本研究是以研製高效能奈米級波洛斯凱特型（Perovskite-type）觸媒，用於合成氣燃燒為目標。採用檸檬酸溶膠凝膠法製備LaCoO3，用於甲烷燃燒反應；並以多種金屬部份取代La與Co對觸媒進行改質，期能提高其催化活性。在篩選出活性較佳的改質觸媒後，進行觸媒穩定性測試及動力學實驗，並求出甲烷燃燒反應之速率表示式。研究中，也藉由觸媒表面性質之鑑定(BET、XRD、SEM及TEM等)，以瞭解觸媒之表面性質與觸媒活性間之關聯性。最後將篩選出活性最佳的波洛斯凱特型觸煤，披覆在蜂巢狀金屬和陶瓷載體上（事先以溶膠凝膠披覆一層γ-Al2O3）上，製成蜂巢狀擔體觸媒。
觸媒篩選的結果，發現活性最佳的觸媒是La0.7Ce0.3Co0.6Mn0.4O3，它可在約275℃讓甲烷起燃，CO的點燃溫度約在100℃，H2的點燃溫度約在125℃，合成氣各成份氣體在此觸媒的反應性為：CO＞H2＞CH4。製備觸媒時最適煅燒溫度是700℃。穩定性測試顯示，該觸媒在高溫或低溫皆具有良好的穩定性。觸媒的活性不會因為生成物的產生及積碳而造成觸媒活性衰退。由混合氣體之反應測試，發現CH4的轉化率會因CO或H2的存在而略為下降。也發現低濃度的硫化氫會使La0.7Ce0.3Co0.6Mn0.4O3此種觸媒產生毒化，且是不可逆的反應。將波洛斯凱特型觸媒（La0.7Ce 0.3Co0.6Mn0.4O3）擔載在蜂巢狀陶瓷上，披覆重量約為陶瓷擔體的2.6 %，厚度約為10 μm，製得之蜂巢狀陶瓷擔體觸媒在約400℃可將甲烷起燃。
利用微分型反應器，以La0.7Ce 0.3Co0.6Mn0.4O3觸媒進行甲烷氧化反應，評估動力模式之適用性。結果發現當氧氣過量時，Mars-Van Krevelen模式適合描述甲烷之氧化反應，根據該模式可推導出甲烷氧化反應之速率表示式：
r=(KRCCH4KOCO2)/(2KRCCH4+KOCCO2)
KR = 4.46×105 exp (-72.3/RT)；Ea = 72.3 KJ/mol
KO = 3.80×105 exp (-79.1/RT)；Ea = 79.1 KJ/mol

The main objective of this research is to prepare high efficiency perovskite-type catalysts for syngas combustion. With the aim of improving catalyst activity, we prepared lanthanum cobaltite LaCoO3 powders via the so called “citric-acid sol-gel method “, and investigated the influence of substituting of several kinds of metals in LaCoO3 perovskite on the activity towards the catalytic combustion of methane. After finding the best one for methane combustion, a kinetic study for finding an appropriate rate expression and stability test were carried out. In order to understand the correlation between physical properties and activities, catalysts were characterized by BET, XRD, SEM, and TEM. Finally, the best perovskite catalyst was washcoated on the cordierite and metallic honeycomb monoliths and their performances were compared.
Experimental results reveal that the best perovskite for methane combustion is La0.7Ce0.3Co0.6Mn0.4O3 catalysts, and the light-off temperature for CH4, CO, and H2 are 275℃, 100℃, and 125℃, respectively. Therefore, the activities of this catalyst for the components of syngas is in the order of CO＞H2＞CH4. The optimal calcination temperature for this catalyst is 700℃. And the stability test shows that this catalyst has a good durability no matter at high or low temperatures. The catalyst would not be deactivated by the production of the products and coke deposition in the reaction. Addition of H2 and CO to the feed slightly inhibited the activity of catalyst for methane combustion. In addition, this catalysts are poison-sensitive to low concentration of H2S in the feed. When the cordierite and metallic monolith were coated with perovskite catalyst （La0.7Ce0.3Co0.6Mn0.4O3）, the loading percentages of active species, based on monolithic support, was about 2.6 ％, and the thickness was about 10 μm. The light-off temperature of methane combustion over both honeycomb monoliths coated with perovskite catalysts is 400℃.
The oxidation kinetics of methane over La0.7Ce0.3Co0.6Mn0.4O3 catalyst was carried out in a differential reactor. The results show that the Mars–Van Krevelen model could satisfactorily fit the experimental kinetic data when excess oxygen was utilized. The rate expression of methane combustion derived from this model is as follows:
r=(KRCCH4KOCO2)/(2KRCCH4+KOCCO2)
KR = 4.46×105 exp (-72.3/RT)；Ea = 72.3 KJ/mol
KO = 3.80×105 exp (-79.1/RT)；Ea = 79.1 KJ/mol

1. 經濟部能源局94年度能源政策白皮書
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