Two-step hydrolysis of Japanese cedar as treated by semi-flow hot-compressed water

Two-step hydrolysis of Japanese cedar (Cryptomeria japonica) was studied as treated by semi-flow hot-compressed water at 230°C/10 MPa for 15 min and 280°C/10 MPa for 30 min as the first and second stages, respectively. At the first stage, hemicelluloses and para-crystalline cellulose, whose crystalline structure is somewhat disordered, were found to be selectively hydrolyzed, as well as lignin decomposition, whereas crystalline cellulose occurred at the second stage. In all, 87.76% of Japanese cedar could be liquefied by hot-compressed water and was primarily recovered as various hydrolyzed products, dehydrated, fragmented, and isomerized compounds as well as organic acids in the water-soluble portion. The remainder, 12.24%, could not be hydrolyzed and remained as the water-insoluble residue composed entirely of lignin. Based on the distribution of various products from hemicelluloses in Japanese cedar, their decomposition pathways were proposed as independent.     

Characterization of lignin-derived products from Japanese beech wood as treated by two-step semi-flow hot-compressed water

Japanese beech (Fagus crenata) wood was treated by two-step semi-flow hot-compressed water (the first stage: 230 °C/10 MPa/15 min, the second stage: 270 °C/10 MPa/15 min), and produced lignin-derived products in the hot-compressed water-soluble portions at the first and second stages, and the final residue of the second stage was characterized with alkaline nitrobenzene oxidation method and gel permeation chromatographic analysis. As a result, the lignin-derived products at the first stage, where hemicellulose was also decomposed, consisted of lignin-based monomers and dimers and oligomers/polymers in the water-soluble portion. A large part of the oligomers/polymers was, however, recovered as the precipitate during 12 h setting after hot-compressed water treatment. By the analysis of nitrobenzene oxidation products, there were relatively higher contents of ether-type lignin in the precipitate at the first stage than in original beech wood. Since the ether linkages of lignin are more preferentially cleaved by this hot-compressed water, lignin-based polymeric fractions were flowed out from the porous cell walls from which hemicellulose was removed. On the other hand, at the second stage condensed-type lignin remained in the precipitate and residue. Based on these results, decomposition behavior of lignin in Japanese beech wood as treated by the two-step semi-flow hot-compressed water was discussed regarding the topochemistry of lignin structure.     

Two-step hydrolysis of Japanese beech as treated by semi-flow hot-compressed water

A two-step hydrolysis of Japanese beech (Fagus crenata) was conducted by semi-flow treatment with hot-compressed water. The first treatment stage was conducted at 230°C/10 MPa for 15 min and the second at 270°C/10 MPa for 15 min. Hemicellulose and lignin were found to be hydrolyzed in the first stage, while crystalline cellulose was hydrolyzed in the second stage. The treatment solubilized 95.6% of the Japanese beech wood flour into water with 4.4% remaining as water-insoluble residue, which was composed mainly of lignin. Hydrolysis products from the first stage were xylose and xylo-oligosaccharides, glucuronic acid and acetic acid from O-acetyl-4-O-methylglucuronoxylan, and hydrolyzed monomeric guaiacyl and syringyl units and their dimeric condensed-type units from lignin. Products from the second hydrolysis stage were glucose and cello-oligosaccharides from cellulose. The dehydrated products levoglucosan, 5-hydroxymethylfurfural (5-HMF), and furfural, as well as fragmented products glycolaldehyde, methylglyoxal, and erythrose, were recovered in the first stage from hemicellulose, and to a greater extent in the second stage from cellulose. Furthermore, organic acids such as glycolic, formic, acetic, and lactic acids were recovered in both stages. Based on these lines of evidence, decomposition pathways of O-acetyl-4-O-methylglucuronoxylan and cellulose are independently proposed.