Abstract

CO2 and H2O are commonly used oxidants for activation of carbonaceous feedstock, which are also major products in biomass pyrolysis. The heated CO2 and H2O from pyrolysis might be used directly to activate biochar without cooling down. This was investigated in a reactor with dual fixed beds with biochar on the bottom and biomass feedstock (poplar sawdust, cellulose, or lignin) of the same origin on top. The CO2 and H2O together with the volatiles generated at 700 °C from the top bed passed through the lower-bed biochar for activation. The results indicated that, except for CO2 and H2O, the volatiles from pyrolysis of upper-bed biomass were highly reactive with the lower-bed biochar, especially for the cellulose-derived aliphatic volatiles. This formed carbonaceous deposit and enhanced the yield of biochar at expense of the volatiles (i.e. aldehydes/ketones and heavy organics of large π-conjugated structures), leading to lower yields of bio-oil. The carbonaceous deposit formed via cracking and/or polymerization filled the pores and substantially decreased the surface specific area by 99.9 % for sawdust-biochar, 87.4 % for cellulose-biochar, and 33.1 % for lignin-biochar. The volatile-char interaction, instead of the activation with CO2 and H2O, dominated the pore development of biochar. Additionally, the interaction of volatiles with biochar enhanced deoxygenation, producing the carbon-rich biochar of higher heating value and energy yield.

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