Green Energy and Technology

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Silvia Daniela Romano Patricio Anbal Sorichetti

Dielectric Spectroscopy in Biodiesel Production and Characterization

123

Prof. Dr. Eng. Silvia Daniela Romano Grupo de Energas Renovables Facultad de Ingeniera Universidad de Buenos Aires Av. Paseo Coln 850 1063 Buenos Aires Argentina e-mail: sromano@.uba.ar and Consejo Nacional de Investigaciones Cientcas y Tcnicas (CONICET) Av. Rivadavia 1917 1033 Buenos Aires Argentina

Prof. Eng. Patricio Anbal Sorichetti Laboratorio de Sistemas Lquidos Facultad de Ingeniera Universidad de Buenos Aires Av. Paseo Coln 850 1063 Buenos Aires Argentina e-mail: psorich@.uba.ar

ISSN 1865-3529 ISBN 978-1-84996-518-7 DOI 10.1007/978-1-84996-519-4

Springer London Dordrecht Heidelberg New York

e-ISSN 1865-3537 e-ISBN 978-1-84996-519-4

British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Control Number: 2010936453 Springer-Verlag London Limited 2011 Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms of licenses issued by the Copyright Licensing Agency. Enquiries concerning reproduction outside those terms should be sent to the publishers. The use of registered names, trademarks, etc., in this publication does not imply, even in the absence of a specic statement, that such names are exempt from the relevant laws and regulations and therefore free for general use. The publisher makes no representation, express or implied, with regard to the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any errors or omissions that may be made. Cover design: eStudio Calamar, Berlin/Figueres Printed on acid-free paper Springer is part of Springer Science+Business Media (www.springer.com)

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Introduction to Biofuels . . . . . . . . . . . . . . . . . 1.2 Production of Biodiesel in the European Union. 1.3 Production of Biodiesel in the World . . . . . . . . 1.4 Concluding Remarks . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Introduction to Biodiesel Production . . . . . . . . . . 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1 Advantages of the Use of Biodiesel . . 2.1.2 Disadvantages of the Use of Biodiesel. 2.2 Raw Materials for Biodiesel Production . . . . . 2.2.1 Typical Oil Crops Useful for Biodiesel 2.2.2 Characteristics of Oils and Fats Used in Biodiesel Production . . . . . . . . . . . 2.2.3 Characteristics of Alcohols Used in Biodiesel Production . . . . . . . . . . . 2.3 Biodiesel Production Process . . . . . . . . . . . . 2.3.1 Treatment of Raw Materials . . . . . . . . 2.3.2 Alcohol-Catalyst Mixing . . . . . . . . . . 2.3.3 Chemical Reaction . . . . . . . . . . . . . . 2.3.4 Separation of the Reaction Products . . 2.3.5 Purification of the Reaction Products. . 2.4 Glycerin . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Uses . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Concluding Remarks . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Standards for Fuel Characterization . . . . . . . . . . . . . . . . . 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Biodiesel Characterization According to International Standards . . . . . . . . . . . . . . . . . . . . . . 3.3 Characterization Properties Required by Standards . . . . 3.4 Characterization Properties not Required by Standards. . 3.5 Quality Control of the Biodiesel Obtained in Different Production Scales. . . . . . . . . . . . . . . . . . . 3.6 Low-Cost Alternatives for Quality Control of Biodiesel . 3.7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Electric Properties of Liquids . . . . . . . . . . . . . . . . . . . . . . 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Electromagnetic Fields and Material Properties . . . . . . . 4.2.1 Electromagnetic Fields in a Vacuum . . . . . . . . . 4.2.2 Characteristic Scales and Approximations . . . . . 4.2.3 Classical Treatment of the Electromagnetic Field in Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.4 Electromagnetic Fields in Materials. . . . . . . . . . 4.3 Electromagnetic Energy Dissipation in Materials. . . . . . 4.4 Dielectric Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . 4.4.1 The Debye Model: Polarization Relaxation with a Single Characteristic Time . . . . . . . . . . . 4.4.2 Dielectrics with Several Relaxation Times . . . . . 4.4.3 Superposition of Multiple Relaxation Times: the HavriliakNegami Dielectric Function . . . . . 4.5 Dielectric Polarization in Liquids . . . . . . . . . . . . . . . . 4.5.1 Electronic Polarization. . . . . . . . . . . . . . . . . . . 4.5.2 Orientation Polarization . . . . . . . . . . . . . . . . . . 4.5.3 Interfacial Polarization. . . . . . . . . . . . . . . . . . . 4.6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Introduction to Dielectric Spectroscopy (DS) . . . . . . . . . . . . . . 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 Measurement of Dielectric Properties at Low Frequencies . . 5.2.1 Admittance, Capacitance, and Permittivity . . . . . . . . 5.2.2 Determination of the Cell Constant . . . . . . . . . . . . . 5.2.3 Dissipation Factor . . . . . . . . . . . . . . . . . . . . . . . . . 5.3 Measurement of Dielectric Properties at Higher Frequencies. 5.3.1 Propagation in Coaxial Transmission Lines . . . . . . . 5.3.2 Transmission Lines Excited by Harmonic Signals . . .

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5.3.3 Reflection Coefficient, Impedance and Admittance . 5.3.4 Transmission Lines under Pulsed Excitation. . . . . . 5.4 Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . 5.4.1 Temperature Control . . . . . . . . . . . . . . . . . . . . . . 5.4.2 Sample Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.3 Sample Handling . . . . . . . . . . . . . . . . . . . . . . . . 5.4.4 Low-Frequency Measuring Instruments . . . . . . . . . 5.4.5 High-Frequency Measuring Instruments . . . . . . . . . 5.4.6 Optical Measurements: Refractive Index . . . . . . . . 5.5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

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Dielectric Techniques for the Characterization of Raw Materials and Efuents in Biodiesel Production . . . . . 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2 Dielectric Properties of Vegetable Oils. . . . . . . . . . . . . . . . 6.3 Dielectric Properties of Treated Vegetable Oils . . . . . . . . . . 6.4 Dielectric Properties of Effluents from Biodiesel Production. 6.5 Refractive Index of Vegetable Oils . . . . . . . . . . . . . . . . . . 6.6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Application of Dielectric Spectroscopy to the Characterization of FAME in Biodiesel Production . 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2 Dielectric Model of FAME and Biodiesel. . . . . . . . . . . 7.3 Dielectric Properties of FAME . . . . . . . . . . . . . . . . . . 7.3.1 Permittivity . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.2 Conductivity. . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 Dielectric Properties of Biodiesel . . . . . . . . . . . . . . . . 7.4.1 Permittivity . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4.2 Conductivity. . . . . . . . . . . . . . . . . . . . . . . . . . 7.5 Refractive Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Relations Between the Properties Required by International Standards and Dielectric Properties of Biodiesel . 8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.2 Determination of Flash Point . . . . . . . . . . . . . . . . . . . . . . 8.3 Correlation Between Flash Point and Methanol Content in Biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.4 Temperature Dependence of Electrical Properties of Biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . .

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8.5

Permittivity and Conductivity in Containing Methanol . . . . . . . . 8.6 Concluding Remarks . . . . . . . . References . . . . . . . . . . . . . . . . . . .

Biodiesel ....................... ....................... .......................

96 97 98 101

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .