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

• Applicant: Professor Dr.-Ing. Kai Sundmacher
• Subject Area: Chemical and Thermal Process Engineering
• Term: from 2019 to 2022
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 411446655

• Final Report Year: 2022

Final Report Abstract

In order to design suitable DES-based extraction process for separating natural product, in this project, we first developed diverse approaches for predicting the formation of DESs, and then proposed a systematic screening methodology for identifying DESs or DES components from a large number of combinations or component candidates. The COSMO-RS model, two UNIFAC models, and a R-S theory-based QSAR model were evaluated for predicting the SLE of DES systems. A COSMO-RS descriptors’ based QSAR model was developed for estimating the melting point depression of ChCl-based DESs. By means of these four models, we could reasonably predict the SLE or at least Te of DES systems for given different HBA-HBD combinations. This helps a lot to estimate whether DES could form, and if so, whether the formed DES will satisfy given constraints regarding the desired operating temperature window. For α-tocopherol extraction when directly using DESs as extracting agents, a systematic DES screening framework was proposed by combining extraction performance evaluation (COSMO-RS), Environment-Health-Safety (EHS) criteria (by VEGA software), SLE and LLE calculations (COSMO-RS), experimental validation and process simulation (Aspen Plus). By using the special DES [P4,4,4,4][Cl]:MEA (at mass mixing ratio of 2:1) as extracting agent in a continuous separation process, 95.1% purity and 55.8% recovery ratio of α-tocopherol could be achieved, of hexane is applied for re-extraction. Furthermore, considering the weak HBD ability of α-tocopherol and linalool, a DES screening was done to select a suitable HBA component, forming a DES in-situ with the target molecules. From initially collected 80 HBA candidates, after the evaluation of their extraction potential and estimation of their DES formation ability, [P4,4,4,4][Cl] and [N4,4,4,4][Cl] were selected as the most promising HBA components for the extraction of α-tocopherol and linalool, respectively. The experimental evaluation and process optimization were performed for the case of linalool extraction, and a complete process flowsheet including the linalool/limonene separation and solvent recycling was developed to obtain 98.8% purity and 89.2% recovery ratio got linalool. To conclude, the proposed screening methodology developed for the selection of DES systems or DES components suitable for natural product extraction is a very versatile tool which can be applied to a broad spectrum of similar separation tasks.

Publications

• Computer-aided screening of deep eutectic solvent systems for separation processes. 4th International Conference on Ionic Liquids in Separation and Purification Technology (ILSEPT), Sitges, Spain.
  Song, Z., Zhou, T., Qi, Z. & Sundmacher, K.
  
• Extending the UNIFAC model for ionic liquid–solute systems by combining experimental and computational databases. AIChE Journal, 66(2).
  Song, Zhen; Zhou, Teng; Qi, Zhiwen & Sundmacher, Kai
  
• Deep Deterpenation of Citrus Essential Oils Intensified by In Situ Formation of a Deep Eutectic Solvent in Associative Extraction. Industrial & Engineering Chemistry Research, 59(19), 9223-9232.
  Li, Jiangwuji; Wang, Jingwen; Wu, Mingyao; Cheng, Hongye; Chen, Lifang & Qi, Zhiwen
  
• Systematic Screening of Deep Eutectic Solvents as Sustainable Separation Media Exemplified by the CO2 Capture Process. ACS Sustainable Chemistry & Engineering, 8(23), 8741-8751.
  Song, Zhen; Hu, Xutao; Wu, Hongyi; Mei, Mingcan; Linke, Steffen; Zhou, Teng; Qi, Zhiwen & Sundmacher, Kai
  
• Computer-aided screening of deep eutectic solvent systems for the associative extraction of α-tocopherol from deodorizer distillate. 31st European Symposium on Computer-Aided Process Engineering (ESCAPE-31), Istanbul, Turkey.
  Song, Z., Zhou, T., Qi, Z. & Sundmacher, K.
  
• Computer-Aided Screening of Deep Eutectic Solvent Systems for the Associative Extraction of α-Tocopherol from Deodorizer Distillate. Computer Aided Chemical Engineering, 341-346. Elsevier.
  Song, Z.; Zhou, T.; Qi, Z. & Sundmacher, K.
  
• Evaluation of COSMO-RS for solid–liquid equilibria prediction of binary eutectic solvent systems. Green Energy & Environment, 6(3), 371-379.
  Song, Zhen; Wang, Jingwen & Sundmacher, Kai
  
• Extractive deterpenation of citrus essential oils using quaternary ammonium-based deep eutectic solvents. Journal of Molecular Liquids, 336, 116868.
  Wu, Mingyao; Cheng, Hongye; Chen, Lifang & Qi, Zhiwen
  
• Neural recommender system for the activity coefficient prediction and UNIFAC model extension of ionic liquid‐solute systems. AIChE Journal, 67(4).
  Chen, Guzhong; Song, Zhen; Qi, Zhiwen & Sundmacher, Kai
  
• Comparative screening of organic solvents, ionic liquids, and their binary mixtures for vitamin E extraction from deodorizer distillate. Chemical Engineering and Processing - Process Intensification, 171, 108711.
  Qin, Hao; Song, Zhen; Qi, Zhiwen & Sundmacher, Kai
  
• Computer-aided design of biphasic system comprising ionic liquid and conventional solvent to extract α-tocopherol from deodorizer distillate. 32st European Symposium on Computer-Aided Process Engineering (ESCAPE-32), Toulouse, France.
  Qin, H., Song, Z., Qi, Z. & Sundmacher, K.
  
• Rational eutectic solvent design by linking regular solution theory with QSAR modelling. Chemical Engineering Science, 262, 118042.
  Chen, Jiahui; Zhu, Fengyuan; Qin, Hao; Song, Zhen; Qi, Zhiwen & Sundmacher, Kai
  
• Rational Screening of Deep Eutectic Solvents for the Direct Extraction of α-Tocopherol from Deodorized Distillates. ACS Sustainable Chemistry & Engineering, 10(25), 8216-8227.
  Cheng, Jie; Qin, Hao; Cheng, Hongye; Song, Zhen; Qi, Zhiwen & Sundmacher, Kai