Corrosion failures due to condensing flue gases containing H2O, SO3, NOx and HCl still occur more often than might be expected. The corrosion failures can be of several types: general corrosion, pitting attack and stress corrosion cracking (SCC). The chemistry of condensing gases is discussed, and some examples of corrosion in large‐scale installations are presented, including blast stoves for steel production, heat recovery steam generators, and waste incineration boilers. The use of thermal insulation inside boiler casings can result in nitrate SCC when the flue gas contains high concentrations of NOx. Nitric acid from flue gas can react with carbon steel and insulation material forming ammonium nitrate and calcium nitrate. Both materials have hygroscopic properties and are very corrosive, even above the water dewpoint of the gases.
Waste Heat Recovery Boilers (WHRB's) enhance the thermal efficiency of gas turbine power generating plants by capturing the heat from the exhaust gas and utilising it to raise steam for increased electricity production or district heating. Under normal conditions the exhaust gas from the turbine is cooled from around 5508C to 808C. Care is taken that condensation will not occur in the cooler parts of the boiler. Nevertheless, during normal operation, dry ammonium nitrate deposits can be formed in the WHRB. These deposits will become wet when the unit is started or shut down, when the temperature falls below the dew point. The deposits may also "sweat" (i.e. absorb atmospheric moisture and become liquid) during extended plant outage periods. In consequence, Intergranular Corrosion Attack (IGA) and Stress Assisted Intergranular Corrosion Attack (SA-IGA) (in general called stress corrosion cracking) can occur in carbon steel construction materials. The sensitivity to IGA of a total of 86 steels, of known compositions, was tested. The steels were subjected to aerated ammonium nitrate solutions of 90 8C with concentrations ranging between 2 and 35 per cent. After an exposure of 65 hours, cross sections of the steels were studied. If IGA occurred, the steel was considered sensitive to ammonium nitrate at that (critical) percentage. During the investigation it was observed that alloying elements in several types of steel influenced its resistance to IGA in ammonium nitrate. Elements such as molybdenum, manganese and chromium had a positive effect on the resistance to nitrate induced IGA, SA-IGA and stress corrosion cracking, whereas carbon and copper were detrimental. The microstructure of the steel also appeared to be important. In many specimens taken from in-service failures, strings of carbide precipitates were found to be present at grain boundaries. The precipitates were identified to be ternary carbides. It seems, therefore, that the presence of carbides at grain boundaries increases the susceptibility of a steel to intergranular corrosion.
Dutch power companies recently have become aware of a hazard due to the presence of radioactive 210Pb in their boilers. In an investigation conducted by KEMA in The Netherlands it was discovered that 210Pb isotope accumulates within fire‐side deposit layers that form on membrane waterwall tubes. Because the measured levels of total radioactivity exceeded the governmental regulation limit of 100 Bq/g, refurbishment activities in the boiler are subject to governmental authorization and must be conducted under the supervision of authorised radiation protection officers. The 210Pb material originates from decay of 238U, which is present in small amounts in coal. During combustion of the coal, heavy metals such as Pb evaporate and are present in the flue gas in the form of Pb, PbCl, PbCl2, PbS, PbS2 or PbSO4, dependent on the gas environment and temperature. These volatile products subsequently will condense at lower temperatures on the waterwall tubes in the boiler.
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