EP3110763A1 - Procédé de dégradation par oxydation des composés azotés présents dans les eaux usées - Google Patents

Procédé de dégradation par oxydation des composés azotés présents dans les eaux usées

Info

Publication number
EP3110763A1
EP3110763A1 EP15713127.7A EP15713127A EP3110763A1 EP 3110763 A1 EP3110763 A1 EP 3110763A1 EP 15713127 A EP15713127 A EP 15713127A EP 3110763 A1 EP3110763 A1 EP 3110763A1
Authority
EP
European Patent Office
Prior art keywords
anode
current density
nitrogen
cathode
water
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Withdrawn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
EP15713127.7A
Other languages
German (de)
English (en)
Inventor
Barbara Behrendt-Fryda
Matthias Fryda
Linda Heesch
Thorsten Matthée
Jens Saalfrank
Rieke NEUBER
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.)
Areva GmbH
Original Assignee
Areva 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 Areva GmbH filed Critical Areva GmbH
Publication of EP3110763A1 publication Critical patent/EP3110763A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C02F1/46104—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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • 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
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical

Definitions

  • the invention relates to a process for the oxidative degradation of nitrogen-containing compounds in wastewaters by means of an electrochemical treatment using a diamond electrode as anode and a cathode as counterelectrode.
  • Diamond electrodes consist of a metallic or non-metallic conductive support on which a layer of diamond crystals is deposited.
  • the diamond layer formed in this way is made conductive by being doped with suitable elements, preferably with boron.
  • the diamond layer is applied to the electrode carrier usually by the CVD (Chemical Vapor Deposition) method and is known to the person skilled in the art by numerous publications (cf. for example, US 5,399,247).
  • Diamond electrodes have the advantage of allowing a high overpotential, which generates in situ strong oxidants such as ozone, hydrogen peroxide and OH radicals from the wastewater. It is therefore possible with diamond electrodes to produce otherwise difficult to obtain oxidation products.
  • wastewater treatment the oxidation is continued by means of the diamond electrodes until the organic constituents have been completely or almost completely mineralized, ie converted into non-critical compounds (for example, CO 2 and water).
  • non-critical compounds for example, CO 2 and water.
  • Such treated water can be reused as service water or discharged as clean wastewater into public waters.
  • an amine-containing wastewater is present.
  • an amine-containing wastewater is present.
  • CONFIRMATION COPY Nuclear power plants used with alkalizing added water, which is present after treatment as waste water with a high amine content.
  • the alkalizing agents used are, for example, ethanolamine, morpholine, dimethylamine and methoxypropylamine.
  • the present invention is therefore based on the object to replace the previous biological denitrification by a simpler and better controlled process.
  • the method of the type mentioned is according to the invention characterized in that in a first stage of the anode, a first current density is set to oxidize the nitrogen-containing compounds and then with a second current density, which is less than the first current density , the dissolved total nitrogen content is reduced by release of molecular nitrogen.
  • the inventive method is based on a plurality of essential principles that have been determined in part by intensive involvement of the inventors with the diamond electrodes.
  • diamond electrodes which are operated with an overvoltage of more than 2 V (preferably with 2.4 V), arise from the water OH radicals.
  • Diamond electrodes are thus not selective as a function of the overvoltage, but produce OH radicals independently of the operating voltage.
  • the formation of hydrogen peroxide ozone results from reactions of the short-lived OH radicals, which form an ozone molecule at a high concentration of three OH radicals and form hydrogen peroxide at a lower concentration of two OH radicals. If the concentration of hydroxyl radicals is insufficient for the formation of said secondary products, they directly oxidize constituents of the water.
  • the solubility of ozone is also dependent on the temperature of the water and decreases with increasing temperature.
  • the adjustment of the current density at the surface of the anode should also be such that no hydrogen peroxide is produced as possible.
  • Hydrogen peroxide has a much lower oxidation potential (1, 8 V) and is therefore not sufficient for the destruction of some alkalizing agents.
  • hydrogen peroxide (H2O2) reacts with ozone to form short-lived OH radicals, delaying the destruction of the alkalizers due to the short-lived nature of OH radicals.
  • a high current density is to be set in order to destroy the nitrogen-containing compounds by oxidation.
  • the second process step must be initiated in good time, in which the adjustment of the low current density results in the setting of a defined and optimal ratio between produced ammonium and produced nitrate.
  • the setting of the currents suitable for a used electrochemical treatment cell and the operating parameters used therein can be easily determined experimentally by measuring the concentrations of ammonium and nitrate. Furthermore, it is possible to determine the reduction of the total nitrogen content by the usual methods, whereby It should be noted that also the ion chromatography allows a fast and meaningful determination of the total nitrogen content.
  • the duration of treatment in the first stage of the process depends on the load on the water with the nitrogen-containing compounds - and possibly additional organic constituents - that is on chemical oxygen demand (COD).
  • COD chemical oxygen demand
  • the user is aware of the COD content of his wastewater. Otherwise, the COD content can readily be determined by measuring methods known to those skilled in the art. It is essential that the charge entry into the wastewater is so high that all nitrogen-containing compounds are destroyed, but that a significant proportion of ammonium remains in the water and is not further oxidized to nitrate.
  • the time of completion of the first stage of the process can easily be determined by measurements of the ammonium content and the nitrate content in a preliminary test, so that the setting of the charge input at the selected current density (current intensity) can be determined so that a sufficient amount of ammonium remains in the wastewater , which in the second stage with the nitrate formed allows the formation of molecular nitrogen, thus contributing to the reduction of the total nitrogen content.
  • an electrode arrangement known from EP 1 730 080 B1 is suitable, as shown schematically in exploded illustration in FIG.
  • the electrode arrangement consists of an anode A, a cathode K and a conductive membrane M, which liquid-tightly seals an anode space AR with respect to a cathode space KR, the cathode space KR being due to an open structure of the anode A directly adjacent to the membrane M and cathode K. with one side of the membrane M and the cathode K and the anode space AR with the opposite side of the membrane M and the anode A is formed.
  • the membrane M is a conductive membrane, which ensures conductivity of between 0.3 and 10uO pS / cm in the case of conductivity waters by transporting hydrogen bonds within the membrane M. Between the electrodes A, K and the membrane M, the charge is transferred via ion diffusion.
  • both electrodes, anode A and cathode K are formed as diamond electrodes, wherein the base body of the electrodes A, K is an expanded metal grid.
  • the expanded metal lattice leads to a rhombic formation of the electrode surface, which abuts the membrane M with the tips of the rhombi (FIG. 2).
  • a region B with a high current density is formed around the tip in each case, in which ozone is predominantly formed at a suitable current intensity.
  • OH radicals are formed on the anode surface in a lower concentration, which thus react oxidatively with contaminants of the water which reach the surface of the anode A.
  • Example 2 An increase in the conductivity of the water leads to an increase in the area in which hydrogen peroxide is formed. Since this is not desirable for the reasons mentioned above, the conductivity of the water should not be too large.
  • Example 2 An increase in the conductivity of the water leads to an increase in the area in which hydrogen peroxide is formed. Since this is not desirable for the reasons mentioned above, the conductivity of the water should not be too large.
  • Example 1 With an anode arrangement of Example 1, different treatment currents of 0.4 A, 1 A and 3 A have been realized. It turns out that, starting from the decomposition of ethanolamine (ETA), with the high current of 3 A, the total nitrogen is not reduced. With the current of 1 A, a slight reduction of the total nitrogen content, while a significant reduction of total nitrogen with the lower current of 0.4 A at a relatively low charge entry succeeds, as shown in Figure 3.
  • FIG. 4 illustrates the reduction of the total nitrogen for the mentioned current intensities.
  • Examples 1 and 2 were carried out starting from the alkalizing agent ethanolamide.
  • the process according to the invention is also suitable for correspondingly other alkalizing agents, such as, for example, morpholine, dimethylamine (DMA) and methoxypropylamine (MPA).
  • DMA dimethylamine
  • MPA methoxypropylamine
  • FIG. 6 shows the degradation of the concentrates of the alkalizing agents ETA, DMA, MPA and morpholine considered here.
  • the concentrates can be completely degraded by the method according to the invention, as shown in FIG. With the second method step according to the invention, the total nitrogen content can then be reduced.

Landscapes

  • 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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne un procédé pour la dégradation par oxydation des composés azotés présents dans des eaux usées à l'aide d'un traitement électrochimique en utilisant une électrode en diamant à titre d'anode (A) et une cathode (K) à titre de contre-électrode. La destruction des composés azotés et une réduction de la teneur globale en azote peuvent s'effectuer dans un procédé commun consistant à ajuster une première densité de courant sur l'anode (A) au cours d'une première étape de procédé afin d'oxyder les composés azotés et, ensuite, une deuxième densité de courant qui est plus faible que la première et qui réduit la teneur globale en azote dissous par libération de l'azote moléculaire.
EP15713127.7A 2014-02-25 2015-02-11 Procédé de dégradation par oxydation des composés azotés présents dans les eaux usées Withdrawn EP3110763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014002450.4A DE102014002450A1 (de) 2014-02-25 2014-02-25 Verfahren zum oxidativen Abbau von stickstoffhaltigen Verbindungen in Abwässern
PCT/DE2015/000076 WO2015127918A1 (fr) 2014-02-25 2015-02-11 Procédé de dégradation par oxydation des composés azotés présents dans les eaux usées

Publications (1)

Publication Number Publication Date
EP3110763A1 true EP3110763A1 (fr) 2017-01-04

Family

ID=52779438

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15713127.7A Withdrawn EP3110763A1 (fr) 2014-02-25 2015-02-11 Procédé de dégradation par oxydation des composés azotés présents dans les eaux usées

Country Status (5)

Country Link
EP (1) EP3110763A1 (fr)
JP (1) JP2017512134A (fr)
CN (1) CN106458653A (fr)
DE (1) DE102014002450A1 (fr)
WO (1) WO2015127918A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016119080B4 (de) 2016-10-07 2020-11-12 Condias Gmbh Vorrichtung zum elektrochemischen Behandeln von Abwasser
DE102018131902B3 (de) * 2018-12-12 2020-02-27 Framatome Gmbh Verfahren zur Konditionierung von Ionenaustauscherharzen und Vorrichtung zur Durchführung des Verfahrens
CA3199877A1 (fr) 2020-12-24 2022-06-30 Framatome Gmbh Mineralisation de composes organiques avec electrode en diamant dope au bore pendant un processus de reextraction de radionucleides

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US5399247A (en) * 1993-12-22 1995-03-21 Eastman Kodak Company Method of electrolysis employing a doped diamond anode to oxidize solutes in wastewater
JP3530511B2 (ja) * 2001-09-19 2004-05-24 三洋電機株式会社 窒素処理方法及び窒素処理システム
JP2004237207A (ja) * 2003-02-05 2004-08-26 Kurita Water Ind Ltd 有機化合物含有水の処理方法および処理装置
DE102004015680A1 (de) * 2004-03-26 2005-11-03 Condias Gmbh Elektrodenanordnung für eine elektrochemische Behandlung von Flüssigkeiten mit einer geringen Leitfähigkeit
DE102004026447B4 (de) * 2004-05-29 2009-09-10 Verein für Kernverfahrenstechnik und Analytik Rossendorf e.V. Verfahren und Vorrichtung zur Abtrennung von Sulfationen aus Wässern und zur Einbringung von Pufferkapazität in Wässer
EP2072472A1 (fr) * 2007-12-19 2009-06-24 Condias Gmbh Dispositif destiné à la réalisation d'une réaction électrochimique et agencement de réacteur électrochimique
CN101234805A (zh) * 2008-02-18 2008-08-06 中国矿业大学(北京) 高效脱氮的电化学氧化水处理方法及系统
DE102008048691A1 (de) * 2008-07-07 2010-01-14 Areva Np Gmbh Verfahren zur Konditionierung einer bei der nasschemischen Reinigung konventioneller oder nukleartechnischer Anlagen anfallenden, organische Substanzen und Metalle in ionischer Form enthaltenden Abfalllösung
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CN103193301B (zh) * 2013-04-27 2014-07-30 国电环境保护研究院 一种处理含氮有机废水的电化学反应器及应用及处理方法

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Also Published As

Publication number Publication date
JP2017512134A (ja) 2017-05-18
WO2015127918A1 (fr) 2015-09-03
DE102014002450A1 (de) 2015-08-27
CN106458653A (zh) 2017-02-22

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