A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol(5-AP)from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal(5-HP,via the ring-openin...A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol(5-AP)from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal(5-HP,via the ring-opening tautomerization of 2-hydroxytetrahydropyran(2-HTHP))and its reductive amination over supported Ni catalysts.The catalytic performances of the supported Ni catalysts on different oxides including SiO2,TiO2,ZrO2,γ-Al2 O3,and MgO as well as several commercial hydrogenation catalysts were investigated.The Ni/ZrO2 catalyst presented the highest 5-AP yield.The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO2 catalyst possessed high reducibility and a high surface acid density,which lead to the enhanced activity and selectivity of the catalyst.The effect of reaction parameters on the catalytic performance of the Ni/ZrO2 catalyst was studied,and a high 5-AP yield of 90.8%was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80℃and 2 MPa H2.The stability of the Ni/ZrO2 catalyst was studied using a continuous flow reactor,and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream.Additionally,the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.展开更多
The efficient synthesis of useful primary amines via reductive amination of biomass-based aldehydes and ketones over earth-abundant base metal catalysts is an attractive biomass value-adding technology yet facing lots...The efficient synthesis of useful primary amines via reductive amination of biomass-based aldehydes and ketones over earth-abundant base metal catalysts is an attractive biomass value-adding technology yet facing lots of challenges.Herein,natural attapulgite(ATP)was applied as support for the fabrication of active Ni catalysts with different Ni loadings(5–30 wt%)by the deposition-precipitation method.The Ni/ATP-550 catalyst with 10–15 wt%Ni loadings was found to present the highest catalytic performance for the synthesis of valuable 5-amino-1-pentanol(5-AP)via reductive amination of biofurfural-derived 2-hydroxytetrahydropyran among a variety of commonly used oxide supports loaded Ni catalysts,as well as ATP supported nickel catalysts with other loadings,achieving 5-AP yield up to 94%.The intrinsic activity of the Ni/ATP catalysts was found to depend strongly on the Ni^(0) crystallite size and Ni^(0) fraction of the catalysts,which generally increased with increasing Ni^(0) crystallite size and fraction,owing probably to the hydrogenation of imine intermediate is a structure-sensitive reaction.The efficient 10Ni/ATP-550 catalyst also exhibited good activity and stability in the reductive amination of several other biomass-derived aldehydes and ketones to their corresponding primary amines with good to excellent yields(81%–99%).This work provided a clean and efficient natural ATP-supported non-noble metal nickel-based catalytic system for the reductive amination of aldehydes and ketones to synthesize high-value-added primary amines,which could be a promising candidate for the industrial production of amines.展开更多
基金supported by the National Natural Science Foundation of China(21872155,21473224)Cooperation Foundation of Dalian National Laboratory for Clean Energy(DNL 180303)+2 种基金Key Research Project of Frontier Science of Chinese Academy of Sciences(QYZDJ-SSW-SLH051)the Youth Innovation Promotion Association,CAS(2016371)the Suzhou Science and Technology Development Plan(SYG201626)~~
文摘A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol(5-AP)from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal(5-HP,via the ring-opening tautomerization of 2-hydroxytetrahydropyran(2-HTHP))and its reductive amination over supported Ni catalysts.The catalytic performances of the supported Ni catalysts on different oxides including SiO2,TiO2,ZrO2,γ-Al2 O3,and MgO as well as several commercial hydrogenation catalysts were investigated.The Ni/ZrO2 catalyst presented the highest 5-AP yield.The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO2 catalyst possessed high reducibility and a high surface acid density,which lead to the enhanced activity and selectivity of the catalyst.The effect of reaction parameters on the catalytic performance of the Ni/ZrO2 catalyst was studied,and a high 5-AP yield of 90.8%was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80℃and 2 MPa H2.The stability of the Ni/ZrO2 catalyst was studied using a continuous flow reactor,and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream.Additionally,the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21872155 and 22102198)the Strategic Pilot Science and Technology Project of the Chinese Academy of Sciences(No.XDA21010700)the Western Young Scholar Program of the Chinese Academy of Sciences and the Open Project of Key Laboratory of Clay Mineral Applied Research of Gansu Province.
文摘The efficient synthesis of useful primary amines via reductive amination of biomass-based aldehydes and ketones over earth-abundant base metal catalysts is an attractive biomass value-adding technology yet facing lots of challenges.Herein,natural attapulgite(ATP)was applied as support for the fabrication of active Ni catalysts with different Ni loadings(5–30 wt%)by the deposition-precipitation method.The Ni/ATP-550 catalyst with 10–15 wt%Ni loadings was found to present the highest catalytic performance for the synthesis of valuable 5-amino-1-pentanol(5-AP)via reductive amination of biofurfural-derived 2-hydroxytetrahydropyran among a variety of commonly used oxide supports loaded Ni catalysts,as well as ATP supported nickel catalysts with other loadings,achieving 5-AP yield up to 94%.The intrinsic activity of the Ni/ATP catalysts was found to depend strongly on the Ni^(0) crystallite size and Ni^(0) fraction of the catalysts,which generally increased with increasing Ni^(0) crystallite size and fraction,owing probably to the hydrogenation of imine intermediate is a structure-sensitive reaction.The efficient 10Ni/ATP-550 catalyst also exhibited good activity and stability in the reductive amination of several other biomass-derived aldehydes and ketones to their corresponding primary amines with good to excellent yields(81%–99%).This work provided a clean and efficient natural ATP-supported non-noble metal nickel-based catalytic system for the reductive amination of aldehydes and ketones to synthesize high-value-added primary amines,which could be a promising candidate for the industrial production of amines.
