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Citation: Zhi-Bin WANG, Zhi-Feng QIN, Xun HAN, Peng-Cheng SUN, Yi LIU, Li-Ping CHANG, Jun REN, Cong-Ming LI. Highly active and sulfur-tolerant MoO3 modified NiO-Al2O3 catalysts for coke oven gas methanation[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(5): 967-978. doi: 10.11862/CJIC.2023.055 shu

Highly active and sulfur-tolerant MoO3 modified NiO-Al2O3 catalysts for coke oven gas methanation

  • 1.

    State Key Laboratory of Clean and Efficient Coal Utilization, College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

  • 2.

    Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030002, China

  • 3.

    Postdoctoral Research Station, Environmental Planning Institute of Shanxi Province, Taiyuan 030002, China

  • 4.

    Environmental Science and Engineering Postdoctoral Mobile Station, Tsinghua University, Beijing 100084, China

Figures(6)

  • A series of xMoO3/NiO-Al2O3 catalysts (x% represented the mass fraction of MoO3) were prepared by double hydrolytic co-precipitation method combined with impregnation method. The methanation reaction activity and sulfur resistance of catalysts were evaluated using a fixed-bed reactor, and the catalysts were characterized in detail fresh and after deactivation. The results showed that the low-temperature methanation activity of the catalyst decreased with the increase in MoO3 loading, whereas the sulfur resistance of the catalyst was significantly enhanced after MoO3 doping. The decrease in catalyst activity for low-temperature methanation was attributed to the fact that the increase in MoO3 loading reduced the active specific surface area of the catalyst, but the introduction of MoO3 also provided a competitive adsorption site for sulfide, which can delay sulfur poisoning at the active site. The xMoO3/NiO-Al2O3 catalyst with 12.5% MoO3 loading (mass fraction) maintained the highest methanation activity for 7 h in the presence of 143 mg·m-3 H2S/H2 (81.1% CO conversion, 550 ℃). The sulfur chemisorption content of 12.5MoO3/NiO-Al2O3 catalyst reaching 0.71% (mass fraction) was 1.48 times that of NiO-Al2O3 catalyst and further XPS also confirmed that the amount of MoS2 generated was the highest, which indicated that Mo preferentially adsorbs more sulfur and protects the active site. In addition, at a MoO3 loading of 12.5%, MoO3 on the surface of the catalyst reached the threshold of monolayer dispersion, which can provide more adsorption sites for sulfides when competitive adsorption occurs.
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