The Coking of a Solid Catalyst Rationalized with Combined Raman and Fluorescence Lifetime Microscopy.

The formation of carbon deposits is a major deactivation pathway for solid catalysts. Studying coking on industrially relevant catalysts is, however, often challenging due to the sample heterogeneity. That is especially true for zeolite-containing catalysts where fluorescence often hampers their characterization with Raman spectroscopy. We turned this disadvantage into an advantage and combined Raman and fluorescence (lifetime) microscopy to study the coking behavior of an equilibrium catalyst material used for fluid catalytic cracking of hydrocarbons. The results presented illustrate that this approach can yield new insights in the physicochemical processes occurring within zeolite-containing catalyst particles during their coking process. Ex situ analyses of single catalyst particles revealed considerable intra-sample heterogeneities. The sample-averaged Raman spectra showed a higher degree of graphitization when the sample was exposed to more hexane, while the sample-averaged fluorescence lifetime showed no significant trend. Simultaneous in situ Raman and fluorescence (lifetime) microscopy, used to follow the coking of single particles, gave more insights in the changing fluorescence dynamics. The rise and decline of the average fluorescence lifetime suggested the prolonged presence of smaller coke species that are quenched more and more by adjacent larger polyaromatics acting as Förster-resonance-energy-transfer acceptors.

The refinery of the future.

Fossil fuels-coal, oil and gas-supply most of the world's energy and also form the basis of many products essential for everyday life. Their use is the largest contributor to the carbon dioxide emissions that drive global climate change, prompting joint efforts to find renewable alternatives that might enable a carbon-neutral society by as early as 2050. There are clear paths for renewable electricity to replace fossil-fuel-based energy, but the transport fuels and chemicals produced in oil refineries will still be needed. We can attempt to close the carbon cycle associated with their use by electrifying refinery processes and by changing the raw materials that go into a refinery from fossils fuels to carbon dioxide for making hydrocarbon fuels and to agricultural and municipal waste for making chemicals and polymers. We argue that, with sufficient long-term commitment and support, the science and technology for such a completely fossil-free refinery, delivering the products required after 2050 (less fuels, more chemicals), could be developed. This future refinery will require substantially larger areas and greater mineral resources than is the case at present and critically depends on the capacity to generate large amounts of renewable energy for hydrogen production and carbon dioxide capture.