BIODIESEL – QUALITY, EMISSIONS AND BY-PRODUCTS Edited by Gisela Montero and Margarita Stoytcheva Biodiesel – Quality, Emissions and By-Products Edited by Gisela Montero and Margarita Stoytcheva Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access distributed under the Creative Commons Attribution 3.0 license, which allows users to download, copy and build upon published articles even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. As for readers, this license allows users to download, copy and build upon published chapters even for commercial purposes, as long as the author and publisher are properly credited, which ensures maximum dissemination and a wider impact of our publications. Notice Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published chapters. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Danijela Duric Technical Editor Teodora Smiljanic Cover Designer Jan Hyrat Image Copyright Jon Nightingale, 2011. Used under license from Shutterstock.com First published November, 2011 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Biodiesel – Quality, Emissions and By-Products, Edited by Gisela Montero and Margarita Stoytcheva p. cm. ISBN 978-953-307-784-0 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Biodiesel: Quality and Standards 1 Chapter 1 Biodiesel Quality, Standards and Properties 3 István Barabás and Ioan-Adrian Todoruţ Chapter 2 Characterization of Biodiesel by Unconventional Methods: Photothermal Techniques 29 Maria Castro, Francisco Machado, Aline Rocha, Victor Perez, André Guimarães, Marcelo Sthel, Edson Corrêa and Helion Vargas Chapter 3 Thermooxidative Properties of Biodiesels and Other Biological Fuels 47 Javier Tarrío-Saavedra, Salvador Naya, Jorge López-Beceiro, Carlos Gracia-Fernández and Ramón Artiaga Chapter 4 Effects of Raw Materials and Production Practices on Biodiesel Quality and Performance 63 Jose M. Rodriguez Chapter 5 The Effect of Storage Condition on Biodiesel 71 Yo-Ping Wu, Ya-Fen Lin and Jhen-Yu Ye Chapter 6 Analysis of FAME in Diesel and Heating Oil 89 Vladimir Purghart Chapter 7 Analytical Methodology for the Determination of Trace Metals in Biodiesel 99 Fabiana A. Lobo, Danielle Goveia, Leonardo F. Fraceto and André H. Rosa VI Contents Part 2 Biodiesel: Development, Performance, and Combustion Emissions 121 Chapter 8 Analysis of the Effect of Biodiesel Energy Policy on Markets, Trade and Food Safety in the International Context for Sustainable Development 123 Rodríguez Estelvina, Amaya Chávez Araceli, Romero Rubí, Colín Cruz Arturo and Carreras Pedro Chapter 9 Current Status of Biodiesel Production in Baja California, Mexico 137 Gisela Montero, Margarita Stoytcheva, Conrado García, Marcos Coronado, Lydia Toscano, Héctor Campbell, Armando Pérez and Ana Vázquez Chapter 10 Development of Multifunctional Detergent-Dispersant Additives Based on Fatty Acid Methyl Ester for Diesel and Biodiesel Fuel 153 Ádám Beck, Márk Bubálik and Jenő Hancsók Chapter 11 Research on Hydrogenation of FAME to Fatty Alcohols at Supercritical Conditions 171 Yao Zhilong Chapter 12 The Use of Biodiesel in Diesel Engines 181 S. Chuepeng Chapter 13 Toxicology of Biodiesel Combustion Products 195 Michael C. Madden, Laya Bhavaraju and Urmila P. Kodavanti Chapter 14 Utilization of Biodiesel-Diesel-Ethanol Blends in CI Engine 215 István Barabás and Ioan-Adrian Todoruţ Chapter 15 The Key Role of the Electronic Control Technology in the Exploitation of the Alternative Renewable Fuels for Future Green, Efficient and Clean Diesel Engines 235 Carlo Beatrice, Silvana Di Iorio, Chiara Guido and Pierpaolo Napolitano Part 3 Glycerol: Properties and Applications 255 Chapter 16 Glycerol, the Co-Product of Biodiesel: One Key for the Future Bio-Refinery 257 Raúl A. Comelli Chapter 17 Antioxidative and Anticorrosive Properties of Bioglycerol 283 Maria Jerzykiewicz and Irmina Ćwieląg-Piasecka Contents VII Chapter 18 Use of Glycerol in Biotechnological Applications 305 Volker F. Wendisch, Steffen N. Lindner and Tobias M. Meiswinkel Chapter 19 Improved Utilization of Crude Glycerol By-Product from Biodiesel Production 341 Alicja Kośmider, Katarzyna Leja and Katarzyna Czaczyk Chapter 20 Utilization of Crude Glycerin in Nonruminants 365 Brian J. Kerr, Gerald C. Shurson, Lee J. Johnston and William A. Dozier, III Preface The use of biodiesel worldwide is becoming increasingly important, because of the widespread shortage of oil resources, which has raised the prices of fossil fuels. This biofuel also offers an opportunity to meet the energy demands with less impact to the environment due its renewable characteristics. This book entitled "Biodiesel – Quality, Emissions and By-Products" comprises 20 chapters and covers topics related to biodiesel quality, performance of combustion engines that use biodiesel, and the emissions they generate. It emphasizes the applications of glycerol, a byproduct of biodiesel production process. It is divided in three sections: i) Biodiesel Quality and Standards, ii) Biodiesel: Development, Performance and Combustion Emissions, and iii) Glycerol: Properties and Applications. The first section, Biodiesel: Quality and Standards is integrated by seven chapters. Chapter 1 presents the main standards on commercial biodiesel quality adopted in different regions of the world and the importance and significance of the main properties of biodiesel. Chapter 2 discusses the determination of photochemical properties, thermal diffusion, thermal conductivity and thermal effusivity as a promising route to characterize biodiesel oils. Chapter 3 explains how to characterize and differentiate each type of biofuel respect to the other ones by pressure differential scanning calorimetry. Chapter 4 comments that raw material source, impurities and production practices, can affect the quality of the biodiesel, performance and commercial approval of the final product. Chapter 5 compares the performance of one commercial biodiesel and three laboratory-produced biodiesels to verify the effect of storage temperature, type of storage container, storage time, as well as the moisture content on the properties of the biodiesel. Chapter 6 describes a method for sample preparation and quantification of FAME in diesel, and Chapter 7 details a research about standardization of procedures used for metal trace in biodiesel. The second section, Biodiesel: Development, Performance and Combustion Emissions include eight chapters. Chapter 8 is a study of biodiesel and food balance, and how they represent opportunities for agriculture and rural development. Chapter 9 describes several studies for producing biodiesel from raw materials native of Baja California, Mexico. Chapter 10 presents the development of multifunctional detergent- dispersant additives based on fatty acid methyl esters. Chapter 11 discusses the results X Preface of a research on hydrogenation of fatty acid methyl esters to fatty alcohol. Chapter 12 is a review of impacts of biodiesel use as a fuel for diesel engines. Chapter 13 focuses on the toxicology of the compounds produced by the combustion of biodiesel. Chapter 14 depicts an assessment of the main properties of binary mixtures and triple mixtures between biodiesel from rapeseed oil, commercial diesel fuel and bioethanol compared to diesel fuel when were used in combustion engines. Chapter 15 exhibits the results of a research activity aimed at studying the high-blending biodiesel use in the “torque controlled” automotive diesel engines. In particular, based on the employment of an innovative biodiesel blending detection methodology, the capability of closed loop combustion control to improve both pollutant emissions and full load engine performance was investigated. The third section, Glycerol: Properties and Applications, focuses on this product obtained as a co-product of biodiesel. Chapter 16 is a review of reactions such as dehydration, hydrogenolysis, oxidation, etherification, and reforming including results obtained by the author. All these uses allow considering the glycerol as one key-compound in the environment of future biorefinery. Chapter 17 is a study about antioxidative and anticorrosive properties of glycerol. Chapter 18 summarizes the state-of-the-art glycerol-based biotechnological processes and discusses future developments. Chapter 19 presents the utilization of glycerol in biotechnological applications and Chapter 20 discusses some unusual applications of glycerol. All the contributing authors are gratefully acknowledged for their time and efforts in preparing the different chapters, and for their interest in the present project. Dr. Gisela Montero and Prof. Margarita Stoytcheva Mexicali, Baja California Mexico [...]... Free glycerin Total glycerin Distillation recovery 95% Phosphorus EN 12 662 ASTM D6854; EN 14 105–6 ASTM D6854; EN 14 105 ASTM D 116 0 ASTM D49 51; EN 14 107 ABNT NBR 714 8, 14 065 ASTM D1298/4052 EN 14 110 EN 14 111 ASTM D6584; EN 14 105 ASTM D6584; EN 14 105 ASTM D6584; EN 14 105 EN 14 108, EN 14 109 EN 14 538 — EN 14 112 report – 0.02 – 0.38 – 360 – 10 Alcohol Iodine number Monoglycerides Diglycerides Triglycerides... EN 14 105 – 0.20 % (m/m) Triglyceride EN 14 105 – 0.20 % (m/m) Free glycerol EN 14 105, EN 14 106 – 0.02 % (m/m) Total glycerol EN 14 105 – 0.25 % (m/m) Metals (Na + K) EN 14 108, EN 14 109 – 5 ppm Metals (Ca + Mg) EN 14 538 – 5 ppm Phosphorous EN 14 107 – 10 ppm Table 7 Japanese Biodiesel Specification 11 Biodiesel Quality, Standards and Properties Property Test method Limits min max Units Ester content EN 14 103... mg/kg – 1 class Copper strip corrosion (3 hours, EN ISO 216 0 50°C) Oxidative stability, 11 0°C EN 14 112 6.0 – hours Acid value EN 14 104 – 0.50 mg KOH/g Iodine value EN 14 111 – 12 0 g I /10 0 g Linolenic acid content EN 14 103 – 12 % (m/m) – 1 % (m/m) Content of FAME with ≥4 double bonds Methanol content EN 14 110 – 0.20 % ( m/m) Monoglyceride content EN 14 105 – 0.80 % (m/m) Diglyceride content EN 14 105 – 0.20... contamination EN 12 662 – 24 mg/kg Copper strip corrosion (3 hours at 50°C) ISO 216 0 – No .1 rating Oxidation stability, at 11 0°C EN 14 112 6 – hours Acid value EN 14 104 – 0.5 mg KOH Iodine value EN 14 111 – 14 0 g I /10 0 g Linolenic acid methyl ester EN 14 103 – 12 % (m/m) – 1 % (m/m) Content of FAME with ≥4 double bonds Methanol content EN 14 110 – 0.2 % (m/m) Monoglyceride content EN 14 105 – 0.8 % (m/m)... 0.20 % (m/m) Triglyceride content EN 14 105 – 0.20 % (m/m) Free glycerine EN 14 105; EN 14 106 – 0.02 % (m/m) Total glycerine EN 14 105 – 0.25 % (m/m) Alkali metals (Na + K) EN 14 108; EN 14 109 – 5.0 mg/kg Earth alkali metals (Ca + Mg) EN 14 538 – 5.0 mg/kg Phosphorus content EN 14 107 – 10 .0 mg/kg Table 3 European biodiesel standard (EN 14 214 ) 7 Biodiesel Quality, Standards and Properties Property Test Method... value EN 14 104 To report – Oxidation stability at 11 0ºC EN 14 112 6 Table 6 Biodiesel standard in India – mg/kg hours 10 Biodiesel – Quality, Emissions and By- Products Property Test method Limits min max Units Ester content EN 14 103 96.5 – % (m/m) Density JIS K 2249 0.86 0.90 g/ml Kinematic Viscosity JIS K 2283 3.5 5.0 mm2/s Flash Point JIS K 2265 12 0 – °C Sulfur JIS K 25 41 1, –2, –6, –7 – 10 ppm 10 % Carbon... Triglyceride content EN 14 105 – 0.20 % (m/m) Free glycerine EN 14 105, EN 14 106 – 0.02 % (m/m) Cold-filter plugging point EN 11 6 – – °C Pour point ISO 3 016 – 0 °C Net calorific value (calculated) DIN 519 00, -1, -2, -3 35 – MJ/kg Table 2 European standard EN 14 213 for biodiesel as heating oil 6 Biodiesel – Quality, Emissions and By- Products Property Test method Limits min max Unit Ester content EN 14 103 96.5 – %... EN 14 105 – 0.2 % (m/m) Triglyceride content EN 14 105 – 0.2 % (m/m) Free glycerol EN 14 105; EN 14 106 – 0.02 % (m/m) Total glycerol EN 14 105 – 0.25 % (m/m) Group I metals (Na + K) EN 14 108; EN 14 109 – 5.0 mg/kg Group II metals (Ca + Mg) EN 14 538 – 5.0 mg/kg Phosphorus content EN 14 107 – 10 .0 mg/kg Cold Filter Plugging Point (CFPP) Winter/Summer EN 11 6 – –4/+3 °C Table 8 South African Biodiesel Standard... 10 370 – 0.30 % (m/m) Sulfated ash content ISO 3987 – 0.02 % (m/m) Water content EN ISO 12 937 – 500 mg/kg Total contamination EN 12 662 – 24 mg/kg Oxidative stability, 11 0°C EN 14 112 4.0 – hours Acid value EN 14 104 – 0.50 mg KOH/g Iodine value EN 14 111 – 13 0 g I /10 0 g – 1 % (m/m) Polyunsaturated methyl esters (>= 4 double bonds) Monoglyceride content EN 14 105 – 0.80 % (m/m) Diglyceride content EN 14 105... (e.g., 18 :1 indicates 18 carbon atoms and one double bond) The ester composition of biodiesel (methyl and ethyl esters) is shown in Table 11 (Bamgboye & Hansen, 2008; Barabás & Todoruţ, 2 010 ; Chuepeng &Komintarachat, 2 010 ) The highest concentrations are C18 :1, C18:2, C18:3, followed by C18:0 A significant exception is biodiesel from coconut oil, in the case of which the highest concentration is C12:0, C14:0 . class Oxidative stability, 11 0°C EN 14 112 6.0 – hours Acid value EN 14 104 – 0.50 mg KOH/g Iodine value EN 14 111 – 12 0 g I /10 0 g Linolenic acid content EN 14 103 – 12 % (m/m) Content of FAME. Preface IX Part 1 Biodiesel: Quality and Standards 1 Chapter 1 Biodiesel Quality, Standards and Properties 3 István Barabás and Ioan-Adrian Todoruţ Chapter 2 Characterization of Biodiesel by Unconventional. EN ISO 12 937 – 500 mg/kg Total contamination EN 12 662 – 24 mg/kg Oxidative stability, 11 0°C EN 14 112 4.0 – hours Acid value EN 14 104 – 0.50 mg KOH/g Iodine value EN 14 111 – 13 0 g I /10 0 g Polyunsaturated