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Chemosphere 58 (2005) 423437

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Experimental design methodology for the preparation


of carbonaceous sorbents from sewage sludge by
chemical activationapplication to air and water treatments
Sebastien Rio a,*, Catherine Faur-Brasquet a,*, Laurence Le Coq a,
Philippe Courcoux b, Pierre Le Cloirec a
a

Ecole des Mines de Nantes, GEPEA UMR CNRS 6144, 4 rue Alfred Kastler, BP 20722, 44307 Nantes Cedex 3, France
b
ENITIAA, SMAD Department, rue de la Geraudiere, BP 82225, 44322 Nantes Cedex 3, France
Received 24 March 2004

Abstract
The objective of this study is to optimize experimental conditions of sorbent preparation from sewage sludge
using experimental design methodology. Series of carbonaceous sorbents have been prepared by chemical activation
with sulfuric acid. The sorbents produced were characterized, and their properties (surface chemistry, porous and
adsorptive properties) were analyzed as a function of the experimental conditions (impregnation ratio, activation
temperature and time). Carbonaceous sorbents developed from sludge allow copper ion, phenol and dyes (Acid Red 18
and Basic Violet 4) to be removed from aqueous solution as well as VOC from gas phase. Indeed, according to
experimental conditions, copper adsorption capacity varies from 77 to 83 mg g1 , phenol adsorption capacity varies
between 41 and 53 mg g1 and VOC adsorption capacities (acetone and toluene) range from 12 to 54 mg g1 . Each
response has been described by a second-order model that was found to be appropriate to predict most of the responses
in every experimental region. The most inuential factors on each experimental design response have been identied.
Regions in which optimum values of each factor were achieved for preparation of activated carbons suitable for use in
wastewater and gas treatments have been determined using response surfaces methodology. In order to have a
high mass yield and to minimize the energetic cost of the process, the following optimal conditions, 1.5 g of H2 SO4 g1
of sludge, 700 C and 145 min are more appropriate for use of activated carbon from sludge in water and gas treatments.
 2004 Elsevier Ltd. All rights reserved.
Keywords: Sewage sludge; Valorization; Activated carbon; Chemical activation; Porosity; Adsorption

1. Introduction
Activated carbon is a highly eective adsorbent that
is widely used for water and gaseous emissions puri*

Corresponding authors. Tel.: +33-2-5185-8295 (S. Rio),


tel.: +33-2-51-85-82-94; fax: +33-2-51-85-82-99 (C. FaurBrasquet).
E-mail addresses: sebastien.rio@emn.fr (S. Rio), catherine.faur@emn.fr (C. Faur-Brasquet).

cation. This is due to their extended specic surface area


between 500 and 2000 m2 g1 , their high pore volume
and the presence of surface functional groups, especially
oxygen groups (Bansal et al., 1988). Activated carbons
are commonly obtained from various organic precursors
such as peat, wood, bituminous coal, coconut shells,
polymers, etc. (Bansal et al., 1988). In the physical
activation process, the precursor is rst carbonized at
600800 C under an inert atmosphere and activated
using steam or carbon dioxide at upper temperature.

0045-6535/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2004.06.003

424

S. Rio et al. / Chemosphere 58 (2005) 423437

When activated carbons are prepared by chemical


activation, the precursor is mixed with chemical compounds such as phosphoric acid or sulfuric acid and
carbonized-activated in a same step at various temperatures (Bagreev et al., 2001a). In recent years, a growing research interest consists in the production of
carbon-based adsorbents from a range of low-cost
precursors, mainly industrial or agricultural by-products. Polymers (Yue et al., 2002), wastes tires (San
Miguel et al., 2003) and numerous agricultural byproducts including wood (Tseng et al., 2003), almond
shells (Toles et al., 2000), apple pulp (Suarez-Garcia
et al., 2001), sugarcane bagasse (Mohan and Singh,
2002) or pecan shells (Bansode et al., 2003) have been
successfully converted into activated carbons on laboratory scale.
On searching for economical and available starting
material, sewage sludge, the by-product generated during wastewater treatment processes, has been identied
as an attractive precursor for activated carbon production (Chiang and You, 1987; Lu et al., 1995; Bagreev
et al., 2001b; Tay et al., 2001; Calvo et al., 2001). In
France, sewage sludge production is about 950 000 tons
of dried matter per year. The traditional ways of sludge
valorization include farmland application, landll and
incineration. But, with some traditional disposal ways
coming under pressure like farmland applications and
others being phased out like landll, it is necessary to
seek cost-eective and innovative solutions to sewage
sludge disposal problem. Activated carbon preparation
from sewage sludge can be considered as an attractive
method in reducing sludge volume, and at the same
time, it produces reusable by-products. But, recent
studies which have shown the feasibility of this conversion rarely determine the eects of activation conditions
on physico-chemical properties of sorbents produced as
well as on adsorption capacities of standard industrial
wastewater pollutants and volatile organic compounds
(VOC) in gas phase.
In this work, we focus on the preparation of activated carbon from sewage sludge. This is carried out by
chemical activation process using sulfuric acid. The
preparation of activated carbon is inuenced by many
factors. For this reason, a preliminary study on the eect
of these factors on activated carbon production has
been carried out in order to determine the most important ones and their regions of interest (Rio et al., 2003).
In this study, the most inuential factors were found to
be impregnation ratio, activation temperature and activation time. Dierent characteristics of the activated
carbon produced are analyzed as a function of these
three factors. The main advantages of experimental designs are: (i) the ability to evaluate the eects of interactions between tested examined parameters; (ii) the
gain in reducing the number of experiments to be

undertaken, in comparison to a classical approach for


the same number of estimated parameters (Box and
Draper, 1987). This methodology is widely used in
chemical engineering notably to optimize adsorption
processes (Ricou et al., 2001; Annadurai et al., 2002) but
also to optimize experimental conditions for activated
carbon preparation from waste (Bacaoui et al., 2001).
An experimental design is used to represent the responses of the factors in all the experimental regions
studied and to optimize the experimental conditions
for carbonaceous sorbents preparation from sewage
sludge.

2. Materials and methods


2.1. Raw material
Viscous liquid sludge collected from the municipal
wastewater treatment plant of Nantes-Tougas, in France,
is used as precursor in this study. In this domestic
wastewater treatment plant, wastewater undergoes a
biological treatment by activated sludges. Viscous liquid
sludge corresponds to aerobically digested sludge dewatered by centrifugation. Dried matter content, ash content
and elemental composition of sludge samples are assessed
by French standard methods (AFNOR NF U 44-171,
1982).
2.2. Activated carbon preparation
Chemical activation with sulfuric acid is carried out
using an impregnation method. Dried viscous liquid
sludge is mixed with H2 SO4 solutions (13 M) for 6 h.
The resulting mixture is ltered and dried at 105 C.
Then, the impregnated sludge is introduced in a 2 l
horizontal furnace and carbonized under nitrogen
atmosphere at 20 C min1 . Nitrogen ow rate is equal
to 2.5 l min1 . The eects of impregnation ratio (0.51.5
g H2 SO4 g1 sludge), activation temperature (600800
C) and activation time (60180 min) are analyzed using
experimental design methodology. The regions of
interest of these factors have been detected in previous
study (Rio et al., 2003). This study, factor by factor,
was carried out by varying activation temperature between 400 and 900 C, activation duration between 1
and 3 h and H2 SO4 concentration from 1 to 3 M. And,
the inuence of these operating conditions on porosity
development have been studied. Notably, higher activating agent concentration is not used because preliminary experiments have shown that, when sulfuric
acid concentration is higher than 3 M, destruction of the
material structure occurs during the thermal treatment
(Rio et al., 2003).

S. Rio et al. / Chemosphere 58 (2005) 423437

2.3. Activated carbon characterization


2.3.1. Porosity measurements
Nitrogen adsorption/desorption isotherms are measured at 77 K with a MICROMERITICS ASAP 2010
surface area analyzer. Samples are outgassed between
100 and 350 C, depending on the materials activated or
not, in a vacuum during 3 d before analysis. The specic
surface area (SBET ) is calculated by BET equation
(Brunauer et al., 1938). The mesopore (250 nm) and
micropore (<2 nm) volumes are estimated according to
Barrett et al. (1951) and Horwath and Kawazoe (1983)
theories, respectively.
Microstructure of dried sludges and chemically activated sludges is observed with a Scanning Electron
Microscope JEOL 6400 F.
2.3.2. Chemical properties of materials
Surface pH is measured by adding 0.4 g of dried
sorbent to 20 ml of deionized water. The suspension is
stirred for 24 h to reach equilibrium. The sample is ltered and the pH of solution is measured (Bagreev et al.,
2001a).
Surface functional groups are estimated according to
Boehm method (1966) based on the titration of total
basic surface groups and four acidic surface groups:
strong carboxylic functions, weak carboxylic and lactone functions, phenolic functions and carbonyl functions.
The elemental analysis of dried sludges and carbonized sludges are realized with a THERMOQUEST
NA2100 elemental analyzer giving the mass percentage
of carbon, oxygen, hydrogen, nitrogen and sulfur.
2.4. Adsorption tests
Prior to adsorption tests, sludge-based adsorbents
are crushed manually and dried at 105 C. The particle
size is estimated to be equal to 0.11 mm.
2.4.1. Adsorption experiments in aqueous solution
A metallic ion: Cu2 , an organic pollutant: phenol,
and two organic dyes: Acid Red 18 and Basic Violet 4,
are used to test the adsorption capacities of the activated
carbons produced. These four pollutants are chosen
because they represent dierent types of standard
industrial wastewater pollution. Adsorption kinetic
experiments are performed with all the activated carbons
produced for each adsorbate: 500 mg of chemically
activated sludges are continuously stirred (300 rpm) in 1
l of aqueous solutions with an initial concentration of
100 mg l1 for copper or phenol adsorption experiments,
30 mg l1 for Acid Red 18 and 50 mg l1 for Basic Violet
4 adsorption experiments. The temperature is 20 1 C.
During copper adsorption experiments, pH is xed to

425

the value 5, if necessary, to avoid copper precipitation in


solution. Copper is analyzed by an atomic absorption
spectrophotometer (PerkinElmer Aanalyst 200) and,
dyes and phenol are analyzed using a spectrophotometer
UV (Shimadzu 1601).
2.4.2. Adsorption experiments in gas phase
Two dierent volatile organic compounds (VOC)
have been used in this study, acetone and toluene.
Adsorption kinetic experiments are carried out at room
pressure and temperature (about 20 C). 200 mg of
activated carbon produced is introduced into 2 l reactor
with initial VOC concentration of 10 mg l1 by injecting
organic pollutants as liquid phase. Acetone and toluene
concentrations are measured using a gas chromatograph
(PerkinElmer Autosystem XL).
Adsorption kinetic equilibrium is reached in 3 d
during copper and phenol kinetics experiments, in 5 d
for dyes adsorption kinetics and in 2 d during VOC
adsorption kinetics in gas phase. When adsorption kinetic equilibrium is reached, adsorption capacities at
equilibrium, qe (mg g1 ), are determined according to the
mass balance between the solid and the liquid/gas phase
in the reactors.
2.5. Experimental design methodology
As detected in previous study (Rio et al., 2003) the
most inuential factors on the physico-chemical characteristics of activated carbon from sludge are activation
temperature X1 , activation time X2 and impregnation
ratio X3 . In order to evaluate the eects and interactions of these three factors, a central composite design is
used. This design is constructed based on a 23 factorial
design, three replicates of the central run and six star
points, allowing each experimental response to be optimized. The experimental conditions required by this
design are dened in Table 1. The levels chosen for each
of the three parameters are also presented in this table
and their values depend on results of preliminary
experiments. A second-order model is selected in order
to predict each response Y in all experimental regions
(Box and Draper, 1987):
Y a0 a1 X1 a2 X2 a3 X3 a12 X1 X2 a13 X1 X3
2
a23 X2 X3 a11 X12 a22 X21
a33 X32

For each response Y , the parameters aij of the


model are estimated from experimental responses by
least squares regression using STATGRAPHICS software.
Following the model tted for each response, we
represent graphically isoresponses surfaces which are
three-dimensional models of the relationship between
the responses and two factors. This response surfaces

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S. Rio et al. / Chemosphere 58 (2005) 423437

Table 1
Experimental design matrix
No. Exp.

1
2
3
4
5
6
7
8
Central run 1
Central run 2
Central run 3
Star point 1
Star point 2
Star point 3
Star point 4
Star point 5
Star point 6

Table 2
Physico-chemical characteristics of raw sewage sludge

Temperature
(C)
X1

Time
(min)
X2

Impregnation
ratio
X3

600
600
600
600
800
800
800
800
700
700
700
532
868
700
700
700
700

60
60
180
180
60
60
180
180
120
120
120
120
120
20
220
120
120

0.5
1.5
0.5
1.5
0.5
1.5
0.5
1.5
1
1
1
1
1
1
1
0.15
1.85

methodology allows experimental responses behavior to


be described as precisely as possible as a function of
factor variation and optimal conditions of the factors to
be determined for each experimental response.
3. Results and discussion
3.1. Characterization of raw sewage sludge
The results of physico-chemical analysis of viscous
liquid sludge are presented in Table 2. First, dried
matter content of viscous liquid sludge is equal to 19.2%.
The relatively high quantity of carbon within viscous
liquid sludge (39.4 wt%) shows that it has the potential
to be converted in carbonaceous sorbent. Viscous liquid
sludge develops low SBET of 2.9 m2 g1 , and the pore
structure of the sludge is mainly macroporous. Finally,
the sludge contains heavy metals like lead or mercury
but their concentration are lower than the values xed
by French regulation. To evaluate the stability of these
toxic metallic compounds, the raw material and the
resulting sorbents have been submitted to leaching test
adapted from the French standard AFNOR X31-210
(2000). The results notably show that these heavy metals
are very stable within the raw material and the resulting
sorbents. The leaching percentage of these metallic
compounds was very low and did not exceed 2% in
demineralized water acidied at pH 5.
3.2. Responses analysis and interpretation
The experimental responses studied include: activation mass yield Y1 , porous structure, surface chemistry

Property/element
2

1

SBET (m g )
Macroporosity (vol.%)
Dried matter (wt%)
Ash content (wt% of dried matter)
Carbon (wt%)
Oxygen (wt%)
Hydrogen (wt%)
Nitrogen (wt%)
Sulfur (wt%)
Phosphorus (wt%)
Calcium (wt%)
Potassium (wt%)
Magnesium (wt%)
Iron (wt%)
Copper (ppm)
Nickel (ppm)
Lead (ppm)
Zinc (ppm)
Mercury (ppb)

Sewage sludge
2.9
97.0
19.2
22.0
39.4
19.8
5.6
6.4
0.9
1.9
2.9
0.7
0.5
0.8
306
76
64
634
<5

and adsorption capacities at equilibrium. Porosity


development is characterized by SBET Y2 , mesopore
volume Y3 and micropore volume Y4 . Surface chemistry evolution during activation is determined by measurements of surface pH Y5 , acidic surface functional
groups Y6 and basic surface functional groups Y7 .
These characteristics are chosen because of their strong
inuence on activated carbon adsorption capacity
(Boehm, 1966). In order to estimate adsorption eciency of sorbents produced towards standard industrial
pollutants, the following responses are also studied:
adsorption capacities of copper Y8 , phenol Y9 , Basic
Violet 4 Y10 and Acid Red 18 Y11 in aqueous solution
and adsorption capacities of acetone Y12 and toluene
Y13 in gas phase. The experiments are carried out in a
random order. The values obtained experimentally for
these characteristics of the carbonaceous sorbents produced as well as coecients of determination R2
between observed values and values predicted by the
second order model are given in Table 3. And, if low
values of these coecients of determination are observed
R2 < 0:8, lack-of-t tests are designed to determine
whether the selected models are adequate to describe the
observed data, or whether another model should be used.
If the model has a signicant lack-of-t, as indicated by
an p-value less than 0.05 at the 95% condence level, this
model should not be used to predict the response.
3.2.1. Mass yield (Y1 )
The results of experimental design show that mass
yield values range from 33% to 49% (Table 3). A satisfying correlation R2 0:941 is obtained between theoretical responses, obtained by the second order

S. Rio et al. / Chemosphere 58 (2005) 423437

427

Table 3
Experimental design responses
No. Exp.
1
2
3
4
5
6
7
8
Central run 1
Central run 2
Central run 3
Star point 1
Star point 2
Star point 3
Star point 4
Star point 5
Star point 6
R2
Lack-of-t test

Yield

Porosity development

Chemical properties

Adsorptive properties

Y1

Y2

Y3

44.3
44.9
44.1
45.2
36.4
37.1
36.4
36.6
38.4
38.6
38.9
49.6
33.3
37.5
35.1
38.7
37.6
0.941

157
259
177
353
77
322
58
327
248
251
255
69
61
200
252
231
352
0.895

0.061
0.048
0.042
0.244
0.048
0.217
0.046
0.239
0.046
0.045
0.047
0.042
0.047
0.046
0.048
0.23
0.231
0.806

Y4

Y5

Y6

Y7

Y8

Y9

Y10

Y11

Y12

Y13

0.084
0.131
0.094
0.129
0.032
0.125
0.023
0.125
0.128
0.13
0.131
0.029
0.024
0.104
0.125
0.085
0.148
0.929

5.8
5.4
6.1
5.9
5.9
5.0
6.5
6.0
6.4
6.3
6.5
6.7
7.1
5.9
5.6
6.9
5.9
0.672
0.03

0.89
0.92
0.77
0.79
0.71
0.80
0.64
0.75
0.83
0.79
0.81
0.84
0.65
0.85
0.76
0.70
0.81
0.967

0.34
0.29
0.27
0.24
0.22
0.18
0.20
0.16
0.23
0.24
0.24
0.39
0.14
0.20
0.20
0.36
0.20
0.914

78
81
79
83
77
82
77
82
81
81
81
77
77
80
81
81
83
0.907

47
52
49
54
41
53
41
53
42
43
43
51
47
54
51
52
54
0.748

69
77
70
89
63
88
62
88
76
77
77
63
64
76
77
75
88
0.895
0.11

50
49
48
54
46
53
48
53
49
50
49
46
46
47
47
53
53
0.901

26
49
24
48
15
48
12
48
49
50
51
14
12
32
49
30
51
0.899

29
51
31
54
18
53
14
54
52
52
52
15
13
40
51
39
54
0.887

Y1 , mass yield (%); Y2 , SBET (m2 g1 ); Y3 , mesopore volume (cm3 g1 ); Y4 , micropore volume (cm3 g1 ); Y5 , surface pH; Y6 , acidic surface
functional groups (meq g1 ); Y7 , basic surface functional groups (meq g1 ); Y8 , adsorption of copper (mg g1 ); Y9 , adsorption of phenol
(mg g1 ); Y10 , adsorption of Basic Violet 4 (mg g1 ); Y11 , adsorption of Acid Red 18 (mg g1 ); Y12 , adsorption of acetone (mg g1 ); Y13 ,
adsorption of toluene (mg g1 ); R2 , coecients of determination between observed values and predicted values, Lack-of-t, p-value of
lack-of-t statistical test.

statistical model, and experimental responses. The effects of the three factors on mass yield Y1 are presented
in Fig. 1. Activation temperature X1 has a highly
negative eect on yield Y1 , i.e., the increase of temperature from 600 to 800 C leads to a decrease of mass
yield, compared with others factors that have a very
weak eect on this response. Indeed, the increase in
temperature quickens the gasication reactions and,
therefore, the removal of amorphous components which
obstruct the pores, leading to a decrease in mass yield
(Bacaoui et al., 2001). Then, no signicant interactions
between the factors have been observed.

Fig. 1. Main eect plot for mass yield (%).

3.2.2. Porosity development


The activation process allows to create and develop
the porous surface and volume giving adsorbent qualities to resulting activated carbon. The nal porous
structure of the activated carbon is governed by the
precursor structure and by activation conditions (Bansal
et al., 1988). Generally, porosity of commercial activated
carbons is mainly constituted of micropores and even
mesopores.
First, the SBET Y2 of the sorbents varies from 59 to
352 m2 g1 according to the experimental conditions
(Table 3). These values are in agreement with literature
datas. Lu and Lau (1996) have obtained, during sewage
sludge chemical activation with 3 M H2 SO4 at 650 C, an
SBET of 220 m2 g1 . Identical experiments have also been
carried out by Rozada et al. (2003) and they have obtained adsorbents developing 390 m2 g1 at 625 C. But,
SBET values obtained in this paper remain lower than
these of commercial activated carbons which usually
vary between 500 and 2000 m2 g1 (Bansal et al., 1988).
Note that commercial activated carbon consists of various mineral compounds (ash) in quantities lower than
10% (Hassler, 1974) where as sorbents produced from
sludge in this study contains between 35% and 40% of
ash (Table 4). That ash content limits the porosity
development occurring within organic matter and behaves only as an inert material which does not contribute

428

S. Rio et al. / Chemosphere 58 (2005) 423437

Table 4
Ash and carbon, hydrogen, oxygen, nitrogen and sulfur contents (wt%)
X1

X2

X3

Ash content

Carbon

Hydrogen

Oxygen

Nitrogen

Sulfur

600
600
600
600
800
800
800
800
700

60
60
180
180
60
60
180
180
120

0.5
1.5
0.5
1.5
0.5
1.5
0.5
1.5
1

35.0
34.5
38.1
37.4
40.3
40.3
41.7
41.2
35.9

42.2
40.8
37.3
35.9
44.5
39.9
42.5
37.0
43.1

1.2
1.2
1.5
1.5
1.5
1.6
1.2
1.3
1.6

11.0
11.6
10.4
10.7
10.1
10.3
8.6
9.1
8.6

4.4
3.7
4.2
3.8
3.0
2.6
2.7
2.5
3.6

3.1
4.1
4.3
4.4
3.9
5.0
4.1
5.0
5.0

to the porosity (Linares-Solano et al., 2000). By this way,


porosity development could be recalculated, taking only
organic matter content into account, and reaches about
500 m2 g1 of organic matter.
A correct correlation between observed responses
and predicted responses is obtained by the statistical
model, with coecient of determination of 0.895 (Table
3). The eects and interaction of the factors on SBET Y2
are presented in Fig. 2. On one hand, response analysis
shows that activation temperature X1 has slightly
negative eect on this response, but, the important
quadratic eect observed suggests that an optimal SBET
value is reach between 600 and 800 C. On the other
hand, the increase in activation time X2 and impregnation ratio X3 allows SBET Y2 to be developed.
Interaction plot is also presented in Fig. 2, it shows the

estimated variable as a function of pairs of factors. In


each plot, the SBET evolves versus the rst written factor
in the X-axis and is parameterized according to the
second written factor. The + curves stand for the
maximum values of the parameter and the ) curves
stand for the minimum values. So, important interactions exist between activation temperature and impregnation ratio X1 X3 (positive) which is more important
than the eects of X1 . Indeed, Fig. 2 shows that when the
impregnation ratio is xed to the lower value (0.5 g
H2 SO4 g1 sludge), the increase of temperature leads to
a dramatic decrease of SBET , while, when experiments are
carried out with high impregnation ratio (1.5 g H2 SO4
g1 sludge), the increase in temperature allows SBET to be
increased. Such interaction is observed between activation time and impregnation ratio X2 X3 .

Fig. 2. Main eect plot and interaction plot for SBET (m2 g1 ) and mesopore volume (cm3 g1 ).

S. Rio et al. / Chemosphere 58 (2005) 423437

429

impregnation ratio X1 X3 and between activation time


and impregnation ratio X2 X3 because the increase of
temperature X1 or time X2 improve mesopore volume
Y3 if impregnation ratio X3 is xed to the value 0.5
while, this response decreases with increasing temperature or time when impregnation ratio is xed to the
value 1.5.
Finally, the observation of pore size distributions of
the resulting sorbents activated at 600 and 800 C, with
an impregnation ratio of 1.5, conrms the positive eect
of temperature on mesopore volume Y3 (between 2 and
50 nm) and the positive eect of activation time (between 1 and 3 h) on mesopore volume (as well as on
micropore volume (<2 nm)) (Fig. 3).
The surface of the dried sludge and the resulting
chemically activated carbons have been observed using
scanning electron microscopy (Fig. 4). The structure of
the raw sludge is very dense and surface is smooth (Fig.
4a). After the activation process, the structure is dierent, less dense, and porosity appears as shown in Fig. 4b
for a same magnitude as Fig. 4a (550). The important
gasication of organic matter and the removal of sulfuric acid during the activation lead to an important
macroporosity (Fig. 4c) formation, yielding microporosity more accessible, and to mesoporosity development (Fig. 4d).

For micropore volume response Y4 which results


are not presented in this paper, exactly the same trends
for SBET response in terms of eects and interactions of
the factors are obtained. In addition, these two experimental responses are very dependent, the coecient of
determination between SBET Y2 and micropore volume
Y4 is equal to 0.937 (Table 5). The increase of
impregnation ratio X3 and activation time X2 improves the micropore volume Y4 of the sorbents obtained. The increase of activation time X2 would cause
the opening of closed or non-accessible micropores. The
increase of impregnation agent concentration improves
SBET and micropore volume because the role of the
impregnation agent is to minimize the formation of tars
and any other liquids that could block the pores and
inhibit the porous structure development within the
sorbent (Guo and Lua, 1999).
The value of coecient of determination (Table 3)
between calculated and observed mesopore volume
Y3 reveals that the statistical model obtained does
not correctly model experimental response because it
explains only 81% of the variability in this response.
Main eect plot shows that all the experimental design
factors have a positive eect on mesopore development (Fig. 2). The continuous increase in mesopore
volume Y3 with the increase of activation temperature X1 and time X2 would result from a micropores
widening phenomenon (Daley et al., 1996; Martin et al.,
1996). Interaction plot reveals that important interactions exist between the three factors of the experimental design within the region of variability studied.
Mesopore volume Y3 increases with increasing temperature X1 if activation time X2 is xed to 60 min
while it decreases with increasing temperature X1
when activation time X2 is xed to 180 min. Important interactions also exist between temperature and

3.2.3. Chemical properties


For surface chemistry characterization, surface pH
Y5 , acidic surface functional groups Y6 and basic
surface functional groups Y7 have been measured. The
surface charge and the quantity of functional groups can
have a signicant inuence on the adsorption properties.
The activated carbon surface chemistry can participate
to ionized molecules removal in aqueous solution
(Petrov et al., 2000).

Table 5
Values of coecients of determination R2 between experimental design responses
Y2
Y3
Y4
Y5
Y6
Y7
Y8
Y9
Y10
Y11
Y12
Y13

Y2

Y3

Y4

Y5

Y6

Y7

Y8

Y9

Y10

Y11

Y12

Y13

1
0.678
0.937
)0.514
0.383
)0.199
0.986
0.525
0.979
0.923
0.927
0.957

1
0.393
)0.219
)0.102
)0.118
0.641
0.604
0.942
0.891
0.395
0.464

1
)0.522
0.543
)0.154
0.935
0.384
0.874
0.838
0.970
0.980

1
)0.505
0.196
)0.480
)0.365
)0.520
)0.303
)0.493
)0.504

1
0.405
0.396
0.338
0.312
0.852
0.472
0.459

1
)0.188
0.076
)0.313
)0.071
)0.214
)0.197

1
0.526
0.961
0.773
0.935
0.962

1
0.575
0.469
0.300
0.381

1
0.835
0.874
0.908

1
0.618
0.671

1
0.989

1

1

1

Y2 , SBET (m g ); Y3 , mesopore volume (cm g ); Y4 , micropore volume (cm g ); Y5 , surface pH; Y6 , acidic surface functional groups
(meq g1 ); Y7 , basic surface functional groups (meq g1 ); Y8 , adsorption of copper (mg g1 ); Y9 , adsorption of phenol (mg g1 ); Y10 ,
adsorption of Basic Violet 4 (mg g1 ); Y11 , adsorption of Acid Red 18 (mg g1 ); Y12 , adsorption of acetone (mg g1 ); Y13 , adsorption of
toluene (mg g1 ).

430

S. Rio et al. / Chemosphere 58 (2005) 423437

Fig. 3. Pore size distributions of sorbent produced with


impregnation ratio of 1.5.

First, every sorbents produced are acidic, surface pH


varying between 5 and 7, due to the important quantity

of acidic surface functional groups as shown in Table 3.


Amount of acidic surface groups Y6 is always at least
two times more important than basic surface groups
Y7 . The quantities of acidic surface groups Y6 and
basic surface groups Y7 can be very correctly described
by a second order model, R2 values are equal to 0.967
and 0.914, respectively (Table 3). In the case of surface
pH response Y5 , the second order model is not adapted. A lack-of-t test is performed to test the adequacy
of the model. The p-value of lack-of-t statistical test is
less than 0.05 and equal to 0.03 (Table 3). So, there is
statistically signicant lack-of-t at the 95% condence
level. This means that the model as tted does not
adequately represent the data. In addition, during the
analysis of variance of surface pH response, the test of
statistical signicance of each factor is also performed. It
is carried out by comparing the mean square against an
estimate of the experimental error. The results show that
only two eects, activation duration X2 and impregnation ratio X3 , have p-values less than 0.05, indicating
that they are signicantly dierent from zero at 95% of
condence level. The statistical analysis of this response
is not carried out in this paper.
Then, Fig. 5 clearly shows that activation temperature
X1 and time X2 have a negative eect on amounts of
acidic surface groups Y6 and basic surface groups Y7 .
As indicated in literature, surface groups decompose at
elevated temperature and their decomposition increases
with increasing activation time (Boehm, 1966). The increase of impregnation ratio X3 leads to increase in
acidic character of the sorbents produced because this
factor has a strong positive impact on amount of acidic
surface groups Y6 and a negative eect on amount of
basic surface groups Y7 (Fig. 5).

Fig. 4. Micrographs of dried sludge (a) and chemically activated sludge (b)(d).

S. Rio et al. / Chemosphere 58 (2005) 423437

Fig. 5. Main eect plots for acidic and basic surface functional
groups (meq g1 ).

The elemental analysis carried out on the resulting


activated carbon shows that oxygen contents decrease
when activation temperature X1 and time X2 increase
(Table 4). It would conrm that amounts of acidic and
basic surface functional groups decrease with the increase of these experimental design factors (Boehm,
1966). Sulfur content varies from 3.1% to 5.0% according to the experimental conditions, the highest values
(between 4% and 5%) being found for the highest
impregnation ratio of 1.5 (Table 4). Sulfur content
within dried sludge being equal to 0.9%, important
quantity of sulfur incorporated into the materials during
impregnation step, is not removed during thermal
treatment. Table 4 also shows that both oxygen and
sulfur contents increase with increasing impregnation
ratio because of the oxydizing eect of H2 SO4 (Daley
et al., 1996). Carbon content varies from 36% to 45%
according to activation conditions and carbon content
seems to decrease with increasing impregnation ratio
due to dilution eect. Finally, ash content varies from
45.0% to 51.7% and it increases with increasing temperature and time. Ash content seems to slightly decrease with increasing impregnation ratio because the
activating agent limits the formation of tars (Martin
et al., 1996).
3.2.4. Adsorption tests in aqueous solution
First, copper adsorption capacity Y8 varies from 77
to 83 mg g1 and this response is correctly modeled by
the statistic model because it explains more than 90% of

431

the variability of the response (Table 3). These values are


in agreement with copper adsorption capacities obtained
with commercial activated carbons (Faur-Brasquet
et al., 2002) and activated carbon prepared from agricultural by-products (Toles et al., 1999). Main eect plot
shows a negative eect of activation temperature X1 ,
while, activation time X2 and impregnation ratio X3
have a positive eect (Fig. 6). But, the important quadratic eect of activation temperature X1 reveals that
optimal value of this factor can be achieved. The eects
of the three factors are similar to those obtained for SBET
Y2 (Fig. 2) and micropore volume Y4 . This observation is conrmed by the important coecient of determination between copper adsorption capacity Y8 and
SBET Y2 , and between, copper adsorption capacity Y8
and micropore volume Y4 (Table 5). So, these porous
characteristics seem to partly control the copper removal
eciency by the sorbents produced. During copper
adsorption experiments, the evolution of calcium concentration in solution has been followed. The evolution
of Cu2 removed and Ca2 exchanged during kinetic
experiment with chemically activated sludge at 600 C
for 180 min and with impregnation ratio of 1.5 are
presented in Fig. 7. The simultaneous desorption of
calcium in solution would indicate that ion exchange
mechanism would also take place in the sorption phenomenon of metallic ion.
Experimental design results show that phenol
adsorption capacity varies from 41 to 54 mg g1
according to activation conditions and the second order
model as tted explains only 75% of the variability of
this response (Table 3). So, a lack-of-t statistical test is
realized to test the adequacy of this model. The p-value
of the lack-of-t is greater than 0.05 (Table 3), the model
appears to be adequate for the observed data at the 95%
condence level. The values of phenol adsorption
capacities remain lower than phenol adsorption capacities obtained with commercial activated carbon (Nevskaia et al., 1999) but they are similar to those obtained
using activated carbon from sludge (Martin et al., 1996;

Fig. 6. Main eect plot for copper adsorption capacity


(mg g1 ).

432

S. Rio et al. / Chemosphere 58 (2005) 423437

Fig. 7. Evolution of Cu2 removed (mM) and Ca2 exchanged


(mM) during kinetic experiment with chemically activated
sludge at 600 C for 180 min and with impregnation ratio of 1.5.

Chen et al., 2002). The increase of activation temperature X1 and time X2 lead to the lightly decrease of
phenol adsorption capacity Y9 when the increase of
impregnation ratio has a positive eect on this response
(Fig. 8). Even no strong dependence between this response and porosity development, notably micropore
development Y4 , has been identied, this increase of
phenol adsorption with increasing impregnation ratio is
attributed to the important microporosity development
(Martin et al., 1996). Experimental results show that
highest phenol adsorption capacities are observed when
important microporosity development occurs during
activation that corresponds to experiments (nos. 2, 4, 6,
8) carried out using impregnation ratio of 1.5 (Table 3).
Finally, an important interaction exists between activation temperature and impregnation ratio X1 X3 . As
shown in Fig. 8, when impregnation ratio X3 is xed to
the lower level (0.5 g H2 SO4 g1 sludge), the increase of
activation temperature X3 leads to important decrease
of phenol adsorption capacity Y9 , and, when impregnation ratio X3 is xed to the value +1 (1.5 g H2 SO4
g1 sludge), phenol adsorption capacity Y9 slightly increase with increasing activation temperature X3 . The
same trend was observed for SBET Y2 and micropore

volume Y4 responses. So, when the quantity of sulfuric


acid is low during impregnation, the increase of activation temperature would lead to a micropore widening
(or destruction) and a decrease of phenol adsorption.
And, when, impregnation ratio and activation temperature increase, an important micropore development
would occur, favoring phenol adsorption.
Finally, similar adsorption experiments have been
carried out to estimate the anity of the sorbents prepared to remove Basic Violet 4, a cationic dye, and Acid
Red 18, an anionic dye, for aqueous solution. The
experimental data can be correctly tted by second order
model, the coecients of determination between experimental and predicted adsorption capacities of Basic
Violet 4 and Acid Red 18 are equal to 0.895 and 0.901,
respectively. Fig. 9 presents the statistical results obtained for Basic Violet 4 adsorption because exactly the
same trend is observed for Acid Red 18 adsorption in
terms of eects of the experimental design factors. First,
activation temperature X1 seems to have no eect on
dye adsorption capacity but important quadratic eect of
this factor allows an optimal value to be determined. The
increase of activation time X2 and impregnation ratio
X3 allow dye adsorption capacity to be increased (Fig.
9). The factors eects are identical to those obtained for
mesopore volume Y3 (Fig. 2). Indeed, a strong dependence would exist between dye adsorption capacities
(Basic Violet 4 and Acid Red 18) and SBET Y2 , mesopore
volume Y3 and micropore volume Y4 (Table 5). Due to
dye molecule size (23 nm) both micropore and mesopore development are important for the adsorption
process of these organic pollutants. Because of anionic
character of Acid Red 18 molecule, an important correlation also exists between Acid Red 18 adsorption
capacity Y11 and the amount of acidic surface groups
Y6 that would participate to adsorption mechanism of
this dye, negatively charged in aqueous solution.
3.2.5. Adsorption tests in gas phase
Adsorption experiments in gas phase are carried out
to estimate the eciency of the sorbents produced to

Fig. 8. Main eect plot and interaction plot for phenol adsorption capacity (mg g1 ).

S. Rio et al. / Chemosphere 58 (2005) 423437

433

and 800 C due to quadratic eect of this factor, and


positive eects of activation time and impregnation ratio
(Fig. 10). The eects of these factors on VOC adsorption
capacities are identical to those obtained for SBET and
micropore volumes responses (Fig. 2). This observation
is conrmed by values of correlation coecients
revealing a strong dependence between these responses
(Table 5). This dependence between VOC adsorption
and microporosity development have been observed in
numerous research works (Subrenat, 1999; Chiang et al.,
2001; Lillo-Rodenas et al., 2002).
3.3. Optimization step

Fig. 9. Main eect plot for Basic Violet 4 and acetone


adsorption capacities (mg g1 ).

remove two dierent VOC: acetone and toluene.


Experimental design results show that adsorption
capacities of acetone Y12 and toluene Y13 vary between 1251 mg g1 and 1354 mg g1 , respectively.
Adsorption capacities of acetone and toluene onto
commercial activated carbons are, in the same experimental conditions, at least two times higher than values
obtained in this study (Subrenat, 1999). These data are
correctly tted by a second order model (Table 3). Solely
statistical results of acetone adsorption capacity Y12
are presented in Fig. 10 because the same trends are
observed for toluene adsorption capacity Y13 . First,
main eect plot shows negative eect of activation
temperature, even an optimal is observed between 600

Table 6 summarizes the eects of experimental design


factors on porous structure and adsorption capacities of
the sorbents produced. It shows that optimization of all
the responses under the same experimental conditions is
impossible because the inuence of the factors is dierent.
Using response surfaces methodology, the ranges of
each factor allowing the ideal activated carbon to be
obtained are determined. The rst step is to establish the
values of structural characteristics of an ideal activated
carbon. This sorbent should have a large SBET Y2 and
important micropore Y4 and mesopore Y3 volumes
allowing their use for removal of a large range of pollutants. Experimental design analysis has shown that
impregnation ratio X3 must be xed to the value 1.5 to
obtain well developed porous structure. The optimal
point for SBET indicated by the model is equal to 376
m2 g1 corresponding to an activation temperature of
691 C and an activation time of 220 min (Fig. 10). The
same optimal temperature is determined to obtain a
maximum micropore volume Y4 of 0.155 cm3 g1 but
for an optimal activation time of 140 min. More developed mesopore volume Y3 is obtained when activation
temperature is equal to 868 C and an activation time of
220 min (Fig. 10). But, as shown in Fig. 10, when activation temperature varies from 532 to 868 C for an
activation time of 220 min, mesopore volume remains

Fig. 10. Estimated response surfaces for SBET (m2 g1 ) and mesopore volume (cm3 g1 ) with impregnation ratio of 1.5; (+) optimal
conditions.

434

S. Rio et al. / Chemosphere 58 (2005) 423437

Table 6
Summary of the eects of experimental design factors on sorbents properties
Response

Activation temperature

Activation time

Impregnation ratio

Micropore volumeSBET
Mesopore volume
Copper adsorption
Phenol adsorption
Dye adsorption
VOC adsorption

)
+
)
)
+
)

+
+
+
)
+
+

+
+
+
+
+
+

nearly unchanged (0.2250.240 cm3 g1 ). So, if activation temperature is xed to the value 691 C in order to
maximize SBET and micropore volume, the mesopore
volume obtained is 0.232 cm3 g1 which is very close to
the optimal one (0.240 cm3 g1 ).
Then, optimization of adsorption capacities of copper Y8 , phenol Y9 , Basic Violet 4 Y10 and Acid Red
18 Y11 have also been carried out. First, the optimal
conditions to maximize copper adsorption capacity Y8
are impregnation ratio of 1.5, activation temperature of
680 C and an activation time equal to 220 min (Fig. 11).
Under these experimental conditions copper adsorption
capacity reaches 84 mg g1 . The response surfaces of
Basic Violet 4 adsorption capacity Y10 is identical to
this of copper adsorption capacity and optimal value of
this response is 91 mg g1 . It conrms that adsorption
mechanisms of these two positively charged molecules in
aqueous solution would be identical and favored under
the optimal conditions determined by response surfaces
methodology. The estimated response surfaces for Acid
Red 18 adsorption capacity Y11 is also presented in Fig.
11 and reveals that this response is maximum when
impregnation ratio is equal to 1.5 with activation temperature of 750 C and activation time of 180 min. But,
the variation of these adsorption capacities weak in the
experimental conditions studied allowing a compromise
to be found.
In the case of acetone Y12 or toluene Y13 adsorption capacities, The optimal conditions maximizing
these responses are impregnation ratio of 1.5, activation
temperature of 703 C and activation time of 145 and

163 min, respectively (Fig. 12). These values are very


close to those obtained during response surface estimation of micropore volume Y4 (X1 : 691 C, X2 : 140
min, X3 : 1.5) because VOC adsorption eciency is
strongly dependent on microporosity development
(Table 4).
To optimize all the responses under the same experimental conditions is dicult because regions of interest
of the factors are dierent. Therefore, a compromise
must be found. The cost of the process must be also
taken into account and this activated carbon should
have a relatively high mass yield (3540%).
The optimal experimental conditions already identied can be classied in two distinct regions. The rst
one: activation temperature of about 700 C, activation
time of 145160 min and impregnation ratio of 1.5,
correspond to optimal conditions of the following responses: micropore volume Y4 , acetone Y12 and toluene Y13 adsorption capacities. The second region of
interest, corresponding to optimal conditions for SBET
Y2 development, copper Y8 and Basic Violet 4 Y10
adsorption capacities, is dened by an activation temperature of about 700 C, an activation time of 220 min
and impregnation ratio of 1.5. Results of response surfaces methodology allow the experimental design responses to be estimated in these two regions of interest
and compared. As shown in Table 7, on one hand, some
experimental responses, like micropore volume Y4 ,
copper Y9 , Acid Red 18 Y11 and toluene Y13
adsorption capacities do not signicantly vary between
the two optimal conditions obtained due to the low

Fig. 11. Estimated response surfaces for copper and Acid Red 18 adsorption capacities (mg g1 ) with impregnation ratio of 1.5; (+)
optimal conditions.

S. Rio et al. / Chemosphere 58 (2005) 423437

435

Fig. 12. Estimated response surfaces for acetone and toluene adsorption capacities (mg g1 ) with impregnation ratio of 1.5; (+) optimal
conditions.

Table 7
Predicted responses for optimal activated carbons
Optimal conditions X1 , X2 , X3

Y2

Y3

Y4

Y8

Y9

Y10

Y11

Y12

Y13

700 C, 145160 min, 1.5 wt/wt


700 C, 220 min, 1.5 wt/wt

350
377

0.175
0.232

0.130
0.125

83
84

50
55

88
91

52
52

58
54

62
61

Y2 , SBET (m2 g1 ); Y3 , mesopore volume (cm3 g1 ); Y4 , micropore volume (cm3 g1 ); Y8 , adsorption of copper (mg g1 ); Y9 , adsorption of
phenol (mg g1 ); Y10 , adsorption of Basic Violet 4 (mg g1 ); Y11 , adsorption of Acid Red 18 (mg g1 ); Y12 , adsorption of acetone
(mg g1 ); Y13 , adsorption of toluene (mg g1 ).

eect of activation time X2 on these responses. On the


other hand, response surfaces curves of SBET Y2 and
mesopore volume Y3 show an increase, even weak, of
these responses between the rst and the second region
of interest (Fig. 10). Finally, a slight decrease of VOC
adsorption capacities is observed between the rst and
the second region of interest (Fig. 12). It could be
attributed to the decrease, even weak, of micropore
volume Y4 , these responses being strongly correlated as
shown on Table 4.
To conclude on this optimization step, in order to
limit the energetic cost of the process and to obtain a
satisfying mass yield, the following conditions: activation temperature of 700 C, activation time of 145 min
and impregnation ratio of 1.5, allow to obtain a satisfying compromise between the dierent responses studied in this paper.

4. Conclusion
Carbonaceous materials with adsorptive properties
have been produced from sewage sludge by chemical
activation process using sulfuric acid. Experimental design methodology has been used in order to determine
the eects of activation temperature (600800 C), activation time (13 h) and impregnation ratio (0.51.5 g of
H2 SO4 g1 of sludge) on chemical properties, porous
structure and adsorption capacities of the sorbents prepared. Response surfaces methodology allowed the
optimal conditions for activated carbon preparation to
be determined.

First, the carbonaceous sorbents produced are acidic


in nature due to the important quantity of acidic surface
functional groups. This acidic character increases with
increasing impregnation ratio while the increase of
activation temperature and activation time lead to an
increase of surface pH of the activated carbons. The
analysis of the responses characterizing the porosity
development shows, on one hand, a negative eect of
temperature on SBET and micropore volume and positive
eects of activation time and impregnation ratio on
these responses. And, on the other hand, the three factors seem to have a positive eect on mesopore volume
in the ranges studied.
The eects of the three factors of the experimental
design on VOC adsorption capacities in gas phase follow
the same trend as micropore volume development, i.e.,
positive eects of activation time and impregnation ratio
and negative eect of activation temperature. Anionic
and cationic dyes adsorption capacities in aqueous
solution are strongly dependent on micropore and
mesopore development. In the case of copper adsorption
capacity, this response depends on porous structure
development but, an ion exchange mechanism has been
identied, taking part in the adsorption process.
The optimization step, carried out using response
surfaces methodology, allows two dierent optimal
experimental conditions for activated carbon production
to be identied. The rst region of interest: activation
temperature of 700 C, activation time of 145 min and
impregnation ratio of 1.5, correspond to optimal conditions for micropore volume and VOC adsorption
capacities. The second region of interest, corresponding

436

S. Rio et al. / Chemosphere 58 (2005) 423437

to optimal conditions for SBET development, copper and


Basic Violet 4 adsorption capacities, is dened by activation temperature of 700 C, activation time of 220 min
and impregnation ratio of 1.5. In order to have a high
mass yield and to reduce the energetic cost of the process, the following optimal conditions, 1.5 g of H2 SO4
g1 of sludge, 700 C and 145 min are more appropriate.
Further experiments should be carried out to increase
the porosity development and adsorptive properties of
activated carbons produced from sludge, like the introduction of a preliminary carbonization step at low
temperature (300400 C) in the overall activation process. A pre-development of porosity could occur allowing a more ecient impregnation step before activation.
Finally, in order to evaluate the economic feasibility
of sludge chemical activation process, a technico-economic approach will be carried out and based on a mass
yield of approximately 38%. This cost analysis would
include equipment, sulfuric acid consumption, nitrogen
consumption, electricity usage. . .

Acknowledgements
The authors wish to acknowledge ADEME and
Region Pays de la Loire for nancial support. The authors are also grateful to Communaute Urbaine de
Nantes and Loire 21 for supplying sewage sludge and to
Y. Gouriou (Ecole des Mines de Nantes) for the
experimental assistance.

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