US3581491A - Prevention of hot corrosion in gas turbine engines - Google Patents

Prevention of hot corrosion in gas turbine engines Download PDF

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Publication number
US3581491A
US3581491A US789578A US3581491DA US3581491A US 3581491 A US3581491 A US 3581491A US 789578 A US789578 A US 789578A US 3581491D A US3581491D A US 3581491DA US 3581491 A US3581491 A US 3581491A
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Prior art keywords
chromium
compound
base
oxide
attack
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Expired - Lifetime
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US789578A
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English (en)
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Norman S Bornstein
Michael A Decrescente
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RTX Corp
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United Aircraft Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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
    • F02C3/00—Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/20—Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
    • F02C3/30—Adding water, steam or other fluids for influencing combustion, e.g. to obtain cleaner exhaust gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1814—Chelates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid

Definitions

  • the present invention relates in general to the prevention of hot corrosion of the gas turbine engine alloys exposed at high temperature to minor quantities of ingested sea salt.
  • the above object and other advantages of the invention are achieved by preventing the adverse interaction of the alkali metal salts, principally sodium sulfate formed by a reaction between sea salt and the combustion products of a gas turbine, with the gas turbine engine alloys or coatings.
  • the alkali metal salts principally sodium sulfate formed by a reaction between sea salt and the combustion products of a gas turbine
  • at least one oxide selected from the oxides of chromium, tin, samarium, or columbium is provided in the hot section of the engine either'upstream of or at the alloy surfaces to be protected.
  • a compound mixed with the fuel yields the desired oxide during the combustion process whereby the undesirable species are rendered harmless.
  • the desired oxide is provided at the surface of the alloy in the form of or as a part of a coating thereon.
  • FIG. I is a graph depicting the weight change of a nickelbase alloy with time when exposed to various gaseous environments.
  • FIG. 2 is a graph, illustrating the effect of various fuel additives on the hot corrosion of a nickel-base alloy.
  • FIG. 3 is a graph demonstrating the hot corrosion of Alloy lB-l 900 with various protective coatings.
  • condensed sodium sulfate (Na SO,,) formed as a result of the reaction between sea salt ingested by the engine and 80,, a product of the combustion of gas turbine engine fuels, is the principal corrosive agent responsible for hot corrosion attack.
  • the alkali metal sulfate attacks the protective oxide present on the alloy surface and exposes the substrate to a sulfidation attack whereby sulfides are formed.
  • the attack is characterized by a loosely adhering oxide scale and sulfide precipitates in an alloy denuded zone which is due primarily to an interaction of condensed salts, liquid or solid, with the alloy, and which can occur with the alloy in either the coated or uncoated condition.
  • the corrosive properties of sodium sulfate are significantly attenuated by the presence of certain oxides, specifically those oxides of chromium, tin, samarium and columbium.
  • the common characteristics of these various compounds is that the metallic components can all exist in more than one valency state and that they all, at elevated temperatures form compounds with sodium which are typically more stable than sulfate.
  • the various compounds formed are Na CrO,, Na SnO Na,sm,o,, Na cb O, in the reaction between the combustion products containing sea salts and the oxides of chromium, tin, samarium, and columbium respectively.
  • the key to effective sulfidation inhibition involves the provision of certain oxides which react with the alkali metal salts to form stable alkali metal derivatives.
  • the beneficial effects may be attained in a number of ways including a solid-solid reaction, solid-liquid and gaseous state reaction.
  • the sulfidation-inhibiting medium may be admitted to the engine inlet, at the hot section as, for example, by injection with the fuel, or the oxide may be provided at the alloy surface.
  • sulfidation attack may be prevented by either preventing the deposition of corrosive: salts onto the hot alloy surfaces or by altering the composition and/or chemical activity of the deposited corrosive salts to render them harmless.
  • the sulfidation inhibitor, chromium oxide (Cr O was injected with the sea salt solution into the air entering the burner section. It was added in the form of the water soluble compound ammonium chromate (NH ),Cr O, which readily decomposed in the burner flame to form the desired Cr O
  • NH water soluble compound ammonium chromate
  • FIG. ll It will be observed that, in the presence of the chromate additive, the weight loss of the exposed components after hours of attack approximates that associated with the normal oxidation-erosion associated with salt-free atmosphere, whereas, absent the chromate addition, the corrosive attack is more than 13 times as great.
  • the hot corrosion may be prevented at the component surface itself through the provision of a suitable oxide as or in a coating provided on the component surface.
  • a suitable oxide as or in a coating provided on the component surface.
  • either a liquid-solid or solid-solid phase reaction may be promoted.
  • the sulfidation inhibitor must be present in the form of the oxide or as compounds readily convertible to the oxide. This occurs since the coating must necessarily be oxidation resistant and not prone to oxidation and, hence, the elemental materials are excluded.
  • the method by which the protective oxide is provided in the coating is immaterial and a number of alternatives for generating such coatings such as (1) electroplating (2) electrophoresis (3) flame spray (4) plasma spray (5) vapor plating (6) or pack cementation or others.
  • the sulfidation inhibitor may be added prior to or concurrently with an existing coating process.
  • a layer of chromium metal applied to the alloy substrate is converted to the oxide by exposure at high temperature to air or by a chemical conversion in an oxidation/reduction reaction.
  • the chromium oxide is flame sprayed onto the alloy surface.
  • the chromium oxide addition is an addition to the usual superalloy coatings wherein a stable aluminide is utilized to provide the desired oxidation-erosion resistance. The improvement afforded by the chromium oxide coating is illustrated in FIG. 3.
  • EXAMPLE 1 Two sets of 8 erosion bars formed of the 13-1900 alloy were exposed for 60 hours at 1650" F. to the exhaust of a gas turbine burner fueled with J P-S. One set was exposed to exhaust gases which contained 3.5 ppm. sea salt. The second set was exposed in a similar manner except that a chromate modified sea salt solution was used.
  • the sulfidation inhibitor, Cr O was added to the sea salt solution as water-soluble ammonium chromate, (NH CrO This compound readily decomposes at low temperatures to form Cr O To insure identical distribution of the corrosive salts and the CR O the inhibitor was added directly to the sea salt solution in the amount of 19.6 grams ammonium chromate for each 3.76 grams sodium chloride, which corresponds to a chromium to sodium molar ratio of about 2/ 1.
  • the first set of erosion bars showed distress in less than 20 hours, all specimens exhibiting the loosely adhering green oxide scale typical of sulfidation attack.
  • Metallographic examination of the bars revealed an alloy depleted zone containing sulfide precipitates.
  • the second set of bars exposed under identical condition to the sea salt solution with inhibitor displayed no detrimental sulfidation attack. After 100 hours of test, the specimen weight loss was only very slightly greater than that associated with normal oxidation-erosion.
  • EXAMPLE 2 Two fuel additives, chromium acetylacetonate and chromium isooctadecylsuccinic anhydride were prepared. The additive, chromium isooctadecylsuccinic anhydride is soluble in J P fuels. The other additive was dissolved in benzene prior to mixing with the fuel.
  • the ingredients effective in abating corrosion in those engines subject to the ingestion of mineral salts are the oxides of those metals which can exist in more than one valency state and which, at elevated temperatures, form more stable compounds with sodium and/or calcium than the sulfates, and which are either less corrosive than the sulfates or do not deposit on the hot component surfaces.
  • these metals are chromium, tin, samarium, columbium and mixtures thereof.
  • One or more of the oxides of the above metals, possibly mixed with other oxides such as alumina, will therefor be present in the system.
  • the sulfidation inhibitor When incorporated into a coating on the parts to be protected, the sulfidation inhibitor is provided as the oxide.
  • the inhibitor may be provided in any form convertible to the oxide at or upstream of the surfaces to be protected.
  • Theinhibitor can thus be mixed with the fuel, in appropriate form; utilized in a water injection system; or otherwise be added to the engine gas stream.
  • a compound of chromium, tin, samarium, columbium, or mixtures thereof which is readily converted to the oxide of such metal or metals at elevated temperatures.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US789578A 1969-01-07 1969-01-07 Prevention of hot corrosion in gas turbine engines Expired - Lifetime US3581491A (en)

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US78957869A 1969-01-07 1969-01-07

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US (1) US3581491A (https=)
JP (1) JPS4825682B1 (https=)
CA (1) CA924089A (https=)
DE (1) DE1962714B2 (https=)
FR (1) FR2032309B1 (https=)
GB (1) GB1257001A (https=)
SE (1) SE364077B (https=)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035530A (en) * 1976-05-07 1977-07-12 Apollo Chemical Corporation Method of inhibiting sulfidation and modifying deposits
EP0048910A1 (en) * 1980-09-29 1982-04-07 Great Lakes Carbon Corporation Protective coatings for the high temperature zones of engines
US5538796A (en) * 1992-10-13 1996-07-23 General Electric Company Thermal barrier coating system having no bond coat
RU2133851C1 (ru) * 1993-09-08 1999-07-27 Сименс АГ Способ эксплуатации газовой турбины с подводом добавки
US20040123923A1 (en) * 1992-10-13 2004-07-01 Walston William S. Low sulfur article having a platinum-aluminide protective layer, and its preparation
EP1255879A4 (en) * 2000-02-15 2009-06-24 Univ California Method and composition for the prevention of high temperature corrosion due to alkali sulfates and alkali chlorides
US20100102835A1 (en) * 2008-10-27 2010-04-29 General Electric Company Method and system for detecting a corrosive deposit in a compressor
US20140137564A1 (en) * 2012-11-19 2014-05-22 General Electric Company Mitigation of Hot Corrosion in Steam Injected Gas Turbines

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE9000487U1 (de) * 1990-01-18 1990-04-05 Rölleke, Norbert, 4755 Holzwickede Vorrichtung zur Kenntlichmachung bevorzugter Positionen mittels Positionsschiebern
DE19614035A1 (de) * 1996-04-09 1997-10-16 Christian Regel Aufnahmebehälter für Lotteriescheine mit integrierter Zahlenmerk- und Suchvorrichtung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673145A (en) * 1948-02-26 1954-03-23 Shell Dev High sulfur content fuel
GB734231A (en) * 1953-04-14 1955-07-27 Standard Oil Dev Co Operation of gas turbine equipment
GB758678A (en) * 1953-01-30 1956-10-10 Exxon Research Engineering Co Elimination of carbon in jet combustors
US2966029A (en) * 1957-04-24 1960-12-27 Gulf Research Development Co Corrosion inhibited fuels containing vanadium
US2993673A (en) * 1958-04-11 1961-07-25 Servo Corp Of America Multi-directional shock mount

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2673145A (en) * 1948-02-26 1954-03-23 Shell Dev High sulfur content fuel
GB758678A (en) * 1953-01-30 1956-10-10 Exxon Research Engineering Co Elimination of carbon in jet combustors
GB734231A (en) * 1953-04-14 1955-07-27 Standard Oil Dev Co Operation of gas turbine equipment
US2966029A (en) * 1957-04-24 1960-12-27 Gulf Research Development Co Corrosion inhibited fuels containing vanadium
US2993673A (en) * 1958-04-11 1961-07-25 Servo Corp Of America Multi-directional shock mount

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4035530A (en) * 1976-05-07 1977-07-12 Apollo Chemical Corporation Method of inhibiting sulfidation and modifying deposits
EP0048910A1 (en) * 1980-09-29 1982-04-07 Great Lakes Carbon Corporation Protective coatings for the high temperature zones of engines
US5538796A (en) * 1992-10-13 1996-07-23 General Electric Company Thermal barrier coating system having no bond coat
US20040123923A1 (en) * 1992-10-13 2004-07-01 Walston William S. Low sulfur article having a platinum-aluminide protective layer, and its preparation
US20050121116A1 (en) * 1992-10-13 2005-06-09 General Electric Company Low-sulfur article having a platinum aluminide protective layer and its preparation
US6969558B2 (en) 1992-10-13 2005-11-29 General Electric Company Low sulfur article having a platinum-aluminide protective layer, and its preparation
US7510779B2 (en) 1992-10-13 2009-03-31 General Electric Company Low-sulfur article having a platinum aluminide protective layer and its preparation
RU2133851C1 (ru) * 1993-09-08 1999-07-27 Сименс АГ Способ эксплуатации газовой турбины с подводом добавки
EP1255879A4 (en) * 2000-02-15 2009-06-24 Univ California Method and composition for the prevention of high temperature corrosion due to alkali sulfates and alkali chlorides
US20100102835A1 (en) * 2008-10-27 2010-04-29 General Electric Company Method and system for detecting a corrosive deposit in a compressor
US20140137564A1 (en) * 2012-11-19 2014-05-22 General Electric Company Mitigation of Hot Corrosion in Steam Injected Gas Turbines

Also Published As

Publication number Publication date
DE1962714A1 (de) 1970-07-23
FR2032309B1 (https=) 1975-12-26
JPS4825682B1 (https=) 1973-07-31
DE1962714B2 (de) 1971-09-16
CA924089A (en) 1973-04-10
GB1257001A (https=) 1971-12-15
SE364077B (https=) 1974-02-11
FR2032309A1 (https=) 1970-11-27

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Owner name: FIRST NATIONAL BANK OF CHICAGO, THE,ILLINOIS

Free format text: LICENSE;ASSIGNOR:ELLIOT TURBOMACHINERY CO., INC.;REEL/FRAME:004940/0562

Effective date: 19871109

Owner name: FIRST NATIONAL BANK OF CHICAGO, THE, ONE FIRST NAT

Free format text: LICENSE;ASSIGNOR:ELLIOT TURBOMACHINERY CO., INC.;REEL/FRAME:004940/0562

Effective date: 19871109