Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59

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Journal of Analytical and Applied Pyrolysis

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Activated carbons from acrylic textile waste

Mohamad Anas Nahil, Paul T. Williams ∗
Energy and Resources Research Institute, The University of Leeds, Leeds LS2 9JT, UK

a r t i c l e i n f o a b s t r a c t

Article history: Acrylic textile waste was pyrolysed in static bed reactor in a nitrogen atmosphere in relation to different
Received 2 March 2010 pyrolysis temperatures between 500 ◦ C and 900 ◦ C. Steam activation of the chars generated at 800 ◦ C and
Accepted 22 May 2010 900 ◦ C was carried out at three different temperatures, 800 ◦ C, 850 ◦ C and 900 ◦ C to produce activated car-
Available online 31 May 2010
bons. The chemical transformations of raw material and chars produced were investigated using FTIR. The
FTIR spectra indicate the formation of condensed aromatic rings with nitrogen at high temperature. The
Keywords:
pyrolysis chars and activated carbons were characterised in relation to process conditions via BET surface
Pyrolysis
area, proximate and elemental analysis and surface characteristics using scanning and transmission elec-
Textile waste
Activated carbon
tron microscopy. The BET surface area of the pyrolysis chars was all less than 2 m2 g−1 , but increased with
Fuels steam activation to produce a maximum surface area of 619 m2 g−1 for the activated carbon produced
from the char generated at 800 ◦ C and steam activated at 900 ◦ C. The temperature of steam activation
influenced the surface areas of the product activated carbon in that activated carbons produced from
chars generated at 800 ◦ C were significantly higher than those produced from chars generated at 900 ◦ C.
Nitrogen adsorption–desorption isotherms, micropore volume, DFT pore size distribution and electron
microscopy showed that the activated carbons were mostly microporous.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction duce a char followed by steam gasification, alternatively, the raw

Activated carbon is a processed carbon material with a highly
developed porous structure and a large internal specific surface
area (500–3000 m2 g−1 ) [1]. Activated carbons are used extensively
in industrial purification, waste water treatment and chemical
recovery operations. They are particularly advantageous because
of their high internal surface areas and active surfaces. In general,
higher surface areas result in higher adsorption capacities. In addi-
tion, the pore characteristics of activated carbons are important in
determining the particular application of the carbon.
Activated carbon can be made from a wide range of source mate-
rials. Theoretically, any raw material with high content of carbon
could be used to produce activated carbon. In practice, coal, coconut
shells, wood, peat and fruit stones are most commonly used to man-
ufacture activated carbon. However, in laboratory scale studies, an
enormous range of alternative raw materials has been used to pro-
duce activated carbons, such as fruit stones [2], tyre [3], municipal
solid waste [4], synthetic polymers [5] and acrylic fibres [6]. The
use of waste materials to produce activated carbon is preferable
because it reduces the cost of the resultant activated carbon.
The activated carbons can be produced by physical or chemical
activation. For example, physical activation via pyrolysis to pro-
∗ Corresponding author. Tel.: +44 1133432504; fax: +44 1132467310.
E-mail address: p.t.williams@leeds.ac.uk (P.T. Williams).
material may be treated with a chemical such as zinc chloride or
phosphoric acid, followed by thermal treatment via pyrolysis to
produce an activated carbon [7,8].
Whilst there have been many studies on the production of acti-
vated carbons from biomass and bio-degradable waste, there are
fewer data related to textile waste. It is estimated that the gener-
ation of clothing and textile waste in the UK was of the order of 2
million tonnes per year [9]. This represents about 33 kg of cloth-
ing and textile waste per person in the UK and with a population of
500 million for the 27 countries of the European Union, this equates
to approximately 16.5 million tonnes of clothing and textile waste
generated per year in the EU27. Textile waste is considered as one
of the fastest growing sectors in terms of household waste and the
amount of waste is forecast to continue growing as sales of new
textiles and clothing continue to increase. The main categories of
clothing and textile waste are composed of synthetic materials such
as acrylic, nylon and polyester fibres and natural materials such as
wool, flax and cotton.
In addition, the fibrous nature of the textile waste material,
as a feedstock precursor for the production of activated car-
bon, enables the production of fibrous activated carbon. Fibrous
activated carbon has significant advantages over other forms of
activated carbon such as granular and powder, depending on the
field of application [10]. In addition, the nature of the fibrous acti-
vated carbon enables potential production as monoliths, fabrics and
felt [11,12].

0165-2370/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2010.05.005
52 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59
Fig. 1. Schematic diagram of the static bed pyrolysis reactor.
The main object of this study was the investigation of the ther-
mal recycling of one category of textile waste, acrylic material, with
the aim of the production of a higher value activated carbon prod-
uct via pyrolysis and activation. In this respect, the pyrolysis chars
and the derived activated carbons were characterised in relation to
process conditions.
2. Materials and methods
2.1. Waste materials
Acrylic textile fabric waste which is one of the most commonly
polymers used in textile field has been investigated. Acrylic fab-
rics are made up of at least 85% by weight of acrylonitrile units.
The remaining 15% is composed of neutral co-monomers such as
vinyl acetate (VA), methyl acrylate (MA) or methyl methacrylate
(MMA) which play an important role in improving the diffusion
rate of dyes into acrylic fibre [13]. The acrylic textile waste fab-
ric was obtained as clothing waste and shredded to produce small
pieces of size 2 cm2 .
2.2. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was applied to determine the
thermal degradation characteristics of the waste sample via the
weight change of the sample as a function of the temperature. A
Shimadza TGA-50H analyser was used to study the thermal degra-
dation of the acrylic fabric waste. The sample weight was 5 mg and
was loaded onto the alumina pan of the TGA and suspended within
the furnace. Nitrogen gas was used during the process to ensure
an inert atmosphere in the unit. The waste sample was heated at a
heating rate 5 ◦ C min−1 to a final temperature 900 ◦ C
2.3. Pyrolysis reactor
Pyrolysis of the textile waste was carried out in static bed batch
reactor, 250 mm in length by 30 mm internal diameter and was
externally heated by a tube furnace 1.2 kW (Fig. 1). The furnace
was controlled to produce the desired heating rate, final temper-
ature and final pyrolysis temperature hold time. The crucible was
filled with 8 g of the shredded acrylic textile waste and heated to
different final temperatures of 500 ◦ C, 600 ◦ C, 700 ◦ C, 800 ◦ C and
900 ◦ C at a heating rate of 5 ◦ C min−1 and held at each final temper-
Fig. 2. Schematic diagram of the char activation reactor.
ature for 2 h. In separate experiments to determine the structural
group composition of the solid product in relation to temperature
of thermal degradation, the textile sample was heated to temper-
atures between 150 ◦ C and 900 ◦ C and held at that temperature for
10 min. Nitrogen was used as the carrier gas to provide an inert
atmosphere and to sweep the evolved pyrolysis gases from the
reactor, which also served to minimise any secondary reactions of
the gases. A stainless steel sample crucible was used to hold the
sample. Three condensers were used to trap the condensable prod-
ucts consisting of a water cooled condenser, followed by two solid
CO2 cooled condensers. A further condenser was packed with glass
wool to remove any oil mist. Following this, a dreschel bottle filled
with deionised water was used to dissolve water soluble gases. Gas
samples were taken during the pyrolysis process at regular inter-
vals (every 15 min) using gas syringes at the gas sampling point
which was located between the last condenser and the dreschel
bottle.
2.4. Activation reactor
The pyrolysis reactor was adapted to activate the chars produced
from the pyrolysis experiments (Fig. 2). Two chars were investi-
gated for activation, those produced at 800 ◦ C and 900 ◦ C. A steam
generator was introduced to produce the activating agent for the
production of the activated carbons from the pyrolysis chars. The
steam generator furnace was maintained at 300 ◦ C. A Sage instru-
ment model 255-2-syringe pump was used to inject deionised
water into the steam generator. The flow rate of the water was
2.34 cm3 /h and the activating molar flow rate per unit weight of
char was calculated as 0.0325 mol g−1 h−1 . The molar flow rate of
water was calculated from the flow rate of water, the molecular
weight of water and the weight of char sample used for activation.
The char samples produced by the pyrolysis of the acrylic waste
at 800 ◦ C and 900 ◦ C were ground and sieved to 211–599 ␮m and
dried at 105 ◦ C overnight. The sample size of char for activation
was 4 g. Nitrogen was the carrier gas and the activation reactor
was heated at a heating rate of 5 ◦ C min−1 to different activation
temperatures of 800 ◦ C, 850 ◦ C and 900 ◦ C. Once the activation tem-
 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59 53

perature was attained, the steam was introduced for a period of 3 h.

The nomenclature used in this paper for the resultant chars and
activated carbons was as follows: C denoted char, followed by the
pyrolysis temperature at which the char was produced, AC denoted
activated carbon, followed by the pyrolysis temperature in which
the char was produced followed by the activation temperature. For
example, C 800 stands for char produced at 800 ◦ C and AC 800 900
stands for an activated carbon derived from the char produced at
800 ◦ C and activated at 900 ◦ C.

2.5. Characterization of chars and activated carbons

The BET surface area and the porosity of the chars and activated
carbons were determined using a Micromeritics TriStar 3000 appa-
ratus. The system operates by measuring the quantity of nitrogen
adsorbed onto or desorbed from a solid sample at different equi-
librium vapour pressures. The micropore volume and total pore
Fig. 3. Thermogravimetric and differential thermograph curve of acrylic textile
volume were obtained by the Dubinin–Radushkevich (DR) method waste in nitrogen.
[14]. The total pore volume was determined from the quantity of gas
adsorbed at a relative pressure of 0.98. Pore size distribution was
determined by the density functional theory (DFT) method [15].
The sample size was 0.5–1.0 g.
The elemental analysis (C, H, N, S, O) of the acrylic waste, char
and activated carbon samples was carried out using a Carlo Erba
Flash EA 1112 elemental analyser. Between 2.5 mg and 4 mg of each
sample was used for the analysis.
A Shimadzu TGA-50H analyser was used to perform the proxi-
mate analysis of raw material, chars and activated carbons. Heating
of the sample in a nitrogen atmosphere to 110 ◦ C corresponded to
the determination of moisture in the sample. Heating to 925 ◦ C pro-
duced weight loss corresponding to the content of volatile matter
and residual fixed carbon, in the sample and introduction of air pro-
duced burn-off of the fixed carbon in the sample and leaving the
ash in the aluminium pan.
FTIR (Fourier transform infrared) spectrometry was used to
characterise pure polyacrylonitrile (PAN), polyvinylacetate (PVA) Fig. 4. Yield of acrylic waste pyrolysis products in relation to temperature.
and the carbon samples in terms of their functional group com-
position. A Nicolet Magna IR-560 FTIR spectrometer was used in
by Pan et al. [16] for polyacrylonitrile precursor. They suggested
conjunction with a PC enabled with OMNIC data-handling software.
that the first peak may be attributed to the cyclisation of chain
The chars and activated carbons were analysed using a high res-
polyacrylonitrile molecules and the second peak, may be due to
olution LEO 1530 FEG scanning electron microscope. The activated
cross-linking of adjacent cyclised molecules
carbon was also analysed using transmission electron microscope
Nabais et al. [10] studied the thermal degradation in nitrogen
TEM. A Philips CM200 FEGTEM to attain high magnification images
of acrylic fibres by FTIR spectrometry of the precursor and samples
of the resultant activated carbons.
collected at different degradation temperatures. They found that
the chemical transformations of the precursor occurred at 250 ◦ C
3. Results and discussion and these transformations continued until 800 ◦ C. Surianarayanan
et al. [17] investigated the thermal degradation of polyacryloni-
3.1. Thermogravimetric analysis trile using pyroprobe-gas chromatography/mass spectrometry and
found that the acrylonitrile polymer degrades to gaseous and
Thermogravimetric analysis (TGA) was used to investigate the volatile products over the temperature range of 150–590 ◦ C with
thermal degradation characteristics of the acrylic textile waste concurrent stabilisation of the solid carbonaceous residue.
sample. Fig. 3 shows the TGA thermograph for the acrylic textile
waste and the differential calculations of the weight loss (DTG) 3.2. Product yield
obtained at a heating rate 5 ◦ C min−1 to a final temperature 900 ◦ C.
The initial decrease in weight is due to the moisture loss, followed The product yields obtained from the pyrolysis of acrylic textile
by the second weight loss which is the main thermal degrada- waste in the static bed reactor in relation to final pyrolysis temper-
tion step. This step occurred between 270 ◦ C and 380 ◦ C. Then a ature are shown in Fig. 4. They correspond to the TGA data which
further weight loss occurred between 380 ◦ C and 500 ◦ C. There- indicated that the main weight loss occurred below 500 ◦ C. The
after there was a gradual weight decrease as the temperature was char mass decreased as the pyrolysis temperature was increased
increased. The amount of solid residue remaining at 900 ◦ C was 44 from 500 ◦ C to 900 ◦ C, while oil/wax and gas yields were raised.
wt%, consisting of the carbonaceous residue or char. The DTG curve Similar trends have been found for other polymeric wastes [18,19].
shows two distinct main weight loss peaks of thermal degradation. The final mass of solid residue at 900 ◦ C was quite similar to that
The two stages could be associated either with decomposition of obtained using the thermogravimetric analyser at about 48 wt%
polyacrylonitrile and polyvinylacetate or with different processes char. Carrott et al. [6] investigated the pyrolysis of acrylic fibres
of polyacrylonitrile decomposition. Similar results were published composed of acrylonitrile and vinyl acetate and they reported that
54 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59

Table 1
Elemental analysis of the acrylic textile waste and chars in relation to final pyrolysis
temperature.

C (wt%) H (wt%) N (wt%) O (wt%)

Acrylic textile waste

66.2 6.0 22.9 4.9

Pyrolysis temperature (◦ C) Chars

C (wt%) H (wt%) N (wt%) O (wt%)

500 71.4 3.0 19.0 6.6

600 72.8 2.1 18.7 6.4
700 73.6 1.9 18.3 6.2
800 76.7 1.8 16.1 5.4
900 79.5 0.8 14.5 5.2
Fig. 5. Activated carbon product yield and burn-off in relation to activation tem-
perature.
Table 2
Elemental analysis of activated carbons in relation to temperature.
sition continues to change and the activated carbon fibres produced
Activation temperature (◦ C) C (wt%) H (wt%) N (wt%) O (wt%) at high burn-off still contain significant amounts of nitrogen (3–4%)
Activated carbon from char produced at 800 ◦ C and oxygen (5–8%).
800 77.8 1.5 12.8 7.9 Table 3 shows the proximate analysis of the acrylic textile
850 79.7 1.4 10.1 8.8 waste material and the chars produced at different final pyrolysis
900 87.3 1.2 5.3 6.2 temperatures. The results indicate that there is a slight reduction
Activated carbon from char produced at 900 ◦ C in moisture content of the char samples as the pyrolysis tem-
800 84.8 0.7 10.6 3.9 perature was increased. While the volatile matter decreased and
850 84.2 1.0 8.8 6.0
fixed carbon contents and ash increased with increasing pyroly-
900 87.4 0.9 6.3 5.4
sis temperature. The product oils/waxes were analysed by Fourier
transform infrared spectrometry to determine the functional group
composition. The spectra indicated the presence of unsaturated
the final mass of carbonised fibres produced at 800 ◦ C of 52 wt%,
nitrile groups, mono- and polycyclic and substituted aromatic
similar to that found in this work at 800 ◦ C.
groups and alkane groups. The pyrolysis gases collected using gas
Table 1 presents the elemental analysis of the acrylic waste
syringes were analysed using packed column gas chromatography.
material and the chars produced from acrylic waste pyrolysed
The main gases produced during the pyrolysis of acrylic textile
to different temperatures. By assumption that all of the nitrogen
waste to different temperatures were CH4 , H2 , C3 H8 and C4 H10 with
existed in acrylic textile waste comes from the acrylonitrile (AN)
lower amounts of other hydrocarbons gases. As the pyrolysis tem-
monomer and that all the oxygen comes from the vinyl acetate (VA)
perature was raised from 500 ◦ C to 900 ◦ C the amount of CH4 , H2
monomer, the AN and VA percentages can be calculated from the
increased whereas the mass of other gases was mostly stable. The
elemental analysis results of acrylic textile waste [6]. The results
evolution of gases in relation to pyrolysis time showed that the
showed that the acrylic textile waste used in this study contained
gases evolved between 270 ◦ C and 900 ◦ C in single stage. The max-
86.8% of AV and 13.2% VA. In regard to the elemental compositions
imum outflow of hydrogen was at 700 ◦ C and for methane was at
of the chars, it is clear that nitrogen, hydrogen and oxygen contents
600 ◦ C, whereas the maximum outflow of other hydrocarbons was
of the chars decreased as the pyrolysis temperature was increased
at around 500 ◦ C. Xue et al. [20] studied the thermal degradation
with a corresponding increase in carbon. The nitrogen contents of
of polyacrylonitrile using TGA/FTIR technique. They noted the for-
the char were high at between 14.5 wt% and 19 wt% depending on
mation of ammonia and hydrogen cyanide in addition to methane
pyrolysis temperature. Nabais et al. [10] studied the effect of pyrol-
and some traces of other hydrocarbons.
ysis temperature on the atomic ratio of acrylic fibres. They observed
Fig. 5 shows the product yield of activated carbon in relation to
that the N/C ratio stayed approximately constant with increasing
the temperature of activation, the duration of the steam activation
the temperature up to 300 ◦ C then showed a slightly decrease dur-
process was 3 h in each case. The product yield of activated carbon
ing the carbonisation up to 800 ◦ C due to the volatilisation of some
is markedly influenced by the activation temperature. The char and
nitrogen with the production of HCN. The O/C ratio showed a small
steam interact to produce mainly carbon dioxide, carbon monoxide,
increase indicating the formation of new oxygenated functional
groups. The atomic ratio H/C increased with the temperature up
to 150 ◦ C and after that decreased. Table 2 shows the elemental Table 3
Proximate analysis of acrylic textile waste and chars in relation to final pyrolysis
composition of the activated carbons produced after 3 h activation temperature.
at 800 ◦ C, 850 ◦ C and 900 ◦ C from chars generated at 800 ◦ C and
900 ◦ C pyrolysis temperature. Compared to the elemental analy- Moisture (wt%) Volatiles (wt%) Fixed carbon (wt%) Ash (wt%)

sis of the chars, the carbon contents of the activated carbons are Acrylic textile waste
quite similar and show little influence of activation temperature. 0.2 80.9 18.6 0.3

However, the nitrogen contents show a reduction compared to

Pyrolysis Chars
the chars and significant reduction was observed as the activa- temperature (◦ C)
tion temperature increased. Carrott et al. [6] studied the elemental
composition changes during the production of activated carbon Moisture Volatiles Fixed carbon Ash
(wt%) (wt%) (wt%) (wt%)
fibres from acrylic fibres. They found that during the carbonisation, 500 4.5 32.2 62.6 0.7
the nitrogen content was approximately halved and the hydrogen 600 4.8 25.2 69.2 0.8
content decreases approximately fivefold, while there are corre- 700 4.6 22.1 72.3 1.0
spondingly large increases in the carbon and the oxygen contents. 800 3.2 19.8 75.9 1.1
900 1.8 17.5 79.5 1.2
They also reported that during the activation the elemental compo-
 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59 55

Fig. 6. FTIR spectra of pure polyacrylonitrile and solids produced at different temperatures.

hydrogen and methane, with a marked reduction or ‘burn-off’ of 3.3. FTIR spectra of solid materials
the carbon. Fig. 5 also shows the ‘burn-off’ in relation to activation
temperature. The FTIR spectra for pure polyacrylonitrile (PAN), polyvinylac-
The degree of carbon loss or burn-off was calculated from: etate (PVA), acrylic waste, and the carbon samples collected at
different temperatures are shown in Figs. 6–8. The acrylic textile
waste fabric was composed of mainly acrylonitrile with a lower
(w1 − w2 )
burn-off = × 100 wt% (daf) content of vinyl acetate. FTIR was used to investigate the chemical
w1
transformations of the acrylic waste during the pyrolysis process.
Figs. 6 and 7 show the FTIR spectra of the polyacrolonitrile and
w1 , initial char mass on a dry, ash free basis, g; w2 , mass of char polyvinylacetate, respectively, as they are thermally degraded dur-
(activated carbon) after activation, on a dry ash free basis, g. ing pyrolysis. Fig. 8 shows that as the temperature of pyrolysis was

Fig. 7. FTIR spectra of pure polyvinylacetate and solids produced at different temperatures.
56 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59

Fig. 8. FTIR spectra of acrylic textile waste and solids produced at different temperatures.

increased from 150 ◦ C to 900 ◦ C the spectral peaks of the acrylic

waste gradually disappear to produce the carbonaceous char with-
out any clear spectral peaks.
With reference to the spectral peaks shown in Figs. 6 and 7
for polyacrlonitrile and polyvinylacetate, the thermal degradation
of the acrylic textile waste material can be discussed. The peaks
appearing at 2930 cm−1 , 2875 cm−1 , 2240 cm−1 , 1465 cm−1 and
1240 cm−1 are attributed to stretching CH2 + rocking CH2, stretching CH2 ,
stretch CN, bending CH2 and wagging CH2 + wagging CH which exist in acry-
lonitrile [10]. The sharp peaks at 1720 cm−1 , 1635 cm−1 and
1372 cm−1 are due to stretching C O, stretching C C and O CO CH3
which are also exist in vinyl acetate (Figs. 6 and 7).
No change on the intensity of the spectral peaks was observed
on the samples collected at the pyrolysis temperatures of 150 ◦ C
and 200 ◦ C. For the sample collected at a pyrolysis temperature of
Fig. 9. Adsorption and desorption isotherms of N2 at 77 K for activated carbons.
250 ◦ C the intensity of the spectral peaks decreased which indicates
that the degradation had started. Some modifications of precursor
peaks were clearly noted on the spectrum of the sample collected at
peratures less than 150 ◦ C. They suggested that the vinyl acetate
300 ◦ C. For example, the aliphatic CH2 groups existed in the acrylic
present in the acrylic material acted as a cyclisation catalyst. In
waste precursor disappear and the intensity of the nitrile band
addition, they suggested that dehydrogenation reactions are of
(stretch CN) decreases. New spectral peaks appeared on the spectrum
minor importance. At temperatures above 250 ◦ C cyclisation and
of the sample collected at 400 ◦ C such as the peaks at 1600 cm−1 and
dehydrogenation reactions co-exist as the acrylic waste material
1385 cm−1 , which results from the merging of peaks at 1465 cm−1
thermally degrades to produce carbon. Nabais et al. [10] pointed
and 1372 cm−1 . The band situated at 1600 cm−1 is ascribed to the
out that during activation, burn-out of the carbon to produce acti-
contribution of several vibrational modes of the aromatic rings in
vated carbon results in the formation of pyrone and lactone groups
carbon materials stretching C N, stretching C C and NH [10].
and rearrangement of amine and amide groups.
For the sample collected at 500 ◦ C the spectrum shows a shoul-
Surianarayanan et al. [17] for the thermal degradation of poly-
der at 1655 cm−1 . Mittal et al. [21] investigated the thermal changes
acrylonitrile suggested that linear polymerisation of nitrile groups
in polyacrlonitrile using infrared spectrometry and attributed the
is the principle reaction in the decomposition process, followed by
presence of this shoulder to the formation of conjugated ketones
cyclisation and extended conjugation.
that disappear at higher temperatures to form crosslink bonds. At
800 ◦ C, the disappearance of the shoulder indicates the formation
of condensed aromatic rings with nitrogen. 3.4. Porous properties of chars and activated carbons
Nabais et al. [10] studied the chemical transformations of
commercial acrylic fibres during the production of activated car- The surface area of the pyrolysis chars were very low and were
bon fibres using Fourier transform infrared spectrometry. They all less than 2 m2 g−1 . Activation of the pyrolysis chars with steam
concluded that thermal degradation of acrylic fibres starts with produced a marked increase in the surface area and porosity of
cyclisation of the polymeric chain of the acrylic material at tem- activated carbons (Table 4).
 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59
Table 4
BET surface area of activated carbons produced at different activation temperatures.
Char produced at 800 ◦ C
Activation BET surface area Micropore volume Total pore volume
temperature (◦ C) (m2 g−1 ) (m3 g−1 ) (m3 g−1 )
800 148 0.058 0.059
850 354 0.148 0.151
900 619 0.281 0.302
Fig. 9 illustrates the adsorption and desorption isotherms
of N2 on the activated carbons produced at different activa-
tion temperatures. The adsorption and desorption isotherms
enable the characteristics of the pore structure to be determined.
According to a classification system devised by IUPAC [22]. The
adsorption–desorption isotherms shown in Fig. 9 for the activated
carbons are mostly of Type I for the activated carbons produced at
800 ◦ C and 850 ◦ C from the chars generated at 800 ◦ C and 900 ◦ C.
The Type I isotherm is concave to the relative pressure (P/P0 )
axis. It rises sharply at low relative pressures and then reaches a
plateau which is horizontal and parallel to the relative pressure
axis. This isotherm occurs due to an increase in the interaction
between the solid surface and the gas molecules in micropores
which lead to an increase in adsorption, especially at low rel-
ative pressure. However, the samples AC 800 900 and AC 900
900 produced adsorption–desorption isotherms characteristic of
Type I/Type IV which exhibit hysteresis (H4 type) in relation to
adsorption–desorption of the N2 , representing the presence of
mesopores in addition to micropores. The hysteresis loop is usually
associated with capillary condensation in mesporous structures
[22].
Table 4 shows the BET surface area, micropore volumes and
total pore volumes of the activated carbons produced at dif-
ferent activation temperatures of 800 ◦ C, 850 ◦ C and 900 ◦ C for
the pyrolysis char samples produced at 800 ◦ C and 900 ◦ C. The
steam activation process produced a significant increase in sur-
face area, from <2 m2 g−1 for the pyrolysis char to 619 m2 g−1 for
the activated carbon at the highest surface area. Increasing the
temperature of activation produced an increase in surface area
of the activated carbons for both chars produced at the pyroly-
sis temperatures of 800 ◦ C and 900 ◦ C. The BET surface areas of
the activated carbon derived from chars generated at 800 ◦ C were
significantly higher than those produced from chars generated
at 900 ◦ C at the same activation temperature, being 148 m2 g−1
compared to 52 m2 g−1 , 354 m2 g−1 compared to 204 m2 g−1 and
619 m2 g−1 compared to 373 m2 g−1 , respectively. This is most
likely due to the higher reactivity of the steam with chars car-
bonised at lower temperature than activation temperature. This
higher reactivity is attributed to the chars produced at tem-
perature lower than activation temperature can be exposed to
further pyrolytic decompositions during the activation process
which causes more mass loss and higher surface area. Other
researches also reported that the activation temperature has a sig-
nificant influence on surface area of the resultant activated carbons
[8,23].
Fig. 5 showed that higher activation temperatures produced
higher degrees of burn-off, representing loss of carbon due to
the reaction with steam. However, Table 4 shows that markedly
higher surface areas are produced at the higher activation temper-
atures. But, higher burn-off represents lower yield of the activated
carbon. For example, to produce the higher surface area acti-
vated carbon of 619 m2 g−1 for the char produced at 800 ◦ C and
steam activated at 900 ◦ C resulted in a loss of 73.3 wt% of the
char.
Micropore volume data presented in Table 4 show that the
majority of the porosity development was due to the formation
57
Char produced at 900 ◦ C
Activation BET surface area (m2 g−1 ) Micropore volume Total pore volume
temperature (◦ C) (m3 g−1 ) (m3 g−1 )
800 52 0.018 0.018
850 204 0.086 0.088
900 373 0.173 0.180
of micropores. The classification of pore size in activated carbons is
that micropores are of pore width <2 nm, mesopores of pore width
2–50 nm and macropores of pore width >50 nm. The pore width
refers to the distance between the walls of slit shaped pores or the
radius of cylindrical shaped pores. The development of the surface
area and porosity characteristics of an activated carbon produced
by the pyrolysis – steam activation route would be determined by
the characteristics of the original raw materials and the process
conditions of pyrolysis and activation. During the initial pyroly-
sis stage the feedstock material, the acrylic textile waste, would
soften and the evolution of volatile matter produces bubbling in
the material followed by hardening and shrinkage of the char. The
subsequent steam activation of the char produced from the acrylic
waste proceeds by micropore formation, followed by pore enlarge-
ment, as the steam reacts with the carbon [24,25]. Increasing the
activation temperature leads to an increase in reactivity between
steam and carbons. This results in the opening of previously inac-
cessible pores through the removal of tars and disorganised carbon.
New pores are also created by selective activation. Thereafter, the
widening of the developed porosity occurs [26,27]. This is in agree-
ment with micropore volume and total pore volume data exhibited
in Table 4 that indicate that wider pores are created as the intensity
of the activation is increased.
Fig. 10 shows the DFT pore size distributions for two samples
of activated carbon, AC 800 900 and AC 900 850. This data con-
firms that the activated carbons produced are mainly micropores
with some mesopores, depending on the pyrolysis and activation
temperatures. The pore size distribution of the activated carbons
produced was mostly below 5 nm. The mesopores produced on
both samples have narrow widths between 2 nm and 5 nm. For
the AC 800 900 sample, higher content of micropores and meso-
pores than the AC 900 850 sample were suggested by the DFT
analysis. This confirms the porosity development during process-
ing, including the creation of new micropores and conversion of
some micropores to mesopores.
Fig. 10. DFT pore size distribution of activated carbon produced at 900 ◦ C from char
generated at 800 ◦ C and 900 ◦ C, respectively.
58 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59
Fig. 11. Scanning electron micrographs of (a) C 800, (b) C 900, (c) AC 800 900 and (d) AC 900 900.
Fig. 12. Transmission electron micrograph of activated carbon AC 800 900.
3.5. Electron microscopy of chars and activated carbons
Fig. 11 shows the scanning electron micrographs of the acrylic
waste textile pyrolysis char produced at 800 ◦ C and 900 ◦ C and
micrographs of the activated carbons produced from 800 ◦ C char
activated at 900 ◦ C and carbons produced at 900 ◦ C and activated at
900 ◦ C. The pyrolysis chars shown in Fig. 11(a) and (b) have smooth
surface characteristics, higher SEM magnification shows few pores
on the surface of the char which corresponds with the low surface
area of the chars.
Fig. 11(c) and (d) shows the scanning electron micrographs of
the steam activated carbons. The surface characteristics showed
clearly that the pores in the range of 10–50 nm could be observed,
i.e. mesoporous and macropores. The magnification of the SEM
system could not identify very small micropores of <2 nm. This is
in agreement with the nitrogen adsorption results obtained dur-
ing the measurement of surface area, corresponding to a marked
increase for the steam activated carbons compared to the pyrolysis
chars.
Transmission electron microscopy (TEM), which enables a much
higher magnification, was used to identify the microporosity in the
product activated carbons. Fig. 12 shows a TEM micrograph of the
acrylic textile waste derived activated carbon for the char produced
at 800 ◦ C and activated at 900 ◦ C. This homogeneous morphology,
together with the DFT porosity analysis, suggests microporosity on
the activated carbon surface for this portion of the carbon anal-
ysed.
4. Conclusions
The present study shows that acrylic textile waste can be
efficiently used as precursor material for the preparation of acti-
vated carbon. The yield, elemental and proximate analysis of char
was influenced by pyrolysis temperature. FTIR analysis confirmed
the formation of condensed aromatic rings with nitrogen in the
structure of the chars produced at high temperature. The BET
surface area of char samples produced at different temperatures
was <2 m2 g−1 . However, steam activation of the chars produced
an activated carbon with a maximum surface area of 619 m2 g−1
produced from the char generated at 800 ◦ C and steam acti-
vated at 900 ◦ C. The surface areas of the activated carbon derived
from chars generated at 800 ◦ C were significantly higher than
those produced from chars generated at 900 ◦ C at the same acti-
vation temperature. Nitrogen adsorption–desorption isotherms,
micropore pore volume, DFT pore size distribution confirm the
microporous nature of the resultant activated carbons. The results
show that acrylic textile waste can be successfully physically acti-
vated to produce a microporous activated carbon with a high
surface area.
Acknowledgements
We would like to thank the Syrian Ministry of Higher Education
and Al Baath University, Homs, Syria, and also to Prof. Saad Kherfan
for support for Mohamad Anas Nahil. We would also like to thank
Dr. Jude Onwudili for help with analyses.
 M.A. Nahil, P.T. Williams / Journal of Analytical and Applied Pyrolysis 89 (2010) 51–59
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