二氧化碳的甲烷重組反應可將同為溫室氣體之甲烷與二氧化碳轉化成合成氣CO+H2，此氣體可用於生產甲醇或更高經濟價值的有機化合物，為一項值得研發的技術。為提高應用於此反應之LaNiO3觸媒的反應活性、穩定性及抗積碳能力，本研究以檸檬酸凝膠法製備LaNiO3觸媒，並藉Mg及Ce的添加及α-Al2O3擔體的利用來製備改質之觸媒，並比較LaNiO3、LaNi0.94Mg0.06O3、La0.96Ce0.04Ni0.94Mg0.06O3與5wt.% LaNi0.94Mg0.06O3 / α-Al2O3四種觸媒之諸特性。
以檸檬酸凝膠法製備之前驅體粉末約在600°C開始形成LaNiO3相，於350°C持溫0.5 h後再以700°C鍛燒2 h所得之LaNiO3觸媒粉末，其比表面積為9.06 m2/g，粒徑約為91.3 nm。此粉末於700°C作活性反應測試，其CH4和CO2之轉化率分別為76.2%和77.9%，但此觸媒在反應過程中易出現嚴重積碳現象，導致觸媒在反應1 h後管線即因阻塞而終止反應。
為了進一步改良適用於二氧化碳甲烷重組反應用的LaNiO3觸媒，本研究選用Mg當添加劑並以二個階段來進行觸媒的改質。第一階段先以檸檬酸凝膠法合成出LaNi1-xMgxO3觸媒，檢討最適當的Mg添加量，其中以LaNi0.94Mg0.06O3觸媒擁有最佳的活性表現，於700°C作活性反應測試，其CH4和CO2之轉化率分別為62.7%和79.3%。
第二階段是希望能再提高觸媒的抗積碳能力及催化活性，將上述觸媒分成以共摻雜及擔體方式作改質。共摻雜方式是將不同計量比的Ce添加至LaNi0.94Mg0.06O3觸媒，其中則以La0.96Ce0.04Ni0.94Mg0.06O3觸媒具有最佳活性的表現，於700°C作活性反應測試，其CH4和CO2之轉化
率分別為75.9%和91.4%。擔體方式是選用200 nm的α-Al2O3為擔體，並比較在不同觸媒用量下其觸媒的活性，其中以觸媒用量為1 g的5wt.% LaNi0.94Mg0.06O3/α-Al2O3觸媒有最佳的活性表現、抗積碳能力及穩定性，於700°C作活性反應測試，其CH4和CO2之轉化率分別為88.9%和98.1%，在反應2 h後之積碳量僅為1wt.%，且在穩定性測試方面可在700°C下反應8 h仍能維持其催化活性而不衰退，此為四組觸媒中最佳者。

The methane reforming of carbon dioxide reaction could transform the greenhouse gas CH4 and CO2 into syngas CO and H2. The syngas could be used to produce methanol or some high value organic compounds. In order to enhance the reaction activity, stability, and carbon resistibility of the LaNiO3 catalyst used in the reforming reaction, the catalyst was prepared by citrate method and promoted by adding Mg, Ce or supported by α-Al2O3. Finally, LaNiO3, LaNi0.94Mg0.06O3, La0.96Ce0.04Ni0.94Mg0.06O3, and 5wt.% LaNi0.94Mg0.06O3 / α-Al2O3 catalysts would be discussed and compared in the catalytic performance.
The LaNiO3 phase was formed at 600°C initially from precursor prepared by the cictrate method. The specific surface area and particle size were 9.06 m2/g and about 91.3 nm respectively of LaNiO3 catalyst pre-heated at 350°C for 0.5 h and calcined at 700°C for 2 h. The conversion of CH4 and CO2 were 76.2% / 77.9% respectively when LaNiO3 catalyst reacted at 700°C, but the reaction was forced to terminate due to the serious carbon deposition after 1 h.
To improve the LaNiO3 catalyst used in the methane reforming of carbon dioxide reaction, magnesium was introduced as promoter to catalyst by two steps. First, the LaNi1-xMgxO3 catalyst was prepared by citrate method and discussed the best Mg adding content. And LaNi0.94Mg0.06O3 showed the best catalytic performance at 700°C, the CH4/CO2 conversion reached to 62.7% / 79.3%.
Second, to improve the catalytic performance and carbon resistability of catalyst, the LaNi1-xMgxO3 catalyst was promoted by co-doping and supported method. In co-doping way, Ce was adding to LaNi0.94Mg0.06O3 catalyst with different content. And La0.96Ce0.04Ni0.94Mg0.06O3 showed the best catalytic performance at 700°C, the CH4/CO2 conversion reached to 75.9% / 91.4%. In supported method way, LaNi0.94Mg0.06O3 was supported by α-Al2O3 with particle size 200 nm. 1 g of 5wt. LaNi0.94Mg0.06O3 / α-Al2O3 catalyst showed the best catalytic performance, carbon resistability, and stability in different using amounts. The CH4/CO2 conversion reached to 88.9% / 98.1%. It was only 1wt.% carbon deposition amount after 2 h activity reaction. And it could maintain the activity and stability(duribility) after reaction at 700°C for 8 h. It was also superior in these four catalysts.
Key words: Catalytic, LaNiO3, CH4, CO2, dry reforming.

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