Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
  • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
  • C10K1/105—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur
  • C10K1/106—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur containing Fe compounds
• • 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
• • 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
  • C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
• • 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
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
  • C02F2101/16—Nitrogen compounds, e.g. ammonia
• • 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
  • C02F2101/16—Nitrogen compounds, e.g. ammonia
  • C02F2101/163—Nitrates
• • 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

Definitions

• the invention concerns a device and a method for removing ⁇ nitrogen compounds from an aqueous liquid containing nitrogen oxides NO and/or nitrates NOT, the device comprising an electrolytical cell with a cathode and an anode and a current source applicable thereto.
• the process for the removal of nitrogen oxides consists in the reduction of the compound to nitrogen.
• several industrial processes are already known ⁇ Chem. Ing. Techn. 57, 1985, page 717 to 727) .
• nitrates in waste waters are also a growing problem.
• the intensive use of natural manure and fertilizers in agriculture leads to an increasing content of nitrates in subsoil water.
• drinking water pro ⁇ ducers have difficulties in maintaining the limit.below 50 mg/m of nitrates in their final product.
• EP-A-0 243 889 discloses a process for the electrolytic de- noxing of flue gases.
• the nitrogen oxides are absorbed in a iron-ethylene diamine-tetraacetic acid (Fe-EDTA) complex.
• Fe-EDTA iron-ethylene diamine-tetraacetic acid
• hypobromide oxidizes ammonia to nit ⁇ rogen according to reaction (4).
• bromine is stable and oxydizes ammonia according to the following reaction:
• the object of the present invention is to provide a simple, compact and reliable process which is apt to be realized on an industrial scale for removing from an aqueous liquid consider ⁇ able amounts of nitrogen oxides, i.e. either NO and/or NO .
• Figure 1 shows schematically an electrolytic cell of the de ⁇ vice according to the invention.
• Figure 2 shows the application of this invention to a flue ga ⁇ purification plant where NO X is removed from the flue gas.
• Figure 3 represents schematically the application of this invention to the purification of liquids, in particular waste water including nitrates (NO .
• the main feature of the present invention is the reduction of nitrogen oxides to ammonia or hydroxylamine and the subsequent oxidation of these compounds to gaseous nitrogen. Both steps can be carried ,out in one single electrolytic cell.
• the catho ⁇ de compartment of this cell is used for the reduction of nit ⁇ rogen oxides and the anode compartment is used for the oxida- tion of ammonia and hydroxylamine, respectively to gaseous nitrogen.
• the two compartments are separated by a cation se ⁇ lective membrane or diaphragm. Surprisingly, it has been ob ⁇ served that the ammonia formed in the cathode compartment of the cell is transported through the membrane to the anode and immediately reacts electrolytically with the bromine formed in the anode compartment.
• Such a cell is schematically shown in figure 1.
• the cell is divided by a cation selective membrane 1 into a cathode com ⁇ partment 2 and an anode compartment 3.
• the membrane is a mic- roporous fabric, especially of polytetrafluorethylene fibers or of fibers containing carbon fluorine backbone chains with perfluoro side chains having sulphuric or carboxylic acid groups.
• the thickness of the membrane is between 10 and 80 ⁇ , preferably between 20 and 40 ⁇ m.
• Both compartments are pro- vided with inlets 4, 5 and outlets 6, 7 respectively, and electrodes 8, 9 are provided in each of the compartments.
• the electrodes may be connected to a DC current source (not shown) .
• the current polarity is such that the compartment 2 constitutes the cathode compartment and the compartment 3 constitutes the anode compartment.
• the inventive method concerns the denoxing of the above mentioned Fe-EDTA complex in the frame of a flue gas purification plant.
• a flue gas purification plant Such a plant is partly indi ⁇ cated in figure 2 and contains a cell 10 in accordance with figure 1.
• the flue gases pass subsequently through a washing column 11 and an absorption column 12. They are then conveyed to a chimney 15.
• These columns are located at the outlet of a flue gas desulphurizing plant as disclosed in the above quoted document EP-A-0 243 889.
• the electrolytic cell 10 is divided, into two compartments, and the two compartments are respectively inte ⁇ grated into two different liquid conveying loops.
• the cathode compartment 2 is fed with an aqueous solution containing Fe(NO)EDTA from the absorption column 12 and supplies to this column an aqueous solution containing Fe(EDTA) .
• the anode compartment 3 is fed with a scrubber liquid from the washing column containing between 0.1 and 0.5% by weight of HBr and between 0.1 and 0.5% by weight of sulphuric acid H2S0 .
• the scrubber liquid leaving this compartment 3 is again supplied to the washing column 11.
• the liquid containing NOx is passed through the cathode com ⁇ partment, where the complex is decomposed into ammonia NH, and Fe(EDTA) according to reaction (3).
• the ammonia formed in the cathode compartment diffuses through the cell membrane and is oxidized in the anode compartment to nitrogen N ? and hydrogen ⁇ .2 .
• In the anode compartment also Br ⁇ is formed (reaction N° 5) , which can be recirculated either to the washing column 11, as is shown in figure 2, or else to the reactor of the desul- phurization process (not shown) .
• the cell used in this laboratory scale experiment is equipped with an anode consisting of a 4 cm 2 graphite cylinder, a cathode consisting of a 10 cm 2 Pt cylinder and a membrane consisting of a PTFE fabric with an surface area of 20 cm 2 and a thickness of 0.02 mm.
• the initial composition of the catho ⁇ lyte is shown in the first column of table I.
• the test tempe ⁇ rature is 25°C and the current applied to the cell is 500 A.
• the second column of table I shows the composition of the catholyte after four hours of operation. It can be seen that the contents of nitrogen oxides and ammonia are substantially reduced.
• This second experiment is well adapted to a de ⁇ ulphurization process in which the anolyte contains a relatively high amount of sulphuric acid and the pH value is low.
• Fe(EDTA) complex cited above can be replaced by other members of the EDTA family such as nitri- lotriacetic acid (NTA) or N(hydroxyethyl) ethylene dia inetri- acetic (Fell-HEDTA) .
• NTA nitri- lotriacetic acid
• Fell-HEDTA N(hydroxyethyl) ethylene dia inetri- acetic
• FIG. 3 Another application of the inventive method concerns the re- moval of nitrates from waste waters.
• the corresponding device is shown in figure 3, and it is a very simple device, as it almost exclusively consists of the cell 10.
• the cathode com ⁇ partment is included in a waste water loop, waste water with nitrates being fed to this compartment and purified waste water without nitrates being collected at the outlet of this compartment.
• the corresponding reaction equation is as follows:
• the anodic loop conveys an anolyte consisting of a bromide or chloride solution, for example 0.5% by weight HBr or NaBr.
• the anodic loop further contains a recirculation pump 13 and a gas separator vessel 14 from which N ? may escape.
• Table III shows the initial and final compositions of the ca ⁇ tholyte and the anolyte obtained in an experiment similar to those referred to in tables I and II and concerning the puri ⁇ fication of NO ⁇ containing waste water.
• the experiment is carried out at a temperature of 60°C, the anode consists of a 4 cm 2 graphite electrode and the cathode of a 210 cm 2 copper cathode.
• the anolyte may contain chlor ⁇ ine or iodine instead of bromine.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Electrochemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Inorganic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Water Treatment By Electricity Or Magnetism (AREA)
• Treating Waste Gases (AREA)
• Removal Of Specific Substances (AREA)
• Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
• Separation By Low-Temperature Treatments (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Gas Separation By Absorption (AREA)
• Treatment Of Water By Oxidation Or Reduction (AREA)
• Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

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Family Applications (1)

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Cited By (15)

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Citations (5)

Family Cites Families (2)

• 1989
  • 1989-08-07 AT AT89114525T patent/ATE82946T1/de not_active IP Right Cessation
  • 1989-08-07 EP EP89114525A patent/EP0412175B1/en not_active Expired - Lifetime
  • 1989-08-07 ES ES198989114525T patent/ES2037355T3/es not_active Expired - Lifetime
  • 1989-08-07 DE DE8989114525T patent/DE68903760T2/de not_active Expired - Fee Related
• 1990
  • 1990-08-03 ZA ZA906136A patent/ZA906136B/xx unknown
  • 1990-08-06 CA CA002059542A patent/CA2059542A1/en not_active Abandoned
  • 1990-08-06 AU AU61869/90A patent/AU635064B2/en not_active Ceased
  • 1990-08-06 MX MX021860A patent/MX172695B/es unknown
  • 1990-08-06 DD DD90343271A patent/DD297143A5/de not_active IP Right Cessation
  • 1990-08-06 PT PT94927A patent/PT94927A/pt not_active Application Discontinuation
  • 1990-08-06 WO PCT/EP1990/001285 patent/WO1991001947A1/en not_active Ceased
  • 1990-08-06 PL PL90286371A patent/PL164483B1/pl unknown
  • 1990-08-06 BR BR909007577A patent/BR9007577A/pt not_active Application Discontinuation
  • 1990-08-06 US US07/829,032 patent/US5354436A/en not_active Expired - Fee Related
  • 1990-08-06 JP JP2511724A patent/JPH04506929A/ja active Pending
  • 1990-08-06 HU HU9200014A patent/HUT70392A/hu unknown
  • 1990-08-07 CN CN90107370A patent/CN1049832A/zh active Pending
  • 1990-08-07 IE IE285590A patent/IE64166B1/en not_active IP Right Cessation
• 1992
  • 1992-01-14 DK DK004592A patent/DK4592A/da not_active Application Discontinuation
• 1993
  • 1993-01-28 GR GR930400151T patent/GR3006904T3/el unknown

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