DE3518974A1 - Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants - Google Patents

Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants

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Publication number
DE3518974A1
DE3518974A1 DE19853518974 DE3518974A DE3518974A1 DE 3518974 A1 DE3518974 A1 DE 3518974A1 DE 19853518974 DE19853518974 DE 19853518974 DE 3518974 A DE3518974 A DE 3518974A DE 3518974 A1 DE3518974 A1 DE 3518974A1
Authority
DE
Germany
Prior art keywords
iron
solution
scrubbing
edta
scrubbing solution
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.)
Granted
Application number
DE19853518974
Other languages
German (de)
Other versions
DE3518974C2 (en
Inventor
Heribert Dipl.-Ing. 4390 Gladbeck Dewert
Heinrich Ing.(grad.) 4600 Dortmund Gresch
Heinz Dipl.-Ing. Hölter
Heinrich Dipl.-Ing. 4390 Gladbeck Igelbüscher
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to DE19853518974 priority Critical patent/DE3518974A1/en
Priority to DE19853519198 priority patent/DE3519198A1/en
Priority to DE19853520377 priority patent/DE3520377A1/en
Priority to DE19853524047 priority patent/DE3524047A1/en
Priority to PCT/EP1986/000317 priority patent/WO1986006981A1/en
Priority to EP86903350A priority patent/EP0223803A1/en
Priority to JP61503502A priority patent/JPS63500781A/en
Publication of DE3518974A1 publication Critical patent/DE3518974A1/en
Application granted granted Critical
Publication of DE3518974C2 publication Critical patent/DE3518974C2/de
Granted legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/464—Sulfates of Ca from gases containing sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/48—Sulfites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

In order to avoid too high an EDTA consumption in the scrubbing solution, according to the invention it is proposed that it is composed of an EDTA or NTA solution, the EDTA being mixed with water and an alkali metal hydroxide solution, preferably sodium hydroxide solution, and containing an iron II masking agent to prevent the oxidation of iron II to iron III and an addition of reducing agents to reduce iron III to iron II at a pH of the scrubbing solution of above 5 and less than 8. The scrubbing solution is advantageously made up with a sodium sulphate content of above 20 g per litre and a sodium sulphite content of above 10 g per litre. The iron II masking agent used in the scrubbing solution is a carboxylic acid, preferably tartaric acid, and the reducing agent used in the scrubbing solution is sodium dithionite.

Description

Beschreibung und Erläuterung zur PatentanmeldungDescription and explanation of the patent application

"Waschlösung zur simultanen Waschung von SO, und NOX in Rauchgasen hinter Kraftwerken und anderen fossilen Verbrennungsanlagen" Es ist bekannt, Rauchgase hinter Kraftwerken bzw. fossilen Verbrennungsanlagen, die mit S02 und NOx belastet sind, simultan zu waschen; jedoch ist ebenso bekannt, daß es keine stabilen Auswaschverhältnisse gibt."Washing solution for the simultaneous washing of SO and NOX in flue gases behind power plants and other fossil incinerators "It is known to smoke gases behind power plants or fossil incineration plants that are polluted with S02 and NOx are to wash simultaneously; however, it is also known that there are no stable washout ratios gives.

Ein sehr hoher EDTA-Verbrauch in der Waschlösung gibt dem Verfahren keine Chance, großtechnisch Einsatz zu finden.A very high EDTA consumption in the washing solution gives the process no chance of being used on a large scale.

Erst durch die Findung der nachstehend speziellen Waschlösung ist es möglich, das simultane SO2# und NO -Waschverfahren wirtschaftlich zu nutzen.Only by finding the following special washing solution is it is possible to use the simultaneous SO2 # and NO scrubbing process economically.

Es wurde gefunden, daß durch das Zerstören des EDTA oder NTA in der Waschlösung ein enorm hoher EDTA-Verbrauch notwendig ist, um eine genügend hohe 502 und NO -Auswaschung zu erzielen.It has been found that by destroying the EDTA or NTA in the Washing solution an enormously high EDTA consumption is necessary in order to achieve a sufficiently high one 502 and NO leaching.

Gefunden wurde, daß durch Verhinderung der Oxidation von Eisen-Il zu Eisen-Ill und gleichzeitige Reduzierung in der Waschlösung von Eisen-Ill zu Eisen-Il durch ein Maskierungsmittel des Eisen-Il und ein Reduktionsmittel des Eisen-III, das in der Waschlösung beim Auswaschprozeß reagiert, der Auswaschgrad unter wirtschaftlichen Bedingungen stabil gehalten werden konnte.It was found that by preventing the oxidation of iron II to iron-III and simultaneous reduction in the washing solution from iron-III to iron-II by a masking agent of iron (II) and a reducing agent of iron (III), which reacts in the washing solution during the washing process, the degree of washing out below economic Conditions could be kept stable.

Gefunden wurde, daß zur Eisen-II-Maskierung gegen die Oxidation vorzugsweise Weinsäure sich hervorragend eignet, jedoch auch andere Carbonsäuren, wie z. B. Zitronensäure, und daß bei gleichzeitiger Zugabe eines Reduktionsmittels in der Waschflüssigkeit - Natriumdithionit, vorzugsweise in pastöser, dosierbarer Form - nur geringe Mengen Eisen-II zu Eisen-ITT reduziert werden, die aber gleichzeitig durch Zugabe des Reduktionsmittels wieder zu Eisen-II zurückgewandelt werden Es wurde weiterhin gefunden, daß der Waschprozeß hervorragend läuft, wenn in der Waschflüssigkeit mehr als 20 g Natriumsulfat pro Liter und mehr als 10 g Natriumsulfit pro Liter zugegen sind und der pH-Wert größer 5, jedoch kleiner 8 in der Waschflüssigkeit gehalten wird.It has been found to be preferable for iron (II) masking against oxidation Tartaric acid is ideal, but other carboxylic acids such as. B. citric acid, and that with the simultaneous addition of a reducing agent in the washing liquid - Sodium dithionite, preferably in pasty, meterable form - only small amounts Iron-II can be reduced to iron-ITT, but at the same time by adding the reducing agent can be converted back to iron (II). It was also found that the washing process works well if there is more than 20 g of sodium sulphate per Liters and more than 10 g sodium sulfite per liter are present and the pH value is greater 5, but less than 8 is kept in the washing liquid.

Auswaschgrade von SO2 und NOx simultan von über 90 % sind unter wirtschaftlichen Bedingungen gefunden worden.Simultaneous leaching degrees of SO2 and NOx of over 90% are below economical Conditions have been found.

Patentanspruche Claims

Claims (1)

Patentansprüche: Anspruch 1 Verfahren zur simultanen Waschung von SO, und NOX in Rauchgasen hinter fossilen Feuerungsanlagen dadurch gekennzeichnet, daß die Waschlösung aus einer EDTA-bzw. NTA-Lösung besteht, wobei das EDTA mit Wasser und einer Lauge, vorzugsweise Natronlauge, angemischt ist und ein Eisen-II-Maskierungsmittel zur Hinderung der Oxidation von Eisen-Il zu Eisen-Th sowie einen Zusatz von Reduktionsmitteln zur Reduktion von Eisen-III zu Eisen-Il besitzt bei einem pH-Wert der Waschlösung von größer 5 und kleiner 8.Claims: Claim 1 method for the simultaneous washing of SO, and NOX in flue gases behind fossil combustion systems characterized by that the washing solution from an EDTA or. NTA solution consists of the EDTA with water and a lye, preferably sodium hydroxide solution, and an iron (II) masking agent to prevent the oxidation of iron (II) to iron (th) and the addition of reducing agents for the reduction of iron-III to iron-II possesses at a pH value of the washing solution greater than 5 and less than 8. Anspruch 2 Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß die genannte Waschlösung mit einem Natriumsulfatgehalt von größer 20 g pro Liter und einem Natriumsulfitgehalt von größer 10 g pro Liter angesetzt ist.Claim 2 method according to claim 1, characterized in that the said washing solution with a sodium sulfate content of greater than 20 g per liter and a sodium sulfite content of more than 10 g per liter is set. Anspruch 3 Verfahren nach Anspruch 1 und 2 dadurch gekennzeichnet, daß das Eisen-II-Maskierungsmittel als Carbonsäure, vorzugsweise Weinsäure, und als Reduktionsmittel Natriumdithionit Anwendung in der Waschlösung finden.Claim 3, method according to claims 1 and 2, characterized in that that the iron (II) masking agent as a carboxylic acid, preferably tartaric acid, and Sodium dithionite is used as a reducing agent in the washing solution.
DE19853518974 1985-05-25 1985-05-25 Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants Granted DE3518974A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE19853518974 DE3518974A1 (en) 1985-05-25 1985-05-25 Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants
DE19853519198 DE3519198A1 (en) 1985-05-25 1985-05-29 Scrubbing liquid for scrubbing SO2 and NOx from flue gases downstream of fossil power stations
DE19853520377 DE3520377A1 (en) 1985-05-25 1985-06-07 Reducing agent stockage for the scrubbing solution for the simultaneous scrubbing of SO2 and NOx
DE19853524047 DE3524047A1 (en) 1985-05-25 1985-07-05 Scrubbing liquid and process for separating SO2 and NOx from flue gases of fossil power stations with simultaneous N2O separation
PCT/EP1986/000317 WO1986006981A1 (en) 1985-05-25 1986-05-24 METHOD FOR SIMULTANEOUSLY REMOVING BY WASHING SO2, NOx AND OPTIONALLY OTHER NOXIOUS SUBSTANCES CONTAINED IN FLUE GASES IN HEATING INSTALLATIONS SUPPLIED WITH FOSSILE FUELS
EP86903350A EP0223803A1 (en) 1985-05-25 1986-05-24 METHOD FOR SIMULTANEOUSLY REMOVING BY WASHING SO 2?, NO x? AND OPTIONALLY OTHER NOXIOUS SUBSTANCES CONTAINED IN FLUE GASES IN HEATING INSTALLATIONS SUPPLIED WITH FOSSILE FUELS
JP61503502A JPS63500781A (en) 1985-05-25 1986-05-24 Method for simultaneous cleaning of SO↓2, NO↓x and possibly other harmful substances from the flue gas of fossil fuel operated combustion furnaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19853518974 DE3518974A1 (en) 1985-05-25 1985-05-25 Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants

Publications (2)

Publication Number Publication Date
DE3518974A1 true DE3518974A1 (en) 1986-11-27
DE3518974C2 DE3518974C2 (en) 1987-07-09

Family

ID=6271722

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19853518974 Granted DE3518974A1 (en) 1985-05-25 1985-05-25 Scrubbing solution for simultaneous scrubbing of SO2 and NOx in flue gases downstream of power stations and other fossil combustion plants

Country Status (2)

Country Link
JP (1) JPS63500781A (en)
DE (1) DE3518974A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3524047A1 (en) * 1985-05-25 1987-01-15 Hoelter Heinz Scrubbing liquid and process for separating SO2 and NOx from flue gases of fossil power stations with simultaneous N2O separation
DE3725715A1 (en) * 1987-08-04 1989-02-16 Karl Clemens Dipl Che Kaeuffer Waste gas de-nitrification by scrubbing with dithionite soln. - and electrochemical regeneration, useful for small or medium scale operations

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2445567A1 (en) * 1973-09-24 1975-04-03 Asahi Chemical Ind PROCEDURE FOR REMOVING NITROGEN MONOXIDE FROM A GAS CONTAINING NITROGEN MONOXIDE
DE2460231A1 (en) * 1973-12-27 1975-07-03 Chisso Eng Co Ltd PROCESS FOR THE REMOVAL OF NITROGEN OXIDES FROM INDUSTRIAL EXHAUST GASES AND SUITABLE AQUATIC TREATMENT SOLUTIONS

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2445567A1 (en) * 1973-09-24 1975-04-03 Asahi Chemical Ind PROCEDURE FOR REMOVING NITROGEN MONOXIDE FROM A GAS CONTAINING NITROGEN MONOXIDE
DE2460231A1 (en) * 1973-12-27 1975-07-03 Chisso Eng Co Ltd PROCESS FOR THE REMOVAL OF NITROGEN OXIDES FROM INDUSTRIAL EXHAUST GASES AND SUITABLE AQUATIC TREATMENT SOLUTIONS

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3524047A1 (en) * 1985-05-25 1987-01-15 Hoelter Heinz Scrubbing liquid and process for separating SO2 and NOx from flue gases of fossil power stations with simultaneous N2O separation
DE3725715A1 (en) * 1987-08-04 1989-02-16 Karl Clemens Dipl Che Kaeuffer Waste gas de-nitrification by scrubbing with dithionite soln. - and electrochemical regeneration, useful for small or medium scale operations

Also Published As

Publication number Publication date
JPS63500781A (en) 1988-03-24
DE3518974C2 (en) 1987-07-09

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