Tesis Dominguez Ramos

Universidad de Cantabria Escuela Tcnica Superior de Ingenieros Industriales y de Telecomunicacin Departamento de Ingeniera Qumica y Qumica Inorgnica
Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Photovoltaic Solar Electro-Oxidation (PSEO) of organic polluted wastewater
en el Programa de Doctorado en Ingeniera Qumica y de Procesos (P.O.P. en Ingeniera Qumica y de Procesos, BOE nm. 165, de 9 de julio de 2008)
Memoria de Tesis Doctoral presentada para optar al ttulo de Doctor por la Universidad de Cantabria
Antonio Domnguez Ramos

Directores de Tesis: Prof. Dr. ngel Irabien Gulas Dr. Rubn Aldaco Garca Santander, Mayo 2010
Esta tesis se presenta como un resumen de trabajos previamente publicados o aceptados para su publicacin en revistas cientficas internacionales incluidas en el Journal of Citation Reports-
Science Edition, cumpliendo con la normativa existente en la Universidad de Cantabria y en el

Departamento de Ingeniera Qumica y Qumica Inorgnica en lo referente a la elaboracin de Tesis Doctorales como compendio de artculos. A continuacin se listan las publicaciones que forman parte de la presente Tesis as como los congresos internacionales a travs de los cuales se ha realizado la difusin de los resultados.
Compendio de artculos publicados/aceptados: 1. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Life cycle assessment as a tool for
cleaner production: Application to aluminium trifluoride. Int. J. Chem. React. Eng. 2007, 5
(A33)
2. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Electrochemical oxidation of
lignosulfonate: Total organic carbon oxidation kinetics. Ind. Eng. Chem. Res. 2008, 47, 9848 3. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Photovoltaic Solar Electrochemical
Oxidation (PSEO) for lignosulfonate waste water treatment. J. Chem. Technol. Biotechnol. 2010, 85, 821 4. Dominguez-Ramos, A., Held, M., Aldaco, R., Fischer, M., Irabien, A. Prospective CO2
emissions from energy supplying systems: photovoltaic systems and conventional grid within Spanish frame conditions. Int. J. Life Cycle Assess. 2010, En prensa, DOI: 10.1007/s11367010-0192-3
Congresos internacionales: 1. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Environmental indicators for
sustainability: application to life cycle assessment of removal of fluoride from industrial wastewater. XXII Interamerican Congress of Chemical Engineering. 2006. (Argentina). Internacional. Comunicacin oral 2. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Life Cycle Assessment of fluoride BUENOS AIRES
wastewater treatment technologies. 6th ANQUE International Congress of Chemistry. 2006. PUERTO DE LA CRUZ (Tenerife). Internacional. Asistencia. Comunicacin oral (presentada por A. Dominguez-Ramos) 3. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Environmental metrics in the Life Cycle
Assessment methodology for use in the process industries. CILCA 2007- International
Conference of Life Cycle Assessment. 2007. SAO PAULO (Brasil). Internacional. Comunicacin
oral
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4.
Dominguez-Ramos, A., Aldaco, R., Irabien, A. Life cycle assessment as a tool for
cleaner production: application to aluminium trifluoride. 1st International Congress on Green
Process Engineering. 2007. TOULOUSE (Francia). Internacional. Asistencia. Comunicacin oral

(presentada por A. Dominguez-Ramos) 5. Dominguez-Ramos, A., Aldaco, R., Margallo, M., Irabien, A. Enviromental references in
the Life Cycle Assessment of chemical processes: application to the aluminum trifluoride manufacture. 10th Conference on Process Integration, Modelling and Optimisation for Energy
Saving and Pollution Reduction (PRES'07). 2007. ISCHIA (Italia). Internacional. Comunicacin
tipo pster 6. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Regional normalization for life cycle
impact assessment: application to process engineering. 3rd International Conference on Life
Cycle Management 2007. 2007. ZURICH (Suiza). Internacional. Comunicacin tipo poster
7. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Influence of Wastewater Treatment Stage
in the Life Cycle Assessment of Aluminium Trifluoride. European Congress of Chemical
Engineering - 6. 2007. COPENHAGEN (Dinamarca). Internacional. Asistencia. Comunicacin

oral (presentada por A. Dominguez-Ramos) 8. Dominguez-Ramos, A., Fuente-Martin, A., Aldaco, R., Irabien, A. Lignosulphonate total
organic carbon treatment using electrochemical oxidation. XVIII International Conference on
Chemical Reactors CHEMREACTOR-18. 2008. LA VALLETA (Malta). Internacional. Comunicacin

tipo pster 9. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Electrochemical wastewater treatment
with photovoltaic energy integration. 11th Mediterranean Congress of Chemical Engineering. 2008. BARCELONA (Espaa). Internacional. Comunicacin tipo pster 10. Dominguez-Ramos, A., Held, M., Aldaco, R., Fischer, M., Irabien, A. Prospective (2007-
2030) CO2 emissions from Photovoltaic Systems and Grid Power in Spain. III Conferencia
Internacional de Anlisis de Ciclo de Vida en Latinoamrica. 2009. PUCN (Chile).

Internacional. Comunicacin tipo pster 11. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Environmental Sustainability
Normalization of Industrial Processes. 19th European Symposium on Computer Aided Process
Engineering - ESCAPE 19. 2009. CRACOW (Polonia). Internacional. Comunicacin tipo poster.
Asistencia 12. Dominguez-Ramos, A., Held, M., Aldaco, R., Fischer, M., Irabien, A. Photovoltaic solar
electro-oxidation processes (PSEO): energy balance and LCA approach. 8th World Congress of
Chemical Engineering. 2009. MONTREAL (Canad). Internacional. Comunicacin oral

(presentada por A. Dominguez-Ramos)
ii
13.
Dominguez-Ramos, A. Towards the scale-up of the Photovoltaic Solar powered Oxidation (PSEO) for lignosulphonate wastewater treatment.
Electrochemical
1st
Electrochemical Engineering Students Workshop and 5th European Summer School on Electrochemical Engineering. 2009. ALMAGRO (Espaa). Internacional. Comunicacin tipo
pster y oral (presentada por A. Dominguez-Ramos) 14. Fuente-Martin, A., Dominguez-Ramos, A., Aldaco, R., Irabien, A. Environmental burdens
assessment (LCA) of electric energy in municipal wastewater treatment plants. European
Meeting on Chemical Industry and Environment EMChIE VI. 2010. MECHELEN (Blgica).
Internacional. Comunicacin tipo oral (presentada por A. Dominguez-Ramos) 15. Dominguez-Ramos, A., Elorza, B., Aldaco, R., Irabien, A. Photovoltaic Solar
Electrochemical Oxidation (PSEO) for urban waste water treatment. Internacional. VII
CONGRESO INTERNACIONAL DE ANQUE. Ciclo integral del agua: presente y futuro. 2010.
OVIEDO (Espaa). Internacional. Comunicacin tipo oral (presentada por A. DominguezRamos), pendiente de celebracin 16. Dominguez-Ramos, A., Aldaco, R., Irabien, A. The role of renewable energy in the
water treatment. VII CONGRESO INTERNACIONAL DE ANQUE. Ciclo integral del agua: presente
y futuro. 2010. OVIEDO (Espaa). Internacional. Comunicacin tipo oral (presentada por A.
Dominguez-Ramos), pendiente de celebracin 17. Dominguez-Ramos, A., Aldaco, R., Irabien, A. Carbon footprint assessment of
photovoltaic modules manufacture. European Symposium on Computer Aided Process
Engineering - ESCAPE 20. 2010. ISCHIA (Italia). Internacional. Comunicacin tipo pster,
pendiente de celebracin
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Este trabajo ha sido realizado con financiacin del Ministerio de Educacin y del Ministerio de Ciencia y Tecnologa de Espaa a travs de los proyectos CTM2006-00317 Sostenibilidad de la
Produccin: Intensificacin e integracin de procesos en la industria qumica y transformadora

y CNIT-SOSTAQUA: Desarrollos tecnolgicos hacia el ciclo urbano del agua autosostenible.
Durante la ejecucin del presente trabajo, su autor, Antonio Domnguez Ramos, ha disfrutado de una beca F.P.U. (Formacin de Profesorado Universitario) del Ministerio de Educacin y Ciencia concedida por resolucin de 30 de marzo de 2006 (BOE de 21 de abril de 2006), con referencia AP2005-1716 y de una plaza de ayudante LOU de la Universidad de la Cantabria.
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Agradecimientos
Deseo expresar mi ms profunda gratitud a mis directores de tesis, Prof. Dr. ngel Irabien Gulas y Dr. Rubn Aldaco Garca, por la enorme confianza que han depositado en m durante a lo largo de estos 5 aos de duro trabajo y la ayuda que en todo momento me han brindado de forma sincera. Sin su paciencia, comprensin, esfuerzo y dedicacin esta tesis doctoral no habra sido posible.
I am very grateful to Dipl.-Ing. Matthias Fischer, Dipl.-Ing. Michael Held and the rest of researchers of the Department of Life Cycle Engineering of the University of Stuttgart, Germany, for giving me the opportunity to complete a short research stay under their supervision. My gratitude is for all of them due to its sincere help at every time I needed. I sincerely thank all the colleagues with whom I had the opportunity to work in Stuttgart for their kindness and lovely daily discussions and for making me feel one more within the research group since the first hour I was there.
A todos los profesores del Departamento de Ingeniera Qumica y Qumica Inorgnica de la Universidad de Cantabria quiero agradecer su empeo diario en darnos a los alumnos una formacin de calidad e introducirme en el mundo de la investigacin. A todos, mi ms sincera gratitud. A todo el personal de administracin y servicios del Departamento de Ingeniera Qumica y Qumica Inorgnica de la Universidad de Cantabria agradecerles por su buen hacer y predisposicin para ayudarme en la gestin de las tareas del da a da y hacerme la vida un poquito ms fcil. A todos los compaeros del Departamento de Ingeniera Qumica y Qumica Inorgnica de la Universidad de Cantabria, gracias por hacer que cada da sea mejor que el anterior. A todos mis amigos, gracias por ser como sois. No cambiis nunca. Y mi agradecimiento ms especial para toda mi familia, especialmente a mis padres y hermana, porque el amor y el cario son sentimientos que se demuestran todos los das: el amor que siento hacia ellos ser eterno.
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ndice RESUMEN / ABSTRACT 1
CAPTULO 1. PLANTEAMIENTO 1.1 La tecnologa de Electro-Oxidacin para el tratamiento de aguas residuales 1.2 Integracin de Energa Solar Fotovoltaica en la tecnologa de ElectroOxidacin 1.3 Anlisis de Ciclo de Vida para la evaluacin de la sostenibilidad ambiental del proceso ESOF 1.4 Aplicacin del proceso ESOF 1.5 Objetivos 1.6 Referencias del captulo 1
9 11 13
14
16 17 19
CAPTULO 2. DESARROLLO 2.1. Planta experimental de laboratorio para el proceso ESOF 2.2. Planta piloto para el proceso ESOF 2.3. Resultados 2.3.1. Anlisis cintico de la electro-oxidacin en laboratorio de lignosulfonato mediante energa de red 2.3.2. Anlisis cintico de la electro-oxidacin de lignosulfonato mediante energa solar fotovoltaica 2.3.3 Demostracin del proceso ESOF a escala piloto para el tratamiento de aguas residuales urbanas 2.3.4. Sostenibilidad ambiental del suministro de energa al proceso ESOF mediante Anlisis de Ciclo de Vida
25 27 34 41 41
46
57
66
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Electro-oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica
2.4 Referencias del captulo 2 2.5 Nomenclatura del captulo 2
75 80
CAPTULO 3. CONCLUSIONES / CHAP TER 3. CONCLUSIONS 3.1 Conclusiones y trabajo futuro
83 85 87
3.1 Conclusions and future work
CAPTULO 4. ARTCULOS CIENTFICOS / CHAPTER
4. SCIENTIFIC
89
ARTICLES
4.1 Dominguez-Ramos, A., Aldaco, R., Irabien, A. Life cycle assessment as a tool for cleaner production: Application to aluminium trifluoride. Int. J. Chem. React. Eng. 2007, 5 (A33) 4.2 Dominguez-Ramos, A., Aldaco, R., Irabien, A., Electrochemical oxidation of lignosulfonate: Total organic carbon oxidation kinetics. Ind. Eng. Chem. Res. 2008, 47, 9848 4.3 Dominguez-Ramos, A., Aldaco, R., Irabien, A. Photovoltaic Solar Electrochemical Oxidation (PSEO) for lignosulfonate waste water treatment. J. Chem. Technol. Biotechnol. 2010, 85, 821 4.4 Dominguez-Ramos, A., Held, M., Aldaco, R., Fischer, M., Irabien, A. Prospective CO2 emissions from energy supplying systems: photovoltaic systems and conventional grid within Spanish frame conditions. Int. J. Life Cycle Assess. 2010, En prensa, DOI: 10.1007/s11367-010-0192-3 123 111 103 91
Resumen
Abstract
Resumen / Abstract
Resumen
El desarrollo de nuevos procesos de tratamiento de aguas residuales con carga orgnica debe estar guiado por criterios de sostenibilidad que integren simultneamente rentabilidad econmica, aceptacin social y proteccin del medio ambiente. La presente tesis doctoral estudia la integracin de la energa solar fotovoltaica con criterios de sostenibilidad como estrategia en el tratamiento de aguas residuales con carga orgnica. Los efluentes contaminados con materia orgnica biodegradable son tratados principalmente mediante procesos biolgicos, caracterizados por ser poco intensivos en energa. Sin embargo, esta clase de tratamientos no son capaces de hacer frente a la presencia de sustancias biorrefractarias. Los procesos avanzados de oxidacin, gracias a la intermediacin de oxidantes fuertes, consiguen la degradacin de la materia orgnica. De entre estos, los procesos basados en tecnologa de electro-oxidacin permiten la transformacin de la materia orgnica en dixido de carbono debido a la generacin de radicales hidroxilos cuando en el electrodo adecuado se establece la suficiente diferencia de tensin entre nodo y ctodo como consecuencia de la corriente elctrica circulante, evitando la formacin de lodos (procedentes de la reproduccin y crecimiento microbiano) como sucede en procesos biolgicos y de coagulacin. De esta forma, con un nivel de conductividad suficiente en el efluente, se evita la necesidad de utilizar reactivos qumicos y se elimina la necesidad de gestionar lodos. De entre los distintos materiales electrdicos existentes, los electrodos fabricados en diamante dopado con boro son bien conocidos por favorecer la generacin de radicales hidroxilos frente a reacciones secundarias al tiempo que presentan excelentes propiedades de resistencia mecnica y qumica. Sin embargo, la tecnologa de electro-oxidacin, al ser intensiva en energa elctrica por unidad de volumen tratado, condiciona el perfil medioambiental de la tecnologa en su comparacin con otras tecnologas para efluentes biodegradables, al transferir los impactos entre los distintos compartimentos ambientales (elevado consumo energtico frente a generacin de lodos y consumo de reactivos). En este sentido, la intensificacin del proceso de electrooxidacin mediante la integracin de energa solar fotovoltaica para generar la corriente entre electrodos permite disponer de un proceso con emisiones mnimas de dixido de carbono por unidad de volumen tratado resultando una opcin que mejora el perfil medioambiental de los procesos convencionales de tratamiento, al utilizar energa renovable y evitar la generacin/gestin de lodos y el consumo de reactivos qumicos. El objetivo de la presente tesis es demostrar la viabilidad tecnolgica de un proceso integrado y autosostenible de Electro-Oxidacin asistido por energa Solar Fotovoltaica (proceso ESOF) para el tratamiento de aguas residuales contaminadas con carga orgnica y evaluar la sostenibilidad ambiental del proceso ESOF al utilizar energa solar fotovoltaica frente a la energa de red en el proceso de electro-oxidacin.
Para ello, en primer lugar se realiz un estudio a escala de laboratorio de la degradacin del Carbono Orgnico Total en disoluciones de lignosulfonato (sustancia orgnica biorrefractaria empleada como modelo) en una planta de electro-oxidacin a escala de laboratorio empleando corriente elctrica de red. Los resultados obtenidos en modo discontinuo mostraron que existe una relacin de tipo hiperblico entre la constante cintica de eliminacin de Carbono Orgnico Total y un parmetro que relaciona corriente aplicada y cantidad de materia orgnica. De esta forma, bajo altos valores de el proceso estar controlado por la transferencia de materia reaccin en la superficie con los radicales hidroxilos. En segundo lugar se estudi la degradacin del Carbono Orgnico Total en disoluciones de lignosulfonato con corriente procedente directamente de mdulos solares fotovoltaicos (proceso ESOF). En tercer lugar se escala a planta piloto el proceso ESOF. Se instal y adapt una planta piloto de electro-oxidacin con una capacidad de tratamiento 50 veces superior, siendo posible la alimentacin con corriente continua y mediante energa solar fotovoltaica en la EDAR de Aguilar de Campoo (Palencia). De la comparacin con los resultados obtenidos a escala de laboratorio para el tratamiento de lignosulfonato y aguas residuales urbanas procedentes de la EDAR con alimentacin de red, se dedujo que el escalado del proceso y del consumo energtico de la planta es posible por cuanto la configuracin de los electrodos es similar en ambos equipos. La planta piloto fue capaz de operar en modo continuo, demostrando la viabilidad tecnolgica del proceso de electro-oxidacin de aguas residuales urbanas de baja carga orgnica y bajas conductividades (menos de 1 mScm-1) en continuo para una relacin caudal por rea de electrodo de 29 Lm-2h-1, con eliminaciones superiores al 50% en Carbono Orgnico Total y Demanda Qumica de Oxgeno con una potencia elctrica por unidad de rea andica de 0,80 kWm-2, lo que conduce a un consumo energtico especfico para la electro-oxidacin del orden de 25 kWhm-3. En cuarto lugar se ha empleado la metodologa del Anlisis de Ciclo de Vida para evaluar la sostenibilidad ambiental de la energa suministrada al proceso de electro-oxidacin mediante corriente de la red y mediante energa solar fotovoltaica. Los resultados mostraron valores del orden de 0,5 kgCO2-eq.kWh-1 y 0,2 kgCO2-eq.kWh-1 para la red elctrica espaola en 2007 y diferentes escenarios para el horizonte 2030 respectivamente. La energa procedente de mdulos solares utilizando diferentes tecnologas fotovoltaicas arrojan valores del orden de 0,030 kgCO2-eq.kWh-1 bajo irradiacin en Espaa para 2007 y de 0,010 kgCO2-eq.kWh-1 considerando la evolucin de las diferentes tecnologas fotovoltaicas en el horizonte 2030. Estos datos se pueden interpretar como una relacin del orden 1/17 en la contribucin al mientras que para bajos valores de , el proceso estar controlado por la corriente aplicada, ya que el proceso tiene lugar en dos etapas en serie: transporte hasta la superficie del electrodo y
Resumen / Abstract
calentamiento global del suministro directo de energa integrada en el proceso de tratamiento por electro-oxidacin frente al suministro de energa de la red en Espaa.
Abstract
The development of new processes for wastewater treatment polluted by organic loading should be guided by sustainability criteria allowing an integration of economic profit, social acceptance and environmental protection. The current doctoral thesis studies the integration of the photovoltaic solar energy with sustainability criteria as essential strategy in the treatment of wastewater polluted by organic loading. Biodegradable organic matter polluted effluents are mainly treated by low intensive energy processes such as biological processes. However, these treatments are not able to deal with biorefractory substances. The advanced oxidation processes, thanks to the presence of strong oxidants leads to the degradation of organic matter. Among these advanced processes, those based in electro-oxidation technology allows the transformation of organic matter into carbon dioxide due to the generation of hydroxyl radicals at suitable electrodes when enough voltage difference between anode and cathode as a consequence of the applied current, avoiding the sludge formation (from microbial growth) as it happens in biological or coagulation processes. When a certain effluent conductivity is reached, there is no need of chemicals and removes the latter management of the sludge. Different electrodes are available: boron doped diamond electrodes are well known for promoting hydroxyl radicals versus secondary reactions and for their excellent mechanical and chemical properties. However, electro-oxidation technology is an energy intensive process per unit of treated volume, which affects the environmental profile of the technology when compared with other technologies for biodegradable effluents (high energy consumption versus sludge formation and chemicals consumption). The intensification of the electro-oxidation process by means of the integration of solar photovoltaic energy to create the current between electrodes gives a process with minimal carbon dioxide emissions per unit of volume treated, so it is a possibility to improve the environmental profile versus the conventional treatment processes due to the use of renewable energy, no need of chemicals and reduction of sludge. The aim of this PhD thesis is to demonstrate the technical viability of an integrated and selfsustainable Photovoltaic Solar Electro-Oxidation process (PSEO process) for the treatment of wastewater polluted by organic loading and to assess the environmental sustainability of the PSEO process versus the use of grid power in the electro-oxidation process. To that end, it was concluded a lab scale study of the removal of Total Organic Carbon lignosulfonate solutions (biorefractory organic substance used as model substance) in a lab scale experimental plant using conventional grid power. The results in batch mode did show that there is an hyperbolic relationship between the kinetic constant for Total Organic Carbon removal and a parameter that relates the applied current and the content of organic matter. At high values of , the process will be controlled by mass transfer. On the other hand, at low
Resumen / Abstract
steps: transfer to the electrode surface and reaction in the surface with hydroxyl radicals.
values of the process will be limited by the applied current, as the process takes place in two As a second step a study of the degradation of Total Organic Carbon from lignosulfonate solutions with current from photovoltaic solar modules (PSEO process) was completed. From the results, it was deduced that under very high values of applied current (high irradiance
values), additional mechanisms to mass transfer plus surface reaction may exist: electrogenerated reagents not controlled by mass transfer due to its excess in the bulk phase. As a third step the scale-up of the process was done. A pilot plant 50 times higher treatment capacity than at lab scale was installed and adapted for operation, being possible the supply of current with grid or photovoltaic solar power at the WWTP of Aguilar de Campoo (Palencia). The comparison of the results at lab and pilot scale for the treatment of lignosulfonate and urban wastewater from the EDAR with grid power showed that the scale-up of the kinetic constants and energy consumption of the plant is possible because of the equivalent electrodes at both scales. The pilot plant was able to work in a continuous mode, assessing the technical viability of the electro-oxidation process for low organic loading urban wastewater and low conductivity below 1 mScm-1 for a ratio flowrate/electrode area of 29 Lm-2h-1, with removal rates higher than 50% as Total Organic Carbon and Chemical Oxygen Demand and an electrooxidation power per unit of anodic area of 0.8 kWm-2, which leads to an specific energy consumption for the electro-oxidation of 25 kWhm-3. As a fourth step the Life Cycle Analysis methodology was applied to assess the environmental sustainability of the supply to the electro-oxidation process by grid power and by photovoltaic solar power. Values of 0.5 kgCO2-eq.kWh-1 and 0.2 kgCO2-eq.kWh-1 were obtained for the Spanish grid in 2007 and several prospected scenarios in the 2030 horizon respectively. The energy from photovoltaic solar modules considering different photovoltaic technologies gave values of 0.030 kgCO2-eq.kWh-1 under Spanish irradiation in 2007 and of 0.010 kgCO2eq.kWh-1 considering the evolution of selected photovoltaic technologies for 2030 horizon; these values can be interpreted as a ratio 1/17 in the contribution to global warming from the direct supply of energy (photovoltaic solar energy) to the electro-oxidation process in comparison to the supply from the conventional grid mix.
Captulo 1. Planteamiento
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1.1 La tecnologa de Electro-Oxidacin para el tratamiento de aguas residuales

La electro-oxidacin (tambin conocida como oxidacin electroqumica) es un tecnologa concebida tanto para la oxidacin electroqumica en el tratamiento de efluentes residuales con carga orgnica como para la electrosntesis selectiva de productos de valor aadido (Chen, 2004). Como tecnologa para el tratamiento de aguas, la electro-oxidacin se enmarca dentro del grupo de los Procesos de Oxidacin Avanzada (POA) por cuanto es posible generar radicales hidroxilos OH bajo ciertas condiciones de operacin y en ciertos electrodos (Rodrigo et al., 2001; Marselli et al., 2003), oxidando la materia orgnica hasta dixido de carbono, no siendo necesario el consumo de reactivos qumicos y evitando la generacin de fangos (Marselli et al., 2003; Panizza et al., 2006). En los procesos de electro-oxidacin, el efluente a tratar se hace circular por un reactor heterogneo, entrando en contacto con nodo y ctodo, en los que tienen lugar respectivamente las reacciones de oxidacin y reduccin. La diferencia de potencial aplicada genera una corriente elctrica continua que circula entre los electrodos, siendo capaz de generar especies de alto poder oxidante en la superficie andica como los radicales hidroxilo OH o bien conducir a la generacin en el medio acuoso de agentes oxidantes electrogenerados como hipoclorito (ClO-) o peroxodisulfato (S2O82-) -en funcin del correspondiente anin precursor-, los cuales se encargan de oxidar la materia orgnica hasta dixido de carbono. Por tanto, es posible distinguir dos mecanismos bsicos de electro-oxidacin en medio acuoso cuya extensin depende del material electrdico, del potencial aplicado y del electrolito soporte empleado: oxidacin directa y oxidacin indirecta (Simond y Comninellis, 1997; Chiang et al., 1995; Szpyrkowicz et al., 2001; Caizares et al., 2002; Marselli et al., 2003). Por otra parte, las caractersticas del efluente como concentracin de materia orgnica, pH, temperatura, velocidad lineal de circulacin y configuracin del reactor afectan de forma notable a la extensin de cada uno de esos mecanismos. La tecnologa de electro-oxidacin trata de hacer frente a aquellas situaciones en las que el efluente residual posee una baja capacidad de ser oxidado, haciendo inviable su tratamiento trmico o bien un bajo nivel de biodegradabilidad, para el que la opcin biolgica no es viable. Para valores de Demanda Qumica de Oxgeno por debajo 5.000 mgO2L-1, la electro-oxidacin es una alternativa interesante como POA (Kapaka et al., 2008). Se ha utilizado en aplicaciones para el tratamiento de efluentes con concentraciones de Demanda Qumica de Oxgeno entre 1.000 mgO2L-1 hasta 100.000 mgO2L-1 (Fryda et al., 2003), aunque la mayora de las aplicaciones prcticas se encuentran por debajo del rango de 5.000 mgO2L-1. La Tabla 1.1.1 resume algunas aplicaciones recientes de la electro-oxidacin, tanto en efluentes reales como sintticos:
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Tabla 1.1.1 Referencias de contaminantes tratados mediante electro-oxidacin en efluentes reales y sintticos Efluente real Industria aceitera Referencia Disolucin sinttica Cianuros Fenol Clorofenol 2-naftol 3-metilpiridina Referencia Perret et al., 1999 Caizares et al., 2002; Moro et al., 2004 Rodrigo et al., 2001 Panizza et al., 2001a Iniesta et al., 2001a
Caizares et al., 2006a; Giannis et al., 2007 Pulpa y pasta de Springer et al., 1995; papel Buzzini et al., 2006 Vlyssides y Israilides, Textil 1998; Malpass et al., 2007 Farmacutica Caizares et al., 2006b Chiang et al., 1995; Chiang et al., 2001; Cabeza et al., Lixiviado de 2007; Deng y Englehardt vertedero et al., 2007; Lei et al., 2007 Rao et al., 2001; Szpyrkowicz et al., 2001; Cuero Szpyrkowicz et al., 2005a; Szpyrkowicz et al., 2005b Fenol Rajkumar y Palanivelu, formaldehido 2004 Rajkumar y Palanivelu, Aceite de refineria 2004 Farmacutica genricos Rajkumar y Palanivelu, 2004
Glucosa Polihidroxibencenos Histidina
Bonfatti et al., 2000 Caizares et al., 2004 Chen et al., 2007 Caizares et al., 2006c; Caizares et al., 2006d; Rajkumar y Kim, 2004; Fernandes et al., 2004, Panizza et al., 2007 Boye et al., 2006; Brillas et al., 2004; Brillas et al., 2007; Flox et al., 2006 Weichgrebe et al., 2004
Tintes sintticos
Lavado de coches Industria del motor
Panizza et al., 2005 Kraft et al., 2003
Herbicidas Frmacos
Por otra parte, la seleccin del material electrdico es clave en el proceso de electro-oxidacin. De los materiales disponibles en el mercado para electro-oxidacin, el diamante dopado con boro ha sido reconocido como un material excelente para la eliminacin de materia orgnica debido a alta estabilidad andica y amplia ventana electroqumica (Iniesta et al., 2001b; Chen, 2004) as como por operar con una elevada eficiencia energtica bajo las condiciones de operacin adecuadas por su elevado sobrepotencial de generacin de oxgeno, es decir, dificulta la generacin de oxgeno como producto principal de la oxidacin en el nodo (Panizza et al., 2001b; Chen, 2004). Entre las debilidades de la tecnologa, el uso de electrodos de baja eficiencia (Polcaro et al., 2003), los costes de inversin (Caizares et al., 2006) y esencialmente el elevado consumo de energa especfico por unidad de volumen tratado (Caizares et al., 2002; Caizares et al., 2006b; Caizares et al., 2006e; De Lucas et al., 2002). Este elevado consumo energtico no solo impacta de forma notable al proceso en cuanto a rentabilidad econmica, sino que lo hace fuertemente sobre la sostenibilidad ambiental del mismo. Es preciso por tanto buscar una intensificacin del proceso en cuanto al cambio de energa
12
procedente de la red por otra forma de energa con un menor impacto ambiental: la propuesta desarrollada es la integracin de energa solar fotovoltaica en el proceso. En el presente estudio se utiliz inicialmente lignosulfonato como compuesto modelo no biodegradable para su eliminacin en el proceso de electro-oxidacin, ya que las ligninas y sus productos derivados han sido descritos como responsables de una fraccin relevante del contenido en materia biorrefractaria procedente de los efluentes de la industria de la pulpa y el papel (Chiang et al., 1997; Chen et al., 2003; Gorenflo et al., 2003; Machado et al., 2003; Kreetachat et al., 2007; Ghoreishi y Haghighi, 2007).
1.2 Integracin de Energa Solar Fotovoltaica en la tecnologa de Electro-Oxidacin

La integracin de las energas renovables no slo en la generacin de energa sino en los procesos productivos es un elemento estratgico que la Ingeniera Qumica debe afrontar en el siglo XXI segn IChemE (2007) en el documento A Roadmap for the 21th Century Chemical Engineering. De entre las diferentes energas renovables, la energa solar fotovoltaica es, sin duda alguna, de gran inters en el mbito de la Ingeniera de Procesos. La energa solar fotovoltaica se basa en la separacin de cargas en la interfase de dos materiales que poseen diferentes mecanismos de conduccin (Grztel, 2004). Bajo irradiacin solar, los materiales como el silicio monocristalino, tienen la capacidad de absorber una fraccin de la energa transportada por los fotones que llegan a su superficie, transformndola en energa elctrica en un dispositivo como la clula solar, cuando se cierra el circuito elctrico con una carga (Luque y Hegedus, 2003). La preferencia por los materiales de silicio monocristalino (obtenidos por el proceso Czochralski) se debe a que su estructura cristalogrfica es preferible por cuanto, al reducir el nmero de granos en el material, dejan de actuar como defectos y por tanto aumentan la eficiencia de la conversin (Markvart, 2006). La energa de origen solar fotovoltaico ha sido demostrada como una excelente opcin para suministrar energa a los procesos electroqumicos en la lnea de la integracin de las energas renovables. Diferentes estudios relativos al estudio de procesos electroqumicos asistidos por energa solar fotovoltaica para tratamiento de efluentes han sido publicados (Tabla 1.2.1): electro-coagulacin con Fe3+ asistida por energa solar fotovoltaica (Valero et al., 2008) y produccin de reactivo Fenton para diferentes efluentes reales y tintes con nodos de carbn vtreo reticulado (Figueroa et al., 2009). En las referencias de la Tabla 1.1.2 se observa que los diferentes trabajos proponen la conexin directa de energa solar fotovoltaica al proceso de tratamiento; esta lnea de trabajo ha sido propuesta en el caso de procesos de smosis inversa (Thomson y Infield, 2003; Thomson y Infield, 2005), electro-dilisis para obtencin de agua potable (Ortiz et al., 2006; Ortiz et al., 2007); desalacin de agua mediante energa elica y solar fotovoltaica controlada a distancia
13
(Weiner et al., 2001); y generacin de hidrgeno con electro-combustin de orgnicos con nodos de BiOX-TiO2 (Hyunwoong et al., 2008). Tabla 1.2.1 Referencias de procesos electroqumicos de tratamientos de efluentes contaminados alimentados por energa solar fotovoltaica Proceso asistido Electrocoagulacin Conexin directa a los mdulos fotovoltaicos Caractersticas de la instalacin fotovoltaica 1x PQ10/40/01-02 AEG de 38,48 WP (silicio policristalino) Caractersticas de la unidad de tratamiento rea andica total: 235 cm2 (nodo central de aluminio entre ctodos de acero inoxidable) Electrodo 3D-RVC (5 cm x 5 cm x 1 cm); 60 poros por pulgadas; Separador de membrana cationes Nafion 117 Referencia
Si
Valero et al., 2008
Oxidacin con reactivo Fenton
Si (con regulador de voltaje)
1x Mdulo solar (50 W; 17 V; 2.9 A; Syscom Inc. Modelo BP 350U)
Figueroa et al., 2009
Por tanto, las principales consecuencias a tratar en un proceso de Electro-Oxidacin con integracin directa de energa Solar Fotovoltaica (proceso ESOF) son: i) la independencia de sistemas de almacenamiento masivo de energa: en definitiva, el volumen/caudal a tratar ser una funcin de la irradiacin solar disponible, por lo que siempre resultar ms efectivo almacenar el agua a tratar que la cantidad equivalente de energa en forma de p.ej.: bateras de plomo-cido sulfrico (Thomson y Infield, 2005) ii) el acoplamiento directo implica que el flujo que puede ser tratado es una funcin de la irradiacin solar (Valero et al., 2008).
1.3 Anlisis de Ciclo de Vida para la evaluacin de la sostenibilidad ambiental del proceso ESOF
El Anlisis de Ciclo de Vida (ACV) ha sido destacado por la Unin Europea como la metodologa apropiada para evaluar el impacto ambiental asociado a productos. El enfoque de ACV es bsico para llevar a cabo una valoracin objetivable, relacionando las actividades humanas y el medioambiente e identificando el impacto ambiental: el ACV es por tanto una herramienta muy potente en los procesos de toma de decisin, para valorar opciones sostenibles en la Ingeniera de Procesos (Azapagic, 1999). Para evaluar ambientalmente las posibilidades de la tecnologa de electro-oxidacin, el enfoque de ACV resulta de mximo inters, ya que la tecnologa de electro-oxidacin tiene una limitacin importante para su aplicacin derivada del elevado consumo energtico por unidad de volumen tratado. Ese valor depende de varios factores, principalmente, la conductividad del efluente existente y el grado de eliminacin deseado (Panizza et al., 2001b): bajos niveles de
14
conductividad llevan a valores elevados de resistencia hmica entre conductores aumentado el consumo de potencia para una densidad de corriente dada; por otra parte, altos niveles de eliminacin conducen a altos niveles de consumo energtico por cuanto es necesario aplicar una elevada cantidad de carga. Los valores de consumo son variables puesto que dependen de la conductividad y el nivel de eliminacin: es factible encontrar por tanto valores en el rango 10-1000 kWhm-3. Sin necesidad de operar en el valor mximo del rango anterior, queda claro que empleando energa de red y para efluentes degradables donde la electro-oxidacin y los procesos biolgicos son tecnolgicamente viables, la electro-oxidacin deja de ser competitiva puesto que el consumo neto de energa en un planta convencional de tratamiento de aguas residuales urbanas se encuentra en el orden de los 0,7 kWhm-3 (Tchobanoglous et al., 2003; California Energy Commision, 2006; European Commision, 2007). Por tanto energticamente, si los dos procesos se alimentan mediante corriente de red, y dejando al margen la energa adicional derivada del consumo de reactivos qumicos, el balance ambiental es notablemente deficitario para la electro-oxidacin. Por esta razn, es primordial emplear energa solar fotovoltaica, ya que slo as es viable la sostenibilidad ambiental del proceso. Por tanto, asumiendo unas emisiones de 0,5 kgCO2-eq.kWh-1 para el mix energtico espaol en 2007 (como se describe en el captulo de resultados) y valores del orden de 0,05 kgCO2-eq.kWh-1 para la energa solar fotovoltaica (Fthenakis et al., 2008), se obtiene la estimacin en kgCO2eq.m-3 para las diferentes opciones consideradas en la Tabla 1.3.1: Tabla 1.3.1 Estimaciones de emisiones de CO2.-eq.m-3 tratado mediante procesos convencionales de tratamiento, electro-oxidacin y electro-oxidacin asistida por energa solar fotovoltaica Energa para tratamiento (kWhm-3) Procesos biolgicos Electro-oxidacin (Red) Electro-oxidacin (Red) Electro-oxidacin (Fotovoltaica) Electro-oxidacin (Fotovoltaica)
a
Energa debida a reactivos qumicos y gestin de lodos (kWhm-3) RL 0 0 0 0

a
Emisiones de kgCO2-eq.kWh-1 (kgCO2-eq.kWh-1) 0,5 0,5 0,5 0,05 0,05

-3
Total de emisiones como kgCO2-eq.m-3 (kgCO2-eq.m-3) 0,35+RL0,5 5 50 0,5 5
0,7 10 100 10 100
RL es la energa asociada a los reactivos qumicos y a la gestin de lodos (kWhm )
En este anlisis se valora exclusivamente el proceso de tratamiento. Por tanto, se observa en la Tabla 1.3.1 que el ajuste del consumo energtico especfico a las condiciones de operacin determina la competitividad del perfil medioambiental. Adicionalmente, es importante sealar que la introduccin de energa renovable en plantas de tratamiento de aguas residuales urbanas tiene sentido siempre que parte de la energa generada se emplee en el propio
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proceso. Desde un enfoque de ACV, no es posible atribuir el beneficio medioambiental de introducir energa renovable en una planta de tratamiento convencional, si la energa generada se inyecta a la red en lugar del propio proceso (se emplea nicamente el espacio disponible en la planta para la instalacin de los equipos). Luego el uso del enfoque de ACV es bsico para cuantificar las distintas opciones disponibles y valorar la sostenibilidad ambiental de la opcin seleccionada.
1.4 Aplicacin del proceso ESOF

La Tabla 1.4.1 muestra un resumen comparativo en trminos cualitativos de sostenibilidad y viabilidad tcnica de los procesos biolgicos convencionales frente a la tecnologa de electrooxidacin alimentada por corriente de red y por energa solar fotovoltaica (proceso ESOF): Tabla 1.4.1 Valoracin cualitativa de los procesos de tratamiento (=Viable/Positivo; =Posiblemente viable/Medio; = No viable/Negativo) Procesos biolgicos convencionales Efluente biodegradable Efluente no biodegradable Consumo energtico Aplicaciones remotas/pequeas poblaciones Coste de inversin Coste de operacin Disponibilidad tecnolgica Aceptacin social Electro-oxidacin alimentada por red Proceso ESOF
El objetivo de la Tabla 1.4.1 es reflejar donde se encuentran los espacios de utilidad, y por tanto nichos de mercado de las tecnologas presentadas. De la Tabla 1.4.1 se puede concluir que el proceso ESOF es una opcin adecuada para el tratamiento de efluentes biodegradables y no biodegradables, con sentido para aplicaciones remotas o pequeas poblaciones. Los costes de operacin asociados al consumo energtico son sustituidos por costes de inversin en el equipo y los mdulos solares fotovoltaicos. La Figura 1.4.1 muestra como la integracin de procesos lleva a la creacin de un proceso innovador y autosostenible: proceso ESOF, cuya evaluacin ambiental se estudia mediante la aplicacin de la metodologa de ACV.
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INTEGRACIN DE PROCESOS ELECTROOXIDACIN SOLAR FOTOVOLTAICA
ACV
PROCESO ESOF
Figura 1.4.1. Relacin del proceso ESOF con la integracin de procesos y el Anlisis de Ciclo de Vida
1.5 Objetivos
La tesis se ha desarrollado en el marco de los proyectos CTM 2006-00317 Sostenibilidad de la
Produccin: Intensificacin e Integracin de Procesos en la Industria Qumica y Transformadora y Sostaqua Desarrollos tecnolgicos hacia un ciclo urbano del agua autosostenible, este ltimo dentro de la convocatoria CENIT, subvencionado por el Centro para
el Desarrollo Tecnolgico Industrial (CDTI). El proyecto Sostaqua est liderado por Aguas de Barcelona (www.agbar.es), respondiendo a un modelo integrador Administracin-UniversidadEmpresa, participando 15 empresas privadas (10 grandes empresas y 5 PYMES) y 13 Organismos Pblicos de Investigacin o Centros de Tecnolgicos distintos. En este proyecto se busca el desarrollo de un ciclo urbano del agua autosostenible, que se cierre realmente sobre s mismo en cuanto a los flujos de agua, y que minimice los requerimientos de energa y la aportacin de residuos al medio ambiente (www.sostaqua.com). La presente tesis doctoral forma parte de la tarea 9D de dicho proyecto: en concreto las actividades realizadas se encuadran en la tarea correspondiente a Integracin de fuentes de
energa renovable en tratamientos de agua.
En este contexto, el objetivo general de esta tesis doctoral es demostrar la viabilidad tecnolgica de un proceso integrado y autosostenible de Electro-Oxidacin asistido por energa Solar Fotovoltaica (proceso ESOF) para el tratamiento de aguas residuales contaminadas con carga orgnica y evaluar la sostenibilidad ambiental del proceso ESOF, al utilizar energa solar fotovoltaica frente a la energa de red del proceso de electro-oxidacin convencional. Esta tesis supone por tanto una contribucin innovadora a la integracin de energas renovables en los procesos de tratamiento de aguas
17
residuales. Para alcanzar este objetivo general fue necesario abordar los siguientes objetivos especficos: 1) Estudiar la eliminacin de materia orgnica no biodegradable (lignosulfonato) mediante una instalacin a escala de laboratorio de electro-oxidacin, operada en modo discontinuo y asistida por corriente controlada y llevar a cabo el anlisis cintico de la degradacin de materia orgnica expresada como Carbono Orgnico Total. 2) Estudiar la integracin de la energa solar fotovoltaica en un proceso a escala de laboratorio de electro-oxidacin para eliminacin de materia orgnica no biodegradable (lignosulfonato) y llevar a cabo el anlisis cintico de la degradacin de materia orgnica expresada como Carbono Orgnico Total. 3) Demostrar la viabilidad tecnolgica de la depuracin de aguas residuales urbanas en continuo mediante una instalacin a escala de planta piloto de electro-oxidacin ubicada en una EDAR y asistida por corriente elctrica controlada. 4) Evaluar la sostenibilidad ambiental en trminos de emisiones de CO2-eq. procedentes de sustituir la alimentacin mediante corriente elctrica de red por energa solar fotovoltaica. De acuerdo con estos objetivos especficos y considerando la estructura requerida para una tesis basada en un compendio de artculos, el documento de la tesis doctoral se desarrolla en 4 captulos, correspondindose el Captulo 1 con el planteamiento de la tesis. En el Captulo 2 se describen los equipos y mtodos empleados junto con los principales resultados obtenidos correspondientes a cada uno de los objetivos especficos. El Captulo 3 resume las conclusiones generales obtenidas y el trabajo futuro a desarrollar. Finalmente, el Captulo 4 conforma el ncleo central de la Tesis, incluyendo la copia de los artculos que la sustentan.
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1.6 Referencias del captulo 1

Bonfatti, F., De Battisti, A., Ferro, S., Lodi, G., Osti, S. Anodic mineralization of organic substrates in chloride-containing aqueous media. Electrochim. Acta 2000, 46, 305 Boye, B., Brillas, E., Marselli, B., Michaud, P., Comninellis, C., Farnia, G., Sandon, G. Electrochemical incineration of chloromethylphenoxy herbicides in acid medium by anodic oxidation with boron-doped diamond electrode. Electrochim. Acta 2006, 51, 2872 Brillas, E., Baos, M.A., Skoumal, M., Cabot, P.L., Garrido, J.A., Rodrguez, R.M. Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes. Chemosphere 2007, 68, 199 Brillas, E., Boye, B., Sirs, I., Garrido, J.A., Rodrguez, R.M., Arias, C., Cabot, P., Comninellis, C. Electrochemical destruction of chlorophenoxy herbicides by anodic oxidation and electro-Fenton using a boron-doped diamond electrode. Electrochim. Acta 2004, 49, 4487 Buzzini, A.P., Miwa, D.W., Motheo, A.J., Pires, E.C. Use of electrochemical oxidation process as post-treatment for the effluents of a UASB reactor treating cellulose pulp mill wastewater.
Water Sci. Technol. 2006, 54, 207

Cabeza, A., Urtiaga, A.M., Ortiz, I. Electrochemical treatment of landfill leachates using a borondoped diamond anode. Ind. Eng. Chem. Res. 2007, 46, 1439 California Energy Commission, California's water energy relationship CEC-700-2005-011-SF, 2005 Caizares, P., Daz, M., Domnguez, J.A., Garca-Gmez, J., Rodrigo, M.A. Electrochemical oxidation of aqueous phenol wastes on synthetic diamond thin-film electrodes. Ind. Eng. Chem.
Res. 2002, 41, 4187

Caizares, P., Sez, C., Lobato, J., Rodrigo, M.A. Electrochemical oxidation of
polyhydroxybenzenes on boron-doped diamond anodes. Ind. Eng. Chem. Res. 2004, 43, 6629 Caizares, P., Martnez, L., Paz, R., Sez, C., Lobato, J., Rodrigo, M.A. Treatment of Fentonrefractory olive oil mill wastes by electrochemical oxidation with boron-doped diamond anodes.
J. Chem. Tech. Biotechnol. 2006a, 81, 1331

Caizares, P., Paz, R., Lobato, J., Sez, C., Rodrigo, M.A. Electrochemical treatment of the effluent of a fine chemical manufacturing plant. J. Hazard. Mater. 2006b, 138, 173 Caizares, P., Gadri, A., Lobato, J., Nasr, B., Paz, R., Rodrigo, M.A., Sez, C. Electrochemical oxidation of azoic dyes with conductive-diamond anodes. Ind. Eng. Chem. Res. 2006c, 45, 3468 Caizares, P., Martnez, F., Lobato, J., Rodrigo, M.A. Electrochemically assisted coagulation of wastes polluted with eriochrome black T. Ind. Eng. Chem. Res. 2006d, 45, 3474
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Caizares, P., Sez, C., Lobato, J., Rodrigo, M.A. Detoxification of synthetic industrial wastewaters using electrochemical oxidation with boron-doped diamond anodes. J. Chem.
Tech. Biotechnol. 2006e, 81, 352

Chen, F., Lu, Z., Tu, B. Electro-degradation of sodium lignosulfonate. J. Wood Chem. Technol. 2003, 23, 261 Chen, G. Electrochemical technologies in wastewater treatment. Sep. Purif. Technol. 2004, 38, 11 Chen, L.C., Chang, C.C., Chang, H.C. Electrochemical oxidation of histidine at an anodic oxidized boron-doped diamond electrode in neutral solution. Electrochim. Acta 2007, 5, 2883 Chiang, L.C., Chang, J.E., Wen, T.C. Indirect oxidation effect in electrochemical oxidation treatment of landfill leachate. Water Res. 1995, 29, 671 Chiang, L.C., Chang, J.E., Tseng, S.C. Electrochemical oxidation pretreatment of refractory organic pollutants. Water Sci. Technol. 1997, 36, 123 Chiang, L.C., Chang, J.E., Chung, C.T. Electrochemical oxidation combined with physicalchemical pretreatment processes for the treatment of refractory landfill leachate. Environ. Eng.
Sci. 2001, 18, 369

De Lucas, A., Caizares, P., Rodrigo, M.A., Garca-Gmez, J. Electrochemical treatment of aqueous phenol wastes: A preliminary economical outlook. Waste Manag. Environ. 2002, 161 Deng, Y., Englehardt, J.D. Electrochemical oxidation for landfill leachate treatment. Waste
Manage. 2007, 27, 380

European Commission, Reference document on best available techniques in common waste water and waste gas treatment / management systems in the chemical sector, 2007 Fernandes, A., Morao, A., Magrinho, M., Lopes, A., C. I. Acid Orange 7. Dyes Pigments 2004, 61, 287 Figueroa, S., Vzquez. L, Alvarez-Gallegos, A. Decolorizing textile wastewater with Fenton's reagent electrogenerated with a solar photovoltaic cell. Water Res. 2009, 43, 283 Flox, C., Cabot, P.L., Centellas, F., Garrido, J.A., Rodrguez, R.M., Arias, C., Brillas, E. Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode. Chemosphere 2006, 64, 892 Fryda, M., Matthe, T., Mulcahy, S., Hampel, A., Schfer, L., Trster, I. Fabrication and application of Diachem electrodes. Diam. Relat. Mater. 2003, 12, 1950 Fthenakis, V.M., Kim, H.C., Alsema, E. Emissions from Photovoltaic Life Cycles. Environ. Sci. alves, I. Electrochemical degradation of
Technol. 2008, 42, 2168
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Ghoreishi, S.M., Haghighi, M.R. Chromophores removal in pulp and paper mill effluent via hydrogenation-biological batch reactors. Chem. Eng. J. 2007, 127, 59 Giannis, A., Kalaitzakis, M., Diamadopoulos, E. Electrochemical treatment of olive mill wastewater. J. Chem. Tech. Biotechnol. 2007, 82, 663 Gorenflo, A., Li, Y., Frimmel, F.H. Improved biodegradability of ligninsulfonic acid and wastewater after ozonation. Chem. Eng. Technol. 2003, 26, 11 Grtzel, M. Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells.
J. Photochem. Photobiol. A 2004, 164, 3

Hyunwoong, P., Vecitis, C.D., Wonyong, C., Weres, O., Hoffmann, M.R. Solar-powered production of molecular hydrogen from water. J. Phys. Chem. C. 2008, 112, 885 IChemE, Institution of Chemical Engineers, A roadmap for the 21th century chemical engineering 2007, http://www.icheme.org/roadmap2007.pdf (acceso en 2009) Iniesta, J., Michaud, P.A., Panizza, M., Comninellis, C. Electrochemical oxidation of 3methylpyridine at a boron-doped diamond electrode: Application to electroorganic synthesis and wastewater treatment. Electrochem. Commun. 2001a, 3, 346 Iniesta, J., Michaud, P.A., Panizza, M., Cerisola, G., Aldaz, A., Comninellis, C. Electrochemical oxidation of phenol at boron-doped diamond electrode. Electrochim. Acta 2001b, 46, 3573 Kapaka, A., Fti, G., Comninellis, C. Kinetic modelling of the electrochemical mineralization of organic pollutants for wastewater treatment. J. Appl. Electrochem. 2008, 38, 7 Kraft, A., Stadelmann, M., Blaschke, M. Anodic oxidation with doped diamond electrodes: A new advanced oxidation process. J. Hazard. Mater. 2003, 103, 247 Kreetachat, T., Damrongsri, M., Punsuwon, V., Vaithanomsat, P., Chiemchaisri, C., Chomsurin, C. Effects of ozonation process on lignin-derived compounds in pulp and paper mill effluents. J.
Hazard. Mater. 2007, 142, 250

Lei, Y., Shen, Z., Huang, R., Wang, W. Treatment of landfill leachate by combined aged-refuse bioreactor and electro-oxidation. Water Res. 2007, 41, 2417 Luque, A., Hegedus, S., Handbook of photovoltaic science and engineering. John Wiley & Sons, Chichester, 1138 2003 Machado, A.E.H., de Miranda, J.A., de Freitas, R.F., Duarte, E.T.F.M., Ferreira, L.F., Albuquerque, Y.D.T., Ruggiero, R., Sattler, C., de Oliveira, L. Destruction of the organic matter present in effluent from a cellulose and paper industry using photocatalysis. J. Photoch.
Photobio. A 2003, 155, 231
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Malpass, G.R.P., Miwa, D.W., Mortari, D.A., Machado, S.A.S., Motheo, A.J. Decolorisation of real textile waste using electrochemical techniques: Effect of the chloride concentration. Water Res. 2007, 41, 2969 Markvart, T. Solar electricity. 2nd, reproduced with corr. John Wiley & Sons, Chichester, 280 2006 Marselli, B., Garcia-Gomez, J., Michaud, P.A., Rodrigo, M.A., Comninellis, C. Electrogeneration of hydroxyl radicals on boron-doped diamond electrodes. J. Electrochem. Soc. 2003, 150, D79 Moro, A., Lopes, A., Pessoa de Amorim, M.T., Gonalves, I.C. Degradation of mixtures of phenols using boron doped diamond electrodes for wastewater treatment. Electrochim. Acta 2004, 49, 1587 Ortiz, J. M., , E., Gallud, F., , V., Montiel, V., Aldaz, A. Photovoltaic
electrodialysis system for brackish water desalination: Modeling of global process. J. Membr.
Sci. 2006, 274, 138

Ortiz, J. M., , E., Gallud, F., , V., Montiel, V., Aldaz, A. Electrodialysis of
brackish water powered by photovoltaic energy without batteries: direct connection behaviour.
Desalination, 2007, 208, 89

Panizza, M., Michaud, P.A., Cerisola, G., Comninellis, C. Anodic oxidation of 2-naphthol at boron-doped diamond electrodes. J. Electroanal. Chem. 2001a, 507, 206 Panizza, M., Michaud, P.A., Cerisola, G., Comninellis, C. Electrochemical treatment of wastewaters containing organic pollutants on boron-doped diamond electrodes: Prediction of specific energy consumption and required electrode area. Electrochem. Commun. 2001b, 3, 336 Panizza, M., Deluchi, M., Cerisola, G. Electrochemical degradation of anionic surfactants. J.
Appl. Electrochem. 2005, 35, 357

Panizza, M., Zolezzi, M., Nicolella, C. Biological and electrochemical oxidation of
naphthalenesulfonates. J. Chem. Tech. Biotechnol. 2006, 81, 225 Panizza, M., Barbucci, A., Ricotti, R., Cerisola, G. Electrochemical degradation of methylene blue. Sep. Purif. Technol. 2007, 54, 382 Perret, A., Haenni, W., Skinner, N., Tang, X.., Gandini, D., Comninellis, C., Correa, B., Foti, G. Electrochemical behavior of synthetic diamond thin film electrodes. Diam. Relat. Mater. 1999,
8, 820
Polcaro, A.M., Vacca, A., Palmas, S., Mascia, M. Electrochemical treatment of wastewater containing phenolic compounds: Oxidation at boron-doped diamond electrodes. J. Appl.
Electrochem. 2003, 33, 885
22
Rajkumar, D., Palanivelu, K. Electrochemical treatment of industrial wastewater. J. Hazard.
Mater. 2004, 113, 123

Rajkumar, D., Kim, J.G. Oxidation of various reactive dyes with in situ electro-generated active chlorine for textile dyeing industry wastewater treatment. J. Hazard. Mater. 2006, 136, 203 Rao, N.N., Somasekhar, K.M., Kaul, S.N., Szpyrkowicz, L. Electrochemical oxidation of tannery wastewater. J. Chem. Tech. Biotechnol. 2001, 76, 1124 Rodrigo, M.A., Michaud, P.A., Duo, I., Panizza, M., Cerisola, G., Comninellis, C. Oxidation of 4Chlorophenol at Boron-Doped Diamond Electrode for Wastewater Treatment. J. Electrochem.
Soc. 2001, 148, D60

Simond, O., Comninellis, C. Anodic oxidation of organics on Ti/IrO2 anodes using Nafion as electrolyte. Electrochim. Acta 1997, 42, 2013 Springer, A.M., Hand, V.C., Jarvis, T.S. Electrochemical removal of color and toxicity from bleached kraft effluents. Tappi J. 1995, 78, 85 Szpyrkowicz, L., Kelsall, G.H., Kaul, S.N., De Faveri, M. Performance of electrochemical reactor for treatment of tannery wastewaters. Chem. Eng. Sci. 2001, 56, 1579 Szpyrkowicz, L., Kaul, S.N., Neti, R.N. Tannery wastewater treatment by electro-oxidation coupled with a biological process. J. Appl. Electrochem. 2005a, 35, 381 Szpyrkowicz, L., Kaul, S.N., Neti, R.N., Satyanarayan, S. Influence of anode material on electrochemical oxidation for the treatment of tannery wastewater. Water Res. 2005b, 39, 1601 Tchobanoglous, G., Burton, F.L., Stensel, H.D. Wastewater engineering: Treatment and reuse.
4th edition, McGraw-Hill, Boston etc., 1819 2003

Thomson, M., Infield, D. A photovoltaic-powered seawater reverse-osmosis system without batteries. Desalination 2003, 153, 1 Thomson, M., Infield, D., Laboratory demonstration of a photovoltaic-powered seawater reverse-osmosis system without batteries. Desalination 2005, 183, 105 Valero, D., Ortiz, J.M., Expsito, E., Montiel, V., Aldaz, A. Electrocoagulation of a synthetic textile effluent powered by photovoltaic energy without batteries: Direct connection behaviour.
Sol. Energy Mater. Sol. Cells. 2008, 92, 291

Vlyssides, A.G., Israilides, C.J. Electrochemical oxidation of a textile dye and finishing wastewater using a Pt/Ti electrode. J. Environ. Sci. Heal. A 1998, 33, 847 Weichgrebe, D., Danilova, E., Rosenwinkel, K., Vedenjapin, A.A., Baturova, M. Electrochemical oxidation of drug residues in water by the example of tetracycline, gentamicine and aspirin.
Water Sci. Technol. 2004, 49, 201

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Weiner, D., Fisher, D., Moses, E. J., Katz, B., Meron, G. Operation experience of a solar-and wind-powered desalination demonstration plant. Desalination 2001, 137, 7
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Captulo 2. Desarrollo
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2.1. Planta experimental de laboratorio para el proceso ESOF

La planta experimental a escala de laboratorio del proceso de Electro-Oxidacin asistido por energa Solar Fotovoltaica (proceso ESOF) fue construida con el objetivo de estudiar la viabilidad de la degradacin de aguas residuales con carga orgnica y se encuentra ubicada en el Laboratorio de Radiocomunicaciones de la ETS de Ingenieros Industriales y de Telecomunicacin (Universidad de Cantabria). La ubicacin de esta instalacin se justifica por las facilidades existentes a la hora de ubicar el set de mdulos fotovoltaicos sobre el tejado del edificio, permitiendo una orientacin sur para los mismos, un anclaje sobre la estructura y evitando al mismo tiempo los efectos de sombras como consecuencia de los edificios prximos. La Figura 2.1.1 muestra un esquema de la planta experimental, la Figura 2.1.2 una fotografa de la instalacin y la Figura 2.1.3 una fotografa del conjunto de mdulos fotovoltaicos.
Reactor de electrooxidacin
Fuente de alimentacin
Caudalmetro
Absorbedor
Bomba centrfuga
Tanque de almacenamiento Multmetro
Set de mdulos solares fotovoltaicos
Figura 2.1.1. Diagrama de la planta experimental de Electro-Oxidacin asistida por energa Solar Fotovoltaica (proceso ESOF)
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Figura 2.1.2. Fotografa de la planta de laboratorio de Electro-Oxidacin asistida por energa Solar Fotovoltaica
Figura 2.1.3. Fotografa del set de mdulos solares fotovoltaicos de la planta de laboratorio de Electro-Oxidacin asistida por energa Solar Fotovoltaica
La planta experimental de electro-oxidacin est formada esencialmente por un reactor de electro-oxidacin equipado con electrodos de Diamante Dopado con Boro (DDB) alimentado por corriente de red, empleando una fuente de alimentacin para operar en condiciones galvanostticas o mediante un set de mdulos solares fotovoltaicos en condiciones de corriente no controlada, de forma que mediante un funcionamiento con recirculacin (modo discontinuo) es posible alcanzar el grado de eliminacin deseado en materia orgnica ajustando el tiempo de operacin y la corriente aplicada, es decir en funcin de la cantidad total de carga elctrica transferida. A continuacin se procede a describir en detalle las caractersticas de los principales elementos de la instalacin de laboratorio para el proceso ESOF:
Reactor de electro-oxidacin:
El reactor de electro-oxidacin Diacell106.02 fue adquirido a Adamant Technologies SA (www.adamantec.com). Dicho reactor se compone de un nico compartimento no dividido con dos electrodos circulares de DDB para un rea total de 70 cm2, entre los que circula el lquido a tratar, encontrndose paralelos y separados por una distancia de 1 mm. Tabla 2.1.1 Principales caractersticas del electrodo del reactor de electro-oxidacin (www.adamantec.com) Substrato Material Silicio policristalino Material Diamante dopado con boro Resistividad mcm 100 Resistividad mcm 100-150 Espesor mm 2 Recubrimiento Espesor m 1-3 Dimetro externo mm 100 rea electrodo cm2 70
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Esta distancia permite disminuir la resistencia hmica impuesta por el fluido circulante con el objetivo de minimizar la cada de tensin entre los electrodos. Una menor distancia entre electrodos podra conllevar problemas asociados a taponamientos en los compartimentos (partculas, etc.). La Tabla 2.1.1 resume las principales caractersticas del electrodo seleccionado. Al ser ambos electrodos de DDB, pueden actuar como nodo y ctodo, facilitando los procesos de limpieza del electrodo simplemente mediante inversin de la polaridad. El material de la carcasa es polipropileno y el ajuste de los electrodos a la misma se realiza apretando los seis tornillos del reactor. La Figura 2.1.4 muestra una fotografa del reactor de electro-oxidacin empleado en la planta del proceso ESOF. La mxima densidad de corriente que se puede aplicar a este reactor es de 1000 mAcm-2.
Figura 2.1.4. Fotografa del reactor de electro-oxidacin de la planta experimental de ElectroOxidacin asistida por energa Solar Fotovoltaica
Fuente de alimentacin
Para poder operar en condiciones de corriente constante fue necesario disponer de una fuente de alimentacin. La fuente de alimentacin Agilent Technologies 6554A fue adquirida a Agilent Technologies (www.agilent.com).
Mdulos solares fotovoltaicos y unidad de medicin de la irradiacin solar

Para alimentar el proceso de electro-oxidacin mediante energa solar fotovoltaica, se dispuso de una instalacin solar fotovoltaica aislada sobre el tejado de la ETS de Ingenieros Industriales y de Telecomunicacin (Universidad de Cantabria). Los mdulos se localizaron exactamente sobre el laboratorio donde se encuentra la planta de electro-oxidacin, de tal forma que se minimizan las prdidas de transporte de la corriente. La instalacin fotovoltaica en cuestin est constituida por 4 mdulos solares SunTech Power STP160 (www.suntech-power.com) para una potencia pico de 160 WP por mdulo (rea efectiva de 1,125 m2), luego la potencia pico total de la instalacin es de 640 WP. La Tabla 2.1.2 recoge las principales caractersticas de los mdulos
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solares fotovoltaicos seleccionados. La salida de los mdulos llega a una caja de conexiones, donde gracias a un set de interruptores diferenciales es posible alimentar al proceso con un nmero de mdulos a elegir. La salida de los mdulos llega a un terminal comn para alimentar as al reactor de electro-oxidacin mediante corriente continua. Los mdulos se dispusieron en una configuracin en paralelo, de tal forma que las corrientes generadas por cada mdulo resultan aditivas. Consecuentemente, al conectar un mayor nmero de mdulos, es posible alimentar al reactor con una intensidad mayor. La orientacin de los mdulos es sur (20 Oeste) y con una inclinacin de 38. Como consecuencia, se evit la presencia de sombras durante los experimentos. Se dispuso una unidad de medicin de la irradiacin solar para conocer los valores de irradiacin solar y temperatura en los mdulos. Dicha unidad SUNREADER (SunTech Corp) permite disponer de los perfiles de irradiacin solar (medidos como Wm-2), as como los de temperatura en los mdulos (C) con una frecuencia de 15 minutos. Tabla 2.1.2. Principales caractersticas de los mdulos solares fotovoltaicos STP160 utilizados en la instalacin experimental de electro-oxidacin a escala de laboratorio (condiciones estndar de 1000 Wm-2 y 25C) iSC,ref A 5,0 vOC,ref V 43,2 iMP,ref A 4,65 vMP,ref V 34,4
Resto del equipamiento

El lquido a tratar se carga en un tanque de alimentacin de vidrio encamisado (diseo propio). Desde ese tanque, una bomba centrfuga (PANWORLD) de 150 W fue la encargada de bombear el fluido a travs del reactor de electro-oxidacin, de tal forma que el lquido es impulsado a travs del reactor y retorna al tanque, operando as en circuito cerrado. Se dispuso una unidad de refrigeracin (SBS) para operar a temperatura constante en el interior del tanque. Mediante una vlvula de bola fue posible ajustar el caudal de lquido que circulaba a travs del reactor y medido mediante caudalmetro.
Procedimiento analtico
Medida de pH y conductividad
Durante los experimentos correspondientes al estudio de la cintica de eliminacin de lignosulfonato, los valores de pH y conductividad al inicio y al final de cada experimento fueron medidos en un pHmetro Crison GLP22 equipado con electrodos de pH 52-02 y en una sonda de conductividad Crison CM35. Posteriormente, durante la etapa de experimentacin mediante energa solar fotovoltaica se emple para la medicin en continuo una unidad de medida Hach HQ40d, equipada con sonda de pH PHC101-01 y conductividad CDC401-01.
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Medida de Carbono Orgnico Total

El Carbono Orgnico Total (COT) fue medido mediante un equipo Shimadzu TOC-V CPH con ASI-V operado con aire sinttico (la presin de trabajo era de 200 KPa y el caudal de trabajo de 150 mLmin-1). Para el calibrado del Carbono Total, se emple una solucin patrn de COT de 1000 mgL-1, mientras que para el Carbono Inorgnico se emple una disolucin de carbonato sdico Na2CO3 de 100 mgCL-1 (AENOR, 1998).
Medida de Demanda Qumica de Oxgeno

La Demanda Qumica de Oxgeno (DQO) fue medida de acuerdo a los Standard Methods (mtodo 5220D, reflujo cerrado, mtodo colorimtrico (APHA, 1998)) utilizando un digestor Hanna COD-reactor HI839800 para la etapa de digestin y un espectrofotmetro Merck Spectroquant NOVA 600 para las correspondientes medidas colorimtricas. Posteriormente, durante la etapa de experimentacin mediante energa solar fotovoltaica se emple para la medicin un espectrofotmetro Hach DR 5000, empleado kits de anlisis LCK314 en los rangos 10-100 mgO2L-1 y 100-1500 mgO2L-1.
Materiales: Lignosulfonato, electrolito, calibracin y otros

La compaa Lignotech Ibrica SA (www.lignotech.com) proporcion las muestras de lignosulfonato de calcio y magnesio en su producto comercial Borrebond 55S, con un peso molecular de aproximadamente 3000 dalton. El lignosulfonato es obtenido como subproducto del proceso de produccin de pasta de papel al sulfito. Este producto es soluble en agua en todas las proporciones y mantiene una concentracin residual de azcares reducidos. Para la preparacin de las disoluciones de lignosulfonato no se realiz ningn proceso de purificacin adicional. Se emple sulfato sdico Na2CO3 (Panreac) y cloruro sdico NaCl (Panreac) como electrolitos soporte comunes. En cuanto a la calibracin y medida de COT, se utiliz: como reactivo para la calibracin de Carbono Total, patrn de COT estabilizado en solucin de 1000 mgCL-1 (Merck); como reactivo para la calibracin de Carbono Inorgnico, disolucin de carbonato sdico Na2CO3 de 100 mgL1
(Panreac) y aire sinttico (Air Liquide)
En cuanto a la calibracin y medida de DQO, se utiliz: sulfato de plata Ag2SO4 10 gL-1 en disolucin de cido sulfrico H2SO4 (Panreac); dicromato potsico K2Cr2O7 0,04 molL-1 con mercurio (II) a 80 gL-1 (Panreac); Kits de anlisis de DQO LCK314 rangos 10-100 y 100-1500 mgO2L-1 (Hach-Lange). Para la preparacin de las disoluciones de lignosulfonato se emple agua ultrapura procedente de una unidad Mili-Q (Millipore). Se emple agua destilada de una unidad Milli-RO (Millipore) para las operaciones de limpieza de la instalacin.
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Procedimiento experimental En la instalacin experimental de electro-oxidacin, el lquido a tratar es bombeado desde el tanque de alimentacin y circula por el interior del reactor impulsado por una bomba centrfuga. A continuacin el lquido regresa al tanque de alimentacin, de tal forma que si se aplica corriente bien a travs de la fuente de alimentacin o bien a travs del set de mdulos solares fotovoltaicos, la concentracin de materia orgnica en el tanque disminuye como consecuencia de la oxidacin hasta dixido de carbono (el exceso de CO2 generado pasa por el absorbedor formando burbujas). La correspondiente disolucin de lignosulfonato se prepara aadiendo la cantidad necesaria de lignosulfonato disuelto en agua ultrapura y ajustando la concentracin correspondiente de electrolito soporte. El bao de refrigeracin se ocupa de mantener el lquido a una temperatura constante a lo largo del experimento: una vez se alcanza la temperatura estacionaria adecuada, es posible alimentar el reactor con corriente continua. Se toman muestras segn la programacin para cada experimento hasta un volumen por muestra de 20 mL, con el objetivo de prevenir modificar en exceso el cociente rea andica-volumen total de lquido. Una vez realizado el correspondiente experimento, se proceda a un primer aclarado con agua destilada (con inversin de la polaridad) ms un segundo y tercer aclarado con agua destilada. Las tres variables seleccionadas para el estudio de la degradacin de la materia orgnica procedente de la disolucin de lignosulfonato fueron: concentracin inicial de DQO (el valor ms bajo es representativo de los efluentes de salida en la industria de la pulpa y el papel), densidad de corriente (para garantizar potenciales entre electrodos suficientemente altos para generar radicales hidroxilos) y naturaleza y concentracin de electrolito soporte (para garantizar un nivel mnimo de conductividad entre electrodos). Para analizar la influencia de cada variable se estudi cada una de ellas en dos niveles diferentes. Los sets de experimentos nombrados como Si son aquellos en los que se emple sulfato sdico como electrolito soporte y Ci aquellos en los que se utiliz cloruro sdico. La Tabla 2.1.3 resume las condiciones de trabajo durante la operacin en condiciones de corriente controlada. Para analizar la degradacin de materia orgnica procedente de lignosulfonato en condiciones de corriente fotovoltaica, se consideraron distintos casos en los que el perfil de irradiacin diaria fuese diferente de tal forma que pudiese observarse el efecto de la irradiacin variable sobre el proceso. Para efectos de comparacin, el valor de densidad de corriente que se recoge en la Tabla 2.1.3 se corresponde al valor promedio de corriente en el experimento. Todos los experimentos en condiciones de corriente fotovoltaica comenzaron a las 10:30 hora local. Independientemente del origen de la corriente elctrica, en los experimentos a escala de laboratorio se emple un caudal de recirculacin de 300 Lh-1 as como una temperatura de trabajo de entre 20-25C.
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Tabla 2.1.3. Condiciones de trabajo en condiciones de corriente de red y fotovoltaica para eliminacin de lignosulfonato Experimento S1, C1 S2, C2 S3, C3 S4, C4 S5, C5 S6, C6 S7, C7 S8, C8 E1b E2b E3b E4b Electricidad Red Red Red Red Red Red Red Red Solar Solar Solar Solar
b
[DQO]0 mgO2L-1 500 500 500 500 1500 1500 1500 1500 1500 1500 500 1500
J mAcm-2 30 30 60 60 30 30 60 60 35a 121a 220a 96a
Electrolito mgL-1 5000 2500 5000 2500 5000 2500 5000 2500 2500 2500 300 2500
a Valor promedio obtenido en el experimento; condiciones de corriente no controlada
Los perfiles de irradiacin se detallan en el apartado de resultados para
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2.2. Planta piloto para el proceso ESOF

La planta experimental a escala de planta piloto del proceso de Electro-Oxidacin asistido por energa Solar Fotovoltaica (proceso ESOF) se ha ubicado en la Estacin Depuradora de Aguas Residuales Urbanas (EDAR) de Aguilar de Campoo (Palencia). En el marco del proyecto Sostaqua y con la colaboracin de los grupos Agbar y Aquagest, se analizaron diferentes posibles ubicaciones para la planta piloto del proceso ESOF. De entre las candidatas, la EDAR de Aguilar de Campoo cumpla satisfactoriamente con los requisitos exigidos para ubicar la planta piloto as como para un funcionamiento con mdulos solares fotovoltaicos (sin problemas de sombras).
Rectificadores
Bombas centrfugas
Tanque de retencin Lnea de reactores de electro-oxidacin
ENTRADA
Bomba centrfuga
Tanque de almacenamiento
Filtro de anillas
Bomba sumergible
Set de mdulos solares fotovoltaicos
SALIDA
Arqueta de alimentacin
Figura 2.2.1. Esquema de la planta piloto de Electro-Oxidacin asistida por energa Solar Fotovoltaica El proceso ESOF est constituido por una planta piloto comercial de electro-oxidacin (ubicada en el interior de una caseta prefabricada de dimensiones especiales) y un set de mdulos solares fotovoltaicos tal y como se muestra en la Figura 2.2.1 Una fotografa del interior de la
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caseta con la planta de electro-oxidacin se muestra en la Figura 2.2.2; la Figura 2.2.3 muestra una fotografa del set de mdulos solares fotovoltaicos ubicados sobre la caseta en la que se encuentra el reactor de electro-oxidacin.
Figura 2.2.2. Fotografa de la planta piloto de Electro-Oxidacin asistida por energa Solar Fotovoltaica ubicada en la EDAR de Aguilar de Campoo
Figura 2.2.3. Fotografa del set de mdulos solares fotovoltaicos de la planta piloto de Electro-Oxidacin asistida por energa Solar Fotovoltaica ubicada en la EDAR de Aguilar de Campoo
El proceso de electro-oxidacin ha funcionado con tres lneas de electro-oxidacin equipadas con cinco reactores (electrodos de DDB) cada una. Cada lnea es capaz de operar independientemente, para lo que dispone de su propia bomba centrfuga vertical as como de un rectificador individual para la alimentacin por corriente de red. Existe un tanque de alimentacin donde se almacena el lquido a tratar: desde ah, el lquido circula a travs de los reactores de la lnea, impulsado por la bomba de su lnea y retorna al mismo, con lo que el sistema opera en modo discontinuo. Al aplicar corriente, tiene lugar la oxidacin de la materia orgnica hasta su combustin como CO2, por lo que la concentracin de materia orgnica (expresada como COT y DQO) disminuye con el tiempo. Ajustando el tiempo de operacin y la corriente aplicada es posible llegar al nivel deseado de eliminacin de materia orgnica. El conjunto de la instalacin se alimenta desde una toma de corriente alterna trifsica prxima a la caseta. Como primera etapa del escalado a planta piloto, se decidi instalar un set de mdulos solares para una nica lnea de operacin, de tal forma, que al igual que suceda con la instalacin de laboratorio, la energa solar fotovoltaica alimenta al proceso de electro-oxidacin. A continuacin se procede a describir en detalle las caractersticas de los principales elementos de la instalacin de planta piloto para el proceso ESOF:
Planta piloto de electro-oxidacin

La planta piloto de electro-oxidacin fue gestionada a travs de la empresa Apria Systems SL (www.apriasystems.es) siendo suministrada por Adamant Technologies SA (www.adamantec.com), la compaa responsable de la distribucin del reactor de electro-
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oxidacin de laboratorio. La adquisicin de datos y el control de la instalacin se realizan mediante un controlador lgico programable (PLC).
Lnea de reactores de electro-oxidacin, bomba centrfuga, rectificador y sistema de control

Cada lnea de electro-oxidacin dispone de 5 reactores de electro-oxidacin Diacell108-01, con 10 compartimentos no divididos: cada compartimento consta de un nodo circular de DDB (mismas caractersticas que las mostradas en la Tabla 2.1.1) y un ctodo de acero inoxidable ASI para un rea total de 70 cm2 por electrodo, entre los que circula el lquido a tratar, encontrndose paralelos y separados por una distancia de 1 mm. Puesto que en este caso el nodo y el ctodo son de distintos materiales, es preciso que la polaridad en la conexin sea la correcta (positiva para DDB y negativa para acero). La conexin elctrica de los electrodos es tal que todos los polos positivos (nodo) van conectados a un mismo punto: en la instalacin existe un ral metlico al cual se conecta la salida positiva del rectificador correspondiente; de la misma forma existe un ral al cual se conectan todos los ctodos. Para la circulacin de lquido, se dispone de una bomba centrfuga vertical (Grundfos) CRN15, capaz de alcanzar hasta 17 m3h-1 con una altura de 22 m (potencia de salida de 2,2 kW). As mismo, se dispone de un rectificador de corriente (Micronic Systems) para alcanzar valores de hasta 750 A a 16 V en continua. La salida del rectificador llega hasta un par de rales que actan como conexin de todos los polos positivos y negativos. Un sistema de control PLC (GeFanuc) se encarga de controlar la instalacin de electro-oxidacin. Dentro de la instalacin existen diversos equipos de medida para garantizar el funcionamiento correcto de la instalacin: interruptores de caudal, caudalmetros y sensores de nivel. El programa de control permite que cuando no circula lquido por uno de los reactores se detenga la corriente que se aplica. A travs de una pantalla tctil frontal se controla el encendido de las bombas centrfugas. Para cada uno de los rectificadores existe un control manual del mismo a la hora de ajustar el par corriente-voltaje.
Mdulos solares fotovoltaicos

Un set de mdulos solares fotovoltaicos se ubic sobre el tejado de la caseta que alberga la instalacin de electro-oxidacin en la EDAR de Aguilar de Campoo. Esta instalacin fotovoltaica est constituida por 7 mdulos solares SunTech Power STP085S (www.suntech-power.com) para una potencia pico de 85 WP por mdulo, luego la potencia pico total de la instalacin es de 595 WP. La Tabla 2.2.1 recoge las caractersticas principales de los mdulos solares fotovoltaicos seleccionados. La salida de los mdulos se conecta a una caja de conexiones, donde gracias a un set de interruptores diferenciales es posible alimentar al proceso con la energa procedente de un nmero de mdulos variable. La salida de los mdulos se conecta directamente a los rales que conectan los polos positivos y negativos. Los mdulos se dispusieron en una configuracin en paralelo, de tal forma que las corrientes generadas por cada mdulo resultan aditivas. La orientacin de los mdulos es sur y con una inclinacin de
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50. En la citada ubicacin no hay influencia de sombras. Este set de mdulos se ha empleado para alimentar una nica lnea. La instalacin existente ser capaz de alimentar el proceso con una corriente mxima de 35 A bajos condiciones de irradiacin de 1000 Wm-2 y 25C. Para dimensionar esta instalacin, teniendo en cuenta que la mxima densidad de corriente recomendable es 1 Am-2 y que el rea de electrodo es de 70 cm2 por compartimento, se utiliz como criterio un valor de corriente medio (35 A) para mantener un nivel de tensin aceptable entre los electrodos para un nivel de eliminacin de materia orgnica adecuada. Tabla 2.2.1 Principales caractersticas de los mdulos solares fotovoltaicos STP085S en la instalacin experimental de electro-oxidacin a nivel planta piloto (condiciones estndar de 1000 Wm-2 y 25C) iSC,ref A 5,15 vOC,ref V 22,2 iMP,ref A 4,8 vMP,ref V 17,8
El diseo original de la instalacin de electro-oxidacin estaba concebido como una planta para el tratamiento en modo discontinuo. Para evaluar la viabilidad de la tecnologa en continuo, se realizaron una serie de modificaciones sobre el diseo original de la instalacin. Bsicamente dichas modificaciones consistieron en la instalacin de un par de bombas centrfugas (Grundfos) CHN2 (2,5 m3h-1 a 19,3 m, potencia de salida de 460 W) conectadas al tanque de alimentacin, siendo su caudal controlado mediante un par de rotmetros (Tecfluid). Adicionalmente, para poder trabajar con caudales en continuo de menor magnitud (y poder as obtener mayores valores de conversin) se instal una bomba centrfuga (Watson-Marlow 323 sciQ).
Resto del equipamiento

En el interior del tanque se dispone de un intercambiador de calor formado por tubos de acero para lograr mantener la temperatura en el interior del tanque por debajo de los valores de 35C (la refrigeracin se realiza mediante agua de servicio disponible de la propia EDAR). La instalacin est construida en tuberas de PVC, salvo el tanque de alimentacin (polipropileno).
Filtro de anillas
Un filtro de anillas (Watflow) con una retencin en slidos de 5 m fue instalado para evitar la presencia de slidos que pudieran taponar la instalacin.
Tanque de retencin
Se dispuso de un tanque de retencin (Reyde) con una capacidad mxima de 1000 L: dicho tanque almacena el agua residual procedente de paso de filtrado previa a su inyeccin en el tanque de alimentacin de la planta de electro-oxidacin.
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Procedimiento analtico Se emple el mismo procedimiento experimental que el descrito en el apartado 2.1 con la salvedad de que la instalacin de electro-oxidacin dispone de medidores de pH y conductividad propios (Kobold). Las muestras fueron estabilizadas mediante acidificacin a pH=2 previo a su transporte y anlisis de COT y DQO (APHA, 1998; AENOR, 1998). El agua residual empleada procede de una arqueta que alimenta al sistema de biodiscos de la EDAR, mientras que el agua de servicio (agua tratada por la planta) se emplea en la refrigeracin del tanque de alimentacin. La Tabla 2.2.2 muestra un resumen de diversas caracterizaciones de muestras puntuales tomadas en distintas fechas. En general, es posible concluir que la concentracin de materia orgnica a la entrada es relativamente baja. En vista de los resultados mostrados, el nivel de conductividad, aunque es menor que el ptimo para la operacin de electro-oxidacin, permite el funcionamiento de la misma. As mismo, este nivel de carga orgnica justifica la potencia solar instalada (ya que para otros niveles de carga sera necesaria una instalacin de mayor potencia). La relacin DQO/COT>3 en la alimentacin est dentro de la referida por Tchobanoglous et al. (2003) para agua no tratada (DQO/COT=2,5-4) y posterior a la sedimentacin primaria (DQO/COT=2). Tabla 2.2.2 Caracterizacin del agua residual procedente de la arqueta de alimentacin al sistema de biodiscos en la EDAR de Aguilar de Campoo NoviembreDiciembre (2009) 70-80 16-29 3,33 0,76-0,85 7,6 Valor medio ref. (2008) g 122 204 115 0,81 8 Valor mn. (2008) 14 27 16 0,35 7 Valor mx. (2008) 950 1398 577 1,10 8,1 Lmites de vertido (RD 509/1996) h 25e 125f 35 2c 15c -
Parmetro [DBO5] a [DQO] a [TSS] a,d Fsforo total b,c Nitrgeno totalAmonio b,c [COT] [DQO]/[COT] pH
a
Unidad mgO2L-1 mgO2L-1 mgL-1 mgPL-1 mgNNH4+L-1 mgCL-1 mScm-1 -
Parmetro exigido en la legislacin segn el Real Decreto 509/1996 (RD 509/1996, 1996); b Parmetro exigido en la legislacin para zonas sensibles cuyas aguas sean eutrficas o con tendencia a serlo segn el Real Decreto 509/1996 (RD 509/1996, 1996); c Zonas sensibles de eutrofizacin, 10000-100000 habitantes-equivalente, medicin por espectrofotometra de absorcin molecular; d Condicin de vertido optativa; e Muestra homogeneizada, sin filtrar ni decantar. Determinacin del oxgeno disuelto antes y despus de cinco das de incubacin a 20C 1C, en completa oscuridad. Aplicacin de un inhibidor de la nitrificacin; f Muestra homogeneizada, sin filtrar ni decantar. Dicromato potsico; g Comunicacin personal Aquagest (Grupo Agbar); h RD 509/1996, Real Decreto 509/1996, de 15 de Marzo, de desarrollo del Real Decreto-ley 11/1995, de 28 de diciembre, por el que se establecen las normas aplicables al tratamiento de las aguas residuales urbanas
38
Procedimiento experimental Una vez cargado el tanque de alimentacin con un volumen suficiente (500 L) bien de agua residual procedente de la arqueta (experimentacin en discontinuo) o bien de agua de servicio (para carga inicial del tanque en la experimentacin en continuo), se inicia el bombeo del lquido a travs de las celdas (la refrigeracin est conectada para que la temperatura no supere los 35 C). En la experimentacin realizada se emple una de las tres lneas de operacin. Para ajustar el caudal de circulacin por reactor a los valores recomendados de operacin, fue necesario utilizar dos bombas centrfugas para una nica lnea de operacin. Al aplicar corriente, tiene lugar la oxidacin de la materia orgnica hasta CO2, eliminndose los gases producidos por la parte superior del tanque de alimentacin. En la operacin en continuo, se conectan las bombas centrfugas para bajo caudal al tiempo en el que se inicia la conexin a los rectificadores. Se toman muestras segn la programacin para cada experimento hasta un volumen por muestra de 100 mL. Puesto que no es posible la inversin de la polaridad en esta instalacin, el protocolo de limpieza consista en un primer aclarado con agua de servicio, lavado cido, segundo aclarado con agua de servicio, lavado bsico y tercer aclarado con agua de servicio, hasta recuperar las condiciones de funcionamiento inicial. Tabla 2.2.3. Condiciones de trabajo en los experimentos previos a la operacin en continuo en la EDAR de Aguilar de Campoo (L=Laboratorio; P=Planta piloto; LS=Lignosulfonato; ARUAC=Agua Residual Urbana de la EDAR de Aguilar de Campoo)
Experimento Electricidad Escala Alimentacin [DQO]0 mgO2L
-1
J mAcm
-2
[Na2SO4] mgL-1
A1 A2 A3 A4 A5 A6 A7 L1 L2 L3 L4 L5 L6 A8 c A9 c
a
Red Red Red Red Red Red Red Red Red Red Red Red Red Red Red
L L L L L L L P P P P P P P P
ARUAC a ARUAC a ARUAC b ARUAC b ARUAC b ARUAC b ARUAC b LS LS LS LS LS LS ARUAC d ARUAC e
27 28 19 17 27 19 20 440 452 444 1254 933 1206 60-80 f 60-75 f
15 30 5 10 10 15 15 30 15 60 30 60 60 10 10
0 0 0 0 2500 0 2500 2500 2500 2500 2500 2500 2500 0 0
Muestras tomadas en el mes de Marzo de 2009; b Muestras tomadas en el mes de Abril de 2009; c Experimentos realizados en continuo; d Muestras tomadas en el mes de Diciembre de 2009; e Muestras tomadas en el mes de Abril de 2010; f Como se describe posteriormente, la concentracin inicial [DQO]0 en el tanque de retencin vara con el tiempo por degradacin natural
39
Operacin de la planta de electro-oxidacin en modo discontinuo Previo a la experimentacin con aguas residuales en la EDAR de Aguilar de Campoo, se completaron una serie de experimentos preliminares para valorar la efectividad del proceso de electro-oxidacin para dichas aguas y proceder a escalar el proceso. La Tabla 2.2.3 resume las condiciones experimentales de los experimentos previos a la operacin con la planta en modo continuo. Se oper con 2 bombas centrfugas para un caudal de circulacin de 45 Lmin-1 y una temperatura constante (en funcin de la temperatura externa).
40
2.3. Resultados
2.3.1. Anlisis cintico de la electro-oxidacin en laboratorio de lignosulfonato mediante energa de red El objetivo del anlisis cintico de la degradacin del COT procedente de una disolucin de lignosulfonato es estudiar el comportamiento de la tecnologa de electro-oxidacin mediante electrodos de DDB para la eliminacin de sustancias biorrefractarias (asumida como lignosulfonato). Las Figuras 2.3.1.1 y 2.3.1.2 muestran los resultados de la eliminacin de COT en forma adimensional ( =[COT][COT]0-1) para lignosulfonato mediante energa de red para los experimentos S1-8 y C1-8 (Tabla 2.1.3). De las Figuras 2.3.1.1 y 2.3.1.2 se deduce que es posible la eliminacin de lignosulfonato mediante la tecnologa de electro-oxidacin en las condiciones experimentales citadas, puesto que es posible alcanzar eliminaciones superiores al 90% en COT.
1 0.9 0.8 0.7 0.6 C (-) 0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 Tiempo (min) 400
Figura 2.3.1.1 Eliminacin de COT en forma adimensional ( ) para la serie de baja DQO inicial. () S1-2; () C1-2; () S3-4; () C3-4; () curva de ajuste para los experimentos S12 y C1-2; () curva de ajuste para los experimentos S3-4 y C3-4 La evolucin de los valores de con el tiempo sugiere una tendencia exponencial, de tal forma
que los valores obtenidos fueron ajustados segn una expresin exponencial, cuyos resultados se presentan en la Tabla 2.3.1.1. Los valores mostrados en la Tabla 2.3.1.1 fueron obtenidos mediante MATLAB (MATLAB, 2007) empleando el algoritmo de Levenberg-Marquardt. El nivel de confianza para los parmetros cinticos se ajust en un 95%. Para todos los valores obtenidos de la constante cintica observada de eliminacin de COT en forma adimensional (con unidades de min-1), se procedi a su correccin a travs de la magnitud extensiva Aevs-1,
41
que representa el cociente entre el rea de electrodo disponible y el volumen de lquido que circula por la instalacin (3,5 m-1 para la configuracin actual) para expresarla en unidades de velocidad referida a la superficie del electrodo k (mmin-1).
1 0.9 0.8 0.7 0.6 C (-) 0.5 0.4 0.3 0.2 0.1 0 0 100 200 300 Tiempo (min) 400
Figura 2.3.1.2 Eliminacin de COT en forma adimensional ( ) para la serie de alta DQO inicial. () S5-6; () C5-6; () S7-8; () C7-8; (---) curva de ajuste para los experimentos S5-6 y C5-6; (- -) curva de ajuste para los experimentos S7-8 y C7-8 A la vista de los valores obtenidos en la Tabla 2.3.1.1 se observa que no existe influencia de la concentracin de electrolito soporte en la constante cintica k en el rango estudiado de concentraciones de 2500-5000 mgL-1. Tabla 2.3.1.1. Parmetro cintico k de ajuste de Experimento S1 S2 C1 C2 S3 S4 C3 C4 S5 S6 C5 C6 S7 S8 C7 C8
42
frente al tiempo. Nivel de confianza 95% r2 k103 r2
k103 (mmin ) 1,220,07 1,270,08 1,730,15 1,170,05 1,550,10 1,620,09 1,450,12 1,440,08 0,810,06 0,880,06 1,030,19 0,790,08 1,180,07 1,340,08 1,480,10 1,370,21
-1
r2 0,99 0,99 0,99 0,99 0,99 0,99 0,98 0,99 0,99 0,99 0,95 0,94 0,99 0,99 0,99 0,97
kS/C103 (mmin ) 1,240.05 1,420,14 1,580,07 1,440,07 0,840,04 0,910,10 1,260,06 1,420,11
-1
(mmin ) 0,99 0,96 0,99 0,99 0,99 0,94 0,99 0,98 1,330,06 0,98 1,330,07 0,97
-1
(mAmgO2-1) 2,1
1,510,05
0,99
4,2
0,870,05
0,96
0,7
1,4
La influencia despreciable de la concentracin de electrolito soporte es tpica en los proceso de electro-oxidacin. Durante la electro-oxidacin de aguas residuales procedentes de la produccin de aceite de oliva, no se observ ninguna influencia como consecuencia de aumentar la concentracin de sulfato sdico de 2% al 3% en una instalacin con electrodos de Ti-Ta/Pt-Ir (Giannis et al., 2007). Consecuentemente, se procedi a agrupar dichos valores en la constante kS/C en la que la influencia de la concentracin de electrolito soporte ha sido eliminada. A su vez, los valores de la constante cintica kS/C se pueden agrupar en una nueva entre la corriente aplicada y la unidad de materia orgnica inicial expresada como DQO (ec. 2.3.1.1): constante k, en base a los valores obtenidos para el parmetro , definido como el cociente
ec. 2.3.1.1 Donde J es la densidad de corriente aplicada (cociente entre la corriente aplicada al reactor i y el rea de nodo disponible Ae). Esta agrupacin permite valorar la influencia de las condiciones de operacin en una sola variable. Por tanto, es el cociente entre la densidad de corriente aplicada y la concentracin de materia orgnica el que influye en la velocidad con la que se elimina dicha materia (Caizares et al., 2002; Caizares et al., 2006a). Para la tecnologa de electro-oxidacin mediante electrodos de DDB se asume que la oxidacin de materia orgnica transcurre en dos etapas en serie. En la primera, tiene lugar el transporte de todas aquellas especies qumicas susceptibles de ser oxidadas hasta la superficie del nodo desde el seno del fluido. En la segunda, una vez la materia orgnica alcanza la superficie andica, es directamente oxidada mediante los radicales hidroxilos generados en su superficie. Las ecs. 2.3.1.2 y 2.3.1.3 muestran la reaccin de generacin de radicales hidroxilo en la superficie de los electrodos de DDB y la oxidacin con la materia orgnica MO respectivamente.
ec. 2.3.1.2 ec. 2.3.1.3 En el electrodo de DDB tiene lugar la reaccin de descarga de la molcula de agua, de tal forma que un radical hidroxilo OH queda adsorbido sobre el correspondiente sitio activo (DDB[OH]). Ese radical hidroxilo reacciona con la materia orgnica MO, de tal forma que tiene lugar la oxidacin hasta CO2, quedando liberado el sitio activo para aceptar un nuevo radical hidroxilo. De la Tabla 2.3.1.1 puede deducirse que cuando es bajo, la cantidad de electrones inyectados al sistema por la corriente es menor que el necesario para la oxidacin; de esta forma el electrones ser la etapa limitante. Por otro lado, para valores relativamente altos de , la
43
proceso operar en un rgimen de control por densidad de corriente, y la cantidad de
cantidad de electrones introducidos es superior a la cantidad de electrones necesarios para llevar a cabo la oxidacin a travs de los radicales hidroxilos. As, el exceso de electrones se emplear en reacciones paralelas, principalmente de generacin de oxgeno en el nodo, y consecuentemente ser la transferencia de materia orgnica la que se convierta en la etapa controlante (ya que al aumentar dicha velocidad de transferencia, se podra llegar a equilibrar la cantidad de materia orgnica que alcanza la superficie del electrodo con la corriente aplicada). Por tanto, aumentar la densidad de corriente aplicada desde J=30 mAcm-2 hasta J=60 mAcm-2 o bien disminuir la concentracin de DQO inicial desde [DQO]0=1500 mgO2L-1 hasta [DQO]0=500 mgO2L-1 aumentan el valor de y por tanto favorecen que el proceso opere en un rgimen ms prximo al control por transferencia de materia. Al representar grficamente los valores de k frente a en la Figura 2.3.1.3 se observa una
tendencia hiperblica cuya interpretacin se ajusta al comportamiento anteriormente enunciado. Esta tendencia pone de manifiesto el hecho de que al aumentar el valor de , la puede corresponder con el coeficiente de transferencia de materia en el sistema.
constante cintica k aumenta con tendencia a alcanza un valor mximo, cuyo valor lmite se
3 2.5
k103 (mmin-1)
1.5 1
0.5
0 0
2 3 (mAmgO-1)
2
Figura 2.3.1.3. Evolucin de la constante cintica k en funcin del cociente entre corriente elctrica aplicada y cantidad de materia orgnica inicial (las barras de error representan los valores mximos y mnimos obtenidos); (--) curva de ajuste De esta Figura 2.3.1.3 se observa que valores por encima de =5 mAmgO2-1 no llevan a
incrementos significativos del valor de k por lo que desde un punto de vista de operacin no
sera recomendable aumentar el valor de , ya que valores mayores de corriente aplicada slo se traduciran en aumentar la velocidad de reacciones secundarias. Los valores de la Figura 2.3.1.3 fueron ajustados a la expresin hiperblica dada por la ec. 2.3.1.4:
44
ec. 2.3.1.4
Donde kS representa la constante cintica de electro-oxidacin en la superficie del nodo y km el de la ec. 2.3.1.4 permite estimar, con un nivel de confianza en los parmetros del 80% (algoritmo de Levenberg-Marquardt) valores de kS=(2,051,29)10-3 mgO2m(mAmin)-1 y kSkm-1=0,8850,827 mgO2mA-1 (r2=0,91). Los valores obtenidos se encuentran en el orden de magnitud tpico para procesos de electro-oxidacin con configuraciones similares y condiciones de operacin experimentales tal y como se muestra en la Tabla 2.3.1.2: Tabla 2.3.1.2. Referencias de constantes cinticas biorrefractarios derivados y/o similares a la lignina Electrodo Ti/PbO2 Si/DDB Si/DDB DiaChem DiaChem Si/DDB Compuesto Lignina Fenol Fenol Fenol Acid Orange 7 Lignosulfonato Eliminacin DQO DQO Fenol DQO DQO COT de oxidacin de compuestos coeficiente de transferencia de materia. El ajuste de los valores de k a la expresin hiperblica
k105 (mmin-1) 2-6 170 127-769 114 88 87-151
Referencia Chiang et al., 1997 Caizares et al., 2002 Polcaro et al., 2003 Moro et al., 2004 Fernandes et al., 2004 Trabajo actual
En cuanto a la evolucin de los valores de pH sealar que mientras que para la serie de experimentos correspondientes al sulfato sdico se observ un ligero incremento en los valores obtenidos (pH(+)1) debido a los aniones de cidos fuertes generados (sulfatos y peroxodisulfatos), en la serie correspondiente al cloruro sdico se observ un descenso en el pH (pH(-)0-3) debido a aniones de cidos dbiles (hipoclorito). La tensin entre los electrodos no mostr variaciones significativas a lo largo del experimento (no se generaron incrustaciones sobre la superficie electrdica). En cuanto al consumo energtico especfico por unidad de volumen Ece,v, para J=30 mAcm-2 el consumo se mantuvo en 45 kWhm-3, mientras que para J=60 mAcm-2 el consumo se mantuvo en torno a 120 kWhm-3.
45
2.3.2. Anlisis cintico de la electro-oxidacin de lignosulfonato mediante energa solar fotovoltaica El objetivo del anlisis cintico de la degradacin de lignosulfonato mediante energa solar fotovoltaica es valorar la viabilidad de introducir una corriente elctrica dependiente de la irradiacin solar para eliminar el COT procedente de una disolucin de lignosulfonato, es decir, comprobar la viabilidad tcnica del proceso ESOF utilizando energa solar fotovoltaica. La Figura 2.3.2.1 muestra el perfil de COT para los experimentos E1-4, donde se muestra claramente que a pesar de la naturaleza estocstica de la irradiacin solar es posible conseguir eliminaciones superiores al 90% de COT en disoluciones de lignosulfonato, lo que confirma el resultado anterior dedicado al proceso en condiciones de corriente controlada. Por tanto, las oscilaciones solares no impiden que si el nivel de corriente es adecuado (en estos casos suficientemente elevados), sea posible llevar a cabo la oxidacin de la materia orgnica al nivel deseado.
700 600 500

COT (mg CL-1)
400 300 200 100 0 0
60
120
180 240 300 Tiempo (min)
360
420
480
Figura 2.3.2.1 Perfil dimensional de COT frente a tiempo. () E1; () E2; ( ) E3; () E4 Balance de energa La Figura 2.3.2.2 muestra el perfil de potencia solar incidente g (producto de la irradiacin solar G en el plano correspondiente a los mdulos fotovoltaicos por el rea total incidente Am) as como la corriente total generada (interior de la Figura 2.3.2.2). Los valores mximos obtenidos para la potencia solar g y para la corriente total generada i fueron 4,53 kW y 19,8 A (que se corresponden con el experimento E2, en el que se emplearon los 4 mdulos en paralelo bajo condiciones de cielo despejado). Este valor de irradiacin se compar con el procedente del Sistema de Informacin Geogrfica Fotovoltaico del Centro (http://re.jrc.ec.europa.eu/pvgis,
JRC of the European Commision) estimando una diferencia inferior al 3% en condiciones de

cielo despejado.
46
5000 4500 4000

i (A)
20
15
10
3500
5
3000
g (W)
0 0 60 120
2500 2000 1500 1000 500 0 0 60 120 180 240 300 Tiempo (min)
180 240 300 T ime (min)
360
420
480
360
420
480
Figura 2.3.2.2 Potencia solar incidente g frente a tiempo. () E1; () E2; ( ) E3; () E4. Interior de la figura: corriente total aplicada i frente a tiempo () E1; () E2; ( ) E3; () E4 La Figura 2.3.2.3 muestra la relacin existente entre el voltaje aplicado entre los electrodos del reactor de electro-oxidacin y la corriente total aplicada procedente de los mdulos fotovoltaicos.
15
10 v (V) 5 0 0
10 i (A)
15
20
Figura 2.3.2.3 Voltaje entre electrodos v frente a corriente total aplicada i. () E1; () E2; () E3; () E4 Debido a la conexin directa entre el set de mdulos solares y el reactor de electro-oxidacin, la tensin entre electrodos es la tensin a la que operan los mdulos y la corriente total generada por los mdulos es la total inyectada al reactor de electro-oxidacin. De la Figura 2.3.2.3 se observa como: i) no se genera corriente hasta que un cierto valor de tensin es aplicado al reactor (en el entorno de los 5 V) ii) existe una relacin lineal entre la tensin aplicada y la
47
corriente generada. La pendiente de dichas rectas se identifica con la resistencia hmica R impuesta por el lquido que circula entre los electrodos (ya que la resistencia impuesta por los electrodos se asume despreciable). En la Figura 2.3.2.3 se distinguen claramente 2 rectas: una de ellas es la correspondiente al experimento E4, debido a la menor conductividad (mnima cantidad de sulfato sdico empleado) y por tanto mayor resistencia hmica en este experimento; la otra recta se corresponde con los experimentos E1-2-3, en los cuales se emple el mismo nivel de electrolito soporte (mismo nivel de conductividad). Los valores de tensin aplicados se ajustaron linealmente (MATLAB, 2009) como una funcin de la corriente total aplicada en la forma mostrada en la ec. 2.3.2.1: ec. 2.3.2.1 Donde el trmino v0 se corresponde con el mnimo voltaje necesario para generar una corriente elctrica entre los electrodos del reactor, siendo frecuentemente utilizado en la prctica electroqumica (Bonvin y Comninellis, 1994; Panizza et al., 2001). El ajuste de los pares de valores v-i llev a los parmetros mostrados en la Tabla 2.3.2.1: Tabla 2.3.2.1. Ajuste de los valores de tensin-corriente aplicada Experimento E1-2-3 E4 v0 5,700,69 3,891,15V R 0,500,06 2,100,40 (mScm-1) 3,3-4 0,4-1
El rango de valores entre los que vari la conductividad de la solucin se muestra en la Tabla 2.3.2.1 para hacer notar la relacin entre dicha variable y la resistencia hmica observada: aproximadamente aumentar la conductividad por cuatro se traduce en una resistencia R cuatro veces menor. Valores estacionarios de se obtuvieron despus de la primera hora de operacin. De la misma forma, los perfiles de pH se estabilizaron despus de la primera hora de operacin, observndose valores de descenso en el pH mayores a los observados durante la experimentacin en condiciones controladas. Al presentar la misma forma los perfiles temporales de y pH es posible afirmar que los protones generados son responsables de ese cambio en la conductividad, lo cual es lgico teniendo en cuenta su elevada conductividad molar (Yaws, 2003). La Figura 2.3.2.4 muestra el perfil temporal de y pH en los experimentos realizados.
48
4.5 4 3.5 3
(mScm-1)
pH(-)
6 5
2.5 2 1.5 1 0.5 0 0 60 120
4 3 2
60
120
180 240 300 Time (min)
360
420
480
180 240 300 Tiempo (min)
360
420
480
Figura 2.3.2.4 Perfil de conductividad frente a tiempo. () E1; ( ) E2; ( ) E3; () E4. Interior de la figura: perfil de pH frente a tiempo () E1; () E2; ( ) E3; () E4 Para el proceso ESOF resulta de inters conocer tanto la relacin v-i como la relacin entre la irradiacin solar G y la corriente total generada i. De la Figura 2.3.2.2 se deduce que existe una relacin entre ambas variables, lo que se pone de manifiesto en la Figura 2.3.2.5: esta relacin debe ser lineal para valores relativamente bajos de i mientras que una desviacin positiva respecto a ese comportamiento lineal se observa para valores relativamente altos de i.
6000 5000 4000 g (W) 3000 2000 1000 0 0 5 10 i (A) 15 20
Figura 2.3.2.5 Potencia solar incidente g frente corriente total generada i. () E1; ( ) E2; () E3; () E4 y valores calculados () E1; () E2; () E3; () E4 El rendimiento de la transformacin de energa solar en energa elctrica debe influir en dicha relacin. La Figura 2.3.2.6 muestra la relacin entre la potencia elctrica solar por unidad de rea de mdulo solar fotovoltaico P frente a la irradiacin solar G. La eficacia de un mdulo
49
solar fotovoltaico se define en el punto de mxima potencia potencia pico (Luque y Hegedus, 2003). Para otro punto diferente de la potencia pico, la relacin P-G debera dar la eficiencia del mdulo segn la ec. 2.3.2.2:
ec. 2.3.2.2 El ajuste de los valores de eficacia para los diferentes experimentos se muestra en la Tabla 2.3.2.2. Como puede observarse, los valores llegan hasta un valor mximo de eficacia del 7%, que estn lejos del valor nominal de eficacia para los mdulos empleados (=14,2%). Este hecho se debe a que el par de valores v-i al que trabaja el reactor de electro-oxidacin est lejos del punto v-i del mdulo que se corresponde con la mxima potencia posible. Para lograr aprovechar al mximo la potencia solar disponible es importante ajustar dichos valores para minimizar las prdidas de energa, por lo que ser necesario adaptar la configuracin de la conexin serie-paralelo de los mdulos a la resistencia hmica impuesta por el reactor (Markvart, 2006). Combinado las ecs. 2.3.2.1 y 2.3.2.2 se obtiene la ec. 2.3.2.3 que relaciona la potencia solar incidente g con la corriente generada i:
ec. 2.3.2.3 Donde se observa que existen dos trminos que contribuyen a la potencia elctrica: el trmino correspondiente al uso electroqumico (iv0) y el trmino de prdidas debidas al efecto Joule (i2R). Por tanto si se dispone del valor de irradiacin solar G y los trminos v0, R y entonces es posible conocer la corriente elctrica que se introduce al proceso ESOF.
80
60
P (Wm )
-2
40
20
0 0
250
750 500 G (Wm-2)
1000
1250
Figura 2.3.2.6 Potencia elctrica solar por unidad de rea de mdulo fotovoltaico P frente a irradiacin solar G. () E1; () E2; ( ) E3; () E4
50
En la Figura 2.3.2.5 aparecen los valores calculados de g mediante el empleo de la ec. 2.3.2.3, observndose un buen ajuste a los valores obtenidos experimentalmente. Mediante la ec. 2.3.2.1 es posible evaluar la tensin de operacin. El modelo desarrollado para relacionar la energa solar incidente con la intensidad aplicada es capaz de describir de forma sencilla los valores experimentales obtenidos. Existen numerosas referencias donde se desarrollan modelos ms complejos basados en elementos de circuitos elctricos para describir la relacin v-i: el modelo de cinco parmetros es un buen ejemplo de estos modelos (Townsend, 1989; Gow y Manning, 1999; Celik y Acikgoz, 2007), existiendo referencias especficas a dicho modelo en trabajos de integracin de energa solar fotovoltaica en procesos electroqumicos (Ortiz et al., 2006; Ortiz et al., 2007). Tabla 2.3.2.2. Valores de eficacia de los mdulos solares y consumos especficos de energa Experimento E1 E2 E3 E4 (%) 5,3 7,0 5,3 5,6 Ece,v (kWhm-3) 294 571 184 100 Ece,m (kWhkgCOT-1) 534 882 1035 176
La Tabla 2.3.2.2 muestra los valores obtenidos para el consumo energtico especfico por unidad de volumen tratado Ece,v y unidad de masa de COT eliminado Ece,m para los experimentos realizados. Tal y como puede observarse, el menor consumo se produce para el experimento E4, que coincide con el perfil de menor irradiacin. Por tanto es posible llevar a cabo la eliminacin de COT con un nivel de consumo energtico de 100 kWhm-3. Los valores obtenidos por el proceso ESOF se han comparado con otros procesos de electro-oxidacin en similares condiciones y configuraciones experimentales en la Tabla 2.3.2.3. Se observa que los valores obtenidos se encuentran dentro del rango esperado para los procesos de electrooxidacin convencionales. Estos valores siempre van a depender de las variables que marcan el consumo energtico como son la corriente aplicada y la conductividad del efluente a tratar. Otro punto importante es que en la Tabla 2.3.2.3 se ha incluido el consumo especfico para el tratamiento de aguas residuales urbanas mediante procesos biolgicos convencionales: como puede observarse, el valor reportado de 0,7 kWhm-3 hace que el proceso ESOF sea difcilmente competitivo en trminos de energa total, por lo que es necesario referir las comparaciones a energa primaria utilizada, donde la energa solar fotovoltaica presenta ventajas notables.
51
Tabla 2.3.2.3. Consumo de energa especfico en procesos de electro-oxidacin

Efluente Sustancia
Ece,v (kWhm-3)
Ece,m (kWh kgCOT-1)
Condiciones experimentales Electrodos de DDB (COT inicial: 4001000 mgCL-1; 5000 mgNa2SO4; densidades de corriente: 15-60 mAcm-2)
Referencia
Sinttico
Fenol
26-91
Caizares et al., 2002
Real
Residuales urbanas
0,7
Tratamiento biolgico convencional Electrodos de DDB (DQO inicial: 700 mgO2L-1, eliminacin de 100% en DQO, 3000 mg Na2SO4) Electrodos de DDB (25 mScm-1, DQO inicial: 6000 mg O2L-1, eliminacin del 90%, densidades de corriente: 15-60 mAcm-2) Electrodos DSA (adicin de 5,85 gL-1 de NaCl; densidades de corriente: 20-160 mAcm-2) Electrodos de DDB
Tchobanoglous et al., 2003; California Energy Commision, 2006; European Commission, 2007 Caizares et al., 2006b
Real
Sustancias refractarias a la oxidacin Fenton
94
150
Real
Agua residual industria farmacutica
200
Caizares et al., 2006c
Real
Agua residual industria textil
154-822
Malpass et al., 2007 Trabajo actual
Sinttico
Lignosulfonato
176
100
Balance de materia La Figura 2.3.2.7 muestra el perfil con el tiempo de eliminacin de COT en forma adimensional; en la Figura 2.3.2.7 se representa as mismo una lnea recta (lnea k), cuya pendiente es la mxima constante cintica obtenida en condiciones de corriente controlada, y cuyo valor es kmax=8,0910-3 min-1 (que puede obtenerse como producto de km(Aevs-1). Por tanto, era esperable que todos los puntos se encontrasen por debajo de esta si no aparecen mecanismos de reaccin adicionales. La evolucin de los valores mostrados en la Figura 2.3.2.7 justifica que en la Tabla 2.3.2.3 se muestren los valores de la constante cintica k ajustados a una expresin cintica de primer orden (nivel de confianza del 95%). Adicionalmente, para poder comparar los valores de k segn diferentes irradiaciones, se decidi incluir un valor de corriente promedio del experimento ip as como uno de potencia solar promedio del experimento gp.
52
2.5
2
Ln C (-)
1.5
0.5
0 0
60
120
180 240 300 Tiempo (min)
360
420
480
Figura 2.3.2.7 Eliminacin de Carbono Orgnico Total adimensional E1; () E2; ( ) E3; () E4; (-) lnea k
frente a tiempo. ()
La Figura 2.3.2.8 muestra la evolucin de los valores de la constante cintica k en funcin de la potencia solar promedio gp: la tendencia en la evolucin de valores es similar a la mostrada en la Figura 2.3.1.3, de tal forma que nuevamente se observa una evolucin hiperblica, en este caso en funcin de la potencia promedio gp, con lo que se justifica que una mayor potencia no lleva a mejorar sustancialmente el valor de la constante cintica. Tabla 2.3.2.3. Corriente promedio, potencia solar promedio y constante cintica en los experimentos con corriente no controlada Experimento E1 E2 E3 E4 ip (A) 8,48 15,39 6,69 2,42 gp (kW) 1,86 3,43 1,47 0,50 k103 (mmin-1) 1,800,18 2,280,20 1,790,24 1,310,09
Los experimentos E2-4 mostraron desviaciones notables positivas y negativas respecto de la lnea k respectivamente. En la Figura 2.3.2.7 se observa como para E2 los valores se encuentran en la lnea k de referencia durante las 3 primeras horas de operacin. A partir de esas 3 primeras horas, se observa una desviacin de los valores por encima de la lnea k (los 2 puntos experimentales registrados en la Figura 2.3.2.7). Esta desviacin nicamente se observa en el caso de E2, que se corresponde con el experimento con el mximo valor i=15,39 A. En vista a las desviaciones experimentalmente observadas se puede considerar que existen mecanismos adicionales que puedan estar contribuyendo a la oxidacin de materia orgnica. Tal y como se describi en el apartado correspondiente en condiciones de corriente controlada,
53
existen dos etapas en serie que explican la electro-oxidacin de materia orgnica en electrodos de DDB: i) transporte de la materia orgnica hasta la superficie andica desde el seno del fluido ii) oxidacin mediante radicales hidroxilos en la superficie andica. El mecanismo adicional sugerido consiste en la oxidacin indirecta mediante oxidantes electro-generados como peroxodisulfatos (si el electrolito soporte tiene un anin sulfato), cuya concentracin en el seno del fluido depende de la corriente aplicada y para los cuales no existen limitaciones a la transferencia de materia por encontrarse en exceso (Michaud et al., 2000; Serrano et al., 2002). Este mecanismo estara actuando en paralelo a la oxidacin mediante radicales hidroxilos. De esta forma, a valores muy elevados de la corriente aplicada, la contribucin de los mecanismos paralelos por agentes electro-generados sera factible, haciendo que la velocidad neta de eliminacin de COT sea ms rpida por cuanto existe un mecanismo adicional contribuyendo a su eliminacin.
2.5
k103 (mmin-1)
1.5
0.5
0 0
2 gp (kW)
Figura 2.3.2.8 Evolucin de la constante cintica k en funcin de la potencia solar promedio en cada experimento gp (las barras de error consideran la desviacin estndar respecto de los valores ajustados) Esta posibilidad resulta difcil de apreciar en el experimento E4. En este experimento, los menores valores de corriente (ip=2,42 A) tuvieron lugar, y los valores experimentales se encuentran por debajo de la lnea k durante todo el tiempo de operacin. En este caso, es esperable que la extensin de las reacciones paralelas de oxidacin mediante oxidantes electrogenerados sea despreciable. Adems, en el ltimo tramo de E4 los valores se desvan de cualquier tendencia lineal, lo que sugerira un cambio a una cintica de orden cero. A valores ms moderados de corriente respecto de E2 (como los observados en los experimentos E1-3), se muestra que tambin es posible alcanzar valores elevados de eliminacin de COT. En los experimentos E1-3 es reseable que a pesar de poseer diferentes perfiles de irradiacin (y
54
consecuentemente diferentes valores de ip), los perfiles de eliminacin de COT son similares. Consecuentemente, el incremento de la corriente aplicada por encima de 6 A no parece mejorar significativamente, con lo que se espera que la contribucin de los mecanismos paralelos de oxidacin ocurran nicamente bajo condiciones de corriente muy elevadas. Como referencia, en el experimento E2, la densidad de corriente promedio fue ip=220 mAcm-2, lo cual supone un nivel de corriente aproximadamente 3,5 veces el mximo valor empleado durante la operacin en condiciones de corriente controlada.
Modelado del proceso ESOF La corriente elctrica i es la variable clave en todo proceso electroqumico. En el apartado dedicado al anlisis cintico de la eliminacin de lignosulfonato en condiciones de corriente controlada, se desarroll una expresin cintica (ec. 2.3.1.4) que permita conocer el valor de la constante cintica como funcin de la variable , que est directamente relacionada con la Desarrollando la ec. 2.3.1.4 en forma explcita en funcin de la corriente elctrica se obtiene la ec. 2.3.2.4: corriente aplicada y la concentracin inicial de materia orgnica expresada como DQO.
ec. 2.3.2.4
Donde rA es la velocidad de reaccin referida al rea de electrodo; kS* y (kSkm-1)* son los parmetros kS y kSkm-1 corregidos al volumen de lquido en el reactor de electro-oxidacin ve. La ec. 2.3.2.4 mantiene la forma hiperblica de la ec. 2.3.1.4, de tal forma que bajo altos valores de i, el proceso estar controlado por la transferencia de materia, mientras que a bajos valores de i, el proceso estar controlado por la densidad de corriente aplicada. Puesto que en el proceso ESOF, la entrada de energa al proceso depende de la irradiacin solar (bajo condiciones de irradiacin solar, la variacin de la corriente elctrica es estocstica), tiene sentido utilizar la ec. 2.3.2.4 para expresar la velocidad de reaccin rA en funcin de la corriente generada por los mdulos i (la cual depende de g), lo que da lugar a la ec. 2.3.2.5:
ec. 2.3.2.5
55
Donde k1 y k2 se obtienen por agrupacin de parmetros en la ec. 2.3.2.4, siendo ki el valor de la constante cintica instantnea en funcin de la corriente i generada por los mdulos solares. Para la configuracin experimental del proceso ESOF a escala de laboratorio y valores de [DQO]01500 mgO2L-1 (como corresponde a los experimentos E1-2-4), se tendran valores de k1=6,8110-4 mmin-1A-1 y k2=2,9510-1 A-1; para [DQO]0500 mgO2L-1 (como corresponde al experimento E3), se tendran valores de k1=2,0610-3 mmin-1A-1 y k2=8,8610-1 A-1. Por tanto, si se genera una importante corriente elctrica, el proceso estar controlado por la transferencia de materia segn la ec. 2.3.2.6 mientras que si el valor de corriente elctrica es relativamente bajo, el proceso estar controlado por la corriente aplicada segn la ec. 2.3.2.7:
ec. 2.3.2.6 ec. 2.3.2.7
56
2.3.3 Demostracin del proceso ESOF a escala piloto para el tratamiento de aguas residuales urbanas Una vez estudiada la viabilidad del proceso ESOF para eliminar materia orgnica procedente de lignosulfonato a escala de laboratorio, se propone demostrar la viabilidad del proceso a una escala de planta piloto. La planta piloto se ubic en la EDAR de Aguilar de Campoo (Palencia). Dicha planta, supone un rea andica de DDB 50 veces superior. Previo a la operacin en continuo con la planta piloto, fue necesario realizar una serie de modificaciones sobre la misma, as como su adaptacin para operar en la citada planta, tal y como se ha descrito en el apartado dedicado a la parte experimental. Adicionalmente, se realizaron varias pruebas preliminares para comprobar: i) la viabilidad del proceso de electro-oxidacin para tratar las aguas residuales de la EDAR de Aguilar de Campoo (escala laboratorio) ii) el efecto del escalado, mediante la electro-oxidacin de lignosulfonato iii) la adecuacin de las modificaciones y puesta a punto realizadas sobre la planta para su operacin en continuo. A continuacin se precisan los detalles de cada una de las pruebas preliminares efectuadas.
Viabilidad del proceso de electro-oxidacin para tratar las aguas residuales de la EDAR de Aguilar de Campoo (escala laboratorio) Una vez demostrada la viabilidad del tratamiento para lignosulfonato tanto mediante corriente controlada como no controlada, se procedi analizar la viabilidad de la eliminacin de la materia orgnica procedente de las aguas residuales de la EDAR de Aguilar de Campoo a escala de laboratorio con el objetivo de estudiar el comportamiento del proceso. Al transcurrir la electrooxidacin por medio de la generacin de radicales hidroxilos, se estim que la eliminacin de la materia orgnica de la EDAR se completase hasta los valores deseados. La experimentacin efectuada (A1-7) sigui una metodologa similar a la empleada para obtener las constantes cinticas de eliminacin de COT en funcin de la variable . Tabla 2.3.3.1. Parmetro cintico k de ajuste de Experimento A1 A2 A3 A4 A5 A6 A7 k103 (mmin-1) 1,610,08 1,770,12 0,570,07 0,880,14 0,960,12 1,050,19 0,950,16 frente al tiempo. Nivel de confianza 95% r2 0,99 0,99 0,95 0,89 0,97 0,88 0,89 Ece,v (kWhm-3) 34 93 8 20 15 34 25
(mAmgO2-1) 20 38 9 21 13 28 27
Los valores de las constantes cinticas obtenidas -ajuste cintica de primer orden mediante MATLAB (2009)- para dicha eliminacin en las condiciones experimentales mostradas en la
57
Tabla 2.2.3 se muestran en la Tabla 2.3.3.1. Se observa que los valores de las constantes cinticas para los experimentos A1-2 (1,6110-3-1,7710-3 mmin-1) son mayores que las obtenidas para el resto de experimentos A3-7 (0,5710-3-1,0510-3 mmin-1), poseyendo mayores valores de la variable . Mediante un anlisis similar al realizado en el anlisis cintico de degradacin de lignosulfonato en condiciones de corriente controlada, se observa que para las muestras de agua residual ensayada, el coeficiente de transferencia de materia estara aproximadamente comprendido entre 1,0010-3-1,5010-3 mmin-1, rango que coincide en orden de magnitud con el valor obtenido para lignosulfonato (2,3110-3 mmin-1). El menor valor de k se obtiene para el experimento A3, que coincide con el menor valor de utilizado. Los valores relativamente altos obtenidos en comparacin con los correspondientes a lignosulfonato para la mAmgO2-1) se deben a que las concentraciones iniciales de DQO son relativamente bajas, por
variable (el valor mximo operado con lignosulfonato en condiciones controladas fue =4,2
lo que cualquier nivel de corriente aplicada que permita generar radicales hidroxilos lleva a valores altos de . En cuanto al consumo energtico, en aquellos experimentos en los que se aadieron cantidades adicionales de sulfato sdico, p.ej.: hasta 2500 mgL-1 para A5 frente a A4, para un mismo nivel de densidad de corriente, el consumo energtico descendi: para una densidad de corriente J=10 mAcm-2 en los experimentos A4-5, los consumos fueron respectivamente de 20 y 15 kWhm-3. Estos valores son comparativamente menores que los existentes para degradacin de lignosulfonato (45-120 kWhm-3 para corriente controlada) puesto que los valores de densidad de corriente aplicada fueron menores. Al analizar estos valores de consumo especfico de energa se observ que como consecuencia de la baja carga orgnica, se propusieron como mejores condiciones de operacin aquellas que disminuyesen dicho consumo hasta valores que, manteniendo los niveles de eliminacin, redujesen el consumo energtico hasta valores aceptables como los obtenidos en A4-5. Por esta razn, se decidi mantener un nivel de densidad de corriente J=10 mAcm-2 para la experimentacin con agua residual urbana, si los niveles de conductividad se mantienen en el entorno de 1 mScm-1.
Pruebas preliminares con lignosulfonato Una vez comprobada la viabilidad de la eliminacin del COT de las aguas residuales de la EDAR a escala de laboratorio, se procedi a analizar la viabilidad de la eliminacin de COT procedente de lignosulfonato en la planta piloto de electro-oxidacin con el objetivo de chequear el efecto del escalado desde la planta de laboratorio hasta la planta piloto. Las condiciones experimentales para los experimentos con lignosulfonato (L1-6) en condiciones controladas de corriente se resumen en la Tabla 2.2.3, utilizando un caudal de recirculacin a travs del reactor de 45 Lmin-1. Para obtener las constantes cinticas de eliminacin de COT en funcin de las constantes cinticas obtenidas -ajuste cintica de primer orden (MATLAB, 2009)- para de la variable se emple la misma metodologa que en el caso del lignosulfonato. Los valores
58
dicha eliminacin se muestran en la Tabla 2.3.3.2. En la experimentacin con lignosulfonato, se emple un tanque supletorio de 100 L para el almacenamiento, de tal forma que al usar una nica lnea de operacin, el parmetro Aevs-1 se mantiene constante. Tabla 2.3.3.2. Parmetro cintico k de ajuste de Experimento L1 L2 L3 L4 L5 L6
Valores extrapolados a 8h de operacin
frente al tiempo. Nivel de confianza 95% r2 0,99 0,99 0,99 0,98 0,98 0,86 Ece,v (kWhm-3) 50 21 123 49 128 a 130 a
k103 (mmin-1) 1,870,15 1,480,13 2,300,13 1,300,12 1,510,14 1,310,29
(mAmgO2-1) 2,4 1,2 4,7 0,8 2,3 1,7
El intervalo de constantes cinticas para la experimentacin con lignosulfonato en condiciones controladas fue 0,8710-3-1,5110-3 mmin-1 a escala de laboratorio. Para el mismo rango de valores de (<5 mAmgO2-1), los valores a nivel de planta piloto fueron de 1,3010-3-2,3010-3 mmin-1. Al representar conjuntamente en la Figura 2.3.3.1 los valores de k frente a , se observa que las diferencias nicamente se pueden interpretar como dispersin de los datos procedente de lignosulfonato, no se observan diferencias significativas para escalar la instalacin. experimentales. Por tanto, es posible afirmar que, en cuanto a cintica de eliminacin de COT
2.5
k103 (mmin-1)
1.5
0.5
0 0
2 3 (mAmgO-1)
2
Figura 2.3.3.1 Evolucin de K frente a . () piloto; () laboratorio (las barras de error consideran la desviacin estndar respecto de los valores ajustados); (--) curva de ajuste para valores de laboratorio
59
En cuanto al consumo energtico, en la Figura 2.3.3.2 se observa la evolucin del consumo energtico especfico por unidad de volumen frente a la densidad de corriente aplicada, la cual se ajusta a una relacin de tipo parablico, en la que se superponen los valores obtenidos a nivel de laboratorio y planta piloto, por lo que el escalado del consumo energtico es directo. Este hecho se justifica por cuanto la conductividad en los diferentes experimentos realizados se encuentra en torno a =4 mScm-1, y por tanto las resistencias hmicas impuestas deberan de ser similares al disponer de la misma distancia entre electrodos (1 mm). La diferencia de tensin entre electrodos sera similar, luego al mismo nivel de densidad de corriente, el consumo energtico por unidad de volumen debera ser similar.
150
125
(kwhm-3) E
ce,v
100
75
50
25
0 0
15
30 -2 J (mAcm )
45
60
Figura 2.3.3.2 Evolucin de Ece,v frente a J. () piloto; () laboratorio Pruebas preliminares en continuo con agua residual urbana de la EDAR de Aguilar de Campoo (20h) Una vez chequeada la viabilidad de la eliminacin de COT procedente de lignosulfonato en la planta piloto en modo discontinuo, se procedi a analizar la viabilidad de la planta piloto para tratar agua residual en continuo. Durante los experimentos en condiciones controladas de laboratorio, se observ como las constante obtenidas para las aguas residuales se encontraban entre k=1,0010-3-1,5010-3 mmin-1, siendo posible alcanzar el valor de k=1,0010-3 mmin-1 para una densidad de corriente J=10 mAcm-2 (i=35 A utilizando una nica lnea). Para determinar el caudal de operacin en continuo, la primera opcin pasar por asumir que la planta se comporta como un reactor de mezcla perfecta operado en continuo, de tal forma que segn la ec. 2.3.3.1:
60
ec. 2.3.3.1
Donde XCOT es la conversin de COT, vs es el volumen de lquido en el tanque de alimentacin (500 L) y Qc el caudal de tratamiento en continuo. Para Qc=50 Lh-1, las conversiones esperadas en COT seran entre X=30-39%, por lo que para niveles tan bajos de carga orgnica, resultaba preferible emplear un caudal menor Qc=10 Lh-1, para obtener mayores conversiones en el orden de X=68-76%. Previamente a la operacin en continuo, se comprob experimentalmente que en modo discontinuo, una corriente de 35 A era suficiente para reducir la concentracin de materia orgnica. Las condiciones experimentales para el experimento A8 con agua residual de la EDAR de Aguilar de Campoo en condiciones controladas de corriente y operacin en continuo (se completaron 20 h de operacin a lo largo de 4 das) se resume en la Tabla 2.2.3.
40 35 30 25 20 15 10 5 0 0 15 30 45 Tiempo (h) 60 75 90
90 80 70
DQO (mgO L-1)
COT (mg CL-1)
60 50 40 30 20 0
15
30
45 Tiempo (h)
60
75
90
Figura 2.3.3.3 Perfil de COT frente a tiempo. () COT Tanque de retencin; () COT salida en continuo
Figura 2.3.3.4 Perfil de DQO frente a tiempo. () DQO Tanque de retencin; () DQO salida en continuo
Las Figuras 2.3.3.3 y 2.3.3.4 muestran que la materia orgnica almacenada en el tanque de retencin disminuye con el tiempo sin necesidad de ninguna accin externa, lo que se interpreta como biodegradacin de la misma (el ajuste a una cintica de orden cero lleva a una constante de eliminacin de COT de ktr=2,210-3 h-1). En cuanto a los valores de COT a la salida del proceso en continuo, se observan mnimas variaciones a lo largo del da, observndose un descenso con el tiempo entre los diferentes das, lo cual se explica como consecuencia del descenso en la concentracin de entrada. Los valores obtenidos para la salida se encuentran entre 10-15 mgCL-1, (valor medio 12,5 mgCL-1) lo que supone una conversin del orden de X=62% (para una concentracin media de entrada de 32,5 mgCL-1). Esta conversin es prxima a la esperada X=68-76% (para la condiciones experimentales ensayadas). La conductividad y el pH permanecieron aproximadamente constantes en un valor de =0,74
61
mScm-1 y pH=8 respectivamente. El consumo energtico fue de aproximadamente 27 kWhm3
, valor que se encuentra por encima de los obtenidos para lignosulfonato, debido a la menor
conductividad del agua residual y en orden de magnitud obtenido en la escala de laboratorio en las mismas densidades de corriente (para A4, sin electrolito adicional, el consumo fue de 21 kWhm-3). Con estos resultados se puede concluir que el proceso de electro-oxidacin es capaz de operar en continuo mediante corriente controlada. Sin embargo, en las 20 h de operacin con corriente controlada, nicamente se reemplaz un 40% del volumen total inicial de agua residual. Para confirmar estos resultados, se decidi completar la experimentacin en continuo mediante un experimento de 120 h, de tal forma que el volumen de lquido en el tanque se reemplazase al menos en 2 ocasiones.
Operacin en continuo con agua residual urbana de la EDAR de Aguilar de Campoo (120h) Las condiciones de trabajo para la operacin en continuo durante 120 h se recogen en la Tabla 2.2.3 como experimento A9. Para la carga inicial del tanque de alimentacin, se utiliz agua de red (500 L) aadiendo cantidades de sulfato sdico para alcanzar una conductividad del orden de 0,76 mScm-1 de tal forma, que fuese posible iniciar el experimento con una corriente total i=35 A y una carga total inicial lo ms baja posible, con lo que posteriormente permitiese observar la estabilizacin de los valores de salida. El caudal individual por reactor se mantuvo en 45 Lmin-1. El tanque de retencin se rellen en dos ocasiones para asegurar un nivel mnimo en el mismo, as como un nivel de concentracin lo ms estable posible. Las Figuras 2.3.3.5 y 2.3.3.6 muestran la evolucin temporal del COT y de la DQO con el tiempo en el tanque de retencin y la salida de la operacin en continuo. Se observa en la Figura 2.3.3.5 que la concentracin como COT en el tanque de retencin desciende ligeramente previo a las operaciones de llenado del tanque. El efecto del llenado se observa principalmente tras el segundo realizado completado a las 95 h de operacin. En cualquier caso es posible definir un valor promedio de COT y DQO a la entrada tal que [COT]ent18 mgCL-1 y [DQO]ent65 mgO2L1
. Por su parte, los valores de COT y DQO en la corriente de salida tienden a estabilizarse
transcurrido un tiempo aproximadamente igual al tiempo de residencia (=50 h), en valores de tal que [COT]sal7-9 mgCL-1 y [DQO]sal30-35 mgO2L-1. Las Figuras 2.3.3.7 y 2.3.3.8 muestran la evolucin de la conversin de la eliminacin de COT y DQO tomando como valor de referencia el valor de COT y DQO respectivamente en cada intervalo de 12 h (correspondiente a la frecuencia de toma de muestras) en el tanque de retencin.
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25
80 70
20
60
DQO (mgO L-1)
COT (mg CL-1)
15
50 40 30 20
10
5
10
0 0
30
60 Tiempo (h)
90
120
0 0
30
60 Tiempo (h)
90
120
Figura 2.3.3.5 Perfil de COT frente a tiempo. () COT Tanque de retencin; () COT salida en continuo
Figura 2.3.3.6 Perfil de DQO frente a tiempo. () DQO Tanque de retencin; () DQO salida en continuo
En las Figura 2.3.3.7 y 2.3.3.8 se observa como la conversin obtenida tanto para la eliminacin de COT como de DQO se encuentra en el orden de X=50-60% (los valores de conversin tomaron como referencia de concentracin de entrada el valor de concentracin en el tanque de retencin en cada intervalo de 12h), una vez se alcanza el estado estacionario transcurrido un tiempo correspondiente al tiempo de residencia. La variabilidad en la conversin final obtenida se debe explicar como consecuencia de las perturbaciones introducidas en el sistema debido a la variacin de concentracin en el tanque de retencin. Estos valores se encuentran por debajo de los valores de conversin obtenidos anteriormente. Considerando que el estado estacionario se alcanza para un tiempo de residencia =50 h, las conversiones obtenidas son XCOT=0,54 para COT y de XDQO=0,51 para DQO. Por tanto, aplicando la ec. 2.3.3.1, y a partir de estos valores de conversin, se obtienen constantes cinticas aparentes k=(0,560,15)10-3 mmin-1 y kDQO=(0,500,08)10-3 mmin-1. El valor =2,15 mAmgO2-1 para la operacin actual sugiere un valor ms prximo al valor inferior reportado anteriormente de k=1,0010-3 mmin-1.
Como era de esperar a tenor de los valores de conversin obtenidos, el valor de k obtenido est por debajo del rango de k=1,00-1,5010-3 mmin-1 para el nivel de laboratorio. Una explicacin de esta reduccin en el valor de la constante cintica puede deberse a la variabilidad de las caractersticas del efluente en el periodo ensayado (fenmeno observado a nivel de laboratorio), lo cual exigira un anlisis en profundidad para estudiar la influencia del efluente en su tratamiento mediante electro-oxidacin. La influencia de una menor temperatura de operacin (en torno a los 12C en planta piloto y 25C en planta de laboratorio) en la planta piloto respecto de la planta de laboratorio podra contribuir a explicar esa reduccin. Para la corriente aplicada, y los niveles de concentracin de trabajo en la EDAR, es posible eliminar ms del 50% de COT y DQO a la entrada.
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1 0.9 0.8 0.7

(-)
1 0.9 0.8 0.7

DQO
COT
0.6 0.5 0.4 0.3 0.2 0 30 60 Tiempo (h) 90 120
(-)
0.6 0.5 0.4 0.3 0.2 0 30 60 Tiempo (h) 90 120
Figura 2.3.3.7 Perfil de conversin XCOT; (--) Conversin de COT en estado estacionario
Figura 2.3.3.8 Perfil de conversin XDQO; (-) Conversin de DQO en estado estacionario
En cuanto al consumo energtico, la experimentacin en continuo durante 120 h, permiti observar la formacin de depsitos que no se haban observado inicialmente como consecuencia de la menor extensin de los experimentos. La Figura 2.3.3.9 muestra la evolucin de la tensin entre electrodos; inicialmente la tensin parte de aproximadamente 8 V y se mantiene constante en ese valor durante las primeras 20 h de operacin. A partir de ese punto se observa un ascenso hasta 13,5 V. Por tanto, el consumo energtico se inicia en 28 kWhm-3 y finaliza en 47 kWhm-3, es decir, unas 1,7 veces el valor inicial. Esto hecho justifica la necesidad de realizar operaciones peridicas de limpieza de la unidad para disolver los depsitos formados. El valor promedio del experimento fue de unos 36 kWhm-3.
14 13 12 11 10 9 8 7 0
v (V)
30
60 Tiempo (h)
90
120
Figura 2.3.3.9 Perfil de tensin entre electrodos v (V)
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Ser por tanto necesario recomendable estudiar desde el punto de vista de ingeniera de procesos la limpieza mediante lavados cido/bsico (nica opcin de eliminacin de depsitos para ctodos de acero inoxidable) frente a la opcin de utilizar nodo y ctodo en diamante dopado con boro, lo que permite la posibilidad de realizar inversiones de polaridad programadas que disuelven los depsitos formados. Consecuentemente, a la vista de los resultados obtenidos, se puede concluir que mediante electro-oxidacin es tcnicamente viable la eliminacin de la materia orgnica procedente de aguas residuales urbanas. Para el caso ensayado de operacin en continuo con agua residual urbana durante 120 h ([COT]ent18 mgCL-1 y [DQO]sal65 mgO2L-1.; conductividad =0,75-0,78 mScm-1), se han obtenido conversiones en COT y DQO del orden del 50-60% para un caudal en continuo de 10 Lh-1, empleando una corriente continua de 35 A y un rea de electrodo de 0,35 m2.
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2.3.4. Sostenibilidad ambiental del suministro de energa al proceso ESOF mediante Anlisis de Ciclo de Vida La metodologa de Anlisis de Ciclo de Vida (ACV) (ISO, 2006a; ISO, 2006b) se ha aplicado a un caso de estudio correspondiente a tecnologa ms limpia para la recuperacin de fluoruros. En el proceso de produccin de trifluoruro de aluminio, se produce fluoruro de hidrgeno que es preciso pasar a una fase lquida para su posterior neutralizacin/precipitacin como fluoruro de calcio al emplear reactivos clcicos. La precipitacin qumica convencional de fluoruros con reactivos clcicos lleva a un producto final hmedo sin posibilidad de recuperacin. Como alternativa, se desarroll un proceso de cristalizacin en lecho fluidizado, de tal forma que la fluorita obtenida posea unas caractersticas tales que permitan su reincorporacin al proceso original de produccin de cido fluorhdrico (utilizado como materia prima en la produccin de trifluoruro de aluminio). Como consecuencia, se evita la generacin de un residuo, sin posibilidades de valorizacin, y se obtiene un producto que permite reducir el consumo original de materias primas en forma de mineral de fluorita. La aplicacin de la metodologa de ACV mostr como la cristalizacin en lecho fluidizado presentaba reducciones en el orden del 2040% respecto a la precipitacin qumica convencional para las diferentes categoras de impacto seleccionadas. Este estudio ha permitido profundizar en la metodologa de ACV de cara a su aplicacin a la tecnologa de electro-oxidacin.
En los apartados anteriores se ha evaluado la viabilidad tcnica de la eliminacin de materia orgnica mediante la tecnologa de electro-oxidacin. Es en el presente apartado donde se completa el anlisis de la tecnologa con criterios de sostenibilidad ambiental mediante aplicacin de la metodologa de ACV. Tal y como se ha sealado anteriormente la tecnologa de electro-oxidacin evita la generacin de fangos y el uso de reactivos qumicos, caracterizndose por un notable inconveniente en forma de elevado consumo energtico por unidad de volumen tratado (Caizares et al., 2002; Caizares et al., 2006a; Caizares et al., 2006b; De Lucas et al., 2002). Entre las principales razones que generan este consumo energtico elevado se encuentra la baja conductividad del efluente a tratar, que supone una prdida hmica considerable, de tal forma que el calor generado por efecto Joule se disipa en el lquido a tratar. La solucin a este inconveniente, aportada en forma de energa solar fotovoltaica, debe entenderse en trminos de energa primaria, tal y como se muestra en la Figura 2.3.4.1. Al utilizar energa de red convencional como base para suministrar energa al proceso de electro-oxidacin, las cargas ambientales estn determinadas por la transformacin de la energa primaria (contenida en los combustibles fsiles) en electricidad a travs de las distintas tecnologas que contribuyen al mix elctrico; en la mayora de las regiones industrializadas, tan slo una pequea parte de esa energa primaria es de origen renovable (en la Figura 2.3.4.1 se muestra como la energa solar fotovoltaica
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contribuye al mix elctrico); por el contrario, al suministrar energa primaria renovable al proceso (mediante mdulos solares fotovoltaicos), las cargas ambientales se derivan nicamente de la energa primaria necesaria para la produccin del mdulo solar fotovoltaico, en tanto que el 100% de la energa primaria inyectada es de origen renovable. Para que ambos procesos tuviesen similar perfil medioambiental, sera necesario un escenario en el que el 100% de la energa inyectada al mix energtico fuese energa solar fotovoltaica o energa renovable equivalente.
NO RENOVABLE
RENOVABLE
ENERGA PRIMARIA
FOTOVOLTAICA
TRANSFORMACIN ELECTRICIDAD
MIX ELCTRICO ELECTRO-OXIDACIN ELECTRO-OXIDACIN CONECTADA A RED ELECTRO-OXIDACIN
PROCESO ESOF
Figura 2.3.4.1 Vinculacin del proceso ESOF y del proceso de electro-oxidacin convencional conectada a red con la energa primaria de origen renovable y no renovable En este apartado se describe el estudio relativo a la evaluacin de la sostenibilidad ambiental del suministro de energa al proceso ESOF. El objetivo es obtener una estimacin cuantitativa de las emisiones expresadas como CO2-eq. procedentes de utilizar energa solar como base del suministro energtico al proceso ESOF frente a las procedentes del empleo de energa de red convencional mediante la metodologa de ACV. El estudio se limita a analizar las cargas ambientales en la categora de calentamiento global. Al ser puramente una cuestin energtica, es razonable analizar los resultados obtenidos considerando nicamente trminos en CO2-eq., en tanto que existe una vinculacin explicita entre el consumo elctrico y las emisiones de CO2 (http://iea.org), elaborando de este modo la huella de carbono. Esta estimacin es la primera etapa para comparar el proceso ESOF con otros procesos convencionales de tratamiento, puesto que inicialmente es necesario cuantificar, al menos de forma preliminar, las ventajas medioambientales esperadas derivadas del uso de la energa solar fotovoltaica. Por supuesto, al no entrar en juego los valores de consumo de las tecnologas de tratamiento, el presente estudio puede ser utilizado como base para comparar otros procesos de tratamiento electroqumicos asistidos por energa solar fotovoltaica. El anlisis realizado considera dos fuentes diferentes de alimentacin a un proceso de electrooxidacin empleando como marco de referencia Espaa en el ao 2007. Este marco se justifica
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en tanto que tiene sentido utilizar la informacin ms actualizada posible sobre el mix elctrico espaol frente a los valores de la tecnologa fotovoltaica en el mismo ao de referencia. Por otro lado, est claro que esos valores no seran representativos de ningn caso real por cuanto la aplicacin de dicha tecnologa se producir siempre en un horizonte futuro. Por esta razn, se complet el mismo estudio analizando el mix elctrico espaol en el horizonte 2030, as como los valores esperados para la energa solar fotovoltaica en ese mismo horizonte. A la hora de describir la generacin de potencia, se tuvieron en cuenta aquellas tecnologas representativas tanto del mix elctrico espaol (en 2007 y 2030), como de aquellas tecnologas fotovoltaicas para las cuales se dispuso de suficientes estudios prospectivos: silicio monocristalino (c-Si), silicio policristalino (mc-Si), silicio en tiras (Ribbon-Si), silicio amorfo (a-Si), telururo de cadmio (CdTe) y cobre-indio-galio-sulfuro (CIGS). Tecnologas emergentes en la actualidad como las basadas en clulas solares sensibilizadas por tinte (Dye-Sensitized Solar Cells (DSCC)) o las basadas en polmeros orgnicos fueron excluidas, por su carcter experimental. Los lmites de los sistemas estudiados para alimentar el proceso de electro-oxidacin se muestran en la Figura 2.3.4.2:
RECURSOS ENERGA NUC GNT COG ANT LIG HE HR PRODUCCIN MDULO SOLAR SOPORTE INC GIND INVERSOR SISTEMA INSTALADO FASE DE USO
MIX ENERGTICO EONS EOFS FV BIO
BALANCE DE ENERGA ENERGA (ALTO VOLTAJE) ENERGA (MEDIO VOLTAJE)
UNIDAD FUNCIONAL: 1kWh EMISIONES
UNIDAD FUNCIONAL: 1kWh
Figura 2.3.4.2 Lmites de los sistemas estudiados en el conjunto de su ciclo de vida (unidad funcional: 1 kWh en media tensin) Los modelos energticos que describen el suministro a un proceso de electro-oxidacin fueron modelados en el software de ACV GaBi 4 (GaBi, 2008). Toda la informacin relativa al consumo de energa y recursos de los procesos implicados proceden de la base de datos ecoinvent v2.0 (ecoinvent, 2008). Los diferentes parmetros empleados para construir los modelos energticos son independientes de la base de datos (la relacin entre los consumos de energa, recursos y emisiones para la unidad funcional correspondiente no proceden de ecoinvent (2008)). La unidad funcional seleccionada en la comparacin de ambas fuentes de energa fue 1 kWh en media tensin.
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Descripcin de los modelos energticos El modelo energtico utilizado para la energa procedente de la red elctrica consta de tres niveles. En el primer nivel, se describe el mix elctrico espaol considerando la contribucin de las diferentes tecnologas existentes. El mix elctrico espaol correspondiente al ao 2007 se resume en la Tabla 2.3.4.1: Tabla 2.3.4.1 Contribucin de las distintas tecnologas al mix elctrico espaol para el ao de referencia 2007 as como para el escenario 2030 2007 Tecnologa Nuclear Gas natural Cogeneracin Antracita Lignito Hidroelctrica Fueloil pesado Elica On Ref. 2007 18,6 24,4 5,7 20,7 4,8 10,3 4,5 9,1 0,0 0,2 0,8 0,8 0,1 MUEGNP 14,1 42,3 6,3 0,2 0,0 9,2 0,0 20,8 3,5 1,6 1,6 0,4 0,0 ENGNP 24,6 32,0 6,3 0,1 0,0 9,2 0,0 20,8 3,5 1,6 1,6 0,4 0,0 MPRGNP 14,0 26,4 6,2 0,0 0,0 10,0 0,0 29,7 10,2 1,6 1,5 0,4 0,0 Escenario 2030 CCMUE- ENENCP CP GNP 18,3 14,1 24,6 34,4 41,6 31,1 6,3 6,3 6,3 4,0 1,0 0,9 0,0 0,0 0,0 9,2 9,2 9,2 0,0 20,8 3,5 1,6 1,6 0,4 0,0 0,0 20,8 3,5 1,6 1,6 0,4 0,0 0,0 20,8 3,5 1,6 1,6 0,4 0,0
MPRCP 14,0 25,5 6,2 0,9 0,0 10,0 0,0 29,7 10,2 1,6 1,5 0,4 0,0
CCCP 14,1 31,0 6,3 11,5 0,0 9,2 0,0 20,8 3,5 1,6 1,6 0,4 0,0
CCEN-CP 18,3 31,1 6,3 7,3 0,0 9,2 0,0 20,8 3,5 1,6 1,6 0,4 0,0
shore
Fotovoltaica Biomasa Incineracin de residuos Gas industrial
shore
Elica Off
Con el objetivo de garantizar la mxima consistencia en los resultados obtenidos, tecnologas como la solar termoelctrica y el aprovechamiento de calor residual fueron excluidos del estudio debido a la falta de datos significativos para completar el estudio de ACV (ecoinvent, 2008). En cuanto al gas natural, se asumi que el 100% del gas natural se consume en plantas de ciclo combinado. Por su parte, se considera que el 85% del carbn importado se considera antracita. En cuanto a la produccin hidroelctrica, se asumi que el 85% de la energa proceda de centrales en corriente de ros y 15% desde centrales en embalses (SGE, 2008). Tabla 2.3.4.2 Contribucin de las distintas tecnologas fotovoltaicas consideradas a la generacin de potencia en 2007 y 2030 en Espaa a-Si 2007 2030 5,2 35 CdTe 4,7 10 CIGS 0,5 1 mc-Si 45,2 27 c-Si 42, 25 Ribbon-Si 2,2 1
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En cuanto a la contribucin solar fotovoltaica, se consideraron instalaciones de produccin elctrica montadas en suelo con una contribucin de las distintas tecnologas igual a las contribuciones de cada tecnologa en el mercado global (EPIA y Greenpeace, 2008; EPIA, 2008), y que se resumen en la Tabla 2.3.4.2. En el escenario 2030, en los que se proponen centrales de carbn con almacenamiento y captura de CO2 (ACC), se utilizaron las emisiones de ciclo de vida de una instalacin de ciclo combinado con gasificacin integrada equipada con ACC -mediante pre-combustin con absorcin fsica con Selexol- (Odeh y Cockreill, 2008). En cuanto a la tecnologa fotovoltaica en 2030 se asume que un 35% de la contribucin corresponde a tecnologas de silicio convencional, un 30% a lmina delgada y el 35% restante a nuevas tecnologas (para simplificar el anlisis, no se consider la contribucin de tecnologas emergentes, obteniendo las contribuciones que aparecen en la Tabla 2.3.4.2). Para cumplir con la demanda de potencia pico en 2030, se asumi el uso de gas natural (UNESA, 2007). En el segundo nivel, se efectu un balance de energa considerando la importacin y exportacin de energa a travs de las redes de intercambio disponibles, los consumos propios en los procesos de produccin de energa y el bombeo de agua en embalses, que se resume en la ec. 2.3.4.1: ec. 2.3.4.1 Donde Egen es la energa disponible para la distribucin; Em es la energa generada por el conjunto de tecnologas consideradas en el mix energtico; Eimp es la energa importada (82% desde Francia y 18% desde Portugal para 2007); Eexp es la energa exportada; Ecp es la energa consumida por los propios procesos de produccin de energa y Ebom es la energa empleada en los bombeos. La Tabla 2.3.4.3 muestra los valores empleados para la energa en 2007; para 2030, puesto que no resulta posible hacer una prediccin de los posibles intercambios de electricidad a tan largo plazo, ni Eexp ni Eimp fueron consideradas. Ebom se asumi como proporcional a la obtenida por generacin hidroelctrica, mientras Ecp se asumi proporcional a la energa total requerida. En un tercer nivel, se consideran las prdidas en distribucin en alto y medio voltaje asumidas por ecoinvent (2008). La prdida de energa hasta media tensin es aproximadamente para Espaa del 2,5%, valor que se emple tanto para 2007 como para el escenario 2030. Tabla 2.3.4.3 Balance de energa considerando importaciones, exportaciones, bombeos y consumos propios para Espaa en 2007 Em (GWh) 296.552 Eimp (GWh) 8.874 Eexp (GWh) 14.630 Ebom (GWh) 4.349 Ecp (GWh) 9.600 Egen (GWh) 276.847
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El modelo energtico utilizado para la energa solar fotovoltaica consta de un nico nivel, en el que se utiliza un modelo de uso del mdulo fotovoltaico, de tal forma que es posible traducir necesidades de energa en necesidades de potencia fotovoltaica y por tanto de rea requerida (para unas condiciones de irradiacin, eficacia y vida til del mdulo definidas). Pacca et al. (2007) consideran que los 4 factores con mayor repercusin en el perfil medioambiental de un mdulo solar son la irradiacin solar, la eficacia en la conversin de la energa luminosa, la vida til y el mix energtico empleado durante su proceso de fabricacin; de esta forma, el modelo de uso vendra dado por la ec. 2.3.4.2: ec. 2.3.4.2 Donde Gh es la irradiacin solar anual en una superficie horizontal para la localizacin seleccionada; es la eficacia del mdulo solar; VUm es la vida til y RD es el ratio de desempeo (factor de correccin que permite corregir desviaciones respecto de los casos ideales por polvo, sombras, etc.). Para la irradiacin se tom un valor promedio de Gh=1.825 kWh(m2ao)-1 (vlido para 2007 y 2030). Los valores de estos parmetros para 2007 y 2030 se muestran en la Tabla 2.3.4.4 (ASIF, 2008; EPIA y Greenpeace, 2008). Se consider un factor de degradacin del 0,5%ao-1 para poder anualizar las prdidas de potencia en la vida til del mdulo. El mix energtico empleado en la produccin de los mdulos se bas en los datos de ecoinvent (2008). Se consider un modelo de inversor de 500 kWp (ecoinvent, 2008) siendo el nmero de estos necesario proporcional a la eficiencia de los mdulos y al ratio de vidas tiles de los mdulos y los inversores. Para el montaje se emple un inventario compatible con Mason et al. (2006) consistente en 5 kg de acero y 2 kg de PVC por cada m2 de mdulo fotovoltaico. Los modelos de inventario de las diferentes tecnologas fotovoltaicas se tomaron de ecoinvent (2008) (excepto para CdTe, para el cual se eligi una configuracin sin marcos). Los mixes energticos empleados en la produccin se describen en ecoinvent (2008). Tabla 2.3.4.4 Parmetros de los mdulos fotovoltaicos empleados en la generacin de energa elctrica en 2007 y 2030 2007 2030 VUm 30 30 30 30 30 30 VUinv 20 20 20 20 20 20
c-Si mc-Si Ribbon-Si a-Si CIGS CdTe 15 13 12 7 10 9
RD 78 78 78 78 78 78
25 25 20 15 15 15
RD 83 83 83 83 83 83
VUm 35 35 35 30 30 30
VUinv 30 30 30 30 30 30
Descripcin de los escenarios Para la prospectiva de generacin de energa en Espaa en 2030, se utiliz la informacin del estudio Prospecciones de Generacin Elctrica 2030 (UNESA, 2007). Los diferentes escenarios
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reconocidos en UNESA (2007) seran: 1) Mxima Utilizacin de las centrales Existentes MUE (fuerte contribucin del gas natural en la demanda base y pico); 2) Expansin Nuclear EN (incremento en la contribucin de la energa nuclear); 3) Mxima Penetracin de Elica MPE (fuerte incremento de las renovables, especialmente energa elica); 4) Captura de CO2 CC (el carbn mantiene una cuota relativamente importante gracias a la captura de CO2); 5) Captura de Carbn y Expansin Nuclear CC-EN (el aumento de la demanda se suple mediante centrales de carbn con captura de CO2 y con incremento de la contribucin de la energa nuclear). Como consecuencia de la incertidumbre en los precios del CO2 en el mercado de comercio de emisiones as como a la evolucin de los mercados del gas y el carbn, se asumen dos opciones diferentes para cada escenario segn un escenario con el gas natural como opcin preferente GNP (bajo precio del gas natural y alto del CO2) y otro escenario con el carbn como opcin preferente CP (alto precio del gas natural y bajo precio del CO2). Las contribuciones de las distintas tecnologas en el escenario 2030 se resumen en la Tabla 2.3.4.1 (dentro de los escenarios GNP, no se asume que suceda el escenario CC). La energa total generada en Espaa en 2007 fue Em=297 TWh (REE, 2008) y se prev un aumento hasta los 428 TWh en 2030 (UNESA, 2007). A la vista de la Tabla 2.3.4.1, queda claro que en todos los diferentes escenarios, independientemente de la preferencia por el gas natural o el carbn, buscan reducir las emisiones de CO2 para cumplir los objetivos del Protocolo de Kioto: este hecho se observa en la transicin hacia un mix energtico en el que se abandonan los combustibles de origen fsil y se promueve la incorporacin de energas renovables, especialmente la energa elica. En cuanto a los valores de los parmetros que influyen en la ec. 2.3.4.2 para el escenario 2030 de energa fotovoltaica, se cruzaron datos de diversas fuentes (Frankl et al., 2005; NREL, 2007a; NREL, 2007b; NREL, 2007c; NREL, 2007d; Morales-Acevedo, 2006; EUPVTP, 2007; Raugei y Frankl, 2009). Para cuantificar las futuras mejoras en los procesos de produccin de mdulos fotovoltaicos, se consider una reduccin general del 20% en el consumo de materiales y energa (Frankl et al., 2005).
Resultados Como factores de potencia para calcular el total de CO2-eq., se utilizaron los correspondientes a la metodologa CML2001 incluida en GaBi (2008). Los valores procedentes de 1 kWh a media tensin de Espaa en 2007 fueron 0,511 kgCO2-eq., lo que supone un valor del 14% por encima del valor obtenido en las emisiones directas de 0,450 kgCO2 para ese mismo ao (SGE, 2008). Las reducciones propuestas en el escenario 2030 se encuentran en el rango 53%-69% frente a los valores de 2007, como consecuencia de la transicin hacia un mix energtico memos intensivo en CO2. Los valores menores se obtuvieron para los escenarios en los que se da la mxima contribucin de energas renovables, MPE-GNP y MPE-CP con valores de 0,159 y 0,165 kgCO2-eq.kWh-1 respectivamente como consecuencia de una contribucin del 40% de energa elica. Por el contrario, los valores mayores se presentaron en los escenarios CC-CP y
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CC-EN-CP (0,208 y 0,201 kgCO2-eq.kWh-1 respectivamente) donde la contribucin del carbn sigue siendo importante (11% y 7% respectivamente frente al 21% en 2007). La Figura 2.3.4.3 resume los valores obtenidos para los diferentes escenarios, mostrando como todos los escenarios futuros mejoran la situacin actual en 2007 como consecuencia de la participacin de renovables y gas natural en ciclo combinado. As mismo es importante considerar que los valores presentados en la Figura 2.3.4.3 deben considerarse como la desfavorable en cuanto a emisiones, puesto que es obviamente esperable que los factores de emisin de las distintas tecnologas de generacin de energa y procesos de produccin implicados mejoren en el horizonte propuesto (nicamente se ha detallado lo que sucede con la evolucin de la energa solar fotovoltaica).
Escenario de referencia para 2007
Emisiones procedentes del imx elctrico espaol (kg CO2 -eq.kWh-1 )
0.5
0.4
0.3
Escenarios Preferidos para Gas Natural en 2030
Escenarios Preferidos para Carbn en 2030
0.2
0.1
0 Ref. 2007 MUE-GNP EN-GNP MPE-GNP CC-EN-GNP MUE-CP EN-CP MPE-CP CC-CP CC-EN-CP
Figura 2.3.4.3 Emisiones del mix elctrico espaol para la referencia 2007 y el escenario 2030 En cuanto a los resultados procedentes del anlisis de 1 kWh procedente de energa solar fotovoltaica en 2007, se obtuvieron valores entre 0,026-0,033 kg CO2-eq.kWh-1 (excepto para CdTe, que al no disponer de marcos tiene un menor impacto). En cuanto a los valores para las tecnologas basadas en obleas de silicio (c-Si, mc-Si), Ribbon-Si y CdTe, los valores se encuentran en el rango propuesto por Fthenakis et al. (2008). Raugei et al. (2007) reportaron valores de 0,052-0,072 kg CO2-eq.kWh-1 para tecnologa cristalina y 0,017 kg CO2-eq.kWh-1 para CdTe: las diferencias se explican por las diferentes hiptesis realizadas en los estudios. En el escenario 2030, se observan reducciones en el orden del 35%-60%, ya que se espera que las
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eficiencias prcticamente se doblen en 2030. Cuando adicionalmente se integra una reduccin del 20% en el consumo de materias primas y energa por mejora de los procesos de produccin, las reducciones suben hasta un 50%-65%. Con las hiptesis realizadas, se obtuvieron valores en el rango 0,008-0,016 kg CO2-eq.kWh-1, valores similares a los propuestos por Raugei (2007) y Raugei y Frankl (2009).
0.045
0.04
Emisiones de las plantas fotovoltaicas en Espaa (kg CO2 kWh-1 )
0.035
0.03
0.025
0.02
0.015
0.01
0.005
0 Ref. 2007 Mejoras en los param. fotovoltaica Mejoras en los param. fotovoltaica + 20% red
Figura 2.3.4.4 Emisiones procedentes de las plantas de generacin de energa solar fotovoltaica en 2007 y escenario 2030. Barras en colores representan valores sin degradacin y las barras negras consideran degradacin del 0,5%ao-1: a-Si; CdTe; CIGS; mc-Si; c-Si; Ribbon-Si. La Figura 2.3.4.4 muestra los valores obtenidos para las diferentes tecnologas fotovoltaicas en 2007 y 2030, destacando el efecto de la degradacin de los mdulos (7% en tecnologas de lmina delgada y 9% en las basadas en obleas de silicio y silicio en tiras). Por tanto, asumiendo las hiptesis realizadas, en 2030 el rango para utilizacin de energa de red es 0,159-0,238 kg CO2-eq.kWh-1, mientras que para los sistemas fotovoltaicos es 0,0080,016 kg CO2-eq.kWh-1. Consecuentemente, se puede afirmar que suministrar energa solar a un proceso de electro-oxidacin mediante energa solar fotovoltaica se traduce en unas emisiones unas 16-17 veces inferiores a las obtenidas mediante energa de red en el proceso convencional: el proceso ESOF ser por tanto mucho ms sostenible ambientalmente que el suministro por red.
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supply. The solar photovoltaic energy in Spain, 2008 Annual Report) 2008, http://www.asif.es
Bonvin, G., Comninellis, C. Scale-up of bipolar electrode stack dimensionless numbers for current bypass estimation. J. Appl. Electrochem. 1994, 24, 469 California Energy Commission, California's water energy relationship CEC-700-2005-011-SF 2005 Caizares, P., Daz, M., Domnguez, J.A., Garca-Gmez, J., Rodrigo, M.A. Electrochemical oxidation of aqueous phenol wastes on synthetic diamond thin-film electrodes. Ind. Eng. Chem.
Res. 2002, 41, 4187

Caizares, P., Gadri, A., Lobato, J., Nasr, B., Paz, R., Rodrigo, M.A., Sez, C. Electrochemical oxidation of azoic dyes with conductive-diamond anodes. Ind. Eng. Chem. Res. 2006a, 45, 3468 , C., Lobato, J., Rodrigo, M.A. Treatment of fentonrefractory olive oil mill wastes by electrochemical oxidation with boron-doped diamond anodes.
J. Chem. Tech. Biotechnol. 2006b, 81, 1331

, C., Rodrigo, M.A. Electrochemical treatment of the effluent of a fine chemical manufacturing plant. J. Hazard. Mater. 2006c, 138, 173 Celik, A.N., Acikgoz, N. Modelling and experimental verification of the operating current of mono-crystalline photovoltaic modules using four- and five-parameter models. Appl. Energ. 2007, 84, 1 Chiang, L.C., Chang, J.E., Tseng, S.C. Electrochemical oxidation pretreatment of refractory organic pollutants. Water Sci. Technol. 1997, 36, 123
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De Lucas, A., Caizares, P., Rodrigo, M.A., Garca-Gmez, J. Electrochemical treatment of aqueous phenol wastes: A preliminary economical outlook. Waste Manag. Environ. 2002, 161 ecoinvent, The Life Cycle Inventory Data version 2.0. Swiss Center for Life Cycle Inventories 2008, http://www.ecoinvent.ch EPIA, EPIA/Production (Relative Share of Technology over Time), accessed in 2009, 2008 http://www.epia.org/datafigures/production.html EPIA, Greenpeace, Solar Generation V-2008 Solar electricity for over billion people and two million jobs by 2020 2008, http://www.epia.org EUPVTP, A strategic research agenda for photovoltaic solar energy technology. Working Group 3 Science, Technology and Applications of the EU PV Technology Platform. Under Sixth Framework Programme, contract n: 513548 2007 European Commission, Reference document on best available techniques in common waste water and waste gas treatment / management systems in the chemical sector 2007 Fernandes, A. Moro I. Acid Orange 7. Dyes Pigments 2004, 61, 287 Frankl, P., Menichetti, E., Raugei, M. Final report on technical data, costs and life cycle inventories of PV applications. Under Sixth Framework Programme, Project n: 502687. NEEDS New Energy Externalities Developments for Sustainability, Deliverable n 11.2-RS Ia 2005 GaBi, GaBi 4 Software-System and Databases for Life Cycle Engineering. Chair of Buildings Physics (University of Stuttgart), PE International 2008, http://www.gabi-software.com Giannis, A., Kalaitzakis, M., Diamadopoulos, E., 2007. Electrochemical treatment of olive mill wastewater. J. Chem. Technol. Biotechnol. 2007, 82, 663 Gow, J.A., Manning, C.D. Development of a photovoltaic array model for use in powerelectronics simulation studies. IEE Proc. Elec. Power Appl. 1999, 146, 193 ISO, Environmental management. Life Cycle Assessment. Principles and framework (ISO 14040:2006). International Organization for Standardization 2006a ISO, Environmental management. Life Cycle Assessment. Requirements and guidelines (ISO 14044:2006). International Organization for Standardization 2006b , I. Electrochemical degradation of C.
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Luque, A., Hegedus, S. Handbook of photovoltaic science and engineering. John Wiley & Sons, Chichester, 1138 2003 Malpass, G.R.P., Miwa, D.W., Mortari, D.A., Machado, S.A.S., Motheo, A.J. Decolorisation of real textile waste using electrochemical techniques: Effect of the chloride concentration. Water Res. 2007, 41, 2969 Markvart, T. Solar electricity. 2nd , repr. with corr John Wiley & Sons, Chichester, 280 2006 MATLAB, v7.5.0 R2007b 2007, http://www.mathworks.com/ MATLAB, v7.9.0 R2009b 2009, http://www.mathworks.com/ Michaud, P. 77 Morales-Acevedo, A. Can we improve the record efficiency of CdS/CdTe solar cells? Sol. Energy , E., Haenni, W., Perret, A., Comninellis, C. Preparation of peroxodisulfuric
acid using boron-doped diamond thin film electrodes. Electrochem. Solid-State Lett. 2000, 3,
Mater. Sol. Cells 2006, 90, 2213

Moro, A., Lopes, A., Pessoa de Amorim, M.T., Gonalves, I.C. Degradation of mixtures of phenols using boron doped diamond electrodes for wastewater treatment. Electrochim. Acta 2004, 49, 1587 NREL, National Solar Technology Roadmap: Wafer-Silicon PV, Management Report NREL/MP520-41733 Draft version 2007a, http://www1.eere.energy.gov/solar/solar_america NREL, National Solar Technology Roadmap: Film-Silicon PV, Management Report NREL/MP-52041734 Draft version, 2007b, http://www1.eere.energy.gov/solar/solar_america NREL National Solar Technology Roadmap: CdTe PV, Management Report NREL/MP- 520-41736 Draft version, 2007c, http://www1.eere.energy.gov/solar/solar_america NREL, National Solar Technology Roadmap: CIGS PV, Management Report NREL/MP- 52041737 Draft version, 2007d, http://www1.eere.energy.gov/solar/solar_america Odeh, N.A., Cockerill, T.T. Life cycle GHG assessment of fossil fuel power plants with carbon capture and storage. Energ. Policy 2008, 36, 367
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, V., Montiel, V., Aldaz, A. Photovoltaic
electrodialysis system for brackish water desalination: Modeling of global process. J. Membr.
Sci. 2006, 274, 138

Ortiz, J.M. , E., Gallud, F. , V., Montiel, V., Aldaz, A. Electrodialysis of
brackish water powered by photovoltaic energy without batteries: Direct connection behaviour.
Desalination 2007, 208, 89

Pacca, S., Sivaraman, D., Keoleian, G.A. Parameters affecting the life cycle performance of PV technologies and systems. Energ. Policy 2007, 35, 3316 Panizza, M., Michaud, P.A., Cerisola, G., Comninellis, C. Electrochemical treatment of wastewaters containing organic pollutants on boron-doped diamond electrodes: Prediction of specific energy consumption and required electrode area. Electrochem. Commun. 2001, 3, 336 Polcaro, A.M., Vacca, A., Palmas, S., Mascia, M. Electrochemical treatment of wastewater containing phenolic compounds: Oxidation at boron-doped diamond electrodes. J. Appl.
Electrochem. 2003, 33, 885

Raugei, M., Bargigli, S., Ulgiati, S. Life cycle assessment and energy pay-back time of advanced photovoltaic modules: CdTe and CIS compared to poly-Si. Energy 2007, 32, 1310 Raugei, M., Frankl, P. Life Cycle Impacts and Costs of Photovoltaic Systems: current state of the art and future outlooks. Energy 2009, 34, 392 REE, Red Elctrica de Espaa, El Sistema Elctrico Espaol 07 (The Spanish Electrical System
07) 2008, http://www.ree.es

Serrano, K., Michaud, P.A., Comninellis, C., Savall, A. Electrochemical preparation of peroxodisulfuric acid using boron doped diamond thin film electrodes. Electrochim. Acta 2002,
48, 431
SGE, Secretara General de Energa, Ministerio de Industria, Turismo y Comercio, Gobierno de Espaa, La Energa en Espaa 2007 (The Energy in Spain 2007) 2008, http://www.mityc.es Tchobanoglous, G., Burton., F.L., Stensel, H.D. Wastewater engineering: Treatment and reuse.
4th McGraw-Hill, Boston etc., 1819 2003

Townsend, T.U. Simplified performance modeling of a direct-coupled photovoltaic systems. Master's Thesis, University of Wisconsin, Madison 1989
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UNESA, Asociacin Espaola de la Industria Elctrica, Prospecciones de Generacin Elctrica 2030 (UNESAs Outlook for Electricity Generation for 2030) 2007, http://www.unesa.es Yaws, C.L. Yaws' handbook of thermodynamic and physical properties of chemical compounds. Knovel, Norwich, New York 2003
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2.5 Nomenclatura del captulo 2

Ae rea de electrodo (nodo disponible) (cm2) Am rea total incidente de mdulos solares fotovoltaicos (m2) Carbono Orgnico Total adimensional [COT][COT]0-1 (mgCL-1) [COT] Concentracin de Carbono Orgnico Total (mgCL-1) [COT]0 Concentracin inicial de Carbono Orgnico Total (mgCL-1) [DQO] Concentracin de Demanda Qumica de Oxgeno (mgO2L-1) [DQO]0 Concentracin inicial de Demanda Qumica de Oxgeno (mgO2L-1) Ebom Energa empleada en los bombeos de agua a embalses (GWh) Ece,m Consumo especfico de energa por unidad de masa de COT eliminada (kWhkgCOT-1) Ece,v Consumo especfico de energa por unidad de volumen (kWhm-3) Ecp Energa consumida por los propios procesos de produccin de energa (GWh) Eexp Energa exportada desde Espaa (GWh) Egen Energa disponible para la distribucin en alta tensin (GWh) Eimp Energa importada hacia Espaa (GWh) Em Energa por el conjunto de tecnologas consideradas en el mix energtico espaol (GWh) g Potencia solar incidente total (W) gp Potencia solar incidente total promedio en condiciones de corriente no controlada (W) G Irradiacin solar incidente sobre la superficie de los mdulos fotovoltaicos (Wm-2) Gh Irradiacin solar anual en una superficie horizontal (kWh(m2ao)-1) i Corriente elctrica total aplicada al reactor de electro-oxidacin (A) ip Corriente elctrica total promedio aplicada al reactor de electro-oxidacin en condiciones de corriente no controlada (A) iMP,ref Intensidad en mxima potencia en condiciones de referencia (1000 Wm-2, 25C) (A) iSC,ref Intensidad de cortocircuito en condiciones de referencia (1000 Wm-2, 25C) (A) I Corriente elctrica total aplicada al reactor de electro-oxidacin por unidad de rea de mdulo fotovoltaico (A)
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J Densidad de corriente (mAcm-2) k Constante cintica de eliminacin de COT (mmin-1) kDQO Constante cintica de eliminacin de DQO (mmin-1) ki Constante cintica instantnea en funcin de la corriente i generada por los mdulos solares (mmin-1) km Coeficiente de transferencia de materia hacia la superficie electrdica (mmin-1) kS Constante cintica de electro-oxidacin en la superficie del nodo (mgO2m(mAmin)-1) kS* Constante cintica de electro-oxidacin en la superficie del nodo con referencia al volumen de lquido en el reactor electroqumico (mgO2m(mAmin)-1) kSkm-1 Cociente entre kS y el coeficiente de transferencia de materia km (mgO2mA-1) kSkm-1* Cociente entre kS y el coeficiente de transferencia de materia km con referencia al volumen de lquido en el reactor electroqumico (mgO2mA-1) kS/C Constante cintica de eliminacin de COT agrupada para las series de sulfato sdico y cloruro sdico (mmin-1) ktr Constante cintica de degradacin de materia orgnica en el tanque de retencin (dia-1) k Constante cintica de eliminacin de COT en funcin del parmetro (mmin-1) k1 Parmetro de agrupacin de constantes en la ec. 2.3.2.4 (mmin-1A-1) k2 Parmetro de agrupacin de constantes en la ec. 2.3.2.4 (A-1) p Potencia elctrica generada por los mdulos fotovoltaicos (W) P Potencia elctrica solar por unidad de rea de mdulo solar fotovoltaico (Wm-2) Qc Caudal de tratamiento en continuo (Lh-1) rA Velocidad de reaccin de eliminacin de COT referida al rea de electrodo (mmgC(minL) -1) R resistencia hmica ejercida por el reactor electroqumico () RD Ratio de desempeo (%) v Tensin entre los electrodos del reactor electroqumico (V) ve Volumen de lquido en el reactor de electro-oxidacin (L) vMP,ref Intensidad mxima potencia en condiciones de referencia (1000 Wm-2, 25C) (V) vo Voltaje mnimo para generar una corriente elctrica entre los extremos del reactor electroqumico (V)
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vOC,ref Voltaje en circuito abierto en condiciones de referencia (1000 Wm-2, 25C) (V) vs Volumen de lquido en el tanque de alimentacin (L) VUinv Vida til del inversor (ao) VUm Vida til del mdulo solar fotovoltaico (ao) XCOT Conversin de COT (-) XDQO Conversin de DQO (-) Conductividad del efluente (mScm-1) Eficacia de un mdulo solar fotovoltaico (%) Tiempo de residencia (h) Cociente entre corriente aplicada y carga orgnica inicial expresada como DQO (mAmgO2-1)
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Captulo 3. Conclusiones
Chapter 3. Conclusions
Captulo 3. Conclusiones / Chapter 3. Conclusions
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3.1 Conclusiones y trabajo futuro

3.1.1 Conclusiones Las conclusiones obtenidas a lo largo de la presente tesis doctoral han sido las siguientes: 1) Se ha demostrado tcnicamente la viabilidad de utilizar la tecnologa de electrooxidacin mediante electrodos de diamante dopado con boro en el tratamiento de aguas residuales con carga orgnica a escala de laboratorio y planta piloto. En el caso de la escala de laboratorio, el suministro energtico se realiz empleando tanto corriente de red como utilizando energa solar fotovoltaica (proceso ESOF, ElectroOxidacin Solar Fotovoltaica). Para la escala de planta piloto, se utiliz corriente de red, disponiendo la instalacin fotovoltaica necesaria para realizar el tratamiento en el futuro prximo. 2) Se ha realizado el estudio cintico de la eliminacin de Carbono Orgnico Total en disoluciones acuosas de lignosulfonato (500-1500 mgO2L-1) mediante una instalacin a escala de laboratorio del proceso ESOF, alcanzando eliminaciones superiores al 90% en Carbono Orgnico Total operando en modo discontinuo. Se ha desarrollado una expresin que permite evaluar la constante cintica del proceso k como una funcin de la corriente aplicada i dependiente de la potencia solar incidente g tal que k=k1i(g)(1+K2i(g))-1, de tal forma que el proceso estar controlado por la densidad de corriente a bajos valores de i mientras que estar controlado por la transferencia de materia a bajos valores de la corriente aplicada, siendo el valor obtenido mximo de k=(2,3110-3 mmin-1) para lignosulfonato. 3) Se ha realizado el estudio del proceso de electro-oxidacin para la eliminacin del Carbono Orgnico Total de aguas residuales urbanas procedentes de la EDAR de Aguilar de Campoo, Palencia (baja carga orgnica y conductividad inferior a 1 mScm-1) mediante una instalacin de electro-oxidacin a escala de planta piloto. Mediante la operacin en continuo para caudales de 10 Lh-1, se alcanzaron conversiones superiores al 50% en Carbono Orgnico Total y Demanda Qumica de Oxgeno, con una constante cintica aparente para Carbono Orgnico Total k=0,5610-3 mmin-1 y un consumo energtico para electro-oxidacin del orden de 25 kWhm-3 (empleando un rea andica de 0,35 cm2). 4) Se ha aplicado la metodologa de Anlisis de Ciclo de Vida para evaluar la sostenibilidad ambiental del suministro energtico al proceso de electro-oxidacin mediante energa de red y mediante energa solar fotovoltaica en Espaa. El anlisis en trminos de CO2-eq. estim valores entre 15-40 veces para el caso del suministro como energa de red (0,2 kgCO2-eq.kWh-1) frente a energa solar fotovoltaica (0,005-0,015 kgCO2-eq.kWh-1) para Espaa en el horizonte 2030.
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3.1.2 Trabajo futuro Como trabajo futuro, se considera la continuacin de la investigacin en relacin a los contenidos desarrollados en esta tesis: 1) Ingeniera del Proceso ESOF: se desarrolla la automatizacin del proceso ESOF para disponer de un sistema de control que regulase el caudal de entrada en continuo en funcin de la corriente inyectada al sistema; a mayor corriente de entrada, mayor caudal a tratar, dependiendo de la energa solar incidente. 2) Estabilidad del proceso ESOF a largo plazo: se propone un estudio en profundidad para conocer qu variables influyen de manera ms significativa en el proceso en un periodo de tiempo significativo. Dentro de este estudio, se incluye cual es la influencia en el sistema de realizar operaciones de lavado continuadas frente a las inversiones de polaridad. 3) Evaluacin de la Sostenibilidad Ambiental mediante Anlisis de Ciclo de Vida del proceso ESOF: se estudian las cargas ambientales asociadas al proceso de electrooxidacin de cara al proceso de toma de decisin sobre posibles mejoras de funcionamiento del proceso, as como para poder comparar sus resultados frente a otros procesos de tratamiento.
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3.1 Conclusions and future w ork

3.1.1 Conclusions
The conclusions which can be withdrawn from the current PhD thesis are showed as follows: 1) It has been technically demonstrated the suitability of using electro-oxidation technology by means of boron doped diamond electrodes for the treatment of wastewater polluted with organic load at both lab and pilot plant scale. At lab scale, the energy supply was based on grid and in photovoltaic solar energy (PSEO process, Photovoltaic Solar Electrochemical Oxidation). At pilot scale, grid current was used and a photovoltaic solar installation to perform the treatment is available. 2) A kinetic study of the removal of lignosulfonate from aqueous solutions (500-1500 mgO2L-1) by a PSEO process lab scale plant showed removals higher than 90% in Total Organic Carbon. It has been developed an expression that allows to assess the kinetic constant of the process k as a function of the applied current i which depends of the solar power g such as k=k1i(g)(1+K2i(g))-1, so the process becomes current density controlled at low i values whereas it is controlled by mass transfer at high i values, with a maximum value of k=(2,3810-3 mmin-1) for lignosulfonate. 3) A study of the electro-oxidation process for the removal of Total Organic Carbon from urban wastewater coming from the WWTP of Aguilar de Campoo (low organic loading and conductivity below 1 mScm-1) by a pilot scale plant was completed. For continuous operation at flowrate of 10 Lh-1, conversions higher than 50% in Total Organic Carbon and Chemical Oxygen Demand, with a kinetic constant for Total Organic Carbon k=0,5610-3 mmin-1 and an energy consumption for electro-oxidation about 25 kWhm-3 (total anodic area of 0.35 m2). 4) Life Cycle Assessment methodology has been applied to assess the environmental sustainability of the energy supply to an electro-oxidation process both by grid current and photovoltaic solar energy. The analysis in terms of kgCO2-eq. considered values about 15-40 times higher for the case of grid energy supply (0,2 kgCO2-eq.kWh-1) versus photovoltaic solar energy (0,005-0,015 kgCO2-eq.kWh-1) for Spain in the 2030 horizon.
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3.1.2 Future w ork

As future work, it is possible to continue the research because of its relation with the contents considered in this thesis: 1) PSEO Process Engineering: PSEO process automation would lead to a system control in which the input current controls the flowrate to the electro-oxidation plant, so the higher the applied current, the higher the flowrate to be treated as a function of the incident solar irradiance. 2) Long-term stability of the PSEO process: an in-depth study related to assessing the variables with greater influence in the process in the long-term is recommended. This study should include the relevance of continuous chemical washing versus the possibility of continuous reversal polarity. 3) Environmental Sustainability Assessment by Life Cycle Assessment
methodology of a PSEO process: a more in-depth study of the environmental loads related to the electro-oxidation process will help in the decision-making process about future process improvements, as well as to compare the performance versus other conventional treatment processes.
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Captulo 4. Artculos cientficos
Chapter 4. Scientific articles
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Captulo 4. Artculos cientficos / Chapter 4. Scientific articles
4.1 Dominguez-Ramos, A., Aldaco, R., Irabien A. Life cycle assessment as a tool for cleaner production: Application to aluminium trifluoride.
I nt. J. Chem . React. Eng. 2007, 5 (A33)

Resumen El Anlisis de Ciclo de Vida (ACV) es una herramienta potente a la hora de identificar opciones ambientalmente sostenibles dentro de la ingeniera de procesos. Esta metodologa se ha aplicado a un caso de estudio correspondiente al tratamiento de efluentes fluorados procedentes de la produccin de trifluoruro de aluminio. Se han analizado las cargas ambientales procedentes de dos opciones de proceso alternativas: i) la precipitacin qumica, que lleva a la formacin de un fango rico en agua, que debe ser deshidratado previo a su traslado a un vertedero de inertes ii) la recuperacin de producto en forma de fluorita mediante un proceso de cristalizacin en un reactor de lecho fluidizado. Mediante la utilizacin de software de ACV y la integracin de los indicadores ambientales publicados The Sustainability Metrics, se identific el proceso de cristalizacin en lecho fluidizado como una alternativa ms sostenible que el proceso convencional de precipitacin, presentando reducciones del orden del 20-40% en los diferentes indicadores seleccionados como consecuencia de la recuperacin de fluorita como producto reutilizable en la produccin de cido fluorhdrico.
Original abstract
Life Cycle Assessment (LCA) is a powerful tool in order to identify sustainable alternatives in process engineering. In this work, the LCA of two fluoride effluent treatment processes in the aluminium trifluoride (AlF3) manufacture has been carried out. Two scenarios have been considered: (i) chemical precipitation for fluoride removal, leading to a water-rich sludge, which has poor dewatering properties and therefore, must be managed in inert waste landfills, and (ii) the recovery of fluoride by crystallization as synthetic fluorite to be reused in the hydrogen fluoride (HF) manufacture. The LCA software SimaPro 7 (PR Consultants BV) makes it possible to compare in terms of different methodologies like Eco-Indicator 99 and CML 2 Baseline 2000. Environmental metrics developed by IChemE were included in the software. The crystallization process in a Fluidized Bed Reactor allows reductions in the range of 20-40% for most metrics because of the recycled synthetic fluorite to the HF manufacture.
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I NTERNATIONAL J OURNAL OF C HEMICAL R EACTOR E NGINEERING

Volume 5 2007 Article A33
Life Cycle Assessment as a Tool for Cleaner Production: Application to Aluminium Triuoride
Antonio Dominguez-Ramos Angel Irabien Ruben Aldaco
Universidad de Cantabria, domingueza@unican.es Universidad de Cantabria, aldacor@unican.es Universidad de Cantabria, irabienj@unican.es ISSN 1542-6580 Copyright c 2007 The Berkeley Electronic Press. All rights reserved.
Life Cycle Assessment as a Tool for Cleaner Production: Application to Aluminium Triuoride
Antonio Dominguez-Ramos, Ruben Aldaco, and Angel Irabien
Abstract
Life Cycle Assessment (LCA) is a powerful tool in order to identify sustainable alternatives in process engineering. In this work, the LCA of two uoride efuent treatment processes in the aluminium triuoride (AlF3) manufacture has been carried out. Two scenarios have been considered: (i) chemical precipitation for uoride removal, leading to a water-rich sludge, which has poor dewatering properties and therefore, must be managed in inert waste landlls, and (ii) the recovery of uoride by crystallization as synthetic uorite to be reused in the hydrogen uoride (HF) manufacture. The LCA software SimaPro 7 (PR e Consultants BV) makes it possible to compare in terms of different methodologies like Eco-Indicator 99 and CML 2 Baseline 2000. Environmental metrics developed by IChemE were included in the software. The crystallization process in a Fluidized Bed Reactor allows reductions in the range of 20-40% for most metrics because of the recycled synthetic uorite to the HF manufacture. KEYWORDS: life cycle assessment, cleaner production, aluminium triuoride, crystallization, precipitation
The authors are grateful for the nancial support of the Ministry of Education and Science of Spain through the project CTM2006-00317. Antonio Dom nguez thanks the Ministry of Education and Science of Spain (FPU fellowship (ref. AP2005-1716)).
Dominguez-Ramos et al.: LCA as a Tool for Cleaner Production: Application to AlF3
1. INTRODUCTION
Sustainable Development is a model of progress that links economic development, protection of the environment and social responsibility. This progress towards Sustainability is a key feature of the policy making in the European Union (EU). As a consequence, an Integrated Prevention and Pollution Control (IPPC) Policy and an Integrated Product Policy (IPP) have emerged. Related to IPP, the Life Cycle Assessment (LCA) has been pointed out in the EU as the appropriate framework to evaluate the potential impact related to products. This LCA approach is essential for an objective quantification, giving a vision of the relationship between human activities and environment, and identifying the environmental impacts. The latest developments show LCA as a powerful decision making tool in order to identify the clean and sustainable alternatives for process engineering (Azapagic, 1999). LCA software is available in the market. This software provides a fast calculation of the environmental indicators based on environmental impact methods (saving time and money). Additionally, comprehensive databases with a large number of system products/processes are included, being the user able to modify/complete the existing databases and the environmental impact assessment methods. These features are included in SimaPro 7, supplied by Pr Consultants BV. There are several environmental impact models that can be applied in the LCA methodology, like EcoIndicator 99 (Goedkoop and Spriensma, 2002) and CML 2 Baseline 2000 (Guine et al., 2001). In this work, the environmental metrics published in The Sustainability Metrics (IChemE, 2002) were implemented. Aluminium trifluoride (AlF3) is a white solid used in the aluminium manufacture as fluxing agent in aluminium smelting cells. Two different processes are available to obtain AlF3: the wet fluorosilicic acid process and the most common Lurgi process, also known as dry fluorspar process (EIPPCB, 2006). In the Lurgi process, a hydrogen fluoride (HF) gas stream reacts with aluminium hydroxide Al(OH)3 obtaining AlF3 in a fluidized bed reactor. As the AlF3 manufacture requires around 0.8 tons of HF per ton of AlF3, high amounts of the acid (obtained by reacting fluorspar and sulphuric acid) are required, being HF production coupled to the AlF3 production. The non-reacted HF gas is absorbed in water in the waste gas treatment section and large volumes of fluoride wastewaters are generated, so a treatment is necessary to reduce fluoride concentration below the required limits. Several methods to remove fluoride from industrial wastewater have been described and applied (Aldaco, 2005a). The most common technology used for fluoride removal from industrial wastewaters is chemical precipitation, which generates large amounts of a water-rich sludge, which must be disposed of with increasing costs. In addition, the high water content (50-60%) and the low quality of the sludge (40-60% of calcium fluoride CaF2) prevent the fluoride recovery because of technical and economic reasons. Fluidized Bed Crystallization (FBC) has been used in different water and wastewater treatments (Aldaco et al., 2005b; Aldaco et al., 2005c). Recently, crystallization in a FBR has been studied to remove fluoride from industrial wastewaters (Aldaco, 2005a). The process is based on the crystallization of calcium fluoride upon calcium carbonate grains instead of mass precipitation in the liquid phase. During the operation, the grains increase in diameter inside a fluidized bed reactor and fluoride-covered grains are removed from the bottom of the reactor and replaced by fresh seed grains. The use of granular calcite as seed material makes it possible to obtain synthetic calcium fluoride acid grade, which can be reused as raw material in the HF manufacture (Aldaco et al., 2006; Aldaco et al., 2007). As can be seen in Table 1, CaF2 sludge from chemical precipitation does not accomplish with purity requirements of acid grade fluorite, so a lower yield would be expected. In the other hand, CaF2 obtained from crystallization process can be reused in HF production. Figure 1 shows CaF2 pellets obtained with crystallization in a FBR.
Published by The Berkeley Electronic Press, 2007
International Journal of Chemical Reactor Engineering
Vol. 5 [2007], Article A33
Table 1. Acid grade fluorite requirements and calcium fluoride from crystallization process and chemical precipitation
PARAMETER Morphology Water content CaF2 content ACID GRADE FLUORITE a Pellets (0.15mm) CRYSTALLIZATION PROCESS a Pellets (0.8-1.0 mm) >98% SiO2 <1% CaCO3 <1% CHEMICAL PRECIPITATION b Sludge (1-10 m) 60-80% 30-40% CaCO3 1.0-5.0 %
>97% SiO2 <1% S (sulfur)<0.01% Others Metallic oxides<0.5% Fe, Pb, Zn traces a Aldaco et al., 2007; b Aldaco et al., 2006;
(a)
(b)
Figure 1. Photographs of seed material (a) and (b) CaF2 Pellets from the crystallization process in a FBR. The objectives of this work are to assess and compare the environmental burdens related to the control of fluoride from industrial waters in the AlF3 production using LCA methodology.
2. LCA METHODOLOGY
Life Cycle Assessment (LCA) is compiled of several interrelated components: goal and scope definition, inventory analysis, impact assessment and interpretation (ISO, 1998).
2.1 Goal and scope definition

The goal of this study is to assess the most relevant environmental metrics in the fluoride removal from industrial wastewaters from the AlF3 production using the LCA methodology for two selected scenarios: Scenario 1: The fluoride wastewaters obtained from the AlF3 production is treated by chemical precipitation, giving a water-rich sludge with poor dewatering characteristics. Therefore, it must be stored in inert waste landfills without any fluoride recovery. Scenario 2: the recovery of fluoride by crystallization as a synthetic fluorite to be reused in the HF manufacture is carried out.
In order to compare both scenarios, different environmental impact assessment methods were applied. These results may be considered by the AlF3 industry to select a more sustainable option in the fluoride wastewater control. The operating costs in the crystallization process are similar to the conventional precipitation. Nevertheless,
http://www.bepress.com/ijcre/vol5/A33
the derived benefits are important (reuse, reduction of chemical waste and reduction of discharge fee). An estimate costs evaluation is shown in Table 2 (Aldaco et al., 2005c). Table 2. Estimate costs and benefits evaluation.
TYPE OF COSTS
Capital costs Operating costs Depreciation Chemicals Energy Staff Maintenance Benefits Reuse Reduction of chemical waste Saving on investment for precipitation plant Reduction of discharge fee
a
COSTS (USD/kg) a
REMARKS
Depending on capacity
3-25 0.502.50 0.25
Depending on capacity Depending on concentration 1 h per day 35% of investment
0-14.50 2-8 3-12 30-40
Depending on concentration in sludge In the case of final treatment In the case of final treatment
Per kg of recovered anion;
The functional unit allows that inputs and outputs are referred to the same unit. In the present study, the functional unit is one tonne of AlF3 in order to refer the analysis to the product unit. The system limits describe the unitary process (subsystems) included in the global product system and establish which system products will be considered, setting up the trade-offs between the system product and the environment. For the present work, a closed-loop system expansion procedure was adopted to take into account the CaF2 obtained in scenario 2: the obtained synthetic CaF2 substitutes the fluorite used as a raw material in the HF manufacture (raw material in the AlF3 industrial process) and no additional step is needed. Process equipment in chemical precipitation and crystallization processes was not accounted in the present life cycle inventory (no available data to support a description of the selected equipment). Consequently, only one subsystem was assumed: the fluoride wastewater treatment stage. The subsystem for the two scenarios is shown in Figure 2.
CaSO4 H2SO4
Water
Al(OH)3
CaSO4
H2SO4
Water
Al(OH)3
CaF2
Generation of gaseous HF
HF (gas)
AlF3 production
AlF3
CaF2
Generation of gaseous HF
HF (gas)
AlF3 production
AlF3
Fluoride wastewater
Energy
Chemical Precipitation
Precipitation
Ca(OH) CaO 2
Fluoride wastewater
Energy
Synthetic Calcium Fluoride (CaF2)
Flocculant
Ca(OH)2
Drying
Settling
Flocculation
Crystallization in a Fluidized Bed Reactor

Seed Material
Filtration
Fluoride free wastewater
Sludge (CaF2+Ca(OH)2)
Fluoride free wastewater
Figure 2. Scenario 1: Chemical precipitation vs Scenario 2: Crystallization process. The resources and emissions for scenario 1 (chemical precipitation) and for scenario 2 (crystallization process) were adapted from the literature (Giesen, 1998; Aldaco, 2005a) to show the resources and emissions in the same functional unit for the two scenarios. The reliability of these two references guaranteed the data quality. Due to the assumed geographical, technological and temporal requirements, the data presented in Table 3 can be considered as representative.
The electricity mix for the UCPTE (Union for the Coordination of the Production and Transport of the Electricity) was assumed (shares of the national production at the busbar contributing to total UCPTE production). In order to include the flocculant, Dimethylethanolamine (DMEA) was the selected substance as best proxy available. The use of Eco-Invent v.1.2 database (Eco-Invent, 2005) leads to Table 4, in which last five years, average resources and emissions from European plants were considered. Geographical, technological and temporal adequacy of the different items was guaranteed. Table 3. Inventory data for selected processes.
CHEMICAL PRECIPITATION Resources Reagent Electricity Seed Flocculant Reused Product Synthetic fluorite Emissions to water Fluoride Solid wastes Fluorite sludge
a
CRYSTALLIZATION PROCESS 77 kg Ca(OH)2/Ton AlF3 b 0.0203 MWh/Ton AlF3 a 3.51 Kg CaCO3/Ton AlF3 a -77 Kg CaF2/Ton AlF3
b b b b
101 Kg CaO/Ton AlF3 b 0.0068 MWh/Ton AlF3 a 0.51 Kg DMEA/Ton AlF3 a 0.163 Kg F-/Ton AlF3
0.163 Kg F-/Ton AlF3
176 Kg CaF2 sludge/Ton AlF3
40 Kg CaF2 fines/Ton AlF3 b
Giesen, 1998; b Aldaco, 2005a;
2.2. Life Cycle Inventory, Impact Assessment and Interpretation

Life Cycle Inventory (LCI) is the LCA step that involves the collection and computation of data to accomplish the goal and scope of the work by quantifying the inputs and outputs related with the product system under study within the whole life cycle (ISO, 1998). The inventory data for the system product under the two selected scenarios were collected from the sources cited in the data quality section. More details about the data shown in the data quality table are explained in the result and discussion section. Table 4. Data quality: geographical, technological and temporal features for selected items. ITEM Calcium oxide, CaO Calcium hydroxide, Ca(OH)2 Calcium carbonate, CaCO3 Electricity Calcium fluoride, CaF2 Solid wastes
a
PLACE a Europe Europe Europe Europe Europe Europe
TECHNOLOGY a High level High level High level Average technology used to transmit and distribute electricity Separation by crushing, grinding and flotation Landfill with restoration after closure
TIME PERIOD a Last updated Last updated Last updated

b b b
Data for 2000 Time of the basedon publications Data for 2000
Eco-Invent, 2005; b Last updated in the Eco-Invent database;
The step involving the assessment of the LCI results is the Life Cycle Impact Assessment (LCIA) step, in order to get a better knowledge on the environmental impacts using environmental indicators to show aggregated resources and emissions (ISO, 2000a). Different methodologies have been developed to complete the life cycle
impact assessment. These methodologies translate the resources consumption and emissions into environmental metrics, which can be directly interpreted. Each methodology performs its own classification and characterization for the LCI values. A summary of the different environmental metrics and units is presented in Table 5, being ordered by safeguard objects (human health, environmental quality and resources conservation). The objectives for the interpretation step are to asses the results, to get conclusions, to explain limitations, to emit recommendations based on all previous steps and to report the results of the interpretation of the life cycle in a clear way, emphasizing the iterative character of the LCA (ISO, 2000b). This information is presented in the results and discussion section.
3. RESULTS AND DISCUSSION 3.1 Life Cycle Inventory

The data presented for the two selected scenarios were assumed to accomplish with the data quality requirements. These data were modified from the original sources to express the data in the same functional unit. Data from Giesen (1998) were originally expressed in terms of fluoride mass removal; the relation Kg F-/Ton AlF3 obtained from Aldaco (2005a) was checked as valid to express the data in the same functional unit. The generated sludge in the precipitation process included the non-reacted CaO and solids from the AlF3 process (Aldaco, 2005a).
3.2 Comparison of the environmental burdens for scenario 1 and 2

Results from the LCIA for the two selected scenarios by using the LCA software SimaPro 7 (Pr Consultans BV) are summarized in Figures 3-5 (in radial charts, negative values corresponding to bar charts were adjusted to zero for clarity). As shown in Figures 3-5, a main conclusion can be pointed out: the crystallization process (scenario 2) is a cleaner possibility when it is compared to the chemical precipitation (scenario 1), regardless of the methodology in the environmental impact life cycle assessment. The crystallization gives better results in most of the environmental metrics. The main reason for this better environmental performance of crystallization is the reused fluorite. When 77 Kg of CaF2 returns to the HF production, the consumption of this raw material is subtracted, decreasing the global environmental load. Excluding some specific metrics, reductions in the order of 20-40% are typical for crystallization. Better results appeared for precipitation only in some metrics. The quicklime was the most important responsible for this worse environmental performance in scenario 1. On the other hand, scenario 2 got better results by the energy avoided related to the extraction and processing of fluorspar. Therefore, the best environmental performance of the crystallization option can be attributed to the recycled synthetic fluorite consumption as raw material in the HF manufacture, more than to the CaF2 sludge formation avoided. The model for the sludge disposal shows that inert waste disposal is not very damaging to environment, if direct comparison with the total environmental burdens is done, the environmental load could be negligible in relation to operational problems due to sludge handling. LCA for fluorspar turns out to be critical, since the better results for crystallization are directly related to this issue.
Table 5. Metrics and units in selected environmental methodologies.

IChemE SUSTAINABILITY METRICS c
ECO-INDICATOR 99 a
CML 2 BASELINE 2000 b
Human Health
Carcinogenics (DALY) Respiratory Inorganics (DALY) Respiratory Organics (DALY) Human Toxicity (Ton 1,4-dichlorobenzene eq) Human Health Effects (Ton benzene eq)
Acidification-Eutrophication (PDF/m2yr) Radiation (DALY)) Climate change (DALY) Ozone Layer (DALY)
Acidification (Ton SO2 eq) Ozone Layer Depletion (Ton CFC-11 eq) Fresh Water Aquatic Ecotoxicity (Ton 1,4-dichlorobenzene eq) Marine Aquatic Ecotoxicity (Ton 1,4-dichlorobenzene eq) Terrestrial Ecotoxicity (Ton 1,4-dichlorobenzene eq) Eutrophication (Ton PO43- eq) Global Warming (Ton CO2 eq) Photochemical Oxidation (Ton C2H4 eq)
Atmospheric Acidification (Ton SO2 eq) Stratospheric Ozone Depletion (Ton CFC-11 eq) Global Warming (Ton CO2 eq) Photochemical Ozone Formation (Ton C2H4 eq)
Air
Ecotoxicity (PAF/m2yr)
Environment
Ecotoxicity to Aquatic Life (metals) (Ton copper eq) Ecotoxicity to Aquatic Life (others) (Ton formaldehyde eq) Eutrophication (Ton PO43- eq) Aquatic Acidification (Ton H+ released eq) Aquatic Oxygen Demand (Ton oxygen eq) Land use (m2) Wastes (Ton wastes)
Water
Land Use (PDF/m2yr)
Depletion
Soil
Resources
Minerals Fossil Fuels (MJ Surplus)
Abiotic Depletion (Kg Sb eq)
Material (Kg resources)
Energy
Energy (GJ)
Goedkoop and Spriensma, 2002; b Guine et al., 2001; c IChemE, 2002;

C 1,000 FF 0,800 CRYSTALLISATION PRECIPITATION RO
0,8 0,7 0,6

RI
0,600 M
PRECIPITATION CRYSTALLIZATION
0,400
0,5 0,4 0,3

CC
0,200
0,000 LU
0,2 0,1 0 -0,1 -0,2 C RO RI CC R OL E AE LU M FF
AE
OL
C: Carcinogenics x 106 (DALYs); RO: Respiratory Organics x 107 (DALYs); RI: Respiratory Inorganics x 104 (DALYs); CC: Climatic Change x 104 (DALYs); R: Radiation x 106 (DALYs), OL: Ozone Layer x 108 (DALYs); E: Ecotoxicity x 10-1 (PAF/m2yr); AE: Acidificationeutrophication x 100 (PDF/m2yr); LU: Land Use x 100 (PDF/m2yr); M: Minerals x 101 (MJ Surplus); FF: Fossil Fuels x 10-2 (MJ Surplus)
Figure 3. Radial and bar environmental charts for Eco-Indicator 99.
AD 1,0 Eu 0,8 0,6 0,4 A 0,2
CRYSTALLIZATION PRECIPITATION GW
0,8 0,6 0,4

OLD
0,2 0
0,0
-0,2
PO HT
-0,4 -0,6 -0,8 AD GW OLD HT FWAqE MAqE TE PO A Eu
TE
FWAqE
MAqE
AD: Abiotic Depletion x 100 (Kg Sb eq); GW: Global Warming x 10-3 (Kg CO2 eq); OLD: Ozone Layer Depletion x 105 (Kg CFC-11 eq); HT: Human Toxicity (Kg 14-dichlorobenzene); FWAqE: Fresh Water Aquatic Ecotoxicity x 100 (Kg 1,4-dichlorobenzene eq); MAqE: Marine Aquatic Ecotoxicity x 10-6 (Kg 1,4dichlorobenzene eq), TE: Terrestrial Ecotoxicity x 101 (Kg 1,4-dichlorobenzene eq); PO: Photochemical Oxidation x 101 (Kg C2H4 eq); A: Acidification x 100 (Kg SO2 eq); Eu: Eutrophication x 101 (Kg PO43- eq)
Figure 4. Radial and bar environmental charts for CML 2 Baseline 2000.
AtA 1,0 W
CRYSTALLIZATION PRECIPITATION
0,8
GW
0,6 0,5
AqA
0,6
0,4 R 0,2
0,4 0,3 0,2 0,1
0,0
LU
OD
EcM
AtA
GW
AqA
OD
EcM
Eu
LU
Eu
AtA: Atmospheric Acidification x 103 (Ton SO2 eq); GW: Global Warming x 100(Ton CO2 eq); AqA: Aquatic Acidification x 1011 (Ton H+ released); OD: Ozone Depletion x 108 (Ton CFC-11 eq); EcM: Ecotoxicity (Sea Water) Metals x 105 (Ton Cu eq); Eu: Eutrophication x 105 (Ton PO43- eq); E: Energy consumed x 101 (MWh); LU: Land Use x 10-1 (m2); R: Resources x 10-3 (Kg CaO eq); W: Wastes x 10-3 (Kg wastes)
Figure 5. Radial and bar environmental charts for IChemE environmental metrics.
3.3 Sensitivity analysis: methods for life cycle environmental impact assessment
Several methods were considered because a single method could not provide comprehensive information on environmental impact (Ulgiati et al., 2006). Eco-Indicator 99, the evolution of Eco-Indicator 95, is a helpful tool for product development. This updated version is oriented to solve the weighting problem: different metrics, like global warning or atmospheric acidification, are difficult to weight together at emissions level. Complex relationships for fate, exposure, effect and damage analysis are used to model and quantify the damage caused by the emissions to the safeguard objects. On the other hand, CML 2 BaseLine 2000 is a problem-oriented method, being an updated version of the LCA guide published in 1992 by the Center of Environmental Studies of Leiden. CML 2 BaseLine 2000 includes metrics at emissions level. Due to the process oriented character of the present work, the environmental metrics in IChemE (2002) provided helpful information for the present case study and gave a process oriented vision to compare with the results presented by the two other methods. In this context, "The Sustainability Metrics environmental method was implemented in SimaPro 7 (Pr Consultans BV). The three methods used agreed with the more friendly environmental performance of crystallization against precipitation. Therefore, the selection of the method did not have influence on the conclusions of the work, due to the same percentages (around 20-40%) for the reductions achieved in the different metrics. As CML 2 BaseLine 2000 and the environmental metrics in IChemE (2002) deals with the problemoriented approach, similar thematic metrics (global warming, ozone layer depletion) at emissions level can be observed. In this sense, the environmental block has the highest number of metrics in Table 5. Since Eco-Indicator 99 is a damage-oriented approach, metrics at damage level are required and a large group of metrics related to human health safeguard object appears. Obviously, only general conclusions can be extracted if the interpretation of the results from the complete set of metrics (integrating a selected method) is done. Conclusions from direct comparison between same thematic-metrics from different methods (damage and problem oriented) can only be obtained in a limited metric set, covering global warming or ozone layer depletion. In summary, a sensitivity analysis for the methodology selected at the life cycle environmental impact step was carried out, concluding that, regardless the selected method, the same reductions ranges for crystallization against precipitation option are obtained.
4. CONCLUSIONS
Using the life cycle approach, two alternatives for fluoride removal from industrial wastewaters have been compared in environmental burdens. Results from this work showed the best environmental performance of the fluidized bed crystallization process against chemical precipitation because of the recycle of synthetic fluorite to the aluminium trifluoride production process. Damage and problem-oriented methods for the life cycle environmental impact assessment, such as EcoIndicator 99 and CML 2 Baseline 2000, were considered to give a complete vision with metrics at different levels. Due to the process-oriented character of this work, the environmental metrics developed by the Institution of Chemical Engineering (IChemE) were included in SimaPro 7 (Pr Consultants BV). For the most relevant metrics, the crystallization option allowed reductions in the order of 20-40% regarding the precipitation option. When it is compared with chemical precipitation, the major advantages of the crystallization process in a Fluidized Bed Reactor are the decrease of sludge formation, the simplification of the materials recovery procedures and the reduction of solid wastes.
REFERENCES
Aldaco, R., Control de fluoruros con recuperacin de productos, PhD Thesis, Universidad de Cantabria (2005a). Aldaco, R., A. Garea, A. Irabien, Fluoride reuse in aluminum trifluoride manufacture: sustainability criteria, AIChE Annual Meeting, Conference Proceedings, 13097-13106 (2005b). Aldaco, R., A. Irabien, P. Luis, Fluidized bed reactor for fluoride removal, Chem. Eng. J., Vol. 107 (1-3), 113-117 (2005c). Aldaco, R., A. Garea, A. Irabien, Fluoride recovery in a fluidized bed: crystallization of calcium fluoride on silica sand, Ind. Eng. Chem. Res., Vol. 45, No. 2, 796-802 (2006). Aldaco, R., A. Garea, A. Irabien, Calcium fluoride recovery from fluoride wastewater in a fluidized bed reactor, Wat. Res., Vol. 41, No. 4, 810-818 (2007). Azapagic, A., Life cycle assessment and its application to process selection, design and optimization, Chem. Eng. J., Vol. 73, No. 1, 1-21 (1999). Eco-Invent, Swiss Center for Life Cycle Inventories, The Life Cycle Inventory Data version 1.2. Available from: <http:www.ecoinvent.ch> (2005). EIPPCB, 2006, Draft Reference Document on Best Available Techniques for the Manufacture of Large Volume Inorganic Chemicals Solids and Others industry, Institute for Prospective Technological Studies, Sevilla, Spain. Available from: <http:eippcb.jrc.es> (2006). Giesen, A., Fluoride removal at low cost, European Semiconductor, Vol. 20, No. 4, 103-105 (1998). Goedkoop, M. and R. Spriensma, The Eco-indicator 99-A damage oriented method for life cycle impact assessment-Methodology report (Pr Consultants BV). Available from: <http:www.pre.nl> (2002). Guine, J.B., M. Gorre, R. Heijungs, G. Huppes, R. Kleinj, A. de Koning, L. van Oers, A. W. Sleeswijk, S. Suh, H. A. Udo de Haes, H. de Bruijn, R. van Duin, M. A. J. Huijbregts, Life Cycle Assessment. An operational Guide to the ISO standards, Center of Environmental Science, Leiden University (CML), The Netherlands (2001). IChemE (Institution of Chemical Engineers), http://www.icheme.org/sustainability/metrics.pdf (2002). The Sustainability Metrics, Available from:
ISO, ISO 14041:1998, Environmental Management-Life Cycle Assessment-Goal and scope definition and inventory analysis (1998). ISO, ISO 14042:2000, Environmental Management-Life Cycle Assessment-Life cycle impact assessment (2000a). ISO, ISO 14043:2000, Environmental Management-Life Cycle Assessment-Life cycle interpretation (2000b). Ulgiati, S., M. Raugei, S.Bargigli, Overcoming the inadequacy of single-criterion approaches to Life Cycle Assessment, Eco. Mod., Vol. 190, No. 3-4, 432-442 (2006).
4.2 Dominguez-Ramos, A., Aldaco, R., Irabien, A. Electrochemical oxidation of lignosulfonate: Total organic carbon oxidation kinetics.
I nd. Eng. Chem . Res. 2008, 47 , 9848

Resumen Los productos derivados de la lignina procedentes de la produccin de pulpa y pasta de papel en el proceso al sulfito representan una fraccin relevante de la carga orgnica biorefractaria en los vertidos finales de dicha industria. En este sentido, los procesos avanzados de oxidacin, como los procesos basados en la tecnologa de Electro-Oxidacin con electrodos de Diamante Dopado con Boro (DDB), son una alternativa interesante por cuanto son capaces de eliminar dicha materia orgnica mediante la generacin de radicales hidroxilos caracterizados por su elevado poder oxidante. Se ha analizado la influencia de los distintos parmetros que influyen de forma notable en los procesos de electro-oxidacin: concentracin de materia orgnica, densidad de corriente y electrolito soporte en una instalacin experimental con un reactor de electro-oxidacin equipado con electrodos de DDB, operando en modo discontinuo e isotermo en condiciones de corriente galvanostticas. Como consecuencia del estudio realizado, en los rangos analizados se observ que la naturaleza y concentracin del electrolito soporte no presentaban una notable influencia en el valor final de eliminacin. El ajuste de los datos de eliminacin de Carbono Orgnico Total (COT) revel un buen ajuste mediante una expresin cintica de primer orden, presentando una dependencia con el valor de corriente aplicada: altos valores de densidad de corriente llevan a una operacin controlada por la transferencia de materia hasta la superficie del electrodo mientras que a bajos valores es la densidad de corriente aplicada la que determina el valor de la velocidad de eliminacin de COT.
Original abstract
Lignin derivatives account for a significant fraction of biorefractory pollutants in wastewater from the pulp and paper industry. Electrochemical Oxidation has been described as an efficient alternative in wastewater treatment based on electrogenerated oxidation. Lignosulfonate was selected in this work as a biorefractory reference pollutant. Total organic carbon (TOC) removal was higher than 80% under the selected experimental conditions, where chemical oxygen demand (COD) was in the range 500-1500 mgO2 L-1, current density was between 30-60 mA cm-2 and the concentrations of sodium sulfate and sodium chloride supporting electrolytes were 2500 and 5000 mg L-1. Experimental conditions were selected to evaluate the technical suitability of the process and to establish a kinetic model and parameters. Experiments were carried out in a lab scale single cell flow electrochemical reactor with boron-doped diamond electrodes. A first order kinetic model is in good agreement with previously reported results,
103
and kinetic parameters depending mainly on the current density agree well with previous references. A model describing the influence of the current density in the kinetic parameters allows us to calculate the surface electrochemical reaction kinetic constant and the mass transfer coefficient.
104
9848
Ind. Eng. Chem. Res. 2008, 47, 98489853
Electrochemical Oxidation of Lignosulfonate: Total Organic Carbon Oxidation Kinetics

A. Dominguez-Ramos,* R. Aldaco, and A. Irabien
Departamento de Ingenier a Qu mica y Qu mica Inorga nica, UniVersidad de Cantabria, ETSIIT, AVda. de Los Castros s/n, 39005, Santander, Spain
Lignin derivatives account for a signicant fraction of biorefractory pollutants in wastewater from the pulp and paper industry. Electrochemical oxidation has been described as an efcient alternative in wastewater treatment based on electrogenerated oxidation. Lignosulfonate was selected in this work as a biorefractory reference pollutant. Total organic carbon (TOC) removal was higher than 80% under the selected experimental conditions, where chemical oxygen demand (COD) was in the range 500-1500 mg O2 L-1, current density was between 30 and 60 mA cm-2, and the concentrations of sodium sulfate and sodium chloride supporting electrolytes were 2500 and 5000 mg L-1. Experimental conditions were selected to evaluate the technical suitability of the process and to establish a kinetic model and parameters. Experiments were carried out in a laboratory scale single cell ow electrochemical reactor with boron-doped diamond electrodes. A rst-order kinetic model is in good agreement with previously reported results, and kinetic parameters depending mainly on the current density agree well with previous references. A model describing the inuence of the current density in the kinetic parameters allows us to calculate the surface electrochemical reaction kinetic constant and the mass transfer coefcient.
Introduction During the past 40 years, the eld of electrochemical oxidation has been very active in the search for new materials to manufacture energy-efcient and mechanically resistant electrodes. Controlling factors of the process and kinetics of different pollutant degradation have also been studied.1 In recent years, the electrochemical oxidation of a large number of industrial wastewater and chemical pollutants has been reported as it is shown in Table 1. Additionally, references of pilot plant scale units for tertiary electrochemical oxidation are also available.2 Electrochemical oxidation has been included within the advanced oxidation processes (AOP)17,41 under the name electrochemical advanced oxidation processes (EAOP). When COD is below 5000 mg O2 L-1, electrochemical oxidation appears to be an interesting alternative to AOP,42 but a wide range of applications ranging from 100000 to 1000 mg O2 L-1 have been suggested,43 although the technical range is generally lower, close to the former reference of 5000 mg O2 L-1. In the comparison among AOP, the reduction of sludge formation and consumption of chemicals are very attractive features of electrochemical oxidation.41,44 On the other hand, the main drawbacks of the electrochemical oxidation for the treatment of wastewater are the energy consumption per unit of wastewater volume8,18,45,46 and the investment costs,18 but practical applications of the technology in a wider extension have been limited by the use of low efciency electrodes.47 Boron-doped diamond (BDD) has been widely recognized as an excellent material for electrodes to perform electrochemical oxidation, not only in electroanalysis or preparation of powerful oxidants, but also for the removal of organics from wastewater due to its high anodic stability and wide potential window.1,48 Derived from the unique surface properties, BDD electrodes
* To whom correspondence should be addressed. Tel.: +34 942200931. Fax: +34 942201591. E-mail: domingueza@unican.es.
can perform the electro-combustion of the organic matter with energetic efciency under the appropriate operational conditions.49 Two basic mechanisms take place in electrochemical oxidation in aqueous media which are related to the electrode, the applied potential, and the supporting electrolyte: the direct and the indirect oxidation.8,22,29,41,50 Wastewater characteristics (concentration of organic matter, pH) and other operating parameters such as temperature, owrate, and cell conguration severely affect the extension of each mechanism. Kinetic studies of lumped variables such as total organic carbon (TOC) in well-dened synthetic efuents are a rst approach to evaluate the technical viability of ow electrochemical reactors using boron-doped diamond electrodes. Phenol has been widely used as reference substance in the eld of electrochemical oxidation to evaluate efuents with hazardous pollutants.8,10,47 This study takes lignin derivatives like lignosulfonate (lignin derivative in sulte mills) as a specic biorefractory compound to be removed.51,52 Some studies of the electrochemical oxidation of lignin derivatives have been reported in the literature: lignin by lead-dioxide-coated titanium electrodes53 and the transformation of lignosulfonate into lower molecular weight products by electro-oxidation with PbO2
Table 1. Electrochemical Oxidation of Industrial Wastewater and Chemical Pollutants industrial wastewater olive mill pulp and paper textile pharmaceutical landll leacheate leather phenol formaldehyde oil renery bulk drug manufacture carwash motor industry ref 3, 4 6, 7 11-16 18 20-24 26-29 31 31 31 60 61 chemical pollutant cyanides phenol chlorophenol 2-naphtol 3-methylpyridine glucose polyhydroxybenzenes histidine synthetic dyes herbicides drugs ref 5 8-10 17 19 25 30 32 33 12, 14, 15, 34, 35 36-39 40
10.1021/ie801109c CCC: $40.75 2008 American Chemical Society Published on Web 11/17/2008
Ind. Eng. Chem. Res., Vol. 47, No. 24, 2008 9849
Figure 1. Experimental setup: (1) power supply, (2) single-compartment ow electrochemical reactor, (3) owmeter, (4) centrifugal pump, (5) refrigerated glass tank, (6) absorber.
membrane electrodes.54 Lignin derivatives have been largely described as responsible for a representative fraction of the biorefractory content in the paper industry wastewater55,56 related to the inherent difculties in breaking down the strong aryl linkages and reducing the color of the efuents.56,57 The main objective of this study is the kinetic analysis and modeling of the removal of the TOC from lignosulfonate solutions with BDD electrodes in a single compartment ow electrochemical reactor. To describe the degradation process of lignosulfonate, TOC has been evaluated to describe the organic matter evolution with time, which is a common reference parameter in environmental regulations. Materials and Methods Laboratory-Scale Experimental Setup. Lignosulfonate solutions were introduced in a single compartment ow electrochemical reactor from Adamant Technologies SA operating in a semibatch mode. Figure 1 shows the basic layout of the laboratory scale plant. The cell is equipped with two parallel thin-lm boron-doped diamond electrodes supported on silicon with an interelectrode gap of 1 mm: anode and cathode are both circular, and they have an area of 70 cm2 per electrode. Borondoped diamond electrodes are well-known for their mechanical and chemical stability under extreme high current densities,1 and in the present work no alteration of the active surface was noticed. A centrifugal pump is responsible for the circulation of the 2 L storage tank solution through the cell (a rotameter was measuring the owrate). Galvanostatic conditions were applied by using an Agilent power supply 6554A. In the experiments, the owrate through the cell was kept constant at 300 L h-1, and the temperature was maintained constantly at 22 ( 2 C. The solution pH slightly changed at the end of the experimental time, which was set up in 8 h and veried to be enough for the kinetic study (TOC removal higher than 80% in all experiments). Samples were withdrawn from the glass tank at regular times preventing the surface electrode to solution volume ratio from changing more than 10%. Analytical Procedure. Total organic carbon (TOC) was measured in the experimental runs. TOC was monitored using a Shimadzu TOC-V CPH with ASI-V operating with synthetic air (pressure, 200 KPa; owrate, 150 mL min-1). Chemical oxygen demand (COD) was monitored at the beginning of each experiment according to standard methods (5220D Close reux, colorimetric method)58 by using a Hanna COD-reactor HI839800 for digestion and a Merck Spectroquant NOVA 600 for
colorimetric measurements. The initial and nal pH and conductivity were measured at the beginning and at the end of each experimental run. A Crison pH meter GLP22 with pH 52-02 electrodes and a Crison CM35 were used for pH and conductivity measurements, respectively. A commercial Borrebond 55S calcium-magnesium lignosulfonate (molecular weight about 3000 Daltons) coming from Eucalyptus globulus (sulte process) was obtained from Lignotech Iberica S.A. (Torrelavega, Spain). This product is water soluble in all proportions and has a residual concentration of reduced sugars (it was utilized as received without additional purication). Synthetic air was from Air Liquide S.A., Spain. The rest of the reagents were purchased from Panreac Qu mica, S.A., with required quality grades. Ultrapure water from Milli-Q was employed for the lignosulfonate solutions. Selection of Variables. Three variables were selected to be studied at two different levels: initial chemical oxygen demand, current density, and concentration of supporting electrolyte. The initial chemical oxygen demand [COD]0 was studied in the range 500-1500 mgO2 L-1, as the lower level would be representative of the COD efuent from the pulp and paper industry.59 The range of the applied current density j was between 30 and 60 mA cm-2 to guarantee that the anodic potential was above 2.3 V versus SHE at the selected supporting electrolyte concentrations (out of the region of water stability on BDD). Finally, the concentration of supporting electrolyte was 2500-5000 mg L-1, which is typical for electrochemical oxidation,8,30 and it allows the conductivity to be above the minimum conductivity (2 mS cm-1) established by the supplier. For electrochemical purposes, a concentration of sodium chloride below 3000 mg L-1 is typically well established.1 Additionally, two different supporting electrolytes were studied: sodium sulfate and sodium chloride. Table 2 summarizes the set of experimental runs, including the ratio ) (j/[COD]0)(A/V) (mA mg O2-1). Experimental run Si stands for test i using sodium sulfate as supporting electrolyte and Ci for sodium chloride (i ) 1-8). Kinetic Model and Parameters. Figures 2 and 3 show the time prole of the dimensionless total organic carbon, (TOC TOC0-1), for the sodium sulfate (Si) and sodium chloride (Ci) electrolytes. As can be seen in Figures 2 and 3, TOC may be removed, showing an exponential trend. In Table 3, the initial and nal pH and average voltage during the experimental runs are summarized. A variability in the initial pH, ranging from 3.60 to 4.26, is observed, leading to minor changes in the nal pH. In the sulfate series, the pH decreases slightly during the electrochemical oxidation within the range 2.81-3.62 due to the presence of relatively strong acids such as sulfuric and peroxodisulphuric acid, but in the chloride medium the pH is higher in the range 3.96-6.78 due to weak acids such as hypochlorous acid. Once the experiments were completed, a small amount of black thin lms was observed during the washing of the electrode with distilled water. In order to describe the kinetics of the electrochemical oxidation processes, different models have been proposed in the literature.9,12,15,22,49 Table 4 summarizes the main assumptions of the primary oxidation and secondary oxidation models. In the experimental cell described in Figure 1, the uid phase ows parallel to the surface of the circular electrodes (70 cm2 per electrode) with an interelectrode gap of 1 mm. A minimum owrate (from bottom input to top output as shown in Figure 1) must be set up to guarantee the contact between the liquid phase and the electrode surface so the total area takes part in the oxidation process. A boundary layer between the circular electrode surface and the bulk of the aqueous phase is
9850 Ind. Eng. Chem. Res., Vol. 47, No. 24, 2008
Table 2. Experimental Variables expt run S1, C1 S2, C2 S3, C3 S4, C4 S5, C5 S6, C6 S7, C7 S8, C8 [COD]0 (mg O2 L-1) 500 500 500 500 1500 1500 1500 1500 j (mA cm-2) 30 30 60 60 30 30 60 60 [Na2SO4]/[NaCl] (mg L-1) 5000 2500 5000 2500 5000 2500 5000 2500 (mA mg O2-1) 0.21 0.21 0.42 0.42 0.07 0.07 0.14 0.14
established, which implies a resistance to the mass transfer of organic matter to the electrode surface. After tting the experimental results with MATLAB v7.5.0 R2007b (Levenberg-Marquardt algorithm) to an exponential equation in all individual runs for the sulfate and chloride series, kinetic constants are shown in Table 5. The condence range for the kinetic parameters is set up to 95%. The kinetic constant is corrected by the extensive magnitude (A/V)-1 to be expressed in terms of a mass transfer coefcient leading to k (m min-1). The experimental kinetic constants referred to the electrode surface are within the range of values shown in Table 6 for electrochemical oxidation. As it is shown in Table 6, electrodes
Table 3. Initial and Final pH and Average Voltage Vaverage (V) between Electrodes (Flowrate ) 300 L h-1, T ) 22 C) expt run S1 S2 S3 S4 S5 S6 S7 S8 C1 C2 C3 C4 C5 C6 C7 C8 initial pH 4.19 4.15 4.26 4.22 3.98 3.84 4.01 4.00 3.71 3.91 3.70 4.19 3.64 3.83 3.64 3.60 nal pH 3.30 3.33 3.62 3.41 3.06 2.93 2.81 2.82 6.6 3.96 6.78 5.92 5.95 4.32 6.22 4.29 Vaverage (V) 5.750 6.093 6.850 7.594 5.193 5.275 6.763 7.313 4.931 5.78 7.385 7.561 5.795 5.322 6.379 6.822
Table 4. Summary of the Main Mechanism of the Electrochemical Oxidation Kinetics approach contribution of hydroxyl radicals (from water) contribution of electrogenerated reagents relevance of the nature organic matter distinction between current controlled and mass transfer controlled operations regimes COD value at which the transition between controlling regimes takes place type of electrodes for which the model has been successfully applied primary oxidation yes yes yes yes secondary oxidation no yes no no
Figure 2. Dimensionless TOC () versus time (low initial COD): (inverted open triangle) S1-2; (upright open triangle) C1-2; (cross) S3-4; (small solid circle) C3-4; (solid line) tting curve for S1-2, C1-2; (dashed line) tting curve for S3-4, C3-4.
COD experimental nonactive (i.e., BDD) low overpotential for Cl2 evolution (i.e., DSA)
based on boron-doped diamond lead to similar kinetic constants in the removal of organic compounds. Discussion Kinetic results from Table 5 for the electrochemical oxidation of lignosulfonate do not show any inuence of the electrolyte concentration. The kinetic constant k is therefore independent of the electrolyte in both sulfate and chloride series at a xed initial COD and current density. Hereby, kinetic results shown in Table 5 show that the concentration of sodium sulfate and sodium chloride supporting electrolyte between 2500 and 5000 mg L-1 at each level of initial COD and applied current density does not have any inuence on the kinetic parameter k, and consequently, the inuence of the electrolyte can be neglected in the studied range of variables. This negligible inuence of the supporting electrolyte concentration above certain values
Figure 3. Dimensionless TOC () versus time (high initial COD): (leftpointing triangle) S5-6; (right-pointing triangle) C5-6; (open circle) S7-8; (open square) C7-8; (dotted line) tting curve for S5-6, C5-6; (dashed line) tting curve for S7-8, C7-8.
Table 5. First-Order Kinetic Parameters of versus Time (Flowrate ) 300 L h , T ) 22 C, Condence Range ) 95%)
-1
expt run S1 S2 C1 C2 S3 S4 C3 C4 S5 S6 C5 C6 S7 S8 C7 C8
k 103 (m min-1) 1.22 ( 0.07 1.27 ( 0.08 1.73 ( 0.15 1.17 ( 0.05 1.55 ( 0.10 1.62 ( 0.09 1.45 ( 0.12 1.44 ( 0.08 0.81 ( 0.06 0.88 ( 0.06 1.03 ( 0.19 0.79 ( 0.08 1.18 ( 0.07 1.34 ( 0.08 1.48 ( 0.10 1.37 ( 0.21
r2 0.992 0.991 0.987 0.996 0.993 0.994 0.983 0.993 0.987 0.988 0.945 0.974 0.992 0.993 0.992 0.965
kS/C 103 (m min-1) 1.24 ( 0.05 1.42 ( 0.14 1.58 ( 0.07 1.44 ( 0.07 0.84 ( 0.04 0.91 ( 0.10 1.26 ( 0.06 1.42 ( 0.11
r2 0.991 0.958 0.993 0.989 0.985 0.940 0.988 0.976
k 103 (m min-1) 1.33 ( 0.07
r2 0.972
(m mg O2-1) 0.21
1.51 ( 0.05
0.989
0.42
0.87 ( 0.05
0.958
0.07
1.33 ( 0.06
0.979
0.14
Table 6. Reported Kinetic Constants (kRs) in the Oxidation of Lignin-Related Biorefractory Compounds by Electrochemical Oxidation (EO) electrode Ti/PbO2 Si/BDD Si/BDD DiaChem DiaChem Si/BDD substance lignin solution phenol solution phenol solution phenol solution AO7 solutions lignosulfonate solutions variable COD COD phenol COD COD TOC kR 105 (m min-1) 2-6 170 127-769 114 88 87-151 ref 53 8 47 10 34 this work
has been recognized as a general behavior in electrochemical processes. No signicant effect of increasing the concentration of sodium sulfate from 2% to 3% was found during the electrochemical oxidation of olive mill wastewater (OMW) at Ti-Ta/Pt-Ir electrodes.4 In this work, a concentration of 2500 mg L-1 of the selected electrolytes leads to the same value of the kinetic constants represented by kS/C, which refers to the sulfate or the chloride media. From Table 5 it can be deduced that there is not any inuence of the selected supporting electrolyte on the TOC removal rate. The electrochemical reactions for hypochlorous anion are summarized in eqs 1-3 throughout the generation of dissolved chlorine and the later disproportionation reaction of chlorine in the aqueous phase: 2Cl- f Cl2(l) + 2eCl2(l) + H2O f HCl + HClO
+ -
in relation to the organic matter reaching the electrode surface. In this case, the process becomes mass-transfer-controlled. According to this statement, decreasing the initial COD from 1500 to 500 mg O2 L-1 increases , and the process becomes mass-transfer-controlled. In the same way, increasing the current density from 30 to 60 mA cm-2 increases so the oxidation would be mass-transfer-controlled and a higher kinetic constant is obtained. The kinetic constants for TOC removal as a function of (k) are shown in Figure 4. Kinetic constants are associated with , which corresponds with each individual combination of j and [COD]0 studied in this work. According to the evolution of Figure 4, a hyperbolic function as is shown in eq 5 describes the experimental behavior R (5) 1 + where R represents the kinetic constant of the electrochemical oxidation at the electrode surface kA and represents the ratio between kA and the mass transfer coefcient km. For the tting of the kinetic constants to , R ) (28.39 ( 9.51) 10-3 (mg O2 m)(mA min)-1 and ) 16.13 ( 7.05 mg O2 mA-1 are obtained (r2 ) 0.988, condence range ) 80%, LevenbergMarquardt algorithm). From Figure 3 it is observed that, at high values of , the process becomes mass-transfer-controlled: there is an excess of current density in the system, and therefore, the transfer of organic matter to the electrode surface is the limiting step to the TOC degradation. At low values of , the process becomes current-density-controlled: the applied current density k )
(1) (2)
(3) HClO f H + ClO The corresponding equation for the generation of peroxodisulphate in aqueous phase is shown in eq. 4:
22SO2 4 f S2O8 + 2e
(4)
Experimental kinetic constants can be considered taking into account those experiments with similar current densities and initial COD but different electrolytes. Consequently, kinetic constants for TOC can be grouped up to 4 values (k), which show the possible combinations summarized in Table 5. These results are in a good agreement with previous results,8,12 which states that the ratio of applied current density to concentration of organic matter () determines the way in which the COD is removed. When the ratio is relatively low, there are no available hydroxyl radicals to oxidize all the organic matter reaching the electrode surface, so the process is kinetically controlled by the applied current. On the other hand, when the ratio is relatively high, there is an excess of hydroxyl radicals
Figure 4. Kinetic constant k as a function of . The error bars describe the maximum and minimum values of k.
9852 Ind. Eng. Chem. Res., Vol. 47, No. 24, 2008
is not enough to degrade the organic matter reaching the electrode surface. The ratio R/ ) 1.76 10-3 m min-1 describes therefore the mass transfer coefcient km when the process is mass-transfer-controlled at large values. As lignosulfonate is based on phenolic structures, it would be expected that different phenolic derivatives could appear after breaking into lower molecular weight species. The nal steps of the reaction would include typical organic acids such as oxalic, maleic, etc., before the nal mineralization to CO2. Conclusions In this work, the technical feasibility of removing the total organic carbon from dilute lignosulfonate solutions by means of a single compartment ow electrochemical cell in sodium sulfate and sodium chloride medium has been demonstrated in the studied range of variables. The oxidation process depends on the initial chemical oxygen demand and the applied current density. Both variables play a major role in the electrochemical oxidation of lignosulfonate with BDD electrodes. In the studied range of sodium chloride and sodium sulfate concentration, it has no signicant effect so a concentration of 2500 mg L-1 is suitable to extend the removal percentage up to the desired values, and the supporting electrolyte does not have any inuence on TOC removal. A rst order kinetic model based on an exponential evolution of the dimensionless TOC with time has shown a good tting of the experimental results leading to the experimental kinetic constants. Kinetics constants have been related to the current densities and initial chemical oxygen demand by a hyperbolic equation containing a rst-order surface electrochemical reaction kinetic constant and a mass transfer coefcient. Acknowledgment This research is nancially supported by the Spanish Ministry of Science and Technology (Project CONSOLIDER CTM200600317) and the Project CENIT SOSTAQUA. A.D.-R. thanks the Ministry of Education and Science for the FPU fellowship reference number AP-2005-1719. Nomenclature
A/V ) electrode surface to solution volume ratio (m-1) [COD]0 ) initial COD (mg O2 L-1) j ) current density (mA cm-2) k ) kinetic constant for TOC removal (m min-1) kA ) kinetic constant of the electrochemical oxidation at the electrode surface (mg O2 m (mA min)-1 km ) mass transfer coefcient (m min-1) kS/C )kinetic constant for TOC removal independent of the selected supporting electrolyte (m min-1) k ) kinetic constant for TOC removal as function of (m min-1) R ) adjusting parameter of k as function of [(mg O2 m)(mA min)-1] ) adjusting parameter of k as function of (mg O2 mA-1) ) dimensionless TOC ) (j/[COD]0) (A/V) (mA mg O2-1)
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(35) Panizza, M.; Barbucci, A.; Ricotti, R.; Cerisola, G. Electrochemical degradation of methylene blue. Sep. Purif. Technol. 2007, 54, 382. (36) Boye, B.; Brillas, E.; Marselli, B.; Michaud, P.; Comninellis, C.; Farnia, G.; Sandona ` , G. Electrochemical incineration of chloromethylphenoxy herbicides in acid medium by anodic oxidation with boron-doped diamond electrode. Electrochim. Acta 2006, 51, 2872. (37) Brillas, E.; Ban os, M. A.; Skoumal, M.; Cabot, P. L.; Garrido, J. A.; Rodr guez, R. M. Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes. Chemosphere 2007, 68, 199. (38) Brillas, E.; Boye, B.; Sire s, I.; Garrido, J. A.; Rodr guez, R. M.; Arias, C.; Cabot, P.; Comninellis, C. Electrochemical destruction of chlorophenoxy herbicides by anodic oxidation and electro-Fenton using a boron-doped diamond electrode. Electrochim. Acta 2004, 49, 4487. (39) Flox, C.; Cabot, P. L.; Centellas, F.; Garrido, J. A.; Rodr guez, R. M.; Arias, C.; Brillas, E. Electrochemical combustion of herbicide mecoprop in aqueous medium using a ow reactor with a boron-doped diamond anode. Chemosphere 2006, 64, 892. (40) Weichgrebe, D.; Danilova, E.; Rosenwinkel, K.; Vedenjapin, A. A.; Baturova, M. Electrochemical oxidation of drug residues in water by the example of tetracycline, gentamicine and aspirin. Water Sci. Technol. 2004, 49, 201. (41) Marselli, B.; Garcia-Gomez, J.; Michaud, P. A.; Rodrigo, M. A.; Comninellis, C. Electrogeneration of hydroxyl radicals on boron-doped diamond electrodes. J. Electrochem. Soc. 2003, 150, D79. (42) Kapaka, A.; Fo ti, G. Comninellis, C. Kinetic modelling of the electrochemical mineralization of organic pollutants for wastewater treatment. J. Appl. Electrochem. 2008, 38, 7. (43) Fryda, M.; Matthe e, T.; Mulcahy, S.; Hampel, A.; Scha fer, L.; Tro ster, I. Fabrication and application of Diachem electrodes. Diamond Relat. Mater. 2003, 12, 1950. (44) Panizza, M.; Zolezzi, M.; Nicolella, C. Biological and electrochemical oxidation of naphthalenesulfonates. J. Chem. Technol. Biotechnol. 2006, 81, 225. (45) Can izares, P.; Sa ez, C.; Lobato, J.; Rodrigo, M. A. Detoxication of synthetic industrial wastewaters using electrochemical oxidation with boron-doped diamond anodes. J. Chem. Technol. Biotechnol. 2006, 81, 352. (46) DeLucas, A.; Can izares, P.; Rodrigo, M. A.; Garc a-Go mez, J. Electrochemical treatment of aqueous phenol wastes: A preliminary economical outlook. Waste Manage. EnViron. 2002, 161. (47) Polcaro, A. M.; Vacca, A.; Palmas, S.; Mascia, M. Electrochemical treatment of wastewater containing phenolic compounds: Oxidation at borondoped diamond electrodes. J. Appl. Electrochem. 2003, 33, 885. (48) Iniesta, J.; Michaud, P. A.; Panizza, M.; Cerisola, G.; Aldaz, A.; Comninellis, C. Electrochemical oxidation of phenol at boron-doped diamond electrode. Electrochim. Acta 2001, 46, 3573. (49) Panizza, M.; Michaud, P. A.; Cerisola, G.; Comninellis, C. Electrochemical treatment of wastewaters containing organic pollutants on boron-doped diamond electrodes: Prediction of specic energy consumption and required electrode area. Electrochem. Commun. 2001, 3, 336. (50) Simond, O.; Comninellis, C. Anodic oxidation of organics on Ti/ IrO2 anodes using Naon as electrolyte. Electrochim. Acta 1997, 42, 2013. (51) Goreno, A.; Li, Y.; Frimmel, F. H. Improved biodegradability of ligninsulfonic acid and wastewater after ozonation. Chem. Eng. Technol. 2003, 26, 11. (52) Machado, A. E. H.; de Miranda, J. A.; de Freitas, R. F.; Duarte, E.T.F.M.; Ferreira, L. F.; Albuquerque, Y. D. T.; Ruggiero, R.; Sattler, C.; de Oliveira, L. Destruction of the organic matter present in efuent from a cellulose and paper industry using photocatalysis. J. Photochem. Photobiol., A 2003, 155, 231. (53) Chiang, L. C.; Chang, J. E.; Tseng, S. C. Electrochemical oxidation pretreatment of refractory organic pollutants. Water Sci. Technol. 1997, 36, 123. (54) Chen, F.; Lu, Z.; Tu, B. Electro-degradation of sodium lignosulfonate. J. Wood Chem. Technol. 2003, 23, 261. (55) Lacorte, S.; Latorre, A.; Barcelo , D.; Rigol, A.; Malmqvist, A.; Welander, T. Organic compounds in paper-mill process waters and efuents. TrAC, Trends Anal. Chem. 2003, 22, 725. (56) Kreetachat, T.; Damrongsri, M.; Punsuwon, V.; Vaithanomsat, P.; Chiemchaisri, C.; Chomsurin, C. Effects of ozonation process on ligninderived compounds in pulp and paper mill efuents. J. Hazard. Mater. 2007, 142, 250. (57) Ghoreishi, S. M.; Haghighi, M. R. Chromophores removal in pulp and paper mill efuent via hydrogenation-biological batch reactors. Chem. Eng. J. 2007, 127, 59. (58) APHA, AWWA, WEF. Standard Methods for the Examination of Water and Wastewater, 20th ed.; American Public Health Association: Washington, DC, 1998. (59) European Commission BREF (12.01) Integrated Pollution Prevention and Control, Reference Document on Best Available Techniques in the Pulp and Paper Industry; December 2001. (60) Panizza, M.; Deluchi, M.; Cerisola, G. Electrochemical degradation anionic surfactants. J. Appl. Electrochem. 2005, 35, 357. (61) Kraft, A.; Stadelmann, M.; Blaschke, M. Anodic oxidation with doped diamond electrodes: A new advanced oxidation process. J. Hazard. Mater. 2003, 103, 247.
ReceiVed for reView July 18, 2008 ReVised manuscript receiVed September 25, 2008 Accepted September 26, 2008 IE801109C
4.3 Dominguez-Ramos, A., Aldaco, R., Irabien A. Photovoltaic Solar Electrochemical Oxidation (PSEO) for lignosulfonate waste water treatment. J. Chem . Technol. Biotechnol. 85 , 821
Resumen La electro-oxidacin se ha mostrado como una excelente alternativa tecnolgica a la hora de tratar con efluentes contaminados con carga orgnica. Sin embargo, su elevado consumo energtico especfico hace que el uso de energa convencional de red difcilmente pueda constituir una alternativa ambientalmente sostenible. En este sentido, se dispone de referencias previas en los que la energa solar fotovoltaica ha sido recientemente utilizada como base para alimentar procesos electroqumicos como electrocoagulacin y oxidacin Fenton. Es en esta bsqueda de procesos autosostenibles dentro del tratamiento de aguas residuales con carga orgnica que se desarrolla un proceso de Electro-Oxidacin asistido por energa Solar Fotovoltaica (ESOF). Un conjunto de mdulos solares fotovoltaicos es capaz de generar corriente continua para alimentar un reactor de electro-oxidacin que utiliza electrodos de diamante dopado con boro. Mediante la operacin en modo discontinuo en distintas condiciones de irradiacin solar para una disolucin sinttica con carga orgnica basada en lignosulfonato, se ha comprobado que es posible eliminar hasta un 90% del Carbono Orgnico Total (COT) presente. Se ha desarrollado un modelo capaz de relacionar de forma sencilla la irradiacin solar incidente sobre los mdulos solares con la corriente que alimenta el reactor de electro-oxidacin; dicha expresin se ha empleado a su vez para disponer de una expresin cintica de eliminacin de COT que depende de la irradiacin solar. A altos niveles de irradiacin solar, la expresin desarrollada propone que el proceso estar controlado por la transferencia de materia a la superficie andica, mientras que a bajos niveles de irradiacin, el proceso est limitado por el nivel de irradiacin incidente. Los valores de las constantes cinticas obtenidas al igual que los de consumo especfico de energa se encuentran en el orden de magnitud de procesos de electro-oxidacin en similares condiciones experimentales operando en condiciones galvanostticas. En conclusin, se ha demostrado la viabilidad tcnica de conectar un conjunto de mdulos solares fotovoltaicos a un reactor de electro-oxidacin al ser posible completar la eliminacin del COT presente en el grado de eliminacin deseado.
Original abstract
Under the current global energy scenario, the need for self-sustainable processes is encouraged. The Photovoltaic Solar powered Electrochemical Oxidation (PSEO) process has been developed to remove the organic matter from a lignosulfonate waste-water. An electrochemical reactor using boron doped diamond electrodes, in a batch configuration, is
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directly supplied with current from a set of photovoltaic solar modules. Experimental results show that the process can oxidize about 90% of the total organic carbon (TOC) of the organic matter in the waste-water under the described operating conditions. The technical suitability of the PSEO process has been demonstrated. A model to relate solar irradiance and electrical current was applied and used in a kinetic expression which depends on solar irradiance to describe the removal of TOC.
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Research Article
Received: 29 September 2009 Revised: 8 January 2010 Accepted: 19 January 2010 Published online in Wiley Interscience: 29 March 2010
(www.interscience.wiley.com) DOI 10.1002/jctb.2370
Photovoltaic solar electrochemical oxidation (PSEO) for treatment of lignosulfonate wastewater

Antonio Dominguez-Ramos, Ruben Aldaco and Angel Irabien
Abstract
BACKGROUND: Under the current global energy scenario, the need for self-sustainable processes is encouraged. The photovoltaic solar powered electrochemical oxidation (PSEO) process has been developed to remove the organic matter from a lignosulfonate wastewater. RESULTS: An electrochemical reactor using boron-doped diamond electrodes, in a batch conguration, is directly supplied with current from a set of photovoltaic solar modules. Experimental results show that the process can oxidize about 90% of the total organic carbon (TOC) of the organic matter in the wastewater under the described operating conditions. CONCLUSION: The technical suitability of the PSEO process has been demonstrated. A model to relate solar irradiance and electrical current was applied and used in a kinetic expression which depends on solar irradiance to describe the removal of TOC. c 2010 Society of Chemical Industry Keywords: electrochemical oxidation; kinetics; mathematical modelling; photovoltaic solar energy; diamond boron-doped electrodes; lignosulfonate
NOTATION
AE AM C C0 EC EU ESC,m ESC,v G g gAV I i iAV iC D Total electrode area (cm2 ) D Total area of photovoltaic modules (m2 ) D Concentration of organic matter expressed as total organic carbon (mgC L 1 ) D Initial concentration of organic matter expressed as chemical oxygen demand (mgO2 L 1 ) D Energy collected by the set of solar modules (kW h) D Energy used in the electrochemical reactor for the oxidation of organic matter (kW h) D Specic energy consumption used in the electrochemical reactor per unit of mass (kW h mgC) D Specic energy consumption used in the electrochemical reactor per unit of volume (kW h m 3 ) D Global irradiance on the plane of the photovoltaic modules (W m 2 ) D Incident solar power on the plane of the photovoltaic modules (W) D Average incident solar power on the plane of the photovoltaic modules (W) D Total current generated by the set of photovoltaic modules per total module area (A m 2 ) D Total current generated by the set of photovoltaic modules (A) D Average total current generated by the set of photovoltaic modules (A) D Total applied current under controlled conditions (mA)
iMP,ref
iSC,ref
J K K1 K2 Kexp Km Kmax
D Current provided by the photovoltaic module at the maximum power point and standard conditions of irradiance (1000 W m 2 ) and module temperature (25 C) at AM1.5 (A) D Current provided by the photovoltaic module under short-current and standard conditions of irradiance (1000 W m 2 ) and module temperature (25 C) at AM1.5 (A) D Current density (mA cm 2 ) D Instantaneous kinetic constant as a function of g (m min 1 ) D Parameter for the assessment of the reaction rate as a function of g (m min 1 A 1 ) D Parameter for the assessment of the reaction rate as a function of g (A 1 ) D Apparent kinetic constant obtained by linear tting of TOC removal values (m min 1 ) D Mass transfer coefcient in the electrochemical reactor (m min 1 ) D Maximum observed kinetic constant for TOC removal (min 1 )
Correspondence to: Antonio Dominguez-Ramos, Departamento de Ingenier a Qu mica y Qu mica Inorg anica, Universidad de Cantabria, Avda. de Los Castros, s/n, 39005, Santander, Spain. E-mail: domingueza@unican.es Departamento de Ingenier a Qu mica y Qu mica Inorg anica, Universidad de Cantabria, Avda. de Los Castros, s/n, 39005, Santander, Spain
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c 2010 Society of Chemical Industry
www.soci.org K NPV rA tOP vE vOC,ref D Kinetic constant expressed as a function of (m min 1 ) D Number of connected photovoltaic modules ( ) D Reaction rate referred to the electrode area (mgC m min 1 L 1 ) D Number of minutes of operation to achieve a 90% removal expressed as TOC (min) D Electrochemical reactor volume (L) D Voltage provided by the photovoltaic module in open circuit and standard conditions of irradiance (1000 W m 2 ) and module temperature (25 C) at AM1.5 (V) D Voltage provided by the photovoltaic module at the maximum power point and standard conditions of irradiance (1000 Wm 2 ) and module temperature (25 C) at AM1.5 (V) D Solution volume (L) D Fitting parameter for batch data under controlled current condition (mgO2 m mA 1 min 1 ) D Fitting parameter for batch data under controlled current condition (mgO2 mA 1 ) D Conductivity of the efuent (mS cm 1 ) D Applied current per mass of O2 (mA mgO2 1 ) D Power conversion efciency by the set of photovoltaic modules (%)
A Dominguez-Ramos, R Aldaco, A Irabien the number of grains in the material, the borders of which act as defects and therefore reduce the efciency of the material.5 As photovoltaic technology matures there is the prospect of low-cost production processes and almost zero nett CO2 -eq emissions throughout the life cycle;8,9 thus, the integration of these energy devices into processes and applications related to chemical technology and water treatment should be considered in the mid-term range. Different research studies using solar energy devices for water treatment have been undertaken, as summarized in Table 1. Electrocoagulation with Fe3C powered by photovoltaic solar energy was studied,10 with the ow rate treated as a function of the instantaneous solar irradiance; photovoltaic solar energy was also used to supply the current required to produce Fentons reagent in a divided cell with reticulated vitreous carbon anodes, and used to oxidize different dyes and real efuents.11 Electrochemical combustion of organics using BiOX TiO2 anodes can improve hydrogen production in stainless steel cathodes.12 It is worth mentioning that the references in Table 1 indicate that different processes using electricity can use photovoltaic technology in an autonomous way. Direct supply from photovoltaic modules is well established and electrochemical oxidation processes can gain advantages from being supplied by photovoltaic energy. The key issues that encourage proper use of water treatment processes powered by photovoltaic energy can be summarized as follows: No need for energy storage systems. The processes can be designed in such a way that solar irradiation is transformed into electricity and used as input for electrochemical oxidation: it is simpler and provides cheaper clean water than other equivalent energy systems (e.g. lead acid batteries).13 Direct supply to the treatment process, which implies that the ow can be treated in a continuous system as a function of solar irradiance Wastewater treatment leading to the removal of organic matter, such as electrochemical oxidation (EO) based on boron-doped diamond electrodes has been claimed as an advanced technology in purication and disinfection applications, promoting water reclamation and close-to-zero nett use of water from natural resources. The reduction of sludge and consumption of chemicals are very attractive features of EO when compared with biological processes. When an electrical current is applied to the electrodes, powerful oxidants are created in the surface or the bulk liquid phase, depending on the operating conditions, promoting oxidation of the organic matter to CO2 and H2 O. Nevertheless,
vMP,ref
vS
INTRODUCTION
Now that mankind is facing great challenges with the supply of energy, water and food one of the most important for societies all over the world more especially if we still continue to live with energy generation based on fossil fuels, which is a main element in climate change.1 The integration of renewable energy sources not only in power generation but in other production systems is a key challenge, as noted in A Roadmap for the 21th Century Chemical Engineering by the Institution of Chemical Engineers.2 Photovoltaic solar conversion energy is based on the separation of charges at the interface of two materials with different conduction mechanisms.3 Solid-state devices such as those based on monocrystalline silicon materials, under light irradiation have the capacity to absorb a fraction of the energy carried by the device surface, displacing photons into electrical current carriers, i.e. electrons and holes.4 Monocrystalline silicon materials can be obtained by the energy-intensive Czochralski process. This crystallographic structure is desirable due to the reduction in
Table 1. Photovoltaic powered processes for wastewater treatment Coupled process Electrocoagulation Direct connection to PV supply Yes PV installation characteristics 1 PQ10/40/01-02 AEG of 38.48 WP (poly-crystalline silicon) 1 solar panel (50 W; 17 V; 2.9 A; Syscom Inc. Model BP 350U) Water treatment unit characteristics Total anodic area: 235 cm2 (central aluminium anode between two stainless steel cathodes) 3D-RVC electrode (5 cm 5 cm 1 cm); 60 pores per inch; tted into centre of catholyte channel; Naon 117 cation permeable membrane separator; stainless steel gauze anode (5 cm 5 cm) and silicon rubber gaskets 70 cm2 BDD electrodes single-compartment ow cell Reference
10
Oxidation with Fentons reagent
Yes (voltage regulator)
11
Electrochemical Oxidation
Yes
4 160 WP SunTech (monocrystalline; total rating 640 WP )
This work
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PSEO for lignosulfonate wastewater treatment this technology has the major drawback of high electrical energy demand per unit of treated volume,14 which can be avoided by using renewable energy sources. The aim of this work is to show the technical feasibility of a photovoltaic solar powered electrochemical oxidation process (PSEO) to remove organic matter from a lignosulfonate solution by performing an energy and mass balance to the coupled process, in order to describe the experimental results.
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MATERIALS AND METHODS

A synthetic solution of calcium and magnesium lignosulfonate was prepared as typical biorefractory organic matter to test the reliability of the PSEO process. To prepare the lignosulfonate solutions a commercial Borrebond 55S calcium-magnesium lignosulfonate (molecular weight about 3000 daltons) from Eucalyptus globulus (sulte process) was obtained from Lignotech Iberica S.A. (Torrelavega, Spain). This product is water soluble and has a residual concentration of reduced sugars. It was used as received without additional purication. Sodium sulfate from Panreac Quimica SA was added as a supporting electrolyte to maintain conductivity between the electrodes. A total solution volume (vS ) of 2 L with the required quantity of lignosulfonate and sodium sulfate in ultrapure water (Milli-Q) was used in each experiment. Lignosulfonate solutions were introduced in a single compartment ow electrochemical reactor (Adamant Technologies SA) operating in a semi-batch mode. The experimental setup is shown in Fig. 1. The external parts of the reactor are made of polypropylene and tightened to prevent leakages. The electrochemical reaction takes place in the cell: the anode and cathode are based on conductive thin-lms of boron-doped diamond (active layer with a thickness in the range 13 m and a total resistivity of 100150 m cm) supported on a silicon substrate (p-silicon with a thickness of 2 mm and a total resistivity of 100 m cm). The electrodes have a parallel conguration characterized by an interelectrode gap of 1 mm. Anode and cathode are both circular with a total wet area (AE ) of 70 cm2 per electrode (during the different experiments no alteration of the active surface was noticed). A centrifugal pump was used to circulate the solution through the electrochemical cell, with ow-rate measured by rotameter. Up to four monocrystalline photovoltaic modules (SunTech Co. Ltd. STP160) were connected giving a total peak power of 640 WP from an effective area of 1.125 m2 per module (see Table 2 for details). Photovoltaic modules were placed on the roof of ETSIIyT, University of Cantabria, Santander, Spain (W3 470 52.1700 , N43 280 22.3300 ) tilted at 38 and south orientation (20 West). The set of modules were directly connected to the electrochemical reactor through a fuse box. No shadowing effect was noted during the experiments. Table 3 summarizes relevant operating conditions in the experiments. All experiments began at 10 : 30 PM (local time) enabling the connection of the photovoltaic modules to the electrochemical reactor: the operating time tOP was extended to guarantee that TOC removal around 90% was obtained. Flow-rate through the electrochemical cell was kept constant at 300 L h 1 . The temperature of the solution was maintained constant between 22 and 24 C for the selected experiments (except for E2 at 32 C). Samples were withdrawn from the solution tank at regular times. The objective of the set of experiments shown in Table 3 was to demonstrate the technical viability of a PSEO process to remove TOC from a lignosulfonate solution under different solar irradiance conditions and initial concentrations, and to obtain experimental
Figure 1. Experimental set-up. 1. Single compartment ow electrochemical reactor Power supply, 2. Flowmeter, 3. Centrifugal pump, 4. Refrigerated glass tank, 5. Absorber, 6. Photovoltaic modules 7. Unit for measurement of current and voltage.
Table 2. Characteristics of the SunTech photovoltaic module STP160 Parameter iSC,ref vOC,ref iMP,ref vMP,ref Value 5 43.2 4.65 34.4 Units A V A V
data to perform the energy and mass balances in the system and to scale up the water treatment. Total organic carbon (TOC) of each sample was analysed using a Shimadzu TOC-V CPH with ASI-V, operating with synthetic air from Air Liquide S.A., Spain (pressure 200 kPa; owrate: 150 mL min 1 ). Both pH and conductivity were measured (values corrected to 25 C) using a Hach HQ40d unit (Hach Lange). Solar irradiance time proles were measured at intervals of 15 min using a SunReader unit (SunTechnics Conergy Group). To obtain current, voltage and power time proles a Fluke 345 unit was used for measurements and recording (logged at intervals of 10 s and displayed at intervals of 15 min after resampling). This unit is able to measure the input current in the electrochemical cell generated by the set of photovoltaic modules in each experiment and the applied voltage between electrodes, i.e. the output voltage of the photovoltaic
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Table 3. Experimental conditions Exp E1 E2 E3 E4 Date 29-04-2008 05-05-2008 07-05-2008 15-05-2008 NPV 2 4 2 1 tOP min 300 240 300 480 C0 mgC L 624 700 200 656
1
20
i (A)
Supporting electrolyte [Na2 SO4 ] g L 1 2.5 2.5 2.5 0.3
4000 3000 2000 1000
15 10 5 0 0 60 120 180 240 300 360 420 480 Time (min)
700 600 TOC (mg CL-1) 500 400 300
g (W)
60
120
180 240 300 Time (min)
360
420
480
Figure 3. Incident solar power g D GAM versus time. () E1; ( ) E2; ( ) E3; ( ) E4. Inset: evolution of total applied current i versus time. () E1; ( ) E2; ( ) E3; ( ) E4.
15
200 100 0
10 v (V) 5 0 0
0 60 120 180 240 300 Time (min) 360 420 480
Figure 2. Evolution of total organic carbon versus time. () E1; ( ) E2; ( ) E3; ( ) E4.
modules. Once the power prole is available, it is possible to evaluate the energy applied to the electrochemical system. All analytical and electrical measurements were in good agreement with expected relative errors from the specied values.
10 i (A)
15
20
Figure 4. Voltage between electrodes v versus input current i: () E1; ( ) E2; ( ) E3; ( ) E4.
RESULTS AND DISCUSSION

Evolution of total organic carbon Figure 2 shows the time prole of TOC for the set of experiments, from which it is clear that the PSEO process is able to remove the organic matter from a lignosulfonate solution. As previously stated, the experiments were extended until relevant data for the kinetic analysis were available. Consequently, higher yields than those presented here could be obtained simply by extending the operation time. Details of the mass balance and the kinetics of the process are discussed later. Energy analysis It is important to complete analysis of the energy input to the electrochemical system. Figure 3 shows the time proles for incident solar power (g) (solar irradiance on the plane dened by the position of the photovoltaic modules G multiplied by the corresponding effective module area AM ) and the total output current (i) (inset of Fig. 3). The maximum experimental value of incident solar power (g) was 4.53 kW and total output current (i) 19.8 A. It can be seen that the higher values of g were obtained for E2, which was operating under clear sky conditions with the maximum number of photovoltaic modules (4) connected in parallel, (Table 3). In contrast, lower values of g were obtained for E4, when only one photovoltaic module was connected and clouds appeared during the experiment. To check the experimental results, the maximum irradiance under clear sky conditions was used as reference. From the photovoltaic geographical information system (PVGIS) of the Joint Research Centre of the European Commission (http://re.jrc.ec.europa.eu/pvgis), accessed in 2009, a maximum daily value of global clear sky solar irradiance of 981 W m 2 was obtained for May (tilt of 38 and south orientation (20 W)) in Santander, so the theoretical maximum value of g was 4.42 kW. Consequently, differences from the maximum values from PVGIS were below 3%, which agrees well with the experimental results. Once consistent energy input is conrmed, it is of interest to relate the generated current directly applied to the electrochemical reactor to the corresponding voltage. In Fig. 4, the relationship between the voltage between electrodes (v ), which is equal to the photovoltaic modules voltage, and the applied current (i) is shown. As can be seen in Fig. 4, there is no nett current through the system until a value around 5 V is reached, and then a linear relationship between v and i is observed. The slope is the ohmic resistance of the electrochemical reactor, which is mainly due to the conductivity of the solution pumped between the electrodes. Therefore, two different curves can be distinguished in Fig. 4: the curve for E4, which has the higher ohmic resistance due to the lower concentration of supporting electrolyte and therefore the lower conductivity, and the curves for E13, which have the
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6000
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(mScm-1) 3
pH(-) 6 5 4 3 2 0 60 120 180 240 300 360 420 480 Time (min)
4000 g (W)
360 420 480
3000 2000 1000
60
120
180
240 300 Time (min)
10 i (A)
15
20
Figure 5. Conductivity of the solution for experiment: () E1; ( ) E2; ( ) E3; ( ) E4. Inset: pH of the solution for experiment () E1; ( ) E2; ( ) E3; ( ) E4.
Figure 6. Incident solar power g versus total applied current i for experiments: () E1; ( ) E2; ( ) E3; ( ) E4 and calculated values () E1; ( ) E2; ( ) E3; ( ) E4.
same supporting electrolyte concentration and therefore similar ohmic resistances. Values of v as a function of i were tted to the relationship shown in the equation:
P (Wm-2)
80
60
v D v0 C iR
(1)
This expression is frequently used for electrochemical purposes with v0 the minimum required voltage to generate a nett current in the system.15,16 The v0 value was 3.89 1.15 V for E4 and 5.70 0.69 V for the set of curves E13. The slope was R D 2.10 0.40 for E4 and R D 0.50 0.06 for the set of curves E13. Corresponding values of R2 for E4 and the set for E13 were R2 D 0.79 and 0.81, respectively. Consequently, the relation between v and i is inuenced by the ohmic resistance due to the solution conductivity. Figure 5 shows the conductivity prole in the experiments. Conductivity shows an asymptotic behaviour, starting from D 3.3 mS cm 1 up to a stationary value around D 3.54 mS cm 1 for E13. On the other hand, for E4, at the beginning of the experiment the conductivity was only D 0.4 mS cm 1 (as the minimum quantity of sodium sulfate was added to the solution) and an increase was observed up to values D 1.0 mS cm 1 . Therefore, stationary conductivity values are obtained after the rst hour of operation. A relationship between solution conductivity and ohmic resistance is also observed due to the fact that increasing the conductivity four-fold (from D 1.0 mS cm 1 to D 3.54 mS cm 1 ) approximately decreases the ohmic resistance four times (from R D 2.1 to R D 0.5 ). Figure 5 shows the pH time prole: initial values of pH were around pH D 4.25 for E1-2-4 due to the same initial concentration of lignosulfonate and pH D 5.22 for E3; in this experiment the higher initial value was obtained due to the lower concentration of lignosulfonate, which has an acidic behaviour. A sharp decrease up to stationary values around pH D 3, 3.5, 2.75 was observed, respectively, for E1, 2, 4. For E3, a sharp decrease is also observed up to stationary values of pH D 4. Therefore, it is observed that the pH values tend to reach a stationary value. Therefore, it could be stated that pH and conductivity should present stationary behaviour under operation with stochastic input current. Additionally, a correlation between pH and conductivity is observed: the increase in the concentration of protons (HC ) increases the conductivity due to the high proton molar conductivity compared with other dissolved species17 such as carbonic acid.
40
20
250
500
750
1000
1250
G (Wm-2)
Figure 7. Electrical power per unit of module area P versus solar irradiance G for experiments: () E1; ( ) E2; ( ) E3; ( ) E4.
Equation (1) makes it possible to relate the voltage between electrodes and the applied current, but of interest is the relationship with the incident solar power (g). It can be observed from Fig. 4 that i follows the same trend as g, so the incident solar power (g) is plotted versus generated current (i) (Fig. 6), from which a linear relationship for low values of g and a positive deviation as g increases can be seen. Consequently, there is a relationship between these variables that should consider the fact that at high g values the relationship is no longer linear. Figure 7 shows the evolution of electrical generated power per module area unit (P) versus the incident solar power per module area unit or solar irradiance (G), and as can be seen from this gure, a linear relationship is observed between P and G. This relationship should be related to the conversion efciency of the modules. The power conversion efciency () is dened at the maximum power point.4 For a point different from the maximum power point, the corresponding slope in the linear relationship between P and G, as shown in Equation (2) gives the power conversion efciency: D pAM1 p lv P D D D G g G gAM1 (2)
The module efciency is presented in Table 4, showing that a higher value of is obtained for E2, which is the experiment in which the higher number of modules was connected and the
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Table 4. Energy variables and efciency in the experiments Exp E1 E2 E3 E4 EC kW h 9.42 13.85 7.46 4.03 EU kW h 0.59 1.14 0.37 0.20 % 5.3 7.0 5.3 5.6
Table 5. Specic energy consumption in the experiments Exp E1 E2 E3 E4 ESC,m kW h kgC 534 882 1035 176
1
ESC,v kW h m 294 571 184 100
minimum ohmic resistance was observed. However, no inuence of the number of modules or ohmic resistance was observed for the whole set of experiments. As shown in Table 4, the efciency of the set of modules is around 57% for the experiments, which is still far from the values for modules efciency ( D 14.2%) and the typical 15% of current monocrystalline silicon photovoltaic modules.7 Therefore, it is possible to make a better use of the energy collected, which should be based on adjusting the load of the electrochemical reactor to the corresponding maximum power point of the module.5 The combination of Equations (1) and (2) provides the following relationship between g and i: iv i(v0 C iR) iv0 C i R p D D gD D where for low values of i g and for high values of i R g i2 So if v0 , R and are known for the system, the solar irradiance (G) gives the input current (i) to the system and using Equation (1) the voltage can easily be obtained. The electrical power (p) considers two terms: the electrical use for electrochemical purposes and thermal losses due to the Joule effect. From Equation (3) it can be seen clearly that if R is increased due to a lower efuent conductivity, a higher solar power g is then required to obtain similar input current (i) values. Full dots in Fig. 6 show the values obtained for g when calculated using Equation (3) with the previous experimental values for v0 , R and ; although some deviations are presented they are consistent with the implicit error when the values of the parameters v0 , R and are used, so an acceptable agreement between calculated and experimental values is observed. An energy analysis based on the i v relationship has been performed and with the corresponding values of v0 , R and , the variation of the electrical variables of the electrochemical system can be obtained as a function of the irradiance (G). The basis of modelling the output current (i) and voltage (v ) from photovoltaic modules as a function of the solar irradiance (G) is available in several references18 20 and specic references applied in the area of wastewater treatment processes are also available.21,22 The complexity of the relationship between current and voltage for the solar module depends on the selected model. A well-known model is the ve parameters model, details of which can be found elsewhere.18,19 In this work the energy analysis relating the input current (i) and the solar power (g) as shown in Equation (3) agrees well with experimental data and it will be applied for the process modelling. v0 i
2
Finally, it is important to complete the energy analysis by checking how efciently the available energy is used for the electrochemical oxidation of the organic matter. To improve crosschecking between references, the concept of energy per order23 was avoided as it is difcult to make explicit the order of the individual kinetics, i.e zero or rst order, in each reference and especially for the experiments, where the random nature of the solar irradiation could make the process move from one order to another. Table 4 shows the energy data related to the experiments. The expression to calculate the total collected energy EC in each experiment is
t
Ec D (3)
0
gdt
(4)
Therefore EC is calculated from integration of the incident solar power over the period corresponding to the total duration of the experiment. As deduced from Table 4, the maximum energy collected EC D 13.85 kWh was for E2, as the number of modules connected was the maximum available under clear sky conditions. On the other hand, the total electrical energy EU in each experiment is calculated from
t
EU D
0
ivdt
(5)
The values of EU account for the energy applied to the electrochemical reactor oxidize the organic matter and the thermal losses due to the Joule effect. In a parallel way to Equation (4), EU is calculated by integration of the energy used over the total duration of the experiment. The maximum utilization of energy also took place in E2. Once the energy EU is available, it is of interest to calculate two ratios to assess how efciently the energy is used for organic matter removal. In Table 5 the specic energy consumption in each experiment is summarized, expressed as the energy required to remove a unit of mass ESC,m :
t
ivdt ESC,m D
0
vs [TOC ]t 0
(6)
or the energy to remove the organic matter per volume unit ESC,v :
t
ivdt ESC,v D
0
vs
(7)
From Table 5, despite having the lower concentration of supporting electrolyte, it is clear that the experiment E4 required a lower specic energy consumption (ESC,m ) of 176 kW h kgC 1 . For the other experiments, ESC,m ranges from 5341035 kW h kgC 1 . In order to compare the estimated values of energy consumption, several references are provided in Table 6 for synthetic and real efuents. For phenol removal with BDD electrodes, values
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PSEO for lignosulfonate wastewater treatment
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Table 6. Specic energy consumption in electrochemical oxidation from the literature Type of origin Synthetic Phenol Efuent ESC,m kW h kgC 26-91
1
ESC,v kW h m
Comments BDD electrodes (initial TOC: 4001000 mgC L 1 ; 5000 mg Na2 SO4 ; current densities: 1560 mA cm 2 ) Conventional treatment BDD electrodes (initial COD: 700 mgO2 L 1 ; removal of 100% of COD; 3000 mgNa2 SO4 ; without additional electrolyte, the energy required is twice-fold) BDD electrodes (25 mS cm 1 ; initial COD: 6000 mgO2 L 1 ; removal of 90%; current densities: 15 60 mA cm 2 ) DSA electrodes (addition of 5.85 g L 1 NaCl; current densities: 20160 mA cm 2 ) BDD electrodes
Ref. 14
Real Real
Urban wastewater Fenton - refractory
94
0.7 150
2426 27
Real
Fine chemical wastewater
200
28
Real Synthetic
Textile wastewater Lignosulfonate
154-822 176 100
29 This work
between 26 and 91 kW h kgC 1 have been reported.14 When the specic energy consumption is compared with that required to treat urban wastewaters, values around 0.7 kW h m 3 are well established.24 26 On the other hand, for industrial wastewaters, values tend to be higher. For example, for a Fenton-refractory olive oil mill wastewater, values of 150 kW h m 3 were reported27 and for ne chemical plant wastewaters less than 200 kW h m 3 .28 The degradation of textile efuents by DSA electrodes required between 154 and 822 kW h kgC 1 and a high concentration of sodium chloride as supporting electrolyte.29 It can be concluded that the energy consumption for this process is of the order of magnitude of electrochemical oxidation and energy consumption depending on the removal, which is a function of applied current and efuent conductivity. Mass balance The energy balance was completed as a prior step to the mass analysis; discussion of the experimental results for the mass balance requires a previous analysis of the use of the energy because it is assumed that the evolution of the removal of organic matter depends on the solar irradiance. For the experiments performed, TOC removal, expressed as log C0 /C versus time has been plotted in Fig. 8. For a better understanding of the results, the maximum theoretical TOC removal rate is also shown as a straight line with zero crossing (K-line), whose slope is based on the maximum observed kinetic constant Kmax D 8.09 10 3 min 1 reported previously for the experimental setup under laboratory controlled current conditions.30 It was expected that all experimental points would be below the K-line as long as no other mechanism was involved. A maximum value of Km D 2.31 10 3 m min 1 from previous laboratory studies was obtained, which was used as reference. The observed kinetic constant Kexp and corresponding standard error (95% condence level) for each experiment according to a rst-order kinetic is reported in Table 7. To compare experiments, an average input current (iAV ) and solar power (gAV ) were dened for each experiment. It is observed that experiments E1 and E3 show similar values of the average input current, solar power and kinetic constant (Kexp ) (Table 7). On the other hand, E2 and E4 show positive and negative deviations from these values. From Fig. 8, removal close to 90% is obtained for both experiments E2 and E4 at different numbers of hours of operation. It is observed from Fig. 8 that experimental values
3 2.5 Ln(C0C-1) (-) 2 1.5 1 0.5 0
60
120
180
240 300 Time (min)
360
420
480
Figure 8. Organic matter removal versus time for experiments: () E1; ( ) E2; ( ) E3; ( ) E4. ( ) K-line. The K-line represents the theoretical maximum removal rate obtained under controlled current conditions.
Table 7. Apparent kinetic constants (standard error at 95% condence level). The maximum kinetic was considered to be Kexp D 2.31 10 3 m min 1 Exp E1 E2 E3 E4 iAV A 8.48 15.39 6.69 2.42 gAV kW 1.86 3.43 1.47 0.50 Kexp 103 m min 1.80 0.18 2.28 0.20 1.79 0.24 1.31 0.09
1
for E2 are on the reference K-line over the rst 3 h of operation. After 3 h, deviation of experimental values above the K-line is observed for the two last experimental points This deviation, only observed for E2, corresponds with the highest value of the average input current iAV D 15.39 A and the higher value of the kinetic constant Kexp D 2.28 10 3 m min 1 . To explain this positive deviation above the K-line, it has been suggested that a mechanism in addition to the electrochemical oxidation involving hydroxyl radicals is present, which could be used to explain the behaviour for the whole set of four experiments. This mechanism assumes that two serial steps could be taking place: (i) direct oxidation by hydroxyl radicals OH in the layer of liquid close to the
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www.soci.org surface of the electrode; (ii) mass transfer of organic matter from the bulk to the electrode surface. Consequently, if the reaction rate in the layer of liquid close to the electrode is fast enough, the process will be mass transfer controlled. Additionally, the indirect oxidation by electro-generated reagents (peroxodisulfates if sodium sulfate is used), whose concentration in the bulk phase depends on the applied current and for which there is no mass transfer limitations31,32 could be contributing in a parallel way. At these values of applied current (15.39 A), the contribution of the parallel reaction by electro-generated oxidants is suggested to have a positive effect, making the reaction rate higher than those obtained for lower values, so a maximum concentration of electro-generated peroxodisulfates was expected. If this additional mechanism is considered and assuming that the higher the applied current the higher is the concentration of oxidants in the bulk phase, an increase in the applied current may lead to reaction rates over the theoretical maximum reaction rate, which only considers the two serial steps mechanism: oxidation by hydroxyl radicals at the layer close to the electrode surface and mass transfer from the bulk phase to the electrode surface. The opposite trend is observed for E4 (Fig. 8) where the experimental values are below the K-line for the whole experiment, especially after the rst 5 h. In E4, lower values of input current did occur (2.42 A) and the kinetic constant Kexp D 1.31 10 3 m min 1 was also lower. Therefore, it was expected that the contribution of parallel reactions from electro-generated reagents was negligible in E4, in which the applied current had the lower values. Additionally, for the last 3 h in E4, the removal of TOC deviated from a linear behaviour suggesting the possibility of a change of the order of the kinetics from rst order. As will be explained in detail later, the kinetic constant depends on the applied current; therefore, at relatively low irradiances it is expected that the process will occur under zero order kinetics. Once the possibility of the involvement of an additional mechanism is considered for relatively high current values, it is worth checking the inuence of the applied current at more moderate applied currents. Despite having different solar irradiance proles and initial concentrations but with similar average input currents, it can be deduced from Fig. 8 that it is possible to achieve up to 90% in TOC removal in E1 and E3 as well as in E2 and E4 but for similar tOP . Considering the K-line in Fig. 8, it is observed that the experimental degradation rate is below the maximum rate in both experiments (Kexp D 1.80 10 3 and 1.79 10 3 m min 1 , respectively, for E1 and E3) for the total experimental time. It is noticeable that despite both experiments having different solar irradiance proles, the evolution of TOC is similar (Fig. 8). Consequently, increasing values from 6 to 9 A did not seem to show faster removal of TOC, so the contribution of parallel reactions by electro-generated reagents may have a negligible contribution as in E4 within the cited current range. equations: BDD[] C H2 O BDD[OH ] C R C HC C e
! BDD[OH ] C HC C e ! BDD[] C mCO2 C nH2 O
(8) (9)
In Equation (8), BDD[] represents an active site in the borondoped diamond layer for the discharge of a water molecule and corresponding generation of a proton and an electron. On the other hand, Equation (9) shows the combustion of organic matter (R) to combustion products (CO2 and H2 O) plus the proton and electron pair: after oxidation of R, the active site in the boron doped diamond layer is able to accept a new water molecule in the water discharge reaction. According to this reaction scheme and based on previous references for this experimental setup and lignosulfonate as organic substrate,30 the reaction rate rA for TOC removal is described bythe equation: 1 C
1
CD r A D K C D 1 C iC AE
J C0 J C0
AE VE AE VE
CD 1C
C 0 vE AE C 0 vE AE
iC AE
(10)
PSEO TOC removal model In electrochemical oxidation, the key variable is the electrical current. A model of the electrochemical oxidation of lignosulfonate under laboratory controlled current conditions has been published.30 References detailing a mechanism involving generation of hydroxyl radicals, responsible for the electro-combustion of organic matter, on the surface of boron doped diamond anodes can be found elsewhere,33,34 and are summarized in the following
where rA is the reaction rate referred to the electrode area; K is the intensity-dependent kinetic constant; C is the concentration of the organic matter R expressed as TOC; is the applied current per mass of O2 ; and are tting parameters for batch data under controlled current conditions; J is the current density; C0 is the initial concentration of the organic matter expressed as TOC in the electrochemical reactor; AE is the electrode area; vE is the electrochemical reactor volume; iC is the applied current under controlled conditions. This kinetic rate in Equation (10) shows a hyperbolic inuence of the applied current on the kinetic constant, thus when the applied current becomes high enough, the process becomes controlled by the mass transfer of organic matter to the electrode surface from the bulk phase. However, if the applied current is lower, the process becomes controlled by the applied current, that is, by the oxidation in the electrode surface, and the mass transfer is no longer the controlling step. Therefore, at relatively high values of iC or , a maximum value for K is obtained: the maximum observed kinetic constant Kmax . However, in these experimental results, the stochastic nature of the solar irradiation makes the applied current changes with time. Then, as the solar irradiance is the main input variable to the process, it was suggested that an expression was needed which correlates i with g so the reaction rate could be expressed in terms of the solar irradiance (G) or solar power (g). A relationship between g and i is shown in Equation (3) that allows the reaction rate rA (degradation of TOC) to be expressed as a function of the solar power (g). The substitution of Equation (3) in Equation (10) leads to Equation (11), with the controlled current (iC ) substituted by the stochastic input current (i): rA D K1 i(g) c KC 1 C K2 i(g) when K2 i(g) >> 1 ) K D K1 K2 1 when K2 i(g) << 1 ) K D K1 i(g) (11)
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PSEO for lignosulfonate wastewater treatment where K is the instantaneous kinetic constant as a function of g and K1 and K2 are parameters derived from tting parameters for batch data under controlled current conditions and , initial concentration C0 and the electrochemical cell volume vE . For the experimental setup and initial concentration corresponded with a chemical oxygen demand (COD) around 1500 mgO2 L 1 (E1-2-4) previous values are K1 D 6.81 10 4 m min 1 A 1 and K2 D 2.95 10 1 A 1 (K1 D 2.06 10 3 m min 1 A 1 and K2 D 8.86 10 1 A 1 for COD around 500 mgO2 L 1 as in E3). As previously discussed, Equation (11) shows that when relatively high values of i are available, the process becomes mass transfer controlled with K D K1 K2 1 and following rst-order kinetics. For relatively low values of i, the process becomes controlled with current K D K1 i(g), so under this regime, the process will follow zero-order kinetics. Advantages of PSEO process The PSEO process is an interesting option that meets most of the requirements of self-sustainable processes for wastewater treatment. This process was justied from an economic point of view by De Lucas et al.35 who stated that electrochemical oxidation could be economically competitive if ow-rates below 1 m3 day 1 were treated. Indeed, electrochemical oxidation has been suggested to be even more competitive than other advanced oxidation processes.36 The scale of solar powered systems required is of interest and tends to be low to medium size,37 e.g. for reverse osmosis powered by solar modules of a few thousands of cubic metres per day. The capabilities of this technology for tertiary treatment and corresponding water reuse possibilities should be mentioned even though it is outside the scope of this work. Not only is it possible to complete the disinfection of water using BDD38,40 or metal oxide electrodes41 up to authorized level for water reuse but to perform it with energy consumption around 27.8 kW h m 3 , depending on the microorganism and supporting electrolyte for platinum clad niobium anodes.40 Values of 2 kW h m 3 have been reported for BDD electrodes in a chlorine-free phosphate medium.39 These values are around two orders of magnitude lower than for normal wastewater treatment. There is a lot of opportunity for improving both electrochemical and photovoltaic solar technologies. Electrochemical technologies can benet from the combination with other technologies such as UV radiation due to synergy in the generation of hydroxyl radicals OH .42 On the other hand, photovoltaic modules producers are focused on reducing manufacturing costs per watt,43 which will end on reaching parity with the grid so the economic analysis will be controlled just by the investment on the electrochemical reactor. The specic energy consumption required by the coupled process was 100 kW h m 3 for E4, which is in the range of values reported previously in Table 6. To optimize the process and make better use of the collected energy, the process should adjust not only the resistance of the electrochemical reactor, assuming it remains as the controlling ohmic resistance, to the corresponding to the maximum operating point but the applied current to the stoichiometric value.34,44 Consequently, it is possible to reduce the specic energy consumption of the coupled process in its current status for a certain efuent based on three points of interest: photovoltaic module conguration (number of serial and parallel modules) and total available area (total power);
www.soci.org characteristics of the efuent: conductivity and load of organic matter; total electrode area. Consequently, the ratio between the area of modules and the electrode area AM AE 1 can be improved: the suggested trend is to decrease the module area and increase the electrode area. In this way, the degradation rate rises due to the higher availability of electrode surface to produce hydroxyl radicals OH and the input current to the reactor is not used in parallel mainly hydrolysis reactions.33
SUMMARY
The technical suitability of a photovoltaic solar electrochemical oxidation (PSEO) process to degrade organic matter from wastewater with removal yields close to 90% TOC has been demonstrated. As the PSEO process performance depends on the applied current, a model which relates the generated input current to the process as a function of incident solar power has been developed. A reaction rate model has been proposed based on the solar power, describing the process under stochastic solar irradiance and therefore, stochastic applied current. Therefore, the TOC removal depends on the electrode area (AE ) and the photovoltaic module area (AM ). Specic energy consumption was around that of cited references. Moreover, the ratio between the photovoltaic module area and electrode area AM AE 1 can be largely optimized for an efuent with xed characteristics to prevent excess applied current and therefore allow the process to perform in a sustainable way and with an appropriate investment economic cost and a friendly environmental prole.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the nancial support of the Ministry of Science and Technology of Spain through the project CTM2006-00317 and the project CENIT Sostaqua.
REFERENCES
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12 Hyunwoong P, Vecitis CD, Wonyong C, Weres O and Hoffmann MR, Solar-powered production of molecular hydrogen from water. J Phys Chem C 112:885889 (2008). 13 Thomson M and Ineld D, Laboratory demonstration of a photovoltaic-powered seawater reverse-osmosis system without batteries. Desalination 183:105111 (2005). 14 Canizares P, D az M, Dom nguez JA, Garc a-Gomez J and Rodrigo MA, Electrochemical oxidation of aqueous phenol wastes on synthetic diamond thin-lm electrodes. Ind Eng Chem Res 41:41874194 (2002). 15 Panizza M, Michaud PA, Cerisola G and Comninellis C, Electrochemical treatment of wastewaters containing organic pollutants on boron-doped diamond electrodes: prediction of specic energy consumption and required electrode area. Electrochem Commun 3:336339 (2001). 16 Bonvin G and Comninellis C, Scale-up of bipolar electrode stack dimensionless numbers for current bypass estimation. J Appl Electrochem 24:469474 (1994). 17 Yaws CL, Yaws Handbook of Thermodynamic and Physical Properties of Chemical Compounds. Knovel, Norwich, New York (2003). 18 Celik AN and Acikgoz N, Modelling and experimental verication of the operating current of mono-crystalline photovoltaic modules using four- and ve-parameter models. Appl Energy 84:115 (2007). 19 Townsend TU, Simplied performance modeling of a direct-coupled photovoltaic systems. Masters thesis, University of Wisconsin, Madison (1989). 20 Gow JA and Manning CD, Development of a photovoltaic array model for use in power-electronics simulation studies. IEE Proc Elec Power Appl 146:193200 (1999). 21 Ortiz JM, Exposito E, Gallud F, Garc a-Garc a V, Montiel V and Aldaz A, Electrodialysis of brackish water powered by photovoltaic energy without batteries: direct connection behaviour. Desalination 208:89100 (2007). 22 Ortiz JM, Exposito E, Gallud F, Garc a-Garc a V, Montiel V and Aldaz A, Photovoltaic electrodialysis system for brackish water desalination: modeling of global process. J Membr Sci 274:138149 (2006). 23 Bolton JR, Bircher KG, Tumas W and Tolman CA, Figures-of-merit for the technical development and application of advanced oxidation technologies for both electric- and solar-driven systems. Pure Appl Chem 73:627637 (2001). 24 California Energy Commission, Californias water energy relationship CEC-700-2005-011-SF (2005). 25 European Commission, Reference document on best available techniques in common waste water and waste gas treatment/management systems in the chemical sector (2007). Available at ftp://ftp.jrc.es/pub/eippcb/doc/cww bref 0203.pdf (accessed in 2009). 26 Tchobanoglous G, Burton FL and Stensel HD, Wastewater Engineering: Treatment and Reuse. 4th edn. McGraw-Hill, Boston, 1819 (2003). 27 Canizares P, Mart nez L, Paz R, S aez C, Lobato J and Rodrigo MA, Treatment of Fenton-refractory olive oil mill wastes by electrochemical oxidation with boron-doped diamond anodes. J Chem Technol Biotechnol 81:13311337 (2006). 28 Canizares P, Paz R, Lobato J, S aez C and Rodrigo MA, Electrochemical treatment of the efuent of a ne chemical manufacturing plant. J Hazard Mater 138:173181 (2006).

29 Malpass GRP, Miwa DW, Mortari DA, Machado SAS and Motheo AJ, Decolorisation of real textile waste using electrochemical techniques: effect of the chloride concentration. Water Res 41:29692977 (2007). 30 Dominguez-Ramos A, Aldaco R and Irabien A, Electrochemical oxidation of lignosulfonate: total organic carbon oxidation kinetics. Ind Eng Chem Res 47:98489853 (2008). 31 Serrano K, Michaud PA, Comninellis C and Savall A, Electrochemical preparation of peroxodisulfuric acid using boron doped diamond thin lm electrodes. Electrochim Acta 48:431436 (2002). E, Haenni W, Perret A and Comninellis C, Preparation 32 Michaud P, Mahe of peroxodisulfuric acid using boron-doped diamond thin lm electrodes. Electrochem Solid-State Lett 3:7779 (2000). 33 Marselli B, Garcia-Gomez J, Michaud PA, Rodrigo MA and Comninellis C, Electrogeneration of hydroxyl radicals on boron-doped diamond electrodes. J Electrochem Soc 150:D7983 (2003). G and Comninellis C, Kinetic modelling of the 34 Kapalka A, Foti electrochemical mineralization of organic pollutants for wastewater treatment. J Appl Electrochem 38:716 (2008). 35 DeLucas A, Canizares P, Rodrigo MA and Garc a-Gomez J, Electrochemical treatment of aqueous phenol wastes: A preliminary economical outlook. Waste Manag Environ 161170 (2002). 36 Canizares P, Paz R, S aez C and Rodrigo MA, Costs of the electrochemical oxidation of wastewaters: A comparison with ozonation and Fenton oxidation processes. J Environ Manage 90:410420 (2009). 37 Fiorenza G, Sharma VK and Braccio G, Techno-economic evaluation of a solar powered water desalination plant. Energy Conv Manage 44:22172240 (2003). 38 Palmas S, Polcaro AM, Vacca A, Mascia M and Ferrara F, Inuence of the operating conditions on the electrochemical disinfection process of natural waters at BDD electrodes. J Appl Electrochem 37:13571365 (2007). 39 Jeong J, Kim JY and Yoon J, The role of reactive oxygen species in the electrochemical inactivation of microorganisms. Environ Sci Technol 40:61176122 (2006). 40 Kerwick MI, Reddy SM, Chamberlain AHL and Holt DM, Electrochemical disinfection, an environmentally acceptable method of drinking water disinfection? Electrochim Acta 50:52705277 (2005). 41 Diao HF, Li XY, Gu JD, Shi HC and Xie ZM, Electron microscopic investigation of the bactericidal action of electrochemical disinfection in comparison with chlorination, ozonation and fenton reaction. Process Biochem 39:14211426 (2004). 42 Pelegrini RT, Freire RS, Duran N and Bertazzoli R, Photoassisted electrochemical degradation of organic pollutants on a DSA type oxide electrode: process test for a phenol synthetic solution and its application for the E1 bleach kraft mill efuent. Environ Sci Technol 35:28492853 (2001). 43 EU PV Technology Platform, Working Group 3, Science, Technology and Applications, A strategic research agenda for photovoltaic solar energy technology (2007). 44 Panizza M, Kapalka A and Comninellis C, Oxidation of organic pollutants on BDD anodes using modulated current electrolysis. Electrochim Acta 53:22892295 (2008).
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4.4 Dominguez-Ramos, A., Held, M., Aldaco, R., Fischer, M., Irabien, A. Prospective conditions. CO2 emissions from energy supplying systems: photovoltaic systems and conventional grid within Spanish frame
I nt. J. Life
Cycle Assess. 2010, En prensa, DOI:
10.1007/s11367-010-0192-3
Resumen El enfoque de Anlisis de Ciclo de Vida (ACV) se ha empleado para evaluar la sostenibilidad ambiental en trminos de CO2-eq. del suministro energtico a un proceso de electro-oxidacin mediante: i) energa convencional de red ii) energa solar fotovoltaica, considerando Espaa como marco de referencia. Se emple el software de ACV GaBi 4 para modelar los dos suministros energticos, considerando como unidad funcional 1 kWh de energa elctrica producida. Esta misma evaluacin, se realiz considerando nueve escenarios para el mix elctrico y la energa solar fotovoltaica en el horizonte 2030 para considerar la transicin hacia un modelo energtico con menores emisiones de CO2 y la evolucin de las diferentes tecnologas fotovoltaicas. Los resultados obtenidos mostraron que en el horizonte 2030, las reducciones para el mix elctrico con respecto a los valores de 2007 fueron del orden del 60%. Las reducciones considerando la evolucin de las diferentes tecnologas fotovoltaicas en 2030 fueron del orden del 60% respecto a 2007. De esta forma, se considera que el suministro energtico al proceso de electro-oxidacin mediante energa solar fotovoltaica es una opcin ambientalmente preferible en trminos de CO2-eq. frente al suministro convencional, debido a las menores emisiones en el orden 1/17, tanto en las condiciones actuales como en las futuras.
Original abstract
In order to assess the environmental sustainability of a novel wastewater treatment process based on power a electrochemical reactor by photovoltaic solar modules (Photovoltaic Solar Electrochemical Oxidation PSEO), a life cycle approach was considered to quantify the CO2-eq. emissions coming from the two supplying power systems to the electrochemical process: conventional grid power or photovoltaic solar power under Spain frame conditions. GaBi 4 software was used to build models to characterize the conventional grid and photovoltaic power generation (corresponding functional unit: 1 kWh). ecoinvent v2.0 was chosen to consider background data. Nine different 2030 scenarios were evaluated versus 2007 reference values to take into account: i) the progressive change to a greener grid mix in Spain ii) the improvements in photovoltaic solar technology.
123
The results showed that under the nine considered scenarios for 2030, the CO2-eq.kWh-1 emissions are always lower than the reference values for 2007 (reductions around 60%). Additionally, the results showed that 2030 values for the CO2-eq.kWh-1 emissions coming from the use of photovoltaic modules for power generation are expected to be around 60% lower than for 2007 values. In order to power an electrochemical process, the direct use of photovoltaic solar energy will give much lower CO2-eq.kWh-1 emissions than the supply from conventional grid. A quantitative study based on Life Cycle Assessment has compared the CO2-eq.kWh-1 emissions coming from supplying an electrochemical reactor by conventional grid and by photovoltaic solar modules under Spain frame conditions and stated that the novel process Photovoltaic Solar Electrochemical Oxidation would be a preferred environmental option due to the lower CO2-eq.kWh-1 emissions under present and future scenarios. The results would suggest that it is worthy to explore not only the possibilities of this technology, but other electrochemical technologies that can be supplied directly by electricity in order to have a better sustainability performance.
124
Int J Life Cycle Assess DOI 10.1007/s11367-010-0192-3
LCA FOR ENERGY SYSTEMS
Prospective CO2 emissions from energy supplying systems: photovoltaic systems and conventional grid within Spanish frame conditions
Antonio Dominguez-Ramos & Michael Held & Ruben Aldaco & Matthias Fischer & Angel Irabien
Received: 7 July 2009 / Accepted: 18 April 2010 # Springer-Verlag 2010
Abstract Background, aim, and scope In order to assess the environmental sustainability of a novel wastewater treatment process based on power an electrochemical reactor by photovoltaic solar modules (photovoltaic solar electrochemical oxidation), a life cycle approach was considered to quantify the CO2 equivalent (CO2-eq.) emissions coming from the two supplying power systems to the electrochemical process: conventional grid power or photovoltaic solar power under Spain frame conditions. Materials and methods GaBi 4 software was used to build models to characterize the conventional grid and photovoltaic power generation (corresponding functional unit, 1 kWh). ecoinvent v2.0 was chosen to consider background data. Nine different 2030 scenarios were evaluated versus
Responsible editor: Niels Jungbluth. A. Dominguez-Ramos (*) : R. Aldaco : A. Irabien Department of Chemical Engineering and Inorganic Chemistry, University of Cantabria, Avda. Los Castros, 39005 Santander, Spain e-mail: domingueza@unican.es M. Held Abteilung Ganzheitliche Bilanzierung, LBP, University of Stuttgart, Hauptstrasse 113, 70771 Echterdingen, Germany M. Fischer Department of Life Cycle Engineering, Fraunhofer Institute for Building Physics, Hauptstrasse 113, 70771 Echterdingen, Germany
2007 reference values to take into account: (a) the progressive change to a greener grid mix in Spain and (b) the improvements in photovoltaic solar technology. Results The results showed that, under the nine considered scenarios for 2030, the CO2-eq.per kilowatt hour emissions are always lower than the reference values for 2007 (reductions around 60%). Additionally, the results showed that 2030 values for the CO2-eq.per kilowatt hour emissions coming from the use of photovoltaic modules for power generation are expected to be around 60% lower than for 2007 values. Discussion In order to power an electrochemical process, the direct use of photovoltaic solar energy will give much lower CO2-eq.per kilowatt hour emissions than the supply from conventional grid. Conclusions A quantitative study based on life cycle assessment has compared the CO2-eq.per kilowatt hour emissions coming from supplying an electrochemical reactor by conventional grid and by photovoltaic solar modules under Spanish frame conditions and stated that the novel process photovoltaic solar electrochemical oxidation would be a preferred environmental option due to the lower CO2-eq.per kilowatt hour emissions under present and future scenarios. Recommendations and perspectives The results would suggest that it is worthy to explore not only the possibilities of this technology but also other electrochemical technologies that can be supplied directly by electricity in order to have a better sustainability performance. Keywords Carbon footprint . Electrochemical oxidation . Grid mix . Photovoltaic solar energy . Solar technology . Spain . Wastewater treatment
Int J Life Cycle Assess
1 Background, aim, and scope 1.1 Background Within the current energy global framework, the integration of renewable energy sources into production systems is a key point to be challenged as mentioned in A roadmap for the 21th century chemical engineering of the Institution of Chemical Engineers (IChemE 2007). Thus, being energy one of the main actors of the process sustainability, the progressive phasing out of fossil fuels ought to be a basic step in the overall transition to a cleaner primary energy. State-of-the-art technology for wastewater treatment makes it possible to transform water scarcity into diverse energyintensive scenarios. Technologies such as electrochemical oxidation (EO) supporting boron-doped diamond (BDD) electrodes has been claimed as a promising technology not only in purification and disinfection applications but also for depuration and therefore promoting water reclamation and reduced net usage of water from original sources. This technology has been successfully applied for different polluted industrial wastewaters such as olive mill, pulp and paper, textile, pharmaceutical, landfill leachate, leather, phenol formaldehyde, oil refinery, bulk drug manufacture, carwash, and motor industry (Dominguez-Ramos et al. 2008). From an operating point of view, EO has been emphasized as a suitable technology in those cases in which the chemical oxygen demand is below 5,000 mgO2 l1, although a wide range of applications ranging from 100,000 to 1,000 mgO2 l1 has been suggested. In the comparison with other advanced oxidation processes, the sludge and consumption of chemicals reduction are very attractive features of electrochemical oxidation from a life cycle (LC) perspective. BDD has been widely recognized as an excellent material for electrodes to perform electrochemical oxidation for the removal of organics from wastewater due to its high anodic stability and wide potential window. Derived from the unique surface properties, BDD electrodes can perform the electrocombustion of the organic matter with energetic efficiency under the appropriate operational conditions. When applying an electrical current to the electrodes, powerful oxidants can be created at the surface or in the bulk liquid phase, depending on the operational conditions and therefore promoting the combustion of the organic matter to CO2 and H2O. Nevertheless, this technology lacks attractiveness due to the electrical energy consumption per unit of volume treated (Caizares et al. 2002), which is a major drawback due to the contribution to global warming as well as other environmental impacts. Life cycle approach shows the shift of burdens between life cycle phases or processes when EO is based on grid power to get high-quality water. In order to
overcome the previously described situation, the integration of photovoltaic solar systems as primary energy source to the EO process was proposed as only electricity as direct current is required. The result is a photovoltaic solar powered electrochemical oxidation (PSEO) process (Dominguez-Ramos et al. 2010), in which electrons collected by the solar modules are used directly to generate powerful oxidants into the liquid phase of the polluted effluent, which remove organic matter up to the desired values. This option annuls the need of massive energy storage systems in the form of leadsulfuric acid batteries, which is typical for photovoltaic systems or other energy storage systems such as Li-ion batteries. Specially for continuous treatment, an appropriate design of raw water tanks will allow the process to accumulate the contaminated effluent and to be working under low or null irradiation periods (e.g., night, overcast conditions, winter, etc.). The integration of photovoltaic solar systems is expected to be an adequate solution for a Mediterranean country such as Spain, with very good perspectives for PV technology issues, not only manufacturing and R&D but also for power generation (Salas and Olias 2008). If water scarcity is added to that previous statement, PSEO processes are likely to be interesting in the mid-term considering water reuse and reclamation objectives. 1.2 Aim and scope of the work The aim of this work is to obtain a quantitative estimation of the environmental benefits in terms of CO2 equivalent (CO2-eq.) emissions of using photovoltaic solar electricity for the self-sustainable PSEO processes instead of conventional grid power by means of LC Assessment (LCA) methodology (ISO 2006a, b). Therefore, an assessment of the quantity of GHG emissions expressed as kilograms of CO2-eq. from grid power and current commercial PV modules in 2007 was performed, being Spain the chosen country for frame conditions such as solar irradiation, performance ratio of the PV modules, country grid mix, etc. Furthermore, a prospective analysis expressed as kilograms of CO2-eq. emissions for 2030 from the future PV modules and grid power in Spain was also carried out to have a quantitative estimation of the benefits in carbon footprint terms that PSEO takes from using solar photovoltaic energy. To describe the grid power generation, only the representative reported technologies contributing to the power grid mix in Spain were considered. Those technologies with an expected minority contribution (such as residual heat or solar thermoelectric) were out of the scope of this work. As many PV technologies are now available for electricity supply, only those that have representative prospective studies were considered in this work. Although
other technologies like dye-sensitized or organic polymer solar cells seem to be occupying a notable share of the market in the future, they were not analyzed as the prospective studies for them are not suitable for the present work. The boundary limits of the modeled systems are shown in Fig. 1.
was used to calculate the output energy from a PV module in its lifetime considering solar irradiation, performance ratio, efficiency, and lifetime.
3 Description of evaluated energy systems The grid power from Spain at medium voltage and the power from different PV technologies have been considered to supply the PSEO process. Between the PV technologies, the wafer silicon-based PV technologies (multicrystalline silicon (mc-Si) and monocrystalline silicon (c-Si)), the silicon ribbon technology (Ribbon-Si), and the thin film technologies (amorphous silicon (a-Si), cadmium telluride (CdTe), and copper indium gallium sulfur selenide (CIGS)) were considered as alternatives. 3.1 Description of the modeled energy systems 3.1.1 Modeled grid power The grid power system was structured in three steps. In the first step, the grid mix was modeled considering the contribution of the different power plants existing in Spain and data availability from ecoinvent (2008). The grid mix for Spain in 2007 is summarized in Table 1. For consistency purposes and because of certain lack of reliable data and in order to match the share of the technologies from the former reference, residual heat and solar thermoelectric were excluded from this study (this assumption would be reasonable as its expected contribution is less than 1%). On the other hand, it was estimated that 85% of imported coal is hard coal for combustion purposes. For electricity generation from natural gas, ecoinvent v2.0 typically considers combustion in gas burners. However, natural gas is mainly combusted using
2 Materials and methods The models described in this work to characterize the behavior of the power grid mix and the photovoltaic system performance were built using GaBi 4 LCA software (GaBi 2008). For the upstream processes, ecoinvent v2.0 (ecoinvent 2008) as background data was used. The collections of data for the grid mix and PV performance in 2007 and 2030 were collected from various studies being given extra details later. Unless the opposite is stated, all unit process data come from ecoinvent v2.0, and the different parameters used along the text are only valid for the models developed for the grid mix and the photovoltaic systems. In order to build the model discussed later for power grid mix generation, different technologies available in ecoinvent 2.0 were utilized to complete the best possible matching with the description of considered technologies in the different references for the grid mix (see Table 1 for selected technologies). A model taking into account the energy balance in the whole grid was used to assess imports, exports, own consumption, and water pumping. Net losses were modeled as background data (it is estimated that 1.025 kWh is required from the grid to get 1 kWh at medium voltage). Therefore, consistency, representativeness, and reliability are guaranteed as the minimum number of modifications (with respect to the models in ecoinvent v2.0) was performed to complete the description of the grid mix and later power distribution. For PV power, a model
Fig. 1 System boundary of the modeled energy systems (left grid power generation and right solar photovoltaic generation). Modules using foreground data are highlighted
RESOURCES ENERGY NUC NTG H&P HRC LIG HYD HFO PV MODULE PRODUCTION MOUNTING SYSTEM WIN ING INVERTER SYSTEM INSTALLED SYSTEM USE PHASE
ENERGY MIX WNS WFS PHV BIO
ENERGY BALANCE ENERGY (HIGH VOLTAGE ) ENERGY (MEDIUM VOLTAGE)
FUNCTIONAL UNIT: 1kWh EMISSIONS
FUNCTIONAL UNIT: 1kWh
Int J Life Cycle Assess Table 1 Shares of technologies for power generation in the Spanish grid mix in 2007 and 2030 (under the nine considered scenarios) Technology Nuclear Natural gas Heat and power Hard coal Lignite Hydro Heavy fuel oil Wind on shore Wind off shore Photovoltaic Biomass Waste Inc Industrial gas Ref. 2007 18.6 24.4 5.7 20.7 4.8 10.3 4.5 9.1 0.0 0.2 0.8 0.8 0.1 MUS-NGP 14.1 42.3 6.3 0.2 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 NE-NGP 24.6 32.0 6.3 0.1 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 MPW-NGP 14.0 26.4 6.2 0.0 0.0 10.0 0.0 29.7 10.2 1.6 1.5 0.4 0.0 CC-NE-NGP 18.3 34.4 6.3 4.0 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 MUS-CP 14.1 41.6 6.3 1.0 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 NE-CP 24.6 31.1 6.3 0.9 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 MPW-CP 14.0 25.5 6.2 0.9 0.0 10.0 0.0 29.7 10.2 1.6 1.5 0.4 0.0 CC-CP 14.1 31.0 6.3 11.5 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0 CC-NE-CP 18.3 31.1 6.3 7.3 0.0 9.2 0.0 20.8 3.5 1.6 1.6 0.4 0.0
Values expressed as percentage
combined cycle stations in Spain; therefore, it was assumed as reference that 100% of the natural gas is combusted in combined cycle stations (in ecoinvent v2.0, the generation of 1 kWh releases 0.425 versus 0.515 kg CO2-eq. when combined cycle is selected). Combined cycle stations were assumed for 2030 scenarios. For those scenarios in which coal stations and carbon capture and storage (CCS) are considered, the emissions from the life cycle of an integrated gasification combined cycle (IGCC) equipped with CCS (precombustion physical absorption with Selexol solvent) from Odeh and Cockerill (2008) was used (this is the only unit process whose emissions inventory does not comes from ecoinvent v2.0). For hydropower plants, 85% of the total power was assumed to come from run-of-river plants and 15% from reservoir plants (SGE 2008). Furthermore, it was estimated that the photovoltaic contribution to power generation was based on ground-mounted installations and modeled as discussed later. Table 2 summarizes the global market shares of PV technologies that were used to consider the PV contribution to the grid power in 2007 and 2030 (EPIA and Greenpeace 2008; EPIA 2008), being remarkable that the wafer silicon-based technology is about 90% of the
market in 2007 and that in 2030 this value is reduced to around 35%. For 2030, a 35% of the share is assigned to conventional silicon technology, a 30% to thin-film technology, and a 35% to new developments such as organic cells. To simplify the current analysis, the contribution of new developments was skipped, keeping the proportions given by the 2007 shares. On the other hand, the share of energy corresponding to meet peak power demand in 2030 was assumed to be based on natural gas (UNESA 2007) and therefore included in the share shown in Table 1. In the second step, an energy balance considering imports, exports, owned consumed, and water pumping energy was completed as second level as summarized in Eq. 1: EGen EM EImp EExp EPum EOC 1
where the EGen stands for the available energy for distribution, EM is the energy given by the set of considered technologies to the grid mix (the contribution in energy units of each technology to the mix can be obtained considering the shares shown in Table 1 and the total energy from the grid mix EM shown in Table 3), EImp is the mix of the imported energy (82% and 18% from France and Portugal grid mix, respectively, using ecoinvent v2.0
Table 2 Shares of PV technologies used for prospected scenarios in 2007 and 2030 a-Si 2007 2030 5.2 35 CdTe 4.7 10 CIGS 0.5 1 mc-Si 45.2 27 c-Si 42.2 25 Ribbon-Si 2.2 1
Table 3 Contribution of each energy term to the total energy generation EGen in 2007 EM 296,552 EImp 8,874 EExp 14,630 EPum 4,349 EOC 9,600 EGen 276,847
Values expressed as percentage
Values expressed as gigawatt hours
references for the grid mix data), EExp is the exported energy, EPum is the energy used for water pumping, and EOC is the energy used as own consumption in the generation of the energy. Table 3 shows the values used for the energy balance in 2007. For the 2030 scenarios, EImp and EExp were not considered as there is not any reliable forecast for the interchange of power between Spain and neighbor countries, EPum were assumed proportional to the energy obtained by hydropower, and EOC was also proportional but to the total energy required. Finally, in the third step, the net distribution losses at high and medium voltage are considered using the ecoinvent v2.0 structure (ecoinvent 2008). The losses ratio of the available energy to the distributed energy at medium voltage was around 2.5% as previously cited and was used for both 2007 and 2030 scenarios. 3.1.2 Modeled PV energy systems Pacca et al. (2007) stated that there are four main factors affecting the environmental performance of PV modules: solar irradiation, efficiency (conversion of sunlight), lifetime and energy consumption, and fuel mix employed in the manufacturing process. For the PV systems, a used phase model was used to convert a set of the first three key parameters: solar irradiation, efficiency, and module lifetime plus performance ratio into energy per unit of area, as expressed in Eq. 2: EPV GEf LTPV PR 2
proportional to the module efficiency and the ratio of the lifetimes of the PV modules and the inverters. Due to the wide range of ground mounting systems available in the market, 5 kg of steel and 2 kg of PVC per 1 m2 of module area were used, being these data compatible with (Mason et al. 2006). No environmental credits are obtained from metal parts or silicon recycling after PV modules dismantling (Jungbluth 2005; ecoinvent 2008). The models for the different PV modules production were taken from (ecoinvent 2008). The values of the PV parameters for 2007 for Spain were adopted among several sources (ASIF 2008; EPIA and Greenpeace 2008; Pfatischer 2008) and summarized in Table 4. A ground-mounted configuration with framed modules (except for CdTe) was adopted for the six PV technologies, and a mean annual irradiation in plane for Spain of 1,825 kWh(m2 year)1 was assumed: A weighted mean value was calculated considering the share of each autonomous communities in Spain for 2007 to PV power generation (ASIF 2008) and the irradiation over each community (PVGIS 2008). PV production data for c-Si modules come from 2004 (except 2005 for Siemens polysilicon and 2002 for metallurgical grade silicon); the production of c-Si by means of the Czochralski silicon ingots and later wafer sawing, cell, and module production processes are supplied by UCTE electricity using 2004 data. For CdTe, data are from 2006 (using the German grid mix for 2004) and for CIGS from 2007 (using also the German grid mix for 2004). 3.2 Description of the prospected scenarios 3.2.1 Power grid mix scenarios The main content of UNESAs Outlook for Electricity Generation for 2030 (UNESA 2007) report is the assessment of the future electric generation mix in Spain based on the established objectives for the planning of the generation, the objectives of the European and Spanish energy policy, and the possible evolution of the Spanish power generation stations under different scenarios. This report was externally reviewed by the Electric Power Research
where G is the annual solar irradiation on a plane over the selected location, Ef is the efficiency for the solar module, LTPV is the lifetime assumed for the PV module, and PR is the performance ratio (correction factor to consider deviation from ideal conditions: dust, shadowing effects, etc.). In Eq. 2, it is assumed that energy production is based on the irradiation on a plane, and a degradation rate of 0.5% per year was used to annualize the total power given the module in its corresponding lifetime. The fuel mix employed was based on the background data taken from (ecoinvent 2008). The number of inverters of 500 kWp required for each installed kWp of PV module is directly
Table 4 Main PV parameters in 2007 and 2030
2007 Ef PR 78 78 78 78 78 78 LTPV 30 30 30 30 30 30 LTINV 20 20 20 20 20 20
2030 Ef 25 25 20 15 15 15 PR 83 83 83 83 83 83 LTPV 35 35 35 30 30 30 LTINV 30 30 30 30 30 30
Values of module efficiency and performance ratio expressed as percentage. Values of lifetime of modules and inverters expressed as years Ef module efficiency, PR performance ratio, LTPV PV module lifetime, LTINV inverter lifetime
c-Si mc-Si Ribbon-Si a-Si CIGS CdTe
15 13 12 7 10 9
Institute, which confirmed the technical assumptions and hypotheses presented by UNESA. Therefore, the different envisaged scenarios guarantee the reliability of the present work. The methodology to build the different scenarios consider the future power demand, the current installed stations, the confirmed and planned connection of new stations to the grid up to 2013, the phase out of old stations, and the stations to produce renewable energy under the plan of renewable energies in Spain (IDAE 2005). More details can be found in UNESA (2007). These scenarios to meet the future energy demand in Spain are now summarized: 1. Maximum usage of current stations (MUS): The extra power demand is supplied by the planned stations for 2013. Base load and peak power demand are supplied essentially by natural gas 2. Nuclear expansion (NE): A strong expansion of the nuclear share is envisaged to meet the base load demand. Natural gas is used for peak power demand 3. Maximum penetration of wind power (MPW): High penetration of renewable energies (specially wind power) to help base load and peak power demand 4. Carbon capture (CC): Coal keeps a relative important share in the grid mix. Hard coal power plants are equipped with CCS stations 5. Carbon capture combined with nuclear expansion (CCNE): Coal combustion equipped with CCS stations and nuclear energy are combined to supply the base load demand Because of the uncertainty in the preferred fossil fuel in the future due to fluctuations in the prices of CO2 in the emission trade market and prices of raw fuels, two different assumptions were considered: natural gas as preferred fuel (NGP) and coal as preferred (CP) which led to nine different scenarios (the CC scenario is not considered within the NGP assumption). The 2007 and 2030 scenarios shares of technologies for power generation are summarized in Table 1. The total electric energy at grid EM for 2007 was 297 TWh (REE 2008). From UNESA (2007), a total of 428 TWh will be required to meet the electricity demand in 2030. From Table 1, it is noticeable that all of envisaged scenarios expect to reduce the CO2-eq. emissions from current levels to meet the Kyotos Protocol objectives for Spain: This fact is clearly shown in the phase out of hard coal, lignite, and fuel oil plants and the commitment with renewable energies. As there are no estimates about the future exchanges with neighboring countries, the selfsufficiency is assumed for Spain as a first step. 3.2.2 PV power scenario A set of parameters related to PV modules for 2030 from several data sources (Frankl et al. 2005; NREL 2007a, b,
c, d; Morales-Acevedo 2006; EUPVTP 2007; Raugei and Frankl 2009) are included in Table 4, considering all those parameters used in Eq. 2 for EPV. In order to quantify future improvements in manufacturing processes of PV modules, a general reduction of 20% in materials and energy required per 1 m2 of module area was applied (Frankl et al. 2005). No modification of annual irradiation is considered.
4 Results and discussion GaBi 4 software (GaBi 2008) was used to build a LCA model and quantify the CO2-eq. emissions for all energy systems when supplying the energy required by the PSEO process. These CO2-eq. emissions were assessed using the global warming equivalence factors proposed in the CML2001 methodology (implemented in GaBi 4), which are based on the IPCC equivalence factors for 100 years (with updated factors for 2007). The 2007 updated available data for the Spanish grid mix is reported in Table 1 and used to assess the current CO2-eq. emissions (REE 2008). From Fig. 2, in Spain 2007, 0.511 kg CO2-eq. kWh1 at medium voltage was released in the life cycle considering all the previous hypotheses for Spain in the year 2007. This value is about 14% higher than the direct emissions reported for electricity production in the same period (0.450 kg CO2 kWh1; SGE 2008), which really fits the percentage of life cycle emissions over direct emissions typically considered around 1015% higher. On the other hand, the nine considered scenarios proposed reductions in the CO2-eq. emissions, which range from 53% to 69% versus 2007 values. This improvement is based in the progressive substitution of hard coal, lignite, and fuel oil power plants for natural gas and wind power plants. Of course, the lowest values from Fig. 2 (0.159 and 0.165 kg CO2-eq.kWh1) were obtained for the scenarios MPW-NGP and MPW-CP, in which the energy demand is met by an important contribution of renewable energies, specially wind power (total share of 40%), being natural gas used for both the baseline and peak demand. Values up to 0.208 and 0.201 kg CO2-eq.kWh1 were obtained, respectively, for CC-CP and CC-NE-CP scenarios as shown in Fig. 3, which are those whose share of hard coal to the grid mix remain relevant (11% and 7%, respectively, compared with the 21% in 2007). Assuming the same probability for each scenario, a mean reduction of 62% is expected for all the NGP scenarios and of 61% for the CP scenarios. Therefore, significant reductions are expected to happen in Spain for CO2-eq. emissions coming from the power generation sector under conditions assumed in this work and based on currently available references.
Int J Life Cycle Assess Fig. 2 Emissions from the Spanish grid mix for the 2007 and 2030 scenarios. Values expressed as kilograms of CO2-eq.per kilowatt hour
0.5
Reference scenario for 2007
Emissions from the Spanish grid mix (kg CO2 -eq.kWh-1 )
0.4
0.3
Natural Gas preferred scenarios for 2030
Coal preferred scenarios for 2030
0.2
0.1
Ref. 2007 MUS-NGP NE-NGP MPW-NGP CC-NE-NGP MUS-CP
NE-CP
MPW-CP
CC-CP
CC-NE-CP
Emissions from the Spanish PV power plants (kg CO2 kWh-1 )
Fig. 3 Emissions from the Spanish PV power plants for the 2007 and 2030 scenarios. Values expressed as kilograms of CO2-eq.per kilowatt hour. Colored bars represent values without degradation, and the corresponding black bar represents the value assuming a degradation rate of 0.5% per year: a-Si, CdTe, CIGS, mc-Si, c-Si, Ribbon-Si
0.045
0.04
0.035
0.03
0.025
0.02
0.015
0.01
0.005
Ref. 2007
Only improvements in PV param
Improvements in PV param + 20% red
As the power generation is due to two main technologies, wind power and natural gas, four main hypotheses had to be assumed: 1. Improvements performed in the manufacturing process of wind power stations are not considered. Consequently, environmental improvements related to a greener grid power for a more sustainable manufacturing process were not computed. 2. The emission factors of combined cycle stations and natural gas burners are critical for the study. A prospective study for those technologies is not considered, so it must be highlighted that lower emission factors (as previously cited 0.425 kg CO2 kWh1 for best combined cycle and 0.515 kg CO2 kWh1 for natural gas burners (ecoinvent 2008)) could be expected and consequently lower CO2-eq. emissions could arise. 3. No CCS stations are incorporated together with natural gas combined cycles or cogeneration. This is due to the fact that the original reference for prospected scenarios (SGE 2008) reports that CCS stations are only integrated in coal stations. Weisser (2007) reviewed emissions from CCS stations, reporting values between 0.0920.145 kg CO2-eq.kWh1 for pulverized coal plants, 0.0650.152 kg CO2-eq. kWh1 for IGCC plants, and 0.0400.066 kg CO2-eq.kWh1 for combined cycle gas turbine plants. Viebahn et al. (2007) reported values below 0.200 kg CO2-eq.kWh1 for pulverized hard coal, pulverized lignite, NGCC, and IGCC technologies equipped with CCS (reaching around 0.150 kg CO2-eq.kWh1 in IGCC plants with CCS). Odeh and Cockerill (2008) reviewed different life cycle analysis of power generation stations with CCS and reported values below 0.250 kg CO2-eq.kWh1 from several authors, pointing out that reductions up to 0.160 kg CO2-eq.kWh1 were possible depending upon the chosen technology. Pehnt and Henkel (2009) also reported values below 0.200 kg CO2-eq.kWh1 for an IGCC station equipped with CCS, based on Selexol and without considering CO2 leakages (this reference was used for the inventory). Consequently, it is expected that, if more demanding measures are considered in a close future, it is reasonable to consider a greater penetration of CCS stations also in NGCC plants, so the expected emissions could be even lower than those reported previously. 4. Dynamic criteria in the background data are not considered. Pehnt (2006) suggested that different estimations can be done for critical parameters affecting the life cycle performance of a system product so it is possible to forecast the future impact. However, in this work, for both energy supplying systems, it was
considered that future scenarios for grid power and PV systems rely on the most updated data from (ecoinvent 2008) in the upstream processes, which is analogous to consider that the power generation in 2030 is based on emissions factors and efficiencies of 2004 and that the PV systems are produced with 2004 energy and materials (date of inventory data on ecoinvent v2.0 database). That leads to the fact that a worst case scenario is assumed and the expected environmental performance should be better than concluded here. Additionally, it seems logical that those values could be also lower if it is considered that renewable energies such as solar thermoelectric are not considered. Therefore, values presented here for the CO2-eq. emissions must be interpreted as a worst case situation as all the presented hypotheses lead to improvements in the environmental performance of both power generation from grid and from PV power plants: An improvement in all upstream processes is of course expected taking into account current global environmental status and legislation. Results for PV power plants in Spain are reported in Fig. 3. Values between 0.026 and 0.033 kg CO2-eq.kWh1 were obtained for the different PV technologies (except CdTe due to the less energy-intensive production process and frameless assumption). For the wafer silicon-based, silicon ribbon, and CdTe technologies, proposed values agree with those reported by Fthenakis et al. (2008), as both studies used ecoinvent as background data. Values between 0.052 and 0.072 kg CO2-eq.kWh1 were obtained for crystalline modules by Raugei et al. (2007b). These authors report values of 0.017 kg CO2-eq.kWh1 for frameless CdTe technology: Divergence in reported values is possible as it depends on the different assumptions made in the goal and scope definition step (also different assumptions could lead to similar final values). For very large-scale PV systems, Ito et al. (2008) reported values of 0.0121, 0.0094, 0.0156, 0.0128, and 0.0105 kg CO2-eq.kWh1 for typical efficiency mc-Si, high efficiency mc-Si, a-Si, CdTe, and CIGS modules, respectively: These values are half those presented in Fig. 3, which means that operating under high irradiation in very large-scale systems reduces the value of the environmental performance expressed as kilograms of CO2-eq.per kilowatt hour. As the PSEO process does not need the use of inverters, previous values shown in Fig. 3 were also assessed assuming no inverters in order to obtain 1 kWh and reductions in the order of 2 3.5% were obtained when the inverter were removed. The future CO2-eq. emissions from selected technologies in 2030 considered two separated steps for a better comprehension of results. In the first step, only the improvements from the set of PV parameters in Table 4
affecting energy performance EPV were considered. These reductions are in the range of 3560%, which is reasonable as the set of future PV parameters are only slightly higher than the current values except for efficiency, for which the values are almost twofold. When the reduction of 20% in energy and materials consumption per 1 m2 of module area is also considered (second step), the reduction went up around to 5065%. Consequently, this reduction in energy and materials may be interesting from a perspective of production costs but with a relatively low impact if compared with making twofold the efficiency of the module. Although the different assumptions are made to build the future scenarios, values in the range 0.008 0.016 kg CO2-eq.kWh1 were obtained, being not really different from others references (Raugei et al. 2007a, b; Raugei and Frankl 2009) that reported values in the same range. The effect of considering a degradation rate of 0.5% per year in the modules lifetime was also presented in Fig. 3 (black bars): The increases in the thin film PV technologies are around 7% and 9% for the wafer siliconbase and silicon ribbon PV technologies, which are due to the lower relative increase of the PV efficiencies and lifetimes of the former technologies. Consequently, it is clear that emissions from grid power in scenarios for 2030 are at different magnitude orders, so the ratio between emissions from grid power (0.159 0.238 kg CO2-eq.kWh1) and from PV systems (0.008 0.016 kg CO2-eq.kWh1 with the 20% reduction and no degradation and 0.0090.017 kg CO2-eq.kWh1 with the 20% reduction and degradation) assuming mean values for the different scenarios and PV technologies are around 17 16, respectively, so that means PSEO process should be considered as a more sustainable option when compared versus supply from grid. This statement is true when Spain is considered as frame for boundary conditions due to the annual irradiation value; however, in those countries with lower irradiation values or with a lower intensity in CO2-eq. per kilowatt hour in the grid mix (such as Norway, with a negligible contribution (Stoppato 2008)), a more detailed study must be performed. 5 Conclusions, recommendations, and perspectives Providing that the aim of this work is to compare the grid power and PV power for the 2030 timeframe in terms of CO2-eq. emissions as supply for a PSEO process, it is clear from this work that, also for the most green grid power scenario MPW-NGP whose emissions are 13 times higher than the average value of the future PV emissions (considering 0.5% per year degradation and 20% reduction in materials and energy required per 1 m2 of module area), the direct use of a PV system based on any of the
considered available technologies to power PSEO process is a low-carbon intensive option. Consequently, this prospect should recognize the PSEO process, which is powered by solar photovoltaic systems, as a sound option over the supply from the grid mix. Additionally, this technological option is more energy efficient due to the fact that the energy is produced in the same place where is consumed, avoiding the consequential transmission network losses.
Acknowledgment This research is financially supported by the Spanish Ministry of Science and Technology (Project CONSOLIDER CTM2006-00317) and the Project CENIT SOSTAQUA. A. Dominguez-Ramos thanks the Ministry of Innovation and Science for the FPU fellowship reference number AP-2005-1719.
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Universidad de Cantabria Escuela Tcnica Superior de Ingenieros Industriales y de Telecomunicacin Departamento de Ingeniera Qumica y Qumica Inorgnica

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Antonio Domnguez Ramos

Science Edition, cumpliendo con la normativa existente en la Universidad de Cantabria y en el

cleaner production: application to aluminium trifluoride. 1st International Congress on Green

Process Engineering. 2007. TOULOUSE (Francia). Internacional. Asistencia. Comunicacin oral

impact assessment: application to process engineering. 3rd International Conference on Life

in the Life Cycle Assessment of Aluminium Trifluoride. European Congress of Chemical

Engineering - 6. 2007. COPENHAGEN (Dinamarca). Internacional. Asistencia. Comunicacin

organic carbon treatment using electrochemical oxidation. XVIII International Conference on

Chemical Reactors CHEMREACTOR-18. 2008. LA VALLETA (Malta). Internacional. Comunicacin

Internacional de Anlisis de Ciclo de Vida en Latinoamrica. 2009. PUCN (Chile).

Normalization of Industrial Processes. 19th European Symposium on Computer Aided Process

Chemical Engineering. 2009. MONTREAL (Canad). Internacional. Comunicacin oral

assessment (LCA) of electric energy in municipal wastewater treatment plants. European

photovoltaic modules manufacture. European Symposium on Computer Aided Process

Produccin: Intensificacin e integracin de procesos en la industria qumica y transformadora

ndice RESUMEN / ABSTRACT 1

Electro-oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

2.4 Referencias del captulo 2 2.5 Nomenclatura del captulo 2

CAPTULO 3. CONCLUSIONES / CHAP TER 3. CONCLUSIONS 3.1 Conclusiones y trabajo futuro

3.1 Conclusions and future work

CAPTULO 4. ARTCULOS CIENTFICOS / CHAPTER

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

1.1 La tecnologa de Electro-Oxidacin para el tratamiento de aguas residuales

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Glucosa Polihidroxibencenos Histidina

Lavado de coches Industria del motor

Panizza et al., 2005 Kraft et al., 2003

1.2 Integracin de Energa Solar Fotovoltaica en la tecnologa de Electro-Oxidacin

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Valero et al., 2008

Oxidacin con reactivo Fenton

Si (con regulador de voltaje)

1x Mdulo solar (50 W; 17 V; 2.9 A; Syscom Inc. Modelo BP 350U)

Figueroa et al., 2009

Energa debida a reactivos qumicos y gestin de lodos (kWhm-3) RL 0 0 0 0

Emisiones de kgCO2-eq.kWh-1 (kgCO2-eq.kWh-1) 0,5 0,5 0,5 0,05 0,05

Total de emisiones como kgCO2-eq.m-3 (kgCO2-eq.m-3) 0,35+RL0,5 5 50 0,5 5

0,7 10 100 10 100

RL es la energa asociada a los reactivos qumicos y a la gestin de lodos (kWhm )

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

1.4 Aplicacin del proceso ESOF

INTEGRACIN DE PROCESOS ELECTROOXIDACIN SOLAR FOTOVOLTAICA

energa renovable en tratamientos de agua.

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

1.6 Referencias del captulo 1

Water Sci. Technol. 2006, 54, 207

Res. 2002, 41, 4187

J. Chem. Tech. Biotechnol. 2006a, 81, 1331

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Tech. Biotechnol. 2006e, 81, 352

Sci. 2001, 18, 369

Manage. 2007, 27, 380

Technol. 2008, 42, 2168

J. Photochem. Photobiol. A 2004, 164, 3

Hazard. Mater. 2007, 142, 250

Photobio. A 2003, 155, 231

Electro-Oxidacin Solar Fotovoltaica (ESOF) de aguas residuales con carga orgnica

Sci. 2006, 274, 138