Haruo Kawamoto

Pyrolysis behavior of levoglucosan as an intermediate in cellulose pyrolysis: polymerization into polysaccharide as a key reaction to carbonized product formation

Pyrolysis behavior of levoglucosan (1,6-anhydro-β-d-glucopyranose), the major anhydromonosaccharide formed during cellulose pyrolysis, was studied at 250°–400°C under nitrogen. The pyrolysis products were found to change stepwise: levoglucosan → MeOH-soluble fraction (lower-molecular-weight products and oligosaccharides) → water-soluble fraction (polysaccharides) → insoluble fraction (carbonized products). From the present experimental results, a pathway of cellulose pyrolysis via anhydromonosaccharide is proposed including polymerization to polysaccharides (a reversible reaction) as a key reaction to carbonized product formation.

Pyrolysis reactions of various lignin model dimers

Primary pyrolysis reactions and relative reactivities for depolymerization and condensation/carbonization were evaluated for various lignin model dimers with α-O-4, β-O-4, β-1, and biphenyl substructures by characterizing the tetrahydrofuran (THF)-soluble and THF-insoluble fractions obtained after pyrolysis at 400°C. Reactivity was quite different depending on the model structure: depolymerization: α-O-4 [phenolic (ph), nonphenolic (nonph)], β-O-4 (ph) > β-O-4 (nonph), β-1 (ph, nonph) > biphenyl (ph, nonph); condensation/carbonization: β-1 (ph) > β-O-4 (ph) > α-O-4 (ph) > β-O-4 (nonph), biphenyl (ph, nonph), α-O-4 (nonph), β-1 (nonph). Major degradation pathways were also identified for β-O-4 and β-1 model dimers: β-O-4 types: Cβ-O cleavage to form cinnamyl alcohols and phenols and Cγ-elimination yielding vinyl ethers; β-1 types: Cα-Cβ cleavage yielding benzaldehydes and styrenes and Cγ-elimination yielding stilbenes. Relative reactivities of these pathways were also quite different between phenolic and nonphenolic forms even in the same types; Cβ-O cleavage (β-O-4) and Cγ-elimination (β-1) were substantially enhanced in phenolic forms.

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.

Catalytic pyrolysis of cellulose in sulfolane with some acidic catalysts

Catalytic pyrolysis of cellulose in sulfolane (tetramethylene sulfone) with sulfuric acid or polyphosphoric acid gave levoglucosenone, furfural, and 5-hydroxymethyl furfural (5-HMF) up to 42.2%, 26.9%, and 8.8% (as mol% yield based on the glucose unit), respectively. Pyrolysis behaviors of the intermediates indicated the conversion pathways, and the conversion: levoglucosenone → furfural was found to require water. The control of the water content in the pyrolysis medium was quite effective in controlling the product selectivity between levoglucosenone and furfural: mild vacuum conditions to remove the product water dramatically enhanced the levoglucosenone yield, while steam distillation conditions increased the furfural and 5-HMF yields.

Condensation Reactions of Some Lignin Related Compounds at Relatively Low Pyrolysis Temperature

Abstract Condensation reactions of some lignin related compounds were studied under the pyrolysis conditions (air/250°C/2 h). Guaiacol, methylguaiacol and methylveratrole were recovered almost quantitatively with small amount of radical coupling products derived from phenoxy and benzyl radicals. Side‐chains (Cα˭Cβ, Cα‐OH) increased the condensation reactivity substantially. From the dimer structures, vinyl condensation and quinone methide mechanisms were indicated as important condensation pathways for these compounds. As for model compounds for the structures formed in lignin primary pyrolysis, coniferyl alcohol (from β‐ether structure) was very reactive, while 4,4′‐dihydroxy‐3,3′‐dimethoxystilbene (from β‐aryl structure) was stable.

Stoichiometric studies of tannin-protein co-precipitation

Co-precipitation of a series of galloylglucoses (hydrolysable tannins) with bovine serum albumin (BSA) was studied stoichiometrically by analysing both galloylglucoses and BSA in the precipitates using HPLC. BSA-precipitating ability increased mainly with an increase in the number of galloyl groups in a galloylglucose molecule but was also affected by the position of the galloyl group (penta- > tetra- > 2,3,6-tri- > 2,3,4-tri- >> di- >> monogalloylglucose). The precipitated BSA increased linearly with an increase in the number of galloyl groups bound to a BSA molecule. BSA-precipitating abilities of the galloylglucoses were closely related to their relative affinities for BSA. These results suggest a two-stage mechanism: initial complexation of galloylglucose with BSA and subsequent precipitation, as a mechanism of the co-precipitation.

Pyrolytic cleavage mechanisms of lignin-ether linkages: A study on p-substituted dimers and trimers

Abstract Pyrolytic cleavage mechanisms of lignin-ether linkages were studied with some dimers and trimers which have various p-substituted Cα-phenoxy groups (-H, -OCH3, -Cl or -COCH3). Pyrolysis of these model compounds provides phenols and isoeugenol type products. To determine whether the reactions mechanisms are heterolytic or homolytic, the reactivities were compared based on Hammetts substituent constant (σ p ) and the ΔBDE parameter, namely the bond dissociation energy (BDE) reduction. The α-ether-linkages in phenolic forms are cleaved in a heterolytic mechanism, while in non-phenolic forms the α-ether linkages are cleaved homolytically. Cleavage of these α-ether linkages is the rate-determining step for the scission of the Cβ-O bond in trimers. The β-ether-linkages in the non-phenolic trimers are cleaved through the β-scission type reaction from the benzyl radical intermediates. On the other hand, quinone methide formation through heterolytic cleavage of the α-ether linkages is the key step for following homolysis of the Cβ-O bonds in the phenolic trimers. Electron attracting character of the quinone methide structure reduces the BDE of the Cβ-O bond.

Effects of side-chain hydroxyl groups on pyrolytic β -ether cleavage of phenolic lignin model dimer

Effects of side chain hydroxyl groups on pyrolytic β-ether cleavage of phenolic model dimers were studied with various deoxygenated dimers under pyrolysis conditions of N2/400°C/1 min. Although phenolic dimer with hydroxyl groups at the Cα− and Cγ−positions was much more reactive than the corresponding nonphenolic type, deoxygenation at the Cγ-position substantially reduced the reactivity up to the level of the nonphenolic type. These results are discussed with the cleavage mechanism via quinone methide intermediate formation, which is activated through intramolecular hydrogen bonds between Cα− and Cγ− hydroxyl groups.

Influence of inorganic matter on wood pyrolysis at gasification temperature

The influence of inorganic matter on the pyrolysis of Japanese cedar (Cryptomeria japonica) wood was studied at a gasification temperature of 800°C with demineralization through acid washing. Some influences on the formation of char, tar, and low molecular weight products coincided with results reported at temperatures lower than the gasification temperature. However, the carbonization behavior of the volatile products and the yield of polysaccharide fraction were not able to be explained as a sum of the pyrolysis of cellulose, hemicellulose, and lignin even after demineralization. These results suggest some interactions between wood constituent polymers other than the influence of inorganic matter.

Reaction behavior of lignin in supercritical methanol as studied with lignin model compounds

Abstract The reaction behavior and kinetics of lignin model compounds were studied in supercritical methanol with a batch-type supercritical biomass conversion system. Guaiacol, veratrole, 2,6-dimethoxyphenol, and 1,2,3-trimethoxybenzene were used as model compounds for aromatic rings in lignin. In addition, 5-5, β-1, β-O-4, and α-O-4 types of dimeric lignin model compounds were used as representatives of linkages in lignin. As a result, aromatic rings and 5-5 (biphenyl)-type structures were stable in supercritical methanol, and the β-1 linkage was not cleaved in the β-1-type structure but converted rapidly to stilbene. On the other hand, β-ether and α-ether linkages of β-O-4 and α-O-4 lignin model compounds were cleaved rapidly, and these compounds decomposed to some monomeric compounds. Phenolic compounds were found to be more reactive than nonphenolic compounds. These results indicate that cleavages of ether linkages mainly contribute to the depolymerization of lignin, whereas condensed linkages such as the 5-5 and β-1 types are not cleaved in supercritical methanol. Therefore, it is suggested that the supercritical methanol treatment effectively depolymerizes lignin into the lower-molecular-weight products as a methanol-soluble portion mainly by cleavage of the β-ether structure, which is the dominant linkage in lignin.