Gas-to-liquids process using multi-phase flow, non-thermal plasma microreactor

A multi-phase flow non-thermal plasma microreactor based on dielectric barrier discharge has been developed for partial oxidation of methane to liquid oxygenates at atmospheric pressure. A pulsed water injection method has been used to remove condensable liquid components from the active discharge region. The effect of the pulsed water injection on methane conversion, yield of oxygenates and hydrogen peroxide (H2O2) formation as an intermediate oxidation product is discussed. H2O2 has been found to oxidize formaldehyde in the post-discharge liquid. The overall kinetics of the gas-to-liquids process is described by dividing process into three different stages: electron impact dissociation of methane and oxygen and radical reactions in the gas phase followed by condensation of oxygenates and oxidation in the post-discharge liquid

[1]  M. Antonietti,et al.  Solid catalysts for the selective low-temperature oxidation of methane to methanol. , 2009, Angewandte Chemie.

[2]  S. Büttgenbach,et al.  A micro plasma reactor for fluorinated waste gas treatment , 2004 .

[3]  J. Gardeniers,et al.  Propane Conversion at Ambient Temperatures C-C and C-H Bond Activation Using Cold Plasma in a Microreactor , 2008 .

[4]  A. Baiker,et al.  Partial oxidation of methane to methanol in a flow reactor at elevated pressure , 1991 .

[5]  A. V. Kozyrev,et al.  METHODOLOGICAL NOTES: Evaporation of a spherical droplet in a moderate-pressure gas , 2001 .

[6]  L. Lobban,et al.  Production of Organic Oxygenates in the Partial Oxidation of Methane in a Silent Electric Discharge Reactor , 2001 .

[7]  Ken Okazaki,et al.  Microplasma synthesis of tunable photoluminescent silicon nanocrystals , 2007 .

[8]  Ken Okazaki,et al.  A single step methane conversion into synthetic fuels using microplasma reactor , 2011 .

[9]  Micro-plasma technology — direct methaneto-m ethanol in extremely confined environment- , 2004 .

[10]  B. Eliasson,et al.  Electron impact dissociation in oxygen , 1986 .

[11]  S. Bugaev,et al.  Plasma-Chemical Conversion of Lower Alkanes with Stimulated Condensation of Incomplete Oxidation Products , 1998 .

[12]  N. Foster.  Direct catalytic oxidation of methane to methanol — a review , 1985 .

[13]  T. S. Anderson,et al.  Multichannel Microchemical Reactor Comprising Replica-Molded Microplasma Devices: Chemiluminescence and Sulfur Deposition in $\hbox{Ar/CS}_{2}$ Flows , 2008, IEEE Transactions on Plasma Science.

[14]  M. Weiss,et al.  Diagnostics of an RF Plasma Flash Evaporation Process Using the Monochromatic Imaging Technique , 2001 .

[15]  R. M. Sankaran,et al.  Synthesis of blue luminescent si nanoparticles using atmospheric-pressure microdischarges. , 2005, Nano letters.

[16]  S. Tsang,et al.  Influence of homogeneous gas phase reactions in the partial oxidation of methane to methanol and formaldehyde in the presence of oxide catalysts , 1991 .

[17]  K. Seshan,et al.  On-chip microplasma reactors using carbon nanofibres and tungsten oxide nanowires as electrodes , 2008 .

[18]  J. Legrand,et al.  Methane conversion by an air microwave plasma , 1995 .

[19]  H. Kojima,et al.  Study of hydroxylation of benzene and toluene using a micro-DBD plasma reactor , 2005 .

[20]  R. Reid,et al.  Analysis of Aqueous Mixtures of Hydrogen Peroxide and Aldehydes , 1954 .

[21]  L. Lobban,et al.  The direct partial oxidation of methane to organic oxygenates using a dielectric barrier discharge reactor as a catalytic reactor analog , 2001 .

[22]  H. Gardeniers,et al.  Alkane activation at ambient temperatures: unusual selectivities, C--C, C--H bond scission versus C--C bond coupling. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[23]  D. Reiter,et al.  Collision processes of CHy and CHy+ hydrocarbons with plasma electrons and protons , 2002 .

[24]  Hyman D. Gesser,et al.  The direct conversion of methane to methanol by controlled oxidation , 1985 .

[25]  B. Langlais,et al.  Guideline for Measurement of Ozone Concentration in the Process Gas From an Ozone Generator , 1996 .

[26]  N. Parkyns,et al.  Progress in the partial oxidation of methane to methanol and formaldehyde , 1991 .

[27]  H. Matsumoto,et al.  Selective Oxidation of Methane to Methanol and Formaldehyde with Nitrous Oxide in a Dielectric-Barrier Discharge−Plasma Reactor , 2001 .

[28]  Stuart H. Taylor,et al.  Catalytic synthesis of methanol and formaldehyde by partial oxidation of methane , 1995 .

[29]  S. Kachi,et al.  The Simultaneous Determination of Bis(hydroxymethyl)-peroxide (BHMP), Hydroxymethylhydroperoxide (HMP), and H2O2 with Titanium(IV). Equilibria Between the Peroxides and the Stabilities of HMP and BHMP at Physiological Conditions. , 1971 .

[30]  U. Kogelschatz.  Dielectric-Barrier Discharges: Their History, Discharge Physics, and Industrial Applications , 2003 .

[31]  J. Gardeniers,et al.  Oxidative conversion of propane in a microreactor in the presence of plasma over MgO based catalysts-an experimental study , 2008 .

[32]  R. Periana,et al.  Catalytic, Oxidative Condensation of CH4 to CH3COOH in One Step via CH Activation , 2003, Science.

[33]  T. Nozaki,et al.  Partial oxidation of methane using a microscale non-equilibrium plasma reactor , 2004 .

[34]  B. Eliasson,et al.  Partial Oxidation of Methane to Methanol with Oxygen or Air in a Nonequilibrium Discharge Plasma , 1998 .

[35]  Yongchun Tang,et al.  Direct methane conversion to methanol by ionic liquid-dissolved platinum catalysts. , 2006, Chemical communications.

[36]  J. Gardeniers,et al.  Catalyst Activation by Microplasma for Carbon Nanofiber Synthesis in a Microreactor , 2009, IEEE Transactions on Plasma Science.

[37]  Masa-aki Suzuki,et al.  Characterization of a capillary plasma reactor for carbon dioxide decomposition , 2006 .

[38]  J. Mora,et al.  Liquid-sample introduction in plasma spectrometry , 2003 .

[39]  L. Lobban,et al.  Product selectivity control and organic oxygenate pathways from partial oxidation of methane in a silent electric discharge reactor , 2001 .

[40]  Masayuki Sato,et al.  Advanced oxidation processes using pulsed streamer corona discharge in water , 2002 .

[41]  N. Koshizaki,et al.  Flow rate effect on the structure and morphology of molybdenum oxide nanoparticles deposited by atmospheric-pressure microplasma processing , 2006 .

[42]  Soon-Bark Kwon,et al.  Decomposition of Toluene with Surface-Discharge Microplasma Device , 2005 .

[43]  D. Graves,et al.  Microhollow Cathode Discharge Reactor Chemistry , 2005 .

[44]  M. Bizjak,et al.  Pseudo first-order reaction rate constant for the formation of hydroxymethylhydroperoxide from formaldehyde and hydrogen peroxide , 1988 .

[45]  Eiji Suzuki,et al.  Selective Oxidation of Methane Using a Non-Thermal Pulsed Plasma , 2000 .