Biofuels from Corn Stover: Pyrolytic Production and Catalytic Upgrading Studies

Due to security issues in energy supply and environmental concerns, renewable energy production from biomass becomes an increasingly important area of study. Thus, thermal conversion of biomass via pyrolysis and subsequent upgrading procedures were explored, in an attempt to convert an abundant agricultural residue, corn stover, into potential bio-fuels.

Pyrolysis of corn stover was carried out at 400, 500 and 600oC and at moderate pressure. Maximum bio-char yield of 37.3 wt.% and liquid product yield of 31.4 wt.% were obtained at 400oC while the gas yield was maximum at 600oC (21.2 wt.%). Bio-char characteristics (energy content, proximate and ultimate analyses) indicated its potential as alternative solid fuel. The bio-oil mainly consisted of phenolic compounds, with significant proportions of aromatic and aliphatic compounds. The gas product has energy content ranging from 10.1 to 21.7 MJ m-3, attributed to significant quantities of methane, hydrogen and carbon dioxide. Mass and energy conversion efficiencies indicated that majority of the mass and energy contained in the feedstock was transferred to the bio-char.

Fractional distillation of the bio-oil at atmospheric and reduced pressure yielded approximately 40-45 wt.% heavy distillate (180-250oC) with significantly reduced moisture and total acid number (TAN) and greater energy content. Aromatic compounds and oxygenated compounds were distributed in the light and middle fractions while phenolic compounds were concentrated in the heavy fraction.

Finally, hydrotreatment of the bio-oil and the heavy distillate using noble metal catalysts such as ruthenium and palladium on carbon support at 100 bar pressure, 4 hours reaction time and 200o or 300oC showed that ruthenium performed better at the higher temperature (300oC) and was more effective than palladium, giving about 25-26% deoxygenation. The hydrotreated product from the heavy distillate with ruthenium as catalyst at 300oC had the lowest oxygen content and exhibited better product properties (lower moisture, TAN, and highest heating value), and can be a potential feedstock for co-processing with crude oils in existing refineries. Major reactions involved were conversion of phenolics to aromatics and hydrogenation of ketones to alcohols. Results showed that pyrolysis of corn stover and product upgrading produced potentially valuable sources of fuel and chemical feedstock.