A Study on the Different Types of Hydrogen in Coal and Its Derivatives by IR and High Resolution NMR Spectroscopy (I):With Special Regard to Coal and Asphaltene from Hydrogenated Coal
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Tke distribution of hydrogen in Hokkaido coal asphaltene was determined by IR and High Resolution NMR Spectroscopy. Asphaltene is an intermediate product in coal hydrogention and is considered to inherit to a certain extent the chemical structure of raw coal. The ratio of extinction coefficient of bands of aromatic CH group and aliphatic CH group ε<SUB>ar</SUB>/ε<SUB>al</SUB>, was calculated.<BR>The value of ε<SUB>ar</SUB>/ε<SUB>al</SUB> and hydrogen distribution of Hokkado coals and derivatives were discussed. The results are summarized as follows:<BR>(1) A markedly qualitative difference in IR spectra of Hokkaido coals of different ranks, asphaltenes (soluble in benzene but insoluble in n-hexane) and pyridinesolubles (insoluble inbenzene) from hydrogenated Hokkaido coals was not found. However, the aromatic CH stretchingband at 3030cm<SUP>-1</SUP> not found in the spectra of coals with a carbon content below 78.4% (Horonai coal) was found in the spectrum of Oyubari coal (C: 85.6%), and in the spectra ofall asphltenes and pyridine-solubles regardless of the rank of raw coal used as starting material.<BR>(2) Analyzing Hokkaido coal asphaltenes by High Resolution NMR Spectroscopy, the ratios of the aromatic hydrogen to the total hydrogen (H<SUB>ar</SUB>) areca. 0.24-0.41, while those of hydrogn insaturated groups α to aromatic rings (H<SUB>α</SUB>) are Ca. 0.24-0.33, and those of the hydrogen of paraffinic methylene, methenyl, and naphthenes or methylene groups, β or further from an aromatic ring, (Ho) are ca.0.30-0.50. The ratios of the aromatic hydrogen to the aliphatic hydrogen (H<SUB><I>ar</I></SUB>/H<SUB><I>al</I></SUB>) are 0.31-0.70.<BR>(3) The ratios of the extinction coefficient of the aromatic CH stretching band at 3030 cm<SUP>-1</SUP> to the aliphatic CH stretching band at 2920 cm<SUP>-1</SUP> of Hokkaido coal asphaltenes, ε<SUB>ar</SUB>/ε<SUB>al</SUB>, were 0.02-0.24 when IR spectra were measured using the potassium bromide technique. These values are smaller than those proposed by Brown and Francis, respectively 0.5 and 0.44.<BR>(4) It was clarified that ε<SUB>ar</SUB>/ε<SUB>al</SUB> of Hokkado coal asphaltenes was related to the chemical structure of raw coal and asphaltene, especially ear/eal was closest to the atomic ratio H/C of asphaltene. Estimating ear/sal of each raw coal by extrapolating to the value of the atomicratio H/C of raw coal, these values are 0.05-0.32 which are also smaller than the valuesproposed by Brown and Francis. Thus, we may determine Har/Hal of pyridine-solubles containing a insoluble part in pyridine at room temperature by using the value of ear/sal in this report.
- 一般社団法人 日本エネルギー学会の論文
一般社団法人 日本エネルギー学会 | 論文
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