Methods in Lignin Chemistry PDF
Preview Methods in Lignin Chemistry
Springer Series in Wood Science Editor: T. E. Timell M. H. Zimmermann Xylem Structure and the Ascent of Sap (1983) 1. F. Siau Transport Processes in Wood (1984) R.R. Archer Growth Stresses and Strains in Trees (1986) W.E. Hillis Heartwood and Tree Exudates (1987) S. Carlquist Comparative Wood Anatomy (1988) L. W. Roberts / P. B. Gahan / R. Aloni Vascular Differentiation and Plant Growth Regulators (1988) C. Skaar Wood-Water Relations (1988) 1.M. Harris Spiral Grain and Wave Phenomena in Wood Formation (1989) B. 1. Zobel/ 1. P. van Buijtenen Wood Variation (1989) P. Hakkila Utilization of Residual Forest Biomass (1989) 1.W. Rowe Natural Products of Woody Plants (1989) K.-E.L. Eriksson/R.A. Blanchette/P. Ander Microbial and Enzymatic Degradation of Wood and Wood Components (1990) R. A. Blanchette / A. R. Biggs Defense Mechanisms of Woody Plants Against Fungi (1992) S. Y. Lin / C. W. Dence Methods in Lignin Chemistry (1992) G. Torgovnikov Dielectric Properties of Wood and Wood-Based Materials (1993) Stephen Y. Lin Carlton W. Dence (Eds.) Methods in Lignin Chemistry With 190 Figures Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest Dr. STEPHEN Y. LIN LignoTech USA Inc. 100 Highway 51 South Rothschild, WI 54474, USA Professor Emeritus Dr. CARLTON W. DENCE 600 Black Walnut Court Hendersonville, NC 28792, USA Series Editor: T.E. TIMELL State University of New York College of Environmental Science and Forestry Syracuse, NY 13210, USA Cover: Transverse section of Pinus lambertiana wood. Courtesy of Dr. Carl de Zeeuw, SUNY College of Environmental Science and Forestry, Syracuse, New York ISBN-13 :978-3-642-74067-1 e-ISBN-13:978-3-642-74065-7 DOT: 10.1007/978-3-642-74065-7 Library of Congress Cataloging-in-Publication Data. Methods in lignin chemistry / Stephen Y. Lin, Carlton W. Dence (eds.). p. em. - (Springer series in wood science) Includes bibliographical references and index. ISBN-13:978-3-642-74067-1 1. Lignin. I. Lin, Stephen Y. II. Dence, Carlton w. III. Series. TS933.L5M47 1992 661'.802-dc20 92-6677 This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplica tion of this publication or parts thereof is permitted only under the provisions of the German Copy right Law of September 9, 1965, in its current version, and permission for use must always be ob tained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. © Springer-Verlag Berlin Heidelberg 1992 Softcover reprint of the hardcover 1st edition 1992 The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Best-set Typesetter Ltd., Hong Kong, and K + V Fotosatz GmbH, Beerfelden 3113145-5 4 3 2 1 0 - Printed on acid-free paper Dedication As this book neared completion, we learned of the sudden and unex pected death of Dr. Kyosti V. Sarkanen, Professor of Wood Chem istry at the University of Washington. Just prior to his passing, Dr. Sarkanen had reviewed several portions of this book and was in the process of co-authoring the section on ozonolysis. Ironically, these activities coincided with the culmination of a professional career that spanned nearly five decades during which he established himself as a dominant figure in the field of wood and, in particular, lignin chemistry. It is not our intention to echo here the numerous eUlogies marking his passing or even to attempt to highlight his scientific accomplish ments. It suffices to say that those of us who were fortunate to know him personally as a teacher, researcher, adviser, colleague, or co worker are fully aware of the enormous impact he made on the devel opment of wood science; others who come to know him indirectly through his published work have the opportunity to gauge his uni queness for themselves. As co-editors, we deem it a privilege to dedicate this book to the memory of Dr. Sarkanen as a fitting tribute to a colleague whose research contributions and scientific insight pro vided the basis for the shaping and refining of many of the concepts expressed within its covers. CARLTON W. DENCE and STEPHEN Y. LIN Preface The structural complexity of lignin has continually challenged the in genuity of researchers to develop suitable methods for its charac terization prior to and following a wide variety of chemical, biologi cal, and physical treatments. Initially, activity along these lines was fueled by a desire to interpret technical delignification (Le., pulping) processes in terms of accompanying structural changes in the lignin. Subsequently, increasingly wide ranging, in-depth investigations on the structure and reactivity of lignin exposed the inadequacy of many of the methods currently in use and underscored the ever-continuing need to develop new methods capable of solving the unique analytical problems associated with lignin. Characteristically, such methods should be selective, sensitive, suitable for quantitative measurements, and capable of being applied directly to, and without destruction of, the lignin or lignocellulose sample. One notable example of the head way being made in reaching this objective is the relatively recent devel opment and refinement of methods based on the use of sophisticated instrumentation, e.g., lH_ and 13C-NMR spectroscopy. Although the utility of many of these and other recently developed methods de scribed in this book has yet to be fully and satisfactorily exploited, we believe that progress already made in this direction will continue and most likely accelerate. The decision to produce this book was prompted mainly by the acknowledged need for an up-to-date, single source compilation of lignin methodology. Hitherto, this need was, in part, satisfied by B. L. Browning's two-volume set of books, Methods of Wood Chemistry, which was published nearly 30 years ago. The recognition that these books had, in part, become outdated was a major consideration in ar riving at our decision to undertake to assemble a book reflecting the current status of lignin methodology. While we envision Methods in Lignin Chemistry as broadly serving the needs of professionals in academia, the pulp and paper industry, and allied industries, we also anticipate that the format adopted here for presenting the informa tion will be particularly useful to those beginning a career in wood and/or lignin chemistry and to those with no previous background in or experience with lignin or lignocellulosics and whose interest is pro jected to be on a one-time-only, short-term basis. VIII Preface The core element common to each chapter in this book is a de tailed, step-by-step description of what, in the judgment of the author(s), is the preferred method for conducting a specific analysis or operation. This particular format was selected to enable the reader to use the book essentially as a laboratory manual thereby obviating the need to search for and evaluate methods scattered throughout the literature. The methods included are a blend of the traditional and the contemporary. In some instances, what appeared to be promising analytical methods were bypassed in favor of more widely accepted methods on the grounds that they had not been field-tested sufficient ly to authenticate their reliability. The description of the preferred method is augmented by supporting information including, for exam ple, a survey of alternative methods, a discussion of the principle underlying the preferred method, the advantages and disadvantages of the method, the type and significance of information provided by the analysis, and the presentation of typical analytical data. From the onset of this undertaking it was obvious to us that the range of topics we wished to include virtually necessitated our draw ing on the expertise of a considerable number of individuals well versed in the principles and applications of the selected methodology. We were also aware that the adoption of a multi-author format entail ed risks that might impact negatively on the uniformity, general quality, and timetable for completion of the book. Without question, some of these concerns did prove to be justified. On the other hand, when this book is viewed in its totality, we believe that the overall quality and usefulness of its contents vindicates our decision to pro ceed as we did. With this in mind, we commend the international team of authors for service well performed in helping to make Methods in Lignin Chemistry a reality. Others who played important roles in its creation are acknowledged below. STEPHEN Y. LIN CARLTON W. DENCE Acknowledgments We are indebted to the following persons who generously contributed their time to review and recommend revision for several chapters in this book: F. Agblevor, L. Amos, S. Black, J. Boxell, H. L. Chum, R. Evans, D. A. I. Goring, M. Himmel, D. K. Johnson, L. Landucci, J. Obst, S. Omori, M. G. Paice, K. V. Sarkanen, and T. P. Schultz. We also acknowledge with gratitude the special contributions of T. E. Timell, Series Editor, who, in addition to reviewing and editing each manuscript, advised us on matters related specifically to organi zation, language, and style conventions during the entire period in which material for the book was being assembled. Our sincere appreciation is also expressed to Sarah Remon for her valued service in retyping promptly and accurately many of the edited and revised manuscripts. Finally, we individually wish to thank G. A. Rasmussen of LignoTech USA, Inc. (SYL) for his support and encouragement in this undertaking and the SUNY College of Environmental Science and Forestry (CWD) for permission to discharge attendant editorial responsibilities concurrently with customary academic duties. Rib Mountain, WI STEPHEN Y. LIN Hendersonville, NC CARLTON W. DENCE August 1992 Contents Chapter 1 Introduction ............................ . 1 Introduction ................................. . 3 C. W. DENeE and S. Y. LIN 1.1 General Structural Features of Lignin ............ 3 1.2 Variations in Concentration and Composition of Lignin in Xylem ............................ 6 1.3 Isolation and Recovery of Lignin ................ 7 1.4 Physical Properties of Lignin ................... 8 1.5 Structure-Modifying Reactions .................. 9 1.5.1 Modification of the Aromatic Ring. . . . .. . . . . . . . . 9 1.5.1.1 Electrophilic Substitution ....................... 9 1.5.1.2 Conversion of Aromatic Rings to Nonaromatic Cyclic Structures .............................. 11 1.5.1.3 Conversion of Cyclic to Acyclic Structures ........ 11 1.5.1.4 Ring Coupling and Condensation Reactions ...... 12 1.5.2 Modification of the Propanoid Side Chain ....... 12 1.5.2.1 Cleavage of Ether Bonds ....................... 12 1.5.2.2 Cleavage of Carbon-Carbon Bonds .............. 13 1.5.2.3 Substitution Reactions ......................... 14 1.5.2.4 Formation and Elimination of Multiple Bond Functionalities ................................ 15 1.5.3 Future Analytical Needs ........................ 16 References ............................................ 17 Chapter 2 Detection and Determination ............. 21 2.1 The Detection of Lignin ...................... . 23 1. NAKANO and G. MESHITSUKA 2.1.1 Introduction ................................. . 23 2.1.2 Reagents for the Detection of Lignin ........... . 23 2.1.2.1 Aliphatic Compounds ......................... . 23 2.1.2.2 Phenols and Aromatic Amines ................. . 23 2.1.2.3 Heterocyclic Compounds ...................... . 24 XII Contents 2.1.2.4 Inorganic Reagents ........................... . 24 2.1.2.5 Unclassified Reagents ........................ . 25 2.1.3 Color-Forming Reaction Sequences ............. . 25 2.1.4 Procedures for the Detection of Lignin ......... . 28 2.1.4.1 Color Reaction with Phloroglucinol-Hydrochloric Acid ....................................... . 29 2.1.4.2 The Maule Color Reaction .................... . 29 2.1.4.3 The Cross and Bevan Color Reaction ........... . 29 2.1.4.4 Color Reaction with Tosyl Chloride/Pyridine, p-Nitrosodimethylaniline/Potassium Cyanide .... . 30 2.1.4.5 Color Reaction with Quinone Monochlorimide .. . 30 2.1.4.6 Color Reaction with Potassium Nitrosodisulfonate 31 2.1.4.7 Color Reaction Based on the Formation of Nitrosophenols (Pearl-Benson Method) ....... . 31 References ............................................ 32 2.2 The Determination of Lignin 33 C.W. DENCE 2.2.1 Introduction ................................ . 33 2.2.2 Direct Methods .............................. . 33 2.2.2.1 Acid Hydrolysis of Wood and Pulp ............ . 33 2.2.2.2 Determination of Acid-Insoluble (Klason) Lignin in Wood and Pulp ..................... . 34 2.2.2.3 Determination of Acid-Soluble Lignin in Wood and Pulp ................................... . 39 2.2.2.4 Acid Hydrolysis of Annual Plants, Developing Wood, and Forage ................. . 40 2.2.2.5 Determination of Acid-Insoluble Lignin in Annual Plants, Developing Wood, and Forage .......... . 41 2.2.3 Indirect Methods ............................ . 42 2.2.3.1 Spectrophotometric Methods .................. . 42 2.2.3.2 Determination of Lignin in Wood and Pulp by the Acetyl Bromide Method ................ . 44 2.2.3.3 Methods Based on Oxidant Consumption ....... . 48 2.2.3.4 Determination of the Kappa Number of Pulp ... . 50 2.2.4 Determination of Lignin in Solution ........... . 54 2.2.4.1 Determination of Dissolved Lignin by the Modified Pearl-Benson (Nitrosation) Method ............. . 55 References ........................................... . 58
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