• Journal of Hydrogen and New Energy
• /
• v.29 no.5
• /
• pp.419-426
• /
• 2018

$Ni-La_2O_3-Ce_{0.8}Zr_{0.2}O_2$ catalysts with various $La_2O_3$ loading were investigated for hydrogen production from steam reforming of methane (SRM). The $La_2O_3$ loading influenced the physicochemical properties of $Ni-La_2O_3-Ce_{0.8}Zr_{0.2}O_2$ catalysts such as BET surface area, Ni dispersion, Ni size and reducibility. Among the prepared catalysts, $Ni-70La_2O_3-Ce_{0.8}Zr_{0.2}O_2$ catalyst showed the highest activity and stability at a very high gas hourly space velocity (GHSV) of $932,556h^{-1}$. This is mainly due to high Ni dispersion, small Ni size and high reducibility.

• 한국신재생에너지학회:학술대회논문집
• /
• 2009.11a
• /
• pp.232-232
• /
• 2009

최근 WGS반응용 Pt 촉매의 성능 향상을 위한 다양한 담체 및 조촉매(Promotor) 개발에 대한 연구가 활발하게 진행되고 있다. 선행 연구결과, 입방(Cubic)구조를 가지는 $Ce_{0.8}Zr_{0.2}O_2$ 담체는 정방 입계(Tetragonal)구조를 가지는 $Ce_{0.2}Zr_{0.8}O_2$ 담체 또는 혼합산화물(Mixed oxide)구조를 가지는 $Ce_{0.5}Zr_{0.5}O_2$ 담체 보다 높은 활성과 안전성을 가진다. 이것은 촉매의 성능 향상이 Ce-$ZrO_2$의 결정구조에 의존한다는 것을 나타낸다. 따라서 WGS 반응에서 Ce/Zr 비에 따라 변화된 담체 특성이 Pt 촉매의 활성에 영향이 있을 것으로 예상되며 실험결과 1% Pt/$CeO_2$ 촉매가 가장 높은 활성을 나타내었다. 따라서 Pt/Ce-$ZrO_2$ 촉매의 성능 향상을 위해 Ce-$ZrO_2$ 담체에 조촉매인 Ni을 첨가하여 촉매적 활성을 비교하여 보았다. 촉매는 2%의 Pt과 15%의 Ni로 고정하였고 Ce/Zr 비를 제조변수로 하였다. 제조된 모든 담체는 공침법(Co-precipitation)을 사용하여 제조하였으며 $500^{\circ}C$에서 6시간 소성하였다. Pt 촉매는 함침법 (Incipient wetness impregnation)으로 담지 시켰다. 2% Pt/Ce-$ZrO_2$ 촉매와 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매는 저온영역($200^{\circ}{\sim}320^{\circ}C$)에서 비슷한 CO 전환율을 나타내었으나 고온영역($360^{\circ}C{\sim}400^{\circ}C$)에서는 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 더 높은 CO의 전환율을 나타내었다. 이것은 Ni의 영향으로 고온에서 부반응인 메탄화 반응(Methanation reaction)이 생긴 것으로 판단되어 메탄($CH_4$)의 선택도를 살펴본 결과 2% Pt/15% Ni-Ce-$ZrO_2$ 촉매가 고온영역($360^{\circ}{\sim}400^{\circ}C$)에서 급격하게 증가하는 것으로 나타나 메탄화 반응이 일어난 사실을 증명한다.

• Journal of Hydrogen and New Energy
• /
• v.23 no.3
• /
• pp.213-218
• /
• 2012

Steam reforming of methane (SRM) is the primary method to produce hydrogen. Commercial Ni-based catalysts have been optimized for SRM with excess steam ($H_2O/CH_4$ > 2.5) at high temperatures (> $700^{\circ}C$). However, commercial catalysts are not suitable under severe conditions such as stoichiometric steam over methane ratio ($H_2O/CH_4$ = 1.0) and low temperature ($600^{\circ}C$). In this study, 15wt.% Ni catalysts supported on $Ce_{0.8}Zr_{0.2}O_2$ were prepared at various calcination temperatures for SRM at a very high gas hourly space velocity (GHSV) of $621,704h^{-1}$. The calcination temperature was systematically varied to optimize 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst at a $H_2O/CH_4$ ratio of 1.0 and at $600^{\circ}C$. 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ exhibited the highest $CH_4$ conversion as well as stability with time on stream. Also, 15wt.% $Ni-Ce_{0.8}Zr_{0.2}O_2$ catalyst calcined at $500^{\circ}C$ showed the highest $H_2$ yield (58%) and CO yield (21%) among the catalysts. This is due to complex NiO species, which have relatively strong metal to support interaction (SMSI).

• Korean Chemical Engineering Research
• /
• v.51 no.1
• /
• pp.47-52
• /
• 2013

In this study, the catalytic performance and characterization of $Ni/Ce_xZr_{1-x}O_2$ were investigated using an autothermal reforming (ATR) process for hydrogen production. The $Ni/Ce_xZr_{1-x}O_2$ catalysts were prepared using the following methods: the water method (CZ-W), urea water method (CZ-UW) and urea, water and ethanol method (CZ-UWA). The performance of $Ni/Ce_xZr_{1-x}O_2$ catalysts in autothermal reforming of propane for hydrogen production was studied in a fixed-bed flow reactor. Reaction tests were conducted by using a feed of $H_2O/C_3H_8/O_2$=3/1/0.37 and $300{\sim}700^{\circ}C$. The CZ-UW and CZ-UWA catalysts showed higher propane conversion and hydrogen yield than the CZ-W catalyst. The activity test confirmed that the improvement in the water-ethanol catalyst was due to the low level of carbon deposition. SEM showed that the surface carbon consisted of clusters on the used CZ-UW catalyst, which is incontrast to the nano-fiber morphology observed on the used CZ-UWA catalyst. It was found that the amount of carbon deposition depends on the preparation method. Especially the $Ni/Ce_{0.75}Zr_{0.25}O_2$ was showed higher propane conversion and hydrogen yield than the other catalysts. Also TGA showed that the resistance of carbon deposition increase to Co addition.

• Journal of the Korean Ceramic Society
• /
• v.56 no.1
• /
• pp.91-97
• /
• 2019

The effect of different Ni-containing additives on the sintering behavior and electric conductivity of the proton conducting electrolyte $BaCe_{0.35}Zr_{0.5}Y_{0.15}O_{3-{\delta}}$ (BCZY5) was investigated. Ni-doped, NiO-added, and $BaY_2NiO_5$(BYN)-added (all 4 mol%) BCZY5 samples were prepared by the solid state synthesis method and sintered at $1400^{\circ}C$ for 6 h. Among the three samples, the onset of densification was observed at the lowest temperature for NiO-added BCZY5, which is attributed to the formation of an intermediate phase at a low melting temperature. The BYN-added sample, where no consumption of the constitutional elements of the electrolyte was expected during sintering, exhibited the highest electrical conductivity whereas the doped sample had the lowest conductivity. The electrical conductivities at $500^{\circ}C$ under humid argon atmosphere were measured to be 2.0, 4.8, and $6.2mS{\cdot}cm^{-1}$ for Ni-doped and NiO- and BYN-added samples, respectively.

• Proceedings of the Korea Institute of Applied Superconductivity and Cryogenics Conference
• /
• 2003.02a
• /
• pp.129-132
• /
• 2003

Yttria stabilized zirconia (YSZ) buffer layers were deposited by a metal organic chemical vapor deposition (MOCVD) technique using single liquid source for the application of YBa$_2$Cu$_3$$O_{7-x}$ (YBCO) coated conductor. Y:Zr mole ratio was 0.2:0.8, and tetrahydrofuran (THF) was used as a solvent. The (100) single crystal MgO substrate was used for searching deposition condition. Bi-axially oriented CeO$_2$ and NiO films were fabricated on {100}〈001〉 Ni substrate by the same method and used as templates. At a constant working pressure of 10 Torr, the deposition temperatures (660~80$0^{\circ}C$) and oxygen flow rates (100~500 sccm) were changed to find the optimum deposition condition. The best (100) oriented YSZ film on MgO was obtained at 74$0^{\circ}C$ and $O_2$ flow rate of 300 sccm. For YSZ buffer layer with this deposition condition on CeO$_2$/Ni template, full width half maximum (FWHM) values of the in-plane and out-of-plane alignments were 10.6$^{\circ}$ and 9.8$^{\circ}$, respectively. The SEM image of YSZ film on CeO$_2$/Ni showed surface morphologies without microcrack.k.

• Journal of the Korean earth science society
• /
• v.27 no.1
• /
• pp.49-60
• /
• 2006

The purpose of this study is to investigate geochemical characteristics for stream sediments in the Naju area. We collected 139 stream sediments samples from primary channels. Samples were dried slowly in the laboratory and chemical analysis was carried out using XRF. ICP-AES and NAA. In order to investigate geochemical characteristics, the geological groups categorized into granitic gneiss area, schist area, granite area, arenaceous rock area, tuff area, andesite area, and rhyolite area. Average contents of major elements for geological groups are $SiO_2\;58.37{\sim}66.06wt.%,\;Al_2O_3\;13.98{\sim}18.41wt.%,\;Fe_2O_3\;4.09{\sim}6.10wt.%,\;CaO\;0.54{\sim}1.33wt.%,\;MgO\;0.86{\sim}1.34wt.%,\;K_2O\;2.38{\sim}4.01wt.%,\;Na_2O\;0.90{\sim}1.32wt.%,\;TiO_2\;0.82{\sim}1.03wt.%,\;MnO\;0.09{\sim}0.15wt.%,\;P_2O_5\;0.11{\sim}0.18wt.%$. According to the comparison of average contents of major elements, $Al_2O_3\;and\;K_2O$ are higher in granitic gneiss area, $Fe_2O_3,\;CaO,\;P_2O_5$ are higher in tuff area, MgO and $TiO_2$ are higher in andesite area, $Na_2O_$ is higher in rhyolite area, $SiO_2$, and MnO are higher in arenaceous rock area. Average contents of minor and rare earth elements for geological groups are $Ba\;1278{\sim}1469ppm,\;Be\;1.1{\sim}1.5ppm,\;Cu\;18{\sim}25ppm,\;Nb\;25{\sim}37ppm,\;Ni\;16{\sim}25ppm,\;Pb\;21{\sim}28ppm,\;Sr\;83{\sim}155ppm,\;V\;64{\sim}98ppm,\;Zr\;83{\sim}146ppm,\;Li\;32{\sim}45ppm,\;Co\;7.2{\sim}12.7ppm,\;Cr\;37{\sim}76ppm,\;Cs\;4.8{\sim}9.1ppm,\;Hf\;7.5{\sim}25ppm,\;Rb\;88{\sim}178ppm,\;Sc\;7.7{\sim}12.6ppm,\;Zn\;83{\sim}143ppm,\;Pa\;11.3{\sim}37ppm,\;Ce\;69{\sim}206ppm,\;Eu\;1.1{\sim}1.5ppm,\;Yb\;1.8{\sim}4.4ppm$. According to the comparison of average contents of minor and rare earth elements for geological groups, Pb, Li, Cs, Hf, Rb, Sb, Pa, Ce, Eu, and Yb are higher in granitic gneiss area; Ba, Co, and Cr in schist area; Nb, Ni, and Zr in arenaceous rock area; Sr in tuff area: and Be, Cu, V, Sc, and Zn are such in andesite area.

• Journal of the Korean Ceramic Society
• /
• v.45 no.12
• /
• pp.766-771
• /
• 2008

We fabricated single cells with a cathode consisting of a $LaNi_{0.6}Fe_{0.4}O_3-Ce_{0.8}Sm_{0.2}O_{1.9}$ composite (LNF-S20DC composite) active layer and an LNF current collecting layer on a ${0.89ZrO_2}-{0.10Sc_2}{O_3}-0.01{Al_2}{O_3}$ electrolyte sheet. The cathode layers were prepared by the screen-printing method. The cathode properties of these cells were measured by the AC impedance method at $800^{\circ}C$. The cathodes with the ceria-LNF composite active layer exhibited high power performance prior to current loading. We investigated the influence of the mixture ratio of LNF and S20DC on the cathodes properties. The Sm in the ceria particles of the composite cathode was substituted with other rare-earth elements. Cathodes with Pr and Gd co-doped ceria in the active layer provided the better performance than those with Sm- or Gd-doped ceria.

• Economic and Environmental Geology
• /
• v.30 no.1
• /
• pp.1-14
• /
• 1997

The shales from the Euiseong area are interbedded along the bedding in Cretaceous Gyeongsang Supergroup, which are composed mainly of quartz, plagioclase, K-feldspar and associated with trace amount of biotite, muscovite, chlorite, pyrite, hematite, carbonate and clay minerals. The ratio of $Al_2O_3/Na_2O$ and $K_2O/Na_2O$ in shales from the Shindong Group are ranged from 9.16 to 24.32 and from 1.70 to 5.97, and the Hayang Group ranged from 2.76 to 8.89 and from 0.42 to 2.74, which are negative correlated between $K_2O/Na_2O$ and $Al_2O_3/Na_2O$ against $SiO_2/Al_2O_3$ respectively. Those are suggested that controlled of mineral compositions in shales due to substitution and migration of elements by sedimentation and diagenesis. These shale formation were deposited in basin of terrestrial environments originated from the igneous rocks, and the REE of these rocks are not influenced with diagenesis and hydrothermal alterations on the basis of $Al_2O_3$ versus La, La against Ce, Zr versus Yb, the ratios of La/Ce (0.43 to 0.62) and Th/U (1.11 to 10.71). The narrow range in trace and REE element characteristics as Co/Th (0.63 to 1.92), La/Sc (1.98 to 5.90), Sc/Th (0.58 to 1.30), V/Ni (0.90 to 3.25), Cr/V (0.45 to 1.78), Ni/Co (1.88 to 6.67) and Zr/Hf (30.04~60.87) of these shales argues for inefficient mixing of the simple source lithologies during sedimentation. These rocks also show much variation in $La_N/Yb_N$ (6.90 to 17.02), Th/Yb (4.17 to 13.68) and La/Th (1.98 to 5.90), and their origin is explained by derivation from a mixture of intermediate to acidic igneous rocks.

• Journal of the Korean Ceramic Society
• /
• v.51 no.4
• /
• pp.271-277
• /
• 2014

To overcome the limitations of the solid oxide fuel cells (SOFCs) due to the high temperature operation, there has been increasing interest in proton conducting fuel cells (PCFCs) for reduction of the operating temperature to the intermediate temperature range. In present work, the perovskite $BaCe_{0.85-x}Zr_xY_{0.15}O_{3-\delta}$ (BCZY, x = 0.1, 0.3, 0.5, and 0.7) were synthesized via solid state reaction (SSR) and adopted as an electrolyte materials for PCFCs. Powder characteristics were examined using X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Brunauer, Emmett and Teller (BET) surface area analysis. Single phase BCZY were obtained in all compositions, and chemical stability was improved with increasing Zr content. Anode-supported cell with $Ni-BaCe_{0.55}Z_{0.3}Y_{0.15}O_{3-\delta}$ (BCZY3) anode, BCZY3 electrolyte and BCZY3-$Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-\delta}$ (BSCF) composite cathode was fabricated and electrochemically characterized. Open-circuit voltage (OCV) was 1.05 V, and peak power density of 370 ($mW/cm^2$) was achieved at $650^{\circ}C$.