Global environmental concerns are motivating a growing interest in broadening the biomass feedstock base in several energy sectors, including (i) the domestic heating sector, presently dominated by stem wood combustion, and (ii) biofuel production, presently dominated by edible crops. The objective of this thesis is to investigate new opportunities to broaden the biomass feedstock in thermochemical conversion technologies. The performance of different feedstocks was therefore investigated for (i) heat production in small-scale combustion systems and (ii) biofuel production in large-scale gasification-based plants. The selected feedstocks were agricultural residues, forest wood, pyrolysis liquid and industrial by-products, such as lignin, black liquor, crude glycerol and fermentation residues.

The alkali metals content in biomass has an important role in combustion and gasification. Alkali metals can cause ash-related problems in small-scale combustion systems, while they can catalyse gasification reactions thus increasing conversion efficiency. Keeping this effect in mind, the present investigation was based on combustion tests with pelletised agricultural residues (non-woody feedstocks with ash contents of 3-8 wt% on a dry basis) to evaluate their combustion feasibility in several small-scale appliances. Moreover, the potential techno-economic benefits of alkali addition in gasification-based biofuel plants were investigated in two different systems: (i) stand-alone biofuel plant operated with wet-alkali-impregnated forest residues and alkali-rich lignin as well as (ii) biofuel plant integrated with a Kraft pulp mill operated with black liquor (an inherently alkali-rich feedstock) mixed with different blend ratios of pyrolysis liquid, crude glycerol or fermentation residues (co-gasification concept). The techno-economic analysis in large-scale entrained-flow-gasification-based biofuel plants was made with the help of simulation tools.

The combustion tests have shown that high alkali feedstocks lead to problems with ash accumulation and slag formation in small-scale appliances. The results indicated that non-woody feedstocks can only be burned in appliances adapted to manage high ash content feedstocks. Effective ash cleaning and enhanced combustion controlling mechanisms are relevant characteristics to have in appliances when using these feedstocks. It has been shown that four out of the seven selected feedstocks can be burned in small-scale appliances, while fulfilling the legal European requirements (EN 303-5:2012) in terms of combustion efficiency and emissions. The nitrogen content and ash composition were shown to be important parameters to evaluate whether a feedstock can be utilised in small-scale combustion appliances.

The techno-economic investigations of the gasification-based biofuel plants have shown that alkali impregnation is an attractive option to increase energy performance and downstream biofuel production. The economic assessment has indicated that alkali impregnation does not significantly increase biofuel production costs, while it allows the application of a new syngas cleaning system that can significantly reduce biofuel production costs. The present study has shown that the vi co-gasification concept has also techno-economic benefits as a result of the (i) alkali content in black liquor and (ii) economy-of-scale effects. These benefits can be enhanced by choosing energy-rich and low-cost blend-in feedstocks. The gasification-based biofuel production routes hereby investigated exhibit a good economic performance since biofuel required selling prices were economically competitive with other biofuel production routes as well as with taxed gasoline.