Integrated solvent and process design exemplified for a Diels–Alder reaction

Abstract

A new kind of solvent descriptor obtained from quantum chemical calculations is introduced. Group contributions to each solvent descriptor are regressed for 71 UNIFAC groups. A reaction kinetic model is built by correlating a set of experimentally determined reaction rate constants in various solvents with the corresponding theoretical solvent descriptors. Based on the kinetic model and the developed group contribution method, a computer-aided molecular design problem is formulated and optimal solvents to achieve highest reaction rates are identified. For considering the multiple and complicated effects of solvents on a chemical process, an integrated solvent and process design is performed. Solvent molecular structures and process operations are simultaneously optimized by the formulation and solution of a mixed-integer nonlinear program. The proposed design methodology is exemplified for a selected Diels-Alder reaction.

Robust design of optimal solvents for chemical reactions—A combined experimental and computational strategy

“…Afterwards, the six area parameters are used as solvent theoretical descriptors to quantify their effects on reaction rates. For more detailed information on the solvent descriptors, please refer to Zhou et al (2015).…”

“…previously developed group contribution (GC) method(Zhou et al, 2015) is an effective and reliable tool to estimate the six solvent descriptors based on the group combination of solvent molecules. With the kinetic models (Eq.…”

Integrating superstructure‐based design of molecules, processes, and flowsheets

“…The discrete molecular structure makes the integrated design problem a challenging mixed‐integer nonlinear programming (MINLP) problem (for a recent review see Papadopoulos et al). In literature, frameworks for integrated design based on CAMD have been developed, for example, for the design of working fluids for ORCs, refrigerants for heat pumps, mixtures, solvents for absorption processes, extraction processes, or reactions . Methods for the integrated design of processes and molecules usually consider a fixed pre‐defined process flowsheet configuration.…”

“…In literature, frameworks for integrated design based on CAMD have been developed, for example, for the design of working fluids for ORCs, [15][16][17][18][19][20][21][22][23] refrigerants for heat pumps, 24,25 mixtures, 25,26 solvents for absorption processes, [27][28][29][30][31][32][33] extraction processes, 34,35 or reactions. 36 Methods for the integrated design of processes and molecules usually consider a fixed predefined process flowsheet configuration. However, the choice of the right flowsheet is crucial to maximize the thermodynamic and thermoeconomic performance of the processes.…”

Outer approximation algorithm with physical domain reduction for computer‐aided molecular and separation process design

“…Although this model is highly nonlinear, the tractability of the problem was ensured by considering a continuous molecular design space. The direct solution of the MINLP arising from the CAMPD problem was adopted by Zhou et al 41 to design a reactive process and the corresponding reaction solvent, including the recovery of the solvent from the reaction products by distillation. The complexity of the process model was tailored to make the problem tractable.…”