Journal of Environmental Science and Management 15(1): 17-27 (June 2012)

ISSN 0119-1144

Recovery of Copper from Spent Solid Printed-Circuit-Board (PCB) Wastes of a PCB

Manufacturing Facility by Two-Step Sequential Acid Extraction and Electrochemical
Deposition
Monet Concepcion C. Maguyon1, Catalino G. Alfafara2, Veronica P. Migo3, Jovita L. Movillon4
and Carmelita M. Rebancos5
ABSTRACT
The recovery of copper from solid printed circuit board (PCB) waste, by sequential acid dissolution and
electrochemical deposition, was investigated as a resource recovery strategy for a local PCB-manufacturing facility.
The rst stage acid dissolution process extracts the embedded copper metal from the solid PCB matrix in the form of
copper ions, and the second-step electrolysis converts the copper ions back to its purer metal form. The copper metal
can then be processed for possible reuse, or sold for income generation. For the acid treatment, the best extractant
was found to be concentrated nitric acid added at a waste loading ratio of 120 mg PCB waste per mL of acid, and
4 hr contact time. Six-hour electrochemical deposition experiments (of the acid extracts from the best dissolution
conditions) showed that a copper removal efciency of 98% (from the acid extract) could be achieved. The charge
dose of the electrochemical deposition process was computed to be 11.987 coulombs mg-1 of copper removed from
the acid extract. From preliminary cost estimates, the reuse of the spent nitric acid from the acid treatment step is
recommended to minimize the total copper recovery cost.
Key words: electrodeposition, printed circuit board, copper, semiconductor, electronics

INTRODUCTION
Modern human productivity has become increasingly
reliant on electronic equipment for enhancing productivity
and for satisfying the hunger for information. The use of
computers, mobile phones, e-book readers, and electronic
analytical instruments has become an indispensable part
of modern human society. The demand for electronic
devices has driven technology to produce more of these
devices. The pace of innovation has also gone so fast,
that within a span of just a few short years, the devices
become obsolete. This has lead to a signicant increase
in the generation of electronic wastes coming from the
manufacture and use of electronic products (Huang et al
2009; He et al 2006; Lee et al 2007; Bereketli et al 2011).
One essential component in the production of electrical
and electronic equipment (EEE) is the printed circuit board
(PCB) (Zhou and Qiu 2010; Guo et al 2010). The printed
circuit board (PCB) serves as a platform where electrical
components (i.e. semiconductor chips and capacitors) are
structured and electrically connected (LaDuo 2006). About
$1 T sales from electronic products per year depends on
PCB manufacture (LaDuo 2006). According to Guo et al
(2010), the average rate of PCB manufacture increased to
about 8.7% worldwide, 10.8% in Southeast Asia and 14.4%
in China. In 2003, Japan manufactured about 29% of PCB
1

worldwide followed by China (17%) and the United States

(15%) (LaDuo 2006).
The selection of materials for the manufacture of PCBs
depends on the application (Hall and Williams 2007).
Typically produced PCBs are made up of polymer lms (Hall
and Williams 2007), glass, or ceramic substrates (LaDuo
2006). Fiberglass mat impregnated with a ame-resistant
epoxy resin is also used for selected commercial applications
(Hall and Williams 2007; LaDuo 2006). PCBs also contain
signicant amounts of metals (i.e. copper, iron, nickel, silver,
gold, palladium). Copper, which is used to form the electrical
circuit on the PCB, is the dominant metal species (Hall and
Williams 2007; Zhou and Qiu 2010). Hence, wastes generated
from PCB manufacture cannot be simply landlled due to
its hazardous nature and the valuable materials present in
PCB waste. Toxic substances in PCB wastes (i.e. cadmium,
mercury, lead, etc) should be treated prior to disposal. On
the other hand, the valuable metals such as gold and copper
should be recovered in order to prevent resource depletion.
Traditional methods of recycling waste PCBs includes
mechanical (i.e. multi-crushing, grinding, electrostatic
separation, gravity-, density-based and magnetic separation)
and hydrometallurgical methods (Duan et al, 2009;

Assistant Professor, Department of Chemical Engineering, College of Engineering and Agro-Industrial Technology (CEAT), University of the Philippines Los Banos,
College, Laguna 4031, Philippines E-mail: mcmaguyon0182@yahoo.com (corresponding author)
2
Associate Professor, Department of Chemical Engineering, CEAT, UPLB
3
Research Associate Professor, National Institute of Molecular Biology and Biotechnology, UPLB
4
Professor, Department of Chemical Engineering, CEAT, UPLB
5
Professor, School of Environmental Science and Management, UPLB

18

Li et al 2009; Eswaraiah et al 2008; Yoo et al 2009; Veit

et al 2005). Hall and Williams (2007) determined the
applicability of pyrolysis to convert the organic portion of
PCB waste into liquid fuel. In their process, a wide variety
of metals from the PCB remained in the char (residue) and
further processing is required to recover each metal. Oishi et
al (2007), on the other hand, employed a three-step process
(leaching, solvent extraction and electrodeposition) to
recover copper from scrap PCB from electronic equipments.
These methods, however, are employed for PCBs from scrap
electronics discarded by end-users. No or little information
is available for treatment of wastes from the manufacture
of PCBs particularly from the etching and lamination steps.
Hence, this study was conceptualized.
In this study, the technical feasibility of recovering
copper from solid PCB waste sheets from the lamination step
in the manufacturing process (Figure 1) was explored. The
technical solution perceived to be useful in recovering copper
from PCB waste was a combination of acid treatment followed
by electrodeposition. Electrodeposition has an advantage
over other conventional metal removal and recovery methods
since in this process copper can be recovered in its metal
form (Cu0). Some studies have proven the electrochemical
method to be effective in removing metals from industrial
wastewaters such as semiconductor wastewater (Aquino
2005) and gold smelting efuent (Vivas 2007). However,
since the PCB waste is in solid form, the copper and other
metals present in the waste must be dissolved rst by acid
treatment prior to electrodeposition. Initially, a screening
experiment for the acid treatment of solid PCB waste was
done by testing different combinations of acid types, waste
loadi ng (expressed as mg PCB waste mL-1 acid) and soaking
times using a 23 full factorial design. The concentration (in
mg l-1) of copper in the acid extract after acid treatment
was evaluated to determine the suitable acid for extraction
as well as the effects of varying the operating conditions
(i.e. waste loading and soaking time). Subsequently,

Figure 1. Printed circuit board waste.

Recovery of Copper from Spent Solid PCB wastes

a general factorial design with two factors (i.e. waste

loading and soaking time) was done using the suitable acid
for extraction to determine the optimum waste loading and
soaking time combination. The electrodeposition process, on
the other hand, was evaluated with respect to residual copper
concentration of the electrolyte. The charge dose of the
electrodeposition process was also calculated to determine
operational and scale-up factors.
MATERIALS AND METHODS
Preparation and Elemental Analysis of Printed Circuit
Board (PCB) Waste
The solid printed circuit board (PCB) waste used in the
experiment was obtained from a local PCB manufacturing
rm. Solid PCB waste sheets were shredded into smaller
chips, approximately 5 mm x 3 mm in size, before acid
treatment to maximize the PCB-acid contact area. A sample
of the PCB waste sheet is shown in Figure 1. Elemental
analysis of the shredded solid PCB waste was done using
X-Ray Fluorescence (XRF) spectroscopy and scanning
electron microscopy. The residue obtained from the acid
treatment step was analyzed for gold content using Energy
Dispersive X-Ray (EDX) analysis.
Preparation of Different Oxidizing Agents (Acids) for the
Acid Treatment Step
Concentrated (65% wt) nitric acid and aqua regia
(a 1:3 volume mixture of concentrated nitric acid and
concentrated (36% wt) hydrochloric acid) were compared
to determine the suitable acid for oxidation and dissolution
of the copper metal embedded in the solid PCB waste.
Acid Treatment
Initially, a screening experiment (23 full factorial
design) was employed to select the suitable acid for copper
extraction from PCB waste. Batch experiments were carried
out in 1-L erlenmeyer asks using two different types of
acids (HNO3 and aqua regia). Fifteen and 75 g of shredded
PCB waste were soaked in a constant volume of acid (500
mL) corresponding to waste load values of 30 and 150
mg PCB waste mL-1 acid, respectively. Samples of acid
extracts were obtained after 1 hr and 24 hours contact time
and subjected to copper analysis using atomic absorption
spectrophotometry. Statistical analysis and cube plot were
generated using Design Expert Version 8.0.6 to determine
the suitable acid for copper extraction.
Subsequently, a general factorial design with two (2)
factors (i.e. waste load and contact time) was conducted using
the best acid for extraction based on the screening experiment.
Varying amounts (15, 30, 60 and 75 g) of PCB waste were

Journal of Environmental Science and Management Vol. 15. No. 1 (June 2012)
soaked in a constant volume of acid (500 mL) corresponding
to waste loads of 30, 60, 120 and 150 mg PCB waste mL-1
acid. Samples were taken at regular intervals during the acid
treatment step for copper analysis. The copper concentration
of the acid extract at different waste load values was plotted
against time to determine the practical operating conditions
for acid treatment.
Copper Electrodeposition
Batch electrolysis set-up. The experimental set-up for the
electrodeposition is presented in Figure 2. Electrolysis
was conducted in a 500-mL beaker reactor with magnetic
stirrer. Working volume was 400 mL. The operating current
was supplied by a DC power source with a variable voltage
ranging from 0 volt to 30 volts (Wheeler WSPS-817,
Taiwan).
In the electrolysis experiment, a stainless steel cathode
and a sintered platinum anode were used as the electrode
system. The dimensions of the electrodes were about 5 cm
x 15 cm. A rubber spacer, approximately 5 mm thick, was
placed in between the electrodes to prevent short circuiting.
Copper electrodeposition experiments at different
dilutions of acid extracts. The acid extract obtained from
acid treatment of solid PCB waste using the best operating
conditions was used as the electrolyte in the electrodeposition
experiments at different dilutions. Electrodeposition of
copper using the raw concentrated solution could not be done
due to problems associated with severe acidic conditions
which could potentially dissolve the metal electrodes and
generation of large amounts of oxidants during electrolysis

19
-

as a consequence of high concentration of chloride (Cl ) ions

in the acid extracts. Thus, several dilution factors were tried
to determine a practical dilution that would favor copper
electrodeposition. Distilled water was used to dilute the raw
concentrated acid extracts using dilution factors of 2, 3.5, 5
and 10. The resulting diluted solution served as the electrolyte
or plating bath in the electrodeposition process operated
at 3A for 6 hours. Samples were taken at regular intervals
during electrolysis and tested for copper concentration using
atomic absorption spectrophotometry. The result of the
experiment was used to assess the practical dilution factor
for copper electrodeposition.
Copper electrodeposition experiments at different
operating currents. The diluted acid extracts prepared
using the optimized acid treatment conditions and dilution
factor was electrolyzed at different operating currents (1A,
2A and 3A). Samples were taken at regular time intervals
and analyzed for copper content using atomic absorption
spectrophotometry. The results of the experiment were used
to obtain useful engineering relationships for a scaled up
process (i.e. charge dose).
Data Analysis. Residual copper concentration during
electrodeposition of acid extracts were plotted against time
for dilution of 2, 3.5, 5 and 10. The trends from the time
proles were observed and evaluated. Also, the time for
copper concentration to level off during electrodeposition
was determined for each dilution. The maximum copper
removal was also determined.
Residual copper concentration time course for
electrodeposition of diluted acid extract (using the optimum
dilution factor) at different operating currents 1A, 2A and 3A
were constructed to evaluate the effect of operating current
on copper removal . Using the time course plot for currents
1A, 2A, and 3A, the time required for copper recovery to
level-off was determined for each current. Secondary effects
of electrolysis, which includes pH and temperature of the
electrolyte were also monitored.
Using the experimental data, the copper charge dose
for electrodeposition of acid extracts (under optimum acid
treatment conditions and dilution factor) was determined.
The charge dose has been dened as the amount of electricity
required to remove a target pollutant. It has been used as
an empirically derived factor for scale-up and operation of
electrolytic reactors (Alfafara et al 2003). Charge dose is
dened as the amount of charge required to remove unit mass
of pollutant with unit of coulombs (Alfafara et al 2002). It
can be calculated using Equation (1).
(1)

Figure 2. Copper electrodeposition experimental set-up.

Recovery of Copper from Spent Solid PCB wastes

20

where: Q = charge dose , C/mg pollutant removed

I = electrical current, A
t = time, s
Co = initial concentration of pollutant, mg L-1
C = nal concentration of pollutant, mg L-1
V = volume of beaker, L
The copper charge dose was then used to calculate the energy
requirement of the process using Equation (2):
(2)
E is the voltage in volts and Q is the charge dose in Coulombs
mg-1 copper.
RESULTS AND DISCUSSION
Analysis of Potential Pollutants in Solid Printed Circuit
Board (PCB) Waste
The shredded solid printed circuit board (PCB)
manufacturing waste was analyzed for elemental components
using X-Ray Fluorescence (XRF) spectroscopy. There were
21 elements embedded in the waste (Table 1). Based on mass
percentage, copper was found as the dominant metalspecies
(96.62% wt), followed by another metallic element,

nickel (1.39% wt), and a non-metallic element, sulfur (0.74%

wt). Aside from copper, there were some valuable metals in
the waste including silver (Ag), nickel (Ni) and titanium
(Ti). Metallic gold may possibly be also present in the waste
since gold is used in the manufacturing process (Zhou and
Qiu 2010). However, since the actual concentration of gold
in the waste may not be within the XRF limits of detection,
metallic gold may not have been detected. To conrm
the presence of gold in the waste, the scanning electron
microscopy was used. The presence of metallic gold (Au) in
the PCB waste was qualitatively conrmed. The differences
in the composition of PCB manufacturing waste and PCB
from scrap electronic equipments were also revealed (Table
1). PCB manufacturing waste mainly consists of copper
(96.62% wt) while the PCB from scrap electronics contains
copper at a relatively lower percentage (26% wt and 47.68%
wt). This may be attributed to the presence of other electronic
components (i.e. resistors, capacitors) and solder (tin, lead)
present in PCB from scrap electronics which may contain
different metallic compositions. Also, electronic scraps
consist largely of non-metallic components (65% wt) and
consequently, relatively lower metallic components (35%
wt) (Park and Fray 2009).
From Table 1, several potentially hazardous
components were also present in the PCB manufacturing

Table 1. Elemental composition (%w/w) of PCB manufacturing waste and PCB from scrap electronics.
Element
Copper (Cu)
Nickel (Ni)
Sulfur (S)
Cobalt (Co)
Rubidium (Rb)
Thorium (Th)
Calcium (Ca)
Mercury (Hg)
Selenium (Se)
Barium (Ba)
Tellurium (Te)
Molybdenum (Mo)
Antimony (Sb)
Cesium (Cs)
Chromium (Cr)
Tin (Sn)
Titanium (Ti)
Palladium (Pd)
Silver (Ag)
Vanadium (V)
Scandium (Sc)
a

Experimental data

PCB manufacturing wastea

PCB from scrap electronics

Oishi et al (2007) Hall and Williams (2007)

96.62
1.39
0.74

26
1.5
---

47.68
2.09
---

0.61
0.38
0.06
0.06
0.04
0.02
0.02
0.01
0.01
0.01
0.01
0.01
4.34x10-3
3.79x10-3
3.75x10-3
2.31x10-3
1.83x10-3
8.67x10-4

0.058
--------------0.012
0.16
----4.9
----0.063
-----

0.00
----4.94
0.00
--0.12
----0.00
--0.01
--0.00
0.00
1.27
-----

Journal of Environmental Science and Management Vol. 15. No. 1 (June 2012)
waste. Although copper (the dominant species) is considered
valuable due to its widespread applications in coinage, water
pipes, roof coverings, pigments and dyes and cooking utensils,
it can cause adverse health effects such as damage in a variety
of organ systems and even death at high concentrations
(Corradi 2011). Vapor or water-soluble salts of mercury is
considered as an acutely hazardous element since it corrodes
membranes of the body. Acute mercury poisoning can cause
bleeding of gums, vomiting and stomach pain. It also causes
irreversible damages to the brain, liver and kidney (Microsoft
Encarta Premium 2006). Low-exposure to mercury can
also negatively affect reproductive health (Wirth 2010).
Chromium, on the other hand, is a carcinogenic metal in its
hexavalent form.
Copper was the most dominant metal (96.62% wt of
total metals in PCB waste) among the 21 metals embedded
in the printed circuit board waste and this paper focused on
the extraction and recovery of copper from the solid PCB
manufacturing waste.
Copper Extraction by Acid Treatment
Selection of Acid Extractant and Extraction Conditions.
Demir et al (2004) and Park and Fray (2009) suggest that
nitric acid (HNO3) and aqua regia, respectively, can be used
to extract copper from PCB wastes. The use of aqua regia in
the acid treatment step was also deemed advantageous for
the extraction of gold from the waste. According to Park
and Fray (2009), gold can be selectively extracted from the
diluted acid (aqua regia) extracts using toluene. However,
the extraction of gold from PCB waste was not covered in
this paper.
The reaction between HNO3 and copper from PCB
waste during acid treatment was characterized by the
evolution of brown gas and green color of the resulting
solution. Based on the known reaction between copper metal
and nitric acid shown in Equation 3 (Park and Fray 2004),
the brownish gas was most likely, nitrogen dioxide (NO2).

21
-

Initially, metallic copper could be oxidized by NO3 ions

from nitric acid to Cu2+ ions accompanied with the evolution
of brownish nitrogen dioxide (NO2) gas. The copper ions
produced may have subsequently reacted with chloride ions
(Cl-) from hydrochloric acid to produce a greenish copper
chloride (CuCl2) liquid. An excess amount of chloride ions
could then possibly react with CuCl2 to produce a yellowish
complex ion (CuCl42-).
A 23 full factorial screening experiment were used to
compare HNO3 and aqua regia based on the concentration
of copper in the acid extracts. Higher concentration of
copper in the acid extracts is more desirable since it
means that more copper was stripped from the PCB waste.
Consequently, more copper can be recovered from the PCB
waste by electrodeposition of the acid extract. The cube plot
for the screening experiment done to compare the two acids
is illustrated in Figure 3. The cube plot shows that HNO3
is more effective in extracting copper from the solid PCB
matrix since higher copper concentrations were observed in
the HNO3 side (right face). One-hour acid treatment at 150
mg PCB waste mL-1 acid, for example, resulted to copper
concentration of 65,078 mg l-1 for HNO3 which is much
higher than that obtained for aqua regia (19,868 mg l-1).
An increase in waste loading (bottom to top face) increases
the amount of copper extracted. For instance, copper
concentration increased from 10,938 mg l-1 (30 mg PCB
waste mL-1 acid) to 62,078 mg l-1 (150 mg PCB waste mL-1
acid) after 1 hour contact time using HNO3. On the other
hand, increasing the soaking time from 1 hour to 24 hours
(front to back face) increases the amount of copper extracted
from the waste. For example, the copper concentration
increased from 19,868 mg l-1 (1 hour) to 48,460 mg l-1 (24
hours) for acid treatment at 150 mg PCB waste mL-1 acid
using aqua regia, At =0.05, the ANOVA result indicates
that the model is signicant at p-value of <0.0001. It also

(3)
The resulting greenish solution could be due to
oxidation and dissolution of copper ions in nitric acid. It also
indicates that copper ions in the acid extract were in its Cu2+
form. On the other hand, the reaction between copper and
aqua regia was characterized by the formation of a yellowishgreen solution and evolution of brownish gas. Equations 4 to
6 show the mechanism for oxidation of copper (Cu0) from
solid PCB waste to Cu2+ ions using aqua regia.
(4) Figure 3. Cube plot for the acid treatment of solid PCB waste
using HNO3 and aqua regia at different waste
(5)
-1
(6)

loadings (30 and 150 mg PCB waste mL acid)

and soaking times (1 and 24 hours).

Recovery of Copper from Spent Solid PCB wastes

22

indicates that the three factors (i.e. acid type, waste loading
and soaking time) as well as the 2-factor interactions
signicantly affect the amount of copper extracted from the
PCB waste.
HNO3 was used in the acid treatment for the extraction
of copper from the solid PCB waste since higher copper
concentrations were obtained using HNO3.
Effect of Acid Treatment Time and Waste Loading. The
time prole for concentration of copper extracted from PCB
waste in nitric acid (HNO3) at different waste loadings
between 30 mg PCB mL-1 nitric acid to 150 mg PCB mL-1
nitric acid is plotted in Figure 4.
At waste loadings of 30 and 60 mg PCB waste
mL HNO3, an initial increase in copper concentration
was observed followed by a level-off at a certain copper
concentration, after approximately 1-hr operation. A similar
trend was observed for the waste loading of 120 mg PCB
waste mL-1 HNO3. However, the level-off period started
after 4 hours treatment.

PCB wastes.
Electrodeposition of Copper
The electrolytes used in the electrodeposition step
were the acid extracts obtained using nitric acid added at 120
mg PCB waste mL-1 acid waste loading and 4 hours soaking
time. The copper concentration of the raw concentrated acid
extracts was found to be approximately equal to 51, 950
mg l-1. The acid extract was also found to be highly acidic
having a pH value of 0.0. Based on Equation 3, copper is
in its ionic form (Cu2+) in the acid extracts obtained from
the acid treatment step using HNO3 as oxidizing agent. To
recover copper from the electrolyte, ionic copper (Cu2+)
should therefore be reduced to metallic copper (Cu0) using
the electrodeposition process.

-1

Operating at 150 mg PCB waste mL-1 HNO3 waste

load, on the other hand, resulted to an initial rise in copper
concentration until a peak copper concentration was reached
after approximately 2-hr treatment. This was followed by
an abrupt uctuation until the copper concentration leveled
off after approximately 8-hr operation. This uctuation
was observed only at the highest loading (150 mg PCB
waste mL-1 HNO3). Repeat experimental runs also showed
the same uctuation only at the highest loading. Complex
interactions (which may be related to equilibrium shifts due
to Cu2+ accumulation and reduction in the reaction system)
were indicated by the observation at higher loadings; these
may need further investigation.
For practical purposes, the waste loading at 120 mg
PCB waste mL-1 HNO3 at a soaking time of 4 hours was
chosen as a practical acid extraction condition, because the
uctuations in copper concentration at 150 mg PCB waste
mL-1 HNO3 loading stabilized only after 8 hours. Operating
at lower waste load values of 30 and 60 mg PCB waste mL-1
HNO3 would entail shorter treatment time (approximately 1
hour). However, it would require large volumes of nitric acid
to extract copper from PCB waste. Although the treatment
time required for copper concentration to level-off at 120 mg
PCB waste mL-1 HNO3 is longer (approximately 4 hours) as
compared to lower waste load values (30 and 60 mg PCB
waste mL-1 HNO3), operating at a waste load of 120 mg PCB
waste mL-1 HNO3 would require lesser amount of acid to
extract copper from the waste. Hence, waste loading of 120
mg mL-1 was chosen as the practical working waste loading
(despite a higher copper extracted at 150 mg mL-1), and a
reasonably high amount of copper was leached from the

Effect of Dilution of Electrolyte. Electrodeposition using

raw concentrated acid extracts from nitric acid treatment step
as electrolyte was not tried since the solution was found to
be still reactive (as evidenced by emission of brownish gas
from the electrolyte container) and highly acidic (pH 0.0). A
highly acidic solution could react with the metal electrodes
used in electrodeposition. Hence, the electrodeposition
process was tested for acid extracts diluted at dilution factors
of 2, 3.5, 5 and 10, operated at a constant current of 3A for 6
hours. The result of the electrolysis time course is drawn in
Figure 5. Dilution factors of 2, 3.5, 5 and 10 were referred
in the graph (and this section) as DF 2, DF 3.5, DF 5 and DF
10, respectively.
The horizontal plot for residual copper concentration
at DF 2 indicates that there was no signicant copper
deposition at the cathode. At DF 3.5, on the other hand,
there was some decrease in residual copper concentration.
However, the level-off concentration of copper in the acid
extract is still relatively high (~13,000 mg l-1) after 6 hours
of electrolysis. At comparatively low dilution values (DF
2 and DF 3.5), there was little or no deposition of copper
at the cathode. This could be due to formation of chlorinebased oxidants during electrolysis (Alfafara et al 2003) and
extremely acidic pH of the acid extract. Chlorine-based
oxidants may have been formed from the naturally-occurring
chloride ions in the acid solution. Both conditions promote a
highly oxidative environment which could cause dissolution
of the deposited metals back to Cu2+ ions. Further dilution
at higher DF values (DF 5 and DF 10), could have possibly
reduced the concentration of the chloride ions and the
acidity of the electrolyte which made copper removal by
electrodeposition feasible.
Residual copper concentration decreased over time
for DF 5 and DF 10 and leveled off at a certain copper
concentration (Figure 5). The residual Cu2+ concentration
proles for DF 5 and DF 10 during the rst 135 minutes of

Journal of Environmental Science and Management Vol. 15. No. 1 (June 2012)
electrolysis were also observed to be parallel. The initial rates
of copper removal (-dCu/dt, from 0 minutes to 135 minutes),
for DF 5 and DF 10 were then calculated using linear
regression, and these were found to be the same (about 32
mg Cu liter-minute-1). This could be further explained using
Faradays Law of Electrolysis, as given by the following
equation:
(7)
where m is moles of metal deposited on the cathode, I is
current, t is time, n is the number of electrons in the redox
equation and F is the Faradays constant.
The derivative of Equation (7) gives the rate of copper
removed from the solution, and deposited at the cathode.

23

The derivative shows that the rate of copper removal is a

constant [dm/dt=(1/nF)]. Since the operating current for DF
5 and DF 10 were the same, then based on Faradays Law,
the rate of copper removal (as indicated by the slope of the
plots in Figure 5) should be the same. This similarity of
slope was observed for the rst 135 minutes of electrolysis.
However, beyond 135 minutes deviation from Faradays
Law was observed. The graphs tended to level off and were
not anymore parallel. Furthermore, the level off time for
DF 10 (270 minutes) was earlier than DF 5 (315 minutes)
as shown in Figure 5. This can be attributed to dilution
effects which include lower Cu2+ concentration and lower
Cl- ions concentration in the electrolyte. Shorter electrolysis
time would be required to remove smaller amount of copper
ions from the electrolyte. Whereas, the concentration of
chlorine-based oxidants during electrolysis would be lower

Figure 4. Copper concentration time courses for acid treatment of solid PCB waste using nitric acid (HNO3) as copperdissolving and oxidizing agent at different waste loadings

Figure 4. Residual copper concentration time courses at different dilution factors and operating current of 3A.

24

if smaller amount of chlorine was present in the electrolyte.

The residual copper concentrations were 161.38 mg
l-1 (98% removal efciency) and 39.25 mg l-1 (99% removal
efciency) at DF 5 and DF 10, respectively (Figure 5). The
copper deposits obtained from the stainless steel cathode after
electrolysis at DF 5 and DF 10 at 3A are shown in Figure 6.

Recovery of Copper from Spent Solid PCB wastes

electrodeposition process to determine the effect of operating

time and current.
The visible color changes in the solution after
electrolytic treatment is seen in Figure 7. The color of the
wastewater changed from green to a clear, yellowish solution
at 2A and 3A. However, only a slight change in color was
observed at 1A. No precipitate was visible after each runs,
hence, the problem in toxic metal sludge disposal could be
eliminated using the electrodeposition process.
The decrease in green color of the electrolyte
could indicate reduction of ionic copper (Cu2+) to metallic
copper (Cuo) according to the half-reaction in Equation (8).

Figure 6. Copper deposits obtained at the cathode after

electrodeposition at 3A.

Although the operating conditions would seem to be

more favorable at DF 10 (99% removal efciency after 270
minutes), diluting the raw concentrated acid extract ten times
(DF 10) would rather be costly since it would require larger
amount of dilution water. Hence, operating at DF 5 would
be quite more practical. The effects of operating current and
electrolysis time were, therefore, studied for electrolytes
diluted at DF 5.
Effect of Operating Current and Time. The initial copper
concentration of nitric acid extracts of solid PCB waste
diluted at DF 5 was 10, 131 mg l-1 and it was highly acidic (pH
0.5). The acid extract, which was green in color indicating
the presence of Cu2+ ions, was used as the electrolyte in the

(8)
At high operating currents, 3A and 2A, copper
removal was progressive with time (Figure 8). Using
linear regression, copper removal rates at 3A and 2A
were about 32 mg Cu liter-minute-1 and 28 mg Cu literminute-1, respectively. A higher operating current could
reduce higher amounts of copper at the cathode resulting

Figure 7. Electrolyte before (a) and after electrodeposition at

3A (b), 2A (c) and 1A (d) for 6 hours.

Figure 8. Residual copper concentration time courses at DF (dilution factor) 5 and different operating currents (1A, 2A and 3A).

Journal of Environmental Science and Management Vol. 15. No. 1 (June 2012)

25

to higher copper removal efciency, which is in accordance

with Faradays Law of Electrolysis. Hence, the maximum
copper removal efciency was also higher at 3A (98%) than
at 2A (96%) after 6 hours electrolysis. At 1A, however,
possible formation of oxidants (HOCl- and OCl-) at the
anode could have potentially counteracted the deposition
of copper at the cathode. Based on the derived rate
equation from Faradays Law of Electrolysis (dCu/dt = I/
nF), the rate of copper removal is proportional to operating
current. Hence, the rate of copper reoxidation by anodically
generated oxidants (HOCl and OCl-) may potentially
overcome the rate of copper reduction at 1A (about 22 mg
Cu liter-minute-1). Oxidant formation may also occur at
higher operating currents. However, at 3A and 2A, the rates
of copper deposition were found to be higher compared to
the rate of copper reduction at 1A (22 mg Cu liter-minute-1).
Consequently, at 3A and 2A, the rate of copper deposition
could potentially overcome the rate of copper reoxidation.

cost of copper recovery from the acid extracts was based

on the energy cost of the electro-deposition process (PhP
1,256 m-3 acid) as shown in Section 3.3.2 and initial copper
concentration of the acid extract of about 51,950 mg L-1
(Section 3.3).

The temperature of the electrolyte increased slightly

with time for all operating currents (1A, 2A and 3A), which
could be attributed to the heat generated by the resistances
at the electrodes and connectors. Also, a higher operating
current resulted to greater increase in temperature. Hence,
the highest degree change in temperature was recorded
at 3A (10.50C), while the lowest recorded temperature
change was only 0.750C at 1A. On the other hand, the
pH of the electrolyte remained highly acidic since no
signicant change in pH was observed after electrolysis.

CONCLUSIONS

The charge dose of the electrolytic process which

serves as a scale-up and operating parameter for an electrolytic
treatment system was calculated using Equation 1 (Alfafara
et al 2002). Based on the slope of It vs (Co-C)V plot, the
charge dose for the electrodepostion process was calculated
to be approximately 12 Coulombs mg-1 Cu removed for
operating currents higher than 2A. Using the charge dose, the
parameters for a scaled-up process such as reactor volume
and treatment time can be computed using Equation 1.
Based on the charge dose value, the corresponding
energy requirement and energy cost at 3A were computed
to be 14.25 kWh kg-1 Cu removed and PhP 1,256 m-3 acid
extract, respectively.
Preliminary cost estimation of the copper recovery
process from solid PCB Waste
Initial cost calculations for solid PCB waste treatment
was also done based on the empirical results obtained. For
convenience of calculations, a basis of 1 gram solid PCB
waste was used. The cost for acid treatment was calculated
using the prevailing price of nitric acid ($705.32 per 25L,
www.shersci.com) and a waste loading of about 120 mg
PCB waste mL-1 acid (Section 3.2.2). On the other hand, the

The computed cost for acid extraction and electrodeposition were approximately equal to PhP 10.06 g-1 PCB
and PhP 0.01 g-1 PCB, respectively. This corresponds to a
copper recovery cost of about PhP 23 g-1 Cu. The results
indicate that a very large portion of the recovery cost was
in the acid treatment step, and the major cost component
was the cost of nitric acid. Therefore, reusing or recycling
the spent nitric acid in the acid treatment step may be a
good option to signicantly minimize the processing cost
of copper recovery. Studies on the cost-reduction aspects of
recycling spent nitric acid from the acid treatment step is
recommended as follow-up to this study.

The technical feasibility for the application of acid

treatment followed by electrodeposition for the recovery
of copper metal from solid printed circuit board (PCB)
waste was investigated, in order to assess the possibility
of developing a metal-recovery technology for solid PCB
manufacturing waste treatment. Operating conditions for
extraction of copper from solid PCB waste in the acid
treatment step (i.e. oxidizing agent, waste loading and
treatment time) and the conversion of copper ions back to
metallic copper by electrodeposition (i.e. dilution factor and
charge dose), were obtained from lab-scale experiments.
For the acid treatment step, higher amounts of copper
were extracted from the solid PCB waste using HNO3. At
waste loadings between 30 mg PCB waste mL-1 acid and
60 mg PCB waste mL-1 acid, the (extracted) copper ion
concentration increased initially through time before attaining
a level-off value. The level-off value was proportional to the
waste loading, i.e. higher waste loadings gave higher leveloff values of the extracted copper ions. At the highest waste
loading of 150 mg PCB waste mL-1 acid, uctuations in
copper concentration was observed, which may be attributed
to equilibrium shift due to Cu2+ accumulation and reduction
in oxidizing power of the system. Based on the results,
practical operating conditions for acid treatment were
addition of HNO3 to PCB waste at 120 mg PCB waste mL-1
acid waste load ratio and 4 hours contact time.
Copper (as Cu2+) extracts from the rst phase acid
treatment of the solid PCB waste were then reduced into
its metallic form (Cu0) by electrodeposition. Dilution of the
raw concentrated acid extract from the acid treatment step
was deemed necessary since the solution was still reactive
and highly acidic. Electrodeposition experiments at different

Recovery of Copper from Spent Solid PCB wastes

26

dilution factors (DF) showed that there was little or no

copper deposition at the cathode at comparatively low
dilution values (DF 2 and DF 3.5). Low copper deposition
as these dilution factors was attributed to the highly
oxidative environment brought about by the formation
of chlorine-based oxidants (from the anodic oxidation of
naturally occurring chloride ions) and the highly acidic
pH. Copper deposition was, however, found to be feasible
after further dilution to DF 5 and DF 10. The initial rates of
electrolytic copper ion removal were found to be the same
for DF 5 and DF 10 (about 32 mg Cu liter-minute-1) which
was in accordance to Faradays Law of Electrolysis. Copper
concentration leveled off faster at DF 10 (270 minutes) than
in DF 5 (315 minutes) which could be attributed to lower
concentration of copper ions in the electrolyte. Copper
removal efciencies were recorded to be equal to 98% for
DF 5 and 99% for DF 10. Dilution at DF 5 was found to
be more economical since it requires less water for dilution.
The effect of operating current and electrolysis time
was consequently assessed using acid extracts diluted at
DF 5. The electrodeposition experiment was conducted at
different operating currents (1A, 2A and 3A) for 6 hours. A
higher operating current resulted to higher copper removal
efciency and faster rate of copper removal. At 3A, the rate
of copper removal was recorded to be about 32 mg Cu literminute-1 and copper removal efciency was 98%. This was
relatively higher as compared to 28 mg Cu liter-minute-1
copper removal rate and 96% removal efciency observed at
2A. These observations were in accordance to Faradays Law
of Electrolysis. At 1A, on the other hand, copper removal was
found to be not feasible which could be attributed to oxidant
formation at the anode in rates that could have counteracted
the deposition of copper at the cathode. The charge dose
for copper electrodeposition at DF 5 was computed to
be about 11.987 Coulombs mg-1 copper removed, which
corresponds to an energy requirement and energy cost at
3A of 14.25 kWh kg-1 Cu removed and 1,256.02 m-3 diluted
acid exract (PhP 123.98 kg-1 Cu removed), respectively.
Preliminary cost estimates indicate that the
contribution of the cost of the acid treatment step (particularly
the nitric acid cost) was much higher than the cost due to the
electrodeposition step. Recycling or reuse of the spent nitric
acid in the acid extraction step is suggested as a strategy for
signicantly reducing the recovery cost. It would not only
help reduce the total cost, but would also help solve the
problem associated with treating the spent acid extracts. The
environmental and cost benets due to the reuse of spent
nitric acid in the recovery process, is recommended as an
area for future study.

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ACKNOWLEDGMENT
One of the authors (MCC Maguyon) would like to
acknowledge the support of the Department of Science and
Technology-Science Education Institute (DOST-SEI) and
Semiconductor and Electronics Industry in the Philippines,
Inc. (SEIPI), during the conduct of this research during her
graduate studies.

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