Kinetic Modeling of Catalytic Olefin Cracking and Methanol-to-Olefins (MTO) over Zeolites: A Review

The increasing demand for lower olefins requires new production routes besides steam cracking and fluid catalytic cracking (FCC). Furthermore, less energy consumption, more flexibility in feed and a higher influence on the product distribution are necessary. In this context, catalytic olefin cracking and methanol-to-olefins (MTO) gain in importance. Here, the undesired higher olefins can be catalytically converted and, for methanol, the possibility of a green synthesis route exists. Kinetic modeling of these processes is a helpful tool in understanding the reactivity and finding optimum operating points; however, it is also challenging because reaction networks for hydrocarbon interconversion are rather complex. This review analyzes different deterministic kinetic models published in the literature since 2000. After a presentation of the underlying chemistry and thermodynamics, the models are compared in terms of catalysts, reaction setups and operating conditions. Furthermore, the modeling methodology is shown; both lumped and microkinetic approaches can be found. Despite ZSM-5 being the most widely used catalyst for these processes, other catalysts such as SAPO-34, SAPO-18 and ZSM-23 are also discussed here. Finally, some general as well as reaction-specific recommendations for future work on modeling of complex reaction networks are given.