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Journal of Hazardous Materials 173 (2010) 750–757

Contents lists available at ScienceDirect

Journal of Hazardous Materials

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

Reduction of COD in refinery 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 a b s t r a c t

Article history: Experiments were carried out to evaluate the batch adsorption of COD from petroleum refinery wastewa-
Received 6 May 2009 ter on a locally prepared date-pit activated carbon (DP-AC), and its adsorption effectiveness was compared
Received in revised form 31 August 2009 to that of commercially available BDH activated carbon (BDH-AC). Adsorption equilibrium and kinetic
Accepted 1 September 2009
data were determined for both adsorbents and fitted to several adsorption isotherm and kinetics models,
Available online 4 September 2009
respectively. The Langmuir monolayer isotherm fitted well the equilibrium data of COD on both adsor-
bents; whereas, the kinetics data were best fitted by the pseudo-second order model. Modeling of the
Keywords:
controlling mechanisms indicated that both intrinsic kinetics and mass transfer contributed to controlling
COD reduction
Petroleum refinery
the adsorption process. Mass transfer seemed to be the dominant mechanism at low COD content, while
Date-pit intrinsic kinetics dominates at high concentrations. In general, the adsorption effectiveness of locally
Controlling mechanism prepared DP-AC was proven to be comparable to that of BDH-AC. Therefore, DP-AC can be utilized as an
Adsorption effective and less expensive adsorbent for the reduction of COD in refinery wastewater.
© 2009 Elsevier B.V. All rights reserved.

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

Various treatment technologies have been used for the reduc-
tion of COD, which is a major contaminant in petroleum refinery
and industrial wastewater. These techniques include filtration, ion
exchange, coagulation/flocculation, reverse osmosis and electro-
dialysis. 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 [2–4]. The use of acti-
vated 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 capac-
ity, which can be appropriately modified 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 pro-
duction 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 generat-
ing 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).
effectiveness of AC from different raw materials for COD removal,
and reported reduction percentages of up to 74% using AC from
coconut shell fiber 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 consti-
tute approximately 10% of the total weight of dates [5–6], making
them the largest agricultural by-product in palm growing countries,
including the UAE. Therefore, finding ways to use this agricultural
by-product profitably will benefit 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 wastewa-
ter adsorption treatment. DP-AC was prepared by physical [7–8]
and chemical activation [9]. In addition, physical activation of DP
has been carried out in different reactor configurations including
fluidized bed [10]. The adsorption effectiveness of DP-AC of alu-
minum was evaluated and compared to that of commercial BDH-AC
[11]. Generally, the effectiveness of DP-AC was found to be compa-
rable 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 refinery
wastewater. Equilibrium and kinetics studies were carried out to
determine the mechanisms of the adsorption process.

0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2009.09.002
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M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757
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 equi-
librium with that at the surface. This equilibrium is described by
expressing the amount of solute adsorbed per unit mass of adsor-
bent, 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:
qm bCe
qe =
1 + bCe
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 Van’t Hoff’s relationship between the equilibrium
constant and the standard enthalpy change associated with the
process under consideration, which leads to the following relations:
qm = ˛(1 + ε T )
 −H  The Lagergren pseudo-first order model is most commonly used
ads
b = ˇ exp
RT
where Hads is the standard enthalpy change accompanying the
reversible adsorption (kJ mol−1 ), R is the universal gas constant, T
is the absolute temperature and ˛, ˇ and ε are constants. The con-
stants 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
Henry’s law at low concentrations.
The Freundlich isotherm can be written as:
1/b
qe = aCe
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 Langmuir–Freundlich form as follows:
KLF CenLF
qe =
1 + (aLF Ce)nLF
where, KLF , nLF and aLF are constants.
Another isotherm that has seen considerable applications in
adsorption processes is the Dubinin–Radushevich:
   2 
1 where, K2 (g/mg/min) is the pseudo-second order rate constant of
qe = qD exp −BD RT ln 1+
Ce
751
where qD is the D–R 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 infinite distance in the solution
(mol2 /kJ2 ). This means free energy can be estimated from the value
of BD using the following equation:
1
E=  (7)
2BD
The above mentioned isotherms are characterized by parame-
ters that express the surface properties and affinity of the adsorbent
towards different pollutants. Different isotherm models can be
used to fit the equilibrium data. The shapes of various model
isotherms depend on the type of adsorbate/adsorbent and the inter-
molecular interactions between the fluid and the surface [1]. The
model that fits the experimental data most accurately can then be
used to describe the system and predict the adsorption behavior
for practical process design.
(1) 1.2. Adsorption kinetics
The adsorption kinetics can be described by diffusion through
the adsorbent, such as film, pore and surface diffusions, and pore-
surface 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 equi-
librium, several kinetics models such as the pseudo-first order,
Elovich’s, pseudo-second order and intraparticle diffusion models
can be used. Brief descriptions of these models are given in the
following sections.
(2) 1.2.1. Lagergren pseudo-first order model
to describe the adsorption of solute from a liquid solution. The
(3)
linearized form of this model is given by:
kt
ln (qe − q) = ln (qe ) − (8)
2.303
where k is the kinetics constant of pseudo-first order adsorption
(min−1 ), qe and q (mg/g) are the amounts adsorbed at equilibrium
and at time t (min), respectively.
1.2.2. Elovich’s model
In recent years, Elovich’s 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):
1 1
(4) q= ln (ab) + ln (t) (9)
b b
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
(5)
phases [13]. The model is usually represented by its linearized form
as follows:
t 1 1
= + t (10)
q K2 q2t qe
(6)
adsorption.
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752 M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757
Table 1
Surface characteristics of BDH and date-pit (DP) activated carbons.
Characteristics BDH
Particle size (␮m) 850–1700
BET surface area (m2 /g) 1220
BET surface area in the 1173
micropore region (m2 /g)
Total pore volume (cm3 /kg) 534
Total pore volume in the 479
micropore region (cm3 /kg)
1.2.4. Intraparticle diffusion model
The intraparticle diffusion model describes adsorption pro-
cesses, where the rate of adsorption depends on the speed at which
adsorbate diffuses towards adsorbent (i.e., the process is diffusion-
controlled), which is presented by Eq. (11).
√ ods [20,21] wet peroxide oxidization [22] bio-regeneration [23],
q = kd t + 
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
2.1. Preparation of DP-AC
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 flow 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 flow 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.
2.2. COD batch adsorption
Batch adsorption equilibrium experiments were carried out by
contacting a specified amount of adsorbent with 50 ml wastew-
ater 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 BDH-
AC, contacted with refinery wastewater samples obtained from a
local petroleum refinery. Wastewater samples of three different ini-
tial 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 filtered and the final COD was
determined. Adsorption efficiencies 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 final COD
concentrations as follows:
(Ci − Cf )V
DP q= (12)
M
125–212
490
where, q is the uptake (mg adsorbate/g adsorbent), Ci is the initial
423 COD concentration, Cf is the final COD (mg/L), M is the adsorbent
amount (g) and V is the solution volume (l).
229
165
2.3. Regeneration
Regeneration is an important aspect in evaluating the capac-
ity 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 meth-
(11) and ultrasound [24]. Although the results depended on the applica-
tion and the type of wastewater treated, in most cases the activated
carbon was fully regenerated and reused for many cycles. These
studies have confirmed that activated carbon can be easily regener-
ated 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 exam-
ined in a future study that evaluates the continuous adsorption of
COD in a packed bed column.
3. Results and discussion
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 BDH-
AC) was evaluated by varying the dose from 1–80 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 [25–26]. Many of the
adsorption sites, therefore, remain unsaturated due to the limited
Fig. 1. Effect of adsorbent dose on COD uptake at initial COD concentration of
3490 mg/L and 25 ◦ C.
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Table 2
Fitted kinetic parameters for the adsorption of COD onto DP-AC and BDH-AC at 25 ◦ C.

Co (mg/L) Pseudo-first order Elovich’s equation Pseudo-second order

−1 2 2
qe (mg/g) k (min ) R a (mg/g/min) 1/b (mg/g) R K (g/mg.min) qe (mg/g) R2

BDH 3490 31.37 0.0122 0.9497 7.7 × 104 10.53 0.93 0.0016 151.52 1.00
DP 12.38 0.0299 0.8658 7.2 × 1016 3.40 0.87 0.0069 147.06 1.00

BDH 1662 19.33 0.0188 0.7716 8.9 × 104 5.03 0.94 0.0051 74.63 1.00
DP 27.54 0.0258 0.8975 294.4 8.68 0.91 0.0029 73.53 1.00

BDH 950 18.24 0.0295 0.9088 15.3 × 106 5.18 0.87 0.0054 42.74 1.00
DP 7.81 0.0208 0.7426 151.3 2.05 0.91 0.0145 42.55 1.00

availability of the sorbate, which in turn lowers the uptake and the Elovich’s model to describe the adsorption mechanism. The best
adsorption efficiency [27]. The figure also shows that increasing straight lines that pass through the data points were used to deter-
the dose beyond 20 g/L had little effect on the COD reduction and mine the kinetics parameters of both models, which are shown in
hence this value was considered as the optimum dose and used for Table 2. The deviation of the values of R2 from unity is a measure
the rest of the experimental work. of the incompatibility of each respective case.
On the other hand, when t/q was plotted against t, according to
3.2. Adsorption kinetics the linearized pseudo-second order model (Eq. (10)), a clear lin-
ear relationship was observed for all cases, as shown in Fig. 5. The
The COD adsorption rate was determined for the two adsorbents data were fitted perfectly well by straight lines, with R2 values of
by contacting refinery wastewater samples with different initial 1.00. This proves that the adsorption kinetics is more accurately
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 first 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 fitted to the different kinetic models described in Section
1.2, namely: Lagergren’s pseudo-first order (Eq. (8)), Elovich’s (Eq.
(9)), pseudo-second order (Eq. (10)) and intraparticle diffusion (Eq.
(11)). Figs. 3–6 present the applicability of the four models at dif-
ferent initial COD, respectively.
Fig. 3 shows the relationship between ln(qe − q) and t, according
to the linearized Lagergren’s pseudo-first order equation (Eq. (8)).
It is observed that the results deviate significantly from a straight
line, which indicates that the pore diffusion is not the sole rate con-
trolling step, as the Lagergren’s pseudo-first 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) accord-
ing to the linearized Elovich’s equation (Eq. (9)), shown in Fig. 4
for both adsorbents, which also proves the incompatibility of the
Fig. 3. ln (qe − q) vs. t according to pseudo-first order model. (䊉) 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 ini-
tial COD contents. (䊉) C0 = 3490 mg/L, () C0 = 1662 mg/L, () C0 = 950 mg/L, (black) Fig. 4. q vs. ln(t) according to Elovich’s model. (䊉) C0 = 3490 mg/L, ()
BDH-AC and (white) DP-AC. C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.
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754 M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757
Fig. 5. t/q vs. t according to the pseudo-second order model. (䊉) 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 confirm this conclusion, q was plotted against t,
which would, according to Eq. (11), give a straight line if intra-
particle 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 resis-
tance; 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 fitted to the Langmuir, Freundlich, Sips
and Dubinin–Radushevich isotherm models using Sigma Plot non-
linear regression, which uses the Marquardt–Levenberg algorithm
to find the parameters that give the best fit 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. (䊉) C0 = 3490 mg/L,
() C0 = 1662 mg/L, () C0 = 950 mg/L, (black) BDH-AC and (white) DP-AC.
Fig. 7. Langmuir fitting for the equilibrium isotherm data of the COD adsorption on
DP-AC at different temperatures.
the experimental data were best fit 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 temper-
ature 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 tempera-
ture, 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 ˛, ˇ and ε found
in Eqs. (2) and (3) were determined by fitting 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 confirms the
Fig. 8. Langmuir fitting for the equilibrium isotherm data of the COD adsorption on
BDH-AC at different temperatures.
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M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757 755

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

Isotherm Parameter 25 ◦ C 40 ◦ C 60 ◦ C

BDH DP BDH DP BDH DP

Langmuir b (L/mg) 1.62 × 10−3 2.07 × 10−3 1.89 × 10−3 2.4 × 10−3 2.05 × 10−3 2.85 × 10−3
qm (mg/g) 252.81 191.58 293.65 217.82 331.19 241.45
R2 0.99 1.00 0.93 0.99 0.99 0.99

Freundlich aF 1.518 2.651 1.304 1.79 0.989 1.59

bF 0.716 0.6022 0.763 0.665 1.006 0.699
R2 0.98 0.99 0.92 0.97 1.00 0.98

Sips (L–F) nLF 1.489 0.902 2.605 1.228 1.312 1.187

aLF 0.005 0.002 0.009 0.0036 0.0041 0.0035
KLF 0.0623 0.833 5.8 × 10−4 0.169 0.147 0.226
R2 0.93 0.94 0.93 0.93 0.93 0.96

D–R qD (mg/g) 128.49 105.3 131.01 102.8 124.66 113.94

BD 0.0021 1.706 × 10−3 0.0011 1.605 × 10−3 0.001 1.1 × 10−3
E (J/mol) 15.43 17.12 21.32 17.65 22.36 21.32
R2 0.76 0.81 0.76 0.85 0.76 0.83

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 affinity than BDH-AC which is reflected in the higher
improvement of the uptake capacity. The values for Hads are con-
sistent 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 evalu-
ated at 25 ◦ C for an initial concentration of 3490 mg/L and different
initial pH values in the range of 2–10. The typical pH of the refinery
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 significant effect on the adsorption process.
Similar results for the optimum range of pH were reported for the
adsorption of COD [29], COD and BOD [30–31] and dyes [32–33].
3.5. Modeling and adsorption mechanisms
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 cer-
tain limit [34]. The ion exchange mechanisms can be significant
if the bonding energy is in the range of 8-16 kJ/mol [35–36]. 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 essen-
tial 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 impor-
tance 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 trans-
port of the adsorbate from the bulk solution to the surface of the
adsorbent can be described by film resistance mechanism:
dp
= aK × 10−3 (C − Ci ) (13)
dt

where q and C are the adsorbate concentrations in the adsorbent

Adsorption of contaminants on any solid surface can take place
(mg/g) and in the solution (mg/L), respectively; a is the surface area
through physical adsorption, chemical adsorption or ion exchange.
of the adsorbent per unit mass (cm2 /g); K is the liquid film mass
It is rather difficult to predict the exact mechanism, since it depends
transfer coefficient (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:

C0 − C
q= (14)
m

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] (15)
dt

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

Fig. 9. Equilibrium isotherm data for the adsorption of COD at different pH values.
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
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756 M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757

Table 4
Model parameters for single and dual control mechanisms.

Mechanism k1 (L/mg/min) K (cm/min)

Intrinsic kinetics 0.00002 –

Mass transfer – 6.3 × 10−8
Combined 0.000049 1.2 × 10−7

[34]:
dC
− = (C − x1 )(C − x2 ) (16)
dt
 
mqm −C0 +C 1
where,  = −3 + k1
; x1 and x2 are the roots of the
maK×10
quadratic equation,

C 2 − ˛C − Kd C0 = 0
 
1
where, ˛ = C0 − mqm − Kd and x1 , x2 = 2
˛±
There are two limiting cases that may be considered here: (1)
intrinsic kinetics control and (2) mass transfer control. In the first
case, the contribution of mass transfer is assumed to be negligible
(i.e. K → ∞) or
1
=
k1
Eq. (16) is then solved with the new value of  and the solution is
fitted 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 × 10−3
Again, Eq. (16) is solved and the solution is fitted to the experi-
mental 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
(17)

˛2 + 4Kd C0
Fig. 11. Effect of the initial COD concentration on the contribution ratio. Adsorbent
dose = 20 g/L.
of the two mechanisms. It is defined as the ratio of the mass transfer
contribution (Eq. (19)) to that of intrinsic kinetics (Eq. (18)):
(18)  
mqm − C0 + Ceq
= k1 (20)
maK × 10−3
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 ini-
(19)
tial 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 refinery 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 adsorp-
tion 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 fit-
ted by the pseudo-second order model, and the equilibrium data
followed the Langmuir isotherm. Modeling the adsorption mech-
anisms 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 acti-
vated carbon currently available commercially. In addition, the
utilization of DP-AC can provide an excellent disposal option for
the date palm industry.

Acknowledgements

The authors would like to acknowledge the financial support

Fig. 10. Predictions of the dual-resistance model compared with experimental data.
Initial COD concentration, C0 = 1662 mg/L, adsorbent dose = 20 g/L.
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 Refining Com-
pany (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.
 Author's personal copy
M.H. El-Naas et al. / Journal of Hazardous Materials 173 (2010) 750–757
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