EP0933595A2 - Method for reducing nitrons fumes in combustion facilities with simultaneous saving of energy - Google Patents

Method for reducing nitrons fumes in combustion facilities with simultaneous saving of energy Download PDF

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Publication number
EP0933595A2
EP0933595A2 EP98120236A EP98120236A EP0933595A2 EP 0933595 A2 EP0933595 A2 EP 0933595A2 EP 98120236 A EP98120236 A EP 98120236A EP 98120236 A EP98120236 A EP 98120236A EP 0933595 A2 EP0933595 A2 EP 0933595A2
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EP
European Patent Office
Prior art keywords
air
heating medium
complete combustion
burners
reducing
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Withdrawn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
EP98120236A
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German (de)
French (fr)
Other versions
EP0933595A3 (en
Inventor
Johannes Haunberger
Engelbert Hack
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Infraserv GmbH and Co Gendorf KG
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Infraserv GmbH and Co Gendorf 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.)
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Application filed by Infraserv GmbH and Co Gendorf KG filed Critical Infraserv GmbH and Co Gendorf KG
Publication of EP0933595A2 publication Critical patent/EP0933595A2/en
Publication of EP0933595A3 publication Critical patent/EP0933595A3/en
Withdrawn legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C6/00—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion
    • F23C6/04—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection
    • F23C6/045—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection with staged combustion in a single enclosure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2201/00—Staged combustion
    • F23C2201/10—Furnace staging
    • F23C2201/101—Furnace staging in vertical direction, e.g. alternating lean and rich zones
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
    • F23J2215/00—Preventing emissions
    • F23J2215/10—Nitrogen; Compounds thereof

Definitions

  • NO x nitrous gases
  • NO x nitrous gases
  • NO 2 nitrous gases
  • the maximum limit for NO x emissions became more industrial in December 1996
  • Incineration plants reduced from 450 mg / Nm 3 to 200 mg / Nm 3 (limit value according to 17th BImSchV).
  • the large energy supply companies use a sub-stoichiometric combustion with respect to oxygen in up to four vertically arranged burner levels for the primary reduction of NO x and compensate for this by supplying so-called "tertiary air" in the upper, somewhat colder part of the radiation boiler.
  • At least two pairs of burners opposite each other are usually installed per burner level, the outlets of which are usually arranged tangentially, so that the fuel-air mixture is set into a strong circular flow and is optimally mixed.
  • the performance of the burners installed on the same level is usually identical or shows only minimal, random deviations.
  • burner 1 is operated with 30% excess air and burner 2 with 10% excess air, in each case based on the amount of air required for the complete combustion of the heating medium, with the proviso that so much air is supplied that the flue gas leaving the boiler is still at least the required Contains excess oxygen.
  • the difference in air supply to the burners installed on the same level is preferably 20 to 40%.
  • a total of 15 to 50% excess of air is particularly preferably used, based on the amount of heating required for complete combustion of the heating medium.
  • natural gas, combustible exhaust gases, heating oils (for example medium and low-viscosity oils), coal dust, but also combustible waste from the production of organic chemicals can be used as equivalent heating means.
  • An example of such combustible waste is the distillation residues from the production of tallow fatty amines, which still contain residues of copper catalysts.
  • the permissible NO x limit value could not be met even by adding urea as a reducing agent, so that initially only expensive external disposal in a hazardous waste facility was considered.
  • this problem waste could be disposed of in a normal incineration plant, the NO x value in the exhaust gas being only 150 mg / Nm 3 .

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Treating Waste Gases (AREA)

Abstract

The method reduces the amount of nitrous gas such as nitrous oxide when operating a combustion system. Compared with the amount of air required for complete combustion, the burner is operated partly with excess and partly with insufficient air. The difference between the amounts of air can be between 20 % and 40 %, and the overall surplus of air can be between 15 % and 50 % of that required for complete combustion. Natural gas, combustible exhaust gases, heating oil, pulverized coal or combustible waste from chemical production can be used as the heating agent.

Description

Die Emission nitroser Gase, die üblicherweise als NOx bezeichnet werden und im wesentlichen aus NO und NO2 bestehen, stellt für Verbrennungsanlagen aller Art ein großes Problem dar. Im Sinne des Umweltschutzes wurde im Dezember 1996 der maximale Grenzwert für die NOx-Emission industrieller Verbrennungsanlagen von 450 mg/Nm3 auf 200 mg/Nm3 reduziert (Grenzwert nach 17. BImSchV). Gemäß dem Stand der Technik verwenden die großen Energieversorgungsunternehmen zur primären Reduzierung von NOx eine bezüglich Sauerstoff unterstöchiometrische Verbrennung in bis zu vier vertikal angeordneten Brennerebenen und kompensieren dies durch Zufuhr sogenannter "Tertiärluft" in den oberen, etwas kälteren Teil des Strahlungskessels. Auf diese Weise wird der vorgeschriebene Überschuß von 3 % Sauerstoff in den austretenden Verbrennungsgasen erreicht. Pro Brennerebene sind üblicherweise mindestens zwei paarweise gegenüberliegende Brenner installiert, deren Auslässe meist tangential angeordnet sind, so daß das Brennstoff-Luft-Gemisch in eine starke zirkulare Strömung versetzt und optimal vermischt wird. Die Leistung der auf derselben Ebene installierten Brenner ist im Regelfall identisch oder weist nur minimale, zufällige Abweichungen auf.The emission of nitrous gases, which are usually referred to as NO x and essentially consist of NO and NO 2 , is a major problem for combustion plants of all kinds. In terms of environmental protection, the maximum limit for NO x emissions became more industrial in December 1996 Incineration plants reduced from 450 mg / Nm 3 to 200 mg / Nm 3 (limit value according to 17th BImSchV). According to the state of the art, the large energy supply companies use a sub-stoichiometric combustion with respect to oxygen in up to four vertically arranged burner levels for the primary reduction of NO x and compensate for this by supplying so-called "tertiary air" in the upper, somewhat colder part of the radiation boiler. In this way, the prescribed excess of 3% oxygen in the exiting combustion gases is achieved. At least two pairs of burners opposite each other are usually installed per burner level, the outlets of which are usually arranged tangentially, so that the fuel-air mixture is set into a strong circular flow and is optimally mixed. The performance of the burners installed on the same level is usually identical or shows only minimal, random deviations.

Es wurde nun völlig überraschend gefunden, daß sich die NOx-Gehalte im Abgas der Verbrennungsanlage erheblich dadurch reduzieren lassen, daß die sich auf einer Ebene befindlichen Brenner mit deutlich unterschiedlichen Luftmengen betrieben werden. Beispielsweise wird Brenner 1 mit 30 % Luftüberschuß und Brenner 2 mit 10 % Luftunterschuß betrieben, jeweils bezogen auf die zur vollständigen Verbrennung des Heizmittels erforderliche Luftmenge, mit der Maßgabe, daß so viel Luft zugeführt wird, daß das den Kessel verlassende Rauchgas noch mindestens den geforderten Überschuß an Sauerstoff enthält. Vorzugsweise beträgt die Differenz der Luftversorgung der auf derselben Ebene installierten Brenner 20 bis 40 %. Besonders bevorzugt wird insgesamt ein Überschuß an Luft von 15 bis 50 % verwendet, bezogen auf die zur vollständigen Verbrennung des Heizmittels erforderliche Heizmenge.It has now been found, completely surprisingly, that the NO x contents in the exhaust gas of the incineration plant can be considerably reduced by operating the burners located on one level with significantly different amounts of air. For example, burner 1 is operated with 30% excess air and burner 2 with 10% excess air, in each case based on the amount of air required for the complete combustion of the heating medium, with the proviso that so much air is supplied that the flue gas leaving the boiler is still at least the required Contains excess oxygen. The difference in air supply to the burners installed on the same level is preferably 20 to 40%. A total of 15 to 50% excess of air is particularly preferably used, based on the amount of heating required for complete combustion of the heating medium.

Als äquivalente Heizmittel können im Rahmen des erfindungsgemäßen Verfahrens Erdgas, brennbare Abgase, Heizöle (beispielsweise mittelflüssige und schwerflüssige Öle), Kohlenstaub, aber auch brennbare Abfälle aus der Produktion organischer Chemikalien verwendet werden. Als Beispiel für solche brennbaren Abfälle seien die Destillationsrückstände aus der Herstellung von Talgfettaminen genannt, die noch Reste von Kupferkatalysatoren enthalten. In diesem Fall konnte der zulässige NOx-Grenzwert auch durch Zusatz von Harnstoff als Reduktionsmittel nicht eingehalten werden, so daß zunächst nur eine teure Fremdentsorgung in einer Sondermüllanlage in Frage kam. Mit Hilfe des erfindungsgemäßen Verfahrens konnte dieser Problemmüll in einer normalen Verbrennungsanlage entsorgt werden, wobei der NOx-Wert im Abgas nur 150 mg/Nm3 betrug.In the process according to the invention, natural gas, combustible exhaust gases, heating oils (for example medium and low-viscosity oils), coal dust, but also combustible waste from the production of organic chemicals can be used as equivalent heating means. An example of such combustible waste is the distillation residues from the production of tallow fatty amines, which still contain residues of copper catalysts. In this case, the permissible NO x limit value could not be met even by adding urea as a reducing agent, so that initially only expensive external disposal in a hazardous waste facility was considered. With the aid of the method according to the invention, this problem waste could be disposed of in a normal incineration plant, the NO x value in the exhaust gas being only 150 mg / Nm 3 .

Im Falle von besonders hohen Stickstoffgehalten des zu verbrennenden Materials kann die an sich bekannte Methode des Eindüsens einer wäßrigen Lösung eines stickstoffhaltigen Reduktionsmittels, bevorzugt einer Lösung von Harnstoff oder von Ammoniak, mit dem erfindungsgemäßen Verfahren kombiniert werden. Dies ist jedoch nur in seltenen Fällen erforderlich und hat den Nachteil, daß durch größere Mengen von eingedüstem Wasser in der Regel die Emissionen von Kohlenmonoxid ansteigen. Ein weiterer Nachteil ist natürlich, daß die Verdampfung des Wassers einen zusätzlichen Energieaufwand verursacht.In the case of particularly high nitrogen contents of the burning material can the known method of Injection of an aqueous solution of a nitrogenous Reducing agent, preferably a solution of urea or of ammonia, combined with the inventive method become. However, this is only necessary in rare cases and has the disadvantage that larger amounts of injected water usually the emissions of Carbon monoxide rise. Another disadvantage is of course that the evaporation of the water is an additional Energy expenditure caused.

Das erfindungsgemäße Verfahren weist folgende Vorteile auf:

  • Der Brennstoffverbrauch (meist Erdgas und/oder Heizöl) wird durch Verbesserung des Wirkungsgrades auf ein Minimum reduziert.
  • Der gesetzlich vorgeschriebene NOx-Grenzwert wird im Dauerbetrieb unterschritten.
  • Es sind keine Investitionskosten und Betriebskosten für eine spezielle NOx-mindernde Anlage (DENOX-Anlage) erforderlich.
  • Abstellungen und Wartungen werden minimiert: Die nach dem erfindungsgemäßen Verfahren betriebene Abfallverbrennungsanlage war im Jahr 1996 zu 93 % der gesamten Jahresstunden in Betrieb.
  • Der Einsatz von wäßrigen Harnstoff- und/oder Ammoniaklösungen kann auf seltene Ausnahmefälle reduziert werden, wodurch sich eine beträchtliche Kosteneinsparung ergibt.
  • Schwer brennbare Heizmittel können mit höherem Wirkungsgrad verbrannt werden.
The method according to the invention has the following advantages:
  • Fuel consumption (mostly natural gas and / or heating oil) is reduced to a minimum by improving efficiency.
  • The legally prescribed NO x limit value is not reached in continuous operation.
  • There are no investment costs and operating costs for a special NO x reducing system (DENOX system).
  • Shutdowns and maintenance are minimized: The waste incineration plant operated according to the method according to the invention was in operation in 1996 for 93% of the total hours of the year.
  • The use of aqueous urea and / or ammonia solutions can be reduced to rare exceptional cases, which results in considerable cost savings.
  • Fires that are difficult to burn can be burned with higher efficiency.

Die Erfindung wird durch folgende Beispiele und Vergleichsbeispiele zur NOx-Bildung noch näher erläutert:The invention is explained in more detail by the following examples and comparative examples for NO x formation:

In einer Abfallverbrennungsanlage werden zwei Versuchsreihen mit jeweils vier Versuchen durchgeführt. In der Brennkammer sind auf einer Ebene zwei Brenner derselben Bauart und Leistung installiert, die wie üblich eine zirkulare Strömung mit starker Verwirbelung erzeugen. Die Zuluftmenge der beiden Brenner ist durch Klappen unabhängig voneinander regelbar. Im Brenner 1 werden stickstoffhaltige Rückstände und im Brenner 2 stickstoffreie Rückstände verbrannt. Es handelt sich um stickstoffhaltige brennbare Rückstände aus der Aminproduktion beziehungsweise stickstoffreie verunreinigte Lösemittel, beispielsweise aus der Glykolherstellung. Die Temperatur in der Nachbrennkammer ist praktisch konstant und beträgt 980 bis 990 °C.Two series of tests are being carried out in a waste incineration plant carried out with four attempts each. In the combustion chamber are two burners of the same type and Power installed which, as usual, is a circular flow generate with strong turbulence. The supply air volume of the two Burner can be controlled independently of each other by flaps. in the Burner 1 are nitrogenous residues and in Burner 2 nitrogen-free residues burned. It deals nitrogen combustible residues from the Amine production or nitrogen-free contaminated Solvents, for example from glycol production. The Temperature in the afterburner is practically constant and is 980 to 990 ° C.

Beispiele 1 bis 4 (erfindungsgemäß)Examples 1 to 4 (according to the invention)

Beispielexample Harnstoff 10,5%ige Lösung in Wasser [l/h]Urea 10.5% solution in water [l / h] % Klappenöffnung% Flap opening Einsatzmenge [l/h]Application rate [l / h] NOx [mg/Nm3]NO x [mg / Nm 3 ] Brenner 1Burner 1 Brenner 2Burner 2 brennbare Stickstoffverbindungenflammable nitrogen compounds brennbare stickstofffreie Verbindungenflammable nitrogen-free compounds 11 00 1010th 4242 210210 240240 150150 22nd 5050 1010th 4242 210210 240240 128128 33rd 8080 1010th 4242 210210 240240 105105 44th 120120 1010th 4242 210210 240240 8585

Vergleichsbeispiele 1 bis 4 (Stand der Technik)Comparative Examples 1 to 4 (prior art)

VergleichsbeispielComparative example Harnstoff, 10,5%ige Lösung in Wasser [l/h]Urea, 10.5% solution in water [l / h] % Klappenöffnung% Flap opening Einsatzmenge [l/h]Application rate [l / h] NOx [mg/Nm3]NO x [mg / Nm 3 ] Brenner 1Burner 1 Brenner 2Burner 2 brennbare Stickstoffverbindungenflammable nitrogen compounds brennbare stickstofffreie Verbindungenflammable nitrogen-free compounds 11 00 2222 2222 210210 240240 575575 22nd 5050 2222 2222 210210 240240 355355 33rd 8080 2222 2222 210210 240240 305305 44th 120120 2222 2222 210210 240240 240240

Wie die erfindungsgemäßen Beispiele zeigen, ist bei dem neuen Verfahren keine Harnstoffzugabe erforderlich, um den NOx-Grenzwert zu unterschreiten. Die CO-Emissionen werden nicht beeinflußt und betragen für beide Versuchsreihen 1,6 bis 1,8 mg/Nm3. Auch der Restsauerstoffgehalt im feuchten Abgas (2,25 %, entspricht 3,0 % im trockenen Abgas) bleibt unverändert.As the examples according to the invention show, no addition of urea is required in the new process in order to fall below the NO x limit value. The CO emissions are not influenced and are 1.6 to 1.8 mg / Nm 3 for both test series. The residual oxygen content in the moist exhaust gas (2.25%, corresponds to 3.0% in the dry exhaust gas) also remains unchanged.

Claims (8)

Verfahren zur Verminderung nitroser Gase (NOx) beim Betreiben von Verbrennungsanlagen, dadurch gekennzeichnet, daß die auf einer Brennerebene angeordneten Brenner teils mit Luftüberschuß, teils mit Luftunterschuß betrieben werden, jeweils bezogen auf die vollständige Verbrennung des verwendeten Heizmittels.Process for reducing nitrous gases (NO x ) when operating combustion plants, characterized in that the burners arranged on one burner level are operated partly with excess air and partly with insufficient air, in each case based on the complete combustion of the heating medium used. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß pro Brennerebene mindestens zwei Brenner verwendet werden, wobei die Differenz der Luftzufuhr der Brenner 20 bis 40 %, vorzugsweise 30 %, beträgt, jeweils bezogen auf die vollständige Verbrennung des Heizmittels.A method according to claim 1, characterized in that per Burner level at least two burners are used, the difference in air supply to the burners being 20 to 40%, preferably 30%, based in each case on the complete combustion of the heating medium. Verfahren gemäß den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß insgesamt ein Überschuß von 15 bis 50 % an Luft, bezogen auf die zur vollständigen Verbrennung des Heizmittels erforderliche Luftmenge, verwendet wird.Process according to claims 1 and 2, characterized characterized that a total of 15 to 50% excess in air, based on that for the complete combustion of the Required amount of air is used. Verfahren gemäß den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man als Heizmittel Erdgas, brennbare Abgase, Heizöle, Kohlenstaub sowie brennbare Abfälle aus der chemischen Produktion verwendet.Process according to claims 1 to 3, characterized characterized in that the heating medium is natural gas, combustible Exhaust gases, heating oils, coal dust and combustible waste chemical production. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß man als Heizmittel stickstoffhaltige, organische Abfälle verwendet.A method according to claim 4, characterized in that nitrogenous organic waste as heating medium used. Verfahren gemäß den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß man bei der Verbrennung von Abfällen mit hohem Stickstoffgehalt mindestens ein Reduktionsmittel zusetzt.Process according to claims 1 to 5, characterized characterized in that when incinerating waste with a high nitrogen content at least one reducing agent adds. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das Reduktionsmittel Harnstoff und/oder Ammoniak ist. A method according to claim 6, characterized in that the Reducing agent is urea and / or ammonia. Verfahren nach Anspruch 1 und mindestens einem der Ansprüche 2 bis 7, dadurch gekennzeichnet, daß das Abgas der Verbrennungsanlage maximal 200 mg NOx/Nm3 enthält.Method according to claim 1 and at least one of claims 2 to 7, characterized in that the exhaust gas of the incinerator contains a maximum of 200 mg NO x / Nm 3 .
EP98120236A 1997-10-31 1998-10-26 Method for reducing nitrons fumes in combustion facilities with simultaneous saving of energy Withdrawn EP0933595A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997148189 DE19748189A1 (en) 1997-10-31 1997-10-31 Nitrous-gas-reduction method in combustion system
DE19748189 1997-10-31

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EP0933595A2 true EP0933595A2 (en) 1999-08-04
EP0933595A3 EP0933595A3 (en) 2000-02-09

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020903A1 (en) * 2002-08-31 2004-03-11 Kuemmel Joachim Method and device for the low nox combustion of tail gases containing soot
CN107859991B (en) * 2017-11-15 2020-02-18 葫芦岛锌业股份有限公司 Natural gas heat supply method for zinc vertical retort smelting

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GB2057115A (en) * 1979-08-06 1981-03-25 Babcock Hitachi Kk Combustion process for reducing nitrogen oxides
US4528918A (en) * 1983-04-20 1985-07-16 Hitachi, Ltd. Method of controlling combustion
EP0190463A2 (en) * 1985-01-28 1986-08-13 Saacke GmbH & Co. KG Method and apparatus for reducing the emission of noxious products from combustion installations
EP0562816A2 (en) * 1992-03-26 1993-09-29 The Boc Group, Inc. Method for combustion of a fuel
DE4306765A1 (en) * 1992-07-22 1994-01-27 Baur Peter Reducing emissions e.g. from boiler furnace - by spraying cold additive esp. urea soln. into furnace

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US3048131A (en) * 1959-06-18 1962-08-07 Babcock & Wilcox Co Method for burning fuel
DE3825291A1 (en) * 1988-07-26 1990-02-01 Ver Kesselwerke Ag METHOD AND COMBUSTION PLANT FOR COMBUSTION OF FOSSILER FUELS WITH REDUCED EMISSIONS OF NITROGEN
US5343820A (en) * 1992-07-02 1994-09-06 Combustion Engineering, Inc. Advanced overfire air system for NOx control

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
GB2057115A (en) * 1979-08-06 1981-03-25 Babcock Hitachi Kk Combustion process for reducing nitrogen oxides
US4528918A (en) * 1983-04-20 1985-07-16 Hitachi, Ltd. Method of controlling combustion
EP0190463A2 (en) * 1985-01-28 1986-08-13 Saacke GmbH & Co. KG Method and apparatus for reducing the emission of noxious products from combustion installations
EP0562816A2 (en) * 1992-03-26 1993-09-29 The Boc Group, Inc. Method for combustion of a fuel
DE4306765A1 (en) * 1992-07-22 1994-01-27 Baur Peter Reducing emissions e.g. from boiler furnace - by spraying cold additive esp. urea soln. into furnace

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DE19748189A1 (en) 1999-05-20
EP0933595A3 (en) 2000-02-09

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Withdrawal date: 20020223