Coking leads to the deactivation of solid acid catalyst. This phenomenon is a ubiquitous problem in the modern petrochemical and energy transformation industries. Here, we show a method based on microwave cavity perturbation analysis for an effective examination of both the amount and the chemical composition of cokes formed over acid zeolite catalysts. The employed microwave cavity can rapidly and non-intrusively measure the catalytically coked zeolites with sample full body penetration. The overall coke amount is reflected by the obtained dielectric loss (ε″) value, where different coke compositions lead to dramatically different absorption efficiencies (ε″/cokes’ wt%). The deeper-dehydrogenated coke compounds (e.g., polyaromatics) lead to an apparently higher ε″/wt% value thus can be effectively separated from lightly coked compounds. The measurement is based on the nature of coke formation during catalytic reactions, from saturated status (e.g., aliphatic) to graphitized status (e.g., polyaromatics), with more delocalized electrons obtained for enhanced Maxwell–Wagner polarization.

Methanol-to-hydrocarbon (MTH) process over acidic zeolite catalysts has been widely utilised to yield many types of hydrocarbons, some of which are eventually converted into the highly dehydrogenated (graphitized) carbonaceous species (cokes). The coking process can be divided into two parallel pathways based on the accepted hydrocarbon pool theory. From extensive investigations, it is reasonable to conclude that inner zeollite cavity/channel reactions at acidic sites generate cokes. However, coke formation and accumulation over the zeolite external surfaces play a major role in reaction deactivation as they contribute a great portion to the total coke amount. Herein we have reviewed previous literatures and included some recent works from KOPRC in understanding the nature and mechanism of coke formation, particularly during an H-ZSM-5 catalysed MTH reaction. We specially conclude that rapid aromatics formation at the zeolite crystalite edges is the main reason for later stage coke accumulation on the zeolite external surfaces. Accordingly, the catalyst deactivation is in a great certain to arise at those edge areas due to having the earliest contact with the incoming methanol reactant. The final coke structure is therefore built up with layers of poly-aromatics, as the potential sp 2 carbons leading to pre-graphite structure. We have proposed a coke formation model particularly for the acidic catalyst, which we believe will be of assistance in understanding-and hence minimising-the coke formation mechanisms.

A series of MoO3/H-ZSM-5 catalysts were prepared via calcination at a lower-than-usual temperature and evaluated.

In this work, some commercial nanoporousbased catalysts, such as USY, beta and mordenite zeolites loaded with Platinum metal acting as bifunctional catalysts, were used for hydroisomerisation experiments in a fixedbed reactor at the atmospheric pressure and at feed space time 5.12 h -1 to hydroisomerise n-heptane over a temperature range of 210-270°C. The study aimed to evaluate the changes with time-on-stream in the catalytic activity, product selectivity and manner of deactivation of metalloaded zeolite catalysts, at constant contact time of 5.13 h -1 and a hydrogen-to-n-heptane molar ratio fixed at 9. Various analytical techniques were used to characterise fresh and aged catalysts. Results show that pore architecture is the most important factor affecting coke formation and deactivation in zeolite catalysts, and those catalysts with three-dimensional pore structures lacking cavities or cages were best able to resist deactivation. In addition, it was found that those catalysts with high Si/Al ratios and those which had been acid-leached or steamed showed better activity, higher selectivity towards isomeric products and better time stability. Moreover, the balance between the number of metal sites and the number of acid sites played an important role in determining the activity, selectivity and stability of the bifunctional catalysts.

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We have recently developed a new extraction process for significantly reducing the olefin content in commercial FCC gasoline. To gain insights into the origins of this process, we have investigated the dissolution of the light liquid olefins 1-pentene and 1-hexene in methanol through computer modelling together with NMR spectroscopy. We find two important hydrogen bonding modes for methanol olefin interactions - namely, O-Hπ and C-HO.

Isobutene is an important intermediate compound in the petrochemical industry for the production of polymers (butyl rubber, polybutene, and isoprene) and methyl tert-butyl ether. In this work, the n-butane dehydroisomerization reaction in a membrane reactor (MR) was investigated by thermodynamic analysis in a wide range of temperatures, reaction pressures, and equilibrium hydrogen partial pressures, by means of a simplified reaction scheme. The shift of the equilibrium conversion in an MR was evaluated by taking into account the chemical reaction equilibrium and the permeative equilibrium through a 100% hydrogen-selective membrane. The evaluated limits imposed by thermodynamics on an MR are much wider than those of a traditional reactor so that a conversion of about 7 times higher could be obtained over that of the traditional process under a set of operating conditions. This gives a powerful indication on how the use of an MR can extend the thermodynamic limits of this reaction, in terms of conversion, even at thermodynamically unfavorable operating conditions.

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