Identifying Synergistic Effects between Biomass Components during Pyrolysis and Pointers Concerning Experiment Design

A review of existing data has shown that “char yield deficits” develop during the pyrolysis of lignocellulosic biomass, relative to char yields expected from pyrolyzing chemically isolated lignins and the proportion of lignin in the particular biomass. This paper describes two sets of pyrolysis experiments. The work done in a thermogravimetric (TG) balance was initiated to probe whether diminishing heating rates might reduce, or even wipe out, the “char yield deficits” identified in previous work, where a wide range of heating rates had been used. Experiments were performed at 2 °C min–1, a lower heating rate than that has hitherto been used to investigate char deficits. The effect was confirmed at this slow heating rate, using samples of birchwood and almond shells. A parallel set of differential scanning calorimetry (DSC) experiments provided evidence that mechanisms by which biomass samples pyrolyze are distinct from those of biomass components pyrolyzing in isolation. Moreover, the observed effects could not be replicated by simply mixing the three biomass components in appropriate proportions. The “lignin char deficit” is consistent with chemical interactions between intermeshed biomass components during pyrolysis altering reaction pathways and product distributions relative to the pyrolysis of biomass components pyrolyzed in isolation. The present work also shows that sample mass loss in TG balances is affected by altering sample loading, leading to potential errors. The design of pyrolysis experiments is discussed and approaches are suggested to prevent masking of key pyrolysis phenomena, viz. synergistic effects between biomass components or onset-of-pyrolysis temperatures, through the appropriate selection of experimental parameters.