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Received 23 June 2016 The removal of Hg from aquatic environments using activated carbon (AC) impregnated with humic acid
Received in revised form 15 July 2016 was investigated. The Hg adsorption capacity of the AC was controlled by the specic surface area and by
Accepted 22 July 2016 surface functional groups, and the Hg adsorption process was exothermic and more effective at low pH.
Available online 28 July 2016 The Hg adsorption process in this study corresponds to a Lagergren pseudo-2nd-order model, indicating
that it is controlled by the chemical rather than the physical properties of the AC. In addition, the
Keywords: equilibrium isotherm data t the Langmuir isotherm better than the Freundlich model, indicating that
Minamata the AC surfaces were uniform and that a Hg adsorbate monolayer formed at equilibrium.
Mercury
2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Activated carbon
reserved.
Impregnation
Humic acid
Isotherm
http://dx.doi.org/10.1016/j.jiec.2016.07.029
1226-086X/ 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652 47
The adsorption of Hg from aqueous solutions by the virgin AC Earlier studies of AC revealed the presence of several surface
and the impregnated samples in a CSTR was assessed as follows. functional groups: carboxylic groups, anhydrides, lactones, and
The ratio of the AC to the Hg solution was 0.25 g to 50 ml, and all the ketenes at 17501630 cm1; CC at 16001450 cm1; OH, NH, and
experiments were conducted at 20 C except the evaluation of the CH stretching in alkyl or aryl groups at 34883100 cm1; and NH
effect of pH and temperature. A magnetic bar rotating at 400 rpm vibrations at 16551590 cm1 [710]. The FTIR spectra shown in
was used for stirring in all the experiments. The Hg solutions were Fig. 3 are similar, which suggests that the samples have similar
prepared by progressive dilution of the stock solution. The quantity chemical groups and structures: OH (3400 cm1), COOH
adsorbed was calculated using the equation (15001600 cm1), phenols and hydroxyl groups (1090 cm1),
and CH (770800 cm1) were noted in the spectra of the AC
V samples. No peaks corresponding to OH (3400 cm1) or COOH
qe C 0 C e 1
m (15001600 cm1) were observed in the spectra of virgin AC,
where qe is the quantity of adsorbed Hg (mg/g), C0 is the initial Hg indicating that novel functional groups were generated only by the
concentration in solution (mg/l), Ce is the equilibrium Hg humic acid impregnation.
48 G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652
Fig. 1. Nitrogen adsorptiondesorption isotherms of activated carbon and modied activated carbon.
Effect of contact time Subsequently, the rates displayed by HAAC1, HAAC3, and
HAAC6 increased slowly and reached adsorption equilibrium at
The effect of contact time was assessed experimentally at pH 300 and 540 min. The adsorption quantities of HAAC1, HAAC3, and
7 and 30 C. As shown in Fig. 4, the quantities adsorbed by all the AC HAAC6 were similar to one another and higher than that of the
samples increased with increasing contact time. In the rst 60 min, virgin AC. The graphs in Fig. 4 show that the adsorption of AC was
the adsorption rate increased rapidly with increasing contact time. dominated by physical adsorption and that the adsorption by
Fig. 2. Micropore (MP) size distributions of activated carbon and modied activated
carbon. Fig. 3. FT-IR spectra of activated carbon and modied activated carbon.
G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652 49
Effect of pH
Table 1
Characteristics of activated carbon and modied activated carbon.
Sample Surface area (m2/g) Micropore volume (cm3/g) Mesopore volume (cm3/g) Total volume (cm3/g) Mean diameter (nm)
Virgin AC 950.89 0.4323 0.0787 0.4316 1.8154
HAAC1 983.87 0.4487 0.1002 0.4611 1.8746
HAAC3 951.15 0.4413 0.1042 0.4494 1.8897
HAAC6 944.6 0.4267 0.0681 0.4229 1.7908
Fig. 5. Effect of pH on Hg(II) removal by activated carbon and modied activated carbon.
50 G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652
Fig. 6. Effect of temperature on Hg(II) removal by activated carbon and modied activated carbon.
G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652 51
Table 2
Kinetic parameters for the adsorption of Hg(II) on virgin AC and modied ACs.
slowly decreased with time. The kinetic results (Table 2) suggest The experimental data were tted to these isotherm models;
that the process of Hg adsorption by AC is a two-speed process the results are shown in Fig. 8, and the parameters are listed in
involving both rapid and slow adsorption [12]. Table 3. The correlation coefcients of the Langmuir isotherm were
slightly better than those of the Freundlich isotherm, which
Equilibrium isotherm indicates that the sample surfaces were uniform and that Hg
adsorbate monolayers were formed when the Hg adsorption
Freundlich and Langmuir isotherm models were tested to reached equilibrium.
investigate the adsorption of a liquid-phase pollutant (Hg(II)) by a
solid adsorbent (AC):
Ce Ce 1
5
qe q0 qo K L
1
lnqe lnK F lnC e 6
n
where Ce is the equilibrium concentration (mg/l), qe is the
experimental adsorption equilibrium value (mg/g), q0 is the
solid-phase concentration corresponding to complete coverage
of available adsorption (mg/g), and KL and KF are characteristic
constants.
Fig. 8. The Langmuir isotherm and Freundlich isotherm plots for the adsorption of
Hg(II) on activated carbon and modied activated carbon.
Table 3
Isotherm parameters for the adsorption of Hg(II) on virgin AC and modied ACs.
q0 KL R2 (%) n KF R2 (%)
Virgin AC 22.3214 0.0963 99.90 1.3900 5.8681 99.14
HAAC1 17.1233 0.4378 99.99 1.6952 37.6877 97.78
HAAC3 17.1527 0.4194 99.91 1.5939 34.4271 98.96
Fig. 7. The Lagergren rst order/second order/pseudo-second order model plots for
HAAC6 17.7233 0.7626 99.91 1.7966 60.3254 97.45
the adsorption of Hg(II) on activated carbon and modied activated carbon.
52 G. Jin et al. / J. Ind. Eng. Chem. 42 (2016) 4652
Conclusions Environment, Korea. The authors also thank Michelle J. Lee for her
help in preparing and analyzing the samples.
In this study, experiments on Hg adsorption by AC impregnated
with humic acid were performed. The humic acid impregnation
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