Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such ...Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.展开更多
The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A se...The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.展开更多
The Fischer-Tropsch synthesis is a significant technology for converting coal,natural gas,and biomass into synthetic fuels.In recent years,the use of microchannel reactors for the Fischer-Tropsch synthesis has attract...The Fischer-Tropsch synthesis is a significant technology for converting coal,natural gas,and biomass into synthetic fuels.In recent years,the use of microchannel reactors for the Fischer-Tropsch synthesis has attracted significant attention.Fischer-Tropsch synthesis experiments were carried out in a microchannel reactor and the influences of reaction conditions on the experimental results were investigated in this study.Based on the experimental data,a dynamic multi-component pseudo-homogeneous variable-volume flow model of microchannel reactors for the Fischer-Tropsch synthesis was built to determine the pressure-,velocity-,conversion-and(component-wise)concentration-distributions in reaction channels.The model takes into account the combined effects of gas volume expansion caused by the frictional pressure drop and gas volume contraction caused by reaction consumption.A novel effective method for calculating the pressure and superficial gas velocity values in microchannel reactors was proposed in the model.Besides that,two sets of experimental data were selected from references to evaluate the validity and accuracy of the model.The reaction performances in the microchannels were analyzed carefully based on the calculated results.展开更多
To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent flu...To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.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
基金the financial support from by the National Key Research and Development Program of China(No.2022YFB4101800)National Natural Science Foundation of China(No.22278298)Program for Introducing Talents of Discipline to Universities of China(No.BP0618007).
文摘Nitrogen(N)-doped carbon materials as metal catalyst supports have attracted signifi cant attention,but the eff ect of N dopants on catalytic performance remains unclear,especially for complex reaction processes such as Fischer-Tropsch synthesis(FTS).Herein,we engineered ruthenium(Ru)FTS catalysts supported on N-doped carbon overlayers on TiO_(2)nanoparticles.By regulating the carbonization temperatures,we successfully controlled the types and contents of N dopants to identify their impacts on metal-support interactions(MSI).Our fi ndings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species.Moreover,pyridinic N demonstrates the highest electron-donating ability,followed by pyrrolic N and graphitic N.In addition to realizing excellent catalytic stability,strengthening the interaction between Ru sites and N dopants increases the Ru^(0)/Ru^(δ+)ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO.Consequently,it improves the catalyst’s overall performance,encompassing intrinsic and apparent activities,as well as its ability for carbon chain growth.Accordingly,the as-synthesized Ru/TiO_(2)@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C_(5+)time yield of 219.4 mol CO/(mol Ru·h)and C_(5+)selectivity of 85.5%.
基金supported by the National Natural Science Foundation of China(21908234)the National Key Research&Development Program of China(2020YFB0606404)+1 种基金the Inner Mongolia Science and Technology Agency Program(2019CG058)Shanxi Province Natural Science Foundation(202103021223063).
文摘The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.
文摘The Fischer-Tropsch synthesis is a significant technology for converting coal,natural gas,and biomass into synthetic fuels.In recent years,the use of microchannel reactors for the Fischer-Tropsch synthesis has attracted significant attention.Fischer-Tropsch synthesis experiments were carried out in a microchannel reactor and the influences of reaction conditions on the experimental results were investigated in this study.Based on the experimental data,a dynamic multi-component pseudo-homogeneous variable-volume flow model of microchannel reactors for the Fischer-Tropsch synthesis was built to determine the pressure-,velocity-,conversion-and(component-wise)concentration-distributions in reaction channels.The model takes into account the combined effects of gas volume expansion caused by the frictional pressure drop and gas volume contraction caused by reaction consumption.A novel effective method for calculating the pressure and superficial gas velocity values in microchannel reactors was proposed in the model.Besides that,two sets of experimental data were selected from references to evaluate the validity and accuracy of the model.The reaction performances in the microchannels were analyzed carefully based on the calculated results.
基金supported by the National Key Research and Development Program of China(2017YFB0602504)the General Program of National Natural Science Foundation of China(22178385).
文摘To produce low olefin gasoline with high octane number by Fischer-Tropsch (F-T) wax fluid catalytic cracking (FCC) process, operating conditions optimization were carried out in the pilot-scale riser and turbulent fluidized bed (TFB) FCC unit. The experimental results in the riser indicated that under the condition of low reaction temperature and regenerated catalyst temperature, large catalyst-to-oil weight ratio (C/O) and long reaction time, the gasoline olefin content could be reduced to 20.28 wt%, but there is large octane number loss owing to a great loss in high octane number olefin. Therefore, a novel FCC process using the TFB reactor was proposed to strengthen the aromatization reaction. The reaction performance of TFB reactor were investigated. The result demonstrated that the TFB reactor has more significant effect in reducing olefins and improving aromatics. At the expense of certain gasoline yield, the gasoline olefin content reduced to 23.70 wt%, aromatics content could increase to 26.79 wt% and the RON was up to 91.0. The comparison of reactor structure and fluidization demonstrated that the TFB reactor has higher catalyst bed density. The reaction heat and coke combustion heat was calculated indicating the feasibility of its industrial application of the TFB process.
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.
