Research and development of nickel based catalysts for carbon dioxide reforming of methane
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Date
2009
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Degree Level
Doctoral
Abstract
Consuming two major greenhouse gases, carbon dioxide (CO2) and methane (CH4), to produce synthesis gas, which is a mixture of carbon monoxide (CO) and hydrogen (H2), CO2 reforming of CH4 shows significant environmental and economic benefits. However, the process has not found wide industrial application due to severe catalyst deactivation, basically caused by carbon formation. Therefore, it is of great interest to develop stable catalysts without severe deactivation. This work is primarily focused on the development of novel nickel-based catalysts to achieve stable operation for CO2 reforming of CH4.
Following Dowden’s strategy of catalyst design, a series of nickel-based catalysts are designed with a general formula: Ni-Me/AlMgOx (Me = Co, Cu, Fe, or Mn). The designed catalysts are prepared using co-precipitation method and tested for CO2 reforming of CH4. Catalyst screening showed that the Ni-Co/AlMgOx catalyst has superior performance in terms of activity and stability to other Ni-Me/AlMgOx (Me = Cu, Fe, or Mn) catalysts. A 2000 h long-term deactivation test has shown that the Ni-Co/AlMgOx has high activity and excellent stability for CO2 reforming of CH4.
Further investigation on the Ni-Co/AlMgOx catalysts shows that adjusting Ni/Co ratio and Ni-Co loading can significantly affect the catalyst performance. Carbon free operation for CO2 reforming of CH4 can be achieved on the catalysts with a Ni/Co close to 1 and Ni-Co overall loading between 4-10 %. In addition, calcination temperature shows important impacts on the performance of Ni-Co/AlMgOx catalysts. A calcination temperature range of 700-900 oC is recommended.
The Ni-Co/AlMgOx catalysts are characterized using various techniques such as ICP-MS, BET, CO-chemiosorption, XRD, TPR, TG/DTA, TEM, and XPS. It has been found that the high activity and excellent stability of Ni-Co/AlMgOx catalysts can be ascribed to its high surface area, high metal disperation, small particle size, strong metal-support interaction, and synergy between Ni and Co.
Kinetic studies have shown that the CH4 decomposition and CO2 activation could be the rate-determining steps. Both Power-Law and Langmuir-Hinshelwood kinetic models can fit the experiment data with satisfactory results.
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Keywords
Carbon Dioxide, Methane, Reforming, Synthesis gas, Catalyst
Citation
Degree
Doctor of Philosophy (Ph.D.)
Department
Chemical Engineering
Program
Chemical Engineering