{"title":"Isomerization of Pentanes on Platinum/Rare Earths-Hydrogen-Zeolite Y Catalysts","authors":"M. Saito, Takahisa Iwasaki","doi":"10.1627/JPI1959.18.117","DOIUrl":"https://doi.org/10.1627/JPI1959.18.117","url":null,"abstract":"","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85816439","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}
Hideyuki Suzuki, T. Hasegawa, C. Horie, O. Takahashi, T. Sakai, T. Iizuka, K. Arata, H. Hattori, K. Tanabe, S. Okazaki
Alumina FE (fibrous powder containing no sodium) and alumina FF (fibrous fine particles with small bulk density) were synthesized, and their surfaces and catalytic properties were studied. Both fibrillar aluminas were found to have high acid strengths and large amounts of oxidizing and reducing sites compared with gibbsite aluminas.For the isomerization of 1-butene, only Al2O3 FF showed no decrease in activity, and the selectivity (the ratio of cis-2-butene to trans-2-butene) was 1.6. In the reaction of propylene oxide, Al2O3 FE produced a larger amount of propion aldehyde compared with a gibbsite. On the other hand, Al2O3 FE predominantly formed ketone in the reaction of 1-methylcyclohexene oxide, while Al2O3 FF formed allyl alcohol predominantly. For the alkylation of phenol with methanol, Al2O3 FF was more active than Al2O3 FE, and it formed a larger amount of anisole than an activated alumina. For the hydrocracking of thiophene, MoO3 CoO mounted on a fibrillar Al2O3 was much more active than the same catalyst mounted on Al2O3 prepared by homogeneous precipitation.
{"title":"Surface Properties and Catalytic Activity of Fibrillar Aluminas","authors":"Hideyuki Suzuki, T. Hasegawa, C. Horie, O. Takahashi, T. Sakai, T. Iizuka, K. Arata, H. Hattori, K. Tanabe, S. Okazaki","doi":"10.1627/JPI1959.18.178","DOIUrl":"https://doi.org/10.1627/JPI1959.18.178","url":null,"abstract":"Alumina FE (fibrous powder containing no sodium) and alumina FF (fibrous fine particles with small bulk density) were synthesized, and their surfaces and catalytic properties were studied. Both fibrillar aluminas were found to have high acid strengths and large amounts of oxidizing and reducing sites compared with gibbsite aluminas.For the isomerization of 1-butene, only Al2O3 FF showed no decrease in activity, and the selectivity (the ratio of cis-2-butene to trans-2-butene) was 1.6. In the reaction of propylene oxide, Al2O3 FE produced a larger amount of propion aldehyde compared with a gibbsite. On the other hand, Al2O3 FE predominantly formed ketone in the reaction of 1-methylcyclohexene oxide, while Al2O3 FF formed allyl alcohol predominantly. For the alkylation of phenol with methanol, Al2O3 FF was more active than Al2O3 FE, and it formed a larger amount of anisole than an activated alumina. For the hydrocracking of thiophene, MoO3 CoO mounted on a fibrillar Al2O3 was much more active than the same catalyst mounted on Al2O3 prepared by homogeneous precipitation.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91360383","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}
This paper describes the kinetic treatment of oxidation of squalane at 60∼120°C.Di-tert-butyl peroxide (DTBP) and 2, 2'-azobisisobutyronitrile (AIBN) were used as initiators and chlorobenzene was used as an inert solvent.The values of kp/(2kt)1/2 in the neat phase are slightly less than those in chlorobenzene solution for a given initiator concentration and temperature. This retardation can be attributed to the solvent effect of chlorobenzene on the decomposition rate of DTBP, since the correction of the solvent effect eliminates the decrease in kp/(2kt)1/2. The values of first-order term "aRi" were calculated from the data, and the values of "a" were found to be 0.77 and 0.65 at 60 and 95°C, respectively, instead of 0.50, which was predicted by simple oxidation scheme.The kinetic order with respect to the initiation rate is 0.57 at 95°C instead of the theoretical value of 0.50 both in the neat phase and in chlorobenzene solution.The values of activation energy (Ep-Et/2) are obtained as 11.6kcal/mole and 14.3kcal/mole in chlorobenzene solution and in the neat phase, respectively, on the assumption that the decomposition rate of DTBP in the neat phase is the same as that in chlorobenzene solution. The correction of the solvent effect also eliminates the difference in both values.The solvent effect on the decomposition rate of DTBP plays an important role especially in the initiated oxidation of aliphatic hydrocarbons.
{"title":"The Effect of Aromatic Hydrocarbons on the Oxidation Stability of Squalane (Part 1)","authors":"S. Yasutomi, T. Sakurai","doi":"10.1627/JPI1959.18.107","DOIUrl":"https://doi.org/10.1627/JPI1959.18.107","url":null,"abstract":"This paper describes the kinetic treatment of oxidation of squalane at 60∼120°C.Di-tert-butyl peroxide (DTBP) and 2, 2'-azobisisobutyronitrile (AIBN) were used as initiators and chlorobenzene was used as an inert solvent.The values of kp/(2kt)1/2 in the neat phase are slightly less than those in chlorobenzene solution for a given initiator concentration and temperature. This retardation can be attributed to the solvent effect of chlorobenzene on the decomposition rate of DTBP, since the correction of the solvent effect eliminates the decrease in kp/(2kt)1/2. The values of first-order term \"aRi\" were calculated from the data, and the values of \"a\" were found to be 0.77 and 0.65 at 60 and 95°C, respectively, instead of 0.50, which was predicted by simple oxidation scheme.The kinetic order with respect to the initiation rate is 0.57 at 95°C instead of the theoretical value of 0.50 both in the neat phase and in chlorobenzene solution.The values of activation energy (Ep-Et/2) are obtained as 11.6kcal/mole and 14.3kcal/mole in chlorobenzene solution and in the neat phase, respectively, on the assumption that the decomposition rate of DTBP in the neat phase is the same as that in chlorobenzene solution. The correction of the solvent effect also eliminates the difference in both values.The solvent effect on the decomposition rate of DTBP plays an important role especially in the initiated oxidation of aliphatic hydrocarbons.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90740446","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. Hisamitsu, Yasuo Shite, F. Maruyama, Mamoru Yamane, Yoshihito Satomi, H. Ozaki
Two different kinds of vacuum gas oils have been hydrodesulfurized and hydrogen consumption has been measured by means of three procedures. It has been proposed that the convenient procedure based on the measurements of the changes in aromatic carbon content in the oil by n-d-M analysis is sufficiently applicable to the measurements of hydrogen consumption.Reaction kinetics has also been studied, and the apparent reaction order has been found to vary with change in the reaction temperature.
{"title":"Studies on Hydrodesulfurization of Heavy Distillates","authors":"T. Hisamitsu, Yasuo Shite, F. Maruyama, Mamoru Yamane, Yoshihito Satomi, H. Ozaki","doi":"10.1627/JPI1959.18.146","DOIUrl":"https://doi.org/10.1627/JPI1959.18.146","url":null,"abstract":"Two different kinds of vacuum gas oils have been hydrodesulfurized and hydrogen consumption has been measured by means of three procedures. It has been proposed that the convenient procedure based on the measurements of the changes in aromatic carbon content in the oil by n-d-M analysis is sufficiently applicable to the measurements of hydrogen consumption.Reaction kinetics has also been studied, and the apparent reaction order has been found to vary with change in the reaction temperature.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79714506","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}
effect of addition of metal oxides to MoO3-Al2O3 as well as the solvent effect of paraffin, aromatics, and naphthenics. By the addition of Cs2O and Tl2O to MoO3-Al2O3 catalyst, the selectivity for disproportionation of olefins increased, showing a tendency similar to that in the gas phase disproportionation reactions. In the presence of linear hydrocarbon solvents, the catalyst life was remarkably enhanced. This tendency was especially intensified in the presence of n-heptane. Disproportionation of propylene in the presence of aromatic or naphthenic hydrocarbons could not be continued for a long time because of the flow resistance in the reactor. In the case of aromatic solvents, large quantities of alkylbenzenes were produced. Infrared spectra of the polymers produced in the presence of various solvents showed absorption bands due to the carbonyl groups. These absorption bands may have resulted from the oxidation of the polymers by the oxygen of the MoO3-Al2O3 catalyst. It is concluded that the reactions in the presence of linear hydrocarbon solvents are prevented from extensive formation of polymers with higher molecular weights.
{"title":"Effects of Solvents and Addition of Metal Oxides on the Liquid Phase Disproportionation of Olefins over MoO3-Al2O3 Catalyst","authors":"T. Sodesawa, E. Ogata, Y. Kamiya","doi":"10.1627/JPI1959.18.162","DOIUrl":"https://doi.org/10.1627/JPI1959.18.162","url":null,"abstract":"effect of addition of metal oxides to MoO3-Al2O3 as well as the solvent effect of paraffin, aromatics, and naphthenics. By the addition of Cs2O and Tl2O to MoO3-Al2O3 catalyst, the selectivity for disproportionation of olefins increased, showing a tendency similar to that in the gas phase disproportionation reactions. In the presence of linear hydrocarbon solvents, the catalyst life was remarkably enhanced. This tendency was especially intensified in the presence of n-heptane. Disproportionation of propylene in the presence of aromatic or naphthenic hydrocarbons could not be continued for a long time because of the flow resistance in the reactor. In the case of aromatic solvents, large quantities of alkylbenzenes were produced. Infrared spectra of the polymers produced in the presence of various solvents showed absorption bands due to the carbonyl groups. These absorption bands may have resulted from the oxidation of the polymers by the oxygen of the MoO3-Al2O3 catalyst. It is concluded that the reactions in the presence of linear hydrocarbon solvents are prevented from extensive formation of polymers with higher molecular weights.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80460806","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}
tert-Butylation of aromatic hydrocarbons with tert-butyl chloride in the presence of AlCl3-tert-butylanisole was investigated. Neither isomerization of the products nor transalkylation of the substrate with the products was observed when the molar ratio of tert-butylanisole to AlCl3 was more than two. Competitive tert-butylation of benzene and toluene showed higher substrate selectivity (kT/kB=21-24). A role of trans-tert-butylation in the tert-butylation was suggested from the results of tert-butylation of toluene in the presence of 2, 4- and 2, 5-dimethylanisole.
{"title":"tert-Butylation of Aromatic Hydrocarbons with AlCl3-tert-Butylanisole Catalyst","authors":"K. Shimada","doi":"10.1627/JPI1959.18.158","DOIUrl":"https://doi.org/10.1627/JPI1959.18.158","url":null,"abstract":"tert-Butylation of aromatic hydrocarbons with tert-butyl chloride in the presence of AlCl3-tert-butylanisole was investigated. Neither isomerization of the products nor transalkylation of the substrate with the products was observed when the molar ratio of tert-butylanisole to AlCl3 was more than two. Competitive tert-butylation of benzene and toluene showed higher substrate selectivity (kT/kB=21-24). A role of trans-tert-butylation in the tert-butylation was suggested from the results of tert-butylation of toluene in the presence of 2, 4- and 2, 5-dimethylanisole.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77150645","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. Matsuda, Jinichi Ogawa, H. Kawashima, Motomu Ojima
A new catalytic hydroboration of olefins in the gas phase has been proposed. The kinetics of the reaction of diborane with ethylene or propylene in the presence of a Pd-carbon catalyst was investigated at 30°C to 50°C The initial rate of the reaction, ri, was expressed by ri=kp1/2BPO, where PB and PO denote the initial partial pressures of diborane and ethylene or propylene, respectively, and k the rate constant. The activation energy was 6 and 1.5kcal/mol for ethylene and propylene, respectively. These activation energies were much smaller than those for noncatalytic hydroboration found in literature. The reaction mechanism was interpreted in terms of the rate-determining step which is the attack of the olefin on the dissociated diborane on the catalyst. The reaction mechanism was further confirmed by the adsorptions of diborane, ethylene and propylene.
{"title":"Catalytic Hydroboration in Gas Phase","authors":"T. Matsuda, Jinichi Ogawa, H. Kawashima, Motomu Ojima","doi":"10.1627/JPI1959.18.67","DOIUrl":"https://doi.org/10.1627/JPI1959.18.67","url":null,"abstract":"A new catalytic hydroboration of olefins in the gas phase has been proposed. The kinetics of the reaction of diborane with ethylene or propylene in the presence of a Pd-carbon catalyst was investigated at 30°C to 50°C The initial rate of the reaction, ri, was expressed by ri=kp1/2BPO, where PB and PO denote the initial partial pressures of diborane and ethylene or propylene, respectively, and k the rate constant. The activation energy was 6 and 1.5kcal/mol for ethylene and propylene, respectively. These activation energies were much smaller than those for noncatalytic hydroboration found in literature. The reaction mechanism was interpreted in terms of the rate-determining step which is the attack of the olefin on the dissociated diborane on the catalyst. The reaction mechanism was further confirmed by the adsorptions of diborane, ethylene and propylene.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76839095","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. Kunugita, Hiroaki Yasuoka, E. Nakanishi, T. Otake
In dehydrogenation of n-butane over alumina-chromia catalyst, a decrease in reaction rate with increase in time of reaction process is due mainly to the catalyst fouling caused by the accumulation of coke on the catalyst pellets. Such cyclic operation in which a catalytic reaction and catalyst regeneration are performed alternately is necessary from economic onsiderations. It. is deduced from the experimental result that in a complete mixed type reactor the rate of coke formation is proportional to the mole fraction of n-butene in the reactor, and the time required for complete generation of the fouled catalyst is proportional to the total amount of n-butene produced. The objective functions are expressed in terms of the amount of n-butene produced, the time of reaction, and the time required for complete regeneration. Criteria for predicting the optimum switching time are associated with maximizing the average production rate of n-butene, minimizing the direct production costs per mole of n-butene, and maximizing the gross profit in one cyclic operation. By expressing the desired substance in the reactor effluent in terms of its mole fraction, these criteria have the advantage in that the optimum switching time can be determined not by the activity of the catalyst, but by the mole fraction of n-butene in the effluent.
{"title":"Optimum Cycle for a Catalytic Dehydrogenation-Regeneration Process","authors":"E. Kunugita, Hiroaki Yasuoka, E. Nakanishi, T. Otake","doi":"10.1627/JPI1959.18.73","DOIUrl":"https://doi.org/10.1627/JPI1959.18.73","url":null,"abstract":"In dehydrogenation of n-butane over alumina-chromia catalyst, a decrease in reaction rate with increase in time of reaction process is due mainly to the catalyst fouling caused by the accumulation of coke on the catalyst pellets. Such cyclic operation in which a catalytic reaction and catalyst regeneration are performed alternately is necessary from economic onsiderations. It. is deduced from the experimental result that in a complete mixed type reactor the rate of coke formation is proportional to the mole fraction of n-butene in the reactor, and the time required for complete generation of the fouled catalyst is proportional to the total amount of n-butene produced. The objective functions are expressed in terms of the amount of n-butene produced, the time of reaction, and the time required for complete regeneration. Criteria for predicting the optimum switching time are associated with maximizing the average production rate of n-butene, minimizing the direct production costs per mole of n-butene, and maximizing the gross profit in one cyclic operation. By expressing the desired substance in the reactor effluent in terms of its mole fraction, these criteria have the advantage in that the optimum switching time can be determined not by the activity of the catalyst, but by the mole fraction of n-butene in the effluent.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84059841","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}
H. Teranishi, K. Hamanoue, Yoshiaki Manki, T. Takagi
The addition reaction of carbon monoxide with ethyl iodide in aqueous hydroiodic acid was investigated under high pressure in the range of 30 to 90kg/cm2. The yield of propionic acid was fairly high and the rate of formation was the first order reaction with respect to carbon monoxide and ethyl iodide. The overall activation energy has been found to be 13.0kcal/mole, which contains the molar enthalpy change of equilibrium reaction (2), i. e., the heat of dissociation of C2H5I and the activation energy of reaction (3), i. e., the reaction between the ethyl cation and carbon monoxide.
{"title":"Studies on the Kinetics of Addition Reactions of Carbon Monoxide with Organic Compounds in Hydroiodic Acid under High Pressure (Part 1)","authors":"H. Teranishi, K. Hamanoue, Yoshiaki Manki, T. Takagi","doi":"10.1627/JPI1959.18.62","DOIUrl":"https://doi.org/10.1627/JPI1959.18.62","url":null,"abstract":"The addition reaction of carbon monoxide with ethyl iodide in aqueous hydroiodic acid was investigated under high pressure in the range of 30 to 90kg/cm2. The yield of propionic acid was fairly high and the rate of formation was the first order reaction with respect to carbon monoxide and ethyl iodide. The overall activation energy has been found to be 13.0kcal/mole, which contains the molar enthalpy change of equilibrium reaction (2), i. e., the heat of dissociation of C2H5I and the activation energy of reaction (3), i. e., the reaction between the ethyl cation and carbon monoxide.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85563659","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":"Activation Volume of Lubricating Oils in Viscous Flow","authors":"Y. Tamai, Toshikazu Yoneda","doi":"10.1627/JPI1959.18.9","DOIUrl":"https://doi.org/10.1627/JPI1959.18.9","url":null,"abstract":"","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80505878","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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