b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5

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Synthesis of palm oil empty fruit bunch magnetic

pyrolytic char impregnating with FeCl3 by
microwave heating technique

N.M. Mubarak a,b,*, A. Kundu c, J.N. Sahu a,d,*, E.C. Abdullah e,

N.S. Jayakumar a
a
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Chemical and Petroleum Engineering, Faculty of Engineering, UCSI University, Kuala Lumpur 56000,
Malaysia
c
Institute of Biological Sciences, University of Malaya, 50603 Kuala Lumpur, Malaysia
d
Department of Petroleum and Chemical Engineering, Faculty of Engineering, Institut Teknologi Brunei, Tungku
Gadong, P.O. Box 2909, Brunei Darussalam
e
Malaysia e Japan International Institute of Technology (MJIIT), Universiti Teknologi Malaysia, Jalan Semarak,
54100 Kuala Lumpur, Malaysia

article info abstract

Article history: Empty fruit bunch (EFB) is one of the most abundant residues of the Palm oil mill industry
Received 26 July 2013 in Malaysia. The novel magnetic bio-char was synthesized by single stage microwave
Received in revised form heating technique, using EFB in the presence of ferric chloride hexahydrate. The effect of
9 December 2013 microwave powers, radiation time and impregnation ratio (IR) of ferric chloride hexahy-
Accepted 22 December 2013 drate to biomass were studied. Also the process parameters such as microwave powers,
Available online 28 January 2014 radiation times and IR were optimized using response surface method. The statistical
analysis revealed that the optimum conditions for the high porosity magnetic bio-char
Keywords: production were at 900 W microwave power, 20 min radiation time and 0.5 (FeCl3:
Magnetic bio-char biomass) impregnation ratio. These newly produced magnetic bio-char have a high surface
Methylene blue area of 890 m2 g
1 and that leads to highly efficient in the removal of methylene blue (MB)
Adsorption with an efficiency of 99.9% from aqueous solution with a maximum adsorption capacity of
EFB 265 mg g
1.
Microwave heating ª 2013 Elsevier Ltd. All rights reserved.

trunks are produced in approximately three million hectares

1. Introduction
Malaysia is famous for production of oil Palm as the agricul-
tural industry. About 90 million metric ton of renewable
biomass such as empty fruit bunch (EFB), kernel shell, and
of oil Palm plantations currently [1]. Among these, EFB
12.4 million tonnes [1] and Palm shell 2.4 million tonnes [2]
waste are produced. The burning of biomass caused emis-
sion of hazardous and toxic chemicals such as dioxins. Limi-
tation of land fill sites and additional cost due to the treatment

* Corresponding authors. Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur,
Malaysia. Tel.: þ60 3 79675295; fax: þ60 3 79675319.
E-mail addresses: mubarak.yaseen@gmail.com (N.M. Mubarak), jay_sahu@yahoo.co.in (J.N. Sahu).
0961-9534/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2013.12.021
266 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5
of the leachates from the sites has grown interest among the
researchers for effective and commercially valuable utiliza-
tion of the EFB. One of the options the EFB can convert to good
quality bio-char.
Bio-char is carbon a rich material produced from pyrolysis
carbonaceous biomass [3]. Bio-char is highly recognized for its
effective agricultural and environmental applications such as
improving soil fertility and effective host of the microor-
ganism [4]. Bio-char can also contribute to the reduction of
greenhouse gas reduction with its carbon storage capacity and
reducing CO2, CH4 and N2O production in soil [5]. Bio-char is a
soil enhancer which stores carbon and makes fertile soils,
reduction of nitrogen leaching into ground water, reduction of
nitrous oxide emission, increasing cation-exchange capacity
for enhanced soil fertility, soil acid moderation, high rate of
water retention and high amount of soil microbes that are
beneficial [6,7]. Furthermore, bio-char in recent year has been
recognized as low cost suitable material for various environ-
mental applications [8e12]. Recently, activated carbon (AC) is
one of the good adsorbents used in the industrial sector;
however regeneration and desperation problem occur in in-
dustrial application. Powdered bio-char, like powdered AC, is
difficult to be separated from the aqueous solution [13]. To
overcome the shortcomings, an innovative technology has
been developed to remove pollutants like heavy metals,
phosphate, and organic compounds, from aqueous solutions
[14,15]. To remove these sorbent effectively, magnetic bio-
char is introduced to the commercially available sorbents
[16,17], so that magnetic separation technique can be applied
to separate organic arsenic [18] with magnetic iron oxide, se-
lenium [19] and phosphate [20]. However, the cost of the
traditional loading-process of magnetic medium is high [21].
Therefore, a new invention of microwave technology is
introduced to defeat the problems. Microwave irradiations
have capability of molecular level heating, which leads to
homogeneous and quick thermal reactions [22e24]. It also
gives a better control [25], energy efficiency [26] and cost
effectiveness [27] over conventional heating. Hence micro-
wave heating offers a potentially attractive alternative to
conventional pyrolysis systems. The thermal conversion of
the bio material requires a uniform heating to maintain the
overall quality of the bio-char. Heating rate should also be fast
to reduce the production cost. Microwave heating can be used
to heat the bio-materials faster and uniformly throughout the
bulk. The microwave penetrates the material and the micro-
wave energy is converted to heat energy. In this way, heat is
generated throughout the bulk of the material. Microwave
heating improved the quality with a less processing time
[28,29]. Till date, study with magnetic bio-char production via
microwave heating using agricultural waste biomass into a
valuable product has not yet been conducted.
In this study, novel magnetic bio-char was produced using
discarded material i.e. EFB by pyrolysis with impregnated
FeCl3. The pyrolysis of the impregnated EFB was carried out
with the help of single stage microwave heating technique.
The details of process parameter were studied such as: mi-
crowave powers, radiation time and impregnation ration
ferric chloride hexahydrate to biomass. The performance of
the produced magnetic bio-char was applied to remove
methylene blue (MB) from aqueous solution. The preparation
conditions were statistically optimized to produce high sur-
face area, high yield of magnetic bio-char and high adsorption
of MB.
2. Materials and methods
2.1. Raw materials
The EFB sample was collected from the Seri Ulu Langat Palm
Oil Mill in Dengkil, Selangor, Malaysia. The EFB was collected
in plastic bags and preserved in a cooling room at 4  C.
Analytical grade Ferric chloride hexahydrate (FeCl3.6H2O) was
purchased from Merck and used as received.
2.2. Experimental procedure for magnetic bio-char
The EFB was first thoroughly washed with distilled water to
remove water soluble impurities and surface adhered parti-
cles and dried at 105  C for 24 h until a constant weight of the
material was obtained. The dry biomass was then crushed and
sieved into a particle size of less than 150 mm. The impreg-
nation ratio (IR) of ferric chloride hexahydrate to biomass for
different amount of sample was prepared. The mixing was
performed in a thermal shaker at controlled temperature
(30  C) for a period of 3 h at 2.5 Hz using 500 mL beaker. After
mixing, the slurry was subjected to vacuum drying at 100  C
for 24 h. The pyrolysis of the biomass was carried out in a
HAMiab-C1500 microwave muffle system oven as shown in
Fig. 1. About 30 g of impregnated biomass sample was placed
in a quartz tube of 35 mm OD, 28 mm ID and 500 mm length. In
all experiments, nitrogen flow 200 cm3 min
1 was kept con-
stant. After the reaction finished, the sample was allowed to
cool at room temperature. Then it was collected from quartz
tube and weighted to determine the yield of the product.
These produced magnetic bio-char then washed with distilled
water until the pH becomes neutral. Finally the sample was
stored in tightly closed bottles.
2.3. Statistical approach of magnetic bio-char
production
Response surface methodology (RSM) is a well known
approach to optimizing the effect of multiple process vari-
ables on the properties of prepared products using a combi-
nation of mathematical and statistical techniques [30,31]. A
standard RSM design called central composite design (CCD)
was applied with three central points and two replicate was
selected for the optimization of magnetic bio-char sample
production. The factors and their levels are described in Table
1. Twenty five experiments were suggested by design of
experiment for magnetic bio-char production. The responses
for each run based on the surface area were further statisti-
cally analyzed by the statistical software to determine the
optimum reaction condition. This method was chosen for
fitting a quadratic model with a minimum number of experi-
ments. It also helps analyze the interaction between the
effective process parameters and identify the factor setting
that optimizes the response [32].
 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5 267

Fig. 1 e Schematic of microwave reactor for production of magnetic bio-char.

2.4. Characterizations of the magnetic bio-char 2.5. Batch equilibrium study

The physical morphology of the EFB derived novel magnetic
bio-char was studied by using (Brand: Zeiss Model: Auriga)
field emission scanning electron microscope (FESEM). The
optimum novel magnetic bio-char sample then was charac-
terized using FESEM (Brand: Zeiss Model: Auriga). Fourier
Transform Infrared (FTIR) spectroscope (Brand: Bruker, Model:
IFS66v/S) was used to analyze the novel magnetic bio-char for
determination of the surface functional groups. Besides
porosity, adsorption behavior of magnetic bio-char is also
influenced by the chemical reactivity of the surface especially
in the form of chemisorbed oxygen in various forms of func-
tional group. These surface oxides have acidic as well as basic
properties [33]. Physical characterization of magnetic bio-char
produced at the optimum condition was analyzed with
Autosorb 1 surface area analyzer by nitrogen adsorption at

77 K. Prior to analysis, the samples were degassed at 200  C
for 3 h. The Brunauer, Emmett, and Teller (BET) surface area
was determined by using “Quanta Chrome Autosorb 6B” BET
analyzer.
MB was chosen in this study due to its wide applications and
toxicity. MB has a chemical formula of C16H18N3SCI, with a
molecular weight of 319.85 g mol
1. Fixed weight (1 g L
1) of
magnetic bio-char was used in all the batch experiments for
MB adsorption. MB concentration was 200 mg L
1. 100 mL of
the solution was taken in a conical flask and agitated at 2 Hz at
30  C until equilibrium is reached. MB concentrations in the
supernatant solutions were measured by a double beam
UVevisible spectrophotometer (Shimadzu, ModeU V 1601,
Japan) at 668 nm after filtering the adsorbent with Whatman
filter paper to make it carbon free. MB uptake at equilibrium,
qe (mg g
1), is determined by Eq. (1):
ðC0
Ce ÞV
qe ¼ (1)
W
where Co and Ce are the initial and equilibrium concentrations
(mg L
1) of MB solution, respectively; V is the volume (L); and
W is the weight (g) of the adsorbent.

Table 1 e Novel magnetic bio-char preparation variations with three levels.

Factor Name Unit Low High Low coded High coded
A Radiation time min 10 30
1 1
B Microwave power (temperature W 600 (390  C) 1200 (650  C)
1 1
inside microwave)
C Impregnation ratio e 0.25 0.75
1 1
268 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5
2.6. Magnetic bio-char yield
The magnetic bio-char yield was defined as the weight of dried
produced magnetic bio-char to the weight of dry raw material
as shown in Eq. (2):
W1
Yieldð%Þ ¼  100
Wo
where W1 and Wo are the dry weight (g) of final magnetic bio-
char produced after chemical pyrolysis and dry weight (g) of
bio-char of precursor as a feed for pyrolysis respectively.
3. Results and discussion
3.1. Effect of process parameters on synthesis of
magnetic bio-char
Synthesis of magnetic bio-char requires the knowledge on the
effect of process parameters such as: microwave power, ra-
diation time and IR. The produced magnetic bio-char was
studied to find out the best level of performance to enhance
the yield with high porosity and adsorption capacity. The ef-
fects of each process parameter were further discussed in the
following section.
3.1.1. Effect of microwave power
The effect of microwave power on yield and adsorption of MB
is illustrated in Fig. 2. It was found that the higher microwave
power has decreased the yield of magnetic bio-char. Higher
microwave power is less effective than lower microwave
power due to the fact that at high microwave power devel-
opment of the pore structure and active sites are insufficient
[34,35]. The reaction between the agent and precursor at high
microwave power [35] do not promotes the development of
the pore structures and active sites [34], possibly was the main
reason for this observation [36,37]. At high microwave power
of 1000 W and above (temperature inside microwave of 600  C
and above), over gasification might occur with detrimental
impact of reducing porosity and surface area, hence the car-
bon yield and adsorption uptake were progressively decreased
Fig. 2 e Effect of microwave power on adsorption uptake of
MB and yield.
[38]. Furthermore, the yield was found to decrease contrari-
wise to the microwave power level, mainly attributed to the
ferric reaction at higher thermal radiation which intensified a
rapid volatilization, dehydration and decomposition. There is
a maximum MB adsorption at 900 W (temperature of 550  C).
At this point, the microwave energy was calculated 54 MJ g
1.
(2) On the other hand, the graph shows the adsorption rate of MB
increased when the microwave power increases. Enhancing
microwave power to 900 W exhibited a drastic increase of
adsorption uptake of MB, possibly related to the combined
effect of internal and volumetric heating responsible for the
expansion of carbon structure [39]. At power levels higher
than the optimum level, the MB adsorption capacity of mag-
netic bio-char progressively decreased because (i) increased
gasification showed the detrimental effect of reducing
porosity and surface area and (ii) microwave energy above the
optimum level resulted in the burning of carbon and
destruction of the pore structures.
3.1.2. Effect of radiation time
Fig. 3 shows the effect of microwave radiation time on yield
and adsorption uptake capacity of MB. It was observed that as
the radiation time increased, the yield of magnetic bio-char
decreased. Possibly sintering effect is responsible for this.
Because of the sintering effect the wall between two adjacent
pores were destroyed and micro and mesopores are widened
which in turn destroyed the carbon framework [39]. Moreover
due to higher radiation time CeFeCl3 and CeCO2 reactions are
facilitated and that leads to destruction of the CeOeC and
CeC bonds and in turn the yield of carbon [40,41]. While,
extending microwave radiation duration from 5 to 20 min
exhibited a drastic enhancement of adsorption from 55 to
265 mg g
1. The condition implied that increasing the expo-
sure supplies energy, which in turn increases the reaction
rates, thus developed the rudiments of the pore structure [39].
It is also observed that the increase in radiation duration
intensified the formation of active sites inside the AC [42].
However, by increasing the microwave radiation period from
25 to 40 min, MB adsorption capacity decreased from 265 to
80 mg g
1. Some pores of carbon would be burnt by increasing
the microwave radiation time beyond the optimum radiation
Fig. 3 e Effect of radiation time on adsorption uptake of MB
and yield.
 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5 269

duration [42]. The MB adsorption capacity decreased when the

activation time increased in the activation stage [34].

3.1.3. Effect of chemical impregnation ratio

Microwave radiations are adsorbed by the activation agents at
the initial stage of activation. Fig. 4 shows the effect of
chemical IR on yield and adsorption uptake capacity of MB. It
was clearly observed that as the IR increased, the yield of
magnetic bio-char decreased. As IR increased from 0.25 to 0.5,
an enhancement of carbon yield occurred from 70 to 89%.
Similarly, increasing IR from 0.25 to 0.5 indicated an incre-
ment of adsorption uptake from 95 to 265 mg g
1, and then
steadily decreased. By increasing the IR of char/FeCl3, the
activation process would play a key role in pore development,
giving a sustaining increase in the BET surface area and pore
volume. Correspondingly, the adsorption uptake was further
enhanced. Beyond this optimum value, the excessive FeCl3
would promote a vigorous gasification reaction, which de-
stroys the carbon framework leading to a dramatic decrease of
accessible area widening and burning of pores could be the
reason for decreasing adsorption capacity [39].

3.1.4. Effect of microwave power on the BET surface area and

pore volume
Fig. 5 shows the influence of microwave heating on the BET
surface area and pore volume of the magnetic bio-char with the
activation of ferric chloride. At low microwave power, it was
observed that low BET surface area and very small pore volume
was developed on the surface of magnetic bio-char. Sharp in-
creases in BET surface area from 250 to 890 m2 g
1 and increase
in pore volume from 0.25 to 0.68 cm3 g
1 was observed when
power increased from 600 to 900 W. Higher microwave power
enhanced the development of porosity of the magnetic bio-
char in this research. Furthermore, increase in microwave
power caused decreases of the BET surface area and pore vol-
ume. This is due to the reduction of pore size at high microwave
power (>900 W), the surface areas of micropore are also lower.
The reduction of micropore sizes and surface area could be
caused by the shrinkage or carbon deposition. Extensive mi-
cropores narrowing could also lead to pores closings.
Shrinkage effects occurred as a function of the bond breaking
processes that facilitate alignment of the structural units.
Fig. 5 e Effect of a) BET surface area and b) Pore volume on
microwave power.
Subsequent bond formation or cross-linking would result in a
further decrease in micropores volume and surface area. These
structural alignments will reduce the interspaces among char
particles, and will promote more compact bulk and more or-
dered structure of the chars [43]. Another reason could be the
polymerization between volatile and non-volatile radical
components in the formation of carbon depositions. The de-
positions could occur in both pore mouth and passages that
lead to pore narrowing [44]. Additionally, microwave heating
had an effect on the development of micropore and mesopores,
the micropore surface area of magnetic bio-char decreased
with the increase of microwave power probably because of the
increased interaction between activation agent and pre-
cursors, resulting in the more intensive pyrolysis of starting
materials. Thus, some microspores were enlarged into meso-
pore. The total pore volume rose as microwave power
increased and the maximum value was obtained at 900 W.

3.2. Statistical analysis of magnetic bio-char production

The CCD is a statistical technique useful for modeling and

analysis during complex optimization [45e47]. The method
used permits reduction of the number of experimental trials
required, and parameters interactions in three dimensional
Fig. 4 e Effect of IR on adsorption uptake of MB and yield. also be evaluated. The results from the experiments were
270 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5

Table 2 e ANOVA for production of magnetic bio-char.

Source Sum of squares DF Mean square F value Prob > F Status
Model 7.653E þ 0.005 9 85027.6 87.57 0.0001 Significant
A 2898.8 1 2898.8 24.43 0.003
B 4798.73 1 4798.73 47 0.002
C 31,239 1 31,239 45.53 0.0001
D 3164 1 3164 32.2 0.0005
A2 81020.9 1 81020.9 14.68 0.001
B2 1945.30 1 1945.3 0.35 0.004
C2 2251.2 1 2251.2 4.08 0.006
AB 59,109 1 59,109 10.17 0.005
AC 24,798 1 24,798 4.49 0.052
BC 1145 1 1145 0.26 0.006
BC 623 1 623 5.06 0.06
Residual 77,287 14 5520
Lack of fit 76,953 5 15,390 414.62 0.0002 Not-significant
Pure Error 334.09 9 37.12

analyzed using analysis of variance (ANOVA) using DOE. The
variables such as microwave power, radiation time and IR
were employed for the analysis in the design to obtain the
high BET surface area of magnetic bio-char. The estimated
regression coefficient and the significance tests on the coef-
ficient are shown in Table 2. The significant of the model is
indicated by the F test value which is 87.57. In addition, the
ANOVA shows the Prob > F value of less than 0.05 indicating
the model is significant. The relationship of the variable was
tested for adequacy of fit by ANOVA. The adequacy of the
model developed was demonstrated by the high coefficient
value (R2 ¼ 0.997) and adjusted coefficient (R2 Adj ¼ 0.987) is
near to one, representing a significance of the model. The
model Eq. (3) is as follows:
BET surface area ¼692:38 þ 86:56A þ 16:33B
118:17C

172:77A2
26:77B2
1:07C2
þ 60:78AB
39:37AC
9:51BC
where, the response was the BET surface area of magnetic bio-
char, A is the coded value of reaction time, B is the coded value
of microwave power and C is the coded value of impregnation
ratio. The coefficient of a single factor indicates a single
interaction for the specific factor. On the other hand, the co-
efficients with two factors represent the interaction between
the two different parameters. The positive sign in the equa-
tion indicates a synergistic effect whereas negative sign in-
dicates antagonistic effect.
Fig. 6 represents the 3-dimensional plot for magnetic bio-
char prepared surface area affect by variables are microwave
power, reaction time and impregnation ratio. The 3-D plot of
the interaction between time and power as depicted in Fig. 6
(a) shows that initially with increasing time BET surface area
increases but after 20 min the BET surface area decrease
which may be due to the fact that if the FeCl3 impregnated
material is exposed to microwave radiation for longer periods
it becomes ash and the material is damaged. When the ma-
terial is exposed to microwave for a shorter period of time the
power has no effect on the BET surface area, but at the higher
exposure time of more than 15 min BET surface area increases
as the power increases. The plot suggests that there is sig-
nificant interaction between time and power. The interaction
between IR and power is shown in Fig. 6 (b). It shows
significant interaction between the two variables mentioned
with power was the actual factor. It can be inferred that lower
IR is more suitable for producing a magnetic bio-char with the
high BET surface area. However at exposure more than 20 min
to microwave again the BET surface area reduces due to
damage to the material. So there exists an optimum point in
between the highest and the lowest level of the two variables
via IR and time. The interaction of IR and time is shown in
Fig. 6 (c). It can be seen that the BET surface area slightly in-
creases as the IR increase at the beginning however at a higher
IR 0.63, BET surface area gradually decrease. Power and IR do
not have a significant interaction.
3.3. Characterization of novel magnetic bio-char
(3) 3.3.1. Analysis of BET surface area
Physical characterization of highest adsorption performance of
the magnetic bio-char produced was analyzed using BET
(Brand: Quanta Chrome Model: Autosorb 6B). Results proved
that higher surface area with higher pore size distribution. The
specific BET surface area of the EFB based magnetic bio-char
prepared was found to be 890 m2 g
1. The results obtained
agreed with previous study [48] which reported that BET surface
area is higher than 350 m2 g
1 after carbonization of lignin at
900  C. In addition, macropores are produced during the acti-
vation stage while carbonization forms only micropores and
mesopores. This development was reported previously in other
studies and explained that the activation not only widens the
size of the existing pores but also forms a new pores [49,50]. The
median pore size for EFB based magnetic bio-char was almost
2 nm, which is in the range of microporous size [45] thus, cor-
robating that the prepared magnetic bio-char is mainly
microporous. Since the diameter of molecules of MB has a
minimum molecular cross-section of 0.8 nm, and the minimum
pore diameter that the MB molecule can enter was estimated to
be 1.3 nm. In contrast, the iodine molecule is significantly
adsorbed because of its smaller size, permitting the penetration
of iodine into micropores larger than 1 nm [51,52].
3.3.2. Field emission scanning electron microscope
The FESEM technique was employed to observe the surface
physical morphology of the selected magnetic bio-char. Fig. 7
 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5 271

Fig. 6 e 3-D plots of BET surface area of magnetic bio-char, (a) interaction of reaction power and reaction time, (b) interaction
of IR and reaction power, (c) interaction of IR and reaction time.

Fig. 7 e (a, b) FESEM image of raw EFB at different magnification, (c, d) FESEM image of magnetic Bio-char produced at
different magnification.
272 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5
Fig. 8 e FTIR absorption spectra, a) Raw EFB b) Magnetic bio-char.
shows images of raw EFB and the prepared novel magnetic
bio-char with different magnification scale (1 mm and 10 mm).
In Fig. 7 (a, b), it can be clearly seen that the surface texture of
raw EFB is intense, slender, and compressed covered by
depositing tarry substances, with a small amount of pores
observed on the surface of the precursor. On the other hand,
after a chemical activation process with the optimum condi-
tions of 900 W microwave power, 20 min radiation time, 0.5 IR
and nitrogen gasification at 200 cm3 min
1, large pores of
different sizes and shapes were well developed porosity, a
distribution of a series of asymmetrical cavities around the
surface of magnetic bio-char as shown in Fig. 7 (c, d). The
microporosity is opened and broadened with a shift to meso-
and micropore as the removal of the exterior of the particle is
significant at high burn-offs [53]. This reflects that N2 is effi-
cient in developing pores on the surfaces of the precursor,
therefore enhancing a novel magnetic bio-char with porous
structure, large surface area and the compactness of the shell
structure is seen to have high adsorption capacity for the
removal of MB from aqueous solution.
3.3.3. Fourier transform infrared spectroscopy
FTIR spectroscope (Bruker, IFS66v/S) was used to analyze the
novel magnetic bio-char for determination of the surface
functional groups. Fig. 8 (a, b) shows the FTIR results for the
surface functional groups of the raw EFB and magnetic bio-
char respectively. Fig. 8 (a) shows raw EFB has no functional
group attachment was observed. On the other hand Fig. 8 (b)
shows that the functional groups have been successfully
impregnated on the surface of magnetic bio-char. The band
located at 3436-3247 cm
1 is related to the NeH groups, while
the region between 2361 and 2270 cm
1 is grouped as C^C
stretch of alkynes. Vibration of C^N is ascribed at intensity
1995 cm
1. The transmittance at 1652e1498 cm
1 is similar to
the OeH (hydroxyl) group, and CH2 and CeOeC (ether, ester
and phenol) functionalities are shown with intensive peaks at
1425 and 1276 cm
1. Similarly, the sharp peaks found at 1053
and 808 cm
1 are corresponds to the CeO (anhydrides) and
CeH derivatives. These results agreed with the surface
chemistry of other agricultural by products [54e56].
3.3.4. EDX analysis of magnetic bio-char
For the confirmation of oxidation reaction, elemental com-
positions of the magnetic bio-char before and after function-
alization were examined by Electron Dispersive X-ray (EDX)
analysis. Table 3 shows a listed of the elemental composition
of the non-magnetic bio-char and magnetic bio-char. The
composition of carbon (C) in non-magnetic and magnetic bio-
char was 76.42% and 10.26% respectively. There was a reduc-
tion of 66.16% from non-magnetic bio-char to magnetic bio-
char, which related to the attachment of iron oxide mag-
netic composite on carbon. Thus, iron oxide functionalization
was successfully achieved by EDX analysis.
3.3.5. Thermogravimetric analysis
Rodriguez-Reinoso and Molina-Sabio [53] stated that three
stages could be identified during the thermal decomposition
of lignocellulosic materials, i.e., (i) evaporation of adsorbed
water in the range of 27e300  C, (ii) primary pyrolysis in the
range of 300e500  C with the release of most gases and early
development of the basic structure of the char; and (iii) further
consolidation of cross-linked product structure between 500
and 850  C with a small weight loss. Fig. 9 shows the variations
of the magnetic bio-char mass with respect to reaction
Table 3 e EDX analysis of the magnetic bio-char.
Element Element mass fraction of dry material
Non-magnetic bio-char Magnetic bio-char
C 76.42 10.26
O 23.3 4.43
F 0.05 1.04
Fe 0.23 84.28
 b i o m a s s a n d b i o e n e r g y 6 1 ( 2 0 1 4 ) 2 6 5 e2 7 5
Fig. 9 e TGA and DTG analysis of the magnetic bio-char produced at optimal conditions.
temperatures at specific time. TGA (Brand; Mettler Toledo
model; Mettler Toledo TGA/STDA 85e) analysis shows one
peak at 360  C indicating weight loss of the magnetic bio-char.
In addition, the peak corresponds to the decomposition of one
element only (carbon), since no other peaks were observed. A
slight loss of weight between 70 and 120  C was observed,
which correspond to the release of adsorbed water. As the
temperature continued to rise from 350 to 650  C, the com-
pound decomposed at a faster rate caused the weight loss due
to the oxidation of magnetic bio-char. There is a steep and
steady weight loss of powdered magnetic bio-char at
400e600  C. The flat profile between 650  C and 850  C showed
that the metal ferric ions were not volatile and thus remain as
residue. These observations revealed the mechanism involved
in the activation progress. Some chemical components might
join to form with bond in the aromatic nucleus of precursors,
followed by recombination and formation of new polymeric
structures with more thermal stability.
4. Conclusion
The aim of the study to produce a novel magnetic bio-char from
a discarded material particularly EFB was successfully ach-
ieved by a single stage microwave heating. The high yield and
high surface area of magnetic bio-char were effectively pro-
duced at microwave power of 900 W, radiation time of 20 min
and IR of 0.5. This optimum condition contributed to a high
surface area of 890 m2 g
1 and that leads to removal of MB with
high efficiency of 99.9% from aqueous solution with a
maximum adsorption capacity of 265 mg g
1. On the whole, the
high performance of the developed novel magnetic bio-char
could replace AC, due its high surface area, high porosity and
273
high adsorption capacity. Therefore, this novel study innovate
new dimension to the various applications of AC.
Acknowledgment
This work was supported by University of Malaya for fully
funding under HIR-MOHE (UM/MOHE HIR, Grant No. D000020-
16001).
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