(285g) Determination of the Reaction Equilibrium and Kinetics of the Hydroamination of β-Myrcene with Morpholine in a Liquid-Liquid-Two-Phase-System

Myrcene is obtained from renewable raw materials such as pine plants and offers the possibility to replace petroleum-based synthesis routes without being in competition with the food production. One example for the possibility of replacing a petroleum-based product is terpenyl amine, which can be produced by hydroamination of myrcene with morpholine. Terpenyl amine is already industrially used in paints or inks.

In this study terpenyl amine is investigated by the hydroamination reaction of myrcene and morpholine and the goal is to set up an experimentally validated process model. The reaction requires a homogeneous platinum catalyst and heat supply to increase the reaction yield. A liquid-liquid-two-phase-system, composed of an organic phase and an aqueous phase, is used to achieve high selectivity in combination with a low catalyst loss. While the organic phase consists only of the reactant myrcene, the catalyst in addition to the second reactant morpholine is dissolved in the aqueous phase. Since the catalyst is practically not soluble in myrcene and myrcene does not dissolve in water, the reaction takes place only at the interface between the organic and the aqueous phase. After the reaction the product terpenyl amine partitions in the organic phase. By the use of this liquid-liquid-two-phase-system the loss of catalyst can be minimized.

For the design of an industrial relevant process, knowledge of the reaction equilibrium and the reaction kinetics is required. Furthermore, the dependency of the reaction equilibrium and the reaction kinetics on temperature has to be measured. The dependence between reaction equilibrium and temperature is experimentally determined in a glass reactor and can be described by the Van’t Hoff equation. In addition the calculation of the reaction enthalpy is possible via the Van’t Hoff equation. For the measurement of the reaction kinetics, a double stirred cell is used. This ensures a stable interfacial area while simultaneously mixing the two individual phases without intermixing them. Thus, the reaction kinetics can be concluded from the measurement of the concentrations of reactants and product at different temperatures over time. By using an Arrhenius approach the experimentally determined reaction rate coefficients are described as a function of the temperature. Hence, the activation energy and the pre-exponential factor are determined. Applying these two approaches, a process model for the calculation of the reaction equilibrium and the reaction kinetics can be developed. Additionally, this process model allows a simulation of an industrial process. With these results of the simulation, both the size of a reactor and the residence time can be defined for the industrial scale to meet production requirements.

Acknowledgement:

The project „Sustainable Chemical Synthesis (SusChemSys)“ is co-financed by the European Regional Development Fund (ERDF) and the state of North Rhine-Westphalia, Germany, under the Operational Programme „Regional Competitiveness and Employment“ 2003 - 2013.