Beruflich Dokumente
Kultur Dokumente
CITATIONS READS
231 1,181
3 authors, including:
All content following this page was uploaded by Shunnian wu on 24 July 2014.
Abstract
In this study, citric acid was used to modify a commercially available activated carbon to improve copper ion adsorption
from aqueous solutions. The carbon was modified with 1.0 M citric acid, followed by an optional step of reaction with 1.0 M
sodium hydroxide. It was found that the surface modification reduced the specific surface area by 34% and point of zero
charge (pH pzc ) of the carbon by 0.5 units. Equilibrium results showed that citric acid modification increased the adsorption
capacity to 14.92 mg Cu / g, which was 140% higher than the unmodified carbon. Higher initial solution pH resulted in
higher copper adsorption. The chemical surface modification adversely affected the copper adsorption rate. Adsorption
kinetic mechanisms were investigated with an intraparticle diffusion model. It was found that the modification did not
change both external diffusion and intraparticle diffusion.
2003 Elsevier Ltd. All rights reserved.
Keywords: A. Activated carbon; B. Chemical treatment, Surface treatment; C. Adsorption; D. Adsorption properties
0008-6223 / 03 / $ see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016 / S0008-6223(03)00197-0
1980 J.P. Chen et al. / Carbon 41 (2003) 19791986
copper ion adsorption behaviour was examined. An in- pure nitrogen gas overnight at a temperature of 150 o C to
traparticle diffusion model was used to investigate the remove any contaminants as well as moisture that might be
adsorption mechanisms. present on the activated carbon surfaces.
The surface morphology of the activated carbon samples
was visualized by scanning electron microscopy (JEOL,
2. Experimental JSM-5600V, Japan). SEM enables the direct observation of
any surface microstructure changes in the activated car-
2.1. Materials bons that would have occurred due to the citric acid
modification.
In this study, Fitrasorb 200 (Calgon, Pittsburgh, PA, Potentiometric titration experiments were carried out
USA) was used. Copper chloride dihydrate from J.T. Baker with an automatic titrator (Metrohm 716 DMS Titrino,
(Phillipsburg, USA), and sodium nitrate, lead nitrate, Switzerland). A 0.25-g amount of activated carbon was
sodium hydroxide, sodium acetate, acetic acid, hydrochlo- added to a conical flask containing 50 ml of 0.1 M sodium
ric acid, nitric acid and citric acid monohydrate from nitrate as background ionic strength. The solution was
Merck (Germany) were used. All chemicals were of shaken for 48 h on a shaker. The titration was carried out
reagent grade. Solution pH was adjusted by 0.1 M HCl or using 0.1 M NaOH and 0.1 M HNO 3 solutions.
0.1 M NaOH. The citric acid has a chemical formula of
HOOCCH 2 COH(COOH)CH 2 COOH, indicating that 2.4. Adsorption equilibrium
it is a small organic compound rich in carboxylic groups.
The concentration of metal ions was measured using The activated carbons of varying amounts were added to
inductively coupled plasma emission spectroscopy (ICP- conical flasks that contained 100 ml buffered or unbuffered
ES) (Perkin-Elmer Optima 3000, USA). Samples were CuCl 2 solutions. Buffered solution with a pH of 4.9 was
acidified with concentrated nitric acid, and filtered with a comprised of 0.07 M sodium acetate and 0.03 M acetic
0.45-mm Whatman Autovial filter (USA) before analysis. acid. The unbuffered solutions pH values ranging from 3
Solution pH was measured using an Accumet basic pH to 11 were adjusted by adding HCl or NaOH. The
meter (Fisher Scientific, USA). solutions were shaken on a shaker with temperature
controlled at 25 8C for 48 h in order to reach equilibrium.
2.2. Preparation of citric acid-modified and base- The final samples were analyzed using ICP-ES.
extracted activated carbons
2.5. Adsorption kinetics
The activated carbon was ground and sieved to retain
the 2032 mesh fraction. It was washed with deionised A 10-g amount of activated carbon was added to 1000-
(DI) water to remove fine powdered activated carbon left ml buffered or unbuffered 1310 24 M CuCl 2 solution. The
after sieving. It was then left to dry in an oven at 110 8C solution was then stirred at a constant rate. Samples were
for 2 h and denoted by WAC. taken at different time intervals and analysed using ICP-
The WAC was reacted with a 1 M citric acid solution at ES. The pH was 4.9 in the buffered solutions; while the
a ratio of 4 g activated carbon to 25 ml citric acid solution. initial and final pH values were 5.0 and 5.2 in the
It was shaken for 30 min before being dried at 50 8C unbuffered solutions.
overnight. The citric acid modified activated carbon was
then washed with DI water until no turbidity could be
observed when a 0.1 M lead nitrate solution was added to 3. Results and discussion
the washed liquid. The modified activated carbon was
dried at 110 8C for 2 h and referred to as CAC. 3.1. Specific surface areas of activated carbon samples
A fraction of CAC was continuously washed with a 1 M
sodium hydroxide solution for at least 2 h. It was then As represented in Table 1, the surface area is 648 m 2 / g
washed with DI water to remove the excess sodium for the WAC, similar to the value reported by Corapcioglu
hydroxide until no pH variation in the washed liquid could and Huang [6], but lower than 1008.8 m 2 / g reported by
be detected. This base-extracted CAC was then dried at Chen and Lin [7]. The difference could be due to the
110 8C for 2 h and referred to as SAC. removal of considerable organic by-products and minerals
present in the activated carbon surface. In this study, the
2.3. Surface properties carbon was washed between 20 and 30 times until the pH
and the conductivity of the water samples became con-
The specific surface areas of the activated carbon stant; while the carbons were normally washed 35 times
samples were determined using a NOVA 300 BET analyzer in most of studies (e.g., Chen and Lin [7]).
(QuantaChrome, USA). Before adsorption isotherms were The citric acid modification of the activated carbon
obtained, the activated carbon sample was purged with further reduces the surface areas of CAC and SAC by 34
J.P. Chen et al. / Carbon 41 (2003) 19791986 1981
Table 1
Summary of specific surface areas of activated carbon samples
Carbon type Description Specific surface area (m 2 / g)
WAC Unmodified activated carbon 648
CAC Citric acid modified activated carbon 431
SAC Sodium hydroxide-extracted CAC 448
and 31%, respectively. This could arise from pore block- reduction in the surface area of CAC as compared with
age by adsorbed citric acid molecules. Because of its small that of WAC (Table 1). It implies that the adsorption
molecular size, citric acid can easily access the pore kinetics in CAC may be much slower than that in WAC
structure of the activated carbon. This finding is consistent since clogging of the cracks and cavities can lead to
with the results reported by Ferro-Garcia et al. [8], resistance in the metal transport from the solution to the
indicating that the surface area of activated carbon de- adsorption sites.
creased from 1086 to 643 m 2 / g after adsorption of gallic
acid [(HO) 3 C 6 H 2 CO 2 H]. Some surface area of CAC is 3.3. Potentiometric titration
recovered after sodium hydroxide treatment. This may be
partially attributed to the removal of the organic substances The effect of the modification was investigated by
within the pore structure, which are soluble in alkali potentiometric titration of the carbon samples before and
solution. after modification. The amphoteric behaviour of activated
carbons can be described by the following ionisation
3.2. SEM micrographs reactions [6,7]:
SOH 1 H SOH 2
1 1
Fig. 1 shows the SEM micrographs of activated carbon Ka1 (1a)
samples before and after citric acid modification. It dem-
onstrates that there are considerable small cavities, cracks SOH SO 1 H
2 1
Ka2 (1b)
and attached fine particles over the activated carbon
surface, forming a system of complicated pore networks. where SOH represents a generalized surface functional
Comparison of these micrographs shows that the modi- group.
fication does not significantly change the morphology of The potentiometric titration data were used in the
the surface matrix of the carbons. However, the citric acid determination of the above the intrinsic surface acidity
modification reduces the number of cracks and cavities on constants (Ka1 and Ka2 ) and the concentration of surface
the carbon surface, which are clogged by the adsorbed functional group of carbons (SOH). An equilibrium con-
citric acid molecules. This also explains the reasons for the stant searching program, called FITEQL developed by
Fig. 1. SEM micrographs of the surfaces of the carbons: (a) WAC; (b) CAC.
1982 J.P. Chen et al. / Carbon 41 (2003) 19791986
qmax bCe
qe 5 ]] (2)
1 1 bCe
Table 2
Surface site properties of activated carbon samples*
Carbon type WAC CAC
Concentration of surface functional groups (mmol / g) 0.19 0.32
Surface acidity constants
pKa1 4.52 3.98
pKa2 8.42 8.77
pH pzc 7.07 6.54
* Units: Ka1 : M 21 ; Ka2 : M.
J.P. Chen et al. / Carbon 41 (2003) 19791986 1983
qe 5 Kf C e1 / n (3)
Table 3
Adsorption isotherm constants at pH 4.9*
Carbon type Langmuir constants Freundlich constants
qmax b r2 Kf 1 /n r2
WAC 6.14 0.18 0.9826 2.16 0.24 0.9934
CAC 14.92 0.08 0.9940 1.66 0.57 0.9025
SAC 11.85 0.20 0.9996 2.72 0.38 0.9361
* Units: qmax : mg / g; b: (mg / l)21 ; Kf : (mg / g) /(mg / l)1 / n .
1984 J.P. Chen et al. / Carbon 41 (2003) 19791986
It can be assumed that the adsorption of copper ions mum adsorption capacity increased from 6.14 mg Cu / g
onto the activated carbons follows mainly these three WAC to 14.92 mg Cu / g CAC and 11.85 mg Cu / g SAC,
consecutive steps of external diffusion, intraparticle diffu- respectively. After the modification, the activated carbon
sion, and finally adsorption reactions. One or more of these surface became more homogeneous; while its specific
steps can control the adsorption kinetics. In most cases, the surface area decreased significantly.
adsorption reactions occur rapidly. Therefore, the first two The adsorption kinetics of the modified carbons was
steps are normally important in the kinetics. There are a slower than that of the unmodified carbon. The modi-
series of theoretical models available to describe the fication does not change both external diffusion and
adsorption kinetics [7,12]. However, the mathematical intraparticle diffusion properties.
solutions are pretty complex and require more input Effect of initial solution pH on the copper adsorption
information, such as adsorption reaction constants. onto the citric acid modified carbons was insignificant;
A simplified intraparticular diffusion model was also however, it became important when the unmodified carbon
employed to elucidate the adsorption mechanisms. It was was used. These modified carbons were able to maintain
first developed by Weber and Morris [13] and has been high metal adsorption capacity in very wide pH range.
used in adsorption kinetic studies [14]. It is assumed that Therefore, they can be useful in treating wastewater with a
the adsorption is controlled by three stages: the first wider pH range.
sharper linear stage being a rapid external diffusion and
surface adsorption; the second linear stage being a gradual
adsorption stage, where the intraparticle diffusion is rate-
Acknowledgements
limited; and the final stage being final equilibrium stage
where the intraparticle diffusion starts to decrease due to
The financial support provided to J.P.C. by the National
low concentration in solution phase as well as less
University of Singapore under RP-3981604 and R-279-
available adsorption sites.
000-104-112 is appreciated.
Adsorption capacity (q, mg / g) can be plotted against
t 1 / 2 . As shown in Fig. 5b, the adsorption has three stages.
The first stage in the four adsorption cases is completed in
about 6.25 min. The second stages in the cases demon- References
strate a linear relationship. The third stage is a slow
process, due to the low concentration gradient. [1] Chen JP, Hong L, Wu SN, Wang L. Elucidation of interac-
The second stage can be described as following: tions between metal ions and Ca-alginate based ion exchange
resin by spectroscopic analysis and modeling simulation.
q | kdt 1 / 2 (5) Langmuir 2002;18(24):941321.
[2] Ravindran V, Stevens MR, Badriyha BN, Pirbazari M.
where k d is an intrinsic kinetic rate constant for intraparti- Modeling the sorption of toxic metals on chelant-impreg-
cle diffusion. nated adsorbent. J AIChE 1999;45:113546.
In the determination of the above k d values, calculation [3] Lakov L, Vassileva P, Peshev O. Sorption of heavy metals on
only takes into account of the range of 10 to 60 min of the pyrazolone-containing carbon sorbents. Carbon
adsorption region. The k d values are 4.15310 22 , 4.293 1999;37:16557.
10 22 , 4.73310 22 and 6.06310 22 (mg / g) / min 1 / 2 , for [4] Monser L, Adhoum N. Modified activated carbon for the
WAS, CAC, SAC and CAC with buffered solution (pH removal of copper, zinc, chromium and cyanide from
wastewater. Sep Purif Technol 2002;26:13746.
4.9), respectively. Higher linear regression coefficients
[5] Morel FMM, Hering JG. Principles and applications of
(r 2 .0.99) are obtained, which indicates the importance of
aquatic chemistry. New York: Wiley; 1993.
intraparticle diffusion in the second stage. [6] Corapcioglu MO, Huang CP. The adsorption of heavy metals
Comparison of the k d values of WAS, CAC and SAC onto hydrous activated carbon. Water Res 1987;21:103144.
indicates that the chemical surface modifications do not [7] Chen JP, Lin MS. Equilibrium and kinetics metal ion
change the kinetic properties in the intraparticle diffusion. adsorption onto a commercial H-type granular activated
It is observed that the CAC case with buffered solution carbon: experimental and modeling studies. Water Res
(pH 4.9) has a larger value. The buffered solution is 2001;35:238594.
comprised of sodium acetate / acetic acid, which may form [8] Ferro-Garcia MA, Rivera-Utrilla J, Bautista-Toledo I,
additional copper complexes and possibly facilitate the Moreno-Castilla C. Adsorption of humic substances on
activated carbon from aqueous solutions and their effect on
metal mass transfer.
the removal of Cr(III) ions. Langmuir 1998;14:18806.
[9] Herbelin AL, Westall JC. FITEQL: a computer program for
determination of chemical equilibrium constants from ex-
4. Conclusions perimental data, version 4.0. Department of Chemistry,
Oregon State University; 1999.
Activated carbon modification by citric acid significantly [10] Adamson AW. Physical Chemistry of Surfaces. New York:
improves its copper ion adsorption capacity. The maxi- Wiley; 1976.
1986 J.P. Chen et al. / Carbon 41 (2003) 19791986
[11] Perrin DD. Dissociation constants of inorganic acids and ters by adsorption. In: Proceedings of the International
bases in aqueous solution. London: Butterworths; 1969. Conference on Water Pollution Symposium, Oxford: Per-
[12] Chen JP, Yiacoumi S, Blaydes TG. Equilibrium and kinetic gamon Press; 1962, pp. 23166, vol. 2.
study of copper adsorption by activated carbon. Sep Technol [14] Juang RS, Wu FC, Tsing RL. Characterization and use of
1996;6:13346. activated carbon prepared from bagasses for liquid-phase
[13] Weber WJ, Morris JC. Advances in water pollution research: adsorption. Colloid Surface A: Physicochemical Eng Aspects
removal of biologically-resistant pollutants from waste wa- 2002;201:1919.