ENVIRONMENTAL ENGINEERING SCIENCE

Volume 25, Number 2, 2008

© Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2006.0102

Kinetic Parameters of Hydrothermal Oxidation Process on

Olive Mill Wastewater

Souad Chkoundali,1,2* Sahbi Alaya,2 Jean-Claude Launay,1 and François Cansell1

1Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB)

33608 Pessac, Cedex, France
2Faculté des Sciences de Gabès

Tunisie, France

ABSTRACT

Olive mill wastewater (OMW) was treated with a batch reactor up to 500°C and 25 MPa to determine the
working pressure and temperature conditions to ensure OMW treatment. From these data, experiments
were performed in tubular reactor, in a temperature range between 200 and 400°C, at 25 MPa. The Runge-
Kutta algorithm method was used in order to obtain kinetic parameters for the hydrothermal oxidation of
olive mill wastewater. The activation energy of the reaction was found equal to 48 kJ.mol1 (regarding
the chemical oxygen demand removal) with an oxygen order equal to 0.15.

Key words: hydrothermal oxidation; olive oil mill wastewater; kinetic parameters; Runge-Kutta algo-
rithm; tubular reactor

INTRODUCTION in absence of specific laws. This land feeling may pres-

ent a danger regarding the water reserves and the pro-

T HERE ARE PRESENTLY 800 million productive olive

trees on the planet, which occupy a surface area of
more than 71010 m2. The worldwide production of olive
oil in 2003–2004 was 3,174 tonnes. The Mediterranean
area alone provides 99.2% of the total olive production
on the period from 1999 to 2005 (http:www.internation-
aloliveoil.org; Sayadi et al., 2000). Around 30 millions
m3 of olive mill wastewater (OMW) are produced annu-
ally in the Mediterranean area (Casa et al., 2003). Today,
in Italy and Portugal, land feeling of OMW is controlled
by legislation procedures. Nevertheless, this practice is
performed illegally in several olive-producing countries,
duction of drinking water because OMWs are not easily
biodegradable. These liquid wastewaters are colored in
brown dark, odorous and characterized by the presence
of a large quantity of organic compounds. Olive extrac-
tion is mainly carried out by the traditional discontinu-
ous press process or by the continuous centrifugation of
a mixture of mille olives and hot water. In both systems,
the process leads to production of three different phases:
olive oil, solid residue, and OMW (Sayadi et al., 2000).
The average weight composition of OMW is: 83% wa-
ter, 15% organic, 1.8% mineral salts (Nafzaoui, 1991).
The organic fraction is composed by sugars (1–8%), N-

*Corresponding author: Institut de chimie de la Matière Condensée de Bordeaux (ICMCB), 87, Avenue A. Schweitzer, 33608
Pessac, Cedex, France. Phone: 335 40006691; fax: 335 40006633; e-mail: Cansell@enscpb.fr

131
132
compounds (0.5–2.4%), acids (0.5–1.5%), fat (0.02–1%),
as well as phenols and pectins (1–1.5%). Concerning phe-
nols, low-molecular weight compounds (hydroxytyrosol,
tyrosol, catechol, caffeic acid) are usually present in
OMW, together with catechol–melaninic polymers
(Greco et al., 1999).
Many different processes have been proposed to treat
OMW, such as treatments with suitable micro-organisms
(Martini et al., 1996; Sayadi et al., 1996; Garcia et al.,
2000), ultra filtration (Turano et al., 2002), water evap-
oration and incineration of dry residues (Annesini and
Gironi, 1991), and hydrothermal oxidation (Chakchouk
et al., 1994; Vitolo et al., 1999; Rivas et al., 2001). Hy-
drothermal oxidation treatment (HOT) concerns oxida-
tion reactions of organic matter in water under high pres-
sure and high temperature. HOT (P  22.1 MPa, 374°C
 T  700°C) is based on the high reactivity of O2 and
organic compounds because of the complete miscibility
of the different reactive species which promotes high
mass transport rates with no interface transport limita-
tions. When the operating conditions are optimized, the
end products are mainly water, carbon dioxide, nitrogen,
and eventually mineral acids with a reaction time close
to 1 min (Dutournier et al., 2001; Rivas et al., 2001).
Thus, if properly treated, OMW could be safely reincor-
porated into natural media because the organic destruc-
tion should be higher than 99.99%. In this context, this
work presents optimum operating conditions and kinetic
parameters, which allow a total destruction of organic
matters of wastewaters from olive oil industry.
EXPERIMENTAL SET-UP
Batch reactor
Figure 1 shows a schematic diagram of the laboratory
scale reactor developed in ICMCB laboratory. The vol-
Figure 1. Schematic diagram of ICMCB laboratory-scale reactor.
CHKOUNDALI ET AL.
ume reactor was equal to 100 cm3. It was made in In-
conel 625. No agitation system was used. This labora-
tory-scale reactor is able to treat aqueous wastes in batch
reactor in a temperature range between 50 and 600°C, at
pressures up to 30 MPa. The reactor is filled at ambient
temperature with oxidant and waste in defined quantities,
which permitted, after heating of the reactor until the
working temperature, to get the working pressure. The
experiments were carried out at five temperatures: 200,
300, 400, 450, and 500°C. The times needed for heating
up to 200 and 500°C were 15 and 30 min, respectively.
During this heating time, the reaction begun, and the
“real” reaction time could not be accurately defined. That
was the reason why the batch reactions were considered
as preliminary experiments. The stoichiometry defined as
the ratio of the number of oxygen moles to twice the num-
ber of carbon moles was equal to 0, 1, or 2. The reaction
time for the experiments was 1 h. The working pressure
was in the range of 1.7 to 25 MPa. The selected oxidant
was hydrogen peroxide (H2O2 solution at 35% in weight).
Hydrogen peroxide was decomposed in O2 and H2O in a
few minutes a 200°C. Thus, it could be assumed that the
oxidant was oxygen. This allowed the comparison of the
results obtained in batch reactor and in continuous reac-
tor. The reaction analysis was based on the evolution of
the chemical oxygen demand (COD) as function of the
operating parameters.
The COD is the oxygen concentration, expressed in
milligram per litter, which is necessary to transform the
organic matter into CO2 and H2O. At the end of the re-
action, the COD measurements were performed on the
liquid phase according to the French normalized
method for water and wastewater analysis (AFNOR,
1998). The accuracy of the COD measurements was
evaluated to 5%. The COD of the raw OMW was equal
to 170 gL1, and in this study the OMW was diluted
to 60 gL1.
HYDROTHERMAL OXIDATION PROCESS ON OLIVE MILL WASTEWATER
Continuous reactor
Figure 2 shows a schematic diagram of the continuous
flow reactor system. This pilot-plant facility is able to treat
up to 3 kg  h1 aqueous wastes in a temperature range of
200–600°C, pressures up to 30 MPa. It is composed of two
injection lines, reactor, cooler, and a gas/liquid separator
(Mateos et al., 2005). The wastewater was pressurized us-
ing a high-pressure pump (LEWA) and was preheated at
the desired reaction temperature by an electric heater (1.5
kW). The oxidant feed was pure oxygen pressurized by a
Haskel compressor that injected the oxygen at 25 MPa,
without preheating, at the input of the reactor. A mass
flowmeter (Brooks 5850S) allowed the selection and con-
trol of the desired oxygen flow rate in the range of 0–100
g  h1. The reactor was made of an Inconel 625 tube of
1.6 mm internal diameter and 42 m length. It was equipped
with 28 thermocouples (type K) attached to the external
surface. The tube was isolated. The insulator included an
electrical heating material in order to reduce thermal loss
(Mateos et al., 2005). At the output of the reactor, the ef-
fluent was cooled by a countercurrent heat exchanger and
afterward, the system pressure was reduced by using a
backpressure regulator. The product stream was then sep-
arated into liquid and vapor phases. The COD of the liq-
uid samples was determined (AFNOR, 1998). The initial
concentration of organic compounds was 10 g  L1 in
terms of COD. Main units of this equipment were con-
nected to a data acquisition and control unit supported
by Labview software (National Instruments, Nanterre,
France). This system allowed the selection and control of
the main parameters (OMW flow rates, oxygen flow rates,
preheater temperature, and reactor temperature). All ex-
periments were carried out in isothermal conditions with
Figure 2. Schematic diagram of ICMCB continuous pilot-plant facility.
133
a temperature ranging from 200 to 400°C and different
OMW flow rates (1, 1.5, 2, and 2.5 kg  h1), at different
oxygen stoechiometries (0, 0.5, 1, 1.5, and 2) at a constant
pressure of 25 MPa.
RESULTS AND DISCUSSION
Results obtained with the batch pilot plant facility are
reported in Fig. 3. The evolution of COD reduction with
stoichiometry is presented for different temperatures and
a working pressure of 25 MPa. A COD reduction of 95%
was obtained at 400°C. This was the maximum COD re-
duction value that could be obtained with our batch re-
actor because of the fact that it was not a perfect mixed
reactor. This suggested that with a plug flow reactor in
which OMW and oxygen are perfectly mixed, it should
be possible to get a COD reduction higher than 99% for
a temperature lower than 400°C and an oxygen stoi-
chiometry equal to 1. At 500°C, the best COD reduction
was obtained without oxygen. This result indicated that
the hydrolysis of the organic matter was almost complete
in 1 h. The fact that COD reduction seemed lower in the
presence of oxygen was not significant and corresponded
to the accuracy of COD measurement (5% variation).
In summary, the results obtained in batch reactor
clearly demonstrated that the oxidation reaction of OMW
began at 200°C with a stoichiometry in oxygen of 1. Con-
sequently, this temperature was chosen as the initial tem-
perature for the kinetics studies in a continuous reactor.
Moreover, the maximum temperature should not exceed
400°C.
Results obtained with the continuous pilot plant fa-
cility are reported in Table 1. In most cases, for a given
ENVIRON ENG SCI, VOL. 25, NO. 2, 2008
134
temperature, the COD reduction did not vary, although
different resident times were used. In these experi-
ments, the stoichiometry in oxygen was different. This
suggested that two approaches could be envisaged in
order to lower the COD of either the residence time or
the amount of oxygen. However, considering that in
our experiments, three parameters varied, accurate
comparison of all the results was difficult. This is the
interest of treating the experimental results by using the
Runge-Kutta algorithm.
As the continuous flow reactor was in a steady state,
the kinetic expression of the global reaction of hy-
drothermal oxidation is classically represented by the fol-
lowing relation:
rate  k[A]a[O2]b[H2O]c (1)
where [A] is the concentration in organic compounds
(mol  l1); [O2] is the oxygen concentration (mol  l1);
[H2O] is the water concentration (mol  l1);  is the res-
idence time (s); a, b, and c are reaction orders of organic
matter, oxygen, and water, respectively; and k is the re-
action rate coefficient [(mol  l1)1-a-b-cs1] assuming an
Arrhenius law:
 
Ea
k  K0exp   (2)
RT
where K0 is the preexponential factor ((mol  l1)1-a-b-c
s1); Ea is the activation energy (J  mol1); R is the uni-
Figure 3. COD reduction of wastewaters of the olive industry vs. temperature and stoichiometry in oxygen.
CHKOUNDALI ET AL.
versal gas constant (8.314 J  mol1;K1); and T is the
temperature (K).
The chemical path of the reactions of hydrothermal
oxidation is generally very complex. COD concentra-
tion is often used instead of the organic molecule con-
centration. Thus, COD concentration was chosen to de-
scribe the global kinetics of organic compound
transformation into CO2 and H2O. This classical ap-
proach avoided taking into account the formation of in-
termediate organic compounds. As already published,
the reaction order of organic compounds in HOT could
be assumed equal to unity (AFNOR, 1998). Also, in a
reaction medium containing more than 90% of water,
the reaction order of water could be considered equal
to zero. On these bases, Equation (1) was simplified to
the following:
 
Ea
rate  K0exp   [COD][O2]b (3)
RT
The Runge-Kutta algorithm was used to solve this equa-
tion. The main advantages of the Runge-Kutta algorithm
for experimental data treatments, regarding the multilin-
ear regression method, were: (1) the possibility of fitting
together all experimental data obtained at the same tem-
perature, and (2) the suppression of experiments with the
same amount of oxygen at any residence time. When an-
alyzing the experimental data using this method, the oxy-
gen concentration at any time was expressed as a func-
HYDROTHERMAL OXIDATION PROCESS ON OLIVE MILL WASTEWATER 135

Table 1. COD reduction of olive mill wastewater treated by hydrothermal oxidation at 25 MPa.

COD
T QOMW Stoichiometry QO2  reduction
(°C) (kg  h1) in oxygen (mol  h1) (s) (%)

200 1.0 1.32 0.31 270 16

1.0 1.99 0.46 273 42
1.5 0.42 0.23 179 4
1.5 0.85 0.47 180 9
1.5 1.63 0.70 181 37
2.0 0.58 0.31 135 22
2.0 1.17 0.62 136 21
2.0 1.74 0.94 136 7
2.0 2.32 1.25 136 26
250 1.0 0.53 0.15 251 22
1.0 1.59 0.47 253 21
1.0 2.12 0.62 254 31
1.5 0.55 0.23 167 20
1.5 0.88 0.37 168 34
1.5 1.59 0.70 169 38
2.0 0.93 0.5 126 26
2.0 1.16 0.62 126 21
2.0 1.74 0.94 126 25
2.0 2.32 1.25 127 27
300 1.0 0.59 0.14 227 31
1.0 0.94 0.22 228 50
1.0 1.18 0.28 228 38
1.0 1.77 0.42 229 45
1.0 2.36 0.56 230 42
1.5 0.57 0.23 151 32
1.5 0.92 0.37 152 52
350 1.0 3.85 0.85 192 56
1.0 6.42 1.40 193 57
2.0 1.44 0.34 96 57
2.0 2.57 0.56 7 59
2.5 0.61 0.135 77 60
2.5 1.03 0.225 77 53
400 1.0 2.13 0.50 34 38
1.0 3.56 0.84 34 39
2.0 0.66 0.15 25 45
2.0 2.37 0.56 26 32
2.5 1.52 0.33 20 43

QOMW: OMW flow rates; QO2: oxygen flow rates; : residence time; T: temperature.

tion of the initial oxygen concentration and the final COD
concentration. The oxygen in the reaction medium could
be expressed as follows:
[O2]  ([O2]0  ([COD]0  [COD]) (4)
According to Equation (3), the global reaction rate was
deduced:
rate  k[COD]([O2]0  ([COD]0  [COD]))b (5)
where [COD]0 and [O2]0 corresponded to   0; k
was the global kinetic constant regarding COD
disappearance. This differential equation was solved
numerically by a method using the Runge-Kutta
algorithm managed by a Fortran program (Hydrother-
male Oxydation Option). In this algorithm, the inte-
gration interval from 0 to the global residence time
(N) was divided into N subintervals with h  n/N. The

ENVIRON ENG SCI, VOL. 25, NO. 2, 2008

136 CHKOUNDALI ET AL.

Table 2. Kinetic parameters of OMW hydrothermal oxidation treatment.

K0
Ea (kJ/mol) [(mol  l1)0.25s1) R2 Order of O2 Order of COD

48 13 140 60 0.98 0.15 0.05 1

set of equations used in this method was reported here- both k and b values were performed in order to get the
after: best fitting between the calculated [COD]N and experi-
mental ones.
⎧ k1  f (n, DCOn) ⎫ Starting from the calculated values of k at the different
⎪ ⎪ temperatures, the activation energy of the OMW was de-
⎪ ⎪ termined by linear regression in an Arrhenius plot (Fig. 4—
 
h k
⎪ k2  f n   , DCOn  h 1 ⎪ Table 2). The activation energy of OMW hydrothermal ox-
⎪ 2 2 ⎪ idation treatment has been found equal to 48 10 kJ 
⎪ ⎪
⎨ hk2 ⎬ n  0,...N mol1 with an oxygen order equal to 0.15 0.5. This value
⎪ k3  f(n  h, DCOn  h  2 ⎪ of Ea was close to the value obtained in hydrothermal ox-
⎪ ⎪ idation of olive mill wastewater treatment (Ea  32.7 kJ 
⎪ k4  f(n  h, DCOn  hk3) ⎪ mol1) carried out at 25 MPa and in the temperature range
⎪ h ⎪
⎪ DCOn1  DCOn   ⎪ 380–500°C (Rivas et al., 2001). However, in this work (Ri-
⎪ 6 ⎪ vas et al., 2001), the process was described by a first-order
⎩ (k1  2k2  2k3  k4) ⎭ kinetics with no dependence on the oxygen concentration
when it is in excess. In our case, the thermal control of the
where n  n h, k1, k2, k3, k4 are the internal parameters reactor was performed by successive oxygen injections.
defined in the Runge-Kutta algorithm; [COD]n and This thermal control of the process was also demonstrated
[COD]n1 were the calculated COD concentrations at n for the industrial feed back of operational unit (Hydrother-
and n1, respectively, k and b values were fixed starting male Oxydation Option). Consequently, the kinetic equa-
values from literature for the first run of algorithm (Ri- tion used for simulation of a multi-injection oxygen pro-
vas et al., 2001). [COD]N, which corresponded to the cess required taking into account the oxygen concentration.
COD concentration calculated for global residence time, Although the activation energy was not an intrinsic pa-
was obtained for all experiments performed on OMW. rameter, it could be considered as a parameter that predicts
These [COD]N were compared to the final experimental the temperature dependence upon the COD disappearance
COD concentrations ([COD]exp) and an adjustment of rate in the operating conditions of the study. Thus, this ki-

Figure 4. Evolution of Ln (k) as a function of 1/T.

HYDROTHERMAL OXIDATION PROCESS ON OLIVE MILL WASTEWATER
netic parameter could be used for the simulation and scale-
up of industrial units, which could be developed with the
same concept and flow sheet as the ICMCB pilot plant fa-
cility.
CONCLUSION
This study allowed the determination of the kinetic pa-
rameters for the hydrothermal oxidation of olive mill waste-
water. In order to simulate the behaviour of industrial pi-
lot-plant facilities, we used the Runge-Kutta algorithm, and
reliable kinetic data for hydrothermal oxidation of OMW
were obtained. The activation energy of the reaction was
found equal to 48 kJ  mol1 (regarding the COD removal)
with an oxygen order equal to 0.15. On the whole, the hy-
drothermal oxidation treatment of olive mill wastewaters
demonstrated to be an efficient technology. Indeed, at
400°C, for a stoichiometry in oxygen equal to 1.5 and a
residence time of 20 s, the COD was reduced down to 43%.
So, there is no need to increase the temperature up to 500°C
that corresponds to higher operating costs than at 400°C.
This process should be able to reduce quasi totally the or-
ganic contaminant load of this type of effluent by increas-
ing the length of the reactor. In the previous example, an
increase of the reactor length by a factor 10 corresponding
to a residence time of 200 s, should lead to a COD reduc-
tion close to 100%. Moreover, this technology was espe-
cially appropriated because the organic content of this type
of wastewater is too high for biological treatment and too
low for incineration.
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