• 한국응용과학기술학회지
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• 제27권1호
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• pp.29-36
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• 2010

The effects of La addition to Ni/$CeO_2$ methane partial oxidation catalysts were investigated. Catalysts were prepared by the impregnation and urea methods. In the preparation of catalysts, La content was changed from 1 wt% to 3wt%. Catalysts that contain 2wt% La showed the highest methane conversion of about 80% and CO selectivity of 84% and $H_2$ selectivity of 70%. This result may be stemmed from that, when La content is 2wt%, a fluorite oxide-type structure is well formed and carbon deposition is also decreased. Among the catalysts, 2.5wt% Ni/Ce(La)Ox showed the highest catalytic activity. From the experiment of changing reaction temperature with 2.5wt% Ni/Ce(La)Ox catalyst, it was found that the optimum reaction temperature is $750^{\circ}C$ and at this temperature methane conversion was about 90%, CO and $H_2$ selectivities were 94 and 80%, respectively.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2615-2620
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• 2014

Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

• 한국환경과학회지
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• 제13권7호
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• pp.619-626
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• 2004

We have studied the catalytic combustion of soot particulates over perovskite-type oxides prepared by malic acid method, The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxide. In addition, the reaction conditions such as temperature and $O_2$ concentration were investigated. The partial substitution of alkali metals into A site in the $LaMnO_3$ catalyst, enhanced the catalytic activity in the combustion of carbon particulate and the activity was shown in the order: Cs > K > Na. For the $La_{1-x}Cs_{x}MnO_{3}$ catalysts, the catalytic activity showed the maximum value with x=0.3 but no more increase on the catalytic activity was shown with x > 0.3. For the $La_{0.8}Cs_{0.2}MnO_{3}$ catalyst, the substitution of Fe or Ni increased the ignition temperature. The ignition temperature decreased with an increase of $O_2$ concentration, however, no more increase in the catalytic activity was shown with $O_2$ concentration > 0.2. The introduction of NO into reactants showed no effect on the catalytic activity.

• 융복합기술연구소 논문집
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• 제9권1호
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• pp.7-12
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• 2019

The aim of this study is to improve the durability performance of catalysts for a catalytic combustor and to obtain operating conditions for stable combustion of the catalytic combustor. It was attempted to improve the durability of the catalysts by adding a promoter in order to reduce the cost of replacing Pt catalyst while maintaining stability. The main catalyst used in the study was Pt and the promoters were Ni and La. Pure Pt3/γ-Al₂O₃ catalyst without promoter was promoted to fast sintering states under harsh conditions and catalytic combustion was turned off, whereas the catalysts added La, Ni as promoter were showed relatively slow sintering states. It can be concluded that the promoter La, Ni effectively contributes to the improvement of the durability of the Pt catalyst, and it is possible to get longer durability and more stable duration than the conventional catalytic combustor.

• 한국결정성장학회지
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• 제28권1호
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• pp.44-50
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• 2018

The improved high-performance Fe-based perovskite-type oxides ($La_{0.7}Sr_{0.3}M_xFe_{1-x}O_3$, M = Cu, Cr, Ni) were synthesized by a citrate method and characterized by SEM, EDS, XRD and NMR spectroscopy analyses. The characterization analyses revealed that the stoichiometric amounts of lattice oxygen were existed in all of perovskite samples except for a nickel-doped perovskite. Fe-based perovskites exhibited a surprising result for ortho-para $H_2$ spin conversion reaction, indicating two orders of magnitude higher conversions and conversion rates than commercial $Fe_2O_3$. It was considered that this conversion difference might be attributed to the presence of oxygen vacancies in Fe-based perovskites prepared in this study.

• Korean Chemical Engineering Research
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• 제49권6호
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• pp.715-719
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• 2011

$LaCrO_{3}$를 기본으로 하는 perovskite형 재료인 $La_{0.7}Sr_{0.3}Cr_{1-x}Ni_{x}O_{3}$(0.1 ${\leq}$ x ${\leq}$ 0.5)를 citric acid와 EDTA를 이용한 졸-겔법(sol-gel method)으로 합성하였다. 제조한 촉매의 특성분석은 BET, XRD, SEM, $H_2$-TPR, EA 그리고 TEM을 이용하였고, 프로판 수증기 개질 반응을 통하여 촉매 활성을 평가하였다. Perovskite 산화물의 A-site에는 Sr을 30 ml% 고정치환하고, B-site에 Ni 치환양을 증가시키면서 프로판 수증기 개질 반응 실험을 수행한 결과 Ni 치환양과 S/C의 비(steam to carbon ratio)가 증가할수록 프로판 전환율과 수소 수율이 향상되었다. $La_{0.7}Sr_{0.3}Cr_{0.5}Ni_{0.5}O_{3}$(LSCN-0.5)촉매가 S/C의 비가 1.7이고, $800^{\circ}C$의 반응온도 조건에서 100%의 프로판 전환율과 95.9%의 높은 수소 수율을 나타내어 가장 좋은 촉매 활성을 보였다. 반응 후의 촉매에서는 filamentous cabon형태의 탄소 침적형태가 나타나며, Ni 치환양이 증가할수록 침적되는 탄소의 양이 증가하는 것을 확인하였다.

• 한국대기환경학회지
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• 제10권4호
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• pp.281-288
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• 1994

The hydrodesulfurization (DBT) were Peformed over NiPtMo catalysts supported on HZSM-5, LaY and ${\gamma}$- $Al_2$O$_3$under high H$_2$ pressure. And the acidities of these catalysts were characterized by using TGA and DSC. The result showed that the order of the acid strength for prepared supports was HZSM -5＞LaY＞${\gamma}$- A1$_2$O$_3$. For the acid amount we obtained the same result for the acid strength The acid strength and the acid amount mainly depended on the kinds of supports whose acid site were strong or not The activity of the hydrodesulfurization decreased for catalysts which had strong acid sites. The origin of acid site was Bronsted in NH50 and NY catalysts And it was Lewis in NA catalyst The order of desorption activation energy for Pyridine was NH50＞NY>NA. And the result was the same for thiophene. The activity of the hydrodesulfurization decreased for catalysts which had strong acid sites. The conversion of DBT over NA catalyst was higher than NH and NY catalysts.

• 청정기술
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• 제18권1호
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• pp.95-101
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• 2012

수소생산을 위한 메탄의 부분산화용 촉매로 알루미나에 담지된 코발트와 니켈 촉매를 함침법으로 제조하였다. 이들 코발트와 니켈 촉매에 조촉매 성분 Mg, Ce, La와 Sr을 첨가하여 초촉매 효과를 조사하였다. 메탄의 부분산화반응을 위한 촉매의 활성은 상압, $CH_4/O_2$ = 2.0에서 450~$650^{\circ}C$의 온도영역으로 조사하였다. 촉매의 특성은 BET, XRD와 SEM/EDX를 이용하여 조사하였다. 0.2 wt%의 조촉매 성분의 첨가로 촉매성능의 상승효과를 얻을 수 있었다. $500^{\circ}C$ 이상의 온도에서는 $Co/Al_2O_3$에 Mg을 첨가한 촉매가 가장 우수한 메탄 전환율과 수소 선택성을 나타내었다. 낮은 온도 영역에서는 $Ni/Al_2O_3$에 Ce와 Sr을 첨가한 촉매가 Co계 촉매보다 우수한 반응특성을 나타내었다. $Co/Al_2O_3$와 $Ni/Al_2O_3$에 조촉매를 첨가한 경우 촉매의 표면적이 증가하는 것으로 나타났다.

• 공업화학
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• 제9권7호
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• pp.1070-1078
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• 1998

농축상을 포함한 다원 반응계의 Gibbs Free Energy 최소화 계산을 수행하여 이산화탄소 개질반응에 대한 열역학적 분석을 수행하였으며, $Al_2O_3$, $La_2O_3$, ZSM-5, MCM-41, 그리고 KIT-1의 담체에 담지된 니켈 촉매와 상업용 개질 촉매 ICI 46-1상에서 이산화탄소에 의한 메탄의 개질 반응 실험을 수행하였다. 메탄의 이산화탄소에 의한 개질반응 열역학 계산은 $CH_4$, $CO_2$, CO, $H_2$, $H_2O$, C계에서 수행하는 것이 바람직하였고, 수증기나 산소의 첨가 효과는 이산화탄소의 개질 반응 기여도를 감소시키는 것으로 예상되었다. Ni/ZSM-5, Ni/MCM-41, Ni/KIT-1등 실리케이트 계열의 분자체 담체에 니켈을 담지시킨 촉매가 메탄과 이산화탄소의 전화율이 우수하며, 일산화탄소 수율도 높은 것을 알 수 있었다. 이산화탄소 개질 반응에 대한 코크의 침적은 칼슘 산화물을 첨가함으로써 감소되었으며, 10% Ni과 3% Ca를 담지시킨 Ni/Ca/KIT-1 촉매가 20시간 동안 $650^{\circ}C$ 이상에서 평형 전화율에 근접한 이산화탄소와 메탄의 전화율을 나타냄이 확인되었다. 또한 상대적으로 높은 공간 속도에도 우수한 활성을 나타내었다.

• 대한환경공학회지
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• 제28권4호
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• pp.368-375
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• 2006

순수한 아나타제 구조로 이루어진 DT51D $TiO_2$에 $CrO_x,\;FeO_x,\;MnO_x,\;LaO_x,\;CoO_x,\;NiO_x,\;CeO_x,\;CuO_x$와 같은 단일 산화물 촉매를 각각 5 wt.% 담지하여 모델반응으로 선택한 기상 TCE 제거반응을 수행하였으며, 이로부터 얻어진 결과를 바탕으로 $CrO_x/TiO_2$-based 복합 산화물 촉매상에서 TCE 산화반응을 연구함으로써 유해 중금속의 사용량을 최소화하기 위한 최적의 촉매 디자인 방법을 도출하고자 하였다. DT51D $TiO_2$에 담지된 여러 단일 금속 산화물들 중에서 기상 TCE 제거반응에 대하여 $CrO_x$가 가장 우수한 촉매활성을 보이는 것으로 나타났으며, 반응온도의 함수로 얻어진 TCE 제거반응의 활성은 $CrO_x$의 담지량에 의존하였다. 5 wt.% $CrO_x$-based 복합 산화물 촉매는 10 wt.% $CrO_x$만으로 이루어진 단일 산화물 촉매와 거의 동일한 수준의 TCE 제거반응 활성을 보였을 뿐만 아니라 이 복합 산화물 촉매들은 10 wt.% $CoO_x,\;MnO_x,\;FeO_x,\;NiO_x$ 등과 같은 단일 산화물 촉매들보다 높은 반응활성을 갖는 것으로 나타났다. 단일 산화물 촉매의 반응활성과 비교하였을 때 5 wt.% $CrO_x$-based 복합 산화물 촉매상에서 TCE 제거반응 동안에 얻어지는 반응활성의 증가 정도는 $420^{\circ}C$ 이하의 반응온도 기준으로 약 $10{\sim}80%$ 이상이었다. 따라서, CVOCs 제거반응을 위하여 널리 사용되고 있는 단일 $CrO_x/Al_2O_3$ 촉매보다는 $CrO_x$의 사용량을 최소화하면서도 우수한 반응활성을 얻을 수 있는 $CrO_x/TiO_2$-based복합 산화물 촉매가 보다 바람직하며 하나의 대안적인 촉매 디자인 방법으로 응용될 수 있을 것으로 생각된다.