In order to clarify the active species of MoO3-Al2O3 catalyst for hydrocracking of diarylmethane, the effects of MoO3 content and calcination temperature on catalytic activity were studied. Moreover, changes in the hydrocracking behavior of diarylmethane over pretreated catalysts with water and aqueous ammonia were investigated.The catalytic activity increased with increasing MoO3 content, calcination temperature, and reduction time. Molybdenum oxide, which is extractable with aqueous ammonia but not extractable with water, was favorable for hydrocracking reaction.These results were well correlated with Giordano's study1). It was suggested that the main active species for hydrocracking were weak acidic sites formed by the reduction of octahedral Mo(VI) interacting with Al2O3.
{"title":"Studies on Diarylmethanes (Part 9)","authors":"T. Kawai, Y. Yamazaki, Muneaki Tsurugaya","doi":"10.1627/JPI1959.18.20","DOIUrl":"https://doi.org/10.1627/JPI1959.18.20","url":null,"abstract":"In order to clarify the active species of MoO3-Al2O3 catalyst for hydrocracking of diarylmethane, the effects of MoO3 content and calcination temperature on catalytic activity were studied. Moreover, changes in the hydrocracking behavior of diarylmethane over pretreated catalysts with water and aqueous ammonia were investigated.The catalytic activity increased with increasing MoO3 content, calcination temperature, and reduction time. Molybdenum oxide, which is extractable with aqueous ammonia but not extractable with water, was favorable for hydrocracking reaction.These results were well correlated with Giordano's study1). It was suggested that the main active species for hydrocracking were weak acidic sites formed by the reduction of octahedral Mo(VI) interacting with Al2O3.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"31 1","pages":"20-24"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90527874","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 oxidation of 1-butene, butadiene, and acetic acid were carried out in the presence of excess air over two series of V2O5-K2SO4-H2SO4 catalysts, V2O5-K2SO4-H2SO4 (2-x-1, mole ratio) and V2O5-K2SO4-H2SO4 (2-1-y) where x and y were varied (X=0∼1.0, y=0∼3), and the relationship between catalytic behavior and acid-base properties of the catalysts was investigated. The acidity and basicity of V2O5-K2SO4-H2SO4 catalysts were obtained from the values of dehydration activity for isopropyl alcohol (IPA), rp, and the ratio of (dehydrogenation activity for IPA)/(dehydration activity for IPA), ra/rp, which were measured in the presence of excess air. It has been found that the acid-base properties of the catalysts are changed largely by the contents of K2SO4 and H2SO4, and that oxidation activity and selectivity can be interpreted in terms of the acid-base properties of the catalysts. It can be concluded that the acid-base conception in which the catalytic activities are governed by the acidbase properties between the catalyst and reactant is still effective in explaining the function of the K2SO4 and H2SO4 added to V2O5.
{"title":"The Oxidation Activity and Acid-base Properties of V2O5-K2SO4-H2SO4 Catalysts","authors":"M. Ai","doi":"10.1627/JPI1959.18.50","DOIUrl":"https://doi.org/10.1627/JPI1959.18.50","url":null,"abstract":"The vapor-phase oxidation of 1-butene, butadiene, and acetic acid were carried out in the presence of excess air over two series of V2O5-K2SO4-H2SO4 catalysts, V2O5-K2SO4-H2SO4 (2-x-1, mole ratio) and V2O5-K2SO4-H2SO4 (2-1-y) where x and y were varied (X=0∼1.0, y=0∼3), and the relationship between catalytic behavior and acid-base properties of the catalysts was investigated. The acidity and basicity of V2O5-K2SO4-H2SO4 catalysts were obtained from the values of dehydration activity for isopropyl alcohol (IPA), rp, and the ratio of (dehydrogenation activity for IPA)/(dehydration activity for IPA), ra/rp, which were measured in the presence of excess air. It has been found that the acid-base properties of the catalysts are changed largely by the contents of K2SO4 and H2SO4, and that oxidation activity and selectivity can be interpreted in terms of the acid-base properties of the catalysts. It can be concluded that the acid-base conception in which the catalytic activities are governed by the acidbase properties between the catalyst and reactant is still effective in explaining the function of the K2SO4 and H2SO4 added to V2O5.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"13 1","pages":"50-54"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75423456","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 type of benzylic oxidation of toluene in vapor-phase was described in which toluene was dehydrodimerized to bibenzyl and stilbene over Bi2O3-SnO2, catalyst in the temperature range 400∼600°C. Effects of temperature, contact time, and oxygen-to-toluene ratio were investigated in detail, and a proposal of reaction scheme was made.The results obtained show that reactions with longer contact time and higher oxygen-to-toluene ratio are favorable to the formation of stilbene, while shorter contact time and lower oxygen-to-toluene ratio favor the formation of bibenzyl. A reaction route for the formation of stilbene consistent with these data involves the following consecutive steps; toluene→benzylic intermediates→bibenzyl→stilbene. This type of benzylic oxidation is considered to be analogous to the oxidative dehydroaromatization of C3-C4 olefins.
{"title":"Catalytic Oxidation of Toluene to Bibenzyl and Stilbene","authors":"K. Liu, Y. Yamazaki","doi":"10.1627/JPI1959.18.45","DOIUrl":"https://doi.org/10.1627/JPI1959.18.45","url":null,"abstract":"A new type of benzylic oxidation of toluene in vapor-phase was described in which toluene was dehydrodimerized to bibenzyl and stilbene over Bi2O3-SnO2, catalyst in the temperature range 400∼600°C. Effects of temperature, contact time, and oxygen-to-toluene ratio were investigated in detail, and a proposal of reaction scheme was made.The results obtained show that reactions with longer contact time and higher oxygen-to-toluene ratio are favorable to the formation of stilbene, while shorter contact time and lower oxygen-to-toluene ratio favor the formation of bibenzyl. A reaction route for the formation of stilbene consistent with these data involves the following consecutive steps; toluene→benzylic intermediates→bibenzyl→stilbene. This type of benzylic oxidation is considered to be analogous to the oxidative dehydroaromatization of C3-C4 olefins.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"20 1","pages":"45-49"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83816093","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 alkylation of phenol with cyclohexene in the vapor phase has been studied over the cation-exchanged X zeolite catalysts. Because of the dealkylation of products, the catalytic activity decreased with rising reaction temperature. The yield of cyclohexylphenol increased linearly with increase in the amount of acid. Furthermore, the catalytic activity decreased by the addition of pyridine. However, the order of catalytic activity for alkylation of phenol with cyclohexene was not in accord with that for the cracking of cumene. On the other hand, the volcanoshape relation was observed between the catalytic activity for alkylation of phenol with cyclohexene and the electronegativity of metal ion in the catalyst. On the basis of these results, it is concluded that the alkylation reaction proceeds on the acid sites, and the active sites are the surface protons and the metal ions of the catalyst.
{"title":"Alkylation of Phenol with Cyclohexene","authors":"Masanori Seino, S. Okazaki, T. Saito","doi":"10.1627/JPI1959.18.32","DOIUrl":"https://doi.org/10.1627/JPI1959.18.32","url":null,"abstract":"The alkylation of phenol with cyclohexene in the vapor phase has been studied over the cation-exchanged X zeolite catalysts. Because of the dealkylation of products, the catalytic activity decreased with rising reaction temperature. The yield of cyclohexylphenol increased linearly with increase in the amount of acid. Furthermore, the catalytic activity decreased by the addition of pyridine. However, the order of catalytic activity for alkylation of phenol with cyclohexene was not in accord with that for the cracking of cumene. On the other hand, the volcanoshape relation was observed between the catalytic activity for alkylation of phenol with cyclohexene and the electronegativity of metal ion in the catalyst. On the basis of these results, it is concluded that the alkylation reaction proceeds on the acid sites, and the active sites are the surface protons and the metal ions of the catalyst.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"29 1","pages":"32-38"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89357837","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 series of nickel catalysts supported on silica-alumina was prepared for hydroalkylation of aromatic hydrocarbons and effects of pretreatment of catalysts and reaction conditions on their catalytic activity were studied. The selectivity of cyclohexylbenzene which is obtained by hydroalkylation of benzene correlated to the surface acidity of silica-alumina support. The most suitable catalyst was nickel (3∼5wt%) supported on silica-alumina (alumina content: ca. 42wt%), and the results obtained with this simple catalyst were compared with those obtained with catalyst of nickel on a silica-alumina carrier containing both tungsten and fluorine reported by Slaugh et al.The molar ratio of cyclohexylmethylbenzenes to cyclohexylbenzene formed by the reaction of equimolar mixture of benzene and methylbenzenes increased with increase in the basicity of the methylbenzenes.
{"title":"Hydroalkylation of Benzene and Methylbenzenes","authors":"Y. Yamazaki, A. Masuda, T. Kawai, S. Kimura","doi":"10.1627/JPI1959.18.25","DOIUrl":"https://doi.org/10.1627/JPI1959.18.25","url":null,"abstract":"A series of nickel catalysts supported on silica-alumina was prepared for hydroalkylation of aromatic hydrocarbons and effects of pretreatment of catalysts and reaction conditions on their catalytic activity were studied. The selectivity of cyclohexylbenzene which is obtained by hydroalkylation of benzene correlated to the surface acidity of silica-alumina support. The most suitable catalyst was nickel (3∼5wt%) supported on silica-alumina (alumina content: ca. 42wt%), and the results obtained with this simple catalyst were compared with those obtained with catalyst of nickel on a silica-alumina carrier containing both tungsten and fluorine reported by Slaugh et al.The molar ratio of cyclohexylmethylbenzenes to cyclohexylbenzene formed by the reaction of equimolar mixture of benzene and methylbenzenes increased with increase in the basicity of the methylbenzenes.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"14 1","pages":"25-31"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75182215","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}
strength and acidity were determined by the amine titration method with the set of Hammett indicators, in the range of -5.6
在-5.6
{"title":"Activity Dependency on Acidic Property of Molybdenum-Alkaline Earth Metal-Arsenic Oxide Catalyst","authors":"T. Ishikawa, T. Hayakawa","doi":"10.1627/JPI1959.18.55","DOIUrl":"https://doi.org/10.1627/JPI1959.18.55","url":null,"abstract":"strength and acidity were determined by the amine titration method with the set of Hammett indicators, in the range of -5.6<pKa<7.1 The acidity of Mo-Ba oxide is decreased remarkably by addition of As component o the binary oxide, although As oxide has high acidity, especially in the range of strong acid strength, and the resultant Mo-Ba-As oxide has acidity of weak acid strength. A comparison of activity with acidic property of Mo-X-As (atomic ratio=1:1:1) type oxide catalyst containing different kinds of X component and Mo-Sr-As (As/Mo=1) oxide catalysts of different amounts of Sr showed that butadiene formation (partial oxidation) and 2-butene formation (isomerization) increased with increasing acidity in weak acid strength (1.5<pKa<7.1, while CO2+CO formation increased with increasing acidity in strong acid strength (pKa<1.5). It is considered that molybdate of alkaline earth metal exists in both Mo-X and Mo-XAs oxides, and plays important roles in the catalytic oxidation reaction. However, the coexistence of As component suppresses the crystallization of this salt, resulting in the decrease of isomerization and increase of selectivity for partial oxidation. By increasing atomic number of X component in Mo-X-As oxide catalyst, acidity and the activity for diene formation decreased but the selectivity for the formation increased. Propylene oxidation was also studied with regard to the acidic property of the catalyst.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"4 1","pages":"55-61"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75245065","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}
Oxidation reactions of ethylene over zeolite loaded with Pd(II) and/or Cu(II) by way of ion exchange were studied in the presence of steam. Neither Pd(II)-zeolite nor Cu(II)-zeolite had good catalytic activity for oxidation of ethylene to acetaldehyde. However, the dual ion catalysts, namely, Pd(II)-Cu(II)-zeolites which were prepared by various ion exchange methods, were found highly active and selective for oxidation of ethylene to acetaldehyde. The degree of conversion of olefins under the same experimental conditions was in the order: ethylene>propylene>1-butene>cis-2-butene≈trans-2-butene. The reaction mechanism was discussed in analogy with that of Wacker-reaction.
{"title":"The Catalysis of Palladium and Cupric Ion-exchanged Zeolite for Oxidation of Ethylene","authors":"H. Arai, Takashi Yamashiro, T. Kubo, H. Tominaga","doi":"10.1627/JPI1959.18.39","DOIUrl":"https://doi.org/10.1627/JPI1959.18.39","url":null,"abstract":"Oxidation reactions of ethylene over zeolite loaded with Pd(II) and/or Cu(II) by way of ion exchange were studied in the presence of steam. Neither Pd(II)-zeolite nor Cu(II)-zeolite had good catalytic activity for oxidation of ethylene to acetaldehyde. However, the dual ion catalysts, namely, Pd(II)-Cu(II)-zeolites which were prepared by various ion exchange methods, were found highly active and selective for oxidation of ethylene to acetaldehyde. The degree of conversion of olefins under the same experimental conditions was in the order: ethylene>propylene>1-butene>cis-2-butene≈trans-2-butene. The reaction mechanism was discussed in analogy with that of Wacker-reaction.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"62 1","pages":"39-44"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82074120","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. Sakurai, Seiichiro Hironaka, M. Furuta, Yasuo Watanabe
Pentaerythritol partial-esters were synthesized and their physical properties, thermal stabilities, heat of adsorption, and lubricity were investigated. It was found that the hydroxyl groups involved in the partial-esters exerted some important effects on their properties. The partial-esters showed higher viscosities than their respective full-esters due to the association of their molecules. They adsorbed strongly onto metal surfaces to control corrosion of the metals, and to give better boundary lubricity.
{"title":"Lubricating Properties of Pentaerythritol Partial-Esters","authors":"T. Sakurai, Seiichiro Hironaka, M. Furuta, Yasuo Watanabe","doi":"10.1627/JPI1959.18.1","DOIUrl":"https://doi.org/10.1627/JPI1959.18.1","url":null,"abstract":"Pentaerythritol partial-esters were synthesized and their physical properties, thermal stabilities, heat of adsorption, and lubricity were investigated. It was found that the hydroxyl groups involved in the partial-esters exerted some important effects on their properties. The partial-esters showed higher viscosities than their respective full-esters due to the association of their molecules. They adsorbed strongly onto metal surfaces to control corrosion of the metals, and to give better boundary lubricity.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"26 1","pages":"1-8"},"PeriodicalIF":0.0,"publicationDate":"1976-05-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82620911","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":"Studies on Catalysts for Low-Temperature Steam-Reforming of Hydrocarbons (III):Outstanding Activity of the Rh-MgWO 4 System","authors":"K. Takami, A. Igarashi, Y. Ogino","doi":"10.1627/jpi1959.18.127","DOIUrl":"https://doi.org/10.1627/jpi1959.18.127","url":null,"abstract":"","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"47 1","pages":"127-132"},"PeriodicalIF":0.0,"publicationDate":"1976-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80409807","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 dehydrosulfurization of ethanethiol over various alkali metal zeolite catalysts was studied. The catalytic activity of NaY zeolite was little affected by the exchange of sodium ion with other alkali metal ions (Li, K, Cs and Rb). The catalytic activity of sodium zeolite was dependent on the types of zeolite (NaX, NaY and NaA), and the order of its catalytic activity was NaX>NaY>NaA. When NaY and NaA were used, the dehydrosulfurization products were only ethylene and hydrogen sulfide. In the case of dehydrosulfurization of ethanethiol on NaX, the products were ethylene, hydrogen sulfide and a substantial amount of diethyl sulfide which was formed by disproportionation of ethanethiol. Furthermore, discussions were made on the active sites of alkali metal zeolite catalysts, and it was concluded that they were the alkali metal ions and the oxygen anion of skeletal structure of zeolite. In the light of the nature of the active sites, the reaction mechanisms were also proposed.
{"title":"Studies of Catalytic Cracking of Organic Sulfur Compounds over Solid Acid Catalyst (Part 9):Dehydrosulfurization of Ethanethiol over Alkali Metal Zeolite Catalysts","authors":"M. Sugioka, T. Kamanaka, K. Aomura","doi":"10.1627/jpi1959.18.14","DOIUrl":"https://doi.org/10.1627/jpi1959.18.14","url":null,"abstract":"The dehydrosulfurization of ethanethiol over various alkali metal zeolite catalysts was studied. The catalytic activity of NaY zeolite was little affected by the exchange of sodium ion with other alkali metal ions (Li, K, Cs and Rb). The catalytic activity of sodium zeolite was dependent on the types of zeolite (NaX, NaY and NaA), and the order of its catalytic activity was NaX>NaY>NaA. When NaY and NaA were used, the dehydrosulfurization products were only ethylene and hydrogen sulfide. In the case of dehydrosulfurization of ethanethiol on NaX, the products were ethylene, hydrogen sulfide and a substantial amount of diethyl sulfide which was formed by disproportionation of ethanethiol. Furthermore, discussions were made on the active sites of alkali metal zeolite catalysts, and it was concluded that they were the alkali metal ions and the oxygen anion of skeletal structure of zeolite. In the light of the nature of the active sites, the reaction mechanisms were also proposed.","PeriodicalId":9596,"journal":{"name":"Bulletin of The Japan Petroleum Institute","volume":"32 1","pages":"14-19"},"PeriodicalIF":0.0,"publicationDate":"1976-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83212128","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：