EP1099747A2 - Process and plant handling nitrogen containing organic compounds by gasification - Google Patents

Process and plant handling nitrogen containing organic compounds by gasification Download PDF

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Publication number
EP1099747A2
EP1099747A2 EP00124099A EP00124099A EP1099747A2 EP 1099747 A2 EP1099747 A2 EP 1099747A2 EP 00124099 A EP00124099 A EP 00124099A EP 00124099 A EP00124099 A EP 00124099A EP 1099747 A2 EP1099747 A2 EP 1099747A2
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Prior art keywords
gasification
entrained
pressure steam
quencher
organic compounds
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EP00124099A
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German (de)
French (fr)
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EP1099747A3 (en
Inventor
Ullrich Dr. rer. nat. Müller
Uwe Dipl.-Ing. Gaudig
Jürgen Dr. rer. nat. Görz
Manfred Dr.-Ing. Schingnitz
Norbert Dipl.-Ing. Fischer
Wolfgang Dipl.-Ing. Seidel
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Future Energy GmbH
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KRC Umwelttechnik GmbH
Noell KRC Energie und Umwelttechnik GmbH
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Publication of EP1099747A2 publication Critical patent/EP1099747A2/en
Publication of EP1099747A3 publication Critical patent/EP1099747A3/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • 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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/006—Hydrogen cyanide
    • 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
    • C10K1/02—Dust removal
    • C10K1/024—Dust removal by filtration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water

Definitions

  • the invention relates to a method according to the preamble of the first Claim and an apparatus for performing the method.
  • the invention is applicable for harmless recycling Organic nitrogen compounds by gasification to produce a carbon monoxide and hydrogen containing gas.
  • organic nitrogen compounds and especially residual and Chemical industry waste materials are mixtures of amines and nitriles or other nitrogenous hydrocarbons to understand as Waste or residues of the intermediate products of chemical syntheses accruing and for various reasons, e.g. B. not as mixed products can be processed directly.
  • gasification agent and gasification agent such as air, oxygen-enriched air or technical oxygen
  • air, oxygen-enriched air or technical oxygen are optionally in the form of a mixture with water vapor Flame reaction, often under elevated pressure, converted into a carbon monoxide and hydrogen-rich gas.
  • the raw gas generated under these conditions is used as synthesis gas or for energy purposes.
  • the nitrogen-organic compounds are oxidized to neutral nitrogen N 2 even at higher pressures. Further oxidation levels are not reached, therefore nitrogen oxides are not detectable in the gasification gas.
  • the expected formation of ammonia NH3 due to the already described high reduction potential of the gasification gas surprisingly does not occur either.
  • the concentration of ammonia in the gasification gas is at the level known from coal and oil pressure gasification.
  • the solution according to the invention provides a method for recycling an im Essentially consisting of organic nitrogen compounds Input material in such a way that the recovery through gasification under Normal pressure or increased pressure takes place, it being advantageous to one Use pressure up to 40 bar.
  • the temperatures during the gasification process should be> 900 ° C.
  • a suitable range is 1 100 to 1 600 ° C for the Partial oxidation using a free oxygen-containing Gasification agent viewed.
  • Another advantage is that in wastewater treatment separated ammonia for disposal back to the gasification reactor is fed.
  • the process will be different Organic nitrogen compounds together or separately Gasification reactor fed and gasified simultaneously. With the procedure it is still possible that organic and inorganic nitrogen compounds be gassed together.
  • a device for performing the method is distinguished in particular from the fact that a feed into an entrained-flow gasifier with a downstream quencher, one over a Pipeline connected to the quencher wastewater treatment is present, a downstream of the entrained flow gasifier High pressure steam generator is present, the hot gas after a Hot gas filter stage of a COS / HCN hydrolysis is supplied, a Subordinate normal pressure steam generator with subsequent cooling is present, after which in a desulfurization, pure gas and sulfur be generated. Between wastewater treatment and entrained flow gasifier furthermore a pipeline for the disposal of the ammonia Water treatment arranged.
  • the invention is based on a figure and subsequent embodiments described in more detail.
  • the figure shows a technological concept for Gasification of nitrogen-organic compounds.
  • a total of 13,300 kg / h of nitrogen-organic compounds consisting mainly of nitriles and amines are fed to the gasification reactor 2 via feed systems 1, which are obtained as residues in a nylon synthesis.
  • the residue contains an organically bound nitrogen content of 1651 kg / h.
  • the chemically bound nitrogen in the synthesis gas in the form of HCN and NH 3 is 24.9 kg / h, this is only 0.19% of the introduced value.
  • the hot raw gas emerges at 25 bar and approx. 1 300 ° C Gasification reactor in quench stage 3, in which by injecting Water is cooled to 800 ° C.
  • the raw gas is through Excess water cooled down to a dew point of approx. 200 ° C.
  • the very low ash content of the nitrogen-organic residue allows it Fall the partial quench to 800 ° C, so that in the following Steam generator 4 high pressure steam is generated.
  • the Catalytic COS and HCN hydrolysis stage 6 are used for protection the catalyst removes dust-like components in a hot gas filter 5.
  • the raw gas is cooled in a low-pressure steam generator 7 and a cooler 8, in which ammonia from the raw gas passes simultaneously Solution in the condensates is removed from the raw gas.
  • a Desulfurization stage 9 the clean gas 10 can be recycled become.
  • the desulfurization stage 9 turns the sulfur 11 in subtracted elementary form.
  • the ammonia-containing condensates are in the Circuit fed back to the partial quenching 3.
  • the excess condensate gets into the wastewater treatment 12, in which, among other things, the Ammonia is separated. This becomes disposal via line 13 abandoned the gasification reactor 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Industrial Gases (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Process for evaluating a material consisting of organonitrogen compounds comprises carrying out gasification under normal or elevated pressure, preferably up to 40 bar at temperatures more than 900, preferably 1100-1600 degrees C as partial oxidation using a gasifying agent containing free oxygen. The gasification occurs as a flame reaction in a fly stream gasifier. An Independent claim is also included for an apparatus for carrying out the process comprising a feed (1) connected to a fly stream gasifier (2) with a quencher (3); an effluent preparation unit (12) connected to the quencher via a pipeline; a high pressure steam generator (4) connected to a fly stream gasifier, the hot gas being introduced to a COS/HCN hydrolysis unit (6) after a hot gas filter (5); a low pressure steam generator (7) with a condenser (8); a desulfurization unit (9) which produces pure gas (10) and sulfur (11); and a pipeline (13) between the effluent preparation unit and fly stream gasifier to supply ammonia to the effluent preparation unit.

Description

Die Erfindung betrifft ein Verfahren nach dem Oberbegriff des ersten Patentanspruches und eine Vorrichtung zur Durchführung des Verfahrens. Die Erfindung ist anwendbar zur schadlosen Verwertung stickstofforganischer Verbindungen durch Vergasung unter Erzeugung eines kohlenmonoxid- und wasserstoffhaltigen Gases.The invention relates to a method according to the preamble of the first Claim and an apparatus for performing the method. The invention is applicable for harmless recycling Organic nitrogen compounds by gasification to produce a carbon monoxide and hydrogen containing gas.

Unter stickstofforganischen Verbindungen und insbesondere Rest- und Abfallstoffen der chemischen Industrie sind Mischungen von Aminen, Nitrilen oder anderen stickstoffhaltigen Kohlenwasserstoffen zu verstehen, die als Abfallstoffe oder Reste der Zwischenprodukte chemischer Synthesen anfallen und aus unterschiedlichsten Gründen, z. B. als Mischprodukte nicht direkt weiterverarbeitet werden können.Among organic nitrogen compounds and especially residual and Chemical industry waste materials are mixtures of amines and nitriles or other nitrogenous hydrocarbons to understand as Waste or residues of the intermediate products of chemical syntheses accruing and for various reasons, e.g. B. not as mixed products can be processed directly.

Es ist bekannt, kohlenstoffhaltige Rest- und Abfallstoffe unter Nutzung der entstehenden Wärme zu verbrennen. Bestehen solche Materialien jedoch vollständig oder teilweise aus stickstofforganischen Verbindungen, so bilden sich während des Verbrennungsvorganges in hohem Maße Stickoxide, die mit den Abgasen in die Atmosphäre gelangen und maßgeblich zur Versäuerung des Regenwassers beitragen. In den letzten Jahren sind eine Vielzahl katalytischer und nichtkatalytischer Verfahren entwickelt worden, die bei hohen NOx-Konzentrationen zu erheblichen Kosten für die Rauchgasentstickung führen. Die heißen und großvolumigen Rauchgasmengen erfordern eine große Apparateabmessung der zur Entstickung vorgesehenen Apparate und Ausrüstungen. Eine umfangreiche Zusammenfassung zum Stand der Technik geht aus W. Fritz et al. "Reinigung von Abgasen", Vogel Buchverlag, Würzburg 1992 hervor. It is known to burn carbon-containing residues and waste materials using the heat generated. However, if such materials consist entirely or partially of nitrogen-organic compounds, nitrogen oxides are formed to a high degree during the combustion process, which enter the atmosphere with the exhaust gases and make a significant contribution to acidifying the rainwater. A large number of catalytic and non-catalytic processes have been developed in recent years, which lead to considerable costs for flue gas denitrification at high NO x concentrations. The hot and large volumes of flue gas require a large apparatus dimension for the apparatus and equipment intended for denitrification. A comprehensive summary of the prior art can be found in W. Fritz et al. "Purification of exhaust gases", Vogel Buchverlag, Würzburg 1992.

In der Technik der Gaserzeugung ist die Vergasung von Brennstoffen sowie von Rest- und Abfallstoffen, die sich in einem fließfähigen Zustand befinden oder in diesen Zustand überführt werden können, durch partielle Oxidation im Flugstrom bekannt. Dabei werden Vergasungsstoff und Vergasungsmittel, wie Luft, sauerstoffangereicherte Luft oder technischer Sauerstoff gegebenenfalls in Mischung mit Wasserdampf in Form einer
Flammenreaktion, vielfach auch unter erhöhtem Druck, in ein kohlenmonoxid- und wasserstoffreiches Gas umgewandelt. Das unter diesen Bedingungen erzeugte Rohgas wird nach entsprechender Kühlung und Reinigung als Synthesegas oder für energetische Zwecke genutzt.In the art of gas generation, the gasification of fuels and of residual and waste materials which are in a flowable state or can be converted into this state by partial oxidation in the entrained flow is known. The gasification agent and gasification agent, such as air, oxygen-enriched air or technical oxygen, are optionally in the form of a mixture with water vapor
Flame reaction, often under elevated pressure, converted into a carbon monoxide and hydrogen-rich gas. After appropriate cooling and purification, the raw gas generated under these conditions is used as synthesis gas or for energy purposes.

Es ist daher Aufgabe der Erfindung, eine Möglichkeit zur schadlosen Verwertung von stickstofforganischen Verbindungen zu schaffen, die die Nachteile des Standes Technik nicht aufweist.It is therefore an object of the invention to provide a way for harmless Recycling of nitrogenous organic compounds to create the Disadvantages of the prior art does not have.

Diese Aufgabe wird durch ein Verfahren mit den kennzeichnenden Merkmalen des ersten Patentanspruches gelöst und eine Vorrichtung zur Durchführung des Verfahrens.
Unteransprüche geben vorteilhafte Ausgestaltungen der Erfindung wieder.This object is achieved by a method with the characterizing features of the first claim and an apparatus for performing the method.
Sub-claims reflect advantageous embodiments of the invention.

In überraschender Weise wurde gefunden, dass trotz der hochreduzierenden Atmosphäre im Flugstromreaktor auch bei höheren Drücken die stickstofforganischen Verbindungen bis zum neutralen Stickstoff N2 oxidiert werden. Weitere Oxidationsstufen werden nicht erreicht, Stickoxide sind deshalb im Vergasungsgas nicht nachweisbar. Die zu erwartende Bildung von Ammoniak NH3 durch das bereits beschriebene hohe Reduktionspotential des Vergasungsgases tritt überraschender Weise auch nicht auf. Die Konzentration des Ammoniaks im Vergasungsgas bewegt sich in der aus der Kohle- und Öldruckvergasung bekannten Höhe.Surprisingly, it was found that despite the highly reducing atmosphere in the entrained flow reactor, the nitrogen-organic compounds are oxidized to neutral nitrogen N 2 even at higher pressures. Further oxidation levels are not reached, therefore nitrogen oxides are not detectable in the gasification gas. The expected formation of ammonia NH3 due to the already described high reduction potential of the gasification gas surprisingly does not occur either. The concentration of ammonia in the gasification gas is at the level known from coal and oil pressure gasification.

Die erfindungsgemäße Lösung sieht ein Verfahren zur Verwertung eines im Wesentlichen aus stickstofforganischen Verbindungen bestehenden Einsatzstoffes in der Weise vor, dass die Verwertung durch Vergasung unter Normaldruck oder erhöhtem Druck erfolgt, wobei es vorteilhaft ist, einen Druck bis 40 bar zu verwenden. Die Temperaturen beim Vergasungsprozess sollten > 900 °C sein. Als geeigneter Bereich wird 1 100 bis 1 600 °C für die Partialoxidation unter Verwendung eines freien Sauerstoff enthaltenden Vergasungsmittels angesehen.The solution according to the invention provides a method for recycling an im Essentially consisting of organic nitrogen compounds Input material in such a way that the recovery through gasification under Normal pressure or increased pressure takes place, it being advantageous to one Use pressure up to 40 bar. The temperatures during the gasification process should be> 900 ° C. A suitable range is 1 100 to 1 600 ° C for the Partial oxidation using a free oxygen-containing Gasification agent viewed.

Vorteilhaft ist es, die Vergasung durch Partialoxidation als Flammreaktion in einem Flugstromvergaser vorzunehmen.It is advantageous to use the gasification by partial oxidation as a flame reaction to make an entrained flow gasifier.

Weiterhin ist es vorteilhaft, dass die Verwertung von stickstofforganischen Verbindungen in folgenden technologischen Stufen erfolgt:

  • Zuführung in eine Flugstromvergasung Dabei ist es vorteilhaft, einen Flugstromvergaser mit feuerfest ausgekleidetem Reaktorraum zu verwenden. Als nächste Stufe erfolgt die
  • Teilkühlung des heißen Rohgases durch Einspritzen von Wasser im Quenchungsprozess. Als weitere Stufe ist eine
  • Hochdruckdampferzeugung vorgesehen, der eine COS-, HCN-Hydrolyse, eine Entschwefelung und eine Abwasseraufbereitung nachgeordnet sind.
It is also advantageous that the recycling of nitrogen-organic compounds takes place in the following technological stages:
  • Feeding into entrained-flow gasification It is advantageous to use an entrained-flow gasifier with a refractory-lined reactor space. The next stage is the
  • Partial cooling of the hot raw gas by injecting water in the quenching process. Another stage is one
  • High-pressure steam generation is provided, which are followed by COS, HCN hydrolysis, desulfurization and wastewater treatment.

Vorteilhaft ist weiterhin, dass das in der Abwasseraufbereitung abgeschiedene Ammoniak zur Entsorgung wieder dem Vergasungsreaktor zugeführt wird. Bei dem Prozess werden unterschiedliche stickstofforganische Verbindungen gemeinsam oder getrennt dem Vergasungsreaktor zugeführt und simultan vergast. Mit dem Verfahren ist es weiterhin möglich, dass organische und anorganische Stickstoffverbindungen gemeinsam vergast werden.Another advantage is that in wastewater treatment separated ammonia for disposal back to the gasification reactor is fed. The process will be different Organic nitrogen compounds together or separately Gasification reactor fed and gasified simultaneously. With the procedure it is still possible that organic and inorganic nitrogen compounds be gassed together.

Eine Vorrichtung zur Durchführung des Verfahrens zeichnet sich insbesondere dadurch aus, dass eine Zuführung in einen Flugstromvergaser mit einem nachgeordneten Quencher vorhanden ist, eine über eine Rohrleitung mit dem Quencher verbundene Abwasseraufbereitung vorhanden ist, ein dem Flugstromvergaser nachgeschalteter Hochdruckdampferzeuger vorhanden ist, dessen Heißgas nach einer Heißgasfilterstufe einer COS-/HCN-Hydrolyse zugeführt wird, ein dem nachgeordneter Normaldruckdampferzeuger mit anschließender Kühlung vorhanden ist, nach dem in einer Entschwefelung Reingas und Schwefel erzeugt werden. Zwischen Abwasseraufbereitung und Flugstromvergaser ist weiterhin eine Rohrleitung zur Entsorgung des Ammoniaks der Aufwasseraufbereitung angeordnet.A device for performing the method is distinguished in particular from the fact that a feed into an entrained-flow gasifier with a downstream quencher, one over a Pipeline connected to the quencher wastewater treatment is present, a downstream of the entrained flow gasifier High pressure steam generator is present, the hot gas after a Hot gas filter stage of a COS / HCN hydrolysis is supplied, a Subordinate normal pressure steam generator with subsequent cooling is present, after which in a desulfurization, pure gas and sulfur be generated. Between wastewater treatment and entrained flow gasifier furthermore a pipeline for the disposal of the ammonia Water treatment arranged.

Vorteilhaft ist bei der Vorrichtung, wenn eine Rohrleitung zur Zuführung von Wasser in die Quenchung aus der Kühlung und der Niederdruck-Dampferzeugung angeordnet ist.It is advantageous in the device if a pipeline for the supply of Water into the quench from cooling and low pressure steam generation is arranged.

Die Erfindung wird an einer Figur und nachfolgenden Ausführungsbeispielen näher beschrieben. Dabei zeigt die Figur eine technologische Konzeption zur Vergasung stickstofforganischer Verbindungen.The invention is based on a figure and subsequent embodiments described in more detail. The figure shows a technological concept for Gasification of nitrogen-organic compounds.

Dem Vergasungsreaktor 2 werden über Zuführungssysteme 1 insgesamt 13 300 kg/h hauptsächlich aus Nitrilen und Aminen bestehende stickstofforganische Verbindungen zugeführt, die als Reststoffe bei einer Nylonsynthese anfallen. Neben Kohlenstoff, Wasserstoff, Sauerstoff und Schwefel enthält der Reststoff einen organisch gebundenen Stickstoffanteil von 1651 kg/h. Durch die Vergasung mit technischem Sauerstoff im mit einer feuerfesten Auskleidung versehenen Flugstromreaktor 2 entstehen daraus 13 134 m3 i.N./h Synthesegas folgender Zusammensetzung: H2 4,2 Vol.-% CO 26, 6 Vol.-% CO2 27,5 Vol.-% CH4 0,2 Vol.-% N2 11,1 Vol.-% HCN 0,04 Vol.-% NH3 0,28 Vol.-% Aus dem organisch gebundenen Stickstoffanteil von 1651 kg/h bilden sich durch den Vergasungsprozess N2 11,10 Vol.-% HCN 0,04 Vol.-% NH3 0,27 Vol.-% A total of 13,300 kg / h of nitrogen-organic compounds consisting mainly of nitriles and amines are fed to the gasification reactor 2 via feed systems 1, which are obtained as residues in a nylon synthesis. In addition to carbon, hydrogen, oxygen and sulfur, the residue contains an organically bound nitrogen content of 1651 kg / h. Gasification with technical oxygen in the entrained flow reactor 2, which is provided with a refractory lining, results in 13 134 m 3 iN / h synthesis gas of the following composition: H 2 4.2 Vol .-% CO 26, 6 Vol .-% CO 2 27.5 Vol .-% CH 4 0.2 Vol .-% N 2 11.1 Vol .-% HCN 0.04 Vol .-% NH 3 0.28 Vol .-% The gasification process creates the organically bound nitrogen content of 1651 kg / h N 2 11.10 Vol .-% HCN 0.04 Vol .-% NH 3 0.27 Vol .-%

Der in Form von HCN und NH3 vorliegende chemisch gebundene Stickstoff im Synthesegas beträgt 24,9 kg/h, dies sind nur 0,19 % des eingebrachten Wertes.The chemically bound nitrogen in the synthesis gas in the form of HCN and NH 3 is 24.9 kg / h, this is only 0.19% of the introduced value.

Das heiße Rohgas tritt mit 25 bar und ca. 1 300 °C aus dem Vergasungsreaktor in die Quenchstufe 3 ein, in der durch Einspritzen von Wasser eine Abkühlung auf 800 °C erfolgt. In Abhängigkeit von der nachfolgenden Gasaufbereitungstechnologie wird das Rohgas durch Überschusswasser bis zum Taupunkt von ca. 200 °C abgekühlt. Der sehr geringe Aschegehalt des stickstofforganischen Reststoffes erlaubt in diesem Fall die Teilquenchung auf 800 °C, so dass im nachfolgenden Dampferzeuger 4 Hochdruckdampf erzeugt wird. Bevor das Rohgas in die katalytische COS- und HCN-Hydrolysestufe 6 gelangt, werden zum Schutz des Katalysators staubförmige Anteile in einem Heißgasfilter 5 entfernt. Die Abkühlung des Rohgases geschieht in einem Niederdruck-Dampferzeuger 7 und einem Kühler 8, in dem gleichzeitig Ammoniak aus dem Rohgas durch Lösung in den Kondensaten aus dem Rohgas entfernt wird. Nach einer Entschwefelungsstufe 9 kann das Reingas 10 der Verwertung zugeführt werden. Aus der Entschwefelungsstufe 9 wird der Schwefel 11 in elementarer Form abgezogen. Die ammoniakhaltigen Kondensate werden im Kreislauf wieder der Teilquenchung 3 zugeführt. Der Kondensatüberschuss gelangt in die Abwasseraufbereitung 12, in der unter anderem das Ammoniak abgetrennt wird. Dies wird zur Entsorgung über die Leitung 13 wieder dem Vergasungssreaktor 2 aufgegeben. The hot raw gas emerges at 25 bar and approx. 1 300 ° C Gasification reactor in quench stage 3, in which by injecting Water is cooled to 800 ° C. Depending on the subsequent gas processing technology, the raw gas is through Excess water cooled down to a dew point of approx. 200 ° C. The very low ash content of the nitrogen-organic residue allows it Fall the partial quench to 800 ° C, so that in the following Steam generator 4 high pressure steam is generated. Before the raw gas enters the Catalytic COS and HCN hydrolysis stage 6 are used for protection the catalyst removes dust-like components in a hot gas filter 5. The The raw gas is cooled in a low-pressure steam generator 7 and a cooler 8, in which ammonia from the raw gas passes simultaneously Solution in the condensates is removed from the raw gas. After a Desulfurization stage 9, the clean gas 10 can be recycled become. The desulfurization stage 9 turns the sulfur 11 in subtracted elementary form. The ammonia-containing condensates are in the Circuit fed back to the partial quenching 3. The excess condensate gets into the wastewater treatment 12, in which, among other things, the Ammonia is separated. This becomes disposal via line 13 abandoned the gasification reactor 2.

Liste der verwendeten BezugszeichenList of the reference symbols used

11
ZuführungFeed
22nd
Reaktorreactor
33rd
QuencherQuencher
44th
HochdruckdampferzeugerHigh pressure steam generator
55
HeißgasfilterHot gas filter
66
COS-, HCN-HydrolyseCOS, HCN hydrolysis
77
Niederdruck-DampferzeugungLow pressure steam generation
88th
Kühlercooler
99
EntschwefelungDesulfurization
1010th
ReingasClean gas
1111
Schwefelsulfur
1212th
AbwasseraufbereitungWastewater treatment
1313
RohrleitungPipeline
1414
Feinstaubparticulate matter

Claims (7)

Verfahren zur Verwertung eines aus stickstofforganischen Verbindungen bestehenden Einsatzstoffes, dadurch gekennzeichnet, dass
die Verwertung durch Vergasung unter Normaldruck oder erhöhtem Druck, vorzugsweise bis 40 bar, bei Temperaturen > 900 °C, vorzugsweise zwischen 1100 - 1600 °C, als Partialoxidation unter Verwendung eines freien Sauerstoff enthaltenden Vergasungsmittels erfolgt, wobei die Vergasung durch Partialoxidation als Flammenreaktion in einem Flugstromvergaser geschieht.Process for recycling a feedstock consisting of nitrogen-organic compounds, characterized in that
the utilization by gasification under normal pressure or increased pressure, preferably up to 40 bar, at temperatures> 900 ° C, preferably between 1100 - 1600 ° C, as partial oxidation using a free oxygen-containing gasifying agent, the gasification by partial oxidation as a flame reaction in one Entrained-flow gasifier happens. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Verwertung der stickstofforganischen Verbindungen in folgenden technologischen Stufen erfolgt: a) Zuführung in eine Flugstromvergasung in einem mit feuerfestem Material ausgekleideten Reaktor, b) Teilkühlung des heißen Rohgases durch Einspritzen von Wasser im Quencher, c) Hochdruckdampferzeugung, d) COS-,/HCN-Hydrolyse , e) Entschwefelung, f) Abwasseraufbereitung. A method according to claim 1, characterized in that the utilization of the nitrogen organic compounds takes place in the following technological stages: a) feeding into entrained-flow gasification in a reactor lined with refractory material, b) partial cooling of the hot raw gas by injecting water into the quencher, c) high pressure steam generation, d) COS, HCN hydrolysis, e) desulfurization, f) wastewater treatment. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass das in der Abwasseraufbereitung abgeschiedene Ammoniak zur Entsorgung wieder dem Vergasungsreaktor zugeführt wird. A method according to claim 2, characterized in that the ammonia separated in the wastewater treatment Disposal is fed back to the gasification reactor. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass unterschiedliche stickstofforganische Verbindungen gemeinsam oder getrennt dem Vergasungsreaktor zugeführt und simultan vergast werden.Method according to claims 1 to 3, characterized in that different nitrogen organic compounds together or fed separately to the gasification reactor and gasified simultaneously become. Verfahren nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, dass organische und anorganische Stickstoffverbindungen gemeinsam vergast werden.Method according to claims 1 to 4, characterized in that organic and inorganic nitrogen compounds together be gassed. Vorrichtung zur Durchführung eines Verfahrens nach den Ansprüchen 1 bis 5, gekennzeichnet durch Eine Zuführung (1) in einen Flugstromvergaser (2) mit einem nachgeordneten Quencher (3), eine über eine Rohrleitung mit dem Quencher (3) verbundene Abwasseraufbereitung (12), ein dem Flugstromvergaser (2) nachgeschalteter Hochdruckdampferzeuger (4), dessen Heißgas nach einer Heißgasfilterstufe (5) einer COS-/HCN-Hydrolyse (6) zugeführt wird, eine dem nachgeordnete Niederdruckdampferzeugung (7) mit anschließender Kühlung (8), wonach in einer Entschwefelung (9) Reingas (10) und Schwefel (11) erzeugt wird und eine Rohrleitung (13) zwischen Abwasseraufbereitung (12) und Flugstromvergaser (2) zur Entsorgung des Ammoniaks der Abwasseraufbereitung (12) angeordnet ist. Device for carrying out a method according to claims 1 to 5, characterized by A feed (1) into an entrained-flow gasifier (2) with a downstream quencher (3), a wastewater treatment unit (12) connected to the quencher (3) via a pipeline, a high-pressure steam generator (4) connected downstream of the entrained-flow gasifier (2), the hot gas of which is fed to a COS / HCN hydrolysis (6) after a hot gas filter stage (5), one of the downstream low-pressure steam generation (7) with subsequent cooling (8), after which in a Desulfurization (9) clean gas (10) and sulfur (11) is generated and a pipe (13) is arranged between waste water treatment (12) and entrained flow gasifier (2) for the disposal of the ammonia of the waste water treatment (12). Vorrichtung nach Anspruch 6, dadurch gekennzeichnet, dass eine Rohrleitung (14) zur Zuführung von Wasser in die Quenchung (3) aus der Kühlung (8) und der Niederdruck-Dampferzeugung (7) angeordnet ist.Apparatus according to claim 6, characterized in that a pipeline (14) for supplying water to the quench (3) from cooling (8) and low-pressure steam generation (7) is arranged.
EP00124099A 1999-11-11 2000-11-07 Process and plant handling nitrogen containing organic compounds by gasification Withdrawn EP1099747A3 (en)

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DE19954188A DE19954188A1 (en) 1999-11-11 1999-11-11 Process and device for recycling organic nitrogen compounds by gasification

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