NEW CARBON MATERIALS

Volume 28, Issue 2, Feb 2013

Online English edition of the Chinese language journal

Cite this article as: New Carbon Materials, 2013, 28(2):108–114. RESEARCH PAPER

Preparation of porous carbons from non-metallic fractions

of waste printed circuit boards by chemical and physical
activation
KE Yi-hu, YANG Er-tao, LIU Xin, LIU Chun-ling*, DONG Wen-sheng
Key Laboratory of Applied Surface and Colloid Chemistry (SNNU), MOE, School of Chemistry and Chemical Engineering,
Shaanxi Normal University, Xi’an 710062, China

Abstract: Non-metallic fractions of FR-3 type waste printed circuit boards were pyrolyzed at high temperatures. The resultant char at
600 oC was used to prepare activated carbons by physical and chemical activation. The influence of pyrolysis temperature on char yields,
and activation conditions on the burn-off and porous properties of the activated carbons were investigated. Results show that char yields
decrease with pyrolysis temperature. A granular activated carbon with a surface area of 1 019 m2·g-1 and a pore volume of 1.1 cm3·g-1
can be obtained by moulding, pyrolysis and physical activation using H2O as an activation agent. An activated carbon powder with a
surface area of 3 112 m2·g-1 and a pore volume of 1.13 cm3·g-1 can be achieved by KOH activation.

Key Words: Non-metallic fractions; Waste printed circuit boards; Activated carbon

1 Introduction various products, such as construction materials, decorating

Printed circuit boards (PCBs) are the typical and
fundamental component for almost all electronic products,
which contain various metals e.g. Cu, Al, Fe, Sn, Sb, Pb, et al.
and nonmetals e.g. thermosetting resins, reinforcing materials,
brominated flame retardants (BFRs) and other additives. It has
been reported that 20–50 million tones of waste electrical and
electronic equipment (WEEE) are generated worldwide each
year due to product replacement. As one of the most important
branches of WEEE, waste PCBs have drawn much attention
from the public and researchers because plenty of toxic
materials including heavy metals and BFRs can cause huge
damage to the environment if they are not treated properly [1–3].
Currently, the metallic fractions of waste PCBs can be
effectively recycled through mechanical separation methods [3].
The non-metallic fractions (NMFs), which take up almost 70
mass% of waste PCBs, are generally treated by incineration or
land filling. However, incineration of the NMFs could cause
the formation of highly toxic polybrominated dibenzodioxins
and dibenzofurans (PBDD/Fs) [4], while land filling of the
NMFs leads to secondary pollution caused by heavy metal
residues and BFRs leaching to the groundwater [5]. Therefore,
recycling of the NMFs environmental friendly from waste
PCBs remains a huge challenge.
It has been reported that NMFs of waste PCBs can be
recycled using physical or chemical method [6]. In the physical
method NMFs are used as fillers or reinforcing fillers for
agent, adhesives and insulating materials [7–9]. For example, Xu
et al. [8] have prepared phenolic molding compound using
NMFs from paper-based waste PCBs as fillers to replace
wood flour. Shen et al. [9] found that both tensile and flexural
properties of the NMFs/polypropylene composites can be
significantly improved by adding the NMFs into the
polypropylene. Whereas, NMFs are recycled by pyrolysis,
gasification, depolymerization with supercritical fluids and
hydrogenolytic degradation in the chemical method[10–14].
Among these methods, pyrolysis as a promising recycling
method has been widely investigated [13,14]. Pyrolysis of
organic materials contained in waste PCBs leads to the
formation of gases, oils and chars, which can be used as
chemical feedstocks or fuels. A process called “Hloclean”
pyrolysis process has been developed by 10 European partners
from industries, universities and research centers to transform
materials like waste PCBs into fuel oils and to recover
bromine from brominated flame retardants in PCBs. Although
a number of researches have been carried out for handing
NMFs in waste PCBs using pyrolysis, few research focused
on the use of residue chars. In the present work activated
carbons with high porosity were prepared from chars derived
from pyrolysis of NMFs in waste paper-based PCBs by using
chemical and physical activation methods. The optimum
conditions for preparing high porosity activated carbons are
recommended.

Received date: 20 December 2012; Revised date: 1 April 2013

*Corresponding author. E-mail: clliutt@snnu.edu.cn
Copyright©2013, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
DOI: 10.1016/S1872-5805(13)60069-4
 KE Yi-hu et al. / New Carbon Materials, 2013, 28(2): 107–114
2 Experimental
2.1 Materials
The NMFs of wasted PCBs in FR-3 type (kraft mat
impregnated with epoxy resin) were provided by Vary Science
and Technology, Ltd., corporation, Hunan, China with particle
sizes less than 0.07 mm after separating metals.
2.2 Pyrolysis
A laboratory-scale fixed bed tubular reactor was used to
carry out the pyrolysis of NMFs. The sample was heated in a
nitrogen flow (20 mL·min–1) at a ramping rate of 5 ºC·min–1
from ambient temperature to the desired temperature i.e. 500,
600, 700, and 800 ºC, and held at the desired temperature for 2
h. Liquid products evolved during pyrolysis were collected by
a cold trap maintained at 0 ºC by an ice/water bath. The
resulting chars were collected for chemical and physical
activation. The obtained samples were denoted as C500, C600,
C700, and C800, where the numbers refer to pyrolysis
temperatures.
2.3 Preparation of granular activated carbon by physical
activation
The granular activated carbon was prepared according to
the following procedure. The char powder derived from the
pyrolysis of the NMFs at 600 ºC for 2 h was formed in an
extruder under a pressure of 20 MPa using coal-tar pitch as
binder. The addition amount of the binder is 30 mass%. The
resultant granules were heated at a rate of 5 ºC·min–1 to 800 ºC
in nitrogen (20 mL·min–1) in the same tubular furnace, and
carbonized at 800 ºC for 30 min. Then, the granular carbon
was activated at 850 ºC in a mixed stream of N2 (20 mL·min–1)
and H2O (2.8 mL·min–1) for different times i.e. 1, 2, 3, 4 h to
achieve different burn-offs. The obtained activated carbons
were denoted as PA1, PA2, PA3, and PA4, where the numbers
refer to physical activation temperatures.
2.4 Preparation of powder activated carbon by chemical
activation
The same char as above was milled to 200 mesh size
(US standard sieve) using a grinder. Then, the char powder
was mixed with solid KOH (KOH/char = 4/1, w/w) and
activated in N2 atmosphere at 600 and 900 ºC for 2 h. After
activation, the sample was first washed with 1 mol/L HCl to
dissolve ash in the samples, and then washed with distilled
water until the pH value of the residual solution was 7. The
Table 1 The elemental compositions of the samples obtained by EDAX
Samples C /mass% O /mass% Al /mass% Cu /mass%
NMFs 72.29 17.06 0.18 0.83
C600 91.19 6.05 0.25 1.54
PA3 88.39 6.34 0.26 2.31
CA900 89.91 7.93 0.25 0.46
resultant products were collected and dried at 120 ºC
overnight. The obtained samples were denoted CA600 and
CA900, where the numbers refer to chemical activation
temperatures.
2.5 Characterization
The surface areas and the pore size distributions (PSDs)
of the activated carbons were obtained from N2 (77 K)
adsorption measurement using a Micromeritics ASAP2020M
system. The PSDs were calculated using density functional
theory (DFT), and the surface area was calculated by BET
method. The micropore surface area Smi was obtained by the
t-plot method. The average pore diameter (D) was estimated
from the SBET and total pore volume (V) according to the
equation D = 4V/S. Powder X-ray diffraction (XRD) was
performed on a Rigaku D/MAX-Ⅲ X-ray diffractometer (35
kV, 40 mA) using a Cu Kα source. Infrared spectra were
recorded on a Bruker EQUINX55 FTIR spectrometer using
KBr disc method. Thermogravimetric (TG) measurement was
performed on a TGA analyzer (TA-Q600SDT, USA) with a
heating rate of 10 ºC·min-1 under a flow of N2. The scanning
electron microscopy (SEM) and energy dispersive analysis of
X-rays (EDAX) were performed on a Philips-FEI Quanta 200
microscope at 20 kV.
3 Results and discussion
3.1 Characterization of the precursor
Table 1 shows the elemental compositions of the NMFs.
FT-IR spectrum of the NMFs is shown in Fig. 1a. The bands
in the spectrum can be assigned according to the literatures
[15,16]
. The peak at 3 440 cm−1 corresponds to O－H stretching.
The peaks at 2 921 and 2 855 cm–1 correspond to C－H
stretching in benzene ring skeleton. The peak at 1 773 cm–1 is
assigned to C═O stretching in carboxymethyl cellulose of
kraft paper. The characteristic stretching vibration of C═C
double bonds in benzene ring skeleton appears at 1 605, 1 504,
1 454 cm-1, C－H deformation vibration of methyl appears at
1 375 cm-1. The band at 1 251 cm-1 corresponds to P－O－Ar
stretching in triphenyl phosphate. The bands at 1 165, 1 109, 1
024 cm-1 correspond to C－O stretching vibration of aryl- and
aryl ester-based ethers in epoxide resin. The peak at 813 cm-1
is due to the absorption of epoxy group. The peak at 609 cm-1
can be assigned to C－Br stretching. The results indicate that
the NMFs mainly contain brominted epoxide resin, together
with triphenyl phosphate as fire retardant.
Ca /mass% P /mass% Br /mass% Others /mass%
0.11 0.42 6.56 1.33
0.25 0.72 0.25
0.62 2.09
0.25 1.20
 KE Yi-hu et al. / New Carbon Materials, 2013, 28(2): 107–114

Fig. 1 (a) FT-IR spectrum and (b) TGA curve of NMFs.

crystalline grows large and get ordered in the chars with
3.2 Pyrolysis
increasing the pyrolysis temperature.
The thermal stability of the NMFs is very important for Lu et al. [20] have found that the precursors pyrolyzed at
pyrolysis process. Fig. 1b shows TGA curve of the NMFs. It high temperatures are more difficult to be activated with KOH
can be seen that the NMFs show a sharp weight loss in the than those at low temperatures. Our results confirm that low
temperature range of 250–325 ºC, followed by a relatively pyrolysis temperature (500 oC) is insufficient to produce chars
slow weight loss in the range of 325–500 ºC and much slower with effective surface area. Therefore, in the following study,
weight loss in the temperature interval of 500–800 ºC. Finally, the pyrolysis temperature was fixed at 600 oC.
it leaves 15% solid residue after finishing TG experiment. In comparison with the starting NMFs, C content in C600
Fig. 2 shows XRD patterns of the chars derived from the increases significantly, the contents of O and Br element
pyrolysis of the NMFs at different temperatures. Besides some significantly decrease, the content changes of Al, Cu and Ca
diffraction peaks at 43, 51, and 74o attributed to Cu residue, are negligible (see Table 1). This is due to the fact that during
the broad diffraction peak near 23o corresponds to the (002) pyrolysis the resin and kraft mat in the NMFs decomposed,
diffraction of carbons. From the position of the (002) peak (2θ) the bands of C—O, C—C and C－Br were broken, producing
in the XRD patterns, the interplanar spacing d(002) was
determined using Bragg equation [17], and the data is shown in
Table 2. The char yields are also shown in Table 2. It is clear
that the char yields decrease with pyrolysis temperature. The
d(002) value is traditionally used to estimate the graphitization
degree of carbons. In general, growing disorder in carbons is
reflected by increased values of d(002) [18,19]. It can be found
that C500 has the maximum d(002) value among all the
samples, and the d(002) values decrease with increasing the
pyrolysis temperature. From the position and full-width at
half-maximum of the (002) peak, the average grain sizes Lc of
the chars were estimated using the Scherrer equation [17], and
the results are summarized in Table 2. It can be found that
with increasing the pyrolysis temperature Lc increases
Fig. 2 XRD patterns of samples derived from the pyrolysis of the
continually from 0.355 4 nm at 500 oC to 0.760 2 nm at 800
o
NMFs at different temperatures.
C. Combined the interplanar spacing d(002) with Lc values of
the samples, it can be concluded that the micrographite

Table 2 Microcrystalline structural parameters and char yields of samples

from the pyrolysis of the NMFs at different temperatures
Samples Pyrolysis temperature t/ºC Char yield w/% 2θ /(º) d(002) /nm Lc /nm
C500 500 36.2 23.31 0.381 6 0.355 4
C600 600 34.5 23.38 0.380 2 0.394 1
C700 700 32.2 23.48 0.378 6 0.446 8
C800 800 30.2 23.74 0.374 5 0.760 2
 KE Yi-hu et al. / New Carbon Materials, 2013, 28(2): 107–114

CO2, CO, HBr, lower molecular weight aliphatic about 3.0 nm.
hydrocarbons and aromatic hydrocarbons [13]. The burn-offs and porous properties of the powder
activated carbons are also shown in Table 3. It can be found
3.3 Physical activation
that the burn-off, surface area, pore volume and pore size of
The adsorption isotherms of N2 on the granular activated the activated carbons increase with increasing activation
carbons derived from physical activation of C600 at 850 ºC temperature. However, the micropore volume decreases
for different times are shown in Fig. 3. The isotherms of PA1, because an excessive carbon burn-off causes the widening of
PA2, PA3 and PA4 samples show that adsorbed volumes pores and even the loss of some walls between the pores,
increase sharply when p/p0 is ≤ 0.05, and then gradual increase leading to an increased large mesopore volume [24].
when p/p0 is ≥ 0.05. The sharp increase in adsorbed volume at
low pressure indicates that these activated carbons mainly
contain micropores. The linear increase in the
medium-pressure region suggests the existence of larger
micropores. As the activation proceeds the pores are widened,
as inferred from opening knee of the isotherm and higher
slope of the plateau [21]. The adsorption capacities of the
activated carbons generally increase with the extent of
burn-off, indicating that the gasification and pore development
mainly occur inside the carbon particles.
The burn-offs and porous properties of the activated
carbons are shown in Table 3. It can be seen that the burn-off
increases monotonously with increasing the activation time;
while, the surface area, total pore volume, mesopore volume Fig. 3 Nitrogen adsorption isotherms of the activated carbons.
and average pore diameter increase with increasing the
activation time up to 3 h. The results suggest that with
increasing activation time the gasification of carbon results in
the opening of closed pores as well as deepening and
widening of the micropores [22]. When the activation time
increases to 4 h (74.98% burn-off), a rapid decrease in the
surface area, total pore volume, and mesopore volume is
observed. This is due to that over-activation (4 h) causes the
destruction of some pores, leading to an overall loss of surface
area and pore volume [23]. The optimal physical activation time
is then fixed at 3 h. The PSDs (see Fig. 4) indicate that all the
samples contain two fractions of pores; one is near 0.5 nm and
another near 1.3 nm, and a dominant pore size near 0.5 nm.
Fig. 4 The pore size distributions of the activated carbons.
3.4 Chemical activation

Fig. 5 shows the adsorption isotherms of N2 on the

powder activated carbons derived from KOH activation of
C600 at 600 and 900 oC for 2 h. The isotherm of the CA600
shows typical characteristics of microporous carbons. The
adsorbed volume increases sharply when p/p0 is ≤ 0.05, and
then remains nearly constant after p/p0 is ≥ 0.1; the knee of the
isotherm is sharp and the plateau is horizontal. Whereas, the
isotherm of CA900 has typical characteristics of meso and
microporous carbons. The adsorbed volume increases sharply
when P/P0 is ≤ 0.05, and then increases continually after p/p0
is ≥ 0.05. Fig. 6 shows the PSDs of the obtained activated
carbons. The CA600 contains mainly three fractions of pores;
one is near 0.5 nm, another near 1.2 nm, and the third near 2.0 Fig. 5 Adsorption isotherms of N2 on the activated carbons prepared
nm. The CA900 contains mainly three fractions of pores; one by KOH activated at 600 and 900 oC
is near 0.5 nm, another near 1.2 nm, and the third centers at
 KE Yi-hu et al. / New Carbon Materials, 2013, 28(2): 107–114

Table 3 The burn-offs and porous properties of the activated carbons prepared by
physical activation and chemical activation
Samples Burn-offs BET surface areas Pore volumes Micropore volumes Mesopore volumes Average pore sizes
/mass% SBET /m 2·g-1 v/cm3·g-1 v/cm3·g-1 v/cm3·g-1 D/nm
PA1 32.8 670 0.37 0.24 0.13 2.22
PA2 42.3 750 0.45 0.25 0.20 2.41
PA3 64.8 1019 0.71 0.21 0.46 2.81
PA4 74.9 726 0.50 0.21 0.29 2.75
CA600 46.9 1940 0.93 0.59 0.34 1.81
CA900 64.2 3112 1.13 0.30 0.83 2.74

4 Conclusions
It has been demonstrated that activated carbons with high
porosities can be prepared from the chars derived from the
pyrolysis of NMFs of waste PCBs using both physical and
chemical activation. The granular activated carbon with a
specific surface area of 1 019 m2·g–1 and a pore volume of 1.1
cm3·g–1 was obtained by physical activation using H2O as an
activation agent. The powder activated carbon with a surface
area of 3 112 m2·g 1 and a pore volume of 1.13 cm3·g 1 can
– –

be achieved by KOH activation. KOH activation has more

power to destroy the turbostratic graphite microcrystallines
than H2O activation.

Fig. 6 The pore size distributions of the activated carbons.
Fig. 7 XRD patterns of C600, PA3 and CA900
3.5 XRD characterization
Fig. 7 shows the XRD patterns of C600, PA3 and CA900.
It is generally expected that activating process could destroy
the turbostratic graphite microcrystallines. In comparison with
the XRD pattern of C600, the (002) peak of PA3 is broad
slightly, and the (002) peak of CA900 almost disappears. The
results suggest that the graphite microcrystallines be etched to
different extents after physical or chemical activation. In
addition, the diffraction peaks assigned to Cu residue are not
observed in the XRD pattern of CA900. EDAX (see Table 1)
confirms that the CA900 has lower content of metallic
residues than PA3, indicating that the washing with 1 mol/L
HCl after chemical activation can remove effectively the
metallic residues.
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