• Title/Summary/Keyword: Ni/MgO-$Al_2O_3$

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Enhancement of coke resistance on Ni/MgO-$Al_2O_3$ catalyst in combined $H_2O$ and $CO_2$ reforming of $CH_4$ for the syngas production (합성가스 생산을 위한 복합개질 반응에서 $Ni/MgO-Al_2O_3$ 촉매의 탄소 침적 저항성 향상에 관한 연구)

  • Koo, Kee-Young;Roh, Hyun-Seog;Jung, Un-Ho;Yoon, Wang-Lai
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.06a
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    • pp.727-730
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    • 2009
  • Highly active and stable nano-sized Ni catalysts supported on MgO-$Al_2O_3$ calcined from hydrotalcite-like materials have been successfully developed with a strong metal to support interaction (SMSI) to enhance the coke resistance in combined $H_2O$ and $CO_2$ reforming of $CH_4$ (CSCRM) for syngas ($H_2$/CO=2) production. The change of the surface area and NiO crystallite size with varying the pre-calcination temperature of support and Mgo content was investigated in relation to the coke resistance. As increasing the pre-calcination temperature, the surface area decreases and the metal to support interaction becomes weak. As a consequence, the coke deposition was more severe on catalysts pre-calcined at high temperature. It was concluded that highly dispersed Ni metal in the surface of Ni/MgO-$Al_2O_3$ catalyst (MgO=30 wt%) pre-calcined at $800^{\circ}C$ had a strong metal to support interaction (SMSI) resulting in an increase of coke resistance and high activity.

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Distribution Behavior of Ni between CaO-SiO2-Al2O3-MgO Slag and Cu-Ni Alloy (CaO-SiO2-Al2O3-MgO 슬래그와 Cu-Ni합금 사이의 Ni 분배거동)

  • Han, Bo-Ram;Sohn, Ho-Sang
    • Resources Recycling
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    • v.24 no.1
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    • pp.35-42
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    • 2015
  • To obtain the fundamental information on the dissolution of nickel into the slag in the pyrometallurgical processes for treatment of wasted PCB, the distribution ratios of nickel between CaO-$SiO_2-Al_2O_3$-MgO slag and copper-5 wt%Ni alloy were measured at 1623 K to 1823 K under a controlled $CO_2$-CO atmosphere. The distribution ratio of Ni increased linearly with increasing oxygen partial pressure. Therefore, the dissolution reaction of nickel into the slags could be described by the following equation; $$Ni(l)_{metal}+\frac{1}{2}O_2(g)NiO(l)_{slag}$$ The distribution ratio of Ni increased linearly with increasing content of basic oxides(CaO and MgO) in slag. However, the distribution ratio of Ni decreased linearly with increasing temperature. From these results, the empirical equation of distribution ratio of Ni was obtained by the following equation from the analysis of experimental conditions by multiple regression. $${\log}L_{Ni}=0.4000{\log}P_{O2}-5.1{\times}10^{-4}T+0.3375\(\frac{X_{CaO}+X_{MgO}}{X_{SiO2}}\)$$

Steam Reforming of Hydrothermal Liquefaction Liquid from Macro Algae over Ni-K2TixOy Catalysts (Ni-K2TixOy 촉매를 이용한 해조류 유래 수열 액화 원료의 수증기 개질 반응 연구)

  • Park, Yong Beom;Lim, Hankwon;Woo, Hee-Chul
    • Clean Technology
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    • v.23 no.1
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    • pp.104-112
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    • 2017
  • Hydrogen production via steam reforming of liquefaction liquid from marine algae over hydrothermal liquefaction was carried out at 873 ~ 1073 K with a commercial catalyst and Ni based $K_2Ti_xO_y$ added catalysts. Liquefaction liquid obtained by hydrothermal liquefaction (503 K, 2 h) was used as a reactant and comparison studies for catalytic activity over different catalysts (FCR-4-02, $Ni/K_2Ti_xO_y-Al_2O_3$, $Ni/K_2Ti_xO_y-SiO_2$, $Ni/K_2Ti_xO_y-ZrO_2/CeO_2$ and Ni/$K_2Ti_xO_y$-MgO), reaction temperature were performed. Experimental results showed Ni/$K_2Ti_xO_y$ based catalysts ($Ni/K_2Ti_xO_y-Al_2O_3$, $Ni/K_2Ti_xO_y-SiO_2$, Ni/$K_2Ti_xO_y-ZrO_2$/ $CeO_2$ and Ni/$K_2Ti_xO_y$-MgO) have a higher activity than commercial catalyst (FCR-4-02) and In particular, a product composition was different depending on support materials. An acidic support ($Al_2O_3$) and a basic support (MgO) led to a higher selectivity for CO while a neutral support ($SiO_2$) and a reducing support ($ZrO_2/CeO_2$) resulted in a higher $CO_2$ selectivity due to water gas shift reaction.

Autothermal Reforming Reaction of Methane using Ni-Ru/$Al_2O_3$-MgO Metallic Monolith Catalysts (Ni-Ru/$Al_2O_3$-MgO 금속 모노리스 촉매체를 이용한 메탄의 자열 개질반응)

  • Lee, Chang-Ho;Lee, Tae-Jun;Shin, Jang-Sik;Lee, Jong-Dae
    • Journal of the Korean Applied Science and Technology
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    • v.28 no.3
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    • pp.321-328
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    • 2011
  • The autothermal reforming reaction of methane was investigated to produce hyd rogen with Ni/$CeO_2-ZrO_2$, Ni/$Al_2O_3$-MgO and Ni-Ru/$Al_2O_3$-MgO catalysts. Honeycomb metalli c monolith was applied in order to obtain high catalytic activity and stability in autothermal r eforming. The catalysts were characterized by XRD, BET and SEM. The influence of various catalysts on hydrogen production was studied for the feed ratio($O_2/CH_4$, $H_2O/CH_4$). The $O_2/CH_4$ and $H_2O/CH_4$ ratio governed the methane conversion and temperature profile of reactor. Th e reactor temperature increased as the reaction shifted from endothermic to exothermic reactio n with increasing $O_2/CH_4$ ratio. Among the catalysts used in the experiment, the Ni-Ru/$Al_2O_3$-MgO catalyst showed the highest activity. The 60% of $CH_4$ conversion was obtained, and th e reactor temperature was maintained $600^{\circ}C$ at the condition of GHSV=$10000h^{-1}$ and feed ratio S/C/O=0.5/1/0.5.

Activity of Deoxygenation Reaction on Ni/MgO-$Al_2O_3$ : Effect of Calcination Temperature (소성온도에 따른 Ni/MgO-$Al_2O_3$ 촉매의 탈산소 반응 활성)

  • Eum, Ic-Hwan;Jeong, Dae-Woon;Kim, Ki-Sun;Roh, Hyun-Seog;Yi, Bo Eun;Na, Jeong-Geol;Ko, Chang Hyun
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.243.2-243.2
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    • 2010
  • 현재 바이오디젤(Bio diesel)은 유지와 메탄올을 염기촉매를 넣고 전이에스테르화(Trans-esterification)반응하여 생산한다. 생산된 1세대 바이오 디젤은 분자 내 산소가 다량 함유되어 여러 가지 단점을 가지기 때문에 전이에스테르화 반응을 대체한 탈산소(Deoxygenation)반응이 주목 받고 있다. 본 연구에서는 유리지방산(Free fatty acid, FFA)인 올레익 산(Oleic acid)의 탈산소반응을 수행하였다. 하이드로탈사이트(Hydrotalcites) 구조인 MgO-$Al_2O_3$(MgO=70 wt%)를 6시간 동안 $500^{\circ}C$에서 예비소성(Pre-calcination)하여 담체로 사용하였다. 제조된 MgO-$Al_2O_3$ 담체에 함침법(Incipient wetness method)으로 20 wt% Ni을 담지 시켰다. 제조된 Ni/MgO-$Al_2O_3$촉매는 소성온도를 변화시켜 반응 실험을 수행하였다. TPR 분석을 통해 산화-환원특성을 분석하였고 생성물의 원소분석을 통해 생성물의 산소함량을 측정하였다.

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Synthesis of (Ni,Mg)Al2O4 Ceramic Nano Pigment by a Polymerized Complex Method (착체중합법을 이용한 (Ni,Mg)Al2O4 Cyan 나노 무기안료 합성)

  • Son, Bo-Ram;Yoon, Dea-Ho;Han, Kyu-Sung;Cho, Woo-Suk;Hwang, Kwang-Taek;Kim, Jin-Ho
    • Journal of the Korean Ceramic Society
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    • v.50 no.3
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    • pp.195-200
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    • 2013
  • Here, we report preparation of cyan ceramic nano-pigment for inkjet printing and the Ni substitutional effects on the cyan color. $MgAl_2O_4$ was selected as the crystalline host network for the synthesis of nickel-based cyan ceramic nano-pigments. Various compositions of $Ni_xMg_{1-x}Al_2O_4$ ($0{\leq}x{\leq}1$) powders were prepared using the polymerized complex method. The powder was then preheated at $400^{\circ}C$ for 5 h and finally calcined at $1000^{\circ}C$ for 5 h. XRD patterns of $Ni_xMg_{1-x}Al_2O_4$ showed a single phase of the spinel structure in all the compositions. The particle sizes ranged from 20 to 50 nm in TEM observations. The characteristics of the color tones of $Ni_xMg_{1-x}Al_2O_4$ were analyzed by UV-Visible spectroscopy and CIE $L^*a^*b^*$ measurement. CIE $L^*a^*b^*$ measurement results indicate that the pigment color changes from light cyan to deep cyan due to the decrease of the $a^*$ and $b^*$ values with an increase of an Ni substitutional amount. In addition, the thermal stability and the binding nature of $Ni_xMg_{1-x}Al_2O_4$ are also discussed using TG-DSC and FT-IR results respectively.

The effect of MgO content on highly active Ni-MgO-$Al_2O_3$ catalysts prepared by homogeneous precipitation method (균일용액침전법으로 제조한 MgO 함량에 따른 고활성 Ni-MgO-$Al_2O_3$ 촉매에 대한 연구)

  • Jung, Youshick;Rhee, Youngwoo;Koo, Keeyoung;Jung, Unho;Youn, Wanglai;Seo, Yongseog
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.155-155
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    • 2011
  • 용융탄산염 연료전지(MCFC)는 $650^{\circ}C$에서 작동하는 고온형 연료전지 시스템이다. 이 시스템은 천연가스 등을 개질하여 생산된 수소를 바로 전기로 생산할 수 있는 시스템으로 열효율이 높으며, 현재 대체 발전시스템으로 각광을 받고 있다. MCFC는 개질방식에 따라 내부개질 방식과 외부개질 방식이 있다. 내부개질 방식은 수소를 생산하는 개질기가 스택내부에 장착된 형식으로 천연가스를 스택내부에서 개질하여 바로 전기를 생산하는 방식이다. 이 내부개질반응에 사용되는 촉매로는 알루미나에 고함량 (약 50 wt.%)으로 담지된 니켈(Ni) 계열촉매이 주로 쓰이고 있다. 이 고함량으로 담지된 촉매는 대부분 높은 활성을 보인다. 비교적 낮은 온도 운전조건 (약 $580{\sim}620^{\circ}C$)을 가지는 MCFC 내부개질에 적용하기 위해서는 활성점인 니켈을 최대한 담지체에 고르게 분산 시켜야한다. 이를 위해서 MgO를 이용하여 촉매의 활성점을 높게 분산시키는 연구를 진행 하였다. 촉매를 제조하는 방법으로 요소(urea)를 이용한 균일용액침전법을 이용하였다. 니켈함량은 50 wt.%로 고정을 한 다음, MgO 양과 $Al_2O_3$ 양을 각각 0 ~ 45 wt.%와 5 ~ 50 wt.%로 조절하면서 촉매를 제조하여 그 특성들을 분석하였다. 물성을 비교하기 위해서, X-선 회절분석 (XRD) 및 TPR, 물리화학흡착 실험을 하였다. 촉매의 활성을 살펴보기 위해서, fresh 상태 및 피독 상태에서 메탄수증기 개질활성 실험을 실시하였다. MgO 함량이 없거나 적은 촉매에서는 높은 BET surface area와 작은 NiO, metallic Ni 결정 크기가 나타났다. 반면 MgO 함량이 높은 촉매에서 낮은 BET surface area와 비교적 큰 NiO, metallic Ni 결정 크기가 나타났다. 또한 XRD 분석에서 MgO 함량이 증가할 수 록 MgO 결정 피크가 명확히 나타났으며, $MgAl_2O_4$ 피크는 나타나지 않았다. TPR 분석에서 촉매들의 환원 피크를 측정한 결과, 저함량의 MgO를 포함한 촉매는 $700^{\circ}C$ 부근에 환원 피크가 관찰되었고 MgO가 고함량인 촉매는 환원 피크가 $400^{\circ}C$ 부근에서 관찰되었다. 촉매의 초기 fresh 상태에서의 활성은 고함량 MgO를 포함한 Ni-90M10A 샘플을 제외하고 모든 촉매가 거의 비슷하게 나타났다. 그러나 $K_2CO_3$ 피독 상태에서는 MgO 함량이 증가할 수 록 활성이 좋지 않았음을 알 수 있었다. 따라서 MgO가 소량 포함된 촉매의 경우 fresh 상태에서는 우수한 물성과 활성을 보이지만, 피독상태에서는 MgO가 포함되지 않은 Ni-$Al_2O_3$ 촉매가 우수한 활성을 보였다.

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The Performance of NI/$MgAl_2O_4$ Coated Metal Monolith in Natural Gas Steam Reforming for Hydrogen Production (NI/$MgAl_2O_4$코팅된 금속 모노리스 촉매의 수소 생산을 위한 천연가스 수증기 개질 반응특성에 관한 연구)

  • Choi, Eun-Jeong;Koo, Kee-Young;Jung, Un-Ho;Rhee, Young-Woo;Yoon, Wang-Lai
    • Journal of Hydrogen and New Energy
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    • v.21 no.6
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    • pp.500-506
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    • 2010
  • The metal monolith catalyst coated with 15wt% Ni/$MgAl_2O_4$ is applied to the natural gas steam reforming for hydrogen production. To address the improvement of adherence between metal monolith and catalyst coating layer, the pre-calcination temperature as well as the coating conditions of $Al_2O_3$ sol are optimized. When the Fe-Cr alloy monolith is pre-calcined at $900^{\circ}C$ for 6 h, $Al_2O_3$ layer was formed uniformly on the entire surface of the metal substrate. It is seen that the formation of $Al_2O_3$ layer on the monolith surface is essential for the uniform coating of $Al_2O_3$ sol onto the monolith substrate. The monolith catalyst coated with 10wt% $Al_2O_3$ sol shows high $CH_4$ conversion and good thermal stability as compared with the monolith catalyst without $Al_2O_3$ sol coating under severe reaction conditions with high GHSV of 30,000 $h^{-1}$ at $700^{\circ}C$. In addition, the metal monolith catalyst shows higher catalytic activity and better thermal conductivity than 15wt% Ni/$MgAl_2O_4$ pellet catalyst.

Geochemical Dispersion and Enrichment of Fluvial Sediments Depending on the Particla Size Distribution (입도분포에 따른 하상퇴적물의 지구화학적 분산 및 부화)

  • 이현구
    • Economic and Environmental Geology
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    • v.32 no.3
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    • pp.247-260
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    • 1999
  • Geochermical characteristics of the fluvial sediments deprnding on particle size distribution size were investigated in the respect of majir, minor and rare eath element chemisitry. Ratios of $Al_{2}O_{3}/Na_{2}O$ and $K_{2}O/Na_{2}O$ of the sediments show the homogeneous valus, and partly positive correlation with $SiO_{2}/Al_{2}O_{3}$, respecively. Characteristics of minor element ratios (V/Ni, Cr/V, Ni/Co and Zr/Hf)are within the lower and narrow range. Thesesuggested that sediment sources may be acidic to intermediate granitic rock, and may be explained by simple weathering and sedimentation. With increasing SiO2 contents, concentrations of $Al_{2}O_{3}$, $Fe_{2}O_{3}$, CaO and MgO decreased, but those of $K_{2}O$ and $Na_{2}O$ increased, Concentrations of Ba, Be, Cs, Cu, Li, Ni, Sr, V and Zr show comparatively normal negative and some positive trends. Compared with the mean composition of granite, concentrations of $Al_{2}O_{3}$, $Fe_{2}O_{3}$, MnO, CaO and MgO in the sediments of the study area were highly enriced. Among some minor and rare earth elements, concentrations of As, Cd, Cu, and V were enriched, but those of Be, Ce, Rb, Sc, Sr and Zn were depleted when compared with average composition of granite. By decreasing of particle size fractions, SiO2, Rb and Sr conterts decreased, but concentrations of $Al_{2}O_{3}$, $Fe_{2}O_{3}$, CaO, MgO, $TiO_{2}$, MgO, $P_{2}O_{5}$, Be, Cu, Hf, Pb, V and Zr increased. From the correlations between particle size fractions and element concenreations, some elements of $Fe_{2}O_{3}$, CaO, MgO, $P_{2}O_{5}$, Cu, Ni, Zn and Zr showed typical trends in the secondary contramination sediments. These trends are typically shown under 100 mesh fractions. It indicates that the fraction of minus 100 mesh is the optimum size fraction for geochemical and environmental survey.

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Synthesis of Ethylamines for the Reductive Amination of Ethanol over Ni Catalysts: Effect of Supports (니켈 촉매상에서 에탄올의 환원성 아민화반응에 의한 에틸아민 제조 : 담체의 영향)

  • Jeong, Ye-Seul;Shin, Chae-Ho
    • Korean Chemical Engineering Research
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    • v.57 no.5
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    • pp.714-722
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    • 2019
  • Catalysts were prepared by using incipient wetness impregnation method with 17 wt% Ni on a support ($SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, $SiO_2$, $TiO_2$, MgO) and the catalytic activity in the reductive amination of ethanol with ammonia in the presence of hydrogen was compared and evaluated. The catalysts used before and after the reaction were characterized using X-ray diffraction, nitrogen adsorption, ethanol-temperature programmed desorption (EtOH-TPD), isopropanol-temperature programmed desorption (IPA-TPD), and hydrogen chemisorption etc. In the case of preparing $ZrO_2$ and $Y_2O_3$ supports, the small amount of Si dissolution from the Pyrex reactor surface provoked the formation of mixed oxides $SiO_2-ZrO_2$ and $SiO_2-Y_2O_3$. Among the catalysts used, $Ni/SiO_2-Y_2O_3$ catalyst showed the best activity, and this good activity was closely related to the highest nickel dispersion, and low desorption temperature in EtOH-TPD and IPA-TPD. The low catalytic activity on Ni/MgO catalysts showed low activity due to the formation of NiO-MgO solid-solutions. In the case of $Ni/TiO_2$, the reactivity was low due to the low nickel metal phase due to strong metal-support interaction. In the case of using a support as $SiO_2-Y_2O_3$, $Al_2O_3$, $SiO_2-ZrO_2$, and $SiO_2$, the selectivities of ethylamines and acetonitrile were not significantly different at similar ethanol conversion.