Waste Management xxx (2017) xxxxxx

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Waste Management
j o u r n a l h o m e p a ge : w w w.e l s e v i e r.c o m / l o c a t e / w a s m a n

A novel approach for reducing toxic emissions during high temperature

processing of electronic waste
R. Saini a,b, R. Khanna b,, R.K. Dutta a,c, R. Cayumil b, M. Ikram-Ul-Haq b, V. Agarwala a, G. Ellamparuthy
d
, K. Jayasankar d, P.S. Mukherjee d, V. Sahajwalla b
a
Centre of Excellence: Nanotechnology, Indian Institute of Technology Roorkee, Roorkee 247667, India
b
Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia
c
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, India
d
Institute of Minerals and Materials Technology (CSIR), Bhubaneswar 751013, Odisha, India

a r t i c l e i n f o a b s t r a c t
Article history: A novel approach is presented to capture some of the potentially toxic elements (PTEs), other particulates
Received 27 July 2016
and emissions during the heat treatment of e-waste using alumina adsorbents. Waste PCBs from mobile
Revised 19 January 2017
phones were mechanically crushed to sizes less than 1 mm; their thermal degradation was investigated
Accepted 19 February 2017
Available online xxxx
using thermo-gravimetric analysis. Observed weight loss was attributed to the degradation of polymers
and the vaporization of organic constituents and volatile metals. The sample assembly containing PCB
powder and adsorbent was heat treated at 600 C for times ranging between 10 and 30 min with air,
Keywords:
nitrogen and argon as carrier gases. Weight gains up to 17% were recorded in the adsorbent thereby
E-waste
Potentially toxic emissions indicating the capture of significant amounts of particulates. The highest level of adsorption was
Particulates observed in N2 atmosphere for small particle sizes of alumina. SEM/EDS results on the adsorbent indi-
Adsorbent cated the presence of Cu, Pb, Si, Mg and C. These studies were supplemented with ICP-OES analysis to
determine the extent of various species captured as a function of operating parameters. This innovative,
low-cost approach has the potential for utilization in the informal sector and/or developing countries,
and could play a significant role in reducing toxic emissions from e-waste processing towards environ-
mentally safe limits.
2017 Elsevier Ltd. All rights reserved.

1. Introduction later recycled, incinerated or deposited in a landfill. Discarded e-

Regular induction of new designs and rapid technology
upgrades in consumer electronics such as mobile phones, comput-
ers, TVs and notebooks, followed by intense global marketing is
causing the early obsolescence of a large number of electronic
items. Electronic waste (e-waste) is one of the fastest growing solid
waste streams in the world; in 2014, nearly 41.8 million metric
tonnes of obsolete equipment was generated worldwide (Bald
et al., 2015). Both formal and informal sectors are engaged around
the world in recycling such e-waste to recover precious and
other metals (up to 4070% value) (Cui and Roven, 2011; Marques
et al.,
2013). Waste printed circuit boards (PCBs), the central component
of electronic devices, contain significant amounts of hazardous/-
toxic constituents in addition to a variety of metals, ceramics and
polymers. Various hazards associated with e-waste arise when
the equipment reaches its end-of-life and is disassembled, and
Corresponding author.
E-mail address: ritakhanna@unsw.edu.au (R. Khanna).
devices contain elements that can pose a risk to human health
and the environment over extended exposure.
With a current recycling rate of only 1018%, most of the dis-
carded electronic equipment is either trashed in landfills or incin-
erated (APC, 2000; Pinto, 2008). Recycling waste PCBs in an
environmentally sustainable manner is a challenging issue. Various
e-waste recycling methods used in the informal sector include
manual dismantling, open burning, chipping, melting, burning
wires to recover copper, acid & cyanide salt leaching, and other
inadequate metallurgical treatments (Dwivedy and Mittal, 2012;
Leung et al., 2015; Li et al., 2015). These activities can release dust
particles loaded with potentially toxic elements (PTEs) and flame
retardants into the atmosphere that may re-deposit near the
emis- sion site, or be transported over long distances depending
on the particulate size (de Oliveira et al., 2012; Seplveda et al.,
2010). The term PTE is collectively used to represent elements
such as Zn, Cu, Ni, Cd, Pb, Hg, Cr, Mo, Se and As, known to
accumulate, per- sist and contaminate soils and the environment;
and could have a detrimental influence on human health (Xie
et al., 2012). Poor

http://dx.doi.org/10.1016/j.wasman.2017.02.023
0956-053X/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Saini, R., et al. A novel approach for reducing toxic emissions during high temperature processing of electronic waste.
Waste Management (2017), http://dx.doi.org/10.1016/j.wasma n.2017.02.023
recycling techniques, especially in developing countries, generate associated with high temperature processing of waste PCBs. The
high levels of environmental pollution that affect both the key challenge here was to develop an environmen-
ecosys- tems and the health of population living near the main
recycling areas (Song and Li, 2014; Zhang et al., 2012).
The environmental fate of particulates, fumes and ashes from
burning activities is similar to that of dismantling dust, with toxic
pollutants such as dioxins, furans, lead and other metals ending up
in soil, ground water and the atmosphere (Stenvall et al., 2013;
Wang and Xu, 2014; Widmer et al., 2005). During controlled pyrol-
ysis of waste PCBs in the temperature range 7501550 C, Rajarao
et al. (2014) observed that more than 90% of the lead present was
lost as emissions during heating to 750 C itself; several other
met- als showed a similar behaviour. The loss of hazardous/other
metals and PTEs as emissions is a serious issue, especially during
uncon- trolled/open burning of waste, causing significant
environmental pollution (Breivik et al., 2014; Fromme et al.,
2016; Ren et al.,
2014). A number of studies have been reported in the literature
on the capture of hazardous metals such as Pb, Cd and Zn from
var- ious incineration processes (Abanades et al., 2002; Srum
et al.,
2004; Uberoi and Shadman, 1991). While high temperatures have
routinely been used to treat different types of wastes (Kim, 2001;
San Miguel et al., 2002; Velghe et al., 2011), not much attention
has been paid towards capturing released particulate matter or
on limiting associated environmental contamination. Most e-
waste recycling activities have been focussed primarily on the
recovery of valuable and other materials from e-waste
(Hagelken, 2006; Cui and Roven, 2011), with limited attention
paid to the environmental sustainability of the processes used
(Bhutta et al., 2011; Bridgen et al., 2005).
Along with the generation of harmful emissions during e-waste
processing, the release of toxic ingredients over an extended period
can pose serious threats to the health and the environment
(Tanskanen, 2013). Ellamparuthy et al. (2017) have investigated
the recycling of waste PCBs at high temperatures (up to 1500 C)
using thermal plasma and have characterized airborne particulates
in the exhaust gas captured in gas-bag filters. Particulate sizes
were found to range between 3 and 200 mm; a high concentration
of carbon was detected along with oxides, metals and other impu-
rities. Results showed clear evidence for the presence of metals
such as Cu, Al, Fe, Sn, Zn, Ni; hazardous metals such as Pb, Sb, As,
Cd, and several other elements in trace amounts. To capture such
metals, PTEs and other harmful emissions, extensive gas cleaning
systems/filters have become integral components of e-waste recy-
cling in developed countries (Chiang and Lin, 2014; Lpez-Fonseca
et al., 2010); these are however rarely used in the informal sector
or in developing countries due to inadequate legislation, cost fac-
tors and technological issues.
Over the past several years, our group has been working
actively on developing optimal e-waste recycling approaches,
including the recovery of copper (Cayumil et al., 2014, 2017),
con- centrating precious metals in small volumes (Cayumil et al.,
2015), the generation of novel carbons, fibers and foams from
waste PCBs (Khanna et al., 2015; Sahajwalla et al., 2015), etc.
During our e- waste recycling studies, we have developed a
novel approach to capture some of the toxic gases/particulates,
metal fumes or dusts generated during the heat treatment of e-
waste. In this study, we report an in-depth investigation on
capturing metal particulates present in the exhaust gas using
alumina adsorbents. Alumina adsorbents have previously been
used to remove heavy metal ions from waste water; this
approach offered simplicity of approach, low costs, high removal
efficiency and operational convenience (Afkhami et al., 2010).
Along with detailed results on captured par- ticulates, optimal
operating conditions were also determined towards enhancing
particulate removal and lowering the environ- mental pollution
tally sustainable approach for processing e-waste that could be
implemented in developing and transitional economies in a cost-
effective and energy-efficient manner.

2. Experimental

Waste PCBs used in this study were taken from a range of end
of life mobile phones. These were crushed and mechanically
size reduced to powder sizes of less than 1 mm. As a first step, the
ther- mal degradation behaviour of these powders was
investigated using thermo-gravimetric analysis (TGA-DTG) using
nitrogen as carrier gas (flow rate: 0.2 L/min). TGA investigations
were carried out to establish the thermal region of maximum gas
release and associated weight loss. Significant amounts of gas
release were expected due to polymer degradation in waste
PCBs; the release of these gases may cause fine particles to
become airborne and be carried away with the flowing N2 gas.
Secondly, the vapour pressures of some volatile metals could
become significant at high operating temperatures of the furnace
resulting in their loss in the vapour phase. TGA results on the
system are shown in Fig. 1. A 20% weight loss was observed in the
temperature range of 300400 C with a further gradual weight
loss up to 6% in the temperature range between 400 C and 700
C. This gradual weight loss contin- ued up to 1200 C without
much change in slope. It was therefore decided to carry out gas
adsorption studies at 600 C as most of the gas release is likely to
have occurred by this stage. This tempera- ture lies just beyond
the degradation temperature of polymers and the associated
release of volatiles from waste PCBs. It is impor- tant to note that
temperatures 800 C are more appropriate for the recycling of
waste PCBs as the generation of harmful dioxins/- furans
generated from e-waste becomes negligible at these tem-
peratures (Mckay, 2002). However lower temperatures were
chosen in this study to maximise the release of metal particulates
along with gases generated during polymer degradation.
Alumina was used as an adsorbent to capture fine particulates
released during thermal degradation of waste PCB powders. Alu-
mina has previously been used for the adsorption & removal of
metallic phases from aqueous solutions (Afkhami et al., 2010;
Hua et al., 2012). Several factors however need to be taken into
account while choosing an appropriate adsorbent for the gas
phase. These include adsorbent stability at high temperatures,
the rate and capacity for adsorption, low toxicity and easy
disposal (Uberoi and Shadman, 1990). Alumina was chosen as the
adsorbent medium in this investigation due to its highly porous
granular nat- ure, surface area and capacity for adsorption (Gupta
et al., 2011). In addition, it has high thermal stability, and does not
react or decom- pose at the temperatures of this investigation.
Alumina surface is also known to be hydrophilic in nature and
has low adsorption affinity for organic compounds (Afkhami et al.,
2010); these adsor- bents will therefore be suitable for metal
adsorption even in the presence of organic compounds released
during polymer degradation.
Specific features of the alumina adsorbent used in this investi-
gation have been summarised in Table 1. These basic characteris-
tics also include the maximum level of impurities present
initially and the solubility of the adsorbent in a range of solvents.
Three commercially available particle sizes of alumina were used
in this investigation with an aim to identify optimal adsorbent
characteristics. Alumina powders were dried in an oven at 150 C
for 24 h prior to their use. The trapping and the capture of partic-
ulates from waste PCBs was investigated at 600 C using a range of
carrier gases and heating times. A schematic representation of the
experimental arrangement is presented in Fig. 2. A quartz tube fur-
nace was used for the heat treatment of waste PCBs; the furnace
was heated at the rate of 10 C/min to 600 C, maintained there
 R. Saini et al. / Waste Management xxx (2017) xxxxxx 3

338 Cel
0.50
mg/min 140. 0.50
10.00
0

130. 0.00
5.00
0

120.
0.00 0 -0.50

110.
-5.00
DTA uV

mg/min
27 Cel -1.00
99.99 %

TG %
200 Cel

DTG
96.18 % 300
-10.00 Cel 100.
100 Cel
98.82 % 93.05 % 0 -1.50

-15.00
90.0

80.0 -2.00
399 Cel
-20.00 1202
72.61 % 500 Cel
600 Cel
69.44
Cel % 700 58.23 %
Cel
67.99 % 800 70.0
66.81 % 900 Cel
Cel 63.81 % 1000 Cel -2.50
-25.00 65.24 % 61.64 % 1100
Cel
59.70 %
60.0

200 400 600 800 1000 1200

Temp Cel

Fig. 1. Thermal analysis of PCB powders from mobile phones in N2 atmosphere.

Table 1
PCB powder weighing 1 g was placed in an alumina crucible,
Basic characteristics of alumina used in this investigation.
while 2 g of alumina powder as adsorbent was placed in a second
Adsorbent Characteristics alumina crucible. First the crucible containing the sample was
Alumina Aluminium oxide active neutral Activated I-II; positioned inside the furnace, and then the second collector cru-
Make: Merck, pH value: 6.87.8 cible containing the adsorbent was placed atop the sample cru-
Solubility with water 0.2%; Chloride (Cl) 0.05%
cible. Gases released during the heat treatment passed over the
Calcium (Ca) 0.15%
collector crucible. Adsorption studies were conducted by calculat-
ing the % adsorption capacity of the adsorbent as

for periods ranging between 10 and 30 min and then cooled down
slowly. Gases evolving during the thermal treatment were passed
over a collector ceramic crucible containing sub-micron size alu-
mina adsorbent located such that there was sufficient contact area
between the adsorbent and the gases. The unidirectional flow of
gases was maintained at 0.2 L/min with the help of a pressurized
gas cylinder; a compressor was used to maintain the carrier gas
supply to the tubular furnace. For some studies, the stop valve
was closed to achieve a maximum level of contact between the
adsorbent and gases and then opened to let the remaining gas
out.
f Mi
Qe 100
Mi
where Qe is the % adsorption capacity of the adsorbent; Mo, Mi and
Mf respectively represent the initial mass of the adsorbent, the mass
of the adsorbent after heat treatment as a blank run in the absence
of PCB powder, and the final mass of the adsorbent after heat treat-
ment in the presence of PCBs. Mi-Mo represents the weight loss
experienced by the adsorbent during exposure to high tempera-
tures in the absence of PCBs; this mass change is attributed to the
degassing of the adsorbent. Mf -Mi represents the weight gain by
the adsorbent during heat treatment in the presence of PCBs, and
4 R. Saini et al. / Waste Management xxx (2017) xxxxxx

Fig. 2. A schematic representation of the experimental arrangement.

represents a measure of particulates being adsorbed on alumina The adsorption was generally found to decrease with decreasing
adsorbent from gases generated from the waste. The adsorbent particle size, a trend opposite to that observed with N2.
powder was collected after the experiment and analysed using a
range of analytical tools including ICP analysis and SEM/EDS inves-
tigations. All studies were repeated at least three times to enhance
overall reproducibility; the relative deviation was typically within
3.2. Chemical and microscopic analysis of adsorbed particulates
1.5%

An in-depth ICP-OES analysis was carried out on the heat trea-

3. Results and discussion
Detailed results are presented for PCBs heat treated in the pres-
ence of an alumina adsorbent; these studies were carried out using
air, N2 and Ar as carrier gases. During blank adsorbent runs, i.e., in
the absence of PCB powder, the differences in the weight loss of
adsorbent were marginal for N2 and Ar (both 12.5%); however
the weight loss was somewhat lower ( 6%) in air probably due
to reduced levels of adsorbent degassing in air. Weight gains expe-
rienced by the adsorbent after heat treatments in the presence of
PCBs are shown in Tables 24. These findings have also been
graphically represented in Figs. 35 for ease of comparison and
for establishing various trends. These observations are discussed
in detail in following sections.
3.1. Adsorption behaviour
Table 2 and Fig. 3 represent results obtained after heat treating
alumina adsorbent in the presence (and in the absence) of waste
PCBs for time periods ranging between 10 and 30 min. With air
as a carrier gas, the weight loss of the adsorbent in the blank run
remained fairly constant over the heating time and different parti-
cle sizes of alumina. The extent of impurity adsorption was 6%
for most particle sizes for times up to 20 min. An increase to
8.639.55% was observed for smaller sized adsorbent particles dur-
ing extended exposure for 30 min. This increase is attributed to
lar- ger surface area available for surface adsorption and
relatively faster kinetics of adsorption.
Corresponding results for the N2 carrier gas are shown in Table 3
and Fig. 4. Once again, the heating times did not have much influ-
ence on the weight loss of the blank adsorbent, which remained
fairly constant for the times investigated. The extent of adsorption
was relatively small for the largest particle sizes of alumina under
investigation (>53 mm), which was not much affected by the heat-
ing time. However, the extent of adsorption was found to increase
with time for smaller particle sizes of alumina; not much differ-
ence could be observed between two smaller mesh sizes. The
results for the argon carrier gas are shown in Table 4 and Fig. 5.
Highest adsorption was observed for largest particle size
(>53 mm) of alumina; it was also found to increase with time.
ted adsorbents to determine the nature and the extent of various
metallic impurities adsorbed. As a representative example,
detailed results are presented in Fig. 6 for alumina (2045 mm) heat
treated in argon for a range of times. These results show that alu-
mina had preferentially adsorbed several metals, including Cu, Zn,
Sn and Pb. Some of these (e.g. Cu) were captured in the particu-
late/dust form as the vapour pressure of Cu is quite low at
600 C. There was a significant capture of hazardous lead and Sn
after 30 min; their concentrations were determined to be 89 ppm
and 197 ppm respectively. The adsorbent was analysed for several
other metals as well, however these were found to be present in
trace quantities and close to the detection limit of the analytical
technique.
SEM/EDS investigations on alumina (2045 mm) heat treated in
Argon for 30 min are presented in Fig. 7. While the presence of lead
could be clearly identified, the presence of Ca, Si and C in phase A
indicates that some of the ceramic particles and carbon char from
waste PCBs were also captured along with volatiles and particulate
metal phases. These results also provide evidence for the physical
adsorption of impurities (A and B). These particulates were cap-
tured within empty spaces in the adsorbent; there was no visual
evidence of any chemical interaction between these particulates
and the adsorbent. With increased packing and reduced empty
spaces with decreasing alumina particle sizes, this result is in good
agreement with the corresponding weight gain results (Fig. 5).
SEM/EDS results indicate physical adsorption to be the key
mechanism operating under inert conditions. An opposite trend
was observed for both air and N2 carrier gases. With smallest par-
ticles presenting the highest surface area, and coupled with the
possibility of impurities undergoing chemical reactions forming
oxides or nitrides, these results point towards the likelihood of
chemical adsorption taking place in the case of air and N2 gases.
These results indicate that nature of the carrier gas could have
an important role in determining the efficiency and the kinetics
of adsorption/capturing of particulates in the gaseous emissions.
Nitrogen showed one of the highest levels of adsorptions. Being
much cheaper than argon, these results also show that inert condi-
tions may not necessarily be the best or economical approach. Fur-
ther studies are currently underway to determine the influence of
gas flow rates and temperature on gas phase adsorption.

Table 2
An analysis of various weight changes after heat treatment in air atmosphere.

Time PCB before HT PCB Adsorbent before Adsorbent after HT - PCB Adsorbent after HT - Adsorbent net weight Adsorption
(min) (g) after HT HT (g) run (g) Blank run (g) gain (g) capacity (%)
(g)

Alumina (Mesh size > 53 mm)

10 1.09 0.77 2.01 2.00 1.88 0.12 6.35
20 1.03 0.79 2.01 2.00 1.88 0.12 6.47
30 1.04 0.71 2.01 1.98 1.88 0.11 5.62

Alumina (Mesh size 4553 mm)

10 1.01 0.70 2.00 1.98 1.87 0.11 6.00
20 1.08 0.69 2.01 1.98 1.88 0.11 5.64
30 1.00 0.76 2.01 2.06 1.88 0.18 9.55

Alumina (Mesh size 2045 mm)

10 1.01 0.74 2.01 1.96 1.88 0.08 4.28
20 1.08 0.71 2.00 1.98 1.87 0.11 5.63
30 1.02 0.66 2.01 2.04 1.88 0.16 8.63
Table 3
An analysis of various weight changes after heat treatment in N2 atmosphere.

Time PCB before PCB after HT Adsorbent before Adsorbent after HT -PCB Adsorbent after HT - Adsorbent net weight Adsorption
(min) HT (g) (g) HT (g) run (g) Blank run (g) gain (g) capacity (%)

Alumina (Mesh size > 53 mm)

10 1.02 0.72 2.00 1.98 1.75 0.23 13.37
20 1.09 0.77 2.00 1.98 1.75 0.23 12.95
30 1.09 0.75 2.01 1.96 1.75 0.21 11.79

Alumina (Mesh size 4553 mm)

10 1.09 0.76 2.00 2.00 1.75 0.25 14.53
20 1.03 0.72 2.00 1.98 1.75 0.23 13.08
30 1.09 0.77 2.01 2.05 1.75 0.30 17.15

Alumina (Mesh size 2045 mm)

10 1.01 0.79 2.01 1.96 1.75 0.21 11.91
20 1.04 0.76 2.01 2.02 1.76 0.27 15.14
30 1.03 0.75 2.00 2.05 1.75 0.30 17.28

Table 4
An analysis of various weight changes after heat treatment in argon atmosphere.

Time PCB before PCB after HT Adsorbent before Adsorbent after HT - PCB Adsorbent after HT - Adsorbent net weight Adsorption
(min) HT (g) (g) HT (g) run (g) Blank run (g) gain (g) capacity (%)

Alumina (Mesh size > 53 mm)

10 1.01 0.77 2.01 1.97 1.75 0.22 12.70
20 1.04 0.79 2.01 2.01 1.75 0.26 15.13
30 1.01 0.76 2.01 2.06 1.75 0.31 17.46

Alumina (Mesh size 4553 mm)

10 1.04 0.79 2.01 1.98 1.75 0.23 13.04
20 1.02 0.76 2.01 1.96 1.75 0.21 12.21
30 1.02 0.77 2.01 1.99 1.75 0.24 13.51

Alumina (Mesh size 2045 mm)

10 1.01 0.77 2.00 1.95 1.75 0.19 10.98
20 1.01 0.76 2.01 1.94 1.76 0.18 10.46
30 1.02 0.75 2.00 1.95 1.75 0.20 11.72

Fig. 3. % adsorption capacity of alumina adsorbent during heating in air at 600 C Fig. 5. % adsorption capacity of alumina adsorbents during heating in Argon at
in the presence of waste PCBs. 600 C in the presence of waste PCBs.

Fig. 4. % adsorption capacity of alumina adsorbents during heating in Nitrogen at Fig. 6. Various impurities adsorbed on alumina as a function of time as determined
600 C in the presence of waste PCBs. using ICP-OES analysis.
 Fig. 7. SEM/EDS analysis of alumina adsorbent (2045 mm) after heat treatment in Argon, for 30 min in the presence of waste PCBs.

3.3. Discussion vaporization of high

3.3.1. Particulate generation

The use of adsorbents to capture particulate matter present in
gaseous emissions from the pyrolysis of waste PCBs was investi-
gated towards developing environmentally sustainable processing
of e-waste. We have previously reported on an in-depth character-
ization of solid products recovered from the high temperature
pro- cessing of e-waste (Cayumil et al., 2014); main metals
present in waste PCBs, e.g. Cu, Pb and Sn, were recovered in
significant quan- tities in the metallic fractions generated during
the process. It is however quite likely that a small fraction of
these elements may get carried away as fine particulate matter
with the gaseous emis- sions/flow. Exposure of metals to high
temperatures can lead to their volatilization or release as
particulates. Depending on their vapour pressure, some of these
metals can pass in to the gaseous phase either as particulates
or metal fumes (Uberoi and Shadman, 1990). Metallic fumes
from evaporated metals generally condense as very fine
particulates upon cooling and can be difficult to capture with
standard gas filters. Adsorbents, on the other hand, are better
suited towards capturing small sized particulates and volatilized
trace metals, retaining and stabilizing these metallic components
from the gas phase (Biswas and Wu, 1998; Ho et al.,
1994).
During their investigations on capturing various metallic ions
including Pb(II), Cd(II), Cr(III), Ni(III) and Mn(II) from waste water
using alumina adsorbent, Afkhami et al. (2010) had investigated
the influence of contact time on the removal efficiency of the
adsorbent. The optimal contact time between metals and the
adsorbent was determined to be 90 min. The waste water treat-
ment scenario however is relatively static in nature; here the
metal particulates were already dissolved in waste water and
were not being generated during the study. In the present case,
there are two dynamic sources of metal particulates in the gas
phase: firstly the metal particulates being carried along with
gases generated from degrading polymers and from in-situ
vapour pressure metals. Once the polymer degradation reaches
completion, typically under 10 min (Sahajwalla et al., 2015), there
will be very little gas generation in-situ, and the associated flow of
loose metal particulates. With gases flowing continuously over the
adsorbent surface, the metal particulates spend a limited time
with the adsorbent. The rapidness & the kinetics of binding,
and the affinities of various metals with appropriate binders
therefore assume great significance in capturing impurities.

3.3.2. Factors influencing adsorption efficiency

Several factors have to be considered while choosing appropri-
ate adsorbents for the removal of PTEs and other compounds from
the gas phase. These include adsorbent stability at high tempera-
tures, the rate and capacity for adsorption, low toxicity and easy
disposal (Uberoi and Shadman, 1990). Alumina was chosen as
the adsorbent medium in this investigation due to its highly por-
ous granular nature, high thermal stability, and capacity for
adsorption (Gupta et al., 2011). In addition, the alumina surface
is known to be hydrophilic in nature and has low adsorption affin-
ity for organic compounds (Afkhami et al., 2010); these adsorbents
will therefore be suitable for metal adsorption even in the
presence of organic compounds released during polymer
degradation.
Three particle sizes of alumina were examined for operations
with three carrier gases. No well-defined trends could be observed
on the influence of particle size. Due to their high surface area, the
extent of adsorption was generally found to be somewhat higher
for smaller particles as compared to larger particles. The processing
time was found to be an important factor especially under air and
N2 atmospheres. Abanades et al. (2002) investigated the release of
three heavy metals (Pb, Cd and Zn) from municipal solid waste.
These authors reported that these metals were likely to vaporize
upon exposure to high temperatures (850 C), with their vapors
later condensing to form particulates that may either deposit or
be adsorbed on the adsorbent surface. Such a precipitation could
have occurred in this study as well, as significant levels of adsor-
bent weight gains were observed at longer times. However, due
to continuously flowing gases, it is also possible that a certain frac- get blocked by ash oxides or other organic matter be released in
tion of these vapors gets carried away by the carrier gas. Such presence of oxygen (San Miguel et al., 2002).
con- densation or precipitation is more likely in the absence of
continuously flowing gases or at very low flow rates.

3.3.3. Role of gaseous atmosphere

The capture of metals from high temperature processes using
alumina adsorbent has been previously reported in the literature
(Pacyna and Ottar, 2012). Smaller alumina particles with higher
exposed surfaces showed higher levels of adsorption. Most of these
studies were carried out on highly volatile metals, such as lead
and cadmium. Other metals present in e-waste that are known to
vola- tilize include selenium, boron, nickel, arsenic, cadmium, tin,
anti- mony, and bismuth. Uberoi and Shadman have reported
that alumina effectively adsorbed lead under an oxidizing
atmosphere; the flue gas had a composition of 15% CO2, 3% O2,
80% N2 and 2% H2O, while the temperatures used for the source
were 495 C and
700 C (Uberoi and Shadman, 1990). When lead is captured in
the alumina matrix, it is very difficult to release it. Zinc also
showed a high level of adhesion with the adsorbent with low
levels of subsequent release and volatilization. Equilibrium
calculations have shown a good adhesion of metals such with
As, Be, Cd, Co, Cr, Hg, Ni, Mn, Pb, Sb and Se with adsorbents such as
alumina, silica and ferrites (Biswas and Wu, 1998). While the
release and the regeneration of these metals from the adsorbent
is important from the perspectives of material recovery, reuse of
adsorbents and pro- cess economics; our focus in this study is to
minimize the release of these metal particulates/fumes in the
atmosphere and their detrimental influence on health and the
environment. Non- biodegradable copper is known to be toxic
and carcinogenic and cause neurotoxicity and kidney failure. On
the other hand exposure to Ni can cause skin irritation and
damage to nervous system and lungs; and exposure to Zn is
associated with gastrointestinal issues (Soffioti and Wagoner,
1976; Parmar and Thakur, 2013).
The adhesion of various metals with alumina has also been
found to depend strongly on the presence of chlorine and atmo-
spheric conditions. Inert atmosphere appears to encourage the sta-
bilization of metals in the solid fraction, and therefore reducing
their release as particulate matter. If these do get released, inert
conditions promote their retention in the adsorbent. When metals
are captured by a porous mineral material, these prefer to undergo
solid state reactions with the mixture instead of being released as
vapours. However, in the presence of chlorine, metals tend to
form volatile metallic chlorides and could get released in the
atmo- sphere (Abanades et al., 2002). Adsorption is therefore less
effec- tive in presence of chlorine, as indicated by the
formation of aerosols and soluble compounds (Biswas and Wu,
1998). Lead forms highly volatile lead chloride in the presence of
chlorine, with has a higher volatility than either Pb or PbO
(Scotto et al., 1994).
Three types of carrier gases were used in this investigation. The
use of inert carrier gases significant increased the adsorption as
compared to air; negligible differences were observed in the
adsorption behaviour between argon and nitrogen. As N2 gas is
much cheaper than Ar gas, the use of nitrogen could be a preferred
option without any detrimental influence on the overall adsorption
and the capture of particulates. As mentioned previously, inert
atmosphere stimulates the settlement of these metals into the
adsorbent surface. For example, the regeneration of spent carbons
is carried out through pyrolysis at temperatures around 800 C, as
the organic matter blocking pores is volatilized and eliminated. On
the other hand, when using air, some of the adsorbent pores might
4. Conclusions

This investigation has shown that metal fumes, dust particles,

and hazardous constituents could be captured by using
adsorbents during the processing of e-waste. Key findings of this
investigation are summarised below:

1. This study presents the successful use of alumina adsorbent for

capturing a range of PTEs emitted, including 89 ppm of lead,
197 ppm of tin and trace amounts of Cu and Zn. These undesir-
able/toxic constituents would otherwise be released to the sur-
rounding atmosphere along with gaseous emissions causing
serious environmental pollution and health issues over
extended periods.
2. Although smallest alumina particle sizes generally showed the
highest amount of adsorption, the influence of adsorbent parti-
cle size was generally found to be marginal. Adsorption was
found to increase with increasing contact times between gases
and the adsorbent.
3. The nature of carrier gases, i.e., air, nitrogen and argon, was
found to play a significant role in determining the adsorption
capacity. With N2 generally showing highest levels of adsorp-
tion, the adsorption was found be lowest in case of air.
4. Further studies are currently underway to optimize this
process by testing a number of other adsorbents on different
types of PCBs, at a range of temperatures, contact times, gas
flow rates, etc. and on capturing a wide range of metals. A
battery of adsor- bents may also be used in series to reduce
metal particulates/- toxic elements further in outgoing gases.
5. This investigation presents a novel concept in enhancing the
environmental sustainability of e-waste recycling approaches.
This low-cost method could find application in the informal
sec- tor, in developing economies and has the potential to play
a sig- nificant role in reducing pollution associated with
recycling e- waste.

Acknowledgements

Authors gratefully acknowledge Department of Science and

Technology (DST) India and Department of Industry, Innovation,
Science, Research and Tertiary Education, Australia for providing
financial support for this project under the Australia-India Strate-
gic Research Fund Round 6. The authors would like to express their
gratitude to the Institute Instrumentation Centre of IIT Roorkee
for the utilization of instrumental facilities, and for the technical
sup- port of the Electron Microscope units and ICP Laboratory
of the Mark Wainwright Analytical Centre, University of New
South Wales Sydney.

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