The Chemical Origins of Plasma Contraction and Thermalization in CO2 Microwave Discharges

Thermalization of electron and gas temperature in CO2 microwave plasma is unveiled with the first Thomson scattering measurements. The results contradict the prevalent picture of an increasing electron temperature that causes discharge contraction. It is known that as pressure increases, the radial extension of the plasma reduces from ∼7 mm diameter at 100 mbar to ∼2 mm at 400 mbar. We find that, simultaneously, the initial nonequilibrium between ∼2 eV electron and ∼0.5 eV gas temperature reduces until thermalization occurs at 0.6 eV. 1D fluid modeling, with excellent agreement with measurements, demonstrates that associative ionization of radicals, a mechanism previously proposed for air plasma, causes the thermalization. In effect, heavy particle and heat transport and thermal chemistry govern electron dynamics, a conclusion that provides a basis for ab initio prediction of power concentration in plasma reactors

The Chemical Origins of Plasma Contraction and Thermalization in CO2 Microwave Discharges

Thermalization of electron and gas temperature in CO2 microwave plasma is unveiled with the first Thomson scattering measurements. The results contradict the prevalent picture of an increasing electron temperature that causes discharge contraction. It is known that as pressure increases, the radial extension of the plasma reduces from ∼7 mm diameter at 100 mbar to ∼2 mm at 400 mbar. We find that, simultaneously, the initial nonequilibrium between ∼2 eV electron and ∼0.5 eV gas temperature reduces until thermalization occurs at 0.6 eV. 1D fluid modeling, with excellent agreement with measurements, demonstrates that associative ionization of radicals, a mechanism previously proposed for air plasma, causes the thermalization. In effect, heavy particle and heat transport and thermal chemistry govern electron dynamics, a conclusion that provides a basis for ab initio prediction of power concentration in plasma reactors.</p

Resolving discharge parameters from atomic oxygen emission

A method is proposed to spatially resolve discharge parameters from experimental measurements of emission intensity and 1D numerical simulations including an O atom collisional-radiative model. The method can be used for different plasmas and conditions. Here, contracted microwave discharges for CO2 conversion are studied at intermediate to high pressures (100–300 mbar). Radial profiles of electron density (ne) are used as input in the model and corrected to successfully simulate the measured Gaussian profiles of emission intensity of the 777 nm transition (I777). As a result, radially-resolved parameters inaccessible in experiments, such as ne, power density (Pabs), electron temperature (Te), electric field and reaction rates, are numerically-obtained for several conditions. ne and Pabs approximately follow Gaussian profiles that are broader than that of I777. For pressures below 150 mbar, the difference in full width at half maximum is typically a factor 1.6. This consists in a phenomenon of optical contraction, which is due to concave profiles of O molar fraction and Te. The implications of the simulated profiles on the study of plasmas for CO2 conversion are discussed and it is shown that these profiles allow to explain high reactor performances at low pressures

Flame bands: CO + O chemiluminescence as a measure of gas temperature

Carbon monoxide flame band emission (CO+O → CO2+hV) in CO2 microwave plasma is quantified by obtaining absolute calibrated emission spectra at various locations in the plasma afterglow while simultaneously measuring gas temperatures using rotational Raman scattering. Comparison of our results to literature reveals a contribution of O2 Schumann-Runge UV emission at T &gt; 1500 K. This UV component likely results from the collisional exchange of energy between CO2(1B) and O2. Limiting further analysis to T &lt; 1500 K, we demonstrate the utility of CO flame band emission by analyzing afterglows at different plasma conditions. We show that the highest energy efficiency for CO production coincides with an operating condition where very little heat has been lost to the environment prior to ∼3 cm downstream, while simultaneously, T ends up below the level required to effectively freeze in CO. This observation demonstrates that, in CO2 plasma conversion, optimizing for energy efficiency does not require a sophisticated downstream cooling method.</p

Insight into CO2 Dissociation Kinetics in Microwave Plasma using Laser Scattering

Embargo 1 year, pdf open access 1-3-202

Insight into CO2 Dissociation Kinetics in Microwave Plasma using Laser Scattering

Embargo 1 year, pdf open access 1-3-202

Thermal instability and volume contraction in a pulsed microwave N-2 plasma at sub-atmospheric pressure

We studied the evolution of an isolated pulsed plasma in a vortex flow stabilised microwave (MW) discharge in N-2 at 25 mbar via the combination of 0D kinetics modelling, iCCD imaging and laser scattering diagnostics. Quenching of electronically excited N-2 results in fast gas heating and the onset of a thermal-ionisation instability, contracting the discharge volume. The onset of a thermal-ionisation instability driven by vibrational excitation pathways is found to facilitate significantly higher N-2 conversion (i.e. dissociation to atomic N-2) compared to pre-instability conditions, emphasizing the potential utility of this dynamic in future fixation applications. The instability onset is found to be instigated by super-elastic heating of the electron energy distribution tail via vibrationally excited N-2. Radial contraction of the discharge to the skin depth is found to occur post instability, while the axial elongation is found to be temporarily contracted during the thermal instability onset. An increase in power reflection during the thermal instability onset eventually limits the destabilising effects of exothermic electronically excited N-2 quenching. Translational and vibrational temperature reach a quasi-non-equilibrium after the discharge contraction, with translational temperatures reaching similar to 1200 K at the pulse end, while vibrational temperatures are found in near equilibrium with the electron energy (1 eV, or similar to 11 600 K). This first description of the importance of electronically excited N-2 quenching in thermal instabilities gives an additional fundamental understanding of N-2 plasma behaviour in pulsed MW context, and thereby brings the eventual implementation of this novel N-2 fixation method one step closer

Influence of hydrogen addition on methane coupling in a moderate pressure microwave plasma

In this paper, the effect of hydrogen addition on methane coupling in a microwave moderate pressure (55 mbar and 110 mbar) plasma reactor has been studied. The use of optical emission spectroscopy allowed the determination of the rotational temperature of heavy particles and showed it to be in the range of 3000–4000 K. Due to the high temperature in the discharge the dominant product was acetylene and it was concluded that the methane coupling process is mainly through thermal decomposition with a key role of H radicals. It was revealed that the addition of hydrogen can increase both methane conversion and acetylene and ethylene yield and selectivity. With the CH4:H2 ratio of 1:1, the methane conversion increased from 31.0% to 42.1% (55 mbar) and from 34.0% to 48.6% (110 mbar), when compared to pure methane plasma. Respectively, the yield of acetylene increased from 14.4% to 25.3% (55 mbar) and from 20.1% to 34.0% (110 mbar). Moreover, the addition of hydrogen decreased the output of the problematic soot-like product. These results indicate that hydrogen addition can be a simple yet effective method of increasing selectivity to desirable products in plasma reforming of CH4

Influence of hydrogen addition on methane coupling in a moderate pressure microwave plasma

In this paper, the effect of hydrogen addition on methane coupling in a microwave moderate pressure (55 mbar and 110 mbar) plasma reactor has been studied. The use of optical emission spectroscopy allowed the determination of the rotational temperature of heavy particles and showed it to be in the range of 3000–4000 K. Due to the high temperature in the discharge the dominant product was acetylene and it was concluded that the methane coupling process is mainly through thermal decomposition with a key role of H radicals. It was revealed that the addition of hydrogen can increase both methane conversion and acetylene and ethylene yield and selectivity. With the CH4:H2 ratio of 1:1, the methane conversion increased from 31.0% to 42.1% (55 mbar) and from 34.0% to 48.6% (110 mbar), when compared to pure methane plasma. Respectively, the yield of acetylene increased from 14.4% to 25.3% (55 mbar) and from 20.1% to 34.0% (110 mbar). Moreover, the addition of hydrogen decreased the output of the problematic soot-like product. These results indicate that hydrogen addition can be a simple yet effective method of increasing selectivity to desirable products in plasma reforming of CH4