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Phys. Status Solidi C 13, No. 1012, 979983 (2016) / DOI 10.1002/pssc.201600114
Secondary indium production
from end-of-life liquid crystal displays
Alessia Amato, Laura Rocchetti, Viviana Fonti, Maria Letizia Ruello, and Francesca Beolchini*
Universit Politecnica of Marche, DISVA, Via Brecce Bianche, 60131 Ancona, Italy
Received 13 July 2016, revised 26 July 2016, accepted 27 July 2016
Published online 13 September 2016
Keywords end-of-life LCD, environmental impact, indium, life cycle assessment
* Corresponding author: e-mail f.beolchini@univpm.it
In 2014, the European Union identified 20 raw materials
critical for economic importance and high supply risk.
Indium, used in several innovative technologies, is
among such critical raw materials. Generally, it is mined
as a by-product of zinc from a mineral named sphalerite,
with a concentration between 1 and 100 ppm. Currently,
the largest producer of indium is China and about 84% of
the worldwide indium consumption is used for liquid
crystal display (LCD) production, in particular to form an
indium-tin-oxide (ITO) film with transparent conductor
properties. The fast evolution of LCD technologies
caused a double effect: the growth of indium demand and
an increase of waste electrical and electronic equipment
(WEEE). Considering these two factors, the aim of this
study is to make the end-of-life LCDs a secondary in-
1 Introduction The European Commission identified
some criteria to classify the critical raw materials and made
a document where 20 critical raw materials were identified.
Following the guidelines, indium was inserted in this list
on the basis of its high supply risk and high economic im-
portance [1]. Indium relevance is connected with the man-
ufacture of electric and electronic equipment (EEE): in
particular, about 84% of the worldwide consumption is due
to liquid crystal display (LCD) production [2]. This metal
is located, with a percentage of 90% [3], in an indium-tin-
oxide (ITO) thin film with the characteristics of a transpar-
ent electrode [4]. Generally, indium is co-extracted from
zinc minerals, where it is present with variable concentra-
tions included between 1 and 100 ppm [5]. The low con-
centration of indium in the ore justifies the interest for end-
of-life LCDs, that show an indium content in a range of
100-200 ppm [6]. Besides the relatively high content of in-
dium, LCDs are interesting for their short medium lifetime,
around 3-8 years [7], that causes a significant increase of
status
physica
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current topics in solid state physics
dium resource. With this purpose, an indium recovery
process was developed carrying out an acidic leaching,
followed by a zinc cementation. The first step allowed a
complete indium extraction using 2M sulfuric acid at
80 C for 10 min. The problem of low indium concentra-
tion in the scraps (around 150 ppm) was overcome using
a cross-current configuration in the leaching phase that
allowed an increase of metal concentration and a de-
crease of reagents consumption. An indium recovery
higher than 90% was obtained in the final cementation
step, using 5 g/L of zinc powder at pH 3 and 55 C for
10 min. Considering its high efficiency, this process is
promising in a context of circular economy, where a
waste becomes a resource.
2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
LCD waste to treat. At present, different processes for in-
dium recovery were developed including several tech-
niques, as chlorination reaction [2, 8], electro etching [9],
pyrolysis [10], acid leaching followed by solvent extrac-
tion and stripping [11-15] or cementation [3]. All treat-
ments found in the scientific literature were performed at
the best conditions, showing different efficiencies and
treatment costs. The present work describes an indium re-
covery process from end-of-life LCD that includes leach-
ing carried out using sulfuric acid, followed by a zinc ce-
mentation. The treatment allows a complete indium recov-
ery in a very short time and its sustainability is improved
with a cross-leaching configuration that increases the metal
concentration in the leach liquor, reducing the reagents
consumption and the wastewater. In order to evaluate the
environmental impact of the developed process, a life cycle
assessment (LCA) is carried out to identify the steps with
the highest environmental load, also highlighting the posi-
tive effect of the cross-leaching configuration.
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980 A. Amato et al.: Secondary indium production from end-of-life liquid crystal displays

2 Materials and methods 2.4 Environmental impact evaluation Figure 1

2.1 End-of-life LCD characterization With the
aim of obtaining a representative characterization of end-
of-life LCDs, we decided to take into account three sam-
ples provided by different companies that collect and treat
waste electric and electronic equipment. LCD panels were
previously ground by a 4-shaft shredder and the biggest
fragments, composed of plastic and glass, without a sig-
nificant metals content, were removed. A final blade grind-
ing of the remaining fraction (about the 90% of the total
amount) allowed to obtain particles with a maximum di-
mension of 10 mm that were treated in the process. Previ-
ous studies [14] showed that additional sieving or separa-
tion were not necessary because all the fractions smaller
than 10 mm, the fine and the coarse materials, contained
indium without significant differences.
summarizes the LCD life cycle, including the production,
the use and the final waste treatment. Nevertheless, the
LCA system boundaries (Fig. 1) took into account only the
panel treatment, after a previous separation of end-of-life
LCD fractions. More in details, in the analysis we com-
pared the impacts obtained treating 90 kg of panel using a
single leaching step treatment with those caused by the in-
novative application of the cross-leaching with three stages,
including wastewater treatment. Deeper considerations are
addressed to the second process configuration in order to
identify the highest criticalities for the environment.

2.2 Recovery treatment The end-of-life LCD

showed an organic content of liquid crystals that could
cause technical problems during the leaching step for their
sticky and gelatinous aspect. A first washing carried out
with deionized water for 30 min with a solid to liquid ratio
(S/L) of 20% allowed the physical removal of this organic
fraction. At the end of this operation, the solid waste was
filtered and treated in the consecutive leaching stage, ap-
plying the best condition identified by Rocchetti et al. [16].
More in details, the LCD amount was treated in a 2 M sul- Figure 1 System boundaries (functional unit: 90 kg of panel cor-
responding to 1 ton of end-of-life LCD).
furic acid solution at 80 C for 10 min on an agitation sys-
tem. The leaching was carried out using a S/L of 20%. Ac-
The end-of-life LCD amount considered for the evaluation
cording to the cross-current configuration, at the end of
is 1 ton, nevertheless, the process described in this work is
this first step, the solid was filtered and 10% of the leach-
performed to treat only the panel, containing the ITO film.
ing solution volume was refreshed with 2 M sulfuric acid
This fraction represents about 9% of the total amount [7],
solution to treat a second amount of waste, at the same
therefore the functional unit selected for LCA is 90 kg of
conditions of the first step. Considering the reduction of
LCD panel. The production processes of the chemicals and
the process efficiency with the increase of leaching steps,
energy were obtained from the database of the GaBi 6 soft-
we decided to carry out three stages. The cementation step
ware (PE International), integrated with the EcoInvent da-
was carried out using the best conditions selected by Roc-
tabase v. 2.01. Energy consumptions due to mixing/ heating
chetti [17]. The leaching solution was heated up to 55-
during leaching and cementation are reported in Table 1.
60 C on an agitation system and solid sodium hydroxide
was added in order to increase the pH value up to 3. When Table 1 Power consumption.
this condition was reached, pure zinc powder was added at
a concentration of 5 g/L and the cementation was carried Step of process Power consumption
out for 10 min. (kWh/kg LCD)
Leaching 0.13
2.3 Chemical analysis Microwave assisted acid di- Cementation 0.06
gestion of the solid samples and inductively coupled plas-
ma (ICP) were carried out to determine indium, tin, gal-
The impacts were evaluated according to the International
lium, aluminium and iron content in the ground LCD pan-
Reference Life Cycle Data System (ILCD) recommenda-
els [18, 19]. On the other hand, the concentration of metals
tion for life cycle impact assessment (LCIA) [21]. Nor-
in the aqueous phase was determined by inductively cou-
malization was carried out according to CML2001 - April
pled plasma-atomic emission spectrometry in accordance
2013, EU25 + 3, and weighting was evaluated following
with EPA [20]. Before the analysis, liquid samples were
CML2001 - December 07, according to the experts of the
centrifuged and diluted 2-fold with a solution of HNO3
Institute for Polymer Testing and Polymer Science (IKP),
(pH 2) to avoid precipitation of metals.
University of Stuttgart, Germany, and referred to southern
Europe.

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Phys. Status Solidi C 13, No. 1012 (2016)
3 Results and discussion
3.1 End-of-life LCD characterization The charac-
terization of three different stocks of end-of-life LCD pro-
duced the results summarized in Table 2. The choice of the
metals to analyse was done on the basis of literature data
and indium, the main target of the recovery process,
showed values similar to those reported by several authors,
included between 100 and 400 ppm [3, 6, 14, 21].
Table 2 Characterization of three different stocks of end-of-life
LCD from different producers.
Stock In Sn Ga Al (%) Fe
1 53 6 260 30 n.a.* 3.3 0.7 3100
600
2 130 30 n.a.* <10 52 600 400
3 110 20 n.a.* <10 n.a.* n.a.*
* Not available.
3.2 Indium recovery treatment The main target of
a cross-current configuration during leaching is the in-
crease of indium concentration in the leaching solution
without a significant reduction of efficiency. Figures 2a, b
report the results obtained for the metals described in Table
2, excluding gallium that did not show a relevant concen-
tration. The efficiencies reported in Fig. 2a prove that
10 min are sufficient to combine a complete indium leach-
ing and a reduced extraction of impurities, with a maxi-
mum of 12% reached by iron. Furthermore, this leaching
time, shorter than what suggested in the literature [3, 23],
allowed to significantly reduce the energy consumption.
On the other hand, Fig. 2b shows the metals concentrations
trend with the number of leaching steps. It can be observed
that after three steps, all metals followed the same trend
and indium increased from a value of 38 mg/L of the first
step to 96 mg/L of the third one. In spite of the low extrac-
tion efficiency, aluminium represents the main critical im-
purity for its concentration, comparable with that of indium.
Nevertheless, the presence of this metal is not a problem
since alloys containing indium and aluminium could have
several applications [24, 25].
Figure 2 Efficiency (a) and metal concentration (b) during the
three steps of the cross-current leaching (leaching operating con-
ditions: 2M sulfuric acid solution, 80C, 10 min for each step).
(Average values of three replicates.)
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Contributed
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981
The next process operation (Fig. 3), including pH adjust-
ment and the cementation by zinc powder, allowed to ob-
tain a complete indium recovery thanks to the low potential
of zinc that promoted the reduction to the metal form. An
efficiency higher than 85% was observed also for alumin-
ium and tin.
Figure 3 Metal recovery efficiencies in the process (cementation
operating conditions: 5 g/L zinc powder, 55 C, pH 3, 10 min).
3.3 LCA The results displayed in this paragraph have
the aim to show the advantages of the cross-current con-
figuration also from an environmental point of view. Fig-
ure 4a-c take into account the categories considered the
most significant for the evaluation: acidification (a), global
warming (b), ozone depletion (c) and resources depletion
(d). The environmental benefit is evident for all the catego-
ries, particularly comparing the single step leaching and
the 2 steps configuration. More specifically, this advantage
can be quantified in the range of 30-40% for all the catego-
ries. It can also be observed that the leaching operation has
the highest contribution, mainly due to the use of sulfuric
acid. On the other hand, the cementation impact is evident
in the category of resources depletion, due to the request of
zinc powder.
Figure 4 Effect of the number of cross-leaching steps on the en-
vironmental impact, in the categories: (a) acidification, (b) global
warming, (c) ozone layer depletion, (f) resources depletion.
(Functional unit: 90 kg of panel corresponding to 1 ton of end-of-
life LCD.)
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status
982 A. Amato et al.: Secondary indium production from end-of-life liquid crystal displays

Considering the satisfying results obtained for the three Acknowledgements This research was carried out within
steps configuration, the achieved data within the LCA the project HydroWEEE-DEMO 308549 funded by the European
characterization phase, were normalized and weighted. Commission.
Two valuable flows, obtained by the panel treatment, are
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