Fuel 87 (2008) 3278–3285

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Fuel
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A novel method for production of activated carbon from waste tea

by chemical activation with microwave energy
Emine Yagmur, Meryem Ozmak, Zeki Aktas *
Ankara University, Faculty of Engineering, Department of Chemical Engineering, Tandogan, 06100 Ankara, Turkey

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

Article history: This study presents the production of activated carbon from waste tea. Activated carbons were prepared
Received 14 December 2007 by phosphoric acid activation with and without microwave treatment and carbonisation of the waste tea
Received in revised form 9 May 2008 under nitrogen atmosphere at various temperatures and different phosphoric acid/precursor impregna-
Accepted 13 May 2008
tion ratios. The surface properties of the activated carbons were investigated by elemental analysis,
Available online 9 June 2008
BET surface area, SEM, FTIR. Prior to heat treatment conducted in a furnace, the mixture of the waste
tea and H3PO4 was treated with microwave heating. The maximum BET surface area was 1157 m2/g
Keywords:
for the sample treated with microwave energy and then carbonised at 350 °C. In case of application of
Activated carbon
Biomass
conventional method, the BET surface area of the resultant material was 928.8 m2/g using the same pre-
Chemical activation cursor and conditions. According to the Dubinin–Radushkevich (DR) method the micropore surface area
Microwave energy for the sample treated with microwave energy was higher than the sample obtained from the conven-
Carbonisation tional method. Results show that microwave heating reasonably influenced the micropore surface area
of the samples as well as the BET surface area.
The samples activated were also characterised in terms of the cumulative pore and micropore volumes
according to the BJH, DR and t-methods, respectively.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Activated carbons have been used for a long time as adsorbents
in many applications in which impurities and contaminations in
low concentration are removed. The adsorption capacities of acti-
vated carbons (ACs) strongly depend on their porosity and surface
area. Since the textural properties of ACs depend on the starting
material and the preparation method, many natural and synthetic
materials have been used as precursors. ACs with high surface area
and pore volumes can be prepared from a variety of carbonaceous
materials such as coal, coconut shell, wood, agricultural wastes or
industrial wastes. In industrial practice coal and coconut shell are
two main sources for the production of ACs. Approximately half
of the raw materials used are lignocellulosic ones [1,2]. Interests
are growing in the use of other low-cost and abundantly available
lignocellulosic materials as precursors for the preparation of ACs
[3–7].
There are two processes for the preparation of ACs: physical and
chemical activation. Physical activation involves carbonisation of a
carbonaceous material followed by activation of the resulting char
in the presence of activating agents such as CO2 or steam. In the
chemical activation, the raw material is impregnated with activat-
* Corresponding author. Tel.: +90 312 2126720x1300; fax: +90 312 2121546.
E-mail address: zaktas@eng.ankara.edu.tr (Z. Aktas).
ing agents such as ZnCl2, H3PO4, KOH, K2CO3; then the impregnated
material is heat-treated in an inert atmosphere at various temper-
atures [2,8,9].
Behaviours of the agents during chemical activation show dif-
ferent effects on the final product. In the use of ZnCl2, the activated
carbons had large surface areas and more micropore structure
[4,6]. As an activation agent, H3PO4 is widely used in the prepara-
tion of ACs from lignocellulosic products and offers some advanta-
ges such as non-polluting character (compared to ZnCl2, for
instance) and ease of elimination by extraction with water
[10,11]. Girgis and El-Hendawy [7] reported that phosphoric acid
inflicted physical and chemical modifications on the botanical
structure by penetration, particle swelling, and partial dissolution
of the biomass, bond cleavage and reformation of new polymeric
structures resistant to thermal decomposition.
In the use of H3PO4 as a chemical activating agent, the pore size
distributions were more heterogeneous for the activated carbons
obtained from olive and peach stones as precursors [6]. Budinova
et al. [5] prepared different activated carbons by impregnation of
H3PO4 on woody biomass birch followed by carbonisation in differ-
ent gaseous atmospheres. They concluded that the properties of
the activated carbons were strongly dependent on the preparation
conditions such as H3PO4 concentration, impregnation ratio and
gases used for activation. Date pits activated with H3PO4 were
pyrolysed at three different temperatures. It was reported that
the activated carbons produced were fairly suitable to adsorb

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.05.005
 E. Yagmur et al. / Fuel 87 (2008) 3278–3285
contaminants in liquids. The advantages of the porous material
activated by H3PO4 were also reported in the same article.
The application of microwave (MW) heating technology for
regenerating industrial waste activated carbon has been investi-
gated with very promising results [12,13]. The main difference be-
tween MW devices and conventional heating systems is in the way
the heat is generated. In the MW device, the microwaves supply
energy directly to the carbon bed. Energy transfer is not by conduc-
tion or convection as in conventional heating, but microwave en-
ergy is readily transformed into heat inside the particles by
dipole rotation and ionic conduction [12–14].
Recently microwave energy has been widely using in several
fields of applications on both research and industrial processes.
Although the use of microwave energy changes the properties of
carbonaceous materials very much, there are relatively few publica-
tions that describe the use of microwaves for producing [15,16] and
regenerating [17–19] activated carbons. Nabais et al. [13] studied on
the surface chemistry modification of activated carbon fibres by
means of microwave heating which was found to be very effective.
This study has focused on the production of ACs from waste tea
collected from a tea factory in Turkey. Dried and cured tea leaves
are widely used for beverage. High quality tea is obtained from the
three or four top leaves of the shoot on the tea plant. While tea pro-
ducers cut the top tea leaves with special tea shears, some over-
grown woody shoots, which may include six to seven top leaves,
mixed in the tea harvest. During the tea production procedure, this
woody overgrown shoots were not treated by tea factory and
formed into tea factory waste. The waste tea (30,000 tones/year) is
not used for any purpose in Turkey. It is deposited in depository
areas or occasionally discarded in small bays in the Black Sea [20].
Although many studies in the literature have been reported
concerning the production of activated carbon from biomasses by
phosphoric acid activation, there is no study regarding activated
carbon prepared from the waste tea treated with microwave en-
ergy in the presence of phosphoric acid. In this study, prior to heat
treatment process conducted in a furnace, the mixture of the waste
tea and H3PO4 was treated with microwave energy. The influences
of some parameters such as carbonisation temperature, phosphoric
acid/precursor ratio on the resultant activated carbon were inves-
tigated and the raw material and final product were characterised
in terms of surface area, pore size, surface morphology and chem-
ical structure. Findings of the experiments performed with conven-
tional method and a new method suggested in this article were
discussed and some conclusions were reported.
2. Experimental
2.1. Materials used and procedure
The tea factory waste (waste tea) was obtained from a tea plant
located in Eastern Black Sea region in Turkey. Prior to the experi-
ments, the raw material was crushed and sieved to 250–500 lm
size fraction. An 85% (wt) H3PO4 (Merck) solution was used as
chemical activating agent. Crushed and sieved waste tea samples
were mixed with H3PO4 to the desired acid/precursor ratio (weight
of H3PO4/weight of waste tea) in teflon beakers. The H3PO4 impreg-
nated samples were immediately subjected to microwave (MW)
treatment for 30 s. Microwave heating treatments were conducted
in a household type microwave furnace (Vestel, MDG-620, 900 W).
The input power of the microwave equipment was set at 900 W
and the microwave frequency used was 2.45 GHz.
The sample impregnated for 72 h, was not subjected to micro-
wave energy treatment. Carbonisation temperature was deter-
mined using DTA/TGA results. The heating rate was chosen
considering geometry of the heat treatment vessel and the studies
3279
in the literature [2,11,21,22]. Carbonisation of each sample was
carried out in crucibles with lid in a stainless steel reactor placed
in a temperature programmable furnace (Nabertherm S27) under
N2 flow. The heating rate for all the samples was constant to be
20 °C min 1 and each sample was held in the furnace at the desired
temperature for 1 h. The resulting samples were used for textural
and chemical characterisation.
2.2. Analyses
The contents of C, H, N, and S of the selected samples were mea-
sured using a LECO CHNS 932 Elemental Analyser. The oxygen con-
tents of samples were calculated by difference.
Nitrogen adsorption–desorption isotherms were determined
using the Quantachrome NOVA 2200 series volumetric gas adsorp-
tion instrument. In order to examine the reliability of the surface
analyser, the two standard solid samples provided by Quanta-
chrome Instruments were periodically analysed in terms of the to-
tal surface area. The surface area measurements (adsorption/
desorption) were repeated at least twice for each sample. The mea-
surements showed that the relative errors were less than 2%.
The total surface areas of the samples were measured according
to the BET method [23] using the nitrogen adsorption isotherm
data (below P/Po = 0.35). The micropore volumes of the samples
were calculated using Dubinin–Radushkevich (DR) method [24]
which relates the characteristic energy of adsorptive to micropore
structure. The micropore surface area of the samples was deter-
mined from the amount of nitrogen adsorbed at P/Po = 0.2. Meso-
pore size distributions of the samples were determined using the
BJH method [25], based on the Kelvin model of pore filling, from
the desorption data. Also the micropore volume and the external
surface area were calculated by applying the t-plot method [26]
based on standard isotherms and thickness curves. The software
provided by Quantachrome Instrument was used for all of the cal-
culations stated above.
The SEM micrographs of the samples were obtained by means
of JEOL 6060 scanning electron microscope. The surface functional
groups of the raw and treated samples were detected by a Mattson
1000 FTIR spectrometer. The spectra were recorded from 4000 to
400 cm 1. Thermal analyses (DTA/TGA) were carried out with Shi-
madzu DTG-60H thermal analyser. Each sample was heated from
30 to 1000 °C at a heating rate of 20 °C/min under N2 atmosphere.
Solubility tests of the waste tea in acetone and water were con-
ducted under a reflux condenser for 3 h. The fractions dissolved
(based on dry basis) in acetone and water were 8.0% and 19.98%
of the raw precursor, respectively. The extracted solid sample
was then dried in an oven at 105 ± 5 °C. This dry sample, which
was extracted with acetone, was used for the analyses of compo-
nents (namely cellulose, hemicellulose and lignin). Details of the
analyses were reported by Li et al. [27]. Elemental, proximate
and composition analyses of the waste tea are reported in Table 1.
3. Results and discussion
3.1. Results of analyses
Carbon, hydrogen and oxygene contents of the waste tea are
50.15%, 6.03% and 41.04% (w/w, dry basis), respectively (Table 1).
The contents of these elements for some biomasses in the literature
[4,5,11,28,29] are in the range of 43.3–49.56 for carbon, 5.6–6.5 for
hydrogen and 45.8–50.2 for oxygene. The results clearly demon-
strate that the contents of carbon, hydrogen and oxygene of the
waste tea are very close to the results reported in the literature.
The elemental analysis results of the activated carbon samples
obtained at different experimental conditions are shown in Table 2.
3280 E. Yagmur et al. / Fuel 87 (2008) 3278–3285

Table 1 The thermal decomposition of the waste tea, which is a ligno-

Characteristics of the waste tea
Property Waste tea,
wt%
9
C 50.15 >
> weight loss beginning at 130 °C where the hemicellulose compo-
>
>
H 6.03 >
= nent begins to break down. The rate of change in weight loss rap-
N 2.40 dry basis
>
> idly rises above 130 °C, as hemicellulose decomposes, until
S >
0.38 >
>
; approximately 280 °C the rate of change in weight loss again in-
O 41.04
Moisture 5.1
Ash 4.4
Volatile 66.3
matters
Fixed carbon 24.2
9 be approximately described by volatile matters. In the carbonisa-
Cellulose 17.5 =
Hemicellulose 41.3 dry basis
;
Lignin 41.2
Naturally the carbon contents of the activated samples substan-
tially increased when compared with the raw waste tea reported
in Table 1.
In order to show the effect of microwave heating on the carbon
content of the activated samples, three experiments were con-
ducted. In the first experiment the raw waste tea was carbonised
at 350 °C (CAR350), the second (MW(3:1)350) and the third
(IMP(3:1)350) experiments were performed with or without micro-
wave treatment using at the ratio of 3:1 (H3PO4/waste tea). The
samples were carbonised at 350 °C. The carbon content of the sam-
ple MW(3:1)350 prepared by microwave heating is 76.30%.
Whereas, as shown in Table 2, the carbon contents for the samples
CAR350 and IMP(3:1)350 are 68.13% and 68.36%, respectively.
The carbon content increases from 66.19% to 79.34% at temper-
atures between 300 and 550 °C, however it decreases to the value
of 69.96% at 700 °C. Variation of the carbon content of the activated
samples with temperature shows a good agreement with the re-
sults reported by Fierro et al. [30].
The effects of ratios (H3PO4/waste tea) on the elemental compo-
sition of the final product were different for the contents of hydro-
gen, carbon and nitrogen. When the ratio varied from 1:1 to 3:1 the
content of hydrogen increased from 2.82% to 3.24% and the content
of carbon also increased from 75.10% to 76.30%. On the contrary
the nitrogen content decreased from 2.90% to 1.44%. These findings
show that the use of excess amount of H3PO4 favoured the com-
pounds having hydrogen and eliminated nitrogenous compounds.
High carbon content also indicates that aromatic structure be-
comes dominant when much amount of H3PO4 is used [11].
3.2. Thermal analysis of raw material
In order to monitor the course of carbonisation thermal analysis
(DTA/TGA) of the waste tea were carried out. The DTA/TGA curves
of the raw waste tea are shown in Fig. 1.
cellulosic material, revealed the following behaviour as the tem-
perature increased. An initial weight loss corresponds to loss of
adsorbed water. The waste tea decomposition is indicated by
creases, as the cellulose and lignin decompose and reaches a max-
imum at 340 °C. At that temperature the cellulose has largely
decomposed while the lignin components continue to break down.
The profile suggests that the weight loss of the raw waste tea can
tion process tar is probably a predominant product of devolatilisa-
tion, indicated by a significant weight loss (48.17 % by weight) in
the temperature range of 200–380 °C. This is reflected in the DTA
curve as two peaks at 340 and 370 °C for evolution of volatiles
[31,32].
3.3. Surface area and pore size distribution of the chemically activated
carbons
The effects of carbonisation temperature on the total surface
area and the pore size distribution are shown in Figs. 2 and 3,
respectively. Fig. 2 shows the BET surface area of the activated car-
bons prepared after H3PO4 (3:1) and MW (30 s) treatments at dif-
ferent carbonisation temperatures.
Many studies were performed on the preparation of porous sol-
ids using biomasses as precursors. Behaviours of raw material may
be different depending on the activating agent, carbonisation tem-
perature and especially composition of the raw biomass. Different
types of biomasses were activated with phosphoric acid at various
concentrations and carbonised at different temperatures [5–
7,10,11,21,28,29]. As seen in Fig. 2 the maximum surface area is
1157 m2/g for the sample activated with phosphoric acid and car-
bonised at 350 °C, while the surface area of the raw material is
1.18 m2/g. At higher carbonisation temperatures, the surface area
values gradually decrease. Pine wood [29], pecan shell [21], fruit
stones [10], date pits [7], woody biomass birch [5], oak and birch
[28] in the literature were activated in the presence of phosphoric
acid to produce porous materials. The maximum BET surface areas
of the samples produced in these studies were 1400 m2/g at 400 °C,
1130 m2/g at 500 °C, 1740 m2/g at 400 °C, 945 m2/g at 700 °C,
1280 m2/g at 700 °C (in the presence of steam), 2199 and
1937 m2/g at 480 °C (in the presence of steam), respectively. The
results show that the maximum surface areas were produced at
the temperatures between 350 and 700 °C. It must be reported that
the raw materials, impregnation ratios and carbonisation temper-
atures are different for these studies.

Table 2
Activation conditions and elemental analysis of the resultant activated carbons

Activation conditions Elemental analysis, wt% (dry basis)

Sample IDa T (°C) H3PO4/WT Time C H H/C N S O
MW(3:1)300 300 3/1 30 s 66.19 3.80 0.06 1.63 – 28.38
MW(3:1)350 350 3/1 30 s 76.30 3.24 0.04 1.44 – 19.02
MW(3:1)550 550 3/1 30 s 79.34 2.47 0.03 1.43 – 16.76
MW(3:1)700 700 3/1 30 s 69.96 1.84 0.03 2.10 – 26.1
MW(1:1)350 350 1/1 30 s 75.10 2.82 0.04 2.90 – 19.18
MW(2:1)350 350 2/1 30 s 74.70 3.24 0.04 1.62 – 20.44
IMP(3:1)350 (conventional method) 350 3/1 72-h impregnation 68.36 2.79 0.04 1.24 – 27.61
CAR350 350 – – 68.13 4.33 0.06 2.84 0.18 24.52

CAR350 denotes the waste tea directly carbonised at 350 °C.

a
MW(3:1)350, IMP(3:1)350, etc., for example, the values in the brackets denote acid/waste tea ratios, the values on the right of the brackets denote carbonisation
temperature, the letters MW or IMP on the left of the brackets denote microwave and impregnation, respectively.
 E. Yagmur et al. / Fuel 87 (2008) 3278–3285 3281

obtained from the sample treated at 350 °C, the differential pore
volumes tend to decrease at higher temperatures. The distribution
curves shown in the figure have almost the same trends. Carboni-
sation temperature applied between 350 and 700 °C did not prac-
tically affect the average pore size (35 Å).
The influences of the H3PO4/waste tea ratio on the surface areas
were also determined. The BET surface areas were 1011, 936.2 and
1157 m2/g for the ratios 1:1, 2:1 and 3:1, respectively. As the
amount of acid (1:1–3:1) used increases the surface area raises
in parallel manner. However the surface area for the sample with
2:1 ratio unexpectedly dropped to the value of 936.2 m2/g. The sur-
face area was maximum (1157 m2/g) for the sample activated at
the ratio of 3:1.
The composition of biomass affects the development of pore
structure of solids during phosphoric acid activation [33] and car-
bonisation processes. The lignin content of the waste tea used in
this study (41.2%) is higher than hard wood biomass such as oak
Fig. 1. DTA/TGA curves of the waste tea. (27.8%) and birch (20.4%) reported by Klijanienko et al. [28]. The
birch was activated with H3PO4 (impregnation ratio: 0.99) and
subsequently subjected to heat treatment under steam flow at
1400 480 °C for 30 min soaking time, the surface area of the final prod-
1157 1151 uct was 1165 m2/g. In our study the surface area of the sample acti-
1200 vated in the presence of H3PO4 (impregnation ratio: 1) and then
1040
BET Surface Area,m 2 /g

969 carbonised at 350 °C under nitrogen atmosphere was 1011 m2/g.

1000 864 Difference between the surface areas might be due to the lignin
content of the raw materials.
800 Figs. 4a and b illustrate the N2 adsorption–desorption isotherms
and pore size distributions of the samples, MW(3:1)350 and
600 451,7 538,2
IMP(3:1)350, respectively. The figures are important to show the
effect of microwave heating on the surface area and the pore size
400 distribution. As seen in Fig. 4a the BET surface areas are 1157 (with
microwave heating) and 928.8 m2/g (without microwave heating
200
that is a conventional method) for the samples, MW(3:1)350 and
IMP(3:1)350, respectively. Microwave heating caused to increase
0
250 300 350 450 550 650 700 the surface area by almost a factor 1.2. The pore size distributions
for these two samples are depicted in Fig. 4b. The distribution
Carbonisation Temperature, ºC curves of the samples are very similar apart from their sharpness.
As reported in the preceding section the reason is the differential
Fig. 2. The effect of carbonisation temperature on the BET surface area (phosphoric
acid/precursor = 3:1, microwave heating period: 30 s).
pore volumes. Although the surface areas of the samples are signif-
icantly different the pore diameters of the samples almost un-
changed. It may be concluded that microwave radiation energy
serves to open the closed pores in the solid matrix. In order to con-
0.030 trol the pore wideness the effects of various parameters on the
MW(3:1)350 pore structure should be investigated.
Differential Pore Volume cm3 /g

MW(3:1)550
0.025 The micropore surface areas of the samples were evaluated
MW(3:1)700
according to the Dubinin–Radushkevich (DR) method using the
adsorption isotherms. The results are listed in Table 3. External
0.020
and micropore surface areas obtained from the t-method are also
tabulated in the same table for comparison purposes. In order to
0.015 avoid superfluous data only four different increasing temperatures
were chosen to report the effect of carbonisation temperature on
0.010 the micropore surface area according to the methods mentioned
above. It is emphasised that the methods stated are based on the
0.005 different theories; naturally the values calculated are different
for each method. The values should be assessed or compared with-
in the same method in the same column rather than different
0.000
methods.
10 100 1000
Pore Diameter, Å According to the DR method the micropore surface area is sub-
stantially higher, which is 1623 m2/g, for the sample MW(3:1)350.
Fig. 3. The effect of carbonisation temperature on the pore size distribution. This obviously reflects that this sample is more microporous than
the other samples conducted at different temperatures. Similar
trend was also observed for the data determined according to the
The effect of carbonisation temperature on pore development is t-method as shown in the last column of the table. In terms of
presented in Fig. 3. The samples reported in Fig. 3 clearly show that H3PO4/waste tea ratio, the micropore surface area was the maxi-
the solid particles mainly consist of mesopores according to BJH mum for the sample with the ratio of 3/1. Whereas there was no
method. As expected, the maximum differential pore volume was parallelism with the results obtained from the t-method. The
3282 E. Yagmur et al. / Fuel 87 (2008) 3278–3285

700 The samples activated were also characterised in terms of the

IMP(3:1)350 Adsorption cumulative pore and micropore volumes according to the BJH, DR
650
IMP(3:1)350 Desorption and t-methods, respectively (Table 4). The cumulative pore vol-
MW(3:1)350 Adsorption
600
MW(3:1)350 Desorption umes were evaluated from both the adsorption and desorption iso-
550 therms using the BJH method. The cumulative pore volume of the
sample MW(3:1)550 was the highest compared with the other
Volume (cc/g)

500
samples. Some narrow open pores may have been merged or
450 1157 m2/g widen at the carbonisation temperature for this sample, that is
550 °C. It is reminded that there is no parallelism between the
400
BET surface area and the cumulative pore volume. The micropore
350 volumes calculated from the DR and t-methods for the sample
300 928.8 m2/g MW(3:1)350 treated at 350 °C were 0.573 and 0.228 cc/g, respec-
tively, which are the maximum values. It is useful to compare
250
the values of samples MW(3:1)350 (with MW heating) and
200 IMP(3:1)350 (without MW heating). The cumulative pore and
0.0 0.2 0.4 0.6 0.8 1.0 micropore volume (DR) values of the sample interacted with MW
P/P0
heating were higher than the other which was impregnated with
0.030 the acid without MW heating.
IMP(3:1)350
Differential Pore Volume, cm3/g

MW(3:1)350 3.4. Electron microscopic examination of the activated carbons

0.025

0.020
0.015
0.010
0.005
0.000
10
Pore Diameter,Å
Fig. 4. The effect of microwave treatment on the N2 adsorption–desorption
isotherms (a) and the pore size distribution (b).
micropore surface area was 1333 m2/g for the sample,
IMP(3:1)350, which was impregnated with H3PO4 for 72 h, as indi-
cated in the some parts of the article, this sample was not inter-
acted with microwave heating. As mentioned above the
micropore surface area of the sample MW(3:1)350 was 1623 m2/
g that is 1.217 (21.7%) times higher than the sample IMP(3:1)350
carried out without microwave heating. These two results show
the effect of microwave heating on the micropore surface area of
the sample as well as the BET surface area.
SEM images of the waste tea and treated samples chosen are
shown in Fig. 5. The surface of the raw material (Fig. 5a) is fairly
smooth, has less cracks and voids, whereas its carbonised sample
at 350 °C (Fig. 5b) has cracks and crevices and some grains in var-
ious sizes in large holes. The image of H3PO4 impregnated sample
(Fig. 5c) shows irregular and heterogeneous surface morphology.
As can be seen in this figure H3PO4 interaction generates brittle
and grainy surface and voids in different widths. In order to ob-
serve the influence of microwave heating on the surface morphol-
ogy, the SEM image is presented in Fig. 5d. The surface is smoother
and distinctly different from Fig. 5c which is H3PO4 impregnated
100 1000 with no microwave heating. Some images taken at a higher magni-
fication for the same samples [MW(3:1)350 and IMP(3:1)350],
which were not included in this article, obviously showed a pitted
surface morphology.
3.5. The FTIR analyses of the raw material and treated samples
Fig. 6 shows the FTIR spectra of the waste tea, directly carbonised
(CAR350), IMP(3:1)350 and MW(3:1)350, respectively. The FTIR
spectra have been evaluated under the light of available literature
[10,21,34]. The first peak at 3400 cm 1 is ascribed to OH stretching
vibration in hydroxyl groups. This peak is stronger for the waste tea
and has weakened for the samples directly carbonised (CAR350),
IMP(3:1)350 and MW(3:1)350. Carbonisation temperature for these
samples was 350 °C. The bands at 2923 and 2853 cm 1, which are

Table 3
Micropore and external surface areas calculated from DR and t-methods

Samples DR method t-method

2
Micropore surface area (m /g) External surface area (m2/g) Micropore surface area (m2/g)
The effect of carbonisation temperature
MW(3:1)300 782.6 189.7 348.5
MW(3:1)350 1623 687.3 470.0
MW(3:1)550 1420 823.9 216.2
MW(3:1)700 1171 737.5 126.5
The effect of H3PO4/WT ratio
MW(1:1)350 1459 433.5 577.0
MW(2:1)350 1352 428.0 508.2
MW(3:1)350 1623 687.3 470.0
The effect of treatment/activation method
Waste tea, WT 1.315 1.178 0
CAR350 1.287 0.94 0.48
IMP(3:1)350 (conventional method) 1333 361.1 567.7
MW(3:1)350 1623 687.3 470.0
 E. Yagmur et al. / Fuel 87 (2008) 3278–3285 3283

Table 4
Cumulative and micropore volumes calculated from BJH, DR and t-methods

BJH method DR method t-method

Cumulative adsorption pore Cumulative desorption pore Micropore volume Micropore volume
volume (cc/g) volume (cc/g) (cc/g) (cc/g)
The effect of carbonisation temperature
MW(3:1)300 0.227 0.145 0.276 0.177
MW(3:1)350 0.829 0.667 0.573 0.228
MW(3:1)550 1.224 1.138 0.502 0.100
MW(3:1)700 1.066 0.992 0.414 0.058
The effect of H3PO4/WT ratio
MW(1:1)350 0.482 0.381 0.515 0.294
MW(2:1)350 0.455 0.344 0.477 0.2559
MW(3:1)350 0.829 0.667 0.573 0.228
The effect of treatment/activation method
WT 0.005 0.005 0.0005 –
CAR350 0.003 0.003 0.0004 0.0002
IMP(3:1)350 (conventional 0.435 0.300 0.471 0.285
method)
MW(3:1)350 0.829 0.667 0.573 0.228

Fig. 5. SEM micrographs of the selected samples at 5.000 magnification.

assigned to asymmetric CAH and symmetric CAH bands, respec-
tively, completely disappeared for the samples IMP(3:1)350 and
MW(3:1)350. Stretching absorption band at 1740–50 cm 1 is as-
signed to carbonyl C@O which is observed for the raw material.
H3PO4 breaks many bonds in aliphatic and aromatic species
present in the raw waste tea leading to liberation and elimination
of many light and volatile substrates cause partial aromatisation
and thus carbonisation. This behaviour is consistent with the dis-
appearance of C@O at 1738 cm 1 in the waste tea [25]. The strong
band is seen at about 1638 cm 1 that may be ascribed to olefinic
C@C vibrations in aromatic region for the raw material. The peak
at about 1692 cm 1 assigned to the vibration of C@O in carbonyl
groups is observed for the samples CAR350, IMP(3:1)350 and
MW(3:1)350. The peak around 1607 cm 1 is resulted from aro-
matic rings or carbon–carbon double bonds [21]. The absorption
around 1223–1000 cm 1 indicates the existence of CAO single
bond in carboxylic acids, alcohols, phenols and esters or the P@O
bond in phosphate esters, OAC bond in PAOAC linkage and
P@OOH bond [10].
Although the mechanisms of chemical activation of wood by
phosphoric acid are not fully understood [33], the experimental re-
sults may be interpreted under the light of literature. During the
acid activation and heat treatment processes, phosphoric acid
causes considerable changes in the chemical structure of the bio-
mass as well as physical changes. Consecutive or simultaneous
changes in the raw material take place during microwave heating
operation. Firstly the dehydration process occurs and then some
gases which are mainly light hydrocarbons are released at about
250 °C [33]. Indeed the temperature of the sample heated with
microwave energy varied in the range of 200–250 °C.
3284 E. Yagmur et al. / Fuel 87 (2008) 3278–3285
Fig. 6. FTIR spectra of the samples; the waste tea, (CAR350), IMP(3:1)350 and
MW(3:1)350.
Due to different effects of phosphoric acid on lignocellulosic
materials [7,33–35] its amount is important for reaction processes
and properties of the final product [21]. It is believed that micro-
wave heating intensifies the reaction between the waste tea and
phosphoric acid. This process is very important to reduce impreg-
nation period. The experiments showed that microwave heating
increased the temperature of the mixture up to 200–250 °C in
30 s. Possibly the pore creation and also arrangement start in this
stage and continue during carbonisation process. Indeed the iso-
therms and pore size distributions in Fig. 4 indicate that the surface
areas and pore structures are different for the samples prepared
with and without microwave heating.
3.6. Conclusions
When the waste tea used as a precursor, the activated carbons
with high total surface areas were obtained from the carbonised
samples by applying the conventional impregnation method. Inte-
gration of microwave heating stage to the conventional impregna-
tion method has caused moderate increases in the total surface
area and the chemical activation process is completed in a very
short time instead of long impregnation periods. The microwave
induced activation method applied in this study provides time
and energy savings.
The method applied in the presence of phosphoric acid, partic-
ularly at the ratio of 3/1, markedly affected surface characteristics
of the solid particles. According to the DR method the micropore
surface area and volume were reasonably improved by the micro-
wave pre-treatment.
Pore size distributions obtained from desorption data exhibited
nearly the same trend and the average pore sizes were also almost
the same for the samples obtained at different conditions. However
differential pore volume of each sample was obviously different
and the highest for the sample, MW(3:1)350, treated with micro-
wave energy. The microwave treatment process causes consider-
able changes in the surface morphology and chemical structure
of the waste tea. Further studies should be performed in order to
control pore size by the method introduced in this article.
Acknowledgements
The authors gratefully acknowledge the support of The Scien-
tific and Technological Research Council of Turkey (TUBITAK), Tur-
key, for this research (Project No. 107M306).
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