The release and transformation of potassium (K), chlorine (Cl), and sulfur (S) from biomass during thermochemical conversion processes may lead to problems, such as the corrosion and fouling of heat transfer surfaces, agglomeration of bed material, and the poisoning of catalysts used in the downstream processes of gasifiers. To predict and to mitigate effectively these problems, information regarding the quantity and mechanism of the release of these elements under relevant operating conditions is required. In the present work, the release of K, Cl, and S from wheat straw under conditions relevant to dual fluidized bed gasification were quantified in a laboratory-scale bubbling fluidized bed reactor. During the pyrolysis step, the bed temperature ranged from 550 to 900 °C, while the residence time for the fuel in the reactor was fixed at 3 min. The char samples obtained from the pyrolysis step were partially combusted at the same temperature at which they were produced for an additional 3 min. The fractions of the elements released from the fuel were quantified by chemical analysis of the char/residual ash obtained in each experiment and a mass balance across the system. Overall, 75%−62% of the Cl, 59%−67% of the S, and 14%−31% of the K in the virgin wheat straw were released during pyrolysis conducted within the investigated temperature range. The char obtained from the pyrolysis process contained significantly higher amounts of K, Cl, and S than the virgin fuel. Furthermore, the ash content of the char was about 5-fold higher than that of the virgin fuel. This suggests that at combustion-relevant temperatures, complete combustion of the char is more likely to result in severe ash-related problems than combustion of the virgin fuel. Partial combustion of the char resulted in additional release of K, Cl, and S. In addition to the experimental results, the transformation and release of the elements during this process are discussed with the aid of chemical thermodynamic equilibrium modeling and leaching.

The corrosion and fouling of heat-transfer surfaces and the agglomeration of bed materials in fluidized beds are some of the ash-related problems caused by the transformation and release to the gas phase of ash-forming elements from biomass during thermochemical conversion processes. The magnitudes of these problems are largely dependent upon the release of potassium (K), chlorine (Cl), and sulfur (S) from the biomass. We investigated the effects of steam on the release of K, Cl, and S during char conversion, under conditions relevant for dual-fluidized-bed gasification (DFBG). The study was carried out with wheat straw in a laboratory-scale bubbling fluidized-bed reactor in the temperature range of 800–900 °C. The release of K, Cl, and S from wheat straw during devolatilization, char gasification, and char combustion was quantified with a mass balance that linked the masses of these elements in the wheat straw to the mass of the solid residue obtained at the end of each experiment. To facilitate analyses of the experimental results, leaching and the Brunauer–Emmett–Teller surface area measurement of the wheat straw and some of the solid residues were carried out. The results show that, during devolatilization, the release of volatile salts, e.g., KCl, is significantly limited by intraparticle diffusion resistance, owing to a compact char matrix (i.e., negligible porosity). However, during char gasification, steam renders the char less compact by expanding and/or creating new pores in the char. As a result, intraparticle diffusion resistance decreases, thereby facilitating the evaporation of volatile salts of K and S from the char matrix. The conversion of the char is also conducive to the release of char-bound K and S, especially at 900 °C. At temperatures of >800 °C, the relative proportions of the elements released and char gasified indicate that the release of K can somewhat be decoupled from the release of S and Cl by maximizing the extent of char conversion in the gasification chamber. The results also show that, during char combustion, the proportions of the char that can be combusted and the extent of the release of the elements are influenced by the extent to which the char is gasified in the gasification chamber.

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Steam-fluidized bed gasification of biomass, which produces combustible gases from which transportation fuels can be synthesized, is a promising option for replacing the use of fossil fuels in the transportation sector. Similar to other thermal conversion processes, the release of potassium (K), chlorine (Cl), and sulfur (S) from biomass fuels to the gas phase during this process may be conducive to ash-related problems. Catalytic tar and char conversion by K has also been observed. In addition to operational conditions, the extent to which these elements are released to the gas phase may be affected by fuel ash characteristics such as the ash composition and the speciation (or association) of ash-forming elements in the fuel matrix. In the present work, the influence of these fuel ash characteristics on the extent to which K, Cl, and S are released from biomass fuels to the gas phase was studied under steam-fluidized bed gasification. The aim was to assess whether these fuel ash characteristics provide information that could be useful in making a quick judgment as to what extent K, Cl, and S would be released to the gas phase. To this end, the release of K, Cl, and S from forest residues and wheat straw during devolatilization and steam gasification of the char was quantified in a laboratory-scale bubbling fluidized bed reactor. The speciation of these elements in the virgin fuels was studied with chemical fractionation. The results reveal that the extent to which S is released from biomass fuels to the gas phase mainly depends on its speciation in the fuel matrix. While both the ash composition (mainly the Cl/K molar ratio) of the fuel and the speciation of K in the fuel matrix are relevant for the release of K, they appear to be unimportant with respect to the release of Cl.

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