EP3849947A1 - Dispositif et procédé d'épuration d'eaux usées - Google Patents

Dispositif et procédé d'épuration d'eaux usées

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Publication number
EP3849947A1
EP3849947A1 EP19762171.7A EP19762171A EP3849947A1 EP 3849947 A1 EP3849947 A1 EP 3849947A1 EP 19762171 A EP19762171 A EP 19762171A EP 3849947 A1 EP3849947 A1 EP 3849947A1
Authority
EP
European Patent Office
Prior art keywords
cathode
waste water
cleaning device
anode
wastewater
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.)
Withdrawn
Application number
EP19762171.7A
Other languages
German (de)
English (en)
Inventor
Andreas Bulan
Rainer Weber
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.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3849947A1 publication Critical patent/EP3849947A1/fr
Withdrawn legal-status Critical Current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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C02F1/46109—Electrodes
    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • 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
    • C02F1/46109—Electrodes
    • C02F2001/46128—Bipolar electrodes
    • 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
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • 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
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46147—Diamond coating
    • 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
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C02F2001/46166—Gas diffusion electrodes
    • 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
    • C02F2101/30—Organic 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
    • C02F2101/30—Organic compounds
    • C02F2101/305—Endocrine disruptive agents
    • 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
    • C02F2103/005—Black water originating from toilets
    • 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
    • C02F2201/008—Mobile apparatus and plants, e.g. mounted on a vehicle
    • 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
    • C02F2201/4612—Controlling or monitoring
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4613—Inversing polarity
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/46135—Voltage
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46125—Electrical variables
    • C02F2201/4614—Current
    • 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
    • C02F2201/4612—Controlling or monitoring
    • C02F2201/46145—Fluid flow
    • 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
    • C02F2201/4616—Power supply
    • C02F2201/4617—DC only
    • 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
    • C02F2201/4618—Supplying or removing reactants or electrolyte
    • C02F2201/46185—Recycling the cathodic or anodic feed
    • 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
    • C02F2201/4619—Supplying gas to the electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/42—Liquid level
    • 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
    • C02F2301/02—Fluid flow conditions
    • C02F2301/024—Turbulent

Definitions

  • the invention relates to a device and a method for purifying waste water using electrochemically generated hydroxide radicals and a gas diffusion electrode as the cathode.
  • Decentralized wastewater treatment is therefore a great challenge.
  • the cleaning processes known from the prior art have a number of disadvantages, which are explained below.
  • the removal of organic contaminants from industrial wastewater can be carried out in a stationary manner according to the prior art by stripping with steam in columns and subsequent treatment of the wastewater with activated carbon. This is hardly feasible for decentralized applications, since corresponding columns are not available or cannot be handled in mobile use.
  • the activated carbon loaded with the contaminants must be disposed of or recycled.
  • the decentralized cleaning processes known from the prior art for cleaning waste water containing organic compounds by using adsorber material such as e.g. Activated carbon has the disadvantage that the activated carbon has to be replaced and refurbished regularly.
  • the content of organic impurities in the cleaned process water must be constantly checked, since the adsorber materials have a limited absorption capacity, which means a further technical effort.
  • Waste water treatment with ozone is complex because ozone has to be produced from oxygen, which has to be provided as an additional component.
  • the poor yield in ozone production typically carried out by means of an ozonizer and the destruction of any excess ozone, require an additional apparatus for the aftertreatment of the process water and the exhaust air during the cleaning process in order to avoid the release of toxic ozone.
  • Decentralized wastewater treatment is also e.g. useful for the treatment of hospital wastewater or wastewater from old people's homes and nursing homes, which in addition to normal waste materials (such as urea, protein, glucose, humic acids), often also drug residues or metabolites of antibiotics, hormones or other compounds that are difficult to break down, such as painkillers, cytostatics or X-ray contrast agents contain.
  • waste materials such as urea, protein, glucose, humic acids
  • Electrochemical wastewater treatment would be a viable method for decentralized wastewater treatment.
  • Boron-doped diamond electrodes (BDD) or other electrodes with a high oxidizing power could be used.
  • anodes coated with lead dioxide CN 000104404566) could be used.
  • a technical solution and a cleaning device were sought which enable electrochemical wastewater treatment in which the evolution of hydrogen at the cathode is avoided and in particular a further oxidizing agent is generated. Furthermore, the purification of waste water without foam formation due to the cathodically generated hydrogen should be able to be carried out.
  • the object of the invention is the removal of organic contaminants from wastewater which can be processed in a simpler manner, e.g. can be carried out without the use of absorbents, for example activated carbon, or by other complex cleaning processes as described above.
  • a compact and efficient wastewater treatment unit is particularly desirable, which can be used without additional auxiliaries (e.g. Disinfectants, chlorinated lime, adsorbents) and there are no other by-products to be disposed of.
  • auxiliaries e.g. Disinfectants, chlorinated lime, adsorbents
  • the invention relates to a purification device for the purification of wastewater from a wastewater source from a tank and / or a collecting device at least comprising an electrolysis toe at least comprising an electrode space with an anode, suitable for generating hydroxide radicals, and a cathode suitable for reducing oxygen , which is designed as a gas diffusion electrode, a, in particular lockable, waste water supply line and a, in particular lockable, discharge line for the cleaned waste water, further comprising a gas space which is separated from the electrode space by the cathode, at least one supply line and a discharge line for an oxygen-containing one Gas, which are connected to the gas space, and electrical connections, which switchably connect the anode and the cathode to a DC voltage source.
  • Condensate formed in the gas space is discharged via an optional condensate drain, which is connected to the supply line to the electrode space.
  • the electrode space is provided with an additional outlet for gases from the electrode space.
  • the gas outlet is preferably connected to a gas cleaning system.
  • Gas cleaning can e.g. activated carbon cleaning. For this, however, only a fraction of activated carbon is required compared to the generally known adsorptive purification of the contaminated wastewater.
  • the anode preferably has a coating with diamond, in particular a coating made of boron-doped diamond (BBD).
  • BBD boron-doped diamond
  • BDD electrodes in wastewater treatment is generally known and is described, for example, at http: // archiv. current newsreel / 2006 / week 8b / week8b tml
  • the electrodes require high mechanical stability, since there may also be particles in the wastewater that mechanically, i.e. attack abrasively and limit their lifespan and functionality.
  • the anode and / or the cathode is therefore designed as a flat structure, in particular as a sheet, expanded metal or metal mesh coated with an electrocatalyst.
  • alkaline earth metal ions are present in most wastewater.
  • the increase in pH at the cathode during wastewater treatment can precipitate the alkaline earth metal hydroxides at the cathode or, if carbonates are present, the alkaline earth metal carbonates, which block the surface of the electrode, so that further electrolysis is hindered or impossible. Removal of the cathode and its cleaning or replacement is necessary and leads to high maintenance costs and worsens the economy of the cleaning process.
  • the cathode is a bifunctional cathode which is suitable for electrochemical oxygen reduction and for electrochemical oxygen production, in particular a bifunctional cathode produced on the basis of a mixed oxide with a perovskite structure with a polymeric hydrophilic component, in particular a fluoropolymer PTFE and a carbon material selected from the series: carbon nanotubes, carbon black, graphite, glassy carbon.
  • a mixed oxide with a perovskite structure is, in particular, a mixed oxide of one or more alkaline earth metals from the series; Calcium, strontium, barium, preferably strontium, barium, understood with at least one metal from the series: lanthanum, manganese, cobalt and iron, preferably lanthanum and manganese, the mixed oxide having the crystal structure of perovskite.
  • a mixed oxide of lanthanum, manganese and strontium with a perovskite structure is particularly preferred.
  • the supply of the waste water is preferably attached to the electrode space below the cathode or laterally to the cathode in the lower third of the electrode space.
  • a preferred variant of the new cleaning device is characterized in that the distance between the anode and cathode is in the range of 1-10 mm. If the gap is less than 1 mm wide, the passage between the anode and cathode can be blocked by suspended matter. Above a gap width of 10 mm, the operating voltage for the operation of the electrolyzer rises noticeably, so that the electrolyzer requires too much electrical energy.
  • the cathode is preferably designed as a gas diffusion electrode and consists of at least one carrier and an electrochemically active layer and a gas diffusion layer.
  • the electrochemically active layer and the gas diffusion layer form a unit.
  • the cathode is a gas diffusion electrode based on carbon material which is suitable for the production of hydrogen peroxide, in particular with at least one carbon material selected from the series: carbon nanotubes, carbon black, graphite, glassy carbon.
  • a new cleaning device is further preferred, which is characterized in that the cathode comprises fine-grained carbon material, in particular with an average grain diameter of 1 to 60 micrometers, and is present in and mixed with a polymeric hydrophilic component, in particular a fluoropolymer, particularly preferably with PTFE a mechanically stable, preferably electrically conductive support is applied.
  • a polymeric hydrophilic component in particular a fluoropolymer, particularly preferably with PTFE a mechanically stable, preferably electrically conductive support is applied.
  • the polymeric hydrophilic component especially the fluoropolymer, particularly preferably the PTFE used to make the cathode fine-grained, i.e. it has an average particle diameter in the range from 100 to 1000 micrometers, preferably 250 to 700 micrometers.
  • the material of the carrier is selected in particular from the series: nickel, gold-plated nickel, silver, PTFE-coated glass fiber, plastic fabric consisting particularly preferably of polypropylene or polyethylene or carbon fibers. Carbon fibers or gold-plated nickel are preferred.
  • the cathode comprises an electrocatalyst for oxygen reduction to form hydroxide ions.
  • the cathode comprises an electrocatalyst or mixed catalyst which is suitable not only for the formation of hydroxide ions but also for the reduction of oxygen to hydrogen peroxide.
  • the cathode comprises a bifunctional catalyst which catalyzes both the oxygen reduction (ORR oxygen reduction reaction) and the oxygen oxidation (OEE oxygen evolution reaction). Mixtures of two different catalysts, each of which enables one of the types of reactions mentioned, can also be used.
  • the waste water feed line connects the electrolysis cell to a waste water tank and / or a waste water collection device.
  • the electrolysis cell is connected to a tank for holding purified water via a waste water discharge line.
  • a waste water discharge line In principle, it is possible to dispose of the cleaned wastewater from the tank for disposal or reuse as industrial water.
  • the cleaning device has a lockable circuit line which is connected in particular to the line for purified water and the waste water supply line, possibly via the electrolyte reservoir.
  • the circulation pump pumps the wastewater from the electrolysis template through the toe and back.
  • the tank can be filled batch-wise from the collection container. When the wastewater from the tank has been cleaned and discharged via the line, the tank can be refilled from the collecting tank.
  • the anode and the cathode are electrically connected to a direct voltage source so that they can be reversed.
  • All basically known DC voltage generators such as rectifiers, batteries and accumulators, can be considered as DC voltage sources.
  • Accumulators are preferably used for mobile operation, which are preferably supplied with current via photo vol tai kzel 1 s.
  • a new cleaning device with at least one monitoring unit for monitoring one or more of the measurement variables from the series is further preferred: electrolysis current, electrolysis voltage, fill level of the tanks for the waste water and the cleaned waste water, volume flow of the waste water, pH value of the waste water and degree of purification of the wastewater in the circuit is provided by the toe and cleaned wastewater.
  • inerting can take place as a safety measure in order to avoid the formation of oxyhydrogen.
  • the amount of hydrogen can be diluted below the explosion limit with an inert gas.
  • a corresponding excess of air can also be used for inerting.
  • an inert gas is fed into the tank, for example.
  • the degree of cleaning is monitored with the aid of a detector for determining the total content of organic compounds (TOC total organic content), particularly preferably with the aid of an optical or IR detector.
  • TOC total organic content particularly preferably with the aid of an optical or IR detector.
  • Another object of the invention is a method for the electrochemical purification of wastewater contaminated with organic substances and optionally additionally with inorganic substances using a new cleaning device as described in this application, which is characterized in that wastewater from a tank and / or a collecting device via the Waste water supply is introduced into the electrode space of the electrolysis toe continuously or discontinuously, preferably continuously, by applying an electrical voltage between the anode and cathode to produce hydroxide ions or hydrogen peroxide on the cathode and hydroxide radicals on the anode and treated and after sufficient Cleaning is derived via the drain.
  • wastewater is recirculated into the electrode space one or more times.
  • the cleaned wastewater is particularly preferably recirculated until a predetermined degree of purification is achieved and particularly preferably recirculated in a closed circuit.
  • the method is particularly preferably carried out such that the waste water flows through the electrode space in a turbulent flow (in particular with a Reynold number> 2300).
  • the average residence time of the waste water in the electrode space is preferably typically 0.1 to 15 seconds.
  • the anode and cathode are electrically reversed at intervals during the operation of the electrolysis toe in order to switch between the oxygen reduction mode and to change Sauer substance development mode on the cathode.
  • the anode then switches between the production of hydroxide ions for the production of hydrogen.
  • the gas diffusion electrode is in ORR mode and the BBD electrode in OEE mode, inerting is necessary to avoid the formation of explosive gas mixtures.
  • the interval is preferably selected so that the possible deposits on the electrode can be removed with a brief operation in the oxygen development mode.
  • the interval time for operating the cathode in the oxygen reduction mode is set depending on the amount of charge that has flowed per liter of wastewater to be cleaned.
  • the amount of charge in the oxygen reduction mode (ORR) is between 10 and 120 Ah / L and in the oxygen development mode (OEE) 0.01 to 10 Ah / L (Ah stands for the charge in ampere-hours).
  • the electrode areas and current densities during operation must be selected so that they are 100 to 6000 A / m 2 in ORR mode and 50 to 4000 A / m 2 in OEE mode.
  • a charge quantity of 0.01 Ah / mg TOC to 5 Ah / mg TOC is introduced per milligram of organic contamination, determined as TOC.
  • the cleaned wastewater is in particular expediently passed into a service water tank or fed to a delivery unit.
  • a chopper pump is preferably used in the waste water feed line or in the feed line to the electrolysis cell for comminuting solid particles to convey the waste water to be cleaned. Possibly.
  • the circulation pump can also be designed as a chopper pump.
  • Another object of the invention is the use of the new cleaning device described above for cleaning waste water in vehicles, in particular in trains, coaches and mobile homes, in airplanes and ships, or in particular in mobile toilets.
  • the cleaning system described can be used as a stationary system for the treatment of problematic waste water in agricultural production facilities, holiday homes, swimming pools, but in particular in hospitals or old people's and nursing homes, preferably for the safe removal of drug residues or metabolites from hormones, painkillers, X-ray contrast media, cytostatics or antibiotics from the wastewater before these wastewaters are diluted with municipal wastewater.
  • the mobile or stationary cleaning device can also be used for cleaning collected waste water from cleaning processes, e.g. in the rinsing / cleaning of devices for applying plant protection products.
  • the cathode is of crucial importance for carrying out the cleaning process.
  • the cathode is designed in particular as a gas diffusion electrode (GDE) with which hydroxide ions and, if appropriate, additional hydrogen peroxide are formed from oxygen, water and electrical energy. Together with the OH radicals generated on the anode, a particularly high cleaning effect can be achieved.
  • GDE gas diffusion electrode
  • the electrical current is used both at the anode and at the cathode to produce oxidants, which makes the process particularly efficient.
  • the electrolysis toe can be operated with reversed polarity, as a result of which the cathode is switched as an anode. Oxygen and protons are developed on the original cathode. The pH value is reduced by the protons, which leads to a dissolution of the alkaline earth carbonates or hydroxides. Sauer substance development also contributes to the removal of the precipitated hydroxides and carbonates.
  • GDE should in particular contain a catalyst which can carry out both oxygen reduction and oxygen oxidation.
  • a reversible GDE should also be referred to here as a bifunctional GDE.
  • a bifunctional GDE is particularly preferably used in the new process and in the new cleaning device, which are produced analogously to the drying process disclosed in DE 102005023615 A1 for the production of silver-based GDEs for chlor-alkali electrolysis.
  • FIG. 1 shows a schematic representation of the new wastewater treatment device
  • the gas diffusion electrode is produced as follows as an example:
  • a mixture consisting of PTFE type TF 2053Z, with a proportion of 20% by weight, a mixed oxide with a perovskite structure obtained from the process described below with a proportion of 60% by weight, and carbon (conductive carbon black) from Timcal, type C65 with 15 wt .-% and graphite Timcal Type KS 6 with a proportion of 5 wt .-% were mixed at an average temperature of 48.5 ° C with an IKA mill in intervals of 5 * 20s.
  • the powder mixture was cooled to 20 ° C. and sprinkled onto a nickel wire mesh with a wire thickness of 0.14 mm and a mesh width of 0.5 mm, so that a powder layer of 4 mm was formed.
  • the powder layer was then pressed with a roller at a line force of 0.65 kN / cm.
  • the resulting electrode had a thickness of 0.68 mm.
  • the mixed oxide with perovskite structure used was produced as follows: A mixed oxide with perovskite structure of the following composition was obtained: Lao , 9Sro , i Mn03.
  • the procedure for producing the perovskite was as follows: A mixture of sodium carbonate, water, lanthanum nitrate, manganese nitrate and strontium nitrate was used in a 30 l kettle, which corresponded to the stoichiometric composition of the perovskite. The resulting precipitate was separated off and washed twice on a filter press. Between the two filter runs, the precipitate was mashed with an Ultraturrax and the mixture was left to stand overnight. The separated solid was dried at 90 ° C. overnight in a vacuum drying cabinet. The solid was then calcined at 1000 ° C. for 5 hours in an air atmosphere. The BET surface area was 5.7 m 2 / g. The phase was confirmed by XRD.
  • alkaline earth mixed oxides with a perovskite structure e.g. based on barium, strontium, cobalt and iron, particularly preferably a mixed oxide of the composition Bao.5 Sro.5 Cou.x Feo.2 O3 or Lao.6Cao.4Co03 can be used.
  • the analysis of the TOC value to maintain the cleaning effect was carried out according to DIN EN 1484, publication date: 1997-08.
  • the vario TOC cube TM device from elementar was used.
  • the pH value was measured using a FiveEasy TM pH electrode from Mettler Toledo.
  • a synthetic wastewater was used for the experiments in the examples because of the reproducibility.
  • the wastewater had the following composition: 10 g / L urea, 10 mg / L glucose, 20 mg / L proteins (protein).
  • the pH was 4.6.
  • Total TOC content 2000 mg / L
  • Example 2 (according to the invention; GDE for H2O2 production)
  • the cleaning device 1 used for carrying out the wastewater treatment is shown schematically in FIG. 1.
  • the representation does not reflect the actual proportions.
  • the main components of the cleaning device are the electrochemical cell 22, a storage tank 3 for the waste water 2 and a pump circuit 15; 18 for the waste water.
  • the electrochemical cell 22 consists of an anode half-shell 25 with an expanded metal made of niobium, which had a boron-doped diamond coating, as anode 6, a cathode half-shell 24 with a gas diffusion electrode (GDE) 7 and a gas space 11.
  • GDE gas diffusion electrode
  • Anode half-shell and anode form with the cathode half-shell and a common electrode space 5 on the liquid side in front of the GDE.
  • the GDE 7 separates the common electrolyte space 5 from the gas space 11. Any condensate is discharged from the gas space 11 via the line 14.
  • An outlet line 20 for gases (essentially CO2) connects the electrode space 5 to a gas cleaning system 21 or a collector. Furthermore, gas was fed from the storage container 3 to the gas cleaning system 21 via the line 20a. Unwanted gas components are removed in the gas cleaning system 21.
  • the storage tank 3 also has a lockable connection line for the possible introduction of inert gases (line 50) or a lockable connection line for the introduction of liquids for pH adjustment (line 51 for acids or bases).
  • the storage tank 3 is connected via a waste water feed line 8 and the feed pump 27 to an external waste water tank (collecting tank 3a) with an external waste water inlet 40a or optionally directly to an external waste water inlet 40.
  • the storage tank 3 is also connected via a waste water discharge line 9 to a tank 17 for purified water 10.
  • Shut-off valves 28a and 28b are provided in lines 8 and 9, respectively.
  • the electrode areas of anode 6 and cathode 7 were each 100 cm 2 in the test .
  • the distance between the cathode 7 and the anode was 5 mm (FIG. 1 represents only the principle and is therefore not an accurate representation).
  • Anode half-shell 25 and cathode half-shell 24 are electrically insulated from one another (by the insulator 23 made of PTFE).
  • An anode 6 consisting of niobium in the form of an expanded metal was used, which had a commercially available BDD coating from CONDIAS, Diachem®.
  • the dimensions of electrodes 6 and 7 were 10 cm in width, 2 mm in depth and 10 cm in height.
  • the anode 6 was installed in the cell 22 in such a way that the solution 2 to be cleaned flows past the anode 6 and the cathode 7.
  • the distance between the anode 6 and the rear wall of the anode half-shell 25 was 2 mm.
  • a hydrogen peroxide-forming GDE was used as the GDE. This was produced in analogy to the production process for gas diffusion electrodes based on silver for chlor-alkali electrolysis (dry production process) described in DE 102005023615 A1.
  • the GDE was specifically produced as follows:
  • the powder mixture was cooled to 20 ° C. and sprinkled onto a gold-plated nickel mesh with a wire thickness of 0.14 mm and a mesh size of 0.5 mm, so that a powder layer of 4 mm was formed.
  • the powder layer was then pressed with a roller at a line force of 0.46 kN / cm.
  • the electrode was then annealed at 340 ° C. for 2 h.
  • the resulting electrode had a thickness of 0.60 mm.
  • Centrifugal pump was used as pump 26.
  • An electrolyte volume flow of 10 l / h was set.
  • Oxygen with a content of at least 99.5 vol% was added via line 12 into gas space 11, excess oxygen was removed again via 13.
  • the oxygen volume flow was 15 L / h.
  • a current of 5.1 mA was set at the voltage supply 19, the initial cell voltage being 12V.
  • the temperature of the electrolyte (waste water) in the cell was initially 24 ° C. Samples were taken every hour to determine the TOC content.
  • a TOC reduction of 1120 mg TOC / L (waste water) could be achieved with 25 Ah / L.
  • Example 3 (According to the Invention - Bifunctional GDE)
  • the resulting electrode had a thickness of 0.68 mm.
  • the electrodes 6 and 7 were electrically connected to a voltage supply 19 with polarity reversal.
  • a current of 5 A was set at the voltage supply, the initial cell voltage being 12 V.
  • the temperature of the electrolyte in the cell was initially 24 ° C. Samples were taken every hour to determine the TOC content.
  • a TOC reduction of 1280 mg TOC / E (wastewater) could be achieved with 25 Ah / kg.
  • Example 2 An experiment was carried out with a device as in Example 2, but instead of a gas diffusion electrode, an electrode was used which develops hydrogen.
  • the cathode was manufactured as follows:
  • a dispersion is made up of the following components:
  • the mixed dispersion was applied by filling in 9 successive coating steps on an electrically conductive support, a carbon fleece (manufacturer SGL Carbon).
  • the coated carrier was dried at 120 ° C. for 1 hour and then sintered at a temperature of approx. 340 ° C. for 2.5 hours.

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  • Chemical & Material Sciences (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 dispositif d'épuration (1) et un procédé pour épurer des eaux usées (2) issues d'un réservoir (3) et/ou d'une installation collectrice (3a). Le dispositif d'épuration présente au moins une cellule d'électrolyse qui comprend : au moins une chambre d'électrodes (5) dotée d'une anode (6) qui est adaptée pour produire des radicaux hydroxyde, et une cathode (7) qui est adaptée pour réduire l'oxygène et se présente sous la forme d'une électrode à diffusion gazeuse ; une conduite d'amenée d'eaux usées (8) et une conduite d'évacuation d'eaux usées (9) pour les eaux usées épurées (10) ; une chambre à gaz (11) qui est séparée de l'espace d'électrodes (5) par la cathode (7) ; au moins une conduite d'amenée (12) et une conduite d'évacuation (13) pour un gaz contenant de l'oxygène, reliées à la chambre à gaz (11) ; et des bornes de contact électrique (19a) et (19b) qui relient de façon commutable l'anode et la cathode à une source de tension continue (19).
EP19762171.7A 2018-09-10 2019-09-05 Dispositif et procédé d'épuration d'eaux usées Withdrawn EP3849947A1 (fr)

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EP18193407.6A EP3620438A1 (fr) 2018-09-10 2018-09-10 Procédé et dispositif de nettoyage des eaux usées
PCT/EP2019/073689 WO2020053063A1 (fr) 2018-09-10 2019-09-05 Dispositif et procédé d'épuration d'eaux usées

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120031852A1 (en) * 2009-04-06 2012-02-09 Sa Envitech S.R.L. Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes
WO2021045191A1 (fr) * 2019-09-05 2021-03-11 デノラ・ペルメレック株式会社 Appareil de production d'une solution aqueuse acide et procédé de production d'une solution aqueuse acide

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
EP0410946B1 (fr) * 1989-07-24 1994-05-04 Tanaka Kikinzoku Kogyo K.K. Décomposition de substances nuisibles
DE10048030A1 (de) 2000-09-26 2002-04-11 Degussa Verfahren zur elektrochemischen Herstellung von Wasserstoffperoxid
DE10048299A1 (de) * 2000-09-29 2002-05-29 Aqua Butzke Werke Gmbh Vorrichtung zur elektrolytischen Wasserdesinfektion unter Vermeidung katodischer Wasserstoffentwicklung
US6949178B2 (en) * 2002-07-09 2005-09-27 Lynntech, Inc. Electrochemical method for preparing peroxy acids
US7645543B2 (en) 2002-10-15 2010-01-12 Polyplus Battery Company Active metal/aqueous electrochemical cells and systems
DE102005023615A1 (de) 2005-05-21 2006-11-23 Bayer Materialscience Ag Verfahren zur Herstellung von Gasdiffusionselektroden
GB201021352D0 (en) * 2010-12-16 2011-01-26 Johnson Matthey Plc Catalyst layer
CN104404566B (zh) 2014-11-05 2016-01-20 环境保护部华南环境科学研究所 一种以修饰TiO2纳米管阵列为中间层的钛基二氧化铅阳极及其制备方法与应用
WO2018029200A1 (fr) 2016-08-10 2018-02-15 Covestro Deutschland Ag Procédé de purification électrochimique de solutions de traitement contenant des chlorures

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120031852A1 (en) * 2009-04-06 2012-02-09 Sa Envitech S.R.L. Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes
WO2021045191A1 (fr) * 2019-09-05 2021-03-11 デノラ・ペルメレック株式会社 Appareil de production d'une solution aqueuse acide et procédé de production d'une solution aqueuse acide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2020053063A1 *

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