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.

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Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis.

Despite substantial advances in crystal structure determination methodology for polycrystalline materials, some problems have remained intractable. A case in point is the zeolite catalyst IM-5, whose structure has eluded determination for almost 10 years. Here we present a charge-flipping structure-solution algorithm, extended to facilitate the combined use of powder diffraction and electron microscopy data. With this algorithm, we have elucidated the complex structure of IM-5, with 24 topologically distinct silicon atoms and an unusual two-dimensional medium-pore channel system. This powerful approach to structure solution can be applied without modification to any type of polycrystalline material (e.g., catalysts, ceramics, pharmaceuticals, complex metal alloys) and is therefore pertinent to a diverse range of scientific disciplines.

https://science.sciencemag.org/content/sci/315/5815/1113.full.pdf

Structure of the polycrystalline zeolite catalyst IM-5 solved by enhanced charge flipping.

One of the major goals in catalysis is to improve the capabilities of microporous materials. This can be accomplished by synthesizing new zeolites with controlled pore architectures. In particular, zeolites containing channels of different sizes in the same structure are desirable. Here, we report a zeolite containing fully interconnected 8-, 10- and 12-membered-ring pores, synthesized by combining the structure-directing effect of the organic 1,5-bis-(methylpyrrolidinium)-pentane and the framework isomorphic substitution of germanium for silicon. Analysis of the crystal structure determined by direct methods from synchrotron powder diffraction data reveals 16 independent tetrahedrally coordinated atoms. This thermally and hydrothermally stable zeolite structure, when synthesized in its acidic form by incorporating aluminium in the framework, presents unique catalytic shape-selectivity effects derived from its particular pore topology.

A zeolite with interconnected 8-, 10- and 12-ring pores and its unique catalytic selectivity.

Four 3D 10-ring zeolites, IM-5, TNU-9, ZSM-11 and ZSM-5, with Si/Al = 14–24 and crystal sizes below 2 microns, were tested as catalysts for the methanol to hydrocarbons reaction (MTH) at atmospheric pressure, 350 °C and WHSV = 9 h−1. All catalysts gave initially full methanol conversion, and showed strikingly similar effluent product selectivities. However, their life-time duration differed significantly, and decreased in the order: ZSM-11 > ZSM-5 ≫ TNU-9 > IM-5. A main difference between the two groups of stability behaviour was the size of cavities formed by channel intersections; larger cavities in TNU-9 and IM-5 leading to polyaromatics formation and a more rapid deactivation compared to ZSM-5 and ZSM-11. Effluent yield–conversion plots suggested that polymethylated benzene intermediates were more important in IM-5 and TNU-9 than in ZSM-5 and ZSM-11, where alkene methylation and cracking reactions seemed to dominate product formation. However, this difference had only minor influence on effluent selectivity.

J.A. Perdigón-Melón

Papers

Determination of the Pore Topology of Zeolite IM-5 by Means of Catalytic Test Reactions and Hydrocarbon Adsorption Measurements