Modeling the thermodynamic and physical properties of Deep Eutectic Solvents

模拟低共熔溶剂的热力学和物理性质

• 批准号: RGPIN-2021-03901
• 负责人: Robelin, Christian
• 金额: $ 2.04万
• 依托单位: École Polytechnique de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2022
• 资助国家: 加拿大
• 起止时间: 2022-01-01 至 2023-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=753754
• 关键词: Modeling; thermodynamic; physical; properties; Deep

The objective of the proposed research program is to develop models for the thermodynamic (mainly phase diagram) and physical (mainly density and viscosity) properties of ternary systems of Deep Eutectic Solvents. The latter have been receiving increasing attention since, compared with "ionic liquids" (which are usually composed of a large organic cation and an inorganic anion, and melt at relatively low temperatures), they are cheaper to produce, less toxic and often biodegradable. For instance, they may be used as solvents for biocatalysis, organic synthesis, and dissolution and extraction processes. A typical binary Deep Eutectic Solvent consists of a mixture of a Hydrogen Bond Acceptor (HBA) - usually a quaternary ammonium salt such as choline chloride - and a Hydrogen Bond Donor (HBD) such as an amide, a carboxylic acid or an alcohol. For the thermodynamic model, the CALPHAD (CALculation of PHAse Diagrams) method will be used. It consists in developing Gibbs energy functions, calibrated on experimental data, for every phase in a chemical system, as a function of temperature, pressure and composition. Then, the combination and composition of phases corresponding to a global energy minimum is found. Models for the density and viscosity of multicomponent inorganic molten salts and "ionic liquid" mixtures of industrial interest, both linked to the thermodynamic model that gives an estimation of the structure of the melt, were previously developed. These models can then be used to estimate the properties of multicomponent salts from the assessed binary (and sometimes ternary) parameters, using standard interpolation techniques. The same methodology will be applied to various ternary Deep Eutectic Solvents, such as choline chloride-ZnCl2-HBA, choline chloride-HBA-HBD, choline chloride-ZnCl2-HBD, and choline chloride-HBD1-HBD2 (where HBA is a quaternary ammonium salt). The thermodynamic and physical property models will be calibrated on both data from the published scientific literature and newly obtained measurements (structural data, phase diagram, density, and viscosity). Using the developed models and databases, one will be able to search for and calculate automatically ternary Deep Eutectic Solvent compositions corresponding to a range of values of the liquidus temperature, density and viscosity, thus permitting to target specific industrial applications while avoiding an extremely tedious and costly trial and error experimental approach. Although Deep Eutectic Solvents emerged only about 15 years ago, they have numerous potential industrial applications, including the dissolution of lignin and the decontamination of recovered paper. A current objective of the scientific community through their use is to achieve a 40% reduction of energy use and an 80% reduction of CO2 emissions in pulp and papermaking, which is of prime importance in Canada.

拟议研究计划的目标是开发低共熔溶剂三元体系的热力学（主要是相图）和物理（主要是密度和粘度）特性模型。后者受到越来越多的关注，因为与“离子液体”（通常由大量有机阳离子和无机阴离子组成，并在相对较低的温度下熔化）相比，它们生产成本更低、毒性较小且通常可生物降解。例如，它们可用作生物催化、有机合成以及溶解和提取过程的溶剂。典型的二元低共熔溶剂由氢键受体 (HBA)（通常是季铵盐，例如氯化胆碱）和氢键供体 (HBD)（例如酰胺、羧酸或醇）的混合物组成。对于热力学模型，将使用 CALPHAD（PHAse 图计算）方法。它包括为化学系统中的每个相开发吉布斯能量函数，根据实验数据进行校准，作为温度、压力和成分的函数。然后，找到对应于全局能量最小值的相的组合和组成。先前开发了工业感兴趣的多组分无机熔盐和“离子液体”混合物的密度和粘度模型，两者都与给出熔体结构估计的热力学模型相关。然后，这些模型可用于使用标准插值技术，根据评估的二元（有时是三元）参数来估计多组分盐的特性。同样的方法将适用于各种三元低共熔溶剂，例如氯化胆碱-ZnCl2-HBA、氯化胆碱-HBA-HBD、氯化胆碱-ZnCl2-HBD 和氯化胆碱-HBD1-HBD2（其中 HBA 是季铵盐）盐）。热力学和物理性质模型将根据已发表的科学文献和新获得的测量数据（结构数据、相图、密度和粘度）进行校准。使用开发的模型和数据库，人们将能够自动搜索和计算与一系列液相线温度、密度和粘度值相对应的三元低共熔溶剂成分，从而可以针对特定的工业应用，同时避免极其繁琐和复杂的计算。昂贵的试错实验方法。尽管低共熔溶剂仅在大约 15 年前出现，但它们具有许多潜在的工业应用，包括木质素的溶解和废纸的净化。科学界目前的目标是通过使用它们来实现纸浆和造纸过程中能源消耗减少 40%，二氧化碳排放量减少 80%，这在加拿大至关重要。