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International Journal of Hydrogen Energy 28 (2003) 1039 1043 www.elsevier.com/locate/ijhydene

Study of a rotarc plasma reactor stability by means of electric discharge frequency analysis
Iulian Rusua ; , Jean-Marie Cormierb
a Faculty

of Industrial Chemistry, Technical University Gheorghe Asachi, Bd. Dimitrie Mangeron 71, Iasi 6600, Romania b GREMI, Universite dOrle ans, 14 rue dIssoudun, BP 6744-45067, Orle ans Cedex 2, France Received 18 June 2002; accepted 20 August 2002

Abstract The paper is dedicated to the study of methane steam reforming using three channels rotating discharge model of glidarc reactor. The process is described in terms of methane conversion, process selectivity, and energy cost as a function of discharge frequency. The analysis gives information on the reactors exploitation parameters in order to optimise its chemical performances. The experimental observations are in good agreement with a proposed model describing the chemical evolution of the system. ? 2003 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.
Keywords: Fourier transform; Mechanism; Conversion; Syngas; Hydrogen production

1. Introduction Glidarc discharge is an auto-oscillating phenomenon developing between at least two electrodes that are submerged in a laminar or turbulent gas ow. Among the glidarc reactors, the rotating discharge reactors (rotarcs) have already proved their usefulness for di erent chemical applications [1,2]. According to previous studies, the discharge frequency can act as an important factor on the energy cost and on the selectivity of the plasma reactors [36], this fact implying in certain situations a so-called non-equilibrium catalytic e ect [79]. On the other hand, the discharge frequency strongly in uences the reaction conversion in multiple electrodes gliding arc reactors. Therefore, the analysis of discharge frequency can give valuable information concerning the reactors functioning stability and the reaction mechanisms in plasma environments. The present paper is dedicated to the study of methane steam reforming using a three channels rotarc reactor, the main aim regarding the determination of operating frequency components and their e ect on the studied reaction.
Corresponding author. Tel.: +40-723-570999; fax: +40-232271-311. E-mail address: rusu iulian@hotmail.com (I. Rusu).

2. Experimental The discharges are generated in a cylinder reactor, whose schematic view was already published [10]. The external electrodes (anodes) are made of three copper tubes. The three inner conic electrodes (cathodes) are made on brass, the rst one being adjusted on a ceramic helical injector. A discharge is ignited in the inlet gap and blown forward by the gas ow. The device is producing three consecutive rotating discharges, whose the lengths are increasing from the inlet gap to the tip of the inner electrode. The discharge column is a plasma string with a visible diameter of 1 2 mm that glides in the rotating ux. The device allows the treatment of CH4= H2 O mixtures at di erent adjustable ratios and temperatures between 100 C and 200 C, with total ow rates going up to 200 l= min at atmospheric pressure. The power supply is a three-channel device connected to the anodes [9]. One channel consists of two transformers with rectiers that allow two running phases: the ignition at high voltage and low current intensity and a complementary energy supply with higher current (about 2 A). This current intensity is su cient to obtain a hot plasma string with the temperature on the surface up to 3000 K [11]. A Hall e ect probe is used for current determination, and a voltage divider with a ratio of 0.01 is connected to the

0360-3199/03/$ 30.00 ? 2003 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved. PII: S 0 3 6 0 - 3 1 9 9 ( 0 2 ) 0 0 1 9 8 - 2

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oscilloscope. The oscilloscope is a Tektronix TDS 460A model and was used with a di erential probe voltage. Voltage and current were recorded at the beginning, and at the end of each experiment in order to verify the running stability. Finally, the signal processing is performed on a PC. Each set of data consisted of six recordings for voltages and currents, corresponding to the power determination of the three-phase reactor. The major gaseous components were analysed on-line and quantied by chromatography (H2 using a TCD detector/HP 5890, respectively, CO, CO2 , CH4 and C2 H2 with an FID detector/Varian 3400CX).

3. Results and discussion Fig. 1 shows an example of voltage variation during the reactors exploitation. We have to mention that the voltage is plotted as a negative signal. The discharge is ignited between the electrodes and moves pushed by the owing gas. As the arc moves, the voltage increases and the highest voltage value corresponds to the breakdown voltage of the starting gap [12]. Finally, the voltage looks like a sawtooth signal, its complexity depending on the reactors feeding parameters (i.e. total inlet gas ow and methane/water molar ratio) and on the position of the electrode in the reactor. The voltage variation data for all experiments have been processed by means of Fourier transform in order to determine the main characteristic frequencies appearing during the reactors functioning. As an example, in Fig. 2 is presented the spectrum, obtained by the Fourier analysis, which is corresponding to the signal from Fig. 1. The main characteristic frequencies for the entire series of experiments ranged between 20 and 455 Hz. Taking as a reference the frequency of the rectied current coming from the power supply (f1 = 100 Hz), we have identied in the spectrum the existence of f1 = 2 frequency and of the harmonic 2f1 . It was also noticeable in the spectra the presence the odd harmonics: 3f1 = 2 and 5f1 = 2. Accurate examination gives rise to the assumption of the existence of a second frequency f2 = 39 Hz, with its harmonics 2f2 ; 3f2 , etc., in order to be able to t well the frequency series. This frequency is independent from f1 and the mechanism linked to its existence is not yet clearly explained. However, in such reactors complex ow arises and this frequency may concern the turbulence and the mass transfer through the discharges [13,14]. It was also noticed in the spectra the presence of f2 = 2 frequency and of the odd sub-harmonics: 3f2 = 4 and 3f2 = 2. These frequencies are issued from a sub-harmonic cascade mechanism. The two-frequency process assumption leads to a non-linear interaction regime that makes the signal denitely more complex. This seems to be real since all the other frequencies could be assigned to di erent combinations involving f1 and f2 : f1 = 2 + f2 = 2; f1 = 2 + f2 ; f1 = 2 + 3f2 = 2; f1 + f2 , etc.

If we analyse the distribution of frequency components for each phase of the power supply one can make some interesting observations. At the reactors inlet (rst electrode) most of the main frequency components come from the power supply. A similar behaviour is noticed for the second electrode. On the other hand, at the reactors outlet (the third electrode) the importance of the second main frequency (f2 ) is strongly increasing for almost the entire series of experiments. Therefore, if the discharge frequency is mostly controlled by the power supply for the rst two electrodes, in the case of the last electrode the frequency is also dictated by the hydrodynamic conditions. In order to get a better impression of how the discharge frequency of the last electrode e ects the chemical reactions, we have plotted the variation of the total methane conversion versus the weight of f2 components in the original time signal. As shown in the above gures, the higher the weight of f2 components in the spectra, the lower the reaction conversion. This behaviour can be explained by the low values of these components (i.e. 20, 29 and 39 Hz) comparing with f1 . The lower discharge frequency leaves larger quantities of gas without electric treatment. Therefore, as expected, the larger the total ow rates the stronger the negative in uence on the reaction conversion (see Fig. 3). A similar dependence could be observed when one takes into account the methane/water ratio at the reactors inlet (see Fig. 4). In this case, the linear trendlines represented for series of experiments performed at increasing concentrations of methane in the inlet mixture have shown a decrease of the total chemical conversion. This negative behaviour is stronger for higher weights of the f2 components in the original time signal. A possible explanation for this fact may regard the chemical properties of the inlet mixture. If one considers the almost non-polar bonds from the methane molecule, higher methane concentrations in the inlet gases could lower the electric conductivity of the gas mixture, fact that prevents the faster ignition of the discharges (f1 components), leading thus to lower conversion values. The discharge frequency is also in uencing the selectivity and the energy costs of the process. This series of experiments did not reveal the formation of carbon dioxide, the reactor being quite selective for the syngas production [11]: CH4 + H2 O CO + 3H2 : (1)

The selectivity values varied between 20% and 80% depending on feeding parameters, but however, the secondary reaction was the methane cracking: CH4 C + 2H2 : (2)

In order to make this aspect clearer to the reader we shall brie y present here our model that describes the chemical processes occurring in the glidarc reactor [11]. According to the model the reactions occur mainly in the discharge string. The gas penetrating the discharge is almost instantly heated up to more than 2000 K. Afterwards, its temperature

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0 -0.02 0 0.02 0.04 0.06 0.08

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0.1

-2

-4

U (V/100)

-6

-8

-10

-12 time (s)

Fig. 1. Voltage record of the rotating discharges.

8.00E-01

6.00E-01

4.00E-01 Modulus 2.00E-01 0.00E+00 0.00E+00

5.00E+02

1.00E+03

1.50E+03

2.00E+03

2.50E+03

-2.00E-01 Frequency (Hz)

Fig. 2. FFT spectrum of the signal from Fig. 1.

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21 20 19 18 Conversion (%) 17 16 15 14 13 12 0

I. Rusu, J.-M. Cormier / International Journal of Hydrogen Energy 28 (2003) 1039 1043

75 l/min 100 l/min 125 l/min Linear (75 l/min) Linear (100 l/min) Linear (125 l/min)
0.1 0.2 0.3 0.4 0.5

Weight of f2 components in the original time signal

Fig. 3. Dependence of the total conversion on the weight of f2 frequency for the last electrode voltage signal recorded at di erent ow rates of the inlet stream.

21

20

19

18

Conversion (%)

17

16

15

14

13

12 0

20% CH4 40% CH4 60% CH4 80% CH4 Linear (20% CH4) Linear (40% CH4) Linear (60% CH4) Linear (80%CH4)
0.1 0.2 0.3 0.4 0.5

Weight of f2 components in the original time signal

Fig. 4. Dependence of the total conversion on the weight of f2 frequency for the last electrode voltage signal recorded at di erent methane concentrations in the inlet stream.

follows the temperature prole of the arc and when it leaves the string, sharply cools down to ambient temperature almost without heat exchange. The thermodynamic

calculations performed according to this model tted quite well with the chemical composition at the reactors outlet and with the measured energy costs.

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If there is heat exchange between the discharge and the gas stream, it means that there are regions in the reactor where the temperature may vary according to the calculations from 400 to 900 K, leading to the CO2 production. The presence of high discharge frequencies in the FT spectra may be considered as an e ect of the ow instabilities and of the plasma mixture composition. In this case, the discharges are very close to one another, the gases evolved from a discharge string meeting the small heated zone which is wrapping another discharge. The overlapping of successive plasma strings is producing medium temperature regions. These zones have temperatures of maximum 900 K (thermodynamic equilibrium) and could explain the presence of CO2 for previous series of experiments [9]. In that case the glidarc reactor functioning presented higher frequency components ranging between 566 and 1055 Hz. However, we have to mention here that the plasma reactor used for that series of experiments was not a rotarc. On the other hand the energy costs strongly increased due to the heat transfer between the discharge and the magnetically stirred gas ow. As told before, in the present series the highest frequency that we have observed was of 455 Hz, explaining the lack of carbon dioxide at the reactors outlet. The energy cost was also very low, going down to 0.4 0:2 Wh= Nl of produced hydrogen. Therefore, we may conclude that the proposed model is in good agreement with the frequency analysis. 4. Conclusions The electric discharge frequency analysis gives valuable information concerning both the reaction mechanism and the performances of glidarc reactors. The constructed device proved to have a stable functioning for all the electrodes. However, both the power supply and the hydrodynamic conditions in uenced the discharges from the last electrode. The results suggest the use of an exploitation frequency of about 500 Hz correlated with an appropriate geometry in order to obtain the best conversion/energy cost ratio. A better selectivity toward the water gas shift reaction request the use of higher frequencies but this will also increase the energy costs. Subsequent studies will try to improve the correlation between model and experiment by the e ect of reactive species present in the volume surrounding the plasma strings.

References
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