Precise oligomeric materials that lie between the low-molecular-weight discrete molecules and high-molecu-lar-weight disperse polymers constitute a growing research area not only in terms of fundamental studies but also for various applications. In the field of silicone (polysiloxane) materials, several research groups have reported various methods for the synthesis of discrete oligosiloxanes but improvement in the control of siloxane sequences is still desirable. This review highlights our recent contributions to the precise synthesis of discrete sequence-defined oligosiloxanes by controlled iteration of B(C 6 F 5 ) 3 -catalyzed reactions. As controlled iteration can be performed in one pot, various discrete sequence-defined oligosiloxanes can be more readily synthesized in com-parison to the other reported methods.
{"title":"Precise Synthesis of Discrete Sequence-defined Oligosiloxanes","authors":"Kazuhiro Matsumoto","doi":"10.1627/jpi.64.307","DOIUrl":"https://doi.org/10.1627/jpi.64.307","url":null,"abstract":"Precise oligomeric materials that lie between the low-molecular-weight discrete molecules and high-molecu-lar-weight disperse polymers constitute a growing research area not only in terms of fundamental studies but also for various applications. In the field of silicone (polysiloxane) materials, several research groups have reported various methods for the synthesis of discrete oligosiloxanes but improvement in the control of siloxane sequences is still desirable. This review highlights our recent contributions to the precise synthesis of discrete sequence-defined oligosiloxanes by controlled iteration of B(C 6 F 5 ) 3 -catalyzed reactions. As controlled iteration can be performed in one pot, various discrete sequence-defined oligosiloxanes can be more readily synthesized in com-parison to the other reported methods.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89832125","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This review of the author’s research introduces the catalytic reactions for the conversion of various biomass feedstocks to liquid transportation fuels, especially to liquid hydrocarbon fuels. Catalytic reactions in the follow-ing chemical processes were included: conversion of synthesis gas (obtained from the gasification of woody biomass) to liquid fuels (hydrocarbons and alcohols); conversion of vegetable oils to liquid hydrocarbons; conversion of algae oils to liquid hydrocarbons; and conversion of bioethanol to liquid hydrocarbons. Polymerization and hydrotreatment were two main catalytic technologies in these chemical processes. The polymerization reactions included Fischer-Tropsch synthesis, mixed alcohols synthesis, and ethylene oligomerization. Hydrotreatment reactions included cracking, isomerization, and deoxygenation. Metal catalysts, solid acid catalysts, and bifunctional catalysts containing metal and solid acid were developed for the reactions. Slurry reactor, fixed-bed flow reactor, and autoclave batch reactor were used according to the requirements of the various reactions. Active metal species, support effect, and balance between metal and solid acid in the bifunctional catalysts were dis-cussed in the development of active catalysts. Using these catalysts and processes, various biomass feedstocks could be converted to hydrocarbon biofuels with the same chemical compositions as conventional petroleum-derived gasoline, diesel, liquefied petroleum gas jet
{"title":"Catalytic Conversion of Various Biomass Feedstocks to Liquid Transportation Fuels","authors":"Yanyong Liu","doi":"10.1627/jpi.64.317","DOIUrl":"https://doi.org/10.1627/jpi.64.317","url":null,"abstract":"This review of the author’s research introduces the catalytic reactions for the conversion of various biomass feedstocks to liquid transportation fuels, especially to liquid hydrocarbon fuels. Catalytic reactions in the follow-ing chemical processes were included: conversion of synthesis gas (obtained from the gasification of woody biomass) to liquid fuels (hydrocarbons and alcohols); conversion of vegetable oils to liquid hydrocarbons; conversion of algae oils to liquid hydrocarbons; and conversion of bioethanol to liquid hydrocarbons. Polymerization and hydrotreatment were two main catalytic technologies in these chemical processes. The polymerization reactions included Fischer-Tropsch synthesis, mixed alcohols synthesis, and ethylene oligomerization. Hydrotreatment reactions included cracking, isomerization, and deoxygenation. Metal catalysts, solid acid catalysts, and bifunctional catalysts containing metal and solid acid were developed for the reactions. Slurry reactor, fixed-bed flow reactor, and autoclave batch reactor were used according to the requirements of the various reactions. Active metal species, support effect, and balance between metal and solid acid in the bifunctional catalysts were dis-cussed in the development of active catalysts. Using these catalysts and processes, various biomass feedstocks could be converted to hydrocarbon biofuels with the same chemical compositions as conventional petroleum-derived gasoline, diesel, liquefied petroleum gas jet","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82589955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Drilling in depleted oil and gas reservoirs, highly developed pores/fractures and other low-pressure areas is often accompanied by serious drilling fluid invasion. Huge fluid intrusion not only causes borehole instability, but also creates severe formation damage and reduces well productivity. Therefore, reducing fluid intrusion is crucial in these reservoirs1). Granular, fibrous, and lamellar solid materials are commonly added in water-based drilling fluids as plugging agents. By designing solid particles size compatible with the pore throat, bridging occurs in the reservoir near the borehole wall to achieve filtration control2). As the long-time circulation in the high temperature and high-pressure wellbore, the solid phase material tends to take place complicated problems such as coalescence, settlement, acid dissolution, gelatinization, viscoelastic damage, etc. Therefore, maintaining the size distribution to ensure good sealing against specific rocks is difficult. Moreover, the solid particles remaining in the reservoir have a negative impact on production. Recently, a colloidal gas aphron (CGA) drilling fluid technology has been successfully applied internationally to solve the huge leakage problems, as listed in Table 1. The fluid system has been proved to have the advantages of reducing fluid invasion and reservoir damage significantly, no need for additional pressurization equipment, high cutting carrying efficiency, shortening drilling cycle and reducing drilling cost3)~5). A large number of aphrons generated by surfactants and polymers exist in the CGA fluid. Aphrons are microbubbles composed of a gas core and a thick multilayered aqueous surfactant shell. These robust and elastic microbubbles are ideal bridging materials with a wide size distribution and can be deformed to adapt to various pores and fractures6)~8). Pasdar et al. observed the changes in the particle size of the aphrons under a microscope with sudden or stepwise pressure, and found that the aphrons can survive under 2000 psig and ambient temperature. Growcock et al. further proposed that aphrons can survive at 4000 psig and ambient temperature. More importantly, aphrons show little affinity for each other and for mineral surfaces. Consequently, aphrons can be cleaned up to the ground [Regular Paper]
{"title":"High Temperature Sealing Performance of Novel Biodegradable Colloidal Gas Aphron (CGA) Drilling Fluid System","authors":"Wenxi Zhu, Xiuhua Zheng","doi":"10.1627/jpi.64.331","DOIUrl":"https://doi.org/10.1627/jpi.64.331","url":null,"abstract":"Drilling in depleted oil and gas reservoirs, highly developed pores/fractures and other low-pressure areas is often accompanied by serious drilling fluid invasion. Huge fluid intrusion not only causes borehole instability, but also creates severe formation damage and reduces well productivity. Therefore, reducing fluid intrusion is crucial in these reservoirs1). Granular, fibrous, and lamellar solid materials are commonly added in water-based drilling fluids as plugging agents. By designing solid particles size compatible with the pore throat, bridging occurs in the reservoir near the borehole wall to achieve filtration control2). As the long-time circulation in the high temperature and high-pressure wellbore, the solid phase material tends to take place complicated problems such as coalescence, settlement, acid dissolution, gelatinization, viscoelastic damage, etc. Therefore, maintaining the size distribution to ensure good sealing against specific rocks is difficult. Moreover, the solid particles remaining in the reservoir have a negative impact on production. Recently, a colloidal gas aphron (CGA) drilling fluid technology has been successfully applied internationally to solve the huge leakage problems, as listed in Table 1. The fluid system has been proved to have the advantages of reducing fluid invasion and reservoir damage significantly, no need for additional pressurization equipment, high cutting carrying efficiency, shortening drilling cycle and reducing drilling cost3)~5). A large number of aphrons generated by surfactants and polymers exist in the CGA fluid. Aphrons are microbubbles composed of a gas core and a thick multilayered aqueous surfactant shell. These robust and elastic microbubbles are ideal bridging materials with a wide size distribution and can be deformed to adapt to various pores and fractures6)~8). Pasdar et al. observed the changes in the particle size of the aphrons under a microscope with sudden or stepwise pressure, and found that the aphrons can survive under 2000 psig and ambient temperature. Growcock et al. further proposed that aphrons can survive at 4000 psig and ambient temperature. More importantly, aphrons show little affinity for each other and for mineral surfaces. Consequently, aphrons can be cleaned up to the ground [Regular Paper]","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80017403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
H. Nagata, Sakiho Izumi, Rin-ichi Yamashita, Y. Johno
2021) Catalytic combustion of an organic compound is characterized by an S-shaped curve for the temperature dependence of the reaction. Expression of this S-shaped curve with a mathematical function would allow highly accurate analysis based on a small number of data points. This study used toluene combustion over a -alumina-supported platinum catalyst as an example of a catalytic combustion reaction, and investigated whether the temperature dependence of the toluene conversion could be expressed by a logistic function. The parameters were obtained from the reaction data using a single regression analysis. The logistic function well represented the experimental data using the linear relationship as the function of temperature. Furthermore, the temperature at which the toluene conversion reaches 50 % can be
{"title":"Application of Logistic Regression Analysis to Combustion of Toluene over γ-Alumina-supported Platinum Catalyst","authors":"H. Nagata, Sakiho Izumi, Rin-ichi Yamashita, Y. Johno","doi":"10.1627/jpi.64.340","DOIUrl":"https://doi.org/10.1627/jpi.64.340","url":null,"abstract":"2021) Catalytic combustion of an organic compound is characterized by an S-shaped curve for the temperature dependence of the reaction. Expression of this S-shaped curve with a mathematical function would allow highly accurate analysis based on a small number of data points. This study used toluene combustion over a -alumina-supported platinum catalyst as an example of a catalytic combustion reaction, and investigated whether the temperature dependence of the toluene conversion could be expressed by a logistic function. The parameters were obtained from the reaction data using a single regression analysis. The logistic function well represented the experimental data using the linear relationship as the function of temperature. Furthermore, the temperature at which the toluene conversion reaches 50 % can be","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90972090","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Takayuki Kurogi, Mayumi Etou, Rei Hamada, Shingo Sakai
The computer technologies of machine learning and multiobjective optimization were introduced to develop the catalyst for fluid catalytic cracking (FCC). Response surface methodology was applied for a training set consist-ing of 1000 data points with varied catalyst compositions which consist of a variety of catalysts compositions, feedstock properties, pseudo-equilibrium conditions, cracking performance test conditions as input parameters and the cracking test results as outputs. At first, response surface model (RSM) was obtained with four approxima-tion methods, among which the radial basis function (RBF) method was found to give the highest score accurate RSM with the smallest average error and the highest coefficient of determination among them. Then the virtual experiments were carried out with the RSM applied with multiobjective genetic algorithm (MOGA) to optimize the catalyst design considering the multiobjective; to yield less bottoms, less coke, more gasoline and less gas. After 5000 virtual experiments with RSM were carried out, we found that the pareto front was obtained. Finally, the optimum catalyst design was selected from the designs on the pareto front. As a result, the selected catalyst design showed 2.7 % higher gasoline yield and was confirmed to show the excellent performance over conventional FCC catalyst.
{"title":"Catalyst Design by Machine Learning and Multiobjective Optimization","authors":"Takayuki Kurogi, Mayumi Etou, Rei Hamada, Shingo Sakai","doi":"10.1627/JPI.64.256","DOIUrl":"https://doi.org/10.1627/JPI.64.256","url":null,"abstract":"The computer technologies of machine learning and multiobjective optimization were introduced to develop the catalyst for fluid catalytic cracking (FCC). Response surface methodology was applied for a training set consist-ing of 1000 data points with varied catalyst compositions which consist of a variety of catalysts compositions, feedstock properties, pseudo-equilibrium conditions, cracking performance test conditions as input parameters and the cracking test results as outputs. At first, response surface model (RSM) was obtained with four approxima-tion methods, among which the radial basis function (RBF) method was found to give the highest score accurate RSM with the smallest average error and the highest coefficient of determination among them. Then the virtual experiments were carried out with the RSM applied with multiobjective genetic algorithm (MOGA) to optimize the catalyst design considering the multiobjective; to yield less bottoms, less coke, more gasoline and less gas. After 5000 virtual experiments with RSM were carried out, we found that the pareto front was obtained. Finally, the optimum catalyst design was selected from the designs on the pareto front. As a result, the selected catalyst design showed 2.7 % higher gasoline yield and was confirmed to show the excellent performance over conventional FCC catalyst.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84268131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Deactivation of a mixture of Rh/Al 2 O 3 and CeO 2 _ ZrO 2 (CZ) by high-temperature ageing was clearly observed in three-way catalytic reactions under lean/rich perturbation conditions. The light-off temperature at which 50 % conversion was achieved was increased in the order of fresh ＜ stoichi. ≈ rich ＜ rich/lean ＜ lean ageing conditions. Rh dispersion and presence of isolated Rh sites, revealed from in-situ FT-IR spectroscopy following CO adsorption, were responsible for the high light-off activity. NO conversion in higher temperature regions under lean/rich perturbation conditions was influenced by the ageing atmosphere. H 2 -TPR measurements suggested the formation of Rh _ CZ interactions with different strengths depending on the atmosphere during high-tempera-ture ageing. The strength of the Rh _ CZ interaction was suspected to be important to achieve high NO conversion in higher temperature regions.
{"title":"Effect of Ageing Atmosphere on Three-way Catalytic Performance of Supported Rh Catalysts","authors":"Yasutaka Tomida, M. Haneda","doi":"10.1627/JPI.64.219","DOIUrl":"https://doi.org/10.1627/JPI.64.219","url":null,"abstract":"Deactivation of a mixture of Rh/Al 2 O 3 and CeO 2 _ ZrO 2 (CZ) by high-temperature ageing was clearly observed in three-way catalytic reactions under lean/rich perturbation conditions. The light-off temperature at which 50 % conversion was achieved was increased in the order of fresh ＜ stoichi. ≈ rich ＜ rich/lean ＜ lean ageing conditions. Rh dispersion and presence of isolated Rh sites, revealed from in-situ FT-IR spectroscopy following CO adsorption, were responsible for the high light-off activity. NO conversion in higher temperature regions under lean/rich perturbation conditions was influenced by the ageing atmosphere. H 2 -TPR measurements suggested the formation of Rh _ CZ interactions with different strengths depending on the atmosphere during high-tempera-ture ageing. The strength of the Rh _ CZ interaction was suspected to be important to achieve high NO conversion in higher temperature regions.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87228861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Han Yu, Lin Ma, Kenji Wada, Ryohsuke Kurihara, Q. Feng, S. Uemura, Kyosuke Isoda
Iridium catalysts supported on anatase with high surface area showed excellent activities for the acceptor-less dehydrogenation synthesis of benzoxazoles from 2-aminophenol and primary alcohols. The catalytic activity greatly depended on the titania supports, iridium precursors, and loading of iridium species. Catalysts supported on anatase JRC (Japan Reference Catalyst)-TIO-10 showed the highest activity for the dehydrogenative reaction. Preparation of catalysts using [Ir(cod)Cl] 2 (cod ＝ 1,5-cyclooctadiene) as an iridium precursor resulted in higher activity than using Ir(acac) 3 (acac ＝ acetylacetonate). Various primary alcohols were reacted to give corresponding benzoxazoles in high to moderate yields. The catalyst could be recycled without significant loss of activity, and no leaching of iridium species occurred into the solution. The hot filtration test strongly suggested that the catalysis occurs on the catalyst surface. Highly dispersed iridium species of less than 2 nm in diameter, which could be reduced at low temperature, were responsible for the excellent activity.
{"title":"Development of Titania-supported Iridium Catalysts for the Acceptor-less Dehydrogenative Synthesis of Benzoxazoles","authors":"Han Yu, Lin Ma, Kenji Wada, Ryohsuke Kurihara, Q. Feng, S. Uemura, Kyosuke Isoda","doi":"10.1627/JPI.64.271","DOIUrl":"https://doi.org/10.1627/JPI.64.271","url":null,"abstract":"Iridium catalysts supported on anatase with high surface area showed excellent activities for the acceptor-less dehydrogenation synthesis of benzoxazoles from 2-aminophenol and primary alcohols. The catalytic activity greatly depended on the titania supports, iridium precursors, and loading of iridium species. Catalysts supported on anatase JRC (Japan Reference Catalyst)-TIO-10 showed the highest activity for the dehydrogenative reaction. Preparation of catalysts using [Ir(cod)Cl] 2 (cod ＝ 1,5-cyclooctadiene) as an iridium precursor resulted in higher activity than using Ir(acac) 3 (acac ＝ acetylacetonate). Various primary alcohols were reacted to give corresponding benzoxazoles in high to moderate yields. The catalyst could be recycled without significant loss of activity, and no leaching of iridium species occurred into the solution. The hot filtration test strongly suggested that the catalysis occurs on the catalyst surface. Highly dispersed iridium species of less than 2 nm in diameter, which could be reduced at low temperature, were responsible for the excellent activity.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90183565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The aromatization of light alkanes including ethane, propane, and n-hexane is an important process for producing value-added aromatic compounds, especially benzene, toluene, and xylenes (BTX), because the aromatization process can be adapted to use natural gas, to meet the increased demands for raw chemicals in the petrochemical industry in recent decades. For the aromatization of alkanes, various metal-loaded zeolite catalysts based on ZSM-51)~14), MCM-2215), ZSM-1116), and L zeolite17)~21) have been extensively developed. In particular, Znor Ga-containing ZSM-5 provides high catalytic activities and selectivities for aromatic compounds because of the combination of the dehydrogenation over the metal species and Brønsted acidity of the ZSM-5 zeolite1),3),5),6),10). Furthermore, the metal species are highly dispersed on ZSM-5 through the replacement of protons on ZSM-5 with the metal species by ion exchange and reducing-oxidizing treatment to provide active sites such as cationic metal species instead of bulk ZnO and Ga2O322)~25). Since the aromatization of alkanes fundamentally proceeds via the dehydrogenation of alkanes, it is important to increase the number of active metal sites for improving the catalytic performances. The incorporation of metal species into the framework of zeolite through the hydrothermal synthesis leads to the formation of highly dispersed and isolated metal species in the zeolite. In addition, the incorporation of trivalent Ga species, instead of Al species, into the zeolite framework generates Brønsted acid sites with weaker acidity than those generated by the incorporation of Al species24), resulting in a bifunctional catalyst for the aromatization of alkanes26)~30). We previously found that Zn-containing MFI zeolite synthesized by the hydrothermal treatment in the absence of Al species exhibited a high catalytic activity for the dehydrogenation of n-butane to produce 1,3-butadiene31). Introducing Zn species into the zeolite would form isolated active Zn sites with high dehydrogenation activity. Therefore, it is expected that the formation of both isolated Zn and Ga sites in zeolite would improve the catalytic performances of zeolite catalysts for the aromatization (dehydrocyclization) of alkanes to selectively produce BTX. Here we report the direct synthesis of MFI-type zeo[Research Note]
{"title":"Synthesis of Zeolite Catalysts Containing Zn and Ga for Aromatization of n-Hexane","authors":"Hiroyuki Imai, Maika Takada, Y. Ike","doi":"10.1627/JPI.64.293","DOIUrl":"https://doi.org/10.1627/JPI.64.293","url":null,"abstract":"The aromatization of light alkanes including ethane, propane, and n-hexane is an important process for producing value-added aromatic compounds, especially benzene, toluene, and xylenes (BTX), because the aromatization process can be adapted to use natural gas, to meet the increased demands for raw chemicals in the petrochemical industry in recent decades. For the aromatization of alkanes, various metal-loaded zeolite catalysts based on ZSM-51)~14), MCM-2215), ZSM-1116), and L zeolite17)~21) have been extensively developed. In particular, Znor Ga-containing ZSM-5 provides high catalytic activities and selectivities for aromatic compounds because of the combination of the dehydrogenation over the metal species and Brønsted acidity of the ZSM-5 zeolite1),3),5),6),10). Furthermore, the metal species are highly dispersed on ZSM-5 through the replacement of protons on ZSM-5 with the metal species by ion exchange and reducing-oxidizing treatment to provide active sites such as cationic metal species instead of bulk ZnO and Ga2O322)~25). Since the aromatization of alkanes fundamentally proceeds via the dehydrogenation of alkanes, it is important to increase the number of active metal sites for improving the catalytic performances. The incorporation of metal species into the framework of zeolite through the hydrothermal synthesis leads to the formation of highly dispersed and isolated metal species in the zeolite. In addition, the incorporation of trivalent Ga species, instead of Al species, into the zeolite framework generates Brønsted acid sites with weaker acidity than those generated by the incorporation of Al species24), resulting in a bifunctional catalyst for the aromatization of alkanes26)~30). We previously found that Zn-containing MFI zeolite synthesized by the hydrothermal treatment in the absence of Al species exhibited a high catalytic activity for the dehydrogenation of n-butane to produce 1,3-butadiene31). Introducing Zn species into the zeolite would form isolated active Zn sites with high dehydrogenation activity. Therefore, it is expected that the formation of both isolated Zn and Ga sites in zeolite would improve the catalytic performances of zeolite catalysts for the aromatization (dehydrocyclization) of alkanes to selectively produce BTX. Here we report the direct synthesis of MFI-type zeo[Research Note]","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90351043","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Methods to catalytic conversion of glucose into lactic acid (LA), which is a versatile platform chemical, have been widely investigated. Herein, various kinds of metal oxide catalysts were used for lactic acid (LA) production from glucose under strong homogeneous base-free conditions. Among the metal oxides tested, Y 2 O 3 afforded LA in moderate yield (33 %) together with trioses (dihydroxyacetone and glyceraldehyde) and fructose. It was found that the Y 2 O 3 /SiO 2 catalyst can effectively catalyze the transformation of glucose into LA. Compared to Y 2 O 3 , the LA yield was remarkably improved (45 %). The characterization results showed that Y(OH) 3 was highly dispersed on the Y 2 O 3 /SiO 2 catalyst, acting as a Brønsted base and promoting LA formation from pyruvaldehyde (PA). Brønsted acid sites (hydroxyl groups) located at the interface between Y(OH) 3 and SiO 2 promoted the dehydration of trioses to form PA. The acid and base sites on the Y 2 O 3 /SiO 2 catalyst functioned in concert to ensure that the overall reaction proceeded efficiently.
{"title":"Lactic Acid Production from Glucose over Y 2 O 3 -based Catalysts under Base-free Conditions","authors":"Daichi Hata, T. Aihara, H. Miura, T. Shishido","doi":"10.1627/JPI.64.280","DOIUrl":"https://doi.org/10.1627/JPI.64.280","url":null,"abstract":"Methods to catalytic conversion of glucose into lactic acid (LA), which is a versatile platform chemical, have been widely investigated. Herein, various kinds of metal oxide catalysts were used for lactic acid (LA) production from glucose under strong homogeneous base-free conditions. Among the metal oxides tested, Y 2 O 3 afforded LA in moderate yield (33 %) together with trioses (dihydroxyacetone and glyceraldehyde) and fructose. It was found that the Y 2 O 3 /SiO 2 catalyst can effectively catalyze the transformation of glucose into LA. Compared to Y 2 O 3 , the LA yield was remarkably improved (45 %). The characterization results showed that Y(OH) 3 was highly dispersed on the Y 2 O 3 /SiO 2 catalyst, acting as a Brønsted base and promoting LA formation from pyruvaldehyde (PA). Brønsted acid sites (hydroxyl groups) located at the interface between Y(OH) 3 and SiO 2 promoted the dehydration of trioses to form PA. The acid and base sites on the Y 2 O 3 /SiO 2 catalyst functioned in concert to ensure that the overall reaction proceeded efficiently.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81235794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Effects of arylimido ligands on the ring-opening metathesis polymerization (ROMP) of norbornene (NBE), norbornadiene (NBD), and tetracyclododecene (TCD) were investigated using a series of (arylimido)niobium(V) _ alkylidene complex catalysts, Nb(CHSiMe 3 )(NAr)[OC(CF 3 ) 3 ](PMe 3 ) 2 [Ar ＝ 2,6-Me 2 C 6 H 3 ( 1 ), 2-MeC 6 H 4 ( 2 ), 2,6-Cl 2 C 6 H 3 ( 3 )]. The catalytic activity in ROMP of NBE for 1 was higher than for 2 and 3 (toluene at 25 °C, initial NBE concentration 0.44 mmol/mL), and the activity increased at 50 °C. Further increase in the activity (TOF 236 s –1 ) was observed using 3 with addition of 1.0 equiv. of PMe 3 , and activity was higher than that for the analogous vanadium(V) _ alkylidene. These complexes ( 1 - 3 ) could also catalyze ROMP of NBD and TCD and the activities were higher than that for the ROMP of NBE. The dichlorophenylimido analogue ( 3 ) showed the highest activity for the ROMP of TCD, whereas 1 showed higher activity than 2 and 3 for the ROMP of NBD.
{"title":"Ring Opening Metathesis Polymerization (ROMP) of Norbornenes by (Arylimido)Niobium(V)–Alkylidene Catalysts, Nb(CHSiMe 3 )(NAr)[OC(CF 3 ) 3 ](PMe 3 ) 2","authors":"Kanchana Chatchaipaiboon, K. Nomura","doi":"10.1627/JPI.64.238","DOIUrl":"https://doi.org/10.1627/JPI.64.238","url":null,"abstract":"Effects of arylimido ligands on the ring-opening metathesis polymerization (ROMP) of norbornene (NBE), norbornadiene (NBD), and tetracyclododecene (TCD) were investigated using a series of (arylimido)niobium(V) _ alkylidene complex catalysts, Nb(CHSiMe 3 )(NAr)[OC(CF 3 ) 3 ](PMe 3 ) 2 [Ar ＝ 2,6-Me 2 C 6 H 3 ( 1 ), 2-MeC 6 H 4 ( 2 ), 2,6-Cl 2 C 6 H 3 ( 3 )]. The catalytic activity in ROMP of NBE for 1 was higher than for 2 and 3 (toluene at 25 °C, initial NBE concentration 0.44 mmol/mL), and the activity increased at 50 °C. Further increase in the activity (TOF 236 s –1 ) was observed using 3 with addition of 1.0 equiv. of PMe 3 , and activity was higher than that for the analogous vanadium(V) _ alkylidene. These complexes ( 1 - 3 ) could also catalyze ROMP of NBD and TCD and the activities were higher than that for the ROMP of NBE. The dichlorophenylimido analogue ( 3 ) showed the highest activity for the ROMP of TCD, whereas 1 showed higher activity than 2 and 3 for the ROMP of NBD.","PeriodicalId":17362,"journal":{"name":"Journal of The Japan Petroleum Institute","volume":null,"pages":null},"PeriodicalIF":1.0,"publicationDate":"2021-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86642053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","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：