Which are the right test conditions for the simulation of high temperature alkali corrosion in biomass combustion?
Authors: Blomberg T. 
Published: February 2006

The use of renewable energy sources for the generation of electricity has gained much interest in recent years. Biomass has the potential of being a CO2 neutral energy source that could provide a significant proportion of the ever‐increasing energy demand. The easiest and most straightforward utilization of the energy content of biomass is direct combustion. The thermal energy of the biomass released in the combustion process is utilized by heating water or steam to produce electricity or heat or both (CHP). Whereas the heat production requires only modest temperatures in the water or steam circuit, producing electricity with high efficiency is not possible without high steam parameters (temperature and pressure). The heat market being quite saturated, the economic potential is in the electricity market. High heat transfer surface temperatures coupled with biomass fired steam generators have resulted, however, in serious corrosion of the heat transfer surfaces, especially in the hottest section of the convection superheaters. The type of corrosion found in biomass boilers is not encountered in fossil fuel fired boilers and the mechanism causing it is not fully understood. The development of new alloys that could withstand these harsh environments would benefit tremendously if the test conditions in the laboratory tests could be chosen so that they adequately resemble the corrosion environment in real boilers. Currently the high corrosion rate is believed to be caused by gaseous KCl that condense on the heat transfer surfaces. While KCl is certainly found in the corroded superheater tubes and probably has an important role in the corrosion reactions with the alloy, the formation of KCl on the cooled surface can also be heterogeneous. In this paper a discussion on the effect of alkali hydroxides, especially KOH, is presented. Biomass fuels have normally a high content of alkali metals and a low content of sulfur and chloride. The excess alkali will produce alkali hydroxides in the combustion environment. Alkali hydroxides then react with CO2 in the flue gases to form carbonates as the flue gases are cooled. The reaction with CO2, is however, very temperature dependent. The equilibrium being completely on the K2CO3 side with a gas temperature below 700 °C and completely on KOH side with a gas temperature above 900 °C. The hottest superheaters are normally located in the area where the flue gas temperature is 850°C–1000 °C. This makes KOH condensation on the tubes possible and subsequent heterogeneous reactions with HCl, SO2 and CO2 in molten phase forming KCl, K2SO2 or K2CO3. Although KOH is not thermodynamically stable at typical tube surface temperatures, a continuous flux condensing from the flue gases results in a corrosion environment on the tube where its activity has to be taken into account. Therefore it is suggested that KOH, either in gaseous or molten phase should be included in the laboratory test environments used for the testing of alloys for biomass combustion applications.