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Abstract: Pyrolysis is known to occur by decomposition processes followed by vapour phase reactions. The goal of this research is to develop a novel device to study the initial decomposition processes. For this, a novel wire-mesh reactor was constructed. A small sample (<0.1g) was clamped between two meshes that were heated fast (up to 10000°C/s, ΔT mesh ±35°C) by an electrical current. The mesh/feedstock was placed inside a vacumized (P <0.3mbar), liquid nitrogen cooled vessel (T wall <−80°C). These two last features were proven to result in a low vapour life time (<15–25ms versus ∼2s in typical pyrolysis). The vapour residence time and temperature could be increased by increasing the pressure inside the reactor and by removing of the liquid nitrogen cooling. Reproducible results concerning yields (mass balance closures 90–110wt%) and analysis were obtained (oil by SEC and NMR, gas by GC, char by FTIR). The yields and oil composition were changing with loading from 0.05g to 0.1g, despite the small sample amounts. Compared to more “conventional” pyrolysis processes, high oil yields (84wt%), very low char yields (5wt%) and low gas yields (8wt%) were obtained. Using a high speed camera, movies were made and together with accompanying pressure profiles, it was possible to estimate the conversion rate. At 500°C the conversion process was finished within 0.8s which is faster than previously reported in the literature. Especially an increase in gas yield (+14wt%, mainly CO) was observed in absence of cooling (P vac/No Cooling), while both the gas (+4wt%) and char yield (+3wt%) increased under atmospheric pressure (P atm/Cooling), all at the expense of oil yield. Compared to more “conventional” pyrolysis oil, the oil did contain: (i) heavier molecules and (ii) a sugar fraction. [Copyright &y& Elsevier]

Abstract: In fast pyrolysis, biomass decomposition processes are followed by vapor phase reactions. Experimental results were obtained in a unique wire-mesh reactor using pine wood, KCl impregnated pine wood and several model compounds (cellulose, xylan, lignin, levoglucosan, glucose). The wire-mesh reactor was typically operated at a set temperature of 500°C, high heating rates (up to 7000°C/s) under vacuum and with liquid nitrogen cooling to ensure a short vapor residence time (<15–25ms) and a low vapor phase temperature. In this way good suppression of vapor phase reactions and reactions inside the decomposing particle were achieved as shown by the (almost) complete recovery of glucose and levoglucosan after pyrolysis. The influence of temperature (250–700°C) and heating rate (50–7000°C/s) was studied on product yields and compositions (GC, SEC, NMR, FTIR, HPLC). A high oil yield of 84wt% and a low char yield of 5wt% was observed for pine wood around 500°C. Above this temperature a slight drop in oil yield was observed, but the oil yield was still 60wt% at 700°C. Also high oil yields and low char were obtained during the pyrolysis of cellulose (oil/char: 95/0wt%) and lignin (oil/char: 78/12wt%). Our data were interpreted with a physical–chemical mechanism. The basic idea behind this mechanism is that the amount and composition of the “decomposing biomass”, which can be in the solid or liquid state under the pyrolysis conditions, is changing in time due to competition between (cross)-linking reactions, scission reactions and mass transfer of decay fragments out of the decomposing particle. Observations such as the twice as large char yield for K-impregnated pine wood (10wt%) compared to untreated pine wood (5wt%) and the 20wt% increase in char yield from lignin when decreasing the heating rate from 6000 to 60°C/s could be explained by this mechanism. [Copyright &y& Elsevier]