Computer-Aided Design (CAMD) of Deep Eutectic Solvent (DES) based Processes for the Separation of Natural Components from Liquid Mixtures

近10年来，人们发现深度共晶溶剂(DES)非常适合于天然产物混合物的温和分离。DES具有低熔点、可忽略的蒸汽压和分子可调的物理化学性质。到目前为止，基于DES的天然产物混合物分离过程的研究主要集中在氢键供体(HBD)和氢键受体(HBA)不同组合形成DES体系的实验研究。DES组分的系统选择、分子设计及其工艺级性能评价研究较少。为了缩小这些知识差距，拟议的项目旨在开发一种基于模型的方法，将DES系统的设计与合成有效分离天然产品混合物的最佳工艺相结合。以从亚油酸甲酯中分离生育酚(维生素E)为例。首先，通过计算机辅助筛选方法确定与目标产物生育酚(作为HBD)形成DES系统的潜在HAB-候选者。其次，对生育酚/HBA二元混合物的固液平衡进行了实验研究。通过这种方式，识别出了在现实中也显示了预测的共晶行为的DES系统。对于这些经过验证的DES体系，测量了HBA/生育酚/亚油酸甲酯三元混合物的液液平衡(LLE)以及与工艺相关的其他性质(如粘度、热容)。第三，基于实验的SLE和LLE数据，用PC-SAFT状态方程模拟了DES的相行为。第四，利用超结构方法确定了每个DES体系的最佳分离过程，包括萃取级和结晶级。此外，还利用a基团贡献法(GC-PC-SAFT)同时进行了最佳分离工艺的合成和DES组分的分子结构优化。通过使用这种设计方法，创新的共晶溶剂系统和高效的萃取-结晶过程将被确定。选定的基于模型的预测在一个模块化的微型工厂中进行了实验验证。

In the last 10 years, deep eutectic solvents (DES) have been discovered that are very suitable agents for the mild separation of natural product mixtures. DES have a low melting point, negligible vapor pressure and molecularly tunable physico-chemical properties. So far, the research activities on DES-based separation processes for natural product mixtures were mainly focused on the experimental investigation of different combinations of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA) to form DES systems. The systematic selection and the molecular design of DES components as well as their process-level performance evaluation were rarely investigated. For closing these knowledge gaps, the proposed project is aiming at the development of a model-based methodology to combine the design of DES systems with the synthesis of optimal processes for the efficient separation of natural product mixtures. The separation of tocopherol (vitamin E) from methyllinoleate is taken as a practically relevant example. First, potential HAB-candidates for the formation of DES systems with the target product tocopherol (acting as HBD) are identified by a computer-aided screening approach. Second, the solid-liquid equilibria (SLE) of the binary tocopherol/HBA-mixtures are investigated experimentally. In this way, the DES systems are identified that show the predicted eutectic behavior also in reality. For these validated DES systems, the liquid-liquid equilibria (LLE) of the ternary HBA/tocopherol/methyllinoleate-mixtures and further process-relevant properties (e.g. viscosity, heat capacity) are measured. Third, based on the experimental SLE and LLE data, the PC-SAFT equation of state is used for modelling the DES phase behavior. Fourth, for each modelled DES system, the optimal separation process consisting of extraction and crystallization stages is determined by means of a superstructure approach. Moreover, a a group contribution method (GC-PC-SAFT) is used to perform the synthesis of the optimal separation process and the optimization of the molecular structure of the DES components simultaneously. By use of this design methodology, innovative eutetic solvent systems and highly efficient extraction-crystallization processes are to be identified. Selected model-based predictions are validated experimentally in a modular miniplant.