Waste Management 29 (2009) 756–760

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

Preparation of activated carbon from coconut shell chars in pilot-scale

microwave heating equipment at 60 kW
Wei Li a,b, Jinhui Peng a,*, Libo Zhang a, Kunbin Yang a, Hongying Xia a, Shimin Zhang a, Sheng-hui Guo a
a
Faculty of Materials and Metallurgical Engineering, Kunming University of Science and Technology, Kunming 650093, PR China
b
Faculty of Science, Kunming University of Science and Technology, Kunming 650093, PR China

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

Article history: Experiments to prepare activated carbon by microwave heating indicated that microwave energy can
Accepted 17 March 2008 decrease reaction temperature, save the energy and shorten processing time remarkably compared to
Available online 1 May 2008 conventional heating, owing to its internal and volumetric heating effects. The above results were based
on the laboratory-scale experiments. It is desirable to develop a pilot-scale microwave heating equip-
ment and investigate the parameters with the aim of technological industrialization. In the present study,
the components and features of the self-invented equipment were introduced. The temperature rise
curves of the chars were obtained. Iodine numbers of the activated carbons all exceed the state standard
of China under the following conditions: 25 kg/h charging rate, 0.42 rev/min turning rate of ceramic tube,
flow rate of steam at pressure of 0.01 MPa and 40 kW microwave heating power after 60 kW pre-activa-
tion for 30 min. Pore structure of the sample obtained at a time point of 46 h, which contained BET sur-
face area, and pore size distributions of micropores and total pores, was tested by nitrogen adsorption at
77 K.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Activated carbons are widely used in many industrial fields
including medical treatment, energy storage, and water purifica-
tion and also in the military field owing to their large surface area,
controllable pore structure, thermostability and low acid/base
reactivity. It is well known that activated carbons can be prepared
from a large variety of raw materials with high carbon content and
low levels of inorganic compounds. Various carbonaceous materi-
als such as coal, lignite, nutshells, wood, and peat are used in the
production of commercial activated carbon. However, abundance
and availability of agricultural by-products make them good
sources of raw materials for activated carbons. Harvesting and pro-
cessing of various agricultural crops result in considerable quanti-
ties of agricultural by-products. Such agricultural by-products are
usually inexpensive, and their effective utilization is a desired out-
come. Many research studies have been performed to prepare acti-
vated carbons from agricultural by-products such as sugarcane
bagasse and nutshells (Ioannidou and Zabaniotou, 2007). Coconut
shells have little or no economic value, and their disposal is not
only costly but may also cause environmental problems. Conver-
sion of coconut shells into activated carbons, which can be used
as adsorbents in water purification or the treatment of industrial
and municipal effluents, would add value to these agricultural
* Corresponding author. Tel.: +86 0871 5192076; fax: +86 0871 5191046.
E-mail address: jhpeng_ok@yeah.net (J.H. Peng).
commodities, help reduce the cost of waste disposal, and provide
a potentially cheap alternative to existing commercial carbons.
Therefore, the preparation of activated carbon with high surface
area from agricultural by-products is an interesting subject.
However, in some cases, the thermal process may take several
hours, even up to a week to reach the desired level of activation
with the conventional heating systems so that the process incurs
extra processing costs. Another problem lies in the furnace such
that the surface heating from the hearth wall does not ensure a
uniform temperature for different shapes and sizes of samples. This
generates a thermal gradient from the hot surface of the sample
particle to its interior and impedes the effective removal of gaseous
products to its surroundings, thereby resulting in a detrimental ef-
fect on the quality of the activated carbons prepared.
Microwaves are now being used in various technological and
scientific fields in order to heat dielectric materials. The main
advantage of using microwave heating is that the treatment time
can be considerably reduced, which in many cases represents a
reduction in the energy consumption as well. In addition, the con-
sumption of gases used in the treatment can also be reduced.
Microwave-induced chemical reactions can be used to solve the
above problems associated with conventional surface heating
because microwave heating is both internal and volumetric heat-
ing (Guo and Lua, 2000). Therefore, the tremendous thermal gradi-
ent from the interior of the char particle to its cool surface allows
the microwave-induced reaction to proceed more quickly and
effectively at a lower bulk temperature, resulting in energy savings

0956-053X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2008.03.004
 W. Li et al. / Waste Management 29 (2009) 756–760
and shortening the processing time. Compared with conventional
heating techniques, microwave heating has the additional advan-
tages as follows: interior heating, higher heating rates, selective
heating, greater control of the heating process, no direct contact
between the heating source and heated materials, and reduced
equipment size and waste (Thostenson and Chou, 1999; Ven-
kateshl and Raghavan, 2004; Jones et al., 2002; Appleton et al.,
2005). With continued development of activated carbons technol-
ogies, the new applications of microwave heating in preparing acti-
vated carbons are succeeding and expanding (Guo and Lua, 2000;
Zhang et al., 2003; Chen et al.,2003). To our knowledge, though,
coconut shells have been successfully converted into a well-devel-
oped activated carbon by conventional thermal activation (physi-
cal activation) and chemical activation using carbon dioxide
(CO2), H2SO4, ZnCl2 and KOH, K2CO3 (Ioannidou and Zabaniotou,
2007), activated carbons prepared from coconut shells by micro-
wave heating have not been reported in the literature. Further-
more, the technology of preparing activated carbons by
microwave heating now remains at the laboratory level. Scale-up
of technology is required to develop its industrial production.
Therefore, it is desirable to develop a pilot-scale microwave heat-
ing equipment and investigate important parameters with the
aim of technological industrialization.
In this study, we invented a pilot-scale microwave heating
apparatus for the preparation of activated carbons from coconut
shell chars with saturated steam activation. The components and
features of the equipment are described. The temperature rise
curves of the chars and in the presence of steam in a microwave
field were investigated. The iodine number of the activated carbons
varying with activation time was researched.
2. Experimental
2.1. Materials
Coconut shells used as raw materials to produce activated car-
bon in this study were obtained from Vietnam. The starting mate-
rials were manually chosen, cleaned with deionized water, dried at
110 °C for 48 h and ground with a roller mill to obtain samples of
4.75–3.35 mm particle size. Proximate analysis was shown in Table
1. The commercial coconut shell-based activated carbon was ob-
tained from Kunming AC plant, China.
2.2. Features of pilot-scale microwave heating equipment
A microwave system typically consists of a generator to produce
the microwaves, a waveguide to transport the microwaves, an
applicator (usually a cavity) to manipulate microwaves for a spe-
cific purpose, and a control system (tuning, temperature, power,
etc.). A schematic diagram of the pilot-scale microwave heating
equipment is shown in Fig. 1. The equipment used in present study
mainly contained several parts as follows:
1. Microwave can be generated by either thermionic devices such
as magnetron, klystron, back wave tube (BWT), and gyrotron; or
solid-state devices such as microwave transistors and diodes.
Among these generators the magnetron is most widely used
Table 1
Proximate analysis results of coconut shells
Sample Moisture Volatile matter Fixed carbon
(wt.%) (wt.%) (wt.%)
Coconut 10.53 78.30 20.96
shells
757
for the industrial applications due to their availability and low
cost. The main components of the magnetron include filament,
inside cylindrical cathode, outside tubular anode, magnet, exit
passage, antenna, vane, and strip ring. Power conversion and
control are realized by power regulator. The main components
in the power regulator are power switches. The first component
is the power unit where microwaves are generated at the
required frequency band. Magnetron tubes are used to generate
microwave power. The energy is coupled into the applicator
(cavity) through a slot, an array of resonant slots, where the
material is subjected to intense microwave fields, and to which
any additional ancillary process equipment such as pumps for
operation under moderate vacuum conditions, steam or hot
air injection, must be connected. The power supply for the
microwave heating equipment was made of 60 magnetrons at
2.45 GHz frequency and 1 kW power, which was cooled by
water circulation. A control system maintains the inert atmo-
sphere in the reactor cavity of the microwave unit, whose size
was accurately calculated by microwave theories addressing
materials that preferably absorb microwave energy.
2. Raw materials were charged into a special ceramic tube inclin-
ing in the reactor cavity by a screw feeder, and those products
were discharged by turning of the tube. The rate of charge vary-
ing from 0 to 70 kg/h was controlled by the rotational speed of
the screw, and the rate of discharge was controlled by the tube’s
turning speed that ranged from 0 to 0.9 rev/min.
3. Steam was introduced into a stainless steel pipe at the bottom
of the ceramic tube and distributed through many proportion-
ally spacing holes, which can uniformly activate raw materials.
The flow rate of steam was controlled by adjusting the pressure
of the steam between 0 and 0.3 MPa.
4. The temperature measurement system consisted of a tempera-
ture indicator and thermocouple fixed in middle of the stainless
steel pipe. The thermocouple provides feedback information to
the control panel that controls the power to the magnetron.
5. The input power of the microwave, rate of charging and dis-
charging, flow rate of steam and the atmosphere were con-
trolled by a control system, which is an on-line automatic
control system.
2.3. Preparation of activated carbons
2.3.1. Carbonization of coconut shells with conventional heating
Coconut shells were loaded on a ceramics boat, which was
placed inside a stainless steel tubular reactor. The coconut shells
were heated up to a carbonization temperature of 723 K at a heat-
ing rate of 10 K/min with conventional heating and was held for at
least 2 h at the carbonization temperature under N2 gas flow. After
carbonization the samples were cooled to room temperature under
N2 flow. The carbonized samples were crushed sieved to obtain
particles with sizes less than 2 mm.
2.3.2. Preparation of activated carbons by microwave heating
Coconut shell chars were placed into the ceramic tube by
turning the screw and ceramic tube. The charging and discharg-
ing processes were stopped when the tube held 100 kg of char.
The chars were heated to a temperature between 860 and
867 °C by applying microwave power at 60 kW. Subsequently,
steam was introduced to activate the chars. At the same time,
the charging and discharging were started up again. The temper-
ature of materials was maintained at 825 ± 5 °C by adjusting the
Ash microwave power from 60 kW to 40 kW and the flow rate of
(wt.%)
steam (at a pressure of 0.01 MPa). In addition, after steam acti-
0.74 vation for 30 min, sampling was initiated each hour and the io-
dine number was measured.
758 W. Li et al. / Waste Management 29 (2009) 756–760

Microwave heating reaction cavity

Power supply of Temperature Water vapor

microwave heating measuring system generator

Continuous charging/ Atmosphere

discharging system control system

Control system

Fig. 1. Schematic diagram of the pilot-scale microwave heating equipment.

2.4. Characterization of the activated carbons produced 1000

Temperature of the chars (ºC)

Characterization of the carbons produced included adsorption 800
properties and pore structures. The test method of the iodine num-
ber of the activated carbons was according to GB/T12496.8-1999
(testing standard of activated carbon of China). 600
The N2-adsorption–desorption isotherms were measured with
an accelerated surface area and porosimetry system (ASAP2000, 400
Micromeritics) in order to determine the surface areas and total
pore volumes. Prior to the measurements, the samples were out-
gassed at a temperature of 300 °C under nitrogen flow for at least 200
2 h. Nitrogen adsorption isotherm was measured over a relative
pressure (P/P0) range from approximately 10 6 to 1. The BET sur- 0
face area was calculated using the BET (Brunauer, Emmett and Tell- 0 50 100 150 200 250
er) equation from selected N2-adsorption data within the range of Microwave heating time (min)
relative pressure, P/P0, from 0.1 to 0.3 (Gregg and Sing, 1982). The
Fig. 2. Temperature rise curve of coconut shell chars in microwave heating fields.
total pore volume was estimated by converting the amount of N2
gas adsorbed (expressed in cm3/g STP) at a relative pressure of
rate, was 0.42 rev/min. Meanwhile, the steam was introduced into
0.99 to liquid volume of the nitrogen adsorbate (Guo and Lua,
tube at a pressure of 0.01 MPa to activate the chars. Fig. 3 illus-
2000). Micropore size distribution was calculated by means of
trates the temperature curve of the chars that had been contacted
the Horvath–Kawazone (HK) method (Ustinov and Do, 2002). Pore
with steam. The temperature of the char decreased to 719 °C in
size distribution was computed by the DFT method by minimizing
10 min and then rose with microwave heating time. When the
the grand potential as a function of the fluid density profile (Kow-
temperature reached 823 °C after 30 min, the microwave power
alczyk et al., 2003; Valladares et al., 1998; Ismadji and Bhatia,
was decreased from 60 kW to 40 kW, maintaining values of other
2001; McCallum et al., 1999).
parameters in order to keep the temperature at 825 ± 5 °C.

3. Results and discussion 3.2. Iodine number changing curve of products

3.1. Temperature rise curve of coconut shell chars After steam activation for 30 min, sampling was initiated each
hour and the iodine number was measured. As shown in Fig. 4, that
According to the interaction with microwave, materials can be
categorized into three principal groups: transparent which are
900
Temperature of the chars (ºC)

low loss materials, where microwaves pass through without any

losses; conductors where microwaves are reflected and cannot
penetrate; and absorbing which are high loss materials, where 850
microwaves are absorbed depending on the value of the dielectric
loss factor. We investigated the relationship between temperature
and microwave heating time in order to know if the coconut shell 800
chars can be heated by microwave heating.
The temperature rise curve of coconut shell chars in microwave
heating fields is illustrated in Fig. 2. After charging, the coconut 750
shells chars were heated up by 60 kW of microwave power. It
was shown that the temperature of the chars varied from 860 °C
700
to 867 °C after 180 min by microwave heating at 60 kW and indi- 0 50 100 150 200
cated that the coconut shell chars were good microwave-absorbing Microwave heating time (min)
materials. Then the charging was re-started at a rate of 25 kg/h; the
rotational speed ceramic tube, which dominated the discharging Fig. 3. Temperature changing curve of the chars after steam imported.
 W. Li et al. / Waste Management 29 (2009) 756–760 759

1090
500
Iodine number (mg/g)

Adsorption Amount (ml/g STP)

400

1070
300

200

1050 100
0 20 40 60 80
Time (h)
0
Fig. 4. Iodine number changing curve of products.
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/P0)

Fig. 5. Adsorption isotherm of N2 at 77 K on activated carbon prepared under the

the iodine number of the product varied from 1070 to 1085 mg/g optimum conditions.

after 30 min activation time, which achieved the first grade of

the state standard of China. The iodine number of the commercial
ultramicropores (width less than 0.7 nm) and supermicropores
coconut shell-based activated carbons was 894 mg/g. The drastic
(width from 0.7 to 2 nm). This distinction is important because
changes in iodine number were in relation to the activation degree
most molecules of gaseous pollutants range in diameter from
of the chars. It was not like that of chars heated by laboratory-scale
about from 0.4 to 0.9 nm. Therefore, gas-adsorbing carbons usually
equipment; there was always un-uniform activation for the chars
have more micropores whilst liquid-adsorbing carbons have signif-
with steam activation by pilot-scale microwave heating equip-
icant mesopores due to the larger size of liquid molecules. An alter-
ment. After continuous production for 20 h, the average yield of
native method proposed by Horvath and Kawazoe (1983) was to
the sample was 69.74% as calculated from the hourly sample
calculate an average potential function inside the micropore, relat-
results.
ing fluid-fluid and solid-fluid interaction of an adsorbed molecule
In conclusion, preparing activated carbon from coconut shell
to its free energy change upon adsorption. The Horvath–Kawazoe
chars with steam activation in pilot-scale microwave heating
method is an improvement over the Kelvin approach in that it
equipment proved feasible. The optimum conditions were ob-
acknowledges the strong desorbent–adsorbate attractive forces in
tained as follows: 25 kg/h charging rate, 0.42 rev/min turning rate
micropores (Horvath and Kawazoe, 1983; Ustinov and Do, 2002).
of ceramic tube, flow rate of steam at pressure of 0.01 MPa and
The method is effective for calculation of micropore size
40 kW microwave heating power after 60 kW pre-activation for
distribution.
30 min.
The micropore size distribution for the activated carbon accord-
ing to the Horvath–Kawazoe method (1983) is shown in Fig. 6.
3.3. Characterization of pore structure of the activated carbon
From the differential pore volume plots, ultramicropores less than
0.7 nm were present, which contribute to selectivity of adsorption
The activated carbon sample obtained at a time point of 46 h
(molecular sieve effect). A heterogeneous micropore size distribu-
and that had an iodine number of 1073 mg/g was selected for pore
tion was obtained with two different peaks at 0.55 and 0.59 nm.
structure analysis.
The average micropore size was equal to 0.65 nm.
The N2-adsorption isotherm obtained for the sample prepared
under the optimum condition is shown in Fig. 5. The isotherms be-
long to type II according to the International Union of Pure and Ap-
plied Chemistry (IUPAC) classification and provide an approximate 0.18
assessment of the pore size distribution. As shown in Fig. 5, the ini-
0.16
Differential Pore Volume (ml/g-nm)

tial part of the type II isotherm for the carbon represents micropore
filling, and the slope of the plateau at high relative pressure is due 0.14
to multilayer adsorption on the nonmicroporous surface, i.e., in
mesopores, in macropores and on the external surface (Rouquerol 0.12
et al., 1999).
The isotherm indicated that the sample was of mesoporous 0.10
structure which contained plenty of mesopores, micropores and
0.08
few macropores. The pore size distribution was broad. The change
in slope at the point P/P0 = 0.02 indicates that monolayer coverage 0.06
was completed and multilayer adsorption began at that stage.
Analysis of the nitrogen adsorption isotherm results yielded a 0.04
BET surface area and total pore volume of the carbon of 891 m2/g
and 0.7233 ml/g, respectively. At the same experimental condi- 0.02
tions, the BET surface area and total pore volume of the commer-
0.00
cial coconut shell-based activated carbon were 671 m2/g and 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
0.3264 ml/g, respectively.
Pore Diameter (nm)
According to the IUPAC definitions, adsorbent pores are classi-
fied into three groups: micropore (size <2 nm), mesopore (2– Fig. 6. Micropore size distribution of the activated carbon prepared under the op-
50 nm), and macropore (>50 nm). Micropores can be divided into timum condition by H–K equation.
760 W. Li et al. / Waste Management 29 (2009) 756–760
0.040
Incremental pore volume (mL/g)
0.035
0.030
0.025
0.020
0.015
0.010
0.005
0.000
0.1 1 10
Pore Width (nm)
Fig. 7. Pore size distribution of the activated carbon prepared under the optimum
condition by DFT.
The PSD obtained by DFT analysis of the nitrogen adsorption
isotherm is shown in Fig. 7 and was consistent with the isotherm
trend discussed earlier. Based upon Fig. 7, the carbon contains
37.06% micropores, 62.85% mesopores and 0.07% macropores.
The PSD was broad with four different peaks at 0.73, 1.18, 2.73
and 3.43 nm.
3.4. Merits of the pilot-scale microwave heating equipment
Four merits of the pilot-scale microwave heating equipment are
as follows:
(1) It has preferable thermal efficiency because heating is based
on the interior heating and selective heating caused by
microwave heating that assures a high heating rate. Conse-
quently, it can shorten the time and improve the perfor-
mances of the object product.
(2) The ceramic tube is a sort of special reactor tube used in
microwave fields. It has many advantages, including high
resistance to elevated temperatures and thermal shock,
transparency to microwave radiation for good penetration
and a large diameter. Furthermore, the ceramic tube remains
stable during the process of preparing activated carbons and
is suitable for a pilot-scale processing of microwave heating.
The cost of a ceramic tube is half that of a quartz glass tube
of the same diameter.
(3) For the purposes of cost reduction, a power supply adapted
to the complex mode of 60 low power magnetrons was
designed instead of using expensive large power
magnetrons.
(4) The pilot-scale equipment can be continually charged and
discharged in a high temperature, controlled reaction atmo-
sphere with variable microwave power without microwave
radiation leakage. Moreover, by optimizing operating
parameters, activated carbons that high adsorption capacity
and quality were produced at lower cost.
4. Conclusions
This study confirmed that preparation of activated carbon from
coconut shell chars in the pilot-scale microwave heating equip-
ment was feasible. The advantages of microwave heating as a ther-
mal resource for manufacturing activated carbon were
demonstrated in pilot-scale equipment. Experimental results
showed that microwave heating could shorten processing time
remarkably, and could achieve a high-quality product presumably
due to its interior and volumetric heating.
100
Acknowledgements
The support of Key Project of Yunnan Province (Grant No:
2002NG19) and the Teaching & Research Award Program for Out-
standing Young Teachers in Higher Education Institutions of MOE
are gratefully acknowledged.
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