Journal of Membrane Science 209 (2002) 519531

An integrated centrifugationultrafiltration system in

the treatment of olive mill wastewater
Edoardo Turano, Stefano Curcio, Maria G. De Paola,
Vincenza Calabr, Gabriele Iorio
Department of Chemical Engineering and Materials, University of Calabria, I-87030 Arcavacata di Rende, CS, Italy
Received 7 March 2002; received in revised form 2 August 2002; accepted 5 August 2002

Abstract
A novel approach in the treatment of olive mill wastewater is presented. Aim of the proposed process is both the reduction of
pollution caused by the wastes and the selective separation of some useful products that are present (fats, sugars, polyphenols,
etc.). The treatment consists in a preliminary centrifugation step, in which the suspended solids are removed, and in an actual
selective separation phase, carried out by ultrafiltration (UF), of the centrifuge supernatant. The combination of centrifugation
and ultrafiltration allows a COD reduction of about 90%. Moreover a complete separation of fats, completely rejected by
the membrane, from salts, sugars and polyphenols, contained in the permeate, is attained. The present experimental study
is directed to investigate the fluid-dynamic aspects related to the ultrafiltration of real olive mill wastewaters. It is based on
a preliminary rheological characterization of the waste and on the evaluation of permeation efficiency that was analyzed
as a function of several parameters such as the importance of pre-treating wastewater, the effects of localized turbulence,
promoted by UF module geometry, and of the main operating variables (trans-membrane pressure and feed flow rate). UF
experimental results, obtained in a lab-scale flat-sheet membrane module, are interpreted using both the cake-filtration and
the resistance-in-series models, thus allowing the evaluation of Rf parameter that represents the effect of fouling on separation
efficiency. An estimation of specific cake resistance, , is, therefore, performed on the basis of the feed concentration of
total non-water compounds present in the waste showing that pre-treated wastewaters give a lower with respect to raw
wastewaters by a factor of about 1000. Moreover, it is found that at the same TMP, lower values of correspond to a greater
Re and that higher local turbulence implies lower specific cake resistances. The results obtained in the present paper could
give useful indications for a preliminary characterization of pilot and industrial modules utilized for olive mill wastewaters
treatment aimed at a significant COD reduction and a selective separation of valuable compounds that are present in the waste.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Ultrafiltration; Olive mill wastewater; Pre-treatment; Turbulence promotion; Centrifugation

1. Introduction

One of the major environmental problem caused

Corresponding author. Tel.: +39-984-49-2118/2035/2038;
fax: +39-984-49-2058/2038.
E-mail addresses: stefano.curcio@unical.it (S. Curcio),
vincenza.calabro@unical.it (V. Calabro), gabriele.iorio@unical.it,
lab.iorio@unical.it (G. Iorio).
by agro-food industry in Mediterranean area is the
treatment of the olive mill wastewaters. These are the
main by-product of olive oil production and are char-
acterized by high concentrations of several organic
compounds, such as organic acids, sugars, tannins,

0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 0 2 ) 0 0 3 6 9 - 1
520 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531

production cycle or as raw material for other processes

Nomenclature [810].
A membrane area (m2 ) Literature data concerning selective separation, per-
cF feed concentration (kg/m3 ) formed by membranes, of valuable compounds con-
Deq equivalent diameter (m) tained in olive mill wastewaters are, still, very scarce.
h height of membrane module channel (m) Moreover, no rheological characterization of olive mill
J0 osmotized water permeate flux (m/s) effluents has been published on the most widespread
Jp permeate flux (m/s) journals dealing with rheology. In the present paper
L channel length (m) a scheme in which real olive mill wastewaters were
m consistency factor (Pa sn ) pre-treated by centrifugation and then ultrafiltered in
n flow index a flat-sheet membrane module is proposed. The aim
Q feed flow rate (m3 /h) of the experiments was to obtain a treated effluent and
r2 correlation coefficient a selective separation of the main components thus al-
R overall resistance (m1 ) lowing the possibility of recovering fats and polyphe-
Re generalized Reynolds number nols both useful for different industrial processes. For
Rf fouling resistance (m1 ) this reason process performances were evaluated tak-
Rm membrane resistance (m1 ) ing into account both the reduction of polluting load
TMP trans-membrane pressure (Pa) and the efficiency of separation system. The complex
Vp permeate volume (m3 ) rheological behavior of olive mill wastewaters has
w width of membrane module channel (m) been preliminary examined; then the individuation of a
simple and economic pre-treatment technique has been
Greek letters performed. Finally, fluid-dynamic effects on UF per-
specific resistance (m/kg) meate fluxes have been investigated in order to analyze
shear rate (s1 ) the system behavior under different operating condi-
apparent viscosity (Pa s) tions and in order to characterize fouling phenomena,
estimating the specific resistance of the cake deposited
density (kg/m3 )
on the membrane on the basis of cake-filtration
shear stress (Pa)
theory.

pectins, polyphenolic substances, that make them 2. Theory

difficult to treat [13]. The presence of these com-
pounds makes olive mill wastewaters phytotoxic and
inhibits bacterial activity [4,5]. Besides, they contain
also inorganic compounds such as chloride, sulfate
and phosphoric salts of potassium as well as calcium,
iron, magnesium, sodium, copper and traces of other
elements [6,7]. Finally, they are produced in a limited
period of time (from October to February) and in
very large quantities and their physical and chemical
characteristics vary according to cultivars, harvesting
time, type of olives and the technology used in the
extraction process (pressing or centrifugation). For all
the above-mentioned reasons, flexible and efficient
treatment plants are needed; these should assure not
only a significant reduction of BOD and COD values,
but also the possibility of selectively recovering some
valuable compounds that could be used in the same
During ultrafiltration of wastewaters severe foul-
ing of the membrane occurs, thus affecting process
performances. Fouling reduces the permeate fluxes
and determines both efficiency decrease and varia-
tion of membrane selectivity [1114]; it also makes
the process highly expensive owing to repeated plant
shut-down for cleaning and washing the membranes.
Permeate flux profiles show, typically, an initial sharp
drop from the value obtained with osmotized water,
then a smoother but continuous decay until a steady
state is reached. That kind of time-dependent profile
is caused by both concentration polarization and foul-
ing. While the former is a reversible process caused
by an increased transport resistance in the boundary
layer [15], the latter is an irreversible phenomenon
comprising the effect of surface fouling, adsorption,
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
gel layer formation, pore blocking or reduction of
pore diameters, cake formation and adhesion of par-
ticles on the membrane. Membrane fouling depends
on several factors, such as membrane characteris-
tics, feed solution properties, such as molecular size
of solutes and their interaction with the membrane,
operating conditions (trans-membrane pressure, flow
rate, temperature) [16,17]. In the literature different
models have been proposed for describing the pro-
cess; models such as the film theory are based on the
knowledge of the transport coefficient and transport
properties of the solution to be ultrafiltered. In the
case of wastewaters, detailed modeling of ultrafiltra-
tion behavior, based on the solution of transient mass
balance equations in both the boundary layer built-up
next to the membrane surface and within the mem-
brane pores, is difficult to be achieved due to the great
complexity of waste transport and physico-chemical
properties.
For this reason in the present paper, olive mill
wastewater treatment has been analyzed in a phe-
nomenological way readapting a simple model, the
cake-filtration theory [18,19], to explain system be-
havior, fit the experimental results and estimate
useful parameters for the evaluation of separation
performances.
The permeate flux, i.e. the volume of permeate ob-
tained in the ultrafiltration per unit time and membrane
surface:
1 dVp
Jp = (1)
A dt
can also be expressed as the ratio between the process
driving force and the transport resistance:
TMP
Jp = (2)
R
The transport resistance, according to the resistance-
in-series model, is the sum of two contributions: the
membrane hydrodynamic resistance, constant in time
and related to the reciprocal of its permeability, and an
unknown overall, time-dependent resistance account-
ing for the membrane fouling. Eq. (2) becomes:
TMP
Jp = (3)
(Rm + Rf )
Fouling resistance can be expressed as a function of
feed concentration, permeate volume and the specific
521
resistance of the cake formed () [19]:
cF Vp
Rf = (4)
A
From Eqs. (1), (2) and (4):
1 dVp TMP
= (5)
A dt (Rm + (cF Vp /A))
Integrating Eq. (5) assuming cF constant in time,
with the initial condition t = 0, Vp = 0, the volume
of permeate can be expressed as a function of time:


Rm + 2 Rm 2 + 2c TMP t
F
Vp = (6)
(cF /A)
Differentiation of Eq. (6) with respect to time and
substitution in Eq. (1) lead to the following expression
for the permeate flux as a function of time:
1
Jp =

(Rm /TMP)2 + (2cF /TMP)t
1
= (7)
a + bt
Eq. (7) can be used to fit experimental data of Jp ver-
sus time. A model parameters optimization procedure
can be used to obtain the quantities (Rm /TMP) and
(2cF /TMP) that, according to the above equations,
allow the evaluation of Rm and Rf and, therefore, of the
specific cake resistance, , due to membrane fouling.
A cross validation of the results obtained by pa-
rameter optimization procedure, can be achieved by
comparing values of Rm to those calculated from ul-
trafiltration, performed in the same conditions, of os-
motized water. In this way, a completely independent
set of experimental data is used.
The fitting analysis was performed by a Levenberg
Marquardt optimization procedure [20], evaluating a
series of numerical information, associated with the
curve fitting, such as the reliability of the fit, the
coefficient standard errors and the confidence limits
for fitted parameter. In particular, for each parameter,
its value, the standard error, the t-student distribution
value, the 95% confidence interval are calculated; for
each experimental data a value predicted by the model,
a percentage residual, a 95% confidence interval are
evaluated; for the regression a value of r2 , a fitting
standard error and the value of the function to opti-
mize are obtained.
522 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
3. Experimental
Samples from different olive mills, characterized by
different stocking times during 19992000 olive oil
production, were used in the experiments in order to
test the process with real wastewaters having different
physical and chemical characteristics.
3.1. Pre-treatment step
The greatest problem in ultrafiltering wastewa-
ters is membrane fouling that drastically reduces
the efficiency of permeation and also changes its
selectivity.
In the present case, a pre-treatment step is neces-
sary to decrease membrane fouling and to increase UF
efficiency, by separating the suspended solids from
the wastewater. Since centrifuge is already used in
the production cycle of olive oil, it can be economi-
cally utilized also in waste pre-treatment, and, for this
reason, it was preferred to other techniques such as
microfiltration. Besides, the simplicity of the centrifu-
gation process and the possibility of operating only
mechanically (without any chemical change) repre-
Fig. 1. Schematic of laboratory UF system.
sent an advantage of this technique with respect to
other ones.
In order to evaluate the actual improvement de-
termined by wastewater centrifugation, ultrafiltration
experiments have been performed on both raw and pre-
treated wastewaters, analyzing, in the two cases,
fluid-dynamic efficiency.
For all the experiments a laboratory centrifuge ALC
4222 MK II was used at a velocity of 4000 rpm for
10 min.
3.2. Ultrafiltration unit
The experimental analysis of the ultrafiltration
process has been carried out by means of an ultrafil-
tration module that has been ad hoc designed and
realized for laboratory experiments. The schematic of
laboratory system is shown in Fig. 1. It consists of the
following parts:
1. A centrifugal pump, model MT 5002 supplied by
Caster pumps, Italy, having a maximum head of
30 m, a maximum flow rate of 6.8 m3 /h and a nomi-
nal power of 1.1 kW.
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
2. A flow meter, ASA, Italy, able to measure a maxi-
mum water flow rate of 10.5 l/min.
3. Two analog manometers, range 06 bars, Spriano,
Italy, used to measure the inlet and the outlet pres-
sure and, therefore, the pressure drop in the axial
direction.
4. A cooling system composed by a copper coil, fed
with tap water at a temperature of 15 C, and by
a feedback temperature controller, Eliwell, USA,
that controls the opening of a two-way electric
valve, positioned on the coil inlet line. The cooling
system is able to control the solution temperature
with a difference, with respect to set-point value,
of 0.5 C.
5. A feed tank having a volume of 5 l, and a vessel
for permeate collection.
The membrane module utilized to perform ultrafil-
tration experiments has been on purpose designed and
realized in order to promote localized turbulence phe-
nomena on the wastewater to be filtered. It consists
of two different channels that may be used indepen-
dently. In the first, the fluid flows along a two-pass
channel and abruptly changes direction of flow ow-
ing to one sharp 180-degree turn; in the second one,
the flow occurs in a four-pass channel and three sharp
180-degree turns are present. Each leg of the channel
has a length, L, of 450 mm and a width, w, equal to
8 mm; the channel height, h, is 2 mm.
A PolySulphone flat membrane (MPPS U002) sup-
plied by Separem, BiellaItaly, was used to perform
UF experiments. The membrane is characterized by
a nominal molecular weight cut-off of 17 kDa and an
89.6% rejection to dextran 20,000. With water, at a
temperature of 25 C and a pressure of 1.5 bar, the per-
meate flux is equal to 67 l/(h m2 ).
The ultrafiltration unit is fed with the centrifuge su-
pernatant, except for the experiments used to compare
the effectiveness of the process with and without the
pre-treatment step.
3.3. Operating conditions
Different values of TMP and two feed flow rates,
Q, were used in the experiments, while operating
temperature was fixed at 30 C. The TMP was cho-
sen in order to have values ranging between 0.5 and
3 bar.
523
A measure of the fluid-dynamic efficiency was ex-
pressed as the ratio between permeate flux obtained
during wastewater ultrafiltration (Jp ) and the one ob-
tained ultrafiltering osmotized water (J0 ), in the same
operating conditions. For this reason, each UF exper-
iment on olive mill wastewaters was preceded by ul-
trafiltration of osmotized water in the same conditions
of temperature and feed flow rate with the purpose of
characterizing the membrane performance and defin-
ing an ideal permeability. After each experiment,
a combined cycle of alkaline (Henkel, Germany, P3
Ultrasil 91) and acid (Henkel, Germany, P3 Ultrasil
75) cleaners was carried out to clean the membrane
that is severely fouled by organic compounds and
minerals contained in the wastewaters.
Besides the fluid-dynamic experiments, also mem-
brane separation effectiveness was evaluated. The se-
lectivity of separation was determined by measuring
total organic and inorganic compounds, ashes, fats (by
Soxhlet extraction), polyphenols (by Folin reagent),
sugars, pectins, tannins and vegetal fragments in all
the streams of the process. The reduction of pollu-
tion attained by the proposed treatment plant was
measured comparing the COD of the final effluent
(permeate) to that of the feed to ultrafiltration module:
CODpermeate
1
CODcentrifuge surnatant
and to the whole process:
CODpermeate
1 .
CODwastewaters
4. Results
The complex fluid-dynamic behavior of the fluid
fed to ultrafiltration unit was investigated perform-
ing a preliminary rheological characterization on
centrifuged olive mill wastewater at the same temper-
ature (30 C) chosen to carry out UF experiments. A
dynamic stress controlled rheometer DSR (mod. 200
Rheometrics, USA) equipped with a plateplate test
cell geometry was used. The wastewater flow curve
(Fig. 2) shows a typical non-newtonian behavior that
can be modeled by the power law equation:
= m n1
524 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
Fig. 2. Flow curve of centrifuged olive mill wastewater.
Generalized Reynolds number Re = (Deq n v
2n / 4.1. Effect of pre-treatment
n3
m2 (n + (1/n))) is to be used when the fluid has a
complex rheological behavior modeled by power law
equation. Deq is the equivalent diameter that takes into
account the feed channel geometry and is defined as:
2hw
Deq =
h+w
The experimental analysis has been carried out in
terms of the following expression of apparent viscosity
as a function of shear rate:
= m n1
The rheological parameters m, consistency fac-
tor, and n, flow index, were found to be 0.544 Pa sn
and 0.196, respectively. On the basis of wastewater
rheological characterization and of the definition of
generalized Reynolds number, operating feed flow
rate values were chosen in order to have turbulent
flow in the membrane module. Two different flow
regimes corresponding to Re = 7500 and 26,000 were
therefore used to perform UF experiments.
The choice of the pre-treatment step of the wastew-
aters appeared to be advantageous for ultrafiltration
efficiency. A comparison of the permeate fluxes pro-
file obtained ultrafiltering raw wastewaters and cen-
trifuge supernatant, Fig. 3, shows higher steady state
flux for the pre-treated waste and a much smoother de-
cay of efficiency to its final value, so that the working
cycle is longer and plant shut-down for washing and
cleaning are less frequent. Steady state values show
that centrifuged wastewater permeate flux is about 13
times higher than raw wastewater one.
Besides, the recovery of membrane permeation ef-
ficiency, evaluated comparing hydraulic permeability
of new and utilized membrane, was found to be eas-
ier if ultrafiltration is carried out after centrifugation.
In fact, using the standard cleaning procedure de-
scribed before, about 83% of the initial permeability
(new membrane) could be recovered when ultrafilter-
ing pre-treated wastewaters, while only 37% is re-
covered when ultrafiltering raw wastewaters (Fig. 4).
Therefore, if no pre-treatment is performed, membrane
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
Fig. 3. Permeate fluxes measured after UF of raw and centrifuged wastewaters.
permeability recovery is not possible with a standard
cleaning technique. If no pre-treatment is performed,
membrane lifetime would be limited to one working
cycle only, with obvious implications. Centrifugation,
as a pre-treatment step, not only allows higher per-
meate fluxes but also makes membrane cleaning pro-
cedure easier and faster, thus improving plant overall
efficiency.
4.2. Fouling and results of the cake-filtration model
Fouling and decrease of permeation fluxes still
remain a severe problem for the process even in pres-
ence of a pre-treatment step; membrane fouling is
evident not only from flux decay but also from the
decrease of steady state ultrafiltration efficiency at
increasing TMPs, due to the increase of the transport
resistance that overbalances the effect of a higher
driving force. The obtained experimental data were
interpreted by the cake-filtration theory and the effect
of fouling was quantified by calculating the value of
the fouling resistance and estimating the cake specific
525
resistance formed on the membrane surface. Mem-
brane fouling is attributed to the oil phase that makes
easier the agglomeration of macromolecules essen-
tially composed by suspended solids, ashes, organic
particles, etc. These, in turn, tend to block membrane
pores, causing a very steep permeate flux drop when
no pre-treatment is used and a smoother one when a
great part of suspended solid has been removed.
Fig. 5 shows, at two different values of generalized
Reynolds number, the fitting of permeate flux exper-
imental data by means of Eq. (7). A good agreement
between experimental values and Eq. (7) is observed,
so that the evaluation of parameter (2cF /TMP)
allows obtaining Rf profile versus time for each ex-
periment. In order to compare the results, Rf was
normalized with respect to Rm ; this was necessary to
take into account that membrane initial permeability
may change, due to its uncompleted recovery after
cleaning.
The first results obtained (Fig. 6) confirm the perfor-
mance improvement of the system after pre-treatment.
In fact, fouling resistance profile, normalized with
526 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
Fig. 4. Membrane permeability recovery (raw and centrifuged wastewater).
respect to the membrane hydrodynamic resistance, is
sharper than that obtained ultrafiltering the centrifuge
supernatant in the same conditions, (temperature,
TMP, Re) and reaches values of one order of magni-
tude greater.
Even with pre-treated wastewaters, membrane foul-
ing becomes more significant at higher pressures, as a
result of a higher normalized fouling resistance Rf /Rm
(Fig. 7a). The effect of fouling can be reduced using
higher feed flow rate that promotes higher turbulence
effects in the system. Indeed, the value of Rf /Rm sig-
nificantly decrease if a greater Reynolds number is
utilized (Fig. 7b). The improvement in ultrafiltration
efficiency and the lower fouling resistance obtained
inducing turbulence is also observed when comparing
the results of ultrafiltration test in the two-pass channel
and those obtained with four-pass channel (Fig. 8); in
the latter case, the effect of three sharp turns promotes
a greater turbulence and gives higher ultrafiltration ef-
ficiency. In terms of fouling resistance an improvement
of about 20% was observed when comparing the final
values of permeate flux measured, under the same op-
erating conditions, if the four-pass channel is used.
The calculation of the fouling resistance profile
takes into account the effect of feed concentration,
with the term cF in Eq. (7). The parameter , also
related to the fouling phenomenon, was easily esti-
mated, being independent on feed concentration. The
feed concentration for UF process has to be defined,
since the experiments were carried out on real so-
lutions characterized by a complex composition; in
order to take into account the presence of different
types of compounds in the feed, the term cF was
defined accounting for the total amount of non-water
compounds present in centrifuge supernatant, includ-
ing the compounds with a molecular weight lower
than the membrane cut-off, that can contribute to
fouling once the cake starts forming on the membrane
surface. This quantity was measured experimentally
using a procedure consisting in a double evaporation
of 50 ml of sample, firstly at room temperature for 1
day and then at 100 C until a constant weight was
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531 527

Fig. 5. Fitting of centrifuged wastewater permeate flux (Re = 7500 and Re = 26,000).

Fig. 6. Normalized fouling resistance for centrifuged and raw wastewaters.

528 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531

Fig. 7. (a) Normalized fouling resistance at different TMP values for centrifuged wastewater (Re = 7500); (b) normalized fouling resistance
at different TMP values for centrifuged wastewater (Re = 26,000).
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
Fig. 8. Normalized fouling resistance in two-pass and four-pass modules for centrifuged wastewater.
obtained. The same measure was also taken on the
permeate stream and it allowed to consider the feed
concentration constant during the operation; in fact,
the ratio between the permeate stream concentration
and cF was around 0.02 for all the experiments, so that
the first one can be considered negligible during oper-
ation time and cF constant. With the cF measured, the
values of in Tables 1 and 2 were calculated at dif-
ferent operating conditions. As expected, pre-treated
wastewaters give a value of three order of magni-
tude lower with respect to that measured with raw
wastewaters. At constant feed flow rate, specific cake
resistance increases with increasing pressure both at
Table 1
Cake specific resistance at different TMP and Re (centrifuged
wastewater ultrafiltered in the two-pass module)
TMP (bar) (m/kg) (Re = 7500) (m/kg) (Re = 26,000)
1 2.69 1015 1.08 1015
2 3.02 1015 1.14 1015
3 3.13 1015 1.17 1015
529
Re = 7500 and 26,000 and this rise is more marked
at lower feed flow rates, when turbulence is lower
and fouling is less significant. At the same TMP the
values of in fact are smaller by a factor of about
2.5 for a greater Re. Finally, the value of , calcu-
lated after UF experiments in the four-pass channel,
is slightly lower, thus confirming the importance of
turbulence promotion on permeation efficiency.
4.3. Process separation
The decay in total solids and ashes are on the
average more than 80%, while COD decay is, on the
Table 2
Effect of turbulence on cake specific resistance (TMP = 1 bar,
Re = 7500)
(m/kg)
Not pre-treated 2.30 1018
Centrifuged wastewater (two-pass channel) 2.69 1015
Centrifuged wastewater (four-pass channel) 2.23 1015
530 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
average, more than 90%, and it is quite totally ob-
tained in the ultrafiltration step, being still 55% after
centrifugation process. However, although COD re-
duction is relevant, permeate, that is the final effluent
from the process, has still a too high value (around
5000 mg O2 /l) for European legislation, and needs,
therefore, a further purification step. Nevertheless,
these preliminary results are undoubtedly good. In
fact, the total rejection of both fatty phase originally
present in the wastewaters, meaning that the permeate
is completely oil-free, and of ethanol-settling or-
ganic substances (pectins, tannins, vegetal pigments)
is attained. Ultrafiltration permeate contains only
polyphenols, ranging from 0.2 to 0.3 g/l depending
on the feed concentration, sugars from 2 to 12 g/l and
mineral salts ranging from 3 to 8 g/l. The obtained
polyphenols may be either converted by means of
enzymes (tyrosinase, polyphenoloxidase, peroxidase,
etc.) immobilized in a membrane bioreactor [2123],
thus reducing permeate polluting load, or recovered
to be used for their high antioxidant and radical
scavenging properties [24,25].
5. Conclusions
The results obtained with a plant in which raw olive
mill wastewaters were treated combining a centrifuga-
tion step and the ultrafiltration in a membrane module
show a significant reduction of waste pollution of
about 80% for ashes and suspended solids and 90%
for COD. In order to start understanding the complex
transport phenomena involved in the process, an ex-
perimental analysis has been performed ultrafiltering
centrifuge supernatant and changing the most signifi-
cant fluid-dynamic parameters involved. The obtained
results were analyzed according to the cake-filtration
theory to calculate fouling additional resistance and to
estimate cake specific resistance. Owing to its simplic-
ity, this theory allows interpreting experimental data
of olive mill wastewaters UF better than other models,
such as film or gel theory, that are not suitable when
feed is greatly complex and mass transport coefficients
are difficult to evaluate. Oil phase concentration in the
retentate from ultrafiltration suggests an economic re-
covery, starting from a lower volume, with reduction
in cost for extraction plant and for selective solvents.
In the permeate stream, the organic fraction mainly
consists of sugars and polyphenols. These compounds
find different applications in pharmaceutical field and
in food preserves, due to their antioxidant properties,
so they can be economically recovered from the per-
meate starting from a low volume and without com-
plex interferences, therefore, with an higher selectivity
of extraction. The decay of phenols content in the re-
tentate stream, according to the decay in its phytotoxi-
city, allows their use as a fertilizer, after an enzymatic
treatment for the production of humic substances.
References
[1] T.H. Ergder, E. Gven, G.N. Demirer, Anaerobic treatment
of olive mill wastes in batch reactors, Process Biochem. 36
(2000) 243248.
[2] A. Rozzi, F. Malpei, Treatment and disposal of olive mill
effluents, Int. Biodeterior. Biodegrad. 38 (3/4) (1996) 135
144.
[3] H.N. Gavala, I.V. Skiadas, N.A. Bozinis, G. Lyberatos,
Anaerobic codigestion of agricultural industries wastewaters,
Water Sci. Technol. 34 (11) (1996) 6775.
[4] A. Ramos-Cormenzana, B. Jurez-Jimnez, M.P. Garcia-
Pareja, Antimicrobial activity of olive mill waste-waters
(alpechin) and biotransformed olive oil mill wastewater, Int.
Biodeterior. Biodegrad. 38 (3/4) (1996) 283290.
[5] L. Saez, J. Perez, J. Martinez, Low molecular weight phenolic
attenuation during simulated treatment of wastewaters from
olive oil mills in evaporation ponds, Water Res. 26 (9) (1992)
12611266.
[6] A. Rozzi, N. Limoni, S. Menegatti, G. Boari, L. Liberti, R.
Passino, Influence of Na and Ca alkalinity on UASB treatment
of olive mill effluents. Part 1. Preliminary results, Process
Chem. 23 (1988) 8690.
[7] L. Di Giovacchino, Caratteristiche delle acque di vegetazione
delle olive. Nota 1, La Rivista Italiana delle Sostanze Grasse
62 (1985) 411.
[8] A. Ramos-Cormenzana, M. Monteoliva-Sanchez, M.J. Lopez,
Bioremediation of Alpechin, Int. Biodeterior. Biodegrad.
35 (13) (1995) 249268.
[9] I. Chatjipavlidis, M. Antonakou, D. Demou, F. Flouri, C.
Balis, Bio-fertilization of olive oil mills liquid wastes. The
pilot plant in Messinia, Greece, Int. Biodeterior. Biodegrad.
38 (3/4) (1996) 183187.
[10] M.J. Lpez, J. Moreno, A. Ramos-Cormenzana, Xanthomonas
campestris strain selection for xanthan production from olive
mill wastewaters, Water Res. 35 (7) (2001) 18281830.
[11] G. Belfort, R.H. Davis, A.L. Zydney, The behaviour of
suspensions and macromolecular solutions in crossflow
microfiltration, J. Membr. Sci. 96 (1/2) (1994) 158.
[12] M. Cheryan, Ultrafiltration Handbook, Technomic Publishing
Company, Lancaster, PA, 1986.
[13] L.J. Zeman, A.L. Zydney, Microfiltration and Ultrafiltration,
Marcel Dekker Incorporated, New York, NY, 1996.
 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531
[14] E.S. Tarleton, R.J. Wakeman, Understanding flux decline in
crossflow microfiltration. Part 1. Effects of particle and pore
size, Chem. Eng. Res. Des. 71 (1993) 399.
[15] M.C. Porter, Concentration polarization with membrane
ultrafiltration, Indus. Eng. Chem. Prod. Res. Dev. 11 (3)
(1972) 234.
[16] J. Hermia, Constant pressure blocking filtration laws: appli-
cation to power law non-newtonian fluids, Trans. Inst. Chem.
Eng. 60 (1982) 183.
[17] R.H. Davis, Modelling of fouling of cross-flow microfiltration
membranes, Separat. Purific. Methods 21 (2) (1992) 75.
[18] W.F. Blatt, A. Dravid, A.S. Michaels, L. Nelsen, Solution
polarization and cake formation in membrane ultafiltration:
causes, consequences, and control techniques, in: J.E. Flinn
(Ed.), Membr. Sci. Technol. Plenum Press, New York, NY,
1970.
[19] J.M. Benito, S. Ebel, B. Gutierrez, C. Pazos, J. Coca,
Ultrafiltration of a waste emulsified cutting oil using organic
membranes, Water Air Soil Pollut. 128 (1/2) (2001) 181.
[20] J.J. Mor, The levenbergmarquardt algorithm: implement-
ation and theory, in: G.A. Watson (Ed.), Lecture Notes in
531
Mathematics, vol. 630, Springer, Berlin, 1978, pp. 105
116.
[21] W. Edwards, R. Bownes, W.D. Leukes, E.P. Jacobs, R.
Sanderson, P.D. Rose, S.G. Burton, A capillary membrane
bioreactor using immobilized polyphenol oxidase for the
removal of phenols from industrial effluents, Enzyme Microb.
Technol. 24 (3/4) (1999) 209217.
[22] N. Durn, E. Esposito, Potential applications of oxidative
enzymes and phenoloxidase-like compounds in wastewater
and soil treatment: a review, Appl. Catal. B: Environ. 28 (2)
(2000) 8399.
[23] V. Calabro, S. Curcio, M.G. De Paola, G. Iorio, Membrane
bioreactor for the enzymatic oxidation of polyphenols,
Proceedings of ICOM 2002 Conference, Toulouse, 712 July
2002.
[24] C.A. Rice-Evans, N.J. Miller, G. Paganga, Structure-anti-
oxidant activity relationships of flavonoids and phenolic
acids, Free Rad. Biol. Med. 20 (7) (1996) 933956.
[25] I.E. Dreosti, Antioxidant polyphenols in tea, cocoa, and
wine, Nutrition 16 (7/8) (2000) 692694.