• Korean Chemical Engineering Research
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• v.48 no.6
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• pp.776-783
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• 2010

Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.

• Clean Technology
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• v.18 no.1
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• pp.95-101
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• 2012

The Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. And the promotion effects of metals such as Mg, Ce, La and Sr in partial oxidation of methane over these $Co/Al_2O_3$ and $Ni/Al_2O_3$ were investigated. Reaction activity of these catalysts for the partial oxidation of methane was investigated in the temperature range of 450~$650^{\circ}C$ at 1 atm and $CH_2/O_2$ = 2.0. The catalysts were characterized by BET, XRD and SEM/EDX. The results indicated that the catalytic performance of these catalysts was improved with the addition of 0.2 wt% metal promoter. The Mg promoted $Co/Al_2O_3$ catalyst showed the highest $CH_4$ conversion and hydrogen selectivity at higher temperature than $500^{\circ}C$. The Ce and Sr promoted Ni catalysts superior to Co-based catalysts in the low temperature range. The addition of metal promoter to $Co/Al_2O_3$ and $Ni/Al_2O_3$ catalysts increased the surface area.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.2
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• pp.124-131
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• 2007

Methane is partially oxidized to produce the syngas by the lattice oxygen of metal oxides in the absence of gaseous oxygen. The present work deals with ferrite including copper component, which does not chemisorb methane, to investigate the suppression of the carbon deposition during the reduction of metal oxides by methane. Iron-based oxides of $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0) was synthesized by the co-precipitation method. Thermogravimetric Analysis(TGA) was used to observe the isothermal reduction behavior of $Cu_xFe_{3-x}O_4$ and $Fe_3O_4$ at $600-900^{\circ}C$ under methane atmosphere. The crystal structures of reduced specimens were characterized by X-rays powder diffraction(XRD) technique. From the analyses of TGA, it is concluded that the reduction kinetics of $CuFe_2O_4$ was the fastest among $Fe_3O_4$ and $Cu_xFe_{3-x}O_4$(X=0.25, 0.5, 1.0). The X-ray diffraction analyses indicated that $Cu_xFe_{3-x}O_4$ was decomposed to Cu and $Fe_3O_4$ phase at $600^{\circ}C$ and was reduced to Cu and Fe phase at $800^{\circ}C$. $Fe_3O_4$, which was reduced at $900^{\circ}C$, showed Fe, graphite and $Fe_3C$ phases. On the contrary, $Cu_xFe_{3-x}O_4$ does not show the graphite or $Fe_3C$ phases. This results infer that Cu component suppress the carbon deposition on Cu-ferrite.

• Journal of the Korean Applied Science and Technology
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• v.23 no.1
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• pp.63-69
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• 2006

Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at $600^{\circ}C$, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through $O_2-TPD$ experiment, it was found that the catalysts showing good catalytic activity showed $O_2$ desorption peak around $800^{\circ}C$.

• Journal of the Korean Applied Science and Technology
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• v.30 no.4
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• pp.649-655
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• 2013

Methanol was directly produced by the partial oxidation of methane with perovskite and mixed oxide catalysts. Perovskite ($ABO_3$) catalysts were prepared by the malic acid method with changing A and B site components. Three-component mixed oxide catalysts that have Mo and Bi as a main component were prepared by the co-precipitation method. Among the perovskite catalysts, $SrCrO_3$ showed the highest methanol selectivity of 11% at $400^{\circ}C$. For the three-component mixed oxide catalysts, there were no remarkable changes in methane conversion. Among the mixed oxide catalysts, Mo-Bi-Cr mixed oxide catalyst showed the highest methanol selectivity of 15.3% at $400^{\circ}C$. The catalytic activity and methanol selectivity of the three-component mixed oxide catalysts were directly proportional to the surface area of the catalysts.

• Membrane and Water Treatment
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• v.8 no.2
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• pp.171-184
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• 2017

This study presents the effect of hydraulic retention time (HRT) on the characteristics of emission of three major greenhouse gases (GHGs) including $CH_4$, $CO_2$ and $N_2O$ during operation of a sequencing batch reactor for aerobic oxidation of methane with denitrification (AeOM-D SBR). Dissolved $N_2O$ concentration increased, leveled-off and slightly decreased as the HRT increased from 0.25 to 1d. Concentration of the dissolved $N_2O$ was higher at the shorter HRT, which was highly associated with the lowered C/N ratio. A longer HRT resulted in a higher C/N ratio with a sufficient carbon source produced by methanotrophs via methane oxidation, which provided a favorable condition for reducing $N_2O$ formation. With a less formation of the dissolved $N_2O$, $N_2O$ emission rate was lower at a longer HRT condition due to the lower C/N ratio. Opposite to the $N_2O$ emission, emission rates of $CH_4$ and $CO_2$ were higher at a longer HRT. Longer HRT resulted in the greater total GHGs emission as $CO_2$ equivalent which was doubled when the HRT increased from 0.5d to 1.0 d. Contribution of $CH_4$ onto the total GHGs emission was most dominant accounting for 98 - 99% compared to that of $N_2O$ (< 2%).

• 한국생태학회:학술대회논문집
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• 1998.05a
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• pp.80-80
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• 1998

• Transactions of the Korean Society of Mechanical Engineers B
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• v.31 no.11
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• pp.942-948
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• 2007

Popular techniques for producing hydrogen by converting methane include steam reforming and catalyst reforming. However, these are high temperature and high pressure processes limited by equipment, cost and difficulty of operation. Low temperature plasma is projected to be a technique that can be used to produce high concentration hydrogen from methane. It is suitable for miniaturization and fur application in other technologies. In this research, the effect of changing each of the following variables was studied using an AC GlidArc system that was conceived by the research team: the gas components ratio, the gas flow rate, the catalyst reactor temperature and voltage. Results were obtained for methane and hydrogen yields and intermediate products. The system used in this research consisted of 3 electrodes and an AC power source. In this study, air was added fur the partial oxidation reaction of methane. The result showed that as the gas flow rate, the catalyst reactor temperature and the electric power increased, the methane conversion rate and the hydrogen concentration also increased. With $O_2/C$ ratio of 0.45, input flow rate of 4.9 l/min and power supply of 1 kW as the reference condition, the methane conversion rate, the high hydrogen selectivity and the reformer energy density were 69.2%, 32.6% and 35.2% respectively.

• Transactions of the Korean hydrogen and new energy society
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• v.23 no.4
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• pp.346-352
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• 2012

The properties of methane oxidation were studied in this research over transition metal containing $CeO_2$ (TM/$CeO_2$, TM=Ni, Co, Cu, Fe) with TM content of 5 wt. % at atmospheric pressure. The characteristics of catalysts were investigated by various characterization techniques, including XRD, GC, SEM and EPMA analyses. The catalytic tests were carried out in a fixed Rmix ratio of 1.5 ($CH_4/O_2$) in a fixed-bed reactor operating isothermally at atmospheric pressure. Only the Ni/$CeO_2$ catalysts showed syngas production above $400^{\circ}C$ via typical partial oxidation reaction whereas other catalysts induced complete oxidation resulting in the production of $CO_2$ and $H_2O$ in whole reaction temperature range. From the quantitative analysis on carbon deposition after catalytic tests, Cu/$CeO_2$ was found to show the highest resistance on carbon deposition. Therefore Cu can be proposed as an efficient catalyst element which can be combined with a conventional Ni-based SOFC anode to enhance the carbon tolerance.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.20 no.1
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• pp.53-62
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• 2015

To elucidate the microbial consortia responsible for the anaerobic methane oxidation in the methane hydrate bearing sediments, we compared the geochemical constituents of the sediment, the rate of sulfate reduction, and microbial biomass and diversity using an analysis of functional genes associated with the anaerobic methane oxidation and sulfate reduction between chimney site (UBGH2-3) on the continental slope and non-chimney site (UBGH2-10) on the basin of the Ulleung Basin. From the vertical profiles of geochemical constituents, sulfate and methane transition zone (SMTZ) was clearly defined between 0.5 and 1.5 mbsf (meters below seafloor) in the UBGH2-3, and between 6 and 7 mbsf at the UBGH2-10. At the UBGH2-3, the sulfate reduction rate (SRR) in the SMTZ exhibited was appeared to be $1.82nmol\;cm^{-3}d^{-1}$ at the depth of 1.15 mbsf. The SRR in the UBHG2-10 showed a highest value ($4.29nmol\;cm^{-3}d^{-1}$) at the SMTZ. The 16S rRNA gene copy numbers of total Prokaryotes, mcrA, (methyl coenzyme M reductase subunit A), and dsrA (dissimilatory sulfite reductase subunit A) showed the peaks in the SMTZ at both sites, but the maximum mcrA gene copy number of the UBGH2-10 appeared below the SMTZ (9.8 mbsf). ANME-1 was a predominant ANME (Anaerobic MEthanotroph) group in both SMTZs of the UBGH2-3 and -10. However, The sequences of ANME-2 were detected only at 2.2 mbsf of the UBGH2-3 where high methane flux was observed because of massive amount of gas hydrate at shallow depth. And Desulfosarcina-Desulfococcus (DSS) that is associated with ANME-2 was detected in 2.2 mbsf of the UBHG2-3. Overall results demonstrate that ANME-1 and ANME-2 are considered as significant archaeal groups related to methane cycle in the subsurface sediment of the East Sea, and ANME-2/DSS consortia might be more responsible for methane oxidation in the methane seeping region than in non-seeping region.