The role of synthesis gas in tomorrow’s sustainable fuels

In a new publication in Nature Communications, a team from the Dutch company Syngaschem BV and the Dutch Institute for Fundamental Energy Research elucidates for the first time some aspects of the Fischer-Tropsch reaction, used for converting synthesis gas into synthetic fuels.

Analysis performed at HIPPIE beamline at MAX IV were instrumental to achieve these results. The adoption of sustainable and renewable energy sources to permanently move beyond the dependence from fossil fuels constitutes one of the great challenges of our time. One that is made more urgent by the effects of climate change we witness on a daily basis. Electrification, such as we see in the development of electric vehicles, seems a promising strategy, but it cannot be the solution for all applications. In many cases liquid fuels are still considered the best and most efficient option. Is there a way to produce liquid fuels in an efficient and sustainable manner, one that does not rely on fossil sources?

>Read more on the MAX IV website

Superfluorescent emission in the UV range

Free-electron laser FLASH coaxes superfluorescent emission from the noble gas xenon

Scientists have for the first time induced superfluorescence in the extreme ultraviolet range. Superfluorescence, or superradiance, could be used to build a laser that does not require an optical resonator. The team headed by DESY’s lead scientist Nina Rohringer used DESY’s free-electron laser FLASH to stimulate xenon, a noble gas, inside a narrow tube, causing it to emit coherent radiation, like a laser. The research team is now presenting its work in the journal Physical Review Letters.

“The phenomenon of superfluorescence was first discovered in the microwave range in the 1970s, and then demonstrated for infrared and optical wavelengths too,” explains Rohringer. “In the meantime, superfluorescence has also been observed in the X-ray domain, and at one time this mechanism was believed to be a promising candidate for building X-ray lasers. Until now, however, superfluorescence had not been demonstrated in the extreme ultraviolet, or XUV, range.”

In superfluorescence, the incident light is amplified and emitted along the axis of the medium as a narrow beam of coherent radiation, like in a laser. To produce superfluorescence in the XUV spectrum, the incoming light needs to have enough energy to knock the electrons out of the inner shell of the atoms that make up the lasing medium. Redistribution within the electron shell (Auger decay) leads to a situation in which more particles find themselves in an excited state than in an unexcited state. Physicists refer to this as population inversion.

>Read more on the FLASH at DESY website

Image: The xenon superfluorescence shows up as a bright line (yellow) superimposed on the averaged free-electron laser spectrum (purple, averaged over many shots).
Credit: European XFEL, Laurent Mercadier

Publication of the first scientific paper

June 1, 2019 marks a historically important accomplishment for SESAME, where the very first scientific paper presenting results using data obtained at SESAME’s X-ray absorption fine structure/X-ray fluorescence (XAFS/XRF) spectroscopy beamline was published in Applied Catalysis B: Environmental.

S: Bac et al. Applied Catalysis B: Environmental, 259, 2019, 117808 https://www.sciencedirect.com/science/article/pii/S0926337319305545

Synchrotron measurements performed at SESAME were carried out by the research group of Associate Professor Emrah Ozensoy (Bilkent University Chemistry Department and UNAM-National Nanotechnology Center Ankara, Turkey), in collaboration with the research group of Professor Ahmet Kerim Avcı (Boğaziçi University, Chemical Engineering Department, Istanbul, Turkey) and Dr Messaoud Harfouche (XAFS/XRF beamline scientist, SESAME, Allan, Jordan).
The paper entitled Exceptionally active and stable catalysts for CO2 reforming of glycerol to syngas is the outcome of a measurement campaign at SESAME in July 2018 and focuses on the catalytic valorization of a biomass waste material (i.e. glycerol) to obtain synthesis gas (or syngas, CO + H2). Glycerol is an important renewable feedstock for the large-scale catalytic production of synthetic liquid fuels through a process called Fischer-Tropsch synthesis. In the words of Emrah Ozensoy “XAFS/XRF experiments performed at SESAME were instrumental for us to understand the electronic structure of the Co/CoOx and Ni/NiOx nanoparticles serving as the catalytic active sites. Particularly, complementing the experimental data acquired in our labs with the results obtained at SESAME allowed us to examine the nature of the fresh catalysts and compare them with that of the spent catalysts obtained after the catalytic reaction, revealing crucial molecular-level insights regarding the catalytic aging and poisoning mechanisms.”

>Read more on the SESAME website

Image: Kerem Emre Ercan Some of the researchers who contributed to the publication and data acquisition (from left to right, Yusuf Koçak, Kerem E. Ercan, and M. Fatih Genişel)

Direct Observation of the Kinetics of Gas–Solid Reactions

… using in-situ kinetic and spectroscopic techniques.

Copper oxide is a widely used adsorptive material that removes trace amounts of H2S from various process streams via chemical reaction to form copper sulfide. At room temperature the thermodynamics favor a near complete conversion of CuO to copper sulfide in the presence of H2S. However, in application, the extent of conversion of the CuO to copper sulfide during reaction can be influenced by many factors, including the initial crystalline state of the CuO, and the rate at which solid products accumulate on the reactive surfaces or within pores of the CuO particles. This incomplete utilization of CuO is problematic for industrial applications because it typically leads to oversized equipment and/or frequent process shutdowns. Developing fundamental insight at the atomic scale for this reaction could overcome these limitations by providing a rational basis for the design of new materials and by leading to predictive models that allow for current materials to be operated toward their thermodynamic limits. Thus, experiments that combine reaction kinetic testing while also simultaneously capturing chemical and structural changes in the solid phase at multiple length scales are necessary to elucidate the fundamentals of these reactions at various length scales.

Previous studies were successful in semi-quantitatively relating properties of materials to performance in fixed-bed systems, however, differences in performance were often attributed to physical properties at the >10 mm scale (e.g., surface area, pore volume, bulk density). The effects of molecular scale material characteristics (e.g., microscopic shape, metal oxide crystallite size, and surface composition) were rarely investigated, thus, it is difficult to extend the conclusions from these studies across a broad range of conditions and materials.

>Read more on the SSRL at SLAC website

Image (extract): (A) CuO and CuS concentration maps derived from XANES analysis of TXM images of individual CuO particle during reaction with 1000 ppm H2S. (B) Fractional conversion versus time (derived from linear combination fitting of Cu K-edge XANES) of fixed beds of CuO particles consisting of 2 different crystallite sizes (red circles are 2.8 nm and blue squares are 28 nm) and of individual CuO particles. See the entire figure here.