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.

该研究计划的目标是建立深共晶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)性质的模型。与“离子液体”(通常由大的有机阳离子和无机阴离子组成，在相对较低的温度下熔化)相比，后者受到越来越多的关注，它们的生产成本更低，毒性更小，而且往往是可生物降解的。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。典型的二元深度共熔溶剂由氢键受体(HBA)和氢键供体(HBD)的混合物组成，氢键受体通常是季铵盐，如氯化胆碱，氢键给体是酰胺、羧酸或酒精。热力学模型采用CALPHAD(相图计算)方法。它包括将吉布斯能量函数发展为温度、压力和组成的函数，该函数是根据实验数据对化学体系中的每一相进行校准的。然后，找到对应于全局能量最小值的相的组合和组成。工业上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都与给出熔体结构估计的热力学模型相关联。然后，这些模型可以利用标准内插技术，从评估的二元(有时是三元)参数中估计多组分盐的性质。同样的方法将适用于各种三元深度共熔溶剂，如氯化胆碱-氯化锌-HBA、氯化胆碱-氯化锌-HBD、氯化胆碱-氯化锌-HBD和氯化胆碱-HBD1-HBD2(其中氯化胆碱是季铵盐)。热力学和物理性质模型将根据发表的科学文献中的数据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液相线温度、密度和粘度的一系列值相对应的三元深度共熔溶剂组成，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试验方法。尽管深度共熔溶剂在大约15年前才出现，但它们具有许多潜在的工业应用，包括溶解木质素和净化回收纸张。科学界目前通过使用它们的一个目标是在纸浆和造纸中减少40%的能源消耗和80%的二氧化碳排放，这在加拿大至关重要。