Traditionally, methanol is produced in large amounts from synthesis gas with heterogeneous Cu/ZnO/Al₂O₃ catalysts under steady state conditions. In this paper, the potential of alternative forced periodic operation modes is studied using numerical optimization. The focus is a well-mixed isothermal reactor with two periodic inputs, namely, CO concentration in the feed and total feed flow rate. Exploiting a detailed kinetic model which also describes the dynamics of the catalyst, a sequential NLP optimization approach is applied to compare optimal steady state solutions with optimal periodic regimes. Periodic solutions are calculated using dynamic optimization with a periodicity constraint. The NLP optimization is embedded in a multi-objective optimization framework to optimize the process with respect to two objective functions and generate the corresponding Pareto fronts. The first objective is the methanol outlet flow rate. The second objective is the methanol yield based on the total carbon in the feed. Additional constraints arising from the complex methanol reaction and the practical limitations are introduced step by step. The results show that significant improvements for both objective functions are possible through periodic forcing of the two inputs considered here.

The Ni/AlMCM-41 was prepared and applied as the catalyst for the direct conversion of ethene to propene. Based on the results of the broad experimental study, two reaction networks were compared, one consisting of dimerization, isomerization and metathesis and a modified network suggesting the cracking of long-chain olefins. To correlate the experimentally obtained data, the classical Langmuir-Hinshelwood-Hougen-Watson model was applied for both reaction networks. The second network involving catalytic cracking offers a satisfying prediction of the observed product distributions.