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WO2005003037A1 - Procede de valorisation d'effluents aqueux provenant d'installations de fabrication d'huile d'olive - Google Patents

Procede de valorisation d'effluents aqueux provenant d'installations de fabrication d'huile d'olive Download PDF

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Publication number
WO2005003037A1
WO2005003037A1 PCT/IB2004/002215 IB2004002215W WO2005003037A1 WO 2005003037 A1 WO2005003037 A1 WO 2005003037A1 IB 2004002215 W IB2004002215 W IB 2004002215W WO 2005003037 A1 WO2005003037 A1 WO 2005003037A1
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WO
WIPO (PCT)
Prior art keywords
filters
resins
omww
turf
filter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2004/002215
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English (en)
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WO2005003037B1 (fr
Inventor
Elias Castanas
Nicolaos Andricopoulos
George Mposkou
Joseph Vercauteren
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMERGO (CYPRUS) Ltd
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EMERGO (CYPRUS) Ltd
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Publication of WO2005003037A1 publication Critical patent/WO2005003037A1/fr
Publication of WO2005003037B1 publication Critical patent/WO2005003037B1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/427—Treatment of water, waste water, or sewage by ion-exchange using mixed beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C02F2103/322—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from vegetable oil production, e.g. olive oil production
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage

Definitions

  • OMWW olive mill wastewater
  • agro-industrial waste is olive mill wastewater (OMWW) , formed by the tissue water from the olive fruits, the water added during the process of oil extraction, soft tissues from olive pulp and oil, in the form of a very stable emulsion.
  • OMWW olive mill wastewater
  • Great amounts of OMWW are produced in Medi- terranean countries, where this waste imposes a great environmental hazard, if it is not treated, due to its very high organic COD loads.
  • the elimination and/or treatment of OMWW is one of the main problems faced by processing companies involved in the extraction of ' olive oil, because they contain ' powerful .pollutants [1] .
  • This waste is an acidic (pH ⁇ 5) , malodor- ous liquid that contains potassium and phosphatic salts and organic substances such as fats, protein, sugars, organic acids, and polyp enols.
  • suspended matter consisting of olive pulp, mucilage, pectin, and oil in a relatively stable emulsion is also present.
  • the amount of OMWW produced, and therefore the environmental impact varies depending on the method of olive oil extraction used. In fact, the traditional press method produces -50% of OMWW relative to the initial weight of the olives, whereas the continuous . process produces 80-110% of OMWW due to the continuous washing of • the olive paste with .warm water before oil separation from the paste.
  • the concentration of the phenolics in the olive oil ranges from 50 to 1000 ⁇ g/g of oil depending on the olive variety [4] . This amount of antioxidants in the olive oil is 1-2% of the available pool of antioxidants in the olive fruit.
  • the 3,4-DHPEA is present in different oleosidic forms: the 3,4-DHPEA form, the form linked to the dialdehyde form of elenolic acid (3,4- DHPEAEDA) , and as an isomer of oleuropein aglycon (3,4-DHPEAEA) [7] . All of these three forms are degradation products of oleuropein. Oleuropein is a glu- coside that contributes to the bitterness of olives. The antioxidant activity of all three forms is different, as well as their biological activity [9] . Their antioxidant activity is also dependent on the concentration of these compounds, and more specifi- cally, it is proportional to the antioxidant concentration in the oil phase [10] .
  • the physicochemical methods are based on OMWW treatment with flocculants and coagulant, cryogenesis, ul- trafiltration, reverse osmosis, thermal concentration and evaporation in ponds. These methods are generally very expensive and/or unable to completely solve the problem because of the need to dispose of a sludge deriving from the process [11] .
  • Biological methods are based on production of proteins, poly-hydroxy-b- butyrates, poly-hydroxy-alcanoates and exopolysaccha- rides, anaerobic digestion and composting [12-14] . These methods have certain clear benefits due to the potential utilization of their by-products.
  • the present invention relates to a system of filters for use in the treatment of olive mill waste waters (OMWW) , wherein said system of filters is com- posed of a combination of sub stratums of natural products selected from a group comprising turf, sand, and sawdust, and optionally one or more filters of resins selected from the group consisting of cationic, mixed-bed, and PVPP.
  • OMWW olive mill waste waters
  • the system of filters is made of inexpensive physical product filters (sawdust, turf, sand) .
  • the system offers a considerably degree of flexibility. As the system is made up of a discrete number of filters, the number of each kind of filter in the system is easily changed.
  • the filters is composed of a combination of sub stratums of natural products selected from the group consisting of turf, sand, and sawdust.
  • Turf is defined as the upper stratum of earth and vegetable mold, which is filled with the roots of grass and other small plants, so as to adhere and form a kind of -mat.
  • sand is defined as fine particles of stone, especially- of siliceous stone,, but ⁇ not reduced to dust as well as comminuted stone in the form of loose grains, which are not coherent when wet.
  • sawdust is defined as dust or small fragments of wood (or stone etc.), which for example is made by the cutting of a saw.
  • one or more filters of resins may be incorporated into the system of filters .
  • the efficacy of the system of filters is increased.
  • the use of resins makes it possible to retain high additive value products, such as antioxidant biophenols, which are present in the waste waters to be treated. A subsequently recovery as the resin is regenerated is then possible. Consequently, the use of the system of filters is made more profitable.
  • the system of filters is made up of one turf filter, one sand filter and one sawdust filter, and optionally two filters of resins . ••
  • the system of filters is made up of one turf filter, one ' sawdust filter, and one sand filter, and optionally two filters of resins.
  • PVPP is defined as a resin made of polyvinylpolypyrrolidone .
  • Another aspect of the invention relates to a method for treatment of OMWW using a system of filters according to the present invention wherein said method comprises the step of: a. producing an effluent by passing the OMWW through said system of filters.
  • the organic filter is further burned at a temperature comprised between 1500 and 800°C, more preferred be- tween 1200 and 900°C, and even more preferred between 980 and 900°C.
  • the produced smoke does not contain any trace of organic material (ex. dioxins) , except C0 2 and its NOx content is lower than 1%.
  • the method further comprises the-, step of : b. regenerating the system of filters composed of the combination of sub stratums of natural products selected from a group comprising turf, sand, and sawdust and/or the filters of resins either simulta- neously or separately by passing on organic solvent through said part of the system of filters.
  • the method further comprises the step of: c. adding a flocculant to the effluent obtained in step a in order to eliminate colour of the effluent .
  • flocculants include Aluminium and other absorbent salts.
  • the effluent obtained from above-mentioned method is used for agricultural irrigation. In this way the subsequent discharge of the treated waste waters is taken care of by recycling both organic matter and nutritive elements to the soil-crop system.
  • Still another aspect relates to a method for retention and recovery of highly valuable products, such as antioxidant biophenols, present in the OMWW by use of the system of filters according to the in- vention, wherein said method comprises the steps of: A. retention of said highly valuable products on the filters of resins by passing the OMWW through said system of filters, B. separating the filters of resins from the other filters, C. washing of the filters of resins by passing a solvent through said filters, and D.
  • the first stage filter is the one presented in Figure 2.
  • Figure 4 depicts a possible construct of the proposed filter.
  • the first stage filter (circles) consists of sawdust, turf, and sand, in different order, as described in the text and in Figure 2.
  • the second stage filter consists of mixed bed, cationic or PVPP resins.
  • an electrochemical conductivity sensor controls the condition of each filter.
  • a pump at the beginning of the filter series controls the flow.
  • the OMWW employed in the experiments was waste water from 3 phase centrifugal olive oil mill (OW) .
  • OW 3 phase centrifugal olive oil mill
  • the following materials were used: commercial sawdust for pets, iron gauge, cheesecloth, canvas sheets and sheets of as- bestos cotton, standard filter paper, sartorius filters of fibreglass lO ⁇ m and cellulose acetate I ⁇ m, plough se . eds of cardamom, soil and turf mix for home gardening, and as resins: Amberlite XAD 16 or XAD 4 5 (Rohm & Haas a.s 63117) or any compatible mixed bed or cationic resin, and polyvinylpolypyrrolidone PVPP (Sigma P-6755) .
  • the following chemicals were used: caffeic acid (Fluka 60018) , gallic acid (Sigma G-
  • Example 1 Description of the filters Treatment of OMWW in view of their purification
  • the main objective of this part of the invention was the direct purification of OMWW, in view of the direct use of the effluent, for agricultural pur- 25 poses.
  • OMWW were treated with a number of substances, in order to eliminate the major part of biophenols.
  • the treatments and results are presented in the following table. We present the combination of two filtrations over turf, combined with
  • the purification of OMWW can be achieved as presented in the flow diagram presented in Figure 2.
  • Example 2 Treatment of OMWW in view of the purification of biophenols
  • the sawdust was sieved through iron gauge and so separated to thin sawdust (SD) and saw chippings (SC) .
  • 800mL of OMWW was mixed with 20g SC (20/1 mixing ratio) in 1L beaker and manually stirred with spatula for 15min.
  • the mix was then sieved through the holes of a Buchner funnel under vacuum and filtered under vacuum through cheesecloth on a Buchner funnel.
  • the first filtrate Fa was mixed with SD, in 20/1 mixing ratio, and stirred manually with spatula for 15 min.
  • the mixture was filtered under vacuum through ' asbestos cotton.
  • the process- was repeated once more with second filtrate Fb .
  • the filtrate Fc was filtered under vacuum through canvas sheets and then mixed with XAD 16, in 10/1 mixing ratio and stir mixed on a magnetic stirrer 15 min.
  • the mixture was filtered under vacuum through asbestos cotton.
  • the process was repeated with the forth filtrate Fd for 3 more times.
  • Tests of phytotoxicity 50mL of treated OW were poured into lOg of soil and turf mix in a glass beaker. After 2 days the excess water was poured off and 30 seeds of cardamom were ploughed, half deep into the wet soil. The bea- ker was covered with a bigger beaker and kept indoors next to a window. After 2 days the number of seeds with sprouts was counted.
  • a reference culture was prepared with 50mL tap water instead of OW. The final effluent resulted in a 70% germination of the seeds, and can be used for agricultural purposes.
  • a flow chart of OMWW purification with a combination of filters is presented in Figure 3.
  • the final effluent can be directly used for agricultural purposes, and the polyphenols can be extracted from the resins.
  • a possible construction for the production of a filter in use in olive mills is presented in Figure 4.
  • a flocculation method can be applied, in order to eliminate the light yellow colour, and produce a more transparent product .
  • a number of commercially available floccu- lants have been assayed with equally good results.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Sludge (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

Système à filtres utilisable dans le traitement des effluents aqueux provenant d'installations de fabrication d'huile d'olive, et procédé mettant en oeuvre ce système à filtres. Le résultat favorable de l'utilisation dudit système à filtres dans le traitement desdits effluents est un effluent que l'on peut utiliser dans l'irrigation agricole, et pour retenir et récupérer des produits de grande valeur présents dans les effluents à traiter.
PCT/IB2004/002215 2003-07-08 2004-07-06 Procede de valorisation d'effluents aqueux provenant d'installations de fabrication d'huile d'olive Ceased WO2005003037A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GRGR20030100295 2003-07-08
GR20030100295A GR20030100295A (el) 2003-07-08 2003-07-08 Μεθοδος για τον καθαρισμο των υδατικων αποβλητων ελaιουργειων

Publications (2)

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WO2005003037A1 true WO2005003037A1 (fr) 2005-01-13
WO2005003037B1 WO2005003037B1 (fr) 2005-05-06

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WO (1) WO2005003037A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016083525A1 (fr) 2014-11-26 2016-06-02 Creta Farm Societe Anonyme Industrial And Commercial Trading As Creta Farm S.A. Extrait d'olive aqueux présentant des propriétés métaboliques et cardioprotectrices
FR3029517A1 (fr) * 2014-12-05 2016-06-10 Veolia Water Solutions & Tech Procede de traitement d'eau comprenant une etape d'adsorption sur resine echangeuse d'ions et une etape de coagulation/floculation lestee et de separation, et installation correspondante.
US9420820B2 (en) 2013-08-09 2016-08-23 University Of Tsukuba Method for isolating polyphenols from olive mill water
PT108658A (pt) * 2015-07-02 2017-01-02 Rauschert Portuguesa Sa Processo de reciclagem e reutilização de efluentes líquidos da extracção do azeite.
GB2633940A (en) * 2022-05-31 2025-03-26 Pathogen Reduction Solutions Ltd Device for reflecting ultraviolet radiation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5232358B2 (fr) * 1971-12-29 1977-08-20
SU1579905A1 (ru) * 1988-05-19 1990-07-23 Пермский политехнический институт Фильтрующий материал дл очистки сточных вод
WO1994002418A1 (fr) * 1992-07-22 1994-02-03 Flocco-Tec Aps Procede et appareil pour purifier des suspensions aqueuses contenant des matieres organiques et des cations
EP1041044A1 (fr) * 1999-03-31 2000-10-04 Argus Umweltbiotechnologie GmbH Procédé pour la purification d'eaux usées contenant des phénols

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5232358B2 (fr) * 1971-12-29 1977-08-20
SU1579905A1 (ru) * 1988-05-19 1990-07-23 Пермский политехнический институт Фильтрующий материал дл очистки сточных вод
WO1994002418A1 (fr) * 1992-07-22 1994-02-03 Flocco-Tec Aps Procede et appareil pour purifier des suspensions aqueuses contenant des matieres organiques et des cations
EP1041044A1 (fr) * 1999-03-31 2000-10-04 Argus Umweltbiotechnologie GmbH Procédé pour la purification d'eaux usées contenant des phénols

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
AL-MALAH ET AL: "Olive mills effluent (OME) wastewater post-treatment using activated clay", SEPARATION AND PURIFICATION TECHNOLOGY, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 20, 2000, pages 225 - 234, XP002212723, ISSN: 1383-5866 *
DATABASE WPI Section Ch Week 197737, Derwent World Patents Index; Class D15, AN 1977-66137Y, XP002308120 *
DATABASE WPI Section Ch Week 199122, Derwent World Patents Index; Class D15, AN 1991-162740, XP002308119 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9420820B2 (en) 2013-08-09 2016-08-23 University Of Tsukuba Method for isolating polyphenols from olive mill water
WO2016083525A1 (fr) 2014-11-26 2016-06-02 Creta Farm Societe Anonyme Industrial And Commercial Trading As Creta Farm S.A. Extrait d'olive aqueux présentant des propriétés métaboliques et cardioprotectrices
FR3029517A1 (fr) * 2014-12-05 2016-06-10 Veolia Water Solutions & Tech Procede de traitement d'eau comprenant une etape d'adsorption sur resine echangeuse d'ions et une etape de coagulation/floculation lestee et de separation, et installation correspondante.
EP3040312A1 (fr) * 2014-12-05 2016-07-06 Veolia Water Solutions & Technologies Support Procede de traitement d'eau comprenant une etape d'adsorption sur resine echangeuse d'ions et une etape de coagulation/floculation lestee et de separation, et installation correspondante
AU2015261726B2 (en) * 2014-12-05 2020-06-25 Veolia Water Solutions & Technologies Support Method for the treatment of water comprising a step of adsorption on ion-exchanging resin and a step of ballasted coagulation/flocculation and of separation, and corresponding plant
PT108658A (pt) * 2015-07-02 2017-01-02 Rauschert Portuguesa Sa Processo de reciclagem e reutilização de efluentes líquidos da extracção do azeite.
PT108658B (pt) * 2015-07-02 2019-02-26 Rauschert Portuguesa Sa Processo de reciclagem e reutilização de efluente liquído da extracção do azeite
GB2633940A (en) * 2022-05-31 2025-03-26 Pathogen Reduction Solutions Ltd Device for reflecting ultraviolet radiation
GB2633940B (en) * 2022-05-31 2025-09-17 Pathogen Reduction Solutions Ltd Device for reflecting ultraviolet radiation

Also Published As

Publication number Publication date
GR20030100295A (el) 2005-03-28
WO2005003037B1 (fr) 2005-05-06

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