Carbon dioxide sequestration in cement kiln dust through miner carbonation

The feasibility of carbon sequestration in cement kiln dust (CKD) was investigated in a series of batch and column experiments conducted under ambient temperature and pressure conditions. The significance of this work is the demonstration that alkaline wastes, such as CKD, are highly reactive with carbon dioxide (CO2). In the presence of water, CKD can sequester greater than 80% of its theoretical capacity for carbon without any amendments or modifications to the waste. Other mineral carbonation technologies for carbon sequestration rely on the use of mined mineral feedstocks as the source of oxides. The mining, pre-processing and reaction conditions needed to create favorable carbonation kinetics all require significant additions of energy to the system. Therefore, their actual net reduction in CO2 is uncertain. Many suitable alkaline wastes are produced at sites that also generate significant quantities of CO2. While independently, the reduction in CO2 emissions from mineral carbonation in CKD is small (~13% of process related emissions), when this technology is applied to similar wastes of other industries, the collective net reduction in emissions may be significant. The technical investigations presented in this dissertation progress from proof of feasibility through examination of the extent of sequestration in core samples taken from an aged CKD waste pile, to more fundamental batch and microscopy studies which analyze the rates and mechanisms controlling mineral carbonation reactions in a variety of fresh CKD types. Finally, the scale of the system was increased to assess the sequestration efficiency under more pilot or field-scale conditions and to clarify the importance of particle-scale processes under more dynamic (flowing gas) conditions. A comprehensive set of material characterization methods, including thermal analysis, Xray diffraction, and X-ray fluorescence, were used to confirm extents of carbonation and to better elucidate those compositional factors controlling the reactions. The results of these studies show that the rate of carbonation in CKD is controlled by the extent of carbonation. With increased degrees of conversion, particle-scale processes such as intraparticle diffusion and CaCO3 micropore precipitation patterns begin to limit the rate and possibly the extent of the reactions. Rates may also be influenced by the nature of the oxides participating in the reaction, slowing when the free or unbound oxides are consumed and reaction conditions shift towards the consumption of less reactive Ca species. While microscale processes and composition affects appear to be important at later times, the overall degrees of carbonation observed in the wastes were significant (> 80%), a majority of which occurs within the first 2 days of reaction. Under the operational conditions applied in this study, the degree of carbonation in CKD achieved in column-scale systems was comparable to those observed under ideal batch conditions. In addition, the similarity in sequestration performance among several different CKD waste types indicates that, aside from available oxide content, no compositional factors significantly hinder the ability of the waste to sequester CO2.

Life cycle assessment of biofuels produced by the new integrated hydropyrolysis-hydroconversion (IH2) process

Biofuels are alternative fuels that have the promise of reducing reliance on imported fossil fuels and decreasing emission of greenhouse gases from energy consumption. This thesis analyses the environmental impacts focusing on the greenhouse gas (GHG) emissions associated with the production and delivery of biofuel using the new Integrated Hydropyrolysis and Hydroconversion (IH2) process. The IH2 process is an innovative process for the conversion of woody biomass into hydrocarbon liquid transportation fuels in the range of gasoline and diesel. A cradle-to-grave life cycle assessment (LCA) was used to calculate the greenhouse gas emissions associated with diverse feedstocks production systems and delivery to the IH2 facility plus producing and using these new renewable liquid fuels. The biomass feedstocks analyzed include algae (microalgae), bagasse from a sugar cane-producing locations such as Brazil or extreme southern US, corn stover from Midwest US locations, and forest feedstocks from a northern Wisconsin location. The life cycle greenhouse gas (GHG) emissions savings of 58%–98% were calculated for IH2 gasoline and diesel production and combustion use in vehicles compared to fossil fuels. The range of savings is due to different biomass feedstocks and transportation modes and distances. Different scenarios were conducted to understand the uncertainties in certain input data to the LCA model, particularly in the feedstock production section, the IH2 biofuel production section, and transportation sections.

Ethanol Production from Hardboard Manufacturing Process Wastewater: Methods for Improving Product Yields from Hemicellulose Hydrolysates

Waste effluents from the forest products industry are sources of lignocellulosic biomass that can be converted to ethanol by yeast after pretreatment. However, the challenge of improving ethanol yields from a mixed pentose and hexose fermentation of a potentially inhibitory hydrolysate still remains. Hardboard manufacturing process wastewater (HPW) was evaluated at a potential feedstream for lignocellulosic ethanol production by native xylose-fermenting yeast. After screening of xylose-fermenting yeasts, Scheffersomyces stipitis CBS 6054 was selected as the ideal organism for conversion of the HPW hydrolysate material. The individual and synergistic effects of inhibitory compounds present in the hydrolysate were evaluated using response surface methodology. It was concluded that organic acids have an additive negative effect on fermentations. Fermentation conditions were also optimized in terms of aeration and pH. Methods for improving productivity and achieving higher ethanol yields were investigated. Adaptation to the conditions present in the hydrolysate through repeated cell sub-culturing was used. The objectives of this present study were to adapt S. stipitis CBS6054 to a dilute-acid pretreated lignocellulosic containing waste stream; compare the physiological, metabolic, and proteomic profiles of the adapted strain to its parent; quantify changes in protein expression/regulation, metabolite abundance, and enzyme activity; and determine the biochemical and molecular mechanism of adaptation. The adapted culture showed improvement in both substrate utilization and ethanol yields compared to the unadapted parent strain. The adapted strain also represented a growth phenotype compared to its unadapted parent based on its physiological and proteomic profiles. Several potential targets that could be responsible for strain improvement were identified. These targets could have implications for metabolic engineering of strains for improved ethanol production from lignocellulosic feedstocks. Although this work focuses specifically on the conversion of HPW to ethanol, the methods developed can be used for any feedstock/product systems that employ a microbial conversion step. The benefit of this research is that the organisms will the optimized for a company's specific system.

SIZE OPTIMIZATION OF A BIOMASS TO LIQUID FUEL CONVERSION FACILITY WITHIN A BIOMASS SUPPLY CHAIN

Bioenergy and biobased products offer new opportunities for strengthening rural economies, enhancing environmental health, and providing a secure energy future. Realizing these benefits will require the development of many different biobased products and biobased production systems. The biomass feedstocks that will enable such development must be sustainable, widely available across many different regions, and compatible with industry requirements. The purpose of this research is to develop an economic model that will help decision makers identify the optimal size of a forest resource based biofuel production facility. The model must be applicable to decision makers anywhere, though the modeled case analysis will focus on a specific region; the Upper Peninsula (U.P.) of Michigan. This work will illustrate that several factors influence the optimal facility size. Further, this effort will reveal that the location of the facility does affect size. The results of the research show that an optimal facility size can be determined for a given location and are based on variables including forest biomass availability, transportation cost rate, and economy of scale factors. These variables acting alone and interacting together can influence the optimal size and the decision of where to locate the biofuel production facility. Further, adjustments to model variables like biomass resource and storage costs have no effect on facility size, but do affect the unit cost of the biofuel produced.

Biochemical Conversions of Lignocellulosic Biomass for Sustainable Fuel-Ethanol Production in the Upper Midwest

Biofuels are an increasingly important component of worldwide energy supply. This research aims to understand the pathways and impacts of biofuels production, and to improve these processes to make them more efficient. In Chapter 2, a life cycle assessment (LCA) is presented for cellulosic ethanol production from five potential feedstocks of regional importance to the upper Midwest - hybrid poplar, hybrid willow, switchgrass, diverse prairie grasses, and logging residues - according to the requirements of Renewable Fuel Standard (RFS). Direct land use change emissions are included for the conversion of abandoned agricultural land to feedstock production, and computer models of the conversion process are used in order to determine the effect of varying biomass composition on overall life cycle impacts. All scenarios analyzed here result in greater than 60% reduction in greenhouse gas emissions relative to petroleum gasoline. Land use change effects were found to contribute significantly to the overall emissions for the first 20 years after plantation establishment. Chapter 3 is an investigation of the effects of biomass mixtures on overall sugar recovery from the combined processes of dilute acid pretreatment and enzymatic hydrolysis. Biomass mixtures studied were aspen, a hardwood species well suited to biochemical processing; balsam, a high-lignin softwood species, and switchgrass, an herbaceous energy crop with high ash content. A matrix of three different dilute acid pretreatment severities and three different enzyme loading levels was used to characterize interactions between pretreatment and enzymatic hydrolysis. Maximum glucose yield for any species was 70% oftheoretical for switchgrass, and maximum xylose yield was 99.7% of theoretical for aspen. Supplemental β-glucosidase increased glucose yield from enzymatic hydrolysis by an average of 15%, and total sugar recoveries for mixtures could be predicted to within 4% by linear interpolation of the pure species results. Chapter 4 is an evaluation of the potential for producing Trichoderma reesei cellulose hydrolases in the Kluyveromyces lactis yeast expression system. The exoglucanases Cel6A and Cel7A, and the endoglucanase Cel7B were inserted separately into the K. lactis and the enzymes were analyzed for activity on various substrates. Recombinant Cel7B was found to be active on carboxymethyl cellulose and Avicel powdered cellulose substrates. Recombinant Cel6A was also found to be active on Avicel. Recombinant Cel7A was produced, but no enzymatic activity was detected on any substrate. Chapter 5 presents a new method for enzyme improvement studies using enzyme co-expression and yeast growth rate measurements as a potential high-throughput expression and screening system in K. lactis yeast. Two different K. lactis strains were evaluated for their usefulness in growth screening studies, one wild-type strain and one strain which has had the main galactose metabolic pathway disabled. Sequential transformation and co-expression of the exoglucanase Cel6A and endoglucanase Cel7B was performed, and improved hydrolysis rates on Avicel were detectable in the cell culture supernatant. Future work should focus on hydrolysis of natural substrates, developing the growth screening method, and utilizing the K. lactis expression system for directed evolution of enzymes.

Organic geochemistry of deep sea sediments from the Nankai Trough and the Southwest Japan forearc region

Earth's largest reactive carbon pool, marine sedimentary organic matter, becomes increasingly recalcitrant during burial, making it almost inaccessible as a substrate for microorganisms, and thereby limiting metabolic activity in the deep biosphere. Because elevated temperature acting over geological time leads to the massive thermal breakdown of the organic matter into volatiles, including petroleum, the question arises whether microorganisms can directly utilize these maturation products as a substrate. While migrated thermogenic fluids are known to sustain microbial consortia in shallow sediments, an in situ coupling of abiotic generation and microbial utilization has not been demonstrated. Here we show, using a combination of basin modelling, kinetic modelling, geomicrobiology and biogeochemistry, that microorganisms inhabit the active generation zone in the Nankai Trough, offshore Japan. Three sites from ODP Leg 190 have been evaluated, namely 1173, 1174 and 1177, drilled in nearly undeformed Quaternary and Tertiary sedimentary sequences seaward of the Nankai Trough itself. Paleotemperatures were reconstructed based on subsidence profiles, compaction modelling, present-day heat flow, downhole temperature measurements and organic maturity parameters. Today's heat flow distribution can be considered mainly conductive, and is extremely high in places, reaching 180 mW/m**2. The kinetic parameters describing total hydrocarbon generation, determined by laboratory pyrolysis experiments, were utilized by the model in order to predict the timing of generation in time and space. The model predicts that the onset of present day generation lies between 300 and 500 m below sea floor (5100-5300 m below mean sea level), depending on well location. In the case of Site 1174, 5-10% conversion has taken place by a present day temperature of ca. 85 °C. Predictions were largely validated by on-site hydrocarbon gas measurements. Viable organisms in the same depth range have been proven using 14C-radiolabelled substrates for methanogenesis, bacterial cell counts and intact phospholipids. Altogether, these results point to an overlap of abiotic thermal degradation reactions going on in the same part of the sedimentary column as where a deep biosphere exists. The organic matter preserved in Nankai Trough sediments is of the type that generates putative feedstocks for microbial activity, namely oxygenated compounds and hydrocarbons. Furthermore, the rates of thermal degradation calculated from the kinetic model closely resemble rates of respiration and electron donor consumption independently measured in other deep biosphere environments. We deduce that abiotically driven degradation reactions have provided substrates for microbial activity in deep sediments at this convergent continental margin.

Estudio técnico-económico de una planta de producción de biodiesel

Se explica las posibles razones que han obligado a varias de las plantas de biodiésel en España a cerrar a pesar de estar siendo auspiciadas por la Unión Europea y fomentadas, mediante normativas específicas y ayudas sustanciales en cada uno de los países miembros, a fin de reforzar la utilización de los biocarburantes, como energía alternativa a los combustibles fósiles, debido a las ventajas medioambientales y sociopolíticas que conllevan. Para ello se ha empezado realizando un estudio del sector y de su funcionamiento así como de la evolución reciente del mercado tanto en Europa como en España. Posteriormente se ha modelizado una planta de biodiesel tipo desde las primeras fases de su construcción hasta su puesta en funcionamiento, para, a continuación analizar su desarrollo haciendo especial hincapié en la evolución de las principales variables económicas anteriormente estudiadas que han llevado finalmente a tener que cerrarla por falta de rentabilidad. El proceso de producción del biodiésel desde aceites vegetales y grasas animales mantiene un fuerte crecimiento en los mercados de la Unión Europea al igual que en Estados Unidos y Canadá. La producción de biodiésel se ha incrementado rápidamente en los últimos años, ya que es una alternativa renovable a los carburantes, como el petróleo o el diésel. La producción por trasesterificación de aceites vegetales y grasas animales, dan al biodiésel una densidad, un punto de encendido, viscosidad, estabilidad a la oxidación similares al diésel. Estas propiedades permiten a la mezcla de biodiésel poder usarlo en motores convencionales sin necesidad de grandes modificaciones. El objetivo fundamental de este proyecto es, dentro de un entorno económico hostil, explicar el posible porqué de la situación de las plantas de biodiésel en España, haciendo un análisis de la viabilidad económico – financiera de una planta de producción de biodiésel. La instalación de la que parte el presente proyecto es la de una planta, situada en la provincia de Jaén, con una capacidad de producción de 100 000 t/año, con una previsión de funcionamiento continua y con una vida útil estimada de 15 años. Una vez finalizado el estudio económico, se ha valorado el impacto del mercado en el funcionamiento de la planta, tanto a nivel internacional debido a la competencia desleal, como nacional, debido a las ayudas en los cultivos. Se deduce que la rentabilidad de una planta de biodiésel es relativamente positiva pero viene dada por un gran número de variables internas y externas que hacen un negocio inestable y poco rentable. ABSTRACT It explains the possible reasons that have forced several biodiesel plants in Spain to close in spite of being sponsored by the European Union and promoted by specific regulations and substantial aid in each of the member countries to strengthen the use of biofuels as alternative energy to fossil fuels because of the environmental and sociopolitical involving VII For this we have begun a study of the sector and its operation as well as the recent market developments in Europe and in Spain. Later was modeled biodiesel plant type from the early stages of construction to commissioning, to then analyze its development with particular emphasis on the evolution of the main economic variables that have been previously studied eventually have to close by unprofitability. The processes and production of biodiesel (methyl ester) from vegetable oil and animal fat feedstocks remain a strong growth market in the European Union as well as the United States and Canada. Biodiesel production has increased rapidly in this last years as producers sought a renewable alternative to petroleum fuel. Produced by the trans-esterification of vegetable oils and animal fats, biodiesel has similar density, flash point, viscosity, oxidation stability to petroleum diesel. These similarities enable biodiesel blends to be used in conventional diesel engines without significant modifications. This proyect gives an overview of current developments with regard to biodiesel technology, the Spain biofuel market, and national biofuel policies, looking at closely the economic-financial feasibility of a biodiesel production plant. The installation, situated at Linares (Jaén), has a production capability of 100 000 t/year. The operation estimated is constant and with a product life of 15 years. Finished the part destined to the economic view of this project, it has been considered the adverse effects on the overall performance and the financial situation of the industry. It follows form the study that biodiesel plant´s profitability is relatively high, but it is given by a large numbers of variables, internals and externals, which have made an unviable and unsustainable business.

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.

Effects of biochar prepared from organic waste on soil properties

Biochar is a carbon-rich solid obtained by the thermal decomposition of organic matter under a limited supply of oxygen and at relatively low temperatures. Biochar can be prepared from the pyrolysis of different organic feed- stocks, such as wood and biomass crops, agricultural by-products, different types of waste or paper industry waste materials . The pyrolysis procedure of waste, i.e. sewage sludge, has mainly two advantages, firstly, it removes pathogens from waste and, secondly, biochar can reduce the leaching of heavy metals present in raw sewage sludge. This trend of the use of waste material as feedstocks to the preparation of biochar is increasing in the last years due to industrial development and economic growth imply an increase in waste generation. The application of biochar may have positive effects on soil physical properties as water holding capacity and structure or on soil biological activity and soil quality. Also, biochar can be used to remove water pollutants and can be used in multiple ways in soil remediation due to its adsorption of pesticides or metals. Also, biochar contribute to carbon sequestration due to carbon stability of biochar materials. The objective of this presentation is to review the positive effects of the biochar prepared from organic waste on soil properties.

Investigación sobre fermentaciones metánicas de desechos estacionales

En el campo agrícola se producen una serie de desechos orgánicos, que por un lado representan serios problemas de contaminación ambiental y por otro el desperdicio de valores energéticos importantes. Es decir una acción contraria a la sostenibilidad que debe buscarse en este siglo XXI. Entre estos productos agrícolas pueden citarse la pulpa de café, residuos herbáceos, bagazo de caña y la fracción insoluble de estiércol de ganado porcino conocida como cerdaza. Un problema añadido para dar solución adecuada es la disponibilidad de estos solo en cortas épocas del año. Todo lo anterior ha sido el origen de la presente investigación, para dar solución adecuada tanto en el aprovechamiento de biogás como en la reducción de la contaminación. La investigación descrita en este documento contempla el desarrollo de los siguientes aspectos: 1) Caracterización y problemática de cada uno de los productos señalados, 2) la solución al problema mediante el proceso de digestión anaerobia con fases separadas con el aprovechamiento del biogás generados y 3) recomendaciones para el arranque del proceso de digestión anaerobia y su mantenimiento en una alternancia de los productos citados. En la primera etapa de la fase experimental se estimó el rendimiento específico de metano para los diferentes sustratos, utilizando reactores batch configurados en una y dos fases concluyendo que la digestión anaerobia en dos fases presenta diferentes ventajas sobre la digestión monoetapa. En general se obtuvo un mayor rendimiento en la producción de metano, una reducción en los tiempos de retención, mayor eficiencia en la eliminación de los sólidos volátiles agregados, y una mayor estabilidad en el proceso reflejado en el mantenimiento de valores de pH en los rangos de operación recomendados. Seguidamente, al comparar dos procesos para la puesta en marcha de digestores metanogénicos operados en forma continua, se concluye que las variables determinantes en la estabilidad del sistema son la alcalinidad total presente en el digestor, el establecimiento de la población de microorganismos y la carga orgánica aplicada. Las dos primeras están determinadas por la calidad y proporción del inóculo suministrado al inicio del proceso. La alternación de sustratos suministrados al sistema de digestión en dos fases, permitió determinar el impacto sobre el desempeño del mismo, registrando una reducción en la producción de biogás, la riqueza de metano y la eficiencia de eliminación de sólidos volátiles durante los primeros días de operación luego del cambio de sustrato. Este periodo corresponde al proceso de aclimatación de los microorganismos el cual requirió de 20 días para asimilar los componentes del nuevo sustrato. Finalmente, entre los sustratos analizados, la menor carga orgánica de operación para mantener la operación del sistema en continuo corresponde a la pulpa de café con 0.1 kg SV/m3. La composición de este sustrato favorece la rápida acumulación de acidez volátil en el sistema, proporcionando una tendencia a la acidificación. Sin embargo, al controlar las cargas orgánicas volumétricas, el sistema permaneció operando sin necesidad de adición de alcalinizantes. La aplicación de los resultados de la presente investigación a la problemática de residuos de café es alentadora, comprobando que el sistema puede ser operado en continuo alternando residuos boreales y pulpa de café, ambos sustratos disponibles en las plantas de procesamiento de la cereza de café. ABSTRACT In the agricultural field there are series of organic wastes, which in one hand are the source of serious problems of environmental pollution and in the other, they represent a residue that could be used as a feedstock with significant energy values. These actions are contrary to efforts towards sustainability, which should be a priority in this century. Among agricultural residues with significant abundance, the coffee pulp, herbaceous waste, sugarcane bagasse and the insoluble fraction of pig manure can be mentioned. An added problem to the development of appropriate treatment systems, which provides a solution to the disposal of such wastes, is the limited availability of these feedstocks only in short seasons. These arguments have been the source of our research, in order to provide properly measures to biogas usage and pollution reduction. The research presented in this document includes the approaches to the following aspects. 1) Characterization and problems regarding the selected feedstocks 2) the solution to the problem by anaerobic digestion process with separate phases and 3) recommendations for starting the process of anaerobic digestion and its maintenance with alternation of the products listed For the first stage of the experimental phase, the specific methane yield of the selected feedstocks was estimated using batch reactors configured in one and two phases. It was concluded that two-phase anaerobic digestion offered distinct advantages over the single-stage digestion. In general a higher methane production yields, lower retention times, higher efficiency in volatile solids removal, and increased stability among the process were obtained. When comparing two processes for starting up methanogenic digesters, it is concluded that the variables that determine the stability of the system are the total alkalinity in the digester, the establishment of the population of microorganisms and the organic load. The first variables are influenced by the proportion and quality of the inoculum supplied at the beginning of the process. The alternation of substrates gave as a result a negative impact on system performance, recording a reduction on biogas production, the methane concentration and the efficiency of volatile solids removal. The situation was observed during the first days of operation after the change of feeding. This period corresponds to the process of acclimatization of the microorganisms which required 20 days to assimilate new substrate components. Finally, among substrates studied, the lowest organic load applied to maintain a continuous operation of the system, corresponds to the coffee pulp with 0.1 kg VS / m3. The composition of this substrate promotes a rapid accumulation of volatile acidity within the system, providing a tendency to acidification. However, by controlling organic loads, the operating system remained stable without addition of alkalizing components. The application of the results of this research to the problem of coffee waste is promising, proving that an anaerobic system can be operated continuously by alternating boreal waste and coffee pulp, both substrates available in coffee processing plants.

Production of biodiesel from animal fat using supercritical ethanol

Biodiesel is currently produced from a catalytic transesterification reaction of various types of edible and non-edible oil with methanol. The use of waste animal tallow instead of edible oils opens a route to recycle this waste. This material has the advantage of lower costs but the problem of high content of free fatty acids, becoming necessary a pre-esterification reaction that increases the cost of the catalytic process. The production of biodiesel using supercritical alcohols is appropriate for materials with high acidity and water content, therefore the use of this process with animal fat is a promising alternative. Ethanol has been used because it can be produced from biomass via fermentation resulting in a complete renewable biodiesel, instead of methanol that derives from fossil feedstocks. Two different processes have been studied: first, the direct transesterification of animal fat using supercritical ethanol and second a two-step process where the first step is a hydrolysis of the animal fat and the second step is the esterification of the resulting fatty acids. The temperature, the molar ratio ethanol:fat and the time have been modified in the different reactions to study the effect in the final conversion and the degradation of the unsaturated fatty acid esters, main inconvenient of these high temperature and pressure processes.

Modelagem matemática do processo industrial de coqueamento retardado.

A unidade de coqueamento retardado é um processo térmico de conversão, utilizado pelas refinarias, para converter cargas residuais em produtos de baixo peso molecular e com alto valor agregado (gases, nafta e gasóleo) e coque verde de petróleo. Um pequeno aumento no rendimento líquido da unidade de coqueamento retardado proporciona benefícios económicos consideráveis, especialmente no destilado líquido. A concorrência no mercado, as restrições sobre as especificações do produto e gargalos operacionais exigem um melhor planejamento da produção. Portanto, o desenvolvimento de novas estratégias e modelos matemáticos, focados em melhores condições de operação do processo industrial e formulações de produtos, é essencial para alcançar melhores rendimentos e um acompanhamento mais preciso da qualidade do produto. Este trabalho tem como objetivo o desenvolvimento de modelo matemático do conjunto forno-reator do processo de coqueamento, a partir de informações obtidas em uma planta industrial. O modelo proposto é baseado na caracterização da carga e dos produtos em pseudocomponentes, modelos cinéticos de grupos e condições de equilíbrio liquido-vapor. Além disso, são discutidos os principais desafios para o desenvolver o modelo matemático do forno e do reator, bem como a caracterização rigorosa do resíduo de vácuo e dos produtos para determinar os parâmetros que afetam a morfologia do coque e a zona de reação no interior do reator de coque.

Conversion of low density polyethylene into fuel through co-processing with vacuum gas oil in a fluid catalytic cracking riser reactor

In this work, mixtures of vacuum gas oil and low density polyethylene, a major component of common industrial and consumer household plastics, were pyrolytically co-processed in a fluid catalytic cracking (FCC) riser reactor as a viable alternative for the energy and petrochemical revalorisation of plastic wastes into valuable petrochemical feedstocks and fuel within an existing industrial technology. Using equilibrium FCC catalyst, the oil–polymer blends were catalytically cracked at different processing conditions of temperatures between 773 K and 973 K and catalyst feed ratios of 5:1, 7:1 and 10:1. The influence of each of these processing parameters on the cracking gas and liquid yield patterns were studied and presented. Further analysed and presented are the different compositional distributions of the obtained liquids and gaseous products. The analysis of the results obtained revealed that with very little modifications to existing process superstructure, yields and compositional distributions of products from the fluid catalytic cracking of the oil–polymer blend in many cases were very similar to those of the processed oil feedstock, bringing to manifest the viability of the feedstock co-processing without significant detriments to FCC product yields and quality.

The EU regime on biofuels in transport: Still in search of sustainability. Egmont Paper No. 68, July 2014

Like other regions of the world, the EU is developing biofuels in the transport sector to reduce oil consumption and mitigate climate change. To promote them, it has adopted favourable legislation since the 2000s. In 2009 it even decided to oblige each Member State to ensure that by 2020 the share of energy coming from renewable sources reached at least 10% of their final consumption of energy in the transport sector. Biofuels are considered the main instrument to reach that percentage since the development of other alternatives (such as hydrogen and electricity) will take much longer than expected. Meanwhile, these various legislative initiatives have driven the production and consumption of biofuels in the EU. Biofuels accounted for 4.7% of EU transport fuel consumption in 2011. They have also led to trade and investment in biofuels on a global scale. This large-scale expansion of biofuels has, however, revealed numerous negative impacts. These stem from the fact that first-generation biofuels (i.e., those produced from food crops), of which the most important types are biodiesel and bioethanol, are used almost exclusively to meet the EU’s renewable 10% target in transport. Their negative impacts are: socioeconomic (food price rises), legal (land-grabbing), environmental (for instance, water stress and water pollution; soil erosion; reduction of biodiversity), climatic (direct and indirect land-use effects resulting in more greenhouse gas emissions) and public finance issues (subsidies and tax relief). The extent of such negative impacts depends on how biofuel feedstocks are produced and processed, the scale of production, and in particular, how they influence direct land use change (DLUC) and indirect land use change (ILUC) and the international trade. These negative impacts have thus provoked mounting debates in recent years, with a particular focus on ILUC. They have forced the EU to re-examine how it deals with biofuels and submit amendments to update its legislation. So far, the EU legislation foresees that only sustainable biofuels (produced in the EU or imported) can be used to meet the 10% target and receive public support; and to that end, mandatory sustainability criteria have been defined. Yet they have a huge flaw. Their measurement of greenhouse gas savings from biofuels does not take into account greenhouse gas emissions resulting from ILUC, which represent a major problem. The Energy Council of June 2014 agreed to set a limit on the extent to which firstgeneration biofuels can count towards the 10% target. But this limit appears to be less stringent than the ones made previously by the European Commission and the European Parliament. It also agreed to introduce incentives for the use of advanced (second- and third-generation) biofuels which would be allowed to count double towards the 10% target. But this again appears extremely modest by comparison with what was previously proposed. Finally, the approach chosen to take into account the greenhouse gas emissions due to ILUC appears more than cautious. The Energy Council agreed that the European Commission will carry out a reporting of ILUC emissions by using provisional estimated factors. A review clause will permit the later adjustment of these ILUC factors. With such legislative orientations made by the Energy Council, one cannot consider yet that there is a major shift in the EU biofuels policy. Bolder changes would have probably meant risking the collapse of the high-emission conventional biodiesel industry which currently makes up the majority of Europe’s biofuel production. The interests of EU farmers would have also been affected. There is nevertheless a tension between these legislative orientations and the new Commission’s proposals beyond 2020. In any case, many uncertainties remain on this issue. As long as solutions have not been found to minimize the important collateral damages provoked by the first generation biofuels, more scientific studies and caution are needed. Meanwhile, it would be wise to improve alternative paths towards a sustainable transport sector, i.e., stringent emission and energy standards for all vehicles, better public transport systems, automobiles that run on renewable energy other than biofuels, or other alternatives beyond the present imagination.