3.1. The Dielectric Constant of the Packed Materials
The literature values for the dielectric constant of the tested materials are presented in
Table 1. Among all tested materials, BaTiO
3 possesses the highest dielectric constant (>1000) [
18]. In general, the dielectric constant of ferroelectric materials, i.e., BaTiO
3, can largely vary depending on the applied frequency and temperature.
Dong et al. [
21] measured the dielectric constant of BaTiO
3 powder, supplied by Alfa Acer, similar to the powder tested in the present study. It was found that the value for the dielectric constant of BaTiO
3 is above 1000 for a wide range of applied frequencies and temperatures. In comparison with BaTiO
3, γ-alumina, α-alumina, and silica-SBA-15 possess significantly lower dielectric constants, as reported in several studies [
18,
22,
23]. Alumina (γ and α) has a higher dielectric constant than silica-SBA-15, which is known for its low dielectric properties [
24].
3.2. The Effect of Packing on Plasma Electrical Parameters
The presence of packing with different dielectric constants influences the plasma electrical parameters, such as applied voltage, discharge power, and the characteristics of discharges. The applied voltage and discharge power are shown in
Table 2 for the nonpacked (blank) reactor and the packed reactor. When the plasma gap is packed with solid particles, a higher voltage of 8.9–10.0 kV is required to keep the input energy in the range of 7–8 W, compared to the voltage applied for the blank reactor (7.6 kV).
Due to the presence of solid particles, the gap between the high-voltage electrode and the ground electrode decreases. This therefore reduces the space for the formation of discharges in comparison with the nonpacked (Blank) reactor. As a result, the breakdown voltage of a packed-bed DBD plasma reactor was expected to be lower than the breakdown voltage of a DBD plasma reactor without packing. This has been experimentally demonstrated in previous studies for different reactions [
22,
25,
26]. According to the present study, presented in
Table 3, all materials utilized as the packing exhibited a lower breakdown voltage compared to the nonpacked reactor. Results indicate that the breakdown voltage was not largely dependent on the dielectric constant of the packing, except for BaTiO
3, which was relatively lower (ca. 30%) than that for γ-alumina, α-alumina, and silica-SBA-15. This indicates that a lower breakdown voltage for the packed-bed DBD reactor originates from the reduction of the discharge gap, as well as the pressure drop of the gas flow across the packed bed [
10].
The plasma volume can be entirely covered with discharges as long as the charges generated on the high-voltage electrode can be fully transferred to the ground electrode, which is a typical case for a nonpacked DBD reactor. This becomes a different case when the plasma discharge gap is occupied by solid particles. In this case, each particle of the packing functioned as a capacitor, which could bridge the transfer of charges across the plasma discharge zone. In addition, at the same time, each particle could trap the charges as well. This phenomenon is called “partial discharging” in packed-bed DBD plasma reactors [
19,
22,
27,
28], where a part of the charges is trapped by solid particles rather than being transferred across the bed. This affects the strength of the generated electric field between the high-voltage electrode and the ground electrode and, consequently, impacts the conversion and the selectivities of the final products.
The presence of dielectric materials increases the overall capacitance of the plasma electric circuit due to their high dielectric constant compared to a nonpacked reactor. The capacitance (C) is inversely proportional to the applied voltage (V) and correlated by C = Q/V, where Q is the amount of the charge, which is transferred across the discharge gap. In order to inhibit the partial discharging, the applied voltage should be sufficiently higher than the breakdown voltage to generate a full discharging across the packed bed. This can be seen in Lissajous figures (
Figure 1), which show that the voltages applied for both cases of a nonpacked and packed reactor are considerably higher than the breakdown voltage of the reactor.
The presence of the packing influences the shape of the Lissajous figure, changing from a parallelogram form, which is a typical form for nonpacked DBD plasma reactors, to an oval form (almond shape), when the discharge gap is packed with a catalyst, as shown in
Figure 1. This can be attributed to the occurrence of a combination of filamentary discharges accompanied with surface discharges, which are formed across the packed bed, rather than only filamentary discharges, which are typically formed when no packing is utilized [
15,
27,
29].
3.3. The Conversion of Methane
The conversion of methane as a function of time is shown in
Figure 2. The BaTiO
3 packed-bed reactor demonstrates a remarkably lower conversion (below 20%), in contrast to γ-alumina, α-alumina, and silica-SBA-15. This indicates that using BaTiO
3 with a high dielectric constant as the packing leads to a lower conversion of methane.
Among low dielectric materials, the silica-SBA-15 packed reactor shows a relatively lower conversion of methane compared to γ-alumina and α-alumina. This can be ascribed to the high surface area of silica-SBA-15 (673 m2/gr) as well as its known high porosity, which therefore can increase the possibilities of partial discharging due to the trapping of charges inside the small pores of silica-SBA-15. This therefore reduces the propagation of plasma discharges across the bed, which is the case for a highly porous silica-SBA-15 packing, where the interrupted plasma propagation causes the formation of a weaker electric field and, consequently, leads to a lower conversion of methane. In addition, the conversion of methane is accompanied with the formation of solid deposits, which can become significantly greater for a highly porous material. The presence of solid products on the packing can additionally influence the formation of discharges and the sustainability of the plasma, leading to a weaker overall electric field.
Zhang et al. [
30] studied the rate of electron impact ionization for a DBD plasma reactor in combination with catalyst particles in a modelling study. The authors considered a wide range of dielectric constants for a catalyst, starting from 4 up to 1000, and investigated the strength of the electric field formed inside the catalyst pores with different sizes. It was found that the formation of microdischarges could be greatly affected by the dielectric constant of the packing, which also depends on the porosity of the utilized catalyst. It was discussed how, for a pore size of 100 µm, the rate of ionization is enhanced only for materials with dielectric constants below 300. In this case, porous structures (i.e., Al
2O
3 and SiO
2) are more likely to allow the formation of discharges even inside the small pores, due to their low dielectric constant in comparison with a high dielectric material (i.e., BaTiO
3). However, the pore sizes studied by Zhang et al. [
30] are in the range of 10 to 100 µm, whereas typical pores in catalytic packings are much smaller.
BaTiO
3 tested in the present study had a pore size distribution within the range of 10–200 nm, as shown in
Figure 3. The pore volume of the tested γ-alumina is shown in
Figure 4. Compared to BaTiO
3, γ-alumina possesses smaller pore diameters with a narrow size distribution of around 20 nm.
The experimental results of the present study indicate that a high dielectric material (i.e., BaTiO3) cannot enhance the plasma electric field. This is related to the combined effect of the dielectric constant and the porosity of BaTiO3. For small pores, the walls of the pore are in close proximity. In this way, for a high dielectric material with small pores, the accumulation of charges inside the pores does not lead to a strong electric field, as the mutual polarization of the walls counteracts the effect of each other. Thus, high dielectric BaTiO3 with small pores functions as a medium that can mainly store the energy rather than transfer it to CH4 molecules. In contrast, γ-alumina with a remarkably lower dielectric constant, and even with smaller pores than BaTiO3, can still improve the strength of the electric field and, consequently, enhance the conversion of methane.
3.4. The Distribution of Products
The selectivities of C
2 products are shown in
Figure 5. BaTiO
3 exhibits a higher selectivity towards unsaturated compounds (C
2H
2 and C
2H
4). For γ-alumina, α-alumina, and silica-SBA-15, the distribution of C
2 products shifts towards a higher production of C
2H
2 and C
2H
4, which is higher than that obtained for the nonpacked reactor. This indicates that the enhancement of the electric filed across the bed for low dielectric materials shifts the distribution of CH
x radicals (i.e., generated by decomposition of CH
4), resulting in a higher production of CH
2 and CH radicals (i.e., obtained via H abstraction reactions) rather than CH
3 radicals. This increases the rate of dimerization of CH
2 and CH radicals, and therefore leads to the formation of a higher amount of C
2H
4 and C
2H
2.
For the BaTiO
3 packed plasma reactor, the selectivity of C
2H
2 and C
2H
4 reached 18% and 32%, respectively, higher than the values of 7% and 6% obtained for the nonpacked reactor; however, a low conversion of methane resulted in a low yield of C
2. For a better comparison, the yield of C
2 products is depicted in
Figure 6. A lower yield of C
2 was obtained for the BaTiO
3 packed plasma reactor. Similarly, the yield of C
2H
4 (
Figure 6) was lower for the reactor packed with BaTiO
3.
Figure 7 clearly shows that for γ-alumina, α-alumina, and silica-SBA-15, C
2H
4 yield increases, except BaTiO
3, which shows almost the same yield as the nonpacked reactor. The C
2H
4 yield reaches a range of 3.3–3.8% for γ-alumina, α-alumina, and silica-SBA-15, nearly two times more than the value of 1.8% obtained for the nonpacked reactor. In this way, the distribution of CH
x radicals appears to be largely influenced for the packed reactor, shifting to a greater production of CH
2 radicals, which consequently leads to a higher production of C
2H
4.
The selectivities of C
3 and larger hydrocarbons (C
4+) are depicted in
Figure 8. The selectivity of C
3H
6 increases to a higher value for the packed reactor in comparison with the nonpacked reactor, as shown in
Figure 8a. In contrast, the formation of C
3H
8 (
Figure 8b) is lower for the packed reactor. Similar to the changes obtained for the selectivity of C
2H
4, the selectivity of C
3 hydrocarbons shifts towards unsaturated C
3H
6. The enhancement of the electric field, due to the presence of the packing particles, increases the energy of the generated electrons and plasma-induced species (e.g., radicals) to a higher level. This extra energy changes the distribution of CH
x radicals and also changes the distribution of C
2H
y radicals (i.e., obtained via recombination of CH
x radicals). In this case, the distribution of C
2H
y radicals shifts to a higher production of C
2H
3 and C
2H radicals rather than C
2H
5 radicals, obtained via H abstraction reactions. As a result, the rate of the formation of unsaturated C
2 products (i.e., obtained from dimerization of CH
2 and CH) and the rate of the formation of C
3H
6 product (i.e., obtained from recombination of CH
2, C
2H
3, and H) become greater, resulting in a higher selectivity of C
2H
2, C
2H
4, and C
3H
6. The formation of C
4+ is slightly influenced by the presence of the packing and it remains at the same level as in the nonpacked reactor, as shown in
Figure 8c.
The selectivity of deposits is depicted in
Figure 9a. A lower amount of deposits is formed for the BaTiO
3 packed reactor. This can be attributed to a lower conversion of methane, which is proportional to a lower yield of H
2 (i.e., obtained from decomposition of CH
4 depicted in
Figure 9b), which therefore leads to a lower formation of deposits. A lower formation of deposits is favourable for the sustainability of the process, but on the other hand, the C
2 yield significantly drops when a low conversion of methane is achieved. Therefore, a low dielectric material (i.e., alumina) is preferred as the packing in a packed-bed DBD plasma reactor rather than a high dielectric material (i.e., BaTiO
3).
3.5. The Behaviour of BaTiO3 and γ-Alumina at Different Discharge Powers
The effect of input power on the performance of BaTiO
3 packed reactor was evaluated, as shown in
Figure 10.
The conversion of methane tends to increase from 7.8% to 16.5% by increasing the discharge power from 3.0 W to 5.5 W. Increasing the discharge power from 5.5 W to 10.2 W does not promote the conversion of methane for the BaTiO
3 packed reactor, whereas the conversion of methane slightly changes from 16.5% to 17.2%. This can be attributed to the small pores of BaTiO
3 in combination with its high dielectric properties. In this way, applying higher values of discharge power can only increase the charge density inside the pores, but does not lead to a strong polarization [
30]. As a consequence, the overall electric field between the high voltage electrode and the ground electrode almost remains at the same level of intensity, and the conversion of CH
4 therefore becomes independent of discharge power.
The selectivity of deposits increases from 36.1% to 44.5% by increasing the discharge power from 3.0 W to 10.2 W, as shown in
Figure 10. In contrast, the selectivity of C
2 products decreases from 48.5% to 38.4%. This indicates that the extra energy provided to the plasma discharges mainly contributes to the decomposition of CH
4, which generates a higher amount of C radicals rather than CH
x radicals (i.e., CH
3, CH
2, CH). In this way, a lower generation of CH
x radicals leads to a lower formation of C
2 products, and consequently, a higher formation of deposits.
Figure 11 depicts the conversion of methane versus discharge power for the reactor packed with BaTiO
3 and γ-alumina, as well as for the nonpacked reactor. It can be seen that increasing the discharge power has a positive effect in improving the conversion of methane in the case of using γ-alumina as the packing, in contrast to the BaTiO
3 packed reactor. Likewise, H
2 yield follows the same trend as the conversion of methane, as shown in
Figure 12.
The yield of C
2 versus discharge power is depicted in
Figure 13. For the nonpacked reactor, the yield of C
2 slightly increases; however, for the γ-alumina packed reactor, the yield of C
2 follows an ascending trend. For BaTiO
3 packed reactor, the yield of C
2 is independent of the discharge power, following the same trend as obtained for the conversion of CH
4 at elevated discharge powers.
Figure 14 shows the yield of C
2H
4 as a function of discharge power. For the nonpacked reactor, the yield of C
2H
4 remains almost unchanged by increasing the discharge power. This indicates that increasing the discharge power mainly increases the rate of CH
4 decomposition to form H
2 and deposits. In contrast, for both the BaTiO
3 and γ-alumina packed reactor, the yield of C
2H
4 improves by increasing the discharge power, whereas this effect is more profound for the γ-alumina packed reactor.
3.6. The Analysis of the Energy Efficiency
In order to analyse the energy efficiency, two definitions are considered. In the first analysis, the energy efficiency is defined based on the amount of converted methane divided by the discharge power, applied for the plasma reaction as shown in the equation below:
These values are presented in
Table 4.
The second definition is based on the high heat value of the products, the amount of converted methane, and the discharge power as represented in the equation below:
where i is product; HHV(i) is high heat value of i (J/mol); molar flow rate of i is in mol/s; and discharge power is in watts.
The results of the second definition are represented in
Figure 15. Similar conclusions can be drawn from both definitions of the energy efficiency. It can be seen that BaTiO
3 could convert a lower amount of methane compared to other packing materials, as well as compared to the nonpacked reactor. This implies that high dielectric BaTiO
3 can transfer a small part of the input energy for the activation of CH
4 molecules. In this case, compared to γ-alumina, α-alumina, and silica-SBA-15, a part of the input energy is dissipated into the BaTiO
3 packed bed, instead of being transferred across the packed bed. This leads to a lower conversion of CH
4 and, consequently, a lower energy efficiency. This becomes a different case when the DBD reactor is packed with alumina particles. A higher energy efficiency is obtained, significantly higher than that obtained for the BaTiO
3 packed reactor.
The silica-SBA-15 packed reactor possesses a relatively lower energy efficiency (0.0938 mmol/kJ) than the values obtained for the γ-alumina (0.1315 mmol/kJ) and α-alumina (0.1468 mmol/kJ) packed reactor, due to the partial discharging, which can become greater for a packing with a high surface area and porosity (i.e., silica-SBA-15). In this way, the charges generated on the high-voltage electrode can be trapped inside the pores, and therefore, discharges are not able to bridge the gap between the high-voltage electrode and the ground electrode. As a result, the strength of the electric field becomes relatively weaker. This has been reported to take place when DBD plasma discharges are combined with different packing materials utilized for other applications [
22,
27,
28]. In order to achieve a complete discharging, charges generated on the high-voltage electrode should be entirely transferred to the ground electrode. In the case of using packing, each particle of the packed bed can behave as a capacitor, which is capable of both transferring as well as trapping the charges inside the pores. This largely depends on the dielectric properties of the packing and its porosity.
The dielectric constants of α-alumina and γ-alumina are nearly the same. The conversion of methane and the energy efficiency for both α-alumina and γ-alumina packed reactors are at the same level, despite their differences in surface area and porosity. Thus, it can be stated that in the case of alumina (γ or α phase), the dielectric constant has a dominant effect compared to its surface area and its porosity. This furthermore indicates that the catalytic activity of γ-alumina does not contribute to improving the conversion and the distribution of products, whereas α-alumina (i.e., having no catalytic activity) can still boost the conversion of methane, due to its dielectric properties.