Bioresource Technology 57 (1996) 237-243 Copyright 1996 El~vier Science Limited Printed in Great Britain.

. All rights reserved 0960-8524/96 $15.00

ELSEVIER
PI I:S0960-8524(96)0005 I-X

ANAEROBIC DIGESTION OF TOTAl. RAW OLIVE-OIL WASTEWATER IN A TWO-STAGE PILOT-PLANT (UP-FLOW AND FIXED-BED BIOREACTORS)
D. Dalis, a* K. A n a g n o s t i d i s , a A. L o p e z , a I. L e t s i o u a & L. H a r t m a n n b aSection of Ecology and Systematics, University of Athens, Panepistimiopolis, Athens 15784, Greece bBiotechnology Department, University of Karlsruhe, Karlsruhe, Germany

(Received 6 August 1995; revised version received 15 March 1996; accepted 3 April 1996)
Abstract

A study was undertaken to evaluate the anaerobic digestion of total raw olive-oil wastewater in a twostage pilot-plant with reactors connected in series. Two different types of anaerobic digesters were used, an upflow type and a fixed-bed type. The main pupose of the study was to evaluate the performance of an up-flowtype reactor working in series with a fixed-bed-type reactor, which was used as a complementary treatment. The pilot-plant system operated in the mesophillic range (35 + 1C) during approximately 390 days, and with organic loading levels that ranged between 2.8 and 12. 7 g COD/l.day. Concentrated aqueous ammonia was added to the total raw wastewater to adjust the C/N ratio to the optimum value of 20/1, and this also achieved stabilisation of the p H values in the digesters within a range about neutrality. In a series of seven consecutive experiments, for the first stage (upflow digester) optimum values of specific biogas production rate stabilised at a value of 2.1 litres/litre digester.day with a very satisfactory COD reduction of 83% (with a volumetric load of 11 g COD/l.day). For the second stage (fixed-bed digester), the biogas production rate stabilised at a value of 0.22 litres/litre digester.day with a COD reduction of 8% (with a volumetric load of 0.19gCOD/l.d). According to the results reported in the literature for total raw wastewater, the performance of the applied system is amongst the best for biogas production, COD reduction and loading rate reported so far, especially for the up-flow digester. Phenols were greatly reduced during the anaerobic digestion process in both digesters, with a concentration reduction which reached 75% in the up-flow digester; with the use of the second stage (fixed-bed reactor) a further reduction of 45% was obtained. With the above encouraging results we may suggest the employment of the up-flow type digester as an economical and effective treatment for significantly reducing the organic load of total raw wastewater. More satisfactory results might be expected from the

use of a fixed-bed-type digester connected in series with a previous one, as a second treatment stage. Copyright 1996 Elsevier Science Ltd. Key words: Anaerobic digestion, olive-oil mill wastewater, biogas production, fixed-bed digester, up-flow digester.
INTRODUCTION

*Author to whom correspondenceshould be addressed. 237

Olive-oil wastewater, together with the wastewater from distilleries (vinasse), is considered as one of the most polluting agro-industrial residues due to its high organic load (the wastewater of an average production capacity olive-oil mill: 50 m3/day, BOD5 of 40g/l, is equivalent to the wastewater of a city with a population of 30 000 inhabitants). The treatment and disposal of such wastewaters is very difficult for reasons that are related to its physical and chemical contents (low pH values, high phenols concentration, volatile fatty acids, phytotoxic properties, etc.); the technical and economical structure of the olive-oil mills (average economic potential mainly private, but also in agro-industrial corporations of seasonal operation); and finally to the fact that the olive-oil mills are geographically scattered along the Mediterranean region, where almost all the world production of olive-oil is concentrated. The olive-oil-producing countries are trying to face the negative impacts of the olive-oil wastewaters in the environment. The most important of these attempts is the anaerobic treatment of olive-oil wastewater for the production of methane (Dalis et al., 1982; Dalis, 1991; Fiestas Ros de Ursinos et al., 1982; Aveni, 1983; Boari et al., 1984, Rozzi et al., 1984; Aveni & Lamarca, 1986; Georgacakis & Dalis, 1993) or for the recovery of valuable materials, such as colouring compounds and polysaccharides (Iniotakis et al., 1989). The wastewater can also be used as a soil-quality recoverer and as liquid fertiliser (Balice et al., 1990).

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D. Dalis, K. Anagnostidis, A. Lopez, I. Letsiou, L. Hartmann

The most important reasons for the choice of anaerobic digestion as a treatment method are the feasibility to treat wastewaters with a high organic load and the techno-economical structure of the olive-oil mills. According to international experience (Hartmann, 1993), the aerobic treatment of such a wastewater requires biological purification systems with high construction and operational costs (energy consumption), besides which stabilisation of the biological reactions is not assured (activated-sludge tanks), or the wastes cause clogging of installations such as aerobic biological filters and biodiscs. In the case of seasonal operation of the production units, the disadvantage of a slow start-up after the nonfeeding conditions makes the aerobic treatment unacceptable for the treatment of mill wastewater. With bioreactors for anaerobic fermentation these problems are not present. The subject of the present paper was the study of the anaerobic digestion of total raw olive-oil wastewater in a two-stage pilot-plant (up-flow and fixed-bed digesters connected in series). Reports on total raw wastewater using two-stage installations are not referred to in the literature.
METHODS

Olive-oil mill

Storage tank

Outflow Fixed-bed Up-flow reactor reactor 1. Flow diagram of the pilot treatment plant.

Fig.

The olive-oil wastewater used in the anaerobic treatment pilot-plant was obtained from the centrifugal olive-oil mill in Kalivia (East Athens). The unit, which was sheltered alongside the olive-oil mill, operated in series from December 1993 to March 1995. The anaerobic digestion system consisted of a 20 m 3 storage tank of raw wastewater at the start, and an up-flow sludge-blanket reactor of 2 m 3 useful volume, and a fixed-bed-type reactor of 2 m 3 useful volume, with filling material consisting of polyethylene plastic rings (PALL), working in series with the previous one. Both digesters were made of ordinary steel and insulated by a 6-cm thick glasswool layer, externally coated with aluminium sheets for protection. Each one of the digesters was surrounded by a heat exchanger which kept the temperature in the mesophillic range (35 + IC). The dimensions of each digester were 0.7 m in diameter

and 2.5 m height. Figure 1 shows a simplified diagram of the anaerobic pilot-plant. The starting of the up-flow operation was done by addition of 350 1 of anaerobic biomass from a similar domestic-wastewater installation, together with 650 1 of raw olive-oil wastewater. At the beginning the system operated in batch conditions for approximately 2.5 months until its stabilisation. The operation of the whole system started in December 1993, first with the up-flow digester, followed by the fixed-bed digester 4 months later. By the end of August the system was stopped because of the lack of olive-oil wastewater, and it restarted its normal operation in December 1994. The biogas produced by each digester was measured by domestic natural-gas meters and stored in an inverted gas holder. For the C/N ratio adjustment to 20/1 concentrated aqueous ammonia was added to the total raw wastewater, and this also stabilised the pH values in the digesters at near neutrality. The quantitative characteristics of the seven series of experiments, expressed as mean values, are listed in Table 1.
Chemical analysis Chemical oxygen demand (COD), total organic nitrogen, phenols concentration and pH were determined as described in Standard Methods (American Public Health Association, 1985). Total organic carbon (TOC) content was determined by photochemical oxidation of the organic compounds.

Table 1. Quantitative average characteristics of the experiments

Experimental parameter Duration, days Retention time up-flow (fixed-bed), l/day Flow rate up-flow (fixed-bed), l/day Inflow COD (TOE), g/l Volume load up-flow, g COD/1.day (g TOC/l.day) Volume load fixed-bed, g COD/l.day (g TOC/l.day)

1 188 14.8 135 46.3 (9.2) 3.6 (0.6)

2 53 15.3 (10) 131 (200)

3 24 10 (10) 196 (200)

4 23 10.7 (10) 187 (200)

5 19 11.1 (5) 181 (400)

6 60 7.5 (5) 267 (400) 54 (15.5) 7.2 (2.1)

7 22 5.6 357 71.3 (15.2) 12.7

46.6 (13.8) 56.8 (14.5) 117.7 (23.3) 59.8 (16) 2.8 (0.9) 5.6 (1.4) ll (2.2) 5.4 (1.4) 0.13 (0.04) 0.15 (0.04) 0.19 (0.07)

0.19 (0.07) 0.25 (0.08)

Digestion of whole raw olive wastewater

239

A SYBRON-E-3500-type photochemical analyser of organic carbon was used. For measurement of the biogas production, the ORSAT meter was employed. The samples from each reactor were taken daily and tested for pH, temperature, biogas production, and chemical oxygen demand. Weekly analysis of phenols, total organic nitrogen, and volatile fatty acids were also performed. RESULTS AND DISCUSSION The performance of the biological fermentation during the seven experiments was tested with the use of the following parameters: degradation level of the organic load expressed as reduction of total organic carbon (TOC) and of chemical oxygen demand (COD) in the up-flow reactor, as well as in the fixed-bed reactor; fluctuation of pH values and specific biogas production (Rg), expressed as litres of biogas produced per litre digester per day; transformation of the dissolved organic carbon into the form of gaseous carbon; overall values of the specific blogas yield (Yg) in steady-state conditions of the processes; reduction of concentration of phenolic compounds in the wastewater and reduction efficiency of volatile fatty acids. pH value The stabilisation of the pH values within a neutral region (6.9-7.4) in the up-flow reactor during the seven consecutive experiments is shown in Fig. 2. It is interesting to note that no buffer solution was used for correction of the unusually low pH values of the initial substrate (5.0-5.5). This was because of the buffer action of the NI-I~ ions which were produced during the anaerobic digestion from the raw wastewater, previously mentioned as being enriched with aqueous ammonia for adjusting the C/N ratio to the optimum value of 20/1 (Fiestas Ros de Ursi-

nos, 1983; Cabbelo et al., 1986; Dalis, 1991). It is worth noting that the C/N ratio of the initial substrate fluctuated between 40 and 45/1. Organic load degradation It is interesting to note that during the fourth experiment the installation operated with a very high volumetric loading rate (2.2 g TOC/l.day or 11 g COD/l.day). In spite of the gradual increase in the volumetric load (Br) in the up-flow reactor, as well as in the fixed-bed, during the seven consecutive experiments (Figs 3-5), a satisfactory reduction of the organic pollutional load of the wastewater was obtained. This ranged between 68 and 77% as TOC up-flow reduction (or 75-85% as COD up-flow reduction). The use of the fixed-bed reactor connected in series gave further TOC and COD reductions which fluctuated between 15 and 20%. Similar high degradation values of the organic load with corresponding high volumetric loading rates have not been mentioned in the literature concerning total raw olive-oil wastewater. Georgacakis and Dalis (1993) reported a COD outflow reduction which fluctuated between 94 and 95%, but only for the supernatant liquid fraction of wastewater obtained after natural sedimentation of the total raw wastewater and removal of the settled sludge. This is easily degradable wastewater compared with the raw olive-oil wastewater. Rozzi et al. (1984), Aveni and Lamarca (1986), Carrieri and Ballice (1986), Carrieri and Ballice (1988) and Tsonis and Grigoropoulos (1988), among others, reported that the outflow organic load reduction fluctuated from 40 to 85% using lower volumetric loadings. Finally, it is worth noting that the observed stabilisation of the biological process in the fourth experiment, besides the gradual increase in the volumetric loading, was apparently due to adaptation with time of the microorganism populations inside the two digesters.
4

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6 11 ~6 21 26 31 36 41 46

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Week Fig. 2. Specific biogas production rate (Rg) (=) and pH ([]) fluctuation in up-flow digester.

240
100 90 80 70 60 50 40

D. Dalis, K. Anagnostidis, A. Lopez, I. Letsiou, L. Hartmann

cO 0 "(3 0 O~ "0

0 k"

30 20 10 0 1 2 3 4 5 6 7

Experiment Fig. 3. Percentage TOC degradation in up-flow (=) and fixed-bed (D) digesters in steady-state conditions. Biogas During the seven consecutive experiments a gradual increase of the specific biogas production (Rg) in the first stage (up-flow reactor) was observed, which fluctuated from 2.1 to 2.3 litre biogas/litre digester day (Figs 2 and 6). These values are considered high
100 90 8O

according to those previously reported [Dalis et al. (1982); Boari et al. (1984); Rozzi et al. (1984); Georgacakis & Dalis (1993)]. In the fixed-bed bioreactor the biogas production stabilised at 0.5 litre biogas/litre digester.day. The optimum values of specific biogas yield (Yg) for the

tO ~

70

I1~ '~

5O 4O 3o 20

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Experiment Fig. 4. Percentage COD degradation in up-flow (m) and fixed-bed ([]) digesters in steady-state conditions.

90 80 7O e" 0

100 90 80 70

so
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6

60

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Week Fig. 5. Dissolved oganic carbon reduction (o) and its transformation into biogas (,,) in up-flow digester.

Digestion of whole raw olive wastewater

241

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Experiment Fig. 6. Specific biogas production (Rg) in up-flow (t) and fixed-bed ([]) digesters in steady-state conditions. up-flow reactor (Fig. 7) during the second and third experiments ranged between 21 and 22 litre biogas/g TOC degraded. Phenols and volatile fatty acids degradation The percentage reduction of phenols in the up-flow reactor reached 73% in the first experiment (Fig. 8).
2,5

Furthermore, in the fixed-bed reactor there was a 35% phenols reduction. The phytotoxicity test showed that the outflow from the fixed-bed reactor did not promote toxicity reactions. It is probable that this was due to the considerable reduction in phenolic compounds, as well as the concentration of volatile fatty acids (Fig. 9), whose degradation

F1,5 "o

-IO t~ >,.

0,5

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Fig. 7. Specific biogas yield (Yg) in up-flow (m) and fixed-bed (D) digesters in steady-state conditions.

7O tO O= "0 q) "0 n

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Experiment

Fig. 8. Percent phenols degradation in up-flow (m) and fixed-bed (D) digesters in steady-state conditions.

242
80

D. Dalis, K. Anagnostidis, A. Lopez, I. Letsiou, L. Hartmann

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"1~

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v,-

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Fig. 9. Percentage volatile acids degradation in up-flow (B) and fixed-bed (D) digesters in steady-state conditions.

reached 75% during the first experiment in the upflow reactor, while with the use of the fixed-bed reactor a further reduction of 45% was produced. As is known, the strong phytotoxicity which the olive-oil wastewater exerts is mainly due to the high concentration of phenols and acids.

Possible useful applications of the method The above satisfactory results from the operation of the pilot-plant confirm the possibility of the practical application of the method resulting from both the considerable reduction of the retention time (in the fourth experiment to 10 days) and the simplification of the total treatment process (without calcium hydroxide addition and pre-treatment systems). As an overall consequence, reduction of the construction and operation costs of the installation should be obtained. In parallel, with an appropriate use of the considerable biogas produced (2.32 litres biogas/litre digester.day) it should be possible to achieve the repayment of the initial capital investment in a short time. However, it should be kept in mind that the success of the proposed methodology relies in not considering the method just as a way to achieve energy recovery, but as a method to control the environmental problems caused by such polluted wastewaters. REFERENCES
American Public Health Association (1985). Standard Methods of Wastewater Analysis. APHA, Washington, D.C. Aveni, A. (1983). Biogas recovery from olive oil production waste by anaerobic digestion, R and D program--recycling of urban and industrial waste Broni (Pavia). Instituto Ricerche, Breda, Italy, 17-19 May 1983. Aveni, A. & Lamarca, A. (1986). Biogas recovery from olive-oil mill wastewater by anaerobic digestion. In

Anaerobic Digestion: Results of Research and Demonstration Projects, ed. M. P. Ferranti, G. L. Ferrero and P. L. Hermite. Elsevier Applied Science, London, UK, pp. 236-240. Balice, C. et al. (1990). Effect of olive-oil mill wastes on soil fertility. In Tratamiento de Alpechines, Cordoba, 2 May-1 June 1990. Boari, G., Brunetti, A., Passino, R. & Rozzi, A. (1984). Anaerobic digestion of olive oil mill wastewaters. Agric. Wastes, 16, 161-175. Cabbelo, L. R. et al. (1986). Determination of polyphenols and carbohydrates in vegetation waters by advanced assay techniques. In Int. Symp. on Olive By-products Valorisation, Seville, pp. 119-127. Carrieri, C. & Ballice, V. (1986). Anaerobic treatment of olive mills effluents and sewage sludge in conventional digesters. In Int. Symp. on Olive By-products Valorisation, Seville, pp. 195-206. Carrieri, C. & Ballice, V. (1988). Anaerobic treatment of olive mill effluents and sewage sludge in conventional digesters. In 5th Int. Symp. on Anaerobic Digestion, ed. A. Niche & A. Rozzi, Bologna, Italy, pp. 481-484. Dalis, D. (1991). Optimisation of the C/N ratio during the anaerobic digestion of olive-oil waste waters. In Proc. 13th National Congress of the Hellenic Biological Sciences Union, Heraklion, Crete (in Greek). Dalis, D., Hartmann, L. & Anagnostidis, K. (1982). Anaerobic treatment of olive oil waste waters. R&D program--recycling of urban and industrial waste (RUW-056), Brussels, Belgium. Fiestas Ros de Ursinos, R. J. (1982). Depuracion anaerobia del alpechin como, fuente de energia. Grasas y Aceites, 5, 265-270. Fiestas Ros de Ursinos, J. A. (1983). Purification of vegetation water by anaerobic digestion as a means of producing energy. Valorisation of Olive By-products. Technical Committee Meeting, Madrid, pp. 132-140. Georgacakis, D. & Dalis, D. (1993). Controlled anaerobic digestion of settled olive-oil mill wastewater. Biores. Technol., 46, 221-226. Hartmann, L. (1993). Biologische Abwassereinigung 3. Uberarbeitete. Springer, Berlin. Iniotakis, N~, Michailidis, P. & Koumakis, M. (1989). KctOctptal~o~ K~.ztrt])~poo #~ z~ozoxpovtI ~tonot~ltrtl Xp~lqtluov t~2tx~ov. Flpct~cr. ~ll~p. FEf~YEE - - Aprlz~l(. Opctx2eto, pp. 81-88. Rozzi, A., Santori, M. & Spinosa, L. (1984). Anaerobic digestion in Italy with special reference to treatment of

Digestion of whole raw olive wastewater

olive-oil mill wastes. In Anaerabic Digestion of Sewage Sludge and Organic Agricultural Wastes, ed. A. M. Bruce, A. Koutzell-Katsiri & P. J. Newman. Elsevier Applied Science, London, UK, pp. 55-65.

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Tsonis, S. P. & Grigoropoulos, S. (1988). High rate anaerobic treatment of olive oil mill waste water. In Proc. 5th International Symp. in Anaerobic Digestion. Pergamon Press, Oxford, UK, pp. 115-124.