Ash Formation and Behavior in Utility Boilers by: Steven A. Benson, Ph.D.

as printed in Microbeam Part 6: Ash Deposit Strength Development and Slag Flow: Low Temperature Process (<2000 oF) In the last newsletter I discussed strength development of ash deposits and slag flow related to high temperature phases (>2000 oF). The discussion was focused primarily on flow of a viscous liquid. In this newsletter, I will discuss ash deposit strength development that results when the vaporized ash components condense and/or react upon gas cooling. The elements that vaporize consist mainly of sodium, potassium, sulfur, phosphorus, chlorine, and minor amounts of other elements. In the vapor state the elements can exist in the elemental, oxide, hydroxide, chloride, sulfate, sulfide, phosphate, and other forms. The form of the vapor phase species depends upon temperature and gas composition. As the temperature of the gases decrease due to the transfer of heat in the boiler more of the inorganic vapor phases species condense. These species can condense heterogeneously on the surfaces of ash particles, deposits, and heat transfer surfaces or homogeneously to form submicron aerosols. In addition to condensation, direct reaction of vapor phase species with solid ash particles can occur (ie., reaction of SO2/SO3 with CaO). Low melting point and low viscosity liquid phases are usually produced as a result of the condensation/reaction of these components. Figure 1 illustrates the type of liquid and other bonding phases present in deposits as a function of temperature. At lower temperatures, condensed phases dominate, while at higher temperatures the bulk of the ash particles produce molten phases such as silicates. As discussed in the last newsletter, in low-temperature fouling, the bonding is a result of the formation of condensed phases including sulfates, chlorides, and phosphates. Condensed sulfur species, principally in the form of sulfate, are the dominant phases that form the matrix or bonding material in the low-temperature deposits when firing coals or biomass containing high levels of alkali and alkaline earth elements. High temperature fouling occurs in regions of the utility boiler where temperatures exceed the stability of the sulfate-bearing phases ( >2000 oF). The higher temperature causes melting and interaction of the particles to form a liquid phase depicted by region (v) in Figure 1. Once a liquid phase has formed on the outside of the deposit, it becomes an efficient collector of ash particles, regardless of the individual melting characteristics of the particles. Low-temperature ash deposition due to condensed phases occurs at temperatures in the range of 1000 - 1650 oF. In systems which exhibit low temperature fouling, the sulfate phases dominate the matrix or bonding mechanism between particles. Detailed examination of low-temperature deposits shows high levels of sodium, potassium and/or calcium in the form of sulfates, chlorides, and phosphates in the deposits. These phases

may have a low melting point due to the formation of Na-Ca-sulfate eutectic (very low melting points) phases. In addition, formation of low-temperature deposits is dependent upon the availability of small calcium oxide particles and the process of sulfation. Calcium oxide-rich particles in a deposit undergo sulfation through reaction with sulfur dioxide in the gas stream. This reaction produces calcium sulfate which causes particleto-particle bonding and fills in the available pore space in the deposits. This pore filling produces very strong, brick-like deposits which are difficult to remove. The low temperature deposition processes depend upon the abundance of alkali and alkaline earth elements in the fuel and their ability to react with volatilized sulfur, phosphorus, and chloride species to form liquid phases or solid phases that cause particle to particle bonding in deposits. The stability of these phases is temperature dependent and most are not stable in a liquid or solid phase at temperatures above 2000 oF in the presence of silicates.

Figure 1. Type of liquid and other bonding phases present in deposits as a function of temperature.