Activation enthalpy, entropy, and volume of viscous flow were determined experimentally with 16 mineral lubricating oils and 4 blends. The relations between these quantities were examined and it was found that the relation between activation enthalpy and volume and that between the enthalpy and entropy were approximately linear. The later relation seems similar to the so-called compensation effect in chemical reactions. The activation enthalpy of the blends was shown to be additive when expressed in volume fraction.
{"title":"Flow Activation Quantities of Mineral Lubricating Oils and Their Correlations","authors":"Y. Tamai, Toshikazu Yoneda","doi":"10.1627/JPI1959.19.17","DOIUrl":"https://doi.org/10.1627/JPI1959.19.17","url":null,"abstract":"Activation enthalpy, entropy, and volume of viscous flow were determined experimentally with 16 mineral lubricating oils and 4 blends. The relations between these quantities were examined and it was found that the relation between activation enthalpy and volume and that between the enthalpy and entropy were approximately linear. The later relation seems similar to the so-called compensation effect in chemical reactions. The activation enthalpy of the blends was shown to be additive when expressed in volume fraction.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"53 1","pages":"17-20"},"PeriodicalIF":0.0,"publicationDate":"1977-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87555517","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 check list has been compiled based on an extensive survey of literature on energy conservation. Major items of energy conservation have been classified into sub-lists in each of the planning, design, and operation phases of petroleum refineries. The check list will be useful for initiating energy conservation programs.
{"title":"A Check List for Energy Conservation in Petroleum Refineries","authors":"K. Shiroko, T. Umeda","doi":"10.1627/jpi1959.19.193","DOIUrl":"https://doi.org/10.1627/jpi1959.19.193","url":null,"abstract":"This check list has been compiled based on an extensive survey of literature on energy conservation. Major items of energy conservation have been classified into sub-lists in each of the planning, design, and operation phases of petroleum refineries. The check list will be useful for initiating energy conservation programs.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"15 1","pages":"193-205"},"PeriodicalIF":0.0,"publicationDate":"1977-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81643184","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}
duced into the zeolite by ion-exchanging it with an aqueous solution containing the metal ion. Isomerization activity leveled off to a maximum at some metal content, whereas that of hydrogenolysis increased with increasing metal content with the exception of Pd/HY. The order of maximum isomerization activities of the catalysts was as follows: Pt/HY>Pd/HY, Rh/HY>Ir/HY>Ni/HY>Co/HY>Ru/HY>Fe/HY The order of hydrogenolysis activities was as follows: Ru/HY>Rh/HY>Ir/HY>Pt/HY>Pd/HY; Co/HY> Ni/HY>Fe/HY From these results, Pd/HY and Pt/HY were found to be the most active and selective among Group VIII metal/HY catalysts for isomerization of n-pentane to isopentane. Finally, the mechanism of isomerization of n-pentane was discussed on the basis of the present experimental results.
{"title":"Isomerization of n-Pentane on Group VIII Metal/Hydrogen-Zeolite Y Catalysts","authors":"M. Saito, Takahisa Iwasaki","doi":"10.1627/jpi1959.19.30","DOIUrl":"https://doi.org/10.1627/jpi1959.19.30","url":null,"abstract":"duced into the zeolite by ion-exchanging it with an aqueous solution containing the metal ion. Isomerization activity leveled off to a maximum at some metal content, whereas that of hydrogenolysis increased with increasing metal content with the exception of Pd/HY. The order of maximum isomerization activities of the catalysts was as follows: Pt/HY>Pd/HY, Rh/HY>Ir/HY>Ni/HY>Co/HY>Ru/HY>Fe/HY The order of hydrogenolysis activities was as follows: Ru/HY>Rh/HY>Ir/HY>Pt/HY>Pd/HY; Co/HY> Ni/HY>Fe/HY From these results, Pd/HY and Pt/HY were found to be the most active and selective among Group VIII metal/HY catalysts for isomerization of n-pentane to isopentane. Finally, the mechanism of isomerization of n-pentane was discussed on the basis of the present experimental results.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"13 1","pages":"30-36"},"PeriodicalIF":0.0,"publicationDate":"1977-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84385183","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 selectivities of C5 hydrocarbons for such solvents as propylene carbonate, N-methyl-2-pyrrolidone, and a mixed solvent consisting of propylene carbonate and ethyl carbitol, were determined by a gas chromatograph connected by a capillary column internally coated with the respective solvents. A convenient method for coating a solvent on the inside surface of a capillary column was devised. Selectivities of hydrocarbons were estimated in the solvent concentration ranging from 70 to 90mol% and good agreement between the calculated and experimental results was obtained.
{"title":"A Method for Determination of Selectivities of Solvents for Multicomponent Mixtures Using a Capillary Column","authors":"Minoru Enomoto","doi":"10.1627/jpi1959.19.81","DOIUrl":"https://doi.org/10.1627/jpi1959.19.81","url":null,"abstract":"The selectivities of C5 hydrocarbons for such solvents as propylene carbonate, N-methyl-2-pyrrolidone, and a mixed solvent consisting of propylene carbonate and ethyl carbitol, were determined by a gas chromatograph connected by a capillary column internally coated with the respective solvents. A convenient method for coating a solvent on the inside surface of a capillary column was devised. Selectivities of hydrocarbons were estimated in the solvent concentration ranging from 70 to 90mol% and good agreement between the calculated and experimental results was obtained.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"146 1","pages":"81-85"},"PeriodicalIF":0.0,"publicationDate":"1977-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85711850","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 vapor-phase reaction of cyclopentadiene (CPD) with acetylene over silicon carbide has been investigated with reference to the formation of 2, 5-norbornadiene (2, 5-NBD) and toluene. The yield of 2, 5-NBD was enhanced with rise in the reaction temperature and showed a maximum yield at 420°C. On the other hand, the formation of toluene initiating at 400°C increased with increasing temperature and with a simultaneous decrease in the yield of (2, 5-NBD). At 550°C, the yield of toluene was 30% and the selectivity was 75%. The formation of toluene was also observed in the reaction of 2, 5-NBD. Therefore, it was concluded that 2, 5-NBD was an intermediate of toluene. This was consistent with the kinetic studies on the formation of toluene. The menchanism of the addition of acetylene to CPD was also discussed and as a result, the role of a radical mechanism, in addition to that of a concerted one, was also assumed.
{"title":"Formation of Toluene in Vapor-Phase Reaction of Cyclopentadiene with Acetylene over Silicon Carbide","authors":"E. Echigoya, M. Akimoto, E. Minomiya","doi":"10.1627/JPI1959.18.153","DOIUrl":"https://doi.org/10.1627/JPI1959.18.153","url":null,"abstract":"The vapor-phase reaction of cyclopentadiene (CPD) with acetylene over silicon carbide has been investigated with reference to the formation of 2, 5-norbornadiene (2, 5-NBD) and toluene. The yield of 2, 5-NBD was enhanced with rise in the reaction temperature and showed a maximum yield at 420°C. On the other hand, the formation of toluene initiating at 400°C increased with increasing temperature and with a simultaneous decrease in the yield of (2, 5-NBD). At 550°C, the yield of toluene was 30% and the selectivity was 75%. The formation of toluene was also observed in the reaction of 2, 5-NBD. Therefore, it was concluded that 2, 5-NBD was an intermediate of toluene. This was consistent with the kinetic studies on the formation of toluene. The menchanism of the addition of acetylene to CPD was also discussed and as a result, the role of a radical mechanism, in addition to that of a concerted one, was also assumed.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"62 2","pages":"153-157"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72613552","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}
After the addition of potassium chloride (90g) and of various amounts of ferrofluid (0.5∼4.0ml) to 3, 000ml of a kerosene-in-water emulsion containing 1, 000ppm of kerosene, it was treated magnetically in a magnetic field of 462, 871 and 1, 480 Oe. The flow rate of the emulsion was varied from 100 to 600ml/min. The effects of the amount of ferrofluid added, the magnetic field and the flow rate of emulsion on the oil removal efficiency were studied. As a result, the oil removal efficiency increased as the amount of ferrofluid added and the strength of magnetic field increased, but it decreased as the flow rate of emulsion increased. Ferrofluid is a stable colloidal dispersion of magnetic particles (D<150A) whose carrier liquid is kerosene.An equation for oil removal efficiency was theoretically derived. The calculated and measured values of oil removal efficiency are shown.
{"title":"Magnetic Treatment of Oily Waste Water","authors":"M. Yorizane, O. Tozawa","doi":"10.1627/JPI1959.18.183","DOIUrl":"https://doi.org/10.1627/JPI1959.18.183","url":null,"abstract":"After the addition of potassium chloride (90g) and of various amounts of ferrofluid (0.5∼4.0ml) to 3, 000ml of a kerosene-in-water emulsion containing 1, 000ppm of kerosene, it was treated magnetically in a magnetic field of 462, 871 and 1, 480 Oe. The flow rate of the emulsion was varied from 100 to 600ml/min. The effects of the amount of ferrofluid added, the magnetic field and the flow rate of emulsion on the oil removal efficiency were studied. As a result, the oil removal efficiency increased as the amount of ferrofluid added and the strength of magnetic field increased, but it decreased as the flow rate of emulsion increased. Ferrofluid is a stable colloidal dispersion of magnetic particles (D<150A) whose carrier liquid is kerosene.An equation for oil removal efficiency was theoretically derived. The calculated and measured values of oil removal efficiency are shown.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"37 1","pages":"183-189"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86901877","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 probability of acetic acid synthesis from n-butenes and isobutene was studied with V2O5-binary catalysts. As a second component, following atoms were added to V2O5 in the form of oxide or metal; Rh, B, Cr, Nb, Zn, Pd, Ta, Zr, Si, Ni, Ge, Fe, Ca, Pt, W, Li, Cd, As, Co, Te, Mg, Mn, Mo, Cu, Ag, P, Ba, Ti, Sn, Al, and Sb.In the presence of water, n-butenes and isobutene were oxidized to acetic acid with more than 40% selectivity based on the carbon atom at about 100% conversion of each butene with air containing 3% of butene over V-Cr(3/7), V-Rh(8/2), V-B(5/5) and V-Nb(5/5) catalysts at 270∼310°C.Acetaldehyde, acetone, formaldehyde, maleic acid, formic acid, propionic acid, acrylic acid and citoraconic acid were obtained in low yields from n-butenes.On the other hand, from isobutene methacrylic acid and isobutylic acid were formed in addition to above by-products in low yields.As to the reaction path, acetic acid was considered to be formed via hydration of butenes to form an alcoholic intermediate1)), followed by oxydehydrogenation on the catalyst which had some different active sites to induce other reactions at the same time.
{"title":"Synthesis of Acetic Acid by Catalytic Oxidation of Butenes (Part 1)","authors":"T. Yamashita, S. Ninagawa, Tetsuya Kato","doi":"10.1627/JPI1959.18.167","DOIUrl":"https://doi.org/10.1627/JPI1959.18.167","url":null,"abstract":"The probability of acetic acid synthesis from n-butenes and isobutene was studied with V2O5-binary catalysts. As a second component, following atoms were added to V2O5 in the form of oxide or metal; Rh, B, Cr, Nb, Zn, Pd, Ta, Zr, Si, Ni, Ge, Fe, Ca, Pt, W, Li, Cd, As, Co, Te, Mg, Mn, Mo, Cu, Ag, P, Ba, Ti, Sn, Al, and Sb.In the presence of water, n-butenes and isobutene were oxidized to acetic acid with more than 40% selectivity based on the carbon atom at about 100% conversion of each butene with air containing 3% of butene over V-Cr(3/7), V-Rh(8/2), V-B(5/5) and V-Nb(5/5) catalysts at 270∼310°C.Acetaldehyde, acetone, formaldehyde, maleic acid, formic acid, propionic acid, acrylic acid and citoraconic acid were obtained in low yields from n-butenes.On the other hand, from isobutene methacrylic acid and isobutylic acid were formed in addition to above by-products in low yields.As to the reaction path, acetic acid was considered to be formed via hydration of butenes to form an alcoholic intermediate1)), followed by oxydehydrogenation on the catalyst which had some different active sites to induce other reactions at the same time.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"90 1","pages":"167-177"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85842991","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 activation volume of viscous flow in mixtures of paraffinic and naphthenic base oils of high and low viscosities, and in those of liquid fatty acids, their esters, and fatty oils have been determined experimentally. The results are used to test the applicability of the semiempirical formula which can estimate the activation volume from the molecular structure of the substance involved. Limitations in its applicability are also discussed.
{"title":"Flow Activation Volume of Mixed Mineral Oils and Fatty Oils","authors":"Y. Tamai, Toshikazu Yoneda","doi":"10.1627/JPI1959.18.113","DOIUrl":"https://doi.org/10.1627/JPI1959.18.113","url":null,"abstract":"The activation volume of viscous flow in mixtures of paraffinic and naphthenic base oils of high and low viscosities, and in those of liquid fatty acids, their esters, and fatty oils have been determined experimentally. The results are used to test the applicability of the semiempirical formula which can estimate the activation volume from the molecular structure of the substance involved. Limitations in its applicability are also discussed.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"24 1","pages":"113-116"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90919044","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, Mitsugu Yumoto, E. Kikuchi, Y. Morita
The reaction between benzene and steam on potassium polyaluminate catalysts was investigated in a flow system under atmospheric pressure at 900°C. The catalytic activity increased with increasing K+ content in the catalyst, showing that the potassium cation constituted the active sites for this reaction. The rate of reaction between the deposited carbon and steam also increased as the K+ content increased. A good linear relationship was obtained between activity and the rate of the carbon-steam reaction.The conversion of benzene to carbon monoxide and dioxide and the amount of deposited carbon decreased with increasing partial pressure of steam, while both of them increased with increasing partial pressure of benzene. The depression with steam was explained by the competition of the steam with benzene for the active sites, resulting in retardation of the formation of intermediate deposited carbon.
{"title":"Steam Reforming of Hydrocarbons on Alkali Polyaluminate Catalysts (Part 1)","authors":"T. Kimura, Nobuhiko Nakabayashi, Mitsugu Yumoto, E. Kikuchi, Y. Morita","doi":"10.1627/JPI1959.18.133","DOIUrl":"https://doi.org/10.1627/JPI1959.18.133","url":null,"abstract":"The reaction between benzene and steam on potassium polyaluminate catalysts was investigated in a flow system under atmospheric pressure at 900°C. The catalytic activity increased with increasing K+ content in the catalyst, showing that the potassium cation constituted the active sites for this reaction. The rate of reaction between the deposited carbon and steam also increased as the K+ content increased. A good linear relationship was obtained between activity and the rate of the carbon-steam reaction.The conversion of benzene to carbon monoxide and dioxide and the amount of deposited carbon decreased with increasing partial pressure of steam, while both of them increased with increasing partial pressure of benzene. The depression with steam was explained by the competition of the steam with benzene for the active sites, resulting in retardation of the formation of intermediate deposited carbon.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"3 1","pages":"133-138"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88636030","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}
reaction product on all these catalysts. Some of the catalysts, however, exhibited considerably high selectivity for production of C2 or higher gaseous hydrocarbons. The following sequence of selectivity for C2 hydrocarbons was obtained: Fe>Pd>Rh>Ru>Pt>Co>Ni. Among the catalysts tested, the graphite-supported Rh catalyst showed the highest rate of production of C2 hydrocarbons. In the whole range of conversions, the graphite-supported Rh catalyst produced C2 hydrocarbons more selectively than the alumina-supported or charcoal-supported catalysts. This difference was considered due to the strong metal-support interaction in the graphite-supported catalyst that involved electron transfer between rhodium and graphite. Among the various pretreatments rendered using different gases, pretreatment in air enhanced most the activity of the graphite-supported Rh catalyst.
{"title":"Synthesis of Gaseous Hydrocarbons from Carbon Monoxide and Hydrogen over Transition Metal Catalysts (Part 1)","authors":"E. Kikuchi, T. Inō, N. Ito, Y. Morita","doi":"10.1627/JPI1959.18.139","DOIUrl":"https://doi.org/10.1627/JPI1959.18.139","url":null,"abstract":"reaction product on all these catalysts. Some of the catalysts, however, exhibited considerably high selectivity for production of C2 or higher gaseous hydrocarbons. The following sequence of selectivity for C2 hydrocarbons was obtained: Fe>Pd>Rh>Ru>Pt>Co>Ni. Among the catalysts tested, the graphite-supported Rh catalyst showed the highest rate of production of C2 hydrocarbons. In the whole range of conversions, the graphite-supported Rh catalyst produced C2 hydrocarbons more selectively than the alumina-supported or charcoal-supported catalysts. This difference was considered due to the strong metal-support interaction in the graphite-supported catalyst that involved electron transfer between rhodium and graphite. Among the various pretreatments rendered using different gases, pretreatment in air enhanced most the activity of the graphite-supported Rh catalyst.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"63 1","pages":"139-145"},"PeriodicalIF":0.0,"publicationDate":"1976-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89211050","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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