International Journal of Hydrogen Energy 31 (2006) 769 774 www.elsevier.

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Modeling of hydrogen-rich gas production by plasma reforming of hydrocarbon fuels

M.S. Benilova , , G.V. Naidisb
a Departamento de Fsica, Universidade da Madeira, Largo do Municipio, 9000 Funchal, Portugal b Institute for High Temperatures, Russian Academy of Sciences, Moscow 125412, Russia

Available online 9 August 2005

Abstract The work is devoted to simulation of plasma reforming of hydrocarbon gases by means of a kinetic approach. It is shown that the use of standard kinetic schemes, without inclusion of specic plasma processes, is sufcient for simulation of hydrogen production in discharges with hot plasmas, in particular, in low-current arc discharges. Results of simulation of methane and octane reforming are compared with data of experiments with low-current arcs available in the literature. An amount of hydrogen produced in octane reforming is calculated for a wide range of mixture compositions, temperatures at the reactor entrance, and discharge powers. 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

1. Introduction Plasma-chemical methods of hydrogen production from natural gas and liquid hydrocarbon fuels through partial oxidation and steam reforming processes are considered among the most promising. Recently, a number of works have appeared on the experimental study of plasma reforming of mixtures of hydrocarbons with air and steam by means of gas discharges of various types [19]. Typically, the efciency of hydrogen production with the use of cold plasmas, at gas temperatures in the discharge being lower than 400500 K (dielectric barrier discharges, coronas), is relatively low: the values of QH2 , the discharge energy required for production of one gram of H2 , exceed 30 kJ/g (or 0.6 eV per one H2 molecule). Higher efciency has been reached with the use of arc discharges at low currents (of the order of 102 101 A) and near atmospheric pressures [6,7]. In particular, values of QH2 in the range 313 kJ/g were obtained in partial oxidation of diesel fuel [6]. Note that though the plasma state in low-current arcs (at discharge currents
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E-mail address: benilov@uma.pt (M.S. Benilov).

about several tens of milliamperes) in molecular gases at atmospheric pressure may deviate from equilibrium, the gas temperature Tc in the arc core is relatively high. For example, values of Tc in atmospheric-pressure arcs in air at currents in the range 102 101 A are about 20003000 K [10]. Similar Tc values have been obtained for this current range also in our calculations of arc discharges in mixtures of air with hydrocarbons [11]. The effect of plasma may consist both in gas heating and in generation of chemically active species (excited molecules, radicals, ions, electrons) in collisions of gas molecules with electrons. The latter process is, evidently, dominating in cold plasmas, where the gas heating is small. Both experiments and calculations show that the energy cost of active species in discharges with cold plasmas is usually rather high, about several electron Volts [12]. The energy cost of active species in discharges with hot plasmas (arcs) is even higher than that in discharges with cold plasmas, because in arc discharges a major part of the energy input goes to gas heating. Therefore, the plasma processing of hydrocarbon gases due to production of active species could be energetically effective only in the case if these active species are capable of participating in chain

0360-3199/$30.00 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2005.06.018

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reactions, that is, to serve as catalysts. (Note that possible mechanisms of plasma catalysis of hydrocarbons due to ionmolecule reactions are discussed in [13,14].) According to the experimental data cited above, discharges with cold plasmas (dielectric barrier discharges, coronas), where the discharge effect is mainly in generation of active species, produce hydrogen less efciently than those with hot plasmas (arc discharges). Therefore, one may assume that for hot plasmas the effect of gas heating plays the major role. In [15,16] an analysis of the reforming process, aimed at the search of optimal conditions for hydrogen production, has been performed on the basis of thermodynamic approach. However, in general such approach is insufcient: the effective time of the overall chemical process should not exceed the residence time of reacting mixture inside the chemical reactor, the latter being typically in the range of seconds. Thus, more realistic estimates of parameters of the reforming process are required. Such estimates can be obtained using a kinetic approach. In this work, the known kinetic schemes for oxidation of hydrocarbon gases are used for simulation of methane and octane reforming in discharges with hot plasmas. On the basis of above considerations, the effect on hydrogen production of active species generated by discharges is assumed to be much smaller than that of gas heating. Therefore, no discharge-related non-equilibrium reactions are taken into account. The conditions are considered close to those realising in experiments with low-current arcs.

anism version 1.5 [19]. Simulation of octane reforming has been performed using the kinetic scheme [20]. Composition of the mixture of hydrocarbon Cn Hm with air and steam at the reactor entrance is characterized by two parameters, O/C ratio, dened as 2[O2 ]/n[Cn Hm ], and H2 O/C ratio, dened as [H2 O]/n[Cn Hm ]. Here [O2 ], [H2 O] and [Cn Hm ] are the volume ow rates of oxygen, water and hydrocarbon.

3. Results of simulation 3.1. Methane reforming Plasma reforming of methaneair mixtures has been simulated for conditions close to those of experiment [6]. The results of simulation are given in Figs. 1 and 2. O/C ratio was varied from 0.4 to 0.8, H2 O/C ratio was taken equal to zero. Fig. 1 shows the ratio H2 /CO of the molar fractions of H2 and CO in the reforming products versus O/C ratio; two lines correspond to the results obtained using two above mentioned mechanisms of methane combustion [18,19]. In the same gure experimental data are shown, for two O/C ratios ([6], Table 10, variants 3 and 4). It is seen that both kinetic schemes give the values of H2 /CO ratio rather close to those measured. However, the results obtained with the Leeds scheme [19] are in a better agreement with the experiment concerning the trend of variation of H2 /CO ratio with the change of O/C.

2. The model To simulate the plasma reforming process, a simple approach is used in which the discharge is accounted for as an additional, with respect to chemical processes, energy source inside the reactor. Calculations of chemical transformations, based on assumption of a perfect mixing of species inside the reactor chamber, are performed using the code PSR from the CHEMKIN-II package [17]. Input parameters for the code are the gas composition and temperature Tent at the reactor entrance, pressure p, the reactor volume V, the total mass ow rate G and the power loss from the reactor Wloss . To account for the energy input from the discharge, the value of Wloss in our calculations is taken negative, Wloss = W , where W is the discharge power. Output parameters are the gas composition at the reactor exit and the temperature inside the reactor. Partial oxidation of two hydrocarbon fuels has been simulated, methane and octane (the latter is conventionally considered as a substitute of gasoline, e.g., [1]), in empty reactors in the absence of catalysts inside the reactor chamber. Kinetic schemes of reforming are based on mechanisms of fuel oxidation available in the literature. For simulation of methane reforming, two kinetic schemes have been used: GRI-Mech 3.0 [18] and the Leeds methane oxidation mech-

Fig. 1. The ratio of the molar fractions of H2 and CO at methane reforming versus O/C ratio at p = 1 bar, V = 103 m3 , W = 1 kW, Tent = 300 K, the ratio of the discharge power to the total volume ow rate 0.59 kWh/m3 (n). Linessimulation, points experiment [6].

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Fig. 2. The ratio of the discharge power to the sum of volume ow rates of produced H2 and CO at methane reforming versus O/C ratio at conditions the same as in Fig. 1. Linessimulation, pointsexperiment [6].

Fig. 3. The molar fractions of H2 , CO, CO2 and CH4 versus the time of methane reforming at O/C = 1.6, p = 1 bar, T = 1270 K.

In Fig. 2 the parameter SER, dened in [6] as the ratio of the discharge power to the sum of volume ow rates of H2 and CO produced, is shown versus O/C ratio. Both schemes give the values of SER somewhat lower than those measured. That is, the calculated efciency of syngas production is higher than that obtained experimentally. Possibly, this discrepancy occurs because the calculation does not account for the thermal losses that are inevitably present in experiment. Note that the calculated gas temperature inside the reactor is rather high under the conditions considered above, in the range 14001600 K. Such strong gas heating at relatively small O/C ratios is mainly due to the energy supplied by the discharge. At low energy inputs from the discharge, when the gas heating is mainly due to the energy released at methane oxidation process, considerably larger O/C ratios should be employed. In [15], on the basis of the thermodynamic analysis, it has been shown that optimal hydrogen yields correspond to the ratios of molar fractions of air and methane in the range 33.5, that is, to O/C ratios in the range 1.31.5. The adiabatic gas temperature, calculated using the relation of equality of the total enthalpies of reactants and products, in these conditions is lower than 1200 K. (Note that the adiabatic gas temperature is an increasing function of O/C ratio.) The kinetic analysis shows that at such low temperatures the time of establishment of equilibrium in an empty reactor (without catalysts) is very large. As an example, in Fig. 3 the results are given for simulation of chemical transformations for O/C = 1.6, p = 1 bar at constant time temperature 1270 K (the equilibrium adiabatic temperature).

Calculations have been performed using the code SENKIN from the CHEMKIN-II package and the Leeds scheme of methane oxidation. The molar fractions of various components are shown as functions of time elapsed since the beginning of chemical processes. It is seen that formation of nal products, H2 and CO, is a result of a complex chain of chemical transformations, with a wide spectrum of reaction times. At the rst, fast stage of the reforming, at t < 0.1 s, there is a steep decrease of XCH4 and a steep increase of XH2 . However, at this stage only about one-third of hydrogen molecules are formed. Most of hydrogen is produced at the second stage, which takes much more time. Therefore, in order to provide fast enough methane reforming in the absence of catalysts and at a relatively small energy input from the discharge, O/C ratios should be taken substantially larger than those corresponding to optimal hydrogen yields estimated using thermodynamic approach. 3.2. Octane reforming In Fig. 4 the composition of products of octane reforming is given versus O/C ratio, simulated for conditions close to those of experiment [7]; H2 O/C ratio is taken equal to zero. In the same gure, the molar fractions of products are presented, measured in [7] at O/C = 1.32. It is seen that the calculated composition of products is consistent with that obtained in the experiment. Calculated temperature inside the reactor increases with O/C ratio from 1300 K (at O/C = 0.8) to 1600 K (at O/C = 1.32) to 1900 K (at O/C = 1.8). Carbon monoxide obtained at partial oxidation of a hydrocarbon fuel may produce hydrogen in water shift reaction

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Fig. 4. The molar fractions of products (in %) of octane reforming versus O/C ratio at p = 1 bar, V = 2 103 m3 , W = 0.27 kW, Tent = 300 K, Gfuel = 0.26 g/s. Linessimulation; pointsexperiment [7]: H2 , CO, CO2 , CH4 .

Fig. 5. The ratio GH2 /Gfuel at octane reforming versus O/C ratio at p = 2 bar, V = 3 103 m3 , Gfuel = 1 g/s.

CO + H2 O CO2 + H2 . (Note that the equilibrium in this process is shifted to the right-hand side only at rather low temperatures, T < 800 K. As partial oxidation proceeds fast enough in the absence of catalysts at much higher temperatures, the water shift can proceed only after cooling of partial oxidation products. At the stage of water shift, the use of a catalyst is required because the time of overall process in the gas phase at T < 800 K is unreasonably large.) One of the parameters characterizing the efciency of reforming process is the ratio GH2 /Gfuel of the mass ow rate of produced hydrogen, potentially accessible after water shift, to the mass ow rate of fuel. In Fig. 5 the ratio GH2 /Gfuel is given versus O/C ratio, calculated for octaneair mixture (without water) for various values of Tent and W. Optimal O/C ratios, resulting in the highest hydrogen yield, are in the range 1.31.5, corresponding to the ratio of air and fuel mass ow rates at the reactor entrance Gair /Gfuel = 67. It is seen that preheating of airfuel mixture leads to a noticeable increase of hydrogen yield. The effect of discharge power is relatively weak due to smallness of the energy input provided by the discharge in comparison with the chemical energy released in partial oxidation process. The role of the discharge in these conditions is, evidently, mainly in the formation of high-temperature regions where an ignition of the reacting mixture occurs. At small values of H2 O/C ratio, the molar fraction of H2 O in the products of partial oxidation is smaller than that of CO. In this case an additional amount of water should be injected before the water shift stage. The effect of addition of water to fuelair mixture at the reactor entrance is illustrated

Fig. 6. The molar fractions of products (in %) of octane reforming versus H2 O/C ratio at O/C = 1.4, V = 3 103 m3 , p = 2 bar, Tent = 800 K, W = 0.3 kW, Gfuel = 1 g/s.

by Fig. 6, where the calculated composition of products is given versus H2 O/C ratio. Increase of H2 O/C ratio results in decrease of the molar fraction of CO and increase of that of H2 O. Fig. 6 shows that the use of mixtures with H2 O/C ratio about 0.5 (corresponding to the ratio of water and fuel mass ow rates at the reactor entrance GH2 O /Gfuel about 0.6) allows one to get, after partial oxidation, the mixture with nearly equal molar fractions of H2 O and CO. Note

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by means of heat exchange with the species before they enter the reactor. Such heat exchange would also preheat the mixture, thus enhancing hydrogen yield at the rst stage of reforming. A use of regimes with high O/C ratios, where the required energy is provided by exothermic chemical reactions of oxidation of fuel, allows one to work at relatively low discharge powers. In these regimes the role of discharge is mainly in mixture ignition, like in spark-ignited gasoline engines. Some threshold value of the discharge power must exist that is required to ensure ignition. An extrapolation of experimental data [7] gives, for the fuel mass ow rate 1 g/s, the discharge power, sufcient for ignition, about 1 kW. Corresponding value of the energy consumption for hydrogen production is about 5 kJ/g (about 0.1 eV per one H2 molecule). Acknowledgements
Fig. 7. The ratio GH2 /Gfuel at octane reforming versus the discharge power at O/C = 1.4, p = 2 bar, V = 3 103 m3 .

The work was supported by the EC through the project No. ENK5-CT-2000-00346.

that the effect of H2 O/C ratio on hydrogen yield is not substantial. It follows that the amount of water required for water shift process may be added to the fuelair mixture not necessarily after fuel reforming in partial oxidation process, but already at the rst stage, before reforming. The effect of discharge power on hydrogen yield is shown in Fig. 7 where the ratio GH2 /Gfuel , potentially accessible after water shift, is given versus W, for various values of Tent and H2 O/C ratio. It is seen that increase of W by about an order of magnitude results in an increase of GH2 not exceeding 10%. Such weak effect of W is due to smallness of the energy input provided by the discharge in comparison with the chemical energy released in partial oxidation process.

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4. Conclusions A kinetic approach to analysis of plasma reforming of hydrocarbon gases based on the use of standard kinetic schemes available in the literature without any additional adjustments gives results which are in a reasonable agreement with experimental data on low-current arc discharges. This approach allows one to specify optimal conditions for reforming process. In particular, for partial oxidation of octane in empty reactor (without a catalyst) the initial mixture composition with O/C ratio about 1.31.5 is preferable. Two stages of reforming, partial oxidation (stage 1) and water shift (stage 2) should proceed separately. Before the second stage, the mixture is to be cooled to temperatures lower than 800 K. For water shift the use of a catalyst (e.g., based on iron oxide) is required. Cooling of the products of partial oxidation before water shift stage may be provided

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