DE4242099A1 - Appts., esp. gas turbine appts. - having coating on its operating parts in contact with fuel gas or waste gas to reduce pollutant emissions - Google Patents
Appts., esp. gas turbine appts. - having coating on its operating parts in contact with fuel gas or waste gas to reduce pollutant emissionsInfo
- Publication number
- DE4242099A1 DE4242099A1 DE4242099A DE4242099A DE4242099A1 DE 4242099 A1 DE4242099 A1 DE 4242099A1 DE 4242099 A DE4242099 A DE 4242099A DE 4242099 A DE4242099 A DE 4242099A DE 4242099 A1 DE4242099 A1 DE 4242099A1
- Authority
- DE
- Germany
- Prior art keywords
- coating
- gas
- appts
- gas turbine
- type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000007789 gas Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 239000002737 fuel gas Substances 0.000 title claims abstract description 5
- 239000003344 environmental pollutant Substances 0.000 title abstract description 4
- 231100000719 pollutant Toxicity 0.000 title abstract description 4
- 239000002912 waste gas Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nitrogenous hydrocarbons Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
- F01D25/007—Preventing corrosion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/88—Handling or mounting catalysts
- B01D53/885—Devices in general for catalytic purification of waste gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
- F01D5/288—Protective coatings for blades
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B77/00—Component parts, details or accessories, not otherwise provided for
- F02B77/02—Surface coverings of combustion-gas-swept parts
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
- F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
- F02C7/30—Preventing corrosion or unwanted deposits in gas-swept spaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23R—GENERATING COMBUSTION PRODUCTS OF HIGH PRESSURE OR HIGH VELOCITY, e.g. GAS-TURBINE COMBUSTION CHAMBERS
- F23R3/00—Continuous combustion chambers using liquid or gaseous fuel
- F23R3/40—Continuous combustion chambers using liquid or gaseous fuel characterised by the use of catalytic means
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B51/00—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines
- F02B51/02—Other methods of operating engines involving pretreating of, or adding substances to, combustion air, fuel, or fuel-air mixture of the engines involving catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
Abstract
Description
Die Erfindung bezieht sich auf eine Vorrichtung,- insbeson dere eine Gasturbineneinrichtung, mit einer Beschichtung von Einrichtungsteilen.The invention relates to a device, in particular a gas turbine device with a coating of furnishings.
Der Konzeption von Gasturbinensystemen liegt ein Anforde rungskomplex zugrunde, der sich einerseits aus dem Streben nach höheren Wirkungsgraden und andererseits aus zunehmend strengeren Umweltschutzvorschriften ergibt. Selbstverständ lich sind alle technischen Maßnahmen, die getroffen werden, um solchen Anforderungen zu genügen, außerdem unter dem Aspekt der Wirtschaftlichkeit zu betrachten. Die Erfindung wird zwar hauptsächlich anhand eines Gasturbinensystems er läutert, läßt sich jedoch auch für andere Einrichtungen, wie z. B. Flugtriebwerke, Turbolader, Auspuffkrümmer oder Auspuffleitungen anwenden.The conception of gas turbine systems is a requirement complex based on the one hand from striving after higher efficiencies and on the other hand increasingly results in stricter environmental regulations. Of course are all technical measures that are taken to meet such requirements, also under the Consider aspect of economy. The invention is mainly based on a gas turbine system refines, but can also be used for other facilities, such as B. aircraft engines, turbochargers, exhaust manifolds or Use exhaust pipes.
Eine Wirkungsgradverbesserung läßt sich bei Gasturbinen durch Erhöhung der Gaseintrittstemperatur erzielen. Mit einer solchen Temperaturerhöhung werden aber auch Einflüsse durch Hochtemperaturkorrosion verstärkt. In der Literatur, und so z. B. auch in der DE 35 43 802 ist deshalb eine kera mische Schutzbeschichtung von Gasturbinenteilen, insbeson dere von Gasturbinenschaufeln, vorgeschlagen worden. Es handelt sich dabei um eine Schutzbeschichtung, die chemi sche Angriffe an der metallischen Oberfläche von Bauelemen ten verringert und/oder durch Wärmedämmwirkung die Tempera tur im Oberflächenbereich des Bauelements absenkt. Als Schutzschicht mit Wärmedämmwirkung wurde z. B. eine Schicht aus Zirkoniumoxid vorgeschlagen, das mit Yttriumoxid stabi lisiert ist. Da eine solche Schicht nicht zufriedendstel lend direkt auf dem Schaufelmetall haftet, wurde außerdem als Haftzwischenschicht eine Legierung mit der Zusammenset zung MCrAlY vorgeschlagen, wobei als Metall M insbesondere Nickel geeignet ist.Efficiency can be improved in gas turbines achieve by increasing the gas inlet temperature. With Such an increase in temperature also has an impact reinforced by high temperature corrosion. In the literature, and so z. B. also in DE 35 43 802 is therefore a kera Mix protective coating of gas turbine parts, in particular those of gas turbine blades, have been proposed. It is a protective coating, the chemi attacks on the metallic surface of building elements ten and / or the temperature due to thermal insulation lowered in the surface area of the component. When Protective layer with thermal insulation was z. B. a layer made of zirconium oxide, which stabilizes with yttrium oxide is identified. Because such a layer is not satisfactory also adheres directly to the blade metal as an adhesive intermediate layer, an alloy with the assembly tongue MCrAlY proposed, with the metal M in particular Nickel is suitable.
Weiterhin ist aus der DE 35 39 029 ein Mischoxidsystem mit Perowskitstruktur als Hochtemperaturkorrosionsschutzschicht bekannt.Furthermore, DE 35 39 029 describes a mixed oxide system Perovskite structure as a high-temperature corrosion protection layer known.
Es sind auch eine Reihe von- Einzelmaßnahmen bekannt, um den Ausstoß einer bestimmten Schadstoffart zu verringern. So wird z. B. in VGB Kraftwerkstechnik 71 (1991) Heft 3, Seite 192 bis 199 erwähnt, daß die Bildung von thermischen Stickoxiden durch die Flammentemperatur und die Verweilzeit bestimmt wird. Als technische Mittel zur NOx-Reduktion durch Verringerung der Flammentemperatur sind dort eine Wasser- oder Wasserdampfeindüsung beschrieben. Eine Verrin gerung der Verweilzeit kann durch Vergrößerung der Brenner zahl und damit einer Flächenverbrennung erreicht werden.A number of individual measures are also known to reduce the emission of a particular type of pollutant. So z. B. in VGB Kraftwerkstechnik 71 (1991) No. 3, pages 192 to 199 mentions that the formation of thermal nitrogen oxides is determined by the flame temperature and the residence time. Water or steam injection are described there as technical means for NO x reduction by reducing the flame temperature. A reduction in the dwell time can be achieved by increasing the number of burners and thus burning the surface.
Eine weitere Möglichkeit besteht darin, zur NOx-Verminde rung eine nichtkatalytische Reduktion im Abgasstrom durch Zusatz von Ammoniak oder Harnstoff oder stickstoffhaltigen Kohlenwasserstoffen bei Temperaturen von 800° bis 1100°C herbeizuführen.Another possibility is to bring about a non-catalytic reduction in the exhaust gas flow by adding ammonia or urea or nitrogenous hydrocarbons at temperatures of 800 ° to 1100 ° C. for NO x reduction.
Die genannten Zusatzstoffe wirken schon bei Temperaturen von 300° bis 450°C, wenn man eine selektive katalytische Reduktion unter Verwendung von Waben- oder Plattenkatalysa toren herbei führt.The additives mentioned already work at temperatures from 300 ° to 450 ° C if you have a selective catalytic Reduction using honeycomb or plate catalysts leads to gates.
Durch Einsatz eines Oxidationskatalysators, ebenfalls ty pisch als Waben- oder Plattenkatalysator, kann auch eine Verminderung des Kohlenmonoxidanteils und der unverbrannten Kohlenwasserstoffe im Abgas erreicht werden.By using an oxidation catalyst, also ty pisch as a honeycomb or plate catalyst, can also Reduction in carbon monoxide and unburned Hydrocarbons can be reached in the exhaust gas.
Nachteilig ist, daß eine Anzahl von ganz unterschiedlichen Maßnahmen getroffen werden muß, um dem gesamten Anforde rungskomplex entsprechen zu können. Insbesondere ist eine Nachschaltung von Einrichtungen zur Abgasbehandlung aufwen dig.The disadvantage is that a number of very different Measures must be taken to meet the entire requirement complex. One is in particular Expenditures of exhaust gas treatment facilities dig.
Der Erfindung liegt die Aufgabe zugrunde, eine Vorrichtung vorzuschlagen, in der eine einfachere Maßnahme oder Maßnah menkombination getroffen ist, um den eingangs genannten An forderungskomplex, nämlich Korrosionsschutz und Schadstoff verringerung zu entsprechen.The invention has for its object a device propose a simpler measure or measure Menkombination is taken to the aforementioned complex of requirements, namely corrosion protection and pollutant reduction to match.
Diese Aufgabe wird gelöst durch eine Vorrichtung, insbeson dere Gasturbineneinrichtung, mit einer Beschichtung auf Einrichtungsteilen, die mit Brenngas oder Abgas in Kontakt treten, wobeiThis object is achieved by a device, in particular dere gas turbine device, with a coating Equipment that comes into contact with fuel gas or exhaust gas kick, being
- - Einrichtungsteile, die sich in einer ersten betriebs mäßigen Gastemperaturzone oberhalb von 600°C befin den, mit einer Beschichtung erster Art versehen sind, die außer einer Hochtemperatur-Korrosionsschutzwir kung auch eine Wirkung als Oxidationskatalysator auf weist und - Furnishing parts that are in a first operating moderate gas temperature zone above 600 ° C which are provided with a coating of the first kind, which apart from a high temperature corrosion protection effect also as an oxidation catalyst points and
- - Einrichtungsteile, die sich in einer zweiten be triebsmäßigen Gastemperaturzone in einem Bereich von 350° bis 600°C befinden, mit einer Beschichtung zwei ter Art versehen sind, die außer einer Hochtempera tur-Korrosionsschutzwirkung auch eine Wirkung als Re duktionskatalysator aufweist.- Furnishing parts, which are in a second driving gas temperature zone in a range of 350 ° to 600 ° C, with one coating two ter type are provided, which except a high temperature tur-corrosion protection effect also an effect as Re has production catalyst.
Mit der Erfindung werden einheitliche Maßnahmen zur Erfül lung der Anforderungen vorgeschlagen, nämlich ausschließ lich Beschichtungen von Einrichtungsteilen einer Vorrich tung, insbesondere einer Gasturbine, um sowohl einen Schutz hinsichtlich Hochtemperaturkorrosion als auch eine Verrin gerung eines Schadstoffausstoßes zu erreichen.With the invention, uniform measures for fulfillment proposed the requirements, namely exclusion Lich coatings of equipment parts of a Vorrich tion, especially a gas turbine, to provide both protection regarding high temperature corrosion as well as a verrin to reduce emissions.
Sowohl die erforderlichen Beschichtungsmaterialien als auch die Verfahren zur Herstellung dieser Beschichtungsmateria lien sowie Verfahren zum Aufbringen der Schichten auf me tallische Teile sind aus dem Stand der Technik bekannt, so daß wenige Hinweise zu Ausführungsmöglichkeiten genügen.Both the required coating materials as well the processes for producing this coating material lines and methods for applying the layers to me metallic parts are known from the prior art, so that a few references to execution options are sufficient.
Erfindungswesentlich ist, daß Beschichtungen gewählt wer den, die eine kombinierte Schutz- und Katalysatorfunktion haben und daß in der Vorrichtung Schichten mit unterschied lichen katalytischen Eigenschaften eingesetzt werden.It is essential to the invention that coatings are chosen the one that has a combined protective and catalytic function have and that in the device layers with difference union catalytic properties are used.
Die grundsätzlichen Anforderungen an solche Schichten, näm lich hoher Ausdehnungskoeffizient, chemische Stabilität gegenüber einer Gasturbinenatmosphäre und hohe Thermo schockbeständigkeit sind selbstverständlich zu beachten.The basic requirements for such layers, näm high coefficient of expansion, chemical stability compared to a gas turbine atmosphere and high thermo shock resistance must of course be taken into account.
Als Schutzschicht mit der Wirkung eines Oxidationskatalysa tors sind z. B. Mischoxide mit Perowskit- oder Spinellstruk tur auf LaMn-Basis geeignet, beispielsweise eines der nach stehenden Werkstoffsysteme:As a protective layer with the effect of an oxidation catalytic converter tors are z. B. mixed oxides with perovskite or spinel structure suitable on LaMn basis, for example one of the following standing material systems:
La0,84Sr0,16MnO3 + (2,5 Gew.% Cr2O3+2,5 Gew.% Bi2O3) (1)
La0,84Ba0,16MnO3 (2)
La0,84Sr0,16MnO3 (3)
La0,8Ba0,2Mn2Cu0,4O3 (4)La 0.84 Sr 0.16 MnO 3 + (2.5 wt.% Cr 2 O 3 + 2.5 wt.% Bi 2 O 3) (1)
La 0.84 Ba 0.16 MnO 3 (2)
La 0.84 Sr 0.16 MnO 3 (3)
La 0.8 Ba 0.2 Mn 2 Cu 0.4 O 3 (4)
Ein solcher Oxidationskatalysator bewirkt eine Nachverbren nung von CO und C-H-Verbindungen in der Temperaturzone oberhalb von 600°C.Such an oxidation catalyst causes afterburning CO and C-H compounds in the temperature zone above 600 ° C.
Als Schutzschicht mit der Wirkung eines Reduktionskatalysa tors ist ein Mischoxid mit Perowskit- oder Spinellstruktur auf LaFeCu-Basis geeignet, beispielsweise eines der nachstehenden Werkstoffsysteme:As a protective layer with the effect of a reduction catalyst tors is a mixed oxide with a perovskite or spinel structure LaFeCu-based, for example one of the following material systems:
La0,84Sr0,16Cu0,6Cr1,6O3 (5)
La0,84Ba0,16Cu0,6Cr1,6O3 (6)
La0,8Fe2,0Cu0,3O3 (7)La 0.84 Sr 0.16 Cu 0.6 Cr 1.6 O 3 (5)
La 0.84 Ba 0.16 Cu 0.6 Cr 1.6 O 3 (6)
La 0.8 Fe 2.0 Cu 0.3 O 3 (7)
Ein solcher Reduktionskatalysator bewirkt eine Reduktion von NOx zu N2 in einem Temperaturbereich von etwa 350° bis 600°C, vorzugsweise bis 500°C.Such a reduction catalyst brings about a reduction of NO x to N 2 in a temperature range from about 350 ° to 600 ° C., preferably up to 500 ° C.
Dieser Vorgang kann noch unterstützt werden durch Zugabe eines Reduktionsmittels, z. B. NH3 oder NH3-Bildner, wie Harnstoff, in das Gasturbinensystem und zwar in einem Über gangsbereich zwischen den beiden Temperaturzonen.This process can be supported by adding a reducing agent, e.g. B. NH 3 or NH 3 formers, such as urea, in the gas turbine system and in a transition area between the two temperature zones.
Die Beschichtungsmaterialien können durch thermische Spritzverfahren, beispielsweise durch Plasma- oder Flamm spritzen, aufgebracht werden.The coating materials can by thermal Spraying processes, for example by plasma or flame spray, be applied.
Je nach Anforderungen, gewählten Materialien und deren Ei genschaften kann die katalytisch wirksame Schicht als al leinige Schicht direkt auf metallische Flächen aufgebracht werden oder auf eine ein- oder mehrschichtige Wärmedämm- und Korrosionsschutzschicht. Praktisch erprobte Schicht dicken für die einzelnen Schichten liegen bei etwa 100 µm bis etwa 700 µm. Depending on the requirements, selected materials and their egg properties can the catalytically active layer as al flax layer applied directly to metallic surfaces or on a single or multi-layer thermal insulation and anti-corrosion layer. Practically proven shift thicknesses for the individual layers are around 100 µm up to about 700 µm.
Soweit Turbinenschaufeln beschichtet werden sollen, kann ein Teil der Schaufeln mit oxydationskatalytischer Wirkung und ein Teil mit reduktionskatalytischer Wirkung beschichtet werden, je nachdem welchem Betriebstemperaturbereich die je weilige Schaufelreihe zuzuordnen ist.As far as turbine blades are to be coated, a part of the blades with an oxidation catalytic effect and a part coated with a reduction catalytic effect be, depending on the operating temperature range the because of the row of blades.
Neben Turbinenschaufeln sind zur Beschichtung auch die In nenwände des Turbinengehäuses sowie des Brennerraums und/oder von Komponenten zur Gasführung geeignet.In addition to turbine blades, the In inner walls of the turbine housing and the burner chamber and / or components suitable for gas routing.
Es versteht sich, daß für die Wahl geeigneter Werkstoffe neben den bereits genannten Anforderungen auch noch weitere Kriterien von Bedeutung sein können, z. B. auch in Abhängig keit von der Art des Brennstoffs für den Gasturbinenbe trieb. So kann z. B. eine Stabilität gegenüber SO2 von Be deutung sein. Es ist in diesem Zusammenhang darauf hinzu weisen, daß mit dem Werkstoffsystem (1) schon eine Lang zeiterfahrung vorliegt, nämlich aus der Verwendung als Kathodenschicht auf Hochtemperaturbrennstoffzellen. Dort hat sich dieses Werkstoffsystem auch bei Verunreinigungen des Brenngases durch Schwefel bewährt. In einem dreimonati gen Versuch mit den Werkstoffsystemen (3), (4) und (7) bei 800°C in einer SO2-Atmosphäre hat sich auch bei diesen Ka talysatoren keine Sulfatbildung gezeigt.It goes without saying that in addition to the requirements already mentioned, other criteria may also be important for the selection of suitable materials, e.g. B. also operated depending on the type of fuel for the gas turbine engine. So z. B. a stability to SO 2 of Be meaning. In this context, it should be pointed out that the material system (1) already has long-term experience, namely from use as a cathode layer on high-temperature fuel cells. This material system has also proven itself there when the fuel gas is contaminated by sulfur. In a three-month test with the material systems (3), (4) and (7) at 800 ° C in a SO 2 atmosphere, no sulfate formation was found even with these catalysts.
Ein weiterer Gesichtspunkt, der bei der Ausführung der Er findung eine Rolle spielen kann, ist die aus strömungstech nischen Gründen bestehende Forderung nach glatter Oberflä che von Turbinenschaufeln und Leitschaufeln, die der Wahl einer katalytisch hochwirksamen rauhen Oberfläche entgegen stehen. Es müssen also optimal, nicht unbedingt maximal wirkende Oberflächengestaltungen gewählt werden. Dies ist möglich, da innerhalb einer Gasturbineneinrichtung insge samt große Flächen zur Verfügung stehen, die mit heißen Verbrennungsgasen in Berührung kommen und somit als Kataly satorflächen genutzt werden können und die andererseits oh nehin eine Schutzbeschichtung erfordern.Another aspect to consider when executing the Er can play a role, is that of flow technology niche reasons existing demand for smooth surface of turbine blades and vanes, the choice against a catalytically effective, rough surface stand. So it must be optimal, not necessarily maximum acting surface designs can be selected. This is possible as a total within a gas turbine facility including large areas that are called hot Combustion gases come into contact and therefore as Kataly can be used and on the other hand oh anyway require a protective coating.
Für das Werkstoffsystem (1) wurde u. a. auch die Hochtempe raturbeständigkeit bis 1200°C in Langzeittest erprobt. Aus den Testergebnissen kann eine mehrjährige Betriebs zeit bei 1000°C und auch eine Thermozyklisierbarkeit gefolgert wer den.For the material system (1) u. a. also the high temperature Temperature resistance up to 1200 ° C tested in long-term test. Out The test results can be subject to several years of operation 1000 ° C and also a thermocyclability inferred who the.
Claims (8)
- - Einrichtungsteile, die sich in einer ersten betriebs mäßigen Gastemperaturzone oberhalb von 600°C befin den, mit einer Beschichtung erster Art versehen sind, die außer einer Hochtemperatur-Korrosionsschutzwir kung auch eine Wirkung als Oxidationskatalysator aufweist und
- - Einrichtungsteile, die sich in einer zweiten be triebsmäßigen Gastemperaturzone in einem Bereich von 350° bis 600°C befinden, mit einer Beschichtung zwei ter Art versehen sind, die außer einer Hochtempera tur-Korrosionsschutzwirkung auch eine Wirkung als Re duktionskatalysator aufweist.
- - Furnishing parts, which are in a first operational gas temperature zone above 600 ° C, are provided with a coating of the first type which, in addition to a high-temperature corrosion protection effect, also has an effect as an oxidation catalyst and
- - Furnishing parts, which are in a second operational gas temperature zone in a range from 350 ° to 600 ° C, are provided with a coating of the second type, which besides a high-temperature corrosion protection effect also has an effect as a reduction catalyst.
La0,84Ba0,16MnO3
La0,84Sr0,16MnO3
La0,8Ba0,2Mn2Cu0,4O3.5. The device according to claim 4, characterized in that the coating of the first type is selected from egg nem of the following material systems La 0.84 Sr 0.16 MnO 3 + (2.5 wt.% Cr 2 O 3 +2.5 % By weight Bi 2 O 3 )
La 0.84 Ba 0.16 MnO 3
La 0.84 Sr 0.16 MnO 3
La 0.8 Ba 0.2 Mn 2 Cu 0.4 O 3 .
La0,84Ba0,16Cu0,6Cr1,6O3
La0,8Fe2,0Cu0,3O3.7. The device according to claim 6, characterized in that one of the following material systems is selected for a coating of the second type: La 0.84 Sr 0.16 Cu 0.6 Cr 1.6 O 3rd
La 0.84 Ba 0.16 Cu 0.6 Cr 1.6 O 3
La 0.8 Fe 2.0 Cu 0.3 O 3 .
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EP0949410A2 (en) | 1998-04-07 | 1999-10-13 | GHH BORSIG Turbomaschinen GmbH | Coated transition duct for a gas turbine |
US6006516A (en) * | 1996-04-19 | 1999-12-28 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
DE19931150A1 (en) * | 1999-07-06 | 2001-01-11 | Volkswagen Ag | Exhaust gas turbocharger for vehicle engines has a turbine wheel with a catalytically active surface |
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Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0718027A1 (en) * | 1994-12-20 | 1996-06-26 | Hitachi, Ltd. | Catalyst-containing heat-insulated member and gas turbine provided with the same |
DE19516815A1 (en) * | 1995-05-08 | 1996-11-14 | Electro Chem Eng Gmbh | Ceramicized light alloy pistons for internal combustion engines |
DE19516829A1 (en) * | 1995-05-08 | 1996-11-14 | Siemens Ag | Fossil fuel gas turbine for power plant |
DE19542944A1 (en) * | 1995-11-17 | 1997-05-22 | Daimler Benz Ag | Internal combustion engine and method for applying a thermal barrier coating |
DE19542944C2 (en) * | 1995-11-17 | 1998-01-22 | Daimler Benz Ag | Internal combustion engine and method for applying a thermal barrier coating |
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US6006516A (en) * | 1996-04-19 | 1999-12-28 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
WO1997040266A2 (en) * | 1996-04-19 | 1997-10-30 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
WO1997040266A3 (en) * | 1996-04-19 | 1998-01-15 | Engelhard Corp | System for reduction of harmful exhaust emissions from diesel engines |
US6256984B1 (en) * | 1996-04-19 | 2001-07-10 | Engelhard Corporation | System for reduction of harmful exhaust emissions from diesel engines |
EP0949410A2 (en) | 1998-04-07 | 1999-10-13 | GHH BORSIG Turbomaschinen GmbH | Coated transition duct for a gas turbine |
EP0949410A3 (en) * | 1998-04-07 | 2000-11-02 | MAN Turbomaschinen AG GHH BORSIG | Coated transition duct for a gas turbine |
US6226978B1 (en) | 1998-04-07 | 2001-05-08 | Ghh Borsig Turbomaschinen Gmbh | Hot gas-carrying gas collection pipe of gas turbine |
DE19815473A1 (en) * | 1998-04-07 | 1999-10-14 | Ghh Borsig Turbomaschinen Gmbh | Hot gas-carrying gas manifold of a gas turbine |
DE19931150A1 (en) * | 1999-07-06 | 2001-01-11 | Volkswagen Ag | Exhaust gas turbocharger for vehicle engines has a turbine wheel with a catalytically active surface |
WO2002097248A1 (en) * | 2001-05-30 | 2002-12-05 | Reinhold Ficht | Internal combustion engine for the combustion of a combustible gas |
EP1878879A1 (en) * | 2006-07-14 | 2008-01-16 | Abb Research Ltd. | Turbocharger with catalytic coating |
WO2008006797A1 (en) * | 2006-07-14 | 2008-01-17 | Abb Research Ltd | Turbocharger having a catalytic coating |
GB2616062A (en) * | 2022-02-28 | 2023-08-30 | Airbus Operations Ltd | Aircraft engine for nitrogen oxide reduction |
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