[논문]메탄의 수증기 개질 반응에서 Ni/CeO2-ZrO2 촉매의 수소 생산에 대한 Ru 및 Pd의 조촉매 효과

성인호; 조경태; 이종대

doi:10.14478/ace.2024.1010

[국내논문] 메탄의 수증기 개질 반응에서 Ni/CeO2-ZrO2 촉매의 수소 생산에 대한 Ru 및 Pd의 조촉매 효과
Effect of Promoter with Ru and Pd on Hydrogen Production over Ni/CeO2-ZrO2 Catalyst in Steam Reforming of Methane

공업화학 = Applied chemistry for engineering, v.35 no.2, 2024년, pp.134 - 139

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

초록
AI-Helper

메탄의 수증기 개질 반응에서 Ni 기반 촉매에 귀금속 Ru 및 Pd을 조촉매로 첨가하여 촉매의 활성 및 수소 생산에 미치는 영향을 분석하였다. 합성된 촉매는 허니컴 구조의 금속 모노리스 구조체 표면에 코팅하여 수증기 메탄 개질 반응을 수행하였다. 촉매의 특성은 XRD, TPR 및 SEM으로 분석하였으며 개질 반응 후 가스를 포집하여 GC로 조성을 분석한 후 메탄의 전환율, 수소 수율 및 CO 선택도를 측정하였다. 0.5 wt%의 Ru 첨가는 Ni의 환원 특성을 개선하였고, 99.91%의 메탄 전환율로 향상된 촉매 활성을 나타내었다. 또한, 다양한 공정 조건에 따른 반응 특성을 분석하였으며, 800 ℃의 반응 온도, 10000 h^-1 이하의 공간속도(GHSV), 3 이상의 H₂O와 CH₄의 비(S/C)에서 90% 이상의 메탄 전환율과 3.3 이상의 수소 수율을 얻을 수 있었다.

Abstract ▼ AI-Helper

In the steam reforming of methane reactions, the effect of adding noble metals Ru and Pd to a Ni-based catalyst as promoters was analyzed in terms of catalytic activity and hydrogen production. The synthesized catalysts were coated on the surface of a honeycomb-structured metal monolith to perform steam methane reforming reactions. The catalysts were characterized by XRD, TPR, and SEM, and after the reforming reaction, the gas composition was analyzed by GC to measure methane conversion, hydrogen yield, and CO selectivity. The addition of 0.5 wt% Ru improved the reduction properties of the Ni catalyst and exhibited enhanced catalytic activity with a methane conversion of 99.91%. In addition, reaction characteristics were analyzed according to various process conditions. Methane conversion of over 90% and hydrogen yield of more than 3.3 were achieved at a reaction temperature of 800 ℃, a gas hourly space velocity (GHSV) of less than 10000 h-1, and a ratio of H2O to CH4 (S/C) higher than 3.

Keyword

표/그림 (9)

그림 Figure 1. (a) Image of the metal monolith with honeycomb structure, (b) Schematic diagram of methane reforming reaction system.
그림 Figure 2. XRD patterns (a) 15 wt% Ni- 1 wt% Pd/Ce_0.80Zr_0.20O₂, (b) 15 wt% Ni- 0.5 wt% Pd/Ce_0.80Zr_0.20O₂, (c) 15 wt% Ni- 1 wt% Ru/ Ce_0.80Zr_0.20O₂, (d) 15 wt% Ni- 0.5 wt% Ru/Ce_0.80Zr_0.20O₂, (e) 15 wt% Ni/Ce_0.80Zr_0.20O₂.
그림 Figure 3. H₂-TPR profiles of of 15 wt% Ni/ Ce_0.80Zr_0.20O₂ catalysts with different noble metal promoters loading.
그림 Figure 4. SEM images of (a) metallic monolith surface, (b) after pre-oxidation at 1050 °C, (c) after Al₂O₃ coating (d) 15 wt% Ni- 0.5 wt% Ru/Ce_0.80Zr_0.20O₂.
그림 Figure 5. Temperature dependence of CH4 conversion over various noble catalyst amounts (reaction conditions: GHSV = 10000 h^-1, S/C = 4).
그림 Figure 6. H₂O/CH₄ ratio dependence of CH₄ conversion over various catalysts (reaction conditions: Temperature = 800 °C, GHSV = 10000 h^-1).
그림 Figure 7. GHSV dependence of CH₄ conversion over various catalysts (reaction conditions: Temperature = 800 °C, S/C = 4).
표 Table 1. H₂O/CH₄ Ratio Dependence of CH₄ Conversion, H₂ Yield, and CO Selectivity over Various Catalysts (Reaction Conditions: Temperature = 800 °C, GHSV = 10000 h^-1)
표 Table 2. GHSV Dependence of CH₄ Conversion, H₂ Yield, and CO Selectivity over Various Catalysts (Reaction Conditions: Temperature = 800 °C, S/C = 4)

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