Particulate Carbon: Formation During Combustion

500 Pages·1981·15.509 MB·English

by  H. Gg. Wagner (auth.), Donald C. Siegla, George W. Smith (eds.)

Donald C. Siegla E ditor
Particulate Carbon
PARTICULATE CARBON
Formation During Combustion
PUBLISHED SYMPOSIA
Held at
General Motors Research Laboratories
Warren, Michigan
1980 R. L. Klimisch, G. T. Wolff, eds., Particulate carbon: Atmospheric life cycle.
Plenum Press, New York. In preparation.
1980 D. C. Siegla, G. W. Smith, eds., Particulate carbon: Formation during com
bustion. Plenum Press, New York, 1981.
1979 R. C. Schwing, W. A. Albers, Jr., eds., Societal risk assessmellt: How safe is
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1978 J. N. Mattavi, C. A. Amann, eds., Combustion modeling in reciprocating
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1977 D. P. Koistinen, N.-M. Wang, eds., Mechanics of sheet metalforming: Mate
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PARTICULATE CARBON
Formation During Combustion
Edited by
DONALD C. SIEGLA and GEORGE W. SMITH
General Motors Research Laboratories
SPRINGER SCIENCE+BUSINESS MEDIA, LLC 1981
Library of Congress Cataloging in Publication Data
Main entry under title:
Particulate carbon, formation during combustion.
"Proceedings of an international symposium on particulate carbon, formation
during combustion, held October IS-16, 1980, at the General Motors Research
Laboratories, Warren, Michigan" - Verso t.p.
Includes bibliographies and index.
1. Combustion - Congresses. 2. Soot - Congresses. 3. Carbon - Congresses. I.
Siegla, Donald C. II. Smith, George W. (George Wolfram), 1932-
QDSI6.P36 S41.3'61 81-15363
ISBN 978-1-4757-6139-9 ISBN 978-1-4757-6137-5 (eBook) AACR2
DOI 10.1007/978-1-4757-6137-5
Proceedings of an international symposium on Particulate Carbon:
Formation During Combustion, held October IS-16, 1980, at the
General Motors Research Laboratories, Warren, Michigan
© 1981 Springer Science+Business Media New York
Originally published by Plenwn Press, New York in 1981
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
v
PREFACE
The goal of the symposium, "Particulate Carbon: Formation During Combustion",
held at the General Motors Research Laboratories on October 15 and 16, 1980, was to
discuss fundamental aspects of soot formation and oxidation in combustion systems
and to stimulate new research by extensive interactions among the participants. This
book contains lhe papers and discussions of that symposium, the 26th in an annual
series covering many different disciplines which are timely and of interest to both
General Motors and the technical community at large.
The subject of this symposium has considerable relevance for man in his effort to
control and preserve his environment. Emission of particulate carbon into the atmos
phere from combustion sources is of concern to scientists and laymen alike. The hope
of reducing this emission clearly requires an understanding of its formation during the
combustion process, itself an area of considerable long-term research interest. It is our
hope that this symposium has served to summarize what is known so that what
remains to be learned can be pursued with greater vigor.
The scientists and engineers who participated in this symposium came from seven
countries and were chosen because of their expertise in physical and chemical charac
terization, formation and oxidation kinetics, premixed and diffusion combustion,
turbulent mixing, spray combustion, and combustion in engines. Attendance was
limited in order to enable a closer contact among the participants, the intent being to
foster not only discussion among experts in related fields but also interaction among
those conducting fundamental research and those responsible for the design of practi
cal combustion systems. Hence, new channels of communication were established in
order to create an awareness of the concerns and objectives of others and thus enhance
the productivity of future research.
The organization of the papers in this volume follows that ofthe symposium itself.
The chapters are arranged in five groups: an overview of the field, characterization of
combustion-formed particulate carbon, basic formation and oxidation mechanisms
and kinetics, formation during continuous combustion, and formation during inter
mittent combustion. Thus the subject matter of the book progresses from the funda
mental to the practical. The volume, like the symposium, concludes with a summary
and look to the future by Prof. Palmer, one of the pioneers in the field.
VI PREFACE
One confusing aspect of the literature of particulate carbon became apparent during
the symposium: the diversity of nomenclature. Various participants used different
terminology in referring to the same entity or concept. (Dr. Medalia addresses this
problem in his remarks on pg. 89.) For instance, several different names have been
used to describe the quasi-spherical units of which a soot agglomerate is composed:
primary particles. elementary particles. spherical particles. and spherical units. The
simple term spherule (which makes no implications concerning the elementary or
primary nature of the quasi-spherical units) was used by some conferees to avoid
confusion. Prof. Hilliard has pointed out that spherule possesses the added merit of
priority, having been used by Lord Rayleigh [Proc. Roy. Soc., Vol. 29 (1879), p. 71]
over 100 years ago to describe colliding droplets. Names applied to describe the total
soot structural entity have ranged from particulate (usually an adjective) to particle.
agglomerate. aggregate. aciniform carbon (see pg. 89), and cluster (all nouns). The
terms agglomeration. coagulation. clustering. and coalescence have been used to
describe aspects of the aggregation process. No confusion arises if the usage is
carefully and properly defined, which, we feel, is the case with the papers in this
volume. Our purpose in this paragraph has been to call attention to a need which all
expanding fields of endeavor share: terminology which is accurate, concise, consist
ent, and capable of growth.
The organization of the symposium and the publication of these proceedings
resulted from the collaboration of many people. We are extremely grateful to our
symposium advisors, John B. Heywood, Jack B. Howard, and Howard B. Palmer, for
helping us to select topics and speakers for a stimulating and worthwhile meeting. To
our session chairmen, Klaus H. Homann, Irvin Glassman, John P. Longwell, and
John B. Heywood, we express our indebtedness for participating in and guiding the
progress of the discussions. And, of course, we are grateful to the speakers and
participants of the symposium who contributed the essential ingredient of a successful
conference: free and enthusiastic exchange of ideas. We thank John D. Caplan,
William G. Agnew, Nils L. Muench, Charles A. Amann, Frank E. Jamerson, and
Leroy R. Buzan, for their support and guidance. Advice on technical and organiza
tional matters from Walter A. Albers, Jr., Richard J. Blint, Donald P. Koistinen,
James A. Mattavi, and Richard C. Schwing was greatly appreciated. The assistance of
R. Thomas Beaman with physical arrangements was invaluable. We are grateful to
Tanvir Ahmad, James H. Bechtel, Richard J. Blint, James P. Myers, Steven L. Plee,
David M. Roessler, Mary Lee Smith, Robin Stevenson, and Richard E. Teets for
aiding in the transcription and editing processes. We appreciate the contributions of
Jane K. Fiebelkorn, Elizabeth L. Kalata, Linda D. Sroda, and Mildred D.
Woodhouse who expertly assisted in typing and the administrative details of the
symposium. Finally, we particularly thank David N. Havelock for supervising the
conversion of the edited manuscripts into this volume.
Donald C. Siegla George W. Smith
Engine Research Department Physics Department
General Motors Research Laboratories General Motors Research Laboratories
Symposium Cochairman Symposium Cochairman
VII
CONTENTS
Preface ..................... , ......................................... v
Organizers, Session Chairmen and Authors x
Soot Formation - An Overview
H. Gg. Wagner, Universitat Gottingen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. I
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 25
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
SESSION I: Characterization of Combustion-Formed
Particulate Carbon
Chairman: K.H. Homann,
Technische Hochschule Darmstadt. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 31
Morphology and Internal Structure of
Soot and Carbon Blacks
1. Lahaye, Centre de Recherches sur la Physico-Chimie des Surfaces Solides, C.N. R.S.
G. Prado, Massachusetts Institute of Technology. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 50
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51
Optical Properties and Morphology of Particulate
Carbon: Variation with Air / Fuel Ratio
D. M. Roessler, F. R. Faxvog, R. Stevenson and G. W. Smith,
General Motors Research Laboratories ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 57
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 82
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 84
The Chemical Analysis of Particulate Carbon
M. L. Lee, Brigham Young University
K. D. Bartle, University of Leeds ....................................... " 91
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 100
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 104
SESSION II: Basic Mechanisms and Kinetics
Chairman: I. Glassman, Princeton University. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 107
Pre-particle Chemistry in Soot Formation
1. D. Bittner and 1. B. Howard,
Massachusetts Institute of Technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 109
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 135
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 137
VIII CONTENTS
Physical Aspects of Nucleation and
Growth of Soot Particles
G. Prado, Massachusetts Institute of Technology
J. Lahaye, Centre de Recherches sur la Physico-Chimie des Surfaces Solides, C. N. R.S. 143
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 163
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 164
Ionic Mechanisms of Soot Nucleation in Premixed Flames
D. B. Olson and H. F. Calcote,
AeroChem Research Laboratories, Inc. ................................... 177
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 200
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 20 I
Laser Light Scattering and Fluorescence Diagnostics of Rich Flames
Produced by Gaseous and Liquid Fuels
A. D'Alessio, University of Naples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 207
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 254
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 256
Soot Oxidation in Flames
K. G. Neoh, J. B. Howard and A. F. Sarofim,
Massachusetts Institute of Technology ................................... 261
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277
SESSION III: Formation During Continuous Combustion
Chairman: J. P. Longwell,
Massachusetts Institute of Technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 283
Soot Formation in let-Stirred Reactors
R. M. Kowalik, L. A. Ruth and W. S. Blazowski,
Exxon Research and Engineering Company ............................... , 285
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 294
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 294
Modeling Soot Emissions in Combustion Systems
R. Farmer, R. Edelman and E. Wong,
Science Applications, Inc. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 299
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 316
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 317
Modeling of Reaction Processes in Turbulent Flames
with Special Emphasis on Soot Formation and Combustion
B. F. Magnussen, The Norwegian Institute of Technology. . . . . . . . . . . . . . . . . . . .. 321
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 334
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 335
CONTENTS ix
Soot Studies in Gas Turbine Combustors and
Other Turbulent Spray Flames
A. M. Mellor, Purdue University. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 343
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 353
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 355
SESSION IV: Formation During Intermittent Combustion
Chairman: J. B. Heywood,
Massachusetts Institute of Technology ................................. 361
A Phenomenological Description of Particulate
Formation During Constant Volume Combustion
T. M. Dyer and W. L. Flower,
Sandia National Laboratories. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 363
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 384
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 385
Time Resolved Soot Particulates in
Diesel Spray Combustion
T. Kadota and N. A. Henein,
Wayne State University. . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . .. 391
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 414
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 414
Effects of Flame Temperature and Air-Fuel Mixing
on Emission of Particulate Carbon from a Divided
Chamber Diesel Engine
S. L. Plee, T. Ahmad, J. P. Myers and D. C. Siegla,
General Motors Research Laboratories ................................... 423
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 477
Appendix ........................................................ 482
Discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 484
Symposium Summary
H. B. Palmer, Pennsylvania State University 489
Participants ....... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 493
Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 499