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: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=742779
• 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.

拟议的研究计划的目的是开发模型的热力学（主要是相图）和物理（主要是密度和粘度）的三元系统的深Eu 3+溶剂的属性。后者受到越来越多的关注，因为与“离子液体”（通常由大的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，它们的生产成本更低，毒性更小，并且通常可生物降解。例如，它们可以用作生物催化、有机合成以及溶解和萃取过程的溶剂。典型的二元深铕溶剂由氢键受体（HBA）（通常是季铵盐，如氯化胆碱）和氢键供体（HBD）（如酰胺、羧酸或醇）的混合物组成。对于热力学模型，将使用CALPHAD（相位图计算）方法。它包括开发吉布斯能函数，校准实验数据，为每个阶段的化学系统，作为温度，压力和组成的函数。然后，相对应的一个全球性的能量minimum. Models的密度和粘度的多组分无机熔融盐和“离子液体”的混合物的工业利益，这两个链接到的热力学模型，给出了一个估计的熔体的结构，相的组合和组合物被发现。然后，这些模型可以用来估计多组分盐的属性，从评估的二元（有时三元）参数，使用标准插值技术。将相同的方法应用于各种三元深度共沸溶剂，例如氯化胆碱-ZnCl 2-HBA、氯化胆碱-HBA-HBD、氯化胆碱-ZnCl 2-HBD和氯化胆碱-HBD 1-HBD 2（其中HBA是季铵盐）。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对应于液相线温度，密度和粘度值范围的三元深Eu 3+溶剂组合物，从而允许针对特定的工业应用，同时避免极其繁琐和昂贵的试验和错误的实验方法。尽管深共晶溶剂大约15年前才出现，但它们具有许多潜在的工业应用，包括木质素的溶解和回收纸的净化。科学界目前的目标是通过使用它们来实现纸浆和造纸中40%的能源使用减少和80%的二氧化碳排放减少，这在加拿大至关重要。