Katsunobu Ehara

A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water

Microcrystalline cellulose (avicel) was treated in supercritical waterusing batch-type and flow-type systems. The flow-type system made it possibletoshorten the heating, treating and cooling times, compared with the batch-typesystem. As a result, the flow-type system was able to liquefy avicel withoutproducing any supercritical water-insoluble residue. Although hydrolyzedproducts such as glucose and fructose, and pyrolyzed products such aslevoglucosan, 5-hydroxymethyl furfural, erythrose, methylglyoxal,glycolaldehydeand dihydroxyacetone were found in common from the water-soluble portiontreatedby both systems, the flow-type system gave a water-soluble portion with morehydrolyzed and less pyrolyzed products, together with water-solubleoligosaccharides consisting of cellobiose to cellododecaose and theirdecomposedproducts at their reducing end of glucose, such as[β–glucopyranosyl]1–11 β–levoglucosan,[β–glucopyranosyl]1–11 β–erythrose and[β–glucopyranosyl]1–11 β–glycolaldehyde. Inaddition, the precipitates of polysaccharides were recovered after 12h setting of the water-soluble portion. These results indicatedthat the flow-type system can hydrolyze cellulose with minimizing pyrolyzedproducts. On the other hand, the batch-type system resulted in a higher yieldof the pyrolyzed products due to the longer treatment, but a higher yield ofglucose due possibly to the higher pressure and concomitantly higher ionicproduct of water. Based on these lines of evidence, the process to increase theyield of the sugar is discussed under supercritical water treatment.

Decomposition behavior of cellulose in supercritical water, subcritical water, and their combined treatments

A comparative study on decomposition of cellulose between supercritical water (400°C, 40 MPa) and subcritical water (280°C, 40 MPa) treatments was made to elucidate the difference in their decomposition behavior. Consequently, the supercritical water treatment was found to be more suitable for obtaining high yields of hydrolyzed products. However, cellulose was found to be more liable to fragment under supercritical water treatment, resulting in a decrease in the yield of hydrolyzed products. On the contrary, cellulose was found to be liable to more dehydration in the subcritical water treatment. Based on these results, we have proposed the combined process of short supercritical water treatment followed by subcritical water treatment so as to inhibit fragmentation. Consequently, this combined treatment was able to effectively control the reaction condition, and to increase the yield of hydrolyzed products.

Characterization of the lignin-derived products from wood as treated in supercritical water

Sugi (Cryptomeria japonica D. Don) and buna (Fugus crenata Blume) woods were treated with supercritical water (>374°C, >22.1 MPa) and fractionated into a water-soluble portion and a water-insoluble residue. The latter was washed with methanol to be fractionated further into a methanol-soluble portion and a methanol-insoluble residue. Whereas the carbohydrate-derived products were in the water-soluble portion, most of the lignin-derived products were found in the methanol-soluble portion and methanol-insoluble residue. The lignin-derived products in the methanol-soluble portion were shown to have more phenolic hydroxyl groups than lignin in original wood. The alkaline nitrobenzene oxidation analyses, however, exhibited much less oxidation product in the methanol-soluble portion and methanol-insoluble residue. These lines of evidence suggest that the ether linkages of lignin are preferentially cleaved during supercritical water treatment. To simulate the reaction of lignin, a study with lignin model compounds was performed;β-O-4-type lignin model compounds were found to be cleaved, whereas biphenyl-type compounds were highly stable during supercritical water treatment. These results clearly indicated that the lignin-derived products, mainly consisting of condensed-type linkages of lignin due to the preferential degradation of the ether linkages of lignin, occurred during supercritical water treatment.

Characterization of low molecular weight organic acids from beech wood treated in supercritical water

Japanese beech (Fagus crenata Blume), its cell wall components, and model compounds were treated by supercritical water (380°C, 100 MPa) for 5 s using a batch-type reactor to investigate the production behavior of low molecular weight organic acids. It was found that cellulose and hemicellulose were decomposed to formic acid, pyruvic acid, glycolic acid, acetic acid, and lactic acid, whereas lignin was barely decomposed to such organic acids under the given conditions. However, after prolonged treatment (380°C, 100 MPa, 4 min) of lignin, some organic acids were recovered owing perhaps to the decomposition of the propyl side chain of lignin. It was additionally revealed that the predominant organic acid recovered was acetic acid, which might be derived from the acetyl group of hemicellulose in Japanese beech.

GC-MS and IR spectroscopic analyses of the lignin-derived products from softwood and hardwood treated in supercritical water

Softwood (Cryptomeria japonica) and hardwood (Fagus crenata) were treated in supercritical water (380°C, 100 MPa) for 8 s. The treated woods were fractionated to the water-soluble portion, methanol-soluble portion, and methanol-insoluble residues. For the methanol-soluble portion, which mainly consisted of lignin-derived products, gel permeation chromatography (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were conducted to clarify the molecular weight distribution and to identify the monomeric products, respectively. GPC analysis revealed that the methanol-soluble portion contains monomeric and some oligomeric products. GC-MS analysis identified 19 guaiacyl compounds in the methanol-soluble portion from softwood, and 15 syringyl monomeric compounds in the methanol-soluble portion from hardwood. The structures of identified products included not only phenyl propane (C6—C3) units but also C6—C2 and C6—C1 units. In addition, the infrared spectra suggested that the methanol-soluble portion maintains the typical structure of lignin, although it is rich in condensed-type linkages with some changes in the propyl side chain. These results indicate that the supercritical water treatment cleaves not only ether linkages but also part of the propyl chains in lignin to give various aromatic compounds.

Gas chromatographic and mass spectrometric (GC-MS) analysis of lignin-derived products from Cryptomeria japonica treated in supercritical water.

Sugi (Cryptomeria japonica D. Don) wood was treated with supercritical water (≫374°C, ≫22.1 MPa), and fractionated into the water-soluble portion, the methanol-soluble portion, and the methanol-insoluble residue. The methanol-soluble portion mainly consisted of the lignin-derived products. To characterize the compounds in the methanol-soluble portion, gel permeation chromatographic (GPC) and gas chromatographic-mass spectrometric (GC-MS) analyses were performed. The GPC analysis indicated that the methanol-soluble portion contained lignin-derived monomeric and dimeric products. GC-MS analysis detected 31 products which were expected to be monomeric compounds, and 18 of these were identified to be guaiacol, methylguaiacol, ethylguaiacol, vinylguaiacol, eugenol, propylguaiacol, vanillin, cis-isoeugenol, homovanillin, trans-isoeugenol, acetoguaiacone, propioguaiacone, guaiacylacetone, 2-methoxy-4-(1-hydroxypropyl)phenol, homovanillic acid, 2-methoxy-4-(prop-1-en-3-one)phenol, coniferyl aldehyde, and ferulic acid. In addition, 22 dimeric products were detected, and 4 of these were believed to be compounds with biphenyl type (5-5), diphenylethane type (Β-1), stilbene type (Β-1), and phenylcoumaran type (Β-5) structures. These results clearly indicated that the methanol-soluble portion included various monomeric and dimeric compounds produced as a result of the cleavage of ether linkages and propyl chains of lignin.

Fermentability of Water-Soluble Portion to Ethanol Obtained by Supercritical Water Treatment of Lignocellulosics

The water-soluble (WS) portion obtained by supercritical water treatment of lignocellulosics was studied for its fermentability to ethanol. A fermentation test of the WS portion showed it was not fermented to ethanol. Therefore, a wood characoal treatment was applied to the WS portion to remove furan and phenolic compounds, which are thought to be the inhibitors to sugar fermentability. It was found that treatment with wood charcoal can be effective at removing these inhibitors and improving the fermentability of the WS portion without reducing the levels of fermentable sugars.