氫能是新能源技術開發重點項目之一，目前氫氣的生成主要來自於甲烷蒸氣重組反應(SRM)，近年來甲烷乾式重組反應(DRM)也受到關注，因為可直接將兩大溫室氣體二氧化碳和甲烷轉化為有用的燃料。本研究探討中溫甲烷重組以降低高溫操作的能量損耗、操作危險性及觸媒燒結積碳等現象，主要探討利用La, Zr及Ce等比例混合氧化物(缺陷螢石結構)擔載Ni及Co觸媒。當以不同方法製備Ni/LZC時，於低擔載量(Ni ≦ 13%)顯示含浸於共沉澱法載體及燃燒法載體(-IP及-IB)所製備的觸媒反應性較佳，高擔載量(Ni ≧ 13%)時則以共沉澱法(-P)及共燃燒法(-B)為佳，其中又以高Ni擔載量Ni/LZC-P表現最佳，於400~600 oC SRM反應中，在接近平衡轉化率反應狀態下能維持碳平衡接近100%，CO/CO2 < 0.1，氫氣產率約為4，顯示中低溫反應的優勢。不同方法(-P, -IP及-IB)製備的Co/LZC觸媒，顯示Co/LZC在中低溫反應過程易因氧化而失活，在較高溫才有穩定活性，在650 oC SRM測試中可維持15小時不失活且反應後觸媒無積碳。在500 oC DRM反應測試上，Ni/LZC-P具有高轉化率，但產生大量積碳，不利反應操作，Co/LZC-P則會因鈷氧化而導致觸媒使轉化率變差，但未見有積碳生成。進一步探討Ni/Co以不同比例混合所形成的NiCo(x)/LZC-P(x = 9及3)，不但能顯著降低Ni/LZC-P積碳問題，也能減少Co氧化的作用，其中NiCo(3)/LZC-P有相對較佳的DRM操作穩定性，XAS分析顯示反應後NiCo(3)/LZC-P的Ni及Co最接近還原態，無CoOx、NiOx或Ni3C的生成，其H2-TPR還原溫度特徵與Ni/LZC-P相似，但還原溫度向高溫偏移，顯示Co的少量摻雜使得Ni與LZC載體間具有更佳的作用力。

With fossil fuels, improving energy efficiency can lead to cut down of greenhouse gas emissions, Hydrogen becomes one of the important alternative energy carriers that can promote energy efficiency. To date, hydrogen is mainly product from steam reforming of methane (SRM). Dry reforming of methane (DRM) has also attracted attention because it can directly convert two major greenhouse gases, carbon dioxide and methane, into useful fuels. This study explores the use of defect fluorite mixed oxide of with La, Zr and Ce (LZC), to support Ni and Co for medium temperature methane reforming. Ni/LZC was prepared by different preparation methods, and that prepared by impregnation method (IP and IB) show better reactivity at Ni loading ≦13% than P(co-precipitation) and B(combustion) methods. On the other hand, Ni/LZC-P and Ni/LZC-B have better activity at ≧13%. The 16.7% Ni/LZC-P operated at near SRM equilibrium conversion at 500 oC can achieve a carbon balance close to 100%, demonstrated the advantage of the medium temperature reaction. Co/LZC catalysts from different preparation methods shows deactivation at mid temperature SRM owing to Co oxidation. Co/LZC-P can maintain good activity without deactivation and no carbon deposition at high temperature (650 oC) SRM for 15 hours. During 500 oC DRM, Ni/LZC-P has high activity, with high carbon deposit, while Co/LZC-P deactivates by Co oxidation but without coking. We demonstrate that NiCo(x)/LZC-P (Ni/Co=9 and 3) not only achieve good DRM activity at 500 oC but also successfully reduces the carbon deposition of Ni/LZC-P and Co oxidationof Co/LZC. The results of H2-TPR indicate a reduction characteristic as Ni/LZC-P with a slight shift to high temperature. This suggests that a small amount of Co leads to a stronger interaction between Ni and LZC supports.

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