BIODIESEL – FEEDSTOCKS AND PROCESSING TECHNOLOGIES Edited by Margarita Stoytcheva and Gisela Montero Biodiesel – Feedstocks and Processing Technologies Edited by Margarita Stoytcheva and Gisela Montero 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 permits to copy, distribute, transmit, and adapt the work in any medium, so long as the original work is properly cited. 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 Dirk Ott, 2011. Used under license from Shutterstock.com First published October, 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 – Feedstocks and Processing Technologies, Edited by Margarita Stoytcheva and Gisela Montero p. cm. ISBN 978-953-307-713-0 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Feedstocks for Biodiesel Production 1 Chapter 1 Non Edible Oils: Raw Materials for Sustainable Biodiesel 3 C.L. Bianchi, C. Pirola, D.C. Boffito, A. Di Fronzo, G. Carvoli, D. Barnabè, R. Bucchi and A. Rispoli Chapter 2 Biodiesel Production from Waste Cooking Oil 23 Carlos A. Guerrero F., Andrés Guerrero-Romero and Fabio E. Sierra Chapter 3 Animal Fat Wastes for Biodiesel Production 45 Vivian Feddern, Anildo Cunha Junior, Marina Celant De Prá, Paulo Giovanni de Abreu, Jonas Irineu dos Santos Filho, Martha Mayumi Higarashi, Mauro Sulenta and Arlei Coldebella Chapter 4 Getting Lipids for Biodiesel Production from Oleaginous Fungi 71 Maddalena Rossi, Alberto Amaretti, Stefano Raimondi and Alan Leonardi Chapter 5 Microbial Biodiesel Production - Oil Feedstocks Produced from Microbial Cell Cultivations 93 Jianguo Zhang and Bo Hu Chapter 6 Algal Biomass and Biodiesel Production 111 Emad A. Shalaby Chapter 7 Microalgae as Feedstocks for Biodiesel Production 133 Jin Liu, Junchao Huang and Feng Chen Chapter 8 Eco-Physiological Barriers and Technological Advances for Biodiesel Production from Microalgae 161 Simrat Kaur, Mohan C. Kalita, Ravi B. Srivastava and Charles Spillane VI Contents Chapter 9 Advantages and Challenges of Microalgae as a Source of Oil for Biodiesel 177 Melinda J. Griffiths, Reay G. Dicks, Christine Richardson and Susan T. L. Harrison Chapter 10 An Integrated Waste-Free Biomass Utilization System for an Increased Productivity of Biofuel and Bioenergy 201 László Kótai, János Szépvölgyi, János Bozi, István Gács, Szabolcs Bálint, Ágnes Gömöry, András Angyal, János Balogh, Zhibin Li, Moutong Chen, Chen Wang and Baiquan Chen Part 2 Biodiesel Production Methods 227 Chapter 11 Production of Biodiesel via In-Situ Supercritical Methanol Transesterification 229 Asnida Yanti Ani, Mohd Azlan Mohd Ishak and Khudzir Ismail Chapter 12 Transesterification in Supercritical Conditions 247 Somkiat Ngamprasertsith and Ruengwit Sawangkeaw Chapter 13 Alternative Methods for Fatty Acid Alkyl-Esters Production: Microwaves, Radio-Frequency and Ultrasound 269 Paula Mazo, Gloria Restrepo and Luis Rios Chapter 14 Transesterification by Reactive Distillation for Synthesis and Characterization of Biodiesel 289 G.B.Shinde, V.S.Sapkal, R.S.Sapkal and N.B.Raut Chapter 15 Gas-Liquid Process, Thermodynamic Characteristics (19 Blends), Efficiency & Environmental Impacts, SEM Particulate Matter Analysis and On-Road Bus Trial of a Proven NO x Less Biodiesel 317 Kandukalpatti Chinnaraj Velappan and Nagarajan Vedaraman Chapter 16 Biodiesel Production with Solid Catalysts 339 Feng Guo and Zhen Fang Chapter 17 Heterogeneous Catalysts Based on H 3 PW 12 O 40 Heteropolyacid for Free Fatty Acids Esterification 359 Marcio Jose da Silva, Abiney Lemos Cardoso, Fernanda de Lima Menezes, Aline Mendes de Andrade and Manuel Gonzalo Hernandez Terrones Chapter 18 An Alternative Eco-Friendly Avenue for Castor Oil Biodiesel: Use of Solid Supported Acidic Salt Catalyst 379 Amrit Goswami Contents VII Chapter 19 The Immobilized Lipases in Biodiesel Production 397 Margarita Stoytcheva, Gisela Montero, Lydia Toscano, Velizar Gochev and Benjamin Valdez Chapter 20 Progress in Vegetable Oils Enzymatic Transesterification to Biodiesel - Case Study 411 Ana Aurelia Chirvase, Luminita Tcacenco, Nicoleta Radu and Irina Lupescu Chapter 21 Adsorption in Biodiesel Refining - A Review 427 Carlos Vera, Mariana Busto, Juan Yori, Gerardo Torres, Debora Manuale, Sergio Canavese and Jorge Sepúlveda Preface The increasing demand for energy worldwide, together with the depletion of crude oil reserves, environmental threats due to greenhouse gas emissions and new national and international legislation, is resulting in the imperative for petroleum-derived fuels to be complemented or substituted by biofuels. Such an alternative, renewable, biodegradable and nontoxic biofuel is biodiesel. The book “Biodiesel: Feedstocks and Processing Technologies” is intended to provide a professional look on the recent achievements and emerging trends in biodiesel production. It includes 21 chapters, organized in two sections. The first book section: “Feedstocks for Biodiesel Production” covers issues associated with the utilization of cost effective non-edible raw materials and wastes, and the development of biomass feedstock with physical and chemical properties that facilitate it processing to biodiesel. Chapter 1 is focused on the possible use of Brassicaceae spp., namely B.juncea in biodiesel production, and demonstrates the sustainability of an agronomic rotation between Brassicacea and nicotiana tabacum to produce vegetable oil from marginal soils. Chapter 2 comments on waste cooking oils transesterification to produce biodiesel, identifying the main types of cooking oils and supplying production process details. The generation of animal fat wastes in Brazil, their characterization and use for biodiesel synthesis is summarized in Chapter 3. The current knowledge advances in oleaginous fungi metabolism, physiology, and strain improvement are discussed in Chapter 4. Oleaginous fungi, and particularly yeasts, are considered as very efficient in the accumulation of intracellular triacylglycerols and it is expected that they will be exploited by the biofuel industry in the future. In continuation of the topic, Chapters 5-9 provide an overview on the various aspects of the use of microalgae as a source of oil for biodiesel, focusing on: a description of algae and their properties with regards to oil production, requirements and key factors in microalgal cultivation, methods and challenges in harvesting and processing of algal biomass, economic and environmental feasibility of microalgal biodiesel, mechanisms to enhance lipid productivity of microalgae, and future research directions. Finally, Chapter 10 discusses the implementation of an integrated waste-free biomass utilization system for an increased productivity of biofuel and bioenergy. X Preface The second book section: “Biodiesel Production Methods” is devoted to the advanced techniques for biodiesel synthesis. Chapters 11 and 12 discuss the technological aspects of the process of supercritical transesterification in biodiesel production, highlighting the effect of the reaction parameters, and the operational conditions. The economical feasibilities and the chemical limitations of supercritical transesterification, as well as process improvements and prospective are commented in details. Chapter 13 reports some alternative methods for biodiesel production reducing the reaction time, the reactive ratio, the quantity of the by-products, and the energy consumption. These include microwaves, radio frequency and ultrasound techniques. Biodiesel production efficiency improvement applying reactive distillation, and optimized transesterification processes are commented in Chapters 14 and 15. Recent advances in solid catalyst method for biodiesel production are reported in Chapters 16-18. Catalyst synthesis and characterization, as well as catalytic mechanism and catalytic activity are discussed, making use of research results. Chapters 19 and 20 comment on some aspects of the enzymatic approach to biodiesel production. Chapter 19 provides an overview on the use of immobilized lipases in biodiesel production, the techniques applied for enzyme immobilization, and the factors affecting the process. Chapter 20 is focused on a case study, namely the transesterification of rapeseed oil with immobilized yeast lipase. Biodiesel refining process is the subject of Chapter 21. The theoretical and practical aspects related to the functioning, design and operation of adsorbers and their application to the purification of biodiesel product and feedstocks are comprehensively reviewed. The adequate and up-to-date information provided in this book should be of interest for research scientist, students, and technologists, involved in biodiesel production. 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. Margarita Stoytcheva Gisela Montero Mexicali, Baja California Mexico [...]... consumption On the other hand, its physico-chemical properties meet the European 1 SUSBIOFUEL project (“Studio di fattibilità per la produzione di biocarburanti da semi oleosi di nuove specie e da sottoprodotti o materiali di scarto” – D.M 27800/7303/09), financially supported by the Ministry of Agricultural, Food and Forestry Policies – Italy 6 Biodiesel – Feedstocks and Processing Technologies specifications... materials for biodiesel production Iodine value, viscosity and density The iodine value (IV) is an index of the number of double bonds in biodiesel, and therefore is a parameter that quantifies the degree of unsaturation of biodiesel Both EN and ASTM standard methods measure the IV by addition of an iodine/chlorine reagent Biodiesel viscosity is directly correlated to the IV of biodiesel for biodiesel. .. for more than 90,000 people 24 Biodiesel – Feedstocks and Processing Technologies The biodiesel advantages are that it is a renewable and biodegradable biofuel; it produces less harmful emissions to the environment than those that produce fossil fuels Specifically the Palm biodiesel pure or mixed with diesel fuel reduces the emissions of CO2, nitrogen oxides (NOx) and particulate material Table 1,... methylester was higher than 98% The analyses of methyl esters and unreacted mono-, di- and triglycerides are accomplished through gas chromatography The detailed requirements for biodiesel according to both EN 14214 and US ASTM D 6751 are listed in paragraph 1 In the US a standard for biodiesel (ASTM D 6751 – Standard Specification for Biodiesel Fuel (B100) does not include the same number of parameters... R3OCOCH3 FAME (Fatty alkyl methyl ester) BIODIESEL Fig 1 Transesterification of a trygliceride C Pirola1, D.C Boffito1, A Di Fronzo1, G Carvoli1, D Barnabè2, R Bucchi2 and A Rispoli2 1 Università degli Studi di Milano – Dipartimento di Chimica Fisica ed Elettrochimica, Milano, Italy, 2 Agri2000 Soc Coop., Bologna, Italy 4 Biodiesel – Feedstocks and Processing Technologies Refined, low acidity oilseeds... J.G.Jr & Lu, C (2008) Stability of sulfated zirconia and the nature of the catalytically active species in the transesterification of tryglicerides Journal of Catalysis, Vol 255, pp 279-286 22 Biodiesel – Feedstocks and Processing Technologies T Ono, K Yoshiharu, US Patent 4,164, 506, 1979 The Royal Society (2008) Sustainable Biofuels: Prospects and Challenges The Clyvedon Press Ltd, ISBN 978 0 85403... 20 Biodiesel – Feedstocks and Processing Technologies Clixoo (2010) Preview of Comprehensive Castor Oil Report, In: Castor Oil Industry Reference & Resources, 30.05.2011, Available from http://www.castoroil.in Curto, G & Lazzeri, L (2006) Brassicacee, un Baluardo Sotterraneo Contro i Nematodi Agricoltura, Vol 34, No 5, (May 2006), pp.110-112 Environment Australia (2003) National Standards for Biodiesel. .. prEN14214 biodiesel standard sets a minimum limit for ester content of >96.5% mass, whereas the US ASTM D 6751 biodiesel standard does not set a specification for ester content Mono- and di-glycerides as well as tri-glycerides can remain in the final product in small quantities Most are generally reacted or concentrated in the glycerine phase and separated from the ester Both in the case of rapeseed oil and. .. required by the standard regulations (see Table 3) The experimental procedures to get the values of such properties are also standardized and are indicated in the regulations The following are parameters for starting oil that can affect the quality of the final biodiesel Sulfur and phosphorous content: High sulphur and phosphorous content in the fuels cause greater engine wear and in particular shorten... manure of B.juncea resulted in nematode infestation drastically decreased and improved soil quality, reflected in higher yield of crops in agronomic succession In the first year of experimentation B juncea was preferred to B.carinata because of its suitability to spring planting (starting period 18 Biodiesel – Feedstocks and Processing Technologies of the project SUSBIOFUEL) Further work will be necessary . BIODIESEL – FEEDSTOCKS AND PROCESSING TECHNOLOGIES Edited by Margarita Stoytcheva and Gisela Montero Biodiesel – Feedstocks and Processing Technologies. materiali di scarto” – D.M. 27800/7303/09), financially supported by the Ministry of Agricultural, Food and Forestry Policies – Italy. Biodiesel – Feedstocks and Processing Technologies 6. biodegradable and nontoxic biofuel is biodiesel. The book Biodiesel: Feedstocks and Processing Technologies is intended to provide a professional look on the recent achievements and emerging