Supported ruthenium nanoparticles for supercritical water gasification - synthesis, activity and stability

Supercritical water gasification (SCWG) is a promising and versatile technology for the conversion of a variety of wet biomass streams into renewable natural gas. In this work, the focus was set on methane production with the help of an active and stable methanation catalyst. The supercritical water (SCW) environment can lead to rapid catalyst deactivation through different mechanisms, namely poisoning, coking, sintering or leaching. Although addressed, it remains challenging to disentangle them in SCWG. The goal of this thesis is to get a better understanding of the aforementioned deactivations pathways by trying to study them individually, in order to tailor an active and robust SCWG catalyst.The intrinsic gasification activity of carbon supports exhibiting different properties was assessed by feeding glycerol at 400°C and 30MPa. The negative effect of micropores was shown by significant coke deposition and surface area loss around 90%, compared to mesoporous carbons that only lost 20%. Carbon nanofibers (CNF) proved to be an interesting support showing very good stability and inertness. The synthesis of 5%Ru catalysts on selected supports confirmed these trends. Highly microporous Ru/C catalysts were less stable than the ones supported on carbon frameworks of more open pore structure. Ru/CNF seemed to be a promising SCWG catalyst, with an enhanced resistance towards coke formation. The completely open pore structure of CNF was found to be a crucial parameter.Ruthenium loss was investigated by measuring the its content in the process waters with ICP-MS. Ru was successfully quantified at levels close to thermodynamic models for Ru/AC and Ru/CNF of different loadings (0.01-0.2 µg L-1). Furthermore, the process parameters had no effect on the quantified Ru, showing that the steady-state loss represents a thermodynamically-driven leaching. Fluctuations in feed rate and pressure damaged the catalyst through friction and led higher Ru losses, mainly through the release of carbon domains containing Ru. Metal oxides were compared to AC by synthesising 2%Ru catalysts on alpha-Al2O3, ZrO2 and TiO2. They yielded 20-40 times higher Ru loss rates than for 2%Ru/AC and a significantly lower activity, confirming once again the superiority of Ru/C as SCWG catalyst. Ru losses were similar on larger rigs during glycerol and sewage sludge gasification, with values around 0.14-0.29 µg gRu-1 h-1.With Ru/CNF proving to be an interesting SCWG catalyst, more in-depth studies were performed on this system. Catalysts of different loadings (1-30%) were successfullysynthesised yielding very small Ru NPs (0.9-2.2 nm) with an easy synthesis method. Ru/CNF catalysts exhibited high gasification activities and improved stability compared to Ru/AC. The initial activity correlated with the Ru dispersion. However, 1%Ru/CNF catalysts underwent rapid deactivation compared to 5%Ru/CNF, showing the importance of site density to avoid rapid deactivation. The effect of surface Ru atom density was shown with a optimum in turnover frequency in the range 0.4-0.7 atomRu,sfc nm-2. For the first time, a particle size effect and more importantly a surface atom density effect was shown during SCWG of glycerol. Coke deposition was also investigated and observed at very high space velocities. The coke deposits could partially be removed by extraction in a mix of solvents, opening a potential new route for the regeneration of Ru/C catalysts.