The great challenge in the aldol condensation of tailored fermentation products(acetone-butanol-ethanol,ABE)into energy intensive fuels is to develop a suitable catalyst with high activity and low-cost.In this study,C...The great challenge in the aldol condensation of tailored fermentation products(acetone-butanol-ethanol,ABE)into energy intensive fuels is to develop a suitable catalyst with high activity and low-cost.In this study,Co,Ni,and Co-Ni supported on Mg-Al oxide catalysts were prepared and their pore diameters were enlarged via adding active carbon as a hard template into Mg-Al hydrotalcite.During the aldol condensation reaction,the catalyst activity was enhanced after enlarging the pore diameter and Co-Ni bimetal supported catalyst presented the highest activity,which was resulted from that the electron transfer between Co and Ni in Co-Ni alloy enhanced the dehydrogenation activity and large pore lowered the mass transfer resistance.After optimizing the reaction conditions,acetone conversion and the total selectivity of C_(5)-C_(11)desired products in the aldol condensation of ABE reached up to 76%and 90%,respectively.The stability study showed that the activity was decreased with the increase of reaction number because of the oxidation of metallic Co and Ni,but this could be solved via a simple hydrogen reduction method.展开更多
Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(D...Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.展开更多
基金supported by the National Natural Science Foundation of China(No.21776236 and 21676225)Scientific Research Fund of Hunan Provincial Education Department(19A478)+2 种基金Natural Science Foundation of Hunan Province(2018JJ2384)Engineering Research Centre of Chemical Process Simulation and Optimization of Ministry of EducationStudents’innovation and entrepreneurship training program of Hunan province。
文摘The great challenge in the aldol condensation of tailored fermentation products(acetone-butanol-ethanol,ABE)into energy intensive fuels is to develop a suitable catalyst with high activity and low-cost.In this study,Co,Ni,and Co-Ni supported on Mg-Al oxide catalysts were prepared and their pore diameters were enlarged via adding active carbon as a hard template into Mg-Al hydrotalcite.During the aldol condensation reaction,the catalyst activity was enhanced after enlarging the pore diameter and Co-Ni bimetal supported catalyst presented the highest activity,which was resulted from that the electron transfer between Co and Ni in Co-Ni alloy enhanced the dehydrogenation activity and large pore lowered the mass transfer resistance.After optimizing the reaction conditions,acetone conversion and the total selectivity of C_(5)-C_(11)desired products in the aldol condensation of ABE reached up to 76%and 90%,respectively.The stability study showed that the activity was decreased with the increase of reaction number because of the oxidation of metallic Co and Ni,but this could be solved via a simple hydrogen reduction method.
基金supported by the National Key R&D Program of China (2022YFB3805401, 2019YFC1905300)the National Natural Science Foundation of China (22178297)+1 种基金the Hunan Provincial Natural Science Foundation (2022JJ40425, 2022JJ40432)the Process Intensification and Green Chemical Engineering Innovation Team of Hunan Province。
文摘Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.
