Fast pyrolysis of biomass produces bio-oil as a dominant product. However, the yield and composition of bio-oil are governed by numerous pyrolysis reactions which are difficult to understand because of the multiphase decomposition phenomena with convoluted chemistry and transport effects at millisecond time scales. In this work, thin-film pyrolysis experiments of biopolymers present in the biomass (i.e., cellulose (∼50 μm), hemicellulose (using xylan as a model biopolymer, ∼12 μm), and lignin (∼10 μm)) were performed over 200–550 °C, to investigate underlying thermal decomposition reactions, based on the product distribution obtained under reaction-controlled operating conditions. Experimental yields of non-condensable gases, bio-oil, and char at different operating temperatures and in the absence of transport limitations were obtained for each biopolymer. Cellulose- and xylan-derived bio-oil comprised of anhydro­sugars, furans, and light oxygenates, in addition to pyrans in cellulosic bio-oil and phenols in xylan-derived bio-oil. Lignin pyrolysis bio-oil contained methoxy­phenols, phenolic aldehydes/ketones, low-molecular-weight phenols, and light oxygenates. With an increase in the operating temperature, the anhydro­sugars, furans (especially HMF and furfural), and pyrans of cellulosic and xylan bio-oils showed further degradation to form light oxygenates and furanic compounds. In the case of lignin, monolignols, initially formed at lower temperatures, further reacted to form low-molecular-weight phenols and light oxygenates with an increase in the operating temperature. In addition, based on the change in bio-oil yield and composition with temperatures, a reaction network/map was proposed for designing the molecular simulation studies of pyrolysis chemistry and developing detailed and accurate kinetics necessary for the bottom-up design of a pyrolysis reactor.

Fast pyrolysis is a promising technology for the production of renewable fuels and chemicals from lignocellulosic biomass. The product distribution (bio-oil, char) and the composition of bio-oil are significantly influenced by the presence of naturally occurring alkali and alkaline-earth metals (AAEMs). In this paper, we investigate, at the molecular level, the influence of Na(I), K(I), Ca(II), and Mg(II) ions on glycosidic bond breaking reactions using density functional theory. Glycosidic bond breaking reactions are categorized as direct C-O breaking mechanisms, namely, transglycosylation, glycosylation, and ring contraction and the two-step pathways, which include the mannose pathway, dehydration, and ring opening. Our calculations show that in the absence of metal, transglycosylation and dehydration pathways (activation barriers ∼55 kcal.mol) are kinetically most facile. The linkage type (α- or β-1,4) has an insignificant effect on kinetics of glycosidic bond cleavage. Mg(II) ions have a pronounced effect on lowering the activation barriers of glycosylation, ring contraction, and the mannose pathway, requiring activation enthalpies of 32-52 kcal.mol. Conversely, Mg(II) and Ca(II) ions inhibit the dehydration pathway. Na(I) and K(I) ions do not significantly influence the activation barriers of glycosidic bond cleavage reactions, as the reduction is only about 5-10 kcal.mol. Thus, AAEM ions exhibit different catalytic effects on glycosidic bond breaking reactions.

Effect of temperature and transport on the yield and composition of pyrolysis-derived bio-oil from glucose

The current study provides molecular-level insights into the CO2–amine functionalized polystyrene complexes, enabling design of newer CO2 selective adsorbents.