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Cover1-
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原稿種別: 目次
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坂東 信雄, 貴傳名 甲, 村田 聡, 野村 正勝
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1-4
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Bond cleavage reactions of the bridge structure in coal are known to be key steps for coal conversion like liquefaction, carbonization, and so on. In the present study, we investigated two kinds of bond cleavage reactions, homolytic cleavage of dimethylene and ether bonds, and ipso-position cleavage of mono- and dimethylene bonds in the presence of hydrogen donor solvent (9,10-dihydroanthracene and 9,10-dihydrophenanthrene). The results suggest that cleavage reaction at ipso-position is also important at temperature range around 420℃.
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三國 真紀, 佐藤 正昭, 服部 英, 永石 博志, 佐々木 正秀, 吉田 忠
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5-8
発行日: 1996/10/28
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For the evaluation of autosolvent effect of bitumen, thermal cracking characteristics of bitumen is discussed from conversion and chemical structure changes. Athabasca tar sand bitumen was separated into light and heavy fractions by distillation. Mixtures of the both fractions at various ratios were heat-treated at 693K under 10MPa of nitrogen for 60min. Conversion of the heavy fraction into the light fraction was calculated with the chemical structure changes based on thermogravimetric analysis, elemental analysis and ^1H-NMR. Negative effect of the light fraction on the heavy fraction cracking was observed with dealkylation and paraffin formation. Polymerization of the light fraction to the heavy fraction was suggested due to lack of hydrogen in the thermal cracking under nitrogen atmosphere.
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奥山 憲幸, 安室 元晴, 佐藤 光一, 小松 信行, 奥井 利明, 嶋崎 勝乗
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9-12
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Effects of heavy solvent (bp.300-420℃) recycling and partial pressure of H_2S with iron/sulfur catalysts on coal liquefaction were investigated using bench scale unit (BSU). Process operations such as gas recycling and CLB (bp.420℃+) recycling were effective to increase distillate (C_5〜420℃) yield. It was confirmed that applying heavy solvent recycling to the operations, content of lighter fraction in product distillate was increased in maximum distillate yield of Victorian brown coal over than 60%mafc. Furthermore, it was proved that the amount of catalyst addition could be reduced to 1% by using γ-FeOOH as catalyst with excess sulfur to keep suitable partial pressure of H_2S in reactors.
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Andrew D. Schmitz, Chunshan Song
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13-17
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Platinum and palladium catalysts supported on H-mordentine (HM) and HY zeolites have been prepared, characterized and tested in the hydrogenation of naphthalene at 25-200℃, with or without added organic sulfur-containing compound (benzothiophene). Catalytic behavior is compared with Pt and Pd on conventional Al_2O_3 and TiO_2 supports. The zeolite-supported catalysts had significantly higher activity. High selectivity for one of two possible decahydronaphthalene (DeHN) isomers was obtained with the zeolite catalysts. For example, at 200℃ and 100% naphthalene conversion, 80% selectivity for cis-DeHN was obtained with Pt/HY; whereas, Pd/HM can be made to give 95% selectivity for trans-DeHN. On HM support, Pt was found to catalyze both hydrogenation and isomerization of cis-DeHN to trans-DeHN, but on HY support, Pt catalyzes only hydrogenation. High DeHN isomer selectivity was not realized with catalysts based on the conventional supports. Addition of sulfur in the form of benzothiophene decreased the activity of all catalysts tested, but sulfur poisoning was much less severe for zeolite-supported catalysts.
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二タ村 森
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p.
18-20
発行日: 1996/10/28
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Hydrogen transfer from tetralin to benzyl-1-methylnaphthalenes at 450℃ was promoted by Ni and active carbon. It has been shown that one of the active carbons shows higher activities than Ni, contrasting with the hydrogenation of trans-stilbene in tetralin at 380℃. These data suggest that carbon materials can act as active catalysts promoting hydrogen transfer from hydrogen donor solvent under coal liquefaction conditions, with a lesser extent of hydrogen acceptor adsorption on them.
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神戸 正純, 斎藤 勝, 石原 篤, 加部 利明
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p.
21-24
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The hydrogen exchange mechanism between tetralin and gaseous hydrogen was investigated in the presence of H_2S and H_2O. It was clarified that H_2S enhanced the hydrogen exchange reaction while H_2O inhibited it. The thermal reaction of tetralin did not affected significantly by H_2S. It was suggested that the hydrogen exchange reaction of tetralin with tritiated hydrogen in the presence of H_2S would proceed not only through a tetralyl radical but also through an electrophilic substitution and concerted reaction.
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伊藤 博徳, 目野 宏之, 上牧 修, 柴田 俊春, 辻 俊郎
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25-28
発行日: 1996/10/28
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Benzyl phenyl ether, n-octylbenzene and dibenzyl were reacted to examine the catalytic ability of three different synthetic pyrites with the lapse of time after production. The reaction was carried out in a 50ml autoclave, into which sample 1g, decalin 5g as solvent, 350mg catalyst and initial hydrogen pressure 10MPa were charged. The autoclave was held at 450 or 475℃ of reaction temperature for 1h. In the reaction of benzyl phenyl ether the conversion was 100% at any condition with and without the catalyst. R-34 catalyst did not show effective results. In the case of 9501 catalyst, benzene and toluene were produced with somewhat higher yield and condensed products decreased. Moreover, no benzylphenol was produced. The addition of sulfur to R-34 catalyst did not improve the ability. n-Octylbenzene showed relatively lower conversion at any condition (18-24%). In the reaction with R-34 catalyst the yield of toluene increased and that of C_2-benzene decreased. In the reaction with 9401 catalyst C_8-benzene (not n-octylbenzene) increased. In the reaction with 9501 catalyst C_8-benzene decreased, and toluene and benzene increased. The newer catalyst has somewhat the activity of splitting bond between aromatic carbon and aliphatic one as well as hydrogenation of aromatic ring.
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平野 勝巳, 高津 淑人, 岡田 俊彦, 小林 正俊
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p.
29-32
発行日: 1996/10/28
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Catalytic activity of pyrite on coal liquefaction has been investigated with a 5L batch-autoclave. The following conclusions are obtained. (1) Pulverized pyrite exhibits high catalytic activity for asphaltene hydrogenating reaction because pulverization increases its contact rate with reactant and the number of active-site on its outer surface. (2) It is inferred that catalytic activity of pyrite is related to chemical state of Fe and S on its surface.
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小方 英輔, 西嶋 昭生, 堀江 一之
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p.
33-36
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Relationships between structure change of iron sulfates and its catalysis were studies in development of highly active iron catalyst for coal hydroliquefaction. Catalytic activities of ferrous sulfate and ferric sulfate on the hydroconversion of 1-methylnaphthalene were very low in the absence of sulfur in the reaction system. But the activities of both sulfates increased with addition of solid sulfur. Ferrous sulfate was easily transformed active pyrrhotite for the aromatic-rings hydrogenation more than ferric sulfate.
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坂西 欣也, 蓮尾 東海, 谷口 秀樹, 永松 友重, 持田 勲
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p.
37-40
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The hydrogenation activity of various carbon-supported metal sulfides catalysts were investigated in order to elucidate the influences of metals and carbon species on the catalytic activity. NiMo sulfides supported on Ketjen Black (KB), Black Pearl 2000 (BP2000), or DIAHOPE active carbon (D-AC) of high surface areas above 1000 m^2/g exhibited the higher activity for the hydrogenation of 1-methylnaphthalene than NiMo sulfides supported on active cokes of lower surface areas and Fe-based catalysts supported on KB. The relationship between the catalytic hydrogenation activity and species of metals and carbon supports is briefly discussed based on the catalytic activity order and the characterization of the carbon-supported catalysts.
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小山 徹, 佐藤 光一, 兼子 隆雄, 嶋崎 勝乗
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p.
41-44
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The changes in the properties of iron-based catalysts during liquefaction using a bench scale unit (BSU) were investigated. It was found that S/Fe, atomic ratio of sulfur to iron in the catalyst system to be charged into a reactor, had great importance for surpression of catalyst deactivation. At the S/Fe of 1.2 a decrease of pyrrhotite content, an increase of troilite content and the crystal growth of iron sulfide were observed with the proceeding of reaction, but at the S/Fe of 3.0 both the formation of troilite and the crystal growth of pyrrhotite were remarkably surpressed.
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田澤 和治, 小山 徹, 兼子 隆雄, 嶋崎 勝乗
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p.
45-48
発行日: 1996/10/28
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The mechanism of pyrrhotite formation has been investigated by using XRD and TEM analysis after sulfiding of iron based catalysts in process solvent at several conditions. Fine crystallites of pyrrhotite were formed from ferric oxyhydroxide catalysts at the salfiding temperature around 250℃, and were grown rapidly With the increase of temperature due to the sintering of fine crystallites. It was found that crystal growth of pyrrhotite could be dependent on catalyst forms. A crystallite size of pyrrhotite formed from γ-FeOOH was smaller than that from α-FeOOH.
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岩崎 幸治, 王 杰, 富田 彰
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p.
49-52
発行日: 1996/10/28
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The mineral matter and catalyst in coal liquefaction residue was characterized. Fe-based catalyst was investigated by X-ray diffraction, scanning electron microscope, energy dispersed analysis of X-ray, and computer controlled scanning electron microscope.
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山本 久敬, 久保 久明, ツェデフスレン ツェーン
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p.
53-56
発行日: 1996/10/28
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Liquefaction tests of Mongolian coal were conducted using autoclve and flow micro reactor. Several sample coals showed to be liquefied easily and suitable coal for the liquefaction process.
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遠藤 浩光, 佐藤 正昭, 千葉 忠俊, 服部 英, 佐々木 正秀
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p.
57-60
発行日: 1996/10/28
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In this study, differences of coal liquefaction characteristics of Wandoan and Tanitoharum coals are discussed with considering of chemical structure of oil fraction. For Tanitoharum coal, the yield of gas and oil is lower than that of Wandoan coal, reflecting the contents of hydroaromatics in oil fraction from the former lower than that in Wandoan coal. The average molecular weight of oil remains almost constant for both coals, while the content of methane gradually increases with the progress of the reaction, suggesting that oil is gradually dealkylated.
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蓮尾 東海, 坂西 欣也, 持田 勲
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p.
61-64
発行日: 1996/10/28
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The catalytic activities of carbon-and alumina-supported NiMo catalysts were exmined for the single and two stage liquefactions of Yalluorn coal to compare their product oil distribution and influences of solvent and reaction conditions on the liquefaction efficiency. The NiMo sulfide supported on Ketjen Black (KB) yielded more lighter oil products both in the single and two stage liquefaction than NiMo/alumina catalyst and Fe-based catalyst, reflecting its higher hydrogenation activity for aromatic rings. Non-donOr solvents of 1-methylnaphthalene (1MN) and fluoranthene (FL) exhibited contrast behaviors in the liquefaction efficiency; the former gave the similar oil yield to that with tetralin solvent, while the latter did the lower yield because of its too high hydrogen acceptability. The liquefaction scheme for the higher efficiency is discussed in terms of reaction conditions including catalysts and solvents.
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畑 和明, 和田 健司, 光藤 武明
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p.
65-68
発行日: 1996/10/28
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Activity of Fe(CO)_5 as a catalyst precusor in the coprocessing using syngas-water was investigated. Fe(CO)_5 showed high catalytic activity to achieve the high conversion into THF-soluble matter (100%) and n-hexane-soluble matter (69.5%) in the coprocessing using Arabian Heavy vacuum residue and Wandoan coal (2:1, 400℃, 60min) in combination with the pretreatment at lower temperature.
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山口 宏, 奥山 泰男, 松原 健次, 加茂 徹, 佐藤 芳樹
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p.
69-72
発行日: 1996/10/28
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Under direct coal liquefaction conditions, coprocessing of Tanitharm coal and plastic using 1:1 Athabasca tar sand bitumen/tetralin mixture as a solvent was carried out with a 500cc autoclave. At 430℃ with 4MPa initial pressure of a simulated coke oven gas (1:1 hydrogen/nirogen mixture), observed value of oil yield for coliquefaction of coal with mixed plastic of PP, PS and PE was higher than calculated value, due to the interaction between coal and the mixed plastic.
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野中 寛, 松村 幸彦, 堤 敦司, 吉田 邦夫, 松野 泰也, 稲葉 敦
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p.
73-76
発行日: 1996/10/28
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Mixture of coal and cellulose was liquefied in supercritical water (390℃, 25MPa), and yields of residue, liquid and gas were compared with the result of separate liquefaction of coal and cellulose. Co-liquefaction did not change the residue yield, but lead to production of compounds with lower molecular weight, thus to a larger gas yield. Liquefaction was completed in 15 minutes.
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上田 知代, 松井 隆雄, 大槻 宗孝, 池永 直樹, 鈴木 俊光
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p.
77-80
発行日: 1996/10/28
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Co-liquefaction of micro algae with coal was carried out at 300℃〜400℃ under pressurized H_2 in 1-methylnaphthalene. Co-liquefaction was successfully proceeded under the conditions employed. However, a slight decrease in the hexane soluble oil yield was observed with Fe(CO)_5-S catalyzed run.
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橋本 友博, 高田 久嗣, 朝見 賢二, 矢野 元威
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p.
81-84
発行日: 1996/10/28
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Illinois No.6 coal was treated with a mixed solvent of water and cyclohexanol at 300-350℃ and 5.6-6.1MPa. The solvent treated coals were prepared by two methods, that is, explosive treatment and normal treatment in which high temperature and pressure are reduced immediately and gradually, respectively. Yield of the treated coal by the explosive treatment was higher than that by the normal treatment. This suggests the suppression of pyrolysis by explosive treatment. The properties of the treated coals were characterized by elemental analysis, CO_2 adsorption, SEM, and FT-IR measurements.
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川端 睦麿, 相原 洋一, 今田 邦弘, 野上 義信, 井口 憲二, 坂木 剛, 柴田 昌男, 廣末 英晴
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p.
85-88
発行日: 1996/10/28
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It has been reported that slurry temperature affects on the change in slurry viscosity. So, in the purpose of studying the effect of slurry temperature, change of slurry viscosity during heating for a few hours were studied. It was found that slurry viscosity increased in a few hours when heated above 70℃.
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坂脇 弘二, 野上 義信, 井口 憲二, 望月 通晴, 今田 邦弘, 立川 登, 茂木 照十三, 石川 勇
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p.
89-92
発行日: 1996/10/28
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To design the coal liquefaction reactor of large scale plant in future, it is important to understand characteristics of fluid dynamics in the coal liquefaction reactor. In this study, to measure fluid dynamics of liquid phase in the coal liquefaction reactor operating under coal liquefaction condition, appling of Neutron Attenuating Tracer (NAT) technique was discussed. Distribution of liquid phase residence time could be measured and, mean residence time and mixing diffusivity were obtained.
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中田 正夫
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p.
93-96
発行日: 1996/10/28
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Irinois #6 coal was liquefied in tetralin at temperature range from 300 to 400℃ in presence or absence of sulphur, hydrogen sulphide or hydrogen. At 300℃ sulphur and hydrogen sulphide have equal potential for conversion but at 370 and 400℃ sulphur promotes liquefaction much higher than hydrogen sulphide dose, despite of low hydrogen donor solvent remaining.
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大隈 修, 清水 孝浩, 井上 聡則, 重久 卓夫, 出口 哲也, 勝島 真一
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p.
97-100
発行日: 1996/10/28
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Victorian brown coal contains low ash and low sulfur. Therefore, we have been developing the Upgraded Brown Coal (UBC) process to refine the coal up to a clean solid fuel with low reactivity for spontaneous heating. The UBC process consists of a coal-oil slurry dewatering, coal-oil separation and oil recovery sections. This paper focuses on the behaviour of the coal during dewatering and the effects of oil and asphalt on the properties of the upgraded coal such as oxidation reactivity and spontaneous heating.
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上杉 研二, 金持 真理子, 兼子 隆雄, 嶋崎 勝乗
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p.
101-104
発行日: 1996/10/28
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Liquefaction conditions combined with prethermal treatment were investigated on Yallourn coal in order to increase oil yield with relation to effect of prethermal treatment on yield and properties of liquefaction product. It was considered that the effect of prethermal treatment is to suppress retrogressive reaction during initial stage of liquefaction. A highly active catalyst contribute mainly to this effect. Furthermore, it was found that concentration of coal slurry after prethermal treatment to decrease solvent/coal ratio at liquefaction reaction was effective to increase oil yield. Remarkable high yield of HS fraction was obtained by combination of prethermal treatment with concentration of slurry after treatment.
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進藤 照浩, 小松 信行, 岸本 充司, 奥井 利明, 兼子 隆雄, 嶋崎 勝乗
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p.
105-108
発行日: 1996/10/28
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It has been reported that the prethermal treatment with hydrogen-donor solvent and/or catalyst could be effective to increase oil yield on brown coal liquefaction. In this paper, prethermal treatment conditions in the initial stage of liquefaction were investigated by using the process solvent and iron-based catalyst in relation to the hydrogen transfer from solvent or catalyst to coal. In the initial stage of liquefaction, highly yield of HS (n-hexane soluble) fraction was obtained by using hydrogen-donor solvent. High H/C value of THFI (THF insoluble) was obtained by adding γ-FeOOH as catalyst, resulted in higher HS yield. It was considered that the combination of hydrogen-donor solvent and highly active catalyst such as γ-FeOOH in the prethermal treatment stage is quite effective to increase oil yield.
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古明地 東, 兼子 隆雄, 嶋崎 勝乗
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p.
109-112
発行日: 1996/10/28
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The effect of decomposition of oxygen-functional groups on coal liquefaction was investigated by means of quantitative analysis of oxygen-functional groups and by CP/MAS^<13>CNMR. In the case of pretreatment at 400〜430℃ in 1-Methyl naphthalene, ether crosslinking like a dibenzofuran was formed by dehydration of phenolic hydroxyl gruop and THFI yield increased in following liquefaction reaction. The addition of donor solvent like a Tetralin decreased the formation of ether crosslinking and decreased THFI yield in following liquefaction reaction.
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池田 耕一, 川端 睦麿, 望月 通晴, 今田 邦弘, 野上 義信, 井口 憲二
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p.
113-116
発行日: 1996/10/28
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Coal slurry sample was withdrawn from outlet of the preheater of NEDOL Process 1t/d Process Supporting Unit (PSU) to investigate the behavior of coal liquefaction reaction in early stage before reactors. At this point, main product was still solid residue with low yields of oil, CO+CO_2 and H_2O.
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池田 耕一, 今田 邦弘, 野上 義信, 井口 憲二
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p.
117-120
発行日: 1996/10/28
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Change in coal conversion before and after the liquefaction reactor of NEDOL Process 1t/d Process Supporting Unit (PSU) has been investigated by sampling test from slurry preheater outlet and reactor. Coal conversion rate in the reactor was estimated on the assumption of multistage complete mixing vessels and effect of temperature condition on the conversion was discussed.
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掛林 博史, 野上 義信, 井口 憲二, 相原 洋一, 今田 邦弘
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p.
121-124
発行日: 1996/10/28
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Three kinds of Ni-Mo catalyst for recycle solvent hydrogenation have been used at 1t/d PSU. It was shown that thier deactivation behavior were different. In this report, thier deactivation behavior was compared by use of the predictable equation of catalyst life. To explicate the difference of deactivation behavior, that is caused by deactivation factor and catalyst property, characterization of used catalyst is estimated by means of XPS and EPMA.
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岡田 康生, 野上 義信, 井口 憲二, 望月 通晴, 今田 邦弘
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p.
125-128
発行日: 1996/10/28
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The pressure drop occurred on the liquefaction reactors of 1t/d Process Supporting Unit (PSU) during Tanito Harum coal operation at coal concentration 50wt% conditions. It is attributable to deposits formed the principal constituent of calcite. The composition of the deposits and the relationship between the deposit formation and the operation of 1t/d PSU were discussed.
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糸永 真須美, 今田 邦弘, 岡田 康生, 井口 憲二
原稿種別: 本文
p.
129-132
発行日: 1996/10/28
公開日: 2017/03/22
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The characteristics of residue in coal liquefaction process were discussed. The heavy organic matter content and the ash content affect the viscosity of residue. The heavy organic matter content of residue at some liquefaction condition was able to be estimated by the simplified kinetic model. Also the ash content of residue was able to be calculated by its balance. So the viscosity of residue at some liquefaction condition was able to be estimated by them. Fare agreements with experiments and these estimation were obtained.
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鈴木 祐一郎, 杉本 義一, 岡田 清史
原稿種別: 本文
p.
133-136
発行日: 1996/10/28
公開日: 2017/03/22
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The biomaker analysis of coals from Japan, China and Indonesia were carried out for the estimation of original materials of coal. Also extractable organic matters from resent plant materials which heated with water were analyzed their biomakers to compare with that of coals. The n-alkane distribution of coals shows that low molecular weight compounds are increased with maturation degree increasing. But on artificial coal made from Metasquoia leafs is not indicated like the phenomena of coals. The diterpenoid whch is originated from coniferous woods is rich in several Japanese coal, but not found in Indonesian coals. The hopanoid distributions between two coals which are constists of low H/C atomic ratio and high H/C atomic ratio from the same seam are not show their distinction. The characteristics of coals which affected with characters of original materials are not valid for Hopanoid distribution.
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杉本 義一, 三木 康朗, 早水 紀久子, 岡田 清史, 鈴木 祐一郎
原稿種別: 本文
p.
137-140
発行日: 1996/10/28
公開日: 2017/03/22
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Cellulose was thermally decomposed in water at 200℃〜400℃, and the artificial coals obtained were hydrogenated over a presulfided Ni-Mo/Al_2O_3 catalyst at 350℃ in tetralin. The toluene-insoluble product containing the catalyst was further hydrocracked at 425℃ in tetralin. The distillable components were analyzed by a capillary GC-MS, and the distribution of the polycyclic compounds were compared each other.
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平戸 瑞穂, 長島 重明, 岡田 修一
原稿種別: 本文
p.
141-144
発行日: 1996/10/28
公開日: 2017/03/22
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Ingeneral, the composition of coal ash has shown the chemical composition. But from a practical point of view, the ash has the mineral composition. So, the corriration between chimical and mineral composition in the coal ash was clarified by use of the equation of material balance.
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愛澤 禎典, 林 潤一郎, 熊谷 治夫, 千葉 忠俊, 諸岡 成治
原稿種別: 本文
p.
145-148
発行日: 1996/10/28
公開日: 2017/03/22
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Four low rank coals were oxidized in 1N Na_2CO_3 aqueous solution at 85℃, into which atmospheric oxygen gas was bubbled. Coal peroxides formed were decomposed by an acid hydrolysis. The carbon conversion to volatiles such as CO_2 was at most 4%. The oxidation-hydrolysis depolymerized the coals and introduced oxygen functionalities such as -COOH and -OH into them. The treatment also dramatically increased the extraction yield of the coals with DMF, DMSO and THF/methanol mixture up to 90% or more. The extractability was correlated to the solubility parameters of the solvents much better than to their donor numbers. The increment of the extractability per amount of consumed oxygen strongly depended on the extent of C-C and C-O bond breaking.
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愛澤 禎典, 熊谷 治夫, 千葉 忠俊
原稿種別: 本文
p.
149-152
発行日: 1996/10/28
公開日: 2017/03/22
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EPR power saturation for both original and iodine doped coals has been measured in order to evaluate paramagnetic species in the coals. The EPR spectra of high rank coal consist of two components, one broad and one narrow singal. The power saturation characteristics of the broad signal changed with iodine doping, while that of narrow signal did not change. For low rank coal, no significant change was observed in EPR spactra and power saturation charactaristics with iodine doping.
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前 一広, 三浦 孝一
原稿種別: 本文
p.
153-156
発行日: 1996/10/28
公開日: 2017/03/22
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A new method was presented to estimate the hydrogen bondings in coal using DSC and FTir. Utilizing the equations proposed by Drago et al. for relating the OH bond energy, δE_<OH>, the energy of formation of a hydrogen bonding, E_<HB>, and the OH wavenumber shift on adduct formation of phenol with donor, an equation was developed for relating the enthalpy difference, ΔH, and the OH wavenumber shift between raw coal and a coal in a different state. Since both ΔH and Δν_<OH> are measurable, an equation relating E_<HB> and Δν_<OH> could be established. Using this equation we estimated the strength distribution of hydrogen bonding in Taiheiyo coal. The peak value of hydrogen bondings of the coal is about 20kJ/mol-OH. The change in the hydrogen bondings through heat treatment was well represented by the method.
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三浦 孝一, 前 一広, 島田 誠
原稿種別: 本文
p.
157-160
発行日: 1996/10/28
公開日: 2017/03/22
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It is essential to clarify the form of sulfur in coal and its emission behaivor during coal conversion in order to develop efficient desulfurization processes. In this paper quantitative analysis of sulfur forms was performed using the CAPTO method for eleven standard coals first. Then the effect of the heating rate on the emission rates of the sulfur containing gases during the pyrolysis was examined. Furthemore, the emission rates of the sulfur containing gases were analyzed using the Distributed-Activation-Energy-Model.
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堤 幸成, 相田 哲夫
原稿種別: 本文
p.
161-164
発行日: 1996/10/28
公開日: 2017/03/22
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Recently, we developed a reliable quantitative analytical method for oxygen containing functionalities in coal such as phenolic -OH and carboxylic -OH. By using this new method the thermal stability of carboxylic acid functionality in coal has been examined comparing to those of model compounds, and it was found that there were interesting differences in the thermal decomposition behavior between low rank coals and high rank coals, that is, the former contained significant amount of relatively unstable form of carboxylic acid functionalities which could be decomposed under 350℃, meanwhile the later seemed to have stable form of functionality like aromatic carboxylic acid.
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王 楠, 佐々木 正秀, 吉田 忠, 小谷川 毅
原稿種別: 本文
p.
165-168
発行日: 1996/10/28
公開日: 2017/03/22
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In our research, both continuous flow and pulse injection methods were applied for characterizing methanol adsorption on a coal surface. Akabira bituminous coal and Yallourn brown coal were used as samples. Akabira bituminous coal was heated in air to increase surface oxygen functional groups, while Yallourn brown coal was heated with tetralin as a solvent to decrease surface oxygen functional groups. These thermally processed coal samples were employed as adsorbents, and the interactions of methanol with such coal surfaces are examined on the basis of molar heats of methanol adsorption. The adsorption profiles had the same shape of Langmuir, regardless of thermal processes. However, the distribution of molar heat shifted to lower positions or to higher positions with the increment or decrement of surface oxygen functional groups.
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清水 和彦, 鷹觜 利公, 飯野 雅
原稿種別: 本文
p.
169-172
発行日: 1996/10/28
公開日: 2017/03/22
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Sorption of various solvents into coals was investigated to clarify micropore and cross-linked structure of coals. Methanol was quickly sorbed into all ranks of coals used, while pyridine slowly was sorbed. The Dual-Sorption Model was applied in analizing the sorption behavior, and several parameters on the coal porocity, the diffusion of the solvents into the coals were estimatid. The sorption behaviors of various solvents into the coals are discussed.
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安田 肇, 海保 守, 山田 理, 曽根田 靖, 小林 光雄, 牧野 三則
原稿種別: 本文
p.
173-176
発行日: 1996/10/28
公開日: 2017/03/22
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Sorption phenomena of methanol on Taiheiyo coal heat treated to 125℃ were investigated by repeated uptake and desorption experiments. From the isotherm changes, it is concluded that larger amount of methanol was sorbed in the 1st run for the sample re-heated at 70℃ compared to the case of both the 1st and the 2nd run for the sample re-heated at 125℃. Heat of sorption and the rate of vapor pressure change during sorption process are almost the same in the 1st and the 2nd run for the sample re-heated at 70℃. It is indicated that a small amount of methanol, which is detached from the sample after re-heated at 70℃, did not interact with the sample so strong. However, some amount of methanol, which might desorb after re-heated at 125℃, still remained in the sample interacting strongly at 70℃. Change in the rate of methanol sorption occured only with the existance of methanol which has strong interaction with a certain site in the coal sample.
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