The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influenc...The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influence on fluid mixing and oil conversion was investigated for a range of operating conditions: Reynolds number(Re = 0.1–100),Temperature(25–75 °C), ethanol/oil molar ratio(6-12), and catalyst concentration(0.75 wt%–1.25 wt%), using three microchannel configurations(Length = 35 mm; Width = 1500 μm; Height = 200 μm): T-shape – channel without obstructions; MCO – channel with 3 obstructions ensemble – equally disposed over longitudinal length;MWO – channel with 7 obstructions ensemble. The MCO micromixer was based on literature work, and the MWO is a totally new micromixer design. Experimental tests were conducted in similar conditions in microreactors using these micromixers(Length = 411 mm) made of polydimethylsiloxane. The MCO configuration presented the highest performance(mixing index of 0.80 at Re = 100), oil conversion of 81.13% at 75 °C, molar ratio of 9 and catalyst concentration of 1%. Experimental results showed high conversions for MCO and MWO configurations(99.99%) at 50 °C, molar ratio of 9 and catalyst concentration of 1%, with a residence time of 12 s.展开更多
The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features ...The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features of these compounds were described, and the possible mechanism of the novel transesterification was suggested.展开更多
The objective of the present study is to examine and compare the performance and emission characteristic of two biodiesel fuels produced from rapeseed oil via transesterification method.Tested biodiesel fuels(ROME(Rap...The objective of the present study is to examine and compare the performance and emission characteristic of two biodiesel fuels produced from rapeseed oil via transesterification method.Tested biodiesel fuels(ROME(Rapeseed Oil Methyl Ester)and ROEE(Rapeseed Oil Ethyl Ester))were selected based on their properties obtained from an optimization of transesterification conditions.A Yanmar diesel engine has led to evaluating their performance parameters such as fuel consumption rate,exhaust gas temperature and emission characteristic corresponding to nitrogen oxides(NOx),carbone monoxide(CO)and carbon dioxide(CO2).A comparative analysis was carried out using normal diesel fuel tested in same experimental conditions.Fuel consumption rate was measured by observing the volumetric rate from the fuel tank of the engine supported by stopwatch.The exhaust gas temperature and emission characteristic were measured simultaneously by using a testo 350 flue gas analyzer.According to the results,biodiesel fuels showed a higher fuel consumption rate and exhaust gas temperature under an increase of engine speed.They also exhibited lower NOx emission with a slight rise in CO and CO2 emission compared to mineral diesel fuel.ROME exhibited low emission gas compared to ROEE and mineral diesel.It can be evaluated as a promising alternative fuel for diesel engine.展开更多
A new methodology for the synthesis of a green plasticizer acetyltributylcitrate through a transesterification reaction was developed. Under the catalysis of alkyl-substituted imidazol-type N-heterocyclic carbenes, tr...A new methodology for the synthesis of a green plasticizer acetyltributylcitrate through a transesterification reaction was developed. Under the catalysis of alkyl-substituted imidazol-type N-heterocyclic carbenes, tributyl citrate can react with vinyl acetate smoothly to give ATBC in high yield.展开更多
Kinetic resolution of racemic 2-chloro-1-(3,4-dichlorophenyl)ethanol was performed by free Alcaligene sp. lipase-catalyzed irreversible transesterification affording the (R)-isomer with ≥95% ee and the (S)-isom...Kinetic resolution of racemic 2-chloro-1-(3,4-dichlorophenyl)ethanol was performed by free Alcaligene sp. lipase-catalyzed irreversible transesterification affording the (R)-isomer with ≥95% ee and the (S)-isomer with ≥90% ee. The activity of lipase Alcaligene sp. strongly depends on the basicity of the reaction system, and an organic base such as triethylamine can enhance the activity of the lipase and enantioselectivity markedly.展开更多
Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-a...Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-anchoring strategy is employed,in which the Mg net is sublimated,transported by Ar,and trapped by defective graphene(producing Mg_(1)/G).Simulated and experimental results demonstrate that Mg single atoms are anchored on graphene in tetra-coordination,and Mg single atoms cooperating with C atoms give superbasicity,which differs from conventional alkali/alkaline earth metal oxides with basicity originating from O atoms.This new solid base is highly active in the synthesis of dimethyl carbonate through transesterification of ethylene carbonate with methanol,which is usually catalyzed by strong bases.The turnover frequency value reaches 99.6 h^(-1) on Mg_(1)/G,which is much higher than that of traditional Mg-related counterparts(1.0–5.6 h^(-1))and even superior to that of typical Na and K-related solid superbases(29.8–36.2 h^(-1))under similar conditions.展开更多
The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for th...The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for the preparation of polymers in a more sustainable way.Nevertheless,due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure,the cross-link density of materials is frequently lowered.In this study,hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids,which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers.It was completely characterized by differential scanning calorimetry test,thermogravimetric analysis,shape memory test and self-healing test.The prepared vitrimers exhibited good self-healing properties,excellent heat resistance(T_(d)=352℃)as well as high mechanical properties(tensile strength of 46.75 MPa).The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton.Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy.Moreover,our work expanded the application field of rosin,increased the added value of rosin,and provided a novel method for preparing rosin-based vitrimers with ideal properties.展开更多
Ordered porous solid strong bases(OPSSBs)have attracted great research interest due to the excellent performance as heterogeneous catalysts in various reactions.The main obstacle for fabricating OPSSBs is the requirem...Ordered porous solid strong bases(OPSSBs)have attracted great research interest due to the excellent performance as heterogeneous catalysts in various reactions.The main obstacle for fabricating OPSSBs is the requirement of high temperature to produce strong basicity on ordered porous materials.For example,the temperatures of 600-650℃ are required for the decomposition of base precursor NaNO_(3)to basic sites on mesoporous silica SBA-15 and zeolite Y.Such high decomposition temperatures are energy-intensive and harmful to the structure of supports.Herein,we report the fabrication of OPSSBs by utilizing the redox interaction between base precursor and low-valence metal centers(e.g.,Cr^(3+))in metal-organic frameworks(MOFs).The base precursor NaNO_(3)on MIL-101(Cr)can be converted to basic sites entirely at 300℃,which is quite lower than those of the conventional thermal conversion on SBA-15 and zeolite Y(600-650℃).The exploration on decomposition mechanism reveals that the valence change of Cr^(3+)to Cr^(6+)takes place during the conversion of NaNO_(3)to basic sites.In this way,MOFs-derived base catalysts have been synthesized successfully by the host-guest redox strategy and exhibit high catalytic activity in typical base-catalyzed reactions.展开更多
The preparation and regeneration conditions of the identified catalyst X/Y/MgO/?-Al2O3 with high catalytic activity were studied and optimized. The biodiesel was prepared by transesterification of Jatropha curcas see...The preparation and regeneration conditions of the identified catalyst X/Y/MgO/?-Al2O3 with high catalytic activity were studied and optimized. The biodiesel was prepared by transesterification of Jatropha curcas seed oil produced in Guizhou with methanol at its reflux temoerature in the presence of X/Y/MgO/?-Al2O3 . The pilot plant tests were carried out in a 100 L reaction vessel. Both average yield and fatty acid methyl esters (FAME) content reached more than 96.50% under the optimum reaction conditions of the pilot plant tests designed with an oil/methanol molar ratio of 1 : 10, catalyst concentration of 1.00%, and reaction time of 3 h at reflux temperature. In addition, analysis shows that the quality of biodiesel meets the standard EN 14214.展开更多
基金the Unicamp Scholarship Program,CAPES and the financial support provided by FAPESP(Sao Paulo Research Foundation,Process 2013/25850-7)Prof.Dr.Milton Mori for giving space to perform the simulations and the Microfabrication Laboratory(Proposal LMF-19844)
文摘The present paper studied numerical and experimentally the transesterification reaction between sunflower oil and ethanol with NaO H catalyst in microchannels with circular obstructions. The micromixer design influence on fluid mixing and oil conversion was investigated for a range of operating conditions: Reynolds number(Re = 0.1–100),Temperature(25–75 °C), ethanol/oil molar ratio(6-12), and catalyst concentration(0.75 wt%–1.25 wt%), using three microchannel configurations(Length = 35 mm; Width = 1500 μm; Height = 200 μm): T-shape – channel without obstructions; MCO – channel with 3 obstructions ensemble – equally disposed over longitudinal length;MWO – channel with 7 obstructions ensemble. The MCO micromixer was based on literature work, and the MWO is a totally new micromixer design. Experimental tests were conducted in similar conditions in microreactors using these micromixers(Length = 411 mm) made of polydimethylsiloxane. The MCO configuration presented the highest performance(mixing index of 0.80 at Re = 100), oil conversion of 81.13% at 75 °C, molar ratio of 9 and catalyst concentration of 1%. Experimental results showed high conversions for MCO and MWO configurations(99.99%) at 50 °C, molar ratio of 9 and catalyst concentration of 1%, with a residence time of 12 s.
基金This work was supported by the National Natural Science Foundation of China(No.20173050)Natural Science Foundation of Shandong Province(No.Z2002F01).
文摘The title compounds, PhX2SnCHECHECO2Me (X = C1, 1a; Br, 1b; I, 1c), readily underwent transesterification into the corresponding analogues, PhX2SnCH2CH2CO2R when reacted with an alcohol ROH. The structural features of these compounds were described, and the possible mechanism of the novel transesterification was suggested.
基金This work was supported by the JICA(Japan International Cooperation Agency)through the program of ABE Initiative(African Business Education Initiative for Youth)and the collaboration with Kumamoto University.
文摘The objective of the present study is to examine and compare the performance and emission characteristic of two biodiesel fuels produced from rapeseed oil via transesterification method.Tested biodiesel fuels(ROME(Rapeseed Oil Methyl Ester)and ROEE(Rapeseed Oil Ethyl Ester))were selected based on their properties obtained from an optimization of transesterification conditions.A Yanmar diesel engine has led to evaluating their performance parameters such as fuel consumption rate,exhaust gas temperature and emission characteristic corresponding to nitrogen oxides(NOx),carbone monoxide(CO)and carbon dioxide(CO2).A comparative analysis was carried out using normal diesel fuel tested in same experimental conditions.Fuel consumption rate was measured by observing the volumetric rate from the fuel tank of the engine supported by stopwatch.The exhaust gas temperature and emission characteristic were measured simultaneously by using a testo 350 flue gas analyzer.According to the results,biodiesel fuels showed a higher fuel consumption rate and exhaust gas temperature under an increase of engine speed.They also exhibited lower NOx emission with a slight rise in CO and CO2 emission compared to mineral diesel fuel.ROME exhibited low emission gas compared to ROEE and mineral diesel.It can be evaluated as a promising alternative fuel for diesel engine.
基金financial support of the Doctor Foundation of Bingtuan(No.2011BB011)and Shihezi University
文摘A new methodology for the synthesis of a green plasticizer acetyltributylcitrate through a transesterification reaction was developed. Under the catalysis of alkyl-substituted imidazol-type N-heterocyclic carbenes, tributyl citrate can react with vinyl acetate smoothly to give ATBC in high yield.
基金Project supported by the Doctoral Foundation of Qingdao University of Science and Technology (No. 0022266), the Program for New Century Excellent Talents in Universities (No. NCET-04-0649), and the Natural Science Foundation of Shandong Province (No. Z2006B01).
文摘Kinetic resolution of racemic 2-chloro-1-(3,4-dichlorophenyl)ethanol was performed by free Alcaligene sp. lipase-catalyzed irreversible transesterification affording the (R)-isomer with ≥95% ee and the (S)-isomer with ≥90% ee. The activity of lipase Alcaligene sp. strongly depends on the basicity of the reaction system, and an organic base such as triethylamine can enhance the activity of the lipase and enantioselectivity markedly.
基金supported by the National Science Fund for Distinguished Young Scholars(22125804)the National Natural Science Foundation of China(22078155,21878149,U20A20151)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘Magnesium-related solid bases have long been considered catalysts with weak or medium basicity.Here we report the fabrication of Mg single-atom catalysts with superbasicity for the first time.A sublimation-migration-anchoring strategy is employed,in which the Mg net is sublimated,transported by Ar,and trapped by defective graphene(producing Mg_(1)/G).Simulated and experimental results demonstrate that Mg single atoms are anchored on graphene in tetra-coordination,and Mg single atoms cooperating with C atoms give superbasicity,which differs from conventional alkali/alkaline earth metal oxides with basicity originating from O atoms.This new solid base is highly active in the synthesis of dimethyl carbonate through transesterification of ethylene carbonate with methanol,which is usually catalyzed by strong bases.The turnover frequency value reaches 99.6 h^(-1) on Mg_(1)/G,which is much higher than that of traditional Mg-related counterparts(1.0–5.6 h^(-1))and even superior to that of typical Na and K-related solid superbases(29.8–36.2 h^(-1))under similar conditions.
基金This research was supported by the National Natural Science Foundation of China(Grant No.32171734)the Scientific Research Funds of Huaqiao University(Grant No.20BS201).
文摘The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for the preparation of polymers in a more sustainable way.Nevertheless,due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure,the cross-link density of materials is frequently lowered.In this study,hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids,which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers.It was completely characterized by differential scanning calorimetry test,thermogravimetric analysis,shape memory test and self-healing test.The prepared vitrimers exhibited good self-healing properties,excellent heat resistance(T_(d)=352℃)as well as high mechanical properties(tensile strength of 46.75 MPa).The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton.Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy.Moreover,our work expanded the application field of rosin,increased the added value of rosin,and provided a novel method for preparing rosin-based vitrimers with ideal properties.
基金This work was supported by the National Natural Science Foundation of China(Nos.21878149,22078155 and 21722606)National Science Fund for Distinguished Young Scholars(No.22125804)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Ordered porous solid strong bases(OPSSBs)have attracted great research interest due to the excellent performance as heterogeneous catalysts in various reactions.The main obstacle for fabricating OPSSBs is the requirement of high temperature to produce strong basicity on ordered porous materials.For example,the temperatures of 600-650℃ are required for the decomposition of base precursor NaNO_(3)to basic sites on mesoporous silica SBA-15 and zeolite Y.Such high decomposition temperatures are energy-intensive and harmful to the structure of supports.Herein,we report the fabrication of OPSSBs by utilizing the redox interaction between base precursor and low-valence metal centers(e.g.,Cr^(3+))in metal-organic frameworks(MOFs).The base precursor NaNO_(3)on MIL-101(Cr)can be converted to basic sites entirely at 300℃,which is quite lower than those of the conventional thermal conversion on SBA-15 and zeolite Y(600-650℃).The exploration on decomposition mechanism reveals that the valence change of Cr^(3+)to Cr^(6+)takes place during the conversion of NaNO_(3)to basic sites.In this way,MOFs-derived base catalysts have been synthesized successfully by the host-guest redox strategy and exhibit high catalytic activity in typical base-catalyzed reactions.
基金supported by the Key Science and Technology Project of Guizhou(No.20076004).
文摘The preparation and regeneration conditions of the identified catalyst X/Y/MgO/?-Al2O3 with high catalytic activity were studied and optimized. The biodiesel was prepared by transesterification of Jatropha curcas seed oil produced in Guizhou with methanol at its reflux temoerature in the presence of X/Y/MgO/?-Al2O3 . The pilot plant tests were carried out in a 100 L reaction vessel. Both average yield and fatty acid methyl esters (FAME) content reached more than 96.50% under the optimum reaction conditions of the pilot plant tests designed with an oil/methanol molar ratio of 1 : 10, catalyst concentration of 1.00%, and reaction time of 3 h at reflux temperature. In addition, analysis shows that the quality of biodiesel meets the standard EN 14214.