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Journal of Industrial and Engineering Chemistry 42 (2016) 4652

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Journal of Industrial and Engineering Chemistry


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

Removal of Hg(II) from aquatic environments using activated carbon


impregnated with humic acid
Gang Jin, Yujin Eom, Tai Gyu Lee*
Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Republic of Korea

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

Article history:
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

Introduction in nature and widely used as a fertilizer in agriculture. Previous


research has demonstrated that nitrogen-, S-, and Cl-containing
Activated carbon (AC) is an effective adsorbent for the removal functional groups, which are present in humic acid, effectively
of various types of heavy metals dissolved in aquatic environments combine with Hg ions [2,3]. The goals of this study were to
due to its exceptionally large surface area and great pore volume. impregnate AC with humic acid for the removal of Hg(II) from
AC is widely used in the treatment of wastewater contaminated aquatic environments, to evaluate the mechanisms of this Hg
with Hg. However, because the adsorption capacity of virgin AC is adsorption, and to determine the kinetics and equilibrium
less than that of modied AC, surface modication of AC is an isotherms of this adsorption.
effective way to enhance the Hg removal efciency. To this end, the
most commonly used impregnation substances are sulfur (S) and Experimental
chlorine (Cl). S-impregnated and Cl-impregnated AC are effective
adsorbents for the removal of Hg from wastewater. However, due All the chemicals used in this study were of analytical reagent
to the high cost of impregnate materials such as Cl, there is a grade. To maintain the concentration of the Hg solution, 2% nitric
growing need for inexpensive substances that can be used to acid was added in accordance with US EPA method 7470A [4].
impregnate ACs. Adsorption of Hg was conducted in a continuously stirred tank
Organic substances are one of the most effective components reactor (CSTR) that was stirred using a magnetic bar. The Hg
for adsorbing Hg ions in the aquatic environment; they can interact concentration was analyzed using a CVAAS (cold vapor atomic
with Hg ions to immobilize them on the AC surface. Moreover, adsorption spectroscopy)-type Hg analyzer (RA-915+/RP-91, Lumex
binding to organic substances usually reduces the toxicity of Hg Ltd., Petersburg, Russia). The condition of the instrument was
[1]. For example, methyl Hg is inhibited when it binds to organic evaluated by analyzing a certain concentration of Hg in a certied
substances. An organic substance, humic acid, was impregnated reference material (CRM: SRM 3133, NIST, Gaithersburg, USA).
into AC in the present study. Humic acid is a promising substance The AC consisted of granular-type virgin material that was
for introduction into AC due to its aromaticity. It is found primarily commercially purchased (Duksan Chemicals Inc., Seoul, Korea) and
had a surface area and total pore volume of 950.89 m2/g and
0.4316 cm3/g, respectively. A Hg stock solution was prepared by
dissolving 0.1361 g of HgCl2 into 700 ml of de-ionized (DI) water;
* Corresponding author. Fax: +82 2 6008 0560.
20 ml of concentrated nitric acid was added, and the volume was
E-mail addresses: yjeom@yonsei.ac.kr (Y. Eom), teddy.lee@yonsei.ac.kr
(T.G. Lee).
brought to 1000 ml using DI water.

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

Preparation of virgin materials concentration in solution (mg/l), V is the volume of the Hg


solution (l), and m is the AC mass (g).
Prior to the impregnation with humic acid, the AC was washed
with DI water until the residues of AC were removed. Afterward,
the AC was dried in an oven at 95  C for 12 h. The dried AC was Results and discussion
cooled to 20  C and stored in a reagent refrigerator.
N2 adsorptiondesorption isotherms
Preparation of the humic acid solution
The N2 adsorptiondesorption isotherms are shown in Fig. 1. All
Humic acid is not soluble in water under acidic conditions but is the samples in this study yielded type IV isotherms, the graphs of
soluble under basic conditions [5]. NaOH and HCl were used to which are very similar to type II isotherms in the low-pressure
dissolve humic acid powder to create a liquid phase. First, 0.1601 g region, which indicates the formation of monolayers followed by
of NaOH was dissolved in 40 ml of DI water, and 0.5 g of humic acid multilayers. The great increase in the adsorbed quantity in the low-
powder was added to the 1 N NaOH solution. Then, the solution pressure region indicates that Hg ions were condensing in the AC
was diluted with approximately 900 ml of DI water and stirred for micropores. Capillary condensation was observed in the high-
2 h at 400 rpm. After mixing, the pH was adjusted to 6 with 0.5 N pressure region; this process is caused by multilayer adsorption in
HCl, the volume was increased to 1000 ml, and the solution was a porous material, which indicates the presence of mesopores in
stirred for 3 h at 400 rpm using a magnetic bar. The solution was the AC.
nally ltered through 40-mm lter paper. HAAC1 adsorbed more Hg than the other AC samples due to its
greater specic surface area. During the impregnation, the reaction
Modication of AC time of HAAC1 with humic acid was shorter than that of the other
samples, and we conclude that much of the free surface area of
Virgin AC (2.5 g) was added to the prepared humic acid solution, HAAC1 did not become impregnated with humic acid. The larger
and separate samples of this solution were left for 1 h, 3 h, and 6 h surface area of HAAC1 created the highest adsorption plateau
at 20  C under a fume hood to allow the impregnation. After the among the plots. Additionally, the plateau of HAAC3 was slightly
impregnation, each AC sample was separated by ltration and higher than that of the virgin AC, and the plateau of HAAC6 was
washed with DI water. Each sample was then dried in an oven for slightly lower than that of the virgin AC, indicating that more
12 h at 95  C. humic acid was impregnated with time. Therefore, the heat
To increase the aromaticity of the AC, each AC sample was heated treatment of the AC increased the surface area, and both the
in a nitrogen atmosphere to 600  C at a heating rate of 5  C/min, and specic surface area and pore volume decreased with increasing
this temperature was then maintained for 2 h. Finally, the samples time of impregnation.
were stored in a reagent refrigerator. The prepared AC samples
obtained by impregnating the virgin AC with humic acid for 1, 3, and Analysis of the pore-size distribution
6 h were labeled HAAC1, HAAC3, and HAAC6, respectively.
Because AC is a porous material, the pore-size distribution of
Pore-size distribution and surface area the AC was measured using Micropore model analysis. The
Micropore model was based on a plot of the t-curve of the
Analyses for specic surface area and pore volume were adsorbed volume of the adsorbates versus the thickness of the
performed by obtaining N2 adsorptiondesorption isotherms using adsorbed layer [6]. As Fig. 2 shows, the impregnation with humic
a BELSORP-max instrument (BEL, Osaka, Japan). Before analysis, acid did not change the pore structure of the AC. The modal pore
the samples were degassed with a nitrogen ow for 2 h at 350  C size was 0.7 nm, and the majority of the micropores in the virgin
under vacuum. A Micropore model was used to calculate the pore- AC, HAAC1, HAAC3, and HAAC6 measured 0.41.4 nm, 0.41.5 nm,
size distribution. 0.41.5 nm, and 0.41.4 nm, respectively.
The specic surface area, pore volume and average pore
Fourier transform infrared (FTIR) spectroscopy diameter of each sample are shown in Table 1. Compared with the
virgin AC, HAAC1 contained greater surface area and higher
The functional groups on the sample surfaces were identied by micropore and mesopore volumes due to the heat treatment.
FTIR spectroscopy. Sample discs were prepared by mixing samples Increasing the impregnation time decreased the surface area and
with KBr to form a pellet and were scanned from 4000 to 400 cm1 pore volume.
on a Vertex 70 spectrometer (Bruker, Coventry, England).

Hg Adsorption process FTIR spectroscopy

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

HAAC1, HAAC3, and HAAC6 was controlled by the chemical


reactions of functional groups and the aromaticity of the humic
acid.
The adsorption by the AC was inuenced by its specic surface
area and pore structure. As shown in Table 1, increasing the contact
time with the humic acid resulted in a decrease in surface area;
however, the quantities adsorbed by HAAC1, HAAC3, and
HAAC6 were similar, which indicates that the functional groups
on the AC surfaces are more important than the specic surface
area.

Effect of pH

The effect of pH on the removal of Hg by the virgin AC, HAAC1,


HAAC3, and HAAC6 was assessed at pH 2, 7, and 12 (Fig. 5). The
quantity of Hg adsorbed by the AC was greatest at pH 2, and
Fig. 4. Effect of contact time on Hg(II) removal by activated carbon and modied increasing the pH decreased the adsorption. Thus, increasing the
activated carbon.

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

pH caused greater inhibition of the ionization of functional groups


on the surfaces of the samples.
1 1
3
qe  qt qe;c k2 t
Effect of temperature

The effect of the aqueous solution temperature on the removal


of Hg by the virgin AC, HAAC1, HAAC3, and HAAC6 was investigated t 1 t
4
at three temperatures: 30, 50, and 70  C (Fig. 6). The quantity of qt k3  q2e qe;c
adsorbed Hg decreased signicantly with increasing temperature, where qe is the experimental adsorption equilibrium value (mg/g);
which indicates that this adsorption is exothermic. Increasing the qt is the adsorption quantity (mg/g); qe,c is the theoretical
temperature caused the adsorbed Hg molecules to be suspended in adsorption equilibrium value (mg/g); t is the reaction time
the internal space due to van der Waals forces between the (min); and k1,k2, and k3 are characteristic constants.
adsorbate and adsorbent. The Hg adsorption capacities of An assumption of a Lagergren 1st-order model is that the Hg
HAAC3 and HAAC6 were greater than those of the virgin AC and adsorption is controlled by the diffusion, and the model relates the
HAAC1. rate of adsorption and the difference between the equilibrium
adsorption quantity and the adsorption quantity at time t.
Kinetic studies Assumptions of Lagergren 2nd-order and pseudo-2nd-order
models are that the Hg adsorption is controlled by the chemical
The study of Hg adsorption kinetics is signicant in water reaction and that the adsorption mechanism involves the exchange
treatment: these kinetics control the solute uptake rate, which of electrons during the adsorption process. Kinetic plots were
in turn controls the residence time of adsorbate uptake at the drawn for the virgin AC, HAAC1, HAAC3, and HAAC6.
solidsolution interface [11]. Lagergren 1st-, 2nd-, and pseudo- As shown in Fig. 7, The Lagergren pseudo-2nd-order model ts
2nd-order models were tested: the results of this study. In this model, the adsorption rate is
lgqe;c  k1 controlled by the chemical reaction. At rst, the rate of Hg
lgqe  qt 2 adsorption increased due to abundant active sites for interactions
2:303  t
with Hg ions and the strong driving force of Hg adsorption, which

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.

Sample Lagergren 1st-order Lagergren 2nd-order Lagergren pseudo-2nd-order


2 2
k1 qm (mg/g) R (%) k2 qm (mg/g) R (%) k3 qm (mg/g) R2 (%)
Virgin AC 0.0001 1.1803 1.04 0.0001 1.1447 0.34 0.0052 13.2275 99.29
HAAC1 0.0016 1.7787 67.16 0.0025 5.3533 68.84 0.0058 14.7059 99.95
HAAC3 0.0025 2.3741 84.54 0.0085 1.1730 84.17 0.0041 14.9477 99.94
HAAC6 0.0021 2.5769 79.68 0.0042 3.6536 84.86 0.0034 14.8809 99.89

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.

Sample Langmuir isotherm Freundlich isotherm

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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