Fuel Processing Technology 95 (2012) 1–7

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Fuel Processing Technology

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Removal of copper from aqueous solutions by low cost adsorbent-Kolubara lignite

Sonja Milicevic a, Tamara Boljanac a, Sanja Martinovic a,⁎, Milica Vlahovic a,
Vladan Milosevic a, Biljana Babic b
a
Institute for Technology of Nuclear and Other Mineral Raw Materials, 86 Franchet d'Esperey Blvd., Belgrade, Serbia
b
University of Belgrade, Institute of Nuclear Sciences “Vinca”, Belgrade, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: Serbian lignite from “Kolubara” deposit was used as a low cost adsorbent for removal of copper ions (Cu2 +)
Received 29 July 2011 from aqueous solutions. Lignite was subjected to the elementary and technical analysis as well as BET and
Received in revised form 28 September 2011 FTIR analysis due to complete characterization. Basic comparison between lignite and activated carbon was
Accepted 2 November 2011
also done. As a method, batch adsorption procedure was applied. Adsorption efficiency was studied as a func-
Available online 26 November 2011
tion of the initial metal concentration, pH of the solution, contact time, and amount of the adsorbent. Opti-
Keywords:
mum removal of copper ions was achieved at pH values of 5.0. About 90% of copper cations were removed
Adsorption in 5 min of contact time from the solution with the lowest copper concentration (50 mg Cu 2 +/l) regardless
Lignite adsorbent amount, while the same effect of adsorption was achieved in 60 min in case of solutions with
Copper higher concentrations of copper. It was concluded that the effect of adsorbent amount on adsorption kinetics
Kinetics is evident but not crucial. It was proved that the experimental results of copper adsorption fit well to a Lang-
muirian type isotherm which was used to describe monitored adsorption phenomena. The calculated adsorp-
tion capacities of lignite for copper adsorption decrease with increasing adsorbent amount. The study proved
that tested lignite is very efficient adsorbent material, especially in case of low copper concentration in aque-
ous solution where the usual methods are either economically unrewarding or technically complicated. This
behavior can be explained by FTIR spectrum despite a small specific surface area of lignite. Namely, many
bands (peaks) are attributed to the functional groups that they are involved in chemisorption and ionic ex-
change, basic mechanisms of copper adsorption.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction reverse osmosis, biological process [2,5]. Each of these methods is

Copper is known as one of the most common toxic and hazardous
metals which is often used in electrical, mining, and electronic indus-
tries, iron, steel and non-ferrous production, electroplating, metal fin-
ishing, printing and photographic procedures. Copper, as well as the
other heavy metals, is released into the environment in a number of dif-
ferent ways and it finds the way to get into the water-streams and thus
make environmental contamination that presents threat to humans,
animals, and plants. This can cause serious and complex problem [1–4].
Concentrations of copper and other heavy metals from the waste-
water and water-streams have to be reduced in order to satisfy rigid
legislative standards. They can be removed by various technologies,
most often expensive or inefficient and technically complicated espe-
cially because of limited low residual concentrations required by the
EPA (Environmental Protection Agency) [2–4]. The conventional tech-
niques for heavy metals removing from aqueous solutions include
oxidation, reduction, chemical precipitation, filtration, ion exchange,
adsorption, membrane techniques, electrolytic or liquid extraction,
⁎ Corresponding author. Tel.: + 381 11 3691 722; fax. + 381 11 3691 583.
E-mail address: s.martinovic@itnms.ac.rs (S. Martinovic).
used only in special cases since it has some limitations in practice [6].
Namely, the major disadvantage of almost all mentioned methods is
production of new hazardous waste, mostly solid, at the end of the
treatment [1]. Nowadays, many researches have been involved in de-
velopment of new inexpensive materials and methods for the treat-
ment of wastewater containing heavy metals, for example natural
adsorbents such are zeolites, wood, lignite, metal oxides, fly ash, coal,
and waste biomass [7–9]. Predominant mechanism in this process is
ion exchange, but also there is surface adsorption, chemisorption, com-
plexation and adsorption-complexation [2–4,10]. Carbon based mate-
rials are very common for the removal of color and organic matter
from wastewater. Activated carbon is a preferred adsorbent, but its ap-
plication is often restricted due to its high cost [11]. On the other side, in
spite of relatively small adsorption capacity of lower quality coals, com-
pared with expensive synthetic materials used for ionic exchange, lig-
nite is considered as a very attractive material for metals removal
since it is widely available and inexpensive [2]. It should be emphasized
that removing heavy metals from the wastewaters present in relatively
low concentration is rather difficult [6]. Recently, the use of lignite in
wastewater treatment has become more and more attractive since it
can be good substitution for synthetic and expensive activated carbon.
Lignite possesses all the necessary characteristics that make it a very

0378-3820/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2011.11.005
2 S. Milicevic et al. / Fuel Processing Technology 95 (2012) 1–7
efficient material for the removal of copper and other heavy metals
from wastewater [2,6,11,12].
Lignite is the youngest type of coal, member of the solid fuels and
one of the abundant natural resorces. Lignite has a high content of
exchangable functional groups that make it suitable and efficient for
the removal of heavy metals from wastewater. Lignites have high cation
exchange capacity forming with metal ions complexes. Namely, lignites
have high content of oxygen fixed in carboxile (−COOH), alcocholic
(−OH) and carbonyl (=C = O) groups representing active centers of
the ion exchange. Owing to these properties, lignites take part in ion ex-
change mechanism and in wastewater treatment as a medium for
heavy metals removing. Lignites are usually amorphous and fibrous or
woody in texture. Their structure consists of water-filled pores and cap-
illaries and exhibits high moisture contents (30–70%) [6,11,13,14].
The primary aim of this study was to determine adsorption pa-
rameters of low cost Kolubara lignite during the removal of copper
from the synthetic aqueous solutions. The idea was to perform exper-
iments with lignite in the form suitable for usage in thermal power
plant for the reason of comparison with the activated carbon. It was
found that this lignite is an excellent adsorbent for copper, especially
in case of aqueous solution with small copper concentration.
2. Experimental
2.1. Adsorbent
Lignite from Kolubara deposit, field B, used as a fuel in power plant
Nikola Tesla, was applied in experiments as an adsorbent material.
First, it was dried at 45 °C for 24 h, and then grounded and sieved. Frac-
tions from 1 to 2 mm were used for the adsorption experiment, while
fine fractions, under 1 mm, were used for elementary analyses. Heating
value was measured using an automatic calorimeter. Activated carbon
(Merk, Germany), most common adsorbent in wastewater treatment,
was used for comparation with lignite as adsorbent agent.
2.2. Surface area
Adsorption and dersorption isotherms of N2 were measured on lig-
nite and activated carbon samples, at −196 °C, using the gravimetric
McBain method. The specific surface area (SBET), pore size distribution
was estimated by applying BJH method [15] to desorption branch of iso-
therms and mesopore surface and micropore volume were estimated
by using the high resolution αs plot method [16–18]. Micropore surface
(Smic) was calculated by substracting Smeso from SBET.
2.3. Fourier transform infrared analysis
Functional groups in organic samples (lignite and activated carbon)
were examined by using the FTIR method of analysis. The IR measure-
ments were carried out by a Fourier Transform Infra Red (FT-IR) spec-
trophotometer based on changes in dipole moment resulting from
bond vibration upon absorption of IR radiation. FTIR-ATR (Fourier trans-
form infrared attenuated total reflection spectroscopy) spectroscopic
analyses were carried out at room temperature using a Nicolet 380
spectrophotometer in the spectral range of 4000 to 400 cm− 1, with a
resolution of 4 cm− 1. The datasets were averaged over 64 scans.
2.4. Adsorption tests
The kinetics of copper adsorption on lignite was conducted by
batch technique at ambient temperature in aqueous solutions under
continuous stirring conditions.
The procedure was as follows: weighted amount of lignite was
placed into a glass vessel with cover. Prepared copper solution was
added and then agitated. In order to quantify adsorption efficiency (per-
cent of adsorbed metal), suspension was filtered and residual copper
ion concentration in the filtrate was determined by Perkin Elmer Atom-
ic Adsorption Spectroscopy (AAS) type AAnalyst 300.
Synthetic aqueous solution of copper was prepared by dissolving of
appropriate amount of CuSO4·5H2O salt in deionised water. Volume of
the solutions was constant (250 ml), as well as stirring conditions. Ef-
fects of three different concentrations of the initial solution (50, 200,
and 330 mg Cu2 +/l) on adsorption were investigated. Influence of the
initial solution's pH on the adsorption efficiency was observed during
the experiment. pH was measured by pH meter and kept in the range
of 2–6 by using diluted 0.1 M HNO3 or 0.1 M NaOH solution. Also, the ef-
fect of three different amounts of air dried lignite (30, 45, and 60 g) on
adsorption was followed during the experiment. All experiments were
monitored depending on contact time up to one hour.
The lignite saturated with copper was treated with deionized
water. The analysis of the obtained solution proved literature assess-
ment that there was no leaching from the adsorbent [2].
3. Results and discussion
3.1. Characterisation of adsorbent
Elementary and technical analysis as well as specific surface area
of lignite from Kolubara deposit, conducted according to the standard
procedure, is given in Table 1.
According to the IUPAC classification [19], nitrogen adsorption–
desorption isotherm for lignite, as the amount of N2 adsorbed as func-
tion of relative pressure at − 196 °C, is of type I which is associated
with nonporous and macroporous materials. Specific surface area cal-
culated by BET equation (SBET) is 1 m 2/g. On the other side, isotherm
for activated carbon is of type IV and with a hysteresis loop which is
associated with mesoporeous materials. The shape of hysteresis
loop is of type H4 which indicates a narrow slit pores and large
amount of micropores [20]. Specific surface area calculated by BET
equation (SBET) is 758 m 2/g.
Pore size distribution of activated carbon shows that the sample is
mostly microporous with certain amount of mesopores and the pores
radius below 7 nm. Actually, activated carbon consists of micropore
amount (Smic) = 683 m 2/g and mesopore amount (Smeso) = 75 m 2/g.
FTIR spectra of analyzed lignite and activated carbon are shown in
Fig. 1. Bands were identify by comparison to the literature [21,22–28].
These two spectra differ significantly in the peaks and it is obvious
that lignite has much more functional groups than activated carbon.
Six peak areas observed in diagram of Fig. 1 are: hydorxyl group region
(3100–3700 cm− 1), aliphatic stretching region (2931–2855 cm− 1), aro-
matic carbon (peaks at 1618 and 1606 cm− 1), aliphatic bending region
(1509–1371 cm− 1), cellulose and lignin region (1300–1000 cm− 1), and
the aromatic out-of-plane region 900–700 cm− 1) were measured. Addi-
tionally, intense vibrations at 3698 cm− 1, 3620 cm− 1, 531 cm− 1 and
469 cm− 1 are attributed to clay and silicate minerals. The small peaks
in the rand of 3698 cm-1 and 3700 cm-1 can be assigned to the crystal
water which exists in clay minerals of the matrix lignite samples [29].
Lignite spectra show typical infrared characteristics of the organic
compound, coal, including aliphatic C-H stretching bands at
2924 cm − 1 and 2856 cm − 1, C = C or C = O aromatic ring stretching
vibrations at 1610 cm − 1 and at 1506 cm − 1, as well as aliphatic
C\H stretching bands at 1455 cm − 1, 1370 cm − 1.
Table 1
Basic characteristics of the lignite Kolubara deposite, field B.
Content (%) Heating value BET
(kJ/kg) (m2/g)
C H N+O S H2O Ash
65.75 5.79 27.76 1.13 46.30 11.14 9499 1
 S. Milicevic et al. / Fuel Processing Technology 95 (2012) 1–7
Fig. 1. FTIR spectrum of lignite and AC.
The broad band at ~ 3406 cm -1 is attributed to –OH stretching vi-
brations of hydrogen bonded hydroxyl groups of absorbed water ei-
ther of clay minerals or phenol groups.
The bands at ~2931 cm− 1 and ~2855 cm− 1 are attributed to ali-
phatic CH vibration of −CH3 and −CH2 stretching vibrations,
respectively.
The strong band at ~1606 cm − 1 is attributed either to C = O or
C = C aromatic ring stretching vibrations.
The band at ~1505 cm − 1 is due to C = O stretching vibrations.
The band at ~ 1454 cm − 1 is attributed to symmetric aliphatic C-H
vibrations of methylene (CH2) and methoxyl (OCH3).
The band at ~ 1370 cm − 1 is due to symmetric aliphatic C-H bend-
ing vibrations of methyl groups (OCH3).
The band at ~1265 cm − 1 is attributed to C-O stretching vibrations.
The peak at ~1033 cm − 1 is due to C\O\H bonds in cellulose as
well as to C-O stretching vibrations of aliphatic ethers (R-O-R`) and
alcohols (R-OH).
Adsorption is a process of mass transfer of adsorbate in solution to
the adsorbent surface driven by physical and/or chemical forces. For
adsorbate, its adsorption capacity and mechanisms are closely associ-
ated with the adsorbent surface characteristics. Based on that, it can
be concluded that driving mechanism of lignite adsorption is based
on chemisorption since there are many functional groups involved
in ion exchange. On the other side, the adsorption properties of acti-
vated carbon are govern by physisorption since it has high values of
specific surface area as well as micro and meso porosity. It can be
explained by diffusion and transport processes within meso- and mi-
cropores. Since lignite is classified as nonporous and macroporous
materials and specific surface area is small, it can be assumed that
all identified functional groups involve in ion exchange during the ad-
sorption are placed at the surface of lignite. Namely, when express in
terms of per unit surface area, lignite seems to give a surprisingly
good adsorption capacity compared with the activated carbon.
3.2. Adsorption kinetics
3.2.1. Effect of the adsorbent amount on copper removal
Effect of the adsorbent amount on adsorption efficiency is shown
in Fig. 2. Increasing amount of lignite from 30 to 60 g for the same
concentration of copper in solution leads to reduction of the adsorbed
metal amount per mass unit of lignite. This is particularly obvious in
the solution with higher copper concentration while this influence
weaks in the solutions with the lowest copper concentration. It sug-
gests that experiments should be directed to the small amounts of lig-
nite in order to achieve better efficiency and to determine capacity of
the adsorbent. On the other hand, tested masses of lignite under
3
Fig. 2. Influence of adsorbent mass on adsorption efficiency (conditions: C0 = 50, 200,
330 mg Cu2 +/l, pH = 5, contact time 30 min).
optimal conditions do not substantially affect the adsorption efficien-
cy regardless the high concentration of the initial solution.
3.2.2. Effect of pH solution on copper removal
Carboxyl and hydroxyl groups are the main exchangeable func-
tional groups that take part in the adsorption of metal ions onto lig-
nite derived adsorbents. With increasing of pH solution, these
functionalities dissociate, i.e., become deprotonated and negatively
charged. During the adsorption, H + and other exchangeable cations
(e.g. Na +, Ca 2 +, and Mg 2 +) are substituted with metal cations and
released from the adsorbent to the solution [11].
Generally, very important parameter that should be controled
during the adsorption process is pH of the initial aqueous solution.
Lignite mass of 30 g and contact time of 30 min used in this part of
study were fixed.
The metal cations in the aqueous solution convert to different hy-
drolysis products. At low to high pH values, copper ions exist as Cu 2 +,
Cu(OH)+, and as neutral compound Cu(OH)2. The dominant species
of copper in the pH range from 3 to 5 are Cu2 + and Cu(OH)+ ions,
while the copper occurs as insoluble Cu(OH)2(s) above pH 6.3. Experi-
ments were performed with the pH values in the range of 2–6, since
Cu(OH)2 started to precipitate above pH of 6. Increase of pH from 2 to
5 leads to the rise of adsorption efficiency from 20 to 94%, respectively
[4–6].
Fig. 3 shows influence of pH value on sorption efficiency of lignite.
Based on the results presented in Fig. 3, it is obvious that the per-
centage of adsorbed copper ions suddenly increases with rising of pH
reaching the highest value at pH of 4–5. It can be explained by obser-
vation that the increase of pH value induces replacement of hydrogen
ions from the surface of the lignite with the copper ions resulting in
improvement of the adsorption effeciency extent.
Hydrogen ions induce metal complexation because they have
great affinity for many complexing and ion exchange sites. At very
Fig. 3. Effect of solution pH on copper adsorption using 30 g of lignite and contact time
of 30 min.
4 S. Milicevic et al. / Fuel Processing Technology 95 (2012) 1–7

low pH (b2.0) functional groups (hydroxyl, carboxyl, phenol, meth-

oxyl, etc.) of the coals are protonated. Equilibrium reaction of metal
adsorption can be considered as follows [6]:
þ
Coal−COOH ¼ Coal−COO þ HðaqÞ ð1Þ

þ2
CuðaqÞ þ 2Coal−COO ¼ ðCoal−COOÞ2 Cu ð2Þ

þ2
CuðaqÞ þ 2OH ¼ CuðOHÞ2 ð3Þ

Due to high concentration of H+ ions for the pH lower than 2, equi-

librium of the Reaction (1) will be shifted to the left side according the
equilibrium law. Since sites of ion exchange on the lignite are mainly
protonated, less available groups for ion exchange become available.
As expected, the efficiency generally increases with increasing pH,
while the effect of pH is indistincitve or even reverse. The increase of
the adsorption effeciency is the most explicit for pH values between 2
and 4, probably reflecting progressive deprotonation of carboxylic
groups. Namely, in mentioned pH range, the carboxyl groups
(−COOH) from the lignite can lose H+ and be appreciably deproto-
nated. That will shift the Reaction (2) to the right, while the increase
of the solution pH increases copper ion removal. In this pH range, pro-
cess of ion exchange is the major mehanism for the removal of copper
ions from the aqueous solution. As already mentioned, hydrolysis Reac-
tion (3) happened at pH ≥ 6 and copper hydroxide precipitation was
occurred [6,30,31]. It is obvious that optimum pH for Cu 2 + adsorption
by lignite is 5.0, so the adsorption experiments regarding influence of
the adsorbent amount, initial concnentration and contact time were
performed with pH value of 5.

3.2.3. Effect of contact time on the copper removal

In order to achieve the equilibrium state with maximally reduced
adsorption time, tests were carried out with greater amounts of coal
thus providing large number of available active adsorption sites on
free adsorbent surface.
Namely, possible use of small amounts of coal that can provide
good adsorption efficiency but for more reasonable time was a goal
of this testing. The efficiency of copper adsorption from aqueous solu-
tions with three different initial concentrations (50, 200, and 330 mg
Cu 2 +/l) on three different amounts of lignite (30, 45, and 60 g) was
observed depending on contact time up to 60 min, as shown in
Fig. 4. Based on the change in metal concentration in the aqueous so-
lution before and after achieving equilibrium adsorption, the adsorp-
tion efficiency was calculated.
Copper removal from the aqueous solutions in the first 5 min has a
significant practical value.
In all cases, the majority of copper ions was removed at the beginning
of the adsorption proceess, during the first 5 min of contact time. Besides,
it is obvious that the adsorption occurred in 3 stages. The first stage
lasted for five minutes. In this period, there was decrease in Cu2 + ions
concentration of 65–92% depending on the solution concentration and
the adsorbent amount. The adsorption of Cu2 + in this stage happened
so quickly. During the second stage within the next 15 min removing
of Cu2 + was more than 90% for all solution concentrations and adsorbent
amounts while the adsorption happened much slowly. It is very impor-
tant to determine the equilibrium time for each type of lignite used as
an adsorbent material. Equilibrium time, that is the contact time charac-
terized by unchanging Cu2 + concentration in the solution, was achieved
after 30 min for all used concentrations of solutions and amounts of ad-
sorbent; this period is denoted as the third stage of the adsorption.
High adsorption rate at the beginning of the adsorption process is
due to the numerous readily available active adsorbing sites on the ad-
sorbent surface; that is the large uncovered surface area of lignite which
was provided by high amount of lignite while the copper ions can inter-
act easily [6]. Additionally, the driving force for the adsorption is the dif-
ference between concentration of copper in the solution and solid/
Fig. 4. Effect of contact time on copper adsorption for three different masses of lignite
as adsorbent: a) 30 g; b) 45 g; and c) 60 g at pH = 5;.
liquid interface which has the highest value at the beginning of the pro-
cess, resulting in fast adsorption. Lower slopes of the curves confirm
that the second stage was a bit lower due to lower diffusion velocity
of copper ions within the pores of the lignite structure. It can be ob-
served that the best adsorption efficiency (>90%) was achieved in the
case of initial solution with the lowest copper ions concentration
(50 mg Cu2 +/l) for all adsorbent amounts. In addition, the smallest dif-
ference in adsorption efficiency of three initial solutions concentration
was observed by using 60 g of lignite.
Sorption efficiency of lignite and activated carbon in case of low
initial concentration depending on contact time is presented in
Fig. 5. It is obvious that activated carbon shows better adsorption ef-
ficiency than lignite for longer contact time, but these differences are
insignificant. Namely, it should be emphasized that used lignite is low
cost raw material and plentiful in Serbia while activated carbon is
more expensive due to pretreatment.
3.2.4. Effect of initial concentration on copper removal and adsorption
isotherm
Effect of the initial solution concentration (50, 200, and 330 mg
Cu 2 +/l) on the copper removal was observed and the obtained results
 S. Milicevic et al. / Fuel Processing Technology 95 (2012) 1–7
Fig. 5. Comparison of contact time influence on copper adsorption for lignite and activated
carbon; 30 g of adsorbent, 50 mg Cu2 + /l, pH= 5.5.
are shown in Fig. 6. Different amounts of the adsorbent were used
(30, 45, and 60 g). It is obvious that for all lignite amounts, the ad-
sorption of Cu 2 + and, therefore, adsorption efficiency decreases
with the increase of the initial solution concentration.
It was found that the equilibrium time was around 30 min, so the re-
sults of the initial solution concentration influence on copper removal
are shown for that period. Effect of the initial solution concentration
on copper adsorption was investigated for the following conditions:
V = 250 ml, pH = 5, t = 20 °C.
For all used initial solutions, the amount of adsorbed Cu2 + ions de-
creases with the increase of the concentration. This is especially empha-
sized in case of the adsorbent mass of 30 g, where the adsorption
efficiency decreases from 94% to 86% for the initial concentrations of
50 mg/l and 330 mg/l, respectively. Based on the results presented in
Fig. 6, it is obvious that lignite is an effective adsorbent material for cop-
per removal from the aqueous solutions, especially in case of low solu-
tion concentration; the adsorption efficiency is 94–97% from the initial
solution with concentration of 50 mg Cu2 +/l.
In solutions with low concentration (regardless the adsorbent
mass), the ratio of surface active sites (funcional groups) on lignite to
the total copper ions in solution is high and hence all metal ions may in-
teract with the adsorbent and be removed from the solution. Since the
driving force that presents concentration gradient is stronger in case
of high concentrations, adsorbed amount of Cu 2 + per unit of absorbent
mass will be higher, Fig. 7.
It is obvious that the influence of lignite mass on adsorption efficien-
cy is visible but not crucial particularly in the cases of low concentra-
tions. The influence of adsorbent mass increases with concentration
Fig. 6. Adsorption of copper ions on lignite for three different initial solution
concentrations.
5
Fig. 7. Influence of initial solution concentration and lignite mass on adsorption
amount of copper.
rising; this is evident in case of initial solution concentration of
330 mg Cu2 +/l.
Isotherm of copper adsorption by lignite is shown in Fig. 8. Initial
experimental conditions were: lignite amount of 30 g, pH = 5.0 and
contact time of 30 min.
Adsorption isotherm used for describing results of copper adsorp-
tion on lignite as an adsorbent is presented using the equation of
Langmuir, Fig. 6. Results for copper adsorption fit excellent to a Lang-
muirian type isotherm expressed by the following equation [2,4]:
q max bC e
q¼ ð1Þ
1 þ bC e
where q is the amount of metal ion absorbed per unit mass of lignite
(mg/g), Ce is the equilibrium copper concentration (mg/l), qmax is the
maximum adsorption capacity (mg/g), b is constant related to ad-
sorption intensity (l/mg) [2,4].
The Lagnmuir model is probably the best-known and most widely
applied adsorption isotherm, since it shows good agreement with a
wide variety of experimental data. It should be emphasized that Lang-
muir isotherm can be applied to the adsorption on completely ho-
mogenous surface with negligible interaction between adsorbed
molecules. Regardless the basic assumption that this model can not
be applied for heterogeneous adsorbent surface, it was quite success-
ful in predicting the experimental saturation capacity of the applied
adsorbent [6].
Comparative adsorption isotherms of activated carbon and lignite
are shown in Fig. 9. It is evident that lignite shows better adsorption
properties than activated carbon.
As seen in Fig. 1., FTIR spectra, lignite has more specific adsorption
bands than activated carbon. On the other side, specific surface area of
Fig. 8. Isotherms of copper adsorption by lignite using Langmuir model.
6 S. Milicevic et al. / Fuel Processing Technology 95 (2012) 1–7
Fig. 9. Comparative isotherms of copper adsorption by activated carbon and lignite.
activated carbon is higher as well as number of micro and meso pores.
It can be concluded that influence of oxygen functional groups is
dominant for explaining adsorption behavior of lignite. Also, results
of FTIR functionality analysis suggests that chemical adsorption
plays important role for high adsorption efficiency of lignite.
Experimental data of the present work were excellent fitted to the
Langmuir equation since the regression analysis gave high correlation
coefficients R2 > 0.9, as shown in Table 2. The maximum adsorption ca-
pacities calculated by the Langmuir equation were 4.045, 3.908 and
2.625 mg/g for lignite masses of 30, 45 and 60 g, respectively (Table 2).
The shape of all the isotherms is of ”L1” type according to Giles
classifications for isotherms [4,32] which indicated that the curves
do not reach any plateau (the adsorbent does not show clearly a lim-
ited adsorption capacity) [4,33]. „L“ or Langmuir isotherm type is usu-
ally associated with ionic substrates, like metal cations, adsorption
with weak competition from the solvent molecules [32,34].
The obtained adsorption capacities are not in accordance with those
that are usually reported in the literature because of high used masses
of the adsorbent. These results indicate that the saturation of lignite
by copper ions was not achieved regardless the initial concentration
of solution. It is obvious that the increasing amounts of lignite from
30 g to 60 g for the same initial solution concentration lead to decrease
of the adsorption capacity value. Numerous free, available, and active
sites on the adsorbent surface prove the assumption that much smaller
lignite amount than 30 g can give good results in means of removing
copper from the aqueous solution.
4. Conclusion
Because of plentiful amounts of lignite in Serbia and rationaliza-
tion of the adsorption process, the idea of this research was to avoid
pre-treatment and use adsorbent in its raw form suitable for applica-
tion in thermal power plant.
This research shown that lignite from Kolubara deposit is highly
effective, inexpensive and naturally available adsorbent for Cu 2 + re-
moval from aqueous solutions because of the environmental protec-
tion. In order to support explanation of lignite adsorption efficiency,
Table 2
Langmuir parameters for copper adsorption on lignite.
R2 qm, mg/g K, l/mg
Lignite
30 g 0.9228 4.045 0.038
45 g 0.9191 3.908 0.025
60 g 0.9740 2.625 0.056
AC 0.9497 3.229 0.026
FTIR analysis and determination of specific surface area were done.
Also, all results were compared with the activated carbon because it
is the most common adsorbent in wastewater treatment.
The effects of pH, initial solution concentration, the adsorbent
amount, and contact time on adsorption process of Cu 2 + on lignite
were followed.
In a metal-lignite system, interaction process happened in the in-
terval of pH = 2,0–5.0. The maximum adsorption is achieved if the pH
solution is around 5.0. It was found that the rate of adsorption is very
high at the beginning of the process in case of low copper concentra-
tion in the initial solution. In the first 5 min, it reaches 90% due to
higher amount of the adsorbent than it is usual. Sufficient contact
time for both adsorbents is 30 min, since they achieve equilibrium
for the mentioned time. Optimal parameters presented in this paper
were: pH = 5.0, C0 = 50 mg Cu 2 +/l, τ = 30 min, the adsorbent
amount of 30 g. The calculated adsorption capacities are not in accor-
dance with literaturely available values because high adsorbent
masses were used. As the surface area of the lignite was significantly
lower than that of the activated carbons, it can be assumed that the
adsorption capacity of the lignite was augmented by chemisorption.
Isothermal tests show that the adsorption data agrees well with
Langmuir isotherm model. The obtained maximum adsorption capac-
ities were 4.045, 3.908 and 2.625 mg/g for lignite masses of 30, 45 and
60 g, respectively.
It can be concluded that in order to achieve better efficiency and
economy, further investigation should be directed to the usage of
much smaller amounts of lignite that can provide complete saturation
by copper ions to the maximum utilization of adsorbent in wastewa-
ter treatment.. Most important advantages of lignite as a potential in-
dustrial absorbent compared to activated carbon are that no pre-
treatment is required, its low cost, high adsorption capacity, and
plentiful resources.
Acknowledgments
This research has been financed by the Ministry of Science and
Technological Development of Republic of Serbia as a part of the project
TR 33007. The authors would like to express their gratitude for this
support.
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