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}
Steam-reforming of n-heptane on rhodium catalysts was investigated under atmospheric pressure and in the temperature range from 550 to 800°C. The degree of dispersion of supported rhodium was determined from hydrogen chemisorption data measured at 25°C by a pulse technique.Rhodium supported on silica was found to sinter considerably on reduction in hydrogen flow, and its activity also decreased. On the other hand, γ-alumina support was found to keep the dispersion of rhodium unchanged on reduction in the temperature range from 550 to 800°C.The activity per weight of a catalyst increased with the concentration of rhodium supported on γ-alumina. The activity was correlated with the amount of hydrogen uptake when more than 0.2% of rhodium was supported.The product composition from reactions at 600°C was compared with the equilibrium composition determined by the following two reactions: i) CH4+H2O=CO+3H2, and ii) CO+H2O=CO2+H2. The composition was found to deviate considerably from the equilibrium at earlier stages of the reaction, but to approach it with increasing conversion of n-heptane. It was suggested that the rate of these equilibrating reactions, especially of the reaction ii), was smaller than that of the initial decomposition of the feed hydrocarbon.
{"title":"Steam Reforming of Hydrocarbons on Noble Metal Catalysts (Part 2)","authors":"E. Kikuchi, Y. Yamazaki, Y. Morita","doi":"10.1627/JPI1959.17.3","DOIUrl":"https://doi.org/10.1627/JPI1959.17.3","url":null,"abstract":"Steam-reforming of n-heptane on rhodium catalysts was investigated under atmospheric pressure and in the temperature range from 550 to 800°C. The degree of dispersion of supported rhodium was determined from hydrogen chemisorption data measured at 25°C by a pulse technique.Rhodium supported on silica was found to sinter considerably on reduction in hydrogen flow, and its activity also decreased. On the other hand, γ-alumina support was found to keep the dispersion of rhodium unchanged on reduction in the temperature range from 550 to 800°C.The activity per weight of a catalyst increased with the concentration of rhodium supported on γ-alumina. The activity was correlated with the amount of hydrogen uptake when more than 0.2% of rhodium was supported.The product composition from reactions at 600°C was compared with the equilibrium composition determined by the following two reactions: i) CH4+H2O=CO+3H2, and ii) CO+H2O=CO2+H2. The composition was found to deviate considerably from the equilibrium at earlier stages of the reaction, but to approach it with increasing conversion of n-heptane. It was suggested that the rate of these equilibrating reactions, especially of the reaction ii), was smaller than that of the initial decomposition of the feed hydrocarbon.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"61 1","pages":"3-8"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84214441","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}
For the gelled JP-4 of an oil-in-water emulsion type which includes 96∼99% oil concentration by volume as an internal phase and has the drainage temperature higher than 70°C in confined vessel, the flame spreading aspects with a pool combustion were observed by taking movie, and the measurement of temperatures, on and above the surface of the gel from the time when the flame is coming over to the time when it has passed away, was carried out with thermocouples fixed in place.While the flame is spreading on the gelled JP-4, an advance liquid flow ahead of the flame can be found in case of the initial gel temperatures lower than the apparent flash points (26∼35°C) measured by means of open cup method. This liquid flow invades on to the surface of the virgin gel, issued from the upstream region covered already with luminous flame, and is not formed by radiative and conductive heat transfer from the flame pillar to the virgin gel surface. In view point that the temperatures of foregoing liquid flow is 10∼20°C at the initial level of gel surface and the flash point of the original JP-4 is -23°C, a large part of the low hydrocarbon fractions seem to have burned in the flame zone before streaming out on the virgin gel surface. The behavior of liquid flow was observed in detail with fine aluminum powders sowed in the vicinity of the ignition position. As the result, it is found that in the foregoing liquid flow there is a strong convection due to temperature gradient. Thus, the covering of the liquid flow on the virgin gel plays a role to reduce the drainage rate of the gel, protecting the gel surface from being exposed in air in the place close to hot flame, and the flame spreading velocity can be suppressed by one-tenth to one-twentieth, compared to that of the original JP-4.
{"title":"Flame Spreading on Gelled JP-4 Pool","authors":"H. Ishida, A. Iwama","doi":"10.1627/JPI1959.17.95","DOIUrl":"https://doi.org/10.1627/JPI1959.17.95","url":null,"abstract":"For the gelled JP-4 of an oil-in-water emulsion type which includes 96∼99% oil concentration by volume as an internal phase and has the drainage temperature higher than 70°C in confined vessel, the flame spreading aspects with a pool combustion were observed by taking movie, and the measurement of temperatures, on and above the surface of the gel from the time when the flame is coming over to the time when it has passed away, was carried out with thermocouples fixed in place.While the flame is spreading on the gelled JP-4, an advance liquid flow ahead of the flame can be found in case of the initial gel temperatures lower than the apparent flash points (26∼35°C) measured by means of open cup method. This liquid flow invades on to the surface of the virgin gel, issued from the upstream region covered already with luminous flame, and is not formed by radiative and conductive heat transfer from the flame pillar to the virgin gel surface. In view point that the temperatures of foregoing liquid flow is 10∼20°C at the initial level of gel surface and the flash point of the original JP-4 is -23°C, a large part of the low hydrocarbon fractions seem to have burned in the flame zone before streaming out on the virgin gel surface. The behavior of liquid flow was observed in detail with fine aluminum powders sowed in the vicinity of the ignition position. As the result, it is found that in the foregoing liquid flow there is a strong convection due to temperature gradient. Thus, the covering of the liquid flow on the virgin gel plays a role to reduce the drainage rate of the gel, protecting the gel surface from being exposed in air in the place close to hot flame, and the flame spreading velocity can be suppressed by one-tenth to one-twentieth, compared to that of the original JP-4.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"52 1","pages":"95-99"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84696178","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}
In order to develop a new method for removing the sulfur compounds in hydrocarbon oils, the extraction behavior of tetrahydrothiophene (THS) with an aqueous copper (II) bromide solution was investigated with special reference made to the mechanism of extraction and the factors which influence the extraction ability of copper complexes.Bromo-copper (II) complexes exhibited excellent extraction efficiency for THS that was more than 50 times as great as that of cupric ion itself. CuBr+, among the bromo complexes, was mainly concerned with the extraction of THS and it formed a white solid complex having a composition of [Cu(I)Br THS]. This solid complex was redissolved in the presence of excess amounts of Br- ion and/or CuBr2; and, thus, THS was extracted into the aqueous phase as water soluble complexes; i. e., copper (I) complex ions, [Cu(II)BrnTHS](n-1)- (n=2, 3) and/or mixed valance polynuclear complex ions, [Cu(II)-Brn-1-Cu(I)THS](2-n)+ (n=1, 2), respectively. The role of Br- ion as an auxiliary ligand was also discussed.
{"title":"Studies on the Removal and Recovery of Organic Sulfur Compounds in Hydrocarbon Oils by Liquid-Liquid Extraction (IV)","authors":"T. Yotsuyanagi, T. Kamidate, K. Aomura","doi":"10.1627/JPI1959.17.108","DOIUrl":"https://doi.org/10.1627/JPI1959.17.108","url":null,"abstract":"In order to develop a new method for removing the sulfur compounds in hydrocarbon oils, the extraction behavior of tetrahydrothiophene (THS) with an aqueous copper (II) bromide solution was investigated with special reference made to the mechanism of extraction and the factors which influence the extraction ability of copper complexes.Bromo-copper (II) complexes exhibited excellent extraction efficiency for THS that was more than 50 times as great as that of cupric ion itself. CuBr+, among the bromo complexes, was mainly concerned with the extraction of THS and it formed a white solid complex having a composition of [Cu(I)Br THS]. This solid complex was redissolved in the presence of excess amounts of Br- ion and/or CuBr2; and, thus, THS was extracted into the aqueous phase as water soluble complexes; i. e., copper (I) complex ions, [Cu(II)BrnTHS](n-1)- (n=2, 3) and/or mixed valance polynuclear complex ions, [Cu(II)-Brn-1-Cu(I)THS](2-n)+ (n=1, 2), respectively. The role of Br- ion as an auxiliary ligand was also discussed.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"604 1","pages":"108-113"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77424694","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. Amemiya, H. Miyake, A. Yokogawa, Mitsuyuki Mitooka, S. Mitsui, K. Ishibashi, J. Kawabata, Y. Tazaki
A process for preparing granular activated carbon has been developed, utilizing petroleum residues such as asphalt. Successful pilot plant operations have been made.The process consists of three steps. They are char production, char activation, and exhaust gas treating. Granular char, hard and uniform, has been produced by reacting asphalt with fuming sulfuric acid or elemental sulfur.A co-current, two-step fluidized bed furnace with unique features developed by the authors has been used for activating char above obtained.The product has indicated some excellent properties such as large specific surface area, extensive methylene blue adsorption, characteristic pore distribution, and high mechanical strength. Some practical applications have shown promising results.
{"title":"Granular Activated Carbon Produced from Asphalt","authors":"T. Amemiya, H. Miyake, A. Yokogawa, Mitsuyuki Mitooka, S. Mitsui, K. Ishibashi, J. Kawabata, Y. Tazaki","doi":"10.1627/JPI1959.17.143","DOIUrl":"https://doi.org/10.1627/JPI1959.17.143","url":null,"abstract":"A process for preparing granular activated carbon has been developed, utilizing petroleum residues such as asphalt. Successful pilot plant operations have been made.The process consists of three steps. They are char production, char activation, and exhaust gas treating. Granular char, hard and uniform, has been produced by reacting asphalt with fuming sulfuric acid or elemental sulfur.A co-current, two-step fluidized bed furnace with unique features developed by the authors has been used for activating char above obtained.The product has indicated some excellent properties such as large specific surface area, extensive methylene blue adsorption, characteristic pore distribution, and high mechanical strength. Some practical applications have shown promising results.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"28 1","pages":"143-149"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78851072","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 apparatus is proposed for measuring isobaric vapor-liquid equilibria of gas-solvent systems. It is based on the determination of vapor-liquid equilibria from boiling point measurements. The vapor composition in equilibrium with liquid solutions is calculated by using the method of Mixon et al. The experimental results are obtained for two binary systems, ammonia-water and propylene-acetone, at 760mmHg. In the ammonia-water system, the experimental data are in good agreement with those found in the literature.
{"title":"A New Apparatus for Measuring Vapor-Liquid Equilibria of Gas-Solvent Systems at Constant Pressure","authors":"Daisuke Hoshino, Kunio Nagahama, M. Hirata","doi":"10.1627/JPI1959.17.9","DOIUrl":"https://doi.org/10.1627/JPI1959.17.9","url":null,"abstract":"A new apparatus is proposed for measuring isobaric vapor-liquid equilibria of gas-solvent systems. It is based on the determination of vapor-liquid equilibria from boiling point measurements. The vapor composition in equilibrium with liquid solutions is calculated by using the method of Mixon et al. The experimental results are obtained for two binary systems, ammonia-water and propylene-acetone, at 760mmHg. In the ammonia-water system, the experimental data are in good agreement with those found in the literature.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"138 1","pages":"9-13"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79191595","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}
Isomerization of n-butenes was investigated over binary oxides ZnO-SiO2 having different mole ratios and the nature of active sites and the mechanism of the reaction were examined.On mixing of ZnO and SiO2, there appeared acidic sites and basic sites on the surface. The type of the acid sites was of Lewis acid which was determined by IR study of adsorbed pyridine.The isomerization was not retarded by acidic molecule of CO2 but by basic molecules such as pyridine and ammonia. The products formed over the deuterated catalyst contained a small amount of D atoms. The results of co-isomerization indicate that the reaction involves intramolecular hydrogen transfer and that the slow step is C-H bond cleavage. Therefore, it is concluded that the isomerization of butenes takes place on Lewis acid sites and is initiated by the abstraction of hydride ion which is the rate determining step.
{"title":"Isomerization of Butene over ZnO-SiO2","authors":"T. Sumiyoshi, K. Tanabe, H. Hattori","doi":"10.1627/JPI1959.17.65","DOIUrl":"https://doi.org/10.1627/JPI1959.17.65","url":null,"abstract":"Isomerization of n-butenes was investigated over binary oxides ZnO-SiO2 having different mole ratios and the nature of active sites and the mechanism of the reaction were examined.On mixing of ZnO and SiO2, there appeared acidic sites and basic sites on the surface. The type of the acid sites was of Lewis acid which was determined by IR study of adsorbed pyridine.The isomerization was not retarded by acidic molecule of CO2 but by basic molecules such as pyridine and ammonia. The products formed over the deuterated catalyst contained a small amount of D atoms. The results of co-isomerization indicate that the reaction involves intramolecular hydrogen transfer and that the slow step is C-H bond cleavage. Therefore, it is concluded that the isomerization of butenes takes place on Lewis acid sites and is initiated by the abstraction of hydride ion which is the rate determining step.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"42 1","pages":"65-70"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79967622","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 effect of mid-range volatility of motor gasoline on warm-up performance of modern Japanese cars was investigated in an all weather chassis dynamometer room, using six late model cars and twelve fuels of different volatility. The warm-up performance of cars and fuels was evaluated in terms of the time required to completely warm-up (warm-up time), the carknock disappearing time and the numerical driveability demerit rating. The warm-up performance was considerably different with different cars tested. Car with a rotary engine performed best. The warm-up performance correlated well with the 30% and 50% evaporated temperatures of a fuel. Also, the warm-up time was best correlated with 50% evaporated temperature, and the carknock disappearing time and driveability demerit were related best to 30% evaporated temperature.
{"title":"Effects of Gasoline Volatility on Warm-up of Automobiles","authors":"Hideo Yokoyama, E. Yoshida, K. Nakajima","doi":"10.1627/JPI1959.17.134","DOIUrl":"https://doi.org/10.1627/JPI1959.17.134","url":null,"abstract":"The effect of mid-range volatility of motor gasoline on warm-up performance of modern Japanese cars was investigated in an all weather chassis dynamometer room, using six late model cars and twelve fuels of different volatility. The warm-up performance of cars and fuels was evaluated in terms of the time required to completely warm-up (warm-up time), the carknock disappearing time and the numerical driveability demerit rating. The warm-up performance was considerably different with different cars tested. Car with a rotary engine performed best. The warm-up performance correlated well with the 30% and 50% evaporated temperatures of a fuel. Also, the warm-up time was best correlated with 50% evaporated temperature, and the carknock disappearing time and driveability demerit were related best to 30% evaporated temperature.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"8 1","pages":"134-142"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84443866","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}
For the purpose of analysing individual alkylnaphthalenes in petroleum middle distillates, an isolating method using liquid chromatography was investigated for simplicity and quantitative reliability. The alkylnaphthalenes could be isolated rapidly and quantitatively from saturates, mono-aromatics and sulfides by liquid solid chromatography using alumina of properly adjusted activity. In this chromatography, alkylbiphenyls and alkylbenzothiophenes showed the same behavior to alkylnaphthalenes.In order to separate alkylnaphthalenes from alkylbenzothiophenes a new liquid-liquid chromatographic technique was developed. Alumina or silica gel impregnated with a polar solvent had the ability to separate these compounds. Using basic alumina as the solid support and dimethylsulfoxide as the stationary liquid phase, naphthalene and benzothiophene were completely separated in preparative scale. Further, using a mixture of dimethylsulfoxide and dimethylformamide as the liquid phase, dimethylnaphthalenes in petroleum middle distillates were also successfully separated from analytically interfering C10 alkylbenzothiophenes.
{"title":"Isolation of Alkylnaphthalenes from the Middle Distillate of Petroleum by Liquid-Solid and Liquid-Liquid Chromatography","authors":"Kyosuke Kasamatsu","doi":"10.1627/JPI1959.17.21","DOIUrl":"https://doi.org/10.1627/JPI1959.17.21","url":null,"abstract":"For the purpose of analysing individual alkylnaphthalenes in petroleum middle distillates, an isolating method using liquid chromatography was investigated for simplicity and quantitative reliability. The alkylnaphthalenes could be isolated rapidly and quantitatively from saturates, mono-aromatics and sulfides by liquid solid chromatography using alumina of properly adjusted activity. In this chromatography, alkylbiphenyls and alkylbenzothiophenes showed the same behavior to alkylnaphthalenes.In order to separate alkylnaphthalenes from alkylbenzothiophenes a new liquid-liquid chromatographic technique was developed. Alumina or silica gel impregnated with a polar solvent had the ability to separate these compounds. Using basic alumina as the solid support and dimethylsulfoxide as the stationary liquid phase, naphthalene and benzothiophene were completely separated in preparative scale. Further, using a mixture of dimethylsulfoxide and dimethylformamide as the liquid phase, dimethylnaphthalenes in petroleum middle distillates were also successfully separated from analytically interfering C10 alkylbenzothiophenes.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"93 11 1","pages":"21-27"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83456796","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}
Masato Tanaka, Yoshihisa Watanabe, T. Mitsudo, Y. Takegami
The carbonylation reaction of ethyl vinyl ether with various cobalt hydrocarbonyls, HCo(CO)4, HCo(CO)3PR3, HCo(CO)3P(OR)3, and HCo(CO)2[P(OR)3]2 was studied. Almost all of the cobalt hydrocarbonyls react with ethyl vinyl ether to form the branched chain acyl complexes, CH3CH(OC2H5)COCo(CO)4-nLn (L; CO, PR3 and P(OR)3), regardless of the character of the ligands at 0∼25°C, while HCo(CO)2[P(OEt)3]2 does not react even at 65°C. The order of the reactivities is parallel to that of the electron-accepting character of the ligand. The addition of an excess of the ligand retards the reaction. The activation parameters of the reaction of HCo(CO)3PPh3 with ethyl vinyl ether were estimated to be ΔH≠=9.88kcal/mol, ΔS≠=-41.0e.u.
{"title":"The Reaction of Cobalt Hydrocarbonyls Substituted by Tertiary Phosphines with an Olefin","authors":"Masato Tanaka, Yoshihisa Watanabe, T. Mitsudo, Y. Takegami","doi":"10.1627/JPI1959.17.83","DOIUrl":"https://doi.org/10.1627/JPI1959.17.83","url":null,"abstract":"The carbonylation reaction of ethyl vinyl ether with various cobalt hydrocarbonyls, HCo(CO)4, HCo(CO)3PR3, HCo(CO)3P(OR)3, and HCo(CO)2[P(OR)3]2 was studied. Almost all of the cobalt hydrocarbonyls react with ethyl vinyl ether to form the branched chain acyl complexes, CH3CH(OC2H5)COCo(CO)4-nLn (L; CO, PR3 and P(OR)3), regardless of the character of the ligands at 0∼25°C, while HCo(CO)2[P(OEt)3]2 does not react even at 65°C. The order of the reactivities is parallel to that of the electron-accepting character of the ligand. The addition of an excess of the ligand retards the reaction. The activation parameters of the reaction of HCo(CO)3PPh3 with ethyl vinyl ether were estimated to be ΔH≠=9.88kcal/mol, ΔS≠=-41.0e.u.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"12 1","pages":"83-87"},"PeriodicalIF":0.0,"publicationDate":"1975-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81669294","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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