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Chemosphere 58 (2005) 423–437

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Experimental design methodology for the preparation
of carbonaceous sorbents from sewage sludge by
chemical activation––application 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 influential factors on each experimental design response have been identified.
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 effective adsorbent that
is widely used for water and gaseous emissions purifi*

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 specific 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 first carbonized at
600–800 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

This methodology is widely used in chemical engineering notably to optimize adsorption processes (Ricou et al. the by-product generated during wastewater treatment processes. Bagreev et al. 2001a). This is carried out by chemical activation process using sulfuric acid. But. ‘‘factor by factor’’. Notably. we focus on the preparation of activated carbon from sewage sludge. wastes tires (San Miguel et al. in comparison to a classical approach for the same number of estimated parameters (Box and Draper. Materials and methods 2. ash content and elemental composition of sludge samples are assessed by French standard methods (AFNOR NF U 44-171. sewage sludge production is about 950 000 tons of dried matter per year. with some traditional disposal ways coming under pressure like farmland applications and others being phased out like landfill. recent studies which have shown the feasibility of this conversion rarely determine the effects 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. was carried out by varying activation temperature between 400 and 900 C.. In this study.. and at the same time. 2003). has been identified as an attractive precursor for activated carbon production (Chiang and You. apple pulp (Suarez-Garcia et al. when sulfuric acid concentration is higher than 3 M. In France. almond shells (Toles et al. 2001). Calvo et al... / Chemosphere 58 (2005) 423–437 When activated carbons are prepared by chemical activation. Annadurai et al. 2001...5 g H2 SO4 g1 sludge).. 1987. it is necessary to seek cost-effective and innovative solutions to sewage sludge disposal problem. 2002) or pecan shells (Bansode et al. Then. 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. activation duration between 1 and 3 h and H2 SO4 concentration from 1 to 3 M. it produces reusable by-products. 2001).. sewage sludge. destruction of the material structure occurs during the thermal treatment (Rio et al. This study. 2003). Nitrogen flow rate is equal to 2. The effects of impregnation ratio (0. the influence of these operating conditions on porosity development have been studied. activation temperature (600–800 C) and activation time (60–180 min) are analyzed using experimental design methodology. 1982). Different characteristics of the activated carbon produced are analyzed as a function of these three factors.5–1.. 2.5 l min1 . (ii) the gain in reducing the number of experiments to be undertaken... 2002) but also to optimize experimental conditions for activated carbon preparation from waste (Bacßaoui et al. 1987). the most influential factors were found to be impregnation ratio. Dried viscous liquid sludge is mixed with H2 SO4 solutions (1–3 M) for 6 h. Viscous liquid sludge corresponds to aerobically digested sludge dewatered by centrifugation. But. . 2003) and numerous agricultural byproducts including wood (Tseng et al. Raw material Viscous liquid sludge collected from the municipal wastewater treatment plant of Nantes-Tougas. 2001b. a preliminary study on the effect 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. Dried matter content. 2003). 2003) have been successfully converted into activated carbons on laboratory scale.1. The traditional ways of sludge valorization include farmland application. mainly industrial or agricultural by-products. 2001). sugarcane bagasse (Mohan and Singh. On searching for economical and available starting material..424 S. wastewater undergoes a biological treatment by activated sludges. a growing research interest consists in the production of carbon-based adsorbents from a range of low-cost precursors.. Activated carbon preparation Chemical activation with sulfuric acid is carried out using an impregnation method. is used as precursor in this study. In this work. activation temperature and activation time. And. Tay et al. The regions of interest of these factors have been detected in previous study (Rio et al. In this domestic wastewater treatment plant. The resulting mixture is filtered and dried at 105 C. 1995. landfill and incineration. 2003). Rio et al. For this reason.. Lu et al.. 2000). 2.2.. Polymers (Yue et al. Activated carbon preparation from sewage sludge can be considered as an attractive method in reducing sludge volume. In recent years. the impregnated sludge is introduced in a 2 l horizontal furnace and carbonized under nitrogen atmosphere at 20 C min1 .. higher activating agent concentration is not used because preliminary experiments have shown that. 2002). in France. 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. The preparation of activated carbon is influenced by many factors. 2001. The main advantages of experimental designs are: (i) the ability to evaluate the effects of interactions between tested examined parameters.

/ Chemosphere 58 (2005) 423–437 2.4 g of dried sorbent to 20 ml of deionized water. if necessary. Adsorption kinetic equilibrium is reached in 3 d during copper and phenol kinetics experiments.4. The elemental analysis of dried sludges and carbonized sludges are realized with a THERMOQUEST NA2100 elemental analyzer giving the mass percentage of carbon.1. hydrogen. sludge-based adsorbents are crushed manually and dried at 105 C. When adsorption kinetic equilibrium is reached. respectively. oxygen. The sample is filtered and the pH of solution is measured (Bagreev et al. 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. are used to test the adsorption capacities of the activated carbons produced. Samples are outgassed between 100 and 350 C.S. activation time ðX2 Þ and impregnation ratio ðX3 Þ.. These four pollutants are chosen because they represent different types of standard industrial wastewater pollution.5. a central composite design is used.. the parameters ‘‘aij ’’ of the model are estimated from experimental responses by least squares regression using STATGRAPHICS software. in 5 d for dyes adsorption kinetics and in 2 d during VOC adsorption kinetics in gas phase. Porosity measurements Nitrogen adsorption/desorption isotherms are measured at 77 K with a MICROMERITICS ASAP 2010 surface area analyzer. 2. weak carboxylic and lactone functions. three replicates of the central run and six star points. Adsorption experiments in aqueous solution A metallic ion: Cu2þ . 30 mg l1 for Acid Red 18 and 50 mg l1 for Basic Violet 4 adsorption experiments. 2. in a vacuum during 3 d before analysis.4. The levels chosen for each of the three parameters are also presented in this table and their values depend on results of preliminary experiments. The specific surface area (SBET ) is calculated by BET equation (Brunauer et al. 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. to avoid copper precipitation in solution. 2. Experimental design methodology As detected in previous study (Rio et al. 2. we represent graphically isoresponses surfaces which are three-dimensional models of the relationship between the responses and two factors. adsorption capacities at equilibrium. 2001a).2. and two organic dyes: Acid Red 18 and Basic Violet 4. (1951) and Horwath and Kawazoe (1983) theories. dyes and phenol are analyzed using a spectrophotometer UV (Shimadzu 1601).3. allowing each experimental response to be optimized. The particle size is estimated to be equal to 0. The mesopore (2–50 nm) and micropore (<2 nm) volumes are estimated according to Barrett et al. Activated carbon characterization 2. 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. Chemical properties of materials Surface pH is measured by adding 0.2. nitrogen and sulfur. Acetone and toluene concentrations are measured using a gas chromatograph (Perkin–Elmer Autosystem XL). Following the model fitted for each response. 1987): Y ¼ a0 þ a1 X1 þ a2 X2 þ a3 X3 þ a12 X1 X2 þ a13 X1 X3 2 þ a23 X2 X3 þ a11 X12 þ a22 X21 þ a33 X32 For each response ðY Þ. During copper adsorption experiments.1.4. Copper is analyzed by an atomic absorption spectrophotometer (Perkin–Elmer Aanalyst 200) and. Rio et al. are determined according to the mass balance between the solid and the liquid/gas phase in the reactors.3. In order to evaluate the effects and interactions of these three factors. Adsorption tests Prior to adsorption tests.3. phenolic functions and carbonyl functions. 1938).1–1 mm. Adsorption experiments in gas phase Two different volatile organic compounds (VOC) have been used in this study. This response surfaces . Adsorption kinetic experiments are carried out at room pressure and temperature (about 20 C). qe (mg g1 ). pH is fixed to 425 the value 5. A second-order model is selected in order to predict each response ðY Þ in all experimental regions (Box and Draper. acetone and toluene. The experimental conditions required by this design are defined in Table 1. Microstructure of dried sludges and chemically activated sludges is observed with a Scanning Electron Microscope JEOL 6400 F. depending on the materials activated or not. The temperature is 20 ± 1 C. 2003) the most influential factors on the physico-chemical characteristics of activated carbon from sludge are activation temperature ðX1 Þ. 2. This design is constructed based on a 23 factorial design. an organic pollutant: phenol.. The suspension is stirred for 24 h to reach equilibrium.

The relatively high quantity of carbon within viscous liquid sludge (39. 3.7 0.2. the sludge contains heavy metals like lead or mercury but their concentration are lower than the values fixed by French regulation. Characterization of raw sewage sludge The results of physico-chemical analysis of viscous liquid sludge are presented in Table 2.9 2.4 19.5 0.8 5. the raw material and the resulting sorbents have been submitted to leaching test adapted from the French standard AFNOR X31-210 (2000). / Chemosphere 58 (2005) 423–437 Table 1 Experimental design matrix No.426 S.0 19. and the pore structure of the sludge is mainly macroporous. Rio et al. 3.9 0. porous structure.6 6. In order to estimate adsorption efficiency of sorbents produced towards standard industrial pollutants.2 22.1.5 1. this model should not be used to predict the response. Viscous liquid sludge develops low SBET of 2.9 1.9 97. The leaching percentage of these metallic compounds was very low and did not exceed 2% in demineralized water acidified at pH 5. if low values of these coefficients of determination are observed ðR2 < 0:8Þ. The experiments are carried out in a random order.5 1 1 1 1 1 1 1 0. dried matter content of viscous liquid sludge is equal to 19.8 306 76 64 634 <5 and adsorption capacities at equilibrium. 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. First. To evaluate the stability of these toxic metallic compounds. or whether another model should be used. surface chemistry Property/element 2 1 SBET (m g ) Macroporosity (vol. as indicated by an p-value less than 0.2. lack-of-fit tests are designed to determine whether the selected models are adequate to describe the observed data.4 0.1. 1966). the following responses are also studied: adsorption capacities of copper ðY8 Þ. phenol ðY9 Þ.15 1. Surface chemistry evolution during activation is determined by measurements of surface pH ðY5 Þ. The results notably show that these heavy metals are very stable within the raw material and the resulting sorbents.5 1. Mass yield (Y1 ) The results of experimental design show that mass yield values range from 33% to 49% (Table 3). These characteristics are chosen because of their strong influence on activated carbon adsorption capacity (Boehm. Finally.2%.0 39. mesopore volume ðY3 Þ and micropore volume ðY4 Þ. If the model has a significant lack-of-fit. And.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. Porosity development is characterized by SBET ðY2 Þ.05 at the 95% confidence level. Basic Violet 4 ðY10 Þ and Acid Red 18 ðY11 Þ in aqueous solution and adsorption capacities of acetone ðY12 Þ and toluene ðY13 Þ in gas phase. Exp. 3.9 m2 g1 .4 wt%) shows that it has the potential to be converted in carbonaceous sorbent.%) 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. acidic surface functional groups ðY6 Þ and basic surface functional groups ðY7 Þ. A satisfying correlation ðR2 ¼ 0:941Þ is obtained between theoretical responses.5 0.5 1. Responses analysis and interpretation The experimental responses studied include: activation mass yield ðY1 Þ.5 0.5 0. Results and discussion 3.5 1. obtained by the second order . The values obtained experimentally for these characteristics of the carbonaceous sorbents produced as well as coefficients of determination ðR2 Þ between observed values and values predicted by the second order model are given in Table 3.

048 0. during sewage sludge chemical activation with 3 M H2 SO4 at 650 C. adsorption of toluene (mg g1 ).6 33..061 0. Y5 . the increase in temperature quickens the gasification reactions and.2. the removal of amorphous components which obstruct the pores. surface pH. adsorption of Acid Red 18 (mg g1 ). 1. Y6 .967 0.83 0.4 36. coefficients of determination between observed values and predicted values.64 0.046 0. 3.18 0. Then.29 0.217 0.131 0.79 0. compared with others factors that have a very weak effect on this response. p-value of lack-of-fit statistical test. The final porous structure of the activated carbon is governed by the precursor structure and by activation conditions (Bansal et al.131 0.094 0.104 0.045 0. micropore volume (cm3 g1 ).14 0. Generally.125 0. Y13 .046 0. Y9 .22 0.16 0.. adsorption of Basic Violet 4 (mg g1 ).23 0.1 45.042 0..9 5. 1988). Lu and Lau (1996) have obtained.085 0. Y4 .34 0.27 0.. Y11 .20 0. First.244 0.239 0.128 0. and experimental responses. These values are in agreement with literature datas.81 0. Exp.89 0.895 0.046 0.7 37.125 0. 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-fit test Yield Porosity development Chemical properties Adsorptive properties Y1 Y2 Y3 44.748 69 77 70 89 63 88 62 88 76 77 77 63 64 76 77 75 88 0. Y2 . porosity of commercial activated carbons is mainly constituted of micropores and even mesopores. Y8 .129 0. The effects of the three factors on mass yield ðY1 Þ are presented in Fig.084 0. But.e.125 0.6 38.39 0. Y10 .231 0.047 0. 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.4 37.042 0.7 7.672 0. the SBET ðY2 Þ of the sorbents varies from 59 to 352 m2 g1 according to the experimental conditions (Table 3). Indeed. Activation temperature ðX1 Þ has a highly negative effect on yield ðY1 Þ.899 29 51 31 54 18 53 14 54 52 52 52 15 13 40 51 39 54 0.36 0. basic surface functional groups (meq g1 ). Y12 . Fig.048 0.929 5.148 0.907 47 52 49 54 41 53 41 53 42 43 43 51 47 54 51 52 54 0.79 0. Rio et al.047 0.3 37.0 6.2 36.84 0.75 0.92 0. therefore.77 0. 1.3 6.023 0.6 6.806 Y4 Y5 Y6 Y7 Y8 Y9 Y10 Y11 Y12 Y13 0.4 38.9 44. mesopore volume (cm3 g1 ).3 44. SBET (m2 g1 ).8 5. R2 .032 0.9 5. an SBET of 220 m2 g1 .81 0. Y3 . adsorption of acetone (mg g1 ).024 0.2.76 0. / Chemosphere 58 (2005) 423–437 427 Table 3 Experimental design responses No.048 0. Lack-of-fit.5 6. Main effect plot for mass yield (%). adsorption of phenol (mg g1 ). the increase of temperature from 600 to 800 C leads to a decrease of mass yield.24 0. That ash content limits the porosity development occurring within organic matter and behaves only as an inert material which does not contribute .5 35. statistical model.9 0. adsorption of copper (mg g1 ).70 0.9 5. no significant interactions between the factors have been observed.03 0.20 0.4 6.0 6.9 5.914 78 81 79 83 77 82 77 82 81 81 81 77 77 80 81 81 83 0.20 0. 1974) where as sorbents produced from sludge in this study contains between 35% and 40% of ash (Table 4). acidic surface functional groups (meq g1 ). Note that commercial activated carbon consists of various mineral compounds (ash) in quantities lower than 10% (Hassler.23 0.941 157 259 177 353 77 322 58 327 248 251 255 69 61 200 252 231 352 0. leading to a decrease in mass yield (Bacßaoui et al.1 38.65 0.S. Identical experiments have also been carried out by Rozada et al.6 38.895 0.1 5.80 0. Y7 . 1988). 2001). Porosity development The activation process allows to create and develop the porous surface and volume giving adsorbent qualities to resulting activated carbon.24 0.9 49.029 0. i.887 Y1 .85 0.13 0.5 6.71 0. (2003) and they have obtained adsorbents developing 390 m2 g1 at 625 C. mass yield (%).901 26 49 24 48 15 48 12 48 49 50 51 14 12 32 49 30 51 0.1 36.20 0.1 5.4 6.11 50 49 48 54 46 53 48 53 49 50 49 46 46 47 47 53 53 0.6 0.24 0.

Fig. oxygen.6 3. Such interaction is observed between activation time and impregnation ratio ðX2 X3 Þ.1 1. The effects and interaction of the factors on SBET ðY2 Þ are presented in Fig.5 0.5 37.2 1.4 40.1 37.0 34.7 41.9 42.5 0. Rio et al. the important quadratic effect observed suggests that an optimal SBET value is reach between 600 and 800 C.3 8. Main effect plot and interaction plot for SBET (m2 g1 ) and mesopore volume (cm3 g1 ). and reaches about 500 m2 g1 of organic matter. By this way. 2 shows that when the impregnation ratio is fixed to the lower value (0. On the other hand. A correct correlation between observed responses and predicted responses is obtained by the statistical model. 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. with coefficient of determination of 0.6 9.6 4. Indeed.3 41. the increase of temperature leads to a dramatic decrease of SBET . The ‘‘+’’ curves stand for the maximum values of the parameter and the ‘‘)’’ curves stand for the minimum values.2 40.3 35.5 1. 2000).5 g H2 SO4 g1 sludge).1 4.5 1.0 5. it shows the estimated variable as a function of pairs of factors. when experiments are carried out with high impregnation ratio (1. 2. while. but. the SBET evolves versus the first written factor in the X-axis and is parameterized according to the second written factor.428 S.1 10.2 1. response analysis shows that activation temperature ðX1 Þ has slightly negative effect on this response. In each plot. On one hand. .4 3.0 4. hydrogen.5 1.3 1.4 10. So.7 2.5 g H2 SO4 g1 sludge).5 1.895 (Table 3). important interactions exist between activation temperature and impregnation ratio ðX1 X3 Þ (positive) which is more important than the effects of X1 .5 1.0 2.5 3.5 38. the increase in temperature allows SBET to be increased.7 4.6 10.7 10.5 1 35. porosity development could be recalculated.0 to the porosity (Linares-Solano et al. Interaction plot is also presented in Fig.6 1.1 5.0 43. taking only organic matter content into account.5 1.1 8.6 11.1 4.2 1.5 39.9 44. 2. / Chemosphere 58 (2005) 423–437 Table 4 Ash and carbon.5 0.0 11.3 40. the increase in activation time ðX2 Þ and impregnation ratio ðX3 Þ allows SBET ðY2 Þ to be developed.3 4. 2.9 5. Fig.2 35.8 3..4 3.9 42.6 2.8 37.5 1.2 3.

4a (·550). Y6 .313 )0.957 1 0.874 0.520 )0..300 0. exactly the same trends for SBET response in terms of effects and interactions of the factors are obtained. 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.979 0.154 0. the coefficient of determination between SBET ðY2 Þ and micropore volume ðY4 Þ is equal to 0. Y4 . The surface of the dried sludge and the resulting chemically activated carbons have been observed using scanning electron microscopy (Fig. .071 )0. 2000). Y11 .937 )0. The increase of activation time ðX2 Þ would cause the opening of closed or non-accessible micropores. Table 5 Values of coefficients of determination ðR2 Þ 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 0.986 0.2. 1996.214 )0. adsorption of copper (mg g1 ). less dense. these two experimental responses are very dependent.641 0.618 0.874 0. acidic surface functional groups ðY6 Þ and basic surface functional groups ðY7 Þ have been measured. 2).835 0.459 1 )0. mesopore volume (cm g ). basic surface functional groups (meq g1 ).989 1 2 1 3 1 3 1 Y2 . Y5 . The continuous increase in mesopore volume ðY3 Þ with the increase of activation temperature ðX1 Þ and time ðX2 Þ would result from a micropores widening phenomenon (Daley et al. confirms the positive effect of temperature on mesopore volume ðY3 Þ (between 2 and 50 nm) and the positive effect of activation time (between 1 and 3 h) on mesopore volume (as well as on micropore volume (<2 nm)) (Fig. 1999).5 while. 3).3.197 1 0. and to mesoporosity development (Fig.970 0.405 0. and porosity appears as shown in Fig. For micropore volume response ðY4 Þ which results are not presented in this paper. 1996). adsorption of toluene (mg g1 ). Martin et al.464 1 )0. 4a).908 1 0. Chemical properties For surface chemistry characterization. Y10 . Interaction plot reveals that important interactions exist between the three factors of the experimental design within the region of variability studied. acidic surface functional groups (meq g1 ).505 0.338 0.604 0. micropore volume (cm g ).937 (Table 5).393 )0.504 1 0. Y9 .526 0.303 )0.102 )0.188 0.469 0.395 0.472 0. Y7 . Main effect plot shows that all the experimental design factors have a positive effect on mesopore development (Fig.923 0. adsorption of acetone (mg g1 ).S.365 )0. 4b for a same magnitude as Fig.196 )0.935 0.383 )0. Y13 .076 )0. Finally.199 0.493 )0. Y12 . Y8 . After the activation process.942 0. adsorption of Acid Red 18 (mg g1 ). The important gasification of organic matter and the removal of sulfuric acid during the activation lead to an important macroporosity (Fig.927 0. with an impregnation ratio of 1.980 1 )0.575 0.396 0. SBET (m g ).5. 4).. the structure is different.381 1 0.678 0.852 0. Rio et al.962 1 0. The structure of the raw sludge is very dense and surface is smooth (Fig. adsorption of phenol (mg g1 ).118 0.525 0. Mesopore volume ðY3 Þ increases with increasing temperature ðX1 Þ if activation time ðX2 Þ is fixed to 60 min while it decreases with increasing temperature ðX1 Þ when activation time ðX2 Þ is fixed to 180 min. Important interactions also exist between temperature and 3.838 0.5.514 0.312 0. 4d).522 0.891 0.961 0.. The increase of impregnation ratio ðX3 Þ and activation time ðX2 Þ improves the micropore volume ðY4 Þ of the sorbents obtained.671 1 0. Y3 .935 0.543 )0. surface pH.219 )0. surface pH ðY5 Þ. adsorption of Basic Violet 4 (mg g1 ). 4c) formation. The value of coefficient of determination (Table 3) between calculated and observed mesopore volume ðY3 Þ reveals that the statistical model obtained does not correctly model experimental response because it explains only 81% of the variability in this response. this response decreases with increasing temperature or time when impregnation ratio is fixed to the value 1. the observation of pore size distributions of the resulting sorbents activated at 600 and 800 C.480 )0. / Chemosphere 58 (2005) 423–437 429 impregnation ratio ðX1 X3 Þ and between activation time and impregnation ratio ðX2 X3 Þ because the increase of temperature ðX1 Þ or time ðX2 Þ improve mesopore volume ðY3 Þ if impregnation ratio ðX3 Þ is fixed to the value 0. The activated carbon surface chemistry can participate to ionized molecules removal in aqueous solution (Petrov et al. yielding microporosity more accessible.384 0. The surface charge and the quantity of functional groups can have a significant influence on the adsorption properties.773 0. In addition.

. The p-value of lack-of-fit statistical test is less than 0. 4. Fig. This means that the model as fitted does not adequately represent the data. surface pH varying between 5 and 7. activation duration ðX2 Þ and impregnation ratio ðX3 Þ. respectively (Table 3). Pore size distributions of sorbent produced with impregnation ratio of 1. every sorbents produced are acidic. Fig. due to the important quantity of acidic surface functional groups as shown in Table 3. The increase of impregnation ratio ðX3 Þ leads to increase in acidic character of the sorbents produced because this factor has a strong positive impact on amount of acidic surface groups ðY6 Þ and a negative effect on amount of basic surface groups ðY7 Þ (Fig. the test of statistical significance of each factor is also performed. In the case of surface pH response ðY5 Þ. have p-values less than 0.914. The results show that only two effects. there is statistically significant lack-of-fit at the 95% confidence level.430 S.05 and equal to 0. The statistical analysis of this response is not carried out in this paper. 3. during the analysis of variance of surface pH response. 5 clearly shows that activation temperature ðX1 Þ and time ðX2 Þ have a negative effect on amounts of acidic surface groups ðY6 Þ and basic surface groups ðY7 Þ.967 and 0. First. A lack-of-fit test is performed to test the adequacy of the model. surface groups decompose at elevated temperature and their decomposition increases with increasing activation time (Boehm. Then. indicating that they are significantly different from zero at 95% of confidence level. The quantities of acidic surface groups ðY6 Þ and basic surface groups ðY7 Þ can be very correctly described by a second order model.05. As indicated in literature.03 (Table 3). In addition. Micrographs of dried sludge (a) and chemically activated sludge (b)–(d). Rio et al. 5). Amount of acidic surface groups ðY6 Þ is always at least two times more important than basic surface groups ðY7 Þ. the second order model is not adapted.5. R2 values are equal to 0. It is carried out by comparing the mean square against an estimate of the experimental error. / Chemosphere 58 (2005) 423–437 Fig. 1966). So.

ash content varies from 45.05 (Table 3). During copper adsorption experiments. Fig. . the model appears to be adequate for the observed data at the 95% confidence level. a lack-of-fit statistical test is realized to test the adequacy of this model. The effects of the three factors are similar to those obtained for SBET ðY2 Þ (Fig.. So. Sulfur content varies from 3. But. 1996). It would confirm that amounts of acidic and basic surface functional groups decrease with the increase of these experimental design factors (Boehm. activation time ðX2 Þ and impregnation ratio ðX3 Þ have a positive effect (Fig. copper adsorption capacity ðY8 Þ and micropore volume ðY4 Þ (Table 5).S. 2002) and activated carbon prepared from agricultural by-products (Toles et al. Sulfur content within dried sludge being equal to 0. This observation is confirmed by the important coefficient of determination between copper adsorption capacity ðY8 Þ and SBET ðY2 Þ. 1999) but they are similar to those obtained using activated carbon from sludge (Martin et al. Carbon content varies from 36% to 45% according to activation conditions and carbon content seems to decrease with increasing impregnation ratio due to dilution effect. 2) and micropore volume ðY4 Þ.0% to 51. while.0% according to the experimental conditions. 6).7% and it increases with increasing temperature and time. 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 fitted explains only 75% of the variability of this response (Table 3). the highest values (between 4% and 5%) being found for the highest impregnation ratio of 1. the evolution of calcium concentration in solution has been followed.5 are presented in Fig. 7. these porous characteristics seem to partly control the copper removal efficiency by the sorbents produced.. Main effect plot for copper adsorption capacity (mg g1 ). is not removed during thermal treatment. The simultaneous desorption of calcium in solution would indicate that ion exchange mechanism would also take place in the sorption phenomenon of metallic ion. / Chemosphere 58 (2005) 423–437 Fig. copper adsorption capacity ðY8 Þ 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).2. Table 4 also shows that both oxygen and sulfur contents increase with increasing impregnation ratio because of the oxydizing effect of H2 SO4 (Daley et al.9%. These values are in agreement with copper adsorption capacities obtained with commercial activated carbons (Faur-Brasquet et al.. Rio et al.5 (Table 4). The p-value of the lack-of-fit is greater than 0... important quantity of sulfur incorporated into the materials during impregnation step. 5. Finally.. and between. Ash content seems to slightly decrease with increasing impregnation ratio because the activating agent limits the formation of tars (Martin et al. The values of phenol adsorption capacities remain lower than phenol adsorption capacities obtained with commercial activated carbon (Nevskaia et al.4. 1996. Main effect plots for acidic and basic surface functional groups (meq g1 ). Adsorption tests in aqueous solution First. 1999). The evolution of Cu2þ removed and Ca2þ exchanged during kinetic experiment with chemically activated sludge at 600 C for 180 min and with impregnation ratio of 1. 3. Main effect plot shows a negative effect of activation temperature ðX1 Þ. the important quadratic effect of activation temperature ðX1 Þ reveals that optimal value of this factor can be achieved. 6. The elemental analysis carried out on the resulting activated carbon shows that oxygen contents decrease when activation temperature ðX1 Þ and time ðX2 Þ increase (Table 4). 1966). 1996). So.1% to 5.

2). Because of anionic character of Acid Red 18 molecule. 6. 2. activation temperature ðX1 Þ seems to have no effect on dye adsorption capacity but important quadratic effect of this factor allows an optimal value to be determined. when impregnation ratio ðX3 Þ is fixed to the value +1 (1. when. this increase of phenol adsorption with increasing impregnation ratio is attributed to the important microporosity development (Martin et al. a strong dependence would exist between dye adsorption capacities (Basic Violet 4 and Acid Red 18) and SBET ðY2 Þ. and Acid Red 18. The factors effects are identical to those obtained for mesopore volume ðY3 Þ (Fig. Indeed. the increase of activation temperature would lead to a micropore widening (or destruction) and a decrease of phenol adsorption. an important micropore development would occur. The increase of activation time ðX2 Þ and impregnation ratio ðX3 Þ allow dye adsorption capacity to be increased (Fig. when the quantity of sulfuric acid is low during impregnation. respectively. 8) carried out using impregnation ratio of 1. The increase of activation temperature ðX1 Þ and time ðX2 Þ lead to the lightly decrease of phenol adsorption capacity ðY9 Þ when the increase of impregnation ratio has a positive effect on this response (Fig.5. 9). Finally. 1996). Main effect plot and interaction plot for phenol adsorption capacity (mg g1 ). Chen et al. Evolution of Cu2þ removed (mM) and Ca2þ exchanged (mM) during kinetic experiment with chemically activated sludge at 600 C for 180 min and with impregnation ratio of 1.. 8). . First.5 g H2 SO4 g1 sludge). favoring phenol adsorption. And. 8. an anionic dye. when impregnation ratio ðX3 Þ is fixed to the lower level (0. 3. As shown in Fig. The same trend was observed for SBET ðY2 Þ and micropore volume ðY4 Þ responses.895 and 0. 7.432 S. has been identified. a cationic dye.. The experimental data can be correctly fitted by second order model. Adsorption tests in gas phase Adsorption experiments in gas phase are carried out to estimate the efficiency of the sorbents produced to Fig. the coefficients of determination between experimental and predicted adsorption capacities of Basic Violet 4 and Acid Red 18 are equal to 0. 8.2. Finally. an important correlation also exists between Acid Red 18 adsorption capacity ðY11 Þ and the amount of acidic surface groups ðY6 Þ that would participate to adsorption mechanism of this dye. an important interaction exists between activation temperature and impregnation ratio ðX1 X3 Þ. So. the increase of activation temperature ðX3 Þ leads to important decrease of phenol adsorption capacity ðY9 Þ. mesopore volume ðY3 Þ and micropore volume ðY4 Þ (Table 5).901. 2002). 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 effects of the experimental design factors.5 g H2 SO4 g1 sludge). notably micropore development ðY4 Þ.5 (Table 3). impregnation ratio and activation temperature increase. 4. Experimental results show that highest phenol adsorption capacities are observed when important microporosity development occurs during activation that corresponds to experiments (nos. Fig. Rio et al. for aqueous solution. Even no strong dependence between this response and porosity development. phenol adsorption capacity ðY9 Þ slightly increase with increasing activation temperature ðX3 Þ. / Chemosphere 58 (2005) 423–437 Fig. Due to dye molecule size (2–3 nm) both micropore and mesopore development are important for the adsorption process of these organic pollutants. and. similar adsorption experiments have been carried out to estimate the affinity of the sorbents prepared to remove Basic Violet 4.5. negatively charged in aqueous solution.

This dependence between VOC adsorption and microporosity development have been observed in numerous research works (Subrenat. / Chemosphere 58 (2005) 423–437 433 and 800 C due to quadratic effect of this factor. 3. It shows that optimization of all the responses under the same experimental conditions is impossible because the influence of the factors is different. and positive effects of activation time and impregnation ratio (Fig. This observation is confirmed by values of correlation coefficients revealing a strong dependence between these responses (Table 5). 10.155 cm3 g1 but for an optimal activation time of 140 min. These data are correctly fitted by a second order model (Table 3). when activation temperature varies from 532 to 868 C for an activation time of 220 min.S. even an optimal is observed between 600 Table 6 summarizes the effects of experimental design factors on porous structure and adsorption capacities of the sorbents produced. the ranges of each factor allowing the ideal activated carbon to be obtained are determined. as shown in Fig.5 to obtain well developed porous structure. remove two different VOC: acetone and toluene.3. Chiang et al. 10). in the same experimental conditions.. respectively. 10 because the same trends are observed for toluene adsorption capacity ðY13 Þ. First. The same optimal temperature is determined to obtain a maximum micropore volume ðY4 Þ of 0. 1999). 2). Rio et al. 10). Using response surfaces methodology. 1999. at least two times higher than values obtained in this study (Subrenat. 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. Main effect plot for Basic Violet 4 and acetone adsorption capacities (mg g1 ). 10). . This sorbent should have a large SBET ðY2 Þ and important micropore ðY4 Þ and mesopore ðY3 Þ volumes allowing their use for removal of a large range of pollutants. Experimental design results show that adsorption capacities of acetone ðY12 Þ and toluene ðY13 Þ vary between 12–51 mg g1 and 13–54 mg g1 . Experimental design analysis has shown that impregnation ratio ðX3 Þ must be fixed to the value 1. mesopore volume remains Fig. Optimization step Fig. 9. Adsorption capacities of acetone and toluene onto commercial activated carbons are. 2002). The first step is to establish the values of structural characteristics of an ideal activated carbon. (+) optimal conditions. Solely statistical results of acetone adsorption capacity ðY12 Þ are presented in Fig. 10. Lillo-Rodenas et al. Estimated response surfaces for SBET (m2 g1 ) and mesopore volume (cm3 g1 ) with impregnation ratio of 1.. The effects of these factors on VOC adsorption capacities are identical to those obtained for SBET and micropore volumes responses (Fig.5. main effect plot shows negative effect of activation temperature. But. More developed mesopore volume ðY3 Þ is obtained when activation temperature is equal to 868 C and an activation time of 220 min (Fig. 2001.

X2 : 140 min. As shown in Table 7.240 cm3 g1 ). Basic Violet 4 ðY10 Þ and Acid Red 18 ðY11 Þ have also been carried out. on one hand. The optimal conditions maximizing these responses are impregnation ratio of 1. like micropore volume ðY4 Þ. acetone ðY12 Þ and toluene ðY13 Þ adsorption capacities. The optimal experimental conditions already identified can be classified in two distinct regions. 11. corresponding to optimal conditions for SBET ðY2 Þ development. activation temperature of 703 C and activation time of 145 and 163 min.434 S. First.5. if activation temperature is fixed to the value 691 C in order to maximize SBET and micropore volume. The second region of interest. (+) optimal conditions.5 with activation temperature of 750 C and activation time of 180 min. 12). is defined by an activation temperature of about 700 C. phenol ðY9 Þ. The first one: activation temperature of about 700 C. 11 and reveals that this response is maximum when impregnation ratio is equal to 1. the mesopore volume obtained is 0. So. These values are very close to those obtained during response surface estimation of micropore volume ðY4 Þ (X1 Þ: 691 C. correspond to optimal conditions of the following responses: micropore volume ðY4 Þ. The response surfaces of Basic Violet 4 adsorption capacity ðY10 Þ is identical to this of copper adsorption capacity and optimal value of this response is 91 mg g1 . some experimental responses. In the case of acetone ðY12 Þ or toluene ðY13 Þ adsorption capacities. copper ðY9 Þ. a compromise must be found. To optimize all the responses under the same experimental conditions is difficult because regions of interest of the factors are different. The estimated response surfaces for Acid Red 18 adsorption capacity ðY11 Þ is also presented in Fig.240 cm3 g1 ). . optimization of adsorption capacities of copper ðY8 Þ. The cost of the process must be also taken into account and this activated carbon should have a relatively high mass yield (35–40%).5. It confirms 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. Estimated response surfaces for copper and Acid Red 18 adsorption capacities (mg g1 ) with impregnation ratio of 1. Under these experimental conditions copper adsorption capacity reaches 84 mg g1 . respectively (Fig.5. Rio et al. X3 : 1. 11). Then. activation time of 145–160 min and impregnation ratio of 1. the optimal conditions to maximize copper adsorption capacity ðY8 Þ are impregnation ratio of 1. But. the variation of these adsorption capacities weak in the experimental conditions studied allowing a compromise to be found. copper ðY8 Þ and Basic Violet 4 ðY10 Þ adsorption capacities.225–0. activation temperature of 680 C and an activation time equal to 220 min (Fig. Results of response surfaces methodology allow the experimental design responses to be estimated in these two regions of interest and compared.5) because VOC adsorption efficiency is strongly dependent on microporosity development (Table 4). Therefore.232 cm3 g1 which is very close to the optimal one (0. an activation time of 220 min and impregnation ratio of 1. / Chemosphere 58 (2005) 423–437 Table 6 Summary of the effects of experimental design factors on sorbents properties Response Activation temperature Activation time Impregnation ratio Micropore volume––SBET Mesopore volume Copper adsorption Phenol adsorption Dye adsorption VOC adsorption ) + ) ) + ) + + + ) + + + + + + + + nearly unchanged (0.5.5. Acid Red 18 ðY11 Þ and toluene ðY13 Þ adsorption capacities do not significantly vary between the two ‘‘optimal conditions’’ obtained due to the low Fig.

Experimental design methodology has been used in order to determine the effects of activation temperature (600–800 C). allows two different optimal experimental conditions for activated carbon production to be identified. X3 Þ Y2 Y3 Y4 Y8 Y9 Y10 Y11 Y12 Y13 700 C. 1. Y13 . correspond to optimal conditions for micropore volume and VOC adsorption capacities. Y9 . mesopore volume (cm3 g1 ). corresponding . micropore volume (cm3 g1 ). adsorption of Basic Violet 4 (mg g1 ). Estimated response surfaces for acetone and toluene adsorption capacities (mg g1 ) with impregnation ratio of 1. On the other hand.e. Table 7 Predicted responses for ‘‘optimal’’ activated carbons Optimal conditions ðX1 . activation time of 145 min and impregnation ratio of 1.125 83 84 50 55 88 91 52 52 58 54 62 61 Y2 . a slight decrease of VOC adsorption capacities is observed between the first and the second region of interest (Fig.175 0. carried out using response surfaces methodology. i. the following conditions: activation temperature of 700 C. And. (+) optimal conditions. The first region of interest: activation temperature of 700 C.S. 4. positive effects of activation time and impregnation ratio and negative effect of activation temperature. 220 min. 10).5 g of H2 SO4 g1 of sludge) on chemical properties. Y4 . It could be attributed to the decrease. allow to obtain a satisfying compromise between the different responses studied in this paper. adsorption of toluene (mg g1 ). In the case of copper adsorption capacity. taking part in the adsorption process. The effects of the three factors of the experimental design on VOC adsorption capacities in gas phase follow the same trend as micropore volume development. Response surfaces methodology allowed the optimal conditions for activated carbon preparation to be determined. effect of activation time ðX2 Þ on these responses. on the other hand. adsorption of Acid Red 18 (mg g1 ). activation time (1–3 h) and impregnation ratio (0. the three factors seem to have a positive effect on mesopore volume in the ranges studied. adsorption of copper (mg g1 ). The analysis of the responses characterizing the porosity development shows. response surfaces curves of SBET ðY2 Þ and mesopore volume ðY3 Þ show an increase. a negative effect of temperature on SBET and micropore volume and positive effects of activation time and impregnation ratio on these responses. SBET (m2 g1 ).5–1.5. Y12 . 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. an ion exchange mechanism has been identified. activation time of 145 min and impregnation ratio of 1. adsorption of phenol (mg g1 ). even weak. on one hand. Finally. Anionic and cationic dyes adsorption capacities in aqueous solution are strongly dependent on micropore and mesopore development. / Chemosphere 58 (2005) 423–437 435 Fig.. The optimization step.5 wt/wt 350 377 0.130 0. Y8 . in order to limit the energetic cost of the process and to obtain a satisfying mass yield. X2 . the carbonaceous sorbents produced are acidic in nature due to the important quantity of acidic surface functional groups. adsorption of acetone (mg g1 ).5. 12). To conclude on this optimization step. First. this response depends on porous structure development but. Y11 . even weak. 12. Rio et al. porous structure and adsorption capacities of the sorbents prepared.5 wt/wt 700 C. Conclusion Carbonaceous materials with adsorptive properties have been produced from sewage sludge by chemical activation process using sulfuric acid. 1. of these responses between the first and the second region of interest (Fig. The second region of interest. of micropore volume ðY4 Þ. 145–160 min. these responses being strongly correlated as shown on Table 4. Y3 .232 0.5. Y10 .

AFNOR Ed. Purif. G. M.. 2001. M. in order to evaluate the economic feasibility of sludge chemical activation process. A pre-development of porosity could occur allowing a more efficient impregnation step before activation.. A. 16. J. Commercial and Environmental. S. Technol.. J. Feasibility of activated carbon production from biological sludge by chemical activation with ZnCl2 and H2 SO4 ..R.. Elucidating the porous structure of activated carbon fibers using direct and indirect methods. 1951. Mohan. Bansode.J. 111–117. 17.J.. 344–348.. Method for the calculation of effective pore size distribution in molecular sieve carbon. Factorial design analysis for adsorption of dye on activated carbon beads incorporated with calcium alginate. Wat. 1983. 2002. 65. F. 922–927.. H. Waste Manage. Bagreev.F. Chem. T. Joyner. Bandosz. .P.. Marshall. The determination of pore volumes and area distributions in porous substances. Carbon 39.. Paris. Mater. 1987..5. A. Mesopor. Characterisation of sewage sludgederived adsorbents for H2 S removal part 2: surface and pore structural evolution in chemical activation.M.. Teller. Physical and chemical properties study of the activated carbon made from sewage sludge. Calvo. 191–198.-C... 2003. Singh. Gas Separat. K. L..and multi-component adsorption of cadmium and zinc using activated carbon derived from bagasse––an agricultural waste. G.. Cazorla-Amoros.N. Finally. F. 16. D. K.. Losso... 2002. 2001... R. Lua. J. Le Cloirec. Linares-Solano. Lillo-Rodenas. N. Chiang. P. References AFNOR NF U 44-171.P. You. 635–643.E. A. 80. M.and almond shell-based granular activated carbons. J Am. Further experiments should be carried out to increase the porosity development and adsorptive properties of activated carbons produced from sludge. C. Surface area development of sewage sludge during pyrolysis. 2000. 6.. Portier..-P. the following optimal conditions. Usefulness of chemically activated anthracite for the abatement of VOC at low concentrations.. 755–760. 667–672. 175–184. J. Technol. . Bagreev. Liu. 143–148.. Technol. 700 C and 145 min are more appropriate.. Garcia.. J.Q. Res. 1988. Res. Activated Carbon: Industrial. 1191–1200.. Salinas-Martinez de Lecea. D. Adsorption of volatile organic compounds by pecan shell. sulfuric acid consumption.... 1971–1979.J. Yaacoubi. J. 331–336. N. Use of sewage sludge for manufacturing adsorbents. P. Chem. John Wiley and Sons. . Empirical Model Building and Response Surface. 1982.. activation time of 220 min and impregnation ratio of 1. 425–432. Low. E.. Halenda. Serrano-Talavera. A. New York. Adv. Environ.-J. 2002.. F.. Kawazoe. R. Economy.. Optimization of conditions for the preparation of activated carbons from olive-waste cakes. Upgrading sewage sludges for adsorbent preparation by different treatments.. G. In order to have a high mass yield and to reduce the energetic cost of the process. a technico-economic approach will be carried out and based on a mass yield of approximately 38%. Martin-Gullon.D. Chemical Publishing Co. G. Fuel 74. Locke..H. L. Inc. Otero.-C. X. 1938..C. Removal of metal ions from aqueous solution by adsorption onto activated carbon cloths: adsorption competition with organic matter.. Juang.D. 470–475. Textural and chemical characterisations of activated carbon prepared from oil-palm stone with H2 SO4 and KOH impregnation. Rio et al. Hippo.. 1996. Chem. 2002. Gouriou (Ecole des Mines de Nantes) for the experimental assistance. E. Acknowledgements The authors wish to acknowledge ADEME and Region Pays de la Loire for financial support.. C. J. 1974. A..F. Chem. 2387–2392.. 10. 309– 319..W. Carratala-Abril. Brunauer.J..Y.H. C. C. Environ. Chemical identification of surface groups. D. Marcel-Dekker. J.. A. Tandon. J Am. Adib. 1999. Rivera-Utrilla.. nitrogen consumption. 2002.J. M..C. Activated carbons from bituminous coal: effect of mineral matter content.. Technol. P. T. Fuel Process. Emmett. Draper. Lau.C. Horwath. The authors are also grateful to Communaute Urbaine de Nantes and Loire 21 for supplying sewage sludge and to Y. Bacßaoui. Y.436 S.. Balaguer. B. R..P.G. M. R.. Carbon 39. A. D. Chiang.5 g of H2 SO4 g1 of sludge. 1966. like the introduction of a preliminary carbonization step at low temperature (300–400 C) in the overall activation process..P.J. Barrett. R. Micropor. Carbon 39. Lu. / Chemosphere 58 (2005) 423–437 to optimal conditions for SBET development.C. 1987. 1995. Eng. 2001b. J. 73.P.Q. Daley. New York. Boehm. 523–534.. Soc.. A.. copper and Basic Violet 4 adsorption capacities. P. Box. J. Pore structure and surface chemistry of adsorbents obtained by pyrolysis of sewage sludge-derived fertilizer. D. K. 32.. pH of activated carbon surface as an indication of its suitability for H2 S removal from moist air streams. Biores. Maldonado-Hodar. Active Carbon. 77–78. Martin. 22. Rao. C. 2001a. Bandosz. Faur-Brasquet. Stoeckli. Graham. 373–380. Moreno-Castilla. Adv. D..B.A.. Kadirvelu. Donnet.-S.. A. A. Biores. Jeyaseelan...E. Linares-Solano.. 1897–1905. Lua.. Huang. M. 90. Single. W. J. is defined by activation temperature of 700 C. Lu. Moran. Carbon 39. G. 1996. 36.. Effects of pore structure and temperature on VOC adsorption on activated carbon. R. 2001.C.J. 2304–2318. Hassler... Phan Tan Luu. S.. Guo. Can.R.. A. Lee.. C. Rigola. F. Chiang.I. 1996. Chen... Cat. Adsorption of gases in multimolecular layer. Carbon 40... Bansal. 103–111. 179–274.. 1. I. P. Eng. New York. Bennouna.. Fuel 79.A. Carbon 34. Soc. Annadurai. Dahbi. This cost analysis would include equipment. electricity usage. 60.C..

1207–1214. San Miguel.L. Calvo. Toles. University of Nantes. Sollars.... Tay. 1009–1016. Res. Surface functional groups on acid-activated nutshell carbons. 1999. Carbon 38..E. P. 2000.. 2003. Otero. Munoz.. McAloon. Ekinci. 2003. A study of the characteristics of activated carbons produced by steam and carbon dioxide activation of waste tyre rubber. 1999. Biores. A. Graham.. M.. Yue. M.. R. Norme AFNOR NF X31-211.A. 2000.H. 75.. Faur-Brasquet. J. Garcia. Z... 2001. L.. Martinez-Alonso. Petrov. Procedes de traitement d’air chargee en COV par adsorption-de sorption sur tissu de carbone active. 1999. G. Carbon 41.. 1103–1116.. S. Marin-Villacorta. 2002. 2000. Tascon.I. Chemosphere 44. C.. Yardim.G. Liquid-phase adsorption of dyes and phenols using pinewood-based activated carbons. Carbon 37... Thesis.J. 53–57. Lecuyer. A.-L.. Steam or carbon dioxide-activated carbons from almond shells: physical.D. chemical and adsorptive properties and estimated cost of production. Technol. Mangun. P.. Jeyaseelan..D. C. I. Oviedo. Marshall. Juang. C.. Wu.M. Minkova. F. In: Proceedings of Carbon’03. Marshall. W. Carbon 37. Guerrero-Ruiz. 2001. Rio et al.H. J. 965–976.M. Preparation and characterization of carbon adsorbents from furfural. V.D. L. Chen. Le Cloirec.S. Wartelle. 1181– 1191.. Budinova....M. Experimental design methodology applied to adsorption of metallic ions onto fly ash. Porous texture of activated carbons prepared by phosphoric acid activation of apple pulp. Le Coq. P.. Carbon 39. E. Razvigorova. 2003. C.. Rio. Subrenat. J.. Ph. N. Carbon 41. . L. G.. Toles..A. Rozada. Carbon 40... A. W. 1065–1074. T.-C. 2003..-S. C.. 35. R. Interaction of aqueous solutions of phenol with commercial activated carbons: an adsorption and kinetic study. France. A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons. Wat. 2069–2075.. Le Cloirec. 221–230.F. M. Economy. A.. Fowler. A. D. 87. 437 Suarez-Garcia. Tseng.. / Chemosphere 58 (2005) 423–437 Nevskaia.. S. Dye adsorption by sewage sludge-based activated carbons in batch and fixed bed systems. F. ZnCl2 activation of polymer-coated fibers. X. Ricou.... F. Technol. V. N. A.. Johns. 487–495. Biores.. 197– 203. Dechets––Essai de lixiviation d’un dechet solide initialement massif ou gene repar un procede de solidification. Preparation of fibrous porous materials by chemical activation: 1.E. F. J. Santianes. Structure characterization of porous carbonaceous materials from sewage sludge.. 2001..