Journal of Cleaner Production 148 (2017) 103e110

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

An efficient extraction of lead metal from waste cathode ray tubes

(CRTs) through mechano-thermal process by using carbon as a
reducing agent
Narendra Singh, Jinhui Li*
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China

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

Article history: An efficient mechano-thermal method was developed for lead removal from the CRTs funnel glass. The
Received 9 May 2016 method comprises the activation of funnel glass with carbon by the planetary ball-milling apparatus. The
Received in revised form mixture has been sintered for different lengths of time. The separation phenomenon was accelerated by
19 December 2016
the thermal treatment in the presence of carbon, the lead oxide (PbO) in a funnel glass quickly reduced
Accepted 21 January 2017
into Pb and assembled on the surface of the glass matrix. With acid leaching, lead was efficiently
Available online 25 January 2017
removed from the treated glass residues. The optimum temperature, carbon powder adding amount, and
holding time were 900
C, 10%, and 30 min, respectively. During the process, more than 99 wt% of lead
Keywords:
Cathode ray tubes
can be volatilized from the funnel glass and 93.60 wt% of lead was removed by the leaching process. The
Mechano-thermal process findings in this study provides an efficient and practical application for CRTs funnel glass detoxification
Recycling and reutilization.
Lead © 2017 Elsevier Ltd. All rights reserved.

1. Introduction
With rapid technological change in display manufacturing
technologies, cathode ray tube (CRT) display technology has been
replaced by new screen technologies such as liquid crystal displays
(Singh et al., 2016a). As a result, the closed loop recycling of CRTs
into CRTs is no longer possible (Gregory et al., 2009; Singh et al.,
2016b). Currently, the worldwide market for CRT has been down-
graded to less than 10 million units on declining demand and
waning supply of core components (Statica, 2015). Therefore, the
generation of waste stream of CRTs devices has seen at the peak in
e-waste around the world (Singh et al., 2016c). According to the
United Nation University, the global quantity of screen waste gen-
eration in 2014 was around 6.3 million tons (Mt) and most of the
screen waste generated in Asia: 2.5 Mt, followed by the highest
screen waste generation in absolute quantities are Europe 1.7 Mt,
America 1.7 Mt, Africa 0.3 Mt and Oceania 0.1 Mt (Balde  et al., 2015).
Therefore, it is necessity requirement to find some alternative
recycling options for end of life CRTs, including their environmen-
tally sound disposal. In the past few years' researcher has discov-
ered some alternative for the waste CRT to utilized in the open loop
recycling process as a raw material for the other glass products
(Dondi et al., 2009; Guo et al., 2010; Singh et al., 2016c). However,
for the open loop recycling of CRT funnel and neck glass is not
suitable for the other glass products to use because of the high lead
content, which is an undesired element in most glass applications
(Herat, 2008; Nnorom et al., 2011; Shaw Environmental, 2013).
Mostly, a CRT device is comprised with a conical shape formed
by three types of glass and the electron gun, that constitutes around
65% of the weight of a television or a computer monitor and is
composed of 85% glass of which the front panel contributes 65%,
funnel 30% and neck glass 5% (Andreola et al., 2007). The lead glass
from the end-of-life CRTs represent a pressing environmental
problem if disposed improperly (Jang and Townsend, 2003;
Nnorom et al., 2011). Naturally, most of the metals are extracted
from minerals and most of them are extracted from an ore by
reduction with carbon or by electrolysis. Therefore, when the metal
oxide loses oxygen, and is consequently reduced. The carbon gains
oxygen, and is therefore oxidized (Chen et al., 2009). For instant,
lead oxide as an example:
Lead (II) oxide þ Carbon / Lead þ Carbon dioxide

Thermal reduction
* Corresponding author. 2PbO ðsÞ þ C ðsÞ ƒƒƒƒƒƒƒƒ! 2Pb ðsÞ þ CO2 ðgÞ
E-mail address: jinhui@tsinghua.edu.cn (J. Li).

http://dx.doi.org/10.1016/j.jclepro.2017.01.122
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
104 N. Singh, J. Li / Journal of Cleaner Production 148 (2017) 103e110

Table 1 then sieved, the obtained glass powder with a particle size
Chemical composition of the investigated funnel dimension range of 150e180 mm was dried at 105
C for 24 h. The
glass by X-ray fluorescence.
chemical composition, determined by using X-ray fluorescence
Elements Weight (%) spectroscopy, the results shown in Table 1.
SiO2 42.86
PbO 35.33 2.2. Activating process
K2O 7.66
Na2O 3.90
Al2O3 2.33
The collected sample of funnel glass was initially broken into the
CaO 2.32 small pieces then after mechanically activated using a planetary
SrO 2.02 ball-mill apparatus (P-7, FRITSCH, Germany). Five grams of the
BaO 1.37 sample was taken into a zirconia pot of 45 mL inner volume with 7
MgO 1.22
zirconia balls of 15 mm in diameter, and the mill was run for
150 min at 15 min grinding and 15 min pause in turn under ambient
atmosphere at rotational speeds of 400 rpm. The pretreated funnel
In order to avoid lead contamination and recover the resources glass, was dried at 105
C for 24 h. Carbon and nitric acid were
metals from the waste CRT devices, in this study we conducted lab supplied from Beijing Chemical Works China. The other chemicals
experiment to remove the lead metal from the CRTs funnel glass were used in experiment exclusive of any additional treatment.
through mechano-thermal process using activated carbon as
reducing agent. Conclusively, the lead successfully extracted from 2.3. Carbon-thermal reduction treatment
the waste CRTs funnel glass, and the main purpose of this study
have been achieved through removal of toxic lead metal from the In this process, 5.0 g amount of activated funnel glass powder
funnel glass which is the main concern for the environment. was equally mixed with 0e20 percent activated carbon powder
Additionally, in the process collected precipitates silica glass ma- through a planetary ball mill. The prepared activated funnel glass
terial can be used as a raw material for non-leaded glass products. and carbon powder mixture was placed in a 45 mL ceramic crucible,
Thus, the method has good practical and industrial application which was then placed in an iron rode inside the electric heating
values. furnace. The carbon powder in the ceramic crucible ensured a
strong reducing environment during the thermal process. The
2. Materials and methods heating furnace was sealed airtight and the mixed powder was
then heated to the preset temperature for 15e60 min, including 15-
2.1. Sample preparation min pre-setup temperature to maintain mounting temperature
value for each of the samples. The maximum operation tempera-
The sample of CRT funnel glass was provided by the Henan ture used in this experiment was 900
C. Therefore, the highest
Ancai Gaoke Corporation. Initially, the funnel glass block was temperature in this study was limited to 900
C. Experiments were
broken into small pieces and then coatings on the glass surface completely operated at normal atmospheric pressure. In the
were cleaned by wet scrubbing and ultrasonic method. The experiment the examined temperatures range were from 600 to
coarsely glass block were powdered by using dry ball-milling, and 900
C and the carbon powder adding amounts were 0%, 5%, 10%,

Fig. 1. Schematic diagram of lead removal through mechano-thermal process for waste CRT funnel glass.
 Fig. 2. SEM images of CRT funnel glass: (A) raw material, (B) Mechanical activation (B) activated sample at the speed of 500 rpm.

Fig. 3. Images of the after the mechano-thermal treatment at 900
C temperature and 30 min holding time. (A) 0% Carbon; (B) 5% Carbon; (C) 10% Carbon; (D) 15% Carbon; (E) 20%
Carbon.
106 N. Singh, J. Li / Journal of Cleaner Production 148 (2017) 103e110

Fig. 4. SEM images of the residue after the treatment, fixed at 900
C and 30 min holding time. (A) carbon adding amount ¼ 10%; (B) carbon adding amount ¼ 20%.

Fig. 5. SEM images of the residue treated at 10% carbon and 30 min holding time. (A) 600
C; (B) 800
C; (C) 1000
C (D) 900
C.

15%, and 20% and the holding periods were 15, 30, 45, and 60 min.
After the thermal treatment of each samples, the heating chamber
was gradually cooled down to room temperature and the residue in
the iron rode was taken out from the furnace, then weighed, and
stored in a safe place for further analysis.
HNO3 (5 mol/L) and then agitated at 90
C for 30min. The solid
residue was then separated from the leaching solution by vacuum
filtration and then dried at 105
C for 24 h.
2.5. Characterization of the samples

2.4. Acid leaching
In this process, the mixture of funnel glass and carbon powder
after the mechanoethermal reduction might be melted into block
form but it is mainly depending on the adding amount of carbon
powder, if the carbon powder adding amount is less than 10%, then
it will be in the block form and obtained residue should have
required to pulverize again through milling. While, the carbon
powder adding amount is more than 10%, then the obtained residue
can be easily formed into powder through mortar and pestle. Then,
1.0 g residue powder obtained from mechano-thermal process was
taken into a 100 mL Teflon digestion bottle that contained 15 mL of
The funnel glass powder before and after the activation and
obtained precipitates were digested in HNO3 þ HCLO þ HF and then
obtained aqueous solution quantitatively analyzed by the induc-
tively coupled plasma atomic emission spectrometry (ICP-AES:
OPTIMA 3300DV) for the available lead metal. Similarly, leaching
aqueous solution was quantitatively analyzed by ICP- AES after each
treatment. In the reduction process, lead oxide was first reduced to
the element lead and was evaporated at a high temperature.
Therefore, lead removal rate can be divided into two parts: vola-
tilization rate and acid leaching rate. Lead volatilization rates and
acid leaching rates were calculated according to lead content before
and after carbon-thermal reduction and acid leaching, respectively.
 N. Singh, J. Li / Journal of Cleaner Production 148 (2017) 103e110
Fig. 6. XRD patterns of before and after the treatment fixed at 10% carbon and 30 min
holding time.
The obtained filtered residue of glassy compounds after each
treatment were identified by X-ray diffractometer over an angle of
20
< 2q < 90
(XRD: MAX2500) using Ni-filtered Cu K radiation.
The morphology of the funnel glass powdery particles before and
after the mechano-chemical treatment was observed by the scan-
ning electron microscope (SEM: JSM-6330F, JEOL). At the same time
as the microstructural observation of lead-glass powdery particles,
the element analysis on particle surface was performed by the
energy-dispersive X-ray spectroscopy (EDS: JED-2140, JEOL). All
experiments mean value are reported, as several times repetition of
the experiment. The measurement errors were around ±1%.
3. Results and discussion
3.1. Characterization of the samples
In order to understand the structural and surface morphology of
the funnel glass used in the experiment, the funnel glass is shown
in Fig. 2. As we can see here that the activated sample in the SEM
image is very fine if compared to raw funnel glass, and it is in a state
of agglomeration typical phenomenon observed with mechanically
Fig. 7. SEM and EDS image of the residue after acid leaching, with temperature, reducing agent, and holding time fixed at 900
C, 10%, and 30 min, respectively.
107
activated samples. It is most important to understand that what has
happened with the activated sample and the relationship between
the activation-induced structural changes and the enhanced
dissolution because it has been observed that the exothermicity of
carbon reduction is reduced by activation of the powders and the
exothermic peak shifts to lower temperatures after activation
during planetary ball milling.Fig. 1
The residues obtained after the mechano-thermal treatment
given in Fig. 3, shows the effect of temperature and carbon adding
amounts with funnel glass powder. As the result shows that the
funnel glass powder was completely melted in the absence of
carbon at 900
C and partially melted with 5% of carbon addition.
Whereas, with the carbon addition in the glass powder, the adhe-
sion of glass powder was then decreased with an increase in carbon
adding amounts and more than 10% of carbon addition with the
glass powder was enough to prevent the agglomeration of the
melted funnel glass. Besides, Fig. 4 shows that the morphological
effects on funnel glass after different amounts carbon addition. The
added amount of carbon were 10 and 20 percent at 900
C for a
period of 30 min the results show that the glass matrix of different
sizes was observed when carbon powder was added with funnel
glass.
Small irregular particles were observed among the glass mi-
crospheres with an increase of carbon addition amount. These
small irregular particles consisted of carbon powder with a melting
point (>3500
C) much higher than that of the funnel glass so that
most of the glass particles can be isolated by carbon powder to
prevent mutual agglomeration (Mingfei et al., 2016). Therefore, the
configuration of glass matrix was mainly presence of the carbon
powder. If we compare between Fig. 4(A) and (B), it indicates that
smaller glass matrix could be obtained when the carbon adding
amount was increased from 10% to 20%.
Additionally, temperature is another factor that affects the
morphology of the glass matrix's that is shown in Fig. 5 shows the
SEM image of glass matrix obtained at 600e900
C temperature,
10% carbon, and holding time for 30 min. At 600
C, the observed
changes in the funnel glass was not significant because of the lower
heating temperature. Most residues remained as irregular as the
raw funnel glass. The size of these irregular particles ranged from 3
to 15 mm. However, the significant changes appeared when the
temperature was increased to 700
C, glass powder began to appear
molten, and spherical particles of different sizes were obtained and
108 N. Singh, J. Li / Journal of Cleaner Production 148 (2017) 103e110

Fig. 8. Effects on lead removal rate. (a) Temperature (10% carbon and 30 min holding time). (b) Carbon (1200
C and 30 min). (c) Holding time (1200
C and 10% carbon).

major changes observed at 900
C.
3.2. Characteristics of changes in the lead after reduction
Fig. 6 shows the XRD patterns of the funnel glass before and
after treatment residues obtained at different temperatures. In the
figure, the funnel glass before treatment shows a strait line without
any peaks, it is because of the non-crystalline nature of the funnel
glass. While, after treatment crystalline PbO appeared at 600
C.
The diffraction peak of PbO weakened gradually with an increase in
 N. Singh, J. Li / Journal of Cleaner Production 148 (2017) 103e110
temperature. Crystalline Pb appeared at 700
C, and the diffraction
peak of Pb became sharp and increased quickly with an increase in
temperature, particularly when temperature more than 700
C.
Therefore, temperature influences the reduction reaction signifi-
cantly. The formation of Pb can be illustrated as follows: Pb3O4 can
be converted upon heating into PbO and O2 at approximately
500
C (Chen et al., 2009).
Therefore, oxygen was reduced from the funnel glass matrix
during carbon-thermal reduction, it was happened because of
changing the oxidizing environment to a reducing environment.
Since the oxygen reduced from the lead oxide bond, PbO can be
quickly reduced into Pb and detached from the funnel glass; thus,
metallic Pb was formed. Similarly, it was also reported by the other
researcher (Mingfei et al., 2016). Besides, when the temperature
was less than 700
C, only PbO near the surface of the glass particle
can be reduced into Pb. When the temperature more than 700
C,
the funnel glass changed gradually into a liquid state as shown in
Fig. 3. The decrease in molten glass viscosity resulted in more PbO
moving to the surface and reacting with the reducing agent. The
separated metallic Pb can be seen in Fig. 3, which was dispatched at
the top of the residue form the glass matrix during the thermal-
reduction process.
Fig. 3, shows the reduction of PbO was mainly attributed to the
CO2 generated by the reaction of oxygen and carbon powder, which
was placed in the furnace. SEM and EDS were also employed to
further examine the morphology of these metal particles. Funnel
glass particles of varying sizes can be found in Fig. 7. Fig. 5(b) and
Fig. 7 present the SEM images of the residue before and after acid
leaching. A number of spherical holes appeared on the surface of
the glass matrix's in Fig. 7. After thermal reduction, many glass
matrix Pb particles were located on the surface of the glass mi-
crospheres. The generated spherical Pb particles could be removed
efficiently during acid leaching; thus, many circular holes remained
on the surface of the glass matrix shown in Fig. 7. In addition,
during leaching, most of the carbon powder floated on the water
surface because of the density difference between the carbon
powder and water. Thus, the carbon powder that remained in the
residue could be recycled by hydraulic power separation before
acid leaching.
3.3. Effects on lead removal rate
The reduced metallic lead particles on the glass matrix and
glassy powder after mechano-thermal treatment easily could be
recovered by acid leaching. These results also show that the lead
could be evaporated from the surface of the glass phase during the
thermal process as shown in Fig. 3(E). Therefore, the total lead
removal rate can be categorized into evaporation rate and acid
leaching rate. Temperature, holding time, and carbon adding
amount plays an important role in lead removal rate. Fig. 8(a)
shows the lead removal rates at different temperatures when the
carbon adding amount and the holding period were fixed at 10%
and 30 min, respectively. The acid leaching result shows that the
lead removal rate was only almost 45% at 600
C and increased
drastically to 85% at 800
C. At 900
C temperature, the increase in
the lead removal rate subsequently slowed down and reached its
maximum of 90%.
The effects evaporation was very less up to 700
C temperature
but rapidly increased from 3% at 800
C to 10% at 900
C. at the
same time the viscosity of the glass phase decreased quickly with
the increase in temperature, which leads to the quick detachment
of PbO from the glass matrix under high temperature (Yot and
Mear, 2009). Thus, lead removal increased with the increase in
temperature because lead evaporation velocity also increased
markedly with the increase in temperature.
109
Fig. 8(b), shows that the holding time of the treatment signifi-
cantly effects the rate of lead removal, it reached 90% when the
holding time was 15 min, and reached its maximum of 99% when
the holding time was 60 min. Therefore, PbO quickly reduced into
metallic Pb and assemble on the surface of glass under high tem-
peratures. Therefore, the result shows that the holding time
significantly influenced the evaporation rate compare to leaching
extraction rate. When the holding time was 15 min, the lead
evaporation rate was only about 20% and increased drastically to
more than 50% when the holding time was extended to 60 min. The
optimum holding time is determined to be 30 min based on the
extraction and evaporation rate at 900
C temperature and 10%
carbon.
Fig. 8(c) shows the effect of carbon adding amount on the lead
removal rate. About 74 wt% lead was removed without addition of
carbon after only the mechanical activation process and increased
rapidly to 85 wt% when 5% of carbon added. The phenomena of lead
extraction rate reached its maximum of about 93 wt% when the
adding amount was increased up to 15% and became constant.
Besides, the carbon powder has played main role to reduced the
PbO to metallic lead during the thermal-reduction process.
4. Conclusions
In this study, we have successfully achieved lead removal from
CRT funnel glass by mechano-thermal carbon reduction process.
The experimental results show that the temperature, carbon add-
ing amount, and holding time were played vigorous role in the lead
removal from leaded glass. The optimum temperature, carbon
powder adding amount, and holding time for the process were
900
C, 10%, and 30 min, respectively. More than 99 wt% of lead has
been volatilized from the funnel glass and 93.60 wt% of lead was
removed by the leaching process. The collected precipitates after
the filtration was non-leaded glass product which can be used for
various glass products as raw material. The findings in this study
can be applicable for CRTs funnel glass detoxification and
reutilization.
Acknowledgements
The work was financially supported by National Nature Science
Foundation of China (Grant No. 71373141) and National Key Tech-
nology R&D Program (Grant No. 2014BAC03B04).
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