Changes of chemical structure for coal hydrogenation oil with reaction times determined by FD mass spectroscopy.
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Characterization of coal hydrogenation oil by mass spectra was carried out to obtain information on the compound types constituted, the number of alkyl carbons attached to the aromatic rings and mol numbers of the respective types. Coal hydrogenation reactions were performed using an autoclave at 450°C, 100kg/cm<SUP>2</SUP> initial hydrogen pressure with red-mud and sulfur catalyst for 10, 30, 60, 90 and 120 min. of reaction times. Coal oils which were benzene-soluble, n-hexane-soluble, were separated into compound classes by means of a modified USBM-API method using liquid chromatography. The distribution of compound types byresolving the Z values from FD-mass spectra were determined for compound classes of LC fractions, which were separated mainly into paraffins (Fr-P) and aromatic ring numbers (Fr-M, D, and T), with varying reaction time. The carbon numbers of alkyl groups were also analysed by molecular weight and ring structure defined by the Z values.<BR>For a short contact reaction time, compound types ranging broadly from Z=-8 to -38 with smaller mol numbers for respective types were produced. Continuing the reaction, predominant distribution for compound types were observed for a reaction time of over 60 min., showing a maximum mol number of components belonging to Z= -20 and -22. Hydroaromatic compound types were also major products. Product distribution ratios of hydroaromatic to aromatic compound types were approximately the same in spite of different reaction times. It can be assumed that the macromolecular structure of the original coal, Miike coal, constitutes various unit structures with different ring sizes of hydroaromatic and aromatic clusters.<BR>For the saturated fractions (Fr-P), structural analyses by FD-mass spectra were carried out in the same way as for the aromatic oils and similar information were obtained. n-/iso-Paraffins (Z=+2) were the predominant type, with monocycloparaffins as the next most common type for each reaction time. The content ratios of cycloparaffins to n-/iso-paraffins increased to maximum at 30 min. and then decreased as reaction time increased to 120 min. It can be suggested for the production of saturated compounds that cycloparaffins are comparatively less stable than aliphatic compound, which are probably n-paraffins.
- 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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