Separation of 2-methylfuran(2-MF)and methanol(MeOH)azeotropes is a key challenge in biofuel production because of the efficiency and sustainability issues of conventional methods.In this study,ionic liquids(ILs)were i...Separation of 2-methylfuran(2-MF)and methanol(MeOH)azeotropes is a key challenge in biofuel production because of the efficiency and sustainability issues of conventional methods.In this study,ionic liquids(ILs)were introduced as green solvents for separation of 2-MF/MeOH through liquid–liquid equilibrium(LLE)experiment.Three ILs,namely 1-ethyl-3-methylimidazole dihydrogen phosphate([EMIM][H_(2)PO_(4)]),1-propyl-3-methylimidazole dihydrogen phosphate([PMIM][H_(2)PO_(4)])and 1-butyl-3-methylimidazole dihydrogen phosphate([BMIM][H_(2)PO_(4)]),were screened out from 425 candidates using the conductor-like screening model for real solvents(COSMO-RS).Then,the ternary LLE data of 2-MF(1)+MeOH(2)+ILs(3)were determined at 30℃ and 101.32 kPa.Results confirmed[EMIM][H_(2)PO_(4)]as the best performer,achieving a selectivity of 343.86 and a distribution coefficient of 36.66 for MeOH—significantly higher than[PMIM][H_(2)PO_(4)]and[BMIM][H_(2)PO_(4)].The accuracy of the LLE data was verified by Othmer–Tobias and Hand equations(R^(2)>0.90).The non-random two liquid model was used to correlate the experimental data(RMSD<2%).Besides,the combination of electrostatic surfaces potential,independent gradient model based on Hirshfeld partition,mean square displacement and radial distribution functions revealed strong electrostatic interactions between[H_(2)PO_(4)]^(–) and MeOH.Interaction energy analysis further emphasizes the mechanism of MeOH separation from a mixture of 2-MF and MeOH by ILs.This work provides a multiscale strategy for the separation of 2-MF and MeOH azeotropes,highlighting the potential of ILs to improve biofuel purification while reducing energy and environmental costs.展开更多
Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promo...Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promoted photocycloaddition approach to synthesize a new kind of spiral fuel from biomass-derived cyclohexanone (CHOE) and camphene (CPE).BrΦnsted acids show higher catalytic activity than Lewis acids,and acetic acid (HOAc) possesses the best catalytic performance,with CHOE conversion up to 99.1%.Meanwhile,the HOAc-catalytic effect has been confirmed for[2+2]photocycloaddition of other biomass-derived ketenes and olefins.The catalytic mechanism and dynamics have been investigated,and show that HOAc can bond with C=O groups of CHOE to form H–CHOE complex,which leads to higher light adsorption and longer triplet lifetime.Meanwhile,H–CHOE complex reduces the energy gap between CHOE LUMO and CPE HOMO,shortens the distance of ring-forming atoms,and then decreases the energy barrier (from 103.3 kcal mol^(-1)to 95.8 kcal mol^(-1)) of rate-limiting step.After hydrodeoxygenation,the targeted bio-spiral fuel shows high density of 0.992 g cm^(-3),high neat heat of combustion of 41.89 MJ L^(-1),low kinetic viscosity of 5.69 mm^(2)s^(-1)at 20℃,which is very promising to serve as high-performance aerospace fuel.展开更多
基金supported by the National Natural Science Foundation of China(22278272)Natural Science Foundation of Liaoning Province(2024-MS-129).
文摘Separation of 2-methylfuran(2-MF)and methanol(MeOH)azeotropes is a key challenge in biofuel production because of the efficiency and sustainability issues of conventional methods.In this study,ionic liquids(ILs)were introduced as green solvents for separation of 2-MF/MeOH through liquid–liquid equilibrium(LLE)experiment.Three ILs,namely 1-ethyl-3-methylimidazole dihydrogen phosphate([EMIM][H_(2)PO_(4)]),1-propyl-3-methylimidazole dihydrogen phosphate([PMIM][H_(2)PO_(4)])and 1-butyl-3-methylimidazole dihydrogen phosphate([BMIM][H_(2)PO_(4)]),were screened out from 425 candidates using the conductor-like screening model for real solvents(COSMO-RS).Then,the ternary LLE data of 2-MF(1)+MeOH(2)+ILs(3)were determined at 30℃ and 101.32 kPa.Results confirmed[EMIM][H_(2)PO_(4)]as the best performer,achieving a selectivity of 343.86 and a distribution coefficient of 36.66 for MeOH—significantly higher than[PMIM][H_(2)PO_(4)]and[BMIM][H_(2)PO_(4)].The accuracy of the LLE data was verified by Othmer–Tobias and Hand equations(R^(2)>0.90).The non-random two liquid model was used to correlate the experimental data(RMSD<2%).Besides,the combination of electrostatic surfaces potential,independent gradient model based on Hirshfeld partition,mean square displacement and radial distribution functions revealed strong electrostatic interactions between[H_(2)PO_(4)]^(–) and MeOH.Interaction energy analysis further emphasizes the mechanism of MeOH separation from a mixture of 2-MF and MeOH by ILs.This work provides a multiscale strategy for the separation of 2-MF and MeOH azeotropes,highlighting the potential of ILs to improve biofuel purification while reducing energy and environmental costs.
基金the support from National Key R&D Program of China (2021YFC2103704)the National Natural Science Foundation of China (22222808)+4 种基金the Natural Science Foundation of Shandong Province (ZR2023QB152)the Youth Innovation Team Plan of Shandong Province (2022KJ270)the China National Postdoctoral Program for Innovative Talents (BX20240251)the Aeronautical Science Foundation of China (2023Z073048003)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Photoinduced[2+2]cycloaddition of biomass-derived cycloolefin is a promising approach to synthesize high-energy bio-fuels,however,the conversion efficiency and selectivity are still low.Herein,we provide an acid-promoted photocycloaddition approach to synthesize a new kind of spiral fuel from biomass-derived cyclohexanone (CHOE) and camphene (CPE).BrΦnsted acids show higher catalytic activity than Lewis acids,and acetic acid (HOAc) possesses the best catalytic performance,with CHOE conversion up to 99.1%.Meanwhile,the HOAc-catalytic effect has been confirmed for[2+2]photocycloaddition of other biomass-derived ketenes and olefins.The catalytic mechanism and dynamics have been investigated,and show that HOAc can bond with C=O groups of CHOE to form H–CHOE complex,which leads to higher light adsorption and longer triplet lifetime.Meanwhile,H–CHOE complex reduces the energy gap between CHOE LUMO and CPE HOMO,shortens the distance of ring-forming atoms,and then decreases the energy barrier (from 103.3 kcal mol^(-1)to 95.8 kcal mol^(-1)) of rate-limiting step.After hydrodeoxygenation,the targeted bio-spiral fuel shows high density of 0.992 g cm^(-3),high neat heat of combustion of 41.89 MJ L^(-1),low kinetic viscosity of 5.69 mm^(2)s^(-1)at 20℃,which is very promising to serve as high-performance aerospace fuel.
