Enhancement of Power-to-Gas via Multi-catalyst Reactors Tailoring Reaction Rate and Heat Exchange.

The Sabatier reaction is a key element of power-to-gas development. For this reason, even though the process is known since more than one century, the Sabatier reaction is currently the object of important research efforts towards the development of new catalysts for performance improvement. However, the industrial exploitation of the Sabatier reaction depends on the development of reactors that match the best catalyst with an appropriate heat management. For this reason, this paper develops a methodology for the contemporary optimization of the reactor concept and the catalysts. It is observed that the reactor can be divided into three sections with contrasting requirements. In the first section, the main requirement concerns the reach of the reaction activation conditions. Hence, an adequate match between catalyst and reactor is needed, for example with an appropriate pre-heater. Once the reaction is activated, a reaction hotspot is formed, so that the cooling becomes determining and the main requirement for the catalyst is the resistance to poisoning and sintering. In the last section of the reactor, the low temperature activity of the catalyst is determining, so that a high-performing catalyst is needed. This paper indicates a strategy for the rational design of this catalyst, based on mechanistic evidences.

Analysis of the current world biofuel production under a water-food-energy nexus perspective.

This paper assesses the sustainability of bioenergy production under a nexus perspective through a new efficiency type index. The index describes 1st generation biofuel production under the perspective of the implied consumption of natural resources. We consider the sustainability of energy production as a sequence of steps, each characterised by its efficiency, and propose an index which returns an overall efficiency value describing the adequacy or inadequacy of the considered processes under a nexus perspective. The direct application of the nexus index entails an indication of the possible improvements needed to move production towards most sustainable processes or places. Moreover, it allows evaluating the efficiency of the main crops currently used in biofuel production with respect to the water-food-energy nexus. The results depict countries presently capable of performing sustainable production of 1st generation biofuel from particular crops. Furthermore, the analysis of the single components of the nexus index allows understanding the effects of possible improvements (e.g. soil and water management, new generation biofuels) on the overall production efficiency under a nexus perspective.

Linking heat and electricity supply for domestic users: an example of power-to-gas integration in a building.

A novel power-to-X system, coupling electricity and gas grid in a building, is presented. This system operates a retrofit of the existing photovoltaic system, consuming the electricity overproduction in the local synthesis of methane instead of injecting it into the electricity grid. Methane can be stored in the gas grid and used in winter in the existing gas burners, providing the required heat to keep the building at a comfortable temperature. Additionally, the methanation system provides waste heat that is used to warm up the sanitary water, eliminating the need for an electric boiler. The system, fed by 800 m2 of solar panels, was optimized according to the weather conditions and the dimensions of the main pieces of equipment were determined. This allows the production of ca. 17 MW h of methane for seasonal storage. By retrofitting the building with the power-to-X unit, the energetic independence of the house is maximized, thanks to the synchronous production of electricity, gas, and heat, including energy storage. Therefore, the profitability of the photovoltaic system is ensured independently from the electricity feed-in tariffs. The system performance was evaluated in a case study in the north of Switzerland. When considering the purchase of renewable natural gas (i.e., from biogas), it was calculated that the system would be profitable for an electricity price below 0.05 € per kW h.

A combined diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy-gas chromatography for the operando study of the heterogeneously catalyzed CO2 hydrogenation over transition metal-based catalysts.

We built an inline diffuse reflectance infrared Fourier transform spectroscopy-mass spectroscopy-gas chromatography (DRIFTS-MS-GC) apparatus aiming at an operando mechanistic study of the heterogeneously catalyzed CO2 hydrogenation reaction. The multifunctional and accurate system enabled the simultaneous utilization of IR, MS, GC, and nuclear magnetic resonance techniques in one single device to analyze the surface, gas, and liquid products formed during the reaction process. To assess the potential of the system, we compared the activity of pristine metal (Fe, Co, Ni, and Cu), metal alloy (LaNi4Cu), and metal-metal oxide (Co-CoO) catalysts with respect to the interactions between gaseous CO2 and the catalyst surfaces. For the quantitative comparison, the rate constants and activation energies of CO2 hydrogenation were determined. The results showed a composition dependent reactivity of the metals. The metal oxide mixed with the metal is essentially important for the formation of observable of the surface species deriving from CO2 adsorption and for the enhancement of the CO2 conversion to CH4.

Fast real time and quantitative gas analysis method for the investigation of the CO2 reduction reaction mechanism.

We present a new fast real time and quantitative gas analysis method by means of mass spectrometry (MS), which has approximately an order of magnitude faster sampling rate in comparison with a traditional gas chromatography. The method is presented and discussed on the example of the CO2 reduction reaction. The advantages of the method are the possibility to analyze the reaction kinetics, where the kinetically determined reaction range is often only tens of degrees wide. Furthermore, due to the fast sampling rate, the experiments are much shorter and effects due to possible aging of the catalyst are significantly reduced. The quantification of the gas partial pressures is achieved by calibrating the Faraday detector in the quadrupole MS for the expected reactants and products. One major challenge to achieve a quantitative measurement with the MS is to correct for the pressure fluctuations over the probing capillary over the course of the experiment. This fluctuation is compensated in the analysis by normalizing the sum of all calculated partial pressures to the measured reaction pressure for every measured spectrum. With that, a precise, fast, and quantitative gas analysis is achieved. This is the fundament for, e.g., the kinetic reaction analysis where a high data point density is required. The method is discussed on the example of the CO2 hydrogenation reaction to CH4 on a commercial Ru/Al2O3 catalyst. Additionally, the key features of the gas controlling and analysis setup built for the CO2 hydrogenation reaction are described.