WO2009062581A2 - Procédé en deux étapes de récupération de produits chimiques dans des eaux usées - Google Patents

Procédé en deux étapes de récupération de produits chimiques dans des eaux usées Download PDF

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Publication number
WO2009062581A2
WO2009062581A2 PCT/EP2008/008704 EP2008008704W WO2009062581A2 WO 2009062581 A2 WO2009062581 A2 WO 2009062581A2 EP 2008008704 W EP2008008704 W EP 2008008704W WO 2009062581 A2 WO2009062581 A2 WO 2009062581A2
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WO
WIPO (PCT)
Prior art keywords
sulfur
production
anaerobic
stage
wastewater treatment
Prior art date
Application number
PCT/EP2008/008704
Other languages
German (de)
English (en)
Other versions
WO2009062581A3 (fr
Inventor
Esa-Matti Aalto
Hans-Ludwig Schubert
Volker Paasch
Original Assignee
Voith Patent Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Voith Patent Gmbh filed Critical Voith Patent Gmbh
Publication of WO2009062581A2 publication Critical patent/WO2009062581A2/fr
Publication of WO2009062581A3 publication Critical patent/WO2009062581A3/fr

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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/286—Anaerobic digestion processes including two or more steps
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/345—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for biological oxidation or reduction of sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • 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
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
    • 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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention relates to a method for the recovery of chemicals from wastewater, which is produced in the production of pulp from lignocellulosic raw material by means of sulfur compounds.
  • the chemicals used in particular the sulfur salts, if not very small amounts be used- be recovered.
  • This is done today by first concentrating the effluent from pulp production by evaporation. Then the concentrated wastewater is burned at temperatures above 1000 0 C. The organic components (carbohydrates, lignin) are decomposed during combustion, the inorganic components are collected and processed for re-use for the production of pulp.
  • the disadvantages here are above all the considerable investment costs for the plants in which the recovery is carried out. is led.
  • a further disadvantage is the complex and complicated process management in the treatment of the digestion chemicals. In particular, the evaporation and burning of the wastewater is energy-consuming and requires expensive equipment.
  • the method requires the treatment of waste water from pulp production by means of anaerobic microorganisms.
  • COD chemical oxygen demand
  • the COD load is degraded by the action of microorganisms (bacteria), the oxygen, usually in the dark and at temperatures of 15 0 C to 25 0 C (psychrophilic microorganisms), from 25 0 C to 45 0 C (mesophilic microorganisms) or from 45 0 C to 70 0 C, isolated even at higher temperatures, (thermophilic microorganisms) these oxygen-consuming substances, mostly organic matter, degrade.
  • bacteria microorganisms
  • the oxygen usually in the dark and at temperatures of 15 0 C to 25 0 C (psychrophilic microorganisms), from 25 0 C to 45 0 C (mesophilic microorganisms) or from 45 0 C to 70 0 C, isolated even at higher temperatures, (thermophilic microorganisms) these oxygen-consuming substances, mostly organic matter, degrade.
  • the microorganisms are mixed as a sludge with the wastewater to be treated, with various methods are known, from mixing reactors via fixed bed reactors to reactors that are used as sludge bed or pellet reactors z.
  • the EGSB process (Expanded Granulated Sludge Blanket process) is also suitable for carrying out the process according to the invention.
  • the description of the construction and method of UASB reactors disclosed in the specified documents is herewith the subject of this patent application. It is expressly noted that the invention is not limited to certain processes or reactors of anaerobic wastewater treatment is limited.
  • wastewater and microorganisms are brought into contact with each other.
  • sludge, filtrate and gaseous components are formed.
  • the sludge makes up only a relatively small part with about 10% of the COD load.
  • the gas usually methane and carbon dioxide, called biogas, accounts for 90% of the COD load and is used to generate energy.
  • the filtrate is fed as purified wastewater to the receiving water.
  • Anaerobic wastewater treatment involves four main reaction steps. First, the organic substances that are detected as COD load are hydrolyzed. The hydrolysis products, eg. b. Oligomers or monomers are converted to acidogenesis into organic acids and / or alcohols. These organic acids or
  • Alcohols are converted by acetogenesis into hydrogen and acetates. Actetate and hydrogen are converted to methane as a result of methanogenesis.
  • the leading to the production of methane reactions are preferred in the known methods of wastewater treatment. At the same time run off unwanted, competing reactions from z. B. lead to the release of carbon dioxide and / or hydrogen sulfide.
  • Acetate compounds in particular serve as nutrients for bacteria, both for sulfur-reducing bacteria and for methane-producing bacteria.
  • the sulfur salts contained in the wastewater should be separated from the base (eg sodium, calcium, magnesium or ammonium) and converted into sulfur and / or sulfur compounds. Preference is given to the production of sulfur, hydrogen sulfide and / or sulfur dioxide. Sulfur floats on the filtrate, hydrogen sulfide is released as gas, sulfur dioxide is either gaseous or dissolved in water or filtrate.
  • the recovery rate of the sulfur salts of the wastewater is with the inventive method at least 10%, preferably up to 50%, usually up to 70%.
  • the anaerobic wastewater treatment has at least one stage for preferential production of sulfur and / or sulfur compounds and at least one stage for preferential production of methane and / or carbon dioxide.
  • microorganisms may be separately conditioned for each stage, on the one hand preferably conditioned for the production of sulfur and / or sulfur compounds, and on the other hand for the production of methane and / or carbon dioxide are conditioned. Competing reactions are thus selectively separated, resulting overall in improved process efficiency and more stable operation of the wastewater treatment leads.
  • the extensive separation of the production of sulfur and / or sulfur compounds, mainly hydrogen sulfide, from the production of biogas also allows easier processing of the released from the anaerobic microorganisms gases.
  • the plants can, for. For example, with regard to the building materials to be used, the gases that are more or less corrosive depending on the stage are better adapted to the different stages.
  • the base separated from the sulfur, which is dissolved in water is discharged with the filtrate.
  • the base is oxidized to carbonate, e.g. For example, sodium, calcium, magnesium or ammonium carbonate. But it can also be converted to hydroxides; a mixture of oxidation products is possible, for example in the form that carbonates and hydroxides are present side by side.
  • the inventive method can be carried out in the simplest case, each with a stage for the production of sulfur and / or sulfur compounds on the one hand and methane and carbon dioxide on the other.
  • multiple reactors can be operated in parallel.
  • the gaseous and / or dissolved in water sulfur compounds conditions and optionally the alkaline filtrate are recovered from wastewater chemicals available.
  • the inventive method operates at temperatures well below 100 0 C.
  • the suitable for the activity of psychrophilic, mesophilic or thermophilic microorganisms temperatures are at most 70 0 C, well below the temperatures at which the known recovery methods work.
  • low-molecular oxygen-consuming substances are also reacted in the at least one stage for the preferred production of sulfur and / or sulfur compounds.
  • Monomers and / or oligomers contained in the waste water of pulp production are degraded by the anaerobic microorganisms, which are preferably conditioned on the conversion of sulfur salts to sulfur and / or sulfur compounds.
  • higher molecular weight oxygen-consuming substances are also reacted in the at least one stage for the preferential production of methane and / or carbon dioxide.
  • Higher molecular oxygen-consuming substances typically lignin or lignin degradation products, but also higher molecular weight carbohydrates are degraded by the anaerobic microorganisms, which are preferably conditioned to the conversion of oxygen-consuming substances to methane and / or carbon dioxide. This special conditioning of the anaerobic microorganisms in each case to the degradation of low or high molecular weight oxygen-depleting substances overall improved degradation of the COD load of the wastewater is achieved.
  • methane and / or carbon dioxide in addition to the implementation of sulfur compounds is an advantageous option of the method according to the invention, because over conventional chemical recovery excess energy can be provided not only in the form of electricity and heat. Rather, a primary energy source is generated, which can be used and used much more diverse. It is particularly advantageous that this energy source can also be stored if necessary.
  • the anaerobic wastewater treatment degrades at least 5%, but preferably more than 25%, particularly preferably up to 50%, of the COD load originally present in the wastewater.
  • the process according to the invention gives priority to the recovery of the chemicals, it nevertheless contributes to the reduction of the COD load.
  • the implementation of sulfur compounds, which does not lead to a corresponding methane generation, contributes to a further improved energy balance of the process.
  • the COD load of the wastewater from the pulp production contains up to 150 g / l of COD, because then the recovery rate of the chemicals and the degradation rate of the COD are particularly high and the process can be carried out accordingly economically .
  • effluents of CTMP pulp or high yield pulp produced using sulfur compounds have COD loads in the aforementioned framework.
  • the recovered chemicals can be implemented in a preferred development with only a few, simple and energy-consuming steps in chemicals that can be used for reuse in a pulp digestion by means of sulfur salts.
  • sulfur is present as the reaction product of the anaerobic wastewater treatment. Sulfur is produced in particular when, in the context of anaerobic wastewater treatment, the sodium component of the spent liquor does not become sodium carbonate but rather essential alkaline sodium hydroxide is reacted.
  • the sulfur can be oxidized by means of oxygen supply, for example by burning, to sulfur dioxide and then further reacted with alkaline filtrate to alkali sulfite.
  • hydrogen sulfide may form during anaerobic wastewater treatment, which may be reacted with oxygen to form sulfur dioxide and then alkaline filtrate to alkali sulfite.
  • gaseous or dissolved in water sulfur dioxide can be reacted with alkaline filtrate to alkali sulfite.
  • It may also be a direct reaction of the hydrogen sulphide with water and alkali, e.g. with filtrate in the course of a gas scrubbing, to alkali sulphide. This demonstrates the simplicity of process management, which provides ready-to-use digestion solution without complex process steps.
  • anaerobic wastewater treatment may be preceded by an aerobic and / or anaerobic pretreatment of the wastewater.
  • a pretreatment for example, a pre-acidification
  • the pre-acidification is an anaerobic wastewater treatment, which proceeds in the acidic pH range, and which preferably leads to the formation of acetates.
  • an aerobic pretreatment can take place, for. B. by white rot fungi act on the waste liquor.
  • This biological pretreatment contributes to increasing the efficiency and stability of the anaerobic wastewater treatment when the chemicals in the wastewater are oxidized as much as possible before the anaerobic wastewater treatment according to the invention. Sulfur compounds are oxidized to sulfate, carbon compounds, as far as they are oxidized, are oxidized to carbonates.
  • a plant for the anaerobic wastewater treatment of waste water from a waste paper treatment sludge is removed containing anaerobic microorganisms.
  • This sludge is supplied over a period of about 3 to 6 months with a wastewater, which, starting from the waste water of waste paper processing, in steps of 5 percent by volume is increasingly replaced by wastewater of an alkaline sulphite process for the production of high-yield pulp, so that the microorganisms are completely converted to the new wastewater substrate at the end of the said period.
  • the alkaline sulfite process is described in DE 10 2006 027006. We expressly declare that the content of this patent application is also intended to be a disclosure of this patent application.
  • sodium sulfite is used to break down wood.
  • the yield of the process is 85% based on the originally used, oven-dry wood pulp. So it go during the digestion about 15% of the wood substance in solution and are discharged with the wastewater.
  • the effluent of such digestion of lignocellulosic raw material, here wood has a COD load of 55 g / l.
  • the pH of the waste water is between 6.5 and 7.0, making it ideal for efficient anaerobic microorganisms.
  • the wastewater leaves the pulp washing with a temperature of about 60 0 C and can thus be fed directly to the aerobic or anaerobic wastewater treatment.
  • the effluent from the high yield sulfite pulping contains lignin, including sulfonated lignin, carbohydrates, including cellulose and hemicelluloses, and digestion chemicals and unused chemicals.
  • This wastewater is then sent to a first stage of anaerobic wastewater treatment.
  • the wastewater is introduced below into a UASB reactor tower and rises in the tower, penetrating through the sludge / mesophilic microorganisms contained therein.
  • the anaerobic microorganisms conditioned on the treatment of this effluent preferably produce sulfur and / or sulfur compounds, especially hydrogen sulfide and sulfur dioxide.
  • the sulfates are first reacted. Most of the hydrogen sulfide escapes as gas, but part of it is also converted into sulfur dioxide with water, which partially escapes in gaseous form, partially remaining dissolved in water. At the same time low molecular weight oxygen-consuming substances, typically monomers or oligomers z. As lignin or carbohydrates) degraded. If the alkaline component of the wastewater is reacted proportionally or predominantly to sodium hydroxide instead of sodium carbonate, elemental sulfur also forms in the reaction of sulfur compounds.
  • the wastewater (the first-stage filtrate), which is largely purified from sulfur-containing compounds in the first stage of anaerobic wastewater treatment, is subsequently subjected to further wastewater treatment in a second anaerobic stage.
  • the reduction of the COD burden through the conversion to methane via the steps of hydrolysis, acidogenesis, acetogenesis and methanogenesis.
  • methane and carbon dioxide is formed.
  • the microorganisms are conditioned in the manner described for the first anaerobic stage.
  • the filtrate which still contains a remainder of the COD load and the sodium carbonate and / or hydroxide, is taken from overflows at the top of the tower.
  • the filtrate withdrawn at the overflow of the first UASB tower designed to produce sulfur compounds is introduced down into the second UASB tower to further reduce the COD load of the effluent and to increase the economic efficiency of the process by generating Further increase biogas.
  • Sulfur and sulfur compounds can be removed at the top of the first UASB tower and introduced directly into the filtrate produced at the overflow of the second UASB tower.
  • Elaborate drainage or storage systems, which must be designed for the corrosive hydrogen sulfide can thus be almost completely avoided. Elemental sulfur floats on the first stage filtrate. It can be withdrawn there and, like hydrogen sulfide, is converted by combustion into sulfur dioxide, which can then be further converted into sodium sulfite in aqueous solution with alkaline filtrate.
  • the filtrate has a reduced by 50% COD load compared to the wastewater.
  • the present in the form of sulfur salts in the wastewater sulfur was converted to 75% to hydrogen sulfide, sulfur dioxide (and subsequently using the alkali see filtrate to sodium sulfite).

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

La présente invention concerne un procédé de récupération de produits chimiques dans des eaux usées qui sont obtenues lors de la production de matière fibreuse à partir d'une matière de départ lignocellulosique par utilisation de sulfates, les eaux usées subissant un traitement anaérobie en au moins une étape, du soufre et/ou des composés de soufre étant produits. L'invention se caractérise en ce que le traitement anaérobie des eaux usées comporte au moins une étape de production préférentielle de soufre et/ou de composés de soufre, et au moins une étape de production préférentielle de méthane et/ou de dioxyde de carbone.
PCT/EP2008/008704 2007-11-12 2008-10-15 Procédé en deux étapes de récupération de produits chimiques dans des eaux usées WO2009062581A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007054207.2 2007-11-12
DE200710054207 DE102007054207A1 (de) 2007-11-12 2007-11-12 Zweistufiges Verfahren zur Chemikalien-Rückgewinnung aus Abwasser

Publications (2)

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WO2009062581A2 true WO2009062581A2 (fr) 2009-05-22
WO2009062581A3 WO2009062581A3 (fr) 2009-07-09

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Publication number Priority date Publication date Assignee Title
CN110694348B (zh) * 2019-10-28 2021-08-20 海南金海浆纸业有限公司 一种造纸涂料废渣解离***及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241943A (en) * 1962-04-13 1966-03-22 Bystrom Sven Gustav Method for the production of a fertilizer or soil improvement agent from sulfite waste liquor while recovering acids and combustible gases formed in the process
GB2143810A (en) * 1983-06-20 1985-02-20 Duncan Lagnese & Ass Inc Process for biological reduction of sulphur oxides
US4614588A (en) * 1985-08-22 1986-09-30 Dorr-Oliver Incorporated Method for sulfide toxicity reduction
EP0241999A1 (fr) * 1986-04-16 1987-10-21 Biothane Systems International B.V. Epuration anaérobie d'eaux résiduaires contenant des sulfates et des matières organiques
EP0356203A2 (fr) * 1988-08-23 1990-02-28 Sappi Limited Traitement d'effluents

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DE19815616A1 (de) 1998-04-07 1999-10-14 Zeppelin Silo & Apptech Gmbh Verfahren und Vorrichtung zum Reinigen von Abwasser
DE102005050997B4 (de) 2005-10-25 2007-10-04 Aquatyx Wassertechnik Gmbh Verfahren und Reaktor zur anaeroben Behandlung von Abwasser
DE102006027006A1 (de) 2006-06-08 2007-12-13 Voith Patent Gmbh Verfahren zum Herstellen von Faserstoff aus Holz

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3241943A (en) * 1962-04-13 1966-03-22 Bystrom Sven Gustav Method for the production of a fertilizer or soil improvement agent from sulfite waste liquor while recovering acids and combustible gases formed in the process
GB2143810A (en) * 1983-06-20 1985-02-20 Duncan Lagnese & Ass Inc Process for biological reduction of sulphur oxides
US4614588A (en) * 1985-08-22 1986-09-30 Dorr-Oliver Incorporated Method for sulfide toxicity reduction
EP0241999A1 (fr) * 1986-04-16 1987-10-21 Biothane Systems International B.V. Epuration anaérobie d'eaux résiduaires contenant des sulfates et des matières organiques
EP0356203A2 (fr) * 1988-08-23 1990-02-28 Sappi Limited Traitement d'effluents

Non-Patent Citations (4)

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Title
CHEN W ET AL: "The Treatment of a High Strength Pulp and Paper Mill Effluent for Wastewater Re-Use II) Biological Sulphate Removal from Effluent with a Low COD/Sulphate Ratio" ENVIRONMENTAL TECHNOLOGY, SELPER LTD, GB, Bd. 19, 1. Februar 1998 (1998-02-01), Seiten 163-171, XP009109749 ISSN: 0959-3330 *
L.H.A. HABETS, H.J. KNELISSEN: "In Line Biological Water Regeneration In A Zero Discharge Recycle Paper Mill" WAT.SCI.TECH., Bd. 35, 1997, Seiten 41-48, XP002526269 Elsevier Science *
VISSER A ET AL: "EFFECTS OF SHORT-TERM TEMPERATURE INCREASES ON THE MESOPHILIC ANAEROBIC BREAKDOWN OF SULFATE CONTAINING SYNTHETIC WASTEWATER" WATER RESEARCH, ELSEVIER, AMSTERDAM, NL, Bd. 27, Nr. 4, 1. April 1993 (1993-04-01), Seiten 541-550, XP000356359 ISSN: 0043-1354 *
WORSTER H E: "Semichemical Pulping for Corrugating Grades" PULP AND PAPER MANUFACTURE, XX, XX, Nr. ED. 3, 1. Januar 1991 (1991-01-01), Seiten 130-138, XP002464677 *

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DE102007054207A1 (de) 2009-05-14
WO2009062581A3 (fr) 2009-07-09

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