• 제목/요약/키워드: Temperature programmed oxidation

검색결과 52건 처리시간 0.028초

TPR/TPO 실험기법을 이용한 전이금속산화물의 산화-환원 특성 연구 (Redox Property of Transition Metal Oxides in Catalytic Oxidation)

  • 김영호;이호인
    • 공업화학
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    • 제10권8호
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    • pp.1161-1168
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    • 1999
  • 3주기 전이금속(Cr~Zn)의 산화물 및 V, Mo, W의 산화물에 대하여 temperature-programmed reduction/trmperature-programmed oxidation(TPR/TPO) 실험을 통하여 그 산화-환원 특성을 조사하였다. TPO 곡선의 산화피크는 TPR 곡선의 환원피크와 비슷하거나 약간 낮은 온도에서 나타났으며, 환원피크에 비하여 온도 폭이 넓었다. 3주기 전이금속한화물의 산화 및 환원 과정의 활성화에너지는 33~149 kJ/mol 범위에 있는 반면, V, Mo, W 산화물에서는 더 컸다. 금속산화물의 산화 및 환원 과정의 활성화에너지 변화는 금속-산소 결합세기에 비례하였다. 환원(TPR) 및 산화(TPO) 과정에 대한 활성화에너지 차이(${\Delta}E_a$)가 작을수록 o-자일렌 산화반응에서 금속산화물 촉매의 활성화에너지도 작았다. 금속한화물 촉매에서 o-자일렌 산화반응은 금속산화물 표면의 산화-환원 과정을 반복하는 Mars-van Krevelen 반응 메카니즘으로 설명될 수 있음을 확인하였다.

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INVESTIGATION OF SOOT OXIDATION CHARACTERISTICS IN A SIMULATED DIESEL PARTICULATE FILTER

  • Lee, H.S.;Chun, K.M.
    • International Journal of Automotive Technology
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    • 제7권3호
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    • pp.261-267
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    • 2006
  • Understanding the mechanism of carbon oxidation is important for the successful modeling of diesel particulate filter regeneration. Carbon oxidation characteristics were investigated by temperature programmed oxidation(TPO) method as well as constant temperature oxidation(CTO) with a flow reactor including porous bed. The activation energy of carbon oxidation was increasing with temperature and had two different constant values in the early and the later stage of the oxidation process respectively in TPO experiment. Kinetic constants were derived and the reaction mechanisms were assumed from the experimental results and a simple reaction scheme was proposed, which approximately predicted the overall oxidation process in TPO as well as CTO.

산화철의 환원-산화 반응을 이용한 수소저장에 미치는 Rh/Ce/Zr의 효과 (The effect of Rh/Ce/Zr additives on the redox cycling of iron oxide for hydrogen storage)

  • 이동희;차광서;박주식;강경수;김영호
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2007년도 춘계학술대회
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    • pp.49-52
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    • 2007
  • We investigated hydrogen storage and production properties using redox system of iron oxide($Fe_{3}O_{4}$ + $4H_{2}$ ${\leftrightarrows}$ 3Fe + $4H_{2}O$) modified with rhodium, ceria and zirconia under atmospheric pressure. Reduction of iron oxide with hydrogen(hydrogen storage) and re-oxidation of reduced iron oxide with steam(hydrogen evolution) was carried out using a temperature programmed reaction(TPR) technique. On the temperature programmed studies, the effects of amounts of cerium and zirconium on the re-oxidation rate of partial reduced iron oxides were increased with increasing metal additives amount, but the rhodium amount showed little effect on the re-oxidation rate. On the thermal studies, the re-oxidation rates were enhanced with increasing temperature(300 $^{\circ}C$ < 350 $^{\circ}C$).

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Redox Property of Vanadium Oxide and Its Behavior in Cataltic Oxidation

  • 김영호;이호인
    • Bulletin of the Korean Chemical Society
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    • 제20권12호
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    • pp.1457-1463
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    • 1999
  • Structure and their redox property of the vanadium oxides prepared by decomposing NH₄VO₃ at various temperatures were studied by XRD, SEM, XPS, and temperature programmed reduction/temperature programmed oxidation (TPR/TPO) experiment. All TPR profiles have two sharp peaks in the temperature range 650-750℃, and the area ratio of the two sharp peaks changed from sample to sample. There were three redox steps in TPR/TPO profiles. The oxidation proceeded in the reverse order of the reduction process, and both the reactions proceeded via quite a stable intermediates. The changes of the morphological factor $(I_{(101)}/I_{(010)})$, the ratio of $O_{1S}$ peak area (O$_{1S}$( α)/O$_{1S}$( β)) in the XPS results, and the ratio of hydrogen consumption in TPR profiles with various vanadium oxides showed the distinct relationship between the structural property and their redox property of vanadium oxides. The change of the specific yield of phthalic anhydride with various vanadium oxides showed a very similar trend to those of the peak area ratio in TPR profiles, which meant that the first reduction step related to the partial oxidation of o-xylene on the vanadium oxide catalyst.

The Complete Oxidation of Ethanol at Low Temperature over a Novel Pd-Ce/γ-Al2O3-TiO2 Catalyst

  • Wang, Yanping;Zhao, Jinshuang;Wang, Xiaoli;Li, Zhe;Liu, Pengfei
    • Bulletin of the Korean Chemical Society
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    • 제34권8호
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    • pp.2461-2465
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    • 2013
  • Pd-$Ce/{\gamma}-Al_2O_3-TiO_2$ catalysts were prepared by combined sol-gel and impregnation methods. Transmission electron microscopy, X-ray diffraction, $H_2$-temperature-programmed reduction, $O_2$-temperature-programmed desorption, and ethanol oxidation experiments were conducted to determine the properties of the catalysts. Addition of an optimal amount of Ce improved the performance of the $Pd/{\gamma}-Al_2O_3-TiO_2$ catalyst in promoting the complete oxidation of ethanol. The catalyst with 1% Ce exhibited the highest activity, and catalyzed complete oxidation of ethanol at $175^{\circ}C$; its selectivity to $CO_2$ reached 87%. Characterization results show that addition of appropriate amount of Ce could enrich the PdO species, and weaken the Pd-O bonds, thus enhancing oxidation ability of the catalyst. Meanwhile, the introduction of $CeO_2$ could make PdO better dispersed on ${\gamma}-Al_2O_3-TiO_2$, which is beneficial for the improvement of the catalytic oxidation activity.

γ-Al2O3에 담지된 Cu-Mn 산화물 촉매의 활성 및 특성 (Activity and Characteristics of Cu-Mn Oxide Catalysts Supported on γ-Al2O3)

  • 김혜진;최성우;이창섭
    • Korean Chemical Engineering Research
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    • 제44권2호
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    • pp.193-199
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    • 2006
  • ${\gamma}-Al_2O_3$에 담지한 Cu-Mn 산화물 촉매에서 톨루엔 완전산화 반응을 $160{\sim}280^{\circ}C$의 온도 범위에서 고정층 반응기로 조사하였다. BET, SEM, TPR, TPO, XPS 및 XRD를 이용하여 촉매 특성분석을 하였다. 톨루엔의 완전산화 반응은 $280^{\circ}C$ 이하에서 이루어졌으며, 적절한 Cu-Mn 담지량은 15.0 wt%Cu-10.0 wt%Mn인 것으로 나타났다. TPR/TPO 및 XPS 분석 결과, 15 Cu-10 Mn 촉매의 산화환원 봉우리가 낮은 온도로 이동하였으며 결합에너지가 높은 값으로 이동하였다. XRD 결과, 고분산된 Mn 산화물과 CuO 보다 $Cu_{1.5}Mn_{1.5}O_4$의 촉매활성 인자로서의 역할이 더욱 우수한 것으로 추측되며, 촉매의 활성은 촉매의 산화환원 능력과 촉매의 높은 산화 상태에 기인하는 것으로 사료된다.

고정층 반응기에서 망간광석(NMD)을 이용한 저농도 일산화탄소 산화특성 (Oxidation Characteristics of Low Concentration CO Gas by the Natural Manganese Dioxide(NMD) in a Fixed Bed)

  • 이영순;박종수;오광중
    • 청정기술
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    • 제2권1호
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    • pp.60-68
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    • 1996
  • 고정층 반응기에서 망간광석을 이용하여 저농도의 일산화탄소 산화제어반응에 대하여 고찰하였다. 고려된 실험변수는 일산화탄소 농도 (500ppm~10000ppm), 산소 농도(500ppm~99.8%)와 촉매의 온도($50{\sim}750^{\circ}C$)이다. 또한 망간광석의 특성은 Thermogravimetric Analysis(TGA), 일산화탄소에 의한 환원, Temperature Programmed Reduction(TPR)실험을 이용하여 규명하였다. 망간광석의 일산화탄소 산화력은 순수이산화망간에 비해서 단위 면적당 높은 산화력과 $750^{\circ}C$까지 가열된 후에도 산화력이 유지될 수 있는 안정된 촉매작용을 보였다. Temperature Programmed Desorption(TPD), TPR 실험과 TG 등의 분석결과 산소의 농도가 낮거나 무산소하에서 망간광석의 격자내 산소가 쉽게 제공될 수 있음을 알 수 있었다. 일산화탄소의 농도가 500~3500ppm일 때 일산화탄소의 반응차수는 0.701이며 3500~10000ppm구간에서 일산화탄소의 농도에 무관한 0차 반응이었다.

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$Pt/CeO_2$ 촉매와 Tight Contact 한 상태의 Model Soot 산화에 NO가 미치는 영향에 관한 실험적 연구 (Effect of NO on Catalytic Soot Oxidation in Tight Contact with $Pt/CeO_2$ Using a Flow Reactor System)

  • 이동일;송창훈;송순호;전광민
    • 한국자동차공학회논문집
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    • 제19권3호
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    • pp.52-56
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    • 2011
  • Active regeneration in CDPF requires $O_2$ which regenerates soot at high temperature. However, small amount of NO can interrupt $O_2$ regeneration in CDPF. To verify this phenomena, soot oxidation experiments using a flow reactor with a $Pr/CeO_2$ catalyst are carried out to simulate Catalyzed Diesel Particulate Filter (CDPF) phenomena. Catalytic soot oxidation with and without small amount of NO is conducted under tight contact condition. As the heating rate rises, the temperature gap of maximum reaction rate is increased between with and without 50ppm NO. To accelerate the $NO_2$ de-coupling effect, CTO process is performed to eliminate interfacial contact for that time. As CTO process is extended, temperature which indicates peak reaction rate increases. From this result, it is found that small amount of NO can affect tight contact soot oxidation by removal of interfacial contact between soot and catalyst.

Influence of $TiO_2$ Thin Film Thickness and Humidity on Toluene Adsorption and Desorption Behavior of Nanoporous $TiO_2/SiO_2$ Prepared by Atomic Layer Deposition (ALD)

  • Sim, Chae-Won;Seo, Hyun-Ook;Kim, Kwang-Dae;Park, Eun-Ji;Kim, Young-Dok;Lim, Dong-Chan
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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    • pp.268-268
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    • 2012
  • Adsorption and desorption of toluene from bare and $TiO_2$-coated silica with a mean pore size of 15 nm was studied using breakthrough curves and temperature programmed desorption. Thicknesses of $TiO_2$ films prepared by atomic layer deposition on silica were < 2 nm, and ~ 5 nm, respectively. For toluene adsorption, both dry and humid conditions were used. $TiO_2$-thin film significantly improved toluene adsorption capacity of silica under dry condition, whereas desorption of toluene from the surface as a consequence of displacement by water vapor was more pronounced for $TiO_2$-coated samples with respect to the result of bare ones. In the TPD experiments, silica with a thinner $TiO_2$ film (thickness < 2 nm) showed the highest reactivity for toluene oxidation to $CO_2$ in the absence and presence of water. We show that the toluene adsorption and oxidation reactivity of silica can be controlled by varying thickness of $TiO_2$ thin films.

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Fuel-Borne Catalyst와 Perovskite로 구성된 복합촉매 시스템에 의한 디젤 탄소입자상 물질의 연소반응: 반응성능과 Perovskite 촉매조성 (La1-x A'xBO3: A' = K, Sr; 0 ≤ x ≤ 1; B = Fe, Cr, Mn)의 상관관계 (Combustion of Diesel Particulate Matters under Mixed Catalyst System of Fuel-Borne Catalyst and Perovskite: Influence of Composition of Perovskite (La1-x A'xBO3: A' = K, Sr; 0 ≤ x ≤ 1; B = Fe, Cr, Mn) on Combustion Activity)

  • 이대원;성주영;이관영
    • Korean Chemical Engineering Research
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    • 제56권2호
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    • pp.281-290
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    • 2018
  • 최근 선진국을 중심으로 고연비-저배출 내연기관 (디젤) 자동차 보급의 필요성이 대두되면서 기존 촉매후처리 장치의 저온성능 강화를 위한 기술적 방안들이 시급히 요구되고 있다. 본 논문에서는 디젤엔진 배출 탄소입자상 물질의 연소반응에 있어 연료함유 촉매(Fuel-Borne Catalyst)와 페로브스카이트(Perovskite)의 복합촉매 시스템이 보이는 상용모델촉매 대비 우수한 저온 연소성능과 이의 Perovskite 촉매 조성에 대한 의존성에 관해 논하였다. Fe/Ce 계열 연료함유 촉매가 A-site 원소(La)에 K이 부분치환되고, B-site 금속이 Fe인 Perovskite 촉매와 복합화될 때 상대적으로 우수한 저온 연소성능 개선효과가 관찰되었다. 이를 관찰하기 위해 연료함유 촉매가 함유되거나 함유하지 않은 탄소 입자상 물질과 다양한 조성의 La 계열 Perovskite 촉매를 혼합한 고정층에 대한 온도상승 산화반응 실험(Temperature-Programmed Oxidation)을 수행하였으며, 이산화탄소 생성과 질소산화물 농도 저하 패턴의 연동특성을 통해 두 촉매의 상호 연계작용을 유추하였다.