Biocrude from hydrothermal liquefaction of biomass provides a sustainable source from which to produce chemicals and fuels. However, just as for fossil crude, the chemical complexity of the biocrude impedes the characterization and hence identification of market potentials for both biocrude and individual fractions. Here, we reveal how fractional distillation of a biocrude can leverage biocrude characterization beyond state-of-the-art and uncover the full biocrude potential. By distillation combined with detailed individual analysis of the distillate fractions and distillation residue, more than 85 % of the total biocrude composition is determined. It is demonstrated that a total mass fraction of 48.2 % of the biocrude is volatile below 350 • C, comprising mainly value-added marketable ketones, oxygenated aromatics and prospective liquid fuel candidates, which are easily fractionated according to boiling points. Novel, high resolution pyr-GCxGC-MS analysis of the residue indicates a high molecular weight aromatic structure, valuable for bio-materials production or for further processing into fuels. The distillate fractions are mildly hydrotreated to show the fuel and chemical precursor potential of the volatile components. This results in the formation of mainly hydrocarbons and added-value phenolics. This work takes a significant step by going beyond the biocrude as an intermediate bulk energy product and addressing actual applications and pathways to these.

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Fast pyrolysis of stem wood was performed in a pilot-scale cyclone reactor with a reactor wall temperature of ∼750°C. Wood powder was introduced to the pyrolyzer at 20 kg/h during the experiments. Stable operation of the pyrolyzer was easily achieved, and the resulting yields of the products were 54.6 wt % of pyrolysis oil, 15.2 wt % of solid residue, and 20.1 wt % of gases. From the ingoing raw material, 3.4 wt % of the mass could be recovered as deposits, mainly on the walls of the reactor and in the oil condensing part of the plant. The mass and energy balance closures were approximately 93% and 89%, respectively. The physicochemical properties of the pyrolysis oil, solid residue, and noncondensable gas were measured and compared to values in the literature. The results also show that it is possible to produce an oil with a very low concentration of ash-forming elements because particle separation has already occurred in the cyclone reactor.

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Integration of renewable raw materials in existing refineries is most likely the shortest way for the successful, largescale introduction of biofuels in the transport sector in the short term and medium term. One possible renewable raw material for this application is fast pyrolysis bio-oil (FPBO), which in this study has been coprocessed (at 0 and 20 wt %) with vacuum residue (VR, 50 wt %) and vacuum gas oil (VGO, balance) in a continuous, as well as a semibatch, slurry hydrocracking process. Experiments both with and without FPBO were performed at 450 °C and 150 bar with a continuous hydrogen flow through the reactor. Oil-soluble molybdenum hexacarbonyl and molybdenum 2-ethylhexanoate were used as catalyst precursors, to be sulfided in situ. The continuous trials resulted in reactor walls completely free of coking, and they resulted in a low overall coke yield (about 1 wt %). The hydrodeoxygenation reached almost 92%, and the total acid number was reduced by nearly 99% in the FPBO experiment. A mass balance of the renewable carbon from FPBO, based on the performed experiments, showed that the fossil CO 2 emissions can be lowered by 1.35 kg per kilogram of processed FPBO if all renewable carbon in gaseous and liquid hydrocarbons is used to replace its fossil counterparts, and all methane formed from FPBO is used to produce hydrogen. Semibatch experiments gave less successful results when upgrading FPBO-containing feedstock, with a high coke yield (8 wt %) as well as a high gas yield (24 wt %). The results of this study demonstrate that FPBO can be successfully coprocessed with heavy fossil oils in a continuous slurry hydrocracking process without negatively affecting the processing of the fossil components of the feed and that a continuous process is preferred over batch or semibatch processes when studying coprocessing of bio-oils.

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Pyrolysis oil is a complex mixture of different chemical compounds with a wide range of molecular weights and boiling points. Due to its complexity, an efficient fractionation of the oil may be a more promising approach of producing liquid fuels and chemicals than treating the whole oil. In this work a sampling system based on fractional condensation was attached to a cyclone pyrolysis pilot plant to enable separation of the produced pyrolysis vapors into five oil fractions. The sampling system was composed of cyclonic condensers and coalescing filters arranged in series. The objective was to characterize the oil fractions produced from three different Nordic feedstocks and suggest possible applications. The oil fractions were thoroughly characterized using several analytical techniques including water content; elemental composition; heating value, and chemical compound group analysis using solvent fractionation, quantitative 13 C NMR and 1 H NMR and GC x GC-TOFMS. The results show that the oil fractions significantly differ from each other both in chemical and physical properties. The first fractions and the fraction composed of aerosols were highly viscous and contained larger energyrich compounds of mainly lignin-derived material. The middle fraction contained medium-size compounds with relatively high concentration of water, sugars, alcohols, hydrocarbonyls and acids and finally the last fraction contained smaller molecules such as water, aldehydes, ketones and acids. However, the properties of the respective fractions seem independent on the studied feedstock types, i.e. the respective fractions produced from different feedstock are rather similar. This promotes the possibility to vary the feedstock depending on availability while retaining the oil properties. Possible applications of the five fractions vary from oil for combustion and extraction of the pyrolytic lignin in the early fractions to extraction of sugars from the early and middle fractions, and extraction of acids and aldehydes in the later fractions.