Kinetic behavior of liquefaction of Japanese beech in subcritical phenol.

Non-catalytic liquefaction of Japanese beech (Fagus crenata) wood in subcritical phenol was investigated using a batch-type reaction vessel. After samples were treated at 160 °C/0.9 MPa-350 °C/4.2 MPa for 3-30 min, they were fractionated into a phenol-soluble portion and phenol-insoluble residues. These residues were then analyzed for their chemical composition. Based on the obtained data, the kinetics for liquefaction was modeled using first-order reaction rate law. Subsequently, the liquefaction rate constants of the major cell wall components including cellulose, hemicellulose, and lignin were determined. The different kinetic mechanisms were found to exist for lignin and cellulose at two different temperature ranges, lower 160-290 °C and higher 310-350 °C, whereas for hemicellulose, it was only liquefied in the lower temperature range. Thus, the liquefaction behaviors of these major cell wall components highlighted hemicellulose to be the most susceptible to liquefaction, followed by lignin and cellulose

Comparison of the decomposition behaviors of hardwood and softwood in supercritical methanol

The chemical conversion of Japanese beech (Fagus crenata Blume) and Japanese cedar (Cryptomeria japonica D. Don) woods in supercritical methanol was studied using the supercritical fluid biomass conversion system with a batch-type reaction vessel. Under conditions of 270°C/27 MPa, beech wood was decomposed and liquefied to a greater extent than cedar wood, and the difference observed was thought to originate mainly from differences in the intrinsic properties of the lignin structures of hardwood and softwood. However, such a difference was not observed at 350°C/43 MPa, and more than 90% of both beech and cedar woods were effectively decomposed and liquefied after 30 min of treatment. This result indicates that the supercritical methanol treatment is expected to be an efficient tool for converting the woody biomass to lower-molecular-weight products, such as liquid fuels and useful chemicals

Fiber Surface Structure and Fiber Liberation in Soda-anthraquinone Kraft and Soda Pulps as Determined by Conventional Electron Microscopy

Comparative studies on the surface structure of defibrated fibers and fiber liberation in nondefibrated chips from three different pulping processes, soda-anthraquinone (soda/AQ), kraft and soda pulping, were performed via conventional electron microscopy. By comparing the exposed fiber surface structure with the degree of fiber liberation, delignification processes in middle lamella regions were elucidated for these pulping systems. Soda/AQ pulping resulted in fiber liberation with less lignin removal than for either kraft or soda pulping process

Two-step hydrolysis of nipa (Nypa fruticans) frond as treated by semi-flow hot-compressed water

Two-step hydrolysis of nipa (Nypa fruticans) frond, one of the monocotyledonous angiosperms, was studied in a semi-flow hot-compressed water treatment at 230°C/10 MPa/15 min (first stage) and 270°C/10 MPa/30 min (second stage). In the first stage, hemicelluloses such as O-acetyl-4-O-methylglucuronoarabinoxylan and pectin and para-crystalline cellulose were selectively hydrolyzed, as well as lignin, which was partially decomposed. In the second stage, hydrolysis of crystalline cellulose and some additional decomposition of lignin were observed. In addition, inorganic constituents and free sugars, composed mainly of glucose, fructose, and sucrose, were recovered in cold water (20°C/10 MPa/30 min) prior to these 2 stages. In total, 97.3% of oven-dried nipa frond sample could be solubilized into cold and hot-compressed water. The degradation products in the water-soluble portion were primarily recovered as various saccharides (hydrolyzed moieties of the polyoses), which were later dehydrated, fragmented and isomerized partly. The residual (2.7%) is composed mainly of lignin associated with 0.4% of Si. A decomposition pathway is proposed for O-acetyl-4-O-methylglucuronoarabinoxylan as the major hemicellulose based on its various hydrolyzed products

Characterization of lignin-derived products from various lignocellulosics as treated by semi-flow hot-compressed water

To elucidate the decomposition behaviors of lignin from different taxonomic groups, five different lignocellulosics were treated with hot-compressed water (230 °C/10 MPa/15 min) to fractionate lignins into water-soluble portions, precipitates, and insoluble residues. The lignin-derived products in each fraction were characterized and compared. The delignification of monocotyledons [nipa palm (Nypa fruticans) frond, rice (Oryza sativa) straw, and corn (Zea mays) cob] was more extensive than that achieved for Japanese cedar (Cryptomeria japonica, gymnosperm) and Japanese beech (Fagus crenata, dicotyledon angiosperm). The water-soluble portions contained lignin monomers like coniferyl alcohol and phenolic acids, while the precipitates contained higher molecular weight lignin with high content of ether-type linkages. Lignin in the insoluble residues was rich in condensed-type structures. In all five lignocellulosics, ether-type linkages were preferentially cleaved, while condensed-type lignin showed resistance to hot-compressed water. In the monocotyledons, lignin–carbohydrate complexes were cleaved and gave lignins that had higher molecular weights than those eluted from the woods. These differences would facilitate the delignification in monocotyledons. Such information provides useful information for efficient utilization of various lignocellulosics

Characterization of three tissue fractions in corn (Zea mays) cob

Corn (Zea mays) cob is composed of three tissue fractions, chaff, woody ring, and pith, with dry weight percentages of 21.1%, 77.5%, and 1.4%, respectively. In this study, the cell wall components in these tissue fractions were characterized to examine their tissue morphology. The chemical compositions in the three fractions were relatively similar, and hemicellulose was the main component. Through sugar composition analysis, hemicellulose was mainly composed of xylan in all fractions, whereas the proportion of arabinose and galactose was different in the woody ring. From the alkaline nitrobenzene oxidation analysis, lignin in all fractions was composed of guaiacyl, syringyl, and p-hydroxyphenyl lignins, whereas their ratios varied in the three fractions. Furthermore, the amounts of cinnamic acids such as ferulic and p-coumaric acids, which are associated with corn lignin, were also different among the three fractions. With respect to the tissue morphology, the component cells in the three fractions were totally different each other. Furthermore, from the ultraviolet microspectrophotometry of each morphological region in the three tissue fractions, lignin concentration and distribution of cinnamic acids were different from one morphological region to another. The differences in chemical composition and lignin structures influence the decomposition behaviors in various treatments; thus, this information provides a clue to promote efficient utilization of corn cob into value-added chemicals

Lignin Distribution in Soda-Oxygen and Kraft Fibers as Determined by Conventional Electron Microscopy

The lignin distribution in loblolly pine (Pinus taeda L.) fibers produced by soda-oxygen and kraft pulping was investigated by electron microscopy of KMnO4 stained ultrathin sections and direct carbon replicas. A more extensive delignification of outer layers of fibers was found in soda-oxygen pulps than in kraft pulps. However, kraft pulping is more effective than soda-oxygen pulping in removing lignin from the lumen side of fibers. These observations were in good agreement with an earlier study of the lignin distribution within pulp fibers performed with SEM-EDXA technique

TiO2-supported Ni-Sn as an effective hydrogenation catalyst for aqueous acetic acid to ethanol

Various Ni and Ni-Sn catalysts supported on TiO2 were prepared and the catalytic activities were evaluated for ethanol formation from aqueous acetic acid. Although catalytic activities of the Ni/TiO2 catalysts were limited, the addition of Sn improved the activity dramatically, and the optimum Ni/Sn ratio was approximately 1:1 (w/w). SnO2, the precursor of Sn, could not be reduced into metal Sn in pure form but did reduce into Ni-Sn alloys in the presence of NiO, the precursor of Ni. Analyses with XRD and SEM-EDS revealed that the Ni-Sn alloys were homogeneously dispersed on the TiO2 surface. Furthermore, IR analysis indicated that the Ti atoms in the catalyst act as a Lewis acid, which coordinates to the oxygen atoms of acetic acid, enhancing the attack of hydrogens activated on neighboring Ni-Sn alloys. Based on these results, Ni-Sn/TiO2 is proposed as an effective hydrogenation catalyst for converting aqueous acetic acid into ethanol

Differential scanning calorimetric study of solidification behavior of monoacylglycerols to investigate the cold-flow properties of biodiesel

Monoacylglycerols (MAG) are impurities present in biodiesel as a result of incomplete reactions. MAG often solidify in biodiesel even at room temperature because of their high melting points. This worsens the cold‐flow properties such as the cloud point and pour point. We hypothesized that several types of MAG solidify simultaneously; therefore, we performed differential scanning calorimetry of binary mixtures of MAG to elucidate their interactions during solidification. Three thermodynamic formulas were then applied to the experimental results: (1) non‐solid‐solution, (2) solid‐solution, and (3) compound formation models. Binary mixtures of MAG showed complicated liquidus curves with multiple upward convex shapes, with which only the compound formation model fitted well. This model was applied to multicomponent mixtures that consisted of MAG and fatty acid methyl esters (FAME) as surrogate biodiesel fuels. We confirmed that the model still worked well. The results show that the compound formation model has good potential for predicting the cold‐flow properties of biodiesel

Influence of neutral inorganic chlorides on primary and secondary char formation from cellulose

The influence of various alkali and alkaline earth metal chlorides (LiCl, NaCl, KCl, MgCl₂, and CaCl₂) on primary and secondary char formation from cellulose was studied at 400°C. Secondary char was formed through carbonization of the volatile products. All chlorides increased the primary char yield while decreasing the secondary char formation, and this situation was promoted in the order of alkaline earth Mg, Ca, alkali Li > alkali Na, K. Levoglucosan yield also decreased along with the secondary char yield. These results indicate that the reduced formation of volatile levoglucosan was related to the decreasing yield of secondary char. A model experiment at 250°C revealed that these chlorides, especially the two alkaline earth metals, had catalytic action on the polymerization of levoglucosan, which serves to reduce the formation of volatile levoglucosan