For hydrocarbon synthesis from mixtures of CO and H2, variation in activity and selectivity of Group VIII metals (except osmium)/Al2O3 catalysts with pretreatment temperature in flpwing H2 at 300°C∼800°C, was investigated at 300°C and 1atm using a pulse method and a circulating flow reactor. In addition, variation in the number of surface metal atoms (mS) in those catalysts with varying treatment temperature was also determined using the chemisorption technique. The activities (per unit weight of catalyst; per metal atom in the catalyst) of Pt, Ir, Pd, and Rh catalysts were maximum when they were treated at 500°C, though their mS values monotonously decreased with increasing treatment temperature due to metal sintering. The activity and the mS value of Ru(A) catalyst decreased slightly with increasing treatment temperature. On the other hand, the initial activity and the mS value of Ru(B) increased with increasing treatment temperature, but the steady-state activity decreased. The activities and mS values of Ni and Co increased with increasing treatment temperature. Fe neither adsorbed hydrogen nor showed any activity. The sequence of specific activity (per surface metal atom) was determined as follows: Ru(B), Ru(A)>Ni>Co>Rh>Pd, Pt>IrThe main reaction product was methane, but the hydrocarbon distribution of products varied over a wide range depending more on metal than on treatment temperature. The average molecular weight of product hydrocarbons changed in the following sequence: Ru(B)>Ir>Rh>Ru(A), Ni, Co>Pt>Pd.
{"title":"The Activity, Selectivity and Thermal Stability of Group VIII Metal/Al2O3Catalysts for Synthesis of Hydrocarbons from CO and H2","authors":"M. Saito, T. Sakabe","doi":"10.1627/JPI1959.19.140","DOIUrl":"https://doi.org/10.1627/JPI1959.19.140","url":null,"abstract":"For hydrocarbon synthesis from mixtures of CO and H2, variation in activity and selectivity of Group VIII metals (except osmium)/Al2O3 catalysts with pretreatment temperature in flpwing H2 at 300°C∼800°C, was investigated at 300°C and 1atm using a pulse method and a circulating flow reactor. In addition, variation in the number of surface metal atoms (mS) in those catalysts with varying treatment temperature was also determined using the chemisorption technique. The activities (per unit weight of catalyst; per metal atom in the catalyst) of Pt, Ir, Pd, and Rh catalysts were maximum when they were treated at 500°C, though their mS values monotonously decreased with increasing treatment temperature due to metal sintering. The activity and the mS value of Ru(A) catalyst decreased slightly with increasing treatment temperature. On the other hand, the initial activity and the mS value of Ru(B) increased with increasing treatment temperature, but the steady-state activity decreased. The activities and mS values of Ni and Co increased with increasing treatment temperature. Fe neither adsorbed hydrogen nor showed any activity. The sequence of specific activity (per surface metal atom) was determined as follows: Ru(B), Ru(A)>Ni>Co>Rh>Pd, Pt>IrThe main reaction product was methane, but the hydrocarbon distribution of products varied over a wide range depending more on metal than on treatment temperature. The average molecular weight of product hydrocarbons changed in the following sequence: Ru(B)>Ir>Rh>Ru(A), Ni, Co>Pt>Pd.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88857714","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}
Steam reforming of methane, n-pentane and n-heptane over Rh catalysts supported on γ-alumina and silica has been carried out under atmospheric pressure and at 550°C to investigate the influence of the degree of dispersion of Rh on steam reforming and aromatization. The specific catalytic activity expressed by the initial rate of reaction per unit surface area of Rh was found to depend on the degree of dispersion. A good correlation was obtained between the gasification activity and the appearance of surface atoms existing in crystal faces and between the aromatization activity and the appearance of surface atoms existing in low-coordinated positions such as edge or corner atoms. The difference in the active sites on Rh crystal for gasification and aromatization was further confirmed by the study using a pulse technique.
{"title":"Steam Reforming of Hydrocarbons on Noble Metal Catalysts (Part 5)","authors":"E. Kikuchi, Kiichi Ito, Y. Morita","doi":"10.1627/JPI1959.19.135","DOIUrl":"https://doi.org/10.1627/JPI1959.19.135","url":null,"abstract":"Steam reforming of methane, n-pentane and n-heptane over Rh catalysts supported on γ-alumina and silica has been carried out under atmospheric pressure and at 550°C to investigate the influence of the degree of dispersion of Rh on steam reforming and aromatization. The specific catalytic activity expressed by the initial rate of reaction per unit surface area of Rh was found to depend on the degree of dispersion. A good correlation was obtained between the gasification activity and the appearance of surface atoms existing in crystal faces and between the aromatization activity and the appearance of surface atoms existing in low-coordinated positions such as edge or corner atoms. The difference in the active sites on Rh crystal for gasification and aromatization was further confirmed by the study using a pulse technique.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76694924","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}
Athabasca bitumen was sudjected to thermal cracking at temperatures of 430-520°C in the presence of hydrogen at 50atm. A significant decrease in viscosity and that in the average molecular weight of the bitumen were attained without excessive coke formation. The reaction mechanism was discussed based on the detailed structural analyses of the bitumen and the oil cracked by visbreaking by use of the various methods including GPC, NMR, and elemental analysis.
{"title":"Hydrovisbreaking of Athabasca Bitumen and its Reaction Mechanism","authors":"H. Tominaga, Seiji Itoh, M. Yashiro","doi":"10.1627/JPI1959.19.50","DOIUrl":"https://doi.org/10.1627/JPI1959.19.50","url":null,"abstract":"Athabasca bitumen was sudjected to thermal cracking at temperatures of 430-520°C in the presence of hydrogen at 50atm. A significant decrease in viscosity and that in the average molecular weight of the bitumen were attained without excessive coke formation. The reaction mechanism was discussed based on the detailed structural analyses of the bitumen and the oil cracked by visbreaking by use of the various methods including GPC, NMR, and elemental analysis.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72749153","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}
Matsui Yasushi, Hiroaki Taniguchi, K. Terada, M. Iriuchijima
Chemical changes of phosphorous ligands in the rhodium complex catalyst system were studied using 31P NMR analysis. Triphenyl phosphite was readily oxidized by the small amount of oxygen contained in the synthesis gas to triphenyl phosphate in the course of hydroformylation. It is conceivable that this oxidation reaction is the cause of deactivation of the catalyst. The treatment of the synthesis gas with triisobutyl aluminum in toluene solution was effective in preventing the oxidation of triphenyl phosphite to triphenyl phosphate and in prolonging the activity of the catalyst for a long period.A 191-hr cotinuous run was made to establish catalyst activity, and 3, 220g of aldehyde was obtained using only 6.5mg of rhodium.
{"title":"Hydroformylation of Olefins Using Rhodium Complex Catalysts (Part 2)","authors":"Matsui Yasushi, Hiroaki Taniguchi, K. Terada, M. Iriuchijima","doi":"10.1627/JPI1959.19.68","DOIUrl":"https://doi.org/10.1627/JPI1959.19.68","url":null,"abstract":"Chemical changes of phosphorous ligands in the rhodium complex catalyst system were studied using 31P NMR analysis. Triphenyl phosphite was readily oxidized by the small amount of oxygen contained in the synthesis gas to triphenyl phosphate in the course of hydroformylation. It is conceivable that this oxidation reaction is the cause of deactivation of the catalyst. The treatment of the synthesis gas with triisobutyl aluminum in toluene solution was effective in preventing the oxidation of triphenyl phosphite to triphenyl phosphate and in prolonging the activity of the catalyst for a long period.A 191-hr cotinuous run was made to establish catalyst activity, and 3, 220g of aldehyde was obtained using only 6.5mg of rhodium.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79124334","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}
Daisuke Hoshino, Yoshiki Unno, Kunio Nagahama, M. Hirata
{"title":"Prediction of Vapor-Liquid Equilibria and Solid-Liquid Equilibria by the Analytical Solutions of Groups Model","authors":"Daisuke Hoshino, Yoshiki Unno, Kunio Nagahama, M. Hirata","doi":"10.1627/JPI1959.19.56","DOIUrl":"https://doi.org/10.1627/JPI1959.19.56","url":null,"abstract":"","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83485498","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 co-oxidation of model compounds of aromatic hydrocarbon with squalane was carried out to investigate the effect of aromatic hydrocarbons on the oxidation stability of squalane. The kinetic parameters for the co-oxidation of some combinations with squalane were determined. The reactivity of squalane peroxy radical is nearly the same as that of cumyl peroxy radical, whereas the estimated value of 2kt for squalane peroxy radical is considerably larger than that for simple tertiary peroxy radicals. From this result, it should be considered that so-called "Optimum Aromaticity" could never occur in the co-oxidation with squalane. Actually, the effect of "Optimum Aromaticity" does not occur at all in the present work as expected.
{"title":"The Effect of Aromatic Hydrocarbons on the Oxidation Stability of Squalane (Part 2)","authors":"S. Yasutomi, T. Sakurai","doi":"10.1627/JPI1959.19.21","DOIUrl":"https://doi.org/10.1627/JPI1959.19.21","url":null,"abstract":"The co-oxidation of model compounds of aromatic hydrocarbon with squalane was carried out to investigate the effect of aromatic hydrocarbons on the oxidation stability of squalane. The kinetic parameters for the co-oxidation of some combinations with squalane were determined. The reactivity of squalane peroxy radical is nearly the same as that of cumyl peroxy radical, whereas the estimated value of 2kt for squalane peroxy radical is considerably larger than that for simple tertiary peroxy radicals. From this result, it should be considered that so-called \"Optimum Aromaticity\" could never occur in the co-oxidation with squalane. Actually, the effect of \"Optimum Aromaticity\" does not occur at all in the present work as expected.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90494059","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}
Matsui Yasushi, Hiroaki Taniguchi, K. Terada, Tetsuo Anezaki, M. Iriuchijima
A new catalyst system is described for producing normal aldekydes predominantly from α-olefins. The catalyst consists of a rhodium compound, triphenyl phosphite and sodium acetate. Effects of various reaction parameters on the ratio of n- to iso-aldehyde are reported. Sodium acetate has been found to be highly selective production of normal isomer and for maintaining the activity of the catalyst for a long period of time.The rate of aldehyde formation depends on the concentration of rhodium as follows:d[aldehyde]/dt∝[Rh]1.0 (at initial state) d[aldehyde]/dt∝[Rh]0.7 (at stationary state)However, the concentration of rhodium has little effect on the n/i ratio.
{"title":"Hydroformylation of Olefins Using Rhodium Complex Catalysts (Part 1)","authors":"Matsui Yasushi, Hiroaki Taniguchi, K. Terada, Tetsuo Anezaki, M. Iriuchijima","doi":"10.1627/JPI1959.19.62","DOIUrl":"https://doi.org/10.1627/JPI1959.19.62","url":null,"abstract":"A new catalyst system is described for producing normal aldekydes predominantly from α-olefins. The catalyst consists of a rhodium compound, triphenyl phosphite and sodium acetate. Effects of various reaction parameters on the ratio of n- to iso-aldehyde are reported. Sodium acetate has been found to be highly selective production of normal isomer and for maintaining the activity of the catalyst for a long period of time.The rate of aldehyde formation depends on the concentration of rhodium as follows:d[aldehyde]/dt∝[Rh]1.0 (at initial state) d[aldehyde]/dt∝[Rh]0.7 (at stationary state)However, the concentration of rhodium has little effect on the n/i ratio.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87512139","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}
T. Kimura, Nobuhiko Nakabayashi, Hiroaki Kubota, E. Kikuchi, Y. Morita
The reaction between steam and carbon deposited on potassium polyaluminate-(β"-Al2O3) from various hydrocarbons was studied in tubular flow reactor with a fixed catalyst bed at elevated temperatures.Carbon deposition fiom n-hexane took place above 600°C, while that from benzene required temperatures higher than 700°C. The reaction between steam and carbon deposited from both n-hexane and benzene, however, proceeded above 600°C. The lowest temperature required for steam reforming on β"-Al2O3 catalyst was decisively dependent on the ease of cracking of feed hydrocarbon to form carbon deposits.The reactivity of carbon with steam deposited from polyaromatic hydrocarbons was almost the same as that from benzene. On the other hand, carbon deposited from n-hexane or ethylene was somewhat less reactive than that from aromatics.By comparing the reaction between steam and several carbon species with different degree of graphitization in the presence of β"-Al2O3, it was shown that intermediate carbon deposited on β"-Al2O3 during steam reforming was as reactive as amorphous charcoal.
{"title":"Steam Reforming of Hydrocarbons on Alkali Polyaluminate Catalysts (Part. 2)","authors":"T. Kimura, Nobuhiko Nakabayashi, Hiroaki Kubota, E. Kikuchi, Y. Morita","doi":"10.1627/JPI1959.19.46","DOIUrl":"https://doi.org/10.1627/JPI1959.19.46","url":null,"abstract":"The reaction between steam and carbon deposited on potassium polyaluminate-(β\"-Al2O3) from various hydrocarbons was studied in tubular flow reactor with a fixed catalyst bed at elevated temperatures.Carbon deposition fiom n-hexane took place above 600°C, while that from benzene required temperatures higher than 700°C. The reaction between steam and carbon deposited from both n-hexane and benzene, however, proceeded above 600°C. The lowest temperature required for steam reforming on β\"-Al2O3 catalyst was decisively dependent on the ease of cracking of feed hydrocarbon to form carbon deposits.The reactivity of carbon with steam deposited from polyaromatic hydrocarbons was almost the same as that from benzene. On the other hand, carbon deposited from n-hexane or ethylene was somewhat less reactive than that from aromatics.By comparing the reaction between steam and several carbon species with different degree of graphitization in the presence of β\"-Al2O3, it was shown that intermediate carbon deposited on β\"-Al2O3 during steam reforming was as reactive as amorphous charcoal.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83611341","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 share of imported LPG in the total energy consumption in Japan has been increasingly encouraged by the future possibilities of larger volume consumption-as in the case of LNG-for power generation and other industrial uses. LPG is a liquefied gas similar to LNG in many aspects but differing markedly in composition, which consists of C3 and C4 fractions, and in cost factors. Since the operating temperature of LPG under atmospheric pressure is not lower than -40°C as opposed to about -160°C for LNG, operating and material costs, in turn the construction costs, particularly, of tanks and tankers, will be substantially less. This paper introduces a practical cost estimation method together with an example of conceptual planning of an LPG project based on experimental data and experience.
{"title":"A Consideration of Approximate C. I. F. Cost of Imported LPG","authors":"S. Hirakawa, S. Tanimizu","doi":"10.1627/JPI1959.19.86","DOIUrl":"https://doi.org/10.1627/JPI1959.19.86","url":null,"abstract":"The share of imported LPG in the total energy consumption in Japan has been increasingly encouraged by the future possibilities of larger volume consumption-as in the case of LNG-for power generation and other industrial uses. LPG is a liquefied gas similar to LNG in many aspects but differing markedly in composition, which consists of C3 and C4 fractions, and in cost factors. Since the operating temperature of LPG under atmospheric pressure is not lower than -40°C as opposed to about -160°C for LNG, operating and material costs, in turn the construction costs, particularly, of tanks and tankers, will be substantially less. This paper introduces a practical cost estimation method together with an example of conceptual planning of an LPG project based on experimental data and experience.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82316429","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 catalysis of phosphonium and sulfonium compounds possessing various kinds of counteranions was investigated in the low-temperature homogeneous liquid-phase oxidation of nonpolar tetralin and polar benzaldehyde with particular reference to the initial oxidation mechanism. The detailed approach to the initiation mechanism on the basis of UV spectroscopic measurements of the interaction between the onium catalyst and O2, molecular orbital calculations of onium catalysts, the simulation analysis of the mechanism, and so on led to a conclusion that the partially electron-occupied d-orbitals of phosphorus or sulfur atom in the onium catalyst is favorably deposited for the interaction of O2 so as to activate the latter through the charge transfer from the catalyst to O2. The activated O2 substantially decreased the activation barrier for the abstraction of the active hydrogen of the hydrocarbons.
{"title":"Distinctive Catalysis of Phosphonium and Sulfonium Compounds in Low-temperature Liquid-phase Hydrocarbon Oxidation","authors":"K. Ohkubo, K. Yoshinaga","doi":"10.1627/JPI1959.19.73","DOIUrl":"https://doi.org/10.1627/JPI1959.19.73","url":null,"abstract":"The oxidation catalysis of phosphonium and sulfonium compounds possessing various kinds of counteranions was investigated in the low-temperature homogeneous liquid-phase oxidation of nonpolar tetralin and polar benzaldehyde with particular reference to the initial oxidation mechanism. The detailed approach to the initiation mechanism on the basis of UV spectroscopic measurements of the interaction between the onium catalyst and O2, molecular orbital calculations of onium catalysts, the simulation analysis of the mechanism, and so on led to a conclusion that the partially electron-occupied d-orbitals of phosphorus or sulfur atom in the onium catalyst is favorably deposited for the interaction of O2 so as to activate the latter through the charge transfer from the catalyst to O2. The activated O2 substantially decreased the activation barrier for the abstraction of the active hydrogen of the hydrocarbons.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88894854","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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