The oxidation kinetics,surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 ℃ for 20 h were investigated.The anti-coking performance and resistance to...The oxidation kinetics,surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 ℃ for 20 h were investigated.The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit.The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage.The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters,while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels.In the pyrolysis tests,the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere.The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10% of that in the air-H2O atmosphere.The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests,while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere.The ethylene,propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.展开更多
Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into synga...Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into syngas before they reach anode. In this work, catalytic activity of a redox-stable perovskite La0.7Sr0.3Cr0.8Fe0.2O3-δ(LSCrFO) for methane conversion was evaluated. The catalyst was fabricated as an anodic protective layer to improve coking resistance of a Ni cermet anode. Using wet CH4 as a fuel, the LSCrFO-modified cell showed excellent power output and good coking resistance with peak power density of 1.59 W cm-2 at 800℃. The cell demonstrated good durability lasting for at least 100 h. While the bare cell without the protective layer showed poor durability with the cell voltage fast dropped from 0.75 V to 0.4 V within 30 min. Under wet coal bed methane (CBM) operation, obvious performance degradation within 35 h (1.7 mV h^-1) was observed due to the influence of heavy carbon compounds in CBM. The pre-and post-mortem microstructures and carbon analysis of the anode surface and catalyst surface were further conducted.展开更多
基金financially supported by the scientific research project of China Petroleum and Chemical Corporation(No.409075)
文摘The oxidation kinetics,surface morphology and phase structure of oxide films grown on 25Cr20Ni alloy in air-H2O and H2-H2O atmospheres at 900 ℃ for 20 h were investigated.The anti-coking performance and resistance to carburization of the two oxide films were compared using 25Cr20Ni alloy tubes with an inner diameter of 10 mm and a length of 850 mm in a bench scale naphtha steam pyrolysis unit.The oxidation kinetics followed a parabolic law in an air-H2O atmosphere and a logarithm law in a H2-H2O atmosphere in the steady-state stage.The oxide film grown in the air-H2O atmosphere had cracks where the elements Fe and Ni were enriched and the un-cracked area was covered with octahedral-shaped MnCr2O4 spinels and Cr1.3Fe0.7O3 oxide clusters,while the oxide film grown in the H2-H2O atmosphere was intact and completely covered with dense standing blade MnCr2O4 spinels.In the pyrolysis tests,the anti-coking performance and resistance to carburization of the oxide film grown in the H2-H2O atmosphere were far better than that in the air-H2O atmosphere.The mass of coke formed in the oxide film grown in the H2-H2O atmosphere was less than 10% of that in the air-H2O atmosphere.The Cr1.3Fe0.7O3 oxide clusters converted into Cr23C6 carbides and the cracks were filled with carbon in the oxide film grown in the air-H2O atmosphere after repeated coking and decoking tests,while the dense standing blade MnCr2O4 spinels remained unchanged in the oxide film grown in the H2-H2O atmosphere.The ethylene,propylene and butadiene yields in the pyrolysis tests were almost the same for the two oxide films.
基金supported by the Coal Seam Gas Joint Foundation of Shanxi(2015012016)Shanxi Province Science Foundation(2016011025)+2 种基金Shanxi Scholarship Council of China(2016-010)Shanxi “1331 Project” Key Innovative Research Team(“1331KIRT”)the Open Funding from State Key Laboratory of Materialoriented Chemical Engineering(No.KL16-03)
文摘Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into syngas before they reach anode. In this work, catalytic activity of a redox-stable perovskite La0.7Sr0.3Cr0.8Fe0.2O3-δ(LSCrFO) for methane conversion was evaluated. The catalyst was fabricated as an anodic protective layer to improve coking resistance of a Ni cermet anode. Using wet CH4 as a fuel, the LSCrFO-modified cell showed excellent power output and good coking resistance with peak power density of 1.59 W cm-2 at 800℃. The cell demonstrated good durability lasting for at least 100 h. While the bare cell without the protective layer showed poor durability with the cell voltage fast dropped from 0.75 V to 0.4 V within 30 min. Under wet coal bed methane (CBM) operation, obvious performance degradation within 35 h (1.7 mV h^-1) was observed due to the influence of heavy carbon compounds in CBM. The pre-and post-mortem microstructures and carbon analysis of the anode surface and catalyst surface were further conducted.