Hydrogen production through autothermal reforming of CH4: Efficiency and action mode of noble (M = Pt, Pd) and non-noble (M = Re, Mo, Sn) metal additives in the composition of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts

• Published in: International journal of hydrogen energy Vol. 45; no. 58; pp. 33352 - 33369
• Main Authors: Matus, Ekaterina V., Ismagilov, Ilyas Z., Yashnik, Svetlana A., Ushakov, Vladimir A., Prosvirin, Igor P., Kerzhentsev, Mikhail A., Ismagilov, Zinfer R.
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 27.11.2020
• Subjects: Hydrogen; Methane; Ni catalyst; Promoter; Reforming; Methane; Promoter; Reforming; Hydrogen; Ni catalyst
• ISSN: 0360-3199; 1879-3487
• DOI: 10.1016/j.ijhydene.2020.09.011

Hydrogen production through autothermal reforming of methane (ATR of CH4) over promoted Ni catalysts was studied. The control of the ability to self-activation and activity of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts was achieved by tuning their reducibility through the application of different types (M = Pt, Pd, Re, Mo or Sn) and content (molar ratio M/Ni = 0.003, 0.01 or 0.03) of additive. The comparison of the efficiency and action mode of noble (M = Pt, Pd) and non-noble (M = Re, Mo, Sn) metal additives in the composition of Ni-M/Ce0.5Zr0.5O2/Al2O3 catalysts was performed using X-ray fluorescence analysis, N2 adsorption, X-ray diffraction, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction with hydrogen, and thermal analysis. The composition-characteristics-activity correlations were determined. It was shown that the introduction of a promoter does not affect the textural and structural properties of catalysts but influences their reducibility and performance in ATR of CH4. At the similar dispersion of NiO active component (11 ± 2 nm), the Ni2+ reduction is intensified in the following order of additives: Mo < Sn < Re ≤ Pd < Pt. It was found that for the activation of Ni and Ni–Sn catalysts before ATR of CH4 tests, the pre-reduction is required. On the contrary, the introduction of Pt, Pd and Re additives leads to the self-activation of catalysts under the reaction conditions and an increase of the H2 yield due to the enhanced reducibility of Ni2+. The efficient and stable catalyst for hydrogen production has been developed: in ATR of CH4 at 850 °C over an optimum 10Ni-0.9Re/Ce0.5Zr0.5O2/Al2O3 catalyst the H2 yield of 70% is attained. The designed catalyst has enhanced stability against oxidation and sintering of Ni active component as well as high resistance to coking. [Display omitted] •ATR of CH4 over Ni-M (M = Pt, Pd, Re, Mo, Sn) without prior reduction was studied.•The addition of Pt, Pd, Re or Mo leads to self-activation and an increase of H2 yield.•The performance of Ni–Re and Ni–Pt catalysts are comparable.•The 10Ni-0.9Re/Ce0.5Zr0.5O2/Al2O3 provides 70% H2 yield at 100% CH4 conversion.