Steam explosion of Aucoumea klaineana sapwood: Membrane separation of acetylated hemicelluloses.

The fractionation of the aqueous effluent of Aucoumea klaineana Pierre (Okoumé) sapwood steam explosion was examined by a sequential-dilution type membrane diafiltration. The permeate and retentate fractions were characterized by HPLC-SEC, HSQC-NMR, FTIR, UV-visible and HPAE-PAD ion chromatography. Diafiltration with 10 kDa regenerated cellulose membrane has been shown to provide efficient fractionation without fouling. O2 and/or O3 acetylated xylans with a lower proportion of O2 and/or O3 acetylated glucomannans were isolated in the retentate (≈35% w/w and 1.08 w/w% based on initial effluent solid content and on initial dry wood respectively, including 65% w/w in the range 9-22 kDa). The molecular weights of the polysaccharides were significantly higher than those obtained by ethanolic precipitation. The permeate concentrated low molecular mass oligomers (90% w/w < 2.3 kDa, 1.88 w/w% based on initial dry wood) composed of pectic sugars, highly acetylated xylans (DS ≈ 0.9) and relatively high proportion of soluble lignin (≈40% w/w) including Lignin-Carbohydrate Complexes (LCCs).

Homolytic and Heterolytic Cleavage of ß-Ether Linkages in Hardwood Lignin by Steam Explosion.

Steam-explosion lignin (SEL) was extracted with ethanol from steam-exploded hardwood (okoumé, Aucoumea klaineana Pierre) pretreated at various severities after neutral or acidic impregnation. The SELs were subjected to structural characterization by 2D HSQC NMR, 31P NMR, and SEC and compared with milled-wood lignin (MWL). A strong decrease in the ß- O-4 content is observed with increasing steam-explosion severity accompanied by a gradual increase in molecular mass. Cα-oxidized S units (S', Hibbert's ketones) were quantified by NMR and used as a marker of the hydrolytic mechanism; naphthol was used as a carbonium-ion scavenger. It has been observed that mixed reactions of hydrolysis and homolysis are involved, but the SEL is mainly cleaved homolytically, favoring recondensation through radical coupling even at low reaction severity. However, acidic preimpregnation of wood prior to steam explosion enhanced the carbonium-ion pathway.