Application of Adsorptive Reactors for the Reverse Water Gas Shift ReactionCarbon dioxide can serve as a C 1 building block for chemical syntheses. To increase the reactivity of CO 2 it may be reduced to carbon monoxide with hydrogen using an adsorptive reactor for the reverse water gas shift (rWGS) reaction. Both model simulations and experimental studies have been conducted to demonstrate the proof of principle and to assess the performance of an adsorptive rWGS reactor. The results show that application of the adsorptive reactor concept increased the equilibrium conversion at 225 -250°C significantly.

A combination of steady-state catalytic tests, transient studies with isotopic tracers, and kinetic modeling was used to derive detailed insights into the individual reaction pathways in the course of toluene acetoxylation over a Pd−Sb/ TiO 2 catalyst. This reaction can be considered as an environmentally friendly route for the production of benzyl alcohol. Benzyl acetate and benzaldehyde are the only products formed from toluene, while acetic acid gives CO 2 in addition to benzyl acetate. The Arrhenius plots revealed apparent activation energies for formation of benzyl acetate and benzaldehyde of 24.9 and 27.5 kJ mol −1 , respectively, thus, indicating that these products originate from the same surface intermediate, i.e. benzyl cation. The corresponding value for CO 2 formation was 152.9 kJ mol −1 . Transient isotopic studies and their kinetic evaluation demonstrated the participation of lattice oxygen and adsorbed oxygen species in activation of acetic acid, with the latter species favoring oxidation of the acid to CO 2 .

An imine synthesis was investigated in a nearly isothermal oscillating segmented flow microreactor at different temperatures using non-invasive Raman spectroscopy. Multivariate curve resolution provided a calibration-free approach for obtaining kinetic parameters. The two different multivariate curve resolution approaches, soft and hard modeling, were applied and contrasted, leading to similar results. Taking heat and mass balance into account, the proposed kinetic model was applied for a model-based scale-up prediction. Finally, the reaction was performed in a 0.5 L semi-batch reactor, followed by in-line Raman spectroscopy and off-line gas chromatography analysis. The successful scale-up was demonstrated with a good agreement between measured and predicted concentration profiles. Highlights • Oscillation segmented flow reactor with inline Raman spectroscopy. • Multivariate Curve Resolution with hard and soft constraints. • High quality kinetic model for scale-up predictions. Graphical abstract

The origins of surface carbon species in the acetoxylation of toluene to benzyl acetate over Pd–Sb/TiO2 catalyst and their formation pathways were systematically investigated.