Rodríguez, María (2021) Producción de hidrogeno a partir del reciclado de aleaciones de magnesio / Hydrogen production from the recycling of magnesium alloys. Maestría en Ingeniería, Universidad Nacional de Cuyo, Instituto Balseiro.
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Resumen en español
En esta tesis se analiza la factibilidad del reciclado de virutas de descarte de aleaciones base magnesio para utilizarlas en producción de H_2 mediante la reacción de hidrolisis. La particularidad del reprocesamiento es que se basa en la molienda mecánica de las virutas en atmosfera de aire. Para esto se llevaron a cabo distintos procedimientos: Se molieron virutas de descarte del maquinado de ánodos de sacrificio sin aditivos durante distintos tiempos. Se probaron distintas estrategias para el agregado de grato como aditivo a estas virutas: (i) se molió durante 5, 10 y 20 horas con grato agregado desde el inicio, (ii) se agrego grato a un material premolido mezclando los polvos con un mortero, y (iii) se realizo una premolienda sin aditivos y luego se incorporo el grato moliendo distintos tiempos adicionales. Se analizo el efecto de la incorporación de hierro durante la molienda. Se probo en dos materiales distintos un procedimiento de reciclado optimizado: virutas de anodos de sacrificio y virutas del maquinado de cajas de velocidad. El mismo consistió en premoler los materiales durante 10 h con el agregado de 15% p/p de Fe e incorporar luego 5% p/p de grato moliendo una hora mas. Los tres primeros procedimientos se realizaron para encontrar una forma satisfactoria de reprocesar las virutas y poder producir H_2 con buen rendimiento y buena cinética. Estos estudios permitieron seleccionar los aditivos a utilizar, la cantidad de los mismos, y el mejor procesamiento de incorporación. Los últimos experimentos permitieron validar la estrategia de reciclado diseñada, probandola exitosamente en dos materiales con características diferentes. Con los materiales descartados de la fabricación de anodos de sacrificio se alcanzo una producción de hidrogeno de 747 ± 24 mL por gramo de material en 5,0 minutos. Esto corresponde a un rendimiento del 78 ± 3 %. La velocidad de producción de hidrogeno fue también satisfactoria ya que se pudieron producir 371 ± 24 mL=g en los primeros 1,2 minutos. Con los materiales descartados en la fabricación de cajas de velocidad se alcanzo una producción de H_2 de 787 ± 24 mL=g en 3,5 minutos (rendimiento del 84 ± 3 %) y con una velocidad de 371 ± 24 mL=g en los primeros 0,5 minutos. Además de haber logrado un reciclado y una producción de hidrogeno muy satisfactorios, se identificaron algunas características interesantes de los procesos involucrados mediante el análisis sistemático de los resultados. Se encontró que la cinética de la reacción se encuentra controlada por un mecanismo de contracción geométrica. Por lo tanto la velocidad de la reacción es directamente proporcional a la velocidad de avance de la interfase de reacción e inversamente proporcional al tamaño de las partículas. Se observo que la presencia de Fe, Mg_17Al_12 y grato acelera la velocidad de avance de la interfase debido a la formación de pares galvánicos con el Mg. Además, el grato agregado luego de una premolienda, actúa como agente regulador del proceso de molienda evitando la soldadura en frio y provocando una disminución en el tamaño de las partículas. Consideramos que la formación de pares galvanicos y la reducción del tamaño son las causas principales que han permitido alcanzar producciones de H_2 satisfactorias tanto en rendimiento como en velocidad a través de la hidrolisis de los materiales reciclados.
Resumen en inglés
In this Master's degree thesis we analyze the feasibility of reprocessing waste chips from Mg-based alloys to produce hydrogen by the hydrolysis reaction. The recycling process is based on mechanical milling the chips under air atmosphere. With this aim, different procedures were carried out: Chips from the manufacturing of sacricial anodes were milled without additives for different times. Different strategies were tested for the addition of graphite as an additive: (i) chips were milled during 5, 10 and 20 hours with graphite added from the beginning, (ii) graphite was added to a pre-milled material by mixing the powders with a mortar, and (iii) chips were pre-milled 10 h milling without additives and after that graphite was added and the mixture was further milled for different times. The effect of iron as an additive was explored. An optimized procedure was tested in two different materials: chips from the manufacturing of sacricial anodes, and chips from the fabrication of gear boxes. The procedure included a 10 h pre-milling with 1.5 wt% of Fe and a further milling of 1 h after adding 5 wt% of graphite. The rst experiments were carried out to identify a satisfactory strategy to reprocess the chips and to be able to produce H_2 with satisfactory yield and kinetics. These studies allowed us to select the used additives, their amount and the best procedure to incorporate them. The last experiments allowed us to validate the designed reprocessing strategy by successfully testing it in two materials with different properties. In the case of the sacricial anodes chips 747 ± 24 mL of hydrogen were produced per gram of material in 5.0 minutes. This corresponds to a yield of 78 ± 3 %. The rate of hydrogen production has also been successful, as 371 ± 24 mL of H_2 per gram of material was produced during the rst 1.2 minutes. In the case of the gear boxes chips, 787 ± 24 mL of H_2 were produced per gram of material (yield of 84 ± 3 %) with 371 ± 24 mL/g of H_2 produced in the rst 0.5 minutes. Besides the successful reprocessing of the chips and the consequent hydrogen production, some interesting characteristics of the involved processes have been identiffed. It has been found that reaction kinetics is controlled by a geometric contraction mechanism. Therefore, the rate of the reaction is directly proportional to the rate of advance of the reaction interface and inversely proportional to the size of the particles. It was observed that the presence of Fe, Mg_17Al_12 and graphite accelerates this rate due to the formation of galvanic pairs with Mg. Furthermore, the addition of graphite after the pre-milling affects as a control agent of the grinding process, avoiding cold welding and causing a decrease in the size of the particles. We think that the formation of galvanic pairs and the particle size decrease are the main causes of the successful kinetics and yield observed when H_2 was produced by the hydrolysis of the reprocessed materials.
| Tipo de objeto: | Tesis (Maestría en Ingeniería) |
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| Palabras Clave: | Hydrogen; Hidrógeno; Magnesium; Magnesio; Iron; Hierro; Graphite; Grafito; Hydrolysis; Hidrólisis |
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| Materias: | Química > Materiales |
| Divisiones: | Gcia. de área de Aplicaciones de la tecnología nuclear > Gcia. de Investigación aplicada > Fisicoquímica de materiales |
| Código ID: | 1039 |
| Depositado Por: | Tamara Cárcamo |
| Depositado En: | 09 Jun 2022 13:13 |
| Última Modificación: | 09 Jun 2022 13:13 |
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