Hydrothermal carbonization can be defined as combined dehydration and decarboxy lation of a fuel to raise its carbon content with the aim of achieving a higher calorific value. It is realized by applying elevated temperatures (180-220 o C) to biomass in a suspension with water under saturated pressure for several hours. With this conversion process, a lignite-like, easy to handle fuel with well-defined properties can be created from biomass residues, even with high moisture content. Thus it may contribute to a wider application of biomass for energetic purposes. Although hydrothermal carbonization has been known for nearly a century, it has received little attention in current biomass conversion research. This review summarizes knowledge about the chemical nature of this process from a process design point of view. Reaction mechanisms of hydrolysis, dehydration, decarboxylation, aromatization, and condensation polymerization are discussed and evaluated to describe important operational parameters qualitatively. The results are used to derive fundamental process design im provements.

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The impact of conversion process parameters in pyrolysis (maximum temperature, inert gas flow rate) and hydrothermal carbonization (maximum temperature, residence time and post-washing) on biochar and hydrochar properties is investigated. Pine wood (PW) and corn digestate (CD), with low and high inorganic species content respectively, are used as feedstock. CD biochars show lower H/C ratios, thermal recalcitrance and total specific surface area than PW biochars, but higher mesoporosity. CD and PW biochars present higher naphthalene and phenanthrene contents, respectively, which may indicate different reaction pathways. High temperatures (>500 • C) lead to lower PAH (polycyclic aromatic hydrocarbons) content (<12 mg/kg) and higher specific surface area. With increasing process severity the biochars carbon content is also enhanced, as well as the thermal stability. High inert gas flow rates increase the microporosity and wettability of biochars. In hydrochars the high inorganic content favor decarboxylation over dehydration reactions. Hydrochars show mainly mesoporosity, with a higher pore volume but generally lower specific surface area than biochars. Biochars present negligible availability of NO − 3 and NH + 4 , irrespective of the nitrogen content of the feedstock. For hydrochars, a potential increase in availability of NO − 3 , NH + 4 , PO 3− 4 , and K + with respect to the feedstock is possible. The results from this work can be applied to "engineer" appropriate biochars with respect to soil demands and certification requirements.

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