Organic acid formation in steam–water cycles: Influence of temperature, retention time, heating rate and O2

Organic carbon breaks down in boilers by hydrothermolysis, leading to the formation of organic acid anions, which are suspected to cause corrosion of steam–water cycle components. Prediction of the identity and quantity of these anions, based on feedwater organic carbon concentrations, has not been attempted, making it hard to establish a well-founded organic carbon guideline. By using a batch-reactor and flow reactor, the influence of temperature (276–352 °C), retention time (1–25 min), concentration (150–2400 ppb) and an oxygen scavenger (carbohydrazide) on organic acid anion formation from organic carbon was investigated. By comparing this to data gathered at a case-study site, the validity of setups was tested as well. The flow reactor provided results more representative for steam–water cycles than the batch reactor. It was found that lower heating rates give more organic acid anions as degradation products of organic carbon, both in quantity and species variety. The thermal stability of the organic acid anions is key. As boiler temperature increases, acetate becomes the dominant degradation product, due to its thermal stability. Shorter retention times lead to more variety and quantity of organic acid anions, due to a lack of time for the thermally less stable ones to degrade. Reducing conditions (or the absence of oxygen) increase the thermal stability of organic acid anions. As the feedwater organic carbon concentration decreases, there are relatively more organic acid anions formed.