• Korean Chemical Engineering Research
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• v.46 no.6
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• pp.1113-1118
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• 2008

Characteristics of reduction properties and carbon deposition of $CuFe_2O_4$ and $Fe_3O_4$ were investigated by using TGA, XRD, SEM, TEM and gas analysis at $900^{\circ}C$. XRD analyses indicated that the reduced $Fe_3O_4$ was composed of Fe, graphite and $Fe_3C$ phases. In contrast, the reduced $CuFe_2O_4$ did not show the graphite or $Fe_3C$ phases. It was observed by SEM analysis that the surface of the $Fe_3O_4$ was completely covered with carbon, after methane partial oxidation. From gas analysis, $CuFe_2O_4$ showed much higher methane conversion and reduction kinetics as compared to the $Fe_3O_4$ under the same reaction conditions and the estimated carbon deposition amounts on the reduced $CuFe_2O_4$ was much lower than those on the reduced $Fe_3O_4$ during the syngas production process. It was found by TEM that carbon on the reduced $Fe_3O_4$ particles has a platelet shape.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.89-92
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• 2007

Partail oxidation(POX) of n-butane was investigated in this research by employing ceria-promoted Ni/calcium hydroxyapatite catalysts ($Ce_xNi_{2.5}Ca_{10}(OH)_2(PO_4)_6$ ; x = $0.1{\sim}0.3$) which had recently been reported to exhibit good catalytic performance in POX of methane and propane. The experiments were carried out with changing ceria content, $O_2/n-C_4H_{10}$ ratio and temperature. As the $O_2/n-C_4H_{10}$ feed ratio increased up to 2.75, n-$C_4H_{10}$ conversion and $H_2$ yield increased and the selectivity of methane and other hydrocarbons decreased. But with $O_2/n-C_4H_{10}$ = 3.0, $n-C_4H_{10}$ conversion and $H_2$ yield decreased. This is considered due to that too much oxygen may inhibit the reduction of Ni or induce the oxidation of Ni, which results in poor catalytic activity. The optimum $O_2/n-C_4H_{10}$ ratio lay between 2.50 and 2.75. $Ce_{0.1}Ni_{2.5}Ca_{10}(OH)_2(PO_4)_6$ showed the highest $n-C_4H_{10}$ conversion and $H-2$ yield on the whole. In durability tests, higher hydrogen yield and better catalyst stability were obtained with the $O_2/n-C_4H_{10}$ ratio of 2.75 than with the ratio of 2.5.

• 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.

• Journal of the Korean Applied Science and Technology
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• v.21 no.3
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• pp.225-230
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• 2004

Synthesis gas is a high valued compound as a basic chemicals at various chemical processes. Synthesis gas is mainly produced commercially by a steam reforming process. However, the process is highly endothermic so that the process is very energy-consuming process. Thus, this study was carried out to produce synthesis gas by the partial oxidation of methane to decrease the energy cost. The effects of reaction temperature and flow rate of reactants on the methane conversion, product selectivity, product ratio, and carbon deposition were investigated with 13wt% Ni/MgO catalyst in a fluidized bed reactor. With the fluidized bed reactor, $CH_4$ conversion was 91%, and Hz and CO selectivities were both 98% at 850$^{\circ}C$ and total flow rate of 100 mL/min. These values were higher than those of fixed bed reactor. From this result, we found that with the use of the fluidized bed reactor it was possible to avoid the disadvantage of fixed bed reactor (explosion) and increase the productivity of synthesis gas.

• Journal of the Korean Applied Science and Technology
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• v.20 no.4
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• pp.289-295
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• 2003

Synthesis gas is produced commercially by a steam reforming process. However, the process is highly endothermic and energy intensive. Thus, this study was conducted to produce synthesis gas by the partial oxidation of methane to cut down the energy cost. Supported Ni catalysts were prepared by the impregnation method. To examine the activity of the catalysts, a differential fixed bed reactor was used, and the reaction was carried out at $750{\sim}850^{\circ}C$ and 1 atm. The fresh and used catalysts were characterized by XRD, XPS, TGA and AAS. The highest catalytic activity was obtained with the 13wt% Ni/MgO catalyst, with which methane conversion was 81%, and $H_2$ and CO selectivities were 94% and 93%, respectively. 13wt% Ni/MgO catalyst showed the best $MgNiO_2$ solid solution state, which can explain the highest catalytic activity of the 13wt% Ni/MgO catalyst.

• Korean Chemical Engineering Research
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• v.51 no.3
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• pp.319-324
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• 2013

The partial oxidation reaction of methane was investigated to produce syngas with $Ni/CeO_2-ZrO_2$, $Ni-Ru/CeO_2-ZrO_2$ and $Ni-Pd/CeO_2-ZrO_2$ catalysts. Honeycomb metallic monolith was applied in order to obtain high catalytic activity and stability in partial oxidation reforming. The catalysts were characterized by XRD and FE-SEM. The influence of various catalysts on syngas production was studied for the feed ratio (O/C), GHSV and temperature. Among the catalysts used in the experiment, the $Ni-Pd/CeO_2-ZrO_2$ catalyst showed the highest activity. The 99% of $CH_4$ conversion was obtained at the condition of T=$900^{\circ}C$, GHSV=10,000 $h^{-1}$ and feed ratio O/C=0.55. It was confirmed that $H_2$ yield increased slightly as O/C ratio increased, while CO yield remained almost constant. Also, $CH_4$ conversion decreased as GHSV increased. It was found that the safe range of GHSV for high $CH_4$ conversion was estimated to be less than 10,000 $h^{-1}$.

• Applied Chemistry for Engineering
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• v.32 no.4
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• pp.478-482
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• 2021

The catalytic yields of partial oxidation of methane (POM) to hydrogen over Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Eu, Pr, and Tb) were investigated in a fixed bed flow reactor under atmosphere. As 1 wt% of Eu was added to Ni(5)/SBA-15 catalyst, the O1s and Si2p core electron levels of Eu(1)-Ni(5)/SBA-15 showed the chemical shift by XPS. XPS analysis also demonstrated that the atomic ratio of O1s, Ni2p_3/2, and Si2p increased to 1.284, 1.298, and 1.058, respectively, and exhibited O^-, and O^2- oxygen and metal ions such as Eu³⁺, Ni⁰, Ni²⁺, and Si⁴⁺ on the catalyst surface. The yield of hydrogen on the Eu(1)-Ni(5)/SBA-15 was 57.2%, which was better than that of Ln(1)-Ni(5)/SBA-15 (Ln = Dy, Pr, and Tb), the catalytic activity was kept steady even 25 h. As 1 wt% of Eu was added to Ni(5)/SBA-15, the oxygen vacancies caused by strong metal-support interaction (SMSI) effect due to the strong interaction between metals and carrier are made. They are resulted in increasing the dispersion of Ni⁰, and Ni²⁺ nano particles on the surface of catalyst, and are kept catalytic activity.

• Journal of Energy Engineering
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• v.20 no.3
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• pp.252-258
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• 2011

Nickel fiber mat was investigated as a potential structured catalyst for steam reforming of biogas in the temperature range of $600-700^{\circ}C$. The activity of as-received catalyst was very low owing to the smooth surface of fibers. Pretreatment of the catalyst by oxidation followed by reduction under methane partial oxidation condition significantly improved the catalytic activity, although degradation of the activity was found during the reaction due to oxidation and sintering. This deactivation was retarded by supplying additional hydrogen in the inlet gases or by coating $CeO_2$ over the catalyst surfaces.

• Applied Chemistry for Engineering
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• v.28 no.6
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• pp.720-725
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• 2017

M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) catalysts were prepared for the partial oxidation of methane (POM) to syngas. The catalysts were characterized by BET, TEM, and XPS. The BET-specific surface area and average pore size for M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm) were 538.8, 504.3, and $447.3m^2/g$ and 6.4, 6.8, and 7.1 nm, respectively. TEM results showed that the mesoporous hexagonol structure was formed for SBA-15, while the homogeneous dispersion of Ni and Ce particles on the surface was formed for Ce(10)-Ni(5)/SBA-15 caused by the confinment effect of SBA-15. XPS data confirmed that $Ce^{4+}$ and $Ce^{3+}$ on the surface catalyst have two oxidation states due to the lattice oxygen species ($O^{2-}$, $O^-$). The yields of POM to syngas over Ce(10)-Ni(5)/SBA-15 were 52.9% $H_2$ and 21.7% CO at 1 atm, 973 K, $CH_4/O_2=2$, $GHSV=1.08{\times}10^5mL/g_{cat.}{\cdot}h$, and these values were kept constant even after 75 h on streams. The same tendency of syngas yields was observed for M(10)-Ni(5)/SBA-15(M=Ce, Nd, Sm). These results confirm that the redox reaction of promoters including Ce, Nd, and Sm enhanced the stability and yield of catalysts.

• 한국가스학회:학술대회논문집
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• 1998.09a
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• pp.271-276
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• 1998