Effect of biomass ash in catalytic fast pyrolysis of pine wood

Abstract

Fast pyrolysis experiments of pine wood have been performed in a continuously operated mechanically stirred bed reactor at 500°C. The effects of the pine wood ash were studied by comparing non-catalytic and catalytic experiments (using a ZSM-5 based catalyst) with their ash-added counterparts. To show the case of ash accumulated from the biomass feeding, the results of catalytic fast pyrolysis obtained after eight reaction/catalyst regeneration cycles were included as well. The objective was to distinguish between the ash-catalyst interactions and the catalyst deactivation. The latter may be caused by thermo-mechanical, chemical and/or structural changes in the catalyst; such as poisoning, fouling, and attrition, as well as by coke deposition. Ash concentrations up to ca. 3wt.% relative to the amount of pine wood fed, and ca. 0.002wt.% relative to the amount of bed material, were found to be sufficient to change the distribution and the composition of pyrolysis products. The addition of ash to the catalytic fast pyrolysis, caused a reduction in the yields of both the organics and coke by 2wt.% (on feed basis), while increases of 1wt.% and 4wt.% in the water and non-condensable gases were observed, respectively. The total yield of CO plus CO2 was boosted by more than 10%, while the CO2 production (decarboxylation reactions) was favoured clearly. Moreover, the presence of added-ash suppressed the conversion of sugars and acids – these were more pronounced in the case of accumulated-ash – as well as of the phenols. The catalyst deactivation during the reaction/regeneration cycles is not only related to the presence of ash but also to changes in the structure and composition of the catalyst. To overcome the drawbacks of biomass ash in catalytic fast pyrolysis, either the biomass feedstock has to be leached (ash removal) before being introduced to the process, or the char (which contains a vast majority of the biomass ash) has to be physically removed from the catalyst before the regeneration step.