Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were performed using a 5 wt% Pd on activated carbon in custom-designed high pressure autoclaves at 323 K. The Cubic-Plus-Association (CPA) equation of state was employed to model the phase behaviour of the experimentally studied systems. CPA binary interaction parameters were estimated based on the experimental vapour–liquid or liquid–liquid equilibria data available in the literature. No experimental data for the CO2–2-butenal binary system were available in the literature; therefore, the bubble points of this mixture of varying composition at three different temperatures were measured in a high-pressure view cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved in the so-called “expanded liquid” region, which is located near the critical point of the reacting mixture. It was also found that in this point the hydrogen concentration achieved its maximum in the CO2-expanded phase. Furthermore, the pressure – temperature regions where the multicomponent reaction system exists in one single phase and in multiphase were calculated.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (128 K)Download as PowerPoint slideHighlights► Pd-catalysed hydrogenation of 2-butenal to butanal in CO2. ► Bubble point pressures for the 2-butenal–CO2 binary were measured. ► Pure fluid and binary interaction parameters of the CPA EoS were estimated. ► Using CPA the number and composition of phases during the reaction were predicted. ► Highest catalytic conversion at the transition from two phases to a single phase.