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Innovative Approaches for Enhancing the Cost-Efficiency of Biological Methane Abatement

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PROGRAMA DE DOCTORADO EN INGENIERÍA QUÍMICA Y AMBIENTAL TESIS DOCTORAL: Innovative approaches for enhancing the cost-efficiency of biological methane abatement Presentada por Sara Cantera Ruiz de Pellón para optar al grado de Doctor/a por la Universidad de Valladolid Dirigida por: Dr. Raúl Muñoz Torre Dr. Pedro Antonio García Encina PROGRAMA DE DOCTORADO EN INGENIERÍA QUÍMICA Y AMBIENTAL TESIS DOCTORAL: Innovative approaches for enhancing the cost-efficiency of biological methane abatement Presentada por Sara Cantera Ruiz de Pellón para optar al grado de Doctor/a por la Universidad de Valladolid Dirigida por: Dr. Raúl Muñoz Torre Dr. Pedro Antonio García Encina Memoria para optar al grado de Doctor, con Mención Doctor Internacional, presentada por la Microbióloga: Sara Cantera Ruiz de Pellón Siendo el tutor en la Universidad de Valladolid: Dr. Raúl Muñoz Torre Dr. Pedro A. García Encina Y en Microbiology Lab, University of Wageningen (The Netherlands): Dr. Irene Sánchez-Andrea Valladolid, Julio de 2018 UNIVERSIDAD DE VALLADOLID ESCUELA DE INGENIERÍAS INDUSTRIALES Secretaría La presente tesis doctoral queda registrada en el folio número _______ del correspondiente libro de registro número _____________________ Valladolid, a ______ de_______________ de 2018 Fdo. El encargado del registro Raúl Muñoz Torre Profesor Contratado Doctor permanente Departamento de Ingeniería Química y Tecnología del Medio Ambiente Universidad de Valladolid y Pedro A. García Encina Profesor Catedrático Departamento de Ingeniería Química y Tecnología del Medio Ambiente Universidad de Valladolid Certifican que: SARA CANTERA RUIZ DE PELLÓN ha realizado bajo su dirección el trabajo “Innovative approaches for enhancing the cost-efficiency of biological methane abatement”, en el Departamento de Ingeniería Química y Tecnología del Medio Ambiente de la Escuela de Ingenierías Industriales de la Universidad de Valladolid. Considerando que dicho trabajo reúne los requisitos para ser presentado como Tesis Doctoral expresan su conformidad con dicha presentación. Valladolid, a ______ de_______________ de 2018 Fdo. Raúl Muñoz Torre Fdo. Pedro A. García Encina Reunido el tribunal que ha juzgado la Tesis Doctoral titulada “Innovative approaches for enhancing the cost-efficiency of biological methane abatement” presentada por Sara Cantera Ruiz de Pellón y en cumplimiento con lo establecido por el Real Decreto 99/2011 de 28 de enero de 2011 acuerda conceder por_______________ la calificación de ________________________. Valladolid, a ______ de_______________ de 2018 PRESIDENTE SECRETARIO VOCAL Table of contents Contenido Resumen ............................................................................................................................... I Abstract ............................................................................................................................. VI List of publications ........................................................................................................... XI Contribution to the papers included in the thesis ....................................................... XII Chapter 1.Introduction ........................................................................................................ 1 1.1 Methane emissions: origin and environmental concerns .............................................. 2 1.1.1 Methane sources and sinks: CH4 budget ................................................................ 3 1.1.2 International initiatives for the reduction of methane emissions ........................... 4 1.2 End of the pipe solutions for methane abatement ......................................................... 5 1.2.1 Methane-oxidizing bacteria as the core of methane abatement biotechnologies ... 6 1.2.2 Biological technologies for CH4 abatement ......................................................... 11 1.3 Current limitations in biological CH4 treatment ......................................................... 12 1.3.1 Methane mass transfer in bioreactors ................................................................... 12 1.3.2 CH4 biodegradation based on a waste-to-value approach .................................... 18 1.3.3 The need for a better understanding of methane-oxidizing bacteria .................... 23 1.4 References ................................................................................................................... 25 Chapter 2: Aims and Scope of the Thesis ........................................................................ 34 2.1 Justification of the thesis ............................................................................................. 35 2.2 Main objectives ........................................................................................................... 35 2.3 Development of the thesis ........................................................................................... 36 Chapter 3: Comparative performance evaluation of conventional and two-phase hydrophobic stirred tank reactors for methane : Mass Transfer and Biological Considerations .................................................................................................................... 38 Table of contents Chapter 4: Valorization of CH4 emissions into high-added-value products: Assessing the production of ectoine coupled with CH4 abatement. .......................................................... 61 Chapter 5: Continuous abatement of methane coupled with ectoine production by Methylomicrobium alcaliphilum 20Z in stirred tank reactors: a step further towards greenhouse gas biorefineries. ............................................................................................. 81 Chapter 6: Ectoine bio-milking in methanotrophs: A step further towards methane-based bio-refineries into high added-value products. ................................................................. 106 Chapter 7: Multi-production of high added market value metabolites from methane emissions by an halotolerant methanotrophic consortia. ................................................. 122 Chapter 8: Novel Alkalophilic and halophilic methanotrophic bacteria: An attempt for enhancing methane bio-refinery . ..................................................................................... 141 Chapter 9: Evaluation of the influence of methane and copper concentration and methane mass transport on the community structure and biodegradation kinetics of methanotrophic cultures. .................................................................................................. 165 Chapter 10: Conclusions and future work ...................................................................... 186 Chapter 11:About the author .......................................................................................... 192 Table of contents Resumen Resumen El metano (CH4), con un potencial de calentamiento global 25 veces mayor que el del CO2 (en un horizonte temporal de 100 años) y unas emisiones a la atmósfera que representan el 18 % de las emisiones totales de gases de efecto invernadero en la UE-28, es el segundo gas de efecto invernadero más importante. La combustión de metano es energéticamente favorable a concentraciones superiores al 20 %, lo que posibilita que se pueda usar para la producción de energía en forma de calor. Sin embargo, más del 56 % de las emisiones antropogénicas contienen concentraciones de este gas inferiores al 5 %, por lo que no pueden ser destinadas a la producción de energía. A pesar de la relevancia medioambiental del metano y de las cada vez más estrictas legislaciones para el control de sus emisiones, el desarrollo de tecnologías de tratamiento de CH4 eficaces, económicas y respetuosas con el medio ambiente ha sido muy limitado. De hecho, incluso las tecnologías fisico/químicas más avanzadas son, a día de hoy, costosas e ineficaces para tratar las emisiones de las fuentes mayoritarias de CH4 (gestión de residuos, ganadería intensiva, minería y combustión de carburantes). A este respecto, el tratamiento biológico de metano, basado en la acción de microorganismos capaces de degradar este gas, emerge como una alternativa más rentable y medioambientalmente respetuosa para el tratamiento de emisiones diluídas de metano. Las tecnologías biológicas han demostrado de forma concluyente ser un método de bajo coste, eficaz y de reducido impacto ambiental para el tratamiento de emisiones gaseosas odoríferas e industriales. Sin embargo, a pesar de que diferentes configuraciones de biorreactores se han implementado exitosamente para el tratamiento de compuestos orgánicos volátiles, el tratamiento de metano está limitado hoy en día por: 1) sus bajas tasas de transferencia desde la fase gas a la fase líquida donde se encuentran generalmente las comunidades microbianas encargadas de degradar el metano; 2) la falta de procesos rentables e industrialmente competitivos para degradar metano; 3) el limitado conocimiento del efecto de los parámetros ambientales sobre la estructura y las características de las comunidades metanotróficas encargadas de degradar el metano, así como de las cinéticas de biodegradación propias del tratamiento de emisiones diluidas de CH4. I Resumen La principal limitación del tratamiento biológico de metano reside en la baja solubilidad de este gas en el medio acuoso donde se encuentra la biomasa encargada de degradarlo (constante de Henry (H) = 30 a 25 ºC), lo que supone mayores tiempos de residencia del gas y por ende mayores inversiones y costes de operación.
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