• Clean Technology
• /
• v.20 no.2
• /
• pp.189-201
• /
• 2014

Partial oxidation, $CO_2$ reforming and the oxidative $CO_2$ reforming of $CH_4$ to produce synthesis gas over supported Ni hydrotalcite-type ($Ni_{0.5}Ca_{2.5}Al$ catalyst) catalysts were carried out and the effects of metal supports (i.e.; Mg and Ca) on the formation of a stable double-layer structure on the catalysts were evaluated. The $CH_4$ reforming stability was determined to be affected by the differences in the interaction strength between the active Ni ions and support metal ions. Only a Ni-Mg-Al composition produced a highly stable hydrotalcite-type double-layered structure; while the Ni-Ca-Al-type composition did not. Such structure provides excellent stability for the catalyst (-80% efficiency) as confirmed by the long-term $CO_2$ reforming test (-100 h), while the Ni-Ca-Al catalyst exhibited deactivation phases starting at the beginning of the reaction. The interaction strength between the active metal (Ni) and the supporting components (Mg and Al) was determined by temperature-programed reduction (TPR) analyses. The affinity was also confirmed by the TPR temperature because the Ni-Mg-Al catalyst required a higher temperature to reduce the Ni relative to the Ni-Ca-Al catalyst. The highest initial activity for synthesis gas production was observed for the $Ni_{0.5}Ca_{2.5}Al$ catalyst; however, this activity decreased quickly due to coke formation. The $Ni_{0.5}Ca_{2.5}Al$ catalyst exhibited a high reactivity and was more stable than the other catalysts because it had a higher resistance to coke formation.

• Journal of the Korean Ceramic Society
• /
• v.40 no.6
• /
• pp.594-600
• /
• 2003

L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ perovskite-type mixed conducting membranes, which could permeate oxygen selectively, have been fabricated and the microstructural features developed by varying the sintering conditions have been analyzed. The effects of surface modification and the membrane thickness on oxygen permeability have been evaluated under He/air environment. With increasing a grain boundary fraction, the overall oxygen permeability decreased. The syngas (CO+ $H_2$) has been produced by partial oxidation reaction of methane with the oxygen permeated through the membrane. Methane conversion and syngas yield have been evaluated as functions of the compositional ratio of feed gas and reaction temperature. In long-term duration test for 600 h, under C $H_4$+He/air environment, L $a_{0.7}$S $r_{0.3}$G $a_{0.6}$F $e_{0.4}$ $O_{3-}$$\delta$/ membrane showed a highly stable performance.

• Korean Chemical Engineering Research
• /
• v.51 no.4
• /
• pp.443-454
• /
• 2013

Various metal ions (transition and base metals) incorporated MCM-41 catalysts can be synthesized using colloidal and soluble silica with non-sodium involved process. Transition metal ion-typically $V^{5+}$, $Co^{2+}$, and $Ni^{2+}$-incorporated MCM-41 catalysts were synthesized by isomorphous substitution of Si ions in the framework. Each incorporated metal ion created a single species in the silica framework, single-site solid catalyst, showing a substantial stability in reduction and catalytic activity. Radius of pore curvature effect was investigated with Co-MCM-41 by temperature programmed reduction (TPR). The size of metallic Co clusters, sub-nanometer, could be controlled by a proper reduction treatment of Co-MCM-41 having different pore size and the initial pH adjustment of the Co-MCM-41 synthesis solution. These small metallic clusters showed a high stability under a harsh reaction condition without serious migration, resulting from a direct anchoring of small metallic clusters to the partially or unreduced metal ions on the surface. After a complete reduction, partial occlusion of the metallic cluster surface by amorphous silica stabilized the particles against aggregations. As a probe reaction of particle size sensitivity, carbon single wall nanotubes (SWNT) were synthesized using Co-MCM-41. A metallic cluster stability test was performed by CO methanation using Co- and Ni-MCM-41. Methanol and methane partial oxidations were carried out with V-MCM-41, and the radius of pore curvature effect on the catalytic activity was investigated.

• Journal of the Korean Electrochemical Society
• /
• v.6 no.1
• /
• pp.59-64
• /
• 2003

We fabricated mixed ionic-electronic conducting membranes, $CH_4\;Using\;{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$, by solid state reaction method for solid oxide fuel cell. The membranes consisted of single perovskite phase and exhibited high relative density, $>95\%$. We coated $La_{0.6}Sr_{0.4}CoO_{3-\delta}$ layer using screen printing method in order to improve surface reactivity of the $La_{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$. As a result, the oxygen permeation flux of the coated $La_{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$ showed higher value, $0.5ml/min{\cdot}cm^2\;at\;950^{\circ}C$ than the uncoated one. Higher oxygen permeation was observed in the porously coated Lao $La_{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$membranes with larger grain sizes. Syngas, $CO+H_2$, was successfully obtained from methane gas, $CH_4$, using the $La_{0.6}Sr_{0.4}CoO_{3-\delta}$ coated $La_{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$, with over $40\%\;of\;CH_4$ conversion and syngas yield. $La_{0.7}Sr_{0.3}Ga_{0.6}Fe_{0.4}O_{3-\delta}$ membrane was stable even when it was exposed to the reducing environment, methane, for 600 hrs at $950^{\circ}C$.