Thermochemical treatments like pyrolysis and gasification, were proposed to circumvent hydrolysis bottleneck of conventional 2nd generation biorefineries. Within this big-picture, the target of this article was to establish the type and amount of bioavailable matter that can be obtained through intermediate pyrolysis of biomass followed by gasification of biochar. To establish the amount of “chemical energy” partitioned among different products’ chemical oxygen demand (COD), which is proportional to higher heating value (HHV) and often utilized for biological systems, was applied for the evaluation of thermochemical conversion of a lignocellulosic feedstock (fir wood). The most abundant product of intermediate pyrolysis was biochar, which retains from 33 % to 40 % of feedstock COD (with temperatures starting from 450 °C). The yield of water-soluble pyrolysis products (WS) slightly increases from 24 % at 450 °C to 27 % at 650 °C, whereas the yield of WI increases considerably with the same temperature. Pyrolysis temperature showed a minor effect on the composition of WS as revealed by GC-MS analysis of main compounds and size exclusion chromatography. Preliminary gasification experiments, performed at 850 °C under CO2 atmosphere, provided gasification rates for different biochars, which was equal to 0.004, 0.005, 0.006 min−1 for biochars obtained at 650, 550, and 450 °C respectively. Syngas obtained from gasification of 450 °C and 550 °C biochar was almost tar-free, whereas gasification of 650 °C biochar yielded a detectable amount of tars (0.4 %). Increasing the gasification temperature to 950 °C sharply increases the gasification rate of biochar obtained at 450 °C, allowing to obtain 55% conversion yield. Within the scope of hybrid thermochemical-biological (HTB) processes, the obtained results show that intermediate pyrolysis, when coupled with subsequent 950 °C CO2 gasification of biochar, can deliver 64% of chemical energy (by COD basis) of the lignocellulosic feedstock as bioavailable constituents, which are defined to syngas and WS based on recent biological studies. Whereas downstream fermentation can process syngas and WS materials in an effective way, such yields could surpass the holocellulose-targeted methods based on hydrolysis.
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