This paper presents an investigation of the production of crude bio-oil, char, and pyrolytic gases from the fast pyrolysis of mallee woody biomass in Australia. The feedstock was ground, sieved to several narrow particle size ranges, and dried prior to pyrolysis in a novel laboratory-scale fluidized-bed reactor. The effects of pyrolysis temperature (350−600 °C), and biomass particle size (100−600 μm), on the yields and composition of bio-oil, gas, and char are reported. In agreement with previous reports, the pyrolysis temperature has an important impact on the yield and composition of bio-oil, char, and gases. Biomass particle size has a significant effect on the water content of bio-oil. It is interesting to note that the temperature for maximum bio-oil yield, between 450 and 475 °C, resulted in an oil with the highest content of oligomers and, consequently, with the highest viscosity. Such observations suggest that the conventional viewpoint of pyrolyzing biomass at temperatures over 400 °C to maximize bio-oil yield needs to be carefully reevaluated, considering the final use of the produced bio-oil. The increases in oil yield with increasing temperature from 350 to 500 °C were mainly due to the increases in the production of lignin-derived oligomers insoluble in water but soluble in CH2Cl2. The yield and some fuel properties of the pyrolysis products were compared with those herein obtained for pine as well as those reported in the literature for other lignocellulosic feedstocks but using similar reactors.

Biochars were prepared from the pyrolysis of the wood, leaf, and bark components of mallee biomass in a fixed-bed reactor at 750 °C. The results show that the volatilization of inherent alkali and alkaline earth metallic (AAEM) species is 10-20% during the pyrolysis of raw wood, bark, and leaf samples. Acid treatment of the biochar samples was also carried out to prepare a set of acid-treated biochar samples. Although the majority of the inherent AAEM species were removed by acid-treatment, there are always some AAEM species that could not be removed for all biochars. Steam gasification experiments of both the raw and acid-treated biochar samples were carried out in a fixed-bed reactor at 750 °C and a steam concentration of 8.2 vol %. Data on the instantaneous syngas composition were obtained as a function of biochar conversion during steam gasification. Our data illustrated the importance of, in the study of steam gasification reaction mechanisms and kinetics of solid fuels such as biochars, optimizing the reaction conditions to minimize steam consumption so that the steam partial pressure in the reactor is kept reasonably constant during the whole course of gasification. The results indicate that Na, K, and Ca retained in the biochars are the key catalytic species, with the catalytic effect appearing to be in the order K > Na > Ca during the steam gasification reaction of these biochars. During steam gasification, almost all of the inherent AAEM species in biochar are retained in the reacting biochar, throughout the course of conversion. Steam gasification of both the raw and acid-treated biochars produces high-quality syngas products that contain little methane. Further analysis shows that during the course of biochar conversion, the primary gasification product is most likely CO, and overall the water-gas-shift reaction is primarily responsible for the CO 2 formation. It is found that the inherent AAEM species, although catalyzing the biochar gasification significantly, appear to have insignificant catalytic effect on the water-gas-shift reaction under the current gasification conditions.