Iron-promoted zirconia-alumina supported Ni catalyst for highly efficient and cost-effective hydrogen production via dry reforming of methane.

Developing cost-effective and high-performance catalyst systems for dry reforming of methane (DRM) is crucial for producing hydrogen (H2) sustainably. Herein, we investigate using iron (Fe) as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance. The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species, enhance the basicity and induce the deposition of oxidizable carbon. By incorporating 1 wt.% Fe into a 5Ni/10ZrAl catalyst, a higher CO2 interaction and formation of reducible "NiO-species having strong interaction with support" was observed, which led to an ∼80% H2 yield in 420 min of Time on Stream (TOS). Further increasing the Fe content to 2wt% led to the formation of additional reducible iron oxide species and a noticeable rise in H2 yield up to 84%. Despite the severe weight loss on Fe-promoted catalysts, high H2 yield was maintained due to the proper balance between the rate of CH4 decomposition and the rate of carbon deposit diffusion. Finally, incorporating 3 wt.% Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO2 interaction, wide presence of reducible NiO-species, minimum graphitic deposit and an 87% H2 yield. Our findings suggest that iron-promoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H2 production via DRM.

Alumina-Magnesia-Supported Ni for Hydrogen Production via the Dry Reforming of Methane: A Cost-Effective Catalyst System.

5Ni/MgO and 5Ni/γAl2O3 are pronounced in the line of cheap catalyst systems for the dry reforming of methane. However, the lower reducibility of 5Ni/MgO and the significant coke deposition over 5Ni/γAl2O3 limit their applicability as potential DRM catalysts. The mixing capacity of MgO and Al2O3 may overcome these limitations without increasing the catalyst cost. Herein, a 5Ni/xMg(100 - x)Al (x = 0, 20, 30, 60, 70, and 100 wt. %) catalyst system is prepared, investigated, and characterized with X-ray diffraction, surface area and porosity measurements, H2-temperature programmed reduction, UV-Vis-IR spectroscopy, Raman spectroscopy, thermogravimetry, and transmission electron microscopy. Upon the addition of 20 wt. % MgO into the Al2O3 support, 5Ni/20Mg80Al is expanded and carries both stable Ni sites (derived through the reduction of NiAl2O4) and a variety of CO2-interacting species. CH4 decomposition at Ni sites and the potential oxidation of carbon deposits by CO2-interacting species over 5Ni/20Mg80Al results in a higher 61% H2-yield (against ~55% H2-yield over 5Ni/γAl2O3) with an excellent carbon-resistant property. In the major magnesia support system, the 5Ni/60Mg40Al catalyst carries stable Ni sites derived from MgNiO2 and "strongly interacted NiO-species". The H2-yield over the 5Ni/60Mg40Al catalyst moves to 71%, even against a high coke deposition, indicating fine tuning between the carbon formation and diffusion rates. Ni dispersed over magnesia-alumina with weight ratios of 7/3 and 3/7 exhibit good resistance to coke. Weight ratios of 2/8 and 7/3 contain an adequate amount of reducible and CO2-interactive species responsible for producing over 60% of H2-yield. Weight ratio 6/4 has a proper coke diffusion mechanism in addition to achieving a maximum of 71% H2-yield.