Obtención de biocombustibles vía Fischer-Tropsch a partir de gas de síntesis procedente de una planta piloto de gasificación

Resumen

Introducción Entre los retos medioambientales actuales destacan, por un lado, dar solución al exceso de CO2 emitido a la atmósfera y, por otro, cómo obtener un combustible de aviación de origen renovable, dado que no existe un sustituto de este tipo para dichos combustibles. La presente tesis tiene como finalidad la obtención de hidrocarburos a partir de un gas de síntesis, mezcla de CO e H2, o de CO2 con H2 de origen renovable. Se emplea como vía de conversión la Síntesis Fischer-Tropsch (FT), utilizando catalizadores bifuncionales que sintetizan hidrocarburos desde dióxido o monóxido de carbono a hidrocarburos de forma directa, sin procesos intermedios. El resultado de la síntesis son varias fases: sólida, líquida acuosa, líquida orgánica y gaseosa, en función de la longitud de la cadena del hidrocarburo que predomine. En concreto, los hidrocarburos buscados son de cadena lineal comprendidos entre C10 y C15 que son los componentes principales de los querosenos de aviación. Desarrollo teórico Durante la experimentación se han sintetizado catalizadores de carburo de hierro, con oxalato de hierro como precursor y empleando como fase activa χ-Fe5C2 (Carburo de Hägg), con el empleo de aditivos de K y Cu, soportes de Grafito y SiO2 y demostrando la viabilidad de los catalizadores bifuncionales mediante pruebas con CO y CO2. Se han obtenido altos rendimientos de conversión a hidrocarburos para el CO, del 98%, y de CO2, próximos al 18%. Dentro de las series experimentales se han probado distintas rampas de activación, resultando la rampa a 34 h en la que se obtuvo los mejores resultados. Los valores de producción de hidrocarburos líquidos obtenidos han sido de 0,17 g de HC líquido·gcat-1·h-1, para un tiempo en corriente de 201 h. A su vez, se han analizado los productos y comprobado que siguen la distribución estadística Anderson-Schulz-Flory (ASF). Los catalizadores fueron probados con gas de síntesis real con alto contenido en azufre para comprobar su resistencia. También se han caracterizado los catalizadores mediante las técnicas de adsorción de N2, XRD y SEM. Además, se tiene como fin demostrar la viabilidad del proceso real, integrando en línea las fases de producción de gas de síntesis, limpieza, depuración, compresión del gas y síntesis a hidrocarburos. Para ello se ha diseñado y construido un reactor catalítico apto para llevar a cabo la síntesis Fischer-Tropsch y una etapa de compresión y almacenamiento de gas de síntesis. Las etapas de generación, limpieza y depuración se realizaron mediante la adaptación de equipos existentes. Por último, se ha realizado un análisis energético y económico de los costes de transformación sobre el proceso propuesto.   Conclusión Las conclusiones más destacables obtenidas en el presente trabajo son las siguientes: 1ª La rampa de activación que presentó mejor comportamiento en cuanto a conversión, producción de C3+ y características superficiales del catalizador fue la rampa 3 de 34 horas. 2ª En general los catalizadores sintetizados presentaron buenos resultados de conversión y selectividad con CO, excepto el 6 que presentó una conversión inferior al resto, pero una producción de hidrocarburos pesados y ceras muy superior. El catalizador sobre el que se obtuvo la mejor relación de conversión y producción de C3+ con CO fue la síntesis 10, que sintetizó a partir de nitrato de hierro y glicerina. 3ª La síntesis con CO2 presentó unos valores de conversión muy inferiores a los obtenidos con CO. El catalizador que mejores resultados obtuvo, atendiendo a la relación entre conversión y selectividad fue la síntesis 7, en la que se empleó oxalato de hierro al que se añadió K y Cu. 4ª En cuanto a la mezcla de CO y CO2 se observó que, de forma general el CO2 inhibe la síntesis del CO, pero en pequeñas cantidades mejora ligeramente la conversión y la producción de hidrocarburos a C3+ 5ª La serie a largo plazo confirmó la robustez de catalizador basado en carburo de hierro, en el que se empleó como precursor oxalato de hierro comercial, en cuanto al mantenimiento de la actividad durante el tiempo de reacción, demostrando su buen comportamiento durante las pruebas. 6ª El mayor valor de productividad obtenido alcanzó los 0,17 g de HC líquido·gcat-1·h-1, obtenido con el oxalato comercial como precursor. 7ª Los resultados obtenidos en el gas de síntesis real contaminado con azufre confirman el buen comportamiento de los catalizadores en las peores condiciones, con ligeras diferencias entre los tipos probados. 9ª El análisis energético del proceso realizado con equipos de proceso a escala de pequeña planta piloto y sin haber tenido ninguna consideración sobre consumo energético durante su diseño, arroja unos resultados mejorables (1,87 y 0,74 kWh/g de HC). 8ª El resultado económico es orientativo sobre los costes reales del proceso, pero si permite ordenar las etapas por consumo, determinando aquellas sobre las que centrar los esfuerzos de eficiencia energética debido al mayor coste que repercuten. En el proceso propuesto, la etapa de generación, seguida de la de compresión son las dos principales etapas para optimizar. 9ª Las distribuciones de hidrocarburos obtenidos tienen valores de densidad y puntos de destilación próximos a los establecidos por la normativa, sin haber sido sometidos a procesos de refinado o mejora. 10ª La experimentación llevada a cabo con la planta de reformado de glicerina permite concluir que la planta, una vez realizadas las modificaciones, ha cumplido plenamente con las expectativas y que el sistema de ajuste de caudales ha funcionado de forma correcta. Sin embargo, también se puede concluir que la planta trabaja por debajo de su capacidad óptima, lo que penaliza la eficiencia energética y aumenta los costes del proceso. 11ª Respecto a la etapa de limpieza y depuración cumple con lo exigido, funcionando a una capacidad inferior a su máxima permitida. 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