Sarika Et Al. 2005
Sarika Et Al. 2005
Sarika Et Al. 2005
www.elsevier.com/locate/envint
Abstract
The pre-treatment of three different olive oil processing effluents by means of direct flocculation (i.e. without prior coagulation) was
investigated. Four cationic and two anionic poly-electrolytes were tested and most of them were found capable of removing nearly
completely total suspended solids (TSS) as well as reducing considerably the concentration of chemical (COD) and biochemical oxygen
demand (BOD5) without altering solution pH. Flocculant dosage was crucial to achieve effective separation. For three cationic and one
anionic poly-electrolytes, the minimum dosage required to initiate separation was about 2.5–3 g/L. The remaining two poly-electrolytes failed
to cause separation even at dosages as high as 7 g/L. Lime and ferric chloride were also tested as reference coagulants and found quite
effective in terms of TSS removal although the degree of COD reduction was generally lower than that with poly-electrolytes. However, lime
treatment would require greater dosages and longer treatment times than that with poly-electrolytes and would also increase considerably
solution pH. A preliminary cost analysis showed that lime treatment for complete solids removal was generally less costly than that with
poly-electrolytes presumably due to its low market price. Nonetheless, cost–benefits may be defied by several drawbacks associated with the
use of lime.
D 2004 Elsevier Ltd. All rights reserved.
complete TSS removal followed by only about 25% COD 2. Experimental and analytical
and 60% phenols removal. However, clay adsorption was
capable of decreasing the residual COD and phenolic 2.1. Materials
contents by as much as 70% and 80%, respectively. The
use of sodium polyacrylate super-absorbent polymers to OME from two three-phase olive mills (W1 and W2) as
detoxify OME has been reported in a recent study (Davies et well as the wash-waters (W3) from the final centrifugation
al., 2004). The absorbent was capable of retaining the of a two-phase mill (all three mills were located in the region
polyphenolic fraction inside the polymeric chains, while of Chania, Crete) were collected and stored at 20 8C. The
large molecules such as proteins were concentrated in the major effluent properties are shown in Table 1.
residual liquid phase whose phyto-toxicity was substantially Four cationic (FO-4700-SH, FO-4490-SH, FO-4350-
reduced. SHU and FO-4190-SH) and two anionic (FLOCAN 23
Coagulation with materials such as lime, alum, ferric and AN 934-SH) poly-electrolytes manufactured by SNF
chloride and ferrous sulphate has also been extensively Floerger were provided by ChemFlo-Hellas. In all cases, the
employed in water/wastewater treatment. Beccari et al. appropriate mass of polymer was dissolved in de-ionized
(1999) proposed a process comprising OME pre-treatment water to give 1% w/v feedstock solutions. This was done
by means of lime coagulation and adsorption on bentonite since addition of polymers directly in the effluent proved
followed by anaerobic digestion. Pre-treatment was capable difficult due to their moderate solubility in water. Calcium
of removing oleic acid, polyphenols and COD by as much oxide (N96%) and ferric chloride (~97%) were supplied by
as 99.5%, 43% and 55%, respectively. The resulting effluent Fluka and used as received.
was subject to 1:1.5 dilution and then treated anaerobically;
for the same dilution level, the original un-treated OME was 2.2. Experimental procedure
not amenable to anaerobic degradation. In further studies
(Aktas et al., 2001), the impact of lime pre-treatment on Experiments were carried out in a jar-test apparatus (Velp
total solids, COD and polyphenols removal for 17 different Scientifica) equipped with six beakers of 1 L volume.
OME was evaluated. OME treatment with lime or ammo- Effluent samples were removed from the freezer, thawed to
nium iron sulphate resulted in about 40–70% COD and ambient conditions and analyzed with respect to their initial
color removal depending on the coagulant dosage employed TSS, dissolved COD and dissolved BOD5 concentrations.
(Zouari, 1998). The resulting effluent was more readily Prior to COD and BOD5 analyses, samples were filtered
degradable anaerobically than the original un-treated efflu- through 0.45-Am disposable filters. The samples were then
ent. Treatment of OME subject to lime or alum coagulation thoroughly shaken, for re-suspension of possible settled
has also been demonstrated by Flouri et al. (1996) and Lolos solids and 300 ml of the sample was transferred to the
et al. (1994). Other recent studies report the use of electro- beaker. The appropriate dosage of flocculant or coagulant
coagulation over iron and aluminium electrodes (Inan et al., was then added while stirring at 200 rpm for 5 to 60 min,
2004) and lime coagulation coupled with the Fenton’s after which separation was complete and sample from the
reagent (Vlyssides et al., 2003) for OME treatment. supernatant was taken and analyzed with respect to the
Although lime is an inexpensive and readily available concentration of TSS, COD and BOD5.
material, lime coagulation generally has several drawbacks, For the runs carried out with poly-electrolytes, the
namely: (i) increase of solution pH and hardness, (ii) low dosage was adjusted using a measured volume of the
COD removal capacity typically between 20–40%, (iii) need respective 1% solution. It should be mentioned that feed-
for large dosages leading to the generation of excessive stock solutions at various concentrations greater than 1%
volumes of sludge which is still quite phyto-toxic and and up to 5% were also prepared but their use proved
cannot be readily disposed of and (iv) need for coupling impractical and, therefore, it was discarded. The 1%
with flocculation to improve efficiency (Tatsi et al., 2003; solution, although slightly viscous, was still easily manage-
Vlyssides et al., 1996). able, while as concentration increased to 2%, the flocculant
The objective of this work was to study for the first time
the destabilization of OME by means of direct flocculation
(i.e. without the addition of coagulants) using various Table 1
Physico-chemical properties of the effluents studied in this work
cationic and anionic poly-electrolytes. Effluents taken from
two-phase and three-phase olive mills were treated to assess Properties W1 W2 W3
the effect of parameters such as flocculant type and dosage, Type of mill Three-phase Three-phase Two-phase
Type of olive Koroneiki Koroneiki Tsounati
treatment time and stirring speed on the removal of TSS,
processed and Liani
COD and biochemical oxygen demand (BOD5). In addition, TSS, mg/L 42 400 101 850 540
lime and ferric chloride were used as reference coagulants COD, mg/L 89 200 57 100 4500
and compared to poly-electrolytes. A preliminary cost BOD5, mg/L 22 800 23 200 1000
analysis was also carried out to evaluate treatment costs BOD5/COD 0.26 0.41 0.22
pH 5.4 5.5 6.7
associated with the materials in question.
R. Sarika et al. / Environment International 31 (2005) 297–304 299
Table 2
Market price for bulk sales of flocculants and coagulants
Material FO-4700 FO-4490 FO-4350 FO-4190 FLOCAN AN 934 Lime FeCl3
Price, o/ton 2980 2800 2800 2800 2500 2550 130 450
With the exception of lime, prices are those quoted by ChemFlo-Hellas. For lime, the price was taken from a local kiln.
Screening experiments showed that, unlike the runs with increased to 15–60 min depending on the coagulant and
poly-electrolytes, treatment for 5 min was not sufficient to the type of effluent.
achieve successful separation. Therefore, the time was Fig. 5 shows data regarding treatment of W2 and W3 at
various CaO dosages. Unlike experiments with poly-
electrolytes, the use of lime expectedly increases the pH
of the liquid phase which, in turn, appears to affect treatment
efficiency. The pH range in which coagulation occurs may
be the single most important factor affecting separation and
optimal values are dependent on the type and dosage of
coagulant as well the effluent characteristics in question. At
the conditions employed in this study, pH effect was more
pronounced for the runs with W2; pH values between 11
and 12 (this corresponds to lime dosages between 6.7 and
13.3 g/L) resulted in successful separation. However,
increasing lime dosage to 20 g/L had a detrimental effect
on the process, possibly due to re-stabilization of the
colloids. Talaat et al. (2002) who studied the lime
Fig. 4. Relative efficiency of various poly-electrolytes to treat 300 ml of Fig. 5. Effect of CaO dosage on separation. (a) Treatment of W2 for 60 min;
(a) W1; (b) W2; (c) W3. (b) treatment of W3 for 15 min.
302 R. Sarika et al. / Environment International 31 (2005) 297–304
Fig. 7. Cost of various materials for treatment of (a) W1; (b) W2; (c) W3.
about 1500–1700 tons of olives. Given that olive processing treatment with polymers. In light of this, an optimum
usually generates about 1.5 m3 of wastewaters per ton of combination of coagulants and flocculants might be
olive processed, this would amount to about 2500 m3 OME. needed to improve process economics.
Cost estimates are shown in Fig. 7.
Treatment of OME (streams W1 and W2) with various Although flocculation appears to be a promising technol-
poly-electrolytes would cost no more than a few cents per ogy for OME pre-conditioning, it is evident that special
kg TSS removed. Of the various polymers tested, FLOCAN attention must be paid to ensure that the resulting liquid and
23 appears to be marginally better than the rest. Nonethe- solid phases are suitable for further treatment, disposal or use.
less, lime and ferric chloride are still substantially less Mineralization of the liquid phase would require some form
expensive than polymers presumably due to their lower of treatment possibly by means of advanced oxidation or
market price. The fact that treatment of W1 with polymers biological processes or a combination of them. In this view,
costs nearly twice as much as treatment of W2 (per kg TSS we are currently investigating the use of high power
removed) is due to the fact that a common flocculant dosage ultrasound for the post-treatment of the liquid phase. On
of about 3 g/L was used for both streams although TSS the other hand, it is well-documented that the solid fraction of
concentration in W1 is only half that in W2. various agro-wastes may be composted to yield soil fertilizers
The low initial TSS concentration of wash-waters W3 (Manios, 2004). In a recent study (Garcı́a-Gómez et al.,
explains the relatively low annual cost of treatment. 2003), sludge from the flocculation pre-treatment of two- and
However, it should be emphasized that data for the various three-phase OME (using a commercial poly-electrolyte) was
materials shown in Fig. 7c are not directly comparable to subject to composting with olive leaves, thus resulting in the
each other since experiments were carried out at different formation of biologically stabilized composts.
flocculant or coagulant dosages. This would explain the
rather unexpectedly high cost associated with lime or ferric
chloride since the dosage on which calculations were based Acknowledgments
(i.e. 2.5 g/L for lime and 0.67 g/L for ferric chloride) might
be well over the stoichiometric amount required for The authors wish to thank Mr. A. Hatzopoulos of
complete removal. ChemFlo-Hellas for donating the poly-electrolytes.
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