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This book advances the use of biodiesel—more environmentally friendly than traditional fossil fuels—by showing how it can be synthesized at a lower cost, with greater efficiency and as a more pure and stable product. It presents methods based on fluorescence spectroscopy, which are less time-consuming than the traditional Rancimat analysis for monitoring stability, and are therefore less prone to allowing oxidative decay in the biofuel. Biodiesel exploits a variety of raw materials, from freshly harvested cottonseed to recycled cooking oil. These are cheap to produce and generate fuel lower in polluting sulphur and aromatic compounds than its petroleum-based equivalent.
Beginning by addressing different protocols for synthesis based on fatty acids, methyl and ethyl esters, it then describes chemical analyses essential to establishing the purity of the biodiesel. It highlights in detail the use of multifunctional and synthetic antioxidants, and investigates the impact of synthetic chalcones and their derivatives on the oxidative stability of biodiesel.
The author goes on to explain how to ameliorate various influences – UV irradiation and metal contaminants for example – which increase the hazards of oxidation, such as degradation and instability. New pre-treatment procedures performed using ultrasonic energies, thermostatic bath and vortex stirring are not only more environmentally friendly, but cut down on the time-consuming process of determining metal content, and allow for the use of more environmentally friendly aqueous reagents. The book investigates and demonstrates these techniques on the basis of real-world results.
Further, it suggests the practical uses of byproducts of biodiesel production, for example, using glycerol as a source of energy and high valuable chemicals. These useful techniques aid any researcher exploring the production process of biodiesel and its stabilization and characteristics.



Chapter 1. Renewable Energy Sources: A Sustainable Strategy for Biodiesel Productions

Nowadays, the world energetic scenario is moving toward a search for renewable energy matrices, allowing energy sources to be enlarged to produce diesel and/or biodiesel. Biodiesel is a renewable and clean-burning biofuel that is gradually being incorporated into conventional diesel as a means of limiting the production of fossil fuels to motivate the productivity of “ecologic friendly” biofuel. However, some oilseed species used as raw materials, even those with lower operational cost for the production of the vegetable oil, are still a great challenge for the petrochemical industry, given the economic competitiveness of biodiesel against the diesel obtained from fossil fuels. The use of alternative oilseed species to produce biodiesel may increase costs, which may exceed the price of the barrel of diesel, leading to non-viable biodiesel production. On the other hand, the high taxes on petroleum products can reduce the difference between them, allowing biodiesel production to become economically viable. This situation makes the exploration of economical alternative non-food feedstocks (e.g., Jatropha curcas) an important research topic. Biodiesel is made from diverse feedstocks including soybean, rapeseed/canola, sunflower, safflower, palm, Jatropha curcas, Raphanus sativus, cottonseed, corn, peanut, coconut, recycled cooking oil, animal fats, and also algae. In the context of renewable sources for biodiesel energy, the great biodiversity of alternative oilseeds and others oily biomass makes Brazil, the USA, Canada, and some countries in Europe and Asia greater potential markets to produce biofuels from these alternative sources. The incentives for using renewable species for biodiesel production rather than conventional petroleum diesel fuel are the absence of sulfur or aromatic compounds, high content of oil, low cost of crop maintenance, improvement of the environment, creation of new jobs, and a significant contribution to the domestic economy.
Kássia R. N. da Silva, Marcela Z. Corazza, Jorge L. Raposo

Chapter 2. Employment of Alternative Raw Materials for Biodiesel Synthesis

The search for renewable fuels has increased in recent times, since petroleum-derived fuels are depleting supplies and contributing to accumulation of carbon dioxide in the environment. In this way, biodiesel presents economic, social, and environmental advantages as a renewable biofuel. This chapter aims to inform the reader about different raw materials that can be used to synthesize biodiesel. Moreover, the main physicochemical parameters are presented based on the standard agencies around the world. In general, the raw materials (algae, castor oil, soybean, waste frying oil, and Chrysomya albiceps larvae) represented satisfactory sources to produce biodiesel.
Bruna Silveira Pacheco, Caroline Carapina da Silva, Samantha Coelho de Freitas, Lucas Moraes Berneira, Vinícius Lenz da Silva, Kathleen Winkel, Letícia Braatz Ferreira, Claudio Martin Pereira de Pereira

Chapter 3. Alternative Multifunctional Additives for Biodiesel Stabilization: Perspectives for More Efficiency and More Cost-Effectiveness

In this chapter, we address the current technologies to cover the alternative blends composed by multifunctional antioxidants—sometimes called secondary antioxidants—used to overcome the problems of degradation and provide more stability to the biodiesel which is derived from different raw materials. To this end, some valuable works with notable studies of conventional antioxidants, and sometimes synergetic binary/ternary blends and their applications, were briefly reviewed. However, the chapter attempts to cover only an overview of the recent advances in the field of multifunctional alternative additives, which provide a more efficient stabilization of the biodiesel. Also, its activities allow lowering the concentration of additives into biodiesel while maintaining their required specification. Furthermore, the chapter brings some aspects of the chemistry behind the multifunctional activities, focusing on the key benefits that afford in their multifunctional properties. Lastly, considering the vast scale in which the biofuel can be processed, we also show that the target additives improve the performance of conventional antioxidants more cost-effectively.
Ana Carolina Roveda, Magno Aparecido Gonçalves Trindade

Chapter 4. Hydroxychalcones: Synthetic Alternatives to Enhance Oxidative Stability of Biodiesel

In this chapter, the main aspects about biodiesel synthesis and established quality parameters are reviewed and discussed in the perspective of oxidative stability. First, the characteristics, which define biodiesel as a promising, renewable green fuel, are listed. On the other hand, the propensity of biodiesel to oxidation is explained as one of the limitations to its application. Along this line of thought, the majority of natural and synthetic antioxidants usually applied in the industry are discussed, in which it can be noted that phenolic compounds are very representative. Chalcones containing hydroxyl groups in its structure are phenolic compounds, and so, their origins, sources, and synthetic approaches to obtain these types of molecules are presented. Antioxidant effects of hydroxychalcones already reported in the literature are pointed, and then an experimental topic shows the influence of two synthetic hydroxychalcones, namely (E)-1-(2-hydroxyphenyl)-3-phenylprop-2-en-1-one and (E)-1-(2-hydroxyphenyl)-3-(3-hydroxyphenyl) prop-2-en-1-one, on the oxidative stability of biodiesel obtained from frying soybean oil. The effects assessed by calorimetric analysis revealed interesting effects on the enhancement of biodiesel oxidative stability.
Caroline Carapina Da Silva, Bruna Silveira Pacheco, Samantha Coelho de Freitas, Lucas Moraes Berneira, Marco Aurélio Ziemann dos Santos, Lucas Pizzuti, Claudio Martin Pereira de Pereira

Chapter 5. Fluorescence Spectroscopy as an Alternative Analytical Tool for Monitoring Biodiesel Oxidative Stability: Thermal Oxidation Effect on the Endogenous Chromophores and Fluorophores in Biodiesel

Thermal stability of biodiesel is an important quality factor and it must be precisely evaluated. Despite the existence of conventional methods, fast, accurate, and robust analytical procedures are needed and still being developed. In this study, soybean and canola biodiesels underwent degradation by heating the samples and a systematic dependence on the concentration of endogenous chromophores (conjugated dienes, trienes, and tetraenes) and fluorophores (conjugated tetraenes) was optically monitored. UV–Vis absorption and fluorescence spectra of biodiesel allowed to identify the molecules formed in the initial thermal degradation stage. Absorbance and fluorescence intensities systematically changed at thermal treatment over 100 °C. Therefore, monitoring of the degradation compounds allows to evaluate the biodiesel degradation and the evolution of the degradation compounds content. The results indicate that analytical methods based on UV–Vis absorption and fluorescence spectroscopy may be able to monitor the biodiesel degradation, providing basis for the development of simple, portable, and low-cost devices.
Keurison Figueredo Magalhães, Anderson Rodrigues Lima Caires, Tiago Andrade Chimenez, Mariele Cappelari Fripp, Fabíola Machado, Samuel Leite Oliveira

Chapter 6. Recent Advances on Sample Preparation Procedures for Elemental Determination in Biodiesel

In recent years, renewable oilseeds have been investigated as viable alternatives sources for enhanced production of biofuels. However, due to the recent investigation for new energy sources, greater attention is being given to ensure quality of the final products, in particular to the elemental content, to increase the diversity of biodiesel. The elemental determination of biodiesel is often performed by spectrometric techniques, and most of them require a sample pretreatment to match the sample characteristics (i.e., high organic matter content, physicochemical properties, and low concentrations of analyte) to the analytical techniques available. Moreover, due to the advances on environment-friendly procedures (based on the principles of green chemistry), alternative sample pretreatments based on nondestructive measurement have been proposed, not only for the determination of metals in biodiesel, but also in the entire biodiesel production chain. By the way, it is important to emphasize that a nondestructive sample preparation procedure does not involve the complete decomposition of the matter by concentrated acid and heating. The use of nondestructive sample preparation in oily matrices for the determination of metals by atomic spectrometry is still a recent practice. Some of these are based on extraction procedures or by the formation of emulsion and microemulsion stable solutions. In many cases, these procedures can be performed using ultrasonic energies, thermostatic bath, centrifuge, vortex stirring, shaker, and other apparatus which improves the efficiency of the sample preparation procedure selected.
Liriana M. Roveda, Marcela Z. Corazza, Jorge L. Raposo

Chapter 7. Alternative Uses for Biodiesel Byproduct: Glycerol as Source of Energy and High Valuable Chemicals

Glycerol was firstly faced as a residue, since it is massively produced from the transesterification of vegetable oils and animal fat, corresponding to roughly 10% of the total amount of biodiesel. The recent high availability of glycerol has decreased its price and increased the risks of environmentally inadequate disposal. Now, this small chain alcohol is faced as a powerful alternative for energy conversion and production of chemicals with commercial interest. Its three hydrated carbons make this organic a noticeable substrate to produce other carbonyl compounds and to be used to produce energy in electrochemical devices collectively known as direct alcohol fuel cells. The development in the electrocatalysis field opened up new strategies to convert glycerol into power and chemicals, by using fuel cells and electrolyzer reactors. In both systems, the efficiency of the process depends on several aspects, as the medium, applied potential, and mainly on the surface reaction taking place at the interface between solution and electrode. In this chapter, we discuss the use of glycerol in these electrochemical systems and illustrate some experimental results regarding fundamental and applied science. Namely, we describe some advances in the understanding of the glycerol electro-oxidation reaction interpreted by spectroscopy and chromatographic techniques. Novel nanomaterials currently applied to improve the catalysis of the reaction are also shown. Moreover, we comment some results regarding fuel cells, microfluidic fuel cells, and electrolyzers fed by glycerol and the perspectives and challenges of its use.
Cauê Alves Martins, Pablo Sebastián Fernández, Giuseppe Abíola Camara
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