Effect of reducibility on the performance of Co-based catalysts for the production of high-calorie synthetic natural gas
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pISSN: 0256-1115 eISSN: 1975-7220
INVITED REVIEW PAPER
INVITED REVIEW PAPER
Effect of reducibility on the performance of Co-based catalysts for the production of high-calorie synthetic natural gas Tae Young Kim*,‡, Seong Bin Jo**,‡, Chul Ho Lee***, Suk-Hwan Kang****, Joon Woo Kim*****, Soo Chool Lee**,†, and Jae Chang Kim*,† *Department of Chemical Engineering, Kyungpook National University, Daegu 41566, Korea **Research Institute of Advanced Energy Technology, Kyungpook National University, Daegu 41566, Korea ***Korea Institute of Industrial Technology, Ulsan 44413, Korea ****Institute for Advanced Engineering, Yongin 41718, Korea *****Research Institute of Industrial Science and Technology, Pohang 37673, Korea (Received 20 February 2020 • Revised 20 May 2020 • Accepted 27 May 2020) AbstractCo-based catalysts were developed for the production of high-calorie synthetic natural gas. The Co reduction in Al2O3- and SiO2-supported catalysts prepared with different Co loading, and their catalytic properties for highcalorie methanation were investigated. The CO conversion of the Co/SiO2 catalysts was superior to that of the Co/ Al2O3 with the same Co loading, due to their better reducibility at 400 oC. The activities of both the Al2O3 and SiO2supported catalysts increased with Co loading, while the growth of hydrocarbon chains decreased as the Co loading increased. As the reduction temperature increased, crystallite size of Co increased in 10Co/SiO2, resulting in decrease of CO conversion and increase of C2+ selectivity. The highest CO conversion (98.7%) was obtained over 10Co/SiO2 reduced at 400 oC. Moreover, the heating value of the product gas (10,405 kcal/Nm3) exceeded the standard heating value without requiring a high reduction temperature (700 oC) or a noble metal (Ru). Keywords: High-calorie Synthetic Natural Gas (HC-SNG), Cobalt, Reducibility, Light Hydrocarbons, Heating Value
crease its heating value. Nevertheless, the LPG addition has significant drawbacks, including high cost and supply chain uncertainty. Therefore, to increase the heating value of SNG without the addition of LPG, Co-based catalysts are used to convert syngas to light chain hydrocarbons (C1-C4), a reaction known as Fischer-Tropsch synthesis (FTS) [12-15]. Several catalysts have already been reported for the production of high-calorie SNG (HC-SNG), which is comparable to natural gas but includes additional C2-C4 hydrocarbons. Inui et al. developed Co-based catalysts on Al2O3 supports for the production of HC-SNG with a 10Co-6Mn-2Ru/Al2O3 catalyst exhibiting high activity and superior selectivity for C1-C4 hydrocarbons [16,17]. Furthermore, Lee et al. reported the effects of the components in CoMn-Ru/Al2O3 catalysts, demonstrating that the Mn promoter acted as a Lewis acid and enhanced the growth of carbon chains but reduced the catalytic activity at low temperature. In contrast, Ru induced a strong H2 spillover effect at active sites, resulting in higher activity and a lower Co species reduction temperature, which, however, reduced the C2
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