Stability of Ni/SiO<sub>2</sub>-ZrO<sub>2</sub> catalysts towards steaming and coking in the dry reforming of methane with carbon dioxide

doi:10.1007/s11705-016-1568-0

Front. Chem. Sci. Eng.

2016, Vol. 10

Issue (2) : 281-293 https://doi.org/10.1007/s11705-016-1568-0

RESEARCH ARTICLE

Stability of Ni/SiO₂-ZrO₂ catalysts towards steaming and coking in the dry reforming of methane with carbon dioxide

Bettina Stolze¹,Juliane Titus¹,Stephan A. Schunk²,Andrian Milanov³,Ekkehard Schwab³,Roger Gläser^1,^*(

)

¹. Institute of Chemical Technology, Universität Leipzig, Linnéstr. 3, 04103 Leipzig, Germany
². hte GmbH, Kurpfalzring 104, 69123 Heidelberg, Germany
³. BASF SE, Carl-Bosch-Straße 38, 67056 Ludwigshafen, Germany

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Abstract

Ni/SiO₂-ZrO₂ catalysts with Ni loadings of 1 to 13 wt-% were prepared, characterized by elemental analysis, X-ray diffraction, N₂ sorption, temperature programmed oxidation, temperature programmed reduction, and tested for their activity and stability in the dry reforming of methane with carbon dioxide at 850 °C, gas hourly space velocity of 6000 and 1800 h^–1 and atmospheric pressure. The SiO₂-ZrO₂ support as obtained through a simple and efficient sol-gel synthesis is highly porous (A_BET = 90 m²·g^–1, d_P = 4.4 nm) with a homogeneously distributed Si-content of 3 wt-%. No loss of Si or formation of monoclinic ZrO₂, even after steaming at 850 °C for 160 h, was detectable. The catalyst with 5 wt-% Ni loading in its fully reduced state is stable over 15?h on-stream in the dry reforming reaction. If the catalyst was not fully reduced, a reduction during the early stages of dry reforming is accompanied by the deposition of up to 44 mg·g^–1carbon as shown by experiments in a magnetic suspension balance. Rapid coking occurs for increased residence times and times-on-stream starting at 50 h. The Ni loading of 5 wt-% on SiO₂-ZrO₂ was shown to provide an optimal balance between activity and coking tendency.

Keywords Ni/SiO₂-ZrO₂ synthesis gas dry reforming coking steaming

Corresponding Author(s): Roger Gläser

Just Accepted Date: 31 March 2016 Online First Date: 27 April 2016 Issue Date: 19 May 2016

Cite this article:

Bettina Stolze,Juliane Titus,Stephan A. Schunk, et al. Stability of Ni/SiO₂-ZrO₂ catalysts towards steaming and coking in the dry reforming of methane with carbon dioxide[J]. Front. Chem. Sci. Eng., 2016, 10(2): 281-293.

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https://academic.hep.com.cn/fcse/EN/10.1007/s11705-016-1568-0
https://academic.hep.com.cn/fcse/EN/Y2016/V10/I2/281

Fig.1 CH₄ conversion and molar ratio n H 2 / n CO as a function of time-on-stream in the DRM over 5Ni/SiO₂-ZrO₂(batch 1) for the first and second use (T=850 °C, GHSV=6.0×10³ h^?¹, n CH 4 / n CO 2 / n Ar = 47.5/47.5/5.0)

Tab.1 CH₄ and CO₂ conversion, n H 2 / n CO -molar ratio and C-selectivity under thermodynamic equilibrium (Td. equil.) and after 15 h on-stream in the DRM over Pt/ZrO₂ and 5Ni/SiO₂-ZrO₂ (batch 1) for the first and second use (T = 850 °C, GHSV= 6.0 × 10³ h^?¹, n CH 4 / n CO 2 / n Ar = 47.5/47.5/5.0)

Fig.2 Mass change Dm and temperature profile during DRM and oxidative regeneration for 5Ni/SiO₂-ZrO₂ (batch 1) (DRM : T = 850 °C, GHSV= 3 × 10⁴ h^?¹, n CH 4 / n CO 2 / n A r = 47.5/47.5/5.0; regeneration: T = 850 °C, F_air = 10 cm³·min^?¹)

Fig.3 PXRD patterns of 5Ni/SiO₂-ZrO₂ (batch 1) before (fresh) and after (regenerated) use in DRM (reaction conditions as in Fig. 1) and oxidative regeneration (T = 850 °C, F_air = 10 cm³·min^?¹). Simulated XRD patterns of cubic (c-ZrO₂) and tetragonal (t-ZrO₂) zirconia are also included [44]

Fig.4 N₂-Sorption isotherms (left) and pore width distribution (from the desorption branch of the isotherms, right) of 5Ni/SiO₂-ZrO₂ (batch 1) before the catalytic experiment (fresh) and after use in DRM and oxidative regeneration (regenerated; conditions as in Fig. 3)

Fig.5 TPR-profiles of 5Ni/SiO₂-ZrO₂(batch 1) before the catalytic experiment (fresh) and after use in DRM and oxidative regeneration (regenerated; conditions as in Fig. 3)

Tab.2 Specific BET surface area, BJH pore volume and average BJH pore diameter, content of Ni, Si and Zr from elemental analysis (EA) and Ni particle diameter d_Ni from XRD (Scherrer equation) for 5Ni/SiO₂-ZrO₂ (batch 2) before and after steaming

Fig.6 PXRD patterns (left) and N₂-sorption isotherms (right) of 5Ni/SiO₂-ZrO₂ (batch 2) before (fresh) and after steaming (T = 850 °C, t = 160 h, m H 2 O = 2 g·h^?¹)

Fig.7 CH₄ and CO₂ conversion as well as n H 2 / n CO -molar ratio and C-selectivity (from TGA) for 5Ni/SiO₂-ZrO₂ (batch 1) after different times-on-stream in DRM (T = 850 °C, GHSV= 1.8×10³ h^?¹, n CH 4 / n CO 2 = 1/1)

Tab.3 Specific BET surface area, BJH pore volume and average BJH pore diameter for 5Ni/SiO₂-ZrO₂ (batch 1) before (fresh) the catalytic experiments and after different times-on-stream in DRM (T = 850 °C, GHSV= 1.8×10³ h^?¹, n CH 4 / n CO 2 = 1/1)

Fig.8 HRTEM images of a CNT (left) and of carbon layers encapsulating a Ni particle (right) formed on 5Ni/SiO₂-ZrO₂ (batch 1) after 60 h on-stream in DRM (T = 850 °C, GHSV= 1.8×10³ h^?¹, n CH 4 / n CO 2 = 1/1)

Fig.9 Diameter distribution of Ni particles determined from TEM images (ESI, Fig. 6S) for 5Ni/SiO₂-ZrO₂ (batch 1) after 2 h (left) and after 60 h on-stream in DRM (T = 850 °C, GHSV= 1.8×10³ h^?¹, n CH 4 / n CO 2 = 1/1)

Tab.4 Ni content x_Ni, specific BET surface area, BJH pore volume and average BJH pore diameter for Ni/SiO₂-ZrO₂ catalysts with different Ni contents

Fig.10 PXRD patterns of Ni/SiO₂-ZrO₂ catalysts (batch 2, fresh) with different Ni loadings in wt-% (● Ni, ▲ NiO)

Fig.11 TPR profiles of Ni/SiO₂-ZrO₂ (batch 2, fresh) with different Ni loadings

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