Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749

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Journal of the Taiwan Institute of Chemical Engineers

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Adsorptive removal of copper(II) from aqueous solutions on activated carbon

prepared from Tunisian date stones: Equilibrium, kinetics and thermodynamics
F. Bouhamed 1, Z. Elouear *, J. Bouzid 2
Laboratoire Eau Energie et Environnement, Ecole Nationale d’Ingénieurs de Sfax, B.P.W 3038 Sfax, Tunisia

A R T I C L E I N F O A B S T R A C T

Article history: In this study, activated carbon produced from Tunisian date stones, a low-cost agricultural by-product,
Received 2 November 2011 by chemical activation using H3PO4 as an activator was used as adsorbent for the removal of copper(II)
Received in revised form 17 February 2012 ions from aqueous solutions. To optimize the preparation method, the effect of the main process
Accepted 23 February 2012
parameters (such as acid concentration, impregnation ratio, and temperature of pyrolysis step) on the
Available online 29 March 2012
performances of the obtained activated carbons was studied. The optimal activated carbon was fully
characterized considering its adsorption properties as well as its chemical structure and morphology.
Keywords:
Optimum adsorption conditions were determined as a function of pH, initial copper concentration,
Activated carbon
Date stones
contact time and temperature of solution for copper(II) removal. The results showed that the adsorption
Adsorption of copper(II) onto activated carbon produced by the optimum conditions was maximal at about pH 5.0.
Copper The rates of adsorption were found to conform to the pseudo-second-order kinetic model. The
Isotherm application of the intra-particle diffusion model revealed that the adsorption mechanism of copper(II) is
rather a complex process and the intra-particle diffusion is involved in the overall rate of the adsorption
process but it is not the only rate-controlling step. The isotherm equilibrium data were well fitted by the
Langmuir and Dubinin–Radushkevich isotherm models with a monolayer maximum adsorption capacity
of 31.25 mg/g. According to the experimental results, the adsorbent derived from this material is
expected to be an economical product for metal ion remediation from water and wastewater.
ß 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction membrane technologies, they may be ineffective or cost-expen-

sive, especially when the metal ion concentrations in solution are
The presence of metal ions in municipal or industrial in the range of 1–100 mg/L [4,5]. Recently, adsorption technology
wastewater and their potential impact have been a subject of has become one of the alternative treatments in either laboratory
scientific environmental research for a long time because of their or industrial scale [6,7]. There are many adsorbents in use.
extreme toxicity even at low concentrations, and their tendency to Activated carbons are known as very effective adsorbents due to
accumulate in the food chain [1]. Copper pollution arises from their highly developed porosity, large surface area, variable
copper mining and smelting, brass manufacture, electroplating characteristics of surface chemistry, and high degree of surface
industries and excessive use of Cu-based agri-chemicals [2]. reactivity [8]. However, due to their high production costs, these
Ingestion of high quantities of copper may cause gastrointestinal materials tend to be more expensive than other adsorbents. This
bleeding, hypotension, convulsions, and significant DNA damage has led a growing research interest in the production of activated
[3]. carbons from renewable and cheaper precursors. The choice of
Therefore, it is urgent to remove those toxic heavy metals from precursor largely depends on its availability, cost, and purity, but
wastewater. Although heavy metal removal from aqueous solu- the manufacturing process and intended applications of the
tions can be achieved by conventional methods, including product are also important considerations [9].
chemical precipitation, oxidation/reduction, electrochemical Several suitable agricultural by-products (lignocellulosics)
treatment, evaporative recovery, filtration, ion exchange and including fruit stones [10], olive waste cake [11,12], pine bark
[13], rice husks [14], pistachio-nut shells [15] and wheat bran [16]
have been investigated in the last years as activated carbon
precursors and are still receiving renewed attention.
* Corresponding author. Tel.: +216 23 543 734; fax: +216 74 665 190. Tunisia produces about 90,000 tons of dates annually, which
E-mail addresses: [email protected] (F. Bouhamed),
can yield a minimum of 9000 metric tons of date stones [17]. A
[email protected] (Z. Elouear), [email protected] (J. Bouzid).
1
Tel. + 216 23 160 511. reasonable fraction of this quantity can be reclaimed easily from
2
Tel. + 216 20 413 488. dates processing plants and can be used as a raw material for

1876-1070/$ – see front matter ß 2012 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jtice.2012.02.011
742 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749

production of activated carbon. The use of this material as Test Method, ASTM Designation D4607-86 by titration with
precursor for the preparation of activated carbon produces not sodium thiosulphate [25]. The concentration of iodine solution
only a useful adsorbent for the purification of contaminated was thus calculated from total volume of sodium thiosulphate
environments, but also contributes to minimizing the undesirable used and volume dilution factor.
solid wastes. In case of methylene blue number, it is also one of the most
Previous studies [18–24] on the production of activated carbon widely recognized probe molecules for assessing the removal
from date stones were concentrated mostly on the development of capacity of the specific carbon for moderate-size pollutant
the high quality activated carbon. They did not consider the molecules (1.5 nm) [26]. Methylene blue adsorption tests were
detailed studies of the adsorption process parameters, the kinetics conducted by mixing 0.3 g of the prepared activated carbons with
or the thermodynamics of heavy metals adsorption. 100 ml of 1000 mg/L methylene blue solution [15]. After agitation
Therefore, the purpose of this work was to evaluate the during 24 h, the suspension was filtered and the MB residual
adsorption potential of date stones-based activated carbon for concentration was measured at 660 nm, using an UV/vis spectro-
copper ions as a model for metallic species. photometer (OPTIMA, SP-3000 plus). A previously established
The adsorbent used in this work was prepared in the laboratory linear Beer–Lambert relationship was used for the concentration
scale, from date stones, via chemical activation using phosphoric determination.
acid as a dehydrating agent. Optimization of some process
parameters and characterization of the optimal activated carbon 2.2.2. Characterization of the activated carbon prepared under
were first investigated. Thereafter, the adsorption of the copper optimal conditions
ions was undertaken. The adsorption isotherms, kinetic and The physico-chemical characteristics of activated carbon
thermodynamic aspects of the retention process were explored. produced by the optimum conditions in this experiment were
determined. Nitrogen adsorption–desorption isotherms at
2. Materials and methods 196 8C were measure with an automatic adsorption instrument
(ASAP 2010, Micromeritics). The specific surface area was
2.1. Preparation of activated carbons determined by the BET isotherm equation, and the total pore
volume (Vtot) was calculated by the adsorption data at P/P0 = 0.995.
The palm dates were initially scraped with a knife to remove all Prior to the measurements, the samples were out gassed at 300 8C
fibers present at surface. The collected date stones were washed under nitrogen for at least 3 h.
and dried in an air oven at 70 8C for 48 h and then crushed and The point of zero charge (pHZPC) of the adsorbent was
sieved to the desired particle size (<1.5 mm). The resultant sieve determined by the method described by Bouzid et al. [27].
cut was used for the production of activated carbons via chemical Bulk density was determined as follows: activated carbon
activation. For this purpose, phosphoric acid (analytical grade) was sample was placed in a graduated cylinder, tapped several times
retained as a dehydrating agent. Each preparation test was until constant volume and then weighted. The bulk density was
conducted as follows: 40 g of the crushed (Ø < 1.5 mm) and dried calculated as the ratio of the weight sample to its volume and
precursor was mixed with H3PO4 solutions having different expressed in g/cm3 [28]. Crystalline phases eventually present in
concentrations (25–85% H3PO4 in weight). The impregnation ratio, the adsorbent material were analyzed by powder X-ray diffraction
defined as: weight of impregnant (H3PO4)/weight of precursor (XRD analyzer Philips X Pert).
(date stones), was 1, 1.25, 1.5, 1.75 and 2. The impregnation was Microstructure of the raw material and the activated carbon
carried out in a stirred pyrex reactor equipped with a reflux prepared in the optimal conditions were examined using a
condenser. Stirring was used to ensure the access of the acid to the scanning electron microscopy (SEM, Philips XL30).
interior of the date stones cake particles.
The temperature and the duration of the reaction were 104 8C 2.3. Batch mode adsorption studies
and 2 h, respectively. Agitation and heating were ensured by a
heating magnetic stirrer with connected temperature regulator All chemicals used in this work, were of analytical reagent grade
probe made of Teflon. The pyrolysis of the impregnated material and were used without further purification. Solutions were
was conducted in a cylindrical stainless steel reactor, inserted into prepared by dissolving the corresponding reagents in bidistilled
a tubular regulated furnace under continuous nitrogen flow (0.5 L/ water.
min). Pyrolysis temperature ranged from 350 to 650 8C, while The activated carbon, prepared under the optimal conditions,
pyrolysis time was maintained at 2 h. After cooling down to room was retained for all the following adsorption experiments.
temperature, under the same flow of nitrogen, the obtained In order to determine the sorption capacity of activated carbon
activated carbon was repeatedly washed with hot distilled water for Cu(II), as well as the influence of the contact time, pH, and
until neutral pH. The sample was then dried at 105 8C overnight, temperature on Cu(II), sorption experiments were performed by
ground (until a granulometry ranging between 100 and 160 mm) batch equilibration technique. Solutions were prepared from
and finally kept in hermetic bottle for subsequent uses. CuSO45H2O salt and distilled water.
After adsorption process the adsorbent separated from the
2.2. Characterization samples by filtering and the filtrate was analyzed for copper(II)
using a flame atomic absorption spectrophotometer (HITACHI Z-
2.2.1. Characterization of the prepared adsorbents 6100). Analytical errors were estimated to be of the order of 3%. All
Some parameters which had effect on the activated carbon the experiments were duplicated to assure the veracity of the
namely acid concentration, impregnation ratio, temperature of experimental results.
pyrolysis step was studied to determine the optimum conditions for
producing the prepared activated carbons. In this work, efficiency 2.3.1. Effect of equilibration time
and quality of the activated carbon were preliminarily characterized Sorption experiments for the kinetics study were conducted as
by measuring both iodine and methylene blue number. follows: 0.5 g of activated carbon was suspended in 200 mL
The iodine number can be used for estimation of the relative solution containing 100 mg/L of Cu(II) ions. The suspensions were
surface area and measurement of porosity, the pores size less than stirred for different time intervals, filtrated, and analyzed to
1.0 nm in diameter. It was obtained on the basis of the Standard determine the Cu(II) ions concentration.
 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749 743

According to literature, several models can be used to express solutions was adjusted from 2 to 7 by adding NaOH or HNO3
the kinetics of the sorption processes, e.g. pseudo-first order, solutions. The suspensions were stirred for 2 h. Measurements
pseudo-second order and intraparticle diffusion models [29]. of the initial pH of the various metal tested solutions are carried
A pseudo-first-order reaction model was applied to our out using a pH meter of laboratory models pH 540 GLP equipped
experimental data in order to determine the sorption rate constant, with an electrode of glass combined SENTIX41. A preliminary
at room temperature. The linear form of pseudo-first-order rate calibration is systematically carried out using suitable buffer
expression is [30,31] solutions.

dqt
¼ K 1 ðqe  qt Þ (1) 2.3.3. Effect of initial Cu2+ concentration
dt Activated carbon was equilibrated with Cu(II) solutions of
where qe and qt refer to the amount of Cu2+ (mg/g) adsorbed at different initial concentrations 10–100 mg/L for 2 h at three
equilibrium and at any time, t (min), respectively, and K1 is the different temperatures, i.e. 10, 20 and 40 8C. After filtration, the
equilibrium rate constant of pseudo-first-order sorption (1/min). final concentrations of copper in the solutions were measured.
Integration of Eq. (1) for the boundary conditions t = 0 to t and The Langmuir, Freundlich and Dubinin–Radushkevich (D–R)
qt = 0 to qt, gives adsorption isotherms, often used to describe the sorption of solutes
from a liquid phase, were applied to our experimental results. Linear
K1
logðqe  qt Þ ¼ log qe  t (2) form of the Langmuir equation can be expressed as follows [34]:
2:303
Ce 1 Ce
Kinetic data were further treated with the pseudo-second-order ¼ þ (7)
qe q0 b q0
kinetic model [29]. The differential equation is the following:
where Ce is the equilibrium concentration (mg/L), qe is the amount
dqt
¼ K 2 ðqe  qt Þ (3) of copper sorbed at equilibrium, b is the sorption constant (L/mg)
dt
(at a given temperature) related to energy of sorption, q0 is the
where K2 is the equilibrium rate constant of pseudo-second-order maximum sorption capacity (mg/g).
adsorption (g/mg min). Integrating Eq. (3) for the boundary Weber and Chakravorti [35] expressed the essential character-
condition t = 0 to t and qt = 0 to qt, gives: istics and the feasibility of the Langmuir isotherm in terms of a
dimensionless constant separation factor or equilibrium parame-
t 1 1
¼ þ t (4) ter RL, which is defined as,
qt K 2 q2e qe
1
The following expression denotes the initial sorption rate h RL ¼ (8)
1 þ bC 0
(mg/g min):
The value of RL indicates the shape of the isotherm to be either
h ¼ K 2 qe2 (5) unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL < 1) or
irreversible (RL = 0).
In addition, the intraparticle diffusion model [32] was consid-
The Freundlich isotherm is an empirical model that is based on
ered in order to determine the participation of this process in the
adsorption on heterogeneous surface and active sites with
sorption of copper(II) by activated carbon. In this model, the rate of
different energy. The linearized Freundlich isotherm equation is
intra-particle diffusion is a function of t0.5 and can be defined by
represented by the following equation [36]:
Eq. (6) as follows:
1
qt ¼ K d t 0:5 þ C (6) ln qe ¼ ln K f þ ln C e (9)
n
where qt is the amount of sorbate on the surface of the sorbent at where Kf and n are Freundlich constants, indicating the adsorption
time t (mg/g), Kd is the intraparticle rate constant (mg/g min0.5), t is capacity and the adsorption intensity, respectively. Kf and n are,
the time (min) and C is the intercept. respectively, determined from the intercept and slope of plotting
According to this model, the plot of uptake (qt), versus the ln qe versus ln Ce.
square root of time (t0.5) should be linear with a slope Kd and The D–R equation, based on the heterogeneous surface of the
intercept C if intraparticle diffusion is involved in the overall adsorbate, has the form [37]:
adsorption mechanism. Further, if this line passes through the ln C ads ¼ ln q0  be2 (10)
origin then the intraparticle diffusion is the rate controlling step of
the process. If the plots do not pass through the origin, this is where Cads (mol/g) is the amount of the metal ions adsorbed per
indicative of some degree of boundary layer control and this unit weight of the adsorbent, q0 (mol/g) is the maximum sorption
further shows that the intraparticle diffusion is not the only rate- capacity, b (mol2/J2) is the activity coefficient related to the mean
limiting step, but also other kinetic models may control the rate of sorption energy, and e is the polanyi potential. e can be calculated
adsorption, all of which may be operating simultaneously. In most in the following way:
cases these plots give general features of three stages; initial  
1
curved portion, followed by an intermediate linear portion and a e ¼ RT ln 1 þ (11)
Ce
plateau. The initial portion due to external mass transfer, the
intermediate linear part is due to intra-particle diffusion and the where R (8.314 J/mol K) is the gas constant and T (K) is the
plateau to the equilibrium stage where intraparticle diffusion temperature. The saturation limit q0 may represent the total
starts to slow down due to extremely low solute concentrations in specific micropore volume of the sorbent. The slope of the plot of
the solution [33]. ln Cads versus e2 gives b and the intercept yields the sorption
capacity, q0. The mean sorption energy E (kJ/mol) can also be
2.3.2. Effect of pH calculated using the following relationship:
Sorption experiments for the influence of pH were conducted as
follows: 0.5 g of activated carbon were suspended in 200 ml 1
E ¼ pffiffiffiffiffiffiffi (12)
solution containing 100 mg/L of copper ions. The pH of the various 2b
744 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749

2.3.4. Estimation of thermodynamic parameters 600

Thermodynamic parameters such as free energy change (DG8),

Iodine number(mg/g)
enthalpy change (DH8), and entropy change (DS8) for the sorption 500
of copper(II) on activated carbon was determined using the
following equations [38,39]: 400

DG ¼ RT ln b (13) 300

D G ¼ D H   T D S  (14) 200

where DG8 is the change in free energy (kJ/mol), DH8 the change in 100
enthalpy (kJ/mol), DS8 the change in entropy (J/mol K), T the
absolute temperature K, R the gas constant (8.314  103), and b is 0
the equilibrium constant of sorption. From Eqs. (13) and (14), it can 0 20 40 60 80 100
be rewritten as: [H3PO4] concentration (Wt%)
DS DH Fig. 2. Effect of H3PO4 concentration on the iodine number (impregnation ratio:
ln b ¼  (15)
R RT 1.75; pyrolysis temperature: 450 8C; pyrolysis duration: 2 h).

The enthalpy and entropy changes can be respectively

determined from the slope and intercept of the plot ln b against the iodine number occurring in the acid concentration range 60–
1/T. 85% H3PO4 and the handling difficulties of the most concentrated
commercial phosphoric acid (85% H3PO4 in weight) owing
3. Results and discussion especially to its high viscosity, a concentration of 60% H3PO4
seems to be the most suitable for the development of the best
3.1. Preparation of activated carbons: effect of processing parameters iodine number and, consequently, to the best development of
microporous structure.
In this work, the efficiency and the quality of the produced Contrary to iodine number, methylene blue is one of the most
activated carbon from date stones were characterized by measur- widely recognized probe molecules for assessing the removal
ing the iodine and the methylene blue numbers. These character- capacity of the specific carbon for moderate-size pollutant
istics were plotted and analyzed for the variables of activation molecules via its macroporosity (1.5 nm) [26]. The effect of
temperature, impregnation ratio and acid concentration of the date temperature on methylene blue number is shown in Fig. 3. It was
stones to find the optimum conditions at which the iodine number noticed that, as the pyrolysis temperature increases from 350 to
and the methylene blue of the activated carbon is obtained. 450 8C the quantity of methylene blue adsorbed begins to increase.
Figs. 1–3 illustrate the effect of the impregnation ratio, acid Beyond 450 8C a decrease on this quantity was noticed. Thus,
concentration and temperature on the iodine and the methylene keeping the pyrolysis temperature at around 450 8C leads to a
blue numbers of the prepared activated carbon. better development of the sorbent porosity. Note that this result is
Fig. 1 shows the effect of changing the impregnation ratio on the in agreement with those reported in several papers dealing with
iodine number. The highest iodine number was obtained at an activation of other agricultural materials (woods, coconut shell,
impregnation ratio of 1.75. At a value more or less than 1.75, the grain sorghum) with H3PO4 [26,40–42].
iodine number decreased. Therefore, 1.75 is the suitable impreg- The above results show that the most efficient activated carbon
nation ratio value leading to the best iodine number and, is that obtained under the following optimal conditions: an acid
consequently, to the best development of microporous structure. concentration equal to 60% in weight, an impregnation ratio of 1.75
The effect of acid concentration on the iodine number is shown and a pyrolysis temperature of 450 8C. It is to note that results
in Fig. 2. As it can be seen from this figure, the iodine number obtained when studying the effect of each parameter (acid
increases rapidly with an increase of acid concentration from 25% concentration, impregnation ratio and pyrolysis temperature) on
to 60% H3PO4 while it increases slightly with acid concentration the whole considered properties, namely iodine and methylene
higher than 60% H3PO4. Taking into account this slight increase of blue numbers and specific area (results not shown), lead to the
same optimal conditions.

300
Methylene blue(mg/g)

250
200
150
100
50
0
200 300 400 500 600 700
Temperature (°C)

Fig. 1. Effect of impregnation ratio on the iodine number (H3PO4 concentration: Fig. 3. Effect of temperature on methylene blue number (H3PO4 concentration: 60%;
60%; pyrolysis temperature: 450 8C; pyrolysis duration: 2 h). impregnation ratio: 1.75; pyrolysis duration: 2 h).
 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749 745

Fig. 6, panels a and b, shows SEM micrographs of the raw date

stones residue and the resulting activated carbon prepared under
the optimal conditions. For the date stones residue, the surface was
quite smooth with very little pores as shown in Fig. 6(a). After
activation process, the sorbent surface demonstrated a well
developed and uniform surface, forming an orderly porous
structure and a predominately microporous character which is
responsible of the high developed surface area of this material
(Fig. 6(b)).

3.3. Metal ion adsorption study

3.3.1. Adsorption kinetics

The effect of equilibration time on the sorption of copper(II) by
activated carbon was investigated for time periods from 15 min up
to 8 h. From Fig. 7, it is concluded that rate of metal ion adsorption
increases sharply at short contact time and slowed gradually as
Fig. 4. Nitrogen adsorption–desorption isotherms of the optimal activated carbon. equilibrium was approached. The necessary time to reach the
equilibrium is about 2 h. This behavior may be due to the,
availability of initial large number of vacant surface active sites for
Table 1 adsorption and sorption rate is very fast thus rapidly increases the
Characteristics of the activated carbon prepared under optimal condition.
amount of adsorbate accumulated on the carbon surface mainly
Parameter Value within the first 2 h of adsorption. Afterward the filling of vacant
Specific surface area (m2/g) 826 sites becomes difficult due to repulsive forces between copper ion
Total pore volume (cm3/g) 0.46 adsorbed on solid surface and copper ion from solution. In order to
pHzpc 3.34 investigate the mechanism of copper(II) adsorption on activated
Iodine number (mg/g) 472 carbon prepared under optimal conditions pseudo-first order,
Methylene blue number (mg/g) 259
pseudo second order and intraparticle diffusion model were used.
Bulk density (g/cm3) 0.56
All kinetic data for the adsorption of copper(II) ions onto activated
carbon, calculated from the related plots, are summarized in Table
2.
3.2. Characteristics of the activated carbon prepared under the The validity of the exploited models is verified by the
optimal conditions correlation coefficient, R2. Comparison of the R2 values for different
models suggests that the pseudo-second-order kinetic model fits
Nitrogen adsorption is a standard procedure for determination best since its highest value (R2 = 0.997). Pseudo-second-order
of porosity of carbonaceous adsorbents. From nitrogen adsorption kinetic model implies that the predominant process here is
isotherm analysis (Fig. 4), it was inferred that the isotherm of the chemisorption, which involves a sharing of electrons between the
activated carbon prepared under the optimal conditions is adsorbate and the surface of the adsorbent [45,46]. The intra-
Langmuirian in shape being typical type I in the BDDT classification particle diffusion model was tested to identify the diffusion
[43]. This type of isotherm is usually exhibited by microporous mechanism. Plot of the quantity of copper(II) adsorbed against
solids. Meanwhile, the desorption branch presents a hysteresis square root of time is given in Fig. 8. It is shown in Fig. 8 that the
loop at high relative pressures, characteristic of mesoporosity [44]. plots were not linear over the whole time range and the graphs of
The results of the physical properties of the adsorbent are shown in this figure reflect a dual nature, with initial linear portion followed
Table 1. by plateau. This implies that the external surface adsorption (stage
The XRD pattern of the sorbent shown in Fig. 5 exhibit broad 1) is relatively very fast and the stage of intra-particle diffusion
peaks and absence of a sharp peak that revealed predominantly (stage 2) is rapidly attained and continued to 120 min. Finally,
amorphous structure. equilibrium adsorption (stage 3) starts after 120 min. The cations
are slowly transported via intra-particle diffusion into the particles
and are finally retained in the pores. The linear portion of the curve
does not pass the origin and the latter stage of copper(II)
adsorption does not follow Webber–Morris equation. It may be
concluded that the adsorption mechanism is rather a complex
process and the intra-particle diffusion was not the only rate-
controlling step. The Values of intercept (Table 2) gave an idea
about the thickness of boundary layer, i.e. the larger the intercept
the greater will be the boundary layer effect [47].The results
obtained agreed with those found by Nadeem et al. [48] for the
adsorption of lead onto chemically modified activated carbon.

3.3.2. Effect of pH
The pH of the aqueous solution has been identified as the most
important variable governing metal adsorption onto adsorbents.
This is partly due to the fact that hydrogen ions themselves are a
strongly competing adsorbate and because the solution pH
influences the ionization of surface functional groups. In order
Fig. 5. The X-ray diffraction pattern of the optimal activated carbon. to establish the effect of pH on the adsorption of copper(II), the
746 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749

Fig. 6. SEM micrographs of (a) the raw date stones residue and (b) the optimal activated carbon.

batch equilibrium studies at different pH values were carried out in moreover, the less functional groups, i.e. R–O are ionized
the range of 2–7 (Fig. 9). We note that as the pH of the solution (deprotonated) in this region, and it is difficult that they form
increased from 2.0 to 7.0, the adsorption capacity of copper(II) Cu complexes. Noted here Cu2+ and Cu(OH)+ are the dominant
increased up to pH 5.0 and then decreased at pH > 5.0. species involved in the adsorption below pH 5.0, thus other species
The amount adsorbed increased as pH increased from 2.0 to 5.0 Cu(OH)2 and Cu(OH)3 were not accounted in the formation of
may be due to the presence of negative charge on the surface of the surface complexes [51].
adsorbent that may be responsible for metal binding. However, as
the pH is lowered, the hydrogen ions compete with the metal ions 3.3.3. Adsorption isotherms
for the sorption sites in the sorbent; the overall surface charge on Graphic presentations of the adsorption isotherms of copper(II)
the adsorbent becomes positive and hinds the binding of positively onto activated carbon prepared under the optimal conditions along
charged metal ions [49]. At pH higher than 5.0, the precipitation of with its validation with the Langmuir and Freundlich isotherms at
insoluble metal hydroxides takes place restricting the true 20 8C are illustrated in Fig. 10. The values of isotherm constants are
adsorption studies [50]. So, an optimized pH of 5.0 is taken for given in Table 3. Comparison of the R2 values shows that the
all the adsorption experiments. The effect of pH may be explained Langmuir isotherm fitted quite well with the experimental data
in relation to the interaction of Cu(II), Cu(OH)+ and Cu(OH)2 with with a high correlation coefficient (R2 = 0.995). The Langmuir
surface functional groups present in activated carbon as follows: model is basically developed to describe the sorption processes
where no interaction between sorbate species occur on sites
ROH2 þ $ ROH þ Hþ (16) having the same sorption energies independent of surface
coverage [52]. Maximum monolayer adsorption capacity q0 of
ROH $ RO þ Hþ (17) copper(II) onto activated carbon was 31.25 mg/g. RL value was
calculated as 0.08, which is greater than zero and less than unity,
RO þ Cu2þ $ ROCuþ (18) showing favorable adsorption of copper(II) onto activated carbon
obtained from date stones residue by chemical activation with
RO þ CuðOHÞþ $ ROCuðOHÞ (19) H3PO4 under optimal conditions.
The Dubinin–Radushkevich (D–R) isotherm fitted quite well
where R represents the surface sites of activated carbon; R–OH2+,
with the experimental data with a high correlation coefficient
R–OH, R–O represent protonated, neutral, and ionized surface
(R2 = 0.999). From the intercept of the plots, the q0 value was found
hydroxyl functional groups; R–OCu+ and R–OCu(OH) are formation
to be 14.9 mg/g. The mean adsorption energy was calculated and
of the bonding complexes. It can be seen that at low pH values, H+
the result indicated that the adsorption of copper(II) onto activated
competes with the Cu ions for the active surface sites and,
carbon may be carried out via chemically.
14
Table 2
12 Kinetic model parameters for the adsorption of copper(II) onto optimal activated
carbon.
10
qt(mg/g)

Kinetic model Parameter Value

8
Pseudo-first order K1 (1/min) 0.029
6
R2 0.959
4 Pseudo-second order K2 (gm/g min) 0.011
R2 0.997
2 h (mg/g min) 2.221
Intraparticle The first phase Kd1 (mg/g min0.5) 0.977
0
diffusion model R21 0.957
0 100 200 300 400 500 C1 1.407
The second phase Kd2 (mg/g min0.5) 0.029
Time (min)
R22 0.954
C2 11.405
Fig. 7. Kinetic study for copper(II) adsorption on optimal activated carbon.
 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749 747

14 Table 3
Equilibrium model parameters for adsorption of copper(II) onto optimal activated
12 carbon.

Isotherms Parameter Value

10
qt(mg/g)

Langmuir q0 (mg/g) 31.25

8 b (L/mg) 0.11
RL 0.08
6 R2 0.99
Freundlich Kf 0.37
4 n 1.16
R2 0.94
2 Dubinin–Radushkevich q0 (mg/g) 14.9
b (mol2/J2) 8.71  109
0 E (kJ/mol) 7.75
R2 0.99
0 5 10 15 20 25
1/2 1/2
t (min )
Table 4
Fig. 8. Plots of copper(II) adsorption against square root of contact time. Results for adsorption of copper(II) by activated carbons obtained from various
plants, agricultural and wood based materials.

14 Activated carbon source pH Adsorbant References

capacity (mg/g)
12
Date stones 6 31.25 This work
10 Apricot stone 6.5 22.85 [53]
Soybean hulls 5 39.37 [54]
qe(mg/g)

8 Olive waste cakes – 12 [11]

Kraft lignin – 136 [55]
6 Rice husk 6 29 [56]
Ceiba pentandra hulls 6 20.78 [57]
4 Phoenix dactylifera stone carbon 6 37.3 [58]
Palm shell carbon 5 22 [59]
2
Coconut coir activated carbon 84.74 [60]
0 Palm oil empty fruit bunch – 0.84 [61]
Grapeseed carbon 5 48.78 [62]
0 2 4 6 8 Cassava peel carbon 6 52 [63]
Rubber wood sawdust carbon 6 5.72 [64]
pH

Fig. 9. Effect of pH on the adsorption of copper(II) on optimal activated carbon.

Table 5
Thermodynamic parameters of copper(II) adsorption onto activated carbon by date
Values of the adsorption capacity of other low-cost activated
stones.
carbons derived by thermal method from the literature are given in
Table 4 for comparison. The value for copper(II) sorption observed Temperature (8C) DG8 (kcal/mol) DH8 (kcal/mol) DS8 (cal/mol K)
in this work is in good agreement with values found by other 10 3.39 39.06 25.22
researchers. Differences of metal uptake are due to the properties 20 3.48 39.06 25.22
of each adsorbent such as structure, functional groups and surface 40 3.72 39.06 25.22

area.

3.3.4. Effect of temperature and thermodynamic parameters process. Similar findings have been reported by other researchers
Temperature has a pronounced effect on the adsorption working on removal of heavy metal ions from aqueous solution by
capacity of activated carbon. It was found that the copper(II) activated carbon [65,66].
adsorption uptake increases with increasing solution temperature The thermodynamic parameters for the adsorption process
from 10 to 40 8C, indicating that the adsorption is an endothermic such as free energy change (DG8), enthalpy change (DH8), and

16
14
12
qe(mg/g)

10
8
6
4
Langmuir isotherm
2
Freundlich isotherm
0
0 20 40 60 80
Ce(mg/L)

Fig. 10. Validation of copper(II) adsorption isotherms on optimal activated carbon

at 20 8C. Fig. 11. Van’t Hoff plot of adsorption equilibrium constant b.
748 F. Bouhamed et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 741–749

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