Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins.In this work,the catalytic effects of V_(2)O_(5) on the pyrolysis of cation exchange resin are investigated for the first time...Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins.In this work,the catalytic effects of V_(2)O_(5) on the pyrolysis of cation exchange resin are investigated for the first time.The results show that it is a better catalyst than others so far studied and achieves a lowering of final pyrolysis temperature and residual rate simultaneously when aided by physical blending.The maximum reductions of the final pyrolysis temperature and the residual rate are 173℃and 11.9%(in weight),respectively.Under the action of V_(2)O_(5),low-temperature(445℃)removal of partial sulfonic acid groups occurs and the pyrolysis of the resin copolymer matrix is promoted.This is demonstrated by the analysis of pyrolysis residues at different temperatures by X-ray photoelectron spectroscopy(XPS)and element analysis.The catalytic activity of V_(2)O_(5) is determined by effects both at acid sites and oxidation-reduction centers via H2-TPR(temperature programmed reduction),V_(2)-TPD(temperature programmed desorption),CV_(2)-TPD,and NH3-TPD.The catalytic effect of oxidation-reduction centers in V_(2)O_(5) is achieved by close contact with the sulfur bond through chemisorption under the effect of acid sites.V_(2)O_(5) is also believed to be the reason for the removal of partial sulfonic acid groups at lower temperatures(445℃).V_(2)O_(5) is an effective catalyst for spent resin pyrolysis and can be further applied in industry.展开更多
A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction ha...A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction has been rarely studied.In this study,a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100%water vapor at 693 K.The co-reaction of methane and methanol was subsequently evaluated.Br?nsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42%at 673 K,which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index.Moreover,the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst,with results showing that excessive acid sites or methanol molecules reduce methane conversion.It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites.Hence,a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.展开更多
In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the i...In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [-OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (〉 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.展开更多
基金Project supported by the National Natural Science Foundation of China(No.20490200)the National Key Technology R&D Program of China(Nos.85-516-06-03,2001BA305B03,and 2007BAF22B08)+1 种基金the National High-Tech R&D Program(863 Program)of China(No.2007AA04Z182)the SINOPEC Technology Project(No.406005),China
基金supported by the National Natural Science Foundation of China(No.91434205)the National Science Fund for Distinguished Young Scholars(No.21525627)+1 种基金the Zhejiang Provincial Natural Science Foundation of China(No.LR14B060001)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20130101110063)
基金Project supported by the National Natural Science Foundation of China(No.U1862203)the National Science Fund for Distinguished Young Scholars(No.21525627)the Science Fund for Creative Research Groups of National Natural Science Foundation of China(No.61621002)。
文摘Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins.In this work,the catalytic effects of V_(2)O_(5) on the pyrolysis of cation exchange resin are investigated for the first time.The results show that it is a better catalyst than others so far studied and achieves a lowering of final pyrolysis temperature and residual rate simultaneously when aided by physical blending.The maximum reductions of the final pyrolysis temperature and the residual rate are 173℃and 11.9%(in weight),respectively.Under the action of V_(2)O_(5),low-temperature(445℃)removal of partial sulfonic acid groups occurs and the pyrolysis of the resin copolymer matrix is promoted.This is demonstrated by the analysis of pyrolysis residues at different temperatures by X-ray photoelectron spectroscopy(XPS)and element analysis.The catalytic activity of V_(2)O_(5) is determined by effects both at acid sites and oxidation-reduction centers via H2-TPR(temperature programmed reduction),V_(2)-TPD(temperature programmed desorption),CV_(2)-TPD,and NH3-TPD.The catalytic effect of oxidation-reduction centers in V_(2)O_(5) is achieved by close contact with the sulfur bond through chemisorption under the effect of acid sites.V_(2)O_(5) is also believed to be the reason for the removal of partial sulfonic acid groups at lower temperatures(445℃).V_(2)O_(5) is an effective catalyst for spent resin pyrolysis and can be further applied in industry.
基金Project supported by the National Natural Science Foundation of China(No.U1663222)。
文摘A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation.However,the effect of catalyst acid properties on the co-reaction has been rarely studied.In this study,a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100%water vapor at 693 K.The co-reaction of methane and methanol was subsequently evaluated.Br?nsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42%at 673 K,which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index.Moreover,the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst,with results showing that excessive acid sites or methanol molecules reduce methane conversion.It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites.Hence,a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.
基金support and encouragement of the National Natural Science Foundation of China(Nos.U1663222 and 21176208)
文摘In this study, a series of aryloxy-aluminoxanes originated directly from the hydrolysis of reaction products of A1Me3 and phenols were synthesized, which could serve as effective polymer-retarding activators for the iron-catalyzed ethylene oligomerization. The molar ratios of [PhOH]/[AlMe3] and [H2O]/[Al] during the preparation were explored and their impacts on the oligomerization activity and product distribution were discussed. To obtain the effective activators with good polymer-retarding effect and relatively high activity, the optimized conditions were proposed to be [PhOH]/[AlMe3] = 0.5 and [H2O]/[Al] = 0.7. Various aluminoxanes with different [-OH] sources confirmed the importance of using phenols in preparing the effective polymer-retarding activators. By utilizing these aryloxy-aluminoxanes, the mass fraction of polymers in the total products could be reduced to lower than 1.0 wt%, which is much lower than that of the MAO-activated systems (〉 30 wt%). This is a potential benefit for the industrial application of the iron-catalyzed oligomerization process.