The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane s...The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.展开更多
A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can reso...A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants,but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse.The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity.Under the conditions covering a VIL/VTfOH ratio of 10:3,a temperature of 25°C,and a reaction time of 25 min,the C8-product selectivity reaches 86.63%.The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance.After many operating cycles,the hydrophobic PEA-IL can be easily regenerated by simply adding water.This study provides a green,economic,and highly efficient method for producing high-octane alkylate gasoline.展开更多
A series of amino-acid-based ionic liquids was synthesized via one-step protonation of the corresponding L-amiiio acid by utilizing an array of proton sources.The catalytic activity of the amino-acid-based ionic liqui...A series of amino-acid-based ionic liquids was synthesized via one-step protonation of the corresponding L-amiiio acid by utilizing an array of proton sources.The catalytic activity of the amino-acid-based ionic liquids for the Baeyer-Villiger oxidation of cyclic ketones was investigated using cyclopentanone as a model cycloketone.Theproline-based ionic liquid[ProH]CF3SO3 was shown to exliibit thebest catalytic activity.The reaction condition was optimized to give the following reagent ratio of h(cyclopentanone):n(catalyst):w(H2O2)=1:0.06:4,60℃and 6 h.Under the optimum conditions,the conversion of cyclopentanone was 96.57%and the selectivity forδ-valerolactone was 73.01%.The catalytic activity was shown to be constant after 4 cycles.A simple treatment was allowed for the recover and the reuse of[ProH]CF3S03.The successful utilization of[ProH]CF3SO3 to catalyze a host of cyclic ketones via Baeyer-Villiger oxidation clearly demonstrated the capacity of[ProH]CF3S03 to tolerate variation in the substrate.展开更多
基金supported by the National Natural Science Foundation of China (21476120)the Shandong Province Prioritized Development Plan (2017GGX40107)the Taishan Scholar Project of Shandong Province in China (ts201511033)
文摘The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.
基金financially supported by the National Natural Science Foundation of China(Nos.21476120,21805158)the Shandong Province Priority Development Plan of China(Nos.2017GGX40107,2019GGX102021)。
文摘A polyetheramine(PEA)-based Br?nsted-acidic ionic liquid(IL)was firstly prepared and used to promote the alkylation of isobutane with isobutene catalyzed by trifluoromethanesulfonic acid(TfOH).PEA-IL not only can resolve the persistent problem of poor solubility of the volatile and refractory reactants,but also can satisfactorily exhibit the separation of the catalyst from product oil for reuse.The PEA-IL/TfOH catalytic system with an adjustable acidity ensures a high alkylate selectivity.Under the conditions covering a VIL/VTfOH ratio of 10:3,a temperature of 25°C,and a reaction time of 25 min,the C8-product selectivity reaches 86.63%.The PEA-IL/TfOH catalyst can be reused 13 times without a decrease in the catalytic performance.After many operating cycles,the hydrophobic PEA-IL can be easily regenerated by simply adding water.This study provides a green,economic,and highly efficient method for producing high-octane alkylate gasoline.
基金Supported by the National Natural Science Foundation of China(No.21878166)the Taishan Scholar Project of Shandong Province,China(No.ts201511033)+1 种基金the Emphasis Development Plan of Shandong Province,China(Nos.2017GGX70102,2017GGX40107)the Open Project of the Chemistry Department in Qingdao University of Science and Technology of China(No.QUSTHX201811).
文摘A series of amino-acid-based ionic liquids was synthesized via one-step protonation of the corresponding L-amiiio acid by utilizing an array of proton sources.The catalytic activity of the amino-acid-based ionic liquids for the Baeyer-Villiger oxidation of cyclic ketones was investigated using cyclopentanone as a model cycloketone.Theproline-based ionic liquid[ProH]CF3SO3 was shown to exliibit thebest catalytic activity.The reaction condition was optimized to give the following reagent ratio of h(cyclopentanone):n(catalyst):w(H2O2)=1:0.06:4,60℃and 6 h.Under the optimum conditions,the conversion of cyclopentanone was 96.57%and the selectivity forδ-valerolactone was 73.01%.The catalytic activity was shown to be constant after 4 cycles.A simple treatment was allowed for the recover and the reuse of[ProH]CF3S03.The successful utilization of[ProH]CF3SO3 to catalyze a host of cyclic ketones via Baeyer-Villiger oxidation clearly demonstrated the capacity of[ProH]CF3S03 to tolerate variation in the substrate.
