• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1265-1272
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• 2007

A solid acid catalyst, NiSO4/CeO2-ZrO2 was prepared simply by promoting ZrO2 with CeO2 and supporting nickel sulfate on CeO2-ZrO2. The support of NiSO4 on ZrO2 shifted the phase transition of ZrO2 from amorphous to tetragonal to higher temperatures because of the interaction between NiSO4 and ZrO2. The surface area of 10-NiSO4/1-CeO2-ZrO2 promoted with CeO2 and calcined at 600 oC was very high (83 m2/g) compared to that of unpromoted 10-NiSO4/ZrO2 (45 m2/g). This high surface area of 10-NiSO4/1-CeO2-ZrO2 was due to the promoting effect of CeO2 which makes zirconia a stable tetragonal phase as confirmed by XRD. The role of CeO2 was to form a thermally stable solid solution with zirconia and consequently to give high surface area and acidity of the sample, and high thermal stability of the surface sulfate species. 10-NiSO4/1- CeO2-ZrO2 containing 1 mol% CeO2 and 10 wt% NiSO4, and calcined at 600 oC exhibited maximum catalytic activities for both reactions, 2-propanol dehydration and cumene dealkylation.

• Korean Chemical Engineering Research
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• 제62권1호
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• pp.125-131
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• 2024

본 연구에서는 제조된 Ni/Ce_xZr_1-xO₂ 촉매를 허니컴 구조의 금속 모노리스 구조체 표면에 코팅하여 수증기 메탄 개질 반응에 대한 활성을 연구하였다. Ce/Zr의 비율을 달리한 지지체를 합성하여 수증기 메탄 개질 반응에서의 거동을 확인하였으며, Ni 함량이 촉매 활성에 미치는 영향을 분석하기 위해 다양한 Ni 함량의 촉매를 제조하였다. 촉매의 특성은 XRD, BET, TPR 및 SEM으로 분석하였으며 TPR 분석에서 활성 금속 Ni이 CeO₂-ZrO₂ 혼합물 지지체와 강한 상호작용으로 Ni-Ce-Zr 산화물을 형성하였음을 나타내었다. 15 wt% Ni/Ce_0.80Zr_0.20O₂ 촉매는 수증기 메탄 개질 반응에서 가장 높은 활성 및 안정성을 보였다. 우수한 산소저장 및 공여 특성의 CeO₂와 열적 특성의 ZrO₂를 복합소재로 제조하여 활성과 안정성이 향상된 촉매를 합성하였다.

• 한국재료학회지
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• 제9권1호
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• pp.73-80
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• 1999

The effect of alloy compositions of the bond coating on the plasma sprayed-thermal barrier coatings was investigated. The performance of the coating composed of Rene80/NiCrAl/ZrO$_2$-CeO$_2$-Y$_2$O$_3$ and Rene80/CoNiCrAlY/ZrO$_2$-CeO$_2$-Y$_2$O$_3$was evaluated by isothermal and thermal cyclic test in an ambient atmosphere at 115$0^{\circ}C$. The failure of Rene80/NiCrAl/ZrO$_2$-CeO$_2$-Y$_2$O$_3$ coatings was occurred at the bond coating/ceramic coating interface while Rene80/CoNiCrAlY/ZrO$_2$-CeO$_2$-Y$_2$O$_3$ coating was failed at the substrate/bond coating interface after thermal cyclic test. The lifetime of Rene80/NiCrAl/ZrO$_2$-CeO$_2$-Y$_2$O$_3$coatings was longer than Rene80/CoNiCrAlY/ZrO$_2$-CeO$_2$-Y$_2$O$_3$coating. The oxidation rate of the NiCrAl bond coating examined by TGA was lower than CoNiCrAlY bond coatings. In summary, these results suggest that Rene80/CoNiCrAlY/ZrO$_2$-CeO$_2$-Y$_2$O$_3$system as thermal barrier coating be not suitable considering the durability of the coating layer for high temperature oxidation and thermal stress.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1989-1996
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• 2006

The $NiSO_4/CeO_2-ZrO_2 $catalysts containing different nickel sulfate and $CeO_2$ contents were prepared by the impregnation method, where support, $CeO_2-ZrO_2$was prepared by the coprecipitation method using a mixed aqueous solution of zirconium oxychloride and cerium nitrate solution followed by adding an aqueous ammonia solution. No diffraction line of nickel sulfate was observed up to 20 wt %, indicating good dispersion of nickel sulfate on the surface of $CeO_2-ZrO_2$. The addition of nickel sulfate (or $CeO_2$) to $ZrO_2$ shifted the phase transition of $ZrO_2$ from amorphous to tetragonal to higher temperatures because of the interaction between nickel sulfate (or $CeO_2$) and $ZrO_2$. A catalyst (10-$NiSO_4/1-CeO_2-ZrO_2$) containing 10 wt % $NiSO_4$ and 1 mole % $CeO_2$, and calcined at $600{^{\circ}C}$ exhibited a maximum catalytic activity for ethylene dimerization. The catalytic activities were correlated with the acidity of catalysts measured by the ammonia chemisorption method. The role of $CeO_2$was to form a thermally stable solid solution with zirconia and consequently to give high surface area, thermal stability and acidity of the sample.

• Korean Chemical Engineering Research
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• 제51권3호
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• pp.319-324
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• 2013

합성가스를 생산하기 위한 메탄의 부분산화반응 특성을 $Ni/CeO_2-ZrO_2$, $Ni-Ru/CeO_2-ZrO_2$와 $Ni-Pd/CeO_2-ZrO_2$ 촉매체를 이용하여 조사하였다. 메탄의 부분 산화 개질 반응에서 촉매의 높은 활성과 안정성을 위하여 허니컴 구조의 금속모노리스 촉매 체를 적용하였다. 촉매분석은 XRD와 FE-SEM을 사용하였으며, 제조된 촉매들의 합성가스 제조 특성은 반응물 비(O/C), GHSV와 온도를 변화시키면서 연구하였다. 개질 실험에서 사용된 촉매 중에서 $Ni-Pd/CeO_2-ZrO_2$ 촉매 체가 가장 높은 활성을 보여 주었으며, $900^{\circ}C$, GHSV=10,000 $h^{-1}$과 O/C=0.55에서 99%의 메탄 전환율을 얻었다. O/C 비가 증가함에 따라 수소 yield는 증가되고, 반면에 CO yield는 거의 일정하게 유지됨을 확인할 수 있었다. 또한 GHSV가 증가할수록 메탄의 전환율은 감소하였으며, 높은 메탄의 전환율을 얻을 수 있는 GHSV의 범위는 10,000 $h^{-1}$ 이하임을 알 수 있었다.

• 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.

• 한국수소및신에너지학회논문집
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• 제29권5호
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• pp.419-426
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• 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.

• Bulletin of the Korean Chemical Society
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• 제34권11호
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• pp.3387-3390
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• 2013

Catalytic gasification of mandarin waste residue was carried out using direct and indirect catalyst-contact methods for the first time. In the indirect method, non-catalytic reaction in a reactor was followed by catalytic upgrading of vapor product in another reactor. Two different catalysts, $Ni/{\gamma}-Al_2O_3$ and $Ni/CeO_2-ZrO_2$, were employed. $CeO_2-ZrO_2$ support was prepared using hydrothermal synthesis in supercritical water. The catalysts were characterized by $H_2$-temperature programmed reduction and Brunauer-Emmett-Teller analyses. Under the condition of equivalent ratio (ER) = 0, the indirect catalyst-contact method led to a higher gas yield than the direct method. Under ER = 0.2, the yield of biogas obtained over $Ni/CeO_2-ZrO_2$ was higher than that obtained over $Ni/{\gamma}-Al_2O_3$. Also, the coke formation of $Ni/CeO_2-ZrO_2$ was lower than that of $Ni/{\gamma}-Al_2O_3$. Such results were attributed to the higher reducibility and better lattice oxygen mobility of $Ni/CeO_2-ZrO_2$, which were advantageous for partial oxidation reaction.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2009년도 추계학술대회 논문집
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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.

• 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.