Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their h...Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.展开更多
This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al2O3 catalysts in the oxidative desulfurization （ODS） of dibenzothiophene （DBT） using ...This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al2O3 catalysts in the oxidative desulfurization （ODS） of dibenzothiophene （DBT） using H2O2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60℃ and 150 min reaction time over Fe-Ni-Mo/Al2O3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al2O3 catalysts following the activity order：Fe-Ni-Mo/Al2O3 〉 Fe-Co-Mo/Al2O3 〉 Ni-Mo/Al2O3 〉 Co-Mo/Al2O3, while H2O2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy （SEM）, X-ray diffraction （XRD）, energy dispersive X-ray （EDX） analysis, Atomic Absorption Spectroscopy （AAS） and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.展开更多
Compared with traditional hydrodesulfurization,new nonhydrodesulfurization methods have the advantage of a high removal efficiency for thiophene compounds under mild conditions.However,independent nonhydrodesulfurizat...Compared with traditional hydrodesulfurization,new nonhydrodesulfurization methods have the advantage of a high removal efficiency for thiophene compounds under mild conditions.However,independent nonhydrodesulfurization technologies are faced with their own shortcomings,such as limitations of the desulfurization performance and regeneration of materials.To overcome these limitations,four nanofluids were prepared by dispersing different metal-modified MCM-41 particles in deep eutectic solvent as multifunctional promoters to develop a comprehensive desulfurization method.Based on the excellent adsorbability and high catalytic activity of the dispersed particles and the outstanding extractability of deep eutectic solvent in nanofluids,a high sulfur removal of 99.33%was achieved for model oil under mild conditions in 15 min.The nanofluids also showed excellent reusability due to their high structural stability.In addition,NF@Cu/Al-MCM-41-2.5%exhibited the best desulfurization performance among the prepared nanofluids.This result was obtained because the introduction of Al ions increased the number of acid sites and defect sites to improve the catalytic activity and adsorbability,and the best affinity of Cu/Al-MCM-41 for the deep eutectic solvent favored the reaction mass transfer.This work opens the door to the development of a comprehensive nonhydrodesulfurization method based on the design of nanofluid materials.展开更多
基金All authors appreciate the financial support from the National Key R&D Program of China(2017YFB0306504)the National Natural Science Foundation of China(No.21722604,21878133 and 21908082)+2 种基金China Postdoctoral Science Foundation(No.2019M651743)Natural Science Foundation of Jiangsu Province(BK20190852,BK20190854)Natural Science Foundation for Jiangsu Colleges and Universities(19KJB530005).
文摘Oxidative desulfurization(ODS)has been proved to be an efficient strategy for the production of clean fuel oil.Numerous metal-based materials have been employed as excellent ODS catalysts,but being hindered by their high-cost and potential secondary pollution.In this work,we employed graphene analogous hexagonal boron nitride(h-BN)as a metal-free catalyst for ODS with hydrogen peroxide(H2O2)as the oxidant.The h-BN catalyst was characterized and proved to be a few-layered structure with relatively high specific surface areas.The h-BN catalyst showed a 99.4%of sulfur removal in fuel oil under the optimized reaction conditions.Besides,the h-BN can be recycled for 8 times without significant decrease in the catalytic performance.Detailed mechanism analysis found that it is the boron radicals in h-BN activated H2O2 to generate·OH species,which can readily oxidize sulfides to corresponding sulfones for separation.This work would provide another choice in choosing metal-free catalysts for ODS.
文摘This work reports the enhancing effect of a highly cost effective and efficient metal, Fe, incorporation to Co or Ni based Mo/Al2O3 catalysts in the oxidative desulfurization （ODS） of dibenzothiophene （DBT） using H2O2 and formic acid as oxidants. The influence of operating parameters i.e. reaction time, catalyst dose, reaction temperature and oxidant amount on oxidation process was investigated. Results revealed that 99% DBT conversion was achieved at 60℃ and 150 min reaction time over Fe-Ni-Mo/Al2O3. Fe tremendously enhanced the ODS activity of Co or Ni based Mo/Al2O3 catalysts following the activity order：Fe-Ni-Mo/Al2O3 〉 Fe-Co-Mo/Al2O3 〉 Ni-Mo/Al2O3 〉 Co-Mo/Al2O3, while H2O2 exhibited higher oxidation activity than formic acid over all catalyst systems. Insight about the surface morphology and textural properties of fresh and spent catalysts were achieved using scanning electron microscopy （SEM）, X-ray diffraction （XRD）, energy dispersive X-ray （EDX） analysis, Atomic Absorption Spectroscopy （AAS） and BET surface area analysis, which helped in the interpretation of experimental data. The present study can be deemed as an effective approach on industrial level for ODS of fuel oils crediting to its high efficiency, low process/catalyst cost, safety and mild operating condition.
基金College Student Innovation and Entrepreneurship Training Program in Hebei Province(Grant No.S202210082057)National Natural Science Foundation Joint Fund Project-Key Support Project(Grant No.U20A20130)+5 种基金Natural Science Foundation of Hebei Province-Key Project(Grant No.B2021208033)Introduction of Talent Research Fund project of Hebei University of Science and Technology(Grant Nos.1181415,1181400)Science and Technology Research Project of Colleges and Universities in Hebei Province(Grant No.QN2020152)Hebei Technological Innovation Center for Volatile Organic Compounds Detection and Treatment in Chemical Industry(Grant No.ZXJJ20210401)Youth Science Fund Project of Hebei Provincial Natural Science Foundation(Grant Nos.B2021208040,B2022208020)Shijiazhuang Science and Technology Bureau(Grant No.211240233A).
文摘Compared with traditional hydrodesulfurization,new nonhydrodesulfurization methods have the advantage of a high removal efficiency for thiophene compounds under mild conditions.However,independent nonhydrodesulfurization technologies are faced with their own shortcomings,such as limitations of the desulfurization performance and regeneration of materials.To overcome these limitations,four nanofluids were prepared by dispersing different metal-modified MCM-41 particles in deep eutectic solvent as multifunctional promoters to develop a comprehensive desulfurization method.Based on the excellent adsorbability and high catalytic activity of the dispersed particles and the outstanding extractability of deep eutectic solvent in nanofluids,a high sulfur removal of 99.33%was achieved for model oil under mild conditions in 15 min.The nanofluids also showed excellent reusability due to their high structural stability.In addition,NF@Cu/Al-MCM-41-2.5%exhibited the best desulfurization performance among the prepared nanofluids.This result was obtained because the introduction of Al ions increased the number of acid sites and defect sites to improve the catalytic activity and adsorbability,and the best affinity of Cu/Al-MCM-41 for the deep eutectic solvent favored the reaction mass transfer.This work opens the door to the development of a comprehensive nonhydrodesulfurization method based on the design of nanofluid materials.
