• 한국수소및신에너지학회논문집
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• 제23권3호
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• pp.213-218
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• 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
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• 제56권2호
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• pp.269-274
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• 2018

All the $Ni-Co-Ce-ZrO_2$ mixed oxides are prepared by co-precipitations methods. Methanation of CO and $H_2$ reaction is screened tested over different fractions of cerium (2, 4, 7 and 12 wt.%) over $Ni-Co/ZrO_2$ bimetallic catalysts are investigated. The mixed oxides are characterized by XRD, CO-Chemisorption, TGA and screened methanation of CO and $H_2$ at $360^{\circ}C$ for 3000 min on stream at typical ratio $CO:H_2=1:1$. In $Ni-Co/CeZrO_2$ series 2 wt.% Ce loading catalyst shows most promising catalyst for $CH_4$ selectivity than $CO_2$, which directs more stability with less coke formation. The high activity is attributed to the better bimetallic synergy and the well-developed crystalline phases of NiO, $ZrO_2$ and $Ce-ZrO_2$. Other bimetallic mixed oxides NCoZ, $NCoC^{4-12}Z$ has faster deactivation with low methanation activity. Finally, 2 wt.% Ce loading catalyst was found to be optimal coke resistant catalyst.

• Korean Chemical Engineering Research
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• 제48권6호
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• pp.776-783
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• 2010

수소생산을 위한 메탄의 부분산화용 촉매로 알루미나에 담지된 코발트와 니켈 촉매를 함침법으로 제조하였다. 메탄의 부분산화반응을 위한 이들 촉매의 반응활성은1기압, $CH_4/O_2=2.0$과 $450{\sim}650^{\circ}C$의 온도영역에서 조사하였다. 담지량이 다른 코발트촉매와 니켈촉매의 반응활성을 비교하고 코발트촉매에 니켈을 첨가한 이성분금속 촉매의 반응활성을 조사하였다. 그리고 코발트촉매와 니켈촉매에 첨가된 Ce와 La의 첨가효과를 조사하였다. 이들 촉매의 특성은 XRD와 SEM/EDX로 분석하였다. 코발트와 니켈은 10 wt%의 담지량이 적절한 것으로 나타났다. 이들 10 wt% 담지 코발트와 니켈촉매는 열역학적 평형값에 가까운 메탄의 전환율과 CO의 선택성을 나타내었으나 $H_2$의 선택성은 평형값보다 다소 낮게 나타났다. 코발트촉매에 니켈을 첨가한 이성분금속 촉매에서 $H_2$의 선택성은 증가하였으나 전환율을 고려하면 니켈을 첨가한 이점은 나타나지 않았다. 코발트촉매에서는 Ce의 첨가와 니켈촉매에서는La의 첨가로 메탄의 전환율과 수소의 선택성을 높일 수 있었다.

• Korean Chemical Engineering Research
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• 제51권1호
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• pp.47-52
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• 2013

본 연구는 $Ni/Ce_xZr_{1-x}O_2$ 촉매를 이용하여 프로판의 자열개질반응을 통한 수소제조에 관한 것이다. $Ni/Ce_xZr_{1-x}O_2$ 촉매는 용매로서 물을 사용한 방법(CZ-W), 우레아와 물을 사용한 방법(CZ-UW), 우레아, 에탄올 및 물을 사용한 방법(CZ-UWA)으로 각각 제조하였다. 반응물질의 조성은 $Steam/C_3H_8$=3, $C_3H_8/O_2$=2.70 이었고, 반응은 상압 고정층 유통식 반응기에서 $300{\sim}700^{\circ}C$ 온도범위에서 진행하였다. 촉매제조시 용매에 우레아 및 에탄올을 첨가할 경우 촉매의 활성이 증가하였다. CZ-UW 촉매의 경우 클러스터형태의 탄소생성에 기인한 활성점 피막으로 인해 쉽게 비활성화가 초래됐다. 하지만 CZ-UWA 촉매의 경우 반응 후 탄소가 활성에 영향을 미치지 않는 나노파이버형태로 존재하여 활성저하가 발생되지 않음을 SEM을 통해 확인했다. 또한 $Ni/Ce_{0.75}Zr_{0.25}O_2$ 촉매의 전환율 및 수율이 더 좋게 나타났으며 또한 소량의 Cobalt를 첨가했을 때 탄소에 대한 저항성이 크게 향상됨을 TGA로 확인하였다.

• Korean Chemical Engineering Research
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• 제47권1호
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• pp.17-23
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• 2009

알루미나가 코팅된 허니컴 구조의 금속모노리스에 담지된 $Ni/Ce_XZr_{(1-X)}O_2$ 촉매특성이 메탄의 자열개질 반응에 대해 연구되었다. Ce/Zr 비를 변화시킨 촉매 중 $Ni/Ce_{0.80}Zr_{0.20}O_2$ 촉매가 가장 높은 $CH_4$ 전환율을 나타내었다. $Ni/Ce_{0.80}Zr_{0.20}O_2$ 촉매의 Ni 함량에 따른 영향이 조사되었고, 15 wt%의 Ni을 담지하였을 때 가장 우수한 활성을 보여주었다. 또한 $H_2O/CH_4$ 비가 증가할수록 $H_2$ 수율은 증가하였다. $O_2/CH_4$ 비가 증가할수록 $CH_4$ 전환율은 향상되고, 반면에 $H_2$ 수율은 감소하였다. $GHSV=30,000h^{-1}$, S/C/O=2/1/0.5, 반응온도=$800^{\circ}C$에서 30시간 자열 개질반응을 테스트 한 결과, $Ni(15wt%)/Ce_{0.80}Zr_{0.20}O_2$ 촉매가 우수한 $CH_4$ 전환율(${\geq}99%$)과 안정성을 보여주었다.

• 에너지공학
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• 제8권2호
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• pp.256-264
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• 1999

본 연구에서는 메탄의 부분산화반응에 미치는 base metal 의 영향을 살펴보기 위하여 6~l2wt%의 Mn, Cu, V, Co, Cr 그리고 Ba 등이 2 wt% Pt, 70 wt% Alumina, 28 wt% Ceria and Zirconia 와 함께 cordierite (2MgO.2Al$_2$O$_3$.5SiO$_2$)에 담지된 Pt-B/cordierite 촉매(B: base metal)를 사용하여 메탄의 부분산화반응 실험을 수행하였다. 메탄의 부분산화반응에 대한 활성은 Ba, Co그리고 Cr 담지 촉매는 Ni담지 촉매와 유사하게 Mn, Cu, V을 담지 했을 때 보다 우수한 것으로 나타났으나, 코크 생성에 대한 활성도 큰 것으로 나타났다. 또한 5wt% Ni/Al$_2$O$_3$촉매를 이용한 메탄의 부분산화반응 실험 후의 촉매에 대한 XRD 분석결과 Ni은 3가지 형태의 상으로 존재하는 것을 확인할 수 있었으며, 촉매층 전단에서는 주로 NiAl$_2$O$_4$와 NiO 형태로 존재하여 메탄의 산화반응이 일어나며, 그리고 촉매층 후단에서는 환원상태의 Ni로 존재는 것으로 보아 개질반응이 일어나는 것을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제30권3호
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• pp.209-219
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• 2019

Methanol is a liquid fuel which could also be produced from renewable energy sources and has appreciably high energy density. In this work, we investigated the application of $Ce_{0.9}Gd_{0.1}O_{2-x}$ supported Cu and Ni catalysts for hydrogen production via methanol steam reforming. Catalysts were synthesized by solution combustion synthesis. The prepared catalysts with various active materials and Cu loading amounts were tested in a reactor at $200-300^{\circ}C$, 0-5 barg range and steam to methanol molar ratio was 1.5. The catalytic properties of Cu and Ni were compared, and the catalytic performance was shown to depend on the amounts of metal loading and operating conditions such as reaction temperature and pressure.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2013년도 제44회 동계 정기학술대회 초록집
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• pp.166-166
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• 2013

Mesoporous $SiO_2$-supported Ni catalysts (Ni/$SiO_2$ and Ni/$TiO_2$/$SiO_2$) were fabricated by atomic layer deposition (ALD), and their catalytic activity and stability were investigated in carbon dioxide reforming of methane (CRM) reaction at $800^{\circ}C$ The Ni/$SiO_2$ catalysts showed high stability as a result of confinement of Ni particles with a mean size of ~10 nm within the pores of $SiO_2$ support. Besides, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that the Ni nanoparticles were partially buried inside the $SiO_2$ support. The strong interaction between Ni and the $SiO_2$ support could also be advantageous for long-term stability of the catalyst. In case of the Ni/$TiO_2$/$SiO_2$ catalyst, it was found that the catalytic activity of 10 nm-sized Ni nanoparticles was not much influenced by $TiO_2$ addition.

• 한국대기환경학회지
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• 제3권1호
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• pp.1-12
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• 1987

A series of supported sulfided Ni-W/$\gamma-Al_2O_3$ and Co-W/$\gamma-Al_2O_3$ catalysts with different nickel and cobalt contents were studied in the hydrodenitrogenation of pyridine dissolved in n-heptane. The ranges of experimental conditions were at the temperatures between 453 and 753 K, and the pressures between 30 and 50 Bar. The catalytic activities with different nickel and cobalt contents were shown to be maximum at Ni/Ni+W = 0.2 - 0.3, Co/Co+W = 0.3 - 0.4. Pyridine conversion increased with pressure and temperature and the step of piperidine formation was found to be irreversible. The reaction orders in Ni-W/$\gamma-Al_2O_3$ and Co-W/$\gamma-Al_2O_3$ catalysts were the first with respect to pyridine and reaction rate constants decreased with increase of initial pyridine concentration and their activation energies were 12.98 and 9.23 kcal/mol, respectively.

• Bulletin of the Korean Chemical Society
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• 제25권12호
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• pp.1881-1888
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• 2004

A series of $NiO-TiO_2$/$WO_3$ catalysts was prepared by drying powdered $Ni(OH)_2-Ti(OH)_4$ with ammonium metatungstate aqueous solution, followed by calcining in air at high temperature. Characterization of prepared catalysts was performed by using FTIR, Raman, XPS, XRD, and DSC and by measuring surface area. Upon the addition of tungsten oxide to titania up to 25 wt%, the specific surface area and acidity of catalysts increased in proportion to the tungsten oxide content due to the interaction between tungsten oxide and titania. Since the -$TiO_2$/stabilizes the tungsten oxide species, for the samples equal to or less than 25 wt%, tungsten oxide was well dispersed on the surface of titania, but for the samples containing above 25 wt%, the triclinic phase of $WO_3$ was observed at calcination temperature above 400 $^{\circ}C$. The catalytic activities of 10-NiO-$TiO_2$/$WO_3$ for 2-propanol dehydration and cumene dealkylation were correlated with the acidity of catalysts measured by ammonia chemisorption method. NiO may attract reactants and enhance the local concentration of reactants near the acid sites, consequently showing the increased catalytic activities.