Quantitative behavior of vibrational excitation in AC plasma assisted dry reforming of methane

Quantitative behavior of non-equilibrium excitation by direct electron impact in low-temperature dry reforming of methane was investigated by integrated studies of experimental validation and kinetic modeling.A plasma chemistry kinetic mechanism incorporating the reactions involving vibrational excitation of CH4,CO2,H2 and CO molecules as well as the low temperature He/CH4/CO2 conversion pathways was developed and validated.The calculation results showed that at lower E/N values(<150 Td)large population of energized electrons generated in a He/CH4/CO2 discharge resulted in an intensification of vibrational excitation.Despite the large generation of vibration,the vibrationally excited molecules in a 0.5/0.25/0.25 of He/CH4/CO2 discharge mixture were easy to relax,due to the strong coupling of the vibration of different molecules in a gas mixture.The results showed that the moderate levels of the vibrational excitation,such as CO2(v10,11,...,18)and CO(v9,10),presented most efficient in the stimulation of species generation including CO,CH2 O,CH3 OH,C2 H4 and C2 H6.Specifically,under conditions of E/N of 108 Td,14.9%of CO formation was estimated from the recombination of CO2(v)with CH3 and H,CO2(v)+CH3→CH3 O+CO,CO2(v)+H→CO+OH.Also,4.8%of C2 H4 formation was from the recombination reaction CH4(v)+CH→C2 H4+H.These results highlight the strong roles of vibrational states in a complex plasma chemistry system.

Investigation of flame structure in plasma-assisted turbulent premixed methane-air flame

The mechanism of plasma-assisted combustion at increasing discharge voltage is investigated in detail at two distinctive system schemes（pretreatment of reactants and direct in situ discharge）.OH-planar laser-induced fluorescence（PLIF） technique is used to diagnose the turbulent structure methane-air flame,and the experimental apparatus consists of dump burner,plasma-generating system,gas supply system and OH-PLIF system.Results have shown that the effect of pretreatment of reactants on flame can be categorized into three regimes：regime I for voltage lower than 6.6 k V;regime II for voltage between 6.6 and 11.1 k V;and regime III for voltage between11.1 and 12.5 k V.In regime I,aerodynamic effect and slower oxidation of higher hydrocarbons generated around the inner electrode tip plays a dominate role,while in regime III,the temperature rising effect will probably superimpose on the chemical effect and amplify it.For wire-cylinder dielectric barrier discharge reactor with spatially uneven electric field,the amount of radicals and hydrocarbons are decreased monotonically in radial direction which affects the flame shape.With regard to in situ plasma discharge in flames,the discharge pattern changes from streamer type to glow type.Compared with the case of reactants pretreatment,the flame propagates further in the upstream direction.In the discharge region,the OH intensity is highest for in situ plasma assisted combustion,indicating that the plasma energy is coupled into flame reaction zone.

Kinetic contribution of CO_2/O_2 additive in methane conversion activated by non-equilibrium plasmas

A temperature-controlled and pressure-controlled coaxial dielectric barrier discharge （DBD） reactor was developed to decouple the thermal and kinetic effects of radio frequency （RF） discharge on methane conversion, and further to compare the kinetic behaviors of the mechanistically similar reactions of methane conversion with O2 and CO2 additives. A kinetic mechanism for RF plasma assisted methane conversion was assembled. The formation of products in the RF plasma reactor was measured with Gas Chromatography （GC-TCD） and the data were used to validate the kinetic model. The experimental and computational results showed the different kinetic roles of carbon dioxide and oxygen additives in methane conversion, due to the different dissociation and ionization energy of the two additive gases, as well as the thus produced electron energy distribution function （EEDF）. Fuel oxidation by plasma generated O, O（1D）, O2（a1△Ag）, O2（b1∑＋g） and O＋ in partial oxidation of methane was observed essential for methane consumption, which resulted in an increase in methane conversion rate, compared to pure methane pyrolysis and dry reforming of methane with CO2 additive. It was also found that dry reforming of methane with CO2 was by far the easier to produce the syngas as well as C2 hydrocarbon species, due to the weak oxidation ability of CO2 and also the significant deposition of the electron energy on CH4 disso- ciation in a dry reforming discharge mixture. This kinetic study produced comparative data to demonstrate the contribution of CO2/O2 additive in non-eauilibrium plasma assisted methane conversion.