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Desalination 185 (2005) 483–490

Experimental study of the removal of copper from aqueous


solutions by adsorption using sawdust

S. Larous, A.-H. Meniai*, M. Bencheikh Lehocine


1-Laboratoire de l’Inge´nierie des Proce´de´s d’Environnement, De´partement de Chimie Industrielle, Universite´
Mentouri, Constantine 25000, Algeria
Tel. þ213 31 61 32; Fax þ213 31 61 32; e-mail: meniai@caramail.com

Received 25 February 2005; accepted 15 March 2005

Abstract
The test and use of natural materials as adsorbents for the removal of various pollutants such as heavy
metals from industrial wastewater is under constant development. Consequently this work concerns the study of
copper adsorption by means of sawdust obtained as by-product from locally used wood.
The copper retention study has been carried out batchwise where the influence of physico-chemical key
parameters such as the solution pH, the temperature, the agitation speed, the initial concentration, the
contacting time, the liquid to solid ratio and the ionic strength has been considered. A desorption study for
the solid support regeneration has also been included.
The equilibrium adsorption capacity of sawdust for copper has been obtained by using linear Freundlich and
Langmuir isotherms. The results tend to explain the retention mechanism as an ion exchange process for
binding the divalent metal ions to the sawdust.

Keywords: Sawdust; Heavy metals; Copper; Adsorption; Ion exchange; Retention

1. Introduction mainly due to their non-degradability and


The discharge of toxic metals into water- toxicity. Numerous metals such as chromium
courses is a serious pollution problem which Cr (III) and Cr (VI), copper (Cu), lead (Pb),
may affect the quality of water supply. manganese (Mn), mercury (Hg), cadmium
Increasing concentrations of these metals in (Cd), etc, are known to be significantly toxic.
the water constitute a severe health hazard Copper, the metal considered in this
study, is a widely used material, where an
intake of excessively large doses by man
*Corresponding author.

Presented at the Conference on Desalination and the Environment, Santa Margherita, Italy, 22–26 May 2005.
European Desalination Society.
0011-9164/05/$– See front matter Ó 2005 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.03.090
484 S. Larous et al. / Desalination 185 (2005) 483–490

may lead, as examples, to severe mucosal irrita- 2. Experimental


tion, a central nervous system irritation, possible 2.1. Apparatus and instrumentation
necrotic changes in the liver and kidney, etc].
These facts have been the motivating  Atomic absorption spectrophotometer AA-
factor for an increasing number of research varian-20 plus operating with an air-acety-
works associated with copper, where the main lene flame has been used for the determina-
objective is the development of various tion of copper concentrations in aqueous
techniques for the the removal and recovery solutions. A priori, a calibration curve has
of these metallic species from wastewater. been established, preparing standard aqu-
These methods include, among others, eous solutions of copper (standard) of 1 g/l
chemical precipitation, electroflotation, ion [5] in order to be able to read the residual
exchange, reverse osmosis and adsorption concentrations of this metal.
which is the scope of this work.  The pH measurements have been per-
The process of adsorption implies the formed with a Multiline P4 phmeter and.
presence of an ‘adsorbent’: solid that efficiently The meter was standardized using buffer
binds molecules by means of physical attractive solutions with pH values: 4.00, 7.00, 10.00.
forces, ion exchange or chemical binding. It is  All filtration’s during this work have been
recommended that the adsorbent is available in carried out by the means of the filter millipore
large quantities, of free or very low cost and easily 0.2 mm – Sartorius MINISART SRP 15.
regenerable [1–3]. Consequently it is always
important to explore and test this kind of materi- 2.2. Adsorbent
als, as far as the surface properties are concerned. Sawdust obtained from locally used wood,
Agricultural by-products may constitute with a mean size of 0.331 mm has been
an important source of this type of materials directly used without any pre-treatment, as
which may be interesting to study and test as an adsorbent for the removal of copper (II)
heavy metal adsorbents and then see how from aqueous solution.
selective they are in retaining certain metallic
ions. In the literature, research in the use of 2.3. Adsorbate solution
agricultural by-products for metal binding
Synthetic aqueous solutions containing
studies has mainly concerned the use of fruit
copper have been prepared by dissolution of
shells and stones, wheat and rice bran, etc but
copper sulphate in locally distilled water.
seldom sawdust [4]. Most cases have con-
firmed that the use of large quantities of
wastes from agricultural products for the 2.4. Experimental procedure
treatment of polluted water is an attractive Batch adsorption experiments have been car-
and promising option with a double benefit ried out by shaking 0.5 g of the sawdust with
for the environment: 100 ml of the copper solution of 10 mg/l con-
 It reduces the residues whose disposal centration at 23 C. The suspension is agitated at
becomes a major, costly problem and 300 rpm for a known period of time ranging
 It converts the wastes into useful and inex- between 5 and 120 min. At the end of the pre-
pensive sorbents for water purification. determined time interval the adsorbent is
The aim of the present work is then to study removed by filtration and a sample of the filtrate
the capacity of sawdust issued from locally used is analysed by means of the atomic adsorption. It
wood for the removal of copper (II). should be noted that the pH of the suspension in
S. Larous et al. / Desalination 185 (2005) 483–490 485

the experiments has been adjusted with NaOH present in sawdust. Decreasing in adsorption
0.1M (1M) and HNO3 0.1M (1M). at high pH may be due to the formation of
soluble hydroxy complexes [6]. At pH 6 there
are three species present in solution as sug-
3. Results and discussion
gested by [7] : Cu2þin very small quantity and
3.1. Effect of pH Cu(OH)þ and Cu(OH)2 in large quantities.
The pH of the aqueous solution is an These species are adsorbed at the surface of
important controlling parameter in the sawdust by ion exchange mechanism with the
adsorption process and thus the effect of pH functional groups present in sawdust or by
has been studied by varying it in the range of hydrogen bonding as shown below
2–10 as shown in (Fig. 1).
It can be observed that the retention of )
2ð  ROHÞ þ Cu2þ ! 2ðROÞCu þ 2Hþ
copper by sawdust increases while the pH
increasing until a certain value, it increases  ROH þ CuOHþ ! ðROÞCuOH þ Hþ
between pH 2.0 and a pH about 6.29, after
Ion exchange
that the capacity of adsorption decreases
slightly in pH range of 8–10. The maximum 2ðROHÞ þ CuðOHÞ2 ! ðROHÞ2
sorption efficiency in the range of 2–8 may be CuðOHÞ2 H  bonding
due to the interaction of Cu2þ, Cu(OH)þ,
Cu(OH)2 with surface functional groups Where-R represents the matrix of sawdust.

pH = 2.06
pH = 4.03
pH = 6.29
pH = 8.04
pH = 10.02

2,0 2.0
q (mg deCu/gd'adsorbant)
q (mg de Cu/g d'adsorbant)

1,5 1.5

Run 1
1,0 1.0 Run 2
Run 3

0,5 0.5

0,0 0.0
0 20 40 60 80 100 120 0 2 4 6 8 10
Temps (min) PH

Fig. 1. Effect of pH on the retention of copper by sawdust Conditions: C0 = 10 mg/l, V = 300 rpm, T = 23 C0,
d = 0.331 mm, t = 120 min, r = 5g/l.
486 S. Larous et al. / Desalination 185 (2005) 483–490

an intimate contact between the phases, a


fact which contributes to the improvement
1.5 of mass transfer.
In order to assess the effect of the agitation
q (mg de Cu/g d'adsorbant)

speed, three different speeds have been chosen


1.0 as shown in Fig. 3, where it can be noted that
the retention of copper increases progressively
T = 20 C°
with the agitation speed as time goes on. There-
0.5 T = 35 C° fore it can be concluded that the agitation speed
T = 45 C° encourages a better transfer of species between
T = 60 C°
the two phases (adsorbent–adsorbate).
0.0
0 20 40 60 80 100 120
Le temps (min) 3.4. Effect of the initial concentration
Fig. 4 shows that the increase in initial
Fig. 2. Effect of the temperature on the retention of copper concentration of copper (II) decreases the
by sawdust Conditions: C0 = 10 mg/l, V = 300 rpm, adsorption and increases the amount of metal
t = 120 min, d = 0.331 mm, pH = 6.29, r = 5g/l.
uptake per unit weight of the adsorbent (mg/g)
The percentage decrease is between 90.4%
3.2. Effect of the temperature (0.180 mg/g) and 70.84% (3.742 mg/g) where
Fig. 2 shows that the retention of copper the initials concentrations are increase between
by sawdust increases while the temperature is 1 and 25 mg/l. This is because at higher initial
increasing until a certain value. The increase concentrations, the ratio of initial number of
in adsorption capacity with temperature sug- moles of copper (II) to the available adsorp-
gested that the active surface sites, available tion surface area, is high.
for adsorption have increased with tempera-
ture. The increase of the temperature
encourages the process of agglomeration in
a very determined sense, until a certain tem-
perature limit, beyond which the desorption 1,5
becomes more important and hence reducing
q (mg de Cu/g d'adsorbant)

the rate of adsorption, as time goes on. This


temperature limit can be regarded as an opti- 1,0

mal temperature that varies around 40 C. V = 80 rpm


Also the increase of the temperature can V = 300 rpm
V = 500 rpm
change the pore sizes which become wider, 0,5

and can induce a certain activation of the


surface of the solid support.
0,0
0 20 40 60 80 100 120
Le temps (min)
3.3. Effect of the agitation speed
The agitation speed is an important para- Fig. 3. Effect of the agitation speed on the retention
meter in any transfer phenomena, since it can of copper by sawdust Conditions: C0 = 10 mg/l,
promote a certain turbulence which insures T = 23 C0, d = 0.331 mm, pH = 6.29, r = 5g/l.
S. Larous et al. / Desalination 185 (2005) 483–490 487

C0 = 1 mg/l important to study its effect on the capacity


C0 = 5 mg/l
C0 = 10 mg/l
of retention of copper by sawdust.
C0 = 25 mg/l Fig. 5 has the typical form of a saturation
4.0
curve. It clearly shows that the equilibrium is
3.5
attained just after only 5 minutes. The
q (mgde Cu/g d'adsorbant )

3.0 increase in contacting time has increased the


2.5 copper uptake and this can be explained by
the affinity of the support towards copper.
2.0

1.5
3.6. Effect of the liquid to solid ratio
1.0
To study the influence of the liquid
0.5
to solid ratio on the retention of copper,
0.0
0 20 40 60 80 100 120
three different values have been taken by
Temps (min) varying the sorbent amount of the support
while keeping the volume of the metal
Fig. 4. Effect of the initial concentration on the retention solution constant as shown in Fig. 6 where
of copper by sawdust Conditions: C0 = 10 mg/l, it can be seen that the adsorption increases
V = 300 rpm, t = 120 min, d = 0.331 mm, pH = 6.29, with the increase in the amount of sawdust.
r = 5 g/l. This can be explained by a greater availability
of the exchangeable sites or surface area at
3.5. Effect of contacting time
higher concentration or amount of the sorbent.
Also contacting time is inevitably a funda-
mental parameter in all transfer phenomena 3.7. Effect of the ionic strength
such as adsorption. Consequently it is
Fig. 7 shows the in fluence of the ionic
strength on the capacity of adsorption. It

1.5
1.5
q (mg de Cu/g d'adsorbant)

q (mg de Cu/mg d'adsorbant)

1.0
1.0

Run n° 1
0.5
Run n° 2
0.5 r = 1 g/l
Run n° 3
r = 3 g/l
r = 5 g/l

0.0
0 20 40 60 80 100 120
0.0
Time (min) 0 20 40 60 80 100 120
Time (min)

Fig. 5. Effect of contacting time on the retention


of copper by sawdust Conditions: C0 = 10 mg/l, Fig. 6. Effect of the liquid to solid ratio on the reten-
V = 300 rpm, T = 23 C0, d = 0.331 mm, pH = 6.29, tion of copper by sawdust Conditions: C0 = 10 mg/l,
r = 5g/l. V = 300 rpm, T = 23 C0, d = 0.331 mm, pH = 6.29.
488 S. Larous et al. / Desalination 185 (2005) 483–490

1.6 3.8. Desorption study

1.5
A desorption study is also important since
q(mg de Cu/g d'adsorbant )

NaCl it is useful in the recycling of the adsorbent


1.4 and recovery of metal. For this study differ-
ent extractant reagents have been tested as
1.3 shown in Fig. 8. The sodium chloride NaCl
0.2M eluted a rather significant quantity of
1.2 copper ions from sawdust. An efficiency of
33.8% has been obtained by using NaCl
1.1
0.2M. In contrast the other extractants
reagents NaNO3, NaCl þ HCl, HNO3, HCl
1.0
were not efficient in the desorption of Cu (II)
0.00 0.02 0.04 0.06 0.08 0.10 ions.
Ionic strength (M)

3.9. Analysis of the adsorption capacity by


Fig. 7. Effect of the ionic strength on the retention of
copper by sawdust Conditions: C0 = 10 mg/l, means of the Langmuir and Freundlich models
V = 300 rpm, T = 23 C0, d = 0.331 mm, t = 120 min. The study of the adsorption isotherm is
fundamental, and plays an important role in
has been tested by the addition of sodium the determination of the maximal capacity of
chloride to the copper solution. The increase adsorption. In order to adapt for the consid-
in ionic strength between 0.001 and 0.1 has ered system, an adequate model that can
decreased the percentage of adsorption reproduce the experimental results obtained,
between 71.20 and 49.70 %. This may be equations of Langmuir and Freundlich
due to the following two reasons : shown in Table 1, have been considered. Gen-
a) The electrostatic attraction seems to be a erally the Langmuir equation applies to the
significant mechanism, as indicated by the cases of adsorption on completely homoge-
results where at high ionic strength, the neous surfaces where interactions between
increased amount of NaCl can help to render adsorbed molecules are negligible. While the
the surface of the sawdust not easily accessi- equation of Freundlich applies fairly well
ble to copper (II) ions and hence decrasing
the adsorption rate. In fact according to the 0.35

Surface Chemistry Theory developed by 0.3

Guoy and Chapman [8], when solid adsor- 0.25


bent is in contact with sorbate species in solu- 0.2
Desorption (%)
tion, they are bound to be surrounded by an 0.15
electrical diffused double layer, the thickness 0.1
of which is significantly expanded by the pre- 0.05
sence of electrolyte. Such expansion inhibits 0
the adsorbent particles and Cu (II) from 7.66 6.62 7.82 7.02 8.038

approaching.
NaNO3 NaCl HNO3 HCl NaCl + HC
b) The relative competition between sodium
ions and copper species for the active sites of Fig. 8. Extractant (0.2 M) Conditions: C0 = 10 mg/l,
sawdust, can also be an explaining factor. V = 300 rpm, T = 23 C0, t = 120 min.
S. Larous et al. / Desalination 185 (2005) 483–490 489

Table 1 Freundlich isotherms, as show the following


Langmuir and Freundlich constants for the Figs. 9a and b.
adsorption of Cu (II) on sawdust Explicitly the Langmuir and the Freun-
Models Equations a b R2 dlich equations are expressed, respectively,
a:b:Ce as follows
Langmuir Qe ¼ 1þb:C e
8.45197 0.0942 0.93877
Freundlich Qe ¼ a:Ceb 1.34776 0.42698 0.93412 ð8:45197Þð0:0942ÞCe
Qe ¼ ð1aÞ
Where Ce is the equilibrium concentration of the 1 þ ð0:0942ÞCe
solution (mg/l); Qe is the amount of solute adsorbed
by unit mass of adsorbent (mg/g); a, b constants; R
Qe ¼ 1:34776Ce0:42698 ð1bÞ
the correlation factor.

when describing the adsorption in aqueous 4. Conclusions


systems. This study shows clearly that sawdust
It can be seen that the correlation factor is which is a cheap and abundant material can
close to unity for both models, indicating a be used as an effective adsorbent for removal
good representation of the experimental of copper from wastewater. This adsorption
results by using linear Langmuir or process is also dependent on numerous

8
7.5
7
qe (mg de Cu / g d'adsorbant )

6
qe ( mg de Cu / g d'adsorbant )

6.0

4.5
4

3
Experimental values
3.0

Experimental values 2

1.5 1

0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Ce (mg de Cu / l) Ce (mg de Cu / l)

(a) (b)
Langmuir isotherm of copper Freundlich Isotherm of copper
Fig. 9. Adsorption isotherms using Langmuir and Freundlich models Conditions: V = 300 rpm, pH = 6.29,
r = 5g/l, d = 0.331 mm, T = 23 0C.
490 S. Larous et al. / Desalination 185 (2005) 483–490

factors such as the solution pH, the tempera- A. Mansri, ‘Study and Identification of Reten-
ture, the agitation speed, the initial concen- tion Process of Heavy Metals by Adsorption on
tration, the contacting time, the liquid to Agricultural By-Products’ Chemical Engineering
& Technology. Eng. Life Sci., 3 (2003) 9.
solid ratio, the ionic strength, etc. The max-
[3] N. Gherbi, A.-H. Meniai, M. Bencheikh-Lehocine,
imum percentage removal occurs between the A. Mansri, M. Morcellet, K. Bellir, M. Bacquet
pH range 2.0–8.0. The study of the ionic and M. Martel, ‘Study of The Retention Phenom-
strength and the pH effects, has confirmed ena of Copper II by Calcinated Wheat Bypro-
that ion exchange is the major mechanism of ducts’. Desalination, 166 (2004) 363–369.
retention of copper by sawdust undergoing [4] S.R. Shukla and V.D. Sakhardane, Column stu-
no treatment, and showing a high efficiency dies on metal ion removal by dyed cellulosic
The isotherm study indicates that the sorp- materials. Journal of Applied Polymer Science,
44 (1992) 903–910.
tion data can be modelled by both Langmuir
[5] K. S. Binay and N.S. Rawat, Comparative sorp-
and Freundlich isotherms.. tion Kinetic studies of phenolic compounds on
The study of desorption was also carried fly ash impregnated fly ash. J.Chem. Technical
out and shows that the sodium chloride Biotechnol, 61 (1994) 57–65.
(NaCl) 0.2 M is the best extractant. [6] K. Anoop Krishnan and T.S. Anirudhan, Removal
of Cadmium (II) from Aqueous Solutions by
Steam-Actived Sulphurised Carbon prepared from
5. References Sugar-Cane Bagasse Pith: Kinetics and Equilibrium
[1] J.V. Rios, L. Bess-Oberto, K.J. Tiemann and Studies, Department of Chemistry, University of
J.L. Gardea-Torresdey, Investigation of Metal Kerala, Water SA, 29(2) 2003.
ion Binding by Agricultural By-Products. Pro- [7] H.A. Elliot and C.P. Huang, Water Res, 15
ceedings of the. Conference on Hazardous (1981) 849.
Waste Research, 1999 125. [8] L. Osipow 1 ‘Surface Chemistry: Theory and
[2] S. Arris, M. Bencheikh-Lehocine, A.-H. Meniai, Industrial Applications’, Krieger, New York
M. Morcellet, M. Bacquet, B. Martel and 1972.