[논문]Ce/Zr 비율에 따른 Ni/CeO2-ZrO2 촉매가 메탄의 수증기 개질 반응에서 미치는 영향

성인호; 조경태; 이종대

doi:10.9713/kcer.2024.62.1.125

[국내논문] Ce/Zr 비율에 따른 Ni/CeO2-ZrO2 촉매가 메탄의 수증기 개질 반응에서 미치는 영향
Effect of Ce/Zr Ratios on Ni/CeO2-ZrO2 Catalysts in Steam Reforming of Methane Reaction

Korean chemical engineering research = 화학공학, v.62 no.1, 2024년, pp.125 - 131

성인호 (충북대학교 화학공학과) , 조경태 (충북대학교 화학공학과) , 이종대 (충북대학교 화학공학과)

초록
AI-Helper

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.

Abstract ▼ AI-Helper

In this study, synthesized Ni/CexZr1-xO2 catalysts were coated on the surface of honeycomb metalic monoliths to investigate catalytic activity in steam reforming of methane reactions. Supports with varying Ce/Zr ratios were synthesized to observe their behavior in the reforming reaction, and catalysts with Ni contents ranging from 5 wt% to 20 wt% were prepared to analyze the effect of Ni loading contents on catalytic activity. The catalysts were characterized by XRD, BET, TPR, and SEM. The TPR analysis indicated the formation of Ni-Ce-Zr oxide with a strong interaction between the active metal Ni and CeO2-ZrO2 support. The 15 wt% Ni/Ce0.80Zr0.20O2 catalyst exhibited the highest activity and stability in the steam reforming of methane reaction. Catalysts with enhanced activity and stability were synthesized by manufacturing composite materials using excellent oxygen storage and donor properties of CeO2 and the thermal properties of ZrO2.

주제어

표/그림 (12)

그림 Fig. 1. Image of the metal monolith with honeycomb structure.
그림 Fig. 2. Schematic diagram of methane reforming reaction system.
그림 Fig. 3. XRD patterns of (a) 15 wt% Ni/CeO₂-ZrO₂ catalysts with various Ce/Zr ratios, (b) Ni/Ce_0.80Zr_0.20O₂ catalysts with various Ni loading.
그림 Fig. 4. H₂-TPR profiles of (a) various supports, (b) 15 wt% Ni/CeO₂-ZrO₂ catalysts with various Ce/Zr ratios, (c) Ni/Ce_0.80Zr_0.20O₂ catalysts with various Ni loading.
표 Table 1. Specific surface areas of various supports and catalysts after calcination
그림 Fig. 5. SEM images of (a) metallic monolith surface, (b) after preoxidation at 1,050℃, (c) after Al₂O₃ coating (d) 15 wt% Ni/Ce_0.80Zr_0.20O₂ on metallic monolith.
그림 Fig. 6. Temperature dependence of CH₄ conversion over various Ce/Zr ratios (reaction conditions: GHSV=10,000 h_-1, S/C=4, 15 wt% Ni loading).
표 Table 2. Temperature dependence of CH₄ conversion, H₂ yield, and CO selectivity over various Ce/Zr ratios (reaction conditions: GHSV=10,000 h^-1, S/C=4, 15 wt% Ni loading)
그림 Fig. 7. Temperature dependence of product composition over Ni/Ce_0.80Zr_0.20O₂ catalyst (reaction conditions: Temperature =800℃, GHSV=10,000 h^-1).
그림 Fig. 8. Temperature dependence of CH₄ conversion over various Ni catalyst amounts (reaction conditions: GHSV=10,000 h^-1, S/C=4, CeO₂/ZrO₂=4).
그림 Fig. 9. Schematic diagram of methane reforming reaction on Ni/CeO₂-ZrO₂ catalyst.
표 Table 3. Temperature dependence of CH₄ conversion, H₂ yield, and CO selectivity over various Ni catalyst amounts (reaction conditions: GHSV=10,000 h^-1, S/C=4, CeO₂/ZrO₂=4)

참고문헌 (22)

Dincer, I., "Renewable Energy and Sustainable Development: a？Crucial Review," Renew. Sust. Energ., 4(2), 157-175(2000).
Abbas, H. F. and Daud, W. W., "Hydrogen Production by Methane Decomposition: a Review," Int. J. Hydrog., 35(3), 1160-1190？(2010a).
Younas, M., Shafique, S., Hafeez, A., Javed, F. and Rehman, F.,？"An Overview of Hydrogen Production: Current Status, Potential, and Challenges," Fuel, 316, 123317(2022).

상세보기
Zhu, X., Liu, X., Lian, H., Liu, J. and Li, X., "Plasma Catalytic？Steam Methane Reforming for Distributed Hydrogen Production," Catal. Today, 337, 69-75(2019).

상세보기
Ogo, S. and Sekine, Y., "Recent Progress in Ethanol Steam Reforming Using Non-noble Transition Metal Catalysts: A Review,"？Fuel Process. Technol., 199, 106238(2020).

상세보기
Ambrosetti, M., Onincontro, D., Balzarotti, R., Beretta, A., Groppi,？G. and Troncori, E., "H 2 Production by Methane Steam Reforming over Rh/Al 2 O 3 Catalyst Packed in Cu Foams: A Strategy for？the Kinetic Investigation in Concentrated Conditions," Catal.？Today, 387, 107-118(2022).
Araujo, J. C. S., Oton, L. F., Bessa, B., Neto, A. B. S., Oliverio,？A. C., Lang, R., Otuobo, L. and Bueno, J. M. C., "The Role of Pt？Loading on La 2 O 3 -Al 2 O 3 Support for Methane Conversion Reactions via Partial Oxidation and Steam Reforming," Fuel, 254,？115684(2019).
Azoncot, L., Bobadilla, L. F., Santos, J. L., Cordoba, J. M.,？Centeno, M. A. and Odriozola, J. A., "Influence of the Preparation Method in the Metal-support Interaction and Reducibility of？Ni-Mg-Al Based Catalysts for Methane Steam Reforming," Int.？J. Hydrog., 44(36), 19827-19840(2019).
Bej, B., Pradhan, N. C. and Neogi, S., "Production of Hydrogen？by Steam Reforming of Methane Over Alumina Supported Nano-NiO/SiO 2 Catalyst," Catal. Today, 207, 28-35(2013).

상세보기
Wang, Y., Peng, J., Zhou, C., Lim, Z.-Y., Wu, C., Ye, S. and Wang,？W. G., "Effect of Pr Addition on the Properties of Ni/Al 2 O 3 Catalysts with An Application in the Autothermal Reforming of？Methane," Int. J. Hydrog., 39(2), 778-787(2014).
Boukha, Z., Gonzalez, C. J., Rivas, B. D., Velasco, J. R. G., Ortiz, J.？I. G. and Fonseca, R. L, "Synthesis, Characterisation and Performance Evaluation of Spinel-derived Ni/Al 2 O 3 Catalysts for Various？Methane Reforming Reactions," Appl. Catal. B., 158-159, 190-201(2014).
Li, M.-R., Lu, Z. and Wang, G.-C., "The Effect of Potassium on？Steam-methane Reforming on the Ni 4 /Al 2 O 3 Surface: a DFT？Study," Catal. Sci. Technol. 7, 3613-3625(2017).
Tada, M., Zhang, S., Malwadkar, S., Ishiguro, N., Soga, J., Nagai,？Y., Tezuka, K., Imoto, H., Matsuo, S. O. Y., Ohkoshi, S. and？Iwasawa, Y., "The Active Phase of Nickel/Ordered Ce 2 Zr 2 O x Catalysts with a Discontinuity (x7-8) in Methane Steam Reforming," Angew. Chem. Int. Ed., 51(37), 9361-9365(2012).
Mohamed, H. O., Kulkarni, S. R., Velisoju, V. K., Zhang, Y.,？Yerrayya, A., Bai, X., Kolubah, P. D., Yoo, X., Morlanes, N. and？Castano, P., "Isolating the Effect of Co and Ce on Ni-X-Y/Al 2 O 3 ？bi- and Trimetallic Reforming Catalysts for Hydrogen Generation," Int. J. Hydrog., 51, 922-935(2024).
Xu, S. and Wang, X., "Highly Active and Coking Resistant Ni/CeO 2 -ZrO 2 Catalyst for Partial Oxidation of Methane," Fuel.,？84(5), 563-567(2005).
Matina, T., Vissanu, M., Thirasak, R. and Somchia, O., "Catalytic？Activity of CeO 2 -ZrO 2 Mixed Oxide Catalysts Prepared via？Sol-gel Technique: CO Oxidation," Catal. Today, 68(1-3), 53-61？(2001).
Querino, P. S., Bispo, J. R. C. and Rangel, M. D. C., "The Effect？of Cerium on the Properties of Pt/ZrO 2 Catalysts in the WGSR,"？Catal. Today, 107-108, 920-925(2005).
Yin, K., Davis, R. J., Mahamulkar, S., Jones, C. W., Agrawal, P.,？Shibata, H. and Malek, A., "Catalytic Oxidation of Solid Carbon？and Carbon Monoxide over Cerium-zirconium Mixed Oxides,"？AIChE J., 63(2), 725-738(2017).

상세보기
El-Solomony, R. A., Acharya, K., Al-Fatesh, A. S., Osman, A.？I., Alreshaidan, S. B., Kumar, N. S., Ahmed, H. and Kumor, R.,？"Enhanced Direct Methanation of CO 2 Using Ni-based Catalysts？Supported on ZrO 2 , CeO 2 -ZrO 2 , and La 2 O 3 -ZrO 2 : The Effect of？Support Material on the Reducible NiO-interacted Species and？Catalytic Activity," Mol. Catal., 547, 113378(2023).
Zhu, X., Wei, Y., Wang, H. and Li, K., "Ce-Fe Oxygen Carriers？for Chemical-looping Steam Methane Reforming," Int. J. Hydrog.,？38(11), 4492-4501(2013).
Laosiripojana, N. and Assabumrungrat, S., "Methane steam Reforming over Ni/Ce-ZrO 2 Catalyst: Influences of Ce-ZrO 2 Support？on Reactivity, Resistance Toward Carbon Formation, and Intrinsic？Reaction Kinetics," Appl. Catal. A-Gen, 290(1-2), 200-211(2005).
Xiu, G. H., Li, P. and Rodrigues, A. E., "Sorption Enhanced Reaction Process with Reactive Regeneration," Chem. Eng. Sci., 57,？3893-3908(2002).

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