Structures and Dynamics of Asphaltenes PDF
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Structures and Dynamics of Asphaltenes Structures and Dynamics of Asphaltenes Edited by Oliver C. Mullins Schlumberger-Doll Research Ridgefield. Connecticut and Eric Y. Sheu Texaco. Inc. Beacon.}Vew York Springer Science+Business Media, LLC Library of Congress Cataloging in Publication Data Structures and dynamics of asphaltenes / edited by Oliver C. Mullins and Eric Y. Sheu. P- cm. "Proceedings of the International Symposium on Asphaltenes, held during the Fine Particle Society Meeting, August 23-24, 1995, in Chicago, Illinois and a Symposium on Asphaltene and Resid Characterization, sponsored jointly by the Fuel and Petroleum divisions of the American Chemical Society, held April 13-17, 1998, in San Francisco, California"—T.p. verso. Includes bibliographical references and index. ISBN 978-1-4899-1617-4 1. Asphaltene—Congresses. I. Mullins, Oliver C. II. Sheu, Eric Y. III. Fine Particle Society. Meeting (1995: Chicago, 111.) IV. American Chemical Society. V. International Symposium on As phaltenes (1995: Chicago, 111.) VI. Symposium on Asphaltene and Resid Characterization (1998: San Francisco, Calif.) QD305.H7S68 1998 98-39452 665.5,388—dc21 CIP Proceedings of the International Symposium on Asphaltenes, held during the Fine Particle Society Meeting, August 23-24, 1995, in Chicago, Illinois, and a Symposium on Asphaltene and Resid Characterization, sponsored jointly by the Fuel and Petroleum Divisions of the American Chemical Society, held April 13-17, 1998, in San Francisco, California ISBN 978-1-4899-1617-4 ISBN 978-1-4899-1615-0 (eBook) DOI 10.1007/978-1-4899-1615-0 © 1998 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1998 Softcover reprint of the hardcover 1st edition 1998 1098 765432 1 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher To Cynthia, Olivia, Stephanie, and Clinton, -OCM To Julie, Jonathan and Anthony -EYS PREFACE The investigative assault upon the enigmatic asphaltenes has recently resulted in sig nificant advances in many varied disciplines. Taken individually, each discipline exposes certain facets of asphaltenes, but each, alone, can never reveal asphaltenes from all van tages. Even seemingly narrowly focused issues such as the molecular structures of asphal tenes, or the colloidal structures of asphaltenes require a confluence of many lines of investigation to yield an understanding which differs from truth by diminishing uncer tainty. An holistic treatment of the asphaltenes is a powerful approach to evolve further their understanding. For example, examination of asphaltenes at the highest resolution yields molecular structure. A slight increase in scale probes asphaltene colloidal structure. Weaving together asphaltene studies performed at different length scales results in a fabric which envelops an encompassing vision of asphaltenes. At the same time, the interfaces of these hierarchical studies provide additional constraints on imagination, more than investi gations at individual length scales alone. These considerations shaped the timing, format, and the content of our book. The editors are very appreciative of the diligence and hard work manifest in each of the contributed chapters herein. We thank the contributing authors for making this project a success. Oliver C. Mullins Eric Y. Sheu vii CONTENTS I. Asphaltenes: Types and Sources ...................................... . TehFu Yen ll. Optical Interrogation of Aromatic Moieties in Crude Oils and Asphaitenes . . . . . 21 Oliver C. Mullins Ill. Molecular Structure and Intermolecular Interaction of Asphaltenes by FT-IR, NMR,EPR .................................................. 79 R. Scotti and L. Montanari IV. Self-Association of Asphaltenes: Structure and Molecular Packing 115 Eric Y. Sheu V. Colloidal Structural Evolution from Stable to Flocculated State of Asphaltene Solutions and Heavy Crudes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145 D. Espinat, E. Rosenberg, M. Scarsella, L. Barre, D. Fenistein, and D. Broseta VI. Molecular and Colloidal Structure of Coal Asphaltenes and Other Heavy Solvent Soluble Components .................................... 203 Masashi lino and Toshimasa Takanohashi VII. Characterization and Phase Behavior of Asphaltenic Crude Oils 227 Kevin A. Ferwom and William Y. Svrcek VIII. Conductivity of Asphaltenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247 Per Fotland and Hilde Anfindsen IX. A New Suspension Viscosity Model and Its Application to Asphaltene Association Thermodynamics and Structures ........................ 267 Moon-Sun Lin, 1. M. Chaffin, R. R. Davison, C. 1. Glover, and J. A. Bullin x. Characterization of Asphaltenes and Heavy Oils Using Hydrodynamic Property Measurements ................................................ 303 Ruth E. Baltus ix x Contents XI. Asphaltene and Resin Stabilized Crude Oil Emulsions: Experimental Characterization and Destabilization .............................. 337 Johan Sjoblom, 0ystein Srether, 0ivind Midttun, Marit-Helen Ese, Olav Urdahl, and Harald Ferdedal XII. The Role of Petroleum Asphaltenes in the Stabilization of Water-in-Oil Emulsions ................................................... 377 Joseph D. McLean, P. Matthew Spiecker, Andrew P. Sullivan, and Peter K. Kilpatrick Index................................................................. 423 Chapter I ASPHALTENES Types and Sources TehFu Yen School of Engineering University of Southern California Los Angeles, California 90089-2531 INTRODUCTION What will be stated in the following is that asphaltenes are not limited to petroleum origins. Asphaltenes can be derived from any fossil fuel sources. These sources include the virgin component, all the intermediates leading to a finished commodity, and to the processed products. A few of the fossil fuel derived asphaltenes are: virgin petroleum, re fining bottoms, coal liquids, tar sands, bitumens, oil shale extracts, shale oils, coal ex tracts, and a great number of naturally-occurring asphaltoids, asphaltites, and asphalts. In order to explore the role of asphaltene in these different sources or types, the unique prop erties of asphaltenes must be discussed here. The properties and behavior of asphalts and bitumens are critically dependent on the nature of the constituents. Chemically these constituents consist of hydrocarbons and het erocyclic or nitrogen-, sulfur-, and oxygen-containing compounds. Separation of the vari ous fractions of asphalt or bitumen is usually based on their different boiling point ranges, molecular weights, and solubilities in solvents of different polarities. Techniques for ob taining narrow fractions include vacuum distillation, solvent extraction, thermal diffusion, crystallization, and others, individually or in combination, followed by chromatographic separation. Often the topped crude and the asphalt are fractionated by solvent partitioning, selective absorption-desorption, and chemical precipitation. The principal classes of con stituents are gas oil, asphaitene, resin, carboid, carbene and mesophase. All fossil based oils contain some asphaltics, ranging from 0.1-50 percent; however, heavy oil has the highest asphaltene content. The amount and the types of asphaltene will greatly influence the constitution and properties of a particular oil. The following Table 1 il lustrates the principle that asphaltenes derived from petroleum, shale oil, and coal liquid are widely different if characterized by even a few structural parameters. The fine structure of a 1 2 Teh Fu Yen Table 1. Ranges of value as expressed by structural parameters of various asphaltenes derived from different sources Parameter* Petroleum Shale Coal fa 0.2-0.5 0.4 0.6-0.7 La(A) 10-15 7-12 7-14 Le(A) 20 15 10 (J 0.5-0.7 0.5-0.6 0.3-0.5 Har.' Car(H/CA) 0.3-0.5 0.8-0.9 0.6-0.8 n 4-6 2-3 1-2 *fa• aromaticity; La. layer diameter; Le, cluster height; cr, degree of substi tution; Hat/Car' degree of ring condensation; n, average chain length. given asphaltene often can be elucidated by a number of structural parameters. At this time, it should be pointed out that although there are distinctive differences among asphaltenes, generally speaking they are very similar when compared in infrared or NMR spectra. SEPARATION OF ASPHALTENE FROM SOURCE MATERIAL Separation of components usually can be achieved by distillation. When a solution of a binary liquid has partially vaporized that component with the higher partial vapor pressure tends to concentrate in the vapor. This vapor may be condensed, and the vapor re sulting from the heating of this condensate is still further enriched in the more volatile component. This process of separation based on successive vaporization and condensation is fractional distillation. The separation factor is based on relative volatility. Multicompo nent distillation is possible at minimum reflux. Average virgin heavy crudes contain a certain portion of volatiles. It is not advisable to use the conventional method of characterizing crude by simple distillation at atmos pheric pressure up to 275 DC or even higher, since some thermal cracking reactions start above 200 DC. The best way is to "top" the volatile portion from the residue by vacuum distillation at very low pressure [1] and to keep the pot temperature below 150 DC. In this manner, the heat-sensitive portion of these fractions will be preserved [2]. In most distilla tion procedures, the bottom of the pot-the heavy fractions--have been severely ther mally altered due to cumulative effects. An empirical method to approximate the boiling point of most compounds has been based on the boiling point number (BPN), and BPN can be computed from the structural component ofa given compound [3]: bP = 230.14 (BPN)1I3 - 543 The segregation of individual components from a mixture can be accomplished by adsorption chromatography. The adsorbent is either packed in an open tube (column chro matography) or shaped in the form ofa sheet (thin layer chromatography, TLC) [4,5]. Sol vent is used to elute from the bed, and the resolution for a two-component system can be expressed as:
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