Fractionating lignocellulose by formic acid: Characterization of major components

Treatment of corn (Zea mays L.) cob under mild reaction conditions (60 °C and atmospheric pressure) in 88% formic acid was an effective method for separating cellulose from hemicellulose and lignin components in lignocellulose. Most of the hemicellulose degradation and lignin removal occurred within the first 90 min. After 6 h treatment, the decomposition of hemicellulose and the recovery of lignin were over 85% and 70%, respectively. Multi-level structures of lignin and solid residues were further characterized by FTIR, XRD, TG/DTG, SEM and SEC. Peaks attributable to lignin or hemicellulose disappeared in FTIR spectra, indicating complete removal of these two components. The remaining solid residues had a higher crystalline index. The major pyrolysis temperature of corncob was increased after formic acid treatment; the molecular weight (MW) of cellulose in solid residues was higher than that in intact cobs, whereas the hemicellulose remaining in the pulp had a lower MW than the original. Lignin was extracted in an esterified form designated as formic acid lignin (FAL). FAL had two thermal decomposition temperatures (Td) at 277 °C and 385 °C. The MW of lignin increased following formic acid treatment, which may make it a better starting material for chemical syntheses.