WO2013068253A1 - Procédé de neutralisation de substances nocives chargées négativement dans des fluides aqueux - Google Patents

Procédé de neutralisation de substances nocives chargées négativement dans des fluides aqueux Download PDF

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Publication number
WO2013068253A1
WO2013068253A1 PCT/EP2012/071331 EP2012071331W WO2013068253A1 WO 2013068253 A1 WO2013068253 A1 WO 2013068253A1 EP 2012071331 W EP2012071331 W EP 2012071331W WO 2013068253 A1 WO2013068253 A1 WO 2013068253A1
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WO
WIPO (PCT)
Prior art keywords
metal ions
cathode
anode
negatively charged
ions
Prior art date
Application number
PCT/EP2012/071331
Other languages
German (de)
English (en)
Inventor
Siegfried Egner
Christiane Chaumette
Alexander Karos
Original Assignee
Fraunhofer Gesellschaft Zur Förderung Der Angewandten Forschung E. V.
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 Fraunhofer Gesellschaft Zur Förderung Der Angewandten Forschung E. V. filed Critical Fraunhofer Gesellschaft Zur Förderung Der Angewandten Forschung E. V.
Publication of WO2013068253A1 publication Critical patent/WO2013068253A1/fr

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    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/01—Waste products, e.g. sludge
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/66—Salts, e.g. alums
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
    • 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
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • 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
    • C02F2303/10—Energy recovery
    • 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
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies

Definitions

  • the invention relates to a method for the neutralization of negatively charged impurities in aqueous media according to the preamble of claim 1.
  • the device comprises an electrolysis cell, wherein a cathode space is separated from an anode space by a cation exchange membrane or a microporous diaphragm.
  • DE 33 12 744 C2 describes a process for the electrochemical treatment of wastewater.
  • the wastewater to be treated is first fed to a first electrolysis cell with insoluble electrodes.
  • This first electrolysis cell comprises a cathode space and an anode space which are separated by a diaphragm. Wastewater leaving the anode compartment of the first electrolysis cell is supplied to the anode compartment of a second electrolysis cell. Wastewater leaving the cathode compartment of the first electrolysis cell is supplied to the cathode compartment of the second electrolysis cell.
  • the anode compartment and the cathode compartment of the second electrolysis cell are separated by a diaphragm.
  • the second electrolysis cell has soluble electrodes.
  • the separation of the waste water into a catalyzed stream which flows through the cathode chambers of both electrolysis cells and an anolyte current which flows through the anode chambers of both electrolysis cells prevents the formation of insoluble salt deposits on the soluble electrodes and thus their passivation.
  • After leaving the electrolysis cells of the anolyte and the catholyte are reunited and there is the formation of metal hydroxides, wherein the impurities in the wastewater are adsorbed by the metal hydroxides and removed with these as foam from the water surface.
  • the object of the invention is to provide a method and an electrolysis cell, with the help of which negatively charged impurities are neutralized without the addition of chemicals such as salts or polymers, and with little equipment.
  • a closed circulation of process water should be possible and a further process step, such as the separation of impurities, can be omitted.
  • the inventive method has the advantage that positively charged metal ions are released by electrolytic processes directly from a metal solid.
  • the inventive method is a cost effective way to conserve valuable resources, such as water or metal salts.
  • the metal ions comprise aluminum ions.
  • Aluminum ions, as Al 3+, are particularly easily produced electrolytically from a soluble anode (sacrificial anode) made of aluminum or an aluminum alloy. Since Al 3+ has the particularly high oxidation state III, it can bind many negatively charged impurities.
  • a pH of between 1 and 7 is established in an anolyte-side fluid.
  • the low pH has a favorable effect on the stability of the metal ions. This prevents or at least retards chemical precipitation as hydroxide.
  • An advantageous embodiment provides that negative charged ions (anions) generated at a cathode are retained in a cathode space.
  • the electrolysis cell is provided with a separator which separates the anode space from a cathode space and thus also restrains the anions formed in the cathode space. Thus, a neutralization is omitted.
  • the spatial separation by the separator also prevents the transport to and the attachment of the positively charged metal ions to the negatively charged cathode. Consequently, the generated metal ions remain in their most reactive form (high oxidation state) until they are fed to their use, the neutralization of negatively charged contaminants.
  • the process according to the invention can be used particularly advantageously if the negatively charged impurities are contained in a process water in papermaking. In papermaking large amounts of process water are needed. In order to save water, a circulation is possible when using the method according to the invention.
  • electrolytically generated metal ions By adding electrolytically generated metal ions, the addition of counterions, usually chloride ions, can be omitted. As a result, a continuous salination of the process water is avoided.
  • the process water does not have to be diluted with fresh water and it can be run in a closed circuit.
  • the positively charged metal ions and chemical and / or physical compounds, which are the positively charged metal ions are received with the negatively charged impurities embedded in the paper produced.
  • the process water without further treatment steps and without further waste stream, such as sludge from flocculation or precipitation can be recycled and eliminated the equipment and energy related costs of further treatment steps.
  • Electrolysis produces molecular oxygen at the anode and molecular hydrogen at the cathode. These two electrolysis gases can be collected and fed to further processes, such as energy conversion in a fuel cell. As a result, a part of the energy required for the electrolysis is recovered.
  • electrolytic reaction products be separated.
  • additional valuable substances such as hydrogen peroxide are formed during electrolysis.
  • the invention provides a process whose primary advantages are that metal ions, in particular aluminum ions in their highest oxidation state, for example as Al (III) ion, are produced electrolytically and remain unchanged until their final use. This is ensured by electrolytic adjustment of the pH and a spatial separation of the anode compartment from the cathode compartment. It goes without saying that the process is not only used in process waters of papermaking but can be used in all similar cases requiring a direct metering of metal ions.
  • the sole figure shows a schematic representation of an electrolytic cell for carrying out the method according to the invention.
  • the electrolysis cell comprises at least one soluble anode 10 (sacrificial anode) and at least one inert cathode 12.
  • the electrolysis cell may be designed as a planar-layered electrolysis cell with an electrode spacing of 1 mm to 5 cm.
  • Other conceivable embodiments of the electrolysis cell include flow and fixed bed cells, spray tower cells, thin-film cells or capillary gap cells.
  • the anode 10 is preferably made of aluminum or aluminum-containing metal alloys. Are also conceivable
  • Materials such as iron and / or magnesium or metal alloys containing iron and / or magnesium.
  • the anode 10 may be formed as a flat material or grid or include beds or porous media.
  • the anode 10 can assume any size, preferably the anode 10 has a surface area between 1 cm 2 and 10 m2.
  • the cathode 12 is preferably made of steel, nickel, precious metal, graphite or is represented by a conductive diamond coating.
  • the cathode 12 is preferably designed as a grid with 4 mm wide slots, for example expanded metal. Other embodiments include any mesh, foam, sintered body, fabric, nonwoven, bedding or sheet.
  • the cathode 12 may take on any size, preferably the cathode 12 has a surface area between 1 cm 2 and 10 m2.
  • the cathode 12 can also assume any size, preferably it has a surface area between 1 cm 2 and 10 m2. Often it is the same size as the anode 10.
  • the anode 10 and the cathode 12 are connected to a respective pole of a current source 14.
  • the current source 14 comprises a DC power source, the positive pole of the current source 14 being connected to the anode 10 and the negative pole of the current source 14 being connected to the cathode 12. It is also conceivable cyclic Umpolung of DC or AC voltage in different frequencies.
  • a space arranged between anode 10 and cathode 12 is divided by a separator 16 into a cathode space 18 and an anode space 20.
  • the separator 16 comprises a semipermeable membrane, for example an ion exchange membrane, preferably a cation exchange membrane (for example Nafion N551 or Fumasep) or a microporous diaphragm with a pore size of 10 nm to 0.1 mm.
  • the separator 16 may be designed with or without a support structure.
  • the cathode compartment 18 and the anode compartment 20 are filled with an electrically conductive material in solid or liquid form. It is conceivable that in the cathode space 18 and / or in the anode space 20 flow-guiding packing, for example, a plastic grid, are arranged.
  • Anolyte-side fluid 24 is fed into the anode compartment 18, represented by arrow 22.
  • the anolyte-side fluid 24 preferably comprises tap water having a pH of 4 to 8 and a conductivity of 300 to 3000 ⁇ S / cm. Also conceivable are any aqueous solutions, such as filtered process water of the paper industry.
  • 10 positively charged metal ions for example, aluminum ions
  • the separator 16 which spatially separates the anode compartment 18 from the cathode compartment 20, prevents transport of the metal ions to the cathode 12.
  • the metal ions remain in the anolyte-side fluid 24.
  • the release of the metal ions causes the pH of the anolyte-side fluid 24 to drop Precipitation of the metal ions as hydroxide delays, or is prevented.
  • the anolyte-side fluid 24 leaves the electrolytic cell at an arrow 26 in the following preferred composition: water with pH values 1 to 7 and aluminum ions in colloidal form. It is also possible that the electrolysis gases, in particular oxygen, water vapor, chlorine gas and an aqueous solution with metal ions leave the electrolysis cell at arrow 26.
  • the cathode chamber 20 is in countercurrent (from an arrow 28 ago) with a conductive katolyt Cruem fluid 30, for example, water or humid air, flows through.
  • a conductive katolyt Cruem fluid 30 for example, water or humid air, flows through.
  • the essentially liquid or essentially gaseous fluid 30 leaves the electrolysis cell at an arrow 32 loaded with electrolysis gases, in particular hydrogen and water vapor and dilute hydrochloric acid solution.
  • ions such as OH -
  • separator 16 At the cathode 12 resulting negative ions, such as OH - , are retained by the separator 16 in the cathode compartment 18, so that neutralization with the positive ions in the anode compartment 18 is prevented.
  • the anolyte-side fluid 24 is added to the process water after leaving the electrolytic cell. There, the positive metal ions combine with the negatively charged impurities contained therein. The resulting chemical / physical compounds are embedded in the paper produced and thus removed from the process water. In this way, the process water can be recycled without further treatment steps.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

L'invention concerne un procédé de neutralisation de substances nocives chargées négativement dans des fluides aqueux par l'addition de substances chargées positivement, caractérisé en ce que les substances chargées positivement contiennent des ions métalliques, les ions métalliques étant produits par électrolyse à partir d'un solide métallique.
PCT/EP2012/071331 2011-11-09 2012-10-29 Procédé de neutralisation de substances nocives chargées négativement dans des fluides aqueux WO2013068253A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011085967.5 2011-11-09
DE201110085967 DE102011085967A1 (de) 2011-11-09 2011-11-09 Verfahren zur Neutralisation negativ geladener Störstoffe in wässrigen Medien

Publications (1)

Publication Number Publication Date
WO2013068253A1 true WO2013068253A1 (fr) 2013-05-16

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Application Number Title Priority Date Filing Date
PCT/EP2012/071331 WO2013068253A1 (fr) 2011-11-09 2012-10-29 Procédé de neutralisation de substances nocives chargées négativement dans des fluides aqueux

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DE (1) DE102011085967A1 (fr)
WO (1) WO2013068253A1 (fr)

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DE102016212048A1 (de) * 2016-07-01 2018-01-04 Erdwärme Neustadt-Glewe GmbH Verfahren zur Behandlung von Geothermalfluid- oder Formationswasserströmen durch kontinuierliche elektrochemische Abtrennung reduzierbarer Metall- und / oder Metalloidionen aus dem Förderstrom
CN115304215A (zh) * 2022-07-29 2022-11-08 绍兴华南纺织印染有限公司 一种印染废水处理方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
DE3312744C2 (fr) 1982-04-13 1987-12-03 Leningradskij Technologiceskij Institut Cholodil'noj Promyslennosti, Leningrad, Su
SU1745692A1 (ru) * 1989-08-07 1992-07-07 Запорожский индустриальный институт Установка дл очистки воды от ионов т желых металлов
JP2008055357A (ja) * 2006-08-31 2008-03-13 Daio Paper Corp 排水の処理方法
DE102009005011A1 (de) 2009-01-17 2010-07-22 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Verfahren und Vorrichtung zur elektrochemischen Desinfektion von Trink- und Brauchwasser mit hohen Härtegehalten
WO2010098492A1 (fr) * 2009-02-25 2010-09-02 国立大学法人山口大学 Floculant de type sel métallique activé et son procédé de production
WO2012139879A1 (fr) * 2011-04-12 2012-10-18 Voith Patent Gmbh Procédé de traitement de liquides et de dispersions avec des ions métalliques produits par voie électrolytique au moyen d'une cellule d'électrolyse à deux chambres

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NL8902195A (nl) * 1989-08-31 1991-03-18 Esmil Water Systems Bv Membraanelektrolyse-inrichting.
US6645366B2 (en) * 2000-11-01 2003-11-11 Sanyo Electric Co., Ltd. Waste water treatment device
US20050167285A1 (en) * 2004-01-30 2005-08-04 Council Of Scientific And Industrial Research Electrochemical method for the removal of arsenate from drinking water

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3312744C2 (fr) 1982-04-13 1987-12-03 Leningradskij Technologiceskij Institut Cholodil'noj Promyslennosti, Leningrad, Su
SU1745692A1 (ru) * 1989-08-07 1992-07-07 Запорожский индустриальный институт Установка дл очистки воды от ионов т желых металлов
JP2008055357A (ja) * 2006-08-31 2008-03-13 Daio Paper Corp 排水の処理方法
DE102009005011A1 (de) 2009-01-17 2010-07-22 Eilenburger Elektrolyse- Und Umwelttechnik Gmbh Verfahren und Vorrichtung zur elektrochemischen Desinfektion von Trink- und Brauchwasser mit hohen Härtegehalten
WO2010098492A1 (fr) * 2009-02-25 2010-09-02 国立大学法人山口大学 Floculant de type sel métallique activé et son procédé de production
WO2012139879A1 (fr) * 2011-04-12 2012-10-18 Voith Patent Gmbh Procédé de traitement de liquides et de dispersions avec des ions métalliques produits par voie électrolytique au moyen d'une cellule d'électrolyse à deux chambres

Non-Patent Citations (2)

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Title
MOUEDHEN ET AL: "Behavior of aluminum electrodes in electrocoagulation process", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 150, no. 1, 19 December 2007 (2007-12-19), pages 124 - 135, XP022394879, ISSN: 0304-3894, DOI: 10.1016/J.JHAZMAT.2007.04.090 *
SRIDHAR R ET AL: "Treatment of pulp and paper industry bleaching effluent by electrocoagulant process", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 186, no. 2, 7 December 2010 (2010-12-07), pages 1495 - 1502, XP028363419, ISSN: 0304-3894, [retrieved on 20101214], DOI: 10.1016/J.JHAZMAT.2010.12.028 *

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