EP1097729B1 - Méthode de conversion catalytique des substances nocives au moyen de plasma - Google Patents

Méthode de conversion catalytique des substances nocives au moyen de plasma Download PDF

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Publication number
EP1097729B1
EP1097729B1 EP00123040A EP00123040A EP1097729B1 EP 1097729 B1 EP1097729 B1 EP 1097729B1 EP 00123040 A EP00123040 A EP 00123040A EP 00123040 A EP00123040 A EP 00123040A EP 1097729 B1 EP1097729 B1 EP 1097729B1
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EP
European Patent Office
Prior art keywords
plasma
added
catalyst
photo
metal
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.)
Expired - Lifetime
Application number
EP00123040A
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German (de)
English (en)
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EP1097729A2 (fr
EP1097729A3 (fr
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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Publication of EP1097729A3 publication Critical patent/EP1097729A3/fr
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Classifications

    • 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 reacting gaseous, liquid and / or solid pollutants in pollutant-free or low-emission decomposition products by the pollutants are excited by a plasma, optionally pre-decomposed or chemically reacted and catalytically decomposed.
  • the pollutants are burned, for example, in a thermal plasma (equilibrium plasma), wherein the thermal plasma can be generated by ionizing a gas by applying a high-frequency electromagnetic field by means of a plasma torch, by electrical discharges or photon beams, by arc or the like.
  • a thermal plasma epithelial plasma
  • the thermal plasma can be generated by ionizing a gas by applying a high-frequency electromagnetic field by means of a plasma torch, by electrical discharges or photon beams, by arc or the like.
  • DE 28 15 430 A1 describes a method for reducing the chemical oxygen demand of contaminated with organic contaminants waters and wastewaters by the water mixed with ionized gases and the impurities contained are oxidatively degraded in the presence of a catalyst.
  • a catalyst In order to maintain the activity of the catalyst, it must be constantly replaced or regenerated or reactivated. This happens, for example, in that the catalyst is continuously conducted in a closed circuit and regenerated with the addition of oxidizing agents in the form of ionized gases.
  • the invention has for its object to provide a simple and inexpensive method for decomposing pollutants by the pollutants excited by a plasma, optionally pre-decomposed or chemically reacted and catalytically decomposed, which ensures complete conversion of the pollutants and in particular requires no regeneration of the catalyst ,
  • this object is achieved in a method of the type mentioned in that the plasma at least one starting material for the formation of at least one under the conditions in the respective active catalyst active catalyst continuously added, the catalyst is formed in the plasma in situ from the starting material and the Pollutants and / or their decomposition products on the catalyst are substantially completely decomposed.
  • the plasma is therefore used on the one hand in a manner known per se to excite the pollutants in order to decompose them or to convert them into intermediates, on the other hand to form the catalyst necessary for complete conversion of the pollutants.
  • the catalyst is constantly being reformed so that neither regeneration or reactivation nor replacement thereof is required.
  • the process according to the invention is suitable for eliminating any pollutants, for example in exhaust gases, waste waters or even solids, which can interact with the plasma.
  • a thermal or a cold plasma can be used, which is produced in any known manner. Accordingly, the choice of catalyst depending on the type and concentration of pollutants and the plasma used.
  • the plasma is added to at least one starting material for forming at least one of the respective plasma activatable photocatalyst continuously, the photocatalyst is formed in the plasma in situ from the starting material and activated and the pollutants and / or their decomposition products on the photocatalyst essentially completely decomposed.
  • photocatalysts are mainly metal oxides or metal sulfides in question, which can be optimized by mixtures of such catalysts, the efficiency of the catalytic decomposition depending on the type of plasma and nature of the pollutants.
  • 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 more preferred Provision is made that oxygen and at least one organometallic compound and / or at least one metal alkoxide be added to the plasma as starting materials for the formation of the photocatalyst, preferably 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 an alkoxide containing at least one such metal is added.
  • organometallic compound and / or at least one metal alkoxide be added to the plasma as starting materials for the formation
  • photocatalysts in the form of metal sulfides, such as CdS, ZnS or mixed sulfides, it is provided in a preferred embodiment that sulfur or a sulfur-containing compound and at least one organometallic compound and / or at least one metal alkoxide are added to the plasma as starting materials for the formation of the photocatalyst.
  • sulfur or a sulfur-containing compound and at least one organometallic compound and / or at least one metal alkoxide are added to the plasma as starting materials for the formation of the photocatalyst.
  • at least one metal from the group cadmium (Cd), zinc (Zn), selenium (Se), tellurium (Te), molybdenum (Mo), tungsten (W) containing organometallic compound and / or at least one metal containing such alkoxide is added.
  • Sulfur-containing compounds include, for example, 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 sulfur-containing organometallic compound or at least one sulfur-containing metal alkoxide can be added.
  • the catalyst activatable by the plasma is a photocatalyst
  • an electromagnetic radiation having a frequency in the region of the excitation frequency of the photocatalyst is used, so that the plasma serves as a light source for activating the photocatalyst
  • at least one additive can be added to the plasma which, by plasma excitation, emits electromagnetic radiation having a frequency in the region of the excitation frequency of the photocatalyst.
  • additives are preferably selected from the group of noble gases, since they do not adversely affect the decomposition of the pollutants.
  • a preferred embodiment of the method according to the invention provides that the plasma additionally added adjuvants and the pollutants are catalytically decomposed by reaction with the excipients.
  • auxiliaries either oxidizing auxiliaries, e.g. Oxygen, can be added, wherein the oxygen in this case can be used on the one hand to oxidize the pollutants, on the other hand to form a photocatalyst in the form of one or more metal oxides.
  • plasma-reducing adjuvants e.g. Hydrogen
  • plasma-reducing adjuvants e.g. Hydrogen
  • hydrogen sulfide may also be used as the starting material for forming the photocatalyst.
  • both oxidatively and reductively acting auxiliaries may be added to the plasma, in particular those excipients which are converted into oxidizing and reducing decomposition products by plasma excitation.
  • water is added, which is split plasma-chemically in acting as an oxidant protons and acting as a reducing agent hydroxide ions.
  • a bulk material made of a dielectric with a high surface area is arranged in the plasma and the catalyst formed in situ is continuously deposited on the dielectric. Due to the large surface of the bulk material, the pollutants are provided with a large contact area with the catalyst and a complete degradation of the same, for example, a complete oxidation to carbon dioxide and water, allows.
  • the latter is deposited, for example, at least on all of a plasma source facing surfaces on the dielectric and optically excited by the plasma source.
  • bulk material primarily porous ceramics or mineral granules, such as clays, clay minerals, zeolites, corundum, or even optically transparent materials, such as glass, quartz wool or the like, are suitable.
  • process according to the invention can be carried out continuously, semicontinuously or batchwise.
  • a plate reactor is filled with dielectric granules in the form of quartz particles, evacuated and charged with argon.
  • argon plasma is generated by ionizing the argon atoms.
  • oxygen for example atmospheric oxygen
  • an organometallic titanium compound or a titanium alcoholate for example Ti (OiC 3 H 7 ) 4
  • TiO 2 is formed, which is photoactive in the ultraviolet range and is deposited as a photocatalytically active layer on the quartz particles.
  • a contaminated with pollutants gas is passed through the reactor, wherein the pollutants are excited by the plasma, pre-decomposed or chemically reacted and catalytically completely decomposed.
  • Continuous addition of oxygen and the Titanalkoholat is constantly formed new TiO 2 , so that always sufficiently active catalyst material is available.
  • the oxygen also serves as an excipient or as a reactant for the pollutants for the oxidative degradation thereof, wherein it is ionized in the high-frequency electromagnetic field.
  • such generated oxygen plasma is reactive, on the other hand it additionally emits electromagnetic radiation in the ultraviolet range in order to activate the photocatalyst deposited on the dielectric granulate.
  • the inventive method is effective at low maintenance over a long period of time and the process can be carried out in particular continuously.
  • suitable for the formation of other catalysts starting materials by varying the energy input of the plasma source and / or by adding other auxiliaries, the method can be optimized for decomposing the respective pollutants and optionally selective reactions for the degradation of pollutants can be effected.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Catalysts (AREA)
  • Treating Waste Gases (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Claims (22)

  1. Procédé de décomposition de substances nocives gazeuses, liquides et/ou solides en produits de décomposition sans substances nocives ou pauvres en substances nocives, selon lequel les substances nocives sont excitées à l'aide d'un plasma, éventuellement décomposées au préalable ou transformées chimiquement et décomposées de façon catalytique,
    caractérisé en ce qu'
    on ajoute au plasma de manière continue au moins une substance de base pour former au moins un catalyseur actif dans ces conditions dans le plasma respectif, le catalyseur dans le plasma étant formé in situ de la substance de base et les substances nocives et/ou leurs produits de décomposition étant décomposé(e)s pour l'essentiel complètement dans le catalyseur.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on ajoute au plasma de manière continue au moins une substance de base pour former au moins un photocatalyseur pouvant être activé par le plasma respectif, le photocatalyseur étant formé et activé dans le plasma in situ à partir de la substance de base et les substances nocives et/ou leurs produits de décomposition étant décomposé(e)s pour l'essentiel complètement dans le photocatalyseur.
  3. Procédé selon la revendication 2,
    caractérisé en ce que
    comme substance de base pour former le photocatalyseur, on ajoute au plasma de l'oxygène et au moins une liaison organométallique et/ou au moins un alcoolat métallique et comme photocatalyseur on forme au moins un oxyde métallique.
  4. Procédé selon la revendication 3,
    caractérisé en ce qu'
    on ajoute une liaison organométallique contenant au moins un métal choisi dans le groupe du titane (Ti), zinc (Zn), niobium (Nb), tungstène (W), étain (Sn), zirconium (Zr), strontium (Sr), tantale (Ta), potassium (K) et/ou un alcoolat présentant au moins un tel métal.
  5. Procédé selon l'une des revendications 2 à 4,
    caractérisé en ce que
    comme substance de base pour former le photocatalyseur on ajoute du soufre au plasma ou une liaison contenant du soufre et au moins une liaison organométallique et/ou au moins un alcoolat métallique et, comme photocatalyseur on forme au moins un sulfure métallique formé.
  6. Procédé selon la revendication 5,
    caractérisé en ce qu'
    on ajoute une liaison organométallique contenant au moins un métal choisi dans le groupe parmi le cadmium (Cd), zinc (Zn), sélénium (Se), tellure (Te), molybdène (Mo), tungstène (W) et/ou un alcoolat contenant au moins un tel métal.
  7. Procédé selon la revendication 5 ou 6,
    caractérisé en ce qu'
    on ajoute au moins une liaison organométallique contenant du soufre ou au moins un alcoolat métallique contenant du soufre.
  8. Procédé selon l'une des revendications 2 à 7,
    caractérisé en ce qu'
    on utilise un plasma émettant un rayonnement électromagnétique à une fréquence comprise dans la plage de la fréquence d'excitation du photocatalyseur.
  9. Procédé selon l'une des revendications 2 à 8,
    caractérisé en ce qu'
    on ajoute au plasma au moins un additif qui émet, lors de l'excitation du plasma, un rayonnement électromagnétique à une fréquence comprise dans la plage de la fréquence d'excitation du photocatalyseur.
  10. Procédé selon la revendication 9,
    caractérisé en ce qu'
    on choisit l'additif parmi le groupe des gaz rares.
  11. Procédé selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    on ajoute au plasma des adjuvants et les substances nocives sont décomposées suite à une réaction avec les adjuvants.
  12. Procédé selon la revendication 11,
    caractérisé en ce qu'
    on ajoute au plasma des adjuvants d'oxydation.
  13. Procédé selon la revendication 12,
    caractérisé en ce qu'
    on ajoute de l'oxygène.
  14. Procédé selon la revendication 11,
    caractérisé en ce qu'
    on ajoute au plasma des adjuvants de réduction.
  15. Procédé selon la revendication 14,
    caractérisé en ce qu'
    on ajoute de l'hydrogène.
  16. Procédé selon la revendication 11
    caractérisé en ce qu'
    on ajoute au plasma des adjuvants aussi bien oxydantes que réductrices.
  17. Procédé selon la revendication 16,
    caractérisé en ce qu'
    on ajoute de l'eau.
  18. Procédé selon l'une des revendications 1 à 17,
    caractérisé en ce qu'
    un matériau en vrac stationnaire composé d'un diélectrique de grande surface est introduit dans le plasma et le catalyseur formé in situ est séparé en continu sur le diélectrique.
  19. Procédé selon la revendication 18,
    caractérisé en ce que
    comme matériau en vrac on utilise des céramiques poreuses.
  20. Procédé selon la revendication 18.
    caractérisé en ce que
    comme matériau en vrac on utilise des granulés minéraux, tels que les argiles, minéraux argileux, zéolithes, corindon ou équivalent.
  21. Procédé selon la revendication 18,
    caractérisé en ce que
    comme matériau en vrac on utilise des matériaux optiquement transparents, tels que la laine de verre ou la laine de quartz ou équivalent.
  22. Procédé selon l'une des revendications 1 à 21,
    caractérisé en ce qu'
    il est mis en oeuvre de manière continue, semi continue ou par charges.
EP00123040A 1999-11-04 2000-10-24 Méthode de conversion catalytique des substances nocives au moyen de plasma Expired - Lifetime EP1097729B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19953110 1999-11-04
DE19953110A DE19953110A1 (de) 1999-11-04 1999-11-04 Verfahren zum katalytischen Umsetzen von Schadstoffen mittels eines Plasmas

Publications (3)

Publication Number Publication Date
EP1097729A2 EP1097729A2 (fr) 2001-05-09
EP1097729A3 EP1097729A3 (fr) 2003-08-13
EP1097729B1 true EP1097729B1 (fr) 2006-03-29

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EP (1) EP1097729B1 (fr)
AT (1) ATE321593T1 (fr)
DE (2) DE19953110A1 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05154392A (ja) * 1991-12-06 1993-06-22 Tanaka Kikinzoku Kogyo Kk 触媒用Ｃｏ基合金基体及び触媒用支持体
GB9216509D0 (en) * 1992-08-04 1992-09-16 Health Lab Service Board Improvements in the conversion of chemical moieties
PL167513B1 (pl) * 1992-10-29 1995-09-30 Inst Chemii Przemyslowej Sposób przemiany dwutlenku siarki z mieszanin gazowych do siarki elementarnej PL
DE4341496A1 (de) * 1993-12-06 1995-06-08 Pcp Photocatalytic Purificatio Mineralisationsverfahren und Anwendungen desselben
DE19525749A1 (de) * 1995-07-14 1997-01-16 Siemens Ag Vorrichtung zur plasmachemischen Zersetzung und/oder Vernichtung von Schadstoffen
JPH09234375A (ja) * 1996-03-01 1997-09-09 Mitsubishi Paper Mills Ltd 光反応性有害物除去材

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EP1097729A2 (fr) 2001-05-09
ATE321593T1 (de) 2006-04-15
DE50013440D1 (de) 2006-10-19
EP1097729A3 (fr) 2003-08-13
DE19953110A1 (de) 2001-05-17

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