The density functional theory has been successfully applied in analyzing pyrolytic carbon deposition by methane pyrolysis from the view of thermodynamics and kinetics based on a total number of 39 elementary reactions...The density functional theory has been successfully applied in analyzing pyrolytic carbon deposition by methane pyrolysis from the view of thermodynamics and kinetics based on a total number of 39 elementary reactions.M06-2X/def2-TZVP level was employed to optimize species structures and locate the transition states.The enthalpy changes and Gibbs free energy changes of all the reactions in the temperature range of 298.15–1800K were derived with optimized species.Results show that the reacting temperature should be above 1200 K based on the equilibrium constant analysis,which is consistent with the typical reaction temperature adopted in experiments.Potential energy surface profiles report that radical attacking reactions have lower energy barriers than those direct decomposition reactions,especially hydrogen radical attacking reactions.The energy barriers of the first steps,dehydrogenations of methane and ethylene,are 272.4 kJ·mol^(-1)and 288.9 kJ·mol^(-1)at 1200 K,which are very close to the experimental activation energy for methane pyrolysis.The most favorable decomposition reaction path is the path of hydrogen radical attacking reactions.The highest energy barrier of the path at 1200K is 185.7kJ·mol^(-1)presented by the C–H bond breaking in ethynyl attacked by hydrogen radical.展开更多
A combined experimental and simulational work was carried out in this paper to investigate the kinetic effects of non-equilibrium excitation by direct electron impact on low temperature pyrolysis of CH4 in a RF dielec...A combined experimental and simulational work was carried out in this paper to investigate the kinetic effects of non-equilibrium excitation by direct electron impact on low temperature pyrolysis of CH4 in a RF dielectric barrier discharge.Special attention was placed on the vibrational chemistry of CH4 and some other important products including H2,C2H2,C2H4,C2H6 and C3H8 largely produced in CH4/He discharge under an intermediate reduced electric field ranging 51-80 Td.A detailed kinetic mechanism incorporating a set of electron impact reactions,electron-ion recombination reactions,negative ions attachment reactions,charge exchange reactions,reactions involving vibrationally excited molecules and the relaxation process of vibrationally excited species was assembled and experimentally validated.The modeling results showed a reasonable agreement with the experimentally measured results in terms of CH4 conversion and products production including C2 hydrocarbons and hydrogen.A linear increasing trend of methane conversion with increasing plasma power input was discovered,which suggested a strong dependence of molecular excitation on energy input.Both the CH4/He mole ratio and the reactor temperature play significant roles in CH4 conversion and major products production.The experimental results showed that the selectivity of value-added products C2H4 and H2 keeps essentially unchanged with increasing energy input,mostly because the contribution CH4 ionization and He excitation effectively compete with vibrational excitation and dissociation of CH4 molecule with the E/N value increasing.The calculated results showed that the typical relaxation time of vibrational states is comparable to the gas-kinetics time in a CH4/He discharge mixture,thus the vibrationally excited molecules can significantly accelerate chemical reactions through an effective decrease of activation energy.The path flux analysis revealed that the vibrationally excited molecules CH4(v)and H2(v)enhanced chain propagation reactions,such as CH4(v)+H→CH3+H2,CH4(v)+CH→C2 H4+H,and H2(v)+C→CH+H,further stimulating the production of active radicals and final products.Specifically,H2(v)+C→CH+H was responsible for 7.9%of CH radical formation and CH4(v)+CH→C2 H4+H accounted for 31.4%of total C2 H4 production.This kinetic study provides new sights in demonstrating the contribution of vibrationally excited molecules in RF plasma assisted methane pyrolysis.展开更多
The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study...The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.展开更多
CARBON fiber is an reinforcing fiber of high performance and plays an important role in the development of advanced composite materials. Vapor-grown carbon fiber (VGCF) has higher tensile strength, Young’s modulus an...CARBON fiber is an reinforcing fiber of high performance and plays an important role in the development of advanced composite materials. Vapor-grown carbon fiber (VGCF) has higher tensile strength, Young’s modulus and conductivity than the polyacrylonitrile (PAN)- and pitch-based carbon fibers, which have been prepared on an industrial scale. It has been reported that the reaction temperature of VGCF from methane on Fe catalysts is higher展开更多
基金supported by the National Natural Science Foundation of China(51821091 and 51472203)the “111”Project of China(Grant No.B08040)the Research Fund of State Key Laboratory of Solidification Processing(NWPU)of China(Grant No.142-TZ-2016)。
文摘The density functional theory has been successfully applied in analyzing pyrolytic carbon deposition by methane pyrolysis from the view of thermodynamics and kinetics based on a total number of 39 elementary reactions.M06-2X/def2-TZVP level was employed to optimize species structures and locate the transition states.The enthalpy changes and Gibbs free energy changes of all the reactions in the temperature range of 298.15–1800K were derived with optimized species.Results show that the reacting temperature should be above 1200 K based on the equilibrium constant analysis,which is consistent with the typical reaction temperature adopted in experiments.Potential energy surface profiles report that radical attacking reactions have lower energy barriers than those direct decomposition reactions,especially hydrogen radical attacking reactions.The energy barriers of the first steps,dehydrogenations of methane and ethylene,are 272.4 kJ·mol^(-1)and 288.9 kJ·mol^(-1)at 1200 K,which are very close to the experimental activation energy for methane pyrolysis.The most favorable decomposition reaction path is the path of hydrogen radical attacking reactions.The highest energy barrier of the path at 1200K is 185.7kJ·mol^(-1)presented by the C–H bond breaking in ethynyl attacked by hydrogen radical.
基金supported by the National Natural Science Foundation of China(Grant No.21676024)the Beijing Natural Science Foundation(Grant No.3182029)the Fundamental Research Funds for the Central Universities(2018YJS141)
文摘A combined experimental and simulational work was carried out in this paper to investigate the kinetic effects of non-equilibrium excitation by direct electron impact on low temperature pyrolysis of CH4 in a RF dielectric barrier discharge.Special attention was placed on the vibrational chemistry of CH4 and some other important products including H2,C2H2,C2H4,C2H6 and C3H8 largely produced in CH4/He discharge under an intermediate reduced electric field ranging 51-80 Td.A detailed kinetic mechanism incorporating a set of electron impact reactions,electron-ion recombination reactions,negative ions attachment reactions,charge exchange reactions,reactions involving vibrationally excited molecules and the relaxation process of vibrationally excited species was assembled and experimentally validated.The modeling results showed a reasonable agreement with the experimentally measured results in terms of CH4 conversion and products production including C2 hydrocarbons and hydrogen.A linear increasing trend of methane conversion with increasing plasma power input was discovered,which suggested a strong dependence of molecular excitation on energy input.Both the CH4/He mole ratio and the reactor temperature play significant roles in CH4 conversion and major products production.The experimental results showed that the selectivity of value-added products C2H4 and H2 keeps essentially unchanged with increasing energy input,mostly because the contribution CH4 ionization and He excitation effectively compete with vibrational excitation and dissociation of CH4 molecule with the E/N value increasing.The calculated results showed that the typical relaxation time of vibrational states is comparable to the gas-kinetics time in a CH4/He discharge mixture,thus the vibrationally excited molecules can significantly accelerate chemical reactions through an effective decrease of activation energy.The path flux analysis revealed that the vibrationally excited molecules CH4(v)and H2(v)enhanced chain propagation reactions,such as CH4(v)+H→CH3+H2,CH4(v)+CH→C2 H4+H,and H2(v)+C→CH+H,further stimulating the production of active radicals and final products.Specifically,H2(v)+C→CH+H was responsible for 7.9%of CH radical formation and CH4(v)+CH→C2 H4+H accounted for 31.4%of total C2 H4 production.This kinetic study provides new sights in demonstrating the contribution of vibrationally excited molecules in RF plasma assisted methane pyrolysis.
基金supported by the C1 Gas Refinery Program through the National Research Foundation of Korea (NRF)funded by the Ministry of Science,ICT&Future Planning (NRF2017M3D3A1A01037001)supported by the Ministry of Trade,Industry and Energy (MOTIE),Korea Institute for Advancement of Technology (KIAT)through the Virtual Engineering Platform Program (P0022334)。
文摘The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.
文摘CARBON fiber is an reinforcing fiber of high performance and plays an important role in the development of advanced composite materials. Vapor-grown carbon fiber (VGCF) has higher tensile strength, Young’s modulus and conductivity than the polyacrylonitrile (PAN)- and pitch-based carbon fibers, which have been prepared on an industrial scale. It has been reported that the reaction temperature of VGCF from methane on Fe catalysts is higher
