Presented at the conference on Desalination and the Environment.

Sponsored by the European Desalination Society

prepared from the peach cores: modelling and optimisation
N. El Hannafi, M.A. Boumakhla, T. Berrama*, Z. Bendjama
Department of Process Engineering and Environment, University of Sciences and Technology Houari
Boumediene, Algeria (USTHB), BP 32, El Alia, 16111 Bab Ezzouar, Algiers, Algeria
Fax +213-2 1710101; email: tarek_ber@yahoo.fr
Received 1 January 2007; accepted 13 January 2007
Abstract
The aim of this paper is to model and optimize the conditions of obtaining the activated carbon prepared from
the date cores, and the elimination of phenol by adsorption.
Several activation chemical agents were tested for the preparation of the activated carbon. Best results is
obtained with the phosphoric acid (54% of yield elimination). The operational parameters of activated carbon
preparation have been study by using the method of the experimental designs; a first degree model has been
established.
The kinetic study showed that the maximum of adsorption is reached after 60 min of contact. The effect of pH
on the yield adsorption has been carried in a range of 210, the maximum of adsorption is obtained towards a
value of 5.5. Many operational parameters can influence the phenol elimination, like the temperature, the speed
stirring, and the activated carbon initial concentration. The temperature is practically without any influence in
phenol elimination; consequently, tests of adsorption will be carried out at the ambient temperature. The method
of simplex has been applied to determining optimum values yield of elimination, the two parameters to be
optimized are the speed stirring and the initial concentration of the adsorbent. The best phenol elimination
obtained is 86%.
Keywords: Phenol; Water pollution; Industrial wastes; Peach cores; Modelling; Optimisation; Simplex;
Adsorption; Experimental design
1. Introduction
The water pollution represents a real danger
to the environment; and consequently for the man.
This pollution is due primarily to the industrial
wastes, with worn water of urban origin, the use
of manures, and the pesticides in agriculture [1].
The phenolic compounds are the ones of pollut-
ant substances.
The activated carbon can be prepared starting
from various raw materials of origins animal,
*Corresponding author.
Desalination 223 (2008) 264268
Elimination of phenol by adsorption on activated carbon
0011-9164/06/$ See front matter 2008 Published by Elsevier B.V.
and Center for Research and Technology Hellas (CERTH), Sani Resort, Halkidiki, Greece, April 2225, 2007.
doi:10.1016/j.desal.2007.01.229
N. El Hannafi et al. / Desalination 223 (2008) 264268 265
mineral and vegetable [2]. For a few years the new
precursors has been used such as natural fibres
(cotton) or synthetic (PVC, viscose, etc.) [3].
Zhonghuahu et al. [4] have elaborated an
activated carbon, of specific surface equal to
2451 m
2
/g, starting from the coconut hulls
treated with KOH. Experiments of adsorption
carried out with compounds phenolic show that
the capacity of fixing these molecules on elabo-
rate coal is higher than that of the commercial
activated carbon.
Calace et al. [5] have studied the capacity of a
worn oil to adsorbing the phenolic compounds.
The purpose of this paper is to model and
optimise the conditions of obtaining the activated
carbon, elaborated from the peach cores, and its
using to phenol elimination by adsorption.
The conditions of the preparation of acti-
vated carbon were optimised and modelling.
The recovery of phenol is controlled by many
parameters, their effects were studied by using
the experimental design and the simplex method.
2. Materials and methods
The cores of peach are washed and dried
with the ambient air during 2 days, the activated
carbon were prepared under various conditions.
Chemical activation was carried out by using
different agent of activation: H
3
PO
4
, H
2
SO
4
, HCl,
HNO
3
and ZnCl
2
.
Then, the cores undergo a carbonization in a
muffle furnace, follow-up of a washing, drying,
crushing and sifting. The solid particles obtained
have an average diameter of 200 m.
The phenol concentration is determined using
a visible spectrometer UV (SAFAS Monaco) at
wavelength of 270 nm.
3. Choices of the activation agent
Numerous agent of activation have been
tested (Table 1).
The yield of phenol elimination is given in
Fig. 1.
The best activation is obtained with the phos-
phoric acid and the nitric acid with approxi-
mately 54% of yield elimination, however with
HNO
3
, the cores become not easily exploitable.
For this reason the phosphoric acid will be used
in the later tests.
4. Modelling of the coal elaboration
parameters
The operational parameters of carbon acti-
vated preparation were put in equation of first
degree by using the method of the experimental
designs.
In this method, each parameter takes two val-
ues coded higher level (+1) and lower (1).
Table 2 gathers the range of the parameters.
Table 1
Different conditions from activation
Agent of
activation
Agent activation
concentration (%)
Yield of
elimination (%)
HCl 20 6.41
HNO
3
20 54.38
H
3
PO
4
20 54.26
H
2
SO
4
20 29.67
HNO
3
10 34.67
ZnCl
2
20 34.00
HCl
(20%)
HNO
3
(20%)
H
3
PO
4
(20%)
H
2
SO
4
(20%)
HNO
3
(10%)
ZnCl
2
(20%)
0
10
20
30
40
50
60
Y
i
e
l
d

e
l
i
m
i
n
a
t
i
o
n

(
%
)
Fig. 1. The yield elimination of phenol by various agent
of activating.
266 N. El Hannafi et al. / Desalination 223 (2008) 264268
We carried out a complete factorial design of 2
4
following the experiment matrix. The answers (Y)
represent the yield of phenol elimination. The
results have been treated by Yates methods [68].
The general model was simplified; indeed
the calculation of the standard deviations showed
that certain coefficients of the general model are
influencing whereas others are not it. The model
obtained can be written as
Y = 52.39 + 8.51x
1
+ 4.71x
2
7.95x
3
3.40x
4
+ 6.04x
2
x
3
7.14 x
3
x
4
3.15x
1
x
2
x
3
+ 3.39x
2
x
3
x
4
.
In order to determine the coal elaboration
optimised conditions, we chose the temperature
of carbonisation like key parameter; then the
field experimental can be represented by three
parameters instead of four.
The experimental field can be represented by
a geometrical form (cube) Fig. 2, each vertex
represents an average yield:
The best average elimination yield are
obtained on the two faces of the cube corre-
sponding to
x
3
= 1:
x
2
= 1 to +1
x
4
= 1 to +1
x
2
= +1:
x
3
= 1 to +1
x
4
= 1 to +1
5. Kinetic of adsorption
The kinetic study showed that the maximum
of adsorption is reached after 60 min (Fig. 3);
this time can be taken as the equilibrium contact
time of phenolic solution and adsorbent.
6. The effect of pH
The study of the influence of pH on the yield
of adsorption was carried out in a range of 210.
The adjustment of solutions pH have been rea-
lised with an acid or a basic solution. The results
are represented in Fig. 4.
The maximum of adsorption is obtained
towards a pH = 5.5; it corresponds to a solution
initial without addition of acid or basic.
Table 2
Range values of parameters
Parameter Designation Level (1) Level (+1)
Carbonisation
temperature
x
1
700C 800C
Time of
carbonisation
x
2
2 h 3 h
Activant
concentration
x
3
10% 20%
Time of
activation
x
4
2 h 3 h
(+1)
(+1)
(1)
(1)
(1) (+1)
49.19
18.64
67.64
48.73
x
2
x
3
x
4
55.67 57.54
61.20
60.49
Fig. 2. Variation yield average in different conditions.
0
10
20
30
40
50
60
0 50 100 150
Time (min)
R
e
c
o
v
e
r
y

(
%
)
Fig. 3. Kinetic of adsorption.
N. El Hannafi et al. / Desalination 223 (2008) 264268 267
7. The effect of temperature
Many parameters can influence the elimina-
tion of phenol: temperature, stirring rate, adsor-
bent concentration. Initially, experiments have
been carried to determine the optimal tempera-
ture of the elimination of phenol, the operating
conditions were
concentration of adsorbent: 1 g/L.
concentration of the phenol: 1.27 g/L.
stirring speed 300 rpm.
contact time is 1 h.
The results from Fig. 5 show that the temper-
ature does not have an effect on elimination of
phenol.
8. Optimisation of the operating parameters
by application of simplex method
Two parameters are studied, stirring rate and
concentration of the activated carbon. The cor-
responding simplex is an equilateral triangle.
Basic points are
stirring rate = 300 rpm;
concentration of the activated carbon = 1 g/L.
The various elimination yield obtained dur-
ing calculations of simplex are given in Table 3.
Fig. 6 shows the various steps of simplex
evolution for optimum determination.
The iterations of simplex stop when there are
will be no more variation of the yield.
9. Modelling of parameters operating
The optimal parameters were modelled by
using the method of the experimental designs.
The ranges of parameter variation is gathered in
Table 4.
0
10
20
30
40
50
60
0 2 4 6 8 10 12
pH
R
e
c
o
v
e
r
y

(
%
)
Fig. 4. Effect of pH solution on phenol recovery.
0
10
20
30
40
50
60
0 10 20 30 40 50 60
Temperature (C)
R
e
c
o
v
e
r
y

(
%
)
Fig. 5. Effect of temperature on phenol elimination.
Table 3
Conditions and values of yield during different steps of
simplex method
Test Stirring rate
(rpm)
Concentration of
adsorbent (g/L)
Yield of
elimination (%)
0 300 1.00 69.81
1 400 1.13 77.18
2 325 1.50 85.23
3 425 1.63 71.14
4 350 2.00 74.15
5 400 1.13 77.18
A
d
s

(
g
/
L
)
2.00 77.18
Simplex 2
71.14
1.50 85.23
Simplex 1
Simplex 0
77.18
1.00 69.81
300 450 425 400 350 325
V (rpm)
Fig. 6. Simplex evolution.
268 N. El Hannafi et al. / Desalination 223 (2008) 264268
A model obtained is
Y = 68.63 + 2.98x
1
+ 9.04x
2
6.82x
3
1.01x
1
x
2
0.93x
1
x
3
+ 4.73x
2
x
3
3.58x
1
x
2
x
3
.
By the same manner the model is simplified,
it then becomes
Y = 68.63 + 9.04x
2
6.82x
3
+ 4.73x
2
x
3
.
10. Conclusion
The aim goal of this study is to model and
optimise the phenol elimination conditions by
adsorption.
The activated carbon preparation is an
important step; it includes the phases of carbon-
ization and activation. The phosphoric acid
gives the best results; 54% of elimination can
been reached with a mass percentage of phos-
phoric acid equal to 20%.
The best elimination is obtained for a pH
equal at 5.5.
The experimental design showed that is pos-
sible to implorer the phenol elimination; 70%
have been reached while the elaboration acti-
vated carbon conditions have been exploited.
The simplex method allows to approach
methodically the optimal zone, and to determine
the optimal point, with a certain error.
The simplex method applied for the optimi-
zation of the operating conditions (stirring rate,
activated carbon concentration) of adsorption
made it possible to improve the elimination
yield; the best elimination is located at the level
of the point of second simplex; its equal to 86%.
A model gathering the parameters optimise
was established.
References
[1] La guerre deau: gense, mouvement et changes,
pollutions et pnurie, Ineris, 2003, France.
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(1993) 7782.
[3] J.S. Matson and H.B. Mark, Activated Carbon-
Surface Chemistry and Adsorption from Solution,
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[4] Zhonghuahu and M.P. Srimivason, Preparation
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(1999) 1118.
[5] N. Calace, E. Nardi, B.M. Petronio and M. Pietroletti,
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91 (2006) 15631570.
Table 4
Conditions of experimental design
Parameter Designation Level
(+1)
Level
(1)
Stirring rate (rpm) x
1
500 300
Concentration of the
activated carbon (g/L)
x
2
2.00 1.00
Concentration of
pollutant (g/L)
x
3
1.00 2.00