Low-Temperature Catalytic CO₂ Dry Reforming of Methane on Ni-Si/ZrO₂ Catalyst

Abstract

The activity of a ZrO 2 -supported nickel catalyst promoted by silica (Ni-Si/ZrO 2 ) in CO 2 dry reforming of methane was carried out at 400 and 450 °C. The catalysts were prepared by an impregnation method and characterized by H 2 -TPR, XRD, TEM, TG-MS, Raman, XPS, and in situ XPS and DRIFTS. It was discovered that Ni-Si/ ZrO 2 showed higher initial conversion of CH 4 (0.50 s −1 ) and CO 2 (0.44 s −1 ), and stability for low temperature (400 °C) DRM reaction in comparison to an SiO 2 -supported nickel catalyst promoted by zirconia (Ni-Zr/SiO 2 ) (0.32 s −1 for both CO 2 and CH 4 ). The Ni-Si/ZrO 2 catalyst featured the formation of active nickel particles with a small size of 6−9 nm and with slightly strong electronic donor ability, stabilization of the initial metal nickel state under the reaction conditions, and the formation of easily removed C 1 coke. However, for the 450 °C DRM reaction, the coke that formed on the Ni-Si/ZrO 2 catalyst was mainly C 2 coke that was difficult to remove, because the CO 2 preferred to combine with H species rather than react with the coke. For the Ni-Zr/SiO 2 catalyst, the Ni 0 species was oxidized to a NiO species under the reaction conditions at 400 °C and could not be restored, leading to its deactivation.

Highly Carbon-Resistant Y Doped NiO–ZrOm Catalysts for Dry Reforming of Methane

“…Two reduction peaks at about 450 and 650 • C, denominated α and β, respectively, are observed on both catalysts. The first peak (α) corresponds to the reduction of the NiO species of weak and strong interaction with Y and/or Zr [23,27]. This first peak shifts to low temperature on NiO-ZrO m -YO n catalyst, as compared to the NiO-ZrO m catalyst.…”

Catalytic Activity of Nickel and Ruthenium–Nickel Catalysts Supported on SiO2, ZrO2, Al2O3, and MgAl2O4 in a Dry Reforming Process

“…Then, solutions of metal salts (nickel(II) nitrate and/or ruthenium(III) chloride) were added dropwise and the pH was adjusted to 9. The precipitate was separated, washed twice with water, and dried at 80 • C. Obtained powders were calcinated at 400, 500, and 600 • C for Al 2 O 3 , MgAl 2 O 4 , SiO 2 , and ZrO 2 supports [30,41,42], respectively. The metal content used for preparation was 7 wt.% and 1 wt.% for nickel and ruthenium, respectively.…”

“…Ruthenium nanoparticles were also successfully used for tuning the hydrogen/carbon monoxide molar ratio [16]. The coupling of nickel particles into alloys or spinel structures with other non-noble elements, such as Co [17,18], Cr [18], Mn [18][19][20], Ce [19,21], Fe [22,23], Zr [24], and Al [20,24], and alkali metals, such as Mg [25,26], K [27,28], and Na [29], was also reported as an effective approach to extend catalyst activity and reduce carbon formation [18,30]. Another technique used to preserve the small size of nickel particles is an application of a support that strongly interacts with the active metal.…”

Recent Progresses in the Design and Fabrication of Highly Efficient Ni-Based Catalysts With Advanced Catalytic Activity and Enhanced Anti-coke Performance Toward CO2 Reforming of Methane

“…Therefore, the metallic Ni nanoparticles can be well-dispersed on the support, which is further conducive to the improvement of the catalytic activity and anti-coke property of the catalyst (Nabgan et al, 2020). Wang Y. et al (2018b) confirmed that the metal-support interaction of the Ni-Si/ZrO 2 catalyst not only facilitated the formation of small metallic Ni active sites with strong electron donor capability but also maintained the state of the Ni particles under CRM reaction conditions.…”

“…Oxide materials, such as CeO 2 (Luisetto et al, 2019), SiO 2 (Zhang L. et al, 2019;de la Cruz-Flores et al, 2020), Al 2 O 3 (Rahbar Shamskar et al, 2017), MgO (Zhou et al, 2018), and ZrO 2 (Wang Y. et al, 2018b), are widely utilized as supports of Nibased catalysts for the CRM process. For example, CeO 2 has been extensively investigated as a support of Ni-based catalysts because of the formation of a strong metal-support interaction, which can contribute to the enhancement of the reactivity by facilitating the CH 4 dissociation over the metallic Ni active site (Yan et al, 2019).…”