T Martens

Conversion of carbon dioxide to value-added chemicals in atmospheric pressure dielectric barrier discharges

The aim of this work consists of the evaluation of atmospheric pressure dielectric barrier discharges for the conversion of greenhouse gases into useful compounds. Therefore, pure CO2 feed flows are administered to the discharge zone at varying discharge frequency, power input, gas temperature and feed flow rates, aiming at the formation of CO and O2. The discharge obtained in CO2 is characterized as a filamentary mode with a microdischarge zone in each half cycle of the applied voltage. It is shown that the most important parameter affecting the CO2-conversion levels is the gas flow rate. At low flow rates, both the conversion and the CO-yield are significantly higher. In addition, also an increase in the gas temperature and the power input give rise to higher conversion levels, although the effect on the CO-yield is limited. The optimum discharge frequency depends on the power input level and it cannot be unambiguously stated that higher frequencies give rise to increased conversion levels. A maximum CO2 conversion of 30% is achieved at a flow rate of 0.05Lmin −1 , a power density of 14.75Wcm −3 and a frequency of 60kHz. The most energy efficient conversions are achieved at a flow rate of 0.2Lmin −1 , a power density of 11Wcm −3 and a discharge frequency of 30kHz. (Some figures in this article are in colour only in the electronic version)

The dominant role of impurities in the composition of high pressure noble gas plasmas

We present in this letter how a molecular gas such as nitrogen at different levels of impurity dominates the ionic composition of an atmospheric pressure noble gas plasma such as in helium. The positive charge in the discharge is only determined by helium ions if the discharge gas contains less than 1ppm of impurity. Above this impurity level, the positive charge is completely determined by the impurity nitrogen. The higher the relative nitrogen concentration, the more N4+ dominates over N2+. If the impurity level is between 1 and about 20ppm, N2+ is clearly the most abundant positive ion but for higher levels of impurity, N4+ almost completely determines the positive charge.

Dielectric barrier discharges used for the conversion of greenhouse gases: modeling the plasma chemistry by fluid simulations

The conversion of methane to value-added chemicals and fuels is considered to be one of the challenges of the 21st century. In this paper we study, by means of fluid modeling, the conversion of methane to higher hydrocarbons or oxygenates by partial oxidation with CO2 or O2 in a dielectric barrier discharge. Sixty-nine different plasma species (electrons, ions, molecules, radicals) are included in the model, as well as a comprehensive set of chemical reactions. The calculation results presented in this paper include the conversion of the reactants and the yields of the reaction products as a function of residence time in the reactor, for different gas mixing ratios. Syngas (i.e. H2 + CO) and higher hydrocarbons (C2Hx) are typically found to be important reaction products. (Some figures in this article are in colour only in the electronic version)

Pulse shape influence on the atmospheric barrier discharge

In this letter we compare the effect of a radio-frequency sine, a low frequency sine, a rectangular and a pulsed dc voltage profile on the calculated electron production and power consumption in the dielectric barrier discharge. We also demonstrate using calculated potential distribution profiles of high time and space resolution how the pulsed dc discharge generates a secondary discharge pulse by deactivating the power supply.

On the regime transitions during the formation of an atmospheric pressure dielectric barrier glow discharge

The atmospheric pressure dielectric barrier discharge in helium is a pulsed discharge in nature. If during the electrical current pulse a glow discharge is reached, then this pulse will last only a few microseconds in operating periods of sinusoidal voltage with lengths of about 10 to 100 µs. In this paper we demonstrate that right before a glow discharge is reached, the discharge very closely resembles the commonly assumed Townsend discharge structure, but actually contains some significant differing features and hence should not be considered as a Townsend discharge. In order to clarify this, we present calculation results of high time and space resolution of the pulse formation. The results indicate that indeed a maximum of ionization is formed at the anode, but that the level of ionization remains high and that the electric field at that time is significantly disturbed. Our results also show where this intermediate structure comes from. (Some figures in this article are in colour only in the electronic version)

Fluid modelling of an atmospheric pressure dielectric barrier discharge in cylindrical geometry

A numerical parameter study has been performed for a cylindrical atmospheric pressure dielectric barrier discharge (DBD) in helium with nitrogen impurities using a two-dimensional time-dependent fluid model. The calculated electric currents and gap voltages as a function of time for a given applied potential are presented, as well as the number densities of the various plasma species. This study shows that for the geometry under consideration the applied voltage parameters have a large impact on the electric current profiles and that the discharge current is always determined by the electron and ion conduction currents while the displacement current is nearly negligible. A relative broadening of the current profiles (compared with the duration of the half cycle of the applied voltage) with an increase in the applied frequency is obtained. Nearly sinusoidal current wave forms, usually typical for radio frequency DBDs, are observed while still operating at the frequencies of tens of kilohertz. For the setup under investigation, the Townsend mode of the DBD is observed in the entire range of applied voltage amplitudes and frequencies. It is shown that the average power density dissipated in the discharge increases with rising applied voltage and frequency. An increase in applied voltage frequency leads to an increase in the electron density and a decrease in electron energy, while increasing the voltage amplitude has the opposite effect.

The influence of impurities on the performance of the dielectric barrier discharge

In this letter, we investigate the effect of various levels of nitrogen impurity on the electrical performance of an atmospheric pressure dielectric barrier discharge in helium. We illustrate the different current profiles that are obtained, which exhibit one or more discharge pulses per half cycle and evaluate their performance in ionizing the discharge and dissipating the power. It is shown that flat and broad current profiles perform the best in ionizing the discharge and use the least amount of power per generated charged particle.

Theoretical Characterization of an Atmospheric Pressure Glow Discharge Used for Analytical Spectrometry

We have investigated the plasma processes in an atmospheric pressure glow discharge (APGD) in He used for analytical spectrometry by means of fluid and Monte Carlo (MC) simulations. Typical results include the potential and electric field distributions in the plasma, the density profiles of the various plasma species throughout the discharge, the mean electron energy, as well as the rates of the various collision processes in the plasma, and the relative importance of the different production and loss rates for the various species. The similarities and differences with low-pressure glow discharges are discussed. The main differences are a very small cathode dark space region and a large positive column as well as the dominant role of molecular ions. Some characteristic features of the APGD, such as the occurrence of the different spatial zones in the discharge, are illustrated, with links to experimental observations.

Modeling of the plasma chemistry and plasma–surface interactions in reactive plasmas

In this paper, an overview is given of modeling activities going on in our research group, for describing the plasma chemistry and plasma–surface interactions in reactive plasmas. The plasma chemistry is calculated by a fluid approach or by hybrid Monte Carlo (MC)–fluid modeling. An example of both is illustrated in the first part of the paper. The example of fluid modeling is given for a dielectric barrier discharge (DBD) in CH4/O2, to describe the partial oxidation of CH4 into value-added chemicals. The example of hybrid MC–fluid modeling concerns an inductively coupled plasma (ICP) etch reactor in Ar/Cl2/O2, including also the description of the etch process. The second part of the paper deals with the treatment of plasma–surface interactions on the atomic level, with molecular dynamics (MD) simulations or a combination of MD and MC simulations.

Modeling study on the influence of the pressure on a dielectric barrier discharge microplasma

In this paper we present a one-dimensional fluid model to study the properties of very small dielectric barrier discharges (DBD), which can be used as microchip plasma sources for analytical spectrometry. The influence of the pressure on this kind of discharge was investigated to obtain more insight in the variations of discharge current and the differences in particle densities that arise when operating at different pressures. The studied discharge gas is helium and is described with passive He background atoms, He+ and He2+ ions, He metastable atoms, higher excited states of He, He2* excimers and electrons. We show that the plasma activity, expressed in discharge current, is remarkably higher for pressures ranging from 50 to 140 mbar. For most pressures the calculated maximum current density is about 0.1 A cm−2, whereas in the range from 50 to 140 mbar the maximum current density is about 0.3 A cm−2. We also report how the plasma densities alter at different operating pressures, with spatially averaged densities at maximum current ranging from about 1016 m−3 to 1018 m−3, depending on the plasma species, and identify the main underlying processes, which are responsible for these evolutions.