High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we...High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.展开更多
A novel Zn-based metal–organic framework Zn(dobdc)(datz)[Zn_(2)(H2dobdc)(datz)2$1.5DMF]with plentiful hydrogen bond donors(HBD)groups was facilely synthesized from mixed ligands.The dual activation of metal Zn sites ...A novel Zn-based metal–organic framework Zn(dobdc)(datz)[Zn_(2)(H2dobdc)(datz)2$1.5DMF]with plentiful hydrogen bond donors(HBD)groups was facilely synthesized from mixed ligands.The dual activation of metal Zn sites and HBD groups for epoxides by forming Zn–O adduct and hydrogen bonds facilitated the ring-opening of epoxide substrate,which is critical for the subsequent CO_(2) fixation.Also,the existence of micropores and N-rich units in Zn(dobdc)(datz)afforded affinity towards CO_(2),which is beneficial to further improvement on catalytic CO_(2) conversion performance.Satisfactorily,Zn(dobdc)(datz)/Bu4NBr system was proved efficient heterogeneous catalyst for the CO_(2) cycloaddition with epoxides,and 98%propylene carbonate yield was obtained under mild conditions(80C,1.5 MPa and solvent-free).In addition,Zn(dobdc)(datz)/Bu4NBr exhibited remarkable versatility to different epoxides and could be completely recycled over six runs with high catalytic activity.The highly stable,easily recycle and solvent-free Zn-based MOF reported here displays eco-friendly and efficient performance to CO_(2)conversion.展开更多
Separation of products from ionic liquid(IL) solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone(GVL) by selective hydrogenation of α-angelica lact...Separation of products from ionic liquid(IL) solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone(GVL) by selective hydrogenation of α-angelica lactone(AL) and separation of the products from the IL solvent were carried out by using subcritical CO_2 as a "switch" at room temperature. After the mixture was separated into two phases by subcritical CO_2, AL and nano Pd/C catalyst were only found in the lower IL-rich phase, GVL was produced with quantitative yield and enriched in the upper methanolrich phase. Pure GVL can be obtained by depressurizing to release CO_2 and evaporation to remove methanol of the upper phase, the lower phase containing IL, catalyst and methanol can be recycled for the next reaction. The strategy may provide a new approach to produce and separate products from IL solvents at mild conditions.展开更多
基金This work was financially supported by the National Natural Science Foundation of China(No.21722604)the Postdoctoral Foundation of China(Nos.2019M651743 and 2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20190852)the National Youth Natural Science Foundation(No.8111310009).
文摘High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.
基金the National Natural Science Foundation of China(21972034,21673060)the State Key Lab of Urban Water Resource and Environment of Harbin Institute of Technology(HIT2019DX12).
文摘A novel Zn-based metal–organic framework Zn(dobdc)(datz)[Zn_(2)(H2dobdc)(datz)2$1.5DMF]with plentiful hydrogen bond donors(HBD)groups was facilely synthesized from mixed ligands.The dual activation of metal Zn sites and HBD groups for epoxides by forming Zn–O adduct and hydrogen bonds facilitated the ring-opening of epoxide substrate,which is critical for the subsequent CO_(2) fixation.Also,the existence of micropores and N-rich units in Zn(dobdc)(datz)afforded affinity towards CO_(2),which is beneficial to further improvement on catalytic CO_(2) conversion performance.Satisfactorily,Zn(dobdc)(datz)/Bu4NBr system was proved efficient heterogeneous catalyst for the CO_(2) cycloaddition with epoxides,and 98%propylene carbonate yield was obtained under mild conditions(80C,1.5 MPa and solvent-free).In addition,Zn(dobdc)(datz)/Bu4NBr exhibited remarkable versatility to different epoxides and could be completely recycled over six runs with high catalytic activity.The highly stable,easily recycle and solvent-free Zn-based MOF reported here displays eco-friendly and efficient performance to CO_(2)conversion.
基金supported by International S&T Cooperation Program of China(2014DFA61670)External Cooperation Program of BIC,Chinese Academy of Sciences(GJHZ201306)National Natural Science Foundation of China(No.21276260,21576269,21476245,21406230)
文摘Separation of products from ionic liquid(IL) solvents is one of the main challenges that hinder their utilizations. In this study, the production of γ-valerolactone(GVL) by selective hydrogenation of α-angelica lactone(AL) and separation of the products from the IL solvent were carried out by using subcritical CO_2 as a "switch" at room temperature. After the mixture was separated into two phases by subcritical CO_2, AL and nano Pd/C catalyst were only found in the lower IL-rich phase, GVL was produced with quantitative yield and enriched in the upper methanolrich phase. Pure GVL can be obtained by depressurizing to release CO_2 and evaporation to remove methanol of the upper phase, the lower phase containing IL, catalyst and methanol can be recycled for the next reaction. The strategy may provide a new approach to produce and separate products from IL solvents at mild conditions.
