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
Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagat...Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.展开更多
As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep ...As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep understanding of its oxidative pyrolysis mechanism is crucial for addressing wax deposition in oil and gas extraction,enhancing product selectivity in cracking processes,and advancing novel clean fuel technologies.Traditional experimental methods face challenges in capturing transient free-radical reaction pathways at high temperatures,whereas molecular dynamics simulations offer a powerful approach to bridge the research gap in elucidating atomic-scale dynamic mechanisms.This database is constructed based on high-precision molecular dynamics simulations,comprising oxidative pyrolysis trajectory data for three paraffin models featuring different straight-chain hydrocarbon distributions within the temperature range of 2100-2500 K.The COMPASS force field was employed to optimize the initial structures,and the ReaxFF reactive force field was used to simulate the oxidative pyrolysis process.The database includes atomic trajectories,species evolution information,and reaction network analysis results for both heating and isothermal cracking processes,with a total data volume of approximately 141 GB(including 150000 atomic configuration frames).The data is stored in a hierarchical directory structure,supporting multi-scale oxidative pyrolysis mechanism studies and providing atomic-scale dynamic evidence for revealing carbon chain length effects and temperature sensitivity.展开更多
The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of a...The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured.The results show that the consumption of NH_(3)/O_(2)and the production of N_(2)/H_(2)change linearly with the increase of voltage,which indicates the decoupling of nonequilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures.Secondly,the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established.Based on the reaction path analysis,the simplified mechanism is obtained.The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism.Finally,based on the simplified mechanism,the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species.The results show that the generation,development,and propagation of the pre-sheath have a great influence on the formation and consumption of species.The consumption of NH_(3)by the cathode pre-sheath is greater than that by the anode pre-sheath,but the opposite is true for OH and O(1S).However,within the sheath,almost all reactions do not occur.Further,by changing the parameters of nanosecond pulse power supply voltage,it is found that the electron number density,electron current density,and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath.Furthermore,the discharge interval has little effect on the sheath structure and gas mixture breakdown.The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.展开更多
The thermal degradation of two synthetic lubricants base oils, poly-a-olefins （PAO） and di-esters （DE）, was investigated under oxidative pyrolysis condition and their properties were characterized in simulated ＂a...The thermal degradation of two synthetic lubricants base oils, poly-a-olefins （PAO） and di-esters （DE）, was investigated under oxidative pyrolysis condition and their properties were characterized in simulated ＂areo-engine＂ by comparing the thermal stability and identifying the products of thermal decomposition as a function of exposure temperature. The characterization of the products were performed by means of Fourier transform infrared spectrometry （FTIR）, gas chromatography/mass spectrometry （GC/MS） and viscosity experiments. The results show that PAO has the lower thermal stability, being degraded at 200℃ different from 300 ℃ for DE. Several by-products are identified during the thermal degradation of two lubricant base oils. The majority of PAO products consist of alkenes and olefins, while more oxygen-contained organic compounds are detected in DE samples based on GC/MS analysis. The related reaction mechanisms are discussed based on the experimental results.展开更多
The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres...The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres containing 02, H2, CO, CH4, and CO2 were studied. The specific surface area of the char was found to decrease with increasing pyrolysis temperature. The interlayer spacing of the char also decreased, while the average stacking height and carbon crystal size increased at higher temperatures, suggesting that the char generated at high temperatures had a highly ordered structure. The char obtained using an ER value of 0.064 exhibited the highest specific surface area and oxidation reactivity. Rela- tively high 02 concentrations degraded the pore structure of the char, decreasing the surface area. The char produced in an atmosphere incorporating H2 showed a more condensed crystalline structure and consequently had lower oxidation reactivity.展开更多
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the grant support from the National Natural Science Foundation of China (No. 21975018, 22278032)。
文摘Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.
基金Supported by Natural Science Foundation of Shanxi Province (202203021221219)Research on the Construction of Scientific and Technological Innovation Think Tank of Shanxi Association for Science and Technology (KXKT202542)Planning Project under Commerce Statistical Society of China (2025STY122)。
文摘As a key component of shale oil,petroleum fractions,and chemical products,the oxidative pyrolysis behavior of paraffin directly influences energy conversion efficiency and the direction of process optimization.A deep understanding of its oxidative pyrolysis mechanism is crucial for addressing wax deposition in oil and gas extraction,enhancing product selectivity in cracking processes,and advancing novel clean fuel technologies.Traditional experimental methods face challenges in capturing transient free-radical reaction pathways at high temperatures,whereas molecular dynamics simulations offer a powerful approach to bridge the research gap in elucidating atomic-scale dynamic mechanisms.This database is constructed based on high-precision molecular dynamics simulations,comprising oxidative pyrolysis trajectory data for three paraffin models featuring different straight-chain hydrocarbon distributions within the temperature range of 2100-2500 K.The COMPASS force field was employed to optimize the initial structures,and the ReaxFF reactive force field was used to simulate the oxidative pyrolysis process.The database includes atomic trajectories,species evolution information,and reaction network analysis results for both heating and isothermal cracking processes,with a total data volume of approximately 141 GB(including 150000 atomic configuration frames).The data is stored in a hierarchical directory structure,supporting multi-scale oxidative pyrolysis mechanism studies and providing atomic-scale dynamic evidence for revealing carbon chain length effects and temperature sensitivity.
基金Fundamental Research Funds for the Central Universities(M23JBZY00050)National Natural Science Foundation of China(22278032)。
文摘The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured.The results show that the consumption of NH_(3)/O_(2)and the production of N_(2)/H_(2)change linearly with the increase of voltage,which indicates the decoupling of nonequilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures.Secondly,the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established.Based on the reaction path analysis,the simplified mechanism is obtained.The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism.Finally,based on the simplified mechanism,the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species.The results show that the generation,development,and propagation of the pre-sheath have a great influence on the formation and consumption of species.The consumption of NH_(3)by the cathode pre-sheath is greater than that by the anode pre-sheath,but the opposite is true for OH and O(1S).However,within the sheath,almost all reactions do not occur.Further,by changing the parameters of nanosecond pulse power supply voltage,it is found that the electron number density,electron current density,and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath.Furthermore,the discharge interval has little effect on the sheath structure and gas mixture breakdown.The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.
基金Supported by the Fund from the Air Force Armament Department of China for Innovative Research Group(Grant KJ2012283)
文摘The thermal degradation of two synthetic lubricants base oils, poly-a-olefins （PAO） and di-esters （DE）, was investigated under oxidative pyrolysis condition and their properties were characterized in simulated ＂areo-engine＂ by comparing the thermal stability and identifying the products of thermal decomposition as a function of exposure temperature. The characterization of the products were performed by means of Fourier transform infrared spectrometry （FTIR）, gas chromatography/mass spectrometry （GC/MS） and viscosity experiments. The results show that PAO has the lower thermal stability, being degraded at 200℃ different from 300 ℃ for DE. Several by-products are identified during the thermal degradation of two lubricant base oils. The majority of PAO products consist of alkenes and olefins, while more oxygen-contained organic compounds are detected in DE samples based on GC/MS analysis. The related reaction mechanisms are discussed based on the experimental results.
文摘The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres containing 02, H2, CO, CH4, and CO2 were studied. The specific surface area of the char was found to decrease with increasing pyrolysis temperature. The interlayer spacing of the char also decreased, while the average stacking height and carbon crystal size increased at higher temperatures, suggesting that the char generated at high temperatures had a highly ordered structure. The char obtained using an ER value of 0.064 exhibited the highest specific surface area and oxidation reactivity. Rela- tively high 02 concentrations degraded the pore structure of the char, decreasing the surface area. The char produced in an atmosphere incorporating H2 showed a more condensed crystalline structure and consequently had lower oxidation reactivity.
