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Fuel 87 (2008) 1355–1359


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Adsorption of Cu2+ from water using raw and modified coal fly ashes
Ting-Chu Hsu *, Chung-Chin Yu, Chin-Ming Yeh
Department of Environmental Engineering, Vanung University, Chung-Li 320, Taiwan, Republic of China

Received 26 October 2006; received in revised form 25 May 2007; accepted 30 May 2007
Available online 16 July 2007

Abstract

In this study, we found that both raw and modified coal fly ashes effectively adsorb Cu2+ from wastewater. The adsorption capacities
followed the order CFA> CFA-600> CFA–NaOH. The adsorption isotherms for Cu2+ on the raw and modified coal fly ashes fit the
Langmuir, Freundlich, and DKR isotherms quite well. These adsorptions were endothermic in nature; the values of E (between 1.3
and 9.6 kJ mol1) were consistent with an ion-exchange adsorption mechanism. The adsorptions of Cu2+ onto CFA, CFA-600, and
CFA–NaOH followed pseudo-second-order kinetics.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Coal fly ash; Cu2+; Adsorption isotherm; Kinetics

1. Introduction as bentonite, lignin, clay, fly ash, blast furnace sludge,


red mud, biomass and bagasse fly ash) for the removal of
Many electroplating and printed circuit board factories heavy metals from water [9–18].
discharge large amounts of poisonous heavy metals in their Coal fly ash is a waste from coal-burning power plants.
wastewater, with copper ions being one of the most com- In Taiwan, coal provides 44% of the total supply of electric
mon. These effluents must be decontaminated to avoid power to generate electricity and coal fly ash production
their toxicity and carcinogenicity [1,2]. Copper is highly exceeds 1.6 million tons per year. Besides, worldwide pro-
toxic because it is non-biodegradable and carcinogenic duction of coal fly ash is ca. 500 million tons per year. This
[3,4]. A number of methods are available to reduce heavy waste must be reduced prior to disposal.
metals in wastewater, including chemical precipitation, In recent years, coal fly ash has been used as an addi-
ion exchange, adsorption, reverse osmosis, and so on [5– tive in cement and concrete, as a structural filler, for
8], but the high costs of these methods restrict their waste stabilization, and for road base stabilization [19].
applicability. It is also an efficient adsorbent for heavy metals [20]. we
Small-scale factories in Taiwan are unable to apply sought to develop a low-cost adsorbent system, using dif-
expensive wastewater treatment methods because of finan- ferent coal fly ashes, for the removal of Cu2+ ions from
cial limitations. Cheap and effective alternatives for the wastewater.
removal of copper ions are expected to reduce these manu-
facturers’ operating costs, reduce the prices of their prod-
2. Materials and methods
ucts, improve their competitiveness, and also benefit the
environment. Many reports have described the different
2.1. Preparation of adsorbents
adsorption abilities of various low-cost adsorbents (such
A sample of the raw coal fly ash (CFA) was collected
*
Corresponding author. Fax: +886 346 22232. from a coal-burning power plant; it was used without pre-
E-mail address: djshue@msa.vnu.edu.tw (T.-C. Hsu). treatment. One portion of the sample was treated in a

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.05.055
1356 T.-C. Hsu et al. / Fuel 87 (2008) 1355–1359

furnace at 600 C for 4 h and then stored in a desiccator fixed at 24 h. For thermodynamic studies, these procedures
prior to use (CFA-600); the other portion was mixed with were repeated at 45 and 60 C.
6 N NaOH in a stainless-steel beaker and maintained at
90 C for 0.5 h with stirring. The latter mixture was left
for 4 h to settle the complexes, which were then dialyzed 3. Results and discussion
against distilled water (until the conductivity was
<300 lS cm1), powdered, ground, and stored in a desicca- 3.1. Characterization of adsorbents
tor prior to use (CFA–NaOH).
The raw coal fly ash contained SiO2 (52.5%), Al2O3
(27.9), CaO (6.27%), MgO (1.6%), Fe2O3 (6.3%), SO3
2.2. Adsorbate (0.79%), and LOI (‘‘loss on ignition’’ – the unburned car-
bon portion in the sample; 5.01%); it can be classified as
Cu(NO3)2 was obtained in analytical grade (Merck Co.) class F. Table 1 provides the characteristics of its porous
and used without further purification. structure. The BET surface area increased in the order
CFA-600 < CFA < CFA–NaOH. We observed the same
2.3. Equipment trends with regard to the mesopore surface area and the
pore volume. The presence of SiO2 (c-quartz) and
XRD patterns of the CFA samples were measured using Al2O3(mullite) was evident from the XRD patterns of the
a Thermo ARL X’TAR instrument and CuKa radiation three adsorbents (Fig. 1). In addition, CFA–NaOH also
(40 mA, 45 kV) over a range of 2h values from 10 to indicated the presence of hydroxysodalite, Pc type zeolite
80. The surface area and total pore volume of the CFA and Na-A zeolite [21].
samples were measured by N2 adsorption under 77 K using
a Micromeritics TRISTAR-3000 apparatus. CFA samples 3.2. Effect of pH
were outgassed with He for 16 h at 105 C prior to per-
forming the adsorption measurements. The chemical com- Fig. 2 indicates that the pH of the solution (2.0–11.0)
positions of the CFA samples were measured using a had a significant effect on the adsorption of Cu2+ at a coal
Hitachi Z-4100 inductively coupled plasma atomic emis- fly ash. At values of pH below 5.0, the adsorptions of Cu2+
sion spectroscopy (ICP-AES). The pH and conductivity on CFA, CFA-600, and CFA–NaOH were in the ranges
were determined using a JenCo 1671 pH meter. CFA-600 149.7–155.2, 109.6–121.6, 62.0–68.6 mg g1, respectively.
was treated at 600 C in a SmartLab TB50 furnace. The Although Cu2+ was removed completely in the presence
resulting suspensions were filtered and analyzed using a of each of the three adsorbents at pH above 6, we believe
Hitachi Z-5000 atomic absorption spectrophotometer that this feature resulted from precipitation of Cu2+ [22].
(AAS). Thus, we fixed the pH to 5.0 in this study.

2.4. Adsorption and kinetics studies 3.3. Effect of adsorbent dose

The Cu2+ adsorption isotherms in aqueous solutions Fig. 3 indicates that the maximum adsorptions capaci-
were obtained using the immersion method. Prior to use, ties of the three adsorbents followed the order
the adsorbents were dried at 105 C for 24 h to remove CFA > CFA-600 > CFA–NaOH at all three different tem-
moisture. Cu2+ solutions were prepared by dissolving peratures (30, 45, and 60 C).
Cu(NO3)2 in distilled water. The adsorption of Cu2+ was
studied after adding 0.1 g of an adsorbent into the aqueous 3.4. Effect of temperature
solution containing a desired Cu2+ concentration (50–
400 mg L1), adjusting the pH of the solution to 5, and We studied the adsorption of Cu2+ at three different
shaking with 200 rpm for 24 h at 30 C in a reciprocating temperatures (30, 45, and 60 C); Fig. 3 displays the results
shaker (DengYng Z-901). The equilibrium time was deter- for CFA, CFA-600, and CFA–NaOH, respectively. We
mined by dynamic adsorption studies and could be estab- found that their adsorption capacities followed the order
lished within 12–24 h; therefore, the contact time was 60 C > 45 C > 30 C.

Table 1
Pore structure data of the CFA samples, obtained through conventional analyzes of N2 adsorption isotherms
Adsorbent BET Micropore Mesopore Pore Micropore Average pore
surface area surface area surface area volume volume diameter
(m2 g1) (m2 g1) (m2 g1) (cm3 g1) (cm3 g1) (nm)
CFA 7.5 3.0 4.5 0.02 0 7.9
CFA-600 3.1 0.1 3.0 0.01 0 13.1
CFA–NaOH 13.9 3.0 10.9 0.05 0 13.6
T.-C. Hsu et al. / Fuel 87 (2008) 1355–1359 1357

Q
3.5. Adsorption isotherms
N
M Table 2 compares the adsorption capacities of various
N fly ash samples for Cu2+ by us and other studies. We find
H that our results are better than some studies. In addition,
Intensity

Q
Q
PM
QQ Q we used the Langmuir, Freundlich, and Dubinin–Kaga-
ner–Radushkevich (DKR) isotherms [23–25] to analyze
the adsorptions of Cu2+ onto the different adsorbents.
(c) The Langmuir isotherm can be represented as
(b) 1=Qe ¼ 1=Q0 þ 1=ðbQ0 C e Þ ð1Þ
(a) 1
where Qe is the amount adsorbed (mg g ), Ce is the equi-
10 20 30 40 50 60 70 80 librium concentration of the adsorbate (mg L1), and Q0
2θ and b are Langmuir constants. When 1/Qe was plotted
against 1/Ce, a straight line was obtained. Table 3 lists
Fig. 1. XRD patterns of (a) CFA, (b) CFA-600, and (c) CFA–NaOH.
Mineral abbreviations: M, mullite; Q, quartz; H, hydroxysodalite; N, Na-
the calculated Langmuir constants Q0 and b. Because the
A zeolite; P, Pc type zeolite. values of R2 were 0.908–0.988, it appears that these adsorp-
tion events fit the Langmuir isotherm quite well. The Fre-
undlich isotherm can be represented as
500
log Qe ¼ log K F þ 1=n logC e ð2Þ
where Qe is the amount adsorbed (mg g1), Ce is the equi-
Amount adsorbed (mg g-1)

400
librium concentration of the adsorbate (mg L1), and KF
and n are Freundlich constants. When log Qe was plotted
300 against log Ce, a straight line was obtained. Table 3 lists
CFA the values of the calculated Freundlich constants KF and
200
CFA-600
CFA-NaOH
n. Because the values of R2 were 0.907–0.993, it appears
that these adsorption events follow the Freundlich iso-
therm quite well. In each case, the value of n was greater
100
than one, indicating that adsorption was favorable. The
DKR equation can be represented as
0
1 2 3 4 5 6 7 8 9 10 11 12 ln Qe ¼ ln Qm  be2 ð3Þ
pH
where Qe is the amount adsorbed (mmol kg1), Qm
Fig. 2. Effect of pH on adsorptions of Cu by the three adsorbents 2+
(mmol kg1) is the DKR monolayer capacity, b (mol2 J2)
(initial concentration of Cu2+, 400 mg L1; coal fly ash concentration, is a constant related to the sorption energy, and e is the
1 g L1; T, 30 C; pH 5.0). Polanyi potential, which is related to the equilibrium con-
centration through the expression
e ¼ RT lnð1=CÞ; ð4Þ
350
o
CFA at 30 C
300
o
CFA at 45 C Table 2
Amount adsorbed (mg g-1)

Adsorption capacities of Cu2+ on various adsorbents


o
CFA at 60 C
o
CFA-600 at 30 C
250 o
CFA-600 at 45 C Adsorbent Adsorption capacity Temperature Reference
o
CFA-600 at 60 C
o
(mg g1) (C)
CFA-NaOH at 30 C
200 o
CFA-NaOH at 45 C CFA 178.5–249.1 30–60 This study
o
CFA-NaOH at 60 C CFA-600 126.4–214.1 30–60 This study
150
CFA–NAOH 76.7–137.1 30–60 This study
Fly ash 207.3 25 [16]
100
Fly ash-washed 205.8 25 [16]
Fly ash-acid 198.5 25 [16]
50
Bagasse fly ash 2.3–2.4 30–50 [4,16]
Fly ash 1.7–8.1 – [16]
0
0 100 200 300 400
Fly ash 1.4 20 [16,20]
Fly ash + wollastonite 1.2 30 [16,20]
-1
Equilibrium concentration (mg L ) Fly ash (I) 0.34–1.4 20 [16]
Fly ash (II) 0.09–1.3 20 [16]
Fig. 3. Adsorption isotherms of Cu2+ CFA, CFA-600, and CFA–NaOH
Fly ash 0.63–0.81 25 [16]
at various temperatures (initial concentrations of Cu2+, 50–400 mg L1;
Fly ash 0.76 32 [16]
coal fly ash concentration, 1 g L1; pH 5.0).
1358 T.-C. Hsu et al. / Fuel 87 (2008) 1355–1359

Table 3
Langmuir, Freundlich, and DKR constants for CFA, CFA-600, and CFA–NaOH
Adsorbent Temp (C) Langmuir Freundlich DKR
1 1
Q0 (mg g ) b (L mg ) R2
n KF R 2
b (mol2 J2) E (kJ mol1) R2
8
CFA 30 163.9 0.192 0.950 19.0 121.1 0.907 –2.0 · 10 5.1 0.937
45 185.2 0.346 0.964 24.9 148.2 0.985 –6.2 · 109 9.0 0.932
60 242.9 0.461 0.908 24.9 197.7 0.992 –5.4 · 109 9.6 0.972
CFA-600 30 138.9 0.047 0.955 7.8 63.5 0.983 –8.9 · 108 2.4 0.912
45 178.6 0.107 0.960 13.7 117.1 0.937 –3.3 · 108 3.9 0.949
60 232.6 0.213 0.979 17.1 169.7 0.993 –1.3 · 108 6.1 0.958
CFA–NaOH 30 84.0 0.016 0.984 4.5 19.3 0.969 –2.7 · 107 1.3 0.981
45 91.7 0.036 0.988 4.8 26.0 0.991 –2.4 · 107 1.5 0.976
60 144.9 0.047 0.939 9.8 76.5 0.975 –7.7 · 108 2.5 0.903

where T is the temperature and C is the equilibrium con- and spontaneous. The decrease of DG upon increasing
centration of Cu2+ in solution. When ln Qe was plotted the temperature indicates that the process is favored at high
against e2, a straight line was obtained. We calculated the temperatures. The positive values of DH and DS indicate
value of b and it is related to the sorption energy, E, that the process is endothermic and aided by increased ran-
through the following relationship: domness for each sample.
1=2
E ¼ 1=ð2bÞ ð5Þ
3.7. Kinetic adsorption studies
Table 3 provides the DKR parameters for the adsorp-
tions of the three adsorbents at various temperatures. The results of the dynamic analysis were performed by
Because the values of R2 were 0.903–0.981, it appears that the pseudo-first-order and pseudo-second-order rate equa-
the adsorptions of Cu2+ on the three adsorbents followed tions [27]. The two models are represented by Eqs. (9), and
the DKR isotherm quite well. The values of E (1.3– (10), respectively
9.6 kJ mol1) are those expected for an ion-exchange mech-
anism [26]. lnðQe  Qt Þ ¼ ln Qe  k 1 t ð9Þ

t=Qt ¼ ½1=ðk 2 Q2e Þ þ ð1=Qe Þt ð10Þ


3.6. Thermodynamic studies

The thermodynamic parameters can be calculated by the where Qt is the amount (mg g1) of material adsorbed at
following equations [23]: time t, Qe is the adsorption capacity (mg g1) at equilib-
rium, k1 is the rate constant (min1) of the pseudo-first-or-
DG ¼ RT ln b0 ð6Þ der model, and k2 is the rate constant (g mg1 min1) of
 pseudo-second-order model.
ln b2 =b1 ¼ ðDH =RÞ½ðT 1  T 2 Þ=T 2 T 1  ð7Þ
DS  ¼ ðDH   DG Þ=T ð8Þ Table 4 provides the kinetic parameters for the adsorp-
tions of Cu2+ on the three adsorbents at various tempera-
where b 0 , b2, and b1 are the Langmuir constants at T, T2, tures. For the pseudo-first-order model, the values of R2
and T1, respectively. In Table 4, the negative value of were lower than those obtained using the pseudo-second-
DG indicates that the adsorption process is favorable order model (shown in Fig. 4), confirming the pseudo-

Table 4
Thermodynamic and kinetic parameters for CFA, CFA-600, and CFA–NaOH
Adsorbent Temp. (C) Thermodynamic parameters Pseudo-first-order model Pseudo-second-order model
1 1 1 1 1
DG (kJ mol ) DH (kJ mol ) DS (J mol K ) K1 (1 min ) R 2
K2 (g mg1 min1) R2
3 3
CFA 30 23.7 3.8 · 10 0.803 2.68 · 10 0.997
45 26.5 24.3 158.9 7.0 · 104 0.620 2.25 · 103 0.991
60 28.5 1.9 · 103 0.771 2.30 · 103 0.999
CFA-600 30 20.2 3.3 · 103 0.782 4.82 · 103 0.999
45 23.4 42.3 206.2 1.9 · 103 0.957 2.82 · 103 0.977
60 26.4 2.2 · 103 0.844 1.01 · 103 0.995
CFA–NaOH 30 17.5 3.5 · 103 0.987 6.81 · 103 0.997
45 20.4 32.0 164.0 2.5 · 103 0.863 6.04 · 103 0.974
60 22.4 2.6 · 102 0.940 1.08 · 102 0.970
T.-C. Hsu et al. / Fuel 87 (2008) 1355–1359 1359

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