Fluid catalytic cracking (FCC) is one of the major conversion technologies in the oil refinery industry. FCC currently produces the majority of the world's gasoline, as well as an important fraction of propylene for the polymer industry. In this critical review, we give an overview of the latest trends in this field of research. These trends include ways to make it possible to process either very heavy or very light crude oil fractions as well as to co-process biomass-based oxygenates with regular crude oil fractions, and convert these more complex feedstocks in an increasing amount of propylene and diesel-range fuels. After providing some general background of the FCC process, including a short history as well as details on the process, reactor design, chemical reactions involved and catalyst material, we will discuss several trends in FCC catalysis research by focusing on ways to improve the zeolite structure stability, propylene selectivity and the overall catalyst accessibility by (a) the addition of rare earth elements and phosphorus, (b) constructing hierarchical pores systems and (c) the introduction of new zeolite structures. In addition, we present an overview of the state-of-the-art micro-spectroscopy methods for characterizing FCC catalysts at the single particle level. These new characterization tools are able to explain the influence of the harsh FCC processing conditions (e.g. steam) and the presence of various metal poisons (e.g. V, Fe and Ni) in the crude oil feedstocks on the 3-D structure and accessibility of FCC catalyst materials.

Hydrocarbon conversion catalysts suffer from deactivation by deposition or formation of carbon deposits. Carbon deposit formation is thermodynamically favored above 350 °C, even in some hydrogen‐rich environments. We discuss four basic mechanisms: a carbenium‐ion based mechanism taking place on acid sites of zeolites or bifunctional catalysts, a metal‐induced formation of soft coke (i.e., oligomers of small olefins) on bifunctional catalysts, a radical‐mediated mechanism in higher‐temperature processes, and fast‐growing carbon filament formation. Catalysts deactivate because carbon deposits block pores at different length scales, or directly block active sites. Some deactivated catalysts can be re‐used, others can be regenerated or have to be discarded. Catalyst and process design can mitigate the effects of deactivation. New analytical tools allow for the direct observation (in some cases even under in situ or operando conditions) of the 3D‐distribution of coke‐type species as a function of catalyst structure and lifetime.

Nickel metal nanoparticles are intensively researched for the catalytic conversion of carbon dioxide. They are commercially explored in the so-called power-to-methane application in which renewably resourced H₂ reacts with CO₂ to produce CH₄, which is better known as the Sabatier reaction. Previous work has shown that this reaction is structure-sensitive. For instance, Ni/SiO₂ catalysts reveal a maximum performance when nickel metal nanoparticles of ∼2-3 nm are used. Particularly important to a better understanding of the structure sensitivity of the Sabatier reaction over nickel-based catalysts is to understand all relevant elementary reaction steps over various nickel metal facets because this will tell as to which type of nickel facets and which elementary reaction steps are crucial for designing an efficient nickel-based methanation catalyst. In this work, we have determined by density functional theory (DFT) calculations and micro-kinetics modeling (MKM) simulations that the two terrace facets Ni(111) and Ni(100) and the stepped facet Ni(211) barely show any activity in CO₂ methanation. The stepped facet Ni(110) turned out to be the most effective in CO₂ methanation. Herein, it was found that the dominant kinetic route corresponds to a combination of the carbide and formate reaction pathways. It was found that the dissociation of H₂CO* toward CH₂* and O* is the most critical elementary reaction step on this Ni(110) facet. The calculated activity of a range of Wulff-constructed nickel metal nanoparticles, accounting for varying ratios of the different facets and undercoordinated atoms exposed, reveals the same trend of activity-versus-nanoparticle size, as was observed in previous experimental work from our research group, thereby providing an explanation for the structure-sensitive nature of the Sabatier reaction.