Kevin McBride

Integrated Reaction-Extraction Process for the Hydroformylation of Long-Chain Alkenes with a Homogeneous Catalyst

Abstract A lingering issue with the hydroformylation of long-chain alkenes is the cost of catalyst leaching. One effective method to recover homogeneous catalysts is the use of thermomorphic solvent systems (TMS). However, catalyst leaching is still too high using the current solvents DMF and decane, limiting economic feasibility. This work presents extraction as a possible method for intensifying catalyst recovery when using a TMS for the hydroformylation of 1-dodecene. A thermodynamic model for determining the LLE of the solvent system and for catalyst leaching is developed for implementation within a process-wide optimization problem. Using this model, the optimal reactor design with an integrated downstream separation including the catalyst loss can be investigated in more detail. It is shown that in this process the reactor design strongly depends on catalyst recovery and that by using the proposed extraction cascade the process becomes economically viable and more robust in regards to reactor performance.

Computer-aided design of solvents for the recovery of a homogeneous catalyst used for alkene hydroformylation

Abstract Recent works have demonstrated the efficiency of thermomorphic solvent systems (TMS) in the recovery of homogeneous catalysts, especially for the hydroformylation of long-chain alkenes such as 1-dodecene. In this case, the TMS mixture was comprised of dimethylformamide and decane; however, these solvents were not rigorously screened and may represent a suboptimal solution for catalyst recovery. Also, in view of other homogeneously catalyzed reactions, a systematic approach to solvent selection for catalyst recycling is desirable. In this contribution we propose using an established approach by estimating solvent effects on catalyst solubility with the Conductor Like Screening Model for Real Solvents (COSMO-RS). A framework for TMS solvent screening based on the relative solubility of the catalyst ligand, reactant, and product as calculated using COSMO-RS is proposed.

Computer Aided Design of Green Thermomorphic Solvent Systems for Homogeneous Catalyst Recovery

Abstract This work presents a new computer-aided thermomorphic solvent system (TMS) design methodology for the recovery of homogeneous catalysts that incorporates quantitative structure-activity relationships (QSAR) to predict various environmental, health, and safety (EHS) criteria using modern software packages. The quantum chemical method Conductor-like Screening Model for Real Solvents (COSMO-RS) (Klamt, 1995) is used for predicting catalyst solubility and the liquid-liquid equilibrium behavior of potential TMS designs. This methodology is then exemplified on the hydroformylation of 1- decene using the rhodium-Biphephos (Rh-BPP) transition metal catalyst and several green TMS designs were identified. Two of these TMS were then selected for experimental validation of both their LLE behavior and reaction performance.