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山田 理, 海保 守, 安田 肇, 曽根田 靖, 小林 光雄, 牧野 三則
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p.
177-180
発行日: 1996/10/28
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Miike coal was quantitatively oxidized at 150℃ using ^<18>O_2 in a closed system equipped with a circulator. Gas evolution during oxidation was monitored by mass spectrometer (MS). To investigate the surface reactivity, the oxidized coal was pulverized under vacuum. Composition of out gas was monitored by MS. Water and carbon monooxide were main products in both oxidation and pulverization. Changes in coal surface before and after oxidation was observed by an environment controlled atomic force microscope (AFM). No pore structure was observed under inert atomosphere and a slight surface deformation was detected when coal surface was exposed to oxygen.
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大木 章, 謝 暁峰, 中島 常憲, 前田 滋
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p.
181-184
発行日: 1996/10/28
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Upgrading of low-rank coals, such as Loy Yang and Yallourn coals, has been performed by use of "Hot Water Drying (HWD)" method. Influence of varying the treatment temperature upon coal properties, such as hygroscopicity, functional group content, and specific surface area, has been investigated. As the treatment temperature was elevated, the hygroscopicity of coal decreased; while the content of hydrophilic groups, such as hydroxyl and carbonyl groups, decreased.
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佐塚 拓郎, 真下 清, 和井内 徹
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p.
185-188
発行日: 1996/10/28
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The effect of pre-heat treatment of Taiheiyo coal on the solvent swelling and the hydrogenolysis reaction was studied. The coal was treated at 200℃ for 1hr. The treatments were practiced by different heating rates and cooling rates. The swelling on the treated coal and the liquefaction yield obtained from the hydrogenolysis were dependent on the heating and cooling rates in the pre-heat treatment.
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吉田 貴紘, 鷹觜 利公, 飯野 雅, 加藤 健次, 深田 喜代志
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p.
189-192
発行日: 1996/10/28
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Coals were heat-treated at heating rate of 3℃/min in an autoclave under nitrogen, and then quenched to room temperature. The heat-treated coals were extracted with a carbon disulfide-N-methyl-2-pyrrolidinone (CS_2-NMP) mixed solvent at room temperature. Molecular weight distribution (MWD) of the extracts (solvent-soluble-component) was investigated by the size exclusion chromatography (SEC) method using the CS_2-NMP mixed solvent as mobile phase. The extraction yields of the heat-treated coals gave a maximum in the softening range, and there was a good correlation between the maximum fluidity and the maximum extraction yield of the coals. Fluidity of heat-treated coals is discussed from the changes of MWD of the extracts.
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村岡 淳一, 熊谷 治夫, 林 潤一郎, 千葉 忠俊
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p.
193-196
発行日: 1996/10/28
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Effects of lithium iodide doping on devolatilization characteristics of two kinds of brown coals were investigated by in-situ FT-IR. The spectra were resolved into several absorptionpeaks on the basis of hydrogen-bond strength. The doping resulted in a shift of the peaks arisen from weakly hydrogen-bonded OH to those from strongly bonded ones. Intensities of the peaks decreased along with the devolatilization and were higher for the doped coals than for the non-doped coals.
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Hiroshi Saito, 山下 安正, 稲葉 敦
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p.
197-200
発行日: 1996/10/28
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To better understand the chemistry of coke formation, a good coking coal was pyrolyzed at 3 and 50℃/min. to peak temperatures ranging from 450 to 600℃. All volatiles were captured (overall material balance closed to within 4%) and quantified gravimetrically or analytically. Weight loss and volatiles production trends were quite different at the two heating rates. Weight loss and volatiles production all increased with temperature at 50℃/min, while different trends were observed at 3℃/min. Study of the resulting coke by polarized-light microscopy also supports the volatiles and weight loss data which suggest different mechanisms of coke formation at the two heating rates.
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岸野 正裕, 坂西 欣也, 光来 要三, 持田 勲
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p.
201-204
発行日: 1996/10/28
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The Australian subbituminous Wandoan coal was pretreated with acid solution and/or tetralin, these coals were studied the reactivity of flash pyrolysis. The decrease of the char amounts were confirmed for the coals. In the simple Image Analysis of the char, the increase of large pores was certified for acid pretreated char. Its increasing of the large pores should be the reason for progressing the plastisity of the pretreated coal.
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呉 志恒, 大塚 康夫
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p.
205-208
発行日: 1996/10/28
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Conversion of coal nitrogen to N_2 during the fixed bed pyrolysis of low rank coals increases with increasing temperature in the range of 600〜1200℃, and reaches 65〜70% at 1200℃, but contrarily char nitrogen decreases with temperature. Demineralization by HCl washing drastically suppresses N_2 formation with the corresponding increase in char nitrogen, and removes mainly Fe- and/or Ca-containing species from these coals. The addition of a nanophase iron catalyst promotes N_2 formation from the demineralized coals. These observations show that Fe species inherently present in the ion-exchangeable forms are responsible for the remarkable formation of N_2, and that N_2 arises mostly from iron-catalyzed solid-phase reactions of char nitrogen and precursors.
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牧 泰輔, 前 一広, 奥津 肇, 三浦 孝一
原稿種別: 本文
p.
209-212
発行日: 1996/10/28
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We have recently proposed that flash pyrolysis of coal-solvent slurry will be a promising process for recovering valuable chemicals in high yields from coal under mild conditions. In this study the improvement of the above method was tried by modifying coal through H_2O_2 oxidation at 60℃. This treatment changes the coal into more flexible structure, and the oxidized coal is dissolved to a large extent in methanol based mixed solvent. The slurry prepared from the oxidized coal and methanol based mixed solvent was pyrolyzed in a free fall pyrolyzer at 923 to 1123K. This method realized significant increases in the yields of total volatiles, liquids and BTX. It was found that the amount of total volatile increased surprisingly up to 85kg/100kg, when the coal dissolved in methanol based mixed solvent was pyrolyzed.
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海保 守, 安田 肇, 小林 光雄, 山田 理, 曽根田 靖, 牧野 三則
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p.
213-216
発行日: 1996/10/28
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Theoretical equations for the excess amount of oxygen consumed by reactions other than CO formation and amount of water decomposed were derived from stoichiometry of C, H and O in a general gasificattion reaction formula. Fluctuate of the composition of gas produced by HYCOL reactor was analyzed using the equations and process of coal gasification reaction was investigated.
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山田 哲夫, 田村 和久, 橋本 晴美, 船木 稔, 鈴木 勉
原稿種別: 本文
p.
217-220
発行日: 1996/10/28
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Coal chars prepared under different carbonization conditions were gasified with CO_2 to different conversion levels. The gasifification rate was decreased with increasing the conversion. Various physical and chemical properties of the chars were measured to clarify the relation to the situation. The items measured were as followed: the composition of C, H and O; carbon crystal structure; surface area and porosity; chemical form of ash components. Oxygen content for char and Lc determined by XRD were increased with increasing the conversion, whereas R value determined by laser Raman band and surface area were decreased. Char with higer conversion gave XRD lines of rankinite, gehlenite, and anorthite, accompanying the agglomeration of mineral matter. These results indicated that the reasons for the diminishing rate of char with increasing the conversion would be dependent on not only the physical and chemical changes in properties but also the activity loss of indigenous calcium by forming chemical bondings with sillica and alumina.
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上宮 成之, 青木 健一, 森 卓, 小島 紀徳
原稿種別: 本文
p.
221-224
発行日: 1996/10/28
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Agglomeration and reaction characteristics of various coal chars were investigated in a jetting fluidized bed coal gasifier. The level of carbon conversion was increased with decreasing carbon content, as properly expected. The effect of carbon content was observed especially in the grid zone; reactions of CO production and steam gasification proceeded for coals with lower carbon content. Agglomeration occurred below the softening temperature of coal ash.
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森下 佳代子, 武井 博基, 原野 安土, 宝田 恭之
原稿種別: 本文
p.
225-228
発行日: 1996/10/28
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In order to clarify the relation between physical and chemical properties of coal char treated at high temperature and gasification reactivity, coal chars of various coal rank were characterized by oxygen gasification, TPD, XRD and AAS.
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松岡 浩一, 林 潤一郎, 熊谷 治夫, 千葉 忠俊
原稿種別: 本文
p.
229-232
発行日: 1996/10/28
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A needle penetration technique combined with a dilatometry was applied to six kinds of coals to evaluate their apparent viscosity during heating. The viscosity of the coals depended on heating rate, nitrogen gas pressure as well as their pyrolysis characteristics. The viscosity change shifted to a higher temperature range for higher heating rates. The minimum viscosity decreased and approached to constant value asymptotically as the heating rate increased. The temperature range for viscosity change roughly coincided with that for the change of yield of pyridine extract. It was suggested that the viscosity depended on the temperature, mass fraction of plastic intermediate and interaction between plastic intermediate and the other components.
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林 石英, G. Benjamin, 阿部 秀臣, 原野 安土, 宝田 恭之
原稿種別: 本文
p.
233-236
発行日: 1996/10/28
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SO_2 capture ability of Ca-ion exchanged coal and limestone was investigated under high pressure (1-20atm) with CO_2 gas presence. It is found that, Ca-ion exchanged coal ash excel limistone in SO_2 capture ability under high paresure. When CO_2 partial pressure is lower than the equilibrium CO_2 pressure for CaCO_3 decomposition, P^*_<CO2>, the SO_2 capture ability of sample decrease with increasing total pressure. It is explained by that CO_2 partial pressure increased with increasing total pressure, and hastened CaO sintering. When total pressure raised letting the CO_2 partial pressure higher than the P^*_<CO2>, the SO_2 capture ability of sample has been improved again.
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庄 前林, 山内 篤子, 大島 康弘, 呉 志恒, 大塚 康夫
原稿種別: 本文
p.
237-240
発行日: 1996/10/28
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Combustion of a char prepared from a Chinese lignite at 1123K was investigated with a batch scale quartz-made fluidized bed reactor to make clear the parameters affecting the conversion of char-N to N_2. Almost all of the N-containing gases during combustion was N_2 under O_2-lean conditions, and only small amounts of NH_3 and HCN but no NO_x and N_2O were detected. The formation of N_2 took place throughout combustion. XPS measurement clearly indicates that, at the final stage of combustion, pyridinic-N disappared completely and pyrrolic-N decreased but O-containing nitrogen complexes became the main component. A mechanism for conversion reactions of char-N in combustion has been discussed.
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Ph. Chambrion, T. Kyotani, A. Tomita
原稿種別: 本文
p.
241-244
発行日: 1996/10/28
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NO reduction by carbon is investigated in the presence and absence of O_2. N_2 and N_2O formation are evidenced in both. N_2 formation mechanism is proposed, which take the presence of nitrogen containing surface compound into account. O_2 is found to increase NO reduction by removing nitrogen containing complexes from the carbon surface.
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丸山 勝久, 吉澤 徳子, 石川 越郎, 小林 光雄, 戸田 雄三, 山田 能生, 白石 稔
原稿種別: 本文
p.
245-248
発行日: 1996/10/28
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Three Japanese coals of different rank were heat-treated with KOH from 300℃ to 850℃, and their changes in pore structure were estimated by the adsorption of nitrogen at -196℃, X-ray diffraction patterns and TEM photographs of them. Furthermore, twelve Japanese coals were KOH - activated only at 800℃, and their variations in pore structure with rank of coal were studied by the N_2 adsorption experiments.
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吉澤 徳子, 山田 能生, 白石 稔, 小島 重行, 玉井 久司, 安田 源
原稿種別: 本文
p.
249-252
発行日: 1996/10/28
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Activated carbons with selective mesoporosities were prepared from the mixture of Morwell coal and metal (Fe, Ni, Co) complex. Pore structure of the activated sample were determined with N_2 adsorption isotherms, and metal-oxide particles included in the carbon matrix were characterized with x-ray diffraction patterns and TEM photographs of them. It was estimated that formation of mesopores in the activated carbons is related with migration of oxide particles. Dependence of metal kinds upon pore structure was also discussed.
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藤本 英和, 松方 正彦, 上山 惟一
原稿種別: 本文
p.
253-256
発行日: 1996/10/28
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Datong and Illinois coal as examples of coal having high and low flotabilities, respectively, were used to study flotability. A film flotation which can be used for evaluating the critical wetting surface tension (γ_c) of each coal particle was performed. When the flotability of coal particles having the same value of γ_c was compared between Datong and Illinois coal, the flotability of Datong coal was greater than that of Illinois coal. It was, hence, suggested that heterogeneous distribution of hydrophobic strength on a surface of each coal particle should be taken into account to understand the attachment of a coal particle and a bubble.
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駒野 隆宏, 真下 清, 和井内 徹, 田中 千晶, 吉岡 稔泰, 杉本 義一, 三木 康朗
原稿種別: 本文
p.
257-260
発行日: 1996/10/28
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Mixtures of glucose and aromatic compound were thermally decomposed at 180℃ in water to examine condensation reactions of carbohydrate and aromatic ring in coalification process. The distillable constituents and their hydrogenated products were analyzed by GC and GC-MS. The solid products were characterized by elementary analysis, FT-IR and NMR.
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村田 聡, 張 岩, 貴傳名 甲, 野村 正勝
原稿種別: 本文
p.
261-264
発行日: 1996/10/28
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In order to obtain insights into structural features of meso-carbon microbeads (MCMB), we examined its butylation reaction promoted by potassium or dibutylzinc. Both reactions gave THF soluble products in ca. 90% yield. This is the first example for effective solubilization of these carbonaceous materials. The resulting products were analyzed by ^<13>C NMR and gel permeation chromatography.
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大川 剛直, 笹井 崇司, 薦田 憲久
原稿種別: 本文
p.
265-268
発行日: 1996/10/28
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Coal structure construction system is proposed in this paper. In this system, first some partial structures are selected from candidates of a structure, which are constructed by connecting input fragments, using construction knowledge found from chemists. Then the partial structures are narrowed down to appropriate one in terms of three-dimensional conformation using partial structure evaluation. We confirmed that the system can construct coal structures far better than the structure constructed by chemists.
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菅野 元行, 関田 美智代, 村松 良活, 真下 清, 和井内 徹
原稿種別: 本文
p.
269-272
発行日: 1996/10/28
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Three coals of different rank were heat-treated at below 473K in a nitrogen atmosphere, and the structural changes in coals were investigated from the pyridine extractabilities, the volumetric swelling ratios using methanol or benzene as solvent and the amounts of carboxyl and phenolic hydroxyl functional groups. Further, the structural changes in deashed coals induced by heat treatment were also discussed.
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王 杰, 富田 彰
原稿種別: 本文
p.
273-276
発行日: 1996/10/28
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The hydrothermal reaction of Ca(OH)_2 with reagent quartz at temperatures between 175℃ and 340℃ has been studied to obtain fundamental information on coal demineralization with Ca(OH)_2. At a Ca/Si atomic ratio of about 1, quartz was first converted to Ca_2Si_7O_4・H_2O which then reacted with residual quartz or residual Ca(OH)_2, forming a silica-rich phase or a calcium-rich phase, and finally all these intermediate compounds were transformed to xonotlite when a prolonged treatment at high temperature was employed. At higher Ca/Si ratios, a fraction of quartz remained unreacted even after severe treatments. On the basis of the above investigations on model reaction, removal of quartz from coal through Ca(OH)_2/HCl leaching were interpreted.
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菊地 毅光, 早坂 和章, 鷹觜 利公, 飯野 雅
原稿種別: 本文
p.
277-278
発行日: 1996/10/28
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Surface tension was studied on solutions in N-methyl-2-pyrrolidinone of the acetone-soluble fraction extracted from the Upper Freeport coal. Ultrasonic waves irradiation was used to homogenize a solution of the coal extract containing both surface-active and surface-nonactive species. The surface tension decreased slowly for the solution in which the coal extract solvated completely. The adsorption of surfactant species to the surface of the solution was found to be very slow, distinguished from other factors such as solvation, re-orientation, and micelle-like association which might lead to a change in the surface tension.
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鷹觜 利公, 磯田 茂紀, 土井 聡, 飯野 雅
原稿種別: 本文
p.
279-282
発行日: 1996/10/28
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Various gel films have been suceeded to be prepared by using sovent-soluble constituents and polar solvents such as N-methyl-2-pyrrodinone and N,N-dimethyl-formamide. The creep compliance behaviors of the gel films showed the existence of viscoelastic properties, suggesting that the gel films have mainly physical cross-linked networks by coal-coal interaction and coal-solvent interaction, since the the solvent-soluble constituents have never original covalent cross-links. When the weight fraction of solvent in the gels was decreased, the viscous strain and the viscoelastic strain decreased, while the elastic strain was almost unchanged. The elastic component may be attributed to original elasticity of coal. The network structure of homogeneous coal-solvent gel films is discussed.
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佐々木 正秀, 永石 博志, 吉田 忠
原稿種別: 本文
p.
283-286
発行日: 1996/10/28
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In order to evaluate the effect of intermolecular cohesion on the conversion of bituminous coal, the reactivity of oxygen-methylated and reductively methylated coals were tested by non-catalytic liquefaction reaction in tetralin solvent at 693K. The yield of oil fraction from oxygen-methylated and reductively methylated coals were increased by 12 and 22wt%, respectively, compared to the raw coal. The increment of oil fraction corresponds to the acceleration of the hydrogenolysis reaction form preasphalten to oil. The effect of hydrogen bonds in bituminous coal on its hydrogenolyisis reaction made about half contributions to oil yield compared with the others such as van der Waals and charge transfer interaction.
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上林 豊, 岡田 清史
原稿種別: 本文
p.
287-290
発行日: 1996/10/28
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Some possible impacts of coal properties were given on the futuer coal utilization technologies, especially coal liquefaction technology, based on the data obtained from analytical and experimental tests. Our previous work has demonstrated that the relationship between the coal properties and their liquefaction characteristics can be developed, and that the degree of coalification and petrographic composition are important coal parameters.
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清水 聖幸, 斎藤 郁夫, 佐々木 進介, 菅沼 彰
原稿種別: 本文
p.
291-294
発行日: 1996/10/28
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Lignite solubilization with superacid, HF/BF_3-toluene or isopentane was studied through ionic reaction at the mild condition (150℃) without gaseous hydrogen. Solubility of the treated coals were examined in terms of kinds of superacid, reaction temperature and solvents.
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大和田 拓央, 真下 清, 和井内 徹
原稿種別: 本文
p.
295-298
発行日: 1996/10/28
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Hydrogenolysis reactions of Taiheiyo coal after deminerarization using HCl or HF were carried out at 693K for 60min. It appeared that the deminerarization using HF solution of high concentration influenced organic molecular structure of the coal.
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金持 真理子, 兼子 隆雄, 嶋崎 勝乗, 熊谷 治夫, 千葉 忠俊
原稿種別: 本文
p.
299-302
発行日: 1996/10/28
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Radical formation in Victorian brown coal has been investigated by using in situ high temperature ESR apparatus which can detect relatively stable π and σ radicals during heat treatment. In this work, it was found that increase in the radical concentration as temperature rising was suppressed by transferable hydrogen (TH) in recycle solvent at around 400℃. And the result of autoclave test suggested that pretreatment of coal at around 350℃ with hydrogen-donating solvent was effective to inhibit retrogressive reactions. It is discussed about the effect of radical stabilization by TH and the influence on structural properties of the products at initial stage.
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山本 光義, 吉田 忠, 小谷川 毅
原稿種別: 本文
p.
303-306
発行日: 1996/10/28
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In the research on upgrading of coal derived oils, the studies on the heteroarom-removal and the nuclear hydrogenation of aromatics are extremely important. We have previously reported the results of the Ru supported on nonacidic-metal oxide catalysts for the nuclear hydrogenation of polycyclic aromatics. In this paper, two types of catalysts such as Ru/Mn_2O_3-NiO and P_2O_5-Mn_2O_3-NiO were tested for the heteroatom-removal of dibenzothiophene and carbazole. The results showed that these catalysts were more active for the hydrodenitrogenation of carbazole than a commercial Ni-Mo catalyst, but less active for the hydrodesulfurisation than the commercial one. Furthermore, it was found that the phosphate on the catalyst behaved the resistance to the sintering of the support.
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森 孝雄, 礒田 隆聡, 草壁 克己, 諸岡 成治, 林 潤一郎
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p.
307-310
発行日: 1996/10/28
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Glass transition temperature of Illinois No.6 coal was determined by differential scanning calorimetry to be 589K. In order to enhance the mobility of protons, the coal was heated to 623K beyond the glass transition at a rate of 5K/min. The coal was then directly transferred to a Curie-point pyrolyzer without exposure to air and was pyrolyzed at 1037K. The char yield was decreased to 59kg per 100kg of original coal, 3kg smaller than that of the original coal. This reduction was ascribed to the effective donation of hydrogen radicals to coal fragments, caused by the increase in proton mobility.
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野中 俊晴, 岸野 正裕, 坂西 欣也, 光来 要三, 持田 勲
原稿種別: 本文
p.
311-314
発行日: 1996/10/28
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The curie point flash pyrolysis (FP) of coals of different rank was carried out for the chracterrization of the FP products with standard reagent spectrum. The distributions of the products pyrolyzed at 450, 590 and 740℃ for 5 sec were chracterized and conated by GC-MS sysytem and calcurated quantitatively. More amounts of phenol derivatives were produced at 740℃. The effect of acid treatment was also investigated.
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松永 利昭, 布田 潔, 村上 賢治, 京 雅史, 細谷 進, 小林 茂治
原稿種別: 本文
p.
315-318
発行日: 1996/10/28
公開日: 2017/03/22
会議録・要旨集
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Production of benzene, toluene and xylene was investigated by in situ contact reforming of low temperature tar from some coals with metallic ion-exchanged Y-zeolite as a catalyst in a gas-flow type thermobalance. BTX yields depended on the type of catalyst, on coal and also on reaction temperature. Ni-exchanged zeolite was found effective for relatively aromatic-abundant tar from PSOC 830 coal and it also showed the most appropriate temperature at around 650℃, while Zn-exchanged one was effective for lower aromatic tar from such as Taiheiyo coal. Since the exchange fraction of Ni ion had a large effect on BTX yield at around 50%, a better result is expected by further investigation.
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G. Benjamin, M.C. Roman, 山崎 由美子, 阿部 秀臣, 原野 安土, 宝田 恭之
原稿種別: 本文
p.
319-322
発行日: 1996/10/28
公開日: 2017/03/22
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The desulfurization behaviors of Ca-exchanged brown coal and limestone toward H_2S gas was examined. CaS obtained was oxidized under various experimental conditions. The desulfurization behavior depended on the reaction temperature and the type of sorbent. Under all the experimental conditions examined, Ca-exchanged brown coal was quite active for both the desulfurization reaction and the oxidation reaction.
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冨田 博, 礒田 隆聡, 草壁 克己, 諸岡 成治, 林 潤一郎
原稿種別: 本文
p.
323-326
発行日: 1996/10/28
公開日: 2017/03/22
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An Australian brown coal (Yallourn; YL) was oxidized at 70℃ for 12h under atmospheric pressure in alcohol containing aqueous hydrogen peroxide, which was added as the radical initiator. The mild oxidization proposed in this study greatly increased the solubility of the coal in methanol. This was accomplished by the cleavage of covalent bonds by H_2O_2 and the alkylation with alcohol. Degradation and alkylation were then evaluated by pyrolyzability. The H_2O_2 oxidation without the presence of alcohols decreased the char yield by 17-18kg per 100kg of raw coal. The presence of 1-PrOH or 3-BuOH further decreased the char yield and greatly increased the BTX yield The degradation of coal was thus promoted by alcohol, which worked as the stabilizer of coal fragment radicals in the primary pyrolysis stage.
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田中 千晶, 吉岡 稔泰, 駒野 隆宏, 真下 清, 和井内 徹, 杉本 義一, 三木 康朗
原稿種別: 本文
p.
327-330
発行日: 1996/10/28
公開日: 2017/03/22
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Hydrous mild pyrolysis of glucose and glycine was performed at 130℃, 200℃ and 300℃, and the nitrogen functionality of the condensation products were examined by X-ray photoelectron spctroscopy. The solid materials were also hydrocracked at 430℃ in tetralin, and the distillable nitrogen compounds were analyzed by GC-FID/NPD and GC-MS.
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