Integrating sustainable biofuel and silver nanomaterial production for in situ upgrading of cellulosic biomass pyrolysis

Abstract Replacing fossil fuels with biomass-based alternatives is a potential carbon neutral, renewable and sustainable option for meeting the world’s growing energy demand. However, pyrolytic conversions of biomass-to-biofuels suffer marginal total energy gain, and technical limitations such as bio-oils’ high viscosity and oxygen contents that result in unstable, corrosive and low-value fuels. This work demonstrates a new integrated biorefinery process for the co-production of biofuels and silver nanomaterials. By impregnating pure cellulose and corn stalk with silver nitrate, followed by pyrolysis, the gas yield (especially hydrogen) increases substantially. The condensable bio-oil components of the impregnated samples are considerably higher in furfurals (including 5-hydroxymethylfurfural). Though the overall activation energy barrier, as determined via the Distributed Activation Energy Model, does not change significantly with the silver nitrate pre-treatment, the increase in gases devolatilized, and improved 5-hydroxymethylfurfural yield, suggest a catalytic effect, potentially increasing decarboxylation reactions. After using this metal impregnation to improve pyrolysis fuel yield, following pyrolysis, the silver-char composite materials are calcined to remove the biomass template to yield silver nanomaterials. While others have demonstrated the ability to biotemplate such nanosilver on cellulosic biomass, they consider only impregnation and oxidation of the template. This is the first work that demonstrates the potential to extract upgraded biorenewable fuels during the biotemplating of nanomaterials, the same nanomaterials often used in catalytic energy applications.