Publication: Estudio termodinámico del proceso de separación de copolímero de Etileno-Vinil Acetato (EVA) en disolución
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2017-05-11
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Universidad Complutense de Madrid
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Abstract
Este proyecto presenta un estudio termodinámico riguroso para las interacciones entre el Copolímero de Etileno- Acetato de Vinilo (EVA) y los disolventes participantes en la etapa de separación (columna de recuperación) del proceso de producción del copolímero EVA en disolución; con el objetivo de modelar dicho proceso y de proveer una herramienta que permita el desarrollo de estrategias adecuadas para la predicción y optimización industrial. Para alcanzar este objetivo, el copolímero EVA ha sido dividido en sus correspondientes homopolímeros, Polietileno y Polivinilacetato. Los disolventes participantes en el mencionado proceso son metanol y acetato de vinilo. Adicionalmente se ha considerado estratégicamente al disolvente ciclohexano. Inicialmente, se han determinado los parámetros termodinámicos tradicionales para los sistemas polímero/disolventes (parámetros de Flory Huggins) a dilución infinita de polímero y de disolvente, a partir de los procedimientos experimentales de determinación de Viscosidad Intrínseca, y de la técnica de Cromatografía Inversa de Gases, respectivamente. Adicionalmente se han determinado las interacciones entre los polímeros mencionados y otros disolventes (representando a los disolventes con propiedades de dispersión, asociación y polares), con el objetivo de desarrollar una evaluación termodinámica intensiva a dichas condiciones diluidas, para reportar y evaluar variables termodinámicas fundamentales del copolímero EVA, el Polietileno y el Polivinilacetato. Seguidamente, se ha propuesto una metodología, para estimar la curva parámetros de Flory Huggins – composición de polímero, y la subsecuente curva de absorción de disolvente (Presión – concentración de polímero), a partir de los parámetros de Flory Huggins obtenidos a los mencionados extremos de las mezclas binarias (dilución infinita de polímero y de disolvente). Dicha metodología se ha basado en los trabajos de Bernard Wolf y ha sido validada para diez sistemas de polímeros/disolventes diferentes, en el rango de pesos moleculares entre 10 y 250 kg/mol, obteniendo un valor promedio de la desviación absoluta (%AAD) alrededor de 1%, entre la presión estimada y bibliográfica. Por lo tanto esta metodología es aplicable para los sistemas polímero/disolvente comunes...
This work presents a rigorous thermodynamic study for the interactions between the Ethylene Vinyl Acetate (EVA) copolymer and the solvents involved in the separation stage (recovery column) of an EVA solution production process; in order to model accurately this process and provide an industrial tool that allows the development of suitable prediction and optimization strategies. To achieve this goal, the EVA copolymer was splitted into its correspondent homopolymers, Polyethylene (PE) and Polyvinylacetate (PVA). The solvents participating in this process are methanol and vinyl acetate, plus the strategic consideration of cyclohexane. Initially, the traditional thermodynamics parameters for these polymer/solvents systems (Flory Huggins parameters) were determined at infinite dilution of polymer and infinite dilution of solvent, by means of the Intrinsic Viscosity procedure and the Inverse Gas Chromatography Technique, respectively. In addition, the interaction between these polymers and other solvents (representing dispersion, association and polar solvents) were determined, in order to develop an intensive thermodynamic assessment at such infinite dilutions conditions; reporting and evaluating several crucial thermodynamic variables for the EVA copolymer, Polyethylene and Polyvinylacetate. Then, a novel methodology to estimate the Flory Huggins – polymer concentration curve, and the subsequent solvent sorption curve (pressure – polymer composition curves), from the mentioned Flory Huggins data measured at the composition extremes of the binary mixture (infinite dilution of polymer and solvent) was proposed, based on the works of Bernard Wolf. This methodology was validated for ten different polymer/solvent systems in a range of molecular weights from 10 to 250 kg/mol, with an overall value of the average absolute deviation (%AAD) between the literature and estimated pressure values around 1%. Therefore, it is applicable for any typical polymer/solvent system...
This work presents a rigorous thermodynamic study for the interactions between the Ethylene Vinyl Acetate (EVA) copolymer and the solvents involved in the separation stage (recovery column) of an EVA solution production process; in order to model accurately this process and provide an industrial tool that allows the development of suitable prediction and optimization strategies. To achieve this goal, the EVA copolymer was splitted into its correspondent homopolymers, Polyethylene (PE) and Polyvinylacetate (PVA). The solvents participating in this process are methanol and vinyl acetate, plus the strategic consideration of cyclohexane. Initially, the traditional thermodynamics parameters for these polymer/solvents systems (Flory Huggins parameters) were determined at infinite dilution of polymer and infinite dilution of solvent, by means of the Intrinsic Viscosity procedure and the Inverse Gas Chromatography Technique, respectively. In addition, the interaction between these polymers and other solvents (representing dispersion, association and polar solvents) were determined, in order to develop an intensive thermodynamic assessment at such infinite dilutions conditions; reporting and evaluating several crucial thermodynamic variables for the EVA copolymer, Polyethylene and Polyvinylacetate. Then, a novel methodology to estimate the Flory Huggins – polymer concentration curve, and the subsequent solvent sorption curve (pressure – polymer composition curves), from the mentioned Flory Huggins data measured at the composition extremes of the binary mixture (infinite dilution of polymer and solvent) was proposed, based on the works of Bernard Wolf. This methodology was validated for ten different polymer/solvent systems in a range of molecular weights from 10 to 250 kg/mol, with an overall value of the average absolute deviation (%AAD) between the literature and estimated pressure values around 1%. Therefore, it is applicable for any typical polymer/solvent system...
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Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, Departamento de Ingeniería Química, leída el 05-02-2016