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Materials Today: Proceedings 5 (2018) 17046–17054 www.materialstoday.com/proceedings

AMPCO-2017

Comparison of different routes for recovery of metals from

electronic scrap
Amit Barnwal*, Shubham Vishvakarma, Nikhil Dhawan
Department of Metallurgical & Materials Engineering, IIT-Roorkee, Uttarakhand-247667, India

Abstract

There is an exponential demand for electronic equipment but, unlike other consumer products, the useful lifetime is relatively
short which calls for the recycling of electronic scrap. Considering the inflow of illegally imported discards from the West, the
electronic waste is expected to reach a total of around 30 million tonnes by 2020. Waste printed circuit boards (WPCB) are
valuable secondary raw material for critical and precious metal industries. In this work, WPCB of different sizes were dissolved
in different lixiviants for metal dissolution. The leach solution contains different metals due to a differential solubility of metals
and associated attachments. With organic solvent DMF, plastic, baseboard, and metallic values are easily detached and separated
without any contamination of plastic and metal. The coarse ground PCB material subjected to dense medium separation resulted
in the clear separation of plastics and metals. Further, the metal fraction is magnetically separated to recover iron-steel values.
With all the three processes almost 90% of metal values are recovered from PCB’s. Based on three processes examined, it can be
concluded that organic solvent processing and physical beneficiation process are better than hydrometallurgical route as the latter
includes extra concentration and separation step.

© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Advances in Materials & Processing: Challenges & Opportunities (AMPCO-2017).

Keywords:Electronic scrap; Recycling; Physical separation; Copper

1. Introduction

The rapid improvement of electric and electronic equipment is steadily growing due to technological advancements
in the information technology sector. A very serious problem facing all over worldwide is ever increasing disposal
of the e-waste due to a short lifespan of electronic commodities. For example, mobile phone is approximately 1.5-2

* Corresponding author. E-mail address: amit.dmt2017@iitr.ac.in

2214-7853© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Advances in Materials & Processing: Challenges & Opportunities (AMPCO-2017).
 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054 17047

years and of a computer and laptop 3-5 years [1]. Since, printed circuit board (PCB) is the main constituent of most
of the electronic commodity as it electrically connects and gives mechanical support to the device. Reduce; reuse
and recycle with recovery are the important techniques for waste management. There are approximately 40% metals
content such as Cu, Fe, Sn, Pb, Zn, Cd, Cr, Ni, and Mn, some amount of precious metals like Au, Ag and Pt and few
rare earth metals (Ta, Ga etc) are also present in waste printed circuit boards (WPCBs). The government sector,
private sectors produce 75% of electronic waste with the individual household being only 16%. 1 million tonnes of
circuit boards contain between 80-150 g of Au and between 160-210 kg of Cu. 43% of total production of gold in
the world is used in electronics [1]. The disposal of the e-scrap in landfills results in loss of high amounts of
valuable metals like gold, silver, copper etc. and also poses a risk of land contamination because of toxic chemical
compounds. The recycling of defective or old scrap is needed because it has an economic gain, and due to high
presence of metals (up to 30% weight of PCB’s). Another advantage of recycling is metal can be recovered easily
compared to primary process and is energy efficient. India is the fifth biggest producer of e-waste in the world,
discarding 1.7 mt of electronic and electrical equipment in 2014 which is expected to rise by ~20 percent in next
three years. There are different methods for the recovery of metals from WPCBs such as Pyrometallurgy,
Hydrometallurgy and Physical Beneficiation Process. In pyrometallurgical process, WPCBs are treated at high
temperature to recover the metals. A lot of hazardous gases are produced during this process and installation of flue
gas cleaning system and fumes collection system is must. The formation of dioxins and furans is unavoidable due to
the use of halogenated flame retardants in PCB’s [2]. Hydrometallurgy process offers comparatively low capital cost
and environmental impact with high metal recovery rate. The amount of metals present in PCB’s varies a lot with
respect to different electronics gazettes such as computer, television, mobile phone etc as shown in Table 1.

Table 1. Composition of different e-waste samples.

Commodity Plastics (wt%) Au (ppm) Ag (ppm) Cu (wt%) Pd (ppm) Fe (wt%)

TV-board 28 20 280 9 10 30
Computer WPCB 23 250 1000 20 10 7
Mobile Phone 56 350 1380 13 110 5
Portable Audio 47 10 150 21 4 23
DVD-player 24 15 115 5 4 62
Calculator 61 50 260 3 5 4

2. Experimental procedure

Due to lack of proper collection, disposal, and sorting system of e-waste in India, it is difficult to find a reliable
source for waste printed circuit board. Printed Circuit Boards (PCBs) of discarded computers were collected from a
local source. Electronic components like diodes, transistors, capacitors, integrated circuits, relay, transformer, and
resistors were manually dismantled and hand removed from PCBs. The photographs of waste printed circuit boards
before and after dismantling are shown in Figure 1. PCBs were cut into small pieces of 4x4cm, 3x3cm, 2x2cm with
the help of a mechanical cutter.

Fig. 1. Photograph of computer PCB a) before dismantling and b) after dismantling.

17048 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054

2.1. Leaching of e-scrap

The solution of sodium hydroxide (40 wt.% NaOH) and potassium hydroxide (56 wt.% KOH) undergoes a
eutectic reaction at 170ºC. The product of the eutectic reaction interacts with the epoxy layer. The solution was
heated up to 170°C (eutectic temperature) on a mechanical stirrer at 400rpm where the hydroxides form a eutectic
mixture and had a pH of 14. A 4x4cm PCB piece was dipped into the solution for 8 minutes. The bromine epoxy
layer (green layer) was removed after the treatment as shown in Figure 3a and 3b. The obtained PCB was washed
using distilled water and was wiped clean for the weight measurement. The alkali solution was found to be reusable
until the solution turns completely yellow from colourless. After treating with NaOH+KOH eutectic solution, HCl
(37%) solution was prepared at different concentrations 1M, 2M, and 3M. The PCB pieces were immersed in the
solution at room temperature without any stirring speed. After the complete dissolution (from visual inspection), the
PCB board was removed and washed with normal tap water. The final weight of dried board was recorded for
further calculations. The leach solution obtained was analyzed using inductively coupled plasma mass spectrometry
(ICP-MS) to evaluate the dissolution of metals which included Cu, Zn, Fe, Sn, and Pb. The epoxy layer was
removed with the help of eutectic solution and the pieces were immersed in Di-methyl-formamide (DMF) solution
at 130°C and were maintained until the boards delaminate.

2.2. Physical Separation

The PCB powder was prepared by using a disc mill and was classified using Vibratory sieving machine. Sieving
was carried out for one hour with different sizes 500μm, 300μm, 150μm, 100μm, 75μm, and 50μm. The WPCB
powder from each sieve was collected separately for magnetic separation. A 2000 gauss magnetic strength T magnet
was used to separate magnetic particles from feed powder and a gap of 1 inch was maintained between magnet and
powder bed to avoid direct contact. Following magnetic separation, dense media separation was carried on the non-
magnetic fraction powders based on differences in the density of metals and plastics. When the powder of different
size fractions +500μm, -500μm+300μm, -300μm+150μm, -100μm +75μm was introduced into Tetrabromoethane
(2.97gm/cc) the metals particles settled at the bottom whereas plastics float to the surface. The different way of the
recycling of the metals performed for the feed sample is shown in Figure 2.

Fig. 2. Experimental plan for processing of e-scrap.

 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054 17049

3. Results and discussions

3.1. Leaching of WPCBs

The presence of harmful substances like fluorine, chlorine, and bromine in the epoxy layer inhibits the direct contact
between the lixiviant and metal; therefore, it is essential to remove an epoxy layer from PCB to dissolve the metal.
PCB pieces were digested in the NaOH-KOH solution at 170ºC for 8-9 minutes. It was found that copper dissolution
increases by manifold in NaOH-KOH treated PCBs. The significant improvement in the dissolution of copper can
be attributed to the removal of epoxy layer [2, 3]. Further, printed circuit board piece was treated with HCl solution
for the dissolution of copper. The photographs of PCB during acid leaching from initial to final stage are shown in
Figure 3. The effect of HCl concentration was investigated in the range of 1-2 M keeping the other parameters
(stirring speed, time of reaction, H2O2 quantity) constant. The results in Figure 4a show that copper dissolution is
steadily increasing with the increase of the hydrochloric acid concentration for a given time which is attributed to
the synergistic effect of hydrochloric ions. H2O2 being an oxidizing agent oxidizes copper to cupric ions and as the
concentration of H2O2 increases, the rate of oxidation also increases. The effect of H2O2 concentration was
investigated in the range of 0-0.5mol/100ml (H2O2 conc./ HCl sol) keeping other parameters constant. The results
shown in Figure 4b depict that the Cu dissolution was negligible till 3-hours in the absence of H2O2 however, with
the addition of H2O2 in leaching solution, the Cu dissolution significantly increased to 98% in 10-12minutes. The
effect of solid to liquid ratio was studied in the range of 0.004 to 0.125g / ml. Two sets of experiments with 1M and
2M HCl concentrations were carried out. Increasing the S/L ratio increased the Cu dissolution with the increase in
acid concentration. This can be attributed to the increase of metal concentration from PCB. Dissolution of the
copper varied if solid to liquid ratio changed which is shown in Figure 4c.
All the experiments were carried out at room temperature and high dissolution was achieved. The use of temperature
is not recommended considering the solution starts to evaporate at temperatures greater than 50°C. All the leach
solutions (lixiviant HNO3, H2SO4, HCl) have a pH of 2 initially and after all the chloride ions get exhausted (metal
chloride formation CuCl2, SnCl2, PbCl2, ZnCl2) the pH became 6. In 1M HCl solution with 0.125 S/L, all the
chloride ions exhausted due to chloride formation. The solution turned into bluish-green colour and further
dissolution doesn’t occur. A 1M HCl with 0.3M H2O2 and 2M HCl with 0.5M H2O2 solutions was used. Initially, the
solutions were colourless with a pH ≃2, but as the metal chlorides mainly CuCl2 starts forming solution turns into
green. In 1M HCl experiment, the solution turned into the dark bluish-green after the introduction of the the5x5cm
board. It dissolved partially, and the reaction stopped. The pH of the final solution was 6 which indicated that all the
Cl- ions got exhausted so no further reaction occurred. Nine boards of different sizes were dissolved in 2M HCl
solution and final pH of the solution remained ≃2. This indicates that free Cl- are still present in the solution and can
dissolve further metal. The metal dissolution and recovery with the different conditions were studied through ICP-
MS. Next, the effect of solid to liquid ratio was studied and based on ICP -MS results it was observed that up to
99% metal dissolution was achieved.

(a) (b) (c)

Fig. 3. Photographs of PCB a) Feed b) After NaOH+KOH treatment c) After copper dissolution in HCl +H2O2.
17050 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054

Fig. 4. Effect of various factors on copper dissolution from PCB (a) acid concentration (b) H2O2concentration (c) S/L ratio.

3.2. Dimethylformamide (DMF) leaching

A special type of flame retardants plastics is affix during the construction of printed circuit boards. The glass fibre
matrix with epoxy resin binder is used in between the different layers of PCB during the manufacture of printed
circuit boards. There is one or number of copper layers present in the boards which are depending on the PCB type.
The rate of reaction of DMF along cross-sectional area is much faster than its facial area. This is because solder
mask and copper tracks on the surface of WPCB are chemically inert and act as a hitch in penetration of DMF [6].
In this work initially, treatment was done with eutectic sodium hydroxide and potassium hydroxide solution at
170°C for 10 minutes for removing the chemically inert layer present in the WPCB. This is due to the fact that DMF
solvent easily penetrated in the board with lesser time so that all the experiments could be at optimum temperature
130°C for maximum delamination of WPCB pieces. The rate of dissolution in DMF increases up to 135°C because
of enhanced vibration of the rigid bond of brominated epoxy resin (BER) at high temperature and reversible
breakage of Vander Waals bonds beyond glass transition temperature (Tg~130°C) promoting ease in bond formation
between BER and DMF [6]. As DMF leaching is based on absorption/diffusion, if more surface area is exposed
more is the metal recovered. The delamination of WPCB pieces is dependent on how much cross-sectional area is in
contact with DMF liquid. Small PCB pieces such as 1x1cm were easily delaminated compared to bigger sizes
(2x2cm, 3x3cm) because DMF solution is easily diffused compared to bigger boards. Initial delaminating from the
cross-sectional area of waste printed circuits board pieces was observed after 15 minutes, 25 minutes and 37 minutes
in case of 1X1 cm, 2X2cm and 3X3cm respectively. So, from the above data 1x1cm proved to be a suitable size for
easy and fast delamination. Due to prior removal of epoxy layer, time to delaminate is considerably decreased as
compared to Verma et al. [6] who reported 4 hours for complete delamination of 1x1cm PCB board. It is observed
from the Figure 5 that at lower S/L ratio, more time is required for metal delamination. This is because of the
 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054 17051

ineffective continuous swelling of the WPCB pieces due to limited solvent availability. Similarly, it was found that
stirring speed also has a positive effect on delamination of WPCB pieces. For example, 1x1 cm PCB was
delaminated in 65 minutes without stirring as compared to 45 minutes with 350rpm stirring speed. Copper wire
(92%) and copper foil (98%) delaminated during DMF treatment is shown in Figure 6. Hence, it can be concluded
that almost pure copper can be extracted using DMF treatment.

Fig. 5. Effect of stirring speed, PCB size and S/L ratio on copper dissolution from PCB’s.

Fig. 6. Photograph and composition (EDX analysis) of recovered copper wire and copper foil.

3.3. Physical Separation

Before size reduction of WPCB pieces, PCB was physically dismantled and metallic values were recovered. The
SEM-EDX analysis was performed to know the exact composition of a recovered dismantled fraction as shown in
Figure 7. It is evident that Al, Si, Ni, Mn are the main elements associated with dismantled values. Waste printed
17052 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054

circuit boards were cut into small pieces and further ground using disc mill for the liberation of metals. Liberated
metallic particles with spherical, rounded and smooth physical characteristics generally lead to efficient separation
of valuable metals with a higher recovery percentage [4]. Due to poor grindability of the metallic and non-metallic
constituents of the PCB pieces, the generation of ultrafine could not be avoided [9].
A representative sample of -100 to +75 µm was taken for the X-ray fluorescence (XRF). The composition of WPCB
grounded powder obtained from XRF analysis reveals the presence of Cu (12.29 %) and Fe (13.31%) respectively as
shown in table 2. The presence of high copper values was promising and hence, further research was carried out. A
representative 250 gm e-scrap ground powder was subjected to sieving using different screens. The material was
classified in size fractions: +1000 µm, -1000 to +500 µm, -500 to +312 µm, -312 to +212 µm, -212 to +150 µm, -
150 to +100 µm, -100 to +75 µm and -75 µm. Magnetic separation using a T-magnet was carried out on different
size fractions. It was found that the ferrous fraction decreased significantly with decreasing particle size. It was seen
that maximum metallic fraction was found in the +1000 µm size i.e. 12.25% compared to 2.16 % for minus 75µm
size. For particle sizes less than 300µm, the degree of separation of metals and non-metals was limited and hence, it
is recommended to limit the particle size up to 300µm. The non-metallic part obtained from the magnetic separator
was carried over to density media separation using Tetrabromoethane solvent. The effect of particle size on both
magnetic and non-magnetic fractions is shown in Figure 8. For particles sizes above 1000µm, almost 25% metallic
fraction was found in sink portion whereas most of the plastics report to floating part. Surprisingly, there was no
separation in the size range of -150 to +100 µm or below, as significant agglomeration of particles was observed.
The photographs of float and sink fractions obtained from physical separation process were characterized using
SEM-EDX analysis are shown in Figure 9. It can be seen that the sink fraction consists mainly of Sn, Ni, Pb, and Cu
whereas float portion contains Br, C, and O.

Al-26.15%
Si-6.74%
Ni-9.56%
Mn-3.24%

Fig. 7. Photograph and composition (EDX) of metal parts during physical dismantling.

Fig. 8. Effect of particle size in physical separation process.

 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054 17053

Table 2. XRF of the powdered feed sample.

Metals Cu Fe Zn Pb Sn Br Ca Al Si Mn
Weight (%) 12.29 13.31 0.653 7.822 8.074 15.81 12.62 5.032 19.55 1.387

Fig. 9. Photographs and composition of separated e-scrap material.

4. Conclusion

In hydrometallurgy process, WPCB pieces were used and obtained higher dissolution compared to WPCB
powder. The chemical coating present on the WPCB was removed with the help of alkali hydroxides (NaOH-KOH)
solution prior to the acid dissolution. The metals present on the WPCB pieces (2X2 cm, 3X3 cm, 4X4 cm) were
dissolved in hydrochloric acid with oxidant H2O2 in just 8 minutes. The most important and beneficial aspect of this
process is that the leach solution can be reused which reduces the environmental burden as compared to one-time
use solvents. DMF promises to be an effective lixiviant to delaminate metals from e-scrap. The time taken for
dissolution of epoxy resin in DMF was gradually decreased in the presence of eutectic alkali hydroxide. The
separation of a glass matrix and the copper laminate was achieved in 45 minutes in case of 1X1 cm at 130°C. The
merit of the process is that solvent is reusable and without requirement of acid dissolution, purification and electro
deposition steps. The physical beneficiation process consisting of milling, size classification, magnetic separation
and dense media separation is observed to be the best process for the recovery of metals considering it avoids the
use of harmful chemicals and high temperature during this process. However, the process application is limited to
particle sizes less than 0.3mm due to agglomeration behavior of particles.
17054 Barnwal et al. / Materials Today: Proceedings 5 (2018) 17046–17054

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