Recovery of Copper

See discussions, stats, and author profiles for this publication at: https://www.researchgate.
net/publication/312346606
High temperature investigations on optimising the recovery of copper from

waste printed circuit boards
Article in Waste Management · January 2017

DOI: 10.1016/j.wasman.2017.01.001
CITATIONS READS
5 107
7 authors, including:
Romina Cayumil Muhammad Ikram Ul Haq

Universidad Andrés Bello UNSW Sydney
18 PUBLICATIONS 167 CITATIONS 27 PUBLICATIONS 140 CITATIONS
SEE PROFILE SEE PROFILE
Rita Khanna Rahul Saini

UNSW Sydney Indian Institute of Technology Roorkee
136 PUBLICATIONS 1,074 CITATIONS 8 PUBLICATIONS 24 CITATIONS
SEE PROFILE SEE PROFILE
Some of the authors of this publication are also working on these related projects:
Recycling of electronic waste for the recovery of value-added materials View project
Materials View project
All content following this page was uploaded by Rita Khanna on 04 January 2018.
The user has requested enhancement of the downloaded file.

Waste Management xxx (2017) xxx–xxx
Contents lists available at ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
High temperature investigations on optimising the recovery of copper

from waste printed circuit boards
R. Cayumil a, M. Ikram-Ul-Haq a, R. Khanna a,⇑, R. Saini a, P.S. Mukherjee b, B.K. Mishra b, V. Sahajwalla a
a
Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia
b
CSIR – Institute of Minerals and Material Technology, Advanced Materials Technology Department, Bhubaneshwar, Orissa 751013, India
a r t i c l e i n f o a b s t r a c t
Article history: High temperature pyrolysis investigations were carried out on waste printed circuit boards (PCBs) in the
Received 23 October 2016 temperature range 800–1000 °C under inert conditions, with an aim to determine optimal operating con-
Revised 2 January 2017 ditions for the recovery of copper. Pyrolysis residues were characterized using ICP-OES analysis, SEM/EDS
Accepted 2 January 2017
and XRD investigations. Copper foils were successfully recovered after pyrolysis at 800 °C for 10–20 min;
Available online xxxx
the levels of Pb and Sn present were found to be quite low and these were generally present near the foil
edges. The relative proportions of Pb and Sn became progressively higher at longer heating times due to
Keywords:
enhanced diffusion of these molten metals in solid copper. While a similar behaviour was observed at
E-waste
PCBs
900 °C, the pyrolysis at 1000 °C resulted in copper forming Cu-Sn-Pb alloys; copper foils could no longer
Pyrolysis be recovered. Optimal conditions were identified for the direct recovery of copper from waste PCBs with
Copper recovery minimal processing. This approach is expected to make significant contributions towards enhancing
Pollution material recovery, process efficiency and the environmental sustainability of recycling e-waste.
Energy efficiency Pyrolysis at lower temperatures, short heating times, coupled with reductions in process steps are
expected to significantly reduce energy consumption and pollution associated with the handling and pro-
cessing of waste PCBs.
Ó 2017 Elsevier Ltd. All rights reserved.
1. Introduction to a materials resource. While the rates for recycling are still quite
low, there is an urgent need to take a critical look at the current e-
High consumption of electronic and electrical equipment (EEE), waste recycling techniques and to optimise the recovery of metals
their short life-spans and subsequent obsolescence has resulted in and other valuable products.
the accumulation of large volumes of electronic waste (e-waste) This article is focussed primarily on optimising the recovery of
worldwide. Rapid technological advancements followed by regular copper from e-waste, one of the main metallic constituents (up to
upgrades of electronic items such as mobile phones, computers, 20 wt%) of waste PCBs. Along with the key aspects of material
TVs, laptops, notebooks etc. are playing a significant role in the recovery, associated waste management perspectives including
generation of such waste. With e-waste volumes increasing at the volumes of wastes processed, energy consumption, secondary
the rate of 4–5% per year, it is one of the fastest growing solid waste generation, and the environmental impact of PCB recycling
waste streams in the world. Nearly 41.8 million tons of e-waste will be discussed. The recovery of copper from e-waste has been
was generated globally in 2014; and the global generation of e- investigated extensively using hydrometallurgical and pyro-
waste in 2018 is expected to be 49.8 Mt (Baldé et al., 2015). metallurgical techniques (Cui and Zhang, 2008; Schluep et al.,
The central components of EEE are printed circuit boards (PCBs), 2009). We first present a brief overview of the current status of
which contain a mixture of polymers, ceramics and metals as part research in the field including techniques/approaches used along
of the boards, circuitry, components, solders, and connectors with details such as the nature/form of copper recovered, the num-
(Lister et al., 2014). With increasing demands for metals, declining ber of process steps, and process efficiency.
mineral resources, costs and environmental impacts associated
with mining and the exploitation of natural resources, there is 1.1. Commercial approaches
immense potential in transforming e-waste from a waste product
Commercial recycling of e-waste is currently carried out in two
⇑ Corresponding author. industrial operations, namely Noranda and Rönnskar as a part of
E-mail address: ritakhanna@unsw.edu.au (R. Khanna). primary copper processing (Veldhuizen and Sippel, 1994). Up to
http://dx.doi.org/10.1016/j.wasman.2017.01.001
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
2 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
14 wt% crushed e-waste is added as an additive/impurity to the 1.3. Pyro-metallurgical techniques

copper ore; the levels of e-waste being recycled are limited by their
influence on furnace operations. Copper present in PCBs is heated Long et al. (2010) heated waste PCBs to 550 °C at a heating rate
at 1250 °C in oxygen-rich atmosphere, converted to copper matte; of 10 °C/min under vacuum, kept these at 550 °C for 2 h followed
high purity copper is then recovered through electro-refining. Umi- by quenching. Solid pyrolysis residues containing glass fibres, cop-
core process uses e-waste (up to 10 wt%) as feedstock for recover- per and carbon were then crushed to fine powders and separated
ing copper and precious metals in the metallic phase, followed by into heavy and light fractions using gravity separation. While up
subsequent purification in a leach–electrowinning plant (Schluep to 99 wt% of copper could be recovered in the heavy fraction, this
et al., 2009). While these processes can be used to recycle large vol- approach required four process steps, and produced secondary
umes of e-waste without producing significant levels of secondary waste in the form of oils and light fractions. Zhou et al. (2007) used
wastes, these multi-stage techniques recover copper in an indirect a multi-stage pyro-metallurgical approach to recover copper and
manner. It is important to note that the copper present initially in other metals. Waste PCBs were mixed with 12 wt% NaOH and heat
waste PCBs generally has quite high purity. These processes how- treated at 1200 °C under reducing atmosphere to produce two
ever treat e-waste as an impurity/copper ore and carry out high types of solid fractions: a metallic fraction containing Fe, Cu, Pb
temperature oxidation of pure copper followed by its reduction and precious metals, and a slag phase containing SiO2, Al2O3 and
and purification in order to extract copper. Some of these processes CaO. The Cu concentrations in the metallic and the slag phase were
were developed nearly 20 years ago, have low energy efficiency/ determined to be 82 wt% and 0.15 wt% respectively. The metallic
productivity and do not represent the state-of-the art recycling fraction was then heat treated at 1200 °C under air; the Cu2O thus
technology. generated was reduced with pyrolysis gas to obtain metallic cop-
per; secondary wastes produced included up to 30% copper as
Cu2O slag.
1.2. Hydrometallurgical techniques Zhan and Xu (2011) crushed waste PCBs in a high speed shear-
ing machine, followed by hammer grinding, sieving and the sepa-
Hydrometallurgy has been used widely to extract copper from ration of metallic and non-metallic fractions using a corona
e-waste; these techniques generally include mechanical process- electrostatic separator, followed by vacuum pyrolysis of these
ing/size reduction followed by extraction through chemical leach- powders at 850 °C. Most of the copper was recovered in the form
ing/reactions. Behnamfard et al. (2013) size reduced waste PCBs in of (Cu, Pb, Sn) alloys containing up to 92.93 wt% Cu, 2.38 wt% Pb,
a hammer crusher followed by pulverisation to particles sizes 3.57 wt% Sn, and small amounts of non-metallic fractions.
300 lm. These powders were then leached in a sulphuric acid Cayumil et al. (2014) carried out high temperature pyrolysis of
solution in the presence of hydrogen peroxide for 3 h/200 rpm/- waste PCB chips in the temperature range 1150–1550 °C for times
room temperature. Up to 85.76 wt% copper was extracted as Cu2+ up to 20 min under argon atmosphere; copper was recovered in
ions in solution; remaining copper could also be recovered through the form of copper rich and lead rich alloys. While pyro-
repeated leachings. However, these solutions contained other metallurgical approaches do not produce much residual waste
metallic ions such as Zn2+, Sn2+, Fe2+ and Ni2+ in addition to copper such as spent acids etc. and can significantly reduce the volumes
ions. Silvas et al. (2015) used a number of process steps including of waste after processing, careful attention needs to be paid to
size reduction, magnetic separation and two chemical leachings the gaseous emissions from PCBs during exposure to high temper-
with H2SO4 and H2SO4/H2O2 to recover copper. Recovered copper atures. The generation of harmful brominated compounds, dioxins,
solution contained Al and Zn as impurities and required further furans from polymer degradation can be a serious issue for pro-
purification/electrowinning steps. Secondary wastes produced cessing at low temperatures. However, the generation of dioxins/-
included magnetic fractions, chemical effluents and residual solids. furans is known to become negligible at temperatures above
Zhang and Zhang (2014) used an eight-step process for the 800 °C (Mckay, 2002).
recovery of copper; waste PCBs were first heat treated at 270 °C
to improve their crushing efficiency. The material was then 1.4. Other approaches
crushed in a hammer mill, followed by air separation. The metallic
fraction obtained in the separation step was mechanically pro- Xiu and Zhang (2009) investigated the recovery of copper from
cessed in a cutting mill to obtain 0.25 mm particle sizes. The mate- waste PCBs using supercritical water oxidation and an electroki-
rial was then leached in a solution of CuSO45H2O and NaCl at netic process. PCBs were size reduced in a cutting mill to get par-
60 °C. After two filtration processes, copper was recovered in the ticles sizes 0.1 mm. The material was then dissolved in solution
form of cupreous chloride. Although 98.5% copper recovery was of distilled water and hydrogen peroxide; and inserted in a reactor
achieved, this approach used a number of process steps, producing consisting of two electrodes and kept at 713 K and 30 MPa for
significant amounts of residual chemicals, spent acids, non- 60 min. Electrodes were then leached in a 5 M HNO3 solution for
metallic fractions, etc. Ou and Li (2015) used mechano-chemistry several hours (overnight). The recovery of copper achieved was
to recover copper, an approach involving the grinding and mixing 84.2%, of which 74% was deposited on the cathode. In this four-
of waste PCB samples with sulphur powder. The mixture was step process, other impurities were present in the spent solutions,
ground in a ball mill for 20 min to form copper sulphide; followed and solid residues were generated as secondary waste. Fogarasi
by leaching into a 3 M sulphuric acid solution containing 30 wt% et al. (2014) investigated the recovery of copper and the concentra-
hydrogen peroxide. While up to 95% copper could be recovered tion of gold from waste PCBs by using electrochemical oxidation
in a solution form, other impurities were also present in this solu- without any mechanical processing. The process consisted of
tion; additional steps were required to recover metallic copper. leaching the samples into an acidic ferric chloride solution (0.3 M
Spent acids and resin residues were generated as secondary waste. HCl + FeCl3) and electrowinning at 4 mA/cm2 density. Up to 99%
While successful in recovering copper, these techniques are copper was recovered in the form of a deposit, along with a gold
severely limited by the volumes of waste processed, significant rich residue. The process was improved further by adjusting the
levels of waste handling/initial processing and by the amounts of flow rate in the leaching step and in the deposit of copper in the
secondary wastes produced, thereby making large scale e-waste EW process (Fogarasi et al., 2015). Bioleaching has been also used
recycling and copper recovery economically and environmentally as an alternative process to recover copper from waste PCBs. How-
unviable. ever, the process took a very long time to leach the metal (Wang
R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx 3
et al., 2009; Yamane et al., 2011), and required an additional pre- lic droplets. The use of inert atmosphere prevented the re-
cipitation step to recover copper from the solution (Chenglong oxidation of metals and the burning of carbons. This single step
et al., 2010). process did not produce any secondary waste, as the carbonaceous
While a number of techniques have been successful in recover- slag phase produced as a side product, was transformed into
ing most of the copper present in waste PCBs, these are still limited value–added carbon foams and fibres (Khanna et al., 2015).
by too much initial handling/mechanical processing, number of However, these pyrolysis temperatures were higher than the
process steps involved, quality/form of copper recovered, sec- melting points of both lead (327.5 °C) and tin (231.9 °C), other
ondary waste generation, emissions as well as environmental con- two key metals present in waste PCBs; these molten metals tended
tamination. Waste PCBs being a valuable/extensive copper to diffuse into molten copper and form Cu-Pb-Sn alloys. As the
resource, there is an urgent need for developing optimal process/ kinetics of diffusion of Pb and Sn is likely to be much slower in
s for efficient copper recovery with minimal side effects or local solid copper, we carried out in-depth investigations on waste PCBs
area contamination. In an previous study by our group (Cayumil at temperatures below the melting point of copper. In this article,
et al., 2014), waste PCB pieces (1 cm2) were heat treated at high we report on the high temperature pyrolysis of waste PCBs in the
temperatures (P1150 °C) for 10–20 min in argon atmosphere. As temperature range 800–1000 °C for 10–60 min in argon atmo-
these temperatures were above the melting point of copper sphere. These temperatures are also high enough to either destroy
(1085 °C), this study was an attempt to melt copper out of the or stop the formation of hazardous emissions such as poly-
PCB matrix. While most of the copper could indeed be extracted, halogenated dioxins (PCDDs/PBDDs) and furans (McKay, 2002;
it was recovered in the form of copper rich and tin-lead rich metal- Striebich et al., 1991). Detailed characterization of pyrolysis resi-
Fig. 1. A schematic representation of the experimental arrangement.
Fig. 2. Representative examples of copper rich products generated after 10, 20, 30 and 60 min of heat treatment of waste PCBs at 800 °C, 900 °C and 1000 °C.
Fig. 3. Relative concentrations of Cu, Pb and Sn in: (A) Copper rich metallic fraction,
(B) Tin/lead rich metallic residue (C) Carbonaceous/slag residue after 10 min of heat
treatment.
Fig. 4B. Influence of heating times on lead and tin concentrations in the copper rich
fractions generated at 800 °C, 900 °C and 1000 °C.
2. Experimental
Waste PCB specimens in this study were taken from a variety of

waste boards such as computers/mobiles/mother boards etc. and
represent a generic e-waste mix. These were size reduced by cut-
ting and manual crushing to typical sizes 1 cm2 and
weights 2 g. Average concentrations of key metals in these raw
PCBs were 13.3% Cu, 4.8% Pb and 3.1% Sn. High temperature
investigations were carried out in a horizontal tube furnace with
inner dimensions as: 1 m length, 5 cm internal diameter, wall
thickness 5 mm (Fig. 1). The temperature near the edges of the fur-
nace (20 cm; the cold zone) was generally 200–300 °C;
Fig. 4A. Influence of heating times on copper concentrations in the copper rich
fractions generated at 800 °C, 900 °C and 1000 °C. whereas the experimental temperatures were maintained in the
central region, (15 cm; the hot zone) with the help of thermocou-
dues was carried out using a variety of analytical techniques. The ples. The furnace tube was purged with 99.99% pure argon
aim of the present investigation is to enhance the quality of copper throughout the duration of the experiment with a flow rate of
recovered from waste PCBs, while optimising the process efficiency 1.0 L/min. The PCB specimens (1 cm2) were placed on an alumina
and the environmental sustainability of the overall process. tray (1 cm 2 cm) and mounted on a sample holder. The assembly
was held in the cold zone for 10 min to avoid thermal shock, and 3. Results
was then inserted into the hot zone of the furnace preventing any
reactions occurring at lower temperatures. The temperatures in the Solid residues recovered after pyrolysis were in the form of red
cold zone were below typical polymer degradation temperatures; and white metallic fractions and a dark carbonaceous slag residue.
the direct insertion of PCB specimens into the hot zone (800– A full characterization of the carbonaceous/slag residue has been
1000 °C) therefore prevented emissions associated with low tem- reported previously (Sahajwalla et al., 2015). Representative exam-
perature polymer degradation as well as the diffusion of Pb and ples of copper rich metallic phases recovered after various heat
Sn into copper during the heating process. The assembly was treatments are shown in Fig. 2. While most of the foils recovered
quenched after fixed periods of reaction time (10–60 min) by with- at 800 °C were coppery red in colour, fractions recovered at higher
drawing the tray into the cold zone of the furnace. Studies were temperatures and longer times had additional dark coloured
carried out at a range of temperatures/time for sake of optimiza- deposits on the foil surfaces. The relative concentration of these
tion. Experiments were repeated at least three times at each tem- deposits was highest after pyrolysis at 1000 °C for 30 and 60 min.
perature/time to enhance the reproducibility of results, and to Further results are given below.
compensate for the initial variability in raw waste specimens.
The deviation on the results could be up to ±5%. Solid products
3.1. Chemical composition of pyrolysis residues
obtained after various heat treatments had phase separated into
a metallic fractions: copper rich red foils/wires/droplets, lead &
Detailed elemental analysis of various fractions was carried out
tin rich white droplets/wires and a dark carbonaceous slag phase.
using ICP-OES. Relative proportions of three main metals, i.e, Cu, Sn
Detailed investigations carried out on metallic phases using tech-
and Pb in the copper rich, lead/tin and carbonaceous residues are
niques such as Scanning Electron Microscopy (SEM)/Energy Dis-
presented in Fig. 3 for a range of pyrolysis temperatures after
persive Spectroscopy (EDS) on model Hitachi 3400X SEM;
10 min of heat treatment. Corresponding results from pyrolysis
elemental analysis using Inductively Coupled Plasma Optical Emis-
at 1250 °C, typical temperature used during commercial recycling
sion Spectrometry (ICP-OES) using model Perkin Elmer Optima
of e-waste, have also been included for sake of comparison. The
7300DV; X-ray diffraction (XRD) on PANanalytical Xpert Multipur-
copper rich fraction (Cu: 87.5%) contained low levels of Pb (0.3%)
pose X-ray Diffraction System. Detailed results on metallic prod-
and Sn (3.1%) after pyrolysis at 800 °C (Fig. 3A). While the corre-
ucts recovered from waste PCBs heat treated at 800–1000 °C for
sponding concentrations of Pb and Sn had increased somewhat at
10–60 min, are presented in the following section.
900 °C and 1000 °C, significantly higher levels of Pb (6.4%) and Sn
Fig. 5. SEM-EDS analysis of copper-rich foils after 20 min of heat treatment at 800 °C.
(9.9%) were observed after pyrolysis at 1250 °C. While the pyroly- 3.2. Electron microscopy investigations
sis temperature did not have much influence on the loss of copper
in the white Pb/Sn rich metal fraction (Fig. 3B), the presence of cop- In-depth SEM-EDS investigations were carried out on the cop-
per in the carbonaceous residue had reduced significantly at lower per rich fractions recovered after various heat treatments. Fig. 5
temperatures: 0.2% at 800 °C as compared to 1.5% at 1250 °C shows a microscopic analysis of a copper rich foil recovered after
(Fig. 3C). Fig. 4A shows the influence of pyrolysis time on the cop- 20 min of heat treatment at 800 °C. Fig. 5a shows a relatively pla-
per recovery in the temperature range 800–1000 °C. These results nar but somewhat granular sheet composed mainly of copper
point towards two specific features. There was a marginal influ- (Fig. 5a; ‘A’) along with trace amounts of Sn and Zn. The regions
ence of heating time on the extent of copper recovered; variations near the edge of the foil showed a lamellar structure; the elemental
observed were typically within statistical errors. It is quite likely composition of this region was very similar to the bulk copper foil.
that most of the copper had already precipitated out of waste PCBs However, a few bright deposits containing small amounts of Pb, Zn,
within the first 10 ten minutes; additional heating for up to 60 min Cu, C and O could also be seen in these areas (Fig. 5b; ‘B’). In addi-
did not serve much purpose. Extended heating at 800 °C was actu- tion, a small number of bright droplets (Fig. 5c; ‘C’), representing
ally detrimental to the quality of copper recovered due to increased molten Cu-Sb alloys were also detected as well; their sizes were
levels of Pb and Sn in the copper foils. Corresponding levels of Pb found to typically range between 1 and 2 lm. The SEM-EDS analy-
and Sn present in copper rich fractions are shown in Fig. 4B. At ses of copper rich fractions obtained after 20 min of heat treatment
800 °C, the concentration/diffusion of lead and tin into copper were at 900 °C are presented in Fig. 6. Instead of the lamellar structure
found to increase with time. While the extent of such an increase observed at 800 °C, the copper foil (Fig. 6a; ‘A’) was overlaid with
was quite small at 900 °C, the corresponding results at 1000 °C a number of metallic droplets (Fig. 6b; ‘B’) and locally melted
showed an increase till 20 min followed by a rapid decrease at regions (Fig. 6c; ‘C’). While the region ‘A’ was almost pure copper,
longer times. This behaviour was attributed to the enhanced the EDS analysis of the region ‘B’ showed Sb-Sn droplets embedded
volatility of both lead and tin at high temperatures, and their loss on the surface of the copper foil. Partially molten and lamellar
in the vapour phase. In addition to these two metals, other metals region ‘C’ was predominantly composed of Pb with trace amounts
such as Ni, Zn, Fe, Al, Mg and precious metals Ag, Au, Pt, Pd were of C and O. In addition, several carbonaceous deposits were also
also present in trace quantities. A detailed report on the behaviour recorded near the edge of copper foils (see top left region in
of precious metals under these operating conditions has been pre- Fig. 6a). These regions represent some of the carbonaceous residue
sented elsewhere (Cayumil et al., 2015). adhering to the copper foils after pyrolysis. A closer look at these
Fig. 7. SEM-EDS images of carbonaceous regions on copper-rich foils after heat treatment at 900 °C.
dark deposits is presented in Fig. 7. These regions contained a large addition, several lead rich partially melted deposits (Fig. 9b; ‘B’)
concentration of Cu-Sb metallic droplets (Fig. 7b; ‘B’), with sizes were also observed on the droplet surface. The composition of
ranging from 2 to 16 lm; these sizes are much larger than corre- the copper recovered was found to evolve with pyrolysis
sponding droplets observed after 800 °C pyrolysis. There were temperature.
additional bright deposits (Fig. 7c; ‘C’) on the surfaces of these dro-
plets; these were primarily composed of Pb, C and O.
3.3. X-ray diffraction investigations
While the copper rich foils were the main product after heat
treatment at 1000 °C, a few copper rich droplets were also pro-
X-ray diffraction analysis was carried out on copper foils recov-
duced indicating the molten state of these alloys at this tempera-
ered after heat treatments at 800 °C and 900 °C for 20 min. The
ture. The SEM-EDS analyses of copper-rich foils and droplets
focus here was on identifying any loss of structural order and pre-
have been presented in Figs. 8 and 9 respectively. The SEM-EDS
ferred orientation, if any, in the copper foils recovered after pyrol-
images of copper foils recovered after pyrolysis at 1000 °C are
ysis. Detailed X-ray diffraction patterns are presented in Fig. 10.
shown in Fig. 8; the results in Fig. 8a–c are shown with increasing
These results show the well-known diffraction pattern for FCC cop-
levels of magnification. Fig. 8a clearly shows the presence of mol-
per; the peak positions and relative intensities of different peaks
ten lead in the grain boundaries on the top surface of the copper
were as per the standard pattern. Except for the presence of a small
foil. Several other deposits could also be seen across the surface;
peak corresponding to PbSb2O6, these results identify the copper
three distinct regions ‘A’, ‘B’, and ‘C’ could clearly be identified.
foils recovered from waste PCBs as being crystalline copper. No
The top surface of the foil (Fig. 8a; ‘A’) was a predominantly Cu-
preferred orientation was observed, thereby indicating the absence
Pb alloy; this result is a significant variation from the pure copper
of localised melting and subsequent solidification of partially
foils recovered at 800 °C and 900 °C. The droplets ‘B’ (Fig. 8b) seen
melted copper in these foils. These X-ray diffraction results are in
on the surface were much depleted in copper and were determined
good agreement, and consistent with ICP and SEM-EDS results on
to be a mixed alloy of Pb and Sn. Deposits of Pb (Fig. 8c; ‘C’) on the
these copper foils, and are indicative of the high quality of copper
top of these droplets appear to represent the precipitation of lead
recovered.
vapour upon quenching. The SEM-EDS images of the copper rich
droplets recovered after 1000 °C pyrolysis are shown in Fig. 9.
The surface region of these primarily Cu-Sn droplets (Fig. 9a; ‘A’) 4. Discussion
was not smooth and appeared to contain several bulges, channels
that appeared to be partially melted regions. A very large number The temperature range (800–1000 °C) used in this investigation
of small droplets were also recorded on the droplet surface. In resulted in the phase separation of pyrolysis products from waste
Fig. 9. SEM-EDS images for copper-rich droplets after 20 min of heat treatment at 1000 °C.
complete physical/chemical separation, and was seen as contain-

ing far too many constituents. Recent developments in the field
are however making consistent efforts towards recovering pre-
cious and other materials, along with reductions in secondary
waste generation and environmental impact. One of the key find-
ings in our earlier study on high temperature pyrolysis of waste
PCBs at P1150 °C (Cayumil et al., 2014), was that the thermal
degradation of polymers, metals and ceramics occurred in different
temperature regimes and that the degradation of these con-
stituents did not interfere much with each other. While the poly-
mer degradation was more or less complete by 600–700 °C; the
segregation of metals from waste PCBs occurred predominantly
in the temperature regime: 700–1400 °C; ceramics and other oxi-
des were still stable at these temperatures and tended to separate
out as residual fractions. Low melting point metals such as Pb and
Sn continued to remain in the metallic phase to a certain extent
and their loss as volatiles became significant only at high temper-
atures. These observations suggest that it may be possible to
untangle the overall complexity of waste PCBs to a great extent
by choosing appropriate operating temperatures and their well-
known material characteristics/behaviour could be exploited
towards optimal material recovery.
There were several key features of this study, which played an
important role in the recovery of copper from waste PCBs in a
single step. The operating temperatures for the pyrolysis of PCBs
under inert atmosphere were chosen in the range 800–1000 °C.
Low temperature (up to 700 °C) pyro-metallurgical approaches
including open burning, incineration, and pyrolysis are known
to have a significant environmental impact in terms of hazardous
and/or toxic emissions and secondary wastes generated. While
Fig. 10. X-ray diffraction analysis of copper-rich foils obtained after heat treatment most of the polymer degradation would have been completed
at 800 °C and 900 °C. by 800 °C; this temperature and operating time (P10 min) is suf-
ficient to completely stop the generation of dioxins/furans from
degrading polymer. However copper, the main metal present in
PCBs into metallic and non-metallic fractions. The metallic phase waste PCBs, will still be solid at 800 °C (M.P. 1085 °C); the diffu-
was generated in the form of ‘red’ foils/droplets and ‘white’ dro- sion of molten Pb and Sn into solid copper is likely to be much
plets, while the non-metallic fraction was in the form of a carbona- slower than their corresponding diffusion in molten copper (e.g.
ceous/slag residue. The elemental analysis of the resulting ‘red’, at 1250 °C; typical temperatures used for copper recovery). The
‘white’ and carbonaceous/slag fractions showed that the concen- upper temperature bound of 1000 °C was chosen to lie below
tration of Pb and Sn in the copper rich fractions was significantly the melting point of copper. However our results show that there
lower than the corresponding results from pyrolysis at 1250 °C was a significant diffusion of both Pb and Sn at this temperature
(Fig. 2). Due to their limited solubility in solid copper, the physical and for longer times at lower temperatures. In this study, PCBs
state of copper (solid vs molten) was found to play an important were inserted directly in the hot temperature zone from the cold
role in the pickup of Pb and Sn by copper during pyrolysis. The zone (200–300 °C) and did not spend any time at intermediate
ICP-OES analysis results in the present investigation were found temperatures. This approach slowed down the diffusion of Pb
to be consistent with these observations. The presence of lead in and Sn and the generation of dioxins/furans at lower tempera-
the copper rich fractions, detected only at 1000 °C is more likely tures. In typical furnaces, it is a common practice to insert spec-
to have been caused by the precipitation of lead vapours than solid imens in the furnace at room temperature and heat these to the
state diffusion. Tin on the other hand has a higher affinity for cop- set temperatures at certain heating rates. The PCBs are thus
per and was present in higher concentrations in copper fractions. A exposed to a wide temperature range and extended heating times
small loss of copper was found to occur in the white droplets that making the segregation of different constituents difficult to
could be attributed to a localised/partial melting of copper or to the control.
difficulty of its separation from Sn at lower temperatures and short Our results from ICP-OES analysis, SEM-EDS and X-ray diffrac-
heating times. Higher levels of localised copper melting were tion have clearly shown that copper foils could be recovered from
observed at 1000 °C as indicated by the formation of Cu-rich dro- waste PCBs in a single step of pyrolysis at 800–900 °C for times
plets. The Pb-Sn solders are a likely source of small amounts of between 10 and 20 min. It was also noticed that the mechanical
Sb present that is known to form solid solution with copper at crushing or powdering of PCBs was not really necessary. Although
these temperatures (Predel, 2012). As antimony is molten at the small PCB pieces (1–2 cm) were used in these laboratory investiga-
operating temperatures (M.P. 630.6 °C), it showed a tendency to tions, these limitations were due to the small size of the furnace
accumulate and concentrate in the copper fraction (Haynes, 2014). used. We have carried out a few studies in larger furnaces where
The focus of earlier research on managing e-waste was primar- an entire PCB or larger pieces of 10 cm 10 cm could be directly
ily on developing recycling approaches as alternatives to landfilling inserted into high temperatures. Sheets of copper were recovered
and incineration. Key issues for these studies were managing large easily from these scaling studies without any difficulty. We also
volumes of waste being produced, reducing their volumes to carried out on some experiments on powdered PCBs; however
manageable proportions and to recover materials wherever possi- the overall phase separation and copper extraction was not very
ble. E-waste was generally regarded as being too complex for a successful in this scenario.
5. Conclusions Cayumil, R., Khanna, R., Ikram-Ul-Haq, M., Rajarao, R., Hill, A., Sahajwalla, V., 2014.
Generation of copper rich metallic phases from waste printed circuit boards.
Waste Manage. (Oxford) 34 (10), 1783–1792.
A number of key results were obtained on optimising the recov- Cayumil, R., Khanna, R., Rajarao, R., Mukherjee, P.S., Sahajwalla, V., 2015.
ery of copper from waste PCBs in the temperature range 800– Concentration of precious metals during their recovery from electronic waste.
Waste Manage. (Oxford).
1000 °C for 10–60 min under inert atmosphere. These are sum-
Chenglong, Z., Yujia, C., Jingwei, W., Jianfeng, B., Yuan, Z., Wenjie, W., Wenxiong, M.,
marised below: 2010. Recovery of copper from bio-leaching solutions of waste printed circuit
boards waste by ion exchange. In: Digital Manufacturing and Automation
(ICDMA), 2010 International Conference on, pp. 138–140.
1. This study has shown that it may be possible to optimise the
Cui, J., Zhang, L., 2008. Metallurgical recovery of metals from electronic waste: a
recovery of copper from waste PCBs through a judicious choice review. J. Hazard. Mater. 158 (2–3), 228–256.
of operating temperatures and heating times. Pyrolysis temper- Fogarasi, S., Imre-Lucaci, F., Egedy, A., Imre-Lucaci, Á., Ilea, P., 2015. Eco-friendly
atures below the melting point of copper and short heating copper recovery process from waste printed circuit boards using Fe 3+/Fe 2+
redox system. Waste Manage. (Oxford) 40, 136–143.
times were found to play an important role in limiting the dif- Fogarasi, S., Imre-Lucaci, F., Imre-Lucaci, Á., Ilea, P., 2014. Copper recovery and gold
fusion/pickup of lead and tin in the copper rich fractions. enrichment from waste printed circuit boards by mediated electrochemical
2. Copper foils with lead and tin levels as low as 0.3% and 3.1% oxidation. J. Hazard. Mater. 273, 215–221.
Haynes, W.M., 2014. CRC Handbook of Chemistry and Physics. CRC Press.
were recovered directly in a single step from the pyrolysis of Khanna, R., Ikram-Ul-Haq, M., Cayumil, R., Rajarao, R., Sahajwalla, V., 2015. Novel
waste PCBs (800 °C, 10 min). Results from the pyrolysis at carbon micro fibers and foams from waste printed circuit boards. Fuel Process.
900 °C were also quite promising. However, the impurity levels Technol. 134, 473–479.
Lister, T.E., Wang, P., Anderko, A., 2014. Recovery of critical and value metals from
in the recovered copper were found to increase with increasing mobile electronics enabled by electrochemical processing. Hydrometallurgy
temperatures and heating times. Low levels of impurities pre- 149, 228–237.
sent in recovered copper are likely to reduce its further refin- Long, L., Sun, S., Zhong, S., Dai, W., Liu, J., Song, W., 2010. Using vacuum pyrolysis
and mechanical processing for recycling waste printed circuit boards. J. Hazard.
ing/processing for commercial applications.
Mater. 177 (1), 626–632.
3. While the loss of copper in Pb-Sn rich white metallic phase was McKay, G., 2002. Dioxin characterisation, formation and minimisation during
unaffected by the pyrolysis temperature, the corresponding loss municipal solid waste (MSW) incineration: review. Chem. Eng. J. 86 (3), 343–
368.
of copper in the carbonaceous phase was significantly lower in
Ou, Z.J., Li, J., 2015. Copper leaching from electronic waste for the improvement of
the temperature range 800–1000 °C as compared to the corre- gold recycling. Waste Manage. (Oxford) 57, 57–63.
sponding loss at 1250 °C, typical temperature used for recycling Predel, B., 2012. Cu - Sb (copper - antimony). In: Predel, B. (Ed.), B - Ba Ellipsis Cu -
e-waste. Zr: Supplement to Subvolumes IV/5B, IV/5C and IV/5D. Springer Berlin
Heidelberg, Berlin, Heidelberg. 262–262.
4. As the temperatures proposed here are much lower than typical Sahajwalla, V., Cayumil, R., Khanna, R., Ikram-Ul-Haq, M., Rajarao, R., Mukherjee, P.
temperatures currently being used, these coupled with short S., Hill, A., 2015. Recycling polymer-rich waste printed circuit boards at high
operating times could significantly reduce the overall energy temperatures: recovery of value-added carbon resources. J. Sustainable Metall.
1 (1), 75–84.
consumption during e-waste recycling, enhance copper recov- Schluep, M., Hagelüken, C., Magalini, R., Maurer, C., Meskers, C., Mueller, E., Wang,
ery, process efficiency and the environmental sustainability of F., 2009. Recycling - From E-Waste to Resources. UNEP United Nations
e-waste management. Environment Programme, Berlin, Germany.
Silvas, F.P., Correa, M.M.J., Caldas, M.P., de Moraes, V.T., Espinosa, D.C., Tenório, J.A.,
2015. Printed circuit board recycling: physical processing and copper extraction
by selective leaching. Waste Manage. (Oxford) 46, 503–510.
Striebich, R.C., Rubey, W.A., Tirey, D.A., Dellinger, B., 1991. High-temperature
Acknowledgments degradation of polybrominated flame retardant materials. Chemosphere 23 (8–
10), 1197–1204.
Veldhuizen, H., Sippel, B., 1994. Mining discarded electronics. UNEP Ind. Environ. 17
Romina Cayumil gratefully acknowledges the support from (3–4), 7–11.
CONICYT PhD scholarship from Chile. The authors would like to Wang, J., Bai, J., Xu, J., Liang, B., 2009. Bioleaching of metals from printed wire boards
by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans and their
express their gratitude to the Mark Wainwright Analytical Centre
mixture. J. Hazard. Mater. 172 (2), 1100–1105.
Electron Microscope and Solid State & Elemental Analysis Units, Xiu, F.-R., Zhang, F.-S., 2009. Recovery of copper and lead from waste printed circuit
the University of New South Wales. Special thanks are due to boards by supercritical water oxidation combined with electrokinetic process. J.
Rabeya Akter from ICP Laboratory for her help. Hazard. Mater. 165 (1–3), 1002–1007.
Yamane, L.H., Espinosa, D.C.R., Tenório, J.A.S., 2011. Recovery of copper from printed
circuit boards waste by bioleaching. In: Recycling of Electronic Waste II:
Proceedings of the Second Symposium, pp. 45–52.
References Zhan, L., Xu, Z., 2011. Separating and recovering Pb from copper-rich particles of
crushed waste printed circuit boards by evaporation and condensation. Environ.
Baldé, C.P., Wang, F., Kuehr, R., Huisman, J., 2015. The Global E-Waste Monitor - Sci. Technol. 45 (12), 5359–5365.
2014. United Nations University, IAS - SCYCLE, Bonn, Germany. Zhang, Z.Y., Zhang, F.S., 2014. A green process for copper recovery from waste
Behnamfard, A., Salarirad, M.M., Veglio, F., 2013. Process development for recovery printed circuit boards. Adv. Mater. Res., 374–379
of copper and precious metals from waste printed circuit boards with Zhou, G., Luo, Z., Zhai, X., 2007. Experimental study on metal recycling from waste
emphasize on palladium and gold leaching and precipitation. Waste Manage. PCB. In: International Conference on Sustainable Solid Waste Management,
(Oxford) 33 (11), 2354–2363. Chennai, India, pp. 155–162.
View publication stats

Recovery of Copper

Uploaded by

Copyright:

Available Formats

Recovery of Copper

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Recovery of Copper

Uploaded by

Copyright:

Available Formats

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

High temperature investigations on optimising the recovery of copper from

Article in Waste Management · January 2017

Romina Cayumil Muhammad Ikram Ul Haq

SEE PROFILE SEE PROFILE

Rita Khanna Rahul Saini

SEE PROFILE SEE PROFILE

Materials View project

The user has requested enhancement of the downloaded file.

Contents lists available at ScienceDirect

High temperature investigations on optimising the recovery of copper

14 wt% crushed e-waste is added as an additive/impurity to the 1.3. Pyro-metallurgical techniques

Fig. 1. A schematic representation of the experimental arrangement.

Waste PCB specimens in this study were taken from a variety of

complete physical/chemical separation, and was seen as contain-

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.