This article was downloaded by:[Pehlivan, Erol]

On: 24 May 2008

Access Details: [subscription number 793295377]
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Energy Sources, Part A: Recovery,

Utilization, and Environmental Effects
Publication details, including instructions for authors and subscription information:
http://www.informaworld.com/smpp/title~content=t713770930
Application of Fly Ash and Activated Carbon in the
Removal of Cu2+ and Ni2+ Ions from Aqueous Solutions
E. Pehlivan a; S. Cetin a
a
Department of Chemical Engineering, Sel uk University, Konya, Turkey

Online Publication Date: 01 August 2008

To cite this Article: Pehlivan, E. and Cetin, S. (2008) 'Application of Fly Ash and
Activated Carbon in the Removal of Cu2+ and Ni2+ Ions from Aqueous Solutions',
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 30:13,
1153 — 1165
To link to this article: DOI: 10.1080/15567030701258220
URL: http://dx.doi.org/10.1080/15567030701258220

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf

This article maybe used for research, teaching and private study purposes. Any substantial or systematic reproduction,
re-distribution, re-selling, loan or sub-licensing, systematic supply or distribution in any form to anyone is expressly
forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents will be
complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses should be
independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or
arising out of the use of this material.
 Energy Sources, Part A, 30:1153–1165, 2008
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

Copyright © Taylor & Francis Group, LLC

ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567030701258220

Application of Fly Ash and Activated Carbon in

the Removal of Cu2C and Ni2C Ions from
Aqueous Solutions

E. PEHLIVAN1 and S. CETIN1

1
Department of Chemical Engineering, Selçuk University, Konya, Turkey

Abstract The main objective of this study was to remove Cu2C and Ni2C ions from
aqueous solution by using fly ash, an industrial solid waste of the sugar industry and
commercial activated carbon at equilibrium, which follows Langmuir and Freundlich
adsorption isotherms. In order to identify influential parameters and to evaluate their
interactions, effects of time, pH, initial metal concentration, and amount of adsorbent
were studied, and the results were compared with those of activated carbon under the
same experimental conditions. Adsorption studies were performed in a time interval
(1–240 min), at various pH values (2.0–8.0) at 25ıC and at metal concentrations of
1–10  1 4 M using different amounts of adsorbent (1–12 g/L). The equilibrium time
was fixed at 60 min in the case of Cu2C and Ni2C , and 8 g/L of fly ash and 6 g/L
activated carbon was sufficient for the optimum removal of both the metal ions. The
sorption of metal ions increased with an increase of pH, and maximum removal was
obtained at 5.0 for fly ash with 97.2% and 78.2% removal for Cu2C and Ni2C ions,
respectively. For AC, on the other hand, maximum removal was obtained at 4.0 for
Cu2C and 6.0 for Ni2C with 95.0% and 63.0% removal, respectively. The adsorption
capacities are 7.0 mg/g for Cu2C , 5.9 mg/g for Ni2C for fly ash, and 6.9 mg/g for
Cu2C, 5.4 mg/g for Ni2C for activated carbon. The orders of adsorption of heavy
metal ions for fly ash and activated carbon change in the order of Cu2C > Ni2C
and Cu2C > Ni2C , respectively. The fly ash was found to be a metal adsorbent as
effective as commercial activated carbon.

Keywords activated carbon, adsorption, copper and nickel, fly ash, solid waste
utilization, sorption isotherms

Introduction
The rapid increase in population and economic growth has led to an increase in energy
demand. Coal reserves are distributed worldwide, and coal is now known to be the most
stable and available energy source. Coal and pulverized coal are used today worldwide
for energy production in thermal power stations and household stoves in developing
countries. Co-combustion of coal products has considerable importance from a technical
and environmental point of view. However, utilization of coal as an energy source involves
the generation of a great amount of coal ash and fly ash. The recycling rate of the ash
is rather low. The management of fly ash produced by coal-fired power plants remains
a major problem in many parts of the world. Although significant quantities are being

Address correspondence to Professor Erol Pehlivan, Selçuk University, Department of

Chemical Engineering, 42079 Konya, Turkey. E-mail: erolpehlivan@gmail.com

1153
 1154 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

used in a range of applications, and particularly as a substitute for cement in concrete,

large amounts are not used, and this requires disposal (Kikuchi, 1999).
Metals and other inorganic compounds are used extensively in industry. Rate of
anthropogenic emissions is typically much greater than the natural cycling of these
elements. Heavy metals discharged in wastewaters can be toxic to aquatic life and cause
natural waters to be unsuitable as potable water sources. Heavy metals are nowadays
among the most important pollutants in source and treated water, and are becoming a
severe public health problem. Research is needed to develop new alternative applications
that can further exploit coal fly ash, which needs to be increasingly regarded as a raw
material, with potential for processing into new products rather than a waste. A number of
workers have used different adsorbent systems, developed from various industrial waste
materials, for the removal of heavy metals (Gupta et al., 2003; Bayat, 2002a; Lin and
Chang, 2001; Rathore et al.,1985; Ferraiolo et al., 1990; Aly and Daifullah, 1998; Gupta
and Ali, 2000). There still exists a need to develop a low cost and efficient adsorbent for
the removal of toxic metal ions from wastewater.
Various treatment technologies have been developed for the removal of heavy metals
from water. The commonly used procedures for removing metal ions from effluents
include chemical precipitation, lime coagulation, ion exchange, electrodialysis, reverse os-
mosis membrane filtration, electro-winning, solvent extraction, and common adsorption,
the latter process being a more useful method for the metal removal than other processes
(Apak et al., 1998; Juang and Shiau, 2000; Gode and Pehlivan, 2003, 2005, 2006;
Pehlivan et al., 2004; Yan and Viraraghavan, 2001). These techniques are economically
expensive and have disadvantages like incomplete metal removal, high reagent and energy
requirements, and generation of toxic sludge or other waste products that require disposal.
Efficient and environmentally friendly methods are thus needed to be developed to reduce
heavy metal content. It is evident that fly ash as coal combustion residue has a great
potential in environmental applications.
Fly ash is an interesting alternative to replace activated carbon or zeolite for ad-
sorption either in air or water pollution treatment. Therefore, there is an increasing trend
for the development of new and especially cheap adsorbents for the removal of heavy
metals from wastewaters. Some research articles reported that alkaline fly ash can serve
as a stabilizer or binding reagent for the fixation of heavy metal and nutrients contained
in hazardous wastes and organic wastes (Demirbas et al., 2006; Gupta et al., 1994;
Lin and Hsin, 1996; Shende et al., 1994; Singer and Berkgaut, 1995). Gupta’s research
group conducted a series of investigations on fly ash adsorption for heavy metals. They
measured the changes in toxicity and heavy metals in a municipal wastewater treatment
plant effluent on treatment with fly ash. The effluent after treatment with fly ash for 4 h
showed a significant reduction in toxicity, Cu and Pb contents (Gupta and Torres, 1998).
Activated carbon is widely used as an adsorbent in industry due to its high adsorption
capacity. This capacity is related to the pore structure and chemical nature of the carbon
surface in connection with preparation conditions (Roy and Griffm, 1982; Mattson and
Mark, 1971).
In the past, fly ash produced from coal combustion was simply taken up by flue
gases and dispersed into the atmosphere. This created significant environmental concerns
and health risks. These days, most power plants are required by law to reduce their
fly ash emissions to less than 1% of ash produced. The remainder is collected using
electrostatic precipitators or filter bags. This collected ash is either sold for use in the
cement/construction industry or disposed of in ash ponds or landfills. Fly ash has been
screened in this regard to serve as a versatile and cost-effective sorbent for heavy metals,
 Application of Fly Ash 1155
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

the ability of which has also been demonstrated in the literature (Lin and Hsin, 1996;
Sen and De, 1987; Rovatti et al., 1988; Sell et al., 1994), and some information on the
sorption and the chemical constituents of fly ashes obtained from various sources has been
reported (Gupta et al., 1994; Lin and Hsin, 1996; Shende et al.,1994; Mott and Weber,
1992). However, the sorption efficiency of toxic metal ions using fly ashes as sorbents
varied, according to the characteristics of the fly ash. Fly ash consists of inorganic,
incombustible matter present in the coal that has been fused during combustion into a
glassy, amorphous structure. Coal can range in ash content from 2–30%, and of this
around 70–85% becomes fly ash. The remaining is called bottom ash and is not lifted up
by the flue gases. Since the particles solidify while suspended in the exhaust gases, fly
ash particles are generally spherical in shape and range in size from 1–150 m. All fly
ash contains the same basic chemical elements but in different proportions. These consist
mostly of silicon dioxide (SiO2 ), aluminum oxide (Al2 O3 ), and iron oxide (Fe2 O3 ), with
smaller amounts of sulfur, magnesium, alkalines, and tracers of many other elements
(Vincini et al., 1994; Héquet et al., 2001).
For many years, fly ash, the inorganic residue from the combustion of powdered
coal has been considered a waste material, the production of which has continued to
increase, and hence, the motivation to look for possible industrial applications. The sugar
industry is one of the most important agro-based industries in Turkey and has tons of fly
ash occur as the result of burning young lignites for obtaining energy. The fly ash, an
industrial solid waste generated from the burning of lignite in the sugar industry, causes
a great disposal problem. In the present study, the adsorption of Cu2C and Ni2C ions on
fly ash particles and commercially available activated carbon was evaluated under various
conditions such as pH, heavy metal concentrations, contact time, and sorbent dosages
through isotherm studies.

Experiment

Materials
Heavy metal solutions (divalent cations of Cu2C and Ni2C) were prepared in stock
solutions from the corresponding nitrate salts. All chemicals used were of analytical
grade and were obtained from Merck (Darmstadt, Germany). All working solutions
were prepared by diluting the stock solutions with deionized water. pH adjustments
of these solutions were made by using 0.1 M HCl and 0.1 M NaOH solutions, and the
measurements were performed with Orion 900S2 Model pH meter (Thermo Scientific,
Ankara, Turkey). Constant ionic strength 0.1 M NaNO3 was used in all experiments. All
solutions were stirred by using the Chiltern Hotplate Magnetic Stirrer HS 31 (Chiltern,
Auckland, New Zealand). The concentrations of metal ions were determined by atomic
absorption spectrometer (AAS) Unicam 929 Model AAS (Cambridge, UK).

Fly Ash and Activated Carbon

The fly ash used in the experiments was collected as a solid waste material of the
sugar industry from Konya Sugar Factory, Turkey. They are formed as the result of the
combustion of lignite from the steam boiler. For comparison, a commercially activated
carbon obtained from Merck Company (Darmstadt, Germany) was used. The fly ash
obtained from burning of young brown coal was dried and sieved into different fractions
(100–150 m). The primary components of fly ash are silica (SiO2 ), alumina (Al2 O3 ),
 1156 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

Table 1
Basic characteristic of activated carbon
(Merck)

Parameter value AC (Merck)

Bulk density, g/ml 0.11

Ash content, % 1.6
pH, 1% solution 7.9
Moisture content, % 10.9
Surface area (m2 /g) BET 921
Solubility in water, % 0.95
Solubility in 0.25 M HCl, % 1.14
Decolorizing power, mg/g 18.3
Iodine number, mg/g 520
Particle size, mm 0.5–2.2

and iron oxides (Fe2 O3 ), with varying amounts of carbon, calcium, magnesium, and
sulphur. Tables 1 and 2 show the chemical composition of the activated carbon and the
fly ash samples used in this study. Pore volumes and average pore diameter greater than
20 Å were determined by mercury porosimeter up to 2,000 kg/cm2 using a Carlo Erba
model 200. The surface area of the fly ash was measured with a surface area apparatus
(BET method). The specific surface area of the fly ash was found to be 0.450 m2 /g by
BET method.

Adsorption Experiments
The fly ash was baked at 500ıC for 2 h to remove the carbon residue. The sorption
process was carried out in batch sorption experiments in the single species system.
An electrolyte consisting of 0.1 M NaNO3 solution was introduced. To determine the
contact time necessary for adsorption, 25 mL of solution containing 1  10 3 M metal
ion and 0.2 g of fly ash were stirred at 200 rpm at varying time intervals (0–240 min)

Table 2
Chemical composition of
the fly ash (Ermenek)

Constituent wt%

SiO2 46.90
Al2 O3 18.80
Fe2 O3 9.87
CaO 10.10
MgO 3.50
Na2 O 1.10
K2 O 0.60
Others 6.50
 Application of Fly Ash 1157
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

in the pH range of 3.0–8.0 at room temperature. At the end of predetermined time

intervals, the contents of the solutions filtered through 0.45 m Whatman filter paper
using a vacuum pump, and the filtrate was analyzed with Unicam 929 Model Atomic 133
Absorption Spectrometer (AAS) at wavelengths of 324.8 and 232.0 nm for Cu2C and
Ni2C , respectively. The adsorption experiments of these two metal ions were conducted
using the same procedure with respect to pH in the solution (3.0–8.0), initial metal
concentration (1  10 4 to 1  10 3 M), amount of adsorbent (0.025–0.300 g). Isotherms
were obtained by adsorbing different concentrations of metal ions. Average values of
three replicates were taken for each determination.
Adsorption experiments were also conducted using a commercially available acti-
vated carbon to compare the ability of both adsorbents in the removal of Cu2C and Ni2C
from aqueous solutions. The same procedures for activated carbon were used as in the
adsorption experiments with fly ash.

Results and Discussion

Fly ash is composed of solid components. They exhibit low water reactivity but possess
surface electric charge (adsorb metal cations, e.g., Cu, Ni, Zn, etc.) and are made of
SiO2 , Al2 O3 , Fel2 O3 , and TiO2 . The chemical behavior and release of heavy metals to
water is highly interrelated to the surface electric properties of oxides. The other group
in the fly ash includes highly water reactive components. Generally, these groups include
oxides of Ca2C , Mg2C , Ba2C , KC , NaC , as well as gypsum (CaSO4
2H2 O) and sulfite
(SO3 ). Fly ashes from high rank coal are low in Ca2C and Mg2C ; hence, the fly ashes
retain little sulfate (Roy and Griffm, 1982; Adriano et al., 1980).

Effect of Contact Time

There is a relationship between adsorption capacity of fly ash and its chemical con-
stituents, such as mineral oxides (aluminum, calcium, and silica oxides) and carbon. Fly
ash and activated carbon remove metal ions by absorbing them inside their sponge-like
structure and/or adsorbing them with chemical bonds. The process of adsorption is also
influenced by the length of time that the fly ash or activated carbon is in contact with
the contaminant in the aqueous solution. Increasing contact time allows greater amounts
of contaminant to be removed from the aqueous solution.
Initial batch studies were conducted to assess the time required to achieve equilibrium
for Cu2C and Ni2C removal. The effect of contact time on the adsorption experiments is
shown in Figures 1a and 1b. Studies on the rate of sorption of 25 mL, 1  10 3 M Cu2C
and Ni2C ions by adsorbents indicated that the process was quite rapid, and maximum
adsorption occurred within the first hour of contact. Therefore, the equilibrium time was
fixed at 60 min in the case of Cu2C and Ni2C in all further experiments.

Effect of pH
Usually, the pH of the fly ash solution determines the predominant mechanism. This
study is focused on the precipitation of Cu2C and Ni2C ions as metal hydroxides by
fly ash, which necessitates a certain pH range of the solution. It is often suggested that
the tendency of metal cations to adsorb to oxide surfaces is highly correlated with their
tendency to undergo hydrolysis reactions in solution. Metal cations in aqueous solutions
 1158 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

(a)

(b)

Figure 1. (a) Effect of contact time on the sorption of Cu2C and Ni2C ions by fly ash (FA)
(adsorption conditions: initial concentration of metal ions, 1  10 3 M; amount of adsorbent, 0.2 g;
volume of adsorption medium, 25 mL; temperature, 25 ˙ 1ıC; stirring rate, 200 rpm; pH 5.0 and
5.5). (b) Effect of contact time on the sorption of Cu2C and Ni2C ions by activated carbon (AC)
(adsorption conditions: initial concentration of metal ions, 1  10 3 M; amount of adsorbent, 0.2 g;
volume of adsorption medium, 25 mL; temperature, 25 ˙ 1ı C; stirring rate, 200 rpm; pH 4.0
and 6.0).

hydrolyze according to the generalized expression (Eq. (1)) for divalent metal ions (Ayala
et al., 1998).
M2C.aq/ C nH2 O D M.OH/2n n
C nHC (1)

SiO2 in fly ash could adsorb either positive or negative contaminants depending on the
pH of the solution. As a result, at low pH on the silica surface is positively charged
and at high pH values it is negatively charged. As long as the solubility product of
the metal hydroxides is constant, the metal solubility decreases as the pH increases and
 Application of Fly Ash 1159
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

increases with complex formation. As a result of these effects, the metal ion concentration
in the aqueous solution decreases until a certain pH value is reached and increases
thereafter as the complex formation becomes important. The CaO content of the fly
ash is more effective in determining the alkalinity of the solution than their total basic
constituent’s content. Therefore, the Cu2C and Ni2C removal capacities of the fly ash
samples are directly proportional to their CaO content. The removal of pollutants from
aqueous solution by adsorption is highly dependent on the pH of the solution, which
affects the surface charge of the adsorbent, the degree of ionization, and speciation of
the adsorbate (Bayat, 2002b). In general, fly ash has a hydrophilic surface and porous
structure. The mechanisms of the interaction between metal and adsorbent are a function
of pH and are found to be precipitation, adsorption, and or ion exchange. So the removal
of Cu2C and Ni2C ions as a function of hydrogen ion concentration was examined over
a pH range of 2.0–8.0, and the graphs are shown in Figures 2a and 2b for fly ash and
activated carbon. It is also quite clear from these data that the fly ash exhibits a greater
potential for Cu2C and Ni2C ion adsorption at the pH 5.0 values tested. In the case of
the activated carbon adsorption of Cu2C and Ni2C ion, maximum sorption is obtained at
around pH 4–6.
The Figures 2a and 2b clearly show that the adsorption of metal ions by fly ash is
strongly pH dependent, as one would expect due to variable charge surfaces of the fly
ash metal oxides. It can be seen from Figure 2a that sorption of metal ions increases with
an increase of pH and maximum removal was obtained at 5.0 for fly ash with 97.2% and
78.2% removal for 25 mL, 110 3 M Cu2C and Ni2C ions, respectively. The equilibrium
pH 5.0 was considered as optimum pH in case of the removal of both metal ions for
further studies. This result for fly ash may be due to the functional oxidized groups (SiO2 ,
Al2 O3 , and Fe2 O3 ) present on the surface of it. Since fly ash contains abundant alkaline
materials, such as CaO and MgO, the hydroxide ion (–OH) is liberated, raising pH during
adsorption. In such cases, Cu2C and Ni2C ions may then form an insoluble product of
Cu(OH)2 (s). For activated carbon, on the other hand, maximum removal was obtained at
4.0 for Cu2C and 5.0 for Ni2C with 95.0% and 63.0% removal, respectively. The effect of
sodium nitrate concentration on metal uptake worked with 0.1 M NaNO3 concentration,
and the electrostatic attraction at low ionic strength appeared to play a negligible role in
the removal of Cu2C and Ni2C ion for both adsorbents in the experiments.

Effect of Amount of Adsorbent

The adsorption capacity of Cu2C and Ni2C ion on to the surface of fly ash increased with
increasing carbon content and adsorbent dosage. The effect of amount of adsorbent on the
sorption of Cu2C and Ni2C is depicted in Figures 3a and 3b. It is seen that the sorption
percentage of metal ions increased with the increase in the amount of both adsorbents.
In the case of both metal ions, significant increase in the sorption was observed when
the amount of adsorbent increased from 1 to 8 g/L, and any additional amount of sorbent
did not influence further removal of Cu2C and Ni2C ions from 8 to 12 g/L. As a result,
8 g/L of fly ash and 6 g/L activated carbon is sufficient for the optimum removal of both
the metal ions.

Adsorption Isotherms
The sorption data of Cu2C and Ni2C ions have been correlated with Langmuir and
Freundlich models (Eqs. (2) and (3)).
 1160 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

(a)

(b)

Figure 2. (a) Effect of pH on the sorption of Cu2C and Ni2C ions by fly ash (FA) (adsorption
conditions: initial concentration of metal ions, 1  10 3 M; amount of adsorbent, 0.2 g; volume
of adsorption medium, 25 mL; temperature, 25 ˙ 1ı C; stirring rate, 200 rpm). (b) Effect of pH
on the sorption of Cu2C and Ni2C ions by activated carbon (AC) (adsorption conditions: initial
concentration of metal ions, 110 3 M; amount of adsorbent, 0.2 g; volume of adsorption medium,
25 mL; temperature, 25 ˙ 1ıC; stirring rate, 200 rpm).

Langmuir equation:
Ce Ce 1
D C (2)
qe Q0 Q0 b

where Ce is the equilibrium concentration (mg/L), qe the amount of adsorbed material

at equilibrium (mg/g), b the “affinity” parameter or Langmuir constant (L/mg), and Q0
the “capacity” parameter (mg/g) (Gode and Pehlivan, 2003, 2005, 2006).
 Application of Fly Ash 1161
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

(a)

(b)

Figure 3. (a) Effect of amount of adsorbent on the sorption of Cu2C and Ni2C ions by fly ash
(FA) (adsorption conditions: initial concentration of metal ions, 1  10 3 M; volume of adsorption
medium, 25 mL; temperature, 25 ˙ 1ı C; stirring rate, 200 rpm; pH 5.0 and 5.5). (b) Effect of
amount of adsorbent on the sorption of copper and nickel by activated carbon (AC) (adsorption
conditions: initial concentration of metal ions, 1  10 3 M; volume of adsorption medium, 25 mL;
temperature, 25 ˙ 1ıC; stirring rate, 200 rpm; pH 4.0 and 6.0).

Freundlich equation:
q D Kf
Cen (3)

where n is Freundlich constant and Kf is the adsorption coefficient, q is the weight

adsorbed per unit weight of adsorbent, and Ce is the equilibrium metal concentration in
fluid. Taking logs and rearranging Eq. (3):

log q D log Kf C n log Ce (4)

 1162 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

(a)

(b)

Figure 4. (a) Effect of initial concentration on the sorption of copper and nickel by fly ash (FA)
(adsorption conditions: initial concentration of metals, 1–10  10 4 M; amount of adsorbent, 0.2 g;
volume of adsorption medium, 25 mL; temperature, 25 ˙ 1ıC; stirring rate, 200 rpm; pH 5.0 and
5.5). (b) Effect of initial concentration on the sorption of copper and nickel by activated carbon
(AC) (adsorption conditions: initial concentration of metals, 1–10  10 4 M; amount of adsorbent,
0.2 g; volume of adsorption medium, 25 mL; temperature, 25 ˙ 1ı C; stirring rate, 200 rpm; pH 4.0
and 6.0).

The data in Figures 4a and 4b show the potential of the fly ash and activated carbon
to adsorb Cu2C and Ni2C ions. Regression values presented in Table 3 indicate that the
adsorption data for Cu2C and Ni2C ion removal fit well to the Freundlich isotherm for
fly ash. The Langmuir isotherm equation provided an excellent fit to the equilibrium
sorption data, giving correlation coefficients of 0.95 on the activated carbon for Ni2C
ion, but the Freundlich isotherm equation was applicable for copper ion adsorption on
the activated carbon. The values of constants indicate favorable conditions for adsorp-
tion. The Langmuir model was more applicable than the Freundlich model, since the
 Application of Fly Ash 1163
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

Table 3
Parameters of Langmuir and Freundlich isotherms for sorption of Cu2C and Ni2C ions
on fly ash and activated carbon

Freundlich isotherm Langmuir isotherm

k n R2 Qoa bb R2

FA Cu(II) 5.15 1.71 0.99 0.1820 1,121.59 0.92

Ni(II) 4.22 1.76 0.99 0.1612 1,241.06 0.98
AC Cu(II) 1.89 1.88 0.98 0.1242 847.74 0.92
Ni(II) 1.19 1.92 0.92 0.1039 576.09 0.97
a mmol/g adsorbent; b 1/mmol.
Note: k, Qo mmol/g resin (capacity of ion-exchanger), R2 : Correlation coefficient.

correlation coefficients for the former were higher for the adsorption of Cu2C ion on
the activated carbon. The Langmuir-type model presupposes homogeneity of the sorbing
surface, with no interactions involving uniform energies of sorption on the surface and no
transmigration of metal cations in the plane of the surface. These data clearly demonstrate
that the fly ash exhibits greater potential as well as the activated carbon to adsorb heavy
metals at higher pH values.
The ionic diameters of the heavy metals used change in the order of Ni2C > Cu2C.
Since the activated carbon used is a microporous adsorbent, heavy metals penetrate easily
into these pores when the ionic diameter becomes small. The Irving-Williams series, that
is the order of complex stabilities of heavy metal ions used as adsorbate is given as
Ni2C < Cu2C (Pandey et al., 2000). According to this order, Ni2C must be the least
adsorbed and Cu2C must be the most adsorbed, because the heavy metal whose complex
is stable will be present in the complex at higher levels, and this will cause the complex
to be adsorbed more. Our experimental results are consistent with this. As can be seen
in Table 3, n constants of the heavy metal ions adsorbed change in the order of Cu2C
> Ni2C. It is seen that the n constants obtained in the Irving-Williams series are high
because the stable complex formed increases the ability of the heavy metal to be adsorbed
and causes the n constant to be high. This is compatible with our experimental results.
The orders of adsorption of heavy metal ions for the fly ash and activated carbon change
in the order of Cu2C > Ni2C and Cu2C > Ni2C, respectively.

Desorption Studies
The reversibility of the process was also investigated. The desorption of Cu2C and Ni2C
ion, which were previously deposited on the fly ash and activated carbon back into the
deionized water, was observed only in acidic pH values during a one-day period and was
generally rather low. The desorption is nowhere near quantitative and in this experiment
(first wash) varied between 3.8 and 6.0% of the metal for 1.0 g of fly ash and 1.8 and
2.5% of the metal for 1.0 g of activated carbon. The second wash removed between 1.3
and 1.8% of the metal for 1.0 g of fly ash and 1.0 and 1.4% of the metal for 1.0 g of
activated carbon. The total loss amount of metal ion released from the fly ash varied
from 5.1 to 7.8% for 1.0 g of fly ash and 2.8 to 3.9% for 1.0 g of activated carbon.
 1164 E. Pehlivan and S. Cetin
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

Conclusion
In this study, tests were performed to evaluate the use of fly ash particles obtained from
the burning of brown coal as an adsorbent for Cu2C and Ni2C ions. It was found that that
Cu2C and Ni2C ions were adsorbed onto the fly ash and activated carbon rapidly (within
the first 40–60 min), while equilibrium was reached in 80–100 min for both metal ions.
Around pH 5, where the influence of precipitation is negligible, the removal for metal
ions was 63–97%, and the percent removal of the heavy metal ions slightly increased
as the pH increased. It was found that the percentage removal of heavy metals was
dependent on the pH of the solution. The removal was high even when small amounts
of fly ash were used at neutral pH conditions (pH 5–8).
The adsorption capacities are 7.0 mg/g for Cu2C, 5.9 mg/g for Ni2C for fly ash and
6.9 mg/g for Cu2C , 5.4 mg/g for Ni2C for activated carbon. More than 67% of studied
cations were removed by fly ash and 63% activated carbon, respectively, from aqueous
solution in a single step.
The adsorption data corresponded well with the Freundlich isotherm. It was postu-
lated that when the adsorption was intense, the surface of the fly ash was covered with
heavy metal ions, resulting in the decreased adsorption rate. The CaO content of the fly
ash sample is more effective in determining the alkalinity of the solution than their total
basic constituent’s content. Therefore, the Cu2C and Ni2C ion removal capacities of the
fly ash samples are directly proportional to their CaO contents.
It can be concluded that it is necessary for various adsorbents to be tested because of
their different surface properties in the determination of optimum conditions in terms of
adsorbents for removal of the heavy metals by adsorption from aqueous solution without
changing the conditions. The reason for this is that a substance that is a good adsorbent
for one adsorbate may not be a good adsorbent for another. The results of the tests using
aqueous solution showed that fly ash and activated carbon were effective in the removal
of Cu2C and Ni2C ions in aqueous solution. The data obtained from the adsorption studies
will be useful for fabrication and design of wastewater treatment plants using fly ash as
sorbents, where standard material such as activated carbon was not available.

Acknowledgment
This study was supported by the Scientific Research Foundation (BAP in Turkish initials)
of Selçuk University (Project No. 2003/028).

References
Adriano, D. C., Page, A. L., Elseewi, A. A., Chang, A. C., and Straughan, I. 1980. Utilization
and disposal of fly ash and other coal residues in terrestrial ecosystems: A review. J. Environ.
Qual. 9:333–344.
Aly, H. M., and Daifullah, A. A. M. 1998. Potential use of bagasse pith for the treatment of
wastewater containing metals. Adsorp. Sci. Technol. 16:33–38.
Apak, R., Tütem, E., Hügül, M., and Hizal, J. 1998. Heavy metal cation retention by unconventional
sorbents (red muds and fly ashes). Water Res. 32:430–440.
Ayala, J., Blanco, F., Garcia, P., Rodriguez, P., and Sancho, J. 1998. Asturian fly ash as a heavy
metals removal material. Fuel 77:1147–1154.
Bayat, B. 2002a. Combined removal of zinc(II) and cadmium(II) from aqueous solutions by
adsorption onto high-calcium Turkish fly ash. Water, Air, Soil Pollut. 136:69–92.
Bayat, B. 2002b. Comparative study of adsorption properties of Turkish fly ashes II. The case of
chromium (VI) and cadmium (II). J. Hazard. Mater. B95:275–290.
 Application of Fly Ash 1165
Downloaded By: [Pehlivan, Erol] At: 09:09 24 May 2008

Demirbas, A., Arslan, G., and Pehlivan, E. 2006. Recent studies on activated carbons and fly ashes
from Turkish resources. Energy Sources, Part A 28:627–638.
Ferraiolo, G., Zilli, M., and Converti, A. 1990. Fly ash disposal and utilization. J. Chem Technol.
Biotechnol. 47:281–306.
Gode, F., and Pehlivan, E. 2003. A comparative study of two chelating ion-exchange resins for the
removal of chromium(III) from aqueous solution. J. Hazard. Mater. B100:231–243.
Gode, F., and Pehlivan, E. 2005. Adsorption of Cr(III) ions by Turkish brown coals. Fuel Process.
Technol. 86:875–884.
Gode, F., and Pehlivan, E. 2006. Chromium(VI) adsorption by brown coals. Energy Sources 28:447–
457.
Gupta, G. S., Prasad, G., and Singh, V. N. 1994. Removal of chrome dye from aqueous solutions
by mixed adsorbents: Fly ash and coal. Water Res. 24:45–50.
Gupta, G., and Torres, N. 1998. Use of fly ash in reducing toxicity of and heavy metals in wastewater
effluent. J. Hazard. Mater. 57:243–248.
Gupta, V. K., and Ali, I. 2000. Utilization of bagasse fly ash (a sugar industry waste) for the
removal of copper and zinc from wastewater. Sep. Purif. Technol. 18:131–140.
Gupta, V. K., Jain, C. K., Ali, I., Sharma, M., and V. K. Saini. 2003. Removal of cadmium and
nickel from wastewater using bagasse fly ash a sugar industry waste. Water Res. 37:4038–4044.
Héquet, V., Ricou, P., Lecuyer, I., and Le Cloirec, P. 2001. Removal of Cu2C and Zn2C in aqueous
solutions by sorption onto mixed fly ash. Fuel 80:851–856.
Juang, R. S., and Shiau, R. C. 2000. Metal removal from aqueous solutions using chitosan-enhanced
membrane filtration. J. Membr. Sci. 165:159–167.
Kikuchi, R. 1999. Application of coal ash to environmental improvement transformation into
zeolite, potassium fertilizer, and FGD absorbent. Resour., Conserv. Recycling 27:333–346.
Lin, C. J., and Chang, J. E. 2001. Effect of fly ash characteristics on the removal of Cu(II) from
aqueous solution. Chemosphere 44:1185–1192.
Lin, C. F., and Hsin, H.C. 1996. Resource recovery of waste fly ash:synthesis of zeolite-like
materials. Environ. Sci. Technol. 29:1109–1117.
Mattson, J. S., and Mark, H. B. 1971. Activated Carbon. New York: Marcel Dekker.
Mott, H. V., and Weber, W. 1992. Sorption of low molecular weight contaminants by fly ash:
Consideration for the enhancement of cutoff barrier performance. Environ. Sci. Technol.
26:1234–1242.
Pandey, A. K., Pandey, S. D., and Misra, V. 2000. Stability constants of metal–humic acid complexes
and its role in environmental detoxification. Ecotoxicol. Environ. Safety 47:195–200.
Pehlivan, E., Richardson, A., and Zuman, P. 2004. Electrochemical investigation of binding of
heavy metal ions to Turkish lignites. Electroanalysis 16:1292–1298.
Rathore, H. S., Sharma, S. K., and Agarwal, M. 1985. Adsorption of some organic acids on fly
ash impregnated with hydroxides of Al, Cd, Cu, Fe and Ni. Environ. Pollut., Series B: Chem.
Phys. 10:249–260.
Rovatti, M., Peleso, A., and Ferraiolo, G. 1988. Susceptibility to regeneration of fly ash as an
adsorbent material. Resour. Conserv. Recov. 1:137–143.
Roy, W. R., and Griffm, R. A. 1982. A proposed classification system for coal fly ash in multidis-
ciplinary research. J. Environ. Qual. 11:563–568.
Sell, N. J., Norman, J. C., and Vandembasch, M. B. 1994. Removing color and chlorinated organics
from pulp mill bleach plant effluent by use of fly ash. Resour. Conserv. Recov. 10:279–299.
Sen, A. K., and De, A. K. 1987. Adsorption of mercury(II) by coal fly ash. Water Res. 21:885–888.
Shende A., Juwarkar, A. S., and Dara, S. S. 1994. Use of fly ash in reducing heavy metal toxicity
to plants. Resour. Conserv. Rec. 12:221–228.
Singer A., and Berkgaut, V. 1995. Cation exchange properties of hydro thermally treated coal
fly-ash. Environ. Sci. Technol. 29:1748–1753.
Vincini M., Carini, F., and Silva, S. 1994. Use of alkaline fly ash as an amendment for swine
manure. Bioresour. Technol. 49:213–222.
Yan, G., and Viraraghavan, T. 2001. Heavy metal removal in a biosorption column by immobilized
M. rouxii biomass. Bioresour. Technol. 78:243–249.

View publication stats