Fundamental gasification-degradation of polyethylene (PE) over glass beads was studied beads by the use of a fixed bed tubular flow reactor at 486∼562°C, as the beginning in researches for direct catalytic gasification of PE by the flow system. Gasification of PE over glass beads proceeded stationarily without depending on reaction time in every reaction condition. The degree of gasification (RgF) or the rate of it increased with contact time and exponentially with temperature. An empirical relationship among RgF, contact time (1/F) and temperature was found to be:RgF=1.56×106exp(-32, 500/RT)(1/F)0.467where F is the mass flow rate of PE melted.Product composition (_??_C8-hydrocarbon fractions) shifted to smaller fractions with temperature rise, but the amount of methane was slightly 5.5% and 16% of all gaseous products at 486°C (RgF=0.023) and 562°C (RgF=0.204), respectively. Ratio of olefin to paraffin for C2∼C4 fractions increased with the rise of temperature and 1/F, and the ratio for C4 fraction went up to 4 at 562°C and 22min/g-PE. On the other hand, product composition and ratios of olefin to paraffin did not depend on reaction time in every condition.
{"title":"Gasification of Polyethylene over Solid Catalysts (Part 2)","authors":"A. Ayame, Tadashi Yoshida, H. Kano","doi":"10.1627/JPI1959.17.226","DOIUrl":"https://doi.org/10.1627/JPI1959.17.226","url":null,"abstract":"Fundamental gasification-degradation of polyethylene (PE) over glass beads was studied beads by the use of a fixed bed tubular flow reactor at 486∼562°C, as the beginning in researches for direct catalytic gasification of PE by the flow system. Gasification of PE over glass beads proceeded stationarily without depending on reaction time in every reaction condition. The degree of gasification (RgF) or the rate of it increased with contact time and exponentially with temperature. An empirical relationship among RgF, contact time (1/F) and temperature was found to be:RgF=1.56×106exp(-32, 500/RT)(1/F)0.467where F is the mass flow rate of PE melted.Product composition (_??_C8-hydrocarbon fractions) shifted to smaller fractions with temperature rise, but the amount of methane was slightly 5.5% and 16% of all gaseous products at 486°C (RgF=0.023) and 562°C (RgF=0.204), respectively. Ratio of olefin to paraffin for C2∼C4 fractions increased with the rise of temperature and 1/F, and the ratio for C4 fraction went up to 4 at 562°C and 22min/g-PE. On the other hand, product composition and ratios of olefin to paraffin did not depend on reaction time in every condition.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"122 1","pages":"226-231"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77166090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A pyridine-soluble matter in a synthetic coal, obtained from Kuwait vacuum residual oil by a coking reaction, has been subjected to a further coking reaction. This stepwise coking reaction was carried out three times. Coking reactions of asphaltene and maltene separated from the residual oil have also been carried out at 430°C for 0.5, 3 and 5 hours.It has become apparent that, in an initial step of the coking reaction, high molecular weight compounds of high sulfur content preferentially form a pyridine-insoluble matter, and it has been proposed that, in a later step, the coking reaction proceeds with cleavage of C-S bonds of thiophene type compounds, resulting in partial desulfurization of the pyridine-insoluble matter.A microscopic observation and an electron probe analysis have made it clear that sulfur is distributed homogeneously over various kinds of textures of the synthetic coal.
{"title":"Studies on Coking of Residual Oils (Part 4)","authors":"H. Ozaki, Mamoru Yamane, T. Tokairin","doi":"10.1627/JPI1959.17.181","DOIUrl":"https://doi.org/10.1627/JPI1959.17.181","url":null,"abstract":"A pyridine-soluble matter in a synthetic coal, obtained from Kuwait vacuum residual oil by a coking reaction, has been subjected to a further coking reaction. This stepwise coking reaction was carried out three times. Coking reactions of asphaltene and maltene separated from the residual oil have also been carried out at 430°C for 0.5, 3 and 5 hours.It has become apparent that, in an initial step of the coking reaction, high molecular weight compounds of high sulfur content preferentially form a pyridine-insoluble matter, and it has been proposed that, in a later step, the coking reaction proceeds with cleavage of C-S bonds of thiophene type compounds, resulting in partial desulfurization of the pyridine-insoluble matter.A microscopic observation and an electron probe analysis have made it clear that sulfur is distributed homogeneously over various kinds of textures of the synthetic coal.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"11 1","pages":"181-187"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86881361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The heats of adsorption of various surface active substances from n-heptane and benzene onto iron oxides and iron sulfide were measured using flow microcalorimeter. The relation between their chemical structures and anti-wear properties was investigated. The anti-wear properties and heats of adsorption of pentaerythritol caprylates increased with an increase of the number of hydroxyl groups involved in an ester molecule. The lubricities and heats of adsorption of the alkyl derivatives of pyridine were dependent on the position of the substituent on the ring. Stearic acid formed the close packing adsorbed film to give the greater antiwear properties than isostearic acid. It was found that the films such as FeS and Fe3O4 formed on the metal surface under extreme pressure lubrication are very active for the adsorption of the polar compounds.
{"title":"Heats of Adsorption and Anti-wear Properties of Some Surface Active Substances","authors":"Seiichiro Hironaka, Y. Yahagi, T. Sakurai","doi":"10.1627/JPI1959.17.201","DOIUrl":"https://doi.org/10.1627/JPI1959.17.201","url":null,"abstract":"The heats of adsorption of various surface active substances from n-heptane and benzene onto iron oxides and iron sulfide were measured using flow microcalorimeter. The relation between their chemical structures and anti-wear properties was investigated. The anti-wear properties and heats of adsorption of pentaerythritol caprylates increased with an increase of the number of hydroxyl groups involved in an ester molecule. The lubricities and heats of adsorption of the alkyl derivatives of pyridine were dependent on the position of the substituent on the ring. Stearic acid formed the close packing adsorbed film to give the greater antiwear properties than isostearic acid. It was found that the films such as FeS and Fe3O4 formed on the metal surface under extreme pressure lubrication are very active for the adsorption of the polar compounds.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"1 1","pages":"201-205"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85126431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Steam Reforming of Hydrocarbons on Noble Metal Catalysts (Part 3)","authors":"E. Kikuchi, Kiichi Ito, Y. Morita","doi":"10.1627/JPI1959.17.206","DOIUrl":"https://doi.org/10.1627/JPI1959.17.206","url":null,"abstract":"","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"1 1","pages":"206-211"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77949127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
E. Echigoya, H. Niiyama, A. Ebitani, H. Iida, Tomohiro Ookawa
The roles of reducing agents such as H2, CO and NH3 in catalytic reduction of NO over supported metal oxide catalysts were studied from the viewpoint of reaction mechanisms. The reaction of NO with H2 or CO was proved to proceed through the redox cycles of the catalyst, that is, catalyst was oxidized by NO and then was reduced, to complete the catalytic sequence by the reducing agents. On the other hand, it was confirmed that NH3 or fragments of NH3 directly reacted with the adsorbed NO.These differences of the roles of reducing agents in the reaction mechanism satisfactorily explain some features of catalytic removal of NO in the practical process containing oxygen.
{"title":"Catalytic Reductions of NO with H2, CO or NH3 over Supported Metal Oxide Catalysts","authors":"E. Echigoya, H. Niiyama, A. Ebitani, H. Iida, Tomohiro Ookawa","doi":"10.1627/JPI1959.17.232","DOIUrl":"https://doi.org/10.1627/JPI1959.17.232","url":null,"abstract":"The roles of reducing agents such as H2, CO and NH3 in catalytic reduction of NO over supported metal oxide catalysts were studied from the viewpoint of reaction mechanisms. The reaction of NO with H2 or CO was proved to proceed through the redox cycles of the catalyst, that is, catalyst was oxidized by NO and then was reduced, to complete the catalytic sequence by the reducing agents. On the other hand, it was confirmed that NH3 or fragments of NH3 directly reacted with the adsorbed NO.These differences of the roles of reducing agents in the reaction mechanism satisfactorily explain some features of catalytic removal of NO in the practical process containing oxygen.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"425 1","pages":"232-235"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78177802","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Selective recoveries of useful gaseous hydrocarbons from polyethylene were attempted over various zeolites and silica-alumina at 420∼580°C by the use of a batchwise reactor. The rates of degradations of polyethylene over these catalysts were promoted 2 to 7 times faster than that of the thermal degradation.The order in degree of total formation of hydrocarbons of 1∼4 carbon atoms (gasification) at 480°C was silica-alumina, CaX, NaX, and NaY>CaA>NaA>thermal. In the thermal degradation and catalytic degradations over A-type zeolites, hydrocarbons of 2 and 3 carbon atoms were mainly produced. In catalytic degradations over others, hydrocarbons of 3 and 4 carbon atoms were main products and isobutane was formed. Over CaX and silica-alumina the amount of isobutane was in the same order or more of hydrocarbons of 3 carbon atoms (C3) and other C4 hydrocarbons were about 1/4 of isobutane. Over NaX and NaY isobutane was about 1/3 of other C4 hydrocarbons.Further, dependences of the gasification and product composition on reaction time and temperatue were revealed in detail.
{"title":"Gasification of Polyethylene over Solid Catalysts (Part 1)","authors":"Tadashi Yoshida, A. Ayame, H. Kano","doi":"10.1627/JPI1959.17.218","DOIUrl":"https://doi.org/10.1627/JPI1959.17.218","url":null,"abstract":"Selective recoveries of useful gaseous hydrocarbons from polyethylene were attempted over various zeolites and silica-alumina at 420∼580°C by the use of a batchwise reactor. The rates of degradations of polyethylene over these catalysts were promoted 2 to 7 times faster than that of the thermal degradation.The order in degree of total formation of hydrocarbons of 1∼4 carbon atoms (gasification) at 480°C was silica-alumina, CaX, NaX, and NaY>CaA>NaA>thermal. In the thermal degradation and catalytic degradations over A-type zeolites, hydrocarbons of 2 and 3 carbon atoms were mainly produced. In catalytic degradations over others, hydrocarbons of 3 and 4 carbon atoms were main products and isobutane was formed. Over CaX and silica-alumina the amount of isobutane was in the same order or more of hydrocarbons of 3 carbon atoms (C3) and other C4 hydrocarbons were about 1/4 of isobutane. Over NaX and NaY isobutane was about 1/3 of other C4 hydrocarbons.Further, dependences of the gasification and product composition on reaction time and temperatue were revealed in detail.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"43 1","pages":"218-225"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84626227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To realize the reaction of allyl radical with ethylene, 1, 5-hexadiene was pyrolyzed in excess ethylene by use of a flow type apparatus at 580∼700°C under atmospheric pressure. First-order reaction kinetics fitted the rate of 1, 5-hexadiene decomposition and the rate constant obtained was k=1012.9 exp (-55, 000/RT) sec-1, which indicated that allyl radical generated was effectively quenched by ethylene. The main primary products were cyclopentene (38.0mol%), 1-pentene (28.5), 1-butene+butadiene (19.0) and propylene (14.5). Minor ones were 1, 4-pentadiene and cyclopentadiene. A mechanism was proposed focussing the discussion on C5 products formation from allyl radical and ethylene.
{"title":"Kinetics and Mechanism on a Reaction of Allyl Radical with Ethylene","authors":"T. Sakai, D. Nohara","doi":"10.1627/JPI1959.17.212","DOIUrl":"https://doi.org/10.1627/JPI1959.17.212","url":null,"abstract":"To realize the reaction of allyl radical with ethylene, 1, 5-hexadiene was pyrolyzed in excess ethylene by use of a flow type apparatus at 580∼700°C under atmospheric pressure. First-order reaction kinetics fitted the rate of 1, 5-hexadiene decomposition and the rate constant obtained was k=1012.9 exp (-55, 000/RT) sec-1, which indicated that allyl radical generated was effectively quenched by ethylene. The main primary products were cyclopentene (38.0mol%), 1-pentene (28.5), 1-butene+butadiene (19.0) and propylene (14.5). Minor ones were 1, 4-pentadiene and cyclopentadiene. A mechanism was proposed focussing the discussion on C5 products formation from allyl radical and ethylene.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"10 6 1","pages":"212-217"},"PeriodicalIF":0.0,"publicationDate":"1975-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76326446","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The oxidation of isobutene to methacrolein using U-Sb and Bi-Mo oxide catalysts were investigated and compared with that of propene to acrolein or butene-1 to butadiene.The oxidation of isobutene was found to be retarded by the reacting olefin. The retardation was decreased by an addition of steam in the reaction system. The added steam enhanced the formation of methacrolein and depressed that of carbon monoxide and dioxide. The retardation action of isobutene and the enhancement effect of steam were discussed from a viewpoint of the nature of adsorbed species.
{"title":"Oxidation of Isobutene to Methacrolein over U-Sb and Bi-Mo Oxide Catalysts","authors":"Y. Morita, M. Miyazaki, E. Kikuchi","doi":"10.1627/JPI1959.17.71","DOIUrl":"https://doi.org/10.1627/JPI1959.17.71","url":null,"abstract":"The oxidation of isobutene to methacrolein using U-Sb and Bi-Mo oxide catalysts were investigated and compared with that of propene to acrolein or butene-1 to butadiene.The oxidation of isobutene was found to be retarded by the reacting olefin. The retardation was decreased by an addition of steam in the reaction system. The added steam enhanced the formation of methacrolein and depressed that of carbon monoxide and dioxide. The retardation action of isobutene and the enhancement effect of steam were discussed from a viewpoint of the nature of adsorbed species.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"105 1","pages":"71-75"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79237892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The analyses of all C10 to C12 alkylnaphthalenes in nine crude oils were made by a combined chromatographic and spectrometric method.The di-aromatic fraction was isolated from the middle distillate (180∼300°C) of crude oil by liquid-solid chromatography, and analyzed by gas chromatography using a capillary column. The components inseparable by gas chromatography were determined by infrared spectrometry of the gas chromatographic effluent.The interference of alkylbenzothiophenes in the infrared spectrometry was avoided by removing them with liquid-liquid chromatography prior to the GC-IR analysis.The correction for alkylbenzothiophenes in the determination of some alkylnaphthalenes by capillary gas chromatography was made by using a sulfur selective flame photometric detector.The precision and accuracy of the method were both 5% relative.The compositions of C10 to C12 alkylnaphthalenes in nine crude oils were determined by this method and compared to each other. As a result, rules were found for the relative distribution of isomers. Furthermore, it was found that there was a marked difference in the relative distribution of isomers in high sulfur crude oils compared to low sulfur ones.
{"title":"Composition of C10 to C12 Alkylnaphthalenes in Various Crude Oils","authors":"Kyosuke Kasamatsu","doi":"10.1627/JPI1959.17.28","DOIUrl":"https://doi.org/10.1627/JPI1959.17.28","url":null,"abstract":"The analyses of all C10 to C12 alkylnaphthalenes in nine crude oils were made by a combined chromatographic and spectrometric method.The di-aromatic fraction was isolated from the middle distillate (180∼300°C) of crude oil by liquid-solid chromatography, and analyzed by gas chromatography using a capillary column. The components inseparable by gas chromatography were determined by infrared spectrometry of the gas chromatographic effluent.The interference of alkylbenzothiophenes in the infrared spectrometry was avoided by removing them with liquid-liquid chromatography prior to the GC-IR analysis.The correction for alkylbenzothiophenes in the determination of some alkylnaphthalenes by capillary gas chromatography was made by using a sulfur selective flame photometric detector.The precision and accuracy of the method were both 5% relative.The compositions of C10 to C12 alkylnaphthalenes in nine crude oils were determined by this method and compared to each other. As a result, rules were found for the relative distribution of isomers. Furthermore, it was found that there was a marked difference in the relative distribution of isomers in high sulfur crude oils compared to low sulfur ones.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"20 1","pages":"28-34"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78579020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new residual desulfurization process using a new type reactor and catalyst had been developed extending over 6 years as a part of the National Research and Development Program. We have taken over the development work comprising catalyst improvement and 500 BPSD test plant operations for vacuum residues and it is planning to construct a 10, 000 BPSD test plant.
{"title":"A New Residual Desulfurization Process","authors":"J. Kubo, Yutaka Oguchi, H. Nomura","doi":"10.1627/JPI1959.17.100","DOIUrl":"https://doi.org/10.1627/JPI1959.17.100","url":null,"abstract":"A new residual desulfurization process using a new type reactor and catalyst had been developed extending over 6 years as a part of the National Research and Development Program. We have taken over the development work comprising catalyst improvement and 500 BPSD test plant operations for vacuum residues and it is planning to construct a 10, 000 BPSD test plant.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"80 1","pages":"100-107"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77554302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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