Bioplásticos a partir de aguas residuales de la conserva

Tania Palmeiro Sáncheza,b, Andrea Fra Vázquezb, José Luis Camposc, Anuska Mosquera Corralb aDept. of Microbiology, School of Natural Sciences, National University of Ireland Galway, Ireland bInstituto de Investigaciones Tecnológicas & Escuela Técnica Superior de Ingeniería, Dpto. Ingeniería Química, Universidad de Santiago de Compostela, España cFaculty of Engineering and Science, University Adolfo Ibáñez, Avda. Padre Hurtado 750, Viña del Mar, Chile
Historia de los plásticos y problemática actual
El primer plástico sintético fue producido por primera vez en la historia en 1907 por Leo Hendrick Baekeland y tal compuesto se le conoce como bakelita. Este momento histórico marcó el nacimiento de la industria plástica tal y como la conocemos actualmente. La bakelita fue conocida en aquel momento como “el material de los mil usos”, ya que era buen aislante, duradera, resistente al calor y tenía un gran potencial para ser utilizada industrialmente en infinidad de aplicaciones debido a la facilidad con la que podía ser moldeada. El segundo gran salto en la industria plástica ocurrió con la Segunda Guerra Mundial, que priorizó y forzó la producción industrial de materiales alternativos a los naturales, debido a la limitada disponibilidad de estos últimos. Un buen ejemplo es el archiconocido Nylon®, inventado por Wallace Carothers y patentado por DuPont en 1935, y cuya manufactura se desarrolló enormemente durante la guerra ya que fue empleado en la fabricación de paracaídas y cuerdas, entre otros. Muchos otros plásticos también encontraron en la Segunda Guerra Mundial un empuje para su producción, como el PTFE (politetrafluoroetileno o más conocido como Teflón®) o el PMA (polimetilmetacrilato). Quizás la historia más agradable de contar sea la del ABS (acrilonitrilobutadienestireno), que se empezó a desarrollar como material antibalas y, entre otras aplicaciones, acabó siendo usado para fabricar los famosos bloques Lego® a partir de 1958. A principios de los años 60 la mayoría de los plásticos que conocemos y usamos en la actualidad habían sido sintetizados (Crawford and Quinn, 2017).
Hoy en día los plásticos tienen tal variedad de utilidades que ya se han convertido en materiales esenciales para nuestra vida cotidiana. Se emplean en construcción, embalaje, aplicaciones médicas, material deportivo y casi cualquier uso imaginable debido a sus múltiples propiedades. Esto se traduce en una producción mundial de 335 millones de toneladas durante el año 2016 (Plastics Europe, 2017) y con tendencia a seguir aumentando debido a la alta demanda existente en los países emergentes.
Es sorprendente ver como un material tan útil y polifacético, que llevamos usando a diario desde hace poco más de 50 años, ha logrado alcanzar unas tasas de contaminación tan altas. De hecho, un innovador estudio publicado a finales de 2017 por la Organización de las Naciones Unidas (ONU) contabiliza por primera vez en la historia los residuos del área mediterránea, siguiendo los compromisos establecidos en Barcelona 1976 con el Plan de Acción del Mediterráneo (MAP). Los resultados no pueden ser menos prometedores: más del 80% de la basura encontrada en las playas del Mediterráneo son plásticos, tendencia que se agudiza durante la temporada turística (United Nations Environment Programme, 2017). Este problema en la actualidad tiene su máximo exponente en la conocida como “Gran Mancha de Basura del Pacífico”, que es una acumulación de residuos flotantes, en su mayoría plásticos, que se pasea entre Japón y la costa oeste de Estados Unidos (Bryant et al., 2016).
La transición hacia los bioplásticos
Debido a estos inconvenientes, y sumados a las periódicas crisis del petróleo que llevan azotando la economía mundial desde 1973, los bioplásticos surgen como una posible alternativa a los plásticos convencionales (Crawford and Quinn, 2017, Ragauskas et al., 2006). Es importante destacar que no hay un acuerdo a la hora de definir los bioplásticos y que éstos pueden ser clasificados como biodegradables o de origen renovable, pero no tienen por qué cumplir ambas características simultáneamente (Ashter, 2016). Ejemplos de esto son Ecoflex® de BASF, considerado un bioplástico biodegradable procedente de crudo de petróleo, o la familia de las poliamidas, que son biopolímeros procedentes de una fuente renovable pero no son biodegradables. Cabe indicar que los autores del presente artículo consideran que el término “bioplástico” debería incluir ambos requisitos (origen renovable y 100% biodegradables), por lo que el presente estudio tiene en cuenta exclusivamente los polímeros de origen microbiano conocidos como polihidroxialcanoatos (PHA) (Figura 1). Esto se debe a que, en términos estrictos, los PHA son considerados por muchos autores como los únicos bioplásticos reales (Dias et al., 2006) puesto que, además de ser de origen renovable y completamente biodegradables, son los únicos compuestos que se polimerizan in vivo, mientras que otros polímeros de origen microbiano (ácido láctico o succínico, por ejemplo) se polimerizan in vitro (Chen, 2010).

Actualmente la síntesis de PHA se realiza industrialmente por empresas como Danimer Scientific, Kaneka, Bio-On o Tianjin GreenBio. Estos procesos industriales habitualmente implican el uso de cepas puras o incluso microorganismos genéticamente modificados capaces de acumular intracelularmente hasta un 90% en peso de biopolímero (Chen, 2010, Lemos et al., 2008). Los costes de producción suelen ser elevados (8-10€/kg bioplástico) debido a que hay que pagar por el sustrato además de mantener estéril el proceso (Reis et al., 2003, Serafim et al., 2008). Debido a todo esto, actualmente la investigación se ha abierto también hacia el empleo de cultivos microbianos mixtos en vez de cepas puras y el uso de residuos como materia prima para intentar abaratar el coste de producción en hasta un 50% (Reis et al., 2003). Con este objetivo, en el presente estudio se plantea el uso de aguas residuales de la industria conservera de atún en Galicia para la producción de bioplásticos.
Producción de bioplásticos en Galicia a partir de aguas residuales de conserva de atún
Según datos de ANFACO, la industria conservera gallega representa el 87% del volumen total de conservas producidas en España. Además, el 70% de esta producción son conservas de atún. Los números facilitados por ANFACO revelan una producción anual en Galicia de 160.000 toneladas en 2004 con unos ingresos superiores a los 450 millones de euros. Sin embargo, por otro lado, las aguas residuales vertidas por este sector generalmente presentan alta carga además de un relevante contenido en sal (Soto et al., 1990), lo que dificulta que puedan ser tratadas convencionalmente. La producción de bioplásticos en la industria conservera aportaría un doble beneficio: por una parte el tratamiento de un agua residual y por otra la obtención in-situ de un producto de alto valor añadido.
Técnicamente la producción de bioplásticos a partir de aguas residuales de conservera de túnidos consta de dos etapas: una primera etapa anaerobia donde el agua residual es fermentada en ácidos grasos y una segunda etapa aerobia donde esa agua fermentada se emplea como sustrato o alimento de los microorganismos productores de biopolímeros.
Etapa Anaerobia – Fermentación del agua residual
En esta primera etapa, el agua residual fue tratada anaeróbicamente para la producción de ácidos grasos volátiles (AGV), que son una forma de carbono orgánico rápidamente asimilable por los microorganismos acumuladores de biopolímeros y que además da lugar a los rendimientos más altos alcanzados hasta ahora (Fradinho et al., 2014, Marang et al., 2013).
El agua residual procedía directamente de los cocederos de atún, por lo que su carga orgánica era elevada (29.9 ± 2.6 g DQO/L, siendo DQO el acrónimo para la demanda química de oxígeno), así como la salinidad, de 22.4 ± 4.3 g NaCl/L.
El reactor a escala laboratorio con un volumen de 2 L operó como un reactor continuo completamente agitado a 150 rpm en rango mesofílico (aprox. 35 °C) con un tiempo de retención hidráulico de 2 días. La configuración del sistema puede verse en la Figura 2. En el diseño se incluyó una membrana para la separación de las fases sólida y líquida, siendo el concentrado la fracción rica en biomasa que se recircula al reactor y el permeado la fracción más rica en AGV, que es el sustrato de la etapa de producción de bioplásticos.

Una vez alcanzado el estado estacionario, la eliminación de materia orgánica alcanzó un valor medio del 87% junto con una composición de ácidos aproximada de 43.1% acético, 38.4% butírico, 12.6% propiónico y 5.9% valérico.
Etapa Aerobia – Obtención del biopolímero
La etapa aerobia a su vez se subdivide en otras dos: enriquecimiento y acumulación (Figura 3). En una primera fase, los microorganismos capaces de acumular biopolímeros necesitan ser seleccionados para aumentar su concentración en el medio. A esta etapa se le conoce como “enriquecimiento”. En la segunda fase, los microorganismos son alimentados indiscriminadamente con el único objetivo de aumentar la cantidad de biopolímero en su interior. Esta etapa se conoce como “acumulación”. En ambas fases se alimentaron los reactores con los ácidos producidos en la etapa anaerobia.

El enriquecimiento habitualmente se hace a partir de lodos activos de una depuradora convencional a una temperatura de 30 °C. El tiempo de retención hidráulico fue de 24 horas y se matuvo siempre igual al tiempo de retención celular. Para promover el crecimiento de microorganismos acumuladores se operó el reactor en secuencias periódicas de 12 horas (720 min) de alimentación (15 min) – reacción (675 min) – descarga (15 min) y siempre con aireación ininterrumpida. La particularidad de trabajar en secuencias es que permite una selección rápida de los microorganismos ya que la materia orgánica solo está presente durante un corto período de tiempo, lo que implica una ventaja para los microorganismos acumuladores de PHA, ya que pueden utilizar los biopolímeros acumulados para crecer aún cuando no hay materia orgánica presente en el medio.
La acumulación emplea los organismos descargados de la etapa de enriquecimiento para alimentarlos con mucha mayor cantidad de ácidos. Para ello se emplea un reactor alimentado por cargas, ya que los AGV en alta concentracióson inhibitorios para el proceso, a una temperatura de 30 °C y completamente aireado y agitado.
En el presente caso se logró una producción de PHA de 55.4 mg/(L • h). Esta producción es aproximadamente unas diez veces menor que el valor obtenido por otros autores estudiando aguas fermentadas de la industria papelera (Albuquerque et al., 2011). Esto es debido a dos factores: por un lado las elevadas concentraciones de amonio presentes en el agua fermentada debido a su riqueza protéica (4.0 ± 0.8 g NH4+/L) que favorecen el crecimiento de los microorganismos en comparación con la acumulación de biopolímero; y, por otro lado, las elevada concentración de sal en los reactores (entre 3 y 14 g NaCL/L, dependiendo de la cantidad de sustrato alimentado). De hecho, es la primera vez que se publica el uso de sustratos salinos fermentados para la producción de bioplásticos. Ensayos realizados sobre el efecto de la salinidad sobre la acumulación de PHA indicaron que la presencia de NaCl afectaba enormemente tanto a la acumulación como al tipo de biopolímero acumulado, encontrándose una inhibición del 50% a 5 g NaCl/L (Palmeiro-Sánchez et al., 2016a, Palmeiro-Sánchez et al., 2016b).
Retos, perspectivas y futuro trabajo
A la vista de los resultados, es posible afirmar la posibilidad de emplear aguas residuales fermentadas de conservera para la producción de biopolímeros a pesar de la evidente necesidad de optimizar el proceso. Una posible vía para mejorarlo sería el aumento de la concentración de sal en el reactor de enriquecimiento, lo que llevaría a una posible adaptación de la biomasa, y evitar así la inhibición observada (Palmeiro-Sánchez et al., 2016a). Además, el hecho de trabajar con microorganismos halofílicos haría posible reducir aún más los costes de producción ya que la extracción del bioplástico podría hacerse por choque osmótico con agua fresca, en vez de emplear otros métodos físicos o químicos que implican costes mucho más elevados (Quillaguaman et al., 2010). Además, varios autores han calculado que el proceso optimizado de producción de PHA sería más rentable y más ecológico que la obtención de biogás, con beneficios entre 20 y 50 veces superiores en función de variables de operación como por ejemplo la velocidad de carga orgánica (Gurieff and Lant, 2007, Reis et al., 2003).
Actualmente el reto ya no es demostrar la posibilidad de obtener bioplásticos a partir de residuos como los de la conservera o trabajar en condiciones inhibitorias. El reto está en optimizar el proceso para que sea rentable y pueda ser implantado en pequeñas empresas que quieran tratar sus aguas y obtener un producto útil en su industria. Actualmente los cuellos de botella estarían en aumentar el rendimiento del proceso y en la extracción del biopolímero (Jiang et al., 2012, Madkour et al., 2013).
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