Multi-scale design of deep eutectic solvents to recover fluorinated greenhouse gases.
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Date
2026
Journal Title
Journal ISSN
Volume Title
Publisher
Universidad de Concepción
Abstract
La creciente preocupación ambiental asociada a hidrofluorocarbonos (HFC) de alto potencial de calentamiento global ha impulsado acuerdos internacionales para su eliminación progresiva. Dado su amplio uso en sistemas refrigerantes, diversas estrategias se han ideado para su recuperación. Entre ellas, la destilación extractiva es una alternativa prometedora, pues permite recuperar componentes refrigerantes para usos alternativos. En este contexto, los líquidos iónicos y los solventes eutécticos han despertado interés como solventes de arrastre debido a sus propiedades termofísicas y versatilidad molecular. Sin embargo, el vasto espacio químico y complejos fenómenos físicos asociados a estos dificultan su diseño racional, resaltando la necesidad de enfoques teóricos predictivos que fundamenten la toma de decisiones en torno a nuevas tecnologías de separación. El modelo de solvatación COSMO-RS y las simulaciones por dinámica molecular proveen un marco robusto para estudiar el efecto de características microscópicas sobre el comportamiento termofísico de solventes eutécticos fluorados. Estos enfoques demuestran que la solubilidad de HFCs es influenciada por interacciones localizadas soluto–solvente y por la disrupción de aglomeraciones de soluto en la fase líquida. La información molecular obtenida permite identificar criterios específicos para el desarrollo de solventes avanzados destinados a la recuperación de HFCs. En una escala más amplia, ecuaciones de estado basadas en SAFT proporcionan modelos robustos para caracterizar equilibrios de fases relevantes para la absorbción de HFCs. Los modelos termodinámicos empleados permiten evaluar líquidos iónicos basados en fosfonio y solventes de eutéctico profundo de tipo III como solventes de arrastre para mezclas refrigerantes en un amplio rango de condiciones operacionales. Su desempeño, cuantificado en torno a métricas de selectividad, permite identificar candidatos para la recuperación de HFCs desde mezclas comerciales. Los modelos termodinámicos generados son integrados en simulaciones de proceso y análisis de ciclo de vida para evaluar su desempeño ambiental en la recuperación de mezclas refrigerantes mediante destilación extractiva. Este proceso constituye una alternativa viable a las rutas de tratamiento basadas en destrucción química, siempre que la demanda por compuestos recuperados permita reemplazar su producción virgen. La evaluación de cadenas de suministro destaca la importancia de adoptar tempranamente esta tecnología, con tal de reducir la huella de carbono asociada a futuros escenarios de eliminación de HFCs. En conjunto, la integración multiescala de enfoques computacionales constituye una metodología efectiva para el desarrollo de tecnologías basadas en solventes avanzados orientadas al tratamiento sostenible de gases fluorados.
The increasing environmental concern associated with high-GWP hydrofluorocarbons (HFCs) has propelled international agreements for their progressive phase-out. Given the widespread use of these compounds in refrigeration applications, considerable efforts have been devoted to the development of strategies for their recovery. Extractive distillation has emerged as a promising route, as it enables the recovery of refrigerant constituents for their use in alternative applications. In this context, ionic liquids and eutectic solvents have attracted growing interest as entrainers due to their suitable thermophysical properties and molecular tunability. However, the vast chemical space and complex physical phenomena associated with these solvents hinder their rational design, highlighting the need for predictive theoretical approaches aimed at supporting decisionmaking in the implementation of novel separation technologies. The COSMO-RS solvation model and molecular dynamics simulations provide a powerful framework to study the effect of microscopic features in the thermophysical behavior of fluorinated eutectic solvents. These approaches demonstrate that HFC solubility is strongly influenced by localized solute–solvent interactions and disruption of solute clustering in the liquid phase. The obtained molecular-level insights highlight specific design criteria for the development of advanced solvents for HFC recovery. At a broader scale, SAFT-based equations of state provide robust mathematical models to characterize phase equilibria in systems relevant to HFC absorption. The employed thermodynamic models allow to evaluate phosphonium-based ionic liquids and type III deep eutectic solvents as entrainers for refrigerant blends over a wide range of operational conditions. The performance of these solvents, quantified through selectivity metrics, is assessed to identify promising candidates for the recovery of HFCs from commercial mixtures. The generated thermodynamic models are integrated into process simulation and life cycle assessment frameworks to evaluate their environmental performance in the reclamation of refrigerant blends. HFC recovery based on extractive distillation provides a viable alternative to destructionoriented management routes, subjected to the extent to which recovered components displace fresh production. Furthermore, supply chain assessments highlight the importance of early deployment of this technology in reducing the carbon footprint of phase-out scenarios for HFCs. Overall, the multiscale integration of computational approaches provides an effective framework for the development of technologies based on advanced solvents aimed at the sustainable management of fluorinated gases.
The increasing environmental concern associated with high-GWP hydrofluorocarbons (HFCs) has propelled international agreements for their progressive phase-out. Given the widespread use of these compounds in refrigeration applications, considerable efforts have been devoted to the development of strategies for their recovery. Extractive distillation has emerged as a promising route, as it enables the recovery of refrigerant constituents for their use in alternative applications. In this context, ionic liquids and eutectic solvents have attracted growing interest as entrainers due to their suitable thermophysical properties and molecular tunability. However, the vast chemical space and complex physical phenomena associated with these solvents hinder their rational design, highlighting the need for predictive theoretical approaches aimed at supporting decisionmaking in the implementation of novel separation technologies. The COSMO-RS solvation model and molecular dynamics simulations provide a powerful framework to study the effect of microscopic features in the thermophysical behavior of fluorinated eutectic solvents. These approaches demonstrate that HFC solubility is strongly influenced by localized solute–solvent interactions and disruption of solute clustering in the liquid phase. The obtained molecular-level insights highlight specific design criteria for the development of advanced solvents for HFC recovery. At a broader scale, SAFT-based equations of state provide robust mathematical models to characterize phase equilibria in systems relevant to HFC absorption. The employed thermodynamic models allow to evaluate phosphonium-based ionic liquids and type III deep eutectic solvents as entrainers for refrigerant blends over a wide range of operational conditions. The performance of these solvents, quantified through selectivity metrics, is assessed to identify promising candidates for the recovery of HFCs from commercial mixtures. The generated thermodynamic models are integrated into process simulation and life cycle assessment frameworks to evaluate their environmental performance in the reclamation of refrigerant blends. HFC recovery based on extractive distillation provides a viable alternative to destructionoriented management routes, subjected to the extent to which recovered components displace fresh production. Furthermore, supply chain assessments highlight the importance of early deployment of this technology in reducing the carbon footprint of phase-out scenarios for HFCs. Overall, the multiscale integration of computational approaches provides an effective framework for the development of technologies based on advanced solvents aimed at the sustainable management of fluorinated gases.
Description
Tesis presentada para optar al grado de Doctor/a en Ciencias de la Ingeniería con mención en Ingeniería Química.
Keywords
Solvents, Fluorinated gases, Greenhouse gases