Superheater Corrosion In Biomass Boilers: Today's Science and Technology

This report broadens a previous review of published literature on corrosion of recovery boiler superheater tube materials to consider the performance of candidate materials at temperatures near the deposit melting temperature in advanced boilers firing coal, wood-based fuels, and waste materials as well as in gas turbine environments. Discussions of corrosion mechanisms focus on the reactions in fly ash deposits and combustion gases that can give corrosive materials access to the surface of a superheater tube. Setting the steam temperature of a biomass boiler is a compromise between wasting fuel energy, risking pluggage that will shut the unit down, and creating conditions that will cause rapid corrosion on the superheater tubes and replacement expenses. The most important corrosive species in biomass superheater corrosion are chlorine compounds and the most corrosion resistant alloys are typically FeCrNi alloys containing 20-28% Cr. Although most of these materials contain many other additional additions, there is no coherent theory of the alloying required to resist the combination of high temperature salt deposits and flue gases that are found in biomass boiler superheaters that may cause degradation of superheater tubes. After depletion of chromium by chromate formation or chromic acid volatilization exceeds a critical amount, the protective scale gives way to a thick layer of Fe{sub 2}O{sub 3} over an unprotective (FeCrNi){sub 3}O{sub 4} spinel. This oxide is not protective and can be penetrated by chlorine species that cause further acceleration of the corrosion rate by a mechanism called active oxidation. Active oxidation, cited as the cause of most biomass superheater corrosion under chloride ash deposits, does not occur in the absence of these alkali salts when the chloride is present as HCl gas. Although a deposit is more corrosive at temperatures where it is molten than at temperatures where it is frozen, increasing superheater tube temperatures through the measured first melting point of fly ash deposits does not necessarily produce a step increase in corrosion rate. Corrosion rate typically accelerates at temperatures below the first melting temperature and mixed deposits may have a broad melting temperature range. Although the environment at a superheater tube surface is initially that of the ash deposits, this chemistry typically changes as the deposits mature. The corrosion rate is controlled by the environment and temperature at the tube surface, which can only be measured indirectly. Some results are counter-intuitive. Two boiler manufacturers and a consortium have developed models to predict fouling and corrosion in biomass boilers in order to specify tube materials for particular operating conditions. It would be very useful to compare the predictions of these models regarding corrosion rates and recommended alloys in the boiler environments where field tests will be performed in the current program. Manufacturers of biomass boilers have concluded that it is more cost-effective to restrict steam temperatures, to co-fire biofuels with high sulfur fuels and/or to use fuel additives rather than try to increase fuel efficiency by operating with superheater tube temperatures above melting temperature of fly ash deposits. Similar strategies have been developed for coal fired and waste-fired boilers. Additives are primarily used to replace alkali metal chloride deposits with higher melting temperature and less corrosive alkali metal sulfate or alkali aluminum silicate deposits. Design modifications that have been shown to control superheater corrosion include adding a radiant pass (empty chamber) between the furnace and the superheater, installing cool tubes immediately upstream of the superheater to trap high chloride deposits, designing superheater banks for quick replacement, using an external superheater that burns a less corrosive biomass fuel, moving circulating fluidized bed (CFB) superheaters from the convective pass into the hot recirculated fluidizing medium and adding an insulating layer to superheater tubes to raise their surface temperature above the dew point temperature of alkali chlorides. These design changes offer advantages but introduce other challenges. For example, operating with superheater temperatures above the dew point of alkali chlorides could require the use of creep-resistant tube alloys and doesn't eliminate chloride corrosion. Improved test methods that can be applied within this project include automated dimensional metrology to make a statistical analysis of depth of penetration and corrosion product thickness, and simultaneous thermal analysis measurements to quantify the melting of complex ashes and avoid the unreliability of the standard ash fusion test. Other important developments in testing include the installation of individually-temperature-controlled superheater loops for corrosion testing in operating boilers and temperature gradient testing.