Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimiz...Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimizing the process,with cobalt-and iron-based catalysts being widely used in industrial applications.Iron-based catalysts,in particular,are favored due to their low cost,broad temperature range,and high water-gas shift reaction activity,making them ideal for syngas derived from coal and biomass with a low H_(2)/CO ratio.However,despite their long history of industrial use,iron-based catalysts face two significant challenges.First,the presence of multiple iron phases-metallic iron,iron oxides,and iron carbides-complicates the understanding of the reaction mechanism due to dynamic phase transformations.Second,the high water-gas shift activity of these catalysts leads to increased CO_(2) selectivity,thereby reducing overall carbon efficiency.In Fischer-Tropsch synthesis,CO_(2) can arise as primary CO_(2) from CO disproportionation(the Boudouard reaction)and as secondary CO_(2) from the water-gas shift reaction.The accumulation of CO_(2) formation further compromises overall carbon efficiency,which is particularly undesirable given the current focus on minimizing carbon emissions and achieving carbon neutrality.This review focus on the ongoing advancements of iron-based catalysts for Fischer-Tropsch synthesis,with particular emphasis on overcoming these two critical challenges for iron-based catalysts:regulating the active phases and minimizing CO_(2) selectivity.Addressing these challenges is essential for enhancing the overall catalytic efficiency and selectivity of iron-based catalysts.In this review,recent efforts to suppress CO_(2) selectivity of iron-based catalysts,including catalyst hydrophobic modification and graphene confinement,are explored for their potential to stabilize active phases and prevent unwanted side reactions.This innovative approach offers new opportunities for developing catalysts with high activity,low CO_(2) selectivity,and enhanced stability,which are key factors for enhancing both the efficiency and sustainability for Fischer-Tropsch synthesis.Such advancements are crucial for advancing more efficient and sustainable Fischer-Tropsch synthesis technologies,supporting the global push for net-zero emissions goals,and contributing to carbon reduction efforts worldwide.展开更多
The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO...The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO_(3),and the acid-alkalinity of the catalyst was regulated by introducing alkaline Ba basic sties.In a co ntinuous fixed-bed reactor with a feed mass space velocity of 1 h~(-1)and reaction temperature of 330℃,BaCO_(3)/γ-Al_(2)O_(3) catalyst can efficiently catalyzed the deoxygenation removal of 1-octanol in Fischer-Tropsch C10mixture oil.It also inhibited the isomerization of 1-decene in the C10 mixture.The catalytic deoxygenation kinetics of 1-octanol were also studied.The reaction was endothermic with an activation energy of 64 kJ·mol^(-1)and a reaction order of 2.In addition,theoretical studies revealed the adsorption and activation of 1-decene on the Lewis acidic site and the alkaline Ba basic sites,1-decene was more easily underwent isomerization into 2-decene at Lewis acid sites.This research provides a useful method to enable the industrial application of catalytic deoxygenation of alcohols in Fischer-Tropsch synthetic oil.展开更多
Fischer-Tropsch synthesis(FTS)and hydroformylation are pivotal chemical processes for converting syngas and olefins into valuable hydrocarbons and chemicals.Recent advancements in catalyst design,reaction mechanisms,a...Fischer-Tropsch synthesis(FTS)and hydroformylation are pivotal chemical processes for converting syngas and olefins into valuable hydrocarbons and chemicals.Recent advancements in catalyst design,reaction mechanisms,and process optimization have significantly improved the efficiency,selectivity,and sustainability of these processes.This Account introduces the relevant research activities in the Research Center for Catalysis in Syngas Conversion and Fine Chemicals(DNL0805)of Dalian Institute of Chemical Physics(DICP),Chinese Academy of Sciences.The reactions of interests include FTS,heterogeneous hydroformylation of olefins,alcohol dehydration and oxidation,andα-olefin polymerization,with the emphasis on developing innovative catalysts and processes to address the challenges of traditional processes.Exemplified by the discovery of robust Co-Co_(2)C/AC for FTS and Rh_(1)/POPs-PPh_(3) for heterogeneous hydroformylation of olefins,it demonstrates how lab-scale fundamental understandings on the active sites of catalysts leads to pilot-plant scale-up and finally commercial technologies.Perspectives on the challenges and directions for future developments in these exciting fields are provided.展开更多
Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical prope...Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.展开更多
The addition of small amounts of ceria to Co/Al2O3 catalysts increases the turnover rate of the catalyst and C5+ selectivity in the Fischer-Tropsch synthesis. In this work, the amounts of ceria, the calcination tempe...The addition of small amounts of ceria to Co/Al2O3 catalysts increases the turnover rate of the catalyst and C5+ selectivity in the Fischer-Tropsch synthesis. In this work, the amounts of ceria, the calcination temperature, the temperature-programmed reduction (TPR), the temperature-programmed oxidation (TPO), and XRD are investigated. The results show that the addition of small amounts of ceria to Co/Al2O3 catalyst (Ce/Co≈1∶ 10 ～1∶ 7, atom) can increase the CO conversion and liquid yield, while the calcination temperature can control both the chain growth probability and CO conversion in a reverse trend. The TPR and TPO experiments show that small amounts of Ceria can improve the reducibility, but the amounts of carbon deposit increase, and two-type carbon deposition is found in the short-term reaction catalyst.展开更多
文摘Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal,natural gas,and biomass into clean fuels and high-value chemicals via syngas.Catalyst development is crucial for optimizing the process,with cobalt-and iron-based catalysts being widely used in industrial applications.Iron-based catalysts,in particular,are favored due to their low cost,broad temperature range,and high water-gas shift reaction activity,making them ideal for syngas derived from coal and biomass with a low H_(2)/CO ratio.However,despite their long history of industrial use,iron-based catalysts face two significant challenges.First,the presence of multiple iron phases-metallic iron,iron oxides,and iron carbides-complicates the understanding of the reaction mechanism due to dynamic phase transformations.Second,the high water-gas shift activity of these catalysts leads to increased CO_(2) selectivity,thereby reducing overall carbon efficiency.In Fischer-Tropsch synthesis,CO_(2) can arise as primary CO_(2) from CO disproportionation(the Boudouard reaction)and as secondary CO_(2) from the water-gas shift reaction.The accumulation of CO_(2) formation further compromises overall carbon efficiency,which is particularly undesirable given the current focus on minimizing carbon emissions and achieving carbon neutrality.This review focus on the ongoing advancements of iron-based catalysts for Fischer-Tropsch synthesis,with particular emphasis on overcoming these two critical challenges for iron-based catalysts:regulating the active phases and minimizing CO_(2) selectivity.Addressing these challenges is essential for enhancing the overall catalytic efficiency and selectivity of iron-based catalysts.In this review,recent efforts to suppress CO_(2) selectivity of iron-based catalysts,including catalyst hydrophobic modification and graphene confinement,are explored for their potential to stabilize active phases and prevent unwanted side reactions.This innovative approach offers new opportunities for developing catalysts with high activity,low CO_(2) selectivity,and enhanced stability,which are key factors for enhancing both the efficiency and sustainability for Fischer-Tropsch synthesis.Such advancements are crucial for advancing more efficient and sustainable Fischer-Tropsch synthesis technologies,supporting the global push for net-zero emissions goals,and contributing to carbon reduction efforts worldwide.
基金supported by the Scientific and technological innovation project of Ningxia Coal Industry Co.,LTD,China Energy Investment(NXMY-24-36)。
文摘The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO_(3),and the acid-alkalinity of the catalyst was regulated by introducing alkaline Ba basic sties.In a co ntinuous fixed-bed reactor with a feed mass space velocity of 1 h~(-1)and reaction temperature of 330℃,BaCO_(3)/γ-Al_(2)O_(3) catalyst can efficiently catalyzed the deoxygenation removal of 1-octanol in Fischer-Tropsch C10mixture oil.It also inhibited the isomerization of 1-decene in the C10 mixture.The catalytic deoxygenation kinetics of 1-octanol were also studied.The reaction was endothermic with an activation energy of 64 kJ·mol^(-1)and a reaction order of 2.In addition,theoretical studies revealed the adsorption and activation of 1-decene on the Lewis acidic site and the alkaline Ba basic sites,1-decene was more easily underwent isomerization into 2-decene at Lewis acid sites.This research provides a useful method to enable the industrial application of catalytic deoxygenation of alcohols in Fischer-Tropsch synthetic oil.
文摘Fischer-Tropsch synthesis(FTS)and hydroformylation are pivotal chemical processes for converting syngas and olefins into valuable hydrocarbons and chemicals.Recent advancements in catalyst design,reaction mechanisms,and process optimization have significantly improved the efficiency,selectivity,and sustainability of these processes.This Account introduces the relevant research activities in the Research Center for Catalysis in Syngas Conversion and Fine Chemicals(DNL0805)of Dalian Institute of Chemical Physics(DICP),Chinese Academy of Sciences.The reactions of interests include FTS,heterogeneous hydroformylation of olefins,alcohol dehydration and oxidation,andα-olefin polymerization,with the emphasis on developing innovative catalysts and processes to address the challenges of traditional processes.Exemplified by the discovery of robust Co-Co_(2)C/AC for FTS and Rh_(1)/POPs-PPh_(3) for heterogeneous hydroformylation of olefins,it demonstrates how lab-scale fundamental understandings on the active sites of catalysts leads to pilot-plant scale-up and finally commercial technologies.Perspectives on the challenges and directions for future developments in these exciting fields are provided.
基金supported by the Key Project of Natural Science Foundation of Ningxia(NZ13010)the National Natural Science Foundation of China(21366025)~~
文摘Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.
文摘The addition of small amounts of ceria to Co/Al2O3 catalysts increases the turnover rate of the catalyst and C5+ selectivity in the Fischer-Tropsch synthesis. In this work, the amounts of ceria, the calcination temperature, the temperature-programmed reduction (TPR), the temperature-programmed oxidation (TPO), and XRD are investigated. The results show that the addition of small amounts of ceria to Co/Al2O3 catalyst (Ce/Co≈1∶ 10 ～1∶ 7, atom) can increase the CO conversion and liquid yield, while the calcination temperature can control both the chain growth probability and CO conversion in a reverse trend. The TPR and TPO experiments show that small amounts of Ceria can improve the reducibility, but the amounts of carbon deposit increase, and two-type carbon deposition is found in the short-term reaction catalyst.
