Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performanc...Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.展开更多
A bimetal-exchanged NaY zeolite(Cu(Ⅰ)-Y(Ⅲ)-Y)with a desirable adsorptive desulfurization(ADS)performance was prepared and characterized by means of X-ray diffraction,specific surface area measurements,X-ray fluoresc...A bimetal-exchanged NaY zeolite(Cu(Ⅰ)-Y(Ⅲ)-Y)with a desirable adsorptive desulfurization(ADS)performance was prepared and characterized by means of X-ray diffraction,specific surface area measurements,X-ray fluorescence spectrometer,X-ray photoelectron spectroscopy,thermal gravity analysis and Fourier transform infrared spectroscopy.The effect of Y(Ⅲ)ions on ADS in the presence of the xylenes was investigated.Results indicated that the ADS performance of Y(Ⅲ)-Y is higher than that of most reported CeY.The Y(Ⅲ)-based Cu(Ⅰ)-Y(Ⅲ)-Y demonstrated the higher breakthrough loading than those of reported Ce(Ⅲ)/Ce(Ⅳ)-based transition metal Y zeolites,showing that Y(Ⅲ)ions play a promoting role in improving the ADS selectivity.For Cu(Ⅰ)-Y(Ⅲ)-Y,a new strong S-M interaction(S stands for sulfur,while M stands for metal)active site was formed,which might be caused by the synergistic effect between Cu(Ⅰ)and Y(Ⅲ).The Cu(Ⅰ)-Y(Ⅲ)-Y,which combined the advantages of Cu(I)-Y and Y(Ⅲ)-Y,is a kind of promising adsorbent.The breakthrough loading decreased in the order of Cu(Ⅰ)-Y(Ⅲ)-Y>Y(Ⅲ)-Y>Cu(Ⅰ)-Y,and the effect of xylene isomers on the sulfur removal was in the order of ortho-xylene>meta-xylene>para-xylene,which exhibited the same trend with the bond order of xylenes.展开更多
文摘Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.
基金the financial supports from the National Natural Science Foundation of China(81172204)。
文摘A bimetal-exchanged NaY zeolite(Cu(Ⅰ)-Y(Ⅲ)-Y)with a desirable adsorptive desulfurization(ADS)performance was prepared and characterized by means of X-ray diffraction,specific surface area measurements,X-ray fluorescence spectrometer,X-ray photoelectron spectroscopy,thermal gravity analysis and Fourier transform infrared spectroscopy.The effect of Y(Ⅲ)ions on ADS in the presence of the xylenes was investigated.Results indicated that the ADS performance of Y(Ⅲ)-Y is higher than that of most reported CeY.The Y(Ⅲ)-based Cu(Ⅰ)-Y(Ⅲ)-Y demonstrated the higher breakthrough loading than those of reported Ce(Ⅲ)/Ce(Ⅳ)-based transition metal Y zeolites,showing that Y(Ⅲ)ions play a promoting role in improving the ADS selectivity.For Cu(Ⅰ)-Y(Ⅲ)-Y,a new strong S-M interaction(S stands for sulfur,while M stands for metal)active site was formed,which might be caused by the synergistic effect between Cu(Ⅰ)and Y(Ⅲ).The Cu(Ⅰ)-Y(Ⅲ)-Y,which combined the advantages of Cu(I)-Y and Y(Ⅲ)-Y,is a kind of promising adsorbent.The breakthrough loading decreased in the order of Cu(Ⅰ)-Y(Ⅲ)-Y>Y(Ⅲ)-Y>Cu(Ⅰ)-Y,and the effect of xylene isomers on the sulfur removal was in the order of ortho-xylene>meta-xylene>para-xylene,which exhibited the same trend with the bond order of xylenes.