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Research Papers

Design of Anode Materials for IT SOFC: Effect of Complex Oxide Promoters and Pt Group Metals on Activity and Stability in Methane Steam Reforming of Ni/YSZ (ScSZ) Cermets

[+] Author and Article Information
Vladislav A. Sadykov, Natalia V. Mezentseva, Rimma V. Bunina, Galina M. Alikina, Anton I. Lukashevich, Vladimir I. Zaikovskii

Boreskov Institute of Catalysis, SB RAS, Novosibirsk 630090, Russia

Oleg F. Bobrenok

Institute of Thermophysics, SB RAS, Novosibirsk 630090, Russia

John Irvine

School of Chemistry, University of St. Andrews, KY16 9AJ, Scotland, UK

Oleksandr D. Vasylyev

 Frantcevych Institute for Problems of Materials Science, Kyiv 03680, Ukraine

Alevtina L. Smirnova

 University of Connecticut, Storrs, CT 06269

J. Fuel Cell Sci. Technol 7(1), 011005 (Oct 06, 2009) (6 pages) doi:10.1115/1.3117255 History: Received July 13, 2007; Revised September 05, 2008; Published October 06, 2009

Ni/YSZ or Ni/ScCeSZ cermets were promoted by up to 10wt% of fluoritelike (Pr–Ce–Zr–О, La–Ce–Zr–О, and Ce–Zr–О) or perovskitelike (La–Pr–Mn–Cr–O) oxides and small (up to 1.4wt%) amounts of Pt group metals (Pd, Pt, or Ru). Reactivity of samples, their lattice oxygen mobility, and their ability to activate methane were characterized by temperature-programed reduction by CH4. The catalytic properties of these samples in methane steam reforming were studied at 500850°C and short contact times (10 ms) in feeds with 8mol% of CH4 and steam/methane ratio of 1:3. Oxide promoters ensure stable performance of cermets in stoichiometric feeds at T>650°C by suppressing carbon deposition. Copromotion with precious metals enhances performance in the intermediate temperature (450600°C) range due to more efficient activation of methane. Factors determining specificity of these cermet materials’ performance (chemical composition, microstructure, oxygen mobility in oxides, interaction between components, and reaction media effect) are considered. The most promising systems for practical application are Pt/Pr–Ce–Zr–O/Ni/YSZ and Ru/La–Pr–Mn–Cr–O/Ni/YSZ cermets demonstrating a high performance in the intermediate temperature range under broad variation in steam/CH4 ratio.

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Figures

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Figure 1

Efficient first-order rate constants of CH4 SR versus T for Ni/YSZ (1), Ce0.5Zr0.5O2/Ni/YSZ (2), 0.3%Pd/10%Ce0.5Zr0.5O2/Ni/YSZ (3), and 0.3%Pt/10%Pr0.3Ce0.35Zr0.35O2/Ni/YSZ ((4) and (5)). 10 ms contact time, feed 8%CH4+8% ((1)–(4)) or 24% (5) H2O.

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Figure 2

(a) Effect of CH4/steam ratio in the feed (CH4 content 8%) on CH4 conversion for Ni/YSZ cermet copromoted with Pd and Ce0.5Zr0.5O2; CH4/H2O=1:1, 1:2, or 1:3. (b) Effect of CH4/steam ratio in the feed (CH4 content 8%) on CH4 conversion for Ni/YSZ cermet promoted with Ce0.5Zr0.5O2; CH4/H2O=1:1, 1:2, or 1:3.

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Figure 3

Effect of steam/CH4 ratio in the feed (CH4 content 8%) on CH4 conversion for Ni/YSZ cermet copromoted with 1.03% Pt+10% Pr0.3Ce0.35Zr0.35O2 ((1) and (2)) or 0.3% Pt+10% La0.3Ce0.35Zr0.35O2 ((3) and (4)). H2O/CH4≔3 ((1) and (3)) or 1 ((2) and (4)).

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Figure 4

Effect of CH4/steam ratio in the feed (CH4 content 8%) on CH4 conversion for Ni/YSZ cermet doped with 10% Pr0.3Ce0.35Zr0.35O2 and promoted by 0.3% Pt ((1) and (2)) or 0.5% Ru ((3) and (4)). CH4:H2O=1:3 ((1) and (3)) or 1:1 ((2) and (4)).

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Figure 5

Efficient first-order rate constants versus T for CH4 SR on Ni/ScCeSZ cermet promoted by La–Pr–Mn–Cr–O (1) and loaded with 0.3% Pd (2) or Ru ((3) and (4)). Feed 8% CH4+8% H2O (1–3) and 8% CH4+24% H2O (4).

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Figure 6

Effect of steam/CH4 ratio in the feed (CH4 content 8%) on CH4 conversion for La–Pr–Mn–Cr–O/Ni/ScCeSZ cermet promoted by 1% Ru ((1) and (2)) or 0.3% Ru ((3) and (4)). H2O/CH4=3 ((1) and (3)) or 1 ((2) and (4)).

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Figure 7

CH4 conversion and efficient first-order rate constants for CH4 SR at 650°C for cermets promoted with perovskite and Pd or Ru. Feed 8% CH4+8% H2O in He (1:1) or 8% CH4+24% H2O in He (1:3).

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Figure 8

Temperature dependence of CH4 conversion for La–Pr–Mn–Cr–O/Ni/YSZ cermet without (1) or with (2) 1 wt % Ru as copromoter. Feed 8% CH4+8% H2O in He.

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Figure 9

CH4 TPR curves for green 0.5% Ru/10%Pr0.3Ce0.35Zr0.35O2/Ni/YSZ cermet

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Figure 10

CH4 TPR curves for green 0.3% Ru /10% La–Pr–Mn–Cr–O/Ni/ScCeSZ cermet

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