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Preparation and Reactivity of Cu-Zn-Al Based Hybrid Catalysts for Direct Synthesis of Dimethyl Ether by Physical Mixing and Precipitation Methods (물리혼합 및 침전법에 의한 DME 직접 합성용 Cu-Zn-Al계 혼성촉매의 제조 및 반응특성)

  • Bang, Byoung Man;Park, No-Kuk;Han, Gi Bo;Yoon, Suk Hoon;Lee, Tae Jin
    • Korean Chemical Engineering Research
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    • v.45 no.6
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    • pp.566-572
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    • 2007
  • Two hybrid catalysts for the direct synthesis of DME were prepared and the catalytic activity of these catalysts were investigated. The hybrid catalyst for the direct synthesis of DME was composed as the catalytic active components of methanol synthesis and dehydration. The methanol synthesis catalyst was formed from the precursor contained Cu and Zn, the methanol dehydration catalyst was used ${\gamma}-Al_2O_3$. As PM-CZ+D and CP-CZA/D, Two hybrid catalysts were prepared by physical mixing method (PM-CZ+D) and precipitation method (CP-CZA/D), respectively. PM-CZ+D was prepared by physically mixing methanol synthesis catalyst and methanol dehydration catalyst, CP-CZA/D was prepared by depositing Cu-Zn or Cu-Zn-Al components on ${\gamma}-Al_2O_3$. The crystallinity and the surface morphology of synthesized catalyst were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM) to investigate the physical property of prepared catalyst. And BET surface area by $N_2$ adsorption and the surface area of Cu by $N_2O$ chemisorption were investigated about the hybrid catalysts. In addition, catalytic activity of these hybrid catalysts was examined with varying reaction conditions. At that time, the reaction temperature of $250{\sim}290^{\circ}C$, the reaction pressure of 50~70 atm, the $[H_2]/[CO]$ mole ratio of 0.5~2.0 and the space velocity of $1,500{\sim}6,000h^{-1}$ were investigated the catalytic activity. From these results, it was confirmed that the reactivity of CP-CZA/D was higher than that of PM-CZ+D. When the conditions of reaction temperature, pressure, $[H_2]/[CO]$ ratio and space velocity were $260^{\circ}C$, 50 atm and 1.0, $3,000h^{-1}$ respectively, CO conversion using CP-CZA/D hybrid catalyst was 72% and the CO conversion of CP-CZA/D was more than 20% compared with the CO conversion of PM-CZ+D. It was known that Cu surface area of CP-CZA/D hybrid catalyst was higher than that of hybrid PM-CZ+D catalyst using $N_2O$ chemisorption. It was assumed that the catalytic activity was improved because Cu particle of hybrid catalyst prepared by precipitation method was well dispersed.

Semi-quantitative Analysis of Manganese Oxide Mineral in Manganese Nodule From the East Siberian Sea (동시베리아해 망가니즈단괴의 산화망가니즈광물 반정량 분석)

  • Yu, Hye Jin;Shin, Eun Ju;Koo, Hyo Jin;Cho, Hyen Goo
    • Korean Journal of Mineralogy and Petrology
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    • v.33 no.4
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    • pp.427-437
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    • 2020
  • Manganese nodules, which are evaluated as potential metal resources, have been found in the Arctic Ocean as well as in the abyssal plains of the Pacific and Indian Oceans. Manganese nodules exhibit strong variations in the morphology, internal texture, chemical composition and mineralogy as they grow. The relationship between the texture and chemical elemental composition during the growth process is well documented, but the mineral composition variation during the growth process is not. Because the manganese oxide minerals in nodules are fine-grained and poorly crystalline, quantitative analysis for the mineral composition is challenging for the bulk nodule sample. This study investigated the internal texture and Mn-oxide mineral composition of manganese nodules obtained from the East Siberian Sea. Semi-quantitative analysis was attempted for three main Mn-oxide minerals constituting the manganese nodules (i.e., todorokite, buserite and birnessite) using the peak area ratio of X-ray diffraction analysis graphs. In the East Siberian Sea manganese nodules, birnessite is more abundant than buserite or todorokite, and no correlation is found between the mineral composition and the internal texture. Instead a correlation is found between the relative content of todorokite and the lamellae depth. The todorokite content tends to increase from the surface to the core of the nodules, which can be attributed to a recrystallization process or difference in the growth rate within the nodule. This study shows that semi-quantitative analysis of manganese oxide minerals using the peak area ratio is useful in the mineralogical study of manganese nodules.