Biofuel production and testing opportunities

Biofuels stand at the forefront of the United States’ energy independence efforts and are the renewable fuels most likely to be used to bridge the growing gap between fossil fuel’s cost effective availability and America’s needs. With a known domestic commercial production capability, many economic, environmental, and geo-political benefits, and an ability to be used in our current transportation infrastructure biodiesel has emerged as the most credible near term alternative energy fuel. The Senior Honors Project described herein in many ways has been an exercise in applied research. Although at first the project focused on the chemical evaluation of reactants and products involved in biodiesel production efforts, it eventually turned to applying the knowledge gained, by in depth review and those chemical evaluations, into concrete suggestions for protocols, procedures and inventions that might improve some of the nation’s biodiesel production and testing effort. To be widely accepted and commercially effective biodiesel must be processed to meet certain known standards published by the American Society for Testing and Materials [ASTM]. An ultimate goal of the research of this Honors Thesis is the establishment at James Madison University, and in accordance with ASTM standards, of an ability to efficiently utilize gas chromatography and specific analysis column to test for glycerin and other reactants in the production of biodiesel. A more immediate goal of the research is to create and demonstrate an ability to perform to ASTM standards the most pertinent of the required small batch biodiesel tests. The ability to improve the reactions involved in the ASTM testing methodology and/or the protocols and procedures acceptable to meet ASTM standards could have great impact on 8 biodiesel production in general and small batch bio-fuel operations such as James Madison University’s [JMU] specifically. After a thorough campus and laboratory inventory was performed, an equipment review was accomplished and a methodology agreement reached. Following an exhaustive literature and JMU project review the necessary laboratory equipment, chemicals, and reactants were identified and assembled. The equipment repair-laboratory assembly process is ongoing. Laboratory protocols and baselines were established and trial experiments were performed to help establish laboratory standards. Acceptable biodiesel samples were obtained and established experimental protocols are currently being performed in the hope of obtaining repeatable results. New protocols and processes have been offered to test for biodiesel and an invention to improve the transesterfication reaction has been proposed. More specifically, the author has proposed the invention of a solid-state, heterogeneous catalyst, embedded onto a static mixer, to improve the necessary biodiesel transesterfication reaction, and not currently ASTM-approved biofuel production and quality testing procedures. A catalyst such as proposed, possibly working in even non-critical laboratory environments, could effectively and efficiently improve the biodiesel ASTM testing protocols

Fuel Quality Monitoring by Color Detection

The quality of automotive fuels—gasoline, diesel, biodiesel, and ethanol—is discussed in the light of their specifications in different countries and regions and in terms of their adulteration, which has such a prejudicial effect on the production chain, distribution chain, tax revenues, the environment, and end consumers. Different ways of adulterating automotive fuels are analyzed, as are the procedures for their detection. Several analytical methods for monitoring quality and detecting adulteration have been addressed in the literature, emphasizing the determination of properties such as density, distillation curve, octane rating, vapor pressure, etc., by means of physicochemical methods and chromatographic and spectrographic techniques, to the detriment of colorimetric methods. This chapter looks at colorimetric techniques designed for quality monitoring and the detection of adulteration in fuels, especially simple, quick, low-cost procedures with potential to be used in the field

A Life Cycle Assessment on Various Alternative Liquid Fuel Options in Western Australia

This thesis assesses the life cycle energy, water and carbon footprints of several biofuels production processed, considering (a) biomass from phase farm with trees; (b) biodiesel from waste cooking oil with utilising the by-product (crude glycerol); and ( c) bioslurry from biochar bio-oil and crude glycerol

Getting Lipids for Biodiesel Production from Oleaginous Fungi

Biomass-based biofuel production represents a pivotal approach to face high energy prices and potential depletion of crude oils reservoirs, to reduce greenhouse gas emissions, and to enhance a sustainable economy (Zinoviev et al., 2010). Microbial lipids can represent a valuable alternative feedstock for biodiesel production, and a potential solution for a bio-based economy.Nowadays, the production of biodiesel is based mostly on plant oils, even though animal fats, and algal oils can also be used. In particular, soybean, rapeseed, and palm oils are adopted as the major feedstock for biodiesel production. They are produced on agricultural land, opening the debate on the impact of the expansion of bioenergy crop cultures, which displace land from food production. Furthermore, their price restricts the large-scale development of biodiesel to some extent. In order to meet the increasing demand of biodiesel production, other oil sources have been explored. Recently, the development of processes to produce single cell oil (SCO) by using heterotrophic oleaginous microorganisms has triggered significant attention (Azocar et al., 2010). These organisms accumulate lipids, mostly consisting of triacylglycerols (TAG), that form the storage fraction of the cell. The occurrence of TAG as reserve compounds is widespread among all eukaryotic organisms such as fungi, plants and animals, whereas it has only rarely been described in bacteria (Meng et al., 2009). In fact, bacteria generally accumulate polyhydroxyalkanoates as storage compound and only few bacterial species, belonging to the actinobacterial genera Mycobacterium, Streptomyces, Rhodococcus and Nocardia produce relevant amounts of lipids (Alvarez & Steinbuchel, 2002).Among heterotrophic microorgansisms, oleaginous fungi, including both molds and yeasts, are increasingly been reported as good TAG producers. This chapter will focus on current knowledge advances in their metabolism, physiology, and in the result achieved in strain improvement, process engineering and raw material exploitation

A techno-economic, sustainability and experimental assessment of the direct methanation of biodiesel waste glycerol

Crude glycerol from biodiesel production is a potential feedstock for energy in many parts of the world. A concept that is yet to be explored is the conversion of glycerol to a methane rich gas known, in this case, as bio-SNG, by taking advantage of steam reforming and methanation reactions in a single reactor. This process is known as direct methanation. Direct methanation is a type of low temperature steam reforming and is performed at temperatures lower than those commonly used for hydrogen production from organic feedstock. When applied to glycerol, it is termed ‘GLT-SR’ in this thesis. GLT-SR allows glycerol to be transformed into a gaseous energy vector that can be converted to energy on-site at the biodiesel refinery to offset fossil natural gas usage, for instance, in the energy intensive bean or seed crushing stage. The present work identifies the feasibility of a GLT-SR process using a design process framework and included process modelling in Aspen Plus, technoeconomic and environmental energy life cycle impacts analysis and laboratory scale experiments using pure glycerol to avoid any unknown impacts of contaminants contained in crude glycerol. Based on the thermodynamic analysis and process model, the optimum conditions favouring methane production and energy efficiency were 8 atm, with a feed molar steam to carbon ratio of 2.56 and an inlet temperature of 474 K. When compared to natural gas, bio-SNG from soybean based glycerol had the potential to decrease global warming potential with a trade-off of increased eutrophication, terrestrial ecotoxicity and freshwater aquatic ecotoxicity potential. The economic analysis based on biodiesel plants located in the USA, determined that a gas price of USD$6-7 per million BTU was necessary to achieve acceptable rates of return and coincided with the states of Missouri and Arkansas. A gasification rig was constructed and laboratory experiments confirmed that reducing the temperature were essential to maximising methane production. At steady state roughly 90% of the glycerol was converted to carbon gases with the most effective conditions achieving 66% of the CH4 conversion at equilibrium at 673 K (400 °C), steam to carbon ratio 2.5, pressure 1 atm and weight hourly space velocity of 0.54 hr-1. Thus current process conditions showed the process was operating away from the desired equilibrium for maximum CH4. Based on economics and environmental analysis, the process is feasible but would rely on an optimised process to maximise CH4 production and further trials to determine the impact of glycerol contaminant

Design and optimization of poly(hydroxyalkanoate)s production plants using alternative substrates

In this work, we propose a Mixed Integer Nonlinear Programming (MINLP) model to determine the optimal design of a poly(hydroxyalkanoate)s (PHAs) production plant configuration. The superstructure based optimization model considers different carbon sources as raw material: glycerol (crude and purified), corn starch, cassava starch, sugarcane sucrose and sugarcane molasses. The PHA extraction section includes four alternatives: the use of enzyme, solvent, surfactant-NaOCl or surfactant-chelate. Model constraints include detailed capital cost for equipment, mass and energy balances, product specifications and operating bounds on process units. The resulting MINLP model maximizes the project net present value (NPV) as objective function and it is implemented in an equation oriented environment. Optimization results show the sugarcane-enzyme option as the most promising alternative (NPV = 75.01 million USD) for PHAs production with an energy consumption of 22.56 MJ/kg PHA and a production cost of 3.02 US$/kg PHA. Furthermore, an economic sensitivity analysis is performed.Fil: Ramos, Fernando Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Delpino, Claudio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Villar, Marcelo Armando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Díaz, María Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; Argentin

IMMOBILIZATION OF LIPASE ON METAL ORGANIC FRAMEWORKS FOR BIODIESEL PRODUCTION

For the economical application of enzymatic processes in biodiesel production, lipase enzyme has to be used in immobilized form to allow easy retention and reuse. The main challenges facing the industrialization of the enzymatic process are the high mass transfer resistance, the tendency to adsorb the by-product glycerol onto the support matrix and poor operational stability. These problems can be solved by a good selection of supports of favourable surface characteristics and pore sizes. In that regard, increasing interest has recently been in Metal-Organic Frameworks (MOFs) as a new kind of porous support for enzyme immobilization. Physical adsorption, which is a fast and easy method of enzyme immobilization ensures limited enzyme denaturation and does not affect the enzyme activity, native structure, and active sites. However, the physically adsorbed enzyme is prone to leaching resulting in low stability, owing to the weak interaction between the enzyme and the support. As an alternative, chemisorption in which the nucleophiles of the enzymes are covalently bonded to the organic linkers of MOFs to form peptide bonds. However, physically immobilized lipase is generally more active reached than chemically immobilized ones, owing to the negative effect of the chemical bonds on the structure of the enzyme. However, enzyme attachment into the internal pores of MOFs may not be efficient, as part of the enzymatic activity may be lost due to conformational changes during diffusion into small cavities. In this process, the enzyme is caged inside the pores of the MOFs during the crystallization process. In addition, enzymes immobilized by this approach exhibit mass transfer limitations and their diffusion are restricted as the substrate may not be able to access the entire active sites. Kinetics and thermodynamics studies of the adsorption process, which are scarce in the literature, could provide invaluable information to explain the different performance of surface adsorption on pre-synthesized MOFs and encapsulation during crystallizations can provide value in terms of (i) chemical affinity between the external surface area of the MOF and the enzyme, (ii) accessibility of enzymes to pores, (iii) enzyme leaching, and (iv) catalytic activities. Therefore, in this work, the mechanism, kinetics, and thermodynamics of lipase adsorption on the surface of different MOFs, namely ZIF-67, ZIF-8 and HKUST-1, have been thoroughly investigated and tested for biodiesel production. The three supports have different structures, pore sizes, chemical properties, and surface areas. The influence of temperature, initial protein loading, and contact time on the adsorption and catalytic properties of the resultant biocatalysts were investigated. The catalytic properties were assessed on biodiesel production from olive oil transesterification. The highest lipase adsorption capacity of 26.9 mg/g was achieved using ZIF-67 at 45oC and an initial protein concentration of 0.6 mg/mL. The maximum capacities of ZIF-8 and HKUST-1 were 18.95 mg/g and 0.50 mg/mL at 35oC and 17.53 mg/mL at 45oC and 0.60 mg/mL, respectively. The equilibrium adsorption data suggested that the lipase adsorbed physically on ZIF-67 and ZIF-8 and chemically of HKUST-1. The data were best fitted with the Langmuir isotherm model for the three supports. Whereas, of the adsorption kinetics data were best fitted using Elovish’s model for ZIF-67 and ZIF-8, and the pseudo-second model for HKUST-1. It was also found that the process was influenced by intraparticle and film diffusion. The prepared bio-catalyst was successfully used to catalyze the transesterification of olive oil to produce biodiesel in a solvent-free medium. The ZIF-8 and ZIF-67 showed better catalytic activity achieving 88% and 90% conversion, whereas HKUST-1 showed better operational stability owing to the stronger chemical adoption. In addition, diffusion-reaction kinetics of biodiesel production using adsorbed lipase on ZIF-8 have been analyzed. The investigation provided insight into adsorption pathways and the probable mechanisms involved and a better understanding of their application in biodiesel production

Cynara cardunculus as an alternative crop for biodiesel production.

Biodiesel is a renewable fuel obtained from vegetable oils or animal fats, with similar propertiesto fossil diesel fuel. It is obtained from the transesterification of the triglycerides with a shortchain alcohol in the presence of a catalyst, giving biodiesel and glycerol in two separated phases.Traditional raw materials for biodiesel production are the oils of rapeseed, sunflower, soybeanand palm. However, some alternative raw materials such as animal fats, recycled oils and nonconventional crops, are also used.This thesis is focused on the use of Cynara cardunculus oil for the production of biodiesel. Cynaracardunculus is a wild cardoon from the family of artichoke that is well adapted to theMediterranean weather. The maximum production reaches 2 tons/ha per year of seeds thatcontain up to 25 % oil, with a similar composition to sunflower oil. Thus, Cynara cardunculuscultivation may represent an alternative for abandoned cropland and a good candidate asrenewable energy source and biodiesel production.In the first part of the work, the reaction conditions where optimised for the transesterificationof unrefined Cynara cardunculus oil. The product obtained was characterised. The acid value of theoriginal oil (11.8 mgKOH/g) was higher than the values recommended for alkalinetransesterification (1-2 mgKOH/g) resulting in the formation of soaps and gels. For some of thereaction conditions, the ester and glycerol phases were not clearly separated, reflecting the needof a preesterification step in order to reduce the acid value of the oil. The preesterification stepwas optimised using different reaction temperatures, catalyst and methanol concentrations andreaction times. The best results were obtained for the reactions conducted at 60ºC, using a 6:1methanol to oil molar ratio and 0.5% sulphuric acid as catalyst. Finally, the oil was pre-treatedusing the best conditions for the preesterification, with an additional degumming step. Thetransesterification of the pre-treated oil was optimised and the results were compared to theprevious ones. The ester yield increased with the pre-treatment and the ester and glycerol phaseswere clearly separated in most of the cases, showing the advantages of the degumming andpreesterification steps.The second part of the work was the characterisation of the mixtures of biodiesel and diesel fuel.European specific normatives for both biodiesel (EN 14214) and fossil diesel fuel (EN 590) weredetailed, together with their requirements and test methods. Mixtures of both fuels at differentproportions, were analysed according to EN 590. Correlations for the mixtures were determinedwith experiments or mass balances, according to each case. There are some properties than canlimit the amount of biodiesel allowed in the mixture in order to satisfy the specifications fordiesel fuel, such as density, viscosity, distillation, oxidative stability and cold weather properties. Itwas detected the need of specific analytical methods and requirements for some of the properties.The third part of the work was the analysis of the biodegradability of mixtures of biodiesel andfossil derived fuels, such as heavy fuel oil, diesel fuel and gasoline. The CO2 evolution test wasused to analyse the biodegradation behaviour of the mixtures. In all the cases cometabolicbiodegradation was observed demonstrating that biodiesel enhances the degradation of the threefossil derived fuels analysed. The physical properties of the mixtures were also analysed.UNIVERSITAT ROVIRA I VIRGILICYNARA CARDUNCULUS AS AN ALTERNATIVE CROP FOR BIODIESEL PRODUCTION.Jorgelina Cecilia PasqualinoEl biodiesel es un combustible de origen renovable que se obtiene a partir de aceites vegetales ygrasas animales y posee propiedades similares a las del gasoil. Se produce mediante latransesterificación de los triglicéridos con un alcohol de cadena corta, en presencia de uncatalizador, obteniendo biodiesel y glicerol en dos fases separadas. Los aceites más utilizados en laproducción de biodiesel son los de soja, colza, girasol y palma, aunque existen alternativas comolos aceites de fritura reciclados, las grasas animales y algunos cultivos no convencionales.En este trabajo se utilizó el aceite de Cynara cardunculus para producir biodiesel. Cynaracardunculus es un cardo silvestre de la familia de la alcachofa, que se encuentra adaptado al climaMediterráneo. Su producción máxima alcanza las 2 toneladas de semilla por hectárea al año, quecontienen hasta un 25 % de aceite, con una composición similar al aceite de girasol. De estemodo, el Cynara cardunculus puede representar un cultivo alternativo para la producción debiodiesel, pudiéndose cultivar en tierras abandonadas.En la primera parte del trabajo se optimizaron las condiciones para la transesterificación de aceitede Cynara cardunculus sin refinar y se caracterizó el producto obtenido. El índice de acidez delaceite original (11.8 mgKOH/g) fue mayor al recomendado para la transesterificación alcalina (1-2 mgKOH/g), resultando en la formación de gel y jabón. En algunos casos no se produjo unaseparación clara de las fases, reflejando la necesidad de una etapa de preesterificación para reducirel índice de acidez. La preesterificación fue optimizada utilizando diferentes temperaturas,concentraciones de metanol y catalizador, y tiempos finales de reacción. Las mejores condicionesde operación se obtuvieron para la reacción realizada a 60ºC, utilizando metanol en una relaciónmolar de 6:1 con respecto al aceite, y un 0.5% de H2SO4 como catalizador. Finalmente, el aceitefue pre-tratado bajo las condiciones óptimas de preesterificación, con una etapa adicional dedegomado. La reacción de transesterificación del aceite pre-tratado fue optimizada y losresultados comparados con los de la reacción del aceite crudo. El contenido en metilésteres fuesuperior al utilizar aceite pre-tratado, y las fases de metilésteres y glicerol se separaron confacilidad en la mayoría de los casos, demostrando la utilidad de las etapas de pretratamiento.La segunda parte fue la caracterización de las mezclas de biodiesel con gasoil. Las normativaseuropeas para el biodiesel (EN 14214) y para el gasoil (EN 590) fueron detalladas junto con susrequisitos y métodos de ensayo. Las mezclas de ambos combustibles en diferentes proporcionesse analizaron de acuerdo a la norma EN 590. Las correlaciones para el comportamiento de lasmezclas se determinaron mediante experimentación y balances de materia, según el caso. Sedeterminó que algunas propiedades como la densidad, la viscosidad, la destilación, la estabilidad ala oxidación y las propiedades en frío pueden limitar la cantidad de biodiesel permitida en lamezcla para que esta cumpla con la normativa vigente para el gasoil. Se detectó la necesidad demétodos específicos de análisis y requisitos para algunas de las propiedades.La tercera parte de este trabajo consistió en el análisis de la biodegradabilidad de las mezclas debiodiesel con combustibles de origen fósil, como fuel pesado, gasoil y gasolina. Labiodegradación se determinó mediante el método de evolución de CO2. En todos los casos seobservó la presencia de cometabolismo, demostrando que el biodiesel incrementa labiodegradabilidad de los tres combustibles fósiles examinados. Se analizaron además laspropiedades físicas de las mezclas.UNIVERSITAT ROVIRA I VIRGILICYNARA CARDUNCULUS AS AN ALTERNATIVE CROP FOR BIODIESEL PRODUCTION.Jorgelina Cecilia Pasqualin