Bridging the gap between industry and synchrotron: an operando study at 30 bar over 300 h during Fischer–Tropsch synthesis

Abstract

Bridging the gap between industry and synchrotron: an operando study at 30 bar over 300 h during Fischer-Tropsch synthesisWe design new infrastructure for operando high-pressure synchrotron experiments. High structural stability of a Fischer-Tropsch catalyst was found during a long-term study under industrial conditions while producing synthetic fuels.In order to reduce CO 2 emissions, it is necessary to substitute fossil fuels with renewable energy using CO 2 as a carbon feedstock. An attractive route for synthetic fuel production is the Fe-or Co-catalysed Fischer-Tropsch process. A profound knowledge of the catalyst deactivation phenomena under industrial conditions is crucial for the process optimisation. In this study, we followed the structural changes of a Co-Ni-Re/γ-Al 2 O 3 catalyst for >300 hours at 30 bar and 250°C during the Fischer-Tropsch synthesis operando at a synchrotron radiation facility. The advanced setup built for operando X-ray diffraction and X-ray absorption spectroscopy allows simultaneous and robust monitoring of the catalytic activity even over 300 h time on stream. We found three activity regimes for the Co-Ni-Re/γ-Al 2 O 3 catalyst during 310 h of operation. Fast decline in activity was observed during the initiation phase in the first hours of operation due to liquid film formation (mass transport limitations). Furthermore, solid state reactions and carbon depositions were found while continuing the exposure of the catalyst to harsh temperature conditions of 250°C. By using this advanced setup, we bridged the gap between industrially oriented catalysts and fundamental studies at synchrotron radiation facilities, opening up new possibilities for operando characterisation of industrial processes that rely on conditions of up to 450°C and 50 bar.

Stability of Cobalt Particles In and Outside HZSM‐5 under CO Hydrogenation Conditions Studied by ex situ and in situ Electron Microscopy

“…Those methods are performed preferably as close as possible to typical operating conditions. However, the detailed molecular understanding remains a significant technical challenge [27–30] …”

“…However, the detailed molecular understanding remains a significant technical challenge. [27][28][29][30] One of the most attractive techniques for characterization on an atomic scale is transmission electron microscopy (TEM), as it provides spatially-resolved information on the cobalt nanoparticle size distribution and the morphology. [31] In particular, environmental TEM (ETEM) allows investigation of the catalyst evolution under controlled gas environment and elevated temperatures.…”

Dynamically Operated Fischer–Tropsch Synthesis in PtL—Part 2: Coping with Real PV Profiles

“…The methods of choice for operando analysis would be X-ray absorption (XAS) techniques, X-ray diffraction (XRD), and a coupled GC-MS analysis [19,[52][53][54]. Those studies have been performed in an accompanied study and are subject of another publication under review [55].…”

CO2‐neutrale Fischer‐Tropsch‐Kraftstoffe aus dezentralen modularen Anlagen: Status und Perspektiven

“…Der getestete Katalysator büßt durch gezielte Prozessführung keine Aktivität ein, was einen Langzeitbetrieb unter dynamischen Betriebsbedingungen ermöglicht. Dies konnte durch In‐situ‐Experimente im Labor und am Synchrotron des KIT (Karlsruhe Research Accelerator KARA) bestätigt werden . Vermutlich existieren auf Syntheseseite keine Einschränkungen hinsichtlich der Geschwindigkeit von Lastwechseln.…”