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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


by agro-food industry in Mediterranean area is the
Corresponding author. Tel.: +39-984-49-2118/2035/2038;
treatment of the olive mill wastewaters. These are the
fax: +39-984-49-2058/2038.
E-mail addresses: stefano.curcio@unical.it (S. Curcio),
main by-product of olive oil production and are char-
vincenza.calabro@unical.it (V. Calabro), gabriele.iorio@unical.it, acterized by high concentrations of several organic
lab.iorio@unical.it (G. Iorio). 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 During ultrafiltration of wastewaters severe foul-
inhibits bacterial activity [4,5]. Besides, they contain ing of the membrane occurs, thus affecting process
also inorganic compounds such as chloride, sulfate performances. Fouling reduces the permeate fluxes
and phosphoric salts of potassium as well as calcium, and determines both efficiency decrease and varia-
iron, magnesium, sodium, copper and traces of other tion of membrane selectivity [1114]; it also makes
elements [6,7]. Finally, they are produced in a limited the process highly expensive owing to repeated plant
period of time (from October to February) and in shut-down for cleaning and washing the membranes.
very large quantities and their physical and chemical Permeate flux profiles show, typically, an initial sharp
characteristics vary according to cultivars, harvesting drop from the value obtained with osmotized water,
time, type of olives and the technology used in the then a smoother but continuous decay until a steady
extraction process (pressing or centrifugation). For all state is reached. That kind of time-dependent profile
the above-mentioned reasons, flexible and efficient is caused by both concentration polarization and foul-
treatment plants are needed; these should assure not ing. While the former is a reversible process caused
only a significant reduction of BOD and COD values, by an increased transport resistance in the boundary
but also the possibility of selectively recovering some layer [15], the latter is an irreversible phenomenon
valuable compounds that could be used in the same comprising the effect of surface fouling, adsorption,
E. Turano et al. / Journal of Membrane Science 209 (2002) 519531 521

gel layer formation, pore blocking or reduction of resistance of the cake formed () [19]:
pore diameters, cake formation and adhesion of par- cF Vp
ticles on the membrane. Membrane fouling depends Rf = (4)
A
on several factors, such as membrane characteris-
tics, feed solution properties, such as molecular size From Eqs. (1), (2) and (4):
of solutes and their interaction with the membrane, 1 dVp TMP
operating conditions (trans-membrane pressure, flow = (5)
A dt (Rm + (cF Vp /A))
rate, temperature) [16,17]. In the literature different
models have been proposed for describing the pro- Integrating Eq. (5) assuming cF constant in time,
cess; models such as the film theory are based on the with the initial condition t = 0, Vp = 0, the volume
knowledge of the transport coefficient and transport of permeate can be expressed as a function of time:
properties of the solution to be ultrafiltered. In the 
Rm + 2 Rm 2 + 2c TMP t
F
case of wastewaters, detailed modeling of ultrafiltra- Vp = (6)
tion behavior, based on the solution of transient mass (cF /A)
balance equations in both the boundary layer built-up Differentiation of Eq. (6) with respect to time and
next to the membrane surface and within the mem- substitution in Eq. (1) lead to the following expression
brane pores, is difficult to be achieved due to the great for the permeate flux as a function of time:
complexity of waste transport and physico-chemical
properties. 1
Jp = 
For this reason in the present paper, olive mill (Rm /TMP)2 + (2cF /TMP)t
wastewater treatment has been analyzed in a phe- 1
nomenological way readapting a simple model, the = (7)
a + bt
cake-filtration theory [18,19], to explain system be-
havior, fit the experimental results and estimate Eq. (7) can be used to fit experimental data of Jp ver-
useful parameters for the evaluation of separation sus time. A model parameters optimization procedure
performances. can be used to obtain the quantities (Rm /TMP) and
The permeate flux, i.e. the volume of permeate ob- (2cF /TMP) that, according to the above equations,
tained in the ultrafiltration per unit time and membrane allow the evaluation of Rm and Rf and, therefore, of the
surface: specific cake resistance, , due to membrane fouling.
1 dVp A cross validation of the results obtained by pa-
Jp = (1) rameter optimization procedure, can be achieved by
A dt
comparing values of Rm to those calculated from ul-
can also be expressed as the ratio between the process trafiltration, performed in the same conditions, of os-
driving force and the transport resistance: motized water. In this way, a completely independent
TMP set of experimental data is used.
Jp = (2) The fitting analysis was performed by a Levenberg
R
Marquardt optimization procedure [20], evaluating a
The transport resistance, according to the resistance- series of numerical information, associated with the
in-series model, is the sum of two contributions: the curve fitting, such as the reliability of the fit, the
membrane hydrodynamic resistance, constant in time coefficient standard errors and the confidence limits
and related to the reciprocal of its permeability, and an for fitted parameter. In particular, for each parameter,
unknown overall, time-dependent resistance account- its value, the standard error, the t-student distribution
ing for the membrane fouling. Eq. (2) becomes: value, the 95% confidence interval are calculated; for
TMP each experimental data a value predicted by the model,
Jp = (3) a percentage residual, a 95% confidence interval are
(Rm + Rf )
evaluated; for the regression a value of r2 , a fitting
Fouling resistance can be expressed as a function of standard error and the value of the function to opti-
feed concentration, permeate volume and the specific mize are obtained.
522 E. Turano et al. / Journal of Membrane Science 209 (2002) 519531

3. Experimental sent an advantage of this technique with respect to


other ones.
Samples from different olive mills, characterized by In order to evaluate the actual improvement de-
different stocking times during 19992000 olive oil termined by wastewater centrifugation, ultrafiltration
production, were used in the experiments in order to experiments have been performed on both raw and pre-
test the process with real wastewaters having different treated wastewaters, analyzing, in the two cases,
physical and chemical characteristics. fluid-dynamic efficiency.
For all the experiments a laboratory centrifuge ALC
3.1. Pre-treatment step 4222 MK II was used at a velocity of 4000 rpm for
10 min.
The greatest problem in ultrafiltering wastewa-
ters is membrane fouling that drastically reduces 3.2. Ultrafiltration unit
the efficiency of permeation and also changes its
selectivity. The experimental analysis of the ultrafiltration
In the present case, a pre-treatment step is neces- process has been carried out by means of an ultrafil-
sary to decrease membrane fouling and to increase UF tration module that has been ad hoc designed and
efficiency, by separating the suspended solids from realized for laboratory experiments. The schematic of
the wastewater. Since centrifuge is already used in laboratory system is shown in Fig. 1. It consists of the
the production cycle of olive oil, it can be economi- following parts:
cally utilized also in waste pre-treatment, and, for this
reason, it was preferred to other techniques such as 1. A centrifugal pump, model MT 5002 supplied by
microfiltration. Besides, the simplicity of the centrifu- Caster pumps, Italy, having a maximum head of
gation process and the possibility of operating only 30 m, a maximum flow rate of 6.8 m3 /h and a nomi-
mechanically (without any chemical change) repre- nal power of 1.1 kW.

Fig. 1. Schematic of laboratory UF system.


E. Turano et al. / Journal of Membrane Science 209 (2002) 519531 523

2. A flow meter, ASA, Italy, able to measure a maxi- A measure of the fluid-dynamic efficiency was ex-
mum water flow rate of 10.5 l/min. pressed as the ratio between permeate flux obtained
3. Two analog manometers, range 06 bars, Spriano, during wastewater ultrafiltration (Jp ) and the one ob-
Italy, used to measure the inlet and the outlet pres- tained ultrafiltering osmotized water (J0 ), in the same
sure and, therefore, the pressure drop in the axial operating conditions. For this reason, each UF exper-
direction. iment on olive mill wastewaters was preceded by ul-
4. A cooling system composed by a copper coil, fed trafiltration of osmotized water in the same conditions
with tap water at a temperature of 15 C, and by of temperature and feed flow rate with the purpose of
a feedback temperature controller, Eliwell, USA, characterizing the membrane performance and defin-
that controls the opening of a two-way electric ing an ideal permeability. After each experiment,
valve, positioned on the coil inlet line. The cooling a combined cycle of alkaline (Henkel, Germany, P3
system is able to control the solution temperature Ultrasil 91) and acid (Henkel, Germany, P3 Ultrasil
with a difference, with respect to set-point value, 75) cleaners was carried out to clean the membrane
of 0.5 C. that is severely fouled by organic compounds and
5. A feed tank having a volume of 5 l, and a vessel minerals contained in the wastewaters.
for permeate collection. Besides the fluid-dynamic experiments, also mem-
brane separation effectiveness was evaluated. The se-
The membrane module utilized to perform ultrafil- lectivity of separation was determined by measuring
tration experiments has been on purpose designed and total organic and inorganic compounds, ashes, fats (by
realized in order to promote localized turbulence phe- Soxhlet extraction), polyphenols (by Folin reagent),
nomena on the wastewater to be filtered. It consists sugars, pectins, tannins and vegetal fragments in all
of two different channels that may be used indepen- the streams of the process. The reduction of pollu-
dently. In the first, the fluid flows along a two-pass tion attained by the proposed treatment plant was
channel and abruptly changes direction of flow ow- measured comparing the COD of the final effluent
ing to one sharp 180-degree turn; in the second one, (permeate) to that of the feed to ultrafiltration module:
the flow occurs in a four-pass channel and three sharp
CODpermeate
180-degree turns are present. Each leg of the channel 1
has a length, L, of 450 mm and a width, w, equal to CODcentrifuge surnatant
8 mm; the channel height, h, is 2 mm.
and to the whole process:
A PolySulphone flat membrane (MPPS U002) sup-
plied by Separem, BiellaItaly, was used to perform CODpermeate
UF experiments. The membrane is characterized by 1 .
CODwastewaters
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- 4. Results
meate flux is equal to 67 l/(h m2 ).
The ultrafiltration unit is fed with the centrifuge su- The complex fluid-dynamic behavior of the fluid
pernatant, except for the experiments used to compare fed to ultrafiltration unit was investigated perform-
the effectiveness of the process with and without the ing a preliminary rheological characterization on
pre-treatment step. centrifuged olive mill wastewater at the same temper-
ature (30 C) chosen to carry out UF experiments. A
3.3. Operating conditions dynamic stress controlled rheometer DSR (mod. 200
Rheometrics, USA) equipped with a plateplate test
Different values of TMP and two feed flow rates, cell geometry was used. The wastewater flow curve
Q, were used in the experiments, while operating (Fig. 2) shows a typical non-newtonian behavior that
temperature was fixed at 30 C. The TMP was cho- can be modeled by the power law equation:
sen in order to have values ranging between 0.5 and
3 bar. = 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 The choice of the pre-treatment step of the wastew-
equation. Deq is the equivalent diameter that takes into aters appeared to be advantageous for ultrafiltration
account the feed channel geometry and is defined as: efficiency. A comparison of the permeate fluxes pro-
file obtained ultrafiltering raw wastewaters and cen-
2hw trifuge supernatant, Fig. 3, shows higher steady state
Deq =
h+w flux for the pre-treated waste and a much smoother de-
cay of efficiency to its final value, so that the working
The experimental analysis has been carried out in
cycle is longer and plant shut-down for washing and
terms of the following expression of apparent viscosity
cleaning are less frequent. Steady state values show
as a function of shear rate:
that centrifuged wastewater permeate flux is about 13
= m n1 times higher than raw wastewater one.
Besides, the recovery of membrane permeation ef-
The rheological parameters m, consistency fac- ficiency, evaluated comparing hydraulic permeability
tor, and n, flow index, were found to be 0.544 Pa sn of new and utilized membrane, was found to be eas-
and 0.196, respectively. On the basis of wastewater ier if ultrafiltration is carried out after centrifugation.
rheological characterization and of the definition of In fact, using the standard cleaning procedure de-
generalized Reynolds number, operating feed flow scribed before, about 83% of the initial permeability
rate values were chosen in order to have turbulent (new membrane) could be recovered when ultrafilter-
flow in the membrane module. Two different flow ing pre-treated wastewaters, while only 37% is re-
regimes corresponding to Re = 7500 and 26,000 were covered when ultrafiltering raw wastewaters (Fig. 4).
therefore used to perform UF experiments. Therefore, if no pre-treatment is performed, membrane
E. Turano et al. / Journal of Membrane Science 209 (2002) 519531 525

Fig. 3. Permeate fluxes measured after UF of raw and centrifuged wastewaters.

permeability recovery is not possible with a standard resistance formed on the membrane surface. Mem-
cleaning technique. If no pre-treatment is performed, brane fouling is attributed to the oil phase that makes
membrane lifetime would be limited to one working easier the agglomeration of macromolecules essen-
cycle only, with obvious implications. Centrifugation, tially composed by suspended solids, ashes, organic
as a pre-treatment step, not only allows higher per- particles, etc. These, in turn, tend to block membrane
meate fluxes but also makes membrane cleaning pro- pores, causing a very steep permeate flux drop when
cedure easier and faster, thus improving plant overall no pre-treatment is used and a smoother one when a
efficiency. great part of suspended solid has been removed.
Fig. 5 shows, at two different values of generalized
4.2. Fouling and results of the cake-filtration model Reynolds number, the fitting of permeate flux exper-
imental data by means of Eq. (7). A good agreement
Fouling and decrease of permeation fluxes still between experimental values and Eq. (7) is observed,
remain a severe problem for the process even in pres- so that the evaluation of parameter (2cF /TMP)
ence of a pre-treatment step; membrane fouling is allows obtaining Rf profile versus time for each ex-
evident not only from flux decay but also from the periment. In order to compare the results, Rf was
decrease of steady state ultrafiltration efficiency at normalized with respect to Rm ; this was necessary to
increasing TMPs, due to the increase of the transport take into account that membrane initial permeability
resistance that overbalances the effect of a higher may change, due to its uncompleted recovery after
driving force. The obtained experimental data were cleaning.
interpreted by the cake-filtration theory and the effect The first results obtained (Fig. 6) confirm the perfor-
of fouling was quantified by calculating the value of mance improvement of the system after pre-treatment.
the fouling resistance and estimating the cake specific 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 values of permeate flux measured, under the same op-
sharper than that obtained ultrafiltering the centrifuge erating conditions, if the four-pass channel is used.
supernatant in the same conditions, (temperature, The calculation of the fouling resistance profile
TMP, Re) and reaches values of one order of magni- takes into account the effect of feed concentration,
tude greater. with the term cF in Eq. (7). The parameter , also
Even with pre-treated wastewaters, membrane foul- related to the fouling phenomenon, was easily esti-
ing becomes more significant at higher pressures, as a mated, being independent on feed concentration. The
result of a higher normalized fouling resistance Rf /Rm feed concentration for UF process has to be defined,
(Fig. 7a). The effect of fouling can be reduced using since the experiments were carried out on real so-
higher feed flow rate that promotes higher turbulence lutions characterized by a complex composition; in
effects in the system. Indeed, the value of Rf /Rm sig- order to take into account the presence of different
nificantly decrease if a greater Reynolds number is types of compounds in the feed, the term cF was
utilized (Fig. 7b). The improvement in ultrafiltration defined accounting for the total amount of non-water
efficiency and the lower fouling resistance obtained compounds present in centrifuge supernatant, includ-
inducing turbulence is also observed when comparing ing the compounds with a molecular weight lower
the results of ultrafiltration test in the two-pass channel than the membrane cut-off, that can contribute to
and those obtained with four-pass channel (Fig. 8); in fouling once the cake starts forming on the membrane
the latter case, the effect of three sharp turns promotes surface. This quantity was measured experimentally
a greater turbulence and gives higher ultrafiltration ef- using a procedure consisting in a double evaporation
ficiency. In terms of fouling resistance an improvement of 50 ml of sample, firstly at room temperature for 1
of about 20% was observed when comparing the final 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 529

Fig. 8. Normalized fouling resistance in two-pass and four-pass modules for centrifuged wastewater.

obtained. The same measure was also taken on the Re = 7500 and 26,000 and this rise is more marked
permeate stream and it allowed to consider the feed at lower feed flow rates, when turbulence is lower
concentration constant during the operation; in fact, and fouling is less significant. At the same TMP the
the ratio between the permeate stream concentration values of in fact are smaller by a factor of about
and cF was around 0.02 for all the experiments, so that 2.5 for a greater Re. Finally, the value of , calcu-
the first one can be considered negligible during oper- lated after UF experiments in the four-pass channel,
ation time and cF constant. With the cF measured, the is slightly lower, thus confirming the importance of
values of in Tables 1 and 2 were calculated at dif- turbulence promotion on permeation efficiency.
ferent operating conditions. As expected, pre-treated
wastewaters give a value of three order of magni- 4.3. Process separation
tude lower with respect to that measured with raw
wastewaters. At constant feed flow rate, specific cake The decay in total solids and ashes are on the
resistance increases with increasing pressure both at average more than 80%, while COD decay is, on the

Table 1 Table 2
Cake specific resistance at different TMP and Re (centrifuged Effect of turbulence on cake specific resistance (TMP = 1 bar,
wastewater ultrafiltered in the two-pass module) Re = 7500)
TMP (bar) (m/kg) (Re = 7500) (m/kg) (Re = 26,000) (m/kg)

1 2.69 1015 1.08 1015 Not pre-treated 2.30 1018


2 3.02 1015 1.14 1015 Centrifuged wastewater (two-pass channel) 2.69 1015
3 3.13 1015 1.17 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- consists of sugars and polyphenols. These compounds
tained in the ultrafiltration step, being still 55% after find different applications in pharmaceutical field and
centrifugation process. However, although COD re- in food preserves, due to their antioxidant properties,
duction is relevant, permeate, that is the final effluent so they can be economically recovered from the per-
from the process, has still a too high value (around meate starting from a low volume and without com-
5000 mg O2 /l) for European legislation, and needs, plex interferences, therefore, with an higher selectivity
therefore, a further purification step. Nevertheless, of extraction. The decay of phenols content in the re-
these preliminary results are undoubtedly good. In tentate stream, according to the decay in its phytotoxi-
fact, the total rejection of both fatty phase originally city, allows their use as a fertilizer, after an enzymatic
present in the wastewaters, meaning that the permeate treatment for the production of humic substances.
is completely oil-free, and of ethanol-settling or-
ganic substances (pectins, tannins, vegetal pigments)
is attained. Ultrafiltration permeate contains only References
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