EP1097729A2 - Method of catalytic conversion of harmful substances by means of plasma - Google Patents

Method of catalytic conversion of harmful substances by means of plasma Download PDF

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Publication number
EP1097729A2
EP1097729A2 EP00123040A EP00123040A EP1097729A2 EP 1097729 A2 EP1097729 A2 EP 1097729A2 EP 00123040 A EP00123040 A EP 00123040A EP 00123040 A EP00123040 A EP 00123040A EP 1097729 A2 EP1097729 A2 EP 1097729A2
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EP
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Prior art keywords
plasma
added
photocatalyst
pollutants
metal
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EP00123040A
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German (de)
French (fr)
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EP1097729B1 (en
EP1097729A3 (en
Inventor
Peter Dr.Ing. Elsner
Michitaka Dr.Rer.Nat. Ota
Mathias Dr. Kaiser
Rudolf Dr. Emmerich
Helfrich Dr. Urban
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/19—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to plasma
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances

Definitions

  • the invention relates to a method for converting gaseous, liquid and / or solid pollutants in pollutant-free or low-pollution decomposition products by the pollutants excited by means of a plasma, if necessary pre-decomposed or chemically converted and catalytic be decomposed.
  • the pollutants For exhaust gas cleaning and treatment with toxic or harmful substances contaminated liquids or solids it is known to be the pollutants to convert plasma chemical into non-toxic decomposition products.
  • the pollutants are, for example, in one thermal plasma (equilibrium plasma) burned, wherein the thermal plasma by ionizing a gas by applying a high-frequency electromagnetic field by means of a plasma torch, by electrical discharges or photon beams, generated by arcing or the like can be.
  • the pollutant molecules in one cold plasma stimulate and by adding oxidizing agents or reducing agents excited by the plasma be transformed into harmless substances.
  • Such cold plasmas are caused, for example, by glow discharges, silent discharges, corona discharges or by applying a high-frequency electromagnetic field Microwave generators generated under vacuum.
  • Such procedures are, however, not very effective, because despite high technical
  • the pollutants are only partially implemented or only a few pollutants are selectively eliminated.
  • the pollutant molecules decompose completely become.
  • the use of catalysts is complex and expensive and performs due to the necessary regeneration very short downtimes of the system. this applies especially when catalyst poisons are in the medium to be cleaned are included.
  • DE 28 15 430 A1 describes a method for reduction chemical oxygen demand from organic contaminants contaminated water and waste water by the Water mixed with ionized gases and the contained ones Impurities oxidative in the presence of a catalyst be dismantled. To maintain the activity of the catalyst this must be constantly replaced or regenerated or reactivated. This happens, for example in that the catalyst is continuously in a closed Cycle and with the addition of oxidizing agents is regenerated in the form of ionized gases.
  • the invention has for its object a simple and cost-effective process for decomposing pollutants propose by pollutants using a plasma stimulated, possibly pre-decomposed or chemically reacted and be catalytically decomposed, which is a complete Sales of pollutants guaranteed and in particular does not require regeneration of the catalyst.
  • this object is achieved in a method of type mentioned in that the plasma at least a starting material to form at least one under the conditions in the respective plasma active catalyst continuously added, the catalyst in the Plasma is formed in situ from the starting material and the Pollutants and / or their decomposition products on the catalyst are essentially completely decomposed.
  • the plasma is on the one hand in itself known way to stimulate the pollutants used to to decompose or convert them into intermediate products, on the other hand, to form the for complete implementation the catalyst required for pollutants.
  • the catalyst is constantly newly formed so that neither regeneration nor reactivation, an exchange of the same is still necessary.
  • the method according to the invention is arbitrary for elimination Pollutants, e.g. in exhaust gases, waste water or solids suitable that interact with the plasma can.
  • a thermal or a cold plasma which is generated in any known manner becomes.
  • the catalyst is selected accordingly according to the type and concentration of the pollutants and the used Plasma.
  • the plasma at least one starting material to form at least one from the respective plasma activatable photocatalyst continuously added to the photocatalyst in the plasma formed and activated in situ from the starting material and the pollutants and / or their decomposition products essentially completely decomposed on the photocatalyst become.
  • Mainly metal oxides come as photocatalysts or metal sulfides in question, whereby by mixtures such catalysts the efficiency of the catalytic Decomposition depending on the type of plasma and The nature of the pollutants can be optimized.
  • photocatalysts in the form of metal oxides, such as TiO 2 , ZnO 2 , Nb 2 O 5 , WO 3 , SnO 2 , ZrO 2 , SrTiO 2 , KTaO 3 , NiK 4 Nb 6 O 17 or the like, is preferred in Design provided that oxygen and at least one organometallic compound and / or at least one metal alcoholate are added to the plasma as starting materials to form the photocatalyst, preferably at least one metal from the group titanium (Ti), zinc (Zn), niobium, (Nb ), Tungsten (W), tin (Sn), zirconium (Zr), strontium (Sr), tantalum (Ta), potassium (K) containing organometallic compound and / or an alcoholate containing at least one such metal is added.
  • Ti titanium
  • Zn zinc
  • niobium Nb
  • Nb Tungsten
  • W tin
  • Sn zircon
  • photocatalysts in the form of metal sulfides, such as CdS, ZnS or mixed sulfides, it is preferred in a preferred embodiment that sulfur or a sulfur-containing compound and at least one organometallic compound and / or at least one metal alcoholate are added to the plasma as starting materials for forming the photocatalyst, preferably an organometallic compound containing at least one metal from the group cadmium (Cd), zinc (Zn), selenium (Se), tellurium (Te), molybdenum (Mo), tungsten (W) and / or at least one alcoholate containing such a metal is added.
  • Cd group cadmium
  • Zn zinc
  • Se selenium
  • Te tellurium
  • Mo molybdenum
  • W tungsten
  • W tungsten
  • sulfur-containing compounds examples include sulfur oxides, such as SO, SO 2 , SO 3 , SO 4 , S 2 O, S 2 O 3 , S 2 O 7 or hydrogen sulfide.
  • sulfur oxides such as SO, SO 2 , SO 3 , SO 4 , S 2 O, S 2 O 3 , S 2 O 7 or hydrogen sulfide.
  • at least one organometallic compound containing sulfur or at least one metal alcoholate containing sulfur can be added.
  • the catalyst that can be activated by the plasma around a photocatalyst so is more preferred Execution provided that an electromagnetic radiation with a frequency in the range of the excitation frequency of the Plasma emitting photocatalyst is used, so that the plasma as a light source to activate the photocatalyst serves.
  • the plasma at least one additive can be added, which by plasma excitation with electromagnetic radiation Frequency in the range of the excitation frequency of the photocatalyst emitted.
  • Such additives are preferred from selected the group of noble gases, since these decompose the Do not negatively affect pollutants.
  • auxiliaries can either oxidizing auxiliaries, e.g. Oxygen, be added the oxygen in this case, on the one hand, for oxidation the pollutants, on the other hand to form a photocatalyst serve in the form of one or more metal oxides can.
  • auxiliary substances reducing the plasma e.g. Hydrogen added.
  • a photocatalyst in the form of one or more Metal sulfides, for example, also as hydrogen sulfide Starting material used to form the photocatalyst become.
  • the plasma can be both oxidative and reductive acting auxiliaries are added, in particular such excipients come into question by plasma excitation into oxidizing and reducing decomposition products being transformed.
  • Water is preferably added, which is plasma chemical in acting as an oxidizing agent Protons and hydroxide ions acting as reducing agents is split.
  • a plasma is used Bulk material arranged from a dielectric with a large surface and the catalyst formed in situ on the dielectric continuously deposited.
  • the surface of the bulk material becomes a large one for the pollutants Contact area provided with the catalyst and complete degradation thereof, e.g. a complete Oxidation to carbon dioxide and water.
  • the latter becomes e.g. at least on all of them Areas facing the plasma source are deposited on the dielectric and optically excited by the plasma source.
  • Bulk materials come primarily from porous ceramics or mineral ones Granules, such as clays, clay minerals, zeolites, corundum, or optically transparent materials, such as Glass, quartz wool or the like, in question.
  • the process according to the invention can be carried out continuously, be carried out semi-continuously or in batches.
  • a plate reactor is filled with a dielectric granulate in the form of quartz particles, evacuated and charged with argon.
  • An argon plasma is generated by ionizing the argon atoms by applying a high-frequency electromagnetic field to the plate reactor.
  • a photocatalyst in the form of titanium dioxide (TiO 2 ) both oxygen, for example atmospheric oxygen, and an organometallic titanium compound or a titanium alcoholate, for example Ti (OiC 3 H 7 ) 4 , are added to the reactor.
  • TiO 2 is formed in the plasma, which is photoactive in the ultraviolet range and is attached to the quartz particles as a photocatalytically active layer.
  • a gas contaminated with pollutants is passed through the reactor, the pollutants being excited, pre-decomposed or chemically converted and catalytically completely decomposed by means of the plasma.
  • the continuous addition of oxygen and the titanium alcoholate continuously forms new TiO 2 , so that there is always sufficiently active catalyst material available.
  • the oxygen also serves as an auxiliary or as a reaction partner for the pollutants for oxidative degradation thereof, whereby it is ionized in the high-frequency electromagnetic field.
  • An oxygen plasma generated in this way is reactive on the one hand, and on the other hand it additionally emits electromagnetic radiation in the ultraviolet range in order to activate the photocatalyst deposited on the dielectric granulate.

Abstract

In decomposing noxious gases, liquids and/or solids (I) into harmless decomposition products by plasma excitation, optional pre-decomposition or chemical reaction and catalytic decomposition, an active catalyst (II) is formed in situ in the plasma and (I) and/or the decomposition products are decomposed completely on (II). In decomposing noxious gases, liquids and/or solids (I) into (almost) harmless decomposition products by plasma excitation, optional pre-decomposition or chemical reaction and catalytic decomposition, starting material(s) for the formation of active catalyst (II) under the plasma conditions is added to the plasma continuously, (II) is formed in situ in the plasma and (I) and/or the decomposition products are decomposed completely on (II).

Description

Die Erfindung betrifft ein Verfahren zum Umsetzen von gasförmigen, flüssigen und/oder festen Schadstoffen in schadstofffreie oder schadstoffarme Zersetzungsprodukte, indem die Schadstoffe mittels eines Plasmas angeregt, gegebenenfalls vorzersetzt oder chemisch umgesetzt und katalytisch zersetzt werden.The invention relates to a method for converting gaseous, liquid and / or solid pollutants in pollutant-free or low-pollution decomposition products by the pollutants excited by means of a plasma, if necessary pre-decomposed or chemically converted and catalytic be decomposed.

Zur Abgasreinigung und zur Behandlung mit toxischen oder gesundheitsschädlichen Substanzen verunreinigten Flüssigkeiten oder Feststoffen ist es bekannt, die Schadstoffe plasmachemisch in ungiftige Zersetzungsprodukte umzuwandeln. Hierbei werden die Schadstoffe beispielsweise in einem thermischen Plasma (Gleichgewichtsplasma) verbrannt, wobei das thermische Plasma durch Ionisieren eines Gases durch Anlegen eines hochfrequenten elektromagnetischen Feldes mittels eines Plasmabrenners, durch elektrische Entladungen oder Photonenstrahlen, durch Lichtbogen od. dgl. erzeugt werden kann. Bei der Zersetzung vieler toxischer, z.B. cancerogener oder mutagener organischer Verbindungen entstehen jedoch in geringem Umfang noch höher toxische Substanzen, die aufgrund ihrer Toxizität einerseits ein erhebliches gesundheitliches Gefährdungspotential darstellen, andererseits aufgrund ihrer geringen Konzentration noch schwieriger zu entsorgen sind.For exhaust gas cleaning and treatment with toxic or harmful substances contaminated liquids or solids it is known to be the pollutants to convert plasma chemical into non-toxic decomposition products. Here, the pollutants are, for example, in one thermal plasma (equilibrium plasma) burned, wherein the thermal plasma by ionizing a gas by applying a high-frequency electromagnetic field by means of a plasma torch, by electrical discharges or photon beams, generated by arcing or the like can be. When many toxic, e.g. carcinogenic or mutagenic organic compounds to a lesser extent, however, arise even more toxic Substances that, on the one hand, are considerable due to their toxicity represent health hazard potential, on the other hand because of their low concentration are more difficult to dispose of.

Weiterhin ist es bekannt, die Schadstoffmoleküle in einem kalten Plasma (Nicht-thermisches Plasma oder Nicht-Gleichgewichtsplasma) anzuregen und durch Zusetzen von Oxidationsmitteln oder Reduktionsmitteln, die von dem Plasma angeregt werden, in unbedenkliche Stoffe umzuwandeln. Solche kalte Plasmen werden beispielsweise durch Glimmentladungen, stille Entladungen, Korona-Entladungen oder durch Anlegen eines hochfrequenten elektromagnetischen Feldes mittels Mikrowellengeneratoren unter Vakuum erzeugt. Derartige Verfahren sind jedoch wenig effektiv, da trotz hohen technischen Aufwandes die Schadstoffe nur unvollständig umgesetzt bzw. nur einige Schadstoffe selektiv eliminiert werden. Um einen möglichst vollständigen Umsatz der Schadstoffe zu erzielen ist es weiterhin bekannt, die in dem Plasma gebildeten Zersetzungsprodukte anschließend über einen Katalysator zu leiten, an dem die Schadstoffmoleküle vollständig zersetzt werden. Der Einsatz von Katalysatoren ist jedoch aufwendig und teuer und führt aufgrund der notwendigen Regenerierung zu sehr kurzen Standzeiten der Anlage. Dies gilt insbesondere dann, wenn in dem zu reinigenden Medium Katalysatorgifte enthalten sind. Furthermore, it is known that the pollutant molecules in one cold plasma (non-thermal plasma or non-equilibrium plasma) stimulate and by adding oxidizing agents or reducing agents excited by the plasma be transformed into harmless substances. Such cold plasmas are caused, for example, by glow discharges, silent discharges, corona discharges or by applying a high-frequency electromagnetic field Microwave generators generated under vacuum. Such procedures are, however, not very effective, because despite high technical The pollutants are only partially implemented or only a few pollutants are selectively eliminated. Around to achieve the most complete possible conversion of the pollutants it is also known to be those formed in the plasma Decomposition products then over a catalyst to conduct, at which the pollutant molecules decompose completely become. However, the use of catalysts is complex and expensive and performs due to the necessary regeneration very short downtimes of the system. this applies especially when catalyst poisons are in the medium to be cleaned are included.

Die DE 28 15 430 A1 beschreibt ein Verfahren zur Reduktion des chemischen Sauerstoffbedarfs von mit organischen Verunreinigungen belasteten Wässern und Abwässern, indem das Wasser mit ionisierten Gasen vermischt und die enthaltenen Verunreinigungen in Gegenwart eines Katalysators oxidativ abgebaut werden. Um die Aktivität des Katalysators aufrechtzuerhalten, muß dieser ständig ersetzt oder regeneriert bzw. reaktiviert werden. Dies geschieht beispielsweise dadurch, daß der Katalysator kontinuierlich in einem geschlossenen Kreislauf geführt und unter Zusetzen von Oxidationsmitteln in Form ionisierter Gase regeneriert wird.DE 28 15 430 A1 describes a method for reduction chemical oxygen demand from organic contaminants contaminated water and waste water by the Water mixed with ionized gases and the contained ones Impurities oxidative in the presence of a catalyst be dismantled. To maintain the activity of the catalyst this must be constantly replaced or regenerated or reactivated. This happens, for example in that the catalyst is continuously in a closed Cycle and with the addition of oxidizing agents is regenerated in the form of ionized gases.

Der Erfindung liegt die Aufgabe zugrunde, ein einfaches und kostengünstiges Verfahren zum Zersetzen von Schadstoffen vorzuschlagen, indem die Schadstoffe mittels eines Plasmas angeregt, gegebenenfalls vorzersetzt oder chemisch umgesetzt und katalytisch zersetzt werden, welches einen vollständigen Umsatz der Schadstoffe gewährleistet und insbesondere keine Regenerierung des Katalysators erfordert.The invention has for its object a simple and cost-effective process for decomposing pollutants propose by pollutants using a plasma stimulated, possibly pre-decomposed or chemically reacted and be catalytically decomposed, which is a complete Sales of pollutants guaranteed and in particular does not require regeneration of the catalyst.

Erfindungsgemäß wird diese Aufgabe bei einem Verfahren der eingangs genannten Art dadurch gelöst, daß dem Plasma wenigstens ein Ausgangsstoff zur Bildung wenigstens eines unter den Bedingungen in dem jeweiligen Plasma aktiven Katalysators kontinuierlich zugesetzt, der Katalysator in dem Plasma in situ aus dem Ausgangsstoff gebildet wird und die Schadstoffe und/oder deren Zersetzungsprodukte an dem Katalysator im wesentlichen vollständig zersetzt werden.According to the invention, this object is achieved in a method of type mentioned in that the plasma at least a starting material to form at least one under the conditions in the respective plasma active catalyst continuously added, the catalyst in the Plasma is formed in situ from the starting material and the Pollutants and / or their decomposition products on the catalyst are essentially completely decomposed.

Erfindungsgemäß wird das Plasma also einerseits in an sich bekannter Weise zur Anregung der Schadstoffe verwendet, um diese zu zersetzen bzw. in Zwischenprodukte umzuwandeln, andererseits zur Bildung des zur vollständigen Umsetzung der Schadstoffe erforderlichen Katalysators. Durch kontinuierliches Zusetzen der Ausgangsstoffe für den Katalysator zusammen mit den Schadstoffen wird der Katalysator ständig neu gebildet, so daß weder eine Regenerierung oder Reaktivierung, noch ein Austausch desselben erforderlich ist. Das erfindungsgemäße Verfahren ist zur Eliminierung beliebiger Schadstoffe, z.B. in Abgasen, Abwässern oder auch Feststoffen geeignet, die mit dem Plasma in Wechselwirkung treten können. Je nach Beschaffenheit und Konzentration der Schadstoffe kann ein thermisches oder ein kaltes Plasma eingesetzt werden, welches auf beliebige bekannte Weise erzeugt wird. Entsprechend erfolgt die Auswahl des Katalysators je nach Art und Konzentration der Schadstoffe und des eingesetzten Plasmas.According to the invention, the plasma is on the one hand in itself known way to stimulate the pollutants used to to decompose or convert them into intermediate products, on the other hand, to form the for complete implementation the catalyst required for pollutants. Through continuous Add the starting materials for the catalyst together with the pollutants, the catalyst is constantly newly formed so that neither regeneration nor reactivation, an exchange of the same is still necessary. The The method according to the invention is arbitrary for elimination Pollutants, e.g. in exhaust gases, waste water or solids suitable that interact with the plasma can. Depending on the nature and concentration of the pollutants can be used a thermal or a cold plasma which is generated in any known manner becomes. The catalyst is selected accordingly according to the type and concentration of the pollutants and the used Plasma.

In bevorzugter Ausführung ist vorgesehen, daß dem Plasma wenigstens ein Ausgangsstoff zur Bildung wenigstens eines von dem jeweiligen Plasma aktivierbaren Photokatalysators kontinuierlich zugesetzt, der Photokatalysator in dem Plasma in situ aus dem Ausgangsstoff gebildet und aktiviert wird und die Schadstoffe und/oder deren Zersetzungsprodukte an dem Photokatalysator im wesentlichen vollständig zersetzt werden. Als Photokatalysatoren kommen vornehmlich Metalloxide oder Metallsulfide in Frage, wobei durch Mischungen solcher Katalysatoren der Wirkungsgrad der katalytischen Zersetzung in Abhängigkeit der Art des Plasmas und Beschaffenheit der Schadstoffe optimiert werden kann.In a preferred embodiment it is provided that the plasma at least one starting material to form at least one from the respective plasma activatable photocatalyst continuously added to the photocatalyst in the plasma formed and activated in situ from the starting material and the pollutants and / or their decomposition products essentially completely decomposed on the photocatalyst become. Mainly metal oxides come as photocatalysts or metal sulfides in question, whereby by mixtures such catalysts the efficiency of the catalytic Decomposition depending on the type of plasma and The nature of the pollutants can be optimized.

Zur Bildung von Photokatalysatoren in Form von Metalloxiden, wie TiO2, ZnO2, Nb2O5, WO3, SnO2, ZrO2, SrTiO2, KTaO3, NiK4Nb6O17 od. dgl., ist in bevorzugter Ausführung vorgesehen, daß dem Plasma als Ausgangsstoffe zur Bildung des Photokatalysators Sauerstoff und wenigstens eine metallorganische Verbindung und/oder wenigstens ein Metallalkoholat zugesetzt werden, wobei bevorzugt eine wenigstens ein Metall aus der Gruppe Titan (Ti), Zink (Zn), Niob, (Nb), Wolfram (W), Zinn (Sn), Zirkonium (Zr), Strontium (Sr), Tantal (Ta), Kalium (K) enthaltende metallorganische Verbindung und/oder ein wenigstens ein solches Metall enthaltendes Alkoholat zugesetzt wird.To form photocatalysts in the form of metal oxides, such as TiO 2 , ZnO 2 , Nb 2 O 5 , WO 3 , SnO 2 , ZrO 2 , SrTiO 2 , KTaO 3 , NiK 4 Nb 6 O 17 or the like, is preferred in Design provided that oxygen and at least one organometallic compound and / or at least one metal alcoholate are added to the plasma as starting materials to form the photocatalyst, preferably at least one metal from the group titanium (Ti), zinc (Zn), niobium, (Nb ), Tungsten (W), tin (Sn), zirconium (Zr), strontium (Sr), tantalum (Ta), potassium (K) containing organometallic compound and / or an alcoholate containing at least one such metal is added.

Zur Bildung von Photokatalysatoren in Form von Metallsulfiden, wie CdS, ZnS oder Mischsulfiden, ist in bevorzugter Ausführung vorgesehen, daß dem Plasma als Ausgangsstoffe zur Bildung des Photokatalysators Schwefel oder eine schwefelhaltige Verbindung und wenigstens eine metallorganische Verbindung und/oder wenigstens ein Metallalkoholat zugesetzt werden, wobei bevorzugt eine wenigstens ein Metall aus der Gruppe Cadmium (Cd), Zink (Zn), Selen (Se), Tellur (Te), Molybdän (Mo), Wolfram (W) enthaltende metallorganische Verbindung und/oder wenigstens ein solches Metall enthaltendes Alkoholat zugesetzt wird. Als schwefelhaltige Verbindung kommen beispielsweise Schwefeloxide, wie SO, SO2, SO3, SO4, S2O, S2O3, S2O7 oder Schwefelwasserstoff in Frage. Alternativ oder zusätzlich kann wenigstens eine Schwefel enthaltende metallorganische Verbindung oder wenigstens ein Schwefel enthaltendes Metallalkoholat zugesetzt werden.For the formation of photocatalysts in the form of metal sulfides, such as CdS, ZnS or mixed sulfides, it is preferred in a preferred embodiment that sulfur or a sulfur-containing compound and at least one organometallic compound and / or at least one metal alcoholate are added to the plasma as starting materials for forming the photocatalyst, preferably an organometallic compound containing at least one metal from the group cadmium (Cd), zinc (Zn), selenium (Se), tellurium (Te), molybdenum (Mo), tungsten (W) and / or at least one alcoholate containing such a metal is added. Examples of suitable sulfur-containing compounds are sulfur oxides, such as SO, SO 2 , SO 3 , SO 4 , S 2 O, S 2 O 3 , S 2 O 7 or hydrogen sulfide. Alternatively or additionally, at least one organometallic compound containing sulfur or at least one metal alcoholate containing sulfur can be added.

Handelt es sich bei dem von dem Plasma aktivierbaren Katalysator um einen Photokatalysator, so ist in bevorzugter Ausführung vorgesehen, daß ein elektromagnetische Strahlung mit einer Frequenz im Bereich der Anregungsfrequenz des Photokatalysators emittierendes Plasma eingesetzt wird, so daß das Plasma als Lichtquelle zur Aktivierung des Photokatalysators dient. Alternativ oder zusätzlich kann dem Plasma wenigstens ein Zusatzstoff zugesetzt werden, welcher durch Plasmaanregung elektromagnetische Strahlung mit einer Frequenz im Bereich der Anregungsfrequenz des Photokatalysators emittiert. Solche Zusatzstoffe werden bevorzugt aus der Gruppe der Edelgase gwählt, da diese die Zersetzung der Schadstoffe nicht negativ beeinflussen. Is it the catalyst that can be activated by the plasma around a photocatalyst, so is more preferred Execution provided that an electromagnetic radiation with a frequency in the range of the excitation frequency of the Plasma emitting photocatalyst is used, so that the plasma as a light source to activate the photocatalyst serves. Alternatively or additionally, the plasma at least one additive can be added, which by plasma excitation with electromagnetic radiation Frequency in the range of the excitation frequency of the photocatalyst emitted. Such additives are preferred from selected the group of noble gases, since these decompose the Do not negatively affect pollutants.

Eine bevorzugte Ausführung des erfindungsgemäßen Verfahrens sieht vor, daß dem Plasma zusätzlich Hilfsstoffe zugesetzt und die Schadstoffe durch Reaktion mit den Hilfsstoffen katalytisch zersetzt werden. Als Hilfsstoffe können entweder oxidierende Hilfsstoffe, z.B. Sauerstoff, zugesetzt werden, wobei der Sauerstoff in diesem Fall einerseits zur Oxidation der Schadstoffe, andererseits zur Bildung eines Photokatalysators in Form eines oder mehrerer Metalloxide dienen kann.A preferred embodiment of the method according to the invention provides that auxiliary substances are additionally added to the plasma and the pollutants catalytically by reaction with the auxiliary substances be decomposed. As auxiliaries can either oxidizing auxiliaries, e.g. Oxygen, be added the oxygen in this case, on the one hand, for oxidation the pollutants, on the other hand to form a photocatalyst serve in the form of one or more metal oxides can.

Alternativ können dem Plasma reduzierende Hilfsstoffe, z.B. Wasserstoff, zugesetzt werden. In diesem Fall kann zur Bildung eines Photokatalysators in Form eines oder mehrerer Metallsulfide beispielsweise auch Schwefelwasserstoff als Ausgangsstoff zur Bildung des Photokatalysators eingesetzt werden.Alternatively, auxiliary substances reducing the plasma, e.g. Hydrogen added. In this case it can lead to education a photocatalyst in the form of one or more Metal sulfides, for example, also as hydrogen sulfide Starting material used to form the photocatalyst become.

Weiterhin können dem Plasma sowohl oxidativ als auch reduktiv wirkende Hilfsstoffe zugesetzt werden, wobei insbesondere solche Hilfsstoffe in Frage kommen, die durch Plasmaanregung in oxidierende und reduzierende Zersetzungsprodukte umgewandelt werden. Vorzugsweise wird Wasser zugesetzt, welches plasmachemisch in als Oxidationsmittel wirkende Protonen und als Reduktionsmittel wirkende Hydroxid-Ionen gespalten wird.Furthermore, the plasma can be both oxidative and reductive acting auxiliaries are added, in particular such excipients come into question by plasma excitation into oxidizing and reducing decomposition products being transformed. Water is preferably added, which is plasma chemical in acting as an oxidizing agent Protons and hydroxide ions acting as reducing agents is split.

In Weiterbildung des Verfahrens wird in dem Plasma ein Schüttgut aus einem Dielektrikum mit großer Oberfläche angeordnet und der in situ gebildete Katalysator an dem Dielektrikum kontinuierlich abgeschieden. Durch die große Oberfläche des Schüttguts wird den Schadstoffen eine große Kontaktfläche mit dem Katalysator zur Verfügung gestellt und ein vollständiger Abbau derselben, z.B. eine vollständige Oxidation zu Kohlendioxid und Wasser, ermöglicht. Beim Zusetzen von Ausgangsstoffen zur Bildung eines photoaktiven Katalysators wird letzterer z.B. zumindest an allen einer Plasmaquelle zugewandten Flächen an dem Dielektrikum abgeschieden und von der Plasmaquelle optisch angeregt. Als Schüttgut kommen vornehmlich poröse Keramiken oder mineralische Granulate, wie Tone, Tonmineralien, Zeolithe, Korund, oder auch optisch transparente Materialien, wie Glas-, Quarzwolle od. dgl., in Frage.In a further development of the method, a plasma is used Bulk material arranged from a dielectric with a large surface and the catalyst formed in situ on the dielectric continuously deposited. By the big one The surface of the bulk material becomes a large one for the pollutants Contact area provided with the catalyst and complete degradation thereof, e.g. a complete Oxidation to carbon dioxide and water. At the Adding raw materials to form a photoactive The latter becomes e.g. at least on all of them Areas facing the plasma source are deposited on the dielectric and optically excited by the plasma source. As Bulk materials come primarily from porous ceramics or mineral ones Granules, such as clays, clay minerals, zeolites, corundum, or optically transparent materials, such as Glass, quartz wool or the like, in question.

Im übrigen kann das erfindungsgemäße Verfahren kontinuierlich, semikontinierlich oder chargenweise durchgeführt werden.Otherwise, the process according to the invention can be carried out continuously, be carried out semi-continuously or in batches.

Nachfolgend ist die Erfindung anhand eines Ausführungsbeispiels näher erläutert:The invention is based on an exemplary embodiment explained in more detail:

AusführungsbeispielEmbodiment

Ein Plattenreaktor wird mit einem dielektrischen Granulat in Form von Quarzpartikeln befüllt, evakuiert und mit Argon beaufschlagt. Durch Anlegen eines hochfrequenten elektromagnetischen Feldes an den Plattenreaktor wird unter Ionisieren der Argonatome ein Argonplasma erzeugt. Zur Bildung eines Photokatalysators in Form von Titandioxid (TiO2) werden sowohl Sauerstoff, z.B. Luftsauerstoff, als auch eine metallorganische Titanverbindung bzw. ein Titanalkoholat, z.B. Ti-(O-i-C3H7)4, dem Reaktor zugesetzt. Im Plasma wird TiO2 gebildet, welches im ultravioletten Bereich photoaktiv ist und als photokatalytisch aktive Schicht an die Quarzpartikel angelagert wird. Gleichzeitig oder anschließend wird ein mit Schadstoffen verunreinigtes Gas durch den Reaktor geleitet, wobei die Schadstoffe mittels des Plasmas angeregt, vorzersetzt oder chemisch umgesetzt und katalytisch vollständig zersetzt werden. Durch kontinuierliches Zusetzen von Sauerstoff und dem Titanalkoholat wird ständig neues TiO2 gebildet, so daß stets hinreichend aktives Katalysatormaterial zur Verfügung steht. Der Sauerstoff dient ferner als Hilfsstoff bzw. als Reaktionspartner für die Schadstoffe zum oxidativen Abbau derselben, wobei er in dem hochfrequenten elektromagnetischen Feld ionisiert wird. Ein solchermaßen erzeugtes Sauerstoffplasma ist einerseits reaktiv, andererseits emittiert es zusätzlich elektromagnetische Strahlung im ultravioletten Bereich, um den auf dem dielektrischen Granulat abgeschiedenen Photokatalysator zu aktivieren.A plate reactor is filled with a dielectric granulate in the form of quartz particles, evacuated and charged with argon. An argon plasma is generated by ionizing the argon atoms by applying a high-frequency electromagnetic field to the plate reactor. To form a photocatalyst in the form of titanium dioxide (TiO 2 ), both oxygen, for example atmospheric oxygen, and an organometallic titanium compound or a titanium alcoholate, for example Ti (OiC 3 H 7 ) 4 , are added to the reactor. TiO 2 is formed in the plasma, which is photoactive in the ultraviolet range and is attached to the quartz particles as a photocatalytically active layer. Simultaneously or subsequently, a gas contaminated with pollutants is passed through the reactor, the pollutants being excited, pre-decomposed or chemically converted and catalytically completely decomposed by means of the plasma. The continuous addition of oxygen and the titanium alcoholate continuously forms new TiO 2 , so that there is always sufficiently active catalyst material available. The oxygen also serves as an auxiliary or as a reaction partner for the pollutants for oxidative degradation thereof, whereby it is ionized in the high-frequency electromagnetic field. An oxygen plasma generated in this way is reactive on the one hand, and on the other hand it additionally emits electromagnetic radiation in the ultraviolet range in order to activate the photocatalyst deposited on the dielectric granulate.

Da die Zersetzung der Schadstoffe und die Neubildung des Photokatalysators parallel verlaufen, ist das erfindungsgemäße Verfahren bei einem geringen Wartungsaufwand über einen langen Zeitraum wirksam und kann das Verfahren insbesondere kontinuierlich durchgeführt werden. Durch Zusetzen weiterer, zur Bildung anderer Katalysatoren geeigneter Ausgangsstoffe, durch Variation des Energieeintrags der Plasmaquelle und/oder durch Zusetzen weiterer Hilfsstoffe kann das Verfahren zum Zersetzen der jeweiligen Schadstoffe optimiert und können gegebenenfalls selektive Reaktionen zum Abbau der Schadstoffe bewirkt werden.As the decomposition of the pollutants and the new formation of the Running photocatalyst in parallel is the invention Procedure with a low maintenance effort over a effective for a long period of time and the procedure in particular be carried out continuously. By clogging further starting materials suitable for the formation of other catalysts, by varying the energy input from the plasma source and / or by adding other auxiliaries optimized the process for decomposing the respective pollutants and can optionally selective reactions to Degradation of pollutants can be effected.

Claims (22)

Verfahren zum Zersetzen von gasförmigen, flüssigen und/oder festen Schadstoffen in schadstofffreie oder schadstoffarme Zersetzungsprodukte, indem die Schadstoffe mittels eines Plasmas angeregt, gegebenenfalls vorzersetzt oder chemisch umgesetzt und katalytisch zersetzt werden, dadurch gekennzeichnet, daß dem Plasma wenigstens ein Ausgangsstoff zur Bildung wenigstens eines unter den Bedingungen in dem jeweiligen Plasma aktiven Katalysators kontinuierlich zugesetzt, der Katalysator in dem Plasma in situ aus dem Ausgangsstoff gebildet wird und die Schadstoffe und/oder deren Zersetzungsprodukte an dem Katalysator im wesentlichen vollständig zersetzt werden.Process for the decomposition of gaseous, liquid and / or solid pollutants in pollutant-free or Low-pollution decomposition products by the pollutants excited by means of a plasma, if necessary pre-decomposed or chemically converted and catalytic be decomposed, characterized in that the plasma at least one starting material for formation at least one under the conditions in the respective plasma active catalyst added continuously, the catalyst in the plasma in situ from the starting material is formed and the pollutants and / or their decomposition products on the catalyst essentially be completely decomposed. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß dem Plasma wenigstens ein Ausgangsstoff zur Bildung wenigstens eines von dem jeweiligen Plasma aktivierbaren Photokatalysators kontinuierlich zugesetzt, der Photokatalysator in dem Plamsa in situ aus dem Ausgangsstoff gebildet und aktiviert wird und die Schadstoffe und/oder deren Zersetzungsprodukte an dem Photokatalysator im wesentlichen vollständig zersetzt werden.A method according to claim 1, characterized in that the plasma has at least one starting material for formation at least one that can be activated by the respective plasma Photocatalyst continuously added to the Photocatalyst in the Plamsa in situ from the starting material is formed and activated and the pollutants and / or their decomposition products on the photocatalyst essentially completely decomposed become. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß dem Plasma als Ausgangsstoffe zur Bildung des Photokatalysators Sauerstoff und wenigstens eine metallorganische Verbindung und/oder wenigstens ein Metallalkoholat zugesetzt werden und als Photokatalysator wenigstens ein Metalloxid gebildet wird.A method according to claim 2, characterized in that the plasma as starting materials for the formation of the photocatalyst Oxygen and at least one organometallic Compound and / or at least one metal alcoholate be added and at least as a photocatalyst a metal oxide is formed. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß eine wenigstens ein Metall aus der Gruppe Titan (Ti), Zink (Zn), Niob (Nb), Wolfram (W), Zinn (Sn), Zirkonium (Zr), Strontium (Sr), Tantal (Ta), Kalium (K) enthaltende metallorganische Verbindung und/oder ein wenigstens ein solches Metall aufweisendes Alkoholat zugesetzt wird.A method according to claim 3, characterized in that one at least one metal from the group titanium (Ti), Zinc (Zn), Niobium (Nb), Tungsten (W), Tin (Sn), Zirconium (Zr), strontium (Sr), tantalum (Ta), potassium (K) containing organometallic compound and / or at least one such an alcoholate containing metal is added becomes. Verfahren nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, daß dem Plasma als Ausgangsstoffe zur Bildung des Photokatalysators Schwefel oder eine schwefelhaltige Verbindung und wenigstens eine metallorganische Verbindung und/oder wenigstens ein Metallalkoholat zugesetzt werden und als Photokatalysator wenigstens ein Metallsulfid gebildet wird.Method according to one of claims 2 to 4, characterized characterized in that the plasma as starting materials for Formation of the sulfur or photocatalyst sulfur-containing compound and at least one organometallic Compound and / or at least one metal alcoholate be added and as a photocatalyst at least one metal sulfide is formed. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine wenigstens ein Metall aus der Gruppe Cadmium (Cd), Zink (Zn), Selen (Se), Tellur (Te), Molybdän (Mo), Wolfram (W) enhaltende metallorganische Verbindung und/oder ein wenigstens ein solches Metall enthaltendes Alkoholat zugesetzt wird.A method according to claim 5, characterized in that one at least one metal from the group cadmium (Cd), zinc (Zn), selenium (Se), tellurium (Te), molybdenum (Mo), Tungsten (W) containing organometallic compound and / or containing at least one such metal Alcoholate is added. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß wenigstens eine Schwefel enthaltende metallorganische Verbindung oder wenigstens ein Schwefel enthaltendes Metallalkoholat zugesetzt wird.A method according to claim 5 or 6, characterized in that that at least one organometallic sulfur-containing Compound or at least one sulfur containing metal alcoholate is added. Verfahren nach einem der Ansprüche 2 bis 7, dadurch gekennzeichnet, daß ein elektromagnetische Strahlung mit einer Frequenz im Bereich der Anregungsfrequenz des Photokatalysators emittierendes Plasma eingesetzt wird.Method according to one of claims 2 to 7, characterized characterized that an electromagnetic radiation with a frequency in the range of the excitation frequency of the photocatalyst emitting plasma used becomes. Verfahren nach einem der Ansprüche 2 bis 8, dadurch gekennzeichnet, daß dem Plasma wenigstens ein Zusatzstoff zugesetzt wird, welcher durch Plasmaanregung elektromagnetische Strahlung mit einer Frequenz im Bereich der Anregungsfrequenz des Photokatalysators emittiert.Method according to one of claims 2 to 8, characterized characterized in that the plasma has at least one additive is added, which by plasma excitation electromagnetic radiation with a frequency in the range the excitation frequency of the photocatalyst emitted. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß der Zusatzstoff aus der Gruppe der Edelgase gewählt wird.A method according to claim 9, characterized in that the additive is selected from the group of noble gases becomes. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß dem Plasma Hilfsstoffe zugesetzt und die Schadstoffe durch Reaktion mit den Hilfsstoffen zersetzt werden.Method according to one of claims 1 to 10, characterized characterized in that additives are added to the plasma and the pollutants by reaction with the auxiliary substances be decomposed. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß dem Plasma oxidierende Hilfsstoffe zugesetzt werden.A method according to claim 11, characterized in that oxidizing auxiliaries are added to the plasma. Verfahren nach Anspruch 12, dadurch gekennzeichnet, daß Sauerstoff zugesetzt wird.A method according to claim 12, characterized in that oxygen is added. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß dem Plasma reduzierende Hilfsstoffe zugesetzt werden.A method according to claim 11, characterized in that reducing agents are added to the plasma. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß Wasserstoff zugesetzt wird.A method according to claim 14, characterized in that hydrogen is added. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß dem Plasma sowohl oxidativ als auch reduktiv wirkende Hilfsstoffe zugesetzt werden.A method according to claim 11, characterized in that the plasma is both oxidative and reductive Auxiliaries are added. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß Wasser zugesetzt wird.A method according to claim 16, characterized in that water is added. Verfahren nach einem der Ansprüche 1 bis 17, dadurch gekennzeichnet, daß ein stationäres Schüttgut aus einem Dielektrikum mit großer Oberfläche in das Plasma eingebracht und der in situ gebildete Katalysator an dem Dielektrikum kontinuierlich abgeschieden wird.Method according to one of claims 1 to 17, characterized characterized in that a stationary bulk material from a Dielectric with a large surface area in the plasma introduced and the catalyst formed in situ the dielectric is continuously deposited. Verfahren nach Anspruch 18, dadurch gekennzeichnet, daß als Schüttgut poröse Keramiken eingesetzt werden.A method according to claim 18, characterized in that porous ceramics are used as bulk material. Verfahren nach Anspruch 18, dadurch gekennzeichnet, daß als Schüttgut mineralische Granulate, wie Tone, Tonmineralien, Zeolithe, Korund od. dgl., eingesetzt werden.A method according to claim 18, characterized in mineral granules such as clays, Clay minerals, zeolites, corundum or the like become. Verfahren nach Anspruch 18, dadurch gekennzeichnet, daß als Schüttgut optisch transparente Materialien, wie Glas-, Quarzwolle od. dgl., eingesetzt werden.A method according to claim 18, characterized in that as bulk material optically transparent materials, such as glass wool, quartz wool or the like, are used. Verfahren nach einem der Ansprüche 1 bis 21, dadurch gekennzeichnet, daß es kontinuierlich, semikontinuierlich oder chargenweise durchgeführt wird.Method according to one of claims 1 to 21, characterized characterized that it is continuous, semi-continuous or carried out in batches.
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WO1994003263A1 (en) * 1992-08-04 1994-02-17 Public Health Laboratory Service Board Improvements in the conversion of chemical moieties
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PL167513B1 (en) * 1992-10-29 1995-09-30 Inst Chemii Przemyslowej Method of converting sulfur dioxide contained in gaseous mixtures into elementary sulfur
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WO1994003263A1 (en) * 1992-08-04 1994-02-17 Public Health Laboratory Service Board Improvements in the conversion of chemical moieties
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