Thermomorphic solvent selection for homogeneous catalyst recovery based on COSMO-RS

https://doi.org/10.1016/j.cep.2015.07.004Get rights and content
Under a Creative Commons license
open access

Highlights

  • TMS solvent selection framework based on catalyst solubility using COSMO-RS proposed.

  • Several hundred TMS mixtures identified based on solubility and phase behavior.

  • Experimental validation of promising TMS in partitioning and reaction performance.

Abstract

One method that has shown much promise due to its simplicity and effectiveness in homogeneous catalyst recovery is the use of thermomorphic solvent systems (TMS). In this contribution, a novel method for TMS solvent selection based on quantum chemical predictions of catalyst solubility and phase equilibrium is presented. This allows for solvent effects on the catalyst to be incorporated directly into the solvent screening process. A framework for TMS design is developed and implemented using the hydroformylation of 1-dodecene and the rhodium-Biphephos catalyst as an example reaction system. In this way, several promising TMS systems were identified. Experiments were then performed to validate the model based on catalyst partitioning and phase equilibrium. This was followed by conducting a series of reactions to investigate feasibility of the new TMS systems in the actual hydroformylation. In the end it was shown that although some problems arise from inconsistencies in phase equilibrium predictions, the method does provide a functioning a priori basis for TMS development.

Abbreviations

COSMO
Conductor-like Screening Model
COSMO-RS
Conductor-like Screening Model for Real Solvents
D
distribution of component between product and catalyst phases (% mass)
DMF
N,N-dimethylformamide
EHS
environment, health, and safety
HRSC
high relative solubility of the catalyst
LLE
liquid–liquid equilibrium
LRSC
low relative solubility of the catalyst
P
phosphorous
Rh
rhodium
TMS
thermomorphic solvent system
Y
yield of tridecanal

Keywords

Solvent screening
Solvent design
COSMO-RS
Homogeneous catalysis
Thermomorphic solvent systems

Cited by (0)