of valuable metals from
spent Li-ion batteries. J. Power Sources 282, 544–551. https://doi.org/10.1016/j.
jpowsour.2015.02.073.
Manzurola, E., Apelblat, A., Markovits, G., Levy, O., 1989. Mixed-metal
hydroxycarboxylic acid complexes formation constants of complexes of UVI
with FeIII, AlIII, InIII and CuII. J. Chem. Soc., Faraday Trans. 1 85 (2), 373–379.
https://doi.org/10.1039/F198985-00373.
Nayaka, G.P., Manjanna, J., Pai, K.V., Vadavi, R., Kenyd, S.J., Tripathi, V.S., 2015.
Recovery of valuable metal ions from the spent lithium-ion battery using
aqueous mixture of mild organic acids as alternative to mineral acids.
Hydrometallurgy 151, 73–77. https://doi.org/10.1016/j.hydro-met.2014.11.006.
Park, K.S., Sato, W., Grause, G., Kameda, T., Yoshioka, T., 2009. Recovery of indium
from In2O3 and liquid crystal display powder via a chloride volatilization
process using polyvinyl chloride. Thermochim. Acta 493, 105–108. https://doi.
org/10.1016/j.tca.2009.03.003.
Puigdomenech, I., 2004. MEDUSA (Making equilibrium diagrams/using
sophisticated algorithms). Royal Institute of Technology, Stockholm, Sweden.
Savvilotidou, V., Hahladakis, J.N., Gidarakos, E., 2014. Determination of toxic metals
in discarded Liquid Crystal Displays (LCDs). Resour. Conserv. Recycl. 92, 108–
115. https://doi.org/10.1016/j.resconrec.2014.09.002.
Smith, T.D., 1965. Chelates formed by tin (II) with citric and tartaric acids, and their
interaction with certain transition-metal ions. J. Chem. Soc. (Resumed), 2145–
2150. https://doi.org/10.1039/JR9650002145.
Wang, X., Lu, X., Zhang, S., 2013. Study on the waste liquid crystal display
treatment: focus on the resource recovery. J. Hazard. Mater. 244–245, 342–347.
https://doi.org/10.10-16/j.jhazmat.2012.11.059.
Yang, J., Retegan, T., Ekberg, C., 2013. Indium recovery from discarded LCD panel
glass by solvent extraction. Hydrometallurgy 137, 68–77. https://doi.org/
10.1016/j.hydromet.2013-.05.008.
Yang, J., Ekberg, C., Retegan, T., 2014. Optimization of indium recovery and
separation from LCD waste by solvent extraction with bis (2-ethylhexyl)
phosphate (D2EHPA). Int. J. Chem. Eng. 2014, 1–9. https://doi.org/10.1155/
2014/186768.
Yoshida, H., Izhar, S., Nishio, E., Utsumi, Y., Kakimori, N., Feridoun, S.A., 2014.
Recovery of indium from TFT and CF glasses in LCD panel wastes using sub-
critical water. Sol. Energy Mater. Sol. Cells 125, 14–19. https://doi.org/10.1016/
j.solmat.2014.02.009.
Yang, J., Lu, B., Xu, C., 2008. WEEE flow and mitigating measures in China. Waste
Manage. 28, 1589–1597. https://doi.org/10.1016/j.wasman.2007.08.019.