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用于丙烷和正丁烷重整制合成气的复合结构M/CeZrO/AlO/FeCrAl(M = Pt、Rh和Ru)催化剂

Composite Structured M/CeZrO/AlO/FeCrAl (M = Pt, Rh, and Ru) Catalysts for Propane and n-Butane Reforming to Syngas.

作者信息

Ruban Natalia, Rogozhnikov Vladimir, Zazhigalov Sergey, Zagoruiko Andrey, Emelyanov Vyacheslav, Snytnikov Pavel, Sobyanin Vladimir, Potemkin Dmitriy

机构信息

Boreskov Institute of Catalysis, Pr. Akademika Lavrentieva, 5, 630090 Novosibirsk, Russia.

Faculty of Natural Science, Novosibirsk State University, Pirogova St., 2, 630090 Novosibirsk, Russia.

出版信息

Materials (Basel). 2022 Oct 20;15(20):7336. doi: 10.3390/ma15207336.

Abstract

Here, we report the preparation, characterization, and performance of reforming propane and n-butane into a syngas of composite structured M/Ce0.75Zr0.25O2/Al2O3/FeCrAl (M = 0.46 wt.% Pt, 0.24 wt.% Rh, and 0.24 wt.% Ru) catalysts. The catalysts are composed of a high-heat-conducting FeCrAl block with preset geometry, with a surface nearly totally covered by θ-Al2O3. Afterwards, a layer of ceria−zirconia mixed oxide was deposited. The formed oxide coating was used as a support for 2−3 nm sized Pt, Rh, or Ru nanoparticles. The performance of the catalysts in propane steam reforming decreased in the order of Rh ≈ Ru > Pt. The reformates obtained in the propane steam reforming over Rh- and Ru/Ce0.75Zr0.25O2/Al2O3/FeCrAl at 600 °C and GHSV = 8300 h−1 contained 65.2 and 62.4 vol.% of H2, respectively, and can be used as a fuel for solid oxide fuel cells. In the oxidative steam reforming of propane at 700 °C and GHSV= 17,000 h−1, the activities of the Rh- and Pt-based catalysts were similar and the compositions of the outlet gas mixtures were quite close to equilibrium in both cases. Increasing the reagent flow rate to 25,600 h−1 showed stability of the Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl performance, whereas the Pt/Ce0.75Zr0.25O2/Al2O3/FeCrAl activity decreased. A mathematical model considering the velocity field, mass balance, pressure, and temperature distribution, as well as the reaction kinetics, was suggested for the propane steam and oxidative steam reforming over the Pt- and Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl catalysts. The model well described the experimental results.

摘要

在此,我们报告了复合结构的M/Ce0.75Zr0.25O2/Al2O3/FeCrAl(M = 0.46 wt.% Pt、0.24 wt.% Rh和0.24 wt.% Ru)催化剂用于丙烷和正丁烷重整制合成气的制备、表征及性能。这些催化剂由具有预设几何形状的高导热FeCrAl块组成,其表面几乎完全被θ-Al2O3覆盖。之后,沉积一层氧化铈-氧化锆混合氧化物。形成的氧化物涂层用作2-3纳米尺寸的Pt、Rh或Ru纳米颗粒的载体。催化剂在丙烷蒸汽重整中的性能按Rh≈Ru > Pt的顺序降低。在600℃和空速GHSV = 8300 h−1条件下,Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl和Ru/Ce0.75Zr0.25O2/Al2O3/FeCrAl上丙烷蒸汽重整得到的重整产物分别含有65.2和62.4 vol.%的H2,可作为固体氧化物燃料电池的燃料。在700℃和空速GHSV = 17,000 h−1条件下丙烷的氧化蒸汽重整中,Rh基和Pt基催化剂的活性相似,两种情况下出口气体混合物的组成都非常接近平衡。将试剂流速提高到25,600 h−1时,Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl的性能表现出稳定性,而Pt/Ce0.75Zr0.25O2/Al2O3/FeCrAl的活性降低。针对Pt/Ce0.75Zr0.25O2/Al2O3/FeCrAl和Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl催化剂上的丙烷蒸汽重整和氧化蒸汽重整,提出了一个考虑速度场、质量平衡、压力和温度分布以及反应动力学的数学模型。该模型很好地描述了实验结果。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/59af/9608493/4dd42ab44632/materials-15-07336-g001.jpg

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