• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.230.2-230.2
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• 2010

천연가스 수증기 개질 반응에 사용되는 펠릿 촉매의 단점인 열 및 물질 전달 제한, 낮은 effectiveness factor, 압력강화와 channeling 등의 문제점을 해결 하고자 모노리스 형태의 금속 구조체 촉매를 본 연구에 적용 하였다. Fecralloy 재질의 금속 구조체에 Ni 촉매를 워시코팅 (wash coating) 하여 제조 하였으며, 이를 천연가스 수증기 개질 반응에 적용하여 수소를 생산하였다. 실험 조건으로는 S/C ratio를 3으로 고정하여 온도를 $600^{\circ}C{\sim}800^{\circ}C$로 변화 시켰으며, GHSV $3000{\sim}30000h^{-1}$에서 진행 되었다. 구조체 촉매 코팅에 사용된 Ni 촉매의 BET, TPR, H2-chemisorption, SEM, EDS의 특성분석을 수행 하였다. 온도별 테스트에서 모노리스 형태의 금속 구조체 촉매가 펠릿 형태의 촉매에 비해 우수한 열전달 효과로 인해 낮은 퍼니스 온도와 높은 반응 활성을 나타내었으며, GHSV 변화에 따른 성능평가 결과도 15wt% $Ni/MgAl_2O_4$펠릿 촉매와 비교하여 금속 구조체 촉매가 높은 활성을 보였다.

• 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.

• 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.

• Korean Chemical Engineering Research
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• v.48 no.6
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• pp.776-783
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• 2010

Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.372-381
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• 2015

The effect of preparation method on the catalytic activities of the $Ni/Al_2O_3$ catalysts on steam reforming of ethylene glycol was investigated. The catalysts were prepared with various preparation methods such as an incipient wetness impregnation, wet impregnation, and coprecipitation method. In the case of coprecipitation method, various precipitants such as KOH, $K_2CO_3$, and $NH_4OH$ were compared. The prepared catalysts were characterized by using $N_2$ physisorption, inductively coupled plasma-atomic emission spectroscopy, X-ray diffraction, temperatureprogrammed reduction, pulsed $H_2$ chemisorption, temperature-programmed oxidation, scanning electron microscopy, and thermogravimetric analysis. Among the catalysts reduced at 773 K, the $Ni/Al_2O_3$ catalyst prepared by a coprecipitation with KOH or $K_2CO_3$ as precipitants showed the best catalytic performance. The preparation method affected the particle size of Ni, reducibility of nickel oxides, catalytic performance (activity and stability), and types of coke formed during the reaction. The $Ni/Al_2O_3$ catalyst prepared by a coprecipitation with KOH showed the increasing catalytic activity with an increase in the reduction temperature from 773 to 1173 K because of an increase in the reduction degree of Ni oxide species even though the particle size of Ni increased with increasing reduction temperature.

• 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.

• Resources Recycling
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• v.13 no.2
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• pp.3-8
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• 2004

A basic study on the recovery of heavy metals such as Zn, Ni, Cu and Fe ions from wastewater was carried out with the spent iron oxide catalyst, which was used in the Styrene Monomer(SM) production company. The heavy metals could be recovered more than 98％ with the spent iron oxide catalyst. The alkaline components of the spent catalyst could be precipitated the metal ions of the wastewater as metal hydroxides at the higher pH 10.6 in Ni, pH 8.0 in Cu, pH 6.5 in Fe, pH 8.5 in Zn. But the metal ions are adsorbed physically on the surface of the spent catalyst in the range of the pH of the metal hydroxides and pH 3.0, which is the isoelectric point of the iron oxide catalyst.

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.394-398
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• 1981

Two types of Ni(II)-polyethyleneimine (PEI) complexes, [Ni(PEI)]$Cl_2$ and [Ni(P-EI)$Cl_2$] were synthesized and their catalytic activities in the decomposition reaction of hydrogen peroxide were investigated. For the purpose of comparison, the corresponding monomeric complexes, $[Ni(en)_3]Cl_2$ and $[Ni(en)_2Cl_2$ were also prepared; it was observed that their activities increase in the following order; $0{\approx}[Ni(en)_3]Cl_2{\le}[Ni(en)_2Cl_2]<[Ni(PEI)]Cl_2<[Ni(PEI)Cl_2]$ On the basis of structural analysis by means of visible and infrared spectroscopy, the catalytic activiy of these Ni(II)-PEI complexes is assumed to depend on the bond strength between the ligand and the nickel ion.

• Applied Chemistry for Engineering
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• v.32 no.6
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• pp.627-631
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• 2021

Research on induction heating catalyst system was conducted to solve problems of the existing catalyst system for removing volatile organic compounds. In the present study, three types of Ni-based commercial catalysts were employed, and induction heating reaction characteristics including the catalyst volume, composition, heat treatment atmosphere, and position in the coil were investigated. The composition and volume of the catalyst affected the exothermic and toluene oxidation performance in the induction heating system. In particular, the Fe-added catalyst showed high exothermic performance compared to that of other catalysts consisting of more than 99% Ni, but had low toluene oxidation performance. In addition, the heat treatment in an air atmosphere of the Ni-based catalyst drastically reduced the performance. In the induction heating system, the optimal condition for the catalyst was to be located in the center of the coil. The catalyst showed similar activities among seven repeated experiments under the optimal condition derived from this work.

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