高分解能固体NMR法およびガス分析による石炭低温酸化反応機構の解析
畑 友輝, 高橋 貴文, 櫻木 潔, 山口 哲正, 齋藤 公児, 則永 行庸
pp. 693-702
抄録
Spontaneous combustion property of low rank coal, an important issue in coal science, has been substantially studied. However, there are few studies discussing quantitative chemical structural changes of coal during its oxidization under 80°C.In the present study, low rank coals of X and Y were oxidized in an adiabatic vessel where their temperature was increased due to spontaneous heating. Generated gases of H2O, CO2, and CO were analyzed by gas chromatography during the oxidization. As a result, coal Y, which was more easily oxidized than coal X, showed higher generation rate of CO2 and CO gas than coal X. Some of H2O generated during the oxidation must have been remained in coal as adsorbed water since the amount of water in the oxidized coal was higher than that before oxidation.13C MAS NMR spectra of coal X and Y indicated that and chemical reaction producing carboxyl acid in coal Y is more activated than that in coal X. Furthermore, the number of aromatic carbon was reduced during the oxidization. It implied that the aromatic carbon might contribute to oxidization reaction. Coal Y before oxidation had smaller number of aromatic carbon per one cluster than coal X, while the structural parameters of aliphatic carbons in coal X and Y were almost the same. It is considered that smaller number of aromatic carbons more destabilize carbon radicals to generate “active” species. Such active carbon radicals are suggested to also react with oxygen in the atmosphere.
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鉄と鋼 Vol.108(2022), No.10
鉄と鋼 Vol.108(2022), No.10
鉄と鋼 Vol.108(2022), No.10