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Powder Technology 229 (2012) 237245

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Powder Technology
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Physical and chemical characteristics of activated carbon prepared by pyrolysis


of chemically treated date stones and its ability to adsorb organics
Muthanna J. Ahmed a, b,, Samar K. Theydan b
a
b

Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, Bangi 43600, Selangor, Malaysia
Department of Chemical Engineering, University of Baghdad, Baghdad, Iraq

a r t i c l e

i n f o

Article history:
Received 20 January 2012
Received in revised form 14 June 2012
Accepted 23 June 2012
Available online 29 June 2012
Keywords:
Activated carbon
Chemical activation
Ferric chloride
Zinc chloride
Date stones

a b s t r a c t
Preparation of activated carbons from date stones by activation with ferric chloride (FAC) and commonly
used zinc chloride (ZAC) has been investigated. The characteristics of such carbons were evaluated and
found to have surface areas of 780.06 and 1045.61 m2/g, respectively. Effects of activation time, activation
temperature, and impregnation ratio on the yield and iodine number of FAC and ZAC were studied. At best
conditions, 761.40 mg/g maximum iodine number and 47.08% yield for FAC were obtained compared to
1008.86 mg/g maximum iodine number and 40.46% yield for ZAC. The experimental equilibrium data for
methylene blue (MB) and phenol (Ph) adsorption on prepared carbons were well tted to the Langmuir isotherm model, showing maximum MB and Ph capacities of 381.79 and 169.55 mg/g for ZAC; and 255.32 and
181.03 mg/g for FAC, respectively. The kinetic data were found to follow closely the pseudo-second order
model for both adsorbates. The calculated thermodynamic parameters, namely G, H, and S showed
that adsorption of MB and Ph on prepared carbons was spontaneous and endothermic under examined
conditions.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Physical characteristics of activated carbon, such as surface area and
bulk density, and chemical characteristics represented by pH, ash content and conductivity, can affect the use of such substance and render
its suitability for specic applications. Generally, for the adsorption of
organic compounds, like methylene blue (MB) and phenol (Ph), high
surface area, high bulk density, neutral pH, low ash and low conductivity, are desirable characteristics. Because of high adsorptive porosity of
activated carbon, it has been widely used as adsorbent, and in catalysis
or separation processes [14]. The discharge of dyes and phenols from
textile, leather, paper, and plastics industries into the environment
poses severe problems to many forms of life. Acute exposure to these
pollutants can cause increased heart rate, vomiting, shock, Heinz body
formation, and tissue necrosis in humans. Therefore, the removal of
such pollutants becomes environmentally important [5].
The characteristics of activated carbon depend on the physical and
chemical properties of the precursor as well as on the activation
method [6]. Activated carbon can be produced from any carbonaceous solid precursor which may be either natural or synthetic. The
choice of precursor is largely dependent on its availability, cost and

Corresponding author at: Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, Bangi 43600,
Selangor, Malaysia. Tel.: +60 172991374.
E-mail addresses: muthanna.ja@gmail.com (M.J. Ahmed),
samarkarim26@yahoo.com (S.K. Theydan).
0032-5910/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2012.06.043

purity. Due to environmental considerations, agricultural wastes are


considered to be very important precursor because they are cheap,
renewable, safe, available at large quantities and easily accusable
sources; in addition they have high carbon and low ash content
[7,8]. Date stones can be considered as one of the best candidate
among the agricultural wastes because they are cheap and quite
abundant, especially in Mediterranean countries. Carbohydrates are
the major components of date stones which are composed of 42% cellulose, 18% hemi cellulose, 25% sugar and other compounds, 11% lignin and 4% ash. This lignocellulosic composition promotes the
preparation of activated carbon from these precursors [9].
Physical and chemical activations are the common methods for production of activated carbons. Physical activation involves carbonization
of carbonaceous materials at elevated temperatures (500900 C) in an
inert atmosphere followed by activation of the resulting char in the
presence of activating agents such as CO2 or steam. In chemical activation, a raw material is impregnated with an activator such as ZnCl2,
H3PO4, KOH, etc., and the impregnated material is heated in an inert
atmosphere. Chemical activation is preferred over physical activation
owing to the higher yield, simplicity, lower temperature and shorter activation time, and good development of the porous structure [10].
The chemical activation process has been widely used by many researchers for the preparation of activated carbons from different agricultural wastes by various activators such as pine fruit shell by H2SO4
[11], walnut shell by ZnCl2 [12], jute ber by KOH [13], pistachio shell
by H3PO4 [14], citrus fruit peel by H3PO4 [15], piassava bers by ZnCl2
[16], leather shaving waste by H3PO4 [17], vetiver root by H3PO4 [18],

238

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

coffee husks by FeCl3 [19], and tobacco residues by KOH [20]. Though,
previous studies have been done on the preparation of activated carbon from date stones [21,22], those studies did not contain any detailed information about the carbon characterization, kinetics and
thermodynamics of MB and Ph adsorption process.
Therefore the main aim of this work is to compare the detailed
characteristics and adsorption capacities towards MB and Ph of activated carbons prepared from date stones by ferric chloride activation
(FAC) and commonly used zinc chloride activation (ZAC). Also, the
equilibrium isotherms, kinetics, and thermodynamics of adsorption
process have been studied.
2. Materials and methods
2.1. Materials
Date stones were used as a precursor for the preparation of activated
carbon. The stones as received were rst washed with water to get rid of
impurities, dried at 110 C for 24 h, crushed using a disk mill, and
sieved. Fraction with average particle size of 2 mm was selected for
the preparation. Ferric chloride and zinc chloride (purchased from
Panreac Company, Espana) of purities 99.9% were used as chemical activators for date stones. MB (supplied by Fischer Scientic International
Company, England) and Ph (supplied by BDH chemicals Ltd company,
England) of purities higher than 99% were used as adsorbates. All
other chemicals used such as hydrochloric acid and sodium hydroxide
(supplied by Poch SA Company, Poland), sodium thiosulfate supplied
by (Fluka Chemika AC Company, USA), and iodine (supplied by BDH
chemicals Ltd company, England) were of analytical grades.
2.2. Experimental procedure
10 g of dried stones was well mixed with 100 ml of ZnCl2 or FeCl3
solution of different impregnation ratios (weight of activator/weight
of dried stones) (0.52.5) for 24 h at room temperature. The impregnated samples were next dried at 110 C until completely dried and stored
in a desiccator. For the carbonization of dried impregnated samples a
stainless steel reactor (2.5 cm diameter 10 cm length) was used. The
reactor was sealed at one end and the other end had a removable
cover with 2 mm hole at the center to allow for the escape of the pyrolysis gases. The reactor was placed in a furnace (Nabertherm N20/H, Germany) and heated at constant rate of 10 C/min and held at different
carbonization temperatures (400800 C) for different carbonization
times (0.53.5 h). At the end of activation time the carbonized samples
were withdrawn from the furnace and allowed to cool. Then the samples were soaked with 0.1 M HCl solution such that the liquid to solid
ratio is 10 ml/g. The mixtures were left overnight at room temperature,
and then ltered and subsequently the samples were repeatedly
washed with distilled water until the pH of ltrate reaches 6.57.
After that, the samples were dried at 110 C for 24 h, and subsequently
were weighed to determine the yield of the product. Finally the samples
were stored in tightly closed bottles.
The performance of chemical activation process was determined
by the product yield, along with iodine number, which is a measure
of micropore content [23]. The yield and iodine number are determined as follows.

and sample titrations (ml), respectively, N is the normality of sodium


thiosulfate solution (mole/l), 126.9 is the atomic weight of iodine, and
M is the mass of activated carbon used (g).
2.3. Characteristics of activated carbons
The characteristics of ZAC and FAC represented by bulk density, ash
and moisture contents, pH, conductivity, surface area, micropore and
mesopore volumes, and pore size distribution were determined. Bulk
density was determined according to procedure followed by Ahmedna
et al. [24]. Ash content was determined by standard method [25]. Moisture content was determined using oven drying method [26]. The pH
value was determined using pH tester (Model H198107 supplied by
Hanna Company, India) according to procedure followed by Egwaikhide
et al. [27]. Electrical conductivity measurements were carried out by the
method of Ahmedna et al. [24] using EC tester (Model H198304 supplied
by Hanna Company, India). Surface area was determined from the application of BET equation to the adsorptiondesorption isotherm of N2 at
77 K [28]. Micropore volume was determined by applying the Dubinin
Radushkevich equation. The mesopore volume was determined using
BJH desorption branch [29] and the pore size distribution was determined from the density functional theory [30]. NOVAWin2 data analysis
software was used to perform these calculations [31]. The morphology of
prepared activated and raw material was examined by scanning electron
microscopy (SEM) (300 K Pixel CMOS, China).
2.4. Adsorption isotherms
The equilibrium isotherms of MB and Ph adsorption on ZAC and FAC
were determined by performing adsorption tests in 100 ml Erlenmeyer
asks where 40 ml of MB or Ph solutions with initial concentrations of
50450 mg/l for MB and 50250 mg/g for Ph was placed in each ask.
The pH of the solutions was gradually adjusted to 7 by adding small
amounts of 0.1 M of HCl or NaOH solution. 0.02 g of each of the prepared
activated carbon, with average particle size of 250 m, was added to
each ask and kept in a shaker (Type TR-1, Germany) of 120 rpm at different temperatures (303323 K) and for equilibrium times of 4.5 and
2 h for MB and Ph solutions, respectively. Aqueous samples were
taken from the solutions and the concentrations were analyzed. All samples were ltered prior to analysis in order to minimize interference of
the carbon nes with the analysis. The concentrations of MB or Ph in
the supernatant solutions were determined using UVVisible Spectrophotometer (Shimadzu UV-160A) at maximum wave lengths of 664
and 269 nm for MB and Ph, respectively. The MB and Ph uptakes at equilibrium, qe (mg/g), were calculated by the following equation:
qe

Iodine number

V b  V S :N:126:9:15=10
M

Where, Wf and Wo are the weight of nal activated carbon product (g) and the weight of dried date stones (g), respectively. Vb and
Vs are volumes of sodium thiosulfate solution required for blank

Where Co and Ce are initial and equilibrium concentrations of the


MB or Ph (mg/l), respectively, V is the volume of the aqueous MB or
Ph solution (l), and W is the weight of activated carbon used (g).
To determine the maximum MB and Ph uptakes of each carbon,
the experimental adsorption data obtained by Eq. (3) were tted to
the Langmuir isotherm model [32], which can be written as follows:
qe

Wf
Yield%
 100
Wo

C o  C e V
W

qm KLC e
1 KLC e

The equilibrium parameter, RL, is the essential characteristics of


this isotherm, which can be expressed as follows [33]:
1
RL
5
1 KLC o
Where qm is the maximum amount of MB or Ph adsorbed per unit
mass of activated carbon (mg/g), B is the Langmuir constant (l/mg).

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

Where Ct (mg/L) is the liquid-phase concentration of MB or Ph solution at time t (min). Pseudo-rst order model [34], pseudo-second
order model [35], and intraparticle diffusion model [36] were used
to analyze the kinetic data. These models can be expressed as:

Pseudosecond order model

t
1
t

qt
K 2 qe
qe

Intraparticle diffusion model qt K 3 t

1=2

N1

10

Where, N is the number of data points, qexp and qcal (mg/g) are the
experimental and calculated adsorption capacities, respectively.
2.6. Adsorption thermodynamics
Thermodynamic behaviors of MB and Ph adsorption onto ZAC and
FAC were evaluated by the thermodynamic parameters including the
change in free energy (G), enthalpy (H), and entropy (S). These
parameters are calculated from the following equations [37,38]:
InK d

S
H

R
RT

G RT InK d
Kd

qe :W=V
Ce

900

51

800

39

700

27

600

0.5

1.0

1.5

2.0

2.5

3.0

3.5

500
4.0

Activation time (h)


Fig. 1. Effect of activation time on yield and iodine number of activated carbon. (ZAC,
T = 500 C, R = 2 g/g; FAC, T = 700 C, R = 1.5 g/g).

Where qe and qt (mg/g) are the uptake of MB or Ph at equilibrium


and at time t (min), respectively, K1 (1/min) is the adsorption rate
constant, K2 (g/mg.min) is the rate constant of second-order equation, K3 (mg/g.min 1/2) is the intraparticle diffusion rate constant,
and C (mg/g) is a constant that gives an idea about the thickness of
the boundary layer. Besides the value of R 2, the applicability of the kinetic models to describe the adsorption process was further validated
by the normalized standard deviation, q (%), which is dened as:
v

i2
u h
u q q
t
exp
cal =qexp

63

15
0.0

11

decrease occurs within the rst 1.25 h for both FAC and ZAC; this is
due to the rapid evolution of volatile materials to form stable compounds as explained by Haimour and Emeish [39]. They showed
that a steep decrease in yield occurs within the rst 1 h for production of activated carbon from date stones using zinc chloride and
phosphoric acid. Since zinc chloride removes more volatile materials
from the particles compared to ferric chloride, the yield of ZAC was
lower than that of FAC as shown in this gure.
The iodine number of FAC and ZAC increases with activation time
and reaches at maximum of 837.54 mg/g for ZAC and 685.26 mg/g for
FAC, at 1.25 h and thereafter it decreases (Fig. 1). Activation until
1.25 h probably increases the formation of mesopores that are more
effective in adsorption process, but with applying extended activation
times, the wall of mesopores perhaps collapses and they turn into
macrospores [40]. Therefore, the time of 1.25 h was chosen as the
best activation time for both activators. Haimour and Emeish [39]
showed that a maximum iodine number was obtained at optimum
activation time of 1 h for chemical activation of date stones by zinc
chloride. Also it can be noted from this gure that iodine number of
ZAC was higher than that of FAC. This may be due to higher activity
of zinc chloride, as compared with ferric chloride, to produce activated carbon with higher developed pores [41].
3.2. Effect of activation temperature
The effects of activation temperature on yield and iodine number
of prepared activated carbons are shown in Fig. 2.

12

------Yield
FAC

13

Where, R is the universal gas constant (8.314 J/mole K), T is temperature (K), and Kd is the distribution coefcient for the adsorption.
3. Results and discussion
3.1. Effect of activation time
The effects of activation time on yield and iodine number of prepared activated carbons are shown in Fig. 1.
The yield of FAC and ZAC decreases with increasing activation
time, as shown in Fig. 1. An increase in time from 0.5 to 3.5 h at
600 C and 1.5 impregnation ratio leads to a decrease in yield from
61 to 41% and 43 to 29% for FAC and ZAC, respectively. A steep

1000

75

Yield (%)

Pseudofirst order model lnqt  qe lnqe  K 1 t

Iodine number
ZAC

Iodine number (mg/g)

_____

______

Iodine number
ZAC

65

900

55

800

45

700

35

600

25
300

400

500

600

700

800

Iodine number (mg/g)

C o  C t V
W

-----Yield
FAC

Yield (%)

The procedure used for kinetic tests was identical to that used for
equilibrium experiments. The aqueous samples were taken at present
time intervals, and the concentrations of MB or Ph were similarly
measured. The adsorbed amount of MB or Ph at time t, qt (mg/g),
was calculated by:

q% 100

1000

75

2.5. Adsorption kinetics

qt

239

500
900

Activation temperature (oC)


Fig. 2. Effect of activation temperature on yield and iodine number of carbon. (ZAC, t =
1.25 h, R = 2 g/g; FAC, t = 1.25 h, R = 1.5 g/g).

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

It can be seen from Fig. 2 that, as the activation temperature increases from 400 to 800 C, the yield decreases from 51 to 37% and 43
to 27% for FAC and ZAC, respectively. This is due to the loss of the volatile materials with increasing temperature. Beyond 700 C a lower rate
of yield decrease was noticed where a stable structure is formed. This
behavior agrees with results obtained from activation of date stones
using phosphoric acid [42].
Fig. 2 shows that the iodine number increases with activation temperature up to 500 C and 700 C for ZAC and FAC, respectively. Therefore, the temperatures of 500 and 700 C were chosen as optimum
activation temperatures for ZAC and FAC, respectively. The decrease in
adsorption ability of prepared activated carbon with further increase
in temperature might be due to the sintering effect at high temperature,
followed by shrinkage of the char, and realignment of the carbon structure which resulted in reduced pore areas as well as volume [43,44].
These results are in agreements with that of Olivares-Marin et al. [45]
who showed that 500 C was the optimum activation temperature for
the preparation of activated carbon from cherry stones by chemical activation with zinc chloride.
3.3. Effect of impregnation ratio
Fig. 3 shows the effects of impregnation ratio on yield and iodine
number of prepared activated carbons, respectively.
It was noticed that, as the impregnation ratio increases the yield decreases, as shown in Fig. 3. An increase in impregnation ratio from 0.5 to
2.5 leads to a decrease in yield of FAC from 61.03 to 33.97% at 700 C and
from 45.06 to 28.63% for ZAC at 500 C. This decrease is due to the continuous removal of tar material from the pores. The decreasing rate of
yield is lowered beyond an impregnation ratio of 2 where a stable structure is formed. This behavior agrees with results obtained by
Sudaryanto et al. [46] for activated carbon production from cassava
peel by chemical activation with potassium hydroxide.
Fig. 3 shows that the iodine number increases with impregnation
ratio up to 2 for ZAC and 1.5 for FAC. For ZAC, an increase in impregnation ratio from 0.5 to 2 leads to an increase in iodine number from 833
to 1009 mg/g while for FAC, the increase from 0.5 to 1.5 leads to an increase from 442 to 846 mg/g. Therefore, the ratios of 2 and 1.5 were
chosen as optimum impregnation ratios for ZAC and FAC, respectively.
More increase in the concentration of activator perhaps leads to the excessive dehydration and destruction of mesopores and turning them to
larger pores which reduces the adsorption efciency [47].

ZAC, and 1.25 h activation time, 700 C activation temperatures, and


1.5 impregnation ratio for FAC.
The experimental equilibrium data for MB and Ph adsorption on
ZAC and FAC prepared at best conditions have been compared.
These data, calculated from Eq. (3), are tted with Langmuir isotherm
model, Eq. (4), and presented in Fig. 4. The calculated constants of
Langmuir isotherm equation for the two samples along with the correlations coefcients values R 2 are presented in Table 1. This table
shows that the maximum MB uptakes of ZAC and FAC are 381.79
and 255.32 mg/g, respectively, and maximum Ph uptakes of ZAC
and FAC are 169.55 and 181.03, respectively. This table also shows
the successful correlation of experimental data by Langmuir isotherm
with high R 2 values. Several authors [48,14] showed the successful
application of Langmuir isotherm for correlation of experimental adsorption data of dyes and phenols on activated carbons. Fig. 4a shows
that the MB uptake of ZAC at a given MB concentration is higher than
that of FAC, while Fig. 4b shows that the Ph adsorption capacity of FAC
is higher than that of ZAC. This may be due to the smaller ionic radius
of the Fe +3 ions (55 pm) when compared to Zn +2 ions (74 pm)
which enable the formation of activated carbon with high portion of
micropores centered at approximately 10 . These micropores are
preferred for adsorption of Ph which has a molecular size of 10 ,
and not preferred for adsorption of MB which has a molecular size
of 15 , as explained by Oliveira et al. [19]. Table 2 shows that the
adsorbed amounts of MB and Ph increase with increasing temperature which indicates the endothermic nature of adsorption process.
Similar trend was reported by several authors [49,50] for adsorption
of dyes and phenols on activated carbon. It was explained that as

a
375
300

qe (mg/g)

240

150

The best preparation conditions were selected as 1.25 h activation


time, 500 C activation temperatures, and 2 impregnation ratio for

70

1100

160

60

900

50

700

40

500

30
0.0

0.5

1.0

1.5

150

225

300

375

2.0

2.5

300
3.0

Impregnation ratio R (g/g)


Fig. 3. Effect of impregnation ratio on yield and iodine number of activated carbon.
(ZAC, t = 1.25 h, T = 500 C; FAC, t = 1.25 h, T= 700 C).

qe (mg/g)

Iodine number
ZAC

Iodine number (mg/g)

_____

75

b
200

----- Yield
FAC

Ce (mg/L)

1300

80

303 K
313 K
323 K
ZAC------FAC

75

3.4. Adsorption isotherms

Yield (%)

225

120
80
303 K
313 K
323 K
ZAC-----FAC

40
0

40

80

120

160

200

Ce (mg/L)
Fig. 4. Equilibrium adsorption isotherm of MB (a) and Ph (b) correlated with Langmuir
equation at pH = 7, dose = 0.5 g/L (MB, t= 4.5 h; Ph, t = 2 h).

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

241

Table 2
Comparison of MB and Ph maximum adsorption capacity onto activated carbon prepared from various precursors.

360
300

Activated carbon

Adsorbate

Activator

Date stonescarbon

MB

FeCl3
ZnCl2
H2SO4
ZnCl2
H3PO4
H3PO4
H3PO4
FeCl3
ZnCl2
ZnCl2
H3PO4
H3PO4
FeCl3
KOH

qt (mg/g)

240
Pine fruit shellcarbon
Walnut shellcarbon
Jute bercarbon
Pistachio shellcarbon
Citrus fruit peelcarbon
Date stonescarbon

180
120
60
0

Co = 50 mg/L
Co = 450 mg/L
ZAC-----FAC

t (h)

Ph

Piassava berscarbon
Leather shaving wastecarbon
Vetiver rootcarbon
Coffee huskscarbon
Tobacco residuescarbon

qmax (mg/g)

529.00
315.00
225.64
129.00
25.51

170.77
147.1
122.0
60.0
45.49

Ref.
This
This
[11]
[12]
[13]
[14]
[15]
This
This
[16]
[17]
[18]
[19]
[20]

study
study

study
study

180

3.5. Adsorption kinetics

150

The experimental kinetic data for MB and Ph adsorption on ZAC and


FAC, calculated from Eq. (6), are shown in Fig. 5. This gure shows that
the adsorption reached equilibrium in about 4.5 h for MB (Fig. 5a) and
2 h for Ph (Fig. 5b). This gure also shows that rapid increase in capacity
for MB is achieved during the rst 0.5 h as compared to 0.15 h for Ph.
The fast adsorption at the initial stage may be due to the higher driving
force making fast transfer of MB or Ph ions to the surface of ZAC or FAC
particles and the availability of the uncovered surface area and the
remaining active sites on the adsorbent [51]. The experimental data of
Fig. 5 are tted with pseudo-rst order, pseudo-second order and
intraparticle diffusion models, Eqs. (7)(9). The calculated constants

qt (mg/g)

120
90
60
Co = 50 mg/L
Co = 250 mg/L
ZAC-------FAC

30
0
0

0.5

1.5

2.5

t (h)

a
0.06

Fig. 5. Effect of contact time on adsorbed amount of MB (a) and Ph (b) at 303 K (pH =
7, dose = 0.5 g/L).

t/qt (h.g/mg)

temperature increased, the surface activity and kinetic energy of MB


and Ph also increased which caused the interaction forces between
the solute and adsorbent to become stronger than solute and solvent.
From Table 1, it can be noticed that the values of RL are less than unity
(RL b 1) for MB and Ph adsorption at three temperatures, which indicate the favorability of adsorption on prepared carbons. The maximum values of adsorption capacities for MB and Ph reported in this
study is compared to those obtained in the literature for activated
carbons prepared from various agricultural wastes (Table 2). It can
be seen from this table that the prepared activated carbon can be classied as one of the effective adsorbents for this purpose.

Co= 50 mg/L
Co= 450 mg/L
ZAC-------FAC

0.05
0.04
0.03
0.02
0.01
0

1.5

2.5

t (h)

b
0.030
Co = 50 mg/L
Co = 250 mg/L
ZAC-------FAC

Table 1
Langmuir adsorption isotherm parameters.
Adsorbent

Adsorbate

T (K)

qm (mg/g)

KL(L/mg)

RL

R2

ZAC

MB

303
313
323
303
313
323
303
313
323
303
313
323

369.38
372.58
381.79
161.14
164.56
169.55
249.46
250.12
255.32
170.96
173.19
181.03

0.0429
0.0477
0.0476
0.0880
0.0887
0.0863
0.0830
0.0982
0.0974
0.1188
0.1378
0.1461

0.0493
0.0445
0.0446
0.0435
0.0432
0.0443
0.0261
0.0221
0.0223
0.0326
0.0282
0.0267

0.9968
0.9937
0.9929
0.9980
0.9995
0.9998
0.9985
0.9973
0.9965
0.9960
0.9942
0.9949

Ph

FAC

MB

Ph

t/qt (h.g/mg)

0.025
0.020
0.015
0.010
0.005
0.000

0.5

t (h)
Fig. 6. Pseudo-second order kinetic for MB (a) and (Ph) at 303 K (pH=7, dose=0.5 g/L).

242

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

Table 3
Kinetic adsorption parameters at 303 K.
Adsorbent

Adsorbate

Co (mg/L)

Pseudo-rst order model


qe,

ZAC

MB
Ph

FAC

MB
Ph

Adsorbent

Adsorbate

ZAC

MB
Ph

FAC

MB
Ph

Adsorbent

Adsorbate

ZAC

MB
Ph

FAC

MB
Ph

50
450
50
250
50
450
50
250
Co (mg/L)

exp

(mg/g)

50
450
50
250
50
450
50
250

of the three kinetics equations along with R 2 values at different initial


MB on Ph concentrations are presented in Table 3. For MB and Ph adsorption the pseudo-rst order equation is of low R2 values (Table 3).
Moreover, this table shows a large difference between the experimental
and calculated adsorption capacity, indicating a poor pseudo-rst order
t to the experimental data. High R2 values are obtained for the linear
plot of t/qt versus t of pseudo-second order equation for MB (Fig. 6a)
and Ph (Fig. 6b), as shown in Table 3. It can be seen that the
pseudo-second order kinetic model better represented the adsorption
kinetics and the calculated qe values agree well with the experimental
qe values (Table 3). This suggests that the adsorption of MB and Ph on
ZAC and FAC follows second-order kinetics. The successful application
of pseudo-second order model was also reported by Banat [52] for the
adsorption of MB on date stonesbased activated carbon prepared by
chemical activation with KOH, and Alhamed [53] for the adsorption of
Ph on date stones-based activated carbon by chemical activation with
ZnCl2. From Table 3, the values of rate constant K2 decrease with

1.5
MB
Ph
ZAC-----FAC

In Kd

0.9
0.6
0.3
0
0.003

0.0031

0.0032

cal

(mg/g)

88.13
4.771
341.8
6.636
79.40
3.349
152.89
4.509
87.75
4.228
241.09
6.611
84.83
3.156
164.89
4.188
Pseudo-second order model
qe, exp (mg/g)
qe, cal (mg/g)
88.13
91.324
341.8
344.62
79.40
79.891
152.89
152.01
87.75
86.957
241.09
240.37
84.83
85.244
164.89
163.29
Intraparticle diffusion model
qe, exp (mg/g)
C (mg/g)
88.13
56.871
341.8
256.57
79.40
60.618
152.89
113.69
87.75
54.541
241.09
151.14
84.83
68.598
164.89
132.85

50
450
50
250
50
450
50
250
Co (mg/L)

1.2

qe,

0.0033

0.0034

1/T (K-1)
Fig. 7. Plot of In Kd versus 1/T for MB and Ph at pH = 7, dose = 0.5 g/L. (ZAC, t = 4.5 h;
FAC, t = 2 h).

R2

q (%)

0.9797
0.9964
0.9652
0.9528
0.9788
0.9888
0.9751
0.9686

2.4523
0.7839
2.1653
0.8945
2.5899
0.8967
2.0123
0.7323

K2 (g/mg.min)
0.0447
0.0199
0.2671
0.1213
0.0499
0.0179
0.3233
0.1464

0.9993
0.9996
0.9998
0.9995
0.9995
0.9994
0.9999
0.9997

0.1895
0.3654
0.2342
0.4456
0.2373
0.4112
0.2216
0.4324

K3 (mg/g.min1/2)
15.035
39.421
13.773
26.215
14.344
39.512
11.866
20.737

0.9697
0.9534
0.8382
0.8788
0.9386
0.9667
0.8593
0.9199

3.7988
4.4563
5.9875
4.0876
3.3578
2.9984
4.9362
3.0278

K1(1/min)
0.7736
0.5612
1.4227
1.0013
0.4183
0.4546
1.4166
0.9463

increasing initial concentration of MB or Ph. The reason for this behavior


can be attributed to the high competition for the sorption surface sites
at high concentration which leads to higher sorption rates. On the
other hand, for the intraparticle diffusion model, the low values of R2
(Table 3) for MB and Ph adsorption indicate that this model could not
t properly in the experimental kinetic data.
3.6. Adsorption thermodynamics
According to Eqs. (11) and (12), the H and S parameters for MB
and Ph can be calculated from the slope and intercepts of the plot of
In(Kd) versus 1/T (Fig. 7). The calculated values of H, S, and G
are listed in Table 4.
The obtained values for Gibbs free energy change (G) are
2451.63, 2922.88, and 3118.85 J/mole for MB and 954.50,
1063.55, and 1181.32 J/mole for Ph adsorption on ZAC at 303,
313, and 323 K, respectively. While for FAC the values are 1933.69,
2345.18, and 2511.41 J/mole for MB and 1662.63, 2027.69, and
2414.73 J/mole for Ph adsorption on FAC at 303, 313, and 323 K,
respectively. The negative G values indicate thermodynamically spontaneous nature of the adsorption process. The increase in G values
with increasing temperature shows an increase in feasibility of adsorption at higher temperatures. The H parameters are 7823.47 and
2535.77 J/mole for MB and Ph adsorption on ZAC, respectively. For
adsorption on FAC, the values are 6967.13 and 9943.54 J/mole for MB
and Ph, respectively. The positive H is an indicator of endothermic
nature of the adsorption process and also its magnitude gives information on the type of adsorption, which can be either physical or chemical.
The enthalpy of adsorption, ranging from 2.1 to 20.9 kJ/mole corresponds to a physical sorption [54,55]. The adsorption heats of MB and
Ph are in range of physisorption. Therefore, the H values show that
the adsorption of MB and Ph on ZAC and FAC was taken place via
physisorption. These results are in agreement with those of Mahmoud
et al. [56] for adsorption of MB on kenaf ber-based activated carbon
and those of Srivastava et al. [57] for adsorption of Ph on activated
carbon.

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

243

Table 5
Characteristics of activated carbon samples.
Characteristic

ZAC

FAC

Yield (%)
Bulk density (g/ml)
Ash content (%)
Moisture content (%)
pH
Conductivity (s/m)
Micropore volume (cm3/g)
Mesopore volume (cm3/g)
Iodine number (mg/g)
Surface area (m2/g)

40.46
0.322
2.04
10.86
6.1
330
0.512
0.129
1008.86
1045.61

47.08
0.271
6.62
12.54
6.5
290
0.468
0.105
761.40
780.06

[19]. The most important characteristics are surface area and iodine
number and the results of this table showed that the surface areas of
FAC and ZAC are 780.06 and 1045.61 m2/g, respectively. This result
for ZAC is in agreement with that reported by Bamueh [58] who
showed that the surface area of activated carbon prepared from date
stones by chemical activation with zinc chloride was between 802 and
1270 m2/g. The iodine numbers of FAC and ZAC in this study is higher
than reported by Haimour and Emeish [39], 495 mg/g, for activated carbon prepared by chemical activation of date stones using phosphoric
acid. Fig. 8 shows the SEM images for the date stones and prepared activated carbons. As shown in Fig. 8a, the surface of date stones is very
smooth and there are very little pores on it. After FeCl3 activation, the
surface of FAC become rough and many pores appear on it (Fig. 8b). It
was reported that the impregnation with FeCl3 had important impact
on the increase in specic surface area and development of micropores

Fig. 8. SEM micrographs (300) of date stones (a), FAC (b), and ZAC (c).

The S values for adsorption on ZAC are 34.06 and 11.52 J/mole
for MB and Ph, respectively. For adsorption on FAC, the values are
29.51 and 38.30 J/mole for MB and Ph, respectively. The positive
S values suggest an increase in the randomness at sorbate-solution
interface during the adsorption process.
3.7. Yield and characteristics
The yield and characteristics of ZAC and FAC prepared at best conditions were determined and summarized in Table 5. This table shows
47.08% yield of FAC compared to 40.46% yield of ZAC. This may be due
to the ability of zinc chloride to remove more volatile materials from
the particles compared to ferric chloride, as explained by Olivera et al.
Table 4
Thermodynamics adsorption parameters.
Adsorbent

ZAC
FAC

Adsorbate

MB
Ph
MB
Ph

H (J/mole)

7823.47
2535.77
6967.13
9943.54

S (J/mole)

34.06
11.52
29.51
38.30

G (J/mole)
303 K

313 K

323 K

2451.63
954.50
1933.69
1662.63

2922.88
1063.55
2345.18
2027.69

3118.85
1181.32
2511.41
2414.73

Fig. 9. Isotherms of N2 adsorption-desorption (a) and pore size distribution (b) for ZAC
and FAC.

244

M.J. Ahmed, S.K. Theydan / Powder Technology 229 (2012) 237245

centered at approximately 10 (Fig. 8b), as compared to the carbon


structure obtained by ZnCl2 activation which has micropores centered
at approximately 15 (Fig. 8c). Fig. 9 displays the isotherms of N2
adsorptiondesorption (Fig. 9a) and pore size distribution (Fig. 9b) for
the activated carbons prepared from date stones. It can be seen from
Fig. 9a, that the isotherm presents a high adsorption at low relative
pressure, characteristics of microporous materials, where the adsorption branch resembles that of a type I isotherm in the international
union of pure and applied chemistry IUPAC classication. From this gure it can be also concluded that the isotherm displayed a small hysteresis loop, indicating the presence of very small mesopore volume.
Fig. 9b presents the pore size distribution for the activated carbons
made in this study. This gure shows that the pore structure consists
basically of micropores, which are mainly dened by IUPAC as pores
smaller than 20 in diameter. This can be also concluded from the results of Table 1, which show a micropore volume of 0.468 cm3/g compared to a mesopore volume of 0.105 cm3/g for FAC; and a micropore
volume of 0.512 cm3/g compared to a mesopore volume of
0.129 cm3/g for ZAC. It is interesting to observe that prepared activated
carbon by ferric chloride activation showed the formation of better dened pores centered at approximately 10 (Fig. 9b) which is preferred
for adsorption of phenol as compared to methylene blue. This result
could be due to the smaller ionic radius of Fe+3 ions (55 ppm).
4. Conclusions
Date stones were used as precursors for the production of activated
carbon by chemical activation with ferric chloride and zinc chloride. The
characteristics of such carbons as well as their adsorption capacities for
methylene blue and phenol were investigated. Activation by ferric chloride leads to carbon with high yield as compared to that obtained by
using zinc chloride. Phenol was more selectively adsorbed than methylene blue by small micropores (10 ) of date stones-based activated
carbon prepared by ferric chloride activation. Small micropores favor
phenol adsorption while large micropores or mesopores favor methylene blue adsorption. The experimental equilibrium data for methylene
blue and phenol adsorption on prepared activated carbons were well
tted to the Langmuir isotherm model. The calculated thermodynamic
parameters, namely G, H, and S showed that adsorption of MB
and Ph on prepared activated carbons was spontaneous and endothermic under examined conditions.
Acknowledgment
We gratefully acknowledge the University of Baghdad and the Department of Chemical Engineering for the assistance and support of
this work.
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