Sub-nanometer ceria-promoted Ni 13X zeolite catalyst for CO2 methanation

Sub-nanometer zeolite 13X-supported Ni-ceria catalysts were synthesized for CO2 methanation. XRD and SEM results show the structure and morphology of 13X zeolite after impregnation and calcination. Ce loading affected the catalysts’ metal dispersion, reducibility, basicity and acidity, and thence their activity and selectivity. STEM-EDX elemental mappings showed that Ce and Ni are predominantly highly dispersed. Ce has a positive effect on the reduction of NiO and leads to a relatively high number of medium basic sites with a low Ce loading. Highly stable 5%Ni2.5%Ce13X had high activity and nearly 100% CH4 selectivity in CO2 methanation at 360 °C, which is mainly due to the high dispersion of metals and relatively high amount of medium basic sites. It can be inferred that this catalyst synthesis strategy has great potential for good catalyst dispersion, since metal uptake by the zeolite is selective for the metal citrate complexes in solution.

Liangyuan Wei, Henrik Grénman, Wim Haije, Narendra Kumar, Atte Aho, Kari Eränen, Liangfu Wei, Wiebren de Jong

Influence of nickel precursors on the properties and performance of Ni impregnated zeolite 5A and 13X catalysts in CO2 methanation

Zeolite 13X and 5A supported Ni catalysts were synthesized for CO2 methanation using the evaporation impregnation method. The influence of using different Ni precursors (nitrate, citrate, and acetate) as well as calcination temperatures on the catalyst properties and performance were investigated. XRD, SEM-EDX, TEM, STEM-EDX, N2 physisorption, H2-TPR, TPD-NH3 and TG/DTA were used for detailed characterization of the catalysts. The parent structure of the zeolites did not change during catalyst synthesis. Using nickel citrate and acetate resulted in smaller NiO particle size compared to nitrate. STEM-EDX results showed that all the Ni-precursor complexes entered more efficiently the 13X zeolite structure, which is mainly due to steric hindrance resulting from the smaller pore size of 5A. Methanation experiments revealed that the 13X catalysts synthesized using nickel citrate (5% Ni) displayed clearly higher activity, compared to the catalysts synthesized using nickel nitrate or nickel acetate. A 79% conversion at 320 °C was obtained with 100% selectivity towards CH4 and the catalyst showed excellent stability during 200 h testing. Overall, it can be concluded that the Ni precursor significantly influences the physico-chemical characteristics and catalytic properties of Ni 13X and Ni 5A zeolite catalysts in CO2 methanation: complex size and pore size matter.

Liangyuan Wei, Wim Haije, Narendra Kumar, Janne Peltonen, Markus Peurla, Henrik Grenman, Wiebren de Jong

Pure methane from CO2 hydrogenation using a sorption enhanced process with catalyst/zeolite bifunctional materials

Methanation is a potential large-scale option for CO2 utilization, and it is one of the solutions for decreasing carbon emission and production of synthetic green fuels. However, the CO2 conversion is limited by thermodynamics in conventional reaction conditions. However, around 100 % conversion can be obtained using sorption enhanced CO2 methanation according to Le Chatelier’s principle, where water is removed during the reaction using zeolite as a sorbent. In this work 5%Ni5A, 5%Ni13X, 5%NiL and 5%Ni2.5%Ce13X bifunctional materials with both catalytic and water adsorption properties were tested in a fixed bed reactor. The overall performance of the bifunctional materials decreased on going from 5%Ni2.5%Ce13X, 5%Ni13X, 5%Ni5A, to 5%NiL. The CO2 conversion and CH4 selectivity were approaching 100 % during prolonged stability testing in a 100 reactive adsorption – desorption cycles test for 5%Ni2.5%Ce13X, and only a slight decrease of the water uptake capacity was observed.

Drs. Liangyuan Wei, Drs. Hamza Azad, Dr. Wim Haije, Wiebren de Jong

Nickel-iron layered double hydroxides for an improved Ni/Fe hybrid battery-electrolyser

Due to over- and under-supply, renewable energy sources can have a major impact on the electricity market and cause fluctuating electricity prices. In their laboratory, dr. Audrey Iranzo and prof.dr. Fokko Mulder developed a Ni-Fe layered double hydroxide for use as a positive electrode in the integrated nickel-iron battery and alkaline electrolyser.

Dr. Audrey Iranzo and prof.dr. Fokko Mulder

Earlier Publications