Biokerosene from coconut, babassu, camelina and palm kernel oils: production and properties of their blends with fossil kerosene

On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights [European Union Emissions Trading System, EUETS). On July 8th 2009, the European Parliament and Conseil agreed that all flights leaving or landing in the EU airports starting from January 1st 2012 should be included in the EUETS. On November 19th 2008, the EU Directive 2008/101/CE [1] included the civil aviation activities in the EUETS, and this directive was transposed by the Spanish law 13/2010 of July 5th 2010 [2]. Thus, in 2012 the aviation sector should reduce their emissions to 97 % of the mean values registered in the period 2004-2006, and for 2013 these emission reductions should reach 95 % of the mean values for that same period. Trying to face this situation, the aviation companies are planning seriously the use of alternative jet fuels to reduce their greenhouse gas emissions and to lower their costs. However, some US airlines have issued a lawsuit before the European Court of Justice based in that this EU action violates a long standing worldwide aviation treaty, the Chicago convention of 1944, and also the Chinese aviation companies have rejected to pay any EU carbon dioxide tax [3]. Moreover, the USA Departments of Agriculture and Energy and the Navy will invest a total of up to $150 million over three years to spur production of aviation and marine biofuels for commercial and military applications [4]. However, the jet fuels should fulfill a set of extraordinarily sensitive properties to guarantee the safety of planes and passengers during all the flights.

PAH occurrence during combustion of biodiesel from various feedstocks

PAHs are pollutants of concern since they are known carcinogenic compounds. Their occurrence is mainly related to combustion or pyrolysis of organic matter such as fossil fuels. In the current scenario where biofuels are growingly important, it is also necessary to characterize PAH emissions due to their combustion. There are a number of works concerning PAH emissions from biodiesel combustion in Diesel engines, however, there are few regarding the difference between them depending on the feedstock and type of alcohol used in the transesterification. The authors have processed and characterized biodiesel from several feedstocks (Le. tallow, palm, rapeseed, soy-bean, coconut, peanut and linseed oils) to obtain FAME and FAEE and they have developed a method to measure the PAHs originated during their combustion in a bomb calorimeter. The tests have been carried out under different oxygen pressure conditions, and samples have been c1eaned from the bomb after each one of these tests. The samples have been prepared for GC-MS analysis, where PAH quantities among some other combustion products have been assessed. This work shows statistical relations obtained between the measured amounts of 18 PAHs of concern and the composition (oil and type of alcohol) used to obtain the biodiesel, and also the oxygen pressure during combustion.

Methodology to assess EU Biofuel Policies: The CAPRI Approach

This report is based on the outcome of a study carried out by the European Commission's Joint Research Centre - Institute for Prospective Technological Studies (JRC-IPTS, Spain) in cooperation with EuroCARE (Bonn, Germany). The report provides a detailed description of the methodology developed to assess the implications of the European Renewable Energy Directive on the agricultural sector, with an explicit focus on regional effects of biofuel targets in the EU. For the analysis, the spatial agricultural sector model CAPRI has been extended to include a global representation of biofuel markets (with endogenous supply, demand and trade flows for biofuels and biofuel feedstocks) while keeping the focus on regional impacts in the EU. The model is capable to simulate the impacts of EU biofuel policies on food production and prices, the potential use of by-products in the feed chain, the increasing pressure on marginal and idle land and the share of imported biofuels (self-sufficiency indicators). CAPRI is now able to jointly assess biofuel and agricultural policies, including policy instruments defined at the Member State level. The CAPRI biofuel module allows for a detailed analysis of most relevant biofuel support instruments like consumer tax exemptions, quota obligations, import tariffs and other trade measures. Additionally, the model allows for analysing scenarios regarding technical progress in 2nd generation technologies for biofuels.

Impacts of the EU Biofuel Target on Agricultural Markets and Land Use - A Comparative Modelling Assessment

The Renewable Energy Directive (2009/28/EC) requires that 20% of the EU's energy needs should come from renewable sources by 2020, and includes a target for the transport sector of 10% from biofuels. This report analyses and discusses the global impacts of this biofuel target on agricultural production, markets and land use, as simulated by three agricultural sector models, AGLINK-COSIMO, ESIM and CAPRI. The impacts identified include higher EU production of ethanol and biodiesel, and of the crops used to produce them, as well as more imports of both biofuels. Trade flows of biofuel feedstocks also change to reflect greater EU demand, including a significant increase in vegetable oil imports. However, as the extra demand is small in world market terms, the impact on world market prices is limited. With the EU biofuel target, global use of land for crop cultivation is higher by 5.2 million hectares. About one quarter is area within the EU, some of which would otherwise have left agriculture.

Las nuevas medidas agroenergéticas mexicanas: un modelo microeconométrico para la evaluación de su impacto sobre los ecosistemas naturales en los estados de Hidalgo, Querétaro y Tamaulipas (México)

La ley para la Promoción y Desarrollo de Biocombustibles aprobada en México en 2007 permite la producción de bioetanol y biodiesel. Esta producción puede entrar en conflicto con la producción de alimentos y con los ecosistemas naturales y en esta tesis se desarrolla un modelo microeconométrico que puede servir de base para anticiparse a esos conflictos y para diseñar medidas de política agraria orientadas a potenciar la compatibilidad de la producción de biocombustibles con la de alimentos y con la conservación de los ecosistemas naturales. A partir de una muestra de explotaciones de tres Estados de México – Hidalgo, Querétaro y Tamaulipas- y de un modelo logit multinomial mixto, se estima la elasticidad de la superficie destinada a cultivos alimentarios respecto a cambios en los márgenes económicos de los cultivos agroenergéticos. Esa elasticidad resulta ser significativa. Mostramos que su estimación es útil para anticipar cambios en la superficie destinada a los cultivos alimentarios y a los forestales. Se evalúa el impacto de varios escenarios relativos a los márgenes brutos de los cultivos sobre las decisiones de los agricultores y se muestra la utilidad del modelo para detectar tendencias de cambio a largo plazo en la alternativa de cultivos, incluyendo los forestales. ABSTRACT The Law for the Promotion and Development of Biofuels in Mexico adopted in 2007 allows for the production of bioethanol and biodiesel. This production may conflict with food production and natural ecosystems and this thesis develops a microeconometric model that can serve as a basis to anticipate such conflicts and to implement agricultural policy measures designed to enhance the compatibility of biofuels with production food and natural ecosystems conservation. We estimate the elasticity of the area devoted to food crops with respect to changes in economic margins of energy crops, using a sample of farms in three states of Mexico - Hidalgo, Queretaro and Tamaulipas - , and a multinomial mixed logit model. We found that this elasticity is significant. And we show how it can be useful to anticipate changes in area under food crops and forests. The impact of various scenarios about gross margins on farmers' decisions is assessed and it is shown the usefulness of the model to detect trends of long-term change in the crops area, including forests.

Potencial de la producción de bioelectricidad de las Comarcas Agrarias de la Comunidad de Madrid en base a centeno y triticale

En el presente trabajo se estudia la producción potencial de biomasa procedente de los cultivos de centeno y triticale en las seis comarcas agrarias de la Comunidad de Madrid (CM) y la posibilidad de su aplicación a la producción de bioelectricidad en cada una de ellas. En primer lugar se realiza un estudio bibliográfico de la situación actual de la bioelectricidad. Uno de los principales datos a tener en cuenta es que en el PER 2011- 2020 se estima que el total de potencia eléctrica instalada a partir de biomasa en España en el año 2020 sea de 1.350 MW, unas dos veces y media la existente a finales de 2010. Además, se comenta el estado de la incentivación del uso de biomasa de cultivos energéticos para producción de electricidad, la cual se regula actualmente según el Real Decreto-ley 9/2013, de 12 de Julio, por el que se adoptaron medidas urgentes para garantizar la estabilidad financiera del sistema eléctrico, y se consideran los criterios de sostenibilidad en el uso de biocombustibles sólidos. Se realiza una caracterización de las seis comarcas agrarias que forman la Comunidad Autónoma de Madrid: Área Metropolitana, Campiña, Guadarrama, Lozoya- Somosierra, Sur-Occidental y Vegas, la cual consta de dos partes: una descripción de la climatología y otra de la distribución de la superficie dedicada a barbecho y cultivos herbáceos. Se hace una recopilación bibliográfica de los modelos de simulación más representativos de crecimiento de los cultivos (CERES y Cereal YES), así como de ensayos realizados con los cultivos de centeno y triticale para la producción de biomasa y de estudios efectuados mediante herramientas GIS y técnicas de análisis multicriterio para la ubicación de centrales de bioelectricidad y el estudio de la logística de la biomasa. Se propone un modelo de simulación de la productividad de biomasa de centeno y de triticale para la CM, que resulta de la combinación de un modelo de producción de grano en base a datos climatológicos y a la relación biomasa/grano media de ambos cultivos obtenida en una experiencia previa. Los modelos obtenidos responden a las siguientes ecuaciones (siendo TN = temperatura media normalizada a 9,9 ºC y PN = precipitación acumulada normalizada a 496,7 mm): - Producción biomasa centeno (t m.s./ha) = 2,785 * [1,078 * ln(TN + 2*PN) + 2,3256] - Producción biomasa triticale (t m.s./ha) = 2,595 * [2,4495 * ln(TN + 2*PN) + 2,6103] Posteriormente, aplicando los modelos desarrollados, se cuantifica el potencial de producción de biomasa de centeno y triticale en las distintas comarcas agrarias de la CM en cada uno de los escenarios establecidos, que se consideran según el uso de la superficie de barbecho de secano disponible (25%, 50%, 75% y 100%). Las producciones potenciales de biomasa, que se podrían alcanzar en la CM utilizando el 100% de la superficie de barbecho de secano, en base a los cultivos de centeno y triticale, se estimaron en 169.710,72 - 149.811,59 - 140.217,54 - 101.583,01 - 26.961,88 y 1.886,40 t anuales para las comarcas de Campiña - Vegas, Sur - Occidental - Área Metropolitana - Lozoya-Somosierra y Guadarrama, respectivamente. Se realiza un análisis multicriterio basado en la programación de compromiso para definir las comarcas agrarias con mejores características para la ubicación de centrales de bioelectricidad en base a los criterios de potencial de biomasa, infraestructura eléctrica, red de carreteras, espacios protegidos y superficie de núcleos urbanos. Al efectuar el análisis multicriterio, se obtiene la siguiente ordenación jerárquica en base a los criterios establecidos: Campiña, Sur Occidental, Vegas, Área Metropolitana, Lozoya-Somosierra y Guadarrama. Mediante la utilización de técnicas GIS se estudia la localización más conveniente de una central de bioelectricidad de 2,2 MW en cada una de las comarcas agrarias y según el uso de la superficie de barbecho de secano disponible (25%, 50%, 75% y 100%), siempre que exista potencial suficiente. Para el caso de la biomasa de centeno y de triticale en base seca se considera un PCI de 3500 kcal/kg, por lo que se necesitarán como mínimo 17.298,28 toneladas para satisfacer las necesidades de cada una de las centrales de 2,2 MW. Se analiza el potencial máximo de bioelectricidad en cada una de las comarcas agrarias en base a los cultivos de centeno y triticale como productores de biomasa. Según se considere el 25% o el 100% del barbecho de secano para producción de biomasa, la potencia máxima de bioelectricidad que se podría instalar en cada una de las comarcas agrarias variaría entre 5,4 y 21,58 MW en la comarca Campiña, entre 4,76 y 19,05 MW en la comarca Vegas, entre 4,46 y 17,83 MW en la comarca Sur Occidental, entre 3,23 y 12,92 MW en la comarca Área Metropolitana, entre 0,86 y 3,43 MW en la comarca Lozoya Somosierra y entre 0,06 y 0,24 MW en la comarca Guadarrama. La potencia total que se podría instalar en la CM a partir de la biomasa de centeno y triticale podría variar entre 18,76 y 75,06 MW según que se utilice el 25% o el 100% de las tierras de barbecho de secano para su cultivo. ABSTRACT In this work is studied the potential biomass production from rye and triticale crops in the six Madrid Community (MC) agricultural regions and the possibility of its application to the bioelectricity production in each of them. First is performed a bibliographical study of the current situation of bioelectricity. One of the main elements to be considered is that in the PER 2011-2020 is estimated that the total installed electric power from biomass in Spain in 2020 was 1.350 MW, about two and a half times as at end 2010. Also is discussed the status of enhancing the use of biomass energy crops for electricity production, which is currently regulated according to the Real Decreto-ley 9/2013, of July 12, by which urgent measures were adopted to ensure financial stability of the electrical system, and there are considered the sustainability criteria in the use of solid biofuels. A characterization of the six Madrid Community agricultural regions is carried out: Area Metropolitana, Campiña, Guadarrama, Lozoya-Somosierra, Sur-Occidental and Vegas, which consists of two parts: a description of the climatology and another about the distribution of the area under fallow and arable crops. It makes a bibliographic compilation of the most representative crop growth simulation models (CERES and Cereal YES), as well as trials carried out with rye and triticale crops for biomass production and studies conducted by GIS tools and techniques multicriteria analysis for the location of bioelectricity centrals and the study of the logistics of biomass. Is proposed a biomass productivity simulation model for rye and triticale for MC that results from the combination of grain production model based on climatological data and the average relative biomass/grain of both crops obtained in a prior experience. The models obtained correspond to the following equations (where TN = normalized average temperature and PN = normalized accumulated precipitation): - Production rye biomass (t d.m./ha) = 2.785 * [1.078 * ln (TN + 2*PN) + 2.3256] - Production triticale biomass (t d.m./ha) = 2,595 * [2.4495 * ln (TN + 2*PN) + 2.6103] Subsequently, applying the developed models, the biomass potential of the MC agricultural regions is quantified in each of the scenarios established, which are considered as the use of dry fallow area available (25%, 50%, 75 % and 100%). The potential biomass production that can be achieved within the MC using 100% of the rainfed fallow area based on rye and triticale crops, were estimated at 169.710,72 - 149.811,59 - 140.217,54 - 101.583,01 - 26.961,88 and 1.886,40 t annual for the regions of Campiña, Vegas, Sur Occidental, Area Metropolitana, Lozoya- Somosierra and Guadarrama, respectively. A multicriteria analysis is performed, based on compromise programming to define the agricultural regions with better features for the location of bioelectricity centrals, on the basis of biomass potential, electrical infrastructure, road network, protected areas and urban area criteria. Upon multicriteria analysis, is obtained the following hierarchical order based on criteria: Campiña, Sur Occidental, Vegas, Area Metropolitana, Lozoya-Somosierra and Guadarrama. Likewise, through the use of GIS techniques, the most suitable location for a 2,2 MW bioelectricity plant is studied in each of the agricultural regions and according to the use of dry fallow area available (25%, 50% , 75% and 100%), if there is sufficient potential. In the case of biomass rye and triticale dry basis is considered a PCI of 3500 kcal/kg, so it will take at least 17,298.28 t to satisfy the needs of each plant. Is analyzed the maximum bioelectricity potential on each of the agricultural regions on the basis of the rye and triticale crops as biomass producers. As deemed 25% or 100% dry fallow for biomass, the maximum bioelectricity potential varies between 5,4 and 21,58 MW in the Campiña region, between 4,76 and 19,05 MW in the Vegas region, between 4,46 and 17,83 MW in the Sur Occidental region, between 3,23 and 12,92 MW in the Area Metropolitana region, between 0,86 and 3,43 MW in the Lozoya-Somosierra region and between 0,06 and 0,24 MW in the Guadarrama region. The total power that could be installed in the CM from rye and triticale biomass could vary between 18.76 and 75.06 MW if is used the 25% or 100% of fallow land for rainfed crop.

Localización óptima de una planta de bioetanol a partir de tubérculos de pataca (Helianthus tuberosus l.) en la Cuenca del Duero

El objetivo del presente trabajo es determinar la localización óptima de una planta de producción de 30.000 m3/año de bioetanol a partir de tubérculos de pataca (Helianthus tuberosus L.) cultivada en regadío, en tierras de barbecho de la Cuenca Hidrográfica del Duero (CH Duero). Inicialmente se elaboró, a partir de datos bibliográficos, un modelo de producción de pataca en base a una ecuación de regresión que relaciona datos experimentales de rendimientos de variedades tardías con variables agroclimáticas. Así se obtuvo una función de producción basada en la cantidad de agua disponible (precipitación efectiva + dosis de riego) y en la radiación global acumulada en el periodo brotación‐senescencia del cultivo. A continuación se estima la superficie potencial de cultivo de pataca en la CH Duero a partir de la superficie arable en regadío cartografiada por el Sistema de Ocupación del Suelo (SIOSE), a la cual se le aplican, en base a los requerimientos del cultivo, unas restricciones climáticas, edafológicas, topográficas y logísticas mediante el uso de Sistemas de Información Geográfica (SIG). La proporción de superficie de regadío restringida se cuantifica a escala municipal con el fin de calcular la superficie de barbecho en regadío apta para el cultivo de pataca. A partir de las bases de datos georreferenciadas de precipitación, radiación global, y la dotación de agua para el riego de cultivos no específicos establecida en el Plan Hidrológico de la Cuenca del Duero a escala comarcal, se estimó la producción potencial de tubérculos de pataca sobre la superficie de barbecho de regadío según el modelo de producción elaborado. Así, en las 53.360 ha de barbecho en regadío aptas para el cultivo de pataca se podrían producir 3,8 Mt de tubérculos al año (80 % de humedad) (761.156 t ms/año) de los que se podría obtener 304.462 m3/año de bioetanol, considerando un rendimiento en la transformación de 12,5 kg mf/l de etanol. Se estiman los costes de las labores de cultivo de pataca así como los costes de la logística de suministro a una planta de transformación considerando una distancia media de transporte de 25 km, en base a las hojas de cálculo de utilización de aperos y maquinaria agrícola oficiales del Ministerio de Agricultura, Alimentación y Medio Ambiente (MAGRAMA). Considerando el balance de costes asociados a la producción de bioetanol (costes de transformación, distribución y transporte del producto, costes estructurales de la planta, ahorro de costes por la utilización de las vinazas generadas en el proceso como fertilizante y un beneficio industrial), se ha estimado que el coste de producción de bioetanol a partir de tubérculos de pataca asciende a 61,03 c€/l. Se calculan los beneficios fiscales para el Estado por el cultivo de 5.522 ha de pataca que suministren la materia prima necesaria para una planta de bioetanol de 30.000 m3/año, en concepto de cotizaciones a la Seguridad Social de los trabajadores, impuestos sobre el valor añadido de los productos consumidos, impuesto sobre sociedades y ahorro de las prestaciones por desempleo. Se obtuvieron unos beneficios fiscales de 10,25 c€ por litro de bioetanol producido. El coste de producción de bioetanol depende del rendimiento de tubérculos por hectárea y de la distancia de transporte desde las zonas de producción de la materia prima hasta la planta. Se calculó la distancia máxima de transporte para que el precio de coste del bioetanol producido sea competitivo con el precio de mercado del bioetanol. Como resultado se determinó que el precio del bioetanol (incluido un beneficio industrial del 15%) de la planta sería igual o inferior al precio de venta en el mercado (66,35 c€/l) con una distancia máxima de transporte de 25 km y un rendimiento mínimo del cultivo de 60,1 t mf/ha. Una vez conocido el área de influencia de la planta según la distancia de transporte máxima, se determinó la localización óptima de la planta de producción de bioetanol mediante un proceso de ubicación‐asignación realizado con SIG. Para ello se analizan los puntos candidatos a la ubicación de la planta según el cumplimiento de unos requerimientos técnicos establecidos (distancia a fuentes de suministro eléctrico y de recursos hídricos, distancia a estaciones de ferrocarril, distancia a núcleos urbanos y existencia de Espacios Naturales Protegidos) que minimizan la distancia de transporte maximizando la cantidad de biomasa disponible según la producción potencial estimada anteriormente. Por último, la superficie destinada al cultivo de pataca en el área de influencia de la planta se determina en base a un patrón de distribución del cultivo alrededor de una agroindustria. Dicho patrón se ha obtenido a partir del análisis del grado de ocupación del cultivo de la remolacha en función de la distancia de transporte a la planta azucarera de Miranda de Ebro (Burgos). El patrón resultante muestra que la relación entre el grado de ocupación del suelo por el cultivo y la distancia de transporte a la planta siguen una ecuación logística. La localización óptima que se ha obtenido mediante la metodología descrita se ubica en el municipio leonés de El Burgo Ranero, donde la producción potencial de tubérculos de pataca en la superficie de barbecho situada en un radio de acción de 25 km es de 375.665 t mf/año, superando las 375.000 t mf requeridas anualmente por la planta de bioetanol. ABSTRACT Jerusalem artichoke (Helianthus tuberosus L.) is a harsh crop with a high potential for biomass production. Its main use is related to bioethanol production from the carbohydrates, inulin mainly, accumulated in its tubers at the end of the crop cycle. The aerial biomass could be used as solid biofuel to provide energy to the bioethanol production process. Therefore, Jerusalem artichoke is a promising crop as feedstock for biofuel production in order to achieve the biofuels consumption objectives established by the Government of Spain (PER 2011‐2020 and RDL 4/2013) and the European Union (Directive 2009/28/EC). This work aims at the determination of the optimal location for a 30,000 m3/year bioethanol production plant from Jerusalem artichoke tubers in the Duero river basin. With this purpose, a crop production model was developed by means of a regression equation that relates experimental yield data of late Jerusalem artichoke varieties with pedo‐climatic parameters from a bibliographic data matrix. The resulting crop production model was based on the crop water availability (including effective rainfall and irrigation water supplied) and on global radiation accumulated in the crop emergence‐senescence period. The crop potential cultivation area for Jerusalem artichoke in the Duero basin was estimated using the georeferenced irrigated arable land from the “Sistema de Ocupación del Suelo” (SIOSE) of Spain. Climatic, soil, slope and logistic restrictions were considered by means of Geographic Information Systems (GIS). The limited potential growing area was then applied to a municipality scale in order to calculate the amount of fallow land suitable for Jerusalem artichoke production. Rainfall and global radiation georeferenced layers as well as data of irrigation water supply for crop production (established within the Duero Hydrologic Plan) were use to estimate the potential production of Jerusalem artichoke tubers in the suitable fallow land according to the crop production model. As a result of this estimation, there are 53,360 ha of fallow land suitable for Jerusalem artichoke production in the Duero basin, where 3.8 M t fm/year could be produced. Considering a bioethanol processing yield of 12.5 kg mf per liter of bioethanol, the above mentioned tuber potential production could be processed in 304,462 m3/year of bioethanol. The Jerusalem crop production costs and the logistic supply costs (considering an average transport distance of 25 km) were estimated according to official agricultural machinery cost calculation sheets of the Minister of Agriculture of Spain (MAGRAMA). The bioethanol production cost from Jerusalem artichoke tubers was calculated considering bioethanol processing, transport and structural costs, industrial profits as well as plant cost savings from the use of vinasses as fertilizer. The resulting bioetanol production cost from Jerusalem artichoke tubers was 61.03 c€/l. Additionally, revenues for the state coffers regarding Social Security contributions, added value taxes of consumed raw materials, corporation tax and unemployment benefit savings due to the cultivation of 5,522 ha of Jerusalem artichoke for the 30.000 m3/year bioethanol plant supply were calculated. The calculated revenues amounted to 10.25 c€/l. Bioethanol production cost and consequently the bioethanol plant economic viability are strongly related to the crop yield as well as to road transport distance from feedstock production areas to the processing plant. The previously estimated bioethanol production cost was compared to the bioethanol market price in order to determine the maximum supply transport distance and the minimum crop yield to reach the bioethanol plant economic viability. The results showed that the proposed plant would be economically viable at a maximum transport distance of 25 km and at a crop yield not less than 60.1 t fm/ha. By means of a GIS location‐allocation analysis, the optimal bioethanol plant location was determined. Suitable candidates were detected according to several plant technical requirements (distance to power and water supply sources, distance to freight station, and distance to urban areas and to Natural Protected Areas). The optimal bioethanol plant location must minimize the supply transport distance whereas it maximizes the amount of available biomass according to the previously estimated biomass potential production. Lastly, the agricultural area around the bioethanol plant finally dedicated to Jerusalem artichoke cultivation was planned according to a crop distribution model. The crop distribution model was established from the analysis of the relation between the sugar beet (Beta vulgaris L.) cropping area and the road transport distance from the sugar processing plant of Miranda de Ebro (Burgos, North of Spain). The optimal location was situated in the municipality of ‘El Burgo Ranero’ in the province of León. The potential production of Jerusalem artichoke tubers in the fallow land within 25 km distance from the plant location was 375,665 t fm/year, which exceeds the amount of biomass yearly required by the bioethanol plant.

A theoretical study on the formation of iodine oxide aggregates and monohydrates

Biotic and abiotic emissions of molecular iodine and iodocarbons from the sea or the ice surface and the intertidal zone to the coastal/polar marine boundary layer lead to the formation of iodine oxides, which subsequently nucleate forming iodine oxide particles (IOPs). Although the link between coastal iodine emissions and ultrafine aerosol bursts is well established, the details of the nucleation mechanism have not yet been elucidated. In this paper, results of a theoretical study of a range of potentially relevant aggregation reactions of different iodine oxides, as well as complexation with water molecules, are reported. Thermochemical properties of these reactions are obtained from high level ab initio correlated calculations including spin–orbit corrections. The results show that the nucleation path most likely proceeds through dimerisation of I2O4. It is also shown that water can hinder gas-to-particle conversion to some extent, although complexation with key iodine oxides does not remove enough of these to stop IOP formation. A consistent picture of this process emerges from the theoretical study presented here and the findings of a new laboratory study reported in the accompanying paper (Gomez Martin et al., 2013).

Producción de biogás a partir de biomasa de la microalga scenedesmus sp. procedente de diferentes procesos

En este trabajo de Tesis Doctoral se ha estudiado la posibilidad de emplear las microalgas, concretamente el género Scenedesmus, como sustrato para la producción de biogás mediante digestión anaerobia, así como los residuos que se producen como consecuencia de su utilización industrial para diferentes fines. La utilización de las microalgas para la producción de biocombustibles es un tema de gran actualidad científica, en el que residen muchas expectativas para la producción a gran escala de biocombustibles que supongan una alternativa real a los combustibles fósiles. Existen numerosas investigaciones sobre la conversión a biogás de las microalgas, sin embargo aún hay poco conocimiento sobre la utilización de la digestión anaerobia como tratamiento de residuos de microalgas en un concepto de biorrefinería. Residuos que pueden ser generados tras la extracción de compuestos de alto valor añadido (p. ej. aminoácidos) o tras la generación de otro biocombustible (p. ej. biodiésel). Es en este aspecto en el que esta Tesis Doctoral destaca en cuanto a originalidad e innovación, ya que se ha centrado principalmente en tres posibilidades: - Empleo de Scenedesmus sp. como cultivo energético para la producción de biogás. - Tratamiento de residuos de Scenedesmus sp. generados tras la extracción de aminoácidos en un concepto de biorrefinería. - Tratamiento de los residuos de Scenedesmus sp. generados tras la extracción de lípidos en un concepto de biorrefinería. Los resultados obtenidos demuestran que la microalga Scenedesmus como cultivo energético para producción de biogás no es viable salvo que se empleen pretratamientos que aumenten la biodegradabilidad o se realice codigestión con otro sustrato. En este último caso, la chumbera (Opuntia maxima Mill.) ha resultado ser un sustrato idóneo para la codigestión con microalgas, aumentando la producción de biogás y metano hasta niveles superiores a 600 y 300 L kgSV-1, respectivamente. Por otro lado, el tratamiento de residuos generados tras la extracción de aminoácidos mediante digestión anaerobia es prometedor. Se obtuvieron elevados rendimientos de biogás y metano en las condiciones de operación óptimas (409 y 292 L kgSV-1, respectivamente). Aparte de la generación energética por medio el metano, que podría emplearse en la propia biorrefinería o venderse a la red eléctrica o de gas natural, reciclando el digerido y el CO2 del biogás se podría llegar a ahorrar alrededor del 30% del fertilizante mineral y el 25% del CO2 necesarios para el cultivo de nueva biomasa. Por lo tanto, la digestión anaerobia de los residuos de microalgas en un concepto de biorrefinería tiene un gran potencial y podría contribuir en gran medida al desarrollo de esta industria. Por último, una primera aproximación al tratamiento de residuos generados tras la extracción de lípidos muestra que éstos pueden ser empleados para la producción de biogás, como monosustrato, o en codigestión con glicerina, ya que son fácilmente biodegradables y el rendimiento potencial de metano puede alcanzar 218 LCH4 kgSV-1 y 262 LCH4 kg SV-1 en monodigestión o en codigestión con glicerina, respectivamente. ABSTRACT This PhD thesis explores the possibility of using microalgae, specifically the strain Scenedesmus, as substrate for biogas production through anaerobic digestion, as well as the residues generated after its use in different industrial processes. The use of microalgae for biofuels production is an emerging scientific issue. The possibility of producing biofuels from microalgae as a real alternative for fossil fuels is raising high expectations. There are several research projects on the conversion of microalgae to biogas; however, there is little knowledge about using anaerobic digestion for treating microalgae residues in a biorefinery scheme. These residues could be generated after the extraction of high value compounds (e.g. amino acids) or after the production of another biofuel (e.g. biodiesel). It is in this area in which this PhD thesis stands in terms of originality and innovation, since it has focused primarily on three possibilities: - The use of Scenedesmus sp. as an energy crop for biogas production. - Treatment of amino acid extracted Scenedesmus residues generated in a biorefinery. - Treatment of lipid extracted Scenedesmus residues generated in a biorefinery. The results obtained in this work show that the use of Scenedesmus as energy crop for biogas production is not viable. The application of pretreatments to increase biodegradability or the codigestion of Scenedesmus biomass with other substrate can improve the digestion process. In this latter case, prickly pear (Opuntia maxima Mill.) is an ideal substrate for its codigestion with microalgae, increasing biogas and methane yields up to more than 600 and 300 L kgVS-1, respectively. On the other hand, the treatment of residues generated after amino acid extraction through anaerobic digestion is promising. High biogas and methane yields were obtained (409 y 292 L kgVS-1, respectively). Besides the energy produced through methane, which could be used in the biorefinery or be sold to the power or natural gas grids, by recycling the digestate and the CO2 30% of fertilizer needs and 25% of CO2 needs could be saved to grow new microalgae biomass. Therefore, the anaerobic digestion of microalgae residues generated in biorefineries is promising and it could play an important role in the development of this industry. Finally, a first approach to the treatment of residues generated after lipid extraction showed that these residues could be used for the production of biogas, since they are highly biodegradable. The potential methane yield could reach 218 LCH4 kgVS-1 when they are monodigested, whereas the potential methane yield reached 262 LCH4 kgVS-1 when residues were codigested with residual glycerin.

Oxygen extended sooting index of FAME blends with aviation kerosene

The use of biofuels in the aviation sector has economic and environmental benefits. Among the options for the production of renewable jet fuels, hydroprocessed esters and fatty acids (HEFA) have received predominant attention in comparison with fatty acid methyl esters (FAME), which are not approved as additives for jet fuels. However, the presence of oxygen in methyl esters tends to reduce soot emissions and therefore particulate matter emissions. This sooting tendency is quantified in this work with an oxygen-extended sooting index, based on smoke point measurements. Results have shown considerable reduction in the sooting tendency for all biokerosenes (produced by transesterification and eventually distillation) with respect to fossil kerosenes. Among the tested biokerosenes, that made from palm kernel oil was the most effective one, and nondistilled methyl esters (from camelina and linseed oils) showed lower effectiveness than distilled biokerosenes to reduce the sooting tendency. These results may constitute an additional argument for the use of FAME’s as blend components of jet fuels. Other arguments were pointed out in previous publications, but some controversy has aroused over the use of these components. Some of the criticism was based on the fact that the methods used in our previous work are not approved for jet fuels in the standard methods and concluded that the use of FAME in any amount is, thus, inappropriate. However, some of the standard methods are not updated for considering oxygenated components (like the method for obtaining the lower heating value), and others are not precise enough (like the methods for measuring the freezing point), whereas some alternative methods may provide better reproducibility for oxygenated fuels.

Airplane materials compatibility with blends of fossil kerosene JET A1 with biokerosenes from babassu, palm kernel and coconut oils

The aviation companies are facing some problems that argue in favor of biofuels: Rising cost of traditional fuel: from 0.71 USD/gallon in May 2003 to 3.09 USD/gallon in January 2012. Environmental concerns: direct emissions from aviation account for about 3 % of the EU’s total greenhouse gas emissions. The International Civil Aviation Organization (ICAO) forecasts that by 2050 they could grow by a further 300-700 %. On December 20th 2006 the European Commission approved a law proposal to include the civil aviation sector in the European market of carbon dioxide emission rights (European Union Emissions Trading System, EUETS)

Dynamics of thermal ignition of spray flames in mixing layers

Conditions are identified under which analyses of laminar mixing layers can shed light on aspects of turbulent spray combustion. With this in mind, laminar spray-combustion models are formulated for both non-premixed and partially premixed systems. The laminar mixing layer separating a hot-air stream from a monodisperse spray carried by either an inert gas or air is investigated numerically and analytically in an effort to increase understanding of the ignition process leading to stabilization of high-speed spray combustion. The problem is formulated in an Eulerian framework, with the conservation equations written in the boundary-layer approximation and with a one-step Arrhenius model adopted for the chemistry description. The numerical integrations unveil two different types of ignition behaviour depending on the fuel availability in the reaction kernel, which in turn depends on the rates of droplet vaporization and fuel-vapour diffusion. When sufficient fuel is available near the hot boundary, as occurs when the thermochemical properties of heptane are employed for the fuel in the integrations, combustion is established through a precipitous temperature increase at a well-defined thermal-runaway location, a phenomenon that is amenable to a theoretical analysis based on activation-energy asymptotics, presented here, following earlier ideas developed in describing unsteady gaseous ignition in mixing layers. By way of contrast, when the amount of fuel vapour reaching the hot boundary is small, as is observed in the computations employing the thermochemical properties of methanol, the incipient chemical reaction gives rise to a slowly developing lean deflagration that consumes the available fuel as it propagates across the mixing layer towards the spray. The flame structure that develops downstream from the ignition point depends on the fuel considered and also on the spray carrier gas, with fuel sprays carried by air displaying either a lean deflagration bounding a region of distributed reaction or a distinct double-flame structure with a rich premixed flame on the spray side and a diffusion flame on the air side. Results are calculated for the distributions of mixture fraction and scalar dissipation rate across the mixing layer that reveal complexities that serve to identify differences between spray-flamelet and gaseous-flamelet problems.

Sostenibilidad de los biocombustibles para autoconsumo en un entorno rural

Se busca relacionar dos sectores que sin tener a priori nada en común, pueden verse beneficiados por una solución que mejore la situación de ambos. Hablamos del sector biocombustibles y del sector algodonero español. El sector de los biocombustibles ha visto un desarrollo espectacular en los últimos diez años, empujado por fuertes políticas gubernamentales. En general estas políticas buscan satisfacer una necesidad, la energía, mediante fórmulas que supongan un menor impacto medioambiental que las actuales. También una disminución de la dependencia exterior para el suministro de energía y otras ventajas. El sector algodonero español es un sector tradicional, que subsiste gracias a las ayudas europeas, y que se ha visto fuertemente afectado por las reformas de esas subvenciones. Se caracteriza por estar en vías de amortizar fuertes inversiones en regadío, por ser viable en suelos con alta salinidad, y por el clima propio del sur de España. Al ser un cultivo no alimentario, se evita la controversia que suscita la producción de cultivos energéticos en suelos factibles de ser usados para producción alimentaria. Se propone la sustitución del algodón por el ricino, cultivo muy experimentado en otros países (Colombia, Ecuador, Argentina, Brasil, Chile e India) y que tendría buena acogida en la tierra andaluza. Se analizan las características del nuevo cultivo y su adecuación para esta región. Se estudian los procesos necesarios para la extracción del aceite y su procesamiento a biodiesel, con el dimensionamiento de los equipos necesarios. Por último, se realiza un estudio económico de la propuesta, haciendo hincapié en los beneficios económicos que se obtienen por la vía del ahorro, tanto en ayudas de la PAC (Política Agraria Común) de la UE (Unión Europea), cómo por la disponer de un producto, biodiesel, que de otro modo deberíamos satisfacer mediante la compra de combustible tradicional. Abstract This Project looks forward the relationship between two different sectors with different troubles in Spain, which could be benefited by a common solution. We are talking about biofuels and the cotton industry. The biofuels sector has been developed along the last ten years because of strong governmental policies. These policies try to find how to supply energy, with the less environmental impact, as well as to decrease the dependency of third countries, and other benefits. The Spanish cotton industry is traditional, it has survived because of the European grants, and it is passing through an uncertain scenario because of the alteration of these grants. It is characterized by the non amortized investment in irrigation, by the high salinity ratio in the ground (which means that is unable for a number of crops), and by weather of this Spanish region. As well as cotton is not a food crop, the controversial of to plant energetic crops in areas able to produce food is avoided. It is aimed to replace cotton with castor, an oilseed which has been experienced in other countries (Colombia, Ecuador, Argentina, Brazil, Chile e India) and which could be accepted in that ground. It is analyzed the main features of the new drop and its ability to be planted in this area. The processes to obtain the oil and then the biofuel are studied. The equipment is sized. At least, it is developed an economic survey about the proposal, deepening in the benefits which are obtained because of savings, in European grants and in diesel.

The role of the secondary cell wall in plant resistance to pathogens

Plant resistance to pathogens relies on a complex network of constitutive and inducible defensive barriers. The plant cell wall is one of the barriers that pathogens need to overcome to successfully colonize plant tissues. The traditional view of the plant cell wall as a passive barrier has evolved to a concept that considers the wall as a dynamic structure that regulates both constitutive and inducible defense mechanisms, and as a source of signaling molecules that trigger immune responses. The secondary cell walls of plants also represent a carbon-neutral feedstock (lignocellulosic biomass) for the production of biofuels and biomaterials. Therefore, engineering plants with improved secondary cell wall characteristics is an interesting strategy to ease the processing of lignocellulosic biomass in the biorefinery. However, modification of the integrity of the cell wall by impairment of proteins required for its biosynthesis or remodeling may impact the plants resistance to pathogens. This review summarizes our understanding of the role of the plant cell wall in pathogen resistance with a focus on the contribution of lignin to this biological process.

A proposal for pellet production from residual woody biomass in the island of Majorca (Spain)

The use of residual biomass for energy purposes is of great interest in isolated areas like Majorca for waste reduction, energy sufficiency and renewable energies development. In addition, densification processes lead to easy-to-automate solid biofuels which additionally have higher energy density. The present study aims at (i) the estimation of the potential of residual biomass from woody crops as well as from agri-food and wood industries in Majorca, and (ii) the analysis of the optimal location of potential pellet plants by means of a GIS approach (location-allocation analysis) and a cost evaluation of the pellets production chain. The residual biomass potential from woody crops in Majorca Island was estimated at 35,874 metric tons dry matter (t DM) per year, while the wood and agri-food industries produced annually 21,494 t DM and 2717 t DM, respectively. Thus, there would be enough resource available for the installation of 10 pellet plants of 6400 t·year−1 capacity. These plants were optimally located throughout the island of Mallorca with a maximum threshold distance of 28 km for biomass transport from the production points. Values found for the biomass cost at the pellet plant ranged between 57.1 €·t−1 and 63.4 €·t−1 for biomass transport distance of 10 and 28 km. The cost of pelleting amounted to 56.7 €·t−1; adding the concepts of business fee, pellet transport and profit margin (15%), the total cost of pelleting was estimated at 116.6 €·t−1. The present study provides a proposal for pellet production from residual woody biomass that would supply up to 2.8% of the primary energy consumed by the domestic and services sector in the Balearic Islands.