In Situ Infrared Spectroscopy as a Tool for Monitoring Molecular Catalyst for Hydroformylation in Continuous Processes

Non-invasive in situ monitoring of catalyzed chemical reactions can show and probe the stability of the catalyst and ensure a high yield of the desired chemical processes. Infrared in situ measurement techniques in attenuated total reflection (ATR) and transmission mode were used to assess the feasibility of these methods and ultimately compare their ability to monitor and detect active or degrading catalyst species. Four different process configurations were used, namely (i) a stirred tank reactor equipped with ATR-IR; (ii) a continuously operated miniplant with ATR-IR; (iii) a continuously operated miniplant with transmission-IR; (iv) a stirred tank reactor equipped with transmission-1R The established hydroformylation of a long-chain olefin catalyzed by a rhodium-phosphite catalyst was taken as a representative reaction. The potential for process monitoring in molecular catalysis was evaluated. Advanced chemometric analyses by Band Target Entropy Minimization (BTEM) were performed following spectral monitoring to obtain pure component spectra estimates as well as relative time-dependent concentration profiles. In general, this study showed that infrared measurements in transmission mode are able to detect active catalytic species and can follow deactivation phenomena in batch reactions and continuously operated miniplants. Apart from the substrates and products, a number of catalytic intermediates appear to be in equilibrium exchange at reaction conditions and hence the deconvolution of multispecies spectra exhibits superimpositions of these species. Quantum chemical calculations support the structural identification of measured vibrational spectra. This comparative study of ATR versus transmission and batch experiment versus continuously operated miniplant shows that transmission IR is capable of getting in-depth spectroscopic data that can be deconvoluted by BTEM. A distinct dosing strategy is important to get meaningful data on the molecular catalyst under process conditions. This study gives a unique perspective on in situ spectroscopic infrared investigations in molecular catalysis and future process control.