Abstrat Oraux

ICEC'13 Keynotes and Orals Abstracts CO -1
TCHES International Chemical Engineering Congress, December 16-19, 2013, Djerba - Tunisia 1
physicochemical properties of the membrane

Evolution of the hydraulic surfaces. As shown by Ochoa et al. on
polymeric membranes [2], the sieving effect
permeability of a low cut-off
of a membrane is not only determined by pore
Na-Mordenite membrane size but also by the hydrophilichydrophobic
during the conditioning and property character of a membrane. Navajas et
the operating steps al. [3] have demonstrated that the
modification of the surface chemistry of a
Mordenite membrane after an alkalin
L. Limousy, P. Dutourni
Institut de Science des Matriaux de Mulhouse (IS2M)
treatment, induced an alteration of the
UMR CNRS 7361, Universit de Haute Alsace, selectivity associated to an increase of the
Mulhouse, France surface hydrophilicity. These results indicated
that the knowledge of the surface chemistry of
Abstract:
the membrane active layer before the filtration
Membrane conditioning and stabilization tests is a crucial point.
are well known, but only few works The aim of this study was to observe and to
described these phenomena. Whatever the understand the different evolutions of the
active layer is made off (polymer, membrane active layer surface during the
mineral,), a period of conditioning is conditioning and the operating steps. The
necessary before the stabilization of the determination of the permeation flux and also
membrane permeability. In this work, we the characterization of the membrane surface
investigate the evolution of a low cut-off properties were used performed during this
UF ceramic membrane during the study.
conditioning step and also during the
operating period of the membrane. Results 2. Experiment
show that the conditioning step could be A Na-Mordenite membrane was prepared
separated in two phases, while the by seeded hydrothermal synthesis onto
evolution observed during the operating commercial alumina tubular support
step directly depends on the composition (length=2510 m; internal radius=3.510-3
-2
of the feed solution m) provided by Pall Exekia (Bazet, France).

The synthesis was performed according to the
Key words: hydraulic permeability, Na- protocol developed by Hincapie et al. [4].
Mordenite membrane, hydration, silicon extraction
Then, the membrane is calcinated at 400C for
1. Introduction 4 h. During the conditioning and the operating
steps, the hydraulic permeability was assessed
Membrane processes, low cut-off
by the measurement of the flux density
ultrafiltration and nanofiltration, are
performed with pure water (<0.5 S.cm-1) at
effective separation technique, at low-
consumption, and that avoids or limits the 25C. The experimental setup used in this
resort to chemical treatments. This study was described in previous works [5].
separation technique is governed by 3. Results and Discussion
different phenomena: steric (pore size and
shape), electrostatic (surface charge, The membrane permeability was calculated by
polarity), and dielectric [1]. There are two measuring the permeation flux at different
transmembrane pressure. The relation between
kinds of membranes: ceramic and organic
the permeate flux and the permeability is
ones. Whatever the membrane is, a
detailed in equation (1).
conditioning step is necessary to reach an
Lp
equilibrium state of the membrane Jw = P Eq.(1)
performances. Particularly, the hydration
of the active layer of the membranes is an Figure 1 displays the evolution of the
important phenomena, which modify the permeability logarithm according to the

2 TCHES International Chemical Engineering Congress, December 16-19, 2013, Djerba - Tunisia
filtration time (black points) observed presence of ionic or alkaline (Na2CO3,

during the stabilization step of a Na- pH=10.9) solutions. The permeability
Mordenite membrane. First, a fast decrease increased from 7.8 10-15m3m-2 to 1.7 10-
14 3 -2
of the permeability was observed, m m after 34 experiments. This behaviour
corresponding to the surface hydration of was attributed to silicon extraction during the
the Na-Mordenite crystals and also to their alkaline treatment, which induced an increase
reorganization. of the membrane surface hydrophilicity
(decrease of the Si/Al ratio) as showed by
Ochoa et al. [2]. Silicon atoms may be
extracted from the extraframework of the
Mordenite crystals, leading to the
modification of the membrane surface
properties and also to a slight increase of the
mean pore diameter. The modification of the
membrane surface properties was detailed in a
previous work [6].
Figure 1: simulation of the membrane permeability 4. Conclusions

stabilization (blue line) with two different equations This work showed that the stabilization of the
corresponding to surface (green line) and
microporosity hydration (red line) membrane performances, during the
conditioning step, could be represented as a
combination of two phenomena: surface
The second phase was attributed to the hydration coupled with crystals reorganization
diffusion of water inside the zeolite pores. and pores hydration. The evolution of the
The evolution of the membrane hydraulic permeability observed during the
permeability was simulated (blue line) by a experiments was attributed to silicon
combination of two equations extraction, leading to an increase of the
corresponding to the surface hydration and membrane surface hydrophilicity and then to
reorganization (green line) and also to the an increase of the water permeation flux.
diffusion of water molecules inside the
membrane pores (red line). A correlation References
between the micropore volume of the [1] Tavolaro A., Drioli E., Zeolite membranes. Adv. Mater.
1999, 11, 975-996.
zeolite (4 different membranes) and the [2] Ochoa N. A., Masuelli M., Marchese J., Effect of
slope of the linear equation corresponding hydrophilicity on fouling of an emulsified oil wastewater
to the pore hydration was determined. with PVDF/PMMA membranes, J. Memb. Sci., 2003,
226, 203-211
[3] Navajas A., Mallada R., Tllez C., Coronas J., Menndez
M., Santamaria J., Study on the reproducibility of
mordenite tubular membranes used in the dehydration of
ethanol, J. Memb. Sci., 2007, 299, 166-173.
[4] Hincapie B.O., Garces L.J., Zang Q., Sacco A., Suib S.L.,
Synthesis of mordenite nanocrystals. Microporous and
Mesoporous Mater. 2004, 67, 19-26
[5] E. Chevereau, N. Zouaoui, L. Limousy, P. Dutourni, S.
Don, P. Bourseau, Surface properties of ceramic
ultrafiltration TiO2 membranes: Effects of surface
equilibriums on salt retention, Desalination, 255, 1-3,
2010, pp 1-8.
[6] L. Limousy, P. Dutourni, E. Chevereau, Descritpion of
Figure 2: Evolution of the membrane permeability the preferential transport of monovalent salts through Na-
after different experimental tests carried out with Mordenite membrane: physico-chemical aspects,
salt and alkaline solutions Microporous and Mesoporous Mater., 167, 2013, pp 133-
136.
Figure 2 displays the evolution of the
hydraulic permeability after several
experimentations carried out in the
STUDY OF BIOREFINERY In the present work two different

biorefinery processes were techno-
SCENARIOS BY PROCESS economically evaluated by process simulation.
SIMULATION 2. Materials and Methods
Araceli Garca, Mara Gonzlez Alriols,
Rodrigo Llano-Ponte, Jalel Labidi 2.1 Process Simulation
Aspen Plus was used to design and
Department of Chemical and Environmental
Engineering, University of the Basque Country UPV- simulate the two organosolv and soda-based
EHU. Plaza Europa 1, 20018 Donostia San Sebastin biorefinery scenarios on the basis of
(Spain), jalel.labidi@ehu.es experimental and literature data [1,2,3].
Abstract: Lignocellulosic material was used as
feedstock for this purpose (45% cellulose,
In the present work, an organosolv and 20% hemicelluloses, 30% lignin, 5% acetate
soda-based biorefineries were proposed, groups, w/w).
designed according to experimental and
literature data and simulated with Aspen 2.2 Main sections in the proposed biorefinery
Plus in order to establish the process mass scenarios
and energy balances, the yield and the Both biorefinery scenarios were designed
water and energy requirements of the for the treatment of 1000 kg/h of
process. Based on the use of lignocellulosic biomass. These designs
lignocellulosic biomass as feedstock, the consisted in several steps: fractionation or
proposed biorefineries were designed for pretreatment of the raw material, lignin
the obtaining of different products recovery, biotransformation of saccharides
(bioethanol, citric acid, and lignin) through and solvent/water recovery.
the application of different process steps The pretreatment steps consisted in the
(fractionation, separation, solvents and fractionation of the biomass with alkali (7.5%
water recovery, polysaccharides NaOH w/w, 90 min, 90 C) or aqueous
biotransformation). In order to maximize ethanol (60% EtOH v/v, 90 min, 180 C) for
yields and to minimize reagents and the soda and organosolv biorefineries,
utilities requirements, different process respectively. After that, different separation
streams were recycled and reused. and washing steps were applied in order to
Key words: biorefinery, process obtain a cellulosic solid fraction and a liquid
simulation, bioethanol, lignin. fraction containing the dissolved lignin and
hemicelluloses.
1. Introduction The resulted cellulosic solid fraction was
In order to become an actual alternative submitted to biotransformation step, where it
to fossil fuels and petroleum derivate was transformed into bioproducts (ethanol and
products, biorefinery processes are being citric acid for the organosolv and soda
widely investigated, searching different biorefineries, respectively) by means of the
pathways for the challenge of being application of several processes (hydrolysis,
competitive and cost-effective [1]. saccharification, microorganisms inoculation
Lignocellulosic biomass biorefining and growth, etc.).
entails a first fractionation step (using Both alkali and organosolv black liquors
aqueous mixtures of acid, basic and were submitted to an ultrafiltration process
organic solvents), as well as further (using ceramic membranes) in order to
treatment and processing. For this revalorize lignin, which was recovered by
proposal, new approaches in production precipitation [1,2].
technologies, research and development Different liquid streams resulted from
are necessary in order to make biorefinery separation and washing processes were
processing competitive and cost-effective processed (by evaporation and/or distillation)
[2]. for the recovery of solvent (ethanol in the
organosolv scenario) and water ( in both heating/cooling utilities. Furthermore, the

soda and organosolv biorefineries). recycling of sugar-enriched concentrates, from
The resulting aqueous effluents were evaporation processes to the biological step
reused in the proposed biorefinery led to an increase of a 64% on the citric acid
scenarios in order to minimize waste production process.
generation and water requirement. Figure 1
(a,b) displays the methodology followed
for this purpose.
Figure 2: Feedstocks and utilities requirements for

the treatment of 1000 kg/h of raw material in the
proposed soda and organosolv biorefineries.
Similarly, the recirculation of the ethanol
containing streams allowed to a 94%
reduction of the fresh ethanol consumption.
Furthermore, the reutilization of the sugar-
containing waste streams and the aqueous
effluents led to an increase of 58% of the
produced bio-ethanol and a reduction of 88%
in the water requirement, respectively.
4. Conclusions
In the present work two different
lignocellulosic biorefinery scenarios were
designed and simulated in order to evaluate
their mass and energy balances. Through the
application of stream integration, several
Figure 1: Schemes of streams recycling for the
aqueous streams were reused in different
proposed a) soda-based and b) organosolv-based
biorefineries. steps, improving yields and reducing water
and chemicals requirements.
3. Results and Discussion
Acknowledgment
3.1 Results
The authors would like to thank the University of
High water, chemicals and the Basque Country (GUI11/10) and Spanish
heating/cooling utilities requirements were Ministry of Economy and Competitiveness
needed for the initial soda and organosolv- (CTQ2010-19844-C02-02) for financially supporting
based biorefineries processes designs this work.
(Figure 2). References
Nevertheless, after the integration of
[1] Gonzlez Alriols, M.; Garca, A.; Llano-Ponte, R.; Labidi,
several process streams, mainly consisting J. Combined organosolv and ultrafiltration lignocellulosic
in the collection and reuse of aqueous biorefinery process. 2010, Chem Eng. J. 2010, 157, 113-120.
streams, significant water and chemicals [2] Garca, A,; Gonzlez Alriols, M.; Llano-Ponte, R.; Labidi,
saving were achieved. The recycling of J. Energy and economic assessment of soda and organosolv
aqueous streams in the soda-based biorefinery processes. Biom. Bioenerg. 2011, 35, 516-525.
biorefinery process attained a 23% [3] Wooley, R.J.; Putsche, V. Development of an ASPEN
reduction of chemicals, 100% of fresh PLUS Physical Property Database for Biofuels Components.
water savings and 11-12% of
1996, NREL/MP-425-20685, National Renewable

Energy Laboratory, Golden, Colorado.
SOLID REACTION EFFECT bed. Erosion by only impact exceeds global

particle attrition in the case of oil shale
ON MECHANICAL particle. Increase of thermal decomposition
IMPACT EROSION OF increases the mass loss from the solid particle
FLUIDIZED BED by impacting. For each value of and we
propose an experimental method to evaluate
REACTOR the capacity of erosion by the granular
Bouhafid A. Hakki A. Elhadi M.A medium inside the bed operated at different
Dpartement de Chimie Facult des velocity. (*) corresponding authors
Sciences Semlalia Marrakech, Maroc
bouhafid@uca.ma(*)
Abstract
In this investigation, we were most
interested in experimental evaluation of
particle attrition due to mechanical impact
by granular bed of particles in laboratory
bubbling fluidized bed reactor (FBR). We
present an experimental methodology to
estimate the effective power erosion of
fluidized bed reactor. The experimental
results concern the local impact effect and
the evaluation of the estimation of
fluidized bed power erosion by impact if
we integrate all the contributions of
measured local particles mass loss. Oil
shale particle from Tarfaya deposit have
been used as candidate for all the
experimented tests. When solid particle
react inside a FBR, thermal decomposition
occurs and starts on the external surface of
the solid particle and the reactant contained
in the particle is gradually affected. For
thermal degradation mass loss of solid
particle is characterized by =
(0)0 , 0 is the initial particle mass
and m the particle masse at time t. Only
gases escape from the fuel particle. The
mass loss by impact process is
characterized by = (M0-Mt)/M0, M0 is the
initial particle mass before impact and Mt
the particle mass at time t after silica
impact in the bed. In this case the detached
solid is removed from the surface of the
solid particle. Oil shale particles have been
heated to different temperatures ranging
from 400C to 850C at during different
times before suffering silica sand particles
impact in FBR operating at 25C.
Fluidized bed velocities used are 1.5 Umf
and 2 Umf. Results show that impact effect
varies with the local position inside the
MODELISATION DE ELECTROFLOTATION
LHYDRODYNAMIQUE COLUMN
DUNE COLONNE FOR THE TREATMENT OF
DELECTROFLOTTATION INDUSTRIAL
POUR LE TRAITEMENT WASTEWATERS
DES EAUX USEES Abstract
In this work, the hydrodynamic study of
INDUSTRIELLES oxygen and hydrogen bubbles flow generated
I. Ksentini, M. Kotti, *L. Ben Mansour in an electroflotation
Laboratoire de recherche: Mcanique des fluides
appliqus, Gnie des Procds et Environnement column working in batch and continuous
Facult des sciences de Sfax, B.P.1171, 3000 Sfax - mode was performed. The method of video
Tunisie recording and image
Email: lassaadbenmansour@yahoo.fr processing was used to determine the diameter
Rsum and the rise velocity of bubbles and also the
Dans ce travail, ltude de gas retention. The
lhydrodynamique des flux de bulle effect of current density applied at the
doxygne et dhydrogne gnre dans electrodes of the electroflotation column, the
une liquid phase
colonne dlectroflottation fonctionnant en physicochemical parameters and the variation
mode batch et continu a t ralise. La of the liquid phase flow has been studied. The
mthode denregistrement overall results were
vido et traitement dimages a t utilise modeled in order to describe the bubble flow
pour dterminer le diamtre et la vitesse regime. These models have been implemented
des bulles ainsi que la in a code
rtention gazeuse. Les effets de la densit programmed in Visual Basic and allowed the
de courant applique aux lectrodes de la development of an executable application.
colonne dlectroflottation, This application was
les paramtres physicochimiques de la then used successfully in order to determine
phase liquide ainsi que la variation du dbit the optimum operating conditions for treating
dalimentation de la phase industrial wastewaters
liquide ont t tudis. Lensemble des by electroflotation process.
rsultats a t modlis pour dcrire le Keywords: Electroflotation Hydrodynamic
rgime dcoulement des bulles. Modeling Visual Basic Treatment
Les modles obtenus ont t implments Wastewaters
dans un code programm en Visual Basic
permettant llaboration
dune application excutable. Enfin cette
application a t exploite a fin de
dterminer avec succs les
conditions opratoires optimales de
traitement des eaux uses industrielles par
le procd dlectroflottation.
Mots cls : Electroflottation
Hydrodynamique Modlisation Visual
Basic Traitement Eaux uses
MODELLING THE
HYDRODYNAMIC OF AN
SIMULATION OF THE continuous or discontinuous feed modes.

DENITRIFICATION Schultess et al. [2] have developed a new
mathematical model including three steps for
BIOLOGICAL PROCESS WITH
the denitrification process: nitrate, nitrite and
A S-SYSTEM: A NON nitrous oxide reduction. Nevertheless, the
CONVENTIONAL APPROACH ASM model was calibrated for specific
experimental conditions and also did not
Adouani Nouceibaa, Limousy Lionelb, include the formation of nitric oxide.
Lendormi Thomasc et Sire Olivierc
a Laboratoire Ractions et Gnie des procds, LRGP, We choose to implement a kinetic model
Nancy, France., using PLAS (Power Law Analysis and
b. Institut de Science des Matriaux de Mulhouse, CNRS Simulation), which was developed by Ferreira
,UMR-7361 , 3 bis rue Alfred Werner, 68093 Mulhouse,
France, to simulate the evolution of biochemical
c .Universit Europenne de Bretagne, LimatB, Pontivy, systems [3]. A lot of considerations associated
France, to dynamic systems suggest that power laws
Abstract: efficiently represent their evolution [4,5].
The modelling of the denitrification
process was compiled by the IAWQ group In this work, we developed a kinetic model
[1]. The ASM model (1, 2 and 3), which is where all the reagents, intermediates and
the most used all over the world, is not products were taken into account. The use of
adapted at the moment to integrate the PLAS allowed the extraction of the best fitted
nitrous and nitric oxide emissions during parameters to match experimental data,
the denitrification process. In the present including the NO and N2O production. In
work, a S-System model (PLAS) was used order to extract the main characteristics of the
to simulate the nitrate reduction observed denitrification pathway, results of the
in specific experimental conditions. Data simulation were compared to these data. An
from a representative experiment were alternative model of the denitrification process
chosen (T=10C, pH=7, COD/N=3, with was proposed.
acetate as substrate) to simulate NO and 2. Experimental procedure
N2O emissions, in order to test some
The experimental setup used in this study is
hypotheses about the corresponding
described in Figure 1.
metabolic pathways. Results showed that
the reduction of nitrate and nitrite is
kinetically limiting, and also that nitrate
reduction was limited by diffusion.
Keywords: Denitrification; Simulation; S-
System; PLAS; Kinetics.
1. Introduction
The production of N2O and NO during
the denitrification process are related to
several parameters such as the COD/N Figure 1: Experimental setup for denitrification
ratio, the concentration of pollutants, the The parameters of the simulated batch
temperature and the substrate nature. The experimentation were: pH=7, T=10C,
modelling of nitrate abatement during the COD/N=3, acetate as carbon source (1.88
biological denitrifcation process was mM), [NO3-]=2.86 mM.
mainly studied by using the ASM model (1, The evolution of acetate concentration
2 and 3), developed by the IAWQ group observed during the experimentation was
[1]. This model is able to represent the time firstly fitted by two stretched exponentials, the
evolution of carbon and nitrogen pollutant first featuring acetate consumption, the second
abatements by activated sludge, for one being associated to EPS formation (which
can erroneously be assigned to hard COD).
The law corresponding to the evolution of was limited by the diffusion (reaction order
acetate concentration was introduced in the close to 0.35).
kinetic model in order to control the
evolution of COD during the
denitrification process. In comparison with
the ASM1 model, the same assumptions
were made, and NO was also added both in
the gaseous and aqueous phases.
The kinetic model we built is presented in
Figure 2. It includes independent variables
(green frames), liquid and gas dependent
variables (blue and red frames,
respectively). A kinetic constant k was
associated to each reaction, and inhibiting
Figure 3: Experimental and simulated values
effects were also represented by specific observed and recovered during the denitrification
exponents (gxy). process performed at 10C.
Figure 3 displays the simulated values
obtained with the power laws model, which
can be compared with the experimental data.
If it fits well during the first 6 hours, the
deviation becomes important beyond this
period. It means that the biological reduction
of nitrate is a complex phenomenon, which
Figure 2: Kinetic model developed for the depends on several parameters and that
simulation of the denitrification process couldnt be globally simulated by a single
The best fitted values of this model were metabolic pathway.
obtained following an operator-driven 4. Conclusion
iterative methodology (Table 1).
The simulation of the denitrification
Table 1: Best fitted parameters obtained with
process was performed with a S-System in
PLAS
Parameters Values Comments order to warrant for observed NO and N2O
k1 0.025 (M. h-1) emissions. Results showed that this process is
k2 3.10-3 (M. h-1) complex and suggest that distinct metabolic
k3 1.75 (M. h-1) k3 >>k1
k4 1.75 (M. h-1) k4 >> k1
pathways must be involved.
k30 0.01 (M. h-1) References
k40 0.22 (M. h-1) [1] Henze, M., Grady, C.P.L. Jr, Gujer, W., Marais, G.v.R.
gx1 0.35 Nitrate reduction order and Matsuo, T. (1987). Activated Sludge Model No. 1.
gx2 1 Nitrite reduction order Scientific and Technical Report No.1, IAWPRC,
gx3 1 NO reduction order London.
gx4 1 N2O reduction order [2] Schulthess R.V. and Gujer W., 1996. Release of
g22 -0.08 Nitrite inhibition over nitrous oxide (N2O) from denitrifying activated sludge:
nitrate reductase Verification and application of a mathematical model.
g25 -1.9 Nitrite inhibition over Water Research, 30, 521-530.
N2O reductase [3] Ferreira, E. N., 2000. Logiciel PLAS in
g44 - 0.45 N2O inhibition over Computational Analysis of Biochemical Systems. E.
NO reductase O. Voit. Cambridge University Press.
[4] Voit, E. O. 1991. Canonical nonlinear modelling. S-
It was observed that nitrate and nitrite system approach to understanding complexity. Van
reductions are kinetically limiting reactions Nostrand Reinhold, New York.
(k1 and k2<<k3 and k4) as described in the [5] Savageau, M.A. 1995. Michaelis-Menten mechanism
reconsidered : implication of fractal kinetics . J.
literature, and also that nitrate reduction Theor. Biol. 176, 115-124.
I nvestigation of grape marc The tested samples of wine residues

(Sylvaner variety) were produced in Alsace
combustion using (France). The grapes were separated manually
thermogravimetric analysis. in three different samples: stalks, skins and
Kinetics modeling using an seeds. The characterization of each sample
was made following the standard XP CEN/TS
extended I ndependent Parallel for the moisture content, the ash content and
Reaction (I PR) model. the calorific value. Ultimate analyses
M. Valente, A. Brillard, C. Schnnenbeck (CHONS) were also performed for each
and J.F. Brilhac samples.
Laboratoire Gestion des Risques et Environnement,
7KHUPRJUDYLPHWULF$QDO\VLV7*$
EA2334 - 3bis, rue Alfred Werner - 68093 Mulhouse Thermal degradation of biomasses was
Cedex - France, jean-francois.brilhac@uha.fr
extensively studied by thermogravimetry
Abstract: analysis [3]. In this investigation, experiments
The increase of the demand for were performed in a thermobalance CAHN
renewable energies leads to diversify the TG121 at heating rates of 5, 10 and 20C/min,
biomass combustible resources. The in the temperature range 30 815C, and
present investigation focuses on the under a synthetic air flow of 10 NL/h (20%
thermal conversion of the grape marc as a O2, 80% N2).
new potential resource. The combustion of .LQHWLFPRGHOLQJ
wine residue is evaluated experimentally
Among the different kinetics approaches,
by thermogravimetry analysis. A model is
the independent parallel reaction (IPR) and the
proposed for the thermal decomposition of
iso-conversional models have been applied to
grape marc considering devolatilization
simulate the thermal degradation ([4] and [5]).
and char combustion using an IPR model
They both show a good accordance regarding
Key words: Biomass, Kinetics, Grape marc, to the experimental data. We have used the
Combustion, Thermogravimetric analysis IPR model in order to describe the biomass
structure with the lignocellulosic materials
1. I ntroduction representation. The kinetic model proposed is
Biomass combustion is one of the routes extended to account for both devolatilization
for the European countries to diversify and char combustion.
their energy production and meet their TGA curves are described by four
environmental engagement, for example in independent parallel reactions. Three reactions
term of carbon balance. The Upper-Rhine for devolatilization of each constituents of the
Region is known for wine production grape marc (Hemicellulose H, Cellulose C and
leading to large quantities of grape marc Lignin L) and one for heterogeneous
which should be a relevant biomass combustion of the Char produced (CH). The
resource. Only few studies are related to overall mass conversion rate during thermal
the combustion of wine residues and to the degradation is expressed according to a first
corresponding emission regulation ([1] and order reaction:
[2]).
In the present work, the kinetics of this
biomass combustion is investigated from a
thermogravimetric point of view and we fit
the values of the kinetic parameters using

the IPR model.

2. M aterials and M ethods
0DWHULDOVDQGFKDUDFWHUL]DWLRQ where: m(t) is the mass sample at time t,

mi (t) is the mass of the i th constituent at time t,
ci is the contribution of the i th constituent Table 1. Grape seed; kinetic parameters extracted
to the overall combustion process, by the extend IPR model
m0 and mash are respectively the initial Contribution
Constituent Ea / J.mol-1 A / s-1
factor (ci )
mass of the sample reaction and the mass H 1.01e+05 4.0e+8 0.136
of ash, C 1.17e+05 5.0e+8 0.222
L 1.31e+05 6.0e+8 0.208

is the mass conversion rate of the
Char 1.66e+05 6.0e+9 0.434
overall sample,
Ai is the pre-exponential factor of the i th 4. Conclusions
constituent, In this contribution, we have studied the
Ei is the energy activation of the i th combustion process of grape marc using a
constituent, thermogravimetric analysis. Using the IPR
R is the gas constant (8.314 J/mol.K). model and solving a first-order reaction
3. Results and Discussion system through the SCILAB software, we
have determined the best set of kinetic
7KHUPRJUDYLPHWULFH[SHULPHQWV
parameters for the combustion process.
The DTG analysis (Fig. 1) shows that
Acknowledgment
during the devolatilization step (occurring
from 150C to 400C) there is no specific This work was performed in the framework of the
difference between skins and stalks. ,17(55(* 3URJUDP 28, %LRPDVVH ,QQRYDWLRQV
for sustainable biomass utilization in the Upper
However, a singular peak may be observed
Rhine Region). The authors wish to thank the
around 350C for seeds. This could be European Community (FEDER) and the Trinationnal
explained by a bigger proportion of lignin Metropolitan Region for their financial support.
in the grape seed. The char combustion
step (from 400C to 520C) starts earlier Reference
and is faster for the stalks (0,141 %/s at [1] Caillat, S.Molcan, P.Perdrix, E.Alleman, L.Campargue,
M.Naudy, V.Lambre, C.Dacquin, H.Douard, F.and Badji,
405C) than for the grape seeds and skins L. In Small-scale combustion experiments of selected
(respectively 0,086 and 0,055 %/s at 441 agricultural by-products potential for biomass pellets
and 466C). production in France, Proceedings of the Fourth
International Symposium on Energy from Biomass and
0,15 Waste, Venice, 2012.
Grape
0,12 skin [2] Miranda, T., Romn, S., Montero, I., Nogales-Delgado, S.,
Arranz, J. I., Rojas, C. V., and Gonzlez, J. F. Study of
DTG (%/s)
0,09 Grape
the emissions and kinetic parameters during combustion
seed of grape pomace: Dilution as an effective way to reduce
0,06 Grape pollution. Fuel Processing Technology 2012, 103, 160
stalk 165.
0,03
0 [3] White, J. E., Catallo, W. J., and Legendre, B. L. Biomass
0 100 200 300 400 500 600 700 pyrolysis kinetics: A comparative critical review with
relevant agricultural residue case studies. Journal of
Temperature (C) Analytical and Applied Pyrolysis 2011, 91, 133.
Figure 1: Grape marc DTG (skin, seed and [4] Damartzis, T., Vamvuka, D., Sfakiotakis, S., and
stalk); Thermal degradation rate (%/s). Heating Zabaniotou, A. Thermal degradation studies and kinetic
rate: 5C/min. modeling of cardoon (Cynara cardunculus) pyrolysis
using thermogravimetric analysis (TGA). Bioresource
.LQHWLFSDUDPHWHUV Technology 2011, 102, 62306238.
The resolution of the above first-order [5] Santos, K. G., Lobato, F. S., Lira, T. S., Murata, V. V.,
system through the SCILAB software leads and Barrozo, M. A. S. Sensitivity analysis applied to
independent parallel reaction model for pyrolysis of
to the following set of kinetic parameters bagasse. Chemical Engineering Research and Design
for the four constituents of the grape marc. 2012, 90, 19891996.
Tab. 1 presents the results obtained for the
grape seed.
Study of non stationary avoids the emissions of carbon dioxide,

nitrogen oxide and sulfur. In addition, it has
behavior of the absorption no adverse effect on people or for generations
phase of an absorption cooling to come. And the potential of solar cooling is
cycle operating intermittently the simultaneity of cooling demand with the
Ibtissem Chattouna1, Yasmina availability of the solar resource. The solar
Bouckchana1, Ali Fellah1, Ammar Ben cooling technologies are still in the process of
Brahim1 development and more research must be done
to reduce costs and increase efficiency. There
1. Research Unit, Applied Thermodynamics are several types of refrigeration cycles, but in
(99/UR/11-21), Gabes University, National this paper we will look at the absorption
School of Engineers, 6072 Gabes, Tunisia,
E-mail addresses: cooling cycle which works with absorption of
ibtissem.chattouna@gmail.com solar energy.
yasmine_boukhchana@yahoo.fr This study is a contribution to the
al.fellah@gmail.com
ammar.benbrahim@enig.rnu.tn. development of the work done on the cycles
of solar absorption refrigeration operating
Abstract: intermittently. The modeling of the absorption
The modelling, in dynamic state, of the phase of an absorption cooling cycle operating
absorption phase of an absorption cooling with the couple ammonia/water was
cycle operating intermittently with the elaborated.
couple ammonia/water was elaborated. The 2. Description of the cooling unit
study based on intermittent operation has
developed, through the heat and material The refrigeration system having low solar
balances, a thermodynamic model relating absorption, designed to operate with the pair
temperatures, flow rates and mass fractions NH3/H2O, basically consists of a generator-
in the different compartments. absorber, a condenser, an evaporator-storage
Representative sunny days of the four tank, a separator, a feed solution reservoir, a
seasons of the year were considered, the reservoir ethylene glycol, a solar collector, a
results thereafter exploited only for the feed pump and five block valves (Figure 1).
ambient temperature Ta = 30 C.
Key words: Refrigeration ; Absorption ; Solar
energy ; Intermittent ; Simulation
1. Introduction
Heating and cooling are two of the
biggest expenses for most human
activities. The use of solar energy to
reduce these expenses is a financial and
ecological necessity. The absorption
refrigeration machine is at the heart of the
cooling system.
While the traditional refrigeration
machines consume a lot of electricity at
times of peak demand for cooling, the
absorption refrigeration machine is
supplied with heat at a relatively low
temperature. Figure 1: Diagram of a system of intermittent solar
Solar cooling is an innovative absorption refrigeration
application of technology established of The cycle operates according to two phases:
solar energy and thermal. This energy a phase of generation and an absorption phase
produces cold without causing pollution. It (cooling). During the generation phase, which
takes place on the day, the ammonia-water Figure 3 shows the variations of the
mixture (NH3/H2O) is heated in the temperature of the absorber, the separator and
generator with ethylene glycol as the supply tank with time.
coolant fluid heated by the incoming solar 360
radiation on the concentrator. 350

At night, during the absorption phase,
Temperature (K)
340
the ammonia present in the evaporator is
330
pure then a solution of H2O/NH3 poor in
refrigerant is in the absorber. The vapor 320
Absorber
pressure of the solution is less than that of 310 Supply tank
Separator
ammonia. There will be, therefore, 300
0 2000 4000 6000 8000 10000 12000 14000 16000
absorption of the ammonia by H2O/NH3 Time (s)
solution until equalization of pressures of Figure 3: Variation of the temperature of the

the absorber and the evaporator, resulting absorber, the separator and supply tank with time.
in production of cold in the evaporator.
We note a sudden increase in the
3. Modeling of the absorption cycle temperature of the absorber which is due to
In order to determine the temperature the instantaneous increase in the mass of
variation of the different elements of the ammonia therein and that will be absorbed by
cycle during the absorption phase and the refrigerant-poor solution. Then there was a
compositions of ammonia solutions, a slight decrease returning to thermal losses that
mathematical model describing the have not been neglected then an increase in
dynamic behavior of each element scheme temperature due to the exothermic reaction of
has been developed. It is writing different absorption.
material balance and heat for each item. The temperature in the separator and the
These reports were written based on the supply tank depend on the temperature of the
following assumptions: It is assumed that absorber which justify their evolution over
absorption is total, the solutions are time.
assumed in thermodynamic equilibrium, 5. Conclusions
there is no heat loss in the various
The modelling of the absorption phase of an
components of the system.
absorption cooling cycle operating
4. Results and Discussion intermittently with the couple ammonia/water
The results thereafter exploited only for was elaborated.
the ambient temperature Ta = 30 C. We followed the evolution of the different
306
parameters of the absorption phase as a
304
function of time of using a MATLAB
302
Water program. By neglecting the thermal loss, there
Ammonia
Temperature (K)
300
was obtained a reduction of 11.27C of the
298
temperature of the water to be cooled during
296
4h 15min.
294
292
0 2000 4000 6000 8000 10000 12000 14000 16000
Time (s)
Figure 2: Variation of the temperature of

ammonia in the evaporator and the water
temperature with time.
The gap between the two curves is due

to the vaporization of the refrigerant which
takes the heat from the local to be cooled.
TCHES International Chemical Engineering Congress, December 16-19, 2013, Djerba - Tunisia
Granular and Pelletized CAGOC-Pas. Temperature- dependent

methane isotherms show that the isosteric heat
activated carbon based on of adsorption reaches 20 kJ/mol for all the
olive stones for methane stages o loading methane.
storage 1. Introduction
Sonia BEN YAHIA, Abdelmottaleb

Methane, as the main component of natural gas
OUEDERNI has received important attention as a future
clean energy source, since its available, and
Research Laboratory: Process Engineering and
more environmentally preferable and cheaper
Industrial Systems GPSI compared to petroleum based fuels. All these
National School of Engineers of Gabes, University reasons, had led human activities to evolve its
of Gabes, Str Omar Ibn Elkhaatb, 6029 Gabs- transportation methods and its uses as a
vehicular fuel by the evolution of storage
Tunisia
process using adsorption on solid materials to
benyahya.sonia@gmail.com,
mottaleb.ouederni@enig.rnu.tn
reduce all security problems. One of these
solid materials is activated carbon based on
many raw materials such biomasses [1], coal,
Keywords: Cyclic operation adsorption- petroleum coke, pitch, synthetic organic
compounds and anthracites. These activated
desorption, Methane, Olive stones,
carbons can be used on many forms (granular,
granular, pellets fibrous, powder or pelletized) [1-4]. In spite of
low cost and simple production process of
granular activated carbon, pellets can be
Abstract chosen as the most important form for methane
storage. Many efforts have been made to
The behavior of an olive stones based activated reduce useless voids and increase the bulk
carbon as an adsorbent for pure methane was density. Typically, carbon adsorbent particles
been investigated at room temperature( 298 K) can be achieved by being bound together to
under low pressure of about 10 bars. Two obtain activated carbon pellets.
forms of activated carbons was obtained
For all these reasons the aim of this work is to
(granular and pelletized) by chemical
compare the behavior of two forms of
activation using phosphoric acid. Methane
activated carbon ( granular and pelletized) as
storage was done using two different measure
methane adsorbents during cyclic operation of
techniques (gravimetric and volumetric). For
charge- discharge to find out the best
volumetric measures, a cyclic operation of 5
condition for the best methane adsorbent for
charge- discharge cycles was carried out using
vehicular uses.
the two forms of adsorbent granular activated
carbon CAGOC, and pelletized one CAGOC- 2. Experimental
Pas. Storage on CAGOC reaches 40 mg/g
under 10 bars with a release of about 30 mg/g 2.1. Materials
at atmospheric pressure. In the other hand,
CAGOC-Pas without binder reaches huge 2.1.1. Sample preparation
amount of adsorbed methane of about 68 mg/g
The present study deals with an activated
under 10 bars with a discharge of about 50
mg/g at atmospheric pressure. For gravimetric
carbon derived from olive stones grains.
measures, under 50 bars a huge increase of For Granular Activated Carbon:
adsorbed amount was seen from granular to This precursor was first washed with water
pelletized activated carbon from 72 mg/g to then impregnated ( 3/1 weight ratio
105 mg/g. The difference in adsorption H3PO4/Olive stones) with orthophosphoric
capacities and behaviors in cyclic operation acid reagent with 90% concentration for 9
can be probably related to best textural hours at 383K to be pyrolysed after at
properties and surface morphologies of 683K for 2,5 hours under nitrogen gas flow
1
and followed by water wash to remove 2.2. Experimental Set-up

impurities and to reach a pH near 6 . This
support activated by chemical way was A cylindrical cell (B), schematic diagram
named CAGOC. shown in figure 1 made of stainless steel
For Activated Carbon pellets: is used to measure gas uptake by granular
The precursor was first washed with water activated carbon sample. The cell volume is
then impregnated ( 3/1 weight ratio about 308 cm3 it can be operated up to 200
H3PO4/Olive stones) with orthophosphoric bars and between 243K to 473K.
acid reagent with 90% concentration for 9
hours at 383K to be compacted and
pelletized using Laboratory press . Then
pyrolyse step at 683K for 2,5 hours under
nitrogen gas flow was carried out and
followed by water wash to remove
impurities and to reach a pH near 6 . These
pellets activated by chemical way were
named CAGOC-Pas.
2.1.2. Sample characterizations

a. Nitrogen Adsorption
Figure 1: Sorption- desorption apparatus
These grain based activated carbons was 3. Results and Discussion
characterized with a gas sorption analyzer.
Quantachrome Autosorb- 1 MP analyzer Figure 2 shows adsorbed amounts
provided by Quantachrome Instruments. evolution during cyclic operation evaluated
Specifically, BET surface area and porous by volumetric measure technique up to 10
characteristics were determined from bars at 298K. In this histogram stability
nitrogen adsorption data (77K). The can be observed t for the two forms of
micropore volume was determinate adsorbents in spite of the difference in
according to te DR (Dubinin- adsorbed amounts due probably to the
Radushkevich) method. Porous volume, reduction of inter particles voids.
Specific area, microporous volume and
porous diamter are collected in table 1. 80
CAGOC
70
Table 1: CAGO characteristics 60
50
na(mg/g)
40
Characteristics CAGOC CAGOC-Pas
30
Sp BET (m/g) 1139 1213 20
V pores (cm3/g) 0,554 0,4141 10
Vmicropores(cm3/g) 0,547 0,4072 0
1 2 NCycle
3 4 5
D pore (A) 19,45 13,6
app (g/cm3) 0,419 0,55 Figure 2 : Adsorbed amounts evolution
real (g/cm3) 1,725 ** during cyclic operation obtained by
volumetric measure on granular and
pelletized activated carbon CAGOC and
CAGOC-Pas
2
To insure this stability isosteric adsorption prepared via binderless method, Energy
heat was calculated using Clausis- conversion and management, vol 52, pp 1258-
clayperon equation by the change of 1262, 2011.
adsorption temperature. Results are shown
[4]: D. Lozano- Castello, J. Alcaniz-Monge,
in figure 3 where an average of 20 kJ/mol
M.A.de la Casa-Lillo, D. Cazorla-Amoros, A.
was obtained for adsorption in pellets for Linares-Solano, Advances in the study of
all the adsorbed amounts at different methane storage in porous carbonaceous
pressures with a few behavior changes for materials, Fuel, vol 81, pp 1777-1803, 2002.
granular adsorbent from 30 to 20 kJ/mol.
35
30
Hads(Kj/mol)
25
20
15
CAGOC
10
CAGOC-Pas
5
0
0 5 10na(mg/g)15 20 25
Figure 3: Isosteric adsorption heat
evolution obtained by methane adsorption
on CAGOC and CAGOC-Pas
4. Conclusion
Compaction and pelletization of an olive

stone precursor increase adsorbed amount
of methane of the activated carbon for the
two measure techniques (gravimetric and
volumetric) from an average of 40 mg/g to
70 mg/g under 10 bars for volumetric
measure and from 72 mg/g to 105 mg/g
under 55 bars for gravimetric one. The
choice of activated carbon pellets as the
better than granular one can be insured by
isosteric adsorption heat stability in the
average of 20 kJ/mol for different adsorbed
amounts.
References
[1]: Marcos J. Prauchner, Francisco
Rodriguez- Reinoso, Preparation of granular
activated carbons for adsorption of natural
gas, Microporous and Mesoporous Materials,
vol 109, pp 581-584, 2008.
[2]: K.Inomata, K. Kanazawa, Y. Urabe, H.
Hosono, T. Araki, Natural gas storage in
activated carbon pellets without a binder,
Carbon, vol 40, pp 87-93, 2002.
[3]: C. Guan, Leslie S. Loo, K. Wang, C.
Yang, Methane storage on carbon pellets
3
Production de bio nergie par la possde un pouvoir nergtique lev et peut

Digestion Anarobie des dchets tre utilis dans de nombreuses applications
comme : le chauffage, la cuisson, la
mnager
production dlectricit, lclairage et en tant
( Etude de lInfluence de la salinit que biocarburant et pouvant tre inject dans
des eaux) le rseau de gaz de ville.
TAHRI Ahmed, KHELAFI Mostefa, KALLOUM Notre travail consiste tudier la digestion
Slimane, DJAAFRI Mohammed, anarobie des dchets mnagers (dchets de
KAIDI Kamel. cuisine) et plus particulirement linfluence du
Unit de Recherche en Energie Renouvelable en la salinit des eaux sur le rendement en
Milieu Saharien /Adrar. Algrie biogaz. Durant cette tude, nous avons suivi
E-mail : tahri@urerms.dz lvolution de pH, et le volume du biogaz
produit en fonction du temps. Les rsultats
obtenus ont permis de dmonter que la
salinit des eaux na pas dinfluence sur la
production du biogaz.
RESUME
La mthanisation ou la digestion anarobie
est un procd naturel de transformation de MOTS CLES
la matire organique en nergie par des Dchets mnagers, digestion anarobie,
bactries mthanognes en labsence biogaz, la salinit des eaux, leau
doxygne. Conduite dans des enceintes douce.
confines appeles digesteurs
lintrieur des quelles les ractions de
fermentation sont optimises et contrles.
Ces digesteurs produisent du biogaz,
compos majoritairement de mthane, tout
en rduisant de moiti le taux de matires
organiques reprsentes par de nombreux
dchets ou sous-produits biodgradables.
Le rsidu de la digestion (ou digestat)
obtenu est stable, dsodoris, dbarrass en
majeure partie des germes pathognes.
Les dchets de matire organiques
proviennent essentiellement des industries
agro-alimentaires, (des activits
domestiques, dabattoir) et des eaux
rsiduaires urbaines. Ces dchets
constituent une nuisance environnementale
prendre en charge pour la sauvegarde
durable de notre environnement. La
valorisation de cette matire organique
serait une solution judicieuse pour attnuer
leurs effets nocifs. Par ailleurs,
lapplication dun procd de
bioconversion la digestion anarobie
offre la possibilit de combiner le
traitement de ces dchets et la production
dune nergie renouvelable qui est le
biogaz. Ce gaz riche en mthane CH4
Application des doptimiser ce dpt en ajustant les

paramtres thermo hydrauliques et chimiques.
impdances Nous avons ensuite tudi des inhibiteurs de
corrosion ainsi que des oxydants chimiques
lectrochimiques qui on attribue un pouvoir stimulant pour
linhibition de la corrosion. Aprs cela nous
ltude des dpts de avons tudi leffet de la prsence de ces
tartre en prsence oxydants et inhibiteurs de corrosion sur la
formation de tartre.
doxydants Les rsultats montrent que le dpt de
tartre dpend des conditions
M.N. Boucherit a, S. Amzert a, F. Arbaoui thermohydrauliques Fig. 1.a & 1.b et quil est
a
, S. Hannini b galement entrav par la prsence dions
boucherit@scientist.com
a permanganates qui ont la capacit damliorer
Centre de Recherche Nuclaire de Birine, BP 180
Ain Oussera, 17200, Djelfa, Algrie. en parallle le comportement face la
b
Universit de Mda, Algrie corrosion Fig 1.c.
Tel. +213 27 87 29 21; Fax: +213 27 87 42 80
Mots cls : impdances lectrochimiques,

permanganate, dpt de tartre,
corrosion
Rsum
La prsence dun matriau dans un
environnement conduit inexorablement (a) au centre de llectrode et en (b) lextrmit de llectrode
lajustement des deux phases. La corrosion absence de permanganates et en absence de permanganates
et le dpt de tartre sont deux
consquences qui surviennent de ce besoin Figure 1 : morphologie des dpts de
dajustement. En pratique, les actions de tartre
prvention dun phnomne peuvent
favoriser lautre. En effet, il est bien connu Ces rsultats obtenus partir
que lacidification dun milieu peut dobservations microscopiques ont t
empcher la formation de tartre [1] mais confirms travers les mesures
elle peut acclrer davantage la corrosion lectrochimiques portant sur les courants
du matriau [2]. Par ailleurs si dans rsiduels Fig. 2. Sur la figure, on constate
certains cas on peut tolrer la prsence de galement que les rsultats obtenus 25C se
tartre parce quil limite la vitesse de confirment 70C.
corrosion, dans des installations dotes Cette fragilisation du dpt de tartre en
dchangeurs de chaleur, la prsence de prsence de permanganates a t confirme
tartre est dangereuse car elle affecte par spectroscopie dimpdances
directement le transfert de chaleur. Dans lectrochimiques. Nous avons appliqu cette
les installations industrielles sujette ces technique pour suivre le processus de
phnomnes le grand dfi serait dinhiber rduction des permanganate menant la
en mme temps la corrosion ainsi que le formation de loxyde MnO2 sur la surface de
dpt de tartre. llectrode. Cet oxyde, qui est la fois
Dans ce travail, nous nous sommes conducteur et homogne, serait lorigine de
intress lacier inoxydable AISI 316L. la rduction de ladhrence du tartre sur la
Nous avons tudi le dpt de tartre par surface de llectrode.
voie lectrochimique et nous avons essay
Figure 2 : courbes chrono

ampromtriques de lacier dans des
solutions de carbonate diffrentes
tempratures avec et sans permanganates
Rfrences
1. Bart Van der Bruggen, Carlo
Vandecasteele, Distillation vs.
membrane filtration: overview of
process evolutions in seawater
desalination, Desalination, 143 (2002)
207-218.
2. Khalid Al-Anezi, Nidal Hilal, Scale
formation in desalination plants: effect
of carbon dioxide solubility,
Desalination, 204 (2007) 385402.
Elaboration, characterization and activating agent, allows the development of a

large porosity in the activated material. To
application in adsorption of metal optimize the conditions for elaboration of our
ion of new adsorbent material adsorbent material, experimental design was
from alga applied to reduce the number of experiment
M. Tarbaoui1, A. Abourriche1, M. Charrouf1, trials needed to evaluate multiple parameters
A. Bennamara1, M. Benzina2, S. Fourmentin3 (percentage of phosphoric acid, temperature
and time of activation) and their interactions
1
Laboratory of Biomolecular and Organic Synthesis, Faculty of on the responses (capacity of adsorption of
Sciences Ben MSik, University Hassan II Mohammedia-
Casablanca, Morocco methylene blue, yield adsorbent)
2
Laboratory 3E, ENIS, Sfax, Tunisia. The textural and structural characterization of
3
Unity of Environmental Chemistry and Interactions of the the materiel optimized was carried out based
Living, ULCO, Dunkirk, France
on different techniques of physicochemical
*Correspondence: meriem_tarbaoui@yahoo.fr analysis and spectroscopic (infrared
spectroscopy, X-ray diffraction, scanning,
Key words: alga, optimization, adsorbent material, electron microscopy and determination of
adsorption, metal ion porosity and pore volume.
1. Introduction 3. Results and Discussion
The valorization of the algal biomass is The adsorbent material optimized is
considered among the most interesting characterized by an internal porosity in the
international programs in the exploitation of the range of 68.76% and a pore volume of 0.88
marine environment. In fact, the algae have Cm3/g, according to the method of
constituted for a long time a great economic for Pycnometer measures [2]. Its application in
the countries that have large coastlines. The water treatment showed important adsorption
seaweeds have already a commercial value properties against certain metallic pollutants
recognized in various fields, such as food, such as, Cu2+, Cd2+, Pb2+ and Cr+6 (Figure 1-
cosmetics, textiles, and pharmaceutical. [1] 2). [3-5]
However the residues of extraction obtained
from these seaweeds, which represent more than
80% of the weight of the raw material, are not
exploited enough. This requires a valorization of
theses residues by developing a new way of
exploitation of these natural resources. The
objective of this study is the valorization of the
part not extractible of seaweeds by the
elaboration of a new adsorbent material,
optimization the preparation conditions of this
adsorbent material and its application in the Figure 1: Kinetics of adsorption of Pb2+, Cu2+ and
Cd2+ ions on the adsorbent material prepared from
adsorption of metallic ions.
the residues of alga.
2. Experiment
The seaweeds were washed with distilled
water and dried in sunlight for a week before
treatment in the laboratory. Prior to use, they
were dried in an oven overnight at 100 C and
then ground using an electric grinder to a
particle size capable of passing through a
100m sieve. The residues of extraction
obtained from these seaweeds have undergone a
chemical activation using phosphoric acid Figure 2: Kinetics of adsorption of Cr6+ ion on the
(H3PO4). This latter is well known as precursors adsorbent material prepared from the residues of
alga
4. Conclusion
The prepared material by chemical activation
with phosphoric acid was an efficient adsorbent
with internal porosity of 68.76% and pore
volume of 0.88 Cm3/g. This study demonstrates
that the prepared material could be used as an
adsorbent for the removal of Cu2+, Cd2+, Pb2+
and Cr+6 from aqueous solutions.
Acknowledgements
This work was funded through the PHC Maghreb
Project No 27959PD and Moroccan-Tunisian integrated
action No 12/MT/23.
References
[1] E. Tarlan, F.B. Dilek, U. Yetis.
Effectiveness of algae in the treatment of a wood-based
pulp and paper industry wastewater,
Bioresource Technology, Vol 84, pp 1-5. (2002)
[2] M. Benzina, A. Bellagi, Ann. Chim., 1990, 15, 315.
[3] Baes C.F., Mesmer RE., "The hydrolysis of cations" John
Wiley & Sons, p 489, 1976.
[4] Charlot G., "Les ractions chimiques en solution -
L'analyse quantitative minrale" Masson & Cie, 6 d,
1969.
[5] K Anoop Krishnan and TS Anirudhan. ISSN 0378-4738 =
Water SA Vol. 29 No. 2 April 2003.
Utilization of cement kiln dust column experimental measurements are also

made to evaluate CKD as an adsorbent for the
in adsorption technology heavy metals. Results obtained are with good
agreement of Langmuir and Freundlich
Yousef SWESI1 , Aisa Milad 1 , Abdelati assumption of multilayer formation on the
Elalem1 and Walid Alfoghy1 adsorbent surface.
1. Chemical Engineering Department, Faculty of
Engineering, University of Tripoli, Libya
ABSTRACT
This paper involves a study of the heavy
metal pollution of the soils around one of
cement plants in Libya called Suk-
Alkhameas and surrounding urban areas
caused by cement kiln dust (CKD) emitted.
Samples of soil was collected from sites at
three directions around the cement factory
at distances 250m, 1000m, and 3000m
from the factory and at (0-10) cm deep in
the soil. These samples are analyzed for
Fe(iii), Zn(ii), and Pb(ii) as major
pollutants. These values are compared with
soils at 25 Km distances from the factory
as background or control samples. The
results show that the surface soil Fe ion
concentration ranged within the acceptable
range of 1000 ppm. However, for Zn and
Pb ions the concentrations at the east and
north sides of the factory were found six
fold higher than the background level. This
high value was attributed to the wind
which blows usually from south to north
and from west to east. This work includes
an investigation of the adsorption
isotherms and adsorption efficiency of
CKD as adsorbent of heavy metal ions
(Fe(iii), Zn(ii), and Pb(ii)) from the
polluted soils of Suk-Alkameas city. The
investigation was conducted in batch and
fixed bed column flow technique. The
adsorption efficiency of the studied heavy
metals ions removals onto CKD depends
on the PH of the solution. The optimum
PH values are found to be in the ranges of
8-10 and decreases at lower PH values.
The removal efficiency of these heavy
metals ions ranged from 93% for Pb, 94%
for Zn, and 98% for Fe ions for 10 gl
adsorbent concentration. The removal
efficiency of the s! e studied ions reached a
maximum at 50-60 minutes contact time
when equilibrium is reached. Fixed bed
The Theranostic Potential of blocks the MSNs pores and usually induces a
Mesoporous Silica dramatic decrease of surface area and pore
Nanoparticles volume. Thereby, these molecules must be
1,2,3
Meryem Bouchoucha , Ren C.-
grafted at the outer surface of MSNs, in order
Gaudreault3, Marc-Andr Fortin2 and
Freddy Kleitz3 to avoid surface area and pore volume losses.
1. Laboratoire des Matriaux Fonctionnels Nanoporeux In this work, we demonstrate how PEGylated
Dpartement de Chimie Centre de Recherche sur les
Matriaux Avancs (CERMA) Universit Laval MSNs which are labeled with DTPA(Gd) can
Qubec Qubec G1V 0A6 Canada.
2. Laboratoire de Biomatriaux pour l'Imagerie Mdicale be engineered to efficient MRI contrast
(BIM) - Centre Hospitalier Universitaire de Qubec (CR-
CHUQ-SFA) Qubec Qubec G1L 3L5 Canada. enhancement, drug loading and controlled
3. Unit des Biotechnologies et de Bioingnierie Centre
de recherche CHUQ Hpital saint-Franois dAssise release. For this, MCM-48-type MSNs were
Qubec Qubec G1L 3L5 Canada.
synthesized and a simple grafting optimization
strategy was carried out. The results, obtained
Abstract: by thermogravimetric (TG-DTA), N2
The new generation of therapeutic systems
physisorption, NMR, IR and XPS analysis,
is based on the engineering of theranostic
show that the grafting of small amounts of
nanomaterials which combine
PEG and DTPA ensures selective grafting of
simultaneous therapeutic and diagnostic
the outer surface while retaining more than
capabilities. Mesoporous silica
90% of the surface area, pore volume and pore
nanoparticles (MSNs) have emerged as
diameter. These quantities are sufficient to
promising materials for drug delivery and
produce biocompatible and non-cytotoxic
imaging applications due to their unique
nanoparticles with desired colloidal stability,
properties (high surface area and large pore
strong relaxometric properties and remarkable
volume)1. Surface functionalization of
MRI contract enhancement capabilities. In
MSNs promotes further their biomedical
addition, the developed nanoparticles showed
applications. In particular, polyethylene
their ability not only to trap acridine (a model
glycol (PEG) grafting improves
molecule) and daunorubicin (anticancer drug),
biocompatibility and colloidal stability
but also to ensure their selective controlled
under physiological conditions. On the
release in physiological conditions mimicking
other hand, grafting of DTPA(Gd), a MRI
in vivo situations. Thus, the developed
probe molecule, enables positive contrast
nanocarriers could be considered as promising
enhancement in MRI (Magnetic Resonance
theranostic materials for drug delivery and
Imaging)3 and promotes nanoparticles
MRI monitoring and diagnosis.
detection and monitoring. However, the
grafting procedure for PEG and DTPA Key words: Mesoporous silica nanoparticles,
controlled release, drug delivery, MRI monitoring.
Elaboration of TiO2 Among them, surfactant-mediated Sol-gel

method is a versatile method for the synthesis
nanoparticles elaborated by of many mesoporous metal oxides, especially,
Sol-gel method with Soluble TiO2. Many surfactants were used such as:
Starch Stabilization and trioctylphosphine [1], cetyl-tri-methyl-
ammonium bromide (CTAB) [2] and cetyl-tri-
coupling of Hydrothermal and methyl-ammonium chloride (CTACl). The
Biological Extraction surfactant removal from the inorganic TiO2
matrix needs post treatments (washing,
Afef Mehri1, Hafedh Kochkar1,2 and Z. calcination). A novel green method for TiO2
Ksibi1 synthesis has been developed by Collone et al.
[3, 4] and Kochkar et al. [5] while using the
1. Laboratoire de Chimie des Matriaux et Catalyse, soluble starch, biodegradable, as a structuring
Facult des Sciences de Tunis, Campus Universitaire El
Manar, Tunis, Tunisie, mehri.afef@yahoo.fr agent. In the present work, two versatile
2. Centre National des Recherches en Sciences des methods for the extraction of starch from the
Matriaux, Technople de Borj-Cdria, Soliman, Tunisie inorganic matrix are developed: Hydrothermal
h_kochkar@yahoo.fr
Treatment (HT) and Enzymatic Treatment
Abstract: (ET). The effect of treatment on the yield of
Mesostructured TiO2 nanomaterials with starch removal and TiO2 crystallites sizes is
large pore sizes were elaborated by a novel studied.
green route using soluble starch as 2. Experiment
structuring agent and titanium (IV)
2.1 Elaboration of TiO2-Starch
isopropoxide as the inorganic precursor.
The effect of key parameters, including the TiO2-Starch was prepared using the method
molar ratio Ti/Starch and soluble starch described by Kochkar et al. [4].
removal processes were discussed. Starch 2.2 Hydrothermal treatment (HT)
removal from the TiO2 matrix by washing
with inorganic polar solvents was not 1.0 g of TiO2-starch powder was treated
successful; showing a strong interaction with15 mL of water Teflon-lined autoclave at
with the inorganic matrix. Post-thermal 423 k for 48 h. The resulting precipitate was
treatment at high temperature (723-823 K) recovered by filtration and washed with
leads to starch removal but to the collapse distilled water. This sample was dried at 353k
of the mesostructure . Using hydrothermal for 24h.
treatment (HT), soluble starch removal is 2.3 Enzymatic treatment (ET)
about 80-wt% against 60 wt% for 1.0 g of TiO2-starch powder was dissolved in
enzymatic one (ET). Coupling the ET and deionised water and 50 mg of -amylase was
HT leads to 90-wt.% of soluble starch added. The solution was stirred at the ambient
removal. The TiO2 crystallites sizes are temperature for 24 hours. Finally, 200 mg of
stabilized at 6 nm. yeast (Saccharomyces- Cerevisiae) was added and
the mixture was kept under magnetic stirring
Key words: TiO2, enzymatic treatment, soluble for 24 hours. The suspension was filtered and
starch washed with 1 L of deionised water to remove
soluble by-products and finally dried at 353 K
1. Introduction
for 24 hours.
Many works are devoted to the
optimisation of the elaboration methods for 3. Results and Discussion
tuned titanium oxide nanomaterial. The 3.1 Characterization
main target in this research topic is to The N2 adsorption-desorption isotherms of
obtain TiO2 having developed textural different TiO2 materials are type IV profile
properties and high thermal stability. with H3 hysteresis loops. The HT (423 K,
48h) leads to a promising result: the TiO2 methods for starch extraction, the combination
crystallites sizes (6-7 nm) are smaller than of ET and HT processes were studied. Indeed,
those obtained by post-thermal treatment at contamination of solid products by yeast is
773 K (11-14 nm). In addition, soluble confirmed. Coupling the ET and HT leads to
starch removal is about 80-wt%. Using the 90-wt.% of soluble starch removal. As with all
ET treatment at room temperature, the synthesis procedures, each of the syntheses
starch was first de-polymerized by - described above has its characteristic scope
amylase (50 mg) in glucose. Final and limitations.
degradation of glucose is performed by Acknowledgment
fermentation with Saccharomyces-
Cerevisiae (50 mg) leading to CO2 and The authors gratefully acknowledge the financial
support by The Tunisian Ministry of Higher
ethanol. The crystallites sizes are about 5
Education and Research.
nm. In fact, we observed here about 60
wt% of starch removal. This result can be References
explained by the strong interaction [1] Antonelli, D.M., Ying, J.Y. Synthesis of Hexagonally
between the soluble starch and the titanium Packed Mesoporous TiO2 by a Modified SolGel Method.
oxide. Angew. Chem. Int. Ed. Engl. 1995, 34, 2014-2017.
In order to extract the major quantity of [2] Tian, C.X., Zhang, Z. Hou, J., Luo, N. urfactant/co-
soluble starch from the inorganic matrix, polymer template hydrothermal synthesis of thermally
stable, mesoporous TiO2 from TiOSO4.Mater. Letters.
we combined the two treatments (Table 1).
2008, 62, 77-80.
Coupling the ET and HT leads to 90-wt.% [3] Callone, E., Carturan, G., Sicurelli, A. Nanopowders of
of soluble starch removal. However, no Metallic Oxides by the Hydrolytic Route with Starch
significant improvement when the Stabilization and Biological Abetment.
treatments are applied in the reverse order. J. Nanosci. Nanotechnol. 2006, 6, 254-257.
Therefore, the ET doesn't have any effect [4] Callone, E., Carturan, G., Ischia M., Sicurelli, A.
on the degradation of starch after Nanometric oxides from molecular precursors in the
hydrothermal process. The DTA analysis presence of starch. Coatings of glass with these oxides in
shows that TiO2 after enzymatic treatment silica sols. J. Mater. Res. 2006, 21, 1726-1737.
[5] Kochkar, H., Triki, M., Jabou, K., Berhault G., Ghorbel
is contaminated by the yeast.
A. Novel synthesis route to titanium oxides nanomaterials
using soluble starch. J Sol-Ge.l Sci. Techn. 2007, 42, 27-
Table 1: Textural properties and starch
33.
removal over TiO2-Starch (Ti/Starch=0.5)
material
Treatments Starch SBET Mean
removal/wt.% /m2.g-1 crystallites
Size /nm
Calcinated 100 59 11
at 773 K
HT 77 90 7
ET 60 50 5
HT+ET 78 63 8
ET+HT 90 32 6
4. Conclusions
Two methods (Hydrothermal Treatment
and Enzymatic Treatment) are applied for
soluble starch extraction from inorganic
TiO2 lattice in mild chemical environment.
Highly crystalline TiO2 nanoparticles are
obtained at low temperature (423 K). In
order to determine the efficiently of
ADSORPTION AND has recently been focused on various materials

based on polysaccharides a special attention
DEGRADATION OF has been given to cyclodextrins (CDs) which
WASTEWATER are natural molecules derived from starch [2].
POLLUTANT BY The potential use of a support containing CD
molecules in the reduction of environmental
CYCLODEXTRINS pollution is based on the formation of
DERIVATIVES AND TiO2 inclusion complexes between CDs and the
PHOTOCATALYSTS. unwanted substances [4].
S. Khaoulani1,2,3, H. Chaker4, E. Secondly the treatment with TiO2 has
Bychkov1,3, L. Cherif4, S. Fourmentin1,2 been widely considered as one of the most
1
Univ Lille Nord de France, F-59000 Lille, France promising photocatalyst because of its high
2
3
ULCO, UCEIV EA-4492, F-59140 Dunkerque, France photocatalytic activity, photo-stability and
ULCO, LPCA EA-4493, F-59140 Dunkerque, France
4
Laboratoire de Catalyse et Synthse en Chimie
non-toxicity. Photocatalytic process is
Organique, Universit de Tlemcen, Algrie initiated when organic pollutants can be
Sohayb.Khaoulani@univ-littoral.fr decomposed by the participation of hydroxyl
radical which is generated on the surface of
Abstract: TiO2 particles, the improving methods can be
broadly divided into two categories, which are
The present study focused on the
the enhancement by increasing the adsorption
analysis of two wastewater samples and
of organic pollutants on the surface of TiO2
their subsequent treatment by adsorption
particles and the enhancement by improving
on cyclodextrins (CD) polymers and/or by
the separation of electronhole of TiO2 [3].
photocatalytic degradation with TiO2
photocatalysts.
2. Experiment
Keywords: wastewater, TOC, The sampling campaigns were
cyclodextrin, TiO2, adsorption. performed 2 times in output of the WWTP.
Water samples analyses were carried out on
1. Introduction the total fraction by liquid-liquid extraction or
by solid phase extraction. Either gas or liquid
The chemical contamination of
chromatography coupled with a mass
water from a wide range of toxic
spectrometry (GC-MS and LC-MS), static-
derivatives, in particular heavy metals,
headspace gas chromatography (HS-GC)
aromatic molecules and dyes, is a serious
analyses were realized for the identification of
environmental problem owing to their
organic pollutants.
potential human toxicity. Therefore, there
Batch studies were realized with real
is a need to develop technologies that can
and synthetic effluent to investigate the
remove toxic pollutants from wastewaters.
adsorption capacities of the CD polymers.
Among all the treatments proposed,
Photocatalytic experiments were
adsorption and TiO2 photocatalysts are a
realized with a Multirays apparatus
procedure of choice for treating industrial
(Helioquartz, Italy). Total organic carbon
effluents, and a useful tool for protecting
(TOC) measurements were used to follow the
the environment [1-3].
adsorption and/or degradation of organic
Firstly, adsorption on polymers and
pollutant in the aqueous solutions.
adsorbent materials are known to remove
pollutants from water. The extending
number of studies on adsorption of toxic 3. Results and Discussion
compounds by modified adsorbents shows Several organic compounds were
that there is a recent increasing interest in identified by GC-MS or LC-MS analyses
the synthesis of new low-cost adsorbents (volatile organic compounds, micropollutants,
used in wastewater treatment. Much effort
pharmaceutical compounds). The total

organic pollutant content was quantified by
TOC measurements.
After adsorption onto CD polymers
and/or photocatalytic degradation we
observed a decrease of the TOC content of
the effluent (from 200mg/L to 0 mg/L).
This decreased is due to the adsorption of
pollutant by CD polymers and to the
mineralization of organic compounds after
photocatalysis.
4. Conclusions
Both remediation technologies
(adsorption and photocatalysis) were
efficient in the removal of organic
compounds from wastewater samples. The
use or either adsorption or photocatalysis
will depend on the nature, concentration of
the pollutant.
Acknowledgment
Authors are grateful to SMCO for the financial
support of S. Khaoulanis PhD thesis and to PHC
Maghreb n27959PD for financial support.
References
[1] Crini G. Recent developments in polysaccharide-
based materials used as adsorbents in wastewater
treatment. Progress in Polymer Science 2005, 30,
3870.
[2] Morin-Crini, N., Crini, G., Environmental
applications of water-insoluble -cyclodextrin-
epichlorohydrin polymers. Progress in Polymer
Science 2013, 38, 344-368.
[3] Nakata K.; Fujishima A., Journal of
Photochemistry and Photobiology C:
Photochemistry Reviews 2012, 13, 169 189.
[4] Landy, D., Mallard, I., Ponchel, A., Monflier, E.,
Fourmentin, S. Remediation technologies using
cyclodextrins: An overview. Environmental
Chemistry Letters 2012, 10(3), 225-237
or the change in compound state [2]. Within

COMPARATIVE STUDY this range of process, the mineral membranes
OF THE ANTIMICROBIAL are often used in food industries and mainly
during treatment and purification of
ACTIVITY OF AN wastewater. These membranes are
EXCHANGED CU- characterized by a high chemical, thermal and
MORDENITE MATERIAL: mechanical stability.
Mordenite membrane is used in several
APPLICATION TO LOW filtration applications because zeolites have
CUT-OFF UF MEMBRANE uniform and molecular-sized pores that cause
significant differences in transport rates for
W. Blela*, A. Boucherb, M. Le Fellicb, L. some molecules, and allow molecular sieving
Limousyc, P. Dutournic in some cases [3].
a
Laboratoire de Gnie des procds environnement However, these membranes are costly and
agro-alimentaire (GEPEA) UMR CNRS 6144, Saint easily fouled (nevertheless less than organic
Nazaire, France
b
Laboratoire dIngnierie des MATriaux de Bretagne membranes) in a reversible or in irreversible
(LIMATB-EA 4250), Universit de Bretagne Sud, manner depending on the attachment strength
Lorient, France. of particles on the membrane surface [4].
c
Institut de Science des Matriaux de Mulhouse (IS2M)
UMR CNRS 7361 , Universit de Haute Alsace, The aim of this study is to develop a new
Mulhouse, France material presenting antibacterial and
antifouling properties, which limit biofilm
Abstract: development on the surface of the active layer,
Ceramic membranes, and more precisely and simultaneously, ensure a good conduct of
zeolite membranes, were widely studied in the filtration process.
the past ten years. One of the most
important drawbacks of these materials is 2. Experiment
that, as for polymeric membranes, their Two experimental setups were used in this
performances could be altered by the study. A home-made reactor was built to
formation of biofilms. In this work, we explore the growth of biofilm under a specific
prepared an exchanged Cu-Mordenite shear rate on Cu-Mordenite platelets (2 cm of
membrane and also Cu-Mordenite platelets side and 0.1 cm of thickness) (Figure 1). The
in order to study the effect of surface tests were carried out with a flow rate of 300
modification on bacteria adhesion. Results L.h-1 (flow velocity of 0.5 m.s-1), a shear rate
showed that the presence of Cu prevents of 1.3 Pa (shear velocity of 1200 s-1) in a
the formation of a biofilm on the active turbulent flux (Reynolds of 7700). Bacteria
layer of the zeolite membrane and also concentration (E. coli or S. aureus) was 1.105
protects the membrane performances. UFC/mL, and the contact period was defined
at 48 h.
Key words: Antimicrobial activity, biofilm, ion
exchange, Mordenite membrane, water
permeability
1. Introduction
Applications of membrane separation
processes have been developed in a wide
range of industries [1]. These processes
have as main advantage, easy control, the
absence of chemical compounds and
essentially, low energy consumption, in Figure 1: experimental setup used during dynamic tests
comparison to competing processes, performed on the Cu-Mordenite pletelets with the
presence of bacteria
because they do not need high temperature
The ultrafiltration unit used for the

filtration tests was described previously
[5]. The experimental tests were carried
out at a constant temperature (25C), with
a pressure range from 1 to 5 bar. The
permeability was calculated by flux
measurements at different transmembrane
pressure.
Three points were explored and consist in
Figure 2: temporal evolution of the Cu-Mordenite
comparing the development of a single- membrane permeability during experiments carried out
species biofilm on the material with and with the presence of bacteria
without antibacterial properties. First,
analyses where conducted in static flow Filtration tests carried out with favorable
conditions using alumina platelets covered conditions for the development of bacterial
with Mordenite and/or Mordenite biofilm showed a decrease of the membrane
exchanged with copper. Bacterial adhesion permeabilitie (both for membranes coated and
was followed using an epifluorescence not with Cu-Mordenite). Nevertheless, this
microscope. decrease was less important for membranes
Analyses showed no bacteria development treated by the Cu-zeolite than untreated ones.
on the surface of the copper exchanged 4. Conclusions
Mordenite platelets. The antibacterial
This work showed that the use of exchange
effect of the Cu-Mordenite active layer
Cu-Mordenite membrane could be of interest
was observed on planktonic and adhered
for the filtration of contaminated solutions.
bacteria on the platelets wall. This
The presence of copper inhibited the
antibacterial effect wass confirmed by
formation of a biofilm on the active layer of
epifluorescence microscopy observations.
the membrane, and then to the preservation of
Secondly, the development of a biofilm the membrane performances.
was investigated on the different platelets
References
under dynamic conditions. Indeed, factors
such as transport of microorganisms from [1] A. Mehta, A. L. Zydney, Permeability and selectivity
analysis for ultrafiltration membranes, Journal of
the solution to the wall or adhesion and Membrane Science, 249, 2005, pp 245249.
biofilm consolidation depend on [2] E. Zondervan, B. Roffel, Evaluation of different cleaning
hydrodynamic within the filtration module, agents used for cleaning ultrafiltration membranes fouled
by surface water, Journal of Membrane Science, 304,
hence the necessity to make trial in 2007, pp 4049.
dynamic conditions. In the last point, [3] E. Chevereau, L. Limousy, P. Dutourni, Effect of
antimicrobial activity (bactericidal or divalent salts on the retention of monovalent salts by
nanofiltration ceramic membrane, Industrial &
bacteriostatic) of functionalized Engineering Chemistry Research, 50, 2011, pp 4003
membranes using an exchanged Cu- 4010.
Mordenite membrane was analyzed in [4] J. S. Baker, L. Y. Dudley, Biofouling in membrane
systems A review, Desalination, 118, 1998, 81.
order to limit the biofilm formation on the [5] E. Chevereau, N. Zouaoui, L. Limousy, P. Dutourni, S.
active layer surface. In this step, the Don, P. Bourseau, Surface properties of ceramic
evolution of the membrane permeability ultrafiltration TiO2 membranes: Effects of surface
equilibriums on salt retention, Desalination, 255, 1-3,
was investigated to estimate the 2010, pp 1-8.
modification of the membrane
performances. The leaching of copper in
solution was followed during the three
analyses.
Nitrogen removal and cyclically to create alternating aerobic and

anoxic conditions.
aeration cycle to minimize Actually, sequencing cycles aeration is
energy consumption of the achieved by the use of simple clocks or by the
two WWTP control of the aeration system measures data
probes dissolved oxygen, pH or redox (Hduit
Choutrana II and Menzel and al, 1990. LEFVRE and al, 1993. PAUL
Bourguiba in Tunisia and al, 1998). More recently, an alternative to
improve the performance of the method
Slim HAJJI1,2, Hedi SHAYEB2 and Mohamed Lotfi consists apply dynamic optimization methods
MAROUANI3 to determine the aeration cycles that minimize
1National Office of Sanitation (ONAS), 32, Rue Hdi
Nouira Tunis 1001, Tunisia, hajji_slim@yahoo.fr
energy consumption under specified
2National Engineering School of Tunis (ENIT), Postal constraints.
Box 37, Le Belvdre, 1002 Tunis, Tunisia, Carbon and nitrogen removal are achieved by
hedi.shayeb@enit.rnu.tn
3National Office of Sanitation (ONAS), 32, Rue Hdi
switching the aeration on and off resulting in
Nouira Tunis 1001, Tunisia, Marouni@yahoo.fr alternated aerobic-anoxic conditions in the
aeration tank. Hence, the process can be seen
In this work, the selected Activated Sludge as a succession of cycles where each cycle
Model (ASM1) was calibrated, validated consists of an aeration period followed by a
and adapted to the effluent of the non-aeration period. Each cycle is then
wastewater treatment plant Choutrana II completely determined by means of two
and Menzel Bourguiba in Tunisia. t was parameters.
used to propose an alternating aerobic and
anoxic processes time. The optimization
problem consists in determining the
aeration air-on and air-off periods that
optimise the energy consumption by the
aeration system according pollution
removal and operating constraints.
Choutrana II plant was designed for
500000 population-quivalents (p.e.) and
consists of a primary treatment stage
(screening, grit removal), followed by a
secondary treatment stage (biological
treatment). The latter consists of a four
oxited ditch of about 60000 m3. Aerobic
volume are equipped with diffusers and
anoxic volume are equipped by agitators.
Aeration is operated cyclically to create
alternating arobic and anoxie conditions.
Menzel Bourguiba plant was designed for
140000 population-quivalents (p.e.) and
consists of a two parallel file. Each one
consists of primary treatment stage
(screening, grit removal), followed by a
secondary treatment stage (biological
treatment). The latter consists of an anoxic
tank followed by two aereted tanks.
Anoxic tank is equipped by agitators and
aeration tanks are eqquipped by two
turbines (one by tank) with are operated
BEHAVIOR OF COPPER of metal-containing effluents [1]. Thus,

adsorption of heavy metal could be reasonably
AND NICKEL AFTER effective considering the olive solid waste
THERMAL TREATMENT composition[2].OSW loaded with metals are
OF CONTAMINATED actually regenerated and reused in different
cycles using ionic and acid extracting agents
OLIVE SOLIDWASTE [3]. At the end, this method generates huge
ChoucheneAjmia1, JeguirimMejdi2, amount of concentrated effluents that need
decontamination processes. Because OSW
TrouvGwenalle3,Said Rachid1
presents high heating value, another solution
1. Unit de Recherche d'Etude des Milieux Ioniss et
Ractifs, IPEIM (UR EMIR), Avenue Ibn El Jazzar, 5019 would be the energy recovery of contaminated
Monastir, Tunisia, ajmiachouchene@gmail.com biomass [4]. If this solution would efficiently
rachid.said@ipeim.rnu.tn reduce the volume, some environmental points
2. Institut de Science des Matriaux de Mulhouse (LRC
CNRS 7361), Equipe Matriaux Porosit Contrle, related to air regulations must be controlled.
Universit de Haute Alsace, 3 bis rue A. Werner 68093 Our investigation focuses on two heavy
Mulhouse Cedex, France, mejdi.jeguirim@uha.fr metals, copper and nickel commonly found in
3. Laboratoire Gestion des Risques et
Environnement,Universit de Haute Alsace, 3 bis rue runoff or industrial waste such as
Alfred Werner, 68093 Mulhouse Cedex, electroplating, printed circuit board, wire
France,gwenaelle.trouve@uha.fr drawing and chemical materials industries.
Abstract The discharge of these metals into receiving
The removal of copper and nickel by Olive waters is detrimental to human health and the
Solid Waste (OSW), provided by an olive environment. The present paper deals with the
oil mill from Tunisia, was performed on removal of these two metals from aqueous
batch experiments. Copper and nickel were solutions using olive solid waste as-received.
adsorbed in a monolayer on OSW surface Hence, it aims to investigate biosorption
with maximal adsorption capacity (qmax) of kinetics and isotherms of OSW by varying
4 mg.g-1 and 2.4 mg.g-1, respectively. The parameters of metal ions concentration,
main objective of this research is to contact time and temperature. The main
concentrate these metal ions in the ash by objective of this research is to concentrate
the combustion of saturated OSW with these metal ions in ashes by the combustion of
metals at 850C and to test the mobility of contaminated OSW. The last point is to test
copper and nickel to environment using the the mobility of copper and nickel to
water as reagent. Results indicate that environment using the water as reagent.
about 96% of each metal was recovered in
2. Experiment
ashes. Thus, this issue may be a friendly
environmental solution of effluents 2.1.Batch adsorption
treatment. Low leaching rates (4.5%) Batch experiments were carried out at 222C
were observed for copper and nickel from in a glass beaker by shaking a fixed mass of
contaminated OSW ashes. Therefore, the OSW (1<d<1.6mm), according to selected
suggested process can be used as an experimental condition (500 rpm. pH = 5.5
alternative to the classical technologies for and contact time =120 min). Metal ions
effluent decontamination. concentrations in the filtrates were determined
Keywords: (Olive solid waste, heavy metal, by flame atomic absorption spectroscopy
biosorption, incineration, leaching) (FAAS) using a Varian Absorption
Spectrometer (AAS). To determine
1. Introduction
biosorption kinetics and isotherms, we have
In the last years, certain raw waste varied temperature, contact time and metal ion
products from industrial or agricultural concentration.
operations i.e. pine bark, grape stalks, crop 2.2 Combustion of contaminated OSW
milling waste, olive solid waste (OSW) Only contaminated OSW by copper and nickel
have been tested for the decontamination (C0=40 mg L-1) were dried and burnt in an
oven at 850C during 45 min. The amount chlorine [7-8] with their oxide forms
of each metal recovered in the ashes was dominating. CuO and NiO are very stable
controlled by microwave mineralization species at high temperatures.These two metals
with acid digestion of the contaminated are poorly vaporized in these our experiments
OSW and the residual. according to literature data.
2.3. Leaching tests
3.3. Metal balance after leaching tests
Leaching tests were performed on residual
Copper and nickel were released as traces (4.5
ashes from combustion tests of
and 4.2 % of initial contaminated OSW) into
contaminated OSW. They were carried out
the water phase. These results show that
with a batch leaching procedure according
nickel and copper are not easily solubilized
the French standard [5] with a liquid ratio
and transferred to the natural environment.
of 10 L/1kg. Leachates were analyzed for
They exist in ashes under not soluble chemical
their levels of copper and nickel using
forms in water, which is in good agreement
AAS.
with other published results. Karlfeldt and
3. Results and Discussion Steenari[9] have found that the leaching
3.1. Biosorption kinetics and isotherms behaviour of an element does not only depend
on the speciation of the element itself, but also
The calculated activation energy, Ea, for on the matrix of the material.
copper and nickel were 36 kJ.mol-(C0=40
mg.L-1) and 26 kJ.mol-1 (C0=60 mg.L-1) 4. Conclusions
respectively. Therefore, Copper and nickel Copper and nickel were adsorbed in
adsorption are established by weak forces monolayer on the surfaces of OSW. Based on
bonding in our tests experiments. maximal adsorption capacities (qmax), OSW
Langmuir model has a better fitting model has a higher affinity to copper than nickel.
than Freundlich model. This indicates a Metal trapping in the ashes revealed that
monolayer of copper or nickel ions copper and nickel are not volatilized at 850C
adsorbed on OSW surface. Thus, maximal (96% of metal recovered in ash). The leaching
adsorption capacities (4 mg.g-1(for Cu) and experiments showed that amounts of copper or
2.4 mg.g-1(for Ni)) indicate the metal ions nickel water-soluble forms in the ashes are
order in the monolayer, copper>nickel. low. Therefore, this pollution was not
3.2 Metal balance after contaminated OSW transferred to the environment. The
incineration incineration of contaminated OSW may be an
The analytical results are given in Table 1. environmentally acceptable solution for
wastes elimination generated during the
Table 1.Total amount of metal in contaminated decontamination of industrial effluents.
OSW and residual ashes
Cu Ni References
mg/g of %/ mg/g of % /
OSW OSW OSW OSW [1] Fiol N., Villaescusa I., Martinez M., Miralles N., Poch J.,
OSW 2.56 -- 1.70 -- Serarols J. SEP PURIF TECHNOL.2006, 50, 132-140.
Ashes 2.46 96 1.63 96 [2] Gharaibeh S.H., Abu-el-shar W.Y., Al-Kofahi M.M. Water
Res. 1998, 32, 498502.
Both amounts of copper and nickel [3] Pagnanelli F., Toro L., Veglio F. Waste Manage 2002, 22,
recovered in ashes are quite close to 901-907.
thatcaptured by OSW during [4] Chouchene A., Jeguirim M., Khiari B., Trouv G., Zagrouba
F. J. Anal ApplPyrol. 2010, 86, 168-174.
contamination process with a recovery
[5] AFNOR T95J6 (1992).
value of 96%. Reddy et al.[6] have [6] Reddy B.R., Mirghaffari N., GaballahI.Resou.Conserv.Recy,
obtained similar result. They recovered 1997, 21, 227-245.
83% of copper under CuO specie in the [7] Klein, D. H., Andren, A. W., Carter, J. A. Environ. Sci.
ashes.Copper and nickel contained in Technol., 1975, 9, 973-979.
organic matrixes (waste and coal) are [8] Fernandez M. A., Martinez, L., Segarra, M., Garcia, J. C.,
Espiell, F. Environ Sci. Technol. 1992, 26, 1040-1047.
slightly transferred in fly ashes during
[9] Karlfeldt K.,Steenari B.-M. Fuel 2007,86, 1983-1993.
combustion whatever the presence of
Pharmaceutical residue reaction of the active ingredient on the

biomass. The results obtained in this study
retention onto marine plant have shown
Posidonia Oceanica that the retention possibilities of these
compounds by the Posidonia are significant
Maroua Ferchichi and Hatem Dhaouadi and is
Monastir University, Faculty of Sciences, about, in the case of paracetamol, of 14 mg g-
1.
Chemistry Department, Research Unit in
Applied
Chemistry and Environment, 5000
Monastir. TUNISIE
Abstract
Drug residues released into the
environment pose nowadays more and
more public
health problems. The observed resistance
to some antibiotics and other drugs is one
of its
illustrious aspects. In this work we have
undertaken a study of drug residues
retention on a
solid support. The choice of the adsorbent
is based on the occurrence of its meeting
with the
concerned residue throughout the journey
from the initial discharge point to the
receiving
environment.
The object of this work is to make an
overview of aquatic contamination by drug
residues. It
seemed interesting to study the drug
residues retention by adsorption on
Posidonia oceanica,
an endemic Mediterranean biomass, which
is a habitat for fish and aquatic organisms
in
general.
After the physico-chemical
characterization of the biomass,
experiments were carried out for
the removal of an active pharmaceutical
ingredient from artificially contaminated
aqueous
solutions. These tests were intended to
identify the isotherms and kinetics of the
adsorption
Biodegradability experimental conditions. The feasibility of

improvement of coupling an electro-Fenton pre-treatment with
a biological degradation of by products in
sulfamethazine solutions by
order to mineralize polluted solutions of
means of an electro-Fenton sulfamethazine was confirmed.
process
Key words: Biodegradability improvement; Electro-
D. Mansour1,2,3,4, F. Fourcade3,4, N. Fenton pre-treatment; Coupled processes; Drug
Bellakhal1,2, D. Hauchard3,4, A. Amrane3,4 removal; Sulfatmethazine.
1. Laboratoire de Chimie Analytique et lectrochimie,

Dpartement de Chimie, Facult des Sciences de Tunis,
Campus Universitaire, 2092 Tunis-Tunisie. 1. Introduction
2. Institut National des Sciences Appliques et de
Technologie, B.P. N676, 1080 Tunis Cedex, Tunisie.
In the last two decades, pharmaceuticals
3. Ecole Nationale Suprieure de Chimie de Rennes, such as analgesics, antibiotics, and
CNRS, UMR 6226, Avenue du Gnral Leclerc, CS antineoplastics, have been found in effluent
50837, 35708 Rennes Cedex 7, France
4. Universit europenne de Bretagne
sewage treatment plants. Some of these
Email: abdeltif.amrane@univ-rennes1.fr compounds were not readily biodegradable
and were also detectable in surface water and
Abstract: groundwater. Biological treatment processes
The main objective of this study was to are considered to be economical but these
examine the effect of an electro-Fenton systems are inefficient for the degradation of
pre-treatment on the biodegradability of complex structured organic compounds such
as pharmaceuticals [1]. The most recent
sulfamethazine polluted solutions. The advances in the treatment of wastewaters
purpose of the pre-treatment was to concern a new range of oxidation techniques,
degrade this target compound in order to the Advanced Oxidation Processes (AOPs).
increase the biodegradability of the The electro-Fenton process is very promising
effluent and therefore allow a subsequent since it achieves high reaction yields with low
treatment costs. This method has been
biological treatment. Preliminary tests successfully applied to the destruction of toxic
showed the absence of biodegradability of and biorefractory organic pollutants [2].
the target compound. The degradation of Fentons reagent (Fe2+/H2O2) has been
sulfamethazine by electro-Fenton process successfully produced electrochemically [3],
was then examined by using a carbon felt at pH 3. Then, the non-selective very powerful
oxidizing agent, hydroxyl radicals (OH), are
cathode and a platinum anode in an produced in solution by reaction of Fe2+ ions
electrochemical reactor containing one liter with H2O2. Sulfamethazine (SMT) is a drug,
of solution. The influence of some which belongs to the group of
experimental parameters, such as the initial pharmaceutically important heterocyclic
concentration, the temperature and the sulfonamides and it is widely used in
medicine and veterinary practice as
current intensity on the degradation by antibacterial drug in pharmaceutical
electro-Fenton step has been investigated. preparations [4]:
In addition, the biodegradability of the
solution after electrochemical pre-
treatment was examined and showed a
BOD5 on COD ratio above the limit of
biodegradability, namely 0.4, for several The main purpose of this study was to
examine possible enhancement of the
biodegradability of polluted solutions of compatible, namely BOD5 on COD ratio

sulfamethazine by means of an electro- above biodegradability threshold, 0.4.
Fenton pre-treatment, which aimed to Table 1: BOD5 (mgO2/L) values of pre-treated
partially degrade the target compound and Sulfamethazine (initial COD value of 88 mg O2/L)
produce biodegradable by-products. The by electro-Fenton process.
SMT Reaction T I BOD5 /
influence of various experimental solution time (C) (mA)
parameters on sulfamethazine kinetic COD
(min)
degradation was studied and monitored by S0 0 0.17
high performance liquid chromatography S1 10 18 300 0.15
(HPLC) analysis. S2 60 18 300 0.22
S3 120 18 300 0.97
S4 60 35 300 0.80
2. Results and Discussion S5 30 18 500 0.21
S6 60 18 500 0.50
Indeed, the degradation of S7 120 18 500 0.80
sulfamethazine by the electro-Fenton Experimental conditions: [SMT]0 = 0.2 mM,
process using a carbon felt cathode and a [Fe2+] = 0.1 mM, [Na2SO4] = 50 mM, pH = 3, V =
platinum anode, has been studied under 1L.
different experimental conditions,
including the current intensity, the
4. Conclusions
temperature and the initial sulfamethazine
concentration. The optimum current This study demonstrates the efficiency of
intensity was 500 mA, at 18C, with a the electro-Fenton process as a pre-treatment
degradation efficiency of 99.1% after 30 method preceding a biological treatment for
min reaction time but these operational the mineralization of non-biodegradable
conditions did not allow to access to the organic substances.
biodegradability of the effluent To confirm the relevance of the proposed
(BOD5/COD value of 0.21 Table 1). The combined process, biological treatment of
degradation efficiency of the target electrolyzed solution should be performed.
molecule was enhanced for increasing The corresponding work is in progress in the
reaction temperature. The sulfamethazine laboratory using activated sludge from local
degradation followed a pseudo-first-order wastewater treatment plant.
kinetic and the apparent kinetic rate References
constant of the degradation at 45C was
[1] Lodha, B.; Chaudhari, S. Optimization of Fenton-
greater than that at 18C. In addition, the
biological treatment scheme for the treatment of aqueous
degradation of sulfamethazine was reduced dye solutions. J. Hazard. Mater. 2007, 148, 459466.
for increasing initial concentrations. [2] Brillas, E.; Stirs, I.; Oturan, M.A. Electro-Fenton Prosess
and related electrochemical Technologies based on
In order to determine the appropriate Fentons reaction chemistry. Chem. Rev. 2009, 109,
operating conditions leading to a 65706631.
biodegradable electrolyzed solution of [3] Xie, Y.B.; Li, X.Z. Interactive oxidation of
sulfamethazine, various electro-Fenton photoelectrocatalysis and electro-Fenton for azo dye
degradation using TiO2_Ti mesh and reticulated vitreous
experiments were carried out. Within this
carbon electrodes. Mater. Chem. Phys. 2006, 95, 3950.
framework, the measurement of the BOD5
[4] Kaniou, S.; Pitarakis, K.; Barlagianni, I.; Poulios, I.
vas considered for biodegradability Photocatalytic oxidation of sulfamethazine. Chemosphere
assessment before and after electro-Fenton 2005, 60, 372380.
treatment (Table 1).
Biodegradability analysis showed that
under several experimental conditions, the
electro-degraded solution of
sulfamethazine was biologically
Evaluation of olive stones as and Freundlich equations. These adsorption

isotherms were seen to be consistent with
activated carbon for heavy Langmuirs adsorption isotherm. Kinetic
metal removal parameters were also calculated from the pseudo-
firstorder
from aqueous phase and pseudo-second-order models for better
Thouraya Bohli1, Abdelmottaleb description of the adsorption mechanism.
Ouederni1, Nuria Fiol2 and Isabel Key Words: Heavy metal, activated carbon,
Villaescusa2 olive stones, adsorption, kinetics, isotherm.
1 Laboratory of Research: Engineering Processes and
Industrials systems (LR11ES54)
National School of Engineers of Gabes, University of
Gabes, Tunisia.
Bohli_th@yahoo.fr; mottaleb.ouederni@enig.rnu.tn
2Departement dEnginyeria Quimica, Agraria i
Tecnologia Agroalimentaria,
Universitat de Girona, Avda Lluis Santolo, 17003
Girona, Spain
Abstract
Heavy metals are common pollutant found
in various industrial effluents. The stricter
environment regulations on the discharge
of heavy metals make it necessary to
develop
various technologies for the removal.
Among various processes, adsorption on
activated
carbon was considered to be the more
effective especially at low concentrations.
The present study has been carried out to
evaluate the applicability of activated
carbon olive
stones suppliedrom prepared by chemical
way in the removal of several metal ions
including
Pb(II), Cd(II), Cu(II) , Ni(II) and Co(II)
from aqueous solutions by batch
adsorption process.
The effect of initial pH, contact time and
initial concentration on metal ions sorption
was
investigated. Sorption kinetic rates were
found to be fast; equilibrium time was
achieved after
4 hours. Kinetic experimental data fitted
very well the pseudo-second order
equation and the
values of sorption rate constants were
calculated. The equilibrium isotherms were
evaluated in
terms of maximum adsorption capacity and
adsorption affinity by the application of
Langmuir
Phosphorus recovery from also marine dead zones [1]. On the other hand,
phosphate rock is a non renewable and a
aqueous solutions by treated critical resource on which modern society is
marble wastes: efficiency and highly dependent. Due to a constant increase
mechanisms demand of phosphates to satisfy the foods
need of the world population, production of
phosphate rock is estimated to peak around
Haddad Khouloud1, Jaouadi Safa1, Benltifa
Mahmoud1, Mlayeh Ammar2, Anane Makram,
2035, after which demand would out-strip
Hamzaoui Ahmed Hichem3, Jellali Salah1 supply [2]. Thus, phosphorus recovery from
renewable resources such as wastewaters has
1
Water research and technologies centre (CERTE), become this last decade an innovative research
wastewater treatment laboratory. E-mail option. The main goals of this experimental
addresses: khouloud_had@hotmail.fr; study are to test the use of TTPMW for
jaouadisafa@yahoo.com; phosphorus removal and recovery from
mahmoud_fsm@yahoo.fr; synthetic aqueous solutions and to evaluate
makram.anane@certe.rnrt.tn; the effect of certain key parameters such as
salah.jallali@certe.rnrt.tn;
2
CERTE, Georesources laboratory, aqueous phosphorus concentration contact
ammarmlayah@yahoo.fr time, pH solutions, TTPMW dosage and
3
Material sciences research centre: temperature. Additional experiments were
mdmihi10@gmail.com also made to assess the efficiency of the
dynamic system to remove and recover
Abstract:
phosphorus from local dairy industry and to
This study aims to study the phosphorus determine the involved mechanisms.
removal efficiencies from both synthetic
2. Experiment
solutions and real wastewaters under
different experimental conditions by The used solid matrix is constituted by
thermally treated powdered marble wastes powdered marble wastes resulting from the
(TTPMW) and to determine the involved manufacturing of large stones of BIANCO
mechanisms. The experimental results GIOIA marble. They were collected as a dry
showed that the TTPMW have high pure powder at the vicinity of the cutting and
phosphorus removal capacities compared polishing devices from a marble manufacture
to several natural mineral or organic located in Borj Cedria city which is situated at
materials cited in the scientific literature. about 25 km at the south of Tunis, Tunisia.
The solutions pH has the highest impact This powder solid matrix was heated at
on the phosphorus removal. In fact, for an 1000C for 1 hour. The batch experiments
initial phosphorus aqueous concentration were conducted at 20 02C in 120 mL
of 150 mg/L, the phosphorus removal capped flasks. During these assays a
capacity decreases from about 120 mg/g to predetermined amount of the adsorbent was
93 mg/g when the pH was increased from shaken in 100 mL of phosphorus solution
5 to 11. The phosphorus removal from the during 60 min at 400 rpm using a Varimag-
aqueous solutions was attributed to both poly15 magnetic stirrer. This time is high
precipitation with calcium ions and the enough to ensure an equilibrium state between
adsorption onto the TTPMW particles. aqueous phosphorus and the solid matrix. The
dissolved phosphorus concentration was
Key words: Phosphorus, recovery, marble,
adsorption, precipitation determined spectrophotometrically after the
suspension filtration through filter paper.
1. Introduction
Phosphorus is an essential nutrient that
is required for the growth of organisms in The batch experiments showed that for an
most ecosystems; however, if it exits in initial aqueous concentration of 350 mg/L, an
excess, it can cause the eutrophication of initial solutions pH of 5 and a TTPMW
not only the surface fresh water bodies but dosage of 1 g/L, the phosphorus removal
capacity and efficiency was evaluated to be the solid particles and also the precipitation
more than 180 mg/g and 51% respectively. with calcium cations dissolved in water when
The contact time necessary to this reaction shaking the TTPMW with the aqueous
was lower than 1 hour which is very solution. The precipitation becomes the
advantageous compared to other supports. predominant process when the solutions pH
The phosphorus removal efficiency increases especially for values higher than pH
increases when increasing the solid matrix of zero charge of the solid matrix.
dosage (Figure 1). It reaches 100% for
relatively low TTPMW doses (8 g/L). This 200
behavior is attributed to the presence of pH=5
pH=8
Adsorbed amount (mg/g)

more active sorption sites and more 150 pH=11
dissolved calcium cations that could
interact with dissolved phosphorus to form 100
calcium phosphates precipitates. The pH

has an adverse impact on the phosphorus 50
removal (Figure 2). This finding may be

due to the fact that at low pH values, the 0
150 200 250 300 350
surfaces of the used particles were Initial aqueous phosphorus concentration (mg/L)
positively charged, which would favour the
phosphorus anions removal by the Figure 2: Effect of the pH on the phosphorus
positively charged surfaces particles. On removal
the contrary, relatively high pH values lead 4. Conclusions
the surface to carry more negative charges Calcinated powdered marble wastes present
and consequently would more repulse the high selectivity and efficiency towards the
negatively charged phosphorus ions. removal of dissolved phosphates from
400
synthetic aqueous solutions and real
Residual phosphorus concentration
wastewaters. The adsorption process

300 effectiveness increased with increasing
adsorbent dosage and initial concentrations
(mg/L)
200 and decreased with increasing pH values. The

phosphates removal is controlled by
100 complexation with some specific functional
groups and also precipitation with calcium
0
0 1 2 4 6 8 10
cations. The use of TTPMW as a low cost
TTPMW dosage (g/L) material for phosphates removal and recovery
ensures both efficient tertiary wastewater
Figure 1: Effect of TTPMW dosage on the
treatment and waste recycling as a fertilizer.
phosphorus removal
The tested wastewater coming from a local References
dairy industry highlighted the relatively [1] WRI: World Resources Institute, Agriculture and
high capacity of the TTPMW in removing DeadZones., 2008. Available at:
the dissolved phosphorus. Indeed, high http://www.wri.org/publication/content/7780.
removal capacities were observed for [2] Cordell, D., Rosemarin, A., Schrder, J. J., Smit, A. L.,.
relatively low TTPMW dosages [3]. Towards global phosphorus security: A systems framework
for phosphorus recovery and reuse options, Chemosphere.
The phosphorus removal mechanisms have 2011, 84, 747-758.
been illustrated through special analysis [3] Jaouadi S., Mlayah, A., Jellali S. Phosphates removal
such as MEB/SEM and FTIR analyses. from aqueous solutions by marble wastes under static
They showed that for both the synthetic conditions. Desalination and water treatment, 2013, under
solutions or the real wastewater, the press
phosphorus was removed through
adsorption process onto the active sites of
Enhancement of methylene efficient in dyes removal, some of them have

the drawback of high cost and the others
blue removal by anodic produce large amounts of sludges.
oxidation using BDD electrode The main goal of this research work is to
combined with adsorption study the combination of the anodic oxidation
onto sawdust degradation and adsorption technologies for
the removal of MB from aqueous solutions
H. Akrout1, S. Jallali1, L.Bousselmi1
under different experimental conditions.
1 Wastewater treatment laboratory, Water Research and 2. Experiments
Technologies Center (CERTE) Echopark Borj Cedria
Touristic road of Soliman, BP 273, 8020, Tunisia During this study, the MB removal has been
hanene.akrout@yahoo.com, salah.jallali@cetre.rnrt.tn performed for initial concentration of 50 mg/L
and pHs of 3; 5; natural (without adjustment);
Abstract: 9 and 11 for the three following cases:
The methylene blue (MB) removal from Anodic oxidation: The synthetic solution
aqueous solutions by adsorption onto containing MB was stored in a glass tank
sawdust and anodic oxidation using BDD (1L) and circulated through the
electrode has been performed. The electrolytic cell by a peristaltic pump
experimental results proved that the MB working in recycling mode. Electrolysis
can be efficiently removed from aqueous cell (mini Diacell PS 500) is made of a
solutions using a combination of an single compartment with parallel plate
electrochemical pretreatment for one hour electrodes. The anode is a monopolar p-
followed by adsorption onto a relatively
silicon covered by boron doped diamond
low dose of sawdust (3 g/L). In this case,
(2-3 m thick) with a 12.5 cm2 rectangular
the obtained coloration removal efficiency
surface (50x25 mm) and the cathode is a
is about 95%. Furthermore, tit appears that
stainless steel with 3 mm as a gap.
not only the MB but also the electro-
generated products were efficiently Adsorption onto sawdust : synthetic
removed by sawdust with an average solutions containing MB at an initial
decrease of the DCO contents of about concentration of 50 mg/L has been stirred
98%. The combination of these two for 4 hours at different adsorbent doses: 1;
treatments permits an energy gain of about 4; 8;12 and 16 g/L;
80 Wh (gDCO)-1 and a net reduction of the Adsorption onto sawdust after anodic
used sawdust amounts: 24 times lower the oxidation during 1 hour. During these
one required when using adsorption alone. assays, the initial used pH corresponded to
Key words: Methylene blue, anodic oxidation, a natural state (without adjustment) and
Adsorption, combined treatment, sawdust. the tested adsorbent doses were: 0.5; 1; 3
1. Introduction and 5 g/L;
The presence of dyes in effluents is a The coloration removal was followed
major concern due to their adverse effects through the measure of the absorbance
to many forms of life. Industries such as spectrum using an UV-Visible
textile, leather, paper, plastics, etc., usually spectrophotometer and the analysis of the
generate a considerable amount of chemical oxygen demand (COD) was
coloured wastewater [1]. Many treatment determined by the standard method involving
processes have been applied for the potassium dichromate.
removal of dyes from wastewater such as 3. Results and Discussion
photocatalytic degradation, membrane 3.1. Effect of pH on the efficiency of methylene
filtration, precipitation, biological blue removal by anodic oxidation
degradation, electrochemical degradation The MB removal by anodic oxidation
and adsorption using low cost materials. seems to be very dependent on the pH (Fig.
Even if these processes were relatively
1). Indeed, for acidic medium, more The combination of MB anodic oxidation
radicals were produced which result in during one hour and adsorption with different
better colour removal efficiency [2]. doses of sawdust showed that this procedure
could be considered as a very interesting
100
option for the treatment of industrial
Colour removal(%)
80 wastewaters. Indeed best removal efficiencies

60 in term of color removal and also COD
pH = 3
degradation of MB and also the electro
40
pH naturel = 6.2 generated products were registered (Fig. 3).
pH = 9
20
pH = 11 Furthermore, an important energy gain of
0 about 80 Wh (gDCO)-1 was obtained and 24
0 60 120 180 240 300 360 times lower of sawdust amount were required.
Time (min)
400 100
Figure 1: Colour removal efficiency by anodic
Removal (%)
300 75
DCO (mg O2/L)

oxidation versus pH Concentration after 1 h AO
Concentration without AO
3.2. Effect of pH and adsorbent dose on 200 Removal after 1 h AO pretreatment 50
Removal without AO
methylene blue removal by adsorption onto
100 25
sawdust
The color removal by adsorption onto 0 0
sawdust is very dependant onto both the 0 4 8 12 16

Dose (g/L)
aqueous pH values and the adsorbent
dosage. The worst removal efficiency Figure 3: DCO removal by sorption onto sawdust
(4.2%) was observed for the lowest pH (3) of effluent pretreated with AO during 1 h.
and adsorbent dose (1 g/L). This finding is 4. Conclusions
to be attributed to the excess of H+ ions The combination of 1 hour of anodic oxidation
and to the relatively low adsorption sites on BDD electrode and the sorption onto
availability [3]. However, for initial pH sawdust improves the MB removal efficiency
values and adsorbent doses higher than 6.2 and also reduces the technology cost. Thus,
and 8 g/L, the color removal efficiencies the use of combined electrochemical and
exceeded 97% (Fig. 2). adsorption processes could be considered as
It is important to underline that the same an attractive technology for MB removal from
finding has been observed for the COD textile effluents.
removal. However, the maximal removal Acknowledgment
efficiency has been estimated to be about This research was done with the support of
80%. International Foundation for Science (IFS), Sweden, by
100
a research following ship to CP: Hanene Akrout-
Colour removal (%)
pH=3 Baccour.
80 pH=5
60
pH naturel = 6.2
pH=9
References
40
pH=11 [1] Martinez-Huitle, CA., Brilllas E. Decontamination of
waste-waters containing synthetic organic dyes by
20 electrochemical methods: a general review. Appl Catal B
0 Environ 2009, 87, 105 145.
1 4 8 12 16 [2] Akrout, H, Bousselmi L. Chloride ions as an agent
Dose (g/L)
promoting the oxidation of synthetic dyestuff on BDD
Figure Y: methylene blue removal efficiency electrode. Desalination Water treatment 2012, 46 171
by adsorption onto sawdust at different pH and 181
adsorbents doses. [3] Jellali, S., Wahab, M. A., Anane, M., Riahi K., Jedidi, N.
3.3. Methylene blue removal by Biosorption characteristics of ammonium from aqueous
solutions onto Posidonia oceanica (L.) bers.
combination of anodic oxidation and
Desalination 2011, 270, 40-49.
adsorption
Study of an oxygen carrier binder NiAl2O4 can also react with the fuel
contributing as an additional reaction to the
performances: Estimation of studied kinetics[3]. Therefore, it is important to
the support contribution by study the contribution of the support
experimental/numerical and (NiAl2O4) in the reaction, to subtract it from
the oxygen carrier kinetics, and thus to
DOE methodology. estimate kinetics of the active phase NiO.
L. Blas1, S. Dorge1, P. Dutourni2, A. In this work, we studied the effects of
Lambert3, S. Bertholin3 reduction parameters (temperature and fuel
1. Laboratoire Gestion des Risques et Environnement,
concentration) on the performances of
Universit de Haute Alsace, 3 bis rue Alfred Werner, NiAl2O4 binder using a full factorial central
68093 Mulhouse, France. composite design. This approach provides the
lucia.blas@uha.fr, sophie.dorge@uha.fr
2.Institut de Science des Matriaux de Mulhouse (IS2M),
maximum information of the operating
CNRS UMR 7361, 3 bis rue Alfred Werner, parameter influences by minimizing the
68093 Mulhouse, France.- patrick.dutourni@uha.fr experimental tests [4] and allows to simulate
3. IFP Energies Nouvelles, BP3, 69360 Solaize, France
arnold.lambert@ifpen.fr, sthephane.bertholin@ifpen.fr
reaction rates of the reduction step of the
binder NiAl2O4.
Abstract: 2. Experimental part

Knowledge of oxygen carrier reactivity is 2.1 Material
strategic for the industrial development of The material used is a NiAl2O4 support
the CLC process. The aim of this research provided by IFPEN (Solaize, France) Particle
is to investigate the contribution of the size is in the range of 0.125-0.3 mm.
support (NiAl2O4) on the oxygen carrier 2.2 Experimental set up
(NiO/NiAl2O4) performances. A design of This study is carried out in a fixed bed
experiment approach is used to estimate reactor placed in a vertical tubular furnace.
the reactivity (total capacity, reduction Gas flow rate is fixed at 50 NL.h-1. CO, CO2
rate) of the support. and O2 concentrations at the outlet of the
Key words: CLC process, nickel aluminate, reactor are measured by two IR analyzers
Design of Experiments, reduction parameters. (Rosemont NG2000 and X-stream).
2.3 Procedure
The procedure used in this study consists of
1. Introduction a first oxidation step, where the sample is
Chemical looping combustion (CLC) is heated under oxidizing atmosphere (air) from
an innovative technology, which allows the room to operating temperature. After an
production of energy with a selective inerting step under N2 during 10 minutes, a
capture of CO2 and low energy penalty [1]. mixture of CO/N2 is injected to reduce the
In this process the oxygen needed for the material (reduction step).
combustion is provided by an oxygen
carrier which is alternatively reduced by
the fuel and oxidized by air. The success of 3. Results and Discussion
a large scale application depends on 3.1 Experimental Results
finding suitable oxygen carriers.
Tests were performed at different
NiO/NiAl2O4 has been widely studied and
temperatures between 700C and 900C and
it is one of the most performing oxygen
at different CO concentrations between 0.1
carriers[2]. The study of reactivity and
and 1 vol.%, according to Design Of
kinetics of the oxygen carrier is essential to
Experiments methodology (DOE). Results
the conception of industrial scale reactors.
obtained for three reduction cycles with an
In the case of NiO/NiAl2O4, it has been
injected CO concentration of 5100 ppm and at
observed that the oxygen available in the
different temperatures are shown in figure 1.
The equations previously determined

(equations 2) for parameters a, b and c are
input in the equation 1. The relative error for
all the experimental tests is lower than 6%.
Figure 2 shows the results obtained for a cycle
Figure 1: CO and CO2 concentration vs. time for

three cycles at different temperatures.
It can be observed that the shape of the 3
cycles is different depending on the
temperature. The total oxygen transfer
capacity of NiAl2O4 and the intersection
time of curves increase with the performed at 800C and 5500 ppm of CO.
temperature. DOE methodology is used to
approximate these two responses as a Figure 2: Rate of oxygen conversion vs. available
function of the operating parameters. oxygen. Experimental points and simulation.
3.2 Calculation of available oxygen in NiAl2O4
and rate of conversion There is a good agreement between
experimental and simulated results. The
An unsteady model is developed to methodology is thus validated and can be used
calculate continually the available oxygen to account for the oxygen amount that stems
in NiAl2O4 and the rate of oxygen from the support in the oxygen carrier.
conversion using mass balance.
4. Conclusions
3.3 Simulation of the rate of oxygen conversion
vs. available oxygen in the NiAl2O4. DOE The reactivity of the support of an oxygen
methodology carrier (NiO/NiAl2O4) has been studied. A
It was observed that the curves of oxygen new methodology combining experimental,
conversion rate (r(t)) vs. available oxygen DOE and numerical investigation has been
(x) for all the tests performed could be used and validated to estimate the support
fitted by the following equation: contribution during the reduction reaction
References
= (1)
[1] Kerr, H.R. Capture and separation technology gaps and
priority research needs. In Thomas, D., Benson, S., Eds.;
a, b and c were calculated for all the Carbon Dioxide Capture for Storage in Deep Geologic
applied reaction conditions by minimizing Formations-Results from the CO2 Capture Project:
a quadratic criterion. Then, using DOE Amsterdam, 2005; Vol. 1, pp.655-660.
[2] Adanez, J. Progress in Chemical-Looping Combustion
methodology, it is possible to approximate
and Reforming technologies. Prog. Energy Combust.
each parameter (a, b, c) via a quadratic
Sci. 2012, 38, 215282.
equation which is function of the operating [3] Dueso, C. Reduction and oxidation kinetics of nickel-
temperature and of the CO concentration based oxygen-carriers for chemical-looping combustion
(equation 2): and chemical-looping reforming. Chem. Eng. J. 2012,
188, 142154.
, , = + + + [4] Chabeaud, A. Application of Response Surface
+ + (2) Methodology to Optimise the Antioxidant Activity of a
Saithe (Pollachius virens) Hydrolysate. Mar. Biotechno.
2008, 11, 445455.
Key words: wetness impregnation, activated

COPPER SUPPORTED ON carbon, heterogeneous catalyst, Nitrobenzene,
ozonation.
POROUS ACTIVATED
CARBON BY WETNESS 1. Introduction
IMPREGNATION: EFFECT The need to improve both the efficiency and
OF PREPARATION environmental acceptability of industrial
CONDITIONS ON processes is driving the development of
heterogeneous catalysts. The use of
CATALYST carbonaceous materials, especially activated
CHARACTERISTICS carbon, in the purification of gases and liquid
continues to increase because of the great
Asma ABDEDAYEM1 , Monia GUIZA2, versatility of these materials [1]. Activated
Abdelmottaleb OUDERNI3
exhibits the most favorable physical and
1, 2, 3
National School of Engineers of Gabes St Omar Ibn chemical characteristics for the preparation of
El Khattab 6029 Gabes, TUNISIA
1
a catalyst, the active metals will be dispersed
asma-abdedayem@hotmail.fr onto the small pores to help further oxidized
2
monia.guiza@enig.rnu.tn the intermediate products into final products
3
mottaleb.ouederni@enig.rnu.tn (carbon dioxide and water) [2]. Recently these
catalysts are used in many chemical processes
such as heterogeneous catalytic ozonation.
Abstract:
The aim of this work is to investigate the
In this study, a new heterogeneous catalyst effect of the metal precursor and the texture of
copper supported on activated carbon was the support on the properties of the final
developed using wetness impregnation catalyst and the catalytic activity in the
process. The effect of different preparing reaction of the degradation of Nitrobenzene.
conditions on catalyst structure was
examined. In this study we focus on two 2. Experiment
key variables: the impregnation rate and 2.1 Catalyst preparation
the calcination atmosphere. The prepared
Heterogeneous copper catalysts was
metallic catalysts were characterized by
means BET, Boehm and developed by wetness incipient impregnation
thermogravemetric analysis. It was found and highly porous activated carbon was used
that the catalyst properties and the surface as a catalyst support and a solution of
functional groups were affected by the Cu(NO3)2.3H2O as a precursor of the active
preparation technique used. The best agent.
surface area was 1040 m2/g and it is
obtained when the AC was impregnate 2.2 Reaction procedure
with 12% Cu loading and calcined at The reaction is carried out in a semi-
550C for 3h. Additionally, the continuous gas-liquid reactor of 2 liters total
performance of Cu/AC catalyst was volume.
investigated on the nitrobenzene ozonation.
As a result it was found that the use of 3. Results and Discussion
Cu/AC for heterogeneous catalytic The effects of impregnation rate, calcination times
ozonation enhanced significantly the and calcination temperatures on the catalyst
degradation efficiency of Nitrobenzene structure was investigated.Than the prepared
comparing to ozonation alone and AC/O3 catalyst was tested on the degradartion of
process. Nitrobenzene.
3.1 Effect of preparing conditions on catalyst specific area. Cu/AC catalyzed ozonation was
structure more effective than ozonation alone and ozonation
catalyzed by AC in the mineralization of
The specific surface area of catalyst
Nitrobenzene.
samples prepared at different conditions
was measured according to the Brunauer-
Emmet-Teller (BET) method with Acknowledgment
Nitrogen adsorption at 77K on a BET The author gratefully acknowledge the Research
sorptometer. laboratory of chemical engineering processes and
industrial systems.
3.2 Effect of preparing conditions on catalyst
structure
References
BET analysis results show that the
conditions for preparing the catalyst have [1] A.M. Fuente, G. Pulgar, F. Gonzlez, C. Pesquera, C.
important effects on the structure of Blanco*.Activated carbon supported Pt catalysts: effect
of support texture and metal precursor on activity of
catalyst and the best surface area was
acetone hydrogenation. Applied Catalysis A: General
1040 m2/g and it is obtained when the AC 208 (2001) 3546
was impregnate with 12% Cu loading and [2] Xijun Hu*, Lecheng Lei, Hiu Ping Chu, Po Lock
calcined at 550C for 3h. Yue, Copper/ activated carbon as catalyst for
3.3. Comparison of the Degradation Efficiency of organic wastewater treatment Carbon 37 (1999)
Nitrobenzene 631637.
The catalytic activity of the catalyst was
investigated on the degradation of the
Nitrobenzene. Results shows that the use
of Cu/AC for heterogeneous catalytic
ozonation enhanced significantly the
degradation efficiency of Nitrobenzene
comparing to ozonation alone and AC/O3
process.
0,8
0,6
(C0-C)/C0
0,4
0,2
0
0 20 40 60 80
time(min)
O3+CA O3+ Cu/CA O2 O3 CA
Figure 1. degradation efficiency of nitrobenzene by
different processes
([O3]= 14.667mg/l, [NB]=20mg/l, T= 18C, pH=5.5,
mCu/CA=1g)
4. Conclusions
Cu/AC catalyst prepared at 12% of copper,
calcined at 550C for 3h has the best surface
Characterization and thermal leaves and part of rhizomes detach off the
marine plant and reach the coasts. These
degradation kinetics of residues represent great environmental,
Posidonia Oceanica economical, social and hygienic problem in all
coastal zones. The great disturb to the bathers
Y. ELMAY*1,2,M. JEGUIRIM1, M. and population, impose their removal and
disposal in the landfill. The latter solution
LAJILI2, L. LIMOUSY1, R. SAID2
causes environmental problems and a high
economical costs (80120 t1 in Italy) [3].
1
Institut de Science des Matriaux de Mulhouse, UMR
7361 CNRS, 15, rue Jean Starcky 68057 Mulhouse,
France
A chemical, physical and spectroscopic
2
characteristics of different beach-cast PO
Unit de Recherche dEtude des Milieux Ioniss et
Ractifs, IPEIM, Avenue Ibn El Jazzar Monastir 5019, debris have been determined by Cocozza et
Tunisie al.[3]. Authors found that the fibrous portion
of posidonia residues can be utilized as
biofuel according to their lower heating values
Abstract: (LHV) ranging between 13.6 and 15.7 MJ
The Thermal degradation characteristics kg1, whereas leaves debris are not so suitable
of Posidonia Oceanica (PO), a marine for the energy recovery because their LHV
biomass abundantly available on the coasts were around 10 MJ kg1.
zone of Mediterranean Basin, were While various marine biomass fuels have
investigated. Both pyrolysis in inert received extensive investigation [4], [5], PO
atmosphere and combustion in presence of energy asses have not been studied in details.
oxygen were carried out in a To the best of our knowledge, there no
thermogaravimetric analysis (TGA) complete information about thermal
system. Different methods were proposed degradation of PO in literature. In the present
(Friedman, Coats-Redfern and Phadnise- study a deep analysis of PO thermal
Deshpande) for the determination of the degradation in both inert and oxidative
main degradation stages corresponding atmospheres is presented along with the
kinetic parameters and the degradation determination of the probable degradation
mechanisms. mechanisms of the different main stages.
Key words: Posidonia Oceanica, Pyrolysis,
2. Experiment
Combustion, Thermogarvimetrie, kinetics.
2.1 Materials
Posidonia Oceanica (PO) balls used in this
1. Introduction study were collected from Chott-Meriem -
Biomass is a renewable energy source, Sousse.
which can be used as substitute for 2.2 Experimental and Methods
petroleum fuels. Marine biomass as
another sort of energy plants are Proximate and ultimate analyses were
abundantly available and represent an carried out to assess biomass characteristics.
interesting resource for energy production. Moreover, the heating values of the samples
Specially, Posidonia Oceanic (PO) is the were measured using an adiabatic oxygen
most abundant seagrass species among the bomb calorimeter (Prolabo). The results are
marine plants in the Mediterranean Basin. summarized in Table 1.
These marine plants form extensive Table 1: Operating conditions
meadows from nearly the water surface to
Ultimate analysis (%),
depths up to 40m [1] and cover wet basis
approximately 40,000 km2 of the seabed C H O N S Na K
[2]. Starting from SeptemberOctober, PO 58.9 8.3 31.3 1.3 0.20 0.049 0.07
*
Corresponding author : yassine.elmay@yhaoo.fr
Proximate analysis (%), HV Friedman and Phadnise-Deshpande methods.

wet basis (MJkg-1)
Table 2: Activation energies of PO
samples Moisture VM FC Ash HHV LHV pyrolysis obtained from the Coats-Redfern
method
PO 7.4 66.6 23.8 2.2 18.9 17.6
The thermal behavior of the PO biomass Mecha First Stage Second Stage
nism Ea Ea
was studied using a CAHN 121
(KJ/mol) R2 (KJ/mol) R2
thermobalance. The experiments were
performed under inert and oxidative F1 55,3 0,9849 23,0 0,9926
atmospheres, from room temperature to R2 48,5 0,9818 12,6 0,9946
900 C, with a gas flow rate of 12 NLh-1, at R3 50,1 0,9824 15,2 0,9939
constant heating rates of 5 Cmin-1 D2 102,6 0,9842 27,6 0,9940
D3 109,0 0,9852 40,4 0,9943
3. Results and Discussion D4 104,7 0,9846 31,1 0,9934
Figure 1 shows the mass loss (X%) and A2 * * 7,04 0,9862
the derivative of mass loss (dX/dt) curves
obtained during the pyrolysis of PO under
4. Conclusions
inert atmosphere at a heating rate of 5
C min1. Thermal behavior and kinetic parameters of
the main stages involved in the thermal
degradation of PO under inert and oxidative
atmospheres were investigated by using
different methods.
Data presented are useful for assessing the
potential impacts during combustion and
pyrolysis of this marine biomass in dedicated
units
References
[1] C. M. Duarte, Seagrass depth limits , Aquat.
Figure 1: Fig. 1: Thermogravimetric analysis of Bot., vol. 40, no 4, p. 363377, 1991.
PO in inert atmosphere [2] J. Cebrian et C. M. Duarte, Detrital stocks
To investigate the solid-state processes and dynamics of the seagrass Posidonia
for the first and second thermal oceanica (L.) Delile in the Spanish
Mediterranean , Aquat. Bot., vol. 70, no 4, p.
degradations stage of PO (Figure 1), Coats-
295309, aot 2001.
Redfern and Phadnise-Deshpande and
[3] C. Cocozza, A. Parente, C. Zaccone, C.
Friedman methods were chosen. Mininni, P. Santamaria, et T. Miano,
As example of calculation results, table Chemical, physical and spectroscopic
2 gives the activation energies and the characterization of Posidonia oceanica (L.)
correlations coefficient at 5 C/min, for the Del. residues and their possible recycle ,
first and second pyrolysis degradation Biomass Bioenergy, vol. 35, no 2, p. 799807,
processes of PO. fvrier 2011.
From table 2 can be seen that the first [4] M. F. Demirbas, Biofuels from algae for
sustainable development , Appl. Energy, vol.
thermal degradation stage of PO under
88, no 10, p. 34733480, oct. 2011.
inert obey to diffusion mechanism D3. For
[5] A. B. Ross, J. M. Jones, M. L. Kubacki, et T.
the second stage, R1 and R2 were both Bridgeman, Classification of macroalgae as
possible mechanisms. In fact, values of fuel and its thermochemical behaviour ,
activation energy in Table 2 were in better Bioresour. Technol., vol. 99, no 14, p.
agreement with that obtained using 64946504, sept. 2008.
Heterogeneous Advanced Photo- Several complementary techniques, including

Fenton oxidation of phenolic XRD, Nitrogen sorption isotherms, UV
visible, IR spectroscopy were used to evaluate
aqueous solutions over iron/CeO2
the final structural and textural properties of
catalysts calcined Fe/CeO2.
Z. Bailiche1,2,3, L.Cherif1, S. Fourmentin2,3, Keywords: Fenton, photo-Fenton,
S. Siffert2,3, S.Royer4 mesoporous, Fe/CeO2, hard template, SBA-15
1
Laboratoire de Catalyse et Synthse en Chimie
Organique, Universit de Tlemcen BP 119, Algrie
2
Universit Lille Nord de France, F-59000 Lille,
France
3
ULCO, UCEIV, F-59140 Dunkerque, France
4
Institut de Chimie des Milieux et Matriaux de Poitiers
(IC2MP), UMR CNRS 72854, 86022, POITIERS,
FRANCE
Abstract
Aromatic compounds are common

pollutants in the effluents of several
industries. The degradation of these
pollutants in wastewater streams has
emerged as an important concern during
last decade. Advanced oxidation
processes(AOPs) such as ozonation, ,
photocatalysis, Fenton and a combination
of photo-Fenton, UV/O3, UV/H2O2 have
received considerable attention as
wastewater treatment processes due to their
ability to degrade , and in many cases,
mineralize various organic compounds that
are otherwise resistant to conventional
biological and chemical treatments.
The purpose of this study is the assessment
of Fe/CeO2 mesostructured materials
prepared by impregnation, CeO2
mesostructured material prepared by hard
template using SBA-15 as template for the
heterogeneous photo-Fenton degradation
of phenolic aqueous solutions.
Activity and stability of these materials
were assessed on the photo-Fenton
degradation of phenolic aqueous solutions
by H2O2 using near UV irradiation
(254nm) at room temperature and initial
neutral pH. Their catalytic performance
was mentioned in terms of phenol
conversion and total organic carbon (TOC)
conversions. Activity and stability of Fe-
SBA15 for treatment of phenolic aqueous
solutions depend Fe /CeO2ratio.
PRODUCTION AND membrane used and the cutoff or particle size

that it can retain [2].
FRACTIONATION OF
To produce simple aromatic compounds
ORGANOSOLV LIGNIN from lignin, selective hydrogenolysis of lignin
FROM OLIVE TREE could lead to high-value-added chemicals and
CLIPPINGS potential fuel precursors by decreasing the
Luis Serrano1, Ana Toledano1, Rafael oxygen content of lignin [2].
Luque2 and Jalel Labidi1 Olive tree clippings were first subjected to
1. Environmental and Chemical Engineering
Department, University of the Basque Country, Plaza
organosolv treatment to dissolve the lignin
Europa, 1 20018, Donostia-San Sebastin (Spain), email: from the raw material. The lignin-rich liquid
jalel.labidi@ehu.es fraction was ultrafiltered to obtain specific
2. Departamento de Qumica Orgnica, Universidad de
Crdoba, Campus de Rabanales Edificio Marie Curie (C-
molecular weight lignin fractions.
3), Ctra Nnal IV-A Km 396, 1014 Crdoba (Spain), Ultrafiltered lignin fractions were subjected to
email: q62alsor@uco.es mild, hydrogenolytic, microwave-assisted
Abstract: protocol to obtain phenolic monomeric
In this study, firstly, the best organosolv compounds.
operational conditions were selected. High
temperature, medium ethanol 2. Experimental section
concentration and medium time were 2.1 Olive tree pruning
selected in a compromise between lignin The raw material was originated by olive
yield and purity of the lignin. Then, a new trees cultivated in Navarra (Spain) belonging
lignin valorization is proposed using to variety called Arrniz. They were
ultrafiltration as a fractionation process characterized following the TAPPI standards
followed by depolymerization using a with a 23% of lignin.
nickel-based catalyst assisted by
microwave irradiation to obtain simple 2.1 Experimental design
phenolic compounds. The applied model uses a series of points
Key words: lignin, organosolv, (experiments) around a central one (central
depolymerization, microwave experiment) and several additional points
1. Introduction (additional experiments) to estimate the first-
and second-order interaction terms of a
Agricultural residues constitute and polynomial [1].
interesting feedstock for biorefineries due
2.3 Ultrafiltration technology
to their abundance, low cost, and
worldwide availability. Spain generates The UF module used membranes made of
significant quantities of olive tree ceramic material, tubular and multichannel
clippings. type. The cutoff levels used were 300, 150,
Lignin is a phenolic polymer built up by 50, 15 and 5 kDa.
oxidative coupling of three major C6-C3 2.4 Lignin characterization
(phenylpropanoid) units, namely, syringyl ATR-IR spectroscopy and TGA were used
alcohol (S), guaiacyl alcohol (G), and p- to determine the lignin purity in the
coumaryl alcohol (H). experimental design [1]. The ultrafiltered
Organosolv treatments could constitute lignin fractions were characterized using the
a viable future pulping alternative [1] and procedures of standard developed by ILI and
membrane technology is successful for MW was determined by using HPSEC [2].
simple and effective separation, 2.5 Lignin depolymerization
concentration, and purification of products.
The extent or effectiveness of membrane Hydrogenolysis reactions were carried out
technology depends on the type of in a microwave reaction system. Formic acid
was used as hydrogen-donating solvent and
10% NiAlSBA 15 catalyst was used as nature and concentration of the isolated
catalyst. phenolic monomeric compounds (Table 1).
3.1 Organosolv experimental design
Three independent variables were varied
during the delignification process: time (t)
(60-120 min), temperature (T) (160-200
C), and ethanol concentration (C) (60-
80%). The results of 27 experiments were
analyzed and the highest concentration in
the liquid fraction, 36.55 g/L, was obtained
at the highest T, the shortest t, and lowest
C.
3.2 Lignin characterization
Figure 1: Up) Obtained oil yields (%, w/w)
ATR-IR results revealed that the referenced to the initial lignin weight for each lignin
precipitate was mainly lignin H:G:S type. fraction. Down) Residual lignin (%, w/w) referenced
TGA analysis showed lignin contamination to the initial lignin weight.
due to hemicelluloses or other degradation 4. Conclusions
products in different proportion depending
on the severity of the treatment. A compromise between the yield of lignin
concentration in the liquid fraction and the
3.3 Ultrafiltration process (UF) composition of lignin was selected in the
The treatment selected in base to the organosolv experimental design. In
previous experimental design was 200 C, ultrafiltration process, the fractions exhibiting
90 min and 70 wt% ethanol with a lower hemicellulosic contamination at
solid/liquid ratio 1:6 (w/w). The decreasing membrane cutoffs. Lignin
organosolv lignin-rich fraction underwent depolymerization took place under the
UF to obtain specific MW lignin fractions. reaction conditions investigated. The main
Six lignin fractions were obtained phenolic monomers obtained were
depending on the cutoff used: >300 kDa desaspinidol, syringaldehyde and syringol.
(F1), 300 kDa< > 150 kDa (F2), 150 kDa < Acknowledgment
> 50 kDa (F3), 50 kDa < > 15 kDa (F4), 15
kDa < > 5 kDa (F5), < 5 kDa (F6), and The authors would like to acknowledge the
financial support of the Spanish Ministry of
their exact composition and MW were Economy and Competitiveness under the projects
determined. CTQ2010-19844-C02-02, CTQ2011-28954-C02-02
3.4 Lignin depolymerization and Juan de la Cierva contract JCI-2011-09399.
After the hydrogenolytic approach, two References

main products were obtained: an enriched [1] Toledano, A.; Serrano, L.; Labidi, J. Enhancement of
bio-oil and residual lignin (Figure 1). Lignin Production from Olive Tree Pruning Integrated in
a Green Biorefinery. Ind. Eng. Chem. Res. 2011, 4, 6573-
The phenolic bio-oil was further 6579.
[2] Toledano, A.; Serrano, L.; Balu, A.M.; Luque, R.; Pineda,
analyzed by GC-MS to determine the
Table 1: Summary of compounds present in the obtained oil.

Concentration in fraction (mg glignin-1)
Compound Retention time (min) F1 F2 F3 F4 F5 F6
Syringol 14.01 0.62 1.47 0.31 0.65 0.47 0.74
Syringaldehyde 18.67 1.66 0.76 0.76 1.10 1.19 0.87
Desaspidinol 19.60 2.43 3.31 0.88 2.25 0.70 1.10
A.; Labidi, J. Fractionation of Organosolv Lignin

from Olive Tree Clippings and its Valorization to
Simple Phenolic Compounds. ChemSusChem 2013,
6, 529-536.
Activated carbon prepared by physical efficient carbonaceous adsorbents from olive

activation of olive stones for the removal stones for the NO2 removal.
of NO2 at ambient temperature.
2. Experiments
Imen Ghouma1,3 , Mejdi Jeguirim2 ,
Sophie Dorge3, Abdelmottaleb Ouderni1 2.1. Activated Carbon Preparation
Two physical activated carbons were
1. Laboratoire Gestion des Risques, prepared by olive stones carbonization at
Environnement 3 bis, rue Alfred Werner 68093
Mulhouse, France. 600C for 2h followed by activation using
2. Institut de Sciences des Matriaux de water vapor (CA_H2O) or CO2 (CA_CO2) at
Mulhouse, 15 rue Jean Starcky, 68057 750 C for 6 h.
Mulhouse, France.
3. Laboratoire Gnie des Procds et Systmes Table 1: Surface Area, Pore Volume, and Pore
Industriels, Universit de Gabs, Tunisie Diameter of the samples
label SBET Vmicrospores Dmicropores
Abstract:
(m2/g) (cm3/g) (A)
The adsorption of NO2 over activated CA_H2O 1398,8 0.346 45.41
carbon (AC) prepared from olive stones
were investigated at ambient temperature. CA_CO2 712,32 0.247 32.04
Different carbonaceous adsorbents were
prepared by physical activations using H2O 2.2. Adsorption tests
and CO2 as activating agents. During The experiments were performed in a fixed
adsorption tests, both NO2 adsorption and bed reactor shown in Figure 1.
reduction into NO were observed.
Temperature programmed desorption NO2
(TPD) was then performed to evaluate the BYPASS
O2
nature and thermal stability of the adsorbed
N2
species. NO/NO2 analyser
H2O
The best NO2 sorption capacities of 187
Mass flow meters
mg/g and 193 mg/g were obtained for AC 1000 ppm NO
1000 ppm NO2

1
7
2
8
3
9
ES
C
ENTER
activated with CO2 and H2O respectively. CO/CO2 analyser

However, a low undesirable NO emission Thermocouple
was obtained with the CO2 AC. Therefore, furnace 500 ppm CO
1
4
2
5
3
6
ES
C
1000 ppm CO2 7 8 9 ENTER
this latter could be used as efficient

soot
adsorbents for NO2 removal.
Porous quartz layer
Key words: (olive stones, adsorption, NO2,
activated carbon) Condenser
Data acquisition system
1. Introduction Figure 1 Scheme of the set-up for the fixed bed

experiments
Recently, the removal of NO2 at low
temperature using activated carbons has
been proved to be a promoting technique. In each experiment 100 mg of activated
Several precursors such sawdust pellets [1] carbon was deposited on a quartz frit (internal
Bituminous Coal [2] and the sorption NO2 diameter 16mm) set in a vertical flow quartz
capacities ranged from 17 to 140 mg/g [3]. reactor. The bed temperature was measured by
However, a significant amount of a thermocouple located 1mm above the AC
undesirable NO was emitted during the sample. The outlet gas was analyzed using an
NO2 adsorption tests and therefore the infrared ROSEMOUNT NGA 2000 analyzer
doping of silver nanoparticles is requested to quantify the outlet NO, NO2 molar
to prevent these emissions [4]. Hence, the fractions. A gas stream mixture consisting of
purpose of this present work is to develop nitrogen and NO2 (500 ppm by volume) was
admitted and passed through the column of and the total emitted NO were calculated. The
adsorbent. Thermogravimetry study of obtained values for the different activated
samples was performed up to 500C at a carbons are shown in Table 1.
heating rate equal to 5C/min. Differential
Table 2: Amounts of gas species adsorbed or
thermogravimetry curves after exposure to emitted during the adsorption
NO2 showed the peaks which is assigned
the decomposition of each component of Sample CA_H2O CA_CO2
the activated carbon. NO2 adsorbed 193.0 187.2
(mg/g)
3. Results and Discussion NO 0.89 0.34
emitted/NO2
3.1 Results
adsorbed
The change in NO2 concentration in the
outlet stream after exposure of the The best sorption capacity of 193mg/g was
activated carbon to 500 ppm NO2 at obtained for AC activated with H2O.
ambient temperature is shown as a function However, although a lower surface area, the
of time on the Fig. 2. CA_CO2 have a higher sorption capacity of
187mg/g without leading to a significant
amount of NO emission. Such behavior may
be attributed to the oxygen surface function
obtained during the physical activation.
Therefore, activated carbon prepared from
olive stones by CO2 activation could be used
as efficient adsorbents for NO2 removal.
4. Conclusions
Figure 2: Outlet concentrations of NO2, NO, during
the NO2 adsorption on CA_H2O. Adsorption step The aim of this research was to investigate
under exposure to 500 ppm NO2 at ambient the effect of the type of activation on NO2
temperature adsorption.
A marked decrease in NO2 concentration It is confirmed that the activation with H2O
(initial value equal to 500 ppm) is observed is much more efficient than the activation with
during the first 200 min as well as a sharp CO2. However, a lower NO/NO2 ratio shows
evolution of NO. Hence, during the NO2 that activated carbon prepared from olive
adsorption step, a significant amount of stones by CO2 activation could be used as
NO2 is reduced and leads to a release of efficient adsorbents for NO2 removal.
NO which reaches a maximum after 16
min of treatment. The emission of NO References
suggests that oxygen is partly fixed on the
[1] R. Pietrzak, Bioresource Technology 2010 (101) 907-
carbon surface in the form of surface 913.
complexes, such as C(O). A nitrogen [2] R. Pietrzak, Energy & Fuels 2009 (23) 36173624.
balance, determined from the consumption [3] S. Bashkova, T.J. Bandosz. Journal of Colloid and
of NO2 and the emission of NO, shows that Interface Science 2009 (333) 97103.
all consumed NO2 is not reduced to NO [4] M. Seredych, S. Bashkova, R. Pietrzak, T.J. Bandosz.
and consequently a part of NO2 is also Langmuir 2010 (26) 9457-9464.
adsorbed on the carbon surface. After 300
min of treatment, both adsorption and
reduction become less pronounced and
tend towards the initial values for time
larger than 500 min. From the nitrogen
balance data, the NO2 sorption capacities
Coupling adsorption and were identical in terms of DMP concentration

decrease over time (DMP total removal in 35
catalytic ozonation using min), suggesting no catalytic effect on DMP
alumino-silica materials for degradation kinetics.
2,4-dimethylphenol However, a synergistic effect was observed in
terms of total mineralization (TOC abatement)
degradation in water. during catalytic ozonation. The best results
were obtained with pure Alumina: more than
Wael Aboussaoud(a,b), Marie-Hlne 60% of TOC was removed after 8 hours
Manero(a,b), Jean-Stphane Pic(c) and experiment, compared to 29% during single
Hubert ozonation. The efficiency of the various
Debellefontaine(c) zeolites was quite lower: 44% TOC abatement
(a) Universit de Toulouse ; INPT, UPS ; with
Laboratoire de Gnie Chimique ; 4, Alle
Mordenite, 35% with Faujasite-Y and 38%
Emile
Monso, F-31432 Toulouse, France
with ZSM-5. The difference between the three
(b) CNRS ; Laboratoire de Gnie Chimique ; zeolites might be related to the binding
F-31432 Toulouse, France material used (clay for both Faujasite-Y and
(c) Universit de Toulouse LISBP ZSM-5
Laboratoire dIngnierie des Systmes and alumina for Mordenite). At last, the by-
Biologiques products evolution during catalytic ozonation
et des Procds (UMR CNRS 5504/INRA 792) showed two different behaviors:
INSA de Toulouse 135 avenue de - some specific by-products (di-hydroxy-
Rangueil 31077 Toulouse Cedex 4 France. benzenes, unsaturated di-acids) are
Keywords eliminated in the presence of pure Alumina
Heterogeneous catalytic ozonation,
alumino-silica materials, 2,4-
dimethylphenol
Abstract
This work aims to study the effectiveness
of heterogeneous catalytic ozonation as an
Advanced Oxidation Process for the
degradation and mineralisation of
refractory organic compounds from water.
The selection of the catalytic material is
one of the key parameters towards
efficiency of this kind of process as
efficient adsorption properties are usually
suspected to determine catalytic activity.
Three types of zeolites (Faujasite-Y,
Mordenite and ZSM-5) and pure Alumina
were selected.
Their catalytic effect regarding oxidation
was evaluated under the same reaction
conditions
(5 g/L material in the form of pellets, 0.075
g/L/h ozone input), using a 2 L semi-batch
reactor and 2,4-dimethylphenol (DMP - 50
mg/L) as a model molecule.
For all the materials tested, the results
obtained by single ozonation and catalytic
ozonation
Abstract
This study focuses on the synthesis and
characterization of pure titanium oxide and
doped with a non-conventional method due
to the presence of two types of activated
carbon (F400 and CECA 1240) and a clay
bentonite by the sol-gel method. Active
carbon and clay are first used without
treatment and then calcined at 700 C
hang two hours. A study of the adsorption
and the overall degradation of the template
molecule (cytarabine) is first made. The
most efficient catalysts under UV were
selected for physicochemical
characterization. Two investigative
techniques were used: XRD and BET
measurement. XRD showed that pure TiO2
is formed by the rutile phase only, so the
presence of the activated carbon in the
preparation causes the appearance of the
anatase phase.
BET measurement demonstrates that the
presence of activated carbon increases the
specific surface of the solid according to
the type of added carbon. At the end, a
demonstration of the influence of certain
reaction parameters (photon flux of the
lamp, initial concentration of pollutant
mass of the catalyst, pH of the solution)
was carried out
2.1. Theoretical considerations and mathematical

Kinetic modelling of textile model
synthetic effluent oxidation at
Depending on the applied current
boron-doped diamond density, two different operating regimes
have been identified for anodic oxidation
Nour El Houda Abdessamad1, Hanene [1,3,4]:
Akrout1, Latifa Bousselmi1 1. Case 1: japp<jlim :
The electrolysis is under current control, the
1. Waste water treatment laboratory, Water Research and
Technologies Center (CERTE) Echopark Borj cedria
current efficiency is 100% and the COD
Touristic road of soliman, BP 273, 8020 Soliman, Tunisia decreases linearly with time and the rate of
nour_houda1@yahoo.fr, hanene.baccour@certe.mrt.tn, COD removal is constant and can be written
latifa.bousselmi@certe.mrt.tn
as :
Abstract:
where =j/jlim0, V= solution volume (m3),
The anodic oxidation of two model dyes
A=electrode area (m2), km= mass transport
Acid Orange 8 (AO8) and Alizarin Blue
coefficient in the electrochemical cell (m s -1)
Black B (ABB) in aqueous solution at boron
and COD0= initial COD (mol O2 m-3).
doped diamond BDD electrode was
Integration this equation to the initial
experimentally investigated for kinetic
condition COD=COD0 at t=0 gives the
modeling. A quite agreement between
temporal evolution of COD (t) in this
theoretical predictions and experimental data
operating regime (j<jlim)
is obtained and confirmed that the anodic
oxidation is under mass transfer control. The
limited discrepancy is attributed to
intermediates produced during electrolysis.
2. Case 2: japp<jlim :
The electrolysis is under mass transport
Key words: Anodic oxidation, BDD electrode,
mass transfer control, Theoretical model. control, secondary reactions (such as oxygen
evolution) can take place. In this regime the
COD removal follows an exponential trend.
1. Introduction In this case, the COD mass balances on the
Theoretical models can offer useful electrochemical cell and the reservoir can be
strategies for both the individuation of the expressed as:
parameters that affect more the competition
between the targeted reactive path and side
unwanted reactions and the design of new Integration of this equation from t=t cr to t,
materials/apparatuses that can favor the and COD= CODcr to COD (t) leads to
selective occurrence of the desired route [1].
The experimental validation of mathematical Where tcr is a critical time, corresponding to
models can, furthermore, provide precious the time at which the applied current density
indications for scale-up stages and confirm is equal to the limiting current density.
the assumptions on which the model based
allowing a reliable description of the process In the frame of this work, the oxidation is
[2]. operated under mass transport control (japp=
In this purpose, a simple model is 40 mA cm-2) and the related equation can be
developed and applied to anodic oxidation of applied. This hypothesis is equivalent to
AO8 and ABB dyes solutions carried out at consider that while there are organic species
BDD electrode. to be degraded at the electrodes surface, no
oxygen evolution occurs.
2. Experiment The development of this model gives:
1
on the assumption that the anodic oxidation

is under mass transfer control.
An extension of the model to take in account
2.2 Experimental Set Up the possible presence of mixture organics in
Experiments were carried out under the same solution is also considered.
galvanostatic mode. The dyes solutions, References
which contain AO8 and ABB, as a model of
azo and anthraquinone dye respectively,
[1] Panizza, M.; Michaud, P.A.; Cerisola, G.; Comninellis,
were circulated through the electrolytic cell Ch. Anodic oxidation of 2-naphthol at boron-doped
by means of a peristaltic pump working in diamond electrodes. J. Electroanal.Chem. 2001, 507, 206
recycling mode. Electrolysis was conducted 214.
in undivided electrochemical cell supplied [2] Scialdone,O.; Galia,A.; Randazzo, S. Electrochemical
by Adamant Technologies, with parallel treatment of aqueous solutions containing one or many
plate electrodes (12.5 cm2 rectangular organic pollutants at boron doped diamond anodes.
Theoretical modeling and experimental data. J.Chem. Eng.
surface), the cathode is a stainless steel 2012,183,124-134
electrode.
[3] Abdessamad, N.; Akrout, H.; Bousselmi, L. Evaluation
3. Results and Discussion and optimization of textile synthetic effluent discoloration
using Anodic Oxidation on BDD electrode: Application of
In both studied cases, theoretical the experimental design methodology. Des. Wat. Treat. In
predictions based on the oxidation are Press.
occurred under transport kinetic control
were in agreement with the experimental [4] Akrout, H.; Bousselmi, L. Chloride ions as an agent
promoting the oxidation of synthetic dyestuff on BDD
data. electrode. des. Wat. Treat. 2012, 46, 171-181.
On the other hand, linear regression of the [5] Gherardini, L.; Michaud, P.A.; Panizza, M.;
experimental data can be also estimated Comninellis, C. ;Vatistas. N. Electrochemical
mass transfer coefficients two dyes studied. oxidation of 4-chlorophenol for wastewater treatment.
So, fitting plot give km values of 1.08 x 10 -5 Definition of normalized current efficiency .
and 0.87 x 10-5 m s-1 of AO8 and ABB, J.Electrochem. Soc. 2001, 148, 78-82.
respectively, against theoretical value about
1.33 x 10-5 m s-1. Obtained value are lowers
than those reported by Gherardini et al [5]
corresponding to km value of about 1.5 x 10-5
m s-1 for a similar single-compartment
electrolytic reactor and 4-chlorophenol as
organic compounds. The slightly
discrepancy between the experimentally
determined and fitted km values can be
attributed to the fact that the model is based
to suppose that one organic compound is
presented in solution. However, previous
studies [4] show that several organic
intermediates can be substantially produced
during electrolysis.
4. Conclusions
The agreement of the experimental data
with the presented theoretical model,
confirmed that the mineralization of AO8
and ABB dyes on BDD electrode are based
2
Design of TiO2 nanotubes and Photocatalytic technology using TiO2 is a

promising green process for environmental
nanorods doped with applications [1]. In order to improve TiO2
lanthanum for the photoactivity by decreasing the recombination
Photocatalytic degradation of rate, scientists explored many routes; among
them doping by different ions like rare earth
formic acid elements [1]. In the present work, we will
M. Meksi1, H. Kochkar1, 2, G. Berhault3, C. highlight the effect of several parameters such
Guillard3 and Z. Ksibi1 as: TiO2 morphology (nanotubes and
1. Laboratoire de Chimie des Matriaux et Catalyse,
nanorods), the effect of doping by lanthanum
Facult des Sciences de Tunis, Campus Universitaire El and post-thermal treatment on the
Manar, Tunis, Tunisie, meksi.manel@gmail.com photocatalytic degradation of formic acid in
2. Centre National des Recherches en Sciences des
Matriaux, Technople de Borj-Cdria, Soliman, Tunisie
aqueous media.
h_kochkar@yahoo.fr
3. Institut de Recherches sur la Catalyse et de
2. Experiment
lEnvironnement de Lyon, CNRS -Universit Lyon I, 2.1 Elaboration and characterization of materials
69100 Villeurbanne, France
TiO2 nanotubes (NT) was elaborated via an
Abstract alkaline hydrothermal method, using TiO2
Lanthanum doped titanates nanotubes and (P25) as described by Turki et al. [2]. The
nanorods were elaborated by wet autoclave is introduced inside the oven at RT
impregnation method using lanthanum before rising the temperature to 403K.
nitrate hexahydrated as precursor (1%wt). However, TiO2 nanorods (NR) was obtained
Firstly, titanate nanotubes were elaborated by introducing the autoclave inside the oven
via an alkaline hydrothermal route and directly at 403K. Then, the resulting products
nanorods were obtained using same (NT or NR) were kept under stirring with acid
conditions excepting that the autoclave HCl (1M) at RT during 30 min for sodium
was introduced directly in the furnace at removal. The products were washed
403K. After post-thermal treatments at intensively with hot ultra-pure water and dried
673/773/873/973K, these materials were at 353 K for 24 h. The obtained materials were
characterized by means of XRD, UV- doped with (1%wt) Lanthanum using
Visible (DRS) and N2 adsorption- lanthanum nitrate hexahydrated via wet
desorption at 77K. Photocatalytic activities impregnation method. Finally, the La-NT and
of these materials were examined and La-NR were calcined under air at 673, 773,
compared to undoped ones in the 873 and 973 K for 2 h. The resulting materials
photodegradation of formic acid in were named La-NT-T or La-NR-T; T is the
aqueous solution. The main results showed post-thermal temperature. Lanthanum free
that the presence of lanthanum stabilizes TiO2 Nanotubes and nanorods were also
the activities of starting materials even at calcined in the same conditions to serve as
high post-thermal treatment. This can be references.TiO2 nanomaterials (NT, NR, La-
due to the reduction of TiO2 crystallites NT and La-NR) were characterized by means
size and inhibition of anatase into rutile of X-Ray Diffraction, UV-Visible (DRS) and
transformation. Moreover, textural textural properties of samples were
properties are improved after doping with determined by nitrogen adsorption-desorption
lanthanum in favor of better formic acid isotherms at 77 K. The photocatalytic tests are
adsorption and photocatalytic properties described elsewhere [2].
enhancement. 3. Results and Discussion
Key words: TiO2 nanotubes, nanorods,
lanthanum, photocatalysis, formic acid. 3.1 Characterization
1. Introduction Figure 1 shows the variation of Anatase

crystallites size of TiO2 nanomaterials versus
the post-thermal treatment. It seems clear constants of Lanthanum free nanomaterials

that doping with lanthanum inhibit the (NT and NR) decrease up-on post-thermal
growth of anatase crystallites size whatever treatment (Table 2). However, La-NT and La-
TiO2 morphology (NT or NR). With NR nanomaterials show so far interesting
respect to NT and NR, smaller TiO2 photocatalytic activities in the degradation of
crystallites sizes (#8 nm) are obtained with formic acid. This is due to the stabilization of
La-NT and La-NR nanomaterials at anatase phase in presence of small TiO2
calcination temperature lower than 773K. crystallites size. In addition, improvement of
For higher temperatures, small TiO2 surface area after doping with lanthanum
crystallite sizes are always obtained for La- favors the formic acid adsorption over La-NT
NT and La-NR. Knowing that the and La-NR nanomaterials and enhances their
transformation of TiO2 from anatase to photocatalytic activities.
ruttile phase requires a crystallite size
around 14 nm. Therefore, La-NT and La- Table 2: Constants rate of nanomaterials un-doped
NR nanomaterials are potential candidates and doped with Lanthanum
in which anatase phase remains stable at TiO2 NT k TiO2 NR k
materials (mol.L- materials (mol.L-
high post-thermal treatment.This result is 1
min-1) 1
min-1)
in accordance with previous works [3, 4]. NT-673 44.5 NR-673 70
Textural properties are summerized in NT-773 44 NR-773 42
Table 1. Results reveal that doping TiO2 NT-873 29 NR-873 16
nanomaterial with lanthanum increases the NT-973 11 NR-973 13
specific surface area. La- NT-673 30 La- NR-673 64.5
La- NT-773 44 La- NR-773 59.5
La- NT-873 47 La- NR-873 62
La- NT-973 43 La- NR-973 43.5
4. Conclusions
TiO2 with controlled morphologies, namely:
nanotubes and nanorods are successfully
obtained. La-doped TiO2 nanomaterials open
new alternatives to highly efficient
photocatalyst for the degradation of formic
acid. The degradation of more complex
molecules is under study.
Figure 1: Anatase crystallite size
References
Table 1: Textural properties [1] Santiago-Morales, J., Aguera, A., Del Mar Gomez, M.,
TiO2 NT Surface TiO2 NR Surface Fernandez-Alba, A. R. Transformation products and
materials area materials area
reaction kinetics in simulated solar light photocatalytic
(m2.g-1) (m2.g-1)
degradation of propranolol using Ce-doped TiO2. Appl.
NT-673 214 NR-673 123
Cata. B. 2013, 129, 13-29.
NT-773 135 NR-773 75
[2] Turki, A., Kochkar, H., Guillard, C., Berhault, G.,
NT-873 81 NR-873 41
Ghorbel, A. Effect of Na content and thermaltreatment
NT-973 30 NR-973 9
oftitanate nanotubes on the photocatalytic degradation of
La-NT-673 183 La- NR-673 140
formic acid. App. Cata. B. 2013, 138-139, 401-415.
La- NT-773 175 La- NR-773 125
La- NT-873 143 La- NR-873 91 [3] Liqiang, J., Xiaojun, S., Baifu, X., Baiqi, W., Weimin, C.,
La- NT-973 77 La- NR-973 48 Hongganga, F. The preparation and characterization of
La doped TiO2 nanoparticles and their photocatalytic
3.2 Photocatalytic tests activity. J. of Solid State Chem. 2004, 177, 33753382.
[4] Kumaresan, L., Prabhu, A., Palanichamy, M., Arumugam,
The kinetic study, conducted under UV
E., Murugesan, V. Synthesis and characterization of Zr4+,
light, showed that photocatalytic
La3+ and Ce3+ doped mesoporous TiO2: Evaluation of
degradation of formic acid followed their photocatalytic activity. J. of Hazard. Mater. 2011,
pseudo-first order kinetic. Moreover, rate 186, 11831192.
Characterization and catalytic isomerization of light alkanes but several

problems are associated to the Pt catalysts.
behaviour of MoO3/TiO2
The present work deals with the preparation,
catalyst in the isomerisation of by sol-gel method, and the characterization of
n-hexane. MoO3/TiO2 catalysts for the isomerisation of
Maroua SOUISSI1*, Jihene ARFAOUI1 n-hexane.
Abdelhamid GHORBEL1 and Zouhaier
KSIBI1
2. Experiment
1
Laboratoire de Chimie des Matriaux et de Catalyse, 2.1 Materials
Universit Tunis El Manar, Campus Universitaire Tunis Titanium propoxide, propanol, nitric acid,
El Manar, 2092, Tunis, Tunisia. ethyl acetoacetate and Molybdenyl
(*) corresponding author: E-mail:
maroua.s.fst@gmail.com
acetylacetonate.
Abstract: 2.2 Catalysts preparation
MoO3/TiO2 catalysts containing different The required amount of molybdenum,
amounts of molybdenum (5, 10, 15 and 20 corresponding to 5, 10, 15 and 20 wt% of
wt% of MoO3) were prepared by sol gel MoO3, was deposited on TiO2 though sol-gel
method and characterized by N2 method, before the hydrolysis stage. The
physisorption, XRD, H2-TPR, FTIR and obtained gel was dried under the hyper-critical
UV-visible spectroscopy. These catalysts conditions of the solvent and then calcinated
were reduced under H2 during 12 h at at 500 C for 11 h.
400 C then tested in the n-hexane
isomerization. The results showed that 2.3 Catalytic tests
MoO3/TiO2 catalysts are characterized by The catalytic behaviors of the MoO3/TiO2
high surface area and developed only the solids, reduced under H2 during 12 h at
anatase phase of TiO2. It was also shown 400 C, were evaluated in the isomerization of
that the reduced MoO3/TiO2 catalysts are n-hexane reaction, using 200 mg of the
active in the n-hexane isomerization in the catalyst.
temperature range of 360-400 C. Their
activity increases with the increase of 3. Results and Discussion
molybdenum amount. The N2 physisorption results (Table 1)
shows that all the MoO3/TiO2 solids are
Key words: Titania; Molybdenum; sol-gel; n- classified as mesoporous materials and exhibit
hexane isomerization. high surface area and pore volume. The
decrease of the textural properties in the case
1. Introduction of Ti-20%Mo catalyst is explained by the
The conversion of linear hydrocarbons to blockage of the pores of this solid by
their corresponding branched isomers by molybdenum species [1]. The XRD patterns
isomerization reaction has taken show that all the catalysts develop only the
importance in recent years for petroleum diffraction peaks of anatase phase of TiO2 and
refining. The isomerization of n-alkane, is the absence of diffraction peak of
an important catalytic process to produce molybdenum species indicate that they are
clean fuel by increasing the octane number highly dispersed on TiO2 support. The
of the gasoline and eliminating undesired infrared spectroscopy demonstrate the
aromatic compound. presence of Mo=O terminal band only for the
catalyst containing 20% of MoO3 [2]. The H2-
The catalytic performances of platinum TPR profiles of MoO3/TiO2 catalysts show
deposited on chlorinated alumina or zeolite two reduction peaks, attributed to the
have been widely explored in the
reduction of molybdenum species from The reduction of these materials under H2

MoO3 to MoO2 and from MoO2 to Mo [3]. during 12 h leads to active catalysts in the n-
hexane isomerization. The high activity is
UV-visible study gives similar results for
all the catalysts. Therefore, several bands obtained, at 380 C, with the catalyst
containing 20 % wt of MoO3.
corresponding to TiO2 anatase are observed
between 200-400 nm. The bands observed Reference
between 350-385 nm are attributed to the [1] Hafsia Belatel, These, Universit Louis Pasteur de
molybdenum species. Strasbourg, (2005)
[2] M.Navgire, A.Yelwande, D.Tayde, B.Arbad, M. Lande.
Table 1: Textural properties of the MoO3/TiO2 Chinese Journal of Catalysis 33( 2.) (2012)2768.
Catalyst SBET Vp Dp () [3] J. B. de Paiva Jr, W. R. Monteiro, M. A. Zacharias, J. A.
(m2/g) (cm3/g) J. Rodrigues, G. G. Cortez. Brazilian Journal of Chemical
Ti-5%Mo 116 0,176 61 Engineering 23( 4) (2006) 517 - 524,
Ti-10%Mo 153 0,305 80 [4] H. Al-Kandari, F. Al-Kharafi, A. Katrib. Isomerization
Ti-15%Mo 177 0,314 57 reactions of n-hexane on partially reduced MoO3/TiO2
Ti-20%Mo 116 0,226 58 Catalysis Communications 9 (2008) 847852.
All the reduced MoO3/TiO2 catalysts are

active in the isomerization reaction (Figure
1) and produces several isomers: the 2,2-
dimethylbutane (22DMB), the 2,3-
dimethylbutane (23DMB), the 2-
methylpentane (2MP) and the 3-
methylpentane (3MP). It seems that the
reduction of the catalysts under H2 leads to
the formation of MoO2(Hx)ac active sites in
the isomerization reaction [4]. The high
catalytic activity is obtained in the case Ti-
20%Mo catalyst.
Figure 1: The catalytic activity of MoO3/TiO2

catalysts in n- hexane isomerization depending on
reaction temperature.
4. Conclusions
This study demonstrates that MoO3/TiO2
catalysts, containing different molybdenum
amounts (5, 10, 15 and 20 wt% of MoO3),
are characterized by high surface area and
developed only the anatase phase of TiO2.
Adsorption and photocatalytic metals. In the literature, a number of studies

have revealed that vanadium doped ZnO
degradation of malachite improve optical and structural properties of
green by vanadium doped zinc ZnO [35]. ZnO:V3% photocatalyst has been
oxide nanoparticles synthesized by a modified sol-gel method
Lotfi Khezami under supercritical conditions. The
photocatalytic effectiveness of this material is
Al Imam Mohammad Ibn Saud Islamic University investigated on malachite green dye under
(IMSIU), College of Sciences, Department of
Chemistry, Riyadh 11432, Saudi Arabia
darkness and visible light.
2. Experiment
Abstract:
The objective of this study is to assess Vanadium doped ZnO and pure ZnO catalysts
the removal of malachite green dye (MG) was prepared by modified sol gel method:
from aqueous medium by vanadium-doped amount of zinc acetate was dissolved in
zinc oxide nanopowder. The nanopowder methanol and appropriate amount of
was characterized by various techniques ammonium metavanadate was added. The
such as particle size analysis, transmission solution was placed in an autoclave and dried
electron microscopy (TEM), X-ray under supercritical conditions. Obtained
diffraction (XRD) and photoluminescence powder was heated under air conditions at
(PL). Batch experimental procedures were 300C during 24 hours. Adsorption and
conducted to investigate the adsorption and photocatalytic activities were studied using
photocatalytic degradation of malachite the systems: catalyst/ MG/obscurity and
green dye from aqueous solution. catalyst/ MG/ halogen 100 W respectively.
Adsorption kinetics investigations were Varied parameters were MG initial solution
performed by varying the amount of the and catalyst concentrations. The concentration
catalyst and the initial dye concentrations. of the dye was determined by
Adsorption and photocatalytic degradation spectrophotometer (Labomed, Inc., UVS-
data were modeled using the pseudo-first- 2800) at its maximum wavelength (618 nm).
order and the pseudo-second-order kinetic
equations, and the mass transfer and intra- 3. Results and Discussion
particular diffusion models. The results 3.1 Nanoparticles characterization
showed that the ZnO:V3% nanopowder was
X-ray diffraction and TEM show a crystalline
particularly effective for the removal of
phase with a particle size ranging between 15-
MG and data were found to comply with
30 nm. Upon heat treatment at 500 oC for 2 hs
pseudo-second-order kinetic model.
in air, room temperature PL spectra of the
Key words: Nanostructures; Sol-gel; Malachite obtained ZnO:V3% nanoparticles showed a
green ; Photocatalytic degradation; Adsorption ;
strong yellow luminescence where the
kinetics.
position depend on wavelength excitation. The
1. Introduction observed luminescence band can be attributed
Nanoparticulates oxides such as TiO2 and to deep level in band gap of zinc oxide. The
ZnO are increasingly being used as defect produced by the incorporation of
photocatalysts for mineralization of toxic vanadium in zinc oxide may improve the
organic compounds. However, it is photocatalytic activity of the obtained semi-
generally known that these semiconductors conductor under visible irradiation.
are poor absorbers of photons in the solar 3.2 Adsorption study
light due to their wide band gap (3.2 eV) 3.2.1 Effect of initial concentration of MG
[1, 2]. One strategy that has been The effect of the initial concentration of MG
investigated for improving photocatalytic was investigated in the range 25 - 700 mg.L-1
activity is to dope semiconductors with with constant amount of ZnO:V3% (0.2 g.L-1).
different elements such as transition 90 to 99% of the initial MG was adsorbed.
3.2.2 Effect of the amount of ZnO:V3% 240 min with pseudo-fisrt order constant of
Three amounts of ZnO:V3% (100, 300 and 7.0 10-3 min-1 .
500 mg.L-1) were considered on the 0.60 1
0 min
kinetic study of the MG removal at 25

0.8
0.53 30 min
0.6
60 min
C/C0
0.4
1C with initial concentration of MG 0.45
0.2
90 min
equal to 30 mg.l-1. Rapid initial rise of

120 min
Absorbance
0
0.38 180 min
0 50 100 150 200 250
adsorption capacities qt and equilibrium 0.30 Time, min

240 min
was almost reached within 120 min. The 0.23
adsorption rate was considerably enhanced 0.15
by the addition of catalyst and equilibrium 0.08
is reached faster with a mass of catalyst 0.00
about 500 mg.L-1 and the adsorption is 300 400 500 600 700
(nm)
better pronounced.
Fig.1: Visible Photocatalytic degradation
3.2.3 Kinetic study spectra of ZnO:V3% at different visible
Two kinetic models are tested in order to irradiation times.
predict the data of MG adsorption: pseudo- Compared to adsorption phenomena, one can
first order and a pseudo-second order. conclude that adsorption is the step controlling
Obtained results are presented in table.1. the kinetic of the global photocatalytic
Table 1: Rate adsorption constants at different
process
mass of catalyst 4. Conclusions
2 2
mZnO:V k1 x 103 r k2 x 10 3
r
3%
(min-1)
t1 Optical properties of the 3% vanadium
(%) (g.mg-1 min- (%) 2
(mg/L) 1
) (min)
doped ZnO shows the existence of the
100 6.45 91.4 0.222 99.6 66.98 promising deep centers for the deterioration of
300 8.06 91.5 0.256 99.4 37.46 MG using visible radiation. The optical study
500 8.75 90.7 0.510 99.6 30.96 illustrates the charge transfer between the
deep levels and the band-gap of the ZnO host
The validity of the kinetic models is tested
matrix. The produced vanadium doped zinc
by the magnitude of the regression
oxide seems to be an effective material for the
coefficient r2, given in table 1. one can
photocatalytic degradation of malachite green
clearly note that adsorption kinetics obey
and the use of visible irradiation improves the
to pseudo-second order model. Indeed this
time of its removal from waste water
model presents the highest correlation
coefficient (> 99.4 %). Moreover, from the Acknowledgment
values of k2 which are proportional to the L. Khezami acknowledges King Abdul-Aziz City for
Sciences and Technology (KACST) for the financial support
mass of the catalyst, one can confirm the under the national Plan for Science and Technology Program
first conclusion made in paragraph 3.2.2., (NPST)-Project No: 08-ENV429-08.
that greater the mass is faster the References
equilibrium is reached.
[1] Xu J., Chang Y., Zhang Y., Ma S., Qu Y., Xu C., Applied
3.3 Photodegradation study Surface Science 2008,225, 1996-1999.
Kinetic photocatalytic activity was studied [2] Xiao Q., Zhang J., Xiao C., Tan X., Materials Science and
for several MG and catalyst initial Engineering 2007, B 142, 121-125.
concentrations. Fig.1 shows the results [3] El Mir L., El Ghoul J., Alaya S., Ben Salem M., Barthou
obtained in the case of a 500 mL
C., von Bardeleben H. J., Physica 2008, B 403, 1770
suspension of 30 mg.L-1 of MG and
1774.
ZnO:V3% (125 mg) irradiated by halogen
lamp 100 W. [4] R. Krithiga, G. Chandrasekaran, Crystal Growth 2009,
Adsorption ratio was found to be equal to 311, 4610-4614.
67% in obscurity. However [5] Wang L., Meng L., Teixeira V., Song S., Xu Z., Xu X.,
photodegradation ration is about 80 % after Thin Solid Film 2009, 517, 3721-3725.
Organic effluent impregnation Comparison of R2 and R3 gives information of

what is really adsorbed: R2 indicates the
on different biomasses at effluent organic part held by the support while
laboratory scale R3 shows the amount of water involved during
G. Daragon1, G. Trouv2, the impregnation. Ratios are given as follow:
G. Leyssens,3 and C. Schnnenbeck4 m m0 R0
i R1
R0
Laboratoire Gestion des Risques et Environnement, m0 % DM s
Institut de Recherche J.B. Donnet, 3 bis, rue A. Werner
(mi md )
68093 Mulhouse, France. R2 R1 * %DMe R3
guillaume.daragon@uha.fr, gwenaelle.trouve@uha.fr m0 * % DM s
gontrand.leysssens@uha.fr
cornelius.schonnenbeck@uha.fr With: m0: mass before impregnation (g); mi: mass
after impregnation (g); %DMs: support dry matter
(%); %DMe: effluent dry matter (%) and md: mass
Abstract: after impregnation and drying (g).
In this study, three types of biomasses
(beech (Bch), miscanthus (Msc) and spruce 3. Results and Discussion
(Spc)) have been tested as impregnation
These first results (Table 1 below) show
media for an industrial organic effluent
that Msc (a dry grass) seems to be an
(IOE). Impregnation ratios have also been
interesting candidate, especially because of its
calculated.
huge adsorption surface comparing to
woodchips. However Spc is less compact and
Key words: Wood impregnation, organic
more porous than Bch, explaining the
effluent, biomass, waste treatment
difference between both.
1. Introduction Table 1: Impregnation ratios results
Tests R0 R1 R2 R3
In recent years, many authors have
focused their attention of using biomass for Bch 0.26 0.42 0.24 0.63
effluent treatment. Indeed those materials Msc 0.67 0.74 0.42 0.98
such as wood, sawdust, bark, straw or even Spc 0.29 0.51 0.29 0.76
sludge, are usually byproducts themselves,
widely available and cost-effective. Due to 4. Conclusions
their good adsorption properties, they are
considered as an interesting impregnation Three different biomasses have been
support alternative [1-3]. impregnated showing they retained from 24%
to 42% of IOE dry. Several studies are
2. Experiment intended concerning the influence of effluent
dilution, biomass moisture and granulometry,
2.1 Impregnation method in order to go further in the impregnation
50 g of each biomass sample (10 for understanding.
Msc) was separately immerged in 1 L of References
IOE for 4 h, and dripped for 4 h to be [1] Crini, G. Recent developments in polysaccharide-based
finally dried at 105 C for 24 h. materials used as adsorbents in wastewater treatment.
2.1 Impregnation ratios calculations Progress in Polymer Science, 2005, 30, 3870.
[2] Ahmaruzzaman, M. Adsorption of phenolic compounds
Four different ratios have been calculated: on low-cost adsorbents: A review. Advances in Colloid
R0, R1, R2 and R3. R0 (g IOE raw / g and Interface Science, 2008, 143, 4867.
biomass raw) and R1 (g IOE raw / g [3] Yu, L.J., Shukla, S.S., Dorris, K.L., Shukla, A.,
biomass dry) are useful indicators since Margrave, J. Adsorption of chromium from aqueous
both ratios directly reveal the amount of solutions by maple sawdust. Journal of Hazardous
effluent retained by the biomass. Materials, 2003, 100, 5363.
EFFECT OF PREPARATION alkanes over bifunctional acid catalysts such

PARAMETERS ON THE SYNTHESIS as catalysts based on Pt/Al2O3 or transition
OF AEROGEL CATALYSTS BASED metals supported by sulfated zirconia.
ON ZIRCONIA DOPED Heteropolyacids (HPAs) can be ecofriendly
HETEROPOLYTUNGSTIC ACID acid solids with high thermal stability and
high surface area by supporting them onto
Samir CHAKHARI1,*, Mohamed Kadri suitable supports like silica [5], titania [6],
YOUNES1, Abdelhamid GHORBEL1, and MCM-41 [7] zirconia [8]. The aerogels
Alain RIVES2 prepared by sol-gel method attracted much
attention in our laboratory for the preparation
1. Laboratoire de Chimie des Matriaux et de Catalyse, of bifunctional acid catalysts [1-3]. The aim of
Campus Universitaire Tunis El Manar, 2092, Tunis, this work is to study the effect of the
Tunisie, (*) corresponding author: E-mail: hydrolysis ratio and the content of the dopant
samir.chakhari@gmail.com. on the characteristics and catalytic properties
2.Unit de catalyse et de chimie du solide, UMR CNRS of aerogel bifunctional acid catalysts based on
8181, Universit des Sciences et de Technologies de Lille,
Bt C3, 59655 Villeneuve dAscq, France. zirconia doped with heteropolytungstic acid.
Abstract: 2. Experiment
Aerogels zirconia doped 2.1 Catalyst preparation
heteropolytungstic acid (HPW) were Aerogels based on zirconia doped
prepared by sol-gel method and dried in heteropolytungstic acid (HPW) were prepared
supercritical solvent conditions. The following the sol-gel process. In the first step,
increase of molar hydrolysis ratio in the the precursor zirconium (IV) propoxide was
catalysts preparation step stabilizes better dissolved in propan-1-ol. Then HPW was
zirconia tetragonal phase. Thus surface added with different atomic ratios nW/nZr.
area is developed. Additional carbide The hydrolysis was performed with dropwise
species appear when the degree of addition of distilled water using variable ratio
hydrolysis increases. These properties h = nH2O/nZr. Drying is the next step of the
confer to catalyst a high reactivity in n- preparation which consists in removing the
hexane isomerization in the whole solvent under its supercritical conditions from
temperature range investigated. However, the wet gel in an autoclave to provide the
the increase in the content of HPW is not a aerogel solids. Obtained catalysts are designed
favorable factor for these properties and as AZrHPWyhx, with A: aerogel, Zr: Zirconia,
therefore the catalytic properties are less HPW: heteropolytungstic acid, y = nW/nZr,
developed. hx: hydrolysis ratio = nH2O/nZr.
Key words: Aerogel; Heteropolytungstic acid; 2.2 Catalyst characterization

Zirconia; n-hexane isomerization
Adsorption-desorption isotherms of N2 at
77 K were performed with a Micromeritics
ASAP 2020 apparatus after outgassing the
1. Introduction
solids at 473 K for three hours.
Skeletal isomerization of alkanes has XRD patterns were obtained on a Siemens
important applications because branched D-5000 powder diffractometer using Ni-
alkanes are useful as clean high-octane filtered Cu K radiation ( = 1,5418 ).
fuel. This process is a refinery process that XPS experiments were performed on a
in fact produces significant quantities of Kratos Analytical AXIS Ultra DLD
the ideal component of reformulated spectrometer. AlK = 1486.6 eV source was
gasoline. There are also a number of used for excitation. The X-ray beam diameter
reports detailing hydroisomerization of n- is around 1 mm. The spectrometer BE scale
was initially calibrated against the Ag The catalytic properties of the aerogels
3d5/2 (368.2 eV) level. Pressure was in the zirconia doped heteropolytungstic acid have
10-10 Torr range during the experiments. been evaluated in the n-hexane isomerization
2.3 Catalytic reaction between 423 and 493 K. The aerogel
AZrHPW0,1h3 exhibits the highest catalytic
n-Hexane isomerization was performed activity. This result is expected given that this
between 150 and 220 C in a U shaped catalyst has more developed texture, structure
tubular reactor operating at atmospheric and contains carbide species which can be
pressure. A mechanica l mixture of 100 mg generators of active site in this type of
of aerogel with 100 mg of Pt/Al2O3 was e reaction.
x posed to a stream of n-hexane (20 Torr)
diluted in hydrogen (total flow rate : 30
cc/min). Reaction products were analyzed 4. Conclusion
by online gas chromatography using a
Aerogels zirconia doped with
flame ionization detector.
heteropolytungstic acid solids were prepared
3. Results and Discussion by the sol-gel and autoclave methods. The
3.1 Results increase in the hydrolysis ratio has a
beneficial effect on the development of texture
The BET surface areas of the prepared and structure. Therefore the stabilization of
aerogels are compiled in Table 1. The the active sites in n-hexane isomerisation
surface area of the aerogels increases with reaction while the enrichment of catalyst by
the hydrolysis ratio. This development of heteropolytungstic acid seems to be
the texture of the catalyst is probably unfavorable factor for the catalytic properties.
related to the structure of the gels formed
during the hydrolysis step performed by
more substitution of alcoholates groups References
(OPr). [1] Miyaji. A, Echizen. T, Li. L, ;T. Suzuki, Yoshinaga.Y,
Okuhara. T, Catal. Today, 2002, 74, 291- 297.
Table 1: Textural properties of the [2] N. Kamoun, Younes. M. K, Ghorbel. A, Mamede. A. S,
aerogels AZHPWxhy. Rives. A, J. Porous Mater, 2012, 19, 375-381.
[3] Mejri. I, Younes. M. K, Ghorbel. A, Eloy. P, Gaigneaux.
E. M, J. Porous Mater 2010 17,545-551
Catalysts SBET (m2/g) [4] Raissi. S, Younes. M. K, Ghorbel. A, F. Garin, J Sol-Gel
Sci Technol 2010, 53,412417
HPW 3.5
[5] Pizzio L.R, Cacares. C.V, Blanco. M.N, J. Appl. Catal. A
AZrHPW0,1h1 113 1998, 167, 283-294.
AZrHPW0,1h3 252 [6] Jalil. P.A, Al-Daous. M.A, Al-Arfaj. A.R.A, Al-Amer.
AZrHPW0,5h3 235 A.M, Bel-tramini. J, Barri. S.A.I, J. Appl. Catal. A, 2001,
207,159-171.
The XRD patterns of the aerogels show [7] Patel. S, Patel. A, Indian J. Chem, Sect A, 2002, 41, 528-
that the increase in the hydrolysis ratio 531.
[8] Maksimov. Y. V, Suzdalev. I. P, Tsodikov. M.V, Kugel.
makes develop ZrO2 tetragonal phase. It is
V.Y, Butenko. O.V, Slivinky. E.V, Navio. J.A, Study of
known that the development of this phase
cumene oxidation over zirconia-titania and alumina-based
is accompanied by the improvement of complex oxides obtained by solgel meth-ods: activity-
textural properties of the catalyst [1-4]. In structure relationships, J. Mol. Catal. A: Chem, 1996,
addition the XPS results reveal the 105,167-173.
presence of carbide species when the
degree of hydrolysis increases. However
when the content of HPW increases the
ZrO2 tetragonal phase is not well
developed.
Experimental study and efficiency was negligible for solar intensities

close to 800 W/m2.
performance testing The time taken for drying of tomato
of an indirect solar dryer slices was 12 hours for mono thin layer
1,2 2
Rda Khama , Farida Aissani and Rezak configuration and 10 hours for the first layer
3 in the four thin layers case. In this last, the
Alkama difference between the four durations of
1. Universit Kasdi Merbah de Ouargla, Laboratoire de
Gnie des Procds, Facult des Sciences et de la drying was one hour between each tray.
Technologie et des Sciences de la Matire, Ouargla Key words: Indirect solar dryer; Convection;
30000 Algrie, redkhama@yahoo.fr Efficiency; Abacus; Kinetics.
2. Universit A. Mira de Bejaa, Dpartement de Gnie
des Procds, Facult de Technologie, Bejaia 6000
Algrie, benissadfarida@yahoo.fr
3. Universit A. Mira de Bejaa, Laboratoire de Gnie
Electrique, Facult de Technologie, Bejaia 6000
Algrie, rezak_alkama@yahoo.fr
Abstract:
In this paper, we present an indirect
solar dryer realized with industrial
dimensions to dry food products and
consisting of two main parts (Flate plate
solar collector and drying chamber). The
major specificity of this device is that it
can operate in natural and in forced
convections, what is rarely found in
previous works and scientific literature.
This work includes a detailed description
with a contribution to the understanding of
some phenomena occurring during the
operation of the solar dryer, knowing that
drying is a unit operation in process
engineering. In order to analyze the
behaviour of the apparatus, we have first
test the solar collector and then we realized
drying of tomato taken as wet product.
All the results from the experiments
led us to conclude the good behaviour and
consequently the proper functioning of the
dryer. Indeed, tests were conducted in
passive and active modes that led to a
relationship between the collector air
temperature at the outlet and the essential
ambience parameters. An abacus was
established for values of the solar radiation
and the velocity respectively in ranges of
2
400 to 800 W/m and 0.2 to 1.40 m/s,
allows determining the collector efficiency
and the air temperature rise (See Figure 1).
The average value of the collector
efficiency was 51.33 % in active mode and
32.32 % in passive one. The effect of the
air velocity in the collector on its
1
A Multiphase Flow Model for dissolution, residual trapping so the

phenomenon of diffusion and convection.
Modelling CO2 Storage in Several authors have studied the problem of
Deep Saline Aquifer CO2 storage in porous media, the mass
Reservoirs transfer of CO2 injected into a homogenous
(1,*)H. JEDLI, (1)S. BOUZGARROU and sub-surface porous formation saturated with a
(2)K.SLIMI
liquid. For this configuration, it was depicted
(1)Ecole Nationale dIngnieurs; Universit de that the density-driven natural convection
Monastir, Rue Ibn Eljazzar, 5019, Monastir, enhances the mass transfer rate of CO2 into the
Tunisie initially stagnant liquid (Farajzadeh, 2007,
(2)Institut Suprieur du Transport et de la 2009). Studies related to natural convection
Logistique, Universit de Sousse, B. P. 247, phenomena can be used as a tool in selecting
Cit Erriadh, 4023, Sousse, Tunisie optimal fields with maximum transfer rates of
*Corresponding author: Tel/Fax: CO2 into water. It has been observed that the
+21673501597; E-mail: jedli.hedi@yahoo.com rate of mass transfer of CO2 into water is
Abstract higher for heterogeneous media (Farajzadeh,
World energy consumption is greatly 2011). The mass transfer of dissolved CO2 and
increasing in recent years. In this context, the coupling behaviors of mass transfer with
fossil fuels such as oil, gas and coal will the mineral reactions of aqueous CO2 with
continue to play an important and rocks over a wide range of spatial and
dominant role. This growth led to an temporal scales has been examined (Ji, 2011).
increase in greenhouse gas emissions, Double diffusive natural convection of CO2 in
which are largely responsible for global cavities filled with brine saturated porous
warming. Faced to this situation, several media has also been investigated (Islam,
solutions are planned to obtain a 2013).
significant reduction in CO2 emissions,
control of energy consumption, the
development of energies with better carbon
footprint and the enhancement of
techniques used for the capture as well as
the underground storage of CO2.
The problem of the long-term storage of
the captured CO2 is complex given the
huge volumes involved. The CO2 must be
stored for several hundreds or thousands of
years, with low cost and low
environmental impact.
Among the possible options, the most
satisfactory solution from the
environmental standpoint is the transport
of the CO2 by pipeline and its injection into
deep geological formations, like gas
reservoirs and oil fields that are depleted or
nearing depletion, or deep saline aquifers.
The later are generally situated at depths
greater than aquifers containing potable
water.
This type of storage is funded by a
combination of chemical and physical
mechanism such as the structural and
stratigraphic trapping, solubility trapping:
applications of this energy is the convergence

Efficiency investigation of a of solar radiation into heat and then transfer
the heat to a fluid. The solar energy collected
flat plate solar collector in is carried from the circulating fluid either
dynamic behavior directly to the hot water or space conditioning
equipment or to a thermal energy storage tank
Hamed Mouna1, Fellah Ali2 and Ben [1].
Brahim Ammar3 Solar collectors are the key component of
Research Unit of Applied Thermodynamics, National
School of Engineers of Gabes, University of Gabes solar-heating systems. There are two types of
St Omar Ibn El-Khattab, 6029 Gabes, Tunisia. solar collectors: non-concentrating and
concentrating [2]. Flat plate solar collectors
E-mails: Hamedm@hotmail.fr (Correspondent author)
al.fellah@gmail.com
(FPSC) belong to the rst category.
ammar.benbrahim@enig.rnu.tn Solar collector thermal performance can be
characterized by a steady-state or a dynamic
Abstract: model. Many authors have studied the
The efficiency of a solar collector is a key performance and optimization of FPSC under
factor for the performance of thermal steady state or quasi-steady conditions [3,4].
facilities. As the weather conditions vary Research concerning dynamic modeling is
continuously during the day, the instant essential to adequately characterize the
collector efficiency depends not only on transient behavior of solar thermal collectors.
the components employed in its At this point it should be mentioned that a
construction but also on the actual dynamic model can be very useful because it
environmental conditions. A theoretical provides information about the collector
research was performed to describe the behavior and facilitates experimental tests. In
transient behavior of a flat plate solar the literature there are several studies about
collector field under outdoor working these types of models, however only a few of
conditions. Considering time dependent, them regard the dynamic performance of solar
thermo-physical properties and heat mass thermal collectors [5, 6].
transfer coefficients the transient model 2. Mathematical model
was established regarding the energy
balance conservation for the glass cover, In the present study, a detailed simulation
the air gap between cover and absorber, the model for a flat plate solar collector
absorber and the working fluid. considering the transient properties of its
The aim of this approach is to find different zones was developed. The collector
different configuration of the system in operations are described by the energy
order to help decisions makers to choose conservation equations written for all the
among a variety of design and system components. The mathematical model
operations. A set of equations representing obtained comprises four primary equation
the model was simultaneously solved. The sets: (i) heat-balance equation of the
results are used to investigate the effect of transparent cover; (ii) heat-balance equation
the design parameters and of the operating of the air trapped between transparent cover
conditions on the performance of the and the absorber; (iii) heat-balance equation of
collector such as outlet water temperature the absorber; and (iv) heat-balance equation
and efficiency. for water in the heat pipe.
Key words: Dynamic simulation, optimization, i) Heat balance for the glass cover
dTC
Efficiency. M C CC h r,C-sky SC Tciel -TV h cv,C-ambSC Tamb -TC h r,C-abs SC Tabs -TC h cv,C-a SC Ta -TC
dt
1 abs
U loss Se,C Tamb -TC CSCG SCG C C 1
1. Introduction 1 C 1 abs
In the recent years solar energy has ii) Heat balance for the air gap
dTa
been strongly promoted as a viable energy a Va Ca h cv,C-a SC TV -Ta h cv,abs-aSabs Tabs -Ta Uloss Se,a Tamb -Ta 2
dt
source. One of the simplest and most direct iii) Heat balance for the absorber
dTabs
MabsCabs h r,C-abs Sabs TC -Tabs h cv,abs-aSabs Ta -Tabs h cv,abs-f Sech,f Tf -Tabs 3 140
dt 120
C abs 120 110
loss,b loss,e Tamb -Tabs SabsG
Outlet water temperature(C)

1 C 1 abs
100
100
90
80
80
70
iv) Heat balance for the transfer fluid 60
60
Dint-Tube Tf T 40
f Cf v f h cv,abs-f Tabs -Tf 4 50

4 dt dx 20
0
40
0.005 20 30
3. Results and Discussion Wate
r flo
w
0.01
rate
(Kg/s
0.015
) 0.02 5
10
Time (h
)
15
Figure 1 shows the evolution of the Figure 3: Variation of outlet water temperature
outlet water temperature versus time and versus water mass flow rate.
the length of the absorber tube. It might be 0.9
noted that the temperature of the fluid is 0.85
0.8
proportional to the length of the absorber 0.75
tube and the solar radiation. From figure 2
Efficiency
0.7
it appears that the efficiency during a day 0.65
0.6
is quite sensitive to the variation of the 0.55
fluid inlet temperature. 0.5
0.45
The plots in figure 3 of outlet fluid 0 0.01 0.02 0.03 0.04 0.05 0.06
Water flow rate (Kg/s)
0.07 0.08 0.09 0.1
temperature versus water flow rate depicts Figure 4: Variation of efficiency versus water mass
that the peak of outlet temperature flow rate for constant time (12:00 h).
increases with the decrease of flow rate. It
appears that the current results are similar 4. Conclusions
to those presented by Dagdougui et al. [4]. In this paper, numerical investigations on
Figure 4 illustrates the effect of the water the thermal behavior of a flat plate solar
flow rate on the flat plate solar collector collector with a single glass cover in transient
efficiency for a constant time (12:00h).It condition have been performed. The goal was
can be seen that the efficiency of the to evaluate the influence of various
collector increases with increasing water meteorological and design parameters on the
mass flow rate. collector performance.
References
80 [1] Szen A; T, Menlik T; nvar, S. Determination of
75
70
efficiency of flat-plate solar collectors using neural
90
80
65 network approach, 2008, 35, 1533-1539. (Expert
70
60
Systems with Applications).
Temperature(C)
55
60
50
[2] Mekhilef, S; Saidur, R; Safari,A. A review on solar
50 45 energy use in industries, 2011, 15, 17771790.
40
40
2
(Renewable and Sustainable Energy Reviews).
35
30
)
(m
1.5
[3] Jinwei, A; Jie, J; Yang, Z; Aifeng, Z; Wen, F.
be
30
tu
1
20
of
0.5
Experimental and theoretical study of the efficiency of
th
18 16
ng
14 12
Le
10 8 0
6
Time (h)
a dual-function solar collector, 2011, 31, 1751-
Figure 1: Variation of the outlet temperature
1756. (Applied Thermal Engineering)
versus the length of tube (21 June).
[4] Dagdougui, H; Ouammi, A; Robba, M; Sacile, R.
Thermal analysis and performance of a solar water
heater flat plat collector: Application to Ttouan
(Morocco). 2011, 15, 630-638. (Renewable and
Sustainable Energy Reviews).
[5] Kong, W; Wang, Z; Fan, J; Bacher, P; Perers, B;
Chen, Z; Furbo, S. An improved dynamic test
method for solar collectors. 2012, 86, 1838-1848.
(Solar Energy).
[6] Amrizal, N; Chemisana, D; Rosell, J; Barrau, J. A
Figure 2: Variation of the efficiency versus time dynamic model based on the piston ow concept for the
at different inlet water temperature. thermal characterization of solar collectors. 2012, 94,
244-250. (Applied Energy).
Disposal of Olive Mill nowadays they undergo a second oil

extraction by chemical process in seed-oil
Wastewater through factories in order to extract residual oil which
Impregnation on Olive Mill leads to generation of Exhausted Olive Mill
Solid Waste and Combustion Solid Waste (EOMSW). OMSW are
Nesrine Kraiem1,2,3, Marzouk Lajili1, constituted by variable quantities of pulp, olive
Sophie Dorge2, Mejdi Jeguirim3, Slimane stone, residual oil and high degree of
Zerelli4, Rachid Said1 polyphenols and fats unlike EOMSW [3].
1. Unit de Recherche dEtude des Milieux Ioniss et Tunisia like the Mediterranean countries
Ractifs (UR EMIR), IPEIM, Avenue Ibn El Jazzar, produces large quantities of olive byproducts
Monastir 5019, Tunisia,
2. Laboratoire Gestion des Risques et Environnement,
estimated in 2009 by ANGED [4] to be
Universit de Haute Alsace, 3 bis rue Alfred Werner, annually in kt: 600-1200 of OMWW, 435-800
68093 Mulhouse, France, OMSW and 120-170 of sludge. In front of
3. Institut de Science des Matriaux de Mulhouse, CNRS,
UMR-7361, 3 bis rue Alfred Werner, 68093 Mulhouse, these quantities [4], Tunisia will face a serious
France, challenge to find an environmentally and
4. Socit Zouila, Route de Boumerdes km 7 BP 8, economically viable solution in handling and
Mahdia 5100, Tunisia,
disposal of OMWW since the common way
Abstract: was soil spreading which has a significant
negative effects. Recently, operational
Oil byproducts introduce economical,
procedures have been tested to recover the
technical and organizational constraints
OMWW energetic potential [5]. For EOMSW,
that make difficult the adoption of
the thermal conversion is the main recovery
environmental approach for waste disposal.
process due to its high heating value around
A combined process which includes
18 MJ.kg-1 and low sulphur (0.01-0.04%)
absorption on low-cost absorbents and an
content [1]. Thermal treatment of combined
energetic valorization via combustion was
disposal of OMWW and EOMSW presents
studied. Exhausted Olive Mill Solid Waste
many environmental advantages such as
(EOMSW) was found to be an effective
reduction of mass, volume disposed solid,
low cost absorbent of OMWW. The
reduction of gaseous emissions to the
thermal degradation of EOMSW and
atmosphere as well as the reduction of energy
impregnated OMWW in EOMSW with
consumed in mills and seed-factories. In fact,
fraction of blend 1/5 named impregnated
adding OMWW to EOMSW with proportions
solid waste (ISW) was studied under inert
suitable with biomass combustion standards is
and oxidative atmosphere by
counterproductive in energy conversion
thermogravimetric analysis (TGA). The
processes which improve governmental
obtained results indicate that the ISW has
economy and avoid factories to pay disposal
interesting physicochemical characteristics
costs. This present work aimed to study the
and thermal degradation behaviour to be
feasibility of the use of EOMSW as
used as a biofuel for energy recovery.
absorbents for OMWW and the combustion of
Key words: Exhausted Olive Mill Solid Waste,
the obtained mixture. Hence, physicochemical
Impregnated Solid Waste, TGA.
charactersitics are detrmined. In addition,
1. Introduction thermogravimetric analysis (TGA) has been
used to evaluate the thermal behaviour in inert
The disposal and treatment of OMWW and oxidative atmospheres of exhausted olive
constitutes a critical environmental
mill solid waste and impregnated exhausted
problem because of the high degree of olive solid waste (1/5).
organic pollution (COD/BOD ratio
between 2.5 and 5), pH slightly acid [1] 2. Experimental procedure
and high content of recalcitrant compounds Sample of OMWW used in this study were
such as lignins and tannins [2]. Virgin collected from olive mill (three-phase
OMSW have been used as animal feed but centrifugal olive mill) located in Mahdia,
100 0,06
Tunisia. EOMSW samples were provided 90

EOMSW_IA
ISW (1/5)_IA
0,05
by a seed-factory also in Mahdia. 20 kg of 80
70
Mass loss X (%)

0,04
dX/dt (%.s-1)
EOMSW with 10% (wb) of moisture were 60
50 0,03
slowly added to 100 kg of OMWW with 40

0,02
89% (wb) of moisture. The impregnated 30
20
0,01
EOMSW are put in a barrel, mixed 10
0 0
regularly, and dried in order to reduce 0 200 400
Temperature (%)
600 800
initial water content in the mixture which Figure 1: TG and DTG curves of EOMSW and
was initially 76% (wb). The water content, ISW (1/5) under inert atmosphere at 5C.min-1.
bulk density, ash content (evaluated 100
90
EOMSW_OA
ISW (1/5)_OA
0,1
according two norms) and low heating 80 0,08
70
Mass loss X (%)

value are initially determined. Secondly,
dX/dt (%.s-1)
60 0,06
Thermogravimetric analyses (TGA) were 50
40 0,04
carried out under inert and oxidative 30
20 0,02
atmospheres. 10
0 0
0 100 200 300 400 500 600
3. Results and Discussion Temperature (%)
Figure 2: TG and DTG curves of EOMSW and

The table 1 shows analyzes performed on
raw samples. Moisture should be further ISW (1/5) under oxidative atmosphere at 5C.
reduced and their density increased by min1.
pellitisation. The values for EOMSW are 4. Conclusion
within the typical ranges in literature for
LHV at reception and ash [1], [6] and meet The combined process of the treatment of
guiding values specified by the European olive mill wastewater presented in this work,
standards. The ash content of ISW is may be a promising issue for the valorization
suitable to maintain high operating comfort of the organic content of OMWW and
for residential heating sector. therefore reduce their environmental impact.
Table 1: Results of the analyses References
Sample property EOMSW ISW (1/5) [1] A. C. Caputo, F. Scacchia, and P. M. Pelagagge,
Moisturewb (%) 12 30 Disposal of by-products in olive oil industry: waste-
Bulk densitywb (kg.m-3) 529 549 to-energy solutions, Applied Thermal Engineering,
LHVdb,R (kJ. kg-1) 18445 17391 vol. 23, no. 2, pp. 197214, Feb. 2003.
Fixed Carbon (%) 24 18 [2] E. Erolu, . Erolu, U. Gndz, and M. Ycel,
Volatile matter (%) 63 64 Comparison of physicochemical characteristics and
photofermentative hydrogen production potential of
Ash, 550db (%) 3 7
wastewaters produced from different olive oil mills in
Ash, 815db (%) 3 5 Western-Anatolia, Turkey, Biomass and Bioenergy,
vol. 33, no. 4, pp. 706711, Apr. 2009.
Figures 1 and 2 shows the mass loss (X) [3] M. T. Miranda, J. I. Arranz, S. Romn, S. Rojas, I.
and the derivative of mass loss (dX/dt) Montero, M. Lpez, and J. A. Cruz, Characterization
of grape pomace and pyrenean oak pellets, Fuel
curves obtained during the degradation of Processing Technology, vol. 92, no. 2, pp. 278283,
EOMSW and ISW under inert and Feb. 2011.
oxidative atmospheres. The impregnated [4] ANGED, Strategic Options for the promotion of
Value of Organic Waste VDO Tunisia. 2009.
EOMSW samples behaved like olive solid [5] M. T. Miranda, A. Cabanillas, S. Rojas, I. Montero,
residue under inert and oxidative. However and A. Ruiz, Combined combustion of various phases
it is important to note that the thermal of olive wastes in a conventional combustor, Fuel,
vol. 86, no. 3, pp. 367372, Feb. 2007.
degradation of ISW degradation starts [6] A. R. Celma, S. Rojas, and F. Lpez-Rodrguez,
earlier. Such behavior is attributed to the Waste-to-energy possibilities for industrial olive and
potassium content in OMWW. In fact, grape by-products in Extremadura, Biomass and
Bioenergy, vol. 31, no. 7, pp. 522534, Jul. 2007.
authors found that added potassium [7] Anker Jensen, Kim Dam-Johansen, Marek A.
catalyze the combustion of biomass unlike Wojtowicz, and Michael A. Serio, TG-FTIR Study of
inherent minerals in the raw product [7]. the Influence of Potassium Chloride on Wheat Straw
Pyrolysis, Energy & Fuels, vol. 12, pp. 929938, Jan.
1998.
Hydrogen storage on But, the success of such economy depends on

our ability to discover efficient and cost-
physically activated carbons effective hydrogen storage materials for
derived from olive stones automotive and stationary applications. In
Najoua Bader1, Renju Zacharia2, Daniel recent year, there has been considerable
Cossement2 and Abdelmottaleb Ouederni1 experimental and theoretical interest in the use
of carbonaceous materials as potential
1. Research Laboratory: Process Engineering and hydrogen sorbents [1]. Therefore, the scope of
Industrials Systems, Chem. Eng. Dept, National School of
Engineers of Gabes, Gabes University, St. Omar Ibn this work is to study the hydrogen adsorption
Khattab, 6029 Gabes, Tunisia properties of a physically activated carbon
Najoua.bader@gmail.com, derived from olive stones. First, we
2. Institut de recherche sur lhydrogne, Universit du characterized its porous texture, using
Qubec Trois-Rivires, 3351 boul des Forges C.P. 500, automatic adsorption systems. Then, hydrogen
Trois-Rivires, Qubec, Canada G9A 5H7 storage was measured at 77K, and at low
renju.zacharia@uqtr.ca, Daniel.cossement@uqtr.ca
pressure(less than 0.1MPa), by the same
porosity analyzer. For high pressure (up to
Abstract: 20MPa), we used a homemade volumetric
An activated carbon derived from olive device, built up at the Institut de recherche sur
stones, and physically activated by CO2 at lhydrogne (IRH, Canada).
1173 K, was tested for hydrogen storage. 2. Experimental
Our carbon had shown a high volume of
micropores(0.43cm3.g-1), with homogenous Lignocellulosic materials such as olive stones
pore size distribution. Its microporosity was used as precursor for granular activated
was of narrow range (<0.7nm). H2 carbon. Physical activation of this precursor
adsorption was measured at 77K and up to was performed by CO2 gas, preceded by a
20MPa. At 77 K and 5 MPa, H2 uptake carbonization under nitrogen atmosphere, and
reached 3wt%, with no considerable the carbon was named CA- CO2. For
hysteresis on the isotherm. characterizing its porous texture we used
nitrogen adsorption/desorption at 77K
Key words: hydrogen storage, activated carbon, (Micromeritics, ASAP2020). From N2
olive stones, CO2 activation, narrow micropores. adsorption isotherm, the DFT pore size
distribution and the apparent BET surface area
1. Introduction (SBET) were obtained. Application of t-plot
As a global society, we need to method led to the internal surface area
aggressively develop sustainable (Sinternal) and the total volume of micropores
renewable integrated energy systems. The (Vt). Further, we used adsorption of CO2 at
technical community agrees that our 273K for measuring the volume of narrow
climate system cannot absorb the carbon micropores (<0.7nm). At 77K and below
(in the form of CO2) that would result in 0.1MPa, hydrogen adsorption isotherms were
the use of our remaining hydrocarbon performed using Micromeritics ASAP 2020.
energy reserves without catastrophic While, at the same temperature and up to
consequences. Our next-generation energy 20MPa the isotherms were carried out in a
systems must be based on essentially an homemade volumetric devise.
infinite resource (wind, solar, nuclear), be 3. Results and Discussion
truly zero emissions in CO2, and be
available to all. Hydrogen has its place in Some of the properties of the carbon are
the upcoming future as an energy vector. summarized in Table 1. The carbon is
microporous with a narrow pore size
distribution and all its surface area is internal.
Table1: Porous texture of CA-CO2 References

[1] Strbel, R.; Garche, J.; Mosely, P.T; Jorissen, L.; Wolf,
SBET Sinternal Vt VCO2 G. Hydrogen storage by carbon materials. Power
Carbon
/m2.g-1 / m2.g-1 /cm3.g-1 /cm3.g-11 Sources. 2006, 159, 781801.
[2] Menon, P.G .Adsorption at high pressures.
Chem.Rev.1968, 68, 277-294.
CA-CO2 1185 1078 0.43 0.47
The adsorption-desorption isotherms are

illustrated in Figure 1. According to the
IUPAC classification, hydrogen adsorption
corresponds to type I.
Figure1:H2adsorption-desorption
isotherms at 77K and up to 20MPa
The excess adsorption typically peaks at an
elevated pressure (5MPa) and then
decreases as the hydrogen gas density
increases yet further. This behavior is
typical for high pressure adsorption at
supercritical temperature [2]. The
adsorption and desorption isotherms show
good reversibility, with no observable
hysteresis, which indicates a pure
physisorption.
4. Conclusions
Hydrogen adsorption at liquid nitrogen
temperature and high pressures was
investigated on a CO2-activated carbon.
Volumetric measurements showed a good
adsorption capacity (3 wt%), which can be
directly related to the considerable narrow
microporosity of our carbon.
Progress in Attrition distribution. The present contribution will

focus on the attrition analysis induced by the
Comprehension during rub of (4 mm radius) hemispherical
Conveying Processes polystyrene particles against smooth and
Rim Ben Arfi1, Achraf Ghorbal2, and functionalized silicon walls. Several
Ammar Ben Brahim2 experimental and structural factors affecting
attrition of polymeric particles such as the
1. National Engineering School of Gabs, Gabs velocity (V), the applied normal force (FN),
University, Rue Omar Ibn-Elkhattab 6029 Gabs,
Tunisia, E-mail: rimbenarfighorbal@yahoo.fr (R.B.A.) polymer molecular weights, and the wall
2. Applied Thermodynamics Research Unit, National surface energy are discussed.
Engineering School of Gabs, Gabs University, Rue
Omar Ibn-Elkhattab 6029 Gabs, Tunisia, E-mails:
achraf.ghorbal.issat@gmail.com (A.G.); 2. Experimental Methods
ammar.benbrahim@enig.rnu.tn (A.B.B.)
A homemade device, depicted in Figure 1,
was used to carry out a single slide of the
Abstract:
polystyrene hemispherical particle onto
The present contribution will focus on the different silicon walls.
attrition analysis induced by the rub of
hemispherical polystyrene particles against
smooth and functionalized silicon walls.
Several experimental and structural factors
affecting attrition of polymeric particles
such as the velocity, the applied normal
force, polymer molecular weights, and the
wall surface energy are discussed.
Key words: Attrition, polystyrene, conveying Figure 1: Homemade original device for attrition
experiments.
process, interface.
This original attrition device has been
essentially developed to carry out a single
1. Introduction passage of the single hemispherical particle
onto silicon substrate (simulating the pipeline
Polystyrene (referred to as PS) is an wall). The sliding velocity was ranged from
engineering thermoplastic, widely used in 0.1 to 25 mm/min (to simulate velocity of
chemical engineering applications, e.g. particles on pipelines wall). The FN was
processes in fluidized beds, materials ranged from 1 to 7 N (to simulate particles
handling and transport processing (e.g., density in conveying pipelines).
screw, pneumatic and hydraulic convey) PS hemispheres were obtained by molding
[1], and so on. In many of these industrial the polymer (obtained by anionic
processes PS is used as granulates and polymerization) at 220 C during 20 minutes.
subjected to various stressing conditions. Hydrophilic substrates silanol-enriched
However, the whole description of silicon wafers (Si-OH) and hydrophobic
chemical, physical, rheological and substrates methyl-terminated silicon surfaces
interfacial origins of aggregates damage (Si-CH3) were obtained after the piranha
(e.g., Attrition) is not yet entirely available treatment and the adsorption of SAMs,
[2]. respectively.
In fact, attrition has harmful effects on Topographical measurements of transferred
product quality and on the process (under attrition effect) PS onto silicon surfaces
reliability because of changes in particle were realized using tapping mode atomic
properties such as particle shape and size force microscopy. Phase and height images
were recorded simultaneously using a break PSs macromolecular chains and

commercial Dimension 3100 AFM therefore generate attrition.
equipped with a Nanoscope IIIa controller Moreover, owing to AFM measurements, it
(Digital Instruments, Santa Barbara, USA). clearly appears that the applied normal force
values required to induce PS attrition
appearance onto methyl-terminated walls are
much higher comparing to values required to
Table 1 shows a summary of the observe the same phenomenon onto hydroxyl-
molecular weight average and the terminated silicon walls. It is important to note
polydispersity index of the polystyrene that no PS-245 and PS-385 attrition has been
samples used in this study observed during experiments onto
Table 1: Average molecular weight and hydrophobic walls.
polydispersity index derived from gel-permeation On the basis of AFM observations, it is
chromatography
well-established that the normal force needed
PS name Mw Ip for PS-26 attrition appearance is always lower
PS-26 25940 1.11 than that required for the PS-118, whatever
PS-118 118098 1.10 the wall surface energy. This implies that PS-
PS-245 245326 1.12 26 softening temperature is more easily
PS-385 384985 1.09 reached. On the other hand, the force required
to pull out shorter macromolecular chains (PS-
Attrition experiments were performed to
26) and generate the attrition appearance is
evaluate the beginning of polymeric
therefore lower.
particles damage against a model wall (see
Figure 2). In this attempt, we varied, at
first, the applied normal force, hemispheres 4. Conclusions
velocity and the wall surface energy. Reported results show that a critical value
of normal force and velocity are necessary to
activate attrition mechanisms. Moreover, PS
hemispheres attrition phenomenon is tightly
related to experimental and structural
parameters.
Acknowledgment
This work was supported in part by the Institut
Suprieur des Sciences Appliques et de
Figure 2: AFM tapping mode images of PS-26 Technologie of Gabs (Tunisia).
attrition appearance on hydrophilic wall. Image
area 2m x 2m. Height range is 15nm. The
References
transfer appears under a FN equal to 3 N and for
a V of about 1 mm.min-1. [1] Kalman, H.; Rabinovich, E. Analyzing threshold
Attrition appearance of PS-26, PS-118, velocities for fluidization and pneumatic conveying,
PS-245 and PS-385, on hydrophilic Chem. Eng. Sci. 2008, 63, 34663473.
[2] Ghorbal, A.; Ben Arfi, R.; Mokhtar, F.; Zrelli, A.; Ismaili,
surfaces, occurred for 1.29 N, 1.8 N, 1.65
S.; Grisotto, F.; Charlier, J.; Palacin, S. Polystyrene
N and 2.03 N tangential forces values, Tribological Performance: Progress in the Understanding
respectively. On the basis of these values, of Polymers Attrition during Chemical Engineering
one can say that quite identical shear stress Processes; In Polystyrene: Properties, Performance and
(a mean value of about 21 MPa, taking into Applications; Gray, J. E., Eds.; Nova Science Publishers
account experimental uncertainties) was New York, 2011. pp. 138.
needed to generate attrition of four PSs. [3] Ghorbal, A.; Ben Arfi, R.; Bistac, S.; Brogly, M.
Thus, one can say that a critical shear Polystyrene chains orientation: A rubbed and non-rubbed
stress is needed in order to disentangle, polymer comparative study, Chem.Phys.Lett. 2007, 443,
352355.
pull-out, reptate, conform [3] and probably
Adsorption equilibrium causing unpleasant odor [3]. The ultimate goal

of this work is to identify an effective and
studies for o-xylene vapour inexpensive adsorbent (HDTMA organoclay)
and clay materials system in order to reduce concentration of volatile
Nesrine DAMMAK1,2*, Nadim organic compounds (VOCs) in effluent
FAKHFAKH1,2, Sophie streams from environmental concern.
FOURMENTIN3,4and Mourad 2. Experiment
BENZINA1,2
The raw clay used in this study was a
1.University of Sfax, 3029 Sfax, Tunisia. bentonite supplied from Jebel Sbih deposits
2.Water, Energy and Environment Laboratory, Code AD located in the south of Tunisia from the area
10-02 ENIS, B.P. 3038, Sfax, Tunisia of Skhira. The
3.Universit Lille Nord de France, F-59000 Lille, France hexadecyltrimethylammoniumbromide
4.ULCO, UCEIV, F-59140 Dunkerque, France
(HDTMA) used for intercalation was obtained
*Corresponding author email: dammak.nes@gmail.com from fluka Analytical. O-xylene was obtained
also from Fluka Chemical and was chosen as
model compound in this study.
Abstract:
Tunisian bentonite was used to prepare 2.1 Experimental Set Up
modified clay by intercalating of HDTMA organoclay material was prepared
hexadecyltrimethylammoniumbromide by dispersing the cationic surfactant HDTMA
(HDTMA). Clay materials were used as equal to twice the cation exchange capacity of
adsorbent for the investigation of the the clay which was of 0.85mmol.g-1, into Na
adsorption isotherms, saturation capacity saturated clay under stirring at 80C for 10h
and thermodynamic parameters of o- [1, 2].
xylene, a toxic volatile organic compound, For the determination of the o-xylene
by gravimetric method at three different adsorption isotherms on raw and modified
temperatures 20, 30, and 40C. The clay materials, we used the gravimetric
adsorption isotherms were analyzed by method (figure 1).
Langmuir, Langmuir-Freundlich and Toth
equations. Mass transfer coefficient of o-
xylene is evaluated using Uptake curve
method. Results show that the isotherm
was well fitted with LangmuirFreundlich
isotherm model. The adsorption capacities
of o-xylene on HDTMA organocly at 20C
were 600mg.g-1. Thermodynamic
parameters revealed an exothermic
adsorption process in nature. Overall mass
transfer coefficient values are in the order
of 10-4s-1.
Figure 1: Experimental set up for adsorption
isotherm studies [4].
Key words: Adsorption isotherm; o-xylene;
organoclay; Mass transfer coefficient 3. Results and Discussion
3.1 Results
1. Introduction
The comparison of different modelss
Adsorption is becoming more and more (Langmuir, LangmuirFreundlich and Toth)
popular technique for removal or recovery predictions with the experimental data for o-
of pollutants. O-xylene is generally xylene adsorption on HDTMA organoclay at
considered to be one of the organic 20C are presented in Figure 2. Therefore, it
pollutants discharged into the environment may be concluded from the above
observations that all of used isotherm Table 1: Equilibrium capacities and overall mass
models satisfactorily explain the transfer coefficients for o-xylene on clay material
equilibrium adsorption behaviour of o-
C q k x 104 (s-1)
xylene on HDTMA organoclay.
(g/g) Law Global Long
(kg.m-3)
time time time
0.006 0.12 0.62 1.97 3.72
0.008 0.16 0.73 2.17 4.13
0.014 0.20 0.79 2.33 4.36
0.22
0.017 0.92 2.46 4.46
4. Conclusions
O-xylene adsorption on clay materials follows
Brunauer type-I adsorption isotherm.
Figure 2: Comparison of different isotherm Langmuir, LangmuirFreundlich and Toth
models with experimental data generated for o- isotherm models well describe the
xylene in clay material at 20C. experimental isotherm data. Heat of
adsorption values both by vant Hoff equation
Isosteric heat of adsorption increases non- and ClausiusClapeyron equation are in the
linearly with increase in saturation order of 104J.mol-1. The overall mass transfer
adsorption capacity (Figure 3) but all the coefficient values lie mostly within 10-4s-1.
values lies in the order of 104J.mol-1.
References
[1] He, H., Frost, R. L., Bostrom, T., Yuan, P., Duong, L.,
Yang, D., Xi, Y., Kloprogge, J. T. Changes in the
morphology of organoclays with HDTMA+ surfactant
loading. Appl. Clay Sci., 2006, 31, 262-271.
[2] Li, Z., Jiang, W. T. A thermogravimetric investigation of
alkylammonium intercalation into rectorite. Thermochimica
Act., 2009. 483, 58-65.
[3] Huang S., Zhang C., He H. In situ adsorption-catalysis
system for the removal of o-xylene over an activated carbon
supported Pd catalyst. Journal of Environmental Sciences.
2009, 21, 985990 .
Figure 3: Variation of isosteric heat of [4] Jarraya, I., Fourmentin, S., Benzina, M., Bouaziz, S. The
adsorption with equilibrium adsorption capacity. characterization of prepared organoclay materials (DDMA)
and gas sorption of chlorobenzene. Can. J. Chem. Eng. 2011,
89, 392-400.
Shape of the particle is very important [5] Ruthven, D.M. Principles of Adsorption and Adsorption
while diffusive transport is concerned. Processes, Wiley, New York, 1984.
However, the overall mass transfer
coefficient can be obtained from the
Deff
equation: k = 15 2 . To assume the
Rp
validity of the approximation of mass
transfer coefficient, low time, long time
and global time are compared (table 1).
A new sol-gel route for the

synthesis of ZnO-SnO2
nanocomposites with
enhanced photocatalytic
activity
Abdessalem Hamrounia, Noomen Moussaa,
Agatino Di Paolab, Francesco Parrinob,
Ammar Houasa, Leonardo Palmisanob
a Unit de Recherche Catalyse et Matriaux pour
l'Environnement et les Procds URCMEP
(UR11ES85); Facult des Sciences de Gabs /
Universit de Gabs; Campus Universitaire -Cit
Erriadh- 6072 Gabs, Tunisie.
b Schiavello-Grillone Photocatalysis Group,
Departemento di Ingegneria, Chimica dei Processi
e dei Materiali, Universita di Palermo, 90128
Palermo, Italia.
Abstract
ZnO-SnO2 mixed photocatalysts were
synthesized by a new sol-gel route and
characterized by X-Ray Diffraction,
Diffraction Ray Spectroscopy, Surface area
analyzer, and Scanning Eelectron
Microscopy. The photocatalytic activity of
the samples was evaluated on the
photodegradation of 4-Nitrophenol and
was found to be relative to the ZnO/SnO2
molar ratio and to the calcination
temperature. The results showed that the
mixed photocatalysts exhibit a higher
activity compared to the pure oxides
because of the heterojunction systems. The
most active photocatalyst was ZnSn0.05
synthesized at 600C for 2h. The high
photocatalytic activity of the
nanocomposites was investigated by the
determination of the flatband potential
using the photovoltage measurements.
Key words: ZnO-SnO2, heterojunction,
sol-gel, photodegradation, 4-nitrophenol.
Study on the chemical Nowadays, attention has been focused on

natural extracts as favoring agents and also
composition of Eucalyptus conservative one against food spoilage. For that
oleosa essential and its effect reason, researches are focused on natural
alternatives, to substitute synthetic additives. This
when incorporated into a study examines the effect of Eucalyptus oleosa
Turkish delight essential oil when incorporated into a Turkish
Dorsaf Ben Hassine1,3,4, Asma Souaihi2, delight, mainly the antimicrobial activity and the
preservative properties.
Hager Dabbebi3, Jalloul Bouajila4 and
Manef Abderrabba1 2. Materials and Methods
1.
Laboratoire Matriaux Molecules et 2.1Plant material
Applications,IPEST, La Marsa, 2070.
dorsaf_benhassine@yahoo.fr; Eucalyptus oleosa leaves were picked from
manef@ecopark.rnrt.tn; Hajem Layoum arboretum, in kairouan, on
2. Institut Superieur des SciencesBiologiques april 2009.
Appliques De Tunis.
asma.souaihi@gmail.com ; 2.2 Eucalyptus essential oil extraction
3. Institut National Agronomique de Tunis,
debbabih@gmail.com;
The extraction of Eucalyptus essential oil was
4. Laboratoire des IMRCP-UMR CNRS-UPS carried out by hydrodistillation using
5623,Universit Paul Sabatier, Toulouse , Clevenger type apparatus during 3 hours.
France.
jalloul.bouajila@univ-tlse3.fr.
2.3 Chemical identification of E.oleosa
essential oil
Abstract: GC-MS was used to identify the chemical
The Turkish Delight Loukoum is a confection composition of E. oleosa essential oil
considered as traditional and occasionally
2.4 Turkish delight monitoring
Different recipes of loukoumTurkish delight
consumed in Tunisia. It is a mixture of sugar,
were prepared (35 trials) by mixing water,
starch, water and lemon juice. starch, sugar and lemon juice [1], and
The aim of this work is the development of a new allowing them cook on low heat by two
formula of loukoum flavored with Eucalyptus
methods (A: malaxing all ingredients together,
B: preparing glucose syrup than adding the
oleosa essential oil. Thus we are interested in the
other ingredients (water, starch). The prepared
physico-chemical analysis of the product, its samples were subjected to sensory analysis by
sensorial characterization, and the antimicrobial 30 untrained consumers (nave panel).
effect of E. oleosa essential oil once incorporated
Microbiological criteria such as the
determination of total bacteria (mesophilic,
into loukoum during storage. This study is carried
thermophilic and psychrophilic) and the
out to investigate the effect of the incorporation of enumeration of yeasts and molds were
Eucalyptus oleosa essential oil on loukoum in established.
both sides: the inhibition of the growth of some 3. Results and Discussion
microbial strains (such as yeasts and fungus) and 3.1 Extraction of essential oil
the determination of the shelf-life of this product.
The yield of E. oleosa essential oil was
In our knowledge, it is a first time that a such study about 6.62%.
is done. 3.2 Chemical composition
The family of oxygenated monoterpenes
Key words: (Eucalyptus, essential oil, GC-MS
was the most prevalent (51.77%), represented
Turkish delight, antimicrobial activity). by the main compound 1,8-cineole with an
amount of (31.94%). Then we noticed the
presence of compounds belonging to the
1. Introduction family of hydrocarbon monoterpenes
(30.23%), represented by the o-cymene, with
an amount of (17.93%). We also noted the established at the end of this step. We found
presence of various other compounds with that the Turkish delight flavored with
a low percentage. Eucalyptus folral water and with 50 L
3.3 Turkish delight monitoring essential oil, were the most valued by the
consumers.
The nine best recipes were selected, and
their sensory profile has been drawn, based In a second step, we determined the
on descriptive characteristics of the microbiological and physicochemical
Turkish delight namely: color, smell, qualities, of different samples of Turkish
elasticity and texture, in order to choose delight flavored with various doses of
the recipe most appreciated to achieve the essential oil stored at three temperatures 25
incorporation of essential oil (Figure 1). C, 35 C and 45 C, and during 15 days.
The Recipe from diagram B was the most A comparison between the various samples
appreciated. showed that the variation of temperature
affects the organoleptic qualities (color,
couleu Color
r recette 8 texture and elasticity). Proper storage
7 temperature was 25 C. It guarantees a better
5 recette7
Appr 3
Global appreciationgout taste texture and keeps the elastic properties and the
ciati -11 recette 6 golden color of our product.
elastici textur recette 5 However, no change in the physico-chemical
t e
recette 9 quality (pH, acidity) was observed.
elasticity
The microbiological control showed that all
Figure 1: Sensory profile of samples of samples supplemented with E. oleosa essential
Turkish Delight. oil inhibited the microbial growth particularly
3.4 Eucalyptus oleosa essential oil of yeasts and molds. It is a dose dependent
incorporation effect, mostly provided by oxygenated
In this part of work, we are interested in monoterpenes such 1,8- cineole [1] .
the incorporation of various essential oil
doses (50L to 200L/500g sample) in the
Turkish delight. The different samples References
were kept at various temperatures 25,35 [1] http://fr.wikipedia.org/wiki/Loukoum
and 45 C. Microbiological analysis [2] Ben Hassine, D.; Abderrabba, M.; Yvon, Y.; Lebrihi , A.;
Mathieu, F.; Couderc, F. ; Bouajila, J. Chemical
showed that essential oils have an Composition and in Vitro Evaluation of the
inhibitory effect on the growth of yeasts Antioxidant and Antimicrobial Activities of Eucalyptus gillii
and molds, as well as mesophilic and Essential Oil and Extracts. Molecules. 2012, 17, 9540-9558.
thermophilic bacteria. We have also shown
that temperature affects the organoleptic,
physicochemical and microbiological
properties. We noticed also that tha
antimicrobial activity is dose dependent.
4. Conclusions
The found results showed that the
monitoring process affects the organoleptic
qualities of Turkish delight. Recipe 9,
from diagram B was chosen. It represents a
smooth texture appreciable elasticity. The
incorporation of different doses of E.
oleosa essential oil in the formulation of
Turkish delight and a sensory analysis was
SIMULATION OF processed. The separation of uranium from

wet process phosphoric acid (WPA) has
URANIUM EXTRACTION gained considerable importance. It is practiced
ALONG A CONTINUOUS for two main reasons: to produce uranium as a
COLUMN by-product and to prevent the contamination
Khleifia Naima, Saanoun Siwar, Hamdi of soil by the radionuclide elements and rare
Rania and Hannachi Ahmed earth metals through fertilizers.
Solvent extraction has been found to be a
Chemical engineering and industrial systems unit, successful process for industrial recovery of
National Engineering School of Gabes, University of uranium from phosphates, although other
Gabes, Tunisia (naima_khleifia@yahoo.fr)
methods such as ion-exchange [4], membrane
Abstract separation [5] and precipitation [6] have been
The increased growth in energy demands investigated.
has a direct impact on the growing interest Uranium recovery from WPA using solvent
of uranium extraction. Phosphoric acid extraction involves these steps: (i) phosphoric
attracts a great attention because of its acid pre- treatment, (ii) uranium extraction,
uranium content. The solvent extraction is (iii) uranium purification by re-extraction, (iv)
the most widely used techniques for product recovery, and (v) post - treatment of
uranium separation from phosphoric acid. uranium depleted acid [1]. Most of these steps
In the present work, the simulation of the are liquid-liquid extraction operations.
uranium extraction along a continuous Because of the complexity of such operations,
counter current column has been the choice of the best operating conditions has
conducted. A computer code that accounts been a challenging task for engineers.
for mass balances and equilibrium data has In the present work, the simulation of the
been developed. The performed uranium extraction from WPA in continuous
simulations allow to obtain the counter current extraction column is
concentration profiles of uranium along the conducted. The simulation is based on a
extraction column and led to assess the fundamental model that integrates the material
effect of operating conditions on the conservation equations with the mass transfer
extraction performances. kinetics data obtained from experimental
Key words: continuous column, simulation, study. The developed computer code allows to
obtain the concentration profiles of uranium
solvent extraction, uranium, phosphoric acid.
along the extraction column. The influence of
1. Introduction the extraction rate on the extraction
performance is studied.
Rock phosphate is a vital input for
increased food grain production, required 2. Modeling of uranium extraction
to feed the growing populations of the In this work, modeling of the uranium
developing countries. Tunisia has a extraction is based on material conservation
number of fertilizer plants, which process equations on the extraction column. Figure 1
the rock phosphates into phosphoric acid describes a continuous counter current
and fertilizers, by the dihydrate process. extraction column. The uranium content xF in
Uranium is known to occur in phosphates feed flow rate F is extracted with an organic
with concentration ranging from 50-200 solvent countercurrent feed flow rate of S with
ppm [1-3]. In the dihydrate process, more a uranium content of ys. The WPA is brought
than of 80% of the uranium contained in into contact with the solvent to lead to a
the raw material passes into the phosphoric raffinate R having a residual uranium content
acid in the form of U(IV) and U(VI) ions of xR. The extract, designed by E, leaves with
[1]. The potential for recovery of uranium uranium content yE. The column extraction is
from the phosphates is substantial when supposed to be of a height H and a cross
large amounts of phosphate rock are section A.
by D2EHPA-TOPO, the equilibrium data are

needed. We have used the experimental data
performed on laboratory scale to determine
the equilibrium isotherm.
For a given set of operating conditions, the
computer code gives the concentration
profiles of uranium in both phases along the
extraction column. A typical result for a
solvent rate of 0.5 and uranium content in the
feed acid xF 30 ppm is reported. Figure 2
shows the simulation raffinate and extract
uranium content profiles. The concentration of
uranium in the aqueous phase decreases from
the top to the bottom of the extraction column.
This result provides valuable information on
Figure 1: Schematic representation of the intensity of uranium transfer along the
extraction column extraction column. Much of the mass transfer
occurs close to the WPA inlet zone in the top
The developed model that accounts for of the extraction column.
mass balances and equilibrium data is 30 50
defined par the following system:
dx A.kC a. y ( x) y y
Uranium content in aqueouse phase, x (ppm)
Uranium content in organic phase, y (ppm)

40
1 x
x
25
dz R
A.kC a. y ( x) y
30
dy 1 y
20
dz E 20
dR
A.kC a. y ( x) y
15
10
dz
dE dR 10 0
dz dz
0 0,2 0,4 0,6 0,8 1
Dimensionless column height
The differential problem has to be solved Figure 2: Uranium concentration profiles

with the following initial and boundary along extraction column
conditions: 3.2 Effect of solvent rate
for z 0, x xR , y yS
(10) The solvent rate is an important parameter of
for z H , x x F uranium extraction process. Hence it is
The equations of the model are solved necessary to consider the impact of this
simultaneously by the method of Runge- parameter on the uranium extraction
Kutta Fehlberg using the Matlab software. performances. The computer code enables to
3. Results and Discussion study the effect of solvent rate on uranium
distribution between the two phases of
3.1 Uranium Concentration profiles extraction.
The computer code has been For different solvent rates, the uranium
implemented to simulate the uranium concentration in the extract, y, along the
extraction using the synergistic mixture of column is shown in figure 3. When the solvent
Di2ethyl Hexyl Phosphoric Acid rate decreases the uranium concentration
(D2EHPA) and TriOctyl Phosphine Oxide increases. That is, the solvent rate has to be
(TOPO) diluted in kerosene as extractant. carefully chosen to find a compromise
In order to simulate the uranium extraction between the uranium concentration of WPA in
the extract and the solvent amount.
liquid membrane from phosphoric acid media.

Hydrometallurgy, 2009 , 96, 117122
80
=0.25 =0.5 =0.75 [6] Weterings, K.; Jansen, J. Recovery of uranium, vanadium,
=1 =1.25
yttrium and rare earths from phosphoric acid by a
Uranium content in organic phase, y(ppm)
precipitation method. Hydrometallurgy, 1985, 15, 173

60
190.
40
20
0
0 0,2 0,4 0,6 0,8 1
Dimensionless column height
Figure 3: Uranium concentration in

organic phase for different solvent rates
4. Conclusions
In the present work, simulation of
uranium extraction in continuous counter
current extraction column was performed.
Steady state material balances and
equilibrium data was integrated to model
the extraction process. A computer code
has been developed to determine the
uranium concentration profiles along
extraction column and to investigate the
effect of operating conditions. Thus, the
developed computer code could be used as
a tool for predicting the uranium extraction
results in order to look for the optimal
operating conditions.
Acknowledgment
The authors thank the Tunisian Chemical
Group for continuing support of this
research.
References
[1] Hurst FJ. Uranium from phosphoric acid, ORNL,
Tennessee 37830, 1983
[2] Botella, T.; Gasos, P. Recovery of uranium from
phosphoric acid: an overview. IAEA-Tecdoc 533,
1989.
[3] Magdi, R.; Mohammed K. Uranium fuel as
byproduct fertilizer production, INREC 10, Jordan,
2010.
[4] Kabay, N.; Demiricioglu, M.; Yayh, S.; Gunay, E.;
Yuksel, M. Recovery of uranium from phosphoric
acid solutions using chelating ion-exchange resins.
Ind Eng Chem Res , 1998, 37, 19831990.
[5] Joshi, JM.; Pathak, PN.; Pandey, AK.; Manchanda,
VK. Study on synergistic carriers facilitated transport
of uranium(VI) and europium(III) across supported
rich content of tannins. The main colouring

Extraction of natural dye compound in the dye is Flavogallol [7] and
from the fresh peel of having reasonable good light, wash and rub
pomegranate fruits fastness to get different shades, apply the dye
on textile material already pretreated with
Process optimization
mordents
Mabrouk Marwa1, Ben Ali Samia2 and 2. Experiment
Ouederni Abdelmotaleb
1
Laboratoire de gnie de procds et systmes industriels Aqueous extraction of color from the fresh
2
Mail : marwa8829@hotmail.fr peel of pomegranate :
Laboratoire de gnie de procds et systmes industriels
Mail : benali.samia@gmail.com The fresh collected peel with average size of
0.1 cm were used for the extraction. Different
Abstract: mass of peel (10g, 5g, 3.33g, 2.5 g, 2 and1g)
Dyes obtained from different natural was taken in 50 ml erlenmeyer flasks. 20 ml
sources have emerged as an important distilled water was added to each flask in
alternative to synthetic dyes [1] [2]. order to keep the plant materials fully
Pomegranate peel (Punica grantum) with immersed in the solvent. The flasks were then
solid applications is one of the most incubated at different temperatures
important sources of natural dyes [3] the (roomtemperature,45C, 50C, 60C,
major colouring component in 70C,80C ). Extract samples were taken at
pomegranate is tannins [4] [5] [6], different time intervals (10 min, 20 min, 30
extracted from the fresh and dried peels. min, 40min
In this study the aim of present work is to ,50min,60min,70min ,80min,90min, 100min,
Optimize of extraction conditions 110min, 120 min). Thus dye from the peel
, natural colorant from the fresh peels of was extracted by aqueous extraction
pomegranate fruits was extracted under procedure. The extraction process was carried
different operating conditions such as out at different temperature, different
extraction time (10 to 120 min), extraction time and with different mass of peel
temperature (room temperature, 45C, in order to obtain the optimal extraction
50C, 60C,70 C, 80 C) and mass of the conditions. At the end of the extraction
peel (1 to10g) by the conventional process, the samples taken from extracts were
extraction technique. The determination of filtered and placed in obscurity
absorbance by spectrophotometer (UV - Analytical method
1700) was used for optimization of the The Absorbance was determined with the help
extraction process and evaluation of of spectrometer (UV-1700) after suitably
interaction effects of different operating diluting the extracted dye with distilled water.
parameters. The optimum conditions for 3. Results and Discussion
dye extraction were found to be 90 min,
60C and 2.5 g, for extraction time, Natural dye from peel of pomegranate fruits
temperature, and mass of the peels was extracted by following aqueous extraction
respectively procedure and the extraction process was
carried out at different temperatures, different
extraction times and with different mass of
Key words: Punica grantum; tannins; Optimize peel with an explicit objective of determining
of extraction the optimum extraction conditions.
1. Introduction
Punuca Granatum peel is used as a raw
material in manufacturing the natural dye.
Peel is also used as a tannin material due to
5 ABSORBANCE temperatures (above 75C), there was charring

1/4 and a blackish shade was obtained .So the
4 ABSORBANCE optimum temperature for dye extraction from
1/6
3
peel was taken as 60 C.
ABSORBANCE
1/8 4. Conclusions
2 ABSORBANCE
1/10
The present work showed that natural dye can
1 ABSORBANCE be successfully extracted from fresh peel of
1/20 pomegranate fruits. Maximum dye extraction
0 ABSORBANCE was observed at 60C using 2.5g of fresh peel
0 50 time 100 150 1/2 . With increasing the extraction time, the dye
extraction efficiency increased, but an
Fig 1: Effect of mass on extraction of dye optimum time of 90 min was considered for
from the fresh peel of pomegranate fruits at extraction of the dye in order to make the
different time. technology more cost effective.
Extraction temperature, time and mass of the
As shown in Fig 1, Dye extraction from peel used markedly influenced the dye
peel depends on the extraction time. With extraction
increase in the mass of peel used for
extraction (1 g to 10 g) as well as the References
extraction time (10 min-120 min), the dye
[1] Adeel, A., Ali Shaukat Bhatti, I.A., Zsila, F., 2009.
extraction was maximum at 90 min
(Dyeing of cotton fabric using pomegranate (Punica
compared to that obtained at other time granatum) )
(10 min-120 min),so the optimum time [2]Lloyd, J.U., 1897. Punica granatum, Chicago
for dye extraction from peel was taken at (consulted in:
90 min using 2,5 g of peel . http://swsbm.henriettesherbal.com/ManualsOther/Punic
3,38 a granatum
[3] Venkatasubramanian Sivakumar, J. Vijaeeswarri, J.
3,36
Lakshmi Anna 2011 .( Effective natural dye
3,34 extraction from different plant materials using
3,32 ultrasound)
[4]Al-Zoreky, N.S., 2009.( Antimicrobial activity of
3,3
pomegranate (Punica granatum L.))
0 50 100 [5] Machado, T.B., Pinto, A.V., Pinto, M.C.F.R.,
temperature
Leal, I.C.R., Silva, M.G., Amaral, A.C.F.,
Kuster, R.M., Nett-dosSantos, K.R., 2003. (In vitro
activity of Brazilian medicinal plants , naturally
Fig 2: Effect of temperatures on extraction occurring naphthoquinones and their analogues against)
of dye from the fresh peel of pomegranate [6] Voravuthikunchai, S., Lortheeranuwat, A., Jeeju,
fruits at different time W., Sririrak, T., Phongpaichit, S.,
Supawita , T., 2004. (Effective medicinal plants
against enterohaemorrhagic)
As shown in Fig 2, at 60 C the dye [7] Gulrajani, M L.; Gupta, D B.; Agarwal, V. and Jain,
extraction was maximum compared to that M. (1992): (Some studies on natural yellow dyes: part
obtained at other temperatures (room IV- Tannins: Terminalia chebula and Punica granatum,
temperature, 45C, 50C, 60C,70 C, 80 Indian Text J, )
C). The reason behind the phenomenon
was that at 60C the chemical groups and
pigments of the fresh peels of pomegranate
fruits were more efficiently disrupted and
the dye present in the peel was efficiently
extracted in the solution. At higher
Simulation of catalytic ozonation simulation of catalytic ozonation of acetic acid

of acetic acid solutions in micro- solutions in the gas-liquid micro-structured
falling film reactor. A detailed computational
structured falling film reactors
fluid dynamics (CFD) model of the catalytic
ozonation micro-reactor is performed.
Jean-Marc Commenge, Nidhal Becheikh,
According to the specificities of the micro-
Thibault Roques-Carmes
reactor (thin liquid film) and the rate of the
reaction of ozone decomposition previously
Universit de Lorraine, Laboratoire
determined, simplification assumptions are
Ractions et Gnie des Procds, UMR
considered. The aim of the model is to
7274 CNRS, Nancy, F-54000, France,
decouple the different processes and to have a
CNRS, Laboratoire Ractions et Gnie des
better comprehension of the rate of absorption
Procds, UMR 7274 CNRS, Nancy, F-
and the catalytic reaction on the surface. The
54000, France
CFD simulations have been performed by
using a simple flow model assuming the water
*Contact author: nidhal.becheikh@univ-
flowing in the micro-reactor with a
lorraine.fr
hemispheric shape at the gas-liquid interface.
The aim of this study is to perform the
simulation of catalytic ozonation of acetic
acid solutions in micro-structured falling
film reactors. The study takes part of an
Keywords: catalysis, ozonation, film reactor,
ambitious project concerning the
simulation.
development of a new micro-fluidic device
to perform catalytic oxidation of Persistent
Organic Pollutants POPs in water by
combining advanced technologies that are
process intensification with micro-systems,
surface engineering, catalysis and non-
thermal plasma processes. The ambition is
to decrease significantly the energetic
consumption compared to conventional
ozone-based technologies. The challenge is
to be able to generate a non-thermal
plasma discharge on the surface of water
flowing as a thin liquid film on a micro-
structured plate recovered by a catalytic
coating with hydrophilic properties.
Gravity driven liquid films on flat

surfaces are prone to decay into droplet or
rivulet pattern. However, micro-structured
surfaces can prevent film break-up and
facilitate very stable liquid films with a
thickness typically below 100 m. The
high liquid based specific interfacial area,
up to 20,000 m2/m3, of falling film micro-
reactors renders them to be ideally suited
to carry out fast exothermic and mass
transfer limited reactions. This paper
concerns a theoretical investigation of the
Notion of viscosity Arrhenius point of pure component in the liquid vapor

equilibrium.
temperature of pure liquids
N,N-dimethylacetamide and Key words: (Binary liquid mixture, Arrhenius
methanol, and their binary activation energy, N,N-dimethylacetamide, Arrhenius
mixtures temperature).
A. Messadi1, M. Dallel2, D. Das3, H. 1. Introduction

Hamda4, N. Ouerfelli2,* and A.H.
Hamzaoui1 Among the physicochemical properties of
binary liquid mixtures, viscosity is valuable
1. Laboratoire de Valorisation des Matriaux Utiles,
Centre National des Recherche en Sciences des tool for developing theoretical models to
Matriaux, Borj Cdria. B.P.95, 2050, Hammam understand the liquid state and structure. On
Lif, Tunisia. messaadi_aymen02@yahoo.fr
mdmihi10@gmail.com the other hand, excess thermodynamic
2. Laboratoire de Technologies Mdicales et properties and deviations of analogous non-
Biophysique, Universit de Tunis El Manar, Institut
Suprieur des Technologies Mdicales de Tunis, 9 thermodynamic functions of liquid mixtures
Avenue Dr. Zouhaier Essafi 1006 Tunis, Tunisie. are fundamental for investigating different
md.dall@live.fr
3. Department of Chemistry, Dinhata College, North types of intermolecular interactions in these
Bengal University, Dinhata-736135, Cooch-Behar, mixtures.
West Bengal, India. debu_nbu@rediffmail.com
4. Laboratoire d'Ingnierie Mathmatique, Ecole Hence, the knowledge and prediction of
Polytechnique de Tunisie. Rue El Khawerzmi physicochemical and thermophysical
B.P.743, 2078 La Marsa, Tunisia.
hatem.hamda@gmail.com
properties of binary liquid mixtures is of great
* Corresponding Author: E-mail: nouerfelli@yahoo.fr importance for understanding and
characterization of intermolecular interactions.
Abstract: In the same context, some models attempt to
Calculation of excess properties in N,N- correlate shear viscosity in liquid mixtures to
dimethylacetamide (DMA) + methanol release information on eventual interactions,
(Met) binary mixtures at (303.15, 308.15, structure and peculiar behaviors.
313.15 and 318.15) K from experimental
density, viscosity and sound velocity 2. Experiment
values were presented in previous work.
Applications of these experimental values The dynamic viscosity (), density () and
to test different correlation equations as ultrasonic sound velocity (u) measured against
well as their corresponding relative mole fraction of DMA in the DMA (1) + Met
functions were also reported. Considering (2) systems utilized in the present study have
the quasi-equality between the Arrhenius been reported earlier [1] where the measured
activation energy Ea and the enthalpy of density and viscosity values of DMA and Met
activation of viscous flow H*, here we binary mixture were used to calculate the
can define partial molar activation energy excess molar volumes (VE) and viscosity
Ea1 and Ea2 for N,N-dimethylacetamide deviations () of this system and then fitted
and methanol respectively along with their to the Redlich-Kister equation [1].
individual contribution separately.
Correlation between the two Arrhenius 3. Results and Discussion
parameters of viscosity in all the domains
Arrhenius parameters of pure components
of composition shows the existence of two
(Met and DMA) as a function of temperature
main distinct behaviors. We add that
can be predicted. Correlation between the two
correlation reveals interesting Arrhenius
Arrhenius parameters for binary mixtures
temperature which is closely related to the
permits us to reveal the viscosity Arrhenius
vaporization temperature and to the boiling
temperature which characterizes the 4. Conclusions

studied binary liquid mixture and can
With this finding, we can predict the boiling
provide information on the vaporization point of the two pure components at constant
temperature of the isobaric liquid vapor pressure through investigation of the
equilibrium. Also, this correlation can give viscosity-temperature dependence in the
evidence of the existence of distinct corresponding liquid phase. We can add that
composition regions with different this very interesting finding is also verified for
behaviours. other studied previous works [2,3] for binary
Thus, assuming that the activation
mixtures of water with DMA or 1,4-dioxane
energy is a thermodynamic quantity, we
and DMA with 2-ethoxyethanol. Taking into
have determined the partial molar
account the accuracy of data and the errors
activation energy to release individual
made in the calculations, we can conclude that
interactions contributions of each pure
the Arrhenius current temperature at very
component within the mixture for each
high concentration of one component (TAi) at
well-defined composition. In earlier study
(xi1), is very close to its corresponding
the treatment of the variation of logarithm
boiling temperature while in the other cases,
of the Arrhenius entropic factor deviation
the Arrhenius current temperatures (TAi) at
against mole fraction (x1) of DMA, shows
(xi1) is in strong correlation with the
the presence of minimum and maximum at
vaporization temperature of the isobaric liquid
two molar fractions, which was explained
vapor equilibrium of the corresponding binary
by the complex formation between DMA
mixture.
and Met. Here, variation of excess partial
molar activation energies as a function of References
the mole fraction of DMA (x1) over the [1] Peshwe, A.G.; Arbad, B.R.; Pachaling, S.P. Volumic and
temperature range indicates the two molar vicosimetric studies on N,N-dimethylacetamide and
fractions that are very close to our earlier methanol binrary mixtures at different temperatures. Int.
reported value, where it is nullify and the J. Chem. Sci. 2009, 7, 1505-1517.
mixture behaves ideally. Correlation [2] Das, D.; Messadi, A, Dhouibi, N.; Ouerfelli, N.;
and Hamzaoui, A.H. Viscosity Arrhenius activation energy
between the partial molar quantities
and derived partial molar properties in N,N-
relative to the activation energies and the Dimethylacetamide + Water Binary Mixtures at Temperatures
logarithm of the entropic factors of from 298.15 K to 318.15 K. Phys. Chem. Liq. 2013, Available
Arrhenius for DMA + Met mixtures over online 19 April 2013. doi: 10.1080/00319104.2013.777960
the temperature range can give an [3] Ouerfelli, N.; Barhoumi, Z. and Iulian, O. Viscosity
approximately linear behavior i.e. no Arrhenius activation energy and derived partial molar
observable change in curvature. This properties in 1,4-dioxane + water binary mixtures from
quasi-straight line behavior suggests us to 293.15 K to 323.15 K. J. Solution Chem. 2012, 41, 458474.
make an empirical equation by introducing
a new parameter TA denoted as viscosity
Arrhenius temperature that characterizes
each binary system. Considering Arrhenius
temperature (TA) is no longer a constant
over the whole range of composition, we
introduce a new concept to find its value at
the two extreme positions i.e., at very high
concentration and very high dilution
respectively. The results derived in the
studied binary system gives an interesting
fact that the isobaric boiling point of the
pure components is very close or strongly
depends upon the viscosity Arrhenius
current temperature.
Optimization Of Sugar Fluid

Bed Drying Process
Conditions
Amira TOUIL1, Ahlem HAJ AMMAR2,

Jihne LITAIEM2, Samia MOTRI2
1 Institut Suprieur des Etudes Technologiques de
Zaghouan (ISET Zaghouan), 1121, Mograne Zaghouan,
Tunisie.
2 Institut National Agronomique de Tunis (INAT), 43,
Avenue Charles Nicolle 1082 -Tunis- Mahrajne, Tunisie.
Abstract
The present study investigated the effect of
operating parameters of a fluid bed dryer
on powder quality and on drying time, in
order to optimize the production of sucrose
powders. A 24-1 fractional factorial design
of experiment has been used. After an
appropriate choice of four critical
variables, 8 experiments led to a
mathematical model as a first degree
polynomial presenting the response
functions (color and drying time) in
relation to the operating parameters. From
the retained model, we were able to
calculate the average response, the
different effects and their interactions. The
results showed that gas flow and sugar
particle size had significant effects (in
absolute values) on the quality of the sugar
dried, at a 95% confidence interval,
whereas temperature and pressure
presented a negligible effect. Sucrose
presented the best quality and the lower
time treatment at the lower gas flow rate
and at larger particle size.
Analyzing the variance (ANOVA) showed
that the model is highly significant and can
adequately describe the experimental
range.
Keywords: Fractional factorial design; Sucrose,
Quality; Fluid bed drying; Optimization.
Effect of the molybdenum formaldehyde [6]. These studies were

occasioned by the interest of Mo-containing
precursor salts on the zeolite because of their possible applications
physicochemical and catalytic as bifunctional catalysts. The impregnation
properties of Mo-Zeolite in method [7] and the solid-state ion exchange
[8] reactions are the main methods to prepare
the ammoxidation of light Mo containing zeolite. The structure and the
hydrocarbon location of molybdenum species in the
E.Mannei1, C.Petitto2, M.Mhamdi1, G. channels of zeolites are under debate. Ma et al
Delahay2, and A. Ghorbel1 [9] suggest two kinds of molybdenum species
1. Laboratoire de chimie des matriaux et catalyse on a MoO3-ZSM-5 prepared by impregnation.
Dpartement de chimie, Facult des Sciences de Tunis,
Compus Universitaire Tunis El Manar 2092 Tunis, The first one was located on the external
Tunisia, emna.mannei@gmail.com surface with an octahedrally coordinated
2. Institut Charles Gerhardt Montpellier, UMR 5253, MoO3. The other was associated with
CNRS-UM2-ENSCM-UM1, Eq. Matriaux Avancs
pour la Catalyse et la Sant, 8, rue Ecole Bronsted acid sites in the lattice channels of
Normale, 34296 Montpellier Cedex 5, France the zeolite as [Mo 2O5]2+ and [MoO2(OH)]+
Abstract: species according to Iglesia et al [10], and Bao
Mo-ZSM-5 catalysts prepared by solid et al [11]. There are many parameters that
state ion exchange from different may have an effect on the distribution of
molybdenum salts were tested in the molybdenum species in the ZSM-5. In this
ammoxidation of ethylene and ethane to paper we focus on the study of the effect of
produce acetonitrile in the temperature molybdenum precursor on the nature of
range 425-500C. These samples were also molybdenum species and the catalytic
characterized by EDX, XRD, N2- properties of Mo-ZSM-5 prepared by solid
Physisorption (77K), H2-TPR, NH3-TPD, state ion exchange (SSIE) in the
UV-Vis DRS and IR spectroscopies. This ammoxidation of ethylene and ethane.
study shows that the catalyst prepared from 2. Experiment
molybdenum chloride exhibited the highest
2.1 Catalyst preparation
yield into acetonitrile. On the basis of DRS
results and other techniques, the (Mo2O5)2+ NH4-ZSM-5(Si/Al=26) furnished by
dimers located at two cation exchange sites Zeolyst, was used as a starting material.
are the main active species. MoO3(Merck), acacMo(Merck-Schuchardt),
Key words: (solid state ion exchange SSIE; Mo- Mo(CO)6 (Aldrich), heptMo:
ZSM-5; ammoxidation; acetonitrile) [(NH)4Mo7O24.4H2O] (Merck) and
MoCl5(Alfa Aesar) were mixed each one with
1. Introduction NH4-ZSM-5(26) in a mortar with the desired
In the last decade, the direct conversion of molar ratio and subsequently exposed to heat
light hydrocarbons into more valuable treatment in helium during 12h at 500C
liquid fuels or chemical compounds has (heating rate 2C). The nominal molar Mo/Al
attracted great interest because of the low ratio was fixed to be equal to 1, which
cost and abundance of methane. Among corresponds to 6 wt% for all the samples.
several process and reactions that have Catalysts were labelled precursor-Z, where Z
been the subject of several works [1,2], the means the zeolite support.
selective ammoxidation of methane into 3. Results and Discussion
acetonitrile over transition metal
exchanged zeolite catalysts [3,4] has been 3.1 Characterization
one of the most studied processes. Many XRD patterns of catalysts are similar to that of
researchers have evaluated a number of parent zeolite this result suggests that
Mo-ZSM-5 catalysts mainly in the molybdenum species are well dispersed
aromatization of methane to aromatics [5] through the zeolite structure. This result is
and in the partial oxidation of methane to
confirmed by EDX analysis. According to catalysts are active and selective towards
textural study, after molybdenum acetonitrile. However MoCl5-Z exhibits the
exchange, the surface area and porous highest yield into acetonitrile.
volume undergo a decrease suggesting the Table 1: C2H4 ammoxidation at 500C
presence of molybdenum aggregates which sample Selectivity Conversion Yield
may block the pore opening. The TPR (%) (%) (%)
profiles of Mo-ZSM-5 showed two MoO3-Z 95.0 11.0 10.5
reduction peaks at 590 and 700C hepMo-Z 94.0 09.0 8.5
corresponding to the reduction of Mo 6+ acacMo-Z 95.2 11.0 10.5
Mo(CO)6-Z 95.0 15.0 14.2
into Mo4+ and to the reduction of Mo 4+ into
MoCl5-Z 98.0 15.5 15.2
Mo metal [12]. IR and UV-vis DRS
spectroscopies reveal the coexistence of
molybdenum associated with exchange 4. Conclusions
cationic sites and molybdenum oxide
Mo-ZSM-5 catalyst synthesized by SSIE,
deposited at the outer surface of zeolite. As
exhibits two kinds of molybdenum species.
shown in figure 1, the deconvolution of
The first one is the octahedrally MoO3 located
DRS spectrum of MoCl5-Z catalyst, by
in the external surface. The second kind was
applying gauss function, leads to three
associated with the Al atom in the lattice
bands attributed to monomers (230nm),
channels of zeolite. The distribution of these
dimers (270nm) and MoO3 (320nm) [13].
species was governed by the nature of the
The amounts of speciation were quantified
molybdenum precursor nature. By using
relative to each other by the area ratio of
molybdenum chloride as precursor,
the different subbands and by considering 2-
molydenum species (Mo2O7) are the major
the same value of extinction coefficient.
species in cationic position which are
Thus from the UV-vis spectra comparison,
proposed as highly active and selective
it seems that the spectrum of MoCl5-Z
species in ammoxidation of ethylene.
catalyst is dominated by the presence of a
band located at 270 nm which is attributed References
to (Mo2O7)2- with tetrahedrally
coordination. NH3-TPD profiles of [1] P.G. Smirniotis, W. Zhang, Appl Catal A: General. 176
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Commun. 10 (2009) 15551557.
suggesting that Mo, loaded in cationic [3] M. Mhamdi, S. Khaddar-Zine, A. Ghorbel, Appl. Catal. A.
positions, consumes preferentially the Gen. 337 (2008) 39 -47
[4] F.Ayari, M. Mhamdi, D.P. Debecker, E. M. Gaigneaux, J.
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(1986).323
0,6
[6] A. de Lucas, J.L. Valverde, L. Rodriguez, P. Sanchez, M.
K.M Function
0,5 T. Garcia, Appl Catal A :Gen 203 (2000) 81-90.

[7] H. Jeziorowski, H. Knnzinger, J. Phys. Chem. 83 (1979)
0,4
1166.
0,3 [8] M. del Arco, S.R.G. Carrazan, V. Rives, F.J. Gil-
0,2
Llambias, P. Malet, J. Catal. 141 (1993) 48-57.
[9] D. Ma, Y. Shu, X. Bao, Y. Xu, J. Catal. 189 (2000) 314.
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0,0 191 (2000) 373.
200 250 300 350 400 450 500 550 600 [11]D. Zhou, D. Ma, X. Liu, X. Bao, J. Mol. Catal. A :
Wavelength (nm) Chemical 168 (2001) 225.
Figure 1: DRS spectrum of MoCl5-Z
3.1 Catalytic results [12 ] Liu Hongmei, Xu Yide, Chin J Catal, 2006, 27(4): 319-
323.
Catalytic performances in ethylene [13]L.Mosqueira, C . Angeles-Chavez, E. Torres-Garcia,
Mater Chem Phys, 126, 2011, 930-937
ammoxidation at 500C for the different
catalyst are compiled in table 1. All
Synthse in situ et et ont permis lassociation de TiO2 avec

HPMC dans une structure msoporeuse. Par
caractrisation de lhybride ailleurs, lhybridation de TiO2 avec le ligand
TiO2/HPMC- Application la organique polyhydroxyl HPMC a permis de
photodgradation de 4-NP modifier
Mohamed Faouzi Nsib 1, Faten Hajji 2,

Ammar Houas 3
1 URCMEP (UR11ES85), ENIG, Universit de
Gabs, 6029 Gabs, Tunisie.
mohamed.faouzi.ncib@gmail.com
2 URCMEP (UR11ES85), Fac. Sc. Gabs,
Universit de Gabs, 6029 Gabs, Tunisie.
faten_hajji@yahoo.fr
3 URCMEP (UR11ES85), Fac. Sc. Gabs,
Universit de Gabs, 6029 Gabs, Tunisie.
amhouas@gmail.com
Rsum
Mots cls : matriau hybride, TiO2,
cellulose, photocatalyse.
Dans la thmatique de recherche gnrale
sur la ralisation de matriaux hybrides
organique-inorganique, notre contribution
a t de montrer quil est possible de
synthtiser de faon reproductible des
vritables matriaux hybrides photoactifs
base de Ti(IV) incorporant des ligands
organiques.
La voie de synthse suivie est base sur la
chimie sol-gel et a fait intervenir, dans une
prparation in situ, Ti(iPr-O)4 comme
prcurseur de Ti (IV) et un driv
cellulosique (lhydroxypropyl
mthylcellulose :HPMC) en tant que
partenaire organique. Le matriau hybride
obtenu est not TiO2/HPMC x%. x%
reprsente le pourcentage massique (5%,
10% et 20%) de HPMC par rapport la
masse de TiO2.
Les matriaux ainsi synthtiss ont t
caractriss par diffrentes techniques
telles que : Spectroscopie infrarouge par
transforme de Fourier (FTIR), diffraction
des rayons X en poudre (DRX),
spectroscopie UV-Visible de rflexion
diffuse (DRS), isothermes dadsorption /
dsorption (BET), spectroscopie de
photolectrons X (XPS), analyse thermique
(ATG / ATD).
Les rsultats obtenus ont montr que des
liaisons covalentes Ti-O-C ont t tablies
Water treatment combined monochloramine was observed to slow down

with the addition of bicarbonate which
chlorine (monochloramine) suggests that there is chloramines formation
degradation using direct
by Cl radical regenerate by the NaOCl
photolysis and homogeneous photodecay .
photo catalysis (UV/H2O2, Besides, the photodecomposition of NH2Cl
UV/NaOCl) with a Medium leads to the formation of nitrite, nitrate and
does not form ammonia.
Pressure (MP) lamp as a
source of UV

The production of OH radicals through the
1
Ala Abdessemed ,3, Amer S. El-Kalliny ,
2,4
H2O2 /UVLP and NaOCl/UVLP process is detected
3 3 22
Kamel E. Djebbar , , Henk Nugteren T. by a photoluminescence (PL) technique using
Sehiliand Peter W. Appel terephthalic acid (TA) as a probe molecule.
1 Biotechnology Research Centre, BPE 73, Ali Mendjeli, Key words: monochloramine, ultraviolet (UV) light,
Nouvelle Ville, 25000 Constantine, Algeria.
photolysis, photoluminescence, OH radical, Cl radical.
2 Product and Process Engineering, Delft University of
Technology, ChemE, Julianalaan 136, 2628 BL Delft, the
Netherlands.
3 Laboratory of Science and Technology of the

Environment, University Mentouri Constantine, Chaabat
Errassas, 25000 Constantine, Algeria.
4 National Research Centre, Water Pollution Research

Department, Dokki, Giza, Egypt
Abstract
The objective of this study is to
investigate the use of ultraviolet (UV) light
photolysis using Medium Pressure lamp (200
- 600 nm), H2O2 /UVMP and NaOCl/UVMP
systems for monochloramine control in
water.
It was found that the direct
photolysis treatment is a suitable method to
deplete monochloramine and the addition
of hydrogen peroxide (H2O2) in the
presence of the UV light increases the
speed and efficiency of the rate
degradation, however no big advantages
were observed after having added
hypochlorite (NaOCl) this can be
explained by the competition between

degradation (with OH) and the formation

of chloramines compounds (with Cl ) by
the addition of NaOCl during the
experiment; to prove that, sodium
bicarbonate is added, its known that

sodium bicarbonate is an effective OH
radical scavenger, the degradation of
Preparation and these catalysts strongly depends on surface

properties and on the dispersion of
characterization of silica molybdenum on the silica support, which are
supported molybdenum in turn influenced by the preparation method
catalysts [1]. In this context, our work focuses on the
preparation through two methods (sol-gel and
Nesrine Boufaden, Rym Akkari and impregnation) of silica supported
Abdelhamid Ghorbel molybdenum catalysts and the
Laboratoire de Chimie des Matriaux et Catalyse, characterization of the synthesized solids in
Dpartement de Chimie, Facult des sciences de Tunis, order to compare their properties.
Campus Universitaire, 2092 El Manar, Tunis, Tunisie
2. Experiment
Abstract:
2.1 Materials and methods:
This work includes a comparative study
Tetra-ethoxy-silane (TEOS, Si(OC2H5)4,
of the properties of silica supported
Acros, 98% purity) was used as silica source,
molybdenum catalysts prepared via two
nitric acid (HNO3, Scharlau, 65% purity) as
methods: sol-gel and impregnation.
hydrolysis catalyst, ethanol (EtOH, C2H5OH,
Silica supports were prepared through the
Sigma-Aldrich, 99,8% purity) as solvent and
sol-gel route by varying the molar
molybdenum acetylacetonate (Mo(Acac),
ratio nHNO3/nSi. For mixed oxides, three
MoO2(C5H7O2)2, Merck-Schuchardt) as
Mo/SiO2 samples were prepared, by sol-
molybdenum precursor.
gel route, aqueous impregnation and
alcoholic impregnation. In order to study 2.2 Experimental Set Up
the effect of the preparation method on Three silica supports were synthesized
catalysts properties, the prepared materials through a one-step method which consists on
were thereafter characterized by N2 mixing the required amounts of HNO3 and
physisorption at 77K, X-Ray Diffraction, EtOH to adjust the molar ratio nHNO3/nSi at
UV-Vis Spectroscopy, IR Spectroscopy 0,03 ; 0,06 and 0,12. TEOS is added dropwise
and Raman spectroscopy. Samples and the mixture was stirred until gelation
prepared via the sol-gel method exhibit while maintaining the temperature at the
interesting textural properties but those initially set value. After gelation, the obtained
prepared using impregnation show more gel is dried in an autoclave under ethanol
varied molybdenum species thanks supercritical conditions: the silica aerogel is
probably to the deposition of the entire then obtained.
molybdenum on the surface. For Mo/SiO2 catalysts prepared by sol-gel
route (referred to as Mo-SiO2 sg), the same
Key words: Molybdenum, Silica support, Sol-
procedure is followed with the addition of
gel, Impregnation.
Mo(acac). For Mo/SiO2 catalysts prepared by
1. Introduction the impregnation method, molybdenum
acetylacetonate was dissolved in water
Silica supported molybdenum oxide (referred to as Mo-SiO2 imp-aq) or alcohol
catalysts are attracting more and more (referred to as Mo-SiO2 imp-alc) at a specific
interest in the field of research owing to temperature and the required amount of non-
their important physico-chemical calcined silica aerogel was added. The sample
properties. Indeed, this type of catalyst is was dried at 120C for 15h. All catalysts were
receiving much attention due to its then calcined at 500C under oxygen.
industrial application in various catalytic
reactions such as hydrodesulfurization, 3. Results and Discussion
dehydrogenation of alkanes, partial 3.1 Results
oxidation of methanol to formaldehyde and
olefin metathesis. The studies already N2 physisorption at 77K showed that silica
made have shown that the effectiveness of aerogels exhibit interesting textural properties
with a specific surface around 1000 m2/g. presence of large MoO3 aggregates,
The molar ratio nHNO3/nSi has a confirming the DRX results.
remarkable effect on the specific surface
SiO2
area, the average pore volume and the
MoO3
gelation time (Table 1). The choice of the
Mo-SiO2 sg
preparation conditions for the silica
Mo-SiO2 imp-acq
support is then based on the ratio allying Mo-SiO2 imp-alc
the best textural properties with the
K.M (u.a)
shortest gelification time. It was also
noticed that the addition of molybdenum
through sol-gel method or impregnation
affects differently the surface properties of
catalysts as in the first case a part of the
molybdenum is probably incorporated in
the bulk while in the second case it would 200 300 400 500
be all dispersed on the surface, leading to a Wavelength (nm)

remarquable decrease of the specific Figure 1: UV-Vis spectra of all catalysts
surface area.
All silica characteristic bands are present on
Table 1 : Textural properties of silica the IR spectra of Mo/SiO2 catalysts. For
aerogels samples impregnated by an aqueous or
Support SBET(m2/g) Vp(cm3/g) Gelation alcoholic solution of Mo(acac), the formation
time of MoO3 crystals over silica supports were
SiO2(0,03) 851 3,12 46 h confirmed by the appearance of characteristic
SiO2(0,06) 1013 2,65 46h bands. This was not the same for sol-gel
SiO2(0,12) 984 2,87 22h sample which could be explained by the small
size of MoO3 crystals and the low amount of
The three mixed catalysts develop a superficial molybdenum compared to
crystalline structure as peaks attributed to impregnated samples. The latter result was
-MoO3 phase are detected. The also revealed by Raman spectroscopy as bands
persistence of the pick corresponding to corresponding to MoO3 appeared.
the amorphous silica (20-30 2) indicates
the high dispersion of tiny clusters of - 4. Conclusions
MoO3 on the silica support. The preparation method affects remarkably
(Mo-SiO2 sg) UV-Vis spectra showed a the textural and structural properties of
broad absorption band (200-330 nm) which Mo/SiO2 catalysts. The impregnation method
can be considered as the overlapping of the insures probably the deposit of all
absorption bands at 200-250 nm molybdenum on the silica surface, which
corresponding to isolated tetrahedral induces the formation of relatively large
(MoO42-, referred to as Td) coordinated MoO3 aggregates on the silica surface and
Mo(VI) species and the band at 290-320 more varied molybdenum species. However,
nm assigned to octahedral (MoO66-, in the case of sol-gel prepared samples, a part
referred to as Oh) coordinated Mo(VI) of the molybdenum phase would integrate the
species. For the two impregnated samples, bulk and then the molybdenum aggregates
this broad band is shifted to higher arent so large which allows a higher
wavelengths which is probably due to a dispersion.
change in local molybdenum symmetry References
from Td to Oh since the amount of
[1] Gervasini, A. Wahba, L. Dario Finol, M. Lamonier, J-F.
molybdenum deposited on the surface
Property and Activity of Molybdates Dispersed on Silica
increased. An intense band at 330 nm also
Obtained from Various Synthetic Procedures. Mat. Sci. and
appeared which is explained by the App. 2012, 3, 195-212.
REAC TION KINETICS OF immobilized by entrapment in aliginate gel

[2,3]. Then the hydrolysis of p-nitrophenyl--
FREE AND IMMOBILIZED D-glucopyranoside (PNPG) to p-nitrophenol
-GLUCOSIDASE IN by -glucosidase was studied at different
ALGINATE GEL substrate (PNPG) concentration. The
Ahmad T. Jameel , Faridah Yusof and performance of the enzyme was studied by
Syaira Johana measuring its activity in terms of generation
of p-nitrophenol which was calculated using
Department of Biotechnology Engineering, absorbance measured by spectrophotometer.
Kulliyyah of Engineering, International Islamic The rate of substrate consumption has 1:1
University Malaysia, Gombak, 50728 Kuala stoichiometric relation with p-nitrophenol
Lumpur, Malaysia
generation. The rate vs. substrate consumption
A.T. Jameel [atjameel@yahoo.com]; Faridah Yusof show Michaelis-Menten type of dependence.
[yfaridah@iium.edu.my]; Syaira Johana Linearized plots are used to evaluate
[syaira.rashid@yahoo.com] Michaelis constants. The efficiency of
Abstract: immobilized enzyme is compared with free
soluble enzyme. Enzyme activity is generally
Kinetics of immobilized -glucosidase
expected to decrease with immobilization,
obtained from almonds (EC 3.2.1.21) on
albeit with enhanced operational performance
calcium aliginate beads was studied by
measuring the activity of the enzyme in in terms of stability, reuseability and easy
terms of the generation of p-nitrophenol separation of the enzyme [1,2].
from the hydrolysis of p-nitrophenyl--D-
glucopyranoside (PNPG).The immobilized 2. Materials and Methods
enzyme activity decreased by 36.6%
compared to native enzyme. The -Glucosidase from almonds (EC 3.2.1.21),
hydrolysis rate data exhibit Michaelis- and p-nitrophenyl--D-glucopyranoside
Menten type kinetics. The Michaelis (PNPG) were obtained from Sigma-Aldrich;
constant were determined using Langmuir sodium alginate was obtained from Fisher
linearized plot which obtained vmax and Km Chemical, and calcium chloride was
as 21.10 mol/ml.min and 0.0148 mol/L purchased from Merck. The lyophilized
respectively for immobilized enzyme enzyme was dissolved in 2 mL of 1M
compared to 24.33 and 0.0073 Potassium Phosphate buffer at pH 6. 40 L of
corresponding values for the free enzyme. enzyme solution was mixed with 960 l
However, the immobilized -Glucosidase
sodium alginate to give a 4% (w/v) final
did not show a sufficiently good
concentration of enzyme in the mixture
operational stability on reuse.
[2,4,5]. This mixture was used to obtain
calcium alginate beads of sizes 3, 4 and 5 mm.
Key words: Immobilized enzyme, enzyme The -glucosidase activity was routinely
activity, Michaelis-Menten kinetics, -glucosidase,
alginate gel, Langmuir plot determined with p-nitrophenyl--D-
glucopyranoside (PNPG) as the substrate [2].
The reaction mixture, containing 1 mL of a 10
mM PNPG solution in 0.05 M sodium citrate
1. Introduction buffer, pH 4.8 and the calcium alginate beads
Immobilization of enzymes is one of was incubated at 50C in a water-bath. After
the methods to impart operational stability 15 min, 1.5 mL of 1.0 M sodium carbonate
and longevity for multiple usage besides was added to stop the reaction and to develop
ease of separation of the enzyme from the the colour of any p-nitrophenol (generating p-
reaction mixture. Different immobilization nitrophenolate) that has been released from
methods are currently in practice [1]. In the substrate. The absorbance was read at 400
the present study, a -glucosidase obtained nm, and the amount of p-nitrophenol liberated
from almonds (EC 3.2.1.21) was was determined. A unit of activity was defined
as the amount of enzyme required to

liberate 1 mol of p-nitrophenol per min
from the substrate. Similarly, the activity
of the free enzyme was determined and
compared with the immobilized enzyme
for the optimum bead size.
2.1 Determination of kinetic constants

Enzymatic reaction was carried out at
50C with different substrate
concentrations. The stock solution for the
substrate was prepared for 0.1 M PNPG Figure 1: Enzyme activity of immobilized
and was diluted till 0.01 M. The kinetic enzyme (4mm beads) and free enzyme.
constants Km and vmax were calculated
using Langmuir, Eadie Hofstee and 2.1 Determination of Kinetic Parameters
Lineweaver-Burk plots [6]. Enzyme activity as a function of substrate
concentration show saturation of reaction rate
2.2 Operational stability of the at high substrate concentration. This behavior
immobilized -Glucosidase is typical of Michaelis- Menten kinetics. Thus
After each -glucosidase activity assay, it can be inferred that the hydrolysis of p-
the beads were removed, washed nitrophenyl--D-glucopyranoside (PNPG) by
thoroughly with distilled water and stored -glucosidase follows Michaelis-Menten
at 4C chiller. Then the beads were kinetics. The Michaelis constants were
reassayed for the second cycle of enzyme evaluated using linearized plots of Langmuir,
activity which is after 4 days (96 hours) Eadie Hofstee and Lineweaver Burk [6].
and the third cycle was at the fifth day (120 However, Langmuir plot (Figs. 2(a & b) gave
hours). a better fit to our experimental data compared
to the other two linear plots (not shown).

Immobilized enzyme activity for different 0.006
bead sizes (3, 4 and 5 mm diameter) were
studied and the highest activity was 0.005
observed for 4 mm beads which were used 0.004
for subsequent experiments and analysis.
0.003
s/v
The enzyme activities for immobilized and

free enzymes are compared in Figure 1. 0.002
y = 0.0474x + 0.0007
Immobilized enzyme shows a decreased 0.001 R = 0.9742
activity by 36.6% as compared to free
enzyme which is obvious due to mass 0
transfer resistance to substrate diffusion 0 0.05 0.1 0.15
through alginate beads.
[6] Doran, P. M. Bioprocess Engineering Principles,

0.005
y = 0.0411x + 0.0003 Academic Press, London, 1995.
0.0045
0.004 R = 0.9927
0.0035
0.003
0.0025
s/v
0.002
0.0015
0.001
0.0005
0
0 0.05 0.1 0.15
s
Figure 2: Langmuir plot for -Glucosidase

at substrate concentration (0.01, 0.04, 0.06,
0.08 and 0.1 M). (a) Immobilized enzyme;
(b) Free enzyme
4. Conclusions
Efficiency of -glucosidase enzyme
immobilized on calcium alginate beads
was compared to the native enzyme by
measuring enzyme activity. Immobilized
enzyme dispalyed decrease in the activity
by 36.5% after immobilization. Hydrolysis
of PNPG by -Glucosidase follow
Michaelis-Menten kinetics. The kinetic
parameters were evaluated using linearized
Langmuir plot which showed a better fit
compared to Linewaever-Burk and Edie
Hofstee plots.
References
[1] Sheldon, R. A. Enzyme Immobilization: The
Quest for Optimum Performance, Adv. Synth.
Catal., 2007, 349, 1289-1307.
[2] Ortega, N., Busto, M. D. & Perez-Mateos, M.
Optimization of -Glucosidase Entrapment in
Alginate and Polyacrylamide Gels, Bioresource
Technology., 1998, 64, 105-111.
[3] Roy, S. K., Raha, S. K., Dey, S. K. & Chakrabarty,
S. L. Enzyme Microb. Technol., 1989, 11, 431-435.
[4] Dey, G., Singh, B. & Banerjee, R. Immobilization of
-Amylase Produced by bacillus circulans GRS
313, Brazilian Archives of Biology and Technology,
2003, 46(2), 167-176.
[5] Workman, W. E. & Day, D. F. Purification and
Properties of -Glucosidase from Aspergillus
terrus, Appl. Environ. Microbiol., 1982, 44, 1289-
1295.
Microwave assisted weight and phenolic compounds 2% of total

oil weight [2].
maceration: A new and green
Aromatic plants have also been used since
procedure for direct ancient times in food flavours, it is well
aromatisation of olive oil with known for its antioxidant activity and
rosemary leaves nutritional value due to its riches with
Hasnia BENMOUSSA1, Asma FARHAT1, essential oil [3, 4].
Mehrez ROMDHANE1, Ilona Di MAIO2 The present work proposes a practice of
and Maurizio SERVILI2 microwave heating to extract the rosemary
1. Unit de recherche MACS, ENIG, Universit de essential oil from their glands to the olive oil.
Gabs Route de Medenine, 6029, Gabs, In order to reduce the extraction time, CO2
Tunisie, b.benmoussahasnia88@yahoo.fr and
mehrez.romdhane@laposte.net
emissions and energy cost. This new
2. Dipartimento di Scienze Economico-Estimative technique, fortify nutritional value of oil and
e degli Alimenti-Sezione di Technologie e increase its shelf life and consequently, create
Biotecnologie degli Alimenti-Universita degli
a health-beneficial traditional foods.
Studi di Perugia-Via S. Costanzo-06126
Perugia,Italy, servimau@unipg.it 2. Materials and methods
Abstract: 2.1. Materials
Microwave assisted maceration (MAM) Rosemary leaves (Rosmarinus officinalis L)

was developed as a new and cleaner were collected from the north area of Tunisia.
procedure for a green enrichment of an EVOO used in this study was produced in 24
olive oil with rosemary leaves. MAM has October 2012.
been compared with conventional 2.2. Conventional maceration
maceration. Microwaves were then applied
Rosemary leaves were added directly to the
in order to accelerate diffusion of the
samples of EVOO at a rate of 10% at room
rosemary volatile compounds into the olive
temperature for several days to follow the
oil. Then the enriched olive oil obtained by
kinetics of aromatization.
MAM was qualitatively (aromatic prole)
similar to those obtained by conventional 2.3. Microwave assisted maceration (MAM)
maceration. However, the processing time Identical amounts of plant material
is reduced from hours or days to few supplied to EVOO. However, the microwave
minutes when comparing traditional heating (type BAUKNECHT MCG 1731) was
maceration and Microwave assisted applied for different powers and periods
maceration. (Figure 1). The final aromatised mixture
subjected to the same analyses as the previous
Key words: Aromatization, Microwave, Olive simples.
Oil, Rosemary.
1. Introduction
Virgin olive oil is highly appreciated for
its sensory and nutritional properties.
Therefore, it confers healthy benefits to the
Figure 1: Microwave oven.
Mediterranean diet [1], it represents the
excellent source of fats 98% of total oil 3. Results and Discussion
3.1 Comparison of microwave assisted

maceration and conventional maceration.
The yield of the essential oil extracted
from rosemary leaves was 2,45%. 17
volatile compounds were identified by the
HS-SPME/GC-MS chromatograph mainly
composed of camphore 25% and cineole
23%, which are not found in EVOO before
maceration (Figure 2), thus these two
compounds were used like keys to estimate
the level of aromatisation of the olive oil.
a Figure 3: Kinetic of aromatisation by microwave
assisted maceration and conventional maceration
(10% de rosemary leaves in EVOO).
Microwaves increased the kinetic of

enrichment, 9min of experiment with
microwave heating MAM are enough to
produce aromatised olive oil with high quality
controlled by several tests of free fatty acid
FFA 0,8% and peroxide value PV 20 mEq
O2/kg.
b 4. Conclusions
Microwave assisted maceration has been
demonstrated its ability to enrich the EVOO
by rosemary volatiles compounds with various
advantage in term of time, yield and energy
cost.
Acknowledgment
The authors are very grateful to thank Ilona Di
MAIO for the GC/MS analyses.
Figure 2: (a) GC/MS chromatogram of
rosemary essential oil; (b) chromatogram of References
no aromatised olive oil. [1] Moldao-Martins, M. Beirao-da-Costa, S. Neves, C.
Cavaleiro, C. Salgueiro, L. Beirao-da-Costa, M.L. Olive oil
We analysed different samples of flavoured by the essential oils of Mentha x piperita and
enriched olive oil that were taken at Thymus mastichinaL. Food Quality and Preference, 2004,
15, 447452.
different moment by GC-MS to fellow the [2] Lesage-Meessen, L. Navarro, D. Maunier, S. Sigoillot, J-
kinetic of enrichment (Figure 3). C. Lorquin, J. Delattre, M. Simon, J-L. Asther, M. Labat, M.
After 9 min of microwave assisted Simple phenolic content in olive oil residues as a function of
maceration MAM, we estimated an extraction systems. Food Chemistry, 2001, 75-501-107.
[3] Erkan, N. Ayranci, G. & Ayranci, E. Antioxidant
increasing yield of cineole and camphore
activities of rosemary extract, blackseed essential oil, carnosic
3,16% and 1,21%, respectively, but with
acid, rosmarinic acid and sesemol. Food Chemistry, 2008,
traditional maceration only 1,05% of 110(1), 7682.
cineole and 0,45% of camphor were found [4] Petersen, M. & Simmonds, M.S. Rosmarinic acid.
in the oil after 12h of natural maceration. Phytochemistry, 2003, 62(2), 121-125.
Drying characteristics of
Eucalyptus Camaldulensis
leaves: Drying experiments
and mathematical modeling
GHODBANE Houdaa, NASFI Nadia,
BAGANE Mohameda
a Applied Thermodynamics Unit Research,
ENIGabes, 6029 Zrig Gabes, Tunisia
e-mail: ghodbanehouda@yahoo.fr
Abstract
Many products such as aromatic and
medicinal plants contain high moisture
content. Such moisture could cause their
deterioration in storage. Drying is an
interesting solution to keep the quality of
these products.
Drying characteristics of Eucalyptus
Camaldulensis leaves have been studied in
a forced convection dryer. This is a wind
tunnel where we can control the
temperature, velocity of the drying air.
To determine the kinetic parameters, the
drying data were fitted to various models
based on the moisture ratios versus drying
time. Among the models proposed, the
Logarithmic model gave the best fit for all
drying conditions applied. The goodness of
fit was determined using the coefficient of
determination (R2).
Knowledge of moisture desorption
isotherms is useful in product dehydration
and drying. The equilibrium moisture
content for Eucalyptus Camaldulensis
leaves was determined by using the
Dynamic Vapor Sorption method with
water activity ranging from 5% to 95 %
and three temperature 25, 35 and 45C.
Many models were used to compare the
experimental data of desorption. The GAB
model was the best model for describing
desorption isotherms curves.
Key words: isotherms; adsorption;
desorption; drying; modelisation.
Comparative Study and into foods. Thus, the value of these by-
products is not only an environmental
Optimization of Several necessity but an economic solution for
Drying Process on Sesame by- confectionery industry. The interest to vary
Products the processes of drying is to choose the
Yakouta KHALDI, Karim KRIAA, adequate process which improves the final
Bilel HADRICH, Mohamed Amine properties of product.
BALTI, Nabil KECHAOU 2. Experiment
Groupe de Recherche en Gnie des Procds 2.1 Physicochemical Characterization of Sesame
Agroalimentaires, Laboratoire de Recherche en Coat
Mcanique des Fluides Applique - Gnie des Procds -
Environnement, Ecole Nationale dIngnieurs de Sfax, All the analytical determinations were
Universit de Sfax, BP 1173 3038, Sfax, Tunisia performed at least in triplicate. Values of
khaldidorra@yahoo.fr; kriaa_karim@yahoo.fr
bilelhadrich@yahoo.fr ; balti-med-
different parameters were expressed as the
a@hotmail.fr;nabil.kechaou@enis.rnu.tn mean standard deviation (SD). The results
of the physico-chemical characterization are
Abstract: presented in Table 1.
The valuation of sesame by-products is one
of the industrial priorities. In order to Table 1: Chemical composition
operate their maximum nutritional value, (g/100 g of dry basis) and water activity of
this approach solves the problems of raw sesame coat
rejection and their impact on the Characteristic Value
environment. Moisture content 0,231 0,004
In a first step, a physico-chemical aw 0,98
characterization of the studied product was pH 4,95
carried out. This is followed by a Protein 6,832 0,676
comparative study of several drying Ash 0,243 0,001
processes, and their impact on the studied Total phenols 1,12 0,05
product quality and stability. Total sugar 25,19 3,41
Iron 1,216
Drying tested processes are: a forced
Potassium 0,742
convective drying, natural convective
Sodium 0,648
drying, fluidized bed and microwave.
Initially sesame coat have a water activity
of about 0.982. This setting will give us 2.2 Forced Convective Drying
idea about the effectiveness of the drying We have tested only one temperature equals to
operation performed. 40C with a speed equals to 1 m/s.
2.3 Free Convective Drying
Keywords: Sesame coat, Physico-chemical
characterization, Frees convective Drying, Natural convection drying was performed in
Microwaves. an oven equipped with a precision balance
1. Introduction coupled to a PC. Taking mass is performed
every 30 seconds until a constant mass. Three
Sesame (Sesamum indicum L.) is the main levels of drying temperatures were tested:
raw material for production of Halwa- 40C, 50C and 60C.
Chamia with a significant annual tonnage
(5,000 tons per year). This results in the 2.4 Fluidized Bed Drying
by-products (sesame coat) production with We have started the experiment with a
an important tonnage. For nutrition, worthless speed of gas and we have increased
sesame coats are rich in fatty acids, this value gradually (gas flow = 2.5 m3/h for
proteins, calcium and iron [1]. For this T=20C and P = 1atm).
reason, the sesame coat can be introduced
2.5 Drying by Microwaves In addition, a sensory analysis had been

Microwave drying is performed at three established on the level of the laboratory
levels of power: 180W, 450W and 850W. showed when that decreasing the power, the
Depending on the fixed power, the catch of bitterness decreases. This is explained by the
mass varies between 30 seconds and 5 fact that the microwave penetration depth in
minutes until obtaining a constant mass. the product is inversely proportionate to the
Taking temperatures is a crucial step at the microwave frequency [4].
end of each drying cycle. 4. Conclusions
3. Results and Discussion The comparison of several processes of drying
3.1 Forced Convective Drying shows that drying by microwaves is more
effective in term of the drying time and the
The test was failed because of ventilation final proprieties of product. Also, micro-
which causes a loss of mass. waves seems to be fast and compatible with
3.2 Natural Convective Drying environment and offers an energy saving.
The water evaporation is a phenomenon References
which needs heat and it is more intense as [1] Elleuch M, Besbes., S., Roiseux O., Blecker, C. and
the temperature of material is high. For this Attia, H. 2007. Quality characteristics of Sesame
reason, the increasing of the drying Seeds and Byproduct. Food Chem., 103: 641-650
temperature generates the decreasing of [2] AOAC (1997) Official methods of analysis
th
drying time (figure 1). (16 ed.). Washington, DC: Association of Official
1.2 Analytical Chemists.
[3] AFNOR, 1996 : dosage des minraux : mthode par
1 spectrophotomtrie dmission de flamme. NF U
0.8 42-245. Paris AFNOR.
[4] Kisselmina Youssouf Kone, 2011 ; amlioration de
X red
T = 40C
0.6 la qualit de la tomate sche par microondes
T = 50C assists par air chaud avec pilotage de la puissance
0.4 spcifique.
0.2 T = 60C
0
0 50 100
Temps (min)
3.3 Fluidized bed Drying

For both the lowest and important speeds,
the solid layer remains on the grid without
visible movements.
3.2 Microwaves Drying
As far as concerning microwaves drying,
the comparison of the drying kinetics for
the three powers level as well as the curves
speed show that by increasing the power,
the drying time decreases substantially.
For instance for P = 850 W a constant

mass is obtained after 10 minutes while it
takes 60 minutes for P = 100W.
Effect of processing on drying activity were studied. Convective drying

preserves texture parameter while the
kinetics, biochemical and radiative one improves chlorophylls and
techno-functional proprieties of biochemical composition
green algae Ulva sp.
Key words: Green seaweeds Ulva sp., drying,
Salma TRABELSI REKIKa,b, Bilel kinetics, fitting, texture, water activity.
HADRICHa Karim KRIAAa, , Nathalie
1. Introduction
BOURGOUGNONb, Nabil KECHAOUa
a
Groupe de Recherche en Gnie des Procds The green alga has been used by mankind as
Agroalimentaires, Laboratoire de Recherche en food and drug since ages. However, the last
Environnement, Ecole Nationale dIngnieurs de Sfax,
few decades have witnessed the
Universit de Sfax, BP 1173 3038, Sfax, Tunisie. unprecedented momentum in research on
b
Universit europenne de Bretagne, Laboratoire de nutritional and medicinal potency of this alga.
Biotechnologie et Chimie Marines (LBCM), Universit
de Bretagne-Sud, Centre de Recherche Yves Coppens,
It has emerged as an undisputed medical food
Campus de Tohannic, 56017 Lorient Cedex, France. with the discovery and validation of a litany of
salmatrabelsirekik@gmail.com ; bilelhadrich@yahoo.fr ; health benefits ranging from antioxidant, anti-
kriaa_karim@yahoo.fr ; nathalie.bourgougnon@univ-ubs.fr; inflammation, hypolipemic, antithrombotic,
nabil.kechaou@enis.rnu.tn;
Abstract: anti-diabetic, anticancer, immunestimulatory,
antimicrobial, cardioprotective. The
The present work is mainly focused on the particularity of this algal biomass is to present
study of two types of drying behavior a very high humidity, which causes problems
(convective and radiative drying) of Ulva on their conservation and extraction. Further
sp. (Chlorophyta, Ulvales). The objective drying step upstream from the extraction is
was to investigate the drying kinetics and often performed.
the effect of process conditions on techno-
functional properties and biochemical 2. Experiment
composition. In this way, Ulva was dried 2.1 Experimental Set Up
by convection for different air
temperatures, ranging between 30C and The Ulva sp. seaweeds were collected
70C; and by radiation with seven raw and fresh from the littoral of Sidi-
microwave intensities (100-850W). Mansour (SfaxTUNISIA). Fresh plants were
For the drying kinetics, the results show thoroughly removed of their epiphytes, rinsed
that the increase on the operating with distilled water and stocked for further
temperature strongly accelerates the drying experiments. The algal biomass was dried
process, so that processing at 30C takes using one of the following drying methods: (a)
25 h while at 70C the drying is finished ambient temperature drying in a lightening,
after only 20 h. On the other side radiative well ventilated room for 2 weeks ( 16C); (b)
drying take place only on few minutes. radiative drying in microwave (100-850W);
Seven mathematical models were tested to (c) natural convective drying within an oven
fit all experimental data. Logarithmic and with different temperatures (30-70C).
model shows the best fitting quality for all Drying kinetics curves were determined.
convective drying experiments (0,995 r The fitting of drying curves allows
0,997 ; 0,019 ES 0,021). Concerning describing the experimental curves with
the radiative drying, the best model is Page empirical models and identifying the useful
and this is for all experiments (0,992 r parameters. Seven models which were tested.
0,998 ; 0,081 ES 0,193). The mathematical treatment boils down to the
The biochemical properties that were use of non-linear regression by the software
analysed in dried algae were: moisture "Curve Expert 1.4". All dried samples, like the
content, total sugars, proteins, lipids, fresh ones, were analysed immediately. The
uronic acids, sulphates groups, crude fibre techno-functional and biochemical
and ash... Also texture, color and water composition of Ulva sp. samples, were
determined: total sugars, proteins, uronic such as lipids and polyphenols were weakly
acids, polyphnols, ash, sulphates groups present.
and total dietary fibre content, mineral
Drying ND Convective drying Radiative drying
amount, water activity, swelling capacities,
type
water and oil holding capacities. Compos. 16C 30 C 50C 70C 100 W 450 W 850 W
3. Results and Discussion T. sugars 19.50 24.50 25.81 24.00 19.40 24.50 29.44
Protein 9.00 9.39 9.52 9.27 9.70 9.75 8.32
3.1 Drying procedure and Kinetics Uronic acids 16.10 16.50 20.10 18.40 17.50 16.90 18.30
Sulfates 15.38 16.49 15.45 17.50 22.95 28.63 48.19
Figures 1 presents the radiative drying T. phenols 0.80 1.40 1.85 1.63 2.40 2.26 2.60
Lipids 2.43 2.33 2.45 2.55 2.98 2.99 3.45
kinetics of Ulva samples.
Table1: Biochimical composition of Ulva sp.
Table 2 shows water activity values of Ulva
sp. obtained after three types of drying
processes.
ND Convective drying Radiative drying
ND 30 C 50C 70C 100 W 450 W 850 W
aw 0.402 0.113 0.124 0.139 0.484 0.361 0.127
Table 2: Water activity of Ulva sp.
Figure 1: Radiative drying kinetics of Ulva sp.
at different drying intensities (100-850W)
Water activity is proportional to the
The drying rate was found to increase increase of convective drying. However it is
with temperature in convective process. inversely proportional to the increase of
However the increase of microwave radiative powers.
powers influences the drying curves and 3.3 Techno-functional properties
the time of dehydration. In addition, the
kinetics curves obtained for both drying Three functional properties of powdered alga
processes reveal similar kinetics behavior, were studied: Swelling capacity (SWC),
not showing a constant drying rate period Water holding capacity (WHC), Oil holding
and not the drying time. In fact, radiative capacity (OHC) at ambient temperature.
drying is operating in a few minutes. While 4. Conclusions
the convective one takes about 20h.
Seven mathematical models were tested The drying kinetics of the Ulva sample have
to fit all experimental data: Logarithmic been studied with three methods: convective
model and Page model show the best (two types) and radiative drying. The drying
fitting qualities for all convective and experiments were conducted at inlet
radiative drying experiments, respectively. temperature of drying air of 30-70C, and at
inlet powers of 100 850W. The Page model
3.2 Biochemical Composition gave the best fitting quality for radiative
Table 1 shows the biochemical experiments, while logarithmic model is the
composition of Ulva sp. obtained after best for convective drying. Nevertheless,
applying three types of drying processes. swelling capacities, water and oil holding
For convective drying, the inlet of capacities decreased significantly. High
temperature seems to have a negligible temperatures gave the best properties.
effect on biochemical compositions of the References
Ulva, since the results obtained after
[1] Lahaye, M., & Jegou, D. (1993). Chemical and
drying at 30C are quite similar to those physicalchemical characteristics of dietary
obtained after drying at 70C. Contrary to fibres from Ulva lactuca (L) Thuret and
radiative process, where total sugar and Enteromorpha compressa (L) Grev. Journal of
Applied Phycology, 5, 195200.
protein increase clearly. Others compounds
Optimisation of sugarcane compounds and to monitor their quality and

their amount with precision and accuracy.
bagasse fractionation process The extracted lignin was then extensively
using Design of Experiments characterized using FTIR, RMN, TGA, DSC,
(DOE) GPC, and CHNOS.
Aboul-Hrouz Soumia 1, Oumam Mina 2, Key words: Bagasse, cellulose, lignin,
hemicelluloses, DOE
Barakat Abdellatif 3, Solhy Abderrahim 4,
References:
Zahouily Mohamed 1, 4 [1] Z. Huang*, X. Liang, H. Hu, L. Gao, Y. Chen, Z. Tong.
1. Laboratory of Materials, Catalysis and Valuation of Influence of mechanical activation on the graft
Natural Resources, URAC 24. Facult des sciences et copolymerization of sugarcane bagasse and acrylic acid.
techniques Mohammedia. University Hassan II- Polymer Degradation and Stability 2009, 94, 17371745.
Mohammedia, casablanca B. P. 146, 20650, Morocco. [2] Mr. Bouchaib IHSSANE, Chimiomtrie et Contrle
2. Team of Thermostructural Materials and Polymer, qualit de substances actives dans Les formes
LIMAT-Faculty of Sciences Ben M'sik. University Hassan pharmaceutiques Mise au point et Validation analytique des
II-Mohammedia, Casablanca. Morocco mthodes dveloppes. Ph.D. Thesis, Hassan II-
3. SUPAGRO-INRA-CIRAD-UMR IATE 1208. Mohammedia. Casablanca University March 2010.
Agropolymer Engineering and Emerging Technologies.
2, Place Pierre Viala, Bldg 31, 34060 Montpellier cedex
1, France.
4. MAScIR Foundation, Institute of Nanomaterials &
Nanotechnology, ENSET, Av. De lArm Royale, Madinat
El Irfane 10100 - Rabat, Morocco.
Abstract
Sugarcane Bagasse is the by-product
obtained after sucrose extraction from the
sugar cane plant. In this work, sugarcane
bagasse was fractionated to cellulose,
hemicellulose and lignin by alkali
treatment. This process consists in
hydrolyzing bagasse by hot water for 120
min to extract hemicelluloses. The residue
obtained is treated with sodium hydroxide.
The black liquor is acidified by the
recovered sulfuric acid to pH 2 to 3. The
precipitate is washed, dried in an oven, and
then ground in a mortar to obtain a uniform
powder.
The yields of lignin and cellulose depend
greatly on factors that affect the process.
So we aimed in this study to identify the
effect of different factors on the extraction
yields and also on the quality of the
obtained compounds. We exploited
Chemometrics methods, such as design
experimental and statistical approaches
applied to optimize and validate the
process of extraction. The optimization of
the process was performed according to the
central composite experimental design, by
studying three factors : the amount of
sodium hydroxide, temperature, and
reaction time.
Thus, the optimized conditions allowed us
to obtain a good separation of the
Recovery of valuable marine underutilized has a nutritional value almost as

good as whole seafood [1]. Although there are
compounds from cuttlefish many approaches to further utilisation of these
by-product hydrolysates: resources, interest has been expressed in
combination of enzyme isolating or processing value-added
components [2].
bioreactor and separation
2. Experiment
technologies
Emna SOUFI-KECHAU1,2 , Raja BEN 2.1 Experimental Set Up
AMAR2, Pascal JAOUEN1 and Jean- A UF/NF Microlab40 pilot plant (VMA
Pascal BERGE3 Industry) with a maximum capacity of 5L was
used. Four organic UF and NF membranes
1. Nantes University, GEPEA-UMR CNRS 6144, B.P. PCI with a tubular configuration were selected
406, Saint-Nazaire, FRANCE, esoufi@gmail.com
for treatment of CH in total recycling mode
2. Laboratory of the Sciences of Material and
Environment, Faculty of Sciences of Sfax, TUNISIA (i.e. permeate + retentate): MT O4 (MWCO
3. Laboratory of the Food Science and Technology, 300Da, PA/PES), MT PO4 (MWCO 4kDa,
Ifremer, Nantes, FRANCE PES), MT 68 (MWCO 8kDa, PS) and MT 120
Abstract: (MWCO 20kDa, PS). Operating conditions
Recognition of limited resources and were :Temperature 15C, tangential velocity
increasing environmental pollution has 2.5 m/s and pressure ranging from 8 to 35
emphasised the need for better utilisation bars: Although operating conditions were not
of fisheries by-products (e.g. heads, optimized, they can be considered as standard
frames, viscera). The present investigation conditions for the membranes, thus allowing a
explores the technical feasibility of "clean comparison of membrane performances,
technologies", i.e. enzymatic hydrolysis which were described by the evaluation of
and ultrafiltration to fractionate and RR.
concentrate Sepia hydrolysates. The 2.2 Materials
selected UF membranes with intermediate
Molecular Weight Cut Off (MWCO The spray-dried cuttlefish hydrolysates CPH
ranging from 2 to 10 kDa) allowed (0,1<Mw<10 kDa) were obtained by
fractionating hydrolysates in several Protamex, Alcalase and Flavourzyme
fractions of different molecular weights. bioreactor hydrolysis at the laboratory.
The combined study of chromatographic 3.3 Process performances
data, amount of peptides and fatty acids The process performances are principally
quantified in permeates and retentates described by the degree of hydrolysis (number
allowed us to study the progression of the of peptide bonds broken/total peptide bonds)
fractionation in correlation with the for enzymatic hydrolysis process. For
increase or decrease in interesting membrane fractionation, the permeation flux,
molecules. and the selectivity of the membrane were
followed. The permeation flux is defined by
Key words: Sepia officinalis, enzymatic the volume of solution crossing the membrane
hydrolysis, ultrafiltration
per unit of surface and of time (L.h.m-2). The
1. Introduction selectivity is defined as the proportion of
Depending on seafood species and peptides retained by the membrane and can be
processing (canning, freezing,), only 50- expressed using molecular weight distribution
70% of this catch is really used in human profile, or as follows, by the retention rate:
diet. The remainder such as fishery by- RR = 1 - Cr
products (e.g. heads, frames, skin, viscera), Cp
are especially converted into animal feed
and oil. However, this material
where Cr and Cp are the concentration of Figure 1: Retention rate of membranes versus
peptides in permeate and retentate molecular weight cut-off of the four organic
respectively. RR varies between 0 (no membranes tested.
retention) and 1 (total retention). The UF membranes of 4kDa and the NF
Molecular weight distribution profile membrane of 0,3 kDa were chosen according
to the results of the screening. The elimination
Molecular weight (Mw) distribution profile of all the peptides of Mw higher than 4kDa
of permeates and retentates were analyzed was observed in the UF permeate, thus
by size exclusion chromatography using a demonstrating a good selectivity of the
Superdex Peptide HR 10/30 column membrane tested. Then, the UF permeate was
(Pharmacia) in FPLC mode (fractionation concentrated using 300Da NF membrane. The
range of the column was 7000 to 100 Da) initial permeation flux of 200 L.h.m-2
according to Guerard and others (2001). remained constant during the 30 minutes of
The mobile phase (isocratic elution) experiment. This result demonstrated the
consisted in water with TFA 0.1% and absence of membrane fouling. The NF
acetonitrile (70:30). The flow rate was 0.5 membrane retained 92% of peptides (Figure
ml/min. 2).
The liquid chromatographic system
0,8
consisted in a Waters 600 automated UF permeate 77,2%
NF permeate 82%
gradient controller pump and a Waters 996 Absorbance (220nm)
0,6 NF retentate 79,4%
photodiode array detector. Millenium 32
software was used to collect, plot and 0,4
process the chromatographic data.

0,2
The retention rate of the tested membranes 0,0
0 10 20 30 40 50 60
Time (min)
is shown in Figure 1. The NF membrane
showed a retention rate of 98 %. Figure 2. Elution of UF permeate, and NF permeate
Consequently, this membrane may be used and retentate from Superdex Peptide HR 10/30 after
fractionation using 0,3 kDa NF membrane (see
for concentration or purification of experimental procedure in Fig.2). The antioxidant
hydrolysates. activity of samples ranged from 77,2 to 82 %.
Conversely, the 20 kDa UF membrane has 4. Conclusions
a relatively low retention rate of about 30
%. This membrane could be used for The present study showed the good
separation of peptides from proteins or performances of the organic membranes tested
enzymes in a membrane enzymatic reactor. to fractionate Cuttlefish protein hydrolysates
The UF membranes of 4 and 8 kDa Future works will explore some fractionation
presented intermediate retention rates criteria other than molecular weight, Then, the
ranging from 70 % to 80 %, and could be optimized process could be applied to
used for peptide fractionation. concentration of peptidic fractions with wide
range biological activities.
Acknowledgment
This work was performed within the
Integrated French/Tunisian Research Project.
References
[1] Synowiecki J, Al-khateeb NAAQ. 2000. The recovery
of protein hydrolysate during enzymatic isolation of chitin
from shrimp Crangon crangon processing discards. Food
Chem 68: 147-152. (Journal article)
[2] Venugopal V, Shahidi F. 1995. Value-added

products from underutilized fish species. Crit
Rev Food Sci Nutr 35(5): 431-453. (Journal
article)
Water vapour desorption and

shelf life prediction of
Tunisian Deglet Nour dates
(Phoenix dactilyfera)
Abdelkader Nabili and Elimame Elaloui
Unit de recherche: Matriaux,
Environnement et Energie . Facult des
sciences de Gafsa, Sidi
Ahmed Zarroug 2112 Gafsa-Tunisie.
Abstract
Desorption experiments were conducted at 5,
30 and 40C for Deglet Nour dates
collected from Degache oasis in west south
of Tunisia . Fruits, sorted out according to
the
CEE-ONU DDP-08 standard (2010), were
hydrated then equilibrated over saturated salt
solutions in the range of relative humidity
from 11 to 92%. Experimental equilibrium
moisture content data versus water activity
were fit to the Guggenheim -Anderson-de
Boer
(GAB) model. Agreement was found
between experimental desorption isotherms
and
predicted values using the mean relative
percentage deviation and the coefficient of
determination. The monolayer moisture
content was 15,47, 11,21 and 9,95% (dry
basis) at
5, 30 and 40C, respectively. Critical
moisture content were estimated to be 25,7
% (dry
basis) at 5C. This value is smaller than what
the CEE-ONU DDP-08 standard imposes for
commercial whole dates. Heat of desorption
estimated using the Clas iusClapeyron
equation
was estimated to be 15,1 Kcalmol-1. The
Heiss and Eichner equation was used to
predict
the shelf life. Theoretically, Deglet Nour
dates packed with a polyethylene film and
stored at
85% relative humidity, can keep their
organoleptic characteristics for 210 days at
5C.
Key words: Desorption isotherms, GAB
model, heat of desorption, critical moisture
content,
shelf life.
EFFECT OF MILK and most of the spoilage microorganisms that

may be present in milk. However, milk
PRETREATMENT ON pasteurization is also known to adversely
CHEMICAL affect the development of many quality
COMPOSITION AND attributes of dairy products [2,3].
Thermization at a sub-pasteurization
SENSORY QUALITY OF temperature (5768 C for at least 15 s) can be
TRADITIONAL TUNISIAN an alternative to pasteurization [4]. The
FERMENTED MILK, objective of this work was to evaluate the
effect of milk heat treatments on the chemical
RAYEB composition and sensory quality of Rayeb that
Hajer Debbabi1 and Hela Gliguem1 may influence the consumers acceptance.
1. Laboratoire de recherche dEconomie, de Sciences 2. Experiment
et de Technologies Agroalimentaires, Institut
National Agronomique de Tunisie, Universit de
2.1 Milk sampling and chemical analysis
Carthage, 43 avenue Charles Nicolle, 1083 Tunis,
Tunisia Fresh cow milk was procured from a local
debbabih@gmail.com,hela.gliguem@yahoo.fr
dairy farm (Cap Bon, Tunisia). Milk total
nitrogen, lactose, fat contents, dry matter and
Abstract: titratable acidity were determined with
The objective of this study was to MilkoScan Minor (Foss, Danemark) and were
investigate the effect of heat pretreatment carried out in triplicates. All milk was tested
of milk on the quality characteristics of for antibiotic residue prior to rayeb making.
Rayeb. The heat treatment methods of cow 2.2 Rayeb Manufacturing and Analysis
milk used included thermization of cow
milk at 65C for 15 min and pasteurization The milk was filtered and heat treated either to
at 91C for 40 s. Fat and proteins contents (i) 65C for 15 min in water bath and (ii)
and pH values were lower in raw milk pasteurized at 91C for 40 s. The milk was
rayeb than thermized and pasteurized milk then cooled to about 30C and added with
products (p<0.05). Milk heat treatment starter culture at 1% under sanitary conditions.
induced a reduced lipolysis The sensory The starter culture (Dlice-Danone, Tunis,
evaluation revealed acceptance of the three Tunisia) consisted of Lactococcus lactis
types of rayebs with preference to the raw subsp. lactis, L. lactis subsp. cremosis, L.
milk rayebs than the other two types of delbrueckii and mesophilic Streptococcus
rayeb. organisms. After stirring inoculated milks
were incubated at 32C for about 10 h, and
then cooled to about 4C for 24h.
Key words: Rayeb, milk, heat treatment, quality
Titrable acidity, pH, dry matter, crude fat, ash
1. Introduction and free fatty acids (FFA) in rayeb samples
were determined as per standard methods [5].
Rayeb is a popular fermented Tunisian
Total protein (6.5 x N) content was
dairy product prepared by spontaneous
determined by the Kjeldahl method [5].
cow milk fermentation. Recently, Rayeb
Sensory analysis of Rayeb was carried out as
has been produced in pasteurized form by
per standard methods for dairy products [6].
most dairy factories in Tunisia. The effects 2.3 Statistical analysis
of heat treatment on the milk major Values were expressed as mean standard
components are important for the final deviation and statistically analyzed using
product quality, since they undergo GraphPad Prism v. 4.00 software (2003).
modifications affecting the quality of dairy
products [1,2]. In dairy processes, heat 3. Results and Discussion
treatment of milk is performed to reduce The physicochemical composition of raw
microbial loads and eliminate pathogens milk and rayebs made from raw, thermized
and pasteurized milks are presented in Table 2. Quantitative descriptive analysis of rayebs
Table 1. made from raw, thermized and pasteurized milks
(n= 12 trained panelists ; a,b in column p<0.05)
Table 1: Physicochemical composition of Treatment Colour Odour Texture Taste
rayebs made from raw, thermized and Control 4.8a 3.9a 6.6a 6.0a
pasteurized milks (n=3; a,b,c in line p<0.05) Thermized 4.2a 2.9a 5.3b 4.9b
Contents Milk Rayeb Pasteurized 4.1a 2.4a 4.9b 4.5b
Raw Thermi- Pasteuri The intensity scores for texture and taste
zed -zed decreased significantly as a result of heat
pH 6.74 4.63 4.85 4.87 pretreatment (p<0.05). A consumers
0.02a 0.03b 0.04c 0.10c acceptance test (n=120 naive panelists)
Titratable 15.1 69.3 54.5 53.6
Acidity 0.8a 0.1b 0.1c 0.5c
showed that 52% preferred raw milk rayeb,
(Dornic) while rayebs made from thermized and
Dry matter 107.6 94.4 97.54 98.9 pasteurized milks were preferred by
(g/L) 0.8a 0.6b 0.9c 0.6c respectively 24% and 24% panelists.
Protein 31.4 21.5 24.9 25.4
(g/L) 0.6a 0.4b 0.4c 0.3c 4. Conclusions
Fat (g/L) 27.9 20.5 23.0 25.4
0.5a 0.3b 0.3b,c 0.5c
Heat pretreatment induced significant changes
Ash (g/L) 7.2 7.1 6.8 6.17 in acidity and chemical composition of rayeb.
0.08a 0.14a 0.8a 0.04a Descriptive sensory data indicated a decrease
FFA (mg/g) - 3.24 0.89 0.88 in taste and texture compared to the raw rayeb
0.10a 0.02 b 0.03 b milk cheese. Several changes could be
Chemical composition of fresh raw milk attributed to the biochemical changes of milk
indicated suitable technological properties. components due to the heat and to the quality
During the curd formation, the pH fell of starter cells. Spontaneous starter cells
faster in raw milk than in heat treated present in raw milk are responsible of a
milks (pH<0.05 ; data not shown). Rayebs typical taste appreciated by consumers. Future
made from thermized and pasteurized milk studies are needed to define the conditions
were characterized by higher pH and lower (time, temperature) required to achieve the
titrable acidity values than raw milk rayeb, correct balance of positive effects of heat
although no significance difference treatment.
between thermized and pasteurized milk
products. This can be due to a high Acknowledgment
microbial content of rayebs from raw milk The authors are grateful to Youssef Bach Hamba
than thermized and pasteurized milk(data and Delice Danone (Tunis) for processing rayebs.
not shown) and the greater utilization of
lactic acid leading to low pH value [1]. References
Heat pretreatments significantly increased
[1] Law, B. A., Tamine A. Technology of Cheesemaking, 2nd
protein and fat contents in rayebs (P ed., Wiley-Blackwell, Hoboken, NJ, USA 2010.
<0.05), in agreement with results obtained [2] Singh, H., Waungana, A. Influence of heat treatment of
with cheese [1-3]. No significant milk on cheesemaking properties. Int Dairy J, 2001, 11, 543-
551.
differences in the ash contents were [3] Imafidon, G. I., & Farkye, N. Y. Composition of Cheddar
noticed between raw and thermized milk cheese made from high-heat treated milk. IDF Seminar
cheese. Milk heat pretreatment Cheese yield and factors affecting its control, Cork, Ireland,
Apr 1993. International Dairy Federation, Brussels, 1993.
significantly (P<0,05) induced a decrease [4] Commission Regulation (EC) No 2074/2005. Off. J. Eur.
in total FFA content in rayebs (Table 1); Union L, 2005, 338, 2759
that could be due to the inactivation of [5] AOAC. Official Methods of Analysis, 19th Ed., AOAC
INTERNATIONAL, Gaithersburg, MD, USA, 2012.
milk lipoprotein lipase which is relatively [6] ISO 22935. Lait et produits laitiers- Analyse sensorielle,
heat-labile enzyme [7]. 2009.
Table 2 showed the effect of milk heat [7] Driessen, F. M.. Heat inactivation of lipases and
proteinases (indigenous and bacterial). In Heat induced
treatment on rayeb sensory quality. changes in milk, International Dairy Federation, Brussels,
1989, Bulletin 238, pp.7193.
Influence of Enzymatic algae. Enzymatic hydrolysis leads to the

extraction of more soluble compounds than
Hydrolysis Conditions on aqueous extraction. Protease is the most
Composition of Ulva Sp. polyvalent enzymes, and the most efficient for
Extracts the extraction of soluble compounds. The
specificity and selectivity of enzymes offer the
Salma TRABELSI REKIKa, b, Bilel
opportunity to guide the extraction toward the
HADRICHa, Karim KRIAAa, Nathalie desired molecules to produce specific interest
BOURGOUGNONb, Nabil KECHAOUa compound. It provides the ability to work at
a
Groupe de Recherche en Gnie des Procds
Agroalimentaires, Laboratoire de Recherche en
low temperature, without chemicals and
Mcanique des Fluides Applique - Gnie des Procds - ensuring a good quality of the products.
Environnement, Ecole Nationale dIngnieurs de Sfax, Key words: Green seaweeds Ulva sp., enzymatic
Universit de Sfax, BP 1173 3038, Sfax, Tunisie. hydrolysis, acidic hydrolysis, extracts composition,
b
Universit europenne de Bretagne, Laboratoire de specificity and selectivity of enzymes.
Biotechnologie et Chimie Marines (LBCM), Universit
de Bretagne-Sud, Centre de Recherche Yves Coppens, 1. Introduction
Campus de Tohannic, 56017 Lorient Cedex, France.
salmatrabelsirekik@gmail.com ; bilelhadrich@yahoo.fr ;
Several algae have been authorized for human
kriaa_karim@yahoo.fr nathalie.bourgougnon@univ- consumption by France authorities, including
ubs.fr; nabil.kechaou@enis.rnu.tn species of Ulva [1]. Therefore, seaweeds have
become a valuable vegetable and an important
Abstract: food ingredient in the human diet. The
The green seaweeds Ulva sp. is nutritional properties of seaweeds are not
widespread on the coasts of Sfax (Tunisia). completely known yet, and they are usually
These seaweeds are opportunistic and estimated for only their chemical composition.
cause major stranding on beaches. Their To our knowledge, the composition and
degradation leads to the toxic gases properties of the Ulva sp. seaweeds had not
production and therefore it causes public been well investigated particularly in Tunisia
health problems. Our objective is to contrary to other countries such as Japan,
valorise them. The cell wall of China and Western countries [1]. Moreover,
Ulvaphyceae is composed of a different authors showed that the chemical
polysaccharide, containing Ulvan with a composition of seaweeds varies with species,
high proportion of rhamnose, arabinose habitats, maturity and environmental
and uronic acids. Proteins are also present conditions [2].
embedded in the matrix phase. Enzymatic
hydrolysis has been chosen as an 2. Experiment
extraction method because of its specifics, 2.1 Experimental Set Up
selective and nontoxic action on cell wall. The Ulva sp. seaweeds were collected
Six commercial enzymes: two protease raw and fresh from the littoral of Sidi-
(endopeptidase, endoprotease) and four Mansour (SfaxTUNISIA). Fresh plants were
carbohydrates (cellulose, xylanase, thoroughly removed of their epiphytes, rinsed
arabinase, -glucanase,) were used on the spot with seawater, and then placed in
separately. The objective of those plastic bags. On their arrival at the laboratory,
experimentations is to study the action of the seaweed samples were again washed with
each enzyme on extracts composition (total distilled water and stocked at -20C for further
sugars, proteins, uronic acids, polyphnols, experiments. The alga sample was hashed,
ash, sulphates groups...). The composition homogenized with water and then reacted with
of the fresh Ulva sp. has been enzymes at a recommended temperature
determined after acidic hydrolysis (HCl, (50C) and free pH for 4 hours. The used
1M, 4 hours, 100C). enzymes and the enzyme/substrate ratios (E/S)
The composition of hydrolysates is are shown in Table 1. After hydrolyzing, the
exposed, for each metabolite, as a enzyme was inactivated in a water bath at
percentage of their respective rates in fresh
95C for 20 min. Each sample was show a low content of total polyphenols and
clarified from the residue by centrifugation lipids (Table 1). Majors monosugars analyzed
(8000 rmp, 15 min). All samples were kept by Gas Chromatography were rhamnose,
in -20C for further experiments. arabinose, glucose, xylose, mannose, ribose
Ratio and glucoronic acid. Figure 1 presents the
Ref. Type
E/S
TN Distilled Water (1L) 0.0% yields of 6 enzymatic extractions for Ulva.
Arabanase / -Glucanase /
V1 0.5%
xylanase / cellulase / hemicellulase 70
dry matters in hydrolysates (% )

C1 Cellulase 0.5%
60
U1 -Xylanase / -Glucanase 0.5%
50
G1 -Glucanase 0.5%
Endopeptidase (alcaline) / Endo-
40
P1 0.5%
protease 30
N1 Metallo endopeptidase 0.5% 20
HA HCl 1M (final) 0.0% 10
Table1: Hydrolysis types and ratios 0
algue brute T (-) V1 C1 U1 P1 G1 N1
Enzymes
The biochemical composition of Ulva
Figure 1: Yields of enzymatic extraction
sp. hydrolysates, were determined: total
sugars, sugars profiles, proteins, uronic
acids, polyphnols, ash, sulphates groups V1, U1 and P1 release the higher level of
and total dietary fiber content, mineral hydrolysates, they shows a selective activity
amount, amino acid profiles. for the production of enriched extracts in
carbohydrates. P1 is the most polyvalent
3. Results and Discussion enzyme used in this main study.
3.1 Composition of Fresh Ulva sp. and 4. Conclusions
Hydrolysates
Ulva sp. was hydrolysed to weaken cell
Table 2 presents the chemical composition of
different hydrolysates (g/ 100 g dry basis). walls at 50C and free pH for 4h. When
enzymatic hydrolysis was applied to algae,
extraction yields increase compared to the
Mineral Total Uronic Sulfates T.
matters sugar
Protein
acid groups Phenols
Lipids extraction investigated when there was no
Fresh Ulva
sp.
17.83 19.5 9 16.1 15.38 0.8 2.56 hydrolysis. Also enzymatic hydrolysis leads to
TN 17.4 24.5 9.39 16.5 16.4 0.86 2.83 the extraction of more sugars than water and
V1 17.9 25.8 9.25 20.1 12.4 1.65 2.45 acid extraction. The most soluble compounds
U1 17.7 21 9.27 18.4 19.5 1.6 2.15
extracted were total sugars, uronic acids and
protein, contrary to lipids and polyphenols.
C1 17.5 29.4 9.7 17.5 12.9 1.4 2.3
Ulva contains precious substances used in
P1 18 24.5 9.75 16.9 13.6 1.99 1.83
medicine and cosmetics. The use of enzymes
G1 17.8 19.4 8.32 18.3 18.1 1.6 2.73 improves the extraction yields of bioactive
N1 17.6 19.4 9.92 17.8 18.9 1.35 2.33 compounds, making it easier to breakdown the
Table2: Biochemical composition of Ulva hydrolysates walls of algae and fractionation of extracts. At
The biochemical compositions of green the precondition to develop the enzymatic
algae evaluate their potential for method which will produce "oligoulvanes".
utilization. But the main objective is to References
extract proteoglycan fraction (total sugars [1] Ortiz, J., Romero, N., Robert, P., Araya, J., Lopez-Hernandez,
19.5-29.4 g/ 100 g d.b. and protein 8.32- J., Bozzo, C., et al. (2006). Dietary fiber, amino acid, fatty acid and
9.92 g/ 100 g d.b.). For Hydrolysates, three tocopherol contents of the edible seaweeds Ulva lactuca and
enzymes V1, C1 and P1 gives the best Durvillaea antarctica. Food Chemistry, 99, 9810.
[2] Kaimoussi, A., Mouzdahir, A., & Saih, A. (2004). Variations
extraction efficiency of total sugar (Table saisonnires des teneurs en mtaux (Cd, Cu, Fe, Mn et Zn) chez
1). As well for protein, P1 and N1 showed lalgue Ulva lactuca prleve au niveau littoral de la ville dEl Jadida
the higher extraction yield. Hydrolystes (Maroc). Comptes Rendus Biologies, 327, 361369.
CONTRIBUTION TO THE need to develop models that are able to

describe accurately their operation. In this
MODELING OF paper, two models are introduced to evaluate
MEMBRANE the influence of heterotrophs arising from the
BIOREACTORS substrate that is coming from the decay of
autotrophs. This evaluation is made through
Ameni LAHDHIRI1,2, Aicha GASMI1, the contribution of this fraction of
Marc HERAN2,Ahmed HANNNACHI1, heterotrophs in the production of SMP.
Alain GRASMICK2
2. Materials and methods
1. Laboratory of process engineering and industrial Five campaigns of measurements were
systems National Engineering School of Gabes- performed. Conditions are listed in table 1.
University of Gabes, Street Omar Ibn Elkhattab 6029-
Tunisia, Tel: +216 75 392 100
amenilah@gmail.com, aicha.gasmi@yahoo.fr, Table 1: Operating conditions.
ahmed.hannachi@enig.rnu.tn, Campaign I II III IV V
2. European Membrane Institute, University of No.
Montpellier II CC05, P.O. Box 34095-France. Tel: Period 45 17 17 46 30
+33(0)4 67 14 37 23, heran@univ-montp2.fr, (day)
alain.Grasmick@univ-montp2.fr SRT 20 20 Infinite* 40 60
(day)
HRT 0.625 0.312 0.334 0.334 0.334
(day)
*No extraction. SRT is taken equal to a value large enough
Abstract (SRT = 400 days).
Membrane bioreactors (MBR) are
perceived to be a promising alternative to SMP considered in this work are protein and
the conventional activated sludge process. polysaccharides.
To optimize the operation of MBRs,
different models are used to predict their 2.1 Determination of protein
behavior and their performances. In this Proteins were assayed by the method of
work, simulations were conducted to Lowry modified by Frolund. Protein
investigate the MBR operation using concentrations standards were carried out
models that are formerly introduced: between 0 and 200 mg/L with bovine serum
Activated Sludge Model No. 1 Soluble albumin.
Microbial Products (ASM1-SMP)
complete model and ASM1-SMP partial 2.2 Determination of polysaccharides
model. These last two models are hybrid The colorimetric method used is that
models incorporating soluble microbial established by Dreywood. The sample is
products (SMP). Simulation results are heated in the presence of sulfuric acid and
compared to experimental ones. It was anthrone (2 g anthrone in 1L in sulfuric acid at
proven that the last model, which 98%). The solution is allowed to cool rapidly
overlooks the effect of heterotrophic for 30 min, then it is homogenized and the
biomass growing on debris of autotrophic absorbance is read in a spectrophotometer in
biomass, is not capable to describe cells of 1 cm with optical path length of 625
properly such a system. nm. The standard range was prepared with
glucose for concentrations between 10 and
Key-words: Aerobic MBR, ASM1-SMP complete 150 mg/L.
model, ASM1-SMP partial model, simulation.
3. Modeling
1. Introduction ASM1-SMP model is a hybrid model
MBR are nowadays increasingly used in consisted of the ASM1 model, but it
the wastewater treatment field, particularly includes an extra differential equation
those with submerged configuration. This describing the influence of SMP, which
interest in MBR goes necessarily with the
allows to quantify these particles and to 4.2 Discussion

predict their effect in the system. Averages of relative error are respectively
79% and 83% for, respectively, ASM1-SMP
3.1 ASM1-SMP complete model complete model and ASM1-SMP partial
This model take in consideration all model. Then, the partial model is less
components present in the system. The accurate. Also, concentration of SMPs given
differential equation for the SMP by the partial model is always lower than the
concentration is given by: one given by complete model. This is due to
dS SMP S NH SO the omission of the contribution of these
fUAP A X BA
dt S NH K NH SO K OA heterotrophs yielded by decay of autotrophs.
SS SO
fUAP H X BH f BAP bA X BA 5. Conclusion
S S K S SO K OA The effect of this fraction of heterotrophic
f BAP bH X BH bSMP X BH S SMP

S SMP ,in S SMP biomass growing on debris of autotrophic
biomass was proven to be important in the
HRT production and the hydrolysis of SMP, and
(1) then this fraction cannot be omitted.
3.2 ASM1-SMP partial model Consequently a model, such as the partial
This model omits the fraction of ASM1-SMP model, based on the omission of
heterotrophs yielded by the decay of this part of heterotrophs is inaccurate and it
autotrophs. We obtain the following cannot predict MBR performances.
differential equation for SMP:
dSSMP S NH SO
fUAP A X BA Acknowledgement
dt S NH K NH SO KOA This study was supported by the National
f BAPbA X BA
S SMP ,in SSMP
(2)
School of Engineering of Gabes, the European
Membrane Institute and Polytechnic National
HRT School of Algiers.
4. Results and discussion References
4.1 Results [1] Henze, M.; Grady Jr, C.P.L.; Gujer, W.; Marais, G.V.R.;
Concentrations of SMP given by Matsuo T. Activated sludge model No.1. IAWQ
Scientific and Technical Report No.1, IAWQ, London,
simulation using ASM1-SMP complete 1987.
model and ASM1-SMP partial model are [2] Hyuk Baek, S.; Ku Jeon, S.; Pagilla K. Mathematical
compared to experimental ones (Figure 1). modeling of aerobic bioreactor (MBR) using activated
sludge model no. 1 (ASM1). Journal of Industrial and
Engineering Chemistry, 2009, 15, 835-840.
[3] Jiang, T.; Myngheer, S.; J.W. De Pauw, D.; Spanjers, H.;
Nopens, I.; D. Kennedy, M.; Amy, G; and A.
Vanrolleghem P. Modelling the production and
degradation of soluble microbial products (SMP) in
membrane bioreactors (MBR). Water Research, 2008, 42,
4955-4964.
[4] Lapisdou, C.S.; Rittmann, B.E. Non-steady state modeling
of EPS, SMPs, and active and inert biomass. Water
Research, 2002, 36(8), 1983-1992.
[5] Gasmi, A. Intrt dun bioracteur membranes
immerges pour le traitement de la pollution azote dans
une eau use carence en matire organique. Ph.D.
Thesis, Montpellier 2 University - National Engineering
School of Gabes, December 2012.
Figure 1: Evolution of the concentration of

SMPs according to the partial ASM1-SMP model
and the complete ASM1-SMP model along with
experimental results.
Adsorptive removal of lead from Cap Bon (NE of Tunisia) to remove lead
and zinc from synthetic aqueous solutions
and zinc from aqueous under different physico-chemical
solutions using Tunisian experimental conditions.
lignite 2. Materials and methods
Ammar Mlayah1, Salah Jellali2 2.1. Adsorbent

1
The used adsorbent is lignite collected from
Water research and technologies centre (CERTE),
Cap Bon deposit (NE of Tunisia). First, it was
Georesources laboratory. E-mail address:
dried at 45C for 24 h, then grounded and
ammarmlayah@yahoo.fr
2
CERTE, wastewater treatment laboratory, E-mail
sieved to obtain several fractions. The BET
address: salah.jallali@certe.rnrt.tn; specific area was determined using a
Quantachrom Autosorb 1 sorptiometr. The pH
Abstract: of zero point charge (pHZPC) was performed
according to the solid addition method [5]
In this study, Tunisian lignite from Cap
Bon (NE Tunisia) was used as a low cost 2.2. Adsorption tests
adsorbent for the removal of lead (Pb) and The lead and zinc adsorption onto the used
zinc (Zn) from aqueous solutions under lignite was performed through batch assays.
static conditions (batch). The experimental Synthetic aqueous solutions of lead and zinc
results showed that the used lignite could were prepared by dissolving of appropriate
be considered as an attractive low cost amount of Pb(NO)3 and Zn(NO)3 salts in
material for lead and zinc removal from distilled water. During these experiments, the
synthetic aqueous solutions. These heavy removal efficiency of the studied ions metals
metals removal increase when increasing was performed for the following experimental
the aqueous pH solutions, the initial conditions:
concentrations and the lignite dosage. The
adsorption capacities for lead and zinc - pH range of 2-5 for initial aqueous
have been evaluated by using Langmuir concentration of 100 mg/L, adsorbent
isotherm to more than 61 and 25 mg/g, dosage of 2 g/L ;
which proves that the used lignite disposes - Metal initial aqueous concentrations of 15;
of a relatively high capacity for industrial 30; 50; 80; 100; 125; 150 and 175 mg/L
wastewaters treatment. for an initial pH of 5 and adsorbent dosage
Key words: lead, zinc, adsorption; Tunisian of 2 g/L ;
lignite, batch. - Adsorbent dose of 0.4; 1; 1.6; 2; 2.4; 3;
3.5 and 4 g/L for an initial metal
1. Introduction
concentrations of 100 mg/L and pH of 5;
Lead and zinc are considered as common
The analysis of metal concentrations was
toxic hazardous metals. They are released
performed by an atomic absorption
into the environment from different ways.
spectrometer (Perkin Elmer AAnalyst). The
Their accumulation in living organisms
pH measurements were done by a pH meter
presents a serious and complex problem
(692 pH/Ion Meter, Metrohm).
that has been a focus of attention all over
the word [1]. The conventional techniques 3. Results and Discussions
for the removal of heavy metals included 1.1. Characterisation of the adsorbent
ion exchange, filtration, electrolytic or
liquid extraction, chemical precipitation, The specific surface area and the pHZPC of the
reverse osmosis and membrane techniques used lignite were evaluated to 11.2 m2/g and
[2-4]. The aim of this experimental study is 3.6 respectively. These values indicated that
to test the efficiency of lignite collected this solid matrix could be used as an efficient
adsorbent for heavy metals.
3.2. Sorption experiments results Increasing the amount of lignite from 0.4 to 4
g/L, leads to an increase of the metals removal
3.2.1. Effect of contact time
from the aqueous solutions. For an adsorbent
The removal of the studied metals by dose of 3 g/L, the maximal removal efficiency
lignite studies showed that relatively high was estimated to be about 92% and 42% for
adsorption rates were observed at the lead and zinc respectively.
beginning of the adsorption process (<5
min). Then the adsorption increases but 3.2.5. Isotherm modelling
with slower rates. The equilibrium is The isotherm modeling of lead and zinc
reached after about 40 min. adsorption onto lignite has been performed
using Freundlich, Langmuir and Temkin
3.2.2. Effect of the pH
isotherms. The results showed that the
The percentage of adsorbed lead and zinc experimental results were well fitted by all the
ions highly increases with increasing the tested models. The adsorption capacities for
pH values (Fig.1). The relatively lower lead and zinc have been evaluated to more
adsorbed amounts at lower pH values than 61.4 and 25.6 mg/g, which proves that
could be explained by the competition the used lignite disposes of a relatively high
between ions metals and H+ and also the capacity for industrial wastewaters treatment.
positively charged external surfaces
(pHPZC=3.6). 4. Conclusions
60
The present study showed that lignite from
Lead Cap Bon could be considered as a highly
Zinc
Adsorbed amount (mg/g)
effective, inexpensive and naturally available

40
adsorbent for lead and zinc removal from
aqueous solutions. The maximum adsorption
20 capacities are achieved when the pH solution,
the initial concentrations and the lignite
0
dosage were relatively high.
2 3 4 5
pH References
Fig.1: effect of pH on Pb and Zn removal 1. B. Volesky, biosorption by fungal biomass. In
biosorption of heavy metals; CRC Press: Boca
by lignite Raton, FL, 1990. pp 139-172.
3.2.3. Effect of the initial concentration 2. H.A. Qdais, H. Moussa, Removal of heavy metals
The adsorbed amount of Pb and Zn from waste water by membrane process: a
comparative study, Desalinisation 164(2) (2004)
decreases with the increase of the initial 105-110.
concentrations. Indeed, the adsorption 3. E. Pehlivan, G. Arslan, Removal of metal ions
efficiency of lead decreases from 100% to using lignite in aqueous solution low cost
about 60% for initial concentrations of 15 biosorbents, Fuel Process. Technol. 88 (2007) 99-
106.
and 175mg/L respectively. This finding is 4. S. Milicevic, T. Boljanac, S. Martinovic, M.
due to the fact that for low concentrations, Vlahovic, V. Milosevic, B. Babic, Removal of
the ratio of surface active sites on lignite to copper from aqueous by low cost adsorbent-
Kolubara lignite. Process. Technol. 95 (2012) 1-7.
the total metals ions in solution is high and 5. W.S.W. Ngah, M.A.K.M. Hanaah, Adsorption of
hence all metal ions may interact with the copper on rubber (Heveabrasiliensis) leaf powder:
adsorbent. Since the driving force that Kinetic, equilibrium and thermodynamic studies,
Biochem. Eng. J. 39 (2008) 521-530.
presents concentration gradient is stronger
in case of high concentrations, adsorbed 6. E.P. Barret, L.C. Joyner, P.P. Halenda, The
determination of pore volume and area distribution
metals amount per unit of adsorbent mass in porous substances. I. Computations from
will be higher. nitrogen isotherms. J Amer. Chem. Society 73
(1951) 373-380.
3.2.4. Effect of the adsorbent amount
pines barks supports a stratum of 50cm of

Impact of nutrients supply on composted wood mulch).
the elimination of hydrogen The reserve of liquid pollutants (DMDS and
sulfide, dimethyl disulfide and EtSH) is a 250 ml cylinder pressurized under
1 bar of air. High concentrated flow of
ethanethiol by biofiltration hydrogen sulfide is provided to the system by
Mouna Ben Jaber1, Benot Anet2, Jalel a gas tank concentrated at 2500 ppm in
Belghaieb1, Abdeltif Amrane1,3 nitrogen.
and Catherine Couriol3,4. Biofilter watering is ensured by a peristaltic
pump for selecting a nutrient solution or
1. Ecole Nationale dIngnieurs de Gabs-Tunisie, Rue deionized water.
Omar Ibn-Elkhattab 6029, Gabs, contact@enig.rnu.tn.
2.2. Operating conditions and start-up
2. Ecole Nationale Suprieure de Chimie de Rennes,
CNRS, UMR 6226, Avenue du gnral Leclerc, CS
50837, 35708 Rennes Cedex 7, France, Table1: Operating conditions.
contact@enscrennes.fr.
Phase Duration [H2S] [EtSH] [DMDS] Qgaz
3. Universit europenne de Bretagne, 5 Boulevard
Lannec 35000 Rennes France.
(days) (mg/m3) (mg/m3) (mg/m3) (m3/h)
1 14 3.8 3.8 3.8 1.07
4. Universit Rennes1, UMR 6226, IUT, 3 Rue du Clos 2 65 7.6 7.6 7.6 1.07
Courtel, 35704 Rennes Cedex 7, France.
Table2: Composition of the nutrient solutions.
Abstract
Biofilter BIO1 BIO2 BIO3
This study is based on the treatment of [K2HPO4] (g.L-1) 0 0.02 0.12
sulfur compounds in mixture: Hydrogen [(NH4)2O4] (g.L-1) 0 0.08 0.48
sulfide (H2S), dimethyl disulfide (DMDS) [Na2CO3] (g.L-1) 0 0.39 1.97
and ethanethiol (EtSH) by biofiltration 3. Results and Discussion
process. A significant effort is focussed on
the impact of nutrients supply and pH
changes on the treatment performance of
the process.
Key words: Biofiltration, Pollutants, Sulfur
compounds, Nutrients, Elimination efficiency.
1. Introduction
Perception thresholds of pollutants, Figure 1: Elimination efficiency (%) of H2S in
especially those of sulfur compounds, very different biofilters.
low, force to achieve high abatement rates,
without these the residual concentration
may cause a significant impact on the well-
being of local populations.
2. Materials and methods
2.1. Experimental Set Up

The biofiltration unit consists of three
PVC columns. The internal diameter of
each column is 150.4 mm. The biofilter is Figure 2: Elimination efficiency (%) of EtSH in
different biofilters.
composed of two stratums of organic
packing materials (a stratum of 50cm of
and less than 3 in the stratum of pines barks in

all biofilters.
Figure 3: Elimination efficiency (%) of

DMDS in different biofilters.
It was observed that H2S is totally Figure 4: Decrease of pH on biofilters for the bed
eliminated from the first day (Figure 1). height of 25 cm and 75 cm.
The supply of nutrients has no influence on
the abatement of H2S. However, by The pH decrease can be explained by the
increasing the concentrations of pollutants production of sulfuric acid (H2SO4) from
(7.6 mg/m3), the influence of nutrients microbial activity [3].
supply on the degradation of EtSH and The nutrient solution or water added to
DMDS can be clearly underlined. The biofilter can maintain pH over the top of the
removal efficiencies of these compounds in bed. Thus, the decrease was more pronounced
the columns sprinkled by nutrient solutions at the bottom (2<pH<7) than at the top
(BIO2 and BIO3) are better than those in (6<pH<8.5).
the first biofilter operated just with Moreover, most biofilters perform best when
deionized water. the bed pH is between 6 and 8 [4]. Therefore,
the decrease of pH can inhibit microbial
After the stop of operation during two activity.
weeks, the system remains unstable. The
abatement of H2S is always of 100%.
However, the removal efficiency of EtSH 4. Conclusions
starts to decrease from the 23rd day to rise The results presented demonstrate that
gradually until reaching 80% (Figure 2). nutrients supply improves the treatment of
For the DMDS, the abatement stabilizes sulfur compounds in mixture, especially the
around 95% (Figure 3). abatement of recalcitrant pollutants (DMDS
The decrease of the removal efficiencies of and EtSH). In addition, the decrease of pH in
EtSH and DMDS can be due to a direct biofilter and the presence of H2S can inhibit
inhibitory effect on the metabolism of the degradation of EtSH and DMDS.
some microorganisms. When treating a References
mixture of sulfur compounds, the presence [1] Ramirez, M. Biofiltration of reduced sulphur compounds
of H2S inhibits the removal of some and community analysis of sulfur-oxidizing bacteria.
organic reduced compounds (EtSH and Bioresource technology. 2011, 102, 40474053.
DMDS) which are more resistant to [2] Hernandez, J; Lafuente, J; Prado, O.J. Simultaneous
biodegradation [1]. removal of H2S, NH3, and Ethyl mercaptan in
biotrickling filters packed with poplar wood and
Moreover, pH has a significant impact on polyurethane foam: Impact of pH during startup and
treatment efficiency. Microbial activity is crossed effects evaluation. 2012, 223, 3485-3497.
disturbed by any modification of pH in the [3] Smith, N. A., Kelly, D.P. Mechanism of oxidation of
biofilter [2]. dimethyl disulphide by Thiobacillus thioparus strain E6.
1998, 134, 3031-3039.
The study shows that the pH was decreased [4] Premkumar, R. Effect of secondary parameters on
in the two stratums of biofilters (Figure 4). biofilter treating industrial effluent. PharmTech. 2012, 4,
On the 71st day, the pH is lower than 6.5 1279-1287.
in the stratum of composted wood mulch
Enhancement in the removal efficiencies varied in the wide range

between 16% and 60%. The polymeric
Physicochemical Treatment aluminum sulfate was the most effective
Efficiency method with 60% COD and 65% turbidity
of Cheese Whey Wastewater: removals
efficiency in the chemical treatment of cheese
Optimization Through whey effluent. The use of a coagulant aid
Response Surface (flocculant) enhances these removals
Methodology efficiency which can attend 91% and 93%
S. Abdelkader, I. Khouni*, A. Ghrabi respectively.
Laboratory of wastewater treatment, Water In addition, a pH variation demonstrated a
Research and technologies centre of Borj- clear influence on the treatment efficiency,
Cedria especially for pH values fixed in the range of
(CERTE) BP 273, 8020 SOLIMAN- 6.5 - 7.5.
Tunisia. In the second part of the experimental study,
*Corresponding author: Imen Khouni, E- advanced treatability experiments were done.
mail adress: imen.khouni@yahoo.fr Response surface methodology (RSM) using
central composite design (CCD) was
Abstract
successfully employed to model and to
Dairy industry is a large scale food
optimize the CF process.
production industry and plays an important
Keywords: Cheese whey wastewater,
role in causing
Coagulation/flocculation, COD removal,
water pollution. Cheese whey wastewater
Turbidity
is showing a very high potential risk of
removal, Optimization, RSM.
environmental pollution by his elevated
organic load. Chemical coagulation was a
common
method for dairy wastewater but it is a new
method for cheese whey effluent. The aim
of this
study was to investigate the
characterization and the treatability of the
cheese whey effluent
from a cheese industry located in Bizerte-
Tunisia using coagulation/flocculation
process (CF).
The wastewater coming out from the
cheese industry is characterized by high
levels of COD
(90 g/L), Nitrogen (2.59 g/L) and
Phosphorus (2.14 g/L).
In the first part of this study, chemical
precipitation studies were applied to the
raw cheese
whey effluent using different coagulant
agents: polymeric aluminum sulfate
(Al2(SO4)3),
ferric chloride (FeCl3), calcium chloride
(CaCl3) and calcium carbonate (CaCO3).
COD
Modelling of Artemisia essential part of dried plants. 30 g plant material charged

with 1 L water in the flask attached to a
oil extraction by steam distillation Clevenger-type apparatus. The plant material was
Nejib BEN ALI1, Houcine BEN DAOUD1, distilled for 4 h and oil samples were collected at
Mehrez ROMDHANE1. different intervals of time. Oil samples collected in
the receiver were separated, measured, dried over
Unit de recherche MACS, ENIG, Universit
anhydrous sodium sulphate and used for further
de Gabs Route de Medenine, 6029, Gabs, analysis.
Tunisie, benali_nejib@yahoo.fr and
2.2. Steam distillation modelling
mehrez.romdhane@laposte.net
Abstract: The mass transport of essential oil through plant
particles during hydrodistillation occurs as
The paper describes the modelling of
unsteady-state diffusion. This,process is basically
Artemisia essential oil extraction by steam
the same as the diffusion of extractive, substances
distillation. This model describes the evolution
through plant particles during solvent extraction
of the yield of the essential oil over time and
(leaching).
the variation of the mass and yield of some
The mass of each component in the trichomes over
major components: 1,8-cineole, alpha.-
Thujone, beta.-thujone and bicyclo [3.1.0] time is given by the equation:
hexan-3-ol. The first part of the model takes
only diffusion into account, in the second the = Ktr Gi W = -W ( )
solution of the transferred species is The mass of each component in the film that forms
additionally modelled. on surface of the vegetable particle:
Key words: steam distillation, essential oil, = Gi - * xivp * (C*- C)

Artemisia, modelling. The mass of each component collected is given by
the equation:
1. Introduction
Artemisia essentiel oil is commonly used in
=( )* xivp *C*
food processing, the pharmaceutical and
cosmetic industries. In the production of Equilibrium between the phases:
alcoholic beverages and many others Dalton's law for the vapor phase
preparations.
P= + Pvp
Artemisia essentiel oil is usually present in
sheets at relatively low concentrations and Raoult's Law: Pvp =
recovery techniques of high performance are
required to achieve high oil yields.Various The composition of the vapor phase yi =
techniques have been used for essentiel oil
extraction such as hydrodistillation [1,2], yw =
supercritical carbon dioxide extraction [36],
solvent extraction [4] and the simultaneous The essential oil concentration is calculated as
distillationextraction method
The present work proposes a simplified model follows: C* =
that considered the oil constituents as major 3. Results and Discussion
components (Y> 3%), anethole, the major
components, was used to describe the mass 3.1 Modeling of the extraction of essential oil by
transfer of steam extraction of Artemisia steam distillation.
essential oil. The yield of the essential oil extracted from
2. Materials and methods Artemisia leaves was 1,78 %. 22 volatile
compounds were identified by the GC-MS
2.1. Materials chromatograph mainly composed of alpha.-
Artemisia atrata were collected from the south Thujone 28%, beta.-thujone 15,65%,
area of Tunisia. The plants were collected in Bicyclo[3.1.0]hexan-3-ol 10,32% and 1,8-
autumn and winter seasons and the CINEOLE 12,22% , thus these compounds were
experiments were conducted using the aerial used like keys to estimate the Physical and
chemical properties of the oil. The evolution of regime extraction and (ii) the second corresponds
the extraction yield is given by the following to the convective transfer based on the equilibrium
figure (Figure a). liquid phase vapor [1]. The model was validated
1.8
by experimental data obtained from a laboratoir
experimental system. Solid-steam mass transfer
1.6
coefficients were determined and a diffusion
1.4
coefficient of the essential oil in the steam was
1.2 considered as a average value of the diffusion
coefficient of the representative essential oils
Yield (%)
1
Experimental
0.8
Model components. Using the Fuller method (Poling et
al, 2000.): D = 6.0460 cm2/min.
0.6
0.4
4. Conclusions
0.2 This model allows following the evolution of
0
extraction of Artemisia essential oil and the mass
0 20 40 60 80 100 120 140 160 180 200
Volume cm3 variation of each constituent of the oil at every
Fig. (a) Yield Artemisia essentiel oil steam distillation stage of distillation. It also helps to understand the
effect of various parameters on the distillation for
3.2 Modeling of essential oil major example the mass transfer coefficient, the
components extraction by steam distillation diffusion coefficient, pressure and temperature...
x 10
-6 Acknowledgment
1.4
1,8-CINEOLE The authors are very grateful to thank Mehrez
1.2 alpha.-Thujone ROMDHANE and Houcine BEN DAOUD, for
beta.-thujone
Bicyclo[ol
help and collaboration.
1
References
mass (g/g)
0.8
1 The kinetic modelling of a steam distillation
0.6
unit for the extraction of aniseed (Pimpinella
0.4 anisum) essential oil
Mehrez Romdhane1 and Chedly Tizaoui.
0.2 80:759766 (2005).
0
2 Kim N-S and Lee D-S, Comparison of different
0 20 40 60 80 100 120 140 160 180 200 extraction methods for the analysis of fragrances
Volume cm3
from Lavandula species by gas chromatography
Figure (b) Evolution of the mass of major
mass spectrometry. J Chromatogr A 982:3147
components essential oil in the trichome.
(2002).
3 Benyoussef E-H, Hasni S, Belabbes R and
14 Bessiere J-M, Modelisation du transfert de
1,8-CINEOLE
12 alpha.-Thujone matiere lors de lextraction de lhuile essentielle
beta.-thujone des fruits de coriandre. Chem Eng J 85:15
Bicyclool
10 (2002).
4 Tuan DQ and Ilangantileke SG, Liquid CO2
Yield (%)
8
extraction of essential oil from star anise fruits
6 (Illicium verum H). J Food
Eng 31:4757 (1997).
4
5 Dias dos Santos PR, Moreira DdL, Guimaraes
2 EF and Kaplan MAC, Essential oil analysis of 10
Piperaceae species
0
0 20 40 60 80 100 120 140 160 180 200 from the Brazilian Atlantic forest. Phytochemistry
Volume cm3
58:547551(2001).
Figure c: Evolution of extraction yield of the 6 Jimenez-Carmona MM, Ubera JL and Luque de
major components essential oil
Castro MD, Comparison of continuous subcritical
The model can be used to optimise and control
water extraction and hydrodistillation of marjoram
the process. Depending on the oil content, two
essential oil. J Chromatogr A
mass transfer regimes were identified (i) the
[1] 855:625632 (1999).
first one corresponds to a molecular diffusion
Modelling of a solar vacuum are direct contact membrane distillation

(DCMD), air gap membrane distillation
membrane distillation (AGMD), sweeping gas membrane distillation
equipped with helically coiled (SGMD) and vacuum membrane distillation
fibers: Effect of the feed (VMD) [2-8]. VMD has attracted increasing
interest for various applications. From energy
concentration on the permeate consumption point of view, it could clearly
flux compete with reverse osmosis, when coupled
Adel Zrelli1,2, Bchir Chaouchi2, Slimane with alternate source of energy like solar
Gabsi2 energy [11]. Furthermore, many
1. High Institute of Applied Science and Technology of configurations of the hollow fiber membrane
Gabes, University of Gabes, Omar Ibn. ElKhattab St.
6072 Gabes, Tunisia, Tel: 75 39 21 08 can be used. Among these configurations we
2. Environmental, Catalysis and Process Analysis found the linear and the helical fibers. In
Research Unity, National Engineering School of Gabes. many studies, we found that the helically
University of Gabes, Omar Ibn. ElKhattab St. -6029
Gabes, Tunisia, Tel: 75 39 21 00, Fax : 75 39 21 90 coiled hollow fibers is preferred than the
E-mail: Adel.Zrelli@yahoo.fr linear hollow fibers. This enhancement is due
to the reduction of polarization concentration
Abstract: and membrane fouling [12-16].
This paper presents the simulation of a In this work, we are trying to build a
solar membrane distillation equipped with mathematical model predicting the
helically coiled fibers. Du to this design of distributions of the concentration,
membrane distillation, a mutual temperature, activity coefficient and permeate
dependence of the mass and heat transfer flow rate. This model takes into account
appears which complicates the solution of hydrodynamics, heat and mass transport and
the system equations. After the investigates the effect of the feed
establishment of these governing concentration on the desalination performance
equations, a resolution was done with the of this projected installation.
finite element method. The results show
2. Experiment
that when feed salt concentration was
varied between 10 to 300 g/l a fall of the
permeate flux of 12% was reported. This 2.1 Design of the experimental Set Up
drop is du only to the reduction of the
activity coefficient of 20% when the salt
concentration increases from 10 to 300 g/l.
This less drop of the permeate flux, for a
high concentration of salt in feed solution,
allows to use the membrane distillation
process for water desalination instead of
other distillation processes.
Keywords: Vacuum membrane distillation; Solar

energy; Helical fiber; Simulation.
1. Introduction Figure 1: Design of the thermal solar membrane

Membrane distillation, (MD), is a distillation.
thermal process based on highly porous
and hydrophobic membrane. It can be
classified into four different configurations
according to the nature of the cold side of
the membrane [1]. These configurations

3.1 Results
Figure 5: Activity coefficient as function of relative

module length.
Figure 2: Effect of initial feed salt concentration
4. Conclusions
on the permeate flux.
In order to study the effect of the inlet salt
feed concentration on the permeate flux, for a
solar vacuum membrane distillation equipped
with helically coiled fibers, a mathematical
model has been developed. This model is able
to describe the evolutions of the
concentration, temperature, activity
coefficient and permeate flow rate along the
membrane module. The obtained results show
a reduction of 12%, for the permeate flux,
when the inlet feed concentration growth from
10 to 300 g/l. The limiting parameter in our
case is the activity coefficient which has
decreased by 20% for the same evolution of
Figure 3: Temperature polarization coefficient as the inlet feed concentration. Nevertheless, the
function of relative module length. contribution of the temperature and
concentration polarization coefficients is very
small compared to that of the activity
coefficient.
References
[1] Mengual J. I., khayet M., Godino , M. P., Heat and mass
transfer in vacuum membrane distillation, International
Journal of Heat and Mass Transfer, 2004, 47, 865-875.
[2] Imdakm A. O., Matsuura T., Simulation of heat and mass
transfer in direct contact membrane distillation (MD): The
effect of membrane physical properties, journal of
Membrane Science, 2005, 262, 117-128).
[3] Yanbin Yun, Runyu Ma, Wenzhen Zhang, A. G.,
Fane,Jiding Li, Direct contact membrane distillation
Figure 4: Concentration polarization coefficient mechanism for high concentration Nacl solutions,
Desalination, 2006, 188, 251-262.
vs. Relative module length. [4] Khayet M., Godino M. P., Mengual J. I., Theoretical and
experimental studies on desalination using the sweeping
gas membrane distillation method, Desalination, 2003,
157, 297-305.
CFD Contribution to plays a very important role in obtaining

suitable conditions for both algae and bacterial
Hydrodynamic study of a rate growth and estimating it facilitates this task.
airlift algal pond
Rym Ben Moussaa, Hatem Dhaouadib1,
Hatem Mhiria
a Universit de Monastir, Ecole Nationale
dIngnieurs de Monastir, Unit
Thermique et
Thermodynamique des Procds
Industriels
b Universit de Monastir, Facult des
Sciences de Monastir, UR Chimie
Applique Environnement
ABSTRACT
The use of numerical modeling became a
natural step in todays engineering work
and Figure 1. Three Dimensional modeling of the
research. Therefore, a three dimensional algal pond and water velocity distribution at
modeling of an existing high rate algal the airlift riser
pond located 1 * : corresponding author
in the water purification plant of Sidi hatem.dhaouadi@fsm.rnu.tn
Bouali in Tunisia is presented. The purpose
of the study
is to propose a numerical model that takes
into account the complexity of the
phenomena
involved despite the application of
simplifying assumptions.
A CFD (Computational Fluid Dynamics)
calculation based on a two-phase approach,
seen
that the physical problem presents a
continuous phase (water) and a dispersed
dilute phase (air
bubbles with a constant particle size), is
carried out using Fluent code. Velocity and
gas
retention distribution are derived by
solving the conservation equations for each
phase.
As the air flow injection rate increases, the
circulating water velocity in the pond
increases
linearly with an average of 0.18 m s-1 for
each additional 1 m3 h-1 of air injected in
each air
diffuser (8 air diffusers).
Circulating water velocity in the algal
pond, which is a function of air flow
injection rates,
Heterogeneous catalytic dissolution and enable the process optimization.
reaction: Modeling of UO2 Keywords:particle dissolution- numerical

particles dissolution in nitric model- coupledhydrodynamic and kinetics -
transfer- bubbles - cracks.
acid
HassanBOUALIAa, Alastair MAGNALDOb,
Philippe MARCb, ricSCHAERa
a:LRGP-CNRS-ENSIC-1, rue Grandville BP

20451-54001 Nancy Cedex France
b:CEA, Nuclear Energy Division,

RadioChemistry & Processes Department,
Service of Fuel Recycling Studies and
Analysis, Laboratory of Dissolution Studies, F-
30207 Bagnols sur Cze, France.
hassan.boualia@univ-lorraine.fr,
alastair.magnaldo@cea.fr, philippe.marc@cea.fr,
eric.schaer@univ-lorraine.fr
Abstract:
Comprehension and optimization of spent
nuclear fuels dissolution, that takes place at
head-end step of their recycling process, are
important to improve the current process and
prepare future fuels recycling processes.
The used nuclear uraniumand

plutoniumparticle dissolution has been usedfor
many yearsat the factoryat AREVALa Hague-
France butnow requiresa deeper
understandingof major phenomena that govern
thecoupled reaction and mass transferin order
to optimizeand improvethe current processes
and prepareplants of the future (4th generation
reactorspark) andthe associated multi-recycling
of plutonium. The dissolution stoechiometric
equation can be described by the overall
equation:
UO2+HNO3 UO2(NO3)2 +NO+H2O

The goal of this project is to establish a
numerical model able to describe the complex
and coupled phenomena occurring during
dissolution reaction of uranium oxides in nitric
acid : mass transfer from the bulk solution to
the particle surface, dissolution reaction at the
surface, impact of surface on the reaction,
bubble formation from gaseous products and
modification of the transfer by the bubbles.
The results of the study show the influence of

these different parameters on the particle
Impact of Thermal composition [1]. Recently, carob has been

investigated in food and pharmaceutical
Pasteurization on Carob Juice industries in some Mediterranean countries.
Composition and However, the use of this fruit has yet limited
Microbiological Stability in Tunisia.
The work search presents a preliminary
Leila TOUNSI, Karim KRIAA, Bilel valorization of Tunisian carob fruit. It seeks to
HADRICH, Nabil KECHAOU produce carob juice and to pasteurize it
thermally. This study focuses on the influence
Groupe de Recherche en Gnie des Procds of thermal pasteurization on microbial quality
Agroalimentaires, Laboratoire de Recherche en
and nutritional composition of carob juice.
Environnement, Ecole Nationale dIngnieurs de Sfax, 2. Experiment
Universit de Sfax, BP 1173 3038, Sfax, Tunisia
leila_enis@yahoo.fr ; kriaa_karim@yahoo.fr ; 2.1 Origin of fruits
bilelhadrich@yahoo.fr ; nabil.kechaou@enis.rnu.tn
The mature carob pods were purchased
from the local market of Sfax (Tunisia). The
Abstract: fruits were kept at room temperature prior to
This study focuses on the thermal juice extraction.
pasteurization effects on microbial stability
2.2 Preparation of carob juice
and nutritional composition of carob juice.
Carob juice was obtained from carob pods Carob juice was prepared using hot water
(Ceratonia siliqua L.) using hot water extraction (50C for 190 min) with solid-
extraction (50C for 190 min) with solid- liquid ratio equal to 1/5 [2]. After extraction,
liquid ratio equal to 1/5. The resulting juice the juice was centrifuged at 5000 rpm for 15
is rich in soluble sugars (~50%) and min to separate the solid particles.
proteins (~5%). Thermal pasteurization of 2.3 Thermal pasteurization
carob juice showed significant changes in
evaluated characteristics. In fact, an After bottling, raw carob juice was heated
important reduction in microflora number in a water bath to 70C for 15 min and then
was observed after pasteurization, cooled with cold water [3].
especially the total flora. Moreover, 2.4 Analysis
nutritional composition of carob juice was Microbial analyses were assessed
also modified after pasteurization: soluble according to Guiraud [4].
sugars content was increased, pectin Sugars were determined using the phenol-
content was decreased, protein content was sulfuric method [5]. Total pectin content was
slightly decreased, polyphenols amounts determined according to the method described
was slightly increased, the acidity value by Englyst et al. [6]. Proteins were determined
was increased, finally, vitamin C level was by the Kjeldahl method [7]. Polyphenols
decreased. content was determined using the colorimetric
FolinCiocalteu method [8]. The acidity of
Key words: (carob juice, hot water extraction, carob juice was determined by a
thermal pasteurization, microbial stability,
nutritional composition) potentiometric titration with NaOH 0,1N [9].
Vitamin C content was determined according
1. Introduction to the titration method using the 2,6-
The carob tree (Ceratonia siliqua L.) is dichlorophenol indophenols [10].
widely grown in Mediterranean area 3. Results and Discussion
including Tunisia. The carob fruits are a
cheap source of natural substances. They 3.1 Influence of thermal pasteurization on microbial
stability of carob juice
are, therefore, very important economically
and medicinally due to their phytochemical
Table 1 shows an important reduction of amounts was slightly increased from 1.6 to
microbiological counts after thermal 1.95 mg gallic acid/l, the acidity value was
pasteurization of carob juice. The total increased from 20.27 to 34.16 mg total acids
flora count was reduced from 1900 to /100ml, finally, vitamin C level was decreased
270 CFU/g, while the fungal flora was from 13.51 to 8.92 mg ascorbic acid/l.
reduced from 930 to 400 CFU/g.
4. Conclusions
Table 1: Effects of thermal pasteurization on Thermal pasteurization (70C, 15 min)
carob juice microflora improved the microbial stability of carob juice
Microbial Microbial counts (CFU/g) and resulted significant changes in its
flora Before After nutritional composition especially the increase
Total flora 1900 270 of soluble sugars content. Therefore, carob
Fungal flora 930 400 juice may be considered as potential sources
of sugar that could be used as additives in
3.2 Influence of thermal pasteurization on many foods.
nutritional composition of carob juice
The main nutritional composition of References
carob juice was analyzed before and after [1] Vekiari, S. A.; Ouzounidou, G.; Ozturk, M.; Grk,
pasteurization. The results are presented in G. Variation of quality characteristics in Greek and
Table 2. Turkish carob pods during fruit development. Procedia -
Social and Behavioral Science. 2011, 19: 750755.
Table 2: Effects of thermal pasteurization on [2] Hadrich, B. Contribution la valorisation alimentaire et
nutritional quality of carob juice non alimentaire de la caroube dorigine tunisienne. Thse
de doctorat en Gnie Chimique-Procds de lEcole
Component Before After Nationale dIngnieurs de Gabes, Universit de Gabes.
Soluble sugars(A) 48.28 4.89 b 73.88 1.14 a Avril 2011.
Insoluble sugars(A) 5.7 0.61 a 5.6 0.24 a [3] Albagnac, G.; Varoquaux, P.; Montigaud, J.C.
(A) a
Total pectin 3.22 0.12 1.9 0.15 b Technologies de transformation des fruits. Editions Tech
(A) a
Protein 4.9 0.09 3.96 0.33 b & Doc, Paris, 2002 ; 324-431.
(B) b
Polyphenols 1.6 0.08 1.95 0.02 a [4] Guiraud, J.P. Microbiologie alimentaire. Dunod, Paris,
(C) b
Acidity 20.27 4.89 34.16 5.37 a 1998 ; 473-483.
(D) a
Vitamin C 13.51 0.72 8.92 1.14 b
[5] Dubois, M.; Gilles, K.A.; Hamilton, J.K.; Rebers, P.A.;
All the given values are means of three Smith, F. Colorimetric method for determination of sugar
determinations standard deviation.
and related substances. Analytical Chemistry, 1956, 28:
Means in line marked by different letters are
350-356.
significantly different (P < 0.05).
(A) g /100 g dry matter [6] Englyst, H.N.; Quigley, M.E.; Hudson, G.J.
(B) mg gallic acid / l Determination of Dietary Fibre as Non-starch
(C) mg total acids /100 ml Polysaccharides with Gas-Liquid Chromatographic or
(D) mg ascorbic acid /l Spectrophotometric Measurement of Constiyuent Sugar.
Analyst, 1994, 119: 1497-1509.
Raw carob juice presented an important [7] AFNOR. Produits Agricoles Alimentaires: Lignes
nutritional composition with high levels of directives gnrales pour le dosage de lazote selon la
soluble sugars and proteins (48.28 and 4.9 mthode de kjeldhal. NF V03-050. AFNOR, Paris, 1970 ;
39-43.
g/100 g d. m., respectively). After thermal
[8] Waterhouse, A.L. Determination of total phenolics. In
treatment, the carob juice composition,
Current Protocols in Food Analytical Chemistry. II.1.1-
mainly, soluble sugars, pectin, protein, II.1.8. Wrolstad, R.E., Wiley.
polyphenols, acids and vitamin C was [9] AFNOR. Produits drivs des fruits et lgumes. NF 05-
significantly changed (P<0.05). Soluble 101. AFNOR, Paris, 1974 ; 26-29.
sugars content was increased from 48.28 to [10] AOAC. Method 967.21- Method IFU n 17: vitamin C
73.83 g/100 g d. m., pectin content was (ascorbic acid) in vitamin preparations and juices. ISO,
decreased from 3.22 to 1.9 g/100 g d. m., 1984 ; 6557-2.
protein content was slightly decreased
from 4.9 to 3.9 g/100 g d.m., polyphenols
MODELING OF THE Key words: adsorption, PSA, modeling, surface

diffusion, stoechiometric time.
ADSORPTION STEP BY
SURFACE DIFFUSION FOR 1. Introduction
THE PROCESS OF The pressure swing adsorption processes
PRESSURE SWING which are appeared with the American patent
of Skarstrom [1], are mainly used in the field
ADSORPTION FOR of drying air, air separation and hydrogen
HYDROGEN purification. The whole study will be based on
PURIFICATION the pure hydrogen production from gas
Belgacem Balsam1 , Chlendi Mohamed2 derived from the cracking of natural gas by
adsorption on activated carbon and molecular
1.2. Department of Chemical Enginnering-Processes, sieve. The present work aims to make a
Research Unit:Applied Thermodynamic,Research
Laboratory:Interactions Fluid-Porous environment,
comparative study between the experiences of
National School of Engineers of Gabes, Omar Ibn the adsorption step and the simulation by
Elkhattab street, Zrig, Gabes 6029, Tinisia solving the equations obtained by modeling.
1.belgacembalsam@yahoo.fr ,2.m.chlendi@topnet.tn
2. PSA process
Abstract: The PSA cycle that is actually appeared in
This work is interested in modeling of the 1958 [1], consists of two main steps which are
adsorption step for the process of pressure adsorption and regeneration, and two
swing adsorption (PSA) for hydrogen intermediate steps; compression to favor
purification. adsorption by increasing pressure and
We are interested in modeling of decompression in order to initiate the purge
adsorption of one or more compounds in a step by pressure reducing.
mixture at different pressure from 8 at 20
bars at ambient temperature. We presented 3. Modeling
the flow by the piston model with axial To model an adsorber, we must know thre
dispersion. The equilibrium isotherm was main agents which are the adsorption
expressed by the Langmuir model for the equilibrium, mass transfer kinetics and
mono-component adsorption and the dynamic behavior of the adsorption bed. The
model of Langmuir extended for the multi- flow in the bed is described by the piston
components adsorption. Moreover, we model with axial dispersion. By a mass
considered the surface diffusion model balance, we obtained the following equation:
(SD) as a model of kinetic transfer between
vCi (1 ) qi Ci 2Ci
phases + + = Daxe 2 (1)
The simulation results obtained after the z t t z
resolution of the equations of the model in Where z is the axial coordinate in m, qi is the
a developed program, compared with the amount of adsorbed gas i in mol/Kg, Ci is the
experimental results from old works, show adsorbed gas concentration in mol/m3 and v is
a rather satisfactory agreement on the level the velocity of the gas flow.
of stchiometric time and kinetic mass The mass transfer between phases is limited
transfer. by internal diffusion in the pores, the equation
As a first step, we studied the adsorption of governing the adsorption process is the
CH4/H2 mixture on activated carbon. In a following, according to the DS model:
second step, we studied the adsorption of qi 2 qi 2 qi
CH4/CO2/H2 on activated carbon and = Ds 2 + (2)
t r r r
CH4/N2/H2 on 5A molecular sieve while
considerating an interaction parameter for Where r is the radial coordinate in m.
the extended Langmuir model.
A third equation, that describes the

variation of the flow velocity of the gas
[2], can be written as follows:
v RT (1 ) q i
z
=
P
i t (3)
To solve these equations, we adopted the

finite differences method and the function
ode15s on the software Matlab which is Fig.2. Breakthrough times of CH4 and CO2.
based on the method of Gear.
4. Simulations and results
The purpose is to compare the
simulation with the experiences from
previous works. The comparison includes
the stchiometric output time of
adsorbable compounds of the column. We
will study the adsorption of methane (CH4) Fig.3. Breakthrough times of CH4 and N2.
on activate carbon, the adsorption of CH4
and carbon dioxide (CO2) on activated 5. Conclusion
carbon and that of CH4 and dinitrogen (N2)
on molecular sieve, to produce pure During this work, we interested in the
hydrogen. The data required for the modeling of adsorption step for a PSA cycle.
simulation are extracted from the work of The choice of the piston model with axial
M. Chlendi [3] and M. Chahbani [4]. dispersion and the kinetic model DS, gives
rather satisfactory results compared with the
The following figure (Fig.1) shows the experimental result, by applying the finite
experimental breakthrough of CH4 and differences method and the function ode15s
following the DS model, which shows an on the software Matlab which bases on the
error less than 10% on the breakthrough method of Gear.
time.
Acknowledgment
The authors gratefully acknowledge the research
unit of Applied Thermodynamics at ENIG and
particularly the laboratory of Fluid Porous
Environment Interactions.
References
[1] Jimmy L. Humphery, George E. Keller II. Procds de
sparation : Techniques, slection, dimensionnement,
DUNOD, Paris, 2001.
[2] Salil U. Rege, Ralph T. Yang, Kangyi Qian, Mark A.
Fig.1: Comparison between the experiment and
Buzanowski. Air-prepurification by pressure swing
the DS model for CH4 adsoprtion.
adsorption using single/layered beds, Chem. Eng. Sc.,
2001, vol 56, 2745-2759.
Drawing the output time of the [3] Chlendi M. Thesis, Sparation de gaz par adsorption
simulation of CH4 and CO2, and the output module en pression, application ltude dun procd de
time of CH4 and N2 according to that purification dhydrogne, National Engineering School of
experimental, as shown in the Fig.2 and Gabes, 1993.
Fig.3, we notice that points are very close [4] Chahbani M. H. Thesis, Sparation de gaz par adsorption
to the y=x, what verifies that the results are modul en pression : Modlisation des coulements et de
comparable and the DS model is adequate. la cintique de transfert de matire, National Engineering
School of Gabes, 1996.
EFFECT OF WATER the thermal power provided in the combustion

chamber. These two parameters can be
STEAM INJECTION ON influenced by the variation of gas mass flow
GAS TURBINE through the turbine. Moreover, the injection of
PERFORMANCES AND water vapor in the combustion chamber
decreases the temperature of the gas; that
NOX RELEASE contributes to the good mechanical strength of
the turbine. In other hand, this injection can
Farhat Hajer1, Khir Tahar1 and Ben Brahim Ammar1 reduce the rate of NOx release. These two
1: National School of Engineers of Gabes, University of
Gabes 6029 Gabes - TUNISIA benefits justify the use of this technique on
Applied Thermodynamics Research Unit gas turbine cycles as a means of improving
(99/UR/11-21) performance and preservation of the
farhathajer79@gmail.com
taherkhir@yahoo.fr environment [2].
ammar.benbrahim@enig.rnu.tn
2.1. Cycle gas turbine with steam injection water
This technology is therefore used to inject
Abstract: an amount of water vapor in the combustion
This paper presents a study on the chamber. The turbine is under these
influence of the injection of water vapor on conditions, fueled by a large amount of gas at
the cycle performance of a gas turbine and higher pressure than the normal cycle without
on NOx releases. A numerical simulation steam injection. In addition this gas has higher
is done with software calculation EES of a moisture content and consequently a large
gas turbine cycle with an injection system heat capacity. Thus produce more power
of steam to the chamber combustion witch output of the turbine.
power equal of 100 Mw for a range of Figure 1 illustrates the principle of operation
variation of the operating variables. The of a cycle gas turbine with
results show that increasing the steam an energy recovery system HRSG at the outlet
injection rate leads to an increase in cycle of the turbine and a device for injecting the
efficiency and lower NOx emissions. generated water steam in the combustion
chamber. The water following from the pump
Key words: gas turbine, thermal efficiency, is returned to the generator collector where it
steam, optimization, Nox releases. is preheated, vaporized and superheated. The
steam generated is thereafter injected into the
1. Introduction
combustion chamber at a fixed proportion to
Gas turbines have been a great the air and the fuel flow rates [3].
development in recent years in the
Fuel
industry. It can be used in many different
industrial sectors such as power
m& f Q& h
Chambre
m& is
generation, oil and gas processing plants, 2 de 3
aviation, as well as domestic applications W&compair
Turbine
Compair
and small industries. G

Significant efforts have been made by
4 7
researchers to improve the efficiency of the i1 ,1 m& a , T1
cycle and control the pollution of the air
due to gas turbine emission, in particular P1 , m& v ,1 , 1 Pomp
6 HRS
5
by reducing the nitrogen oxide emissions
m& is
(NOx) [1]. Figure 1: Cycle of a gas turbine with steam
2. Experiment injection
The cycle efficiency of a gas turbine can 2.2. Numerical simulation:
vary by changing the specific net work and
45
The considered cycle for numerical 40
simulation is a standard cycle gas turbine 35
with steam injection in the combustion
NO (ppm)
30
chamber as shown in Figure 1. 25
To analyze the influence of water vapor 20
injection, a simulation code is established 15
0 0,05 0,1 0,15 0,2 0,25

in language EES for which a net power of yvap
100 MW is considered. The operating

conditions and the properties of the Figure 3: The amount of nitrogen monoxide
surrounding air are defined according to generated as a function of steam injection rate.
those usually considered for the STEG
power plant installed in Bouchemma The amount of nitrogen monoxide released
Gabes (South-Est of Tunisia). decreases with increasing the steam injection
The variation range of the injection rate of rate into the combustion chamber. This
water vapor is shown in Table 1: decrease can be explained that chemical
Table 1: Range of changes in operational reaction between Nitrogen and Oxygen is
variable more "efficient" for lower combustion
Variables Gammes de temperature (for higher injected steam water
rate).
opratoires variations
The variation of the gas turbine cycle
Steam injection rate 0 - 25% efficiency according to the NO emissions
level is shown in Figure 5. The cycle
efficiency decreases of about 17% for an
3. Results and Discussion increase fo NOx emissions of about 19%.
3.1. Influence of steam injection on the 4. Conclusions
cycle efficiency
According to obtained results, related to the
The influence of the steam injection on the influence of the steam injection effects,
cycle performance is shown in Figure 3. following remarks can be pointed out:
0,41
0,4
The cycle efficiency increases with the
0,39
increase of steam injection rate into the
0,38 combustion chamber.
Rcycle
0,37
Emissions of NO decreases with the increase
0,36
0,35
the steam injection rate
0,34 The cycle efficiency decreases with the
0,33
0 0,025 0,05 0,075 0,1 0,125 0,15 0,175 0,2 0,225
increase of NO release.
yvap
References
Figure 2: Evolution of cycle efficiency as a
[1] Claire Soares, Gas turbines in simple cycle & combined
function of steam injection rate. cycle applications
Cycle efficiency increases linearly of about Gas Turbines in Simple Cycle, The Gas Turbine Handbook,
ASME, USA, 2006.
20, 89 for an increase of the steam
[2] techno-science.net ; physique ; turbine gaz ; Dfinition
injection rate of about 20%. sous licence CC-BY-SA 3.0
[3] Meherwan P.Boyce, Gas turbine engineering handbook,
3.2. Influence of steam injection on the NOx Second Edition, USA, 2002
release rate.
The variation of the nitrogen monoxide
amount generated according to steam
injection flow rate in show in Figure 4
Modelling of biofuel biofuel is modeled by an overall reaction in a

single step. This model takes into account the
combustion engine: rich oxygen molecules biofuel portion. The rich
mixture and NOx emission mixture was varied to obtain the optimum
operation of the engine. The NOx formation is
(1,*) H. HEDFI and (2) K. SLIMI modeled by using a six-step mechanism with
(1) Ecole Nationale dIngnieurs, Universit de eight species. The effect of the various steps
Monastir, Rue Ibn Eljazzar, 5019, Monastir, of the formation of NOx in combustion is
Tunisie considered by using a phenomenological
(2) Institut Suprieur du Transport et de la model of combustion speed.
Logistique, Universit de Sousse, B. P. 247, This simplified model, which has been
Cit Erriadh, 4023, Sousse, Tunisie validated with available experimental results,
*Corresponding author: hedfi22@gmail.com is used to characterize and to control, in real
time, the impact of biofuel on the engine
Abstract performances and NOx emissions.
Keywords : biofuel; combustion engine; rich-
In this paper, we aim to address mixture; finite-rate kinetics; NOx
simultaneously the issues of air/biofuel
mixture combustion, emissions and post-
processing of soots. Fossil fuels (gasoline,
diesel, natural gas, etc.), in addition to the
limited planet earth characters, they are
knows as major sources of pollution.
Among the solution to the rarity of this
type of fuel, researches are oriented to
renewable fuels or biofuels. Therefore, the
impact of biofuels on the current engine
technologies for transportation should be
examined in details.
Many studies treated the influence of
biodiesel on combustion engine
characteristics. Indeed, the fuel is
considered as pure biodiesel (Kegl, 2011).
Others studies address the parameters
which influence the efficiency conversion
of diesel/biodiesel mixture (Gogoia and
Baruahb, 2010; Tziourtzioumis and
Stamatelos, 2012; Tompkins et al., 2012,
Wu and Wu, 2013). Others are focused on
the addition of an additive to the
combustion mixture in order to improve
the engine performance (Sudheesh and
Mallikarjuna, 2010).
A physical model based on a
thermodynamic analysis was established to
characterize the reaction parameters. The
time-variation of pressure and temperature
required for the calculation of rate
constants for reaction are obtained from
the solution of the energy conservation
equation. Chemical combustion of the
Membrane contactors made of composite hollow fibers: a promising tool for CO2 capture
Contacteurs membranaires fibres creuses composites: un outil prometteur pour le captage du CO2
Camel Makhloufi, Denis Roizard, Eric Favre
Laboratoire de Ractions et Gnie des Procds (CNRS UMR 7274), ENSIC Universit de Lorraine, 1
rue Grandville, 54001 Nancy France email: Denis.Roizard@univer-lorraine.fr
Keywords : membrane contactor - ammonia perfluorinated polymers gas separation CO2 capture
We reported for the very first time, the feasibility of an ammonia based CO2 capture process using
hollow fiber membrane contactors. Up to now, the reference technology for CO2 capture in
postcombustion makes use of monoethanolamine (MEA) as chemical solvent in a packed column.
Despite high capture efficiencies, MEA induces too high energy penalties. Consequently, an abundant
literature is discussing the use of aqueous ammonia for flue gas scrubbing. Indeed ammonia is cheaper
than MEA, shows a higher absorption capacity and, most of all, its energy regeneration demand is
much lower. Nevertheless, the high ammonia volatility is a considerable drawback, and its entrainment
in absorption column, causes a high NH3 slip within the flue gas. Specific operatic conditions must be
used to limit NH3 losses and in addition a post absorber scrubbing step is therefore required.
Amongst growing technologies, membrane contactor appears as a promising technology able to allow
significant process intensification when compared with conventional gas/liquid contactors. Recently,
intensification factors close to 5 have been reported for CO2 capture with MEA. So far, no study
dealing with the use of membrane contactors for the CO2 capture in aqueous ammonia has been
disclosed. It is worth noting that specific membrane contactors were specifically designed to favor CO2
absorption and, in the same time, to limit ammonia slip in the flue gas.
Indeed, reviewing the literature data shown us that up to date no polymer was known to exhibit a
selective permeation favoring CO2 versus NH3. Thus taking into account the gas permeation transport
through polymers, we analyze the permeation process of gases and vapors through dense polymers to
explain it and, if possible, overcome this problem. Usually the solution diffusion mechanism applies
quite well to qualitatively explain the permeability range and the selectivity. Hence molecules such as
H2, H20, CO2 are known to be so called fast molecules compared to O2, N2 or CH4; considering
respective characteristic of NH3 and CO2, higher permeability coefficient for NH3 can also be expected.
However it is known that reverse selectivity can occur in some specific cases, hence corresponding for
instance to the higher permeability of the biggest molecule of a mixture. Until our pioneering work,
only a very small number of permeation data was available for NH3, all showing that ammonia followed
the expected solution diffusion pattern versus any other molecules. Hence ammonia was classified as
a fast gas, exhibiting for instance much higher permeability compared to CO2, in agreement with the
solution diffusion model predictions. In this study we extended the type of studied polymeric
membranes to fluorinated and perfluorinated glassy structures (FEP, PTFE) as well as to superglassy
polymers such as Hyflon AD and Teflon AF; we got undoubting result showing that fluorinated
networks induce much lower permeability than expected ones. Thus we discovered that a reverse
NH3/CO2 permeation selectivity could be reached with fluorinated polymers, even with polymers
having a high free volume. This unusual behavior will be discussed and its potential interest in industrial
applications will be presented.
Consequently, composite hollow fiber membrane contactors having a thin skin layer facing the liquid
phase were used. This involved carefully selecting a thin and highly permeable dense layer, selective
for CO2 over NH3. Indeed this should allow to reach high CO2 mass transfer coefficient and to
drastically reduce the ammonia slip in the flue gas. This was undoubtedly one of the main challenges.
Indeed, it must be recalled that a faster permeation of CO2 compared to NH3 in dense polymers was
totally unexpected and to our knowledge unexplored. For the first time, the permeation properties of
4 different polymers showing a reverse selectivity CO2/NH3 were established. These meaningful
results were obtained thanks to time lag experiments (Fig.1&2).
Furthermore, CO2 absorption experiments in aqueous ammonia using lab scale composite hollow fiber
membrane contactors (CHFMC) have been successfully carried out. The effect of the main operating
conditions on the CO2 absorption performances and the ammonia loss has been studied, namely
ammonia concentration, temperature, gas and liquid flow rates, nature of the dense layer. The overall
volumetric CO2 absorption capacity in CHFMC has been compared to the one obtained in packed
column. It has been concluded that membrane contactors strongly enhance the CO2 absorption
performances in comparison to conventional contactor. Moreover, a sharp decrease of the ammonia
slip has been observed. The above results will be detailed in the presentation and the performances
and advantages of this new CO2 absorption process will be discussed further.
Acknowledgment. This project was sponsored by lAgence Nationale pour la Recherche grant ANR-
09-EESI-001-01 AmliE_CO2.
References
[1] B.D , Lin H. and Freeman,. Materials selection guidelines for membranes that remove CO2 from gas
mixtures, Journal of Molecular structure 739, 57-74
[2] C. Makhloufi, E.Favre, D. Roizard, Reverse selective NH3/CO2 permeation in fluorinated polymers
using membrane gas separation, J. Memb. Sci. 441 (2013) 6372
Effect of pyrolysis products effect of pollutant composition on flow rate,

biomass mass loss rate and temperatures in the
composition on heat transfer different active zones of the pilot plant are
in a biomass pyrolysis pilot presented. Correlations for temperature and
plant with heat recovery from mass
loss are determined as function of pyrolysis
combustion of pyrolysis gases composition.
products
Mohammed Ammar Abbassia*, Kamel
Halouanib
a*Unit de Recherche Matriaux, Energie
et Energies Renouvelables (MEER)
Facult des Sciences de Gafsa,
B.P.19, Zarroug, Gafsa, 2112.
bMicro-Electro-Thermal Systems -
Industrial Energy Systems Group (METS-
ENIS) IPEIS, University of Sfax,
B.P: 805 3019, Sfax Tunisia
abbassima@gmail.com, and
Kamel.Halouani@ipeis.rnu.tn
A pilot plant of biomass pyrolysis using
pyrolysis products as fuel has been tested
and shown
to improve energy balance of the process
and to be environmentally friendly by
avoiding
rejection of pyrolysis pollutants fumes into
the atmosphere. The high number of
parameters
involved in a pyrolysis process makes it
difficult to specify an optimum procedure
for
charcoal yield and pyrolysis cycle
durability. So the knowledge of the
essential parameters
which govern the kinetics mechanisms of
the biomass thermal decomposition and the
combustion of pyrolysis gases is very
useful to understand the operating cycle of
the plant. In
the present study a thermochemical model
is developed in order to simulate the
operating
cycle of the system. The fumes are
supposed to be composed of CO, CH4,
CO2, and H2. Tars
are supposed to take cracking reactions and
give the same gases as those of pyrolysis.
The
Thermodynamic equilibrium analysis of hydrogen production from sunflower waste
frying oil
HAJJAJI Noureddine , CHRIKI Aya, CHRIKI Insaf, KHILA Zouhour

1
Unit de Recherche Catalyse et Matriaux pour l'Environnement et les Procds URCMEP
(UR11ES85), Facult des Sciences de Gabs, Ecole Nationale dIngnieurs de Gabs,
Universit de Gabs, Rue Omar Ibn Alkhattab 6029 Gabs, Tunisia.
Abstract
Hydrogen production via steam and autothermal reforming of sunflower waste frying oil
(SFO) is thermodynamically investigated via the Gibbs free energy minimization method.
SFO is considered as a mixture of triglycerides consisting of three same fatty acid groups in
their backbone and it is assumed to be, in molar percent: 62% trilaurin, 20% trioleate, 6%
tristearin, 9% tripalmitin, 1% trimyristin and 2% trilinolenin. Equilibrium calculations are
performed at atmospheric pressure in a wide range of temperature (4271127 C), steam-to-
SFO ratio S/C (114) and oxygen-to-SFO ratio O/C (0.02.0).
Results shows that the optimum conditions for steam reforming of SFO, determined for
maximum hydrogen production with minimum of methane and carbon monoxide contents and
without the danger of coke-formation, can be achieved at reforming temperatures between
575C and 625C and S/C ratio around 6. The optimal operation conditions for the SR of SFO
are proposed as T=600 C, S/C ratio= 6. With this condition, a hydrogen yield of 172.65 mole/
kg SFO and CO concentration in synthesis gas of 2.56% with trace content of CH4 (0.06%) can
be obtained without the danger of coke formation.
* Corresponding author. Phone: +216 24 04 04 00, Fax: +216 75 29 00 41

E-mail address: Hajjaji.nour@gmail.com
The most favorable conditions for hydrogen production from autothermal system are achieved
with the temperatures, S/C ratio and O/C ratio of 600-800C, 3-5 and 0.0-0.5, respectively.
Thermoneutral conditions under this condition can be accomplished with O/C ratio of 0.1-0.5.
The recommended condition are S/C=5, T=600C and O/C =0.455. Under this thermoneutral
condition, 146.4 mole H2/ kg SFO can be produced with only 0.78% and 0.01% content of CO
and CH4, respectively, in the synthesis gas.
Thermodynamic equilibrium investigation is an important tool to obtain equilibrium products
composition and identify thermodynamically favorable operating conditions of the process.
This work provides an original thermodynamic investigation useful to start experimental
research for high purity hydrogen production via SFO reforming.

autant dans la manipulation que dans

Etude et amlioration du linstallation. Malgr ces avantages, leur haute
rendement dune turbine influence de la temprature de lair ambiant
gaz dans un champ ptrolier qui varie considrablement quotidiennement
et dans saisonniers, fait quon saperoit
Slim Toumi1, Jalel Belghaieb1 leffet sur la performance thermique des
machines.
1. Ecole Nationale dIngnieurs de Gabs- 1. Cycle et modlisation de la Turbine
Tunisie, Rue Omar Ibn-Elkhattab 6029,
Gaz
Gabs, contact@enig.rnu.tn.
1.1. Cycle de la Turbine Gaz
Rsum Dans son architecture la plus simple, la
Le rle des turbines gaz, dans la turbine gaz, qui aspire l'air ambiant et rejette
production dlectricit, de lindustrie des gaz brls l'atmosphre, fonctionne en
ptrolire a pris une attention particulire circuit ouvert. Le cycle thermodynamique
ces dernires annes. A cet effet, rsultant est appel cycle de Brayton,
diffrentes mthodes (rgnration, reprsent dans la Figure 1.
refroidissement dair dadmission,
prchauffage et injection de la vapeur
deau) ont t utilises afin damliorer les
performances des cycles des turbines gaz.
Dans cette optique, la mthode dinjection
de la vapeur deau dans la chambre de
combustion dune turbine gaz et le
refroidissement de lair dadmission, ont
t proposs et tudis et compars avec un
cycle simple. Pour cela, on a conu un
programme avec Engineering Equation
Solver (EES) de calcul de linfluence des
conditions ambiantes sur les
caractristiques des diffrents composants
de la turbine gaz, telles que la Figure 1: Diagramme Temprature-Entropie du cycle
compression, la combustion et la dtente. thorique et rel de Brayton.
Ce cycle est compos principalement de trois

Mots cls : Cycle simple, rendement
tapes : Compression, Combustion et Dtente.
thermique, turbine gaz, logiciel EES,
injection de vapeur, tude conomique. 1.2. Modlisation de la Turbine Gaz
En se fondant sur des modles
Introduction thermodynamique de turbine gaz, un
La turbine gaz ou "turbine programme de calcul a t dvelopp pour le
combustion" est une machine thermique calcul des paramtres de performance et
flux continu, ralisant diffrentes lanalyse paramtrique dun cycle simple et
transformations thermodynamiques, dans dun cycle inject par la vapeur deau. Les
une succession dorganes comportant un calculs ont t raliss sur des gammes des
compresseur, une turbine couple rapports de pression, de la temprature
mcaniquement sur un arbre, et une ambiante et quelques autres dtails de
chambre de combustion intercale entre constructeurs sur la turbine gaz tel que le
ces deux derniers. Ces machines sont rendement de compression polytropique et
connues pour leurs court temps de celui de la dtente, le rendement thermique, et
dmarrage et leur indiffrence de la le rendement adiabatique de la chambre de
variation de rgime et leur simplicit combustion etc.
1
T
TCHES Inteernational Ch
hemical Engiineering Con
ngress, Decem
mber 16-19, 22013, Djerba - Tunisia
Lalgoriithme a suivvi utilis daans les calcuuls 33 (%)

est si deessous. 31 y=0
0,067x+31,06
Lecture ,PCIetrr 29
27
25
23
Donnes Demmande 21
19 y=0,308
8x+32,94
mto
orologiques:TT,P lecctrique
17
T amb(C)
15
0 10 20 30 40 50
REND
DSANSINJ RENDAVEECINJ
Figure
F 3: influennce de la temprature sur le reendement de la
turbine gaz pour
p les deux ccas avec et sanss injection de
Dbittsdair vapeeur.
2.2. Refroiddissement dde lair S2

A partir des d relevs journalieers de laa
T2,W
Wc,H2 teemprature ambiante, de la temp prature dess
hermocouples placs enn aval de laa turbine dee
th
puuissance et du dbit dee gaz conso omm par laa
tu
urbine, on dtermine
d laallure du reendement dee
E
Excsdair
laa machine en fonctioon de la temprature
t e
Bilanenthallpiquesurla ammbiante, comme
c lee montre la figuree
chambredecombustion prrcdente. Donc, le rendement thermiquee
diiminue quaand la tem mprature dadmission
d n
auugmente.
3.. Etude tech
hnico-con nomique
CalculT3 S1 S2
Gain nergtiq
que
(kWh)
1 3255 360,74 495 269,12
Gain conomiqque
CalculT4,Wnet annuel (DT)
185 550,5 69 338
Figuree 2: Algorithmee de calcul des paramtres
p de Investissements
I (
(DT) 366 698 64 523
perf
rformances
Temps
T de retourss (an) 00,2 0,9
2. Soluttion proposss
Conclusion
C
Linnjection de la vapeur deau
d dans la Le but dee ce travail est loptiimisation ett
chammbre de commbustion. lamlioratioon du rendeement de la turbine
La diminutionn de la tempratuure gaaz du cham mp ASHTART de la l SEREPT T
denntre de lair daddmission du d enn vue dune rattionalisation n de laa
coonsommatioon en combbustible de la turbine
com
mpresseur. gaaz. Une fois les param mtres dee
2.1. Inj
njection de vapeur
v deaau S1 foonctionnement optimaaux sont connus, c less
peerformances de liinstallation ont t
Il resssort de lannalyse des rsultats,
r quue coonduits, pour less deux solutionss
pour unne tempratture ambiannte de 30C, damlioratioons du renddement therm mique de laa
on note une augmeentation du rendement
r de tu
urbine propposes. Laanalyse co onomique a
rvl que laa solution dinjection dee vapeur estt
23.5% 29%, soit une amlioratioon laa plus rentabble.
relative de lordre 19%
2
INFLUENCE OF CYCLYC 2. Experiment

APPLICATION OF The AC used in our study was prepared from
olives stones by means of chemical activation
METHANE ADSORPTION method (the olives stones are impregnated by
ON SURFACE phosphoric acid then activated at 410 C
PROPERTIES OF under N 2 flow, called C.A.G.O.Chim)
ACTIVATED CARBON Tableau X: Properties of AC
Properties C.A.G.O.Chim
Abir Soli 1 , Abdelmottaleb Ouederni2
S BET (m/g) 1139
1. RL: Processes and Industrial System, Nat. School Total pore 0,5541
Eng.Gabes ,University of Gabes abir.soli @ gmail.com
volume(cm3/g)
2. RL: Processes and Industrial System, Nat. School Micropore volume 0,5474
Eng.Gabes ,University of Gabes,mottaleb.ouederni @
enig.rnu.tn (cm3/g)
Diameter of pore des 19,45
Abstract: pores (A)
The evolution of the properties of the Bulk density (g/cm3) 0,4197
surface adsorbent for cyclic application of
methane adsorption was tested in our study Real density (g/cm3) 1,7251
on AC prepared by chemical method. It
was concluded that the diffusion of
2.1 Experimental Set Up
methane molecule into the pore of
activated carbon produces these The experimental apparatus is shown in fig X.
modifications: appearing of lactone Two stainless steel cells are used. Within them
function, increasing of carbonyl and a cell was filled with a given weight of
decreasing of phenolic function. prepared carbon particles.
Concerning the desorption, we conclude 1
that carbonyl and phenolic functions need 0
an important desorption that delivered

more than 15 mg/g of adsorbed methane.
Besides, we noticed that carboxylic 5
functions are sensitive to the desorption, 6

9
hence we suggest that it desorbed as CO or 7 8 B
1
CO2 . 3
2
Key words: Methane storage, Activated carbon,
A
Adsorption, surface function
4 2
1. Introduction
Natural gas (NG) is considered as an
appropriate alternative fuel due to its huge
resource and low toxic gas emission. B-cell of storage; A-cell of feed ; 9-Basket of AC;
Nevertheless, for large scale use to be 2,3- heat balloon of enclosure A and B
feasible, it is necessary to store NG in a respectively; 4-device of volumetric desorption ;
safe and economical way. Adsorbed NG 7-Bill-poster and regulator of temperature of
enclosure B; 8- Bill-poster and regulator of
can be an alternative solution to store NG
temperature of enclosure A; 6- Pressure gauge of
at relatively low pressure (35-40 bars) and enclosure B; 5- Pressure gauge of enclosure A ;
at room temperature if adequate adsorbent 10-Agitator ; 1-bottle of methane
is developed [1]. Figure X: Sheme of the experimental set

3.1 Results 4. Conclusions
The histogram in figure Y shows that both In this paper, we study the modifications of
adsorptive capacity of the activated carbon surface chemistry of activated carbon for
and the carbonyl function have the same cyclic operation charge-descharge of methane
sens of variation. As a general trend, when storage. We used an AC prepared by chemical
carbonyl function increase from 0,275 method . As a result, we found that the
mq/g to 0,75, the adsorbed capacity diffusion of methane molecule into the pore of
increase from 26 28 mg/g. activated carbon produces the increasing of
carbonyl and decreasing of phenolic function.
Also, we concluded that carbonyl and
phenolic functions need an important
desorption that delivered more than 15 mg/g
of adsorbed methane. Besides, we noticed that
carboxylic functions are sensitive to the
desorption, hence we suggest that it desorbed
as CO or CO2 .
References
[1] A. Celzard, V. Fierro, Energy 19, 2005, pp. 573
[2] J. W. Lee, M. S. Balathanigaimani, H.C. Kang, W. G.
shin, C. Kim, H. Moon, Methane storage on phenol-based
activated carbons at 293,15 , 303,15 and 313,15 K, J. Chem.
Figure 1 : Evolution of carbonyl function for the Eng. Data 52, 2007, pp. 66-70
cyclic application (Na : adsorbed methane)
[3] Y.P. Guo, D. A. Rockstraw. Physical and chemical
properties of carbons synthesized from xylan, cellulose, and
Kraft lignin by H3PO4 activation, Carbon, 44, 2006,1464-
The histogram in figure Z shows that the
1475.
adsorption of methane molecule into the
pores of activated carbon produce the
diminution of phenolic function about 0,5
mq/g.
Figure Z : Evolution of phenolic function for the

cyclic application (Na : adsorbed methane)
Atomic Force Microscopy: A lms by coupling, in situ, electrochemistry

and AFM analysis, in the first instance, and
Multifaceted Tool to Study then the potential AFM as an electrochemical
Macro- and Nano- lithographic tool will be explored.
Electrografting Processes
Achraf Ghorbal1, Federico Grisotto2, 2. Experimental Section
Julienne Charlier2, Serge Palacin2, and
4-Nitrobenzenediazonium tetrauoroborate
Ammar Ben Brahim1
[NBD](C6H4N3O2 BF4), Tetraethylammonium
1. Applied Thermodynamics Research Unit, National perchlorate [TEAP]((C2H5)4N(ClO4)), Acrylic
Engineering School of Gabs, Gabs University, Rue acid [AA](C3H4O2) were purchased from
Omar Ibn-Elkhattab 6029 Gabs, Tunisia, E-mails:
achraf.ghorbal.issat@gmail.com (A.G.);
SigmaAldrich and used as received. Macro-
ammar.benbrahim@enig.rnu.tn (A.B.B.) electrografting experiments substrates were
2. CEA-Saclay, DSM/IRAMIS/SPCSI, 91191 Gif-sur- slices of n-type Si(100) wafers (coated with a
Yvette Cedex, France, E-mails: fedecfedec@gmail.com
(F.G.); julienne.charlier@cea.fr (J.C.);
continuous gold layer (180 nm thick) on a (15
serge.palacin@cea.fr (S.P.) nm thick) chromium underlayer evaporated on
the back of the substrate to ensure an ohmic
contact). Nano-electrografting experiments
Abstract: substrates were pyrex glass plates coated with
Scanning probe microscopy techniques, 2 nm of chromium and 100 nm of gold by
such as atomic force microscopy, are of vacuum evaporation. Nano-electrografting
great interest for fundamental and technical experiments and the in situ analysis of macro-
applications. Herein, an atomic force electrografted films were performed with a
Molecular Imaging PicoSPMLe commercial
microscope is used as a patterning tool so AFM microscope (PicoScan 2100 controller,
as to nano-characterize electrografted Scientec, France) equipped with a home-
polymeric films and as a new modied uid cell containing the electrolytic
electrochemical lithographic tool to locally solution. X-ray photoelectron spectroscopy
nano-electrograft conducting substrates. (Kratos Axis Ultra DLD) analysis and
mapping were performed with a high-
resolution monochromatic Al(K) X-ray
Key words: AFM, Electrografting process, source (1486.6 eV).
Polymers, Thin films, Nanotechnology.

1. Introduction 3.1 Macro-electrografted films AFM and XPS study
Atomic force microscopy (AFM) is a By combining AFM and XPS
technique with many different applications characterizations we investigated not only the
in fundamental and technical fields. This threshold conditions necessary for the PNP
methodological platform offers several appearance on n-type silicon but we also
advantages over more traditional defined the chemical changes in the organic
approaches and overcomes some of the films under the AFM tip shear. Figure 1 gives
barriers in the study and the realization of the voltammogram recorded when reducing
electrografting processes [1]. Indeed, AFM NBD on n-type silicon with the evolution of
was proved to be not only a technique for the measured thickness of the resulting PNP
imaging surfaces but also the suitable tool films grafted after one voltammetric scan as a
for the chemical and physical patterning of function of the applied potential. This result is
surfaces [2, 3]. The present work is related consistent with our expectation that the film
to these phenomena. In the present paper, thickness increases with the absolute value of
we wish to investigate the multilayer the applied potential. Indeed, the more
formation of polynitrophenylene [PNP] negative the applied potential, the higher the
amount of electro-generated radicals, and electrolyte solution may play the role of
the thicker the final grafted film. trappers which also limit free-radical diffusion
and initiate a vinylic radical polymerization.
Figure 1: (a) Cyclic voltammogram in the

cathodic range recorded with a sweep rate of 10
mV.s-1 for the electrolytic solution (NBD 5.10-3
mol.dm-3/TEAP 8.10-2 mol.dm-3) on n-type
silicon substrate. (b) Applied potential Figure 3: A simplified schematic representation of
dependence of the PNP thickness growth on reactions leading to the nano-grafting. (1) Reduction
silicon substrates. of the NBD on the substrate to form a PNP film. (2)
Water oxidation at the electrode. (3) Concomitant
3.2 Nano-electrografting process reduction of protons on the substrate and formation
The nano-electroinitiated polymerization of a localized grafted coating onto the top of the
primer PNP film by radical reaction. (3a) Formation
technique consists in applying of a phenyl radical and reaction with PNP film. (3b)
chronoamperometric technique by setting Phenyl radical initiates the first vinylic (plausible)
the potential to -0.8 V vs. Ag wire. A 5 m radical polymerization. (3c) Formation of radical
working distance and a low scan velocity monomer, initiation of the second (plausible) vinylic
of about (18 m.s-1) were found to be radical polymerization.
optimal to allow nano-electrografting. The
resulting localized thin films were 4. Conclusions
characterized by topographical AFM
analysis (see Figure 2). This study shows unambiguously that AFM
allows polymeric films nano-characterization
and vinylic monomers to be electrografted
onto a conducting substrate to form motifs
with few hundred nanometres wide.
References
[1] Charlier, J.; Ghorbal, A.; Grisotto, F.; Clolus, E.;
Figure 2: (a) AFM image in tapping mode of the Palacin, S. Main Strategies to Direct Localized Organic
line pattern drawn with direct NBD/AA Grafting on Conducting and Semiconducting Substrates.
reduction. (b) Cross section of the electrografted In New Nanotechniques; Malik, A., Rawat R. J., Eds.;
line (180 nm width and 40 nm height). Nova Science Publishers: New York, 2009; chap. 9, pp
In fact, as shown in Figure 3, the cathodic 319350.
current produces nitrophenyl radicals from [2] Ghorbal, A.; Grisotto, F.; Laud, M.; Charlier, J.;
Palacin, S. The in situ characterization and structuring of
NBD in the vicinity of the cathode, which
electrografted polyphenylene films on silicon surfaces.
immediately graft onto the electrode An AFM and XPS study, J. Colloid Interface Sci. 2008,
surface and generate a thin PNP film. 328, 308313.
Moreover, the narrow working distance [3] Ghorbal, A.; Grisotto, F.; Charlier, J.; Palacin, S.; Goyer,
limits the diffusion time of the radical C.; Demaille, C. Localized Electrografting of Vinylic
species generated at the working electrode Monomers on a Conducting Substrate by Means of an
surface and ensures a small reaction area. Integrated Electrochemical AFM Probe, ChemPhysChem
Hence, the vinylic monomers in the 2009, 10, 10531057.
Influence of alkaline treatment the these raw materials is their low cost as this is a
structure and adsorptive relevant parameter in the activated carbon
production. The primary objective of this
properties of olive stones based
study is to discuss phenol adsorption capacity
activated carbon of H3PO4 activated olive stone carbon and
basic surface modified activated carbons. The
SOUDANI Nouha1, NAJAR-SOUISSI effects of important factors such as the phenol
Souad 2 and OUEDERNI Abdelmottalab 3 concentration of the solution, the
concentration of basic solutions and the
LR: Chemical Reactors and Process Control, University surface functional groups of the adsorbents on
of Gabes, National School of Engineers of Gabes, the equilibrium capacities are discussed. The
Mednine Street 6029, Tunisia.
textural modifications are carried out by
Abstract: means of the adsorption of N2 at 77 K. The
In this work we studied the effect of the changes in the chemical structure of the
concentration of alkaline solutions on the samples are analyzed by the Boehm titration
properties of activated carbons obtained methods. The model molecule phenol is
from the oxidation of a parent activated adsorbed into the different AC samples.
carbon. For this purpose olive stone from 2. Experiment
Tunisia has been used as raw material to
The activated carbon prepared on the Lab,
prepare the parent active carbon (OSAC).
labeled as OSAC, was treated with alcaline
This was further treated with different
solutions. Four different concentrations of
concentrations of sodium hydroxide
sodium hydroxide solutions was used 1, 2, 3
solutions to determine suitable
and 4M. For this purpose, 30 g of AC were
modication for improving adsorption
mixed with 250 mL of alkaline solution and
ability of phenol. Results showed that
the mixture was boiled for 3 h. The samples so
OSAC modied by alkalis had better
prepared with sodium hydroxide were labeled
adsorption capacity. To identify the
OSAC 1M/H, 2M/H, 3M/H and OSAC 4M/H
structural characteristics of the tested
respectively.
samples BET and DubininRadushkevich
(DR) was used, while IR Boehms titration 3. Results and Discussion
were applied to analysis the surface 3.1 Pore structure development
functional groups. Further analysis results
by the Langmuir equation showed that In order to estimate the structure parameters
modified OSAC has larger adsorption characterizing the activated carbon and to
capacity of phenol from aqueous solution. study the inuence of its modication on the
Key words: Activated carbon, Alkaline solution, changes of pore structure, adsorption
Surface characteristics, Adsorption. isotherms of nitrogen at 77 K were measured.
1. Introduction
3.2 Surface fonctionnel groups: Boehm titration
In recent years wastewaters has became an The Boehm titration method allows the
increasing concern and represent a serious determination of the surface functional groups
potential hazard for human health and such as phenolic group (OH), lactone group
aquatic life. Phenolic compounds are (C=O), carbonyl and carboxylic group
indeed very toxic, with a xed low (COOH) as well as the basic groups.
admissible level of 0.5mg/L of water [1,
2]. Numerous precursors have been used 3.3 Surface functional groups IR analysis
with success for the preparation of Figure 1 shows FTIR spectra of the OSAC/H
activated carbons including peat [3], treated at different concentration of basic
bagasse, sawdust, desert plants, rice bran, solutions. Four mains peaks were detected on
husk, fruit peel, waste tee, and coffee
grounds [4]. An important reason to select
the spectra of sodium hydroxide modified Nylosan Red N-2RBL, Journal of Hazardous Materials,
activated carbons. 2010, 175, 779788.
Figure 1: FT-IR spectra of the untreated

activated carbon (OSAC) and NaOH treated
activated carbons.
4. Conclusions
Both micropore volume and N2 BET
specific surface area decrease during
treatment of activated carbon with sodium
hydroxide and quantities of nitrogen
functional groups incorporated into the
carbon structure increase. At the same
time, sodium hydroxide-treated carbons
exhibit higher adsorption capacity toward
phenol from water. Taking into account
these facts, it was concluded that the
increased adsorption capacity results from
the changes in surface chemistry of
activated carbons occurring during treating
with alkalis.
Acknowledgment
The analysis of IR and XPS by the University of
Granada is gratefully acknowledged.
References
[1] P. Girodsa, A. Dufoura,V.Fierrob, Y. Rogaumea, C.
Rogaumea, A. Zoulaliana, A. Celzardc, Activated
carbons
prepared from wood particleboard wastes:
Characterisation and phenol adsorption capacities,
Journal of Hazardous Materials, 2009,166, 491501.
[2] H. Polat, M. Molva, M. Polat, Capacity and
mechanism of phenol adsorption on lignite, International
Journal of Mineral Processing, 2006, 79,264273.
[3] A. Veksha, E. Sasaoka, M.D. Azhar Uddin, The
inuence of porosity and surface oxygen groups of peat-
based activated carbons on benzene adsorption from dry
and humid air, Carbon, 2009, 47, 23712378.
[4] A. Reffas, V. Bernardet, B. David, L. Reinert, M.B.
Lehocine, M. Dubois, N. Batisse, L. Duclaux, Carbons
prepared from coffee grounds by H3PO4 activation:
characterization and adsorption of methylene blue and
Valorisation of an Industrial reaction parameters (photon flux of the lamp,

initial concentration of pollutant mass of the
Waste Water to Produce a catalyst, pH of the solution) was carried out
Rigid Polyurethane Foams
Mohamed Ammara*, Ramzi KHIARIb, c,

Naceur BELGACEMc, Elimame
ELALOUIa
a: Materials, Environment and Energy Laboratory,
Faculty of Sciences of Gafsa, University of Gafsa
Tunisia;
b: Research Unity of Applied Chemistry & Environment,
Department of Chemistry, Faculty of Sciences, University
of Monastir, 5019 Tunisia;
c: Laboratoire de Gnie des Procds Papetiers UMR
CNRS 5518, Grenoble INP-Pagora, 461, rue de la
papeterie, B.P. 65, 38402 Saint Martin dHres Cedex,
France ;
*Corresponding author. Tel.: +216 97504823;
ammarmohamed10@yahoo.fr
Abstract
Soda lignin (SL), a solid by product
obtained from pulping of alfa grass (Stipa
Tenacissima) was isolated and carefully
characterized by different analytical
methods namely: FTIR and NMR
spectroscopy, and titration methods. These
techniques showed that SL is composed
primarily of p-hydroxyphenyl-guaiacyl-
syringyl (HGS) sequences. When
compared the obtained lignin to
commercial samples, the structure of SL
was found to be slightly degraded. Thus it
can be explain by the high degradation of
isolate lignin during the cooking process.
Then, SL was oxypropylated in order to be
converted into liquid polyol using
propylene oxide at 160C at high pressure.
The ensuing product was characterized by
its hydroxyl number, viscosity. Moreover,
its structure was investigated by FTIR and
NMR spectroscopis. The prepared polyol
was then introduced into rigid
polyurethane foams formulations
containing a cross linking polyisocyanate
reagent, a blowing product and a mixture
of surfactants and catalysts. The prepared
foams showed promising and interesting
properties to use in potential application.
KEYWORDS: Soda lignin, Stipa Tenacissima,
oxypropylation reaction, Foams.
the type of added carbon. At the end, a
demonstration of the influence of certain
PRODUCTION OF activating agent such as carbon dioxide, steam

or a combination of both. On the other hand,
ACTIVATED CARBON in chemical activation the precursor is
FROM POMEGRENATE impregnated with a given chemical agent after
PEELS BY CHEMICAL that, is pyrolyzed at temperature of 400-800C
under nitrogen atmosphere. Several activating
PROCESS agents have been reported for the chemical
activation process: phosphoric acid, zinc
Wafa SAADI1, Souad NAJAR SOUISSI1 and chloride and potassium hydroxide [2, 3].
Abdelmottaleb OUEDERNI1
1: National School of Engineers of Gabes, University of An important advantage of chemical
Gabes 6029 Gabes - TUNISIA
activation is that the process normally takes
saadiwafa@yahoo.fr place at a lower temperature and shorter time
souad.najar@enig.rnu.tn than those used in physical activation.
Moreover, the yields of carbon in chemical
Abstract: activation are usually higher than in physical
activation. In addition, it allows us to obtain
Using pomegranate peels, the preparation
very high surface area activated carbon.
of activated carbon has been undertaken in
the present study by chemical activation The objective of the present paper is to
with potassium hydroxide. prepare activated carbon using pomegranate
A series of KOH-activation products was peels as a precursor and KOH as activating
prepared by varying the impregnation agent.
ratio. Such products were characterized by 2. Experiment
N2 adsorption at 77 K, iodine, phenol and
methylene blue number. 2.1. Impregnation with potassium hydroxide
The maximum BET surface area is about The raw material was washed with distilled
to 833 m2/g obtained at impregnation ratio water and dried at ambient temperature. After
of 4 and carbonization temperature of drying, the pomegranate peels was crushed to
700C for 2.5 h. obtain grains of varying sizes.
Key words: activated carbon, pomegranate A mass of dried pomegranate peels was mixed
peels, potassium hydroxide, characterization.
with KOH solution with different
impregnation ratio (imp) for about 3h at
1. Introduction 102C. imp varies between 2 to 5.
Due to its special characteristics as an This parameter is defined as:
adsorbent, catalyst, or catalyst support,
imp = (weight of KOH solution) / (weight of
activated carbon has found various
pomegranate peels)
applications in the industries dealing with
separation or catalytic process. 2.2. Carbonization
Lignocellulosic materials are attractive as The impregnated pomegranate peels are
precursor for preparation of activated placed in a fixed bed tubular reactor in a small
carbons [1]. stainless steel horizontal.
There are, in general, two different The reactor is placed in turn in a horizontal
processes for the preparation of activated electric furnace with adjustable temperature.
carbon: physical and chemical activation A purge is carried out for 15 minutes with
process. The physical activation involves nitrogen flow.
carbonization of a carbonaceous precursor This mixture was dehydrated at 700C for
followed by gasification (800-100C) of 2.5 h under nitrogen flow. Subsequently, the
the resulting char or direct activation of the samples were repeatedly washed with hot
starting material in the presence of an distilled water until the pH of solution reach
6.5. After that, the samples were dried at

110C overnight.
3.1. Yield and surface area of activated
carbon
Impregnation ratio has as effects on both
the yield of product and the surface area as
shown in table 1.
Increasing imp from 2 to 4 leads to more
developed porosity, reaching a maximum Figure 2: Influence of impregnation ratio
BET surface area equal to 833 m2/g at on methylene blue number.
impregnation ratio of 4. Thus, at high KOH The activated carbon which has the highest
solution/precursor the effect of the metallic specific surface area (833 m2/g), has the
salt in the formation of microporosity is important adsorption capacity of methylene
more pronounced reaching a maximum blue equal to 333 mg/g.
value for an impregnation ratio of 4 [2].
4. Conclusions
Table 1: Physical properties of activated Activated carbon was prepared from
carbon at different impregnation ratio pomegranate peels using potassium hydroxide
Sample imp SBET
2
Yield as activating agent. The influence of
(m /g) (%) impregnation ratio between 2 and 5 on the
E01 2 563 23.2
characteristics and adsorption properties was
E02 3 735 20.7
E03 4 833 14 studied. The maximum specific area of 833
E04 5 654 11.2 m2/g was reacted at an impregnation ratio of
4.
The yield of activated carbon decreases
References
with the increase of impregnation ratio as
seen in table 1. Potassium hydroxide [1] Arjmand, C. Kaghazchi, T. Latifi, S.M. Soleimani M.
Chemical Production of Activated Carbon from Nutshells
promotes the oxidation process; with high
and Dates Stones. Chem.Eng.Technol. 2006, 29, 986
KOH ratio the gasification of surface 991.
carbon atoms is the predominant reaction [2] Lozano-Castello, D. Lillo_Rodenas, M.A. Cazorla-
leading to the increase in the weight loss of Ameros, D. Linares-Solano A. Preparation of activated
carbon [4]. carbon from Spanish anthracite I. Activation by KOH.
Carbon. 2001, 39, 741-749.
3.2. Methylene blue adsorption
[3] Creanga, M. Procd AD-OX dlimination des
Figure 1 shows methylene blue polluants organiques non biodgradables (par adsorption
adsorption capacities of activated carbon puis oxydation catalytique). Ph.D. Thse, Institut
samples. Those carbons exhibit much National Polytechnique de Toulouse, Mai 2007.
[4] Sudaryanto. Y, Hartono. S.B, Irawaty. W, Hindarso. H,
higher adsorption capacities varying from
Ismadji. S, High surface area activated carbon prepared
321 to 333 mg/g. from cassava peel by chemical activation. Bioresource
In general, the higher the amount of Technology. 2006, 97, 734739.
methylene blue adsorbed, the better the [5] Zou, Y. and Han. B.X. High-Surface-Area Activated
quality of the activated carbon [5]. Carbon from Chinese Coal. Energy & Fuels. 2001, 15,
1383-1386.
SYNTHESIS AND the chemical synthesis of precursor materials

for carbon by using the sol-gel process. This
CARACTERIZATION OF method consists on obtaining a pure activated
MICROPOROUS XEROGEL carbon.
P/F In this work we propose to synthesize a new
microporous xerogel P/F by polycondensation
MOUSSAOUI Rebah1,3, NOURI Saleh1,3 , of pyrogallol with formaldehyde in aqueous
MOUSSAOUI Younes 1,2,3, ELALOUI medium and catalysed by hydrochloric or
Elimame1,3 perchloric acid. This polycondensation seems
to be very little studied.
1
Materials, Environment and Energy Laboratory
(06/UR/12-01), Science Faculty of Gafsa, University 2. Experiment
2112, Gafsa,, Tunisia
2
Physical Organic Chemistry Laboratory, Science
To synthesize the Pyrogallol-formaldehyde
Faculty of Sfax, 3018, Sfax, University of Sfax, Tunisia resin we have follow this stapes:
3
Science Faculty of Gafsa, Gafsa University, Zarroug Pyrogallol (0.11 mol) was reacted at room
city, 2112, Gafsa, Tunisia.
temperature with formaldehyde (0.33 mol) in
60 mL of water, in the presence of perchloric
Abstract: acid HClO4 as catalyst. The sample was
Nowadays several researches were prepared with 2 molar ratio of pyrogallol /
interested to study the porous materials catalyst.
obtained by sol-gel because this method After gelation, the obtained sample was aged
consists on obtaining very pure products by placing it in a water bath to stabilize its
from selected precursors. This paper temperature at 50C for 48 h. The gel is then
reports the synthesis of a microporous demolded and rinsed or not before drying it in
material by polycondensation of pyrogallol at 150C.
with formaldehyde in aqueous solution.
We have used the perchloric or 3. Results and discussion
hydrochloric acid us catalyze. The samples The first step that we have done is the The
is synthesized and characterized by various measurement of gelation time. So the tg (min)
techniques such as FTIR adsorption = 20 for this synthesized sample.
spectra. Then we have analysis the xerogel by the
Nitrogen adsorption- desorption by means of
Keys Words: sol-gel process, FTIR, BET, an apparatus ASAP2000 Micromeretics. The
microporous material, polycondensation.
obtained isotherm was type I of classification
BET, it characterize microporous materials
1. Introduction
Several researchers are interested to study (Figure 1).
the porous carbon materials which are The specific area is about 628 m2g-1.
known and used by man for centuries [1].
Because of their various applications such
as adsorbents for gas separation [2,3],
catalyst support [4-5], electrode for fuel
cell or super capacitor [6,7].
Those particles have a specific properties
like their porous texture and surface
properties. They are produced by different
methods like heating treatment of natural
organic materials however this gives
materials nothing guarantees of texture,
surface properties, mechanical strength or
composition of charcoal. This is why the
Figure 2: Nitrogen adsorption-desorption isotherm
development of carbon materials turned to
of P/F
Then we have used the FTIR spectra and adsorbents for gas separation. Carbon, 42 (2004) 1671-1676.
[3] Sircar, S.; Golden, T.C.; Rao, M.B. Activated carbon for
compared the PF polymer with the RF gas separation and storage, Carbon 34 (1996) 112.
(Figure 2) prepared by condensation of [4] Rodrguez-Reinoso, F. Carbon as a catalyst support. In:
resorcinol with formaldehyde in identical J.W. Patrick (Ed.), Porosity in carbons, Wiley, UK, 1995, p.
253.
conditions. The FTIR spectra of RF and PF [5] Tonanon, N.; Wareenin, Y.; Non-Cryst, J. Solids 352
samples are very similar when they were (2006) 5683.
dried in an oven after removal of the acid [6] Li, W.; Reichenauer, G.; Fricke, J. Carbon aerogels
derived from cresol-resorcinol-formaldehyde for
catalyst by washing the resin. We found supercapacitors, carbon, 40 (2002) 2955-2959.
substantially the same frequencies of [7] Probstle, H.; Schmitt, C.; Frick, J. Power Sources 105
vibration excepting a shoulder that appears (2002) 87.
around 1685 cm-1 in the spectrum of the PF
resin (Figure 2).
Trs
1,8
1,6
1,4
1,2
1
PF
0,8
RF
0,6
0,4
0,2
0
4000 3500 3000 2500 2000 1500 1000 500
cm-1
Figure 2: FTIR spectra of the PF and RF

samples.
Conclusions
The main purpose of this work is the
preparation of activated carbon by sol-gel
process and its physiochemical
characterization by FTIR spectroscopy and
nitrogen adsorption-desorption (BET).
We have used a new method that controls
the properties of texture and porosity.
In this synthesis, it appears that that
thecatalysis by perchloride is the best in
aqueous media.
Acknowledgment
The authors express sincere thanks to the
Tunisian Higher Education and Scientific
Research Ministry for its financial support.
References
[1] Derbyshire, F. ; Jagtoyen, M. ; Thwaites,M. Activated
carbons-Production and applications. In: J.W. Patrick
(Ed.), Porosity in carbons, Wiley, UK, 1995, p. 227.
[2] Yamamoto, T.; Endo, A.; Ohmori, T.; Nakaiwa, M.

Porous properties of carbon gel microspheres as
Insulator semiconductor (TOPO) as an ionophore due to its high

sensitivity for hexavalent chromium [3-6].
structures coated with a The pH influence on the response of the
polymeric membrane detector was studied. In order to determine
including tributyl phosphine the best pH interval for the sensor
sensitivity to chromium (VI), the sensor
oxide (TOPO) for in-situ Cr6+ response (potential vs. saturated calomel
micro-sensors electrode) as a function of the pH value
(2.428.26) was determined. The study of
A.Zazoua1,*, N. Jaffrezic-Renault2 the influence of several interfering ions on
the detector response was limited to three
1
Universit de Jijel, BP 98, Ouled Aissa, 18000 Jijel, elements, namely, SO42-, CO32-, Cl-.
Algeria, azazoua@yahoo.fr
2
Universit de Lyon - LSA - UMR 5180 CNRS -
Universit Claude Bernard Lyon 1, 69622 Villeurbanne
cedex, France
Abstract:
In this work we have developed and
studied a chemical micro-sensor with the
deposition of the selective membrane on
the surface of an ISFET derived from well- Figure 1 : Tri n-octylphosphine oxyde
established metal oxide semi-conductor
field effect transistor (MOSFET) devices 2. Experiment
well known into silicon-integrated circuits. 2.1. Composition and deposition of the
The ISFET was functionalized with a membrane
polymer layer containing tributyl
phosphine oxide (TOPO) as a ligand for In the preparation of Cr(VI) ISFET
the selective detection of in-situ hexavalent membrane, a typical procedure was applied
chromium in water. The sensitivity for using siloprene, cross-linker and TOPO
hexavalent chromium was found to be ionophore (tributyl phosphine oxide)
26.71 mV/logaCr6+ in the range of 10-2 to (Fig.1) in a ratio of 10:1:2 (w/w/w) diluted
10-4 M. The detection limit was found to be in THF. Before deposition of the siloprene
10-5 M. membrane, a treatment of the ISFET
insulator surface with a sulphochromic
Key words: ISFET, TOPO, Sensors, Hexavalent mixture was performed. The siloprene
chromium. membranes were performed by depositing
0.1 L of the aforementioned
siloprene/ionophore suspension on the
1. Introduction ISFET surface.
A chemical sensor consists to a sensitive 40
specific part of the species to be detected 35
and a system for providing a signal via 30
different transduction modes [1, 2]. Our 25

E (mV)/ SCE
attention was mainly focused on one type 20
15
of ion, the oxidized form the more toxic of
10
chromium called hexavalent chromium and 5
designated by Cr (VI) (standard toxicity 0
from 50 mg / L). -5
-7 -6 -5 -4 -3 -2
In the present work, we have used the log a
tributyl phosphine oxide (C24H51OP) Figure 2 : The gate voltage shift E is plotted vs. logaCr6+
2.2. Measurements (concentrations calculated from PbSO4

The output voltage of the modified ISFET and CdSO4). Fig. 3 presents the chromium
immersed in buffer solution (Tris sensitivity in the presence of a fixed
hydroxymethyl aminomethane adjusted at concentration of interfering cations. The
pH 7.5 with HCl at 0.5 M) was measured highest interfering sensitivity was found in
with a source follower type ISFET SO42-, CO32-, followed by Cl- ions. The
amplifier. detection limit differs in each case. It
should be mentioned that this parameter is
governed by the presence of the interfering
3.1. Sensor characterization cations.
The potentiometric response of the
chromium hexavalent sensor has been 4. Conclusions
determined in Tris solutions adjusted to an We presented in this work a
HCl pH value of 7.5. The increasing thermodynamic approach by measuring the
variations of the Cr(VI) concentrations are output voltage of ISFET based on the
maintained by successive injections of variation of the concentration of Cr (VI).
chromates solutions such as potassium The results showed that the sensitivity of
chromates, K2Cr2O7, at different both sensors produced depends on the
concentrations. Fig. 2 shows the ligand concentration in the polymer
corresponding sensitivity plot, in which the membrane. Among the advantages of the
gate voltage shift E is plotted vs. logaCr6+ . developed sensors, we can report that they
The obtained sensibility is linear with a have almost Nernstian sensitivities over the
slope value of 26.71 mV/logaCr6+; it is Cr (VI) ions in the form Cr2O72-and short
quasi-nernstian for concentrations ranging response time. A major disadvantage is the
from 10-4 M to 10-2 M. For lower interference and the changing of the
concentrations, the response is about 3 detection limit in the presence of CO32-.
mV/logaCr6+. The detection limit was found
Acknowledgment
to be less than 10-5 M.
40 This work was supported by PHC Maghreb
35
pure Cr2O7
2-
2-
No14.
SO4
30 2-
CO3
25 Cl
-
References
E (mV)/ SCE
20
15
[1] R.L. Twite, G.P. Bierwagen, Prog. Org. Coat.
1998, 33, 91.
10
[2] S. Langard, T. Norseth, Hand Book on the
5
Toxicity of Metals, Elsevier, New York, 1979.
0 [3] F.L. Petrilli, S. Deflora, Appl. Environ. Microbiol.
-5 1977, 33, 805.
-7 -6 -5 -4 -3 -2 -1
log a
[4] T. Norseth, Environ. Health Perspect. 1981,
40,121.
Figure 3 : EIS response depending on the concentration
[5] W.W. Tro, W.P. Fung, Toxicol. Lett. 1981, 8, 195.
of Cr (VI) ions in the presence of interfering ions.
[6] M.C. Taylor, S.W. Reeder, A. Demayo, in:
Guidelines for Surface Water Quality, Inorganic
3.2. Selectivity of the EIS structures Chemical Subtances, vol. 1., Water Quality Branch,
Inland Waters Directorate, Environment Canada,
The Cr6+ EIS response was examined in Ottawa, 1979.
[7] N. Jaffrezic-Renault, C. Clechet et P. Martelet,
the presence of various interfering Capteurs Chimiques et BiochimiquesX Techniques de
elements. The potentiometric selectivity lIngnieur, 1994, 3, 360-1242.
coefficient (Kpot) was evaluated by the [8] T.E. Edmonds, Chemical Sensors, Blackied & Son,
fixed interference method [7-9]. The Glasgow, 1988.
[9] M.L. Hamlaoui, R. Kherrat, M. Marrakchi, N.
concentrations of SO42-, CO32- and Cl- in Jaffrezic-Renault, A. Walcarius, Mater. Sci. Eng., C
the support solution were fixed to 10-3 M 2002, 21, 25.
Effect of Infra-red drying on

phenolics, flavonoids ,
antioxidant
and antibacterial activity of
Allium sativum.
LITAIEM Jihne a,b, TOUIL Amirac ,
CHEMKHI Saberd, ZAGROUBA Fethib
a Agronomical National Institute of Tunisia
b Higt Institute of Environmental Science and
Technology, Borj-Cdria, Tunisia
c Institut Suprieur des Etudes Technologiques de
Zaghouan, Tunisia
d Higt Institute of Environmental Science and
Technology, Gafsa, Tunisia
Abstract
Garlic (Allium Sativim L.,) is commonly

used as an essential ingredient in many
cooked
dishes. Drying conditions, particularly
temperature, leads to garlic modifications
that can
cause quality degradation. In this work, the
effect of infrared drying temperatures
between
40C and 70C on antioxidant capacity and
antibacterial activity of Allium Sativum
was
investigated. Total phenolics and
flavonoids contents were analyzed. The
antioxidant activity
was evaluated in vitro by means of DPPH,
ABTS and -carotene assay. The
antibacterial
activity was tested in vitro against a panel
of Gram+ and Gram- bacteria using the
disc
diffusion assay. Results have shown that
thermal processing augmented total
antioxidant
activity. Both total phenolic content and
total flavonoid content decreased as drying
temperature decreased. It was also noted
that antibacterial activity of garlic extract
was heat
sensitive. The antibacterial activity
decreased as drying temperature increased.
Keywords: Garlic, Infrared drying,
antioxidant activity; antibacterial activity.
CHEMICAL INTERACTION transmission system. It is a consequence of

electrochemical interaction between materials
OF C-MN STEELS IN SOIL steel and soil environment in order to return in
SIMULATED SOLUTION oxide state form thermodynamically more
AND PROTECTION BY stable.
Corrosion behaviour of C-Mn steel pipeline in
BORATE AS CORROSION soil environment after failure of the anti-
INHIBITOR corrosive protection systems (AC) motivates
A.Bendjebbour1 , A.Benmoussat1 our research. Steels have been protected by
coating containing bitumen binders or
1. Materials sciences Equip of LAEPO Research extruded polyethylene (EP) and a cathodic
Laboratory & Faculty of technology &Tlemcen
University & BP 230 - Chetouan University pole 13000 protection (CP) which the potential is
- Tlemcen - ALGERIA maintained to 850 mV Cu/CuSO4 in order to
Email: abbenmoussa@gmail.com isolate the steel from the soil environment and
Abstract: to prevent any risk of chemical interaction.
Unfortunately, corrosion problems have been
In hydrocarbons transmitting the external developed under certain conditions generating
chemical interaction between steel and the of pitting corrosion.
soil environment after failure of the anti Chemical interaction study has been simulated
corrosive protection systems are in laboratory while approaching the industrial
preoccupying phenomenon. Chemical context by choosing a most aggressive soil
interactions were simulated in laboratory simulated solution. Soil simulating solution
by choosing a most corrosive soil was chosen according to results obtained of
simulated solution. The selection criterion the most environments corrosive chemical
was mainly the contents of chlorides and composition .The selection criterion was
sulphates. The potentiodynamic mainly the chlorides, sulphates and
polarization measurements were bicarbonate content. However, the analysis
established with and without corrosion should also include a concentration of sodium,
inhibitor containing sodium borate. Results potassium and calcium ions so that an ionic
showed the low carbon steels sensitivity to balance can be struck. Electrochemical
chemical interaction and the corrosive impedance spectroscopy (EIS) and
character of the studied soil solution. potentiodynamic polarisation were carried out.
When increasing the temperature, the We present experimental data obtained by
polarization resistance decreases and the electrochemical measurements on the
corrosion speed increases as well as the behaviour of steel in soil simulating solution
densities of corrosion current ICorr . The with borate ions as corrosion inhibitors. The
tests with corrosion inhibitors containing electrochemical parameters such as potential
borate showed a displacement of the corrosion (Ecorr), corrosion current density
corrosion potential towards positive values. (Icorr) and polarization resistance (Rp) can
serve as the parameters to be determined
Key words: C-Mn steels simulated soil quickly to estimate soil corrosivity with
solution chemical interaction - corrosion accuracy and ease. The likely corrosion rate of
inhibitors borate of sodium potentiodynamic underground corrosion can be assessed in
polarization. terms of the soil pH, resistivity, temperature,
and redox potential. Steel mechanical
characteristics and physic chemical properties
1. Introduction have been established.
Corrosion risks such as external chemical
interaction are preoccupying phenomena in
oil industry and the major threats that can
reduce the structural integrity of pipelines
2. Experiment which presents a corrosive character with a

2.1 C-Mn steel parameter of conductivity 65.5ms/cm and a
pH 8.8.
Elemental composition of the cutting
samples (table 1) has been determined by
emission spectroscopy analysis type Table 3 - Chemical composition of soil
Spectro RP 212. Measured values were
compared to values quoted in the material Mass (mg/l)
test certificates [1]. Composition and
Ca2+ Mg2+ K+ Cl- SO42- HCO3-
microstructure can vary significantly
between pipes. These variations result in 94.60 56 7.6 76.9 736 117
substantial differences in corrosion
performances of pipeline steel in a 18.96 16.44 11.7 47.33 458.4 183
corrosion regime.
Table 1 - Elemental composition of - - 6 7.8 74 218
C-Mn steel pipeline
(Ti is the considered test) 2.00 29.04 1.82 22.69 37.48 160
% C Mn Si S P Cr
T1 0.13 1.03 0.3 0.01 0.017 0.01
Table 4 - Chemical composition of soil
T2 0.13 1.01 0.28 0.009 0.016 0.02 simulating solution (g/l)
T3 0.12 1.02 0.29 0.009 0.016 0.03 CaSO4 MgSO4 K2SO4 NaCl Na2SO4 NaHCO3
2.00 29.04 1.82 22.69 37.48 0.16
2.2 Soil simulated solution:
2.3 Corrosion inhibitors
The chemical interaction is related to soil
conditions in which the structures are
The corrosion inhibitor used is the borate ions
buried. The technique available to
BO2- , it is in various forms, boric acid H3BO3
determine the aggressiveness of the site
, and in alkaline medium, the
may include laboratory tests based on a
dihydrognoborate ion H2BO3-, the
chemical analysis of the soil. This
hydrogenoborate borate ion HBO32- and
technique can be used by itself for the
finally the borate ion. The borate can form
determination of the aggressiveness of a
various polymeric ions. Most common is the
specific location. Several soil samplings
ion tetraborate, B4O72- , there is also the ion
have been taken from various Algerian
hydrogenotetraborate HB4O7-. One also finds
sites from which we have chosen the most
triborate, pentaborate... The various ions
aggressive composition, shown in table 3.
metaborate have as an empirical formula
The criteria of aggressiveness to steel
BO2- and form metaborates compounds.
which have been adopted is principally the
Borate of sodium or borax of formula
chloride and sulphate content. [2]
Na2B4O710H2O [3] is an ore of boron called
also tetraborate of sodium or borate of
Si is the considered soil sites. Finally, we sodium.
have reconstituted the chemical
composition of the soil in a solution called The inhibitors solutions have been obtained
soil simulating solution (Table 4). by dissolution in distilled water to obtain
However, the analysis should also include different concentrations (10-3, 10-2, 10-1, 5.10-
1
a concentration of sodium, potassium and M).
calcium ions so that an ionic balance can
be struck. We have chosen the S4 solution
2.4 Corrosion tests Table 5 - Polarization parameters for the

Potentiodynamic polarization and corrosion of C-Mn steel in soil simulating solution
impedance spectroscopy (EIS) were according to the temperature (pH 8.8)
carried out by means of potentiostat
equipment of type Galvanostat PGP 201 Temperature Ecorr/SCE Icorr Rp
electrochemical Interface and controlled K (mV) (A.cm-2) kohms.cm2
with Tacussel corrosion analysis software 298 -637.2 3.44 14.11
(Voltamaster 4) to follow and record the 318 -695.0 5.36 5.64
polarization curves. The anodic and 333 -737.4 6.72 2.68
cathodic polarization curves were recorded
by a constant sweep rate of 0.5 mV.S-1. A
sine wave with 10 mV amplitude was used Table 6 - Polarization parameters for the corrosion
of C-Mn steel in soil simulating solution with
to perturb the system. Before recording
inhibitor containing borate of sodium at 25C
the polarization curves, the open circuit (C concentration)
potential was stable within 30 min. The
cathodic branch was always determined C Ecorr/ I Rp bc E%
first, the open circuit potential was then ml SCE corrosio kohm.c mV
reestablished and the anodic branch mV n m
determined. Inhibition efficiencies were A/cm
determined from corrosion currents 0.1 -825.4 1.6523 14.45 -94.3 57.77
calculated by the Tafel extrapolation 0.2 -527.0 0.3253 42.34 -116.8 91.11
method and fitting the curve to the 1 -492.9 2.1696 14.92 -307.0 66.66
polarization equation. Impedance spectra 0.5 2
were obtained in the frequency range 100 -473.9 2.2436 16.67 -246.0 64.44
kHz to 10 MHz with ten points per decade 3 -476.9 2.2079 11.94 -237.6 64.44
at the corrosion potential after 24 h of 1 -433.7 1.0855 16.60 -81.6 71.11
immersion. All tests were performed at 1 -454.5 4.3550 14.28 -497.0 75.55
25C in non-de-aerated solutions under 2
unstirred conditions. Square sheets of steel
of size (5 cm by 5 cm by 0.06 cm), with
exposed area of 3.88 cm2, were used as the
working electrode. Polarization parameters
values; corrosion current density (Icorr),
corrosion potential (Ecorr), cathodic Tafel
slopes (bc) and polarization resistance (Rp)
are considered.
3. Results and Discussions

3.1 Results
The potentiodynamic polarization tests showed
that the anodic and cathodic polarization curves
are recorded on study steel in de-aerated soil
simulating solution at various pH and
temperatures .The potentiodynamic polarization
curves of C-Mn steel are modified for the
various soil solutions:
Figure 1 Potentiodynamic polarization curves of C-Mn

carbon steel in Different corrosive soil solution at
25C
simulates conditions of pipe soil environment.

Figure 1 show that the potentiodynamic
polarization curves of steel are modified for
the various soil solutions: not filtered soil
solution, filtered soil solution and simulating
soil solution. Steel corrosion pitting is a
function of pH and temperature. For
corrosion potential value ((Ecorr = -637.2
mV/SCE), the corrosion of low carbon
pipeline steel in acidic soil simulating solution
is obtained by free potential. Results show that
the corrosion of iron as a function of pH
increases considerably at acidic environments.
If values of pH decrease toward the neutral or
acidic pH in the range 6 - 8, steel corrosion
increases and polarization resistance
decreases. In alkaline pH from pH 8, the
corrosion of steel decreases and polarization
Figure 2 Potentiodynamic polarization curves of C- resistance increases.
Mn carbon steel in Soil simulated solution with Temperature effect on the steel resistance
corrosion inhibitor containing borate of sodium at
25C
corrosion was carried out using
1.1 Study material potentiodynamic measurements. In the
The chemical composition of study temperature range (25 60C) the corrosion
material (table1) was made by current density increases with increasing
spectrophotometric analysis showing a temperature and the steel corrosion potential
microallied steel with a low carbon moves towards the negative values when the
percentage and the presence of manganese temperature increases in the studied solution.
particularly where makes it possible to The anodic polarization curves present
give to steel a good weldability having the parallel Tafel straight lines indicating that the
advantage of increasing the perlitic time hydrogen reduction reaction to steel surface is
of incubation. Steel contains low contents always done according to activation
carbon of order 0.13%, a strong mechanism in all the temperature range
concentration (1.03%) in manganese, and studied.
a low sulphur content (0.009%), giving to 1.3 Corrosion inhibitors
steel a better chemical resistance. Corrosion inhibitors tests for various
Chemical composition and mechanical soil medium showed a displacement of the
properties are in conformity with the API corrosion potential towards increasingly
norm, but contents high sulphur which in positive potentials with the increase in the
the presence of manganese can lead to the concentration of inhibitor. It was noticed that
formation of the manganese sulphides the effectiveness of the inhibitor increases
(MnS) inclusions which are not wished in very appreciably between proportioning going
the microstructure being able to generate of 0.1 10 -3 g/l with 0.2 10 -3 g/l and at the
the starting of a corrosion pit and its same time decrease effectiveness by
propagation. exceeding the 0.2 10 -3 g/l. The addition of
1.2 Corrosion pitting the disodic hydrogno-phosphate of sodium to
The potentiodynamic polarization concentrations ranging between 0.05 10 -3
tests showed that the anodic and cathodic and 0.5.10 -3 causes to lower the densities of
polarization curves are recorded on study corrosion currents and decrease effectiveness
steel in de-aerated soil simulating solution by exceeding the 0.5.10 -3 g/l
at various pH and temperatures that
4.Conclusions References
Chemical interaction of C-Mn steel and [1] API specification 5L (SPEC 5L), Specification for Line
soil solution has been simulated in pipe, 14th edn. Washington, 1992Klingler, J.
[2] K,Belmokr, N. Azzouz, F. Kermiche, Corrosion Study
laboratory while approaching the industrial
of steel protection by a primer, by electrochemical impedance
context by choosing a most corrosive soil spectroscopy (EIS) in 3% NaCl medium and in a soil
simulated solution. The selection criterion simulating solution, Materials and corrosion, p. 108-113,
was mainly the contents of chlorides and 1998.
sulphates. The physicochemical [3] A.Bendjebbour, localized corrosion of API steels solicited
characteristics of study steel and in Algerian soil - ASR/MP line, magister thesis, Tlemcen
potentiodynamic polarization University, 2012.
measurements were established with and [4]A.Benmoussat and all, Corrosion Behavior of API 5L X
without corrosion inhibitor containing 65 pipeline steel exposed to near neutral pH simulating
solution, Materials and corrosion, Wiley Inter science, vol. 57
sodium borate ions. Corrosion tests carried
N10 (2006) pp 771
out in the various soil mediums: non [5] A. Benmoussat, Corrosion Study of API 5L X60 Gas
filtered soil, filtered soil and simulating Pipelines Steels in NS4 Simulated Soil, integrity of pipelines
soil showed that steel corrodes with transporting hydrocarbons, NATO science for peace and
variable proportions. Steel corrosion is a security, DOI 10. 1007/978940070588-3_12, Springer
function of pH and temperature. The sciences (2011), pp 167-181
corrosion of iron increases considerably at
acidic environments. If values of pH
decrease toward the neutral or acidic pH in
the range 6 - 8, steel corrosion increases
and polarization resistance decreases. In
alkaline pH from pH 8, the corrosion of
steel decreases and polarization resistance
increases. The corrosion current density
increases with increasing temperature and
the steel corrosion potential moves towards
the negative values when the temperature
increases in the studied solution. Corrosion
inhibitors containing borate of sodium ions
are used in order to neutralize corrosion
without harmful effect on the environment.
The maximum inhibiting efficacy was
obtained for a weak concentration of the
inhibitor. It was noticed that the
effectiveness of the inhibitor increases very
appreciably with a concentration lower
than 0.2 10 -3 g/l for borate.
Acknowledgment
The authors are very grateful to the
LAEPO research laboratory of Tlemcen
university for their great help to make a
part of this work to be done.
Effect of Macromolecular still not completely understood. Clearly then,

information about the tribological behavior of
Weight on Nanotribological a single asperity must be useful in
Behavior of Polystyrene: understanding of how a multitude of asperities
progress in nano-attrition will behave. In this case, AFM has some
advantages over other small-scale techniques
comprehension during in that the interactions between the AFM tip
conveying processes and a substrate can act as a mimic for a single-
Achraf Ghorbal1, Rim Ben Arfi2, and nanoscale asperity.
Ammar Ben Brahim1 In the experimental work presented here,
the evolution of the nano-adhesion force and
1. Applied Thermodynamics Research Unit, National the nano-friction force between the AFM tip
Engineering School of Gabs, Gabs University, Rue
Omar Ibn-Elkhattab 6029 Gabs, Tunisia, E-mails: and four amorphous atactic polystyrenes (PS-
achraf.ghorbal.issat@gmail.com (A.G.); 26, PS-118, PS-245 and PS-385) surfaces is
ammar.benbrahim@enig.rnu.tn (A.B.B.) discussed.
2. National Engineering School of Gabs, Gabs
University, Rue Omar Ibn-Elkhattab 6029 Gabs,
Tunisia, E-mail: rimbenarfighorbal@yahoo.fr (R.B.A.)
2. Experiment
In order to carry out tests at the nano-scale,
Abstract:
a commercial atomic force microscope
Silicon nitride AFM tips were used so as to (D3100, Nanoscope IIIa controller, Digital
mimic the contact between amorphous Instruments, Santa Barbara, CA) was used.
polystyrene surfaces and a hard asperity, Experiments were performed at a relative
which is useful in understanding of how a humidity controlled within the range of 35-40
% in order to keep the same capillary force
multitude of asperities behave in a
contribution.
macroscopic contact. The frictional
2.1 Nano-adhesion Measurements
behavior of polystyrene showed a
dependence on macromolecular weight Adhesion force measurements are
performed in the so-called force calibration
with varying applied normal forces.
mode. In this mode, force distance curves are
obtained by recording the cantilever
Key words: Nano-adhesion, Nano-friction, deflection. The deflection of the cantilever
Polystyrene, Interface, Interactions. (i.e., the cantilever bends vertically toward or
away from the sample in response to attractive
and/or repulsive forces acting on the tip.) is
1. Introduction detected by an optical device while the tip is
Recent progress in polymer behavior vertically moved forward and backward
tests [1] has been due in large part to thanks to a piezoelectric ceramic. Thus, one
experimental instruments giving access to can obtain a deflection distance curve.
molecular scales, such as the Surface 2.2 Nano-friction Measurements
Forces Apparatus (SFA), the quartz-crystal
In the friction mode, the sample is scanned
microbalance and the Atomic Force
back and forth in a direction orthogonal to the
Microscope (AFM). Contact between solid
long axis of the cantilever beam. A friction
surfaces (e.g. solid granules onto a pipeline
force between the sample and the tip will
wall) is generally made through a
produce a twisting of the cantilever. Friction
multitude of asperities that constitute the
forces mean values were extracted from lateral
microscopic roughness of any real
diffraction (friction loop: the trace minus
surface [2]. Macroscopic mechanisms of
retrace value (TMR)) over scan areas of (1 m
polymer attrition are well-established,
x 1 m). Friction forces were averaged for
however the nanometric mechanisms are
more than 50 data points per sample at significant contribution of Van der Waals and
different locations on the surface. acidbase interactions.

Figure 1 shows the nano-friction force
of PS-26, PS-118, PS-245 and PS-385 as a
function of the normal force, which is
composed of the applied load and the pull-
off force. These data were obtained at the
sliding velocity of 1 m.s-1. In fact, the net
contact force, FN, corresponds to the
applied load only when it is positive. Figure 2: Adhesion forces with corresponding
Negative values are due to adhesion forces. capillary forces and (VdW/acide-base) forces
histograms of PS-26, PS-118, PS-245 and PS-385.
In fact, polymers are less entangled in the
boundary layer than in the interfacial sublayer.
Consequently, molecular weight increase with
significant macromolecules mobility leads to a
greater density of chains in contact with the
AFM tip (single asperity). Higher chains
density allows then the Van der Waals and
acidbase interactions to take place.
Therefore, higher adhesion is expected, which
Figure 1: Friction force vs applied normal leads to a higher friction coefficient for higher
force for PS-26, PS-118, PS-245 and PS-385 macromolecular weights.
recorded at 1 m.s-1 sliding velocity.
The linear increase of the friction force
as a function of the normal load can be 4. Conclusions
modeled by a modified form of the The nanofriction force variation showed
generalized Amontons law where the that the PS nano-frictional behavior obeys the
friction force (Ff) is given by [3] generalized Amontons law. Residual force
and friction coefficient values increase was
attributed in the major part to adhesive forces
and particulary to VdW and acide-base
Here, FN is the applied normal force, Ff
interactions.
is the friction force, F0 called the residual
force is the friction force when FN is zero,
and =Ff/FN is the coefficient of friction. References
We found that residual force values [1] Ghorbal, A.; Ben Arfi, R.; Bistac, S.; Brogly, M.
decrease in the following order: F0PS-385 > Polystyrene chains orientation: A rubbed and non-rubbed
F0PS-245 > F0PS-118 > F0PS-26. These results polymer comparative study, Chem.Phys.Lett. 2007, 443,
are in good agreement with the nano- 352355.
adhesion experiments (see Figure 2). [2] Ghorbal, A.; Ben Arfi, R.; Mokhtar, F.; Zrelli, A.; Ismaili,
As measurements were performed at the S.; Grisotto, F.; Charlier, J.; Palacin, S. Polystyrene
Tribological Performance: Progress in the Understanding
same relative humidity, one can definitely
of Polymers Attrition during Chemical Engineering
confirm that the contribution of the Processes; In Polystyrene: Properties, Performance and
capillary forces during the nano-friction of Applications; Gray, J. E., Eds.; Nova Science Publishers
PS-26, PS-118, PS-245 and PS-385, is New York, 2011. pp. 138.
identical. Hence, the friction coefficient [3] Bistac, S.; Schmitt, M.; Ghorbal, A.; Gnecco, E.; Meyer,
increase as the macromolecular weight E. Nano-scale friction of polystyrene in air and in
increase is necessarily related to a vacuum, Polymer 2008, 49, 37803784.
COMBINED PROCESS FOR Key words: 2,4-D; Carbon felt electrode;

Electrochemical pre-treatment; Biodegradability;
THE DEGRADATION OF A Biological treatment.
PESTICIDE, 2,4-D:
COUPLING OF AN 1. Introduction
ELECTROCHEMICAL
2,4-Dichlorophenoxyacetic acid (2,4-D
PROCESS WITH A Fig.1) is a chlorinated phenoxy herbicide
BIOLOGICAL widely used in gardens and farming to control
TREATMENT broadleaf weeds. Although the World Health
Jean-Marie Fontmorin1,2, F. Fourcade1,2, F. Organization considers 2,4-D as a moderately
Geneste2,3, D. Floner2,3, A. Amrane1,2 toxic compound (class II or III), it is known to
produce moderate and serious skin and eye
irritation. This chlorinated organic compound
1. Ecole Nationale Suprieure de Chimie de Rennes, is poorly biodegradable. Literature disclosed
CNRS, UMR 6226, Avenue du Gnral Leclerc, CS many studies focusing on 2,4-D degradation,
50837, 35708 Rennes Cedex7, France.
2. Universit Europenne de Bretagne
especially using Advanced Oxidation
3. Universit de Rennes 1, CNRS, UMR 6226, Processes such as Photocatalysis [1] or
Equipe Matire Condense et Systmes Fentons processes [2]. Although these
Electroactifs, Campus de Beaulieu, 35042 Rennes
Cedex, France
methods often lead to a complete
Email : abdeltif.amrane@univ-rennes1.fr mineralization of the pollutant, they are
expensive and by-products of higher toxicity
Abstract: can be produced because of the non selectivity
A combined process coupling an of the processes. The aim of this work was to
electrochemical pretreatment with a study a promising electrochemical pre-
biological treatment was examined for the treatment that would increase the
biodegradability of the 2,4-D prior to a
removal of a pesticide, 2,4-D. The classical biological treatment.
electrochemical pre-treatment was based
on a home-made flow cell using a porous
graphite felt of high specific area as a
working electrode. Biological treatments
were carried out in aerobic conditions with
activated sludge from a local WWTP. Figure 1. Chemical structure of 2,4-
Dichlorophenoxyacetic acid
The performance of the electrochemical
process was first studied in oxidation (1.6
V/ECS) to degrade a halogenated herbicide
The degradation of 2,4-D was studied, the
(2,4-D). 96 3% of the initial 2,4-D were
major by-products were determined and
degraded after the pre-treatment stage and quantified and the biodegradability of
34 4% of the dissolved organic carbon electrolyzed solutions has been assessed, prior
were mineralized. The following biological to activated sludge cultures.
treatment led to an overall mineralization The electrochemical pre-treatment was
based on a home-made flow cell and a bare
of 85%, while the activated sludge was not
graphite felt was used as a working electrode.
beforehand acclimated to the target The electrolyte solution (500 mg L-1 2,4-D in
compound. 0.1 M Na2SO4) percolated the porous
electrode at a constant flow rate of 1 mL min-
1
. Preliminary cyclic voltammetry studies
helped setting the potential of electrolysis electrochemical cell, may be carried out in
at 1.6 V/SCE. order to improve effluent biodegradability.
The residual 2,4-D concentrations were - Most of the persistent organic pollutants
measured by HPLC after the electrolysis. being halogenated compounds, the specific
For four similar experiments, high removal of halogen groups from the substrate
elimination yield of 96 3% was obtained could be considered. The graphite felt is a
in only one pass through the flow-cell. cheap material that can be easily derivatized
Dissolved Organic Carbon (DOC) by chemical or electrochemical methods. For
measurements showed that 34 4% of the this purpose, Nickel and Cobalt mediators can
initial organic carbon were mineralized be immobilized on the electrode surface,
during the pre-treatment step. These results covalently linked to the electrode. Works are
confirmed the feasibility and the relevance in progress in the laboratory regarding the
of the electrochemical process. The electrocatalytic reduction of carbon-halogen
biodegradability of 2,4-D and of the bonds of some halogenated target compounds,
electrolyzed solutions was subsequently as well as the influence of the dehalogenation
estimated by means of BOD5 and COD on the biodegradability of these compounds.
measurements. Since the BOD5/COD ratio - The acclimation of activated sludge to the
of 2,4-D was 0.04, the pesticide was non by-products could be also a solution to
biodegradable. After electrolysis, the improve the mineralization of the electrolyzed
BOD5/COD ratio of the oxidized solution solution.
was 0.25, showing that the
biodegradability was significantly References
improved.
[1] Fontmorin, J.-M.; Huguet, S.; Fourcade, F.; Geneste, F.;
Degradation by-products were identified
Floner, D.; Amrane A. Electrochemical Oxidation Of 2,4-
by LC/MS/MS or GC/MS and then more D: Analysis Of By-products And Improvement Of The
precisely quantified by HPLC. LC/MS/MS Biodegradability. Chem. Eng. J. 2012, 195196, 208-217.
results showed the presence of [2] Fontmorin, J.-M.; Fourcade, F.; Geneste, F.; Floner, D.;
Chlorohydroquinone and 4-Chlorocatechol Huguet, S.; Amrane, A. Coupling of an electrochemical
as the main products in the oxidized 2,4-D process with a biological treatment for the removal of 2,4-
solution. Quantification by HPLC revealed Dichlorophenoxyacetic acid. Biochem. Eng. J. 2013, 70,
that these species represented respectively 17-22.
35 and 10% of the residual DOC. Other
more volatile compounds have also been
detected by GC/MS, such as 2,4-
Dichlorophenol and a LC/MS/MS study
led to the determination of glycolic acid.
Finally, the formation of major degradation
by-products was discussed and a
mechanism scheme was implemented.
The following biological treatment led
to an overall mineralization of 85% with
no acclimation of the activated sludge
[1,2].
3. Conclusions
To continue this work some research
avenues can be considered:
- electrochemical conditions such as flow
rate, solution recycling in the
Study of the performances of - The integration of a membranes planes in a flat

plate solar collector.
different configurations for The scientific interest is that solar flow is
seawater variable and intermittent during the day and all
the
desalination with a solar year. This will lead to a study of the system in
membrane distillation transient regime.
Nader FRIKHA1, Samira The following figures show some examples of
BENABDALLAH, Bchir CHAOUACHI, possible configurations.
Slimane GABSI
Ecole Nationale des Ingnieurs de Gabs,
Rue Omar Ibn-Elkhattab 6029, Gabs
Tunisie
Abstract
The objective of this work is to study, design
and propose new systems for producing
drinking water from seawater using systems
based on coupling of membrane distillation
and
solar energy. The use of solar energy can be:
_ Provided by the heating of sea water by a
coolant from the solar collector. The
distillation module is separated from the
solar system (system not integrated),
_ The module is integrated in the solar
collector (integrated system).
_ The module is immersed in the solar
collector,
For the first configuration, control of the
temperature level of water feeding the
membrane
module is possible; we can provide storage if
temperature admissible by membrane
module is
exceeded and we can also used an auxiliary
energy when needed.
The second configuration is more original it
makes it possible to reduce the components
of the
installation and the heating of sea water is
direct.
It is necessary to study and evaluate the
contribution of the sun and the possibilities
of energy
storage either to the lover or with the
downstream.
Various configurations of membranes
modules integrated in the solar collector can
be
designed. The study related to:
- The integration of a fiber module in an
absorber of a cylindro-parabolic collector,
NO AND N2O EMISSIONS (NO) and nitrous oxide (N2O) as described by

DURING WASTEWATER Wrage et al. [2]. They proposed a global
diagram for the biological treatment of nitrates
DENITRIFICATION STEP:
(Fig 1). The denitrification process depends on
INFLUENCE OF THE biological and physico-chemical parameters
TEMPERATURE ON THE (pH, temperature, viscosity, concentrations)
BIOLOGICAL PROCESS [3-5]. The carbon source may also affect the
denitrification process [6].
Adouani Nouceibaa, Limousy Lionelb, Figure 1: Biological ways for the transformation of
Lendormi Thomasc et Sire Olivierc mineral nitrogen [1]
a Laboratoire Ractions et Gnie des procds, LRGP,
Nancy, France., In this work, we investigate the effect of
b. Institut de Science des Matriaux de Mulhouse, CNRS
,UMR-7361 , 3 bis rue Alfred Werner, 68093 Mulhouse,
France,
c .Universit Europenne de Bretagne, LimatB, Pontivy,
France,
Abstract:
During biological denitrification in Waste
Water Treatment Plants (WWTPs), many
parameters (chemical, physical and
biological) are responsible for greenhouse
gas emissions such as nitrous oxide (N2O)
and nitric oxide (NO). The present study temperature on the production and more
intends to investigate the impact of the especially the emissions of NO and N2O
temperature (5, 10 and 20C) on N2O and during the denitrification step. Three
NO emissions. The experiments were temperatures were studied: 20C, 10C and
achieved in a bioreactor performing batch 5C. These values were chosen since they span
denitrification at a laboratory scale. those observed in the north of Europe. The
Acetate was used as the carbon source and present study focused on the impact of
the pH was 7. The nitrogen source was temperature on nitrogen abatement kinetic.
nitrates (NO3) and the COD/N ratio was
set to 3. Results showed that NO and N2O 2. Experimental procedure
emissions increased as the temperature Experimentations were achieved in a batch
decreases. NO emissions, not observed at reactor of 10 Liters (utile volume), stirred at
20C, appeared after 7 hours at 10C and 400 rpm, pH 7. The synthetic effluent was
after 1.5 hour at 5C. Low temperatures composed of 1 Liter of synthetic effluent and
affect the enzymatic activity as well as the 9 Liters of activated sludge collected from the
kinetic of nitrate conversion. biological basin of the Pontivy Waste Water
Keywords: Denitrification; Nitrous oxide; Nitric Treatment Plant (WWTP) (South Brittany,
oxide; Wastewater, Enzymatic kinetics. France). Initial conditions were: 40 mg.L-1 of
N-NO3 and 120 mg.L-1 of carbon ( acetate).
1. Introduction The gasliquid transfer of N2O and NO
Nitrogen abatement in wastewater emissions to the atmosphere was enhanced by
(biological treatment) firstly starts by an upstream bubbling of He gas (0.42 L/min).
nitrification process, which transforms Nitrites, nitrates and COD concentrations
ammonia (NH4+) into nitrates (NO3-), were determined from the liquid phase by
followed by denitrification, which colorimetric methods according to French
transforms nitrates into molecular nitrogen normalized methods. The reactor head space
(N2) [1]. During the denitrification step, was continuously analyzed by using an online
two intermediates are produced and may be gas chromatograph (Varian CP-4900) to
present into the aqueous phase: nitric oxide monitor N2O emissions, and an ultraviolet
analyzer (Emerson analytical) to monitor Table 1: Characteristic data obtained from

NO emissions. experiments carried out at different temperature
In addition to gas and liquid phase analyses during the denitrification step
Temperature C 20 10 5
performed during denitrification in the
N-N2O emission (mg N) 42 142 165
batch reactor, respirometric assays were N-NO emission (mg N) 0 28 36
performed for each experiment to Emission mean rate of N2O
characterize the sludge. 0,15 0,19 0,21
(mg N.gMVS-1.h-1)
Emission mean rate of NO (mg
3. Results and Discussion N.gMVS-1.h-1)
0 0,04 0,05
Nitrogen consumption mean
1,2 0,5 0,25
The respirometric experiments showed that rate (mg N.gMVS-1.h-1)
the kinetic of COD degradation was not % N-N2O/N denitrified 13 40 82
affected by the temperature under aerobic % N-NO/N denitrified 0 8 18
conditions. Nevertheless, the maximal MVS (g.L-1) 3,48 3,28 3,1
oxygen rate consumption significantly
decreased when the temperature was below 4. Conclusion
20C.
The effect of temperature upon NO and
Figure 2 shows the time evolution of the N2O emission during the biological treatment
reagents and the gas produced during the
of nitrate presented in this work, indicates that
experiment performed at 10C. At the
it is a critical point for wastewater treatment.
opposite of the experiment carried out at
20C, we observed the emission of NO Low temperatures induce important emission
after 7h at 10C and after 1.5h at 5C. of N2O and also of NO, which cause a
Table 1 summarizes the data relative to the significant pollution transfer to the
different experiments. atmosphere.
References
[1] Beline, F. Martinez, J., Chadwick, D., Guiziou, F. and
Coste, C.M., Factors affecting nitrogen
transformations and related nitrous oxide emissions
from aerobically treated piggery slurry. Journal of
Agricultural Engineering Research, 1999, 73, 235-243.
[2] Wrage N., Velthof G.L., van Beusichem M.L.,
Oenema O., Role of nitrifier denitrification in
theproduction of nitrous oxide. Soil Boil. Biochem.,
2001, 133, 1723 1732.
[3] Young K.,, Yuhei I., Motoyuki M., and Ahn Kyu H.,
Emission and Control of Nitrous Oxide from a
Biological Wastewater Treatment System with
Intermittent Aeration. Journal of bioscience and
Figure 2: Time evolution of the concentration of bioengineering. 2000, 90 : 247-252.
the reagents and the gases emitted during the [4] Foglar L. and Briski F., Wastewater denitrification
experiments performed at 20, 10 and 5C process - the influence of methanol and kinetic
analysis. Process Biochemistry. 2003, 39, 95-103.
Results showed that the lower temperature, [5] Elefsiniotis P., Wareham, D.G., and Smith M.O., Use
of volatile fatty acids from an acid-phase digester for
the larger the N2O emissions: 13%wt, denitrification. Journal of Biotechnology, 2004, 114,
40%wt et 82% wt of denitrified N-NO3- at 289-297.
20C, 10C and 5C, respectively. This [6] Adouani N., Lendormi T., Limousy L., Sire O., Effect
of the carbon source on N2O emissions during
result may be explained by an enzymatic biological dnitrification, Resources, Conservation and
slow down. Moreover, NO emissions were Recycling, 2010, 54, 299-302.
only observed at 10C and 5C. These
emissions may be explained by a partial
inhibition of N2O reductase, which induces
a massive accumulation of NO into the
liquid phase at low temperatures.
Use of cellulosic waste orange agitation time, adsorbent dosage and agitation
rate were investigated in batch-mode
peel for removal of dyes from adsorption studies.
aqueous solutions 2. Experiment
Khoualdia Besma1, Guiza Sami2 and
Bagan mohamed Methods
The suit orange was obtained from a local
Environmental Chemistry Division, Department of market and peeled. The peels were cut into
process and chemistry, National School of Engineers,
University of Gabes small pieces, dried in sunlight and were
Khoualdia Besma12@gmail.com crushed. The powdered orange peel was
Sami_guiza@yahoo.fr sieved. The particle sizes were < 250 m.
Drmbag1420@yahoo.fr
Adsorption studies
Abstract: Adsorption equilibrium experiments were
The adsorption of dyes such as congo red carried out by adding the dried adsorbent in
(CR) and methylene blue (MB) by waste 100 ml of dye solution with desired
orange peel was examined at different conditions. After 3 h the suspension was
centrifuged at 2000 rev.min -1 for 10 min and
concentrations of dyes, adsorbent dosage, the final concentration of dye in solution was
processing time, temperature, agitation rate measured using an UVVIS
and pH. It is a spontaneous exothermic spectrophotometer therme Sxientific,
physical adsorption which obeyed both the Genesys 10 S UV-VIS. The wavelengths
Langmuir and Freundlich isotherms and 492, 665 nm were used as the monitoring
wavelengths for CR and MB, respectively.
the process of uptake followed second- The amount of dye adsorbed onto the peels, qe
order rate kinetics. (mg/g), was calculated by the following
Key words: Waste orange peel, congo red, relationship.
Methylene Blue, adsorption, modeling. qe = (C0 Ce) [5]
1. Introduction Where C0 and Ce are the initial and
Wastewaters from food coloring, cosmetics equilibrium liquid-phase concentrations of
and textile industries are polluted by dyes dyes, respectively (mg/l), v the volume of the
and they are one of the main environmental solution (L), and m the weight of the dry peel
problems. There are various conventional used (g).
methods for the removal of dyes including For the kinetic experiments a closed jacketed
coagulation and flocculation, oxidation and reactor fitted with a paddle stirrer and a motor
membrane separation. However, these for obtaining agitation speeds between 100
methods are not widely used because of and 300 rev / min was used. The aqueous
their economic disadvantages. Low-cost samples were taken at preset time intervals,
treatment methods have, therefore, been and the concentrations of dyes were similarly
investigated for a long time. measured.
A number of low-cost adsorbents have 3. Results and Discussion
been tried for dye removal. These include
Since the aqueous extract of orange peel in
the banana and orange peel [1], tamarind
water also absorbs at the monitoring
fruit shell [2], bark yellow passion [3], rice
wavelengths. The effect of this color on the
husk [4]. The present investigation is
absorbent measurement was studied and no
undertaken to test the use of a cellulosic
considerable effect is shown.
waste, orange peel, for the removal of Effect of different parameters on sorption
different types of dyes: CR (acid), and MB process
(basic), from aqueous solution. The
Removal of dye by adsorption on orange peel
parameters which affect wastewater increased rapidly in the beginning and then
treatment, such as dye concentration, pH,
more slowly until the equilibrium time. peel obeyed both the Langmuir and
The equilibrium time for the dyes CR and Freundlich isotherms.
MB were 100, and 35 min, respectively. Pseudo-second-order plot for dyes removal
The increase in the initial dye from aqueous solution ( versus time)
concentration increased the amount of dye
adsorbed but it slows the kinetics. The gives correlations coefficients of about 0.95,
adsorption of dyes increased with the then the sorption of dyes on orange peels
adsorbent dosage and reached a constant follows second order kinetics.
value after a particular dosage. The 4. Conclusions
sorption of MB is favorable at acidic pH
Based on the present investigation, it could be
while the RC supports basic pH. The
concluded that some simple and low-cost
Increase in the speed accelerates the
adsorbent as the waste orange peel are useful
adsorption kinetics therefore equilibrium
for the removal of dyes from colored
time decreases. The increase of
discharges. Sorption isotherms were better
temperature accelerates the adsorption
represented by Langmuir model than the
kinetics but the adsorption of dyes
Freundlich model. This process followed
decreased. It is therefore better to work at
second-order rate kinetics.
room temperature.
Isotherms Acknowledgment
Experimental isotherm is useful for Thanks to my two trainers, Guiza Sami and
describing adsorption capacity to facilitate Bagan Mohamed, and all members of the process
and chemistry department.
evaluation of the feasibility of sorption.
Moreover, the isotherm plays an important References
role in the predictive modeling procedures [1] Gurusamy, Annadurai; Ruey-Shin, Juang b; Duu-
for analysis and design of sorption Jong, Lee. Use of cellulose-based wastes for adsorption
systems. The Langmuir and Freundlich of dyes from aqueous solutions. Journal of Hazardous
isotherms are most frequently used to Materials. 2002. B92. 263274.
represent the data of sorption from [2] M C Somasehkara, Reddy. Removal of direct dye
solution. Figures 1 and 2 show the sorption from aqueous solutions with an adsorbent made from
isotherms of MB and CR on orange peel. tamarind fruit shell, an agricultural solid waste. Journal
of Scientific and Industrial Research. 2006. 65. 443-
446.
150
T=25 C
T=35 C
[3] Flavio, Andr Pavan; Ana Cristina, Mazzocato;
T=50 C
T=65 C
Yoshitaka, Gushikem. Removal of methylene blue dye
100
from aqueous solutions by adsorption using yellow
qe (mg/g)
passion fruit peel as adsorbent. Journal of Bio-resource

50 Technology. 2008. 99. 31623165.
[4] Upendra, Kumar; Manas, Bandyopadhyay. Sorption
0
0 20 40 60
Ce (mg/l)
80 100 120 of cadmium from aqueous solution using pretreated rice
Fig 1: Isotherms of sorption of BM by orange husk. Journal of Bio-resource Technology. 2006. 97.
peel (m = 0.1 g / 100 ml, pH = 7.5) 104109.
50
[5] Baghriche, Oualid. Contribution de mthodes
T=25 C
T=35 C
destructives (Photolyse et P.O.A's) et non destructives
40 T=50 C
T=65 C
l'limination de deux colorants (Bleu de mthylne et
30 rouge Congo) en solution aqueuse. Master. Mentouri
qe (mg/g)
20
Constantine University, Algrie. 2005.
10
0
0 20 40 60 80 100 120 140 160 180 200
Ce (mg/l)
Fig 2: Isotherms of sorption of CR by orange

peel (m = 0.1 g / 100 ml, pH = 8)
Based on correlation coefficients R2 the
adsorption of CR and MB on waste orange
Simulation model of a process biomass manifested as lower substrate

biodegradability. In addition, the treatment of
for anaerobic digestion complex wastewaters containing significant
Hmissi Maha*,Shayeb Hedi
amounts of fat may cause problems of scum
Laboratory of Hydraulic and Environmental Modeling, and sludge layer on top of the reactors with
National Engineering School of Tunis, University of El- subsequent biomass washout (Hanaki et al.,
Manar, 37 Le Belvdre, 1002 Tunis, Tunisia
Maha.hmissi@hotmail.fr 1981; Rinzema et al., 1994). Anaerobic
Digestion Model 1 (ADM1) gives clear
insight into the anaerobic digestion process. It
Abstract: is comprised of 24 components and 19
The anaerobic digestion model No. 1 processes, in order to simulate all possible
(ADM1), conceived by the international reactions occurring in anaerobic digestion
water association (IWA) task group for including biological reactions, such as
mathematical modeling of anaerobic disintegration, hydrolysis of suspended solids,
digestion processes is a structured generic uptake (growth) and decay of microorganisms.
model which includes multiples steps The number of processes that need to be
describing biochemical and accounted for in the modelling of the
physicochemical processes encountered in anaerobic process and the high number of
the anaerobic degradation of complex stoichiometric and kinetic parameters used
organic substrates and a common platform make this a model relatively complex.
for further model enhancement and (N.Coelho et al., 2006)
validation of dynamic simulations for a Taking into account the ADM1 potential
variety of anaerobic processes. In this advantages in modeling and continuing the
study the ADM1 model was applied to research of ADM1 implementations for
simulate the thermophilic anaerobic simulating the anaerobic digestion of more
digestion of olive mill wastewater (OMW) complex organic mixed substrates such as the
with olive mill solid waste (OMSW). The mixture of OMW with OMSW, the main
ADM1 equations were coded and objective of the present work is to develop and
implemented using the simulation software implement the ADM1 for simulating the
package MATLAB/Simulink. The most thermophilic anaerobic digestion of OMW
sensitive parameters were calibrated and with OMSW. Then, it will be calibrated and
validated using updated experimental data validated using some experimental results
of Fazzanis 2008 work. The results from Fazzanis 2008 work.
indicated that the ADM1 model could
2. Dynamic state
simulate with good accuracy: gas flows,
methane and carbon-dioxide contents, pH 2.1 Model calibration
and total volatile fatty acids (TVFA). Experimental results of the thermophilic
anaerobic digestion of OMW (TCOD = 130
Key words: Anaerobic digestion; ADM1; g/l) and OMSW at HRT for 36 days, in semi-
Simulation; MATLAB/Simulink continuous tubular digesters were used to
assist the model calibration and are given by
Fazzani (2008).
1. Introduction
Tab1: Initial and estimated values of kinetic
Dairy effluents are considered complex parameters
wastewaters, due to their high organic Estim
Kinetic Names Units Initial ated
content, comprised of several types of paramet values value
compounds, such as carbohydrates, ers s
proteins, and lipids. Lipids are considered Half Kg
to be problematic in anaerobic treatment, Ks,aa saturation DCO 0,3 0,99
constant for /m3 9
because they accumulate inside the
amioacids
reactors and lead to inhibition of the utilisers
Half Kg 0,5 0,1

Ks,su saturation DCO
constant for /m3
sugars
utilisers
Half Kg 7 E-6 0,05
Ks,h2 saturation DCO E-6
constant for /m3
hydrogens
utilisers
The rate m3/K 1E10 7,6
KAB,co2 constant of mol/j E8
the acid-
base Fig 1: Biogas ow, CH4 and CO2 percentages, euent pH
reaction of and TVFA concentrations were predicted with high accuracy
CO2
It can be seen that methane and carbon-
2.2 Results and discussion dioxide contents were well predicted by the
(a) ADM1 model with some deviations between
simulation and measurements in the dynamic
state for CO2 percentages.
As well, we can say that TVFA concentrations
show a high stability of the digester and were
in agreement with the experimental results
except for the first ten days they were under
predicted.
It can be seen that biogas ow, was predicted
with high accuracy, it was well predicted by
(b) the ADM1 model for both the steady state and
dynamic state.
Finally, euent pH were well simulated by
the ADM1 and were stable, however, these
results show that the reactor has a good
stability in terms of pH.
3. Conclusions
The ADM1 model was successfully
implemented to simulate the anaerobic
(c)
digestion of OMW and OMSW under
thermophilic conditions. In fact, this model
was able to yield similar results as found in
experimental trials. Gas ow, methane and
carbon-dioxide contents, pH and TVFA
concentrations of euents were well
predicted by the ADM1 model.
References
(d) [1] Batstone, D. J., Keller, J., Angelidaki, I., Kalvuzhny, S.
[2] V., Pavlostathis, S. G., Rozzi, A., Sanders, W. T. M.,
Siegrist., H. and Vavilin, V. A. (2002a) Anaerobic digestion
model No. 1 (ADM1). IWA Publishing, London, UK
[3] Christian, Rosen and Ulf, Jeppsson.,2005. Aspects on
ADM1 implementation within the BSM2 framework,1-20.
[4] Fazzani, B. Etude Experimentale et Modelisation

Mathematique de la Co-digestion Anarobie Msophile et
Thermophile des dchets des huileries dolives.
[5] Fazzani B., et Ben Cheikh R., (2008) Modelling of the

mesophilic anaerobic co-digestion of olive mill
wastewater with olive mill solid waste using anaerobic
digestion model No. 1 (ADM1) 6571-6577
[6] Hanaki, K., Matsuo, T., Nagase, M., (1981)

Mechanisms of inhibition caused by long chain fatty
acids in anaerobic digestion process, Biotechnology and
Bioengineering, 23, 1591-1560.
[7] IWA; (2002) Anaerobic Digestion Model No. 1
(ADM1), International Water Association Scientific and
Technical Report No. 13, IWA Publishing, London, UK.
[8] N. Coelho, I. Capela and R.L. Droste APPLICATION
OF ADM1 TO A UASB TREATING COMPLEX
WASTEWATER IN DIFFERENT FEEDING
REGIMES, 7123-7124
[9] Rinzema, A., Boone, M., Knippenberg, K., Lettinga,
G., (1994) Bactericidal effect of long chain fatty acids in
anaerobic digestion, Water Environment Research, 66(1),
40-48.

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ICEC'13 Keynotes and Orals Abstracts CO -1

physicochemical properties of the membrane

of the feed solution m) provided by Pall Exekia (Bazet, France).

filtration time (black points) observed presence of ionic or alkaline (Na2CO3,

Figure 1: simulation of the membrane permeability 4. Conclusions

STUDY OF BIOREFINERY In the present work two different

organosolv scenario) and water ( in both heating/cooling utilities. Furthermore, the

Figure 2: Feedstocks and utilities requirements for

1996, NREL/MP-425-20685, National Renewable

SOLID REACTION EFFECT bed. Erosion by only impact exceeds global

SIMULATION OF THE continuous or discontinuous feed modes.

I nvestigation of grape marc The tested samples of wine residues

0DWHULDOVDQGFKDUDFWHUL]DWLRQ where: m(t) is the mass sample at time t,

Study of non stationary avoids the emissions of carbon dioxide,

radiation on the concentrator. 350

solution until equalization of pressures of Figure 3: Variation of the temperature of the

Figure 2: Variation of the temperature of

The gap between the two curves is due

Granular and Pelletized CAGOC-Pas. Temperature- dependent

Sonia BEN YAHIA, Abdelmottaleb

and followed by water wash to remove 2.2. Experimental Set-up

2.1.2. Sample characterizations

Compaction and pelletization of an olive

Production de bio nergie par la possde un pouvoir nergtique lev et peut

Application des doptimiser ce dpt en ajustant les

Mots cls : impdances lectrochimiques,

Figure 2 : courbes chrono

Elaboration, characterization and activating agent, allows the development of a

Utilization of cement kiln dust column experimental measurements are also

Elaboration of TiO2 Among them, surfactant-mediated Sol-gel

ADSORPTION AND has recently been focused on various materials

pharmaceutical compounds). The total

or the change in compound state [2]. Within

The ultrafiltration unit used for the

Nitrogen removal and cyclically to create alternating aerobic and

BEHAVIOR OF COPPER of metal-containing effluents [1]. Thus,

Pharmaceutical residue reaction of the active ingredient on the

Biodegradability experimental conditions. The feasibility of

1. Laboratoire de Chimie Analytique et lectrochimie,

biodegradability of polluted solutions of compatible, namely BOD5 on COD ratio

Evaluation of olive stones as and Freundlich equations. These adsorption

Adsorbed amount (mg/g)

calcium phosphates precipitates. The pH

removal (Figure 2). This finding may be

wastewaters. The adsorption process

200 and decreased with increasing pH values. The

Enhancement of methylene efficient in dyes removal, some of them have

80 wastewaters. Indeed best removal efficiencies

Figure 1: Colour removal efficiency by anodic

DCO (mg O2/L)

sawdust is very dependant onto both the 0 4 8 12 16

Abstract: 2. Experimental part

The equations previously determined

Figure 1: CO and CO2 concentration vs. time for

Key words: wetness impregnation, activated

Proximate analysis (%), HV Friedman and Phadnise-Deshpande methods.

Heterogeneous Advanced Photo- Several complementary techniques, including

Aromatic compounds are common

PRODUCTION AND membrane used and the cutoff or particle size

After the hydrogenolytic approach, two References

Table 1: Summary of compounds present in the obtained oil.

A.; Labidi, J. Fractionation of Organosolv Lignin

Activated carbon prepared by physical efficient carbonaceous adsorbents from olive

0DWHULDOVDQGFKDUDFWHUL]DWLRQ where: m(t) is the mass sample at time t,