Mild peroxyformic acid fractionation of Miscanthus × giganteus bark. Behaviour and structural characterization of lignin

Miscanthus × giganteus bark was subjected to mild fractionation with peroxyformic acid by a two stage process. A factorial experimental design was used to study and quantify the effect of the variables (formic acid concentration (80-90%), hydrogen peroxide concentration (0.2-0.4%), temperature of the first stage (60-80 °C), and treatment time of the second stage (60-120 min)) on the main parameters of fractionation: pulp yield, remaining lignin and total polysaccharides in pulp. The dependence of lignin precipitation rate on hydrogen peroxide concentration in liquor was also studied. Hydrogen peroxide concentrations inferior to 0.5% seems to be suitable to recover high percentages of lignin. The isolated lignin was analysed by 2D-HSQC, ¹³C- and ³¹P NMR spectroscopy, FTIR spectroscopy, size-exclusion chromatography and chemical analysis. The most important chemical modifications taken place in the lignin during the fractionation were identified: β-O-4′ cleavage and hydrolysis of LC-bond structures. The C9-formula was also determined: C₉H_6.81O_2.90(OCH₃)_0.68(COOH)_0.07(OH^Ph)_0.38(OH^Al)_0.33.