Wat. Res. Vol. 22, No. 12, pp, 1491-1494, 1988 01M3-1354/88 $3.00+0.

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Printed in Great Britain. All rights reserved Copyright 1988 Pergamon Press plc

OLIVE MILLS WASTEWATER TREATMENT BY

COMBINED MEMBRANE PROCESSES
PIETRO CANEPA,1 NAZZARENO MARIGNETTI,2 UMBERTO ROGNONI3 and SEBA CALGARI4
~Istituto di Chimica Industriale, Universita' di Genova; 2Dipartimento di Chimica, Universita' di Ferrara;
3SNIA FIBRE SpA, Centro Sperimentale, Cesano Maderno (Mi) and 4IREOS SpA, Genova, Italy

(First received November 1987' accepted in revised form May 1988)

Abstract--The purpose of this work was to verify the combined application of membranes and adsorption
processes to the treatment of vegetation waters coming from olive oil factories. The described pilot plant
worked for about 6 months using polysulfone ultrafiltration membranes, absorbing polymers and
polypiperazine amide reverse osmosis membranes. The process was optimized so that from wastewater
entering with a COD content of about 90,000 ppm it was possible to obtain a COD reduction of about
99% with the recovery of polyphenols to use in alimentary industries and of a "concentrated paste" for
oil extraction, phurphurale production or combustion. Also evaluated was the economical feasibility of
industrial application calculating that the total cost of the treatment was close to 3 c per liter.

Key words--membrane, vegetation waters, ultrafiltration, reverse osmosis depuration

INTRODUCTION promising possibilities, as reported by many authors

As it is well known the olive oil extraction is one of
the ancient agricultural industry all over the
Mediterranean area and up to day it is of funda-
mental economic importance for many countries. The
olive mills wastewater, commonly called vegetation
water, is formed during industrial extraction of oil
from olives and its physico-chemical characteristics
vary with place, age of growth, season, year, etc.
The Italian olives production is evaluated in the
range of 2,500,000-3,000,000 tons per years leading
to a production of about 2,000,000 tons of vegetation
water causing serious environmental problems. It is
well known that 4 0 - 8 0 k g of vegetation water is
formed from 100 kg of olives using batch or con-
tinuous extraction plant respectively, with an average
composition as reported in Table 1,
The organic content is mainly formed by poly-
phenols, carbohydrates, polysaccharides, sugars,
nitrocompounds polyalchols and oil, substances
worthy of recovery (Di Giovacchino, 1985); Ielmini et
al., 1986; Balice et al., 1982).
F r o m the point of view of pollution control the
distribution of vegetation of water on agricultural
soil or in the surface waters is no more acceptable
because of a very high secondary pollution effect on
water and cultures.
In the last year many pollution disposal methods,
such as concentration evaporation, aerobic treat-
ment, anaerobic digestion, lagooning, lime precip-
itation, etc. (Della Monica et al., 1978; Busacca, 1981;
Vitagliano, 1975; Carola et al., 1975; Amirante and
Mongelli, 1982; Fiestas Ros de Ursinos, 1977; Vigo
et al., 1983a, b) were tested but none of them lead to
industrial application.
As treatment with membrane techniques showed
1491
(Pompei and Codovilli, 1974; Carrieri, 1975; Vigo et
al., 1981, 1983a, b), experimental investigations on
laboratory scale pilot plant were built and a long term
integrated treatment started.
In the present work the results obtained with such
an integrated membrane process on pilot scale and
long-term running time are reported.
EXPERIMENTAL
Following the indications from previous laboratory re-
searches whose data were recently published (Canepa et al.,
1987; Marignetti et al., 1986), a pilot plant was built to treat
the vegetation water with a process combining ultrafiltration
and reverse osmosis techniques with adsorbtion on porous
polymers. The following process scheme was studied:
storage of vegetation water; ultrafiltration; recovery of
ultrafiltration concentrate; treatment of ultrafiltration
permeate with adsorbing polymers; recovery of adsorbed
polyphenols; reverse osmosis of resins eluate; recovery of
reverse osmosis concentrate; and discharge of permeated
fresh water.
The ultrafiltration pilot unit was made of four multiple
modules in series (300 cm length) containing three tubular
membranes each of 1 i.d., for a total area of about 2 m z, and
the operating conditions were kept constant for the whole
work at a pressure of 3.0 x 102 kPa, temperature of 20C
and flow rate of 3 m s-~; polysulfones membranes with
nominal cut-off of 20,000 D were used.
The resin column was made of stainless steel, with an i.d.
of about 60 cm, 8 of about 200 cm and a resin active volume
of about 3001. On laboratory scale four different types of
resins, with fundamental characteristics shown in Table 2,
were tested; the type A resins was chosen for the pilot plant
working at a temperature of 20C and with a flow rate of
2001. min- ~.
The ultraflltration permeate was percolated with a flow
rate of about 2501 h- t and the saturation of the resin bed
was obtained after about 30001.; the resin was then rinsed
with a merry-go-round cycle using process water (OI perme-
ate) and a NaOH 4% solution.
1492 P]ETRO CANEPA et al.

Table I decrease with a plateau after about 20 h of work; as the

Chemical oxygen demand gl 100-150 performance, in terms of chemical oxygen demand and total
Biochemical oxygen demand gl 3(~60 dissolved solids reduction, does not change in the same
Total solids gI 80--120 working time, it becomes obvious that a daily washing
Suspended solids gI 20-60 period obtains the best performances of the ultrafiltration
Total phenols gI 10-15 plant.
Total sugars gI 20-40 From the point of view of pollution control, the balance
Pectines gI 10-15
25 between the analytical characteristics of ultrafiltration feed,
Fats and oils gl
Organics acids gI 1-5 permeate and retentate, as reported in Table 3, show good
Total nitrogen gI 12 14 performances of the membranes with a C O D reduction of
P:O~ gI 2-3 about 63% and a final volume reduction factor of about 11.
K,O g 6-8 The ultrafiltration permeate was then percolated through
Na,O g I 1.5 the described resin column with the results reported in Fig. 3
FeO g 0.1-1 and in Table 4 showing the aspect of good performance in
CaO g I 1.5
the retention of polyphenols (Marignetti et al., 1986).
MgO g 0.07
0.05 The behaviour of the permeate flux of the two stages of
SiO, g
the reverse osmosis section as reported in Fig. 4 shows that
the flux reduction, due to the membranes fouling, becomes
Table 2 important after about 30 h of work: also in this case a daily
Polymer A B C D washing period permits the best performances of the plants
to be obtained in terms of total a m o u n t of permeate.
Specific surt~ace m ~g ~ 40 67 400 850 In Table 5 the analytical data obtained on RO feed (resins
Pore size distribution: eluate), permeate and concentrated are reported. The results
Mode IA) 680 350 70 120
Range (A) 80 700 90-500 25 110 20-145 show a C O D rejection of about 93%, a total dissolved solids
Apparent density gml ~ 0.67 0.96 0.82 0.47 rejection of 99% with a volume reduction factor of about
6. The final permeate shows very good characteristics and
could be easily recycled in the same olive oil mill while the
whole concentrate obtained from the ultrafiltration reten-
Two reverse osmosis units, working in series, were tate and the reverse osmosis concentrate could be used as
equipped with one spiral wound module each, 4 in. dia and
100cm length; polypiperazine ammide membranes with
nominal rejection to NaC1 of 97% in RO I unit and of 95% 5O
in RO 2 unit were used working at a pressure of 40, 102 kPa
JE
and temperature of 20C.
The whole pilot plant, whose schematic drawing is shown
~- 9o

in Fig. 1, was built at Avegno (Liguria) and it worked from

January to May 1987 treating 80,0001. of vegetation waters. 3O
Due to the bad 1986/87 olive season in northern Italy it was ~ , ,
necessary to achieve vegetation water from different coun- 2O 20 6'0 80
hours
tries so the pilot plant treated a mixture of waters received
between December and January. Fig. 2 Performance of ultrafiltration pilot plant. Permeate
The behaviour of the permeate flux of ultrafiltration flux J vs working time. Operating conditions: pressure
section, reported in Fig. 2, shows the aspected regular 3 x 10~ kPa, temperature 20'~C.

Fig. 1. Schematic drawing of integrated membrane pilot plant. (1-4), service tanks; (5-8), washing tanks;
(9), polyphenols recovery tank; (10), concentrated recovery tank; (11), fresh water discharge; (12), U F
pilot plant: (13), resins column; (14-15), reverse osmosis pilot plants.
 Membrane treatment of olive mills waters 1493

Table 3 Table 4
UF UF Influent Effluent
Analytical data UF feed permeate retentate
Density at 20"C 1.0144 1.0013
Total suspended solids gI 24.2 -- 250 Viscosity at 20"C (cp) 0.53 0.47
Total dissolved solids gI 42.6 23.7 210 Total acids (mequiv. I ~) 16.77 8.12
Ashes gl 12.9 I1.1 17.1 Total phenols (g I ~) 2.26 0.12
Chemical oxygen demand gl 72.4 26.8 Monomer phenols (g 1 i) 1.35 0.07
Phenols index gl 1370 400 8800 Red polymer phenols (g I ~) 0.45 0.02
Oil gl 0.5 0.3 2.3 Dark polymer phenols (gl ~) 0.46 0.03
Total nitrogen gl 2.4 0.5 19.8 Total sugars (g I i) 11.32 10.04

"'paste" for oil extraction, phurphurale production or com- Variable costs

bustion for energy recovery; recovery of polyphenols, to use M e m b r a n e supplies, 50% o f the area 11,530
in alimentary and pharmaceutical industry, is also obtained.
C h e m i c a l s a n d w a t e r for m e m b r a n e
Finally on the basis of the results shown, an economical
evaluation was made considering a vegetation water treat- cleaning 1300
ment plant with a capacity of 10,000 tons year -~, working Electricity: 3 k W 7200 h 0.1 $ 2160
300days year L. L a b o u r : 3000 h 15 $ h 1 45,000

ECONOMICAL EVALUATION 59,990

Adsorbing resins: 2 300 1. BV
T h e o p e r a t i n g cost evaluation, b a s e d o n a capacity
Fixed charges
o f 10,000 t o n s year ~ a n d 300 o p e r a t i n g days year ~,
Maintenance 4% of investment 1080
gives the following results:
D e p r e c i a t i o n 10% o f i n v e s t m e n t 2690
U.S. $
Storage facilities: 5000 m 3 t a n k s 3770
a n d fittings Variable costs
Fixed charges Resins supplies 10% o f the BV 374
Maintenance 5% of investment 2860 C h e m i c a l s a n d w a t e r for resins s t r i p p i n g 2800
D e p r e c i a t i o n 10% o f i n v e s t m e n t 14.308 Electricity: 0.8 k W 7200 h x 0.1 $ 576
L a b o u r : 3000 h 15 $ h - ~ 45,000
17,168
Variable costs 48,950
Electricity: 1 2 k W day t 1 2 0 d x 0.1 $ 144 Reverse osmosis: 2 42 m 2 m e m b r a n e area
L a b o u r : 900 h / y e a r J x 15 $ h - l 13,500 Fixed charges
Maintenance 6% of investment 9324
13,500 D e p r e c i a t i o n 10% o f i n v e s t m e n t 15,540
Uhrafiltration: 1 45 m 2 m e m b r a n e area
Fixed charges 24,864
Maintenance 4% of investment 5170
D e p r e c i a t i o n 10% o f i n v e s t m e n t 12.923 100t_
18,093

Z~ Sorption operation "~2 I , ~"-------

(3 Stripping by NaOH
,o 20 s'o ~'o
hours

Fig. 4(a) Performance of reverse osmosis pilot plant (n = 1).

Permeate flux J vs working time. Operating conditions:
3 pressure 40 102 kPa, temperature 20"C.
O
~2 1 L

1
20
i i i L i i i i t 10 20 30 40
2 6 6 8 10 hours
E f f l u e n t bed volumes(BV)
Fig. 4(b) Performance of reverse osmosis pilot plant (n = 2).
Fig. 3. Operating results of resins columns. Total phenols Permeate flux J vs working time. Operating conditions:
content effluent bed volumes. pressure 40 I02 kPa, temperature 20~C.
W.R. 22'12--C
1494 PIETRO CANEPAet al.

Table 5
Data Feed RO Permeate Concentrated R%
T.D.S. gl ~ 22.5 0.19 133 >99
Ashes g1 i I 1.0 0.08 61 > 99
COD gl I 16.1 1.0 84 93.2
Phenols index 86 16 490 93
Oil mg I i 8 0.8 45 88
Total N2 mgl i 310 7 1800 97.7
p20~ mgl ~ 250 2 1783 >99
Na mgl r 2750 12 16,500 >99
K mgl I 3700 40 21,000 >99
Ca mgl I 13 0.1 73 >99
Mg mg I i 67 0.05 345 >99
Fe mgl ~ 8 0.06 41 >99

Variable costs REFERENCES

M e m b r a n e supplies 30% o f the area
Chemicals and water for m e m b r a n e
cleaning
Electricity: 2.3 kW x 7200 h x 0.1 $
Labour: 3000 h x 15 $ h
Total o f fixed charges per liter of
treated w a t e r =
Total o f variable costs per liter o f
treated w a t e r =
Expected financial costs per liter o f
treated w a t e r =
Expected administrative costs per liter o f
treated water =
Expected overhead costs per liter o f
treated water =
Total treatment costs per liter of
treated w a t e r =
CONCLUSIONS
The p r o p o s e d integrated m e m b r a n e process,
without adding any chemicals or thermal energy,
permits the treatment o f the olive mills, wastewaters,
vegetation water, obtaining about 70% o f fresh water
with good characteristics both for recycling than for
agricultural irrigation. The concentrate, 30% o f
initial volume, containing all the organic matter
it is usable for oil extraction, phurphurale production
and c o m b u s t i o n for energy recovery. Also valuated
was the economical feasibility o f the industrial appli-
cation demonstrating that the total cost o f such a
treatment was close to 3 c per liter.
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