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28th ICPIG, July 15-20, 2007, Prague, Czech Republic

Topic number: 10

Chemistry of Methane-Nitrogen in a dielectric barrier discharge at atmospheric pressure


G. Scarduelli1, P. Franceschi1, G. Guella1, G. Dilecce2,3, S. De Benedictis3 and P. Tosi1
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Department of Physics, University of Trento, via Sommarive 14, 38050 Povo, Trento, Italy Istituto di Fotonica e Nanotecnologie - CNR, sede di Trento, via alla Cascata 56/C, 38050 Povo, Trento, Italy 3 Istituto di Metodologie Inorganiche e dei Plasmi - CNR, sede di Bari, via Orabona 4, 70126 Bari, Italy
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Methane is the principal component of natural gas, coal-bed methane and associated gas. The valorization of methane into higher hydrocarbons and oxygenates has been desired for several decades. Moreover the direct conversion of methane into more valuable chemicals and versatile fuels constitutes an important task. In this contribution we present a preliminary investigation of the liquid deposit obtained treating a methane-nitrogen mixture in a dielectric barrier discharge working at atmospheric pressure. The deposit was analyzed by means of various techniques (Nuclear Magnetic Resonance, Fourier Transform Infrared Spectroscopy and Matrix-Assisted Laser Desorption/Ionisation -Time Of Flight Mass Spectrometry), in order to explain its polymeric nature. Nevertheless its composition is at present not completely identified.

1. Introduction Methane is the main component of gaseous/solid fossil fuel resources and constitutes one of the largest organic carbon reserves. The direct conversion of CH4 into more valuable chemicals is very attractive [1, 2]. However, there is still no practical technology for such conversion [3]. Both thermal and nonthermal plasmas have been widely used for CH4 conversion. However nonthermal plasmas are the choice for chemical synthesis of higher hydrocarbons and oxygenates since the electron temperature is high (up to 10 5 K), while the gas remains at room temperature. Most of products produced using corona, microwave and radio frequency discharges are small molecules, like ethylene, acetylene, hydrogen and carbon monoxide. Products can be more complex under the condition of dielectric barrier discharge including light hydrocarbons, liquid fuels, alcohols and acids [4]. The distribution of products depends on the different parameters, such as dielectric material, length, distance of discharge gap and electrode configuration. In this contribution we present a preliminary investigation of CH4-N2 mixtures treated in a dielectric barrier discharge (DBD) working at atmospheric pressure. In particular, we have observed the deposition of a viscous liquid polymer. 2. Experimental 2. 1. Dielectric Barrier Discharge The methane-nitrogen mixtures are treated in a dielectric barrier discharge (DBD) working at atmospheric pressure. Different amounts of CH4

were admitted in the plasma reactor and mixed with N2. Our DBD consists of a quartz tube ( = 10 mm) surrounded by a metal outer electrode (a spiral electrode). The internal electrode is a metallic rod embedded in a glass tube ( = 4 mm). The length of the plasma system is about 5 cm. Electrodes are powered at a frequency variable between 6 kHz and 15 kHz by a variable high voltage transformer. The energy transferred to the plasma is evaluated by measuring both the applied voltage (with an HV probe) and the charge (with a HV capacitor in series with the discharge) by the standard Manleys charge-voltage plot method [5]. The average power transmitted is ~10 W working at 16 kV with a frequency of 10 kHz. The reactor is vacuum sealed to allow control of the gas sample under treatment. 2. 2. NMR Nuclear Magnetic Resonance (NMR) spectra were taken at 298.2 K by an Avance 400 Bruker spectrometer operating at 400.13 MHz for 1H and equipped with a 5 mm inverse broad band (BBI) probe. Data were collected with XWINNMR (version 1.3) and processed using both Bruker TOPSPIN (version 1.3) and MestReC data processing software. 2. 3. FT-IR Fourier Transform Infrared (FT-IR) Spectra were acquired by a spectrometer FT-IR EQUINOX 55 Bruker Optics capable of 0.2 cm-1 maximum resolution, equipped with a DTGS detector and a Kbr beam splitter. Acquisitions have been performed with a resolution of 4 cm-1 by a Silver

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28th ICPIG, July 15-20, 2007, Prague, Czech Republic

Gate Reflection Attenuated Total Reflection (ATR) System. 2. 4. MALDI-TOF MS Matrix-Assisted Laser Desorption/Ionisation Time Of Flight (MALDI-TOF) spectra were taken by an Ultraflex II (Bruker Daltonics) spectrometer operating in reflectron mode with the following experimental parameters: delay time 0 ns, IS1 25 V, IS2 21.65 V, IS lens 10.5 V, laser energy (N2, 337 nm) 72.3 J. 3. Preliminary results During DBD plasma treatment we have observed the formation of a liquid deposit on the surface of the plasma reactor. This material has been dissolved in a suitable solvent for NMR, FTIR and MALDITOF analysis. MALDI-TOF spectra (Fig. 1) of the deposit show, in the 200-1500 m/z region, the typical peak distribution of a polymeric compound. The repeated clusters of peaks present a constant mass difference, that is evaluated in 14 Da, as shown in Fig. 1. This value corresponds to a CH2 group. The polymeric nature of the deposit is confirmed also by broad signals in the 1H-NMR spectrum of the liquid deposit taken in acetone-d6, as shown in Fig. 2. In order to obtain further structural information on the chemical functions present in the deposit, FTIR measurements were also carried out. IR spectrum (Fig. 3) indicates the presence of CN groups possibly due to nitrogen containing impurities, and confirms the nature of polymer-like branched chain structure.

Fig.2: 1H-NMR spectrum of the liquid deposit taken in acetone-d6.

Fig.3: FT-IR spectrum of the deposit obtained by DBD plasma on methane/N2 reacting system compared to FT-IR spectrum of the deposit obtained by DBD plasma on methane/Ar reacting system.

Observations of the time evolution of the CN(B2+X2+) violet system emission during the DBD plasma treatment of a CH4-N2 mixture are presented in [6]. 4. References [1] J.H. Lunsford, Catal. Today 63 (2000) 165. [2] J.M. Fox, Catal. Rev., Sci. Eng. 35 (1993) 169. [3] Y. Xu, X. Bao and L. Lin, J. Catal. 216 (2003) 386. [4] Y. Zhang, Y. Li, Y. Wang, C. Liu and B. Eliasson, Fuel Process. Technol. 83 (2003) 101. [5] T. Manley, Trans. Electrochem. Soc. 84 (1945) 83. [6] G. Scarduelli, P. Franceschi, G. Dilecce, S. De Benedictis and P. Tosi, ICPIG 2007, this book.

Fig.1: MALDI-TOF spectra of the deposit obtained by DBD plasma on methane/N2 reacting system: in (a) we report the spectrum of the deposit dissolved in acetone, while in (b) we present the spectrum of the solution diluted 10 times.

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