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

在过去的10年中，已经发现深共熔溶剂（DES）是非常适合于天然产物混合物的温和分离的试剂。DES具有低熔点、可忽略的蒸气压和分子可调的物理化学性质。目前，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给体（HBD）和氢键受体（HBA）不同组合形成DES体系的实验研究上。DES组分的系统选择和分子设计以及它们的工艺水平性能评价很少被研究。为了弥补这些知识差距，拟议项目的目标是开发一种基于模型的方法，将DES系统的设计与有效分离天然产物混合物的最佳工艺的合成联合收割机结合起来。以生育酚（维生素E）与亚油酸甲酯的分离为例，进行了实际应用。首先，通过计算机辅助筛选方法鉴定用于与目标产物生育酚（充当HBD）形成DES系统的潜在HAB候选物。其次，实验研究了生育酚/羟基丁酸二元混合物的固液平衡。以这种方式，DES系统被识别为在现实中也显示预测的共晶行为。对于这些经验证的DES系统，测量了三元HBA/生育酚/亚油酸甲酯混合物的液液平衡（LLE）和其他工艺相关性质（例如粘度、热容）。第三，基于实验的SLE和LLE数据，PC-SAFT状态方程被用来模拟DES相行为。第四，对于每个建模DES系统，最佳的分离过程，包括萃取和结晶阶段的确定通过一个超结构的方法。此外，一个a基团贡献法（GC-PC-SAFT）进行合成的最佳分离工艺和DES组分的分子结构的优化，同时进行。通过使用这种设计方法，创新的低共熔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验证实验在一个模块化的微型工厂。

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.