Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in ...Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.展开更多
Ga-Al-MFI samples were synthesized in hydrothermal conditions from gels of composition 1.08CH3NH2- 0.134TPABr-1SiO2-xAl2O3-yGa2O3-40H2O at 175 ℃ for 7 days, with x = 0.005 and 0.0025, y = 0.005, 0,010 and 0.020. The ...Ga-Al-MFI samples were synthesized in hydrothermal conditions from gels of composition 1.08CH3NH2- 0.134TPABr-1SiO2-xAl2O3-yGa2O3-40H2O at 175 ℃ for 7 days, with x = 0.005 and 0.0025, y = 0.005, 0,010 and 0.020. The samples were characterized by XRD, BET measurements, thermal analysis （TGA-DTA） atomic absorption and high resolution solid state MAS 27Al and 71Ga NMR measurements. The aromatization of propane was studied as catalytic test. The activity and selectivity of the catalysts were determined for benzene, toluene and xylenes on the one hand and for methane and ethane on the other hand. The most active sample was obtained with the highest Ga/AI ratio. For this sample, the BTX selectivity obtained by aromatization was always higher than the hydrocracking selectivity leading to methane and ethane. The relative amount of toluene was higher than that of benzene and ofxylenes. The samples were deactivated by coke formation that was revealed more severe for the most active sample,展开更多
Regulation of aluminum distribution in zeolite framework is an effective method for improving its catalytic performance for propane aromatization.Herein,we found that recrystallization and post-realuminization of ZSM-...Regulation of aluminum distribution in zeolite framework is an effective method for improving its catalytic performance for propane aromatization.Herein,we found that recrystallization and post-realuminization of ZSM-5 cannot only create hollow structures to enhance the diffusion ability,but also adjust the content and position of paired aluminum species in its framework.Various characterizations results confirmed that increase of paired aluminum content and inducement of more aluminum atoms sited in the intersection cavity are beneficial to the formation of aromatic products in propane aromatization.As a result,the hollow-structured ZSM-5 zeolite with more paired aluminum(H-200-hollow)showed higher propane conversion and aromatics selectivity than other samples at the same conditions.The catalytic performance of H-200-hollow can be further improved by ion-exchanging with a small amount of Ga(III)species.The propane conversion and aromatics selectivity of Ga-200-hollow reached as high as 95%and 70%,respectively,at 540℃ and 1 atm.展开更多
Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owin...Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owing to the quick evolution of the metallic active sites and the complex reaction processes including direct propane aromatization,CO_(2) hydrogenation,reverse water-gas shift reaction,and propane-CO_(2) coupling aromatization.Herein,Ga/ZSM-5 catalysts were constructed to study the dynamic evolution of the metallic active sites and the role of CO_(2) during the propane and CO_(2) coupling reaction.After optimizing the reaction conditions,a notable propane conversion rate of 97.9%and an impressive aromatics selectivity of 80.6%in hydrocarbons can be achieved at the conditions of 550℃and CO_(2)/C_(3)H_(8) of 4.^(13)CO_(2)isotope experiments illustrate that C-atoms of CO_(2) can enter into CO(86.5%)and aromatics(10.8%)during the propane-CO_(2) coupling reaction process.In situ XANES and FTIR spectroscopies at 550℃and H_(2)/C_(3)H_(8) atmosphere reveal that GaO_(x) species can be gradually dispersed into[GaH_(2)]^(+)/[GaH]^(2+)on the Bronsted acid sites of ZSM-5 zeolite during H_(2) and/or C_(3)H_(8) treatment,which are the real active sites for propane-CO_(2) coupling conversion.In situ CO_(2)-FTIR experiments demonstrate that the[GaH_(2)]^(+)/[GaH]^(2+)species can react with CO_(2) and accelerate the propane and CO_(2) coupling process.This work not only presents a cost-effective avenue for CO_(2) utilization,but also contributes to the active site design for improved alkane and CO_(2) activation in coupling reaction system.展开更多
文摘Direct converting carbon dioxide(CO_(2))and propane(C_(3)H_(8))into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO_(2)emission and adequately utilize C_(3)H_(8) in shale gas.Owing to their thermodynamic resistance,converting CO_(2)and C_(3)H_(8) respectively remains difficult.Here,we achieve 60.2%aromatics selectivity and 48.8%propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO_(2)and C_(3)H_(8).Operando dual-beam FTIR spectroscopy combined with ^(13)C-labeled CO_(2)tracing experiments revealed that CO_(2)is directly involved in the generation of aromatics,with its carbon atoms selectively embedded into the aromatic ring,bypassing the reverse water-gas shift pathway.Accordingly,a cooperative aromatization mechanism is proposed.Thereinto,lactones,produced from CO_(2)and olefins,are proven to be the key intermediate.This work not only provides an opportunity for simultaneous conversion of CO_(2)and C_(3)H_(8),but also expends coupling strategy designing of CO_(2)and alkanes over acidic zeolites.
基金supported by MIUR PRIN 2010–2011 2010H7PXLC Project on“Innovative downstream processing of conversion of algal biomass for the production of jet fuel and green diesel”
文摘Ga-Al-MFI samples were synthesized in hydrothermal conditions from gels of composition 1.08CH3NH2- 0.134TPABr-1SiO2-xAl2O3-yGa2O3-40H2O at 175 ℃ for 7 days, with x = 0.005 and 0.0025, y = 0.005, 0,010 and 0.020. The samples were characterized by XRD, BET measurements, thermal analysis （TGA-DTA） atomic absorption and high resolution solid state MAS 27Al and 71Ga NMR measurements. The aromatization of propane was studied as catalytic test. The activity and selectivity of the catalysts were determined for benzene, toluene and xylenes on the one hand and for methane and ethane on the other hand. The most active sample was obtained with the highest Ga/AI ratio. For this sample, the BTX selectivity obtained by aromatization was always higher than the hydrocracking selectivity leading to methane and ethane. The relative amount of toluene was higher than that of benzene and ofxylenes. The samples were deactivated by coke formation that was revealed more severe for the most active sample,
基金supported by the National Key R&D Program of China(Grant No.2023YFB4103700)National Natural Science Foundation of China(Grant Nos.U1910203,21991090,21991092,22322208,22272195,U22A20431)+2 种基金Natural Science Foundation of Shanxi Province of China(Grant No.202203021224009)Innovation foundation of Institute of Coal Chemistry,Chinese Academy of Sciences(Grant No.SCJC-DT-2023-06)Youth Innovation Promotion Association CAS(Grant No.2021172).
文摘Regulation of aluminum distribution in zeolite framework is an effective method for improving its catalytic performance for propane aromatization.Herein,we found that recrystallization and post-realuminization of ZSM-5 cannot only create hollow structures to enhance the diffusion ability,but also adjust the content and position of paired aluminum species in its framework.Various characterizations results confirmed that increase of paired aluminum content and inducement of more aluminum atoms sited in the intersection cavity are beneficial to the formation of aromatic products in propane aromatization.As a result,the hollow-structured ZSM-5 zeolite with more paired aluminum(H-200-hollow)showed higher propane conversion and aromatics selectivity than other samples at the same conditions.The catalytic performance of H-200-hollow can be further improved by ion-exchanging with a small amount of Ga(III)species.The propane conversion and aromatics selectivity of Ga-200-hollow reached as high as 95%and 70%,respectively,at 540℃ and 1 atm.
基金supported by the National Key Research and Development Program of China (No.2022YFE0116000)the National Natural Science Foundation of China (No.22288101,21991092,21991090,22202193,and 22172166)+1 种基金the Youth Innovation Promotion Association CAS (2021182)the Innovation Research Foundation of Dalian Institute of Chemical Physics,Chinese Academy of Sciences (DICP I202429 and I202217)。
文摘Alkane coupling with CO_(2) by metal-containing zeolites catalysis is found to be a promising way to produce aromatics and syngas in recent years,but the real active sites and the role of CO_(2) are still unclear owing to the quick evolution of the metallic active sites and the complex reaction processes including direct propane aromatization,CO_(2) hydrogenation,reverse water-gas shift reaction,and propane-CO_(2) coupling aromatization.Herein,Ga/ZSM-5 catalysts were constructed to study the dynamic evolution of the metallic active sites and the role of CO_(2) during the propane and CO_(2) coupling reaction.After optimizing the reaction conditions,a notable propane conversion rate of 97.9%and an impressive aromatics selectivity of 80.6%in hydrocarbons can be achieved at the conditions of 550℃and CO_(2)/C_(3)H_(8) of 4.^(13)CO_(2)isotope experiments illustrate that C-atoms of CO_(2) can enter into CO(86.5%)and aromatics(10.8%)during the propane-CO_(2) coupling reaction process.In situ XANES and FTIR spectroscopies at 550℃and H_(2)/C_(3)H_(8) atmosphere reveal that GaO_(x) species can be gradually dispersed into[GaH_(2)]^(+)/[GaH]^(2+)on the Bronsted acid sites of ZSM-5 zeolite during H_(2) and/or C_(3)H_(8) treatment,which are the real active sites for propane-CO_(2) coupling conversion.In situ CO_(2)-FTIR experiments demonstrate that the[GaH_(2)]^(+)/[GaH]^(2+)species can react with CO_(2) and accelerate the propane and CO_(2) coupling process.This work not only presents a cost-effective avenue for CO_(2) utilization,but also contributes to the active site design for improved alkane and CO_(2) activation in coupling reaction system.
