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Yildiz Technical University, Chemical Engineering Department, Davutpasa Campus, 34210 Esenler, Istanbul, Turkey
National University of Mongolia, Faculty of Organic Chemistry, Ikh Surguuliin Gudamj 1, P.O. Box 46a/523, 210646 Ulaanbaatar, Mongolia
c
Istanbul Technical University, Chemical Engineering Department, Maslak, Istanbul, Turkey
b
a r t i c l e
i n f o
Article history:
Received 31 January 2009
Received in revised form 9 May 2009
Accepted 21 August 2009
Available online 14 November 2009
Keywords:
Pyrolysis
Renewability
Activated carbon
Adsorption
Phenol
a b s t r a c t
Cherry stone based activated carbon derived from a canning industry was evaluated for its ability to
remove phenol from an aqueous solution in a batch process. A comparative adsorption on the uptake
of phenol by using commercial activated carbon (Chemviron CPG-LF), and two non-functional commercial polymeric adsorbents (MN-200 and XAD-2) containing a styrenedivinylbenzene macroporous hyperreticulated network have been also examined. Equilibrium studies were conducted in 25 mg L1 initial
phenol concentrations, 6.59 solution pH and at temperature of 30 C. The experimental data were analyzed by the Langmuir and Freundlich isotherm models. Besides, the cherry stone based activated carbons
were carried out by using zinc chloride and KOH activation agents at different chemical ratios (activating
agent/precursor), to develop carbons with well-developed porosity. The cherry stone activated carbon
prepared using KOH as a chemical agent showed a high surface area. According to the results, activated
carbons had excellent adsorptive characteristics in comparison with polymeric sorbents and commercial
activated carbon for the phenol removal from the aqueous solutions.
2009 Elsevier Ltd. All rights reserved.
Introduction
Industrialization and agricultural development together with
the population growth reduced the clean water resources. Petroleum and petrochemical, coal gasication and carbonization, pharmaceutical, wood preserving chemicals, plastic, pesticide, paper
and pulp industries generate highly toxic and carcinogenic phenolic compounds. Wastewaters containing phenolic compounds are
considered as priority serious problems since they are not only carcinogenic but also cause bad taste and odor even at low concentrations. For that reason, The US Environmental Protection Agency
(EPA) regulations call for lowering phenol content in the wastewater to less than 1 mg L1 [1]. Therefore, it is considered necessary to
remove the phenol from wastewaters before discharging into the
water stream.
Various removal technologies such as oxidation, precipitation,
adsorption, ion exchange and solvent extraction methods have
been developed for the removal phenol from wastewater. Generally, solvent extraction treatment for high levels of phenol (above
500 ppm), biological and physico-chemical treatments for intermediate levels of phenols (5500 ppm), adsorption treatments
such as ion exchange and biosorption methods for low level of phe* Corresponding author. Tel.: +90 212 383 4734; fax: +90 212 383 4725.
E-mail address: ubeker@gmail.com (U. Beker).
0196-8904/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.08.035
nol are the most widely used methods for the removal of phenol.
Adsorption method is well-established technique for treating
domestic and industrial efuents. The adsorption of phenol and related compounds from wastewater has been the subject of numerous studies by using novel adsorbents. A proper evaluation of
industrial byproducts is very important for the environment and
economy, since it would not only help assuage disposal problems,
but would also help reduce shortages of several materials [24].
Activated carbon is the most effectively used adsorbent since it
has a porous structure consisting of a network of interconnected
macropores, mesopores, and micropores due to the high surface
area and the surface chemistry such as polarity, ionic nature, functional groups.
Cherries are one of the most abundant fruits, with a world production of 1,896,522 metric tons (Mt) in 2004 [5]. Cherry stones
are obtained as a byproduct of the food industry and an inexpensive material that is available in large quantities, thus presenting
a promising application for the production of cheap and efcient
activated carbons. In Turkey, cherry stones are one of the main
byproducts of the food industry. The cherry production in Turkey
increased by 10% to 600,000 metric tons (Mt) in 2008/2009 [5].
There are very little studies in the literature relating to the preparation of activated carbons from cherry stone [6,7]. However, there
is no systematic study related to the preparation of adsorbents
from cherry stones and sorption experiments.
236
The FTIR (Fourier transform infrared spectroscopy) spectrometry was applied in the characterization of the surface functional
groups of the sorbents. The spectra were measured and recorded
(2500500 cm1) on a Mattson 1000 spectrometer.
Potentiometric titration data for the samples were carried out
using a method described by Helfferich [11]. The obtained proton-binding isotherms are positive for the proton-binding process
and negative for proton dissociation.
The electrophoretic mobilities of the equilibrated samples were
measured using a Malvern Instruments Zetasizer 3000HSA.
2.3. Batch sorption studies and analytical procedure
Phenol solution was prepared by diluting 1 g L1 of stock phenol
solution. Stock phenol solution was obtained by dissolving an exact
quantity of phenol (Merck) in distilled water. In adsorption equilibrium, experiments were conducted in a set of 250 mL Erlenmeyer
asks, in which solutions of phenol (100 mL) with initial concentration (25 mg L1) were added. Different masses of samples between 0.01 and 0.1 g were added to the phenol solutions and
each sample was kept in an isothermal shaker of 120 rpm at
30 1 C for 24 h to reach equilibrium of the solidsolution mixture. The pH of the solutions was adjusted by adding a few drops
of diluted 0.1 N NaOH or 0.1 N HCl. The nal concentration of phenol in the solution was analyzed using a UVvis spectrophotometer
(Analytic Jena Specord 40) at 270 nm wavelength. The samples
were ltered prior to analysis in order to minimize interference
of the carbon nes with the analysis. The amount of uptake capacity at equilibrium, qe (mg/g), was calculated by
qe
VC 0 C e
M
Table 1
Properties of adsorbents.
0
Sample
Surface area
(m2 g1)
Pore volume
(cc/g)
K-500
KK-1
KK-2
KK-3
KK-4
KZ-1
KZ-2
KZ-3
KZ-4
CPG-LF
MN-200
XAD-2
360
456
465
431.3
261.9
298.2
333.6
287.4
170.3
648.5
8001000
300
565
589
621
830
1250
147
183
406
646
4450
850950
90
0.2157
0.3018
0.3258
0.3133
0.3047
0.0758
0.1836
0.2788
0.2151
0.1767
11.1
0.9345
237
Fig. 1. Proton binding curves of activated carbons: (a) KK series, (b) KZ series and
(c) polymeric adsorbents and commercial activated carbon.
238
and external surface, and the IEP refers only to the external surface
of the adsorbent. It can be deduced that the distribution of acidic
surface groups is not homogeneous since the IEP is located at lower
pH values. This indicates that the concentration of acidic groups is
higher at the external surface as compared to the interior of the
activated carbon samples produced from cherry stones. The zeta
potential curves for the KZ and KK samples fall steeply with
increasing pH until pH 6 and then start to level off. Dissociation
of relatively strong carboxylic surface groups is probably responsible for this effect. Indeed, the dissociation of this type of group occurs at pH values between 2 and 6, thereby enhancing the
negativity of the surface. In those carbons produced, weaker surface functional groups are more prevalent than in the CPG-LF.
Therefore, it is zeta potential curve that changes more gradually
in comparison to those of the KZ and KK samples. The IEP for the
two non-functional polymeric adsorbents (MN-200 and XAD-2)
are close to 5. This value is somewhat high when compared with
the IEP for carbon samples.
The effect of solution pH on phenol removal by different adsorbents was examined and the results are presented in Figs. 3 and 4.
Phenol was better adsorbed to carbon adsorbents at the pH 6.5.
This behavior can be explained considering the nature of the adsorbent at different pH in phenol adsorption.
The surface of the activated carbon contains a large number of
functional groups. The pH dependence of phenol adsorption can
largely be related to the type and ionic state of these functional
groups and also on the phenol chemistry in solution. This might
have resulted from neutralization negative charges at the surface
of carbons with increasing hydrogen ion concentration, thereby
reducing hindrance to diffusion and making available more active
surface of carbons. The isoelectric point of activated carbon samples are between pH 1and 3; as the pH was lowered, the overall
surface charge became positive, and this led to donoracceptor
interactions between the aromatic ring of phenol activated by
the OH and the groups of the activated carbon. As the pH increased, however, the overall surface charge became negative
and sorption decreased. Phenols are adsorbed at the carbonyl oxygens on the activated carbon surface according to a donoracceptor
complexation mechanism. As seen in Figs. 3 and 4, the activated
carbons showed a better sorption capacity at pH 6.5 for phenol
since the undissociated species of the adsorbate is preferred by
the negatively charged surface groups. Such specic interaction
may play a positive role in phenol adsorption from aqueous solution; however, it will be effectively weakened in aqueous solution
due to the competitive effect of water.
The pKa value of phenol is 9.89 at 298 K, the pH-dependent nature may be explained by the fact that only the phenol molecules
adsorb effectively onto the adsorbents through van der Waals
interaction, while the phenolate anions do not, due to their hydrophilic nature. The pH at which this decrease occurs depended on
the difference between the external and internal surface charge
239
Fig. 5. Phenol removal percentage of the activated carbons and polymeric adsorbents at pH 6.5 and 9.0.
240