There is relatively extensive knowledge available concerning ash transformation reactions during combustion of woody biomass. In recent decades, the use of these energy carriers has increased, from a low-technology residential small-scale level to an industrial scale. Along this evolution, ash chemical-related phenomena for woody biomass have been observed and studied. Therefore, presently the understanding for these are, if not complete, fairly good. However, because the demand for CO 2 -neutral energy resources has increased recently and will continue to increase in the foreseeable future, other biomasses, such as, for instance, agricultural crops, have become highly interesting. The ash-forming matter in agricultural biomass is rather different in comparison to woody biomass, with a higher content of phosphorus as a distinctive feature. The knowledge about the ash transformation behavior in these systems is far from complete. Here, an attempt to give a schematic but general description of the ash transformation reactions of biomass fuels is presented in terms of a conceptual model, with the intention to provide guidance in the understanding of ash matter behavior in the use of any biomass fuel, primarily from the knowledge of the concentrations of ash-forming elements. The model was organized in primary and secondary reactions. Restrictions on the theoretical model in terms of reactivity limitations and physical conditions of the conversion process were discussed and exemplified, and some principal differences between biomass ashes dominated by Si and P, separately, were outlined and discussed.

The in-bed behavior of ash-forming elements in fluidized bed combustion (FBC) of different biomass fuels was examined by SEM/EDS analysis of samples collected during controlled agglomeration test runs. Eight fuels were chosen for the test. To cover the variations in biomass characteristics and to represent as many combinations of ash-forming elements in biomass fuels as possible, the selection was based on a principal-component analysis of some 300 biomass fuels, with respect to ash-forming elements. The fuels were then combusted in a bench-scale fluidized bed reactor (5 kW), and their specific agglomeration temperatures were determined. Bed samples were collected throughout the tests, and coatings and necks formed were characterized by SEM/EDS analyses. On the basis of their compositions, the corresponding melting behaviors were determined, using data extracted from phase diagrams. The bench-scale reactor bed samples were finally compared with bed samples collected from biomass-fired full-scale fluidized bed boilers. In all the analyzed samples, the bed particles were coated with a relatively homogeneous ash layer. The compositions of these coatings were most commonly constricted to the ternary system K2O−CaO−SiO2. Sulfur and chlorine were further found not to “participate” in the agglomeration mechanism. The estimated melting behavior of the bed coating generally correlated well with the measured agglomeration temperature, determined in the 5 kW bench-scale fluidized bed reactor. Thus, the results indicate that partial melting of the coating of the bed particles would be directly responsible for the agglomeration.

Limited availability of sawdust and planer shavings and an increasing demand for biomass pellets in Europe are pushing the market toward other, more problematic raw materials with broader variation in total fuel ash content and composition of the ash forming elements as well as in their slagging tendencies. The main objective in the present work was therefore to determine the influence of fuel−ash composition on residual ash and slag behavior. Twelve different biomass pellets were used: reed canary grass (two different samples), hemp (two different samples), wheat straw, salix, logging residues (two different samples), stem wood (sawdust) as well as spruce, pine, and birch bark. The different pellet qualities were combusted in a commercial under fed pellet burner (20 kW) installed in a reference boiler. Continuous measurements of O2, CO, CO2, HCl, SO2, and total particle matter mass concentrations were determined in the exhaust gas directly after the boiler. The collected slag deposits, the corresponding deposited bottom ash in the boiler and the collected particle matter were characterized with X-ray diffraction (XRD) and scanning electron microscopy combined with energy dispersive X-ray analysis (SEM/EDS). For biomass fuel pellets rich in silicon (either inherent or contaminated with sand) and low content of alkaline earth metals the main part of the potassium reacted with the silicon rich ash-residual, forming sticky alkali−silicate particles, which were not entrained from the burner and thereby giving rise to/initiating slag formation. Silicon rich fuels, i.e. fuels were the ash characteristics were dominated by silicate−alkali chemistry, therefore generally showed relatively high slagging tendencies. Straw fuels have typically this ash composition but exceptions to these general trends exists (e.g., one of the hemp fuels used in this work). Wood derived fuels with a relatively low inherent silicon content therefore showed low or relatively moderate slagging tendencies. However, contamination of sand material to these fuels may greatly enhance the slagging tendencies.