Simulación de procesos químicos (curso 2011-2012)

Apuntes en formato html que incluyen los siguientes temas de la parte de simulación en la asignatura «simulación y optimización de procesos químicos» TEMA 1. Introducción 1.1 Introducción. 1.2 Desarrollo histórico de la simulación de procesos. Relación entre simulación optimización y síntesis de procesos. 1.3 Tipos de simuladores: Modular secuencial. Modular simultáneo. Basada en ecuaciones. TEMA 2. Simulación Modular Secuencial 2.1 Descomposición de diagramas de flujo (flowsheeting) 2.2 Métodos basados en las matrices booleanas Localización de redes cíclicas máximas. Algoritmo de Sargent y Westerberg. Algoritmo de Tarjan. 2.3 Selección de las corrientes de corte: 2.3.1 Caso general planteamiento como un "set-covering problem" (algoritmo de Pho y Lapidus) 2.3.2 Número mínimo de corrientes de corte (algoritmo de Barkley y Motard) 2.3.3 Conjunto de corrientes de corte no redundante (Algoritmo de Upadhye y Grens) TEMA 3. Simulación Modular Simultánea 3.1 Efecto de las estrategias tipo cuasi Newton sobre la convergencia de los diagramas de flujo. TEMA 4. Simulación Basada en Ecuaciones 4.1 Introducción. Métodos de factorización de matrices dispersas. Métodos a priori y métodos locales. 4.2 Métodos locales: Criterio de Markowitz. 4.3 Métodos a priori: 4.3.1 Triangularización por bloques: a. Base de salida admisible (transversal completo). b. Aplicación de los algoritmos de Sargent y Tarjan a matrices dispersas. c. Reordenación. 4.3.2 Transformación en matriz triangular bordeada. 4.4 Fase numerica. Algoritmo RANKI 4.5 Comparación entre los diferentes sistemas de simulación. Ventajas e Inconvenientes. TEMA 5. Grados de libertad y variables de diseño de un diagrama de flujo 5.1 Teorema de Duhem y regla de las fases 5.2 Grados de libertad de un equipo 5.3 Grados de libertad de un diagrama de flujo 5.4 Elección de las variables de diseño.

Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.

Surface growth for molten silicon infiltration into carbon millimeter-sized channels: Lattice–Boltzmann simulations, experiments and models

The process of liquid silicon infiltration is investigated for channels with radii from 0.25 to 0.75 [mm] drilled in compact carbon preforms. The advantage of this setup is that the study of the phenomenon results to be simplified. For comparison purposes, attempts are made in order to work out a framework for evaluating the accuracy of simulations. The approach relies on dimensionless numbers involving the properties of the surface reaction. It turns out that complex hydrodynamic behavior derived from second Newton law can be made consistent with Lattice-Boltzmann simulations. The experiments give clear evidence that the growth of silicon carbide proceeds in two different stages and basic mechanisms are highlighted. Lattice-Boltzmann simulations prove to be an effective tool for the description of the growing phase. Namely, essential experimental constraints can be implemented. As a result, the existing models are useful to gain more insight on the process of reactive infiltration into porous media in the first stage of penetration, i.e. up to pore closure because of surface growth. A way allowing to implement the resistance from chemical reaction in Darcy law is also proposed.