There is a consensus worldwide that the share of renewable energy sources should be increased to mitigate climate change. The strive to increase the renewable energy fraction can partly be met by an increased utilization of different biomass feedstocks. Many of the "new" feedstocks puts stress on certain challenges such as air pollution emissions and operation stability of the combustion process. The overall objective was to investigate, evaluate, and explain the effects of fuel design and combustion control - fuel engineering - as primary measures for control of slag formation, deposit formation, and fine particle emissions during biomass combustion in small and medium scale fixed-bed appliances. The work in this thesis can be outlined as having two main focus areas, one more applied regarding fuel engineering measures and one more fundamental regarding the time-resolved release of ash forming elements, with particular focus on potassium. The overall conclusion related to the abatement of particle emissions and slag formation, is that the release of fine particle and deposit forming matter can be controlled simultaneously as the slag formation during fixed-bed biomass combustion. The methodology is in this perspective denoted “fuel engineering” and is based on a combined approach including both fuel design and process control measures. The studies on time-resolved potassium release showed that a Macro-TG reactor with single pellet experiments was a valuable tool for studying ash transformation along the fuel conversion. The combination of dedicated release determinations based on accurate mass balance considerations and ICP analysis, with phase composition characterization by XRD, is important for the understanding of potassium release in general and time-resolved data in particular. For wood, the results presented in this work supports the potassium release mechanism from "char-K" but questions the previously suggested release mechanism from decomposition of K-carbonates. For straw, the present data support the idea that the major part of the potassium release is attributed to volatilization of KCl. To further explore the detailed mechanisms, the novel approach developed and applied in this work should be complemented with other experimental and analytical techniques. The research in this thesis has explored some of the challenges related to the combined phenomena of fuel conversion and ash transformation during thermochemical conversion of biomass, and has contributed with novel methods and approaches that have gained new knowledge to be used for the development of more effective bioenergy systems.

Biomass is increasingly used as a feedstock in global energy production. This may present operational challenges in energy conversion processes which are related to the inorganic content of these biomasses. As a larger variety of biomass is used the need for a basic understanding of ash transformation reactions becomes increasingly important. This is not only to reduce operational problems but also to facilitate the use of ash as a nutrient source for new biomass production. Ash transformation reactions were examined in the present work using the Lewis acid-base concept. The model presented in Paper I was further extended and discussed, including the definition of tertiary ash transformation reactions as reaction steps where negatively charged molecular ions, Lewis bases, other than hydroxides are present in the reactants. The effect of such reactions for bonding of various metal ions, Lewis acids, were discussed. It was found that the formation of various phosphates through secondary and tertiary ash transformation reactions is important for the behaviour of biomass ash in combustion. The suggested model was supported by findings in Papers II-VIII. The experimental findings in Papers II-VIII were discussed in terms of ash transformation reactions. The fuel design choices made to investigate the effect of phosphorus in particular on ash transformation reactions were high-lighted. Addition of phosphoric acid to woody-type and agricultural biomasses showed that phosphate formation has a large influence on the speciation of Si, S, and Cl. Co-combustion of a problematic agricultural residue with other biomasses showed that the relation between phosphorus, alkali and alkaline earth metal content is important. Co-combustion of biosolids with wheat straw was shown to greatly improve the combustion properties of wheat straw. It was suggested that fuel analyses should be presented using molar concentration (mole/kg) in diagrams based on ash transformation reactions and elements forming Lewis acids or bases. This may facilitate the assessment of the combustion behaviour of a fuel. Some comments were made on fuel design and additives, specifically pointing out that phosphorus content should always be carefully considered in relation to alkali and alkaline earth metals in fuels and fuel blends.