Table Of ContentWolf
Methane
Conversion
By Oxidative
Processese
METHANE
CONVERSION BY
OXIDATIVE
PROCESSES
METHANE
CONVERSION BY
OXIDATIVE
PROCESSES
Fundamental and
Engineering Aspects
Edited by
E. E. Wolf
VAN NOSTRAND REINHOLD CATALYSIS SERIES
~SPRINGER SCIENCE+BUSINESS MEDIA, LLC
Copyright© 1992 by Springer Science+Business Media New York
Originally published by Van Nostrand Reinhold in 1992
Library of Congress Catalog Card Number 91-28504
ISBN 978-94-015-7451-8
All rights resetved. No part of this work covered by the
copyright hereon may be reproduced or used in any form or
by any means-graphic, electronic, or mechanical, including
photocopying, recording, taping, or information storage and
retrieval systems-without written permission of the
publisher.
Manufactured in the United States of America
16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1
Library of Congress Cataloging-in-Publication Data
Methane conversion by oxidative processes: fundamental and
engineering aspectsj[edited by] Eduardo E. Wolf.
p. em.
ISBN 978-94-015-7451-8 ISBN 978-94-015-7449-5 (eBook)
DOI 10.1007/978-94-015-7449-5
1. Synthetic fuels. 2. Methane. 3. Oxidation. I. Wolf, Eduardo E.
TP360.058 1991
662'.669-dc20 91-28504
CIP
VAN NOSTRAND REINHOLD
CATALYSIS SERIES
Burtron Davis, Series Editor
Metal-Support Interactions in Catalysis, Sintering, and Redispersion, edited
by Scott A. Stevenson, R.T.K. Baker, J.A. Dumesic, and Eli Ruckenstein
Molecular Sieves: Principles of Synthesis and Identification, R. Szostak
Raman Spectroscopy for Catalysis, John M. Stencel
Theoretical Aspects of Heterogeneous Catalysis, John B. Moffat
Biocatalysis, edited by Daniel A. Abramowicz
Methane Conversion By Oxidative Processes: Fundamental And Engineering
Aspects, edited by E. E. Wolf
v
Contents
Series Introduction IX
Preface XI
Part I. Fundamentals
1. Formation and Reactions of Methyl Radicals over Metal Oxide
Catalysts
J. H. Lunsford, TexasA&M University, College Station, TX 3
2. The Role of Gas-Phase Reactions during Methane Oxidative
Coupling
Z. Kalenik and E.E. Wolf, University of Notre Dame, Notre Dame,
IN 30
3. Partial Oxidation of Methane over Metal Oxides: Reaction
Mechanism and Active Oxygen Species
K. Otsuka and M. Hatano, Tokyo Institute of Technology, Tokyo,
Japan 78
4. The Oxidative Coupling of Methane: Reaction Pathways and Their
Process Implications
A. Ekstrom, CSIRO, Lucas Heights Laboratory, Australia 99
5. The Role of Lattice Oxygen in the Oxidative Coupling of Methane
K. Peil, G. Marcelin, and J.G. Goodwin, Jr., University of
'Pittsburgh, Pittsburgh, PA 138
6. The Development of Doped LijMgO Catalyst Systems for the
Low-Temperature Oxidative Coupling of Methane
S.J. Korf, J.A. Roos, and J.R.H. Ross, University of Twente,
Enschede, The Netherlands 168
7. Studies of the Mechanism of the Oxidative Coupling of Methane
Using Oxide Catalysts
G.J. Hutchings, The University of Liverpool, Liverpool, England,
and M.S. Scu"ell, CSIRO, Pretoria, South Africa 200
8. Elementary Reactions and Kinetic Modeling of the Oxidative
Coupling of Methane
K. van der Wiele, J.W.M.H. Geerts, J.M.N. van Kasteren,
Eindhoven Technische Universiteit, Eindhoven, The
Netherlands 259
vii
viii CONTENTS
9. Mechanism of Cooxidative Methane Dimerization Catalysis:
Kinetic and Thermodynamic Aspects
J.G. McCarty, SRI International, Menlo Park, CA 320
10. Morphological Aspects of Catalysts for Oxidative Coupling of
Methane
G.A. Martin and C. Mirodatos, Institut de Recherches sur Ia
Catalyse, CNRS, Villeurbanne, France 351
11. Basic Solids as Catalysts for the Oxidative Coupling of Methane
M. Baems, Ruhr-Universitiit, Bochum, Germany 382
12. The Direct Conversion of Methane to Methanol (DMTM)
H.D. Gesser and N.R. Hunter, University of Manitoba,
Canada 403
Part II. Engineering Aspects
13. The OXCO Process: The Direct Conversion of Natural Gas to
Olefins and Liquid Fuels Using Fluidized-Bed Technology
J.H. Edwards, K.T. Do, and R.I. Tyler, CSIRO, North Ryde,
Australia 429
14. Direct Conversion of Methane to C 's and Liquid Fuels: Process
2
Economics
J.L. Matherne and G.L. Cu/p, Union Carbide Chemicals and
Plastics Company, Inc., South Charleston, WV 463
15. Engineering Evaluation of Direct Methane Conversion Processes
J.C.W. Kuo, Mobil Research and Development Corporation,
Paulsboro, NJ 483
16. Summary
E.E. Wolf, University of Notre Dame, Notre Dame, IN 521
Index 541
Series Introduction
A reasonable case could be made that the scientific interest in catalytic
oxidation was the basis for the recognition of the phenomenon of catalysis.
Davy, in his attempt in 1817 to understand the science associated with the
safety lamp he had invented a few years earlier, undertook a series of
studies that led him to make the observation that a jet of gas, primarily
methane, would cause a platinum wire to continue to glow even though
the flame was extinguished and there was no visible flame. Dobereiner
reported in 1823 the results of a similar investigation and observed that
spongy platina would cause the ignition of a stream of hydrogen in air.
Based on this observation Dobereiner invented the first lighter. His lighter
employed hydrogen (generated from zinc and sulfuric acid) which passed
over finely divided platinum and which ignited the gas. Thousands of these
lighters were used over a number of years. Dobereiner refused to file a
patent for his lighter, commenting that "I love science more than money."
Davy thought the action of platinum was the result of heat while
Dobereiner believed the ~ffect ~as a manifestation of electricity. Faraday
became interested in the subject and published a paper on it in 1834; he
concluded that the cause for this reaction was similar to other reactions.
Berzelius viewed things differently from Faraday and introduced the
concept of catalysis in 1835. Berzelius is credited with the recognition of
catalysis even though his view that it was the result of a catalytic force was
incorrect.
From the beginning, catalysis has been associated with practicality.
Over the years, and especially in our century, industrial applications have
been a strong driving force in determining the areas of intense catalytic
research efforts. This is especially true in the case of natural gas,
and of methane in particular. Within the past 20 years, real-or
perceived-shortages have provided the basis for a period of intense
research on methanation catalysis. During the same period, recognition of
vast supplies of natural gas in locations where the demand is low or
nonexistent has provided motivation for extensive research to convert
methane to more valuable products, preferably liquid, by partial oxidation.
A science partly driven by economics will not always show an orderly
progression of activity. An analogous situation applies to a series of books
ix
X CONTENTS
on catalysis: It is never possible to develop a series in orderly fashion.
Potential authors find it increasingly difficult to justify the time needed to
write a book. The current economics of book publishing in a specialized
area such as catalysis requires the author to work primarily for personal
satisfaction-the reward must be found in a paraphrase of the words of
Dobereiner: "I love catalysis more than money."
This book provides another volume that surveys an emerging
process-the partial oxidation of methane-and provides coverage of
both basic and engineering aspects. This is entirely justified by the practi
cal nature of catalysis.
Burtron H. Davis
Preface
The editor of the Catalysis series, Dr. Burtron Davis, approached me
some time ago with a proposal to write a book on methane activation. This
is an active field in the area of catalysis and energy conversion, and,
although several review articles exist in the area, a comprehensive state-of
the-art book summarizing the latest research and economic status of
methane conversion has not been put forward. Although I have been
involved in research in this area since relatively early on, writing a book on
the subject was quite beyond what my time commitments permitted. As I
felt that a book in this subject was badly needed, I proposed instead to
edit a book to which the main researchers in the area would contribute.
Fortunately, the response from every coauthor that I approached was
positive and, moreover, all but one delivered.
The objective of the book is not to summarize again what is already
known from existing reviews, but to provide a comprehensive, in-depth
report of the latest available research or engineering results on the
conversion of methane via oxidative processes from each author's group.
The book focuses primarily on the oxidative coupling of methane because
this is the conversion route that has received the most attention, with one
chapter devoted to partial oxidation because it has been less studied.
Indirect conversion of methane is excluded because it is a mature subject
that is discussed in many articles, books, and textbooks.
The book is organized into two parts. The first deals with fundamental
aspects, consisting of chapters describing state-of-the-art work done in the
leading laboratories around the world, whereas the second part deals with
engineering aspects, including economic evaluations. The fundamental
portion contains descriptions of studies concerning the reaction mecha
nism, catalyst characterization and evaluation, and the latest techniques
used in such studies.
The engineering evaluation work is more restricted because it comes
from leading industrial researchers subject to publication restrictions. It
describes the engineering problems involved in the large-scale implemen
tation of the process, including reaction and reactor engineering as well as
economic evaluations of the process alternatives. The economic informa
tion is quite important because, due to proprietary restrictions, very little
is known in the open literature of the latest economic assessment of the
technology. Unfortunately, I was able to convince only a few authors from
industry to write about the economic and engineering assessments and
xi
