A new method was presented to estimate the strength distribution of hydrogen bonds in coal. The hydrogen bonds include the coal intramolecule hydrogen bonds and coal-water hydrogen bonds formed by hydroxyls in coal. The method analyzes the FTIR spectrum ranging from 2400 to 3700 cm -1 obtained using the in-situ diffuse reflectance IR Fourier transform (DRIFT) technique with neat, undiluted, coal samples. The FTIR spectra during the heat-up of eight coals (seven Argonne premium coals and an Australian brown coal), an ion-exchange resin, and a lignin were measured every 20 °C from room temperature to 300 °C. Each spectrum was divided into six hydrogen-bonded absorption bands by a curve-resolving method, then the amount of hydroxyls contributing to each hydrogen bond was estimated by Beer's law by using different absorptivity for each band. The strength of each hydrogen bond was estimated using a relation presented by Drago et al. that is known as one of the "linear enthalpy-spectroscopic shift relations". Using this analysis method, changes in hydrogen bond distributions (HBD) with increasing temperature were successfully estimated for all the samples examined. By utilizing the HBD the changes in enthalpies associated with the desorption of adsorbed water, the glass transition, and the decomposition of COOH groups were well estimated. Only FTIR spectra measurements were found to be enough to obtain such enthalpies. This greatly simplified the calculation procedure and increased the accuracy of the enthalpies. The validity of the proposed in situ FTIR measurement method and the analysis method for obtaining HBD was well clarified.

There has been a great interest in converting lignin into chemicals, but lignin is not used as feedstock for chemical production at present. Considering the rigid structure of lignin, we have developed a new method to recover chemicals from lignin under severe conditions. This method is the hydrothermal oxidative degradation using 0.1% hydrogen peroxide solution in the flow reactor at 150-200 °C. When alkali lignin was oxidized for 2 min at 200 °C, the total yield of organic acids was as large as 0.45 g/g-lignin. The organic acids consisted of formic, acetic, and succinic acids, and the high-molecular-weight lignin also remained after the oxidation. On the other hand, when organosolv lignin was oxidized at 160 °C, lignin molecules were depolymerized into the oligomer of M W = ca. 300 and the total yield of organic acids was 0.20 g/g-lignin. The product distribution depended on the difference in the structures between the two lignin samples. It was clarified that the proposed method is valid to produce valuable chemicals from any kind of lignin.

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Friedel-Crafts reactions of aromatic and heteroaromatic compounds with an N-acyliminium ion pool were studied. The reaction of 1,3,5-trimethylbenzene in a batch reactor gave rise to the selective formation of a monoalkylation product (69%). Presumably, the second alkylation is slower than the first alkylation because of the protonation of the monoalkylation product that decreases its reactivity. The reaction of 1,3,5-trimethoxybenzene, however, gave rise to the formation of both monoalkylation (37%) and dialkylation (32%) products. Disguised chemical selectivity due to faster reaction than mixing seems to be responsible for the lack of selectivity. The use of micromixing was found to be quite effective to solve this problem to increase the selectivity. The monoalkylation product was obtained in 92% yield together with a small amount of the dialkylation product (4%). The reaction with various aromatic and heteroaromatic compounds revealed that the low mono/dialkylation selectivity was observed only for highly reactive aromatics. In such cases, the use of micromixing was quite effective to improve the selectivity. On the basis of micromixing, the selective sequential dialkylation using two different N-acyliminium ions was achieved. CFD simulations using a laminar flow and finite-rate model are consistent with the experimental observations and clearly indicate the importance of mixing.