Journal of Hazardous Materials 173 (2010) 750757

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Reduction of COD in renery wastewater through adsorption on date-pit

activated carbon
Muftah H. El-Naas , Sulaiman Al-Zuhair, Manal Abu Alhaija
Chemical and Petroleum Engineering Department, United Arab Emirates University, 17555 Al-Ain, United Arab Emirates

a r t i c l e

i n f o

Article history:
Received 6 May 2009
Received in revised form 31 August 2009
Accepted 1 September 2009
Available online 4 September 2009
Keywords:
COD reduction
Petroleum renery
Date-pit
Controlling mechanism
Adsorption

a b s t r a c t
Experiments were carried out to evaluate the batch adsorption of COD from petroleum renery wastewater on a locally prepared date-pit activated carbon (DP-AC), and its adsorption effectiveness was compared
to that of commercially available BDH activated carbon (BDH-AC). Adsorption equilibrium and kinetic
data were determined for both adsorbents and tted to several adsorption isotherm and kinetics models,
respectively. The Langmuir monolayer isotherm tted well the equilibrium data of COD on both adsorbents; whereas, the kinetics data were best tted by the pseudo-second order model. Modeling of the
controlling mechanisms indicated that both intrinsic kinetics and mass transfer contributed to controlling
the adsorption process. Mass transfer seemed to be the dominant mechanism at low COD content, while
intrinsic kinetics dominates at high concentrations. In general, the adsorption effectiveness of locally
prepared DP-AC was proven to be comparable to that of BDH-AC. Therefore, DP-AC can be utilized as an
effective and less expensive adsorbent for the reduction of COD in renery wastewater.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Various treatment technologies have been used for the reduction of COD, which is a major contaminant in petroleum renery
and industrial wastewater. These techniques include ltration, ion
exchange, coagulation/occulation, reverse osmosis and electrodialysis. Adsorption provides an attractive alternative treatment,
especially if the adsorbent is inexpensive and readily available.
Adsorption of COD has been previously studied to evaluate the
overall adsorption behavior in wastewaters [1]. Considerable effort
has been devoted to the production of low cost adsorbents using
less expensive and readily available materials [24]. The use of activated carbon (AC), as an absorbent, has proven to be effective in a
wide range of applications, including the removal of both organic
and inorganic pollutants from wastewater [5]. The versatility of
high surface area, porous structure and surface adsorption capacity, which can be appropriately modied by physical and chemical
treatments, are among the reasons for the use of such adsorbent.
However, the cost of commercially available AC is relatively high
[2], and therefore great attention has been focused on the production of low-cost AC of properties comparable to those of the
commercially available. In order to achieve this target, agricultural
waste was considered as a promising raw material for generating AC capable of removing various pollutants including COD from

Corresponding author. Tel.: +971 3 713 3637; fax: +971 3 762 4262.
E-mail address: muftah@uaeu.ac.ae (M.H. El-Naas).
0304-3894/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.09.002

industrial wastewater. Mohan et al. [4] investigated the adsorption

effectiveness of AC from different raw materials for COD removal,
and reported reduction percentages of up to 74% using AC from
coconut shell ber and rice husk. Recently, date-pits (DP) have
received considerable attention as a lignin origin for preparing
AC. In addition to producing AC from inexpensive raw material,
using DP is considered a waste minimization process. DP constitute approximately 10% of the total weight of dates [56], making
them the largest agricultural by-product in palm growing countries,
including the UAE. Therefore, nding ways to use this agricultural
by-product protably will benet date farmers substantially and
offers a useful alternative for its disposal or current use as animal
feed [6].
Several studies have examined different activation processes
of DP and the possibility of using the produced AC in wastewater adsorption treatment. DP-AC was prepared by physical [78]
and chemical activation [9]. In addition, physical activation of DP
has been carried out in different reactor congurations including
uidized bed [10]. The adsorption effectiveness of DP-AC of aluminum was evaluated and compared to that of commercial BDH-AC
[11]. Generally, the effectiveness of DP-AC was found to be comparable to that of BDH-AC, and was even preferable under certain
conditions, such as low Al concentrations and low pH.
The objective of the present work is to explore the viability
of using DP-AC, locally prepared by physical activation, as a low
cost adsorbent for the reduction of COD from petroleum renery
wastewater. Equilibrium and kinetics studies were carried out to
determine the mechanisms of the adsorption process.

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

1.1. Adsorption isotherms

Adsorption is a process that results in the removal of a solute
from a solution and concentrating it at the surface of the adsorbent,
until the amount of the solute remaining in the solution is in equilibrium with that at the surface. This equilibrium is described by
expressing the amount of solute adsorbed per unit mass of adsorbent, qe , as a function of the concentration of solute remaining
in solution, Ce . An expression of this type is termed adsorption
isotherm.
Many theoretical and empirical models have been developed
to represent the various types of adsorption isotherms. At present,
there is no single model that satisfactory describes all mechanisms
and shapes. Langmuir and Freundlich equations are examples
of such models that are commonly used to describe adsorption
isotherms in water and wastewater treatment applications. The
Langmuir isotherm assumes uniform and constant binding of the
sorbate on the surface of the adsorbent, which is usually described
by:
qe =

qm bCe
1 + bCe

(1)

751

where qD is the DR isotherm constant related to the degree of

sorbate sorption by the sorbent surface (mg/g) and BD is related to
the free energy of sorption per mole of sorbate as it migrates to
the surface of the adsorbent from innite distance in the solution
(mol2 /kJ2 ). This means free energy can be estimated from the value
of BD using the following equation:
E=

(7)

2BD

The above mentioned isotherms are characterized by parameters that express the surface properties and afnity of the adsorbent
towards different pollutants. Different isotherm models can be
used to t the equilibrium data. The shapes of various model
isotherms depend on the type of adsorbate/adsorbent and the intermolecular interactions between the uid and the surface [1]. The
model that ts the experimental data most accurately can then be
used to describe the system and predict the adsorption behavior
for practical process design.
1.2. Adsorption kinetics

where qe is the equilibrium amount of solute adsorbed (mg/g of

solid), Ce is the equilibrium concentration of solute in solution
(mg/L), and qm (mg/g) and b (mg/L)1 are constants, representing
the maximum adsorption capacity for the solid phase loading and
the energy constant related to the heat of adsorption, respectively.
The parameters qm and b are temperature dependent parameters. A
convenient way of expressing this temperature dependence takes
advantage of Vant Hoffs relationship between the equilibrium
constant and the standard enthalpy change associated with the
process under consideration, which leads to the following relations:

The adsorption kinetics can be described by diffusion through

the adsorbent, such as lm, pore and surface diffusions, and poresurface adsorption or any combination of these four steps. In order
to examine the controlling mechanism of an adsorption process
and to determine the minimum necessary time to achieve equilibrium, several kinetics models such as the pseudo-rst order,
Elovichs, pseudo-second order and intraparticle diffusion models
can be used. Brief descriptions of these models are given in the
following sections.

qm = (1 + T )

1.2.1. Lagergren pseudo-rst order model

The Lagergren pseudo-rst order model is most commonly used
to describe the adsorption of solute from a liquid solution. The
linearized form of this model is given by:

b = exp

 H

ads

(2)

(3)

RT

where Hads is the standard enthalpy change accompanying the

reversible adsorption (kJ mol1 ), R is the universal gas constant, T
is the absolute temperature and , and are constants. The constants found in Eqs. (2) and (3) can be determined experimentally
by measuring the equilibrium adsorption at different temperatures.
Unlike the Langmuir isotherm model, the Freundlich isotherm
(Eq. (4)), which has been widely used in correlating equilibrium
data, does not have any thermodynamic basis and does not offer
much physical interpretation of the adsorption data [12]. This
model is not bound by a maximum uptake, and it does not approach
Henrys law at low concentrations.
The Freundlich isotherm can be written as:
1/b

qe = aCe

(4)

where, a and b are constants

The Sips isotherm combines the Langmuir and Freundlich
isotherms into one equation. At low sorbent concentration, the
Sips isotherm approaches the Freundlich isotherm, whereas it
approaches the Langmuir isotherm at a high concentration. This
model is presented in the LangmuirFreundlich form as follows:
qe =

KLF CenLF
1 + (aLF Ce)nLF

(5)

where, KLF , nLF and aLF are constants.

Another isotherm that has seen considerable applications in
adsorption processes is the DubininRadushevich:

qe = qD exp

BD RT ln

1+

1
Ce

2 

(6)

ln (qe q) = ln (qe )

kt
2.303

(8)

where k is the kinetics constant of pseudo-rst order adsorption

(min1 ), qe and q (mg/g) are the amounts adsorbed at equilibrium
and at time t (min), respectively.
1.2.2. Elovichs model
In recent years, Elovichs model has been successfully used to
describe the adsorption of pollutants from aqueous solutions. The
linearized form of this model is given by Eq. (9):
q=

1
1
ln (ab) + ln (t)
b
b

(9)

where, a is the initial adsorption rate (mg/g/min), and 1/b (mg/g) is

a parameter related to the number of sites available for adsorption.
1.2.3. Pseudo-second order model
In this model, the rate limiting step is the surface adsorption
that involves chemisorption, where the adsorbate removal from
a solution is due to physicochemical interactions between the two
phases [13]. The model is usually represented by its linearized form
as follows:
1
1
t
=
+
t
2
q
q
K2 qt
e

(10)

where, K2 (g/mg/min) is the pseudo-second order rate constant of

adsorption.

752

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

Table 1
Surface characteristics of BDH and date-pit (DP) activated carbons.
Characteristics
Particle size (m)
BET surface area (m2 /g)
BET surface area in the
micropore region (m2 /g)
Total pore volume (cm3 /kg)
Total pore volume in the
micropore region (cm3 /kg)

BDH
8501700
1220
1173
534
479

concentrations as follows:
q=

DP
125212
490
423
229
165

(12)

where, q is the uptake (mg adsorbate/g adsorbent), Ci is the initial

COD concentration, Cf is the nal COD (mg/L), M is the adsorbent
amount (g) and V is the solution volume (l).
2.3. Regeneration

1.2.4. Intraparticle diffusion model

The intraparticle diffusion model describes adsorption processes, where the rate of adsorption depends on the speed at which
adsorbate diffuses towards adsorbent (i.e., the process is diffusioncontrolled), which is presented by Eq. (11).

q = kd t + 

(Ci Cf )V
M

(11)

where, kd is the rate constant of the intraparticle transport

(mg/g/min1/2 ) and  (mg/g) is a constant related to the thickness
of the boundary layer. High values of  indicate greater boundary
layer effect.

2. Experimental methods

Regeneration is an important aspect in evaluating the capacity and practicality of any adsorbent. The regeneration of activated
carbon has been meticulously examined in the literature and many
researchers have successfully regenerated activated carbon using
different methods. These included the utilization of pyrolysis [14],
steam [15], water under sub-critical conditions [16], surfactants
[17], direct ozonation [18], microwave [19], electrochemical methods [20,21] wet peroxide oxidization [22] bio-regeneration [23],
and ultrasound [24]. Although the results depended on the application and the type of wastewater treated, in most cases the activated
carbon was fully regenerated and reused for many cycles. These
studies have conrmed that activated carbon can be easily regenerated and that the cost associated with the regeneration process can
be substantially reduced. In the present study, the regeneration of
activated carbon was not addressed and will be thoroughly examined in a future study that evaluates the continuous adsorption of
COD in a packed bed column.

2.1. Preparation of DP-AC

3. Results and discussion
DP-AC was prepared from raw DP granules, obtained from
Al-Saad Date Processing Factory, Al-Ain, UAE. The granules were
washed, dried, grinded and screened. The collected granules were
carbonated and activated to produce DP-AC. The carbonization is
performed in a tube furnace (Thermolyene, USA) which has been
initially purged with a ow of nitrogen for 10 min. After that, the
furnace was heated at a rate of 10 C/min up to 600 C and then kept
at this temperature for 4 h. After cooling to room temperature, the
material is considered carbonized, but still inactive. After weighing
the inactive carbon, it was activated in the same tube furnace at
a temperature of 900 C using a ow of carbon dioxide instead of
nitrogen. The resulting AC was then degassed under vacuum (Shel
Lab, USA) for about 2 h before use. The main surface characteristics
of the prepared DP-AC and commercially available DBH-AC were
determined using a surface area analyzer (Micromeritics, Model
ASAP-2010) and presented in Table 1.

3.1. Effect of adsorbent dose

The amount of adsorbent, which is usually referred to as the
adsorbent dose (grams of adsorbent per 1 L of solution) plays an
important role in the adsorption process. The effect of the adsorbent
dose on COD removal for the two adsorbents (DP-AC and BDHAC) was evaluated by varying the dose from 180 g/L. The results
are presented in Fig. 1 and indicate that higher percent removal
is achieved for higher adsorbent dose, but the uptake decreases
with increasing the amount of adsorbent. This may be attributed
to many factors such as availability of solute, interference between
binding sites, electrostatic interactions, and reduced mixing due to
high adsorbent concentration in the solution [2526]. Many of the
adsorption sites, therefore, remain unsaturated due to the limited

2.2. COD batch adsorption

Batch adsorption equilibrium experiments were carried out by
contacting a specied amount of adsorbent with 50 ml wastewater sample, of a known initial COD concentration, in a sealed
glass bottle. The bottle was kept on a shaker (WSB-30, Korea) at
different temperatures for 24 h to reach equilibrium. At regular
intervals, samples were withdrawn and the COD was measured
using UV Spectrophotometer (DR-5000, Germany). The COD uptake
was determined as a function of time, using 20 g/L DP-AC and BDHAC, contacted with renery wastewater samples obtained from a
local petroleum renery. Wastewater samples of three different initial concentrations, namely, 3490, 1662 and 950 (0.5) mg/L were
tested. In addition, the experiment was carried at different values
of temperature and pH to determine their effects.
After 24 h, the samples were ltered and the nal COD was
determined. Adsorption efciencies of the prepared DP-AC were
compared to those of commercial BDH-AC. The uptake, q, was then
calculated from the difference between the initial and the nal COD

Fig. 1. Effect of adsorbent dose on COD uptake at initial COD concentration of

3490 mg/L and 25 C.

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

753

Table 2
Fitted kinetic parameters for the adsorption of COD onto DP-AC and BDH-AC at 25 C.
Co (mg/L)

Pseudo-rst order
qe (mg/g)

Elovichs equation
1

k (min

a (mg/g/min)
7.7 104
7.2 1016

Pseudo-second order
2

R2

1/b (mg/g)

K (g/mg.min)

qe (mg/g)

10.53
3.40

0.93
0.87

0.0016
0.0069

151.52
147.06

1.00
1.00

BDH
DP

3490

31.37
12.38

0.0122
0.0299

0.9497
0.8658

BDH
DP

1662

19.33
27.54

0.0188
0.0258

0.7716
0.8975

8.9 104
294.4

5.03
8.68

0.94
0.91

0.0051
0.0029

74.63
73.53

1.00
1.00

BDH
DP

950

18.24
7.81

0.0295
0.0208

0.9088
0.7426

15.3 106
151.3

5.18
2.05

0.87
0.91

0.0054
0.0145

42.74
42.55

1.00
1.00

availability of the sorbate, which in turn lowers the uptake and the
adsorption efciency [27]. The gure also shows that increasing
the dose beyond 20 g/L had little effect on the COD reduction and
hence this value was considered as the optimum dose and used for
the rest of the experimental work.
3.2. Adsorption kinetics
The COD adsorption rate was determined for the two adsorbents
by contacting renery wastewater samples with different initial
COD contents (3490, 1662 and 950 mg/L) using an adsorbent dose
of 20 g/L. The results indicate that most of the COD reduction takes
place during the rst 30 min for both absorbents as shown in Fig. 2.
After that the COD contents remained almost unchanged, which is
assumed to be the equilibrium amount. The adsorption rate data
were tted to the different kinetic models described in Section
1.2, namely: Lagergrens pseudo-rst order (Eq. (8)), Elovichs (Eq.
(9)), pseudo-second order (Eq. (10)) and intraparticle diffusion (Eq.
(11)). Figs. 36 present the applicability of the four models at different initial COD, respectively.
Fig. 3 shows the relationship between ln(qe q) and t, according
to the linearized Lagergrens pseudo-rst order equation (Eq. (8)).
It is observed that the results deviate signicantly from a straight
line, which indicates that the pore diffusion is not the sole rate controlling step, as the Lagergrens pseudo-rst order model suggests.
The adsorption data shows a curvature in the initial period, which
is attributed to the intraparticle diffusion or external mass transfer
effects. Similar results were found by plotting q vs. ln(t) according to the linearized Elovichs equation (Eq. (9)), shown in Fig. 4
for both adsorbents, which also proves the incompatibility of the

Elovichs model to describe the adsorption mechanism. The best

straight lines that pass through the data points were used to determine the kinetics parameters of both models, which are shown in
Table 2. The deviation of the values of R2 from unity is a measure
of the incompatibility of each respective case.
On the other hand, when t/q was plotted against t, according to
the linearized pseudo-second order model (Eq. (10)), a clear linear relationship was observed for all cases, as shown in Fig. 5. The
data were tted perfectly well by straight lines, with R2 values of
1.00. This proves that the adsorption kinetics is more accurately

Fig. 3. ln (qe q) vs. t according to pseudo-rst order model. () C0 = 3490 mg/L, ()
C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.

Fig. 2. Kinetics of COD uptake using 20 g/L adsorbents at 25 C and different initial COD contents. () C0 = 3490 mg/L, () C0 = 1662 mg/L, () C0 = 950 mg/L, (black)
BDH-AC and (white) DP-AC.

Fig. 4. q vs. ln(t) according to Elovichs model. () C0 = 3490 mg/L, ()

C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.

754

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

Fig. 5. t/q vs. t according to the pseudo-second order model. () C0 = 3490 mg/L, ()
C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.

described by pseudo-second order model. The kinetics parameters

of the model are shown in Table 2.

To further conrm this conclusion, q was plotted against t,

which would, according to Eq. (11), give a straight line if intraparticle diffusion was the limiting process. However, the results
in Fig. 6 show that this is not the case. The early stage sharper
portion is assumed to be due to the mass transfer external resistance; whereas the later linear portion is an indication of some
intraparticle diffusion control.
3.3. Adsorption isotherms
The equilibrium adsorption isotherms of COD were determined
at different temperatures of 25, 40 and 60 C, and the results are
shown in Figs. 7 and 8 for DP-AC and BDH-AC, respectively. The
experimental data were tted to the Langmuir, Freundlich, Sips
and DubininRadushevich isotherm models using Sigma Plot nonlinear regression, which uses the MarquardtLevenberg algorithm
to nd the parameters that give the best t between a set of data
and a proposed non-linear equation. Values for the determined
parameters of each isotherm are shown in Table 3, together with
the respective R2 value for each regression. The results show that

Fig. 6. q vs. t according to the intraparticle diffusion model. () C0 = 3490 mg/L,

() C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.

Fig. 7. Langmuir tting for the equilibrium isotherm data of the COD adsorption on
DP-AC at different temperatures.

the experimental data were best t by the Langmuir model with R2

values of almost 1.0.
3.4. Effect of temperature and pH
As shown in Table 3, the adsorption isotherms of COD from
wastewater were determined at different temperatures of 25,
40 and 60 C. The results show that increasing the temperature
resulted in increasing adsorption capacity. Increasing the temperature from 25 to 60 C, resulted in improving the uptake capacity
by 30% and 53% for BDH-AC and DP-AC, respectively. This is due to
the increase in the kinetic energy of the adsorbate with temperature, which enhances the adsorbate availability at the active sites of
the adsorbent. In addition, raising the solution temperature results
in expansion of the pores within the adsorbent particles, which in
turn enhances the adsorption capacity.
The value of standard enthalpy change accompanying the
reversible adsorption, Hads and the constants , and found
in Eqs. (2) and (3) were determined by tting the values of qm and
b at different temperatures. The values of Hads for BDH-AC and
DP-AC were found to be 5.48 and 7.36 kJ/mol which conrms the

Fig. 8. Langmuir tting for the equilibrium isotherm data of the COD adsorption on
BDH-AC at different temperatures.

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

755

Table 3
Isotherm model parameters for the adsorption of COD on DP-AC and BDH-AC at different temperatures.
25 C

40 C

60 C

Isotherm

Parameter

Langmuir

b (L/mg)
qm (mg/g)
R2

Freundlich

aF
bF
R2

1.518
0.716
0.98

2.651
0.6022
0.99

1.304
0.763
0.92

1.79
0.665
0.97

0.989
1.006
1.00

1.59
0.699
0.98

Sips (LF)

nLF
aLF
KLF
R2

1.489
0.005
0.0623
0.93

0.902
0.002
0.833
0.94

2.605
0.009
5.8 104
0.93

1.228
0.0036
0.169
0.93

1.312
0.0041
0.147
0.93

1.187
0.0035
0.226
0.96

DR

qD (mg/g)
BD
E (J/mol)
R2

BDH

DP

BDH

DP

BDH

DP

1.62 103
252.81
0.99

2.07 103
191.58
1.00

1.89 103
293.65
0.93

2.4 103
217.82
0.99

2.05 103
331.19
0.99

2.85 103
241.45
0.99

128.49
0.0021
15.43
0.76

105.3
1.706 103
17.12
0.81

endothermic nature of the adsorption. The enthalpies of adsorption

on both adsorbent were in the same order of magnitude, which is
the reason for the comparable adsorption effectiveness. However,
the higher absolute value of DP-AC indicates that it has a higher
adsorption afnity than BDH-AC which is reected in the higher
improvement of the uptake capacity. The values for Hads are consistent with physical adsorption, where the heat of adsorption is
known to be of the order of 10 kJ/mol [28].
The effect of initial pH on the adsorption of COD was also evaluated at 25 C for an initial concentration of 3490 mg/L and different
initial pH values in the range of 210. The typical pH of the renery
wastewater was about 8, and it was adjusted to the desired value
by the addition of few drops of 0.1 M HCl or 0.1 M NaOH. Fig. 9
shows equilibrium uptake as a function of pH for both adsorbents.
Although there was a slight enhancement in COD adsorption for pH
values ranging from 7.5 to 8, the initial pH of the wastewater did
not seem to have any signicant effect on the adsorption process.
Similar results for the optimum range of pH were reported for the
adsorption of COD [29], COD and BOD [3031] and dyes [3233].
3.5. Modeling and adsorption mechanisms
Adsorption of contaminants on any solid surface can take place
through physical adsorption, chemical adsorption or ion exchange.
It is rather difcult to predict the exact mechanism, since it depends

131.01
0.0011
21.32
0.76

102.8
1.605 103
17.65
0.85

124.66
0.001
22.36
0.76

113.94
1.1 103
21.32
0.83

on the characteristics of the sorbent as well as the sorbate. Ion

exchange is expected to be less important with increasing pH, since
most functional groups become dissociated if the pH is above a certain limit [34]. The ion exchange mechanisms can be signicant
if the bonding energy is in the range of 8-16 kJ/mol [3536]. The
estimated bonding energy (E) for the adsorption of COD on DP-AC
was found to be 0.017 kJ/mol, which suggests that ion exchange
does not play an important role and that physical adsorption or
chemisorptions is the major adsorption mechanism.
Mathematical modeling of the adsorption process is an essential step in understanding the relative contributions of the different
mechanisms. Mao et al. [37] modeled protein adsorption with
porous and non-porous particles to determine the relative importance of the main controlling mechanism: surface reaction and
mass transfer. The model was also applied to the biosorption of
lead [12] and copper [38] by C. vulgaris. It is assumed that the transport of the adsorbate from the bulk solution to the surface of the
adsorbent can be described by lm resistance mechanism:
dp
= aK 103 (C Ci )
dt

(13)

where q and C are the adsorbate concentrations in the adsorbent

(mg/g) and in the solution (mg/L), respectively; a is the surface area
of the adsorbent per unit mass (cm2 /g); K is the liquid lm mass
transfer coefcient (cm/min); and Ci is the concentration of the
adsorbate in the solution at the internal solid/liquid interface. The
adsorbate concentration in the adsorbent, q, is related to that in the
solution, C, through mass balance on the adsorbate:
q=

C0 C
m

(14)

where, C0 is the adsorbate concentration in the bulk solution (mg/L)

and m is the adsorbent dose (g/L).
The interaction between the adsorbate and the active sites on
the surface of the adsorbent can be described by the following
second-order reversible equation:
dp
= k1 [(qm q)Ci Kd q]
dt

Fig. 9. Equilibrium isotherm data for the adsorption of COD at different pH values.

(15)

where, k1 is the second-order forward rate constant (L/mg/min); qm

is the maximum adsorption capacity of the adsorbent (mg/g); Kd is
the adsorption equilibrium constant (mg/L), which is the reciprocal
of the constant, b, in Langmuir isotherm.
Combining Eqs. (13)(15) to eliminate Ci , q and dq/dt, will give
the rate of change in the adsorbate concentration in the solution

756

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

Table 4
Model parameters for single and dual control mechanisms.
Mechanism

k1 (L/mg/min)

K (cm/min)

Intrinsic kinetics
Mass transfer
Combined

0.00002

0.000049

6.3 108
1.2 107

[34]:


dC
= (C x1 )(C x2 )
dt

where,  =

mqm C0 +C
3

maK10

(16)
1
k1


; x1 and x2 are the roots of the

quadratic equation,
C 2 C Kd C0 = 0
where, = C0 mqm Kd and x1 , x2 =

1
2

2 + 4Kd C0

(17)

There are two limiting cases that may be considered here: (1)
intrinsic kinetics control and (2) mass transfer control. In the rst
case, the contribution of mass transfer is assumed to be negligible
(i.e. K ) or
=

1

Eq. (16) is then solved with the new value of  and the solution is
tted to the experimental data to estimate the kinetics parameter
k1 . In the second case, the surface reaction is assumed to have very
fast kinetics (i.e.k1 ) or
=

mqm C0 + C
maK 103

of the two mechanisms. It is dened as the ratio of the mass transfer

contribution (Eq. (19)) to that of intrinsic kinetics (Eq. (18)):

(18)

k1

Fig. 11. Effect of the initial COD concentration on the contribution ratio. Adsorbent
dose = 20 g/L.

(19)

Again, Eq. (16) is solved and the solution is tted to the experimental data to estimate the mass transfer parameter K. In all cases
the model differential equations were solved numerically using
EZ-Solve software. Values for the estimated model parameters for
kinetics control, mass transfer control and dual control are shown
in Table 4; the surface area a (490 m2 /g) was estimated by surface
area analysis (Micromeritics, Model ASAP-2010). A comparison of
the model parameters for single and dual control reveals that there
is no single control and that both mass transfer and intrinsic kinetics
contribute to the adsorption process.
The model predictions for the reduction of COD are compared
with the experimental data in Fig. 10. El-Naas et al. [12] developed
a dimensionless parameter, , to assess the relative contributions

= k1

mqm C0 + Ceq
maK 103


(20)

where, Ceq is the adsorbate concentration when the system reaches

equilibrium, which is equal to the positive root (x1 ) of Eq. (17). The
parameter  was calculated for three initial COD contents (950,
1662 and 3490 mg/L) and found to decrease with increasing the initial concentration C0 as shown in Fig. 11. This suggests that for low
initial concentrations (less than 1300 mg/L), the mass transfer is the
more dominant mechanism, while intrinsic kinetics dominates for
high initial concentrations. For the renery wastewater evaluated
in this study, the COD content is usually higher than 1300 mg/L and
hence surface reaction will be the dominate mechanism.
4. Conclusions
The kinetics and equilibrium of the adsorption of COD were
examined using two types of adsorbents, namely commercial BDH
and locally prepared date-pit (DP) activated carbons. The adsorption effectiveness of DP-AC was found to be comparable to that of
the commercial BDH-AC and the equilibrium data for both were
almost equivalent. For both adsorbents, kinetic data were best tted by the pseudo-second order model, and the equilibrium data
followed the Langmuir isotherm. Modeling the adsorption mechanisms indicated that mass transfer was dominant for low COD
content; whereas for high concentrations the intrinsic reaction
kinetics is the dominant mechanism. Overall, the study revealed
that DP-AC is a promising alternative for the highly expensive activated carbon currently available commercially. In addition, the
utilization of DP-AC can provide an excellent disposal option for
the date palm industry.
Acknowledgements

Fig. 10. Predictions of the dual-resistance model compared with experimental data.
Initial COD concentration, C0 = 1662 mg/L, adsorbent dose = 20 g/L.

The authors would like to acknowledge the nancial support

provided by the Japan Cooperation Center, Petroleum (JCCP) and
the technical support of the Nippon Oil Research Institute Co., Ltd
(NORI). They would also like to thank Abu Dhabi Oil Rening Company (TAKREER) and the Research Affairs at the UAE University for
their support. Special thanks are also due to Sami Abdulla for his
help with the experimental work.

M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750757

References
[1] D.D. Duong, Adsorption Analysis: Equilibria and Kinetics, Imperial College
Press, London, 1998.
[2] S. Babel, T.A. Kurniawan, Low-cost adsorbents for heavy metals uptake from
contaminated water: a review, J. Hazard. Mater. 97 (2003) 219243.
[3] A. Baran, E. Blcak, S.H. Baysal, S. Onal, Comparative studies on the adsorption
of Cr (VI) ions on to various sorbents, Bioresour. Technol. 98 (2007) 661665.
[4] D. Mohan, K. Singh, V. Singh, Wastewater treatment using low cost activated
carbons derived from agricultural by-products: a case study, J. Hazard. Mater.
152 (2008) 10451053.
[5] E. El-Sharkawy, A. Soliman, K. Al-Amer, Comparative study for the removal
of methylene blue via adsorption and photocatalytic degradation, J. Colloid
Interface Sci. 310 (2007) 498508.
[6] J. Hamada, I. Hashim, F. Sharif, Preliminary analysis and potential uses of date
pits in foods, Food Chem. 76 (2002) 135137.
[7] F. Banat, S. Al-Asheh, D. Al-Rousan, A comparative study of copper and zinc ion
adsorption on to activated and non-activated date-pits, Adsorpt. Sci. Technol.
20 (2002) 319335.
[8] F. Banat, S. Al-Asheh, L. Al-Makhadmeh, Kinetics and equilibrium study of cadmium ion sorption onto date pits: an agricultural waste, Adsorpt. Sci. Technol.
21 (2003) 245260.
[9] F. Banat, S. Al-Asheh, L. Makhadmeh, Preparation and examination of activated
carbons from date pits impergnated with potassium hydroxide for the removal
of methylene blue from aqueous solutions, Adsorpt. Sci. Technol. 21 (2003)
597606.
[10] F. Banat, S. Al-Asheh, L. Makhadmeh, Utilization of raw and activated date
pits for the removal of phenol from aqueous solutions, Chem. Eng. Technol.
27 (2004) 8086.
[11] S.A. Al-Muhtaseb, M.H. El-Naas, S. Abdullah, Removal of aluminum from aqueous solutions by adsorption on date-pit and BDH activated carbons, J. Hazard.
Mater. 158 (2008) 300307.
[12] M.H. El-Naas, F. Abu Al-Rub, I. Ashour, M. Al Marzouqi, Effect of competitive
interference on the biosorption of Lead(II) by C. vulgaris, Chem. Eng. Process.
46 (2007) 13911399.
[13] Y.S. Ho, Removal of copper ions from aqueous solution by Tree Fern, Water Res.
37 (2003) 23232330.

[14] E. Sabio, E. Gonzlez, J.F. Gonzlez, C.M. Gonzlez-Garca, A. Ramiro, J. Ganan,

Thermal regeneration of activated carbon saturated with p-nitrophenol, Carbon
42 (2004) 22852293.
[15] G. San Miguel, S.D. Lambert, N.J.D. Graham, The regeneration of eld-spent
granular-activated carbons, Water Res. 35 (2001) 27402748.
[16] F. Salvador, C. Snchez Jimnez, A new method for regenerating activated carbon by thermal desorption with liquid water under subcritical conditions,
Carbon 34 (1996) 511516.
[17] M.K. Purkait, A. Maiti, S. DasGupta, S. De, Removal of congo red using activated
carbon and its regeneration, J. Hazard. Mater. 145 (2007) 287295.
[18] P.M. lvarez, F.J. Beltrn, V. Gmez-Serrano, J. Jaramillo, E.M. Rodrguez, Comparison between thermal and ozone regenerations of spent activated carbon
exhausted with phenol, Water Res. 38 (2004) 21552165.
[19] C.O. Ania, J.A. Menndez, J.B. Parra, J.J. Pis, Microwave-induced regeneration
of activated carbons polluted with phenol. A comparison with conventional
thermal regeneration, Carbon 42 (2004) 13831387.

757

[20] H. Zhang, Regeneration of exhausted activated carbon by electrochemical

method, Chem. Eng. J. 85 (2002) 8185.
[21] C.-H. Weng, M.-C. Hsu, Regeneration of granular activated carbon by an electrochemical process, Sep. Purif. Technol. 64 (2008) 227236.
[22] K. Okawa, K. Suzuki, T. Takeshita, K. Nakano, Regeneration of granular activated
carbon with adsorbed trichloroethylene using wet peroxide oxidation, Water
Res. 41 (2007) 10451051.
[23] . Aktas, F. Cecen, Bioregeneration of activated carbon: A review, Intern. Biod.
Biodegr. 59 (2007) 257272.
[24] J.-L. Lim, M. Okada, Regeneration of granular activated carbon using ultrasound,
Ultra Sonochem. 12 (2005) 277282.
[25] E. Fourest, J.C. Roux, Heavy metal biosorption by fungal mycelial byproducts: mechanisms and inuence of pH, Appl. Microbiol. Biotechnol. 37 (1992)
399403.
[26] A.J. Meikle, G.M. Gadd, R.H. Reed, Manipulation of yeast for transport studies:
critical assessment of cultural and experimental procedure, Enzyme Microb.
Technol. 12 (1990) 865872.
[27] F. Abu Al-Rub, M.H. El-Naas, I. Ashour, M. Al-Marzouqi, Biosorption of copper
on Chlorella vulgaris from single, binary and ternary metal aqueous solutions,
Process Biochem. 41 (2006) 457464.
[28] J.m. Smith, Chemical engineering kinetics, 3rd Edition, McGraw-Hill, New York,
1981, pp. 310-322.
[29] A.K. Parande, A. Sivashanmugam, H. Beulah, N. Palaniswamy, Performance evaluation of low cost adsorbents in reduction of COD in sugar industrial efuent,
J. Hazard. Mater. 168 (2009) 800805.
[30] R. Devi, R.P. Dahiya, COD and BOD removal from domestic wastewater generated in decentralised sectors, Bioresour. Technol. 99 (2008) 344
349.
[31] R. Devi, V. Singh, A. Kumar, COD and BOD reduction from coffee processing wastewater using Avacado peel carbon, Bioresour. Technol. 99 (2008)
18531860.
[32] A. Mittal, V. Gajbe, J. Mittal, Removal and recovery of hazardous triphenylmethane dye, Methyl Violet through adsorption over granulated waste
materials, J. Hazard. Mater. 150 (2008) 364375.
[33] R. Jain, S. Sikarwar, Adsorptive removal of Erythrosine dye onto activated low
cost de-oiled mustard, J. Hazard. Mater. 164 (2009) 627633.
[34] A. Delgado, A.M. Anselmo, J.M. Novais, Heavy metal biosorption by dried
powdered mycelium of Fusarium Flocciferum, Water Environ. Res. 70 (1998)
370375.
[35] Y.S. Ho, J.F. Porter, G. McKay, Equilibrium isotherm studies for the sorption
of divalent metal ions onto peat: copper, nickel and lead single component
systems, Water Air Soil Pollut. 141 (2002) 133.
[36] A. zcan, T. Sibel, A. Tamer, K. Ismail, Determination of the equilibrium, kinetic
and thermodynamic parameters of adsorption of copper(II) ions onto seeds of
Capsicum annuum, J. Hazard. Mater. 124 (2005) 200208.
[37] Q.M. Mao, R. Stockmann, I.G. Prince, M.T.W. Hearn, Modeling of protein adsorption with non-porous and porous particles in a nite bath, J. Chromatogr. 646
(1993) 6780.
[38] M.A. Hashim, K.H. Chu, Modeling of the batch adsorption of copper by the
Miroalga Chlorella vulgaris, in: Proceedings of the Sixth World Congress of
Chemical Engineering, Melbourne, Australia, 2001.